12-2008

English Edition
International Journal for Applied Science
Personal Care Detergents Specialties

S. Herrwerth, H.H. Wenk, U. Kortenmeier,

B. Grnung,
I. Ulrich-Brehm, M. Quadir

Hydroxypropyl
Methylcellulose:
A Unique Surface Active
Polymer with Outstanding
Versatility for Rinse-Off
Applications
 CO S M ET I C S
ORAL CARE H Y D ROX Y P RO P Y L M ET H Y LC E L LU LO S E

S. Herrwerth*, H.H. Wenk*, U. Kortenmeier*, B. Grnung*, I. Ulrich-Brehm*, M. Quadir**

Hydroxypropyl Methylcellulose:
A Unique Surface Active Polymer with
Outstanding Versatility for Rinse-Off Applications

Keywords: HPMC, polymer, rinse-off applications

Introduction (e.g. for technical, cosmetic, food, and

Abstract pharmaceutical applications), and the
Hydroxypropyl Methylcellulose is a modi- properties of HPMC are determined by
fied natural carbohydrate polymer de- the degree of methyl and hydroxypropyl

G
egenstand derMethylcellu-
vorliegenden

H
ydroxypropyl
rived from cellulose, the most abundant substitution, as well as by its molecular
Arbeit ist dieisEntwicklung
lose (HPMC) a multifunc-
polymer occurring in nature (Fig. 1). Cel- weight. Due to its excellent toxicological
einer
tionalkosmetisch
additive that akzepta-
offers a lulose, a linear polysaccharide composed profile, it is approved for use by the FDA
blen und
broad in ihren
range Bestandteilen
of impressive proper- of 1,4-linked -D-glucopyranose as mono- as a direct (21 CFR 172.74) and an indi-
optimal
ties abgestimmten
addressing multipleO/W-Cre-
needs in saccharide repeat units, is a truly renew- rect food additive, as well as for use as a
me. Hierzuapplications
Rinse-off soll ein neuerevenmulti-
at low able raw material produced by all plants food additive in the EU (E 464).
funktioneller
use levels. TheO/W-Emulgator,
most importantdas and is therefore practically inexhaustible. HPMC is used in many Personal Care
The annual production of cellulosic mat- products throughout the world, display-
PEG/PPG-25/25
properties includeDimethicone zum
its foam boost-
ter from photoinitiated biosynthesis is ing a multitude of functions, and pri-
Einsatz
ing gelangen.
effect, a significantly im- estimated to be approximately 1.3x109 marily due to this abundance of perfor-
proved skin feel and viscosity con- metric tons (1). mance properties HPMC enjoys a grow-
trol in cleansing and conditioning Due to its strong tendency to form crys- ing popularity with experienced formu-
Personal Care formulations. talline regions through hydrogen bond- lators.
HPMC also contributes to increased ing, cellulose itself is an insoluble mate- The main focus of this article is the ap-
rial and has to be modified to render it plication of Hydroxypropyl Methylcellu-
economic efficiency in many sur-
water soluble (2). Most commercially im- lose in Rinse-Off products. A similar pa-
factant based skin cleansing and portant cellulose derivatives are cellu- per with regard to Leave-On applications
shampoo formulations. The incor- lose ethers, which are formed by partial is in preparation.
poration of HPMC reduces the re- or complete derivatization of the hy- The TEGOCEL series (product of Evonik
quired amount of certain ingredi- droxyl groups of cellulose by ether sub- Goldschmidt GmbH, Essen) comprises
ents, such as surfactants, thicken- stituents (3). For HPMC, a mixed cellu- two different viscosity grades of Hy-
lose ether, these substituents are hy- droxypropyl Methylcellulose: TEGOCEL
ers and emollients, without sacri-
droxypropyl and methyl groups, which, HPM 50 and TEGOCEL HPM 4000, the
ficing performance. On the con- in addition to water solubility, impart numbers indicating the achieved viscosi-
trary the performance can even be surface activity to the polymer. A variety ty in mPas measured at 2 % concentra-
superior in some cases. of HPMC types is commercially available tion in water at 20 C.
Compared to the traditional pow-
dered forms of HPMC, the newly
available TEGOCEL fluid versions
set new benchmarks with regard
to fast processability. The ease of
use offered by the fluidized poly-
mer suspensions allows significant
savings, in process time and costs.

