EP1572139A1

EP1572139A1 - Cosmetic composition and method for treating keratinous materials, comprising a photodimerizable compound

Info

Publication number: EP1572139A1
Application number: EP03813178A
Authority: EP
Inventors: Henri Samain; Gabin Vic; Aude Livoreil; Franck Giroud
Original assignee: LOreal SA
Current assignee: LOreal SA
Priority date: 2002-12-13
Filing date: 2003-12-12
Publication date: 2005-09-14
Also published as: WO2004054527A1; AU2003296830A1

Abstract

The invention concerns generally a cosmetic composition comprising at least one cosmetic active principle and at least one photodimerizable compound enabling a material deposit to be provided on the keratinous materials, which is resistant to washing, and whereof the location is precisely controlled, capable of providing long-lasting cosmetic properties to keratinous materials, and of being removed at any time.

Description

Cosmetic composition and method for the treatment of keratin materials, comprising a photodimerizable compound.

The present invention relates in general to a cosmetic composition comprising at least one cosmetic active agent and at least one photodimerizable material allowing the production of a deposit of material on keratin materials, and in particular on the hair, which is persistent in washing , whose location is precisely controlled, capable of providing lasting cosmetic properties to keratin materials, and can be removed at any time.

The resistance of a deposit of material to washing can be provided by a low solubility of the deposit in aqueous detergent media. The fact of causing crosslinking by the action of light

(photocrosslinking) makes it possible to selectively crosslink a deposit, in particular on specific zones of keratin materials previously coated with the photocrosslinkable composition, and thus to create a lasting deposit on certain zones and not others. The non-irradiated parts of the deposit (for example covered with a mask), and therefore not crosslinked, remain soluble. They can then be easily removed during rinsing or shampooing after irradiation. It thus becomes possible, for example, to create patterns on keratin materials and images using “stencils” and various masks with a photocrosslinkable composition, for example colored, or even to treat only specific sensitized areas, such as the tips in the case of hair, with a conditioning composition or the like.

It is known to those skilled in the art to use photocrosslinkable materials such as materials derived from vinyl monomers, and in particular (meth) acrylate monomers.

Thus, US Patent 5,300,285 describes a process for waving the hair and a composition for it. implementation of this process, and in particular a neutralizing composition based on silicone, comprising a silicone with vinyl function, a phonitoinitiator with free radicals and a solvent. This composition acts as a substitute for neutralizing solutions based on hydrogen peroxide when applied to the hair after a process of permanent deformation of the hair and photocrosslinking of the composition. This composition has the advantage of functioning simultaneously as a crosslinking agent for keratin, while conferring advantages on the hair such as conditioning and

soft touch. The photocrosslinking of the composition is triggered by the photoinitiator (generally a derivative of acetophenone), which releases a radical under irradiation in the UVA domain (350-385 nm).

In other cosmetic fields, such as nail varnishes, compositions are also sought which are resistant to various attacks, such as water or mechanical shock, as well as compositions providing shine and long-lasting.

Unfortunately, the photopolymerization of vinyl-functional silicone in the presence of a photoinifier leads to an irreversible photocrosslinking of the vinyl-functional silicone. In other words, once photocrosslinked, the deposit cannot be easily and at any time removed from the hair.

In addition, in addition to the toxicologically unfavorable aspects of these monomers and of the photoinitiator, the compositions containing these materials derived from vinyl monomers are known to be unstable, in particular because of their sensitivity to oxygen and to humidity. In addition, photocrosslinking is sometimes obtained with prolonged irradiation, hence the risks of hair degradation under the action of UV.

Finally, Japanese patent JP 09249812 describes interpenetrating networks containing molecules forming chelates and their uses, and more particularly compositions containing polymers of polyvinyl acetate type partially saponified with stilbazolium groups, crosslinked and containing chelating agents. This previously crosslinked material can then be used as it is in medical or cosmetic applications. However, there is no mention in this patent (JP 09249812) of applying a composition containing non-crosslinked polymers to the hair or the skin before irradiation.

The object of the present invention is therefore to provide a cosmetic composition which, after application to keratin materials, in particular to keratin fibers such as the hair, is photocrosslinked in a possibly reversible manner, and results in a crosslinked deposit which does not dissolve , is persistent in washing and does not degrade the keratinous fiber, thus guaranteeing the durability of the cosmetic effects provided by this deposit.

By reversible photocrosslinking of a material or a composition is meant, within the meaning of the present application, a crosslinking by action of light of the material or composition, resulting in a deposit which can be removed at any time and easily removed from the hair. Thus, irradiation in the UVB domain (around 250 nm) leads to the reformation of the original double bonds and to the disappearance of the crosslinking. i In particular, the subject of the present invention is a cosmetic composition for the treatment of keratin materials comprising at least one cosmetic active agent, characterized in that it additionally comprises at least one compound comprising at least one photodimerizable group, this compound having a molecular weight greater than 500g / mol; Advantageously, in the compositions of the invention, the compound comprising at least one photodimerizable group has a molecular mass greater than 700 g / mol, more advantageously greater than 850 g / mol, and even more preferably greater than 1000 g / mol.

By cosmetic active is meant, within the meaning of the present invention, any active compound having cosmetic or dermatological activity.

By photodimerizable group is meant, within the meaning of the present invention, a chemical group leading to photodimerization reactions under irradiation.

By photodimerization is meant, within the meaning of the present invention, a chemical reaction between two double bonds (of type 2 + 2) or two pairs of double bonds (of type 4 + 4).

The case of a reaction between two double bonds can be schematized as follows:

These photodimerization reactions are defined in the document "Advanced Organic Chemistry, J Marck, 4 ^th edition, Wiley Interscience, NY 1992, p 855".

Materials having photodimerizable groups according to the invention have the advantage of being stable with respect to oxygen, humidity, and heat, and leading to reversible crosslinking. In addition, the photodimerizable groups according to the invention are very photosensitive. Consequently, even low energy irradiation leads to rapid and effective crosslinking of the material, which, in the case of a cosmetic application, induces a short duration and low energy irradiation which does not lead to degradation of the keratin materials. This is especially advantageous for a hair or nail polish application.

Preferably, the photodimerizable groups which can be used according to the invention are chosen from monovalent radicals of formulas: A Y = Z B (I)

in which :

- Y and 2 independently of one another denote a carbon or nitrogen atom,

- A is a divalent linking group chosen from alkylene radicals, cycloaromatic radicals, heterocyclic radicals, carbonyl radicals, alkenylene radicals and their combinations, - B is a monovalent group chosen from alkyl radicals, cycloaromatic radicals, heterocyclic radicals, carbonyl radicals, alkenyl radicals and combinations thereof,

- X is a divalent group chosen from alkylene radicals, cycloaromatic radicals, heterocyclic radicals, carbonyl radicals, alkenylene radicals and their combinations, and each of the groups mentioned may optionally be substituted by one or more groups chosen from alkyl, hydroxy, amino, mono or dialkylamino, halogens, aryies, carboxy groups, alkoxy, alkoxycarbonyls, hydrogen carbonyls, sulfonato, amide, and acyls.

The dimerizable groups according to the invention are in particular those cited in patents US-2,811,510, EP 0 313 220, EP 0 313 221, E 092 901, GB 2 030 575 and GB 2 076 826, as well as in the articles "Chemical review Vol 83.5 1983, p 507 "" Polym, Paint color Journal 1988, 178, p 209 "and" Current Trends in Polymer Photochemistry, Ellis Morwood Edition, NY, 1995 ".

