WO2014020167A2

WO2014020167A2 - Dye composition comprising at least one sulfonic compound and a thickening polymer, dyeing process and suitable device

Info

Publication number: WO2014020167A2
Application number: PCT/EP2013/066321
Authority: WO
Inventors: Delphine Charrier; Géraldine Fack
Original assignee: L'oreal
Priority date: 2012-08-02
Filing date: 2013-08-02
Publication date: 2014-02-06
Also published as: FR2994088B1; WO2014020167A3; FR2994088A1

Abstract

The present invention relates to a composition for dyeinghuman keratin fibres such as the hair, comprising: (a) at least one oxidation dye precursor; (b) at least one aminoalkane sulfonic, sulfonothioic or sulfinic acid, and salts or amide derivatives or functional analogues thereof; (c) at least 0.1% by weight, relative to the weight of the composition, of at least one thickening polymerchosen from nonionic, cationic and amphoteric polymers. The invention also relates to a process for dyeing human keratin fibres in which this composition is applied to the said fibres, in the presence of at least one oxidizing agent other than atmospheric oxygen, and also to a multi-compartment device that is suitable for performing this process.

Description

DYE COMPOSITION COMPRISING AT LEAST ONE SULFONIC COMPOUND AND A THICKENING POLYMER, DYEING PROCESS AND SUITABLE DEVICE

The present invention relates to a dye composition comprising at least one oxidation dye precursor, at least one particular sulfonic compound, and at least 0.1 % by weight of at least one non ionic, cationic or amphoteric thickening polymer, and also to a dyeing process using the said composition in the presence of an oxidizing agent other than atmospheric oxygen. The present invention also relates to a suitable multi-compartment device.

Among the methods for dyeing human keratin fibres, such as the hair, mention may be made of oxidation dyeing or permanent dyeing. More particularly, this form of dyeing uses one or more oxidation dyes, usually one or more oxidation bases optionally combined with one or more couplers.

In general, the oxidation bases are chosen from ortho- or para- phenylenediamines, ortho- or para-aminophenols and heterocyclic compounds. These oxidation bases are colourless or weakly coloured compounds which, when combined with oxidizing products, can give access to coloured entities.

The shades obtained with these oxidation bases are often varied by combining them with one or more couplers, these couplers being chosen especially from aromatic meta-diamines, meta-aminophenols, meta-diphenols and certain heterocyclic compounds, such as indole compounds.

The variety of the molecules used as oxidation bases and couplers allows a rich range of colours to be obtained.

Permanent dyeing processes thus consist in using, with the dye composition containing the oxidation dyes, an aqueous composition comprising at least one oxidizing agent such as hydrogen peroxide, under alkaline pH conditions in the vast majority of cases. The alkaline agent conventionally used is aqueous ammonia or it may be chosen from other alkaline agents, such as alkanolamines.

It has been recommended to use aminocarboxylic acids in oxidation dyeing, in particular as pH agents. These formulations afford numerous advantages, especially inasmuch as they make it possible to reduce the content of ammonia or of alkanolamines, thus affording a very marked improvement in the user's comfort (less of an unpleasant odour and less risk of stinging). Patent application US 2009/0 089 940 discloses oxidation dye compositions containing sulfonic compounds such as taurine.

However, these compositions are not entirely satisfactory especially in terms of the working qualities and particularly in terms of the ease of application and ease of rinsing after the leave-on time. Moreover, the dyeing properties, especially in terms of power and selectivity, are still not optimal.

There is thus a need for more efficient compositions.

This objective and others are achieved by the present invention, the subject of which is thus a composition for dyeing human keratin fibres, such as the hair, comprising:

(a) at least one oxidation dye precursor;

(b) at least one aminoalkane sulfonic, sulfonothioic or sulfinic acid, and salts or amide derivatives or functional analogues thereof;

(c) at least 0.1 % by weight, relative to the weight of the composition, of at least one thickening polymer chosen from nonionic, cationic and amphoteric polymers, and mixtures thereof.

A subject of the invention is also a dyeing process in which such a composition is used, in the presence of an oxidizing agent other than atmospheric oxygen.

Finally, the invention relates to a multi-compartment device comprising a compartment containing a composition free of oxidizing agent other than atmospheric oxygen, comprising at least one oxidation dye precursor, at least one aminoalkane sulfonic, sulfonothioic or sulfinic acid, and also salts or amide derivatives or functional analogues thereof; at least 0.1 % by weight of at least one thickening polymer chosen from nonionic, cationic and amphoteric polymers, and mixtures thereof ; and a compartment containing an oxidizing composition.

The composition of the invention makes it possible to obtain good dyeing properties, such as strength of the colour, resistance to external agents (shampoo, perspiration, light) and homogeneity, which are particularly efficient.

It also has a texture suitable for the application. Indeed, the composition according to the invention is easy to apply to the fibres. Similarly, it rinses off easily after the leave-on time.

Other characteristics and advantages of the invention will emerge more clearly on reading the description and the examples that follow.

In the text hereinbelow, and unless otherwise indicated, the limits of a range of values are included in that range.

The term "at least one" associated with an ingredient of the composition signifies "one or more". The human keratin fibres treated by means of the process according to the invention are preferably the hair.

Oxidation dye precursors

As indicated previously, the dyeing composition according to the invention comprises at least one oxidation dye precursor.

As oxidation dye precursors, use may be made of oxidation bases and couplers.

By way of example, the oxidation bases are chosen from para- phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, ortho- aminophenols and heterocyclic bases, and the addition salts thereof.

Among the para-phenylenediamines that may be mentioned, for example, are para-phenylenediamine, para-tolylenediamine, 2-chloro-para-phenylenediamine, 2,3- dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl- para-phenylenediamine, 2,5-dimethyl-para-phenylenediamine, N,N-dimethyl-para- phenylenediamine, Ν,Ν-diethyl-para-phenylenediamine, N,N-dipropyl-para- phenylenediamine, 4-amino-N,N-diethyl-3-methylaniline, N,N-bis( -hydroxyethyl)- para-phenylenediamine, 4-N,N-bis( -hydroxyethyl)amino-2-methylaniline, 4-N,N- bis( -hydroxyethyl)amino-2-chloroaniline, 2- -hydroxyethyl-para-phenylenediamine, 2-fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine, Ν-(β- hydroxypropyl)-para-phenylenediamine, 2-hydroxymethyl-para-phenylenediamine, N,N-dimethyl-3-methyl-para-phenylenediamine, N-ethyl-N-( -hydroxyethyl)-para- phenylenediamine, N-( ,y-dihydroxypropyl)-para-phenylenediamine, N-(4'- aminophenyl)-para-phenylenediamine, N-phenyl-para-phenylenediamine, 2-β- hydroxyethyloxy-para-phenylenediamine, 2- -acetylaminoethyloxy-para- phenylenediamine, N-( -methoxyethyl)-para-phenylenediamine, 4- aminophenylpyrrolidine, 2-thienyl-para-phenylenediamine, 2-p-hydroxyethylamino-5- aminotoluene and 3-hydroxy-1 -(4'-aminophenyl)pyrrolidine, and the addition salts thereof with an acid.

Among the para-phenylenediamines mentioned above, para-phenylenediamine, para-tolylenediamine, 2-isopropyl-para-phenylenediamine, 2- -hydroxyethyl-para- phenylenediamine, 2- -hydroxyethyloxy-para-phenylenediamine, 2,6-dimethyl-para- phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,3-dimethyl-para- phenylenediamine, N,N-bis( -hydroxyethyl)-para-phenylenediamine, 2-chloro-para- phenylenediamine and 2- -acetylaminoethyloxy-para-phenylenediamine, and the addition salts thereof with an acid, are particularly preferred.

Mention may be made, among bis(phenyl)alkylenediamines, by way of example, of N,N'-bis( -hydroxyethyl)-N,N'-bis(4'-aminophenyl)-1 ,3-diaminopropanol, N,N'-bis( -hydroxyethyl)-N,N'-bis(4'-aminophenyl)ethylenediamine, N,N'-bis(4- aminophenyl)tetramethylenediamine, N,N'-bis(P-hydroxyethyl)-N,N'-bis(4- aminophenyl)tetramethylenediamine, N,N'-bis(4- methylaminophenyl)tetramethylenediamine, N,N'-bis(ethyl)-N,N'-bis(4'-amino-3'- methylphenyl)ethylenediamine, 1 ,8-bis(2,5-diaminophenoxy)-3,6-dioxaoctane and the addition salts thereof.

Among the para-aminophenols that may be mentioned, for example, are para- aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 4-amino-3- chlorophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2-methylphenol, 4-amino-2- hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2- aminomethylphenol, 4-amino-2-( -hydroxyethylaminomethyl)phenol and 4-amino-2- fluorophenol, and the addition salts thereof with an acid.

Among the ortho-aminophenols that may be mentioned, for example, are 2- aminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol and 5-acetamido-2- aminophenol, and the addition salts thereof.

Among the heterocyclic bases, mention may be made, by way of example, of pyridine derivatives, pyrimidine derivatives and pyrazole derivatives.

Among the pyridine derivatives that may be mentioned are the compounds described, for example, in patents GB 1 026 978 and GB 1 153 196, for instance 2,5- diaminopyridine, 2-(4-methoxyphenyl)amino-3-aminopyridine and 3,4- diaminopyridine, and the addition salts thereof.

Other pyridine oxidation bases of use in the present invention are the 3- aminopyrazolo[1 ,5-a]pyridine oxidation bases or addition salts thereof described, for example, in patent application FR 2 801 308. Mention may be made, by way of example, of pyrazolo[1 ,5-a]pyrid-3-ylamine, 2-(acetylamino)pyrazolo[1 ,5-a]pyrid-3- ylamine, 2-(morpholin-4-yl)pyrazolo[1 ,5-a]pyrid-3-ylamine, 3-aminopyrazolo[1 ,5- a]pyridine-2-carboxylic acid, 2-methoxypyrazolo[1 ,5-a]pyrid-3-ylamine, (3- aminopyrazolo[1 ,5-a]pyrid-7-yl)methanol, 2-(3-aminopyrazolo[1 ,5-a]pyrid-5-yl)ethanol, 2-(3-aminopyrazolo[1 ,5-a]pyrid-7-yl)ethanol, (3-aminopyrazolo[1 ,5-a]pyrid-2- yl)methanol, 3,6-diaminopyrazolo[1 ,5-a]pyridine, 3,4-diaminopyrazolo[1 ,5-a]pyridine, pyrazolo[1 ,5-a]pyridine-3,7-diamine, 7-(morpholin-4-yl)pyrazolo[1 ,5-a]pyrid-3-ylamine, pyrazolo[1 ,5-a]pyridine-3,5-diamine, 5-(morpholin-4-yl)pyrazolo[1 ,5-a]pyrid-3-ylamine,

2- [(3-aminopyrazolo[1 ,5-a]pyrid-5-yl)(2-hydroxyethyl)amino]ethanol, 2-[(3- aminopyrazolo[1 ,5-a]pyrid-7-yl)(2-hydroxyethyl)amino]ethanol, 3-aminopyrazolo[1 ,5- a]pyridin-5-ol, 3-aminopyrazolo[1 ,5-a]pyridin-4-ol, 3-aminopyrazolo[1 ,5-a]pyridin-6-ol,

3- aminopyrazolo[1 ,5-a]pyridin-7-ol, and the addition salts thereof.

Among the pyrimidine derivatives that may be mentioned are the compounds described, for example, in patents DE 2359399, JP 88-169571 , JP 05-63124 and EP 0 770 375 or patent application WO 96/15765, such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4- dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine and addition salts thereof, and tautomeric forms thereof, when a tautomeric equilibrium exists.

