FR2947820A1 - Ethylenic copolymer comprising ethylenic monomer, cationic monomer e.g. N-(3-dimethylamino-propyl)-acrylamide and anionic monomer comprising maleic anhydride, useful for treating keratin materials - Google Patents

Abstract

Ethylenic copolymer (I) and its salt comprising: 25-95 wt.% of ethylenic monomer (a); 4-50 wt.% of cationic monomer (b) or its salts; and 1-35 wt.% of anionic monomer (c) and/or its salts comprising maleic anhydride, is claimed. Ethylenic copolymer (I) and its salt comprising: 25-95 wt.% of ethylenic monomer of formula (H 2C=CR 1>(-Z-(R 2>) m-(CH 2CH 2O) n)-R 3>) (a); 4-50 wt.% of cationic monomer of formula (H 2C=CR 1>(-(Z1a) x1-(R2a) m1-X)) (b) or its salts; and 1-35 wt.% of anionic monomer and/or its salts, comprising maleic anhydride of formula (H 2C=CR 1>(-(Z1a) x1-(R2a) m1-Y 1>)) (c), is claimed. R 1> : H or CH 3; Z : divalent group comprising -COO- or -CONH; R 2> : 1-18C divalent carbon group optionally saturated, aromatic, and comprising 1-4 heteroatoms of O, N or S; m : 0 or 1; n : 65-700, preferably 100-200; R 3> : H or carbon group, optionally saturated, aromatic, and comprising 1-4 heteroatoms of O, N or S; Z1a : divalent group comprising -COO-, -CO or -CONH; x1 : 0 or 1; R2a : 1-18C divalent carbon group optionally saturated, aromatic, and comprising 1-4 heteroatoms of O, N or S; m1 : 0 or 1; X : group of formula (-NR 6>R 7>) or (-R6a-N-R7a-); either R 6>, R 7> : H, or 1-12C alkyl (optionally saturated and aromatic); or NR 6>R 7> : optionally saturated 5-7 membered aryl ring comprising CH, CH 2, O, N, NH, S, or CO; R6a-N-R7a : optionally saturated 5-7 membered aryl ring comprising CH, CH 2, O, N, NH, S, or CO; R 3> : H or carbon group, optionally saturated, aromatic, and comprising 1-4 heteroatoms of O, N or S; Y 1> : COOH, -SO 3H, -OSO 3H, -PO 3H 2or -OPO 3H 2; and n : 65-700. An independent claim is included for a cosmetic composition comprising the copolymer in a medium.

Description

The present invention relates to novel polymers, to their use in particular in cosmetics, and to the compositions comprising them. It is known to employ polymers in the cosmetic field, and in particular in the capillary, for example to provide hold or styling to the hair. In the field of so-called rinsed hair compositions, such as shampoos or conditioners, water-soluble synthetic cationic polymers, which are known to provide good hair cosmetics, are used, however, these polymers can not be used. 'bring no effect of shaping the hair. It is the same with cationic natural derivative polymers such as modified guais which also provide a cosmetic character without allowing formatting. In the field of rinsed compositions, it is not known to provide hair styling polymers and an acceptable cosmetic. In the field of so-called non-rinsed hair compositions, such as styling products such as hairsprays, gels or styling sprays, one is constantly looking for polymers providing styling effects, and resistance to the hair. Amine polymers, such as polymers based on vinylpyrrolidone and on methylaminoethyl methacrylate (Gaffix polymers), are known in hairstyling products. The compositions obtained, however, have insufficient durability over time. Luviquat-type polymers, based on quaternized vinylimidazole and vinylpyrrolidone, are also known, which provide softness but thicken the compositions. Polymers comprising both polyethylene glycol (meth) acrylate (meth) acrylate units and cationic units have also been proposed. Thus, it is known from EP372546, copolymers based on MPEG and monomers of (meth) acrylamides type C1-C8 alkyl, which may comprise cationic monomers. However, these polymers comprise a small proportion of cationic monomers, which does not allow them to generate adequate cosmetic effects, in particular a deposit on the hair which is sufficient to provide the desired properties. JP2002-322219 discloses polymers containing MPEG units in combination with hydrophobic monomers based on polypropylene glycol (PPO) or tetramethylene polyoxide, and cationic monomers. However, it has been found that these polymers do not make it possible to obtain satisfactory cosmetic properties. JP2002-284627 also discloses a composition comprising cationic polymers in which the PEG-type monomers are associated with monomers comprising quaternary amine units. However, the presence of quaternary units may induce, as and when applications occur, an increase in deposition which may, in certain cases, adversely affect the cosmetic quality of the composition. Moreover, these polymers contain a low cationic charge rate which does not allow an optimal affinity for the hair. Polymers containing MPEG-type units are also known from JP2003-055164, but these polymers are crosslinked, which makes it difficult to control their synthesis. Document JP2000-302649 further describes a hair composition comprising a polymer which comprises cationic monomers comprising quaternary amines, monomers containing a polyether group, in particular of the PEG or PPO type, as well as optional monomers which may be predominantly hydrophobic (for example methacrylate). stearyl). It is also known from JP07-285831, hair compositions comprising a polymer which comprises MPEG-type monomers in combination with ionic, cationic or amphoteric monomers, and additional monomers of (meth) acrylates type. C1-C24 alkyl, predominantly hydrophobic. In these documents, the presence of hydrophobic comonomers, for example of the butyl acrylate or stearyl type, does not make it possible to obtain adequate cosmetic properties, in particular do not make it possible to obtain a good disentangling of wet hair just after the shampoo.

