WO2000018359A1 - Cosmetic composition comprising at least a polymer obtainable from a hydroxystyrene - Google Patents

Abstract

The invention concerns a cosmetic composition designed to be applied on the hair, comprising, in a cosmetically acceptable medium, at least a film-forming linear or branched polymer obtainable by a process comprising homopolymerisation or a (co)polymerisation of at least a hydroxystyrene monomer, one of its precursors or one of its salts, said composition further comprising at least another film-forming polymer. The invention also concerns a hairstyling or hair fixing method using said composition and its use for formulating hairdressing products such as lacquers, sprays or foams, for hair fixing or styling.

Description

 COSMETIC COMPOSITION COMPRISING AT LEAST ONE POLYMER WHICH CAN BE OBTAINED FROM HYDROXYSTYRENE

The subject of the invention is a cosmetic composition intended to be applied to the hair, comprising, in a cosmetically acceptable medium, at least one linear or branched film-forming polymer capable of being obtained by a process comprising a homo- or a (co) -polymerization of at least one hydroxystyrene monomer, one of its precursors or one of its salts, this composition further comprising at least one other film-forming polymer. It also relates to a process for shaping or maintaining hair using this composition as well as its use for the formulation of styling products such as hairsprays, sprays or mousses, with a view to obtaining maintenance or shaping the hairstyle.

The most common hair products for fixing the hair on the cosmetics market are aerosol or pump spray compositions such as hairsprays, sprays or mousses, essentially consisting of a solution, most often alcoholic or hydroalcoholic and a film-forming polymer soluble in water or in alcohol, mixed with various cosmetic adjuvants.

Numerous compositions for maintaining and / or shaping the hair of the prior art, which contain in their formulation styling polymers, can alter the cosmetic properties of the hair. These can, after application of such compositions, for example become rough, lose their natural softness or their pleasant appearance.

We are therefore looking for cosmetic compositions for maintaining and / or fixing the hairstyle which provide the hair, in addition to fixing satisfactory, good cosmetics, including good detangling, softness and a pleasant touch.

Surprisingly and unexpectedly, the Applicant has discovered that it was possible to remedy the technical problems mentioned above by combining with conventional film-forming polymers at least one other particular linear or branched polymer.

The subject of the invention is a cosmetic composition comprising, in a cosmetically acceptable medium:

(i) at least one linear or branched film-forming polymer (A) capable of being obtained by a process comprising a homo- or a (co) - polymerization of at least one hydroxystyrene monomer, one of its precursors or the a salt thereof, the phenyl of this monomer group comprising at least one hydroxyl moiety and being optionally substituted by one or more radicals selected from the group comprising alkyl radicals Ci to C12 alkoxyalkyl Ci -C _12, halogen, SO ₃ H, acyls (C ₂ to C ₁₂ ) amino, carboxy, carboxyalkyls Ci to C-ι ₂ , and

(ii) at least one film-forming polymer (B) different from the first and chosen from anionic, cationic, amphoteric and nonionic film-forming polymers.

Another object of the present invention relates to a method of shaping or maintaining the hairstyle comprising the use of this composition.

Yet another object of the present invention relates to the use of this composition for the manufacture of hair cosmetic compositions, with a view to obtaining maintenance or shaping of the hairstyle. The linear or branched film-forming polymers (A) particularly targeted by the present invention are those distributed by Clariant under the name PHS-E, PHS-PG, PHS-N or even PHS-PG-L.

For the purposes of the present invention, the term "precursor of a hydroxystyrene monomer" means any phenolic derivative capable of leading to hydroxystyrene by the way of a degradation reaction in an acid medium, in particular by dehydration in an acid medium. By way of example, the precursor can be acetoxystyrene or 4-hydroxyphenylmethyl carbinol and the degradation reaction can, in this case, be diagrammed as follows:

acid.

PHS-E is a homopolymer corresponding to the formula:

PHS-E is obtained from acetoxystyrene by means of radical polymerization followed by hydrolysis. Its molecular mass is between 8,000 and 100,000 g / mol. PHS-E is a linear polymer. PHS-PG is a polymer corresponding to the formula:

PHS-PG is obtained by catalyzed polymerization in an acid medium, from 4-hydroxyphenylmethyl carbinol. Its molecular mass is between 4000 and 7000 g / mol.

PHS-N is a polymer corresponding to the formula:

Le PHS-N est un polymère branché Obtenu par polymérisation catalysée en milieu acide du 4-hydroxyphénylmétylcarbinol. Sa masse moléculaire est comprise entre 4 000 et 7 000 g/mol.

PHS-N is a branched polymer Obtained by catalyzed polymerization in an acid medium of 4-hydroxyphenylmetylcarbinol. Its molecular mass is between 4,000 and 7,000 g / mol.