By way of example, mention may be made more particularly of the photodimerizable groups chosen from monovalent radicals of the following compounds:

- stilbene,

- styrylpyridinium (stilbazolium) of formula:

OR

- R represents the hydrogen atom, an alkyl or hydroxyalkyl group, and

- R 'represents the hydrogen atom or an alkyl, styrylazolium group of formula:

where A denotes a sulfur atom, an oxygen atom, or a group NR 'or C (R') ₂ , R and R 'being as defined above,

- styrylpyrazine,

- chalcone,

- (thio) cinnamate and (thio) cinnama ide,

- maleimide, - (thio) coumarin,

- thymine,

- uracil,

- butadiene - anthracene,

- pyridone,

- pyrrolizinone,

- acridizinium salts,

- furanone, - phenylbenzoxazole, and

- their derivatives.

Such chemical groups have activated double bonds, so that the photodimerization of these double bonds is triggered spontaneously in the UVA domain, without requiring a photoinitiator.

Advantageously, in the compositions of the invention, the compound comprising at least one photodimerizable group is a polymer. Even more advantageously, it is in the form of particles, in particular dispersed particles. By photoinitiator is meant, within the meaning of the present invention, a compound which initiates the photodimerization reaction and releases a radical under irradiation, in particular in the UV field.

Consequently, when the composition according to the invention comprises a compound comprising at least one photodimerizable group chosen from the photodimerizable groups previously mentioned, it is preferably free of photoinitiator.

The compounds with photodimerizable group (s) according to the invention are preferably not dyes.

The photodimerizable groups according to the invention can be easily grafted onto any type of support compound.

Advantageously, the support compound is a filler forming a particle. Particles include mineral particles and organic particles. The mineral particles can consist of oxides, dihydrate oxides, hydroxides, carbonates, sulfides, silicates, phosphates of silicon, calcium, magnesium, zinc, aluminum, titanium, zirconium, of cerium, nacres, micas, particles consisting of native metals, that is to say alkali metals, alkaline earth metals, transition metals, rare earth metals, coated or not and their alloys. Among the metals, aluminum, copper, silver, gold, indium, iron, platinum, nickel, molybdenum, silicon, titanium, tungsten, antimony are preferred. palladium, cadmium, zinc, retain, selenium and their alloys. Among the previous list, gold, silver, palladium and platinum and their alloys are preferred, silver and gold being the preferred metals. The organic particles can consist of latexes, polystyrene, polystyrene derivatives, silicones, fluoropolymers, polypropylene, polyethylene, poly (meth) acrylic acid, polymethacrylate, polyurethane, polyamide, polycarbonate, polyvinyl chloride, polyvinyl acetate, fluoropolymers, polyethylenes, polypropylene, polysobutylene, poly (1 -butylene), the copolymers and mixtures of the polymers mentioned, alkyl cellulose, hydroxyalkyl cellulose, cellulose ethers, cellulose esters, hydroxypropylcellulose, hydroxypropyldextran, hydroxypropylmethyl cellulose, cellulose acetate, carboxyethylcellulose, cellulose sulfate, dextran sulfate, polyvinyl alcohol, polyethylene oxide , polyvinyl chloride, polyvinylpyrolidone.

The polystyrene particles are commercially available from Polyscience Inc (Warrington, PA) or Duke Scientific Corporation (Palo Alto, CA). These organic particles can be crosslinked using crosslinkers such as, for example, divinylbenzene, glutaraldehyde, 1, 4- bis (acryloyl) piperazine, carbodiimides, N-hydroxysuccinimide and derivatives, divinylsufone, dithiobis (succinimidyl) propionate, N-succinimidyl-3- (2-pyridyldithio) propionate.

Preferably, the support compound is chosen from polymers, and even more preferably from poly (vinyl) polymers and polydiorganosiloxanes.

Among the polyvinyl polymers, polyvinyl acetate, preferably partially saponified, are particularly preferred. The compound (s) comprising at least one photodimerizable group according to the invention are advantageously, thus a polymer soluble or dispersed in the composition, or, more advantageously still, a polymer adsorbed on polymer particles, themselves dispersed in the composition. In the latter case, the polymer particles are very preferably particles of vinyl polymers, and better still particles of polyvinyl acetate.

The invention relates very particularly, as compound (s) comprising at least one photodimerizable group,. aqueous dispersions of a partially saponified polyvinylacetate type polymer carrying stilbazolium groups, brought into contact, in particular mixed, with polyvinylacetate particles.

The photodimerizable material can also form all or part of a material of the core / shell type as defined in application FR 2 838 052, filed by the Applicant.

The compound (s) comprising at least one photodimerizable group according to the invention preferably represent (s) 0.01 to 25%, better still 0.1 to 20%, and better still 1 to 15% of the total weight of composition. The cosmetic composition according to the invention may, in addition, comprise an effective amount of at least one photosensitizer.

By photosensitizer is meant within the meaning of the present invention, an ingredient which modifies the wavelength of the irradiation, thus triggering the photodimerization reaction.

For example, the photodimerization of dimethylmaleimide groups is triggered by irradiation centered on the wavelength range ranging from 270 to 300 nm. In the presence of a photosensitizer such as thioxanthone, photodimerization becomes effective with irradiation centered on the wavelength range from 360 to 430 nm.

Among the photosensitizers which can be used according to the invention, there may be mentioned in particular thioxanthone, bengal rose, phloxin, eosin, erythrosin, fluorescein, acriflavin, thionin, riboflavin, proflavin, chlorophylls , hematoporphyrin, methylene blue and mixtures thereof.

In practice, the photosensitizer which can be used according to the invention represents 0.00001% to 5% by total weight of the composition.

The cosmetic active ingredient (s) according to the invention is (are) chosen from:

* saccharides, oligosaccharides, polysaccharides hydrolyzed or not, modified or not, * amino acids, oligopeptides, peptides, proteins hydrolyzed or not, modified or not, poly amino acids, enzymes,

* fatty acids and alcohols branched or not,

* animal, vegetable or mineral waxes, * ceramides and pseudo-ceramides,

* hydroxylated organic acids,

* UV filters,

* antioxidants and anti-free radical agents,

* chelating agents, * dandruff agents,

* seborrhea regulating agents,

* soothing agents,

* cationic surfactants,

* cationic, amphoteric polymers, * organomodified or unorganized silicones,

* mineral, vegetable or animal oils,

* polyisobutenes and poly (α-olefins),

* esters,

* soluble or dispersed anionic polymers, * soluble or dispersed nonionic polymers, * reducing agents,

< _. * coloring matters, and in particular hair dyes,

* foaming agents,

* film-forming agents, * particles, and their mixtures.

In general, the saccharide, oligosaccharide or polysaccharide type compounds, hydrolyzed or not, modified or not, which can be used in the present invention, are chosen from those which are especially described in "Encyclopedia of Chemical Technology, Kirk-Othmer, Third Edition , 1982, volume 3, pp. 896-900, and volume 15, pp 439-458 ", in" Polymers in Nature, by EA MacGREGOR and CT GREENWOOD, Editions John Wiley & Sons, Chapter 6, pp 240-328, 1980 "and in the Industrial Gums - Polysaccharides and their Derivatives, Edited by Roy L. WHISTLER, Second Edition, Edition Académie Press Inc.", the content of these three works being fully included in this request for reference.

