Cosmetic fixative composition providing shine

The present invention relates to a cosmetic composition for the treatment of keratin materials, in particular the hair, comprising at least one fixing polymer, at least 5% by weight of a non-volatile arylated silicone and at least one volatile silicone, as well as 'to the process for treating keratinous materials using this composition.

Hair holding or shaping compositions containing, in their formulation, styling polymers (fixing polymers) generally have the drawback of making it difficult to disentangle, recoiffer or brush the hair, in particular during brushing. Styling polymers also tend to make hair dull.

The association of silicone derivatives with fixing polymers is known in cosmetic compositions for maintaining and / or fixing the hairstyle. It has been found that these silicone derivatives improve the disentangling, softness and shine properties of the hair treated with these compositions. However, on the one hand, the silicone derivatives are not favorable to the styling properties of the compositions containing fixing polymers and, on the other hand, the gloss properties are not yet satisfactory.

There are so-called "shiny" products that apply as a finishing treatment, that is to say on dried hair. These products are difficult to apply because if the amount applied is too large or poorly distributed, the hair generally has a greasy feel and visual appearance. In addition, these products do not provide any fixation.

The document <nplcit id="ncit0001" npl-type="s"><text>SOAP, COSMETICS, CHEMICAL SPECIALTIES p 30-39, 72, 73 vol 63, Nº 10, October 1887</text></nplcit> describes the benefit of silicones in hair fixing compositions.

The object of the present invention is therefore to propose compositions making it possible to fix and / or to shape the hairstyle, these compositions having to have good properties of resistance over time and to provide excellent properties of shine.

However, the Applicant has surprisingly discovered that by using compositions containing a fixing polymer in combination with at least one non-volatile arylated silicone and at least one volatile silicone in a cosmetically acceptable medium, excellent properties are obtained. <u>shine</u>, a good drying time while having excellent styling properties and / or <u>fixing</u>.

The present invention therefore relates to a cosmetic composition comprising, in a cosmetically acceptable medium, at least one fixing polymer, at least 5% by weight of a non-volatile arylated silicone and at least one volatile silicone, as claimed.

Surprisingly, the reduction in the fixing power of compositions is limited despite the presence of a large amount of silicone. The styling properties are substantially the same degree as those of a composition containing only the fixing polymer. In particular, the fixing power, the resistance over time and the volume of hair are very good.

After drying, these compositions do not powder on the hair during brushing or combing (there are no white films) and are invisible on the hair. The treated hair has<u>a non-greasy touch and visual appearance</u>.

In addition, brushing and / or combing the hair after applying the product further improves the shine.

In the context of the present application, the term “cosmetic compositions for maintaining the hairstyle” means any composition having the function of temporarily fixing the shape of the hairstyle, such as, for example, hairstyling hairsprays and sprays. By fixing power of the composition, is meant the ability of the latter to give the hair cohesion so that the initial shaping of the hairstyle is preserved. The term “fixing polymer” means any polymer having the function of temporarily fixing the shape of the hairstyle.

According to the invention, any fixing polymer known per se can be used. It is possible in particular to use a fixing polymer chosen from anionic, cationic, amphoteric, nonionic polymers and their mixtures. The fixing polymers can be used in dissolved form or in the form of dispersions of solid polymer particles.

The cationic fixing polymers which can be used according to the present invention are preferably chosen from polymers comprising primary, secondary, tertiary and / or quaternary amine groups forming part of the polymer chain or directly linked thereto, and having an average molecular weight in weight between 500 and around 5,000,000 and preferably between 1,000 and 3,000,000.

Among these polymers, there may be mentioned more particularly the following cationic polymers:<ul id="ul0001" list-style="none"><li>(1) homopolymers or copolymers derived from acrylic or methacrylic esters or amides and comprising at least one of the units of the following formulas:<chemistry id="chem0001" num="0001"><img file="EP0822802B2_D0001.tif" /></chemistry>in which:<ol id="ol0001" compact="compact"><li>R₃ denotes a hydrogen atom or a CH radical₃;</li><li>A is a linear or branched alkyl group of 1 to 6 carbon atoms or a hydroxyalkyl group of 1 to 4 carbon atoms;</li><li>R₄, R₅, R₆, identical or different, represent an alkyl group having from 1 to 18 carbon atoms or a benzyl radical;</li><li>R₁ and R₂ represent hydrogen or an alkyl group having from 1 to 6 carbon atoms;</li><li>X denotes a methosulfate anion or a halide such as chloride or bromide.</li><li /></ol>The copolymers of family (1) additionally contain one or more monomer units which can be chosen from the family of acrylamides, methacrylamides, diacetones, acrylamides, acrylamides and methacrylamides substituted on nitrogen by lower C1-C6 alkyls, acrylic acids or methacrylic or their esters, vinyllactams such as vinylpyrrolidone or vinylcaprolactam, vinyl esters. Thus, among these copolymers of family (1), cn may be cited:<ul id="ul0002" list-style="dash" compact="compact"><li>copolymers of acrylamide and of dimethylaminoethyl methacrylate quaternized with dimethyl sulphate or with a dimethyl hologenide such as that sold under the name HERCOFLOC by the company HERCULES,</li><li>copolymers of acrylamide and methacryloyloxyethyltrimethylammonium chloride described for example in the patent application <patcit id="pcit0001" dnum="EP080976A"><text>EP-A-080976</text></patcit> and sold under the name BINA QUAT P 100 by the company CIBA GEIGY,</li><li>the copolymer of acrylamide and methacryloyloxyethyltrimethylammonium methosulfate sold under the name RETEN by the company Hercules,</li><li>vinylpyrrolidone / acrylate or methacrylate of dialkylaminoalkyl 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<patcit id="pcit0002" dnum="FR2077143"><text>French patents 2,077,143</text></patcit> and <patcit id="pcit0003" dnum="FR2393573"><text>2.393.573</text></patcit>,</li><li>dimethyl methacrylate amino ethyl terpolymer / vinylcaprolactam / vinyipyrrolidone such as the product sold under the name GAFFIX VC 713 by the company ISP.</li><li>and the vinylpyrrolidone / methacrylamide dimethylaminopropyl quaternized copolymer such as the product sold under the name "GAFQUAT HS 100" by the company ISP.</li></ul></li><li>(2) the quaternized 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;</li><li>(3) quaternary copolymers of vinylpyrrolidone and vinylimidazole;</li><li>(4) chitosans or their salts; the salts which can be used are in particular the acetate, lactate, glutamate, gluconate or the pyrrolidone carboxylate of chitosan.</li></ul>