PHS-PG-L is a polymer with the same crude formula as PHS-E. It is also linear. However, the process for obtaining it is different since the polymerization is carried out from hydroxystyrene monomers.

According to a first embodiment of the compositions in accordance with the invention, a film-forming polymer (A) is used which can be obtained by the copolymerization of:

(iii) at least one hydroxystyrene monomer, one of its precursors or one of its salts, the phenyl group of this monomer comprising at least one hydroxyl unit and being optionally substituted by one or more radicals chosen from the group comprising C _1-6 alkyl radicals, C 12 -C alkoxyalkyls C ₂ , halogens, S0 ₃ H, acyls (C ₂ C ₁₂ ) a ino, carboxy, carboxyalkyl C D _{2 C} , and

(iv) at least one other monomer copolymerizable with said hydroxystyrene monomer, one of its precursors or one of its salts, this other monomer being chosen from the group comprising acrylic, methacrylic monomers or their derivatives, in particular acrylates or linear, cyclic or branched C1 to C10 alkyl methacrylates, such as methyl, ethyl, propyl, butyl, isobutyl, tert-butyl, and ethyl-2-hexyl acrylates or methacrylates, N-substituted or N, N'-substituted acrylamides or methacrylamides, vinyl monomers such as vinyl halides, vinyl esters, in particular vinyl benzoate, vinyl tert-benzoate or vinyl acetate. The vinyl, acrylic or methacrylic monomers may advantageously contain one or more siioxane groups. In this case, they are chosen, in particular, from the group comprising:

- the monomers of formula CH ₂ = C (CH3) -CO- (CH ₂ ) 3-Si-0-Si (CH ₃ ) ₂ -CH ₃ ,

- silicone macromonomers with vinyl, allyl monofunctional termination, ether ester or amide of acrylic or methacrylic acid, of formula CH ₂ = C (Rι) -CXR ₂ -Si (CH ₃ ) (R ₄ ) -0-Si ( CH ₃ ) ₂ -R3, in which:

- Ri represents H or CH ₃ ,

- X represents O or NH,

- R ₂ represents (CH ₂ ) _P , p being an integer which can be zero,

- R ₃ and R independently represent CH ₃ or an aliphatic, cycloaliphatic or aromatic group; vinyl, allylic, ether ester or amide monomers of acrylic or methacrylic acid comprising one or more halogen groups, in particular chlorinated and / or fluorinated groups, and / or comprising an absorbing group in UVA and / or UVB, in particular the benzylidene camphor and benzotriazole groups, substituted or not.

According to a second embodiment of the invention, the film-forming polymer (A) is obtained by a homopolymerization reaction. This can advantageously be carried out from acetoxystyrene to obtain the poly-p-acetoxystyrene and be followed by hydrolysis. It can also be carried out in an acid medium from 4-hydroxyphenylmethyl carbinol.

According to this embodiment of the invention, the film-forming polymer (A) is advantageously a homopolymer belonging to the family of poly-p-hydroxystyrene, and preferably poly-4-hydroxystyrene is chosen. The composition in accordance with the invention may in particular comprise, as film-forming polymer (A):

- only a linear homopolymer,

- only a branched homopolymer, or - a mixture of linear homopolymers and branched homopolymers.

The film-forming polymer (A) is advantageously chosen from those which have a molecular mass of between 5,000 and 300,000 g / mol, and preferably between 8,000 and 100,000 g / mol.

The cationic, anionic, amphoteric and nonionic film-forming polymers (B) which can be used in accordance with the invention are described below.

The cationic film-forming 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 to it, and having a molecular weight of 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:

(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 a hydrogen atom or a CH3 radical;

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;

R-] and R2 represent hydrogen or an alkyl group having from 1 to 6 carbon atoms;

X denotes a methosulfate anion or a halide such as chloride or bromide.

The copolymers of family (1) also contain one or more units deriving from comonomers which can be chosen from the family of acrylamides, methacrylamides, diacetones, acrylamides, acrylamides and methacrylamides substituted on nitrogen with lower alkyls, acrylic or methacrylic acids or their esters, vinyllactams such as viπylpyrrolidone or vinylcaprolactam, vinyl esters.

Thus, among these copolymers of family (1), there may be mentioned:

- copolymers of acrylamide and of dimethylaminoethyl methacrylate quaternized with dimethyl sulphate or with a dimethyl halide such than that sold under the name HERCOFLOC by the company HERCULES,

the copolymers of acrylamide and of methacryloyloxyethyltrimethylammonium chloride described for example 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 methacryloyloxyethyltrimethylammonium methosulfate sold under the name RETEN by the company HERCULES,

- 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 French patents 2,077,143 and 2,393,573, - dimethyl amino ethyl methacrylate / vinylcaprolactam / vinylpyrrolidone terpolymers such as the product sold under the name GAFFIX VC 713 by the company ISP,

- And the vinylpyrrolidone / methacrylamide dimethylaminopropyl quaternized copolymer such as the product sold under the name "GAFQUAT HS 100" by the company ISP.

