MXPA96003212A - Fixing power and/or conditioning cosmetic composition containing particular acrylic copolymer - Google Patents

Abstract

The present invention refers to a pulverizable or vaporizable cosmetic composition, particularly in the form of an aerosol, comprising a cosmetically acceptable aqueous or hydroalcoholic media, at least a fixing and/or conditioning polymer and at least an alkyl/acrylic acid alkyl/methacrylate acrylate.

Description

COSMETIC COMPOSITION OF FIXED POWER AND / OR CONDITIONER CONTAINING AN ACRYLIC COPOLYMER PARTICULAR FIELD OF THE INVENTION The invention relates to an easily sprayable and / or vaporizable cosmetic composition comprising, in a cosmetically acceptable aqueous or hydroalcoholic medium, at least one fixing and / or conditioning polymer and at least one particular acrylic copolymer, as well as the use of this particular copolymer. to improve the vaporization or spraying of the composition including at least one fixing and / or conditioning polymer.

BACKGROUND OF THE INVENTION The hair compositions for spraying on the hair are essentially constituted by a solution most often hydroalcoholic and by a polymer optionally mixed with various cosmetic adjuvants. This solution is conditioned either in a pump bottle, or in a suitable aerosol container that is put under pressure with the help of a REF: 22891 propellant gas. For essentially ecological reasons, efforts are made to reduce the volatile compounds to atmospheric pressure, called VOCs (Volatile Organic Compounds) that are present in the compositions. VOCs are mainly propellants and some solvents such as ethanol. Thus, the legislation of some countries has imposed a maximum percentage of VOCs in aerosol cosmetic compositions. To reduce the amount of VOC, we have tried to replace solvents such as ethanol with water. These modifications can cause problems in particular on the quality of the spray of the liquid jet. The liquid particles sprayed are not fine, the jet of liquid is often pinched, that is to say non-diffuse and the formation of a light foam and / or bubbles may occur. Spraying, since it is an essential element for the final quality of a composition for spraying on the hair, it is essential to remedy these drawbacks in order to obtain a good distribution over the whole of the hair and a fixation and / or a correct conditioning of the hair. EP-A-590604 discloses an aqueous composition based on an anionic acrylic copolymer and hair spray compositions comprising this aqueous composition based on anionic acrylic copolymer. This polymer-based composition is compatible with numerous solvents. It has good cosmetic properties. However, the appearance of the sprays is still not satisfactory. The Applicant has now discovered, unexpectedly and surprisingly, that by associating the polymers customarily used in the compositions for maintaining and / or conditioning the styling agent with the particular anionic polymer described above, it is possible to obtain aqueous or hydroalcoholic compositions easily sprayable and / or vaporizable.

