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

Abstract
egenstand
derMethylcelluvorliegenden
ydroxypropyl
Arbeit
ist dieisEntwicklung
lose (HPMC)
a multifunceiner
akzeptationalkosmetisch
additive that
offers a
blen und
in ihren
Bestandteilen
broad
range
of impressive
properoptimal
abgestimmten
ties
addressing
multipleO/W-Creneeds in
me. Hierzuapplications
soll ein neuer
multiRinse-off
even
at low
funktioneller
use
levels. TheO/W-Emulgator,
most importantdas
PEG/PPG-25/25
Dimethicone
zum
properties
include
its foam boostEinsatz
gelangen.
ing
effect,
a significantly improved skin feel and viscosity control in cleansing and conditioning
Personal Care formulations.
HPMC also contributes to increased
economic efficiency in many surfactant based skin cleansing and
shampoo formulations. The incorporation of HPMC reduces the required amount of certain ingredients, such as surfactants, thickeners and emollients, without sacrificing performance. On the contrary the performance can even be
superior in some cases.
Compared to the traditional powdered 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 polymer suspensions allows significant
savings, in process time and costs.

G
H

Introduction
Hydroxypropyl Methylcellulose is a modified natural carbohydrate polymer derived from cellulose, the most abundant
polymer occurring in nature (Fig. 1). Cellulose, a linear polysaccharide composed
of 1,4-linked -D-glucopyranose as monosaccharide repeat units, is a truly renewable raw material produced by all plants
and is therefore practically inexhaustible.
The annual production of cellulosic matter from photoinitiated biosynthesis is
estimated to be approximately 1.3x109
metric tons (1).
Due to its strong tendency to form crystalline regions through hydrogen bonding, cellulose itself is an insoluble material and has to be modified to render it
water soluble (2). Most commercially important cellulose derivatives are cellulose ethers, which are formed by partial
or complete derivatization of the hydroxyl groups of cellulose by ether substituents (3). For HPMC, a mixed cellulose ether, these substituents are hydroxypropyl and methyl groups, which,
in addition to water solubility, impart
surface activity to the polymer. A variety
of HPMC types is commercially available

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

pharmaceutical applications), and the
properties of HPMC are determined by
the degree of methyl and hydroxypropyl
substitution, as well as by its molecular
weight. Due to its excellent toxicological
profile, it is approved for use by the FDA
as a direct (21 CFR 172.74) and an indirect food additive, as well as for use as a
food additive in the EU (E 464).
HPMC is used in many Personal Care
products throughout the world, displaying a multitude of functions, and primarily due to this abundance of performance properties HPMC enjoys a growing popularity with experienced formulators.
The main focus of this article is the application of Hydroxypropyl Methylcellulose in Rinse-Off products. A similar paper with regard to Leave-On applications
is in preparation.
The TEGOCEL series (product of Evonik
Goldschmidt GmbH, Essen) comprises
two different viscosity grades of Hydroxypropyl Methylcellulose: TEGOCEL
HPM 50 and TEGOCEL HPM 4000, the
numbers indicating the achieved viscosity in mPas measured at 2 % concentration in water at 20 C.

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 properties of HPMC also in electrolyte rich
systems are dominating its use in cosmetic formulations. Even though primarily used as a thickener in liquid formulations or as a binder in solid / semisolid products this ingredient also provides a multitude of additional benefits
to Personal Care products. Enhanced
foam quality of surfactant based formulas, improved skin feel, optimized stabilization of emulsions and increased surface 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 formulations certain ingredients like surfactants, 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 increased mildness, a feature that is highly desirable for products like shampoos.
The foam enhancing property is especially advantageous in pump foamer liquids, where the addition of HPMC provides a dramatic improvement in foam
quality. Today, dispenser foam applications 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

of more uniform and smaller bubbles delivers a denser, creamier foam with increased stability, leaving a rich and luxurious skin feel. At the same time the required low viscosity of the formulation
for the pump foamer bottle is guaranteed 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