It has also been proposed, for example in Applications EP1769011 and EP1765893, polymers capable of providing a styling effect and an acceptable cosmetic; these polymers consist of cationic units in a majority quantity and MPEG units, and can be neutralized. The MPEGs employed may be of low molecular weight. However, it has been found that the cosmetic properties provided by these polymers can be further improved; in particular the cosmetic properties such as touch especially in a humid environment (on damp or wet hair); as well as build-up (loaded hair).

In the field of hair care, in particular of sensitized hair, especially having undergone coloring, it is sought to provide cosmetic properties on wet hair, in particular an improved feel, as well as shine, softness and detangling in dry conditions (on dry hair). It is known that hair that is sensitized, that is to say damaged and / or weakened, to varying degrees by the action of atmospheric agents, especially light, as well as by the repeated action of various treatments. mechanical or chemical, such as perms, defrosting, staining and discoloration, may exhibit an alteration of the hair fiber, including a decrease in their mechanical properties such as tensile strength, tensile strength and 'elasticity. The hair may be more hydrophilic, losing part of the scales, which results in great difficulty in disentangling and styling the hair, as well as a loss of softness. To remedy this, it is possible to use cationic surfactants of the cetyltrimethylammonium type, in oil-in-water emulsion, in the presence of fatty alcohols. However, the cosmetic properties are not optimal and the formulation of these compositions is complicated: compromise between the stability of the emulsion and the non-greasy feel to be found, in particular.

The purpose of the present invention is to overcome all these drawbacks and to propose polymers which, put into a cosmetic composition, in particular a capillary composition, make it possible to provide improved cosmetic properties, especially disentangling and touching, mainly in a moist environment but also in a dry environment Furthermore, the use of polymers avoids the problems of build-up, that is to say the obtaining of 'heavy' hair, too heavily loaded as and when applications.

The present invention therefore relates to an ethylenic copolymer, or its salts, comprising, in% by weight relative to the total weight of the polymer a) 25 to 85% by weight of monomer of formula (1), alone or as a mixture, as defined below, b) 10 to 50% by weight of cationic monomer or a salt thereof, alone or as a mixture, of formula (II) as defined below; c) 1 to 35% by weight of anionic monomer and / or its salts, alone or as a mixture, selected from maleic anhydride and those of formula (III) as defined below. It has been found that the polymers according to the invention provide adequate conditioning effects, in particular softness to the touch and disentangling on wet hair (in a humid medium) and on dry hair (in a dry medium). Without being bound by this explanation, it can be considered that this is due to the presence and length of the PEG chain. Because of their cationic character, they also have an excellent affinity for keratin substrates such as hair, nails and the corneous layer of the epidermis to which keratin gives a negative charge. Finally, thanks to their anionic nature, they make it possible to avoid the problems of load (build-up). The polymers according to the invention have interesting cosmetic properties, for example when they are applied in a shampoo-type formulation: the hair is easily disentangled during shampooing and has a good peel; the compositions according to the invention also make it possible, once the hair has dried, to form the hair particularly well.

The polymers according to the invention are transportable in water, that is to say soluble. Another object of the invention is a cosmetic composition comprising said ethylenic copolymer. or dispersible in water, which allows them to be used in cosmetic compositions, including capillaries, which are generally water-based. By water-soluble or water-soluble it is meant that the polymer forms a clear solution in water, at least 5% by weight, at 25 ° C. By hydrodispersible or dispersible in water is meant that the polymer forms in water, at a concentration of 5% by weight, at 25 ° C, a stable suspension or dispersion of fine particles, generally spherical. The average particle size constituting said dispersion is less than 1 μm and, more generally, varies between 5 and 600 nm, preferably from 10 to 250 nm. These particle sizes are measured by light scattering. The ethylenic copolymer according to the invention. therefore comprises at least one monomer of formula (I), which may be present alone or as a mixture, Z (R 2) m (CH 2 CH 2 O) n -R 3 in which R 1 is a hydrogen atom or a methyl radical, - Z is a divalent group selected from -COO-, -CONH-, R2 is a divalent carbon radical, saturated or unsaturated, optionally aromatic, linear, branched or cyclic, comprising 1 to 18 carbon atoms, which may comprise 1 to 4 selected heteroatoms from 0, N, S; - mest0ou1 - n is an integer between 65 and 700; R 3 is a hydrogen atom or a carbon radical, saturated or unsaturated, optionally aromatic, linear, branched or cyclic, comprising 1 to 30 carbon atoms, which may comprise 1 to 4 heteroatoms selected from 0, N, S.