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

The anionic fixing polymers generally used are polymers comprising groups derived from carboxylic, sulphonic or phosphoric acid and have a weight-average molecular weight of between approximately 500 and 5,000,000.<ol id="ol0002" compact="compact"><li>1) The carboxylic groups are provided by mono or unsaturated dicarboxylic acid monomers such as those corresponding to the formula:<chemistry id="chem0002" num="0002"><img file="EP0822802B2_D0002.tif" /></chemistry>where n is an integer from 0 to 10, A₁ denotes a methylene group, optionally linked to the carbon atom of the unsaturated group or to the neighboring methylene group when n is greater than 1 via a heteroatom such as oxygen or sulfur, R₇ denotes a hydrogen atom, a phenyl or benzyl group, R₈ denotes a hydrogen atom, a lower C alkyl group₁-VS₆ or carboxyl, R₉ denotes a hydrogen atom, a lower C alkyl group₁-VS₆, a group -CH₂-COOH, phenyl or benzyl; In the above formula a lower alkyl radical preferably denotes a group having 1 to 6 carbon atoms and in particular, methyl and ethyl.</li></ol>

The preferred anionic fixing polymers with carboxylic groups according to the invention are:<ul id="ul0003" list-style="none"><li>A) homo- or copolymers of acrylic or methacrylic acid or their salts and in particular the products sold under the names VERSICOL E or K by the company ALLIED COLLOID and ULTRAHOLD by the company BASF. The copolymers of acrylic acid and acrylamide sold in the form of their sodium salt under the names RETEN 421, 423 or 425 by the company HERCULES, the sodium salts of polyhydroxycarboxylic acids.</li><li>B) Copolymers of acrylic or methacrylic acids with a monoethylenic monomer such as ethylene, styrene, vinyl esters, esters of acrylic or methacrylic acid, optionally grafted on a polyalkylene glycol such as polyethylene glycol and optionally crosslinked. Such polymers are described in particular in the<patcit id="pcit0004" dnum="FR1222944"><text>French patent 1,222,944</text></patcit> and demand <patcit id="pcit0005" dnum="DE2330956"><text>German 2,330,956</text></patcit>, copolymers of this type comprising in their chain an optionally N-alkylated and / or hydroxyalkylated acrylamide unit as described in particular in patent applications <patcit id="pcit0006" dnum="LU75370"><text>Luxembourgish 75,370 </text></patcit>and <patcit id="pcit0007" dnum="LU75371"><text>75371</text></patcit> or offered under the name QUADRAMER by the company AMERICAN CYANAMID. Mention may also be made of copolymers of acrylic acid and of C 1 alkyl methacrylate.₁-VS₄ and terpolymers of vinylpyrrolidone, acrylic acid and C-alkyl methacrylate₁-VS₂₀ for example lauryl such as that sold by the company ISP under the name ACRYLIDONE LM and the methacrylic acid / ethyl acrylate / tert-butyl acrylate terpolymers such as the product sold under the name LUVIMER 100 P by the company BASF.</li><li>C) copolymers derived from crotonic acid such as those comprising in their chain vinyl acetate or propionate units and optionally other monomers such as allyl or methallyl esters, vinyl ether or vinyl ester of a linear or branched saturated carboxylic acid with a long hydrocarbon chain such as those containing at least 5 carbon atoms, these polymers possibly being grafted and crosslinked or else a vinyl ester, allylic or methallylic of an α- or β-cyclic carboxylic acid. Such polymers are described inter alia in patents<patcit id="pcit0008" dnum="FR1222944"><text>French 1,222,944</text></patcit>, <patcit id="pcit0009" dnum="FR1580545"><text>1.580.545</text></patcit>, <patcit id="pcit0010" dnum="FR2265782"><text>2.265.782</text></patcit>, <patcit id="pcit0011" dnum="FR2265781"><text>2.265.781</text></patcit>. <patcit id="pcit0012" dnum="FR1564110"><text>1.564 110</text></patcit> and <patcit id="pcit0013" dnum="FR2439798"><text>2.439.798</text></patcit>. Commercial products falling into this class are resins 28-29-30, 26-13-14 and 28-13-10 sold by the company NATIONAL STARCH</li><li>D) copolymers derived from cu acids of C4-C8 monounsaturated carboxylic anhydrides chosen from:<ul id="ul0004" list-style="dash"><li>copolymers comprising (i) one or more maleic, fumaric, itaconic acids or anhydrides and (ii) at least one monomer chosen from vinyl esters, vinyl ethers, vinyl halides, phenylvinyl derivatives, acrylic acid and its esters , the anhydride functions of these copolymers being optionally monoesterified or monoamidified. ; Such polymers are described in particular in patents<patcit id="pcit0014" dnum="US2047398A"><text>US 2,047,398</text></patcit>, <patcit id="pcit0015" dnum="US2723248A"><text>2.723.248</text></patcit>, <patcit id="pcit0016" dnum="US2102113A"><text>2.102.113</text></patcit>, the patent <patcit id="pcit0017" dnum="GB839805A"><text>GB 839.805</text></patcit> and in particular those sold under the names GANTREZ AN or ES by the company ISP.</li><li>copolymers comprising (i) one or more maleic, citraconic, itaconic anhydrides and (ii) one or more monomers chosen from allylic or methallylic esters optionally comprising one or more acrylamide, methacryiamide, α-olefin group, acrylic or methacrylic esters, acids acrylic or methacrylic or vinylpyrrolidone in their chain, the anhydride functions of these copolymers being optionally monoesterified or monoamidified. These polymers are for example described in the <patcit id="pcit0018" dnum="FR2350384"><text>French patents 2,350,384</text></patcit> and <patcit id="pcit0019" dnum="FR2357241"><text>2.357.241</text></patcit> of the plaintiff.</li></ul></li><li>E) polyacrylamides comprising carboxylate groups.</li></ul>

The polymers comprising the sulfonic groups are polymers comprising these vinylsulfonic, styrene sulfonic, naphthalene sulfonic or acrylamido alkylsulfonic units.

