Allured Publishing Corporation Hair Care From Physiology To Formulation

Hair Care: From Physiology to Formulation
Cosmetics & Toiletries, the international magazine of cosmetic

technology, is the cosmetic and personal care industrys preferred
destination for the latest information on formulations, new
technologies, ingredients, testing and news. Cosmetics & Toiletries

is the first-read industry magazine for cosmetic chemists, R&D
management, and key to the development of new formulations
and product concepts.

Pulling from its most popular articles written by world-renowned
experts, Hair Care: From Physiology to Formulation delivers the same
quality and international appeal as the magazine.
This informative collection of articles covers a variety of topics

to create a solid foundation of knowledge about hair care in
cosmetics industry.
Topics include:
Physiology
Shampoo and conditioning
Ethnic hair care
Styling
Color
Sun protection
Hair Care Formulary
And more!
This informative collection provides professionals with invaluable

knowledge from well-known experts.
Rachel Chapman
Senior Editor, Cosmetics & Toiletries magazine
Allured Publishing Corporation

336 Gundersen Drive, Suite A
Carol Stream, IL 60188
www.allured.com/bookstore
books@allured.com
Phone: 630-653-2155
Fax: 630-653-2192
Hair Care Cover07_1_2.indd 1 10/5/07 2:08:27 PM

Hair Care:
From Physiology to Formulation
Hair_Front Matter.fcx.indd 1 9/15/07 12:51:44 AM

ISBN: 978-1-932633-35-1
Copyright 2008, by Allured Publishing Corporation. All Rights Reserved.

Editorial
Book Editor: Angela C. Kozlowski
Copy Editor: Jean Allured
Indexer: Joy Dean Lee
Designer: Jennifer J. Kauffman
Administration
Publisher: Marian S. Raney
Book Manager: Marie Kuta
Book Coordinator and Web Support: Anita Singh
Neither this book nor any part may be reproduced or transmitted in any form by any means,
electronic or mechanical, including photocopying, microfilming and recording, or by any
information storage retrieval system, without permission in writing from the publisher.
NOTICE
To the best of our knowledge the information in this book is accurate. However, in a time
of rapid change, it is difficult to ensure that all information provided is entirely accurate
and up-to-date. Therefore, the author and the publisher accept no responsibility for any
inaccuracies or omissions and specifically disclaim any liability, loss, or risk, personal or
otherwise, which is incurred as a consequence, directly or indirectly, of the use and/or
application of any of the contents of this book. Mention of trade names or commercial
products does not constitute endorsement or recommendation for use by the Publisher.

336 Gundersen Drive, Suite A, Carol Stream, IL 60188 USA
Tel: 630-653-2155 Fax: 630-653-2192
E-mail: books@allured.com
Hair_Front Matter.fcx.indd 2 9/18/07 9:28:06 AM

Table of Contents
Introduction ................................................................... I
Part I. Overview
Chapter 1. Hair Care Rides the Curl, Jeffries ..................................................... 1
Chapter 2. Happier Days for Hair Care?, Davies .............................................. 9
Chapter 3. Extending the Hair Care Line with Fragrance, Brewster .............. 15
Part II. Ethnic

Chapter 4. Global Hair Care Report: a Feel for Innovation, Jeffries ............... 23
Chapter 5. Debunking Ethnic Hair Care Myths, Doyle .................................. 29
Chapter 6. Maintaining Ethnic Hair Care Leverage:
an Interview with Patrick Obukowho, Obukowho . ................................ 35
Chapter 7. Meeting the Needs of African Hair Care:
an Interview with Chuck Warren, Warren . ............................................ 39
Chapter 8. Paradigm Shift for Indias Hair Care, Bhattacharya ...................... 43
Chapter 9. Asian Hair: Its Properties, Physiology, Protection and the
Market for Asian Hair Care, Rocafort et al. ............................................ 49
Chapter 10. Ethnic Hair and Disorders of the Scalp, Callender . .................... 61
PART III. Physiology

Chapter 11. Inside the Hair: an Advanced Hair Biology Model,
Schueller, Romanowski ............................................................................... 71
Chapter 12. Approaches to and Characterization of
Hair Growth, Westgate et al. . ................................................................... 81
Hair_TOC.fcx.indd 1 9/15/07 12:53:29 AM

Table of Contents Hair Care
PART IV. Shampoo

Chapter 13. Shampoo Formulation: The Basics, Klein . ................................... 93
Chapter 14. New Technology for Shampoos and Conditioners:
Between the Shock Waves, Westman ...................................................... 99
Chapter 15. Working Up a Lather, Vazquez . ................................................. 109
Chapter 16. Deposition from Conditioning Shampoo:
Optimizing Coacervate Formation, Lochhead et al. .............................. 115
Chapter 17. Advances in Polymers for
Hair Conditioning Shampoos, Lochhead, Huisinga .............................. 123
Chapter 18. Efficacy of Coal Tar vs. Sodium Shale Oil Sulfonate for
Treating Dandruff, Gayko et al. ............................................................. 137
Chapter 19. Esters from Vegetable Sources with
Care Effects for Hair, Morris et al. ........................................................ 155
Chapter 20. Silicone Technologies as Delivery Systems via
Physical Associations, Newton et al. ...................................................... 169
Chapter 21. Performance and Sensorial Benefits of
Cationic Guar in Hair Care Applications, Chiron ............................... 183
PART V. Condition
Chapter 22. Formulating Hair Conditioners: Hope and Hype!, Klein ......... 195
Chapter 23. Silicones for Hair Strengthening, Johnson et al. . ........................ 201
Chapter 24 Anionic/Cationic Complexes, OLenick ...................................... 211
Chapter 25. Anionic Organosilicones: Complexing Agents for
Quaternary Compounds, Vondruska et al. ............................................. 217
Chapter 26. Silicone Quaternary Microemulsion:
a Multifunctional Product for Hair Care, Ostergaard et al. .................. 231
Chapter 27. Using Polyquaternium-64 to
Condition Damaged Hair, Shimada et al. ............................................. 243
Chapter 28. Quaternium-91: a New, Multifunctional Hair
Conditioning Ingredient, Gao et al. ...................................................... 257

Hair Care Table of Contents
PART VI. Styling

Chapter 29. Innovations in Hair Styling Technology,
Schueller, Romanowski ............................................................................. 271
Chapter 30. Advances in Polymers for Hair Styling, Lochhead, Huisinga ...... 283
Chapter 31. Silicone Amino Elastomer Emulsion for
Conditioning and Styling Performance, Gomes et al. ........................... 297
Chapter 32. Designing Emulsions for Relaxer Actives, Obukowho ............... 311
Chapter 33. Styling Polymers in Mousses, Brewster ...................................... 317
Chapter 34. Evaluating Polyimide-1, a Styling Resin for
Gel and Mousse Formulations, Clements . ............................................ 327
Chapter 35. Antichaotropic Salts for Stabilizing Cysteine in
Permanent Waving Solutions, Shansky ................................................. 341
Chapter 36. Refractive Index Matching:
Principles and Cosmetic Applications, Sun et al. ................................. 347
Chapter 37. A New Dimension in Hair Styling:
VP/Methacrylamide/Vinyl Imidazole Copolymer, Wood et al. . .......... 361
PART VII. Color

Chapter 38. Dyeing to Get it Right, Mason ................................................... 375
Chapter 39. Forever YoungAntiaging Hair Care:
an Interview with Beth Johnson, Schaefer . ........................................... 383
Chapter 40. A Controllable Progressive Hair Dye Process, Shansky ............. 387
Chapter 41. Advances in Polymers for Hair Coloring, Lochhead . ................. 397
Chapter 42. Multilayer Lamella Vesicles in Oxidative Dye Formulations:
Characterization and Performance, Gao et al. ...................................... 413
PART VIII. Sun Protection

Chapter 43. Using Natural Keratin Biopolymers to
Protect the Hair, Roddick-Lanzilotta et al. ............................................ 433

Table of Contents Hair Care
Chapter 44. Protecting Against UV-Induced Degradation and

Enhancing Shine, Maillan et al. ............................................................ 447
Chapter 45. Polyamide 2: an Innovative Photoprotection Polymer for
Hair Care, Hessefort et al. ....................................................................... 459
PART IX. Testing

Chapter 46. Texture Analysis to Formulate Hair Care Products and
Select Packaging, Smewing, Jachowicz ................................................... 477
Chapter 47. Torsional Behavior of Human Hair by
Single Fiber Torsion Pendulum Method, Kamath ............................... 487
Chapter 48. In Vivo Quantitative Evaluation of Gloss, Clmenceau et al. ..... 493
Chapter 49. Effect of New Regulations on
Hair Coloring Products in the EU, Hefford ......................................... 503
Chapter 50. Using Texture Analysis to
Substantiate Hair Care Claims, Jachowicz, Smewing ............................ 511
Chapter 51. Recent Polymer Technologies for Hair Care, Brewster . ............ 527
PART X. Directory
Chapter 52. Hair Care Formulary .................................................................. 555
Index ......................................................................... 579

Introduction
For many, hair care simply means a visit to a professional stylist.
However, hair care is a multi-billion dollar world industry with a
growth potential that is astronomical. An incredibly diverse assort-
ment of opportunities and experiences are available in this industry,
with companies involved ranging from huge multi-national con-
glomerates to local neighborhood shops. Hair care products may
have advanced chemical components or the purest natural botani-
cals. It is a fascinating industry!
destination for the latest information on formulations, new technol-
ogies, ingredients, testing and news. Its sister publications, Perfumer
& Flavorist and Global Cosmetic Industry (GCI), are two of the most
respected resources for information in the perfumer and flavorist
and cosmetic industries.
Pulling from all three magazines most popular articles written
by world-renowned experts, Hair Care delivers the same quality and
international appeal as the magazines.
to create a solid foundation of knowledge about Hair Care in the
cosmetics industry.
Topics include:
Physiology
Ethnic hair care
Styling
Color
Sun protection
Hair Care Formulary
And more!
Hair_Intro.fcx.indd 1 9/15/07 12:53:49 AM

II
Introduction Hair Care
We hope you will find this compilation a thought-provoking

jump-off point for your future work.
Editors Note: Each chapter has been edited from its original publication for style
consistency, but otherwise remains mostly unchanged from its original publication in
Cosmetics & Toiletries, Perfumer & Flavorist or GCI magazine. Therefore some author
affiliations and/or company information may have changed. While the publisher has
attempted to note changes, we may have missed some and cannot accept liability for
inaccuracies or omissions. The original month, year and publication is noted at the end of
each chapter.
Hair_Intro.fcx.indd 2 9/15/07 12:53:49 AM

Chapter 1
Hair Care Rides the Curl

KEY WORDS: marketing statistics, shine, shampoo, conditioner, styling
products
ABSTRACT: Discussion of the global hair care market including categories
of products that thicken, strengthen, style, retain color,
straighten, smooth, control curl and frizz; niches such as
mens and childrens products; and the role of fragrance.
In the sixties, Broadway celebrated the glories of Hair, in Americas

first tribal love rock musical. Gimme a head with hair, long beauti
ful hair, shining, gleaming, steaming, flaxen, waxen. The root
of this celebration is supported by anthropological evidence that
braiding, ingenious accoutrements, botanical treatments coloring
and curling rituals have adorned the crowning glory across cultures
throughout history.
Today, research lends a hand to treatments that work with nature
to restore strength and elasticity, add volume, retain color, minimize
frizz and maximize style, and marketers are riding the curl on the
hair care markets lucrative wave.
Hair Care Categories Grow

The hair care sector has been wrought with fierce competition over
the last year, reports Euromonitor, as new products fill the shelves
and styling agents, colorants, multi-dimensional shine technology
and new interest in restoring tired, lifeless hair comes to the fore.
The flood of new interest in products grew the global hair care
market by 4.7%. The permanent and relaxer products segment got a
10.7% lift, yet colorants still owned 64.9% of the global hair market,
brightening its growth prospects and size by 5%.
Brilliant Brunette by John Frieda has introduced new life into
the market, giving brunette a revival where traditionally blonde
products held sway. Youth targeted brands, like Wellas ShockWaves
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2
Overview Hair Care Rides the Curl
for styling and Shaders & Toners in color have been supported by
elaborate campaigns. In the U.K., Boots chose another approach
with the extension of its Botanics range into colorants and opted for
a natural and healthy positioning with colorants containing plant
extracts claimed to be kinder to hair. Global hair care sub-sectors
exhibited healthy sales, and diverse product offerings for consumers
were strong.
Diverse Customer Base

Efficacy and a sophisticated market have impacted research and
development noted Anna Gripp, senior technical marketing man
ager, DSM Nutritional Products, Inc. She cited ready to wear hair,
fragrance and aromatherapy, and the quest for healthy looking,
manageable hair as consumer must-haves. Products with multi
functional properties also have impact. Manufacturers are targeting
specialized areassuch as the mens market, kids, culturally diverse
consumerswith products that thicken, style and condition, mois
turize, retain color, straighten, smooth, control curl and frizz.
There is also a trend to provide protection from environmental
factors like UV rays, thermal effects and VOCs (volatile organic
compounds). Paul Labrecques Colour Shampoo for color reten
tion and Labrecques Moisture Silk Daily Moisturizer Shampoo
with Seaweed Extract are among the options. Theres also Collec
tive Wellbeings color maintenance system with marigold, evening
primrose and antioxidants to prevent color fading and provide
sulfate-free, gentle cleansing.
Women want their hair to stay the color they intended it to be,
and color protection systems provide this support. Parsol SLX
(polysilicone-15), a product of DSM Nutritional Products, is a UV
filter that provides UV protection, utilizing liquid mineral technol
ogy to protect hair color, said Gripp. In addition to protecting hair
color from UV-induced degradation, Parsol SLX is said to enhance
combability and improve fragrance retention on hair in leave-on
formulations. The use of UV filters in formulations has gained
popularity and numerous formats contain them.
Gel products appear to provide more targeted application than
sprays, said Gripp, due to their ability to lift hair at the roots and

3
Jeffries Chapter 1
provide product where needed. Nioxins Smoothing Reflectives

Extra Hold Styling Gel is said to style and care for both hair and
scalp, while providing control and shine. Highlighting shampoos are
also popular, like Lancmes Hair Sensation Radiant Color Shampoo
and Conditioner to preserve color radiance and Paul Labrecque
Salons Spectrum multi-tonal highlighting.
As consumers do more to their hair, like using blow dryers and
heating appliances, they also create more damage, hence the growing
need for specialized care and the expectation that better products
will correct the problems. Vitamin enriched shampoos, like Pantene,
with vitamins B1 and B5 (Panthenol) add moisturizing plus hair
repair protection to their roster; and products providing shine and
luster are in the forefront.
Shine is actually the number one claim today, with consumers
wanting this benefit from hair products, said Gripp. Citr Shine
Fresh Fusion shampoos, from Schwarzkopf and Henkel, reportedly
nourish and protect with Citrus Vita Actives for colored or permed
hair. The ingredients blend multi-vitamins and strengthening
proteins, while adding moisture and shine. Shine Miracle, Anti-
Frizz Serum treats split ends and smoothes with vitamins, silicones
and UV protectant. For shine and hydration, there is Vitapointes
Lightweight Moisture Lock formula to protect, strengthen, smooth
cuticles to reduce damage and frizz, and add shine. It is also a de-
tangler and massage crme for hair.
Environmental stresses, pollution, UV rays and blow drying all
effect how hair performs and responds, said Gripp. Regardless of
the type of hair you have and the stresses it has endured, there is
awareness that products can treat and improve its condition.
Consumers are being taught how to work with what they have
and bring out their best. Theyre being educated by their stylists,
says Gripp. This has resulted in a variety of looks that have the goal
of healthy, shining, manageable hair at their core.
The same kind of fusion that occurs with foods is also seen in
hair products influenced by exotic ingredients and blends, indi
cated Gripp. Diverse tastes and interest in naturals and health
drive consumers choices in numerous marketsand hair care is
no exception.

4
Hair That Smells and Tastes Good

Smell and taste are two strong allures for consumers, and fruity florals
and tropical notes have retained popularity in hair care. Jeanine
Szweda, VP creative fragrance management consumer products,
North America, Givaudan, commented, In hair care, we continue
to see fruity floral notes that are comfortable and familiar. Floral
blends are an emerging trend that can be seen in Matrix Color
Smarta rich, full-bodied floraland in Alberto VO5 Nourishing
Oasis Revive and Shine with watery green top notes. Theres also a
trend to sparkling citrus blends with notes of mandarin, bergamot and
tangerine, which marry well with tropical notes like kiwi, papaya
and mango. Fresh and clean citrus and moisturizing fruity elements
are in Herbal Essences Citrus Lift.
Today, in hair, we see gourmand done in a variety of ways. John
Friedas Brilliant Brunette is a sophisticated gourmand, LOreal
Color Vive is a fresh, fruity gourmand and Bumble & Bumble
offers Crme de Coco with coconut and milk thistle, said Szweda.
At minimum, hair care fragrances need to reinforce the attributes
of clean, fresh and healthy hair, she added. This is consistent with
hair care products being good for your hair and providing fragrances
conveying that message.
Performance Improvement Strategies

When it comes time to develop new hair care products, a major
theme on the minds of formulators and marketers is performance
improvement. Providing products that deliver performance at a cost
that allows for competitive price points in the marketplace is a
key mission.
In todays environment where suppliers are continually being
asked to look at the bottom line, reduce costs and come up with
something better at lower costs, there is a need to develop the kind
of technologies that fit with the latest trends in product formulat
ing, said Penny Vanemon, director of marketing, National Starch
Personal Care. When the right technology is developed that enables
performance improvement at the right price, then chances are good
that a product will make it through to commercial development.

5
Jeffries Chapter 1
Accordingly, we have changed the way we look at technology

development over the past few years, said Vanemon.
National Starch Personal Cares newest ingredient, Celquat LS-50
polymer, is a targeted polymer that is designed to deliver improved
manageability performance in the areas of volume building for
straight hair and long-lasting definition of curly hair. Designed
for the hair mousse market, the styling ingredient is said to deliver
improved performance, while demonstrating its value to formulators
with cost considerations.
Improved performance is only valuable to hair care formulators
if it comes at a cost that allows a great deal of formulation flexibil
ity, said Vanemon. According to National Starch, Celquat LS-50
offers the hair industry a polymer that delivers improved manage
ability at a total polymer cost contribution as much as 40% lower
than industry benchmarks.
Vanemon says Celquat LS-50 provides a combination of volume
and conditioning benefits in styling mousse products, allowing for
mulators to satisfy customer needs. Across the hair styling market,
delivering conditioning benefits from styling systems is increasingly
common. Celquat LS-50 polymer is a patented technology that
can be used to deliver both volume and conditioning from a single
polymer ingredient, said Vanemon.
As the gel and mousse markets grow, new forms emerge. Gel
foams, aerosol mousses, color mousses and texturizers are all
designed to provide benefits like styling hold, hair repair, protection
and shine. Mousse moisturizing and styling is found in three prod
ucts from Condition 3-in-1. Formulated for all hair types, the line
includes Moisturizing Mousse, Extra Hold Mousse and Maximum
Hold Mousse. A small amount worked into towel-dried hair will
prepare the hair for styling. The line offers a Paba-free sunscreen,
plus pro-vitamin B5 for volume, shine and hold.
For curly hair definition, Paul Brown Hawaii has introduced a
ringlets curl enhancing trio, which includes shampoo, curl enhanc
ing conditioner and curl enhancing mist. Said to enhance curl
retention, the trio offers softness, shine, definition, strength and
smoothness. The shampoo contains oat kernel extract and kukui nut
lipids, while the rinse-off conditioner contains panthenol, Vitamin

6
E and coconut. Olive oil and kukui nut lipids are included for curls.
Schwarzkopf & Henkel launched Big Volume Styling Mousse from
Citr Shine designed for volume and conditioning with fresh fruit
fusions and Wound Up Curling Mousse to tame frizz, boost bounce
and add shine.
The Feel Good Factor

The feel of hair after rinsing and drying is an important performance
trait of mass market shampoo formulations, and conditioning effects
delivered by products often influence consumer purchasing deci
sions. While dimethicone is known to provide consumer-desirable
conditioning effects, said Dennis Fost, Business Development,
Uniquema, its use has been problematic because of the difficulties it
presents in remaining substantive on hair.
According to Uniqema, its Arlasilk Phospholipid series supports
formulating mildness and a greater reliance on the natural-based
products todays customers seek. Arlasilk Phospholipid PLN, a
water-soluble organosilicone that incorporates patented pyrrolidone
and phospholipid chemistry to increase polarity, is said to result
in a high level of substantivity and provide a highly functional
ingredient to build in a soft, silky after feel to opaque and clear for
mulations, according to Fost.
The Arlasilk Phospholipid series of bio-mimetic phospho
lipid complexes starts with nature and improves upon it to deliver
a range of formulation effects in skin and hair care products, and
each ingredient is derived from a specially selected vegetable oil and
modified to enhance its effectiveness in personal care formulations,
indicated Fost.
Supporting the trend toward naturally derived ingredients in
personal care, Uniqema also offers specialties that allow formulators
to include natural oils and actives into shampoo formulations, said
Craig Queen, rinse-off applications manager.
Formulators can rebuild consumer-desirable foam and viscosity
in clear and opaque systems with the Promidium series. Prom
idium 2 is ideal for solubilizing natural oils, actives and emollients,
serving as the effect enabler, while allowing for ideal rheology and

7
Jeffries Chapter 1
flow behavior of formulations. The series includes Promidium

LTS, said to offer viscosity building and rheology control applied to
thicken formulations. Promidium LTS offers five to 10 times the
viscosity building performance compared to liquid thickening
products currently on the market and a much higher degree of
control and predictability than traditional thickening approaches,
added Queen.
Hair Strengthening
Hair strength is a key selling point for consumers longing for or just
maintaining healthy hair. A new active by Croda called Keravis is a
hair strengthening protein designed to penetrate the cortex of the
hair to bind moisture as well as form a protective film on the out
side of the hair fiber to lubricate and reinforce the cuticle. The dual
action provides a complex said to be effective even in rinse-off systems.
In Crodas Flexabrasion Fatigue Lifetime Test, the strengthening
properties of Keravis were determined to improve the strength of
hair in different systems.
We compared it to the industry benchmark, D-Panthenol, and
proved that D-Panthenol did not significantly contribute to hairs
strength, whereas Keravis did in both a leave-on and wash-off
system, said a study by Croda.
Strengthening damaged hair and restoring health to dry hair
is the goal of the new Bio-Ionic Super-Hydrator series. With
chemical usage and changing climate exposure factors in dry, unman
ageable hair, Bio-Ionic introduced Super-Hydrator Intensive
Moisturizing Shampoo, Moisturizing Reconstructor and Super-
Hydrator Weightless Shine Sealer. With a blend of micro-milled
Japanese minerals delving into the cortex to accelerate absorption
of water molecules and keep them there during the repair process,
the areas of damage within the hair become filled in, resulting in a
smooth hair cuticle. Ingredients include hydrolyzed wheat and soy
proteins, Japanese green tea, ginger root, lotus flower and a hydrating
blend of avocado, apricot kernel and Vitamin E oils.
Across all ages, genders, cultures and ethnicities, there is consid
erable consumer interest in a vast array of hair care needs. Currently,

8
the craze for shine has prompted the proliferation of new products
promising to make your hair shimmer, and the marketers response
to these needs has injected new life into this mature market.
Nancy Jeffries, Contributing Editor

GCI, Carol Stream, IL USA
Published October 2005 GCI

Chapter 2
Happier Days for

Hair Care?
KEY WORDS: marketing statistics, international hair care market,
shampoo, conditioner, styling products
ABSTRACT: Discussion of the growth in the global mature hair care sector
led by shampoos, conditioners and styling products.
Growth of more than 4% in 2004 indicates that manufacturers

attempts at revival of the mature hair care sector are working. This
chapter discusses key trends from the last year both in the US
and globally.
Asia Pacific, Eastern Europe and Latin America

Outperform
Although Western Europe, Asia Pacific and North America
together account for more than 70% of sales in terms of value, man-
ufacturers with plans for global domination need to look outside of
these mature markets to realize the sectors full potential. Forecast
average annual growth of slightly more than 1% in Western Europe
and North America to 2010 is smaller in actual terms than that
predicted for Eastern Europe, Latin America and, especially, Asia
Pacific, where figures are buoyed by China and India. Manufacturers
keen to reignite growth should prioritize these markets.
Development in both Latin America and Eastern Europe since
2000 has been underpinned by the increased spending power of
working women. Economic recovery and awareness of global fash-
ion fads in Brazil and Russia also have helped create demand for
more sophisticated products. Asia Pacifics hair care performance
has, until recently, been underpinned by Japan. China and India,
however, are beginning to plug the gap filled by the low-growth
forecasts for Japan.

10
Overview Happier Days for Hair Care?
Brazil and China Boost Sales

Although Venezuela has been the most dynamic market in terms
of hair care sales over the last five years, Brazil, Russia, India and
China are the individual markets of distinctionwith dynamic
growth resulting in sizeable value gains. Looking forward to 2010,
Brazil and China are set to sustain current growth rates, with aver-
age annual growth of 8% and 12% respectively.
In Brazil, hair care accounts for more than 25% of the total cos-
metics and toiletries market, and has posted double digit growth for
the last five yearsin spite of relatively high penetration. This
is largely due to the attention that consumers pay to their hair.
Washing hair twice daily is not uncommon in Brazils humid cli-
mate. Given that basic products are accepted by the vast majority of
the population, manufacturers have stimulated demand by refining
segmentation strategies: demographic group, hair type and treat-
ment benefits.
s re-launch of Seda (Sunsfilk) findficates that the company
is employing a mega brand strategy, offering products for all hair
types, colors and seasons. Given that the aging population is at the
forefront of government concerns, with forecasts that the number
of Brazilians over the age of 70 will rise from 7.7 million in 2004 to
34.3 million in 2050, hair care manufacturers could prosper by tar-
getfing thfis group specfificallyas dfid wfith Sunsfilk Agfing
Care in Thailand.
Shampoo Staying Strong

The largest subsector within hair care is shampoo, with sales of
$14.8 billion in 2005. At a global level, it is evolving at a slightly
higher rate than hair care overall. In mature markets, the increased
penetration of highly sophisticated, technologically advanced
product formulations within the upper mass market segment
has been a key strategy. Several mainstream brandsincluding
Pantene, Clairol Herbal Essences and LOral Elsve/Elvive
increasingly offer premium attributes such as vitamins, sun
protection and aromatherapeutic qualities to push products higher
up the price platform.

11
Davies Chapter 2
Last year, the trend toward upper mass products was especially
evident in the Japanese market, where new shampoos such as
Fino from Shiseido, Asience from Kao and Resche from Kanebo
contributed to an increase in average unit prices. In the U.K.,
Alberto-Culver stole share from due to the roll-out of
its TRESemm brand in 2005. Enjoying high credibility among
consumers with its salon heritage, TRESemm struck a nerve in the
U.K. by offering what is perceived as premium hair care at afford-
able prices. Other professional hair care brands, including John
Frieda and Nicky Clarke, suffered in turn, and are expected to lose
value share in the future.
Already struggling with brand loyalty, the shampoo sector faces
more difficulties due to discounting and expanded availability
through supermarkets and other mass outlets. Budget and private
label formulations also have become more sophisticated, with con-
sumers increasingly able to spend less for more. In mature markets
manufacturers need to differentiate themselves to ensure that they
continue to win consumer loyalty in the face of ongoing price wars
between supermarkets, discounters and pharmacies.
Conditioners Captivates Consumers

The conditioner sector, with 9% growth globally, was the most
dynamic hair care subsector in 2005. The sales decline of two-in-
ones is fueling conditioners growth, and consumers preference for
separate products is becoming common even in emerging markets.
China is the largest global market for two-in-ones, but Chinese
consumers appear to be ditching the format in favor of conditioners.
This may be attributed to successful marketing by manufacturers
that convince consumers of the need to protect hair against colorants,
styling agents and daily pollutants. Manufacturers keen to seize the
share of sizeable growth forecast for India, already the fourth largest
market in the world, need to grasp local nuances.
Styling Agents Lost Their Stick

Once the darling of hair care, styling agents appear to be losing
their grip with less than 2% growth over the last year. The US,

12
Overview Happier Days for Hair Care?
Japan, France, Germany and the U.K., all large markets, have regis-
tered minimal growth since 2004. With a natural look in vogue and
shampoos increasingly taking on styling properties, the future of
styling products looks bleak.
Doves range of styling products, however, is a notable success
story. The range was launched in 2005 in the US, and rapidly seized
a 2% share of a market in which it had no presence. Its success can
be attributed to both its unique positioning and the extensive adver-
tising campaign that supported the launch. The campaign focused
on four female cartoon characters: Wilma from The Flintstones,
Marge from The Simpsons, Velma from Scooby Doo and Jane from
The Jetsonseach known for a particular, unchanging hairstyle.
The idea is that these women have been forever stuck in their styles,
which is a metaphor for real-world women whose use of traditional
styling products has left their hair stiff and sticky. The advertisements
show these characters with new, more appealing hairdos styled
wfith Dove products. Manufacturers could follow s lead by
attempting to create a need for such products even when fashion
trends say they are not in vogue.
Complacency Not an Option

While growth potential is high in the less mature regions, manufac-
turers must continue developing their product ranges in the US, the
U.K., France and Japan to keep a foothold in the global market. The
rising disposable income of tweens and teens is creating distinct
consumer segments in these countries.
Mens hair care also presents an area of opportunity that is
relatively untapped. The majority of mens hair care consists of
male-focused colorants to hide grey. However, this market is nearing
maturity. The majority of potential for growth lies with male-
focused shampoos, conditioners and styling products. For the most
part, male-specific shampoos and conditioners have yet to meet with
great success. There is a needs-based question here. Unlike deodor-
ants, where manufacturers have convinced men and women that
they need separate products, that division has not been established
with shampoos and conditioners. Were manufacturers to push to
convince men that unisex shampoos were not strong enough for

13
Davies Chapter 2
their hair, there might be greater segmentation and development of

a new category.
The Fall of the Mega Brand?

The expansion of hair care lines into a broader range of products
has been apparent over the last year with the rise of the mega
brand. Major players such as Shfisefido, Avon, and Procter
& Gamble chose to focus innovation on a handful of high-impact
brands. Brands have been split into new categories and extended
into different sectors to scoop up sales and broaden appeal among
a wider consumer base. The theory is that manufacturers can milk
broader industry trends and target new lucrative groups such as
ethnics, teens and tweens and grays while reinforcing brand equity.
In the US and Western Europe in particular, ethnic consumers
have become an important niche for mainstream manufacturers.
LOral has a Chicago-based center that does nothing but research
ethnic hair and skin, and P&Gs Pantene Pro-V has a complete
range of products for the ethnic consumer. Given the potential for
this segment, manufacturers cannot afford to ignore a lucrative
group. By professing expertise in Hispanic hair, straight hair, long
hair and so on, however, it remains to be seen whether these com-
panies run the risk of loosing credibility by overextending products
and their images.
Briony Davies, Contributing Editor

Published September 2006 GCI

Chapter 3
Extending the Hair Care

Line with Fragrance
KEY WORDS: fragrance evaluation, regional fragrance preferences,
fragrance consistency
ABSTRACT: Discussion of ethnic and geographic fragrance preferences
and the technical issues when formulating various hair care
products for scent consistency.
Unlike any other cosmetic product form that you apply to the body,
hair care products have to meet specific needs of specific consumers.
And those consumers know they have genuinely different needs,
says Annette Toms, the London-based professional hair care expert
with International Flavors and Fragrances (IFF).
Hair has to smell fresh and clean. Unfortunately the ingredients
in hair care products that make your hair look great do not smell
great. What delivers the fresh and clean message is the fragrance,
says Jayne Rodgers, New York-based global fragrance development
manager for hair care at IFF.
Thus, fragrance is essential in hair care products. But how can
it be selected to meet the differing needs of consumers in different
parts of the world and products that perform different functions on
the hair especially when the goal is to extend that fragrance across
a range of geographies and product types? This column looks at
work being done at IFF and at hair care product manufacturers to
extend a hair care fragrance across regions and products.
Geographic Extension
In April 2003, IFF and Anderson French Salons opened Anderson
French at IFF, a full-service hair salon in the IFF Building in
Manhattan at 533 West 57th Street.

16
Overview Extending the Hair Care Line with Fragrance
Traditionally, perfumers who created fragrances for hair care

applications had to evaluate them out of a bottle, diluted in water
or on swatches. But to create great fragrances for hair care products,
IFF believes that fragrance must be evaluated in-use on real heads
of hair. Having an on-site salon allows the perfumers to experiment
and get useful feedback on how the fragrance performs on wet hair,
during the drying process, and after styling.
During our year at Anderson French, we have made some
discoveries, all of which are now proprietary or confidential either
for our clients or for IFF, Rodgers said. But we have also looked
at the usage of hair care products in general and discovered how
they behave on different cultural hair types, such as Latino, Asian,
African American, or Caucasian. Experiencing those differences has
helped us to better understand fragrancing for a brand and key into
what type of fragrance notes are needed to support a brand benefit.
IFF has gone beyond the salon in its Texture Awareness Program
(TAP), which is led by Annette Toms. TAP is a sensory evaluation
performed by a specially trained salon technologist working in areas
such as Asia (Thailand) and Brazil (So Paulo and Recife) to under-
stand the emerging market needs from within those markets.
Our new approach in the TAP is were working with people in
real life conditions, looking at it from a realistic viewpoint, as well as
within a salon scene to make sure results in both settings correspond
to the results obtained in a controlled setting, Toms said.
Rodgers has accompanied Toms on TAP activities in Brazil. She
feels that the ultimate goal for a good hair fragrance is that it per-
forms the same on as many different types of hair as possible.
Manufacturers, if theyre selling global megabrands, desire to
have one fragrance profile for every single hair type out there. So
you must develop a fragrance that is going to smell, within a win-
dow of acceptability, the same on every single head, Rodgers said.
But weve learned that scalp odor can strongly affect fragrance
performance. What people of different cultures eat, the environ-
ment in which they live and even the temperature and the odor
of the water they use, can affect the way scalp odor is going to be
covered. Scalp odor is a very important factor and TAP taught
us that.

17
Brewster Chapter 3
There are regional differences in odor preferences. For example,

in the Philippines, highly fragrant hair is a part of beauty. Strong
hair fragrance residual that lasts for 24 hours would be desirable in
the Philippines, but in the United States, that kind of substantivity
would be way too much, according to Rodgers. To develop a good
hair care fragrance for a region, you must have a keen understanding
of 1) consumer odor preferences, 2) hair types and textures and 3)
the needs of a specific brand.
You cant take a single scent and expect it to perform the same
in every country, Rodgers believes. Years ago and somewhat still
today, the industry tried to globalize fragrances. But we now see the
trend clearly moving toward regional fragrances. When youre talking
about maximum hedonic preference, global is not the way to go, and
I dont think it is the trend of the future.
Product Extension
Product types also present unique technical challenges, when
attempting to extend a fragrance across a line of hair care products.
These challenges were discussed three years ago in C&T by Carrubba
et al.1 Their conclusion was that fragrancing various hair care prod-
ucts presents a different set of technical issues for each product type.
Garnier Fructis: Earlier this year LOral extended its Garnier
Fructis shampoo and conditioner line to include Fructis Style,
the brands first line of styling products in the United States.
Fructis Style consisting of five gels, a milk, two mousses and
four sprays is aimed at men and women aged 15 to 34.
The line is formulated with a fruit-based micro-wax tech-
nology using kernels of mango and apricot seeds to moisturize hair,
according to the company. It is scented with notes of lemon, lime
and green apple, with lemon fruit extract to add strength to hair
and enhance shine.2
Nourishing Oasis: In March, Alberto VO5 launched a new line
of restorative, heat-activated shampoos and conditioners called
Nourishing Oasis. The line includes shampoos and conditioners in
four scents. These scents contain 70-100 synthetic fragrance com-
pounds and are heat-activated to release top notes when the product
is combined with warm or hot water, according to the company.3

18
Nourishing Oasis shampoos and conditioners are designed to

nourish hair with rich, patented conditioning ingredients while they
nourish the soul with aromatherapy fragrances, said Shannon L.
McKenzie, research scientist in fragrance, at the Alberto-Culver
Company.
The fragrances are composed of 70-100 compounds to create an
overall fragrance effect that fits the product concept as well as to
provide optimal performance benefits, according to McKenzie.
These fragrance compounds can be classified into three catego-
ries based on their volatility. The most volatile compounds, known
as top notes, are what the consumer smells first. The heavier, less
volatile compounds (often referred to as middle and bottom notes)
help fragrances bloom in the shower, provide substantivity to hair
and help the smell to linger during and after use. Combined, these
top, mid and bottom notes create an overall fragrance experience for
the consumers using the products.
Noville Comments on Trends in Hair Care Fragrance

Trends in cologne and body products have a strong influence on hair
care fragrances. The salon and upscale products are especially sensitive to
these trends. We see tropical fruit notes in this category, apples taken to a
new level (apple cider) and bright sophisticated citruses, like grapefruit.
Mass hair care follows closely on the heels of the salon, doing blends of
fruits and citruses with floral, musky backgrounds, such as Fructis, FreshVive
and Herbal Essence Fruit Fusion. Occasionally one finds wood notes with a
retro balsamic feeling, but primarily the average hair care consumer loves
apples, melons and citruses.
Another strong influence in hair care is the burgeoning mens market.
LOral Vive for Men, which has a fruity topnote with citrus, green and
herbal notes, is gaining momentum. Fructis is simultaneously targeting male
and female consumers, as well as GenY in its ad campaigns. We know that
men are beginning to evolve as personal care consumers, and so will the
male factor in hair care fragrances.
Most shampoo and conditioner bases are easily fragranced. Style and
straightening products are a bit more challenging.
Betty Beighley, Senior Evaluator
Noville Inc, South Hackensack, New Jersey

19
Brewster Chapter 3
We designed each pair of shampoos and conditioners to have

the same fragrance, McKenzie said. These fragrances were devel-
oped in the shampoo base first because it is generally the more
difficult base to cover due to the stronger fatty, surfactant odor.
Once we identified the shampoo fragrance we experimented with
the same fragrance in the conditioner. We optimized the fragrance
level so it simultaneously complemented the shampoo while covering
the conditioner base odor.
McKenzie admits there could be a problem extending the line
while maintaining the fragrance. Although a fragrance used in a
shampoo typically works in a conditioner, this isnt always the case
in styling or treatment products, she said. These types of formulas
generally contain propellants and solvents that can be very difficult
to cover. If we wanted to carry these fragrances into other product
forms we would need to work with the fragrance houses to develop
appropriate modifications that would sufficiently cover the base as
well as suitably match the current shampoo/conditioner fragrances.
Flawless: Now appearing in your local Walgreens stores is
Ken Pavs celebrity hair care line called Flawless intended for use
on dry, damaged hair. It includes a shampoo, two conditioners and
five treatment and styling products. All of the products are formu-
lated with a strengthening complex consisting of wheat and soy
proteins, as well as polymers that lubricate and add shine, according
to company sources.4
The Flawless products reject synthetic fragrances in favor of
essential oils, both for benefits and for scent. The benefit ingredients
include rose and chamomile oils combined with burdock and ginseng
root extracts. The scent comes from a complex of essential oils from
lavender, geranium, orange, clementine and lemon.
Alec Batis is head of product development and marketing for
Pavs Products. He formulated and scented the line. Ken Pavs
is a hair stylist to celebrities such as Celine Dion, Jennifer Lopez
and Heather Locklear. They came together, the chemist and
the stylist.
We approached it from both angles, Batis said. I, as a chemist
wanted something that was very good for the hair. Ken wanted the
same, but the smell was very important because he gives this to all

20
his celebrity clientele, so it must not embarrass him. When the scent
is naturally based, its somehow more inviting. Ken liked that.
Also, essential oils are more nutrient giving, according to Batis.
So in spite of the fact that synthetic fragrances are cheaper and can
provide exactly the scent you want, Batis and Pavs chose to use
essential oils, even though they are very limited to what scents they
can achieve and marketers rule them out because of cost.
In this case, Ken didnt care about that, Batis said. He just
wanted the product to be as good as possible, and he wanted it to
have a point of difference.
Achieving the same scent from product to product in the line
was not easy. Usually, with other clients and working with synthetic
fragrances, Batis could just make adjustments in the concentrations.
But Flawless has no synthetics, so the only thing he could do is cull
out one or another of the essential oils in the complex.
It was much harder, especially in the conditioner and then the
shampoo, to achieve the scent; those bases were harder to cover. So
what we did was we pushed up the citruses more, Batis said. And
in the styling products, whose bases take the scent more easily, we
brought the citruses down and pumped up the lavender. The result
is that you dont get exactly the same scent throughout the whole
line, but you get sort of variations on a theme.
Batis recalls that extending the line presented the same challenge
when he was formulating skin care and hair care products at LOral.
And its the same for every brand. But you work with the fragrance
chemists and theyll adjust the scent according to the base to achieve
a similar scent. For instance, its very difficult to use the same fra-
grance formula when going from a moisturizer to a cleanser. So
the goal is to make them as close as possible. The scent is never the
same, of course, but you get it as close as possible so the consumer
feels that the two are similar. If this is a kiwi line, you definitely
want the consumer to think there is a kiwi smell in each product.
Another point of difference in the Flawless line is that its
products contain no sulfates. Instead, they use surfactants, such as
sarcosinates, that are gentler, especially on the scalp.
There was no goal to make Flawless an all natural line. Im a
chemist. Im not against chemistry, Batis said. The goal was to

21
Brewster Chapter 3
make a good product. That means some things were coming from
nature and some things were coming from chemistry. Both sulfates
and sarcosinates come from chemistry, but sarcosinates are better for
dry, damaged hair. Fragrance can be either synthetic or natural, but
we think essential oils are better for dry, damaged hair. So were not
against technology and chemistry. Were just picking and choosing
what we think will make a good product.
Conclusion
Extending the line in fragranced hair care products apparently runs
into barriers that are regional and technical. Overcoming these
barriers will take close cooperation between marketing, product
development, R&D and the fragrance house. The fragrance chemist
should be on the team early on.
References
1. P Carrubba, E Matson and E Carrubba, Fragrancing hair care products An overview,
Cosmet Toil 116(12) 73-76 (2001)
2. LOreal Garnier Fructis gets stylish with new entries, The Rose Sheet (Nov 24, 2003) p 5
3. Alberto VO5 offers Oasis for aromatherapy, conditioning hair care, The Rose Sheet (Nov
17, 2003) p 7
4. Ken Pavs celebrity hair care to bow exclusively in Walgreens, The Rose Sheet (Jan 5,
2004) p 3
Bud Brewster, Associate Editor

Cosmetics & Toiletries, Carol Stream, IL USA
Published May 2004 Cosmetics & Toiletries

Chapter 4
Global Hair Care Report:

a Feel for Innovation
KEY WORDS: marketing statistics, leave-in conditioners, shine, lipids,
silicones, polymers
ABSTRACT: Discussion of consumer demands for skin care benefits in
hair care products provided by ingredients such as silicones
and polymers.
As consumers search for products that make hair shiny, silky, clean,
soft, manageable and healthy, the emphasis on cleansing, condition-
ing and treatment has become more important than ever.
The global hair care market grossed $50.94 billion in 2005,
according to Euromonitor. Growth will continue to result from an
emphasis on product development, as manufacturers strive to offer
consumers sophisticated value-added products. Antiaging, anti-
pollution and sun-protective products will enjoy higher levels of
penetration, as skin care benefits are increasingly incorporated into
hair care products, according to Euromonitor. Color maintenance,
vitamin and protein-enriched products, diverse needs and male-
specific hair care segments also will continue to make gains.
Consumers Looking For Benefits

Today, men and women are increasingly looking at the products
benefits while perusing retail store and salon shelves. The need for
these benefits is challenging formulators to new scientific break-
throughs and the use of innovative combinations of ingredients.
Ingredient suppliers are meeting the demands of the market-
place with new product offerings. According to Erik Gyzen, Dow
Cornings major market strategy leader for hair care, the company
is offering six new silicone-based formulations for leave-in condi-

24
Ethnic Global Hair Care Report: a Feel for Innovation
tioners, developed at its research and development laboratory in

Shanghai, China. The company says leave-in conditioners help to
restore moisture in the hair and minimize damage caused by exter-
nal factors. Silicones, a major focus of todays treatment materials,
improve conditioners by providing shine, split-end repair, silky
conditioning effects and moisture retention.
In Asia, a womans beauty starts with the appearance of her
hair. It needs to be shiny, soft, silky and healthy looking, said Vince
Ungvary, marketing director, Dow Corning Personal Care, Asia.
This need can be met by leave-in conditioners, one of the fastest-
growing segments of the global hair care market.
Combining Lipids and Silicones

According to the company, Dow Corning natural lipids are stabil
ized against oxidation so they can be formulated with silicones to
improve the feel of hair and skin products. The lipids line is the result
of an alliance with International Cosmetic Science Centre (ICSC), a
research and development center and supplier of high-quality natural
ingredients to the cosmetic industry. Dow Corning stated its lipids,
rich in fatty acids, are good moisturizers and hair conditioners, espe-
cially for ethnic hair care products, and can restore the skins barrier
function. They can be used in combination with silicones, which are
good emollients that improve the feel of formulations to create prod-
ucts with low film residue, greasiness and tackiness.
Incorporating natural lipids in formulations had been difficult
because of their inherent oxidative instability, especially for lipids
with a high content of essential fatty acids. Rosemary extract has
been found to stabilize the lipids against oxidation. To deliver these
lipids in concentrated emulsions combined with silicones provides
additional benefits for the cosmetic formulator, said Gyzen. Rep-
licating practices that have been used for centuries, Dow Cornings
lipids are naturally derived from plant seeds, fruit nuts or kernels,
mango, kokum, black currant, evening primrose, borage, camelina
and shea, which are sourced from such locations as India, Pakistan,
East Africa, Mexico, Central America and China.
Dow Corning also offers a thickening agent called Dow Corning
RM 2051, which is a ready-to-use polymer in a silicone base that

25
Jeffries Chapter 4
thickens and emulsifies a wide variety of oils in water-based formu-

lations while imparting recognized silicone properties. This product
is designed for leave-on hair conditioners and hair styling products.
It contains trideceth-6, an inverting agent that helps bring the
polymer into contact with the aqueous solution of a formulation.
When the emulsion is added to water, the polymer expands imme-
diately into the water phase to thicken and stabilize the formulation.
As the formulation thickens, the oil phase ingredients are emulsified
and stabilized, said Gyzen.
Filling the Niches in Hair Care

When science and sales combine in the marketplace, the results can
be impressive. New products that fill niches also place an important
emphasis on building relationships with customers and point-of-sale
purveyors. The products benefits and presentation are among the
key points that support todays marketing efforts.
Marketing continues to retain an important place in the determi-
nation of hair care product development. For example, a consumer
poll sponsored by National Starch Personal Care showed that
43 percent of all women surveyed in the US find hair volume to
be important. Among the respondents who believe volume to be
important, more than 80 percent want to increase volume, said
Kathy Maurer, hair care marketing manager, National Starch Per-
sonal Care. This survey provides clarity on the types of consumers
in search of better volume and the types of products consumers are
relying on to obtain it.
Women tend to rely on shampoo, conditioners and mousse for
volume while men rely substantially on shampoo and gel to obtain
hair volume, Maurer added. With this detail in hand we looked
at our own technologies to determine if we could improve upon the
offerings already in the marketplace. National Starch unveiled the
Art of Volume formulating kit in May 2006, featuring some of its
technology and formulating expertise within a system of prototypes.
The offering represented by the Art of Volume responds to the
needs of consumer product companies facing increased pressure
to commercialize high performing, consumer-pleasing products
quickly, Maurer said. We packaged several areas of our expertise to

26
give our customers everything they need to get off to a fast start in
creating winning volumizing products.
Science and Ceramides

While marketing and innovative formulation are part and parcel of
product development, there are some new and interesting products
on the market today that reflect the synergy of science and consumer
need across the country. The Matrix Biolage Fortethrapie range, a
professional hair care brand, includes ceramide, silicones and con-
ditioning polymers to protect against heat damage, condition, and
close the cuticle to control frizz and add shine.
Dow Corning brand silicones have been designed to provide
heat protection. The materials produce protective films that help
prevent water loss, which is critical to avoiding cuticle breaks and
cracks. At the same time, according to the company, these silicones
contribute to improved sensory characteristics such as softness, easy
combing and shine. Thermogravimetric (TGA) analyses show a
range of silicones helps prevent moisture loss when hair is subjected
to heat. According to the company, the 5-7070 Si Amino Elastomer
Emulsion offers conditioning, good fixative strength, positive aesthe
tics and a natural look from one ingredient.
This approach provides a solution to a common formulating
challenge: a number of polymers currently used for styling benefits
have poor sensory properties and impart an unnatural look to hair.
This one was designed for hair styling applications such as mousses
and hair sprays, as well as leave-on and rinse-off conditioners, and
shampoos. Delivered in emulsion form, the material allows easy
addition and mixing in aqueous-based formulations, said Gyzen.
Synergistic effects occur with the silicone emulsion in combination
with other styling polymers, allowing blends that suggest versatility
for formulating or extending the range of products developed for
specific market needs.
Products for Shine, Gloss, Sculpting and

Straightening
Product performance is a top priority in hair care. With superior
shine being among the most highly sought attributes for hair today,

27
Jeffries Chapter 4
high performance ingredients have taken center stage. Dow Corning

2-2078 Fluid is a silicone copolymer with both amino and phenyl
functionality. Its amino functionality is said to enhance deposition
and substantivity on hair, particularly damaged hair, while its phenyl
functionality provides superior shine. According to the company,
the liquid silicone resin also enhances straightening while providing
heat and color protection. The properties of this material suggest a
range of benefits for ethnic hair care products, and have the ability to
aid in straightening and protecting hair that is typically drier, curlier
and more fragile, thus allowing formulators to create products that
meet the specialized requirements of global markets, said Beth
Johnson, global hair care technology leader, Dow Corning.
For example, Frdric Fekkai introduced Fekkai Glosing Sheer
Shine Mist, which includes shine-reflecting olive oil extract and
an exclusive blend of sheer silicones to impart brilliant and long-
lasting shine, while helping to lock in moisture and keep strands
soft and conditioned.
PureOlogy recently introduced an Anti-Fade Complex Glossing
Mist with a blend of silicone technology, including panthenol,
wheat amino acids and soy proteins, while utilizing a nanotechnology
approach to color and thermal protection.
Repairing, Styling and Texturizing

Consumers crave shiny, healthy and manageable hair; therefore the
use of distinctive hair styling polymers for a variety of applications
has grown. Customers formulate these products into pump and
aerosol sprays, gels, mousses, putties, muds and pomades, among
others, and each hair styling polymer is formulated to provide a
different benefit, said Dierdre Crowley, market manager, Rohm and
Haas Personal Care, North America. Rohm and Haas polymers are
durable and not brittle to help reduce flaking, according to the com-
pany. We understand how water reacts with these polymer films,
so we can design our polymers to have excellent humidity resistance
and improve all-day hold; and while we dont supply silicone-based
materials, we do have products that allow formulators to easily
suspend silicones in hair care products, said Crowley. While the
consumer wont feel or see the hair spray in the hair, they get all-day

28
hold because the film was designed to be very strong and flexible so
it wont break easilywhich is exactly what happens when a product
stops holding the hairthe polymer breaks. Its hair science in plain
terms, but you need to understand polymers if youre going to make
an effective product those consumers want.
Rohm and Haas noted both the DHR and 180 products were
developed with the trend to reduce VOC emissions in mind. Both
work in 55 percent VOC or 80 percent VOC pump and aerosol
sprays, an important element not only to meet regulatory require-
ments in some countries, but for customers who are looking at
various aspects related to the sustainability profile of their products.
Clearly, products today display the scientific skill and nimbleness
of innovative formulators seeking to serve a diverse and educated
consumer base. As consumers learn more about ingredients and
the interplay between science, aesthetics and execution continue,
both marketers and formulators will need to remain dexterous and
articulate about their products capabilities.
Nancy Jeffries, Contributing Editor


Chapter 5
Debunking Ethnic Hair

Care Myths
KEY WORDS: marketing statistics, product line extensions, UV protection
ABSTRACT: Discussion of innovative ethnic hair care products including
general-use brand extensions that have been developed to
provide consumer-desired functions.
For a long time, the ethnic hair care market seemed to have worked
itself into a rut. Many products were harsh, leaving the hair with
unfortunate side effects, including dandruff, dryness and frizz;
conditioning and softness benefits were at a minimum; and, the
assumption was that non-Caucasians were most likely to purchase
ethnic-specific brands first.
The tides are rapidly turning, however. Increased market explora-
tion and R&D have led to a wave of new ethnic hair care products
that deliver on function claims and meet the ever-changing needs
of the consumer. Moreover, according to market researcher Pack-
aged Facts, developments in this market may be what keeps the
US$7.6 billion US hair care market, down nearly US$300 million
from 2003, from declining even further.
Different Demographics
As America grows more diverse, the countrys demographics are
undergoing significant changes. Currently, while 74% of Americans
are Caucasian, that figure is slated to drop to about 53% by 2050,
according to census bureau projections. The influx of minorities-
turning-majorities has meant big business for health and beauty
care companies, as the spending power of US Asians, Hispanics and
African-Americans reached US$1.9 trillion in 2003, according to
Packaged Facts. However, the firm also found that, contrary to pop-

30
Ethnic Debunking Ethnic Hair Care Myths
uflar beflfief, generafl-use brands, such as s Suave shampoo,

are top choices among ethnic consumers, rather than ethnic-specific
products. Companies will need to extend mainstream product lines
to attract ethnic consumers, said Don Montuori, acquisitions editor,
Packaged Facts.
One brand finding success with such tactics is Pantene, one of
the star lines from global personal care giant Procter & Gamble.
Every year, we conduct research among thousands of women to
understand their needs, wants, habits and practices. We identified
that moisture was the number-one need for women of color, so
we developed a proprietary moisturizing system in our Pantene
Pro-V Relaxed & Natural line that utilizes petrolatum, a natural
moisturizing ingredient recommended by dermatologists as best for
moisturization, said Christina Matthews, spokesperson, Procter &
Gamble, Ethnic Hair Care. The petrolatum in the shampoos has
been formulated to provide moisturizing benefits while leaving the
hair free from being weighed down.
Other companies formulate products to be effective for all hair
types. Paul Brown Hawaii products are researched and formulated
by company owner Brown and his team of stylists to work with the
varying hair types of multinational and multiethnic peoples who
live on and visit the Hawaiian islands. New Hapuna Paul Brown
Forme is a creamy paste that combines the best qualities of a wax
and a gel that molds and holds almost every style, yet feels light
and looks natural in any hair texture, said Brown. Plus, natural
antioxidants and sunscreens help protect against color fading from
UVA/UVB rays.
Shedding Some Light

In the past, it was believed that the hair of people of African
descent was not susceptible to UVB damage due to the high content
of melanin in the hair, said Patrick Obukowho, executive program
manager, Ethnic Product Development, Croda. But this is no
longer true if hair is relaxed or chemically processed. Indeed, as
more research and development has been conducted, the assump-
tions about ethnic hair are slowly becoming reversed, thus driving

31
Doyle Chapter 5
the need for new formulations. Croda now offers Crodasorb UV-HPP
(hair protein protector), a polyester polyquat that will absorb
damaging UVB light. With the addition of Crodasorb UV-HPP to
a formula, the product is quaternized and very substantive, so it will
stay on to protect the hair, explained Obukowho. Other products
on the market are not quaternized, which means they can easily
rinse off.
Revlon Professional Realistic, one of Colomer USAs flagship
brands, addresses the need for UVB protection in its Color Pro-
tection No-Lye No-Mix Relaxer. According to the company, the
ultra-gentle formulation protects hair that has been both relaxed
and color-treated, and prevents UVB damage as well. In addition,
the product provides the often-needed conditioning and moisturiza-
tion benefits.
Style and Substance

Not only is African-American hair vulnerable to UVB damage,
it has its own set of challenges for consumers and formulators
alike. For the most part, people of African descent tend to have
sometimes-coarse hair that tends to dry out and is susceptible to
breakage, noted Obukowho. However, as trends change from year
to year, so do hairstyles and the consumers expectations of hair
product offerings. Consumers continue to want more choices and
products that meet their specific hair needs, explained Matthews.
As a result, formulators have launched a variety of options to
keep in step with current and future trends. Current trends are
pretty much moving in the direction of ingredients for mainte-
nance products because of the harshness of relaxers, Obukowho
added. A lot of companies look for raw materials that make
some kinds of improvements in quality. Croda has also recently
launched Crodazolsoft DBQ, a conditioning quat specially
designed to provide softness. The quat is self-emulsifying in the
presence of synthetic or natural oils and water and also allows for
the deposition of vitamin E into the hair and scalp.
Both contract manufacturers and marketers are responding in
kind as consumers seek both styling flexibility and relief from dry

32
Ethnic Debunking Ethnic Hair Care Myths
hair and frizz. Raani Corp. now offers No Mix/No Lye Relaxer
Systems and Intensive Hair Treatment Conditioners designed to
provide maximum protection for ethnic hair.
Colomer USAs African Pride brand launched Multi-Length
Texturizer, a product designed to promote volume, body and
shine after only 10 minutes of use. The kit also contains texturizer
cream, neutralizing shampoo and a leave-in conditioner. Likewise,
the companys Lottabody brand released the Tress Tranzitions line
of products formulated to smooth and tame frizz while leaving
hair conditioned and shiny. Flexibility in styling is what everyone
desires and our new Tress Tranzitions line provides the versatility
to wear your hair how you want, when you want, without flyaways
and frizz, said Patricia Grant Williams, technical and artistic
director, Colomer USAs Multicultural Group. This simple but
effective chemical-free system allows for beautiful styling trans-
formations from curly to straight hairor the reversewith
minimum care.
Keep it Natural
As natural and organic ingredients have been on the rise in all areas
of personal care, ethnic hair care has been no exception. [Brands]
shouldnt abandon niche positioning, such as developing more natu-
ral product lines for African-Americans that are not reliant on harsh
chemicals, noted Montuori. Luster Products, Inc.s Pink brand
launched the Smooth Touch line, a relaxer and maintenance system
that features tea tree oil to relieve dry scalp and restore softness
to the hair. Additionally, now available from Arum is Cherimoya
Drops, a lightweight conditioning and moisturizing lotion for the
hair, skin and scalp. The product contains concentrated silk and is
fortified with botanicals and vitamin E.
As consumers begin to expect more from their ethnic hair care
products, the challenge is up to formulators and marketers to launch
products that deliver on promise. A lot of people will say, Yes,
this product will provide anti-breakage and give you long-lasting
conditioning, or, This product will impact sheen. All of these are
very good claims, but then again, do they work? asked Obukowho.
It goes back to the work of the chemist who built the formula.

33
Doyle Chapter 5
The knowledge of all the ingredients, plus the knowledge of the

active ingredient and how all of these come together in a formula to
impact the desired function is very important.
Lisa Doyle, Contributing Editor

Published June 2006 GCI

Chapter 6
Maintaining Ethnic
Hair Care Leverage: an
Interview with Patrick
Obukowho
KEY WORDS: raw materials, conditioners, moisturizers, relaxers, melanin
ABSTRACT: Discussion of future of ethnic hair care products including
broad scope of ethnic differences requiring different
products.
Shifting Gears
According to Croda Inc.s Executive Program Manager-Ethnic Prod
uct Development Patrick Obukowho, ethnic hair care in the past
centered on the chemical treatment arena. I believe now [the hair
industry] is going to shift their focus, stated Obukowho in a C&T
interview. The area targeted for rapid growth and high-demand:
maintenance products such as conditioners and moisturizers. The
market is endless since most consumers damage their hair chemically
via perms, relaxers or coloring.
Raw material suppliers, like Croda, will funnel more and more
financial and technical resources betting on creating advances in
raw materials to meet the specific needs of problem areas. Croda
has already formulated products that improve hair strength (as a
conditioning agent), minimize tensile strength damage and have
created molecules to improve the hydrophobicity of hair.
In addition, the industry will dictate the need for multifunction
al novel raw materials that are extremely user-friendly, such as esters,
which improve the condition of hair. We need breakthroughs in quater-
nary, conditioning or protein-derived compounds, said Obukowho.

36
Ethnic Maintaining Ethnic Hair Care Leverage
Relaxing is Irritating
What about nonirritating relaxers? Wishful thinking, he said. A
more realistic approach to the problem is to create a relaxer with the
function to reduce the scalp irritation discomfort during the process.
But to completely eliminate the irritation doesnt equate as the
high chemical pH balance (12-13.5much higher than skins 5-6
pH) coupled with the very aggressive active ingredients they contain
seem to make that goal an impossibility. A nonirritating relaxer is a
something people wish to achieve. Nothing more, he said.
Genetic Clues
But the biggest research misconception within the ethnic niche deals
with the generalization that the term ethnic can be used broadly
and interchangeably. Ethnic hair embraces a large scope of people
comprising different genetics. That differing background allows hair
to behave differently and positions the hair to behave differently.
Dollar Power
The African-American consumer wields an incredible amount of
purchasing power; however, the supply doesnt seem to equal the demand.
Hair type, inherent dryness and chemical and mechanical damage create
significant demands for hair care products to address those niche needs.
African-Americans spend an estimated US$1.7 billion on ethnic and
general market hair care products and account for 30% of all hair care
product purchases. The majority, 70-80%, utilize chemical relaxers followed
by moisturizing products. Efficacy seems to be the make-or-break factor
regarding product purchases.
African-American women specifically represent a powerful consumer
group. It is expected that their spending will increase 32% to US$342
billion in 2006.The average annual expenditures by African Americans on
health and beauty aids are 11.2% higher than all races and are estimated at
around $6 billion.
Population growth projections (37.5 million by 2010) coupled with
increased spending power from US$645.9 billion in 2002 to US$852.8
billion by 2007 suggest this market will soar.
Source: Hunter-Miller Group

37
Obukowho Chapter 6
There are people of pure African descent who have very straight
hairno kinks, no coils. People of African origin with mixed blood
tend to have hair, thick with intense coils. Others have very little
sulfur content, said Obukowho.
The tighter the coils, the more difficult the sebum distribution
will be, i.e., the more hydrophilic and the less protection the hair
possesses. Genetics also determine the type of sulfide bonds
which determine hair strength/resiliencyuseful knowledge
for formulators.
Location, Location, Location

Obukowho, whos traveled the world conducting research, stressed
geographys role in the equation of successful formulation. Hair will
differ from region to region, said Obukowho.
Although there might be an assumption that people residing
in climates with year-round sunshine would be fraught with UVB
damage, thats not always the case. Just as skin melanin will be
modified on people living with more continual sun exposure, so it
works with the hair. Melanin is across-the-board in peoples skin;
but the environmental component of sun activates the growth of
the melanin.
In Closing
Although many have seen a dip in the ethnic market potential,
breakthroughs are on the horizon. Very little research and new
developments were made in the last 40 years. Theres a serious
need to encourage new research, to encourage the innovation of raw
materials and to encourage new formulations, said Obukowho.
Patrick Obukowho, Executive Program Manager-Ethnic

Product Development
Croda Inc., East Yorkshire, UK
Published February 2002 Cosmetics & Toiletries

Chapter 7
Meeting the Needs of

African Hair: an interview
with Chuck Warren
KEY WORDS: hair texture softener, sunflower oil
ABSTRACT: Discussion of the evolution of a product from physiology,
market research and formulation, to use instructions.
Chuck Warren, senior director of research and development for

Culver Business Units has been involved with hair care for 25 years.
He began to work on Culvers Pro-Line International after realizing
how few products there were on the market for individuals with pre-
dominantly African hair. When developing the Just for Me Texture
Softener, Warren kept this targeted group of consumers in mind,
but shifted the focus to a traditionally underserved group, children
with predominantly African hair. Since it primarily was the mothers
choosing and applying products to their childrens hair, the company
interviewed them, asking what features they were looked for in hair
treatment products for their child.
Predominantly African hair is not one specific classification of
hair but rather any mixture of hair types where African hair char-
acteristics are most dominant, according to Warren. Unlike Asian
or European hair types, African hair is typically very curly or kinky
and is more elliptical in shape. Because of the curly or kinky pattern,
African hair is more susceptible to tangling and breaking than other
hair types. The bonding pattern of African hair is tight, consisting
of hydrogen and polypeptides; therefore, African hair is more coiled
and susceptible to damage. Researchers discovered that parents of
children with African hair desired products without harsh chemicals

40
Ethnic Meeting the Needs of African Hair
that were easily applied to and removed from the hair, and products
that provided moisture to make their childrens hair more manageable.
Warren focused on creating products to address the specific
needs of not only just African hair but also multiethnic or multi-
racial children with predominantly African hair. He observed that
multiracial hair was becoming more balanced, meaning more equal
in percentages of hair types. You cant get a comb through [multi-
ethnic hair] yet it is not coarse enough to leave it in a natural state.
It can be frustrating to the mom, said Warren. He added that,
although the parents of children with this type of hair do not want
to straighten their childrens hair completely, they want to make it
curly or wavy so that it is manageable.
Warrens solution was to find a balance of oils and creams to
produce a product that could be combed through hair rather easily
while maintaining its consistency. In addition, the formula needed
to provide moisturization. He took all of these requirements into
account when he chose the main ingredient in the hair texture
softener: sunflower oil. According to Warren, sunflower oil (INCI:
Helianthus annuus (sunflower) seed oil) often is used in the formula-
tion of black hair care products for its relatively easy distribution in
the hair. There are only two oils that are easy enough to distribute
in African hairjojoba and sunflower, said Warren.
A large percentage of oils are incorporated into the hair texture
softener. In addition to sunflower oil, safflower, soybean, corn and
meadowfoam oils are formulated in the antibreakage product. Its
a blend of well-chosen oils that are light, but still oils. When you
mix the oils with the cream, they have to mix easily and lightly,
said Warren.
Excessive oil allowed the mixture to spread more easily, a char-
acteristic that Warren found beneficial both to mothers applying
the product and the children themselves. The excess oil allows the
product to be spread out easily and uniformly. One of the concerns
is that the children do not like to have the product on their hair for
a very long period of time. Just as this product is easy to use, its easy
to remove, said Warren.
The sunflower oil is only one of the three components of the
texture softener; the others being an activator and a cream. The pet-

41
Warren Chapter 7
rolatum in the softener cream is the ingredient that holds together

the water and oil emulsion. One of the most unique elements of the
texture softener, according to Warren, is the ability to use it imme-
diately after the three components are mixed together, shortening
the length of time that children have to wait.
By addressing the concerns of children and parents, Warren
believes that the texture softener successfully treats children with
predominantly African hair. According to Warren, the gentle no-lye
ingredients make the product easy and effective to use on children.
We want to manage their hair, not chemically treat it.
Chuck Warren, Senior Director

R&DCulver Business Units for Alberto Culver
Published September 2006 Cosmetics & Toiletries

Chapter 8
Paradigm Shift for Indias

Hair Care
KEY WORDS: marketing statistics, consumer behavior, hair oils, shampoos,
conditioners, coloring products
ABSTRACT: Discussion of consumer behavior changes in Indias hair care
industry as well as recent growth in product categories such
as shampoos, conditioners and coloring products.
With a growth rate curving upward, the hair care market in India
is going through a major paradigm shift. With consumers ready to
experiment with new products and services and marketers churning
out new products at an impressive rate, there is a sense of excitement
in the industry. The potential is such that major Indian manufactur
ers are now relaunching hair care brands that did not survive in
earlier market scenarios.
According to a recent study by AC Nielsen Global Services, the
Indian hair care market has shown a growth of 3.8% over the previ
ous year. While the numbers may not look impressive at first glance,
they are positive compared to earlier market growth trends and the
industry is excited about this change.
The change is visible at two levelsconsumer behavior and
marketers trying to grow the market by introducing new product
categories and services.
What was once considered to be an occasion-linked beauty regi
men has now become a consumer way of life. The traditional hair
care and styling methods are changing, which means that buyers are
now ready to accept newer product categories. With globalization
and greater purchasing power, the consumers are willing to pick up
higher-priced brands. There is an increase of awareness amongst
Indian women about hair care, said Samantha Kochhar, hair expert

44
Ethnic Paradigm Shift for Indias Hair Care
and trainer, Pivot Point India. While hair colors as a market has
matured, slowly we are seeing a demand for hair styling and care
products from the consumers. There are still more female buyers
than male buyers. The companies also are launching separate mens
hair care ranges, but that still has to mature.
This also shows that there is a deeper market penetration. The
aspiration value has increased beyond consumers in the tier one/
urban markets across the cities. Consumers in the tier two and tier
three markets, including those in rural areas, also are demanding
more and new products.
At the second level, marketers are trying to sell the items more as
a benefit proposition rather than just as cosmetic product. They also
are trying to increase awareness among consumers through creative
marketing strategies. Some of the marketers are, in fact, going for
a try-before-you-buy method to educate the consumers about the
products. While existing marketers are changing their marketing
strategies, there are newer international players who are looking to
establish business in India.
Changing Consumer Behavior

Traditionally, Indian women have been very nonexperimental with
hair care and hairstyling. Most preferred to go for conventional
methods, using oil to condition hair, henna to color it and shikakai
powder or soaps to wash hair. Other than this routine, most of them
did not use any hair styling or care products.
But since 2000, the usage pattern has been changing, resulting in
an impressive growth for the hair care industry. There is increased
awareness among all levels of consumersfrom the elite buyers
to lowerincome customers. Male consumers also have evolved as
a category, and products are being introduced to meet the specific
needs of men.
The purchasing power of women has improved, and they now
are willing to spend more on personal groomingwith hair care
taking precedence. In addition, with more available global fashions
and trends, women consumers also are ready to try out new hair
styles and colors.

45
Bhattacharya Chapter 8
The Indian women today are much more up-to-date about

trends, and do appreciate good service, said Smira Bakshi, business
manager, Kerastase Paris, LOral India. In fact, our studies show
that they are also more willing to pay for good service and are ready
to accept the latest hair treatments.
Over the last year, there is an increased demand for aspirational
products. Women are willing to pay a higher priceparticularly
urban customers in tier one markets across Indias five major met
ropolitan areas. Our clientele prefers to spend some extra money
to buy international brands, said Dharmendra Khanna, business
manager, Kunchalsa leading beauty retail outlet in Delhi. And
there is strong demand for high-end hair styling products like Tigi.
They even demand brands like Paul Mitchell and Vidal Sassoon.
They can pay as much as 1,200 rupees for a shampoo.
Men are fast emerging as a separate consumer category in a
market traditionally dominated by women. The change in the buy
ing pattern includes men looking for care and styling products that
cater to their specific needs. This has led to marketers launching
SKUs specific to male buyers needsShwarzkopf s BC men
hair therapy range of products, for example, has been designed
for men. Similarly, styling gel brands such as Brylcreem, Marico
Industries Parachute After Shower Hair Cream and Set Wet
Hair Gel by Paras Industries all target the men with male-specific
advertisements.
In addition, consumers in rural areas are buying products further
up the value chain. Market research done to gauge the consumer-
buying pattern in rural areas showed that only one Indian state had
25% penetration in 2000.
Hair Cosmetics Market

The Indian hair cosmetics market, which includes both hair care
and hair styling products, has a unique characteristic. This is one
segment where the traditional hair treatments sell as much as newer
category hair styling and care products. Traditional herbal powders
and hair oils for hair conditioning share the same shelf space with
high-end conditioners and hair care products.

46
Providing a feel of the market, Anmol Sherpa, coordinator of AC

Nielsen Global Services, said that unlike any international markets,
India has a large proportion of consumers whose hair care expendi
ture also includes hair oils. In fact, hair oils showed a growth of 6%
in 2005 over the previous year. Rural India saw a faster growth rate
of about 11%, while urban India grew by 4%.
The AC Nielsen study on the Indian hair care market identified
shampoo as the fastest-growing hair care product category, while
conditioners have the maximum growth potential. The shampoo
usage has increased across the board in both urban and rural
markets. According to AC Nielsen, shampoo is one of the fastest-
growing categories within the Fast Moving Consumer Goods
sector, registering a value growth of 10.9% between April 2004 and
March 2005.
Marketers have responded by launching newer variants of their
shampoosor by bringing in a whole new range of products. Some
established brands also have entered the shampoo and hair care seg
ment to ride this growth waveHindustan Levers leading cosmetic
and skin care brand Lakme is one such example. The company has
ventured into the shampoo and hair conditioner market with a new
sub-brandLakme HairNext. We are extremely pleased to bring
to the Indian woman a wide range of hair styling products that will
transform her hair into gorgeous tresses within minutes, said Anil
Chopra, vice president, Lakme Lever, when the product launched.
The aim was to get a complete hair solution on the market.
Meanwhile, conditioners are showing a steady growth rate in the
urban markets. In fact, this is one product category that is expected
to show exponential growth this year. To push this market, mid-
range consumer brands such as Garnier Fructis, P&Gs Pantene
and Lakmes HairNext are selling shampoo-conditioner duos as a
complete hair care solution.
Hair Color Market

Once only bought by the affluent as a beauty treat, hair colorants
have now become a lifestyle need, according to a AC Nielsen report.
Overall, the hair colorant segment is showing a strong growth rate
of 8% year on year. It is expected to show even stronger growth in

47
Bhattacharya Chapter 8
2006. In India, hair colorants have proven to be the hair care indus
trys crowning glory, said Nielsens Sherpa.
The hair colorants market has two distinct segmentsthe
professional coloring service offered by salons and the at-home hair
color market.
LOral Professional, followed by Schwarzkopf and Wella,
dominates the professional market. This segment has seen a steady
growth, predominantly in the metropolitan market because the
pricing of the color services can be prohibitive for tier two market
consumers. Hair color has been big in the country for some time
now, said Adhuna Akhtar, hair stylist and director, B: Blunt Salon.
Today, we can say the Indian consumer, especially women custom
ers, is very mature when it comes to hair color and other chemical
treatments. They follow the international hair trends very closely,
and are willing to spend more to get the style they want.
However, it is the at-home hair color market that has really
excited the big marketers. It is the market that is generating the
highest volumes for most of them, and it also is the segment that is
going through a transition phase. In addition to LOral and Labo
ratoires Garnier, some big Indian players have entered the market.
This market can be divided into permanent hair-color products,
powder hair dye and oil-based hair dye segments.
Revlon, which has been selling its ColorStay range of hair
colors, now is looking at introducing an India-specific hair color
brand. The company already is in the process of test marketing its
Top-Speed brand in the south Indian markets. Till now, we were
choosing the brands from our international portfolio, said Deepak
Bhandari, marketing manager, Modi Revlon. But now, we will
be creating region-specific brands for countries such as India and
Chinaespecially in the hair coloring segment. With this strategy
in place, the company expects to grow 40% in the hair color cat
egory by the end of 2006.
Fostering Aspirations
As the market matures, marketers are looking to create more
awareness and feed the fashion and beauty aspirations of Indian
consumers. Companies now are tying their retail products in with

48
salon services. LOral has even introduced its Kerastase Institutes

premium hair care service to meet the need. The company already
has opened hair spas in Delhi and Mumbai, and the company has
plans to increase the number of Kerastase Institutes across the coun
try, targeting major metropolitan areas.
In terms of services awareness, the consumers are still not
mature, said Kerastases Bakshi. But the potential is immense.
Through our services, we are trying to create more consciousness and
bring in the awareness that hair care is as customized and as evolved
as a skin care regimen. We are hoping to bring in that change
amongst the consumers in the country. In fact, we are looking to
foster their need for world-class hair treatments.
In offering such treatments, marketers have strategically kept
the pricing on the premium side. This can be interpreted as a way
to create a more mature customer base in the country in addition to
generating higher revenues for the companies.
Priyanka Bhattacharya, Journalist

New Woman, India

Chapter 9
Asian Hair: Its Properties,

Physiology, Protection
and the Market for Asian
Hair Care
KEY WORDS: hair and hair care, Asian hair care market, bending rigidity,
hair softness, conditioning agents, ethnic hair care
ABSTRACT: This article discusses the Asian hair care market, properties of
Asian hair, its unique physiology, and prototype conditioning
formulations to protect and care for this hair type.
When it comes to hair care, consumers seek those products that

satisfy their specific hair care needs and hair care habits. Some
want to emphasize the curly or wavy nature of their hair, while
others desire to tone it down or control it. One of the growing
ethnic populations in the US is the Asian population. In America,
the Asian population represents 4.2% of the US population and is
growing faster than the total US populace. Formulators have yet to
address the special needs of this market segment as they have done
with products specific to other ethnic groups.
Asian hair is typified as being straight. Fibers are usually longer in
length and are more round in cross-section. Due to this configura-
tion, there is a tendency for Asian hair to tangle, knot and break;
and damage such as split ends and scale lifting that is observed
from environmental factors can be exacerbated by chemical treat-
ments. Asian hair is typically very thick and coarse. It gets oily
much quicker than the hair of other ethnic groups. Thick hair is
much more difficult to comb, requiring a regimen of daily con
ditioning shampoos and rinse-off conditioners. Ambient high

50
Ethnic Asian Hair
temperature and high humidity conditions also play havoc on the

hair causing it to become frizzy and unmanageable.
This article will discuss the Asian hair care market, properties of
Asian hair, the unique physiology, and how to protect and care for
this hair type.
The Asian Hair Care Market

The Asian market: The Asian hair care market represents approxi-
mately 8 billion US dollars.1 Table 1 details the market by segment.
The shampoo segment, which includes both the beauty shampoos
and 2-in-1 shampoos, is the largest market segment (47%), with
conditioners close behind at (25.5%), followed by hair colorants at
(14%). Styling agents and hair sprays represent only 10% of the total
hair care market.
If we calculate the segment growth (Table 1) over the 5-year
period from 1996 through 2000, we see a slight (4%) decline in the
total Asian market for shampoos (beauty shampoos plus 2-in-1
shampoos), but an increase of more than 14% in the consumption
of 2-in-1 shampoos. Use of hair colorants increased by 40%. Use
of styling agents (mousse products) and hair sprays decreased by
almost 22%; gels and gel-like products are the most popular in this
market segment.
Table 1. Market (retail value of sales) for hair care in Asia-

Pacific 1996-2000 and growth over the five years
Retail value of sales (millions of $US)
Market Sector 1996 1997 1998 1999 2000 Growth

Beauty shampoos 2,550.7 2,289.0 1,840.5 2,060.7 2,185.9 14.3%
2-in-1 shampoos 1,354.1 1,365.6 1,243.6 1,424.7 1,552.2 +14.6
Conditioners 2,191.5 1,963.6 1,744.3 1,931.9 2,045.3 6.7
Styling agents/
hairsprays 1,013.6 884.9 733.0 760.1 791.1 21.9
Perms & relaxants 57.6 52.5 45.7 53.3 57.7 +0.2

51
Rocafort et al. Chapter 9
Asian-American demographics: US census figures2 show that

in 2000 the US population was 281.4 million people. The total
Asian population of 11.9 million included 10.2 million people who
identified themselves as Asian alone and an additional 1.7 million
people who identified themselves as Asian in combination with one
or more other races.3 The total Asian population represents 4.2%
of the US population in 2000 and is growing faster than the total
US population.
From 1990 to 2000, census figures show an increase of 5 million
Asians equating to a growth of 72%, while the US population grew
only 13% during this same decade.
Ethnic Groups in the United States

The Chinese represent the largest ethnic group in the US (23%),
followed by Filipinos (20%), Asian Indians (16%), Vietnamese
(10%), Korean (10%) and Japanese (9.6%).
The population is split by region. The highest saturation of the
Asian population is in the West (49%), followed by the Northeast
(20%), the South (19%) and the Midwest (12%).
With respect to the states, California has the largest number of
Asians followed by New York, Hawaii, Texas, New Jersey, Illinois,
Washington, Florida, Virginia, and Massachusetts.
Based on 2001 Statistical Abstracts of the US,4 the income and
educational level of Asian Americans is higher than that of other
ethnic groups; 42.4% of Asian Americans have a college degree.
The approximate medium family income is $52,000 for Asian
Americans, compared to $49,000 for Caucasians and $29,000 for
Blacks and Latinos.
Word of mouth is very important in the Asian-American com-
munity. Trends that start in Asia quickly make their way to the US
There is a new focus on individuality in Asia.
Properties and Physiology of Asian Hair

Properties: Asian hair is typified as being straight. Fibers are
usually longer in length and are more round in cross section. Due
to this configuration, there is a tendency for Asian hair to tangle,

52
Ethnic Asian Hair
knot, and break. It is a preference of Japanese, ASEAN, Chinese

and Indian women to keep their hair long; therefore the hair is
exposed for extremely long periods to environmental conditions,
harsh and extensive combing, brushing, as well as pinning or clamp-
ing and twisting. Damage such as split ends, can be observed even
on virgin hair and can be exacerbated by chemical treatments. This
is illustrated in Figure 1 with the SEM photos of Japanese, mixed
Oriental, and Indian hair.
Table 2 describes the properties and physiology of Asian hair
and the consequences for the end consumer.
Physiology: Todays Asian hair style trends favor straight hair
that appears silky and soft. Changing the hair color (not just
covering the grey hair but actually going lighter in shade) is also
popular. Because Asian hair is highly pigmented, the absorption
of the hair dye is more difficult. Higher bleaching is needed to
achieve some of the fashionable colors. This results in hair that is
more damaged.
Two of the major negatives of over-bleached hair are harsh hair
feel and poor combability. Bleaching causes the Asian hair fibers to
swell and the cuticles to lift making the hair more difficult to comb
and harsher feeling to the consumer. To avoid this damage, condi-
tioning polymers that are not oily in nature are incorporated into
formulations to help lay the cuticle down and bring it closer to its
natural state.
a b c
Figure 1. SEM photos of virgin hair

a = Japanese
b = mixed Oriental
c = Indian

53
Table 2. Properties and physiology of Asian hair and the

consequences for Asian consumers
Property Physiology Consequence

Configuration straight to wavy Combing/styling/managing is
more difficult.
Pigmentation highly pigmented Adsorption of hair dye is difficult
Higher bleaching is necessary,
causing more damage.
Hair shaft easily fractured More difficult to comb. Mechanical
damage occurs.
Cross sectional diameter large (92 microns) More difficult to
comb/style/manage.
Oiliness/Dryness oily Hair gets oilier faster, causing
limp hair/tangling/knotting.
Oily type conditioners not needed.
Elipticity nearly round to More difficult to detangle/comb.
slightly oval Hair is stiff. Difficult to curl hair
and maintain style.
Thickness coarse to fine More difficult to comb/style/manage.
Takes longer to dry hair.
Combing studies: In order to illustrate

the conditioning of Asian hair, a tensile
testera (Figure 2) was utilized to measure
the combability of hair.5 This instru-
mental method involves the continuous
recording of combing forces that oppose
the motion of the comb through the hair
tress. The experimental data produced
shows the combing force generated as a
function of the comb position along the
length of the hair tress.
Figure 2. Combability
testing instrument a
Dia-stron Miniature Tensile Testing System Mttl170,
(Diastron Tensile Tester) Dia-Stron Limited, Broomall, Pennsylvania USA

54
Ethnic Asian Hair
Wet and dry combing force measurements were conducted on

Japanese hair untreated and after various chemical treatments. The
chemical treatments investigated were bleaching for 15 minutes,
bleaching for 30 minutes, perming, and dyeing with several shades
of hair color. Percent reduction of combing was calculated and
reported in Table 3. As predicted, the combing forces increased with
the various chemical treatments imposed. This is an important point
because of the increasing popularity of hair colorants, straighteners
and bleaches for the Asian market segment.
Table 3. Average Diastron combing results for various Asian

commercial hair colorants, perms and bleaches
Wet Comb Dry Comb

Combing force Combing force
(gmf) (gmf)
Natural Japanese hair - virgin 20 60.7
Commercial hair colorant shade 3 395 160
Commercial hair colorant shade 6 510 397
Commercial hair colorant shade 4G 389 269
Commercial hair colorant shade 7G 301 407
Commercial perm for black hair 225 414
Commercial perm for natural hair 225 332
Commercial perm natural/cysteine 249 275
Natural hair bleached 1 x for 15 min 320 288
Natural hair bleached 1 x for 30 min 590 928
Protection and Care

To combat the various problems highlighted earlier in this article,
it is essential to keep the hair conditioned at all times. Hair dam-
age is caused by both mechanical and chemical trauma that alters
any of the physical structural components of the hair. Damage
either weakens hair or makes it more susceptible to additional
breakage from shampooing and other activities of everyday groom-
ing. Sunlight, high humidity and products such as perms, bleaches,

55
straighteners and permanent hair dyes chemically alter the hair and
increase its propensity to further breakage, resulting in cuticle abra-
sion, or erosion, or even split ends.
Conditioning agents do not repair hair. Once the hair is dam-
aged it cannot be repaired. Conditioning agents will temporarily
improve the cosmetic value and appearance of the hair.The cuticle
is the main hair structure affected by conditioning agents. An intact
cuticle is responsible for the strength, shine, smoothness, softness
and manageability of healthy hair. A layer of sebum coating the
cuticle also adds to hair shine and manageability.
Conditioning the hair can reduce the hair damage by improv-
ing sheen, decreasing brittleness, decreasing porosity and increasing
strength.
Figure 3a is a scanning electron microscopic (SEM) picture of
Japanese hair6 that has been damaged by bleaching for 30 min-
utes. Figure 3b shows damaged hair that was subsequently treated
with a conditioning shampoo containing polyquaternium-7 plus
acrylamidopropyltrimonium chloride/acrylates copolymer. Figure
3c shows damaged hair treated with a prototype rinse-off condi-
tioner formulation containing a combination of conditioning agents
(acrylamidopropyltrimonium chloride/acrylates copolymer plus
polyquaternium-32 (and) mineral oil (and) PPG-1 trideceth-6).
a b c
Figure 3. SEM photos of Japanese hair damaged by bleaching for 30 minutes

a = damaged hair with no subsequent treatment
b = damaged hair subsequently treated with silkening shampoo
c = damaged hair subsequently treated with prototype cream conditioner

56
Ethnic Asian Hair
As can be seen in these photos, the use of conditioning poly-

mers in a shampoo or rinse-off conditioner improves the surface of
the hair fiber by sealing the cuticle, which results in hair that feels
softer and is smooth to the touch. This is proven further by hair
softness studies.
Hair Softness Measurement

The measurement of hair softness can be conducted via a technique
called bending rigidity measurements.7 Bending rigidity is one of
the factors that govern hair body. Due to its straight configuration,
Asian hair tends to be stiff and somewhat unmanageable from a
consumer point of view. The addition of conditioning and mois-
turizing agents in a formulation tends to soften hair fibers. An
independent labb conducted this testing.
In this study, damaged hair ( Japanese hair which was bleached
for 30 minutes) was utilized for the testing. Five hair tresses were
submitted. One was an untreated bleached hair tress, and the other
4 hair tresses were treated with conditioning hair treatments. Two of
the treatments were conditioning shampoos and two were rinse-off
conditioners:
A prototype shampoo (containing polyquaternium-7 plus acryl-
amidopropyltrimonium chloride/acrylates copolymer);
The leading commercial shampoo in Japan for 2002;
A prototype rinse-off conditioner (containing acrylamidopropyl-
trimonium chloride/acrylates
copolymer plus polyquaternium-32 (and) mineral oil (and)
PPG-1 trideceth-6);
The leading commercial conditioner in Japan for 2002.
A standard application protocol was utilized for each of the
treatments. All of the tresses were held in an environmental room
set at 21C and 65% RH overnight prior to testing.
The independent lab measured bending rigidity using a
cantilever method and an instrumentc whose platform can be pro-
b
Textile Research Institute (TRI), Princeton, New Jersey USA
c
TRI/SCAN bending rigidity apparatus, Textile Research Institute (TRI), Princeton, New
Jersey USA

57
grammed to ascend or descend at specified speed and record small

forces through a Cahn microbalance with a mass resolution of 0.1
micrograms (Figure 4). In the cantilever method, hair fibers are sus-
pended from one end of the programmable platform and the fiber is
bent by the microbalance, which records the bending force.
Medium thickness hair fibers are removed from the tresses and a
section 3 cm long in the middle of the fiber is mounted in between
two brass ferrules. The cross-sectional area of the fiber is then mea-
sured using a laser micrometer to ensure that the fibers are of the
same thickness before testing. For each hair tress, the bending of 6
fibers is measured.
Bending rigidity is calculated according to the following formula:
R = FL3 3D
where F is the bending force, L is the bending length from the

secure end of the fiber to the hook (5 mm), D is the bending or flex-
ing distance, and R is the bending rigidity in mg/mm2.
The average cross sectional area for all samples was 0.0065
0.0005 mm2.
To Microbalance
Figure 4. Apparatus to measure bending rigidity (TRI/SCAN)

58
Ethnic Asian Hair
The bending force is plotted against bending distance. Bending

rigidity in this case was tested at a bending distance of 0.86 mm.
This value was selected because it was located on the linear por-
tion of the bending curve for almost all the samples tested, and also
because perfect bending would still occur. Values for bending rigid-
ity were calculated for each individual fiber and the average values
for each group are displayed in Figure 5.
Figure 5. Hair softness results from Japanese hair treated with commercial products and
prototype products, compared to untreated control. (Error bars show 95% confidence limits.)
As shown in Figure 5, the untreated bleached sample shows

the highest bending rigidity; the higher the number on the vertical
scale, the higher or more rigid the hair fiber is. Both of the shampoo
products tested displayed a lower rigidity than the untreated control;
however the differences are not significant. Both of the condition-
ers tested produced substantial reductions in the bending rigidity
versus the untreated hair. These were determined to be at the 95%
confidence level and confirmed by the results of a t-test. The proto-

59
type cream conditioner showed the lowest average rigidity out of the
five groups tested. In this case, the commercial shampoo is a high
conditioning formulation and contains a quaternary ingredient, a
polyquaternium and a blend of non-volatile silicones. We believe the
blend of silicones is contributing to the hair softness values, which
are better with the commercial shampoo than they are with the
more basic prototype conditioning shampoo formulation.
As seen by the SEM pictures, combing studies and hair soft-
ness testing, the use of conditioning agents temporarily improves the
cosmetic value and appearance of the hair and has a positive effect on
Asian hair. More studies are in progress to determine optimal condi-
tioning agents and concentration levels.
Conclusions
There is a large, highly educated, untapped group of consumers
with special hair needs, with a high disposable income waiting for
products designed especially for them. Unlike the African-American
market, there are very few US-produced products targeted specifi-
cally for Asian hair. Cultural, economic and physiological differences
must be considered when formulating for this market segment.
Colleen Rocafort, Emily Bazemore and Ellen Werner

Ciba Specialty Chemicals Corp., High Point, North Carolina USA
Acknowledgements
The authors wish to acknowledge the assistance of Yash Kamath, Ph.D., and Sigrid
Ruetsch, Ph.D., from Textile Research Institute (TRI), Princeton, NJ, USA for useful
discussions on Asian hair and for conducting topical studies of Asian hair utilizing Scanning
Electron Microscopy and softness studies utilizing bending rigidity measurements.
Also acknowledged are colleagues Susan Cellura, Chong Su Lee, Madeline Tan, Koji
Sekiya, Ph.D., Claire Schwenker and Wilfrid Gambade for helping to supply specific
information and for their help in understanding the hair care needs of the Asian and Asian-
American hair care market segments.
References
1. Euromonitor data, www.euromonitor.com (2001)
2. US Census data (2000) www.census.gov/prod/2002pubs/c2kbr01-16.pdf
3. http://www.infoplease.com/ipa/A0778584.html
4. Statistical Abstracts of the US (2001) http://www.asian-nation.org/demographics.html

60
Ethnic Asian Hair
5. J Pate-Linton, Use of Dia-Stron Miniature Tensile Tester to conduct combability

measurements on human hair, a test method documented by Ciba Specialty Chemicals
(Mar 2003)
6. TRI/Princeton, Contract Research Project Report ARS# 0919 (Nov 2002)
7. TRI/Princeton, Contract Research Project Reports ARS# 0919 (Jan 2003) and ARS# 984
(Sep 2003)

Chapter 10
Ethnic Hair and Disorders

of the Scalp
KEY WORDS: African-American hair, hair structure, hair density, hair
grooming practices, hair straightening, scalp disorders
ABSTRACT: This chapter surveys the racial differences of hair, and then
focuses on African-Americans, their hair grooming practices
and how these practices relate to the common hair and scalp
disorders unique to this population.
In recent years, literature has acknowledged that race and ethnicity

are important factors to consider in the clinical presentation, man-
agement and treatment of skin and hair disorders. Following a survey
of the literature on the racial differences of hair, this chapter will
focus on the curly hair of blacks, the grooming practices of blacks,
and the relation of those practices to common hair and scalp disor-
ders unique to this population.
Racial Variations of Hair

Shape: There are no biochemical differences in hair between racial
groups, however morphological differences have been documented.1
Caucasian hair is typically straight or wavy; round/oval on cross-
section and the hair follicle is straight. Asian hair is straight, round
on cross-section, contains a straight follicle and the diameter tends
to be greater than in the other groups. The hair of blacks tends to
be curly, elliptical on cross-section and emanates from a curved hair
follicle. Lindelof et al determined that the shape of the hair follicle
is what produces the shape of the hair.2
Breakage: Breakage is a frequent problem with the hair of blacks.
Khumalo et al examined hair samples from African, Caucasian and
Asian volunteers and compared the damage caused by normal hair

62
Ethnic Ethnic Hair and Disorders of the Scalp
grooming.3 Light and scanning electron microscopic examination

revealed 10-16% of black African hairs exhibited knots and were
intertwining, interlocking and appeared broken. Repeated breaks
of the hair shaft with no attached roots were present in the African
hairs, and the hair was shorter than in the other two groups.
Density: There are racial differences in hair density. A retro-
spective study of scalp biopsies on 22 African-Americans and 12
Caucasians showed that the total hair density, number of terminal
follicles and number of anagen hairs were lower in the African-
American subjects.4 A study by Bernstein and Rassman5 found that
variations in follicular units per square millimeter were less in Afri-
cans (0.6%) than in Caucasians (1.0%), Asians (1.0%) or Chinese
(0.7%) patients. Even though the hair density was less in Africans,
their predominant hair grouping was greater, i.e. three hairs per
follicular unit, as compared to two hairs per follicular unit in Cauca-
sians, Asians, and Chinese. Clinically, these racial variations in hair
density become important in interpreting scalp biopsies and evaluat-
ing hair restoration in black patients with hair loss.6
Dryness: Black hair has less shine and appears dry.7 This dry-
ness is related to the decreased ability of sebum to coat the hair
adequately. Therefore moisturizing maintenance hair styling prod-
ucts are used frequently to add shine and assist with combing and
manageability.6-8
Ethnic Hairstyles and Hair Grooming Practices

Black hair styling is extremely diverse. The hair often needs higher
levels of attention to achieve manageability, convenience and style.
Although some blacks choose natural or chemical-free hair styles
(see Natural Alternatives to Hair Straightening), others commonly
use techniques of hair straightening, which can be achieved by
either thermal (hot-combing) or chemical (hair relaxing) means.
Thermal straightening: Thermal straightening is a temporary
process that involves hydrogen bond rearrangement within the hair
shaft. This process is accomplished by lubricating the hair with
pressing oil, containing substances such as mineral oil, petrolatum,
ceresin wax or cetyl alcohol, and combing the hair in sections with a
metal comb heated to 300-500F. Because this method is temporary,

63
Callender Chapter 10
exposure to shampooing, water or humidity can cause reversion and

return the hair to its natural curly state.6
Chemical straightening: In contrast, chemical straightening is
the permanent rearrangement of disulfide bonds within the hair
shaft. The process uses several principal chemical agents: sodium
hydroxides (lye relaxers), lithium and quanidine hydroxides (no-lye
relaxers), and ammonium thioglycolate (permanent waves, curly
perms). It has been estimated that approximately 70-80% of black
women chemically relax their hair7 and require touch-ups to
straighten the new growth every 6-8 weeks.
Common Hair and Scalp Disorders in Blacks

Several hair and scalp disorders occur more often in the black
populations (see Common Ethnic Hair and Scalp Disorders).
Halder et al in 1983 examined the most common conditions seen
in a predominantly black dermatology practice. Among the top
five conditions were seborrheic dermatitis and alopecia.9 We will
discuss clinical observations and treatment strategies for seborrheic
dermatitis, psedofolliculititis barbae, traction alopecia and central
centrifugal cicatricial alopecia.
Natural Alternatives to Hair Straightening

Natural or chemical free hairstyles include afro, braids, twists,
and locks:
Afro - Natural curly hair is trimmed evenly at different lengths.
Braids - Natural hair is braided in sections close to the scalp
(cornrows) or in individual braids; hair extensions can be added for
fullness or length.
Twists - Natural hair is divided into two sections, wrapped and held
together by styling gel or beeswax.
Locks - Formed by allowing the twisted hair to permanently
intertwine and interlock.
Interestingly, in a shift that has clinical significance, more and more
women are accepting these hair styles and abandoning the straighter
hair styles.

64
Common Ethnic Hair and Scalp Disorders

Seborrheic dermatitis chronic papulousquamous disorder affecting
sebaceous-rich areas
Irritant contact dermatitis dermatitis caused by hair care products
resulting in erythema
Allergic contact dermatitis allergic reaction of the scalp resulting from
hair care products
Traction alopecia hair loss occurring in the front temporal areas due to
mechanical loosening of the hair from the follicle
Central centrifugal cicatricial alopecia hair loss affecting the crown and
vertex of the scalp resulting in scarring
Acne keloidalis chronic granolomatus condition resulting in papules and
or pustules on the nape of neck and occipital scalp
Dissecting cellulitis chronic inflammatory disorder of the scalp resulting
in tender cysts and sinus tracts
Pseudofolliculitis barbae (known as razor bumps) a common condition
of the beard area resulting when curved hairs grow back into the
skin causing inflammation and, over time, keloidal scarring
Tinea capitis infection of the scalp caused by trichophytontonsurans
resulting in delicatescaling of the scalp with or withou alopecia
Cutaneous sarcoidosis multisystem granulomatous disease of the scalp
Discoid lupus erythematosus Autoimmune disease that can result in
alopecia and/or discord lesions on the scalp.
Seborrheic dermatitis: Seborrheic dermatitis is a chronic papu-

losquamous disease of sebum rich areas of skin that is caused by an
inflammatory response to yeast, Malassezia furfur (Pityrosporum
ovale). The incidence varies from 2-5% of the total population.
Although no racial or ethnic predisposition has been reported in
the literature, the incidence may be higher in black women due to
the frequency of hair washing. While males with short natural hair
cuts wash their hair daily, many black females wash their hair less
frequently, from once per week to every four weeks, depending upon
their current hairstyle. Thus, an overgrowth of yeast occurs and
places this population at a higher incidence of disease.
Besides the common erythema and scaling or dry scalp appear-
ance that is characteristic of seborrheic dermatitis, hypopigmentation

65
or hyperpigmentation of the skin and scalp may also occur. Common

locations include the scalp, anterior hair line, forehead, eyebrows,
eyelashes, ears and malar areas of the face. In men, the condition
may appear in the mustache, beard and chest areas. Pruritus of the
scalp is the most common symptom.
Treatment strategies consist of over-the-counter (OTC) or
prescription-strength anti-dandruff shampoos. Common ingredients
include: sulfur, salicyclic acid, tar derivatives, zinc pyrithione (ZPT),
tea-tree oil, sulfacetamide, ketoconazole or ciclopirox (anti-fungals)
and fluocinolone acetonide (corticosteroid).
Because these agents can cause excessive dryness of black hair,
after-shampooing conditioners and daily moisturizing lotions
must be used as part of the treatment regimen. In moderate to
severe cases of seborrheic dermatitis, a decrease in hair washing is
recommended as well as daily application of a topical corticoster-
oid between hair washings. The vehicle selected must be carefully
chosen and compatible with the hair styling practices of the patient.
Traditionally, these patients are frequently prescribed ointment-
based topical corticosteroids. More recently, foam-based treatments
have been found to be efficacious and cosmetically acceptable.10
Traction alopecia: Traction alopecia, also known as traumatic alo-
pecia marginalis, is a condition of hair loss commonly seen in black
women and children11 who prefer hairstyles (such as tight braids,
ponytails, weaves and dredlocks) that cause tension on the hair.6, 11, 12
Hair rollers have also been implicated as a factor in traction alopecia.
The mechanism of hair loss is thought to be mechanical loosen-
ing of the hairs from the follicle with an associated perifolliculitis
of the scalp.9 The condition is observed in patients showing sym-
metrical hair loss in the fronto-temporal areas of the scalp, with hair
loss in the occipital area being less common.9 Sustained tension on
the hair can result in follicular atrophy, leaving only thinner vellus
hairs intact. This hair loss may also be accompanied by perifollicular
erythema, papules, pustules and/or a seborrhea-like hyperkeratosis.9
Treatment of traction alopecia involves discontinuing hairstyles
that result in sustained tension of the hair. In early cases of traction
alopecia, this may result in reversal of the hair loss. In more severe
cases, patients are treated with topical and intralesional corticos-

66
teroids if inflammation is present.6 Topical minoxidil has also been

used as a treatment for traction alopecia and has been successful in
some patients.6, 14
In cases where folliculitis is present, topical and oral antibiotics
are prescribed. In advanced cases where re-growth of the hair is
unlikely and permanent loss of the hair follicles has taken place,
surgical treatment is an option. Punch grafting and rotation flaps
have been used previously for the treatment of traction alopecia.15
More recently other surgical techniques have been used with suc-
cess, including mini-grafting, micro-grafting and follicular unit
transplantation.6
Central centrifugal cicatricial alopecia: Central centrifugal cicatri-
cial alopecia (CCCA) is a type of alopecia that denotes the presence
of scar tissue in the scalp. This condition was previously known as
hot comb alopecia16 and follicular degeneration syndrome.17 Histo
logically, the earliest sign is premature desquamation of the inner
root sheath.17 The etiology of this condition is unknown but appears
to be multifactorial (genetic and environmental).
This type of alopecia is found on the crown and vertex of the
scalp. Early in the disease process, the involved area is well
defined and minute. Early on it may resemble hair breakage and/
or female-patterned baldness. As the disease progresses, it spreads
circumferentially and the involved area increases in size.9 The scalp
is usually shiny and there is a decrease in hair density in the affected
area. The hairs that remain in the scarred area are shorter and more
brittle than those found in the normal area of the scalp and the
symptoms experienced may include pruritus, burning and tender-
ness of the scalp.6
Treatment of CCCA is multifaceted and based upon the symp-
toms experienced by the patients. Aggressive anti-inflammatory
treatment is very important in treating CCCA. The inflammation
is suppressed by using topical high-potency corticosteroids and
intralesional corticosteroids.6 This treatment not only reduces the
present inflammation, but it also retards the progression of the
inflammatory process.
It is also important to educate the patient regarding hair care
practices because it is important that he or she discontinue all

67
practices that may be damaging to the hair. Patients should increase

the time between relaxer applications (every eight to ten weeks)
and they should also decrease the use of hardening gels, sprays, and
heat to the scalp.6 Once the disease process has been stabilized and
inflammation is no longer present, surgical hair transplantation
is an option for treatment.6 This technique is reserved for those
patients whose hair follicles are no longer viable.
Pseudofolliculitis barbae: Pseudofolliculitis barbae (PFB) is a
chronic condition seen commonly in black men who shave, but
it is also is seen in black women who experience hirsutism and
use shaving and/or tweezing as a mechanism of hair removal.
This condition is commonly referred to as razor bumps and is
caused by a foreign-body reaction surrounding ingrown hairs.18
The mechanism of hair penetration is both extrafollicular and
transfollicular.19 Patients often see papules, pustules and hyperpig-
mentation in the chin, neck, axilla or bikini area. In severe cases
of PFB, keloid formation may be observed. Treatment of PFB
involves topical therapy to treat the cutaneous signs as well as
preventive measures to decrease the ingrown hairs. Topical
therapies include the use of corticosteroids that help reduce
inflammation as well as topical antibiotics such as clindamycin 1%.
Topical tretinoin, adapalene and tazarotene have also been used
with some success to treat the papules and hyperpigmentation
resulting from PFB.18 In more severe cases of PFB, low dose
oral antibiotics (doxycycline 100 mg twice a day) may be used for
1-3 months.
Laser hair removal is also effective in treating PFB. The
Q-switched Nd:YAG laser is effective and safe for laser hair
removal. We recently performed a retrospective study20 on 100
black patients with hirsutism, PFB and postimflammatory hyper-
pigmentation. In our study population we used the Q-switched
Nd:YAG laser along with eflornithine hydrochloride cream to treat
hirsutism in black women. Eflornithine hydrochloride irreversibly
inhibits the enzyme ornithine decarboxlyase, decreasing the rate
of re-growth of the hair.12 We also noticed that this combination
therapy causes the hair to grow thinner, therefore making it less
likely to develop ingrown hairs.