In the radical R2, the one or more heteroatoms, when present, may be intercalated in the chain of said radical R2, or said radical R2 may be substituted by one or more groups including them such as OH, SH or amino (NR "R" with R ', R ", identical or different, representing a hydrogen or a linear or branched C1-C4 alkyl, in particular methyl or ethyl). In particular, R2 may be a C1-C18 alkylene radical such as methylene, ethylene, propylene, n-butylene, isobutylene, tert-butylene, n-hexylene, n-octylene, n-dodecylene, noctadecylene, n-tetradecylene, n-docosanylene; optionally substituted with OH, NR'R "; - a phenylene radical -C6H4- (ortho, meta or para), optionally substituted by a C1-C12 alkyl; - a benzylene radical -C6H4-CH2-, optionally substituted by a C1-C10 alkyl, a linear or branched C1-C12 alkylenoxydivalent radical, for example -CH2-CH2-CH2-O (propyloxy), Preferably R2 is a linear C1-C6 alkylene radical.

Preferably, n is between 75 and 500, better still between 80 and 400, even between 90 and 300, and preferably between 95 and 250, and even better between 100 and 200.

Preferably, R3 is a hydrogen atom; a benzyl radical; a phenyl radical optionally substituted with a C1-C12 alkyl; a C1-C30 alkyl radical, in particular a C1-C22 or even a C2-C16 radical, optionally comprising 1 to 4 heteroatoms chosen from O, N and S. Mention may especially be made of the methyl, ethyl, propyl, benzyl and ethylhexyl radicals, lauryl, stearyl, behenyl.

Among the preferred monomers of formula (I), there may be mentioned polyethylene glycol (meth) acrylate) in which R1 is H or methyl; Z is COO, m = 0 and R3 = H; (methyl) polyethylene glycol (meth) acrylate), also known as methoxy-poly (ethylene glycol) methoxy acrylate, wherein R 1 is H or methyl, Z is COO, m = 0 and R 3 = methyl; the alkyl (poly) ethylene glycol (meth) acrylate in which R 1 is H or methyl, Z is COO, m = 0 and R 3 alkyl - the phenyl-poly (ethylene glycol) (meth) acrylates, also called (meth) acrylate of poly (ethylene glycol) phenyl ether, wherein R1 is H or methyl, Z is COO225 m = 0 and R3 = phenyl. The monomers of formula (I) that are most particularly preferred are chosen from polyethylene glycol (meth) acrylates) and methylpolyethylene glycol (meth) acrylates, preferably those having a molecular weight of between 2800 and 30,000 g. mol, in particular between 3500 and 20 000 g / mol, or even between 4000 and 10 000 g / mol.

Examples of commercial monomers are: polyethylene glycol 8000 or 4000 methacrylates from Monomer & Polymer Dajac laboratories; the PMG5000 PEG methacrylates of ARKEMA, having the trade name NORSOCRYL N-405; the methoxy-poly (ethylene glycol) methacrylates of PM5000, available from EVONIK under the trade designation MPEG-5000-MA; Methacrylates of methoxypolyethylene glycol) 5K; 10K, 12K, 20K and 30K from Sunbio.

The monomer of formula (I), alone or as a mixture, is present in a proportion of 25 to 85% by weight, relative to the weight of the final polymer, in particular in the proportion of 30 to 80% by weight, preferably 32 to 75% by weight. by weight, or even 35 to 70% by weight.

