WO2012069639A2

WO2012069639A2 - Composition for treating keratin fibres comprising a cationic surfactant comprising a hydroxylated chain

Info

Publication number: WO2012069639A2
Application number: PCT/EP2011/071046
Authority: WO
Inventors: Alain Lagrange; Bruno Laguitton
Original assignee: L'oreal
Priority date: 2010-11-25
Filing date: 2011-11-25
Publication date: 2012-05-31
Also published as: WO2012069639A3

Abstract

One subject of the invention is a composition comprising: (a) at least one cationic surfactant of formula (I) or (I´) below: where: R_1, represent a hydrogen, a C₁-C₆ alkyl, optionally bearing at least one hydroxyl or alkoxy; R₂, which may be identical or different, represent a C₁-C₆ alkyl; R₃ representing a C₈-C₃₂ hydrocarbon-based radical, optionally bearing at least one hydroxyl; -CH₂0-R'₃ with R'₃ representing a C₈-C₃₂ hydrocarbon-based radical, optionally bearing at least one hydroxyl; n is equal to 2 or 3; p is equal to 0 or 1 and the sum of n and p is equal to 3; R'₁, represents a C_1-C₆ alkyl, optionally bearing at least one hydroxyl or alkoxy; R'₂ represents a C_1-C₆ alkyl, optionally bearing at least one hydroxyl or alkoxy; a radical -CH₂-CH(OH)-[CH(OH)]_n'-H with n' representing an integer ranging from 1 to 4; R'₃representing a C₈-C₃₂hydrocarbon-based radical, optionally bearing at least one hydroxyl; a radical -CH(OH)-(CH20)P-R"₃ with R"₃ representing C₈-C₃₂ hydrocarbon- based radical, optionally bearing at least one hydroxyl, p being equal to 0 or 1; m is an integer ranging from 1 to 3; X" represents a counterion; and (b) at least one oxidizing agent; (c) at least one dye or at least one alkaline agent, or mixtures thereof. Other subjects of the invention include a method for treating keratin fibres, in which this composition is applied, and also a multicompartment device comprising, in a first compartment, a composition that is free of oxidizing agent and, in another compartment, a composition comprising this oxidizing agent, the cationic surfactant(s) of formula (I) or (I´) being, without preference, in one and/or the other of the compartments. The invention finally relates to the use of these cationic surfactants of formula (I) or (I´) for dyeing or bleaching human keratin fibres, especially the hair.

Description

COMPOSITION FOR TREATING KERATIN FIBRES COMPRISING A CATIONIC SURFACTANT COMPRISING A HYDROXYLATED CHAIN

One subject of the present invention is a composition for treating keratin fibres, in particular dyeing processes using an oxidizing agent, and that contains a cationic surfactant comprising at least one hydroxylated chain.

Among the methods for dyeing human keratin fibres, such as the hair, mention may be made of oxidation dyeing or permanent dyeing. This dyeing method uses one or more oxidation dye precursors, more particularly one or more oxidation bases optionally combined with one or more couplers which, in the presence of an alkaline agent and an oxidizing agent form, by a process of oxidative condensation, coloured species. The mixing of the dye precursors and the oxidizing agent is carried out at the moment of use.

These oxidation bases are especially selected from ortho- or para- phenylenediamines, ortho- or para-aminophenols, and heterocyclic compounds. These oxidation bases are generally combined with one or more couplers, these couplers being chosen especially from aromatic mefa-diamines, mefa-aminophenols, mefa-diphenols and certain heterocyclic compounds, such as indole compounds. The variety of molecules used as oxidation bases and couplers allows a wide range of colours to be obtained.

One of the drawbacks of the oxidation dyeing processes lies in the fact that the coloration of the composition applied to the fibres changes considerably between the moment of mixing, the start of application and when the composition is finally removed. This phenomenon, entirely conventional, is characteristic of the degree of progression of the aforementioned reaction of oxidative condensation, leading to the appearance of the coloured species.

Thus, depending on the shade chosen, the composition is of a more or less deep or more or less chromatic colour and does not always correspond perfectly to the final coloration of the hair, which may be misleading for the user.

Moreover, the stronger the colour of the composition, the greater are the risks of marking of the skin and the scalp.

The coloration of the composition also results in a drop in the effectiveness of the dyeing operation, the formation of the coloured species taking place in the bowl before application and not in the keratin fibre. Consequently, it is often necessary to use larger amounts of dye precursors than are needed for dyeing the hair in order to compensate for this loss of reagents, giving rise, amongst other things, to an increase in the cost of the composition.

For bleaching keratin fibres use is made, usually, of an oxidizing agent, generally hydrogen peroxide, optionally combined with persalts such as persulphates.

Another drawback observed is linked to the presence of aqueous ammonia or organic amines in the dyeing or bleaching compositions applied to the hair. These alkaline agents are used not only for adjusting the pH of the composition but also for swelling the keratin fibre in order to promote the penetration of the dyes and/or oxidizing agent into the fibre.

As aqueous ammonia is very volatile, the user experiences some annoyances owing to the strong, rather offensive characteristic odour of this agent and sometimes irritation of the scalp, in the form of stinging.

Organic amines also have a certain odour and may also cause scalp irritations. All these drawbacks have to a large extent been overcome by the use of particular formulations that especially comprise fatty-chain cationic surfactants. Such formulations are described, for example, in document FR 292371 1.

To optimize these results it is however necessary to use large amounts of cationic surfactants which is detrimental to the ecotoxic profile of the composition. Consequently, it is important to develop cosmetic compositions that have an improved ecotoxic profile, especially by reducing the amount of cationic surfactants or by using surfactants that are more environmentally-friendly, while retaining identical usage properties.

The objective of the present invention is therefore to propose compositions that are less ecotoxic and that limit the aforementioned drawbacks linked to the coloration of the composition before application to the hair, and to the unpleasant odour linked to the use of an alkaline agent such as aqueous ammonia or organic amines and without degrading the dyeing properties.

One subject of the present invention is thus a composition comprising:

(a ctant of formula (I) or (Γ) below:

(I)

in which formula:

F , which may be identical or different, represent a hydrogen atom, a linear C C₆ alkyl radical or a branched C₃-C₆ alkyl radical, optionally bearing at least one hydroxyl or alkoxy group, the alkyl part of which is a C C₄ alkyl;

R₂, which may be identical or different, represent a linear C C₆ alkyl radical or a branched C₃-C₆ alkyl radical;

R₃ representing a linear or branched C₈-C₃₂ hydrocarbon-based radical that is saturated or that comprises one or more conjugated or unconjugated unsaturated groups, optionally bearing at least one hydroxyl group; a radical -CH₂0-R'₃ with R'₃ representing a linear or branched C₈-C₃₂ hydrocarbon-based radical that is saturated or that comprises one or more conjugated or unconjugated unsaturated groups, optionally bearing at least one hydroxyl group;

n is equal to 2 or 3; p is equal to 0 or 1 and the sum of n and p is equal to 3;

in which formula:

R represents a linear C C₆ alkyl radical or a branched C₃-C₆ alkyl radical, optionally bearing at least one hydroxyl or alkoxy group, the alkyl part of which is a

C1-C4 alkyl;

R'₂ represents a linear C C₆ alkyl radical or a branched C₃-C₆ alkyl radical, optionally bearing at least one hydroxyl or alkoxy group, the alkyl part of which is a C1-C4 alkyl; a radical -CH_rCH(OH)-[CH(OH)]_n ^»H with n' representing an integer ranging from 1 to 4;

R'₃ representing a linear or branched C₈-C₃₂ hydrocarbon-based radical that is saturated or that comprises one or more conjugated or unconjugated unsaturated groups, optionally bearing at least one hydroxyl group; a radical -CH(OH)-(CH₂0)_p- R"₃ with R"₃ representing a linear or branched C₈-C₃₂ hydrocarbon-based radical that is saturated or that comprises one or more conjugated or unconjugated unsaturated groups, optionally bearing at least one hydroxyl group, p being equal to 0 or 1 ;

m is an integer ranging from 1 to 3;

X^" represents a counterion; and

(b) at least one oxidizing agent;

(c) at least one dye chosen from oxidation dye precursors, direct dyes or mixtures thereof, or at least one alkaline agent, or mixtures thereof.