By way of examples of saccharides, oligosaccharides, polysaccharides hydrolyzed or not, modified or not, which can be used in the invention, mention may be made especially of glucans, starches modified or not (such as those obtained, for example, from cereals such as wheat, corn or rice, vegetables like light peas, tubers like potatoes or cassava) and different from starch betainate as described above, amylose, amylopectin, glycogen dextrans, β-glucans, celluloses and their derivatives (methylcelluloses, hydroxyalkylcelluloses, ethylhydroxyethylcelluloses, carboxymethyl-celluloses), fructosans, inulin, levane, mannans, xylans, lignins, arabans, galactans, galacturonans, chitin, glucoronoxylans, arabinoxylans, xyloglucans, galactomannans, glucomannans, pectic acids and pectins, alginic acid and alginates, arabinogalactans, carragh enins, agars, glycosaminoglucans, gum arabic, Tragacanth gum, Ghatti gum, Karaya gum, locust bean gum, guar gum and xanthan gum. As amino acids, there may be mentioned, for example, cysteine, lysine, alanine, N-phenylalanine, arginine, glycine, leucine, and mixtures thereof. As oligopeptides, peptides, proteins hydrolyzed or not, modified or not, which can be used according to the invention, mention may in particular be made of hydrolysates of wool or silk proteins, modified or not, proteins vegetables such as wheat proteins.

Among the amino acids which can be used, mention may be made of polylysine. Among the enzymes which can be used, mention may be made of laccases, peroxidases, lipases, proteases, glycosidases, dextranases, uricases, alkaline phosphatase.

Among the branched fatty acids or not suitable in the present invention, mention may in particular be made of Cs-C-30 carboxylic acids, such as palmitic acid, oleic acid, linoleic acid, myristic acid, stearic acid, lauric acid, and mixtures thereof. The fatty alcohols which can be used in the present invention include in particular the C8-C30 alcohols such as, for example, palmityl, oleyl, linoleyl, myristylic, stearyl and lauryl alcohols.

A wax, within the meaning of the present invention, is a lipophilic compound, solid at room temperature (about 25 ° C), with reversible solid / liquid state change, having a melting temperature above about 40 ° C and which can range up to 200 ° C, and having an anisotropic crystalline organization in the solid state. In general, the size of the crystals of the wax is such that the crystals diffract and / or scatter light, giving the composition which comprises them a more or less opaque cloudy appearance. By bringing the wax to its melting point, it is possible to make it miscible with oils and to form a homogeneous mixture microscopically, but by bringing the temperature of the mixture to room temperature, the wax is recrystallized from the oils of the mixture, microscopically and macroscopically detectable (opalescence).

As waxes which can be used in the present invention, mention may be made of waxes of animal origin such as beeswax, spermaceti, lanolin wax and lanolin derivatives; vegetable waxes such as Camauba, Candellila, Ouricury, Japanese wax, cocoa butter or cork fiber or sugar cane waxes; mineral waxes, by example, paraffin, petrolatum, lignite or microcrystalline waxes or ozokerites.

Among the ceramides, mention may be made in particular of the ceramides of classes I, II, III and V according to the classification of DAWNING, and more particularly N-oleyldehydrosphingosine.

The hydroxylated organic acids are chosen from those well known and used in the art. Mention may in particular be made of citric acid, lactic acid, tartaric acid, malic acid.

The active UV-A and / or UV-B sun filters that can be used according to the invention are those well known to those skilled in the art. Mention may in particular be made of dibenzoylmethane derivatives such as 4-methyldibenzoylmethane, 4-isopropyldibenzoylmethane, 4-tert-butyldibenzoylmethane, 2,4-dimethyldibenzoylmethane, 4-tert-buty 4'-diisopropyldibhane p-amino benzoic acid and its esters such as 2-ethylhexyl p-dimethylaminobenzoate and N-propoxylated ethyl p-aminobenzoate, salicylates such as triethanolamine saltcylate, cinnamic acid esters such as 4- 2-ethylhexyl methoxy-cinnamate, methyl diisopropylcinnamate, menthyl anthranilate, benzotriazole derivatives, triazine derivatives, β, β'-diphenylacrylate derivatives such as 2-cyano-3,3-diphenylacrylate 2-ethylhexyl and ethyl 2-cyano-3,3-diphenylacrylate, 2-phenylbenzimidazole-5-sulfonic acid and its salts, benzophenone derivatives, benzylidene-camphor derivatives, silicone filters, etc. ..

As antioxidants and anti-free radical agents which can be used in the present invention, there may be mentioned, for example, ascorbic acid, ascorbylated compounds such as ascorbyl dipalmitate, t-butylhydroquinone, polyphenols such than phloroglucinol, sodium sulfite, erythorbic acid, flavonoids.

The chelators can be chosen in particular from EDTA (ethylenediaminetetraacetic acid) and its salts such as disodium EDTA and dipotassium EDTA, phosphate compounds such as sodium metaphosphate, sodium hexametaphosphate, tetrapotassium pyrophosphate, phosphonic acids and their salts such as the salts of ethylenediaminetetramethylenephosphonic acid.

The anti-dandruff agents are chosen, for example, from: - benzethonium chloride, benzalkonium chloride, chlorhexidine, chloramine T, chloramine B, 1, 3-dibromo-5,5-dimethylhydantoin, 1,3-dichloro 5,5-dimethylhydantoin, 3- bromo-chloro 5,5-dimethylhydantoin, N-chlorosuccinimide; - 1-hydroxy-2-pyridone derivatives such as, for example, 1-hydroxy-4-methyl-2-pyridone, 1-hydroxy-6-methyl-2-pyridone and 1-hydroxy-4, 6-dimethyl-2-pyridone;

- trihalogenocarbamides;

- triclosan; - azole compounds such as climbazole, ketoconazole, clotrinazole, econazole, isoconazole and miconazole b;

- antifungal polymers such as amphotericin B or nystatin;

- selenium sulfides; sulfur in its various forms, cadmium sulphide, allantoin, coal or wood tars and their derivatives in particular, cade oil, undecylenic acid, fumaric acid, allylamines such as terbinafine.

They can also be used in the form of their physiologically acceptable acid addition salts, in particular in the form of salts of sulfuric, nitric, thiocyanic, hydrochloric, hydrobromic, hydroiodic, phosphoric, acetic, benzoic, glycolic, aceturic or succinic acids. , nicotinic, tartaric, maleic, palmitic, methane sulfonic, propanoic, 2-oxopropanoic, propanedioic, 2-hydroxy-1, 4-butanedioic, 3-phenyl-2-propenoic, α-hydroxybenzene acetic, ethanesulfonic, 2-hydroxyethane-sulfonic, 4-methylbenzenesulfonic, 4-amino-2-hydroxybenzoic, 2-phenoxybenzoic, 2-acetyloxybenzoic, picric, lactic, citric, malic, oxalic and amino acids.

The anti-dandruff agents mentioned above can also optionally be used in the form of their physiologically acceptable organic or inorganic base addition salts. Examples of organic bases are in particular low molecular weight alkanolamines such as ethanolamine, diethanolamine, N-ethylethanolamine, triethanolamine, diethylaminoethanol, 2-amino-2-methylpropanedione; non-volatile bases such as ethylenediamine, hexamethylenediamine, cyclohexylamine, benzylamine, N-methylpiperazine; quaternary ammonium hydroxides, for example, trimethylbenzyl hydroxide; guanidine and its derivatives, and in particular its alkyl derivatives. Examples of inorganic bases are in particular the salts of alkali metals, such as sodium or potassium; ammonium salts, alkaline earth metal salts, such as magnesium, calcium; the cationic di, tri or tetravalent metal salts, such as zinc, aluminum and zirconium. Alkanolamines, ethylenediamine and inorganic bases such as the alkali metal salts are preferred. The seborrhea regulating agents are, for example, succinylchitosan and poly-β-alanine.