Fig. 1 Chemical structure of cellulose and Hydroxypropyl Methylcellulose (HPMC)

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Performance Properties
HPMC is a multifunctional substance
with a unique combination of properties.
Generally the viscosity building proper-
ties of HPMC also in electrolyte rich
systems are dominating its use in cos-
metic formulations. Even though pri-
marily used as a thickener in liquid for-
mulations or as a binder in solid / semi-
solid products this ingredient also pro-
vides a multitude of additional benefits
to Personal Care products. Enhanced
foam quality of surfactant based formu-
las, improved skin feel, optimized stabi-
lization of emulsions and increased sur-
face active properties are just some of
the examples by which skin and hair care
rinse-off formulations can benefit by
adding HPMC in even extremely low
concentrations.
In many skin cleansing and shampoo for-
mulations certain ingredients like sur-
factants, thickeners and emollients, can
be employed in lower amounts without
sacrificing performance by using HPMC.
On the contrary HPMC brings increased
performance benefits to formulations,
while the formulations become more
economical.
easily compensate the cost of HPMC. As
certain surfactants can be irritating to
skin or hair, a reduction in concentration
creates the additional benefit of in-
creased mildness, a feature that is high-
ly desirable for products like shampoos.
The foam enhancing property is espe-
cially advantageous in pump foamer liq-
uids, where the addition of HPMC pro-
vides a dramatic improvement in foam
quality. Today, dispenser foam applica-
tions are very popular in various market
segments such as infant and youth
cleansing products, hand soaps and hair
care styling products, just to name a few.
The addition of only 0.5% TEGOCEL
HPM 50 is sufficient to improve foam
properties tremendously. The generation
A B
of more uniform and smaller bubbles de-
livers a denser, creamier foam with in-
creased stability, leaving a rich and lux-
urious skin feel. At the same time the re-
quired low viscosity of the formulation
for the pump foamer bottle is guaran-
teed because TEGOCEL HPM 50 as a
short chain product leaves the viscosity
almost unchanged.
Fig. 2 and 3 show a comparison of the
foam quality in two formulations that
differ only by the fact that one contains
HPMC: the basic composition (formula
A) of 10 % Disodium PEG-5 Laurylcitrate
Sulfosuccinate / Sodium Laureth Sulfate
(REWOPOL SB CS 50 B) and 8% Sodium
Coco-amphoacetate (REWOTERIC AM C)
was stabilized by the addition of 0.5%

Formulation without HPMC Formulation with 0.5% HPMC

Foam Boosting Effect
Hydroxypropyl Methylcellulose contributes
Fig. 2 Comparison of foam quality on a flat plane
to significantly improved foam charac-
teristics such as creaminess and foam
stability as well as volume. This truly
unique advantage is based on a proper- A B
ty referred to as interfacial gelation.
The inherent surface activity of HPMC
combined with a certain gelling behav-
iour leads to the spontaneous formation
of highly viscous films within the foam,
more precisely between and around the
bubbles. The development of this poly-
mer network occurs even in very dilute
systems because the surface activity of Formulation with 0.5% HPMC
HPMC induces its enrichment near the
gas/liquid interface leading to concen-
trations which are significant for viscos-
ity building. By strengthening the bub-
ble walls and slowing the rate of water
drainage, the foam gets denser and more
stable in cleansing products of all types. Formulation without HPMC
Viscosity and foam properties can be
maintained with lower additions of salt Fig. 3 Comparison of foam quality on an inclined plane
and surfactant (4). These possible savings