A subject of the invention is also a method for treating human keratin fibres, in which the aforementioned composition is applied to the fibres.

The invention furthermore relates to a multicompartment device comprising a first compartment containing a composition comprising at least one dye chosen from oxidation dye precursors, direct dyes or mixtures thereof, or at least one alkaline agent, or mixtures thereof and a second compartment containing a composition comprising one or more oxidizing agents, at least one of the two compartments comprising at least one cationic surfactant of formula (I) or (Γ).

The invention finally relates to the use of cationic surfactant(s) of formula (I) or (Γ) for dyeing or bleaching human keratin fibres, especially the hair. Other features and advantages of the invention will emerge more clearly on reading the description and the examples that follow.

It should be noted that, in the text hereinbelow, unless otherwise indicated, the limits of a range of values are included in that range.

The human keratin fibres treated according to the invention are preferably the hair. The expression "at least one" is understood to mean "one or more".

As indicated previously, the composition according to the invention comprises at least one cationic surfactant of formula (I) or (Γ) below.

formula (I)

x

are such that:

RL which may be identical or different, represent a hydrogen atom, a linear C C₆ alkyl radical or a branched C₃-C₆ alkyl radical, optionally bearing at least one hydroxyl or alkoxy group, the alkyl part of which is a C C₄ alkyl;

R₃ representing a linear or branched C₈-C₃₂ hydrocarbon-based radical that is saturated or that comprises one or more conjugated or unconjugated unsaturated groups (groups containing carbon-carbon double bonds), optionally bearing at least one hydroxyl group; a radical -CH₂0-R'₃ with R'₃ representing a linear or branched C₈-C₃₂ hydrocarbon-based radical that is saturated or that comprises one or more conjugated or unconjugated unsaturated groups (groups containing carbon-carbon double bonds), optionally bearing at least one hydroxyl group; n is equal to 2 or 3; p is equal to 0 or 1 and the sum of n and p is equal to 3;

X^" represents a counterion.

According to one particular embodiment of the invention, the cationic surfactant(s) of formula (I) are such that R₃ represents a C₈-C₃₂, preferably Ci₀-C₃₀, alkyl radical or a radical -CH₂0-R'₃ with R'₃ representing a C₈-C₃₂, preferably Ci₀-C₃₀, alkyl radical.

Preferably, the radical represents a hydrogen atom.

Furthermore, R₂, which may be identical or different, more particularly represent a Ci-C₄ alkyl radical, preferably a methyl radical.

Preferably, n is equal to 2 and p is equal to 1. The electroneutrality of the cationic surfactants of formula (I) is ensured by the counterion X^" which may be an organic or mineral anion or a mixture of organic or mineral anions.

X^" represents, for example, a halide ion such as chloride, bromide, fluoride or iodide; a hydroxide ion; a sulphate ion; a hydrogensulphate ion; an alkylsulphate ion in which the linear or branched alkyl part is a C C₆ alkyl, such as the methylsulphate or ethylsulphate ion; carbonate and hydrogencarbonate ions; ions derived from carboxylic acids, such as formate, acetate, citrate, tartrate and oxalate ions; alkylsulphonate ions for which the linear or branched alkyl part is a C C₆ alkyl, such as the methylsulphonate ion; arylsulphonate ions for which the aryl part, preferably phenyl, is optionally substituted by one or more C C₄ alkyl radicals, such as, for example, 4-tolylsulphonate; and alkylsulphonyl ions such as mesylate.

As cationic surfactants of formula (I) that are suitable for the implementation of the invention, mention may be made of the following compounds, taken alone or as a mixture:

X^" denotes a counterion as defined previously.

Preferably X^" denotes a chloride ion.

These compounds are known and may, for example, be prepared using one or other of the following two reaction schemes:

Pathway no.1 :

The composition according to the invention advantageously has a content of cationic surfactant(s) of formula (I) ranging from 0.01 % to 20%, more particularly from 0.1 % to 10%, and preferably from 0.5% to 5% by weight relative to the total weight of the composition.

The cationic surfactant(s) of formula (Γ) below:

are such that:

R represents a linear C C₆ alkyl radical or a branched C₃-C₆ alkyl radical, optionally bearing at least one hydroxyl or alkoxy group, the alkyl part of which is a C1-C4 alkyl;

R'₂ represents a linear C C₆ alkyl radical or a branched C₃-C₆ alkyl radical, optionally bearing at least one hydroxyl or alkoxy group, the alkyl part of which is a C1-C4 alkyl; a radical -CH₂-CH(OH)-[CH(OH)]_n-H with n' representing an integer ranging from 1 to 4;

R'₃ representing a linear or branched C₈-C₃₂ hydrocarbon-based radical that is saturated or that comprises one or more conjugated or unconjugated unsaturated groups (groups containing carbon-carbon double bonds), optionally bearing at least one hydroxyl group; a radical -CH(OH)-(CH₂0)_p-R"₃ with R"₃ representing a linear or branched C₈-C₃₂ hydrocarbon-based radical that is saturated or that comprises one or more conjugated or unconjugated unsaturated groups (groups containing carbon-carbon double bonds), optionally bearing at least one hydroxyl group, p being equal to 0 or 1 ;

m is an integer ranging from 1 to 3;

X^" represents a counterion. According to one particular embodiment of the invention, the cationic surfactant(s) of formula (Γ) are such that R'₃ represents a C₈-C₃₂, preferably Ci₀-C₃₀, alkyl radical, or a radical -CH(OH)-(CH₂0)p-R"₃ with R"₃ representing a C₈-C₃₂, preferably Ci₀-C₃₀, alkyl radical, p being equal to 0 or 1.

Moreover, and more particularly, m is equal

Preferably, the radical R'^ represents a C C₄ alkyl radical.

Furthermore, R'₂ more particularly represents a C C₄ alkyl radical or a radical -CH₂- CH(OH)-[CH(OH)]n'-H with n' representing an integer ranging from 1 to 3. Advantageously, n' is equal to 3. More advantageously still, R'₂ represents a C C₄ alkyl radical.

The electroneutrality of the cationic surfactants of formula (Γ) is ensured by the counterion X^" which may be an organic or mineral anion or a mixture of organic or mineral anions.

X^" represents, for example, a halide ion such as chloride, bromide, fluoride or iodide; a hydroxide ion; a sulphate ion; a hydrogensulphate ion; an alkylsulphate ion in which the linear or branched alkyl part is a C C₆ alkyl, such as the methylsulphate or ethylsulphate ion; carbonates and hydrogencarbonates; an ion derived from a carboxylic acid, such as formate, acetate, citrate, tartrate and oxalate ions; alkylsulphonate ions for which the linear or branched alkyl part is a C C₆ alkyl, such as the methylsulphonate ion; arylsulphonate ions for which the aryl part, preferably phenyl, is optionally substituted by one or more C C₄ alkyl radicals, such as, for example, the 4-tolylsulphonate ion; and alkylsulphonyl ions such as mesylate.

As cationic surfactants of formula (Γ) that are suitable for the implementation of the invention, mention may be made of the following compounds, taken alone or as a mixture:

X^" denoting a counterion as defined previously.

