EP1461002A1 - Hair treatment composition comprising an cosmetic active principle bound to biotin or a complexing agent thereof - Google Patents

Abstract

The invention concerns cosmetic compositions comprising a biotin derivative and/or a complexing agent of said derivative and, covalently bound to one of those two compounds or to both, at least an active principle other than dyes. The invention also concerns a hair treatment method based on said compositions, for producing on the hair a deposition of substance providing novel cosmetic properties.

Description

COMPOSITION FOR THE TREATMENT OF HAIR COMPRISING A COSMETIC ACTIVE AGAINST BIOTIN OR A COMPLEXING AGENT

The present invention relates to a cosmetic composition comprising at least one biotin compound (modified or unmodified biotin) carrying at least one group with non-coloring cosmetic activity.

The present invention also relates to a cosmetic composition comprising at least one complexing agent for modified or unmodified biotin, carrying at least one group with non-coloring cosmetic activity.

The present invention also relates to a composition

15 cosmetic comprising biotin modified or not associated with at least one complexing agent, the biotin or the complexing agent being carrying at least one group with non-coloring cosmetic activity.

The present invention also relates to several

20 hair treatment methods based on these compounds, aimed at creating a deposit on the fiber of the material providing new cosmetic properties.

It is advantageous to be able to fix on keratin materials and in particular the hair, active agents providing a benefit in a lasting manner. To achieve this objective, direct chemical grafting is a possible solution. Unfortunately, these chemical grafting techniques pose safety problems or lead to a degradation of the integrity of keratin materials. There therefore remains a need to create a deposit of material on the hair which is remanent to shampoos, does not degrade the hair fiber which can be removed as desired, and which may be crosslinkable. Biotin, also called vitamin H or B8, is a water-soluble vitamin made up of an imidazoline nucleus and a tetrahydrothiophene ring carrying a side chain with five carbon atoms. Biotin is a nutrient for hair and skin.

Biotin naturally binds with great affinity for avidin, a glycoprotein found in raw egg white. Biotin and avidin together form a complex by non-covalent bond among the most stable existing between biological molecules with a dissociation constant of 1.3 10 ^"15 at pH5. In addition, avidin has four sites of interaction for biotin.

The Applicant has discovered that by using the forces of association between two exogenous compounds of the hair, cosmetic active agents (previously fixed on at least one of the compounds) can be deposited on the surface of the hair.

The first object of the invention is therefore a composition, in particular a cosmetic composition, comprising at least one biotin compound (biotin modified or not) carrying at least one group with non-coloring cosmetic activity.

The second object of the invention is a composition, in particular a cosmetic composition, comprising at least one compound capable of forming, with a biotin compound, carrying or not having at least one group with ^~ non-coloring cosmetic activity, a complex whose dissociation constant is lower or equal to 10 ^-1 at the temperature of 25 ° C, the said complexing compound carrying at least one group with non-coloring cosmetic activity.

The third object of the invention is therefore a composition, in particular a cosmetic composition, comprising: a biotin compound a) chosen from biotin and modified biotins a compound b) capable of forming with compound a) a complex whose dissociation constant is less than or equal at 10 ^"1 at a temperature of 25 ° C, at least one of these compounds a) or b) being the carrier of at least one group with non-coloring cosmetic activity.

Another object of the invention is the set of cosmetic treatment methods for keratin materials using these compositions or the constituents a) and b) of the third object of the invention.

Other objects of the present application will emerge on reading the description and the examples which follow.

The compounds a), that is to say the biotin and the modified biotins, are preferably chosen from the compounds of formula (I)

* with A denoting a divalent radical comprising from 1 to 100 carbon atoms, linear or branched, saturated or not, interrupted or not by one or more heteroatoms and optionally substituted by one or more groups chosen from hydroxyl, amino, halogen groups, aryl, phosphate, phosphorate, sulfate, sulfonate, carboxy, alkoxycarbonyl, alkoxy. * with Y denoting a group Z chosen from carboxy, mercaptan, alkoxycarbonyl, amino, ammonio or a radical BW, W being a residue with cosmetic activity and B an entity for fixing the residue W to the skeleton derived from biotin.