Among the pyrazole derivatives that may be mentioned, for example, are the compounds described in the patents DE 3843892, DE 4133957 and patent applications WO 94/08969, WO 94/08970, FR-A-2 733 749 and DE 195 43 988, such as 4,5-diamino-1 -methylpyrazole, 4,5-diamino-1-( -hydroxyethyl)pyrazole, 3,4- diaminopyrazole, 4,5-diamino-1 -(4'-chlorobenzyl)pyrazole, 4,5-diamino-1 ,3- dimethylpyrazole, 4,5-diamino-3-methyl-1 -phenylpyrazole, 4,5-diamino-1 -methyl-3- phenylpyrazole, 4-amino-1 ,3-dimethyl-5-hydrazinopyrazole, 1 -benzyl-4,5-diamino-3- methylpyrazole, 4,5-diamino-3-ie f-butyl-1 -methylpyrazole, 4,5-diamino-1 -ie f-butyl-3- methylpyrazole, 4,5-diamino-1 -(P-hydroxyethyl)-3-methylpyrazole, 4,5-diamino-1 - ethyl-3-methylpyrazole, 4,5-diamino-1 -ethyl-3-(4'-methoxyphenyl)pyrazole, 4,5- diamino-1 -ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-1 - methylpyrazole, 4,5-diamino-3-hydroxymethyl-1 -isopropylpyrazole, 4,5-diamino-3- methyl-1 -isopropylpyrazole, 4-amino-5-(2'-aminoethyl)amino-1 ,3-dimethylpyrazole, 3,4,5-triaminopyrazole, 1 -methyl-3,4,5-triaminopyrazole, 3,5-diamino-1 -methyl-4- methylaminopyrazole, 3,5-diamino-4-( -hydroxyethyl)amino-1 -methylpyrazole, and the addition salts thereof. Use may also be made of 4,5-diamino-1-(P- methoxyethyl)pyrazole.

Use will preferably be made of a 4,5-diaminopyrazole and even more preferentially of 4,5-diamino-1-( -hydroxyethyl)pyrazole and/or a salt thereof.

Pyrazole derivatives that may also be mentioned include diamino-N,N- dihydropyrazolopyrazolones and especially those described in patent application FR- A-2 886 136, such as the following compounds and the addition salts thereof: 2,3- diamino-6,7-dihydro-1 H,5H-pyrazolo[1 ,2-a]pyrazol-1 -one, 2-amino-3-ethylamino-6,7- dihydro-1 H,5H-pyrazolo[1 ,2-a]pyrazol-1 -one, 2-amino-3-isopropylamino-6,7-dihydro-

1 H,5H-pyrazolo[1 ,2-a]pyrazol-1 -one, 2-amino-3-(pyrrolidin-1 -yl)-6,7-dihydro-1 H,5H- pyrazolo[1 ,2-a]pyrazol-1 -one, 4,5-diamino-1 ,2-dimethyl-1 ,2-dihydropyrazol-3-one,

4,5-diamino-1 ,2-diethyl-1 ,2-dihydropyrazol-3-one, 4,5-diamino-1 ,2-di(2-hydroxyethyl)- 1 ,2-dihydropyrazol-3-one, 2-amino-3-(2-hydroxyethyl)amino-6,7-dihydro-1 H,5H- pyrazolo[1 ,2-a]pyrazol-1 -one, 2-amino-3-dimethylamino-6,7-dihydro-1 H,5H- pyrazolo[1 ,2-a]pyrazol-1 -one, 2,3-diamino-5,6,7,8-tetrahydro-1 H,6H-pyridazino[1 ,2- a]pyrazol-1 -one, 4-amino-1 ,2-diethyl-5-(pyrrolidin-1 -yl)-1 ,2-dihydropyrazol-3-one, 4- amino-5-(3-dimethylaminopyrrolidin-1 -yl)-1 ,2-diethyl-1 ,2-dihydropyrazol-3-one or 2,3- diamino-6-hydroxy-6,7-dihydro-1 H,5H-pyrazolo[1 ,2-a]pyrazol-1 -one. Use is preferably made of 2,3-diamino-6,7-dihydro-1 H,5H-pyrazolo[1 ,2-a]pyrazol-1 -one and/or a salt thereof.

Use will preferably be made, as heterocyclic bases, of 4,5-diamino-1-(P- hydroxyethyl)pyrazole and/or 2,3-diamino-6,7-dihydro-1 H,5H-pyrazolo[1 ,2-a]pyrazol- 1 -one and/or a salt thereof.

Among the couplers that may be used in the composition according to the invention, mention may be made in particular of meta-phenylenediamines, meta- aminophenols, meta-diphenols, naphthalene-based couplers, heterocyclic couplers, for instance indole derivatives, indoline derivatives, sesamol and derivatives thereof, pyridine derivatives, pyrazolotriazole derivatives, pyrazolones, indazoles, benzimidazoles, benzothiazoles, benzoxazoles, 1 ,3-benzodioxoles, quinolines, and the addition salts of these compounds with an acid.

These couplers are more particularly chosen from 2,4-diamino-1-(P- hydroxyethyloxy)benzene, 2-methyl-5-aminophenol, 5-N-( -hydroxyethyl)amino-2- methylphenol, 3-aminophenol, 1 ,3-dihydroxybenzene, 1 ,3-dihydroxy-2- methylbenzene, 4-chloro-1 ,3-dihydroxybenzene, 2-amino-4-( -hydroxyethylamino)-1 - methoxybenzene, 1 ,3-diaminobenzene, 1 ,3-bis(2,4-diaminophenoxy)propane, sesamol, 1 -amino-2-methoxy-4,5-methylenedioxybenzene, oc-naphthol, 6- hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole, 6-hydroxyindoline, 2,6- dihydroxy-4-methylpyridine, 1 H-3-methylpyrazol-5-one, 1 -phenyl-3-methylpyrazol-5- one, 2-amino-3-hydroxypyridine, 3,6-dimethylpyrazolo[3,2-c]-1 ,2,4-triazole and 2,6- dimethylpyrazolo[1 ,5-b]-1 ,2,4-triazole, the addition salts thereof with an acid, and mixtures thereof.

The addition salts of the oxidation bases and couplers are in particular chosen from the addition salts with an acid, such as the hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates.

The oxidation base(s) are generally each present in an amount from 0.0001 % to 10% by weight relative to the total weight of the composition of the invention, and preferably from 0.005% to 5% by weight relative to the total weight of the composition.

The coupler(s) each generally represent from 0.0001 % to 10% by weight relative to the total weight of the composition and preferably from 0.005% to 5% by weight relative to the total weight of the composition of the invention.

The composition used in the process according to the invention may optionally comprise synthetic or natural, cationic or nonionic, direct dyes. Examples of particularly suitable direct dyes that may be mentioned include nitrobenzene dyes; azo direct dyes; azomethine direct dyes; methine direct dyes; azacarbocyanin direct dyes, for instance tetraazacarbocyanins (tetraazapentamethines); quinone and in particular anthraquinone, naphthoquinone or benzoquinone direct dyes; azine direct dyes; xanthene direct dyes; triarylmethane direct dyes; indoamine direct dyes; indigoid direct dyes; phthalocyanine direct dyes, porphyrin direct dyes and natural direct dyes, alone or as mixtures. In particular, mention may be made of direct dyes from among: azo; methine; carbonyl; azine; nitro (hetero)aryl; tri(hetero)arylmethane; porphyrin; phthalocyanine and natural direct dyes, alone or as mixtures.

When they are present, the direct dye(s) more particularly represent from 0.0001 % to 10% by weight of the total weight of the dye composition and preferably from 0.005% to 5% by weight.

Sulfonic, sulfonothioic or sulfinic compounds

The composition according to the invention comprises at least one aminoalkane sulfonic, sulfonothioic or sulfinic acid, and salts or amide derivatives or functional analogues thereof.

Preferably, such compounds are chosen from the compounds corresponding to formula (A) or (B) below:

in which:

R denotes hydrogen or a linear Ci-C₄ alkyl radical;

Y denotes S or O;

X denotes hydrogen, a cation M^p+ of valency p, or an organic amine;

Z denotes hydrogen, a cation M^p+ of valency p, or an organic amine;

n is an integer greater than or equal to 2;

p is an integer greater than or equal to 1 .

Preferentially:

R denotes hydrogen or a linear d-C₄ alkyl radical and more preferentially methyl; p is 1 or 2;

n is 2 or 3;

X denotes hydrogen or a cation M^p+ chosen from alkali metals (K⁺, Na⁺), alkaline- earth metals (Mg ²⁺, Ca ²⁺) and the ammonium ion; Z denotes hydrogen or a cation M^p+ chosen from alkali metals (K⁺, Na⁺), alkaline-earth metals (Mg ²⁺, Ca ²⁺) and the ammonium ion.

Among the compounds of formula (A), mention may be made more particularly, alone or as mixtures, of:

- taurine or 2-aminoethanesulfonic acid;

- thiotaurine or 2-aminoethanesulfonothioic acid;

- homotaurine or 2-aminopropanesulfonic acid;

salts thereof such as:

- potassium taurate, in particular potassium taurate as a mixture with lauric acid (I NCI name: Potassium Taurate Laurate) such as the commercial product L-TK sold by the company NOF Corporation;

- sodium taurate, in particular as a mixture with lauric acid, such as the commercial product L-T2 sold by the company NOF Corporation. Among the compounds of formula (B), mention may be made more particularly of hypotaurine or 2-aminoethanesulfinic acid, and salts thereof.

The aminoalkane sulfonic, sulfonothioic or sulfinic acid compounds, and also the salts thereof or amide derivatives thereof may also be chosen from functional analogues of taurine such as those described in the article Taurine analogues, a new class of therapeutics: retrospect and prospects, Gupta R.C., Win T., Bittner S. Curr.

Med. Chem.

Taurine, homotaurine or hypotaurine or salts thereof will be chosen more particularly, and even more particularly taurine and salts thereof.

Preferentially, the aminoalkane sulfonic, sulfonothioic or sulfinic acid compound(s), and the salts thereof, amide derivatives thereof or functional analogues thereof in accordance with the invention are present in the composition in concentrations ranging from 0.001 % to 20% by weight, preferably from 0.005% to 10% by weight, more particularly from 0.01 % to 5% by weight and advantageously from 0.1 % to 3% by weight relative to the total weight of the composition.

Thickening polymer

The composition also comprises at least one thickening polymer chosen form nonionic, cationic and amphoteric polymers, and mixtures thereof, and preferably a thickening polymer chosen from non-ionic and cationic polymers, and mixtures thereof.

This thickening polymer is chosen from nonionic, cationic and amphoteric non- associative polymers, or from non ionic, cationic and amphoteric associative polymers, and also mixtures thereof. For the purpose of the present invention, the term "thickening polymer" means a polymer which, when introduced at 1 % in a pure aqueous solution or an aqueous- alcoholic solution containing 30% ethanol, and at pH 7, makes it possible to achieve a viscosity of at least 100 cps and preferably of at least 500 cps, at 25°C and at a shear rate of 1 s^' This viscosity may be measured using a cone/plate viscometer (Haake R600 rheometer or the like).

Preferably, these polymers increase, by virtue of their presence, the viscosity of the compositions into which they are introduced by at least 50 cps and preferably 200 cps, at 25°C and a shear rate of 1 s^"1.

Non-associative polymers

As regards the non-associative thickening polymers, it is first recalled that, for the purposes of the present invention, non-associative thickening polymers are thickening polymers not containing any C₈-C₃₀ fatty chains.

Among these non-associative thickening polymers, mention may be made of: a) nonionic guar gums,

b) biopolysaccharide gums of microbial origin, gums derived from plant exudates, c) celluloses, in particular hydroxypropyl- or carboxymethylcelluloses,

d) pectins and alginates,

mixtures thereof.

Non-associative thickening polymers that may be mentioned include nonionic guar gums, for instance the unmodified nonionic guar gums sold under the name Vidogum GH 175 by the company Unipectine and under the name Jaguar C by the company Meyhall.

The nonionic guar gums that may be used according to the invention are preferably modified with Ci-C₆ hydroxyalkyl groups. Among the hydroxyalkyl groups that may be mentioned, for example, are hydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxybutyl groups.

These guar gums are well known in the prior art and may be prepared, for example, by reacting the corresponding alkene oxides, for instance propylene oxides, with the guar gum so as to obtain a guar gum modified with hydroxypropyl groups.

The degree of hydroxyalkylation, which corresponds to the number of alkylene oxide molecules consumed by the number of free hydroxyl functions present on the guar gum, preferably ranges from 0.4 to 1 .2.

Such nonionic guar gums optionally modified with hydroxyalkyl groups are sold, for example, 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. Suitable non-associative thickening polymers that may also be mentioned include biopolysaccharide gums of microbial origin such as scleroglucan gum or xanthan gum.

Gums that are also suitable for use are those derived from plant exudates, such as gum arabic, ghatti gum, karaya gum and gum tragacanth; celluloses, in particular hydroxypropyl- or carboxymethyl- celluloses; pectins and alginates.