Preferably X^" denotes a chloride ion.

These surfactants are known and are especially described in WO 01/05224, and also in the publication by Gregan et al., Chem Papers, 50 (5), 310-315 (1996).

The composition according to the invention advantageously has a content of cationic surfactant(s) of formula (I) or (Γ) ranging from 0.01 % to 20% by weight, more particularly from 0.1 % to 10% by weight, and preferably from 0.5% to 5% by weight relative to the total weight of the composition.

The composition according to the invention comprises at least one oxidizing agent.

In particular, this oxidizing agent is chosen from hydrogen peroxide, urea peroxide, alkali metal bromates or ferricyanides, peroxygenated salts, for instance persulphates, perborates and percarbonates of alkali metals or alkaline-earth metals, such as sodium, potassium and magnesium.

The oxidizing agent is preferably hydrogen peroxide. As was indicated previously, the composition according to the invention may comprise one or more oxidation dye precursors. These oxidation dye precursors are chosen from oxidation bases and couplers.

The oxidation bases may be chosen from para-phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, orf 70-aminophenols and heterocyclic bases, and the addition salts thereof.

Among the para-phenylenediamines that may be mentioned, for example, are para- phenylenediamine, para-toluenediamine, 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, N- -hydroxypropyl)-para- phenylenediamine, 2-hydroxymethyl-para-phenylenediamine, N,N-dimethyl-3-methyl- para-phenylenediamine, N,N-(ethyl^-hydroxyethyl)-para-phenylenediamine, Ν-(β,γ- dihydroxypropyl)-para-phenylenediamine, N-(4'-aminophenyl)-para-phenylenediamine, N- phenyl-para-phenylenediamine, 2-β-hydroxyethyloxy-paΓa-phenylenediamine, 2-β- acetylaminoethyloxy-para-phenylenediamine, N-^-methoxyethyl)-para-phenylenediamine, 4-aminophenylpyrrolidine, 2-thienyl-para-phenylenediamine, 2-β-hydroxyethylamino-5- aminotoluene, 3-hydroxy-1-(4'-aminophenyl)pyrrolidine, and the addition salts thereof with an acid.

Among the para-phenylenediamines mentioned above, para-phenylenediamine, para-toluenediamine, 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-β-acetylaminoethyloxy-para-phenylenediamine, and the addition salts thereof with an acid, are particularly preferred.

Among the bis(phenyl)alkylenediamines that may be mentioned, for example, are N,N'-bis(β-hydroxyethyl)-N,N'-bis(4'-aminophenyl)-1 ,3-diaminopropanol, N,N'-bis(β- hydroxyethyl)-N,N'-bis(4'-aminophenyl)ethylenediamine, N,N'-bis(4-aminophenyl)- tetramethylenediamine, N,N'-bis^-hydroxyethyl)-N,N'-bis(4-amino- phenyl)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-(β-hydroxyethylaminomethyl)phenol and 4-amino-2-fluorophenol, and the addition salts thereof with an acid.

Among the o/f/70-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 that may be mentioned, for example, are 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 that are useful in the present invention are the 3- aminopyrazolo[1 ,5-a]pyridine oxidation bases or the addition salts thereof described, for example, in patent application FR 2 801 308. Examples that may be mentioned include pyrazolo[1 ,5-a]pyrid-3-ylamine, 2-acetylaminopyrazolo[1 ,5-a]pyrid-3-ylamine, 2-morpholin- 4-ylpyrazolo[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- ylpyrazolo[1 ,5-a]pyrid-3-ylamine, pyrazolo[1 ,5-a]pyridine-3,5-diamine, 5-morpholin-4- ylpyrazolo[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 and 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 the patents DE 2359399; JP 88-169571 ; JP 05-63124; EP 0770375 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 their addition salts and their tautomeric forms, when a tautomeric equilibrium exists.

Among the pyrazole derivatives that may be mentioned 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-methyl- pyrazole, 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-phenyl- pyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1 ,3-dimethyl-5-hydrazino- pyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-te/f-butyl-1-methyl- pyrazole, 4,5-diamino-1-te/f-butyl-3-methylpyrazole, 4,5-diamino-1-^-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-(β-hydroxyethyl)amino-1-methylpyrazole, and the addition salts thereof. 4,5-Diamino-1-^-methoxyethyl)pyrazole may also be used.

Pyrazole derivatives that may also be mentioned include diamino-N,N- dihydropyrazolones and especially those described in patent application FR 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, 2,3-diamino-6-hydroxy-6,7-dihydro-1 H,5H-pyrazolo[1 ,2-a]pyrazol-1- one.

Heterocyclic bases that will preferentially be used include 4,5-diamino-1- - hydroxyethyl)pyrazole and/or 2,3-diamino-6,7-dihydro-1 H,5H-pyrazolo[1 ,2-a]-pyrazol-1- one and the addition salts thereof.

Among the couplers, mention may be made of mefa-phenylenediamines, meta- aminophenols, mefa-diphenols, naphthalene-based couplers and heterocyclic couplers, and also the addition salts thereof.

Mention may be made, for example, of 1 ,3-dihydroxybenzene, 1 ,3-dihydroxy-2- methylbenzene, 4-chloro-1 ,3-dihydroxybenzene, 2,4-diamino-1-(B-hydroxyethyloxy)- benzene, 2-amino-4-(B-hydroxyethylamino)-1-methoxybenzene, 1 ,3-diaminobenzene, 1 ,3- bis(2,4-diaminophenoxy)propane, 3-ureidoaniline, 3-ureido-1-dimethylaminobenzene, sesamol, 1-B-hydroxyethylamino-3,4-methylenedioxybenzene, a-naphthol, 2-methyl-1- naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole, 2-amino-3- hydroxypyridine, 6-hydroxybenzomorpholine, 3,5-diamino-2,6-dimethoxypyridine, 1-Ν-(β- hydroxyethyl)amino-3,4-methylenedioxybenzene, 2,6-bis(B-hydroxyethylamino)toluene, 6- hydroxyindoline, 2,6-dihydroxy-4-methylpyridine, 1-H-3-methylpyrazol-5-one, 1-phenyl-3- methylpyrazol-5-one, 2,6-dimethylpyrazolo[1 ,5-b]-1 ,2,4-triazole, 2,6-dimethyl[3,2-c]-1 ,2,4- triazole and 6-methylpyrazolo[1 ,5-a]benzimidazole, the addition salts thereof with an acid, and mixtures thereof.

In general, the addition salts of the oxidation bases and couplers that may be used in the context of the invention are especially selected from the addition salts with an acid such as the hydrochlorides, hydrobromides, sulphates, citrates, succinates, tartrates, lactates, tosylates, benzenesulphonates, phosphates and acetates.

The oxidation base(s) each represent, when they are present, 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.

The coupler(s) each represent, when they are present, 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. The composition may also comprise one or more direct dyes. These direct dyes are chosen, for example, from neutral, acidic or cationic nitrobenzene direct dyes, neutral, acidic or cationic azo direct dyes, tetraazapentamethine dyes, neutral, acidic or cationic quinone and in particular anthraquinone dyes, azine direct dyes, triarylmethane direct dyes, indoamine direct dyes and natural direct dyes.