68
Conclusion
Treating ethnic hair and scalp disorders can be very challenging. A
thorough knowledge and understanding of the hair structure and
hair grooming practices are essential in the proper diagnosis and
successful management of ethnic patients. Based upon the various
ethnic hair and scalp disorders that exist in this population, prod-
uct formulation, such as superior moisturizing agents specifically
designed for ethnic hair and chemical alternatives for hair relaxing
must be developed that focus on the special needs of ethnic hair.
Valerie D. Callender
Howard University College of Medicine, Washington, D.C. USA
References
1. A Rook, Racial and other genetic variations in hair form, Br J Dermatol 92 599-600 (1975)
2. B Lindelof, B Forslind, MA Hedblad and U Kaveus, Human hair form, Arch Dermatol
124 1359-1363 (1988)
3. NP Khumalo, PT Doe, PR Dawber and DJP Ferguson, What is normal black African hair?
A light and scanning electron-microscopic study, J Am Acad Dermatol 43 814-820 (2000)
4. LC Sperling, Hair density in African-Americans, Arch Dermatol 135 656-658 (1999)
5. RM Bernstein and WR Rassman, The aesthetics of follicular transplantation, Dermatol
Surg 23 785-799 (1997)
6. VD Callender, AJ McMichael and GF Cohen, Medical and surgical therapies for
alopecias in black women, Dermatologic Therapy 17 164-176 (2004)
7. BA Johnson, Requirements in cosmetics for black skin, Dermatol Clin 6 400-492 (1988)
8. AJ McMichael, Ethnic hair update: Past and present, J Am Acad Dermatol 48 S127-33
(2003)
9. RM Halder, PE Grimes, CI McLaurin, MA Kress and JA Kenney, Jr, Incidence of common
dermatoses in a predominantly black dermatologic practice, Cutis 32 378-380 (1983)
10. YA George et al, Betamethasone valerate 0.12% in foam vehicle for scalp seborrheic
dermatitis in African-Americans, Cosmet Dermatol 15 25-29 (2002)
11. RN Halder, Hair and scalp disorders in blacks, Cutis 32 378-380 (1983)
12. AH Shepyan, Traction alopecia, Arch Dermatol 78 395-398 (1958)
13. MJ Lipnik, Traumatic aloepecia from brushrollers, Arch Dermatol 84 183-185 (1961)
14. WS Wilborn, Disorders of hair growth in African-Americans, In: E Olsen, Disorders of
Hair Growth
15. RM Earkes, Surgical correction of traumatic alopecia marginalis ortraction alopecia in
black women, J Dermatol Surg Oncol 12 78-82 (1986)
16. P lopresti, CM Papa, AM Kligman, Hot comb alopecia, Arch Dermatol, 98 234-238 (1968)
17. LC Sperling, P Sac, The follicular degeneration syndrome in black patients: Comb
alopecia revisted and revised, Arch Dermatol (128 68-74 (1992)
18. RM Halder and GM Richards, Therapeutic approaches for pseudofolliculitis barbae,
Cosmetic Dermatology 16 42-45 (2003)
19. RM Halder, Pseudofolliculitis barbae and related disorders, Dermatol Clin 6(3) 407-412
(1988)

69
20. VD Callender and CM Young poster presentation, Study: Combination laser and E
Plornithine HCL 13.9% cream: A first line therapy for Fitzpatrick Type IV-VI patients with
excessive facial hair, presented at the 63rd Annual Meeting of the American Academy
of Dermatology, New Orleans, LA (Feb 2005)
21. CJ Rogers, DA Glaser, Treatment of pseudofolliculitis barbae using the Q-switched Nd:
YAG laser with topical carbon suspension, Dermatol Surg 26 737-742 (2000)
22. EV Ross et al, Treatment of pseudofolliculitis barbae in skin types IV, V and VI with a
long-pulsedreodymium: Yttrium aluminum garnet laser, Arch Dermatol 47 263-270 (2002)
23. AN Kauvar, Treatment of pseudofolliculitis with a pulsed infrared laser, J Cutan Laser
Ther 1 109-111 (1999)

Chapter 11
Inside the Hair: an

Advanced Hair Biology
Model
KEY WORDS: hair and hair care, hair structure, cuticle, cortex, lipids
ABSTRACT: In this literature review, various writers describe a model of
the inside of a hair strand, showing a multilamellar structure
of the cuticle cells, a multifibril structure of the cortex, and a
variety of lipids that are thought to be major contributors to
the hairs physical properties.
Give me a head with hair. Long beautiful hair

Shining, gleaming, streaming, flaxen, waxen - Hair!
These lyrics from the popular Broadway musical Hair are humorous,
but they do raise a very serious question: what exactly is hair?
Simply put, the answer is that hair is protein. This simple answer,
however, does not even begin to explain the complexity and sophis-
tication of the hair fiber.
Science is like that sometimes; it starts with a simplistic model
that evolves to explain more subtle and complex details. For example,
consider how the conception of the atom has evolved over time. The
ancient Greeks originally described atoms as simple, tiny, indivis-
ible particles. This notion was expanded on by Bohrs theory that
atoms were more like miniature solar systems with electron planets
revolving around a solar nucleus. Other theories have evolved to
the point where atomic structure now is viewed as an electron density
cloud swirling around a diverse collection of subatomic particles.
The concept of hair biology has gone through a similar evolution.
The simplistic view that hair is made of protein has been replaced
by a more detailed picture of the three structural components of

72
Physiology Inside the Hair: an Advanced Hair Biology Model
hair: the cuticle, the cortex, and the medulla. This three-component
model has evolved even further to include a variety of substructures.
This chapter will begin with a review of the basic components of
hair and then describe the current understanding of its more com-
plex physical and chemical substructure.
By gaining a greater understanding of the complex structure of
hair, cosmetic chemists should be able to identify new targets for
improving current products and maybe even create whole new prod-
uct categories.
Physical Structurethe Simple Version

In a simplistic view, each hair can be thought of as being made up
of two structures: the follicle and the hair shaft. Since cosmetics are
designed only to affect the surface appearance of hair, the rest of this
chapter will focus on the structure of the hair shaft.
The hair shaft is composed primarily of the same hard mate-
rial that animal hooves and horns are made ofkeratin protein.
Depending on the hair type, this protein can make up anywhere
from 6595% of the hairs mass.
Hair keratin is arranged into three primary elements: the cuticle,
the cortex and the medulla. The outermost element is the cuticle,
a protective layer that resembles the shingles on a roof. An average
human hair has seven to ten layers of cuticles covering it. As hair
grows it is exposed to months, or even years, of grooming that wears
down the edges of the cuticle. Once these shingles are chipped and
broken away, the inside of the hair is exposed. This portion of the
hair shaft, known as the cortex, is composed of bundles of protein.
While the cuticle provides outside protection for the hair, the cortex
gives it its inner strength. The third component in this simple hair
schematic is the medulla, a spongy vacuole that runs through the
center of the cortex. The medulla is considered to be a minor com-
ponent that is present in only a portion of hair fibers and probably is
a vestigial component that once provided an insulating effect when
hair was the primary protective covering for humans.
The cuticle, cortex and medulla constitute a simplified picture of
the hairs true structure. But the whole story is much more complex.

73
Schueller and Romanowski Chapter 11
A more complete examination of these structures can inspire new

approaches to designing hair care formulas.
Physical Structurethe Cuticle

Despite their simple shingle-like appearance, cuticle cells have a
complex multilamellar structure (Figure 1). Multiple layers are
attached to one another in sheets that form overlapping scales.
Each cuticle cell is a square sheet about 50 m on each side and
about 0.5 m thick. They are composed of the following discrete
layers: the outer -layer, the epicuticle, the exocuticle, the endocu-
ticle, the inner layer and the cell membrane complex. Each of these
layers has its own substructure that is described below. Despite
their simple shingle-like appearance, cuticle cells have a complex
multilamellar structure.
Outer -layer: As its name implies, the outer -layer (OBL)
(sometimes called the upper -layer) is the outermost surface of the
hair, although the OBL also may appear in inner layers (see Figure
1) because of the way the hair is formed in the follicle. The OBL
is primarily composed of a hydrophobic fatty acid that protects the
surface of the hair. (The composition of this and other hair lipids
will be described later in this chapter.) The outer -layer also is
present as part of the cell membrane complex.
Epicuticle: This hydrophobic coating on the outside of the cuticle
is responsible for many of the surface properties of hair. It is approx-
imately 10 nm thick and consists of three subsections:
F-layer. This layer of covalently bonded fatty acids lays on top
of the epicuticle. It is composed of the same material as the
outer -layer. In fact, the F-layers of the epicuticles closest to
the surface create the outer -layer.
Protein matrix. This is a layer of highly water-insoluble pro-
teins sandwiched in the middle of the epicuticle.
A-layer. This cystine-rich layer approximately 110 nm thick
is cross-linked with an isopeptide. This combination makes
the A-layer very tough and resistant to mechanical damage.
Because the proteins in this segment are so cross-linked,
the A-layer does not swell in water. It tends to be brittle,

74
which allows small segments of the cuticle to break away

when damaged.
Exocuticle: This structure lies just beneath the A-layer and is
slightly lower in cystine content. It is the single largest component of
the cuticle and takes up about 50% of the cell by cross-sectional area.
Outer surface of cuticle cell
Outer -layer
Epicuticle
A-layer
Exocuticle
Endocuticle
Inner Layer
{
Inner -layer
Cell
Membrane -layer
Complex Outer -layer (bottom) of this cell
and top layer of the cell below
to follicle to tip
Hair strand with shingles
Figure 1. Physical structure of a hair cuticle cell

75
Endocuticle: This layer is formed when residual cytoplasm dehy-

drates and hardens. It is a region free of cystine and so it tends
to behave more like a gel in that it swells considerably in water.
When the endocuticle is damaged, water-soluble materials can slip
inside the hair. This is the current theory of how materials penetrate
the hair shaft; they diffuse along the planes of the endocuticle as
opposed to penetrating straight through the cuticle.
Inner layer: This layer is similar in composition to the exocuticle,
but is much thinner. The inner layer is bonded to the next cell by
the cell membrane complex.
Cell membrane complex: The cell membrane complex (CMC) is
like a cuticle glue and is actually composed of three internal layers:
two -layers separated by a -layer.
Inner -layer. This is sometimes called the lower -layer. It is
composed of the same material as the outer -layer.
-layer. The composition of this layer is not fully understood,
but it is believed to be a mixture of lipids and glycoproteins.
Outer -layer (OBL). This layer (like the OBL mentioned
earlier) is composed of a covalently bonded fatty acid.
Together, these sandwiched layers form the sheet-like structure
of the cuticle that covers the outside of the hair shaft. Below the lay-
ers of the cuticle lies the next major structure: the cortex.
Physical Structurethe Cortex

A close look at the core of the hair reveals that it is far more than a
simple bundle of protein fibers. Much of what is known about the
cortex was published in the 1930s by Astbury and colleagues2 who
showed that the proteins in these bundles have a folded structure.
It wasnt until the 1950s that Pauling, Corey and Branson3 discov-
ered that the proteins forming this folded structure have a helical
configuration.
Today, there is a much clearer understanding of this structure.
The cortex is built from protofibrils, microfibrils (also known as
intermediate filaments), macrofibrils and the intermacrofibrillar
matrix. The macrofibrils and intermacrofibrillar matrix are arranged
to form the cells of the cortex. Depending on the arrangement,
these cells are classified as either paracortical or orthocortical. These

76
components are organized into cortical cells that form the body of
the cortex. Below are the major features of each of these elements.
Protofibrils: These elements consist of five individual protein
molecules about 1 nm across that wind around each other in a helix
arrangement to form a protofibril rod that is approximately 2.5 nm
in diameter. Protofibrils are the building blocks of the cortex.
Microfibrils: Five protofibril rods are twisted together to form a
larger structure known as a microfibril (also known as an intermedi-
ate filament, or IF). These microfibrils are entangled such that the
protein molecules become tied together, thus giving the hair a high
degree of tensile strength.
Macrofibrils: The microfibrils then bundle together to form a
still larger cable known as a macrofibril. Macrofibrils can form
two different kinds of cortical cells depending on how they are
packed together.
Intermacrofibrillar matrix: This is a nonkeratin material that is
high in cystine and is found packed inside cortical cells.
Paracortical and orthocortical cells: Paracortical cells contain
macrofibrils that are packed so closely together that they fill the
entire cell. There is no intermacrofibrillar matrix filling the intercel-
lular spaces in this type of cortical cell. This configuration makes the
paracortical cells more dense and unable to absorb much moisture.
Orthocortical cells consist of macrofibrils loosely packed together
and surrounded by intermacrofibrillar matrix. This packing con-
figuration makes the orthocuticle cells less dense, so they are able to
easily take in or lose moisture. Therefore this type of cortical cell is
very reactive to humidity.
The cortex is a combination of these para and ortho cells hooked
together. Each microscopic cortical cell is shaped like a tiny spindle,
about 100 m long and 510 m wide. These spindles end with
finger-like extensions that can hook onto nearby cells. The para
cells tend to be oriented along the inner edge of the cortex while the
ortho cells are grouped on the outer side.
By itself, the paracortex region is very hard and moisture-resistant
and would cause the hair to grow straight. When combined with the
softer orthocortex, which tends to buckle when exposed to mois-
ture, the hair shaft is made to bend, creating curl. More orthocortex

77
results in more and tighter curls. According to Swift, the ratio and
distribution of these two cells controls the degree of curliness of the
hair. Asian hair has almost all paracortex, Afro-ethnic hair is mostly
orthocortex, and Caucasian hair has a more balanced proportion
of each.
Lipids in the Hair Shaft

While most people are aware of the fact that follicles produce lipid
materials (sebum) that coat the surface of the hair, they may be sur-
prised to know there are numerous lipids found within the hair and
even bonded to it. These internal lipids affect the hairs structure
and properties.
Lipid composition of the hair: Various analytical studies of hair
have shown that lipids comprise approximately 5% of the total mass
of hair. They also have identified numerous types of internal hair
lipids including 18-methyl eicosanoic acid, hydrocarbons, squalene,
wax esters, triglycerides, fatty acids, cholesterol and ceramides. A
recent study by Masukawa et al.4 showed that all of these hair lipids
can be arranged into different groups based on their biological
source and function. One group, called exogenous lipids, contains
compounds originating from sebum. In this group are materials such
as squalene, wax esters, triglycerides and fatty acids. While some
of these compounds are found throughout the hair, they are not
believed to be directly involved in hair structure.
Another group, called endogenous lipids, is biosynthesized in
the hair matrix cells of the follicle. Compounds in these groups are
involved in the structure of the hair, and will be discussed next.
Structural fatty acids: At the top surface of the hair is the OBL.
This layer really is just the outer surface of the first epicuticle
(F-layer) and is composed of a wide range of endogenous fatty
acids. The primary component (more than 40%) is a fatty acid
known as 18-methyl eicosanoic acid (18-MEA). It is a branched,
21-carbon compound that is most likely biosynthesized in the hair
follicle from the amino acid isoleucine. The fatty acids in these lay-
ers are covalently bonded to the epicuticle via thio-ester linkages.
According to Ward et al.,5 the layer formed is approximately 0.9

78
nm thick. This layer is believed to add extra protection and water-

proofing to the cuticle.
Another lipid-containing structure previously described is the
CMC. Both of the -layers of this structure are composed primar-
ily of 18-MEA. Less is known about the exact composition of the
-layer, but it is believed1 to be a mixture of endogenous lipids and
glycoproteins. This structure helps hold the cuticles together and
may assist in hair moisture retention.1 However, low cohesive forces
between the -layers and -layers may explain the ease with which
cuticle shingles are broken off.1 It is possible that if this layer were
stronger, there would be less hair damage.
Affect on hair properties: The various lipids found throughout
the hair are thought to be major contributors to the hairs physical
properties. Evidence has shown that they influence a host of charac-
teristics such as strength, feel and condition.
Work by Duvel et al.6 showed that loss of hair lipids (both exog-
enous and endogenous) due to environmental exposures resulted in
increased cortex degradation and decreased tensile properties of hair.
A study by Wills et al.7 showed that hair lipid content signifi-
cantly impacts the perceived shine, smoothness and softness of hair.
In this case, a higher level of lipids in hair resulted in improvements
in each of these properties.
Studies such as these suggest possible development routes for
products designed to restore hair to its natural state.
Conclusion
Scientists spend much of their time investigating their world and
creating models to reflect observations. In the initial stages of these
investigations the models are understandably crude. They become
more sophisticated over time as more and more observations are
collected. The changing model for the structure of hair is a perfect
example of how this process can work.
For cosmetic chemists, models for the structure of both hair and
skin are helpful for generating ideas for future products. Only by
knowing how hair or skin is put together will significant improve-
ments be made in the type of products offered tomorrow.

79
Randy Schueller and Perry Romanowski

Alberto-Culver Company, Melrose Park, IL USA
Published November 2005 Cosmetics & Toiletries
References
1. JA Swift and JR Smith, Microscopical investigation on the epicuticle of mammalian
keratin fibres, J Microscopy 204(3) 203211 (2001)
2. DAD Parry, Protein chains in hair and epidermal keratin IF: Structural features and
spatial arrangements, In: Formation and Structure of Human Hair, P Jolles, H Zahn and
H Hocker, eds, Basel: Birkhauser Verlag (1997)
3. L Pauling, RB Corey and HR Branson, The structure of proteins: Two hydrogen-bonded
helical configurations of the peptide chain, Proc Natl Acad Sci 37 205211 (1951)
4. Y Masukawa, H Narita and G Imokawa, Characterization of the lipid composition at the
proximal root regions of human hair, J Cosmet Sci 56(1) 116 (2005)
5. RJ Ward, HA Willis, GA George, GB Guise, RJ Denning, DJ Evans and RD Short,
Surface analysis of wool by x-ray photoelectron spectroscopy and static secondary ion
mass spectrometry, Text Res J 63 362368 (1993)
6. L Duvel, H Chun, D Deppa and PW Wertz, Analysis of hair lipids and tensile properties
as a function of distance from scalp, Int J Cosmet Sci 27(4) 193198 (2005)
7. J Wills, S Dolphin, L Albiston, P Parmar, GE Westgate and GJ Harrap, Free internal lipids
in hair from pre- and post-menopausal women, IFSCC Magazine 7(4) 293297 (2004)

Chapter 12
Approaches to and
Characterization of
Hair Growth
KEY WORDS: Hair growth, hormones, follicle, stress, hair diameter
ABSTRACT: There is still more to learn about hair growth control and
what influences the follicle. The translation of what is
learned into effective treatments is not keeping pace. This
review offers some biology of the hair cycle and comments on
differences between kinds of hair and hair treatments.
Men, especially, know that hair thins with age and that there are
many products on the market to assist with hair growthbut what
exactly is meant by a hair growth solution? Does it deliver more
hair, thicker hair, hair that grows longer before it breaks or hair
that grows faster? Biologically, hair growth is a well-described cycle
involving four phases: growth (anagen), regression (catagen), resting
(telogen) and shedding (exogen).1-4 This cycle occurs in virtually all
hair-bearing species and the dynamics of the hair cycle have been
the subject of recent studies.5
The hair follicle is a multicellular tissue that retains an element
of developmental dynamics recapitulated in the adult hair cycle.
This is reflected in the continual interplay between the mesenchy-
mal and epithelial elements. This review offers a brief summary of
some of the biology of hair growth and comments on some of the
differences between hairs that are critical to describing what kind of
hair is produced by hair growth technologies.
Hair growth is not completely understood, despite a rapid
increase in research in recent years. Although factors regulating
the transition between the key stages in adult hair cycling are well-

82
Physiology Approaches to and Characterization of Hair Growth
documented,5 it is perhaps not surprising that the two US Food and

Drug Administration (FDA)-approved treatments for hair loss were
existing drugs for which hair growth is a side effect of their primary
use. Originally, minoxidil was developed for hypertension, and finas-
teride was designed for prostate disease. Disappointingly, few clues
about hair follicle changes in hair loss have been gleaned from these
serendipitous findings.6
History of Growth Technologies

The commercial potential to treat hair loss in a cosmetic yet effec-
tive way was realized by the early work with minoxidil. Upjohn
translated its hair growth side effect into a topical product with
clinical proof and widespread use. This success was followed by
increased research interest in hair biology. Questions still being
addressed include: How is the hair cycle regulated? What is the
genetic basis for androgen-driven hair loss? Is blood supply to the
follicle relevant to hair loss? What drives the changes from small,
fine, vellus hair to larger, terminal hair and back again? Is there a
link to overall diet, stress and other lifestyle factors?
There are now scores of treatments in development or on the
market making claims for prevention of hair loss and hair re-growth
(see Table 1). Note that of those listed, only minoxidil and finas-
teride have proven activity in trials acceptable to the FDA. Many
others are contained in marketed products that have some support,
if not FDA review.
The diversity of technologies and modes of action are driven
by both the assay tools available for discovery and through ser-
endipity. Assays available include hair follicle cell cultures, the
culture of whole human hair follicles and mouse models. The two
FDA-approved routes have led to significant follow-up research.
Interestingly, little attempt has been made to develop products based
on two other drugs with well-described hair growth side effects:
cyclosporine A and latanoprost, which are immunophilin and pros-
taglandin analogs, respectively.
Examples of hair loss treatments can be found in more tradi
tional approaches in Chinese and ayurvedic medicines as well as
in herbal remedies. These combine several ingredients such as

83
Westgate et al. Chapter 12
bringraj, black sesame, gingko, silica, he shou wu and saw palmetto

for a personalized holistic approach to treatment to restore hair
growth. Often these are characterized by a whole body approach
the treatments are consumed as opposed to applied topically and
their use is surrounded by strong belief systems. Translating these
into topical formulations brings challenges including delivery
through the skin and into hair follicles, as well as the possibility for
skin reactions and sensitization.
The pharmaceutical approach to developing a novel treatment
for a disorder is to identify a key drug target, develop suitable
screening tools, discover or design materials to alter the function of
the selected target, and then test these treatments in vivo. This can
take many years. So why has this approach not been adopted within
the cosmetics industry?
Table 1. Selected candidate agents with anti-hair loss

potential
Agent Product Claimed Routes

Minoxidil Regaine/Rogaine Stimulate proliferation, anti-apoptotic,
antioxidant and protective
Adenosine Adenogen to the hair bulb
Copper peptides Tricomin
Procyanidin
Proteasome inhibitor Niosil (in Phase II clinical)
(NEOSH101)
Ketaconazole Nizoral Anti-inflammatory/antifungal
Finasteride Propecia Anti-androgen to inhibit 5-
Reductase
Saw Palmetto Revivogen*
Azeleic acid Crinagen*
Aminexil (2,4 DPO) Dercos Anti-fibrotic
Kopexil
* mixtures with other actives
Note: Only minoxidil and finasteride have proven activity in trials acceptable to the FDA. Many
others are contained in marketed products that have some support if not FDA review.

84
Possibly an analysis of costs, development time and the risk

associated with the complexity of the hair follicle and hair cycle
have led to a belief that finding the right target, in the right cell
type, at a specific stage in the cycle of hair growth, may be too great
a challenge. From a hair biologists perspective the more interest-
ing question might be which of the more recent research findings
provide directions for future technology searches?
The fact that hormones do affect hair growth is without ques-
tion. Consider puberty, for example. The actual mechanisms of
hormonal activity, however, are still not fully understood.
One exception is the work done to demonstrate the importance
of the enzyme 5- in the metabolism of testosterone within the
pilosebaceous unit.7 The role of estrogens in hair cycle dynamics
remains a conundrum. Evidence from studies with 17-estradiol in
mice suggests that it acts via the estrogen receptor ER to delay the
telogen to anagen transition.8,9 In man, it is not yet clear whether
estrogens are important for anagen maintenance and delay in hair
shedding; however, this is purported to be the case in pregnancy.10,11
It is also possible that estrogen receptor signaling may well delay
hair shedding in mice by delaying anagen onset.
Interestingly, during pregnancy, hair diameter has been shown to
increase,12 suggesting some anabolic actions at the level of the fol-
licle during anagen. The use of estrogen treatment for male pattern
baldness has not been pursued.
The follicle is influenced by its surrounding dermis, although
concrete evidence for the mechanisms remains only associative.
Both male and female pattern hair loss appears to be associated with
fibrosis.13, 14, 15 Even in hair loss with strong inflammatory compo-
nent, Olsen16 suggests that visible inflammation is lacking and that
visual inspection may not reveal an underlying degree of inflamma-
tion. In contrast, Deloche17 claims that peripilar signs around hair
follicles correlate with inflammation of hair follicles in subjects with
androgenic alopecia (AGA).
Current Approaches
Recent clinical studies with ketoconazole and zinc pyrithione
indicate that targeting the scalp microflora can relieve symptoms

85
of balding in men. Pierard-Franchimont,18, 19 Berger,20 and Mahe21

hypothesized that micro-inflammation is relevant in about one-
third of men with AGA. Dandruff cycling was studied in relation to
telogen hair loss22 and although an association was found in period-
icity between telogen loss and dandruff, it could not be concluded
that these were linked causally.
All this suggests that the correlation between dermal inflamma-
tion and hair loss is complex and variable. The human hair follicle
has long been considered as immune-privileged.23, 24 Ito25 re-visited
this phenomenon employing the human hair follicle model. They
showed that the immune cytokine, interferon gamma could force
the collapse of the immune privilege in vitro, confirming the inflam-
matory link to hair loss. Such findings are particularly relevant for
the more immune-mediated hair loss disorder Alopecia areata.
The neuro-endocrine system of skin has been the subject of
a recent study.26, 27, 28 Skin is now acknowledged as a peripheral
neuro-endocrine organ that needs no central regulation but pro-
vides front-line defense and contributes to general homeostasis.
Interestingly, the hair follicle itself expresses the full complement of
these stress factors, which suggests hair follicles can be influenced
by local and central neuro-endocrine factors.26 Chronic stress has
been suggested to influence hair loss in women,27 although as yet,
no mechanistic studies exist to provide evidence for a direct link.
However, this type of research might lead to both local and holistic
routes to treatment of hair loss.
Demonstrating Hair Growth

The outcomes tracked in hair growth studies include consumer
self-assessments, clinical grades, and photographs of hair and
style.29 Some studies have invested in phototrichometry to measure
both growth rates and numbers of hairs.30 Notably, some studies
sample the hair and characterize it by careful measurement off of
the head.31
Successful hair growth treatment requires sufficient change for
the growth to be perceived. This can be driven by more hairs per
square centimeter or hairs of greater diameter. More hair can also be
a result of faster-growing hairs, hopefully of the same diameter. Hair

86
growth solutions should produce terminal hair that is strong and not
brittle, not vellus hair.
To better illustrate the importance of the fibers, following are some
measurements performed at TRI/Princeton of the variability of hair.
These studies were conducted on untreated, blended, virgin Euro-
pean medium-brown haira. The first measurement (Figure 1) shows
how variable the hair diameter is along a single fiber. Each hair was
mounted on a special purpose stage. This stage rotates the hairs in a
laser scanning micrometerb. The laser micrometer tracks the major
and minor axes of the hair with an accuracy of 50 nm or 0.05 m.
This diameter measurement was repeated every millimeter along the
fiber, a distance equivalent to approximately two days growth.
Figure 1. Diameter scans of several long hair fibers. Hair diameters change not only from
root to tip, but also due to biological cycling during growth.
The combination of regular sectioning and high-precision

dimensional measurement illustrates the semi-regular cycling of the
hair growth process. It is also clear that there are occasional events
when the hair suddenly becomes thinner or thicker. These may
include incidental damage to the fiber during the normal regimen of
washing, drying and combing.
a
Hair samples were obtained from DeMeo Brothers, NY.
b
The scanning micrometer is a product of Mitutoyo.

87
For these fibers, the diameters vary along the fiber with an aver-
age standard deviation of only 2.5%, but the range of diameters
along each fiber is a full 14% of the mean. The cross-sectional area
within a single fiber similarly has an average standard deviation of
6.5% and an average range of 31%.
In these scans of long fibers, it is obvious that for a single hair
type, the fiber diameter can vary widely. To better describe this hair-
to-hair variation, the diameters and cross sectional areas of 50 fibers
of blended virgin European medium brown hair were measured (see
Figures 2 and 3). The cross-section of these hairs is oval and in this
case, the largest dimension or the major axis was plotted in m. To
characterize this distribution, it is fit to a normal distribution with
a mean of 88 and a width of 15m. The mean hair in this sample
measured 88 m. The width of the distribution was a full 18 m, a
20% variation in diameter between hairs.
With this larger sample, the subject of the variability of hair
diameter along individual fibers can be revisited. For each hair, the
diameters were measured 5 times. The distribution standard devia-
tions, divided by the mean, are shown in Figure 4. The vast majority
of fibers have a diameter that is constant to within 5%. The distribu-
tion, however, is closer to a log-Normal with a long tail representing
many highly variable hairs.
Figure 2. The distribution of hair diameters (m) in a sample of blended hairs. The cross
section of these hairs is oval; in this case, the largest dimension or the major axis is
plotted in microns. To characterize this distribution, it is fit to a normal distribution:
p=exp (()2/2) with a mean of =88 and a width =15m.

88
Few studies carefully characterize the quality of the hair fibers.

The exceptions, however, demonstrate that this information is
interesting and valuable.12,32 Even the rate of hair growth can vary
significantly from fiber to fiber.12,33-35
Figure 3. Distribution of the cross-sectional area of the hairs whose diameters are plotted
in Figure 2. The average area is 4,400 m2 and the standard deviation is 1,215 m2; more
than 25%.
Figure 4. Distribution of the standard deviation of hair diameter along a 5-mm segment.
In this figure the within-hair standard deviation is measured as a percentage of the mean.
Most hairs have the same diameter, to within better than 5%, but the distribution is
skewed and is better described by a log-Normal distribution: p=exp ((ln())2/2);
=0.80, =0.44.

89
Recently, a number of hair fibers were sampled from a single

scalp on the seventeenth day after a hair dye treatment. The length
of the newly grown hair in each fiber was measured. The average
growth rate was 0.7 mm/day, or 10 in/year, compared with the gen-
erally accepted population average growth rate of 6 in/year. Notably,
individual hairs grew with different rates; the standard deviation
measured was 0.04 mm/day or about 5% between hairs. Perhaps the
need for regular styling is, in part, a result of this between-hair vari-
ability in growth rates.
Conclusions
There is still more to learn about hair growth control and what
influences the follicle. The translation of this knowledge into effec-
tive treatments is not keeping same pace. Care must be taken to
clearly identify the benefit or end point associated with each treat-
ment. Concrete benefits of biological treatments could be increased
number, size, strength or growth rates of hair.
With minoxidil and finasteride offering somewhat effective
treatments, it would perhaps require a considerable step-change
in benefit for a new product to compete at the global level; how-
ever, the available hair loss blogospheres or chat rooms might
point to future directions. The informal trials of many and varied
combinations of treatments reported with diaries, discussions and
photographs suggest that the complex problem of hair loss requires
a complex solution, which may not come from the traditional drug-
target approach.
Gillian E. Westgate, PhD

Westgate Consultancy Ltd., Bedford, UK
Don Harper, K. Ramaprasad, PhD, and Peter D. Kaplan, PhD
TRI/Princeton, Princeton, NJ USA
References
1. HB Chase, Growth of the hair, Physiol Rev 34(1) 113-26 (1954)
2. AM Kligman, The human hair cycle, J Invest Dermatol 33 307-16 (1959)
3. K Stenn, Exogen is an active, separately controlled phase of the hair growth cycle, J Am
Acad Dermatol 52(2) 374-5 (2005)

90
4. CR Robbins, Chemistry and Physical Behavior of Human Hair, 3rd ed., Springer Verlag,
NY (1997)
5. K Stenn and R Paus, Controls of hair follicle cycling, Physiol Rev 81 449494 (2001)
6. AG Messenger and J Rundegren, Minoxidil: Mechanisms of action on hair growth,
British J Dermatol 150 186195 (2004)
7. VA Randall et al, The hair follicle: A paradoxical androgen target organ, Hormone
Research 54 243250 (2000)
8. S Chanda, C Lee Robinette, JF Couse and RC Smith. 17-Estradiol and ICI-1882780
regulate the hair follicle cycle in mice through and estrogen receptor-pathway. Am. J.
Physiol. Endocrinol. Metab. 278: E202-E210, 2000
9. U Ohnemeus et al, Hair cycle control by Estrogens: Catagen Induction via estrogen
receptor (Era) is checked by ERb signaling, Endrocinology 146 (3) 12141225 (2005)
10. YL Lynfield, Effect of pregnancy on the human hair cycle, J Invest Dermatol 35
323327 (1960)
11. JT Headington, Telogen Effluvium: New concepts and review, Arch Dermatol 129
356363 (1993)
12. J Nissimov and U Elchalal, Scalp hair diameter increases during pregnancy, Clinical
and Exper Dermatol 28 525530 (2003)
13. DA Whiting, Chronic telogen effluvium: Increased scalp hair shedding in middle-aged
women, J Am Acad Dermatol 35(6) 899906 (1996)
14. D Whiting. Possible mechanisms of miniaturization during androgenetic alopecia or
pattern hair loss. J Am Acad Dermatol 45 S8186 (2001)
15. AG Messenger, R Sinclair. Follicular Miniaturisation In Female Pattern Hair Loss: Clinico-
Pathological Correlations. British J Dermatol 155 926930 (2006)
16. EA Olsen, Female pattern hair loss and its relationship to permanent/cicatricial
alopecia: A new perspective, J Invest Dermatol Symp Proc 10 217221 (2005)
17. C Deloche et al, Histological features of peripilar signs associated with androgenetic
alopecia, Arch Dermatol Res 295 422428 (2004)
18. C Pierard-Franchimont, P DeDoncker, G Cauwenbergh and GE Pierard, Ketoconazole
shampoo: Effect of long-term use in androgenic alopecia, Dermatology 196(4)
474477 (1998)
19. C Peirard Franchiment, V Goffin, F Henry, I Uhoda, C Braham, G Pierard. Nudging hair
shedding by antidandruff shampoos. A comparison of 1% ketokonazole, 1% pitoctone
olamine and 1% zinc pyrithione formulations. Int J Cosmet Sci 24 249256 (2002)
20. RS Berger et al, The effects of minoxidil, 1% pyrithione zinc and a combination of both
on hair density: A randomized controlled trial, Brit J of Dermatol 149(2) 354362 (2003)
21. Y Mahe et al, Androgenetic alopecia and micro-inflammation, Int J Dermatol 39
576584 (2000)
22. C Pierard-Franchimont et al, Dandruff associated smouldering alopecia: A
chronobiological assessment over 5 years, Clin and Exp Dermatol 31 2326 (2006)
23. RE Billingham and WK Silvers, A Biologists reflections on dermatology, J Invest
Dermatol 57 227240 (1971)
24. GE Westgate, RI Craggs and WT Gibson, Immune privilege in hair growth, J Invest
Dermatol 97 417420 (1991)
25. N Ito, T Ito, A Bettermann and R Paus, The human hair follicle is a source and target for
CRH, J Invest Dermatol 122 235237 (2004)
26. A Slominski, Neuroendocrine System of the Skin, Dermatology 211 199208 (2005)
27. N Ito et al, Human hair follicles display a functional equivalent of the hypothalamic-
pituitary-adrenal axis and synthesis cortisol, FASEB J 19 13321334 (2005)
28. EMJ Peters, PC Arck, R Paus. Hair growth inhibition by psychoemotional stress: a
mouse model for neural mechanisms in hair growth control. Experimental Dermatology
15 (1) 113 (2006)
29. J York, T Nicholson, P Minors and DF Duncan, Stressful life events and loss of hair
among adult women, a case-control study. Psychol Rep. 82 10441046 (1998)
30. EA Olsen, Current and novel methods for assessing efficacy of hair growth promoters in

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pattern hair loss, J of the Amer Acad of Dermatol 48 253262 (2003)

31. R Hoffmann, Tricloscan: What is new? Dermatology 211(1) 5462 (2005)
32. J Nissimov, Normal head-hair length is correlated with its diameter, Clin and Exper
Dermatol, 29 649657 (2004)
33. O de Lacharriere et al, Hair diameter diversityA clinical sign reflecting the follicle
miniaturization, Archives of Dermatol 137(5) 641646 (2001)
34. PE Hutchinson and JR Thompson, The cross-sectional size and shape of human
terminal scalp hair, Brit J of Dermatol 136(2) 159165 (1997)
35. D Van Neste, Thickness, medullation and growth rate of female scalp hair are subject to
significant variation according to pigmentation and scalp location during ageing, Euro J
of Dermatol 14(1)2832 (2004)

Chapter 13
Shampoo Formulation:
The Basics
KEY WORDS: shampoo, surfactants, cleansing agent, viscosity, foam
booster, stabilizer, conditioner, preservative
ABSTRACT: Once marketing requirements are known the ingredients of a
shampoo formulation can be selected.
To the uninitiated, formulation of shampoos seems easy! Its a one-

phase, water-based surfactant blend that foams! Simple, isnt it?
While that may indeed be the case when compared to inherently
unstable systems, such as emulsions, many complications may arise
that make it a more complex task than may first meet the eye.
Lets start with the basics. Table 1 presents an overview of the
raw materials that go into making a typical shampoo. Now lets
discuss how to get started.
Marketing Requirements
The first thing we need to have is a discussion with our marketing
friends, and yes they are (or should be) our friends. We need to
determine who will be using the shampoo (men, babies, women,
teenagers, etc.), hair type, the packaging, selling price/cost of raw
material target and claims that will be made. Once we have this key
information we can begin. Please recognize that this short article
can only touch the surface of formulation intricacies.
Primary Surfactant
The primary surfactant is the key foaming/cleansing agent in the
shampoo. When I first got started formulating shampoos the most
popular primary surfactant was SLS (sodium lauryl sulfate). In more
recent year it has been replaced by ALS (ammonium lauryl sulfate).

94
Shampoo Shampoo Formulation: The Basics
Im not really sure why this change was made, because they both
foam and clean the same and their irritation potential is also the
same. One possible reason is that ALS shampoos are formulated at
a lower pH (to insure we dont get liberation of ammonia), and at
this low pH (typically 4.5-6.0) we can add polyquaternium materi-
als that are more substantive to hair at a low pH.
Table 1. Shampoo components
Ingredient Chemistry Options % Function

(Active)
Primary surfactant Sulfates, sulfonates, etc. 8-12 Foaming, cleansing
Secondary surfactant Betaine, sarcosinate, 2-5 Foaming, cleansing,
sulfosuccinate, taurate, reduce irritation
ether sulfate, glucoside,
glutamates, etc.
Viscosity builder Alkanolamide, salt, amine 2-3 Control viscosity
oxide, PEG-distearate, etc.
Foam booster Amine oxide, sarcosinate, 1-2 Boost foam
lactylate, etc.
Foam stability Lactylate, gum, etc. 0.1-1 Stabilize foam
Active (when Zinc pyrithione, salicylic As per FDA Antidandruff agent
appropriate) acid, etc.
Suspending agent Xanthan gum, carbomer, 0.1-1.0 Suspend zinc pyrithi-
guar, etc. one or other materials
Conditioner Polyquat., silicone, etc. 0.1-1.0 Hair conditioning
Opacifier EGMS, EGDS, etc. 1.0-2.0 Pearlizer
Preservative Paraben, etc. 0.1-0.5 Preservation
Fragrance Fragrance 0.2-1.0 Fragrance
Humectant Propylene glycol, 0.25-1.0 Improve clarity,
glycerin, etc. reduce cloud point,
modify viscosity
Color Approved colorants As needed Color
Marketing additives Vitamins, aloe, As dictated Marketing claims
antioxidants,
UV absorbers, etc.
Chelating agent EDTA salt 0.05-0.15 Color/odor stability,
preservative
enhancer

95
Klein Chapter 13
If the target users are babies, then the lauryl sulfates would not be
used, but we would then find amphoteric surfactants such as propi-
onates and highly ethoxylated sulfates and carboxylates being used.
Very often, cost plays a major role in the choice of a primary
surfactant. Shampoos are, by far, the personal care category most
sensitive to pricing. This must be kept in mind when choosing all
ingredients and the percentages of those ingredients used.
Secondary Surfactant
Very often the secondary surfactant is used to reduce the drying
effect of the primary surfactant and modify the aesthetic properties
of the shampoo. The most popular secondary surfactant is the ether
sulfate analogue of the primary surfactant (ALES). Most often we
see the 1 and 2 mole (ethylene oxide) material being used. This
is the case because if we chose a more highly ethoxylated version,
viscosity building would be a problem. And who wants to buy a
water-thin shampoo?
The second most popular secondary surfactant is the betaine.
Betaines (most often cocamidopropyl) have a permanently quater-
nized nitrogen. Because of this they can be a good hair conditioning
agent and also complex with the sulfate to build viscosity and
improve clarity. While it was believed that they also reduce the
irritation of anionics, more recent information (personal communi-
cation with Tom Schoenberg of McIntyre Chemical) disputes this
and presents data to show quite the opposite is true. Other surfac-
tants such as sulfosuccinates, glutamate and sarcosinates can also
have a very beneficial effect but will substantially increase the raw
material cost.
Viscosity Builder
Few things are more important to consumers than seeing/using a
thick (rich) shampoo. They equate it with value and concentration.
Of course neither necessarily is true.
Alkanolamides have historically been used to increase the
viscosity. Experienced shampoo formulators actually know that
alkanolamides dont really boost viscosity but only change the posi-

96
tion of the salt curve; in other words, less salt is required to build
viscosity so it appears that they are boosting the viscosity. Alkano-
lamides have in recent years come under attack (particularly the
DEA amides) and we now see the MEA amides being widely used.
Alkanolamides also improve shampoo clarity by acting as fra-
grance couplers while also improving foam stability (to a very
limited extent when they are used at low use levels) and offering
some hair conditioning (due most likely to their water insolubility).
Other more effective viscosity builders include betaines. They
complex with the anionics to form an enlarged surfactant micelle
that builds viscosity. Additionally, they contribute electrolyte
(sodium chloride) that also builds viscosity. Electrolytes are almost
always used to build viscosity of shampoos. They are inexpensive
and effective. If too much is used, then a low cloud point will be
the result.
While sodium chloride is most used, ammonium chloride is also
widely used. Ammonium chloride is more efficient than sodium
chloride and will also not raise the cloud point. When it is used, like
ALS, the pH should be kept below 6.5 to insure that ammonia is
not liberated.
Foam Booster/Stabilizer
Consumers equate foaming with cleansing and believe that unless
copious amounts of foam are generated, their hair will not be
cleaned. This, of course, is not true. All shampoos, even the low
foaming baby shampoos, contain more than enough surfactant to
clean the grimiest, dirtiest hair. Low levels of secondary surfactant
(lactylates, glutamates, taurates, sulfocuccinates, sarcosinates, amine
oxides, etc.) can effectively boost foam at low concentrations (1-2%).
It is also crucial to deal with foam stabilizers. Having a volu-
minous quick breaking foam doesnt make sense. We need to add
materials that slow the breakage of the foam bubbles. This can be
accomplished by stabilizing the wall of the foam bubble. We have
several materials that can play this role for us: gums (cellulose, guar,
xanthan, etc., at 0.05-0.15%) and surfactants that form a liquid
crystal layer at the bubble wall and thus slow the break and stabilize
the foam.

97
Klein Chapter 13
Suspending Agents
When we have the need, based on marketing input, to incorporate
materials that must be suspended, we need to incorporate a sus-
pending agent. Most often we will use one or more of the following
materials: xanthan gum, carbomer, magnesium aluminum silicate,
cellulose gum. The choice will depend on factors such as cost, elec-
trolyte content, pH, the desire for clarity and the feel of foam.
Conditioner
Practically all shampoos sold today will contain a hair conditioner
of some type. This is even true for those shampoos that make no
conditioning claim whatsoever. Consumers expect and demand that
their hair is smooth and conditioned after shampooing.
Conditioning agents are most often quaternary in nature because
they possess a negative charge that makes them substantive to hair.
They will also have at least one fatty group to improve wet comb
and gloss. Most often polyquats are used in shampoos since they
are (due to stearic hindrance) more compatible with the primary
anionic surfactants. We also see wide usage of silicone and other
fatty materials to provide conditioning and gloss to the hair. These
materials plate out onto the hair during the rinsing process.
Opacifiers
To the consumer, a pearlescent shampoo connotes richness. Often
it can be used to hide a cloudy shampoo, turning a negative into a
positive. EGDS (glycol distearate) and EGMS (glycol stearate), or
a combination of both, are effective in this endeavor. Both crystal-
lize out and form a lovely pearlescense. Be careful to slowly cool the
shampoo to maximize this visual effect. Also, the addition of elec-
trolyte can help.
Preservative, Chelating Agent, Color

Every shampoo must be preserved. Very often the primary surfac-
tant will contain some preservative but additional must be added to
insure a well protected product. Since shampoos are rinse off prod-
ucts, we have a wide range of preservatives from which to choose.

98
The addition of a salt of EDTA will also help preservation and color
stability. Speaking of color stability, we should consider the addition
of a UV absorber to insure color stability on the shelf.
Fragrance
No fragrance-free shampoo has ever been successfully marketed, and
I doubt one ever will! The fragrance adds to the shampoo experience
and is thus a crucial part of the shampoo. It should be presolubilized
into some surfactant to insure good product clarity.
Marketing Additives
While its easy to make fun of the myriad of ingredients that mar-
keting asks (demands?) we incorporate (such as vitamins, minerals,
aloe, fruit, nuts, bark, twigs just kidding here), they are important
to the overall picture/image of the shampoo and must be added even
though science tells us that they have no function whatsoever.
Conclusion
So you can see that formulating a shampoo offers us lots of oppor-
tunity for individual creativity. Just let your minds wander, but keep
in mind the cost of goods!
Ken Klein
Cosmetech Laboratories Inc., Lincoln, CA USA

Chapter 14
New Technology
for Shampoos and
Conditioners: Between
the Shock Waves
KEY WORDS: shampoo, conditioner, cationic polymer, silicone, structured
surfactant technology, multifunctionality, combinatorial
chemistry
ABSTRACT: Though shampoo and conditioner technology is not
presently experiencing sudden and dramatic change, this
chapter reviews several recent advances in materials, test
methodology (combinatorial chemistry) and formulation
approaches (structured surfactant technologies).
There have been technical innovations in hair care of such impor-

tance as to cause a quantum level of change in formulation practices,
ingredient supply, and consumer usage. As a relative rarity, there
have only been two such events in shampoo technology during the
last 30 years. These are the incorporation of a cationic polymer
into an anionic surfactant system in the early 1970s,1 and the func-
tional incorporation of silicone in the late 80s2,3,4. In each case, the
improvement served as a technological shock wave causing a flurry
of competitive patent activity and product emulation. While we are
not experiencing such a period at this time, both suppliers and mar-
keters have achieved significant advances in the development of new
ingredients and the meaningful improvement of existing materials,
formulation approaches and test methodology.
Continual Advances / Old Challenges

Interestingly, in many cases these efforts have direct application to

100
Shampoo New Technology for Shampoos and Conditioners
the cited innovations of the 70s and 80s. For example, more than
25 years after its usage in anionic shampoo systems was patented,5
work continues towards improving the functionality, selectivity
and aesthetics (e.g., clarity) of cationic guar when used in these
applications. In one such case, Rhodia has recently determined
that in addition to their inherent conditioning properties, Jaguar
cationic guar polymers also function as deposition aids for other
non-substantive conditioning agents such as silicones. Their stud-
ies revealed a significant difference in the amount of their Mirasil
DME silicones deposited onto hair from SLES/Amphoacetate
systems, with and without their Jaguar C14S. In general, Rhodia
reports test results demonstrating Jaguar polymers to improve
silicone deposition up to three times. They attribute this deposi-
tion to the liberation of the silicone from a complex that it forms
with cationic guar upon dilution with water. Further, they report
the availability of Jaguar polymers specially designed to enhance
the deposition of additional active ingredients.
Related to improving the resultant performance of cationic
polymer-containing shampoos, National Starch has recently
demonstrated their Flexan II polymer to be effective in removing
cationic polymeric residue from hair. FlexanII is a high molecular
weight polystyrene sulfonate, sodium salt, with high anionic charge
density and excellent surfactant compatibility. National Starch
reports this material to effect removal through the formation of
a complex with the cationic polymeric buildup. In their studies,
Polyquaternium-10 was fluorescently labelled and deposited onto
hair tresses to simulate cationic build-up. Fluorescence spectros-
copy was then used to quantify the amount of labelled cationic
polymer on the hair tresses before and after treatment. Their
results indicate the inclusion of 1% (active) FlexanII in a mild
cleansing shampoo to increase polymer removal by 25%. They
report similar results using reflectance measurements of lumicrease
dye to track the removal of cationic polymer. In addition to pro-
viding an option other than strong surfactancy for the removal
of polymeric buildup, bearing an anionic charge leaves this
material novel among the predominantly cationic, static
flyaway suppressants.

101
Westman Chapter 14
Structured Surfactants: The Next Shock Wave?

The mention of quantum level changes and the infrequency with
which they occur in shampoo systems logically leads to speculation
as to the nature of the next major technological advance and when
it will occur. In this regard, it may be worthwhile to note that the
functionality of each of the technologies referred to above as pro-
viding quantum level change is based upon the ability to retain the
activity of a highly functional material in a medium where, hitherto,
it was lost.
The potential to provide this same type of protection leaves
structured surfactant technology a favored candidate for creating
significant change. As defined by Clapperton et al.6
The term structured surfactant is used . . . to refer to
pourable, fluid, non-Newtonian compositions which have the
capacity physically to suspend solid particles by virtue of the
presence of a surfactant mesophase or solid phase, which may
be interspersed with a solvent phase. The latter is commonly
an aqueous electrolyte phase. The surfactant phase is usually
present as packed spherulites dispersed in the aqueous phase.
Alternatively a thin mobile lamellar phase or a bicontinuous
reticular interspersion of aqueous and lamellar phases may be
present. Hexagonal phases are usually insufficiently mobile to
form the basis of a structured surfactant, but may, exception-
ally be present.
While these and similar systems have already gained usage in
liquid cleanser formulations, they have yet to leave their mark
in shampoos.
Advancing the potential application of this technology to sham-
poos, Huntsman Surface Sciences has recently developed optically
clear structured systems that can be made using surfactant, carbo-
hydrate and water. X-ray diffraction studies indicate these systems
to have repeat spacing of 20 to 50nm, which is approximately
twice the typical repeat spacing measured for electrolyte-structured
expanded G-phase systems, and approximately four times that of a
conventional spherulite system.
Towards the delivery of functional or active ingredients, this
technology is capable of suspending solid, liquid and gaseous

102
particles. Of interest to hair care formulators, such particles could

include anti-dandruff agents, silicones and encapsulated actives.
This technology provides polymer-free, transparent formulations
having excellent suspending power, pseudoplastic rheology; low
freezing point; wide thermal stability range (-5C to +50C). Fur-
ther, Huntsman reports these systems to be easy to formulate and
manufacture using readily available raw materials and to be surpris-
ingly self-preserved.
On a lighter, but nonetheless important note, these systems are
capable of providing a variety of interesting visual effects due to
low-miscibility color regions. These include: horizontal and verti-
cal stripes, vertical segments, marbling and, when viewed through
crossed polarizers, a visually impressive birefringence phenomena.
Hair Dye Multifunctionality

It is worthwhile to note that for the above cited examples of quantum
level changes in shampoo technology, the notable improvements were
not related to the primary purpose of cleansing, but instead, towards
the multifunctional benefit of conditioning. Importantly, the deliv-
ery of multifunctional benefits continues to be of vital importance to
shampoo and conditioner technology (and marketing).
The incredible growth of hair coloring during the past 10 years
has further stimulated and encouraged this trend. Here, all manner
of hair products have been enticed to include color protection as
a secondary benefit, or to directly add hair coloring functionality.
The latter has frequently and conveniently been achieved through
the inclusion of basic/cationic dyes such as James Robinsons,
JaracolTM, or Warner Jenkinsons Arianor dyes that provide
temporary to semi-permanent deposition of dye. (Conversely, most
hair color products claim conditioning as a secondary benefit.)
Such multifunctional hair coloring products must be carefully
formulated to provide meaningful color effects while maintaining
their primary functionality. This is particularly true of color-sham-
poo systems where the use of cationic dyes generally precludes the
use of anionic surfactants. Further, in shampoo systems the compe-
tition is keen between attraction of the dye for the anionic sites of
hair and resolubilization and removal by the surfactant system.

103
Westman Chapter 14
Tilting the competition in favor of the hair, Huntsman Surface

Sciences has recently developed a high purity cocamidopropyl
betaine (CAPB), which they report to improve the deposition
of these basic dyes from shampoo formulations. The Huntsman
material is substantially lower than conventional CAPB in sodium
chloride and sodium dichloroacetate, electrolytes known to inter-
fere with cationic dye functionality. They investigated the dye
uptake of basic dyes on tresses of bleached blonde human hair from
coloring shampoos based on either conventional CAPB, disodium
cocoamphodipropionate or high purity CAPB. Color results
revealed the high purity CAPB based formula to significantly out-
perform the other materials without compromise of either foam or
mildness characteristics.
While the Huntsman material is reported to aid the deposition
of color, several recent materials have been demonstrated to pro-
tect existing color while also providing conditioning functionalities.
Among these is Dow Corning HMW 2220 Non-ionic Emulsion
(INCI: Divinyldimethicone / Dimethicone Copolymer (and) C12-
C13 Pareth-3 (and) C12-C13 Pareth-23), an ultra high molecular
weight silicone emulsion with an internal viscosity of over 120
million centistokes. Dow Corning reports that, when employed in
rinse-off conditioners, HMW 2220 provides strong color protection
from shampoo and UV treatments and reduces wet detangling time
in shampoos and conditioners up to 50% (at 3% dosage) on Cauca-
sian hair. Finally, and somewhat surprisingly, it enhances delivery
of fragrance in shampoos. Here Dow Corning reports that expert
panelists at Takasago perceived up to 30% more fragrance intensity
on hair after lathering, rinsing, blow drying and even 6 hours after
use. This was further validated through consumer tests.
Another recently introduced material providing color protection
to dyed hair is Silsoft A 454 from Crompton OSi Specialties. This
material is reported to provide a unique feel to hair, along with the
performance properties expected of a functional silicone, while less-
ening the loss of dyed hair color when washed with a conditioning
shampoo containing this ingredient. Demonstrating this function-
ality, Crompton OSi Specialties evaluated the color fastness of dyed
bleached blonde hair after ten shampoos with a conditioning sham-

104
poo containing 1% Silsoft A-454 Conditioner versus that with a

cleansing shampoo. They report a significant difference between
the two treatments as evidenced both through visual comparison as
well as reflectance measurements.
Crodas Crodazofsoft DBQ, a recently introduced conditioning,
and softening agent for hair, has also been determined to improve
the shampoo resistance of dyed hair. Crodazosoft DBQ is a qua-
ternary compound combining the imidazoline functional group
and two behenyl alkyl chains. In Crodas testing, a rinse-out con-
ditioning formulation containing 1% (active) Crodazosoft DBQ
was applied to blonde hair that was dyed to a deep red with Clai-
rols Herbal Essence, Radiant Ruby (a semi-permanent oxidation
dye product). The dye fastness of these tresses was then compared
before and after 15 shampoos with that of identical dyed tresses,
either treated with a commercial rinse-out conditioning color
sealant, or given no after coloring treatment (untreated control).
Application of each rinse-out conditioner was repeated after each
fifth shampoo and color measurements were made with a Hunter
Lab Scan XE. At the completion of testing, Croda determined
that both instrumental data and visual observations indicate tresses
treated with Crodazosoft DBQ exhibit extremely little color fade
and shade change, and far less than the other groups.
Conditioning Advances
In addition to those related to color enhancement and protec-
tion, a number of interesting new conditioning and strengthening
ingredients have recently been introduced. Among these, is Crodas
Keravis (INCI: Hydrolyzed vegetable protein PG-propyl silan-
etriol), a unique copolymer of hydrolyzed vegetable protein and
silicone. Croda describes Keravis as a powerful hair-strengthening
complex that dramatically improves the strength of damaged hair,
and demonstrated its performance using a technique they term
flexabrasion. This interesting technique draws weighted fibers across
a tungsten wire in cycles, with the fibers fatigue lifetime being rep-
resented by the number of cycles that it is able to endure prior to
breaking. Contrasting flexabrasion with more static measurements,
Croda reports that the movement and forces it creates are more rep-

105
Westman Chapter 14
resentative of those experienced during grooming. Using flexabrasion

measurements, they determined treatment with Keravis to signifi-
cantly increase hairs resistance to breakage, and therefore strength.
In one study, Croda reports that treatment with a conditioner
containing 1% Keravis was determined to increase the strength of
bleached hair by 180%, as contrasted to an increase of 60% for the
same conditioner without Keravis.
Another new entry is Uniqemas Arlasilk Phospholipid PLN,
a water-soluble organosilicone composition that the manuacturer
reports to deliver exceptionally high silicone levels to hair care for-
mulations. They attribute patented pyrrolidone and phospholipid
chemistry with increasing the polarity of this organosilicone, yield-
ing a product that is extremely mild, substantive and water-soluble.
While approximately 70% silicone by weight, a major benefit of
Arlasilk Phospholipid PLN usage is considered to be its ability to
deliver excellent wet combing and conditioning performance in
clear formulations.
Combinatorial Chemistry: Accelerated Innovation

Early in this chapter, it was noted that, among other things, this is
a period during which emphasis is being given to the meaningful
improvement of test methodology. Prominent among these is an
exciting new strategy for materials discovery that combines minia-
turization and automation to produce and test very large numbers
of new materials in a parallel manner. Here, ingredient synthesis
is typically carried out in parallel on arrays of 10 to 1000 elements,
each containing 100 to 1000 mg of material. These arrays, or
libraries, are then formulated into model products and screened
for chemical and physical properties of interest. This quickly identi-
fies the most promising formulations, which are then scaled up to
larger quantities and evaluated by conventional techniques. Unsuc-
cessful formulations, in contrast, are identified and rejected before
considerable time and money have been spent on their development.
This approach, known as high throughput screening or com-
binatorial chemistry, is capable of evaluating hundreds or even
thousands of new formulations per week. Originally developed in
the pharmaceutical industry for the rapid identification of new drug

106
candidates, these methods have since been extended to cover all of

materials science. Their successful application to the very differ-
ent materials and methods found in the personal care industry has
required new and innovative ways of rapidly synthesizing polymers
and small molecules in small quantities; blending these materials
into small-scale model formulations which could be solutions, dis-
persions, or emulsions; applying these formulations to appropriate
surfaces (such as hair); and measuring their physical characteristics.
For example, using high throughput approaches, one can cre-
ate arrays of new water-soluble segmented polymers, incorporate
promising candidates into model formulations, determine relevant
properties of these formulations, treat hair with the most promising
candidates and then measure the resultant physical changes. Clearly,
such testing could play an important role in increasing the frequency
with which we experience quantum level of change in shampoo and
conditioner technology. However, this may provoke future argu-
ments similar to those existing in the sports world, where one could
be required to note by asterisk: *Achieved with the assistance of high
throughput technology, when comparing a chemists accomplishments
to that of an earlier generation.
Summary
There have been few major innovations in shampoo and conditioner
technology during the last 30 years. Notably, there have been only
two innovations in shampoo chemistry that have been of adequate
significance to have created a quantum level of change. These were
the incorporation of a cationic polymer into an anionic surfac-
tant system in the early 70s, and the functional incorporation of
silicone in the late 80s. While significant time has elapsed since
these discoveries, their shock waves persist though the continual
improvement of these technologies, and the ever-growing emphasis
on the achievement of multifunctionality through the intact deliv-
ery of functional ingredients. As examples: Efforts continue to
improve cationic guar based shampoo systems; new silicone deriva-
tives continue to be introduced; and a number of new shampoo and
conditioner ingredients focus on multifunctional benefits. Here,
given the incredible growth of this product category during the past

107
Westman Chapter 14
decade, multifunctional benefits related to hair dyes are the prime

focus of a number of new chemical ingredients.
In response to the logical speculation as to the basis for the next
major advance in shampoo technology, the use of structured sur-
factant technology is offered as a prime candidate. With unique
properties resulting in the ability to suspend and deliver ingredi-
ents from surfactant systems, these materials have the potential to
deliver advanced multifunctional benefits the primary basis for the
last two quantum levels of change. Further, the application of high
throughput methods (or combinatorial chemistry) offer the possibil-
ity of dramatically reducing the time lapse between major advances.
Employing these methods, steps from ingredient synthesis to incor-
poration in model formulations and evaluation on hair are executed
in miniaturization, resulting in 100 to 1000-fold reduction in time.
Given such methods, and innovations in chemical ingredients, it
appears that we have a number of tools in place for the development
of the next significant quantum level of change. Regardless of its
composition and timing, one can be certain that it will be exciting
to experience, and interesting to track its conformance to history, as
well as its impact on the future.
Mort Westman
Westman Associates, Inc., Oak Brook, IL USA
References
1. T.Gerstein Shampoo Conditioner Formulations US3990991 Nov 9,1976.
2. Bolich, Jr. et. al. Shampoo Composition Containing Non-volatile Silicone and Xanthan
Gum US Patent 4,788,006 November 29, 1988.
3. Oh, et. al. Shampoo Composition US Patent 4,704,272 November 3, 1987.
4. Gtete, et. al. Shampoo Composition U. S. Patent 4,741,855 May 3, 1988.
5. Oberstar, Westman Conditioning Shampoo Containing Cationic Guar US Patent
4,061,602 December 6, 1977.
6. Clapperton , et al. Aqueous Based Surfactant Systems US Patent 6,177,396, January
23, 2001.

Chapter 15
Working up a Lather
KEY WORDS: marketing statistics, natural raw materials, shampoos, foam,
lather, preservatives, parabens
ABSTRACT: Discussion of formulating challenges of benefit-driven rather
than aromatherapy- based natural hair care products to
attract new consumers and bring natural shoppers back into
the hair care category.
Driven by increasing awareness and concern by consumers about

the source and properties of the ingredients in their personal care
products, the conversion to more natural formulations in per-
sonal care is gathering momentum. The natural hair care category
is undergoing a shift as technology and formulations improve,
enhancing performance and functionality while maintaining the
natural integrity and positioning of the products.
Traditionally, many consumers shopping in natural product
stores have been disappointed with natural hair care products,
and often have continued to buy hair care products in mainstream
outlets due to the noticeable differences in texture, lather and
functionality that non-naturals provided. Some of the features
expected from a shampooa rich creamy lather, for exampleare
created with synthetic or harsh chemicals that natural formulators
do not use. In addition, the natural hair care category has con-
sisted primarily of shampoos and conditioners differentiated by
scent and aromatherapy benefits rather than function or hair
care solutions.
Marketers of natural hair care products are increasingly devel-
oping and introducing products that are benefit driven rather than
aromatherapy based to attract new consumers and bring shoppers
back into the natural hair care category. Based on current consump-
tion data, this strategy seems to be working. The natural hair care

110
Shampoo Working Up a Lather
category is the second fastest-growing HBA naturals category, up

19.4% on an annual basis.
Defining and Differentiating Naturals

Natural formulations often are defined by what they do not include:
parabens, sodium lauryl/laureth sulfates, and petroleum-based and
animal-derived ingredients. Excluding these ingredients often
extends the development time because new ingredients have to be
sourced, evaluated and tested for effectiveness.
Increasingly, natural marketers also are seeking to differentiate
themselves with unique plant-based ingredients not available in
mainstream products. Research to support the topical benefits of
these ingredients is being conducted by both ingredient suppliers
and marketers to support the effectiveness and help persuade con-
sumers that natural products can effectively address their hair care
needs. In addition, suppliers are discovering new botanicals and
indigenous ingredients more rapidly due to global sourcing.
Just a few years ago, most marketers and consumers were not
aware of the moisturizing benefits of babassu oil from Brazil or the
antioxidant benefits of rooibis red tea from South Africa. These new
ingredients supported by research data and a better understanding
of natural formulation techniques have enhanced natural hair care to
more effectively meet consumer demand and expectations.
Lather and Foam

Formulating hair care products presents numerous challenges due
to the characteristics and needs of every individuals hair. Human
hair varies enormously depending on race, gender, age and genet-
icswhich, in turn, affect the diameter, color and texture of the
hair. In addition to cleansing and conditioning, consumers demand
hair care products that solve specific hair problems or complement
a particular style. To achieve these goals, all the characteristics of
hair must be taken into account during the development phase.
The first challenge formulators face in developing natural sham-
poos and conditioners is foam and lather that both reinforce the
perception that the product is working. Consumers expect foam

111
Vazquez Chapter 15
and lather. Many traditional surfactants and foaming agents, such

as sodium lauryl/laureth sulfates and cocamide DEA, are harsh and
extremely irritating to the scalp. There also has been some pre-
liminary research implying that these agents may be carcinogens,
however, there has not been sufficient research to prove this claim.
Natural formulators seek out mild, naturally derived surfactants such
as sodium myreth sulfate, which is derived from coconut oil.
A second challenge for natural formulators is enhancing the
cleansing properties with plant-derived ingredients that solve
specific hair needs. Natural oils, such as jojoba oil, effectively
condition and hydrate the hair, while wheat proteins add shine. As
natural ingredients become more popular, additional research is
being conducted by both manufacturers and suppliers to support
ingredient effectiveness and discover new properties and applica-
tions. For decades, tea tree oil has been known for its therapeutic
benefits to the skin. Now, it has found its place in hair care formu-
lations as an effective ingredient to soothe scalp irritation and help
eliminate dandruff.
Natural Preservation
Effectively preserving natural products is perhaps the most chal-
lenging aspect of developing naturally based shampoos and
conditionersas well as other natural personal care products.
Parabens are the most commonly used preservative system out-
side the natural industry. They are economical, broad spectrum,
petroleum-based preservatives that usually appear as methylparaben
or propylparaben on an ingredient list, are used in many pharma-
ceutical, food and cosmetic products. Due to consumer demand,
however, the natural industry is eliminating the use of parabens
as a preservative system in all formulations. While effective at low
levels, parabens have been found in breast tumors, leading many to
question the ingredients safety. Although there is no firm evidence
or causal linkage established between parabens and breast cancer,
consumers are increasingly selecting paraben-free brands. Jason was
the first brand to remove parabens from its line. Avalon Organics,
Kiss My Face and Burts Bees also are paraben-free.

112
Shampoo Working Up a Lather
Paraben-free formulations often require the combination of

multiple ingredients to effectively preserve the product. Varying
pH levels, viscosity and water content combined with the different
properties of antimicrobial agents require that each formula utilize
a different preservative systemor at least a different combination
of preservatives. Certain preservatives may reduce the viscosity of a
formula, change the color or alter the performance. Common para-
ben alternatives are sodium benzoate, phenoxyethanol and enzymes
such as glucose oxidase and lactoperoxidase.
Challenges Offset by Opportunity

Along with challenges, natural product marketers and formula-
tors are presented with the opportunity to bring innovation and
creativity to the formulation of hair care through the sourcing of
new natural ingredients and developing new ingredient combina-
tions to achieve the desired results. As traditional assumptions are
questioned and new data collected, there is a greater opportunity
to bring unique products to market and address consumer needs.
Natural product marketers are increasingly developing ranges that
target specific consumer needshelping to differentiate products
within the natural category while also enabling these brands to
better compete with mainstream products that are perceived to be
more effective. Although many consumers are demanding more
natural ingredients and seeking out information about the ingre-
dients in their personal care products, they are not willing to give
up performance or effectiveness. Natural product marketers are
addressing these concerns and perceptions through advertising,
education and sampling.
The double-digit growth the natural hair care category is experi-
encing confirms the success that natural marketers are having. The
introduction of functional-based products is driving the growth in
the styling category, up 22.6%* annually, representing the fastest-
growing segment of the natural hair care category. Consumers can
look forward to additional product introductions that address their
*SPINS SCAN 52 weeks ending June 17, 2006

113
Vazquez Chapter 15
need for functional, solution-driven hair care products that fit into
their natural lifestyle and values.
Luis Vazquez
The Hain Celestial Group, Boulder, CO USA
Published October 2006 GCI

Chapter 16
Deposition from
Conditioning Shampoo:
Optimizing Coacervate
Formation
KEY WORDS: deposition, coacervate, polymers, hair conditioning,
shampoos
ABSTRACT: New techniques are being offered to produce formulations
faster and more cost effectively than ever before. Researchers
at the Institute for Formulation Science have addressed this
challenge by developing robotic combinatorial techniques for
the preparation and investigation of complex mixtures.
Most conditioning shampoos depend on deposition of a poly-

mer-surfactant coacervate to confer good wet-combing and
manageability. Complex coacervate formation is crucially depen-
dent on the molecular characteristics of the polymer and surfactant
species, and it is significantly affected by the presence of other
ingredients such as cosurfactants and dissolved salts. The optimiza-
tion of these systems presents a challenge to the formulator because
of the astronomical number of possible compositions with different
performance outcomes.
Conventional formulation practice requires literally years of labo-
ratory experimentation to characterize and optimize products that
depend on complex coacervate formation. Robotic combinatorial
techniques that accelerate the characterization and optimization of
complex coacervate formulations have been explored at the Institute
for Formulation Science. There has been success in constructing
compositional phase diagrams that fingerprint the compositional

116
Shampoo Deposition from Conditioning Shampoo
range of complex coacervate formation as a function of polymer

and surfactant molecular characteristics and the presence of other
ingredients. These diagrams quickly guide the formulator to com-
positions of interest, and dramatically reduce the time and effort
required for the screening of new ingredients, the formulation of
new products and optimization of existing products. This chapter
briefly describes the application of combinatorial techniques to
the detailed study of complex coacervation from the system: guar
hydroxypropyltrimonium chloride (and) sodium lauryl ether sulfate
(and) water (aqua) (GHCSL).a
Goddards original research into the nature of the interaction of
cationic polymers with anionic surfactants formed the technological
platform for modern conditioning shampoos.1 For systems com-
prised of a cationic hydroxyethylcellulose and anionic surfactants,
Goddard showed that below the surfactant critical micelle concen-
tration (CMC), an insoluble coacervate phase was formed and this
phase was resolubilized at a surfactant concentration that was above
the CMC. This mechanism formed the basis of the now familiar
dilution-deposition concept for conditioning shampoos that relied
on formulation of the solubilized coacervate in the shampoo and
deposition of phase-separated coacervate as the system was diluted
below the CMC upon rinsing.
However, behind this apparently simple mechanism there lies a
complexity that continues to engage formulators to this day. Thus,
patents continue to be issued in this area although more than 30
years have passed since the original discovery. The nature of the
coacervate in these systems critically depends on factors such as
polymer molecular weight, charge density, charge density distribu-
tion, and details of surfactant structure, cosurfactant ratio, and the
presence of electrolyte. The coacervate properties must depend upon
the conformation of the cationic polyelectrolyte and the hydration
of that polyelectrolyte. The conformation of the polyelectrolyte
depends, in turn, upon the ionic strength of the system as well as
the exact nature of the ion-exchange process that causes surfactant
to bind to the cationic sites. The overall hydration will be affected
a
INCI name Guar hydroxypropyltrimonium chloride/sodium laureth sulfate/water.

117
Lochhead et al. Chapter 16
by the availability of water binding groups such as hydroxyl groups

on the polymer. Interaction of the cationic polymer with anionic
surfactant micelles would be expected to change the micellar struc-
ture. It is well known that an increase in ionic strength will cause
structural transitions from spherical to rod-like micelles, worm-like
micelles or even lamellar phase. All of these micellar structures have
distinct rheological properties and kinetics. Prediction and optimi-
zation of these systems is complicated by the complexities of the
interactions. Alternatively, empirical formulation for ultimate under-
standing and optimization of the systems would require the study
of a large number of possible polymers, charge densities, structures,
molecular weights, surfactant types and ratios, ionic strength and
electrolyte type. Such a study would require an army of formulators
or a very long time to complete.
This challenge has been addressed by the Institute for Formula-
tion Science with its development of robotic combinatorial methods
for the study of these types of formulation problems requiring the
generation of large data sets. At the present time researchers at the
institute are engaged in developing their understanding of complex
coacervates systems by the rapid generation and investigation of
thousands of formulations in short time periods. The properties of
these formulations are plotted as composition diagrams to guide
the formulator.
The Combinatorial Investigation of Complex

Coacervation
At the current time the preferred method for the preparation of
complex mixtures at the institute is to utilize a robotic liquid han-
dlerb and to prepare mixtures in 96-well plates in which each well
contains a sealable glass vial of appropriate size for the system being
studied. The robotic equipment is limited to handling low-viscosity
liquids. Therefore, researchers at the institute have developed mul-
tiple manual pipetting techniques to handle high-viscosity liquids.
New pipette tips were used for each solution in order to avoid
cross-contamination of the samples. When high throughput screen-
b
A product of Beckman-Coulter, Inc., Fullerton, Calif., USA

118
ing is conducted, it is necessary to include standard compositions

to ensure the accuracy of the results; because instruments do drift
with time, components such as pumps can fail. It is important to
correct these deviations to avoid flawed data. With this in mind, at
least two standard compositions in each 96well plate were included
and the measured values of these compositions were plotted. Any
significant deviation was investigated immediately and, if necessary,
corrective measures were taken.
The compositions were mixed by vortexing the 96-well plate. In
order to ensure that the samples adequately were mixed, two dyed
samples were included in each 96-well plate. Measurement of max
of the dye solution was a monitor for adequate mixing (see Figure
1) (see Color Insert 1).
Figure 1. A combinatorial approach to the formulation of liquid products.
High Throughput Analytical Techniques

Measurement using light or other common electromagnetic radia-
tion is quick and nondestructive. Therefore, whenever possible, a

119
spectrometerc capable of reading 96 samples as a single batch was

utilized. This instrument provided the capability to measure entire
spectra, to measure wavelength shifts and to measure concentra-
tions of desired species in a few minutes using Beers Law.
The samples were viewed through crossed polarizers to detect
birefringent phases such as liquid crystals. Microviscosities were
measured by observing depolarization of biphenyls. The amount of
coacervate in a sample was assessed by measurement of the absor-
bance in the visible region.
The data was collected in an interactive database and then
visualized as color-coded composition maps. These composition
maps showed the volume of complex coacervate formed as a func-
tion of polymer structure and composition, surfactant composition
and electrolyte concentration. In original work to date, these maps
have been shown to be distinctive for each polymer investigated.
The precise mechanisms of coacervate formation and the driving
forces involved were deduced from the characteristic patterns in
the maps.
An important and usually time consuming aspect of each of the
studies is the validation of the high throughput experimentation
methods with standard laboratory procedures and confidence that
the methods will scale-up reliably.
Results
Cationic polymers, such as guar hydroxypropyltrimonium chloride,
provide hair conditioning from shampoos. Guar hydroxypropyltri-
monium chloride compounds, with varying molecular weights and
charge densities, were combined with the anionic surfactant sodium
lauryl ether (3EO) sulfate to form complex coacervates. Generating
more than 350 compositions for each polymer/surfactant combi-
nation, researchers used high-throughput screening formulation
methods to identify the structure and amount of coacervate formed.
These results were represented using contour phase diagrams in
order to map specific areas to study in detail. The detailed struc-
c
The Safire UV/VIS is a product of Tecan Systems, Inc., San Jose, Calif. USA.

120
tures of the lyotropic association colloids that were selected from

Figures 2, 3 and 4, were identified using polarized light microscopy.
One might expect that coacervate amount and composition
range would increase with increase in polymer charge density. This
indeed was observed as displayed in Figure 2 (see Color Insert
1), which shows increased amounts of coacervate as the polymer
cationic charge density is increased from 0.14 to 0.17 moles per
equivalent anhydroglucose unit.
The influence of polymer molecular weight on coacervate for-
mation can be seen from Figure 3 (see Color Insert 2). Each of the
three cationic guar samples possessed the same degree of cationic
substitution (0.14), but they ranged in molecular weight from 1
million daltons (d) to 2 million d. It clearly is observed that the
amount of coacervate formed increased in amount and concentra-
tion range as the polymer molecular weight was increased, despite
the constancy of polymer charge density. There is a minimum poly-
mer concentration that must be exceeded for coacervate formation
to be observed. The lowest molecular weight polymer displays two
islands of coacervate formation. It is suspected that this indicates
two distinct mechanisms; one relying primarily on ion-exchange
between the polymer and the anionic surfactant, and the other
being driven by a change in surfactant micelle size and shape.
It is reasonable to assume that the interaction between oppo-
sitely charged polymer and surfactant should result in a collapse
of the electrical double layers of both species. If this is the case,
the response of the surfactant micelle should be to increase in size
and to adopt a shape having lower surface curvature. Ultimately,
the micelles might be expected to grow into lyotropic liquid crys-
tals. Anisotropic lyotropic liquid crystals are optically birefringent;
that is they rotate the plane of plane-polarized light. If lyotropic
liquid crystals are present, they should be detectable by observ-
ing the compositions through crossed polarizers. This experiment
was conducted for the systems shown in Figure 3. The result of
the birefringence measurements are shown in Figure 4 (see Color
Insert 2).
It is notable that the compositional regions of birefringence
correspond closely to the coacervate compositions reported in

121
Figure 2. Composition diagrams for GHCSL. The diagrams are color-coded in accordance with
the visual spectrum with blue representing the absence of coacervate and red indicating
the maximum concentration of phase-separated coacervate. Each diagram was constructed
from observations on at least 368 separate compositions and each composition was
duplicated to check accuracy. The molecular weight was identical for both cationic guars
but the degree of cationic substitution is 0.14 in diagram (a) and 0.17 in diagram (b).
Figure 3. Composition diagrams showing regions of coacervate formation for GHCSL for
cationic guars having the some change density but different molecular weights.
Figure 4. Composition diagrams showing regions of birefringent compositions for GHCSL

for cationic guars having the some change density but different molecular weights.
Birefringent compositions are these shown in red.

122
Figure 3. It was concluded, therefore, that the micellar structure of

these coacervates is lyotropic liquid crystalline in nature.
Summary
Todays competitive environment demands that formulators produce
tangible results at a greatly accelerated pace. Composition maps
can be constructed rapidly to clearly show the effect of polymer
molecular weight and charge density on the composition range of
coacervation. Studies of birefringence indicate that the coacervates
contain lyotropic liquid crystals. The composition maps provide
valuable direction to formulators and can accelerate the develop-
ment of new products and novel intellectual property.
Robert Y. Lochhead, Lisa R. Huisinga and Tara Waller

The Institute for Formulation Science,
The University of Southern Mississippi, Hattiesburg, MS USA
Published December 2005 Cosmetics & Toiletries
References
1. ED Goddard and KP Ananthapadmanabhan, eds, Interactions of Surfactants with
Polymers and Proteins, CRC Press: Florida, Chapter 4 (1993)

Chapter 17
Advances in Polymers
for Hair Conditioning
Shampoos
KEY WORDS: polymers, hair conditioning, shampoos
ABSTRACT: The dilution-deposition mechanism is the core of the
modern conditioning shampoo. It is described here,
along with polymer inventions that enhance benefits and
improve the clarity of conditioning shampoos, and enable
conditioning from shampoos that do not contain a
cationic polymer.
Cationic polymers, specifically polyquaternium-10 and guar

hydroxypropyltrimonium chloride, have been included in sham-
poos to confer wet-conditioning benefits and style to the hair after
drying. Interest in these systems has recently been revived due to
advances in our knowledge of the nanoscience of self-assembling
systems and polymer-surfactant coacervates. The trend has
been driven commercially by the desire to enhance deposition of
actives and benefit agents from cleansing compositions during
the rinsing.
Conditioning Shampoos
The origin of conditioning shampoos can be traced to the Balsam
Shampoos of the 1960s followed by the introduction of polyquater-
nium-10 and the groundbreaking work and scientific insight of
Des Goddard1 in the 1970s and 1980s in which he introduced the
concept of polymer-surfactant complex coacervates that phase-
separated and deposited on the hair during rinsing. During the

124
Shampoo Advanced in Polymers for Hair Conditioning Shampoos
1980s and into the 1990s, complex coacervates were employed

as vehicles for the deposition of silicone on hair as conditioning
shampoos evolved.2 This trend continues today and the two original
polyelectrolytespolyquaternium-10 and guar hydroxypropyltrimo-
nium chloridecontinue to be the dominant polymer actives in
conditioning shampoos.
Polyions in aqueous solution are surrounded by small-molecule
counterions (Figure 1). If the counterions are very soluble in water
they will be driven by chemical potential to diffuse to regions of
lower counterion concentration and away from the polyion and
towards the free water. However, because the polyion and the
counterions carry charges of opposite sign, the counterion diffusion
away from the polyion chain is restrained by the electrochemical
potential due to ion-ion attraction. The balance between counte-
rion chemical potential and electrochemical potential determines
the ultimate location of the counterions with respect to the polyion
chain. This balance between chemical potential and electrochemi-
cal potential is called the Donnan Equilibrium. If the counterions
diffuse far away from the polyion chain, then the like charges that
are covalently attached to the polyion will mutually repel and the
polyion will swell.
Wetting of the Hair
Wetting of the hair by the applied polymer solution is extremely

important because capillary forces are necessary to pull adjacent fibers
together in order to form inter-fiber seam-welds and to cause migration
of the solution to inter-fiber cross points where it will be captured due
to a balance of Laplace Pressure between the curvature at the hair-
liquid curvature and opposite curvature at the air-liquid interface. This
phenomenon is commonly observed as the adhesion between the bristles
when a paint-brush is loaded with paint. Dewetting of the hair can
cause the fibers to be driven apart and this would inhibit migration of
the fixative solution to cross points of the hair matrix and prevent the
formation of seam welds between fibers.

125
Surfactant ions contain a large hydrophobic group and this

makes them intrinsically less soluble in water than inorganic ions
such as chloride or bromide. When surfactant ions interact with
an oppositely charged polyion, they bind strongly and displace
the water-soluble inorganic ions from the polyion; that is, they
ion-exchange (Figure 2a). Once the surfactant ions bind, hydro-
phobic interaction between the hydrophobic surfactant tails causes
the polymer-surfactant complex to collapse (Figure 2b). If the
surfactant concentration is sufficiently high to form micelles or
hemi-micelles along the polyion chain, then the charge on the poly-
ion is reversed and the polymer-surfactant complex will re-expand
and will be solubilized (Figure 2g).
Conditioning shampoos are formulated within the range of
surfactant concentrations that correspond to this solubilized regime.
If this solubilized complex (shampoo) is diluted to a concentration
in the vicinity of the critical micelle concentration, then the complex
coacervate phase-separates (Figure 2f). If the separated phase has
the correct mechanical and electrical properties it will be depos-
ited on the hair during rinsing. This so-called dilution-deposition
mechanism lies at the heart of modern conditioning shampoos.
Conditioning shampoos are expected to confer the wet hair
attributes of hair softness and ease of wet-combing, and the dry hair
attributes of manageability, good cleansing efficacy, long-lasting
Figure 1. Polyelectrolyte solubility in water is governed by Donnan Equilibrium

126
Antidandruff Discoveries at P&G

Procter & Gamble researchers have discovered that the coverage and
bio-availability of the antidandruff agent is a better measure of antidandruff
efficacy than the absolute deposited amount.20 Thus, the antidandruff active
will be more bio-available if it is co-deposited on the surface of coacervate
particles rather than if it is encapsulated inside the coacervates and if the
coacervate is soft and spreadable rather than elastic on the hair surface.
These researchers also define a bioavailability coverage index that
is measured by the following method. Samples of product, control, and
placebo were applied to portions of pigskin, which were then lathered
and rinsed. Agar contact plates inoculated with Malassezia furfur were
exposed to the pigskin surface, and after an incubation period, the plates
were analyzed using commercially available software to determine the area
of the agar surface which had been colonized by M. furfur. An index was
calculated comparing the area colonized in a control relative to the area
colonized in each sample. The inhibition of M. furfur growth on the plates
is indicative of the bioavailability of the antidandruff agent and coverage of
the antidandruff agent, which together and independently are indicative of
overall antidandruff efficacy.
Also, they defined first and second conditioning indexes that were
measured respectively by wet-combing and expert panel clean-feel
assessment. Based upon this, they claim improved antidandruff shampoos
based upon
An anionic surfactant that can be one of the following:

o Alkyl sulfates or alkyl ether sulfates
o Alkyl sulfonates alkyl / aryl sulfonates, beta-alkyloxyalkane
sulfonates
o Sarcosinates or sarcosinate derivatives
A non-volatile conditioning agent, such as silicones or organic

conditioning oils
An antidandruff agent. Zinc pyridinethiol-N-oxide is preferred.
A cationic polymer. The preferred cationic polymers have a molecular

weight in the range 350,000 to 500,000 and a charge density in the
range 0.6 to 0.9 meq/g.

127
Figure 2. The dilution-deposition mechanism of modern conditioning shampoos

128
moisturized feel, with no greasy feel. Recent research efforts have

been directed towards:
Optimizing polymer and surfactant structure and formulation
variables to seek enhanced benefits
Adding other components to enhance the conditioning benefits
Improving the clarity of conditioning shampoos, and
Seeking new methods of conferring conditioning from sham-
poos that do not contain a cationic polymer.
Optimizing Polymer and Surfactant Structure and

Formulation Variables
A combination of anionic detersive surfactant with guar hydroxy-
propyltrimonium chloride in the molecular weight range 10,000
to 10 million and charge density from 1.25 to 7 meq/g is taught to
form coacervates that confer excellent conditioning benefits.3
Precise optimization of a conditioning shampoo formulation is
exemplified in a patent application by Peffly et al4 who teach optimi-
zation of coacervate in a conditioning shampoo from a composition
comprising:
From about 0.01 to about 5 wt. % of a cationic cellulose poly-
mer, wherein the cationic cellulose polymer has a molecular
weight of at least 800,000; and
From about 5 to about 50 wt. % of an anionic surfactant system
having specified levels of ethoxylate and sulfate. The ethoxy-
late level is in the amount of 1.04 multiplied by the molecular
weight of the cationic cellulose polymer divided by 1,000,000
plus from about 0.75 to about 3.25. The sulfate level is in the
amount of 0.42 multiplied by the charge density of the cat-
ionic cellulose polymer plus from about 1.1 to about 3.6; and
From about 0.01 to about 5 wt. % of a mono or divalent
salt; and
At least about 20 wt. % of an aqueous carrier.
Adding Other Components to Enhance Conditioning

Benefits
By the use of microscopic identification, with and without dyes,
Wells et al showed that the inclusion of polyalkylene oxide alkyl

129
ether particles in a conditioning shampoo led to larger coacervate

flocs (20-500 microns) that resulted in cohesive flocs that resisted
shear and gave superior deposition efficiency on hair that conferred
good wet conditioning.5 Typical components of such a shampoo are
shown in Table 1.
A conditioning shampoo containing a polyester oil formed from
a condensate of a polyprotic acid and a polyprotic alcohol is taught
to provide manageability for dry hair (possibly from reduced hair
friction), no greasy feel, and a moisturized feel.6 For example the
polyester is a polycondensate of adipic acid and pentaerythritol
polycondensate with a molecular weight in the range 800 to 10,000.
This is exemplified by Formula 1.
Researchers at Johnson and Johnson teach that shampoos
containing more than one cationic conditioning polymer and a qua-
ternary silicone give more uniform deposition on hair than standard
shampoos based on Polyquaternium-10 as the sole conditioning
polymer.7 According to claims in the invention, the conditioning
polymer cocktail comprises poly(acrylamide-co-acrylamidopropy-
ltrimonium) chloridea, guar hydroxypropyltrimonium chloride, and
silicone quaternium-13. The claims are based upon multiple testing
and analysis, namely:
A Multiple Attribute Consumer Assessment Study against
Pantene Pro-V for normal hair and J&Js pH 5.5 regular
shampoo. The attributes measured were cleaning, wet-comb,
dry-comb, hair softness, lather amount and creaminess.
Secondary Ion Mass spectrometry to detect silicon on the
hair surface. This method revealed that Pantene Pro-V
concentrates silicone on cuticle edges whereas the Patent
Application shampoo distributed silicone more evenly.
X-Ray photoelectron Spectroscopy (XPS ) to measure thick-
ness of silicone polymer layer on hair from Si:C:O ratios. This
method revealed that Pantene deposited a significant amount
of silicone, and the Patent Application shampoo deposited
only one or two molecular layers.
Instron Ring Compression as a measure of combability
a
An example is Salcare SC 60 from Ciba.

130
Table 1. Adding components to enhance the conditioning

benefits of a shampoo
Function Ingredient
Anionic cleansing detergents Ammonium lauryl sulfate

Sodium lauryl ether sulfate (2 or 3 EO)
Amphoteric surfactant Cocamidopropyl betaine
Conditioning agent Polyalkylene oxide alkyl ether (e.g. PPG-15 stearyl ether*)
Particle size >l micron and <50 microns
HLB <7
Water-soluble carrier Ethanol
Cationic polymer 1-2 meq/g < charge density < 7 meq/g

Molecular weight 100,000 to 3 million
Polyquaternium-10 is preferred at concentration 0.1-1%.
Ratio of cationic polymer to polyalkylene oxide alkyl
ether is 1:2 to 1:10.
Silicone conditioning agent Silicone fluid

Silicone resin improves deposition and gloss (high
refractive index)
Silicone conditioning agent 100,000 cSt < Viscosity < 1.5 million csks
Small particle deposition (Number average particle
diameters = 0.01-0.5 micron)
Large particle deposition (Number average particle
diameter from 12-181 micron)
Particle sizes below 5 microns deposit more efficiently
on hair.**
* Arlamol E, Uniqema
** Trapped within the coacervate upon dilution?

131
Elubiol and Salicylic Acid Skin Permeation studies to deter-

mine the efficiency of deposition.
Complex coacervates can also be formed from mixtures of
cationic and anionic polymers. This could be the underlying
mechanism in shampoos that include a carbomerb with cationic
polymer to enhance the deposition of silicone and to improve con-
ditioning benefits.8
Formula 1. Conditioning shampoo
Function Ingredient Amount

Anionic detersive surfactant Ammoniun lauteth-3-sulfate 10.00% w/w
Anionic detersive surfactant Ammonium lauryl sulfate 2.00
Amphoteric surfactant Cocamidopropyl betaine 2.00
Cosurfactant Cetyl alcohol 0.60
Cosurfactant/foam builder Cocamide MEA 0.80
Conditioner Polyquaternium-10 0.50
Suspending agent Ethylene glycol distearate 1.50
Conditioner Dimethicone 2.00
Conditioning polyester Pentaerythritol adipic acid 2.00
Fragrance Polymeric ester perfume solution 0.70
Chelation Sodium citrate 0.40
pH adjustment Citric acid 0.40
Water (aqua) qs 100.00
Improving the Clarity of Conditioning Shampoos

Silicones are excellent for adsorbing at interfaces and spreading and
wetting hair to provide smoothing and conditioning benefits but
there are challenges in making stable suspensions of silicones in
shampoos. Silicones also tend to reduce foaming and usually silicone
shampoos are not visibly clear. Silicone copolyols were introduced to
b
Carbopol SF-1, Noveon

132
overcome these challenges. They have better solubility in shampoo

compositions but their deposition onto hair is much lower. There-
fore, conditioning performance is compromised.
Scientists at Kao Corporation have now invented a method
to make clear conditioning shampoos that contain a hydrophobic
silicone.9 Adding a solubilizer reduced the silicone droplet size suf-
ficiently to maintain a light transmission value of greater than 97%.
The preferred solubilizer is trideceth-2 carboxamide MEAc.
Peffly et al have reported clear conditioning shampoo formu-
lations that include a silicone microemulsion in a conditioning
shampoo containing guar hydroxypropyltrimonium chloride and an
anionic detersive surfactant.10,11
The anionic surfactant has a specified level for ethoxylate and
sulfate. The ethoxylate level is in the amount of about 1.97
multiplied by the molecular weight of the cationic guar poly-
mer divided by 1,000,000 plus from about 0.15 to about 3.5
The sulfate level is in the amount of about 0.97 multiplied by
the charge density.
The cationic polymer is guarhydroxypropyltrimonium chlo-
ride having a molecular weight of at least 300,000 and a
charge density of at least about 0.1 meq/g.
The silicone microemulsion is selected from among several
productsd from Dow Corning.
Seeking New Methods of Conferring Conditioning

from Shampoos
Organic conditioning oils such as polybutenee have been claimed to
confer conditioning benefits from a shampoo.12 Addition of poly-
butene is taught to increase the deposition of silicone conditioners,
and provides improved conditioning benefits such as wet and dry
feel and combing. It is interesting to try to figure out the mechanism
by which these shampoos provide conditioning. Perhaps these oils
are solubilized by the surfactant micelles in the shampoo and then
c
Aminol A15, Finetex
d
Examples include DC2-5791, DC2-5791-sp, DC2-1470, DC2-1870, DC2-1845, DC2-1845HV
and DC2-1550 from Dow Corning.
e
L14 polybutene from Amoco Corp

133
released during rinsing when the system drops below the critical
micelle concentration.
Conditioning can be achieved by including chain extended
silicones in an anionic surfactant-based shampoo. Specific examples
of useful silicones include a Dow Corning emulsionf containing
divinyldimethicone/dimethicone copolymer with a viscosity about
1.30x108 to 1.5x108 cP.13
There is a need to increase hair volume and styling from condi-
tioning shampoos, and an interesting method to meet this need is
to include particles that can deposit on the hair to increase inter-
fiber friction. Wells et al have revealed that cationic guar polymers
can enhance the deposition of particles on hair.14 In this case the
guar is specified to have a charge density less than 4.5 meq/g and
a molecular weight in the range 100,000 to 3 million. Pigment
particles can be included for color, friction-conferring particles for
style (titanium dioxide, clay, pearlescent mica, silica), and platelet
or spherical particles for slip and conditioning (hollow silica, hol-
low polymer). Shampoos containing ethoxylated alcohols have been
found to enhance the deposition of large particle silicones (5 to
2000 microns) and in this case it is claimed that cationic polymer is
not required.15
Hollow particles can be included in shampoo to increase hair
volume in people with fine hair that tends to lie flat.16,17 Factors that
influence hair body and fullness include hair diameter, hair fiber-
to-fiber interactions, natural configuration (kinky, straight, wavy),
bending stiffness, hair density and hair length.
Deposited hollow particles that can increase fiber-fiber interac-
tion comprise:
Complexes of gas-encapsulated microspheres such as silica
modified ethylene/methacrylate copolymer microsphereg and
talc-modified ethylene/methacrylate copolymer microsphereh
from Kobo
Selected polyestersi from Akzo Nobel
f
HMW2220 from Dow Corning
g
DSPCS-I2TM from Kobo
h
SPCAT-I2TM from Kobo
i
Examples include EXPANCELTM 091 DE and 551DE 50 from Akzo Nobel.

134
Selected inorganic hollow particlesj from 3M.

The deposition is claimed to be improved by including a cationic
polymer of molecular weight 10,000 to 10 million and charge den-
sity 0.9 to 7.0 meq/g.
Cationic polysaccharide polymers having a molecular weight of
from about 10,000 to about 10 million and a charge density from
about 1.4 meq/gm to about 7.0 meq/gm have been claimed to
enhance the deposition of antidandruff particulate ingredients on
surfaces.18
Johnson & Johnson have also directed attention to new composi-
tions for enhancement of actives deposition from shampoos.19 The
Johnson & Johnson shampoos comprise:
A water-soluble silicone. More preferred silicones are silicone
quaternium 13, cetyltriethylammonium dimethicone copolyol
phthalate, stearalkonium dimethicone copolyol phthalate.
A cationic conditioning agent. Most preferred conditioning
agents include acrylamidopropyltrimonium chloride/acrylam-
ide copolymerk, guar hydroxypropyltrimonium chloridel.
A cleansing detergent
Suspending agents are necessary to ensure homogeneous dis-
tribution of insoluble active ingredients. Among the preferred
suspending agents are carbomerm, hydroxyethylcellulose, and
PVM MA decadiene crosspolymern. Enhanced deposition
of particulate actives, such as zinc pyrithione, was shown on
cadaver skin treated in a Franz diffusion cell.
Conclusion
This chapter has traced advances in conditioning shampoos that
have bween announced in the last year or so. Significant progress
has occurred driven by technological breakthroughs in our under-
standing of the nanoscience of coacervates and also the marketplace
j
Examples include 3M Scotchlite Glass Bubbles, 3M Zeeospheres ceramic microspheres, and
3M Z-Light Spheres ceramic microspheres.
k
Salcare SC 60 from Ciba
l
Jaguar C-17 from Rhodia
m
Carbopol resin from Noveon
n
Stabilize 06 and QM from ISP

135
demand for stimuli-responsive compositions for enhanced deposi-

tion of benefit agents.
We can expect this trend to accelerate due to five factors. First,
the growing availability and awareness of advanced instrumental
methods such as atomic force microscopy, nanoindentation, photo-
acoustic spectroscopy, and small-angle neutron scattering. Second,
the introduction of combinatorial methods for formulation that
with allow investigation of the complete composition space in
reasonably short times and this will allow the formulator to rapidly
optimize systems of interest. Third, the international interest and
focused national funding for nanoscience that will greatly enhance
our understanding of the structure/property relationships of these
complex fluids. Fourth, advances in polymer science, such as living
free-radical polymerization and modern catalysis that will allow the
syntheses of polymers with well-defined precise microstructures.
Fifth, consolidation of the finished goods industry and the chemical
suppliers will channel more and better technological resources to the
production of advanced high performance products and will empha-
size the importance of diligent protection of intellectual property.
The end result will be a pronounced increase in the sophistica-
tion and diversity of products that will be offered to the consumer.
Robert Y. Lochhead and Lisa R. Huisinga

The School of Polymers & High Performance Materials,
Published December 2005 Cosmetics & Toiletries
References
1. ED Goddard, Polymer surfactant interaction, Parts I and II, chapters 4 and 5 in
Interactions of Surfactants with Polymers and Proteins, ED Goddard and KP
Ananthapadmanabhan, eds, Boca Raton, Florida: CRC Press (1993)
2. US Pats 5,104,646 and 5,106,609, R Bolich et al, assigned to Procter & Gamble (Apr
14, 1992)
3. US Pat Application 20030199403, RL Wells and ES Johnson, filed by Procter & Gamble
(Oct 23, 2003)
4. US Pat Application 20040146475, MM Peffly, NW Geary and JA Staudigel, filed by
Procter & Gamble (Jul 29, 2004)
5. US Pat application 20030143 74 Al, DR Royce and and R Wells, assigned to Procter &
Gamble (Jul 31, 2003)
6. US Pat application 20030138392, DR Royce and R Wells, assigned to Procter &
Gamble (Jul 24, 2003)
7. US Pat application 20030176303Al , SM Niemec, H Yeh, R Gallagher and KL Hoe, filed

136
by Johnson & Johnson (Sep 18, 2003)

8. US Pat Application 20030108503, Cosmetic compositions containing a methacrylic
acid copolymer, a silicone and a cationic polymer, and uses thereof, M Maubru and B
Liebard (Jun 12, 2003)
9. US Pat 6,803,050, H Denzer, H Abe, M Pytlik, R Jansen and A Buhmann, assigned to
Kao (Oct 12, 2004)
10. US Pat Application 20040234483, MM Peffly and DW Chang, assigned to Procter &
Gamble (Nov 25, 2004)
11. US Pat Application 20040234484, MM Peffly and DW Chang, assigned to Procter &
Gamble (Nov 25, 2004)
12. US Pat 6,221,817, Conditioning shampoo composition, SM Guskey, TW Coffindaffer, EM
Schrader, RL Wells and JT Baravetto, assigned to Procter & Gamble (Apr 24, 2001)
13. US Pat Application 20030143177, Q Stella, assigned to Procter & Gamble (Jul 31, 2003)
14. US Pat application 20030199403Al, RL Wells and ES Johnson, assigned to Procter &
Gamble (Oct 23, 2003)
15. US Pat 6,200,554, Conditioning shampoo compositions having improved silicone
deposition, T Yeoh, TW Coffindaffer, H Uchiyama, JG Schroeder and Y Okuyama (Mar
13, 2001)
16. US Pat Application 20030086896, S Midha, BD Hofrichter and SR Thomson, assigned
to Procter & Gamble (May 8, 2003)
17. US Pat Application 20030091521, S Midha and BD Hofrichter, assigned to Procter &
Gamble (May 15, 2003)
18. US Pat Application 20030202952, RL Wells, ES Johnson and DA Royce, filed by Procter
& Gamble (Oct 30, 2003)
19. US Pat Application 20030176303, SM Niemiec, H Yeh, R Gallagher and KL Ho, filed by
Johnson & Johnson (Sep 18, 2003)
20. US Pat Application 20020102228, DS Dunlop, RA Boyd, SM Guskey, JR Schwartz and
AR Marchetta, filed by Procter & Gamble (Aug 1, 2002)

Chapter 18
Efficacy of Coal Tar

vs. Sodium Shale Oil
Sulfonate for Treating
Dandruff
KEY WORDS: antidandruff efficacy, coal tar, sodium shale oil sulfonate,
dandruff, erythema, itch, shampoo
ABSTRACT: Coal tar is an effective antidandruff active, but it contains
compounds that are proven carcinogens. In this chapter
sodium shale oil sulfonate is shown in preliminary results for
the first time to have antidandruff efficacy equivalent to that
of coal tar with none of coal tars toxic potential.
In the face of spreading concerns about the safety of the antidan-

druff agent coal tar, personal care formulators are seeking a safe
substitute with equivalent efficacy. One alternative is sodium shale
oil sulfonate, a proprietary ingredient that is used in antidandruff
shampoos in Europe but is not presently approved for use in the
United States as an antidandruff agent. This chapter describes the
first ever comparison test of these two ingredients on the basis of
their efficacy in treating dandruff and two of its concomitant symp-
toms, which are skin redness and itching.
Coal Tar
Antidandruff activity: Coal tar (CT) has been used in the treatment
of dandruff for many years because of its broad action profile, which
includes anti-mitotic,1 antimicrobial,2 anti-seborrhoic3 as well as
keratolytic,4 anti-itching5 and anti-inflammatory actions.5,6

138
Shampoo Efficacy of Coal Tar vs. Sodium Shale Oil Sulfonate
In dandruff (dry and greasy forms), all the characteristics men-

tioned in Table 1 are interconnected in such a way that dandruff
is referred to as a vicious cycle of excessive desquamation.7 Active
ingredients with a broad action profile obviously offer different
starting points and approaches to treat this problem.
Table 1. Characteristics of dandruff and the

pharmacological counteraction provided by sodium shale
oil sulfonate (SSOS) or coal tar (CT), with cited references
Pharmacological
Characteristics of dandruff counteraction SSOS CT
Excessive cell reproduction of
epidermal cells Antimitotic 31 1
Formation of scales Keratolytic 4
Overproduction of oil glands
(with greasy dandruff) Antiseborrhoica 26, 27 3
Excessive colonization of the
scalp with micro-organismsb Antimicrobial 28-30 2
Formation of free fatty acids Antimicrobial 28-30 2
Itching Antipruriginous 32 5
Localized inflammations
(with skin redness) Anti-inflammatory 21-25 5,6
a
sebosuppressive
b
e.g.,Pityrosporum ovale
Safety: Although the regulatory status of CT in the United

States allows its application in OTC products for dandruff
treatment,8 there is ongoing discussion regarding its tolerance and
safety. Because CT is a thick liquid or semi-solid obtained in the
destructive distillation of coal at temperatures of about 1000C, it is
a complex mixture of thousands of compounds, many of which have
been identified as benzenes, xylenes, naphthalenes, cresols, phenols
and polycyclic aromatic hydrocarbons (PAH). Among the PAH
are found many substances that are carcinogenic. Benzo[a]pyrene

139
Gayko et al. Chapter 18
is regarded as a leading substance in this respect. Dermatologically

used CT contains about 0.5 to 0.7% (5000-7000 ppm) of carcino-
genic benzo[a]pyrene.9,10
The World Health Organization has summarized and indicated
the carcinogenic risk of benzo[a]pyrene and CT in two IARC
monographs as early as 1973 and 1985.11,12 In conclusion the data
indicate that CTs are causally associated with cancer in humans.
Although this conclusion was not made on basis of dermatologically
used CT preparations like dandruff shampoos, it is known that the
relevant mechanisms may take place in this case.
The penetration of components of CT through the skin is
beyond doubt.10,13 Following dermal penetration, PAH are converted
to epoxy and hydroxy derivatives by various cytochrome-P450-
dependent monooxygenases. The metabolites may react with cell
constituents and, as a consequence, may alter the genetic infor-
mation and cause malignant cell growth.14 The penetration of
components of coal tar through the skin is beyond doubt.)
In a study on the dermal uptake of PAH after washing of hair
with a CT shampoo, increased excretion of PAH metabolite 1-hy-
droxypyrene (1-OH-P) was observed after single use.15 Data from
animal studies suggest that medications containing CT may readily
penetrate the skin and produce toxicity, including carcinogenicity in
extra-cutaneous tissues (e.g., lung).16
As a result of these findings, in Europe coal tar was forbid-
den to be used in cosmetic products according to the European
Cosmetic Directive (76/768/EEC, 22nd amendment 1998). Since
July 1, 1999, cosmetic products containing CT can no longer be
offered in the EU. Under Californias Proposition 65, products
containing carcinogens have to carry a warning label. This is true
for shampoos containing CT as well. Recently, the CIR published
a safety assessment for CT with the conclusion that the available
data are insufficient to support the safety of CT as used in cosmetic
formulations.17,18
As a conclusion, it would be advantageous for cosmetic appli-
cations to have available a well-tolerated alternative from natural
origin with a comparative action profile that can replace coal tar
without losing efficacy.

140
Sodium Shale Oil Sulfonate

Sodium shale oil sulfonate (CAS 1340-06-3) (SSOS) could be a
suitable alternative for coal tar as an active ingredient in antidan-
druff shampoos. Just like CT it is derived from a natural source.
However, the natural raw material for its production is sulfur-rich
oil shale containing decomposition products of marine micro-
organisms and plants. By dry distillation of the shale rock a (crude)
shale oil is obtained that is fractionated in a vacuum column. A
volatile oil fraction obtained thereby is mixed with sulfuric acid
under gentle conditions and subsequently neutralized with sodium
hydroxide solution.
The resulting finished substance appears as a sodium salt of
sulfonated shale oil (INCI: Sodium shale oil sulfonate). As main
constituents, sulfonated thiophene derivatives (such as sodium salts
of methyl-thiophenesulfonates or benzo[b]thiophenesulfonates)
can be found by applying GC/MS (SIM) technique after methyla-
tion of the corresponding sulfonic acids. Routine analysis of product
composition (peak pattern) carried out by HPLC does not show any
fundamental deviations between different batches. The substance is
manufactured in a GMP-certified process and has been marketed as
a proprietary producta since about 1995. It is also called pale sul-
fonated shale oil.
Purity and toxicology: SSOS is different from (crude) shale oil
(CAS 68308-34-9). It is not a tar. Contrary to tars, the main com-
ponents of SSOS are strongly polar, water-soluble and surface-active
salts of sulfur-rich compounds (sulfonated thiophene-derivatives)
which do not pose any health risk in topical treatment. The most
important difference, however, is found in its purity with regard to
PAH. For each batch of SSOS manufactured by the German pro-
ducer a PAH profile with components as proposed by the United
States Environmental Protection Agency (EPA) is determined.
For instance, the leading substance benzo[a]pyrene is found in
an order of magnitude less than 0.0001 ppm in the SSOS. This is
more than 10,000,000 times less than is found in CT and even less
a
Ichthyol Pale is a product of Ichthyol Gesellschaft, Hamburg, Germany. Ichthyol is a
registered trademark of Ichthyol Gesellschaft.

141
than is allowed in water for human consumption. In drinking water

the maximum contaminant level (MCL) for benzo[a]pyrene set
by the EPA is 0.0002 ppm.19 In shampoos containing about 1% of
SSOS, benzo[a]pyrene originating from this agent is not detectable
any more (about 1 nanogram/kg). The most important difference,
however, is found in its purity with regard to PAH.)
The low content of PAH may be regarded as one of the main
reasons for the good tolerance of this active ingredient observed in
toxicological studies conducted on the acute and chronic toxicity,
phototoxicity, sensitization, photosensitization as well as the muta-
genic (see Comparing the Mutagenic Effect of SSOS and CT),
carcinogenic and teratogenic potential. In summary, the application
of SSOS gives no hint of any toxic or phototoxic effect. All studies
verify its good tolerance for short- and long-term use. A summary
of its toxicological data has been published.20
Comparing the Mutagenic Effect of SSOS and CT

The AMES test analyzing back mutations in strains of Salmonella bacteria
with defective genes may serve as an example for the different tolerance
of SSOS and CT. Whereas no mutagenic effect was observed for SSOS,37
evidence of mutagenicity was reported for CT.38
In course of the European Maximum Residue Limits procedure (MRL)
sulfonated shale oils (synonym bituminosulfonates) were evaluated
by the European Medicines Agency (EMEA) in London, recently. As a
result, SSOS was found to be safe and allowed for topical application in
all food-producing animals including animals producing milk for human
consumption.39,40 CT, on the other hand, failed in the same EMEA procedure
because of its perilous toxicological profile.
Therefore, the question to be dealt with is not the use of (crude)

shale oil versus coal tar in dermatological treatments as it was raised
by Jackson.8 On the contrary, a comparison has to be made between
SSOS (which can be regarded as a derivative from a volatile shale oil
fraction) and coal tar. From a toxicologists point of view SSOS is on
the safe side.