Soothing agents are, for example, azulene and glycyrrhetinic acid.

The cationic surfactants are those well known per se, such as the salts of primary, secondary or tertiary fatty amines, optionally polyoxyalkylenated; quaternary ammonium salts such as chlorides or bromides of tetraalkylammonium, alkylamidoalkyl-trialkylammonium, trialkylbenzylammonium, trialkylhydroxy-alkylammonium or alkylpyridinium; imidazoline derivatives. By "cationic polymer" is meant any polymer containing cationic groups and / or groups which can be ionized into cationic groups.

The cationic polymers which can be used in accordance with the present invention can be chosen from all those already known per se as improving the cosmetic properties of hair treated with detergent compositions, namely in particular those described in patent application EP-A-0 337 354 and in French patent applications FR-A- 2 270 846, 2 383 660, 2 598 611, 2 470 596 and 2 519 863.

The preferred cationic polymers are chosen from those which contain units comprising primary, secondary, tertiary and / or quaternary amine groups which can either be part of the main polymer chain, or be carried by a lateral substituent directly linked thereto. The cationic polymers used generally have a number average molecular mass of between 500 and 5.10 ⁶ approximately, and preferably between 10 ³ and 3.10 ⁶ approximately.

Among the cationic polymers, mention may be made more particularly of polymers of the polyamine, polyaminoamide and polyquaternary ammonium type. These are known products.

The polymers of the polyamine, polyaminoamide, and quaternary polyammonium type which can be used in the composition of the present invention are those described in French patents Nos ^. 2,505,348 and 2,542,997. Among these polymers, mention may be made of:

(1) homopolymers or copolymers derived from esters or amides of acrylic or methacrylic acid;

(2) derivatives of cellulose ethers comprising quaternary ammonium groups described in French patent 1,492,597; (3) cationic cellulose derivatives such as cellulose copolymers or cellulose derivatives grafted with a water-soluble quaternary ammonium monomer, and described in particular in US Pat. No. 4,131,576, such as hydroxyalkylcelluloses, such as hydroxymethyl-, hydroxyethyl- or hydroxypropyl-celluloses grafted in particular with a salt of methacryloylethyl-trimethylarpmoniύm, of methacrylamidopropyl-trimethylammonium or of dimethyldiallylammonium;

(4) the cationic polysaccharides described more particularly in US patents 3,589,578 and 4,031,307 such as guar gums containing cationic trialkylammonium groups; (5) polymers consisting of piperazinyl units and divalent alkylene or hydroxyalkylene groups with straight or branched chains, optionally interrupted by oxygen, sulfur, nitrogen atoms or by aromatic or heterocyclic rings, as well as the products of oxidation and / or quaternization of these polymers. Such polymers are described in particular in French patents 2,162,025 and 2,280,361;

(6) water-soluble polyaminoamides, such as those described in particular in French patents 2 252 840 and 2 368 508;

(7) polyaminoamide derivatives, for example, adipic acid / diakylaminohydroxyalkyldialkylene-triamine polymers in which the alkyl group contains from 1 to 4 carbon atoms and preferably denotes a ^' methyl group, ethyl, propyl, and the alkylene group contains from 1 to 4 carbon atoms, and preferably denotes the ethylene group. Such polymers are described in particular in French patent 1,583,363.

(8) polymers obtained by reaction of a polyalkylene polyamine comprising two primary amine groups and at least one secondary amine group, with a dicarboxylic acid chosen from diglycolic acid and saturated lipid dicarboxylic acids having from 3 to 8 atoms of carbon. The molar ratio between the polyalkylene polylamine and the dicarboxylic acid being between 0.8: 1 and 1.4: 1; the resulting polyaminoamide being reacted with epichlorohydrin in a molar ratio of epichlorohydrin relative to the secondary amine group of the polyaminoamide of between 0.5: 1 and 1.8: 1. Such polymers are described in particular in the patents American 3,227,615 and 2,961,347; (9) alkyldiallylamine or dialkyldiallylammonium cyclopolymers such as the homopolymer of dimethyldiallyl ammonium chloride and copolymers of diallyldimethylammonium chloride and acrylamide;

(10) quaternary diammonium polymers having a number-average molecular weight generally between 1000 and 100,000, such as those described, for example, in French patents 2,320,330, 2,270,846, 2,316,271, 2,336,434 and 2,413,907 and US Patents 2,273,780, 2,375,853, 2,388,614, 2,454,547, 3,206,462, 2,261,002, 2,271,378, 3,874,870, 4,001,432, 3,929,990, 3,966,904, 4,005,193, 4,025,617, 4,025,627, 4,025,653, 4,026,945 and 4,027,020; (11) quaternary polyammonium polymers such as those described in particular in patent application EP-A-122 324;

(12) quaternary polymers of vinylpyrrolidone and of vinylimidazole, such as, for example, the products sold under the names Luviquat ^® FC 905, FC 550 and FC 370 by BASF; (13) polyamines such as Polyquart ^® H sold by HENKEL, referenced under the name of "POLYETHYLENEGLYCOL (15) TALLOW POLYAMINE" in the CTFA dictionary;

(14) crosslinked polymers of methacryloyloxyalkyl (Cι-C) trialkyl (Cι-C4) ammonium salts such as those marketed under the name of SALCARE.RTM SC 92, Salcare ^® SC 95 and Salcare ^® SC ^'96 by Allied Colloids; and their mixtures.

Other cationic polymers which can be used in the context of the invention are cationic proteins or hydrolysates of cationic proteins, polyalkyleneimines, in particular polyethyleneimines, polymers containing vinylpyridine or vinylpyridinium units, condensates of polyamines and epichlorohydrin, quaternary polyureylenes and chitin derivatives. The amphoteric 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 derived 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 carboxybétaines or 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 group, or although B and C form part of a chain of a polymer with an ethylene-dicarboxylic unit, one of the carboxylic groups of which has been caused to react with a polyamine comprising one or more primary or secondary amine groups. The amphoteric 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 carboxyl group such as more particularly acrylic acid, methacrylic acid, maleic acid, alpha-chloroacrylic acid, and of a basic monomer derived from a substituted vinyl compound containing at least one basic atom such as more particularly the dialkylaminoalkyimethacrylate and acrylate, the dialkylaminoalkyl-methacrylamide and acrylamide. Such compounds are described in US Pat. No. 3,836,537. Mention may also be made of copolymer of sodium acrylate / ammonium chloride acrylamidopropyltriméthyl- sold under the name ^® POLYQUART KE 3033 by Henkel.

The vinyl compound can also be a dialkyldiallylammonium salt such as diethyldiallylammonium chloride.

The copolymers of acrylic acid and the latter monomer are offered under the names Merquat ^® 280, Merquat 295 and Merquat ^® ^® Plus 3330 by Calgon.

(2) polymers comprising units derived from: a) at least one monomer chosen from acrylamides or methacrylamides substituted on nitrogen with an alkyl group, b) from at least one acidic comonomer 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 product of quaternization of dimethylaminoethyl methacrylate with dimethyl or diethyl sulfate.

The N-substituted acrylamides or methacrylamides which are more particularly preferred according to the invention are groups whose alkyl groups contain from 2 to 12 carbon atoms and more particularly N-ethylacrylamide, N-tertiobutylacrylamide, N-tertiooctylacrylamide, N- octyl. N-decylacrylamide, N-dodecylacrylamide and the corresponding methacrylamides.