DESCRIPTION OF THE INVENTION The subject of the present invention is therefore a cosmetic composition comprising, in a cosmetically acceptable aqueous or hydroalcoholic medium, at least one fixing and / or conditioning polymer and at least one acrylic copolymer formed by (a) approximately 35 to 74% by weight of an alkyl acrylate, (b) about 25 to 65% by weight of alkyl methacrylate and (c) about 1 to 15% by weight of one or more ethylenic carboxylic acids having from 3 to 5 carbon atoms, the alkyl radicals having from 1 to 5 carbon atoms having these percentages by weight, based on the total weight of the copolymer. The subject of the invention is also the use of the copolymer described above for improving the quality of vaporization or spraying of cosmetic compositions packaged, for example, in a pump bottle or in an aerosol, and comprising a fixing and / or conditioning polymer. The powders obtained with the compositions according to the invention are further diffused, the drops are thinner. The compositions do not foam or very little. In the context of the present application, cosmetic compositions for the maintenance of the hairstyle are understood as any composition whose function is to temporarily fix the shape of the hairstyle, such as, for example, the lacquers, the marking compositions and the styling sprays. By the fixing power of the composition, the behavior of the latter is designated in giving the hair a cohesion in such a way that the initial shape of the hairstyle is conserved. By "fixing polymer" is meant any polymer which has the function of temporarily fixing the shape of the hairstyle. In the context of the present application, the term "conditioning polymer" means any polymer whose function is to improve the cosmetic properties of the hair, in particular the softness, the unraveling, the touch, the static electricity. According to the invention, the acrylic copolymer described above generally has a vitreous transition temperature comprised between about 10 and 50 ° C and preferably between 20 and 40 ° C and even more particularly between 25 and 35 ° C. This copolymer can have a number average molecular weight between 10000 and 50000, and preferably between 20,000 and 40,000. The alkyl acrylate is preferably chosen from methyl acrylate, ethyl acrylate, propyl acrylate and sodium acrylate. butyl. Ethyl acrylate is particularly preferred. The concentration of alkyl acrylate is preferably between 40 and 70% by weight and more particularly between 50 and 60% by weight relative to the total weight of the copolymer. The alkyl methacrylate is preferably chosen from methyl methacrylate, ethyl methacrylate, propyl methacrylate and butyl methacrylate. Methyl methacrylate is particularly preferred. The concentration of alkyl methacrylate is preferably between 30 and 50% by weight and more particularly between 30 and 40% by weight relative to the total weight of the copolymer. Preferred ethylenic carboxylic acids are acrylic acid, methacrylic acid, crotonic acid, itaconic acid or mixtures thereof. Acrylic acid and methacrylic acid are particularly preferred. According to the invention, it is possible to use salts of these carboxylic acids. The concentration of ethylenic carboxylic acids or their salts is preferably between 5 and 15% by weight and more particularly between 8 and 12% by weight relative to the total weight of the copolymer. In a particularly preferred embodiment of the invention, the acrylic acid is used with methacrylic acid, each in a concentration comprised between 2 and 10% by weight, the total of these two acids not exceeding 15% by weight of the total weight of the copolymer. The copolymer can also contain small amounts, ie less than 10%, preferably less than 5% and more particularly less than 2%, of a polymerizable monomer other than those mentioned above. The copolymer can be used in the form of an aqueous dispersion. Generally, the dispersion then comprises at least 0.05% surfactant which allows the dispersion and the dispersion maintenance of the polymer. According to the invention, any type of surfactant can be used in the said dispersion, but preferably a nonionic surfactant, and more particularly polyoxyalkylenated alkyl (CeC? 2) phenol. The average particle size of the copolymer in the dispersion is preferably between 0.1 and 1 micron. According to a particularly preferred embodiment of the invention, a copolymer comprising from 50 to 60% by weight of ethyl acrylate, from 30 to 40% by weight of methyl methacrylate, from 2 to 1 is used. 10% by weight of acrylic acid, from 2 to 10% by weight of methacrylic acid, not exceeding the total concentration of acrylic and methacrylic acid by 15% by weight relative to the total weight of the acrylic copolymer. A copolymer of this type is described, for example, in the patent application EP-A-590604 which is included herein by way of reference. An aqueous dispersion of the acrylic copolymer described above comprising 25% by weight of ethyl acrylate / methyl methacrylate / methacrylic acid / acrylic acid copolymer having a vitreous transition temperature of about 30 ° C is particularly sold under the name AMERHOLD DR -25 by the AMERCHOL Society. According to the invention, the carboxylic acid functions of the acrylic copolymer can be partially or totally neutralized. According to the invention, any fixing polymer and / or conditioning agent known per se can be used. In particular, a fixing and / or conditioning polymer selected from anionic, cationic, amphoteric, nonionic polymers and mixtures thereof can be used. The conditioning polymers are preferably chosen from cationic, amphoteric polymers and mixtures thereof. The fixing and / or conditioning polymers can be used in solubilized form or in the form of a latex (aqueous dispersion of solid polymer particles). Thus, the anionic polymers generally used are polymers which include carboxylic, sulfonic or phosphoric acid derivative groups and have a number average molecular weight between about 500 and 5000,000. 1) The carboxylic groups are provided by unsaturated mono or dicarboxylic carboxylic monomers such as those which correspond to the formula: wherein n is an integer from 0 to 10, A designates a methylene group, optionally attached to the carbon atom of the unsaturated group or to the next methylene group when n is greater than 1 by mediating a heteroatom such as oxygen or sulfur, Ri denotes a hydrogen atom, a phenyl or benzyl group, R 2 denotes a hydrogen atom, a lower alkyl or carbonyl group, R 3 denotes a hydrogen atom, a lower alkyl group, a -CH 2 -COOH, phenyl or benzyl group. In the aforementioned formula a lower alkyl radical preferably designates a group having from 1 to 4 carbon atoms and in particular, methyl and ethyl. The anionic polymers with preferred carboxylic groups according to the invention are: A) The 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, ULTRAHOLD by the company BASF, the acrylic acid and acrylamide copolymers sold in the form of their sodium salt under the names RETEN 421, 423 or 425 by the company HERCULES, the sodium salts of the polyhydroxycarboxylic acids. B) The copolymers of acrylic or methacrylic acid with a monoethylenic monomer such as ethylene, styrene, vinyl esters, esters of acrylic or methacrylic acid, 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, including copolymers of this type in their chain an optionally N-alkylated and / or hydroxyalkylated acrylamide motif such as are particularly described in the Luxembourg patent applications 75370 and 75371 or proposed under the name QUADRAMER by the AMERICAN CYANAMID Society. Mention may also be made of the copolymers of acrylic acid and C 1 -C 4 alkyl methacrylate and the terpolymers of vinyl pyrrolidone, acrylic acid and C 1 -C 20 alkyl methacrylate, for example of lauryl such as that sold by the ISP Company under the designation ACRYLIDONE LM and the terpolymers of methacrylic acid / ethyl acrylate / tert-butyl acrylate such as the product sold under the name LUVIMER 100 P by the company BASF. C) Copolymers derived from crotonic acid such as those which include in their chain vinyl acetate or propionate and optionally other monomers such as allyl or metalyl esters, vinyl ether or vinyl ester of a linear or branched saturated carboxylic acid of long hydrocarbon chain such as those which include at least 5 carbon atoms, these polymers possibly being grafted and crosslinked or else a vinyl, allyl or metalyl ester of an α- or β-cyclic carboxylic acid. Such polymers are described among others in French patents 1,222,944, 1,580,545, 2,265,782, 2,265,781, 1,564,110 and 2,439,798. Commercial products that fall into this class are resins 28-29-30, 26 13-14 and 28-13-10 sold by the NATIONAL STARCH Company. D) Polymers derived from acids or anhydrides maleic, fumaric, itaconic with vinyl esters, vinyl ethers, vinyl halides, phenyl vinyl derivatives, acrylic acid and its esters; these polymers can be esterified. 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 ISP company. The polymers also included in this class are the copolymers of maleic, citraconic, itaconic anhydrides and of an allyl or methallyl ester optionally including an acrylamide, methacrylate, an α-olefin, acrylic or methacrylic esters, acrylic or methacrylic acids or the vinylpyrrolidone in its chain, the anhydride functions are monoesterified or monoamidified. These polymers are described, for example, in French patents 2, 350,384 and 2,357,241 of the applicant company. E) Polyacrylamides including carboxylate groups. 2) The polymers comprising the sulfonic groups are polymers including vinylsulfonic, styrene sulfonic, naphthalene sulphonic or acrylamido alkylsulfonic motifs. These polymers can be chosen in particular from: - the polyvinylsulfonic acid salts having a number average molecular weight between about 1,000 and 100,000 as well as the 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. - the salts of the polystyrene sulphonic acid the sodium salts having a number average molecular weight of approximately 500,000 and of 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 sulphonic acids mentioned in US Pat. No. 4,128,631 and more particularly the salts of polyacrylamidoethylpropane sulfonic acid. According to the invention, the anionic polymers are preferably chosen from acrylic acid copolymers such as the terpolymers of acrylic acid / ethyl acrylate / N-tert-butyl acrylamide sold, for example, under the name ULTRAHOLD STRONG by the company BASF, the copolymers derived from crotonic acid such as the vinyl acetate / tertiary butyl benzoate / crotonic acid terpolymers and the crotonic acid / vinyl acetate / vinyl neododecanoate terpolymers sold in particular under the name Resine 28-29-30 by the National Starch Society, polymers derived from maleic, fumaric, fumaric, itaconic anhydrides with vinyl esters, vinyl ethers, vinyl halides, phenyl vinyl derivatives, acrylic acid and their esters such as methyl vinyl ether / maleic esterified monohydric anhydride copolymers sold in particular under the name GANTREZ ES 425 by the ISP society, the c methacrylic acid and methyl methacrylate copolymers sold under the name EUDRAGIT L by the company ROHM PHARMA, the copolymers of methacrylic acid and ethyl acrylate sold under the name LUVIMER MAEX by the company BASF, the terpolymers of vinylpyrrolidone / acrylic acid / Lauryl methacrylate sold under the name ACRYLIDONE LM by the ISP Company, the terpolymers methacrylic acid / ethyl acrylate / tert-butyl acrylate sold under the name LUVIMER 100 P by the company BASF. The cationic polymers which can be used according to the present invention are preferably chosen from polymers including primary, secondary, tertiary and / or quaternary amine groups forming part of or directly linked to the polymer chain, and having a number average molecular weight of between 500 and approximately 5,000,000 and preferably between 1,000 and 3,000,000. In the context of cationic fixing polymers, cationic polymers with a conductivity lower than or equal to 1 mohm "1 cm" 1 and whose viscosity at 1% in water is less than 20 cps (20 mPa.s) are preferred. The viscosity was measured with the aid of a Rheo at RM 180 (Contraves TV mobile 1) from Mettler. Among these polymers, the following cationic polymers may be mentioned more directly: (1) homopolymers or copolymers derived from esters or from acrylic or methacrylic amides and which include at least one of the following formulas -C wherein: Ri and R2 represent hydrogen or an alkyl group having from 1 to 6 carbon atoms; R3 designates H or CH3; A is a linear or branched alkyl group of 