142
Pharmacological actions and efficacy: Regarding efficacy in treat-

ment of dandruff, SSOS has not been compared with CT so far.
However, it is applied presently as active ingredient in about 20
antidandruff shampoos in Europe alone (brand names found include
Kertyol, T/Gel Total, Phytolithol, Nod and Interactives).
For SSOS a broad action profile nearly similar to the one of
CT is claimed. As a multi-component mixture of natural origin,
different compounds interact to give synergistic effects favorable
in treatment of dandruff. Regarding its anti-inflammatory effects,
in the UVB erythema test a similar efficacy was observed for a
preparation containing 4% of SSOS as for one containing 0.5% of
hydrocortisone.21 In vitro studies showed that on the cellular level,
sulfonated shale oils are able to inhibit the activity of enzymes
(lipoxygenase, cyclooxygenase) taking action in the degradation of
arachidonic acid. Thereby, the secretion of inflammation media-
tors is restrained.22-24 Besides, an inhibition of cell migration that is
normally caused by chemotactic factors could be observed as well as
an inhibition of the formation of reactive oxygen compounds.22,25
A sebosuppressive action of SSOS could be proved in
humans.26,27
Regarding antimicrobial effects, some of the results obtained
in studies on the minimum inhibitory concentration (MIC) and
development of inhibiting zones on agar plates are given in
Table 2.28-30
Table 2. Effect of sodium shale oil sulfonate (SSOS) at

1% and 5% in aqueous solution on minimum inhibitory
concentration (MIC) and diameter of inhibiting zones of
selected micro-organisms28-30
Micro-organism MIC [%] Inhibiting zone diameter [mm]

1% SSOS 5% SSOS
Staphylococcus aureus 0.039 1.0 2.5
Pseudomonas aeruginosa 0.039 0.5 1.0
Pityrosporum species - 2.0 11.0

143
As shown by Gloor, the shale oil sulfonate slows the desqua-

mation of the scalp effectively. In fact, an equivalent reduction of
enhanced cell growth could be observed for CT and SSOS.31
The anti-itching properties of sulfonated shale oils have been
reported in many clinical studies.32
A review article on available data regarding treatment of
dandruff with SSOS has been published recently.33 In monitor-con-
trolled comparison studies SSOS was reported to be superior to well
established antidandruff agents as zinc pyrithione and piroctone
olamine due to its multifunctionality.34,35 The tolerance of the active
ingredient was judged to be very good by subjects and investigating
physicians.
No comparison of efficacy for SSOS versus CT had appeared
in the literature so far. For the first time results of such a test are
described in the following.
Materials and Methods

Study design: A cosmetic, monitor-controlled double-blind study
with a treatment period of eight weeks was conducted in 40 men
and women suffering from dandruff to compare the different effi-
cacy of shampoos containing 1% of SSOS and 1% of CT. The
study was carried out in the dermatological department of a clinic
in Svidnik, Slovakia. A cosmetic, monitor-controlled double-blind
study was conducted to compare the different efficacy of shampoos
containing 1% of SSOS and 1% of CT.)
An investigating physician selected the study subjects based on a
dandruff scoring (Table 3) and other established criteria (see Inclu-
sion and Exclusion Criteria for Subjects in Comparison Test)
evaluated during visit 1 before the start of the treatment period. A
dandruff score of 2 (moderate) or 3 (severe) was required for admis-
sion to the treatment phase of the study.
In total, 20 male and 20 female subjects between 16 and 65 years
of age participated in the study. Subjects were allocated to both
treatment groups in a randomized way but balanced by sex. The
investigating physician did not know which kind of preparation was
used by the different subjects. In the same way, the subjects did not
know which active ingredient their test shampoos contained.

144
Table 3. Score system for classification of dandruff by the

investigating physician.
Condition of hair upon inspection Score Meaning

No scales are visible. No scales can be 0 No dandruff
detached when scratching the scalp
with a comb.
Isolated scales are visible. Isolated 1 Mild

scales can be detached when scratching
the scalp with a comb.
Hair scales are visible. Scales can be 2 Moderate

detached from several places when
scratching the scalp with a comb.
Hair scales are clearly visible. Numerous 3 Severe

scales can be detached from several
places when scratching with a comb.
During the eight-week treatment phase, the shampoos had to

be applied every two days. According to the length of hair, sub-
jects were instructed to apply 5-10 ml of the test shampoo (beaker
marking) on the wet hair and to massage it into the scalp vigor-
ously. After an exposure time of 2-3 minutes the shampoo had to
be rinsed off. If the dandruff score for any subject dropped to 1, the
washing rhythm could be reduced to every three days according to
the instructions of the investigating physician. Washing of hair was
suspended in the two days prior to each efficacy assessment, which
occurred after 2, 4, 6 and 8 weeks (visit 2-5).
Objectives: The main objective under assessment was the change
in the appearance of dandruff during the treatment phase. Severity
of dandruff was scored from 0 to 3 by the investigating physician
according to the explanation in Table 3.
Erythema (skin redness) and itching were examined as secondary
objectives. Skin redness was scored from 0 (none) to 3 (severe) by
the investigating physician. Assessment of itching was done by the
subjects, using a scale from 0 (none) to 10 (severe).

145
Inclusion and Exclusion Criteria for Subjects in

Comparison Test
Inclusion criteria
Age 16-65 years
Length of hair 3-20 cm
Scalp thick with hair
No hair cut during the treatment period
Written agreement for voluntary and single participation
Written and oral explanation on application of shampoo and
shampooing scheme
Dandruff score 2 or 3
Exclusion criteria
Dermatitis seborrhoica capiliti, psoriasis vulgaris capiliti
Dandruff score < 2
Application of local or systemic drugs/cosmetics influencing
dandruff, itching, erythema and/or inflammatory signs before and
during the treatment period
Diabetics, pregnant women, nursing mothers, taking
of contraceptives
Lacking qualification to follow the instructions of the
investigating physician
Subjects with incompatibilities regarding ingredients of
the shampoos
Subjects with severe illnesses (e.g. infectious skin disorders)
Absence during treatment period (e.g. vacation)
Additionally, the success of therapy was evaluated by the investi-

gating physician and the subjects at the time of visit 3 and 5 (after 4
and 8 weeks, respectively). The tolerance of therapy was evaluated at
every visit. At the end of the whole treatment period, the overall tol-
erance was assessed by the physician and separately by the subjects.
Compliance of the subjects was assessed according to the protocol.
Test shampoos: Except for the presence of either SSOS or CT,
the test shampoos all had the same formula (Formula 1) to guar-

146
antee comparability regarding efficacy. Preparation of the shampoo

was carried out according to GMP guidelines in the laboratories of
Ichthyol-Gesellschaft.
Formula 1. Test shampoo (with concentration of ingredients

according to the FDA code*)
Water (aqua) A
Sodium laureth sulfate C
Alcohol E
Sodium chloride E
Active ingredient 1%
Coal tar (from Alfa Aesar Johnson Matthey, Germany)
or
Sodium shale oil sulfonate (from Ichthyol-Gesellschaft, Germany)
Cocamidopropyl betaine F
Fragrance (parfum) F
Sodium phosphate F
* FDA code (A: >50%; B: 25-50%; C: 10-25%; D: 5-10%; E: 1-5%; F: 0.1-1%; G: <0.1%)
Results
All 40 volunteers completed the studys eight-week treatment
period. No adverse events were reported during the course of the
study. Overall excellent treatment results were obtained in both
treatment groups with considerable improvements in all objectives
investigated (Figure 1) (see Color Insert 3).
According to the evaluation of the subjects at the time of the
last visit, the success of treatment was very good for both groups
(an average score of 1.25 on a scale between 1 and 6 for the 40
subjects). This is in agreement with the evaluation of the investi-
gating physician who rated the overall success of treatment with a
score of 1.30 for the SSOS group and the same score for the CT
group. No subject showed a deterioration (efficacy score 6) in any
of the objectives.

147
Figure 1. Efficacy of shampoos containing coal tar (red) or sodium shale oil sulfonate (green)
in treating dandruff (top), skin redness or erythema (middle) and itching (bottom) during an
8-week treatment period

148
Dandruff: In the beginning, the average dandruff score could be

evaluated as almost severe in both treatment groups. The average
dandruff score was determined to be 2.75 in the SSOS group and
2.65 in the CT group. During the eight-week treatment phase a
continuous decrease in the severity of dandruff could be observed
(Figure 1a). The success of treatment was most prominent after two
weeks with a decrease by 42% and 47% in the SSOS and CT group,
respectively. A continuous decrease in the severity of dandruff could
be observed.)
Whereas CT appears to be a little more effective in the first
weeks, in the end no difference in efficacy can be made out. The
average dandruff score was rated at almost severe in both treat-
ment groups at the start of the test. In the SSOS group, the overall
improvement regarding dandruff is about 86% with an average score
of 0.40 after eight weeks. The average dandruff score for the SSOS
group fell to 0 in 14 of 20 subjects. Virtually the same is true for
the CT group with an overall improvement of about 83% and an
average dandruff score of 0.45 determined in visit 5. Eleven out of
20 subjects in the CT group were free from dandruff symptoms at
the end of eight weeks.
Skin redness: Regarding skin redness, subjects were only slightly
to moderately affected on the average with an erythema score of
about 1.3 in the beginning. However, after the treatment phase of
eight weeks virtually no skin redness was left on the scalp of the
subjects (Figure 1b). This means an improvement by more than
90% in both treatment groups.
Itching: In contrast to skin redness most of the subjects were
affected by severe itching on the scalp. In the beginning, on a scale
between 0 and 10 the severity of itching was assessed at 7.2 and 8.0
by the subjects in the SSOS and CT group, respectively.
In course of the treatment the degree of itching was reduced
continuously and nearly eliminated in both groups (Figure 1c). In
the end, 80% of subjects in the SSOS group were free from itching
symptoms in this respect, whereas this was true for 75% of subjects
in the CT group.
Examination of subgroups: A closer look at some subgroups
discloses that, on average, the subjects with the very severe itching

149
score of 9 or 10 at the beginning of treatment suffered from more

severe dandruff as well. In the SSOS group an average dandruff
score of 2.88 was found in the very severely itching subgroup com-
pared with 2.67 for the rest of the group.
In the subgroup with most severe itching and dandruff, the suc-
cess of treatment was better than average in the SSOS group. The
degree of dandruff under these conditions could be reduced by 91%
(from 2.88 to 0.25) whereas the reduction rate was 81% (from 2.67
to 0.5) for the rest of the group. In 75% of subjects in the subgroup
with severe dandruff and itching, dandruff was eliminated com-
pletely after eight weeks (score 0).
This result cannot be confirmed for the CT group. Although
subjects with itching score of 9 or 10 suffered from more severe
dandruff in this case as well (starting score 2.71 compared with
2.50), the success of treatment was not much better than average in
this case (84% compared with 82%). These findings are elucidated
in Figure 2 (see Color Insert 4).
Figure 2. Reduction of average dandruff score in the subgroup of subjects with itching
score of 9 or 10

150
Tolerance: The tolerance was very good for both types of test
shampoos; 95% of all subjects were very satisfied with the treatment.
Comparable scorings of 1.10 and 1.15 were reported by the investi-
gating physician and the subjects, respectively. No side effects were
reported and no interruption of treatment occurred on account of
intolerance reactions.
Discussion
Limitations of the study: This preliminary study was intentionally
limited to an efficacy comparison of two antidandruff agents. It is
recognized that the study could be extended to include instrumental
measurements, placebo controls and statistical analysis. The exact
mechanism of action of the two agents at the site of application has
not yet been fully identified. However, the pharmacological actions
known for both substances give a lot of information in this respect.
Much is known about the constituents and identity of CT and
SSOS. As products of natural origin, certain variations in composi-
tion may appear. Especially for CT the composition varies mainly
depending on manufacturing temperature and further processing
steps. The basic assumptions regarding presence of toxicologically
critical compounds, however, cannot be denied.
For SSOS, there is presently only one grade of quality from one
established manufacturing procedure. Analytical means (GC/MS)
are available for detecting the main single compounds in SSOS.
Routine analysis by HPLC gives no hint of any fundamental varia-
tions in product composition. This study was focused only on the
concept that the ideal antidandruff agent should be a substance that
is safe and well-tolerated in long-term treatment with a broad action
profile offering relief from dandruff and all concomitant symptoms.
Antidandruff activity: The well-known antidandruff properties
of coal tar (CT) and sodium shale oil sulfonate (SSOS) could be
confirmed in this study. With respect to the initial findings in the
different efficacy criteria investigated (dandruff, skin redness and
itching), excellent success of treatment of comparable degree can
be stated for both active ingredients. This may be due to the fact
that both active ingredients exhibit an action profile matching the
requirements of an all-embracing treatment.

151
On the whole, the CT shampoo appears to be a little more

effective in reducing the number of visible scales on scalp and hair
in the beginning of the treatment phase (reduction by 47% for CT
compared to 42% for SSOS after two weeks). However, after eight
weeks no difference can be observed in this respect between the
two groups.
The SSOS shampoo, on the other hand, seems to be more effec-
tive in cases of severe dandruff. An improvement rate of 91% in the
SSOS group can be compared to 84% in the CT group. However,
the differences mentioned are only of tentative nature.
Regarding tolerance no difference is observed in the two groups
during the treatment period of eight weeks. Both test shampoos are
very well tolerated and accepted by the 40 participants.
Safety: Despite its undisputed curative potential, CT is known
to possess carcinogenic properties via polycyclic aromatic hydro-
carbons, which are its main components. They penetrate the skin
even after short-time exposure by means of a shampoo. Therefore,
allowing an uncontrolled use of CT on the skin (as can occur with
OTC shampoos over long time periods) does not seem to be reason-
able. In Europe, cosmetic CT shampoos have been banned for this
reason. In Germany, as an example, an accurate diagnosis by derma-
tologists is imperative before CT is prescribed. A long-term therapy
should be avoided.36 However, as long as cosmetic CT shampoos
are available over the counter, they may be used by consumers in an
unrestrained way and over long time periods.
Conclusion
Stimulated by the cosmetic ban in Europe, legislation in California
and CIR evaluations, the safety of coal tar is an on-going discussion
in the United States. Fear is expressed sometimes that an effective
and broad spectrum therapy in treatment of dandruff and other skin
disorders might get lost.
The comparative study reported here demonstrates that, in terms
of efficacy, sodium shale oil sulfonate is a viable alternative. It is
safe, well-tolerated and, above all, similarly effective. It is naturally
sourced, and has a broad spectrum of activity against dandruff.
Sodium shale oil sulfonate is available to substitute for coal tar in

152
cosmetic dandruff shampoos. In Europe, this exchange has already

been done successfully.
Guido Gayko, PhD, Jrgen Warnecke, MD and Claudia Volger

Scientific Department, Ichthyol-Gesellschaft, Hamburg, Germany
Hana Zelenkova, MD, PhD
Private Department of Dermatovenerology, Svidnik, Slovakia
Published March 2005 Cosmetics & Toiletries
References
1. JJ Leyden and AM Kligman, Dandruff cause and treatment, Cosmet Toil 94(3) 23-28
(1979)
2. P Nenoff and UF Haustein, Der Effekt anti-seborrhoischer Substanzen gegenber
Pityrosporum ovale in vitro, Hautarzt 45 464-467 (1994)
3. M Gloor, E mattern and HC Friederich, ber die Wirkung eines Steinkohlenteerzusatzes
zu Kopfwaschmitteln auf Menge und Zusammensetzung der Kopf- und Haarlipide,
Dermatol Monatsschr 162 678-683 (1976)
4. Harrys Cosmetology, 7th edn, J Wilkinson and R Moore, eds, New York: Chemical
Publishing (1982) p 499
5. O Braun-Falco, G Plewig, HH Wolff and RK Winkelmann, Dermatology, Berlin: Springer
(1991) p 1149
6. M Gloor, K Thoma and J Fluhr, Dermatologische Externtherapie, Berlin: Springer (2000)
p 330
7. C Chavigny, Soins Capillaires: de plus en plus cibls, Parfums Cosmtiques Actualits
166 73-87 (2002)
8. EM Jackson, The use of shale oil versus coal tar in dermatological treatments, Cos
Dermatol 10 21-22 (1997)
9. H Ippen and G Grimmer, Carcinogene Kohlenwasserstoffe in therapeutischen Teeren,
Zeitschrift fr Hautkrankheiten 68 88-92 (1993)
10. JGM Van Rooij, JHC De Roos, MM Bodelier-Bade and FJ Jongeneelen, Absorption of
polycyclic aromatic hydrocarbons through human skin: differences between anatomical
sites and individuals, J Toxicol Environ Health 38 355-368 (1993)
11. Certain polycyclic aromatic hydrocarbons and heterocyclic compounds, Monographs
on the Evaluation of Carcinogenic Risk of the Chemical to Man, vol 3, Lyon, France:
World Health Organisation (WHO), International Agency for Research on Cancer (1973)
12. Polynuclear aromatic compounds, Part 4, Bitumens, coal-tars and derived products,
shale-oils and soots, Monographs on the Carcinogenic Risk of Chemicals to Humans,
vol 35, Lyon, France: World Health Organisation (WHO), International Agency for
Research on Cancer (1985)
13. RT Veenhuis, J van Horssen, RP Bos, RB Anzion and PG Van Der Valk, Highly increased
urinary 1-hydroxypyrene excretion rate in patients with atopic dermatitis treated with
topical coal tar, Arch Dermatol Res 294(4) 168-171 (2002)
14. G Grimmer, J Jacob, G Nettbard and KW Naujack, Determination of urinary metabolites
of polycyclic aromatic hydrocarbons (PAH) for the risk assessment of PAH-exposed
workers, Int Arch Occup Environ Health 69, 231-239 (1997)
15. FJ Van Schooten, EJC Moonen, E Rhijnsburger, B Van Agen, HHW Thijssen and JCS
Kleinjans, Dermal uptake of polycyclic aromatic hydrocarbons after hairwash with coal-
tar shampoo, Lancet 344 1505-1506 (1994)
16. H Mukhtar, P Asokan, M Das, RM Santella and DR Bickers, Benzo[a]pyrene diol
epoxide-I-DANN adduct formation in the epidermis and lung of sencar mice following
topical application of crude coal tar, Cancer Letters 33 287-294 (1986)

153
17. Coal tar, Scientific Literature Review, Washington, DC: Cosmetic Ingredient Review (May
17, 2002)
18. Cosmetic Ingredient Review Expert Panel, Final report on safety assessment of coal tar,
Washington, DC: Cosmetic Ingredient Review (Mar 16, 2004)
19. US Environmental Protection Agency, 40 CFR Parts 141 and 142, Drinking water
monitoring requirements for certain chemical contaminants Chemical monitoring
reform (CMR) and permanent monitoring relief (PMR); Proposed rule, Fed Reg 62(128)
36100-36136 (Jul 3, 1997)
20. W Cholcha, J Leuschner and F Leuschner, Experimental studies on the tolerance of pale
sulfonated shale oil following local and systemic application, Arnzeim-Forsch/Drug Res
44(II) 2 170-177 (1994)
21. J Warnecke and A Wendt, Anti-inflammatory action of pale sulfonated shale oil (Ichthyol
Pale) in UVB erythema test, Inflamm Res 47 75-78 (1998)
22. BM Czarnetzki, Inhibitory effects of shale oils (ichthyols) on the secretion of chemotactic
leukotrienes from human leukocytes and on leukocyte migration, J Invest Derm 87 694-
697 (1986)
23. W Diezel, T Schewe, E Rohde, T Rosenbach and RM Czarnetzki,
Ammoniumbituminosulfonat (Ichthyol). Antientzndliche Wirkung und Hemmung des
Enzyms 5-Lipoxygenase, Hautarzt 43 772-774 (1992)
24. C Schewe, T Schewe, E Rohde, W Diezel and BM Czarnetzki, inhibitory effects of
sulfonated shale oils (ammonium bituminosulphonates, ichthyols) on enzymes of
polyenoic fatty acid metabolism, Arch Dermatol Res 286 137-141 (1994)
25. KF Rabe, RS Perkins, G Dent, H Gustmann and PJ Barnes, Inhibitory effects of
sulfonated shale oil fractions on the oxidative burst and Ca++ mobilization in stimulated
macrophages, Arzneim-Forsch/Drug Res 44(I) 2 166-170 (1994)
26. JW Fluhr, M Gloor, W Merkel, J Warnecke, U Hffler, W Lehmacher and J Glutsch,
Antibacterial and sebosuppressive efficacy of a combination of chloramphenicol and
pale sulfonated shale oil, Arzneim Forsch/Drug Res 48(I) 2 188-196 (1998)
27. M Gloor, V Steingrber and HC Friederich, ber den antiseborrhoischen Effekt von
Bituminosulfonaten bei Acne Vulgaris, Hautarzt 24 288-289 (1972)
28. H Listemann, A Schlermann and W Meigel, Antimyzetische Aktivitt von sulfonierten
Schieferlen, Arzneim-Forsch/Drug Res 43(II) 7 784-788 (1993)
29. A Wendt, Helles sulfoniertes Schieferl fr eine natrliche Haarpflege, Parfm Kosmetik
75(1) 22-25 (1994)
30. V Grimm, R Engst, P Seidl and J Ring, Untersuchungen zur antimikrobiellen Wirksamkeit
von Natriumbituminosulfonat (hell), Poster No 201, Congress of the German
dermatological society (DDG), Berlin, 1-5 May, 2001
31. M Gloor, Lipide der Hautoberflche, ber die Beziehung zwischen Stratum corneum-
Lipiden und Funktion und Morphe des normalen Stratum corneum. In Stratum corneum:
Struktur und Funktion, F Klaschka, ed, Berliner Dermatologisches Symposium, Berlin:
Grosse (1981) p 77
32. G Mays, Ichthyol pale: Clinically approved anti-dandruff efficacy, Eurocosmetics 6(6)
30-32 (1998)
33. G Gayko, Sulfonate dhuile de schiste sodique contre les pellicules, Parfums
Cosmtiques Actualits 170 73-81 (2003)
34. G Wilbrand, Dealing with dandruff, Soap Perfumery & Cosmetics 72(4) 79-83 (1999)
35. G Wilbrand and G Gayko, Beyond dandruff, Soap, Perfumery & Cosmetics 73(3) 101-
104 (2000)
36. E Mutschler, G Geisslinger, HK Kroemer and M Schfer-Korting, Arzneimittelwirkungen,
Lehrbuch der Pharmakologie und Toxikologie, 8th edn, Stuttgart: Wissenschaftliche
Verlagsgesellschaft (2001) p 726
37. J Leuschner, Mutagenicity Study of Sulfoniertes Schieferl, hell in the AMES
Salmonella/Microsome Plate Test (in vitro), unpublished report, LPT Laboratory of
Pharmacology and Toxicology, Hamburg, May 1993
38. MD Saperstein and LA Wheeler, Mutagenicity of coal tar preparations used in the

154
treatment of psoriasis, Toxicology Letters 3 325-329 (1979)

39. EMEA, Committee for Veterinary Medicinal Products, Summary Report on
Bituminosulfonates, Ammonium and Sodium Salts, London, UK, EMEA/MRL/511/98-
Final-Corrigendum, February 1999
40. EMEA, Committee for Veterinary Medicinal Products, Summary Opinion, Ammonium and
Sodium Salts of Bituminosulfonates, London, UK, EMEA/CVMP/792/04, September 2004

Chapter 19
Esters from Vegetable

Sources with Care Effects
for Hair
KEY WORDS: esters, glyceryl oleate, cetyl palmitate, glycol distearate,
gloss, combing, protection, feel
ABSTRACT: Esters derived from vegetable sources are becoming
increasingly important as a class of active ingredients that
deliver effective care benefits when properly formulated into
personal cleansing products.
Ingredients providing care in personal cleansing products for skin

and hair are becoming increasingly important. When optimum use
is made of these care ingredients, the positive effects on skin and
hair can actively support the marketing claims of finished products.
Maintaining the right balance of care ingredients and surfactant
base is important in order to avoid an overload of effects that can
negatively influence properties such as cleansing, lathering and feel.
In this chapter, we will focus on cleansing applications for hair and
will feature the positive effects of esters produced from vegetable
raw materials as active ingredients.
Function
Esters are present as components in many products that accom-
pany us unnoticed in our daily lives. They are involved in forming
fragrances and flavors in wines, brandies and whiskeys. Esters are
found in many food products to provide flavor and nutrition. In
addition, they are essential ingredients in leave-on cosmetic prod-
ucts for face and body care. By virtue of their versatility and their
natural presence in human skin, ingredients with functional ester-

156
Shampoo Esters from Vegetable Sources with Care Effects for Hair
groups provide a wide range of possible applications in personal

cleansing products.
Here, we will focus on selected esters from vegetable sources and
describe their uses for personal cleansing preparations with varied
effects on hair. These esters (Figure 1) are glyceryl oleate (GMO),
cetyl palmitate (CP) and glycol distearate (EGDS).
Figure 1. Ester structures
In terms of applied technology, these selected ingredients can be

classified according to their use in two types of cleansing formula-
tions: clear or opaque. In general, we found that effective levels
of GMO can be incorporated into surfactant-based formulations
at concentrations up to 1.5% for clear product concepts. CP and
EGDS, which are waxy materials, provide appreciable effects when
incorporated into personal cleansing formulations as finely dispersed
particles. As such, CP and EGDS are suitable for opacified or
pearlized products. Figure 2a (see Color Insert 4) shows the opti-
cal appearance of various wax dispersions in relation to their particle
size. Figure 2b (see Color Insert 4) demonstrates the effect of finely
dispersed EGDS concentration on the final product opacity.

157
Morris et al. Chapter 19
Figure 2a. Wax dispersion selection and optical appearance in relation to particle size
Figure 2b. EGDS fine wax dispersion (2-4 mm)
GMO, CP and EGDS esters are solid materials at room tem-

perature and therefore require significant heating and process time
to utilize in production. A growing requirement in the cosmetic
industry is the production of personal care products with ingredients
that are cold-processable; using cold-processable ester ingredients
can save time and energy costs. To meet this growing need, we have
developed cold-processable liquid compounds based on these esters.
For example, a cold-processable blend based on GMO (and) coco
glucoside; and a cold-processable wax dispersion based on EGDS
(and) coco glucoside (and) glyceryl oleate (and) glyceryl stearate.
Another advantage of producing these ester compounds in easy-
to-handle liquid form is the ability to consistently supply EGDS
and CP wax dispersions with closely defined particles of uniform
size. This aspect is very important to the final formulations perfor-

158
mance. In general, ester-based wax dispersions in pearlized products

with a mean particle size significantly larger than 10 microns show
a low effectivity on skin and hair. As the particle size decreases, the
positive effects of these wax particles become more appreciable. In
general we found that wax dispersions are optimal for skin and hair
effects when 50% of the particles are approximately 1 micron in size.
Ester Care Effects on Hair

Ester deposition: Effects on hair are usually easier to measure than
effects on skin. This is due to the large surface area of hair. There-
fore it was not surprising that higher amounts of ester adsorption
result on hair when compared to skin. As with skin, hair has a cer-
tain natural GMO content. The test designed was based on washing
1g hair (medium bleached) with 1g product for 5 min., then rins-
ing the strands for 1 min. with water 1 liter per min. at 38C. The
hair was then dried and lipids were extracted from the hair strands;
quantitative analysis of glyceryl oleate was taken by GC/MS.
In Figure 3, we see that shampoo compositions containing
GMO show a higher GMO deposition after use compared to
cleansing the hair without GMO as shown in Formula 1. An
insignificant variation is noted between the untreated hair and hair
without GMO. This is due to the fact that hair innately has a base-
line level of GMO present, which can vary.
Figure 3. Adsorption

159
Formula 1. Hair cleanser formulations without GMO
weight % active
Formulation A B
Sodium laureth sulfate 8.4 8.4
Cocamidopropyl betaine 1.5 1.5
Coco glucoside 2.0 2.0
Polyquaternium-10 0.4 0.4
Glyceryl oleate 0.8 1.32
Water (aqua) qs 100.0 qs 100.0
pH value 5.5
viscosity 5000 mPa.s
Hair surface and hair roughness: To measure fine changes on

the hair surface, the AFM-method (atomic force microscope) was
used. Besides visualizing changes on the hair surface, correspond-
ing changes in surface area and roughness can be measured as well.
Figure 4 illustrates the AFM method and Formula 2 describes
the shampoo compositions containing GMO and CP that
were evaluated.
Figure 4. Atomic force investigations on hair fibers and strands
To demonstrate the effects of the ester substances more clearly,

the surfactant effect (placebo) was subtracted from the GMO and
CP results. Referring to Figure 5 (see Color Insert 5), it is evident

160
that both esters reduce the surface area, when used frequently over a
prolonged period, counteracting the swelling effect of the surfactant.
Formula 2. Shampoo compositions evaluated containing

GMO and CP
Formulation placebo GMO CP

Sodium laureth sulfate 11.3 11.3 11.3
Cocamidopropyl betaine 2.2 2.2 2.2
Coco glucoside 1.5 1.5 1.5
Glyceryl oleate 0.8
Cetyl palmitate 0.9
Preservative 0.1 0.1 0.1
Water (aqua) ad 100%
pH value 5.5
viscosity 60008000 mPa.s
Figure 5. AFM hair surface

161
Referring to Figure 6 (see Color Insert 5), microscopic rough-

ness is reduced in much the same way with the compositions
containing GMO and CP. To approximate practical use situations,
the duration of these treatments was 75 minutes and is based on 15
separate applications lasting 5 minutes each.
Figure 6. AFM hair roughness
Wet combing force: These AFM-results were then correlated with

the other important hair effects, such as wet combing and hair gloss.
The absorption behavior of GMO and CP shows a decrease in the
force required for combing wet hair (Figure 7)(see Color Insert 6).
Reducing the surface roughness of hair leads to a smoother, softer
appearance and facilitates gentle combing.
Hair gloss: Loss of hair shine (or gloss) is the consequence of a
decrease in scattered light that can occur when there is an increase
in the hairs protruding cuticle edges. Also, dirty and/or dry hair
will have reduced hair shine. The first step to improved hair gloss is
a thorough cleansing to remove surface dirt.1,2 Figure 8 (see Color
Insert 6) clearly illustrates this cleansing effect to improve gloss by

162
the placebo. In our evaluations, the first treatment period produced

the maximum gloss increase for all compositions. The positive
influence of GMO and CP on hair gloss is clearly seen. The gloss
percentage increase values are higher than those of the placebo with
its pure surfactant effect. Further treatments with all of the compo-
sitions tested, i.e. placebo, GMO and CP, did not improve the gloss.
Figure 7. Combability of hair strand
Figure 8. Hair gloss measurement by goniometrie

163
Heat protection: The structure of human hair and its stability are
determined by the cuticle-layers and the cortex, which in turn is
composed of a variety of components and layers, down to the a-he-
lix. The protein composition of hair is approximately 65-95%. Its
moisture content is extremely variable; up to 32%.3 The remainder is
made up of lipids, pigments, and trace elements. It has always been
the objective of the different studies to simulate the various detri-
mental influences on the hair, and to develop test methods that can
measure improvement or protection against their damaging effects.
Referring to Figure 9 (see Color Insert 6), a DSC-measurement
(differential scanning calorimeter) on hair clippings led to two dif-
ferent findings regarding hair. This method measures the energy
uptake and the temperature of the hair. Pre-damaged European hair,
during energy uptake at approximately 150C, was near-constant
temperature. That peak is due to hair denaturation when the hair
loses its a-helical structural element. At the same time, an analysis
of the peak area provides a measure of cortex resistance. Our study
focused only on the temperature change.4
Figure 9. Different scanning calorimeter investigation on human hair

164
Temperatures this high are not routinely encountered in the

every day routines. However, when using a hair drier close to the
hair, relatively high temperatures can result. Regular use of a hair
dryer in combination with all the other environmental influence can
damage hair making it dry, rough, and brittle with split ends.
When introduced into two different hair care applications (i.e.,
shampoo and hair conditioner, Formulas 3 and 4, respectively),
GMO had the effect of increasing the denaturing temperature
(Figure 10)(see Color Insert 7). The damaging effect of the sur-
factants in the shampoo is counteracted by the presence of GMO
as indicated by the higher denaturing temperature (148.9C) of
the shampoo with GMO compared to shampoo without GMO
(147.8C). The hair conditioner with GMO exhibited similar posi-
tive result.
Sensory evaluation: In our final assessment, we evaluated the
sensory benefits of EGDS (particle size range 2-4 microns) in
shampoos formulation using the simultaneous half-head tests
conducted by professional hair stylists. Referring to Formula 5, two
shampoo formulas (with and without EGDS) are applied to either
side of the test persons head. The sensory assessment which con-
sists of many different attributes or parameters including foam,
feel, foam volume, distribution, combability of wet hair and volume
and gloss, is performed by the professional hair stylist conducting
the test. The test is administered with ten subjects on which one
product is applied to one side of the head, and another product is
applied to the other side of the head. A comparison is then made
between the two sides based on the same parameters. A sensory rat-
ing system used to rate the relative differences between the products
applied to either side of the head. These differences are given a
relative score, i.e.: -30, -20, -10, 100, 10, 20 and 30. A score of 100
meant the products rated identically in the same parameters; 10
reflected minor differences, only detectable by the half-head test;
20 reflected differences detectable by the hair care experts; and 30
reflected distinct differences noticeable by test candidates.
Referring to Figure 11 (see Color Insert 22), it is evident that
during the pre-wash, the foam performance of the EGDS-contain-
ing formulation is not as good as the control without EGDS. This

165
Formula 3. GMO introduced into a shampoo formulation
Shampoo 13 14
% active substance
Glyceryl oleate 0.8
Cationic polymer (guar) 0.3 0.3
Water (aqua) qs 100%
pH value 5.5 5.5
viscosity 7100 7400
Formula 4. GMO introduced into a conditioner formulation
Hair Conditioner 1 2
% active substance
Cetearyl alcohol 4.0 4.0
Glyceryl stearate 0.5 0.5
Esterquat 2.5 2.5
Propylene glycol 0.5 0.5
Coco glucoside 0.9
Glyceryl oleate 0.65
preservative/Water (aqua) qs 100%
pH value 3.5 3.5
Figure 10. Hair drying protection by GMO

166
result is probably because soils in the hair affect the flash foam and
foam stability of the EGDS formulation as indicated by the blue
line. Both of these properties however are improved in the main
washing step. In addition, a significantly higher foam volume was
achieved. The EGDS formulation showed a slight improvement in
combability. The hair feel and gloss properties were found to be sig-
nificantly better than the control without EGDS. All the additional
properties tested are comparable.
Formula 5. Two shampoo formulas with and without EGDS

used in half head test
Formulation % active substance % active substance

Opacifier (styrene/acrylates copolymer) 1.0 ---
EGDS --- 1.1
Preservative qs 100 qs 100
Water (aqua) qs 100 qs 100
Summary
The positive effects of these vegetable-based ester ingredients on
hair were confirmed by these evaluations. The improved revital-
ization effect on hair and hair structure can actually be proven by
objective as well as subjective results, including effects that can be
seen and felt. These esters have been shown to improve properties
such as gloss, protection, combability and feel of hair. Effective lev-
els of GMO can be incorporated into surfactant based formulations
at concentrations up to 1.5% for clear product concepts. CP and
EGDS, which are waxy materials, provide appreciable effects when
incorporated into personal cleansing formulations as finely dispersed
particles. As such, CP and EGDS are suitable for opacified or

167
Figure 11. Half head test
pearlized products. When optimum use is made of these ester ingre-

dients in cleansing formulations, the positive effects on skin and hair
can actively support the marketing claims of finished products.
Acknowledgements
Compiling, understanding, and interpreting the results of this chapter required significant
effort from many contributors. The authors would like to thank the Cognis colleagues from
the departments of Applied Technology and Performance Testing, whose contributions
made this comprehensive study possible.
Tim Morris and Michael Hansberry

Cognis Corporation, Ambler, PA USA
Werner Seipel and Claus Nieendick
Cognis Deutschland GmbH & Co. KG, Dsseldorf, Germany

168
References
1. RF Stamm, MK Garcia and JJ Fuchs, The optical properties of human hair I:
Fundamental considerations and goniophotometer curves, J Soc Cosmet Chem 28 571-
599 (Sep 1977)
2. RF Stamm, MK Garcia and JJ Fuchs, The optical properties of human hair II, The luster
of hair fibers, J Soc Cosmet Chem 28 601-609 (Sep 1977)
3. H Deutz, Thermische und mikroskopische Charakterisierung von Keratinen, TH Aachen
H94 B 1479
4. P Morganti and G Morganti, Hair and cosmesis, Soap & Cosmetics 26-31 (Sep 2001)

Chapter 20
Silicone Technologies
as Delivery Systems via
Physical Associations
KEY WORDS: active ingredient, alkylmethylsiloxane, delivery, dimethicone
copolyol, silicone polyether, quaternary polymer
ABSTRACT: In physical association with active ingredients, silicones
can act as delivery vehicles for actives in skin and hair; they
can also provide improved sensory and aesthetic benefits,
enhanced SPF and prolonged fragrance intensity.
Todays consumers worldwide are looking for personal care products

that supply multiple benefits with minimal effort. They also expect
the latest technology advances to be incorporated into innovative
formulations. Faced with these trends, formulators strive to develop
highly differentiated, multifunctional products that focus on treat-
ment as well as aesthetics. A significant number of novel products
are based on a new generation of active ingredients. With these
emerging actives comes a range of formulation challenges, including
stability control and the complications of combining several actives
into a single cosmetic product.
Background
A recent research focus at Dow Corning has been directed toward
delivering or enhancing actives in final formulations. Studies have
highlighted the ability of silicone-based technologies to meet these
objectives while providing a range of desirable features and ben-
efits. A delivery system is usually defined as any type of material
capable of making an active available for a targeted site of action.
Using this definition, personal care delivery systems range from the

170
simplest concepts such as volatile carriers for actives, to increasingly

sophisticated technologies like encapsulation, with the capability
of providing controlled or sequential release of the active. Table 1
describes the different categories of delivery systems and the fea-
tures of each.
Table 1. Categories of delivery systems and respective

features
Physical Encapsulation Encapsulation/ Controlled and/or Sequential

association with no release Entrapment sustained release release
with release
Combination Coating of Protection of Delivery of active Multiple
of ingredients ingredients to active prior to at the site of action actives that
protect active use. Release on at the desired time, need to be
in pre- and application; level, etc., or over released in a
post- application one shot a long period of well-defined
time order, at
some specific
time
Here, the use of silicone delivery technologies in skin and hair

care applications is presented. This chapter focuses on how silicones
in physical association with various active ingredients can function
as delivery vehicles for the actives.
In the most basic example of this concept, aluminum zirconium
tetrachlorohydrex GLYa, an active ingredient used in antiperspirant
applications, is suspended in a vehicle based on volatile silicones.
The anhydrous vehicle reduces stickiness and protects the activated
salts from hydrolysis.1 The active is released when the volatile sili-
cone evaporates. This approach has been expanded to ingredients
such as fragrances and conditioning ingredients in product forms
such as cuticle coats.
a
Rezal 36 G (INCI: aluminum zirconium tetrachlorohydrex GLY) Concentrate 46% Solution is
a product from Reheis Inc, New Jersey, USA

171
Newton et al. Chapter 20
Enhancing SPF with Alkylmethylsiloxanes

Recent market information reports that the sun care market
is evolving toward higher SPF values as consumers become
increasingly aware of the dangers of UV radiation resulting from
excessive skin exposure to the sun.2 Consequently, formulators are
turning toward additives that can be combined with UV filters to
improve sunscreen efficiency, compensate for some of the nega-
tive attributes of the filters, or both. Some cosmetic raw materials
function in this way, including a variety of silicone-based poly-
mers. Excellent examples are found in the alkylmethylsiloxane
(AMS) family.3
Alkylmethylsiloxanes are organo-modified silicones whose
methyl groups have been partially replaced by long chain alkyl
groups (Figure 1). By varying the chain length of the silicone
backbone (x + y) and the alkyl group (R), as well as the degree of
substitution (y), it is possible to produce three classes of alkylmeth-
ylsiloxanes: volatile fluids, nonvolatile fluids and silicone waxes with
melting points ranging from 25C to 70C.
Figure 1. Chemical structure of alkylmethylsiloxanes
Three different alkylmethylsiloxanes, cetyl dimethicone (AMS

fluid), stearyl dimethicone (AMS wax) and C30-45 Alkyl Methicone
(AMS wax), were evaluated to determine their effect on the SPF
of selected European oil-in-water formulations containing organic
sunscreens. The formulation ingredients and mixing procedure are
described in Formulas 1 and 2.

172
Formulas 1 and 2. European oil-in-water sun care

formulations with organic sunscreens
1 2
A. Ethylhexyl methoxycinnamate (Parsol MCX, Roche) 4.00 6.0
Butyl methoxydibenzoylmethane (Parsol 1789, Roche)* 1.50 3.0
4-Methylbenzylidene camphor (Uvinul MBC 95, BASF) - 3.0
Phenyl trimethicone
(Dow Corning 556 Cosmetic Grade Fluid, Dow Corning) 3.0 -
Alkylmethylsiloxane (e.g. Stearyl dimethicone, Dow Corning) 4.0 2.0
Caprylic/capric triglyceride (Crodamol GTCC, Croda) 4.0 -
Glyceryl stearate (Cithrol GMS, Croda) 3.0 3.0
C12-15 alkyl benzoate (Finsolv TN, Finetex Inc) - 4.0
Cetyl alcohol - 0.25
Methyl/propyl paraben qs qs
Butylated hydroxy toluene qs qs
B. Potassium cetyl phosphate (Amphisol K, Roche) 2.0 2.0
C. Carbomer, 1% (Carbopol 980, Noveon Inc.) 10.0 10.0

Propylene glycol 3.5 2.5
Disodium EDTA 0.1 0.1
Water (aqua) qs 100.0 qs 100.0
D. Potassium hydroxide, 10% sol to pH 7 qs qs

E. Cyclopentasiloxane (Dow Corning 245 Fluid, Dow Corning) 4.0 4.0
Tocopheryl acetate - 0.5
F. Phenylbenzimidazole sulfonic acid (Parsol HS, Roche)c 2.0 2.0
Water (aqua) 20.0 20.0
G. Potassium hydroxide, 10% sol to pH 7 qs qs
H. Bis-PEG-18 methyl ether dimethyl silane
(Dow Corning 2501 Cosmetic Wax, Dow Corning) - 2.0
Procedure: Combine C. Adjust pH to 7 with D and heat to 75C. Mix A and heat to 85C. Add B
to A with gentle mixing. Add CD to AB under strong agitation. Continue mixing while cooling to
45C. Combine E and add to ABCD with strong agitation. Combine F and adjust to pH 7 with G.
Heat to 30C and add H. Add FGH to ABCDE. Check pH of final formulation. If necessary, adjust to
pH 7 with potassium hydroxide. Add deionized water to compensate for water loss during heating.
* In the US, the FDA does not permit the combination of Butyl methoxydibenzoylmethane
(Parsol 1789) with Phenylbenzimidazole sulfonic acid (Parsol HS)

4-Methylbenzylidene camphor (UVINUL MBC 95) is only approved for use in European suncare
formulations

173
Based on in-vitrob and in vivoc SPF evaluations of Formulas 1

and 2, it was determined that stearyl dimethicone contributed to
increased SPF compared to the formulation without stearyl dime-
thicone (Figure 2) and to the other two alkylmethylsiloxanes (data
not shown) used for comparison. As shown in Figure 2, stearyl
dimethicone allows the use of less UVB filter to achieve the same
SPF value as that of the formulation with more UVB filter, but with
no stearyl dimethicone. The impact of these results is the ability to
decrease both cost and potential irritancy of the final sun care for-
mulation, but to retain the same level of sun protection.
Figure 2. In vitro SPF results for different levels of UVB filters with and without stearyl
dimethicone
Values for thixotropy also were higher with the stearyl dime-
thicone. This property allows the product to be evenly distributed
on skin, improving sun protection by the formation of a uniform,
homogeneous film. From the study results, it is apparent that certain
b
In-vitro test method: Diffey and Robson method using a Optimetrics 290 SPF analyzer,
using Transpore tape from 3M as the substrate
c
In vivo test method: conducted by Australian Photobiology testing facility Pty Ltd,
University of Sydney Australia

174
alkylmethylsiloxanes, in particular stearyl dimethicone, demonstrate

synergistic effects when combined with organic UV filters. They
help improve the distribution of sunscreen actives on the skin,
which increases the SPF value for a particular formulation.
Silicones and Fragrance Synergies in Hair Care

Silicones have a long history of use in hair care, where they are rec
ognized for their ability to provide conditioning, shine, manageability,
improved combing, reduced flyaway and a number of other benefits.4
We have collaborated with researchers at Takasago International
Corporation, one of the worlds leading fragrance houses, to study
the synergies between fragrance and silicones in rinse-off hair care
applications.5 In particular, the team focused on divinyldimethi-
cone/dimethicone copolymer (and) C12-C13 pareth-3/C12-C13
pareth-23.d This ingredient is a 60% nonionic emulsion of very
high viscosity (>120x106 mm2/s at 0.01 Hz) polydimethicone/vinyl
copolymer.
The synergies could be described as a physical interaction
between fragrance molecules and the silicone emulsion. The syner-
gies are optimized based on the detailed knowledge of the physical
properties, including perfume polarity, vapor pressure and clogP
values of the individual fragrance components. Subsequently,
Takasago researchers evaluated fragrance delivery in shampoo
formulations with and without the silicone. The objective was to
demonstrate the effects of the incorporation of silicones into hair
care products on fragrance performance during the normal product
use cycle.
Takasago proprietary fragrances were incorporated with silicone
into a shampoo and hair conditioner product, and fragrance per-
formance was followed by olfactory evaluation of intensity levels.
A premix containing fragrance and the emulsion of ultra high
molecular weight silicone was prepared prior to addition into the
formulations. This premix was then added to Takasagos in-house
d
Dow Corning HMW 2220 Nonionic Emulsion (INCI: divinyldimethicone/dimethicone
copolymer (and) C12-C13 pareth-3/C12-C13 pareth-23) is a product of Dow Corning Corp.,
Midland, Michigan USA.

175
shampoo and conditioner bases. Half-head experiments were con-

ducted with four subjects in Takasagos in-house salon. Fragrance
intensity evaluations (using a scale of 1 to 5) were conducted by a
trained, four-member panel of experts (perfumers and odor evalua-
tors) at the following stages:
Neat product
Hair during lathering
Hair after rinsing
Hair after blow drying
Hair six hours after drying
Figure 3 summarizes the average scores of ten fragrance evalu-
ations in half-head tests. Comparisons were made with a prototype
shampoo containing 3.2% emulsion of high molecular weight
silicone and 0.8% fragrance, and a control containing 0.8% fragrance
and no silicone. The presence of the silicone emulsion in the test
shampoo resulted in greater perceived fragrance intensity of hair
during the in-use phases of lather, rinse, after blow-drying and six
hours after blow-drying, when compared to the results of the same
formulation without the silicone emulsion.
Formula 3 is an example of a prototype shampoo with light to
medium conditioning and long-lasting fragrance properties.
Prototype shampoo with
Figure 3. Fragrance performance in silicone-containing shampoo, based on half-head testing

176
Formula 3. Light to medium conditioning shampoo with and

long-lasting fragrance properties
A. Water (aqua) 21.00% wt
B. Hydroxypropyl methylcellulose (Methocel, Dow Chemical) 0.30
C. Water (aqua) 43.40

Tetrasodium EDTA (Versene 100, Dow Chemical) 0.05
D. TEA lauryl sulfate (Standapol T, Cognis) 18.00

Ammonium lauryl sulfate (Standapol A, Cognis) 8.00
Lauramide DEA (Standamid LD, Henkel KgaA)* 4.00
Divinyldimethicone/dimethicone copolymer (and)
C12-13 pareth-3 (and) C12-13 pareth-23
(Dow Corning HMW 2220 Nonionic Emulsion, Dow Corning) 3.20
Palmitic acid 0.30
E. DMDM hydantoin 0.15

Sodium chloride 0.30
Citric acid 0.50
F. Fragrance (parfum) (Florafresh/Takasago) 0.80
Procedure: Heat A to 80C. Add B and mix until completely dissolved. In a separate container,
combine C. Add C to AB with gentle mixing. Cool to RT. Continue mixing for an additional 15
min. Add D to ABC. Add E to batch, and add F to batch.
* Lauramide DEA is no longer used in the US
Synergy Between Silicone Polyether and Organic

Quat Systems6
One of the appealing novelties in the personal care field relates to
the introduction of clear or colorless products. This trend has given
rise to the category of clear, and mild conditioning shampoos.
Consumers who look for clear products associate the clarity with
naturalness, lightness, freshness and a young, modern image. These

177
clear, mild products claim many related features such as high purity,
non-greasy feel, noncomedogenicity, nonallergenic properties, and
a smooth, silky feel on hair. Dimethicone copolyols (silicone poly-
ethers) can easily be incorporated into clear shampoo formulations
without affecting their appearance.
In contrast to opaque shampoos, clear shampoos are marketed
as mild and light. In addition to gentle cleansing, several other
attributes must be built into such formulations to complete the
creation of a clear, mild and light conditioning shampoo. Mildness
is associated with the generation of rich and creamy foam during
the washing step, and after rinsing, the hair must appear natural
and healthy. A number of additional benefits must be built into the
system, including easy detangling and combing, body, good manage-
ability, and strength with good elasticity.
In general, clear, mild and light conditioning shampoos contain
milder surfactant types than the more irritating anionic surfactants
used in traditional formulations. Amphoteric cosurfactants such
as betaines and anionic cosurfactants such as sulphosuccinates are
examples of such milder surface-active cleansing agents.7 Additional
ingredients are also required, including foam boosters, thickening
agents or solubilisers.
Conditioning benefits are known to be enhanced by the use of
moderate molecular weight quaternary ammonium polymers (quats).
These include, for example, polymers based on hydroxyethylcellulose
cationic modifiede and hydroxypropyl guar hydroxypropyltrimonium
chloride.f Both products enable the formulation of clear shampoos.
Furthermore, these polymer types have various benefits, including
improvement of both wet combing and hair manageability.
The addition of certain silicone polymers to the above mentioned
systems has been found to improve conditioning performance.
However, the synergy between these two types of materials has
only recently been demonstrated.6 Silicone polyethers are a class
of functionalized silicones that have been found to help deliver
e
UCARE polymers (INCI: polyquaternium-10) are products from Amerchol Corporation,
Edison, New Jersey, USA.
f
Jaguar C162 (INCI: hydroxypropyl guar hydroxypropyltrimonium chloride) is a polymer
from Rhodia, Lyon, France.

178
some of the benefits expected by consumers from clear, mild and

light conditioning shampoos. The pendant hydrophilic ethoxylated
chains on the hydrophobic siloxane backbone provide surface-active
properties. Such properties enable certain silicone polyethers to be
easily solubilized or dispersed in surfactant systems. The following
silicone polyethers were selected for evaluation with the previously
mentioned quaternary-modified polymers: PEG-12 dimethiconeg,
characterized by a low molecular weight and (EO)n type function-
ality; and Lauryl PEG/PPG 18/18 methiconeh, characterized by a
medium molecular weight,-(EO)n(PO)n and C12 pendant chains.
To demonstrate that the dimethicone copolyols produce useful
synergistic effects when combined with quaternary polymers typi-
cally used in shampoo, a clear and light conditioning shampoo was
formulated (Formula 4).
The performance of Formula 4 with and without different
polymeric quaternary polymers and selected silicone copolyols
was evaluated for foam generation and stability, detangling ability,
flyaway (antistatic) and sensory benefits (softness, body, volume,
shine). The detangling properties (Figure 4) of the shampoos were
evaluated by measuring the time needed for panelists to completely
detangle hair tresses. Results on some of the other properties for
polyquaternium-10 and either PEG-12 dimethicone or lauryl PEG/
PPG 18/18 methicone are summarized in Figure 5.
Foam generation and foam stability were evaluated by measur-
ing the quantity of foam generated by a diluted shampoo sample,
stirred under standard conditions. The dimethicone copolyols
studied did not negatively impact the foam quantity of the shampoo
with or without the quaternary-modified polymers. They were able
to improve the foam generation and the resulting sensory profile
(density, creaminess etc.). The surface activity of the dimethicones
copolyols is believed to be responsible for these benefits.
The surface activity of the silicone polyethers is responsible for
the benefits observed. It is well recognized that if properly chosen,
g
Dow Corning 5324 Fluid (INCI: PEG-12 dimethicone) is a product of Dow Corning Corp.,
Midland, Michigan, USA.
h
Dow Corning 5200 Formulation Aid (INCI: lauryl PEG/PPG 18/18 methicone), Dow Corning
Corp., Midland, Michigan, USA.

179
Formula 4. Mild and light shampoo
A. Sodium laureth sulfate (Empicol ESB3/M/A, Albright & Wilson UK Ltd) 30.0% wt
Cocamidopropyl betaine (Amonyl 380 BA, SEPPIC) 3.0
Disodium ricinoleamideo MEA sulfonosuccinate
(Rewoderm S 1333, Degussa Care Specialties) 3.0
Water (aqua) qs 100.0
B. Cocamide DEA (Comperlan KD, Cognis Corp)* 4.0
C. Guar hydroxypropyltrimonium chloride (Jaguar C-13S, Rhodia Inc) 0.1 to 1.0
D. PEG-120 methyl glucose dioleate (Glucamate DOE-120, Amerchol Corp) 1.0 to 2.0
E. Lauryl PEG/PPG 18/18 methicone
(Dow Corning 5200 Formulation Aid, Dow Corning) or
PEG-12 dimethicone (Dow Corning 5324 Fluid, Dow Corning) or
Bis-PEG-18 methyl ether dimethyl silane
(Dow Corning 2501 Cosmetic Wax,. Dow Corning) 2.0
DMDM hydantoin 0.1
Citric acid qs
Procedure: Combine A in appropriate vessel and heat to 65C with a water bath. Keep some
water for dispersing C and D (approximately 10 g for each ingredient in C and D). Heat B
separately to 65C with a water bath. Disperse C in sufficient water and heat to 65C. Disperse
D in sufficient water and heat 65C. Add A to B. Add C to AB. Add D and E to batch. Neutralize
with citric acid if required.
* Cocamide DEA is no longer used in the US due to safety concerns
Figure 4. Wet detangling results (time in sec) for hair treated with and without silicone
polyethers and quaternary polymers

180
certain silicone copolyols provide additional stabilization at the gas/

liquid interface. It is believed that by lowering the total free energy
of a gas/liquid system, silicone polyethers increase the elasticity of
the air/liquid interfacial film, leading to foam-boosting effects.8
Figure 5. Summary of synergistic effect of selected silicone polyethers and quaternary

polymers in shampoos. Units of improvement of parameter versus control shampoo
without dimethicone copolyol or quaternary polymer.
The results shown indicate that the combination of dimethicone

copolyols and quaternary polymers in clear, mild and light-con-
ditioning shampoos provides improved conditioning. Moreover,
their combination brings synergistic benefits that are not perceiv-
able when the two materials are used separately in a shampoo. One
possible explanation for this behavior is that quaternary polymers
form ion pair complexes in the presence of anionic surfactants.
The complex coacervates precipitate when diluted (e.g., during the
rinsing step, thereby allowing deposition of the quaternary polymer
onto the hair). By modifying the spreading coefficient and reduc-
ing the surface tension to lower levels than achievable with organic
surfactants, the silicone surfactant forms a more homogeneous film
of quaternized polymer on hair.
The silicone polyethers, which are partially water dispersible,
have been demonstrated to deposit by flocculating along with the
quaternary polymer. Due to their physico-chemical properties, sili-
cone polyethers help the quaternary polymer to form an improved

181
conditioning film, thereby providing additional silicone feel benefits.

Another hypothesis proposed is that the pendant ethoxylated chains
of the silicone polyethers form weak hydrogen bonds with the amino
acids of the hair shaft, thereby providing a light conditioning effect.
In spite of such weak bonding forces, the greater affinity of silicone
polyethers for water would allow them to be easily removed from the
hair during the rinsing process when additional water is provided.
Conclusions
Several different silicone-based technologies illustrate the synergis-
tic properties of silicones with a variety of personal care actives via
physical associations. These techniques offer wide scope for a range
of innovative personal care applications.
Joanna Newton and Catherine Stoller

Dow Corning Europe, Seneffe, Belgium
Michael Starch
Dow Corning Corporation, Midland, MI USA
References
1. A DiSapio, New approaches to antiperspirant and deodorant formulations, HAPPI (Feb
1986)
2. I Van Reeth and A Urrutia, New silicone-based solutions for suncare, SEPAWA
conference proceedings p53-66 (Oct 2003)
3. I Van Reeth and JM Blakely, Use of current and new test methods to demonstrate the
benefits of alkylmethylsiloxanes in sun care products, Dow Corning internal publication
22-1793-01 (1999)
4. S Marchioretto, Optimizing the use of silicones in hair care products, Dow Corning
internal publication 22-1720-01 (1998)
5. US 60/106399, Compositions comprising silicone-in-water emulsions and fragrances
and hair care preparations containing such compositions, AL Girboux, L Marteaux, J
Newton and I Van Reeth, assigned to Dow Corning Corporation (Sept 2003)
6. S Marchioretto and JM Blakely, Substantiated synergy between silicone and quats for
clear and mild conditioning shampoos, SFW special edition 1B 10303D, 12 1-7
(Oct 1997)
7. HI Leidreiter et al., Internatl J Cosm Science Vol 19, Issue 5 p 239
8. MJ Owen, The surface activity of silicones: a short review, Ind. Eng. Chem.- prod. Res.
Dev., 19, p97-103 (1981)

Chapter 21
Performance and
Sensorial Benefits of
Cationic Guar in Hair
Care Applications
KEY WORDS: cationic guar, shampoo, hair repair, foaming power, foam
rheology, sensorial attributes
ABSTRACT: Cationic guars have demonstrated ability to manage the
surface of the hair. This article discusses their physico-
chemical properties, their hair conditioning and repairing
properties, and their impact on foam sensorial aspects.
The consumers interest in multifunctional benefits is what cur-

rently drives the global personal care market. Within the hair care
market, rinse-off products such as shampoos remain the most
popular means for hair care because consumers spend more time
washing their hair and less time applying additional treatments.
This being the case, consumers are more likely to rely on shampoo
that conditions, protects and repairs the hair, as well as provides
enhanced sensorial attributes.
From a formulation standpoint the challenge is to control depo-
sition of benefit agents such as cationic polymers, silicones and/or
vegetal oils under rinse off in order to provide optimum performance.
One response is cationic polymer derivatives such as cationic guar for
surface management and delivery of multifunctional benefits.
Hair Surface Management

Cationic guars are polysaccharide derivatives, produced from the
quaternization of guar gum. Guar gum is a natural and renewable

184
Shampoo Performance and Sensorial Benefits of Cationic Guar
resource extracted from the seeds of guar bean (Cyamopsis tet-

ragonoloba taub). Guar gum is made of beta 1,4-glycosidic mannose
units that statistically alternate between having and not having one
alpha 1,6-bound galactose unit forming a side branch (Figure 1).
Figure 1. Cationic guar gum structure
The study of the physico-chemical behavior of polymers in

surfactant environment has enabled more perfect control of cationic
guar properties for optimum uptake on the hair.
The deposit of cationic guars does not rely solely on the fact that
they are cationic and the hairs surface is anionic. Due to the unique
structure of cationic guars they interact well with surfactants to
reach the hairs surface.
The challenge is to formulate a stable shampoo system that con-
tains oppositely charged species (cationic guar, mixture of anionic
and amphoteric surfactants) that will eventually need to become
destabilized to allow for polymer deposition. Within a few seconds
of shampoo application onto wet hair, dilution occurs as a result of
increased water content in the system. Driven by entropy, a surfac-
tant/polymer complex forms due to the release of the counter-ions
into the bulk.1
The three-phase diagram in Figure 2 (see Color Insert 7) illus-
trates the typical destabilization mechanism that leads to polymer
uptake onto the hair.

185
Chiron Chapter 21
Figure 2. Three-phase diagram
Besides its intrinsic effectiveness, the polymer/surfactant com-

plex acts as a net to capture and deliver dispersed particles on the
hair fiber during precipitation. Thus, cationic guar can be used to
perfectly control and enhance the delivery of particulate agents,
such as silicone emulsion, to modify the hairs surface.2 Hair surface
modification could ultimately be translated into consumer benefits.
Hair Conditioning and Repairing Performance

Uptake: The uptake efficacy of cationic guar from a given sham-
poo formulation was tested on a hair-like surface. We monitored
the amount of a fluorescence-tagged cationic guar deposited onto a
negatively charged surface that mimics the hair. When applied onto
wet hair, a shampoo is diluted by six to ten times according to the
quantity of water retained in the hair. Thus, for optimum polymer
deposition, precipitation should take place when diluted between
six and ten times. As depicted in Figure 3, maximum uptake of
guar hydroxypropyltrimonium chloride occurs at the dilution factor
six before the rinsing stage regardless of the type of shampoo for-
mulation system. This performance is achieved by optimizing the
physico-chemical characteristics of the polymer.

186
Figure 3. Disposition of a fluorescence-tagged cationic guar on a negatively charged surface
Conditioning: Beyond optimum uptake properties, when used in

conjunction with silicone emulsions, cationic guar allows the best
conditioning system to be created. Furthermore, when compared to
other types of cationic polymers classically used in shampoo formu-
lations, such as polyquaternium-10 (PQ-10) or polyquaternium-7
(PQ-7), cationic guar helps to optimize conditioning performance.
Figure 4 represents the silicone deposition yield obtained from
a sodium laureth sulfate and sodium cocoamphoacetate (SLES/
CAMA) shampoo base containing different types of cationic poly-
mers. Silicone emulsion deposition yield has increased by almost
two fold when using guar hydroxypropyltrimonium chloridea com-
pared to polyquaternium-10. The use of cationic guar contributes
to reducing the total amount of silicone needed in a shampoo, while
maintaining conditioning performance.
Cationic guar delivers conditioning attributes at low usage
concentration levels. Ease of wet combing and half-head salon
tests illustrate such conditioning performance effectiveness. Ease
a
Jaguar single derivatized cationic guars. Examples include C-13S, C-14S, C-17 condition
ing cationic guars for opaque formulations. Jaguar is a registered trade name of Rhodia,
Cranbury, New Jersey, USA.

187
Chiron Chapter 21
of wet hair combing was carried out using Diastron equipment.

Shampoos containing from 0.1% to 0.3% of hydroxypropyl guar
hydroxypropyltrimonium chloride and polyquaternium-10 were
compared for their conditioning effect using Caucasian hair tresses
treated with one shampoo application. As little as 0.1% cationic
guar in the shampoo was sufficient to minimize wet-combing force,
whereas 0.3% polyquaternium-10 was originally required.
Figure 4. Enhanced deposition of silicone emulsion* onto hair surface

* SLES/CAMA: 14/2, pH 6, salt 1%, cationic polymer 0.3% wt, UV-tagged silicone particles
3% active
** Guar hydroxypropyltrimonium chloride
Half-head salon tests were performed at the Schrader Institute

(Germany) with 20 female volunteers to compare conditioning
attributes of shampoos based on either guar hydroxypropyltrimo-
nium chloride or polyquaternium-10. Cationic guar alone at 0.1%
outperforms polyquaternium-10 at 0.3% for all the shampoo char-
acteristics and most of the conditioning attributes. Shampoos foam
texture and wet-combing were significantly improved.
Repair: Beyond hair conditioning, there is an increasing con-
sumer need for hair repair in order to achieve healthier looking

188
hair. The condition of the hair can deteriorate as a result of fre-

quent shampooing, applying chemical treatments (such as dyes
or perms) or exposure to environmental aggressions (such as UV
and pollution).3 From a microscopic view, damaged hair results in
cuticle uplift and cracking. As the cuticle separates from the cortex
the hair fiber becomes weaker and porous, thus leading to increased
water absorption, which impacts its mechanical properties.
As demonstrated by Scanning Electron Microscropy, multiple
treatments of a hair fiber with a shampoo containing cationic
guar reversed hair damage by cementing the uplifted cuticle back
onto the cortex. This contributes to the restoration of the hair
fiber strength.
In another demonstration of cationic guars impact on hair
repairing, the porosity and hydrophilic nature of damaged hair were
shown by use of a Kruss balance apparatus to measure the wetability
of a hair fiber as it is immersed in distilled water.4 Damaged hair
fiber absorbs water as it is submerged, which generates abnormally
high wetting forces. Virgin hair is more hydrophobic and repels the
water as cuticle uplift is reduced. Thus, hydrophobic hair is being
pushed up from the water and the load on the balance is reduced.
As illustrated in Figure 5, the hydrophobic character of Cau-
casian virgin healthy hair could well be differentiated from the
hydrophilic characteristics of damaged hair. Sodium laureth sulfate
shampoo formulations containing either guar hydroxypropyltri-
monium chloride or polyquaternium-10 were compared for their
ability to restore hydrophobic character of damaged hair. Shampoo
formulations were applied six times on damaged hair fibers and the
results clearly indicated that cationic guar repairs damaged hair by
greatly reducing its hydrophilic nature in comparison to polyquater-
nium-10.
Enhancement of Sensorial Benefits

Beyond the primary properties of shampoocleaning, condition-
ing or repairingshampoo sensorial aspects provided through the
foam are essential. Lather characteristics of shampoo are critical as
consumers tend to associate first sensory experience with product

189
Chiron Chapter 21
performance. For psychological and sensitive reasons, consumers

want to feel foam when they use a shampoo. Therefore foam must
remain stable in the presence of soil and sebum that cover the hair,
so it should not begin to dissipate immediately when used.
Figure 5. Cationic guars help in restoring hydrophobic character of damaged hair
Foam bubble size distribution: Foam can be described as a non-

equilibrium dispersion of gas bubbles in a liquid.5 Foam stability is
greatly influenced by properties of air/water interface. To study the
effect of cationic guar on foam stability, we first compared foam
bubble size distribution of two shampoos, one of which was formu-
lated with hydroxypropyl guar hydroxypropyltrimonium chlorideb
(Figure 6). Foam bubbles generated out of the cationic guar-con-
taining shampoo were found to have a mono disperse distribution
with particle size centered around a small diameter. As a result,
bubbles become more compact and uniform, leading to nicer, whiter
and shinier foam.
Foam bubble size over time: Next, we measured foam stability by
monitoring average bubble diameter over time (Figure 7). The rate
of bubble coalescence from a shampoo base containing hydroxypro-
pyl guar hydroxypropyltrimonium chloride was slower than that of
the same shampoo without the polymer. As a consequence of
b
Jaguar double derivatized cationic guars. Examples include C-162 and Excel conditioning
cationic guars for clear formulations.

190
increased film elasticity, the bubbles expand or rupture more slowly.

Cationic guar contributes to extending foam life by modifying
bubble film characteristics.
Figure 6. Cationic guars impact on foam bubble size distribution
Figure 7. Cationic guars enhance foam life

191
Chiron Chapter 21
Foam firmness: Evaluation tests were specifically developed to

further compare foam sensorial attributes to measurable physi-
cal parameters. The objective was to set up easy-to-use equipment
enabling a fast screening of cationic polymers and their impact on
foam properties such as foaming power and rheology.
One of the most commonly used methods to characterize foam-
ing power is the Ross-Miles characterization methods (ASTM
standardized) measuring both foaming ability and stability. A
known amount of shampoo solution is poured into a column;
measurements are taken of the foam height initially and again after
5-10 minutes. Furthermore, foaming power measurement was also
achieved in the presence of sebum well known to have detrimen-
tal effects on foam stability. A known amount of synthetic sebum
emulsion is introduced to the solution tested in order to represent
moderately dirty hair.
The characterization of foam rheology is an important aspect
of foam sensorial attributes. Although a creamy and dense lather
can be directly felt by the consumers fingers and could be linked to
foam consistency, we wanted a specific test to measure the consis-
tency of freshly produced foam or its resistance to an applied force.
Therefore, we developed a device to reproduce the foam that would
match the characteristics of the foam generated from a shampoo
worked through wet hair. A deformation force is applied onto the
calibrated foam. The absolute maximum resistance force (mN) is
then recorded over time. This force value relates to the foams firm-
ness. A variation of 2 mN in force would translate to a significant
change in sensorial signals for an untrained consumer panel.
Different sources of cationic polymers were assessed for their
influence onto physical foam properties. Polymer derivatives were
from guar origin (guar hydroxypropyltrimonium chloride), cellu-
lose (polyquaternium-10) or synthetic origin (polyquaternium-2,
polyquaternium-7). All the cationic polymers were formulated
at 0.2% active content in ALS/ALES/CAPB (ammonium lauryl
sulfate / ammonium laureth sulfate / cocamidopropyl betaine: 7/7/2
respective ratio) added with 0.15% NH4Cl shampoo base.
The effect of each the cationic polymers on foam firmness of
the ALES shampoo base is shown in Figure 8. Most of cationic

192
guars tested, including the one shown in Figure 8, show higher

foam firmness than the levels achieved by the other tested cationic
polymers. Similarly, all cationic guars, including the one shown in
Figure 9 (see Color Insert 7), outperformed polyquaternium-2 and
polyquaternium-10 as foam height was significantly improved in the
presence of sebum.
Figure 8. Cationic guars impact on foam firmness
Figure 9. Cationic guars impact on foam volume

193
Chiron Chapter 21
Furthermore, changing the co-surfactant nature, from coc-

amidopropyl betaine to sodium cocoamphoacetatec or sodium
lauroamphoacetated impacted the foam properties. Combining
amphoacetate surfactant derivatives with cationic guar enhances
both foam volume in the presence of sebum (Figure 10) and foam
firmness compared to polyquaternium-10.
Figure 10. Fine tuning foam abundance with cationic guar and amphoacetate base surfactants
Conclusion
With appropriate choice of cationic guar, formulators can adjust
hair surface management and delivery of benefits agents from
shampoos. Cationic guars can significantly improve the mechanical
and sensorial attributes of foaming shampoos. Foam abundance and
elastic property can be fine tuned in order to give a different senso-
rial trigger to consumers. With a better understanding of the in-use
interactions between cationic guar and the different ingredients of a
rinse-off formulation, formulators can achieve outstanding perfor-
mance that translates into multifunctional consumer benefits.
c
Miranol Ultra C-32, Rhodia, Cranbury, New Jersey, USA. Miranol is a registered trade name
of Rhodia.
d
Miranol Ultra L-32, Rhodia, Cranbury, New Jersey, USA

194
Acknowledgements
The author wishes to acknowledge Olivier Anthony, Patrick de Lanty, Anne-France Leron
and Mlissa Manuszak for their contribution to the work discussed in this article.
Stephanie Chiron
Rhodia Research, Aubervilliers, France
References
1. B Jnsson, B Lindman, K Holmberg and B Kronberg, Surfactants and Polymers in
Aqueous Solution, Chichester, WS, England: J Wiley & Sons Ltd (1998) pp 219-244
2. US Pat 5,085,857, Conditioning shampoo comprising a surfactant, a non-volatile
silicone oil and guar hydroxypropyltrimonium chloride as a cationic conditioning
polymer, AM Murray and ES Reid (Feb 4, 1992)
3. KF De Polo, A Short Textbook of Cosmetology, Augsburg, Germany: Verlag fr
chemische Industrie, H Ziolkowsky GmbH (1998) pp 49-80
4. S Rogasik, N Martin, JM Ricca, W Wielinga and O.Anthony, The challenge of damaged
hair shampoos which links between benefits on damaged hair and measurable physical
parameters?, SOFW Journal 125(11) 32-39 (1999)
5. S Ross, Foams, Encyclopedia of Chemical Technology, 4th edn, New York: J Wiley &
Sons, volume 11, pp 783-804

Chapter 22
Formulating Hair
Conditioners: Hope and
Hype!
KEY WORDS: conditioner, gloss, viscosity, humectants, preservatives
ABSTRACT: Discussion of hair conditioner claims and some guidelines for
formulating products.
Hair conditioners are one of the most widely used products in the
personal care arena. A recent perusal of two Web sites (www.ulta.
com and www.drugstore.com) showed that there are more than
150 different SKUs (stock keeping units) out there to choose from.
It certainly must be confusing to consumers I know it is to me!
There is probably no other personal care category that uses more
hype words and makes more promises to users than the hair care
industry. Some of the claims that I found are listed in the sidebar
Hair Product Claims along with some common questions I cant
help but ask. These are what I call some amazing claims hair is
dead. It cant be fed and doesnt eat. If it was alive, then every time
we got a haircut we would scream in pain and bleed to death!
Table 1 is a simplistic (but fairly accurate) accounting of hair
conditioner components. As you can see, this is a fairly simple
formulation. While most hair conditioners are oil-in-water lotions
designed to be applied to wet hair after shampooing then rinsed out,
there are many variants on this theme. We see spray aqueous condi-
tioners designed for squirming children, cream leave-in conditioners
targeting heavily damaged permed or relaxed hair, mousses, oils and
many, many other products and product forms.
Practically all hair conditioners start out with a primary condi-
tioning agent. This positively charged species is substantive to hair

196
Condition Performance and Sensorial Benefits of Cationic Guar
Hair Product Claims

100% Vegan Formula
DEA free
No animal testing
Moisturizer
Revitalizes dry parched hair
Stimulates scalp
Aromatherapeutic benefits
Incredible shine
Detangles
Energizes
Feather light (Are they selling a vacuum?)
No harsh chemicals
No oils
Seals in moisture
Rehydrates
Moisturize split ends
Advanced ingredients
Leaves hair soft, manageable and renewed
Revitalized sun, heat, styled or damaged hair
Free your mind and spirit (Is this a hair conditioner or a course in Yoga?)
Delivers 300% of the vitamins and nutrients
(What percentage does hair need?)
Strengthens
Dramatic hair recovery
Volumizing
Root lifter
Increase thickness and diameter of hair
Smooth rough cuticle
Reconstruct hair inside and out
With certified organic ingredients
High potency
Restores critical moisture
99.25% natural (Is the rest supernatural?)
Vitamins preserve pH balance (I didnt know vitamins effect pH of the hair.)
Shine-infusing citrus extracts
Makes hair up to 5 time stronger and more elastic
Pure, genuine and authentic essential oils
Hair Product Claims continued on the following page...

197
Klein Chapter 22
Hair Product Claims continued from the previous page...
Texture and volume for thin, wimpy hair

Leaves hair ultra-shiny
Awaken you hairs natural beauty... with Kiwi, Kumquat and fig
With Planthenol-3 (Not in INCI dictionary)
With Nutrium-23 complex (Also not in INCI dictionary)
With ISOflex (Again, also couldnt find in INCI dictionary.)
Burst of juicy grape
With advanced NexxuSphere technology
Contains activated moisturizing blend of Hawaiian awapuhi and
instant moisture complex
Scientifically designed (As opposed to being designed by plumbers?)
Heat activated
Tri-level protein complex
Massive conditioning power
Restores protein and moisture lost due to chlorine damage
Super-structure builder, reconditions flat deflated hair
Natural bamboo whips lifeless hair into shape
Table 1. Hair Conditioner Components
Function % Active
Water qs to 100%
Primary conditioner 1.0 - 2.0
Secondary conditioner 0.5 - 1.0
Tertiary conditioner 0.0 - 0.5
Viscosity control agent 1.0 - 1.5
Emulsifier 0.5 - 2.0
Gloss agent 0.25 - 2.0
pH adjuster 0.2 - 0.3
Preservative 0.05 - 1.0
Fragrance 0.1 - 2.0
Specialty additives 0 - 1.0

198
Condition Performance and Sensorial Benefits of Cationic Guar
(and skin), which has a net negative charge due to the presence of
protein. Generally, this material is a difatty quaternary ammonium
compound such as dicetylmonium chloride, for example. The fatty
portion is typically saturated and composed of 16-18 carbons, but
we occasionally see longer chain lengths. As a general rule, with
an increase in the number of carbons we get more shine and con-
ditioning. These difatty quats also function as emulsifiers due to
their polar heads (positively charged nitrogen) and fatty tails. For
this reason, we do not see trifatty quats used as much since stearic
hindrance prohibits their function as effective emulsifiers.
Formulators often combine several conditioning agents to
give more complete conditioning. We also see extensive use of
cationic polymeric materials, which also form a film on the hair
shaft and can increase the viscosity. Examples of these materials
are polyquaternium-10, polyquaternium-11 and guar hydroxy-
propyltrimonium chloride. Sometimes we see a tertiary amine
(stearamidopropyl dimethylamine) used, which becomes positively
charged (protonated) as the pH is dropped with an appropriate acid
(lactic, glutamic, citric, etc.).
When comparing the differences between rinse-out and leave-in
conditioners, sometimes the only difference is in the fact that rinse-
out conditioners contain a higher percentage of conditioners with
(sometimes) a longer chain length. As mentioned previously, the
primary conditioner can also function as the primary emulsifier, but
often cosmetic chemists employ another emulsifier. It can be non-
ionic or cationic in nature. If nonionic emulsifiers are used, they are
typically ethoxylated fatty materials (for example, glyceryl stearate
(and) PEG-100 stearate or cetearyl alcohol (and) ceteareth-20).
It should be pointed out that when using these highly ethoxylated
emulsifiers, there may be some decrease seen in substantivity of
the conditioning agents. Thus, the use of cationic emulsifiers is
preferred. It has also been observed that amine oxides (nonionic)
can enhance the deposition of the conditioning agents, which is
particularly true at the low pH levels (3.5-5.0) most often found in
conditioners.
Achieving gloss in hair conditioners is a key goal. While the
primary conditioner may impart some gloss, other fatty materials

199
Klein Chapter 22
are added in most cases. They can be silicones (dimethicone, dime-

thiconol, amino-functional silicones, silicone gums), natural oils or
even materials specifically designed for this function (castor isostear-
ate succinate, for example).
While we often see fatty alcohols used to build the viscos-
ity, more recently we notice use of cationic polymeric thickeners
(polyquaternium-37). Occasionally we will see nonionic and hydro-
phobically modified cellulose thickeners used. The hydrophobically
modified cellulose can also act as en effective emulsion stabilizer. Be
careful not to employ the popular anionic thickeners (carbomer or
xanthan gum) since they will complex with the cationic condition-
ing agents and a gloppy mass will result.
Humectants are used to moisturize the hair and improve
freeze-thaw stability. As a result, we find extensive use of: propylene
glycol, hexylene glycol, butylene glycol and M,P diol along with
some cationic humectants (quaternium-22). One can certainly raise
the question whether these humectants actually increase the mois-
ture content of hair. I for one doubt it!
Preserving hair conditioners is usually much easier than with
most cosmetic emulsions since the cationic conditioning agents
often are weak preservatives themselves and thus the addition of
even low levels of conventional preservatives if often adequate.
However, if materials are added to the conditioner that can act as
food for the buggies (cellulosic thickeners, proteins, etc.), then
additional preservatives will be required.
When performing stability testing of these systems, be particu-
larly careful of freeze/thaw and high temperature (45C) conditions.
I recommend performing three freeze/thaw cycles of 45C for 24
hours followed by 20C for 24 hours. Be sure not to let the product
return to room temperature between stations.
Formulating hair conditioners is fairly easy and funand just
think of the claims your marketing friends will be making!
Ken Klein
President, Cosmetech Laboratories, Inc., Lincoln, CA USA

Chapter 23
Silicones for Hair

Strengthening
KEY WORDS: hair damage, hair strengthening, silicone, single fiber, tensile
testing
ABSTRACT: Single-fiber tensile testing demonstrates the hair-
strengthening properties of several silicone materials in
leave-in and rinse-off applications.
Consumers have become increasingly aware of hair damage caused

by chemical processes, heat styling and environmental factors. In
addition to healthy, shiny, smooth and silky hair, both men and
women look for protection against split ends and breakage, along
with greater strength and resilience.
Many women believe they have damaged hair, and products that
make hair-strengthening claims have caught the attention of these
consumers. Silicones hold promise for providing hair-strengthening
benefits, especially in products designed for damaged or ethnic hair.
A New Role for Silicones

A variety of silicone materials are recognized for their sensory and
functional benefits in hair care products. Initially incorporated into
formulations for their conditioning properties, silicones also provide
shine,1 aid color retention2 and protect against heat damage3 from
curling irons and blow dryers.
In the study described in this chapter, a method was developed to
determine whether silicones could also provide strengthening prop-
erties to hair, helping to counteract potentially damaging treatments.
In combination with the other multifunctional properties of sili-
cones, hair strengthening would offer additional consumer benefits
from individual products.

202
Condition Silicones for Hair Strengthening
The hair care industry has responded to these market needs, and
a number of commercially available products incorporate organic
ingredients traditionally used to strengthen or repair hair. These
typically include various wheat, soy or hydrolyzed vegetable pro-
teins. Another conventional ingredient, panthenol, is claimed to
provide hair strengthening as well as some degree of conditioning.
Assessing Hair Strength

Hair strength can be evaluated by methods such as tensile testing,
fatigue testing, microscopic analyses, light scattering measurements,
and simple combing and counting, which involves combing a swatch
of hair and physically counting the number of hairs that break.
The hair-strengthening properties of a range of silicones, both
functional (e.g., amino, polyether, alkyl) and nonfunctional (e.g.,
fluids, gum blends, elastomers and resins), were evaluated in dilute
form in leave-on and rinse-off applications, and also in a proto-
type leave-on conditioner. Single-fiber tensile testing was used in
this study for several reasons. First, the method is both scientific
and quantitative, and it is a recognized measure of hair strength.46
In addition, results are not affected by friction resistance; silicones
are already known for reducing friction. Finally, in-house expertise
already existed for other fiber materials; this expertise was translated
to measurements of single hair fibers.
In the single-fiber tensile test, the diameter of hair fibers was
measured using a laser micrometera. Using modeling glue, a single
unaltered European brown hair fiberb was mounted to two tabs to
create both a control and a treated sample from this one hair fiber
(Figure 1). This hair type was selected because it shows the least
amount of variability in damage fiber-to-fiber.7
Hair fibers having diameters of 5080 mapproximately 65%
of the fibers for this hair typewere selected for this study. The con-
trol and the treated samples were prepared by placing the mounted
fiber into the test solution, which was maintained at a constant
a
The Mitutoyo Laser Scan Micrometer (LSM-500) is a product of Mitutoyo Corp.,
Kanagawa, Japan.
b
Hair samples were obtained from DeMeo Brothers Inc., New York, NY USA.

203
Johnson et al. Chapter 23
temperature of 40C for two minutes to simulate water temperature

during bathing. In the case of the control, the solution was deionized
water. The section of the fiber (i.e., whether closer to the root or to
the tip) was randomized to remove bias from the study.
Figure 1. Mounting arrangement for single hair fiber
Three sets of tests were conducted:

Leave-on application: Dilute silicone material at 2% active
level in deionized water (Formula 1).
Leave-on application: Hair conditioner formulations at 2%
active level (Formula 2).
Rinse-off application: Dilute silicone material at 2% active
level in deionized water, followed by rinse. To simulate a

204
rinse-off application, treated samples were placed in an ultra-

sonic bathc of deionized water at 40C for an additional
two minutes.
Formula 1. Prototype leave-on conditioner (aqueous

system)
Acrylates/C10-30 alkyl acrylate crosspolymer 0.5% w/w

Water (aqua) qs
Triethanolamine qs
Cetearyl alcohol 1.0
PEG-100 stearate (and) glyceryl stearate 1.0
Siliconea 2.0
DMDM hydantoin 0.4
a
Based on level of actives. Emulsions were used for the aqueous systems and they vary in their
% active level.
Formula 2. Prototype leave-on conditioner (nonaqueous

system)
Ethanol 5.0% w/w

Silicone 2.0
Cyclopentasiloxane qs
Once treated, the control sample and the treated sample were
conditioned overnight at a constant relative humidity of 60%. The
need to control humidity during testing was based on literature and
c
The Branson 200 Ultrasonic Cleaner is a product of Branson Ultrasonics Corp., Danbury,
CT USA.

205
internal testing, which indicated humidity level was a critical factor

in hair strength; higher humidity results in lower hair strength.8 A
universal testing machined was used to pull test fibers to their break-
ing point; 50 fibers were tested for each material.
For each fiber, a curve was generated giving the load force vs.
the total displacement (sometimes called elongation) traveled for
both control and treated samples. Work is the calculated value of
total energy or force needed to stretch the fiber multiplied by the
displacement, which would be represented by the area under the
curve in Figure 2 for a given elongation. Based on information in
the literature, analysis was performed on the data at the fixed point
of 20% elongation.5,6
Work at 20% for the control was compared to the treated sam-
ple (for each of the individual values) using statistical softwaree.
Average work for the population was also compared using the same
statistical software.
Figure 2. Load force vs. displacement for treated sample and control
d
The Instron 4464 universal testing machine is manufactured by Instron Corp., Norwood,
MA USA.
e
Minitab 14 Statistical Software is a product of Minitab Inc., State College, PA USA.

206
Results showed that three silicones in particular demonstrated

hair-strengthening properties:
Silicone quaternium-16/glycidoxy dimethicone crosspolymer
(and) trideceth-12f
Silicone quaternium-16 (and) undeceth-11 (and) butyloctanol
(and) undeceth-5g
Aminopropyl phenyl trimethiconeh
Hair fibers treated with these silicones required higher average
work values at 20% elongation than the control, with a 90% confi-
dence level or greater (Table 1).
Table 1. Work of elongation (the product of kilograms of

force and millimeters of fiber displacement) for silicone-
treated and untreated hair fibers
A = Aminopropyl phenyl trimethicone

B = Silicone quaternium-16 (and) undeceth-11 (and) butyloctanol (and) undeceth-5
C = Silicone quaternium-16/glycidoxy dimethicone crosspolymer (and) trideceth-12
Leave-on Leave-on Rinse-off

dilute silicone solution conditioner formulation dilute silicone
solution
Silicone Treated Untreated Treated Untreated Treated Untreated
A 0.208 0.202 0.232 0.220 0.215 0.207
B 0.211 0.206 - - - -
C - - 0.242 0.222 0.215 0.202
The Hair-strengthening Mechanism

To better understand the mechanism for hair strengthening, the
authors examined hair fibers using a scanning electron microscope
(SEM). Figure 3 shows an untreated hair fiber in which the well-
f
Dow Corning 5-7070 Si Amino Elastomer Emulsion is a product of Dow Corning Corp.,
Midland, MI USA. Dow Corning is a registered trade name of Dow Corning Corp.
g
Dow Corning 5-7113 Silicone Quat Microemulsion is a product of Dow Corning Corp.,
Midland, MI USA.
h
Dow Corning 2-2078 Fluid is a product of Dow Corning Corp., Midland, MI USA.

207
defined cuticles overlap. Also shown is a hair fiber treated with

silicone quaternium-16/glycidoxy dimethicone crosspolymer (and)
trideceth-12 incorporated into a prototype rinse-off conditioner.
Note that the silicone forms a continuous film along the fiber shaft,
and hair cuticles are not visible.
Figure 3. Untreated hair fiber (left) and hair fiber treated with leave-on silicone
quaternium-16/glycidoxy dimethicone crosspolymer (and) trideceth-12 (right), both at 500x
Figure 4 illustrates SEM results on a hair fiber treated with

aminopropyl phenyl trimethicone, again as a dilute leave-on appli-
cation. The result is a medium-weight, semicontinuous film along
the hair shaft. The SEM also shows a hair fiber treated with dilute
silicone quaternium-16 (and) undeceth-11 (and) butyloctanol (and)
undeceth-5 in a leave-on application. The silicone leaves a medium-
weight film deposited primarily at the open edges of the cuticle.
Two possible mechanisms may explain how a silicone film con-
tributes to hair strength. The film may protect the hair cuticle during
elongation, and it may assist in sealing the hair cuticle, helping
prevent moisture penetration into and out of the hair cortex, main-
taining an optimal moisture level for hair strength. Although the
cortex provides the principal strength, it seems likely that the cuticle
provides additional protection, including strengthening properties.

208
Figure 4. Hair fibers treated with dilute aminopropyl phenyl trimethicone (left) and dilute
silicone quaternium-16 (and) undeceth-11 (and) butyloctanol (and) undeceth-5 (right),
both at 500x
Summary
The hair-strengthening properties of these materials, combined
with the other functional benefits of silicones for hair care, differen-
tiate silicones from other traditional ingredients promoted for hair
strengthening. In addition, silicones offer a range of benefits, includ-
ing conditioning, color protection, heat protection and shine. When
evaluated in specific applications, silicones can allow formulators
to develop highly differentiated products that will provide hair-
strengthening properties and meet specialized global market needs
such as those for damaged hair.
Bethany K. Johnson, Kim M. Quackenbush and Brian J. Swanton

Dow Corning Corp., Midland, MI USA
Published March 2007 Cosmetics &Toiletries
References
1. M Starch, Screening silicones for hair luster, Cosmet Toil 114(11) 5558 (1999)
2. B Moss, V Ungvary, S Marchioretto and B Johnson, Silicones combine color retention
for hair and new spray opportunities, Dow Corning White Paper 27-1171-01 (2005)
3. A Gomes and S Aguiar, Silicones protect thermally-treated hair by preventing moisture
loss, Dow Corning Advertorial 27-1124-01 (2005)

209
4. T Scharfeld, C DArrigo and KH Lim, A single hair fiber tensile tester for operation
under a scanning electron microscope, Massachusetts Institute of Technology, (http://
scholar.google.com/scholar?hl=en&lr=&q=cache:a5TEzkf9tc0J:web.mit.edu/tas/www/
HairStretch/HairTensileTest.pdf+single+hair+fiber+tensile+tester+for+operation+und
er+a+scanning+electron+microscope, Accessed Jan 18, 2007). See also J Woodruff,
Improving hair strength, Cosmet Toil 117(3) 3336 (2002)
5. AN Syed and H Ayoub, Correlating porosity and tensile strength of chemically modified
hair, Cosmet Toil 117(11) 5764 (2002)
6. AN Syed, H Ayoub and A Kuhajda, Recent advances in treating excessively curly hair,
Cosmet Toil 113(9) 4756 (1998)
7. JA Swift, PC Surinder, DL Coulson and NI Challoner, Flexabrasion: A method for
evaluating hair strength, Cosmet Toil 116(12) 5360 (2001)
8. CR Robbins, The physical and cosmetic behavior of hair, In: Chemical and Physical
Behavior of Human Hair, 3rd edition, Chapter 8, New York: Springer-Verlag (1994) pp
300309

Chapter 24
Anionic/Cationic
Complexes
KEY WORDS: foam, anionic/cationic interaction, quats, SLS, SLES-3,
compatibility
ABSTRACT: Understanding the interactions of surfactants is important
to optimizing their properties in formulations. The author
describes how the anionic/cationic interaction is critical to
properties such as foam, viscosity, conditioning properties,
and minimal irritation.
There have been a multitude of approaches to the formulation of

hair care products that provide multifunctional benefits. This par-
tially is because the various functions expected from products do
not co-exist well in one formulation. Consumers demand cleans-
ing, viscosity, foam, wet conditioning (antistat and wet comb), and
longer-term conditioning (dry-property conditioning). It would be
ideal if a universal surfactant existed that had just the right amount
of each property so formulation would be easy, but there is none.
Any step toward increasing the level of understanding related to
the interaction of surfactants and providing optimized properties in
formulation is desirable.
One major area in which interactions are critical is the anionic/
cationic interaction. Most formulators of 2-in-1 shampoos under-
stand that indiscriminate mixing of anionic and cationic materials
can result in undesired insoluble gunky solids. Anionic and cat-
ionic materials that are incompatible when mixed together have
been classified as hard complexes. As the expression implies, the
cationic and anionic compound possess properties that when
added together form insoluble complexes such as salts. In contrast,
anionic and cationic compounds that can be mixed over a wide

212
Condition Anionic/Cationic Complexes
range of ratios and provide a clear, viscous, high-foaming complex,

are defined as soft complexes. Optimized soft complexes have many
desirable properties including high levels of foam, viscosity build
without alkanolamides, conditioning properties, and low levels of
eye and skin irritation.
The terms used for quats and anionic materials are an adaptation
of the work of Pearson used to describe acids and bases. Pearson
proposed that hard acids bind strongly to hard bases and soft acids
bind softly to soft bases,1 the anionic and cationic interactions of
surfactants are exactly analogous.
Structural changes can soften cationic surfactant molecules,
making them more compatible with anionic systems. The com-
patibility of specific quats with sodium lauryl sulfate (SLS) and
sodium laureth-3-sulfate (SLES-3), the foam properties of the
combinations with SLS and SLES-3, and the substantivity of these
combinations with SLS and SLES-3, are key factors in understand-
ing the function of conditioners.
In order to understand the interaction, several quats were studied
in combination with SLS and SLES-3 (see Figure 1 and Table 1).
The entire work is published.2
R2
|
R -N+-R3
1
Cl-
|
R2
R1: R2:
1. Alkyl (C12) 1. Methyl (CH3)
2. Ricinoleylamidopropyl 2. 2-hydroxy ethyl
3. Dilinoleylamidopropyl (CH2CH2OH)
4. Cocamidopropyl

R2:
1. Methyl (CH3)
2. 2-hydroxy ethyl (CH2CH2OH)
Figure 1. Several quats were studied.

213
OLenick, Jr. Chapter 24
Table 1. Compounds studied
Name R1 R2 R3 Description
AMB Alkyl (C12) CH3 Benzyl Coco dimethyl benzyl
ammonium chloride
AME Alkyl (C12) CH2CH2OH CH3 Coco di-2 hydroxyethyl

methyl ammonium chloride
AMG Alkyl (C12) CH3 Glyceryl Coco dimethyl Glyceryl

ammonium chloride
AMM Alkyl (C12) CH3 CH3 Coco tri-methyl

ammonium chloride
AEB Alkyl (C12) CH2CH2OH Benzyl Coco di-2 hydroxyethyl

benzyl ammonium chloride
AEG Alkyl (C12) CH2CH2OH Glyceryl Coco di-2 hydroxyethyl

glyceryl ammonium chloride
CaMB Castor Amido CH3 Benzyl Ricinoleylamidopropyl

dimethyl benzyl ammoniu
chloride
CaMG Castor Amido CH3 Glyceryl Ricinoleylamidopropyl

dimethyl glyceryl ammonium
chloride
DMB Dimer Amido CH3 Benzyl Dilinoleylamidopropyl

dimethyl benzyl ammonium
chloride
DMG Dimer Amido CH3 Glyceryl Dilinoleylamidopropyl

dimethyl glyceryl ammonium
chloride
DMM Dimer Amido CH3 CH3 Dilinoleylamidopropyl

trimethyl ammonium
chloride
MMB Cocamido CH3 Benzyl Cocamidopropyl dimethyl

benzyl ammonium chloride
MMG Cocamido CH3 Glyceryl Cocamidopropyl dimethyl

glyceryl ammonium chloride
MMM Cocamido CH3 CH3 Cocamidopropyl trimethyl

ammonium chloride

214
Test Methodology
A determination of compatibility of a variety of quats with the
anionic surfactants, SLS, and SLES-3 was made. A 100 g sample of
10% active solution of SLS and SLES-3 was prepared, as was one
for each of the quats evaluated. The 100-g solution of sulfate was
added to a 250-ml beaker and under good agitation the solution was
titrated with the 10% quat solution. The endpoint was the first sign
of (a) an insoluble complex, (b) haziness, or (c) viscosity build.
Results
The quats that were compatible with SLS or SLES-3 are shown in
Table 2. All others in the study group were incompatible. The use
of the proper quat with a given anionic will allow the formulator to
maximize the performance of formulations.
Table 2. Soft quatsgel formers
Soft quats in SLS Soft quats in SLS-3

Quat Sample (viscosity of gel) Quat Sample (viscosity of gel)
MMB 14,000 AME 7,000
MMM 13,400 DMM 6,200
DMM 6,000 MMM 50,000
CaMB 1,000 CaMB 1,000
MMG 19,200 AMG 1,000
DMG 12,000 MMB 9,800
MMG 40,000
DMG 6,800
AEG 1,000
CaMG 1,000
Foam Testing
The solutions shown above were cut with water to 1% active and
evaluated in cylinder shake foam tests. The foam data is shown in
Table 3.

215
OLenick, Jr. Chapter 24
Table 3. Foam heights (cylinder shake foam test)
Quat sample Foam height (ml) (SLS) Foam height (ml) (SLES-3)
AMB Does not foam Does not foam
AME 190 90
AMG 500 400
AMM 600 500
AEB 300 200
AEG 200 100
CaMB 250 150
CaMG 200 100
DMB 400 300
DMG 300 200
DMM 250 150
MMB 400 300
MMG 400 300
MMM 400 300
Control (no quat) 600 450
Conclusions
Quaternium compounds can be classified as hard or soft by their
ability to form gelled systems with anionic systems. Cationic sys-
tems that form a gel at near stoichiometric amounts are classified as
soft quats; those that form precipitates of haze without appreciable
viscosity build-up are classified as hard quats. Soft quats can pro-
duce foam in the systems they gel, albeit at levels below the volume
of foam generated by the anionic, per se.
Quaternium compounds titrated with SLES-3 produced greater
viscosities with amido quats. The exception was amido quats con-
taining a benzyl group that exhibited a low viscosity in SLES-3.
Good foaming results also were seen with a number of com-
plexes. Additional work needs to be performed to expand the testing
to a variety of compounds including silicone-based compounds.

216
Acknowledgements
This study was sponsored by Phoenix Chemical (Somerville, NJ USA) and SurfaTech
Corporation (Dacula, GA USA). It was conducted by Thomas OLenick, a graduate student
pursuing a doctorate at The University of Tennessee (synthesis); and Tim Brockman, a
senior Chemistry major at Bloomsburg College (evaluation).
Anthony J. OLenick, Jr.

Siltech LLC, Dacula, GA USA
References
1. R.G. Pearson, J Am Chem Soc, 85 335 (1963)
2. A.J. OLenick, Surfactants: Strategic Personal Care Ingredients, Allured Publishing, 112-
129 (2005)

Chapter 25
Anionic Organosilicones:
Complexing Agents for
Quaternary Compounds
KEY WORDS: anionic, silicone, quat, complex, conditioners, deposition,
wet comb, carbomer
ABSTRACT: A new formulating technique allows for the preparation of
clear gels containing both anionic rheology control polymers
and cationic conditioning agents, ingredients which were
traditionally thought to be incompatible with one another.
It is well known that anionic thickeners such as carbomer and related

polymers are generally incompatible with cationic ingredients.1-3
Combining carbomers with quaternary compounds or other cationic
ingredients often leads to viscosity instability and high turbidity.
In addition, the carbomer and quat can strongly interact resulting
in the precipitation of a white, gummy mass. This has limited the
formulators options for novel rheological properties in rinse-out
conditioners. It has also restricted the choice of rheology modi-
fiers that can be used when creating gel-based styling products that
contain quaternary conditioning agents, resulting in products with
less than optimal aesthetic properties. However, when quats are first
complexed with anionic functional organosilicones, they can be suc-
cessfully combined with carbomers and related polymers.
Because complexation with an anionic silicone apparently shields
the cationic material from the anionic polymer, one might expect
interference with the ability of the cationic material to deposit on
anionic hair. Such interference would negatively affect conditioning
properties such as wet comb-through, which is generally improved
by the addition of low molecular weight (MW) quats.

218
Condition Anionic Organosilicones
Complexing low molecular weight quats with anionic silicone

does not, however, reduce the deposition of the quat onto hair. In
fact, it can actually serve to increase the deposition of silicone onto
hair, thereby improving conditioning properties.
Anionic Silicones
The anionic silicones used for complexation are based on the modi-
fication of dimethicone copolyol (PEG-7 dimethicone or PEG-8
dimethicone) with carboxylic,4 sulfamic5 or phosphoric acid.6
Variations in the product can be created by altering the nature of
the silicone backbone, the degree of alkoxy substitution and the
functional group. The anionic silicones used in this study resulted
from reacting dimethicone copolyol with phthalic anhydride, suc-
cinic anhydride, polyphosphoric acid and sulfamic acid to make,
respectively, dimethicone PEG-7 phthalatea, dimethicone PEG-7
succinateb, dimethicone PEG-8 phosphatec and ammonium dime-
thicone PEG-7 sulfated. Their molecular structures are shown in
Figure 1. All are supplied as 100% active products, except for the
ammonium dimethicone PEG-7 sulfate, which is supplied as 35 wt
% in water. All products are liquid at room temperature.
Figure 1. Molecular structures of the anionic silicones used in this study

a) Dimethicone PEG-7 phthalate b) Dimethicone PEG-7 succinate
c) Dimethicone PEG-8 phosphate d) Ammonium dimethicone PEG-7 sulfate
a
Ultrasil CA-1 Silicone. Ultrasil is a registered trade name of Noveon, Inc. Brecksville OH USA.
b
Ultrasil CA-2 Silicone, Noveon, Inc.
c
Ultrasil PE-100 Silicone, Noveon, Inc.
d
Ultrasil SA-1 Silicone, Noveon, Inc.

219
Vondruska et al. Chapter 25
Compatibility of Quats with Carbomer

Quaternary compounds are often used in hair conditioning applica-
tions where they provide excellent wet comb, shine and anti-static
properties.7 The drawback to these quats is their incompatibility
with carbomer and other synthetic anionic polymers, making it
difficult to formulate clear gels or gels with consumer-preferred
aesthetic properties.
Low molecular weight quaternary ammonium compounds
(cetrimonium chloride and stearalkonium chloride) were complexed
with dimethicone PEG-7 phthalate and separately added to acry-
lates/C10-30 alkyl acrylate crosspolymere mucilages. As the level
of dimethicone PEG-7 phthalate was increased, the viscosity of
the gel increased and turbidity trended toward that of a gel contain-
ing no quaternary material whatsoever. When a sufficient amount
of anionic silicone was used, precipitate was no longer generated.
These data are shown in Figure 2. Dashed lines in the graphs sig-
nify presence of precipitate. Conversely, a solid line signifies absence
of precipitate.
Figure 2. Compatibility of 0.4 wt % acrylates/C10-30 alkyl acrylate crosspolymer with 0.3

wt % of a low molecular weight quaternary ammonium compound at pH 7.0 with NaOH
as the level of dimethicone PEG-7 phthalate is increased. The quaternary ammonium
compound is cetrimonium chloride (left) and stearalkonium chloride (right).
e
Carbopol ETD 2020 polymer. Carbopol is a registered trade name of Noveon, Inc.

220
The dimethicone copolyol precursor (PEG-7 dimethicone) to

dimethicone PEG-7 phthalate has very limited capacity to compat-
ibilize such systems when compared to the functionalized, anionic
silicone. Complexing 0.3 wt % cetrimonium chloride with 0.5 wt
% dimethicone PEG-7 phthalate in a carbomer-based gel yielded
high viscosity (15,000 mPas) and low turbidity (13 NTU). Replac-
ing dimethicone PEG-7 phthalate with PEG-7 dimethicone in the
same system resulted in a viscosity of 2,650 mPas, a turbidity of
459 NTU and the presence of precipitate. This demonstrates that
the observed enhanced compatibility was due to complexation, and
not the steric effects of the silicone.
Although not detailed here, this concept is broad in scope and
applies to a wide range of anionic polymers, anionic silicones and
cationic materials (such as polyquaternium compounds and diva
lent cations).
Silicone-Quat Mole Ratios

When formulating with silicone-quat complexes, the existence of a
precipitate-free system is a mandatory success parameter. The level
of silicone needed to create such a system was explored and found to
be pH-dependent. This is due to the fact that the acid groups on the
anionic silicone are the active moieties, and their degree of ioniza-
tion is a function of pH. The pH-dependent mole-ratio of silicone
to quaternary active functional groups may be mathematically
expressed as Silicone-Quat Molar Ratio (SQMR). The minimum
silicone level required to produce precipitate-free systems has been
found to obey SQMRmin1.
Because the fraction of functional groups that are ionized
(and thus able to complex with cationic materials) is pH-depen-
dent, the pKas of the various silicones are required to perform
relevant calculations. Key quantities, including pKas, are shown in
Table 1.
In order to calculate the silicone-quat ratio, the quats must be
similarly examined. This is a much simpler task, because the cationic
character of quats is independent of pH. Table 2 shows pertinent
quat information8 for selected materials.

221
Table 1. Functionality of anionic silicones
Moles of functional
groups in 100 g
pKa(1) pKa(2) product (Csil)
Dimethicone PEG-7 phthalate 5.82 - 0.0872
Dimethicone PEG-7 succinate 6.47 - 0.1056
Ammonium dimethicone PEG-7 sulfate 3.75 - 0.01773
Dimethicone PEG-8 phosphate 3.79 8.10 0.03872 (1)
0.03872 (2)*
* 2 active hydrogens per phosphorous atom
Table 2. Molecular information on selected quaternary

ammonium compounds
Degree of
Molar mass functionality
Quat Chemical formula (g/mol) (DF)
Cetrimonium chloride C19H42NCl 319.5 1
Stearalkonium chloride C27H50NCl 423.5 1
Olealkonium chloride C27H48NCl 421.5 1
The number of ionized functional groups in a given sample at a

given pH can be determined using the information in Tables 1 and
2 and the Henderson-Hasselbach equation shown here:

pH = pKa + log([salt]/[acid]) Eq. 1
These can together be used to derive an expression for the

Silicone-Quat Molar Ratio (SQMR), shown in Equation 2. This
equation describes the molar ratio of active functional groups in
the silicone to quaternary nitrogen atoms in the cationic ingredi-

222
ent. Several systems were analyzed using this equation. At the point
where the level of silicone was just sufficient to create a precipitate-
free system, the SQMR was calculated. Data are shown in Table 3.
Table 3. SQMR values for known systems
System pH SQMR
0.4 wt % Carbomer
0.5 wt % Dimethicone PEG-7 phthalate 7.0 0.44
0.3 wt % Cetrimonium chloride
0.4 wt % Acrylates/C10-30 alkyl acrylate crosspolymer

0.5 wt % Dimethicone PEG-7 phthalate 7.0 0.58
0.3 wt % Stearalkonium chloride
0.4 wt % Carbomer
0.8 wt % Dimethicone PEG-7 succinate 7.0 0.92
0.3 wt % Stearalkonium chloride
0.4 wt % Acrylates/C10-30 alkyl acrylate crosspolymer

3.0 wt % Ammonium dimethicone PEG-7 sulfate 7.0 0.74
0.3 wt % Olealkonium chloride
The fact that the observed lower silicone limits of precipitate-

free systems are at SQMR<1 makes physical sense. The quat is fully
complexed at SQMR=1. There is no un-complexed quat remaining
when silicone levels are in excess of SQMR=1, so any such silicone
is essentially useless from a complexation standpoint. Stated simply,

223
SQMRmin 1. This, of course, presumes that the quat is the only

cationic material in the formulation. Instances where this is not the
case (e.g., formulations containing betaines, amphoterics, amines
and salts) may not adhere as stringently to SQMRmin1. It is simi-
larly theorized that any quat-carbomer precipitation in a system at
SQMR=1 can not be resolved by raising the level of silicone. In each
of the examples in Table 3 as well as in numerous other systems, the
minimum SQMR of a precipitate-free system is consistently less
than one.
Silicone levels above SQMR=1 are possible but the result is a
net anionic charge which may not be ideal for all systems. It is also
important to note that the SQMR at which point a precipitate-free
system is first formed may not correspond to the level of silicone
needed to achieve optimal viscosity or turbidity. Formulators should
refine the level of silicone in order to achieve the best combina-
tion of properties for their specific application needs. It is therefore
recommended that when formulating at a given pH and with a
given level of quat, a system should first be tested using the amount
of silicone that corresponds to SQMR=1. With precipitate-free
systems, the silicone content can be reduced to determine its lower
limit, or increased if necessary to gain potential clarity and/or vis-
cosity enhancements. If a system contains precipitate at SQMR=1,
it is unlikely that including more silicone will yield positive results.
System adjustments (pH, quat type, quat level, etc.) will be neces-
sary in such cases.
The SQMR concept is not only useful as a usage level indica-
tor; it is also a product selection tool. Consider an experimental
formulation containing 0.25 wt % cetrimonium chloride. The chem-
ist wishes to formulate at pH 5. A few quick calculations would
show that the dimethicone PEG-7 phthalate would need to be
used at 6.6% to reach SQMR=1 and the dimethicone PEG-7 suc-
cinate would need to be used at 24%. These carboxylates therefore
might not be the best choices for the cost-conscious formulator.
The ammonium dimethicone PEG-7 sulfate and the dimethicone
PEG-8 phosphate, on the other hand, would require only 4.7%
(equivalent to 1.6% actives) and 2.1%, respectively. The sulfate or
the phosphate would therefore be viable candidates for inclusion in

224
this example formulation. Even though they have fewer functional

groups (Csil) than the carboxylates, the phosphate and the sulfate
have a greater number of ionized functional groups at pH 5, due to
their low pKas.
If the same formulation were prepared at pH 6.5, calculations
would show that the dimethicone PEG-7 phthalate and dimethi-
cone PEG-7 succinate would require usage levels of 1.1% and 1.5%,
respectively, to reach SQMR=1. The sulfate and the phosphate
silicones would require 4.4% (equivalent to 1.5% actives) and 2.0%,
respectively. The higher formulation pH reduces the dependency on
pKa. Any of the silicones could reasonably be included in this for-
mula but the dimethicone PEG-7 phthalate, with a high Csil and a
moderate pKa, would be the most cost-effective choice.
When formulating with complexes, using the SQMR equation
can save the formulator time by reducing the number of experiments.
One can apply the equation to a particular formulation and nar-
row down the list of potential silicone complexing agents. Once the
proper silicones have been identified, the guidelines outlined above
can be used to quickly determine the correct silicone usage level.
Conditioning Efficacy
Conditioning efficacy of the silicone complexes was evaluated in
two ways; by deposition of the cationic conditioning ingredient onto
the hair (characterized by Rubine dye tests) and by wet combability.
Deposition on hair: The Rubine dye test9 is commonly used to
measure deposition of cationic ingredients on hair. The amount of
uptake of red dye by the hair is related to the amount of cationic
material deposited on the hair.
Results of Rubine testing are shown in Figure 3. Hair is treated
with a conditioning system consisting of cetrimonium chloride
complexed with dimethicone PEG-7 phthalate. A conditioning
system consisting of the same quaternary compound blended with
the dimethicone copolyol precursor to dimethicone PEG-7 phtha-
late was also tested (this is the same conditioning system, but the
silicone and quat are blended rather than complexed). No significant
deposition difference was observed (Figure 3a) between the two

225
Figure 3. Results of Rubine dye test showing deposition of selected cationic ingredients
on hair from a conditioning system consisting of
1) no conditioner
2) cationic conditioner at 1%,
3) cationic conditioner at 1% plus PEG-7 dimethicone at 1.67%,
4) cationic conditioner at 1% plus dimethicone PEG-7 phthalate at 1.67%.
The selected cationic ingredients are:
a) cetrimonium chloride
b) steralkonium chloride
c) olealkonium chloride

226
conditioning systems, which suggests that complexation does not

affect cationic deposition on hair. A conditioning system consist-
ing only of cetrimonium chloride deposited slightly better than the
other two, which can be attributed to the absence of steric effects
from other ingredients.
Figure 3b shows similar results with stearalkonium chloride.
Again, complexation is shown to not reduce deposition. In fact,
more deposition was measured with the silicone-complexed condi-
tioning system than with the silicone-blended conditioning system.
Figure 3c shows no significant differences between three
olealkonium chloride conditioning systems. Although differences
were measured, they were of roughly the same magnitude as
the differences between duplicate tresses for a given condition-
ing system.
Wet comb-through: Wet comb-through is defined as the total
work required to pull the wet hair completely through a comb five
times, as measured by a tensiometer. An untreated control tress is
tested, and the work needed to comb through this tress is normal-
ized to 100. Treated tresses are measured versus this control.
As previously shown in Figure 3a, a conditioning system con-
taining a cetrimonium chloride /PEG-7 dimethicone blend and
one containing a complex of cetrimonium chloride / dimethicone
PEG-7 phthalate deposited equally on hair (as evidenced by the
Rubine dye tests).
However, these systems were shown to perform differently in
wet comb-through tests (Figure 4). The results shown in Figure
4a indicate that the complex of cetrimonium chloride and dime-
thicone PEG-7 phthalate reduces wet combing forces significantly
more than the cetrimonium chloride alone or the blend of cetrimo-
nium chloride and PEG-7 dimethicone. The difference in efficacy
between the silicone-quat blend and the silicone-quat complex can
be attributed to differing levels of silicone on the hair. It can be con-
cluded that not only does cationic material that has been complexed
still deposit on the hair, but it brings the anionic silicone along with
it, in quantities greater than the anionic silicone would otherwise
deposit (assuming anionic silicone and dimethicone copolyol have
similar deposition on hair).

