6-2009

English EditionInternational 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 forPremium Hair Conditioningwith Additional Benefits

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S. Herrwerth**, I. Ulrich-Brehm*, U. Kortemeier*, P. Winter*, M. Ferenz*, B. Grüning*

Silicone Quaternium-22:New Silicone Technology for PremiumHair Conditioning with Additional Benefits

COSMETICSHAIR CARE

� Material

Conditioning agents must adsorb to thesurface of hair in order to perform ef-fectively. The surface of the hair containsprotein structures forming anionic cen-ters. In instances of chemical damage,e.g. by bleaching, dying or perming, thenumber of anionic groups is even high-er due to the generation of oxidized pro-tein groups such as cysteic acid. There-fore cationic molecules are a preferredclass of conditioning agents providingthe required affinity towards hair. Cation-ic conditioners ensure a pronounced con-ditioning effect, especially on damagedareas.The currently available cationic modifiedpolydimethylsiloxanes (Fig. 1) are com-posed either of unmodified linear silox-ane backbones with quaternary groupsat each end or comb-like siloxane chainswith quaternary groups attached to thesilicone chain.The undisturbed silicone backbone of thelinear siloxanes provides a good condi-tioning effect, but each molecule pos-sesses only two cationic groups at thesides which can cling to the hair’s sur-face.In the comb-like cationic siloxanes aswell as in the often used amodime-thicone derivatives, the silicone chainsare disturbed by organic modificationsand thus do not provide a conditioningeffect that is as good as the linear struc-tures. On the other hand, more than twocationic anchor groups can be incorpo-rated into the molecules leading to animproved substantivity.The new patent protected technology ofSilicone Quaternium-22 represents a clear

improvement over the traditional struc-ture. The T-shaped silicone backbone car-ries three quaternary groups, while at thesame time the silicone domain is ex-panded in another dimension (Fig. 2).The length of the uninterrupted siliconechain is a decisive factor contributing to

the exceptional properties of silicone.Correspondingly, the T-shape further im-proves the already excellent characteris-tics of silicone conditioners while at thesame time the increase in cationic cen-ters enhances the adherence to hair andother protein surfaces.

Silicone Quaternium-22 (Trade name: ABIL® T Quat 60) represents amajor step ahead in silicone conditioning technology. Verified by Con-focal Laser Scanning Microscopy, ABIL® T Quat 60 shows excellent sub-

stantivity to hair due to its unique triple cationic charge. In addition to theoutstanding conditioning profile, Silicone Quaternium-22 offers impressiveheat protection properties, an improved color wash-fastness of dyed hair, asuperior skin feel and enhanced foam properties. The excellent process-ability of Silicone Quaternium-22 ultimately turns it into a premium and atthe same time easy to use conditioning agent.

Abstract

Fig. 1 Current cationic modified siloxane technology

The composition of the new SiliconeQuaternium-22 is 65% active SiliconeQuat and 35% PPG-3 Myristyl Ether.The substantivity of Silicone Quaterni-um-22 on hair via delivery out of a con-ditioner rinse was confirmed by Confo-cal Laser Scanning Microscopy (CLSM)(1). For this trial a special derivative ofSilicone Quaternium-22 was preparedand labeled with fluorescein, a fluores-cent marker (Fig. 3). The covalent bondbetween fluorescein and the silicone en-sures a true labeling without signifi-cantly changing the molecular structureand surface interaction.Themodified Silicone Quaternium-22wasincorporated into a conventional condi-tioner rinse formulation (Table 1).After application and rinsing of this testformulation, single hair fibers were ex-amined with CLSM (Fig. 4). The reflec-tion mode (a) shows the topography ofthe hair fiber. The image in fluorescencemode (b) shows the localization of thelabeled material on the same fiber area.This demonstrates that due to its uniquetriple cationic charge, Silicone Quaterni-um-22 is highly substantive to hair outof a conditioner rinse application. Con-versely, untreated hair used as a control,did not display any fluorescence.

� Performance Tests

The multiple performance benefits ofSilicone Quaternium-22 can be demon-strated in various tests.The prototypical conditioning profile wasscored by sensory assessments. To exam-ine the additional benefit of heat pro-tection the thermal stability of hairfibers was examined using DifferentialScanning Calorimetry (DSC). Employingthe use of a spectrophotometer, the ef-ficiency of Silicone Quaternium-22 inimproving color wash fastness was es-tablished by the measurement of colorvalues. Subsequently skin feel and foamquality were evaluated through handwashing trials.