3 SOFW-Journal | 134 | 12-2008

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H Y D ROX Y P RO P Y L M ET H Y LC E L LU LO S E

HPMC, resulting in formula B. Both foams
were generated simultaneously with a
finger pump foamer with the pictures
being taken 15 seconds after the foam
was produced.
The optimization of formula B on the
right hand side is clearly evident: The
formula containing HPMC produces a
foam which is much denser and less wa-
tery, resulting in enhanced stability and
creaminess. The adherence to the in-
clined surface is significantly better.
Improvement of Skin Feel
In skin cleansing formulations, the com-
bination of enhanced surface activity
and strengthened film-forming proper-
ties in addition to increased lubricity all
together combine to provide a remark-
able improvement of wet and dry skin
feel. With the incorporation of low con-
centrations of Hydroxypropyl Methyl-
cellulose a more pleasant skin feel can
be achieved, both during and after
washing.
The improvement of the skin feel and
the already mentioned positive impact
on the foam characteristics of HPMC are
demonstrated in a sensory hand wash
test, in which the effect of the incorpo-
ration of 1.2% TEGOCEL fluid HPM
4000 (0.3% HPMC active) in a premium
shower gel is evaluated. TEGOCEL HPM
4000 was used in this experiment be-
cause of its additional rheological effect
in a shower gel formulation. The for-
mulation and the test results with and
without HPMC are represented graphi-
cally in Fig. 4.
With regard to foam characteristics the
formulation containing HPMC clearly
performed better in flash foam genera-
tion and foam creaminess. The percep-
tion of skin feel during washing as well
as the afterfeel of the skin, expressed in
skin smoothness and softness at 3 min-
utes, is also greatly improved by HPMC.
From the consumers perspective, the
foam properties as well as the skin feel
are aspects of particular importance.
The results of the sensory hand wash
test reveal once again the striking im-
provements in both areas facilitated by
the addition of Hydroxypropyl Methyl-
cellulose to the formulation.
Viscosity Control
Finally, the incorporation of HPMC al-
lows viscosity control by efficient thick-
ening, independent of primary surfac-
tants or other ingredients, including
electrolytes.
The increase in viscosity of an aqueous
solution is due to the development of
hydrogen bonding between water and
the cellulose chain combined with its lin-
ear, rather stiff structure, resulting in a
large hydrodynamic volume (5). Differ-
ences in molecular weight of HPMC re-
sult in different viscosities. Long cellu-
losic chains induce high viscosities in so-
lution, which can further be fine tuned
by the amount of HPMC added, as vis-
cosity is of course also a function of con-
centration. Very low molecular weight
HPMC on the other hand has little or no
thickening effect. By using a short chain
product all the benefits of using HPMC
regarding foam quality and skin feel can
be employed in low viscous formulations
as well.
The TEGOCEL line provides two differ-
ent viscosity grades: TEGOCEL HPM 50,
a short chain product with only margin-

1.2% TEGOCEL fluid HPM 4000

Control

Fig. 4 Results of sensory hand wash test, conducted by a trained group of 10 panelists
Formulation: 9.0 % Sodium Laureth Sulfate (Texapon NSO)
3.0 % Cocamidopropyl Betaine (TEGO Betain F 50)
0.7 % Sodium Chloride
2.0 % Polyglyceryl-3 Caprate (TEGOSOFT PC 31)
0.3 % Hydroxypropyl Methylcellulose (1.2 % TEGOCEL fluid HPM 4000) resp. 0 % TEGOCEL fluid HPM 4000
in control formulation

SOFW-Journal | 134 | 12-2008 4

 CO S M ET I C S
H Y D ROX Y P RO P Y L M ET H Y LC E L LU LO S E
al influence on viscosity and TEGOCEL
HPM 4000 with excellent thickening
properties. Providing the choice of two
viscosity grades ensures that the right
product is available for a specific appli-
cation.

