Hair conditioning foams formulations

45 years of FCE&T of Cracow University of Technology

Marta OLSZAŃSKA, Rafał SADOWSKI, Jan OGONOWSKI – Institute of Organic Chemistry
and Technology, Cracow University of Technology, Cracow

Please cite as: CHEMIK 2011, 65, 10, 936-945

Introduction [10], a base formulation was developed. The formulation was then
There are a number of substances used as hair conditioning agents. used to produce 7 foams with conditioning and styling properties. Each
Those include fatty substances, ethylene glycols, silicones, protein formulation contains ingredients (INCI) provided in Table 1.
hydrolysates, cationic surface-active agents, vitamins and other [1÷6]. In the comparative study market products with the following
They are mainly applied to products such as: rinses, foams, creams, composition were used:
balms, lotions, gels, pomades, hair oils, shampoos [7].
Hair washing and care are among the most fundamental hygienic Market product 1 (INCI):
activities. Conditioning agents and shampoos are one of the most Aqua, Butane, Propane, Cyclomethicone, Quaternium – 80, Panthenol,
crucial and most competitive segments of the cosmetics market. Cetrimonium Chloride, Polyquaternium – 11, PVP, Dimethiconol, Octyl
Consumers appreciate the benefits of nice-looking and easily combed Methoxycinnamate, Hydrolyzed Keratin, Persea Gratissima, Propylene
hair, and in recent years the conditioners market has witnessed Glycol, Parfum.
the most rapid growth in the whole industry [7]. Hair conditioners are
supposed to facilitate combing of wet and dry hair, provide antistatic Market product 2 (INCI):
and moisturizing effect, increase the hair shine and volume, as well as Aqua, Alcohol Denat., Butane, Propane, VP/VA Copolymer,
repair the damaged hair shafts. Polyquaternium-11, Cetrimonium Chloride, Isobutane, Parfum, Phenoxy
Hair foams can be used as conditioners and/or styling agents. ethanol, Benzyl Acetate.
Foam products can be applied to both wet and dry hair. As with most
conditioners, they can either be left on the hair until next washing or Market product 3 (INCI):
be rinsed after some time. The foam created by the propellant allows Aqua, Alcohol Denat., Butane, Propane, VP/VA Copolymer,
for even coverage of the hair with the product, thus ensuring easy Polyquaternium-16, Cetrimonium Chloride, Isobutane, Parfum, Phenoxy
combing, conditioning properties and hairstyle duration. ethanol, Benzyl Acetate.
Foam products soften the hair, at the same time providing excellent Table 1
stabilisation for the hairstyle. Applying the abovementioned products Ingredients of the hair foam formulations
allows the consumers to instantly change their hairstyle; the products Trade name INCI Name Application Additional Information
can change the direction of locks and waves, increase hair volume or
Quartamin Cetrimonium Max. concentration in the
give the hairstyle a wet appearance. Foam products differ from other Conditioner
60W30 chloride product – 5%
styling products in that they do not leave the hair stiff and sticky. Ampholytic polymer,
Styling
Applying hair foam is very easy and convenient, therefore products in Aquaflex XL30 Polyimide – 1
polymer
water-soluble, compatible
the foam form are appreciated by a wide group of consumers [8]. with all surfactants
First hair styling foam products were introduced to the market in Molecular weight
125,000. Water-soluble.
1970, however, they were not particularly popular at the time. Only in Kerasol
Hydrolyzed
Conditioner Settles as residual
Keratin
1973 did Helene Curtis introduce a product line for professional styling in pH < 5. Max. concen-
under the name „Balsam & Body”. Other products by that company tration in product - 10%
include: „Last Word” and „Heats On Self – Heating Foam Conditioner”. Ercasorb 2020 Polysorbate – 20
Solubilizer, foam-
HLB = 16.7
creating agent
Those products were applied to wet hair and left until next washing. In
Europe foams were introduced to retail in 1983 (L’Oreal). At the same Dow Corning PEG – 12 Dimet-
Conditioner Water-soluble
193 FLUID chicone
time, foam styling product „Valence” was introduced to the American
Cocamidopropyl
market. The product intended solely for conditioning was „Flone”, Tego Betaine ZF
Betaine
Foam stabilizer Ampholytic surfactant
introduced by L’Oreal Paris. The product was available in two versions:
Uvinul P25 PEG – 25 PABA UV Filter Nonionic
moisturizing, whose aim was to replenish and retain moisture in the
Farnesol (and)
hair, and volume-enhancing. The years 1986-1987 saw further growth in Unistab S69 Scent cartridge -
Linalool
foam products production. Increasingly higher consumer demands and Styling
PVP/VA W635 VP/VA Copolymer Water-soluble
changing hairstyle trends pushed foam products off the market and gave polymer
way to hairsprays. Hairsprays provided hairstyle stabilisation, something Styling
Luviskol K30 PVP Water-soluble
the foams were unable to do [8]. The general foam composition is as polymer
follows: solvent, active ingredients/polymers, propellant/s, emulsifier/ Citric acid Citric Acid pH regulator -
surfactant, preservatives, fragrance, additional ingredients. Propane/Butane Propane/Butane Propellant Density – 0.56 g/cm3
The aim of this study was to develop a formulation for a hair foam D – Panthenol
Panthenol Conditioner Water-soluble
with conditioning and styling properties, at the same time retaining USP
good organoleptic and utility parameters. Furthermore, the image “CINDY” Parfum
Parfum
Parfum
-
of hair structure prior to and after application of keratine solution Composition Composition
was made, using SEM technique. DMDM – Hydan-
toin (1),
Methylchloroisot- Water-soluble, applied in
EUXYL K510 Preservative
Experimental part hiazolinone (2), pH < 8
Basing on the analysis of foam product formulations [9] and the Methylisothia-
zolinone (3)
information on cosmetic raw materials provided by manufacturers