* with n denoting 0 or 1 * with B denoting for example an amino group, imine, amide, ester, disulfide, thioester, urethane, urea, ether, thioether, azo, methine, epoxy, an aromatic or heterocyclic residue, dialkylpolysiloxane. * with W can be derived from UV filtering molecules, moisturizing or emollient molecules, conditioning agents, antistatic agents, antiperspirant agents, perfuming materials, reducing molecules, oxidizing molecules, antimicrobial agents, anti-dandruff agents, mineral or organic particulate agents possibly in the form of nanotubes or other three-dimensional assemblies such as fullerenes (eg fullerenes C60-C70) on which one or more polymers, anionic film-forming agents or nonionic, amphoteric or cationic on which organic or mineral particles are possibly adsorbed.

Particles include mineral particles and organic particles. The mineral particles can consist of the oxides, the dihydrate oxides, the hydroxides, the carbonates, the sulphides, the silicates, the phosphates of silicon, of calcium, of magnesium, of zinc, of aluminum, of titanium, of zirconium, of cerium, nacres, micas, particles constituted by 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, cadnium, zinc, tin, 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 (l-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 crosslinking agents 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.

The term “particles” means particles whose size is between 1 nm and 100 μm, preferably between lnm and 1000 nm and even more preferably between lnm and 50 nm. The term “particle size” is understood to mean the maximum dimension which it is possible to measure between two diametrically opposite points of the particle. The particles according to the invention can be spherical, lamellar, fibrillar, or completely random.

The biotin derivatives which can be used according to the invention are for example available from Sigma-Aldrich or Carbomer Inc and can be chosen from bovine albumin biotin, bovine albumin biotin gold labeled (5 or 20 nm), biotin dextran, biotin fluorescein, latex biotin, biotin carboxymethylcellulose, biotin chitosan, peroxidase biotinamidocaproyl, alkaline phosphatase-biotinamidocaproyl, biotin agarose, concanavalin A- biotin, β-galactosidase biotin, biotin-biotin

B-phycoerythrin-biotin.

The group W can be derived from the following active ingredients: * saccharides, oligosaccharides, polysaccharides hydrolyzed or not, modified or not, * amino acids, oligopeptides, peptides, hydrolyzed proteins or not, modified or not, polyamino acids, enzymes,

* branched and unbranched fatty acids and alcohols, * animal, vegetable or mineral waxes,

* ceramides and pseudo-ceramides,

* hydroxylated organic acids,

*. UV filters,

* antioxidants and anti-free radical agents, * chelating agents,

* dandruff agents,

* seborreal 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 anionic polymers,

* soluble or dispersed nonionic polymers,

* reducing agents and their mixtures.

In general, the saccharide, oligosaccharide or polysaccharide type compounds, hydrolysed or not, modified or not, which can be used in the present invention, are chosen from those which are in particular 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 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. As examples of saccharides, oligosaccharides, polysaccharides hydrolyzed or not, modified or not, which can be used in the invention, mention may be made in particular 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, carboxymethylcelluloses), 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 nines, agars, the glycosaminoglycans, arabic gums, tragacanth gums, ghatti gums, karaya gums, carob gums, guar gums and the xanthan gums.

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 for the present invention, mention may in particular be made of C ₃ -C ₃₀ carboxylic acids, such as palmitic acid, oleic acid, linoleic acid, myristic acid, l stearic acid, lauric acid, and their mixtures. The fatty alcohols which can be used in the present invention include in particular C ₈ -C ₃₀ 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 wax crystals 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 Carnauba, Candellila, Ouricury, Japanese wax, cocoa butter or cork fiber or sugarcane waxes; mineral waxes, for 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 which 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-butyl-4 '-diisopropyldibenzoyl-methane, p-amino-benzoic acid and its esters such as p-amino-benzoic acid and its esters such as 2-ethylhexyl dimethylaminobenzoate and N-propoxylated ethyl p-aminobenzoate, salicylates such as triethanolamine salicylate, cinnamic acid esters such as 2-ethylhexyl 4-methoxy-cinnamate, methyl diisopropylcinnamate , menthyl anthranilate, benzotriazole derivatives, triazine derivatives, β, β'-diphenylacrylate derivatives such as 2-ethylhexyl 2-cyano-3,3-diphenylacrylate and 2-cyano-3, 3- ethyl 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 salt 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 1-chloro 5,5-dimethylhydantoin, N-chlorosuccinimide;

the derivatives of l-hydroxy-2-pyridone such as, for example, 1-hydroxy-4-methyl-2-pyridone, l-hydroxy-6-methyl-2-pyridone and l-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 tar or wood tar 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-l, 4-butanedioic, 3-phenyl-2-propenoic, α-hydroxybenzene acetic, ethanesulfonic, 2-hydroxyethanesulfonic, 4- methylbenzenesulfonic, 4-amino-2-hydroxybenzoic, 2-phenoxy benzoic, 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 alkylated derivatives. Examples of inorganic bases are in particular the salts 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. The . 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 connected 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 more particularly be made of polymers of the polyamine, polyaminoamide and quaternary polyammonium type. These are known products.