These polymers can in particular be chosen from:<ul id="ul0005" list-style="dash"><li>the salts of polyvinylsulfonic acid having a weight average molecular weight of between approximately 1,000 and 100,000 as well as copolymers with an unsaturated comonomer such as acrylic or methacrylic acids and their esters as well as acrylamide or its derivatives, vinyl ethers and vinylpyrrolidone.</li><li>the salts of polystyrene sulfonic acid the sodium salts having a weight average molecular weight of approximately 500,000 and approximately 100,000 sold respectively under the names Flexan 500 and Flexan 130 by National Starch. These compounds are described in<patcit id="pcit0020" dnum="FR2198719"><text>FR patent 2,198,719</text></patcit>.</li><li>the salts of polyacrylamide sulfonic acids those mentioned in the <patcit id="pcit0021" dnum="US4128631A"><text>US patent 4,128,631</text></patcit> and more particularly polyacrylamidoethylpropane sulfonic acid sold under the name COSMEDIA POLYMER HSP 1180 by Henkel.</li></ul>

According to the invention, the anionic fixing polymers are preferably chosen from acrylic acid copolymers such as the acrylic acid / ethyl acrylate / N-tert-butylacrylamide terpolymer sold under the name ULTRAHOLD STRONG by the company BASF, copolymers derived from crotonic acid such as the vinyl acetate / vinyl tert-butyl benzoate / crotonic acid terpolymers and the crotonic acid / vinyl acetate / vinyl neododecanoate terpolymers sold under the name Resin 28-29-30 by the company NATIONAL STARCH, polymers derived from maleic, fumaric or itaconic acids or anhydrides with vinyl esters, vinyl ethers, vinytic halides, phenylvinyl derivatives, acrylic acid and its esters such as the methyl ester / maleic anhydride mono esterified copolymer sold under the name GANTREZ ES 425 by the company ISP, the copolymers of methacrylic acid and methyl methacrylate sold under the name EUDRAGIT L by the company ROHM PHARMA, the copolymer of methacrylic acid and ethyl acrylate sold under the name LUVIMER MAEX or MAE by the company BASF and the vinyl acetate / crotonic acid copolymer sold under the name LUVISET CA 66 by the company BASF and the acetate copolymer of vinyl / crotonic acid grafted with polyethylene glycol under the name ARISTOFLEX A by the company BASF.

The most particularly preferred anionic fixing polymers are chosen from the methyl vinyl ether / mono esterified maleic anhydride copolymer sold under the name GANTREZ ES 425 by the company ISP, the acrylic acid / ethyl acrylate / N-tertiobutylacrylamide terpolymer sold under the name ULTRAHOLD STRONG by the company BASF, the copolymers of methacrylic acid and this methyl methacrylate sold under the name EUDRAGIT L by the company ROHM PHARMA, the vinyl acetate / vinyl tert-butyl benzoate / crotonic acid terpolymers and the crotonic acid / vinyl acetate / vinyl neododecanoate terpolymers sold under the name Resin 28-29-30 by the company NATIONAL STARCH, the methacrylic acid copolymer and ethyl acrylate sold under the name LUVIMER MAEX OR MAE by the company BASF, the vinylpyrrolidone / acrylic acid / lauryl methacrylate terpolymer sold under the name ACRYLIDONE LM by the company ISP.

The amphoteric fixing polymers which can be used in accordance with the invention can be chosen from polymers comprising units B and C distributed statistically in the polymer chain where B denotes a unit deriving from a monomer comprising at least one basic nitrogen atom and C denotes a unit deriving from an acidic monomer comprising one or more carboxylic or sulphonic groups or else B and C can denote groups deriving from zwitterionic monomers of carboxybetaines or sulfobetaines; B and C can also denote a cationic polymer chain comprising primary, secondary, tertiary or quaternary amine groups, in which at least one of the amine groups carries a carboxylic or sulphonic group linked via a hydrocarbon radical or else B and C form part of a chain of a polymer with an ethylene motif a, b-dicarboxylic whose one of the carboxylic groups has been reacted with a polyamine comprising one or more primary or secondary amine groups.