1 to 6 carbon atoms or a hydroxyalkyl group of 1 to 4 carbon atoms; R4, R5, R6, identical or different, represent an alkyl group having from 1 to 18 carbon atoms or a benzyl radical; X designates a methosulfate anion or a halide such as chloride or bromide. The copolymers of the family (1) also contain one or more motifs which are derived from comonomers which can be chosen from the family of acrylamides, methacrylamides, diacetone acrylamides, acrylamides and methacrylamides substituted on nitrogen by lower alkyls, acrylic or methacrylic acids or its esters, vinylactams such as vinylpyrrolidone or vinylcaprolactam, vinyl esters. Thus, among these copolymers of the family (1), mention may be made of: - the copolymers of acrylamide and of dimethylaminoethyl methacrylate quaternized by dimethyl sulphate sold under the name HERCOFLOC by the Company HERCULES, the copolymers of acrylamide and methacryloyloxyethyltrimethylammonium chloride described, for example, in the patent application EP-A-080976 and sold under the name BINA QUAT P 100 by the CIBA Company GEIGY, - the acrylamide and methacryloyloxyethyltrimethylammonium methanesulfate copolymers sold under the name RETEN by the company HERCULES, - the quaternized or not quaternized dialkylaminoalkyl vinylpyrrolidone / acrylate copolymers, such as the products sold under the name "GAFQUAT" by the ISP Company such as "GAFQUAT 734" or "GAFQUAT 755" or the products called "COPOLYMER 845, 958 and 937". These polymers are described in detail in French patents 2,077,143 and 2,393,573, the terpolymers dimethyl methacrylate to ethno / vinyl caprolactam / vinylpyrrolidone such as the product sold under the name GAFFIX VC 713 by the ISP Company, and the copolymers quaternized dimethylaminopropyl vinylpyrrolidine / methacrylamide such as the product sold under the name "GAFQUAT HS 100" by the ISP Company. (2) the quaternized polysaccharides described more particularly in the American patents 3,589,578 and 4,031,307 such as the product marketed under the name JAGUAR C 13 S by the company MEYHALL. (3) the quaternary copolymers of vinylpyrrolidone and vinylimidazole. (4) Chitosans or their salts, the usable salts are in particular acetate, lactate, glutamate, gluconate or pyrrolidone carboxylate of chitosan. Among these compounds, mention may be made of chitosan having a 90.5% deacetylation percentage 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 amphoteric polymers which can be used according to the invention can be chosen from polymers including A and B-motifs distributed statistically in the polymer chain where A denotes a moiety derived from a monomer which includes at least one basic nitrogen atom and B denotes a A motif derived from an acidic monomer that includes one or more carboxylic or sulphonic groups or A and B can designate groups derived from zwitterionic monomers of carboxybetaines or sulfobetaines; A and B may also designate a cationic polymer chain including primary, secondary, tertiary or quaternary amine groups, in which at least one of the amine groups bears a carboxylic or sulphonic group attached via a hydrocarbon radical or A and B they form part of a chain of a polymer of ethylene α, β-dicarboxylic motif of which one of the carboxylic groups has been brought to react with a polyamine which includes one or more primary or secondary amine groups. The amphoteric polymers which meet the above given definition are more particularly preferred among the following polymers: 1) polymers resulting from the copolymerization of a monomer derived from a vinyl compound bearing a carboxylic group such as more particularly acrylic acid, methacrylic acid, maleic acid, alpha-chloracrylic acid, and a basic monomer derived from a substituted vinyl compound containing at least one basic atom such as more particularly dialkylaminoalkylmethacrylate and acrylate, dialkylaminoalkyl ethacrylamide and acrylamide. Such compounds are described in U.S. Patent No. 3,836,537. (2) polymers derived from diallyldialkyl ammonium and from at least one anionic monomer such as polymers that include about 60 to about 99% by weight of units derived from a diallyl dialkyl ammonium quaternary monomer in which the alkyl groups are independently chosen from alkyl groups having from 1 to 18 carbon atoms and in which the anion is derived from an acid having an ionization constant greater than 10"13 and from 1 to 40% by weight of this polymer, from an anionic monomer selected from the ometacrylic acrylic acids, the number average molecular weight of this polymer being between about 50,000 and 10,000,000 determined by gel permeation chromatography Such polymers are described in the application EP-A-269,243. Preferred among others are polymers which include alkyl groups selected from the groups having 1 to 4 carbon atoms and more particularly methyl, ethyl groups. Among these polymers, copolymers of dimethyldiallyl onium chloride or diethyldiallylammonium chloride and of acrylic acid are particularly preferred. These polymers are for example sold under the names "MERQUAT 280" and "MERQUAT 295" by the MERCK Company. It is also possible to use the terpolymers of dimethyldiallylammonium chloride / acrylic acid / acrylamide sold under the name "MERQUAT PLUS 3330" by the company MERCK. (3) polymers including derivative motifs: a) of at least one monomer selected from acrylamides or methacrylamides substituted on nitrogen by an alkyl radical, b) of at least one acid comonomer containing one or more reactive carboxylic groups , and c) of at least one basic comonomer such as esters with primary, secondary, tertiary and quaternary amine substituents of the 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 those groups whose alkyl radicals contain from 2 to 12 carbon atoms and more particularly N-ethylacrylamide, N-tert-butyl acrylamide, N-tertiooctyl acrylamide, N- octylacrylamide, N-decylacrylamide, N-dodecyl acrylamide as well as the corresponding methacrylamides. Acid comonomers are chosen more particularly from acrylic, methacrylic, crotonic, itaconic, maleic, fumaric acids as well as alkyl monoesters having from 1 to 4 carbon atoms of the maleic or fumaric acids or anhydrides. Preferred basic comonomers are aminoethyl, butyl aminoethyl, N, N-dimethylaminoethyl, N-tert-butylaminoethyl methacrylates. Copolymers whose CTFA name (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 (4), are partially crosslinked and alkylated polyamino amides. totally derived from polyaminoamides of general formula: - [- CO-Rio - CO - Z -] - (II) wherein Rio represents a divalent radical derived from a saturated dicarboxylic acid, from an aliphatic mono or dicarboxylic acid of ethylene double bond, from an ester of a lower alkanol having from 1 to 6 carbon atoms, from these acids or from a radical which is derived from the addition reaction 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: a) in the proportions of 60 to 100 mol%, the radical -NH - [- (CH2) x-NH -] - n (III) where x = 2 and n = 2 or 3 or x = 3 and n = 2 deriving this radical from diethylene triamine, from triethylene tetraamine or from dipropylene triamine; b) in the proportions of 0 to 40 mol% the radical (III) indicated above, in which x = 2 and n = l and which is derived from ethylenediamine, or the radical derived from piperazine: c) in the proportions of 0 to 20 mol% the radical -NH- (CH2) 6-NH- which are derived from hexamethylenediamine, these polyaminoamides being cross-linked by the addition reaction of a bifunctional crosslinking agent selected from epihalohydrins, diepoxides, the dianhydrides, the bis-unsaturated derivatives, by means of 0.025 to 0.35 moles of crosslinking agent per amine group of the polyaminoamide and alkylated by the action of acrylic acid, chloroacetic acid or an alkane sultone or its salts. Saturated carboxylic acids are preferably chosen from acids having from 6 to 10 carbon atoms such as adipic acid, 2,3,4-trimethyl and 2,4,4 adipic, terephthalic, ethylenic double bond acids are example acrylic, methacrylic, itaconic acids. The sultone alkanes used in the alkylation are preferably propane or butane sultone, the salts of the alkylating agents are preferably the sodium or potassium salts. (5) polymers that include zwitterionic motifs of the formula: wherein Rn designates a polymerizable unsaturated group such as an acrylate, methacrylate, acrylamide or methacrylamide group, x and y represent an integer from 1 to 3, R12 and R13 represent hydrogen, methyl, ethyl or propyl, R1 and R15 represent a hydrogen or an alkyl radical such that the sum of the carbon atoms in Ri4 and R15 does not exceed 10. Polymers comprising such units may also include motifs derived from non-zwitterionic monomers such as vinylpyrrolidone, acrylate or methacrylate. dimethyl or diethylaminoethyl or alkyl acrylates or methacrylates, acrylamides or methacrylamides or vinyl acetate. By way of example, mention may be made of the copolymer of methyl methacrylate / dimethyl carboxymethylammonium methyl methacrylate such as the product sold under the name DIAFORMER by the company SANDOZ. (6) Polymers derived from chitosan that include monomeric motifs that respond to the following formulas: the reason D being present in proportions comprised between 0 and 30%, the motif E in proportions comprised between 5 and 50% and the motif F in proportions comprised between 30 and 90%, it being understood that in this reason F, R 6 represents a radical of formula: wherein if n = 0, Ri7, Ie and R19, identical or different, each represents a hydrogen atom, a methyl, hydroxyl, acetoxy or amino radical, a monoalkylamine radical or a dialkylamine radical optionally interrupted by one or more carbon atoms; nitrogen and / or optionally substituted by one or more amine, hydroxyl, carboxyl, alkylthio, sulphonic groups, an alkylthio radical whose alkyl group carries an amino residue, at least one of the radicals R? 7 Ris and R19 in this case being one atom of hydrogen; or if n = l, Ri7, Ris and R? 9 each represent a hydrogen atom, as well as the salts formed by these compounds with bases or acids. (7) Polymers derived from the N-carboxyalkylation of chitosan such as N-carboxymethyl chitosan or N-carboxybutyl chitosan sold under the name "EVALSAN" by the JAN DEKKER Company. (8) Polymers corresponding to the general formula (IV) are described in French patent 1,400,366: wherein R2o represents a hydrogen atom, a radical CH30 'CH3CH20' phenyl, R2? denotes hydrogen or a lower alkyl radical such as methyl, ethyl, R22 designates hydrogen or a lower alkyl radical such as methyl, ethyl, R23 designates a lower alkyl radical such as methyl, ethyl or a radical that corresponds to the formula: -R24- N (R22) 2, R24 which represents a group -CH2-CH2 - -CH2-CH2-CH2-, CH2-CH (CH3) -, having R <2> the meanings mentioned above, as well as the higher homologs of these radicals and which contain up to 6 carbon atoms. (9) Amphoteric polymers of the type -A-Z-A-Z selected from. a) polymers obtained by the action of chloracetic acid or sodium chloracetate on the compounds that include at least one of the formula: -A-Z-A-Z-A- (VI) where A designates a radical \ / and Z denotes the symbol B or B ', B or B' identical or different designate a bivalent radical which is a straight or branched chain alkylene radical including up to 7 carbon atoms in the main chain unsubstituted or substituted by hydroxyl groups and which may further include oxygen, nitrogen, sulfur atoms, from 1 to 3 aromatic and / or heterocyclic cations; the oxygen, nitrogen and sulfur atoms being present in the form of ether, thioether, sulfoxide, sulfone, sulfonium, alkylamine, alkenylamine, hydroxyl, benzylamine, amine oxide, quaternary ammonium, amide, imide, alcohol, ester and / or urethane. b) The polymers of formula: -A-Z-A-Z- (VI ') where A designates a radical and Z denotes the symbol B or B 'and at least one time B'; having B the meaning indicated above and B "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 unsubstituted by one or more hydroxyl radicals and including one or more Nitrogen atoms, the nitrogen atom being replaced by an interrupted alkyl chain, optionally by an oxygen atom and obligatorily including one or more carboxyl functions or one or more hydroxyl functions and betainized by reaction with chloroacetic acid or soda chloracetate (10) alkyl (C1-C5) vinyl ether / maleic anhydride copolymers partially modified by semi-dialysis with a N, N, -dialkylaminoalkylamine such as N, N-dimethylaminopropylamine or by semi-esterification with an N, N-dialkylaminoalkanol. These copolymers can also include other vinyl comonomers such as vinylcaprolactam.