nr 10/2011 • tom 65 • 941

 For the SEM-study of hair structure a market hair lightener was measurements were carried out at constant temperature. Base density
45 years of FCE&T of Cracow University of Technology
used. The composition (INCI) of the lightener is as follows: Potassium was calculated using the following formula:
Persulfate, Sodium Stearate, Sodium Silicate, Sodium Persulfate, Ammonium
Persulfate, Magnesium Carbonate, Sodium Metasilicate, Cyanopsis
Tetragonoloba, Cetrimonium Bromide, Silica, Cyclodextrin, Sodium Lauryl
Suifate, Ttetrasodium EDTA, Parfum. where: mb – batch mass, [g]; Vb – batch volume, [g/cm3]; d – batch
All foams were prepared in the amount of 100 g, with deducted density, [g/cm3].
amount of water and Panthenol placed into the beaker (A). In the
event of the formulation providing for film-forming agent, such agent The solid content was determined gravimetrically by weighing out
was also placed into the beaker A. The beaker contents were then 10 g of foam base in the beaker and placing it in the dryer at 105ºC for
carefully mixed. 24 hours. After drying and cooling down, the beaker with its content
The following ingredients were subsequently weighed out into was weighed against dry mass.
beaker (B): Polysorbate – 20, Parfum, Cetrimonium Chloride, PEG-12 The solid content (X) per 100 g was calculated using the following
Dimethicone, Cocamidopropyl Betaine, contents were carefully mixed, formula:
and, depending on the formulation, Polysilicone – 19 or PEG – 25 PABA X = [(m3 – m1) * 100%] / m2
and the mixture of DMDM – Hydantoin, Methylchloroisothiazolinone and
where: m1 – beaker mass [g]; m2 – base mass [g]; m3 – beaker and base
Methylisothiazolinone were added.
mass after drying [ g].
The contents of beaker B were then placed into beaker A and
mixed. Next, the pH of the resulting mixture was measured. This was
Foam liquefaction time was measured by weighing out approx.
followed by adding the hydrolyzed keratin solution and, depending on
3 g of the given foam on a watch glass and then, using a stopwatch,
the requirements, acidifying the mixture with a 30% citric acid in order
the time was measured until the foam was liquefied.
to reach the desired pH value. In some formulations the fragrance was
The study of electrostatic properties of hair was conducted on
added at the end.
the basis of hair volume measurement [12, 13]. This comprises
The obtained foam bases (75 cm3) were then placed in aluminium
measuring the width of the shadow cast by the hairpiece on a graph
containers and kneaded; the containers were filled with propellant.
paper sheet, after prior washing of the hairpiece, applying the foam
The formulations of the obtained foams are provided in Table 2.
and drying in a hot air stream. On the basis of the shadow width
Table 2 measurement we can infer the efficacy of electrostatic charge reduction
Hair foam formulation 1÷7 by the given conditioner.
Prior to measurements, hairpieces were washed in shampoo,
P1 P2 P3 P4 P5 P6 P7 carefully dried with a towel and combed bottom-up with a plastic
Trade name
fine-tooth comb. This activity was repeated 14 times. After applying
100 g 100 g 100 g 100 g 100 g 100 g 100 g
the foam (0.5 g), the hairpiece was mounted on a tripod and dried
Water 87.73 86.93 91.30 86.93 88.76 88.65 90.98 completely with a hairdryer. The hair was then again combed
(14 times) and the width of the shadow cast by the hairpiece on graph
Propane/Butane - - - - - - -
paper was measured. The width of the shadow was read out on the
Luviskol K30 2.78 millimetre scale. In order to standardize results, the readout is carried
Aquaflex XL 30 5.56 5.56 - -
out at 6 cm and 13 cm from the top of the hairpiece.
The obtained results are provided in Table. 3
PVP W 635 - - 5.56 5.56
Table 3
Quartamin 60W30 5.56 5.56 1.11 1.11 1.11 1.11 1.11
Physical and user properties of the foam formulations studied
Kerasol 3.33 - 2.22 2.22 - 2.22 -
Base Solid Foam Hairpiece
DC 193 Fluid 1.11 1.11 0.56 0.56 0.56 0.56 0.56 Foam
density content, final pH liquefaction shadow
no.
Ercasorb 2020 0.56 0.56 0.56 0.56 0.56 0.56 0.56 d, g/cm3 % time, min width, cm