The amphoteric fixing polymers corresponding to the definition given above which are more particularly preferred are chosen from the following polymers:<ul id="ul0006" list-style="none"><li>1) polymers resulting from the copolymerization of a monomer derived from a vinyl compound carrying a carboxylic group such as more particularly acrylic acid, methacrylic acid, maleic acid, alpha-chloroacrylic acid, and d 'a basic monomer derived from a substituted vinyl compound containing at least one basic atom such as more particularly the dialkylaminoalkylmethacrylate and acrylate, the dialkyiaminoalkylmethacrylamide and acrylamide. Such compounds are described in U.S. Patent No. 3,836,537</li><li>(2) polymers comprising units derived from:<ol id="ol0003" compact="compact"><li>a) at least one monomer chosen from acrylamides or methacrylamides substituted on nitrogen with an alkyl radical,</li><li>b) at least one acidic comonomer containing one or more reactive carboxylic groups, and</li><li>c) at least one basic comonomer such as esters with primary, secondary, tertiary and quaternary amine substituents of acrylic and methacrylic acids and the quaternization product of dimethylaminoethyl methacrylate with dimethyl or diethyl sulfate. The N-substituted acrylamides or methacrylamides more particularly preferred according to the invention are the groups in which the alkyl radicals contain from 2 to 12 carbon atoms and more particularly N-ethylacrylamide, N-tertiobutyl acrylamide, N-tertiooctyl acrylamide, N-octylacrylamide, N-decylacrylamide, N-dodecylacrylamide and the corresponding methacrylamides. The acid comonomers are chosen more particularly from acrylic, methacrylic, crotonic, itaconic, maleic, fumaric acids as well as alkyl monoesters having 1 to 4 carbon atoms of maleic or fumaric acids or anhydrides. The preferred basic comonomers are aminoethyl, butyl aminoethyl, N, N'-dimethylaminoethyl, N-tert-butylaminoethyl methacrylates. Copolymers are particularly used, the name CTFA (4th Ed., 1991) being Octylacrylamide / acrylates / butyiaminoethylmethacrylate copolymer such as the products sold under the name AMPHOMER or LOVOCRYL 47 by the company NATIONAL STARCH.</li></ol></li><li>(3) crosslinked and alkylated polyamino amides partially or totally derived from poyaminoamides of general formula:<chemistry id="chem0003" num="0003"><img file="EP0822802B2_D0003.tif" /></chemistry>in which R₁₀ represents a divalent radical derived from a saturated dicarboxylic acid, from a mono or dicarboxylic aliphatic acid with ethylenic double bond, from an ester of a lower alkanol having 1 to 6 carbon atoms of these acids or from a derivative radical the addition of any one of said acids with a primary bis or secondary bis amine, and Z denotes a radical of a bis-primary, mono or bis-secondary polyalkylene polyamine and preferably represents:<ol id="ol0004" compact="compact"><li>a) in the proportions of 60 to 100 mol%, the radical<chemistry id="chem0004" num="0004"><img file="EP0822802B2_D0004.tif" /></chemistry>where x = 2 and p = 2 cu 3, or else x = 3 and p = 2 this radical deriving from diethylene triamine, triethylene tetraamine or dipropylene triamine;</li><li>b) in the proportions of 0 to 40 mol% the radical (IV) above, in which x = 2 and p = 1 and which derives from ethylenediamine, or the radical deriving from piperazine:<chemistry id="chem0005" num="0005"><img file="EP0822802B2_D0005.tif" /></chemistry></li><li>c) in the proportions of 0 to 20 mol% the radical -NH- (CH₂)₆-NH- derived from hexamethylenediamine, these polyaminoamines being crosslinked by addition of a bifunctional crosslinking agent chosen from epihalohydrins, diepoxides, dianhydrides, bis unsaturated derivatives, using 0.025 to 0.35 mole of crosslinking agent by amine group of the polyaminoamide and alkylated by the action of acrylic acid, chloracetic acid or an alkane sultone or their salts. The saturated carboxylic acids are preferably chosen from acids having 6 to 10 carbon atoms such as adipic, trimethyl-2,2,4-adipic acid and trimethyl-2,4,4-adipic, terephthalic acid, ethylenic double bond such as for example acrylic, methacrylic, itaconic acids. The alkane sultones used in the alkylation are preferably propane or butane sultone, the salts of the alkylating agents are preferably the sodium or potassium salts.</li></ol></li><li>(4) polymers comprising zwitterionic units of formula:<chemistry id="chem0006" num="0006"><img file="EP0822802B2_D0006.tif" /></chemistry>in which R₁₁ denotes a polymerizable unsaturated group such as an acrylate, methacrylate, acrylamide or metriacrylamide group, y and z represents an integer from 1 to 3, R₁₂ and R₁₃ represent a hydrogen, methyl, ethyl or propyl atom, R₁₄ and R₁₅ represent a hydrogen atom or an alkyl radical such that the sum of the carbon atoms in R₁₄ and R₁₅ does not exceed 10 The polymers comprising such units may also contain units derived from non-zwitterionic monomers such as dimethyl or diethylaminoethyl acrylate or methacrylate or alkyl acrylates or methacrylates, acrylamides or methacrylamides or vinyl acetate. By way of example, there may be mentioned the copolymer of methyl methacrylate / dimethyl carboxymethylammonio ethyl methacrylate such as the product sold under the name DIAFORMER Z301 by the company SANDOZ.</li><li>(5) polymers derived from chitosan comprising monomer units corresponding to the following formulas:<chemistry id="chem0007" num="0007"><img file="EP0822802B2_D0007.tif" /></chemistry>the pattern D being present in proportions of between 0 and 30%, the pattern E in proportions of between 5 and 50% and the pattern F in proportions of between 30 and 90%, it being understood that in this pattern F, R₁₆ represents a radical of formula:<chemistry id="chem0008" num="0008"><img file="EP0822802B2_D0008.tif" /></chemistry>in which if q = 0, R₁₇, R₁₈ and R₁₉, identical or different, each represents a hydrogen atom, a methyl, hydroxyl, acetoxy or amino residue, a monoalkoylamine residue or a dialkoylamine residue optionally interrupted by one or more nitrogen atoms and / or optionally substituted by one or more groups amine, hydroxyl, carboxyl, acoylthio, sulfonic, an alkylthio residue in which the alkyl group carries an amino residue, at least one of the radicals R₁₇, R₁₈ and R₁₉ being in this case a hydrogen atom; or if q = 1, R₁₇, R₁₈ and R₁₉ each represents a hydrogen atom, as well as the salts formed by these compounds with bases or acids</li><li>(6) Polymers derived from the N-carboxyalkylation of chitosan such as N-carboxymethyl chitosan or N-carboxybutyl chitosan sold under the name "EVALSAN" by the company JAN DEKKER.</li><li>(7) The polymers corresponding to the general formula (VI) are for example described in the <patcit id="pcit0022" dnum="FR1400366"><text>French patent 1,400,366</text></patcit> : <chemistry id="chem0009" num="0009"><img file="EP0822802B2_D0009.tif" /></chemistry>in which R₂₀ represents a hydrogen atom, a CH radical₃O, CH₃CH₂O, phenyl, R₂₁ denotes hydrogen or a lower alkyl radical such as methyl, ethyl, R₂₂ denotes hydrogen or a lower alkyl radical such as methyl, ethyl, R₂₃ denotes a lower alkyl radical such as methyl, ethyl or a radical corresponding to the formula: -R₂₄-N (R₂₂)₂, R₂₄ representing a group -CH₂-CH₂-, -CH₂-CH₂-CH₂-, -CH₂-CH (CH₃) -, R₂₂ having the meanings mentioned above, as well as the higher counterparts of these radicals and containing up to 6 carbon atoms.</li><li>(8) Amphoteric polymers of the -DXDX type chosen from:<ol id="ol0005"><li>a) the polymers obtained by the action of chloracetic acid or sodium chloroacetate on the compounds comprising at least one unit of formula:         -DXDXD- (VII) where D denotes a radical<chemistry id="chem0010" num="0010"><img file="EP0822802B2_D0010.tif" /></chemistry>and X denotes the symbol E or E ', E or E', which are identical or different, denote a bivalent radical which is an alkylene radical with a straight or branched chain containing up to 7 carbon atoms in the main chain unsubstituted or substituted by groups hydroxyl and may also contain oxygen, nitrogen, sulfur atoms, 1 to 3 aromatic and / or heterocyclic rings; the oxygen, nitrogen and sulfur atoms being present in the form of ether, thioether, sulfoxide, sulfone, sulfonium, alkylamine, alkenylamine groups, hydroxyl groups, benzylamine, amine oxide, quaternary ammonium, amide, imide, alcohol, ester and / or urethane.</li><li>b) The polymers of formula:         -DXDX- (VII ')</li></ol>where D denotes a radical<chemistry id="chem0011" num="0011"><img file="EP0822802B2_D0011.tif" /></chemistry>and X denotes the symbol E or E 'and at least once E'; E having the meaning indicated above and E 'is a bivalent radical which is a straight or branched chain alkylene radical having up to 7 carbon atoms in the main chain, whether or not substituted by one or more hydroxyl radicals and comprising a or more nitrogen atoms, the nitrogen atom being substituted by an alkyl chain optionally interrupted by an oxygen atom and necessarily having one or more carboxyl functions or one or more hydroxyl functions and betainized by reaction with chloracetic acid or sodium chloroacetate.</li><li>(9) alkyl (C1-C5) vinyl ether / maleic anhydride copolymers partially modified by semiamidation with an N, N-dialkylaminoalkylamine such as N, N-dimethylaminopropylamine or by semiesterification with an N, N-dialcanolamine. These copolymers can also contain other vinyl monomers such as vinylcaprolactam</li></ul>