(2) the quaternized polysaccharides described more particularly in US patents 3,589,578 and 4,031,307 such as guar gums containing cationic trialkylammonium groups.

Such products are marketed in particular under the trade names of JAGUAR C13 S, JAGUAR C 15, JAGUAR C 17 by the company MEYHALL.

(3) quaternary copolymers of vinylpyrrolidone and of vinylimidazole such as the products sold by BASF under the name Luviquat

TFC; (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.

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.

(5) cationic cellulose derivatives such as copolymers of cellulose or of cellulose derivatives grafted with a water-soluble monomer comprising a quaternary ammonium, and described in particular in US Pat. No. 4,131,576, such as hydroxyalkyl celluloses, such as hydroxymethyl- , hydroxyethyl- or hydroxypropyl celluloses grafted in particular with a salt of methacryloyloxyethyl trimethylammonium, of methacrylamidopropyl trimethylammonium, of dimethyl-diallylammonium.

The marketed products meeting this definition are more particularly the products sold under the name "CELQUAT L 200" and "CELQUAT H 100" by the National Starch Company.

The anionic film-forming polymers generally used are polymers comprising groups derived from carboxylic, sulfonic or phosphoric acid and have a molecular weight of between approximately 500 and 5,000,000.

1) The carboxylic groups are provided by mono or unsaturated dicarboxylic acid monomers such as those corresponding to the formula:

in which n is an integer from 0 to 10, Ai 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, Rβ denotes a hydrogen atom, a lower alkyl or carboxyl group, Rg denotes a hydrogen atom, a lower alkyl group, a -CH2 group -COOH, phenyl or benzyl;

In the above formula a lower alkyl radical preferably denotes a group having 1 to 4 carbon atoms and in particular, methyl and ethyl.

The anionic film-forming polymers with carboxylic groups preferred according to the invention are:

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 of 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.

B) Copolymers of acrylic or methacrylic acids with a monoethylenic monomer such as ethylene, styrene, vinyl esters, acrylic or methacrylic acid esters, optionally grafted onto a polyalkylene glycol such as polyethylene glycol and optionally crosslinked. Such polymers are described in particular in French patent 1,222,944 and German application 2,330,956, copolymers of this type comprising in their chain an acrylamide unit, optionally N-alkylated and / or hydroxyalkylated. as described in particular in the Luxembourg patent applications 75370 and 75371 or proposed under the name QUADRAMER by the company AMERICAN CYANAMID. Mention may also be made of copolymers of acrylic acid and of C1-C4 alkyl methacrylate and of terpolymers of vinylpyrrolidone, of acrylic acid and of C1-C20 alkyl methacrylate, for example of lauryl, such as that sold by the ISP company under the name ACRYLIDONE LM and methacrylic acid / ethyl acrylate / tert-butyl acrylate terpolymers such as the product sold under the name LUVIMER 100 P by the company BASF.

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 able to be grafted and crosslinked or else a vinyl, allylic or methallylic ester of an α- or β-cyclic carboxylic acid. Such polymers are described inter alia in French patents 1,222,944, 1,580,545, 2,265,782, 2,265,781, 1,564,110 and 2,439,798. Commercial products falling into this class are resins 28-29-30, 26-13-14 and 28-13-10 sold by the company NATIONAL STARCH.

D) copolymers derived from C ₄ -C ₈ monounsaturated carboxylic acids or anhydrides chosen from:

- the 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, phenyl vinyl derivatives, acrylic acid and its esters, the anhydride functions of these copolymers being optionally monoesterified or modified. ; Such polymers are described in particular in US patents 2,047,398, 2,723,248, 2,102,113, GB patent 839,805 and in particular those sold under the names GANTREZ AN or ES by the company ISP. the copolymers comprising (i) one or more maleic, citraconic, itaconic anhydrides and (ii) one or more monomers chosen from allyl or methallyl esters optionally comprising one or more acrylamide, methacrylamide, α-olefin groups, acrylic or methacrylic esters, acrylic or methacrylic or vinylpyrrolidone acids in their chain, the anhydride functions of these copolymers being optionally monoesterified or modified. These polymers are for example described in French patents 2,350,384 and 2,357,241 of the applicant.

E) polyacrylamides containing carboxylate groups.

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

These polymers can in particular be chosen from

- the salts of polyvinylsulfonic acid having a 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 the vinylpyrrolidone.

the salts of polystyrene sulfonic acid the sodium salts having a 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 patent FR 2,198,719. - The salts of polyacrylamide sulfonic acids those mentioned in US Pat. No. 4,128,631 and more particularly the polyacrylamidoethylpropane sulfonic acid sold under the name COSMEDIA POLYMER HSP 1180 by Henkel.

