Silicone Quaternium-22: New Silicone

6-2009
English Edition
International Journal for Applied Science
• Personal Care • Detergents • Specialties
S. Herrwerth, I. Ulrich-Brehm,
U. Kortemeier, P. Winter,
M. Ferenz, B. Grüning:
Silicone Quaternium-22:
New Silicone Technology for
Premium Hair Conditioning
with Additional Benefits
CO S M ET I C S
HAIR CARE
S. Herrwerth**, I. Ulrich-Brehm*, U. Kortemeier*, P. Winter*, M. Ferenz*, B. Grüning*
Silicone Quaternium-22:
New Silicone Technology for Premium
Hair Conditioning with Additional Benefits
Material
Conditioning agents must adsorb to the
surface of hair in order to perform effectively. The surface of the hair contains
protein structures forming anionic centers. In instances of chemical damage,
e.g. by bleaching, dying or perming, the
number of anionic groups is even higher due to the generation of oxidized protein groups such as cysteic acid. Therefore cationic molecules are a preferred
class of conditioning agents providing
the required affinity towards hair. Cationic conditioners ensure a pronounced conditioning effect, especially on damaged
areas.
The currently available cationic modified
polydimethylsiloxanes (Fig. 1) are composed either of unmodified linear siloxane backbones with quaternary groups
at each end or comb-like siloxane chains
with quaternary groups attached to the
silicone chain.
The undisturbed silicone backbone of the
linear siloxanes provides a good conditioning effect, but each molecule possesses only two cationic groups at the
sides which can cling to the hair’s surface.
In the comb-like cationic siloxanes as
well as in the often used amodimethicone derivatives, the silicone chains
are disturbed by organic modifications
and thus do not provide a conditioning
effect that is as good as the linear structures. On the other hand, more than two
cationic anchor groups can be incorporated into the molecules leading to an
improved substantivity.
The new patent protected technology of
Silicone Quaternium-22 represents a clear
SOFW-Journal | 135 | 6-2009
Abstract
ilicone Quaternium-22 (Trade name: ABIL® T Quat 60) represents a
major step ahead in silicone conditioning technology. Verified by Confocal Laser Scanning Microscopy, ABIL® T Quat 60 shows excellent substantivity to hair due to its unique triple cationic charge. In addition to the
outstanding conditioning profile, Silicone Quaternium-22 offers impressive
heat protection properties, an improved color wash-fastness of dyed hair, a
superior skin feel and enhanced foam properties. The excellent processability of Silicone Quaternium-22 ultimately turns it into a premium and at
the same time easy to use conditioning agent.
S
improvement over the traditional structure. The T-shaped silicone backbone carries three quaternary groups, while at the
same time the silicone domain is expanded in another dimension (Fig. 2).
The length of the uninterrupted silicone
chain is a decisive factor contributing to
the exceptional properties of silicone.
Correspondingly, the T-shape further improves the already excellent characteristics of silicone conditioners while at the
same time the increase in cationic centers enhances the adherence to hair and
other protein surfaces.
Fig. 1 Current cationic modified siloxane technology
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The composition of the new Silicone
Quaternium-22 is 65% active Silicone
Quat and 35% PPG-3 Myristyl Ether.
The substantivity of Silicone Quaternium-22 on hair via delivery out of a conditioner rinse was confirmed by Confocal Laser Scanning Microscopy (CLSM)
(1). For this trial a special derivative of
Silicone Quaternium-22 was prepared
and labeled with fluorescein, a fluorescent marker (Fig. 3). The covalent bond
between fluorescein and the silicone ensures a true labeling without significantly changing the molecular structure
and surface interaction.
The modified Silicone Quaternium-22 was
incorporated into a conventional conditioner rinse formulation (Table 1).
After application and rinsing of this test
formulation, single hair fibers were examined with CLSM (Fig. 4). The reflection mode (a) shows the topography of
the hair fiber. The image in fluorescence
mode (b) shows the localization of the
labeled material on the same fiber area.
This demonstrates that due to its unique
triple cationic charge, Silicone Quaternium-22 is highly substantive to hair out
of a conditioner rinse application. Conversely, untreated hair used as a control,
did not display any fluorescence.
Performance Tests
The multiple performance benefits of
Silicone Quaternium-22 can be demonstrated in various tests.
The prototypical conditioning profile was
scored by sensory assessments. To examine the additional benefit of heat protection the thermal stability of hair
fibers was examined using Differential
Scanning Calorimetry (DSC). Employing
the use of a spectrophotometer, the efficiency of Silicone Quaternium-22 in
improving color wash fastness was established by the measurement of color
values. Subsequently skin feel and foam
quality were evaluated through hand
washing trials.