Particularly preferred amphoteric polymers according to the invention are those of the family (3) such as copolymers whose CTFA name is octylacrylamide / acrylates / butylaminoethyl methacrylate copolymers such as the products sold under the name AMPHOMER or LOVOCRYL 47 by the company NATIONAL STARCH. The fixative and / or conditioning polymers are for example present in concentrations of between 0.1% and 20% by weight, and preferably in concentrations of between 1% and 10% by weight, based on the total weight of the composition. composition. The concentration of acrylic copolymer is generally between 0.01 and 15% by weight relative to the total weight of the composition and preferably between 0.05 and 8% by weight. The weight ratio between the fixing polymer and / or conditioner and the acrylic copolymer may be between 0.1 and 10 and preferably between 0.5 and 5. The cosmetically acceptable medium is preferably constituted by water or a mixture of water and of cosmetically acceptable solvents such as monoalcohols, polyalcohols, glycol ethers, which may be used alone or in admixture. Mention may be made more particularly of lower alcohols such as ethanol, isopropanol, polyalcohols such as diethylene glycol, glycol ethers, such as glycol or diethylene glycol alkylethers. The concentration in solvents is generally between 0 and 80% by weight and preferably between 0 and 55% by weight relative to the total weight of the composition. Preferably, the cosmetically acceptable medium is essentially constituted by water. The pH of the compositions according to the invention is generally between 2 and 9, and in particular between 3 and 8. It can be adjusted to the chosen value by means of alkalizing agents or acidulants usually used in cosmetics for this type of application. When the composition according to the invention is pressurized in the form of an aerosol in order to obtain a lacquer, it comprises at least one propellant agent which can be chosen from volatile hydrocarbons such as n-butane, propane, isobutane, pentane. , chlorinated and / or fluorinated hydrocarbons and their mixtures. It is also possible to use carbon dioxide, nitrous oxide, dimethyl ether, nitrogen, compressed air and mixtures thereof as the propellant. The propellant concentration is generally between 10 and 50% by weight relative to the total weight of the pressurized composition and preferably between 15 and 35% by weight. The compositions according to the invention pressurized or can not also contain surfactants, preservatives, sequestering agents, softeners, colorants, viscosity modifying agents, foam modifying agents, anti-foam agents, pearlizing agents, moisturizing agents, antipyretic agents, antiseborrhoeic agents, sunscreens, proteins, vitamins, plasticizers, hydroxy acids, electrolytes and perfumes. The compositions according to the invention can also contain other conditioning agents. These can then be chosen from natural and synthetic oils and waxes, fatty alcohols, polyhydric alcohol esters, glycerides, silicone gums and resins or mixtures of these various compounds.