Among the nitrobenzene direct dyes that may be mentioned, in a non-limiting manner, are the following compounds:

1 ,4-diamino-2-nitrobenzene, 1-amino-2-nitro-4^- hydroxyethylaminobenzene, 1- amino-2-nitro-4-bis^-hydroxyethyl)aminobenzene, 1 ,4-bis^-hydroxyethylamino)-2- nitrobenzene, 1-β-hydroxyethylamino-2-nitro-4-bis(β-hydroxyethylamino)benzene, 1-β- hydroxyethylamino-2-nitro-4-aminobenzene, 1^-hydroxyethylamino-2-nitro-4-(ethyl)^- hydroxyethyl)aminobenzene, 1-amino-3-methyl-4^-hydroxyethylamino-6-nitrobenzene, 1- amino-2-nitro-4^-hydroxyethylamino-5-chlorobenzene, 1 ,2-diamino-4-nitrobenzene, 1 - amino-2^-hydroxyethylamino-5-nitrobenzene, 1 ,2-bis^-hydroxyethylamino)-4- nitrobenzene, 1-amino-2-tris(hydroxymethyl)methylamino-5-nitrobenzene, 1-hydroxy-2- amino-5-nitrobenzene, 1-hydroxy-2-amino-4-nitrobenzene, 1-hydroxy-3-nitro-4- aminobenzene, 1 -hydroxy-2-amino-4,6-dinitrobenzene, 1 ^-hydroxyethyloxy-2^- hydroxyethylamino-5-nitrobenzene, 1 -methoxy-2^-hydroxyethylamino-5-nitrobenzene, 1 - β-hydroxyethyloxy-3-methylamino-4-nitrobenzene, 1^,v-dihydroxypropyloxy-3- methylamino-4-nitrobenzene, 1^-hydroxyethylamino-4^,Y-dihydroxypropyloxy-2- nitrobenzene, 1-β,γ-dihydroxypropylamino-4-trifluoromethyl-2-nitrobenzene, 1-β- hydroxyethylamino-4-trifluoromethyl-2-nitrobenzene, 1^-hydroxyethylamino-3-methyl-2- nitrobenzene, 1^-aminoethylamino-5-methoxy-2-nitrobenzene, 1-hydroxy-2-chloro-6- ethylamino-4-nitrobenzene, 1 -hydroxy-2-chloro-6-amino-4-nitrobenzene, 1 -hydroxy-6- bis^-hydroxyethyl)amino-3-nitrobenzene, 1 ^-hydroxyethylamino-2-nitrobenzene, 1 - hydroxy-4^-hydroxyethylamino-3-nitrobenzene.

Among the azo direct dyes, mention may be made of the cationic azo dyes described in patent applications WO-95/15144, WO-95/01772 and EP-714 954, the content of which forms an integral part of the invention.

Among these compounds, mention may be made very particularly of the following dyes: 1 ,3-dimethyl-2-[[4-(dimethylamino)phenyl]azo]-1 H-imidazolium chloride, 1 ,3- dimethyl-2-[(4-aminophenyl)azo]-1 H-imidazolium chloride, 1-methyl-4-[(methylphenyl hydrazono)methyl]pyridinium methyl sulphate.

Among the azo direct dyes, mention may also be made of the following dyes, described in the Colour Index International 3rd edition:

Disperse Red 17, Acid Yellow 9, Acid Black 1 , Basic Red 22, Basic Red 76, Basic

Yellow 57, Basic Brown 16, Acid Yellow 36, Acid Orange 7, Acid Red 33, Acid Red 35, Basic Brown 17, Acid Yellow 23, Acid Orange 24, Disperse Black 9.

Mention may also be made of 1-(4'-aminodiphenylazo)-2-methyl-4-bis - hydroxyethyl)aminobenzene and 4-hydroxy-3-(2-methoxyphenylazo)-1- naphthalenesulphonic acid.

Among the quinone direct dyes that may be mentioned are the following dyes:

Disperse Red 15, Solvent Violet 13, Acid Violet 43, Disperse Violet 1 , Disperse Violet 4, Disperse Blue 1 , Disperse Violet 8, Disperse Blue 3, Disperse Red 1 1 , Acid Blue 62, Disperse Blue 7, Basic Blue 22, Disperse Violet 15, Basic Blue 99, and also the following compounds: 1-N-methylmorpholiniumpropylamino-4-hydroxyanthraquinone, 1- aminopropylamino-4-methylaminoanthraquinone, 1-aminopropylaminoanthraquinone, 5-β- hydroxyethyl-1 ,4-diaminoanthraquinone, 2-aminoethylaminoanthraquinone, 1 ,4-bis^,v- dihydroxypropylamino)anthraquinone.

Among the azine dyes that may be mentioned are the following compounds:

- Basic Blue 17 and Basic Red 2.

Among the triarylmethane dyes, mention may be made of the following compounds: Basic Green 1 , Acid Blue 9, Basic Violet 3, Basic Violet 14, Basic Blue 7, Acid Violet 49, Basic Blue 26, Acid Blue 7.

Among the indoamine dyes, mention may be made of the following compounds: -2-β-hydroxyethlyamino-5-[bis(β-4'-hydroxyethyl)amino]anilino-1 ,4-benzoquinone;

-2-β-hydroxyethylamino-5-(2'-methoxy-4'-amino)anilino-1 ,4-benzoquinone;

-3-N-(2'-chloro-4'-hydroxy)phenylacetylamino-6-methoxy-1 ,4-benzoquinone imine;

-3-N-(3'-chloro-4'-methylamino)phenylureido-6-methyl-1 ,4-benzoquinone imine;

-3-[4'-N-(ethyl,carbamylmethyl)amino]phenylureido-6-methyl-1 ,4-benzoquinone imine.

Among the natural direct dyes, mention may be made of lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, protocatechaldehyde, indigo, isatin, curcumin, spinulosin and apigenidin. Extracts or decoctions containing these natural dyes and especially henna-based poultices or extracts, may also be used.

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

The composition may also comprise at least one alkaline agent. More particularly, the alkaline agent is chosen from mineral or organic or hybrid alkaline agents, or mixtures thereof.

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

The organic alkaline agent(s) are preferably chosen from organic amines with a pK 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 pK corresponding to the function of highest basicity.

Hybrid compounds that may be mentioned include the salts of the amines mentioned previously with acids such as carbonic acid or hydrochloric acid.

The abovementioned organic amines, with a pK at 25°C of less than 12 are chosen, for example, from alkanolamines, oxyethylenated and/or oxypropylenated ethylenediamines, amino acids and the compounds of formula (A) below:

^ N - W- N

Ry Rt

(A)

in which W is a C 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 C C₆ alkyl, C C₆ hydroxyalkyl or C C₆ 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 C C₈ alkyl groups bearing one or more hydroxyl radicals.

Alkanolamines such as monoalkanolamines, dialkanolamines or trialkanolamines comprising from one to three identical or different C C₄ hydroxyalkyl radicals are in particular suitable for performing the invention.

Among the 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, sulphonic acid, phosphonic acid or phosphoric acid functions. The amino acids may be in neutral or ionic form.

As amino acids that may 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, taurine, 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 formula

(B) below:

NH

/ ²

R— CH₂— CH_X (B)

C0₂H

i enotes a group chosen from:

-(CH₂)₃NH₂

-(CH₂)₂NH₂ -(CH₂)₂NHCONH₂

-(CH₂)₂NH C— NH₂

NH

The compounds corresponding to formula (B) 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 may 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 baleine.

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 that 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, 4-guanidinobutyric acid and 2- ([amino(imino)methyl]amino)ethane-1-sulphonic acid.

Mention may be made in particular of the use of guanidine carbonate or monoethanolamine hydrochloride as hybrid compounds. The composition of the invention preferably contains aqueous ammonia and/or an alkanolamine such as monoethanolamine.

Advantageously, the composition according to the invention has a content of alkaline agent(s), if it (they) is (are) present, ranging from 0.01 % to 30% by weight and preferably from 0.1 % to 20% by weight relative to the total weight of said composition. The composition according to the invention may also comprise one or more fatty esters.