According to the invention, the anionic film-forming 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, the 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, vinyl halides, phenylvinyl derivatives, acrylic acid and its esters such as the methyl vinyl ether / mono ester maleic anhydride copolymer sold under the name GANTREZ ES 425 by the company ISP, methac acid copolymers rylic 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, the vinyl acetate / crotonic acid sold under the name LUVISET CA 66 by the company BASF and the vinyl acetate / crotonic acid copolymer grafted with polyethylene glycol under the name ARISTOFLEX A by the company BASF.

The most particularly preferred anionic film-forming polymers are chosen from the methyl ester / maleic anhydride mono esterified 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 BASF, the copolymers of methacrylic acid and methyl methacrylate sold under the name EUDRAGIT L by the company ROHM PHARMA, the vinyl acetate / vinyl tertiary 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 copolymer of methacrylic acid and ethyl acrylate sold under the name LUVIMER MAEX OR MAE by the company BASF, the terpolymer of vinylpyrrolidone / acrylic acid / lauryl methacrylate sold under the name ACRYLIDONE LM by the company ISP.

The amphoteric film-forming 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 of sulphobetaines; 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 are part of a chain of a polymer containing an ethylene α, β-dicarboxylic unit, one of the carboxyl groups of which has been reacted with a polyamine comprising one or more primary or secondary amine groups.

The amphoteric film-forming polymers corresponding to the definition given above which are more particularly preferred are chosen from the following polymers: 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 dialkyiamino-alkylmethacrylamide and acrylamide. Such compounds are described in US Patent 3,836,537.

(2) polymers comprising units derived from: a) at least one monomer chosen from acrylamides or methacrylamides substituted on nitrogen by an alkyl radical, b) from at least one acidic comoπomer containing one or more carboxylic groups reactants, and 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 as well as 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.

Preferred basic comonomers are methacrylates of aminoethyl, butyl aminoethyl, N.N '.- dimethylaminoethyl, N-tert-butylaminoethyl. Particularly used are the copolymers whose designation CTFA (4th

Ed., 1991) is Octylacrylamide / acrylates / butylaminoethylmethacrylate copolymer such as the products sold under the name AMPHOMER or LOVOCRYL 47 by the company NATIONAL STARCH.

(3) crosslinked and alkylated polyamino amides partially or totally derived from polyaminoamides of general formula:

- Eco— R— co— z-Ξl- ⁽ m ⁾

in which Ri o represents a divalent radical derived from a saturated dicarboxylic acid, from an aliphatic mono or dicarboxylic acid having an ethylenic double bond, from an ester of a lower alkanol having 1 to 6 carbon atoms of these acids or d 'a radical deriving from the addition of any one of said acids with a primary or secondary bis amine, and Z denotes a radical of a bis-primary, mono or bis-secondary polyalkylene polyamine and preferably represents: a ) in the proportions of 60 to 100 mol%, the radical

NH— £ (CH ₂ ) _X NH ^] - ( ^IV )

where x = 2 and p = 2 or 3, or else x = 3 and p = 2 this radical deriving from diethylene triamiπe, triethylene tetraamine or dipropylene triamine; 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:

/ \ N N

\ / c) in the proportions of 0 to 20 mole% of 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 per 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 acid, 2,2,2,4-thmethyl adipic and 2,4,4,4-adipic trimethyl, 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.

(4) polymers comprising zwitterionic units of formula:

dans laquelle R-j -j désigne un groupement insaturé polymérisable tel qu'un groupement acrylate, méthacrylate, acrylamide ou methacrylamide, y et z représente un nombre entier de 1 à 3, R-] 2 et R-13 représentent un atome d'hydrogène, méthyle, éthyle ou propyle, R14 et R15 représentent un atome d'hydrogène ou un radical alkyle de telle façon que la somme des atomes de carbone dans R14 et R-15 ne dépasse pas 10. Les polymères comprenant de telles unités peuvent également comporter des motifs dérivés de monomères non zwittérioniques tels que l'acrylate ou le méthacrylate de diméthyl ou diéthylaminoéthyle ou des alkyle acrylates ou méthacrylates, des acrylamides ou méthacrylamides ou l'acétate de vinyle. A titre d'exemple, on peut citer le copolymère de méthacrylate de méthyle / diméthyl carboxyméthylammonio éthylméthacrylate de méthyle tel que le produit vendu sous la dénomination DIAFORMER Z301 par la société SANDOZ. (5) les polymères dérivés du chitosane comportant des motifs monomères répondant aux formules suivantes :