227
Figure 4. Reduction in work needed to comb through wet tresses treated with selected
cationic ingredients, compared to work needed to comb through untreated (control)
tresses (normalized to 100)
1) no conditioner
2) cationic conditioner at 1%,
3) cationic conditioner at 1% plus PEG-7 dimethicone at 1.67%,
4) cationic conditioner at 1% plus dimethicone PEG-7 phthalate at 1.67%.
The selected cationic ingredients are:
a) cetrimonium chloride
b) steralkonium chloride

228
Decreases in the work needed to comb through wet tresses were

also observed when the silicone was complexed with stearalkonium
chloride, as shown in Figure 4b.
Complexing low molecular weight quaternary ammonium com-
pounds with anionic silicone does not reduce the deposition of the
quat onto hair, but may serve to increase the deposition of silicone
onto hair which enhances overall conditioning properties.
Formulations
The combination of anionic silicones and quaternary condition-
ers is an exciting new development in hair conditioning and styling
products. Using anionic silicones and quats together, the formulator
can create products that have a novel and appealing appearance, the
performance benefits of excellent combing and styling properties,
lightweight and long-lasting body, and clean conditioning.
When creating products with silicone complexes, the ideal
system will feature enhanced compatibility with anionic rheology
control polymers (characterized by acceptable viscosity and clarity
for the application, and absence of precipitate). Systems will also
have improved conditioning properties (as noted by excellent wet
and dry comb properties) and display improved hair appearance.
To achieve these benefits, it is important to use a formulating
technique that maximizes the effects of the silicones and quats,
while enhancing the formulation appearance and aesthetics. The
following order of addition is recommended:
1. Prepare dispersion of the anionic rheology control polymer.
2. Adjust to desired pH.
3. Prepare aqueous silicone-quat complex, adjusting pH to
match that of polymer mucilage.
4. Slowly add complex to mucilage with vigorous agitation.
As previously discussed, the proper level of silicone for a given
amount of quat is pH-dependent. Higher silicone-quat ratios are
needed at low pH because the number of ionizable groups on the
silicone will decrease as pH decreases. The silicone-quat ratio for
each system is a function of system pH, the charge density of the
quat, and the pKa of the silicone.

229
Conclusions
Low molecular weight quaternary ammonium compounds, when
complexed with anionic silicones, can be made compatible with sys-
tems containing anionic rheology control agents, such as carbomer
and related polymers. Increased compatibility is defined as reduced
tendency to form precipitation, reduced turbidity, and/or improve-
ment in viscosity profile.
The use of silicone-quat complexes will allow the formulator
to achieve multiple new product benefits. This formulating system
serves to maximize quat performance as shown by the improved
compatibility of the ingredients and elimination of precipitation
from products.
Conditioning benefits are not hampered by using quats in com-
plex with siliconesin fact they are improved. This allows for the
creation of new and novel product forms with enhanced perfor-
mance and excellent consumer appeal. Products in clear gel forms
that contain both carbomer or other anionic polymers and quater-
nary compounds are now possible. Improved rheology and aesthetics
can be achieved in conditioning products and styling aids, and the
concept can be used to create such hair care products as lightweight
gels for detangling, leave-in conditioner gels, highlighting gels with
peroxide, conditioning sprays and detangling mousses.
Brian Vondruska, Laurie Marshall, Pamela McCalister and Kittie Ramey

Noveon, Inc., Brecksville, OH USA
Published April 2004 Cosmetics & Toiletries
References
1. K Klein, Formulating hair conditioners, hope and hype, Cosmet Toil 118(5) 28-31 (2003)
2. G Polotti and F Coda, Thickener for cationic surfactant solutions, Proceedings of the
28th CED Annual Meeting, Barcelona, Spain, 1998
3. J Knowlton and S Pearce, Handbook of Cosmetic Science and Technology, 1st ed,
Oxford: Elsevier Advanced Technology (1993) p 17
4. Noveon Technical Data Sheet, TDS 262, Brecksville, OH: Noveon Inc (2003)
7. J Pavlichko, Quaternary ammonium conditioners: Their utility and value in personal
care, in Cosmetics and Toiletries Manufacture Worldwide, Hemel Hempstead,
Hertfordshire, UK: Aston Publishing Group (2002) pp 1-9
8. International Cosmetic Ingredients Dictionary and Handbook, Ninth Ed, Washington,

230
DC: Cosmetic, Toiletry and Fragrance Association (2002) Vol 1 p 286, Vol 2 p 1061, Vol
2 p 1638
9. US Pat 3,769,398, G Hewitt, Polyethylenimine shampoo compositions, assigned to
Colgate-Palmolive Company (Oct 1973)

Chapter 26
Silicone Quaternary
Microemulsion: a
Multifunctional Product
for Hair Care
KEY WORDS: conditioner, multifunctional, silicone quaternary polymer,
microemulsion, heat protection, permanent color retention,
body, volume
ABSTRACT: A new multifunctional silicone quaternary polymer
microemulsion for hair offers conditioning, as well as
protection from heat, improved permanent color retention,
enhanced body and volume, and product clarity.
While silicones can impart specific feel characteristics to keratinous

fibers, formulators find that supplementary additives or combina-
tions of silicones are usually needed to create a hair care formulation
that can deliver multiple attributes beyond conditioning. This chap-
ter describes a new silicone quaternary polymer that conditions and
protects hair from heat. A microemulsion form of this polymer also
improves permanent color retention, enhances body and volume,
and can be used to create both opaque and clear formulations, as
demonstrated in tests described here.
A New Silicone Quaternary Polymer

Because of their positive charge, quaternary ammonium functional
silicones are useful in treating materials and surfaces that are primarily
negatively charged, such as in many textile and personal care applica-
tions. The quaternary ammonium functionality of the material makes
possible ionic interactions that are the basis of many useful properties.

232
Condition Silicone Quaternary Microemulsion
A proprietary stable microemulsiona containing silicone

quaternium-16 allows formulators to more easily incorporate the
quaternary polymer into formulations. The microemulsion contains
a silicone-based amino-polymer in which the amine-functional
groups have been cationized with quaternary groups (Figure 1). The
quaternary amine functional polymer exhibits a viscosity in excess
of 1 MM cP and thus would be difficult to incorporate into per-
sonal care formulations as a neat polymer. Due to its hydrophobic
nature, incorporation into water-based systems can be challenging.
To overcome this formulating obstacle, a cosmetically acceptable
solvent (2-butyl octanol) is combined with the polymer to reduce
the overall bulk viscosity. The polymer is then emulsified to further
aid the cosmetic formulator by enabling straightforward incorpora-
tion into water-based formulations. The nonionic, amine-functional
microemulsion is a mechanical microemulsion that contains 23%
quaternized siloxane polymer. Because the new material is a micro-
emulsion, it can be used to produce clear formulations.
Figure 1. Generic structure of silicone quaternium-16
Protecting from Heat

The moisture content of hair is crucial to maintaining its healthy
appearance and feel. Processes such as blow drying and curling with
a
Dow Corning 5-7113 Silicone Quat Microemulsion is a product of Dow Corning Corporation,
Midland, MI USA.

233
Ostergaard et al. Chapter 26
hot irons can rapidly reduce hair moisture content below its normal
level and can lead to damage. If the heated appliances are too hot,
they can actually cause the water in the hair to boil, forming minute
bubbles of steam inside the softened hair shaft, weakening the fiber
and potentially leading to total fracture.
Heat protection evaluations were completed by researchers at
the Istituto de Pesquisas Technolgicas, Sao Paulo, Brazil, using
dynamic thermogravametric analysis (TGA) techniques. The
analytical assessments were completed to establish the possible role
silicones could play in reducing the loss of water from hair fibers.
Hair tresses were treated with the neat silicone quaternium-16
applied at a level of 0.125 g silicone per gram of hair. Treated hair
was then subjected to various heating cycles in a nitrogen atmo-
sphere. Heating occurred at a rate of 10C per minute, ranging
from 25C to 300C. The results in Figure 2 show a positive trend
in reduction of weight loss for hair treated with the silicone quat
polymer, compared to an amine polymer or a control, at tempera-
tures typically experienced when consumers use a heated appliance
on their hair. The heat protection claim is based on the reduction
of water loss from the hair fiber upon heating. We understand this
effect to be caused by a film being formed on the hair fiber that
forms a barrier against water loss.
Figure 2. Results for TGA dynamic analysis indicate that hair treated with the silicone quat
polymer experiences less water loss.

234
Retaining Permanent Color

An increasing number of consumers are permanently coloring their
hair. Concurrently, there has been a proliferation of hair care products
that advertise claims regarding retention of permanent hair color.
Researchers at Dow Corning have investigated the role of sili-
cones in preventing loss of permanent color from dyed hair. Hair
tresses dyed with a leading commercial permanent hair dye were
subjected to a rigorous 4-step treatment cycle: 1) Washing with a
non-silicone commercial shampoo; 2) Conditioning with a rinse-off
conditioner (Formula 1); 3) Air drying; 4) Exposure to intense UV
radiation for an extended time (7 hr). The formulation of the rinse-
off conditioner was varied to show the effect of the tested silicones.
In Formula 1, the silicone content is based on silicone active level.
For the silicone quat microemulsion, the emulsion content would be
8% because it is 25% active. For the amino silicone and the elastomer
used in this comparison, the silicone content would be 2% because
they are 100% active. The control was Formula 1 with no silicone.
Formula 1. Color retention conditioner

% w/w
A. Hydroxyethyl cellulose 1.5
Water (aqua), deionized 50.0
Cetrimonium chloride 0.3
B. Cetyl alcohol 1.0
Benzophenone-3 1.0
C. Silicone actives 2.0
D. Water (aqua), deionized Up to 100.0
Phenoxyethanol (and) paraben 0.1
Tocopherol acetate 0.1
Glycerin 1.0
E. Citric acid qs to pH 3.5
Procedure: Combine A and heat to 75C. Add B to A, mixing until melted. Cool to approximately
40C with stirring. Add C with mixing. Add D and mix until uniform. Adjust pH with E.

235
Hair color was measured and recorded following each treatment

cycle. The hair color was assessed using a spectrophotometer-col-
orimeter. The value of D is a composite measure of the color depth
and similarity to the original hair color. A low value for D corre-
sponds to the measured hair color (following the treatment regimen
described above) that is most like the original dyed hair color.
Compared to hair treated with no silicone or with either of two
other tested silicone technologies, hair treated with the silicone quat
microemulsion retained significantly more hair color after seven
treatment cycles (Figure 3). These data are based on delivering the
active silicone from a rinse-off hair conditioner (Formula 1) contain-
ing 2% active silicone. Again, we think the effect might be explained
by the film-forming capability of the silicone polymer, which helps
to reduce the color loss over time.
Figure 3. The effect of selected silicones on color retention, delivered from a rinse-off
conditioner formulation
Body, Volume and Conditioning

Because consumers want to spend less time on personal care with-
out sacrificing results, there is a need for multifunctional cosmetic
products. In the hair care industry, a current major market need is
conditioning plus body for consumers with thin or fine hair, which

236
can appear limp, lifeless and unmanageable. In response, many com-

mercial hair care products specifically targeted at consumers with
fine hair are promoting claims of increased body or volume.
Conditioning may be defined as the action of a hair treatment
product to improve combability relative to a control, or for the
product to reduce the combing forces after application to the hair.
Hair body may be defined as thickness or apparent volume of a hair
assembly, involving sight and touch for assessment. Usually there is
a trade-off between the two benefits. This effect may be due to the
conditioner decreasing the inter-fiber friction of the hair fibers.
We tested the silicone quat microemulsion in a rinse-off con-
ditioner against other silicones for its ability to increase body or
improve conditioning.
Body: Evaluations were performed on a variety of hair tress sam-
plesb including European virgin brown, European slightly bleached
blonde and Oriental hair. Each hair tress used for evaluation was
assembled by attaching 2.5 g of hair to a plastic tab using an acry-
late-based glue and trimming hair fibers to a length of 15 cm.
The prepared tresses were shampooed with a 9% solution of
sodium lauryl sulfate, rinsed with water and allowed to air dry in
ambient conditions. After drying, some of the tresses were treated
with 0.8 g of a rinse-off conditioner (Formula 2) containing 2%
active silicone from amodimethicone emulsion, quaternium-80 or
the silicone quat microemulsion. The tresses were then left to air dry
overnight. Care was taken to ensure that all evaluations were con-
ducted on hair tresses produced from the same lot of hair.
For example, in Figure 4 (see Color Insert 8), all four samples
of European slightly bleached hair were washed, water-rinsed, and
allowed to dry. Then three of the tresses were treated with one of
the rinse-off conditioners and allowed to air dry over night. The
increase in body and volume is thought to be a charge repulsion
effect between fibers, although we have not been able to verify
this completely.
Conditioning: Silicones, particularly amine-functional, are known
to provide excellent conditioning for both wet and dry hair.1 A study
b
Hair samples obtained from DeMeo Brothers Inc., New York, NY USA

237
Formula 2. Clear rinse-off conditioner

% w/w
A. Water (aqua) 90.85
Tetrasodium EDTA (Versene 220, Dow Chemical) 0.20
Hydroxyethyl cellulose (Natrosol 250 HHR, Hercules) 0.90
B. Olealkonium chloride (Ammonyx KP, Stepan) 2.00
Cetrimonium chloride (Ammonyx CETAC, Stepan) 1.50
C. Propylene glycol (Propylene glycol USP/FCC, Fisher Chemical) 2.00
Polyquaternium-10 (Ritaquta 400, Rita) 0.15
D. Silicone quaternium-16 (and)
undeceth-11 and butyloctanol (and)
undeceth-5 (Silicone Quat Microemulsion 5-7113, Dow Corning) 2.0
DMDM hydantoin (Glydant, Lonza) 0.40
Fragrance (parfum) qs
E. Citric acid qs
100.00
Procedure: Combine A and heat to 80C while mixing. Add B to A with mixing. Combine C. Add
with mixing to AB. Begin cooling. When temperature is less than 40C, add D. Adjust pH to 5.5
with E.
Figure 4. Slightly bleached Caucasian hair tresses treated with rinse-off conditioner
containing specified silicones and left to air dry

238
done in our labs compared the silicone quat microemulsion with a

commonly used organic conditioning agent, cetrimonium chloride.
Each was delivered from a rinse-off conditioner (Formula 3 without
the fragrance). Compared to cetrimonium chloride, the microemul-
sion performed well (Figure 5) in reducing the combing forces in
both wet and dry stages, even at very low levels of actives (0.25%).
Formula 3. Volumizing conditioner

% w/w
Tetrasodium EDTA (Versene 220 Crystals, Dow Chemical) 0.20
Hydroxyethyl cellulose (Natrosol 250 HHR, Hercules) 1.50
Cetrimonium chloride (Arquad 16-29, Akzo Nobel) 0.30
B. Cetearyl alcohol (Lanette O, Cognis Care Chemicals) 1.00
Glyceryl stearate (and) PET-100 stearate (Arlacel 165, Uniqema) 1.00
C. Silicone quaternium-16 (and)
D. DMDM hydantoin (Glydant, Lonza) 0.40
100.00
Procedure: Combine A and heat to 75C. Add B to A, mixing until melted. Cool to approximately
40C with stirring. Add C with mixing. Add D and mix until uniform.
In the hair care industry, performance comparisons are routinely

made against a known industry benchmark. Researchers in our lab
performed a similar evaluation, comparing a commercial rinse-off
conditioner against a base conditioner formulation containing the
silicone quat microemulsion with silicone quaternium-16 active
at 1%. The results illustrate that the conditioning performance of
a commercial, fully-formulated conditioner can be matched by a
simple conditioner formulation (Formula 3) containing the silicone
quat microemulsion. We found that combing force reduction was

239
89.6% and 88.0% for the silicone quat microemulsion prototype for-
mulation and the commercial benchmark conditioner, respectively,
in wet hair. In dry hair those percentages were 75.6% and 86.8%.
Figure 5. Wet (black) and dry (light gray) conditioning performance of silicone quat
microemulsion vs. cetrimonium chloride, delivered from a rinse-off conditioner
Formulations
Cosmetic formulators continue to seek materials that allow them to
create novel formulations with distinctive performance or appear-
ance attributes to attract and retain consumer interest. Most hair
care brands have several variations in their shampoo, conditioner,
colorant and styling product lines to address diverse consumer
needs. For example, Formula 3 is a prototype conditioner that
enhances hair body, volume and waving, while improving wet and
dry combing.
Formulations with water-like clarity have become increasingly
important in the marketplace because consumers perceive them as
natural, pure, simple, elegant, light on the hair and invisible. The
market need for clear formulations is answered by solutions such
as those in prototype Formulas 2 and 4. Formula 2 demonstrates a

240
clear, rinse-off conditioner that improves wet combing. Formula 4

is a clear shampoo with conditioning effects that improve wet and
dry combing.
Formula 4. Clear conditioning shampoo

% w/w
A. Ammonium lauryl sulfate (Standapol A, Cognis Care Chemicals) 28.6
Decyl glucoside (Disodium EDTA, Universal Preserv-A-Chem) 0.2
PEG-120 methyl glucose dioleate (Glucamate DOE 120, Chemron Corp) 0.5
Water (aqua) 21.6
B. Ammonium laureth sulfate (Standapol EA-3, Cognis Care Chemicals) 25.0
Cocamidopropyl betaine (Lonzaine C, Lonza) 7.0
Cocamide DEA (Comperlan KD, Cognis) 3.0
C. Hydroxypropyl guar hydroxypropyltrimonium chloride
(Jaguar C-162, Rhodia) 0.3
D. Water (aqua) 11.2
E. PEG-15 Stearmonium chloride (Ethoquad 18/25, Akzo Nobel) 0.3
F. DMDM Hydantoin (Glydant, Lonza) 0.3
Silicone quaternium-16 (and)
G. Citric acid qs
H. Fragrance (parfum) qs
100.0
Procedure: Combine A and heat to 70-75C, mixing until uniform. Combine B and add B to A
with mixing. Disperse C into D; add E to this mixture. Add CDE to AB with additional mixing.
Cool to 40C and add F. Adjust pH to 6.5 with G. Add H.
Next-Generation Hair Care Products

Because todays hair care market is increasingly competitive, it can
be difficult to develop products that offer distinctive benefits while
not infringing on other patents. The new silicone quat microemul-
sion is covered by product and application patents for use in hair
care,2,3 so manufacturers have freedom to formulate highly differ-

241
entiated shampoos, conditioners, body washes, moisturizers, hair

styling aids, fixatives and shine products.
From clarity to color retention, heat protection to condition-
ing, the new silicone quat microemulsion provides formulators with
creative solutions for innovative hair care products.
Todd Ostergaard, Alvaro Gomes, Kim Quackenbush and Bethany Johnson

References
1. CA Hoag, Evaluating silicone emulsions for global hair care applications, GCI 44-55
(April 1999)
2. US Pat 6,482,969, Silicone based quaternary ammonium functional compositions and
methods for making them, LR Helmrick and JJ Kennan, assigned to Dow Corning (Nov
19, 2002)
3. US Pat 6,607,717, Silicon based quaternary ammonium functional compositions and
their applications, BK Johnson, JJ Kennan and F Lin, assigned to Dow Corning (Aug
19, 2003)

Chapter 27
Using Polyquaternium-64
to Condition Damaged
Hair
KEY WORDS: polyquaternium-64, MPC, cationic polymer, hair bleach,
hair condition, gel, ESCA, fluorescence-labeled polymer,
biocompatibility
ABSTRACT: Studies reported here show that by forming a gel layer that
coats the surfaces of damaged hair fibers, this new, cationic,
biomimetic copolymer helps to restore the appearance of
healthy hair.
Products developed to cleanse the skin and bleach the hair also
remove fatty acids, lipids, proteins, amino acids and other essential
components, leaving the skin and hair rough and dry. Bleaching,
for example, removes the fats and proteins that are important for
the binding of water to hair.1 A conditioner is needed to correct
these losses.
NOF Corporation has developed a synthetic water-soluble poly-
mer that mimics the structure of skin surface lipid, has the ability
to coat the skin and hair surface, and holds moisture.2 Now from
that polymer, NOF Corporation has developed a cationic varianta,
polyquaternium-64, that binds with skin and hair, forms a protec-
tive barrier, and helps to prevent the loss of moisture and other
components from skin and hair. Its structural similarity to naturally
occurring skin phospholipids enables this material to stabilize the
lamellar structure of skin and to coat the hair, offering protection
from surfactants and harsh chemical treatments.
a
Lipidure-C (INCI: polyquaternium-64) is a product of NOF Corporation, Tokyo, Japan.

244
Condition Using Polyquaternium-64 to Condition Damaged Hair
This chapter reports polyquaternium-64s effect on damaged

hair by evaluating moisture retention, combing friction, condition-
ing efficacy, and tensile strength of damaged hair treated with the
copolymer. Other studies report on its ability to form gels on the
hair surface and to adhere to that surface. Scanning electron micro-
graphs show its ability to restore moisture to the cuticle and prevent
the cuticle from lifting.
Materials
Polyquaternium-64: Polyquaternium-64 is based on the monomer
2-methacryloyl-oxyethyl phosphorylcholine (MPC). The structure
of MPC is similar to the polar head group of the phospholipids that
compose the extracellular leaflet of human plasma membranes. This
chemical moiety is biocompatible, binds copious water, and effec-
tively maintains a quiescent cellular state qualities that suggest its
use in personal care.3,4
MPC polymers have the ability to repair the epidermal bar-
rier. They bind water and normalize transepidermal water loss
(TEWL).5 As synthetic monomers, these prosthetic groups can
be synthesized into many copolymers, such as polyquaternium-51,
which protect human skin cells from detergents or other surfactants,
prolong the persistence of perfume, and reduce surface tension.6,7
In MPCs zwitterions, the phosphate moiety contributes the
anion, while the choline moiety contributes the cation. We have
rendered polyquaternium-64 as a cationic polymer by effectively
doubling the molar ratio of choline to phosphate.
Polyquaternium-64 (Figure 1) is a copolymer of MPC and
the cationic monomer, 2-hydroxy-3-methacryloyl-oxypropyltrim-
ethylammonium chloride. The average molecular weight of the
polyquaternium-64 was approximately 600,000.
A 5% polyquaternium-64 solution was used in these studies for
evaluating the effects on damaged hair.
Other materials: Samples of normal undamaged black hair that
has never been subjected to bleaching or dyeing were obtainedb from
b
From Beaulax Co., Ltd, Tokyo, Japan

245
Shimada et al. Chapter 27
Figure 1. Chemical structure of polyquaternium-64
a single donor. Damaged hair was obtained by repeated bleaching as

described in the methods section.
Lyophilized porcine skin was obtainedc and swelled in saline
before measurements of frictional coefficients were taken.
Instrumentation
Mean friction coefficient, measured as MIU (a popular term to cali-
brate friction coefficient in Japan), was measured using a feel testerd.
MIU is equivalent to the friction factor, , the quotient of frictional
force and normal force for a sliding body.
Tensile strength was measured using a rheometere. The adhesion
of polyquaternium-64 to hair fibers was determined by analysis of
phosphorous using ESCA X-ray photoelectron analysis equipmentf.
ESCA stands for Electron Spectroscopy for Chemical Analysis.
In Vitro Studies of Polyquaternium-64

Moisture retention by polyquaternium-64: The effect of polyquater-
nium-64 to retain moisture was compared with two common hair
c
Alloask S, from Taiho Pharmaceutical Co, Ltd, Tokyo, Japan
d
KSE-SE friction tester, Kato Tech Corporation, Tokyo, Japan
e
Reona RE3305 rheometer, Yamaden Corporation, Tokyo, Japan
f
ESCA-3300 X-ray photoelectron analysis equipment, Shimadzu Corporation, Kyoto, Japan

246
care agents: polyquaternium-7 and dimethicone. While the use

percentage for each product was different (polyquaternium-64: 5%
solution; polyquaternium-7: 9% solution; dimethicone: 50% emulsi-
fied solution), the weight of the polymers used in the studies was
kept equal at 0.02 grams each. This was confirmed by measuring
the dry weight of the polymer film used in the studies. An aque-
ous solution of each polymer was poured into a petri dish and dried
completely. 20 mg of each of the polymer films formed on the
dishes was incubated in 80% relative humidity (RH) for 72 hours
and then another 72 hours at 30% relative humidity. The amount
of water absorbed by the polymer was determined by weighing the
membrane several times during the incubation.
As seen in Figure 2 (and Color Insert 8), among those three
samples, polyquaternium-64 showed the highest degree of water
binding, retaining 15-10% water content, even at 30% RH. These
results suggest that polyquaternium-64 may have a better ability
to form a gel layer on the damaged hair surface when compared to
other hydrating agents.
Figure 2. Water holding capacity of polyquaternium-64 () in comparison with two other

commonly used hair conditioning ingredients, dimethicone () and polyquaternium-7 ()
Friction on combing: Generally, hair care products such as sham-

poos and conditioners are expected to smooth the hair for finger
combing. We measured the friction coefficient of polyquaterni-

247
um-64 on a porcine skin. This test was conducted by swelling a

lyophilized porcine skinc in saline, dropping 0.5 ml of 1% polymer
solution on the skin, and measuring the mean friction coefficient by
a friction testerd with a silicon adapter.
The observed skin friction coefficient values, measured as MIU
and averaged for each tested ingredient, were 1.55, 1.95, 2.85 and
3.60 for polyquaternium-64, dimethicone, polyquaternium-7 and
saline solution, respectively. Polyquaternium-64 reduced the skin
friction coefficient. The effect was significant compared to skin
treated with saline solution only. Polyquaternium-7 and dimethi-
cone were much less effective in reducing friction on skin. Although
dimethicone-treated skin also showed significant improvement,
the effects were less pronounced than that of polyquaternium-64.
Polyquaternium-7 did not demonstrate any significant improvement
over control in reducing the friction on porcine skin.
This data clearly suggests not only that polyquaternium-64 binds
more water, but also prevents build up of friction on skin surface.
The data also suggests that this material would be more effective
than polyquaternium-7 or dimethicone in reducing the friction of
combing on hair.
Methods for Analysis with Damaged Hair

Preparation of hair: In the washing and drying process, the hairb
was soaked in 1% aqueous solution of SLES for 1 min at 30-35C,
rinsed, squeezed by a towel, and blow-dried.
In the bleaching process, hair was soaked in 1:1 mixture of 4.5%
hydrogen peroxide and 2.5% ammonia solution for 20 min, rinsed,
squeezed by a towel, and blow-dried. Each bleaching process was
repeated 10 times.
The hair was treated with one of three polymers: polyquaterni-
um-64, dimethicone or polyquaternium-7. Hair was soaked in the
specified concentration of polymer for specified time, rinsed in stock
water, squeezed by a towel, and blow-dried.
Friction coefficient measurement: The damaged hair and the
polymer-treated hair were dried. The hair was kept at 20C and
40% relative humidity. The hair was fixed on a glass slide using a
transparent tape, and the measurement was taken using a silicone

248
attachment that has a friction close to that of human skin. The fric-
tion (MIU) was then measured instrumentallyd.
The value for MIU obtained from the instrument indicates the
friction of the hair. The lower the MIU, the lower the friction on the
hair, and the better the feel of hair and the combability of hair. This
reflects better conditioning of hair. A single strand of hair was used
to measure frictional coefficient. Measurements were performed at
least five times and the average values were obtained.
Tensile strength measurement: Hair tensile strength was mea-
sured using a rheometere. Hair was maintained at 20C and 40%
relative humidity during the measurement. Treated hair was com-
pared with untreated damaged hair for tensile strength. Ten strands
of hair were tested multiple times for tensile strength and average
values were obtained.
ESCA: Electron Spectroscopy to Chemical Analysis (ESCA)
involves irradiation of the hair surface with X-rays of known energy
that cause core electrons to be ejected from the hair surface. This
measuring provides semi-quantitative data for the polymer adhe-
sion volume.
Hair samples were placed on the measuring table of the ESCA
equipment and vacuum-dried at 60C for 12 hrs. The settings used
for the various elements were as follows: Carbon300-280 eV;
Nitrogen410-390 eV; Oxygen543-523 eV; Phosphorus142.9-
122.9 eV.
Measurements were taken at intervals of 0.1 eV. Each peak was
then quantitated for the respective element concentration (atomic
concentration as %). From the data, the ratio of phosphorus to
carbon concentration was calculated and expressed as a P/C value.
Statistics: Multiple measurements on single or multiple strands
of hair were taken and data was expressed as an average of multiple
measurements. Typically, standard deviation did not vary over 5% of
the mean values. Wherever the effects were statistically significant,
it was indicated in the Results section.
Results of Studies with Damaged Hair

In order to determine the effect of polyquaternium-64 on reducing
the level of friction in damaged hair compared to that of healthy

249
hair, damaged hair was prepared according to the procedures

described in the Methods section.8 Unbleached, washed and dried
black hair was used as the normal control (healthy hair). The dam-
aged hair was then treated with different polymers by soaking the
damaged hair (bleached) in each of the polymer solutions for 20
minutes. The friction coefficient and tensile strength of these poly-
mer-treated hair samples were then measured. In addition, scanning
electron micrographs were obtained and the gel-forming ability of
polyquaternium-64 was evaluated.
Conditioning efficacy of polyquaternium-64: The friction coef-
ficient of the specimens was measured according to the method
of Mastuzawa et al.9 using a friction testerd at 40% RH and 20C.
Resulting MIU values were 2.82, 2.90, 2.79, 2.92 and 2.91 for
healthy hair, damaged hair, polyquaternium-64-treated hair, dime-
thicone-treated hair and polyquaternium-7-treated hair, respectively.
Healthy hair shows low frictional coefficient (low MIU value), con-
sistent with no damage. Bleached, damaged hair shows higher MIU
values, consistent with increased damage to hair. Both dimethicone
and polyquaternium-7 failed to reduce the friction on damaged hair;
this indicates that these compounds neither coated the hair nor
moisturized it. On the other hand, hair treated with polyquaterni-
um-64 displayed a friction coefficient similar to that of healthy hair,
suggesting that polyquaternium-64 coats the hair and binds mois-
ture to make the hair soft and smooth to reduce friction.
From these results, it could be concluded that the hair treated
with polyquaternium-64 would be easy to finger comb.
Tensile strength of polymer-treated hair: A rheometere mea-
sured the tensile strength at 20C and 40% RH. Weight at breakage
averages (gf/hair) were 120, 87, 110, 110 and 108 for healthy hair,
damaged hair, polyquaternium-64-treated hair, dimethicone-treated
hair and polyquaternium-7-treated hair, respectively.
As expected, damaged hair showed low tensile strength
indicating that hair breakage occurs at low tension. All three hair-
conditioning agents increased the strength of hair significantly.
Treatment with conditioning agents including polyquaternium-64
restored the tensile strength of the damaged hair to levels closer to
that of healthy hair.

250
SEM comparison: Figure 3 presents the SEM pictures of the

healthy hair, damaged hair and hair treated with polyquaternium-64.
As shown in Figure 3b, the cuticle is lifted up on the surface of the
damaged hair by the repeated bleaching. Figure 3c shows that treat-
ment with polyquaternium-64 restored the damaged hair morphology
closer to normal hair. The cuticle in the treated hair resembled
normal unbleached hair more than it did the bleached hair. This
indicates the benefit of polyquaternium-64 in correcting hair cuticle
damage caused by hair bleaching. Polyquaternium-64 may bind to
the cuticles, restoring the moisture of the cuticle (that is lost dur-
ing bleaching) and preventing the cuticle from lifting. A lifted hair
cuticle is the main reason for damaged hair being sticky and brittle.
Figure 3. SEM images of hair fibers (X1000)

a = untreated normal hair
b = bleached damaged hair
c = bleached, damaged hair treated with polyquaternium-64
Gel-forming ability of polyquaternium-64 on hair surface: The

cationic polymer conditions the hair effectively by adhering to it.
There are detailed reports about the relationship between the adhe-
sion volumes of cationic cellulose and the duration of treatment.10,11
In view of this, the adhesion of polyquaternium-64 to hair fibers
was measured by analysis of phosphorous using ESCA, and based
on the fact that polyquaternium-64 contains phosphorous ions that
are normally not present in large quantities in normal hair. Any
detected presence of phosphorous atoms in treated hair was an indi-
cation of adhesion of polyquaternium-64 on hair fibers.

251
ESCA (XPS) (Electron Spectroscopy for Chemical Analysis by

X-ray Photoelectron Spectroscopy) involves irradiation of the hair
surface with X-rays of known energy that cause core electrons to be
ejected from the hair surface. This measurement provides quantita-
tive data for the polymer adhesion volume.
As seen from Figure 4 (and Color Insert 9), no peak for phos-
phorous atoms was observed for the healthy hair or the damaged
hair because the chemical structure of human hair consists of mostly
water and keratins. On the contrary, damaged hair treated with
polyquaternium-64 demonstrated a peak specific for phosphorous
(at 135 eV), indicating the presence of phosphorous atoms adhered
to the hair. Because the carbon atom is universal to all organic
matter, the ratio of P/C was used as a quantitative measure for the
adherence of polyquaternium-64 to hair surface.
Figure 4. ESCA measurement of phosphorous atoms on hair fiber, showing phosphorous

atoms at 135 eV for polyquaternium-64 coated hair
This novel method can be applied to determine the adhesion

volumes of polyquaternium-64 and other phosphorous-containing
ingredients on hair or skin surfaces by measuring the volumetric
ratio of phosphorous atoms to carbon atoms (P/C values).
Kinetics of adhesion of polyquaternium-64 to hair surface: Next,
we examined the concentration dependence for the adhesion volume

252
of polyquaternium-64 and hair, the time dependence for this adhe-

sion, and resistance to washing on removal of polyquaternium-64 by
using the ESCA method.
Concentrations as low as 0.01% of polyquaternium-64 indicated
phosphorous association with hair. Increasing the concentration of
the active up to 1.00% did not show any significant increase in the
association of phosphorous atoms on hair surface, suggesting that
even low concentrations of 0.01% of polyquaternium-64 saturate all
the binding sites in hair. This indicates that even a small quantity of
polyquaternium-64 is enough to form a gel layer on the hair surface.
In the time course study, phosphorous atoms originated by poly-
quaternium-64 gel are observed on the hair surface within only 30
seconds after the treatment. This indicates that polyquaternium-64
forms a gel layer almost immediately upon contact with hair. These
tests demonstrate the high affinity of polyquaternium-64 for dam-
aged hair (a short treatment with a very small quantity).
We evaluated the long-lasting efficacy of polyquaternium-64
after repeated shampooing. Damaged human hair treated with
polyquaternium-64 was washed repeatedly using sodium lauryl
sulfate solution as shampoo up to 10 times, and the amount of the
phosphorous bond to hair was measured. The levels of phosphorous
appeared to decrease with repeated washings, but after 10 washings
phosphorous could still be detected on the hair fibers.
This series of experiments demonstrates that polyquaternium-64
has high affinity for hair fibers, and that even small quantities
applied in short treatments are enough to coat the hair.
Visual images of polyquaternium-64 adhering to hair: In order to
confirm the results obtained by ESCA, we carried out a test using a
fluorescence indicator, polyquaternium-64-F. It was prepared by co-
polymerizing polyquaternium-64 with 5% aminoethylmethacrylate,
forming a precursor that was reacted with fluorescein isothiocyanate
(FITC) to form the FITC-conjugated polyquaternium-64, which
well call polyquaternium-64-F. The unreacted FITC was then
removed by dialysis.
The damaged hair was treated with 0.5% polyquaternium-64-F,
rinsed with water and then blown dry. The fluorescent bond to hair
was visualized in Figure 5 (see Color Insert 9) using a fluorescent

253
Figure 5. Fluorescence microscopic images of damaged hair fiber

a = non-treated (bright field)
b = non-treated (dark field)
c = FITC-bound polyquaternium-64 treated (bright field)
d = FITC-bound polyquaternium-64 treated (dark field)
Figure 6. Fluorescence microscopic images of damaged hair cross sections


254
microscope. Figure 6 (see Color Insert 10) shows the cross section
of the hair from the same experiment. Non-treated hair (Figures 6a
and 6b in a bright field and a dark field, respectively) showed
no fluorescence while the hair treated with polyquaternium-64-F
(Figure 6d) clearly showed fluorescence in a dark field.
Because only the periphery of the hair fluoresces, as shown in
Figure 6, we concluded that polyquaternium-64 adheres only to
the hair surface and produces the conditioning effect. From this
observation and the measurement by ESCA, we concluded that
polyquaternium-64 coated the surface of the damaged hair as a
gel layer.
Discussion and Conclusion

This chapter reports on a newly developed cationic variant of a
water-soluble, synthetic polymer that mimics the structure of skin
surface lipids, has the ability to coat the skin and hair surface, and
holds moisture. The variant, called polyquaternium-64, binds with
skin and hair, forms a protective barrier, and helps to prevent the loss
of moisture and other components from skin and hair. Its structural
similarity to naturally occurring skin phospholipids enables this
material to stabilize the lamellar structure of skin and coat the hair,
offering protection from surfactants and harsh chemical treatment.
Film formers, such as polyquaternium-64, help protect hair
by coating it with a moist gel. As demonstrated in this work,
polyquaternium-64 binds water, reduces the frictional coefficient,
improves softness, reduces the surface electrostatic potential, and
improves electrical conductivity of hair. ESCA measurements and
the fluorescent-labeling method showed that a water gel layer exists
on the surface of hair treated with polyquaternium-64. The result
is maintenance of moisture, improved smoothness and reduction of
damage to hair caused by bleaching and dyeing. (See Tips on For-
mulating with Polyquaternium-64.)
We conclude that polyquaternium-64 is a very effective hair-
conditioning ingredient because it combines cationic characteristics
with the various functionalities of biocompatible MPC polymer for
high affinity binding to hair fibers.

255
Tips on Formulating with Polyquaternium-64

In working with polyquaternium-64, it is wise to consider the following
points.
Because polyquaternium-64 is a polymer, in an alkaline system with
pH>10, its ester bonds will be broken. An amine odor can result.
Polyquaternium-64 is a cationic polymer. Interaction with an anionic
surfactant or polymer may cause precipitation or turbidity.
Kunio Shimada, PhD

NOF Corporation, Life Science Division, Tokyo, Japan
Kiyoshi Inomata
NOF Corporation, Tsukuba Research Laboratory, Ibaraki, Japan
Sreekumar Pillai, PhD, and James Hayward, PhD
Engelhard Corporation, Stony Brook, NY USA
References
1. CR Robbins, Chemical and Physical Behavior of Human Hair, 4th edn, New York, NY:
Springer-Verlag (2001) p 63
2. M Tschudia and K Shimada, An MPC phospholipid polymer with skin protection
benefits, Cosmet Toil 118(3) 63-68 (2003)
3. M Sakakida, K Nishida, M Shichiri, K Ishihara and N Nakabayashi, Ferrocene-mediated
needle-type glucose sensor covered with newly designed biocompatible membrane,
Sensor and Acturators B 13-14 319-322 (1993)
4. K Ishihara, K Fukumoto, J Aoki and N Nakabayashi, Improvement of blood compatibility
on cellulose dialysis membrane. 1. Grafting of 2-methacryloyloxyethyl phosphorylcholine
on to a cellulose membrane surface, Biomaterials 13(3) 145-149 (1992)
5. M Syaku, H Kuroda, A Ohba, S Ohkura, K Ishihara and N Nakabayashi, Enhancing
stratum corneum functions with a bi-functional phospholipid polymer, J Soc Cosmet
Chem Jpn 30(3) 273-285(1996)
6. K Shimada, H Irie, Y Murata, K Ishihara and N Nakabayashi, Synthesis and application
of 2-methacryloyloxyethyl phosphorylcholine copolymer, Fragrance J 26(7) 97-104
(1998)
7. M Tsuchida and K Shimada, Development and application of Lipidure-PMB, Fragrance
J 28(12) 118-121 (2000)
8. H Kouno, K Suganuma and T Hurukawa, Effect of thermal environmental changes on the
physical characteristics of human hair, J Soc Cosmet Chem Jpn 33(4) 377-385 (1999)
9. S Mastuzawa and N Mikami, PCA-Na smoothing effect on wet hair, J Soc Cosmet Chem
Jpn 29(3) 227-233 (1995)
10. JA Faucher and EJ Goddard, Sorption and desorption of a cationic polymer by human
hair: Effects of salts solution, Colloid Interface Sci 55 313 (1976)
11. JA Faucher et al, Influence of surfactants on the sorption of a cationic polymer by
keratinous substrates, Textile Res J 47 65 (1997)

Chapter 28
Quaternium-91: A New
Multifunctional Hair
Conditioning Ingredient
KEY WORDS: Quaternium-91, hair softening, hair conditioning, vitamin E
delivery, hair color protection
ABSTRACT: A new di-behenyl imidazolinium product, Quaternium-91,
provides hair conditioning, hair softening, vitamin E delivery
and hair color protection. This article compares Quaternium-
91 conditioners to corresponding behentrimonium chloride
conditioners, and correlates experimental results to salon
subjective evaluations.
Di-alkyl imidazoline quaternaries have been widely used as fabric

softeners industrially and for home use in the rinse cycle of wash-
ing machines.1 They impart a fluffy, soft feel to fabrics by adsorbing
onto them with hydrophobic groups oriented away from fiber.
The most widely used imidazolinium-type fabric softener has
been the tallow alkyl derivative. The hydrogenated tallow product
shows better softening performance than the nonhydrogenated
material because the former contains a higher portion of saturated
stearic chains. The distribution of hydrocarbon chains in nonhydro-
genated tallow product is 5% myristic, 30% palmitic, 20% stearic (C18
saturated) and 45% oleic (C18 unsaturated), while the hydrogenated
tallow product contains 65% saturated stearic chain. It is obvious that
the improved softening performance is due to the higher amount of
saturated stearic chain in the hydrogenated product.
Imidazoline quats also show the best performance in static
control compared to dialkyl dimethyl quats or diamido alkylated
quats having the same hydrocarbon chains.2 The physical form of

258
Condition Quaternium-91
imidazoline quats changes dramatically with an increase in the chain

length and saturation degree. At 75% solids of quat in isopropyl
alcohol, the oleyl product is a clear amber liquid; the tallow material
is an opaque liquid; the hydrogenated tallow product is a nonpour-
able opaque paste; and the di-behenyl imidazoline quat is a solid.
To date, no studies on the use of behenyl imidazoline quat in
personal care applications have been published. This is presumed to
be due to the materials solid form and the difficulty in its manufac-
turing process.
Recently, we have successfully developed and manufactured a
new producta whose INCI name is Quaternium-91 (and) cetrimo-
nium methosulfate (and) cetearyl alcohol. The main component
in this product is the Quaternium-91, which is di-behenyl imida-
zolinium methosulfate (Figure 1). Quaternium-91 is prepared by
reacting a behenyl moiety with diethylenetriamine and cyclizing
to produce the imidazoline. The imidazoline is then reacted with
dimethyl sulfate to produce imidazolinium.
Figure 1. Di-behenyl imadolinium methosulfate
Various cream hair conditioners containing Quaternium-91

(and) cetrimonium methosulfate (and) cetearyl alcohol were pre-
pared in our laboratory for study of hair care applications. The
following measurements were performed to determine the attributes
and efficacy:
Hair conditioning: dry and wet combing forces of treated
virgin and bleached hair tresses
a
Crodazosoft DBQ is a product of Croda Inc., Parsippany, New Jersey. Patents are pending
for Crodazosoft DBQ and Quaternium-91.

259
Gao et al. Chapter 28
Hair softening: bending storage modulus of treated virgin hair

bundles
Deposition of vitamin E on virgin and bleached hair
Hair color washfastness: color fading for dyed hair after
shampooing
Cuticle abrasion after repeated combing strokes
Half-head salon evaluations were also conduced in our applica-
tion laboratory to ascertain consumer perceptions and corroborate
our experimental results.
Experimental
Materials: Rinse-off cream conditioners containing either Quater-
nium-91 (and) cetrimonium methosulfate (and) cetearyl alcohol
or behentrimonium chloride (BTMC) were prepared in the Croda
application lab for performance measurements and salon evaluations.
Virgin brown hair samples were purchasedb. Bleached hair tresses
were prepared in our lab using a regular bleaching procedure.
Methods: We made the following instrumental measurements:

Wet combing force of hair tress was measured on a tensile
testerc.
Bending storage modulus of hair bundles was measured by a
dynamic mechanical analyzerd.
Cuticle appearance of hair fibers was inspected by a scanning
electron microscopee.
Hair color (CIE L*, a*, b* system) was measured by a spectro-
colorimeterf.
Substantivity of vitamin E on hair was determined by a sol-
vent extraction method using a spectrophotometerg.
b
International Hair Importers & Products Inc., Bellerose, New York USA
c
Miniature Tensile Tester (MTT-160), Dia-Stron Limited, Hampshire, UK
d
Dynamic Mechanical Analyzer (DMA) from TA Instruments, New Castle, Delaware, USA
e
Scanning Electronic Microscope (ISI SS-60) from International Instruments, Santa Clara,
California, USA
f
LabScan XE Spectrocolorimeter, Hunter Associates Lab, Reston, Virginia, USA
g
UV-VIS HP 8452 A Diode Array Spectrophotometer from Hewlett-Packard Co., San
Fernando, California USA

260
Results and Discussion

Reduction in wet combing force: Two rinse-off hair conditioners con-
taining either Quaternium-91 (Formula 1a) or BTMC (Formula 1b)
were used for measurements of wet combing forces of virgin brown
tresses and bleached hair tresses before and after the treatment.
Formula 1. Hair conditioners used in combing tests
a b
Quaternium-91 (and) cetrimonium methosulfate (and)
cetearyl alcohol (Crodazosoft DBQ, Croda) 2.14% wt -
Behentrimonium chloride (Incroquat BTMC-85, Croda) - 1.76% wt
Stearyl alcohol (Crodacol S-70, Croda) 3.00 3.00
Cetyl alcohol (Crodacol C-70, Croda) 1.00 1.00
Polysorbate 60 (Crillet, Croda) 1.00 1.00
Stearamidopropyl dimethylamine (Incromine SB, Croda) 0.50 0.50
Cyclopentasiloxane (and) dimethicone (SF1214, GE Silicones) 4.00 4.00
Dimethicone (HL-88, Barnet Products) 0.50 0.50
Propylene glycol (and) diazolidinyl urea (and)
methylparaben (and) propylparaben
(Germaben II, ISP Sutton Labs) 1.00 1.00
Citric acid 0.40 0.40
Disodium EDTA 0.20 0.20
Water (aqua), deionized 86.26 86.64
100.00 100.00
The data on percent reductions in both peak load and total work
of treated hair samples are presented in Figure 2. As a general
principle, the higher the reduction in combing force, the better the
conditioning performance.
After treatment with the Quaternium-91 conditioner, the average
peak load and total work were reduced for bleached hair (by 97.2%
and 96.3%, respectively) and for virgin hair (94.1% and 88.5%, respec-
tively). It is apparent that the Quaternium-91 conditioner provides
excellent conditioning performance on both virgin and bleached hair.

261
The average peak load and total work of BTMC-treated hair tresses
were also reduced for bleached hair (by 96.2% and 89.6%, respec-
tively) and for virgin hair (76.1% and 73.0%, respectively), but the
Quaternium-91 conditioner showed better conditioning performance
especially on the virgin hair compared to the corresponding BTMC
conditioner in our instrumental measurements.
Figure 2. Reduction in wet combing force by the Quaternium-91 and BTMC conditioners
applied to virgin (V) or bleached (B) hair
Salon evaluation: Salon studies with a panel of 20 female par-

ticipants were conducted to assess consumer perceptions. The
evaluation results were correlated to the previous instrumental
measurements. The same two Formula 1 rinse-off conditioners were
used for half-head salon studies.
The average scores obtained from salon evaluations are summa-
rized in Figures 3 and 4, respectively, for wet and dry conditioning
performances.
It can be seen that the Quaternium-91 conditioner received
significantly better average scores in wet detangling, wet combing,
dry combing and hair bounce/body compared to those obtained

262
from the corresponding BTMC conditioner. These data agreed with

the results of instrumental measurements and indicate that there
are good correlations between the instrumental measurements (wet
combing force) and the subjective evaluations (wet detangling, wet
feel and wet conditioning).
Figure 3. Salon evaluation of wet conditioning performance
Changes in bending storage modulus: Dynamic mechanical testing

of the force or modulus to bend a bundle of hair fibers characterizes
the stiffness or softness of the hair bundle, which is its resistance
to a controlled normal force imposed on the bundle in the verti-
cal direction. If the bending modulus increases after treatment,
the bundle becomes stiffer. If the bending modulus decreases after
treatment, the hair bundle is less stiff or softer; fibers have reduced
interfiber friction.3
The hair bundle sample was composed of 250 virgin brown hair
fibers with a length of 3.5 cm. Two simple conditioner formulations
containing either Quaternium-91 (Formula 2a) or equivalent level
of BTMC (Formula 2b) were used for the hair bundle treatment.

263
Figure 4. Salon evaluation of dry conditioning performance
Formula 2. Hair conditioners used in hair softness tests
a b
100.00 100.00
The average bending storage modulus of hair bundles before and

after treatments was measured. It was determined that the average
bending storage modulus of hair bundles treated with the Quater-
nium-91 conditioner was decreased by 15.6%, while the average
bending storage modulus of hair bundles treated with the BTMC
conditioner was only reduced by 5.4%. It is evident that hair bundle

264
treated with the Quaternium-91 conditioner became softer com-

pared to hair bundles treated with the BTMC conditioner.
Substantivity of vitamin E on hair: A solvent (methanol) extrac-
tion method was developed and used to determine the amount of
vitamin E deposited on the treated hair. The hair samples were
treated with either a Quaternium-91 conditioner (Formula 3a) or a
BTMC conditioner (Formula 3b) containing 0.5% vitamin E and
then rinsed off under tap water. Hair samples were air-dried and
then immersed in methanol to extract the vitamin E.
Formula 3. Hair conditioners used in tests of vitamin E

deposition
a b
dl-Alpha tocopherol acetate (Vitamin E Acetate, Cognis) 0.50 0.50
100.00 100.00
At 180 versus 86.3 mg vitamin E deposited per 100 g of hair,

the amount of vitamin E deposited on virgin hair delivered from
the Quaternium-91 conditioner was more than twice as much as
that deposited from the BTMC conditioner. The corresponding
findings for bleached hair were 80.9 and 57.6 mg, indicating that
the Quaternium-91 conditioner delivered approximately 40% more
vitamin E than the BTMC conditioner.
It is interesting to note that the amount of deposited vitamin E
on virgin hair is much higher than that on bleached hair. This may
be attributed to the lipophilic characteristics of vitamin E, which
shows stronger affinity to the hydrophobic surface of virgin hair.

265
The experimental results indicate that the Quaternium-91

conditioner is a very good delivery system for oil-soluble actives.
Berthiaume4 pointed out that imidazoline quat showed better depo-
sition of dimethicones on hair surface from conditioning shampoos
than other quats such as mono-alkyl, di-alkyl and tri-alkyl quats.
Our experimental results are consistent with her observations.
Protection from cuticle abrasion: As indicated in the combing
studies already described, Quaternium-91 dramatically reduces
the friction force between hair fibers and the comb. According to
our bending modulus measurements, the interfiber friction was
decreased after the Quaternium-91 conditioner treatment. There-
fore, it was expected that the hair cuticle would undergo much less
abrasion even after many repeated combing strokes.
SEM photos of hair fibers before and after 1,500 consecutive
combing strokes with and without treatment with the Quaterni-
um-91 conditioner (Formula 1a) are presented in Figure 5. It is
apparent that the hair treated with Quaternium-91 conditioner
showed no cuticle abrasion, while the hair fiber without treatment
showed severe cuticle damage after combing.
Hair color washfastness: A hair color washfastness test method
was developed and performed to determine the changes in color
indexes of dyed hair samples after multiple shampoo washings.
Bleached hair tresses were treated with a dyeh according to the
manufacturers instructions. A specially designed after-dye condi-
tioner (Formula 4) containing Quaternium-91 (and) cetrimonium
methosulfate (and) cetearyl alcohol was used to treat the dyed hair
and prevent the hair color loss from multiple shampoo washings.
The dyed hair tresses were washed with a regular shampoo for 15
cycles with or without treatment with the after-dye conditioner. The
hair color was measured and recorded using an L*(lightness index),
a* (red index), b* (yellow index) system. The changes in theses color
indexes indicate the directions of color shifts: if Delta L* is posi-
tive, hair turns lighter; if Delta a* is positive, hair becomes redder; if
Delta b* is positive, hair is yellower. Delta E reflects the total color
h
Herbal Essences #44 Radiant Ruby Deep Red, from Clairol, a part of Procter & Gamble,
Cincinnati, Ohio USA

266
changes; an increase in Delta E means more change in total color.

The determined changes in color indexes of hair samples before and
after 15 shampoo washes are plotted in Figure 6.
Figure 5. SEM images of effect of Quaternium-91 treatment on combed hair fibers. Images
on the left are cuticles of untreated hair fibers before (above) and after (below) 1500
combing strokes. Images on the right are cuticles of treated hair fibers before (above) and
after (below) 1500 combing strokes.
Formula 4. After-dye hair conditioner
Quaternium-91 (and) cetrimonium methosulfate (and) cetearyl

alcohol (Crodazosoft DBQ, Croda) 2.14% wt
Stearyl alcohol (Crodacol S-70, Croda) 3.86
Amodimethicone (and) trideceth-12 (and) cetrimonium
chloride (DC 939 Silicone Emulsion, Dow Corning) 3.00
Phenoxyethanol (and) propylparaben (and) butylparaben (and)
methylparaben (and) ethylparaben (Phenonip, Nipa Labs) 1.00
Water (aqua), deionized 90.00
100.00

267
Figure 6. Color Index changes of dyed hair after 15 shampoo washes
It can be seen that the untreated hair showed significant color

changes: hair became lighter (Delta L* is positive 10.67) and the
hair color shifted in an orange direction because both Delta a* and
Delta b* are large positive values. In comparison, the hair treated
with the Quaturnium-91 conditioner showed only relatively small
changes in all color indexes. The total changes in hair chromaticity
(Delta C) and hair color (Delta E) of conditioner-treated hair were
about 70% less than those for the untreated hair.
These experimental results clearly demonstrated that the
Quaternium-91 after-dye conditioner provided good protection for
hair color. One explanation may be that when the Quaternium-91 is
deposited on the hair surface, the ingredients hydrophobic charac-
teristics prevent the hair dye from washing out.
Figure 7 (see Color Insert 10) shows the three dyed hair tresses.
This photo clearly illustrates the visual differences in hair color
of hair tresses with and without treatment. The middle hair tress
treated with the Quaternium-91 conditioner remained almost the
same color as the original (left) after 15 shampoo washes. In con-
trast, the hair tress (right) without any treatment turned lighter and

268
more orange after washes. These visual observations are consistent

with our instrumental measurements on changes in color indexes.
Figure 7. Color changes of dyed hair tresses pre-treated once with Quaternium-91 (center)
or untreated (right) and then shampoo washed 15 times, compared to original tress (left)
without treatment or washing
Conclusion
Quaternium-91 conditioners provide outstanding softening and wet
conditioning performance. They impart hydrophobicity to hair for
better slip and lubricity during the combing process. They deliver a
high amount of vitamin E to virgin and bleached hair. They prevent
cuticle abrasion and protect dyed hair from color change.
Timothy Gao, Ph.D., Ann Bedell, Jung-Mei Tien, Abel Pereira,

Patrick Obukowho and Rob Comber, Ph.D.
Croda Inc., North American Technical Center, Edison, NJ USA
Published May 2003 Cosmetics and Toiletries
References
1. R Laughlin, Fabric softening, in Cationic Surfactants: Physical Chemistry, D Rubingh
and P Holland, eds, New York: Marcel Dekker (1991)

269
2. C Earl, Imidazoline surfactants, in Cationic Surfactants: Organic Chemistry, J

Richmond, ed, New York: Marcel Dekker (1990)
3. US Pat 5,968,286, Heat-medicated conditioning from shampoo and conditioner hair
care compositions containing silicone, J Crudele, W Bergmann, K Kamis, P Milezarek
and V Shan, assigned to Helene Curtis (Oct 3, 1999)
4. MD Berthiaume, Silicone chemistry and personal care application, an SCC education
course (Mar 1997)

Chapter 29
Innovations in Hair
Styling Technology
KEY WORDS: VOCs, aerosol hair spray, pomades, hair dressing, packaging,
solvents, polymers
ABSTRACT: The regulatory climate for cosmetic products is becoming
more difficult for formulators. Here, the authors describe how
new rules have inspired cosmetic chemists to use a variety
of strategies and partner with raw material suppliers and
packaging houses in order to provide consumers with what
they want.
In previous publications we reviewed the basic technologies behind

the primary styling product forms including aerosols, pumps and
gels.1 This chapter reviews how changes in technology and regula-
tory pressures have inspired innovation. In order to understand
how and why chemists are innovating to accommodate regulations
presently, we need to start by looking at where it all began.
A History of Styling Technology

For almost as long as there have been cosmetic chemists, there have
existed regulatory agencies to control their work. The incursion of
regulatory requirements has forced changes in hair styling products
more than in any other type of hair product.
Since their introduction in the 1940s, hair sprays led the popu-
larization of modern styling products. The first sprays were pump
type systems, but public demand for a better product prompted the
development of the aerosol hair spray. The aerosol spray was based
on Goodhue and Sullivans patent of low-pressure propellants (fluo-
rocarbon 12) and Abplanalps patented valve design.

272
Styling Innovations in Hair Styling Technology
The first aerosol hair spray was introduced to the public in

1949 in Chicago by the Global Liqinet Corporation, and created
a multi-million dollar business. These early formulas used shellac
as the fixative polymer but shellac exhibited several major draw-
backssuch as being difficult to wash out of hairthat led to the
development of synthetic polymers with properties that could be
better controlled.
For the next 20 years business boomed but by the late 1960s
environmental and safety concerns began to threaten the industry.
While styling formulations gave good fixative properties, many
contained environmentally sensitive solvents and propellants. Chlo-
rofluorocarbons (CFCs) were the first to gain notoriety because
they depleted the ozone layer, prompting fears that an unhealthy
amount of UV radiation could reach the Earths surface.
In 1979, regulatory agencies banned CFC propellants from aerosol
formulations in most industrialized nations. (Despite what anyone
may tell you, CFCs are no longer used in hair care aerosols today.)
Shortly thereafter, the popular co-solvent methylene chloride came
under scrutiny after it was discovered to be a potential carcinogen.
Fortunately, the cosmetic chemists of the day found innovative
solutions to these regulatory realities. Ethyl alcohol and alcohol/
water systems became increasingly popular substitutes as solvents
and dimethyl ether/hydrocarbon mixtures replaced CFCs as the
primary propellant system. All was right in the world of cosmetic
science at least for a short while.
By the early 1980s this new breed of eco-friendlier formu-
lations was coming under scrutiny because of concern for air
pollution. These formulations relied heavily on ethanol and other
hydrocarbons which belong to a class of chemicals known as volatile
organic compounds (VOCs). Researchers found that when exposed
to sunlight, VOCs were capable of combining with nitrogen oxides
(NOx) to form ground level ozone, or smog. Ironically, the industry
had swapped one material that destroyed ozone for another that
created it. But this ozone stays near the Earths surface and has
negative health effects.
Concerns about smog led to VOC reductions in 1983, just after
CFCs were banned. Originally, the South Coast Air District in

273
California wanted to ban aerosols but industry activists succeeded

in obtaining amendments to the law to preempt California Districts
from doing just that. The result was the establishment of legal
safeguards for development of regulations by the California Air
Resources Board (CARB). These rules were developed through
intense negotiations that occurred in the early 1990s. They ulti-
mately limited the amount of VOCs that could be used in any
cosmetic aerosol product.
Federal laws soon followed that supplemented an ever-growing
number of state rules, but California remained the most stringent.
California proposed still more rules during the late 1990s and the
trend continued through the new millennium.
History of Consumer Product VOC Regulations in

the USA
1978: CFC Ban
1983: South Coast AQMD (Los Angeles)
1988: California Clean Air Act
1989-1992: California Rules
1990: Federal Clean Air Act Revisions
1990-1995: Other State Rules
1996: EPA National Rule
1997-1999: More California Rules
2000: Reactivity-Based Aerosol Paint Rule in California Rule
in California
2000-2004: Northeastern State Rules 2004
2003: New California Rule
2005 -2010: More California Rules
In 2000-2004 the Northeastern State Rules were first proposed

and they were followed by still more California rules in 2003. As of
2005, California remains the state with the most stringent require-
ments. Texas, New York, Massachusetts, New Jersey, Delaware,
Pennsylvania, Maryland and Virginia are somewhat less stringent
than California, but more stringent than the National Rule. Arizona

274
and Georgia have local rules that affect products other than aerosols.
All states are subject to the EPA National Rule.
As of 2005 the rules state that hair mousse may contain no more
than 6% VOCs, hair shine and hair holding sprays no more than
55%, and gels no more than 6%. And according to industry experts,
we can expect to see even more rulings in California through 2010.
Strategies to Create Low VOC Formulas

What do all these rules mean to the formulator? Well, to begin
with, we can no longer use ethyl alcohol as the major solvent in
styling products. This limitation is a huge impediment because
ethanol is really an ideal ingredient. It solubilizes holding polymers,
has excellent spray properties, is easy to use, dries quickly, smells
nice, and has no serious toxicological issues. Instead of ethanol,
many manufacturers have resorted to adding water to their products.
However, an increase in the water concentration can adversely affect
the performance of a hair spray by accelerating the initial curl droop
and/or increasing the dry time on the hair. Other styling products
have similar issues related to drying time and application properties.
Cosmetic formulators must rise to the challenge to do more with
less, to create formulations that satisfy consumers despite rigorous
regulatory constraints.
To achieve these goals, various strategic approaches have been
suggested. Douglas Fratz, of the Consumer Specialty Products
Association, listed several approaches for creating VOC-compliant
products by using the following: exempt compounds, low vapor
pressure compounds, water-based formulations, increased amounts
of inorganic compounds and solids, innovative product exemptions,
alternative compliance plans and product use instruction labeling.2
To achieve these goals, various strategic approaches have been
suggested. At the 24th International Aerosol Congress in Septem-
ber, 2003, the Consumer Specialty Products Associations Douglas
Fratz discussed creating VOC-compliant products and suggested
the seven approaches described next.2
Use exempt compounds: This strategy involves formulating with
compounds that the authorities consider exempt from VOC con-
sideration. For example, hydroflourocarbons (HFCs) are exempt

275
propellants and acetone is an exempt solvent. Certain types of

silicones can be used in some products but they are very expensive.
Chemicals with negligible photochemical reactivity (e.g., com-
pounds that have less ozone formation potential than ethane) are
also exempt. There is also an exemption for materials with vapor
pressures less than 0.1 mm Hg at 20C. Similarly, fragrances are
exempt. It is best to check with the Cosmetic, Toiletry and Fra-
grance Association (CTFA) or the Consumer Specialty Products
Association (CSPA) to find a list of exempt compounds.
Use low vapor pressure compounds: Materials with low vapor
pressure such as glycol ethers and propylene glycol can be used
without affecting VOC content. This strategy is useful for products
such as gels but less useful for hair sprays.
Use water-based formulations: By using water-based formulas
the amount of VOCs is easily reduced. Unfortunately, adding water
usually requires surfactants or emulsifiers to be added to the for-
mula. These compounds will have various effects on the product
performance, many of which are not desirable. Water itself also has
negative impacts on the finished products such as increasing drying
time and decreasing hold. To date, most hair spray manufactur-
ers have used this formulation strategy even though it results in an
arguably inferior product.
Use increased amounts of inorganic compounds and solids: Com-
pressed gas propellants like carbon dioxide and nitrogen are not
considered VOCs so they could be used as substitutes. However,
their use is limited due to technological challenges. The major
hurdle yet to be solved is the loss of pressure that products using
compressed gas experience. A consumer using such a product
will notice a weaker spray over time until eventually nothing gets
dispensed. If product remains in the container but can not be
removed, the consumer will be turned off and likely never purchase
the product again.
This strategy is more effective for products like antiperspirants,
where VOC levels can be decreased by adding non-volatile organic
solids, such as surfactants and polymers.
Use innovative product exemptions: CARB allows an exemption
for certain innovative formulations. To use this strategy, the chemist

276
has to be able to provide clear and convincing evidence that, due

to some characteristic of the product formulation, design, delivery
systems or other factors, the use of the product will result in less
VOC emissions3 than a product with a comparable amount of
VOCs. For example, a concentrated hair spray can be produced to
have more active ingredients but be dispensed with less solvent.
Use alternative compliance plans: California allows the VOC
emissions of some products to be averaged, or grouped together.
This allows mixing products that can be over-reduced with others
than cannot be reduced much at all. To use this strategy, cosmetic
manufacturers have to submit an application to show the VOC
content of the products in the plan, a sales verification method, and
other emission tracking information.
Use product use instruction labeling: Another way to reduce VOC
emissions is to educate consumers on an alternative method for
using a product. This approach attempts to change consumer behav-
ior to increase use efficiency and deter excessive VOC emissions. For
example, instructing consumers to use less hair spray at a given time
will make the product last longer and reduce emissions over a given
time. While this method is not currently applied to hair care prod-
ucts, it could be in the future.
Styling Technology Today

All of the strategies have been attempted (with various degrees
of success) to face the challenges of ever-increasing regulations of
hair care products and more specifically, styling products. Lets take
a closer look at some of the specific innovations that have been
employed by formulators in todays styling products.
A quick review of some recent patents shows how formulators
have compensated for VOC regulations in all types of styling cat-
egories including hair sprays, gels, and mousses. Well begin with
aerosol hair sprays because they are arguably the most complex,
dynamic systems of all personal care products, and have also been
subject to the most difficult regulations.
Aerosol hair spray: Aerosols face all the standard formulation
problems imaginable such as phase separation, sedimentation, mal-
odor generation, discoloration, pH drift, and so on. But additionally,

277
they have a set of potential problems unique to their delivery system,

including can corrosion, poor spray-ability, dry time, film formation,
Department of Transportation pressure issues, can evacuation, dip-
tube elongation, and so forth.
The two most successful methods for creating new VOC-com-
pliant aerosol products are as follows.
First, the formulator can try to modify the solvent/propel-
lant mix to optimize its properties. This approach typically
involves finding substitutes for ethanol as a solvent or replac-
ing hydrocarbon propellants. In the latter case, a choice
between using either HFC-152a propellant (a non-VOC
classified material which allows for anhydrous systems) or
dimethyl ether (DME) with hydrocarbon combinations
(which allow water-compatible systems) is the norm.
Second, the formulator may choose to alter the holding resins
in the formula to improve the way the product functions.
The technical literature indicates formulators have had some
degree of success with both approaches.
Optimizing the solvent/propellant mix is the most common
solution to the VOC issue. While using HFC-152a propellant in an
aerosol formulation is a straightforward replacement, it usually results
in a product that is of significantly higher cost. DME formulations
can be made less costly but have required innovative solutions to deal
with the presence of water. Ethanol replacements have been harder
to develop, but progress has been made. Consider the following three
patents which deal with optimized solvent systems.
US Patent No. 6,752,983 discloses the replacement of etha-
nol and isopropanol by alkyl acetates, particularly methyl
acetate and t-butyl acetate.4 These solvents can be problem-
atic because they hydrolyze in the presence of water to form
harmful acids. They may also have pungent chemical odors
and may stain clothing. This patent discloses a way to mix
alkyl acetates with lower levels of alcohols to over come these
difficulties while lowering VOC content.
US Patent No. 6,464,960 involves the use of acetone as a sol-
vent.5 Acetone is not widely used in hair sprays because it has
an unacceptable odor, it evaporates too quickly, and it is a poor

278
solvent for some polymers. This patent discloses the use of a

hair-setting polymer in a solvent/propellant system containing
a 1- to 4-carbon alcohol, water, a cosolvent such as acetone,
and a propellant mixture consisting of dimethyl ether and a
fluorocarbon. According to the patent, this invention allows
for water containing, reduced VOC hair spray that approxi-
mates the performance properties of conventional water-free
hair sprays.
In a similar vein, US Patent No. 6,432,390 uses a concentrate
blend of alcohol and methyl acetate along with dimethyl ether
propellant.6 The composition consists of 50 to 90 weight per-
cent concentrate and 10 to 50 weight percent propellant and
it provides competitive styling properties with minimal VOC
emissions.
Recent examples of formulators changing styling polymer prop-
erties can also be found.
US Patent No. 6,638,992 discloses a styling product that
involves the incorporation of latex chemistry in the formula.7
It uses a spray-dried hybrid-graft copolymer of a sulfopoly-
ester and an acid-functional polymer segment. Purportedly,
such compositions exhibit superior curl retention even at high
humidity and they may be prepared over a wide range of VOC
concentrations.
US Patent No. 6,562,325 relates to a non-aerosol hair spray
based on polyacrylic acid and nonionically derivatized starch-
es.8 The starches are hydrolyzed and modified by cationic
substitution to give a clear solution with a stable viscosity.
Furthermore, this formula provides a clear film which is not
tacky, that has good stiffness and improved humidity resis-
tance and is substantive to hair.
Gels and mousses: Hair sprays are not the only product category of
interest. Other styling product categories such as gels and mousses
have their own unique formulation challenges as well.
While not necessarily focused on low VOC content, US Pat-
ent No. 6,663,855 does reveal a clever approach to formulating a
mousse.9 It uses graft copolymers which allow physical and chemical
attributes like glass transition temperature and solubility to be varied

279
independently. The result is a novel class of polymers that can be

tailored to the particular application, particularly related to provid-
ing longer-lasting hold and/or improved feel.
Hairdressings and pomades: Finally, no discussion of styling
products would be complete without a reference to hairdressings
and pomades. US Patent 6,649,154 discloses a method to make
conventional hairdressings less sticky and oily-feeling.10 This is
accomplished by incorporating a polysaccharide such as beta-1,3-
glucan. Formulas based on this type of polymer provide an excellent
hairdressing effect and hair-setting power when applied with heat at
reduced VOC levels.
US Patent No. 6,579,517 reveals a way to make a dual com-
ponent system using at least one cross-linked, water-soluble or
water-dispersible polyurethane combined with at least one polymer
having isocyanate-reactive groups.11 This is a new way to achieve
benefits of these polymers from a low VOC system.
The Role of Packaging

As you can see from even this brief review, VOC regulations have
prompted a tremendous innovation effort for new hair styling for-
mulations but the story does not end there. Packaging companies
have been busily innovating to help aid formulators in the develop-
ment of lower VOC products.
Typically, changes in formulation technology help drive pack-
aging development and the recent low VOC formulas are no
different. Consider these recent attempts by packaging suppliers
to develop new, more functional packaging and dispensers. For
example, TricorBraun has a new line of special fine mist spray-
ers designed for lower VOC hair sprays and spray gels. Similarly,
SeaquistPerfect Dispensing now offers actuators for new high
viscosity styling products.
Companies have developed new anti-clog pumps that do not
clog even with high resin content products. Some of these dispens-
ers are also available in a 360 spray version that can be used upside
down. Emsar offers a directional spray pump that provides precise
application that is ideal for concentrated products such as root

280
volumizers. Similarly, Saint-Gobain Calmar markets the Mark VI

fine mist sprayer with a spray extender. It is a pressure build-up type
of sprayer that delivers performance for 55% VOC formulations.
Finally, there is Airspray International, who has introduced the
first foam pump on the market, the Finger Pump Foamer. It is a
mechanical foamer and therefore does not require gas propellant to
create thick foam. The dispenser is suitable for simple water-based
(non-VOC) formulations such as mousses.
Packaging companies have also aided formulators in dealing with
low VOC issues by creating options for different kinds of styling
products. While hair spray is still the biggest part of the styling cat-
egory sub-segment, waxes and gels are rapidly growing in popularity.
A recent trend in styling products is the use of putties and pastes
which tend to have fewer VOC issues. This shift in product choice
is attributed to the consumers desire for a messy, matte look, but
could also be a reaction to the lower performing, VOC-compliant
products now being produced.
Pastes and putties are typically sold in tubes and jars and these
containers dictate a certain formula texture and viscosity which
chemists must take into consideration when formulating. The
trend toward hair that is grungy, unkempt and wild has led to
products which support that look. These include products that can
create a tousled or stringy look like D:fi Beach Bum, Este Laud-
ers Bumble and Bumble Surf Spray, Redkens In the Loop, and
Sebastians Bondage.
Packaging technology allows these products to match the look
that the consumers want. For example, they give the packaging a
matte look with special resins such as Velva-soft. Or they can use
bi-injection molding to give the package a different, softer feel. In
addition to making them VOC-compliant, formulators are also
using newer types of styling polymers to help meet consumer expec-
tations for these products.
Conclusion
The regulatory climate for cosmetic products is arguably becoming
more and more difficult for formulators. Different states have dif-
ferent regulations that are constantly changing. This does not even

281
take into consideration regulations proposed around the world. And

these new rules have been particularly hard on cosmetic chemists
who are responsible for developing styling products.
Fortunately, innovation is alive and well in the styling field of
cosmetic chemistry. By using a variety of strategies and partnering
with raw material suppliers and packaging houses, formulators have
found ways to reduce VOCs released and still provide the consum-
ers with what they want. Future regulations will likely make the
formulating job even more difficult, but they will also spark true
innovation and that cant be all bad, right?
Randy Schueller and Perry Romanowski

Alberto-Culver, Melrose Park , IL USA
References
1. P Romanowski and R Schueller, Aerosols for apprentices, Cosm Toil 111(5) 35-40
(1996)
2. D Fratz, USA VOC Regulations and Compliance Alternatives for Aerosol Products,
presented at the 24th International Aerosol Congress, Consumer Specialty Products
Association (September 2003) Available at: http://www.aerosols-info.org/nic02/t_cspa.
pdf
3. California Air Resources Board (CARB) regulations 94511, Innovative Products, Div. 3,
Ch. 1, Sub 8.5, Consumer Prod. Art. 2 (2004)
4. US Pat 6,752,983, Hair spray and consumer sprays with reduced volatile organic
compounds (2004)
5. US Pat 6,464,960, Water containing aerosol hair spray with a reduced content of volatile
organic compounds (2002)
6. US Pat 6,432,390, Low VOC methyl acetate hair sprays (2002)
7. US Pat 6,638,992, Hair care compositions (2003)
8. US Pat 6,562,325, Use of stabilized starches in low VOC, polyacrylic acid-containing
hair cosmetic compositions (2003)
9. US Pat 6,663,855, Cosmetic and personal care compositions (2003)
10. US Pat 6,649,154, Hairdressing cosmetic preparation and hairdressing method using
the same (2003)
11. US Pat 6,579,517, Cosmetic product (2003)

Chapter 30
Advances in Polymers for

Hair Styling
KEY WORDS: polymers, fixative, hair spray, styling, straightening,
conditioning
ABSTRACT: Block and graft copolymers, including some produced by
living free-radical polymerization, are among the new
hair fixative polymers surveyed in this chapter. Other
new polymers offer advantages in hair styling gels, hair
straightening and hair conditioning.
Hair spray consists of more than polymer. All components must be

considered and these comprise fixative polymer, solvent, propellant,
adjuvant and the valve system of the aerosol. Hair styling also has
numerous components. In this article well discuss the hair styling
components that depend on polymers. They include hair fixatives,
styling gels, straighteners and conditioners. (For a brush-up on the
classes of polymer architecture discussed in this chapter, see Figure 1.)
Hair Fixatives
The desired attributes of hair fixatives include: hair style hold
improvement, ease of application on wet hair, ease of combing, no
sticky feel, quick drying, not powdery or flaky during grooming,
assurance of hair body and bounce, increased hair volume, no clump-
ing of the hair, formation of a non-hygroscopic binding film that is
removable by shampoo, good hair gloss, and no excessive stiffness.
Hair style hold improvement must be achieved with a minimal
amount of fixative polymer applied easily from an aerosol spray, a
pump spray, a gel or a mousse. For ease of application on wet hair,
the solvent must be compatible with water and the polymer must
not phase-separate as water permeates the system. The fixative

284
Styling Advances in Polymers for Hair Styling
Classes of Polymer Architecture
a b c d
Figure 1.
a.) Homopolymers consist of long molecular chains in which each link is an identical
monomer.
b.) Random copolymers consist of long molecular chains in which there are two
different monomers and these are arranged randomly along the chain.
c.) In Block copolymers: the monomers are homopolymer blocks joined together. The
figure depicts an ABA block copolymer.
d.) In Graft or comb copolymers: branches consisting of one type of monomer are
hung from a main chain consisting of another type of monomer.
system must also be safe; especially upon ocular exposure or inhala-

tion.1 For ease of combing, the cohesive strength of the polymer film
must be less than the tensile strength and shear strength of the hair;
and the adhesive bond of the film to the hair must be weaker than
the shear strength of the hair. For conventional systems, sticky feel
is avoided if the polymer in the dried film is immobile during the
time of touch and has insufficient time to interact with the stratum
corneum of the fingertips. Quick drying can be achieved either by
judicious choice of solvent and propellant or by causing the system
to gel. The mechanical property aesthetics of hair body and bounce,
increased hair volume non-clumping and lack of extreme stiffness
depend upon the hair matrix being lightly crosslinked rather than
being coated by the applied polymer film. The film must be non-
hygroscopic; otherwise it will be plasticized by absorbed water vapor
under humid conditions. Such uncontrolled plasticization leads to
loss of hold.
Random copolymers: During the last two decades the US
aerosol hair spray industry has been driven to develop low volatile
organic compound (VOC) systems to comply with the Clean Air
Act. In most cases this has meant the development of aqueous

285
Lochhead and Huisinga Chapter 30
systems in which a significant portion of the solvent is replaced by

water. This has posed two main challenges. First, the kinetics and
thermodynamics of fiber wetting is less favorable for aqueous sys-
tems than the original solvent-based systems (see Wetting of the
Hair). This results in a reduction of capillarity and a concomitant
loss of holding power due to the inter-fiber effects discussed above.
The second challenge arises form the fact that the water rapidly
penetrates into the hair cortex, plasticizing the hair and causing
droop of the style.
Wetting of the Hair

Wetting of the hair by an applied polymer solution is extremely
important because capillary forces are necessary to pull adjacent fibers
together in order to form inter-fiber seam-welds and to cause migration
of the solution to inter-fiber cross-points where it will be captured due
to a balance of Laplace pressure between the curvature at the hair-
liquid interface and opposite curvature at the air-liquid interface. This
phenomenon is commonly observed as the adhesion between the bristles
when a paint-brush is loaded with paint. Dewetting of the hair can cause
the fibers to be driven apart (Figure 2) and this would inhibit migration
of the fixative solution to crosspoints of the hair matrix and prevent the
formation of seam welds between fibers.
Figure 2. Contact angle greater than 90 causes the fibers to be pushed apart

286
Random copolymers have a solubility parameter that is inter-

mediate between homopolymers made from the same monomers.
Twenty years ago, conventional hair spray resins were designed to
be soluble in a propellant mixture of ethanol solvent and propane/
isobutane. As water was added to the polymer solution, the solvent
mixtures solubility parameter could move out of range of that of the
polymer and if this happened the polymer would phase separate.
The configurational entropy of mixing increases as the polymer
molecular weight decreases and this is manifested by solubility of
the lower molecular-weight polymer in a wider range of solvents
than a higher molecular-weight polymer. Therefore the polymer
suppliers initially responded to the need for aqueous-compatible
polymer by merely lowering the molecular weights of their polymer
products. However, the lowering of molecular weight also resulted
in poorer film properties and the consequent loss of holding proper-
ties imposed limitations on the extent to which this approach could
be adopted.
Block and graft copolymers: Compared to random copolymers,
block and graft copolymers can show dual solubility zones, with
each zone corresponding to the solubility parameter of the respec-
tive homopolymers. Homopolymer mixtures do not, in general,
form compatible blends because the large molecules have low entro-
pies of mixing, and in the absence of large enthalpies of mixing, the
free energies of mixing favor segregation of the polymer mixture
into two phases one rich in one of the homopolymers and the
other phase that is rich in the other homopolymer.
Each of the component molecular blocks of block and graft
copolymers also display such segregative phase separation. How-
ever, in this case because the molecular blocks are constituent parts
of the same molecule, the segregation is limited to microdomain or
nanodomain dimensions. This limited segregation leads to polymer
alloys in which glassy microdomains confer mechanical rigidity and
rubbery microdomains confer rubbery and shock-absorbing proper-
ties. These materials are thermoplastic elastomers and they often
display enhanced mechanical properties. Thermoplastic elastomers
comprise block copolymers containing rigid glassy blocks and soft
rubbery blocks incorporated within each molecule and precise

287
control of molecular weight of the blocks produces separation into

exact micro- and nano-structures that can be tuned to display
exact mechanical properties. Moreover, if the block copolymer is
amphipathic (that is it comprises at least one hydrophilic polymeric
segment and at least one hydrophobic polymer segment) it may
form films that exhibit the desired resistance to humidity but sus-
ceptibility to shampoo.
In this context, it is interesting that Dubief et al2 have reported
that the inclusion of a non-thickening amphiphilic block copolymer
in a fixative formulation with a conventional hair fixative polymer
enhances the cosmetic and styling properties of the conventional
polymer fixatives. The improvements are manifested by an increase
in conditioning or styling power without increasing the total poly-
mer concentration in the formula, or the same conditioning and
styling benefits at reduced polymer concentration. The non-thick-
ening polymer in this case is defined as a copolymer which when
dispersed or dissolved in water leads to dynamic viscosities that are
less than 0.1 Pa.s measured at a shear rate of 200 sec-1. Examples
of such amphiphilic block copolymer/ fixative polymer blends are
demonstrated in Table 1.
The influence of the block copolymer on the morphology of the
bulk material and/or on the adhesion of the fixatives to the hair
surface could be speculated to follow the following scheme:
Block copolymers tend to exhibit morphology of separated micro-
domains, each of which is rich in one of the blocks.
Separation of discontinuous glassy domains in rubbery matrix
would confer the properties of an elastomer
Separation of rubbery domains in a glassy matrix would confer
impact resistance.
Separation of ionic microdomains within a nonpolar matrix
would confer increases in toughness and tensile modulus.
Ionic microdomains might be expected to confer susceptibility
to shampoo that would lead to ease of removability from the hair
after use.
Alternatively, preferred adsorption of the block copolymer at the
hair/fixative interface could lead to improved adhesion and conse-
quently higher fixing of the hair.

288
Table 1. Examples of amphiphilic block copolymer/fixative

polymer blends from Dubief2
Fixative Polymer Amphiphilic Block Copolymer

Vinylpyrrolidone/vinylcaprolactam copolymer Poly(styrene-b-2-hydroxyethyl meth-
(Luvitec VPC 55K65W, BASF) acrylate) having block molecular
weights: PS = 1500; PHEMA = 44,000
Vinylpyrrolidone / dimethylaminoethylmeth- Poly(styrene-b-acrylic acid) having

acrylate copolymer (Copolymer 845, ISP) block molecular weights: PS = 1500;
PAA = 44,000
Polyurethane (Luviset PUR, BASF) Poly(methylmethacrylate-b-acrylic acid)

having block molecular weights:
PMMA = 1200; PAA = 38,000
PPG-1/IPDI/DMPA copolymer
(Avalure UR 450, Noveon)
Acrylic copolymer (Avalure AC115, Noveon)
The polydimethylsiloxone (dimethicone) chain is extremely

flexible and hydrophobic and, as a consequence, this material is
an excellent lubricant that confers conditioning benefits such as
softness, disentangling and feel to hair. Thus, Dupuis3 has claimed
a terpolymer consisting of t-buty1 acrylate, acrylic acid and a
silicone macromer that is taught to provide softness, disentangling
and feel benefits with simultaneous excellent styling and fixing
properties.
Hair fixatives with improved flexibility are needed in Asia and
in the United States. They should have good hold, natural feel,
good combability, and they should be tack-free. BASF has sought
to address this need by synthesizing a polyurethane/silicone poly-
mer that provides smoothness and sleekness to the hair while being
easy to wash out.4 It is interesting that independent claim 1 of this
patent lists polysiloxane as optional.

289
A polymer of t-butyl acrylate/methacrylic acid/N-butylacrylam-

ide is taught to give easily washed-off hair hold with soft touch.5
The attributes in this case were tested by a curl-retention test and a
panel-test for wash-off, hair feel and setting effect.
Improved shine, reduced flaking and better compatibility with
modern solvent/propellant blends are taught for a product prepared
from the polymerization of the following:6
A C2-C22alkyl (e.g. t-butyl) (meth)acrylate
A vinyllactam such as N-vinylpyrollidone
A cationic acrylate or acrylamide monomer
A silicone copolyol.
In another approach directed towards these combined attributes,
BASF has introduced polyureas7 prepared from a polyethoxylated
diamine (e.g., Poly ESP 520 from Rachig), an amine-containing
or hydroxyl-containing polysiloxane (e.g., MAN and MAR brands
from Degussa-Huls or the FINISH brands from Wacker) and a
di-isocyanate.
Block copolymers from free radical polymerization: Block
copolymers are well known. For example, styrene-butadiene,
styrene-isoprene, styrene-ethylene, and styrene-propylene block
copolymers have been available under the trademark Kraton for
more than a quarter of a century. However, these are made by
anionic living polymerization. This technique requires the absence
of protons or abstractable hydrogen atoms and these constraints
severely limit the choice of monomers and reaction media. More-
over, the costs of manufacture are relatively high due to the high
reactant purity required for anionic polymerization.
These limitations are being overcome by the advent of living
free-radical polymerization which offers the prospect of economi-
cally producing a wide range of block copolymer compositions in
a broad array of reactant media. There are two main techniques for
the polymerization of block copolymer elastomers by free radical
living polymerization:
The technique of free-radical polymerization by reaction with a
nitroxide consists in blocking the growing free-radical species in
the form of a bond of C-ONR1R2 type.8-12
The RAFT (reversible addition-fragmentation chain transfer)

290
polymerization technique consists in blocking the growing free-

radical species in the form of a bond of C--S type.13-14 Dithio
compounds such as thiobenzoates, dithiocarbamates or xanthan
disulfides are used to do this.
Mougin15 has used free-radical living polymerization to prepare
hair fixative polymers comprising (a) at least one rigid block having
a glass transition temperature (Tg) of greater than or equal to 20C,
consisting of units derived from one or more ethylenic monomers,
and (b) at least one flexible block having a glass transition tempera-
ture (Tg) of less than 20C, consisting of units derived from one
or more ethylenic monomers. These block copolymers produce a
film having an instantaneous recovery of between 5% and 100%.
Such mechanical properties are characteristic of elastomers and the
physical properties of these block copolymers should be distinctly
different from the hard, glassy, brittle properties of conventional
hair spray resins. Block copolymers having flexible blocks consist-
ing exclusively of ethylene, propylene, butylene, butadiene and/or
isoprene units are excluded in the patent claim.
Restylable fixatives: In a drive to satisfy a market that is
moving towards water-soluble, low-VOC fixatives, National
Starch has introduced nonionic derivatized starches,16 poly-N-
vinylacetamide,17 amphoteric urethanes,18 and dehydroxanthan
gum.19 Dehydroxanthan gum provides both thickening and hair
fixative properties with high holding even in humid conditions. An
added advantage is that it can be restyled by merely spritzing with
water and combing or brushing.
Restyling has become an important attribute and several
approaches have been adopted to bring restylable fixatives to market.
These approaches include:
Products similar to hot melt adhesives that allow remodeling of
the hairstyle under the influence of a hair dryer.20-22 These are
based upon Structure O from National Starch that is reported to
consist of 10 weight percent acrylic acid and 90 weight percent
n-octadecyl methacrylate, and to have a crystalline melting point
of 46C.
Semi-solids products that are prepared by including a polyal-
kylene glycol in which the hair-fixative resins is soluble.23 This

291
provides reformable welds that are liquid or semisolid at ambient

temperature.
Hair Styling Gels

Hair styling gels are largely aqueous compositions and they are eas-
ily formulated to comply with the VOC requirements of the Clean
Air Act but most preferred hair fixative polymers are incompatible
with carbomer gels and this has restricted the formulations in this
category to the early workhorse fixative polymers PVP and PVP/
VA. These fixatives are marginally effective in hair styling, especially
in conditions of high humidity. Moreover, PVP and PVP/VA copo-
lymers impart an undesirable tacky or sticky feel to the hair. It has
been reported that the tack can be reduced by the use of a reactive
non-silicone polymer that produces tack on the hair that does not
transfer to the hands.24
Some new polymers have been developed to be compatible with
the traditional carbomer thickeners of this category. For example,
National Starch introduced poly-N-vinylacetamide25 to this market
segment and researchers at Nalco have prepared fixative polymers
that contain up to 10 weight percent of 2-acrylamido-2-methyl-
1-propane sulfonic acid or its salts in combination with anionic or
nonionic monomers.26 These polymer fixatives provide a better bal-
ance between conflicting requirements of good curl retention at high
humidity augmented by rapid and complete removal from the hair
when rinsed with water. The additional polymers of this invention
are also compatible with anionic thickening systems.
A possible extension of this class of polymers has been intro-
duced by Clariant in the form of fluorine-modified comb polymers
based on acryloydimethyltaurine acid.27 There polymers can be
optimally crosslinked to improved their efficiency as associative
thickeners. Perfluorocarbon chains do not easily associate or mix
with hydrocarbon chains and the use of these thickeners could offer
more formulation versatility.
Ease of dispersibility is water is an important criterion that is
desired by gel manufacturers who wish fast process times or who
are sensitive to the capital cost of mixing equipment. To meet this
need, some polymer manufacturers have supplied inverse emulsion

292
polymers or dispersions of thickening polymers in oil. However, the

hydrocarbon oil vehicles have not always been desirable in personal
care products. In this context, it is interesting that Ciba researchers
have addressed the challenge by developing inverse emulsion poly-
meric thickeners as dispersions in silicone fluids.28 As with other
inverse emulsion polymers these are supplied with high HLB
activating surfactant to enable the polymer to be dispersed and to
thicken quickly when the phase is inverted when flooding with large
amounts of water.
A new family of polymers has been introduced to simultaneously
deliver thickening and film-forming capabilities. These Fixate Plus
polymers from Noveon are reported to provide thickening and hair
fixing from aqueous and/or hydro-alcoholic systems.29 The polymers,
called rheology modifying hair setting (RMHS) polymers, contain:
An acidic vinyl monomer (for example methacrylic acid)
A nonionic monomer (for example ethyl acrylate)
An associative monomer (for example a long chain alkyl ethoxy-
lated methacrylate)
Optionally a semi-hydrophobic monomer (for example an alkyl
polyethoxylated methacrylate) and a cross linker (for example
trimethylolpropanetriacrylate).
Hair Straightening
There are two main processes for relaxing or straightening hair:
Hair treatment with a reducing agent to cleave of the disulphide
cystine bridges (S--S) within the hair structure, mechanical
stretching followed by an oxidizing treatment to reset the
disulphide cystine bridges in a new, desired straightened hair
conformation.
Treatment of stretched hair with a strong alkaline agent.
Repeated relaxation treatments can result in rough hair that
tends to become tangled.
The fundamental hair structure is damaged by the process
of alkaline relaxing. Cationic and amphoteric polymers such as
Polyquaternium-6, Polyquaternium-7 and Polyquaternium-39 are
added to hair relaxer formulations to mitigate degradation of the
hair structure.

293
The extent of damage can be assessed by measuring the porosity

of the hair and the porosity of the keratin fibers can be measured by
fixing 2-nitro-para-phenylenediamine at 0.25% in an ethanol/buf-
fer mixture (10/90 volume ratio) at pH 10 at 37C for 2 minutes.30
Samain et al30 reveal that the inclusion of high molecular-weight
(>106 g/mole) polymers in the relaxing formula results in significant
reduction in the hair structural damage caused by alkaline relaxation.
The polymers are synthesized by precipitation polymerization in salt
solution. The salt solution is of sufficient in strength to cause the
growing polymer to precipitate upon reaching a critical molecular
weight. The polymers are delivered to the substrate as a particulate
dispersion in a concentrated salt solution. The claimed polyelectro-
lytes can be anionic, nonionic or cationic. The anionic polymers can
be made from acrylic acid, methacrylic acid, acrylamido-2-methyl-
propanesulphonic acid, and itaconic acid. The nonionic monomers
can be polymerized from the monomers acrylamide, methacryl-
amide, N-vinylformamide, N-vinylacetonamide, hydroxypropyl
acrylate, and hydroxypropyl methacrylate. The cationic polymer
can be, for example, copolymers of acrylamide and diallyldimethyl
ammonium chloride, acryloyloxytrimethylammonium chloride, or
acryloyloxyethyldimethylbenzylammonium chloride. Interestingly,
these polymers are not effective for oxidation-reduction restyling.
Hair Conditioning
Conventional conditioner formulations are based upon either
ceto-stearyl trimethylammonium chloride plus ceto-stearyl alco-
hol or distearyldimethylammonium chloride. These have been
the workhorses of conditioners for decades and they do provide
excellent detangling, wet- and dry-combing, and good anti-static
properties, but they can leave the hair feeing lank and greasy. Poly-
meric conditioners can improve wet combability and ameliorate
electrostatic charging of the hair (manifested by flyaway). For
example, Polyquaternium-10 can be applied as a conditioner to
confer such benefits. Polyquaternium-7, a copolymer of acrylamide
and diallyldimethylammonium chloride, and the homopolymer of
polydiallyldimethylammonium chloride (Polyquaternium-6) are
found in conditioner formulations.

294
Recently, a patent was granted to Alzo International for polyure-

thane conditioners with enhanced conditioning properties.31 These
are made by reacting trialkanolamine (preferably triethanolamine)
with a hydroxy fatty acid (ricinoleic acid, lactic acid or salicylic acid)
to make a mono-, di- or triester, then reacting with a di-isocyanate
to produce a polyurethane with tertiary amine functionality, then
quaternizing the tertiary amines. The benefits claimed are better
adhesion to hair and skin than conventional cationic conditioners.
This leads to lower usage levels that in turn result in cost savings.
The polyurethane conditioners confer excellent surfactancy, sheen,
wet combing, dry combing, antistatic and conditioning properties.
Leave-on silicone conditioners specifically targeted to non-
shampoo appflficatfions have been reveafled by . 32
These
contain emulsified vinyl-terminated silicones applied in combina-
tion with a conventional cationic conditioner. A preferred product
type is a mousse. The significance of this claimed invention rests on
the basis that these silicone block copolymers can achieve excellent
conditioning at relatively high viscosities (100 KPa.s-1). Aqueous
foaming shampoo compositions containing emulsified vinyl silicone
polymers are described in a copending application.33
Effective clear conditioners have been one of the long-standing
challenges of cosmetic formulators. Conventional conditioners,
comprising cationic surfactant and long chain alkanols form a gel
matrix that confers conditioning benefits from rinse-off products
but they give a long-lasting slippery feel during rinsing and this
is perceived by some consumers as unclean hair feel. There is a
need for clear conditioning compositions with suitable condition-
ing rheology conferred from something other than a gel matrix
(defined as having a Brookfield RT viscosity of 5,000 to 20,000
cps at 2 sec-1) and rinse-off to leave a clean feel while depositing
sufficient material to confer benefits such as softness and reduced
tangling of wet hair, and good wet-combing. Crystal clarity in the
formulation is also desired as a visual cue to the consumer. Such
conditioners should not weigh down the hair and should offer the
opportunity to volumize fine hair. A recent patent application34
claims that these benefits can be achieved from aqueous-based
conditions comprising a cationic crosslinked thickening polymer

295
and nonionic, cationic surfactants or mixtures of these. It is notable

that these claimed conditioners contain no water-insoluble high-
melting-point oils or waxes. The cationic crosslinked polymers are
copolymers of dimethylaminomethacrylate and acrylamide cross-
linked with methylene-bis-acrylamide. (Polyquaternium-32 for
example Salcare SC92 from Ciba) A homopolymer of quaternized
dimethylaminoethylmethacrylate crosslinked with methylene-bis-
acrylamide is especially preferred.
Similarly, scientists at BASF have recently been awarded a
patent for a process of conditioning hair by the application of a
crosslinked cationic thickening polymer.35 The polymer comprises
N-vinylimidazoline or a derivative, an N-vinyllactam such as N-vi-
nylpyrollidone, and a short chain alkyl (meth)acrylate.
The application of cross-linked cationic polymers could herald a
new innovative era for hair conditioners.
Robert Y. Lochhead and Lisa R. Huisinga

The School of Polymers & High Performance Materials,
References
1. C Zviak, The Science of Hair Care, New York: Marcel Dekker (1986)
2. US Pat Application 2004/00338246, Hair treatment compositions containing at least one
non-thickening of amphiphilic diblock copolymer and at least one fi lm-forming polymer
which is benefi cial for the hair, C Dubief, F Giroud and I Rolla (Feb 19, 2004)
3. US Pat 6,592,854, C Dupuis, assigned to LOral (Jul 15, 2003)
4. US Pat 6,579,517, SN Kim, A Samir and V Schehlman, assigned to BASF (Jun 17, 2003)
5. US Pat 6,482,393, V Schehlmann, K Sperling- Vietmeier, A Sanner and R Blankenburg,
assigned to BASF (Nov 19, 2002)
6. US Pat 6,737,049, SN Kim, A Sanner and V Schehlmann, assigned to BASF (May 18,
2004)
7. US Pat 6,800,276, SN Kim, A Sanner, P Hossel, assigned to BASF (Oct 5, 2004)
8. Intl Pat Application WO 9718247 A1, Improved processes based on atom (or group)
transfer radical polymerization and novel (co)polymers having useful structures and
properties, K Matyjaszewski, S Coca, S Gaynor, D Greszta, T Patten, J Wang and
J Xia (1997)
9. K Matyjasezwski et al, J American Chem Soc 117 5614 (1995)
10. S Kobatake, HJ Harwood, RP Quirk, Synthesis of nitroxy-functionalized polybutadiene
by anionic polymerization using a nitroxy-functionalized terminator, Macromolecules 30
4238-4242 (1997)
11. Intl Pat Application WO 9903894 A1, Polymerizable compositions containing
alkoxyamine initiators derived from nitroso- or nitrone compounds, P Nesvadba, A
Kramer, A Steinmann and W Stauffer (1999)
12. E Malmstroem, C Hawker and J Craig, Macromolecular engineering via living free

296
radical polymerizations, Macromol Chem Phys 199 923-935 (1998)

13. WO-A-98/58974, E Malmstroem, C Hawker and J Craig (1998)
14. Y K Chong, Tam PT Le, G Moad, E Rizzardo and SH Thang, A more versatile route
to block copolymers and other polymers of complex architecture by living radical
polymerization: the RAFT process, Macromolecules 32 2071-2074 (1999)
15. US Pat 6,805,872, N Mougin, assigned to LOral, (Oct 19, 2004)
16. US Pat 6,562,325, Use of stabilized starches in low VOC, polyacrylic acid-containing
hair cosmetic compositions, M Vitale, M Tolchinsky, G Martino, D Solarek and L Cottrell,
assigned to National Starch (May 13, 2003)
17. US Pat 6,599,999, Hair care compositions containing polymeric N-vinyl acetamide and
methods of treating hair, R Chandran, J-P Leblanc and H Hanazawa (Jul 29, 2003)
18. US Pat 6,737,069, Cosmetic compositions containing amphoteric polyurethanes, S
Asaoka, K Koyama, T Tsuzuki and T Hashimoto (May 18, 2004)
19. H Cao, K Maurer and M Vitale, Dehydroxanthan gum, Happi p 82 (May 2004)
20. US Pat Application 2003/0143180, Hairstyling composition which makes possible
remodeling of the hairstyle and process for remodeling the hairstyle using such a
composition, H Samain (Jul 31, 2003)
21. US Pat 6,667,378, Reshapable hair styling composition comprising heterogeneous
(meth)acrylic copolymer particles, I Rollat, H Samain and O Morel (Dec 23, 2003)
22. US Pat 6,645,478, Reshapable hair styling composition comprising (meth)acrylic
copolymers of four or more monomers, I Rollat, H Samain and O Morel (Nov 11, 2003)
23. US Pat 6,585,965, Hair care compositions comprising polyalkylene glycol styling
agents, J Caballada, D Kuhlman and M Schneider (Jul 1, 2003)
24. US Pat Application 2003/0157136, Cosmetic composition forming a tackifying coating
comprising a polymer with a non-silicone skeleton and reactive functional groups, H
Samain, I Rolla-Corvol, F Giroud, N Mougin and A Livorel (Dec 26, 2002)
25. US Pat 6,599,999, Hair care compositions containing polymeric N-vinyl acetamide and
methods of treating hair, R Chandran, J-P Lebranc and H Hanazawa (Jul 29, 2003)
26. US Pat 6,569,413, Hair fi xative composition containing an anionic polymer, YZ Hessefort,
DE Betts and WM Carlson, assigned to Ondeo Nalco Company (May 27, 2003)
27. US Pat 6,833,419, R Morschhauser, C Kayser and M Loffl er, assigned to Clariant (Dec
21, 2004)
28. US Pat 6,833,406, M Green, HR Dungworth, DE Gavin and DB Ridley, assigned to Ciba
(Dec 21, 2004)
29. US Pat Application 2003/0202953, Hair setting compositions, polymers and methods, K
Tamaraselvy and KL Ramey (Oct 30, 2003)
30. US Pat Application 20040265256, H Samain and A Livoreil (Dec 30, 2004)
31. US Pat 6,800,716, A Zofchak and J Obeji, assigned to Alzo International (Sayreville, NJ)
(Oct 5, 2004)
32. US Pat Appflficatfion 20050002871, K Ivanova and SK Pratfley, fi fled by
(Jan 6, 2005)
33. Patent Application GB 0102657.4 (fi led Feb 2, 2001)
34. US Pat Application 20050002892, GF Khan, SM Guskey and RL Wells (Jan 6, 2005)
35. US Pat 6,682,725, R Dieing, P Hossel, S Kothrade, A Sanner, K Zeitz, H-J
Raubenheimer and V Schehlmann, assigned to BASF (Jan 27, 2004)

Chapter 31
Silicone Amino
Elastomer Emulsion for
Conditioning and Styling
Performance
KEY WORDS: conditioning, combing force, curl retention, hair care, styling,
silicone emulsion, antifrizz
ABSTRACT: A nonionic emulsion based on silicone amino elastomer
technology enhances hair conditioning and styling, as
demonstrated in tests of combing force, curl retention,
sensory characteristics, thermal protection and frizz control.
Raw materials for innovative hair care applications have evolved

significantly in recent years, as have formulation technologies
that bring consumers high-performance products. Despite these
advances, it can remain a challenge to deliver good fixative strength,
positive aesthetics and a natural look in one package. One approach
is a new silicone amino elastomer emulsion that combines condi-
tioning and styling performance.
Silicone Amino Elastomer Emulsion

A new crosspolymer combines amino functionality for enhanced
conditioning performance and elastomer technology for styling
benefits. Quaternary and hydroxyl groups also are attached to the
silicone backbone, as shown in Figure 1. A cross-linker provides
elastomeric characteristics that aid styling properties.
A proprietary nonionic microemulsiona based on this amino
elastomer technology was designed for hair styling applications
such as mousses and hair sprays, as well as shampoos and leave-on

298
Styling Silicone Amino Elastomer Emulsion
and rinse-off conditioners. Because the nonionic emulsion is

water-based, it is easy to formulate into hair care products. Its mul-
tifunctional nature can be translated to several enhanced properties:
curl retention, including styling memory, bounce-back and flexible
hold; shine; a soft feel without tackiness; thermal protection; frizz
control; and lack of flaking.
Figure 1. Polymer structure
The conditioning benefits of the amino elastomer emulsion,

including good wet and dry combing, are comparable to those
obtained with a cationic amodimethicone emulsionb, which is an
amine-only emulsion.1 Sensory properties associated with the mate-
rial are superior to those of amine-only emulsions. The film-forming
characteristics associated with silicone and the three-dimensional
network of the polymer aid its styling properties.
a
Dow Corning 5-7070 Si Amino Elastomer Emulsion (INCI: Silicone quaternium-16/
glycidoxy dimethicone crosspolymer and trideceth-12) is a product of Dow Corning
Corporation, Midland, MI USA. Dow Corning is a registered trademark of Dow Corning
Corporation.
b
Dow Corning 949 Cationic Emulsion is a product of Dow Corning Corporation.