Conditioning Profile viaSensory AssessmentTwo types of cosmetic hair treatmentshave been applied as model systems: astandard shampoo (Table 2) and condi-

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Test material Silicone Quaternium-22with fluorescein marker 1.5%

VARISOFT® 300 Cetrimonium Chloride (CTAC) 1.0% active

TEGINACID® C Ceteareth-25 0.5%

TEGO® Alkanol 16 Cetyl Alcohol 5.0%

Citric acid to pH 4

Water ad. 100.0%

Table 1 Test formulation 1: Conditioner rinse

Fig. 2 T-shaped cationic modified siloxane technology of Silicone Quaternium-22

Fig. 3 Structure of the covalently Fluorescein labeled Silicone Quaternium-22

Fig. 4 Substantivity of Silicone Quaternium-22was proven by Confocal Laser Scan-ning Microscopy with covalently Fluorescein labelded Silicone Quaternium-22

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tioner rinse (Table 3). The test compoundSilicone Quaternium-22 has been incor-porated into these base formulations ina standardized procedure.The evaluation was carried out usingbundled European hair (length = 18 cm,weight = 4 g, supplier: Kerling Interna-tional Haarfabrik GmbH, Germany). Thehair was predamaged by an intensivestandardized bleaching process, whichsimulates typical damage by productscommonly found in the market.The conditioning performance was as-sessed in a sensory hair swatch test by apanel of 10 experts using a standardizedscale of 1–5, with »1« representing poorperformance and »5« characterizing ex-cellent performance. The findings of thesensory assessment for Detangling, WetComb and Wet Feel as the most impor-tant sensory parameters are shown inFig. 5 for a conditioner rinse with vari-ous amounts of Silicone Quaternium-22and in Fig. 6 for a shampoo formulationwith 0.8%weight percent Silicone Quater-nium-22.The conditioner rinse formulation wasbased on Ceteareth-25 and Cetyl Alco-hol, using Cetrimonium Chloride (CTAC)as the organic standard conditioningagent (Table 3). It is common in the Per-sonal Care industry to use silicone deriv-atives in combination with organic quatsbecause of their known synergistic ef-fects. Therefore the testmaterial SiliconeQuaternium-22 was examined in a baseformulation containing CTAC. As can beseen in Fig. 5 thewell known, sound con-ditioning properties of CTAC can be im-proved significantly by the addition ofSilicone Quaternium-22 in low concen-trations.The shampoo formulation was based ona combination of Sodium Laureth Sul-fate and Cocamidopropyl Betaine withCationic Guar as the standard condition-er (Table 2). Due to the pronounced sub-stantivity of this cationic modified, hy-drophilic polymer, Cationic Guar is ap-plied as a so-called »deposition polymer«in shampoo formulations. In this func-tion it supports the activity of siliconebased conditioning agents and increasesthe amount of the silicone based condi-tioning agents that are adsorbed ontothe substrate.

Fig. 6 illustrates the explicit improvementin score for the combination of CationicGuar and Silicone Quaternium-22.The sensory assessment shows that Sili-cone Quaternium-22 exhibits outstand-

ing conditioning properties on hair fromconditioner rinse and shampoo formula-tions. It significantly improves the com-bability of the hair and leads to excellentmanageability.

ABIL® T Quat 60 Silicone Quaternium-22 0.8% versus 0% incontrol formulation

Texapon NSO Sodium Laureth Sulfate 24.0%(28% a.m.)TEGO® Betain F 50 Cocamidopropyl Betaine 6.0%(38% a.m.)