The ethylenic copolymer according to the invention also comprises at least one cationic monomer, or one of its salts, which may be present alone or as a mixture, of formula (II) in which - R 1 is a hydrogen atom or a methyl radical; Z 'is a divalent group chosen from -COO-, -C (O) - and -CONH-, - x is or R1 is a divalent carbon radical, saturated or unsaturated, optionally aromatic, linear, branched or cyclic, from 1 to 18 carbon atoms, which may comprise 1 to 4 heteroatoms selected from O, N, S; m 'is 0 or 1; X is selected from (a) a group of formula -N (R6) (R7) with R6, R7 representing, independently of each other, either (i) a hydrogen atom or (ii) a linear, branched or cyclic, saturated or unsaturated, optionally aromatic, alkyl group comprising from 1 to 12 carbon atoms, or (iii) R 6 and R 7 form, with the nitrogen atom, a saturated or unsaturated, optionally aromatic ring, comprising 5, 6 or 7 members selected from CH, CH 2, O, N, NH, S, C (O); or (b) X represents a group -R'6-N-R'7- in which R'6 and R'7 form with the nitrogen atom a saturated or unsaturated, optionally aromatic ring, comprising 5, 6 or 7 members selected from CH, CH 2, O, N, NH, S, C (O). By cationic monomer is meant a monomer comprising units capable of having a cationic charge in the pH range between 3 and 12. These units do not have a permanent charge whatever the pH. The cationic unit does not need to be protonated at each of these pH's.

In the R'2 radical, the heteroatom (s), when present, can be. Intercalated in the chain of said radical R'2, or said radical R'2 may be substituted by one or more groups including them such as OH, SH or NR'R "(with R ', R", identical or different, representing a hydrogen or a linear or branched C1-C4 alkyl, in particular methyl or ethyl). In particular R'2 can be; A C1-C18 alkylene radical such as methylene, ethylene, propylene, n-butylene, isobutylene, tert-butylene, n-hexylene, n-octylene, n-dodecylene, n-octadecylene, n-tetradecylene, n-docosanylene; optionally substituted with OH, NR'R '- a phenylene radical -C6H4- (ortho, meta or para), optionally substituted with a C1-C12 alkyl; a benzylene radical -C6H4-CH2- optionally substituted with a C1-C6 alkyl;

Cl O. - a linear or branched C1-C12 divalent alkylenoxy radical; especially propyloxy -CH2CH2CH2O- Preferentially, R'2 is a C1-C6 alkylene radical; linear, phenylene benzylene. Preferably, R 6 and R 7 may be chosen, independently of one another, from hydrogen or a linear C 1 -C 18 alkyl radical, and in particular methyl, ethyl, propyl, isopropyl or n-butyl, butyl, isobutyl, octyl, lauryl, stearyl. Preferentially, R6 and R7 are chosen, independently of one another, from H, CH3 and C2H5. In particular, X may be a radical -NH2, -N (CH3) 2, -N (C2H5) 2. When R6 and R7 form a ring with the nitrogen atom, this ring is preferably 5- or 6-membered, including the nitrogen atom, and may comprise another heteroatom as a link. In particular, X may be a radical: ## STR2 ## When X represents a group -R'6-N-R'7-, this ring preferably comprises 6 links, including the nitrogen atom, and may comprise another heteroatom as a link. In particular, X may be a radical: Among the preferred monomers of formula (II), and their salts: 2947820, CH.sub.3. Among the monomers of formula (II) that are particularly preferred, mention may be made of (meth) dimethylaminopropyl acrylamide, dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, vinylimidazole, vinylpyridine, morpholinoethyl (meth) acrylate. The monomer of formula (II), alone or as a mixture, is present in a proportion of 10 to 50% by weight, relative to the weight of the final polymer, especially in the proportion of 12 to 48% by weight, preferably 13 to 45% by weight. % in weight.

The ethylenic copolymer according to the invention also comprises at least one anionic monomer and / or its salts, chosen from maleic anhydride and / or those of formula. (III): It is understood that according to the state of the art, the groups SO4H2 and PO4H2 are linked to R'2 by the oxygen atom while the groups S03H and PO3H are bound to R'2 res respectively. via the atoms of S and P.

Among the preferred anionic monomers, mention may be made of maleic anhydride, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, acrylate of carboxyethyl (CH 2 = CH-C (O) -O- (CH 2) 2 -COOH); styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, vinylbenzoic acid, vinylphosphoric acid, sulfopropyl (meth) acrylate, and salts thereof. The monomer of formula (III), alone or as a mixture, is present in a proportion of 1 to 20% by weight, relative to the weight of the final polymer, in particular in the proportion of 2 to 32% by weight, preferably 3 to 30% by weight. % in weight.

In a preferred embodiment, the ethylenic copolymer according to the invention consists essentially of monomer (s) of formula (I), formula (II) and formula (II), which means that it does not include , optionally, other monomers than those mentioned above:

The copolymers according to the invention are uncrosslinked. They are in the form of random ethylenic copolymers, generally filenogenic, of one or more ethylenic monomers containing PEG groups (the PEG groups being pendant along the backbone), of one or more ethylenic monomers comprising cationic functions. (Neutralized and non-quaternary amines) and one or more ethylenic monomers having anionic functions. The term "film-forming polymer" means a polymer capable of forming, on its own or in the presence of a film-forming auxiliary agent, a continuous and adherent film on a support, in particular on keratin materials.

