WO2011027076A2

WO2011027076A2 - Dyeing method consisting in applying a metallic salt and a composition containing a hydrophobic dye and a specific compound

Info

Publication number: WO2011027076A2
Application number: PCT/FR2010/051820
Authority: WO
Inventors: Boris Lalleman; Alain Lagrange
Original assignee: L'oreal
Priority date: 2009-09-02
Filing date: 2010-09-01
Publication date: 2011-03-10
Also published as: FR2949335A1; FR2949335B1; WO2011027076A3

Abstract

The invention relates to a method for dyeing keratin fibres, in particular human keratin fibres, comprising: a) a step in which a composition is applied to the keratin fibres, said composition comprising one or more mineral or organic metallic salts; and b) a step in which a dyeing composition is applied to the keratin fibres, said dyeing composition containing one or more hydrophobic direct dyes with a logP greater than or equal to 2 and one or more compounds (I) having a structure containing chain: Formula (I), wherein n is an integer between 0 and 4 and Formula (II) denotes a group: Formula (III) or Formula (IV) or Formula (V), whereby step (a) is performed before, during or after step (b).

Description

A coloring process comprising applying a metal salt and a composition comprising a hydrophobic dye and a

particular compound

The present invention relates to a process for the coororation of keratinous fibers comprising a step of applying to said keratinous fibers a composition comprising one or more organic or inorganic metal salts, and a step of application to the keratin fibers of a dyeing composition comprising one or more hydrophobic direct dyes of logP greater than or equal to 2 and one or more particular compounds (I).

Two major modes of staining human keratin fibers, and in particular hair, are known.

The first, called oxidation or permanent staining, consists in using one or more oxidation dye precursors, more particularly one or more oxidation bases possibly associated with one or more couplers.

Usually, oxidation bases are selected from ortho- or para-phenylenediamines, ortho- or para-aminophenols as well as heterocyclic compounds. These oxidation bases are colorless or weakly colored compounds which, combined with oxidizing products, make it possible to access, by a process of oxidative condensation, colored species which remain trapped inside the fiber.

Very often, the shades obtained with these oxidation bases are varied by combining them with one or more couplers, the latter being chosen in particular from aromatic meta-diamines, meta-aminophenols, meta-diphenols and certain heterocyclic compounds, such as indolic.

The variety of molecules used in the oxidation bases and couplers makes it possible to obtain a rich palette of colors. This type of co - loration also makes it possible to obtain permanent co - lorations, but the use of oxidizing agents may lead to degradation of the keratinous fibers.

The second mode of dyeing, called direct or semi-permanent dyeing, comprises the application of direct colors which are mo lecules having an affinity for the fibers and dyes even in the absence of an oxidizing agent added in the compositions containing them. . Given the nature of the molecules used, they remain rather on the surface of the fiber and penetrate relatively little inside the fiber, compared to the small molecules of precursors of oxidation dyes.

The direct dyestuffs generally employed are selected from nitrobenzene, anthraquinone, nitropyridine, azo, methine, azomethine, xanthene, acridine, azine or triarylmethane direct dyes. The chemical species used may be nonionic, anionic (acidic dyes) or cationic (basic dyes). Direct colors can also be natural dyes.

Most of the direct dyes used have sufficient solubility in aqueous medium and there are now many staining supports adapted to implement them.

These compositions containing one or more direct dyes are applied to the keratin fibers for a time necessary to obtain the desired coloring, and then rinsed.

However, the resulting colourations are particularly chromatic, but temporary or semi-permanent, dyes because the nature of the interactions which bind the direct colors to the keratinous fiber, and their desorption of the surface and / or the core of the fiber are responsible for their low dyeing power and their poor resistance to washes or light.

In order to effectively stain keratinous fibers, most hydrophobic direct colors are to be used in the presence of particular solvents whose role is to vectorize them in the fiber. Among the known cosmetic solvents for this purpose, frequently aromatic solvents. Mention may more particularly be made of benzyl alcohol, benzyloxyethanol or phenoxyethanol.