The amphoteric fixing polymers which are particularly preferred according to the invention are those of the family (3) such as the copolymers whose name CTFA is Octylacrylamide / acrylates / butylaminoethylmethacrylate copolymer such as the products sold under the names AMPHOMER, AMHOMER LV 71 or LOVOCRYL 47 by the company NATIONAL STARCH and those of the family (4) such as methyl methacrylate / dimethyl carboxymethylammonio ethyl methyl methacrylate copolymer, for example sold under the name DIAFORMER Z301 by the company SANDOZ.

The nonionic fixing polymers which can be used according to the present invention are chosen, for example, from:<ul id="ul0007" list-style="dash" compact="compact"><li>polyalkyloxazolines such as the polyethyloxazolines offered by the company DOW CHEMICAL under the names PEOX 50,000, PEOX 200,000 and PEOX 500,000;</li><li>vinyl acetate homopolymers such as the product offered under the name of APPRETAN EM by the company HOECHST or the product offered under the name of RHODOPAS A 012 by the company RHONE POULENC;</li><li>copolymers of vinyl acetate and of acrylic ester such as the product offered under the name of RHODOPAS AD 310 from RHONE POULENC;</li><li>copolymers of vinyl acetate and ethylene such as the product offered under the name of APPRETAN TV by the company HOECHST;</li><li>copolymers of vinyl acetate and of maleic ester for example of dibutyl maleate such as the product offered under the name of APPRETAN MB EXTRA by the company HOECHST;</li><li>vinyl chloride homopolymers such as the products offered under the names of GEON 460X45, GEON 460X46 and GEON 577 by the company GOODRICH,</li><li>polyethylene waxes such as the products offered under the names AQUACER 513 and AQUACER 533 by the company BYK CERA;</li><li>polyethylene / polytetrafluoroethylene waxes such as the products offered under the names DREWAX D-3750 by the company DREW AMEROID and WAX DISPERSION WD-1077 by the company RT NEWEY;</li><li>polyethylene and maleic anhydride copolymers;</li><li>homopolymers of alkyl acrylates and homopolymers of alkyl methacrylates such as the product offered under the name MICROPEARL RQ 750 by the company MATSUMOTO or the product offered under the name LUHYDRAN A 848 S by the company BASF;</li><li>copolymers of acrylic esters such as, for example, copolymers of alkyl acrylates and of alkyl methacrylates such as the products offered by the company ROHM &amp; HAAS under the names PRIMAL AC-261 K and EUDRAGIT NE 30 D, by the company BASF under the names ACRONAL 601, LUHYDRAN LR 8833 or 8845, by the company HOECHST under the names APPRETAN N 9213 or N9212;</li><li>copolymers of acrylonitrile and of a nonionic monomer chosen, for example, from butadiene and alkyl (meth) acrylates; we can cite the products offered under the names NIPOL LX 531 B by the company NIPPON ZEON or those offered under the name CJ 0601 B by the company ROHM &amp; HAAS</li><li>homopolymers of styrene such as the product RHODOPAS 5051 offered by the company RHONE POULENC;</li><li>copolymers of styrene and of alkyl (meth) acrylate such as the products MOWILITH LDM 6911, MOWILITH DM 611 and MOWILITH LDM 6070 offered by the company HOECHST, the products RHODOPAS SD 215 and RHODOPAS DS 910 offered by the company RHONE POULENC;</li><li>copolymers of styrene, alkyl methacrylate and alkyl acrylate such as the product DAITISOL SPA offered by the company WACKHERR;</li><li>copolymers of styrene and butadiene such as the products RHODOPAS SB 153 and RHODOPAS SB 012 offered by the company RHONE POULENC;</li><li>copolymers of styrene, butadiene and vinylpyridine such as the products GOODRITE SB VINYLPYRIDINE 2528X10 and GOODRITE SB VINYLPYRIDINE 2508 offered by the company GOODRICH;</li><li>polyurethanes such as the products offered under the names ACRYSOL RM 1020 or ACRYSOL RM 2020 by the company ROHM &amp; HAAS, the products URAFLEX XP 401 UZ, URAFLEX XP 402 UZ by the company DSM RESINS;</li><li>copolymers of alkyl acrylate and of urethane such as the product 8538-33 by the company NATIONAL STARCH;</li><li>polyamides such as the product ESTAPOR LO 11 offered by the company RHONE POULENC.</li></ul>

The alkyl radicals of nonionic polymers have from 1 to 6 carbon atoms unless otherwise stated.