The polymers of the polyamine, polyaminoamide, 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-trimethylammonium, 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 denotes preferably a methyl, ethyl, propyl group, 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) the 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 the acid diglycolic and saturated aliphatic dicarboxylic acids having 3 to 8 carbon atoms. 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 epichlorhyd.rine 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 U.S. patents 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 the BAS .F; (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 (C ₁ -C ₄ ) trialkyl (Cι-C ₄ ) ammonium salts such as those marketed under the name

SALCARE ^® SC 92, SALCARE ^® SC 95 and SALCARE ^® SC 96 by the company 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 deriving from a monomer comprising at least one basic nitrogen atom and C denotes a unit deriving from an acidic monomer comprising one or more carboxylic or sulphonic groups or alternatively 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 carboxylic group such as more particularly acrylic acid, methacrylic acid, maleic acid, alpha-chloroacrylic acid, and d 'a basic monomer derived from a substituted vinyl compound containing at least one basic atom such as more particularly the dialkylaminoalkylmethacrylate and acrylate, the dialkylaminoalkylmethacrylamide and acrylamide. Such compounds are described in US Patent No. 3 836 537. One can also cite the acrylate copolymer sodium / chloride acrylamidopropyltrimethylammonium 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 quaternization product 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 Rι ₀ represents a divalent group derived from a saturated dicarboxylic acid, from a mono or dicarboxylic aliphatic acid with ethylene double bond, from an ester of a lower alkanol having 1 to 6 carbon atoms of these acids or of a group deriving from the addition of any one of said acids with a primary bis or secondary bis amine, and Z denotes a group of a polyalkylene polyamine bis- primary, mono or bis-secondary and preferably represents: a) in the proportions of 60 to 100% by moles, the group

NH I - fΓ - ((CCHH ₂₉ >) _Y -NH- (III) where x = 2 and p = 2 or 3, or else x = 3 and p = 2 this group derived 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 = l and which is derived from ethylenediamine, or the piperazine group / \

^• 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 alkyls by action of acrylic acid, chloracetic acid or an alkanesultone 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 alkanesultones 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 R _n 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, R ₁₂ and R ₁₃ represent a hydrogen atom, a methyl group , ethyl or propyl, R ₁₄ and R, ₅ represent a hydrogen atom or an alkyl group such that the sum of the carbon atoms in R ₁₄ and R ₁₅ does not exceed 10.

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

For example, there may be mentioned methyl methacrylate copolymer and dimethylcarboxymethylammonioethyl methyl ethylmethacrylate such as the product sold under the name Diaformer Z301 ^® by the company Sandoz.

(5) polymers derived from chitosan containing monomer units corresponding to the following formulas: the motif (V) being present in proportions of between 0 and 30%, the motif (VI) in proportions of between 5 and 50% and the motif (VII) in proportions of between 30 and 90%, it being understood that in this motif F, R ₁₆ represents a group of formula:

Ri 8 R 19

R 17 -Ç- (O) _α -Ç (VIII)

in which if q = 0, R ₁₇ , R ₁₈ and R ₁₉ , 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 several nitrogen atoms 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 R ₁₇ , R _1g and R ₁₉ being in this case a hydrogen atom; or if q = 1, R ₁₇ , R ₁₈ and R ₁₉ 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:

^R 20

- (CH-CH ₂ ) - -CH- ^• CH- (IX)

COOH CO

NR ₂₁ R 24

NR ₂₃

^R 22

in which R ₂₀ represents a hydrogen atom, a CH ₃ O 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 ₂₃ denotes a lower alkyl group such as methyl, ethyl or a group corresponding to the formula: -R ₂₄ -N (R ₂₂ ) ₂ , R ₂₄ representing a group -CH ₂ - CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -, -CH ₂ -CH (CH ₃ ) -, R ₂₂ 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 type -D-X-D-X- chosen from: a) the polymers obtained by the action of chloracetic acid or sodium chloracetate on the compounds comprising at least one unit of formula:

-DXDXD- (X) where D denotes a group

/ \

- N N-

\ /

and X denotes the symbol E or E ', E or E', which may be 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 groups, 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

/ \

-N N-

\ /

and X denotes the symbol E or E 'and at least once E'; E having the meaning given above and E ¹ 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 and betaine functions by reaction with chloracetic acid or sodium chloracetate. (9) Alkyl (CC ₅ ) vinyl ether / maleic anhydride copolymers - partially modified by semiamidation with an N, N-dialkylaminoalkylamine such as N, N-dimethylaminopropylamine or by semiesterification with an N, N-dialcanolamine These copolymers can also include other vinyl comonomers such as vinylcaprolactarne.