Foam Boosting Effect
Hydroxypropyl Methylcellulose contributes
to significantly improved foam characteristics such as creaminess and foam
stability as well as volume. This truly
unique advantage is based on a property referred to as interfacial gelation.
The inherent surface activity of HPMC
combined with a certain gelling behaviour leads to the spontaneous formation
of highly viscous films within the foam,
more precisely between and around the
bubbles. The development of this polymer network occurs even in very dilute
systems because the surface activity of
HPMC induces its enrichment near the
gas/liquid interface leading to concentrations which are significant for viscosity building. By strengthening the bubble walls and slowing the rate of water
drainage, the foam gets denser and more
stable in cleansing products of all types.
Viscosity and foam properties can be
maintained with lower additions of salt
and surfactant (4). These possible savings

Formulation with 0.5% HPMC

Fig. 2 Comparison of foam quality on a flat plane

Formulation with 0.5% HPMC

Formulation without HPMC

Fig. 3 Comparison of foam quality on an inclined plane

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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 watery, resulting in enhanced stability and
creaminess. The adherence to the inclined surface is significantly better.

Improvement of Skin Feel

In skin cleansing formulations, the combination of enhanced surface activity
and strengthened film-forming properties in addition to increased lubricity all
together combine to provide a remarkable improvement of wet and dry skin
feel. With the incorporation of low concentrations of Hydroxypropyl Methylcellulose 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 incorporation 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 because of its additional rheological effect
in a shower gel formulation. The formulation and the test results with and
without HPMC are represented graphically in Fig. 4.
With regard to foam characteristics the
formulation containing HPMC clearly
performed better in flash foam generation and foam creaminess. The perception of skin feel during washing as well
as the afterfeel of the skin, expressed in
skin smoothness and softness at 3 minutes, 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 improvements in both areas facilitated by
the addition of Hydroxypropyl Methylcellulose to the formulation.

Viscosity Control
Finally, the incorporation of HPMC allows viscosity control by efficient thickening, independent of primary surfactants 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 linear, rather stiff structure, resulting in a
large hydrodynamic volume (5). Differences in molecular weight of HPMC result in different viscosities. Long cellulosic chains induce high viscosities in solution, which can further be fine tuned
by the amount of HPMC added, as viscosity is of course also a function of concentration. 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 different 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

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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 application.

Fast Processing with Fluid Types
In the form of a white to off-white freeflowing powder, Hydroxypropyl Methylcellulose dissolves in water by swelling.
The chains of the linear macromolecule
hydrate and disentangle, resulting in
volume expansion (6). During the hydration process, hydrogen bonding occurs
between water and the cellulose chain,
and as a consequence a gradual viscosity build-up is achieved, depending on
the length of the polymer chain. To prevent clumping, the product has to be dispersed thoroughly to ensure a complete
wetting of all powder particles. Without
sufficient agitation the development
of a gelatinous membrane prevents remaining powder from hydration. The processing time can be reduced by adding
HPMC to the water phase above the flocculation temperature (~ 65 C) at which
the cellulose derivative is insoluble. This
insolubility at higher temperatures is due
to an inverse solubility-temperature behaviour that is displayed by most watersoluble cellulose derivatives (7). As the
temperature decreases, e.g. by the addition of cold water, the completely dispersed powder begins to hydrate, resulting in an increase of viscosity.
In some cases it might be advisable to accomplish the dissolution of HPMC in water separately and to add the HPMC solution to the rest of the formulation. In
general the incorporation of Hydroxypropyl Methylcellulose in powder form
demands the proper technical equipment in production and the time to allow complete hydration of the polymer.
To meet the special needs of the Personal Care industry Hydroxypropyl Methylcellulose is now also available in liquid
versions, offering decisively improved
ease of use due to the fact that processing time is reduced tremendously. TEGOCEL fluid HPM 50 and TEGOCEL fluid
HPM 4000 are fluidized polymer suspensions, whereby the HPMC is uniformly