The expression "fatty esters", within the meaning of the present invention, is understood more particularly to mean an ester of a carboxylic acid comprising in its structure a fatty chain with at least 10 carbon atoms, preferably having from 10 to 30 carbon atoms, preferably from 10 to 22 carbon atoms, and of an alcohol which is preferably a monoalcohol, especially CrC₃₀, more particularly C C₂2, or a sugar.

More particularly, these compounds are chosen from:

- esters of saturated, linear or branched CrC₃₀ monoalcohols, with Ci₀-C₃₀ monofunctional fatty acids, it being possible for the latter to be linear or branched, saturated or unsaturated;

- esters of linear or branched C₃-C₈ monoalcohols, with Ci₀-C₃₀ bifunctional fatty acids, it being possible for the latter to be linear or branched, saturated or unsaturated;

- esters and diesters of sugars and of Ci₀-C₃₀ fatty acids: and

- mixtures thereof.

As regards the esters of saturated, linear or branched C C₃₀ monoalcohols, with Cio-C₃₀ monofunctional fatty acids, the latter may be linear or branched, saturated or unsaturated. If they are unsaturated, these compounds may comprise one to three conjugated or unconjugated carbon-carbon double bonds (-C=C-).

According to one preferred embodiment of the invention, these esters may be selected in particular from oleate, laurate, palmitate, myristate, behenate, cocoate, stearate, linoleate, linolenate, caprate, arachidonate, or mixtures thereof, in particular such as the oleopalmitates, oleostearates and palmitostearates of C C₃₀ monoalcohols. Among these esters, use is more particularly made of isopropyl palmitate, isopropyl myristate, octyldodecyl stearate and isononyl isononaoate.

Among the esters of linear or branched C₃-C₈ monoalcohols, with bifunctional, linear or branched, saturated or unsaturated Ci₂-C₃₀ fatty acids, that may be more particularly cited are the isopropyl diester of sebacic acid, also known as diisopropyl sebacate.

The composition may also comprise, as fatty ester, sugar esters and diesters of Ci₀- C₃₀ fatty acids. It is recalled that the term "sugar" means compounds that have several alcohol functions, with or without aldehyde or ketone functions, and which comprise at least 4 carbon atoms. These sugars may be monosaccharides, oligosaccharides or polysaccharides.

Examples of suitable sugars that may be mentioned include sucrose (or saccharose), glucose, galactose, ribose, fucose, maltose, fructose, mannose, arabinose, xylose and lactose, and derivatives thereof, especially alkyl derivatives, such as methyl derivatives, for instance methylglucose.

The sugar esters of fatty acids may be selected especially from the group comprising the esters or mixtures of esters of sugars described previously and of linear or branched, saturated or unsaturated C10-C22 fatty acids. If they are unsaturated, these compounds may comprise one to three conjugated or unconjugated carbon-carbon double bonds.

The esters may also be selected from monoesters, diesters, triesters, tetraesters and polyesters, and mixtures thereof.

These esters may be, for example, oleates, laurates, palmitates, myristates, behenates, cocoates, stearates, linoleates, linolenates, caprates and arachidonates of sugar(s), or mixtures thereof such as, especially, oleopalmitate, oleostearate and palmitostearate mixed esters of sugar(s).

More particularly, use is made of monoesters and diesters and especially sucrose, glucose or methylglucose monooleates or dioleates, stearates, behenates, oleopalmitates, linoleates, linolenates and oleostearates.

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, F110, F90, F70 and SL40 by the company Crodesta, respectively denoting sucrose palmitostearates 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, triester and polyester;

-the sucrose monodipalmitostearate sold by the company Goldschmidt under the name Tegosoft® PSE.

Preferably, use is made, as fatty ester, of compounds chosen from esters of saturated, linear or branched C Ci₈ monoalcohols, with Ci₄-Ci₈ monofunctional fatty acids, it being possible for the latter to be linear or branched, saturated or unsaturated.

When they are present, the composition according to the invention has a content of fatty ester(s) ranging advantageously from 0.3% to 12.5% by weight, preferably from 0.5% to 10% by weight relative to the total weight of the composition. The composition according to the invention may furthermore comprise one or more fatty alcohols.

More particularly, said fatty alcohol is chosen from non-(poly)oxyalkylenated (the alkyl having 1 to 3 carbon atoms) and non-(poly)glycerolated alcohols, comprising one or more fatty chains having from 10 to 30 carbon atoms, more particularly from 14 to 22 carbon atoms and more advantageously still from 16 to 18 carbon atoms, which are saturated or unsaturated, the fatty chains optionally being substituted by one or two additional hydroxyl groups. When the alcohol is unsaturated, it comprises from 1 to 3 conjugated or unconjugated carbon-carbon double bonds (-C=C-). Preferably, the fatty alcohol is a monoalcohol.

As examples of fatty alcohols, mention may be made of lauryl, cetyl, stearyl, behenyl, myristyl, linoleyl, undecylenyl, palmitoleyl, linolenyl, arachidonyl, erucyl, isocetyl, isostearyl and isobehenyl alcohols, oleyl alcohol and mixtures thereof.

Preferably, the composition comprises one or more non-(poly)oxyalkylenated and non-(poly)glycerolated fatty monoalcohols, comprising from 14 to 22 carbon atoms and more specifically from 16 to 18 carbon atoms, which are saturated.

According to one embodiment of the invention, the composition has a content of fatty alcohol(s) ranging from 1 % to 25% by weight, relative to the total weight of the composition, preferably from 3% to 20% by weight and in accordance with one even more preferred variant of the invention, from 5% to 18% by weight. The composition according to the invention comprises water or a mixture of water and one or more organic solvents.

Examples of organic solvents that may be mentioned include linear or branched C₂-

C₄ alkanols, such as ethanol and isopropanol; glycerol; glycols and glycol ethers, for instance 2-butoxyethanol, propylene glycol, dipropylene glycol, propylene glycol monomethyl ether and diethylene glycol monomethyl ether or monoethyl ether, and also aromatic alcohols, for instance benzyl alcohol or phenoxyethanol, and mixtures thereof.

The solvent(s) may be present in proportions preferably ranging from 1 % to 90% by weight relative to the weight of the composition, and even more preferentially from 5% to

80 % by weight.

The composition according to the invention may also optionally comprise one or more cationic or amphoteric substantive polymers.

The substantive character (i.e. the capacity for deposition on the hair) of the polymers is determined conventionally using the test described by Richard J. Crawford, Journal of the Society of Cosmetic Chemists, 1980, 31 - (5) - pages 273 to 278 (detection by Red 80 acid dye).

These substantive polymers are described especially in Patent Application EP 557 203.

More particularly, use may be made of polymers selected from cationic cellulose derivatives, homopolymers of dimethyldiallylammonium halide and copolymers of dimethyldiallylammonium halide and of (meth)acrylic acid; homopolymers and copolymers of methacryloyloxyethyltrimethylammonium halide; quaternary polyammonium polymers; vinylpyrrolidone polymers with cationic units; cationic polysiloxanes; and mixtures thereof. Among the substantive polymers of the dimethyldiallylammonium halide copolymer type that can be used according to the invention, mention may be made in particular of: - the copolymers of diallyldimethylammonium chloride and acrylic acid such as that with proportions (80/20 by weight) sold under the name Merquat 280 by the company Calgon;

- the copolymers of dimethyldiallylammonium chloride and acrylamide sold under the names Merquat 550 and Merquat S by the company Merck.