However, the presence of aromatic solvents, which are not very soluble in an aqueous medium, requires the use of large amounts of co-solvents (usually ethanol) to make them compatible with conventional dye formulations.

Moreover, even under these conditions, the intensity of the corations obtained remains insufficient or the selectivity remains too high.

In addition, reducing compounds such as hydrosulfites are sometimes used in the textile field to reduce reducible hydrophobic colorants. But these compounds have a negative effect on the environment, they contaminate wastewater at a high level. On the other hand, they give off very uncomfortable odors for a cosmetic application.

There is therefore a need to provide new compositions for dyeing human hair that are more effective, compatible with hydrophobic colorants, that respect the nature of the hair and that make it possible to obtain powerful, selectively resistant and resistant dyes.

The Applicant has surprisingly discovered that this technical problem could be solved by a method for dyeing keratinous fibers, in particular human keratinous fibers, comprising a step of applying to said keratinous fibers a composition comprising one or more metal salts. organic or inorganic, and a step of application to the keratinous fibers of a dye composition comprising one or more hydrophobic direct dyes of logP greater than or equal to 2 and one or more particular compounds (I).

The object of the invention is therefore to provide a process for dyeing keratinous fibers, in particular human keratinous fibers, in particular the hair, comprising: a) a step of applying to said keratinous fibers a composition comprising one or more organic or inorganic metal salts,

b) a step of applying to the keratinous fibers a dyeing composition comprising one or more hydrophobic direct dyes of logP greater than or equal to 2 and one or more compounds (I) having in their structure a sequence:

with n denoting an integer ranging from 0 to 4, and

- Χ designating a grouping:

step a) being performed before, during or after step b).

For the purposes of the present invention, the term "metal salts" means the salts of the metals of columns 3 to 14 of the periodic table of elements. Preferably, the metal salts are chosen from organic or inorganic salts of iron, copper, zinc, tin, aluminum, manganese, copper and silver.

Even more preferentially, the metal salts are chosen from inorganic or organic salts of zinc, in particular zinc chloride, zinc sulphate and zinc gluconate.

The metal salt (s) preferably have a molecular weight of less than 500 g / mol, preferably less than 250 g / mol.

The concentration of the organic or inorganic metal salt (s) in the composition or the container (s) can vary from 0.01 to 20%, preferably from 0.1 to 10%, better still from 0.5 to 5%, expressed by weight of metal relative to the total weight of the composition containing them.

As explained above, the method according to the invention comprises a step b) of application to the keratinous fibers of a dye composition comprising especially one or more hydrophobic direct dyes of logP greater than or equal to 2.

The logP value conventionally represents the coefficient of partition of the dye between octanol and water. The logP can be calculated according to the method described in the article by Meylan and Howard "Atom / Fragment contribution method for estimating octanol-water partition coefficient", J. Pharm. Sci. 84: 83-92, 1995. This value can also be calculated from many commercially available software that determines LogP based on the structure of a molecule. By way of example, mention may be made of the Epiwin software from the United States Environmental Agency.

It should be noted that the logP value is usually given for a temperature of 25 ° C. and at atmospheric pressure (760 mmHg, ie 1.013 × 10 ⁵ Pa).

In particular, the hydrophobic direct dye (s) present in the dyeing composition used in the process according to the invention may be chosen from the following compounds, alone or as a mixture:

LogP chemical structure dye

Disperse Red 17 3.69

Disperse Violet 1 3.0

HC Yellow 7 2.38

OH

Solvent Orange

3.90

15

Solvent Orange 7 4.40

O N ^^ - ^ ~ ^ ~ ^

Solvent Blue 14 8.18

O HN ^ _ / \ __ / \

Disperse Yellow

3.68

82

The hydrophobic direct dye (s) present in the composition used in the process according to the invention may also be chosen from indigo-type colorants.