Of course, the person 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 linked to the composition according to the invention are not or substantially altered by the addition considered. . The compositions used according to the invention are, for example, clarified or unclarified hair compositions. They are more particularly marking lotions, lotions for brush marking, fixing compositions (lacquers) and styling. The lotions may be conditioned in various forms, particularly in vaporizers, pump bottles or aerosol containers in order to ensure application of the composition in vaporized form. The subject of the invention is also a method for the cosmetic treatment of keratin materials, such as hair, characterized in that it consists of applying a cosmetic composition as defined above to keratin materials, then optionally rinsing with water, after a period of time. eventual exposure time. Concrete but by no means limiting examples will now illustrate the invention. In the examples, MA means active material.

EXAMPLE 1 Two compositions according to the invention A and B were prepared and compared with compositions C and D each containing only one of the two polymers. The four compositions have been conditioned in a bottle-pump. A staff of 5 experienced testers assessed the appearance of the spray and the presence or absence of foam at the outlet of the container or on the hair. For the evaluation of the appearance of the spray, the note went from 0 (bad) which means that the spray was not diffuse, that the sprayed droplets were not fine at 5 (excellent) which means that the spray was very diffuse and that the droplets powdered were very thin. For the evaluation of the presence or absence of foam at the exit of the container or in the hair, the note went from 0 (bad) which means that there was a foam abounding unacceptable to 5 (excellent) which means that there was nothing of foam. The results are grouped in the table given below: (11ULTRAHOLD STRONG from BASF: acrylic acid terpolymer / ethyl acrylate / N-tertiobutylacrylamide. (2) AMERHOLD DR 25 from AMERCHOL: ethyl acrylate / methyl ethacrylate / methacrylic acid / acrylic acid copolymer with a glass transition temperature of approximately 30 ° C in aqueous dispersion comprising 25% by weight of acrylic copolymer (3) AMP: 2-amino-2-methylpropanol The compositions according to the invention A and B have a diffuse spray and no foam is produced at the outlet of the bottle-pump or on the hair.