Conditioning Profile via
Sensory Assessment
Two types of cosmetic hair treatments
have been applied as model systems: a
standard shampoo (Table 2) and condi-
2
Fig. 2 T-shaped cationic modified siloxane technology of Silicone Quaternium-22
Fig. 3 Structure of the covalently Fluorescein labeled Silicone Quaternium-22
Test material
VARISOFT® 300
TEGINACID® C
TEGO® Alkanol 16
Citric acid
Water
Silicone Quaternium-22
with fluorescein marker
Cetrimonium Chloride (CTAC)
Ceteareth-25
Cetyl Alcohol
1.5%
1.0% active
0.5%
5.0%
to pH 4
ad. 100.0%
Table 1 Test formulation 1: Conditioner rinse
Fig. 4 Substantivity of Silicone Quaternium-22 was proven by Confocal Laser Scanning Microscopy with covalently Fluorescein labelded Silicone Quaternium-22
SOFW-Journal | 135 | 6-2009
CO S M ET I C S
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tioner rinse (Table 3). The test compound
Silicone Quaternium-22 has been incorporated into these base formulations in
a standardized procedure.
The evaluation was carried out using
bundled European hair (length = 18 cm,
weight = 4 g, supplier: Kerling International Haarfabrik GmbH, Germany). The
hair was predamaged by an intensive
standardized bleaching process, which
simulates typical damage by products
commonly found in the market.
The conditioning performance was assessed in a sensory hair swatch test by a
panel of 10 experts using a standardized
scale of 1–5, with »1« representing poor
performance and »5« characterizing excellent performance. The findings of the
sensory assessment for Detangling, Wet
Comb and Wet Feel as the most important sensory parameters are shown in
Fig. 5 for a conditioner rinse with various amounts of Silicone Quaternium-22
and in Fig. 6 for a shampoo formulation
with 0.8% weight percent Silicone Quaternium-22.
The conditioner rinse formulation was
based on Ceteareth-25 and Cetyl Alcohol, using Cetrimonium Chloride (CTAC)
as the organic standard conditioning
agent (Table 3). It is common in the Personal Care industry to use silicone derivatives in combination with organic quats
because of their known synergistic effects. Therefore the test material Silicone
Quaternium-22 was examined in a base
formulation containing CTAC. As can be
seen in Fig. 5 the well known, sound conditioning properties of CTAC can be improved significantly by the addition of
Silicone Quaternium-22 in low concentrations.
The shampoo formulation was based on
a combination of Sodium Laureth Sulfate and Cocamidopropyl Betaine with
Cationic Guar as the standard conditioner (Table 2). Due to the pronounced substantivity of this cationic modified, hydrophilic polymer, Cationic Guar is applied as a so-called »deposition polymer«
in shampoo formulations. In this function it supports the activity of silicone
based conditioning agents and increases
the amount of the silicone based conditioning agents that are adsorbed onto
the substrate.
SOFW-Journal | 135 | 6-2009
ABIL® T Quat 60
Silicone Quaternium-22
Texapon NSO
(28% a.m.)
TEGO® Betain F 50
(38% a.m.)
Jaguar C 162
Sodium Laureth Sulfate
NaCl
ANTIL® 171
Oleate/Cocoate
Citric Acid
Water
Cocamidopropyl Betaine
Hydroxypropyl Guar
Hydroxypropyltrimonium Chloride
0.8% versus 0% in
control formulation
24.0%
6.0%
0.2%
1.2%
PEG-18 Glyceryl
2.5%
to pH 5.5
ad. 100.0%
Table 2 Test formulation 2: Shampoo
ABIL® T Quat 60
VARISOFT® 300
Silicone Quaternium-22
Cetrimonium Chloride (CTAC)
TEGINACID® C
TEGO® Alkanol 16
Citric acid
Water
Ceteareth-25
Cetyl Alcohol
various % active
1.0% active versus 0%
in control formulation
0.5%
5.0%
to pH 4
ad. 100.0%
Table 3 Test formulation 3: Conditioner rinse
Fig. 6 illustrates the explicit improvement
in score for the combination of Cationic
Guar and Silicone Quaternium-22.