Fragrance 0.56 0.56 0.56 0.56 0.56 0.56 0.56 -

WATER 0.997 - - 60/110
Citric acid 0.48 - 0.25 1.89 2.22 0.11 -
1 0.985 4.25 5.70 15.13 34/39
Panthenol 0.28 0.28 0.28 0.28 0.28 0.28 0.28

Tego Betaine ZF 0.22 0.22 0.22 0.22 0.22 0.22 0.22 2 0.996 2.60 3.80 15.30 35/40

EUXYL K510 0.11 0.11 0.11 0.11 0.11 0.11 0.11 3 0.996 4.55 5.37 16.40 37/48

Uvinul P25 0.06 0.06 0.06 0.06 0.06 0.06 0.06 4 0.989 4.64 5.40 9.20 38/47

5 0.993 3.98 4.98 16.10 37/42

For the obtained foams the examination of physicochemical 6 0.990 4.42 5.35 15.41 37/45
properties of foam bases were conducted (pH and density
7 0.995 4.27 5.14 16.10 37/46
measurement), and for ready products - the curl retention of
hairpieces, picking up static and foam liquefaction time. Commer-
- - - 15.28 43/50
The pH was measured using electronic MetereLab PHM210 cial foam
pH-meter.
The base density measurement [11] was done using a pycnometer. The curl retention (CR) [13, 14] was assayed in a climatic chamber
For this purpose, first a dry pycnometer, filled with distilled water, (W = 50%,T=20oC). The assay included hairpieces made from natural
was weighed, followed by pycnometer filled with foam bases. Both hair (Fig.1) with the following parameters:

942 • nr 10/2011 • tom 65

• European, non-dyed, dark-brown hair Prepared hair was then placed on the so-called holders and dusted

