EP2073786A2

EP2073786A2 - Leave-in hair dyeing process using a composition comprising a coloured polymer and an active cosmetic agent

Info

Publication number: EP2073786A2
Application number: EP07823844A
Authority: EP
Inventors: Maxime De Boni; Bruno Laguitton; Jean-Daniel Debain
Original assignee: LOreal SA
Current assignee: LOreal SA
Priority date: 2006-09-15
Filing date: 2007-09-17
Publication date: 2009-07-01
Also published as: JP2010503646A; KR20090040915A; MX2009002542A; WO2008032003A2; WO2008032003A3

Abstract

The invention relates to a hair dyeing process consisting of the application of a composition containing at least one anionic coloured polymer comprising an anionic chromophore and at least one active cosmetic agent selected from among a non-silicon oil, an alkylpolyglucoside surfactant, a carboxylic anionic or cationic, amphoteric, nonionic non-associative setting polymer, an organic silicon compound comprising less than 6 silicon atoms. According to the invention, there is no rinsing stage after said application. Such a process makes it possible to obtain a coloration which is easy to carry out and which preserves the cosmetic appearance of the keratin fibres.

Description

METHOD FOR COLORING HAIR NOT RINSE FROM A COMPOSITION COMPRISING A COLORED AND ACTIVE POLYMER

COSMETIC

The subject of the invention is a process for staining unralued hair from a composition comprising a colored polymer and a particular cosmetic active agent.

It is known to dye keratinous fibers and in particular human hair with dye compositions for obtaining temporary colorations. Temporary stains are stains that have low water or rubbing toughness and are largely removed with the first shampoo. For example, patent applications EP 747 036 and EP 852 843 propose temporary staining from water dispersible color polymers containing sulfo groups and which comprises carbonyloxy bonds and a chromophore. US Patent 4 91 1731 discloses a temporary coloring method which consists of applying to the hair a complex formed of a particular cationic polymer and an anionic colored polymer, then rinsing the hair thus colored.

These temporary stains, also known as fugitive staining, are generally not used to perform a true coloring: they serve essentially to enhance a fading of a color obtained by permanent or direct coloring. They are hardly visible on dark hair.

The object of the present invention is to provide a novel process for temporary staining of keratinous fibers which does not have the drawbacks of the prior art stains, in particular, a method which respects the integrity of the keratinous fibers and which makes it possible to obtain intense coloring, visible on light hair as on dark hair that resists water or friction but are largely eliminated in the first shampoo and are easy to implement.

This object is achieved with the present invention which relates to a method for dyeing keratinous fibers comprising applying a composition containing at least one anionic chromophore anionic color polymer and at least one cosmetic active agent chosen from a non-silicone oil, an alkylpolyglucoside surfactant, a non-associative and nonionic, amphoteric, cationic or anionic carboxylic fixing polymer, an organic silicon compound comprising less than 6 silicon atoms, this application not being followed by a fiber rinsing step .

The method of the present invention makes it possible in particular to obtain a fast temporary keratinic fiber staining which can be implemented in a single stage, without degradation of keratin fibers with a silky touch and a significant shine.

The resulting color is instantly visible. Drying for example with a hairdryer or helmet can be practiced immediately. The hair can also be dried in the open air.

The colorations obtained are fleeting since they fade from the first shampoo and disappear in a few shampoos.

The method of the invention makes it possible in particular to obtain a visible coloration of natural or discolored clear hair as well as dark hair that is natural or colored for example by oxidation or direct dyeing.

By colored polymer is meant a polymer chain with pendant grafts consisting of coloring units. This colored polymer can be charged but the anionic charge of the polymer is carried by the colored graft. The nature of the charge of the polymer may be the same or different to that of the colored graft. There may be multiple charges per repetitive unit. The overall nature of the charge of the compound in solution is pH dependent. This polymer chain may be nonionic, anionic, cationic or amphoteric and may be wholly or partially soluble in water. The overall charge of the polymer must be anionic.

Such a polymer comprises, for example, at least one unit represented by:

in which COL represents the chromophore which is attached to the polymer backbone either directly or via a linear or branched saturated or unsaturated hydrocarbon-based X chain comprising from 1 to 10 carbon atoms, preferably from 1 to 6 carbon atoms, carbon and at least one of the carbon atoms can be replaced by a heteroatom selected from sulfur, silicon, phosphorus, selenium, nitrogen, oxygen, an SO ₂ group, the hydrocarbon chain may be substituted for the no, the polymer comprising at least one negative charge carried by the chromophore, and n represents the number of repeating units of this type present in the polymer. Generally, n is between 1 and 1000, preferably between 1 and 500. Y is the counter-ion. These polymers can be in blocks, sequences or statistics.

As substituent of the carbon chain, there may be mentioned radicals, alkyl, hydroxy, alkoxy, hydroxyalkyl, halogens, amino radicals, amino radicals mono or disubstituted by an alkyl or hydroxyalkyl radical. As chromophores, there may be mentioned radicals derived from nitrobenzene dyes, azo, phenotiazine, xanthene, phenanthridine, phthalocyanine, those derived from triarylmethane, and those obtained from direct dyes with carbonyl group. Among the chromophores of this type, mention may be made, for example, of chromophores derived from the dyes chosen from acridone, benzoquinone, anthraquinone, naphthoquinone, benzanthrone, anthranthrone, pyranthrone, pyrazolanthrone, pyrimidinoanthrone, flavanthrone, indanthrone, flavone, (iso) violanthrone, isoindolinone. , benzimidazolone, isoquinolinone, anthrapyridone, pyrazoloquinazolone, perinone, quinacridone, quinophthalone, indigo, thioindigo, naphthalimide, anthrapyrimidine, diketopyrrolopyrrole, coumarin.

By way of example of colored polymers, mention may be made of:

By way of examples of anionic chromophore, mention may be made of chromophores substituted with at least one sulphonate, carboxylate, phosphate, phosphonate and sulphate group. By way of example, mention may be made of radicals derived from acid nitro-acid direct dyes, acidic azo dyes, acidic azine dyes, acidic triarylmethane dyes, acidic indoamine dyes and non-quinonic acidic natural dyes.

As anionic colored polyelectrolyte, mention may be made of those described in US Pat. No. 4,971,231, US Pat. No. 6,306,182, EP 852,943, EP 747,036, US Pat. No. 4,381,260, US Pat. No. 4,314,808 and US Pat. 4,051,138.

By way of example, the anionic colored polymer corresponds to the formula:

_{* *} or or in which COL is an anionic chromophore radical and Y is counter-ions.

The amount of colored polyelectrolyte in the composition applied to the fibers is generally from 0.01 to 20%, preferably from 0.1 to 5%. According to a particular embodiment, the composition is an aqueous composition.

For the purposes of the present invention, the term "oil" means a substance which is liquid at ambient temperature, for example at 25 ° C. and at atmospheric pressure, and insoluble in water.

For the purposes of the present invention, the term "insoluble in water" means a substance which has a solubility in pure water of less than 1% at 25 ° C. and at atmospheric pressure.

The oils used in the present invention have a dynamic viscosity at 25 ^° C., less than 1 Pa · s (1000 cps), preferably between 10 ^'3 and 0.1 Pa · s (1 and 100 cps). The dynamic viscosity is measured at 25 ^° C. with a shear rate of 100 s ^-1 , for example with the apparatus referenced RM 180 Rheomat by the company METTLER.

The oils which can be used in the present invention are preferably chosen from vegetable oils, mineral oils, synthetic oils, liquid fatty acid esters and liquid fatty acids.