According to the invention, it is also possible to use fixing polymers of the grafted silicone type comprising a polysiloxane portion and a portion consisting of a non-silicone organic chain, one of the two portions constituting the main chain of the polymer the other being grafted on the said main channel. These polymers are for example described in the applications for<patcit id="pcit0023" dnum="EP0412704A"><text>Patent EP-A-0 412 704</text></patcit>, <patcit id="pcit0024" dnum="EP0412707A"><text>EP-A-0 412 707</text></patcit>, <patcit id="pcit0025" dnum="EP0640105A"><text>EP-A-0 640 105</text></patcit> and <patcit id="pcit0026" dnum="WO9500578A"><text>WO 95/00578</text></patcit>, <patcit id="pcit0027" dnum="EP0582152A"><text>EP-A-0582 152</text></patcit> and <patcit id="pcit0028" dnum="WO9323009A"><text>WO 93/23009</text></patcit> and the <patcit id="pcit0029" dnum="US4693935A"><text>US patents 4,693,935</text></patcit>, <patcit id="pcit0030" dnum="US4728571A"><text>US 4,728,571</text></patcit> and <patcit id="pcit0031" dnum="US4972037A"><text>US 4,972,037</text></patcit>. These polymers are preferably anionic or nonionic. Such polymers are, for example, the copolymers capable of being obtained by radical polymerization from the mixture of monomers constituted by:<ol id="ol0006" compact="compact"><li>a) 50 to 90% by weight of tert-butyl acrylate;</li><li>b) 0 to 40% by weight of acrylic acid;</li><li>c) 5 to 40% by weight of silicone macromer of formula:<chemistry id="chem0012" num="0012"><img file="EP0822802B2_D0012.tif" /></chemistry>with v being a number ranging from 5 to 700; the weight percentages being calculated relative to the total weight of the monomers.</li></ol>

Other examples of grafted silicone polymers are in particular polydimethylsiloxanes (PDMS) onto which are grafted, via a thiopropylene-type connecting link, mixed polymer units of the poly (meth) acrylic acid type and of the poly type. alkyl (meth) acrylate and polydimethylsiloxanes (PDMS) onto which are grafted, via a thiopropylene-type connecting link, polymeric units of the isobutyl poly (meth) acrylate type.

According to the present invention, the fixing polymers are preferably anionic polymers.

The anionic or amphoteric fixing polymers can be partially or totally neutralized if necessary. Neutralizing agents are, for example, sodium hydroxide, potassium hydroxide, 2-amino-2-methyl-propanol-1, monoethanolamine, triethanolamine or triisopropanolamine, mineral or organic acids such as hydrochloric acid or citric acid .

By volatile silicone is meant according to the present invention, any silicone having a measurable vapor pressure and in particular which measured at 25 ° C. at atmospheric pressure (10⁵ Pa) is preferably greater than 0.01 mm Hg (2.6 Pa). Oils are preferably used whose boiling point at atmospheric pressure is of the order of 80 to 260 ° C.

Among the volatile silicones, there may be mentioned:<ul id="ul0008" list-style="dash" compact="compact"><li>(i) cyclic volatile silicones having from 3 to 7 silicon atoms and preferably from 4 to 5 which can correspond to the following formula (VIII):<chemistry id="chem0013" num="0013"><img file="EP0822802B2_D0013.tif" /></chemistry></li></ul>in which r varies from 3 to 7 (limits included).

These are, for example, cyclotetradimethylsiloxane, cyclopentadimethylsiloxane or cyclohexadimethylsiloxane,<ul id="ul0009" list-style="dash" compact="compact"><li>(ii) linear volatile silicones having from 2 to 9 silicon atoms. They can respond to the following formula (IX):<chemistry id="chem0014" num="0014"><img file="EP0822802B2_D0014.tif" /></chemistry></li></ul>in which s varies from 1 to 8 (limits included). These are, for example, hexamethyldisiiloxane or octamethyltrisiloxane, The volatile silicones are preferably cyclotetradimethylsiloxane and hexamethyldisiloxane.

The term “non-volatile silicone” is understood to mean, according to the present invention, any silicone having a vapor pressure measured at 25 ° C. at atmospheric pressure (10⁵ Pa) preferably less than 0.01 mm Hg (2.6 Pa).

The non-volatile arylated silicones comprise at least one optionally substituted aryl type radical. The aryl radicals are for example phenyl, naphthyl, benzyl or phenethyl.

The non-volatile arylated silicones preferably have the following formula (X):<chemistry id="chem0015" num="0015"><img file="EP0822802B2_D0015.tif" /></chemistry>in which :<ul id="ul0010" list-style="none" compact="compact"><li>R₂₄, identical or different, denotes a C 1 alkyl radical₁-VS₁₀.</li><li>R₂₆, identical or different, denotes an aryl group, this aryl group possibly comprising one or more aryl rings, optionally substituted</li><li>R₂₅, identical or different, denotes R₂₆, R₂₄ or If (R₂₄)₃</li><li>t varies from 0 to 1000,</li><li>u varies from 1 to 1000,</li><li>the sum t + u can vary from 1 to 2000.</li></ul>

The substituents of the aryl groups can be alkyl, alkenyl, acyl, ketone, halogen (for example Cl and Br) groups, amines. Examples of aryl groups are phenyl, a phenyl group substituted by alkyl radicals or C alkenyl radicals.₁-VS₅ such as allylphenyl, methylphenyl, ethylphenyl, vinylphenyl and mixtures thereof.

Preferably, R₂₄ denotes a methyl radical. Preferably, R₂₅ denotes a phenyl radical. Preferably, R₂₅ denotes a methyl, phenyl or trimethylsilyl radical. More particularly, the sum t + u varies from 1 to 1000.