The sensory assessment shows that Silicone Quaternium-22 exhibits outstand-
ing conditioning properties on hair from
conditioner rinse and shampoo formulations. It significantly improves the combability of the hair and leads to excellent
manageability.
uFig. 5 Sensory Assessment of hair tresses. Various % Silicone Quaternium-22 in
conditioner rinse formulation. Low concentration of Silicone Quaternium-22 provides outstanding conditioning performance in combination with organic quats
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uFig. 6 Sensory assessment of hair tresses. 0.8% Silicone Quaternium-22 in a shampoo formulation. Silicone Quaternium-22 boosts the conditioning performance
significantly
Heat Protection
Hair is subjected to thermal stress by the
application of high temperature styling
devices, commonly used for curling or
straightening. But already the thermal
stress caused by blow-drying results in
thermal damages of the keratinous
structure. Specialty silicones enable formulators to create products that help
protect hair. This protective effect can be
explained by the low thermal conductivity of silicone derivatives, resulting in reduced heat flow from the heat source to
the hair fiber.
The method of choice in this study to determine a compound’s effectiveness in
protecting hair fibers against heat is the
analysis of the fiber’s keratin structure
via Differential Scanning Calorimetry
(DSC) (2). The denaturation temperature
delivered by DSC is a significant parameter in determining the degree of damage to the fiber’s keratin structure.
The protective effect provided by Silicone Quaternium-22 when delivered in
the form of a conditioner rinse was tested on damaged bleached hair as well as
on undamaged brown hair. In the test
setup flat tresses (European human hair,
single bleached) of 0.5 cm width were
used and the hair tresses underwent 4
treatment cycles, consisting of shampooing (0.5 g / tress for 1 min, 1 min at rest,
1 min rinsing) followed by conditioning
(0.5 g / tress for 1 min, 1 min at rest, 1 min
rinsing with a standard conditioner rinse
formulation or a conditioner rinse formulation with 1.5% Silicone Quaternium-22 (Table 3). After drying at room
temperature and a defined humidity the
uFig. 7 Thermal damaging of undamaged brown hair tresses. 1% Silicone Quaternium-22 in conditioner application provides about 40% heat protection
4
tresses were treated three times for 10
seconds each application with a hair
straightener at approx. 180 °C. Subsequently the contact area of the hair
tresses with the straightener was prepared for the DSC measurement.
The tresses that were not thermally damaged and treated with CTAC only were
used as the control. The chart in Fig. 7
depicts the results for undamaged brown
hair.
The decrease in denaturation temperature induced by thermal damage is
strongest with CTAC treated tresses. The
incorporation of Silicone Quaternium22 makes the hair less susceptible to
thermal damage. As can be seen in Fig. 7
an improvement in heat protection of
approximately 40% is achieved on the
brown undamaged hair, clearly indicating how radical damaging effects of
thermal styling tools are reduced.
Similarly, by incorporating Silicone Quaternium-22 in the test formulation an approximately 40% increase in heat protection was observed in experiments using damaged bleached hair tresses. Silicone Quaternium-22 effectively provides
defense against the intense heat that is
generated by modern appliances for different hair types.
Color Protection / Improved Color Wash
Fastness
Hair coloring became very popular in the
last decade and therefore one of the key
areas in the hair care market is color protection. It is no surprise that most manufacturers are developing products that
are tailored for the hair color market.
No single source causes hair color fading. However, the application of shampoo inevitably leads to the continual
fading of color and a diminished brilliance of the hair. This effect is one of the
reasons why it is highly desirable for
shampoo formulations to contain ingredients which counteract this phenomenon and effectively improve the color
wash fastness.
The measurement of the color wash fastness can be done by using a spectrophotometer. For this study a CIE-L*a*b* Colorimeter (Comission Internationale d’Eclarage,
international committee of illumination)
was used (CIE-L*a*b* Colorimeter, Dr.
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CO S M ET I C S
HAIR CARE
Lange, Duesseldorf, Germany).
In the operating procedure flat glued
tresses of single bleached European human hair, 4 g weight, 16 cm length and
2 cm width, were used. A demipermanent
hair dye (»L’Oreal Garnier Movida Nr. 27
Granatrot«) was applied according to the
operating guidelines delivered with the
product. After drying a minimum of 24 h,
the initial color value was determined
by 12 single measurements of the CIEL*a*b* color values. The tresses were treated with the shampoo test formulations
(Table 2) according to a defined washing procedure of fifteen cycles. After
standardized drying, the color values were
measured after one, ten and 15 washing
cycles and the »delta-E-values« (∆E) were
calculated as described in the literature
(3).
The lower the difference in the color values before and after the shampoo treatments, the better the wash fastness
property of the tested formulation. The
color variations are expressed as the integral difference ∆E, based on changes
of brightness (L*), red-green (a*) and blueyellow (b*) shift.