Fast Processing with Fluid Types
In the form of a white to off-white free-
flowing powder, Hydroxypropyl Methyl-
cellulose dissolves in water by swelling.
The chains of the linear macromolecule
hydrate and disentangle, resulting in
volume expansion (6). During the hydra-
tion process, hydrogen bonding occurs
between water and the cellulose chain,
and as a consequence a gradual viscosi-
ty build-up is achieved, depending on
the length of the polymer chain. To pre-
vent clumping, the product has to be dis-
persed thoroughly to ensure a complete
wetting of all powder particles. Without
sufficient agitation the development
of a gelatinous membrane prevents re-
maining powder from hydration. The pro-
cessing time can be reduced by adding
HPMC to the water phase above the floc-
culation temperature (~ 65 C) at which
the cellulose derivative is insoluble. This
insolubility at higher temperatures is due
to an inverse solubility-temperature be-
haviour that is displayed by most water-
soluble cellulose derivatives (7). As the
temperature decreases, e.g. by the addi-
tion of cold water, the completely dis-
persed powder begins to hydrate, result-
ing in an increase of viscosity.
In some cases it might be advisable to ac-
complish the dissolution of HPMC in wa-
ter separately and to add the HPMC so-
lution to the rest of the formulation. In
general the incorporation of Hydroxy-
propyl Methylcellulose in powder form
demands the proper technical equip-
ment in production and the time to al-
low complete hydration of the polymer.
To meet the special needs of the Person-
al Care industry Hydroxypropyl Methyl-
cellulose is now also available in liquid
versions, offering decisively improved
ease of use due to the fact that process-
ing time is reduced tremendously. TEGO-
CEL fluid HPM 50 and TEGOCEL fluid
HPM 4000 are fluidized polymer suspen-
sions, whereby the HPMC is uniformly
5 SOFW-Journal | 134 | 12-2008
suspended, but not dissolved. The poly-
mer is pre-swollen but dissolution is
blocked by a patented blend of elec-
trolytes and suspending agents. Con-
taining 25 % active HPMC the dispersion
is stabilized by sodium chloride.
The fluidized HPM types allow direct ad-
dition to the aqueous phase at any stage
of the formulation under ambient con-
ditions. They dissolve extremely fast, sav-
ing time and energy by eliminating the
necessity of establishing a thorough dis-
persion and additionally the heating and
cooling of large amounts of water.
Fig. 5 compares the processing times of
HPMC as powder and as a fluid type.
Both TEGOCEL products lead to the
same viscosity, the dispersion of 2 % ac-
tive material of each sample in water re-
sults in a viscosity of about 4000 mPas.
Agitation was accomplished with an an-
chor / MIG stirrer with 350 rpm at 25 C.
In case of the fluid version complete hy-
dration can be achieved with only 5 min-
utes of mixing. In comparison, the disso-
lution of Hydroxypropyl Methylcellulose
as powder requires almost one hour. This
time saving is the principal advantage
afforded by the use of the newly avail-
able fluid types.
Formerly tied up production capacities
are liberated since the time-consuming
preparation of a separate HPMC solution
in an extra tank is rendered unnecessary.
Fig. 5 Comparison of processing time in cold water, left: HPMC as powder,
right: HPMC as fluid
The quick and easy incorporation of the
TEGOCEL fluid types helps to reduce the
overall process costs and contributes to
faster cycle times. Also companies with
limited production facilities that until
now have refrained from using Hydrox-
ypropyl Methylcellulose are now able to
take advantage of the manifold benefits
that are offered by the HPMC in the flu-
idized versions (TEGOCEL fluid 50 and
TEGOCEL fluid 4000).