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 which are insoluble in water; they can be in the form of oils, waxes, resins or gums.

Organopolysiloxanes are defined in more detail in Walter NOLL's book "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 still from: (i) cyclic silicones containing from 3 to 7 silicon atoms and preferably 4 to 5. It is, for example, octamethylcyclotetrasiloxane 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 of "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 "SILICONE

VOLATILE FZ 3109 "sold by the company UNION CARBIDE, with a chemical structure: (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 in particular be made of polyalkylsiloxanes, polyarylsiloxanes, polyalkylarylsiloxanes, 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 C ₆ -C ₂₄ alkyl groups such as the products called dimethicone-copolyol sold by the company Dow

CORNING under the name DC 1248 or SILWET ^® L 722 oils,

L 7500, L 77, L 711 from the company UNION CARBIDE and the alkyl (C ₁₂ ) - 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 C 1 - 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 carboxylic acid type such as, for example, in the products described in patent EP 186 507 from 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 oil, sunflower oil. , wheat germ oil, sesame oil, peanut oil, grape seed oil, soybean oil, rapeseed oil, 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 (-olefins) are chosen from those well known in the art. Examples of esters that may be mentioned include esters of fatty acids 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, sulfonic or phosphoric acids, and having a molecular weight by weight of between 500 and 5,000,000. The carboxylic groups are provided by monoacid monomers or unsaturated dicarboxylic acids such as those corresponding to the formula:

Ri _{\ /} (A) _n -COOH yC = C _s (XII) R ₃ 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 group neighboring methylene when n is greater than 1, via a heteroatom such as oxygen or sulfur, R _j denotes a hydrogen atom, a phenyl or benzyl group, R denotes a hydrogen atom, an alkyl group lower or carboxyl, R ₃ denotes a hydrogen atom, a. lower alkyl group, a -CH ₂ -COOH, phenyl or benzyl group.

In formula (XII) above, a lower alkyl group preferably contains from 1 to 4 carbon atoms and denotes by. in particular, the methyl and ethyl groups. The anionic polymers comprising carboxyl groups 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 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, acrylic or methacrylic acid esters, optionally grafted on a polyalkylene glycol such as polyethylene glycol, and optionally crosslinked. Such polymers are described in particular in French patent 1 222 944 and German application No. 2 330 956, copolymers of this type comprising in their chain an acrylamide unit, optionally N-alkylated and / or hydroxyalkylated as described in particular in 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 alkyl methacrylate CC ₄ and the copolymer of methacrylic acid and of ethyl acrylate sold under the name Luvimer ^® by the company MAEX

BASF.

C) copolymers derived from crotonic acid such as those comprising in their chain vinyl acetate or propionate units, and optionally other monomers such as the allyl or methallyl ester, vinyl ether or vinyl ester of a saturated carboxylic acid, linear or branched, with a long hydrocarbon chain, such as those comprising at least 5 carbon atoms, these polymers possibly being grafted and crosslinked, or alternatively a vinyl, allylic or methallylic ester of an α or β-cyclic carboxylic acid. Such polymers are described inter alia in French patents numbers 1 222 944, 1 580 545, 2 265 782, 2 265 781, 1 564 110 and 2 439 798. Commercial products falling into this class are resins 28-29- 30, 26-13-14 and 28-13-10 sold by the company NATIONAL STARCH. D) Polymers derived from maleic, fumaric or 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 falling into this class are the copolymers of maleic, citraconic, itaconic anhydrides and an allyl or methallyl ester optionally comprising a 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 plaintiff;

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;

- salts of polystyrenesulfonic acid, the sodium salts having a molecular weight of about 500,000 and about 100,000 sold respectively under the names Flexan 500 and Flexan ^{® ®} 130 by

National Starch. These compounds are described in patent FR 2198719;

- polyacrylamide-sulphonic acid salts such as those mentioned in US Patent 4,128,631, and the polyacrylamidoethylpropanesulphonic acid sold under the name Cosmedia Polymer HSP 1180 by Henkel ^®.