The acid comonomers are chosen more particularly from acrylic, methacrylic, crotonic, itaconic, maleic, fumaric acids as well as alkyl monoesters having 1 to 4 carbon atoms of maleic or fumaric acids or anhydrides. The preferred basic comonomers are aminoethyl, butylaminoethyl, N, N'-dimethylaminoethyl, N-tert-butylaminoethyl methacrylates. On The copolymers whose CTFA (4th edition, 1991) is octylacrylamide / acrylates / butylaminoethyl methacrylate copolymer such as the products sold under the name or Lovocryl AMPHOMER® ^® ^® 47 by the company National Starch.

(3) crosslinked and alkylated polyaminoamides partially or totally derived from polyaminoamides of general formula: - -CO-R ₁₀ - CO— Z- - (II)

in which Rio represents a divalent group 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 a group deriving from the addition of any one of said acids with a primary bis or secondary derivative bis amine, and Z denotes a group of a bis-primary, mono or bis-secondary polyalkylene polyamine and preferably represents: a ) in the proportions of 60 to 100% by moles, the group

where x = 2 and p = 2 or 3, or else x = 3 and p = 2 this group deriving from diethylene triamine, triethylene tetraamine or dipropylene triamine; b) in the proportions of 0 to 40 mol%, the group (III) above, in which x = 2 and p = 1 and which derives from ethylenediamine, or the group deriving from piperazine

/ \

- N N—

\ /

c) in the proportions of 0 to 20 mol%, the group -NH- (CH ₂ ) ₆ -NH- deriving from hexamethylenediamine, these polyaminoamines being crosslinked by addition of a bifunctional crosslinking agent chosen from epihalohydrins, diepoxides, dianhydrides, bis unsaturated derivatives, using 0.025 to 0.35 mole of crosslinking agent by amine group of the polyaminoamide and alkylated by the action of acrylic acid, chloracetic acid or an alkane-sultone or their salts. The saturated carboxylic acids are preferably chosen from acids having 6 to 10 carbon atoms such as adipic, 2,2,4-trimethyladipic and 2,4,4-trimethyladipic, terephthalic acids, acids with ethylenic double bonds 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:

in which Ru denotes a polymerizable unsaturated group such as an acrylate, methacrylate, acrylamide or methacrylamide group, y and z each represent an integer from 1 to 3, Rι ₂ and R ₁₃ represent a hydrogen atom, a methyl group, ethyl or propyl, R and R ₁₅ represent a hydrogen atom or an alkyl group such that the sum of the carbon atoms in R ₄ and R ₁₅ does not exceed 10.

The polymers comprising such units can also comprise units derived from non-zwitterionic monomers such as acrylate or methacrylate of dimethyl- or diethylaminoethyl, or alkyl acrylates or methacrylates, acrylamides or methacrylamides, or vinyl acetate .

Examples include methyl methacrylate copolymer and dimethylcarboxymethylammonioethyl methacrylate methyl such as the product sold under the name Diaformer® ^® Z301 by Sandoz.

(5) polymers derived from chitosan containing monomer units corresponding to the following formulas: the pattern (V) being present in proportions of between 0 and 30%, the pattern (VI) in proportions of between 5 and 50% and the pattern (VII) in proportions of between 30 and 90%, it being understood that in this motif F, Ri ₆ represents a group of formula :.

in which if q = 0, Rice, Rie and R19, identical or different, each represent a hydrogen atom, a methyl, hydroxyl, acetoxy or amino residue, a monoalkylamine residue or a dialkylamine residue optionally interrupted by one or more atoms of nitrogen and / or optionally substituted by one or more amine, hydroxyl, carboxyl, alkylthio, sulfonic groups, an alkylthio residue in which the alkyl group carries an amino residue, at least one of the groups Rι, Rie and R ₁ 9 being in this case a hydrogen atom; or if q = 1, Rι, Ris and R ₁ 9 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.

(7) The polymers corresponding to the general formula (IX) described for example, in French patent 1,400,366: (IX)

in which R ₂ 0 represents a hydrogen atom, a CH3O group, CH ₃ CH ₂ O, phenyl, R ₂ ι denotes hydrogen or a lower alkyl group such as methyl, ethyl, R ₂₂ denotes hydrogen or a lower alkyl group such as methyl, ethyl, R ₂ 3 denotes a lower alkyl group such as methyl, ethyl or a group corresponding to the formula: -R ₂ 4-N (R ₂ 2) 2, R24 representing a group -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -, -CH ₂ -CH (CH ₃ ) -, R22 having the meanings mentioned above, as well as the higher homologs of these groups and containing up to 6 carbon atoms. (8) Amphoteric polymers of the -DXDX- type chosen from: a) the polymers obtained by the action of chloracetic acid or sodium chloroacetate on the compounds comprising at least one unit of formula:

-D-X-D-X-D- (X) where D denotes a group

/ \

NOT

\ /

and X denotes the symbol E or E ', E or E', identical or different, denote a bivalent group which is a straight or branched chain alkylene group containing up to 7 ^" carbon atoms in the main chain unsubstituted or substituted by hydroxyl groups, and which may also contain oxygen, nitrogen, sulfur atoms, 1 to 3 aromatic and / or heterocyclic rings; the oxygen, nitrogen and sulfur atoms being present in the form of ether, thioether, sulfoxide, sulfone, sulfonium, alkylamine, alkenylamine, hydroxyl groups, benzylamine, amine oxide, quaternary ammonium, amide, imide, alcohol, ester and or urethane. b) The polymers of formula:

-D-X-D-X- (XI) where D denotes a group

/ \

I N—

\ /

and X denotes the symbol E or E 'and at least once E'; E having the meaning given above and E 'is a bivalent group which is a straight or branched chain alkylene group having up to 7 carbon atoms in the main chain, whether or not substituted by one or more hydroxyl groups 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 betaiized by reaction with chloracetic acid or sodium chloracetate.

(9) Alkyl (Cι-C ₅ ) vinyl ether / maleic anhydride copolymers partially modified by semiamidification with an N, N-dialkylaminoalkylamine such as N, N-dimethylaminopropyl-amine or by semiesterification with an N, N-dialcanolamine These copolymers can also include other vinyl comonomers such as vinylcaprolactam.

The silicones which can be used in accordance with the invention may be soluble or insoluble in water, and they may in particular be polyorganosiloxanes insoluble in water; they can be in the form of oils, waxes, resins or gums.

Organopolysiloxanes are defined in more detail in the work of

Walter NOLL "Chemistry and Technology of Silicones" (1968) Académie Press. They can be volatile or non-volatile.

When they are volatile, the silicones are more particularly chosen from those having a boiling point of between 60 ° C. and

260 ° C, and more particularly among: (i) cyclic silicones containing from 3 to 7 silicon atoms and preferably 4 to 5. This is, for example, octamethylcyclotetra-siloxane marketed in particular under the name of "VOLATILE SILICONE 7207" by UNION CARBIDE or "SILBIONE 70045 V 2" by RHODIA, decamethylcyclopentasiloxane marketed under the name "VOLATILE SILICONE 7158" by UNION CARBIDE, "SILBIONE 70045 V 5" by RHODIA.