These polymers are well known to those skilled in the art and are especially described in the book by Robert L. Davidson entitled Handbook of water-soluble gums and resins published by the McGraw-Hill Book Company (1980).

Associative polymers

It is recalled that associative polymers are hydrophilic polymers that are capable, in an aqueous medium, of reversibly associating with each other or with other molecules.

Their chemical structure more particularly comprises at least one hydrophilic region and at least one hydrophobic region.

The term "hydrophobic group" means a radical or polymer with a saturated or unsaturated, linear or branched hydrocarbon-based chain, comprising at least 8 carbon atoms, preferably from 10 to 30 carbon atoms, in particular from 12 to 30 carbon atoms and more preferentially from 18 to 30 carbon atoms.

Preferentially, the hydrocarbon-based group is derived from a monofunctional compound. By way of example, the hydrophobic group may be derived from a fatty alcohol such as stearyl alcohol, dodecyl alcohol or decyl alcohol. It may also denote a hydrocarbon-based polymer, for instance polybutadiene.

Among the associative polymers that are suitable for use in the invention, mention may be made of:

a) associative celluloses modified with groups comprising at least one fatty chain, such as alkyl, arylalkyl or alkylaryl groups comprising from 8 to 30 carbon atoms. b) quaternized hydroxyethylcelluloses modified with groups comprising at least one fatty chain, such as alkyl, arylalkyl or alkylaryl groups comprising from 8 to 30 carbon atoms.

The alkyl radicals borne by the above quaternized celluloses or hydroxyethylcelluloses preferably comprise from 8 to 30 carbon atoms. The aryl radicals preferably denote phenyl, benzyl, naphthyl or anthryl groups.

Examples of quaternized alkylhydroxyethylcelluloses containing C₈-C₃₀ fatty chains that may be mentioned include the products Quatrisoft LM 200®, Quatrisoft LM-X 529-18-A®, Quatrisoft LM-X 529-18B® (C_i2 alkyl) and Quatrisoft LM-X 529-8® (Ci8 alkyl) sold by the company Amerchol, and the products Crodacel QM®, Crodacel QL® (Ci2 alkyl) and Crodacel QS® (Ci₈ alkyl) sold by the company Croda. c) the cationic polymer(s) obtained by polymerization of a monomer mixture comprising one or more vinyl monomers substituted with one or more amino groups, one or more hydrophobic nonionic vinyl monomers, and one or more associative vinyl monomers.

In particular, among these cationic polymers, mention may be made especially of the compound sold by the company Noveon under the name Aqua CC and which corresponds to the I NCI name Polyacrylate-1 Crosspolymer.

Polyacrylate-1 Crosspolymer is the product of polymerization of a monomer mixture comprising:

- a di(CrC₄ alkyl)amino(Ci-C₆ alkyl) methacrylate,

- one or more C1-C30 alkyl esters of (meth)acrylic acid,

- a polyethoxylated Ci₀-C₃₀ alkyl methacrylate (20-25 mol of ethylene oxide units),

- a 30/5 polyethylene glycol/polypropylene glycol allyl ether,

- a hydroxy(C₂-C₆ alkyl) methacrylate, and

- an ethylene glycol dimethacrylate.

i) amphoteric associative polymers prepared by copolymerizing:

1 ) at least one monomer of formula (la) or (lla) below:

in which R-i and R₂, which may be identical or different, represent a hydrogen atom or a methyl radical, R₃, R₄ and R₅, which may be identical or different, represent a linear or branched alkyl radical containing from 1 to 30 carbon atoms,

Z represents an NH group or an oxygen atom,

n is an integer from 2 to 5,

A^" is an anion derived from an organic or mineral acid, such as a methosulfate anion or a halide such as chloride or bromide;

2) at least one monomer of formula (Ilia):

in which R₆ and R₇, which may be identical or different, represent a hydrogen atom or a methyl radical;

and 3) at least one monomer of formula (IVa):

R₆ _ ^COXR₈

R₇

in which R₆ and R₇, which may be identical or different, represent a hydrogen atom or a methyl radical, X denotes an oxygen or nitrogen atom and R₈ denotes a linear or branched alkyl radical containing from 1 to 30 carbon atoms;

at least one of the monomers of formula (la), (I la) or (Ilia) comprising at least one fatty chain containing 8 to 30 carbon atoms.

The monomers of formulae (la) and (I la) of the present invention are preferably chosen from the group consisting of:

- dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate,

- diethylaminoethyl methacrylate, diethylaminoethyl acrylate,

- dimethylaminopropyl methacrylate, dimethylaminopropyl acrylate,

- dimethylaminopropylmethacrylamide, dimethylaminopropylacrylamide, these monomers optionally being quaternized, for example with a Ci-C₄ alkyl halide or a C C₄ dialkyl sulfate.

More particularly, the monomer of formula (la) is chosen from acrylamidopropyltrimethylammonium chloride and methacrylamidopropyltrimethylammonium chloride.

The monomers of formula (Ilia) of the present invention are preferably chosen from the group consisting of acrylic acid, methacrylic acid, crotonic acid and 2- methylcrotonic acid. More particularly, the monomer of formula (Ilia) is acrylic acid.

The monomers of formula (IVa) of the present invention are preferably chosen from the group consisting of C12-C22 and more particularly Ci₆-Ci₈ alkyl acrylates or methacrylates.

The monomers constituting the fatty-chain amphoteric polymers of the invention are preferably already neutralized and/or quaternized.

The ratio of the number of cationic charges/anionic charges is preferably equal to about 1 .

The amphoteric associative polymers according to the invention preferably comprise from 1 mol% to 10 mol% of the monomer comprising a fatty chain (monomer of formula (la), (I la) or (IVa)), and preferably from 1 .5 mol% to 6 mol%.

The weight-average molecular weights of the amphoteric associative polymers according to the invention may range from 500 to 50 000 000 and are preferably between 10 000 and 5 000 000.

The amphoteric associative polymers according to the invention may also contain other monomers such as nonionic monomers and in particular such as C C₄ alkyl acrylates or methacrylates. Amphoteric associative polymers according to the invention are described and prepared, for example, in patent application WO 98/44012.

Among the amphoteric associative polymers according to the invention, the ones that are preferred are acrylic acid/(meth)acrylamidopropyltrimethylammonium chloride/stearyl methacrylate terpolymers.

d) nonionic associative celluloses modified with groups comprising at least one fatty chain containing 8 to 30 carbon atoms and preferably from 10 to 22 carbon atoms, such as alkyl, arylalkyl or alkylaryl groups, or mixtures thereof, and in which the alkyl groups are preferably C₈-C₂2, for instance the product Natrosol Plus Grade 330 CS® (Ci₆ alkyls) sold by the company Aqualon, or the product Bermocoll EHM 100® sold by the company Berol Nobel.

Also suitable for use are those modified with alkylphenyl polyalkylene glycol ether groups, such as the product Amercell Polymer HM-1500® (polyethylene glycol

(15) nonylphenyl ether) sold by the company Amerchol.

e) associative nonionic hydroxypropyl guars modified with groups comprising at least one fatty chain containing 8 to 30 carbon atoms and preferably from 10 to 22 carbon atoms, such as the product Esaflor HM 22® (C22 alkyl chain) sold by the company

Lamberti, and the products RE210-18® (C_i4 alkyl chain) and RE205-1 ® (C₂₀ alkyl chain) sold by the company Rhodia.

f) associative nonionic copolymers of vinylpyrrolidone and of fatty-chain hydrophobic monomers containing 8 to 30 carbon atoms and preferably from 10 to 22 carbon atoms, of which examples that may be mentioned include:

- the products Antaron V216® or Ganex V216® (vinylpyrrolidone/hexadecene copolymer) sold by the company ISP,

- the products Antaron V220® or Ganex V220® (vinylpyrrolidone/eicosene copolymer) sold by the company ISP,

g) associative nonionic copolymers of Ci-C₆ alkyl acrylates or methacrylates and of amphiphilic monomers comprising at least one fatty chain containing 8 to 30 carbon atoms and preferably from 10 to 22 carbon atoms, preferably oxyethylenated, for instance the oxyethylenated methyl acrylate/stearyl acrylate copolymer sold by the company Goldschmidt under the name Antil 208®.

h) associative anionic copolymers of hydrophilic acrylates or methacrylates and of hydrophobic monomers comprising at least one fatty chain containing from 8 to 30 carbon atoms and preferably from 10 to 22 carbon atoms, for instance the polyethylene glycol methacrylate/lauryl methacrylate copolymer.

i) associative nonionic polyurethane polyethers comprising in their chain both hydrophilic blocks, which are preferably polyoxyethylenated, and hydrophobic blocks which may be aliphatic sequences alone and/or cycloaliphatic and/or aromatic sequences comprising from 8 to 30 carbon atoms and preferably from 10 to 22 carbon atoms.

j) associative nonionic polymers bearing an aminoplast ether backbone containing at least one fatty chain comprising from 8 to 30 carbon atoms and preferably from 10 to 22 carbon atoms, such as the Pure Thix® compounds sold by the company Sud- Chemie.

mixtures thereof.

Preferably, the thickening polymer(s) are chosen from nonionic and cationic polymers.

In a preferred embodiment of the invention, the thickening polymer(s) are chosen from nonionic non-associative polymers and in particular from guar gums.

Advantageously, the content of non-ionic, cationic and amphoteric thickening polymer ranges from 0.1 % to 10% by weight, preferably from 0.2% to 5% by weight and better still from 0.5% to 3% by weight relative to the total weight of the composition.

The composition according to the invention may contain, in addition to the cationic, amphoteric or nonionic thickening polymer, an anionic thickening polymer, that may be chosen from anionic non-associative polymers, or from anionic associative polymers, and also mixtures thereof.

Among the anionic non-associative polymers that are suitable for use in the invention, mention may be made of:

a) crosslinked homopolymers or copolymers of acrylic or methacrylic acid,

b) crosslinked homopolymers of 2-acrylamido-2-methylpropanesulfonic acid, and crosslinked acrylamide copolymers thereof,

c) ammonium acrylate homopolymers or copolymers of ammonium acrylate and of acrylamide,

A first family of suitable non-associative thickening polymers is represented by crosslinked acrylic acid homopolymers, such as those crosslinked with an allyl ether of an alcohol from the sugar series, for instance the products sold under the names Carbopol 980, 981 , 954, 2984 and 5984 by the company Noveon or the products sold under the names Synthalen M and Synthalen K by the company 3 VSA.

The non-associative thickening polymers may also be crosslinked (meth)acrylic acid copolymers, such as the polymer sold under the name Aqua SF1 by the company Noveon. The non-associative thickening polymers may be chosen from crosslinked 2- acrylamido-2-methylpropanesulfonic acid homopolymers and the crosslinked acrylamide copolymers thereof.

As regards these homopolymers and copolymers, which may be partially or totally neutralized, mention may be made of polymers comprising from 90% to 99.9% by weight, relative to the total weight of the polymer, of units of formula (j) below:

in which X⁺ denotes a cation or a mixture of cations, or a proton.

More particularly, the cations are chosen from alkali metals (for instance sodium or potassium), ammonium ions optionally substituted with 1 to 3 alkyl radicals, which may be identical or different, containing from 1 to 6 carbon atoms, optionally bearing at least one hydroxyl radical, cations derived from N-methylglucamine or from basic amino acids, for instance arginine and lysine. Preferably, the cation is an ammonium or sodium ion.

Moreover, the polymer comprises from 0.01 % to 10% by weight, relative to the total weight of the polymer, of crosslinking units derived from at least one monomer containing at least two ethylenic unsaturations (carbon-carbon double bond).

The crosslinking monomers containing at least two ethylenic unsaturations are chosen, for example, from diallyl ether, triallyl cyanurate, diallyl maleate, allyl (meth)acrylate, dipropylene glycol diallyl ether, polyglycol diallyl ethers, triethylene glycol divinyl ether, hydroquinone diallyl ether, tetraallyloxyethane, tetra- or diethylene glycol di(meth)acrylate, triallylamine, tetraallylethylenediamine, trimethylolpropane diallyl ether, trimethylolpropane triacrylate, methylenebis(meth)acrylamide or divinylbenzene, allylic ethers of alcohols of the sugar series, or other allylic or vinyl ethers of polyfunctional alcohols, and also allylic esters of phosphoric and/or vinylphosphonic acid derivatives, or mixtures of these compounds.