According to the invention, anionic polymers are preferably chosen from acrylic acid copolymers such as the terpolymer acrylic acid / ethyl acrylate / N-tert-butylacrylamide sold under the name ULTRAHOLD STRONG ^® by the company BASF, copolymers derived from crotonic acid such as vinyl acetate / vinyl tert-butylbenzoate / crotonic acid terpolymers and crotonic acid / vinyl acetate / neododecanoate terpolymers. vinyl sold under the name Resin 28-29-30 by the company NATIONAL STARCH, polymers derived from acids or anhydrides maleic, fumaric, itaconic with vinyl esters, vinyl ethers, vinyl halides, phenylvinyl derivatives, acrylic acid and its esters such as the methyl vinyl ether / maleic anhydride monoesterified copolymer 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 of ethyl acrylate sold under the name Luvimer ^® MAEX by BASF, the vinyl acetate / crotonic acid copolymer sold under the name

LUVISET ^® CA 66 by BASF and the vinyl acetate / crotonic acid / polyethylene glycol terpolymer under the name ARISTOFLEX ^® A by BASF.

According to the invention, anionic polymers can also be used in the form of latex or pseudolatex, that is to say in the form of an aqueous dispersion of insoluble polymer particles.

As nonionic polymers which can be used according to the present invention, there may be mentioned in particular:

- vinylpyrrolidone homopolymers; - copolymers of vinylpyrrolidone and of vinyl acetate;

- polyalkyloxazolines such as polyethyloxazolines by Dow Chemical under the names Peox ^® 50000, 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, alkyl acrylates and copolymers of 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; we can cite the products offered under the names NIPOL ^® LX 531 8 by the company NIPPON ZEON or those offered under the name CJ

0601 8 by the company ROHM &HAAS;

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

- copolymers of alkyl 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 nonionic 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 CC 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, Jaguar HP60 ^® and

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 composition according to the invention may contain one or more of the biotin compounds and complexing agents described above, in a total amount of between 0.001 and 90% by weight, preferably between 0.01 and 25% by weight, better still between 0, 1 and 20% by weight, relative to the total weight of the cosmetic treatment composition.

The cosmetically acceptable medium may consist solely of water, or of a solvent or mixture of solvents, or of a mixture of water and one or more cosmetically acceptable solvents such as a lower Cx- alcohol, such as ethanol, isopropanol, tert-butanol, n-butanol; alkylene glycols such as propylene glycol, glycol ethers.

The pH of the compositions according to the invention is between 4 and 8, preferably between 5 and 7. The compositions according to the invention can also contain additives such as natural or synthetic, anionic, amphoteric, zwitteronic, nonionic polymeric thickeners or cationic, associative or not, non-polymeric thickeners such as acids or electrolytes, anionic, nonionic, amphoteric surfactants, nacrants, opacifiers, perfumes, dyes, mineral or organic particles, preservatives, agents pH stabilization.

A person skilled in the art will take care to choose the optional additives and their quantity so that they do not harm the properties of the treatment compositions.

These additives are present in the composition according to the invention in an amount ranging from 0 to 20% by weight relative to the total weight of the composition.

The compounds b) are preferably chosen from compounds of structure:

D (A ') _n , (X) _m (II) in which m denotes 0 or 1 and X denotes Z' or CW; Z ', W', A 'and n' having the same possible meanings as Z, W, A and n respectively in formula (I) and C being an entity for fixing the residue W to the active element D of complexing, D being such that the set D (A ′) _n (X) _m can form with the compound (s) a) a complex whose dissociation constant is less than 10 ⁻¹ at the temperature of 25 ° C. For example, D (A ') _n . (X) _m denotes avidin (n' = m = 0) or streptavidin (n '= m = 0) or the antibiotin antibodies and their fragments (n' = m = 0) or avidin alkaline phosphatase (n '= 0, m = l) or avidin peroxidase (n' = 0, m = l). These compositions can be in the form of more or less thick solutions, creams, fluid gels, sticks or foams. They can be packaged as an aerosol.

An object of the invention is a set of cosmetic treatment methods for keratin materials and in particular for the hair.

A first method according to the invention consists firstly in depositing on the hair by adsorption on keratin materials a compound b) in which m = 0 or m = l, X denoting Z ′ if m = l, then in a second time to apply a compound a) in which

Y denotes BW.