It is possible to neutralize one or both of the moieties constituting the copolymer before polymerization, or to neutralize the copolymer once formed. Preferably, the copolymer is neutralized after formation. wherein R1, Z ', x', R'2 and m 'have the same meaning as given above for formula (II); Y is a group chosen from -000H, -SO3H, -OSO3H, -PO3H2 and -OP03H2.

Preferably, the amine units are neutralized, the neutralization of the acidic units is optional. Preferably, the copolymer is neutralized until a pH less than or equal to 7.5 is obtained for a 5% aqueous solution of said polymer. The neutralization of the amine units, belonging to the polymer and / or the monomers, can be carried out by a Bronsted acid, or a mixture of such acids; in particular by a mineral acid such as sulfuric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid, boric acid, or with an organic acid, which may comprise one or more carboxylic, sulfonic or phosphonic acid groups. They may be linear, branched or cyclic aliphatic acids or else. unsaturated or aromatic acids. These acids may furthermore comprise one or more heteroatoms chosen from O or N, for example in the form of hydroxyl groups. There may be mentioned in particular acetic acid, terephthalic acid, HOOC-PEG-000H acid; citric acid, tartaric acid; betaine HCl or betaine hydrochloride of formula (CH3) 3N + CH2CO2H.Cl-; gluconic acid, 2-ethylcaproic acid. Preferentially, betaine hydrochloride is used. The acid groups may be neutralized, partially or completely, with a mineral base, such as LiOH, NaOH, KOH, Ca (OH) 2, NH 4 OH, Mg (OH) 2 or Zn (OH) 2; or by an organic base such as a primary, secondary or tertiary alkylamine, which may comprise one or more nitrogen and / or oxygen atoms, for example one or more alcohol functions. There may be mentioned triethanolamine, amino-2-methyl-2-propanol, triethylamine, butylamine.

The polymers according to the invention can be prepared according to the usual conventional radical polymerization methods, which are well known to those skilled in the art. In particular, these polymers can be prepared by direct polymerization in solution in water with or without pre-neutralization of the cationic and / or anionic unit; emulsion polymerization in water with or without pre-neutralization of the cationic and / or anionic unit, using a surfactant; polymerization in an organic solvent, such as ethanol or methylethyl butone, with or without pre-neutralization of the cationic and / or anionic unit, followed by a solution or water dispersion stage with evaporation of solvent. These polymerizations may be carried out in the presence of a radical initiator, especially of the peroxide (Trigonox 21S: tert-butyl peroxy-2-ethylhexanoate) or azo (AIBN V 50: 2,2'-azo-bis (2-amidinopropane) dihydrochloride) type. which may be present in a proportion of 0.3 to 5% by weight relative to the total weight of monomers. The copolymers according to the invention have a weight average molecular weight (Mw) which is preferably between 5000 and 1,000,000, in particular between 7,000 and 750,000, preferably between 10,000 and 500,000 g / mol. The weight average molecular weights (Mw) are determined by gel permeation chromatography or by light diffusion, according to the accessibility of the method (solubility of the polymers in question).

The polymers according to the invention are preferably transportable in an aqueous medium, that is to say that they are preferably water-soluble or water-dispersible. The dissolution or dispersion in water may be carried out by direct solubilization of the polymer if it is soluble, or by neutralization of the amine and / or acid units, so as to render the polymer soluble or dispersible in the polymer. water. The dissolution or aqueous dispersion can also be carried out via an intermediate step of solubilization in an organic solvent followed by the addition of water before evaporation of the organic solvent. The polymers according to the invention find a very particular application in the field of cosmetics. They may be present in the composition in solubilized form, for example in water or an organic solvent, or in the form of an aqueous or organic dispersion. They may be used in cosmetic compositions in a proportion of 0.1 to 20% by weight of dry matter, in particular from 0.5 to 15% by weight, or even from 1 to 10% by weight, more preferably from 2 to 8% by weight. % by weight, relative to the total weight of the composition.

The cosmetic compositions according to the invention comprise, in addition to said polymers, a cosmetically acceptable medium, that is to say compatible with keratin materials such as the skin of the face or the body, the hair, the eyelashes, the eyebrows and nails.

Preferably, the cosmetically acceptable medium comprises a solvent or dispersion medium of the polymers according to the invention, which may comprise at least one compound chosen from water, alcohols, polyols, esters and carbonated oils. silicone oils, fluorinated silicone oils, and mixtures thereof.