Among the compounds of formulas (X), it is possible to use, for example, phenyl trimethicone, diphenyl dimethicone or phenyl methicone (names INCI 5th edition 1993). By way of example of these compounds, mention may be made of those sold by the company BAYER under the name BAYSILONE FLUID PD5 oil, by the company DOW CORNING under the name DOW CORNING 556 FLUID, by RHONE POULENC under the names MIRASIL DPDM, RHODORSIL HUILE 510 V 100, RHODORSIL HUILE 550, RHODORSIL HUILE 510V500, RHODORSIL HUILE 710, under the name WACKER BELSIL PDM 20, FDM 200, PDM 1000 by the company WACKER.

According to the present invention, use is preferably made of non-volatile arylated silicones having a refractive index greater than or equal to 1.46, and in particular between 1.48 and 1.7. The refractive index is measured using a refractometer according to well known methods.

The fixing polymer (s) are present in concentrations of between 1% and 10% by weight relative to the total weight of the composition.

The volatile silicone (s) are present in concentrations of between 5% and 40% by weight, and preferably in concentrations of between 10% and 30% by weight and even more particularly of 15 to 25% by weight relative to the weight total composition

The non-volatile arylated silicone (s) are present in concentrations of between 5% and 40% by weight, and this preference in concentrations of between 10% and 30% by weight and even more particularly of 12 to 20% by weight relative to the total weight of the composition.

The sum of the concentrations of non-volatile aryl silicone and of volatile silicone is generally between 10% and 60% by weight, and preferably between 20% and 40% by weight, relative to the total weight of the composition.

The cosmetically acceptable medium generally comprises solvents compatible with the fixing polymer and the non-volatile aryl silicone. These solvents are preferably C alcohols₁-VS₅, which can be used alone or as a mixture.

Among these alcohols, mention may be made of ethanol, isopropanol, polyalcohols such as diethylene glycol, glycol ethers, monoalkyl ethers of glycol, of diethylene glycol, of propylene glycol or of dipropylene glycol. Ethanol is particularly preferred.

The compositions according to the invention are preferably free of water, that is to say that they contain less than 8% by weight of water relative to the total weight of the composition and preferably less than 5%. The drying of the compositions is thus faster

According to the invention, the volatile silicones and the non-volatile arylated silicones are preferably dissolved in the compositions.

The composition of the invention may also contain at least one additive chosen from thickeners, fatty acid esters, fatty acid esters of glycerol, non-volatile and non-arylated silicones, surfactants, perfumes, preservatives, sunscreens, proteins, vitamins, polymers, vegetable, animal, mineral or synthetic oils and any other additive conventionally used in the cosmetic field.

These additives are present in the composition according to the invention in proportions which may range from 0 to 20% by weight relative to the total weight of the composition. The precise amount of each additive depends on its nature and is easily determined by those skilled in the art.

Of course, those skilled in the art will take care to choose the optional compound (s) to be added to the composition according to the invention in such a way that the advantageous properties intrinsically attached to the composition according to the invention are not, or substantially not, altered by the proposed addition.

The compositions according to the invention can be in the form of milk, cream, more or less thickened lotion.

The compositions according to the invention can be used as rinsed products and preferably as leave-in products, in particular for maintaining the hairstyle or shaping keratin materials such as the hair.

They are more particularly styling products such as fixing compositions (lacquers) and styling. Lotions can be packaged in various forms, in particular in vaporizers, pump bottles in order to ensure application of the composition in vaporized form.

The subject of the invention is also a method of cosmetic treatment of keratin materials such as the hair, consisting in applying a composition to them as defined above.

The compositions according to the invention are prepared according to methods well known from the state of the art. In particular, the ingredients are mixed and then packaged in an appropriate container according to the intended use.

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. (In what follows MA stands for Active Matter).

<u>EXAMPLE 1</u>

A fixing spray composition was prepared packaged in a pump-bottle of the following composition:<ul id="ul0011" list-style="dash" compact="compact"><li>Vinyl acetate / crotonic acid copolymer sold by BASF under the name LUVISET CA 66 3 g</li><li>2-amino-2-methyl-propanol-1 qs 100% neutralization of the polymer</li><li>Phenylated silicone sold under the name DC 556 by the company DOW CORNING 5 g</li><li>Octamethyltetracyclosiloxane (MIRASIL CM4 from RHONE POULENC) 15 g</li><li>Ethanol qs 100 g</li></ul>

This composition is sprayed on dry hair, the hairstyle remains in place. The hair is very shiny and does not have a greasy feel.

<u>EXAMPLE 2</u>

A fixing spray composition was prepared packaged in a pump-bottle of the following composition:<ul id="ul0012" list-style="dash" compact="compact"><li>Methyl ester / maleic anhydride mono esterified copolymer sold by the company ISP under the name GANTREZ ES 425 8 g</li><li>2-amino-2-methyl-propanol-1 qs 20% neutralization of the polymer</li><li>Phenylated silicone sold under the name DC 556 by the company DOW CORNING 15 g</li><li>Octamethyltetracyclosiloxane (MIRASIL CM4 from RHONE POULENC) 15 g</li><li>Ethanol qs 100 g</li></ul>

The composition has the same properties as those of Example 1.

<u>EXAMPLE 3</u>

A fixing spray composition was prepared packaged in a pump-bottle of the following composition:<ul id="ul0013" list-style="dash" compact="compact"><li>Methyl ester / maleic anhydride mono esterified copolymer sold by the company ISP under the name GANTREZ ES 425 5 g</li><li>2-amino-2-methyl-propanol-1 qs 20% neutralization of the polymer</li><li>Diphenyldimethicone sold under the name Mirasil DPDM by the company RHONE POULENC 5 g</li><li>Octamethyltetracyclosiloxane (MIRASIL CM4 from RHONE POULENC) 25 g</li><li>Ethanol qs 100 g</li></ul>

The composition has the same properties as those of Example 1.

<u>EXAMPLE 4</u>

A fixing spray composition was prepared packaged in a pump-bottle of the following composition:<ul id="ul0014" list-style="dash" compact="compact"><li>Vinyl acetate / p-tert-butyl benzoate / crotonic acid terpolymer sold under the name MEXOMERE PW by the company CHIMEX 10 g</li><li>2-amino-2-methyl-propanol-1 qs 100% neutralization of the polymer</li><li>Diphenyldimethicone sold under the name Mirasil DPDM by the company RHONE POULENC 25 g</li><li>Octamethyltetracyclosiloxane (MIRASIL CM4 from RHONE POULENC) 20 g</li><li>Ethanol qs 100 g</li></ul>

The composition has the same properties as those of Example 1.