299
Gomes et al. Chapter 31
Evaluations Establish Multifunctional Properties

The amino elastomer was evaluated to help quantify its styling,
conditioning and sensory properties. Hair swatches treated with the
emulsion were subjected to high humidity conditions in a closed
chamber to observe the antifrizz effect and curl retention ability
of the emulsion. Combing force assessments were obtained instru-
mentallyc. Sensory evaluations were obtained with a trained panel.
Differential Scanning Calorimetry (DSC) tests evaluated thermal
protection properties. Tests were performed using well-established
protocols developed by Dow Corning for hair care evaluations, with
similar testing being used within the industry.
Combing force: A standard combing technique for the combing
force assessment device was used for testing wet and dry combing
performance, which measured the load necessary to pass a hair tress
through two finely spaced combs. Polyquaternium-10, amodime-
thicone and guar hydroxypropyltrimonium chloride (also referred to
as cationic guar polymer) are typical conditioning agents that show
good reduction of combing force. These materials were used for
comparison with the amino elastomer emulsion. Evaluations were
conducted using 2.0% active silicone for the amino elastomer and
amodimethicone, and 0.25% active for the polyquaternium-10 and
cationic guar polymer.
As shown in Figure 2, all conditioning agents demonstrated
good combing force reduction. The amino elastomer emulsion
reduced combing force by approximately 70%, significantly higher
than that observed for the other conditioning agents.
The combing results for dry hair in Figure 3 show the emulsion
and amodimethicone both reduced combing force in the range of
30%, a significant improvement over polyquatermiun-10 and the
cationic guar polymer, both of which increased combing force.
In summary, the amino elastomer emulsion has wet and dry
combing profiles similar to that of amodimethicone. It is compa-
rable to polyquaternium-10 and the cationic guar polymer in wet
combing assessments, but it performed better than these ingredients
on dry hair.
c
An Instron device manufactured by Instron Corporation, Norwood, MA USA

300
Figure 2. Combing force reduction measurements on wet hair. Materials evaluated include
the amino elastomer emulsion (Am-El), amodimethicone (Am-Si), polyquaternium-10
(PQ-10) and cationic guar polymer (GGQ).
Figure 3. Combing force reduction measurements on dry hair. Materials evaluated include
the amino silicone elastomer (Am-El), amodimethicone (Am-Si), polyquaternium-10
(PQ-10) and cationic guar polymer (GGQ).

301
Curl retention: Tresses treated with several polymers were

subjected to four hours at 90% relative humidity and 22C in a
closed chamber. The amino elastomer emulsion was evaluated at
2% active, polyquaternium-55 at 1%, octylacrylamide/acrylates/
butylaminoethyl methacrylate copolymer (also referred to as acry-
lates copolymer) at 2% and polyvinylpyrrolidone (PVP) at 5%. Two
blends also were evaluated: PVP (2.5%) with the amino elastomer
emulsion (1%) and acrylates copolymer (1%) with the amino elas-
tomer emulsion (1%). The results in Figure 4 (see Color Insert 11)
are expressed as percentage of curl retention vs. elapsed time of
exposure. Curl retention with the amino elastomer emulsion was
comparable to that of PVP and polyquaternium-55.
Figure 4. Curl retention results for the silicone amino elastomer emulsion (Am-El); other
styling polymers including acrylates copolymer (Co-Ac), polyquaternium-55 (PQ-55) and
polyvinylpyrrolidone (PVP); and blends of the emulsion with acrylates copolymer or PVP
Sensory profile: To assess sensory profiles, the amino elastomer

emulsion was compared with PVP, polyquaternium-55 and acrylates
copolymer. These styling agents were applied to curled hair tresses
and evaluated by a trained 10-member panel. Six attributes were

302
considered in the assessments: general sensory characteristics (e.g.,

softness and smooth feel), curl shape, shine, tackiness, curl flexibility
and curl retention. In addition, 1:1 blends of the silicone and each
resin were tested to study possible synergistic effects.
Overall, sensory characteristics were better with the amino
elastomer emulsion. Figure 5 (see Color Insert 11) shows results
with the emulsion, polyquaternium-55 and 1:1 blend of the two
materials. The emulsion improved shine and curl shape, while curl
retention properties associated with the two materials were similar.
A 1:1 blend of the two materials resulted in a synergistic effect on
smoothness: a hair tress treated with the blend was smoother than
tresses treated with the emulsion or polyquaternium-55 alone.
Figure 5. Sensory characteristics of hair tress treated with the amino elastomer emulsion
(Am-El), polyquaternium-55 (PQ-55) and a 1:1 blend of the two materials
In Figure 6, (see Color Insert 12) a comparison of the amino

elastomer emulsion and acrylates copolymer shows the emulsion
has a better sensory profile with less tackiness. The two materi-

303
als have similar shine, curl shape and curl retention characteristics.
Synergistic effects again were observed between the emulsion and
the resin at 1:1 proportions. In this case, the combination resulted in
improvements to curl shape.
(Am-El), acrylates copolymer (Co-Ac) and a 1:1 blend of the two materials
Sensory evaluations also compared the amino elastomer emul-

sion to PVP. Tresses treated with the silicone were smoother than
those treated with PVP or the 1:1 silicone and PVP blend. Figure
7 (see Color Insert 12) shows that other sensory properties were
not significantly different. The combination of silicone and PVP
significantly improved the sensory profile of the tresses but slightly
reduced curl retention.
In general, tresses treated with the amino elastomer emulsion
had improved sensory profiles compared to those treated with the
conventional resins. The behavior of the amino elastomer emul-
sion on curled hair was similar to that of the resins, while in some

304
instances it reduced tackiness and enhanced the perception of

attributes such as shine and feel, without the flaking often associated
with organic polymers. Synergistic effects occurred with the silicone
emulsion and some of the other polymers, allowing blends that sug-
gest versatility for formulating or extending the range of products
that may be developed for specific market needs.
(Am-El), PVP and a 1:1 blend of the two materials
Thermal protection: Maintaining hair moisture is a critical fac-

tor in preventing damage from thermal treatments such as drying,
curling with hot rollers or straightening with irons. Evaluations with
DSC show the total amount of heat absorbed for the total vola-
tilization of water existing in hair fibers. The higher this value the
greater the water retention and heat protection. Results indicate that
the amino elastomer emulsion may help hair retain approximately
180% more water than nontreated hair after thermal treatments.

305
The heat protection phenomenon also is reflected by temperature

changes relative to the higher water loss of untreated hair.
Frizz control: When hair is exposed to high humidity, it absorbs
moisture and expands, and small curls may appear. To evaluate
the amino elastomer emulsion with respect to this frizzing effect,
curled tresses were brushed and left in a humidity chamber at 90%
RH and 22C for two hours. The tresses were monitored over this
period and the percent increase of frizzing was measured using
analysis of images.
Figure 8 shows the result of frizz control evaluations. The amino
elastomer emulsion was significantly more effective at controlling
frizz than the control, a commercial benchmark hair serum and
a silicone styling aidd. Due to its film-forming ability, the amino
elastomer emulsion decreased the frizzing effect more than two fold
compared to the control.
Figure 8. Frizz control profile of tested materials
Easy Formulation for Hair Care

The amino elastomer emulsion was designed for easy addition
and mixing in aqueous-based formulations. No neutralization is
required. The recommended use level for styling products is 7.4% to
d
Dow Corning 2-9027 Styling Aid is a product of Dow Corning Corporation.

306
13% (23.5% active silicone) and 3.7% to 7.4% (12% active sili-
cone) for rinse-off products. The emulsion is compatible with many
cosmetic ingredients, although formulators should confirm compat-
ibility with anionic thickeners and anionic surfactants.
Depending on concentration, the amino elastomer emulsion
exhibits different behaviors in ethanol and water systems. The
ternary diagram in Figure 9 (see Color Insert 13) illustrates the
compatibility ranges.
Figure 9. Ternary diagram for a system formed by the silicone amino elastomer, absolute
ethanol and water
Based on concentration of the amino elastomer emulsion, three

classes of formulations were developed for different fixative and
conditioning levels:
Natural: 6.7% emulsion (2% active silicone) for medium fixa-
tive qualities and a natural look.

307
Firm: 11.7% emulsion (3.5% active silicone) for strong fixative

and conditioning qualities.
Extra hold: 16.6% emulsion (5.0% active silicone) for strong,
long-lasting fixative properties and robust conditioning.
Formula 1 represents a clear shampoo that incorporates the
amino elastomer emulsion for improved wet and dry comb-
ing while also imparting a smooth feel. Formula 2 is a product
designed for sprayable conditioning and hold. Formula 3, a
styling mousse, is an alcohol-free product that adds volume to
hair and light-to-medium conditioning. Formula 4 is a spray-
able gel that provides humectancy and thermal protection for hair.
Formula 5, a pump spray for styling and shine, has a VOC level
of 30%; this formula combines a smooth after-feel with improved
hair shine.
Formula 1. Clear shampoo

% w/w
A. Water (aqua), deionized 53.60
Sodium laureth sulfate (Genapol LPO, Clariant) 33.00
Cocamidopropyl betaine (Dehyton, Cognis) 3.00
Cocamide DEA (Comperlan KD, Henkel) 3.00
B. DMDM hydantoin (Glydant, Lonza) 0.10
C. PEG-120 methylglucose dioleate (Glutamate DOE 120, Amerchol) 0.60
D. Citric acid solution, 20% qs
E. Silicone quaternium-16/glycidoxy dimethicone
crosspolymer and trideceth-12 (Dow Corning 5-7070 Si
Amino Elastomer Emulsion, Dow Corning) 6.70
F. Sodium chloride; 10% solution in distilled water
(Sodium Chloride, Fisher Scientific) qs
100.00
Procedure: Combine A. Add B to A. Add C to AB with mixing. Heat ABC to 80C with mixing until
completely melted. Cool to room temperature with gentle mixing. Add D to adjust pH to 5.5.
Add E slowly, with gentle mixing, and homogenize. Add F to adjust viscosity.

308
Formula 2. Hair styling lotion
% w/w
A. Mineral (paraffinum liquidum) oil 3.00 3.00
Cyclopentasiloxane (Dow Corning 245 Fluid) 2.00 2.00
Phenyl trimethicone (Dow Corning 556 Fluid) 2.00 2.00
Steareth-2 (Volpo S-2, Croda) 2.00 2.00
B. Water (aqua), deionized 78.20 73.20
Glycerin 4.00 4.00
DMDM hydantoin 0.10 0.10
Steareth-20 (Volpo S-20, Croda Inc.) 2.00 2.00
C. Silicone quaternium-16/glycidoxy dimethicone
crosspolymer and trideceth-12 (Dow Corning 5-7070 Si
Amino Elastomer Emulsion, Dow Corning) 6.70 11.70
100.00 100.00
Procedure: Combine A, heat to 80C and homogenize. In a separate container, combine B, heat
to 85C and homogenize. Add A to B using medium shear mixing. Cool to room temperature.
Slowly add C to AB with low shear mixing. Homogenize.
Formula 3. Conditioning mousse

% w/w
A. Water (aqua), deionized 82.1 81.6 76.7
DMDM hydantoin (Glydant, Lonza) 0.1 0.1 0.1
Polyquaternium-10 0.1 0.1 0.1
PEG-60 hydrogenated castor oil - 0.5 0.5
(Cremophor HCO-60, Lipo Chemicals)
B. Cocamidopropyl betaine (Dehyton, Cognis Corporation) 4.0 4.0 4.0
Decyl glucoside (Plantaren 2000, Henkel KgaA) 4.0 1.0 1.0
C. Cetyl dimethicone (Dow Corning 2502 Cosmetic Fluid) 1.0 1.0 1.0
D. Silicone quaternium-16/glycidoxy dimethicone
crosspolymer and trideceth-12 (Dow Corning 5-7070
Si Amino Elastomer Emulsion, Dow Corning) 6.7 11.0 16.7
100.0 100.0 100.0
Procedure: Combine A. In a separate container, combine B. Add B to A with mixing. Add C,

mixing until uniform. Add D, mixing until uniform.

309
Formula 4. Jelly hair spray
% w/w
A. Water (aqua), deionized 78.20
B. DMDM hydantoin 0.10
C. PEG-150/decyl alcohol/SMDI copolymer 5.00
(Aculyn 44 Polymer, Rohm and Haas)
D. Glycerin 6.00
Ethanol (Ethyl Alcohol Absolute, VEL) 4.00
E. Silicone quaternium-16/glycidoxy dimethicone
Si Amino Elastomer Emulsion, Dow Corning) 6.70
100.00
Procedure: Add B to A and dissolve completely. Add C to AB. Mix slowly to homogenize and
increase viscosity. Add D to ABC. Slowly add E with mixing.
Formula 5. Shine and styling pump spray
% w/w
A. Water (aqua), deionized 55.2 50.2 45.2
B. DMDM hydantoin (Glydant, Lonza) 0.1 0.1 0.1
C. Glycerin 6.0 6.0 6.0
Ethanol (Ethyl Alcohol Absolute, VEL) 30.0 30.0 30.0
PEG/PPG-15/15 dimethicone
(Dow Corning 5330 Fluid, Dow Corning) 2.0 2.0 2.0
D. Silicone quaternium-16/glycidoxy dimethicone
Si Amino Elastomer Emulsion, Dow Corning) 6.0 11.7 16.7
100.0 100.0 100.0
Procedure: Add B to A and dissolve completely. Add C to AB and homogenize. Slowly add D with
mixing.
Summary and Conclusions

The new silicone amino elastomer emulsion offers a useful combi-
nation of properties that target conditioning with adjustable fixative

310
properties. The multifunctional attributes of the silicone offer for-

mulators flexibility when designing hair care products, and mixing is
easy because the material is delivered in emulsion form.
The amino elastomer emulsion imparts smoothness and the
typical conditioning profile associated with silicones in hair care
applications to reduce wet and dry combing force. The film-forming
ability of the silicone provides positive sensory effects, while reducing
frizz and helping hair retain moisture for protection from heat. Curl
shape and retention is comparable to that of the conventional styling
polymers evaluated in this article. Synergistic properties with other
styling polymers suggest formulating versatility that can lead to a
range of highly differentiated product for todays global consumers.
lvaro Gomes, Daniel F. de Almeida and Camilla Abbehausen

Dow Corning do Brazil Ltda., Hortolandia, Brazil
Bethany K. Johnson
References
1. CA Hoag, BM Rizwan and KM Quackenbush, Evaluating silicone emulsions for global
hair care applications, GCI 164(4) 4455 (1999)

Chapter 32
Designing Emulsions for

Relaxer Actives
KEY WORDS: hair care, relaxer, emulsion, emulsifier, irritation, ethylene
oxide, propylene oxide
ABSTRACT: Relaxer emulsions have unique requirements regarding pH,
hydrophilic-lipophilic balance and minimizing irritation
potential. This chapter suggests ways to meet these
requirements and provide an ideal emulsion base for relaxer
actives.
Hair relaxer formulations require an emulsion whose characteristics

differ in important ways from those of emulsions used in lotions and
creams. Understanding those differences can help formulators design
better emulsions for relaxer actives. This chapter describes the emul-
sions, emulsifiers and relaxer actives used in relaxer formulations.
Emulsions
Emulsions are the essential base for the delivery of active ingredi-
ents in personal care and pharmaceutical products. Over the years,
formulating chemists have used different types of ingredients in
designing different types of emulsions. In most cases, the charac-
teristics of emulsions depend on how the ingredients interact and
how the emulsions are formulated and manufactured. Predicting
emulsion behavior is difficult if little is known about the chemi-
cal composition of the ingredients and actives used. Overcoming
difficulties in emulsion formulation requires first-hand knowledge
of all reactive compounds in the formulation and the outcome of
their reaction.
The difficulties vary depending on emulsion types. Such dif-
ficulties can be managed if all of the necessary steps of ingredient

312
Styling Designing Emulsions for Relaxer Actives
selection and investigation are done carefully before drawing out a

final formula.
One example is emulsion stabilization. The simple process of
putting together a water-in-oil emulsion or an oil-in-water emul-
sion with actives could be very challenging. A general knowledge
of using a surfactant with a low hydrophilic-lipophilic balance
(HLB) as the primary emulsifier for water-in-oil emulsions and
using a high-HLB surfactant for oil-in-water emulsions is in the
right direction of thinking, but other factors must be considered to
guarantee a stable emulsion. The correct amount of heat energy is
needed to promote the reaction. The correct amount of mixing and
homogenizing will ensure the correct amount of mechanical energy
to reduce particle size and improve emulsion formation. The chemi-
cal reaction of the ingredients must be studied to determine the
overall effect on the emulsion.
Emulsion definition: The term emulsion has been defined in vari-
ous ways over the years. Some definitions are more elaborate than
others. Some are simply the general definition that will apply in this
chapter. An emulsion is a complex mixture of ingredients dispersed
in either a water phase or an oil phase. The combination is aided by
emulsifiers and co-emulsifiers that help to reduce interfacial tension
between the oil phase and the water phase.
Types of emulsions: Oil and water can make primarily three types
of emulsion: oil-in-water (o/w), water-in-oil (w/o), and water-in-oil
and oil-in-water co-existing (w/o/w). The o/w emulsion is the base
for most creams and lotions. Typically, high-HLB surfactants are
used to stabilize the system. The w/o emulsions can be difficult to
stabilize if surfactants with inappropriate HLB are used.
Emulsifiers
Emulsifiers are surfactants, also known as surface active agents.
Each emulsifier has a hydrophilic portion and a lipophilic portion.
The composition of the emulsifier plays a key role in the overall
emulsion behavior and function.
Emulsion formation is influenced by secondary emulsifiers
such as the ethoxylates and propoxylates (Figure 1). The degree of
ethoxylation or propoxylation will help to shift the hydrophilic and

313
Obukowho Chapter 32
lipophilic balance of the entire emulsion. If the number of moles

of ethylene oxide or propylene oxide is less than 5, the emulsion
will be w/o; if that number is 5 or greater, the emulsion will be o/w.
Compounds with a high degree of ethoxylation with high-HLB
surfactants will favor the formation of an o/w emulsion. On the
other hand, compounds with a high degree of propoxylation with
low-HLB surfactants will favor the formation on a w/o emulsion.
There are situations where a combination of ethoxylated materials
and propoxylated materials will provide unique characteristics of
emulsion behavior, especially with actives.
Figure 1. Ethylene oxide and propylene oxide
Emulsions for Relaxer Actives

To understand the type of emulsion formation that is ideal for
relaxer actives, one must have general knowledge of what a relaxer is
(see Marketing Relaxers). Relaxers are o/w cream emulsions with
actives such as sodium hydroxide, lithium hydroxide, potassium
hydroxide and guanidine hydroxide. Figure 2 illustrates the chemis-
try of these relaxer actives. The mechanical manipulation of the hair
by combing and stretching during relaxer application produces the
straightening effect.

314
Figure 2. Relaxer actives and chemistry
Marketing Relaxers
Over the years, different types of relaxers have been marketed under
different names to describe their possible reactivity. These are marketing-
driven names. For example, the No-Lye Relaxer refers exclusively to sodium
hydroxide relaxers. The term Base Relaxer refers to a base product used to
base the scalp before relaxer application. The No-Base Relaxer is normally
a relaxer without a scalp-basing ingredient such as petrolatum. Typically,
the user will apply a separate scalp-basing product when using the no-base
relaxer.
The No-Lye (Mix) and the No-Lye (No-Mix) have actives other than
sodium hydroxide. The No-Lye (Mix) has a combination of calcium hydroxide
and guanidine carbonate. This is a two-part system that is mixed to
generate guanidine hydroxide and calcium carbonate and water.
The No-Lye (No-Mix) usually is made with lithium hydroxide (and in some
cases calcium hydroxide and lithium hydroxide) all in one step.
Relaxer emulsion: Relaxer emulsions are composed of mineral oil,

petrolatum, primary emulsifiers, fatty alcohols, fatty alcohol ethoxy-
lates, lanolin and lanolin derivatives. In most cases, the primary
emulsifiers used in relaxers are the nonionic emulsifiers because non-
ionics are unique in their high tolerance for salts and their ability
to withstand very high pH. These emulsifiers can be liquid or solid.

315
Obukowho Chapter 32
They can function as the primary or secondary emulsifier. They are

electrolyte-tolerant and stable at high and low pH. They are good
solubilizers and dispersing agents.
Improperly manufactured relaxers can have the potential for irri-
tation. Proper selection of ingredients is a key factor in minimizing
irritation potential in a relaxer.
Mineral oil and petrolatum in the relaxer: Mineral oil and petro-
latum used in relaxers comes in various grades and viscosities that
are very important in forming relaxer emulsions. The objective of
increasing levels of petrolatum and mineral oil in relaxer formulae
was to reduce irritation. This objective is still a problem for many
relaxer manufacturers. Properly selected emulsifers and co-emulsifi-
ers in combination with the appropriate manufacturing techniques
are essential to minimize irritation and promote effective release of
oils and actives.
Surfactant effect on relaxer emulsions: This is an area of emulsion
formation that requires a lot of attention. The HLB of the emulsi-
fiers used in relaxer emulsion formation plays an important role in
controlling the wetting behavior of the emulsion and the detergency
effect. A high degree of wetting the hair can speed up penetration
of actives and increase contact with the scalp. This can lead to more
hair damage and scalp irritation during application.
Use of alkyl sulfates, amphoteric surfactants, esters and natural
oils in relaxer emulsions should be evaluated carefully. Esters and
natural oils will hydrolyze in high-pH environments, causing sepa-
ration and promoting irritation.
Ideal Emulsion Base for Relaxer Actives

A good relaxer base should excel in the following characteristics:
emulsion stability without separation;
spread out during application;
relaxation by way of gradual release of active ingredients;
ability to maintain good hydrophobic surface after relaxation;
and
minimum irritation.
Emulsifiers that promote phase inversion should be studied
carefully for use in relaxer emulsions. In phase inversion, the exter-

316
nal phase becomes the internal phase. This process prevents the
complete emulsification of the oil phase but forms a stable emulsion
with properly selected emulsifiers. Phase inversion will ensure parti-
cle size reduction that is ideal for relaxer emulsions. It also improves
stability and provides benefits to the overall emulsion behavior.
Although phase inversion sometimes is viewed as emulsion separa-
tion or destabilization, it is a useful process that can provide benefits
in the hands of one skilled in the art of making relaxers.
It is important to note that relaxer emulsions are not body
creams or lotions. All ingredients for relaxer emulsion formation
should be studied carefully to avoid unnecessary emulsion problems
and irritation.
Conclusion
A good understanding of the lipophilic portion and the hydrophilic
portion of emulsifiers will allow formulators to design emulsions
that will improve the base for relaxer actives.
Patrick Obukowho
Croda Inc., North American Technical Center, Edison, NJ USA
References for Additional Reading

1. P Obukowho, M Gamez and KF Gallager, A new approach in formulating hair relaxer,
Happi 23(4) 6270 (1995)
2. C Fox, An introduction to multiple emulsions, Cosmet Toil 11(101) 109111 (1986)
3. GM Eccleston, Application of emulsion stability theories, Cosmet Toil 11(101) 135 (1986)
4. P Obukowho and B Woldin, Ethnic emulsion design, DCI 4244 (Nov 1996)

Chapter 33
Styling Polymers in
Mousses
KEY WORDS: mousse, The Science of Hair Care, styling polymers, film
forming, cationic polymer, bimodal polymer, patents
ABSTRACT: Survey of formulating ideas in mousses for hair styling
including a book, raw materials and several patents.
A book, 2 polymers, and several patents are the raw materials of

this chapter that surveys some new formulating ideas in mousses
for hair styling. In a market whose demands range from natural to
sophisticated, and from flexible hold to stiff hold in a regulatory
environment demanding low volatile organic compounds (i.e., high
water compounds), new ideas are always welcome. We will look at
a few.
A Book
You might say LOral wrote the book on hair care. Well, they cer-
tainly wrote most of The Science of Hair Care, whose second edition
was published in 2005. The chapter titled Temporary Restyling of
the Hair was written by four researchers in hair care development
(and a specialist in environmental safety) at LOral Recherche in
France.1 These authors write styling polymers are selected for their
film forming properties (the polymers invisible film covers the hair
strands and binds them together at points of contact) and for their
compatibility (especially their solubility, which means water-soluble
polymers are typically preferred).
The various styling polymers can have different charges (non-
ionic, anionic, cationic, amphoteric) and different properties.
According to these LOral authors, the ideal styling polymer must
create (with the other ingredients) a film having high affinity for the

318
Styling Styling Polymers in Mousses
hair. It must be readily washed out. It must not form white particles
on brushing and it must not become sticky under high humidity
conditions.
The choice of monomers determines a polymers properties, as
described by these authors. Polymers formed from acrylic monomers
are often used because they are readily soluble in water. Polymers
formed from vinylcaprolactame monomers increase rigidity. The
structure of a polymer can affect its properties. Combining several
polymers in a product can modulate the products properties or
provide synergism. In one example cited in the book, an anionic
polymer for style control and a cationic polymer for conditioning
provide the hair style with long lasting hold and the hair fiber with a
soft feel.
In actual fact, no type of polymer is recommended for a specific
intrinsic property, these authors write. All kinds of material can
be prepared from a single chemical class of polymer. The polymers,
even if restricted to soluble polymers, can yield a palette of intrinsic
properties of the film formed on the hair from the most flexible to
the most rigid, from fragile to resistant, from plastic to elastic.2
A Cationic Polymer
Luviquata Supreme is one of the series of BASF polyquaterium
styling and conditioning polymers shown in Table 1. Luviquat
Supreme reportedly delivers good stiffness, hold, and curl retention.
Vittoria Signori tells us what those terms mean. Signori is group
leader for hair care, Technical Services, Cosmetic Solutions for
BASF in North America.
Stiffness is the property of a polymer film or material that
defines its strength and resistance toward mechanical deformation.
Stiffness is not strictly related to curl retention, humidity resistance,
and flexibility.
Hold is the ability of a formulation to hold a style over time.
Hold is related to stiffness, but is more a property of the treated
substrate than just of the hair fixative polymer applied to it. Hold is
imparted by the hair fixative, but the concept of hold encompasses
a
Luviquat is a registered trade name of BASF.

Table 1. Luviquat styling polymers from BASF
Hair_Chapter 33.fcx.indd 319

Brewster
Hair styling Hair and skin conditioning

Approximate
Molecular Mousse. Conditioning rinse. Shampoo,
INCI Name weight lotion Gel Spray Hair treatment Shower
Luviquat Supreme Polyquaternium-68 300,000

Luviquat UltraCare Polyquaternium-44 200,000
Luviquat Hold Polyquaternium-46 700,000
Luviquat PQ 11 PN Polyquaternium-11 1,000,000
Luviquat HM 552 Polyquaternium-16 400,000
Luviquat Style Polyquaternium-16 400,000
Luviquat FC 370 Polyquaternium-16 100,000
Luviquat FC 550 Polyquaternium-16 80,000
Luviquat Excellence Polyquaternium-16 40,000
especially recommended
recommended

dependant on formulation

not recommended
Chapter 33
319
9/15/07 1:03:57 AM
320
a broader set of properties closer to the final application and use,

rather than closer to the physical properties of a polymer film inves-
tigated by itself.
Curl retention is strongly related to the ability of the film to not
be influenced by humidity in the air. Unlike hold and stiffness, curl
retention is measured in a standard way. Curl retention is measured
when the formulation is applied to hair curls, and it measures, in
numeric terms, the ability of the curl to survive several hours in a
high humidity climate, Signori said.
The Luviquat Supreme polymer consists of 55% vinyl pyrroli-
done (VP), 10% vinyl imidazole (VI), 29% methacrylamide (MA)
and 6% quatenized vinyl imidazole (QVI). Each of the monomers
makes its own contribution.
VP is the basic building block of many BASF hair styling poly-
mers. It provides an excellent setting effect and water solubility that
enables the resin to be washed from the hair. MA and VI support curl
retention and stiffness. QVI provides substantivity to the hair plus
a conditioning effect and stiffness, Signori said. The choice of the
monomers and the molecular weight of the polymer (approximately
300,000) contribute to the stiff, film forming effect and provide a
polymer especially recommended for hair mousses and lotions.
According to Signori, the formulator can vary the hold from
strong to flexible by considering 3 parameters:
The amount of fixative (the more polymer, the stiffer the film)
The level of emollients and foaming agents, which also acts as
plasticizing agents toward the polymer film (the more plasti-
cizers, the more the film will become flexible)
The choice of using one or more polymer fixatives (blending
polymers will usually result in overall properties somehow
between the 2 polymers blended)
Formula 1 uses Luviquat Supreme in a mousse composition
developed in BASFs laboratory in Roxbury, New Jersey. This
formulation has been evaluated extensively against the same formu-
lation made with a competitive polymer. It was chosen by a majority
of respondents in an in-use test conducted by an independent
testing facility. It showed excellent setting and hold and was found
to provide a longer lasting style, Signori said.

321
Brewster Chapter 33
Formula 1. BASF test mousse
A. Water (aqua) 72.20% w/w

Polyquaternium 68 (Luviquat Supreme, BASF) 10.00
DMDM hydantoin (and) iodopropynyl butylcarbamate
(Glydant Plus liquid, Lonza) 0.40
B. Water (aqua) 10.00
Ceteareth-6 (and) stearyl alcohol (Cremophor A6, BASF) 0.20
Hydroxyethyl cetyldimonium phosphate (Luviquat Mono CP, BASF) 0.40
Laureth-4 (Rhodasurf L-4, Rhodia) 0.70
C. Fragrance (parfum) 0.10
D. Propane/Isobutane (Propellant A46, Technical Propellants, Inc) 6.00
100.00
Procedure: Add ingredients of A in order listed with adequate agitation, making sure all
components are completely dissolved before adding the next. Premix ingredients of B and heat
to 65C-70C. Mix until all ingredients are completely dissolved. Cool to 40C and add C to B
below 40C. Add BC to A with adequate agitation. Fill into appropriate containers and charge
with D.
Packaging:
Can: Exal 38 X 138 mm Epoxy Lined
Valve: Precision Valve S90 018 inverted
Actuator: White Mars inverted conical spout
A Bimodal Polymer
Interpolymers Syntranb styling polymers are listed in Table 2. They
all use Interpolymers unique patent-pending bimodal technology
designed to produce quick-setting hold, high humidity resistance,
and effective curl retention in hair styling aids.
The bimodal polymer technology uses a bimodal interpenetrat-
ing network to deliver both cationic and anionic functions. The
result is a reversible, cross-linked polymer complex achieved by the
ionic association of the 2 types of polymer chains, explained Laeti-
tia Marlier, a technical service representative at Interpolymer Srl,
Wissembourg, France.
These polymers are composed of 2 different types of acrylic
polymer chains: one with anionic functionalities and the other with
b
Syntran is a registered trade name of Interpolymer Corporation.

322
cationic functionalities. The anionic chain contributes to the poly-

mers removal properties and the cationic chain imparts strong hold
and ease of styling, Marlier said.
Table 2. Syntran styling polymers from Interpolymer
Approximate
Syntran molecular
Trade name INCI designation weight
PC 5100 Styrene/Acrylates/Ammonium methacrylate copolymer 45,000
PC 5112 Polyacrylate-16 80,000
PC 5107 Polyacrylate-18 (and) polyacrylate-19 35,000
PC 5117 Polyacrylate-18 (and) polyacrylate-19 50,000
The cationic functionalities are achieved with strong electroposi-

tive groups, such as amino functions. The anionic functionalities
are achieved by modifying the anionic chain only with carboxylic
groups, which contain an acid part.
It is the selection of the co-monomer and the control of its
molecular weight that allows us to optimize the placement of the
amino functional group that controls the steric hindrances of the
cationic polymer. The polymer composition plays an important role
in this geometrical and electrical interaction, Marlier explained.
Because the amino function is in an exposed position, it can
interact very well with the anionic functions from the other chain.
This results in a strong ionic association, which we call a strong
interpenetrating network, and provides an important role in the
polymers cohesive and adhesive properties, Marlier added.
The 2 acrylate chains are co-manufactured. The amino func-
tions role in the formation of the polymer is governed by monomer
choice. Since the polymers are co-manufactured, it is the selection
of the co-monomer, molecular weight control, charge density of
each chain, and chain ratios that permit the ionic interaction to
occur during the drying phase. These variables permit the change

323
Brewster Chapter 33
in properties exhibited by the various bimodal polymers. During

manufacturing and in the wet stage, the charges are blocked to pre-
vent interaction. It is during the drying phase that this unique ionic
association occurs.
There are significant structural differences between polymers in
this series, enabling the formulator to select the desired aesthetic
properties required for a particular formulation. Targeted usage is
5%-20%, according to Interpolymer documents.
We recommend PC 5100 for medium hold and PC 5112 for
a softer, more natural hold or feel. PC 5107, which has the hardest
hold attributes of the 3, is ideal for use in formulating alcohol- or
solvent-containing hair styling aids and clear mascaras, Marlier
said. Our PC 5117 launched in July was created for formulators of
aerosols with low levels of volatile organic compounds. These for-
mulators are seeking to control the amount of water they introduce
into their formulas.
Formula 2 shows a mousse composition in which a bimodal
polymer combined with silk proteins is claimed to surround and
support each strand to give root lift, manageability, and excellent
shine to lifeless hair. This firm-hold formula adds style-support
and texture while leaving hair with a natural feel, Marlier said.
Recent Patents
A search at www.uspto.gov and www.freshpatents.com revealed
several patents and patent applications addressing styling agents and
mousses. Here is a sample from inventors in the United States, the
UK and France.
Dry hair restyling agents: In a patent assigned to Procter &
Gamble,3 Bolich et al. describe hair styling compositions containing
select polyalkylene glycol styling agents that provide for improved
dry hair restyling performance without reapplication of the compo-
sition and/or any additional hair styling aids.
These authors discovered that certain polyalkylene glycols
can provide for a fluid film to be left on the hair. The film can be
characterized as a reformable weld that allows the hair fibers to
be separated by forces such as wind, and then readhere using styl-

324
ing techniques such as combing, brushing, or running the fingers

through the hair. A single application applies restyling without reap-
plication over a period of up to several days.
Formula 2. Silky-smooth styling/volumizing mousse from

Interpolymer
A. Water (aqua) 79.95% w/w

Disodium EDTA (Dissolvine Na2-S, Akzo Nobel) 0.05
PEG-75 meadowfoam seed oil (Meadowsol 75:75, Fancor) 0.50
Fragrance (parfum) 0.05
C. Sodium methyl cocoyl taurate (Tauranol WS Concentrate, Finetex) 1.50
Panthenol (Ritapan DL, RITA) 0.20
Diazolidinyl urea and iodopropynyl butylcarbamate (Germall Plus, ISP) 0.35
Silk amino acids, (Crosilk Liquid, Croda) 0.20
Hydrolyzed silk (Crosilk 10,000, Croda) 0.20
D. Styrene/acrylates/ammonium methacrylate copolymer
(Syntran PC 5100, Interpolymer) 15.00
100.00
Procedure: Prepare A and warm to 35-40C with moderate stirring. In a separate vessel prepare
B and warm to a temperature not to exceed 45C. Add B to A and stir until clear, homogenous
mixture obtained. Individually add C ingredients to AB, stir between each addition until clear
and homogenous. Add D; stir until homogenous. Cool to room temperature. Fill into Airspray WR
T4 Foamer.
Appearance: Clear, aqueous solution. Final pH = 7.40.
In the case of a hair mousse described in the patent, the polyal-

kylene glycol styling agents have a number average molecular weight
from about 190 d to about 1500 d. The mousse optionally contains
silicones or silicone derivatives having a molecular weight of greater
than about 40,000 d.
High humidity styling agents: Two patents address the
problem of hair styling under high humidity conditions.
A United States patent application4 fifled by earflfier thfis
year discloses a styling agent composed of an ABA block copolymer,

325
Brewster Chapter 33
wherein the A groups are polymeric blocks built up from an ethyl-

enically unsaturated polymersible monomer (especially preferred are
polyacrylate blocks or polymethacrylate blocks) and the B group is a
poly(alkylene oxide) block.
Several of the inventors are apparently based in the UK (in
Wirral, northwest England). They discovered that these triblock
copolymers not only show good solubility in water/alcohol solvent
systems, but also perform very well under high humidity conditions.
Writing in the patent, the inventors say this effective performance at
high humidity was totally unexpected, given the hydrophilic nature
of the poly(alkylene glycol) block. Formula 3 shows an example
mousse composition from the patent.
Formula 3. A styling mousse
Silicone Emulsion (DCX2-1787, Dow Corning) 1.2% w/w

Triblock copolymer according to US Pat Appl 20050106117 1 to 3
Ceteareth-50 (VOLPO CS 50, Croda) 0.3
Phenoxyethanol (Sepicide LD, Seppic) 0.4
PEG-40 Hydrogenated Castor Oil (Cremophor RH410, BASF) 0.2
Ethanol 7.5
Propane/Butane (CAP 40) 8.0
Water (aqua) to 100.0
In an earlier patent,5 some of these same inventors report their

discovery that the use of certain fluoroamines significantly improves
the holding power of styling resins under high humidity conditions.
Compositions according to the patent consist of a hair styling
polymer, a partially or fully fluorinated compound, and a cosmeti-
cally acceptable diluent, or carrier. The styling polymer will have
1 or more groups selected from acidic functional groups, anionic
groups derived from the acidic functional groups, or a mixture of
those groups. The fluorinated compound will have 1 or more groups

326
selected from amino groups, acid salts of the amino groups, or a

mixture of those groups, wherein the fluorinated compound com-
prises an aromatic ring.
For this earlier patent, the inventors provide exactly the same
mousse formulation as Formula 3, except that in the earlier patent
the styling polymer is polyurethane-1 (Luviset PUR, BASF) neu-
tralized to 95% with aminomethyl propanol (AMP, Angus) and an
equimolar amount of fluoroamine 4-(trifluoromethyl)aniline. This
polymer is in the composition at a level of 1.5%.
Improving mousse properties: For our last example, we return to
LOral and, in fact, to Claude Dubief, a LOral hair care develop-
ment specialist who cowrote the chapter titled Hair Care Products
in The Science of Hair Care. He also is a coinventor of an aerosol
mousse based on at least 1 associative polyurethane and at least
1 anionic polymer, and claimed to improve certain properties of
mousses.6 At least 1 of the 2 polymers must have foaming power.
The inventors discovered that the properties of aerosol mousses
based on anionic polymers can be improved by adding an associative
polyurethane. In particular, the rigidity, the expansion, and the sta-
bility of the mousse can be markedly improved, according to claims
in the patent.
Bud Brewster
August 2005 Cosmetics & Toiletries
References
1. R Beitone, JM Sturla, H Paty, P Meurice and H Samain, Temporary restyling of the hair,
in The Science of Hair Care, 2nd edn, C Bouillon and J Wilkinson, eds, Boca Raton:
Taylor & Francis (2005) pp 169-200
2. Ibid, p 178
3. US Pat 6,635,240, RE Bolich Jr et al, Hair styling compositions containing select
polyalkylene glycol styling agents, assigned to Procter & Gamble (Oct 21, 2003)
4. US Pat Application 20050106117, G Adams, MDEason, E Khoshdel and SH Rogers,
Triblock copolymers for cosmetic or personal care compositions
5. US Pat 6,653,353, G Adams and E Khoshdel, Cosmetic and personal care
compositions, assigned to Home & Personal Care USA (Nov 25, 2003)
6. US Pat 6,767,532, C Dupuis and C Dubief, Composition in the form of an aerosol
mousse based on polyurethane and anionic polymer, assigned to LOral (Jul 27, 2004)

Chapter 34
Evaluating Polyimide-1, a
Styling Resin for Gel and
Mousse Formulations
KEY WORDS: hair styling resin, gel, mousse, polyimide-1, testing and
instrumentation
ABSTRACT: This chapter surveys a variety of tests used to evaluate
polyimide-1, a new hair styling resin, by comparing
its performance against that of PVP in gel and mousse
formulations.
Variations of hair gels and mousses comprise approximately half

of the global styling product market and are the key growth area
within the category. New technology is required to sustain this
growth and to meet the challenge of providing longevity of style
(style memory), volume creation, style definition, and a smooth/
touchable hold while maintaining compatibility with polyacrylic
acid rheology modifiers.
This chapter surveys a variety of tests ISP uses to evaluate new
hair styling resins for gels and mousses. Tests for high humidity
curl retention, film clarity, flexibility, durability, toughness, film
surface friction and versatility/compatibility are used to compare
the in-product performance of a new resin (polyamide-1) versus an
established styling resin (polyvinylpyrrolidone).
Polyimide-1
Polyimide-1a was specifically designed by ISP to meet consumer
needs for the gel and mousse market. It is a water-soluble, amphoteric
a
Aquaflex XL-30 (INCI: Polyimide-1) is a product of International Specialty Products.

328
Styling Evaluating Polymide-1, a Styling Resin
polymer comprised of an isobutylene/dimethylaminopropylmaleim-

ide polymer backbone derivatized with ethylene oxide/propylene
oxide (EO/PO) oligomers and dimethylaminopropylamine
(DMAPA) (Figure 1). ISP is the sole supplier of polyimide-1.
Figure 1. Structure of polyimide-1
EO/PO oligomers provide the unique, natural feel and water

resistance properties of polyimide-1. These oligomers are typically
used in other industries for their flexibility and natural humec-
tant ability, i.e. the ability to take up water without impacting
other properties. DMAPA is a self-associating, secondary amine
that imparts good cohesive strength, toughness and overall good
mechanical performance. The ratios of EO/PO and DMAPA in
polyimide-1 were optimized to work synergistically with anionic
rheology modifiers (especially polyacrylic acid-based rheology
modifiers such as carbomer). Performance benefits of formulations
with polyimide-1 and polyacrylic acid polymers can be tailored to
provide customized functionality/esthetics and tactical differences
based on the ratio of polyacrylic acid to polyimide-1.
To demonstrate the uniqueness and effectiveness of polyimide-1,
various hair gel formulations containing polyimide-1 and carbomer
and other typical styling products were prepared in ISPs laboratory

329
Clements Chapter 34
to study performance properties. The following measurements were

performed to determine the attributes and efficacy of polyimide-1/
carbomer systems:
High humidity curl retention
Film clarity
Flexibility, durability, and toughness
Dynamic Hair Spray Analysis (DHSA)
Cantilever 3-point bending
Stress/Strain testing
Film surface properties: coefficient of friction
Volume and consumer perception: salon studies
Versatility/compatibility: formulation stability
Half-head salon evaluations were also conducted in ISPs
applications laboratory to ascertain consumer perceptions and to
corroborate our experimental results.
Water Resistance and High Humidity Curl

Retention
Polyimide-1 is a water-based polymer that produces hydrophobic
films that are easily removed from hair by shampooing; there is
no resulting buildup of polymer on the hair. Polyvinylpyrrolidone
(PVP) is an established styling resin used by a significant por-
tion of the current hair gel market. PVP K-30 is a specific grade of
PVP offered by multiple suppliers. We used PVP K-30 for all tests
reported here, so for the remainder of this chapter we will use only
the term PVP and it will refer to PVP K-30.
Figure 2 illustrates a hair swatch treated with a 2% polyimide-1
/ 0.5% carbomer gel (4:1 blend ratio), dried as a flat ribbon spike,
dipped in water for 5 seconds and then held horizontally to dem-
onstrate resistance to water. The polyimide tress maintains its
holding ability after the 5 second immersion while the PVP/car-
bomer tress fails.
Water resistance for a measurable time period is only one of
the key benefits of polyimide-1. Its films are also resistant to high
humidity. Figure 3 (see Color Insert 13), shows a comparison
chart of high humidity curl retention of polyimide-1/carbomer

330
systems versus the most popular hair gel system, PVP/carbomer.

The test was conducted by applying 0.5 g styling gel per 2 g tress of
6.5" European dark brown hair and then rolling the tress in spiral
curl. The graph depicts the significant humidity resistance of the
polyimide-1 formulations, even at very low use levels of polymer,
demonstrating the superior curl retention properties of this polymer.
Figure 2. Water resistance and high humidity curl retention of hair swatches treated with
2% polyimide-1 / 0.5% carbomer gel (upper) or 2% PVP / 0.5% carbomer gel (lower)
dipped in water for 5 seconds
Figure 3. High humidity curl retention of polyimide-1/carbomer blends versus PVP/

carbomer over 5 hours at 90% RH and 80F

331
Clements Chapter 34
High humidity resistance is an essential factor for creating and

maintaining a hairstyle, but there are other consumer perceivable
features that are also important to a multifunctional resin, including
stiffness, durability and conditioning benefits.
Gel Film Clarity

Dry film properties are a key attribute for evaluation of polymer
performance on hair. Typical hair gel formulations containing
polyimide-1 and carbomer were compared to the most widely used
formulations on the market. Films were drawn on a glass plate
using a Bird Applicator 0.003" and allowed to dry at 70F and
50% relative humidity. As can be seen in Figure 4, the dry films of
polyimide-1 are clear while PVP/carbomer films are hazy.
Figure 4. Clarity of dry films of polyimide-1/carbomer (left) and PVP/carbomer (right)
Formulation Clarity
Formulation clarity is an important factor for any hair gel system,
especially those with polyacrylic acid or anionic rheology modifiers.
Anionic rheology modifiers are acidic polymers that are insoluble

332
in water until they have been neutralized. They need time or heat
to hydrolyze fully before adding other ingredients or neutraliz-
ing. When hydrolyzed, they are in the acidic form and may form
insoluble complexes with other ingredients. Therefore, the order of
addition is crucial to formulate clear gels. This is especially true for
polyimide-1 formulations because polyimide-1 has been designed to
complex with carbomer to create synergistic performance benefits.
Polyimide-1 was tested with a variety of rheology modifiers
including carbomer, acrylates C20-30 alkyl acrylate copolymer,
PVM/MA decadiene crosspolymer, and acrylates/beheneth-25
methacrylate copolymer. Within this group of rheology modifiers,
acrylates C20-30 alkyl acrylate copolymer furnished gels with the
highest clarity when using typical component ratios. An acrylates
C20-30 alkyl acrylate copolymer gel measured 25 NTU as opposed
to 45 NTU with carbomer using the same component ratios.
Viscosities are typically in the 20-30,000 cps range using 2% poly-
imide-1 and 0.5% of the rheology modifier.
Acrylates C20-30 alkyl acrylate copolymer was used to observe
the effects of: changes to the neutralizer; concentration; and addi-
tion of ethanol. It was found that reduction of the polyimide-1 /
acrylates C20-30 alkyl acrylate copolymer ratio from 4:1 to 2:1 not
only reduced haze by 50%, but also resulted in a more flexible film.
Addition of ethanol to carbomer gels can prove to be a problem,
even in the absence of polyimide-1, because it reduces both the
ability of carbomer to be quickly dispersed in the solvent system
and the extent of solvation. It was found that addition of ethanol
after a gel is fully neutralized and mixed is superior to adding it
prior to neutralization.
Use of increasingly more hydrophilic amines (particularly inor-
ganic bases) resulted in gels having increased haze and decreased
viscosity. Use of the more hydrophobic bases, such as triisopropa-
nolamine, drastically improved hydroalcoholic gels in terms of both
clarity and viscosity. A hydroalcoholic gel prepared with NaOH
measured 37 NTU and 8800 cps while the same gel prepared with
triisopropanolamine measured 23 NTU and 20000 cps.
A typical procedure for preparing a gel formulation of polyim-
ide-1 is:

333
Clements Chapter 34
1. Prepare a diluted solution of the thickener;

2. Achieve 100% neutralization of the thickener solution to
form the gel;
3. Add polyimide-1.
Flexibility, Toughness and Durability

By conducting studies with the Dynamic Hair Spray Analysis
(DHSA) on omega loops of hair (Figure 5) and the Cantilever
3-Point Bending method (Figure 6) on flat hair tresses, the stiff-
ness, stiffness ratio, flexibility and durability under normal and high
relative humidity of polyimide-1 have been quantified.
Figure 5. Flexibility of the polymer film on hair and durability of the hair set, from Dynamic
Hair Spray Analysis on omega loops of hair treated with selected polymer combinations

334
DHSA: When a treated omega loop of hair is depressed and bent

10 times at 50% RH using DHSA, the maximum force needed to
depress the curl and the resiliency of the curl is obtained (Figure
5). The smooth curve at the top of the peaks and the overlapping
multiple hysteresis loops indicate the flexibility of the polymer film
on hair and durability of the hair set. The vertical Y axis shows the
number of grams of force needed to depress the curl at the depth (in
mm) shown on the X axis.
Using DHSA, the resiliency and durability of polyimide-1, car-
bomer, PVP/carbomer and polyimide-1/carbomer were compared
on hair set into omega loops. F1 is the maximum force attained dur-
ing the first 4 mm depression. The stiffness ratio can be calculated
from the force needed to depress the set hair to 1 mm (a region that
is mostly elastic and reproducible after several depressions if 1 mm
isnt exceeded) divided by the force needed to depress untreated hair
1 mm. Then resilience and durability measurements are calculated
by the ratios of the maximum force at the first depression compared
to the maximum force at the 10th depression (F1/F10), the slope of
the 1st depression curve versus the 10th (E1/E10), and the depth of
penetration into the hair loop in order to sense plasticity, 1st ver-
sus 10th (H1/H10). The data in Figure 5 shows that polyimide-1 +
carbomer provides significantly improved resiliency as compared to
carbomer alone or PVP/carbomer systems.
Examination of the DSHA curves indicates the importance of
the ratio of carbomer to polyimide-1. Chart I shows a carbomer
film on hair. Notice the roughness of the first curve. This roughness
indicates that the film is deforming to the point of fracture.
Chart II shows a polyimide-1 film. The first curve is smooth,
indicating deformation without fracture of the film. Chart IV shows
a 4:1 ratio of polyimide-1 to carbomer film. Notice the tightness of
all 10 curves, indicative of a resilient film. Deformation occurs and
the system returns to almost its initial state.
Chart V shows a profile of a 2.6:1 ratio of polyimide-1 to car-
bomer film. This profile indicates some film fracture; the 2.6:1 ratio
blend begins to exhibit properties of a carbomer system.
Chart VI shows a profile of a 6.6:1 ratio blend. All 10 curves are
extremely tight without much deformation. The 6.6:1 ratio blend

335
Clements Chapter 34
exhibits both stiffness (no deformation) and elasticity (returns to

the same position). As with gel clarity, our data indicates that this
synergistic effect with carbomer is also seen with other polyacrylic
rheology modifiers, acrylic-based resins and VP-based resins. The
ratios of polymer to polyimide-1 are dependent on the composition
of the polymer.
Cantilever 3-point bending: Three-point bending measure-
ments were also preformed utilizing a texture analyzer equipped
with a cantilever apparatus. 2 g tresses of 6.5" European dark brown
hair were treated with 1 g of styling gel formulated with 4:1 ratio
of polyimide-1 to carbomer (2.0% active to 0.5% active in water)
and compared to gels formulated with a 1:1 ratio of 2% PVP to
2.0% carbomer. The tresses were allowed to dry straight. The probe
pressed the hair sample until a 2.0 g force was detected and then
a 3.00 mm deformation of the fiber assembly was performed. The
probe returned to the control height and repeated the cycle for a
total of 10 deformations.
We plotted the maximum force ratio of the first to the tenth
deformation at 50% and 90% relative humidity (RH). The force
ratio for the polyimide-1 gel at 90% was close to the value at 50%
RH; the values were 0.835 and 0.695, respectively. For the PVP gel,
the corresponding force ratios were 0.912 and 0.050. Thus, polyim-
ide-1 retains its film integrity even upon exposure to high humidity,
while the PVP fails.
Stress/Strain testing: DSHA and cantilever 3-point bending help
to assess the toughness and durability of a polymer film on a con-
sumers hair when touched, but these tests do not take into account
a consumers motion and activity. ISP is investigating new methods
to more fully quantify and understand polymer performance on con-
sumers hair in real life conditions. One such test evaluates the stress
of a polymer film on a felt substrate as a function of percent of strain
during a twisting motion.
While more work is required to fully validate this method, some
conclusions can be drawn from the results. By examining the curves
in Figure 6 (see Color Insert 14), it is easy to conclude that as
humidity increases, 4:1 polyimide-1/carbomer gel film retains its
strength, while a PVP/carbomer gel film fails.

336
Figure 6. Stress-Strain test on a felt substrate treated with polyimide-1 / carbomer gel
versus a PVP/carbomer gel at moderate and high humidity
Film Surface Properties: Coefficient of Friction

The coefficient of friction has been used to quantify a measurement
for a consumer sense of touch. The coefficient of friction (COF) is
determined by the ease with which two surfaces slide against each
other and is calculated as the ratio of the force required to slide the
surfaces to the force perpendicular to the surfaces. A lower COF
indicates that a surface is smoother, i.e. there is less resistance to the
sliding motion.

337
Clements Chapter 34
Polymers were tested instrumentallyb as dry films on a glass

substrate at 25C and 50% relative humidity. The results shown in
Table 1 indicate that polyimide-1/carbomer systems are smoother
than glass or satin and much smoother than the current gel systems
on the market.
Table 1. Film surface properties of selected materials
Material Average Coefficient of Friction

Teflon 0.341
Polyimide-1/Carbomer gel 0.502
Satin 0.739
Polyimide-1 0.828
PVP K-30/Carbomer gel 0.972
Glass 1.053
PVP K-30 1.101
Sandpaper 1.948
Salon Evaluation of Volume and Body

Better performance in the laboratory does provide information on
how well a styling polymer will perform, but it is not a substitute
for consumer-rated performance of a formulation on a consumers
hair. The results of a 10 person half-head blind-coded salon study
comparing polyimide-1 in a styling gel formulation versus a com-
mercial PVP styling gel are shown in Figure 7 (see Color Insert
14). Polyimide-1 rendered noticeable body versus PVP. Eight out of
ten panelists were of the opinion that hair treated with polyimide-1
provided longer lasting style and more volume. Other attributes that
consumers expect from styling products performed well.
b
SP-2000 Slip/Peel Tester from IMASS Inc.

338
Figure 7. Consumer-rated blow drying performance of a polyimide-1 styling gel (red) versus a
commercial PVP styling gel (blue) in a salon evaluation
Formulation Versatility and Compatibility

The last key factor for a polymer to be successful in the styling
marketplace is formulation versatility and compatibility with other
polymers and materials typically used in hair styling formulations.
Two prototype formulations demonstrate the versatility of polyim-
ide-1 in typical styling formulations.
Formula 1 shows a traditional styling gel that delivers a smooth
feel to hair yet provides a long-lasting, durable style with body and
volume. This product eases blow dryer styling and does not stick to
a curling iron. The end result is manageable hair that can easily be
restyled.
Formula 2 demonstrates polyimide-1 functionality in mousse
applications. This high-powered root lifter leaves hair feeling tex-
tured, yet smooth, with excellent volume and manageability.
Conclusions
The complex styling needs of todays marketplace demand styling
products that provide style longevity, smooth feel and durability in
high humidity conditions. Various test methodologies are needed to

339
Clements Chapter 34
Formula 1. Classical styling gel
Ingredients % w/w
Carbomer 25.00
iodopropynyl butylcarbamate (Liquid Germall Plus, ISP) 0.50
Disodium EDTA (Versene NA, Dow) 0.05
B. Triethanolamine, 99% 0.26
C. Water (aqua) 18.00
Polyimide-1 (Aquaflex XL-30, ISP) 6.67
Triethanolamine, 99% 0.26
100.00
Procedure: Mix A. Add B after A is uniform. Premix C separately. Add C to AB with sweep mixing
to avoid aeration. Continue mixing until uniform. Physical Properties: Appearance - viscous gel;
pH - 6.8; Viscosity - 26,000 cps (DV II/T-C/10 rpm/1 min, 25 C).
Formula 2. 6% VOC root-lifting spray foam
Ingredients % w/w
Water (aqua) 69.56
Polyimide-1 (Aquaflex XL-30, ISP) 13.34
PEG/PPG-25/25 dimethicone (Si-Tec DMC 6031, ISP) 0.15
Polysorbate 20 (Tween 20, Uniqema) 0.15
Cetrimonium chloride (Carsoquat CT-429, Lonza) 0.15
Caprylyl pyrrolidone (Surfadone LP-100, ISP) 0.10
Glyceryl polymethacrylate (and) propylene glycol (and)
PVM/MA copolymer (Lubrajel Oil, ISP) 0.05
iodopropynl butylcarbamate (Liquid Germall Plus, ISP) 0.50
Hydrofluorocarbon 152a (Dymel 152a, DuPont) 10.00
Isobutane 6.00
100.00
Procedure: Add ingredients in order listed, mixing well between each addition. Fill into lined
aluminum cans and charge with propellant. Valve: Precision; Stem S90 013, Body 013 S90
Capillary DT, 040 Capillary Diptube; Actuator: Precision; Kosmos Ext/Nozzle 020 x 041 FT;
01-8894

340
demonstrate a new styling products performance. The tests sur-

veyed here demonstrate that polyimide-1 meets consumer demands
and outperforms current products on the gel and mousse market.
Acknowledgements
J. Albanese, M. Martin, J. Jachowicz, R. McMullen, D. Tobia, J. Katirgis, H. Ulmer, M.
Drzewinski, L. Foltis
Nancy Clements
International Specialty Products, Wayne, NJ USA

Chapter 35
Antichaotropic Salts
for Stabilizing Cysteine
in Permanent Waving
Solutions
KEY WORDS: antichaotropic salts, cysteine, permanent waving solutions,
reducing agents, thioglycolic acid, mercaptans
ABSTRACT: Antichaotropic salts stabilize cysteine by lowering the water
activity in an aqueous solution. This technique can be used
to extend the shelf life of cysteine permanent wave solutions.
Since the 1940s,1 it has been common practice to curl or wave

human hair with a reducing agent at a relatively high alkaline pH.
The theory of this process is that the reducing agent severs the
cystine (disulfide) linkages in the keratin (hair) molecule, thereby
permitting them to be reformed in new positions by an oxidizing
agent after being wound around a mandrel or curling rod, thus caus-
ing a curl formation to occur.
This process has not changed in more than 60 years, but there
have been different suggestions in the choice of reducing agent
employed. By far, the reducing agent used the most is a suitable
saltthioglycolic acid, HS-CH2COOH. There have been other
mercaptanschemicals with a sulfhydryl (SH) groupsuggested2
such as thiolactic acid, thiomalic acid and -mercaptoproproionic
acid; however, these 3 mercaptans are all highly malodorous, causing
them to be rejected by the consumer as inelegant and nonaesthetic.
For this reason, certain inorganic reducing agents have been pro-
posed (e.g., ammonium bisulfite and other bisulfite salts.). Although
these reducing agents have a lower inherent odor, they also have

342
Styling Antichaotropic Salts for Stabilizing Cysteine
limited wave producing potentiality, thus making them unsuitable

for universal use.
Cysteine is an amino acid with a mercaptan group: HS-
CH2CHNH2COOH (see Mercaptan Groups). Cysteine has
demonstrated its ability to produce efficient waving when it is
substituted for thioglycolic acid in permanent wave solutions. It
has a lower odor value than thioglycolic acid, which, if need be, can
be effectively masked with essential oils. Cysteine, however, has a
very short shelf life when dissolved in an aqueous solution, wherein
it quickly reverts to the cystine form that contains the disulfide,
which is insoluble in an aqueous solution and eventually appears as
a precipitate. For this reason, commercial products have contained
a separate component of the dry cysteine crystals to be added to
the aqueous solution just prior to use on the hair. In addition, there
have been stabilizers suggested such as sucrose, which, although it
protects cysteine in aqueous solutions, seems to inhibit its reducing3
potential by producing permanent solutions of lower efficiency.
Mercaptan Groups
Thiols are sulfur analogs of alcohols with an SH group in place of the
OH. The SH group is called a mercaptan, meaning captures mercury,
because thiols have the ability to form stable heavy-metal derivatives.
This ability of complexing heavy metals is useful for treating people
with heavy-metal poisoning from mercury or arsenic. Thiols also have a
characteristically strong odor associated with them. For example, thiols
are responsibible for skunk scent and garlic scent. Thiols are named like
alcohols with a thiol suffix. Common names use the alkyl group with the
word mercaptan attached.
Source: University of Pennsylvania School of Arts and Sciences. Available at http://www.sas.

upenn.edu/-snmartin/Chem501-2.html. Accessed June 13, 2005
This chapter proposes the use of certain salts for the stabilization
of cysteine. These salts are referred to as antichaotropic salts because
they are structure making, in that they increase the ordering of

343
Shansky Chapter 35
water molecules at interfaces.4 Antichaotropic salts, when dissolved

in water, raise the surface tension of the medium by increasing the
ordering of water molecules at interfaces, which effectively lower the
activity of water at the interface.5 Other components dissolved in
the medium (e.g., cysteine) also present an interface at a molecular
level. The lowered water activity at this molecular interface, particu-
larly around the less polar moieties, will enhance the ability of these
components to resist chemical change.6 Therefore, cysteine in the
presence of an antichaotropic salt will be prevented from being oxi-
dized to the insoluble cystine because the chemical activity of such a
reaction will be lowered by the lowered water activity.
Some antichaotropic salts found useful for this purpose are
shown in Table 1.
Table 1. Molal surface tension increment, x 103, and

solubility for various salts
Dyne g Solubility
cm mol gm/100 cc
Sodium citrate, Na3C6H5O7 . 2H20 3.12 72.50
Sodium sulfate, Na2SO4 2.73 142.04
Potassium sulfate, K2SO4 2.58 12.00
Ammonium sulfate, (NH4)2SO4 2.02 70.60
Potassium tartrate, K2C4H4O6 . H2O 1.96 100.00
Sodium chloride, NaCl 1.64 35.70
Ammonium chloride, NH4Cl 1.39 29.20
Sodium bromide, NaBr 1.32 116.00
Sodium nitrate, NaNO3 1.06 92.10
In addition to high molal surface tension increment ( x 103),

solubility of the salt is an ancillary consideration. Salts of high
solubility together with high molal surface tension are most desired.
For this reason, sodium citrate is optimum, as shown in Table 1, fol-
lowed by sodium sulfate, ammonium sulfate and potassium tartrate.

344
Ammonium chloride is the least suitable followed by potassium

sulfate. Also, salts that tend to have specific binding effects (e.g.,
magnesium chloride, calcium chloride) should be avoided despite
their high molal surface tension increment.
Formula 1 lists the ingredients in a typical cysteine permanent
wave solution.
Formula 1. A typical cysteine permanent wave solution
Water (aqua) 60.00% w/w

Sodium citrate 5.00
L-cysteine HCl 15.00
Ammonium hydroxide, 28% 19.00
Nonoxynol-9* 1.00
100.00
pH=9.4
*The ethoxylated alkyl phenol that conforms generally to the formula:

C9H19C6H4(OCH2CH2)nOH n=9
The percentage of sodium citrate can vary from 1% to 6%, with

an optimum of approximately 2.5% The percentage of cysteine
can vary from 8% to 15%, with an optimum of approximately 12%.
The ammonium hydroxide must produce a pH range of pH 9.0 to
pH 9.6, with an optimum of pH 9.3. The ammonium hydroxide
may be replaced with a fixed alkali such as monoethanolamine. All
replaceable alkalis must exhibit partial dissociation. Alkalis that
completely dissociate sodium and potassium hydroxide are not suit-
able for this system.
In addition to the aforementioned formula, it is possible to
substitute part of the cysteine with other reducing agents such as
cysteamine as shown in Formula 2.
Also, an example of a cysteine formula containing a partial
amount of thioglycolate is show in Formula 3.

345
Shansky Chapter 35
Formula 2. A typical cysteine permanent wave solution

substituting part of the cysteine with other reducing agents

L-cysteine HCl 6.00
Cysteamine HCl* 7.00
Sodium citrate 2.50
Monoethanolamine 12.00
Nonoxynol-9 1.00
100.00%
pH=9.4
*Cysteamine HCl is the amine salt that generally conforms to the formula: HSCH2CH2NH2 HCl
Formula 3. A cysteine formula containing a partial amount

of thioglycolate

L-cysteine HCl 8.00
Ammonium thioglycolate, 60% 4.00
Sodium citrate 2.50
Monoethanolamine 10.00
Nonoxynol-9 1.00
100.00
pH=9.2
These formulas may all be prepared with conditioning agent

adducts such a protein derivatives, cationic agents, silicones, oils
and hydrocolloidal gums. The formulas may include small quanti-
ties of fragrance and emulsion or resin opacifying agents for elegant
appearance, odor and haptic sensation.
Albert Shansky, PhD

Albert Shansky Consultants Inc., Norwalk, CT USA

346
References
1. British Pat 589,956, Sales Affiliates (1941)
2. EG McDonough, Mercaptans in cosmetics, Am Perfumer (Nov 1947)
3. US Pat 4,947,878 Crews et al. (1990)
4. RE Shansky, SL Wu, A Figueroa, BL Karger, HPLC of Biological Macromolecules, New
York: Marcel Dekker Inc. p 103 (1990)
5. C Tanford, The Hydrophobic Effect: Formation of Micelles and Biological Membranes,
2nd ed, New York: Wiley-Interscience (1973)
6. R Scopes, Protein Purification, New York: Springer-Verlag, p 199 (1982)

Chapter 36
Refractive Index
Matching: Principles and
Cosmetic Applications
KEY WORDS: refractive index matching, clear emulsion, formulation
strategies, skin care, hair care
ABSTRACT: Clear emulsion formulas can be achieved by matching
refractive indexes (RI) of water phase and oil phase. The
match is achieved by varying the ratio of water and glycols,
as shown in several skin and hair care formulas.
Current consumer trends favor clear products in the cosmetic mar-

ket. To meet this requirement, chemists have developed two ways
to make clear emulsions: by micro emulsion1 and by refractive index
matching.2 The former has been widely explored, leading to many
microemulsion-conditioning products in the market. In contrast, the
latter has not been widely explored because the physical principle is
not well explained and there has been no practical methodology to
follow to realize many different applications.
In our exploration of refractive index matching in formulation of
cosmetics, a practical method has been developed and leads to many
unique formulations. Refractive index matching enables chemists to
make many unique formulas that cannot be achieved by other meth-
ods. Refractive index matching should become a common technique
for formulation chemists.
Physical Principle of Index Matching

Optical refraction: Consider a beam of light transmitted through air
and directed onto the surface of a body of water. Some of the light
is reflected at the interface between the air and water; the remainder

348
Styling Refractive Index Matching: Principles and Cosmetic Applications
enters the water and is transmitted through it. Every transparent

material has a property called optical density, which is an inverse
measure of the speed of light through the material. Because water
has a higher optical density than air, the speed of light is reduced
as the light enters the water. The beam of light changes direction
abruptly as it enters the water because of the change in speed. This
bending of the light ray is called optical refraction.
Index of refraction: The ratio of the speed of light in a vacuum
to its speed in a substance is called the index of refraction for that
substance or the refractive index (RI). The index of refraction of
a homogeneous substance is a constant quantity that is a definite
physical property of the substance. Consequently, the identity
of such a substance can be determined by measuring its index of
refraction with an instrument known as a refractometer. Some
indexes of refraction for common cosmetic ingredients are listed in
Table 1.
What cosmetic chemists want to know is how to calculate the
refractive index of a solution and how to design a formula with the
refractive index of each ingredient in solution. Experimentally, it
turns out that if one mixes several miscible ingredients together to
form a clear homogeneous liquid phase, the refractive index of the
mixture can be calculated from each individual components refrac-
tive index in the composition. The calculated value of refractive
index normally is very close to the value measured instrumentally.
For example if one mixes glycerin (RI = 1.468) and water (RI
= 1.330) at 50:50 (weight ratio) compositions, the final refractive
index of mixture is calculated by taking average of refractive index
of these two components (RI = [1.468+1.330]/2 = 1.399). A plot of
refractive indexes versus the percentage concentration of glycerin
in aqueous solution is given in Figure 1. The measured RI values
of solutions at different concentrations also compare to the values
calculated from two components. It is apparent that experimental
values deviate only very slightly from calculated values.
One can generalize a universal equation for calculating RImix, the
refractive index of a clear homogeneous liquid mixture (Figure 2).
If W represents the weight percentage of each component and RI
represents the refractive index of each component, then the RI of

349
Sun et al. Chapter 36
Table 1. Selected refractive index (RI) values of some

common cosmetic ingredients
Ingredient RI value
Water, deionized 1.3300
Glycerin 1.4680
Hexylene glycol 1.4276
Butylene glycol 1.4401
Propylene glycol 1.4355
Glycereth-7 (Liponic EG-7, Lipo Chemicals) 1.4720
PEG-4 (Carbowax PEG 200, Union Carbide) 1.4582
PEG-6 (Carbowax PEG 300, Union Carbide 1.4615
VP/VA Copolymer (Luviskol VA 73W, BASF AG) 1.4275
PVP (Luviskol K30, BASF AG) 1.3805
Cyclomethicone and dimethicone (DC 1501, Dow Corning) 1.3972
Cyclomethicone (Rhodorsil 45V5, Rhodia) 1.3960
Cyclomethicone (and) phenyltrimethicone (and)
dimethicone (Gelaid 5565, Chemsil) 1.4015
Cyclomethicone and dimethicone copolyol (DC 5225, Dow Corning) 1.3975
Polyacrylamide, C13-14 isoparaffin, laureth-7 (Sepigel 305, Seppic) 1.4460
Sodium acrylate/acryloyldimethyl taurate copolymer, isohexadecane,
polysorbate 80 (Simugel EG, Seppic) 1.4450
Hydroxyethylacrylate/sodium acryloyldimethyl taurate copolymer,
squalane and polysorbate 60 (Simugel NS, Seppic) 1.4475
C13-14 Isoparaffin (Isopar M, Exxon Mobil Chemical) 1.4380
C11-13 Isoparaffin (Isopar L, Exxon Mobil Chemical) 1.4255
the mixture will be determined by equation 1 and 2, which simpli-

fies to equation 3.
Refractive index matching: By using equation 3, one can calculate
clear water solutions containing several functional cosmetic ingredi-
ents and also clear oil phase solutions containing several functional
cosmetic ingredients. It is possible to match the refractive index
of the water phase to that of the oil phase. Furthermore, it is pos-
sible to make a clear or opalescent emulsion by combining a water
phase and an oil phase that have equal refractive indexes. In order to
directly use equation 3 for refractive index matching in an emulsion,

350
equation 3 could be modified as shown (Figure 3) in equation 4 for

RIoil and equation 5 for RIwater.
Figure 1. RI values - measured and calculated - of glycerin aqueous solution
Figure 2. A universal equation for calculating the refractive index of clear homogeneous
liquid mixtures
Figure 3. Refractive index matching for an emulsion

351
In reality, emulsifiers have to be dissolved in either oil phase or

water phase, so it is necessary that either phase has to be clear or
close to clear.
There are some limitations for using equations 4 and 5.
Firstly, there should be no reactions between ingredients in either
the water phase or the oil phase. Even neutralization will change
the refractive index of ingredients. For example, 10.0% glycolic acid
at pH = 3 has RI = 1.3450; at pH = 4, RI =1.3555. Glycolic acid
and glycolate anion (neutralized by triethanolamine) have different
refractive indexes.
Secondly, the ingredients in the oil phase should be physically
insoluble in the water phase, and vise versa. In another words, the
ingredients chosen for use in the formula should not have dual dis-
tribution in both the water phase and the oil phase. Any emulsifier
(or blended emulsifier ingredients) should stay only at the interface
of their original phase and cannot be allowed to permeate into the
other phase.
Thirdly, it is necessary to produce the emulsions at room temper-
ature because RI values are temperature-dependent, and normally
the oil phase and the water phase differ in their temperature depen-
dency. If the clear emulsion were made at elevated temperature, the
emulsion most likely would be cloudy or hazy at room temperature.
Choosing an emulsifier is also a crucial step to get a clear emul-
sion. Based on the nature of the emulsions, some recommended
emulsifiers are shown in Table 2.
Chemists can take advantage of these equations to design their
formula to meet the specific requirement of appearance and perfor-
mance. After the RI of the two phases has been matched (become
equal) and the two phases have been mixed together, the emulsion
could be slightly cloudy at first. Longer mixing time is needed to
make the emulsion homogeneous and clear. It is worth noting that
water-in-silicone oil emulsions perform the best in skin care prod-
ucts and oil-in-water emulsions perform best for hair care products.
Example applications: The following examples show RI applica-
tions in cosmetic formulations based on the principles previously
described. Two formulas for skin care and two formulas for hair care
are illustrated. To illustrate the formulation designing process, only

352
simplified formulas are used. They are by no means the formulas

with the best performance.
Table 2. Recommended emulsifiers for obtaining clear

emulsions
Emulsifier Emulsion type

Cyclomethicone (and) dimethicone copolyol
(Dow Corning 5225, Dow Corning) water-in-silicone
Polyacrylamide, C13-14 isoparaffin (and)
laureth-7 (Sepigel 305, Seppic) silicone- or isoparaffin-in-water
Sodium acrylate/acryloyldimethyl taurate
copolymer, isohexadecane (and) polysorbate 80
(Simugel EG, Seppic) silicone- or isoparaffin-in-water
Hydroxyethylacrylate/sodium acryloyldimethyl
taurate copolymer, squalane (and)
polysorbate 60 (Simugel NS, Seppic) silicone- or isoparaffin-in-water
The applications are not limited to the examples shown. The

chemist can design many different formulas with many different
ingredients by using the principles already described. This method
could also be used for designing general dual-phase products with
two different colors in two phases.
RI Matching in Skin Care Products

Clear AHA gel: Alpha hydroxy acids (AHAs) have been determined
to have antiaging and antiwrinkle effects. AHAs have been widely
used in skin care formulations.3,4 However, AHAs are also skin
irritants. By incorporating an AHA complex (glycolic acid and argi-
nine) to form a water-in-silicone oil emulsion, we are able to obtain
a clear eye gel product with AHAs that are much less irritating.
Formula 1 shows the preliminary formula with the corresponding
RI. The related RI calculation is also given for RIoil (1.3966) and
RIwater (1.3964) as an example for using equations 4 and 5.

353
Formula 1. Clear eye-moisturizing gel
Ingredient Weight % RI value
Silicone oil phase

Cyclomethicone and dimethicone (DC 1501, Dow Corning) 10.0 1.3971
Cyclomethicone and dimethicone copolyol
(DC 5225, Dow Corning) 10.0 1.3975
Cyclomethicone (DC 344, Dow Corning) 5.0 1.3942
AHA water phase

Water, deionized 35.5 1.333
Glycerin 27.0 1.468
Glycolic acid and arginine (AHCare G-60, Cognis) 12.5 1.428
100.0
RIoil = (10x1.397 + 10x1.398 + 5x1.394)/25 = 1.3966
RIwater = (35.5x1.333 + 27x1.468 + 12.5x1.428)/75 = 1.3964
Antiaging gel containing ascorbic acid or sodium ascorbyl phos-

phate: Ascorbic acid (vitamin C) has a confirmed ability to stimulate
collagen synthesis in human dermal fibroblasts by increasing the rate
of transcription of the collagen genes.5,6 It has also been found to
act as a major antioxidant, anti-inflammatory and inhibitor of the
enzyme tyrosinase.7 However, ascorbic acid has been found to be
easily oxidized in aqueous solution. Therefore a gel-like product is
recommended to prevent oxidation of ascorbic acid.
The alternative form of ascorbic acid is sodium (or magnesium)
ascorbyl phosphate.8,9 Sodium ascorbyl phosphate is a stable form
of ascorbic acid and will deliver ascorbic acid after applied on skin.
Formula 2 gives the preliminary formula with corresponding RI for
an antiaging gel. The related RI calculation yields 1.3971 for RIoil
and 1.3970 for RIwater.

354
Formula 2. Clear W/O gel containing sodium ascorbyl

phosphate
Silicone oil phase

Cyclomethicone and dimethicone (DC 1501, Dow Corning) 4.00 1.3972
Cyclomethicone and dimethicone copolyol
(DC 5225, Dow Corning) 10.00 1.3975
Cyclomethicone (Rhodorsil 45V5, Rhone Poulenc) 11.00 1.3942
Sodium ascorbyl phosphate water phase

Glycereth-7 (Liponic EG-7, Lipo) 28.60 1.4720
Sodium ascorbyl phosphate, 13.16% soln 38.00 1.3550
DMDM hydantoin (Glydant, Lonza Group) 0.15 1.4250
100.00
RIoil = (4x1.3972 + 10x1.3975 + 11x1.3942)/25 = 1.3971
RIwater = (8.25x1.3330 + 28.6x1.4720 + 38x1.3550 + 0.15x1.425)/75 = 1.3970
This is an interesting example because it shows that one can

incorporate solid ingredients to get an RI match to achieve clear or
opalescent products. Magnesium ascorbyl phosphate could also be
used in the same way to make clear gel.
RI Matching in Hair Care Products

O/W hair silicone styling gel: Silicone oil has been widely used to
deliver shine, luxury feel, anti-frizz and manageability in hair care
products. Hair fixative ingredients (such as PVP/VA or PVP) have
also been widely used in carbopol gels, giving styling effects for hair.
The interesting point here is that if one can combine silicone oil and
hair fixatives into a clear gel-like product, the new product will have
great shine, luxury feel and manageability from silicone. At the same

355
time, the product will also have styling function from the fixative
resins. As shown in Formula 3, the principle of RI matching can be
used to make the clear silicone styling gel with a value of 1.4060 cal-
culated for both the RIoil and the RIwater.
Formula 3. Clear O/W silicone gel containing PVP/VA
Silicone oil phase

Cyclomethicone (Rhodorsil 45V5, Rhodia) 4.00 1.396
Polyacrylamide, C13-14 isoparaffin, laureth-7
(Sepigel 305, Seppic) 3.00 1.446
Cyclomethicone (and) phenyltrimethicone (and)
dimethicone (Gelaid 5565, Chemsil) 20.00 1.402
PVP/VA water phase

PVP/VA copolymer soln (50% active)
(Luviskol VA 73W, BASF) 25.00 1.427
100.00
RIoil = (4x1.396 + 3x1.446 + 20x1.402)/27 = 1.4060
RIwater = (26.5x1.333 + 21.35x1.472 + 25x1.427 + 0.15x1.425)/73 = 1.4060
O/W isoparaffin glossing styling gel: It has become a general

knowledge that an oil ingredient with higher refractive index usually
will give more shine for hair. The isoparaffins usually have higher RI
than silicones. This suggests incorporating isoparaffin with PVP/VA
in a formula, such as Formula 4, to get a clear glossing gel. This gel
will deliver silicone-free, high glossing, moisture-balanced styling
performance to hair. For this gel, a value of 1.4369 was calculated
for both the RIoil and the RIwater.

356
Formula 4. Clear O/W isoparaffin gel containing PVP/VA
Isoparaffin oil phase

C11-13 Isoparaffin (Isopar L, Exxon Mobil) 4.00 1.425
Polyacrylamide, C13-14 isoparaffin, laureth-7
(Sepigel 305, Seppic) 3.00 1.446
C13-14 Isoparaffin (Isopar M, Exxon Mobil) 20.00 1.438
PVP/VA water phase

PVP/VA copolymer soln (50% active)
(Luviskol VA 73W, BASF) 25.00 1.427
100.00
RIoil = (4x1.425 + 3x1.446 + 20x1.438)/27 = 1.4369
RIwater = (10.25x1.333 + 37.6x1.472 + 25x1.427 + 0.15x1.425)/73 = 1.4369
Deviations and Practical RI Adjustment

The calculation of refractive index for solutions only applies for
the ideal solutions or ideally dilute solutions. In ideal solutions,
the molecules of the various species are so similar to one another
that molecules of one component can replace molecules of another
component in the solution without changing the solutions energy
or spatial structure. In ideally dilute solutions, all solutes are pres-
ent in very low concentrations and the solvent weight percentage
approaches 100%.
In cosmetic formulations, the solutions are neither ideal nor ide-
ally dilute solutions because the solvent and solutes can not be very
similar, and the concentrations of solutes can not be impractically
low. They are nonideal solutions containing both electrolytes and

357
nonelectrolytes. The precise calculations will need to use chemical

potential (mi), solutes activities (ai) and activity coefficients (gi). The
calculation will become very complicated and impractical for cos-
metic chemists. Fortunately, a simplified calculation is sufficient to
serve the purpose of designing the formulation.
In the process of making the oil phase and water phase for
Formulas 1 through 4, RI will deviate slightly from the calculated
value. The deviation in the oil phase is usually very small because all
the RI values of the oil phase ingredients are very close. The molec-
ular structures of oil phase ingredients are also similar so that the
molecular interaction between these ingredients is not very different.
However, there is a noticeable RI deviation in the water phase
preparation because water has a very low RI value and glycols have
very high RI values. In addition, the molecular interaction between
glycol and water is different than the interaction between glycol
molecules or the interaction between water molecules. Therefore the
formula needs further refinements to assure index matching of oil
phase and water phase.
Various glycols are used to raise the refractive index of the aque-
ous phase to match the silicone oil (RI ~ 1.4) or isoparaffin (RI ~
1.43). The refractive index values for several glycols as a function
of concentration are shown in Figure 4 for a two-components
system. The glycol aqueous concentrations are varied from 10% to
80%. Different deviations are seen in the plot. Glycerin has slightly
negative deviation and all others show positive deviation. Hexylene
glycol shows the biggest positive deviation. The deviation is also
concentration dependent.
To demonstrate the positive and negative deviation, we plotted
the refractive index values of hexylene glycol and glycerin aqueous
solution versus percentage concentration in Figure 5.
In Figure 5, the largest negative deviation is seen for glycerin at
the concentration of 30%, where there is a -0.51% deviation (1.367-
1.37395 = -0.00695) from the calculated value.
Hexylene glycol shows the largest positive deviation among all
the studied glycols (Figure 4). The experimental RI value of hexy-
lene glycol is even larger than the value of glycerin solution (Figure
5) at concentrations in the range of 10-35%. The largest deviation

358
of refractive index for hexylene glycol is at the concentration of 60%,

where it deviated 0.97% from the calculated value.
Figure 4. RI values of glycol aqueous solutions
Propylene glycol, butylene glycol and hexylene glycol all show

positive deviation (Figure 4). However, propylene glycol has least
deviation and hexylene glycol has largest deviation. The nature of
the deviation may be related to the molecular interaction between
water molecules and between glycol molecules as well as between
water and glycol molecules. These three glycols have the same diol
(dihydroxy) function groups on two carbon atoms. The more carbon
the molecule has, the more difference there will be in the molecular
interaction between glycol and water molecules. The more differ-
ence there is in the molecular interaction between glycol and water
molecules, the more positive is the observed deviation (Figure 4).
It is apparent that the most efficient way to raise the refractive
index of the aqueous phase is use a combination of hexylene glycol
in the range of 20-30% with either glycerin, glycereth-7 or buty-

359
lene glycol. Propylene glycol is less efficient at raising the RI of the

water phase because it has the least positive deviation and the lowest
refractive index value in the group.
In the formulation process, one has to consider, among other
factors, the formulation performance, ingredient cost and ease of
operation. Although the examples presented here are not the best
performers or the best formulas, they do illustrate the use of refrac-
tive index matching to design new formulas by combining equation
4, 5 and Figure 4.
Figure 5. RI deviation of glycerin and hexylene glycol aqueous solutions
Refractive index matching enables chemists to make unique

formulas that are unachievable by other methods. Refractive index
matching could become a common means for developing the next
generation of cosmetic formulas.
Summary
A simple calculation scheme has been developed for designing
clear emulsion formulas by matching the refractive indexes of the

360
water phase and the oil phase. The RI value of the water phase was
adjusted by varying the ratio of water and glycols. Some positive
deviations and negative deviations were observed for water-glycol
two-component system. The use of index calculation and deviations
leads to more precise formulation design.
James Ziming Sun, PhD, Michael C. E. Erickson and James W. Parr

Advanced Research Laboratories, Costa Mesa, CA USA
Published January 2003 Cosmetics & Toiletries
References
1. Clear gels of ethnic hair care, Formulary Ideas and Innovations for Personal Care, a
technical publication from Croda Inc (1996) p A23
2. Using Silicone Formulation Aids to Formulate Cosmetic System, a technical publication
from Dow Corning (1995) p 6
3. K Kostarelos, T Tselepi and A Teknetzis, AHA and exfoliative skin diseases, Cosmet Toil
114(6) 43-50 (1999)
4. DS Orth, J Widjaja, L Ly, N Cao and WB Shapiro, Stability and skin persistence of
topical products, Cosmet Toil 113(10) 51-63 (1998)
5. H Zhai and HI Maibach, Skin-Whitening agents, Cosmet Toil 116(1) 20-25 (2001)
6. GM Silva and PMBG Maia Campos, Influence of a formulations pH on cutaneous
absorption of ascorbic acid, Cosmet Toil 116(1) 73-75 (2001)
7. C Fox, Ascorbic acid for photodamage, Cosmet Toil 115(3) 27-28 (2000)
8. A Jentzsch, H Streicher and K Engelhart, The synergistic antioxidative effect of ascorbyl
2-phosphate and alpha-tocopheryl acetate, Cosmet Toil 116(6) 55-64 (2001)
9. PMBGM Campos and DM Silva, Ascorbic acid and its derivatives in cosmetic
formulations, Cosmet Toil 115(6) 59-62 (2000)

Chapter 37
A New Dimension
in Hairstyling VP/
Methacrylamide/Vinyl
Imidazole Copolymer
KEY WORDS: Styling polymer, hair gels, hair mousses, nanoindentation,
mechanical measurements
ABSTRACT: Data on friction, hardness, tack and other mechanical
properties obtained from a nanoindenter on an atomic
force microscope combined with conventional stress
strain measurements demonstrate the potential of VP/
methacrylamide/vinylimadazole copolymer, a new
hairstyling polymer.
Hair gels and mousses have a high rank among styling products.
Approximately half of the styling polymers are employed in
these application forms, and approximately 25% are used in
gel formulations.1
Gels are favored for short hairstyles and are particularly used by
men. Due to VOC regulations, the trend in the United States is
toward water-based styling gels and mousses away from aerosol
hairsprays with propellant and solvent. In Asia, water-based and
alcohol-free styling formulations are correlated with purity and
traditionally preferred. On strong, dark Asian hair, styling gels and
mousses accomplish good setting without flaking.
Most of the hair gels on the market have cross-linked poly-
acrylic acid as the thickener because it gives them an important
advantage: they are thixotropic and have a yield point. This means
that they are effortlessly taken from a container, do not flow from

362
Styling A New Dimension in Hairstyling
the hand, and are easily dispersed on hair. But, only a limited number
of setting polymers in these gels are compatible with the thickener.
Almost every cationic or anionic setting polymer is incompatible
with cross-linked polyacrylic acid, which leads to turbid formulations
or precipitation, poor gel rheology, or instability.
Therefore, we set out to create a specialty polymer for clear hair
gels. The required properties were excellent clarity in hair gel for-
mulations with cross-linked polyacrylic acid, very low tack, high
setting effect and high resistance to humidity. Many of these prop-
erties were determined conventionally on human hair as well as with
a nanomechanical testing device.
New material development and understanding existing market
products requires testing of surfaces or thin films at smaller scales
for elastic and friction properties. Nanomechanical testing with a
nanoindenter on the atomic force microscope (AFM) provides data
with small forces and high lateral resolution, especially thin surface
layers down to 100 nm.
Viscoelastic materials such as hair care polymers for styling
applications were investigated with this method. These data were
compared with data on the sensory assessment of personal care for-
mulations applied to human hair. Subjective manual test results and
nanomechanical AFM data of various hair care products evidently
correlate to each other. Accordingly, the combability of hair after
polymer application is associated to the reduced microscopic friction
coefficient determined by a nanoscratching device on polymer films.
Polymer raw materials as well as complete cosmetic formulations
such as styling gels were tested regarding their performance.
These insights into the mechanical properties of materials
were used to create new polymers with defined structures. Nano-
mechanical testing was recognized as a useful method for the
investigation of cosmetic polymers and polymer-containing
cosmetic formulations.
The specialty polymera we developed has the INCI name VP/
methacrylamide/vinyl imidazole copolymer. In this article, we will
refer to it as VPMVI copolymer. It is a 20% aqueous solution of a
a
Luviset Clear, BASF, Ludwigshafen, Germany

363
Wood et al. Chapter 37
copolymer of N-vinylpyrrolidone, methacrylamide and N-vinylimi-

dazole (Figure 1).
Figure 1. Structure of VPMVI copolymer
Mechanical Properties of Films

The mechanical properties of VPMVI copolymer were opti-
mized during its development. An important requirement for high
setting effect is a high tensile strength of the polymer film (Figure
2). The mechanical properties of several polymer films (34.5mm
long by 6.0mm wide by0.13-0.15 mm thick) were determined
with a solids analyzerb in a measuring chamber with defined relative
humidity of 55%. The VPMVI copolymer was compared to PVP
K90 and PVP K30c which are the conventional setting polymers
used in hair styling gels. The comparison shows the much higher
tensile strength of the VPMVI copolymer.
Tack at various humidities: The nanoindentation method is
appropriate to study material properties fast and reliably at various
relative humidities in a climate chamber. A nanoindenterd was used
for the nanomechanical measurements (Figure 3). During opera-
tion, the probe tip is first lowered into contact with the sample,
then indented into the surface, and finally lifted off the sample
surface. The indentation depth and the actual force applied to the
tip are recorded simultaneously by an electromechanical capacitative
b
Rheometric Scientific Solids Analyzer RSA II, New Castle, Delaware, USA
c
Luviskol K30 and Luviskol K90, BASF Corp., Mt. Olive, New Jersey, USA
d
Hysitron Nanoindenter, Hysitron, Minneapolis, Minnesota, USA

364
2D-transducer. A plot of the vertical force as a function of inden-

tation depth for one complete indentation and retraction cycle is
called a load displacement curve. Such curves were obtained from
about 20 different areas on duplicate surfaces. Hardness and reduced
E modulus were calculated from the load displacement curves using
an algorithm for an elastic/plastic indentation.2-5
Figure 2. Stress-Strain measurement of polymer films VPMVI, PVP K90 and PVP K30 (250-
500 m; 55% RH)
Figure 3. Hysitron nanoindenter (DI-AFM D3100)

365
The low tackiness of VPMVI copolymer (panel test, subjective

and objective tests on glass plates) is supported by the nanoindenta-
tion measurements. Contrary to PVP, there is almost no dependence
on relative humidity with the new setting polymer (Figure 4).
Figure 4. Tackiness of polymer films measured with Hysitron nanoindenter
Friction coefficient: The nanoscratch experiment was performed

by applying a constant vertical force of 10N and a constant
lateral velocity of 500nm/s. The so-called friction coefficient R
from nanoscratching was determined from the ratio of lateral force
to normal monitored during scratching. VPMVI copolymer has a
strikingly low friction coefficient at high relative humidity (Figure
5). The experience with different polymers substantiates a cor-
relation between friction and combability of hair.6 A low friction
coefficient (as in the new setting polymer) goes along with ease
of combing.
Tack while drying: A tack testere revealed substantially lower
tackiness than PVP during the drying period of the polymer film
(Figure 6).
e
Tack Tester, A. Coesfeld Ltd., Dortmund, Germany

366
Testing the Properties of Gels or Mousses

Tackiness of gels after drying: The tackiness is evaluated with
mechanical testing as well as with sensory assessment.
Figure 5. Friction coefficient of polymer films measured by Hysitron nanoindenter

(Nanoscratching, load = 50 N)
Figure 6. Tackiness of polymer films during drying. Measured by Diastron method. Hair gels
with setting polymer at 3%.

367
During the mechanical testing, the tested gel is spread with a

120 m spiral coater on a glass plate. The dry film on the glass
plate is put into a climate chamber at 25C and 90% relative
humidity overnight. A rubber stamp presses a carbon band for 10
seconds onto the polymer film. The stickier the polymer surface is,
the more printing ink from the carbon band adheres to the polymer
film. The print is evaluated to a ranking from 0 (not tacky) to 5
(very strongly tacky).
For the sensory assessment, the tested gel is applied to a hair
swatch. After drying, the tackiness is evaluated by at least two
persons. They press their hands on a damp cloth and subsequently
compress the hair swatch for 10 seconds in their hands. At release,
the stickiness is evaluated with a ranking from 0 (not tacky) to 3
(strongly tacky). For comparison, always a standard should be used
in parallel.
Tackiness of gels during drying: With a tensile testerf, the force
until separation (given in Newtons) of a metal stamp pressed on a
drying polymer film is measured as a function of drying time. The
measurement is performed in a climate chamber at 20C and 65%
relative humidity.
Stiffness test: The stiffness test is the determination of the bend-
ing stiffness of a gel. The tested gel is diluted until a low viscous
mass is formed. Hair tresses are dipped repeatedly into the diluted
gel. Excess gel is wiped off and formed by hand to a round cross-
section. At 20C and 65% relative humidity, the tresses are dried
overnight. The measurement of the bending stiffness is performed
with a tensile tester. During testing, the gel film breaks, and the
needed force in Newtons is monitored. Each sample of diluted gel is
tested with at least five different hair tresses for its bending stiffness.
With mousses, the wet hair tresses are dipped into the solution
of the mousse formulation containing setting polymer and prepared
as described above. The measurement of the bending stiffness is
performed as described above.
Curl retention of a gel or a mousse: A sufficient amount of the
tested gel is spread on a glass plate, and the gel is applied with a
f
Tensile Tester, A. Coesfeld Ltd., Dortmund, Germany

368
scoop evenly on a hair tress. Excess gel is squeezed off and the hair
tress is coiled around a Teflon curler. After that, the prepared tresses
are dried overnight at 70C. After 30 minutes of cooling to room
temperature, the curl is carefully removed from the curler. The
curls are hung up at one end, and their starting length is recorded.
The determination of the curl retention is performed at 25C and
90% relative humidity. After 5 hours, the final length of the curls is
recorded. The stability of the curls in the particular climate is calcu-
lated and given in percent.
With mousses, the wet hair tresses are dipped into the solution
of the mousse formulation containing setting polymer and prepared
as already described. The determination of the curl retention is
performed at 25C and 75% relative humidity and determined as
already described.
Combing force measurement for mousse application: The mousse is
dispersed into the wet hair swatch. Prior to measurement, the hair
swatch is detangled until no loops or coils remain. Next, the swatch
is positioned into a clamp and combed into the testing comb that
is part of the tensile tester. The combing force reduction is given in
percent and calculated from the force ratio between treated swatch
value and blank value (untreated swatch).
Light transmittance of gels (clarity measurements): The mea
surement of the transmittance is carried out with a UV/VIS
spectrometer. Macro cuvettes with layer thickness of 1 cm were
used. The transmittance value is determined at a wavelength of
600 nm. For comparison, the transmittance of distilled water
is measured.
Results: Excellently transparent hair gels were made with
VPMVI copolymer as the setting polymer. The precondition is
a transparent thickener base, such as acrylates / C10-C30 alkyl
acrylate crosspolymerg. Figure 7 shows the clarity of a formulation
consisting of this thickener at 0.4% and VPMVI copolymer at 3.0%
in distilled water. The light transmission of the gel base with 0.4%
thickener is 97.4% (middle image). The addition of VPMVI copoly-
mer enhances transparency to more than 99% (right image).
g
Ultrez 21, Noveon, Cleveland, USA

369
Figure 7. Clarity of a hair gel with VPMVI copolymer
With 3% content of the setting polymer, one can achieve a very

strong setting that outperforms most of the commercially available
gels on the market. As shown in Table 1, VPMVI copolymer is rec-
ommended at levels between 1% and 5% with the commonly used
thickeners for the manufacture of clear gels. The details of formula-
tion procedure vary from one formulation to the next, but in general
the recommended procedure requires these steps:
1. Making of a diluted solution of the thickener;
2. 100% neutralization of the thickener solution and formation
of the gel;
3. Addition of the 20% VPMVI copolymer solution
In Table 2, the properties of VPMVI copolymer in hair gels are
pointed out. The clarity of certain formulations is even better than
that of polyvinylpyrrolidone formulations. The setting effect is high.
The curl retention is above 90%.
As Table 3 shows, VPMVI copolymer is appropriate in hair
mousses also. It can be used as a single setting polymer or in combi-
nation with various polyquaterniums. For example, the combination
with polyquaternium-46h is recommended for extra strong hold and
h
Luviquat Hold, BASF Corp., Mt. Olive, New Jersey, USA

370
Table 1. Recommended percentages of some common

thickeners used with VPMVI copolymer
INCI name Trade name Supplier Solid content (%)

Acrylates / C10-C30 alkyl Ultrez 21 Noveon 0.4-0.5
acrylate crosspolymer
Acrylates beheneth Aculyn 28 Rohm & Haas ca. 1.0
25 methacrylate copolymer
Carbomer Carbopol 940 Noveon 0.4-0.5
Table 2. Properties of 3.0% VPMVI copolymer in hair gels

thickened with 0.5% acrylates / C10-C30 alkyl acrylate
crosspolymer
VPMVI PVP K90 PVP K30

Clarity* crystal clear clear clear
Transmission* (%) 99.2 96.8 98.8
Tackiness at 90% RH (rating) 0-1 3 3
Stiffness test (cN) 190-200 125-145 70-80
Curl retention at 90% RH (%) > 90 61 47
*Visually in 250 ml glass tubes; Transmission T at 600 nm
Table 3. Properties of 3.0% VPMVI copolymer in hair mousses
Setting Curl retention Combability

(cN)* (%)** (%)***
VPMVI (3%) 217 81 70
VPMVI (2%) and PQ-46 (1%) 299 66 72
VPMVI (2%) and PQ-16 (1%) 295 24 78
PVP/VA 64 (3%) 67 2 62
* Stiffness Test in Newtons

** measured at 75% RH
*** Combing Force Reduction in %

371
high humidity resistance. Combined with polyquaternium-16i, it

achieves high conditioning performance and better curl retention
than with conventional VP/VA copolymers.
Sample formulations are shown in Formulas 1, 2 and 3.
Formula 1. Spiky hair gel for very strong hold
A. Water (aqua), distilled 48.95% w/w

Preservative qs
B. Acrylates/C10-30 alkyl acrylate crosspolymer
(Ultrez 21, Noveon) 0.5
Triethanolamine 0.75
C. Water (aqua), distilled 22.00
PEG-40 hydrogenated castor oil
(Cremophor CO 40, BASF) 0.10
D. PEG-8 (Pluracare E 400, BASF) 2.00
Panthenol 0.50
PEG-25 PABA (Uvinul P25, BASF) 0.10
Dimethicone copolyol (DC190, Dow Corning) 0.10
VP/methacryamide/vinyl imidazole copolymer
(Luviset Clear, BASF) 25.00
Procedure: Put A into a beaker, stir and disperse B into it until the particles sink to
the bottom. Then add C and stir until a homogeneous gel has been formed. Prepare D and stir
until dissolved. Then add D to the gel.
pH value: 7.2
viscosity (Brookfield): 30500 mPas
transmission: 97% (600 nm)
Summary
VPMVI copolymer is an innovative ingredient for clear hair
gels, hair mousses and other styling products. New is the combina-
tion of the ability to formulate clear hair gels based on cross-linked
polyacrylic acid with improved properties during application and
i
Luviquat Style, BASF Corp., Mt. Olive, New Jersey, USA

372
Formula 2. Shiny hair gel

PEG-40 hydrogenated castor oil
(Cremophor CO 40, BASF) 0.10
B. VP/methacryamide/vinyl imidazole copolymer
Acrylates beheneth-25 methacrylate copolymer
(Aculyn 28, Rohm & Haas) 5.00
Glycerol 87% 5.00
Dimethicone copolyol (SF 1288, GE Silicones) 0.10
PEG-25 PABA (Uvinul P25, BASF) 0.10
Preservative qs
C. Triethanolamine 0.60
Procedure: Solubilize A. Weigh the components of B into A and stir until homogeneous.
Neutralize AB with C and stir until homogeneous.
pH value: 7.0
viscosity: 90200 mPas
transmission: 97.0% (600 nm)
Formula 3. Volumizing aerosol mousse 6% VOC

VP/methacryamide/vinyl imidazole copolymer
Polyquaternium-46 (Luviquat Hold, BASF) 5.00
Preservative qs
B. Water (aqua), distilled 30.00
Ceteareth-25 (Cremophor A-25, BASF) 0.20
Cocotrimonium methosulfate (Luviquat Mono LS, BASF) 0.40
Laureth-3 (Rhodasurf L-3, Rhodia) 0.70
C. Propellant A70 (propane/isobutane) 6.00
Procedure: Add ingredients of A in order listed with adequate agitation, making sure all components
are completely dissolved before adding the next. Premix ingredients of B until homogeneous. Add B
to A with adequate agitation. Fill into appropriate containers and charge with C.