suspended, but not dissolved. The polymer is pre-swollen but dissolution is

blocked by a patented blend of electrolytes and suspending agents. Containing 25 % active HPMC the dispersion
is stabilized by sodium chloride.
The fluidized HPM types allow direct addition to the aqueous phase at any stage
of the formulation under ambient conditions. They dissolve extremely fast, saving time and energy by eliminating the
necessity of establishing a thorough dispersion 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 % active material of each sample in water results in a viscosity of about 4000 mPas.
Agitation was accomplished with an anchor / MIG stirrer with 350 rpm at 25 C.
In case of the fluid version complete hydration can be achieved with only 5 minutes of mixing. In comparison, the dissolution of Hydroxypropyl Methylcellulose
as powder requires almost one hour. This
time saving is the principal advantage
afforded by the use of the newly available 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.

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 Hydroxypropyl Methylcellulose are now able to
take advantage of the manifold benefits
that are offered by the HPMC in the fluidized 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 rheological effect the positive impact on foam
characteristics, is of particular importance, because a stable creamy foam denotes richness and quality and is of high
relevance to the consumer. The capability of HPMC to improve the wet and dry
skin feel out of skin cleansing applications adds to an overall pleasant perception, which increases consumer acceptance even more. This acceptance combined with the recognized versatility of
Hydroxypropyl Methylcellulose has al-

Fig. 5 Comparison of processing time in cold water, left: HPMC as powder,

right: HPMC as fluid

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ready resulted in the widespread use of

HPMC in many personal care products.
The TEGOCEL line provides products
that are easy to formulate as they offer
cold processability and rapid wetting
and hydration. They are completely soluble in water, leading to crystal clear solutions.
Compared to the traditional powder types
the newly available TEGOCEL fluid versions set new benchmarks with regard to
fast processability. As pre-swollen polymer suspensions, they are quickly incorporated into formulations. Even with
limited production facilities, the ease of
use offered by the fluidized polymer suspensions allows significant savings in
process time leading to savings in production costs.

Guideline Formulations
Hydroxypropyl Methylcellulose is a valuable component in many cosmetic products, and some examples are given below.
Formula 1 represents a moisturizing Body
Wash. This creamy skin cleansing formula 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
is described. The formulation provides a
creamy and stable foam and is suitable
for application in a pump foamer, e.g. of
Airspray, NL.
The Conditioning Foam in Formula 3 provides conditioning and hair repair properties as well as scalp moisturization. Just
as Formula 2 it is also applicable for pump
foamers, both formulations containing
TEGOCEL HPM 50 that improves foam
characteristics without increasing the
viscosity.
The moisturizing Body Wash in Formula 4
contains a complex of skin conditioning
agents (silicone based and organic).

Phase

INCI

Ingredient

Hydroxypropyl Methylcellulose
Water
Sodium Laureth Sulfate, 28 %
Polyglyceryl-3 Caprate
Sodium Cocoamphoacetate
Disodium PEG-5 Laurylcitrate
Sulfosuccinate; Sodium Laureth
Sulfate
Cocamidopropyl Betaine;
Glyceryl Laurate
Glycerin
Myristic Acid
C12-15 Alkyl Benzoate
Sunflower Oil
Lactic Acid, 80 %
Preservative, Perfume

TEGOCEL fluid HPM 4000 1

weight %

TEGOSOFT PC 31 1
REWOTERIC AM C 1

0.7
17.6
38.0
0.3
25.0

REWOPOL SB CS 50 B 1

4.0

ANTIL HS 60 1

2.0
3.0
5.3
1.8
1.8
0.5
q.s.

TEGOSOFT TN 1

Evonik Goldschmidt

Processing:
Hydroxypropyl Methylcellulose is dispersed in water (Phase A). Phases B and C are
prepared separately. Phase A is added to phase B while stirring. Phases A+B and C are heated separately to 65 C, then Phase C is added to A+B. After cooling under gentle stirring the pH is adjusted to approximately 6.