Conclusion
Hydroxypropyl Methylcellulose is a safe
and effective multifunctional polymer
that offers a broad range of distinctive
features addressing multiple needs. Its
primary functions like thickening and
binding are performed with reliability
and efficiency. Along with this rheologi-
cal effect the positive impact on foam
characteristics, is of particular impor-
tance, because a stable creamy foam de-
notes richness and quality and is of high
relevance to the consumer. The capabili-
ty of HPMC to improve the wet and dry
skin feel out of skin cleansing applica-
tions adds to an overall pleasant percep-
tion, which increases consumer accep-
tance even more. This acceptance com-
bined with the recognized versatility of
Hydroxypropyl Methylcellulose has al-
 CO S M ET I C S
H Y D ROX Y P RO P Y L M ET H Y LC E L LU LO S E

ready resulted in the widespread use of

Phase INCI Ingredient weight %
HPMC in many personal care products.
The TEGOCEL line provides products A Hydroxypropyl Methylcellulose TEGOCEL fluid HPM 4000 1 0.7
that are easy to formulate as they offer Water 17.6
cold processability and rapid wetting B Sodium Laureth Sulfate, 28 % 38.0
and hydration. They are completely sol-
uble in water, leading to crystal clear so- Polyglyceryl-3 Caprate TEGOSOFT PC 31 1 0.3
lutions. Sodium Cocoamphoacetate REWOTERIC AM C 1 25.0
Compared to the traditional powder types Disodium PEG-5 Laurylcitrate
the newly available TEGOCEL fluid ver- Sulfosuccinate; Sodium Laureth REWOPOL SB CS 50 B 1 4.0
sions set new benchmarks with regard to Sulfate
fast processability. As pre-swollen poly- Cocamidopropyl Betaine; ANTIL HS 60 1 2.0
mer suspensions, they are quickly incor- Glyceryl Laurate
porated into formulations. Even with
Glycerin 3.0
limited production facilities, the ease of
use offered by the fluidized polymer sus- C Myristic Acid 5.3
pensions allows significant savings in C12-15 Alkyl Benzoate TEGOSOFT TN 1 1.8
process time leading to savings in pro- Sunflower Oil 1.8
duction costs.
Z Lactic Acid, 80 % 0.5
Preservative, Perfume q.s.

Guideline Formulations 1 Evonik Goldschmidt
Hydroxypropyl Methylcellulose is a valu- Processing:
able component in many cosmetic prod- Hydroxypropyl Methylcellulose is dispersed in water (Phase A). Phases B and C are
ucts, and some examples are given be- prepared separately. Phase A is added to phase B while stirring. Phases A+B and C are heated separate-
ly to 65 C, then Phase C is added to A+B. After cooling under gentle stirring the pH is adjusted to ap-
low.
proximately 6.
Formula 1 represents a moisturizing Body
Wash. This creamy skin cleansing formu- Formula 1 Moisturizing Body Wash
la based on mild surfactants and a high
amount of caring lipids provides a creamy
foam and silky skin feel.
In Formula 2 a mild Facial Cleansing Foam Phase INCI Ingredient weight %
is described. The formulation provides a A Hydroxypropyl Methylcellulose TEGOCEL fluid HPM 4000 1 2.0
creamy and stable foam and is suitable Water 79.4
for application in a pump foamer, e.g. of
B Perfume 0.2
Airspray, NL.
The Conditioning Foam in Formula 3 pro- PEG-7 Glyceryl Cocoate TEGOSOFT GC 1 1.0
vides conditioning and hair repair prop- Capryl/Capramidopropyl Betaine TEGO Betain 810 16.9
erties as well as scalp moisturization. Just Sodium Lactate; Sodium PCA; LACTIL 1 0.5
as Formula 2 it is also applicable for pump Glycine; Fructose; Urea; Niacinamide;
foamers, both formulations containing Inositol; Sodium Bezoate; Lactic Acid
TEGOCEL HPM 50 that improves foam
Preservative q.s.
characteristics without increasing the
1
viscosity. Evonik Goldschmidt
The moisturizing Body Wash in Formula 4
Processing:
contains a complex of skin conditioning
Hydroxypropyl Methylcellulose is dispersed in water (Phase A). The ingredients of Phase B are mixed
agents (silicone based and organic).
in the given order. Finally both Phases are combined.