373
after drying on hair. The new setting polymer can be employed as

single polymer or in combination together with other styling poly-
mers. VPMVI copolymer provides low polymer film tackiness. The
values of curl retention at 90% relative humidity (values above 90%)
and the setting effect are high. The advantages of the new setting
polymer over conventional setting polymers are demonstrated by
application assessments and conventional mechanical studies.
In particular, nanomechanical measurements are well suited to
differentiate between polymer film properties on substrates. This
method of nanoindentation and nanoscratching was introduced
into the material science for cosmetics for the first time. It is can
be applied to polymer films as well as films of complete cosmetic
formulations. Tack, hardness and friction of the VPMVI copoly-
mer films correlate with important application properties on hair,
such as tackiness, setting effect and combability. These insights
into the mechanical properties of materials were used to tailor the
new polymer, which takes formulations to a higher level of product
performance.
C. Wood, S. Nguyen-Kim and P. Hoessel

BASF AG, Ludwigshafen, Germany
References
1. P Hoessel, Hair styling gels and alternative styling products Market trends and
polymer formulation concepts, Euro Cosmetics 3 40-45 (2001)
2. GM Pharr, Measurement of mechanical properties by ultra-low load indentation, Mat Sci
Eng A 253 151 (1998)
3. GM Pharr, WC Oliver, FR Brotzen, On the generality of the relationship between contact
stiffness, contact area, and elastic modulus during indentation, J Mater Res 7(3) 613
(1992)
4. WC Oliver, GM Pharr, An improved technique for determining hardness and elastic
modulus using load and displacement sensing indentation, J Mater Res 7(6) 1564
(1992)
5. WC Oliver, Alternative technique for analyzing instrumented indentation data, J Mater
Res 16(11) 3202 (2001)
6. C Wood, Nanomechanical Measurements in Hair Care, PCIA Conference, 5-7 March
2003, Manila, The Philippines

Chapter 38
Dyeing to Get it Right

KEY WORDS: hair dye trends, highlighting, home hair dye kits, temporary
hair dye, product development considerations, natural
products
ABSTRACT: Discussion of in home and salon hair dye products with
features like longer-lasting color or temporary hair color,
conditioning and natural ingredients.
Hair color evolves like art and fashion, said Brad Johns, global
color director, Clairol. From New York to Milan, fashion has a
huge influence on hair trends. Therefore, marketers and suppliers
carefully monitor those trends and incorporate them into product
development.
According to Johns, three color trends from the fall of 2006
include: a warm, solid color; a warm base with tiny highlights all
through, so its multi-tonal but not drastic; and a warm base with
highlighted pieces around front. Celebrities also are bringing back
darker shades, providing richness, sex appeal and sophistication for
brunettes. For a more drastic look, Sue Pemberton, artistic director,
Vero, translated todays cultural duality and fall fashion trends into
hair by placing contrasting hues diagonally, horizontally and verti-
cally to simulate the graduations in texture and color of traditional
Scottish Highland tartans and tweeds.
In response to these trends, consumers are looking for bold
highlights, multihued layers and rich hues in all-over color. This
has led to the introduction of deep tones of eggplant, burgundy and
mahogany. Also, strategically placed highlights, lowlights or panels
that accentuate the texture in hairstyles are on the rise this season.
Trends, however, extend beyond color. Educated consumers
demand a lot from their hair products. While a large percent-
age is looking to distinguish themselves or make statements with

376
Color Dyeing to Get it Right
their hair color, many also desire results with as little damage to the
hair as possible, said Mabel Covey, vice president of science and
technology, Hair Systems Inc. This need to minimize damage due
to chemical processes and environmental elements has led to the
introduction and promotion of demi and nonammonia hair colors
over the past several years. We are also seeing a strong desire on the
trendsetting consumers part to have shiny hair and longer-lasting
color, she added.
About two-thirds of women, for whatever reason, color their
hair. But the growing social acceptability of coloring ones hair
for purely fashion purposes, rather than to conceal gray, says
something about how women perceive hair color as part of their
personality. At the same time, consumers are looking to enhance
those aspects of their hair that they find desirable while also tam-
ing the undesirable ones. These consumer needs represent product
opportunities that deserve consideration by marketers and ingredi-
ent suppliers alike.
To accommodate the trend for multidimensional hair color,
Revlon Custom Effects Highlighting and Lowlighting Kits pro-
vide subtle or dramatic highs and lows that give hair color depth
and movement. In this two-step process, either highlighting cream
or lowlighting hair color is applied using a comb applicator. Then
the patented shampoo-in Smart Toner, formulated with a low level
of oxidative hair dye, cleanses the hair and deposits brightening
color to the highlighted/lowlighted strands. The oxidative dye in
the Smart Toner reacts with the residual peroxide left in the high-
lighted or lowlighted strand after rinsing.
The key to great highlighting is proper placement of the high-
lights following the removal of melaninthe hairs natural color.
Innovations in how the highlighting products are applied make it
easier for consumers to use them at home. Herbal Essences High-
lights from Clairol offers a unique color-indicating formula so
consumers can see where they are placing the highlights. In this
case, the success of the product also goes beyond the formulation.
Three Herbal Essences Highlighting kits also include a newly
designed two-in-one comb, giving consumers the option for either
fine or bold highlights. The comb has two chambers on one end

377
Mason Chapter 38
and a single chamber on the other end, further enabling users to

vary highlights.
Todays beauty consumer is much more savvy and experimental
than in the pasteven eager to try different products to create a
variety of looks and styles, said Mercedes Orpin, product devel-
opment manager, Bumble and bumble . Bumble and bumble Hair
Powder products provide temporary color thats applied directly
onto the roots and hair, and then can be brushed through the hair.
The powders feature a unique blend of iron oxides for color and
aluminum starch, magnesium carbonate and silica for oil absor-
bency, volume and texture. The powders provide a subtle hint of
color while providing a dry texture so styles stay put, said Orpin.
Bumble and bumbles interest in powder stemmed from session
stylist Laurent Phillippons frustration that only white versions,
which were noticeable on all but blonde hair, were available.
Three technical considerations in product development were
significant. The first was finding the appropriate tone for each
shade. Submissions were tested on a variety of hair colors to see if
they blended, enhanced or shifted the color. Second was striking
the balance of powder base to propellant. We needed the right
amount of powder for the product to perform properly, but we had
to take into consideration spray pattern, amount of powder dis-
pensed, force of propellant and overall drying time, said Orpin.
The third consideration was packaging componentsspecifically
finding the best combination of valve and gasket options for opti-
mal product application.
Herbal Essences Colorflirt Mousse also allows consumers to
experiment with new colors. The semi-permanent colorant prod-
uct uses a very different technology from permanent colorants,
explained Frauke Neuser, PhD, senior scientist, Clairol. It does not
contain any ammonia or peroxide and the dye molecules, known
as direct dyes, are pre-formed so there is no product mixing. The
color molecules dont penetrate the hair; they get stuck in the
cuticle layers and wash out, Neuser explained. Consumers also have
control over the intensity of the colorthe longer they leave it on,
the more color they get.
On the ingredient side, suppliers have accommodated fashion

378
trends characterized by vibrant colors, highlights and unique effects

by providing formulators with chormophores of high brilliancy and
tinctorial strength. Ciba Specialty Chemicalss Vibracolor hair dye
is one such example. It combines the most brilliant shades with
excellent stability and fastness properties, said Michael Schork,
marketing manager, colorants and stabilizers, Ciba.
Lasting Impressions
Glazing and post-color treatment products that promote longer-
lasting color represent a potential area of growth in the hair color
segment, especially considering the vibrancy of todays colors. In
fact, the most recent product launches from Clairol have been based
on the realization that consumers desire to maintain the look and
feel of just-colored hair longer. We have found that there is a roller
coaster of emotions for consumers, explained Clairols Neuser.
Following an initial exuberance, they tend to feel a decline in satis-
faction. This has led to the development of products that maintain
or boost color appearance and hair quality between colorings. Nice
n Easy Color Boosting Glaze is just one salon-inspired product that
delivers a boost of color and shine in five minutes.
Ingredient innovation plays a substantial role in longer-lasting
color. Croda introduced Keratint EZ hair tint emulsifying system.
Keratint EZ helps increase the dye penetration, thus longer-lasting
color, explained Charles Moses, research manager, ethnic products
and hair color, Croda. Designed to simplify hair color formulations,
the pastille is a one-step conditioning and emulsifying package
for creating stable, cost-effective emulsions. Keratint consists of a
balanced ratio of Crodafos CES, a phosphate ester that provides
better hair dye penetration for truer, longer-lasting color; Incroquat
Behenyl TMS, a quaternary conditioning agent that contributes to
detangling; and Procetyl AWS, a pH-stable ether that contributes
to moisturization.
Crodafos HCE, from Crodas line of phosphate esters, works by
aiding in the delivery of dye actives to promote a faster coloring rate
inside the hair cortex. This allows hair color formulators to create
hair dyes with more color uptake, greater color intensity and better

379
Mason Chapter 38
color wash-fastness, as shown by studies using a Hunter LabScan

Spectrocolorimeter.
Looking Natural
Despite the vibrant colors available, consumers have become selec-
tive in choosing natural-looking colors in the right tone. A study
by Redken showed that 85% of those looking to change their
hair color are looking for a subtle to moderate color change, rather
than a dramatic or unusual change. In response, Redken offers
an ammonia-free, one-level lift permanent color cream to salons.
Shimmer One is a permanent color that uses a chemical process
to permanently alter the state of hair, replacing melanin with a dye.
Yet, it also has several characteristics of a demi-permanent color,
depositing color only on the surface of the hair. Shimmer One lifts
the hair from its natural color up one level in the 10-level scale of
tonality of natural color. This provides consumers with more natu-
ral-looking, longer-lasting color but a less drastic commitment and
less visible re-growth. The formulation features Tri-Light Technol-
ogy, an active complex of luminizing dye molecules for long-lasting
color, mango butter to smooth and moisturize and rice protein to
strengthen the hair. This branded technology is being marketed in
all of Redkens future products to communicate the importance of
key active ingredients that help differentiate our products among
other brands, explained Kirsten Marsh, senior director, hair color
and texture, US marketing, Redken.
Similarly, LOral Paris offers its one-level lift Natural Match.
LOrals Color-Calibrated Technology creates a spectrum of
24 refined ammonia-free, permanent shades that could not be
delivered using traditional, nonpermanent technology. In addition,
the unique package features a before swatch on the front and
a convenient mirror on the box to guide consumers in their
color selection.
Sensory Benefits
Consumers are looking for more than longer-lasting color and
easier-to-use products. They also desire secondary benefits like

380
improved sensory properties, said Steve Carbone, marketing man-

ager, polymer systems, Ciba.
Coloring pre-treatments, for example, prepare the hair to opti-
mize color deposition along the hair fiber and at the root area while
providing even color coverage from root to tip. Hair tips usually are
porous (caused by environmental damage and excessive styling), and
can grab color like a sponge, which leads to uneven color results,
said Clairols Neuser. Hydrience Crme Moisturizing System is a
three-step system that provides hair with moisturizing protection
before, during and after the coloring process to provide even, rich
color. Positively charged conditioning ingredients deposit onto the
hairs surface and help neutralize the negative charge of stressed hair
to protect it and keep it moisturized, explained Neuser. Clairol also
has the ColorSeal Gloss Conditioner, featured in its Nice n Easy
products, to lock in color and impart lasting conditioning properties.
Innovative ingredients and concepts play a significant role in
bringing enhanced quality of products to consumers. The sole
purpose of a hair color used to be to deliver the expected color and,
as a side benefit, the hair had body and fullness after the process,
explained Hair Systems Covey. Nowin an effort to minimize
damage and to help maintain healthy hairfunctional proteins,
moisturizers, silicones, cationic conditioners and UV protectors are
all included in hair color formulations, none of which would be pos-
sible without new technology and R&D.
Burgeoning Markets
The hair coloring market has struggled due to a combination of
product over-saturation and stiff competition among a few manu-
facturers. The previously dynamic sector has lost ground in the US,
France and Spain, yet sales in Italy improved slightly in 2005, driven
largely by the performance of conditioners and hair colorof which
LOral is the indisputable leader, according to Mintel International
Group Ltd.
Innovation and catering to burgeoning consumer groups inter-
ested in coloring can breathe new life into the market. Driven by
the empowerment of women and the antiaging trend, men recog-

381
Mason Chapter 38
nize the need to compete to look better, said Redkens Marsh. Of

the three top major manufacturers, Combe, Inc. has seen the most
positive gains, indicating the potential power of the mens market.
Combes Just For Men, which recently introduced three new colors,
is the world leader in mens hair color. The brand has a no-mess,
five-minute maxim, and its new True Color formula targets only
the gray hair for a natural look. Men want to look younger longer,
but they want it quick and simpleand they dont want anyone to
notice, said Marsh.
Redken, which introduced its mens line in 2004, is just one
company that has made a commitment to steady long-term growth
in this market. Its about changing the entire mentality and lifestyle
of the population and redefining masculinity. Thats not going to
happen overnight, Marsh added.
The growing tendency for teens to experiment with appearance
also has potential to increase sales in the market. This is espe-
cially true in the UK, where the hair color market is being driven
by trendsmultitonal, highlighted and temporary effectsthat
have burgeoned from the youth market. In addition, the emerging
and extremely experimental youth market in Japan is influenc-
ing Europe, which in turn influences the US. We are seeing more
young girls, even boys, experimenting with hair color, added Marsh.
It is a form of self-expression for teenagers to define who they are.
Salon Service
In order to ensure growth for the future, the hair color market will
need to reconcile the tension between the options of home color
and the salon services. The salon hair care segment continues to
be plagued by product diversionthe selling of salon products
through retail channelswhich has increased over the last five years.
In addition, salon products are facing increased competition from
masstige brands. (A trip to the salon) used to be about quality,
but now salon-inspired retail products can give consumers the same
quality at home, said Clairols Johns. Yet, while manufacturers have
developed at-home beauty alternatives, the indulgent nature of salon
treatments is still a powerful draw. According to a study by Redken,

382
the percentage of women coloring only in salons at the end of 2005

already was up 40% from 2002.
It comes down to customization and the salon experience.
Stylists really listen to clients and prescribe, in partnership with
the clients, what they need to meet their desires, said Redkens
Marsh. Redken is utilizing a new Web site and aggressive consumer
advertising in fashion magazines, in addition to special events, to
de-mystify hair color for consumers.
Global Growth
As the market grows, manufacturers continue to be inspired by
new ingredient innovations, resulting in enhanced products for the
consumer. Better dyes, better delivery systems and better color
production and maintenance additives are critical to the evolution
of hair color, said Cibas Carbone. Future products must be mul-
tifunctionalmeaning offering color, conditioning and protection
all in one product. Manufacturers also must consider ingredient
safety, intensity of color, ease of use and impact on sensory proper-
ties of hair.
Manufacturers must continue to focus on formulating globally
acceptable products, meaning they must keep up with constantly
changing regulations in international markets. Many hair dyes have
been de-listed in some countries, and the fate of some dyes is yet to
be determined, said Hair Systems Covey. Although many of the
dyes for vibrant tones have been de-listed for safety and regulatory
reasons, the consumers demand for rich tones has not changed. As
new products are introduced, developers will have to ensure that
formulations are globally acceptable before incorporating them into
products destined for a global market.
Sara Mason

Chapter 39
Forever YoungAntiaging
Hair Care: an Interview
with Beth Johnson
KEY WORDS: antiaging, hair dyes, silicones, color retention
ABSTRACT: Discussion of aging hair and the use of silicones to provide
color retention and strengthening properties.
When most consumers think about aging, they think about skin.
Contrary to popular belief, however, hair also ages. The visible sign
of aging hair is lack of pigment, which is a result of hair follicles no
longer producing melanin.1 Accompanying this decrease in pig-
ment is a decrease in hair strength and thickness. Although there is
no way to prevent hair from becoming gray and thin, there may be
a way to slow the process by which it happens. To slow hair aging,
researchers are turning to an ingredient that has been formulated
into personal care products for quite some timesilicone.
Research
Beth Johnson, senior industry specialist and global hair care tech-
nology leader for Dow Corning Corp., is researching ways to use
silicones to provide color retention and strengthening properties
to hair.
The trends that are in skin care carry over to hair care, said
Johnson. Aging hair is drier and wiry. Silicones provide more pro-
tection to hair that is losing its strength.
Johnson and fellow researchers chose to test the efficacy of
silicones on enhancing hair strength. According to Johnson, amino
functional silicones are able to strengthen hair by forming a film

384
Color Forever Young: Antiaging Hair Care
along the fiber shaft, essentially sealing in the cuticles. It is hypoth-

esized that the film can provide protection to hair, sealing the hair
cuticle, helping prevent moisture penetration into and out of the
hair cortex to maintain an optimal moisture level for hair strength.
Amino silicones have a benefit in enhancing hair strength. The
amino silicones have a better deposition on hair [than other sili-
cones], so they can better bind to damaged hair, said Johnson.
The amino silicones were formulated into dilute leave-on and
rinse-off conditioners for its ability to seal in moisture. If the hair is
properly conditioned, less damage is being done to it.
Benefits
Although silicones provide a film to the hair, according to Johnson,
they do not build up, which is a significant concern for consumers.
Members of Johnsons research team conducted studies in which
hair treated with amino silicones were washed a number of times.
We have shown through different amounts of washing that the
silicone does wash off, said Johnson.
Increasing hair strength can only mean good things to come in
terms of hair aging. Johnsons researchers have recently launched a
program that demonstrates the benefits of silicones in enhancing
hair strength using single fiber testing, whereby a single fiber of hair
is mounted and elongated using tensile measurement.
More consumers are coloring their hair, according to Johnson,
and formulators must provide products that ensure long-lasting
color. Hair colorants are known to damage the hair cuticle and
leave hair brittle, dull and dry, so consumers seek specialized
treatments to maintain healthy colored hair, Added Johnson. Spe-
cialized hair care products, therefore, have been designed specifically
for hair treated with permanent colorants. Studies by Johnsons team
have demonstrated that amino functional silicones enhance hair
strength and aid in color retention when incorporated into perma-
nent hair colorants or rinse-off conditioners.
The future of silicones involves branching into other arenas of
hair care, according to Johnson. [The silicone industry] is getting
into the styling market. It is developing new methods to see if sili-
cones can provide body and volume, said Johnson.

385
Schaefer Chapter 39
One thing is for sure, the silicone industry will continue as it has
for many years because it continues to reinvent itself, thereby main-
taining its youth.
Katie Schaefer, Assistant Editor

Cosmetics & Toiletries magazine, Carol Stream, IL USA
References
1. RM Trueb, Aging of hair, J Cosmet Dermatol 4(2) 60-72 (2005)

Chapter 40
A Controllable
Progressive Hair Dye
Process
KEY WORDS: graying, hair dye, oxidation, color rinse, -phenylenediamine,
urea peroxide
ABSTRACT: Product innovation consistently sparks new consumer
interest in hair coloring. The application of the product
must be convenient and simple; therefore, a gradual color-
enhancement shampoo is a preferred choice for its ease of
application and needless color commitment. These traits
make it marketable to all age groups and sexual categories
as a low-risk, high satisfaction cosmetic accessory.
Lead and bismuth salts have been used for years in the United
States to produce progressive hair dyeing solutions,1 which are more
socially acceptable hair coloring processes than one-step dyes, and
offer merchandising potential.
Due to its slow and gradual change, graying hair often goes
unnoticed at first, until it eventually becomes obvious and pro-
nounced. Once an individual becomes aware of their graying hair,
they typically desire a hair color treatment but fear the attention
that surrounds immediate and dramatic color restoration. This is
particularly true of men, since women tend to begin coloring their
hair at earlier stages of graying, thereby preventing and avoiding
exposure to the public.
In addition, target hair coloring, a specific and more radical color
change, is considered a female cosmetic gesture. This process gener-
ally is only exercised by men when the truth can be kept secret.2
In an ideal world, the graying process could be reversed. The
individual could control the reversal, reducing the number of years

388
Color A Controllable Progressive Hair Dye Process
that the graying process takes and making it gradual so that a psy-
chological advantage may be gained, in terms of peer awareness.
A gradual approach to coloring haira persons best method in a
non-ideal worldshould be incomplete in its ultimate effect so that
the process can be stopped with subsequent maintenance, or contin-
ued with successive and sequential color build-up; the result should
be permanent and resist easy removal.
The application of the hair coloring product must be convenient
and simple. Therefore, shampoo is considered the preferable choice
of application.
Theory
The most controllable color reaction on hair is that which employs
oxidation-type dyes. According to Brown and Pohl,3 the oxidation
process, in its simplest form, proceeds in three distinct steps. First,
the primary intermediate is oxidized to a reactive imino compound.
Second, this reactive imine couples with nucleophiles in the solu-
tion to give the dye precursors that are oxidized in the final step
to the dye. This can be best demonstrated by the reaction of para
phenylene diamine (p-phenylenediamine) with an oxidizer to form
Bandrowskis Base (Figure 1).
NH2 NH
Ox
NH2 NH
NH NH2 NH2
N NH2
H2 N N
NH NH2 NH2
Figure 1. Bandrowskis Base

389
Shansky Chapter 40
It has been proposed4 that p-phenylenediamine diffuses into the

hair fibers and is oxidized to diamine, which in turn condenses with
p-phenylenediamine to form Bandrowskis Base, a brown-black indo
dye (see The Formation of Indo Dye).
The Formation of Indo Dye

A dye precursor (e.g., p-phenylene diamine) is oxidized to its
corresponding diiminium ion, and this active intermediate condenses with
an electron-rich dye coupler forming a dinuclear product that oxidizes to an
indo dye. There are dinuclear indo dyes, polynuclear indo dyes and trinuclear
indo dyes, all of which appear in the brown-black Bandrowskis base.
The formation of Bandrowskis Base is consistent with the fol-

lowing: The polymerization process of color bodies in the hair fiber
depends on the concentration of dyes and oxidizing potential of the
oxidizing agent. This seesaw effect can be advantageously exploited
to give variations of color intensity, which are controllable by the use
of pre-measured quantities of oxidizing agent. The oxidizing agent
of choice is urea peroxide, since it can be tableted and/or solubi-
lized in a mutual solvent such as glycerol for easy dispensing by an
untrained individual. The color reaction would be as follows: 5
Eq. 1. p-phenylenediamine + oxidizer color ( p-phenylenediamine-ox)

Eq. 2. p-phenylenediamine-ox + coupler color ( final)
Since color couplers do not produce colors by themselves when

oxidized, but only in the presence of oxidized dye, a measurable
control can be realized from adjustment in dye concentration. In
addition, the adjustment of oxidation quantity can be appreciated
as a second measure of possible control. These two variables in the
reaction mechanism can together produce a product that suits the
stated parameters.
In order to ascertain the feasibility of this method, two separate
variables must be investigated. The first concerns the 5-min time

390
period that the oxidation dyes take to work. All commercial hair
dyes are formulated to operate between 3045 min. This dyeing time
would have been impractical for any potential marketing concept.
All commercial hair dyes are formulated to operate with equal
parts of 6% hydrogen peroxide. That is, to every ounce of shampoo/
color, an equal ounce of 6% hydrogen peroxide is added. This is
determined to be a high concentration for practical purposes. Rather
than a ratio of 1:1, it is deemed necessary to have a maximum ratio
of approximately 1:0.17 because in the former case, there was poten-
tial for excessive skin staining, harsh color rendition and possible
hair damage.
As an additional requirement, low levels of total dye are main-
tained. A subjective concentration of half the quantity of most
oxidation hair dyes will be selected in order to avoid skin staining,
harsh color rendition and hair damage
Therefore, a range of 23% of dyes is chosen. In doing so, it is
believed that the color uniformity associated with commercial hair
dyes, which often gives an artificial appearance to the finished hair
color, may be avoided.
Method
In order to test these premises, it was felt prudent to use a standard
oxidation hair dye system. The variables were kept at a minimum
without introducing uncertainties and a standard base formula was
employed (Formula 1).
Due to the unpleasant odor of ammonium hydroxide, it could
be replaced with a fixed alkali of similar partial ionization, such as
monoethanolamine. The detergent system could be modified for
better shampoo (foaming) performance by introducing salts of fatty
alcohol sulfates. The formula for the oxidizing medium varied from
the base formula (Formula 2).
Of course, hydrogen peroxide and its other salts can be con-
sidered for this application. The most important aspect of urea
peroxide is its stability in the oxidizer formula.
A color shampoo treatment was made by mixing 1 oz of For-
mula 3 (blonde) with one gram of Formula 2 (urea peroxide). Three
hair swatches were placed in this color bath for 5 min at room

391
Shansky Chapter 40
Formula 1. Base formula
Nonoxynol-9 18.30%w/w
Laureth-4 9.00
Oleic acid 20.00
Octoxynol-5 9.00
Isopropyl alcohol 17.50
Ammonium hydroxide 8.00
Trisodium EDTA 0.40
Water (aqua) 15.60
Sodium sulfite 0.70
Sodium borate 1.50
100.00
Formula 2. Oxidizer
Propylene glycol 70.0%w/w

Urea peroxide 30.0
100.00
Procedure: Heat to 60 C. Mix and cool.
Formula 3. Blonde
Base formula (Formula 1) qs to 100.00

Para phenylene diamine 0.50
p-Aminophenol 0.20
p-Methylaminophenol sulfate 0.16
Alpha naphthol 0.09
Resorcinol 0.20

392
temperature. The hair swatches were then removed and rinsed with
lukewarm water until the rinse water runs clear.
The color results were barely perceptible in the first swatch. The
two remaining swatches were next placed in a color bath contain-
ing 1 oz of blonde and 2 g of urea peroxide, again for 5 min at room
temperature. After 5 min, the swatches were removed and rinsed. By
visual assessment, the rendered color was almost twice the depth in
the second phase.
Finally, the last hair swatch of the series was placed in a 1 oz
color shampoo bath containing 4 g of urea peroxide for 5 min at
room temperature. Again, the swatch was removed and rinsed. The
rendered color was deeper than the result of phase two, and it was
therefore observed that a progressive and linear relationship in color
value existed between the three hair swatches.
Indeed, the color relationship appeared to be almost geometric in
performance and controllable by concentration of oxidizing agent.
In order to confirm this hypothesis, another color of the opposite
spectrum was employedblack (Formula 4).
Formula 4. Black
Base formula (Formula 1) qs to 100.00

Resorcinol 0.50
Para phenylene diamine 1.50
2,5 diaminoanisol sulfate 0.20
The same series of experiments was repeated with the black

color. It became immediately evident from the results of the second
group of hair swatches that the same linear relationship in color
rendition existed for the black color as for the blonde color. It is a
notable fact that in both blonde and black color cases, the results
show a pragmatic approach to a formulation system for a progressive
hair color product.

393
Shansky Chapter 40
Results
It is clear from the blonde and black color shampoo experiments
that the following relationships exist to produce a progressive color
rendition per color category:
1 oz of color plus 1 g of oxidizer yields barely perceptible color

1 oz of color plus 2 g of oxidizer yields definite color
1 oz of color plus 4 g of oxidizer yields target color
This would be true in the four major categories of hair color:

blonde, red, brown and black, as well as their subcategories.
Discussion
The results of the color shampoo tests are not intended to directly
represent marketable items; they are to be considered only for their
scientific value and as proof of a feasible concept. The desirability of
a product that could overcome natural graying in sequential appli-
cations has been one of the long-standing goals in development of
commercial hair dyes. The purpose of such a progressive color sys-
tem is to minimize the attention surrounding such a marked change
in appearance and avoid perceived embarrassment by the recipient.
Holmes6 has discussed the theoretical aspects of the diffusion of
dye molecules into hair fibers and concludes that the mechanism
can be explained by passage of a molecule across a porous barrier. In
this dyeing system, the key ingredientsammonia, water, hydroxyl
ion, peroxide, -Phenylenediamine, resorcinol and -amino phe-
nolare small molecules that can penetrate the hair fiber readily,
where, within a designated time, they polymerize to form large
molecules of predetermined color.
The suggested mechanism of increasing coloration on hair by
increasing oxidation potential has shown an ability to satisfy mar-
keting needs. The idea of varying the dye bath concentration with a
fixedas opposed to varyingamount of oxidizing agent, while a
possibility, could potentially cause gross untidiness or an almost arti-
ficial looking color rendition which appears harsh together with skin
staining and hair damage and is probably not commercially feasible.

394
Product technology has always sparked new consumer interest

in hair coloring. Those who had never considered coloring their
hair before are now giving it a try, enticed by new product formulas
and application types. Because it is easier to apply and requires less
color commitment, a color shampoo method can be marketed to
all groups and sexual categories as a low-risk, high satisfaction
cosmetic accessory.
Oxidation dyes are permanent dyes in that they are not eas-
ily removed until the hair grows out at an approximate rate of one
half-inch per month. Color shampoo makes use of this permanent
property, which is not available in semi-permanent ionic dyes such
as acid dyes and basic dyes, or metallic ingredients such as lead or
bismuth salts.
The composition and dyeing conditions of oxidative hair dyes
consist of the following: 7
1. Dye precursors, which form active intermediates;
2. Dye couplers, which condense with the active intermediates;
3. An oxidizing agent (usually a peroxide); and
4. the reactions are carried out at an alkaline pH.
The results of the above experiments are based on a preliminary
investigation. Therefore, the discoveries found should be used to
guide further research. The work proposed in this disclosure indicates
rather succinctly that progressive dyeing is possible through control
of the oxidizer moiety of oxidative dyes. It is for the researcher with
general experience to bring this idea to a complete conclusion.
Albert Shansky
Albert Shansky Consultants Inc., Norwalk, CT USA
References
1. US Pat 4,583,986, Catalyzed Bismuth Dye System for Human Hair, H Lapidus and A
Shansky (Apr 22, 1986)
2. Hair Colorants, Chapter 27 in Harrys Cosmeticology, Seventh Edition, JB Wilkinson and
RJ Moore, eds, New York: Chemical Publishing, (1980) pp 521-554
3. KC Brown and JF Corbett, The role of meta difunctional benzene derivatives in oxidative
hair dyeing, II reactions with p-amino phenols, J Soc Cosmet Chem, 30(3), 191211
(1979)
4. KC Brown and S Pohl, Permanent hair dyes, Soc. Cosmet Chem Monograph, 1-10
(1996)

395
Shansky Chapter 40
5. R Heald, Solvent Assissted Dyeing Systems, American Perfumer and Cosmetics,

78(40), 1-8 (1963)
6. HW Holmes, The Theoretical Aspects of the Diffusion of Dye Molecules Into Hair, J Soc
Cosmet Chem, 15(20), 595 (1964)
7. CR Robbins, Chemical and Physical Behavior of Human Hair, New York: Van Nostrand
Reinhold Co. (1979) pp 113

Chapter 41
Advances in Polymers for

Hair Coloring
KEY WORDS: polymer, hair care, hair dyes, color retention, lightening,
associative thickeners, non-associative thickeners, HASE
thickeners, HEUR thickeners
ABSTRACT: This chapter surveys patents and technical literature,
principally from the past 10 years, to report advances in
polymers used for dyeing hair, color retention and hair
lightening. Associative thickeners (anionic, cationic,
amphoteric, nonionic, HASE, HEUR), non-associative
thickeners, and silicones are discussed.
Polymers play several roles in the coloring of hair. They act as

thickeners for oxidation dyes. In this role polymers include a range
of associative thickeners (anionic, cationic, amphoteric, nonionic,
and hydrophobically modified alkali swellable) as well as hydro-
phobically modified ethoxylated urethanes. Alkylmethicones and
aminosilicones play a role in color retention. Non-associative thick-
eners help in achieving hair lightening.
This chapter surveys patents and technical literature, princi-
pally from the last 10 years, to report advances in polymers for
hair coloring.
Thickeners for Hair Dyes

Oxidation dyes are made up of dye precursors (such as ortho- and
paraphenylenediamine, or ortho- and paraamino phenols). The dye
precursors are colorless compounds that can penetrate the hair fiber
and in the presence of oxidizing agent, they condense to become
colored compounds. The color can be modified by including cou-
plers such as meta-phenylenediamine.

398
Color Advances in Polymers for Hair Coloring
The oxidation dye compositions are usually thickened to localize

the dye action on the hair and to prevent the dye composition from
flowing down the face and into the eyes. Originally, thickeners such
as carbomers,1 hydroxyethylcellulose or low HLB surfactants were
used. The structure of carbomers consists of microgels of cross-
linked poly(acrylic acid), whereas hydroxyethylcellulose thickens
by entanglement of the relatively rigidbackboned cellulose mac-
romolecules. It has been reported that oxidation dye compositions
thickened with these traditional thickeners result in a dull shade on
the hair and as a result, high concentrations of dyes are required to
obtain intense colors.2
The challenges that must be overcome with two-part dye
systems are: prevention of separation during storage; enhancing
the slow diffusion of dye precursor onto the hair fibers; and
ensuring efficient rinseability of the colorant after application.3
Casperson listed the following conditions of thickened oxidation
dye compositions:4
1. The formulations must be stable to insure a reasonable
shelf life.
2. The compositions formed by mixing the lotion and
developer must have rheological properties to allow the
applied composition to readily distribute the dye throughout
the hair mass and avoid dripping or running from the hair
during the color development period.
3. The dye mixture, as applied to the hair, should allow rapid
diffusion of the dye precursors from the dye mixture into the
hair fiber.
4. The thickened mixture should be readily rinseable from the
hair with water.
5. The mixture should contain conditioning agents that leave
the hair easy to detangle while wet and should feel smooth
and be readily managed when dry.
6. The lotion and developer should preferably, but not
necessarily, have comparable viscosities in order to
facilitate mixing.
7. The dyeing effect should be rapid, with a dyeing time
preferably under 30 minutes.

399
Lochhead Chapter 41
Oxidation dyeing in the presence of a thickener is a complex

process in which it is reasonable to assume that adsorption of the
thickener and the structure of the thickener can alter the rate and
mechanism of diffusion of dye precursor and condensate into the
hair. Therefore, it is interesting to consider the structure of the
thickeners with their reported performance in oxidation dyeing. In
many modern oxidation dyes, associative thickeners are employed
(see The Difference Between Associative And Non-Associative
Thickeners). A range of associative thickeners is now available.5-7
Examples of 4 different types are shown next.
Anionic associative polymers: Steareth-10 allyl ether/acrylates
copolymer is the INCI nomenclature for terpolymers of methacrylic
acid ethyl acrylate and steareth-10 allyl ether (for example Salcare
SC80 or SC90 from Ciba Specialty Chemicals).
Acrylates/Steareth-20 methacrylate copolymer is the INCI
nomenclature for methacrylic acid/ethyl acrylate/stearyl methacry-
late oxyalkylenated terpolymer (for example, Aculyn 22 from Rohm
& Haas).
Acrylates/C10-C30 alkyl acrylate crosspolymer are cross-linked
copolymers of acrylic acid and C10-C30 alkyl (meth)acrylates (for
example, Pemulen polymeric emulsifiers and selected Carbopol
resins from Noveon; Coatex polymers from Seppic).
Maleic anhydride/C30-C38 alpha olefin/alkyl maleate terpoly-
mers (for example Performa V from New Phase Technologies) are
another example.
Polyacrylate-3 is a copolymer of methacrylic acid, methyl meth-
acrylate, methylstyreneisopropyl isocyanate and PEG-40 behenate
monomers. (Examples include the anionic associative polyurethanes,
Viscophobe DB 1000 from Dow Chemical.)
Cationic associative polymers: These include associative polyure-
thanes, such as polyureas or polythioureas, prepared by reaction of
selected amines, diisocyanates and hydrophobic compounds that are
capable of coupling to form telechelic end groups on the polymer.
Polyquaternium-24 is the quaternized ammonium salt of
hydroxyethylcellulose reacted with a lauryl dimethyl ammonium
substituted epoxies. (An example is the Quatrisoft family of poly-
mers from the Amerchol division of Dow Chemical Company.)

400
PG hydroxyethylcellulose coco-dimonium chloride, PG

hydroxyethylcellulose lauryldimonium chloride and PG hydroxy-
ethylcellulose stearyldimonium chloride are quaternary ammonium
salts of hydroxyethylcellulose. (An example is the Crodacel family of
polymers from the Croda Company.)
Associative Thickeners
The association in associative thickeners is actually hydrophobic
interaction. The simplest mechanism of non-associative thickening is
exemplified by polymers like hydroxyethylcellulose and it depends upon
simple entanglement of large molecules to provide the thickening. For
this type of thickening, the usual range of polymer concentrations is 0.5%
to 3%. When thickened solutions are subjected to shear, they exhibit an
elastic recoil due to the entangled molecules relaxing to their solution
conformation.
The addition of a low percentage of hydrophobic groups (typically
dodecyl, cetyl or nonylphenyl) on hydroxyethylcellulose produces the
associative thickener, hydrophobically-modified hydroxyethylcellulose.
The hydrophobic groups are molecularly sticky in aqueous solution
and this makes it possible for the dissolved polymer to form networks at
concentrations below the normal entanglement concentration (usually called
the critical overlap concentration, c*). The hydrophobic associations readily
break under shear and then reform in their new place when the shearing
force ceases. This mechanism alleviates the recoil and confers desirable
rheology on the thickened system.
A second type of non-associative thickening is produced by
polyelectrolytes such as carbomer or other alkali swellable thickeners
that operate in the range 0.1% to about 1%. In these products, the
thickening mechanism relies upon repulsion between swollen cross-
linked polyelectrolyte microgels. The inclusion of hydrophobic groups in
these molecules trims them into associative thickeners. Addition of these
hydrophobes causes the polyelectrolyte molecules to stick together in
aqueous media and gives enhancement of thickening.
A third mechanism of associative thickening involves hydrophobic
association of relatively small polymer molecules into large micelles that are
linked into a network by occasional polymer molecules stretching between
micelles. This is the mechanism of hydrophobically-modified ethoxylated
urethanes (HEUR thickeners).

401
Lochhead Chapter 41
Amphoteric associative polymer: One example is acrylic acid/

(meth)acrylamidopropyl-trimethylammonium chloride/stearyl
methacrylate terpolymers.
Nonionic associative polymers: Cetyl hydroxyethylcellulose is the
cetyl ether of hydroxyethylcellulose (for example, Natrosol Plus CS
modifi ed hydroxyethylcellulose from Aqualon).
Hydroxyethyl ethylcellulose is the ethylene glycol ether of ethyl-
cellulose (for example, Bermocoll EHM 100 from Berol Nobel).
Alkyl hydroxypropyl guars are the alkyl ethers of hydroxy propyl
guar. [Examples include Esafl or HM 22 (C22 alkyl chain) from
Lamberti and RE210-18 (C14 alkyl chain) and RE205-1 (C20
alkyl chain) from Rhone-Poulenc.]
VP/Hexadecene copolymer and VP/Eicosene copolymer are
copolymers of N-vinyl pyrrolidine with hexadecane and eicosene,
respectively. [For example, Antaron V216 and Ganex V216
(vinylpyrrolidone/hexadecene copolymer) and Antaron V220
or Ganex V220 (vinylpyrrolidone/eicosene copolymer)
from I.S.P.]
PEG-150/stearyl alcohol/SMDI copolymer is a copolymer of
PEG-150 saturated methylene diphenyldiisocyanate and stearyl
alcohol monomers. (Examples include the HEUR thickeners Acu-
lyn 46 and Aculyn 48 from Rohm & Haas.)
PPG-l4 palmeth-60 hexyl dicarbamate is the carbamic acid
diester of the polypropylene, polyoxyethylene ether of the fatty alco-
hols derived from Elaeis guineensis (palm) kernel oil. (An example is
the HEUR thickener Elfacos T212 from Akzo Nobel.)
Polyether-1 is a copolymer of PEG-180, Dodoxynol-5, PEG-25
tristyrylphenol and tetramethoxy-methylglycouril monomers. The
aminoplast skeleton of these thickeners offers enhanced stability.
(Examples of polyether-1 include Pure Thix 1442, Pure Thix 1450
and Pure Thix HH from Sud-Chemie.)
Hydrophobically modified alkali swellable associative polymers:
Pohl et al. have reported that acrylates/steareth-20 methacrylate
copolymer (Acrysol ICS-1 from Rohm and Haas) was capable of
thickening hydrogen peroxide solution and this made it possible to
prepare a 2-part system in which the acrylates/steareth-20 meth-
acrylate copolymer, hydrogen peroxide and dye precursors in one

402
part were thickened by adding a second part consisting of a base

such as ammonium hydroxide.8
However, anionic acrylate thickeners tend to form complexes
with the quaternary ammonium surfactant conditioners in the
composition. Also, formulations thickened with simple aqueous
polyacrylate are difficult to rinse from the hair and it is difficult to
formulate to a consistent viscosity with Acrysol ICS-1.4
Casperson et al. reported that the use of the acrylates/steareth-20
methacrylate copolymers Aculyn 22 and Aculyn 33 overcame
these problems.4 Acrylates/steareth-20 methacrylate copolymer is
a hydrophobically-modified alkali-swellable (HASE) thickener. In
this case there are two mechanistic components that work jointly to
produce the observed thickening.
The first component is polyion swelling, which occurs when
the polymer is neutralized with base and becomes a polyelec-
trolyte; the resulting polyion swells as a result of mutual ionic
repulsion of the carboxylate ions that are covalently attached
to the polymer chain.
In the second mechanistic component, swollen thickener
molecules are hydrophobically associated to form an overall
network structure. The hydrophobic associations between the
macromolecules are easily disrupted by shear and are reformed
in a new conformation when the shear force is ceased.
The hydrophobic associations confer useful properties. For
example, the efficiency of a molecular network is obtained without
the elastic recoil that would normally be connected with crosslinked
elastomers. However, steric hindrance of the polymer chains results
in a significant proportion of the hydrophobic groups being isolated
and unassociated in the aqueous environment.
This leads to the interesting observation that addition of sur-
factant causes first an increase in measured viscosity followed by a
viscosity decrease when the surfactant concentration exceeds the
critical micelle concentration. Such behavior is observed because co-
micellization between the isolated polymer hydrophobes causes an
increase in the number of crosslink sites. However, when sufficient
micelles are present, the stoichiometry of co-micellization favors at
most only one polymer hydrophobe per micelle and mutual repul-

403
Lochhead Chapter 41
sion between the micelles causes disruption of the network.9

The effect of surfactant on the viscosity of HASE thickener
solutions with a schematic molecular explanation is shown in Fig-
ure 1. Hydrophobic interactions between the macromolecules can be
disrupted by associating surfactant micelles.
Figure 1. The effect of surfactant on HASE thickener. (i) When no surfactants are present
some of the polymer hydrophobes are isolated and do not participate in network formation.
(ii) In the vicinity of the cmc, the co-micelles enhance the associative network. (iii) Above
the cmc the co-micelles mutually repel and the associative network is disrupted.
Consider the case of hydrophobically modified copolymers of

acrylamidopropane sulphonic acid or salt and methacrylate esters of
ethoxylated or propoxylated fatty alcohols. When these ingredients
are incorporated with hydrogen peroxide in a developer formula
used with an oxidation dye precursor compound, they have been
claimed to achieve improved stability against separation that leads
to an enhancement of hair coloration.3 The polymer in this case is
ammonium acryloyldimethyltaurates/beheneth-25 methacrylate
crosspolymer (Aristofl ex HMB from Clariant Corporation).
Hydrophobically modified ethoxylated urethanes: Enhanced color
intensity from thickened oxidation dyes is achieved if the thickener

404
is an amphiphilic polyether urethane.2 These thickeners are com-

monly called hydrophobically modified ethoxylated urethanes, often
shortened to the acronym HEUR.10-12 In this particular case, the
HEUR that is revealed is PPG-14 palmeth-60 hexyl dicarbamate
(Elfacos T-212 and T-210 from Akzo Nobel).
The HEUR thickeners are ABA triblock copolymers in which
the A blocks are hydrophobic and the B blocks are hydrophilic poly
(alkoxylate).
HEURs are also available as graft/block copolymers with comb
architecture. In the micelle, these molecules are bent into hair-pin
confirmation with the hydrophobic ends in the micelle core and the
hydrophilic middle interacting with water in the micelle corona
(Figure 2).
Figure 2. The HEUR molecules form multimolecular micelles with hydrophobic cores and
poly(alkoxylate) coronas that are hydrophilic.
A network is formed by some HEUR molecules that stretch

between and link the micelles (Figure 3).13 Comb-type HEURS
show low aqueous solution viscosity, but they do offer better net-
work formation and co-micelle association.14-16
Systems thickened by HEURS display pronounced shear thin-
ning when the shear stress exceeds a critical value that corresponds to
the stress that is necessary to extract the linking molecules from the
micelles (Figure 4).17 This model is supported by the fact that these

405
Lochhead Chapter 41
systems can display a single relaxation time that corresponds to the

process of the hydrophobic group being extracted from the micelle.18
The addition of even low concentrations of conventional sur-
factants to HEUR-thickened systems results in a dramatic loss of
viscosity due to competition for residence of the micelle core between
the surfactants and the HEUR linking molecules (Figure 5).13
Figure 3. The HEUR molecules form micelles that are connected into networks by molecules
that stretch between micelles.
Figure 4. Shear thinning occurs when the shear rate exceeds the value that is necessary to
pull out the linking molecules between the micelles.

406
Figure 5. Surfactants cause a dramatic loss of viscosity in HEUR-thickened systems. This is

due to loss of network as a result of displacement of linking molecules by co-micellization
with surfactant.
Aminoplast thickeners function by similar rheological mecha-

nisms as HEUR thickeners. Aminoplast reagents are the aldehyde
reaction products of melamines, ureas, benzoguanamines and gly-
colurils (Figure 6).19
Figure 6. Aminoplast thickeners

407
Lochhead Chapter 41
The aminoplast thickeners are taught to cause bleaching20 and

dyeing21 formulations to remain localized at the position of appli-
cation on the hair so that they do not run over the face. They are
claimed to leave the hair less coarse than the currently used thick-
eners. The polymers described in this work include PEG-180/
octoxynol-40/TMMG copolymer, PEG-180/laureth-50/TMMG
copolymer and polyether-1 (Pure Thix L, M and HH, respectively,
from Sud-Chemie).
Color Retention
Once the hair has been dyed with either a direct dye or an oxidative
dye, the color must be maintained. Color retention can be enhanced
by the addition of silicones during the hair coloring process.
Longer-lasting hair color retention and volumizing has been
claimed by the addition of alkylmethicones either before, during or
after the hair has been dyed.22 Suitable alkylmethicones are hexyl-
methicone (Silcare 41 M10 from Clariant or DC2-1731 from Dow
Coming), octylmethicone (Silsost 034 from Crompton & Knowles
or DC2-1732 from Dow Corning), caprilylmethicone (Silcare 41
M15 from Clariant) and stearoxytrimethylsilane (Silcare 1 M71
from Clariant). In this study, the color retention was evaluated by
half head tests in which the color was measured at root, middle and
tip of hair by a chromometer. 23 Pretreatment of hair with an amino-
silicone is claimed to confer better color retention from direct dyes
and oxidative dyes.24 Preferred aminosilicones are Belsil ADM 652
and Fluid WR 1300 and microemulsions such as Finish CT 964
or SLM 28020 from Wacker Silicones. These compositions confer
water contact-angles greater than 90 on the hair surface measured
by the Wilhelmy plate method using the hair fiber as the plate.
Adsorption of silicones to hair has been claimed to be too weak
to provide lasting protection. On the other hand, covalent binding
of silicones to hair causes damage to and weakening of the fiber.
However, the covalent attachment of trimethylpyridinium molecu-
lar hooks to the silicone chain is claimed to produce a silicone
that adsorbs to the hair and is durable, while maintaining intact
hair structure.25-26

408
Hair Lightening
Hair can be lightened with bleaching agents such as hydroquinone
or kojic acid but hydroquinone is known to be cytotoxic to melano-
cytes and kojic acid derivatives are expensive.
It has been revealed that hair lightening can be achieved by
application of compositions containing a fluorescent dye and a cat-
ionic polymer and it appears that these compositions give improved
fixing of the dye on the hair surface. The cationic polymer must
have a charge density of at least 1 meq/g.27 The fluorescent dye
absorbs light in spectral wavelengths between 360 and 760 nanome-
ters and converts it into light of longer wavelength that is emitted
in the visible region. This is distinguished from optical brighteners,
which absorb only ultraviolet light (200 to 400 nanometers).
It has also been claimed that hair lightening can be achieved
by application of compositions containing a fluorescent dye and a
non-associative thickener. Suitable non-associative thickeners can be
found among crosslinked acrylic acid homopolymers, nonionic guar
gums and dimethylaminoethyl methacrylate homopolymers and
copolymers quaternized with methyl chloride.
Crosslinked acrylic acid homopolymers:
Carbopol 980, 981, 954, 2984, and 5984 from Noveon
Synthalen M and Synthalen K from 3 VSA
Crosslinked 2-acrylamido-2-methylpropanesulphonic acid
homopolymers and their partially or totally neutralized acryl-
amide crosslinked copolymers
Ammonium acrylate homopolymers or copolymers of ammo-
nium acrylate and of acrylamide
Nonionic guar gums:
Vidogum GH from Unipectine
Jaguar C, Jaguar HP and Jaguar DC series from Meyhall
Galactasol 4H4FD2 from Aqualon
Biopolysaccharide gums of microbial origin, such as scleroglu-
can gum or xanthan gum
Gums derived from plant exudates, such as gum arabic, ghatti
gum, karaya gum and gum tragacanth
Hydroxypropyl or carboxymethyl celluloses

409
Lochhead Chapter 41
Pectins
Alginates
Dimethylaminoethyl methacrylate homopolymers and copolymers
quaternized with methyl chloride:
Microsap PAS 5193, Bozepol C Nouveau or PAS 5193 and
PAS 5194 from Hoechst
Salcare 95, 96 and SC92 from Ciba
Conclusion
Hair coloring is the second-largest market in hair care and we
can expect to see significant advances in this segment during the
upcoming years. Polymers are important ingredients in hair coloring
products.
In the initial stages, thickeners ease application on the hair,
mediate the diffusion of the dye precursor and prevent the highly
alkaline compositions from dripping into the eyes. The precise
mechanism of associative thickeners in this respect still requires
investigation to gain a fundamental understanding of their role and
their function in optimizing performance.
Polymers are also used to maintain color in the hair and to allevi-
ate hair damage caused by the coloring process. There is a need to
thoroughly understand the mechanisms involved in color protection
and minimization of hair damage. Advances in spin echo pulsed
gradient NMR and fluorescence microscopy may allow us to follow
the diffusion of molecular components through the formulation and
into hair. Advances in atomic force microscopy should allow us to
view the effects at the molecular level on the hair surface.
Robert Y. Lochhead
The Institute for Formulation Science,
Published July 2005 Cosmetics & Toiletries
References
1. US Pat 4,130,501, Stable viscous hydrogen peroxide solutions containing a surfactant
and a method of preparing the same, CW Lutz and LE Cohen, assigned to FMC (Dec
19, 1978)
2. US Pat 6,010,541, Oxidation dye composition for keratin fibers comprising a nonionic

410
amphiphilic polymer, R De la Mettrie and F Boudy, assigned to LOral (Jan 4, 2000)

3. US Pat App 2004/0255399, Method and compositions for coloring hair with taurate
copoflymers, J Yang, fifled by (Dec 23, 2004)
4. US Pat 5,376,146, Two-part aqueous composition for coloring hair, which forms a gel
on mixing of the two parts, S Casperson, S Pohl and M Wong, assigned to Bristol-Myers
Squibb (Dec 27, 1994)
5. US Pat App 2005/0000037, Dye composition comprising 2-chloro-6-methyl-3-
aminophenol as coupler, para-aminophenol and 3-methyl-4-aminophenol as oxidation
bases and at least one associative thickening polymer, M-P Audousset (Jan 6, 2005)
6. US Pat App 2005/0000038, Dye composition comprising 2-chloro-6-methyl-3-
aminophenol, at least two oxidation bases chosen from para-phenylenediamine
derivatives and at least one associative thickening polymer, M-P Audousset (Jan 6,
2005)
7. US Pat App 2005/0000039, Composition comprising at least one coupler chosen from
2-chloro-6-methyl-3-aminophenol and addition salts thereof, at least one oxidation base,
and at least one associative polymer comprising at least one C8-C30 fatty chain, M-P
Audousset (Jan 6, 2005)
8. US Pat RE 33,786, S Pohl and M Hnatchenko, assigned to Clairol (Jan 7, 1992)
9. LM Landoll and AC Sau, Synthesis and solution properties of hydrophobically modified
(hydroxyethyl) cellulose, ACS Adv Chem Ser 223 343-364 (1989)
10. US Pats 4,079,028, 4,155,892, 4,426,485, 4,496,708, 5,281,654, 4,499,233 and
5,023,309, describing HEURS with hydrophobes in bunches
11. US Pat 4,327,008, describing branched and terminal HEURS (Apr 27, 1982)
12. EU Pat Application 0498,442 A1, describing silicone HEURS
13. H Hoffmann and G Wanka, The aggregation behavior of poly(oxyethylene)-
poly(oxypropylene)-poly(oxyethylene) block copolymers in aqueous solution, Colloid
Polym Sci 268 101-117 (1990)
14. B Xu et al, Langmuir 13 6896 (1997)
15. B Xu et al, Langmuir 13 6903 (1997)
16. US Pat 5,496,908, B Xu et al
17. R Yekta and M Winnik, Fluorescence studies of associating polymers in water:
Determination of the chain end aggregation number and a model for the association
process, Macromolecules 28 956-966 (1995)
18. T Annable and R Buscall, The rheology of solutions of associating polymers:
comparison of experimental behavior with transient network theory, J Rheol 37 695-726
(1993)
19. US Pat 5,914,373, Water soluble aminoplastether copolymers, CW Glancy and AL
Steinmetz, assigned to United Catalysts, Inc (Jun 22, 1999)
20. US Pat 6,800,096, Composition, process and kit for bleaching keratin fibers comprising
at least one thickening polymer with an aminoplastether skeleton, F Legrand and D
Allard, assigned to LOral SA (Oct 5, 2004)
21. US Pat 6,800,098, Oxidation dye composition for keratinic fibres containing a thickening
polymer with an ether plastic skeleton, D Allard and F Legrand, assigned to LOral SA
(Oct 5, 2004)
22. US Pat 6,805,856, Hair care compositions which reduce color loss in hair and methods
of using the compositions, M Wong and E Memisha, assigned to LOral (Oct 19, 2004)
23. MD Berthiaume et al, Effects of silicon pretreatment on oxidative hair damage, J Soc
Cos Chem 46 231-245 (Sep/Oct 1995)
24. US Pat 6,824,764, Use of particular aminosilicones as a pretreatment of processes for
coloring keratin fibers with direct dyes or with oxidation dyes, P Devin-Baudoin and A
Sabbagh, assigned to LOral (Nov 30, 2004)
25. US Pat 6,841,164, Silicone compositions for personal care products and method for
making, MD Butts, SA Nye, CM Byrne, AR Katritzky and JW Merkert, assigned to
General Electric Company (Jan 11, 2005)
26. US Pat 6,844,002, Silicone compositions for personal care products and method for

411
Lochhead Chapter 41
making, MD Butts, SA Nye, CM Byrne, AR Katritzky and JW Merkert, assigned to

General Electric Company (Jan 18, 2005)
27. US Pat Appl 2004/0258641, Cosmetic composition for dyeing human keratin materials,
comprising at least one fluorescent dye and at least one cationic polymer, and a dyeing
process therefore, G Plos and H Samain (Dec 23, 2004)

Chapter 42
Multilayer Lamella
Vesicles in Oxidative
Dye Formulations:
Characterization and
Performance
KEY WORDS: multilayer lamella vesicles, emulsion rheology, image
analysis, hair color washfastness, ammonia odor
ABSTRACT: Well-structured multilayer lamella vesicle phase encapsulated
actives enhance the diffusion of dye intermediates
and coupling agents into the hair cortex, reducing the
evaporation rate of volatile ammonia in coloring mixtures
and showing better bleaching/coloring performance.
The bleaching and coloring of hair has become increasingly

popular over the years. Color is produced inside the hair fiber by
hydrogen peroxide-induced oxidation and coupling reactions of
aromatic amines and phenols. Oxidative dyeing usually is carried
out under alkaline conditions, preferably at a pH level of 9 to 10.
At the time of dyeing, an alkaline emulsion containing dye com-
ponents is mixed with a peroxide developer, which is stabilized for
storage at a pH level of 3 to 5. The resulting color mixture then
is applied to hair for 20 min to 40 min before being rinsed off
with water.
Surfactants in color mixtures play important roles in the efficacy
of hair color products:
Emulsificationsurfactants form stable and well-organized

414
Color Multilayer Lamella Vesicles in Oxidative Dye Formulations
o/w emulsions for better solubility and distribution of dye

intermediates and coupling agents.
Wettingsurfactants provide fast and uniform wetting to
accelerate the diffusion of dye intermediates and coupling
agents into hair the cortex.
Spreading and cleansingsurfactants ensure uniform dye
coverage and help to remove dye residue on the hair surface
that contributes to a poor feel, dull appearance and difficult
combing.
Many studies have been performed on factors that affect the
bleaching and coloring process. These factors include: dye solubility
and distribution, coupling rates between the dye and coupling agent,
diffusion rates of dye intermediates and coupling agents into the
hair cortex, hair swelling rate, effect of different alkali on the dyeing
process and the efficiency of dye use.
Multilayer lamella vesicles (MLVs) are a good delivery system
for active ingredients and have been used widely in health care and
personal care products. MLVs improve the dispersion of difficult-
to-solubilize compounds such as drugs and sunscreen oils and
enhance adhesion on the skin surface and in the sustained release of
active ingredients.
Phosphate esters have long been used in hair and skin care
formulations, including hair relaxers, perms, sunscreens and color
bases, as excellent emulsifiers and viscosity-thickening agents. In a
previous study,1 MLV structures were reported to form in sunscreen
formulas with phosphate ester emulsifiers and played an impor-
tant role in enhancing the deposition of sunscreen oil on the skin
surfacethus improving the SPF water-wash resistance. As of yet,
no research paper has been published on studies of MLV phases in
oxidative hair dye formulas.
The major challenges for developing new oxidative hair color
formulas are: better color washfastness, faster color processing to
decrease hair damage, richer color uptake and less ammonia odor.
In this paper, researchers report on recent studies of MLV structures
formulated with different phosphate-ester emulsifiers in oxidative
hair dye formulas, and the correlation between the phase structure
and bleaching/coloring performance.

415
Materials
Four hair bleach bases, which are referred to as samples CES-B,
HCE-B, CS20-B and ceteth-B, and four oxidative hair dye
(auburn) bases, samples CES-D, HCE-D, CS20-D and ceteth-D,
containing different phosphate ester/nonionic emulsifiers were
obtained and are listed in Table 1. A hydrogen peroxide color devel-
oper was prepared and is listed in Formula 1. Bleached hair was
purchased from International Hair Importers Inc., New York.
Test Methods
MLV phase identification: The phase structure of emulsions depends
on various factors including emulsion type (o/w or w/o), concen-
trations of surfactants and ingredients, molecular structures of
emulsifiers, and production conditions (shearing speed and tempera-
ture). Generally, micelles exist in two-component systems and their
shape can be spherical, cylindrical, prolate, oblate or inverse. At
higher concentrations, surfactant or mixed surfactant solutions can
form liquid crystalslamellar and hexagonal phases. The structure
of liquid crystals can be identified using an optical microscope with
crossed polarizers according to their special patterns.2-3
In the current experiments, an oxidative hair dye or bleach base
sample was placed on a glass slide with a cover glass on a thermal
stage at a constant temperature of 25C. Digital images of dye or
bleach bases were captured using a digital camera system attached to
a polarizing microscopea and image analysis was performedb.
Hair color development rate, color washfastness: Hair color
indexes (CIE L*, a*, b* system) were measured using a spectrocolo-
rimeterc. The changes in color indexes after cosmetic treatments
indicate directions of hair color shifts: if L* increases, hair turns
lighter; if a* increases, hair becomes redder; if b* increases, hair is
more yellow. E is the total color index. The greater the change in E,
the more alternations to the total color of the hair.
a
Nikon ACT-2U Digital Camera System and Nikon Optiphot-Pol Polarizing Microscope are
products of Nikon Inc.
b
Image-Pro Plus 4.5 is a product of Media Cybernetics.
c
LabScan XE Spectrocolorimeter is a product of Hunter Associates Lab.

416
Table 1. Hair dye/bleach base formulas
Ingredients Weight %
HCE-D Ceteth-D HCE-B Ceteth-
CES-D CS20-D CES-B CS20-B B
Cetearyl alcohol (and)
dicetyl phosphate (and)
ceteth-10 phosphatei 5.00 5.00
Cetearyl alcohol (and)
dicetyl phosphate (and)
ceteth-20 phosphateii 5.00 5.00
Oleth-5 phosphate (and)

dioleyl phosphateiii 5.0 5.00
Ceteth-20 5.00 5.00
Petrolatum 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00
Beeswax 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00
Stearyl alcohol 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00
Cetearyl alcohol 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00
BHT 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05
Glycerin 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00
P-Aminophenol 0.30 0.30 0.30 0.30 - - - -
Resorcinol 0.20 0.20 0.20 0.20 - - - -
4-Amino-2-hydroxytoluene 0.10 0.10 0.10 0.10 - - - -
Ascorbic acid 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30
Disodium EDTA 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20
Sodium sulfite 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20
Ammonium hydroxide (25%) 9.00 9.00 9.00 9.00 9.00 9.00 9.00 9.00
Water (aqua) 60.65 60.65 60.65 60.65 61.25 61.25 61.25 61.25
i.
Crodafos CES is a product of Croda Inc.
ii.
Crodafos CS-20 acid is a product of Croda Inc.
iii.
Crodafos HCE is a product of Croda Inc.
A hair tress was placed on a special sample holder for color mea-
surement. Five readings at different portions of each side of the hair
tress were taken and a total of 10 readings were averaged on each
hair tress. The differences in color indexes of a hair tress, before and
after dyeing at different dyeing periods, were calculated to deter-

417
mine the color developing rate. The differences in color indexes of

a dyed hair tress before and after multiple shampoo washings were
calculated to evaluate the color washfastness performance. Less of a
change measured in color indexes after washing meant better color
washfastness.
Emulsion rheology: The rheological profiles of dye formulas and
their mixtures with the developer (weight ratio of 1:1) were deter-
mined using a rheometer at constant temperature of 25C and the
data analysis was performed using computer softwared.
Formula 1. Hydrogen peroxide color developer
Cetearyl alcohol (and) dicetyl phosphate (and) ceteth-20 phosphate 5.00% w/w
Paraffinum liquidum (mineral) oil 5.00
Cetyl acetate (and) acetylated lanolin alcohol 0.50
Steareth-20 0.50
Hydrogen peroxide, 35% 17.00
Water (aqua) 72.00
Viscosity = 7000 cps @10 rpm, pH = 3.0
The correlation between shear rate, shear stress and viscosity of

liquids can be expressed as the power law:4
Eq.1 = KDn
Eq.2 = /D = KDn-1
where D is the shear rate (1/s), is the shear stress (Pascal), is

the calculated viscosity (mPa.s), K is the consistency index, and n is
the flow index. K and n are characteristic constants of the material.
d
The Brookfield DV-III Rheometer and Rheocalc 2.3 software are products of Brookfield
Engineering Lab.

418
Liquids with an n value greater than 1 are shear thickening; those

with an n value of less than 1 are shear thinning. Shear sensitivity, S,
is defined as 1-n. The smaller the n value, the larger the shear sen-
sitivity and the faster the decrease in viscosity with increasing shear
rate. When n=1 and = K, then is the Newtonian viscosity. The
viscosity remains constant at various shear rates.
Evaluation of ammonia odor: The evaluation of ammonia odor
of various bleach bases was conducted with panelists. Each panelist
gave a score in ammonia odor and the total scores were averaged.
Results and Discussion

Emulsion structure: Figure 1 shows digital images of oxidative hair
dye bases containing different phosphate esters or nonionic surfac-
tant ceteth-20 under a microscope without using crossed polarizers.
The determined average particle sizes are: Ceteth-D: 3.8 m;
CS20-D: 6.0 m; CES-D: 8.8 m; and HCE-D: 12.5 m (broad
distribution). The average particle sizes are in the following decreas-
ing order: HCE-D > CES-D > CS20-D > Ceteth-D.
Figure 2 shows digital images of the same dye base samples
under the microscope with crossed polarizers. No typical liquid
crystal pattern was observed in the hair dye formula containing
nonionic ceteth-20 (Figure 2a). In contrast, all other dye formulas
containing phosphate esters showed clear liquid crystal patterns
well-defined maltese crossesthe evidence of MLV formation
From Figure 2, it is apparent that the addition of different phos-
phate esters formed different structures of MLV particles and the
formed MLV structures were related to the molecular structure of
the added phosphate ester. Schematic molecular structures of three
phosphate esters are shown in Figure 3 and their major composition
and molecular differences are summarized in Table 2.
It can be seen that HCE has unsaturated 18-carbon chains.
These carbon chains mainly have a cis-configuration, which is
a rigid and extended carbon chain. Therefore, HCE has longer
extended dynamic molecular size compared to CES and CS20, both
of which have saturated 16-carbon chains, which are more flexible.
It also was noted that the CS20 diester has the same 16-carbon
chain but with 10 more ethylene oxide (EO) groups in the molecule,

419
Figure 1. Micrographs of different dye bases (X400)

1-1 Ceteth-D, 1-2 CS20-D, 1-3CES-D, 1-4 HCE-D

420
Figure 2. Micrographs of different dye bases under crossed polarizers (X400)

2-1 Ceteth-D, 2-2 CS20-D, 2-3CES-D, 2-4 HCE-D

421
Table 2. Structural differences between phosphate esters
Phosphate
Ester Diester Monoester Fatty Alcohol
CES Di-Cetyl (C16) Ceteth-10 (C16, 10EO) Cetearyl Alcohol (C16 + C18)
CS-20 Acid Di-Cetyl (C16) Ceteth-20 (C16, 20EO) Cetearyl Alcohol (C16 + C18)
HCE Di-Oleyl (C18=) Oleth-5 (C18=, 5EO) None
Figure 3. Schematic structures of different phosphate esters

3-1 CES, 3-2 CS20, 3-3 HCE

422
compared to CES. The additional 10 EO groups in the molecule

increase the chain length and the molecular flexibility or the ten-
dency to form coils. Therefore, it is expected that CS20 has smaller
than average molecular dynamic sizes compared to CES.
In summary, the average dynamic molecular sizes of these
phosphate esters in emulsions can be arranged in the following
decreasing order: HCE > CES > CS20, which is the same order of
the average sizes of formed MLV particles. Based on these observa-
tions, it may be concluded that the larger the dynamic molecular
size of the phosphate ester, the greater the average sizes of formed
MLV particles in the corresponding dye formula.
Hair bleaching/coloring performance: In order to determine the
color developing rate, changes in color indexes of dyed hair at differ-
ent time periods were measured. Digital images of hair tresses dyed
with different dye bases at 5 min and 10 min are shown in Figure 4
(see Color Insert 15). Changes in the red color index of a* and total
color index of E at different dyeing periods are shown in Figures 5
and 6, respectively.
It can be deduced from the above hair images and graphs that
hair dyed with dye bases containing phosphate esters showed faster
changes in color indexes of a* and E than those of hair dyed with
ceteth-D. The hair dyed with HCE-D demonstrated the fastest col-
or-developing rate. It is apparent that the replacement of nonionic
emulsifier with the same amount of phosphate ester in the oxidative
auburn dye formula accelerated the dyeing process and generated a
richer final color.
To further confirm the faster dyeing processes provided by dye
formulas containing phosphate esters, bleaching tests were con-
ducted using the same oxidative dye formulations but without dye
intermediates. Changes in hair color index L* (lightness) of hair
samples bleached with these formulas at different bleaching periods
are presented in Figure 7. The same trend was observed; the bleach
formulas containing phosphate esters showed faster bleaching rates
compared to the formulation incorporating ceteth. The HCE-B
formula demonstrated the fastest bleaching rate among all tested
formulas. These results are consistent with those obtained from hair
dyeing experiments.

423
Figure 4. Images of dyed hair at different dyeing times

4-1 Dyed hair tresses after 5 min, 4-2 Dyed hair tresses after 10 min

424
Figure 5. Changes in red color index of dyed hair at different dyeing periods
Figure 6. Change in total color of dyed hair at different dyeing periods

425
Figure 7. Change in lightness index L* of bleached hair at different bleaching periods
Correlation between MLV structure and dyeing rate: In order to

understand the mechanism of enhancement in coloring performance
by addition of phosphate esters in the oxidative dye base, the color
development processes of mixtures of dye bases and the developer
were investigated. Digital images of color mixtures at different
mixing times were taken to monitor the color developing process.
Figure 8 (see Color Insert 16)shows the color developing processes
of two typical color mixtures: HCE-D and ceteth-D. It can be seen
that color developing processes were different for the two color
mixtures; the HCE-D color mixture showed slower color develop-
ing than ceteth-D.
Most dye intermediates and coupling agents are slightly water-
soluble and have a tendency to stay in the oil phase inside MLV
particles. Hydrogen peroxide molecules in the developer are water-
soluble and distributed in the continuous water phase. After the
HCE-D dye base was mixed with the developer, the phase structure
of the color mixture was examined and most of the MLV particles
found to be present. Thus, the dye intermediates inside the MLV

426
1 2
3 4
5 6
Figure 8. Color-developing processes of two color mixtures

8-1 2 min (ceteth-D), 8-2 5 min (ceteth-D), 8-3 20 min (ceteth-D)
8-4 2 min (HCE-D), 8-5 5 min (HCE-D), 8-6 20 min (HCE-D)

427
particles must have less chance to contact with the hydrogen perox-
ide molecules in the continuous water phase to be oxidized. When
the color mixture was applied and spread onto the hair surface, both
the non-oxidized color intermediates and coupling agents were
released and diffused separately into the hair cortex. Then the dye
intermediates were oxidized and further reacted with the coupling
agent inside the hair, thus locking in more color rather than the
color laying on top of the hair. As a result, hair dyed with color mix-
tures containing MLV structures showed better color uptake, faster
coloring rate and richer final color.
In ceteth-D color mixture, the oxidation of dye intermediates and
coupling reaction began immediately in the bulk water phase after
mixing the dye base with the developer. This is because of the lack of
a structured phase to protect dye intermediates. The molecular weight
of the dye intermediate complex increased and the portion of dye
intermediates entering into hair cortex decreased. As a result, the hair
color development rate was lower and the final color was not satisfied.
Color washfastness: Changes in chromaticity index C and total
color index E of dyed hair samples after 20 consecutive shampoo
washes are shown in Figure 9. Hair dyed with dye formulas contain-
ing phosphate esters showed better color washfastness performance
compared to the hair dyed with ceteth-D dye formulas, which is a
direct result of the better dye uptake described above.
Figure 9. Changes in color indexes after 20 shampoo washes

428
Rheological properties of dye bases and their mixtures with devel-

oper: The determined rheological parameters of oxidative dye bases
and their color mixtures are summarized in Table 3. Rheological
profiles of color mixtures (1:1) of different dye formulas and the
color developer are presented in Figure 10.
Table 3. Rheological properties of dye bases and color

mixtures
Color Base/Mixture Yield Stress Shear Viscosity @ 10RPM,

(D/cm2) Sensitivity cps
CS20-D 250.5 0.76 7942
CES-D 265.9 0.79 7286
HCE-D 46.6 0.64 2535
Ceteth-D 64.8 0.57 5011
CS20-D+ Developer (1:1) 133.3 0.70 5011
CES-D + Developer (1:1) 256.6 0.68 5100
HCE-D+ Developer (1:1) 41.7 0.62 2112
Ceteth-D + Developer (1:1) 106.4 0.67 3854
Figure 10. Plot of viscosity vs. shear rate for color mixtures

429
From Table 3, it can be seen that the HCE-D color mixture

showed the smallest viscosity and the least yield stress and low shear
sensitivity (shear-thinning) among all tested color mixtures. Low
viscosity is favorable for fast diffusion of dye intermediates and
coupling agents into the hair cortex. Comparing the calculated shear
sensitivity of dye formulas with their emulation structure in Figure
1, ceteth-D, which showed the least average particle size, was shown
to have the lowest shear sensitivity and low yield stress. This can be
attributed to the smallest average particle size and lack of organized
MLV structures in the formula.
CES-D and CS20-D dye formulas showed more pronounced
shear-thinning characteristicshigher initial viscosity at low shear
rates and lower viscosity at high shear ratesand larger yield stress
values compared to HCE-D and ceteth-D formulas. This corre-
sponds to their predominant MLV structures and relatively larger
average particle sizes. It is interesting to note the emulsion structure
of HCE-D dye formula. It is composed of some large-sized par-
ticles but with broad size distribution. Its lowest viscosity, smallest
yield stress and relatively low shear sensitivity can be related to this
special structure and broad size distribution.
Reduction in ammonia odor: Subjective evaluations of ammonia
odor were conducted and the results are summarized in Figure
11. The lower ammonia odor of CS20-B bleach base also may be
attributed to its well-formed MLV structure. Ammonia molecules
in CS20-B bleach base are water-soluble and tend to remain inside
the lamellar water phase (structured water), which is separated from
the bulk continuous water phase.
Ammonia molecules are microencapsulated and therefore the
evaporation rate of ammonia molecules inside the lamellar phase is
much lower than that of free ammonia molecules in the bulk water
phase. As a result, the ammonia odor level is lower. In ceteth-B for-
mula, no microencapsulation occurred and all ammonia molecules
are in the bulk water phase or easily evaporated. It is not surprising
that the ammonia odor level of the ceteth-B bleach base would be
higher.

430
Figure 11. Evaluation of ammonium odor of bleach bases
Conclusions
In summary, addition of phosphate ester to the oxidative hair dye
formula enhanced the formation of liquid crystals and MLVs. The
MLV structure in oxidative hair dye formulas increases the coloring
rate and provides a richer final shade and better color washfastness
performance. MLV structures reduced ammonia odor in oxidative
hair dye and bleach formulas. The MLV structures formed in hair
oxidative dye formulas and bleach bases depend on the molecu-
lar structure of the added phosphate ester: the larger the average
dynamic molecular size of the phosphate ester, the greater the aver-
age size of the MLV particles formed. MLV particle size and size
distribution show great effects on the rheological properties of the
formula, including: viscosity, yield stress and shear thinning.
Structured surfactant fluids (SSF) have widely been used in
personal care applications as delivery systems for active agents. This
is the first report on formation of MLVs in hair dye/bleaching base
formulas. These structures could be used to improve hair dyeing/
coloring efficiency and reduce unpleasant ammonia odor in formu-

431
lations. With a better understanding of the delivery mechanism,

formulators now can produce SSFs in their labs to enhance efficacy
in their formulations.
Timothy Gao, PhD, Robert Bird and Abel Pereira

Croda Inc., Edison, NJ USA
Ryuji Akatsuka
Croda Japan KK, Tokyo, Japan
References
1. T Gao, J Tien and Y Choi, Sunscreen formulas with MLV structure, Cosm & Toil, 118 10,
4148 (2003)
2. D Roux and F Gauffre, The onion phase and its potential use in chemistry, ECC
Research 1724 (1999)
3. J Zipfel et al, Shear induced structures in lamellar phases of amphiphilic block
copolymers, Phys Chem 1 390510 (1999)
4. P Miner, Emulsion rheology: creams and lotions, in Rheological Properties of Cosmetics
and Toiletries, D. Laba, ed, New York: Marcel Dekker (1993)

Chapter 43
Using Natural Keratin

Biopolymers to Protect
the Hair
KEY WORDS: hair, antiaging, pollution, keratin, intermediate filament
protein, combing force, tryptophan fluorescence, UV,
pollution, cigarette smoke, ozone, sulfur dioxide
ABSTRACT: UV protection and sacrificial targets for aggressive pollutants
are two hair-protection strategies employed by a new keratin
biopolymer manufactured from wool.
Consumers are becoming ever more conscious of the damaging

effects of environmental insults such as pollution and sunlight. Such
concerns have helped to establish key trends within skin care and
now are fueling innovation within the hair care arena where antiag-
ing and antipollution technology is becoming increasingly relevant.
Hair is a complex biological system that has been designed by
nature to perform specific functions. The intricate structure of hair
is being discussed more than ever in articles and scientific meetings
involving cosmetic chemists.1 Increasingly, attention is directed to
the relationship between the structure and function of hair and how
this impacts on ensuring the delivery of effective and innovative
ingredients.
Hair consists principally of keratin protein and a small amount
of lipid. The chemistry of hair can be modified by aging, by length-
ening and by environmental insults such as pollution and sunlight.
When the hair chemistry is modified, some of the natural properties
of hair are compromised. The mechanism by which this dam-
age occurs is understood now more than ever.2 For example, UV
radiation photo-oxidizes proteins. Protein photo-oxidation leads to

434
Sun Protection Using Natural Keratin Biopolymers to Protect the Hair
cleavage of disulfide bonds, cross-linking of proteins, and breaking

of thioester bonds, resulting in the release of bound surface lipids.
These reactions lead to a deterioration of the hair properties, notice-
able to consumers in the form of poor manageability, dryness and
brittleness, loss of shine and, in extreme cases, decreased strength
(fiber breakage).3 Actives that can address these negative issues and
prevent them from occurring clearly have antiaging efficacy and
have the potential to maintain youthful hair.
This chapter discusses two strategies to counter the damag-
ing effects of age and pollution on hair: UV protection and the
implementation of sacrificial target components. Both strategies are
employed in a biopolymer made from intact keratin proteins and
keratin peptides from the wool of New Zealand sheep.
Keratin Biopolymer
A keratin biopolymera has been designed to operate by sacrificial
and chemical protection means:
It protects the hairs natural protein by providing preferential
binding sites and degradation sites for aggressive influences.
The protected cystine groups present in the keratin biopoly-
mer provide a site for reactivity. The biopolymer components
acting on the surface of the fiber provide a shielding effect.
It provides antioxidant activity against aggressive influences.
This keratin biopolymer is a purified form of keratin intermedi-
ate filament protein (IFP). This purified form is manufactured solely
from wool of New Zealand origin. This material is predominantly
intact protein, meaning it has not been degraded in any form; it
retains both its original size (molecular weight ~55 kD) and amino
acid composition. It also contains a smaller amount of peptide (aver-
age molecular weight 34 kD). IFP (Figure 1) was selected as the
protein source because it is the protein that gives natural hair fibers
their strength. Table 1 shows the amino acid profile of this propri-
etary keratin biopolymer, which will be called keratin IFP in this
chapter to distinguish this keratin biopolymer from other existing
a
Keratec IFP [INCI: Aqua (and) Keratin (and) Hydrolyzed keratin] is a product of Keratec
Ltd. distributed exclusively by Croda Chemicals Europe.

435
Roddick-Lanzilotta et al. Chapter 43
Figure 1. Hair structure
Table 1. Amino acid profile of the keratin biopolymer
Mole (%)
Aspartate 7.9
Glutamate 15.3
Serine 11.0
Glycine 8.2
Histidine 0.9
Arginine 7.7
Threonine 6.5
Alanine 7.5
Proline 5.5
Tyrosine 1.1
Valine 6.5
Methionine 0.2
Lanthionine 0.2
Isoleucine 3.6
Leucine 8.7
Phenylalanine 2.4
Lysine 2.1
Cystine 4.3

436
keratin blends, especially those containing synthetics (see More on

IFP from New Zealand).
More on IFP from New Zealand

David A. D. Parry is distinguished professor of biophysics and head
of institute at Massey University in Palmerston North, New Zealand. His
research focuses on determining the structure and function of fibrous
biological macromolecules. His Web site reports that a major advance in
the past year or so has been the detailed determination of the structure
of the hair intermediate filament. We have shown that the expression
and assembly of these intermediate filament proteins, which occurs under
reducing conditions at a point just above the dermal papilla, leads to
a structure that is very closely similar to that seen for other classes of
intermediate filaments.
However, when the intermediate filament associated proteins are
laid down at a point higher in the hair follicle and conditions change
to an oxidizing one following cell death, there is a significant structural
rearrangement of the constituent molecules. This leads to a unique
structure. These observations have brought together a diverse group of
experimental observations that previously seemed incompatible. Following
on from these studies, it has been possible to explain the different
organization of sheets of IF in the para- and orthocortex of hair.
www.massey.ac.nz/~wwifs/staff/parry.shtml (Accessed Apr. 2, 2006)
The intact keratin protein has excellent film-forming properties

that allow it to be substantive to the hair from a range of hair care
formulations. The lower molecular weight peptide component is
capable of penetrating the cortex of the hair fiber. The dual action
of surface coating and penetration of the peptide leads to antiag-
ing efficacy (i.e., prevention of age-related damage) through a
mechanism of sacrificial degradation of surface active proteins and
antioxidant activity from the fractions within the cortex.
In summary, a liquid form of hair is being applied to the surface
and interior of the fiber. This liquid form is somewhat more reactive
than the hair itself. Hence any aggression that would normally react
with the hair leading to deterioration of its properties will preferen-

437
tially attack the applied keratin biopolymer, offering protection to

the fiber.
Environmental Pollution and Hair Damage

The impact of environmental pollutants on the hair is well-rec-
ognized and becoming increasingly important as pollution levels
continue to be of concern. Work was undertaken to determine how
hair properties are affected by pollutants commonly found in the
environment. These pollutants include cigarette smoke, ozone and
gaseous sulfur dioxide.
Combing force analysis and hair tryptophan content analysis
were used to assess the condition of hair. Combing force analysis
is an accepted method for measuring the hair surface health, and is
related to the consumer perception of manageability.3 Tryptophan
is an amino acid that is sensitive to damage from reactants and UV
radiation and is therefore a useful indicator of age-related damage in
hair.4 Figure 2 shows the steady decrease in tryptophan content from
root to tip in hair from a healthy volunteer. The regular decrease
illustrates the effect of environmental exposure over time and vali-
dates the use of tryptophan analysis as a probe for hair damage.
Figure 2. Tryptophan content on the hair surface measured at different distances from the scalp

438
Cigarette smoke: Cigarette smoke contains more than 4,000

components, including many that are known to be aggressive toward
biological materials. Among the aggressors are formaldehyde, car-
bon monoxide, ammonia and reactive oxygen species (ROS).
Combing force analysis was used to investigate the effect of ciga-
rette smoke exposure on untreated (virgin) hair, hair treated with a
base conditioner and hair treated with 1% keratin biopolymer added
to the conditioner base. A rinse-off protocol was used. Tresses were
exposed to smoke from eight cigarettes with application of condi-
tioner prior to initial exposure and reapplication after four cigarettes.
The results following smoke exposure (Figure 3) indicate that
compared to the force required to comb the untreated hair, only 38%
as much combing force was required in the keratin IFP-treated hair
(and 68% for the conditioner base without keratin IFP).
Figure 3. Effect of smoke exposure on average force to comb hair tresses that were pre-treated
with keratin biopolymer conditioner, pre-treated with base conditioner or untreated
Ozone: The pollutant ozone is formed by the reaction of nitrogen

oxides, hydrocarbons and sunlight, and is a component of photo-
chemical smog. This extremely powerful oxidant reacts with proteins,
attacking amino acids such as cystine and tryptophan. Even very
small amounts of ozone can cause significant damage to the hair,
particularly when it is wet. This is illustrated in Figure 4a, which

439
shows a scanning electron micrograph of a wet hair fiber exposed

to 0.1 ppm of ozone for 30 sec. In this instance a bubbling effect
was observed and holes were generated in the outer cuticle layer,
exposing the cortex of the fiber and likely causing cuticle loss during
routine grooming practices.
a)
b)
c)
Figure 4. Effect of ozone exposure on hair

a) Scanning electron micrograph of untreated wet hair exposed to 0.1 ppm of ozone for 30 sec
b) Effect of ozone exposure (20 ppm for 2 min) on average force to comb hair tresses that
were untreated or pre-treated with a base conditioner with or without 1% keratin IFP
c) Effect of ozone exposure (20 ppm for 2 min) on relative tryptophan content of hair tresses
that were untreated or pre-treated with a base conditioner with or without 1% keratin IFP

440
Combing force and tryptophan analysis studies were used to

assess the effect of ozone on untreated hair, and hair to which a con-
ditioner base or 1% keratin IFP conditioner had been applied using
a rinse-off protocol. Wet hair tresses were exposed to 20 ppm ozone
for 2 min.
The results of the combing force study are displayed in Figure
4b. Addition of the keratin IFP had the effect of decreasing the
combing force (i.e., increasing manageability) of ozone-exposed hair
to 59% of the untreated control.
Interestingly, treatment with the conditioner base alone had a
detrimental effect, markedly increasing the required combing force
(to 169% of the control). It is believed that this increase arises from
reaction between the substantive conditioning agents and the ozone.
The reaction exacerbates the damage to the fiber surface. This was
supported by SEM investigations (not shown).
Ozone is known to react quickly with organic matter that con-
tains double bonds, activated aromatic groups or amines, and it reacts
more rapidly with ionized and dissociated organic compounds, such
as quaternaries found in conditioning systems. These reactions in
turn lead to bi-products such as peroxide and carboxyl compounds.
It is thought that in the presence of keratin IFP, ozone reacts pref-
erentially with the active, protecting the hair fiber from damage
associated with these reactions. Further work is being undertaken to
investigate whether this effect is typical of many conditioning systems.
Tryptophan fluorescence studies also were carried out on the
ozone-exposed fibers and the results are shown in Figure 4c. It was
found that exposing untreated control hair to ozone reduced the
emission intensity due to tryptophan. Treatment with the condi-
tioner base also resulted in tryptophan loss, but no loss was observed
in hair treated with the conditioner containing keratin biopolymer.
Sulfur dioxide gas: Sulfur dioxide (SO2) gas is produced by
burning coal, high-sulfur oil and diesel fuel, and together with
particulates makes up the main pollutant load in many cities. It is
a reducing gas and thus can potentially cleave disulfide bonds that
hold the hair together.
Experiments were carried out to investigate the effect of SO2
on hair fiber properties. Tresses were exposed to 40 ppm of gas-

441
eous SO2, which decayed to 0 ppm over 12 h. Figure 5 shows

combing force and tryptophan analysis of sulfur-exposed hair that
was untreated or pre-treated with either a conditioner base or the
conditioner containing 1% keratin biopolymer. Application of the
keratin conditioner decreased the combing force to 80% of the force
required to comb the control untreated sample. No improvement
was observed when the conditioner base was used. The keratin
conditioner treatment also provided complete protection of the
tryptophan in the cuticle, whereas in the absence of treatment the
SO2 gas decreased the tryptophan content of the hair to approxi-
mately 80% of its original value.
a)
b)
Figure 5. Effect of sulfur dioxide exposure on hair

a) Effect of gaseous SO2 exposure (40 ppm for 12 h) on average force to comb hair tresses that
were untreated or pre-treated with a base conditioner with or without 1% keratin biopolymer
b) Effect of gaseous SO2 exposure (4 ppm for 60 h) on relative tryptophan content of hair tress-
es that were untreated or pre-treated with a base conditioner with or without 1% keratin IFP

442
UV Radiation and Hair Damage

Ultraviolet radiation, particularly UVB, is another major source of
hair damage from the environment. The effect of UVB on hair and
the protective properties of keratin biopolymers were examined
using tryptophan analysis and single fiber tensile strength mea-
surements. Tryptophan is particularly sensitive to UVB radiation,
being readily destroyed, and thus is an extremely sensitive probe for
photo-oxidative damage of hair. Fiber tensile strength is a rec-
ognized method for assessing the structural integrity of the fiber
cortex, giving a useful indication of overall health.
An experiment was performed to mimic the progressive hair
damage from exposure to sunlight and grooming practices. The
baseline tryptophan content was measured using a fluorescence
spectrophotometer. The hair then was irradiated with UVB for the
equivalent of 96 h of sunshine, and washed with surfactant sham-
poo. This cycle of irradiation and wash was repeated several times.
The resulting decay in tryptophan content is shown in Figure 6a.
This experiment then was repeated, with the modification that this
time the hair was treated with a 5% solution of keratin IFP using a
rinse-off protocol before UVB irradiation in each cycle. The results
of the tryptophan assessment are displayed in Figure 6b. It was
observed that treatment with the keratin IFP protected the trypto-
phan of the hair, leaving it in an undamaged state.
A further fluorescence experiment was performed using a rinse-
off protocol to investigate the delivery of the keratin IFP from a
conditioner formulation. The results are displayed in Figure 6c. The
tryptophan levels of the untreated hair and conditioner base-treated
hair decreased to approximately 6070% of the initial value, whereas
treatment with the base conditioner formulation containing the
keratin biopolymer at a level of 1% maintained the surface fluores-
cence levels of the hair fiber.
Finally to assess the effect of UV radiation on the bulk
mechanical properties of hair, tensile measurement was applied to
UVB-exposed hair with and without treatment with the keratin
biopolymer at a level of 5% in a conditioner. The resulting data are
displayed in Figure 6d. The effect of UVB light exposure on virgin
untreated hair was to decrease the work required to extend the fiber

443
by 20%; in other words, the fiber was damaged and thus weakened.
Application of the conditioner base did not protect the underly-
ing hair fibers from UV damage as evidenced by a reduction in the
amount of work required for fiber extension. However, applying
conditioner base formulation containing 5% of the keratin biopoly-
mer resulted in tensile properties that were very similar to the tensile
properties of the fiber before exposure, indicating that the biopo-
lymer was successfully preventing aging damage to the fiber, and
maintaining the fiber in its original condition.
a)
b)
Figure 6. Effect of UVB exposure on hair

a) Effect of UVB irradiation (equivalent of 96 h sunshine) on tryptophan content of
surfactant-washed hair tresses that were not pre-treated
b) Effect of UVB irradiation (equivalent of 96 h sunshine) on tryptophan content of surfactant-
washed hair tresses that were pre-treated with 5% solution of keratin IFP

444
c)
d)
Figure 6. Effect of UVB exposure on hair

c) Effect of UVB irradiation (equivalent to 96 h sunshine) on tryptophan content of hair tresses
that were untreated or pre-treated with a base conditioner with or without 1% keratin IFP
d) Effect of UVB irradiation (equivalent to 125 h sunshine) on work required to achieve a 20%
extension of wet hair fibers that were untreated or pre-treated with a base conditioner with or
without 5% keratin IFP
Conclusions
Age-related damage to hair occurs as a result of exposure to the
external environment. The detrimental effect of commonly encoun-
tered pollutants (cigarette smoke, ozone and sulfur dioxide) and
sunlight has been demonstrated using a combination of analysis
techniques and consumer-relevant measurements. Damage to the
proteins and lipids of the hair cuticle and cortex can be prevented

445
through the sacrificial effect of a unique keratin biopolymer ingre-

dient that essentially undergoes the same degradation processes in
preference to the hair fiber.
Alisa Roddick-Lanzilotta and Rob Kelly

Keratac Ltd., Christchurch, New Zealand
Sonya Scott
Canesis Network Ltd., Christchurch, New Zealand
Grant Mitchell and Surinder Chahal
Croda Chemicals Europe, East Yorkshire, England
References
1. R Schueller and P Romanowski, Inside the hairAn advanced biology model, Cosmet
Toil 120(11) 5358 (2005)
2. V F Monteiro, AS Pinheiro, ER Leite, JAM Agnella, MA Pereira-Da Silva and E Longo, UV
radiation: Aggressive agent to the hairAFM, a new methodology of evaluation,
J Cosmet Sci 54 271281 (2003)
3. P Maillan, Measurement of UV protection in the hair, Business Brieifing: Global
Cosmetics Manufacturing 15 (2004)
4. C M Pande and J Jachowicz, Hair photodamageMeasurement and prevention, J Soc
Cosmet Chem 44 109122 (1993)

Chapter 44
Protecting Against UV-

Induced Degradation and
Enhancing Shine
KEY WORDS: UV protection, hair combability, hair structure protection,
hair shine, chromophores
ABSTRACT: The data presented shows polysilicone-15 demonstrates
the ability to perform as a UV filter for hair protection and
decreases the combing force necessary after irradiation
to sample hair tresses in addition to enhancing the shine
attribute of a formulated product.
Healthy, shiny hair starts with proper protection and care. Unfortu-
nately, hair is exposed to daily stress and without proper treatment
it will become weakened and may appear unhealthy and dull. In a
recent nationwide survey conducted in the United States, consum-
ers demonstrated a high awareness to what UV radiation can do to
hair; 61% of 1,002 respondents indicated they knew that sun visibly
damages their hair.1
Artificially colored hair and natural uncolored hair of Asian and
Caucasian origin are susceptible to fading upon prolonged exposure
to UV radiation. Polysilicone-15 has been shown to reduce such
fading.2 The integrity of hair was shown to be affected by exposure
to UV radiation as demonstrated in one study in which the content
of amino acids such as cysteine and tryptophane present in hair
were protected against UV-induced degradation.3
In this chapter, we will explore two additional effects of poly-
silicone-15 on hair: hair combability and hair thermal stability via
Differential Scanning Calorimetry (DSC). These measurements
demonstrate the structural damage of hair caused by UV radiation

448
Sun Protection Protecting Against UV-Induced Degradation and Enhancing Shine
and how polysilicone-15 can help to protect the hair against

this damage.
Polysilicone-15
Polysilicone-15 has the benefits of a silicone plus the added ben-
efit of UV protection because the molecule has UV filter moieties
attached to the silicone backbone. The silicone provides shine, con-
ditioning and smoothening to the hair while the UV filters provide
protection against UV degradation and color change of the hair.
Polysilicone-15a is comprised of polysiloxane chains (Figure 1)
containing benzyl malonate chromophores (see Chromophores).
It is photostable and has a good safety profile due to its large
molecular size. Polysilicone-15 is approved in the European Union
as a UVB filter with an allowed dosage of up to 10% in sun care
products. It is not an approved sunscreen for skin protection in the
United States, but it may be used for hair care. The specifications of
polysilicone-15 are given in Table 1.
Figure 1. Structure of polysilicone-15
a
Parsol SLX is a product of DSM Nutritional Products AG

449
Maillan et al. Chapter 44
Chromophores
Organic molecules in sunscreens contain a chromophore which absorbs
light at certain wavelengths. Chromophores are groups of atoms bonded
together that share electrons. When wavelengths of light, whether visible or
UV, match the resonance of these electrons, they will be absorbed and cause
an excitation. This energy can then be released in many different ways.
The organic molecules in sunscreens usually emit a thermal release of
energy through vibrational relaxation or nonradiative decay. The molecule
goes from the excited state back to the ground state where it can continue
to absorb more UV light. Today, most sunscreens contain molecules than
have chromophores that absorb both UV-B and UV-A. The three most
common protective molecules found in most daily moisturizers were
oxybenzone, octisalycate and oxtinoxate.
Source: University of Pennsylvania School of Arts and Sciences Web site.

Available at: http://www.sas.upenn.edu/~hasty/work.html. Accessed: January 17, 2005.
Table 1. Specifications of polysilicone-15
Specifications
Appearance: Clear, pale yellow, liquid
Specific extinction E(1%, 1cm): 160 190
max: 310-314 nm in ethanol
Refractive index: 1.44
Specific gravity: 1.015 1.045
Protecting Hair Combability

The outermost layer of keratin fibers consists of approximately three-
quarters protein and one quarter lipid. UV degradation of amino
acids will result in a fragmented keratin structure and significant
structural changes of the surface cuticle cells (e.g. lifting, thinning).
UV-induced lipid degradation will also contribute to altered surface
properties. The state of the cuticle governs the frictional proper-
ties of hair fibers and determines how the hair feels to the touch and

450
how easily it combs out. These physical changes lead to a rough hair
surface and can directly relate to the stronger forces required to comb
UV damaged hair. Combability measurements are taken to assess
any alteration of the hair cuticle due to external stress and have been
proven sensitive toosl to detect UV-induced hair damage.4, 5
Methods: The wet combing forces on hair tresses Cau-
casian (bleached and permanently colored) and virgin Asian
samples were measuredb before and after irradiation [Irradi-
ance (300-400nm):6.5mW/cm2 @ 70% r.h and 23C, Atlas
ES25 Weather-Ometer; Dose: (over 140h): 3.2kJ/cm2] under
environmentally controlled conditions (20C, 65% r.h.). Before
irradiation, tresses were washed, dried, acclimated, wetted and ini-
tial combability was measured. The tresses were then treated with
the leave-on formulations (Formula 1) and irradiated. Prior to the
final combability measurements, the hair tresses were again washed,
dried, acclimated, wetted and final combability was measured.
Formula 1. Leave-on mousse formulations in hair

combability study
A B
Water (aqua) ad 100% w/w ad 100% w/w
Cocamidopropyl oxide 0.40 0.40
Polysilicone-15 - 3.00
Preservative 0.60 0.60
Propane/butane 10.00 10.00
Each tress was massaged with a generous amount of mousse for

2 minutes. The tresses were then combed to remove excess mousse
and dried under climatized conditions.The tresses were reacclimated
back to 60% humidity (wet combability) and combed at 100mm/
min on a length of 10 cm with an INSTRON 1122c.
b
Atlas ES25 Weather-Ometer, Atlas Material Testing Technology, LLC.
c
INSTRON 1122, Instron

451
Results: Figure 2 illustrates the level of protection attained when

treating the hair with a leave-on conditioner containing a UV filter
prior to irradiation.
Figure 2. Relative change in combing force (after application of formulation, irradiation

and washing)
Both the placebo and test mousses led to decreased combing

forces after irradiation and washing. The treatment with pure water
resulted in an increase of combing force after UV irradiation. This
confirmed that higher forces are needed to comb UV damaged hair.
The placebo mousse provided some protection due to the condi-
tioning effect of cocamidopropyl oxide. However, under the same
conditions, the swatch treated with 3% polysilicone-15 (Formula
1B) showed a much stronger effect on reducing the combing force
for both hair types.
The difference between damaged Caucasian hair (bleached and
permanently colored) and virgin Asian hair is limited. This indi-
cates both hair types are affected by the treatment. Although the
dark melanin pigments (eumelanin) present in virgin Asian hair are
known to act as natural UV absorbers, they are present in the cortex
of the hair and not in the cuticle. This means that the proteins and
lipids in the cuticle of both hair types are equally sensitive to UV

452
irradiation and the resulting degradative processes. Since the state

of the cuticle governs the frictional properties of hair fibers, it is not
surprising to see that both Asian and Caucasian hair were similarly
affected in terms of UV-induced loss of combability.
Protecting Hair Structure

Background on Differential Scanning Calorimetry: As illustrated
in the previous studies, the condition of the hair cuticle determines
important attributes for the consumer such as ease of combabil-
ity and shine. However, other attributes including hair strength
are determined by the condition of the hair cortex. The complex
structure of hair can be simplified using the matrix/filament model
proposed by Feughelman.6
The main part of the fiber is composed of an amorphous matrix
into which crystalline -helical filaments are embedded. The amor-
phous matrix contains proteins with a high sulphur content and is
responsible for structural fiber integrity. The crystalline -helical
filaments contain proteins with a low sulphur content and are
responsible for fiber elasticity.
DSC is a method of choice in assessing the state of both amor-
phous matrix and crystalline -helical filaments of keratin fibers.7-9
Upon heating, the structure of the hair samples becomes denatured
and this denaturation can be quantified by measuring the two fol-
lowing endpoints:
Denaturation Temperature (TD) which indicates the

structural integrity of amorphous matrix
TD (virgin hair) > TD (damaged hair)
Denaturation Enthalpy ( HD) which indicates the

content of native -keratin in the crystalline filaments.
HD (virgin hair) > HD (damaged hair)
Methods: We measured the denaturation temperature (TD) and

denaturation enthalpy ( HD) of hair tresses Caucasian (bleached
and permanently colored) and virgin Asian samples before
and after irradiation. Before irradiation (under the same param-

453
eters in the first study, at a dose over 150h: 3.4kJ/cm2), the tresses
were washed and towel dried. DSC measurements were made on
untreated hair. The tresses were then treated with the formulations
in Formula 2 and irradiated. Final DSC measurements were made.
Formula 2. Leave-on mousse formulas in hair structure

study
A B C
Water (aqua) ad 100% w/w ad 100% w/w ad 100% w/w
Cocamidopropyl oxide 0.40 0.40 0.40
Polysilicone-15 - 1.00 3.00
Preservative 0.60 0.60 0.60
Propane/butane 10.00 10.00 10.00
Each tress was massaged with a generous amount of mousse for

2 minutes. The tresses were combed to remove excess mousse and
dried under environmentally controlled conditions. DSC measure-
ments were taken: wet state [(50 l water + 10 mg hair), 80-180C,
10C/min, n=2].
Results: Figures 3 and 4 illustrate the level of protection achieved
when treating the hair with a leave-on conditioner containing a UV
filter prior to irradiation.
The protection of the hair follicles matrix and -helical compo-
nents can be expressed using the following equation:
Protection (matrix, %) = ( TDUntreated - TDFormulation)

TDUntreated X 100
Protection ( -helical, %) = ( HUntreated - HFormulation)

HUntreated X 100
Using this equation, calculations reveal the hair will be protected

if the use of the test formulation versus no treatment leads to no

454
change in denaturation temperature/enthalpy. When compared to

no treatment, no protection is obtained when the change in dena-
turation temperature/enthalpy for the test formulation equals the
values obtained for the untreated hair.
Figure 3. UV protection of hair structure using DSC measurements (bleached Caucasian hair)
Figure 4. UV protection of hair structure using DSC measurements (virgin Asian hair)
For both hair types, the amorphous matrix and the crystalline
-helical filaments are significantly protected when polysilicone-15
is present in the formulation (in both B and C samples). The
amount of protection is clearly concentration dependent. Interest-

455
ingly, the best protection of the amorphous matrix was obtained

for virgin Asian hair while the best protection of the crystalline
-helical filaments was obtained with bleached Caucasian hair.
Enhancement of Hair Shine

Background on hair shine: Consumers perceive shiny hair as healthy
hair. Shine is in and it is the number one claim for most hair care
products. The surface of a hair fiber is such that perceived hair
shine not only depends on the intensity of visible light reflected at a
90-degree angle (specular reflection) but also on the light reflected
at other angles (diffuse reflection). Polysilicone-15, being a liq-
uid, does not recrystallize when used in leave-on applications and
spreads uniformly on the hair fiber. Its relatively high refraction
index enhances hair shine as indicated by the results below.
Method: Varying amounts of polysilicone-15 in a UV protection
spray (Formula 3) was applied by spraying the formulations on hair
tresses at a 10-cm distance using 6 pumps from a pump bottle. The
product was allowed to dry for 30 minutes before measurements
were taken using a gloss meter.
Formula 3. Leave-on formulas for shine enhancement
A B C
Isododecane ad 100% w/w ad 100% w/w ad 100% w/w
Polysilicone-15 - 2.00 4.00
Phytantriol 0.25 0.25 0.25
Vitamin E acetate 0.25 0.25 0.25
Fragrance (parfum) 0.05 0.05 0.05
Methyldibromo glutaronitrile
(and) phenoxyethanol 0.20 0.20 0.20
Figure 5 illustrates the level of shine enhancement obtained by

adding polysilicone-15 to the formulations.

456
Figure 5. Enhancement of hair shine (Glossmeter measurements) using polysilicone-15 in

aqueous solution (top) and commercial hair protection spray product (bottom)
Discussion: The chemical binding of chromophores attached to a

silicone polymer, such as for polysilicone-15, is a new concept in the
development of effective types of sun filters. The experimental data
presented in this chapter indicates that the performance of a UV
filter for hair protection cannot be predicted by solely considering its
capacity in absorbing UV radiation [E (1%, 1cm) value]. Whenever
compared to the filter ethylhexyl methoxycinnamate, polysilicone-15
always performed better in terms of hair protection, despite its rela-
tively low absorption value (about one fourth compared to EHMC).

457
The high performance of polysilicone-15 is linked to its structure:

internal results have shown that the distribution and the loading
of the UV chromophores on the siloxane chains are optimized for
highest performance in terms of UV protection. The silicone moiety
of polysilicone-15 favors uniform spreading on the hair fibers while
the polymeric structure offers substantivity in rinse-off applications.
In the combability study, the very significant decrease of comb-
ing forces observed after irradiation is the result of the properties of
the two moieties of polysilicone-15 (UV chromophore and silicone
polymer) working in synergy.
Ingredients which enhance hair shine usually have high refrac-
tion indexes and spread uniformly on the hair fiber. Polysilicone-15,
with a refractive index of 1.44 and its silicone backbone, increases
perceived hair shine when added in cosmetic formulations as shown
in the shine study.
Additionally, panel studies have shown that no build-up effect
is observed upon consecutive use of a shampoo containing polysili-
cone-15.10 This is probably also due to the structure of the molecule.
The large size of the chromophores attached to the silicone back-
bone sterically disfavor excessive buildup.
Polysilicone-15 also delivers benefits such as improving fragrance
retention on hair tresses using leave-on formulations.11
Conclusion
Our studies indication polysilicone-15 protects the structure of hair
against UV radiation as measured by DSC and enhances combabil-
ity of hair after exposure to UV radiation. Furthermore, it enhances
the shine attribute of a formulated product.
Philippe Maillan, Anna Gripp, Fintan Sit, Roland Jermann and

Hrst Westenfelder
DSM Nutritional Products AG, Basel, Switzerland
References
1. Caravan Consumer Survey, USA 2002 (commissioned by DNPI)
2. P Maillan, UV protection of artificially coloured hair using a leave-on formulation, Int. J.
Cosmet. Sci. 24 1-7 (2002)

458
3. H Gonzenbach, W Johncock and K-F De Polo, UV damage on human hair, Cosm. Toil.
113 43-49 (1998)
4. J Jachowicz, M Helioff and C Rocafort, Photodegradation of hair and its photoprotection
by a substantive photofilter, DCI (Dec 1995)
5. P Maillan, Protecting hair combability from UV irradiation using a leave-on formulation,
Cosmetic and Toiletries Manufacture Worldwide 22-26 (2003)
6. M Feughelman, Physical properties of hair, Hair and hair care, Editor: DH Johnson,
Cosmetic Science and Technology series 17, M Dekker 13-32 (1997)
7. F-J Wortmann an H Deutz, Characterizing keratins using high pressure differential
scanning calorimetry, J. of Applied Polymer Science 48 137-150 (1993)
8. F-J Wortmann, C Springob and G Sendelbach, Investigations of cosmetically treated
human hair by differential scanning calorimetry in water, J. Cosmet. Sci. 53 219-228
(2002)
9. H Schmidt and F-J Wortmann, High pressure differential scanning calorimetry and wet
bundle tensile strength of weathered wool, Textile Res. J. 64(11) 690-695 (1994)
10. Study report June 2004, Institute Dr Schrader, Holzminden, Germany
11. World patent filed: WO 2003035022 A1 by DSM Nutritional Products

Chapter 45
Polyamide-2:
an Innovative
Photoprotection Polymer
for Hair Care
KEY WORDS: hair care, UV protection, polyamide-2, substantivity,
photodegradation, photostability, tensile strength
ABSTRACT: Polyamide-2 is shown to be an effective sun protection
polymer for hair care, protecting from photodegradation
and preventing artificial hair color fading. Photostability of
polyamide-2 was also studied.
Many investigators have implicated UV light as causing hair

damage.1,2 This damage to the hair can be manifested in a number
of ways including loss of color and tensile strength, the degrada-
tion of disulfide bonds and an increase in hair surface roughness.
As consumer awareness about photodamage to hair has increased,
sun protection products are expected more than ever to perform in a
more visually perceptible way. However, the UV protection products
for hair care in the current market place, mainly monomeric and
adopted from skin care, lack substantivity and water solubility. Thus,
they do not possess conceivable UV protection efficacy.
Polyamide-2a, a photoprotective polymer, was specifically
designed for UVB and UVA protection of hair. This chapter reviews
the detrimental effects of each range of UV light to hair and then
presents the experimental results showing the sun protection per-
formance of polyamide-2 for both hair morphology and artificial
a
Solamer is a product of Nalco Company, Naperville, IL USA

460
Sun Protection Polyamide-2
hair color fading. Finally, photostability, an important subject for all

sunscreen products, will be discussed in detail.
Effects of UVA and UVB on Hair

Ultraviolet radiation is divided into three primary regions: UVC
(<290 nm), UVB (290-320 nm) and UVA, including UVA II
(320-340 nm) and UVA I (340-400 nm). Of the three ranges of
UV radiation, the shortest wavelength, UVC, is filtered out by the
stratosphere and is not likely to contribute to the photodamage
reactions of hair proteins. UVB radiation is the primary cause of
natural photodamage since the most significant chromophores in
hair proteins absorb UVB.3 Photodegradation of hair is believed to
follow the photolysis mechanism proposed by Togyesi.4 Cystine,
tyrosine, phenylalanine and tryptophan absorb UVB radiation,
resulting in the formation of free radicals. Homolytic scission of dis-
ulfide bonds occurs. Dryness, reduced tensile strength, rough surface
texture, brittleness and hair color bleaching are the direct conse-
quences from UVB induced hair photodegradation. Although UVA
is not the primary cause of UV damage to hair, scientists have found
that visible and UVA light are largely responsible for artificial hair
color fading.5 In summary, both UVB and UVA radiation play a role
in the photodamage of hair, the former associated with deteriorated
hair integrity and the latter leading to dye fading.
Polyamide-2
Hair fibers contain a natural melanin coloring component that
provides partial sun protection to the hair. It acts in a sacrificial
manner and its degradation results in the lightening of hair color.
However, melanin in hair cannot fully protect against UV dam-
age when hair is repeatedly exposed to sunlight. Synthetic UV
protection molecules are therefore necessary to protect hair against
the adverse effects of solar radiation. Polyamide-2 was specifically
designed to absorb a broad range of UVA II and UVB radiation.
The development of polyamide-2 represents a major contribution of
chromophore chemistry and an advanced technology in hair protec-
tion from UV rays.

461
Hessefort et al. Chapter 45
As shown in Figure 1, both chromophore groups of methyl

salicylamide and 1,3-diimine (or its tautomer), the former used as
a capping agent and the latter incorporated in the polymer chain,
provide a wide range of UVB and UVA II absorption.
Figure 1. Chemical structure of polyamide-2
Polyamide-2 is cationic at neutral pH range (pH = 5.0 7.0)

due to its protonated nature of amine functionality. This cationic
characteristic gives the polymer good substantivity on hair, which
was proven in the following evaluation. Polyamine-2 is also water
soluble, so it can be easily formulated in water-based hair care for-
mulations. The importance of combining the substantivity and UV
protection properties of polymeric materials with typical properties
of water solubility, low toxicity, and lasting protection efficacy is
self-evident.
Hair Treatment and Test Formulations

Hair samples and treatment: Virgin blond and medium bleached
brown hair was purchasedb. Hair was washed by applying 1 g sodium
laureth sulfate (SLES) on a 2 g hair tress from top to bottom and
massaged for 1 minute. The tresses were rinsed under 40 +/- 2C tap
water for 1 minute and soaked in deionized water overnight.
Three treatments were applied on separate hair tresses: surfactant
solution, shampoo, and conditioner formulations. There are three
b
International Hair Importers & Products, Inc. Glendale, New York USA

462
variants of each formulation: no polymer (control), polyamide-2

and benchmark (polyquaternium-59 with butylene glycol). For the
treatment, 1 g of the respective test formulation was applied to each
washed tress for 1 minute, rinsed off under DI water for 30 seconds
and air-dried before the next treatment. The treatment was per-
formed a total of three times.
For the artificial color fading study, pre-washed, medium
bleached brown hair was dyedc following the manufacturers instruc-
tions. The dyed hair then received the same 1 g of the respective test
formulation, as described above.
Test formulation: Surfactant solution used 10% sodium lauryl
sulfate (SLS) with 2% (solid basis) test polymer. Clear shampoo and
conditioner formulations are listed in Formulas 1 and 2.
Formula 1. Clear shampoo formulation
Water (aqua) qs to 100% w/w

Ammonium laureth sulfate (Standapol EA-1, Cognis) 43.0
Cocamidopropyl betaine 9.3
Sodium lauroyl sarcosinate
(Hamposyl L-30, Hampshire Chemical Corp.) 5.0
Testing polymer 2.0 (solid)
Preservative 0.2
Citric acid qs to pH = 5.8 to 6.10
Sodium chloride 1.0
Sunlight simulation: An accelerated weathering testerd with a

340 UVA bulb has a spectrum similar to sunlight in the range of
290-400 nm. The irradiation of the fluorescent bulb is at 340 nm
maximum with an energy dose of 450 J/cm2. Hair tresses of 1.5 g
each were arranged in a single layer and were placed 10 cm from
the UV lamps. Each side of the hair tresses was equally exposed and
total exposure time was 400 hours.
c
LOral Feria, Multi-Faceted, Shimmering Color 67 is a product of LOral, Paris, France.
d
QUV Accelerated Weathering Tester is a product of Q-Panel Lab Products, Cleveland, OH USA

463
Formula 2. Clear conditioner formulation
Water (aqua) qs to 100% w/w

Hydroxyethylcellulose (Natrosol 250 HHR, Hercules) 0.8
Testing polymer 2.0 (solid)
Panthenol, 50% 0.7
Cetrimonium chloride (Varisoft 300, Degussa) 2.0
Glycerin 1.0
Polysorbate 20 (Tween 20, ISP Technologies) 0.5
Preservative 0.2
Sodium hydroxide (or) citric acid qs to pH 5.5
Evaluation
We have completed work on updated methods for evaluating the
performance of polyamide-2. These evaluations encompass a range
of performance characteristics including hair color, hair morphology,
hair integrity, substantivity, and photostability.
Color fading: The total color change of D E = [9*D L2 + D a2 +
D b2]1/2 was used to calculate color fading.6 It was determined by
measuringe the L, a, b Tristimulus color values of hair tresses, where
L stands for lightness, a for color of green to red, and b for
blue to yellow. For the sun protection study, virgin blond hair was
selected as the test substrate due to its susceptibility to sun dam-
age. The same three treatments described above (i.e., surfactant
solution, shampoo and conditioner with three variantsno polymer,
poloyamide-2 and benchmark) were applied to hair tresses. The
determined changes in D E values are presented in Figure 2.
The total color change (D E) represents the hair color difference
of hair tresses before and after UV exposure. Since the bleaching
effect of brown melanin in hair is an indication of hair photo-
damage, unquestionably, a lower D E value represents better sun
protection. One can see from Figure 2 that hair tresses treated with
formulations containing polyamide-2 show the lowest D E values
e
Hunter Colorimeter LabScan XE, Hunter Associates, Reston, VA USA

464
in all three treatments. Similarly, total color change was also used
to evaluate artificial hair color fading. In addition, color changes in
lightness index (D L), in red-green index (D a), and in blue-yellow
index (D b) were also included in the evaluation. As one would
expect, the smallest color change represents the least artificial hair
color fading after UV exposure.
Figure 2. Total color change evaluation for hair protection
Manually dyed and dried hair tresses were treated with condi
tioner formulations (control, polyamide-2, and benchmark).
Polyamide-2 treated tresses show the lowest values for all indices.
The color differences among these tresses were so apparent that
they could be easily identified by visual inspection. The polyamide-2
treated hair remained red while the other two largely faded to brown.
Tensile strength: The strength of hair directly reflects its health.
Hair strength comes from the helical chains of keratin polypeptides,
which are stabilized by hydrogen bonding, cystine cross-linkages,
coulombic interactions and hydrophobic interactions.7 Scission of
cystine linkages due to excessive UV exposure will disrupt the heli-
cal structure and weaken the hair. Thus tensile strength, the total
work required to break a hair strand, is another means of evaluating
the photodamage of hair fiber.