Among the vegetable oils that can be used in the present invention, mention may in particular be made 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 and calophyllum oil.

Examples of mineral oils are paraffin oil and vaseline oil.

The synthetic oils may in particular be chosen from polydecenes, squalane, poly (α-olefins) such as isododecane or isohexadecane, transesterified vegetable oils and fluorinated oils.

It is also possible to use fatty acid esters, such as, for example, compounds of formula RaCOORb in which Ra represents the residue of a higher fatty acid having from 6 to 29 carbon atoms and Rb represents a hydrocarbon-based chain containing from 3 to at 30 carbon atoms, such as purcellin oil (stearyl octanoate), isopropyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, diisopropyl adipate, isononyl isononanoate, 2-ethylhexyl palmitate, 2-hexyldecyl laurate, 2-octyldecyl palmitate, myristate or 2-octyldodecyl lactate.

Liquid fatty acids such as oleic acid can also be used.

Particularly preferred oils are liquid fatty acids, liquid fatty esters and vegetable oils.

The oil (s) as defined above is or are preferably present in an amount of between 0.01 and 95% by weight, more preferably in an amount between 1 and 60% by weight relative to the weight of the composition.

The alkylpolyglucoside surfactants present in the composition are surfactants well known in the state of the art. These surfactants may be more particularly represented by the following general formula:

R ₁ O- (R ₂ O) ₁ (G) _V wherein R represents an alkyl radical and / or linear or branched alkenyl containing from about 8 to 24 carbon atoms, an alkylphenyl radical whose linear or branched alkyl radical comprises 8 to 24 carbon atoms, R ₂ represents an alkylene radical having about 2 to 4 carbon atoms, G represents a sugar unit comprising from 5 to 6 carbon atoms, t denotes a value ranging from 0 to 10, preferably O at 4, preferably 0 to 4 and v is a value from 1 to 15.

According to one particular embodiment, the alkylpolyglucoside surfactants are compounds of formula (II) in which R 1 denotes more particularly a saturated or unsaturated, linear or branched alkyl radical containing from 8 to 18 carbon atoms, t denotes a value ranging from from 0 to 3 and more particularly still equal to 0, G may denote glucose, fructose or galactose, preferably glucose. The degree of polymerization, ie the value of v in formula (II), may range from 1 to 15, from preferably from 1 to 4. The average degree of polymerization is more particularly between 1 and 2.

The glucosidic bonds between the sugar units are of type 1 -6 or 1 -4 and preferably 1 -4.

Compounds of formula (II) are in particular represented by the products sold by the company COGNIS under the names PLANTAREN® (600 CS / U, 1200 and 2000) or PLANTACARE® (818, 1200 and 2000). It is also possible to use the products sold by the company SEPPIC under the trade names TRITON CG1 10 (or ORAMIX CG 10) and TRITON CG312 (or ORAMIX® NS 10), the products sold by B.A.S.F. under the name LUTENSOL GD 70 or those sold by CHEM Y under the name AG10 LK.

Mention may also be made of C ₈ / C ₁₈ alkyl polyglucoside 1, 4 in a 53% aqueous solution marketed by COGNIS under the reference PLANTACARE® 818 UP.

The amount of alkylpolyglucoside surfactants present in the composition is generally between 0.6 and 30%, preferably between 0.5 and 10% relative to the total weight of the composition.

For the purposes of the present application, the term "fixing polymer" is intended to mean a polymer which makes it possible to form or maintain the shape of the keratinous fibers such as the hair.

By non-associative polymer is meant a polymer not containing a hydrophobic chain, especially carbon chains comprising more than 10 carbon atoms.

All cationic, amphoteric, nonionic fixing polymers and mixtures thereof used in the art can be used in the compositions according to the present application. Anionic fixing polymers are anionic polymers with carboxylic function.

The fixing polymers are soluble in the cosmetically acceptable medium.

The anionic fixing polymers have a number average molecular weight of between about 500 and 5,000,000.

The carboxylic groups are provided by unsaturated mono- or di-carboxylic acid monomers, such as those corresponding to the formula:

^R \., - (.A ₁ ) -COOH

RR in which n is an integer from 0 to 10, Ai denotes a methylene group, optionally linked to the carbon atom of the unsaturated group or to the neighboring methylene group when n is greater than 1, via a heteroatom such as Oxygen or sulfur, R ₇ denotes a hydrogen atom, a phenyl or benzyl group, R ₈ denotes a hydrogen atom, a lower alkyl or carboxyl group, R ₉ denotes a hydrogen atom, a lower alkyl group, a -CH ₂ -COOH group, phenyl or benzyl group.

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

The anionic fixing polymers with preferred carboxylic groups according to the invention are:

A) copolymers of acrylic or methacrylic acid or their salts and in particular the products sold under the names Ultrahold ^® by the company BASF, acrylic acid and of acrylamide sold in the form of their sodium salt under the denominations RETEN 421, 423 or 425 by the company HERCULES, the sodium salts of polyhydroxycarboxylic acids;

B) copolymers of acrylic or methacrylic acid with a monoethylenic monomer such as ethylene, styrene, vinyl esters, esters of acrylic or methacrylic acid, optionally grafted onto a polyalkylene glycol such as polyethylene glycol, and optionally crosslinked. Such polymers are described in particular in French Patent No. 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 such as described in particular in the Luxemburg patent applications Nos ^. 75370 and 75371 or proposed under the name QUADRAMER by the company AMERICAN CYANAMID. Mention may also be made of copolymers of acrylic acid and of C ₁ -C ₄ alkyl methacrylate and terpolymers of vinylpyrrolidone, acrylic acid and C ₁ -C ₂ alkyl methacrylate, for example lauryl, such as the one sold by the company ISP under the name Acrylidone ^® LM, and methacrylic acid / ethyl acrylate / butyl acrylate terpolymers such as the product sold under the name Luvimer ^® 100 P by the company BASF;

Mention may also be made of methacrylic acid / acrylic acid / ethyl acrylate / methyl methacrylate copolymers in aqueous dispersion, sold under the name AMERHOLD® DR 25 by the company Amerchol;

C) Crotonic acid copolymers, such as those comprising in their chain acetate or vinyl propionate units, and possibly other monomers such as allyl or methallyl esters, vinyl ethers or vinyl esters of a saturated carboxylic acid, linear or branched, with a long hydrocarbon chain, such as those containing at least 5 carbon atoms, these polymers possibly being grafted or crosslinked, or still another vinyl, allyl or methallyl ester monomer of an α- or β-cyclic carboxylic acid. Such polymers are described, inter alia, in French Patents ^Nos 1222944, 1580545, 2265782, 2265781, 1564 1 10 and 2 439 798. Commercial products coming within this class are the resins 28- 29-30, 26-13-14 and 28-13-10 marketed by National Starch;

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

copolymers comprising (i) one or more maleic, fumaric and itaconic acids or anhydrides and (ii) at least one monomer chosen from vinyl esters, vinyl ethers, vinyl halides, phenylvinyl derivatives, acrylic acid and its esters, the anhydride functions of these copolymers being optionally monoesterified or monoamidified. Such polymers are described in particular in US Patents ^Nos 2,047,398, 2,723,248, January 13 2102, GB Patent No. 839 805. Commercial products include those sold under the names Gantrez AN or ES by ^® the ISP company;

copolymers comprising (i) one or more maleic, citraconic and itaconic anhydride units and (ii) one or more monomers chosen from allylic or methallyl esters optionally containing one or more acrylamide, methacrylamide, α-olefin or acrylic or methacrylic ester groups; acrylic or methacrylic acids or vinylpyrrolidone in their chain, the anhydride functions of these copolymers being optionally monoesterified or monoamidified.