Mention may also be made of cyclocopolymers of the dimethylsiloxane / methylalkylsiloxane type, such as the "SILICONE VOLATILE FZ 3109" sold by the company UNION CARBIDE, with a chemical structure:

r— D-D 'D-D' 1

with D Si-O— with D -Si-O -

T I I

CH ₃ ^C 8 .7

(ii) linear volatile silicones having 2 to 9 silicon atoms and having a viscosity less than or equal to 5.10 ^"6 m ² / s at 25 ° C. This is, for example, decamethyltetrasiloxane marketed in particular under the name" SH 200 "by TORAY SILICONE. Silicones included in this class are also described in the article published in Cosmetics and toiletries, Vol. 91, Jan. 76, p. 27-32 - TODD &BYERS" Volatile Silicone fluids for cosmetics ".

Among the non-volatile silicones, mention may especially be made of polyalkylsiloxanes, polyarylsiloxanes, polyalkylaryisiloxanes, gums and silicone resins, polyorganosiloxanes modified with; organofunctional groups.

The organomodified silicones which can be used in accordance with the invention are silicones as defined above and comprising in their structure one or more organofunctional groups attached via a hydrocarbon group. Among the organomodified silicones, mention may be made of polyorganosiloxanes comprising: - polyethyleneoxy and / or polypropyleneoxy groups optionally comprising alkyl groups, C ₆ -C ₂ 4 as the products known as dimethicone copolyol sold by the company Dow Corning under the name DC 1248 or the oils Silwet ^® L 722, L 7500, L 77, L 711 from the company UNION CARBIDE and the alkyl (Cι ₂ ) -methicone-copolyol sold by the company DOW CORNING under the name Q2 5200;

- substituted or unsubstituted amino groups, such as the products sold under the name GP 4 Silicone Fluid and GP 7100 by the company GENESEE or the products sold under the names Q2 8220 and DOW CORNING 929 or 939 by the company DOW CORNING. The substituted amino groups are in particular C1-C4 aminoalkyl groups;

- thiol groups, such as the products marketed under the names "GP 72 A" and "GP 71" from GENESEE;

- alkoxylated groups, such as the product sold under the name "SILICONE COPOLYMER F-755" by SWS SILICONES and ABIL WAX ^® 2428, 2434 and 2440 by the company GOLDSCHMIDT;

- hydroxylated groups, such as the polyorganosiloxanes with a hydroxyalkyl function described in the French patent application FR-A-85

16334,

- Acyloxyalkyl groups such as, for example, the polyorganosiloxanes described in patent US-A-4957732.

- anionic groups of the carboxyic acid type such as, for example, in the products described in patent EP 186 507 of the company

CHISSO CORPORATION, or of the alkyl carboxylic type such as those present in the product X-22-3701E from the company SHIN-ETSU; 2- hydroxyalkylsulfonate; 2-hydroxyalkylthiosulfate such as the products sold by the company GOLDSCHMIDT under the names "ABIL ^® S201" and "ABIL ^® S255".

- hydroxyacylamino groups, such as the polyorganosiloxanes described in application EP 342 834. Mention may be made, for example, of the product Q2-8413 from the company Dow Corning.

Mention may in particular be made, as oils of vegetable origin, of sweet almond oil, avocado oil, castor oil, olive oil, jojoba, sunflower oil, wheat germ oil, sesame oil, peanut oil, grape seed oil, soybean oil, rapeseed oil, l safflower oil, coconut oil, corn oil, hazelnut oil, shea butter, palm oil, apricot kernel oil, calophyllum oil; as oil of animal origin, perhydrosqualene; as oils of mineral origin, paraffin oil and petrolatum oil.

The polyisobutenes and poly (α-olefins) are chosen from those well known in the art.

Examples of esters that may especially be mentioned are fatty acid esters such as isopropyl myristate, isopropyl palmitate, 2-ethylhexyl palmitate, Purcellin oil (stearyl octanoate), l 'isononyl or isostearyl isononanoate, isopropyl lanolate, and mixtures thereof.

The anionic polymers generally used in the present invention are polymers comprising groups derived from carboxylic, sulphonic or phosphoric acids, and having a molecular weight by weight of between 500 and 5,000,000.

The carboxylic groups are provided by monoacid or unsaturated dicarboxylic acid monomers such as those corresponding to the 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, Ri denotes a hydrogen atom, a phenyl or benzyl group, R ₂ denotes a hydrogen atom, a lower alkyl or carboxyl group, R3 denotes a hydrogen atom, a lower alkyl group, a group -CH ₂ -COOH, phenyl or benzyl.

In formula (XII) above, a lower alkyl group preferably contains from 1 to 4 carbon atoms and denotes in particular the methyl and ethyl groups. The anionic polymers with carboxylic groups preferred according to the invention are:

A) homo- or copolymers of acrylic or methacrylic acid or their salts, in particular the products sold under the names VERSICOL ^® E or K by the company Allied Colloid, Ultrahold ^® by the company BASF copolymers of acrylic acid and acrylamide sold in the form of their sodium salt under the names Reten ^® 421, 423 or 425 by the company Hercules, the sodium salts of polyhydroxycarboxylic acids. B) Copolymers of acrylic or methacrylic acids with a monoethylenic monomer such as ethylene, styrene, vinyl esters, esters of acrylic or methacrylic acid, optionally grafted on a polyalkylene glycol such as polyethylene glycol, and possibly crosslinked. Such polymers are described in particular in French Patent 1,222,944 and German Application No. 2,330,956, copolymers of this type comprising in their chain an optionally N-alkylated acrylamide and / or hydroxyalkyl unit as described in particular in Luxembourg patent applications 75370 and 75371 or offered under the name QUADRAMER ^® by the company AMERICAN CYANAMID. May also be mentioned the copolymers of acrylic acid and methacrylate of C ₁ -C ₄ and the copolymer of methacrylic acid and of ethyl acrylate sold under the name Luvimer ^® MAEX by BASF.

C) copolymers derived from -crotonic acid such as those comprising vinyl acetate or propionate units in their chain, and optionally other monomers such as the allyl or methallyl ester, vinyl ether or vinyl ester of a saturated carboxyic acid , linear or branched, with a long hydrocarbon chain, such as those containing at least 5 carbon atoms, these polymers possibly being grafted and crosslinked, or else a vinyl, allyl or methallyl ester of an α or β-cyclic carboxyic acid. Such polymers are described inter alia in French patents numbers 1 222 944, 1 580 545, 2265 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) Polymers derived from maleic, fumaric, itaconic acids or anhydrides with vinyl esters, vinyl ethers, vinyl halides, phenylvinyl 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 Gantrez ^® AN or ES by the company ISP denominations. _

Polymers also belonging to this class are the copolymers of maleic, citraconic, itaconic anhydrides and an allylic or methallylic ester optionally comprising an acrylamide, methacrylamide group, an α-olefin, acrylic or methacrylic esters, acrylic or methacrylic acids or vinylpyrrolidone in their chain, the anhydride functions are monoesterified or monoamidified. 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 mass of between approximately 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 polystyrene-sulfonic acid, the sodium salts, having a molecular mass 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 2198719; - The salts of polyacrylamide-sulfonic acids such as 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 polymers are preferably chosen from acrylic acid copolymers such as the acid terpolymer acrylic / ethyl acrylate / N-tertiobutylacrylamide sold under the name ULTRAHOLD STRONG® by the company BASF,. copolymers derived from crotonic acid such as vinyl acetate / vinyl tert-butyl benzoate / crotonic acid terpolymers and acid terpolymers crotonic / vinyl acetate / vinyl neododecanoate sold under the name Resin 28-29-30 by the company NATIONAL STARCH, polymers derived from maleic, fumaric, itaconic acids or anhydrides with vinyl esters, vinyl ethers, vinyl halides, phenylvinyl derivatives, acrylic acid and its esters such as the methyl vinyl ether / monoesterified maleic anhydride sold under the name Gantrez ^® ES 425 by the company ISP, copolymers of methacrylic acid and of methyl methacrylate sold under the name EUDRAGIT® L by the company ROHM PHARMA, the copolymer of methacrylic acid and eth acrylate yl sold under the name LUVIMER® MAEX by the company BASF, the vinyl acetate / crotonic acid copolymer sold under the name LUVISET® CA 66 by the company BASF and the vinyl acetate / crotonic acid / polyethylene glycol terpolymer under the name ARISTOFLEX ^® A by BASF. According to the invention, it is also possible to use anionic polymers in the form of latex or of pseudolatex, that is to say in the form of an aqueous dispersion of particles of insoluble polymers.