465
Hair tresses that were treated with a conditioner formulation

containing either water (control), polyamide-2, or the benchmark
were exposed to UV for 400 hours. An unexposed hair tress was also
included in the test to provide an example of undamaged hair. Sixty-
five hair strands were randomly selected from each tress and hair
diameter was measured using a fiber dimensional analysis systemf.
The hair samples were then placed in a miniature tensile testerg.
To eliminate the effect of hydrogen bonding, the test was conducted
in a wet condition. Each individual hair strand was pulled at a rate
of 20 mm/min until breakage occurred. Load and extension were
automatically recorded and converted to stress and strain using
application softwareg. The mean values were then calculated and a
Tukey HSD statistical analysis was performed for all testing pairs
(ANOVA one-way analysis of variance from JMP statistical soft-
wareh) (Figure 3).
Figure 3. Tensile strength
It was found that the tress that received no UV protection from

the control showed an obvious reduction in tensile strength com-
pared to undamaged hair proving hair undergoes photodegradation.
f
Fiber Dimensional Analysis System, Model LSM 5000, is a product of Mitutoyo, DiaStron
Limited, UK.
g
DiaStron Miniature Tensile Tester Model 170/670 and model MTTWIN Version 5.0 are
products of DiaStron Limited, UK.
h
JMP statistical software is a product of SAS Institute, Cary, NC USA

466
The overall decrease in tensile strength upon UV exposure is

believed to be related to the scission of cystine disulfide bonds in
the hair proteins. This will be explained in more detail in the next
section. Hair strands protected by polyamide-2 required a signifi-
cantly higher breaking force than those that were unprotected or
treated by the benchmark. Hair protected by polyamide-2 showed
no statistical difference from undamaged hair. Although the cause
or mechanism is unknown, the benchmark-treated hair was weaker
than the control. The statistical analysis illustrates a significant
difference at 95% confidence interval (Figure 3). The test results
indicate that polyamide-2 provides effective protection of the hair
from UV damage.
Hair integrity via FTIR spectroscopy: It is generally accepted
in the industry that the photodamage of hair protein proceeds via
oxidation of cystine following the S-S scission pathway, whereby
oxidative scission yields S-sulfonic acid that is finally degraded to
cysteic acid. While the S-S bonds are susceptible to this degrada-
tion, the Amide I band is not affected by UV radiation. The ratio of
the S-O bond/Amide I band measured by Fourier Transform Infra-
red Spectroscopy (FTIR spectroscopy) is, therefore, an indication of
the degree of photo-degradation of hair fibers. In other words, the
higher the S-O/Amide I ratio, the more severely degraded the hair.
A hair tress treated with conditioner formulation and UV
exposed was pressed on a single reflectance cell with the hair aligned
along the axis of the beam path of an FTIR spectroscopei. One
hundred twenty eight scans were signal averaged. The detector
employed was deuterated triglycine sulphate (DTGS). The Amide
I peak at 1633 cm-1 was used as an internal standard. Peak height
of the SO band at 1041 cm-1 was measured and normalized to the
Amide I band. Each type of hair tress was measured five times at
ambient temperature and humidity.
It is clear that the polyamide-2 treated hair tress showed a lower
amount of oxidative products than both the benchmark and control
(Figure 4). Unexpectedly, we also observed that the benchmark
showed a higher mean value of SO/Amide I ratio than the control,
i
Nicolet Avatar 360 FTIR is a product of Varian Instruments, Walnut Creek, CA USA

467
which is consistent with the prior tensile strength measurement;

that is, benchmark-treated hair seems to have more deterioration
than the control. For the statistical analysis, the center lines of the
means diamonds are the group means (Figure 5).
Figure 4. FTIR analysis of SO/Amide-I band
Figure 5. Statistical analysis of FTIR results
The top and bottom of the diamonds form the 95% confidence
intervals for the means. It can be said that the probability is 95%
that this confidence interval contains the true group mean. If the

468
confidence intervals shown by the means diamonds do not overlap,

the groups are significantly different at 95% confidence. None of
the confidence intervals displayed overlap (Figure 5); therefore, the
results are statistically valid.
Substantivity: As mentioned earlier, sun protection products
commonly used in hair care today have been adopted from those
used for skin care. Octylmethoxy cinnamate (OMC) is a typical
example. However, these oil-soluble UV filters do not normally have
affinity to the hair and, in many cases, they only deposit in mini-
mum amounts from rinse-off formulations.8 Substantivity, therefore,
is of much importance since it is a key factor to determine the UV
protection efficacy for hair care.
The authors developed a non-traditional weighing method to
measure substantivity using a fine micro-balance in a humidity- and
temperature-controlled environment. Pre-tabbed hair tresses were
washed and dried and then the initial mass (W0) was recorded using
a 5 decimal-place micro-balancej.
The hair was then treated in a 5% polymer solution (solid base)
for five minutes and rinsed under deionized water for 30 seconds
and dried. The treatment was repeated three times in total and then
the treated hair was weighed again (Wt). The hair tab was carefully
removed and weighed as Wb. The substantivity is expressed as:
Substantivity (mg Polymer/g Hair) = [(Wt-W0)]/ (W0-Wb).
The absolute values of substantivity are largely related to the type

of test method used. Some traditional methods such as 14C radio
labeling and gel permeation chromatography can detect the polymer
deposition on hair at low levels when a low concentration of treat-
ment solution is used.9 The typical substantivity measured in these
methods is around 7-10 mg polymer/mg of hair, or 7-10 mg of
polymer/g of hair.10 The substantivity listed (Table 1) is expected to
be higher than these conventional methods due to the higher con-
centration treatment solution used. Nevertheless, the data provides
a relative comparison for the amount of deposition of polyamide-2
j
Mettler AE 163 micro-balance is a product of Mettler Toledo, Columbus, OH USA

469
compared with the benchmark (Table 1). Obviously, polyamide-2

shows better deposition, which results in better sun protection in
rinse off formulations.
Table 1. Means and standard deviations of substantivity
Mean Value
of substantivity
(mg Polymer/ No. Of Standard Standard Lower Upper
Test Name g Hair) replication Deviation Error Mean 95% 95%
Benchmark 26.2101 5 6.26019 2.7996 20.110 32.310
Control 4.0566 5 1.29621 0.5797 2.794 5.320
Polyamide-2 34.2807 5 1.90899 0.8537 32.421 36.141
Hair morphology via AFM: Atomic Force Microscopy (AFM) is

a technique that allows for direct interaction between a sharp probe
and a sample surface as the probe is brought into contact with this
surface. Using piezo electronics and laser deflection, these interac-
tions can be precisely measured. A common measurement provided
by this technique is to compute height variations in a surface profile
as recorded within the scanned area.
The specific method used here was to incorporate a low force
contact probe to directly measurek points within the scanned surface
of each hair fiber. The method would easily scan over the surface
while maintaining constant tip contact via an electronic feedback
system within the AFM. This method would generally correspond
to the technique of surface profilometry.
The collected data points are then plotted along a Z-scale
defined by a specified and matching color palette for each image.
This palette was then projected as a 3D image by using a defined
image pitch (30) and image rotation (45) to qualitatively exhibit
the distinct surface profiles.
k
VEECO Methrology, Digital Instruments Div. Dimension 3100 is a product of VEECO
Metrology, LLC, Santa Barbara, CA USA

470
Three hair strands were tested using the AFM method: undam-
aged (virgin), control, and polyamide-2 treated. The latter two had
been UV exposed. Typical 3-D projected images from these separate
samples are shown (Figures 6-8) (see Color Insert 17). The undam-
Figure 6. AFM image for undamaged hair
Figure 7. AFM image for UV protected hair
Figure 8. AFM image for UV unprotected hair

471
aged image displays a smooth cuticle edge indicating no evidence

of damage.
The polyamide-2 treated hair has an image similar to the
undamaged image even after UV exposure. The control image
displays clear evidence for cuticle edge damage where a portion
of this edge has been broken off. The similar findings were also
observed from an SEM study,11 where the damaged cuticle cells
were found to be thinning or fusion due to photodegradation.
The AFM method provides a different perspective to identify
the photodamage and prevention. This work was also supported
by the frictional analysis of the cuticle, which proves that the
polyamide-2 treated hair tresses have a significantly less friction
coefficient than the control.12
Photostability: If a UV filter loses its absorbance over time, it
may be called photo-unstable. The cause of the photolabile or
photo-unstability can be explained by the energy dissipation mech-
anism. The absorption of UV radiation by some organic molecules
can cause the excitation of one of a pair of electrons in a low energy
orbital to a higher energy unoccupied orbital.13 An excited molecule
can return to its ground state by a combination of several mecha-
nistic steps. Two of these steps, fluorescence and phosphorescence,
involve the release of a photon of radiation.14 The other deactiva-
tion steps are radiationless processes. The favored route to the
ground state is the one that minimizes the lifetime of the excited
state. Thus, if deactivation by fluorescence is rapid with respect
to the radiationless processes, such emission is observed. Fluores-
cence is, therefore, considered one of the pathways that dissipates
the energy in a non-destructive pathway. On the other hand, if a
radiationless path has a more favorable rate constant, fluorescence
is either absent or less intense. Energy dissipation can also follow
the destructive pathways, which possibly belong to radiationless
steps where the fragmentation, or certain types of isomerization
and bimolecular reactions likely happen.13 If the destructive path-
way predominates, the molecule will be photo-unstable.
To study the photostability, both polyamide-2 and the bench-
mark were prepared at 10% in water. The solutions were scanned for
UV absorption before and after UV exposure (200 hours) using a

472
UV-visible spectrophotometerm to detect the change in absorbance

(Figures 9-10).
Figure 9. UV absorbence before and after UV exposure for polyamide-2
Figure 10. UV absorbence before and after UV exposure for polyquaternium-59 with
butylene glycol
m
Cary 3 Bio UV Visible Spectrophotometer is a product of Varian Instruments, Walnut Creek,
CA USA.

473
The absorbance of solutions was recorded against the wavelength

of 400 to 250 nm. Polyamide-2 shows almost no reduction in UV
absorbance compared to the benchmark. Fluorescence microscopyn
was used to further understand the energy dissipation mechanism
(Figures 11-12).
Figure 11. Fluorescence excitation peak for polyamide-2
Figure 12. Fluorescence emission peak for polyamide-2
n
F-4500HITACHI Fluorescence Microscopy is a product of Hitachi High-Technology, UK.

474
Polyamide-2 solution was prepared in 1ppm concentration in

water and scanned at 30000 nm/min speed with sampling interval
10.0 nm. Both figures clearly indicated that polyamide-2 has fluo-
rescence property. It absorbs the radiation near 300 nm and emits
near 400nm. The longer wavelength emitted is due to the phenom-
enon called stokes shift. The same fluorescence microscopy was
also tested for benchmark, but no fluorescence was observed. This
investigation not only provides the substantial understanding of the
photostable nature of polyamide-2, it also explains why polyamide-2
exhibits high UV protection efficacy on hair.
Summary
Polyamide-2 is a wide-range, UV-absorbing polymer that was
specifically designed to incorporate a unique chromophore group
and methyl salicylate endcaps. Further, additional functionality was
added to ensure water solubility. These novel structural attributes
provide a wide-range of UV absorption capabilities and ease-of-
formulation. Polyamide-2 has been proven to be an effective UV
absorbing polymer that offers numerous benefits when formulated
into hair treatment products. It helps maintain hair tensile strength,
lessens the degradation of cystine disulfide bonds and minimizes
the fading of hair color (both natural and artificial). Further, this
innovative UV-absorbing polymer is photo-stable, and it has been
demonstrated to be substantive and improve hair morphology.
Polyamide-2 is an important tool that can be used to protect hair
from the harmful effects of UV radiation.
Acknowledgements
The authors gratefully acknowledge the valuable contributions of Richard Cloud, Hua
Zheng, and Cheryl Slabozeski for their help in providing analytical results of AFM and FT-IR
work and sample preparations.
Yin Z. Hessefort, Wayne M. Carlson and Mingli Wei

Nalco Company, Naperville, IL USA
References
1. S Nacht, Sunscreens and hair, Cosm Toil 105 (December 1990)

475
2. SB Ruetsch, Y Binhua and YK Kamath, Role of melanin and artificial hair color in
preventing photo-oxidative damage to hair, IFSCC magazine 7, No. 2 (April/June 2004)
3. CM Pande and J Jachowicz, Hair photodamage - Measurement and prevention, J Soc
Cosmet Che 44 109-122 (March/April 1993)
4. E Tolgyesi, Weathering of hair, Cosmet Toil 98 29-33 (1983)
5. B Locke and J Jachowicx, Protection of artificial hair color, J of Cosmetic Science 54(2)
p. 212, (March/April 2003)
6. J Jachowicz, M Helioff, and C Rocafort, Photodegradation of hair and its photoprotec
tion by a substantive photofilter, Drug and Cosmetics Industry (December 1995)
7. C Zviak, The Science of Hair Care, New York: Marcel Dekker (1986)
8. C Pande and J Jachowicz, Hair photodamage: Measurement and prevention, J Cosmet
Sci 44 109-122 (1993)
9. AR Sykes and PA Hammes, The use of merquat polymers in cosmetics, Drug and
Cosmetics Industry (Feb 1980)
10. B Blanco, BA Durost and RR Myers, Gel permeation chromatography: An effective
method of quantifying the absorption of cationic polymers by bleached hair, presented
at the Annual Scientific Seminar of the Society of Cosmetic Chemists, Nashville, TN
(May 1997)
11. SB Ruetsch, Y Kamath and HD Weigmann, Photodegradation of human hair: An SEM
study, J Cosmet Sci 51 103-125 (Mar/Apr 2000)
12. RW Cloud and YZ Hessefort, Characterization of Friction Properties for Photo-Degraded
Hair Fibers Using AFM, to be presented at the 23rd IFSCC (October, 2004)
13. NJ Turro, Modern Molecular Photochemistry, Menlo Park, CA: Benjamin/Cummings:
(1978) p 3
14. DA Skoog and DM West, Principles of Instrumental Analysis, 2nd edn, Philadelphia:
Saunders College (1980)
15. Private correspondence from Craig Bonda of C.P. Hall Company, Chicago, IL, US (2004)

Chapter 46
Texture Analysis to
Formulate Hair Care
Products and Select
Packaging
KEY WORDS: texture analysis, extrusion, hair spray, styling waxes, aerosols
ABSTRACT: Texture analysis provides quantitative information about
a materials response when deformed by a controlled
force. Examples illustrate the use of a texture analyzer to
evaluate shampoo extrusion, hair spray film toughness, hair
spray tackiness, styling wax hardness and aerosol canister
deployment.
Texture analysis instrumentation can be used to substantiate claims

in hair care,1 but the equipment and test methods are equally valu-
able in the development of the product as they are in confirming
its efficacy. Manufacturers can use instruments such as a texture
analyzer to help with all aspects of R&D and production, including
formulation and the suitability of specific types of packaging.
Hair care products must fulfill the claims manufacturers make
about the products effect on hair quality, and these products also
must be easy and pleasant to use. Achieving this latter requirement
demands attention to numerous aspects of both product formulation
and packaging.
Testing Shampoo Extrusion

A thin, easy-to-pour shampoo will require the addition of different
ingredients and/or ingredient quantities than that required for a
thick conditioner. A product developer may wish to create a product

478
Testing Texture Analysis
that squeezes out of a tube and breaks sharply after squeezing. One
of the most common methods for testing the effect of changes in
formulation on product consistency is extrusion. A texture analyzera
with a back extrusion rig and forward extrusion rig (Figure 1a) can
simulate the force required by the consumer to extrude the sample
and provide simple and objective analysis of the formulation of vis-
cous liquids, including shampoos and conditioners. Such extrusion
tests give an indication of product physical failure and consistency.
Typical results are shown in Figure 2.
a b
c d
Figure 1. Texture analyzer used in testing hair care formulations (photos courtesy of
Stable Micro Systems Ltd.)
a) Backward and forward extrusion test to analyze the formulation of viscous liquids
b) Film support rig to measure the biaxial extensional properties of films
c) Wax penetration test
d) Thermal cabinet for measurements at constant and realistic temperatures
a
Model TA.XT Plus Texture Analyzer from Stable Micro Systems is the instrument on which
this article is based.

479
Smewing and Jachowicz Chapter 46
Figure 2. Typical curves produced from tests of two shampoo formulations carried out in a
75% full, standard-sized back extrusion container that had been stored at 25C
Test results obtained from two shampoo formulations (stored

and tested at 25C) give the typical mean maximum positive force,
mean positive area, mean maximum negative force and mean nega-
tive area values as shown in Table 1. Maximum positive force (for
the portions of the force-versus-time curves from 0 to approxi-
mately 10 sec) characterizes the firmness or hardness of a shampoo.
The area under the positive force values corresponds to the move-
ment of the probe into the product; it represents the consistency
of the product and is related to product viscosity. The maximum
negative force is termed cohesiveness; the more negative the value
the more cohesive is the sample. The area under the negative force
values is referred to as the work of cohesion; the higher the value,
the more resistant the sample is to withdrawing the probe, which is
an indication of the cohesiveness and also consistency/viscosity of
the sample.

480
Table 1. Typical results (means) from back extrusion tests

on two shampoo formulations ( S.D.) (N=5) (G = gram
force) (g s = gram seconds)
Maximum positive Positive area Maximum negative Positive area or

force or firmness or consistency force or cohesiveness index of viscosity
Sample (G) (g s) (G) (g s)
A 17.9 0.9 156.5 6.7 10.4 0.2 97.7 3.7
B 47.2 0.8 404.9 10.0 25.5 0.6 309.3 4.3
Testing Hair Fixatives

Texture analysis is valuable in all the main fixative categories. A wide
range of tests has been developed for hair gels, including backward
and forward extrusion, which measures the products consistency, gel
strength, rupture force, adhesiveness and elasticity. These character-
istics are driven primarily by formulation, but can be influenced also
by temperature and humidity and other external factors. It is also
possible to quantify textural characteristics of hair sprays.
Hair spray film toughness test: A desirable fixative is one that
gives good flexible hold without giving hair a stiff feel. This flex-
ibility is one of the attributes of a hair styling product described as
touchable. Polymers can be evaluated for mechanical properties
using an objective film toughness test. Polymeric films can be cast
out of aqueous solutions and conditioned in constant temperature
and humidity conditions. Each film would then be stretched using
a tensile test that determines a variety of measurements, such as
modulus, stress and strain.
A film support rig (Figure 1b) can be employed for the measure-
ment of biaxial extensional properties of films. Before performing
the test, the sample is placed over a hole in a raised acrylic glassb
platform. A top plate prevents the sample from slipping during test-
ing. The test is carried out as the arm of the texture analyzer brings
b
Perspex, a polymethylmethacrylate. Perspex is a registered trademark of Lucite International.

481
a 5 mm stainless steel ball probe down into the aperture. The maxi-
mum force to rupture the film is recorded and is referred to as the
burst strength of the film. The resilience and relaxation properties of
the film can also be measured.
Resilience can be assessed by depressing the film surface to a
chosen distance before retracting the ball probe. The property is
calculated using a ratio of the work of compression and work of
withdrawal. Similarly, relaxation can be measured with the addi-
tion of a hold period within the test to allow the products recovery
to be evaluated. Rupture strength, resilience and relaxation are
important factors in determining the mechanical properties of the
product, allowing manufacturers to optimize product structure
and formulation.
Hair spray tackiness: The test used to assess tackiness, or lack
of it, on hands and hair during drying is the application of a fixed
amount of aqueous polymeric solution to two horizontal and par-
allel mounted pads. The texture analyzer moves the pads toward
each other until they come into contact; the force then required to
separate the two pads indicates the tackiness of the solution. As the
solution dries, this procedure should be repeated in a series of cycles
until no more tack is observed.
Alternatively, a polymer solution or a fixative product may be
applied in a specified quantity to a special substrate characterized by
rheological properties similar to skin.2 A texture analyzer equipped
with a flat or spherical probe may be employed to produce a series of
substrate deformations with simultaneous measurements of posi-
tive and negative tackiness-related forces as a function of time. The
results may be interpreted in terms of maximum tackiness force,
integrated adhesion and duration of tackiness.
Wax hardness: When waxes are used in hair styling products,
the measurement of their hardness is valuable in ascertaining their
contribution to final product texture. Hardness, which is also called
firmness and is affected by the melting point of the wax, may have a
significant effect on other physical properties. Therefore, measuring
this characteristic can determine whether a wax is suitable for use
in products to provide rigidity and good molding properties, or is
capable of producing soft emollient films with good luster.

482
Wax hardness can be assessed by a simple penetration test using

a cylinder probe (Figure 1c) or, if the product surface is uneven, a
spherical probe. The arm of the texture analyzer moves the probe
downward a defined distance and the user records the force required
to penetrate into the product container. The higher this force, the
firmer or harder the product. Such measurements are useful for
selecting or specifying a wax of a particular consistency or hardness
depending upon the required texture of the end product.
Wax, gel and putty stickiness and tackiness: The adhesive proper-
ties of waxes and softer, more malleable hair styling gels and putties
can be measured using a range of adhesive tests. These products can
be heavy and greasy if not used in the correct quantity. Normally,
they hold hair through seam welds. This holding power is created
by the internal stickiness or cohesiveness of the materials. These
materials do not dry because they are not water-soluble. This
characteristic is useful because the bonds can be remolded easily
when the hair is combed by the hands, but potential stickiness is a
negative aspect.
To evaluate this kind of stickiness and tackiness, softwarec pro-
vides the means of controlling the texture analyzer in a specialized
adhesive test. A probecylindrical for a flat surface or spherical
for a curved surfaceapplies a defined force to the surface of the
sample for a specified duration to achieve a good bond between the
two surfaces. Then the probe is moved away from the product and
the force to separate the two surfaces is measured and defined as an
assessment of product stickiness or adhesiveness or tackiness.
In an example shown in Figure 3, the magnitude of the abso-
lute positive value corresponds to the stickiness. The area under the
profile represents the energy required to separate the wax from the
probe; this energy is referred to as work of adhesion. The larger the
maximum peak force, the stickier the sample. The results in Table 2
show that the strong wax (sample A) was stickier than the regular
wax (sample B). The regular wax required greater total force (work
of adhesion) to separate from the probe because it was softer and
c
Exponent software is a product of Stable Micro Systems Ltd. in Godalming, Surrey UK.
Exponent is a trademark of Stable Micro Systems Ltd.

483
flowed with the probe as it withdrew from the sample. Strong wax
showed higher absolute value of stickiness (maximum positive force)
and this should correspond to the consumer perception of a product
feeling stiffer on hair.
Table 2. Mean maximum force and mean area values

( S.D.) from five hair wax samples of each sample type
(G = gram force) (g s = gram seconds)
Maximum peak force Mean area

or stickiness or work of adhesion
Sample (G) (g s)
A 169.0 17.5 50.0 3.0
B 387.7 13.6 24.9 3.9
Figure 3. Typical curves showing a comparison of stickiness properties of two types of soft
molding hair wax using a 1-inch ball probe. These curves were produced from tests carried
out in the original hair wax container at 25C.

484
Temperature testing for waxes: Severe temperature changes will

affect the firmness and stickiness of hair wax. These changes impact
on the ease of use of the product, and its ultimate consumer appeal.
Studies can be carried out at different temperatures with the use of a
thermal cabinet (Figure 1d) attached to the texture analyzer. Tex-
ture tests can be performed within the cabinet, ensuring consistent
and realistic environmental conditions.
Testing Packaging
A products packaging is as important as its formulation and per-
formance. Packaging plays an essential branding role. On the shelf,
packaging helps the product stand out from its competitors and
attract the consumers eye. After the product is purchased, the pack-
aging must enable the consumer to use the product easily and safely.
Tube extrusion: Gels, some travel-sized shampoos and condition-
ers, and other hair products supplied in tubes can be difficult to use
if the packaging material is too stiff, or if the aperture of the tube is
too small. Stable Micro Systems has developed a test that imitates
the extrusion process, allowing manufacturers to specify the correct
materials and production specifications for tube packaging.
The tube is positioned vertically on the texture analyzer between
two rollers, with the closed end clamped with a grip at the top.
The grip pulls the tube upward through the rollers, forcing out the
contents. The higher the force recorded during this test, the more
difficulty a consumer would experience in squeezing out the prod-
uct. This test not only assesses the suitability of the packaging itself,
but also the textural consistency of its contents.
Aerosol canister deployment: Using aerosols can be problematic,
particularly for the elderly or infirm, if the buttons on the canisters
are stiff. It is important to prevent triggering sprays accidentally
during production or transport, they must deploy easily when
needed at home. Using a cylinder probe, the texture analyzer can
imitate a finger depressing the button of an aerosol. The product
is held in grips on the base of the texture analyzer, while the probe
moves vertically downward a defined distance toward the button.
The lower the force required to press the button and release the
spray, the easier its use will be for the consumer.

485
Summary
Texture analysis techniques are valuable for all manufacturers of per-
sonal care products. From concept development through to quality
control testing of finished, commercialized products, these tech-
niques allow accurate and repeatable measurements of characteristics
that are central to product performance and acceptance.
Jo Smewing
Stable Micro Systems Ltd., Godalming, Surrey UK
Janusz Jachowicz
International Specialty Products Inc., Wayne, NJ USA
References
1. J Jachowicz and J Smewing, Using texture analysis to substantiate hair care claims,
Cosmet Toil 121(9) 6976 (2006)
2. J Jachowicz and K Yao, Characterization of cosmetic products by texture analysis,
Proceedings of the International Conference of IFSCC and the 4th Hungarian Congress
on Cosmetics and Household Chemicals, Budapest, April 1416, 1997, G Hangay, ed,
Budapest: Hungarian Chemical Society (1997) pp 297314

Chapter 47
Torsional Behavior of
Human Hair by Single
Fiber Torsion Pendulum
Method
KEY WORDS: torsion pendulum, shear modulus, conditioner effects, fiber,
cortex, sheath
ABSTRACT: Torsional properties are described by the author as a method
to distinguish between the surface and the bulk effects of
actives in hair formulations.
Undamaged hair consists of a cortex (the core) surrounded by

eight to 10 layers of cuticle cells (the sheath). The cortex consists
of spindle-shaped cells held together by cell membrane complexes
(CMCs). The tensile strength of hair depends mainly on the
cortex that forms the major component of the fiber, with little
effect from the cuticle. Some actives in cosmetic formulations are
capable of diffusing into the fiber cortex and affect the fiber
properties significantly.
Compounds that are not capable of diffusing into the fiber
penetrate the cuticular sheath and deposit only on the surface of the
fiber.1 Since cuticle cells have little effect on the tensile mechanical
properties of hair, tensile mechanical properties cannot distinguish
between the surface and the bulk effects. Torsional properties, on
the other hand, are more likely to distinguish between the surface
and the bulk effects because in torsional deformation the strain is
at the maximum at the surface and decreases towards the center of
the fiber.

488
Testing Torsional Behavior of Human Hair
Torsion Pendulum Studies

Torsional properties were evaluated with a single fiber torsion pen-
dulum2 and are shown schematically in Figure 1. The instrument
consists of a cylindrical weight attached to the end of a 30-mm
length of hair. The pendulum is set into motion by rotating the
weight 360 degrees. The period and the decay of the amplitude of
the pendulum were determined to evaluate the shear modulus and
the average log decrement. These were used in the interpretation of
the data.
Figure 1. Schematic representation of single fiber torsion pendulum
The shear modulus is given by the equation:
Eq. 1 G = (Ml 2)/ Ip
where G is the shear modulus, M is the moment of inertia of the

pendulum mass, l is the length of the fiber, is the angular velocity
(2/T, where, T is the period of the pendulum), and Ip is the polar
moment of inertia of the fiber cross section that is given by (/4)

489
Kamath Chapter 47
(a3b + ab3), a and b being the semi-axes of the elliptical cross-section

of the fiber.
Average log decrement (ALD = ) is given by:
Eq. 2 = (1/m) log (wn+m /wn)
where n and m are the cycle numbers for which the amplitudes
were measured. Average log decrement is a measure of the energy
dissipation in the fiber. The shear modulus and the ALD go in the
opposite direction, i.e., when the shear modulus increases ALD
decreases.
To show the difference between the effects of fiber penetration
and surface effects, a study was conducted on European dark brown
haira taken from different sources (i.e., not from a single head), with
high and low molecular weight conditioners.
Two conditioning compounds were usedpolyquaternium-10
(PQ-10) and cetrimonium bromide (CETAB) with high (400,000)
and low (380) molecular weightsas examples of actives that
deposit on the surface and diffuse into the bulk of the fiber, respec-
tively. Hair fibers were bleached with a commercial product, then
actives as 0.5% solutions were applied to test strands. Fibers were
kept in the bleach product for 30 minutes for the actives to pen-
etrate the fiber and then were rinsed and air-dried. Long treatment
times were used to ensure the deposition of actives on the fiber. In
practice this can be considered as the cumulative effect of repeated
treatments.
Results
The shear moduli of hair bleached and treated with PQ-10 and
CETAB are shown in Figure 2 as a function of fiber cross-sectional
area. The dependence of shear modulus on the fiber cross-sectional
area is due to the core-sheath nature of the fiber as well as ellipticity.
However, the conditioner effects can be seen clearly as statistically
significant increases in the shear modulus. The increases are much
higher for CETAB as compared to PQ-10 because the former pen-
a
Supplied by DeMeo Brothers

490
Testing Torsional Behavior of Human Hair
etrates both the cortex and the cuticle, whereas the latter penetrates
only the upper cuticular regions of the fiber. Although not shown
here, as expected, ALD shows a decrease with the application of the
conditioner in the same order.
Figure 2. Shear moduli of bleached hair treated with (a) PQ-10 and (b) CETAB

491
Kamath Chapter 47
To show the advantages of shear modulus measurements over

tensile mechanical properties, the tensile mechanical of the same
samples of hair in Table 1 have been listed. The data is an average
for 50 hair specimens and clearly demonstrates that conditioner
effects are not manifested in tensile mechanical properties. The
method can be applied to other types of actives, such as moisturizers
and humectants.
Table 1. Tensile mechanical properties of over-processed

bleached hair
Elastic Work at Work to Break

modulus 20% ext. break stress
Fiber (GPa) (MJ/m2) (MJ/m2) (MPa)
Untreated 2.870.064 0.560.008 1.330.059 195.623.24
Bleached 2.950.104 0.550.015 1.510.102 185.515.42
Bleached with PQ-10 2.890.110 0.540.023 1.660.083 196.626.18
Bleached with CETAB 3.060.120 0.570.030 1.610.090 197.447.78
Y. K. Kamath
TRI/Princeton, Princeton, NJ USA
References
1. S Ruetsch, Y Kamath, and HD Weigmann, The role of cationic compounds in
reinforcement of the cuticula, J Cosmet Sci 54 6383 (Jan/Feb 2003)
2. D Persaud and YK Kamath, Torsional method of evaluating hair damage and
performance of hair care ingredients, J Cosmet Sci, 55 (supplement) S65S77 (2004)

Chapter 48
In Vivo Quantitative
Evaluation of Gloss
KEY WORDS: Gloss, shine, skin, hair, light scattering, polarization, imaging
ABSTRACT: A real time polarization analysis technique that differentiates
components of scattered light in video images enables in vivo
quantitative evaluation of gloss from hair and skin during
quality control and claims substantiation.
Cosmetic manufacturers need to quantify the visual appearance of

their products objectively and accurately to study skin and hair, to
improve the performance, quality and the reproducibility of cos-
metic products, and to substantiate their claims. In vivo non-contact
testing provides the most meaningful results since it is carried out
in realistic conditions directly on a model. For this chapter, in vivo
gloss measurements were conducted on commercially available hair
and skin products.
Color and Gloss

Color and gloss are two important parameters that define the visual
appearance of an object. To simply explain the physics of the light-
scattering phenomena, lets consider the case of a planar object
illuminated by an incident light coming from one direction (see
Figure 1) (see Color Insert 18). The outgoing scattered light can be
divided into different categories.1-3
Mirror-like reflected light or specular reflection: A portion of light
is optically reflected by the surface of the object at a symmetrical
angle (mirror-like reflection at specular angle) just like a bouncing
ball. Specular light does not usually penetrate the object, so in most
cases it does not carry any information related to the color pigment.
Thus, the color of the specular light is related to the color of the

494
Testing In Vivo Quantitative Evaluation of Gloss
illumination. Indeed, one can easily observe a white reflection when

looking at an object from the specular angle. Artists call it a high-
light3, to scientists its a specular reflection or surface scattering, and
cosmeticians term it gloss, shine or luster.
Figure 1. Light scattered by an object
Volume scattering: A portion of light penetrates inside the object

and is scattered and/or absorbed by the color pigments. The volume-
scattered light that is not fully absorbed leaves the object carrying the
color information of the pigments. Indeed, when viewing an object
from an angle other than the specular angle, one can observe the color
of the object. Volume-scattered light is also called diffused light.
Surface scattering: Finally, a portion of light is scattered at the
surface of the object because of the presence of surface defects. The
surface-scattered light carries the information of surface quality
and surface defects. It is of particular importance for the analysis of
metallic surfaces, when there is no volume-scattered light.
Degrees of Gloss: Gd and Gd*
Based on the above parameters, we can define two gloss degrees
(abbreviated Gd and Gd*):
Gd, ranging from 0% (low gloss) to 100% (high gloss), is
the percentage of specular light in the total amount of
reflected light.

495
Clmenceau et al. Chapter 48
Gd*, ranging from 0 (low gloss) to (high gloss), is the ratio

of specular light divided by the volume-scattered light in the
direction of observation. Gd* allows the classification of high
gloss objects.
Both Gd and Gd* cover a large range of glosses and allow the
evaluation and classification of cosmetics products. Furthermore,
because they take into account the total reflectivity of the object,
they are correlated to the visual assessment carried out by the
human eye. Dark objects, for example, appear glossier (because of
their low reflectivity) than light objects (high reflectivity).
Operating Principle
Our evaluation technique is based on differentiating and measur-
ing the types of scattering events. Depending on its origin, the light
scattered exhibits various polarization signatures1,2,4. Specular light
for example, has the property of preserving the original polarization
state whereas diffused light is fully depolarized. We use an inno-
vative real time polarization analysis5,6 technique to quantify the
scattering events described above (see Polarization Analysis).
Polarization Analysis
Using a polarized illumination, specular and diffused components of
light can be retrieved by measuring parallel and crossed polarizations. This
separation has already been used and explained in past literature for hair
luster analysis7.
Thanks to recent advancements in electro-optics technology, a

fast polarimetric camera with a high polarization contrast (>100)
was developed in order to perform real-time analysis. The following
scattering parameters can now be measured1,2,4 at a video rate (15 to
30 fr/s): specular light, surface-scattered light, and volume-scattered
light, all in black and whiteor if needed, in the red, green and blue
colorimetric space. It is critical to use a high polarization contrast
(>100) technique in order to well separate the components and carry

496
out accurate gloss measurements. Figure 2 (and Color Insert 18)

presents three images delivered by this imaging systema.
Figure 2. RGB scattering images of a face
The classical image is the real image delivered by a usual cam-

era. It presents both color and gloss information. It contains the
information of totally reflected light and is the sum of the parallel
polarization (P) and the crossed polarization (C).
In the case of skin, the surface image does not provide any color
information and is black and white. It shows the distribution of
the surface scattered light on the complex shape of the face, high-
lighting the surface imperfections (pores, wrinkles). In addition, it
extracts and displays the specularly reflected light. Mathematically,
it is the exact difference between the P and the C image.
The volume-scattering image presents no specular light and
shows the diffused light and the true colors of the skin. It was calcu-
lated by multiplying by two the crossed polarization image C.
Using the definitions previously given, the images are then pro-
cessed and combined to provide accurate and consistent gloss values
Gd and Gd* on areas of the object specifically chosen by the user.
The primary innovation of our technique is that it allows for the
gloss characterization of curved and highly textured surfaces which,
until now, was not possible with classical gloss meters.
a
SAMBA is a product of Bossa Nova Technologies, Venice, CA, U.S.A.

497
Experimentation
The experimental set-up for gloss measurement includes: a pola-
rimetric imaging sensor; a polarized illumination system; and a
computer with software dedicated to fast polarization image acqui-
sition, processing and display of results (Figure 3).
Figure 3. Experimental set up for gloss measurement
The illumination can be based on fluorescent lights (cool white)

or white Light Emitting Diodes (LEDs), which make it compact,
cold and easily controllable. The software was developed to provide
calibration, acquisition of polarization images, gloss measurement,
real-time analysis, display and recording of various images. A chin
rest or a head rest is also used to control the position of the face for
optimum repeatability.
Results
In vivo gloss measurement of foundation: Foundations presenting
various levels of gloss were tested with the system. A Region of

498
Interest (ROI) in the T area of the face was chosen for the mea-
surement. The gloss degree was measured over the ROI. Results of
eight commercially available foundations are shown in Figure 4 (see
Color Insert 18).
Figure 4. Gloss results measured in the T area of the face
The gloss results correlate to visual observation and confirm the

matte/glossy nature of each foundation. The glosses ranged from
19% to 45% on the Gd scale, which demonstrates large differ-
ences between commercially available products. The accuracy of our
measurement was better than 0.5 gloss unit on the Gd scale without
using any additional time averaging with the video imaging sensor.
Efficiency testing of hair product: We also quantified the evolution
of hair shine in the following five different conditions: uncombed;
combed; combed with a reference conditioner; combed with a shine
improvement conditioner; and combed with a shine improvement
conditioner plus a liquid polish. Since hair is a highly reflective
object with low diffusion (Gd>70%), we chose to plot the results on
a Gd* scale as shown in Figure 5 (see Color Insert 19).
The results show a large range of Gd* values depending on hair
conditions and the products that were applied. Combing drastically
increases the reflected light by 50% and makes hair shinier. A classi-
cal conditioner increased the shine of combed hair by another 10%
while a second conditioner, claiming to improve the shine, increased

499
it by 40%. By adding a liquid polish, we could further increase the

shine of combed hair by 60% reaching a Gd* value of 7.85. The total
uncertainty of the measurement was 0.3 on the Gd* scale.
Figure 5. Measurement of hair shine
The Gd* measurements obtained correlate to the visual assess-

ment and depend on the hair color of the model. The present
measurements were carried out on light brown hair. Higher values
of Gd* as well as larger gloss effects due to the application of the
products are expected in the case of dark brown or black hair.
Gloss distribution: We calculated the Gloss Degree Gd (per-
centage of specular light in totally reflected light), pixel by pixel, in
order to instantly represent the spatial distribution of the gloss of
a complex 3D surface such as a human face using the formula Gd
= (P - C)/(P+C). The color of the images of Figure 6 (see Color
Insert 19) was encoded by the Gloss Degree Gd using the color
scale shown in each image. This gloss mapping mode allows the
user to visualize immediately the gloss distribution and efficiently
communicate the differences between two products. Figure 6 shows
two examples of a model face with a matte and a glossy foundation.
Here, the red color corresponds to a gloss of 50% while blue cor-
responds to 0%.The right image (glossy foundation) shows that Gd
is larger in specific areas where specular light can be observed by the
camera: tip of nose, T area, eye lids. A matte foundation presents a
more uniform, low Gd on the face.

500
Figure 6. Screen shot of Gloss Image; Color coding gloss levels, Matte foundation Glossy
foundation; Red = 50 %; Blue = 0%; Green = 25%
Advantages to Gloss Measurement

Gloss measurement is a perfectly standardized procedure in the
industry. Classical gloss meters are already widely used in the tex-
tile industry, paint industry, etc. and measure the intensity of light
reflected from the object in the specular direction. However, they
use single detectors and work only on flat surfaces8 with low texture.
They cannot quantify accurately the gloss of complex 3D surfaces.
Thanks to the scattering/polarization analysis it offers, the
described imaging technique is well adapted to cosmeticians and
provides an objective, accurate assessment of skin optical properties
independently of the object shape. In addition, the scattering analy-
sis technique offers non-contact in vivo measurement independent
of texture and shape as well as fast analysis with 5 to 25 Hz real time
operating speed for simultaneous display and calculation of polariza-
tion images and results. The speed of the system developed provides
the user with optimum experimental conditions and allows real time
measurements. The measurements presented in this chapter cor-
related to human eye assessment. High accuracy (0.3% on Gd scale)
and high consistency (0.3%) is obtained, depending on the applica-
tion. The technique leads to other light scattering characterizations
such as the measurement of whitening powers, radiance, soft focus
power and calibrated color measurement of scattered light.

501
The main limitation of the technique remains in the reposition-

ing of the object. Indeed, between treatments or applications of
new make-ups or products, the object (human face, nails) should
be repositioned at the same location with the same orientation.
Therefore, for face measurements for example, accurate mechanical
positioning systems such as chinrests and headrests are being used
to maximize the accuracy of our technique.
Conclusion
The described imaging technique opens the possibility of measuring
objectively the gloss of textured, complex 3D objects. The examples
presented in this chapter demonstrate the efficacy of the technique
for crucial applications such as the in vivo gloss measurement of skin
and hair. The technique is well adapted for the cosmetic industry to
formulate, evaluate products and substantiate claims.
Acknowledgements
The authors gratefully thank Carole Protat from Sebastian Intl, Woodland Hills, CA USA for
her participation in this work.
P. Clmenceau, S. Breugnot and B. Pouet

Bossa Nova Technologies, Venice, CA USA
Published October 2004 Cosmetics & Toiletries
References
1. S Breugnot, L Le Hors, D Dolfi and P Hartemann, Phenomenological Model of Paints for
Multispectral Polarimetric Imaging, Orlando: Aerosense (2001)
2. HC Van De Hulst, Light Scattering by Small Particles, New York: Dover (1981)
3. The Munsell Book of Color, Baltimore, MD: Munsell Color Company (1976)
4. E Collett, Polarized Light, New York: M Dekker, Inc (1993)
5. M. Rowe, EN Pugh Jr., JS Tyo and N Engheta, Polarization difference imaging: a
biologically inspired technique for observation through scattering media, Optics Letters
20(6), 608-610 (Mar 15, 1995)
6. S Breugnot and P Clmenceau, Modeling of a polarization active imager at g=806 nm,
Optical Engineering 39(10) 2677-2680 (Oct 2000)
7. R McMullen, J Jachowicz, Optical properties of hair: Effect of treatments on Luster as
quantified by image analysis, Journal of Cosmetic Science, 54, 335-351 (July/August
2003)
8. R Korichi, Video imaging in the measurement of make-up efficacy and performance,
Cosmet Toil 117(10) 39-48 (2002)

Chapter 49
Effect of New
Regulations on Hair
Coloring Products in
the EU
KEY WORDS: regulatory affairs, EU, hair care, hair color, hair dye, Cosmetic
Directive, positive list
ABSTRACT: The author suggests that current and evolving regulations
may lead to a positive list and fewer allowed raw materials
for hair coloring products in the European Union.
As we enter 2005 the status of hair dye materials in the European

Union (EU) is very unclear. Making sure a hair coloring product is
regulatory compliant and safe has always been an issue because these
products often contain intrinsically hazardous materials such as
ammonia, hydrogen peroxide and para-phenylene diamine (PPD),
which is perhaps the material with the most chequered history of all
materials used in cosmetics. Who is to say whether by the end of the
decade we will still have an hair coloring industry in the EU, based
on current chemistry, or not? To understand the position in the EU
at present we need to consider how we got here.
The History
In 1976, when the Cosmetic Directive was created, a positive list
for hair coloring ingredients was envisaged (along with one for
antioxidants) but was not created at that time. However, the leg-
islators saw the need to control materials used for the purpose of
coloring the hair as they are generally considered to be nasty.

504
Testing Effect of New Regulations on Hair Coloring Products in the EU
This was done by assessing selected materials and either banning or

regulating them via a series of Commission Directives (see Glos-
sary of Terms).
Glossary of Terms
COLIPA: The European Cosmetics and Toiletries Association
SCCP: Scientific Committee on Cosmetic Products. You can find out
who they are through the Europa DG Web site.
SCCNFP: Scientific Committee on Cosmetic and Non-Food Products.
This predecessor of the SCCP also has a Web site (that, presumably, is
completed).
Health and Consumer Protection: A Directorate General (DG) in the
European Commission. The DGs used to have numbers but this
was changed in a product relaunch sometime ago. This DG deals
with risk assessment and controls the expert committees who form
opinions based on dossiers.
Enterprise: A DG dealing with Enterprise and Industry. They form the
legislation that goes into the Cosmetic Directive acting on the
opinions of the expert committees.
European Commission: The Civil Service of the European Union (EU).
Commission Directives: Bits of European Law that can, for instance,
add ingredients to annexes. These can be created without the say of
the European Parliament (at the moment anyway).
The safety of cosmetic raw materials has been assessed for the
European Commission by a committee made up of expert repre-
sentatives from the Member States. This group has had a number
of names but was until recently known as the Scientific Committee
on Cosmetic and Non-Food Products (SCCNFP) and is currently
known as the Scientific Committee on Consumer Products (SCCP).
The SCCP reviews dossiers (or files) of safety data usually
provided by the cosmetics industry. Submission of dossiers to the
Commission often occurs through the European Cosmetics and
Toiletries Association (COLIPA) although individuals/companies
can approach the Commission directly. The safety assessment could

505
Hefford Chapter 49
result in a dye ending up banned and on Annex 2 (Table 1). If

found to be safe, it could be placed on Annex 3 Part 1. Recently,
dyes found to be not unsafe were placed onto Annex 3 Part 2 (a
provisional list with a time limit, recently extended to the end of
2005). Currently any material not in Annex 2 or 3 could be used
as a hair dye as long as it has been assessed as safe for use within a
product by the safety assessor working for the producer.
Table 1. Annexes of the EU Cosmetic Directive
Annex Title
I Illustrative list by category of cosmetic products
II List of substances which must not form part of the composition of
cosmetic products
III part 1 List of substances which cosmetic products must not contain except
subject to restrictions and conditions laid down
III part 2 List of substances provisionally allowed
IV* List of coloring agents allowed for use in cosmetic products
V* List of substances excluded from the scope of this directive
VI* List of preservatives which cosmetic products may contain
VII* List of UV filters which cosmetic products may contain
VIII Relates to off-package information and the hand symbol
VIIIa Relates to Period After Opening and the durability symbol
IX Relates to validated alternative (to animal) test methods
Next? List of substances allowed for use in hair coloring products
* Also had part 2 provisional lists in the past but these are generally empty.
For many years the submission of hair dye safety dossiers (most
often through COLIPA) continued on a voluntary basis with the
supply of dossiers outstripping the Committees ability to assess
them. However, relatively recently publications alleging a link
between bladder cancer and hair coloring product usage stimulated
a demand for a positive list and more complete control of hair dye
materials. Because a positive list (still envisaged today as a poten-

506
tial Annex 10) requires an 8th council amendment to the Cosmetic

Directive and no one really has the stamina for another one just yet,
an alternative way had to be found.
The Route to a Positive List and Its Consequences

The process to a positive list has been generally laid out by the
Commission and has gone (and is proposed to go) as indicated in
Table 2. In general the linkage from the producers of hair color-
ing products and materials (with respect to the submission of raw
material safety dossiers) has been through COLIPA who provide a
coordination function. It would be quite possible for a company to
interact directly with the Commission in this respect but in general
this has only occurred in rare circumstances.
We can look at a few of these points in a little more detail. You
will have noticed that there are a number of places where current
hair dye materials will be lost to you.
The legislation concerning Point 4 should happen soon. The
opinion contains a list of materials likely to be banned. These are
unlikely to affect you when was the last time you used isoleucine
as a hair dye? In general ingredients placed on Annex 2 will be
lost because there is no data, not because they have been shown to
be unsafe.
Point 5 is important because all dossiers even those for materi-
als on Annex 3 Part 1 must conform to the most recent SCCNFP
requirements (see The Contents of a Safety Dossier). The list of
hair dyes that will be supported is not available in the public domain.
Due to the increased and altered testing requirements, the
majority of recent opinions have the following conclusion the
information submitted is inadequate to assess the safe use of the
substance and this is the case for most of those materials already
included in Annex 3 Part 2. In many cases the inadequate infor-
mation is in the area of genotoxicity and physical characterisation
of the material. It is not really possible to put a meaningful figure
to the cost of these additional requirements because this depends
entirely on what has already been done, which tests remain to be
done and the complexity of the chemical characterisation. Suffice it
to say, none of this testing usually comes cheap.

507
Hefford Chapter 49
Table 2. Route to a positive list on hair dyes
Task Comments
1. Ask how many hair dyes to be This was an on-going process brought to a
supported by the submission conclusion by task 2.
of safety dossiers.

2. Ask to see the dossiers. Deadline was end September 2003.
3. Issue an opinion on hair dyes This had been done see SCCNFP/0807/04
(on the INCI list) but without complete with list of unsupported dyes.
a dossier.

4. Put the supported dyes onto Annex 2. This has yet to be done. There is usually a
time lag between opinions and legislation.
Time for implementation can therefore
be short.
5. Ask for safety dossiers according Deadline July 2005. Will this be enforced?
to new SCCNFP requirements. Watch this space.
6. Evaluate the safety dossiers and No dates given for this.

issue opinions (SCCP).
7. Legislate on basis of opinions. No timescale. Those that pass to Annex 3

part 1? Those that are unsafe to Annex 2?
Those that dont meet requirements to
Annex 3 part 2?
8. Submission of dossiers covering Deadline December 2007. An initial

combinations of ingredients opinion has been published on
(i.e. oxidative systems). this subject.
9. Set up positive list. Could be Annex X or later. No deadline

for this.
Note: This exercise covers all permanent and non-permanent hair dyes but currently does miss
some materials (e.g. old hair dyes no longer used that are not on the INCI list). It probably
also does not cover materials that colour the hair in a wash-in/wash-out fashion. These may
be regarded as cosmetic colourants and thus fall under Annex IV with consequent labelling as CI
numbers. They will still need a safety dossier!

508
As a result of the evaluation of the new dossiers, some additional

materials may be lostbut which ones? In addition, a number of
dyes, initially intended to have dossiers prepared, may not get them
because of the cost of additional testing. We should get to know the
contents of the new defended list sometime after July 2005 when
the deadline expires.
The Contents of a Safety Dossier

The required contents of a safety dossier to go to the EU Commission are
too extensive to go into in detail here, however, the requirements for a hair
dye dossier include:
1. Checklist
2. Chemical specification (purity and impurities)
3. Test for dyes/dye precursors alone and/or in combination with other
substances to simulate conditions of use
4. Data on genotoxicity
5. All available data on carcinogenicity
6. Justifications if any deviations from the above
If you want more detail of the requirements, a start is the Guidelines for
Cosmetic Products volume 3 which can be found on the Commission Web
site (at http://pharmacos.eudra.org/F3/cosmetic/cosmetlex.htm). However,
this is not kept up to date and better perhaps to go to another area of the
Commissions Web site (at http://europa.eu.int/comm/health/ph_risk/
committees/sccp/documents/out242_en.pdf). This gives you the 5th revision
of The SCCNFPs notes of guidance for the testing of cosmetic ingredients
and their safety evaluation.
To keep up to date with what is required for mutagenicity/genotoxicity
stay at the same Web page (at http://europa.eu.int/comm/health/ph_risk/
committees/sccp/documents/out273_en.pdf) this is Recommended
mutagenicity/genotoxicity tests for the safety testing of cosmetic
ingredients to be included in the annexes to council directive 76.768/
EC. These documents may be amended further and in addition it will be
necessary to be sure of what alternative tests will be validated. I assume
that these will become available initially through the SCCP. No one can
accuse the Commission of being short of words.

509
Hefford Chapter 49
Task 8 is interesting and represents a difficult area. Safety assess-

ments performed on cosmetic materials have, in general, been based
upon the properties of the individual material. With oxidative hair
dyes a number of precursors are reacted to form something else so
what are the toxicological properties of the reaction products and
the intermediates? One opinion has already emerged on this sub-
ject1 but this really only considers method validation. At this stage
it is impossible to predict what the outcome of this work might be.
Generally the species that are created during the oxidative reaction
to form the coloured materials only exist transiently and this makes
meaningful studies difficult.
Non-Organic and Organic Coloring

We have recently seen two hair dye events that are worthy of
comment.
Firstly we have the loss of the final metal to be used in hair
coloring products in the EU. Lead has become a victim of
the 7th Amendment to the Cosmetic Directive which enables
the banning of materials on the basis of hazard (class 1 and
2 CMRs) rather than of risk. A small loss, you might think,
but if this is the start of a trend (i.e. the use of hazard and not
risk as a criterion in safety assessment) we will have a lot more
difficulties on our hands.
Lawsone has been found to be unsafe for use as a hair dye and
may well find its way onto Annex 2 (i.e., be banned). Lawsone
is an active ingredient in henna, a natural and organic hair
coloring material. However, henna is rumoured to be on its
way onto Annex 3. This situation is complicated by the natu-
ral nature and traditional usage of henna, on skin as well as on
hair. Im certain a suitable compromise will be reached.
Conclusion
It is likely that over the next few years a significant number of hair
dye materials will be lost to the formulator as an effective and then
a final hair dye positive list is created. This means, at best, that
products will need to be reformulated for the EU market. At pres-

510
ent there is no real sign that US regulations will keep up with these
changes. If recent practice is followed by the Commission it is likely
that formulators will be given very little official time to make the
changes so it is very important for hair coloring producers (particu-
larly outside of LOral, Henkel and P&G) to keep their attention
on this area to get as much warning as possible.
However, it should also be remembered that the EU Cosmetics
Directive simply instructs the Member States to enact the regula-
tions into their local law and that the time this takes as well as
the time given for compliance (also the degree of enforcement) may
well vary from one country to the next. The loss of any of the most
important materials could cause a major change to the face of the
EU hair coloring product industry.
R.J.W. Hefford
Independent Cosmetic Advice, Ltd., Newcastle upon Tyne UK
Published April 2005 Cosmetics & Toiletries
References
1. SCCNFP/566/02

Chapter 50
Using Texture Analysis

to Substantiate Hair Care
Claims
KEY WORDS: texture analysis, claims substantiation, hair care, testing,
combability, tensile strength, bending strength, tackiness,
stiffness, flexibility, conditioning, styling
ABSTRACT: Texture analysis provides quantitative information about a
materials response when deformed by a controlled force.
When texture analysis is applied to hair treated with various
conditioners and styling fixatives, the results can help
substantiate claims made about the effectiveness of these
hair care products.
For manufacturers wanting to differentiate their products and sub-

stantiate their claims, texture analysis is a valuable tool. Scientific
texture analysis provides quantifiable, repeatable and accurate data
on the physical properties of food, cosmetic, pharmaceutical and
chemical products. It is now an established procedure in research
and a valuable tool in the quest for improved quality control meth-
ods (see Exploring New Dimensions in Texture Analysis). This
chapter describes the use of texture analysis to substantiate claims in
hair care by testing treated hair samples.
Equipment for Texture Analysis

In cosmetic applications, texture is an important attribute that
is sensed by the hands, lips, skin, hair and scalp. It encompasses
the products feel, such as the hardness of a soap bar. It also
encompasses that products effectiveness, such as the ability of a
conditioner to soften hair. Texture affects processing and handling,
and influences buying habits and consumer acceptance of products.

512
Testing Using Texture Analysis to Substantiate Hair Care Claims
Exploring New Dimensions in Texture Analysis

Two recent developments in the field of texture analysis are the testing
of acoustic emissions from food products during deformation and the video
recording of the test during texture measurements to supplement traditional
force-distance-time information. Although initiated in the food industry,
both have implications for cosmetic and personal care products.
Acoustic data is useful in the analysis of products like bath bombs,
whose satisfying fizz is central to consumer appeal. The benefits of video
recording are greatest in tests that happen quickly, such as the bursting of
a gel capsule. The synchronized video data can be replayed frame by frame
to correlate with force measurements.
This information is easily shared between different departments or
countries. It is useful especially if samples are limited or expensive, which
makes repeated testing unfeasible.
Texture traditionally has been assessed, or analyzed, through

human sensory analysis: smell, sight, taste, sound and touch. But
these methods are subject to wide variability, even when using
trained assessors. The use of instruments to measure texture defines
and improves controlled conditions and enhances test accuracy,
quantification and repeatability.
Figure 1 shows three devices used in the texture analysis
described in this chapter: a texture analyzer, tensile grips and a hair-
combing device.
Texture analyzers: Texture analyzers, such as the onea shown
in Figure 1a, are used to measure many properties, such as hard-
ness, brittleness, fracturability, adhesiveness, elasticity and bloom
strength, on a vast range of materials. They subject the material
to a controlled force and they generate a deformation curve of the
materials response.
Depending on the product to be tested and the textural char-
acteristic being investigated, the texture analyzer is fitted with an
attachment designed for specific tests. Usually, each attachment
consists of two parts. One part fits to the base of the analyzer and
a
Model TA.XT Plus Texture Analyser from Stable Micro Systems, Godalming, Surrey, UK.

513
Jachowicz and Smewing Chapter 50
normally holds the sample. The other part is attached to the under-
part of the analyzers arm. This upper fitting normally is the one
that carries out the measurement using electronics contained in the
arm and sophisticated software. The arm of the texture analyzer
moves up and down according to a pre-determined test program.
Users can define individual arm movement sequences at various
speeds and distances, enabling compressive or tensile action on the
sample, even for complex test protocols.
a c
Figure 1. Equipment used for texture analysis of hair care products (photos courtesy of Stable
Micro Systems Ltd.)
a) Texture Analyser
b) Tensile grips, used to support hair fibers to determine their stiffness and bending strength
c) Hair combing device
Tensile grips: Tensile grips, such as the onesb shown in Figure 1b,
are devices to hold a hair strand or a hair tress firmly at either end
for the purpose of determining its tensile strength.
Hair-combing device: A hair-combing device, such as the onec
shown in Figure 1c, holds a hair tress firmly at either end and draws
a comb through the hair. When assessing combability, a researcher
b
Tensile Grips from Stable Micro Systems
c
Hair Combing Device from Stable Micro Systems

514
typically performs the comb force test for a certain number of

combing cycles in order to obtain a complete assessment of the
effects of a treatment with repeated combing.
The hair-combing device can be set up in such a way that the
combing fixture is positioned onto the texture analyzer and the sup-
ported length of hair tress held vertically near the comb. The arm of
the texture analyzer is then instructed to move downward through
the hair tress at a user-defined speed. In doing so, it combs through
the length of hair. If repeated combing is required, the comb can
be disengaged mechanically at the end of its combing stroke. The
comb fixture then returns to its starting position away from the hair
tress. At the starting position the comb is mechanically returned
to its combing position within the hair, ready to commence the
next combing cycle. This can be continued for as many cycles as is
required within one test to complete the assessment.
Dynamic Hair Spray Analysis

ISP recently developed a new method, termed dynamic hair spray
analysis, to study the mechanical behavior of preset hair tresses,
untreated tresses and tresses modified by hair spray resins, under a
wide range of bending deformations.1 This technique also employs
a texture analyzer, which acts as vertical tensile testing machine
and measures force in both compression and extension modes. The
instrument, which includes a sample holder and spraying devices,
performs the test in three stages:
Applying low intermittent deformations to a preformed hair
tress in order to determine the properties of untreated hair.
Treating the fibers with a hair spray.
Measuring the changes both in adhesive properties of a hair
spray solution on the surface and in mechanical stiffness of
the fiber assembly as a function of drying time.
This approach allows the simultaneous determination of param-
eters such as stiffness of untreated and resin-modified hair, duration
of tack, maximum value of tack force and time of drying.
Experimental setup: The complete dynamic hair spray analysis
system, including the texture analyzer, sample holder and spraying

515
devices, is housed in an acrylic glass box equipped with a humidity

controller. A drawing of the experimental setup is shown in Figure 2.
Figure 2. Experimental setup for dynamic hair spray analysis
Two aerosol cans, each containing 100 g of the same hair spray
formulation, are positioned nine inches away from the hair tress at
an angle of 60 degrees from the horizontal plane, using three-prong
clamps. The hair is wetted, dried and shaped into an omega loop,
and dried at 50% relative humidity (RH) for at least 12 h to form
a set maintaining geometrical dimensions at low humidity for a
period of time necessary to apply the fixative.
Test method: The hair tress is weighed and positioned under
the texture analyzers probe. It is fastened to the base plate with
two plastic tabs set 1.2 cm apart as shown in Figure 3. Each test
is performed by oscillating a clear plastic probe (25 mm in diam-
eter) between the fiber surface and the calibration height of 10 cm.
After touching the surface of hair and sensing a 2 g force, the probe
produces an additional 1mm deformation of the loop before return-
ing to the calibration height. Initially, the stiffness of untreated hair
is measured. After a baseline value has been established, each side of

516
the tress is sprayed with an aerosol hair spray formulation for 2 sec.
The measurements are continued for 80 min, after which the tress is
weighed again to determine the amount of deposited resin.
Figure 3. Scheme showing the geometry of hair samples shaped into omega loops
For a hair spray drying experiment as described above, the plot of

force as a function of time is a series of peaks, with each peak cor-
responding to one deformation cycle of a hair loop. The maximum
positive and negative values of force are recorded along with the cor-
responding displacement values. The peak forces have been found to
be proportional to the stiffness modulae of the fiber assembly.
Curve interpretation: Figure 4 shows a typical hair spray drying
curve in which the force (peak force in grams) is plotted as a func-
tion of time.
The variation of the geometrical dimensions of a loop is
described by the plot of the differential tress height as a function
of time (upper curve and the right hand y axis). The initial por-

517
tion of each drying curve corresponds to untreated hair. After the

assessment of unmodified hair as a reference point, the fibers were
sprayed for 2 sec, followed by intermittent measurements of stiff-
ness and tackiness forces for 10004000 sec. The negative peak
forces indicate the adhesion of the probe to the resin-modified hair
surface and can be used as a measure of the magnitude of hair spray
tackiness (maximum tackiness). The duration of tackiness and the
total amount of time elapsed between hair spray application and the
disappearance of stickiness (dry time) also can be calculated. Other
parameters shown in this figure include the stiffness ratio (the ratio
of the maximum stiffness of resin-modified hair to the stiffness of
untreated hair) and the total time to reach maximum stiffness (total
dry time).
Figure 4. Force and differential tress height as a function of drying time for a typical hair
spray composition (55% VOC)
Substantiating Claims for Conditioners and

Conditioning Shampoos
The condition of hair degenerates for three main reasons:
mechanical (brushing, friction), chemical (coloring, perms) and

518
environmental (UV damage, heat from blow drying). Conditioning

shampoos and conditioners aim to nourish and protect the hair, and
sometimes even to reverse previous damage. Agents such as cationic
surfactants, polymers, emollients, vitamins, amino acids and UV
filters are commonly used for this purpose. When used successfully,
these agents increase the hairs softness, smoothness and shine. They
reduce static properties, breakage and split ends. They also improve
the hairs manageability and combability.
Wet combability testing: Combability tests on wet hair treated
with conditioning agents have provided interesting results. Wet
combability is measured under controlled conditions using an objec-
tive method in which the force required to push a comb through a
wet hair tress is measured. Before testing, hair should be detangled
and then tangled again in a controlled and reproducible way to
ensure consistency. Hair tresses containing only water are tested to
establish an initial benchmark. For this, the hair is brought to a wet
state by spraying the tresses with water until a the amount of water
absorbed by the hair, also called the water regain, is 60% by weight.
The initial force necessary to comb the hair tress is measured by a
texture analyzer under conditions of 20C temperature and 65% RH.
Then, the conditioner or other test solution is applied to the
same tress, which is then washed with a standard shampoo, dried
and held in a climate-controlled condition for 24 h. The hair is
brought back to a wet state by spraying with water until a water
regain of 60% by weight is achieved, and combed at 20C in the
same way as before treatment. Again, the final force necessary to
comb the hair is measured, which shows whether the hair care
product provided any improvement in combability.
The maximum force to comb and the total work done are taken
as comparative measures, usually calculated as a percentage in terms
of the treated sample versus the earlier, untreated one. Where these
forces are reduced, easier wet combability is implied. This is associ-
ated with the removal of entanglements of the hair fibers and can
therefore be used to substantiate claims of improved manageability.
Dry combability testing: This type of test is equally effective for
assessing combability of dry hair. When they are resin-modified,
all hair types show an increase in dry combing forces (compared to

519
virgin hair) as quantified by combing measurements. The combing

work is calculated as the area under the curve as measured in g cm.
The combing work and force as a function of tress distance would
be substantially higher for all modified hair types than for virgin
hair. This method can therefore be used to assess, for example, the
effect of applying smoothing serums to dry hair.
Tensile testing: Assessing the tensile strength of a tress or a single
strand of hair is another way to evaluate the effectiveness of strength-
ening properties of conditioners and conditioning shampoos. The
strand, or fiber bundle, is held in tensile grips (Figure 1b). As the
arm of the texture analyzer rises, the sample is stretched to break-
ing point to assess its tensile properties. Maximum load, extension
at maximum load, energy (or work) required to extend fibers by a
specific percentage and total energy to break are all valuable proper-
ties closely related to the consumer perception of hair strength.
Styling and Fixatives

Consumers today demand shinier, healthier hair coupled with a
more natural, but long-lasting, style. Hair fixatives, particularly hair
sprays, have traditionally fixed a style by increasing the stiffness of a
fiber assembly. But this sticky, stiff or unnatural style has fallen out
of favor: touchable now is the buzzword. However, the consumers
perception of touchable actually is comprised of a number of physi-
cal and aesthetic characteristics, including flexibility and memory
properties of the style set, hair softness and the lack of stickiness.
The next generation of hair fixative polymers will reflect these new
sensory performance measures.
Synthetic polymers are the ones most commonly found in the
mass and salon markets. Naturally derived polymers, such as modified
starches, can provide similar hair-holding properties with the added
benefits of touchable hold, low tack and a natural feel. But switching
to natural polymers necessitates objective analysis to measure the
extent of these changes and quantify (and substantiate) the desirable
claims. Various tests can be employed to assess the hairs physical
qualities that potentially are affected by formulation modifications.
Dynamic hair spray analysis is used to measure the kinetics of
the drying of a fixative on hair. That includes measurements of

520
tackiness. To simulate product application by spraying, this analysis

uses a test method already described in reference to Figure 3. One
also can use a micropipette to apply product to the surface of hair in
an omega loop.
Test of hair bending strength: In a simple and objective stiffness
or bending strength test, hair tresses are treated with polymeric
solution, dried, and allowed to equilibrate at constant temperature
and humidity conditions. The hair swatch then is placed in tensile
grips and bent to a certain degree. The force that has to be exerted
is measured by the texture analyzer. The test can yield informa-
tion about the strength or stability of the examined hairs (the more
resistance, the greater the stiffness) and the resulting hair volume,
because flexural strength is one of the factors that have a consider-
able influence on hair volume.
Analysis of hair tackiness: Most hair spray solutions become
tacky after partial evaporation of the solvent. Parameters such as
tack duration or the magnitude of the adhesive force are crucial hair
spray attributes that are perceptible to consumers.
The analysis of hair tackiness during drying of hair spray resins
on the hair surface was carried out at ISP by applying 0.07 g of a
hair spray solution (polymer concentration 5.71% w/w) to a dry loop
of hair and following the time dependence of adhesive forces by
intermittent flexing by a texture analyzer.
A typical example of this experiment is presented in Figure 5.
This diagram illustrates an increase in duration of adhesive forces for
compositions based on the ethyl ester of PVM/MA copolymer and
containing progressively higher levels of water. The observed average
tackiness periods (three measurements) were 1946 s, 29228 s and
540100 s for 100% VOC, 80% VOC and 55% VOC compositions,
respectively. It is also noteworthy that the magnitude of the tack
forces does not increase for water-containing hair spray solutions.
On the contrary, the results of the experiments point to a progressive
reduction in adhesion for compositions of lower VOC content.
Measuring dry film adhesive force: ISP also has evaluated the
tackiness of dry films exposed to high humidity levels. The hair
was shaped into omega loops and treated with hair spray solution
using an Eppendorf pipette. The deposited hair spray (0.15 g per

521
Figure 5. Comparison of the time dependence of adhesion forces for a) 100%, b) 80% and
c) 55% VOC hair spray compositions based on the ethyl ester of PVM/MA copolymer

522
0.2 g hair sample) was uniformly distributed over the tress surface,
thoroughly saturating the fibers between the plastic tabs. In order to
preserve the circular shape of the loops for stiffness measurements,
Teflond-coated, cylindrical rods were inserted into the loops imme-
diately after treatment and left in place while the hair was dried and
conditioned overnight (50% RH, 70F) prior to measurement at 90%
RH. The measurements consist of intermittent loop deformation
with a given force or deformation strain, and monitoring the negative
force in each deformation cycle as a function of time for 80 min.
Example results are shown in Figure 6, which displays the
variation in tackiness forces for PVP/VA copolymer E-735 and for
a blend PVP/VA copolymer (E-735vinyl caprolactam/PVP/dim-
ethylaminoethyl methacrylate copolymer). The data demonstrates a
large reduction in both the magnitude and duration of tackiness for
a polymer blend (System D) compared to the one-component PVP/
VA copolymer (System A). The results can be presented in the form
of plots such as those in Figure 6 or, after integration, as the values
of the work of adhesion.
Analyzing the stiffness and flexibility of polymer-treated hair:
The mechanical behavior of preset hair tresses modified with styl-
ing polymers can be examined using a texture analyzer. Wet hair
tresses are prepared and secured in the shape of omega loops 16 mm
in diameter using special holders. Hair samples then are dried on a
roller under controlled humidity to form a permanent set.
The mechanical measurements are carried out by oscillating a
plastic probe between the fiber surface and the calibration height of
4 cm (see Figure 3). After touching the surface of hair and sensing
a 2.0 g force, the probe deforms the loop by an additional 14 mm
(6.2525%) before returning to the calibration height. Deformation
of 1 mm typically is within the elastic limit of both untreated and
resin modified-hair.2,3 Deformation of 4 mm (25%) usually results
in irreversible damage to polymer-treated hair and is employed to
study the flexibility of styling products.4
The raw data from the experiment includes the values of force
and distance as a function of time. Plotting force as a function of
d
Teflon is brand of DuPont

523
time gives a series of peaks, with each peak corresponding to one

deformation cycle of a hair loop. Plotting force as a function of
distance provides an immediate test of the linearity and allows a
judgment about the elasticity of the treatment.
Figure 6. Tackiness as a function of time for PVP/VA copolymer E-735 (System A) and a
blend PVP/VA copolymer E-735Vinyl caprolactam/PVP/dimethylaminoethyl methacrylate
copolymer (1:2) (System D)
For most of the systems investigated in 06% deformation, the

mechanical response was a linear plot of force = f (distance). It is
usually reversible, showing only a small hysteresis. A typical force
corresponding to 1 mm deformation for untreated hair varies from
10 to 15 g, depending on the batch of hair and its type. After treat-
ment with styling solutions, this value increases 1040 times. A

524
parameter to characterize the stiffness of hair after treatment was

defined as a ratio of the measured maximum force at 1 mm defor-
mation for treated and untreated hair.
Ftreated (1mm)
Stiffness Ratio =
Funtreated (1mm)
Experimental data at high deformation of 25% (4 mm) can be

presented in a plot of force as a function of distance, as shown in
Figure 7, for the first deformation (Figure 7a) and the first 10 con-
secutive deformation cycles (Figure 7b). The data in these figures
correspond to a brittle polymer characterized by an elastic response
in the deformation range of 01 mm. It is in this deformation range
that one can calculate the modulus E as the slope for the depen-
dence of force = F (distance) in the linear portion of the curve. Then
one can calculate the ratio of modulae, E10/E1 at the 10th and first
deformations, and use that ratio as a measure of flexibility of the
sample, which is hair treated with a polymer in this case.
To further characterize the flexibility of the polymer used as a
hair treatment a parameter F10/F1 can be calculated as a ratio of the
maximum force in the tenth deformation (F10) to the maximum
force in the first deformation (F1). As illustrated by the curves in
Figure 7, at a deformation of about 2 mm in the first cycle, the
polymer bonds between fibers break, resulting in a reduction of
maximum force (F) and modulus (E) in subsequent deformations. A
plasticity parameter denoted as H10/H1 can be calculated as:
2H1 H10
H1
where H1 and H10 are deformation distances in the first and 10th
deformations. H1 is equal to 4 mm while H10 represents 4 mm plus
the distance resulting from the omega loop geometry change. The
plasticity parameter scales from 1 corresponding to the case of no
change in sample dimensions (no plasticity, H10=H1), to 0, which
corresponds to doubling of the deformation (2H1=H10).

525
Figure 7. Typical experimental trace of force as a function of distance obtained in a

dynamic hair spray analysis experiment. E1, E10 = Elastic modulae (slope) in the first and
10th deformations.
Conclusion
This chapter has focused on texture analysis as a method for assess-
ing the effectiveness of hair care products. In these examples, texture
analysis was performed on hair that was untreated, treated or in
some way modified by the product. Future work will illustrate the
use of texture analysis performed on the product itself as a way to
help resolve formulation issues with these products.
Janusz Jachowicz
ISP, Wayne, NJ USA
Jo Smewing
Stable Micro Systems Ltd., Godalming, Surrey, UK
References
1. J Jachowicz and K Yao, Dynamic hairspray analysis. I. Instrumentation and preliminary
results, J Soc Cosmet Chem 47 7384 (1996)
2. J Jachowicz and K Yao, Dynamic hairspray analysis. II. Effect of polymer, hair type, and
solvent composition, J Cosmet Sci 52 281 (2001)
3. J Jachowicz, Dynamic hairspray analysis. III. Theoretical considerations, J Cosmet Sci
53(5) 249 (2002)
4. J Jachowicz and R McMullen, The mechanical analysis of elasticity and flexibility of
virgin and polymer-modified hair, J Cosmet Sci 53(6) 344 (2002)

Chapter 51
Recent Polymer
Technologies for Hair
Care
KEY WORDS: hair and hair care, polymers, resins, styling, conditioning,
rheology
ABSTRACT: More than 20 polymers from seven companies are reviewed
in this survey of recent polymer technologies for hair care. A
variety of new functions and multifunctionalities are seen in
these products launched within the past two years.
Todays hair care polymers offer a range of functionalities, such as

color enhancement, hair strengthening, antiaging, sun protection,
color retention and moisturization. It is hard to beat the old stand-
bys: styling, conditioning and rheology modification.
In this roundup of recent polymer technologies for hair care, we
hear from seven companies and more than a score of authors report-
ing on the claims, tests and functionalities of two dozen polymers.
We hope this roundup will help the reader identify new possibilities
from polymers.
A Rheology Modifier from Ciba

The polymer: Acrylates/beheneth-25 methacrylate copolymera is a
new associative rheology modifier manufactured by Ciba Specialty
Chemicals Corp. designed to give effective thickening in crystal
clear gel systems over a wide pH range. It is a hydrophobically
a
Tinovis GTC (INCI: Acrylates/beheneth-25 methacrylate copolymer) is a product of Ciba
Specialty Chemicals.

528
Testing Recent Polymer Technologies for Hair Care
modified (long C-22 alkyl chain) alkali-activated aqueous emulsion,

with an acrylate backbone modified to allow thickening at pH >6
while maintaining the solids content at 30% active polymer.
Acrylates/beheneth-25 methacrylate copolymer is supplied as
a 30% active aqueous emulsion. The development of viscosity in
aqueous solutions of this copolymer occurs on the addition of a
suitable base. The acid groups present in the alkyl backbone become
ionized and structuring occurs by electrostatic repulsion. The pres-
ence of the hydrophobically modified associative group enhances
the rheology modification by the formation of inter- and intra-
molecular micelles that provide extremely high apparent viscosities
at very low shear rates. The presence of such groups also allows
association with other hydrophobic moieties that may be present in
personal care formulations.
The combination of the optimized acrylic backbone, hydro-
phobic associative monomer and the level of cross-linking in
the polymer results in a shear-thinning nonthixotropic rheology
modifier with excellent yield value and suspension characteristics.
Acrylates/beheneth-25 methacrylate copolymer provides good
thickening over a pH range of 6.012.5. It provides excellent,
cost-effective viscosity development along with the easy handling
properties of a liquid. For optimum thickening efficiency, solutions
of this polymer need to be adjusted to greater than pH 6.0 using
common neutralizing bases.
Clarity: One of the best differentiating features of acrylates/
beheneth-25 methacrylate copolymer is that it can be used to
produce crystal-clear gel systems, with gel clarity exceeding any
that can be obtained with competitive products (lower value for
nephelometric turbidity units (NTU) means better clarity). Figure 1
illustrates the clarity measurement of acrylates/beheneth-25 meth-
acrylate copolymer versus two commercial rheology modifiers in
the marketplace at pH 6.0 and 7.0. The picture to the right of the
graph illustrates the visual differences of this new copolymer versus
polymer C in deionized water. The jar on the left contains the copo-
lymer in water at pH 6.0, and the jar to the right contains polymer
C in water at pH 6.0. The acrylates/beheneth-25 methacrylate
copolymer produces a crystal-clear gel.

529
Brewster Chapter 51
Figure 1. Clarity of acrylates/beheneth-25 methacrylate copolymer and competitive

products in deionized water (from Ciba)
Stability: The second differentiating feature is its stability profile,

especially in clear packaging. Acrylates/beheneth-25 methacrylate
copolymer, tested at 1% active polymer in deionized water at pH
6.5, passed five freeze/thaw cycles without a significant loss in
viscosity, separation or sedimentation. The copolymer tested in
clear packaging is stable at room temperature (RT), 45C, and after
exposure to ultraviolet (UV) light. Gel formulations with traditional
carbomer-type thickeners (polymers C and D) were shown to lose
viscosity quite significantly after only four weeks when exposed to

530
daylight. Formulations with acrylates/beheneth-25 methacrylate

copolymer remained stable even when exposed to daylight. Figure 2
illustrates the percent change of viscosity over a four-week period.
Figure 2. Stability results of gel formulations containing acrylates/beheneth-25

methacrylate copolymer or traditional carbomer-type thickeners (from Ciba)
Summary: Acrylates/Beheneth-25 methacrylate copolymer pro-

vides these benefits in clear gel systems:
It is an effective alternative to carbomer-type rheology modi-
fiers in clear gel systems, providing crystal-clear gels.
It provides good thickening over a pH range of 6.012.5.
It provides a shear-thinning nonthixotropic rheology modifier
with excellent yield value and suspension characteristics.
It offers the advantage of being supplied in an easy-to-use
liquid form that can alleviate the formulation problems and
lengthy processing times commonly encountered with car-
bomer-type rheology modifiers.
It offers a better stability profile than carbomer-type rheology
modifiers.
A Rheology Modifier from Noveon

There can be no doubt that aesthetic properties are some of the most
important features in personal care products. While almost any sham-

531
Brewster Chapter 51
poos can cleanse the hair, those with more attractive shelf-appeal and
a better sensory experience during use are the ones that ultimately
win the battle for market share. Thus, the need to enhance the sen-
sory experience, rather than focus solely on product functionality, is a
critical challenge facing formulators. This is why, for example, surfac-
tants are not used solely for cleansing, but also to deliver richer, more
billowy lather while minimizing the risk of irritation.
Similarly, rheology-control agents are not used solely for thick-
ening. Todays rheology modifiers must offer not only the functional
aspects of thickening, suspension and stabilization, but must also
provide more enhanced appearance to the finished product, superior
flow and pour properties; a pleasant after-feel, and a smooth, light,
cushiony feel in use.
Noveon reports on three novel technologies specifically designed
to surpass previous expectations for functionality as well as sensory
attributes: acrylates copolymer for use in surfactant-cleansing
systems, acrylates/C10-30 alkyl acrylate crosspolymer for use in
surfactant-cleansing or aqueous-based systems, and polyacrylate-14
for use primarily in aqueous-based systems. Polyacrylate-14 will be
discussed next as will two other technologies.
Polyacrylate-14: Polyacrylate-14b was designed specifically to
improve hair style longevity while enhancing sensory and aesthetic
properties, both in formulation and in use. Polyacrylate-14 is a
unique, multifunctional polymer that delivers film-forming fixative
and rheology-modifying properties in formulations. It is supplied
as a milky white liquid with a viscosity of 15 mPas, active polymer
30% w/w and pH 3.0.
The patent-pending design of this alkali-swellable, associa-
tive polymer combines hard hydrophilic, soft hydrophobic and
semi-hydrophobic components to deliver an optimized balance
of properties. This novel combination leads to these performance
advantages: excellent hold and good solubility; clear, uniform films
with good adhesion; superior humidity resistance; and a smooth,
natural feel on hair.
b
Fixate PLUS polymer (INCI: Polyacrylate-14) is a trademarked product of Noveon, Inc.,
a wholly owned subsidiary of The Lubrizol Corporation. The trademark is owned by The
Lubrizol Corporation.

532
Traditional hydrophobic associative polymers, particularly those

with long chain hydrophobes, can build very strong hydrophobic
associations in solution. The resulting gels can be highly thixotropic,
with poor texture and appearance in the presence of shear stress. In
contrast, the semi-hydrophobic pendants in the structure of polyacry-
late-14 enable controlled hydrophobic association. Thus, this uniquely
designed polymer enables improved thickening efficiency while main-
taining the smooth, buttery feel and classic shear-thinning rheology
characteristic of gels formulated with carbomerc polymers.
When neutralized with a base, the polymer opens and develops
viscosity with high clarity at approximately pH 6.5. At 1.0% active
polymer, viscosity reaches 7,000 mPas, with viscosity increasing
rapidly as concentration is increased, while maintaining high clarity
(Figure 3). 6
Figure 3. Viscosity and clarity of polyacrylate-14 at selected concentrations (from Noveon)
Due to its hydrophobic modification, polyacrylate-14 offers

exceptional efficiency with hydrophobically-modified carbomer
copolymers (such as acrylates/C10-30 alkyl acrylate crosspolymer) due
to association between the hydrophobic groups. Again, clarity in
formulations is very high.
c
Carbopol is a registered trademark of The Lubrizol Corporation.

533
Brewster Chapter 51
As noted, polyacrylate-14 is a multifunctional polymer. Even at

low use levels, it provides fixative properties with exceptional high
humidity curl retention (HHCR), whether used alone (Figure 4) or
when used in combination with leading rheology modifiers.
Figure 4. High-humidity curl retention of neat polyacrylate-14 at 0.8% TS (from Noveon)
In laboratory evaluations, styling gels formulated with just 1.0%

w/w total solids (0.5% w/w polyacrylate-14 with 0.5% w/w acry-
lates/C10-30 alkyl acrylate crosspolymerd) demonstrated greater than
90% curl retention after 24 hours (h) at 90% relative humidity
(RH), 25C.
In qualitative salon tests, styling gels formulated with 0.8% w/w
polyacrylate-14 and 0.2% w/w carbomer7 were observed to impart
greater fullness and body, without stickiness or heaviness, when
compared to a commercial styling gel formulated with polyvinyl
pyrolidone (PVP).
Other polymers from Noveon: Here are two additional Noveon
polymers that enable versatility in formulation while providing effi-
ciency essential to managing cost constraints.
d
Carbopol Ultrez 21 polymer (INCI: Acrylates/C10-30 alkyl acrylate crosspolymer) is a product
of The Lubrizol Corporation.

534
Acrylates copolymere is an alkali-swellable, lightly cross-linked

acrylic emulsion polymer designed especially for use in high-sur-
factant-content (1230% w/w) cleansing applications. Although
not an associative polymer by chemistry, it does show some associa-
tive behavior and favors surfactant structuring. Thickening occurs
via hydrodynamic volume expansion and through interaction of
the hydrophobic portion of the polymer backbone with surfactant
micelles. This three-dimensional structuring network builds vis-
cosity and other rheological properties. In the presence of typical
anionic and amphoteric surfactants, this copolymer displays the
ability to back acid thicken while maintaining the inherent proper-
ties of the polymer.
Another benefit observed with acrylates copolymer is synergistic
thickening with surfactants and salt. In the past, it proved difficult
to produce a truly high clarity surfactant-based formulation with
exceptional suspension properties. The three-dimensional structur-
ing network provided by acrylates copolymer enables formulators to
suspend beads, exfoliating agents and other insoluble agents without
sacrificing the clarity of the formulation. Optimal clarity can be
achieved at approximately pH 6.5.
Acrylates/C10-30 alkyl acrylate crosspolymerf is a hydrophobi-
cally modified, cross-linked polyacrylate polymer. As supplied, the
polymer molecules are coiled and impart relatively little suspension
and viscosity. Upon neutralization, the molecules ionize and expand
due to charge repulsion, and provide suspending and thickening
properties to the aqueous system in which they are present. In this
hydrodynamic thickening mechanism, it is primarily the physi-
cal packing (space-filling mechanism) of polymer molecules that
is responsible for the development of viscosity and suspending
capability. This is distinctly different from associative thickening.
Acrylates/C10-30 alkyl acrylate crosspolymer provides the user with
e
Carbopol Aqua SF1 polymer (INCI: Acrylates copolymer) is a trademarked product of
Noveon, Inc., a wholly owned subsidiary of The Lubrizol Corporation. The trademark is
owned by The Lubrizol Corporation.
f
Carbopol Ultrez 20 polymer (INCI: Acrylates/C10-30 alkyl acrylate crosspolymer) is
a trademarked product of Noveon, Inc., a wholly owned subsidiary of The Lubrizol
Corporation. The trademark is owned by The Lubrizol Corporation.

535
Brewster Chapter 51
consistent dispersion viscosity and efficient thickening. The polymer

features patented self-wetting technology, so it wets and disperses
quickly, without requiring agitation.
A Styling Resin from Rohm and Haas

Rohm and Haas has introduced two new hair fixative resins within
the last two years geared to formulators who want to create hair
sprays, gels, mousses or pomades that deliver a durable hold, a novel
texture and shine to the hair.
Acrylates/hydroxyesters acrylates copolymer: Conventional hair
fixative resins meeting the limit of 55% volatile organic compounds
(VOC) in sprays tend to be stiff and humidity resistant leaving an
acrylic type of crunchiness to the hair. Acrylates/hydroxyesters
acrylates copolymerg is a durable hold resin that goes beyond conven-
tional resins to enable the formulator to create soft-to-strong-hold
hair sprays where the style lasts longer, i.e., is more durable, than
sprays formulated with the conventional acrylic fixative resins.
The difference is all the more remarkable when the formulator
wants to enable a hairstyle that has a strong hold and a more natural
movement to it; i.e., not the helmet-head artificial style. Three
factors in the polymer design and mechanism make this possible.
First, the polymer consists of a dispersion of interpenetrat-
ing hard and soft acrylic film-forming polymers that create
tough spot welds that hold the hair style together. Because
considerable stress is put on the spot welds that hold the hair
style together during the day, tough spot welds help keep the
hair style more durable because they do not break easily except
when they are combed out.
Second, the bimodality of the polymer tends to reduce the
formulation viscosity relative to the same solids concentration
of a conventional acrylic hair fixative resin. This results in a
finer spray pattern for pump and aerosol sprays, leaving a less
wet feel on the hair at a given stiffness. This also allows more
resin to be optionally formulated into the pump or aerosol,
g
Acudyne DHR Durable Hold Resin (INCI: Acrylates/hydroxyesters acrylates copolymer) is a
product of the Rohm and Haas Company.

536
as in 80% VOC formulations, to build hair stiffness without

causing a wet feel to the hair.
Third, the hydroxyester-type monomers on the polymer chain
improve shampoo removability without reducing humidity
resistance. This is because the polymer does not have a ten-
dency to form tacky hydrates with water. The result is that this
durable hold resin provides good humidity resistance (Figure
5 and Color Insert 20), is easy to remove by shampoo and has
a fast set time.
Figure 5. Dia-Stron durability testing. Curled tress was treated with hair fixative and
compressed 5X in sequence. The work required to compress the curl is measured. The
acrylates/hydroxyesters acrylates copolymer resin-treated tress maintained its stiffness
after the compressions. (from Rohm and Haas)
Two other add-on benefits are the excellent film-forming prop-

erties of the resin, which when applied to the hair result in a slight
shine benefit noticed in salon testing, and the ability to reform the
film, enabling consumers to restyle their hair without adding more
hairstyling product.
Other polymers from Rohm and Haas: Acrylamide/sodium
acryloyl-dimethyltaurate/acrylic acid copolymerh is a water-soluble
h
Acudyne SCP Styling Conditioning Polymer (INCI: Acrylamide/sodium acryloyldimethyl
taurate/acrylic acid copolymer) is a product of the Rohm and Haas Company.

537
Brewster Chapter 51
anionic terpolymer. This styling conditioning polymer enables the

formulation of soft-to-medium-hold, humidity-resistant hair gels,
pomades and mousses that provide a conditioned feel to the hair.
This polymer is also biphasic. The humidity resistance is engi-
neered into the polymer design by having one phase of the polymer
able to form hydrates with water at high humidity while the film is
not plasticized. The second phase has similar humidity resistance
to PVP. With this combination, the styling conditioning polymer
provides a durable hold to the hair in high humidity. It is capable
of forming clear, bubble-suspending gels with carbomer types of
rheology modifiers. The conditioning aspect to the hair is evident
from salon evaluations and microscopy, which shows the smooth-
ness of the hair shaft after treatment compared with conventional
hair gel products.
A Styling Polymer from ISP

Copolymers of vinyl pyrrolidone and vinyl caprolactam find numer-
ous applications in cosmetic technologies requiring water-soluble
polymers with film-forming properties.1 For hairstyling applications,
one copolymer of this type is polyquaternium-69.
Polyquaternium-69 is a stiff-feel film former with long-lasting
hold for clear formulations. It provides excellent high humidity curl
retention as well as high shine and clarity. It also is compatible with
carbomer, which allows for production of clear styling gels.
Polyquaternium-69 is sold as a 40% w/w colorless, low odor solu-
tion in water (48% w/w) and ethanol (12% w/w).
Polyquaternium-69 has been found to form clear, transparent
films when cast on glass substrates. Similarly, clear films also are
formed as fixative deposits on the surface of hair. Vigorous combing
of polymer-treated hair does not lead to flaking as judged by fiber
examination at low illumination angles and by taking high magnifi-
cation images of hair with a flatbed scanner.
Polyquaternium-69 is characterized by high resistance to high
humidity, which is reflected in the measured HHCR curves (Figure
6). This phenomenon primarily is due to the high vinyl caprolactam
content in the structure of the polymer.

538
Figure 6. HHCR from polyquaternium-69 at 90% RH for the deposition amounts on hair of
5 mg/g, 7.5 mg/g and 10 mg/g. The test was carried out on very thick Chinese hair with
a major elliptical axis of 110 m. (from ISP)
The films of polyquaternium-69 are characterized by high luster

as indicated by visual observations of hair tresses as well as the
quantitative results of image analysis (an increase in the maximum
specular reflection intensity from 2104 for untreated hair to 2263
for the polymer-treated hair, Figure 7a (see Color Insert20)).2
Combination of styling and optical properties of polyquaternium-69
result in a significant improvement in reflectivity of frizzy and curly
hair (elimination of frizziness and the appearance of high intensity
reflection pattern, Figure 7b).3
The mechanical properties of hair treated with polyquaterni-
um-69 have been characterized using stiffness parameters as well as
the ratios of flexibility and plasticity; all were obtained experimen-
tally using a texture analyzer.4 The results suggest relatively high
stiffness (F1 = 473.314.8 G, stiffness ratio = 20.5 at the deposition
of 22 mg/g), moderate flexibility (F10/F1 = 0.85, E10/E1 = 0.35) and
low plasticity (H10/H1 = 0.89).
Thanks to its predominantly nonionic character (weakly cat-
ionic), polyquaternium-69 has broad compatibility with cosmetic

539
Brewster Chapter 51
ingredients, including other fixative resins and anionic polymers.

Polyquaternium-69 can be used to prepare transparent gels by using
a variety of thickeners such as carbomer, acrylates/C10-30 alkyl acry-
late crosspolymer and PVM/MA decadiene crosspolymer. A typical
product based on 0.5% carbomer and 3% polyquaternium-69 is
characterized by a haze value of 10-20 NTU. This polymer also can
be used to formulate hair mousses, lotions and shine products.
Figure 7. Specular and diffuse reflections (left) from untreated and polyquaternium-69
modified (with 1% aqueous solution) straight, dark brown hair. Light intensity plot (right)
for free-hanging, untreated frizzy hair and the same hair treated with a 3% lotion based
on polyquaternium-69. (from ISP)
A Bimodal Styling Polymer from Interpolymer

Regulatory legislation and environmental consumer groups continue
to challenge the personal care industry to reformulate aerosolized
hair styling aids in an effort to lower levels of VOCs. The industry
has contested that there may not be sufficient technology to per-
mit the formulation of marketable aerosolized products that would
deliver performance attributes economically, aesthetically and safely.
A new polymer technology is ideally suited to bridging such gaps.
Consumers expect a number of often contradictory properties
from hair styling sprays yet the ultimate goal is the same: the uni-
form application of a clear polymeric material to the hair to achieve
certain improvements in appearance and manageability. The hair

540
style must be held firmly in place under conditions of high temper-

ature and humidity, yet the hair must not feel too stiff. The spray
dispersion must be fine enough to avoid nozzle clogging and sput-
tering yet not a pose an acute inhalation risk. The formula must
contain enough non-VOC components to meet regulatory require-
ments, yet even though it is an aqueous-based formula it must dry
quickly after application. The resin solution must be able to flow
along the hair shaft to help promote adherence to the adjacent
hair fiber as the polymer dries, yet not create flakes during subse-
quent brushing or combing when either wet or dry. The hair must
appear natural and glossy yet not feel tacky or sticky, even under
conditions of high humidity. Finally, the fixative polymer must be
long lasting yet readily removable from the hair during subsequent
shampoo applications.
Acrylic copolymer technologies offer an alternative approach to
traditional polymers such as PVP, PVP/VA and other high molecu-
lar weight copolymers. Interpolymer recently has developed an
innovative technology identified as bimodal. This refers to its struc-
ture, which is composed of two different types of acrylic polymer
molecules: one with anionic and the other one with cationic func-
tionalities (patent pending). The unique bimodal technology was
designed to enhance hairstyling products by improving hold perfor-
mance in quick-setting low-VOC aqueous-based formulations.
Bimodal polymers: The bimodal technology is designed to
enhance hairstyling products by improving hold performance.
These properties are accomplished through an innovative
technology that uses a bimodal interpenetrating network that
simultaneously delivers both cationic and anionic polymers to the
hair shaft.
The result is a reversible, cross-linked polymer complex achieved
by the ionic associations of the two oppositely charged polymer
chains providing both excellent holding power and ease of removal.
The anionic chain is designed to contribute to the polymers
removal properties while the cationic chain imparts strong hold and
ease of styling. The ionic combination of the two oppositely charged
polymer chains during drying allows the bimodal polymer to mimic
the functions of higher molecular weight polymers.

541
Brewster Chapter 51
This combination of lower molecular weight and high charge

density allows the bimodal polymers to be easily sprayed and yield
adequate hold when applied. The bimodal polymers have film
formation temperatures that are balanced to give a pleasant feel
without flaking.
A strong ionic association can be formed when 2 or more chains
associate to form an interpenetrating network. The amino function
is placed in an exposed position to interact with the acidic part of
the anionic acrylic copolymer chain to form the interpenetrating
network. Co-monomer selection and molecular weight control allow
Interpolymer to optimize the steric hindrances and ionic interac-
tions that result in specific setting and hold properties.
Polymer composition plays an important role in this geometrical
and electrical interaction. The inclusion of strongly electropositive
or electronegative groups on separate molecules causes an inductive
shift of electrons. This shift affects the polymers cohesive and adhe-
sive properties. Because the bimodal polymers are composed of both
electropositive and electronegative groups, there is a great potential
for the polymer chains to exhibit this shift in electron density. At
large distances, these polymer chains would behave like an electri-
cally neutral system. However, as the ionic groups are brought into
close proximity to their counterion during the drying process, strong
secondary bond forces begin to exert their influence and give the
bimodal polymers their unique characteristics.
This novel technology relies on the ability to produce stable dis-
persions and solutions containing polymer molecules with different
ionic changes. During the drying process, the bimodal polymer will
form an ionic complex, as already described, before the final film is
completely dry and sets on the hair.
The resultant polymer complex prevents the formulation from
migrating before the water or solvent has evaporated completely.
This ability of the bimodal polymers to set quickly under high
humidity conditions makes them a reliable alternative to current
hair care polymers.
Bimodal polymers in very low VOC aerosols: Bimodal polymers
were incorporated into aerosol sprays in an effort to determine if
an aqueous-based 35% VOC formula could deliver comparable

542
performance to existing branded 55% VOC hair sprays. An addi-

tional resin was incorporated into the control formula to assist with
ancillary benefits such as gloss and luster. The bulk concentrate
component of the control formula is shown in Formula 1.
Formula 1. Low VOC aerosol bulk concentrate for a very low

VOC aerosol (from Interpolymer)
A. Alcohol denatured 70.00% by wt

Aminomethyl propanol 0.50
PEG-12, dimethicone 0.10
PEG-45 Palm kernel glycerides 0.05
B. Polyacrylates-18 (and) polyacrylates-19 19.35
Ammonium acrylates copolymer 10.00
100.00
Procedure: Add ingredients to appropriate vessel as listed. Stir between each addition
until batch is clear and homogenous. Adjust pH to 8.48.8 with AMP-95 at end, stir until
homogenous. Product is a slightly turbid solution.
For the final 35% VOC formulation, the ingredients were 50%
w/w of the Formula 1 bulk concentrate and 50% w/w of hydrofluo-
rocarbon 152A. For the final 55% VOC formulation, the ingredients
were 63% of the bulk concentrate, 10.5% dimethyl ether, and 26.5%
hydrofluorocarbon 152A w/w.
A curl retention study was conducted to determine the efficacy
of the bimodal technology in 35% and 55% low VOC aerosol hair
spray formulations. Materials chosen for this evaluation were the
polyacrylate 18 (and) polyacrylate 19 bimodal and the ammonium
acrylate copolymer as stipulated in the control formula in Formula
1. Also evaluated was a major brand with flexible hold (labeled as
containing no chlorinated fluoro carbons (CFCs) but no mention of
CAS compliance).
Two swatches for each spray were prepared by washing with a
commercial shampoo per manufacturers instructions and blown

543
Brewster Chapter 51
dry using a standard consumer-grade, hand-held hair dryer set on a

low setting. To insure that the swatches were dry, the swatches were
placed in a 38C circulating air oven for 10 minutes before styling.
The swatches were then cooled before styling with a consumer-
grade curling iron set on its highest setting. Curls were held in the
iron for 45 seconds to set the curl. When the swatch was removed,
it was set immediately on its side while the second curl for the same
test spray was prepared. After both swatches were prepared and
still lying on their sides, the test spray was applied by spraying each
swatch with approximately a one-second burst of hair spray. The
swatches were then flipped and then sprayed again on the oppo-
site side. This was done for each spray. The swatches were allowed
to dry for five minutes before moving into a vertical position for
measurement. Before the tresses were measured, they each received
another one-second application of spray while in the vertical posi-
tion and allowed to dry.
The swatches were divided into the test groups and hung for
evaluation. Ambient conditions were 74F and 45% RH. Humidity
conditions were 84F and 95% RH.
Curl length was determined as a function of time. The percent
curl retention (PCR) was calculated by means of the following
equation:
PCR = 100 x [(L Lt ) / ( L L0)]
where
L = length of hair fully extended (before curling),
L0 = length of curled hair before exposure, and
Lt = length of curled hair after exposure as a function of time.
Table 1 shows the results of the measurements of curl length and
PCR under ambient conditions and high humidity conditions for
periods of four hours.
Conclusion: This novel bimodal polymer technology is based on
unique, interpenetrating polymer networks. By incorporating both
cationic and anionic functionalities, the bimodal polymers offer a
formulator the opportunity to create alternative very low or low
VOC aqueous-based hair sprays.

544
Table 1. High-humidity curl retention of hair swatches

curled and sprayed with 35% and 55% low VOC aerosol
hair sprays containing bimodal polymer or with a major
brand flexible hold spray without bimodal polymer (from
Interpolymer)
Curl Length (and Percent Curl Retention) at Hourly Intervals

Sample Start Hour 1 Hour 2 Hour 3 Hour 4
Ambient Conditions
35% Control 14.5 15.5 (69.7) 15.0 (84.8) 15.0 (84.8) 15.3 (75.8)
55% Control 14.0 15.0 (73.7) 14.5 (86.8) 14.5 (86.8) 14.5 (86.8)
Major Brand 12.5 14.0 (71.7) 13.5 (81.1) 13.5 (81.1) 13.8 (75.5)
High Humidity Conditions

35% Control 14.0 15.0 (73.7) 15.9 (50.0) 15.7 (55.3) 16.0 (47.4)
55% Control 13.5 14.5 (76.7) 15.0 (65.1) 15.0 (65.1) 15.5 (53.5)
Major Brand 12.5 14.0 (71.7) 14.7 (58.5) 14.7 (58.5) 14.7 (58.5)
The test data indicates that bimodal polymers can provide good
high-humidity curl retention and can set quickly. Furthermore, due
to the molecular weight of these polymers, formulators can deliver
excellent dispersion patterns and particle size distributions (data not
shown). And finally, the polymers exhibit good aesthetic character-
istics when evaluated on wet and dried hair. This versatility makes
them a reliable alternative to current hair care polymers and for the
next generation of lower VOC hair styling products.
A Conditioning Polymer from Croda

Croda strives to provide quality raw materials with proven efficacy
that help personal care companies create innovative products. With
this goal in mind, five new raw materials for hair care were launched
in the past year. These raw materials are used in numerous types of
hair care applications and provide a range of claims from enhanced
color uptake to cuticle smoothing. All of these materials were
developed in one of Crodas core technology areas: esters, phosphate
esters, proteins and quaternary compounds.

545
Brewster Chapter 51
The polymer: Utilizing years of work in protein chemistry, Croda

has entered the styling polymer market with hydroxypropyltrimo-
nium hydrolyzed maize starchk, a trimethyl quaternized hydrolyzed
maize starch with an average molecular weight of 250,000 d. This
high molecular weight compound is able to provide excellent style
retention properties and has been proven to reduce static flyaway,
provide antifrizz properties from both leave-on and rinse-off prod-
ucts, and retain style even in high humidities (Figure 8).
Figure 8. Curl retention studies show hydroxypropyltrimonium hydrolyzed maize starch is

able to preserve style better even at high RH (from Croda)
Hydroxypropyltrimonium hydrolyzed maize starch (5% inclu-

sion level) helps maintain a controlled sleek look. The tresses in
Figure 9 (see Color Insert21)were treated with a retail product and
a cream form of the Croda polymer. The naturally curly hair then
was exposed to 85% RH for 15 minutes.
Hydroxypropyltrimonium hydrolyzed maize starch was evaluated
at 10% inclusion in a Croda conditioner concentrate to be described
later. This combination showed excellent antifrizz benefits (not
k
MiruStyle MFP (INCI: Hydroxypropyltrimonium hydrolyzed maize starch) is a product of
Croda Inc.

546
presented here) demonstrating that hydroxypropyltrimonium hydro-

lyzed maize starch is effective from a rinse-off system.
Figure 9. The antifrizz effect of hydroxypropyltrimonium hydrolyzed maize starch (left) at

5% versus a commercial conditioner (right) (from Croda)
Other polymers: A second protein launched this year and based

on keratin was designed to moisturize and condition the hair.
This keratin hydrolysatem is extracted from wool keratin fibers. It
contains an unusually high level of cystine (~4%), the highest pro-
portion of which (~65%) is S-sulfo cystine, occurring as a Bunte
salt. This Bunte salt is charged inherently, giving it semireactivity
in oxidative/reductive-type environments. As a result, this kera-
tin hydrolysate is the ideal protein of choice for use in hair color,
bleaching or permanent wave systems, and is suitable for pre- and
post-treatment products.
As the winner of the 2004 Frost and Sullivan Excellence in
Technology award in the field of fatty ester technology, Croda
builds on this distinction with the introduction of an oligo estern
derived from sebacic acid and hydrogenated castor oil. This product
m
Keratec Pep (INCI: Water (aqua) (and) hydrolyzed keratin) is a product of Croda Inc.
n
Crodabond CSA (INCI: Hydrogenated castor oil / sebacic acid copolymer) is a product of
Croda Inc.

547
Brewster Chapter 51
was engineered specifically to seal down hair cuticles that have been
damaged through coloring, bleaching, perming or thermal straight-
ening. It adheres to the lifted cuticles, cementing them together and
smoothing out the hair fiber. Its high refractive index, in combina-
tion with its smoothing action, contributes to shiny, glossy hair,
and its substantivity will maintain this look even through multiple
shampooings. It is recommended for use in deep conditioners, after-
salon treatments or any other product designed for damaged hair.
Crodas work in phosphate ester technology has resulted in a color
enhancer for hair dyes that also functions as an emulsifier in the tint.
This complex mixturep of mono- and di-phosphate esters displays
rheological behavior that slows down the initial oxidation rate in
the emulsion and then promotes faster release of the oil-based dye
active inside the hair. The smaller hair dye and coupler molecules are
able to penetrate and react within the hair cortex, which allows more
color to developed inside the hair fiber. This yields more vibrant
color and better shampoo durability for long-lasting color.
In addition to the functional raw materials that Croda launched
this year, the company also has released a conditioner concentrateq
designed for the salon hair care market. As the superior blend
selected from a scientific screening process of 30 different proto-
types, this concentrate is an optimized blend of conditioning agents,
emulsifiers and stabilizers designed to create an elegant daily con-
ditioner or intensive treatment. It is proven to deliver premium
quality performance by adding only water and fragrance. This
proprietary blend has been evaluated at 9% in a conditioner for wet
comb benefits and tested for salon performance against a premium
salon conditioner, where it performed as well as the commercial
product. This provides a means for a formulator to create a high
performance, salon-tested product with little development time and
expense. As a conditioning base, the conditioner concentrate also
provides for the creation of a range of products by the simple addi-
tion of carefully selected actives. A new dimension in functionality is
provided by each variant.
p
Crodafos HCE (INCI: Oleth-5 phosphate (and) dioleyl phosphate) is a product of Croda Inc.
q
KeraMax+ is a proprietary blend from Croda Inc.

548
A hair-strengthening proteinr from Croda is composed of a

copolymer of hydrolyzed vegetable protein and silicone. It is able
to penetrate the cortex to bind moisture as well as form a protec-
tive film on the hair fiber to lubricate and reinforce the cuticle. It
was evaluated at 1% inclusion in Crodas conditioner concentrateq
by the flexabrasion fatigue lifetime method that evaluates the hairs
resistance to breakage (strength). The addition of the protein to the
conditioner increased the hairs flexabrasion lifetime by 68% over the
conditioner alone and increased the strength of untreated bleached
hair by 125% (data not shown).
An age-defying hair complexs has been derived from smaller
molecular weight peptides and the higher molecular weight inter-
mediate filament protein. Operating through sacrificial degradation
and antioxidant mechanisms, this complex shields the hair from
the aging and damaging effects of the environment (in particular,
UV light and pollution). Evaluating tryptophan degradation as a
marker for damage, the inclusion of 1% of this complex in Crodas
conditioner complexq gave 100% protection of the hair from
tryptophan damage caused by UV irradiation, thus providing an
antiaging claim.
A polyester, polyquaternized UV absorbert has been designed to
protect hair from the suns UV rays. Previous studies demonstrated
that it could preserve hair fiber tensile strength, hydrophobicity,
combing properties and natural color. A conditioner comprised of
9% of Crodas conditioner concentrateq plus 2% of this UV absorber
showed a 99.5% protection of the hairs tryptophan content (data not
shown), implying complete UVB and total hair protein protection.
A hydrolyzed vegetable proteinu capable of penetrating the
hairs cortex brings moisture into the hair shaft. Studies show that
addition of 4% of this protein to the Crodas conditioner complexq
significantly improves its moisture regulating ability, showing a 37%
improvement in the hydration protection index (data not shown).
r
Keravis (INCI: Hydrolyzed vegetable protein BG-propyl silanetriol) is a product of Croda Inc.
s
Keratec IFP (INCI: Water (aqua) (and) keratin (and) hydrolyzed keratin) is a product of
Croda Inc.
t
Crodasorb UV-HPP (INCI: Butylene glycol (and) polyquaternium-59) is a product of Croda Inc.
u
Hydrosolanum (INCI: Hydrolyzed vegetable protein) is a product of Croda Inc.