These polymers are for example described in the French patents Nos ^. 2,350,384 and 2,357,241 of the Applicant;

E) Polyacrylamides having carboxylate groups.

Homopolymers and copolymers comprising sulphonic groups are polymers comprising vinylsulphonic, styrene-sulphonic, naphthalenesulphonic or acrylamido-alkylsulphonic units.

These polymers may especially be chosen from:

salts of polyvinylsulphonic acid having a molecular mass of between about 1,000 and 100,000, as well as copolymers with an unsaturated comonomer such as acrylic or methacrylic acids and their esters, as well as acrylamide or its derivatives, vinyl ethers and vinylpyrrolidone; - salts of polystyrene sulfonic acid such as the sodium salts are sold under the name Flexan 500 and Flexan ^® ^® 130 by National Starch. These compounds are described in patent FR 2 198 719;

the polyacrylamidesulfonic acid salts such as those mentioned in US Pat. No. 4,128,631, and more particularly the polyacrylamidoethylpropanesulphonic acid sold under the name COSMEDIA POLYMER HSP 1180 by HENKEL. As another anionic fixing polymer that may be used according to the invention, mention may be made of the anionic block polymer connected with the anionic copolymer type of (meth) acrylic acids, alkyl esters of (meth) acrylic acids and of allyl methacrylate called MAP- Acrylate / Allyl methacrylate copolymer sold under the name Fixate G-100 by the company Noveon.

According to the invention, the anionic fixing polymers are chosen from acrylic acid copolymers such as the acrylic acid / ethyl acrylate / N-tert-butylacrylamide sold under the name Ultrahold ^® STRONG by the company BASF, copolymers crotonic acid derivatives such as vinyl acetate terpolymers / vinyl tert-butylbenzoate / crotonic acid and crotonic acid / vinyl acetate / vinyl neododecanoate terpolymers sold in particular 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 methylvinylether / monoesterified maleic anhydride copolymers sold for example, under the name GANTREZ ^® by ISP, the copo lymères of methacrylic acid and of methyl methacrylate sold under the name Eudragit ^® L by the company Rohm Pharma, the copolymers of methacrylic acid and of ethyl acrylate sold under the name Luvimer ^® MAEX or MAE by the company BASF and vinyl acetate / crotonic acid copolymers sold under the name Luviset CA 66 by the company BASF and the vinyl acetate / crotonic acid copolymers grafted with polyethylene glycol sold under the name Aristoflex ^® A by the company BASF, the polymer sold under the name Fixate G-100 by the company NOVEON.

Among the anionic fixing polymers mentioned above, are more particularly preferred use in the context of the present invention, the methyl vinyl ether / maleic anhydride copolymers sold under the name Gantrez ^® ES 425 by the company ISP, the acrylic acid / acrylate ethyl / N-tert-butylacrylamide sold under the name Ultrahold ^® STRONG by BASF, the vinyl acetate / vinyl tert-butylbenzoate vinyl / crotonic acid and the crotonic acid / vinyl acetate / vinyl neododecanoate terpolymers sold under the name Resin 28-29-30 by the company National Starch, the copolymers of methacrylic acid and ethyl acrylate sold under the name Luvimer ^® MAEX or MAE by the company BASF, the vinylpyrrolidone / acrylic acid / lauryl methacrylate terpolymers sold under the name Acrylidone ^® LM by the company ISP, the polymer sold under the name Fixate G-100 by Noveon.

The cationic fixing film-forming polymers that can be used according to the present invention are preferably chosen from polymers containing primary, secondary, tertiary and / or quaternary amine groups forming part of the polymer chain or directly connected thereto, and having a molecular weight included between 500 and about 5,000,000 and preferably between 1,000 and 3,000,000.

Among these polymers, mention may be made more particularly of the following cationic polymers:

(1) homopolymers or copolymers derived from acrylic or methacrylic esters or amides and comprising at least one of the following units of formulas:

R

-

R ₅ R ₅ in which:

R ₃ denotes a hydrogen atom or a CH ₃ radical;

A is a linear or branched alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group having 1 to 4 carbon atoms;

Fi ₄ , R ₅ , R ₆ , which may be identical or different, represent an alkyl group having from 1 to 8 carbon atoms or a benzyl radical;

R 1 and R ₂ , which are identical or different, each represent a hydrogen atom or an alkyl group having from 1 to 6 carbon atoms; X denotes a methosulphate anion or a halide such as chloride or bromide.

The copolymers of family (1) also contain one or more units derived from comonomers which may be chosen from the family of acrylamides, methacrylamides, diacetones-acrylamides, acrylamides and methacrylamides substituted on the nitrogen by lower alkyl groups (Ci-C ₄ ), groups derived from acrylic or methacrylic acids or their esters, vinyllactams such as vinylpyrrolidone or vinylcaprolactam, vinyl esters.

Thus, among these copolymers of the family (1), mention may be made of:

copolymers of acrylamide and of dimethylaminoethyl methacrylate quaternized with dimethyl sulphate or with a dimethyl halide, such as that sold under the name HERCOFLOC® by the company Hercules,

the copolymers of acrylamide and of methacryloyloxyethyltrimethylammonium chloride described for example in the patent application EP-A-080976 and sold under the name BINA QUAT P 100 by the company CIBA GEIGY,

the copolymer of acrylamide and methacryloyloxyethyltrimethylammonium methosulphate, such as that sold under the name Reten by the company Hercules,

vinylpyrrolidone / dialkylaminoalkyl acrylate or methacrylate copolymers, whether or not quaternized, such as the products sold under the name "GAFQUAT®" by the company ISP, for example "GAFQUAT® 734" or "GAFQUAT® 755", or the products referred to as " COPOLYMER® 845, 958 and 937 ". These polymers are described in detail in French Patents 2,077,143 and 2,393,573, the terpolymers dimethylaminoethyl methacrylate / vinylcaprolactam / vinylpyrrolidone such as the product sold under the name GAFFIX VC 713 by the company ISP, and

and the quaternized vinylpyrrolidone / dimethylaminopropyl methacrylamide copolymers, such as the products sold under the name "GAFQUAT® HS 100" by the company ISP.

(2) cationic, preferably quaternary ammonium polysaccharides such as those described in US Pat. Nos. 3,589,578 and 4,031,307, such as guar gums containing cationic trialkylammonium groups. Such products are marketed in particular under the trade names JAGUAR C13 S, JAGUAR C 15, JAGUAR C 17 by MEYHALL.

(3) quaternary copolymers of vinylpyrrolidone and vinylimidazole;

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

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

The amphoteric fixing polymers that may be used in accordance with the invention may be chosen from polymers comprising units B and C statistically distributed 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 derived from an acidic monomer having one or more carboxylic or sulfonic groups, or B and C may denote groups derived from zwitterionic monomers of carboxybetaines or sulfobetaines;

B and C may also designate 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 sulfonic group connected via a hydrocarbon group, or Well B and C are part of a chain of an ethylene-α, β-dicarboxylic-based polymer, one of whose carboxylic groups has been reacted with a polyamine having one or more primary or secondary amino groups.

The amphoteric fixing polymers corresponding to the definition given above, which are more particularly preferred, are chosen from the following polymers:

(1) copolymers with acidic vinyl units and basic vinyl units, such as those 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 a basic monomer derived from a substituted vinyl compound containing at least one basic atom, such as, more particularly, dialkylaminoalkyl methacrylate and acrylate, dialkylaminoalkylmethacrylamide and acrylamide. Such compounds are described in U.S. Patent No. 3,836,537.