For further details regarding these polymers, reference may be made to document EP 815 828.

Among the partially or totally neutralized crosslinked copolymers of 2- acrylamido-2-methylpropanesulfonic acid and of acrylamide, mention may be made in particular of the product described in Example 1 of document EP 503 853, and reference may be made to the said document as regards these polymers.

The composition may similarly comprise, as non-associative thickening polymers, ammonium acrylate homopolymers or copolymers of ammonium acrylate and of acrylamide. Among the ammonium acrylate homopolymers that may be mentioned is the product sold under the name Microsap PAS 5193 by the company Hoechst. Among the copolymers of ammonium acrylate and of acrylamide that may be mentioned is the product sold under the name Bozepol C Nouveau or the product PAS 5193 sold by the company Hoechst. Reference may be made especially to documents FR 2 416 723, US 2 798 053 and US 2 923 692 as regards the description and preparation of such compounds.

The composition may also comprise dimethylaminoethyl methacrylate homopolymers quaternized with methyl chloride or dimethylaminoethyl methacrylate copolymers quaternized with methyl chloride and acrylamide.

Among the homopolymers of this type, mention may be made of the products sold under the names Salcare SC95 and Salcare SC96 by the company Ciba. Among the copolymers of this family, mention may be made of the product Salcare SC92 sold by Ciba or the product PAS 5194 sold by Hoechst. These polymers are especially described and prepared in document EP 395 282, to which reference may be made.

Among the anionic associative polymers that are suitable for use in the invention, mention may be made of:

a) anionic associative polymers comprising at least one hydrophilic unit of the type such as an ethylenic unsaturated anionic monomer, in particular a vinyl carboxylic acid, and most particularly an acrylic acid or a methacrylic acid or mixtures thereof, and at least one fatty-chain allyl ether unit comprising from 8 to 30 carbon atoms, corresponding especially to the monomer of formula (I) below:

CH₂ = C R' CH₂ O B„ R (I)

in which R' denotes H or CH₃, B denotes an ethylenoxy radical, n is zero or denotes an integer ranging from 1 to 100, R denotes a hydrocarbon-based radical chosen from alkyl, arylalkyl, aryl, alkylaryl and cycloalkyl radicals, containing from 8 to 30 carbon atoms, preferably 10 to 24 carbon atoms and even more particularly from 12 to 18 carbon atoms. A unit of formula (I) that is more particularly preferred is a unit in which R' denotes H, n is equal to 10, and R denotes a stearyl radical (Ci₈).

Anionic associative polymers of this type are described and prepared, according to an emulsion polymerization process, in patent EP-0 216 479.

Among these anionic associative polymers, those that are particularly preferred according to the invention are polymers formed from 20% to 60% by weight of acrylic acid and/or of methacrylic acid, from 5% to 60% by weight of lower alkyl (meth)acrylates, from 2% to 50% by weight of fatty-chain allyl ether of formula (I), and from 0 to 1 % by weight of a crosslinking agent which is a well-known copolymerizable unsaturated polyethylenic monomer, for instance diallyl phthalate, allyl (meth)acrylate, divinylbenzene, (poly)ethylene glycol dimethacrylate or methylenebisacrylamide.

Among the latter polymers, those most particularly preferred are crosslinked terpolymers of methacrylic acid, of ethyl acrylate and of polyethylene glycol (10 EO) stearyl alcohol ether (Steareth-10), in particular those sold by the company Ciba under the names Salcare SC 80® and Salcare SC 90®, which are aqueous 30% emulsions of a crosslinked terpolymer of methacrylic acid, of ethyl acrylate and of steareth-10 allyl ether (40/50/10);

b) anionic associative polymers comprising at least one hydrophilic unit of unsaturated olefinic carboxylic acid type and at least one hydrophobic unit of the type such as a (Ci₀-C₃o)alkyl ester of an unsaturated carboxylic acid.

These polymers are preferably chosen from those in which the hydrophilic unit of unsaturated olefinic carboxylic acid type corresponds to the monomer having the following formula (II):

(ID

in which R-i denotes H or CH₃ or C₅H₅, i.e. acrylic acid, methacrylic acid or ethacrylic acid units, and of which the hydrophobic unit of the type such as a (Cio-C₃₀)alkyl ester of an unsaturated carboxylic acid corresponds to the monomer having the following formul

in which R₂ denotes H or CH₃ or C₂H₅ (i.e. acrylate, methacrylate or ethacrylate units) and preferably H (acrylate units) or CH₃ (methacrylate units), R₃ denoting a Ci₀- C₃₀ and preferably C12-C22 alkyl radical.

(Cio-C₃₀)alkyl esters of unsaturated carboxylic acids according to the invention include, for example, lauryl acrylate, stearyl acrylate, decyl acrylate, isodecyl acrylate and dodecyl acrylate, and the corresponding methacrylates, lauryl methacrylate, stearyl methacrylate, decyl methacrylate, isodecyl methacrylate and dodecyl methacrylate.

Anionic polymers of this type are described and prepared, for example, according to patents US 3 915 921 and US 4 509 949.

Among anionic associative polymers of this type that will be used more particularly are polymers formed from a monomer mixture comprising:

• essentially acrylic acid, • an ester of formula (II I) described above in which R₂ denotes H or CH₃, R₃ denoting an alkyl radical containing from 12 to 22 carbon atoms, and

• a crosslinking agent, which is a well-known copolymerizable unsaturated polyethylenic monomer, for instance diallyl phthalate, allyl (meth)acrylate, divinylbenzene, (poly)ethylene glycol dimethacrylate and methylenebisacrylamide.

Among anionic associative polymers of this type that will be used more particularly are those consisting of from 95% to 60% by weight of acrylic acid (hydrophilic unit), 4% to 40% by weight of Ci₀-C₃o alkyl acrylate (hydrophobic unit) and 0 to 6% by weight of crosslinking polymerizable monomer, or alternatively those consisting of from 98% to 96% by weight of acrylic acid (hydrophilic unit), 1 % to 4% by weight of Ci₀-C₃o alkyl acrylate (hydrophobic unit) and 0.1 % to 0.6% by weight of crosslinking polymerizable monomer such as those described above.

Among the said above polymers, those most particularly preferred according to the present invention are the products sold by the company Goodrich under the trade names Pemulen TR1 ®, Pemulen TR2® and Carbopol 1382®, and even more preferentially Pemulen TR1 ®, and the product sold by the company SEPPIC under the name Coatex SX®.

Mention may also be made of polymers which, besides the monomers of formula (I I) and of formula (II I), contain one or more other monomers. This additional monomer may especially be a vinyllactam and in particular vinylpyrrolidone.

An example of a polymer that may be mentioned is the acrylic acid/lauryl methacrylate/vinylpyrrolidone terpolymer sold under the name Acrylidone LM by the company ISP.

c) maleic anhydride/C₃₀-C₃₈ oc-olefin/alkyl maleate anionic associative terpolymers, such as the product (maleic anhydride/C₃₀-C₃₈ oc-olefin/isopropyl maleate copolymer) sold under the name Performa V 1608® by the company Newphase Technologies, d) acrylic anionic associative terpolymers comprising:

(i) 20% to 70% by weight of an α,β-monoethylenically unsaturated carboxylic acid,

(ii) 20% to 80% by weight of a non-surfactant α,β-monoethylenically unsaturated monomer other than (i),

(iii) 0.5% to 60% by weight of a nonionic monourethane, which is the product of reaction of a monohydric surfactant with a monoethylenically unsaturated monoisocyanate,

such as those described in patent application EP-A-0 173 109 and more particularly the terpolymer described in Example 3, namely a methacrylic acid/methyl acrylate/behenyl alcohol dimethyl-meta-isopropenylbenzylisocyanate ethoxylated (40 EO) terpolymer, as an aqueous 25% dispersion.

e) anionic associative copolymers comprising among their monomers an α,β- monoethylenically unsaturated carboxylic acid and an ester of an α,β- monoethylenically unsaturated carboxylic acid and of an oxyalkylenated fatty alcohol.

Preferentially, these compounds also comprise as monomer an ester of an α,β- monoethylenically unsaturated carboxylic acid and of a Ci-C₄ alcohol.

An example of a compound of this type that may be mentioned is Aculyn 22® sold by the company Rohm & Haas, which is a methacrylic acid/ethyl acrylate/oxyalkylenated stearyl methacrylate terpolymer.

Advantageously, the content of thickening polymer(s) ranges from 0.1 % to 10% by weight, preferably from 0.1 % to 5% by weight and better still from 0.2% to 3% by weight, relative to the total weight of the composition.

Alkaline agent

The composition according to the invention also preferably comprises at least one alkaline agent other than the sulfonic, sulfonothioic or sulfinic compounds (b).

The basifying agent may be mineral or organic or hybrid (amine salts).

The mineral basifying agent(s) are preferably chosen from aqueous ammonia, alkali metal carbonates or bicarbonates such as sodium or potassium carbonates and sodium or potassium bicarbonates, sodium hydroxide or potassium hydroxide, or mixtures thereof.

The organic amine(s) are preferably chosen from organic amines with a pKb at 25°C of less than 12, preferably less than 10 and even more advantageously less than 6. It should be noted that it is the pKb corresponding to the function of highest basicity.

Compounds that are suitable for use which may be mentioned include the salts of the amines mentioned previously with acids such as carbonic acid or hydrochloric acid.

The organic amine(s) are chosen, for example, from alkanolamines, oxyethylenated and/or oxypropylenated ethylenediamines, amino acids and the compounds having the following formula:

Rx Rz

\ /

N - W - N

^Ry Rt

in which W is a Ci-C₆ alkylene residue optionally substituted with a hydroxyl group or a Ci-C₆ alkyl radical; Rx, Ry, Rz and Rt, which may be identical or different, represent a hydrogen atom or a Ci-C₆ alkyl, CrC₆ hydroxyalkyl or CrC₆ aminoalkyl radical. Examples of such amines that may be mentioned include 1 ,3-diaminopropane, 1 ,3-diamino-2-propanol, spermine and spermidine.

The term "alkanolamine" means an organic amine comprising a primary, secondary or tertiary amine function, and one or more linear or branched CrC₈ alkyl groups bearing one or more hydroxyl radicals.

Alkanolamines such as monoalkanolamines, dialkanolamines or trialkanolamines comprising from one to three identical or different CrC₄ hydroxyalkyi radicals are in particular suitable for implementing the invention.

Among compounds of this type, mention may be made of monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, N- dimethylaminoethanolamine, 2-amino-2-methyl-1-propanol, triisopropanolamine, 2- amino-2-methyl-1 ,3-propanediol, 3-amino-1 ,2-propanediol, 3-dimethylamino-1 ,2- propanediol and tris(hydroxymethylamino)methane.

More particularly, the amino acids that may be used are of natural or synthetic origin, in their L, D or racemic form, and comprise at least one acid function chosen more particularly from carboxylic acid, phosphonic acid or phosphoric acid functions. The amino acids may be in neutral or ionic form.

As amino acids that can be used in the present invention, mention may be made especially of aspartic acid, glutamic acid, alanine, arginine, ornithine, citrulline, asparagine, carnitine, cysteine, glutamine, glycine, histidine, lysine, isoleucine, leucine, methionine, N-phenylalanine, proline, serine, threonine, tryptophan, tyrosine and valine.

Advantageously, the amino acids are basic amino acids comprising an additional amine function optionally included in a ring or in a ureido function.

Such basic amino acids are preferably chosen from those corresponding to the formula below:

NH₉

/ ²

R CH₂— CH^

C0₂H

i enotes a group chosen from:

-(CH₂)₂NH₂ -(CH₂)₂NHCONH₂

-(CH₂)₂NH C— NH₂

NH

The compounds corresponding to the formula above are histidine, lysine, arginine, ornithine and citrulline. The organic amine may also be chosen from organic amines of heterocyclic type. Besides histidine that has already been mentioned in the amino acids, mention may be made in particular of pyridine, piperidine, imidazole, triazole, tetrazole and benzimidazole.

The organic amine can also be chosen from amino acid dipeptides. As amino acid dipeptides that may be used in the present invention, mention may be made especially of carnosine, anserine and balenine.

The organic amine is chosen from compounds comprising a guanidine function. As amines of this type that may be used in the present invention, besides arginine, which has already been mentioned as an amino acid, mention may be made especially of creatine, creatinine, 1 ,1 -dimethylguanidine, 1 ,1 - diethylguanidine, glycocyamine, metformin, agmatine, N-amidinoalanine, 3- guanidinopropionic acid and 4-guanidinobutyric acid.