Mention may in particular be made, as nonionic polymers which can be used according to the present invention: - vinylpyrrolidone homopolymers;

- vinylpyrrolidone and vinyl acetate copolymers;

- polyalkyloxazolines such as polyethyloxazolines by 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; - vinyl acetate copolymers and acrylic ester, such as the product sold under the name Rhodopas AD 310 ^® from Rhône-Poulenc;

- vinyl acetate copolymers and ethylene as the product sold under the name Appretan of ^® TV by the company Hoechst;

- vinyl acetate copolymers and maleic ester, for example of dibutyl maleate, such as the product sold under the Appretan MB Extra name ^® by the company Hoechst;

- copolymers of polyethylene and maleic anhydride; - homopolymers of alkyl acrylates and alkyl methacrylate homopolymers, such as the product sold under the name Micropearl RQ 750 ^® by the company Matsumoto or the product sold under the name Luhydran ^® A 848 S by the company BASF;

- acrylic ester copolymers such as, for example, copolymers of alkyl acrylates and alkyl methacrylates such as the products sold 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 N 921 2; - copolymers of acrylonitrile and of a nonionic monomer chosen, for example, from butadiene and alkyl (meth) acrylates; include the products provided under the names Nipol ^® LX 531 8 by Nippon Zeon or those provided under the name CJ 0601 8 by the company Rohm &Haas; - polyurethanes, such as the products provided under the names Acrysol ^® RM 1020 and RM 2020 ACRYSOL® by Rohm & Haas, URAFLEX products ^® XP 401 UZ, URAFLEX® XP 402 UZ by the company DSM Resins;

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

- polyamides such as the product ESTAPOR ^® LO 11 by Rhone-Poulenc;

- chemically modified or unmodified non-ionic guar gums. Nonionic unmodified guar gums are, for example, 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 art and can, for example, be prepared by reacting corresponding alkene oxides, such as, for example, propylene oxides, with guar gum so to obtain a guar gum modified with hydroxypropyl groups.

Such gums guar nonionic optionally modified with hydroxyalkyl groups are, for example, sold under the trade names Jaguar ^® HP8, HP60 and JAGUAR® Jaguar® HP120, Jaguar DC 293 ^® and JAGUAR® HP 105 by the company Meyhall, or under the name GALACTASOL ^® 4H4FD2 by the company AQUALON.

The alkyl groups of the nonionic polymers preferably contain from 1 to 6 carbon atoms. The reducing agents can be chosen from thioacids and their salts (thioglycolic or thiolactic acid, cysteine or cysteamine), sulphites of alkali or alkaline earth metals, reducing sugars such as glucose, vitamin C and its derivatives, derivatives of sulfinic acid, phosphines. The amounts of these various cosmetic active agents are those conventionally used in the fields under consideration, for example from 0.001 to 30% by weight relative to the total weight of the composition.

The composition according to the invention can also comprise a solvent or a mixture of cosmetically acceptable solvents. By cosmetically acceptable is meant within the meaning of the invention physiologically acceptable solvents, non-toxic and capable of being applied to the skin or hair of human beings.

As solvents which can be used according to the invention, mention may in particular be made of water, alcohols, preferably lower C 1 -C 6 alkanols and in particular ethanol, propanol and isopropanol, polyols such as propyplene glycol, hexylene glycol, glycerin and pentanediol, polyol ethers, and mixtures thereof.

The solvent (s) generally represent 0.1% to 99% of the total weight of the composition. The pH of the compositions according to the invention is preferably between 2 and 12, and even more preferably between 3 and 11.

The composition of the invention may also contain conventional adjuvants such as perfumes, fillers, pH adjusters (acidic or basic), and preservatives. The amounts of these various adjuvants of the composition according to the invention are those conventionally used in cosmetics.

Of course, a person skilled in the art will take care to choose any additional adjuvants and / or their amount in such a way that the advantageous properties of the composition according to the invention are not or 'substantially not altered by the envisaged addition.

The present invention also relates to a process for treating keratin materials comprising the application to said keratin materials of a composition as defined above, and the irradiation of this composition to obtain a crosslinked deposit. In particular, the present invention relates to a process for treating keratin materials comprising the following steps: a) application to the keratin materials of a cosmetic composition according to the invention as defined above, and b) irradiation of said composition on keratin materials to crosslink the composition.

The composition can be applied to wet or dry keratin materials, clean or not. Preferably, the keratin materials are dried after application of the composition and before irradiation. It is also possible to include in the process, before or after step b) of irradiation, a pause at ambient temperature, or under heat, or under red light.

Finally, the process can comprise, prior to step b) of irradiation, a step of partial masking of keratin materials, and, after step b) of irradiation, a rinsing step, or when keratin materials are hair, a shampooing or styling step.

You can also make patterns on keratin materials. Preferably, the method comprises, in the case of the production of such patterns, a drying step prior to the step of partially masking said keratin materials and after the step of applying the composition. Thus, in practice, it is dried after application of the composition, then a part of the substrate is masked, for example with aluminum foil, and the whole area is irradiated. A rinse is then carried out. In the case of hair, this rinsing can be followed by a shampoo.

This masking technique makes it possible in particular to obtain localized cosmetic effects by subsequent action of cosmetic active agents (for example dyes) having a selective affinity for the areas treated by the irradiation.

The irradiation is preferably irradiation with radiation in the UVA or in the visible region, and even more preferably radiation in the UVA.

By irradiation in the visible range is meant in the sense of the present invention, either an irradiation carried out with an appropriate device (laser or lamps), or the simple action of sunlight.

When the keratin materials are hair, the method according to the invention can comprise, before or after step b) of irradiation, a step of shaping the hair, for example using tweezers, or curlers ...

When the compound (s) comprising at least one photodimerizable group according to the invention is (are) also thermodimerizable (s), the various methods described above can be implemented by replacing the irradiation step by a heating step between 40 and 200 ° C.

Advantageously, the keratin materials are hair or nails. The following example illustrates the invention without however limiting its scope. The quantities are given, unless otherwise indicated, in mass percentages.

EXAMPLE

An aqueous dispersion D is used of a polymer of the partially saponified polyvinylacetate type and carrying stilbazolium groups, adsorbed on polyvinylacetate particles.

This dispersion contains a dry extract of 40%.

We make the following composition from this aqueous dispersion D:

Dispersion D 11.25 g Dimethicone Copolyol 0.5 g

(marketed by Zshimmer Schwarz, under the name of 'SKINOTAN SIQ)

Water qs 100g

0.3 g of this composition is applied per g of hair.

The lock is kneaded, combed and dried with a hair dryer.

The lock was irradiated at 360 nm for 10 s for a total energy of 50 mJ / cm ² , or placed in daylight for 15 minutes.

There is a deposit on the wick which is resistant to at least 5 successive shampoos.