Among the substantive polymers of the methacryloyloxyethyltrimethylammonium halide polymer type that can be used according to the invention, mention may be made in particular of the products that are known in the CTFA dictionary (5th edition, 1993) as "Polyquaternium 37", "Polyquaternium 32" and "Polyquaternium 35", which correspond respectively, with respect to "Polyquaternium 37", to crosslinked poly(methacryloyloxyethyltrimethylammonium chloride), in dispersion at 50% in mineral oil, and sold under the name Salcare SC95 by the company Allied Colloids; with respect to "Polyquaternium 32", to the crosslinked copolymer of acrylamide and methacryloyloxyethyltrimethylammonium chloride (20/80 by weight), in dispersion at 50% in mineral oil, and sold under the name Salcare SC92 by the company Allied Colloids; and with respect to "Polyquaternium 35", to the methosulphate of the methacryloyloxyethyl- trimethylammonium/methacryloyloxyethyldimethylacetylammonium copolymer, sold under the name Plex 7525L by the company Rohm GmbH.

The substantive polymers of the quaternary polyammonium type that can be used according to the invention are as follows:

- the polymers prepared and described in French patent 2 270 846, constituted of repeating units corresponding to formula (1) below:

CH₃ CH₃

especially those whose molecular weight, determined by gel permeation chromatography, is between 9500 and 9900;

- the polymers prepared and described in French patent 2 270 846, constituted of repeati ula (2) below:

especially those whose molecular weight, determined by gel permeation chromatography, is about 1200; - the polymers prepared and described in US patents 4 157 388, 4 390 689, 4 702 906, 4 719 282, constituted of repeating units corresponding to formula (3)

below:

CH, CI CI CH,

' + i ₊

-N - (CH^ NH-CO D -NH-(CH₂)p - N - (CH₂)₂ - O— (CH₂)₂ ^■

I

CH, CH₃ in which p denotes an integer ranging from 1 to 6 approximately, D may be zero or may represent a group (CH₂)_r-CO- in which r denotes a number equal to 4 or 7,

and especially those whose molecular weight is less than 100 000, preferably less than or equal to 50 000; such polymers are especially sold by the company Miranol under the names "Mirapol A15", "Mirapol AD1", "Mirapol AZ1" and "Mirapol 175";

Among the vinylpyrrolidone polymers (PVP) with cationic units that can be used in accordance with the invention, mention may be made in particular of:

a) vinylpyrrolidone polymers containing dimethylaminoethyl methacrylate units; among these, mention may be made of:

- the vinylpyrrolidone/dimethylaminoethyl methacrylate copolymer (20/80 by weight) sold under the trade name Copolymer 845 by the company ISP,

- the vinylpyrrolidone/dimethylaminoethyl methacrylate copolymers quaternized by diethyl sulphate, sold under the names Gafquat 734, 755, 755 S and 755 L by the company ISP,

- the PVP/dimethylaminoethyl methacrylate/hydrophilic polyurethane copolymers sold under the trade name Pecogel GC-310 by the company U.C.I.B., or under the names Aquamere C 1031 and C 1511 by the company Blagden Chemicals,

- the quaternized or unquaternized PVP/dimethylaminoethyl methacrylate/C8 to C16 olefin copolymers, sold under the names Ganex ACP 1050 to 1057, 1062 to1069, 1079 to 1086, by the company ISP,

- the PVP/dimethylaminoethyl methacrylate/vinylcaprolactam copolymer sold under the name Gaffix VC 713 by the company ISP,

b) vinylpyrrolidone polymers containing methacrylamidopropyltrimethylammonium chloride (MAPTAC) units , among which, mention may be made especially of:

- the vinylpyrrolidone/MAPTAC copolymers sold under the trade names Gafquat

ACP 101 1 and Gafquat HS 100 by the company ISP,

c) the vinylpyrrolidone polymers containing methylvinylimidazolium units, and among which, mention may be made more particularly of:

- the PVP/methylvinylimidazolium chloride copolymers sold under the names Luviquat FC 370, FC 550, FC 905, HM 552 by the company BASF,

- the PVP/methylvinylimidazolium chloride/vinylimidazole terpolymer sold under the name Luviquat 8155 by the company BASF, - the PVP/methylvinylimidazolium methosulphate copolymer sold under the name Luviquat MS 370 by the company BASF.

Among the cationic polysiloxanes, mention may especially be made of:

(a) the compounds corresponding to formula (4) below:

(R1)a(T)₃-a-Si[OSi(T)₂]_n-[OSi(T)_b(R1)₂._b]_m-OSi(T)₃-a-(R1)a (4)

in which:

T is a hydrogen atom or a phenyl, hydroxyl (-OH) or Ci-Cs alkyl radical, and preferably methyl, or a C C₈ alkoxy, preferably methoxy,

a denotes the number 0 or an integer from 1 to 3, and preferably 0,

b denotes 0 or 1 , and in particular 1 ,

m and n are numbers such that the sum (n + m) can range especially from 1 to 2000 and in particular from 50 to 150, it being possible for n to denote a number from 0 to 1999 and in particular from 49 to 149, and for m to denote a number from 1 to 2000 and in particular from 1 to 10;

R1 is a monovalent radical of formula -C_qH_2qL in which q is a number from 2 to 8 and L is an optionally quaternized amino group chosen from the following groups:

-N(R2)-CH₂-CH₂-N(R2)₂;

-N(R2)₂; -N⁺(R2)₃Q^";

-N⁺(R2)(H)₂Q-;

-N⁺(R2)₂HQ-;

-N(R2)-CH₂-CH₂-N⁺(R2)(H)₂Cr,

in which R2 can denote a hydrogen atom, a phenyl, a benzyl or a saturated monovalent hydrocarbon-based radical, for example a CiC₂₀ alkyl radical, and Q^" represents a halide ion such as, for example, fluoride, chloride, bromide or iodide.

In particular, the amino silicones corresponding to the definition of formula (5) are chosen from the compounds corresponding to the following formula:

in which R, R' and R", which may be identical or different, denote a C C₄ alkyl radical, preferably CH₃; a C C₄ alkoxy radical, preferably methoxy; or OH; A represents a linear or branched, C₃-C₈ and preferably C₃-C₆ alkylene radical; m and n are integers dependent on the molecular weight and whose sum is between 1 and 2000. According to a first possibility, R, R' and R", which may be identical or different, represent a C C₄ alkyl or hydroxyl radical, A represents a C₃ alkylene radical and m and n are such that the weight-average molecular weight of the compound is between 5000 and 500 000 approximately. Compounds of this type are referred to in the CTFA dictionary as "amodimethicones".

According to a second possibility, R, R' and R", which may be identical or different, represent a C C₄ alkoxy or hydroxyl radical, at least one of the radicals R or R" is an alkoxy radical and A represents a C₃ alkylene radical. The hydroxy/alkoxy molar ratio is preferably between 0.2/1 and 0.4/1 and advantageously equal to 0.3/1. Moreover, m and n are such that the weight-average molecular weight of the compound is between 2000 and 10⁶. More particularly, n is between 0 and 999 and m is between 1 and 1000, the sum of n and m being between 1 and 1000.

In this category of compounds, mention may be made, inter alia, of the product Belsil® ADM 652 sold by Wacker.

According to a third possibility, R and R", which are different, represent a C C₄ alkoxy or hydroxyl radical, at least one of the radicals R or R" is an alkoxy radical, R' represents a methyl radical and A represents a C₃ alkylene radical. The hydroxy/alkoxy molar ratio is preferably between 1/0.8 and 1/1.1 and advantageously is equal to 1/0.95. Moreover, m and n are such that the weight-average molecular weight of the compound is between 2000 and 200 000. More particularly, n is between 0 and 999 and m is between 1 and 1000, the sum of n and m being between 1 and 1000.

More particularly, mention may be made of the product Fluid WR® 1300 sold by Wacker.

