FR2709954A1 - Cosmetic compositions containing a polysiloxane-polyoxyalkylene linear block copolymer and a cationic polymer, and their uses - Google Patents

Abstract

The invention relates to cosmetic compositions comprising, in a cosmeticaly acceptable medium, at least one cationic polymer displaying fixing power and of conductivity less than 1 mohm<-1> cm<-1> and at least one polysiloxane-polyoxyalkylene linear block copolymer, as well as to their uses. These compositions, besides their properties of disentangling hair and imparting softness and sheen thereto, display, in addition, good fixing power.

Description

COSMETIC COMPOSITIONS CONTAINING A BLOCK COPOLYMER
LINEAR POLYSILOXANE-POLYOXYALKYLENE AND A POLYMER
CATIONIC. AND ZURS USES.

The present invention relates to novel cosmetic compositions containing at least one linear polysiloxane-polyoxyallylene block copolymer and. on the other hand at least one cationic polymer with fixing power and with a conductivity less than or equal to 1 mohm-1 cm-1, as well as their uses.

In the context of the present application, the term “cosmetic compositions for maintaining the hairstyle” will be understood to mean any composition having the object of temporarily fixing the shape of the coirrre such as, for example, lacquers, styling compositions, foams, coiflåge gels and sprays. The term “fixing power” of the composition will denote the ability of the latter to give the hair a cohesion such that the initial shaping of the hairstyle is retained.

The use of silicone derivatives in combination with catlonlques polymers with fixing power is widely known in the preparation of cosmetic compositions, in particular for maintaining the hairstyle. It has been observed that these silicone derivatives markedly improve the disentangling properties. of softness and shine of the hair treated using these compositions. Conversely, they are not favorable to the fixing power of the latter, which is provided by the polymer resin alone.

Also known in the prior art is application EP 492 657 A1 which describes the use of linear polysiloxane-polyoxyalkylene block copolymers in cosmetic compositions useful for skin care and hair care. According to this application, the use of these copolymers alone or with an agent for treating the skin or the hair makes it possible to obtain improved properties of gloss, durability and / or softness of the formulation. These copolymers are generally described as having, compared with the silicone compounds of the prior art used in these compositions, properties of the same nature but of a substantially higher degree.

Those skilled in the art should therefore expect that the copolymers described in the aforementioned European patent application will further aggravate the deterioration of the fixing power. although otherwise he expects an improvement in disentangling characteristics. shine and softness. This point is not contradicted by reading the examples of this application, in particular by example 19, the reproduction of which leads to a composition having a very low fixing power which is incompatible with a marketing of the latter.

In this application, it is also described to associate the linear block copolymers polysiloxane-polyoxyalkylene with any cationic polymer in general. but without any particular advantage likely to result from this association being mentioned.

Now, the Applicant has now surprisingly discovered that the combination of certain cationic polymers with linear polysiloxane-polyoryalkylene block copolymers made it possible to obtain compositions which confer good cosmetic properties of disentangling, softness and shine while providing power. fixing substantially at the same level as that of the cationic polymer alone, and in any case higher than that of the combination of the cationic polymer and the silicone derivatives of the prior art.

The subject of the invention is therefore a cosmetic composition comprising, in a cosmetically acceptable medium, at least one linear polysiloxane-polyoxyalkylene block copolymer and at least one cationic polymer with fixing power and with a conductivity of less than or equal to 1 mohm-1 cm-1.

Indeed, 11 has been found by the Applicant that cationic polymers with a conductivity greater than 1 mohm-1cm-1, either do not have a fixing power, or have a fixing power which is greatly reduced by association with the silicone derivative. used in the context of the invention.

Another subject of the invention consists of the use of this composition for maintaining the hairstyle, treating or washing the hair or any other keratin material.