(2) polymers comprising units derived from: a) at least one monomer chosen from acrylamides or methacrylamides substituted on the nitrogen atom with an alkyl group; b) with at least one acidic comonomer containing one or more several reactive carboxylic groups, and c) at least one basic comonomer such as primary, secondary, tertiary and quaternary amine substituted esters of the acrylic acids and methacrylic acid, 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 the compounds whose alkyl groups contain from 2 to 12 carbon atoms, and more particularly N-ethylacrylamide, N-tert-butylacrylamide, N-tert-octylacrylamide, N octylacrylamide, N-decylacrylamide, N-dodecylacrylamide and the corresponding methacrylamides.

The acid comonomers are chosen more particularly from acrylic, methacrylic, crotonic, itaconic, maleic and fumaric acids as well as alkyl monoesters having 1 to 4 carbon atoms of maleic or fumaric acids or anhydrides.

Preferred basic comonomers are aminoethyl, butylaminoethyl, N, N'-dimethylaminoethyl, N-tert-butylaminoethyl methacrylates.

Particularly The copolymers whose CTFA (4th Ed. 1991) is octylacrylamide / acrylates / butylaminoethyl-methacrylate copolymer such as the products sold under the name AMPHOMER® ^® or Lovocryl ^® 47 by the company National Starch.

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

CO R ^ - CO Z ^ - (SO

wherein R ₁ represents a divalent group derived from a saturated dicarboxylic acid, an ethylenically double-bonded mono or dicarboxylic aliphatic acid, an ester of a lower alkanol having 1 to 6 carbon atoms of these acids, or a group derived from the addition of any of said acids with a bis-primary or bis-secondary amine, and Z denotes a group derived from a bis-primary, mono- or bis-secondary polyalkylene polyamine, and preferably represents: a) in the proportions of 60 to 100 mol%, the group where x = 2 and p = 2 or 3, or x = 3 and p = 2 this group derived from diethylene triamine, triethylene tetraamine or dipropylene triamine; b) in the proportions of from 0 to 40 mol%, the group (IV) above, in which x = 2 and p = 1 and which is derived from ethylenediamine, or the group derived from piperazine: c) in the proportions of 0 to 20 mol%, the -NH- (CH ₂ ) S-NH- group derived from hexamethylenediamine, these polyaminoamides being crosslinked by addition reaction of a bifunctional crosslinking agent chosen from the epihalohydrins, diepoxides, dianhydrides, bis-unsaturated derivatives, by means of 0.025 to 0.35 mole of crosslinking agent per amino group of the polyaminoamide, and acylated by the action of acrylic acid, chloroacetic acid or a alkane-sultone or their salts.

The saturated carboxylic acids are preferably chosen from acids having 6 to 10 carbon atoms, such as adipic, trimethyl-2,2,4-adipic and trimethyl-2,4,4-adipic acids, terephthalic acids, and double acids. ethylenic bond such as, for example, acrylic, methacrylic, itaconic acids.

The alkane sultones used in the acylation are preferably propane or butane sultone, the salts of the acylating agents are preferably the sodium or potassium salts.

(4) polymers having zwitterionic units of formula:

in which Rn denotes a polymerizable unsaturated group such as an acrylate, methacrylate, acrylamide or methacrylamide group, y and z represent an integer from 1 to 3, Ri ₂ and Ri ₃ represent a hydrogen atom, a methyl or ethyl group; 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 may 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.

By way of example, mention may be made of methyl methacrylate / dimethylcarboxymethylammonioethyl methacrylate copolymers, such as the product sold under the name DIAFORMER Z301 by Sandoz.

(5) The polymers corresponding to the general formula (V) are, for example, described in French Patent 1,400,366 and consist of units:

in which R ₂ o represents a hydrogen atom, a group CH ₃ O, CH ₃ CH ₂ O, phenyl, R ₂ i denotes a hydrogen atom or a lower alkyl group such as methyl, ethyl, R ₂₂ denotes a hydrogen or lower alkyl -C ₆ such as methyl, ethyl, R ₂₃ denotes a lower alkyl dC ₆ such as methyl, ethyl or a group of 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.

(6) The polymers derived from the N-carboxyalkylation of chitosan, such as N-carboxymethylchitosan or N-carboxybutylchitosan, sold under the name "Evalsan" by the company Jan Dekker.

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

-DXDXD- (Vl) where D denotes a group and X denotes the symbol E or E ', E or E', which may be the same or different, denotes a divalent group which is a straight or branched chain alkylene group having up to 7 carbon atoms in the unsubstituted or substituted backbone. hydroxyl groups and may further comprise oxygen, nitrogen, sulfur, 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 groups, alcohol, ester and / or urethane. b) polymers of formula:

-DXDX- (Vl ') where D denotes a group and X denotes the symbol E or E 'and at least once E'; E having the meaning indicated above and E 'is a divalent group which is a straight or branched chain alkylene group having up to 7 carbon atoms in the main chain, substituted or unsubstituted by one or more hydroxyl groups and comprising one or more nitrogen atoms, the nitrogen atom being substituted by an alkyl chain optionally interrupted by an oxygen atom and having obligatorily one or more carboxyl functions or one or more hydroxyl functions and betainized by reaction with the acid; chloroacetic acid or sodium chloroacetate.

(8) alkyl (dC ₅ ) vinyl ether / maleic anhydride copolymers partially modified by semiamidation with an N, N-dialkylaminoalkylamine such as N, N-dimethylaminopropylamine or by semi-esterification with an N, N-dialkylaminoalkanol. These copolymers may also comprise other vinylic comonomers such as vinylcaprolactam.

Among the amphoteric fixing polymers mentioned above that are most particularly preferred according to the invention, mention will be made of those of the family (3) such as the copolymers whose CTFA name is Octylacrylamide / acrylates / butylaminoethylmethacrylate copolymer, such as the products sold. under AM PH OM denominations ER ^®, Amphomer ^® LV 71 or Lovocryl ^® 47 by the company National Starch and those of family (4) such as copolymers of methyl methacrylate / dimethyl méthylammonio-carboxy-ethyl methacrylate sold, for example methyl under the name DIAFORMER Z301 by SANDOZ.

The nonionic fixing polymers that can be used according to the present invention are chosen, for example, from:

polyalkyloxazolines;

homopolymers of vinyl acetate;

vinyl acetate copolymers such as, for example, copolymers of vinyl acetate and acrylic ester, copolymers of vinyl acetate and ethylene, or copolymers of vinyl acetate and of maleic ester, for example, dibutyl maleate;

- homopolymers and copolymers of acrylic esters 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 BASF under the name 8845, by Hoechst under the name APPRETAN ^® 9212;

copolymers of acrylonitrile and of a nonionic monomer chosen, for example, from butadiene and alkyl (meth) acrylates; mention may be made of the products sold under the name CJ 0601 B by the company Rohm &Haas;

homopolymers of styrene;

- copolymers of styrene such as, for example, copolymers of styrene and of alkyl (meth) acrylate such as Mowilith LDM ^® products 691 1 Mowilith ^® DM 61 1 and Mowilith ^® LDM 6070 sold by the company Hoechst, the RHODOPAS ^® SD 215 and RHODOPAS ^® DS 910 products offered by RHONE POULENC; copolymers of styrene, alkyl methacrylate and alkyl acrylate; copolymers of styrene and butadiene; or copolymers of styrene, butadiene and vinylpyridine;

polyamides;

- vinyllactam homopolymers such as vinylpyrrolidone homopolymers, polyvinyl caprolactam sold under the name Luviskol ^® Plus by BASF; and vinyllactam copolymers such as poly (vinylpyrrolidone / vinyllactam) copolymer sold under the trade name Luvitec VPC 55K65W ^® by the company BASF, poly (vinylpyrrolidone / vinyl acetate) such as those sold under the name ^® S630L by PVPVA ISP, Luviskol ^® VA 73, VA 64, VA 55, VA 37 and VA 28 by the company BASF; terpolymers and poly (vinylpyrrolidone / vinyl acetate / vinyl propionate), for example, that marketed under the name Luviskol ^® VAP 343 by BASF.