549
Brewster Chapter 51
A Conditioning Polymer from Dow Corning

Silicones have a long history of use in hair care, where they are rec-
ognized for providing conditioning, shine, manageability, improved
combing and reduced flyaway. These versatile raw materials also offer
heat and color protection, aid detangling, provide body, enhance
straightening, or impart flexible styling properties. Here some novel
properties and traditional conditioning functions of recently intro-
duced silicone materials for hair care applications are reviewed.
Multifunctional silicone emulsions: Efficient formulating can
be aided by silicones delivered in emulsion form, an approach that
facilitates incorporation of potentially incompatible ingredients.
It also allows simple pouring and mixing, as part of cold processes
or with the addition of heat. Several recently introduced silicone
emulsions offer processing advantages along with multifunctional
properties in formulations.
Divinyldimethicone/dimethicone copolymer (and) C12-C13
pareth-3/C12-C13 pareth-23 is an emulsionv of ultra high molecu-
lar weight silicone for use in shampoos, rinse-off and leave-on
conditioners and styling products to meet several objectives. Among
these objectives are increased fragrance intensity, extended fragrance
release and prolonged hair color retention without loss of condition-
ing performance. The material is a 60% nonionic emulsion of very
high viscosity (>120x106 mm2/s at 0.01 Hz) polydimethicone/vinyl
copolymer. It is dispersed easily in water and is suitable for cold
processing. Researchers at Takasago International Corp. showed
that presence of the silicone emulsion in a test shampoo resulted in
greater perceived fragrance intensity of hair during the in-use phases
of lathering, rinsing, blow drying and six hours after blow drying,
when compared to the results of the same formulation without the
silicone emulsion.5
Silicone quaternium-16 (and) undeceth-11 (and) butyloctanol
(and) undeceth-5 microemulsionw performs multiple functions
v
HMW 2220 Nonionic Emulsion (INCI: Divinyldimethicone/dimethicone copolymer (and)
C12-C13 pareth-3/C12-C13 pareth-23) is a product of Dow Corning Corp.
w
Dow Corning 5-7113 Silicone Quat Microemulsion (INCI: Silicone quaternium-16 (and)
undeceth-11 (and) butyloctanol (and) undeceth-5) is a product of Dow Corning Corp.

550
without sacrificing conditioning. The patented quaternary silicone

polymer also has demonstrated protection from heat, improved
permanent color retention, and enhanced body and volume. For still
greater versatility, this silicone quat microemulsion can be used to
create opaque and clear formulations.
An antifrizz silicone emulsion: Silicone quaternium-16/glycidoxy
dimethicone crosspolymer (and) trideceth-12 emulsionx is modi-
fied by amine and elastomer technologies, resulting in an all-in-one
solution for styling aids and fixatives. The effect in formulations is a
soft feel combined with flexible hold.
This multifunctional ingredient protects hair from heat styling
by helping to retain its moisture. It improves wet and dry combing,
protects from heat, aids curl retention, adds shine, controls frizz and
imparts superior aesthetics. The material also can be used in rinse-
off products such as shampoos and conditioners. Its emulsion form
simplifies formulation, particularly because the material is compat-
ible with many other hair care ingredients.
Figure 10 illustrates how silicone quaternium-16/glycidoxy
dimethicone crosspolymer (and) trideceth-12 controls frizz, which is
measured by the expansion of hair over time at 90% relative humid-
ity. The material shows a marked improvement in frizz control over
a silicone gum, cyclic and elastomer blendy and a commercial bench-
mark hair serum.
Multifunctional silicone fluids: In addition to silicone emul-
sions, a number of silicone fluids have multifunctional properties in
hair care formulations. These materials range from polyether- and
amino-based fluids to silicone resins.
PEG/PPG-15/15 dimethiconez is a silicone polyether polymer
that can be incorporated into clear and opaque product forms, where
it imparts ultra shine with light-to-medium conditioning. The result
is improved wet and dry detangling and a smooth feel, without
weighing down the hair. In rinse-off conditioners, the silicone fluid
x
Dow Corning 5-7070 Si Amino Elastomer Emulsion (INCI: Silicone quaternium-16/glycidoxy
dimethicone crosspolymer (and) trideceth-12) is a product of Dow Corning Corp.
y
Dow Corning 2-9027 Styling Aid (INCI: Cyclopentasiloxane (and) dimethiconol (and)
dimethicone crosspolymer) is a product of Dow Corning Corp.
z
Dow Corning 5330 Fluid (INCI: PEG/PPG-15/15 dimethicone) is a product of Dow Corning Corp.

551
Brewster Chapter 51
helps control flyaway hair. The water-soluble material allows easy

formulation for cold and hot processes, without the need for pre-
emulsification, solubilizers or suspending agents.
Figure 10. Silicone quaternium-16/glycidoxy dimethicone crosspolymer (and) trideceth-12

emulsion reduces the hair expansion associated with frizz after 2 h and 90% RH. (from
Dow Corning)
Bis (C13-15 alkoxy) PG amodimethiconeaa is an amino-functional

silicone polymer. It was designed for clear and opaque conditioning
shampoos, semipermanent and permanent colorants, and leave-in
conditioning treatments such as detanglers, cuticle coats, hot oils,
hair masks and mousses. It can be used in anhydrous as well as
water-based systems for superior conditioning, excellent wet and
dry detangling, a smooth feel and color retention. Formulators may
choose cold or hot processing, and the silicone can be added at any
stage. The material requires no solubilizers or suspending agents and
is easy to emulsify.
Aminopropyl phenyl trimethiconebb is a silicone resin that con-
tains both amino- and phenyl-functional groups. Amino-functional
aa
Dow Corning 8500 Conditioning Agent (INCI: Bis (C13-15 alkoxy) PG amodimethicone) is a
product of Dow Corning Corp.
bb
Dow Corning 2-2078 Fluid (INCI: Aminopropyl phenyl trimethicone) is a product of Dow
Corning Corp.

552
silicones are known in the hair care industry for their ability to
improve deposition on negatively charged hair.6 The phenyl group
imparts shine due to its high refractive index, and the liquid nature
of the resin provides good film-forming capabilities to help ensure
efficacy and uniformity once it is delivered onto the hair. Further-
more, because it is able to withstand a high pH environment, the
silicone resin can be incorporated into relaxers and permanent
wave formulations.
Conclusion
Consumer demand for hair care products goes beyond traditional
washing and conditioning. Todays hair care marketplace is a com-
petitive arena of highly differentiated products that offer a range of
functions, including ease of combing, softness and manageability,
easy styling, body and elasticity, and color retention. Fragrance is an
enhanced part of the sensory experience, and consumers increasingly
select products based on scent as well as performance. Multi-
functional materials provide a route to innovative product forms,
allowing formulators to capitalize on efficient product development
and ease of processing.
Acknowledgments
C&T thanks the following companies and authors for contributing to this article: Bernice
Ridley at Ciba Specialty Chemicals plc and Colleen M. Rocafort at Ciba Specialty
Chemicals Corporation Julie Shlepr, with Julie Castner and Dale Willis at Noveon Inc. M.
Creamer, A. Keenan, M. Merlau Johnson, A. Kar, A. Nakatani, D. Routzahn, C. Schwartz, M.
Wang and F. Zeng at Rohm and Haas Company J. Jachowicz, J.C. Chuang, T. Winkler,
R. McMullen, S. Chen and D. Streuli at International Specialty Products Tom Burns at
Interpolymer Corporation Jennifer Lee at Croda Inc. Bethany K. Johnson at Dow Corning
Corporation and Erik Gyzen at Dow Corning Australia.
Bud Brewster, Associate Editor

References
1. International Cosmetic Ingredient Dictionary and Handbook, Washington, DC:
Cosmetic, Toiletry, and Fragrance Association (1997)
2. R McMullen and J Jachowicz, Optical properties of hair Effect of treatments on luster
as quantified by image analysis, J Cosmet Sci 54 335 (2003)

553
Brewster Chapter 51
3. R McMullen and J Jachowicz, Optical Properties of Hair Detailed examination of

specular reflection patterns in various hair types, J Cosmet Sci 55 2947 (2004)
4. J Jachowicz and R McMullen, Mechanical analysis of elasticity and flexibility of virgin
and polymer-treated hair fiber assemblies, J Cosmet Sci 53 345 (2002)
5. A Vagts et al, An emulsion of ultra high molecular weight silicone for enhanced hair care
with fragrance delivery, presented at Personal Care Ingredients Asia (PCIA), Manila,
March 57, 2003
6. CA Hoag, Evaluating silicone emulsions for global hair care applications, GCI 4455
(Apr 1999)

Chapter 52
Hair Care
Formulary
Shampoos 556
Styling Products 564
Conditioners 569
Treatments 573
Supplier Listing 576

556
Directory Hair Care Formulary
Shampoos Volumizing Shampoo

(National Starch)
This shampoo uses polymers to improve hair
Luxurious Sulfate-free Shampoo volume. It gives the hair a conditioned feel during
(Croda Inc.) and after application, with no residual after feel.
This sulfate-free shampoo system is creamy in ap- A. Water (aqua) 24.50%

pearance and enriched with silk and pearls. B. Polyquaternium-4
(Celquat L-200, National Starch) 0.25
A. Sodium lauroyl sarcosinate C. Sodium chloride 2.50
(Crodasinic LS-30, Croda) 30.00% D. Water (aqua) 26.27
Cocamidopropyl hydroxysultaine E. Sodium laureth sulfate
(Crosultaine C-50, Croda) 15.00 (Texapon NSO BX, 28% active, Cognis) 42.90
Polyquaternium-70 (and) diporpylene glycol F. Cocamidopropyl betaine
(Lustreplex, Croda) 1.50 (Tego Betain L7, 30% active, Degussa) 3.34
Glyceryl stearate 2.00 G. DMDM hydantoin (Glydant 2000, Lonza) 0.24
PEG-150 pentaerthrityl tetrastearate (and) H. Citric acid qs
PEG-6 caprylic/capric glycerides (and) 100.00
water (aqua) 5.00
Water (aqua) 45.20 Procedure: Slowly sift B into A and mix until
B. Water (aqua) (and) glycerin (and) pearl dissolved. Add C to D and mix until dissolved. Add
powder (and) maris sal (Crodarom Pearl E to AB and mix until homogeneous. Add F to ABE
Extract, Croda) 0.50
and mix until homogeneous. Add G to ABEF and
Silk amino acids (Crosilk Liquid, Croda) 0.30
mix until homogeneous. Add CD to ABEF and mix
Hydrolyzed silk (Crosilk 10,000, Croda) 0.30
Isopropyl myristate (and) soybean oil until homogeneous. If needed, adjust pH with H.
(and) Carthamus tinctorius (safflower)
seed oil (and) linoleic acid (and)
tocopheryl acetate (and) retinyl palmitate Baby Shampoo (TRI-K Industries)
(Crodarom Vitamin A, E, F OS, Croda) 0.05
A. Water (aqua) 57.95%
Polysorbate 80 (and) water (aqua) (and)
B. Disodium EDTA (Hampene NA2, Akzo Nobel) 0.05
Simmondsia chinensis (jojoba) seed oil
Panthenol (DL-Panthenol, TRI-K) 1.00
(Crodarom Jojoba P20 WS, Croda) 0.05
Water (aqua) decyl glucoside (and)
C. Methylisothiazolinone
cocamidopropyl betaine (and)
(Neolone 950, Rohm and Haas) 0.10
sodium lauroyl lactylate (and)
100.00
sodium cocoyl iesthionate (and)
sodium lauroyl glutamate
Procedure: Combine A in main vessel. Heat to
(Prolutene SF, TRI-K) 30.00
70C. Once solids have dissolved, cool to 40C. Disteareth-75 IPDI
Add B to A with mixing. Add C to batch. Adjust (Dermothix 75, Akzo International) 0.50
pH with 3% citric acid solution. Sodium babassu oil amphoacetate
(VaMasoft Babassu, TRI-K/VaMa) 7.00
Benzyl PCA (and) phenoxyethanol (and)
butylene glycol (Twincide BG, TRI-K/VaMa) 1.00
Aloe barbadensis leaf juice
(Aloe Vera Gel 1X, TRI-K) 0.50
Butylene glycol (and) Chamomilla recutita
(matricaria) flower extract
(German Chamomile Extract-BG, TRI-K) 0.50
C. Citric acid, 10% to pH 6.00
Procedure: Heat A to 6065C. Add B individually

and mix, ensuring uniformity after each addition.
Mix until uniform and cool under the propeller.
After cooling, add C to the batch to adjust the
pH to 6.0.

557
Chapter 52
Wash N Style Shampoo Thickening Shampoo

(Interpolymer) (Ajinomoto USA Inc.)
This lathering shampoo not only cleanses hair, The formulation has excellent conditioning prop-
but also volumizes and texturizes fine, limp hair. erties. Its high viscosity formula is a result of new
The polymers surround and support each strand thickening technology, free of polymer molecule-
to give root-lift, manageability and shine to life- thickening agents.
less hair. This texturizing shampoo formula adds
style-support and texture while leaving hair clean A. Polyquaternium-10 10.40%
and soft. B. Water (aqua) 19.60
C. TEA-cocoyl glutamate
A. Water (aqua) 48.08% (Amisoft CT-12S, 30%, Ajinomoto) 40.00
Disodium EDTA TEA-cocoyl alaninate
(Dissolvine Na2-S, Akzo Nobel) 0.10 (Amilite ACT-12, 30%, Ajinomoto) 6.00
Sodium laureth sulfate (Steol CS-230, Stepan) 16.00 Cocamidopropyl betaine 2.00
Ammonium lauryl sulfate Sodium cocoamphoacetate 2.00
(Stepanol AM, Stepan) 14.00 Glycerin 2.00
Cocamidopropyl betaine Sodium PCA (Ajidew NL-50, 50%, Ajinomoto) 1.00
(Amphosol HCG, Stepan) 8.00 Glyceryl caprate 5.00
Sodium cocoyl taurate PEG-150 distearate 1.00
(Tauranol WS-conc, Finetex) 3.00 Water (aqua) qs to 100.00
Cocamide MEA (Mackamide CMA, McIntyre) 1.00 D. Magnesium chloride 0.60
PEG-150 pentaerythrityl tetrastearate E. Fragrance (parfum) qs
(Crothix, Croda) 0.25 F. Citric acid qs
Glycol stearate 0.50
B. Polyacrylate-15 Procedure: Thoroughly disperse A in B at RT. Add
(Syntran PC 5208, Interpolymer) 6.00 AB to C and heat to 80C. Mix until uniform and
Polyacrylate-21 (and) acrylates/dimethyl- add D to batch. Cool to 50C and add F. Cool to
aminoethyl methacrylate copolymer RT with stirring. Adjust pH to5.3 with F. Stir
(Syntran PC 5100, Interpolymer) 1.50 until homogeneous.
Panthenol (Ritapan DL, RITA) 0.75
C. DMDM hydantoin (and) IPBC
(Liquid Glydant Plus, Lonza) 0.35
Fragrance (parfum) 0.40 Shampoo with Amino Acid-Based
Citric acid 0.07 Surfactant
100.00
(Ajinomoto USA, Inc.)
Procedure: Combine and heat to 75C with mod- A shampoo formulated using a new amino acid-
erate agitation. Stir at 75C until homogeneous. based surfactant that has good foaming proper-
Cool slowly with moderate agitation to avoid ties even in weak acidic pHs and offers superior
aeration to 60C. At 60C, individually add B to conditioning.
main batch with continuous agitation until a ho-
mogeneous mixture is obtained. Cool slowly with A. Polyquaternium-10 0.20%
moderate agitation to avoid aeration to 4045C. B. Water (aqua) 9.80
Individually add C to batch, stirring between each C. Sodium cocoyl alaninate (Amilite ACS-12,
addition until homogeneous. Adjust pH of batch 30%, Ajinomoto) 6.00
Cocamidopropyl betaine, 30% 9.00
between 6.16.5.
Sodium laureth sulfate, 70% 19.30
Cocamide DEA 2.00
Methylparaben qs
Water (aqua) qs to 100.00
D. Fragrance (parfum) qs
E. Citric acid qs
Procedure: Thoroughly disperse A in B at RT. Add

AB to C and heat to 80C. Cool to 50C and add
D. Cool to RT with stirring. Adjust pH to 6.3 with
E. Stir until homogeneous.

558
Clear Conditioning Shampoo Mass Market Shampoo

(Nalco Company) (Zenitech)
This clear conditioning shampoo contains A. Water (aqua) 74.95%
polyquaternium-10 and polyquaternium-7 taking B. PEG-175 diisostearate 0.75
advantage of their synergy. This provides for excel- C. Sodium laureth sulfate (and) disodium
oleamido MEA sulfosuccinate (and)
lent detangling, combability and hair smoothness.
cocamide DEA (and) cocamidopropyl
betaine 11.00
A. Sodium laureth sulfate, 2 mol type as
Sodium laureth sulfate, 28% 10.00
70% active) 14.00%
D. Tetrasodium ethylene diamine
Water (aqua) 56.47
tetraacetate tetrahydrate 0.05
B. Cocamidopropyl betaine, as 30% active) 2.00
Preservative 0.30
Sodium cocoamphoacetate, as 40% active) 1.00
PEG-8 dimethicone (and) PEG-8 ricinoleate
Glyceryl caprylate 1.00
(and) polyquaternium-57
Sodium benzoate 0.40
(Zenicone XQ, Zenitech) 0.30
C. Polyquaternium-10
PEG-10 dimethicone/dimmer dilinoleic acid
(Merquat 10, Nalco Company) 0.40
copolymer (Zenester ME, Zenitech) 0.25
D. Water (aqua) 3.60
E. Polysorbate 20 0.35
E. Polyquaternium-7
(Merquat 550L, Nalco Company) 0.20
F. Citric acid, 20% solution 0.30
F. PEG-12 dimethicone 1.00
G. Sodium chloride 1.00
G. Sodium chloride 1.00
100.00
H. Citric acid qs
Procedure: Heat A to 75C. Add B to A and
Procedure: Mix A and heat to 70C, ensuring all mix until dissolved. Add C and continue mixing
is dissolved. Add B to A, maintain at 70C and until uniform. Remove heat from batch and start
ensure dissolution. Disperse C in D and prepare cooling to 40C. When batch reaches 40C, add
just before addition and do not let sit longer than D in order, with continuous mixing until uniform.
10 min. Add CD to the batch and ensure dissolu- Premix E and add to batch. Mix until uniform. Add
tion. Start cooling the mixture. At 60C, add F. F to batch and mix until uniform; pH: 5.26. Add G
When the mixture cools to 45C, add G and make to desired viscosity.
sure all is dissolved. Adjust the pH to 6.0 with
H. The final viscosity should be 1500, spindle 3,
1200 rpm.

559
Chapter 52
Antidandruff and Antibacterial Amide and Sulfate-free Shampoo

Hair Shampoo (Noveon)
(Ciba Specialty Chemicals) This amide-free and alkyl ether sulfate-free
This traditional formulation is based on zinc formula creates a shampoo with excellent foaming
pyrithione. and cleansing characteristics.
A. Triclosan (Part Irgasan DP 300, Ciba) 0.30% A. Water (aqua) 31.72%

B. Cocamide DEA (Part Comperlan KD, Cognis) 3.00 Disodium laureth sulfosuccinate, 40%
Glycol distearate (Cutina AGS, Cognis) 2.00 (Chemccinate DSLS Surfactant, Noveon) 27.68
PEG-120 methyl glucose Cocamidopropyl betaine, 35%
(Glucamate DOE-120, Amerchol) 1.00 (Chembetaine CGF Surfactant, Noveon) 17.89
Fragrance (parfum) qs Ammonium cocoyl isethionate, 30%
Preservative qs (Jordapon ACI-30 G, BASF) 13.92
Sodium laureth sulfate Lauramine oxide, 30%
(Texapon NSO, Cognis) 35.70 (Chemoxide LO Surfactant, Noveon) 4.83
Cocamidopropyl betaine PEG-30 glyceryl cocoate
(Tego Betain F 50, Degussa) 10.00 (Chemonic LI-63 Emollient, Noveon) 1.00
C. Part water (aqua) qs to 100.00 Polyquaternium-7, Mirapol 550, Rhodia, Inc.) 0.60
D. Part zinc prithione 0.80 B. PEG-120 methyl glucose dioleate
E. Part sodium chloride qs (Glucamate DOE-120 Thickener, Noveon) 1.91
C. Methylchloroisothiazolinone (and)
methylisothiazolinone
Procedure: Dissolve A into B and 30% of C by
(Kathon CG, Rohm and Haas) 0.05
heating up to approx. 40C. Disperse D into ABC.
D. Citric acid 0.40
Add remaining C and adjust the viscosity with E. 100.00
Appearance: white pearlescent; pH value: 5.5;
viscosity (Brookfield DVIII+, LV), 90,000 m.Pas. Procedure: Add A into a suitable vessel and heat
to 70C. Add B to A and mix until dissolved.
Begin cooling batch. Add C after temperature is
below 45C. Adjust pH to 6.06.5 with D and
adjust viscosity with sodium chloride if necessary.

560
Sun Protection Daily Shampoo Mild Conditioning Shampoo

(B&T Srl) (Extracts & Ingredients Ltd.)
This daily shampoo helps prevent color fading due This hydrating formula contains two olive oil-
to exposure to the sun, sea water and sand. This based ingredients for a luxurious feel.
formula restores the hairs barrier to give softness
and silky feeling to the hair. A. Water (aqua) 29.10%
Inositol 0.50
A. Sodium PEG-7 olive oil carboxylate Citric acid 1.00
(Olivem 460, B&T Srl) 4.00% Arginine 1.60
Olive oil PEG-7 esters (Olivem 300, B&T Srl) 1.00 Polyquaternium-16 1.50
Sodium laureth sulfate, 70% B. Magnesium laureth sulfate 12.00
(Texapon N 70, Cognis) 10.00 Disodium laureth sulfosuccinate 13.00
Sodium cocoamphoacetate Sodium lauroyl sarcosinate 8.00
(Dehyton MC, Cognis) 10.00 Zinc coceth sulfate 15.00
Polyquaternium-7 Olivoyl hydrolyzed wheat protein (Olivoil
(Conditioner P7, 3V Sigma) 1.20 Surfactant TA, Extracts & Ingredients) 10.00
Sodium chloride 2.00 C. Potassium olyvoil PCA (Olivoil PCA,
B. Water (aqua) qs to 100.00 Extracts & Ingredients) 5.00
Acrylates copolymer Phenoxyethanol (and) methylparaben (and)
(Carbopol Aqua SF1 Polymer, Noveon) 3.00 butylparaben (and) ethylparaben (and)
C. Olea europaea (olive) leaf extract propylparaben (and) isobutylparaben 0.80
(Eurol BT, B&T Srl) 0.10 PEG-120 methyl glucose dioleate 1.00
Butylene glycol (and) tocopherol (and) Fragrance (parfum) qs
tocotrienol (and) oryzanol
(Hidrahair O2, Chemyunion) 1.00 Procedure: In the main mixer, add A in order,
2-Bromo-2-nitropropane-1,3-diol (and) mixing after each addition until completely
methyldibromo glutaronitrile (and) dissolved. Stop mixing and make vacuum. Add B
dipropylene glycol (Euxyl K446, to A; keep vacuum. After the final addition, mix
Schlke & Mayr) 0.20 for around 15 min. Add, still under vacuum and
D. Cocamidopropyl betaine (and) glycol
in order, C; mixing after each addition until homo-
distearate (and) cocamide MEA (and)
geneous. Note: Avoid foam forming excessively
cocamide DEA (Tego Pearl B-48, Degussa) 4.00
Fragrance (parfum) qs during the preparation phase.
E. Citric acid, 30% qs
Procedure: Mix A and B separately under gentle

stirring. Slowly add B to A always under gentle
stirring. Add C always under gentle stirring.
Finally, add D under gentle stirring. Adjust the pH
with E, if necessary.

561
Chapter 52
Gentle Shampoo Clear Mild Shampoo

(Extracts & Ingredients Ltd.) (Stepan Company)
The presence of the fatty acids combined with This mild formulation provides rich, creamy foam
hydrolyzed wheat protein make a shampoo that and conditioning properties.
gives hair softness and manageability.
A. Water (aqua) qs to 100.00%
A. Sodium lauroyl sarcnsinate, 30% 10.00% B. Sodium laureth sulfate
Olivoyl hydrolyzed wheat protein (Steol CS-230, Stepan) 46.60
(Olivoil Surfactant, Extracts & Ingredients) 13.00 Sodium lauroyl lactylate
Lauryl glucoside, 50% 5.00 (Stepan SLL-FB, Stepan) 3.00
Sodium laureth sulfate, 27% 8.00 Sodium stearoyl lactylate
Cocamidopropyl betaine, 30% 7.00 (Stepan SSL-CB, Stepan) 2.00
Dimethicone copolyol 0.10 C. Hydrolyzed wheat protein 1.00
Water (aqua) qs to 100.00 Panthenol (DL-Panthenol, Roche) 0.50
B. Tea lauryl sulfate, 40% 8.00 D. Preservative qs
Fragrance (parfum) 0.35 Color qs
Polysorbate 20 1.00 Fragrance (parfum) qs
C. Water (aqua) 10.00 E. Citric acid, 50% solution qs
D. PEG-120 methyl glucose dioleate 2.00 Sodium hydroxide, 50% solution qs
E. Sodium chloride 1.50 F. Sodium chloride qs
Preservatives qs
F. Lactic acid qs to pH 66.5 Procedure: Charge vessel with A. Start agitation.
Add B to A. Start heating to 160165F. Mix at
Procedure: Combine A in order and mix until 160165F for 1520 min. Cool the batch to
homogeneous. Combine B and add to A. Heat C 80F. Add C to batch. Mix well. Add D, if desired.
up to 70%. Disperse under stirring. Allow to cool Adjust pH to 5.56.5 with E as necessary. Adjust
down to RT. Add CD to AB. Add E under stirring. viscosity with F.
(The amount of salt can vary in order to reach the
desired viscosity.) Add F to pH 6.06.5.
Conditioning Shampoo
(Stepan Company)
This pearlized shampoo provides cleansing as well
as conditioning to the hair.

Ammonium lauryl sulfate
(Stepanol AM, Stepan) 40.00
Cocamidopropyl betaine
(Amphosol HCA, Stepan) 6.00
Glycerin 3.00
B. Cocamide MEA (Ninol COMF, Stepan) 2.00
Stearamidopropyl dimethylamine
(Stepan SAA, Stepan) 1.50
Glycol distearate (Stepan EGDS, Stepan) 2.00
C. Glutamic acid (L-Glutamic Acid, 99% active,
Aldrich Chemical) qs
D. Panthenol (DL-Panthenol 50 L, Roche) 0.15
Preservative qs
Color qs
Procedure: Combine A and begin mixing. Heat

to 7580C. Add B to A. Mix until dissolved.
Start cooling. At 4550C, add C to adjust pH to
4.85.2. Continue cooling, below 40C. Add D.

562
Shampoo/Conditioner with Pearlized Moisturizing Shampoo

No Buildup (Colonial Chemical)
(Sasol Olefins & Surfactants) A. Water (aqua) 72.65%
B. Xanthan gum (Ticaxan Xanthan Clear Powder,
This adult 2-1 shampoo/conditioner does not
TIC Gum) 0.50
show any buildup. C. Sodium decylglucosides hydroxypropyl
sulfonate (Suga Nate 100,
A. Sodium laureth sulfate Colonial Chemical) 17.50
(Marlinat 242/70, Sasol) 12.00% Lauryldimonium hydroxypropyl decyl-
Water (aqua) 30.00 glucoside chloride (Suga Quat S-1210,
B. Cocoamidopropyl betaine Colonial Chemical) 2.00
(Ampholyt JB 130 K, Sasol) 6.00 Cocamidopropyl betaine (Cola Teric COAB,
PEG-6 caprylic/capric glycerides Colonial Chemical) 5.00
(Softigen 767, Sasol) 0.20 Fragrance (parfum) 0.25
Sodium laureth sulfate (and) Na2 EDTA 0.10
glycol distearate (and) lauramide MEA Alpha tocopherol 0.50
(Cosmacol P 50, Sasol) 1.50 Meadowfoam oil (and) shea butter extract 1.00
C1213 alkyl lactate (Cosmacol ELI, Sasol) 0.50 Mica (and) titanium dioxide
Tridecyl salicylate (Cosmacol ESI, Sasol) 0.30 (Timeron Transwhite MP-18, Rona) 0.50
Polyquaternium-10 0.15 100.00
Preservative qs
Procedure: Disperse B in A. Mix until B is fully
C. Water (aqua) qs to 100.00
hydrated. Add C to batch and mix until uniform.
Citric acid qs
NaOH qs
D. NaCI qs
Color-boosting Conditioning
Procedure: Combine A and homogenize. Heat to Shampoo
20C. Add B to A in order while stirring. Maintain
temperature. Adjust with C as needed. Add D (Degussa)
while stirring. A. Hydroxypropyl guar hydroxypropyltrimonium
chloride (Jaguar C-162, Rhodia) 0.30%
Water (aqua) 64.85
Dandruff Shampoo B. Water (aqua) qs
Disodium PEG-5 laurylcitrate sulfosuccinate
(Silab) (and) sodium laureth sulfate
(Rewopol SB CS 50 K, Degussa) 8.25
C. Sodium cocoamphoacetate
Sodium laureth sulfate (EMAL 270D, Kao) 30.00
(Rewoteric AM C, Degussa) 20.90
Cocoamidopropyl betaine
Methoxy PEG/PPG-7/3 aminopropyl
(Amonyl 380BA, SEPPIC) 10.00
dimethicone (Abil Soft AF 100, Degussa) 0.50
Decyl glucoside (Oramix NS 10, SEPPIC) 5.00
PEG-200 hydrogenated glyceryl palmate (and)
Divinyl dimethicone/dimethicone copolymer
PEG-7 glyceryl cocoate (Antil 200, Degussa) 2.50
(and) C1213 pareth-3 (and) C1213
PEG-150 distearate
pareth-23 (DC HMW 2220, Dow Corning) 5.50
(Rewopal PEG 6000 DS, Degussa) 0.50
Steareth-21 (Brij 72, Uniqema Americas) 2.10
Pigment (depending on shade) qs
Phenoxyethanol (and) methylparaben (and)
Citric acid, 30% in water 2.20
ethylparaben (and) butylparaben (and)
Preservative qs
propylparaben (and) isobutylparaben
(Phenonip, Clariant) 0.70
NaOH qs pH 5.5
Water (aqua) (and) butylene glycol (and) Procedure: Combine A until fully dissolved. Com-
triethanolamine (and) Punica granatum bine B until melted and dissolved. Heat to approx.
extract (Adandrine, Silab) 4.00 6065C. Add C in order to B. Add BC to A.
Procedure: Combine A with moderate mixing.

Continue homogenizing until the shampoo is
uniform.

563
Chapter 52
Soothing Dandruff Shampoo Light Conditioning Shampoo

(Rohm and Haas Company) (Pilot Chemical Company)
This shampoo soothes the scalp while eliminating This formulation is a shampoo that is mild and
the itching and flaking symptoms associated with has light conditioning characteristics.
dandruff.
A. Water (aqua) qs to 100%
A. Water (aqua) 70.75% Glycerin 5.00
B. Sodium laureth sulfate Polyquaternium-10 (Mirapol PQ-10, Rhodia) 0.50
(Steol CS-3-70S, Stepan) 10.00 Sodium laureth sulfate
C. Cocamidopropyl betaine (Calfoam ES-302, Pilot) 20.00
(Empigen BS/FA, Huntsman) 8.50 Cocamidopropyl betaine
Acrylates/vinyl neodecanoate crosspolymer (Caltaine C-35, Pilot) 10.00
(Aculyn 38, Rohm and Haas) 7.50 Disodium laureth sulfosuccinate
D. Aminomethyl propanol (AMP 95, Angus) 0.50 (Calinate LE, Pilot) 20.00
E. Phenoxyethanol (and) methylparaben (and) PEG-7 glyceryl cocoate (Glycerox, Croda) 2.00
propylparaben (and) methylisothiazolinone Sodium chloride 2.50
(Neolone MxP, Rohm and Haas) 0.30 Preservative qs
Zinc pyrithione (Zinc Omadine Slurry, Arch) 2.00 Fragrance (parfum) qs
Fragrance (parfum) 0.20 Dye qs
F. Citric acid ~ 0.25 Citric acid qs to pH 5.5
100.00
Procedure: Combine A in order with constant mix-
Procedure: Disperse B in A. Add C in order. ing. Mix well after each addition until the batch
Neutralize mixture D to pH of 6.5. Add B to batch. is uniform, smooth, homogenous and free of any
Reduce the pH to between 5.56.0 with F. Mix lumps or particles.
slowly so as not to trap air into the formulation.
Triple Protein Shampoo

(Pilot Chemical Company)
This protein shampoo has noticeable performance.

B. Sodium laureth sulfate
(Calfoam ES-302, Pilot) 20.00
Sodium lauryl sulfate
(Calfoam SLS-30, Pilot) 20.00
Cocamidopropyl betaine
(Caltaine C-35, Pilot) 10.00
Cocamide MEA (Calamide MC, Pilot) 2.00
Hydrolyzed wheat protein 1.00
Hydrolyzed soy protein 1.00
Hydrolyzed vegetable protein 1.00
C. Preservative qs
Dye qs
Procedure: Heat A to 70C and maintain its

temperature. Add B to A in order with appropri-
ate mixing. Mix well after each addition until the
batch is smooth, homogenous and free of lumps
or particles. Cool to 35C. Add C to batch. Con-
tinue mixing and cooling to RT. Mix well to ensure
a clear, smooth and homogenous batch. Let the
batch stand until the air is out.

564
Styling Products Sculpting and Smoothing Fiber

Crme
(Interpolymer)
Pomade for Blondes This sculpting and smoothing cream contains
(Rona/EMD Chemicals) nylon fibers and can be applied to wet or dry
hair. The crme provides firm yet flexible hold and
This paste, designed especially for blondes, offers
shapes hair for sleep-straight look or natural look-
a smooth, nongreasy feel and adds a bright,
ing curls/waves. The formulation restores moisture
clean, golden appearance to the hair.
and natural oils to dry hair. It also creates a
A. Cera alba (beeswax) 6.50% glossy finish and smoothes away frizz.
Euphorbia cerifera (candelilla) wax 3.00
Butyrospermum parkii (shea butter) fruit 24.00 A. Water (aqua) 69.45%
Polyglyceryl-3-diisostearate Propylene glycol, 99% 5.00
(Emerest 2453, Cognis) 19.25 B. Polyacrylate-18 (and) polyacrylate-19
Octyldodecanol 16.15 (Syntran PC 5117 8.00
Mangifera indica (mango) seed butter 14.50 C. C1215 alkyl benzoate (Finsolv TN, Finetex) 3.00
Preservative 0.10 Dimethicone (DC 200 Fluid, 20 cst,
B. Zea mays (corn) starch 7.00 Dow Corning) 1.50
Sodium polystyrene sulfonate Dimethicone (DC 200 Fluid, 100 cst,
(Flexan II, National Starch) 1.00 Dow Corning) 1.00
C. Calcium aluminum borosilicate (and) Simmondsia chinensis seed oil
titanium dioxide (and) silica (and) tin oxide (Jojoba Oil, Desert Whale) 3.00
Ronastar Gold Cosmetic Pigment, Rona) 7.00 Sorbitan monoleate
Mica (and) titanium dioxide (and) silica (and) (Protachem SMO, Protameen) 0.20
iron oxides (and) tin oxide (Colorona Ethylhexyl methoxycinnamate
Precious Gold Cosmetic Pigment, Rona) 1.50 (Escalol 557, ISP) 1.00
100.00 Cetearyl alcohol (and) ceteareth-20
(Procol CS-20D, Protameen) 2.00
Procedure: Combine A. Heat to 8085C with Stearyl alcohol 0.75
Cetyl alcohol 0.75
mixing. The mixture should be smooth and
Isodecyl neopentanoate (Ceraphyl SLK, ISP) 2.00
uniform. Blend in B and C with mixing. Continue D. Sodium polyacrylate (and) hydrogenated
until the blend is smooth and homogeneous. polydecene (and) trideceth-6
(Rapithix A-60, ISP) 1.50
E. DMDM hydantoin (and) IPBC
(Germall Plus Liquid, ISP) 0.70
Nylon-6 (and) silica (Fiberlon Y10, LCW) 0.03
100.00
Procedure: Add A to vessel and begin heating

to 75C. Add B to A. Stir until batch is homoge-
neous. When batch is at 75C, add C, in order, to
batch. Stir between each addition until homoge-
neous emulsion results. Cool batch to 55C and
add D. Batch will thicken. Stir until homogeneous
and smooth. Cool batch to 45C and add E to
batch. Stir and cool batch to RT. Adjust pH to
6.87.0.

565
Chapter 52
Volumizing Gel Mango-enriched Styling Wax

(National Starch Personal Care) (Dow Corning Corp.)
This alcohol-free cationic hair gel provides lift This is a moisturizing styling wax enriched with
and volume. It provides excellent hold, dry comb, mango butter and specialty silicones.
and feel. The formulation incorporates a cationic
compatible rheology modifier that thickens the A. Water (aqua) 58.45%
system and gives additional hold and humidity Glycerin 5.00
PVP/VA copolymer (Luviskol VA-64E, BASF) 10.00
resistance.
B. Sodium polyacrylate (and) dimethicone
(and) cyclopentasiloxane (and) trideceth-6
(and) PEG/PPG-18/18 dimethicone (DC
B. Polyquaternium-4
RM 2051 Thickening Agent, Dow Corning) 4.00
(Celquat H-100, National Starch) 1.00
C. Cera alba (beeswax) 3.00
C. Acrylates/aminoacrylates/C1030 alkyl
Petrolatum 5.00
PEG-20 itaconate copolymer
Cetyl alcohol 3.00
(Structure Plus, 20%, National Starch) 12.50
C3045 alkyl methicone (and) C3045 olefin
PEG-12 dimethicone (DC-193, Dow Corning) 0.10
(DC AMS-C30 Cosmetic Wax, Dow Corning) 2.00
Cetrimonium chloride
Dimethicone (DC 225 Fluid, Dow Corning) 2.00
(Arquad 1629, 29%, Akzo Nobel) 0.86
Phenyl trimethicone
(DC 556 Fluid, Dow Corning) 2.00
butylparaben (and) ethylparaben (and)
Manifera indica (mango) seed butter
propylparaben (Phenonip, Clariant) 0.37
(DC HY-4001 Mango Butter, Dow Corning) 3.00
D. Glypure high purity glycolic acid, 70%
Caprylic/capric triglyceride
(Glycolic Acid, Dupont) 0.63
(Myritol 318, Henkel KGaA) 2.00
100.00
D. Propylene glycol (and) diazolidinyl urea (and)
iodopropynyl butylcarbamate
Procedure: Charge beaker with A and begin mix-
(Liquid Germall Plus, ISP Sutton) 0.45
ing in an overhead mixer. Slowly sift B into A. Mix Fragrance (parfum) 0.10
until homogeneous. Add C to AB. Mix well. Slowly 100.00
add D to batch. Mix well until solution becomes
clear and viscous. Procedure: Combine A with mixing. Heat to 80C.
Add B to A. The mixture will quickly become very
viscous. Mix using sufficient agitation to obtain
Shine Spray a homogeneous mixture. In a separate vessel,
combine C and heat to 80C with gentle mixing
(Presperse Inc.)
until all wax is melted and mixture is uniform.
A. C1214 isoparaffin (and) C1821 alkane Add C to AB for about 3 min, while stirring at less
(Permethyl 296C, Presperse) 86.90% than 1500 rpm. Reduce mixer speed to 500 rpm
Octyldodecyl stearoyl stearate
and keep stirring as the batch cools to RT. Add D
(Jeechem OSS, Jeen) 8.00
to batch.
Phenyl trimethicone (SF-1550, GE Silicones) 5.00
Tocopheryl acetate (Vitamin E Acetate, BASF) 0.10
100.00
Procedure: Combine A at RT with propeller mix-

ing. Mix until clear and uniform.

566
Natural Hold Pomade Lanolin-free Hair Molding Crme

(TRI-K Industries) (Lipo Chemicals)
This combing cream formula includes polyure- This lanolin-free, smooth, thick cream provides
thane-14 (and) acrylates copolymer for long- a pliable hold when applied to towel-dried hair.
lasting curl definition and frizz control. The cream provides thickening and hair styling
properties.
A. Ricinus communis (castor) seed oil (and)
hydrogenated castor oil (and) Copernica A. Water (aqua) 50.30%
cerifera (carnauba) wax Phenoxyethanol (and) methylparaben (and)
(Vegelyna R25, G. Balestrini/TRI-K) 30.00% ethylparaben (and) butylparaben (and)
Butyrospermum parkii (shea butter) propylparaben (and) isobutylparaben
(Tomasa Shea Butter, TRI-K) 20.00 (Liposerve PP, Lipo) 0.30
Olea europaea (olive) oil unsaponifiables Propylene glycol 1.50
(Cerafruit OL, G. Balestrini/TRI-K) 20.00 Tetrasodium EDTA
Hydrogenated hemp seed oil (Versene 220, Dow Chemical) 0.10
(TRI-K Hemp Wax, TRI-K) 20.00 B. Acrylates/C1030 alkyl acrylate crosspolymer
Theobroma cacao (cocoa) seed butter (PemulenTR-1, Noveon) 0.25
(Tomasa Cocoa Butter, TRI-K) 10.00 C. bis-Behenyl/isostearyl/phytosteryl dimmer
100.00 dilinoleyl dimmer dilinoleate
(Plandool G, Nippon) 10.00
Procedure: Combine A and heat slowly while mix- Synthetic beeswax (Lipobee 102, Lipo) 15.00
ing until all are melted (~75C). Start cooling the Cetearyl alcohol (Lipocol SC, Lipo) 2.50
batch. Continue mixing as long as the mixture is Tribehenin (Lipovol GTB, Lipo) 1.50
in liquid state and then let it solidify. Tridecyl stearate (Liponate TDS, Lipo) 1.00
PEG-4 diheptanoate (Liponate 2-DH, Lipo) 1.00
Tridecyl trimellitate (Liponate TDTM, Lipo) 1.00
Ceteareth-20 (Lipocol SC-20, Lipo) 1.00
Styling Gel PEG-8 stearate (Lipopeg 4-S, Lipo) 1.00
(Lipo Chemicals) PEG-40 hydrogenated castor oil
(Lipocol HCO-40, Lipo) 1.00
A lightweight gel that eliminates a heavy, stiff D. Triethanolamine (TEA, 99%, Ruger) 0.50
feeling to hair. The gel provides a stronghold, yet E. PVP (PVP K-90, ISP) 2.00
allows for a flexible style. SD alcohol 40/B 10.00
F. FD&C Yellow No. 5, 1% sol 0.05
A. Water (aqua) 45.20% 100.00
Hydroxypropyl guar (Jaguar HP-60, Rhodia) 1.00
B. Glycerin (and) diglycol/CHDM/isophthales/ Procedure: Mix A at 7580C with medium speed
SIP copolymer (and) water (aqua) (Lipo propeller stirring. Add B to main batch. Use me-
PE Base G-55, Lipo) 40.00 dium to high speed stirring until fully dissolved.
C. AD alcohol 40B-190 12.50 Premix C and heat to 75C. Add C slowly to main
D. Water (aqua) 1.00 batch at medium speed. Add D to batch and allow
Imidazolidinyl urea (Liposerve TM IU, Lipo) 0.30
to cool. Premix E until ingredients have dissolved.
100.00
Add E to main batch when batch has cooled to
60C. Add F to batch.
Procedure: In the main kettle, slowly combine
A while mixing with propeller mixer at medium
speed. Mix until clear and uniform. Add B to A
with propeller mixing. Add C and premixed D to
batch and mix well.

567
Chapter 52
Superhold Sculpting Taffy Hair Styler

(Noveon) (Rohm and Haas Company)
Cut loose and style wild with this blue, stretchy, This is a two-in-one conditioner styling cream
taffy-like glue. With 5% polymer solids, this with UV absorbers for color protection.
formula gives shaping power, super stiff hold and
humidity resistance. The addition of PEG-90M A. Isoceteth-20 (Arlasolve 200, Uniqema
makes this formula extra stretchy and stringy. Americas) 10.00%
Oleth-2 (Brij 93, Uniqema Americas) 3.00
A self-wetting polymer provides thickening and
Mineral oil (Drakeol 7LT, Penreco) 8.00
stability in this hair gel.
B. Propylene glycol 5.00
Carbomer (Carbopol 940, 2% soln, Noveon) 10.00
Sorbitol (Sorbitol Soln 70%, Lipo) 7.00
B. Acrylates/C 10-30 alkyl acrylate crosspolymer
Water (aqua) 46.00
(Carbopol Ultrez 21 Polymer, Noveon) 0.30
Acrylamide/sodium acryloyldimethyltaurate/
C. Aminomethyl propanol, 95%
acrylic acid copolymer (Acudyne SCP,
(AMP-Ultra PC 2000, Dow/Angus) 0.15
Rohm and Haas) 0.50
D. Polyacrylate-2 crosspolymer, 30%
Aminomethyl propanol (AMP 95, Angus) 0.50
(Fixate Superhold Polymer, Noveon) 16.67
C. Acrylates/steareth-20 methacrylate
E. Diisostearyl fumarate
crosspolymer (Aculyn 88, Rohm and Haas) 5.00
(Schercemol DISF, Noveon) 1.00
D. Silk amino acids (Crosilk, Croda) 0.20
Ethanol 3.00
Cinnamidopropyltrimonium chloride
FD&C Blue No. 1, 0.10% 0.10
(Incroquat UV283, Croda) 0.10
DMDM hydantoin (and) iodopropynyl butylcar-
E. Capryl glycol (and) methylisothiazolinone
bamate (Glydant Plus Liquid, Lonza) 0.30
(Neolone CapG, Rohm and Haas) 1.10
F. Aminomethyl propanol 95%
Fragrance (parfum) (Blossom Crema,
(AMP-Ultra PC 2000, Dow/Angus) 1.72
Custom Essence) 0.10
G. PEG-90M (Polyox WSR-301, Dow/Amerchol) 0.70
100.00
Propylene glycol 5.00
H. Water (aqua) 20.00
Procedure: Combine A and heat to 80C. In a
100.00
separate vessel, combine B and heat to 80C. Add
Procedure: Add A into a vessel large enough to C to B and stir well to combine. Add A to BC. Stir
provide adequate mixing while preparing batch. for approximately 10 min. Add D to batch. Allow
Side sweep agitation is recommended. Sprinkle to cool to 40C. Add E and stir to combine.
B onto the surface of A. Allow B to fully wet for
approximately 5 min. Mix for 10 min. Partially
neutralize for dispersion with C. Mix until uni-
form. Slowly add D to the mixing vessel. Mix for
approximately 5 min or until uniform. Slowly add
E in order to batch. Mix well after each addition.
Slowly add F to neutralize the batch. Allow the
product to mix for approximately 5 min or until
uniform. Scrape sides of the vessel to incorporate
all ingredients into the gel, assuring homogeneity.
Premix G in a separate vessel with good mixing.
Mix until uniform. Add H to G and continue mix-
ing. Add GH to main vessel. Increase agitation.
Note: This mixture is very stringy and sticky. If
necessary, adjust final pH to 6.87.2 with F.

568
Hair Styling Cream All-Day Hold Clear Tub Gel

(MMP Inc.) (International Specialty Products)
This is a light cream that gives a silky and shiny This cost-effective, clear styling gel demonstrates
appearance to the hair, gives hair flexible hold, the dual functionality of both styling benefits
sets any style and acts as an anti-itching agent. and rheology modification (thickening plus yield
value).
Carbomer (Carbopol Ultrez 10, Noveon) 0.70 A. Water (aqua) 95.855%
B. Polyglycerin-3 (Polycast 3, MMP) 3.00 B. Disodium EDTA (Versene Na2, Dow Chemical) 0.100
Triethanolamine, 99% 0.70 Aminomethyl propanol (AMP-95,
C. Water (aqua) 20.00 Dow Chemical) 0.040
PVP K-30 powder 4.00 Glycerin (and) glyceryl acrylate/acrylic acid
D. Oxidized corn oil (Ulline 46, MMP) 2.00 copolymer (Lubrajel NP, ISP) 1.000
Petrolatum (Sofmetic LMP, MMP) 10.00 Butylated PVP (Ganex P904 LC, ISP) 0.250
Beta-Sitosterol (and) sucrose stearate (and) Oleth-10 (Brij 97, Uniqema) 0.075
sucrose distearate (and) cetyl alcohol (and) Acrylic acid/VP crosspolymer
stearyl alcohol (Crystalcast MM, MMP) 3.00 (Ultra Thix P-100, ISP) 1.500
Sucrose tetrastearate triacetate Propylene glycol (and) diazolidinyl urea (and)
(Sisterna A10E-C, MMP/Sisterna) 2.00 iodopropynyl butylcarbamate
E. Isododecane (and) isononyl isononanoate (Liquid Germall Plus, ISP) 0.500
(Clearcast 550, MMP) 4.00 Aminomethyl propanol
F. Water (aqua) (and) Citrus madurensis fruit (AMP-95, Dow Chemical) 0.680
juice (and) polyglycerin (Kalamans PLG-4 100.000
Ext., MMP) 1.00
Preservative 0.30 Procedure: Add A to the main vessel and begin
Fragrance (parfum) 0.30 mixing. Add B in order, ensuring each is dissolved
100.00
before adding the next.
Procedure: Combine A for 15 min until free from
lumps. Add B to A. Mix for 15 min. In a separate
vessel, combine E. Mix until clear. Add C to batch.
Heat to 7580C. In a separate vessel, combine
D. Heat to 7580C. When both ABC and D are at
7580C, combine. Mix for 15 min. Homogenize
for one pass. Start to cool down to 55C. Add E
individually. Start to cool down to 45C and add F.

569
Chapter 52
Conditioners Sebo-regulating Conditioner for

Damaged Hair
(MMP Inc.)
Anti-frizz Hair Gel This formulation gently conditions the hair while
(International Specialty Products) neutralizing the excess sebum. It provides relief
from flaking and leaves the hair feeling soft and
This ultra hold hair gel provides a durable hold
silky.
even at high humidity; conditions while delivering
anti-frizz effects and adding to shine. A. Water (aqua) 82.48%
Disodium EDTA 0.10
B. Polyglycerin-3 (Polycast 3, MMP) 3.00
B. Glycerin 3.00
Scleroglucan (Clearogel CS 11D, MMP) 0.20
C. Acrylates/C1030 alkyl acrylates crosspolymer
C. Water (aqua) (and) montmorillonite (and)
(Carbopol Ultrez 21, Noveon) 0.35
cetyl alcohol (and) glycerin (and)
D. Aminomethyl propanol
pentylene glycol (and) sucrose stearate
(AMP-95, Dow Chemical) 0.30
(and) scleroglucan (Matte Lite
E. Water (aqua) 6.60
Concentrate 269, MMP) 10.00
Polyquaternium-69 (AquaStyle 300, ISP) 13.40
Polyquaternium-46 0.10
F. Water (aqua) 5.00
Cholesterol (and) potassium sulfate
Disodium EDTA (Versene Na2, Dow Chemical) 0.05
(Potassium Cholesterol Sulfate, MMP) 0.10
G. PEG-40 hydrogenated castor oil
D. Oxidized corn oil (Ulline 46, MMP) 0.50
(Cremaphor RH-40, BASF) 0.50
E. Isododecane (and) isononyl isononanoate
H. Propylene glycol (and) diazolidinyl urea (and)
(Clearocast 550, MMP) 3.00
iodopropynyl butylcarbamate (Liquid
Sclareolide
Germall Plus, ISP) 0.50
(Clary Sage Fermented Extract, MMP) 0.02
100.00
F. Preservative 0.30
Procedure: Add A to main container and mix with 100.00
moderate sweep agitation. Add B to A and mix
until dissolved. Disperse C into AB and mix until Procedure: In main vessel, combine A. Mix B into
uniform. Add D to batch and mix until clear and slurry. Then add B to main vessel. Start to heat
uniform. Slow agitation when solution gets thick up to 80C. Add C to batch. Maintain temperature
so as to not entrap air. Premix E and mix until to 80C and homogenize for 30 min. Start to cool
uniform. Add E to batch and mix until uniform. to 6065C; add D. Homogenize for 10 min. Start
Combine F and mix until uniform. Add G to F and to cool to 5560C; add E. Start to cool to 45C;
heat gently to about 40C. Mix until uniform. add F.
Add FG to batch and mix until uniform. Add H to
batch and mix until uniform.

570
Shine and Condition Cream Ethnic Nourishing Conditioner

(Dow Corning Corp.) (Gattefoss Corporation)
This formula is a luxurious, leave-in hair cream This conditioner is an intensive care leave-on
for shiny, soft, healthy hair and contains a liquid formula for ethnic hair damaged by aggressive
amino phenyl silicone resin for superior, long- treatment such as straightening and excessive
lasting shine. dyeing.
A. Lauryl PEG/PPF-18/18 methicone A. Propylene glycol dipelargonate

(DC 5200 Formulation Aid, Dow Corning) 3.00% (DPPG, Gattefoss SAS) 1.00%
Aminopropyl phenyl trimethicone Acrylate C130 alkyl acrylate crosspolymer
(DC 2-2078 Fluid, Dow Corning) 2.00 (Pemulen TR-2, Noveon) 0.05
Isopropyl myristate (Stepan IPM, Stepan) 2.50 B. Water (aqua) 49.45
Isopropyl palmitate (Cognis IPP, Cognis) 2.50 Citrus grandis (grapefruit) fruit water
Mineral oil 5.00 (Original Extract Grapefruit, Gattefoss SAS) 2.00
B. Water (aqua) 79.40 Glycerin 10.00
Tetrasodium EDTA Panthenol (D-Panthenol, Roche) 0.20
(Versene 220 Crystals, Dow Chemical) 0.20 C. Cetyl alcohol (and) glyceryl stearate (and)
Propylene glycol ceteth-20 (and) steareth-20
(Propylene Glycol USP, Fisher Chemical) 3.00 (Tefose HC, Gattefoss SAS) 5.00
DMDM hydantoin Paraffinum Liquidum (mineral oil) (Light
(Glydant, Lonza) 0.40 Liquid Paraffin Codex AA B2, Sarcga Aiglon) 12.00
Sodium chloride 2.00 Paraffinum Liquidum (mineral oil) (and) Cera
100.00 microytallina (and) paraffin (White
Petrolatum Jelly P 23 TF, Sarcga Aiglon) 3.00
Procedure: Combine A. In a separate container, Octyldodecyl myristate (MOD, Gattefoss SAS) 1.00
combine B and mix. Add B to A very slowly using Cetearyl alcohol 0.50
a separating funnel, while mixing A very rapidly Jojoba oil (Lipovol J-Clear, Lipo) 1.50
Caprylic/capric triglycerides (Labrafac CC,
in a 1000 mL beaker at 1376 rpm (see A Guide
Gattefoss SAS) 12.00
to Formulating Water-in-Silicone Emulsions, Dow
Corning form no. 25-713-01). Continue mixing for butylparaben (and) ethylparaben (and)
an additional 15 min. propylparaben (Phenonip, Clariant) 0.70
D. Sodium hydroxide, 10% solution 0.10
E. Hydrolyzed soy protein
Conditioner for Damaged Hair (Phylderm Vegetal C, Gattefoss SAS) 0.50
FD&C No. 6 (W 082, 0.5% sol, LCW) 0.50
(Zenitech) Fragrance (parfum)
A. Water (aqua) 89.350% (Taxi Sunrise RS 15014, Technico-Flor) 0.50
Guar hydroxypropyltrimonium chloride 0.400 100.00
Panthenyl hydroxypropyl steardimonium
chloride 0.300 Procedure: Combine A and homogenize. Add A
B. Cetearyl alcohol 4.000 to B and mix for 5 min under rotor stator mixing.
PEG-40 stearate (Jeemate 2000-DPS, Combine C. Heat AB and D separately to 35C.
Jellice Co., Ltd.) 0.250 Add C to AB under rapid mixing (rotor stator
Behentrimonium methosulfate (and) 3,000 rpm). Mix for 10 min and neutralize with
cetearyl alcohol 2.500 D. Mix batch for 2 min, then cool under planetary
Polyquaternium-57 (Zenigloss Q
mixing. At 35C, add E. Complete cooling.
Polyquaternium 57, Zenitech) 3.000
C. Methylchloroisothiazolinone (and)
methylisothiazolinone 0.050
Fragrance (parfum) herbal type 0.150
NaOH, 20% soln qs to pH 4.5
Procedure: Combine A and heat to 75C. Combine

B and heat to 75C. Add B to A. Cool to 45C and
add C.

571
Chapter 52
Ethnic Leave-in Conditioner Cream Rinse Conditioner

(Degussa) (Inolex)
A. Cetyl PEG/PPG-10/1 dimethicone This is a classic conditioner formula for daily use.
(Abil EM 90, Degussa) 2.00% It leaves a light, silky-smooth coating on the
Paraffinum perliquidum (mineral oil) 2.00 hair. It contains no alkylquats, and, therefore,
Petrolatum 2.00
has less buildup and less eye irritation than most
Stearyl dimethicone (Abil Wax 9800, Degussa) 2.00
typical formulas. It is ethoxylate- , paraben- and
Persea gratissima (avocado) oil 2.00
Olea europaea (olive) oil 2.00 formaldehyde-free.
Ethylhexyl palmitate (Tegosoft OP, Degussa) 3.00
Isopropyl palmitate (Tegosoft P, Degussa) 3.00 A. Water (aqua) 88.10%
Buxus chinensis (jojoba) oil 2.00 Disodium EDTA 0.10
Tocopheryl acetate 0.20 Aspartic acid (L-Aspartic acid, Ajinomoto) 0.30
B. Methoxy PEG/PPG-7/3 aminopropyl dimethi- Panthenol (D,L-Panthenol 50W, BASF) 0.10
cone (Abil Soft AF 100, Degussa) 0.50 Brassicamidopropyl dimethylamine
Glycerin 3.00 (ProCondition 22, Inolex) 1.50
NaCl 0.70 B. Stearyl alcohol 4.00
Water (aqua) 75.60 Cetyl alcohol 3.00
Pigment qs Cyclomethicone (DC 245 Fluid, Dow Corning) 2.00
Preservative qs Dimethicone
Fragrance (parfum) qs (DC 200 Fluid, 50 cst, Dow Corning) 0.10
C. Caprylyl glycol (and) hexylene glycol (and)
methylisothiazolinone (and) water (aqua)
Procedure: Combine A and blend. Combine B and
(Spectragard, Inolex) 0.80
blend to RT. Add B to A and homogenize.
100.00
Procedure: Combine A and B separately and heat

Super Conditioner for to 75C with gentle agitation until uniform. Add
Damaged Hair B to A and mix at 75C until uniform. Homog-
enize for 5 min at 3500 rpm. Sweep mix to 40C.
(Colonial Chemical)
Add C to batch. Cool to 30C with sweep mixing.
Tetrasodium EDTA 0.10
Glycerin, 96% 2.50
Guar hydroxypropyl trimonium chloride 0.50
B. Stearyl dimethyl ammonium hydroxypropyl
lauryl polyglucoside (Suga Quat S-1210,
Colonial Chemical) 3.50
Glyceryl stearate 0.50
Behenyl alcohol 2.00
Stearalkonium chloride 1.50
DC 200-100CS 1.00
DC 345 5.00
C. Methylchloroisothiazolinone (and) methyliso-
thiazolinone (Kathon CG, Rohm and Haas) 0.05
D. Fragrance (parfum)
(Fragrance D1083, Carrubba) 0.30
Citric acid, 25% solution 0.14
100.00

B and heat to 75C. Slowly add B to A with agita-
tion. Add C to batch. Cool to 30C and add D.

572
Soothe and Repair Conditioner Leave-on Hair Conditioner

(Inolex) (Presperse)
This is an intensive conditioning treatment to A. C1315 alkane (and) C1220 isoparaffin
help repair and soothe damaged hair. It leaves (Permethyl 222C, Presperse) 25.00%
a light, silky-smooth coating on the hair. It Laureth-23 (Lipocol L-23, Lipo Chemical) 2.00
PEG-7 olivate (Olivem 300, B&T Srl) 5.00
contains no alkylquats, and, therefore, has
Petrolatum 3.00
less buildup and less eye irritation than most
Sorbitan olivate (Olivem 900, B&T Srl) 7.00
typical formulas. It is ethoxylate- , paraben- and Steareth-10 (Lipocol S-10, Lipo Chemical) 2.50
formaldehyde-free with no synthetic oils. Propylparaben 0.15
Stearic acid 0.70
A. Water (aqua) 72.10% B. Water (aqua) 43.65
Disodium EDTA 0.10 Butylene glycol 0.75
Aspartic acid (L-Aspartic acid, Ajinomoto) 0.70 Methylparaben 0.30
Panthenol (D,L-Panthenol 50W, BASF) 0.10 Panthenol
Brassicamidopropyl dimethylamine (DL-Panthenol Powder, TRI-K Industries) 0.25
(ProCondition 22, Inolex) 4.00 C. Triethanolamine, 99% 0.20
Glyceryl caprylate (Lexgard GMCY, Inolex) 1.00 D. Water (aqua) (and) Chondrus crispus
B. Cetearyl alcohol 12.00 (carrageenan) extract
Sweet almond oil (Lipovol ALM, Lipo) 4.00 (Gelalg, Presperse) 3.00
Sunflower oil (Pureco HOS, Abitec) 6.00 Water (aqua) (and) Chondrus crispus
100.00 (carrageenan) extract (Oligogelane,
Presperse) 3.00
Procedure: Combine A and B separately and heat Hydrolyzed rhodophycea extract
to 75C with gentle agitation until uniform. Add (Bio-Extender, Presperse) 3.00
B to A and mix at 75C until uniform. Homog- E. Fragrance (parfum)
enize for 5 min at 3500 rpm. Sweep mix to 40C. (Fragrance CM032502, Mane) 0.50
Cool to 35C with gentle sweep agitation. 100.00

B with mixing and heat to 60C. Add C to B and
mix well. Add BC to A. Mix well until completely
dispersed under propeller mixer. Add D to Batch.
Mix well with every addition. Add E at 45C and
mix well. Cool to RT.

573
Chapter 52
Treatments Expresso Hair Color

(LCW)
A. Preservative 0.30%
UV Hair Shield Laureth-8 (and) cocotrimonium chloride (and)
butoxyethanol (and) PEG-7 glyceryl cocoate
(B&T Srl) (and) quaternium-80 (Solvariane, LCW) 14.00
This formula is a leave-on hair treatment, and re- Semi permanent hair dyes (Covariane, LCW)
stores the hairs barrier and prevents sun damage according to shade
Erythorbic acid (Covastyle AEB, LCW) 0.10
and color fading. It does not create buildup.
PEG-8 10.00
PEG-12 dimethicone 5.00
A. Ceteareth-6 olivate (Olivem 800, B&T Srl) 2.00%
B. Sodium polyacrylate (Covacryl MV60, LCW) 5.00
Olive oil PEG-7 esters (Olivem 300, B&T Srl) 1.00
Xanthan gum (and) hectorite (and) cellulose
Dimethicone (DC Fluid 200/350, Dow Corning) 1.00
(Thickagent LC, LCW) 0.80
Cyclomethicone (Mirasil CM, Rhodia) 6.00
Methylmethacrylate crosspolymer
Ethylhexyl salicylate (Eusolex OS, Merck) 2.00
(Covabead LH 85, LCW) 28.00
Benzophenone-3 (Uvasorb MET/C, 3V Sigma) 0.50
Mica (Submica M, LCW) 6.00
Simmondia chinensis (jojoba) seed oil
Zea mays (corn) starch
(Jojoba Seed Oil, B&T Srl) 0.50
(Amidon demais MST, LCW) qs to 100.00
Cetyl palmitate (Cutina CP, Cognis) 3.50
100.00
B. Hydroxypropyl starch phosphate
(Structure XL, National Starch) 4.00
C. Water (aqua) qs to 100.00 Procedure: Combine A, dissolving dye entirely
D. Polyquaternium-7 under stirring and gentle heating (max 50C). In
(Conditioner P7, 3V Sigma) 2.00 a coffee miller, weigh B. Pour A into B and stir
Cetrimonium chloride (about 30 sec) until you obtain a homogeneous
(Dehyquart A-OR, Cognis) 1.00 powder.
E. Citric acid, 30% solution qs
butylparaben (and) ethylparaben (and)
Black Shine Hairstick
(Euxyl K300, Schlke & Mayr) 0.80 (LCW)
A. D&C black No. 2 (and) glycerin (and)
Procedure: Combine A and heat to 7580C
disodium cetyl phenyl ether disulfonate
Disperse B into C using a suitable dispersion unit (Noir Covarine W 9793, LCW) 10.00%
(e.g. Ultra Turrax, Silverstone) and warm it up B. Propylene glycol 40.00
to 75C. Add D to BC. Slowly add A to BCD and Sodium stearate 7.00
homogenize for a couple of minutes. Start cooling PEG-12 dimethicone 3.00
down under gentle stirring. At 3035C, add E if Sodium stearyl fumarate (Covafluid FS, LCW) 1.00
necessary. Tetrasodium EDTA (Covastyle ED, LCW) 0.20
Preservative 0.30
Water (aqua) 22.00
C. Gellan gum 0.50
D. Sodium chloride 0.50
E. Quaternium-18 hectorite 1.50
Octyldodecanol 5.00
Hydrogenated polyisobutene (Squatol S, LCW) 2.00
Laureth-8 3.00
F. Acrylates copolymer (Covacryl P12, LCW) 4.00
100.00
Procedure: Disperse A into B under stirring and

heat to 8590C. Add C to batch. Add D to batch.
Maintain temperature to 8690C. In a separate
container, mix E. Add E to batch at about 60C.
Check water loss and readjust, then homogenize.
Add F.

574
Intensive Cream Mask Brilliant Oil Gel

(Sasol Olefins & Surfactants) (Gattefoss Corp.)
A. Cetearyl alcohol (Nafol 1618 H, Sasol) 4.50% This is a quick absorbing leave-on gel formula
bis-Diglyceryl polyacyladipate-2 that nourishes and smoothes hair.
(Softisan 649, Sasol) 4.00
Di-C1213 alkyl malate (Cosmacol EMI, Sasol) 1.00 A. Paraffinum liquidum (mineral oil)
Cetrimonium chloride (Dehyquart A CE, Cognis) 4.00 (Light Liquid Paraffin Codex AAA B3,
Glycerin 3.00 Sarcga Aiglon) 57.60%
Propylene glycol 2.00 Paraffinum liquidum (mineral oil) ethylene/
B. Hydroxypropylmethylcellulose propylene/styrene copolymer (and)
(Methocel E4M Premium, 2% in water, butylene/ethylene/styrene copolymer
Dow Chemical) 30.00 (Versagel M 1600, Penreco) 30.00
Water (aqua) 50.83 B. Octyldodecyl myristate (MOD, Gattefoss SAS) 1.00
C. Citric acid, 10% in water 0.35 Simmondsia chinensis (jojoba) seed oil
Sodium citrate 0.02 (Jojoba Oil, Lipo) 1.50
Preservative qs Ethoxydiglycol oleate
Fragrance (parfum) qs (Softcutol O, Gattefoss SAS) 0.80
Macadamia ternifolia nut oil
Procedure: Combine A and heat to approx. 75C. (Lipovol MAC, Lipo) 0.50
Combine B and heat to approx. 60C. Add A to B Isostearyl isostearate
while stirring. Homogenize for a short time. Cool (Isostearate Isostearyle, Gattefoss SAS) 2.00
while gently stirring to approx. 30C and add C. C. Cl 12150 (Ecarlate Au Gras W3200,
0.05% solution, LCW) 4.80
Polyglyceryl-3 diisostearate
(Plurol Diisostearique, Gattefoss SAS) 2.00
Damaged Hair Treatment Octyldodecyl myristate (and) Capparis spinosa
(Centerchem Inc.) fruit extract (Gatuline Derma-sensitive,
Gattefoss SAS) 0.10
This light emulsion for intensive treatment regen- Citrus aurantium dulcis (orange) fruit water
erates damaged hair by forming a biofilm on the (Original Extract Grapefruit, Gattefoss SAS) 0.10
outer layers of the hair surface. It also exerts a Fragrance (parfum)
soothing and hydrating effect on irritated scalp. (Taxi Sunrise RS 15014, Technico-Flor) 0.50
100.00
A. Steareth-21 (Brij 721, Uniqema) 5.60%
Steareth-2 (Brij 72, Uniqema) 1.20 Procedure: Combine A and mix under homog-
Cetyl alcohol 4.00 enizer and planetary stirring. Combine B. Add B to
Paraffinum liquidum (mineral oil) 5.00 A. In a separate beaker, add C in sequential order
Isopropyl palmitate 5.00 under propeller mixing. Add C to batch under
Dicaprylyl ether (Cetiol V, Henkel) 3.00 planetary mixing. Maintain planetary mixing for
15 min.
Hydrolyzed sericin (Setakol, Pentapharm) 3.00
C. Glycerin 5.00
ethylparaben (and) butylparaben (and)
(Phenonip, Clariant) 0.50
D. Fragrance (parfum)
(Neptune 0/233392, Dragoco) 0.30
100.00

B and heat to 75C. Under stirring, add B to A.
Cool to 50C. Homogenize and cool to 30C. Add
C and D one after the other and stir cold.

575
Chapter 52
Anti-hair Loss Tonic

(Sederma)
This formula fights the follicle aging process to
prevent hair loss
A. Citric acid 0.26%

Trisodic acid 1.20
Potassium sorbate 0.10
Water (aqua) qs to 100
B. Methylparaben 0.20
PPG-5 ceteth 20 (Procetyl AWS, Croda) 2.00
C. Butylene glycol (and) water (aqua) (and)
PPG-26-buteth-26 (and) PEG-40
hydrogenated castor oil (and) apigenin
(and) oleanic acid (and) biotinoyl
tripeptide-1 (Procapil, Sederma) 3.00
D. Polysorbate 20 (Crillet 1, Croda) 1.00
100.00
Procedure: Combine A. Separately melt B. Add

B to A with helix stirring (s = 200). Add C to AB
with helix stirring (s = 200). Mix D and add to
batch with helix stirring (s = 200).
Leave-on
(Sederma)
This formula moisturizes and soothes the scalp.
A. Cetrimonium chloride
(Incroquat CTC 30, Croda) 1.00%
Citric acid 0.22
Trisodic citrate 1.20
Potassium sorbate 0.10
Water (aqua) qs to 100
B. Methylparaben 0.20
PPG-5 ceteth 20 (Procetyl AWS, Croda) 2.00
C. (Hairspa, Sederma) 2.00
D. Polysorbate 20 (Crillet 1, Croda) 1.00
100.00
Procedure: Combine A. Separately combine B

and heat until dissolved. Add B to A. Add C to
AB. Separately combine D. Add D to batch and
homogenize well.

576
Supplier Listing
Ajinomoto USA Inc. International Specialty Products (ISP)
Fort Lee, NJ, USA Wayne, NJ, USA
Tel: 1-201-292-3180 Tel: 1-973-628-4000
Fax: 1-201-346-5638 Fax: 1-973-628-4001
E-mail: specialty_chemicals_cst@ajiusa.com E-mail: info@ispcorp.com
www.ajichem.com www.ispcorp.com
B&T Srl Sensient Cosmetic Technologies/LCW

Milano, Italy Milwaukee, WI, USA
Tel: 39-039-6180447 Tel: 1-800-558-9892
Fax: 39-039-6188946 E-mail: corporate.communications@sensient-tech.com
E-mail: rdlab@btcompany.com www.sensient-tech.com
www.btcompany.com
Lipo Chemicals
Centerchem Inc. Paterson, NJ, USA
Norwalk, CT, USA Tel: 1-973-345-8600
Tel: 1-203-822-9800 Fax: 1-973-345-8365
Fax: 1-203-822-9820 E-mail: a-cappetta@lipochemicals.com
www.centerchem.com www.lipochemicals.com
Cognis Deutschland Lonza

GmbH & Co. KG Basel, Switzerland
Monheim am Rhein, Germany Tel: 41-61-316 -81-11
Tel: 49-2173-4995-412 Fax 41-61-316-91-11
Fax: 49-2173-4995-500 E-mail: info@lonza.com
www.cognis.com www.lonza.com
Croda Inc. MMP Inc.

Edison, NJ, USA South Plainfield, NJ, USA
Tel: 1-732-417-0800 Tel: 1-908-561-4435
Fax: 1-732-417-0804 Fax: 1-908-561-4780
www.crodausa.com E-mail: dwillbergh@mmpinc.com
www.mmpinc.com
EMD Chemicals Inc./Rona Cosmetic Business Unit
Hawthorne, NY, USA Nalco Company
Tel: 1-914-592-4660 Naperville, IL, USA
Fax: 1-914-785-5889 Tel: 1-630-305-1000
E-mail: rona@emdchemicals.com Fax: 1-630-305-2998
www.emdchemicals.com E-mail: personalcare@nalco.com
www.nalco.com/cosmetics
Extracts & Ingredients
Union, NJ, USA Noveon
Tel: 1-908-688-9009 Cleveland, OH, USA
Fax: 1-908-688-9005 Tel: 1-216-447-5000
www.morretec.com Fax: 1-216-447-5740
www.personalcare.noveon.com
Gattefoss Corporation
Paramus, NJ, USA Pilot Chemical Company
Tel: 1-201-265-4800 Cincinnati, OH, USA
Fax: 1-201-265-4853 Tel: 1-513-326-0636
E-mail: info@gattefossecorp.com Fax: 1-513-326-0601
www.gattefosse.com E-mail: rerechtin@pilotchemical.com
www.pilotchemical.com

577
Chapter 52
Presperse Inc.
Somerset, NJ, USA
Tel: 1-732-356-5200
Fax: 1-732-356-3533
www.phoenix-chem.com
RITA Corporation
Crystal Lake, IL, USA
Tel: 1-815-337-2500
Fax: 1-815-337-2522
www.ritacorp.com
Rohm and Haas

Spring House, PA, USA
Tel: 1-215-641-7250
Fax: 1-215-619-1636
E-mail: akeenan@rohmhaas.com
www.rhpersonalcare.com
Rona
Hawthorne, NY, USA
Tel: 1-888-444-7662
Fax: 1-914-785-5804
www.emdchemicals.com
Sasol Olefins & Surfactants

Westwood, NJ, USA
Tel: 1-201-666-9918
Fax: 1-201-666-9623
E-mail: Barbara.pagliocca@us.sasol.com
www.sasol.com
Sederma SAS
Le Perray en Yvelines Cedex, France
Tel: 33-(0)-1-34-84-10-10
Fax: 33-(0)-1-34-84-11-30
E-mail: olga.gracioso@sederma.fr
www.sederma.fr
SEPPIC
Fairfield, NJ, USA
Tel: 1-973-882-5597
Fax: 1-973-882-5178
E-mail: pcseppicinc@airliquide.com
www.seppic.com
SILAB
Brive, France
Tel: 33-555-84-58-40
Fax: 33-555-84-95-64
E-mail: silab@silab.fr
www.silab.fr
Zenitech, LLC
Haskell, NJ, USA
Tel: 1-973-835-7660
E-mail: samples@zenitech.com
www.zenitech.com
Published June 2007 Cosmetics & Toiletries


Hair Care Color Insert 1
Chapter 16. Figure 1. A combinatorial approach to the formulation of liquid products.
Chapter 16. Figure 2. Composition diagrams for GHCSL. The diagrams are color-coded in
accordance with the visual spectrum with blue representing the absence of coacervate
and red indicating the maximum concentration of phase-separated coacervate. Each
diagram was constructed from observations on at least 368 separate compositions and
each composition was duplicated to check accuracy. The molecular weight was identical
for both cationic guars but the degree of cationic substitution is 0.14 in diagram (a) and
0.17 in diagram (b).
Hair_Color Insert.fcx.indd 1 9/15/07 12:54:31 AM

Chapter 16. Figure 3. Composition diagrams showing regions of coacervate formation for
GHCSL for cationic guars having the some change density but different molecular weights.
Chapter 16. Figure 4. Composition diagrams showing regions of birefringent compositions

for GHCSL for cationic guars having the some change density but different molecular
weights. Birefringent compositions are these shown in red.

Chapter 18. Figure 1. Efficacy of shampoos containing coal tar (red) or sodium shale
oil sulfonate (green) in treating dandruff (left), skin redness or erythema (center) and
itching (right) during an 8-week treatment period

Chapter 18. Figure 2. Reduction of average dandruff score in the subgroup of subjects
with itching score of 9 or 10
Chapter 19. Figure 2a. Wax dispersion selection and optical appearance in relation to
particle size
Figure 2b. EGDS fine wax dispersion (2-4 mm)

Chapter 19. Figure 5. AFM hair surface
Chapter 19. Figure 6. AFM hair roughness

Chapter 19. Figure 7. Combability of hair strand
Chapter 19. Figure 8. Hair gloss measurement by goniometrie
Figure 9. Different scanning calorimeter investigation on human hair

Chapter 19. Figure 10. Hair drying protection by GMO
Chapter 21. Figure 2. Three-phase diagram
Chapter 21. Figure 9. Cationic guars impact on foam volume

Chapter 26. Figure 4. Slightly bleached Caucasian hair tresses treated with rinse-off
conditioner containing specified silicones and left to air dry
Chapter 27. Figure 2. Water holding capacity of polyquaternium-64 () in comparison with two
other commonly used hair conditioning ingredients, dimethicone () and polyquaternium-7 ()

Chapter 27. Figure 4. ESCA measurement of phosphorous atoms on hair fiber, showing
phosphorous atoms at 135 eV for polyquaternium-64 coated hair
Chapter 27. Figure 5. Fluorescence microscopic images of damaged hair fiber


Chapter 27. Figure 6. Fluorescence microscopic images of damaged hair cross sections
Chapter 28. Figure 7. Color changes of dyed hair tresses pre-treated once with
Quaternium-91 (center) or untreated (right) and then shampoo washed 15 times,
compared to original tress (left) without treatment or washing

Chapter 31. Figure 4. Curl retention results for the silicone amino elastomer emulsion
(Am-El); other styling polymers including acrylates copolymer (Co-Ac), polyquaternium-55
(PQ-55) and polyvinylpyrrolidone (PVP); and blends of the emulsion with acrylates
copolymer or PVP
Chapter 31. Figure 5. Sensory characteristics of hair tress treated with the amino elastomer
emulsion (Am-El), polyquaternium-55 (PQ-55) and a 1:1 blend of the two materials

Chapter 31. Figure 6. Sensory characteristics of hair tress treated with the amino elastomer
emulsion (Am-El), acrylates copolymer (Co-Ac) and a 1:1 blend of the two materials
Chapter 31. Figure 7. Sensory characteristics of hair tress treated with the amino
elastomer emulsion (Am-El), PVP and a 1:1 blend of the two materials

Chapter 31. Figure 9. Ternary diagram for a system formed by the silicone amino
elastomer, absolute ethanol and water
Chapter 34. Figure 3. High humidity curl retention of polyimide-1/carbomer blends versus
PVP/carbomer over 5 hours at 90% RH and 80F

Chapter 34. Figure 6. Stress-Strain test on a felt substrate treated with polyimide-1 /
carbomer gel versus a PVP/carbomer gel at moderate and high humidity
Chapter 34. Figure 7. Consumer-rated blow drying performance of a polyimide-1 styling gel
(red) versus a commercial PVP styling gel (blue) in a salon evaluation

Chapter 42. Figure 4. Images of dyed hair at different dyeing times

4-1 Dyed hair tresses after 5 min, 4-2 Dyed hair tresses after 10 min

1 2
3 4
5 6
Chapter 42. Figure 8. Color-developing processes of two color mixtures

8-1 2 min (ceteth-D), 8-2 5 min (ceteth-D), 8-3 20 min (ceteth-D)
8-4 2 min (HCE-D), 8-5 5 min (HCE-D), 8-6 20 min (HCE-D)

Chapter 45. Figure 6. AFM image for undamaged hair
Chapter 45. Figure 7. AFM image for UV protected hair
Chapter 45. Figure 8. AFM image for UV unprotected hair

Chapter 48. Figure 1. Light scattered by an object
Chapter 48. Figure 2. RGB scattering images of a face
Chapter 48. Figure 4. Gloss results measured in the T area of the face

Chapter 48. Figure 5. Measurement of hair shine
Chapter 48. Figure 6. Screen shot of Gloss Image; Color coding gloss levels, Matte
foundation Glossy foundation; Red = 50 %; Blue = 0%; Green = 25%

Chapter 51. Figure 5. Dia-Stron durability testing. Curled tress was treated with hair
fixative and compressed 5X in sequence. The work required to compress the curl is
measured. The acrylates/hydroxyesters acrylates copolymer resin-treated tress maintained
its stiffness after the compressions. (from Rohm and Haas)
Chapter 51. Figure 7. Specular and diffuse reflections (left) from untreated and
polyquaternium-69 modified (with 1% aqueous solution) straight, dark brown hair. Light
intensity plot (right) for free-hanging, untreated frizzy hair and the same hair treated
with a 3% lotion based on polyquaternium-69. (from ISP)

Chapter 51. Figure 9. The antifrizz effect of hydroxypropyltrimonium hydrolyzed maize

starch (left) at 5% versus a commercial conditioner (right) (from Croda)

Index
A cuticle, 7375
shaft lipids, 7778
Acne keloidalis, ethnic scalp disorders, 64
simple physical structure, 7273
actives, silicones, 169170
body, silicone quaternary microemulsions, 235239
Adenosine, anti-hair loss agent, 83
Brazil, sales boost, 10
aerosol hair sprays, modern styling technology, 276278
breakage, racial hair variations, 6162
alkylmethylsiloxanes, SPF enhancement, 171174
Allergic contact dermatitis, ethnic scalp disorders, 64
amide shampoos, hair care formulary, 559 C
Aminexil, anti-hair loss agent, 83
care benefits, vegetable esters
anionic/cationic complexes, 211213
effects on hair, 158166
foam testing, 214215
functions in cleansing, 155158
testing methods, 214
categories, hair care growth, 12
anionic organosilicones, 217218
cationic guar
conditioning efficacy, 224228
conditioning and repair performance, 185188
formulations, 228229
hair surface management, 183185
quats with carbomer compatibility, 219220
sensorial benefits, 188193
silicone-quat mole ratios, 220224
cationic polymers, styling mousses, 318321
silicones, 218
Celquat LS-50, 5
anti-frizz hair gels, hair care formulary, 569
Central centrifugal cicatricial alopecia, ethnic scalp
anti-hair loss, agents, 83
disorders, 64, 6667
antiaging hair care, Johnson, Beth
chemical straightening, ethnic hair grooming, 63
benefits, 384385
China, sales boost, 10
research, 383384
Ciba, rheology modifier, 527530
antibacterial shampoos, hair care formulary, 559
cigarette smoke, keratin biopolymers hair protection, 438
antichaotropic salts, cysteine stabilizer, 341346
clear conditioning shampoos, hair care formulary, 558
antidandruff shampoos, hair care formulary, 559
clear emulsions, refractive index matching, 347
Asia Pacific, development trends, 9
deviations, 356359
Asian hair, 4950
physical principle, 347352
market, 5051
skin care products, 352354
properties and physiology, 5154
clear mild shampoos, hair care formulary, 561
protection, 5456
clear shampoos, Silicone Amino Elastomer Emulsion
softness measurement, 5659
formulation, 308
United States, 51
coal tar, antidandruff activity, 137139
Azeleic acid, anti-hair loss agent, 83
color-boosting conditioning shampoos, hair care
formulary, 562
B coloring hair
controlling progressive process, 387388
baby shampoos, hair care formulary, 556
conclusions, 393394
bending rigidity, 57
method, 390392
bimodal polymers, mousses, 321323 theory, 388390
biology (hair), 7172 European Union (EU) regulations
cortex, 7577 history, 503506
Hair_Index.fcx.indd 579 9/15/07 1:09:41 AM

580
Index Hair Care
non-organic and organic coloring, 509 cortex, hair biology, 7577

route to positive list, 506509 curl retention, Silicone Amino Elastomer Emulsion
India, 4647 evaluation, 301
multilayer lamella vesicles, 413414 customers, diverse base, 23
materials, 415
Cutaneous sarcoidosis, ethnic scalp disorders, 64
results, 418430
cuticle, hair biology, 7375
testing methods, 415418
cysteine, stabilizing antichaotropic salts, 341346
polymer advancement
color retention, 407
hair lightening, 408409
thickeners, 397407 D
retaining, silicone quaternary microemulsions, damaged hair, polyquaternium-64, 243245
234235 methods for analysis, 247248
trends, 375378 study results, 248254
desire for longer lasting color, 378379
in vitro studies, 245247
global growth, 382
dandruff
markets, 380381
natural looks, 379 coal tar, 137139
salons, 381382 Proctor & Gamble discoveries, 126
sensory benefits, 379380 shampoos, hair care formulary, 562
colorless products, silicones, 176181 sodium shale oil sulfonate, 140143
combing, Silicone Amino Elastomer Emulsion results of study, 146150
evaluation, 299300 study methods and materials, 143146
delivery systems, silicones
conditioners
colorless products, 176181
cationic guar, 185188
enhancing actives, 169170
components, 197
fragrance synergies in hair care, 174176
formulating, 195199
SPF enhancement with alkylmethylsiloxanes,
hair care formulary, 569572
171174
hair styling polymers, 293295
demographics
Quaternium-91, 257259
Asian-American hair, 51
experiments, 259
testing results, 260268 ethnic hair, 2930
sales growth, 11 density, racial hair variations, 6162
shampoo formulation, 97, 115117 Discoid lupus erythematosus, ethnic scalp disorders, 64
analysis results, 119122 Dissecting cellulitis, ethnic scalp disorders, 64
combinatorial testing of complex Donnan Equilibrium, 124
coacervation, 117118 dryness, racial hair variations, 6162
polymers. See polymers
dyes
spectrometer analysis, 118119
controlling progressive process, 387388
Silicone Amino Elastomer Emulsion formulation, 309
conclusions, 393394
silicone quaternary microemulsions, 235239
method, 390392
technology advancements, 104105 theory, 388390
texture analysis, 517519 European Union (EU) regulations
conditioning shampoos, hair care formulary, 561 history, 503506
copolymers non-organic and organic coloring, 509
route to positive list, 506509
block and graft, 286289
multilayer lamella vesicles, 413414
block from free radical polymerization, 289290
materials, 415
random, 284286 results, 418430
Copper peptides, anti-hair loss agent, 83 testing methods, 415418

581
Hair Care Index
polymer advancement irritating relaxers, 36

color retention, 407 scalp disorders
hair lightening, 408409 black populations, 6368
thickeners, 397407 hair variations, 6162
trends, 375378 hairstyle grooming practices, 6263
desire for longer lasting color, 378379 styling substances, 3132
global growth, 382
UVB damage, 3031
markets, 380381
Warren, Chuck interview, 3941
natural looks, 379
salons, 381382 European Union (EU), regulations
sensory benefits, 379380 history, 503506
non-organic and organic coloring, 509
E route to positive list, 506509

exocuticle, hair cuticle, 74
Eastern Europe, development trends, 9
efficacy, pharmacology effects on dandruff, 142143
emulsions F
designing for relaxer actives, 311312 fatty acids, hair shaft lipids, 7778
emulsifiers, 312313 Finasteride, anti-hair loss agent, 83
ideal base, 315316
Flawless, product extension, 1921
relaxers basics, 313315
flexabrasion, 104105
refractive index matching, 347
foam, natural products, 110111
deviations, 356359
physical principle, 347352 formularies
skin care products, 352354 conditioners, 569572
endocuticle, hair cuticle, 75 shampoos, 556563
environmental pollution, keratin biopolymers hair styling products, 564568
protection, 437441 treatments, 573575
epicuticle, hair cuticle, 7374 formulation
esters, care benefits anionic organosilicones, 228229
effects on hair, 158166 conditioners, 195199
functions in cleansing, 155158 shampoos
ethnic hair conditioners, 97
foam stabilizers, 9697
Asian hair, 4950
marketing, 93
market, 5051
marketing additives, 98
properties and physiology, 5154
opacifiers, 97
protection, 5456
preservatives, 9798
softness measurement, 5659
primary surfactant, 9395
United States, 51
secondary surfactant, 95
consumer spending power, 36
suspending agents, 97
differing demographics, 2930 viscosity builder, 9596
India silicone quaternary microemulsions, 239240
changing consumer behavior, 4445
fragrances
coloring, 4647
geographic considerations, 1517
fostering aspirations, 4748
hair care shift, 4344 product considerations, 1721
market, 4546 shampoo formulation, 98
natural products, 3233 silicone synergies in hair care, 174176
Obukowho, Patrick interview, 35 trends, 4
genetics, 3637 frizz control, Silicone Amino Elastomer Emulsion
geography, 37
evaluation, 305

582
Index Hair Care
G heat protection, silicone quaternary microemulsions,

232234
Garnier Fructis, product extension, 17
gels
modern styling technology, 278279 I
polyimide-1 performance evaluation, 327329 IFF (International Flavors and Fragrances), 15
coefficient of friction, 336337
fragrances
flexibility, toughness, and durability, 333336
geographic considerations, 1517
formulation, 338339
product considerations, 1721
formulation clarity, 331333
trends, 4
gel film clarity, 331
high humidity curl retention, 329330 in vivo testing, gloss evaluation
salon volume and body evaluation, 337338 advantages of gloss management, 500501
water resistance, 329330 experimentation, 497500
polymers, 291292 object visual appearance, 493495
VP/ methacrylamide/vinylimadazole copolymer, operating principle, 495496
361363 India
mechanical properties, 363365 changing consumer behavior, 4445
testing gel or mousse properties, 366371
coloring, 4647
gentle shampoos, hair care formulary, 561
fostering aspirations, 4748
geography, fragrance considerations, 1517
hair care shift, 4344
gloss
market, 4546
hair products, 2627
inner layers, hair cuticle, 75
in vivo testing
innovations
advantages of gloss management, 500501
experimentation, 497500 combining lipids and silicones, 2425
object visual appearance, 493495 filling niches, 2526
operating principle, 495496 product attributes, 2627
growth (hair) product benefits, 2324
demonstration, 8589 repairing, 2728
hair, 8182 science and ceramides, 26
current approaches, 8485 styling, 2728
history of technology, 8284
texturizing, 2728
intermacrofibrillar matrix, hair cortex, 76
H International Flavors and Fragrances (IFF), 15

fragrances
hair geographic considerations, 1517
biology, 7172 product considerations, 1721
cortex, 7577 trends, 4
cuticle, 7375 Irritant contact dermatitis, ethnic scalp disorders, 64
shaft lipids, 7778
simple physical structure, 7273
growth, 8182
current approaches, 8485
JK
demonstration, 8589 jelly hair sprays, Silicone Amino Elastomer Emulsion
history of technology, 8284 formulation, 310
hair dyes, multifunctional, 102104 Johnson, Beth, antiaging hair care
hair loss, potential anti-loss agents, 83 benefits, 384385
hair sprays, modern styling technology, 276278 research, 383384
hard complexes, 211 keratin biopolymers, hair protection, 433437

583
Hair Care Index
environmental pollution, 437441 microfibrils, hair cortex, 76

UV radiation, 442444 mild conditioning shampoos, hair care formulary, 560
Ketaconazole, anti-hair loss agent, 83 minerals, relaxers, 315
Minoxidil, anti-hair loss agent, 83
mousses
L modern styling technology, 278279
lanolin-free hair molding cremes, hair care formulary, polyimide-1 performance evaluation, 327329
566 coefficient of friction, 336337
lather, natural products, 110111 flexibility, toughness, and durability, 333336
formulation, 338339
Latin America, development trends, 9
leave-on hair conditioners, 204 gel film clarity, 331
hair care formulary, 572 high humidity curl retention, 329330
light conditioning shampoos, hair care formulary, 563 salon volume and body evaluation, 337338
lipids water resistance, 329330
combining with silicone, 2425 polymers

bimodal, 321323
hair biology, 7778
cationic, 318321
LOreal authors, 317318
M recent patents, 323326

Silicone Amino Elastomer Emulsion formulation,
macrofibrils, hair cortex, 76 309
mango-enriched styling waxes, hair care formulary, 565 VP/ methacrylamide/vinylimadazole copolymer,
marketing 361363
Asian hair, 5051 mechanical properties, 363365
diverse customer base, 23 testing gel or mousse properties, 366371
feel of hair, 67 multilayer lamella vesicles, dye formulations, 413414
fragrance, 4 materials, 415
growing categories, 12 results, 418430
hair strengthening, 78 testing methods, 415418
India, 4546 mutagenic effects, sodium shale oil sulfonate versus
innovations coal tar, 141
combining lipids and silicones, 2425 myths, ethnic hair
filling niches, 2526 differing demographics, 2930
product attributes, 2627
natural products, 3233
product benefits, 2324
styling substances, 3132
repairing, 2728
science and ceramides, 26 UVB damage, 3031
styling, 2728
texturizing, 2728
natural products, 109110
N
challenges, 112113 natural hold pomades, hair care formulary, 566
defining, 110 natural products
lather and foam, 110111
attracting new customers, 109110
preservatives, 111112
challenges, 112113
performance improvement strategies, 46 defining, 110
relaxers, 314 lather and foam, 110111
shampoo formulations, 93 preservatives, 111112
mass market shampoos, hair care formulary, 558 ethnic hair, 3233
mega brands, trends, 13 hair straightening, 6364

584
Index Hair Care
nices, filling, 2526 flexibility, toughness, and durability, 333336

Niosil, anti-hair loss agent, 83 formulation, 338339
Nourishing Oasis, product extension, 1719 formulation clarity, 331333
Noveon, rheology modifiers, 530535 gel film clarity, 331
Noville Inc., hair care influence on fragrances, 18 high humidity curl retention, 329330
salon volume and body evaluation, 337338
water resistance, 329330
O polyimide-2, 459460
Obukowho, Patrick, ethnic hair maintenance, 35 basics, 460461
genetics, 3637 evaluation, 463474
geography, 37 hair treatment and formulation, 461463
irritating relaxers, 36 UVA and UVB effects on hair, 460
opacifiers, shampoo formulation, 97 polymers
orthocortical cells, hair cortex, 76 conditioning shampoos, 123128
outer B-layers, hair cuticle, 73 clarity improvements, 131132
conferring conditioning benefits, 132134
ozone, keratin biopolymers hair protection, 438440
enhancing conditioning benefits, 128131
surfactant structure, 128
P hair dyes
color retention, 407
packaging hair lightening, 408409
thickeners, 397407
styling innovations, 279280
keratin biopolymers hair protection, 433437
texture analysis, 484485
environmental pollution, 437441
paracotrical cells, hair cortex, 76
UV radiation, 442444
patents, mousses polymers, 323326
mousses
pearlized moisturizing shampoos, hair care formulary, 562 bimodal, 321323
performance cationic, 318321
feel of hair importance, 67 LOreal authors, 317318
recent patents, 323326
improvement strategies, 46
polyimide-2, 459460
permanent waves, cysteine stabilizing antichaotropic
basics, 460461
salts, 341346
evaluation, 463474
petrolatum, relaxers, 315 hair treatment and formulation, 461463
photodegradation, polyimide-2, 459460 UVA and UVB effects on hair, 460
basics, 460461 recent technologies
evaluation, 463474 bimodal styling polymer, 539544
Ciba rheology modifier, 527530
hair treatment and formulation, 461463
Croda conditioning polymer, 544548
UVA and UVB effects on hair, 460
Dow Corning conditioning polymer, 549552
physical associations, silicones Noveon rheology modifier, 530535
colorless products, 176181 polyquaternium-69, 537539
enhancing actives, 169170 Rohm and Haas styling resin, 535537
fragrance synergies in hair care, 174176 styling hair
conditioners, 293295
SPF enhancement with alkylmethylsiloxanes,
gels, 291292
171174
hair fixatives, 283291
physiology, Asian hair, 5154 straightening, 292293
polyelectrolyte solubility, 125 VP/ methacrylamide/vinylimadazole copolymer,
polyimide-1, performance evaluation, 327329 361363
coefficient of friction, 336337 mechanical properties, 363365

585
Hair Care Index
testing gel or mousse properties, 366371 repairing, innovations, 2728

polyquaternium-64, conditioning damaged hair, 243245 rheology modifiers
methods for analysis, 247248 Ciba, 527530
study results, 248254 Noveon, 530535
in vitro studies, 245247
polyquaternium-69, 537539
polysilicone-15, UV radiation, 448449 S
enhancing hair shine, 455457 Saw Palmetto, anti-hair loss agent, 83
hair structure protection, 452455 scalp disorders, ethnic hair
protecting hair combability, 449452 black populations, 6368
pomade for blondes, hair care formulary, 564 hair variations, 6162
preservatives hairstyle grooming practices, 6263
natural products, 111112 sculpting, hair products, 2627
shampoo formulation, 9798 sculpting and smoothing fiber cremes, hair care
primary surfactants, shampoo formulation, 9395 formulary, 564
Procyanidin, anti-hair loss agent, 83 sebo-regulating conditioners, hair care formulary, 569
products Seborrheic dermatitis, ethnic scalp disorders, 6465
attributes, 2627 secondary surfactant, shampoo formulation, 95
fragrance considerations, 1721 sensorial benefits, cationic guar, 188193
properties, Asian hair, 5154 sensory profiles, Silicone Amino Elastomer Emulsion
Proteasome inhibitor, anti-hair loss agent, 83 evaluation, 301304
protections, Asian hair, 5456 shampoos
protofibrils, hair cortex, 76 conditioners, 115117
Pseudofolliculitis barbae, ethnic scalp disorders, 64, 67 analysis results, 119122
combinatorial testing of complex oacervation,
117118
QR polymers. See polymers
spectrometer analysis, 118119
quantum level changes, 101
continued sales strength, 1011
Quaternium-91, 257259
formulation basics
experiments, 259 conditioners, 97
testing results, 260268 foam stabilizers, 9697
rasor bumps, ethnic scalp disorders, 64 fragrance, 98
Reductase, anti-hair loss agent, 83 marketing, 93
marketing additives, 98
refractive index matching
new technologies. See technologies
deviations, 356359 opacifiers, 97
physical principle, 347352 preservatives, 9798
skin care products, 352354 primary surfactant, 9395
regulations, European Union (EU) secondary surfactant, 95
suspending agents, 97
history, 503506
viscosity builder, 9596
non-organic and organic coloring, 509
hair care formulary, 556563
route to positive list, 506509
shapes, racial hair variations, 61
relaxers
shine products, 2627
emulsions design, 311312
shine sprays, hair care formulary, 565
emulsifiers, 312313
ideal base, 315316 Silicone Amino Elastomer Emulsion, 297298
relaxer basics, 313315 easy formulation, 305309
Obukowho, Patrick interview, 36 multifunctional properties evaluation, 299305

586
Index Hair Care
silicone quaternary microemulsions gels, hair care formulary, 566

body, volume, and conditioning, 235239 innovations, 2728
formulations, 239240 low VOC formula strategies, 274276
heat protection, 232234 modern trends, 276279
packaging, 279280
new polymer, 231232
technology history, 271274
next-generation hair products, 240241
mousse polymers
retaining permanent color, 234235 bimodal, 321323
silicones cationic, 318321
anionic organosilicones, 218 LOreal authors, 317318
combining with lipids, 2425 recent patents, 323326
delivery systems via physical associations polymers

colorless products, 176181 conditioners, 293295
enhancing actives, 169170 gels, 291292
fragrance synergies in hair care, 174176 hair fixatives, 283291
SPF enhancement with alkylmethylsiloxanes, straightening hair, 292293
171174 VP/ methacrylamide/vinylimadazole
copolymer, 361363
hair strengthening
assessing hair strength, 202206 product hair care formulary, 564568
mechanisms for hair strengthening, 206208 Silicone Amino Elastomer Emulsion, 297298
new role, 201202 easy formulation, 305309
polysilicone-15, 448449 multifunctional properties evaluation,
enhancing hair shine, 455457 299305
hair structure protection, 452455 styling resins, polyimide-1 performance evaluation,
protecting hair combability, 449452 327329
sodium shale oil sulfonate, antidandruff studies, 140143 coefficient of friction, 336337
results of study, 146150 flexibility, toughness, and durability, 333336
study methods and materials, 143146 formulation, 338339
softness measurements, India, 5659
soothing dandruff shampoos, hair care formulary, 563
gel film clarity, 331
spectrometer analysis, conditioners, 118119
high humidity curl retention, 329330
SPF, enhancement with alkylmethylsiloxanes, 171174
salon volume and body evaluation, 337338
straightening
water resistance, 329330
ethnic hair grooming
sulfate-free shampoos, hair care formulary, 559
chemical, 63
thermal, 6263 sulfur dioxide gases, keratin biopolymers hair protection,
hair products, 2627 440441
polymers, 292293 sun protection daily shampoos, hair care formulary, 560
strengthening superhold sculpting taffy, hair care formulary, 567
consumer desires, 78 supplier listings, 576577
silicones surfactants
assessing hair strength, 202206 anionic/cationic complexes, 211213
mechanisms for hair strengthening, 206208 foam testing, 214215
new role, 201202 testing methods, 214
styling cationic guar, 183185
agents downward trend, 1112 conditioning shampoo polymers, 128
emulsion design for relaxer actives, 311312 relaxers emulsions design, 311312
emulsifiers, 312313 emulsifiers, 312313
ideal base, 315316 ideal base, 315316
relaxer basics, 313315 relaxer basics, 313315
ethnic hair, 3132 structured, 101102

587
Hair Care Index
T U
TAP (Texture Awareness Program), 16 UV radiation, 447448
technologies keratin biopolymers hair protection, 442444
conditioner advancements, 104105 polysilicone-15, 448449
multifunctional hair dye, 102104 enhancing hair shine, 455457
hair structure protection, 452455
old challenges, 99100
protecting hair combability, 449452
parallel material production and testing, 105106
UVB damages, ethnic hair myths, 3031
polymer recent changes
bimodal styling polymer, 539544
Croda conditioning polymer, 544548
Dow Corning conditioning polymer, 549552
V
structured surfactants, 101102 vegetable esters, care benefits
texture analysis effects on hair, 158166
hair fixatives, 480484 functions in cleansing, 155158
packaging, 484485 VOCs (volatile organic compounds)
shampoo extrusion testing, 477480 formula strategies, 274276
using to substantiate care claims history of regulations, 272273
conditioners and conditioning shampoos, 517519 volatile organic compounds (VOCs)
dynamic hair spray analysis, 514517 formula strategies, 274276
equipment, 511514
history of regulations, 272273
hair fixatives, 519525
volume, silicone quaternary microemulsions, 235239
Texture Awareness Program (TAP), 16
volumizing gels, hair care formulary, 565
texturizing innovations, 2728
volumizing shampoos, hair care formulary, 556
The Science of Hair Care, 318
VP/methacrylamide/vinylimadazole copolymer, 361363
thermal protection, Silicone Amino Elastomer
mechanical properties, 363365
Emulsion evaluation, 304305
testing gel or mousse properties, 366371
thermal straightening, ethnic hair grooming, 6263
thickeners, hair dye polymers, 397407
thickening shampoos, hair care formulary, 557 WZ
Tinea capitis, ethnic scalp disorders, 64
Warren, Chuck, ethnic hair, 3941
torsion pendulum, 487
wash n style shampoos, hair care formulary, 557
results, 489491
testing, 488489
Traction alopecia, ethnic scalp disorders, 64, 6566
treatments, hair care formularies, 573575
trends
Asia Pacific, 9
Brazil, 10
China, 10
complacency not option, 1213
conditioners sales growth, 11
Eastern Europe, 9
Latin America, 9
mega brands, 13
shampoo continued sales, 1011
styling agents, 1112
triple protein shampoos, hair care formulary, 563

For Further Reading . . .
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Biotechnology in Cosmetics: Concepts, Tools Physiology of the Skin II
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The Chemistry & Manufacture of Cosmetics Silicones for Personal Care
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Pulling from its most popular articles written by world-renowned
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to create a solid foundation of knowledge about hair care in
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Topics include:
Physiology
Ethnic hair care
Styling
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And more!
This informative collection provides professionals with invaluable

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Hair Care: From Physiology to Formulation

Cosmetics & Toiletries, the international magazine of cosmetic

Hair Care: From Physiology to Formulation

This informative collection of articles covers a variety of topics

This informative collection provides professionals with invaluable

Allured Publishing Corporation

Hair Care Cover07_1_2.indd 1 10/5/07 2:08:27 PM

Hair_Front Matter.fcx.indd 1 9/15/07 12:51:44 AM

Copyright 2008, by Allured Publishing Corporation. All Rights Reserved.

Allured Publishing Corporation

Hair_Front Matter.fcx.indd 2 9/18/07 9:28:06 AM

Part II. Ethnic

PART III. Physiology

Hair_TOC.fcx.indd 1 9/15/07 12:53:29 AM

PART IV. Shampoo

Hair_TOC.fcx.indd 2 9/15/07 12:53:30 AM

PART VI. Styling

PART VII. Color

PART VIII. Sun Protection

Hair_TOC.fcx.indd 3 9/15/07 12:53:30 AM

Chapter 44. Protecting Against UV-Induced Degradation and

PART IX. Testing

Index ......................................................................... 579

Hair_TOC.fcx.indd 4 9/15/07 12:53:30 AM

Hair_Intro.fcx.indd 1 9/15/07 12:53:49 AM

We hope you will find this compilation a thought-provoking

Hair_Intro.fcx.indd 2 9/15/07 12:53:49 AM

Hair Care Rides the Curl

In the sixties, Broadway celebrated the glories of Hair, in Americas

Hair Care Categories Grow

Hair_Chapter 1.fcx.indd 1 9/15/07 12:56:04 AM

Diverse Customer Base

Hair_Chapter 1.fcx.indd 2 9/15/07 12:56:04 AM

provide product where needed. Nioxins Smoothing Reflectives

Hair_Chapter 1.fcx.indd 3 9/15/07 12:56:04 AM

Hair That Smells and Tastes Good

Performance Improvement Strategies

Hair_Chapter 1.fcx.indd 4 9/15/07 12:56:04 AM

Accordingly, we have changed the way we look at technology

Hair_Chapter 1.fcx.indd 5 9/15/07 12:56:04 AM

The Feel Good Factor

Hair_Chapter 1.fcx.indd 6 9/15/07 12:56:04 AM

flow behavior of formulations. The series includes Promidium

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Nancy Jeffries, Contributing Editor

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Happier Days for

Growth of more than 4% in 2004 indicates that manufacturers

Asia Pacific, Eastern Europe and Latin America

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Brazil and China Boost Sales

Shampoo Staying Strong

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Conditioners Captivates Consumers

Styling Agents Lost Their Stick

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Complacency Not an Option

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their hair, there might be greater segmentation and development of

The Fall of the Mega Brand?

Briony Davies, Contributing Editor

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Extending the Hair Care