The conductivity of the polymers is measured from an aqueous polymer solution containing 1% of active material with a Pbilips PW 9501 conductivity meter.
Cell PW 9510 at 21 C. the cationic polymers which can be used according to the present invention are firstly chosen from polymers comprising primary, secondary, tertiary and / or quaternary amine groups forming part of the polymer chain or directly linked to it, and having a molecular weight of between 500 and approximately 5,000,000 and preferably between 1,000 and 3,000,000, it being understood that these polymers dolvent have a conductivity less than or equal to 1 mohm-1cm-1.

dans lesquelles:
R3 désigne H ou CH3;
A est un groupe alkyle linaire ou ramifie de 1 à 6 atomes de carbone ou un groupe hydroxyalkyle de 1 à 4 atomes de carbone;
R4,R5,R6, identiques ou diSerents, représentent un groupe aikyle ayant de 1 à 18 atomes de carbone ou un radical benzyle; R1 et R2 représentent hydrogène ou un groupe allyle ayant de 1 à 6 atomes de carbone;
X désigne un anion méthosullate ou un halogenure tel que chlorure ou bromure.Among these polymers, there may be mentioned more particularly the following cattonic polymers:
(1) homopolymers or copolymers derived from acrylic or methacrylic esters or amides and comprising at least one of the units of the following formulas:

in which:
R3 denotes H or CH3;
A is a linear or branched alkyl group of 1 to 6 carbon atoms or a hydroxyalkyl group of 1 to 4 carbon atoms;
R4, R5, R6, identical or different, represent an alkyl group having from 1 to 18 carbon atoms or a benzyl radical; R1 and R2 represent hydrogen or an allyl group having 1 to 6 carbon atoms;
X denotes a methosullate anion or a halide such as chloride or bromide.

The copolymers also contain one or more units derived from comonomers which can be chosen from the family of acrylamides, methacrylamides, diacetones acrylamides, acrylamides and methacrylamides substituted on nitrogen by lower alkyls, acrylic or methacrylic acids or their esters, vinyllactams such as vinylpyrrolidone, vinyl esters.

Among these compounds, mention may be made of: - the copolymer of acrylamide and of dimethylaminoethyl methacrylate quatersized with dimethyl sulfate sold under the name HERCOFLOC by the company
HERCULES, - the copolymer of acrylamide and methacryloyloxyethyltrtmethylammonium chloride described in patent application EP-A-080976 and sold under the name BINA QUAT P 100 by the company CIBA GEIGY, - the copolymer of acrylamide and methosulfate of methacryloyloxyethyl trimethylammonium sold under the name RETEN by the company
HERCULES, - vinylpyrrolidone J acrylate or dialkylaminoalkyl methacrylate copolymers, quaternized or not, such as the products sold under the name "GAFQUAT 'by the company ISP such as for example" GAFQUAT 734 "or" GAFQUAT 755 "or else the products called" COPOLYMER " 845, 958 and 937 ". These polymers are described in detail in French patents 2,077,143 and 2,393,573, - and the vinylpyrrolidone / quaternized dlmethylaminopropyl methacrylamide copolymer such as the product sold under the name" GAFQUAT HS 100 "by the ISP company.

(2) the quatenized polysaccharides described more particularly in US patents 3,589,578 and 4,031,307, such as the product sold under the name JAGUAR C 13 S by the company MEYHALL;
(3) quaternary copolymers of vinylpyrrolidone and of vinylimidazole;
(4) chitosans or their salts; the useful salts are in particular the acetate, lactate, glutamate, gluconate or pyrrolldone carboxylate of chitosan.

Among these compounds, mention may be made of chitosan having a deacetylation rate of 90.5% sold under the name KAN BRUT STANDARD by the company
ABER TECHNOLOGIES, the chitosan pyrrolidone carboxylate sold under the name KYwrAMER PC by the company AMERCHOL.

According to the invention, cationic polymers having film-forming properties are preferably used.

The linear polysiloxane-polyoxyalyylene block copolymers used in the context of the present invention preferably have the following general formula: ((Y (R2510) a R'2SiY011 (CnH2nO) bl) C in which: - R and R 'are identical or different represent a monovalent hydrocarbon radical not containing aliphatic unsaturation, - n is an integer between 2 and 4.

- a is an integer greater than or equal to 5, - b is an integer greater than or equal to 4, - c is an integer greater than or equal to 4, - Y represents a divalent organic group which is linked to the atom of adjacent silicon by a carbon-silicon bond and to a polyoxyalkylene block by an oxygen atom, - the average molecular weight of each siloxane block is between approximately 400 and approximately 10,000, that of each polyoxyalkylene block being between approximately 300 and approximately 10,000, - the siloxane blocks represent from approximately 10% to approximately 90% by weight of the block copolymer, - the average molecular weight of the block copolymer being at least 3,000.