in which Rj -j denotes a polymerizable unsaturated group such as an acrylate, methacrylate, acrylamide or methacrylamide group, y and z represents an integer from 1 to 3, R-] 2 and R-13 represent a hydrogen atom, methyl, ethyl or propyl, R14 and R15 represent a hydrogen atom or an alkyl radical in such a way that the sum of the carbon atoms in R14 and R-15 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. (5) polymers derived from chitosan containing monomer units corresponding to the following formulas:

le motif D étant présent dans des proportions comprises entre 0 et 30%, le motif E dans des proportions comprises entre 5 et 50% et le motif F dans des proportions comprises entre 30 et 90%, étant entendu que dans ce motif F, R₁₆ représente un radical de formule :

the motif D being present in proportions of between 0 and 30%, the motif E in proportions of between 5 and 50% and the motif F in proportions of between 30 and 90%, it being understood that in this motif F, R ₁₆ represents a radical of formula:

R 19

R 17 - (°) α— Ç

in which if q = 0, R-17, RJ S ^e * ^ 19. 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 amine groups , hydroxyl, carboxyl, alcolylthio, sulfonic, an alkylthio residue in which the alkyl group carries an amino residue, at least one of the radicals R17, R-18 and R19 in this case being a hydrogen atom; or if q = 1, R17, R <| 6 and Rj g each represent a hydrogen atom, as well as the salts formed by these compounds with bases or acids.

(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.

dans laquelle R20 représente un atome d'hydrogène, un radical CH3O, CH3CH2O, phényle, R21 désigne l'hydrogène ou un radical alkyle inférieur tel que méthyle, éthyle, R22 désigne l'hydrogène ou un radical alkyle inférieur tel que méthyle, éthyle, R23 désigne un radical alkyle inférieur tel que méthyle, éthyle ou un radical répondant à la formule : -R24-N(R22)2. ^R24 représentant un groupement -CH₂-CH₂- , -CH₂-CH₂-CH₂- , -CH₂-CH(CH₃)- , R₂2 ayant les significations mentionnées ci-dessus, ainsi que les homologues supérieurs de ces radicaux et contenant jusqu'à 6 atomes de carbone.(7) The polymers corresponding to the general formula (VI), for example described in French patent 1,400,366:

in which R20 represents a hydrogen atom, a CH3O, CH3CH2O, phenyl radical, 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. ^R 24 representing a group -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -, -CH ₂ -CH (CH ₃ ) -, R ₂ 2 having the meanings mentioned above, as well as the homologs higher of these radicals and containing up to 6 carbon atoms.

(8) Amphoteric polymers of the type -D-X-D-X- chosen from: a) the polymers obtained by the action of chloracetic acid or sodium chioracetate on the compounds comprising at least one unit of formula:

-D-X-D-X-D- (VII) where D denotes a radical

/ \

-N N-

\ / and X denote the symbol E or E ', E or E' 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 not substituted or substituted by hydroxyl groups and which may additionally 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. b) The polymers of formula:

-D-X-D-X- (VII ') where D denotes a radical

/ \ N N

\ / 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, substituted or not 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 chloracetate.

(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 comonomers such as vinyicaprolactam.

The amphoteric film-forming polymers which are particularly preferred according to the invention are those of family (3) such as copolymers, the CTFA name 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 carboxymethylammonioethylmethacrylate methyl for example sold under the name DIAFORMER Z301 by the company SANDOZ.

The nonionic film-forming polymers which can be used according to the present invention are chosen, for example, from: - vinylpyrrolidone homopolymers;

- copolymers of vinylpyrrolidone and of vinyl acetate;

- polyalkyloxazolines such as the polyethyloxazolines offered by the company DOW CHEMICAL under the names PEOX 50,000, PEOX 200,000 and PEOX 500,000; - 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;

- the vinyl acetate and acrylic ester copolymers such as the product offered under the name RHODOPAS AD 310 from RHONE POULENC; - copolymers of vinyl acetate and ethylene such as the product offered under the name of APPRETAN TV by the company HOECHST;

- the 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; - copolymers of polyethylene and maleic anhydride;

- the homopolymers of alkyl acrylates and the 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; - 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 & 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; - 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 &HAAS; - polyurethanes such as the products offered under the names ACRYSOL RM 1020 or ACRYSOL RM 2020 by the company ROHM & HAAS, the products URAFLEX XP 401 UZ, URAFLEX XP 402 UZ by the company DSM RESINS;

- copolymers of alkyl acrylate and urethane such as the product 8538-33 by the company NATIONAL STARCH;

- polyamides such as the product ESTAPOR LO 11 offered by the company RHONE POULENC.

- chemically modified or unmodified nonionic guar gums. Unmodified non-ionic guar gums are for example the products sold under the name VIDOGUM GH 175 by the company UNIPECTINE and under the name JAGUAR C by the company MEYHALL. The modified nonionic guar gums which can be used according to the invention are preferably modified with C 1 -C 6 hydroxyalkyl groups. Mention may be made, by way of example, of the hydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxybutyl groups.