Jaguar C 162 Hydroxypropyl GuarHydroxypropyltrimonium Chloride 0.2%

NaCl 1.2%

ANTIL® 171 PEG-18 Glyceryl

Oleate/Cocoate 2.5%

Citric Acid to pH 5.5

Water ad. 100.0%

Table 2 Test formulation 2: Shampoo

ABIL® T Quat 60 Silicone Quaternium-22 various % active

VARISOFT® 300 Cetrimonium Chloride (CTAC) 1.0% active versus 0%in control formulation

TEGINACID® C Ceteareth-25 0.5%

TEGO® Alkanol 16 Cetyl Alcohol 5.0%

Citric acid to pH 4

Water ad. 100.0%

Table 3 Test formulation 3: Conditioner rinse

uFig. 5 Sensory Assessment of hair tresses. Various % Silicone Quaternium-22 inconditioner rinse formulation. Low concentration of Silicone Quaternium-22 pro-vides outstanding conditioning performance in combination with organic quats

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Heat ProtectionHair is subjected to thermal stress by theapplication of high temperature stylingdevices, commonly used for curling orstraightening. But already the thermalstress caused by blow-drying results inthermal damages of the keratinousstructure. Specialty silicones enable for-mulators to create products that helpprotect hair. This protective effect can beexplained by the low thermal conductivi-ty of silicone derivatives, resulting in re-duced heat flow from the heat source tothe hair fiber.The method of choice in this study to de-termine a compound’s effectiveness inprotecting hair fibers against heat is theanalysis of the fiber’s keratin structurevia Differential Scanning Calorimetry(DSC) (2). The denaturation temperature

delivered by DSC is a significant para-meter in determining the degree of dam-age to the fiber’s keratin structure.The protective effect provided by Sili-cone Quaternium-22 when delivered inthe form of a conditioner rinse was test-ed on damaged bleached hair as well ason undamaged brown hair. In the testsetup flat tresses (European human hair,single bleached) of 0.5 cm width wereused and the hair tresses underwent 4treatment cycles, consisting of shampoo-ing (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 minrinsing with a standard conditioner rinseformulation or a conditioner rinse for-mulation with 1.5% Silicone Quaterni-um-22 (Table 3). After drying at roomtemperature and a defined humidity the

tresses were treated three times for 10seconds each application with a hairstraightener at approx. 180 °C. Subse-quently the contact area of the hairtresses with the straightener was pre-pared for the DSC measurement.The tresses that were not thermally dam-aged and treated with CTAC only wereused as the control. The chart in Fig. 7depicts the results for undamaged brownhair.The decrease in denaturation tempera-ture induced by thermal damage isstrongest with CTAC treated tresses. Theincorporation of Silicone Quaternium-22 makes the hair less susceptible tothermal damage. As can be seen in Fig. 7an improvement in heat protection ofapproximately 40% is achieved on thebrown undamaged hair, clearly indicat-ing how radical damaging effects ofthermal styling tools are reduced.Similarly, by incorporating Silicone Quater-nium-22 in the test formulation an ap-proximately 40% increase in heat pro-tection was observed in experiments us-ing damaged bleached hair tresses. Sili-cone Quaternium-22 effectively providesdefense against the intense heat that isgenerated by modern appliances for dif-ferent hair types.

Color Protection / Improved ColorWashFastnessHair coloring became very popular in thelast decade and therefore one of the keyareas in the hair care market is color pro-tection. It is no surprise that most manu-facturers are developing products thatare tailored for the hair color market.No single source causes hair color fad-ing. However, the application of sham-poo inevitably leads to the continualfading of color and a diminished bril-liance of the hair. This effect is one of thereasons why it is highly desirable forshampoo formulations to contain ingre-dients which counteract this phenome-non and effectively improve the colorwash fastness.Themeasurement of the color wash fast-ness can be done by using a spectropho-tometer. For this study a CIE-L*a*b* Colori-meter (Comission Internationale d’Eclarage,international committee of illumination)was used (CIE-L*a*b* Colorimeter, Dr.

uFig. 6 Sensory assessment of hair tresses. 0.8% Silicone Quaternium-22 in a sham-poo formulation. Silicone Quaternium-22 boosts the conditioning performancesignificantly

uFig. 7 Thermal damaging of undamaged brown hair tresses. 1% Silicone Quaterni-um-22 in conditioner application provides about 40% heat protection