R and R 'are more preferably chosen from the group comprising alkyl radicals such as, for example, methyl, ethyl and propyl radicals. butyl, pentyl, hexyl, octyl, decyl, dodecyl. aryl radicals such as, for example, phenyl, naphthyl, aralkyl radicals such as, for example, benzoyl, phenylethyl, the tolyl, xylyl and cyclohexyl radicals.

Y is preferably -R "-, -R" -CO-, -R "-NHCO-, -R" -NH-CO-NH-R "'- NHCO, -R" -OCONH-R "-NHCO- , or R "is a divalent alkylene group such as for example ethylene, propylene or butylene and R" 'is a divalent alkylene group or a divalent arylene group such as -C6H4-, -C6H4-C6H4-, -C6H4- CH2 -C6H4-, -C6H4-CH (CH3) 2-C6H4-.

Even more preferably Y represents a divalent alkylene radical, more particularly the -CH2-CH2-CH2- radical.

The preparation of the block copolymers used in the context of the present invention is described in European application EP 0 492 657 A1, the teaching of which is included by way of reference in the present description.

The preferred linear polysiloxane-polyoxyauWlene block copolymers according to the invention are chosen from those of formula: [C4H8 (CnH2nO) b - C4H8 - SiMe2O (SiMe2O) aSiMe2ic or Me represents methyl, n is an integer from 2 to 4, a and b are integers greater than or equal to 4, c is a number greater than or equal to 4.

According to a particular embodiment of the invention, the block copolymer is chosen from the following copolymers: [[(CH3) 2SiO] 41 (CH3) 2SiCH2CH (CH3) CH2-O (C2H4O) 18- (C3H6O) 33CH2CH (CH3) CH2] 16.1 [[(CH3) 2SiO] 31 (CH3) 2SiCH2CH (CH3) CH2-O (C2H4O) 20- (C3H6O) 29CH2CH (CH3) CH2] 13.3 [[(CH3) 2SiO] 9 (CH3) 2SiCH2CH (CH3 ) CH2-O- (C2H4O) 20- (C3H6O) 29CH2CH (CH3) CH2] 26.3 [[(CH3) 2SiO] 16 (CH3) 2SiCH2CH (CH3CH2-O (C2H4O) 18- (C3H6O) 20CH2 (CH3) CH2] 2.1.5 [[[(CH3) 2SiO] 9 (CH32SiCH2CH (CH3) CH2-O (C2H4O) 5-CH2CH (CH3CH2] 4.8
The cationic polymer is presently used in an amount comprised between 0.1 and 25% by weight of the total weight of the composition. Even more preferably, this amount is between 0.5 and 20%.

As regards the linear block copolymer, it is preferably used in an amount of between 0.05 and 20% by weight of the total weight of the composition.

Even more preferably, this amount is between 0.1 and 10%.

The compositions according to the invention can be provided in the form of a gel or an emulsion (milk or cream). of more or less thickened aqueous alcoholic or hydroalcoholic lotion, dispersion or foam.

They are more particularly styling lotions, brushing lotions, fixing compositions (lacquers) and styling. The lotions can be packaged in various forms, in particular in vaporizers, pump dispensers or in aerosol containers in order to ensure application of the composition in vaporized form or in foam form. Such forms of packaging are indicated. for example. when it is desired to obtain a spray, a lacquer or a mousse for fixing the hair.

The compositions can also be shampoos, compositions to be rinsed out or not, to be applied before or after shampooing. coloring, bleaching, perming or straightening, hair coloring, bleaching, perming or straightening compositions
The cosmetically acceptable medium is for example constituted by water. an organic solvent such as for example an alcohol and their mixtures.

The compositions according to the invention can also contain the additives usually used in cosmetics.

When the composition according to the invention is packaged in aerosol form with a view to obtaining a lacquer or an aerosol foam. it comprises at least one propellant which can be chosen from volatile hydrocarbons such as n-butane, propane, isobutane, pentane and their mixtures, optionally with at least one chlorinated and / or fluorinated hydrocarbon. use carbon dioxide, nitrous oxide, dlmethylether, nitrogen or compressed aSr as propellant.