Organic amine salts that may be mentioned in particular include guanidine carbonate and monoethanolamine hydrochloride.

Preferably, the organic amine is chosen from alkanolamines and is most particularly monoethanolamine.

The composition more particularly has a content of basifying agent(s) and preferably of organic amine(s) of at least 0.01 % and preferably of at least 0.5% by weight relative to the weight of the composition, advantageously ranging from 0.01 % to 30% by weight and better still from 0.5% to 10% by weight relative to the weight of the said composition.

Fatty substances

The composition may comprise one or more fatty substances, preferably to a proportion of at least 10% by weight relative to the weight of the composition.

The term "fatty substance" means an organic compound that is insoluble in water at ordinary temperature (25°C) and at atmospheric pressure (760 mmHg) (solubility of less than 5%, preferably less than 1 % and even more preferentially less than 0.1 %). They have in their structure at least one hydrocarbon-based chain containing at least 6 carbon atoms or a sequence of at least two siloxane groups. In addition, the fatty substances are generally soluble in organic solvents under the same temperature and pressure conditions, for instance chloroform, dichloromethane, carbon tetrachloride, ethanol, benzene, toluene, tetrahydrofuran (THF), liquid petroleum jelly or decamethylcyclopentasiloxane.

The fatty substances of the invention do not contain any salified carboxylic acid groups. In particular, the fatty substances of the invention are also not (poly)oxyalkylenated or (poly)glycerolated ethers.

The term "o/T means a "fatty substance" that is liquid at room temperature (25°C) and at atmospheric pressure (760 mmHg).

The term "non-silicone o/T means an oil not containing any silicon (Si) atoms and the term "silicone o/T means an oil containing at least one silicon atom.

More particularly, the fatty substances are chosen from C₆-Ci₆ hydrocarbons, hydrocarbons containing more than 16 carbon atoms, non-silicone oils of animal origin, plant oils of triglyceride type, synthetic triglycerides, fluoro oils, fatty alcohols, fatty acid and/or fatty alcohol esters other than triglycerides and plant waxes, non- silicone waxes and silicones, and mixtures thereof.

It should be remembered that fatty alcohols, esters and acids more particularly exhibit at least one saturated or unsaturated and linear or branched hydrocarbon- based group which comprises from 6 to 30 and better still from 8 to 30 carbon atoms and which is optionally substituted, in particular with one or more hydroxyl groups (in particular 1 to 4). If they are unsaturated, these compounds may comprise one to three conjugated or unconjugated carbon-carbon double bonds.

As regards the C₆-Ci₆ hydrocarbons, they are linear, branched or optionally cyclic, and are preferably alkanes. Examples that may be mentioned include hexane, dodecane and isoparaffins such as isohexadecane and isodecane.

Mention may be made, as hydrocarbon-based oils of animal origin, of perhydrosqualene.

The triglyceride oils of plant or synthetic origin are preferably chosen from liquid fatty acid triglycerides comprising from 6 to 30 carbon atoms, for instance heptanoic or octanoic acid triglycerides, or alternatively, for example, sunflower oil, corn oil, soybean oil, marrow oil, grapeseed oil, sesame seed oil, hazelnut oil, apricot oil, macadamia oil, arara oil, castor oil, avocado oil, caprylic/capric acid triglycerides, for instance those sold by the company Stearineries Dubois or those sold under the names Miglyol® 810, 812 and 818 by the company Dynamit Nobel, jojoba oil and shea butter oil.

The linear or branched hydrocarbons of mineral or synthetic origin having more than 16 carbon atoms are preferably chosen from liquid paraffins, petroleum jelly, liquid petroleum jelly, polydecenes or hydrogenated polyisobutene, such as Parleam®.

As regards the C₆-Ci₆ alkanes, they are linear, branched or optionally cyclic. By way of example, mention may be made of hexane, dodecane and isoparaffins such as isohexadecane and isodecane. As oils of animal, plant, mineral or synthetic origin that may be used in the composition of the invention, examples that may be mentioned include:

fluoro oils which may be chosen from perfluoromethylcyclopentane and perfluoro- 1 ,3-dimethylcyclohexane, sold under the names Flutec^® PC1 and Flutec^® PC3 by the company BNFL Fluorochemicals; perfluoro-1 ,2-dimethylcyclobutane; perfluoroalkanes such as dodecafluoropentane and tetradecafluorohexane, sold under the names PF 5050^® and PF 5060^® by the company 3M, or alternatively bromoperfluorooctyl sold under the name Foralkyl^® by the company Atochem; nonafluoromethoxybutane and nonafluoroethoxyisobutane; perfluoromorpholine derivatives such as 4-trifluoromethyl perfluoromorpholine sold under the name PF 5052^® by the company 3M.

The fatty alcohols which are suitable for the implementation of the invention are more particularly chosen from saturated or unsaturated and linear or branched alcohols comprising from 6 to 30 carbon atoms and preferably from 8 to 30 carbon atoms. Examples that may be mentioned include cetyl alcohol, stearyl alcohol and the mixture thereof (cetylstearyl alcohol), octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol, oleyl alcohol and linoleyl alcohol.

As regards the fatty acid and/or fatty alcohol esters, which are advantageously different from the triglycerides mentioned above, mention may be made in particular of esters of saturated or unsaturated and linear or branched Ci-C₂6 aliphatic monoacids or polyacids and of saturated or unsaturated and linear or branched C C₂6 aliphatic monoalcohols or polyalcohols, the total carbon number of the esters being greater than or equal to 6 and more advantageously greater than or equal to 10.

Among the monoesters, mention may be made of dihydroabietyl behenate; octyldodecyl behenate; isocetyl behenate; cetyl lactate; Ci₂-Ci₅ alkyl lactate; isostearyl lactate; lauryl lactate; linoleyl lactate; oleyl lactate; (iso)stearyl octanoate; isocetyl octanoate; octyl octanoate; cetyl octanoate; decyl oleate; isocetyl isostearate; isocetyl laurate; isocetyl stearate; isodecyl octanoate; isodecyl oleate; isononyl isononanoate; isostearyl palmitate; methylacetyl ricinoleate; myristyl stearate; octyl isononanoate; 2-ethylhexyl isononate; octyl palmitate; octyl pelargonate; octyl stearate; octyldodecyl erucate; oleyl erucate; ethyl and isopropyl palmitates, 2- ethylhexyl palmitate, 2-octyldecyl palmitate, alkyl myristates such as isopropyl, butyl, cetyl, 2-octyldodecyl, myristyl or stearyl myristate, hexyl stearate, butyl stearate, isobutyl stearate; dioctyl malate, hexyl laurate, 2-hexyldecyl laurate.

Still within the context of this variant, esters of C4-C22 dicarboxylic or tricarboxylic acids and of C1-C22 alcohols and esters of mono-, di- or tricarboxylic acids and of C₂-C₂6 di-, tri-, tetra- or pentahydroxy alcohols may also be used. Mention may in particular be made of: diethyl sebacate; diisopropyl sebacate; diisopropyl adipate; di(n-propyl) adipate; dioctyl adipate; diisostearyl adipate; dioctyl maleate; glyceryl undecylenate; octyldodecyl stearoyl stearate; pentaerythrityl monoricinoleate; pentaerythrityl tetraisononanoate; pentaerythrityl tetrapelargonate; pentaerythrityl tetraisostearate; pentaerythrityl tetraoctanoate; propylene glycol dicaprylate; propylene glycol dicaprate; tridecyl erucate; triisopropyl citrate; triisostearyl citrate; glyceryl trilactate; glyceryl trioctanoate; trioctyldodecyl citrate; trioleyl citrate; propylene glycol dioctanoate; neopentyl glycol diheptanoate; diethylene glycol diisononanoate; and polyethylene glycol distearates.

Among the esters mentioned above, use is preferably made of ethyl, isopropyl, myristyl, cetyl or stearyl palmitate, 2-ethylhexyl palmitate, 2-octyldecyl palmitate, alkyl myristates, such as isopropyl, butyl, cetyl or 2-octyldodecyl myristate, hexyl stearate, butyl stearate, isobutyl stearate, dioctyl malate, hexyl laurate, 2- hexyldecyl laurate, isononyl isononanoate or cetyl octanoate.

The composition may also comprise, as fatty ester, sugar esters and diesters of

C₆-C₃o and preferably C12-C22 fatty acids. It is recalled that the term "sugar" means oxygen-bearing hydrocarbon-based compounds containing several alcohol functions, with or without aldehyde or ketone functions, and which comprise at least 4 carbon atoms. These sugars can be monosaccharides, oligosaccharides or polysaccharides.

Mention may be made, as suitable sugars, for example, of sucrose (or saccharose), glucose, galactose, ribose, fucose, maltose, fructose, mannose, arabinose, xylose and lactose, and derivatives thereof, in particular alkyl derivatives, such as methyl derivatives, for instance methylglucose.

The sugar esters of fatty acids may be chosen in particular from the group comprising the esters or mixtures of esters of sugars described previously and of linear or branched, saturated or unsaturated C₆-C₃o and preferably C12-C22 fatty acids. If they are unsaturated, these compounds may comprise one to three conjugated or unconjugated carbon-carbon double bonds.

The esters according to this variant may also be chosen from mono-, di-, tri- and tetraesters, polyesters, and mixtures thereof.

These esters can, for example, be oleates, laurates, palmitates, myristates, behenates, cocoates, stearates, linoleates, linolenates, caprates, arachidonates or mixtures thereof, such as, in particular, oleate/palmitate, oleate/stearate or palmitate/stearate mixed esters.

More particularly, use is made of monoesters and diesters and in particular mono- or di-oleate, -stearate, -behenate, -oleate/palmitate, -linoleate, -linolenate or - oleate/stearate of sucrose, of glucose or of methylglucose. An example that may be mentioned is the product sold under the name Glucate® DO by the company Amerchol, which is a methylglucose dioleate.

Examples of esters or mixtures of esters of sugar and of fatty acid that may also be mentioned include:

- the products sold under the names F160, F140, F1 10, F90, F70 and SL40 by the company Crodesta, respectively denoting sucrose palmitate/stearates formed from 73% monoester and 27% diester and triester, from 61 % monoester and 39% diester, triester and tetraester, from 52% monoester and 48% diester, triester and tetraester, from 45% monoester and 55% diester, triester and tetraester, from 39% monoester and 61 % diester, triester and tetraester, and sucrose monolaurate;

- the products sold under the name Ryoto Sugar Esters, for example referenced B370 and corresponding to sucrose behenate formed from 20% monoester and 80% diester-tri ester-polyester;

- the sucrose monopalmitate/stearate-dipalmitate/stearate sold by the company Goldschmidt under the name Tegosoft^® PSE.

The non-silicone wax(es) are chosen in particular from carnauba wax, candelilla wax, esparto wax, paraffin wax, ozokerite, plant waxes, such as olive tree wax, rice wax, hydrogenated jojoba wax or absolute flower waxes, such as the blackcurrant blossom essential wax sold by the company Bertin (France), or animal waxes, such as beeswaxes or modified beeswaxes (cerabellina); other waxes or waxy starting materials which can be used according to the invention are in particular marine waxes, such as that sold by the company Sophim under the reference M82, polyethylene waxes or polyolefin waxes in general.

The silicones that can be used in the dye composition according to the present invention are volatile or non-volatile, cyclic, linear or branched silicones, which are unmodified or modified by organic groups, having a viscosity from 5x 10^"6 to 2.5 m²/s at 25°C, and preferably 1 x 10^"5 to 1 m²/s.

The silicones that may be used in accordance with the invention may be in the form of oils, waxes, resins or gums.

Preferably, the silicone is chosen from polydialkylsiloxanes, in particular polydimethylsiloxanes (PDMSs), and organomodified polysiloxanes comprising at least one functional group chosen from amino groups and alkoxy groups.

Organopolysiloxanes are defined in greater detail in Walter Noll's "Chemistry and Technology of Silicones" (1968), Academic Press. They may 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 polydialkylsiloxanes containing from 3 to 7 and preferably from 4 to 5 silicon atoms. These are, for example, octamethylcyclotetrasiloxane sold in particular under the name Volatile Silicone^® 7207 by Union Carbide or Silbione^® 70045 V2 by Rhodia, decamethylcyclopentasiloxane sold under the name Volatile Silicone^® 7158 by Union Carbide, and Silbione^® 70045 V5 by Rhodia, and mixtures thereof.