According to a fourth possibility, R and R" represent a hydroxyl radical, R' represents a methyl radical and A is a C₄-C₈ and preferably C₄ alkylene radical. Moreover, m and n are such that the weight-average molecular weight of the compound is between 2000 and 10⁶. More particularly, n is between 0 and 1999 and m is between 1 and 2000, the sum of n and m being between 1 and 2000.

A product of this type is especially sold under the name DC 28299 by Dow Corning. Note that the molecular weight of these silicones is determined by gel permeation chromatography (room temperature, polystyrene standard; μ styragem columns; THF eluent; flow rate of 1 mm/m; 200 μΙ of a solution containing 0.5% by weight of silicone in THF are injected, and detection is performed by refractometry and using a UV-meter).

A product corresponding to the definition of formula (5) is in particular the polymer known in the CTFA dictionary as "trimethylsilylamodimethicone", corresponding to formula (6) below: (CH₃)₃ i(CH₃)₃

NH,

(6)

in which n and m have the meanings given above in accordance with formula (5).

Such compounds are described, for example, in patent EP 95238; a compound of formula (5) is sold, for example, under the name Q2-8220 by the company OSI.

(b) the compounds corresponding to formula (7) below:

R—

in which:

R³ represents a monovalent C Ci₈ hydrocarbon-based radical, and in particular a C Ci₈ alkyl or C₂-Ci₈ alkenyl radical, for example methyl;

R⁴ represents a divalent hydrocarbon-based radical, especially a C Ci₈ alkylene radical or a divalent C Ci₈, and for example C C₈, alkylenoxy radical;

Q^" is a halide ion, especially chloride;

r represents a mean statistical value from 2 to 20 and in particular from 2 to 8;

s represents a mean statistical value from 20 to 200 and in particular from 20 to 50.

Such compounds are described more particularly in patent US 4185087.

A compound falling within this class is the product sold by the company Union Carbide under the name Ucar Silicone ALE 56.

(c) the quaternary ammonium silicones of formula (8):

2X

R₇ OH

i ; I I ' I

- N - C TCH-CH - R, - Si - - Si - - R_E - CH ₂ CHOH - CH₂ - N - R,

I ² I

R, R, R, R,

(8)

in which:

R₇, which may be identical or different, represent a monovalent hydrocarbon-based radical containing from 1 to 18 carbon atoms, and in particular a C Ci₈ alkyl radical, a C₂-Ci₈ alkenyl radical or a ring comprising 5 or 6 carbon atoms, for example methyl; R₆ represents a divalent hydrocarbon-based radical, especially a C Ci₈ alkylene radical or a divalent C Ci₈, and for example C C₈, alkylenoxy radical linked to the Si via an SiC bond;

R₈, which may be identical or different, represent a hydrogen atom, a monovalent hydrocarbon-based radical containing from 1 to 18 carbon atoms, and in particular a C

Cis alkyl radical, a C₂-Ci₈ alkenyl radical or a radical -R₆-NHCOR₇;

X^" is an anion such as a halide ion, especially chloride, or an organic acid salt (acetate, etc.);

r represents a mean statistical value from 2 to 200 and in particular from 5 to 100;

These silicones are described, for example, in patent application EP-A-0 530 974.

(d) the amino silicones of formula (9):

(9)

in which:

- RL R₂, R3 and R₄, which may be identical or different, denote a C C₄ alkyl radical or a phenyl group,

- R₅ denotes a C C₄ alkyl radical or a hydroxyl group,

- n is an integer ranging from 1 to 5,

- m is an integer ranging from 1 to 5,

and in which x is selected such that the amine number is between 0.01 and 1 meq/g.

When they are present, the concentration of cationic or amphoteric substantive polymer may range from 0.01 % to 10% approximately relative to the total weight of the composition, and preferably from 0.1 % to 5% by weight relative to the weight of the composition.

The dyeing composition according to the invention may also comprise various additives conventionally used in the field of dyeing human keratin fibres.

The composition may thus comprise mineral or organic thickeners, and in particular fillers such as clays, optionally associative nonionic, anionic, cationic or amphoteric polymers; binders such as vinylpyrrolidone; lubricants such as polyol stearates or alkali metal or alkaline-earth metal stearates; hydrophilic or hydrophobic silicas; pigments; matting agents such as titanium oxides; anionic, nonionic, cationic, amphoteric or zwitterionic surfactants; penetrants, sequestrants, such as ethylenediaminetetraacetic acid or salts thereof; moisture absorbers such as amorphous silicas, buffers; dispersants; film-forming agents; preserving agents; opacifiers; vitamins; fragrances; ceramides; and volatile silicones.

The additives as defined above may be present in an amount, for each of them, of between 0.01 % and 40% by weight and preferably between 0.1 % and 30% by weight relative to the total weight of the composition.

The process according to the invention consists in applying the composition which has just been described in detail to human keratin fibres, it being possible for the latter to be wet or dry.

If the composition comprises at least one dye, it is a dyeing process.

If it contains no dye, it is a bleaching or lightening process.

Customarily, the composition applied is obtained by prior extemporaneous mixing of the various ingredients, including the oxidizing agent. Generally, this composition is obtained by mixing a composition that is free of oxidizing agent, with a composition comprising it (oxidizing composition).

It should be noted that the oxidizing composition and the composition comprising the dye(s) and/or the alkaline agent(s), may one and/or the other contain one or more cationic surfactants of formula (I) or (Γ).

This oxidizing composition advantageously comprises water and optionally one or more solvents such as are, for example, listed within the context of the description of the composition of the invention.

The oxidizing composition may take the form of a solution, an emulsion or a gel. It may optionally comprise one or more additives conventionally used in the field of dyeing human keratin fibres, as a function of the desired galenic form. Once again, reference may be made to the list of additives given above.

The composition of the invention generally has a pH above 7 and preferably ranging from 8 to 12.

It is specified that the pH of the composition that is free of oxidizing agent and that consequently comprises the dye(s) and/or the alkaline agent(s) is generally above 8, generally between 8 and 12, and preferably between 9 and 11.

The pH of the oxidizing composition is customarily below 7 and preferably between 3 and 6.

The pH of these compositions may be adjusted to the desired value by means of one or more acidifying agents or one or more alkaline agents customarily used in the field.

Among the acidifying agents, examples that may be mentioned include mineral or organic acids, for instance hydrochloric acid, orthophosphoric acid, sulphuric acid, carboxylic acids, for instance acetic acid, tartaric acid, citric acid or lactic acid, and sulphonic acids. Among the alkalinizing agents, reference will be made to the lists given above.

It would also be possible to envisage applying, successively and without intermediate rinsing, the composition that is free of oxidizing agent and the oxidizing composition, in either order.

The cationic surfactant(s) of formula (I) or (Γ) are, without preference, in one and/or the other of the two compositions. Irrespective of the variant selected, the composition applied (resulting from extemporaneous mixing or from successive application) is left in place for a time generally from about 1 minute to 1 hour and preferably from 10 minutes to 30 minutes.

The temperature during the process conventionally ranges from room temperature (between 15°C and 25°C) to 80°C and preferably from room temperature to 60°C.

At the end of the treatment, the human keratin fibres are optionally rinsed with water, washed with shampoo, rinsed again with water, and then dried or left to dry.

As indicated above, another subject of the invention is formed by a multicompartment device comprising a first compartment containing a composition comprising at least one dye chosen from oxidation dye precursors, direct dyes or mixtures thereof, or at least one alkaline agent, or mixtures thereof and a second compartment containing a composition comprising one or more oxidizing agents, at least one of the two compositions comprising at least one cationic surfactant of formula (I) or (Γ); the dye, the alkaline agent, the oxidizing agent and the cationic surfactant of formula (I) or (Γ) being as defined above.