Formula 2 Mild Facial Cleansing Foam

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References
INCI Ingredient weight %
Quaternium-80 ABIL Quat 3272 1 0.6 (1) W. Sanderman, Holz Roh Werkst. (1973), 31, 11

PEG-40 Hydrogenated Castor Oil TAGAT CH 40 1 0.5 (2) D. Klemm, B. Philipp, T. Heinze, U. Heinze, W.
Perfume 0.3 Wagenknecht in Comprehensive Cellulose
Chemistry, Volume 1, Wiley-VCH, 1998
Capryl/Capramidopropyl Betaine TEGO Betain 810 1 2.0
(3) Cellulose Ethers in Ullmanns Encyclopedia of
Water 93.9 Industrial Chemistry, Release 2006, 7th edition)
Creatine TEGO Cosmo C 100 1 0.5
(4) E. DiAntonio, X. Zhang, J. Conklin, W. Li, T. Drovet-
1
Hydroxypropyl Methylcellulose TEGOCEL HPM 50 0.3 skaya, Society of Cosmetic Chemists Annual
Scientific Meeting and Technology Showcase
Cetrimonium Chloride VARISOFT 300 1 1.3 2007, 55-56
Sodium Lactate; Sodium PCA; LACTIL 1 0.5
Glycine; Fructose; Urea; Niacinamide; (5) J. Bigorra, E. Graupera, O. Par, Comunicaciones
presentadas a las Jornadas del Comit Espanol
Inositol; Sodium Bezoate; Lactic Acid de la Detergencia (2007), 37, 123-131
Citric Acid, 30 % 0.1
(6) E. Doelker, Studies in Polymer Science (1990), 8
Preservatives q.s. (Absorbent Polym. Technol.), 125-45
1
Evonik Goldschmidt (7) Y. Yuguchi, H. Urakawa, Sh. Kitamura, Sh. Ohno,
K. Kajiwara, Food Hydrocolloids, Vol. 9 no. 3,
Processing: 173-179 (1995)
Creatine is dissolved in water, then Hydroxypropyl Methylcellulose is added and given time to swell un-
der agitation. The remaining ingredients are combined in the given order. The pH value is adjusted to
approximately 5.5.

Formula 3 Clear leave-in Conditioning Foam Authors addresses:

* Dr. Sascha Herrwerth
Dr. Hans Henning Wenk
Uta Kortenmeier
INCI Ingredient weight % Dr. Burghard Grning
Dr. Isabella Ulrich-Brehm
Sodium Laureth Sulfate, 28 % 30.0
Evonik Goldschmidt GmbH
1
Polyglyceryl-3 Caprate TEGOSOFT PC 31 0.5 45127 Essen
Bis-PEG/PPG-20/20 Dimethicone ABIL B 8832 1 0.3 Germany
Perfume 0.3 Email: sascha.herrwerth@evonik.com
Water 54.1
Hydroxypropyl Methylcellulose TEGOCEL HPM 4000 1 0.3 ** Dr. Murat Quadir
Sodium Cocoamphoacetate REWOTERIC AM C 1 10.0 Evonik Goldschmidt Corp.
Citric Acid Monohydrate 0.5 Hopewell, USA
PEG-200 Hydrogenated Glyceryl REWODERM LI S 80 1 2.0 Email: murat.quadir@evonik.com
Palmate; PEG-7 Glyceryl Cocoate
Glycol Distearate; Laureth-4; TEGO Pearl N 300 2.0

Cocamidopropyl Betaine
1 Evonik Goldschmidt

Processing:
Hydroxypropyl Methylcellulose is dispersed in water. The remaining ingredients are added in the given
order.

Formula 4 Moisturizing Body Wash

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