The process for treating keratin fibers, in particular the hair, consists in applying to the fibers at least one composition as defined above.

The invention will now be more fully illustrated with the aid of the following examples which should not be considered as limiting it to the embodiments described.

Example 1
A brushing spray is prepared in a pump-action bottle of the following composition: - Vinylpyrrolidone / dimethylamino ethyl methacrylate copolymer in aqueous solution at 2A of active material sold under the name COPOLYMERE 845 by the company ISP 0.35 gMA (conductivity = 0.06 m # - 1cm-1) - Block copolymer of formula: 1gMA [[(CH3) 2SiO] x (CH3) 2SiCH2CH (CH3CH2-O (C2H4O) y- (C3H6O) zCH2CH (CH3) CH2] nx = 9â 11, y = 18 a 25. z = 28 to 35 and n is such that the viscosity of a 10% solution of polymer in methanol is approximately 50 mPa.s.

- Parfium, colorant, preservative qs - Ethanol 42.5 g - Water qs 100 g
This composition has good fixing power and good cosmetic properties.

Exe: mp1e2
A shaping lotion of the following composition is prepared: - Vinylpyrrolidone / dimethylamino ethyl methacrylate copolymer quaternized with diethyl sulfate in an alcoholic solution containing 50% of active material sold under the name GAFQUAT 734 by the company ISP 1gMA (conductivity = 0 , 29 m # -1cm-1) - Block copolymer of formula: 0.5 gMA [[(CH3) 2SiO) x (CH3) 2SiCH2CH (CH3) CH2-O (C2H4O) y- (C3H6O) zCH2CH (CH3) CH2 ] nx = 9 to 11, y = 18 to 25, z = 28 to 35 and n is such that the viscosity of a 10% solution of polymer in ethanol is approximately 50 mPa.s.

-Perfume, coloring. preservative qs - Ethanol 20.5 g - Water qs 100 g
Example 3
A shaping lotion of the following composition is prepared: - Guar gum hydroxypropylated and quaternized with 2.3-epoxypropyl trimethyl ammonium chloride sold under the name JAGUAR C13 S by the company MEYHALL 1 g (conductivity = 0.85 m # -1cm- 1) - Block copolymer of formula: 1 gMA [[(CH3) 2SiO) x (CH3) 2SiCH2CH (CH3) CH2-O (C2H4O) y- (C3H6O) zCH2CH (CH3) CH2] nx = 9 to 11, y = 18 at 25. z = 28 to 35 and n is such that the viscosity of a 10% solution of polymer in ethanol is approximately 50 mPas.

- Perfume, colorant, preservative qs - Ethanol 8.6 g - Water qs 100 g
Example 4
A shaping lotion of the following composition is prepared: - Chitosan pyrrolidone carboxylate sold under the name KYTAMER PC by the company AMERCHOL 0.5 g (conductivity = 0.95 m # 1cm-1) - Block copolymer of formula: 1 gMA [ [(CH3) 2SiO) x (CH3) 2SiCH2CH (CH3) CH2-O (C2H4O) y- (C3H6O) zCH2CH (CH3) CH2] nx = 9 to 11, y = 18 to 25, z = 28 to 35 and n is such that the viscosity of a 10% solution of polymer in ethanol is about 50 mPa.s.

- Perfume, colorant, preservative qs - Ethanol 8.6 g - Water qs 100 g
Example 5
A styling mousse of sutvante composition is prepared: - Vinylpyrrolidone / dimethylamino ethyl methacrylate copolymer quaternized with diethyl sulfate in an alcoholic solution containing 50% of active material sold under the name GAFQUAT 755 by the company ISP 1.5 gMA (conductivity = 0.41 m # -1cm-1) - Block copolymer of formula: 2gMA [[(CH3) 2SiO) x (CH3) 2SiCH2CH (CH3) CH2-O (C2H4O) y- (C3H6O) zCH2CH (CH3) CH2] nx = 9 to 11, y = 18 to 25, z = 28 to 35 and n is such that the viscosity of a 10% polymer solution in methanol is about 50 mPas.