The indigo-coloring agents that can be used in the dyeing composition used according to the invention can be chosen from:

It is also possible to use, as hydrophobic direct co-ortors of LogP greater than or equal to 2, the following indigo-directing colorants: leucoindigo, leucoisoindigo, leucoindirubin and leucoisoindirubin.

Preferably, the direct dyes of LogP greater than or equal to 2 are chosen from indigo-rich colorants. The hydrophobic direct dye (s) of LogP greater than or equal to 2 generally represents from 0.01 to 20% by weight, preferably from 0.05 to 10% by weight, better still from 0.1 to 5% by weight of the total weight. of the dyeing composition.

As explained above, the dye composition used in step b) of the process according to the invention also comprises one or more specific compounds (I).

Preferably, n is 0, 1 or 2.

Preferably, the compound (s) (I) have in their structure a sequence:

^{0 0H} (A) or ^{0H 0H} (B).

(B) being the tautomeric form of (A).

The compound (s) (I) preferably correspond to the following formula (C):

with:

n designating an integer ranging from 0 to 4, preferably from 0 to 2, and denoting a grouping:

R 1 and R ₂ represent, independently of one another, a hydrogen atom; a substituted or unsubstituted phenyl radical; a hydroxy radical; a C ₁ -C ₄ alkoxy radical; a linear or branched C 1 -C ₄ alkyl radical, unsubstituted or substituted by one or two radicals chosen from the radicals -OR ', -C (O) R ", -COOR'", with R ', R "and R'" representing, independently of each other, a hydrogen atom, a linear or branched C ₁ -C ₄ alkyl radical, or

R 1 and R ₂ forming, with the carbon chain to which they are attached, an unsubstituted 5- or 6-membered non-aromatic carbon ring.

The particular compound or compounds (I) are preferably chosen from the following compounds:

The preferred compound (s) (I) are the α-hydroxyacetone compounds, such as hydroxyacetone, acetoin, glutaroin, adipoin, benzoin, dihydroxyacetone, glycol aldehyde, and 2,3-dihydroxyacryl- aldehyde.

The compound (s) (I) generally represent from 0.01% to 20% by weight, preferably from 0.05% to 10% by weight and better still from 0.1% to 5% by weight relative to the total weight of the cosmetic composition.

The dye composition used in step b) of the process according to the invention may also also comprise one or more organic compounds (II) having a value of the parameter

1/2 δΗ of Hansen with a solubility of less than or equal to 16 MPa,

1/2

preferably less than 16 MPa, more preferably ranging from 5 to 15.8 MPa ^1/2 and better still 8 to 15.8 MPa ^1/2 , and molecular weight less than 250 g / mol.

Preferably, these compounds are liquid at a temperature of 25 ° C. and at atmospheric pressure (760 mmHg, ie 1.013 × 10 ⁵ Pa). The organic compound or compounds having a Hansen solubility parameter δΗ value, as defined above, are for example described in the reference book "Hansen solubility parameters A user's handbook, Charles M. HANSEN", CRC Press, 2000, pages 167 to 185, or in the book "Handbook of Solubility Parameters and Other Cohesion Parameters", CRC, Press, pages 95 to 121 and pages 177 to 185.

This value of the solubility parameter δΗ is related to the formation of hydrogen bonds.

In particular, the book "Handbook of Solubility Parameters and Other Cohesion Parameters", CRC Press, pages 95-12 1 and pages 177-185, gives the equation δΗ = (Σ- ^z U _h / V) ^1/2

or,

zU _h (in J.mo l- ¹ ) describes the contributions of the functional group considered in the parameters of solubility linked to the hydrogen bonds (values in table 14, page 1 83), this parameter ^z U _h also being described in the book "The relation between surface tension and soubility parameter in liquids", Bagda, E, Farbe Lack, 84, 212, 1978;

and V is the volume of the molecule.

It should be noted that the value of the solubility parameter δΗ is usually given for a temperature of 25 ° C. and at atmospheric pressure (760 mmHg, ie 1.01 3. 10 ⁵ Pa).