A concentration of 0.8% Silicone Quaternium-22 was used in the test shampoo
formulation (Table 2) and 0% Silicone
Quaternium-22 in the control formulation. The efficiency of Silicone Quaternium-22 for color protection is demonstrated in Fig. 8, where the ∆E values after a single shampoo treatment, as well
as after 10 and 15 shampoo treatments
are represented.
Immediately after one single washing
the color protection afforded by Silicone
Quaternium-22 becomes apparent. With
each subsequent washing cycle the shielding effect of the new T-shaped Silicone
Quaternium-22 conditioning agent becomes more pronounced.
This demonstrated color protection for
dyed hair is decidedly attractive as it is a
consumer perceivable property. More and
more, consumers now prefer their hair
care products to provide a color protection benefit. Approximately 20% of the
hair care products now on the market
claim color protection and about 13%
heat protection (4). Using Silicone Quaternium-22 enables the formulator to differentiate hair care products in an attractive way, namely with the proven
SOFW-Journal | 135 | 6-2009
claim for longer lasting color retention
and heat protection.
Skin Feel and Foam
Consumers will value heat protection in
the long term and color retention in the
short term, but definitely will desire
certain sensorial benefits immediately.
From the consumer’s perspective, the
foam properties as well as skin and hair
conditioning are aspects of particular
importance which are observed immediately.
In particular sensory methods are useful
in determining the influence of a certain
ingredient on skin feel and foam properties. When performed by trained personnel, sensory use data will closely parallel
consumer preferences.
The impressive skin conditioning benefits
of Silicone Quaternium-22 are demonstrated in a sensory hand wash test conducted by a trained group of 10 panelists
in a standardized washing procedure. The
effect of the incorporation of 0.5% Silicone Quaternium-22 was evaluated and
has been represented graphically in Fig. 9.
In skin cleansing formulations Silicone
Quaternium-22 is able to provide a remarkable improvement of wet and dry
skin feel. Both during and after-use, the
skin feels soft and smooth with a pleasant
perception of moisturization. Furthermore the foam properties are enhanced
providing the formulator a more rich and
denser foam with better stability.
The results of the sensory hand wash test
∆
Fig. 8 Color Fading – 0.8% Silicone Quaternium-22 provides improved color wash
fastness in a shampoo formulation (Table 2)
Fig. 9 Sensory hand wash test results judging foam and skin feel ba a scale
(1-5; 5 = best)
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CO S M ET I C S
HAIR CARE
confirm the striking improvements in
foam properties as well as in skin feel
facilitated by the addition of Silicone
Quaternium-22 to the formulation.
The formulation of the sensory hand
wash test is described in Table 4.
Advantages in Processing
Silicone Quaternium-22 can be used versatile in various rinse-off applications
e.g. conditioning shampoos, hair rinses,
balms, styling products, body washes and
leave-in formulations. Silicone Quaternium-22 is soluble in surfactant systems
and ethanol and therefore highly suitable for clear formulations. At room temperature Silicone Quaternium-22 is a clear
and easy to process liquid.
The lactate based counter ion chemistry
makes it also applicable at low pH without the associated odor problems.
In general a decrease in viscosity of surfactant formulations is commonly associated with the use of silicone derivatives.
This phenomenon is typically counteracted by increasing the amount of thickener in order to maintain the desired viscosity.
Since this new technology shows a much
less pronounced influence on viscosity,
when using Silicone Quaternium-22 the
amount of thickener in a formulation
can be reduced significantly. This in turn
leads to substantial cost savings for the
formulator.
Fig. 10 shows an example of a shampoo
formulation containing 9% SLES, 3%
CAPB, 0.3% HP Guar HP Chloride and
0.7% NaCl. At the active matter content
of 0.5% cationic modified siloxane, the
formulation with Silicone Quaternium22 requires 28% less hydrophilic thickener (ANTIL® 171, PEG-18 Glyceryl Oleate/
Cocoate) to achieve the desired viscosity of 4000 mPas compared to the formula with a linear cationic modified
siloxane.
ABIL® T Quat 60
Silicone Quaternium-22
Texapon NSO
(28% a.m.)
TEGO® Betain F 50
(38% a.m.)