<u>EXAMPLE 5</u>

A composition (A) of fixing spray according to the invention was prepared, packaged in a pump-bottle of the following composition:<ul id="ul0015" list-style="dash" compact="compact"><li>Terpolymer acrylic acid / ethyl acrylate / n-tertio butylacrylamide sold under the name ULTRAHOLD STRONG by the company BASF 5 g</li><li>2-amino-2-methyl-propanol-1 qs 100% neutralization of the polymer</li><li>Diphenyldimethicone sold under the name Mirasil DPDM by the company RHONE POULENC 14 g</li><li>Octamethyltetracyclosiloxane (MIRASIL CM4 from RHONE POULENC) 20 g</li><li>Ethanol qs 100 g</li></ul>

A composition (B) of fixing spray according to the invention was prepared, packaged in a pump-bottle of the following composition:<ul id="ul0016" list-style="dash" compact="compact"><li>Terpolymer acrylic acid / ethyl acrylate / n-tertio butylacrylamide sold under the name ULTRAHOLD STRONG by the company BASF 5 g</li><li>2-amino-2-methyl-propanol-1 qs 100% neutralization of the polymer</li><li>Phenylated silicone sold under the name DC 556 by the company DOW CORNING 14 g</li><li>Octamethyltetracyclosiloxane (MIRASIL CM4 from RHONE POULENC) 20 g</li><li>Ethanol qs 100 g</li></ul>

Compositions which were not in accordance with the invention (C) and (D) were also prepared by replacing the phenylated silicone with the same amount of a non-arylated non-volatile silicone known to provide shine and softness properties.

Composition (C)

:

Dimethiconecopolyol sold under the name POLYMER ABX by the company OSI

Composition (D)

:

Dimethiconecopolyol sold under the name Mirasil DMCO by the company RHONE POULENC

Each of these compositions was applied to washed and dried hair. A panel of 5 experienced testers evaluated the properties of each composition.

The results are collated in the following table:<tables id="tabl0001" num="0001"><table frame="all"><tgroup cols="4"><colspec colnum="1" colname="col1" colwidth="41mm" /><colspec colnum="2" colname="col2" colwidth="31mm" /><colspec colnum="3" colname="col3" colwidth="24mm" /><colspec colnum="4" colname="col4" colwidth="42mm" /><thead valign="top"><row><entry align="center"><b>TESTED FORMULATION</b></entry><entry align="center"><b>Fixing</b></entry><entry align="center"><b>Shine</b></entry><entry align="center"><b>To touch</b></entry></row></thead><tbody><row><entry align="center"><b>A (Invention)</b></entry><entry align="center">very good fixation</entry><entry align="center">very bright</entry><entry align="center">Non-greasy touch</entry></row><row><entry align="center"><b>B (Invention)</b></entry><entry align="center">very good fixation</entry><entry align="center">very bright</entry><entry align="center">Non-greasy touch</entry></row><row><entry align="center"><b>C (Comparative)</b></entry><entry align="center">no fixing</entry><entry align="center">no shine</entry><entry align="center">Very sticky and fatty touch</entry></row><row><entry align="center"><b>D (Comparative)</b></entry><entry align="center">no fixing</entry><entry align="center">no shine</entry><entry align="center">Acceptable touch</entry></row></tbody></tgroup></table></tables>

Only the compositions (A) and (B) according to the invention have good gloss, fixing and touch properties. Although the compositions contain 34 g of silicone, the compositions according to the invention (A) and (B) have very good fixing power.

The composition (A) according to the invention was also compared with the same composition (A) not containing volatile silicone (Octamethyltetracyclosiloxane) (Composition (E)).

The two compositions (A) and (E) were applied to washed and dried hair. A panel of 5 experienced testers evaluated the properties of each composition.<tables id="tabl0002" num="0002"><table frame="all"><tgroup cols="4"><colspec colnum="1" colname="col1" colwidth="41mm" /><colspec colnum="2" colname="col2" colwidth="31mm" /><colspec colnum="3" colname="col3" colwidth="21mm" /><colspec colnum="4" colname="col4" colwidth="34mm" /><thead valign="top"><row><entry align="center"><b>TESTED FORMULATION</b></entry><entry align="center"><b>Fixing</b></entry><entry align="center"><b>Shine</b></entry><entry align="center"><b>To touch</b></entry></row></thead><tbody><row><entry align="center"><b>A (Invention)</b></entry><entry align="center">very good fixation</entry><entry align="center">very bright</entry><entry align="center">Non-greasy touch</entry></row><row><entry align="center"><b>E (Comparative)</b></entry><entry align="center">good fixation</entry><entry align="center">not very bright</entry><entry align="center">Touch a little fat</entry></row></tbody></tgroup></table></tables>

<u>EXAMPLE 6</u>

A fixing spray composition was prepared packaged in a pump-bottle of the following composition:<ul id="ul0017" list-style="dash" compact="compact"><li>Vinyl acetate / crotonic acid copolymer sold by BASF under the name LUVISET CA 66 8 g</li><li>2-amino-2-methyl-propanol-1 qs 100% neutralization of the polymer</li><li>Phenyl dimethicone sold under the name BELSIL PDM 200 by the company WACKER 5 g</li><li>Octamethyltetracyclosiloxane (MIRASIL CM4 from RHONE POULENC) 20 g</li><li>Ethanol qs 100 g</li></ul>

<u>EXAMPLE 7</u>

A fixing spray composition was prepared packaged in a pump-bottle of the following composition:<ul id="ul0018" list-style="dash" compact="compact"><li>Methyl ester / maleic anhydride mono esterified copolymer sold by the ISP group under the name GANTREZ ES 425 4 g</li><li>2-amino-2-methyl-propanol-1 qs 20% neutralization of the polymer</li><li>Phenyl dimethicone sold under the name BELSIL PDM 200 by the company WACKER 20 g</li><li>Hexamethyldisiloxane (BELSIL DM 0.55 from WACKER) 25 g</li><li>Ethanol qs 100 g</li></ul>