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Lange, Duesseldorf, Germany).In the operating procedure flat gluedtresses of single bleached European hu-man hair, 4 g weight, 16 cm length and2 cm width, were used. A demipermanenthair dye (»L’Oreal Garnier Movida Nr. 27Granatrot«) was applied according to theoperating guidelines delivered with theproduct. After drying aminimumof 24 h,the initial color value was determinedby 12 single measurements of the CIE-L*a*b* color values. The tresses were treat-ed with the shampoo test formulations(Table 2) according to a defined wash-ing procedure of fifteen cycles. Afterstandardized drying, the color values weremeasured after one, ten and 15 washingcycles and the »delta-E-values« (∆E) werecalculated as described in the literature(3).The lower the difference in the color val-ues before and after the shampoo treat-ments, the better the wash fastnessproperty of the tested formulation. Thecolor variations are expressed as the in-tegral difference ∆E, based on changesof brightness (L*), red-green (a*) and blue-yellow (b*) shift.A concentration of 0.8% Silicone Quater-nium-22 was used in the test shampooformulation (Table 2) and 0% SiliconeQuaternium-22 in the control formula-tion. The efficiency of Silicone Quaterni-um-22 for color protection is demon-strated in Fig. 8, where the ∆E values af-ter a single shampoo treatment, as wellas after 10 and 15 shampoo treatmentsare represented.Immediately after one single washingthe color protection afforded by SiliconeQuaternium-22 becomes apparent. Witheach subsequent washing cycle the shield-ing effect of the new T-shaped SiliconeQuaternium-22 conditioning agent be-comes more pronounced.This demonstrated color protection fordyed hair is decidedly attractive as it is aconsumer perceivable property. More andmore, consumers now prefer their haircare products to provide a color protec-tion benefit. Approximately 20% of thehair care products now on the marketclaim color protection and about 13%heat protection (4). Using Silicone Quater-nium-22 enables the formulator to dif-ferentiate hair care products in an at-tractive way, namely with the proven

claim for longer lasting color retentionand heat protection.

Skin Feel and FoamConsumers will value heat protection inthe long term and color retention in theshort term, but definitely will desirecertain sensorial benefits immediately.From the consumer’s perspective, thefoam properties as well as skin and hairconditioning are aspects of particularimportance which are observed immedi-ately.In particular sensory methods are usefulin determining the influence of a certainingredient on skin feel and foam proper-ties. When performed by trained person-nel, sensory use data will closely parallel

consumer preferences.The impressive skin conditioning benefitsof Silicone Quaternium-22 are demon-strated in a sensory hand wash test con-ducted by a trained group of 10 panelistsin a standardized washing procedure. Theeffect of the incorporation of 0.5% Sili-cone Quaternium-22 was evaluated andhas been represented graphically in Fig. 9.In skin cleansing formulations SiliconeQuaternium-22 is able to provide a re-markable improvement of wet and dryskin feel. Both during and after-use, theskin feels soft and smooth with a pleasantperception of moisturization. Further-more the foam properties are enhancedproviding the formulator a more rich anddenser foam with better stability.The results of the sensory hand wash test

Fig. 8 Color Fading – 0.8% Silicone Quaternium-22 provides improved color washfastness 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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confirm the striking improvements infoam properties as well as in skin feelfacilitated by the addition of SiliconeQuaternium-22 to the formulation.The formulation of the sensory handwash test is described in Table 4.

� Advantages in Processing

Silicone Quaternium-22 can be used ver-satile in various rinse-off applicationse.g. conditioning shampoos, hair rinses,balms, styling products, body washes andleave-in formulations. Silicone Quater-nium-22 is soluble in surfactant systemsand ethanol and therefore highly suit-able for clear formulations. At room tem-perature Silicone Quaternium-22 is a clearand easy to process liquid.The lactate based counter ion chemistrymakes it also applicable at low pH with-out the associated odor problems.In general a decrease in viscosity of sur-factant formulations is commonly asso-ciated with the use of silicone derivatives.This phenomenon is typically counter-acted by increasing the amount of thick-ener in order to maintain the desired vis-cosity.Since this new technology shows a muchless pronounced influence on viscosity,when using Silicone Quaternium-22 theamount of thickener in a formulationcan be reduced significantly. This in turnleads to substantial cost savings for theformulator.Fig. 10 shows an example of a shampooformulation containing 9% SLES, 3%CAPB, 0.3% HP Guar HP Chloride and0.7% NaCl. At the active matter contentof 0.5% cationic modified siloxane, theformulation with Silicone Quaternium-22 requires 28% less hydrophilic thick-ener (ANTIL® 171, PEG-18 Glyceryl Oleate/Cocoate) to achieve the desired viscosi-ty of 4000 mPas compared to the for-mula with a linear cationic modifiedsiloxane.