Claims

1. Cosmetic composition for the treatment of keratin materials comprising at least one cosmetic active agent, characterized in that it additionally comprises at least one compound comprising at least one photodimerizable group, this compound having a molecular mass greater than 500 g / mol.

2. Cosmetic composition according to claim 1, characterized in that the photodimerizable group (s) is (are) chosen from monovalent radicals of formulas:

in which: - Y and Z denote independently of one another a carbon or nitrogen atom,

A is a divalent linking group chosen from alkylene radicals, cycloaromatic radicals, heterocyclic radicals, carbonyl radicals, alkenylene radicals and their combinations,

B is a monovalent group chosen from alkyl radicals, cycloaromatic radicals, heterocyclic radicals, carbonyl radicals, alkenyl radicals and their combinations,

- X is a divalent group chosen from alkylene radicals, cycloaromatic radicals, heterocyclic radicals, carbonyl radicals, alkenylene radicals and their combinations, and each of the groups mentioned may possibly be substituted by one or more groups chosen from alkyl, hydroxy, amino, mono or dialkylamino, halogen, aryl, carboxy groups, alkoxy, alkoxycarbonyls, hydrogen carbonyls, sulfonato, amide, acyls.

3. Cosmetic composition according to claim 2, characterized in that the photodimerizable group (s) is (are) chosen from monovalent radicals of the following compounds:

- stilbene,

- styrylpyridinium (stilbazolium) of formula:

or

- R represents the hydrogen atom, an alkyl or hydroxyalkyl group, and

- R 'represents the hydrogen atom or an alkyl, styrylazolium group of formula:

- styrylpyrazine,

- chalcone,

- (thio) cinnamate and (thio) cinnamamide,

- maleimide,

- (thio) coumarin,

- thymine,

- uracil,

- butadiene

- anthracene,

- pyridone, - pyrrolizinone,

- acridizinium salts,

- furanone,

- phenylbenzoxazole, and - their derivatives.

4. Cosmetic composition according to any one of the preceding claims, characterized in that it is free of photoinitiator.

5. Cosmetic composition according to any one of the preceding claims, characterized in that the photodimerizable group (s) is (are) grafted on a support compound.

6. Cosmetic composition according to claim 5, characterized in that the support compound is chosen from poly (vinyl) polymers and polydiorganosiloxanes

7. Cosmetic composition according to claim 6, characterized in that the poly (vinyl) polymers are chosen from poly (vinyl acetate), preferably partially saponified.

8. Cosmetic composition according to any one of the preceding claims, characterized in that the compound (s) comprising at least one photodimerizable group is a polymer soluble or dispersed in the composition.

9. Cosmetic composition according to any one of the preceding claims, characterized in that the compound comprising at least one photodimerizable group is adsorbed on polymer particles, themselves dispersed in the composition.

10. Cosmetic composition according to claim 9, characterized in that the particles are particles of vinyl polymers.

11. Cosmetic composition according to claim 10, characterized in that the (poly) vinyl polymer is a poly (vinyl acetate).

12. Cosmetic composition according to claim 9, characterized in that it is aqueous dispersions of a polymer of the partially saponified polyvinylacetate type and carrying stilbazolium groups, brought into contact, in particular mixed, with polyvinylacetate particles.

13. Cosmetic composition according to any one of the preceding claims, characterized in that the compound comprising at least one photodimerizable group represents 0.01 to 25%, preferably 0.1 to 20%, and better still 1 to 15% by weight total of the composition.

14. Cosmetic composition according to any one of the preceding claims, characterized in that it also comprises an effective amount of at least one photosensitizer.

15. Cosmetic composition according to claim 13, characterized in that the photosensitizer (s) is (are) chosen from thioxanthone, Bengal rose, phloxine, eosine, erythrosine, fluorescein, acriflavin, thionine, riboflavin, proflavin, chlorophylls, hematoporphyrin, methylene blue and mixtures thereof.

16. Cosmetic composition according to claim 14 or 15, characterized in that the photosensitizer (s) represents (s) 0.00001% to 5% of the total weight of the composition.

17. Cosmetic composition according to any one of the preceding claims, characterized in that the (or) active (s) cosmetic (s) is (are) chosen (s) from saccharides, oligosaccharides, polysaccharides hydrolysed or not , modified or not; amino acids, oligopeptides, peptides, hydrolyzed proteins or not, modified or not, poly amino acids, enzymes; branched and unbranched fatty acids and alcohols; animal, vegetable or mineral waxes; ceramides and pseudoceramides; hydroxylated organic acids; UV filters; antioxidants and anti-free radical agents; chelators; anti-dandruff agents; seborrhea regulating agents; soothing agents; cationic surfactants; cationic, amphoteric polymers; organomodified silicones or not; mineral, vegetable or animal oils; polyisobutenes and poly (α-olefins); esters; soluble or dispersed anipnic polymers; soluble or dispersed nonionic polymers; reducing agents; coloring matters; foaming agents; film-forming agents; the particles ; and their mixtures.

18. Cosmetic composition according to claim 17, characterized in that the (or) active (s) cosmetic (s) represents (s) 0.001 to 30% of the total weight of the composition.

19. Cosmetic composition according to any one of the preceding claims, characterized in that it also comprises a solvent or a mixture of cosmetically acceptable solvents.

20. Cosmetic composition according to claim 19, characterized in that the solvent is chosen from water, alcohols, polyols, polyol ethers and their mixtures.

21. Cosmetic composition according to claim 20, characterized in that the alcohols are C ₁ -C 6 lower alkanols, and preferably chosen from ethanol, propanol and isopropanol.

22. Cosmetic composition according to claim 20, characterized in that the polyols are chosen from propylene glycol, hexylene glycol, glycerin, and pentanediol.

23. Cosmetic composition according to one of claims 19 to 22, characterized in that the solvent (s) represents (s) 0.1% to 99% of the total weight of the composition.

24. Cosmetic composition, characterized in that it has a pH of between 2 and 12, and preferably between 3 and 11.

25. Cosmetic composition according to any one of the preceding claims, characterized in that it comprises at least one adjuvant chosen from perfumes, fillers, pH adjusters, and preservatives.

26. A method for treating keratin materials comprising the following steps: a) application to the keratin materials of a composition as defined according to any one of claims 1 to 24, and b) irradiation of said composition on the keratin materials for crosslink the composition.

27. The method of claim 26, characterized in that it comprises, before the irradiation step and after the application step, drying of the keratin materials.

28. The method of claim 26 or 27, characterized in that it includes before or after step (b) of irradiation a pause at room temperature, or under heat, or under red light.

29. Method according to one of claims 26 to 28, characterized in that it comprises, prior to step (b) of irradiation, a step of partial masking of keratin materials and, after step (b) of irradiation, a rinsing step, or when the keratin materials are hair, a shampooing or styling step.

30. The method of claim 29, characterized in that it comprises, prior to the step of partially masking keratin materials and after the step of applying the composition, a step of drying keratin materials.

31. Method according to any one of claims 26 to 30, characterized in that the irradiation is an irradiation with radiation in the UVA or in the visible range, and preferably radiation in the UVA.

32. Method according to any one of claims 26 to 31, characterized in that, when the keratin materials are hair, it further comprises, before or after step (b) of irradiation, a step of hair shaping.

33. Method according to any one of claims 26 to 31, characterized in that the compound (s) comprising at least one photodimerizable group is (are) also thermodimerizable (s), and in that the step irradiation is replaced by a heating step between 40 and 200 ° C.

34. Method according to any one of claims 26 to 33, characterized in that the keratin materials are hair or nails.