The alkyl groups of the nonionic polymers mentioned above preferably have from 1 to 6 carbon atoms.

Can also be used as fixing polymers, functionalized or non-functionalized polyurethanes, silicone or non-silicone, cationic, nonionic, anionic or amphoteric, or mixtures thereof.

As polyurethanes are particularly suitable in the present invention include the anionic polyurethane polymer block / polysiloxane products sold under the name Luviset PUR ^® and Luviset ^® Si PUR by BASF.

In a particularly advantageous manner, the compositions according to the invention comprise, as nonionic fixing polymer, a vinyllactam copolymer such as polyvinylpyrrolidones, a poly (vinylpyrrolidone / vinyllactam) copolymer, a poly (vinylpyrrolidone / vinyl acetate) copolymer or a poly (vinylpyrrolidone / vinyl acetate / vinyl propionate) terpolymer.

According to one particular embodiment, the cosmetic composition according to the invention comprises, as fixing polymer, an anionic or nonionic polymer, preferably a nonionic polymer.

The concentration of fixing polymer (s) used in the compositions according to the present invention is between 0.1 and 20%, preferably between 0.5 and 10% by weight relative to the total weight of the composition.

ORGANIC SILICON COMPOUNDS

As an organic silicon compound, there may be mentioned silicones and silanes.

The silicones that can be used in the composition according to the invention can be soluble or insoluble in said composition.

The insoluble silicones are in particular dispersed in the composition in the form of particles generally having a number average size of between 2 nanometers and 100 microns, preferably between 20 nanometers and 20 microns (measured with a particle size analyzer).

Polyorganosiloxanes are further defined in Walter NOLL's "Chemistry and Technology of Silicones" (1968) Academy Press. They can be volatile or nonvolatile.

Thus, the composition according to the invention may comprise at least one volatile polyorganosiloxane chosen from those having a boiling point of between 60 ^° C. and 260 ^° C., and more particularly from:

(i) cyclic silicones having from 4 to 5 silicon atoms. It is, for example, octamethylcyclotetrasiloxane marketed in particular under the name "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, as well as their mixtures.

Mention may also be made of cyclocopolymers of the dimethylsiloxane / methylalkylsiloxane type, such as the "VOLATILE SILICONE FZ 3109" marketed by UNION CARBIDE, of chemical structure: with D: - O - 1 ₇

Mention may also be made of cyclic silicone mixtures with organic compounds derived from silicon, such as the mixture of octamethylcyclotetrasiloxane and tetramethylsilylpentaerythritol (50/50) and the mixture of octamethylcyclotetrasiloxane and oxy-1, 1 '- (hexa -2,2,2 ', 2', 3,3'-trimethylsilyloxy) bis-neopentane;

(ii) linear volatile silicones having 2 to 5 silicon atoms and having a viscosity of less than or equal to 5 × 10 -6 m 2 / s at 25 ^° C. It is, for example, decamethyltetrasiloxane marketed in particular under the name "SH 200 "by the company 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".

Useful siloxanes may also be chosen from organosiloxanes of formula:

in which :

R 1, R ₂ , R ₃ , R 5 and R ₆ are defined as above;

R ' ₄ represents a halogen or an ORn group;

R ₇ represents a halogen, a group ORi ₀ or R "i;

R ₉ represents a halogen, a group OR ₈ , R " ₂ or R ₃ NRiR ₂ ;

R "i, R" _2, R _8, R ₁ 0 and R ₁₁ represents a hydrocarbon group, saturated or unsaturated, linear or branched, optionally bearing additional chemical groups such as basic solubilizing groups;

R ₁₁ , R ₁₀ and R ₈ may further denote hydrogen. Preferably R "i, R" _2, R ₈ or R ₀ and R represents an alkyl group of C _{2 H,} aryl, C _{5 I-4} alkyl group, a _(d-8) -aryl (C _5- - _{I 4} ), and aryl (C _5-14 ) alkyl (C _1-8 ).

At least one of the groups R ₆ , R 7 and R ₉ denotes a halogen or a group OR '', OR ₁₀ or OR ₈ .

Preferably, the halogen is chlorine.

The silicones that are particularly preferred in the invention are polydimethylsiloxanes, such as polydimethylsiloxanes with trimethylsilyl end groups.

As an organic silicon compound, there may be mentioned silanes.

For example, silanes of formula (1)

(R ₁ O) _x (R ₂ Si Si - (A) _p - [NR ₃ - (A ') _p ] _q - [N Ff ₃ - (A ") _p ] _q - Si - (R' ₂ ) _y (OR'i) _x (1) in which

R 1, R ₂ , R ' ₁ and R' ₂ each independently represent a saturated or unsaturated hydrocarbon chain, linear or branched, optionally containing one or more heteroatoms, optionally interrupted or substituted by one or more groups selected from ether, ester, amine, amide, carboxyl, hydroxyl and carbonyl, x is an integer ranging from 1 to 3, y = 3-x, x 'is an integer ranging from 1 to 3, y' = 3-x ', p = 0 or 1 , p '= 0 or 1, p "= 0 or 1, q = 0 or 1, q' = 0 or 1, with the proviso that at least q or q 'is other than zero,

A, A 'and A "each independently represent a linear or branched C ₁ -C ₂₀ divalent alkylene radical,

R ₃ and R ' ₃ each independently represent a hydrogen atom or a saturated or unsaturated hydrocarbon chain, linear or branched optionally containing one or more heteroatoms, optionally interrupted or substituted by one or more ether groups, C ₁ -C ₂₀ alcohol ester; , amino, carboxyl, alkoxysilane, C ₆ -C ₃₀ aryl, hydroxyl or carbonyl, or an aromatic ring, heterocyclic or not, optionally substituted by one or more C ₃ -C ₂₀ alcohol ester, amine or amide groups, carboxyl, alkoxysilane, hydroxyl, carbonyl or acyl, said cosmetic composition further comprising at least one cosmetic agent selected from polymers having a molecular weight of at least 500, surfactants and non-silicone fatty substances.

According to a particular embodiment, the silanes of formula (1) are such that R ₁ Z = RY R ₂ = RV x = X ', y = y', p = p ', A = A', q = 1, and q '= 0.

In particular, there may be mentioned compounds of formula (1) in which R 1, R ₂ , R ' ₁ and R' ₂ , which are identical or different, represent a C ₄ alkyl. According to another embodiment, p = p '= 1 and A and A', which may be identical or different, represent a linear C ₁ -C ₄ alkylene.

It is also possible to mention compounds with R ₃ representing hydrogen.