45 years of FCE&T of Cracow University of Technology

• single hairpiece weight approx. 2 g, length 17.5 cm
• all hairpieces made from the same hair type.
In order to acquire locks with proper curl, metal rollers with
1.5 cm in diameter were used. Prior to curling, the hairpieces were
washed in 10% solution of a market shampoo, drained (in a paper
towel) and then placed into a holding oven (45oC) for the night in
order to dry off.
In the study of one foam type, 6 hairpieces were used plus one
for the so-called blank test. 0.5 g of foam was rubbed into each of the
6 hairpieces; the hair was then curled on the roller. It is important for
the hair to be curled strongly and tightly adhere to the roller. Curled
hair was secured against uncurling with the use of clips. Identical
procedure was applied to the blank test, using distilled water instead
of foam. The prepared rollers were placed into the holding oven
for 2 hours at 45oC. After that time the hairpieces were removed
from the rollers and placed in a climatic chamber (temperature
20oC, humidity 50%). Immediately after hanging the hairpiece in
the chamber, the „zero” time was marked. This is very important,
since the set temperature and humidity are already present in the
chamber. After hanging all of the hairpieces the measurement was
started. Usually the readout takes place after: 15, 30, 45, 60, 90, 120
and 150 minutes.
The degree of hairpiece straightening was marked on the scale on
the chamber wall after each readout. The hair shape retention was
calculated using the following formula:
where: L – length of fully straightened hair [cm]; L0 – length of hair prior
to high humidity exposure [cm]; Lt - length of hair after high humidity
exposure over time t, cm.
The obtained mean results of hair curl retention for the tested
products are provided in Table 4.
Table 4
Curl retention data of the foams 1÷7
with gold, and placed in the apparatus to conduct measurements. Finally,
the hair was immersed in Kerasol solution with 0.39% concentrated
keratine.
Discussion
All acquired foams contain a conditioning agent (Quartamin
60W30 – cetrimonium chloride). Aside from the abovementioned
quat, also keratine hydrolysates were added to four foams (1, 3, 4, 6).
Foam 2 was the placebo (did not contain keratine hydrolysate). Both
foam 1 and 2 did not contain conditioning and styling resins. Foam
3 contained Luviskol K30 resin, foams 4 and 5 contained Aquaflex
XL 30, and foams 6 and 7 contained PVP W 635 resin.
The pH values of foam base 1 with conditioning agent (keratine),
not containing stabilizing resin, was 5.70 and required correction. The
foam base 5 (4÷8, 14), based on Aquaflex XL 30 resin, required a
minor addition of citric acid solution. The PVP W 635 resin in foam 6
reduced the base pH. In bases with keratine (pH approx. 5.84) higher
pH values were observed than in bases without keratine (pH approx.
5.14). Foam 3 with Luviskol K30 resin had the pH of 6.04. Similarly,
bases with PVP W 635 and Luviskol K30 resins required minor additions
of citric acid solution to reduce the pH value. The lowest pH value was
observed in the foam base 2 (3.80).
Comparing the density of acquired products, it was established
that the highest reduction of foam base density was caused by PVP W
635 (PVP/VA) resin.
The dry mass indicator informs on the causalities of production
and the quality of the given foam product. Low solid content value of
other foams might indicate the absence of resin from the formulation;
with higher SC value the foam is considered to have better conditioning
and styling properties. This is not entirely correct, since high presence
of volatile ingredients might distort the results. Those ingredients might
escape at the measurement temperature (105oC) and thus be absent
from the solid content. The analysis of solid content (Fig. 1) shows
that the lowest solid content value (0.61) was observed in the market
product 1, which was most likely caused by high content of volatile
ingredients therein.

P1 P2 P3 P4 P5 P6 P7 MP 1
TIME
CRav., %

0 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00

15 82.58 78.77 91.58 90.29 92.68 91.13 89.10 85.79

30 75.00 68.77 84.72 81.97 83.41 83.64 81.24 77.03

45 68.41 63.42 80.75 77.36 78.91 80.37 77.22 70.24

60 65.55 60.78 77.74 73.81 74.79 77.94 74.66 68.55

Fig. 1. Comparison of total solid contents of the foams studied (1-7)
with that of commercial foams (MP1, MP2, MP3)
90 61.17 58.28 75.48 69.66 69.82 75.49 72.20 64.77

Average SC value was observed in foam 2 (2.60) and market

120 57.57 55.57 72.90 66.83 64.27 73.86 68.67 64.18
product MP3. In foam 2 the lower SC value (2.60) as compared to
other foams is related to the absence of keratine and resin from its
150 55.28 53.76 70.90 66.83 63.55 73.86 68.11 61.88
formulation. A higher SC is observed in products with keratine, i.e.
4 (4.64) and 6 (4.42), as compared to their counterparts without this
The analysis of the hair structure image was carried out with SEM ingredient, i.e. 5 (3.98) and 7 (4.27).
technique, using the JEOL JSM-5410 scanning electron microscope Liquefaction time of foam in the ready product cannot be too
with an EDS detector by NORAN. The analysis was carried out on short. After „leaving” the container the foam should maintain stability
„bundles” of dyed, dark-brown European hair. Next, the hair was on the hand for a few minutes.
subjected to harsh conditions by placing it into a market hair lightener As evident from the values cites in Table 3, keratine hydrolysates
with 9% distilled water for 12 hours. have a minor impact on the reduction of foam liquefaction time. Foams