These guar gums are well known in the state of the art and can for example be prepared by reacting oxides of corresponding alkenes, such as for example propylene oxides, with guar gum so as to obtain a gum of guar modified by hydroxypropyl groups. Such nonionic guar gums optionally modified by hydroxyalkyl groups are for example sold under the trade names JAGUAR HP8, JAGUAR HP60 and JAGUAR HP120, JAGUAR DC 293 and JAGUAR HP 105 by the company MEYHALL, or under the name GALACTASOL 4H4FD2 the AQUALON company.

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 film-forming 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 patent applications EP-A- 0 412 704, EP-A-0 412 707, EP-A-0 640 105 and WO 95/00578, EP-A-0582 152 and WO 93 / 23009 and US patents 4,693,935, US 4,728,571 and US 4,972,037. 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 consisting of: a) 50 to 90% by weight of tert-butyl acrylate; b) 0 to 40% by weight of acrylic acid; c) 5 to 40% by weight of silicone macromer of formula:

avec v étant un nombre allant de 5 à 700 ; les pourcentages en poids étant calculés par rapport au poids total des monomères. D'autres exemples de polymères siliconés greffés sont notamment des polydiméthylsiloxanes (PDMS) sur lesquels sont greffés, par l'intermédiaire d'un chaînon de raccordement de type thiopropylène, des motifs polymères mixtes du type acide poly(méth)acrylique et du type poly(méth)acrylate d'alkyle et des polydiméthylsiloxanes (PDMS) sur lesquels sont greffés, par l'intermédiaire d'un chaînon de raccordement de type thiopropylène, des motifs polymères du type poly(méth)acrylate d'isobutyle.

with v being a number ranging from 5 to 700; the weight percentages being calculated relative to the total weight of the monomers. 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.

It is also possible to use, as film-forming polymers, polyurethanes which are functionalized or not, silicone or not.

The polyurethanes particularly targeted by the present invention are those described in patents EP 0 751 162, EP 0 637 600, FR 2 743 297 and EP 0 648 485 of which the Applicant is the Holder, as well as patent EP 0 656 021 or WO 94 / 03510 from the company BASF and EP 0 619 111 from the company National Starch.

In the compositions in accordance with the invention, the film-forming polymer (s) (A) are preferably present at concentrations of between 0.1 and 20% by weight, and preferably between 0.5 and 10% by weight relative to the total weight of the composition.

The film-forming polymer (s) (B) are present, for their part, preferably at concentrations of between 0.1 and 20% by weight, and preferably between 0.5 and 10% by weight relative to the total weight of composition.

The cosmetically acceptable medium preferably consists of water or one or more cosmetically acceptable solvents such as monoalcohols, polyalcohols, glycol ethers or fatty acid esters or mixtures of water and solvent (s), these solvents preferably being Cι-C ₄ alcohols.

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

The composition of the invention can also contain at least one additive chosen from thickeners, fatty acid esters, fatty acid esters of glycerol, volatile or non-volatile silicone, modified or not, soluble or insoluble in the composition, the surfactants, the perfumes, the preservatives, the sunscreens, the proteins, the vitamins, the non-fixing polymers, the vegetable, animal, mineral or synthetic oils and any other additive conventionally used in cosmetic compositions intended to be applied on the hair.

These additives are optionally present in the composition according to the invention in proportions which can range, advantageously, from 0.001 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.

These compositions can be packaged in various forms, in particular in pump dispensers or in aerosol containers, in order to ensuring application of the composition in vaporized form or in the form of a foam. Such forms of packaging are indicated, for example, when it is desired to obtain a spray, a lacquer or a foam for fixing or treating the hair. The compositions in accordance with the invention can also be in the form of creams, gels, emulsions or waxes.

When the composition according to the invention is packaged in the form of an aerosol in order to obtain a lacquer or a foam, it comprises at least one propellant which can be chosen from volatile hydrocarbons such as n-butane, propane, isobutane, pentane, a chlorinated and / or fluorinated hydrocarbon and their mixtures. Carbon dioxide, nitrous oxide, dimethyl ether (DME), nitrogen, compressed air can also be used as a propellant. Mixtures of propellants can also be used. Preferably, dimethyl ether is used.

Advantageously, the propellant is present at a concentration between 5 and 90% by weight relative to the total weight of the composition in the aerosol device and, more particularly, at a concentration between 10 and 60%.

The invention will be more fully illustrated with the aid of the following nonlimiting examples.

All the percentages are relative percentages by weight relative to the total weight of the composition and m. at. means active ingredient.