By way of example, mention may be made of:

bis [3- (triethoxysilyl) propyl] amine, of formula: (CH ₃ CH ₂ O) ₃ - Si - (CH ₂ ) ₃ - NH - (CH ₂ ) ₃ - Si - (OCH ₂ CH ₃ ) ₃ ,

bis [trimethoxysilylpropyl] amine, of formula: (CH ₃ O) ₃ - Si - (CH ₂ ) ₃ - NH - (CH ₂ ) ₃ - Si - (OCH ₃ ) ₃ ,

bis [methyldiethoxysilylpropyl] amine, of formula: (CH ₃ CH ₂ O) ₂ CH ₃ - Si - (CH ₂ ) ₃ - NH - (CH ₂ ) ₃ - Si - CH ₃ (OCH ₂ CH ₃ ) ₂ ,

bis [(3-trimethoxysilyl) propyl] -ethylenediamine, of formula: (CH ₃ O) ₃ - Si - (CH ₂ ) ₃ - NH - (CH ₂ ) ₂ - NH- (CH ₂ ) ₃ - Si - (OCH ₃ ) ₃

Among these compounds, bis [3- (triethoxysilyl) propyl] amine is preferred. nte:

or

R ₂ i and R ₂₂ each independently represent a saturated or unsaturated hydrocarbon chain, linear or branched, optionally containing one or more heteroatoms, optionally interrupted or substituted with one or more groups chosen from ether, ester, amine, amide and carboxyl groups, hydroxyl and carbonyl,

Xi = 2 or 3,

D ₁ = O OR 1,,

A and A 'each independently represent a divalent linear or branched C ₁ -C ₂₀ alkylene radical, R ₂₃ and R ₂₄ each independently represent hydrogen or a saturated or unsaturated hydrocarbon chain, linear or branched optionally containing one or more heteroatoms, optionally interrupted or substituted with one or more ether groups, C ₁ -C ₂₀ alcohol ester, amino, carboxyl, alkoxysilane, C ₆ -C ₃₀ aryl, hydroxyl or carbonyl, or an aromatic ring, heterocyclic or non-heterocyclic, optionally substituted with one or more C ₁ -C ₂₀ alcohol ester groups, amine, amide, carboxyl, alkoxysilane, hydroxyl, carbonyl or acyl, qi is an integer ranging from 0 to 4, The one or more R ₂₅ groups each independently represent hydrogen or a saturated or unsaturated hydrocarbon chain, straight or branched optionally containing one or more heteroatoms, optionally interrupted or substituted by one or more ether, ester alcohol -C _20, amino, carboxyl, alkoxysilane, C ₆ -C ₃₀ aryl, hydroxyl or carbonyl, or an aromatic ring, heterocyclic or non-heterocyclic, optionally substituted with one or more C ₁ -C ₂₀ alcohol ester groups, amine, amide, carboxyl, alkoxysilane, hydroxyl, carbonyl or acyl, said composition further comprising at least one compound selected from hydroxylated solvents, polymers, surfactants and fats. According to one embodiment, R ₂ i is a C ₁ -C ₄ alkyl. According to another embodiment X ₁ = 3. According to a different embodiment

In ₁ = n ' ₁ = 1. q1 and q'1 can be equal to 0.

R ₂₃ and R ₂₄ may independently represent hydrogen or a group selected from alkyl C ₁ -C ₄ hydroxyalkyl, C ₁ -C ₄ aminoalkyl, C ₁ -C _4. By way of example of compounds of formula (2), mention may be made

3- (m-aminophenoxy) propyltrimethoxysilane, of formula:

p-aminophenyltrimethoxysilane, of formula

N- (2-aminoethylaminomethyl) phenethyltrimethoxysilane, of formula

As a silane compound, mention may also be made of organic silicon compounds of formula:

(R ¹ NO) _x (R " ₂ ) _y - Si - (A) _p - CH = O (3)

or formula

(R ¹ NO) _x (R " ₂ ) _y - Si - (A) _p - CH (OR" ₃ ) (OR " ₄ ) (4) where

R "i, identical or different, and R" ₂ each independently represent a saturated or unsaturated hydrocarbon chain, linear or branched, optionally containing one or more heteroatoms, optionally interrupted or substituted with one or more groups selected from ether, ester, amine, amide, carboxyl, hydroxyl and carbonyl, x "= 2 or 3, y" = 3-x ',

A represents a linear or branched alkylene divalent radical -C _20, optionally interrupted or substituted by one or more alcohol ester groups -C ₃₀ amine, carboxyl, alkoxysilane, aryl in C ₆ -C _30, hydroxy or carbonyl, p " = O or 1,

R " ₃ and R" ₄ each independently represent a saturated or unsaturated hydrocarbon chain, linear or branched optionally containing one or more heteroatoms, optionally interrupted or substituted by one or more ether groups, C ₁ -C ₂₀ alcohol ester, amine, carboxyl, alkoxysilane, C ₆ -C ₃₀ aryl, hydroxyl or carbonyl, or an aromatic ring, heterocyclic or non-heterocyclic, optionally substituted by one or more C ₁ -C ₂₀ alcohol ester groups, amine, amide, carboxyl, alkoxysilane, hydroxyl, carbonyl or acyl.

According to a first embodiment, R "1 and R" ₂ are chosen from C ₁ -C ₄ alkyls. According to a second embodiment, p "= 1.

In another embodiment, A is linear C ₁ -C ₄ alkylene.

By way of example of silane compounds of formulas (3) or (4), mention may be made of: triethoxysilylbutyraldehyde, of formula: (CH ₃ CH ₂ O) ₃ - Si - (CH ₂ ) ₃ - CH = O

triethoxysilylundecanal, of formula:

(CH ₃ CH ₂ O) ₃ - Si - (CH ₂ ) ₁₀ - CH = O

triethoxysilylundecanal, ethylene glycol acetal, of formula:

(CH ₃ CH ₂ O) ₃ - Si - (CH ₂ ) ₁₀ - CH (OCH ₂ ) ₂

According to a particularly preferred embodiment, the silane compound is chosen from triethoxysilylbutyraldehyde.

Other useful organosilanes have the formula: f ^" 1 / R '

> N - R ₃ - Si - R _f

R-

in which :

R ₄ represents a halogen, a group OR 'or R'i;

R ₅ represents a halogen, a group OR "or R '₂;

R ₆ represents a halogen, a group OR "'or R' ₃ , and R ₁ , R ₂ , R ₃ , R ', R", R "', R 1, R ₂ , R ' ₃ represent, independently of one another another, a saturated or unsaturated hydrocarbon group, linear or branched, optionally carrying additional chemical groups such as acidic or amino groups, R ₁ , R ₂ , R ', R "and R"' may further denote hydrogen , and at least two of the groups R ₄ , R ₅ and R ₆ being different from the groups R 1, R ' ₂ and

R ' ₃ .

Preferably, R _1, R _2, R ', R "and R"', R ^, R _'2 and R' ₃ represent an alkyl group C ₁ - _{I 2,} aryl, C _5. ₁₄ alkyl group, a (d ^ -aryl _(C5 _14), and aryl _(C5 ₁₄₎ alkyl (C ₁ - _S);.. And R ₃ is preferably an alkylene C _{M 2,} arylene, C ₅ _14, alkyl (C _{_1-8).} -arylene _(C5. ₁₄₎ and aryl (C _{_5-14)} -alkylene _(d-8).

Preferred organic silicon compounds are 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane and 3- [bis (hydroxyethyl) amino] propyltriethoxysilane.

The most preferred compound is 3-aminopropyl triethoxysilane.