Preferably, the cosmetically acceptable medium may comprise water or a mixture of water and hydrophilic organic solvent (s) such as alcohols, and especially linear or branched C1-C6 monoalcohols, such as ethanol, tert-butanol, n-butanol, isopropanol or n-propanol, or 2-butoxyethanol; and polyols such as glycerine, diglycerine, ethylene glycol, propylene glycol, sorbitol, pentylene glycol, and polyethylene glycols, or alternatively ethers of polyols or glycols, especially C 2 such as monoethyl ether and diethylene glycol monomethyl ether, and hydrophilic C2-C4 aldehydes. The composition according to the invention may also comprise at least one cosmetically acceptable adjuvant conventionally used in cosmetic compositions, in particular intended to be applied to keratinous fibers. Mention may in particular be made, as a cosmetically acceptable adjuvant, of gelling agents and thickeners; polymers, associative or not; anionic, nonionic, cationic and / or amphoteric surfactants; propenetrating agents, emulsifiers, perfumes, preservatives, pigments, dyes, fillers, sunscreens; dyestuffs, proteins, vitamins, provitamins; polymers, fixing or non-fixing, moisturizing agents, emollients, softening agents; mineral, vegetable or synthetic oils; hydrophilic or lipophilic active agents, ceramides, pseudoceramides; anti-foam agents, antiperspirants, anti-free radical agents, bactericidal agents, anti-dandruff agents, hair loss agents, pearlescent agents, and mixtures thereof. Those skilled in the art will take care to choose these optional adjuvants and their quantity in such a way that the advantageous properties of the composition according to the invention are not; or substantially not, impaired by the addition contemplated.

The compositions according to the invention may be in any of the galenical forms conventionally used for topical application, and especially in the form of an aqueous or alcoholic or aqueous-alcoholic solution or suspension, of an oily solution or suspension, of a solution or lotion or serum dispersion, oil-in-water, water-in-oil or multiple emulsion; an aqueous or anhydrous gel, a dispersion of vesicles, in particular lipids; a biphase or multiphase lotion; a composition of this spray may have the appearance of a lotion thickened or not, a cream thickened or not, an aqueous or anhydrous gel, a mousse, a milk, a serum , an ointment, a soft paste, an ointment, a cast or molded solid and especially a stick or a cup, or a compacted solid. It can optionally be packaged in a pump bottle or in an aerosol container. Those skilled in the art may choose the appropriate dosage form, as well as its method of preparation, on the basis of its general knowledge, taking into account, on the one hand, the nature of the constituents used, in particular their solubility in the support, and on the other hand the application envisaged for the composition.

The cosmetic composition according to the invention may be in the form of a product for the care, cleaning and / or make-up of the skin of the body or the face, the lips, the eyelashes, the nails and the hair. , a sunscreen or self-tanning product, a personal care product, a hair product, especially care, cleaning, styling or hair dyeing. It particularly finds a particularly interesting application in the 2.947820 maine.capillaire, including the maintenance of the hairstyle, shaping the hair and cleaning the hair. The hair compositions are preferably shampoos, conditioners, styling or care gels, lotions or care creams, conditioners, styling lotions, blow-dry lotions, fixing compositions and the like. styling such as lacquers or spray. The lotions may be packaged in various forms, in particular in vaporizers, pump-bottles or in aerosol containers to ensure application of the composition in vaporized form or in the form of foam. It may also be in the form of a hair dye composition; a composition of permanent, defrisage or discoloration; a composition to be rinsed, to be applied before or after a coloring, a discoloration, a permanent, a stripping or between the two stages of a perm or a defrisage. It may also be in the form of a care composition for the skin, lips and / or integuments, or in the form of a composition for cleaning the skin, for example a makeup remover or a gel for bath or shower. It can also be in the form of a care product, not colored, intended to treat the skin and in particular to moisturize it, smooth it, depigment it, nourish it, protect it from the sun's rays, or give it a specific treatment . It may also be in the form of a personal hygiene composition, especially in the form of a deodorant product, antiperspirant, or in the form of a depilatory composition. It may also be in the form of a makeup product, in particular a colored product, of the skin of the body or of the face, or of the hair, in particular a foundation, which may have care properties, blush, blush, eye shadow, eyeliner, eyeliner; a lip makeup product such as a lipstick, possibly with skincare properties, a lip gloss, lip pencils; a make-up product of skin dander such as nails, eyelashes especially in the form of a bread mascara, eyebrows and hair, a temporary tattoo product of the skin of the body.

Advantageously, the composition according to the invention is a hair conditioning hair composition, and may be in the form of a lotion, cream, gel, mousse or spray. The subject of the invention is also a process for the cosmetic treatment, in particular of make-up, care, cleaning, coloring, shaping, keratinic materials, in particular of the skin of the body or of the face, nails hair, eyelashes, lips, comprising the application on said materials of a cosmetic composition as defined above. Preferably, it is a cosmetic treatment method for shaping and / or maintaining the hair, comprising the application of a composition 294.7820

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according to the invention on said hair; possibly followed by a rinsing step.