nr 10/2011 • tom 65 • 943

 2, 5, 7 (not containing keratine – Kerasol) exhibited liquefaction time
45 years of FCE&T of Cracow University of Technology
of (15.30; 16.10 min), whereas the liquefaction times of foams with
keratine (1, 3, 4, 6) were shorter and amounted to (15.13; 16.40;
9.20; 15.41 min respectively). The liquefaction time values of foam
products acquired in the laboratory (with the exception of foam 4,
containing Aquaflex XL30, Quartamin 60W30 and Kerasol resins) were
characterised by comparable liquefaction times to market product 1.
Electrostatic properties of hair are often the crucial parameter
determining the demand for the given product on the market.
The CR value for foam 1, containing 3% keratine hydrolysates,
is (55.28%), while for foam 2, which was the placebo, the value was
(55.76%). In both those foams the keratine hydrolysates exhibit no
positive impact on the curl retention rate.
SEM analysis of the hair structure has confirmed the layer
structure. Photographs 1 and 2 present the exterior hair layer
– the cuticle. On photograph 2 we can see jagged, fractured and open
hair scales, indicating that the hair is considerably damaged.

Fig. 2. Effect of the antistatic agent on electrostatic properties of hair

It is important that the electrostatic properties of hair are significantly

reduced after applying the foam. Figure 2 presents the impact of the Photo. 1. Open hair scales
studied products on the electrostatic properties of hair. The diagram
indicates that the lowest electrostatic properties are exhibited by
foam 1 (without resin), containing a conditioning mixture of keratine
hydrolysates (3%) and cetrimonium chloride (5%). When foam 1 was
applied, a considerable reduction in the hairpiece shadow width was
observed from 60 to 39 cm. In the case of foams containing resins,
the lowest electrostatic properties of hair is attributed to foam 6 with
a 5% PVP W 635 addition and conditioning agents: keratine 2% and
Quartamin 60W30 1% (shadow width reduction from 60 to 45 cm).
In general, all of the studied products exhibit very good antistatic
properties, comparable to market foam (MP1).
Figure 3 presents the curl retention of hairpiece, depending on the
applied resin or absence thereof.

Photo. 2. A broken hair scale is indicated

The hair sample subjected to harsh conditions (market hair

lightener + 9% distilled water for 12 hours) is presented on
photographs 3 and 4. We can observe complete destruction of the
cuticle and revealed hair cortex, confirming its structure (protofibril
rods). Photograph 4 shows the interior of the hair after partial
removal of cortex.

Fig. 3. Dependence of curl retention of the foams studied on time

The highest curl retention rate was observed for foam 6 (5% PVP/
VA), exhibiting curl retention of 73.86%, higher than the rate for foam
7 (68.11%) which contains similar ingredients, with the exception of
keratine hydrolysates. In the case of foams based on Aquaflex XL30
resin, the addition of keratine had increased the CR value. Foam 5,
with similar content of Aquaflex XL30 but without Kerasol, had lower
CR value (CR = 63.55%) than foam 4, containing 2% Kerasol (CR =
66.83%). Foams based on Aquaflex resin provide lower curl retention
rate than foams containing PVP/VA.
High curl retention rate (70.90%) was also observed in
hairpieces treated with foam 3, containing 2.5% Luviskol K30 resin
Photo. 3. SEM image of hair interior after removal of cuticle
and 2% Kerasol.