The at least one organic compound (II) may be chosen from alkanoids, aliphatic esters, ethers, aromatic alcohols, alkylaryl alcohols, aromatic acids, aliphatic acids and alkylene carbonates, such as propylene carbonate. lactones such as γ-butyro lactone, and mixtures thereof.

Preferably, the one or more organic compounds (II) are chosen from alkanols, aliphatic esters, ethers, aromatic alcohols, alkylaryl alcohols, aromatic acids, aliphatic acids, and mixtures thereof.

Even more preferentially, the one or more organic compounds (II) are chosen from 1-octanol, 1-decanol, tridecyl alcohol, dipropylene glycol monomethyl ether acetate, dipropylene glycol methyl ether, tripropylene glycol methyl ether, propylene glycol n-butyl ether, propylene glycol n-propyl ether, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, 3-phenyl-1-propanol, 2-phenyl-1-propanol, benzyl alcohol, benzyloxyethanol, phenoxyethanol, and mixtures thereof.

The organic compound (II) is preferably chosen from aromatic alcohols, alkylaryl alcohols and even more preferably benzyl alcohol.

The organic compound (s) (II), when present, generally represent from 0.1% to 20%, preferably from 1% to 5%, by weight of the total weight of the composition.

The dye composition used in step b) of the process according to the invention may also comprise one or more additional dyes. In particular, the dye composition used according to the invention may also comprise at least one additional dye different from hydrophobic dyes of logP greater than or equal to 2 chosen from natural dyes and non-natural direct dyes, dye precursors d. oxidation, or combinations thereof.

By "natural colors" is meant any dye or dye precursor having a natural occurrence and produced either by extraction, and optionally purification, from a plant matrix, or by chemical synthesis.

The additional natural colors which are suitable in particular for the implementation of the invention may be chosen, for example, from carminic acid, kermetic acid, isatin, chlorophyllins, haematein, hematoxylin, brazilin, braziline, betanin, flavonoids, anthocyanins.

It is also possible to use the extracts or decoctions containing these natural colors, and in particular the extracts based on henna.

The composition may also comprise one or more additional non-natural direct colorants, different from the hydrophobic character described above, and selected from ionic or nonionic species, preferably cationic or nonionic.

Examples of suitable direct dyes include direct azo, methine, carbonyl, azine, nitro (hetero) aryl, tris (hetero) aryl methanes, porphyrins and phthalocyanines, singly or in combination. mixed.

More particularly, the azo dyes comprise a function -N = N-, the two nitrogen atoms of which are not simultaneously engaged in a ring. However, it is not excluded that one of the two nitrogen atoms of the sequence -N = N- is engaged in a cycle.

The colorants of the family of methines are more particularly compounds comprising at least one sequence selected from> C = C <and -N = C <, the two atoms are not simultaneously engaged in a ring. It is however specified that one of the nitrogen or carbon atoms of the chains can be engaged in a cycle. More particularly, the dyes of this family are derived from compounds of the true methine type, comprising one or more -C = C- above-mentioned sequences, azomethine, comprising at least one or more -C = N- sequences with, for example, azacarbocyanines and their isomers, diazacarbocyanines and their isomers, tetraazacarbocyanines, mono- and di-arylmethanes, indoamines or diphenylamines, indophenols, indoanilines.

As regards the dyes of the carbonyl family, mention may be made, for example, of unnatural colorants chosen from acridone, benzoquinone, anthraquinone, naphthoquinone, benzanthrone, anthranthrone, pyranthrone, pyrazolanthrone, pyrimidinoanthrone, flavanthrone, idanthrone, flavone, (iso) vio lanthrone, isoindo linone, benzimidazolone, isoquino linone, anthrapyridone, pyrazoloquinazolone, perinone, quinacridone, quinophthalone, naphthalimide, anthrapyrimidine, diketopyrrolopyrrole, coumarin.

As regards the dyes of the family of cyclic azines, there may be mentioned in particular azine, xanthene, thioxanthene, fluorindine, acridine, (di) oxazine, (di) thiazine, pyronine. The nitro (hetero) aromatic colors are more particularly nitrobenzene or pyridine nitro direct dyes.