� Conclusion

Silicone Quaternium-22 represents amajor step forward in silicone condition-ing technology. Due to the unique triplecationic charge it shows excellent sub-

Fig. 10 Required thickener concentration (ANTIL® 171, PEG-18 Glyceryl Oleate/ Cocoate) for a viscosity of 4000 mPas in a shampoo formulation

ABIL® T Quat 60 Silicone Quaternium-22 0.5% versus 0% in control formulation

Texapon NSO Sodium Laureth Sulfate 32.0%(28% a.m.)

TEGO® Betain F 50 Cocoamidopropyl Betaine 8.0%(38% a.m.)

NaCl 2.0%

Water ad. 100.0%

Table 4 Test formulation 4: Sensory hand wash test

Ingredient INCI %

Sodium Laureth Sulfate, 28% 32.0

VARISOFT® PATC* Palmitamidopropyltrimonium Chloride 1.5

ANTIL® 200* PEG-200 Hydrogenated Glyceryl Palmate; 1.9PEG-7 Glyceryl Cocoate

ABIL® T Quat 60* Silicone Quaternium-22 1.5

Perfume 0.25

Water 56.05

Polymer JR 400** Polyquaternium-10 0.3

TEGO® Betain F 50* Cocamidopropyl Betaine 6.5

Preservative q.s.* Evonik Goldschmidt ** Amerchol

Manufacture:Dissolve the Polyquaternium-10 in water and let it swell. Dissolve the ingredients in the given order inSLES. Then add water/PQ-10 and the Betain.

Formulation 1 Conditioning shampoo for coarse and damaged hair with color pro-tecting properties

� Guidelines Formulations

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stantivity to hair as confirmed by CLSM.In addition to the outstanding condi-tioning profile, Silicone Quaternium-22offers impressive heat protection prop-erties, improved color protection fordyed hair, superior skin feel and en-hanced foam properties. Because of aless pronounced thinning effect in sur-factant formulations cost savings can berealized. Highly suitable for clear formu-lations Silicone Quaternium-22 can beincorporated into shampoo and condi-tioner rinse applications likewise. Thelactate based counter ion chemistrymakes it also applicable at low pH with-out the associated odor problems. The excellent processability of SiliconeQuaternium-22 ultimately makes it intoa premium and at the same time easy touse conditioning agent.

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. Har-tung, 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-BrehmUta KortemeierPatrick Winter

Dr. Michael FerenzDr. Burghard Grüning

Evonik Goldschmidt GmbHGoldschmidtstrasse 100

45127 EssenGermany

** Corresponding author:Email: sascha.herrwerth@evonik.com

�

Ingredient INCI %

Water 90.2

VARISOFT® EQ 65* Distearyl Dimonium Chloride, 2.0Cetearyl Alcohol

VARISOFT® BT 85 Pellets* Behentrimonium Chloride 2.0

ABIL® T Quat 60* Silicone Quaternium-22 0.8

TEGO® Alkanol 1618* Cetearyl Alcohol 5.0

Preservative, Perfume q.s.

* Evonik Goldschmidt

Manufacture:Add all ingredients to water and heat to 75 °C with adequate mixing. Homogenize at 75 °C andcool down while stirring. Add perfume and preservative at a temperature below 40 °C. Homogenize asecond time at room temperature.

Formulation 2 Conditioning hair rinse with heat protecting properties

Ingredient INCI %

ABIL® Quat 60* Silicone Quaternium-22 0.5

TAGAT® CH 40* PEG-40 Hydrogenated Castor Oil 0.5

Perfume 0.3

TEGO® Betain 810* Capryl/Capramidopropyl Betain 2.0

Water 940

TEGO® Cosmo C 100* Creatine 0.5

TEGOCEL® HPM 50* Hydroxypropyl Methylcellulose 0.3

VARISOFT® 300* Cetrimonium Chloride 1.3

LACTIL®* Sodium Lactate; Sodium PCA, Glycine; 0.5Fructose; Urea; Niacinamide; Inositol;Sodium Benzoate; Lactic Acid

Citric Acid, 30% 0.1

Preservative q.s.* Evonik Goldschmidt

Manufacture:Dissolve TEGO® Cosmo C 100 in water, then the Cellulose and let it swell with agitation. Mix the ingre-dients in the given order. Adjust the pH value to approximately 4.5.

Formulation 3 Clear leave-in conditioning foam with heat protecting properties