The invention is illustrated in more detail in the following examples.

Polymer Examples In a 50 ml reactor, under temperature control and provided with orbital stirring, 20 g of methyl ethyl ketone (MEK), 4.5 g of dimethylaminopropyl methacrylamide (DMAPMA), 4.5 g of polyethylene glycol methacrylate are introduced. (MW = 5000, Norsocryl N-405 from Arkema) and 1 g of acrylic acid, and heated at reflux for 30 minutes. 0.1 g of initiator (Trigonox 21S) is then added, followed by continuous flow; after 2 hours, another 0.05 g of initiator is added; the reflux is continued for another 2 hours and another 0.05 g of initiator is added. The mixture is heated under reflux for a total of 7 hours. The reaction is monitored by NMR. The reaction medium is neutralized to 100% by adding 4.5 g of betaine hydrochloride in 30 ml of water; the solvent (MEC) is then evaporated in a rotavapor. A copolymer of MPEG (5000) -co-DMAPMA-co-acrylic acid, in proportion 45/45/10, dissolved in water, with a dry extract of 30% is obtained. Similarly, the polymers 2-4 according to the invention and the following non-invention polymers 5 and 6 are prepared by varying the amounts of starting monomers. % MPEG 5000 ° A DMAPMA% Acry- Acid Dry Extract (%) Example 1 45 45 10 Example 2 Example 3 68.2 13.6 18.2 21 Counter-example 5 Counter-50 50 36 36 Example Test The slipperiness of the polymers is evaluated using a pion-disk tribometer: solutions are prepared to 3% by weight in water of the above polymers, and then deposited on a moving substrate which is brought into contact with a ball. The friction force between the ball and the moving substrate is then measured. The lower the friction force between the two surfaces, the greater the slipperiness of the polymer. The friction force is expressed in Newton (N). The following results are obtained Hydrophilic substrate (N) friction force Example 2 0.28 Example 3 0.25 Against Example 5 0.35 Against Example 6 0.35 It is found that the polymers according to the invention have a better sliding character than comparative polymers.

Cosmetic composition A cosmetic composition comprising (% by weight) - polymer of Example 1 (MS: dry matter) is prepared. 5 ml of this composition is applied to hair (2.5 g strands). There is a very good disentangling in a humid environment and a soft touch in a dry environment.

Claims (7)