- Perfume, dye. preservative qs - Ethanol 8,6 g - Water qsp îoog
This composition is packaged according to the following pressurization scheme: - Composition above 90% - Butane / propane / isobutane mixture sold under the name AEROGAZ 3.2 N by ELF AQUITAINE: 10% Example 6
A styling lotion of the following composition is prepared: - Vinylpyrrolidone / dimethylamino ethyl methacrylate copolymer in aqueous solution a. 20% of active material sold under the name COPOLYMERE 845 by the company ISP 1 gMA (conductivity = 0.06 m # -1cm-1) - Block copolymer of formula: 1 gMA [[(CH3) 2SiO) x (CH3) 2SiCH2CH (CH3) CH2-O (C2H4O) y- (C3H6O) zCH2CH (CH3) CH2] nx = 9 to 11, y = 18 to 25, z = 28 to 35 and n is such that the viscosity of a polymer solution at 10% in methanol, ie approximately 50 mPa.s.

- Parfim, colorant. preservative qs - Ethanol 8,6 g - Water qs 100 g
This composition has good fixing power and good cosmetic properties.

Comparative Example 7
In the composition of Example 6, COPOLYMER 845 (conductivity = 0.06 m # -1 cm-1) is replaced by the same quantity of a cationic cellulose sold under the name POLYMER JR 400 by the company UNION CARBIDE (conductivity = 1, 2m # -1cm-1)
The composition exhibits a binding power very markedly lower than that of Example 6, whereas without the silicone derivative in accordance with the invention, the two cationic polymers have a fixing power which is substantially equivalent.

Claims (18)

- at least one linear polysiloxane-polyoxyalkylene block copolymer. - at least one cationic polymer having a fixing power and a conductivity less than or equal to 1 mohm-1cm-1, and CLAIMS 1. Cosmetic composition. characterized in that it comprises, in a cosmetically acceptable medium: 2. Composition according to claim 1, characterized in that the cationic polymer is chosen from polymers comprising primary, secondary, tertiary and / or quaternary amine groups forming part of the polymer chain or directly linked to it. and having a molecular weight of between 500 and about 5,000,000. 3. Composition according to claim 2. caractéssée in that said molecular weights are between 1000 and 3,000,000. 4. Composition according to claim 2, characterized in that the polymers cationic are chosen from the following polymers: (1) homopolymers or copolymers derived from esters or amides acrylic or methacrylic and comprising at least one of the units of formulas following:

in which: R3 denotes H or CH3; A is a linear or branched allyl group of 1 to 6 carbon atoms or a hydroxyalkyl group of 1 to 4 carbon atoms; R4. R5, R6, identical or different, represent an allyl group having from 1 to 18 carbon atoms or a benzyl radical; R1 and R2 represent hydrogen or an allyl group having 1 to 6 carbon atoms; X denotes a methosulfate anion or a halide such as chloride or bromide; (2) quatersized polysaccharides; (3) quaternary copolymers of vinylpyrrolidone and of vinyllmidazole; (4) chitosans or their salts. 5. Composition according to claim 4, characterized in that said copolymers containing said units of formula (A). (B) or (C) also contain units derived from comonomers chosen from the family of acrylamides, methacrylamides, diacetone acrylamide, acrylamides and methacrylamides substituted on nitrogen by lower allyls. acrylic or methacrylic acids or their esters. vinyllactams such as vinylpyrrolidone, vinyl esters. 6. Composition according to claim 4, characterized in that said chitosan salts are chosen from acetates. chitosan lactate, glutamate, gluconate or pyrrolidone carboxylate. 7. Composition according to claim 4, characterized in that the polymers are chosen from: - copolymers of acrylamide and of dimethylaminoethyl methacrylate quaternized with dimethyl sulfate - copolymers of acrylamide and of methacryloyloxyethyltrimetbylammonium chloride or methosulite - copolymers vinylpyrrolidone / dialkylaminoalkyl acrylate or methacrylate, quaternized or not, and - vinylpyrrolidone / methacrylamide copolymers of dialkylaminoalkyl, quaternized or not. 8. Composition according to any one of claims 1 to 7, characterized in that the linear block copolymer corresponds to the general formula: (IY (R2SiO) a R'2SiYO [(CnH2nO) bjlc in which: - R and R 'identical or different. Represent a monovalent hydrocarbon radical not containing aliphatic unsaturation, - n is an integer between 2 and 4 , - a is an integer greater than or equal to 5, - b is an integer greater than or equal to 4. - c is an integer greater than or equal to 4. - Y represents a divalent organic group which is bonded to the adjacent silicon atom via a carbon-silicon bond and to a polyoxyalkylene block via an oxygen atom, - the average molecular weight of each siloxane block is between approximately 400 and about 10,000. that of each polyoxyalkylene block being between approximately 300 and approximately 10,000. - the siloxane blocks represent from 10% to about 90% by weight of the block copolymer, - the average molecular weight of the block copolymer being at least 3,000. 9. Composition according to claim 8, characterized in that R and R 'are chosen from the group comprising methyl radicals. ethyl. propyl, butyl, pentyl, hexyl, octyl. decyle, dodecyle. phenyl, naphthyl, benzoyl, phenylethyl, total, xylyl and cyclohexyl. 10. Composition according to any one of claims 8 or 9 characterized in that Y is chosen from the group comprising -R "-, -R" -CO-, -R "-NHCO-, '-NH-CONH-R "'NHCO, -R" -OCO & HR "' - NHCO-, where R" represents an ethylene, propylene or butylene radical and R "'represents a group -C6H4-, -C6H4 C6H4-. -C6H4-CH2-C6H4-, or -C6H4-CH (CH3) 2-C6H4-. 11. Composition according to one of claims 8. 9 or 10, characterized in that the linear polysiloxane-polyoxyalyiene block copolymers are chosen from those of formula: [C4H8 (Cn112n0) b - C4H8 - SiMe2O (SIMe2O) aSiMe2Jc where Me represents methyl. n is an integer from 2 to 4.a and b are integers greater than or equal to 4, c is a number greater than or equal to 4. 12. Composition according to any one of claims 8 to 11, characterized in that the block copolymer is chosen from the group comprising the following compounds: [[(CH3) 2SiO] 41 (CH3) 2SiCH2CH (CH3) CH2-O ( C2H4O) 18- (C3H6O) 33CH2CH (CH3) CH2] 16.1 [[(CH3) 2SiO] 31 (CH3) 2SiCH2CH (CH3) CH2-O (C2H4O) 20- (C3H6O) 29CH2CH (CH3) CH2] 13.3 [[( CH3) 2SiO] 9 (CH3) 2SiCH2CH (CH3) CH2-O (C2H4O) 20- (C3H6O) 29CH2CH (CH3) CH2] 26.3 [[(CH3) 2SiO] 16 (CH3) 2SiCH2CH (CH3) CH2-O (C2H4O ) 18- (C3H6O) 20CH2CH (CH3) CH2] 21.5 [[(CH3) 2SiO] 9 (CH3) 2SiCH2CH (CH3) CH2-O (C2H4O) 5-CH2CH (CH3) CH2] 4.8 13. Composition according to any one of claims 1 to 12. characterized in that the cationic polymer is present in proportions of between 0.1 and 25% by weight and preferably between 0.5 and 20% by weight, relative to to the whole composition. 14. Composition according to any one of claims 1 to 13, characterized in that the linear polysiloxane-polyoxyalkylene block copolymer is present in proportions of between 0.05 and 20% by weight and preferably between 0.1 and 10. % in weight. compared to the whole composition. 15. Composition according to any one of claims 1 to 14, characterized in that it is in gel form. emulsion, aqueous lotion. alcoholic or hydroalcoholic, dispersion or foam. 16. Use of the composition as defined in any one of claims 1 to 15, as, or for the manufacture, styling lotion. brushing lotion, styling or fixing composition, as a shampoo composition, as a rinse-out or not to be applied before or after shampooing, coloring, bleaching, perming or curling, coloring or bleaching compositions . perm or straightening hair 17. Process for treating keratin fibers. characterized in that at least one composition as defined in any one of claims 1 to 15 is applied to said fibers. 18. Use of a linear polysiloxane-polyoxyalkylene block copolymer as an agent for enhancing the fixing power of a composition for maintaining the hairstyle containing a cationic polymer with fixing power and of conductivity less than or equal to 1 mohm-1cm-1.