Mention may also be made of cyclocopolymers of the dimethylsiloxane/methylalkylsiloxane type, such as Volatile Silicone® FZ 3109 sold by the company Union Carbide, of formula:

with D" : —

Mention may also be made of mixtures of cyclic polydialkylsiloxanes with organosilicon compounds, such as the mixture of octamethylcyclotetrasiloxane and tetra(trimethylsilyl)pentaerythritol (50/50) and the mixture of octamethylcyclotetrasiloxane and oxy-1 ,1 '-bis(2,2,2',2',3,3'- hexatrimethylsilyloxy)neopentane;

(ii) linear volatile polydialkylsiloxanes containing 2 to 9 silicon atoms and having a viscosity of less than or equal to 5x10^"6 m²/s at 25°C. An example is decamethyltetrasiloxane sold in particular under the name SH 200 by the company Toray Silicone. Silicones belonging to this category are also described in the article published in Cosmetics and Toiletries, Vol. 91 , Jan. 76, pp. 27-32, Todd & Byers, Volatile Silicone Fluids for Cosmetics.

Use is preferably made of non-volatile polydialkylsiloxanes, polydialkylsiloxane gums and resins, polyorganosiloxanes modified with the organofunctional groups above, and mixtures thereof.

These silicones are more particularly chosen from polydialkylsiloxanes, among which mention may be made mainly of polydimethylsiloxanes having trimethylsilyl end groups. The viscosity of the silicones is measured at 25°C according to Standard ASTM 445 Appendix C.

Mention may be made, among these polydialkylsiloxanes, without limitation, of the following commercial products:

- the Silbione^® oils of the 47 and 70 047 series or the Mirasil^® oils sold by Rhodia, such as, for example, the oil 70 047 V 500 000;

- the oils of the Mirasil^® series sold by the company Rhodia; - the oils of the 200 series from the company Dow Corning, such as DC200 with a viscosity of 60 000 mm²/s;

- the Viscasil^® oils from General Electric and certain oils of the SF series (SF 96, SF 18) from General Electric.

Mention may also be made of polydimethylsiloxanes bearing dimethylsilanol end groups known under the name dimethiconol (CTFA), such as the oils of series 48 from the company Rhodia.

In this category of polydialkylsiloxanes, mention may also be made of the products sold under the names Abil Wax® 9800 and 9801 by the company Goldschmidt, which are polydi(CrC₂o)alkylsiloxanes.

The silicone gums that may be used in accordance with the invention are in particular polydialkylsiloxanes and preferably polydimethylsiloxanes with high number-average molecular weights of between 200 000 and 1 000 000, used alone or as a mixture in a solvent. This solvent may be chosen from volatile silicones, polydimethylsiloxane (PDMS) oils, polyphenylmethylsiloxane (PPMS) oils, isoparaffins, polyisobutylenes, methylene chloride, pentane, dodecane and tridecane, or mixtures thereof.

Products that may be used more particularly in accordance with the invention are mixtures such as:

- the mixtures formed from a polydimethylsiloxane hydroxylated at the chain end, or dimethiconol (CTFA), and from a cyclic polydimethylsiloxane, also known as cyclomethicone (CTFA), such as the product Q2 1401 sold by the company Dow Corning;

- the mixtures of a polydimethylsiloxane gum and of a cyclic silicone, such as the product SF 1214 Silicone Fluid from General Electric; this product is a gum SF 30 corresponding to a dimethicone, having a number-average molecular weight of 500 000, dissolved in the oil SF 1202 Silicone Fluid corresponding to decamethylcyclopentasiloxane;

- mixtures of two PDMSs with different viscosities, and more particularly of a PDMS gum and a PDMS oil, such as the product SF 1236 from the company General

Electric. The product SF 1236 is a mixture of a gum SE 30 defined above, with a viscosity of 20 m²/s, and of an oil SF 96 with a viscosity of 5x10^"6 m²/s. This product preferably comprises 15% of gum SE 30 and 85% of an oil SF 96.

The organopolysiloxane resins that may be used in accordance with the invention are crosslinked siloxane systems containing the following units:

R₂Si0₂/₂, R3S1O1/2, RS1O3/2 and Si0₄/₂ in which R represents an alkyl containing 1 to 16 carbon atoms. Among these products, those that are particularly preferred are those in which R denotes a Ci-C₄ lower alkyl group, more particularly methyl.

Mention may be made, among these resins, of the product sold under the name Dow Corning 593 or those sold under the names Silicone Fluid SS 4230 and SS 4267 by the company General Electric, which are silicones of dimethyl/trimethylsiloxane structure.

Mention may also be made of the resins of the trimethylsiloxysilicate type, sold in particular under the names X22-4914, X21 -5034 and X21 -5037 by the company Shin-Etsu.

The organomodified silicones that 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-based group.

In addition to the silicones described above, the organomodified silicones can be polydiarylsiloxanes, in particular polydiphenylsiloxanes, and polyalkylarylsiloxanes functionalized by the abovementioned organofunctional groups.

The polyalkylarylsiloxanes are particularly chosen from linear and/or branched polydimethyl/methylphenylsiloxanes and polydimethyl/diphenylsiloxanes with a viscosity ranging from 1 x10^"5 to 5x 10^"2 m²/s at 25°C.

Mention may be made, among these polyalkylarylsiloxanes, by way of example, of the products sold under the following names:

. the Silbione^® oils of the 70 641 series from Rhodia;

. the oils of the Rhodorsil^® 70 633 and 763 series from Rhodia;

. the oil Dow Corning 556 Cosmetic Grade Fluid from Dow Corning;

. the silicones of the PK series from Bayer, such as the product PK20;

. the silicones of the PN and PH series from Bayer, such as the products PN 1000 and PH 1000;

. certain oils of the SF series from General Electric, such as SF 1023, SF 1 154, SF 1250 and SF 1265.

Mention may be made, among the organomodified silicones, of polyorganosiloxanes comprising:

- 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, d-C₄ aminoalkyl groups;

- 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. More particularly, the fatty substances are chosen from compounds that are liquid or pasty at room temperature (25°C) and at atmospheric pressure.

Preferably, the fatty substance is a compound that is liquid at a temperature of 25°C and at atmospheric pressure.

The fatty substances are advantageously chosen from C₆-Ci₆ alkanes, non- silicone oils of plant, mineral or synthetic origin, fatty alcohols, fatty acid and/or fatty alcohol esters, or mixtures thereof.

Preferably, the fatty substance is chosen from liquid petroleum jelly, C₆-Ci₆ alkanes, polydecenes, liquid fatty acid and/or fatty alcohol esters, liquid fatty alcohols, or mixtures thereof.

Preferably, as indicated previously, the fatty substance content is at least 10% by weight relative to the total weight of the composition.

According to a more particular embodiment, this content is advantageously at least 15% by weight, more particularly at least 20% by weight, preferably at least 25% by weight and even more particularly at least 30% by weight relative to the total weight of the composition, and may be up to 70% by weight relative to the total weight of the composition. Reductone

In accordance with one variant of the invention, the composition preferably comprises at least one reductone.

In a manner known per se, the term "reductone" denotes a compound comprising an enediol structure -(HO)C=C(OH)- adjacent to a carbonyl group >C=0.

Thus, the reductone(s) that may be used in the present invention are of general formula (C):

R— (HO)C=C(OH) C— R₂

⁰ (C)

with R-i and R₂, which may be identical or different, each denoting a group containing at least one carbon and/or oxygen atom, R-i and R₂ possibly forming with the three carbon atoms of the compound of formula (II) a ring, which is preferably 5- or 6-membered, the additional constituent atoms of which consist of carbon and/or oxygen atoms.

Preferably, Ri and R₂ form with the three carbon atoms of the compound of formula (II) a ring containing 5 carbon and/or oxygen atoms.

The compound(s) of formula (C) may be in acid form, or in the form of salts, especially in the form of salts of alkali metals such as sodium and potassium, or salts of alkaline-earth metals such as calcium and magnesium, or in the form of esters, especially of C₈ to C₃₀ fatty acids.

In a particularly preferred manner, the compound of formula (C) is a lactone.

The reductone(s) may be chosen especially from reductic acid, ascorbic acid, erythorbic acid or isoascorbic acid, and the salts of these compounds, especially the sodium or potassium salts, ascorbyl palmitate, and mixtures of these compounds.

In a particularly preferred manner, the reductone(s) are chosen from ascorbic acid, erythorbic acid, and the salts of these compounds, especially the sodium or potassium salts.

Preferably, the amount of reductone(s) represents from 0.01 % to 1 % by weight, preferably from 0.05% to 0.5% by weight and even better still from 0.1 % to 0.25% by weight relative to the weight of the composition.

Oxidizing agent

The composition according to the invention may also comprise at least one oxidizing agent.

It should be noted that the oxidizing agents present in the composition are different from atmospheric oxygen.

In particular, the oxidizing agent(s) suitable for use in the present invention are chosen, for example, from hydrogen peroxide, urea peroxide, alkali metal bromates or ferricyanides, peroxygenated salts, for instance persulfates, perborates, peracids and precursors thereof and percarbonates of alkali metals or alkaline-earth metals. Advantageously, the oxidizing agent is hydrogen peroxide.

The oxidizing agent(s) generally represent from 0.1 % to 50% by weight and preferably from 1 % to 20% by weight relative to the total weight of the composition according to the invention.

Additives

The composition may also contain various adjuvants conventionally used in compositions for dyeing or lightening the hair, such as anionic or nonionic polymers, or mixtures thereof; nonionic, anionic, amphoteric or zwitterionic or cationic surfactants; antioxidants such as sulfites; penetrants; sequestrants; fragrances; dispersants; film- forming agents; ceramides; preserving agents; opacifiers, vitamins.

The above adjuvants are generally present in an amount, for each of them, of between 0.01 % and 20% by weight relative to the weight of the composition.

Additives

The composition may also contain various adjuvants conventionally used in compositions for dyeing or lightening the hair, such as anionic or nonionic polymers, or mixtures thereof; cationic surfactants; antioxidants; penetrants; sequestrants; fragrances; dispersants; film-forming agents; ceramides; preserving agents; vitamins, opacifiers.

In a specific embodiment, the composition of the invention contains at least one vitamin.

The vitamins that may be of use in the composition of the invention can in particular be chosen from vitamin C, A vitamins, B vitamins, D vitamins, vitamin E and vitamin F, and derivatives thereof.

Vitamin C

Vitamin C corresponds to ascorbic acid which is generally in L form, since it is usually extracted from natural products. Ascorbic acid derivatives are, more

particularly, its salts, such as in particular sodium ascorbate, magnesium ascorbyl phosphate or sodium ascorbyl phosphate; it esters, for instance in particular its esters such as ascorbyl acetate, ascorbyl palmitate and ascorbyl propionate; its oxidized form, dehydroascorbic acid; or its sugars, such as in particular glycosylated ascorbic acid, and mixtures thereof.

Vitamin B3

Vitamin B3, also known as vitamin compound of formula

in which R can be -CONH₂ (niacinamide), -COOH (nicotinic acid or niacin), or CH₂OH (nicotinyl alcohol), -CO-NH-CH₂-COOH (nicotinuric acid) or -CO-NH-OH (niconityl hydroxamic acid).

As vitamin B3 derivatives, mention may, for example, be made of nicotinic acid esters such as tocopheryl nicotinate, amides derived from niacinamide by substitution of hydrogen groups of -CONH_2, products of reaction with carboxylic acids and amino acids, and esters of nicotinyl alcohol and of carboxylic acids such as acetic acid, salicylic acid, glycolic acid or palmitic acid. Mention may also be made of the following derivatives: 2-chloronicotinamide, 6-methylnicotinamide, 6-aminonicotinamide, N- methylnicotinamide, Ν,Ν-dimethylnicotinamide, N-(hydroxymethyl)nicotinamide, quinolinic acid imide, nicotinanilide, N-benzylnicotinamide, N-ethylnicotinamide, nifenazone, nicotinaldehyde, isonicotinic acid, methylisonicotinic acid,

thionicotinamide, nialamide, 2-mercaptonicotinic acid, nicomol et niaprazine. As other vitamin B3 derivatives, mention may also be made of its inorganic salts, such as chlorides, bromides, iodides or carbonates, and its organic salts, such as the salts obtained by reaction with carboxylic acids, such as acetate, salicylate, glycolate, lactate, malate, citrate, mandelate, tartrate, etc.