The organosilicon compounds presented above are or are preferably present in an amount of between 0.01 and 95% by weight, still more preferably in an amount of between 1 and 60% by weight relative to the weight. of the composition. Optionally, the composition may contain a silicone oil. By way of examples, there may be mentioned in particular polydimethylsiloxanes (PDMS), phenyl polyorganosiloxanes such as phenyltrimethicones, phenyltrimethylsiloxydiphenylsiloxanes, diphenylmethyldimethyltrisiloxanes, diphenyldimethicones, phenyldimethicones and polymethylphenylsiloxanes, which may be fluorinated; polysiloxanes modified with fatty acids, fatty alcohols or polyoxyalkylenes, fluorinated silicones, perfluorinated silicone oils.

Mention may be made, for example, of polydimethylsiloxanes, polymethylphenylsiloxanes, silicones comprising polyoxyalkylene sequences or grafts, in particular polyoxyethylene or copoly (oxyethylene / oxypropylene) such as dimethiconecopolyols, silicones bearing both hydrophobic hydrocarbon groups (for example C ₂ -C ₃₀ alkyl groups) and polyoxyethylenated or copoly (oxyethylenated / oxypropylenated) sequences or grafts such as alkyldimethiconecopolyols, silicones carrying fluorinated or perfluorinated groups such as perfluoroalkylated polydimethylsiloxanes and perfluoroalkylated polymethylphenylsiloxanes, and mixtures thereof.

These silicone oils may optionally comprise alkyl or alkoxy groups at the end of a silicone or pendant chain.

According to one variant, the composition containing the colored polymer contains an organic and / or inorganic salt. As an organic salt, mention may be made of sodium citrate. As inorganic salt, mention may be made of sodium chloride, ammonium sulfate, magnesium chloride or calcium chloride.

The amount of organic or inorganic salts is in general between 10 ^-4 and 2 mol / l, preferably between 10 ³ and 1 mol / l. According to a particularly preferred embodiment, the amount of salts is 10 ^-2 and 1 mol / l.

The composition useful in the process of the present invention may comprise water or a mixture of water and at least one non-oily organic solvent to solubilize compounds that are not sufficiently soluble in water. As organic solvent, there may be mentioned, for example lower alkanols dC ₄ , such as ethanol and isopropanol; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol, and mixtures thereof.

The non-oily solvents are preferably present in proportions preferably of between 0.5 and 80% by weight approximately relative to the total weight of the composition, and still more preferably between 5 and 60% by weight approximately. The colored polymers will preferably be chosen from colored polymers which are soluble or partially soluble in water at room temperature.

The compositions which are useful in the process of the invention may also contain various adjuvants conventionally used in compositions for dyeing hair, such as mineral or organic thickeners, and in particular anionic, cationic, nonionic and amphoteric polymeric associative thickeners. antioxidants, penetrating agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents, ceramides, preservatives, opacifying agents.

The compositions useful in the process of the invention may further contain at least one thickening polymer also called "rheology adjusting agents".

The thickening agents may be chosen from fatty acid amides (diethanol or coconut monoethanol amide, oxyethylenated alkyl ether carboxylic acid monoethanolamide), cellulose thickeners (hydroxyethylcellulose, hydroxypropylcellulose, carboxymethylcellulose), guar gum and its derivatives (hydroxypropylguar), gums of microbial origin (xanthan gum, scleroglucan gum), crosslinked homopolymers of acrylic acid or acrylamidopropanesulfonic acid and associative polymers (water-soluble polymers comprising hydrophilic zones, and hydrophobic zones to fatty chain capable, in an aqueous medium, to associate reversibly with each other or with other molecules.)

The useful compositions may further contain other types of surfactants such as anionic surfactants, nonionic surfactant (s), amphoteric (s) or zwitterionic surfactant (s), cationic surfactants. :

The compositions applied to the keratin fibers may also comprise one or more oxidation dye precursors: one or more oxidation bases and / or one or more couplers. By way of example, the oxidation bases are chosen from para-phenylenediamines, bisphenylalkylenediamines, para-aminophenols, ortho-aminophenols, heterocyclic bases and their addition salts.

The oxidation base (s) present are generally present in an amount ranging from 0.001 to 20% by weight approximately of the total weight of the dyeing composition, preferably ranging from 0.005 to 6%.

The compositions may contain one or more couplers conventionally used for dyeing keratinous fibers. Among these couplers, there may be mentioned meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalenic couplers, heterocyclic couplers and their addition salts.

The coupler or couplers are generally present in an amount ranging from 0.001 to 20% by weight of the total weight of the dyeing composition, preferably ranging from 0.005 to 6%.

In general, the addition salts of the oxidation bases and couplers that can be used in the context of the invention are chosen especially from the addition salts with an acid such as hydrochlorides, hydrobromides, sulphates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates and addition salts with a base such as sodium hydroxide, potassium hydroxide, ammonia, amines or alkanolamines.

The compositions that are useful may also contain one or more additional direct dyes that can be chosen in particular from nitro dyes of the benzene series, neutral, acidic or cationic dyes, acid or cationic neutral azo direct dyes, direct quinone dyes and in particular neutral anthraquinone dyes. acidic or cationic, direct azine dyes, triarylmethane direct dyes, indoamine direct dyes and natural direct dyes.

The direct dye (s) generally represent from 0.001 to 20% by weight approximately of the total weight of the aqueous solution in which they are present, still more preferably from 0.005 to 10% by weight approximately.

The pH of the composition applied to the fibers is in general between 2 and 12, preferably between 3 and 8. It can be adjusted to the desired value by means of acidifying or basifying agents usually used for dyeing keratin fibers or else still using conventional buffer systems.

Among the acidifying agents, mention may be made, by way of example, of mineral or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid, sulphonic acids.

Among the alkalinizing agents that may be mentioned, for example, ammonia, alkaline carbonates, alkanolamines such as mono-, di- and triethanolamines and their derivatives, sodium or potassium hydroxides and following formula (II):

N W - N

RR _H d (ll) in which W is a propylene residue optionally substituted by a hydroxyl group or an alkyl radical in dC ₄ ; R _3, R b, R _c and R _d, identical or different, represent a hydrogen atom, an alkyl radical -C ₄ hydroxyalkyl or Ci-C _4.

When the composition comprises at least one oxidation dye precursor or when it is desired to use a lightening coloring, an oxidizing agent may be used.

The oxidizing agents conventionally used for the oxidation dyeing of keratin fibers are, for example, hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, peracids and oxidase enzymes. among which there may be mentioned peroxidases, 2-electron oxidoreductases such as uricases and 4-electron oxygenases such as laccases. Hydrogen peroxide is particularly preferred.

This oxidizing agent may also be present in one or other of the compositions useful in the invention or applied independently.

The oxidizing composition may also contain various adjuvants conventionally used in compositions for dyeing hair and as defined above.

The composition containing the colored polymer may be in different galenic forms, in particular in the form of emulsions, microemulsions or nanoemulsions, two-phase lotions or in anhydrous form.

According to the method of the invention, the exposure time of each of the compositions is not a limiting factor since it is possible to obtain the coloration of the keratin fibers instantly, which makes it possible to carry out the drying of the fibers at the end of the application of the composition comprising the colored polyelectrolyte. It is however possible to respect a time of installation.

According to a particular embodiment, the method of the invention may comprise one or more pre-treatment steps, for example a pretreatment step for a cationic polymer, this or these pre-treatment steps being able to be followed by a step of rinsing.

The process of the invention may be carried out at a temperature varying between room temperature (20-25 ^° C.) and 200 ^° C., preferably between room temperature and 60 ^° C.