A second method according to the invention consists firstly of depositing, by adsorption on keratin materials, a compound b) in which X denotes CW ′ and m = l, then in a second step in applying a compound a) in which Y denotes BW.

A third method according to the invention consists firstly of depositing on the keratin materials by adsorption a compound a) in which Y denotes Z, then in a second step of applying a compound b) in which X denotes CW ′ and m = l.

A fourth method according to the invention consists firstly in depositing on the keratinous materials by adsorption a compound a) in which Y denotes BW, then in a second time at

_ apply a compound b) in which m = 0 or m = l with X denoting Z 'if m = l.

A fifth method according to the invention consists firstly of depositing simultaneously on the keratin materials by adsorption a compound a) in which Y denotes BW then in a second step of applying a compound b) in which X = CW ′ and m = l. A sixth method according to the invention consists in depositing simultaneously on the keratin materials by adsorption a compound a) in which Y denotes Z and a compound b) in which X = CW ′ and m = l. A seventh method according to the invention consists in depositing simultaneously on the keratin materials by adsorption a compound a) in which Y denotes BW and a compound b) in which m = 0 or m = l with X denoting Z ′ if m = l. An eighth method according to the invention consists in depositing simultaneously on the keratin materials by adsorption a compound a) in which Y denotes BW and a compound b) in which m = l and

X = CW.

Optionally for all the processes, it is possible to supply, in one or more additional steps, one or more compounds a) or b). It is thus possible to form multilayer deposits.

Another object of the invention is constituted by multi-compartment kits. A first kit contains in a first compartment a compound a) in which Y = Z and in a second compartment a compound b) in which X = CW and m = l.

A second kit contains in a first compartment a compound a) in which Y = BW and in a second compartment a compound b) in which m = 0 or m = l, X denoting Z ′ if m = l. A third kit contains in a first compartment a compound a) in which Y = BW and in a second compartment a compound b) in which m = l and X = CW.

The hair treatment method according to the invention may comprise a preliminary step which consists of a cosmetic treatment chosen from the group formed by reducers or oxidants for permanent deformation of the hair, oxidation dyes, bleaches, shampoos or styling compositions .

The following examples are intended to illustrate the invention, without however being limiting in nature. Example 1:

In order to demonstrate the remanence properties of the invention compared to a simple physicochemical adsorption, nanoparticles of gold were deposited on the hair fiber with or without avidin in the medium, the biotin being attached to the particles to drop.

1) Particles deposited with biotin and avidin (sample 1)

30 mg of hair (about 20 hairs) is taken from a lock of natural hair previously washed, which is placed in a small glass bottle.

An avidin solution (Sigma-Aldrich A9275) is prepared at

1.5 mg / ml in a phosphate buffer solution (pH 7.2; 0.15 M). 3 ml of this avidin solution are brought into contact with the hair to be treated by bubbling nitrogen through the solution at room temperature until complete evaporation.

Rinsing is then carried out in several stages:

* rinsing with 3 ml of 0.05% phosphate + Tween 20 buffer solution for 1 minute 30 * rinsing with 3 ml of phosphate + Tween 20 buffer solution at

0.05% for 30 s

* four rinses with 5 ml of distilled water for 30 s.

The hair is then dried with the gentle heat of a dryer.

_ hair (around 30 ° C). 5 of these hairs treated with avidin are placed in a glass vial. 100 μl of a solution containing suspended gold particles (20 nm) (SIGMA; Albumin-biotin 20 nm gold labeled) are added to 700 μl of a phosphate buffer solution containing 0.05% Tween 20 and 0.5% BSA (bovine serum albumin). This solution is placed in contact with the 5 hairs previously treated with avidin and allowed to incubate for 24 hours, with shaking and at room temperature.

Rinsing is carried out in several stages:

* rinsing with 2 ml of phosphate buffer solution, Tween - 0.05% and BSA 0.5% "for 30 s * rinsing with 2 ml of a phosphate buffer solution for 1 min

* 3 rinses with 2 ml of distilled water for lmn30.