Vitamin B5

Vitamin B5 is pantothenic acid

As vitamin B5 derivatives, use may be made of panthenol or panthenyl alcohol or 2,4-dihydroxy-N-(3-hydroxypropyl)-3,3-dimethylbutanamide, in its various forms: D- panthenol, DL-panthenol which is the alcohol form of pantothenic acid and one of its precursors. Use may also be made, as derivatives, of calcium pantothenate, pantethine, pantotheine, panthenyl ethyl ether, pangamic acid, pyridoxine, pantoyl lactose, and natural compounds containing same, such as royal jelly.

Vitamin D

As vitamin D, mention may be made of vitamin D1 (lumisterol(1 )/calciferol(1 ) complex), vitamin D2 (calciferol) and vitamin D3 (colecalciferol). By way of derivatives, mention may be made of vitamin D analogues such as those described in document WO-A-00/26167, for instance:

- 3-hydroxymethyl-5-{2-[3-(5-hydroxy-5- or 6-methylhexyl)phenyl]vinyl}phenol,

- 3-[3-(5-hydroxy-1 ,5-(dimethyl)hexyl)phenoxymethyl]-5-hydroxymethylphenol, - 6-[3-(3,4-bis(hydroxymethyl)benzyloxy)phenyl]-2-methylhepta-3,5-dien-2-ol,

- 6-[3-(3,4-bis(hydroxymethyl)benzyloxy)phenyl]-2-methylhexan-2-ol,

- 6-[3-(3,4-bis(hydroxymethyl)phenoxymethyl)phenyl]-2-methylheptan-2-ol,

- 7-[3-(3,4-bis(hydroxymethyl)phenoxymethyl)phenyl]-3-ethyloctan-3-ol,

- 5-{2-[4-(5-hydroxy-5-methylhexyl)phenyl]-vinyl ou -ethyl}benzene-1 ,3-diol,

- 5-{2-[3- or 4-(6-hydroxy-6-methylheptyl)phenyl]vinyl}benzene-1 ,3-diol,

- 5-{2-[3- or 4-(6-hydroxy-6-methylheptyl)phenyl]ethyl}benzene-1 ,3-diol,

- 2-hydroxymethyl-4-{2-[3- or 4-(5-hydroxy-5-methylhexyl)phenyl]vinyl}phenol,

- 2-hydroxymethyl-4-{2-[3 or 4-(6-hydroxy-6-methylheptyl)phenyl]vinyl}phenol,

- 2-hydroxymethyl-4-{2-[3- or 4-(5-hydroxy-5-methylheptyl)phenyl]ethyl}phenol, - 2-hydroxymethyl-4-{2-[3- or 4-(6-hydroxy-6-methylheptyl)phenyl]ethyl}phenol,

- 2-hydroxymethyl-5-{2-[4-(5-hydroxy-5-methylhexyl)phenyl]vinyl}phenol,

- 6-[3-(3,4-bis(hydroxymethyl)benzyloxy)phenyl]-2-methylheptan-2-ol,

- 4-[3-(5-hydroxy-1 ,5-(dimethyl)hexyl)phenoxymethyl]-2-hydroxymethylphenol,

- 6-{3- or 4-[2-(3,4-bis(hydroxymethyl)phenyl)vinyl]phenyl}-2-methylhexan-2-ol, - 7-{4-[2-(3,4-bis(hydroxymethyl)phenyl)vinyl]phenyl}-2-methylheptan-2-ol,

- 5-{2-[3-(6-hydroxy-6-methylheptyl)phenyl]-1 -methylvinyl}benzene-1 ,3-diol,

- 5-{2-[3-(5-hydroxy-5-methylhexyl)phenyl]vinyl}benzene-1 ,3-diol,

- 5-[3-(6-hydroxy-6-methylheptyl)phenoxymethyl]benzene-1 ,3-diol, - 5-{2-[3-(7-hydroxy-7-methyloct-1 -enyl)phenyl]vinyl}benzene-1 ,3-diol,

- 5-{2-[3-(7-hydroxy-7-methyloctyl)phenyl]vinyl}benzene-1 ,3-diol,

- 4-{2-[3-(6-hydroxy-6-methylheptyl)phenyl]vinyl}benzene-1 ,2-diol,

- 3-{2-[3-(6-hydroxy-6-methylheptyl)phenyl]vinyl}phenol,

- 6-{3-[2-(3,5-bis(hydroxymethyl)phenyl)vinyl]phenyl}-2-methylhexan-2-ol,

- 3-{2-[3-(7-hydroxy-7-methyloctyl)phenyl]vinyl}phenol,

- 7-{3-[2-(3,5-bis(hydroxymethyl)phenyl)vinyl]phenyl}-2-methylheptan-2-ol,

- 7-{3-[2-(3,4-bis(hydroxymethyl)phenyl)vinyl]phenyl}-2-methylheptan-2-ol,

- 7-{3-[2-(4-hydroxymethylphenyl)vinyl]phenyl}-2-methylheptan-2-ol,

- 4-{2-[3-(7-hydroxy-7-methyloct-1 -enyl)phenyl]vinyl}benzene-1 ,2-diol,

- 7-[3-(3,4-bis(hydroxymethyl)phenylethynyl)phenyl]-2-methylheptan-2-ol,

- 5-{2-[3-(6-hydroxy-6-methylhept-1 -enyl)phenyl]vinyl}benzene-1 ,3-diol,

- 5-{2-[3-(7-ethyl-7-hydroxynon-1 -enyl)phenyl]vinyl}benzene-1 ,3-diol,

- 5-{2-[3-(7-hydroxy-1 -methoxy-1 ,7-dimethyloctyl)phenyl]vinyl}benzene-1 ,3-diol, - 5-{2-[3-(6-hydroxy-1 -methoxy-1 ,6-dimethylheptyl)phenyl]vinyl}benzene-1 ,3-diol,

- 5-{2-[3-(5-hydroxypentyl)phenyl]vinyl}benzene-1 ,3-diol,

- 5-{2-[3-(5-hydroxy-6-methylheptyl)phenyl]vinyl}benzene-1 ,3-diol,

- 5-{2-[3-(6-hydroxy-7-methyloctyl)phenyl]vinyl}benzene-1 ,3-diol,

- 5-{2-[3-(5-hydroxy-6-methylhept-1 -enyl)phenyl]vinyl}benzene-1 ,3-diol,

- 5-{2-[3-(6-hydroxy-7-methyloct-1 -enyl)phenyl]vinyl}benzene-1 ,3-diol,

- 5-{2-[3-(1 ,6-dihydroxy-1 ,6-dimethylheptyl)phenyl]vinyl}benzene-1 ,3-diol,

- 5-{2-[3-(6-hydroxy-1 ,6-(dimethyl)hept-1 -enyl)phenyl]vinyl}benzene-1 ,3-diol.

Vitamin F

Vitamin F is a mixture of essential fatty acids, i.e. of unsaturated acids which have at least one double bond, such as linoleic acid or 9,12-octadecadienoic acid and its stereoisomers, linolenic acid in a form (9,12,15-octadecatrienoic acid) or yform (6,9,12- octadecatrienoic acid) and their stereoisomers, arachidonic acid or 5,8,1 1 ,14- eicosatetraenoic acid and its stereoisomers.

Vitamin F, or mixtures of unsaturated acids which have at least one double bond and in particular mixtures of linoleic acid, linolenic acid and arachidonic acid, or the compounds containing same, and in particular oils of vegetable origin containing same, for instance jojoba oil, can be used in the composition of the present invention.

Vitamin E

Vitamin E is alpha-tocopherol.

The vitamin E derivatives can be chosen from esters of vitamin E, and in particular the acetate, succinate or nicotinate.

The composition of the invention can comprise one or more vitamins, of the same category or of different categories. Preferably, the vitamins are chosen from water-soluble vitamins and in particular vitamins B or C.

According to one particular embodiment, the composition comprises at least vitamin C in ascorbic acid form.

The vitamin(s) may be present in an amount ranging from 0.005% to 1 % by weight, and preferably from 0.1 % to 1 % by weight, of active material relative to the total weight of the composition.

The composition according to the invention may comprise water and/or one or more organic solvents.

Examples of organic solvents that may be mentioned include linear or branched and preferably saturated monoalcohols or diols, comprising 2 to 10 carbon atoms, such as ethyl alcohol, isopropyl alcohol, hexylene glycol (2-methyl-2,4-pentanediol), neopentyl glycol and 3-methyl-1 ,5-pentanediol, butylene glycol, dipropylene glycol and propylene glycol; aromatic alcohols such as benzyl alcohol or phenylethyl alcohol; polyols containing more than two hydroxyl functions, such as glycerol; polyol ethers, for instance ethylene glycol monomethyl, monoethyl or monobutyl ether, propylene glycol or ethers thereof, for instance propylene glycol monomethyl ether; and also diethylene glycol alkyl ethers, especially Ci-C₄ alkyl ethers, for instance diethylene glycol monoethyl ether or monobutyl ether, alone or as a mixture.

The organic solvents, when they are present, generally represent between 1 % and 40% by weight relative to the total weight of the dye composition, and preferably between 5% and 30% by weight relative to the total weight of the dye composition.

The composition is preferably aqueous.

In this case, it preferably comprises from 30% to 95% by weight of water, better still from 40% to 90% by weight of water and even better still from 50% to 85% by weight of water relative to the total weight of the composition.

The pH of the composition according to the invention, if it is aqueous, generally ranges from 6 to 1 1 and preferentially from 8.5 to 1 1.

It can be adjusted by adding acidifying agents, such as hydrochloric acid, (ortho)phosphoric acid, sulfuric acid, boric acid, and also carboxylic acids, for instance acetic acid, lactic acid or citric acid, or sulfonic acids. Alkaline agents such as those previously mentioned may also be used.

Dyeing process

The composition described previously is applied to wet or dry keratin fibres, in the presence of at least one oxidizing agent other than atmospheric oxygen. The composition, in the presence of the said oxidizing agent, is usually left in place on the fibres for a time generally of from 1 minute to 1 hour and preferably from 5 minutes to 30 minutes.

The temperature during the dyeing process is conventionally between room temperature (between 15°C and 25°C) and 80°C and preferably between room temperature and 60°C.

After the treatment, the human keratin fibres are advantageously rinsed with water. They may optionally be washed with a shampoo, followed by rinsing with water, before being dried or left to dry.

The composition applied in the process according to the invention is generally prepared extemporaneously before the application, by mixing at least two compositions.

In particular, just before application, a composition (A) free of oxidizing agent other than atmospheric oxygen and comprising at least one oxidation dye, at least one aminoalkane sulfonic, sulfonothioic or sulfinic acid and also salts or amide derivatives or functional analogues thereof, and at least 0.1 % by weight relative to the weight of the said composition of at least one thickening polymer ch osen from n on ion i c, cation ic an d am ph oteri c polym ers , an d m ixtu res th ereof , is mixed with a composition (B) comprising at least one oxidizing agent other than atmospheric oxygen.

Advantageously, compositions (A) and (B) are aqueous.

The term "aqueous composition" means a composition comprising at least 5% by weight of water relative to the weight of this formulation.

Preferably, an aqueous composition comprises more than 10% by weight of water and even more advantageously more than 20% by weight of water.

Composition (A) preferably comprises at least one alkaline agent. It also advantageously comprises one or more fatty substances that are preferably liquid, and advantageously at a total content of at least 10% by weight, and even more preferentially at least 10% by weight of fatty substances that are liquid at room temperature (25°C), relative to the weight of this composition (A).

Advantageously, composition (A) is a direct emulsion (oil-in-water: O/W) or an inverse emulsion (water-in-oil: W/O), and preferably a direct emulsion (O/W).

As regards composition (B) comprising the oxidizing agent as defined previously, it may also comprise one or more acidifying agents as indicated previously.

Usually, the pH of the oxidizing composition, when it is aqueous, is less than 7. Preferably, the oxidizing composition comprises hydrogen peroxide as oxidizing agent, in aqueous solution, the concentration of which varies, more particularly, from 0.1 % to 50%, more particularly between 0.5% and 20% and even more preferably between 1 % and 15% by weight, relative to the weight of the oxidizing composition.