NaCl
Water
Sodium Laureth Sulfate
Silicone Quaternium-22 represents a
major step forward in silicone conditioning technology. Due to the unique triple
cationic charge it shows excellent sub-
6
Cocoamidopropyl Betaine
8.0%
2.0%
ad. 100.0%
Table 4 Test formulation 4: Sensory hand wash test
Fig. 10 Required thickener concentration (ANTIL® 171, PEG-18 Glyceryl Oleate/
Cocoate) for a viscosity of 4000 mPas in a shampoo formulation
Guidelines Formulations
Ingredient
INCI
Sodium Laureth Sulfate, 28%
VARISOFT® PATC*
ANTIL® 200*
ABIL® T Quat 60*
Perfume
Water
Polymer JR 400**
TEGO® Betain F 50*
Preservative
*
Conclusion
0.5% versus 0% in
control formulation
32.0%
Evonik Goldschmidt
Palmitamidopropyltrimonium Chloride
PEG-200 Hydrogenated Glyceryl Palmate;
PEG-7 Glyceryl Cocoate
Silicone Quaternium-22
Polyquaternium-10
Cocamidopropyl Betaine
**
%
32.0
1.5
1.9
1.5
0.25
56.05
0.3
6.5
q.s.
Amerchol
Manufacture:
Dissolve the Polyquaternium-10 in water and let it swell. Dissolve the ingredients in the given order in
SLES. Then add water/PQ-10 and the Betain.
Formulation 1 Conditioning shampoo for coarse and damaged hair with color protecting properties
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CO S M ET I C S
HAIR CARE
Ingredient
INCI
Water
VARISOFT® EQ 65*
VARISOFT® BT 85 Pellets*
ABIL® T Quat 60*
TEGO® Alkanol 1618*
Preservative, Perfume
*
Distearyl Dimonium Chloride,
Cetearyl Alcohol
Behentrimonium Chloride
Silicone Quaternium-22
Cetearyl Alcohol
%
90.2
2.0
2.0
0.8
5.0
q.s.
Evonik Goldschmidt
Manufacture:
Add all ingredients to water and heat to 75 °C with adequate mixing. Homogenize at 75 °C and
cool down while stirring. Add perfume and preservative at a temperature below 40 °C. Homogenize a
second time at room temperature.
Formulation 2 Conditioning hair rinse with heat protecting properties
Ingredient
INCI
*
ABIL® Quat 60
TAGAT® CH 40*
Perfume
TEGO® Betain 810*
Water
TEGO® Cosmo C 100*
TEGOCEL® HPM 50*
VARISOFT® 300*
LACTIL®*
Citric Acid, 30%
Preservative
*
Silicone Quaternium-22
PEG-40 Hydrogenated Castor Oil
Capryl/Capramidopropyl Betain
Creatine
Hydroxypropyl Methylcellulose
Cetrimonium Chloride
Sodium Lactate; Sodium PCA, Glycine;
Fructose; Urea; Niacinamide; Inositol;
Sodium Benzoate; Lactic Acid
stantivity to hair as confirmed by CLSM.
In addition to the outstanding conditioning profile, Silicone Quaternium-22
offers impressive heat protection properties, improved color protection for
dyed hair, superior skin feel and enhanced foam properties. Because of a
less pronounced thinning effect in surfactant formulations cost savings can be
realized. Highly suitable for clear formulations Silicone Quaternium-22 can be
incorporated into shampoo and conditioner rinse applications likewise. The
lactate based counter ion chemistry
makes it also applicable at low pH without the associated odor problems.
The excellent processability of Silicone
Quaternium-22 ultimately makes it into
a premium and at the same time easy to
use conditioning agent.
%
0.5
0.5
0.3
2.0
940
0.5
0.3
1.3
0.5
0.1
q.s.
Evonik Goldschmidt
Manufacture:
Dissolve TEGO® Cosmo C 100 in water, then the Cellulose and let it swell with agitation. Mix the ingredients in the given order. Adjust the pH value to approximately 4.5.
Formulation 3 Clear leave-in conditioning foam with heat protecting properties
References
(1) M. Minsky, Scanning 10, 128-138 (1988)
(2) F.-J. Wortmann, C. Springob, G. Sendelbach, J.
Cosmet. Sci., 53, 219-228 (July/August 2002)
(3) S. Herrwerth, H. Leidreiter, U. Kortemeier, C. Hartung, B. Grüning, Cosmetics & Toiletries, 123,
101-110, 2008
(4) S. Marchioretto, S. van Doorn, Happi, 54-58,
February 2009
* Author’s address:
Dr. Sascha Herrwerth
Dr. Isabella Ulrich-Brehm
Uta Kortemeier
Patrick Winter
Dr. Michael Ferenz
Dr. Burghard Grüning
Evonik Goldschmidt GmbH
Goldschmidtstrasse 100
45127 Essen
Germany
** Corresponding author:
Email: [email protected]
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