2) Particles deposited with biotin and without avidin

(sample 2)

5 hairs which are placed in a glass flask and to which 500 μl of a phosphate buffer solution (pH 7.2; 0.15 M) are taken from a lock of natural hair previously washed. It is incubated for 24 hours, with shaking and at room temperature. After having seen the supernatant removed, the hair is rinsed 3 times with distilled water for lmn30. It is dried in the gentle heat of a dryer (around 30 ° C). 100 μl of a solution containing suspended gold particles (20 nm) (SIGMA; Albumin - biotin - 20 nm gold labeled) are added to 700 μl of a phosphate buffer solution containing 0.05% Tween 20 and 0.5% BSA. This solution is placed in contact with the 5 control hairs and incubated for 24 hours, with shaking and at room temperature. The same rinsing is carried out as described above.

The hair is analyzed by Scanning Electron Microscopy and EDX (Energy dispersive X-ray). After several washes, the sample treated with the avidin / biotin system (sample 1) still shows the presence of gold nanoparticles on the surface. There is therefore a marked afterglow after washing. On the other hand, no gold nanoparticle is detected on the hair not treated with avidin (sample 2).

This example clearly shows the advantage of the ligand-avidin / biotin receptor pair for the creation of a deposit of residual material in washes. Example 2: Remanent grafting on washing of an enzyme (peroxidase) thanks to the biotin / avidin couple.

* Adsorption of peroxidase derivatized with biotin on the hair treated with avidin (sample 1):

30 mg of hair (approximately 20 hairs) is taken from a lock of white hair previously washed in white, which is placed in a small glass bottle. A solution of avidin (Sigma-Alrich A9275) at 1.5 mg / ml is prepared in a phosphate buffer solution (pH 7.2; 0.15 M). 3 ml of this avidin solution are brought into contact with the hair to be treated for 24 hours at room temperature.

Rinsing is then carried out in several stages:

1. rinse with 3ml of 0.05% phosphate buffer + Tween 20 for lmn30

2. rinse with 3ml of 0.05% phosphate buffer + Tween 20 for 30s

3. four rinses with 5ml of distilled water for 30s.

This hair treated with avidin is then dried with the gentle heat of a hair dryer (approximately 30 ° C.) for approximately 20 min.

A biotinylated peroxidase solution (reference P 9568, sold by Sigma) at 0.1 mg / ml is prepared in phosphate buffer. The biotinylated peroxidase solution is diluted to the tenth, lml of this solution is brought into contact with the samples (5 hairs) for 1 h at room temperature. Then rinse with 2 ml of distilled water for 1 minute three times in succession.

To demonstrate the peroxidase attached to the hair, a kit sold by Sigma (AEC-101 Staining Kit) is used. One ml of substrate is poured into each bottle, and it is left in contact with the hair for exactly 5 minutes. The samples are rinsed 3 times with 2 ml of distilled water. Two hairs are taken with the clamp for each sample and fixed on a glass slide. * Adsorption of peroxidase derivatized with biotin on the hair not treated with avidin (sample 2):

The same protocol as described above is used on hair not treated with avidin.

After these experiments, the hair is analyzed by optical microscopy in white light over its entire length.

After several washes, the sample treated with the avidin / biotin system (sample 1) still shows the presence of peroxidase (red coloration) on the surface. There is therefore a marked afterglow after washing. On the other hand, no peroxidase (absence of red coloration) is detected on the hair not treated with avidin (sample 2).

Claims

1. Cosmetic composition comprising: a biotin compound a) and an agent b) capable of forming a complex, of dissociation constant less than or equal to 10 -1 at the temperature of 25 ° C., with the biotin compound, the biotin compound or l complexing agent carrying at least one group with non-coloring cosmetic activity.

2. Composition according to Claim 1, characterized in that the compound a) is chosen from the compounds of formula (I) * with A denoting a divalent radical comprising from 1 to 100 carbon atoms, linear or branched, saturated or not, interrupted or not by one or more heteroatoms and optionally substituted by one or more groups chosen from hydroxyl, amino, halogen groups, aryl, phosphate, phosphorate, sulfate, sulfonate, carboxy, alkoxycarbonyl, alkoxy.

* with Y denoting a group Z chosen from carboxy, mercaptan, alkoxycarbonyl, amino, ammonio or a radical BW, W being a residue with cosmetic activity and B an entity for fixing the residue W to the skeleton derived from biotin, * with n denoting 0 or 1,

* with B denoting for example an amine, imine, amide, ester, disulfide, thioester, urethane, urea, ether, thioether, azo, methine, epoxy group, an aromatic or heterocyclic residue, dialkylpolysiloxane, * with W possibly being derived from molecules filtering UV, hydrating or emollient molecules, conditioning agents, antistatic agents, antiperspirant agents, perfuming materials, reducing molecules, oxidizing molecules, antimicrobial agents, anti-dandruff agents, mineral or organic particulate agents on which one or more polymers are optionally adsorbed, anionic or nonionic, amphoteric or cationic film-forming agents on which organic or mineral particles are optionally adsorbed.