EXAMPLE 2 Two compositions according to the invention E and F were prepared and compared with compositions G and H each containing only one of the two polymers. The four compositions were conditioned in a bottle-pump. A staff of 5 experienced testers evaluated the appearance of the spray and the presence or absence of foam at the outlet of the container or in the hair. For the evaluation of the appearance of the spray, the note went from 0 (bad) which means that the spray was not diffuse, that the sprayed droplets were not fine at 5 (excellent) which means that the spray was very diffuse and that the droplets powdered were very thin. For the evaluation of the presence or absence of foam at the exit of the container or in the hair, the note went from 0 (bad) which means that there was an unacceptable abundant foam at 5 (excellent) which means that there was nothing foam. The results without indicate in the table given below: (1) LOVOCRYL 47 from NATIONAL STARCH: Octylacrylamide / acrylates / butylaminoethyl methacrylate copolymer (CTFA). (21AMERHOLD DR 25 of AMERCHOL: ethyl acrylate / methyl ethacrylate / methacrylic acid / acrylic acid copolymer having a vitreous transition temperature of about 30 ° C in an aqueous dispersion comprising 25% by weight of copolymer. (3, AMP: 2-amino-2-methyl propanol) The compositions according to the invention E and F have a diffuse spray and there is no foam at the outlet of the pump bottle or on the hair.