REVENDICATIONS1. Ethylenic copolymer, or its salts, comprising, in% by weight relative to the total weight of the polymer - a) 25 to 85% by weight of monomer of formula (I), alone or as a mixture: R CC H2Z (R2) m ( Wherein R1 is a hydrogen atom or a methyl radical; Z is a divalent group selected from -COO-, -CONH-, R2 is a divalent carbon radical, saturated or unsaturated, optionally aromatic; linear, branched or cyclic, comprising 1 to 18 carbon atoms, which may comprise 1 to 4 heteroatoms selected from O, N, S; m is 0 or 1 - n is an integer from 65 to 700; R 3 is a hydrogen atom or a saturated or unsaturated, optionally aromatic, linear, branched or cyclic, carbon radical comprising 1 to 30 carbon atoms, which may comprise 1 to 4 heteroatoms selected from O, N, S; b) 10 to 50% by weight of cationic monomer or one of its salts, alone or as a mixture, of formula (II): (Z 1) X in which - R 1 is a hydrogen atom or a methyl radical ; Z 'is a divalent group chosen from -COO-, C (O) - and -CONH-, - x is O or 1, R'2 is a divalent carbon radical, saturated or unsaturated, optionally aromatic, linear, branched or cyclic from 1 to 18 carbon atoms, which may comprise 1 to 4 heteroatoms selected from O, N, S; - m 'is0ou1; X is selected from: (a) a group of formula = N (R6) (R7) with R6, R7 representing, independently of each other, either (i) a hydrogen atom, or (ii) ) a linear, branched or cyclic, saturated or unsaturated, optionally aromatic, alkyl group comprising from 1 to 12 carbon atoms, or (iii) R 6 and R 7 form, with the nitrogen atom, a saturated or unsaturated ring, optionally aromatic, comprising 5, 6 or 7 members selected from CH, CH 2, O, N, NH, S, C (O); or (b) X represents a group -R'6-N-R'7- in which R'6 and R'7 form with the nitrogen atom a saturated or unsaturated, optionally aromatic, ring comprising 5, 6 or 7 members selected from CH, CH 2, O, N, NH, S, C (O); c) 1 to 35% by weight of anionic monomer and / or its salts, alone or as a mixture, chosen from maleic anhydride and those of formula (III): embedded image in which: R 1, Z ', x ', R'2 and m' have the meaning given above for the formula (II); and Y is a group chosen from -COOH, -SO3H, -OSO3H, -PO3H2 and OPO3H2. 15 2. Copolymer according to claim 1, wherein in the formula (I), n is between 75 and 500, better still between 80 and 400, even between 90 and 300, and preferably between 95 and 250, even better between 100 and 200. . 3. Copolymer according to one of the preceding claims, whereinmo-20 nomères of formula (I) are selected from - the (meth) acrylate of poly (ethylene glycol) wherein RI is H or methyl; Z is COO, m = 0 and R3 = H; methyl (poly) ethylene glycol (meth) acrylate wherein R 1 is H or methyl, Z is COO, m = 0 and R 3 is methyl; Alkyl polyethylene glycol (meth) acrylate) wherein R 1 is H or methyl; Z is COO, m = 0 and R3 alkyl. the (meth) acrylates of phenyl-poly (ethylene glycol) in which R1 is H or methyl, Z is COO, m = 0 and R3 phenyl. 30 4. Copolymer according to one of the preceding claims, wherein the monomer of formula (I), alone or as a mixture, is present in a proportion of 30 to 80% by weight, preferably 32 to 75% by weight, or 35 to 70% by weight, based on the weight of the final copolymer. 35 5. Copolymer according to one of the preceding claims, wherein the monomer of formula (II) is chosen from, alone or as a mixture, the following monomers and their salts, CH3 and dimethylaminopropyl (meth) acrylamide, dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, vinylimidazole, vinylpyridine, morpholinoethyl (meth) acrylate. 6. Copolymer according to one of the preceding claims, wherein the mono-mother of formula (II), alone or as a mixture, is present in a proportion of 12 to 48% by weight relative to the weight of the final copolymer, especially 13 to 45% by weight. 7. Copolymer according to one of the preceding claims, wherein the anionic monomer is chosen from, alone or as a mixture, maleic anhydride, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fucic acid, maleic acid, 2-carboxyethyl acrylate; styrene sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, vinylbenzoic acid, vinylphosphoric acid, sulfopropyl (meth) acrylate, and salts thereof. Copolymer according to one of the claims preceding, wherein the mono-mother of formula (III), alone or in mixture, is present in a proportion of 2 to 32% by weight relative to the weight of the final copolymer, in particular in the proportion of 3 to 30% by weight. 9. Copolymer according to one of the preceding claims, wherein the copolymer is neutralized with a Bronsted acid, or a mixture of such acids, in particular with a mineral acid such as sulfuric acid, hydrochloric acid hydrobromic acid, hydroiodic acid, phosphoric acid, boric acid; or with an organic acid, such as acetic acid, terephthalic acid, HOOC-PEG-000H acid; citric acid, tartaric acid; betaine hydrochloride, gluconic acid, 2-ethylcaproic acid. 10. Cosmetic composition comprising, in a cosmetically acceptable medium, at least one copolymer as defined in one of Claims 1 to 9. 11. Composition according to Claim 10, in which the copolymer is present in the form solubilized in water or an organic solvent, or in the form of an aqueous or organic dispersion. 12. Composition according to one of claims 10 to 11, wherein the copoly mother is present; alone or as a mixture, in a proportion of 0.1 to 20% by weight of dry matter, especially 0.5 to 15% by weight, or even 1 to 10% by weight, more preferably 2 to 8% by weight. , relative to the total weight of the composition. 13. Composition according to one of claims 10 to 12, in which the cosmetically acceptable medium comprises at least one compound selected from water, alcohols, polyols, polyol ethers, esters, carbon oils, silicone oils, fluorinated silicone oils, gelling agents, thickeners; Associative or non-associative polymers, anionic, nonionic, cationic and / or amphoteric surfactants; propenetrating agents, emulsifiers, perfumes, preservatives, pigments, dyes, fillers, sunscreens; dyestuffs, proteins, vitamins, provitamins; polymers, fixing or non-fixing; moisturizing agents, emollients, softening agents; mineral, vegetable or synthetic oils; hydrophilic or lipophilic active agents, ceramides, pseudoceramides; anti-foam agents, antiperspirants, anti-free radical agents, bactericidal agents, anti-dandruff agents, hair loss agents, pearlescent agents, and mixtures thereof. 14. Composition according to one of claims 10 to 13, being in the form of a care product, cleaning and / or makeup of the skin of the body or face, lips, eyelashes, nails and hair, a solar product 16. A cosmetic process for treating keratin materials comprising the application to said materials of a cosmetic composition as defined in one of claims 10 to 15 or self-tanning, of a product body hygiene; a hair product, especially care, cleaning, styling, permanent, straightening, fading, hair coloring. 15. Composition according to one of claims 10 to 14, in the form of a hair conditioning hair composition.