EXAMPLE 1 (Comparison in pump bottle):

The following two styling compositions I and II were prepared. Composition I is in accordance with the prior art and comprises a film-forming polymer conventional, while composition II comprises, in addition to the same conventional film-forming polymer, poly-4-hydroxystyrene. These compositions are summarized in Table 1 below.

Table 1

A sensory test is carried out by implementing the protocol below.

The compositions I and II packaged in a pump bottle equipment are sprayed on locks of 5 grams of natural hair. After drying, an identical lacquering power is obtained and the ease of disentangling and the feel for each of these compositions is evaluated (panel of 6 testers). For each of the 2 criteria, the testers assign a score between 0 and 50 and calculate the average. This average is reported in Table 2 below.

Table 2

Consequently, the combination according to the invention has a significant advantage in disentangling and in touching it.

EXAMPLE 2 (Comparative aerosol):

The two styling compositions III and IV indicated in Table 3 were compared. Composition III is in accordance with the prior art, while composition IV is in accordance with the present invention.

Table 3

The compositions III and IV packaged in an aerosol are sprayed on a panel of 10 models. After drying, an identical lacquering power is obtained and the ease of disentangling and the feel for each of these compositions is evaluated. The average of the results is collated in Table 4 below. Table 4

The results show that the disentangling is clearly improved and the feel is better with composition IV according to the invention than with composition III according to the prior art.

Claims

1. Cosmetic composition for fixing and / or maintaining the hairstyle, characterized in that it comprises, in a cosmetically acceptable medium: (i) at least one linear or branched film-forming polymer (A) capable of being obtained by a process comprising a homo- or a (co) - polymerization of at least one hydroxystyrene monomer, one of its precursors or the one of its salts, the phenyl group of this monomer comprising at least one hydroxyl unit and being optionally substituted by one or more radicals chosen from the group comprising C 1 to C ₁₂ alkyl, C 1 to C ₁₂ alkoxyalkyl, halogen, SO ₃ radicals H, acyls (C ₂ to C ₁₂ ) amino, carboxy and carboxyalkyls Ci to Cι ₂ , and (ii) at least one film-forming polymer (B) different from the first and chosen from anionic, cationic, amphoteric and nonionic film-forming polymers. 2. Composition according to Claim 1, characterized in that the film-forming polymer (A) is capable of being obtained by the copolymerization: (iii) at least one hydroxystyrene monomer, one of its precursors or one of its salts, the phenyl group of this monomer comprising at least one hydroxyl unit and being optionally substituted by one or more radicals chosen from the group comprising alkyls radicals Cι _2, alkoxyalkyl d Cι _2, halogen, S0 ₃ H, acyl _(C2-C12) amino, carboxy, carboxyalkyl -C 12, and (iv) at least one other monomer copolymerizable with said hydroxystyrene monomer, one of its precursors or one of its salts, this other monomer being chosen from the group comprising acrylic, methacrylic monomers or their derivatives, in particular acrylates or linear, cyclic or branched C 1 to C 6 alkyl methacrylates, N-substituted or N, N'-substituted acrylamides or methacrylamides, vinyl monomers such as vinyl halides, vinyl esters, in particular vinyl benzoate , vinyl tertiobenzoate or vinyl acetate. 3. Composition according to claim 2, characterized in that the acrylic or methacrylic monomers or their derivatives are chosen from the group comprising methyl, ethyl, propyl, butyl, isobutyl, tert-butyl acrylates or methacrylates , and ethyl-2-hexyl. 4. Composition according to claim 2 or 3, characterized in that the vinyl, acrylic or methacrylic monomers comprise, in addition, one or more siloxane groups and are chosen from the group comprising in particular: - the monomers of formula CH ₂ = C (CH3) -C-0- (CH ₂ ) 3-Si-0-Si (CH ₃ ) 2-CH ₃ , - silicone macromonomers with vinyl, allyl monofunctional termination, ether ester or amide of acrylic or methacrylic acid, of formula CH ₂ = C (Rι) -CXR ₂ -Si (CH ₃ ) (R ₄ ) -0-Si ( CH ₃ ) ₂ -R3, in which: - Ri represents H or CH ₃ , - X represents O or NH, - R ₂ represents (CH ₂ ) _P , p being between 0 and 20, - R and R independently represent CH ₃ or an aliphatic, cycloaliphatic or aromatic group; vinyl monomers, allyl, ether ester or amide of acrylic or methacrylic acid having one or more halogen groups. 5. Composition according to claim 1, characterized in that the film-forming polymer (A) is obtained by homopolymerization and is of the optionally substituted poly-p-hydroxystyrene type, and preferably poly-4-hydroxystyrene. 6. Composition according to any one of the preceding claims, characterized in that the film-forming polymer (A) has a molecular weight of between 5,000 and 300,000, and preferably between 8,000 and 100,000. 7. Composition according to any one of the preceding claims, characterized in that the film-forming polymer (A) is a linear polymer. 8. Composition according to any one of claimsl to 6, characterized in that the film-forming polymer (A) is a branched polymer. 9. Composition according to any one of the preceding claims, characterized in that the polymer (B) is an anionic polymer chosen from: - polymers comprising carboxylic units derived from mono or unsaturated dicarboxylic acid monomers of formula:

in which n is an integer from 0 to 10, A 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, Rβ denotes a hydrogen atom, an alkyl group lower or carboxyl, Rg denotes a hydrogen atom, a lower alkyl group, a group -CH2-COOH, phenyl or benzyl; - polymers comprising units derived from sulfonic acid such as vinylsulfonic, styrenesulfonic, acrylamido alkylsulfonic units. 10. Composition according to the preceding claim, characterized in that the anionic film-forming polymer is chosen from: - acrylic acid copolymers such as the acrylic acid / ethyl acrylate / N-tert-butylacrylamide terpolymer; - 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; - polymers derived from maleic, fumaric or itaconic acids or anhydrides with vinyl esters, vinyl ethers, vinyl halides, phenyl vinyl derivatives, acrylic acid and its esters such as methyl vinyl ether / mono ester maleic anhydride copolymers ; - copolymers of methacrylic acid and methyl methacrylate; - the copolymer of methacrylic acid and ethyl acrylate; - the vinyl acetate / crotonic acid copolymer; - the vinyl acetate / crotonic acid / polyethylene glycol terpolymer. 11. Composition according to any one of claims 1 to 8, characterized in that the film-forming polymer (B) is an amphoteric polymer chosen from polymers comprising units deriving from: a) at least one monomer chosen from acrylamides or methacrylamides substituted on nitrogen by an alkyl radical, b) at least one acidic comonomer containing one or more reactive carboxylic groups, and 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 the dimethylaminoethyl methacrylate with dimethyl or diethyl sulfate. 12. Composition according to any one of claims 1 to 8, characterized in that the film-forming polymer (B) is a nonionic polymer chosen from: - polyalkyloxazolines; - vinyl acetate homopolymers; - copolymers of vinyl acetate and acrylic ester; - copolymers of vinyl acetate and ethylene; - copolymers of vinyl acetate and maleic ester; - copolymers of polyethylene and maleic anhydride; - homopolymers of alkyl acrylates and homopolymers of alkyl methacrylates; - copolymers of acrylic esters such as, for example, copolymers of alkyl acrylates and alkyl methacrylates; - copolymers of acrylonitrile and of a nonionic monomer chosen for example from butadièπe and alkyl (meth) acrylates; and - copolymers of alkyl acrylate and urethane. 13. Composition according to claim 1 to 8, characterized in that the film-forming polymer (B) is a cationic polymer chosen from: the copolymer of acrylamide and of dimethylaminoethyl methacrylate quaternized with dimethyl sulphate, the copolymers of acrylamide and of methacroyloyloxyethyltrimethylammonium chloride, the copolymer of acrylamide and methacryloyloxyethyltrimethylammonium methosulfate, - vinylpyrrolidone / acrylate or methacrylate of dialkylaminoalkyl quaternized or not, - terpolymer of dimethyl amino ethyl methacrylate / vinylcaprolactam / vinylpyrrolidone, - And the vinylpyrrolidone / methacrylamide dimethylaminopropyl quaternized copolymer. 14. Composition according to any one of claims 1 to 8, characterized in that the film-forming polymer (B) is a polyurethane functionalized or not, silicone or not. 15. Composition according to any one of the preceding claims, characterized in that the film-forming polymer (s) (A) are present at concentrations of between 0.1 and 20% by weight, and preferably at concentrations of between 0, 5 and 10% by weight relative to the total weight of the composition. 16. Composition according to any one of the preceding claims, characterized in that the film-forming polymer (s) (B) are present at concentrations of between 0.1 and 20% by weight, and preferably at concentrations of between 0, 5 and 10% by weight relative to the total weight of the composition. 17. Composition according to any one of the preceding claims, characterized in that it also contains conventional cosmetic additives chosen from the group comprising fatty substances, thickening agents, softeners, anti-foaming agents, agents moisturizers, aπtiperspirants ^agents', basifying agents, dyes, pigments, perfumes, preservatives, surfactants, volatile or non-volatile silicone, modified or not, polyols, proteins and vitamins. 18. Aerosol device formed by a container containing an aerosol composition according to any one of the preceding claims and a propellant gas, as well as a means of dispensing the composition. 19. Method for maintaining or shaping the hairstyle, characterized in that it comprises the use of a composition according to any one of claims 1 to 17. 20. Use of a composition according to any one of claims 1 to 17, for the manufacture of a hair cosmetic product in order to maintain and / or fix the hairstyle.