In accordance with one particular variant of the invention, composition (B) comprises at least one fatty substance. Preferably, in the case of this variant, the fatty substance content is at least 5% by weight, and even more preferentially at least 10% by weight, and better still at least 15% of fatty substances that are liquid at room temperature (25°C), relative to the weight of this formulation.

Moreover, compositions (A) and (B) are preferably mixed together before use, in an (A)/(B) weight ratio ranging from 0.2 to 10 and better still from 0.5 to 2.

In addition, the composition used in the process according to the invention, i.e. the composition resulting from mixing together the two compositions (A) and (B), has a fatty substance content preferably of at least 10% by weight of fatty substance, relative to the weight of the composition resulting from mixing together the two abovementioned compositions.

Everything that has been described previously concerning the ingredients of the composition according to the invention remains valid in the case of compositions (A) and (B), the contents taking into account the degree of dilution during mixing.

According to a particularly advantageous embodiment, the mixture of compositions (A) and (B) applied to the fibres is in the form of a foam, in particular in the form of a temporary foam produced just before use.

The composition in foam form is formed from a mixture of air or an inert gas.

At least one of the compositions (A) and (B) may be conditioned in a container pressurized by means of a propellant gas, the foam being obtained after passage through the dispensing orifice(s).

It may also be a case of products dispensed from a container by means of a mechanical pump connected to a dispensing head, the passage of the composition through the dispensing head transforming into foam at the very latest at the outlet orifice of such a head.

It may also be a case of products dispensed from a closed container by means of a dispensing head, the passage of the composition through the dispensing head transforming the composition into foam at the very latest at the outlet orifice of such a head, this being effected by a hand pressing on the container.

Finally, the foam may be obtained by shaking the mixture of the composition according to the invention with an oxidizing composition in a shaker. The example that follows serve to illustrate the invention without, however, being limiting in nature. EXAMPLE

The following compositions are prepared (the amounts are expressed in g% of active material):

Composition 1 :

Composition 2:

Capryl/caprylyl glucoside 1 .8

Tetrasodium etidronate 0.06

Sodium salicylate 0.035

Glycerol 4

Hydrogen peroxide 6

Phosphoric acid qs pH 2.2

Water qs 100 Application method:

The two compositions are mixed together at the time of use in the following proportions: 9 g of composition 1 with 12 g of composition 2.

The mixture thus obtained is readily applied to locks at a rate of 10 g of mixture per 1 g of hair, for 30 minutes at room temperature (20°C).

The hair is then easily rinsed, then washed with a standard shampoo and dried. A light chestnut colour is obtained.

Claims

Composition for dyeing human keratin fibres, comprising:

(a) at least one oxidation dye precursor;

Composition according to Claim 1 , characterized in that the oxidation dye precursor(s) are chosen from oxidation bases, in particular from para- phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, ortho- aminophenols and heterocyclic bases, and the addition salts thereof.

Composition according to Claim 1 , characterized in that the oxidation dye precursor(s) are chosen from couplers, in particular from meta- phenylenediamines, meta-aminophenols, meta-diphenols, naphthalene-based couplers and heterocyclic couplers, and the addition salts of these compounds with an acid.

Composition according to any one of the preceding claims, characterized in that the aminoalkane sulfonic, sulfonothioic or sulfinic acid(s) and also the salts or amide derivatives or functional analogues thereof are chosen from the compounds corresponding to formula (A) or (B) below:

in which:

R denotes hydrogen or a linear Ci-C₄ alkyl radical;

Y denotes S or O;

X denotes hydrogen, a cation M^p+ of valency p, or an organic amine;

Z denotes hydrogen, a cation M^p+ of valency p, or an organic amine;

n is an integer greater than or equal to 2;

p is an integer greater than or equal to 1 . Composition according to the preceding claim, characterized in that, in formulae (A) and (B):

- R denotes hydrogen or a linear C1-C4 alkyl radical and more preferentially methyl;

- p is 1 or 2;

- n is 2 or 3;

- X denotes hydrogen or a cation M^p+ chosen from alkali metals (K⁺, Na⁺), alkaline-earth metals (Mg ²⁺, Ca ²⁺) and the ammonium ion;

- Z denotes hydrogen or a cation M^p+ chosen from alkali metals (Κ⁺' Na⁺), alkaline-earth metals (Mg ²⁺, Ca ²⁺) and the ammonium ion.

Composition according to either of Claims 4 and 5, characterized in that the aminoalkane sulfonic, sulfonothioic or sulfinic acid compounds or salts or amide derivatives thereof are chosen from taurine, N-methyltaurine, thiotaurine, homotaurine and hypotaurine, salts thereof, or mixtures thereof, and preferably taurine, homotaurine or hypotaurine and salts thereof, and even more particularly taurine and salts thereof.

Composition according to any one of Claims 1 to 6, characterized in that the content of aminoalkane sulfonic, sulfonothioic or sulfinic acid compound(s) and also salts or amide derivatives thereof represents from 0.001 % to 20% by weight, preferably from 0.005% to 10% by weight, better still 0.01 % to 5% by weight and even better still 0.1 % to 3% by weight relative to the total weight of the composition.

Composition according to any one of the preceding claims, characterized in that the thickening polymer is chosen from nonionic, cationic and amphoteric non- associative polymers, or nonionic, cationic and amphoteric associative polymers, and also mixtures thereof.

Composition according to any one of the preceding claims, characterized in that the thickening polymer(s) are chosen from:

Non-associative polymers:

a) nonionic guar gums,

b) biopolysaccharide gums of microbial origin, gums derived from plant exudates,

c) celluloses, in particular hydroxypropyl- or carboxymethylcelluloses, d) pectins and alginates,

mixtures thereof; Associative polymers:

a) associative celluloses modified with groups comprising at least one fatty chain comprising from 8 to 30 carbon atoms;

b) quaternized hydroxyethylcelluloses modified with groups comprising at least one fatty chain comprising from 8 to 30 carbon atoms;

c) the cationic polymer(s) obtained by polymerization of a monomer mixture comprising one or more vinyl monomers substituted with one or more amino groups, one or more hydrophobic nonionic vinyl monomers, and one or more associative vinyl monomers;

d) amphoteric associative polymers prepared by copolymerizing:

1 ) at least one monomer of formula (la) or (I la) below:

Z represents an NH group or an oxygen atom,

n is an integer from 2 to 5; one monomer of formula (Ilia):

and

3) at least one monomer of formula (IVa): in which R₆ and R₇, which may be identical or different, represent a hydrogen atom or a methyl radical, X denotes an oxygen or nitrogen atom and R₈ denotes a linear or branched alkyl radical containing from 1 to 30 carbon atoms;

at least one of the monomers of formula (la), (I la) or (Ilia) comprising at least one fatty chain containing 8 to 30 carbon atoms;

e) nonionic associative celluloses modified with groups comprising at least one fatty chain containing 8 to 30 carbon atoms, or modified with alkylphenyl polyalkylene glycol ether groups;

f) associative nonionic hydroxypropyl guars modified with groups comprising at least one fatty chain containing 8 to 30 carbon atoms; g) associative nonionic copolymers of vinylpyrrolidone and of fatty-chain hydrophobic monomers containing 8 to 30 carbon atoms;

h) associative nonionic copolymers of Ci-C₆ alkyl methacrylates or acrylates and of amphiphilic monomers comprising at least one fatty chain containing 8 to 30 carbon atoms;

i) associative nonionic copolymers of hydrophilic acrylates or methacrylates and of hydrophobic monomers comprising at least one fatty chain containing 8 to 30 carbon atoms;

j) associative nonionic polyurethane polyethers comprising in their chain both hydrophilic blocks, which are preferably polyoxyethylenated, and hydrophobic blocks which may be aliphatic sequences alone and/or cycloaliphatic and/or aromatic sequences comprising from 8 to 30 carbon atoms;

k) associative nonionic polymers with an aminoplast ether backbone bearing at least one fatty chain comprising from 8 to 30 carbon atoms; and mixtures thereof.

Composition according to any one of the preceding claims, characterized in that the thickening polymer is chosen from non-ionic and cationic thickening polymers.

Composition according to the preceding claim, characterized in that the thickening polymer(s) are chosen from nonionic non-associative polymers and in particular from guar gums.

12. Composition according to any one of the preceding claims, characterized in that the content of thickening polymer(s) ranges from 0.1 % to 10% by weight, preferably from 0.1 % to 5% by weight and better still from 0.2% to 3% by weight, relative to the total weight of the composition.

13. Composition according to any one of the preceding claims, characterized in that it comprises one or more alkaline agents preferably chosen from aqueous ammonia, alkali metal carbonates or bicarbonates, sodium hydroxide, potassium hydroxide and organic amines whose pKb at 25°C is less than 12, preferably less than 10 and even more advantageously less than 6, and also salts thereof; and mixtures thereof.

14. Composition according to the preceding claim, characterized in that the alkaline agent(s) are chosen from organic amines of the alkanolamine type and basic amino acids, and preferably alkanolamines such as monoethanolamine. 15. Composition according to Claims 12 and 13, characterized in that the content of basifying agent(s) and preferably of organic amine(s) is at least 0.01 % and preferably at least 0.5% by weight relative to the weight of the composition, and advantageously ranges from 0.01 % to 30% by weight and better still from 0.5% to 10% by weight relative to the weight of the said composition.

16. Composition according to any one of the preceding claims, characterized in that it comprises at least one fatty substance preferably chosen from compounds that are liquid or pasty and preferably liquid at room temperature and at atmospheric pressure.

17. Composition according to the preceding claim, characterized in that the fatty substance(s) are chosen from C₆-Ci₆ lower alkanes, non-silicone oils of mineral or synthetic origin, fatty alcohols other than fatty alcohols that are solid at room temperature, esters of fatty acids and/or of fatty alcohols, or mixtures thereof.

18. Composition according to either of Claims 15 and 16, characterized in that the fatty substance concentration is at least 10% by weight, better still at least 15% by weight and more particularly at least 20% by weight, relative to the total weight of the composition, and up to 70% by weight relative to the total weight of the composition.

19. Composition according to any one of the preceding claims, characterized in that it comprises at least one reductone corresponding more particularly to the following formula: R— (HO)C=C(OH) C— R₂

⁰ (C)

with R-i and R₂, which may be identical or different, each denoting a group containing at least one carbon and/or oxygen atom, R-i and R₂ possibly forming with the three carbon atoms of the compound of formula (A) a ring, which is preferably 5- or 6-membered, the additional constituent atoms of which consist of carbon and/or oxygen atoms,

the compound(s) of formula (C) being in acid form, or in the form of salts, especially in the form of salts of alkali metals or of alkaline-earth metals, or in the form of esters, especially of C₈ to C₃₀ fatty acids.

20. Composition according to the preceding claim, characterized in that the reductone(s) are chosen from ascorbic acid, erythorbic acid, and the salts of these compounds, especially the sodium and potassium salts. 21. Composition according to either of Claims 18 and 19, characterized in that the amount of reductone(s) represents from 0.01 % to 1 % by weight, preferably from 0.05% to 0.5% by weight, and better still from 0.1 % to 0.25% by weight, relative to the total weight of the composition. 22. Composition according to any one of the preceding claims, characterized in that it comprises at least one oxidizing agent other than atmospheric oxygen.

23. Process for dyeing human keratin fibres, in which a composition according to any one of Claims 1 to 20 is applied, in the presence of at least one oxidizing agent other than atmospheric oxygen.

24. Process for dyeing human keratin fibres, in which a ready-to-use composition obtained by extemporaneous mixing is applied, before application of the composition according to any one of Claims 1 to 20 with an oxidizing composition comprising at least one oxidizing agent other than atmospheric oxygen.

25. Process according to Claim 23, characterized in that the composition comprising the oxidizing agent other than atmospheric oxygen comprises one or more fatty substances that are liquid at room temperature (25°C), the total content of which represents at least 5% by weight, even more preferentially at least 10% by weight and better still at least 15% of fatty substances that are liquid at room temperature (25°C), relative to the weight of the composition comprising the oxidizing agent other than atmospheric oxygen.

Process according to either of Claims 22 and 23, characterized in that a composition in the form of a foam is applied.

Multi-compartment device suitable for performing the process according to one of Claims 22 to 24, comprising a first compartment containing a composition free of oxidizing agent other than atmospheric oxygen according to any one of Claims 1 to 20; a second compartment containing an oxidizing composition.