EXAMPLE 3: A composition J according to the invention was prepared and compared with compositions K and L each containing only one of the two polymers. The three compositions were conditioned in aerosol. A staff of 5 experienced testers evaluated the appearance of the spray and the absence or presence of foam at the outlet of the container or on the hair. For the evaluation of the appearance of the spray, the note went from 0 (bad) which means that the spray was not diffuse, that the sprayed droplets were not fine at 5 (excellent) which means, that the spray was very diffuse and that the Powdered droplets were very thin. For the evaluation of the presence or absence of foam at the exit of the container or on the hair, the note went from 0 (bad) which means that there was an unacceptable abundant foam at 5 (excellent) which means that there was no foam . The results are indicated in the table given below: (1) ULTRAHOLD STRONG from BSF: acrylic acid terpolymer / ethyl acrylate / N tertiary butylacrylamide. (2) AMERHOL AMERHOLD DR 25: ethyl acrylate / methyl methacrylate / methacrylic acid / acrylic acid copolymer having a vitreous transition temperature of about 30 ° C in aqueous dispersion comprising 25% by weight of copolymer. (3! AMP: 2-amino-2-methyl propanol (4) DME: dimethyl ether (propellant) The composition according to the invention J has a diffuse spray and there is no foam at the outlet of the aerosol or on the hair.

EXAMPLE 4: A concrete example of a composition according to the invention pressurized in an aerosol with the following composition is provided: - Octylacrylamide / acrylates / butylaminoethyl-methacrylate copolymer (LOVOCRYL 47 from NATIONAL STARCH) 2 gMA -Colopolymer ethyl acrylate / methyl methacrylate / methacrylic acid / acrylic acid sold in aqueous dispersion at 25% MA under the name AMERHOLD DR 25 by AMERCHOL 3 gMA - 2-amino-2-methyl-1-propanol is pH 9 - Ethanol 20 g - Dimetileter 35 g - Water esp 100 g EXAMPLE 5 A concrete example of a composition according to the invention packaged in a pump bottle with the following composition is provided: - Dimethyl amino ethyl methacrylate terpolymer / vinylcaprolactam / vinylpyrrolidone in 37% ethanol solution in MA (GAFFIX VC 713 from ISP) 2 gMA - Copolymer ethyl acrylate / methyl methacrylate / methacrylic acid / acrylic acid sold in aqueous dispersion at 25% MA under the name AMERHOLD DR 25 by AMERCHOL 2 gMA - 2-amino-2-methyl-1-propanol is pH 7 - Water esp 100 g EXAMPLE 6 A concrete example of a composition according to the invention packaged in a bottle-pump with the following composition is provided: - Copolymer methacrylic acid / hydroxyethyl methacrylate / butyl acrylate / methyl methacrylate sold in aqueous dispersion at 41% active material under the name ACUDYNE 255 by the SEPPIC Society 4 gMA - Ethyl acrylate / methyl methacrylate / methacrylic acid / acrylic acid copolymer sold in aqueous dispersion at 25% MA under the name AMERHOLD DR 25 by AMERCHOL 2 gMA - 2-amino-2-methyl-l-propanol is pH 7 - Water esp 100 g It is noted that, in relation to this date, the best method known by the applicant to carry out the aforementioned invention is that which is clear from the present description of the invention. Having described the invention as above, the content of the following is claimed as property.