That which has been described above regarding the composition according to the invention, the oxidizing composition, and the various ingredients, the nature and respective proportions thereof, remains valid and will not be repeated again. The example that follows serves to illustrate the invention without, however, being limiting in nature.

EXAMPLES A 1. Compositions

The following compositions are prepared: C (comparative) and 11 to I4 in accordance with the invention, the ingredients of which are listed in Tables 1 and 2 below. These compositions differ due to the nature of the cationic surfactant used.

It is specified that the amounts are expressed as % by weight of active materials, unless otherwise indicated. Table 1

Table 2

Surfactants 11 to I4' are more environmentally-friendly than surfactant C.

N.B.: the surfactants are first mixed with the fatty substances before being mixed with the other ingredients of the composition. 2. Hair dyeing

At the time of use, each composition is mixed with an equal weight of 20-volumes aqueous hydrogen peroxide solution (6% by weight). A final pH of 9.8 is obtained.

Each mixture obtained is applied to locks of natural or permanent-waved grey hair containing 90% white hairs.

After a leave-in time of 30 minutes at 25°C, the locks are rinsed, washed with a standard shampoo, rinsed again and then dried.

The dyeing results obtained after dyeing the hair are similar with all of compositions C to 14'.

On the other hand, the compositions 11 ', I2', I3' and I4', which are acceptable from an ecotoxicity viewpoint unlike composition C, make it possible to obtain compositions as a mixture with aqueous hydrogen peroxide solution that are less coloured than the mixture resulting from composition C and which have a less noticeable odour of ammonia. EXAMPLES B

1. Compositions The following compositions are prepared: C (comparative) and 11 to I4 in accordance with the invention, the ingredients of which are listed in Tables 1 and 2 below. These compositions differ due to the nature of the cationic surfactant used.

It is specified that the amounts are expressed as % by weight of active materials, unless otherwise indicated.

Table 1

Table 2

Cationic surfactants J1 to J4' are more environmentally-friendly than surfactant C.

N.B.: the surfactants are first mixed with the fatty substances before being mixed with the other ingredients of the composition.

2. Hair dyeing

After a leave-in time of 30 minutes at 25°C, the locks are rinsed, washed with a standard shampoo and rinsed again.

The dyeing results obtained after dyeing the hair are similar in all of compositions D to J4'.

On the other hand, the compositions J1', J2', J3' and J4', which are acceptable from an ecotoxicity viewpoint unlike composition D', make it possible to obtain compositions as a mixture with aqueous hydrogen peroxide solution that are less coloured than the mixture resulting from composition D and which have a less noticeable odour of ammonia.

Claims

Composition comprising:

rfactant of formula (I) or (Γ) below:

X

(I)

in which formula:

Ri , which may be identical or different, represent a hydrogen atom, a linear C C₆ alkyl radical or a branched C₃-C₆ alkyl radical, optionally bearing at least one hydroxyl or alkoxy group, the alkyl part of which is a C C₄ alkyl;

X^" represents a counterion;

in which formula:

m is an integer ranging from 1 to 3;

X^" represents a counterion; and

(b) at least one oxidizing agent;

Composition according to the preceding claim, characterized in that the cationic

surfactant(s) of formula (I) are such that R₃ represents a C₈-C₃₂, preferably Ci₀-C₃₀, alkyl radical or a radical -CH₂0-R'₃ with R'₃ representing a C₈-C₃₂, preferably Ci₀-C₃₀, alkyl radical.

Composition according to any one of the preceding claims, characterized in that the cationic surfactant(s) of formula (I) are such that represents a hydrogen atom.

Composition according to any one of the preceding claims, characterized in that the cationic surfactant(s) of formula (I) are such that R₂, which may be identical or different, represent a C C₄ alkyl radical, preferably a methyl radical.

5. Composition according to any one of the preceding claims, characterized in that the cationic surfactant(s) of formula (I) are such that n is equal to 2 and p is equal to 1.

Composition according to any one of the preceding claims, characterized in that the

cationic surfactant(s) of formula (I) are chosen from the following compounds, alone or as mixtures:

X^" denotes a counterion and preferably a chloride ion.

7. Composition according to Claim 1 , characterized in that the cationic surfactant(s) of formula (Γ) are such that R'₃ represents a C₈-C₃₂, preferably Ci₀-C₃₀, alkyl radical, or a radical -CH(OH)-(CH₂0)p-R"₃ with R"₃ representing a C₈-C₃₂, preferably Ci₀-C₃₀, alkyl radical, p being equal to 0 or 1.

8. Composition according to either one of Claims 1 and 7, characterized in that the cationic surfactant(s) of formula (I) are such that m is equal to 3.

9. Composition according to any one of Claims 1 , 7 or 8, characterized in that the cationic surfactant(s) of formula (Γ) are such that R represents a C C₄ alkyl radical. 10. Composition according to any one of Claims 1 , 7 to 9, characterized in that the cationic surfactant(s) of formula (Γ) are such that R'₂ represents a C C₄ alkyl radical or a radical -CH₂-CH(OH)-[CH(OH)]n -H with n' representing an integer ranging from 1 to 4, and preferably 3, R'₂ representing more preferentially still a C C₄ alkyl radical.

1 1. Composition according to any one of Claims 1 , 7 to 10, characterized in that the cationic surfactant(s) of formula (Γ) are chosen from the following compounds, alone or as mixtures:

X^" denoting a counterion and preferably a chloride ion.

Composition according to any one of the preceding claims, characterized in that the content of cationic surfactant(s) of formula (I) or (Γ) ranges from 0.01 % to 20% by weight, more particularly from 0.1 % to 10% by weight and preferably from 0.5% to 5% by weight relative to the total weight of the composition.

Composition according to any one of the preceding claims, in which the oxidizing agent is chosen from hydrogen peroxide, urea peroxide, alkali metal bromates or ferricyanides and peroxygenated salts, preferably hydrogen peroxide.

Composition according to any one of the preceding claims, characterized in that the dye precursor(s) are chosen from the following oxidation bases: para- phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, ortho- aminophenols, heterocyclic bases and the addition salts thereof and the following couplers: mefa-phenylenediamines, mefa-aminophenols, mefa-diphenols, naphthalene-based couplers, heterocyclic couplers, and also the addition salts thereof.

15. Composition according to any one of the preceding claims, characterized in that the direct dye(s) are chosen from neutral, acidic or cationic nitrobenzene direct dyes, neutral, acidic or cationic azo direct dyes, tetraazapentamethine dyes, neutral, acidic or cationic quinone and in particular anthraquinone dyes, azine direct dyes, triarylmethane direct dyes, indoamine direct dyes and natural direct dyes.

16. Composition according to any one of the preceding claims, characterized in that the alkaline agent is chosen from mineral or organic or hybrid alkaline agents, or mixtures thereof.

17. Composition according to any one of the preceding claims, in which the alkaline agent is aqueous ammonia and/or an alkanolamine such as monoethanolamine.

18. Method for treating keratin fibres, in which a composition according to any one of the preceding claims is applied to the fibres.

Multicompartment device comprising a first compartment containing a composition comprising at least one dye chosen from oxidation dye precursors, direct dyes or mixtures thereof, or at least one alkaline agent, or mixtures thereof and a second compartment containing a composition comprising one or more oxidizing agents, at least one of the two compositions comprising at least one cationic surfactant of formula (I) or (Γ); the dye(s), the alkaline agent(s), the oxidizing agent(s), the cationic surfactant(s) of formula (I) or (Γ) being as defined according to any one of Claims 1 to 1 1.

Use of cationic surfactant(s) of formula (I) or (Γ) as defined according to one of Claims 1 to 11 , for dyeing or bleaching human keratin fibres.