944 • nr 10/2011 • tom 65


Photo. 4. SEM image of hair after removal of a part of hair cortex
In order to examine the conditioning impact of keratine, a hair
sample was immersed in 0.39% solution of keratine hydrolysate
(Kerasol) for 3 minutes. After drying the sample was observed under
a microscope. Photographs 5 and 6 show the image of the hair sample
after conditioning. As we can see, the keratine with low hydrolyse
degree (M = 125,000) creates a protective film, covering the open
scales and cortex.
Photo. 5. Damaged cortex coated with keratin film
Photo. 6. SEM image of hair after conditioning showing
the keratin film
Conclusions
When using keratine hydrolysate solution as the hair conditioning
agent, it is important to select the appropriate pH of the foam base
(optimum pH = 5.00).
The solid content (SC) of the ready product (foam) depends on its
composition. The lowest SC value was observed for foams containing
extremely volatile ingredients.
The curl retention (CR) depends on the type and concentration
of resin used in the foam. The addition of PVP, PVP/VA or Polyimide
nr 10/2011 • tom 65
– 1 (2.5% of mass) resins allowed for achieving average CR rate.
45 years of FCE&T of Cracow University of Technology
The highest CR rate (73.86%) is provided by foam 6 (5% PVP/VA).
The cationic surface-active agents effectively reduce the electrostatic
properties of hair. A 64% (1.5% cetrimonium chloride) and an average
59% (0.30% cetrimonium chloride) reduction of hairpiece shadow was
observed after applying products containing that complex.
Aquaflex XL 30 (Polyimide – 1) in 2.5% mass concentration failed
as ingredient in hair styling foam products.
Keratine with high molecular weight (M=125,000) creates
a protective film on the hair surface, instead of penetrating the
interior.
Literature
1. Williams D. H., Schmitt W. H., Chemistry and technology of the cosmet-
ics and toiletries industry. Blackie Academic & Professional, Glasgow,
1992.
2. Schueller R., Romanowski P., Conditioning agents for hair and skin. Marcel
Dekker, Inc. New York, 1999.
3. Arct J., Skład i zasady komponowania szamponów. Wiadomości PTK,
2000, 3, 1(5), 10-20.
4. Secchi G., Role of protein in cosmetics. Clinics in Dermatology, 2008,
26, 321.
5. Roddick – Lanzilotta A., Kelly R., Scott S., Mitchell G., Chahal S., Pro-
tecting the hair with natural keratin biopolymers. Cosmetic & Toiletries
magazine, 2006, 5, 61 – 68.
6. Romanowski P., Schueller R., Polymers in personal – care products. Co-
smetic & Toiletries magazine, 1998, 11, 51 – 56.
7. Wiśniowolski A., Wiśniowolska M., Rynek pielęgnacji włosów- dobry, bo
polski. Cosmetic Reporter, 2007, 10, 17-18.
8. Johnson Dale H., Hair and hair care. Marcel Dekker. New York, 1997.
9. Flick. E.W., Cosmetic and Toiletry Formulations, Volume 8 (2nd Edi-
tion). William Andrew Publishing/Noyes. Wersja elektroniczna Knovel,
2003.
10. Karty informacyjne surowców firm: Croda, ISP, Evonik – dostęp elek-
troniczny.
11. Norma PE-EN ISO 3838. Oznaczanie gęstości lub gęstości względnej.
12. Matthias, Pfaffernoschke D., Aerosol Styling Mousses: Polymer Technology
Meets Consumer Needs. International Journal for ASAP, 2006, 4, 3-13.
13. Leidreiter H.I., Kortemeier U., Hair type and required specific ingredients
for conditioning treatments. Cosmetic & Toiletries Manufacture Worl-
dwide, 2006, 127 – 133.
14. Johensen A.M., Aerosol handbook (2nd edition). Industry Publications.
New York, 1982.
Jan OGONOWSKI – Professor (Ph.D., Eng) is a graduate of the Faculty
of Chemistry of the Silesian University of Technology (1996). Currently He is
employed as Head of the Organic Technology and Refining Processes Chair
on the Faculty of Chemical Engineering and Technology, Cracow University
of Technology. Specialization: organic technology, biotechnology, catalytic
processes.
Marta OLSZAŃSKA – Ph.D., (Eng), is a graduate of the Faculty of Chemi-
cal Engineering and Technology of the Cracow University of Technology
(1971). Currently She is employed at the Institute of Organic Chemistry
and Technology. Specialization: low-tonnage products technology, cosmetic
chemistry and technology.
Rafał SADOWSKI – Ms.Sc., (Eng), is a graduate of the Faculty of
Chemical Engineering and Technology of the Cracow University of Tech-
nology (2010).
• 945