According to a particular embodiment, the method of the invention is implemented on dark hair, naturally or after dyeing, in particular hair having a pitch of less than 6, preferably less than or equal to 4. The heights of tone are commonly used in hair coloring. They are in particular described in "Science of Capillary Treatments" by C. ZVIAK, Ed. Masson 1988, p. 278.

This classification is as follows:

1) Black

2) Brown

3) Dark chestnut

4) Chestnut

5) Light brown

6) Dark blonde

7) Blonde

8) Light blond

9) Very light blonde

10) Clear light blond

The examples which follow serve to illustrate the invention without, however, being limiting in nature.

EXAMPLES

Example 1

A biphasic lotion consisting of 80% water and 20% oleic acid and containing 0.5% poly S-1 19 is applied to a lock of natural hair with 90% white hair. The application is not followed by a rinsing step or a drying step. The orange color obtained is very aesthetic and fades from the first shampoo. Example 2

The lotion of Example 1 containing 0.3% Poly (Disperse Red 13 methacrylate) in place of 0.5% Poly S-1 19 is applied to a lock of hair 90% natural white. The application is immediately followed by a drying step in the dryer. The hair is colored in red aesthetically. This color fades with the first shampoo. Example 3

A solution consisting of 3% of alkyl (C ₈ / C ₀ 50/50) polyglucoside in 60% aqueous solution of water (qspl OO) and containing 0.5% of poly S-1 19 is applied using 'a pump bottle generating foam on a lock of natural hair with 90% white hair. The application is followed by a drying step. The hair is colored in orange. Example 4 A solution consisting of 3% of alkyl (C ₈ / C ₀ 50/50) polyglucoside in 60% aqueous solution of water (qspl OO) and containing 0.5% PAZO is applied using a pump bottle. foam generator on a strand of natural hair with 90% white hair. The application is followed by a drying step. The hair is colored yellow. Example 5

A solution consisting of hydroxyethylcellulose (2.5%), FIXATE G 100 (4.2%) and containing 0.5% of poly S-1 19 and 3-amino-2-methyl-1-propanol in an amount such that the solution has a pH 7 is applied on a lock of natural gray hair with 90% white hair. The application is followed by a drying step. The orange color obtained is very aesthetic. Example 6

An aerosol is prepared from a composition comprising 33% DME, 20% ethanol, 0.5% poly S-1, 19.5% LUVISET Si PUR, 3-amino-2-methyl-1-propanol in an amount such that the pH of the composition is equal to 7, and water (qs 100%). The composition is then applied to a lock of natural gray hair with 90% white hair by means of an aerosol. A very aesthetic orange color is obtained upon application. Example 7

A lock of discolored hair (high alkaline solubility) is pretreated with an aqueous solution of 3-aminopropyl triethylsilane at 10% and at pH 8. After rinsing, a hydroalcoholic lotion (50/50) containing 0.5% PAZO is applied. The hair is colored yellow. This color fades with the first shampoo.

Claims

A method of dyeing hair comprising applying a composition containing at least one anionic color polymer which comprises an anionic chromophore and at least one cosmetic active agent selected from a non-silicone oil, an alkylpolyglucoside surfactant, a non-silicone fixing polymer, associative nonionic, amphoteric, cationic or anionic carboxylic, an organic silicon compound comprising less than 6 silicon atoms, this application is not followed by a fiber rinsing step.

2. The method of claim 2 wherein the chromophore is substituted by at least one sulfonate group, carboxylate, phosphate, phosphonate, sulfate.

3. Method according to any one of the preceding claims wherein the colored polymer is present in the composition in an amount of between 0.01 to 20%, preferably between 0.1 to 5%.

4. Process according to any one of the preceding claims, in which the colored polymer or polymers are chosen from:

5. Method according to any one of the preceding claims wherein the non-silicone oil is selected from vegetable oils, mineral oils, synthetic oils, fatty acid esters and liquid fatty acids.

6. The method of claim 5 wherein the oil is selected from liquid fatty acids, liquid fatty esters and vegetable oils.

7. Method according to any one of the preceding claims wherein the amount of oil contained in the composition is between 0.01 and 95% by weight and preferably between 1 and 60%.

8. Process according to any one of claims 1 to 7 wherein the alkylpolyglucoside surfactant is represented by the following general formula:

R ₁ O- (R ₂ O), (G) _v in which R, represents an alkyl radical and / or linear or branched alkenyl containing from about 8 to 24 carbon atoms, an alkylphenyl radical whose linear or branched alkyl radical comprises from 8 to 24 carbon atoms, R ₂ represents an alkylene radical having about 2 to 4 carbon atoms, G represents a sugar unit comprising from 5 to 6 carbon atoms, t denotes a value ranging from 0 to 10, preferably 0 to 4, preferably 0 to 4 and v denotes a value ranging from 1 to 15.

9. The process as claimed in claim 8, in which the alkylpolyglucoside surfactants are such that R 1 denotes a linear or branched, saturated or unsaturated alkyl radical containing from 8 to 18 carbon atoms, t denotes a value ranging from 0 to 3, and G may denote glucose, fructose or galactose, v varies from 1 to 15.

The method of claim 9 wherein the alkylpolyglucoside surfactants are such that t is 0 and G is glucose.

11. Method according to any one of the preceding claims wherein the amount of alkylpolyglucoside surfactants is between 0.1 and 90% and preferably between 0.5 and 10% by weight relative to the total weight of the composition.

12. Process according to any one of the preceding claims, in which the fixing polymer is chosen from anionic and nonionic polymers.

13. The method of claim 12 wherein the fixing polymer is anionic.

14. Process according to any one of the preceding claims, in which the fixing polymer is chosen from monoesterified methyl vinyl ether / maleic anhydride copolymers, acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers, vinyl acetate terpolymers / tert-butyl benzoate terpolymers. vinyl / crotonic acid and crotonic acid / vinyl acetate / neododecanoate terpolymers, methacrylic acid and ethyl acrylate copolymers, vinylpyrrolidone / acrylic acid / lauryl methacrylate terpolymers, anionic acid copolymers (meth) acrylic, alkyl esters of (meth) acrylic acid and allyl methacrylate, homopolymers of vinylpyrrolidine, polyurethanes of the polyurethane / polysiloxane block anionic polymer type.

15. The method of claim 14 wherein the amount of fixing polymer contained in the composition is between 0.01 and 20% by weight and preferably between 0.5 and 10%.

16. Process according to any one of the preceding claims, in which the organic silicon compound is chosen from silicones and silanes.

17. The method of claim 16 wherein the silane compound is selected from 3-amino propyltriethoxysilane, 3-aminopropylmethyldiethoxysilane and 3- [bis (hydroxyethyl) amino] propyltriethoxysilane.

18. The method of claim 8 wherein the silane compound is 3-aminopropyl triethoxysilane.

19. Process according to any one of the preceding claims, in which the organic silicon compound is present in an amount of between 0.01 and 95% by weight and preferably between 1 and 60%.

20. Process according to any one of the preceding claims wherein the composition contains one or more organic and / or inorganic salts.

21. The method of claim 20 wherein the organic and / or inorganic salts are selected from sodium citrate, sodium chloride, ammonium sulfate, magnesium chloride or calcium chloride.

22. A method according to any one of claims 20 or 21 wherein the amount of salts is between 10 ^{~ 4} and 2 mol / l, preferably between 10 ^{~ 3} and 1 mol / l.

23. A method according to any one of claims 1 to 22 for dyeing hair having a pitch of less than or equal to 4.