Claims (18)

1. Cosmetic composition, characterized in that it comprises in a cosmetically acceptable aqueous or hydroalcoholic medium, at least one fixing and / or conditioning polymer and at least one acrylic copolymer formed by (a) approximately 35 to 74% by weight of a alkyl acrylate, (b) from about 25 to 65% alkyl methacrylate and (c) from about 1 to 15% of one or more ethylenic carboxylic acids having from 3 to 5 carbon atoms, having the alkyl radicals of 1 to 5 carbon atoms and the percentages expressed in relation to the total weight of the copolymer.

2. Composition according to claim 1, characterized in that the acrylic copolymer has a vitreous transition temperature comprised between about 10 and 50 ° C, a number average molecular weight between 10000 and 50000.

3. Composition according to any one of claims 1 and 2, characterized in that the acrylic copolymer is a copolymer of ethyl acrylate / methyl methacrylate / methacrylic acid / acrylic acid.

4. Composition according to the preceding claim, characterized in that the acrylic copolymer comprises from 50 to 60% by weight of ethyl acrylate, from 30 to 40% by weight of methyl methacrylate, from 2 to 10% by weight. weight of acrylic acid, from 2 to 10% by weight of methacrylic acid, not exceeding the total concentration of acrylic and methacrylic acid of 15% by weight with respect to the total weight of the copolymer.

5. Composition according to any one of the preceding claims, characterized in that the fixing and / or conditioning polymer is present in concentrations comprised between 0.1% and 20% by weight with respect to the total weight of the composition.

6. Composition according to claim 5, characterized in that the fixing and / or conditioning polymer is present in concentrations comprised between 1% and 10% by weight, based on the total weight of the composition.

7. Composition according to any one of the preceding claims, characterized in that the concentration in acrylic copolymer is between 0.01 and 15% by weight with respect to the total weight of the composition.

8. Composition according to claim 7, characterized in that the concentration in acrylic copolymer is between 0.05 and 8% by weight with respect to the total weight of the composition.

9. Composition according to any one of the preceding claims, characterized in that the fixing and / or conditioning polymer is chosen from anionic, cationic, amphoteric, non-ionic polymers and their mixtures.

10. Composition according to the preceding claim, characterized in that the anionic polymer is chosen from: - the acrylic acid copolymers such as the terpolymers acrylic acid / ethyl acrylate / N-tert-butyl-butylacrylamide; -the crotonic acid-derived copolymers such as the terpolymers vinyl acetate / tertiary butyl benzoate / crotonic acid and the terpolymers crotonic acid / phenyl acetate / vinyl neododecanoate; polymers derived from acids or maleic, fumaric, itaconic anhydrides with vinyl esters, vinyl ethers, vinyl halides, phenyl vinyl derivatives, acrylic acid and their esters such as the methyl vinyl ether / maleic esterified anhydride copolymers. - the copolymers of methacrylic acid and methyl methacrylate; - the copolymers of methacrylic acid and ethyl acrylate; the terpolymers of vinylpyrrolidone / acrylic acid / lauryl methacrylate; - the terpolymers methacrylic acid / ethyl acrylate / tert-butyl acrylate.

11. Composition according to claim 9, characterized in that the cationic polymer is chosen from: - the copolymers of acrylamide and of dimethylaminoethyl methacrylate quaternized with dimethyl sulfate, the copolymers of acrylamide and of methacryloyl chloride xiethyltrimethylammonium, - the copolymers of acrylamide and of methacryloyloxyethyltrimethylammonium methosulfate, quaternized or not quaternized dialkylaminoalkyl vinylpyrrolidone / acrylate or methacrylate copolymers, dimethyl amino ethyl methacrylate / vinylcaprolactam / vinylpyrrolidone terpolymers, and quaternized dimethylaminopropyl vinylpyrrolidone / methacrylamide copolymers.

12. Composition according to claim 9, characterized in that the amphoteric polymer is chosen from among the polymers including derived motifs: a) from at least one monomer selected from acrylamides or methacrylamides substituted on nitrogen by an alkyl radical, b) from at least one acid comonomer containing one or more reactive carboxylic groups, and c) of at least one basic comonomer such as esters with primary, secondary, tertiary and quaternary amine substituents of the acrylic and methacrylic acids and the quaternization product of dimethylamino methacrylate ethyl with dimethyl sulfate or diethyl sulfate.

13. Composition according to claim 12, characterized in that the amphoteric polymer is chosen from copolymers whose CTFA name is octylacrylamide / acrylates / butylaminoethylmethacrylate copolymer.

14. Composition according to any one of the preceding claims, characterized in that it is pressurized in the form of an aerosol.

15. Composition according to claim 14, characterized by the fact that it comprises from 10 to 50% by weight of a propellant relative to the total weight of the composition.

16. Use of an acrylic copolymer as defined in any one of claims 1 to 4 for improving the quality of vaporization and / or spraying of cosmetic compositions comprising a fixing and / or conditioning polymer.

17. Use of an acrylic copolymer described in any one of claims 1 to 4 for improving the quality of vaporization and / or spraying of aerosolized pressurized cosmetic compositions comprising a fixing and / or conditioning polymer.

18. Process for the cosmetic treatment of keratin materials, such as hair, characterized in that it consists of applying a cosmetic composition on the keratin materials as defined in any one of claims 1 to 15, then optionally rinsing with water, then of an eventual exposure time.