3. Composition according to any one of claims 1 and

2, characterized in that the compound b) is chosen from compounds of structure:

D (A ') n' (X) m (II) * in which m denotes 0 or 1 and X denotes Z 'or CW';

* Z ', W', A 'and n' having the same possible meanings as Z, W, A and n respectively in formula (I)

* C being an entity for fixing the residue W to the active element D of complexing, * D being such that the set D (A ') n' (X) m can form with the compound (s) a) a complex of which the dissociation constant is less than 10-1 at the temperature of 25 ° C.

4. Composition according to any one of claims 1 to

3, characterized in that the compound b) denotes avidin.

5. Composition according to any one of claims 1 to

3, characterized in that the compound b) denotes streptavidin.

6. Composition according to any one of claims 1 to 3, characterized in that the compound b) denotes an antibiotin antibody.

7. Composition according to any one of claims 1 to

6, characterized in that it is in the form of a more or less thick aqueous, alcoholic or hydroalcoholic solution, a cream, a fluid gel, a stick, a foam, optionally packaged in aerosol form.

8. Cosmetic treatment process for keratin materials and in particular hair, consisting in depositing on keratin materials by adsorption, firstly a compound b) in which m = 0 or m = l, X denoting Z ′ if m = l, then in a second step to apply a compound a) in which Y denotes BW.

9. A method of cosmetic treatment of keratin materials and in particular of the hair, consisting in depositing on keratin materials by adsorption, firstly a compound b) in which X denotes CW ′ and m = l, then in a second step apply a compound a) in which Y denotes BW.

10. Cosmetic treatment process for keratin materials and in particular hair, consisting in depositing on keratin materials by adsorption, a compound a) in which Y denotes Z, then in a second step applying a compound b) in which X denotes CW 'and m = l.

11. Cosmetic treatment process for keratin materials and in particular hair, consisting in depositing on keratin materials by adsorption a compound a) in which Y denotes BW, then in a second step in applying a compound b) in which m = 0 or m = l with X denoting Z 'if m = l.

12. A method of cosmetic treatment of keratin materials and in particular of the hair, consisting in depositing simultaneously on keratin materials by adsorption a compound a) in which Y denotes BW then in a second step applying a compound b) in which X = CW 'and m = l.

13. Process for the cosmetic treatment of keratin materials and in particular of the hair, consisting in depositing simultaneously on the keratin materials by adsorption a compound a) in which Y denotes Z and a compound b) in which X = CW ′ and m = l.

14. Cosmetic treatment process for keratin materials and in particular hair, consisting in depositing simultaneously on keratin materials by adsorption a compound a) in which Y denotes BW and a compound b) in which m = 0 or m = l with X denoting Z ¹ if m = l.

15. A method of cosmetic treatment of keratin materials and in particular of the hair, consisting in depositing simultaneously on the keratin materials by adsorption a compound a) in which Y denotes BW and a compound b) in which m = l and X = CW '.

16. Process for treating keratinous materials, characterized in that it comprises a subsequent step in which at least one compound a) or a compound b) is brought.

17. Kit for treating keratin materials, characterized in that it comprises in a first compartment a compound a) in which Y = Z and in a second compartment a compound b) in which X = CW 'and m = l.

18. Kit for treating keratin materials, characterized in that it comprises in a first compartment a compound a) in which Y = BW and in a second compartment a compound b) in which m = 0 or m = l, X denoting Z 'if m = l.

19. Kit for treating keratin materials, characterized in that it comprises in a first compartment a compound a) in which Y = BW and in a second compartment a compound b) in which m = l and X = CW '.

20. Process for treating keratinous materials, characterized in that it comprises a preliminary step consisting of a cosmetic treatment chosen from the group formed by reducing agents or oxidants for permanent deformation of the hair, oxidation dyes, discoloration, shampoos or styling compositions, then a cosmetic composition as defined in any one of Claims 1 to 7, which is applied in sufficient quantity.

21. Cosmetic composition comprising a biotin compound a) as defined in claim 3, Y denoting BW.

22. Cosmetic composition comprising a complexing agent b) as defined in claim 4, with m = 1 and X denoting CW ′.