Formula 1 Moisturizing Body Wash

Phase

INCI

Hydroxypropyl Methylcellulose TEGOCEL fluid HPM 4000 1

Water
Perfume
PEG-7 Glyceryl Cocoate
TEGOSOFT GC 1
Capryl/Capramidopropyl Betaine TEGO Betain 810
Sodium Lactate; Sodium PCA;
LACTIL 1
Glycine; Fructose; Urea; Niacinamide;
Inositol; Sodium Bezoate; Lactic Acid

Preservative
Evonik Goldschmidt

Ingredient

weight %
2.0
79.4
0.2
1.0
16.9
0.5

q.s.

Processing:
Hydroxypropyl Methylcellulose is dispersed in water (Phase A). The ingredients of Phase B are mixed
in the given order. Finally both Phases are combined.

Formula 2 Mild Facial Cleansing Foam

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INCI

Ingredient

Quaternium-80

ABIL Quat 3272 1

weight %
0.6

(1) W. Sanderman, Holz Roh Werkst. (1973), 31, 11

PEG-40 Hydrogenated Castor Oil TAGAT CH 40 1

0.5

Perfume

0.3

(2) D. Klemm, B. Philipp, T. Heinze, U. Heinze, W.

Wagenknecht in Comprehensive Cellulose
Chemistry, Volume 1, Wiley-VCH, 1998

Capryl/Capramidopropyl Betaine TEGO Betain 810 1

2.0

Water
Creatine

93.9
TEGO Cosmo C 100 1

Hydroxypropyl Methylcellulose TEGOCEL HPM 50

Cetrimonium Chloride

0.5
0.3

VARISOFT 300 1

1.3

0.5

Sodium Lactate; Sodium PCA;

LACTIL
Glycine; Fructose; Urea; Niacinamide;
Inositol; Sodium Bezoate; Lactic Acid

References

(3) Cellulose Ethers in Ullmanns Encyclopedia of

Industrial Chemistry, Release 2006, 7th edition)
(4) E. DiAntonio, X. Zhang, J. Conklin, W. Li, T. Drovetskaya, Society of Cosmetic Chemists Annual
Scientific Meeting and Technology Showcase
2007, 55-56
(5) J. Bigorra, E. Graupera, O. Par, Comunicaciones
presentadas a las Jornadas del Comit Espanol
de la Detergencia (2007), 37, 123-131

Citric Acid, 30 %

0.1

Preservatives

q.s.

Evonik Goldschmidt

(6) E. Doelker, Studies in Polymer Science (1990), 8

(Absorbent Polym. Technol.), 125-45
(7) Y. Yuguchi, H. Urakawa, Sh. Kitamura, Sh. Ohno,
K. Kajiwara, Food Hydrocolloids, Vol. 9 no. 3,
173-179 (1995)

Processing:
Creatine is dissolved in water, then Hydroxypropyl Methylcellulose is added and given time to swell under 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

INCI
Sodium Laureth Sulfate, 28 %
Polyglyceryl-3 Caprate
Bis-PEG/PPG-20/20 Dimethicone
Perfume
Water
Hydroxypropyl Methylcellulose
Sodium Cocoamphoacetate
Citric Acid Monohydrate
PEG-200 Hydrogenated Glyceryl
Palmate; PEG-7 Glyceryl Cocoate
Glycol Distearate; Laureth-4;
Cocamidopropyl Betaine
1

Ingredient
TEGOSOFT PC 31
ABIL B 8832 1

weight %
1

TEGOCEL HPM 4000 1

REWOTERIC AM C 1
REWODERM LI S 80 1
TEGO Pearl N 300

30.0
0.5
0.3
0.3
54.1
0.3
10.0
0.5
2.0
2.0

Authors addresses:
* Dr. Sascha Herrwerth
Dr. Hans Henning Wenk
Uta Kortenmeier
Dr. Burghard Grning
Dr. Isabella Ulrich-Brehm
Evonik Goldschmidt GmbH
45127 Essen
Germany
Email: sascha.herrwerth@evonik.com

** Dr. Murat Quadir

Evonik Goldschmidt Corp.
Hopewell, USA
Email: murat.quadir@evonik.com

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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