With regard to porphyrin or phthalocyanine dyes, it is possible to use cationic or non-cationic compounds, optionally comprising one or more metals or metal ions, for example alkali and alkaline earth metals, zinc and silicon.

By way of example of additional particularly suitable direct synthesis colors, mention may be made of nitro dyes of the benzene series, azo, azomethine, methine direct dyes, azacarbocyanines such as tetraazacarbocyanines and tetraazapentamethines, quinone direct dyes and in particular anthraquinone, naphthoquinone or benzoquinone, direct azinic, xanthenic, triarylmethane, indoamine, phthalocyanine and porphyrin, alone or in admixture. Even more preferably, these additional direct colors are chosen from nitro dyes of the benzene series, azo, azomethine, methine, tetraazacarbocyanine and tetraazapentamethine direct dyes, alone or as a mixture.

These colorants may be monochromophoric colorants, that is to say comprising only one coloring agent, or polychromophoric, preferably di- or tri-chromophoric, the chromophores may be identical or not, of the same family chemical or not. It should be noted that a polychromophoric dye comprises several radicals each derived from an absorbing molecule in the visible range, between 400 and 800 nm. Moreover, this absorbance of the dye does not require any prior oxidation thereof, nor any association with other chemical species.

In the case of polychromophoric colorants, the chromophores are connected to one another by means of at least one linker which may or may not be cationic. Among the polychromophoric colorants, mention may be made more particularly of di- or tri-chromophoric dyes azo and / or azomethine, such as hydrazonic, symmetrical or not, comprising, on the one hand, at least one aromatic heterocycle comprising 5 or 6 optionally condensed linkages comprising at least one quaternized nitrogen atom engaged in said heterocyclic ring and optionally at least one other heteroatom, such as nitrogen, sulfur, oxygen, and at the same time at least one group optionally substituted phenyl or naphthyl, optionally bearing at least one -OR group, with R representing a hydrogen atom, an optionally substituted C 1 -C ₆ alkyl radical, an optionally substituted phenyl ring, or at least one N group (R ') ₂ , with R' being identical or different, representing a hydrogen atom, an optionally substituted C 1 -C ₆ alkyl radical, an optionally substituted phenyl ring, the radicals R 'which can form, with the nitrogen atom to which they are bonded, a saturated 5- or 6 - membered heterocycle, or else one and / or both radicals R' may each form with the carbon atom of the aromatic ring placed in ortho of the nitrogen atom, a 5- or 6 - membered saturated heterocycle.

As aromatic cationic heterocycle, there may be mentioned, preferably, 5- or 6-membered rings comprising 1 to 3 nitrogen atoms, preferably 1 or 2 nitrogen atoms, one being quaternized, said heterocycle being otherwise optionally fused to a benzene ring. It should also be noted that the heterocycle may optionally comprise another heteroatom different from nitrogen, such as sulfur or oxygen.

If the heterocycles or phenyl or naphthyl groups are substituted, they are substituted, for example, with one or more C 1 -C ₅ alkyl radicals optionally substituted by a hydroxyl, C 1 -C ₂ alkoxy or C ₂ -C ₄ hydroxyalkoxy group. acetylamino, amino substituted with one or two C 1 -C ₄ alkyl radicals, optionally carrying a hydroxyl group or both radicals which can form, with the nitrogen atom to which they are attached, a 5- or 6-membered heterocycle, optionally comprising another heteroatom identical or different from nitrogen, a halogen atom, a hydroxyl group, a C1-C2 alkoxy radical, a C2-C4 hydroxyalkoxy radical, an amino radical, an amino radical substituted with one or two identical alkyl radicals, or different, C1-C4 optionally carrying a hydroxyl group.

Preferably, the linking arm is a linear, branched or cyclic C 1 -C 20 alkyl chain, optionally interrupted by at least one heteroatom, such as nitrogen, oxygen and / or by at least one group comprising CO, S0 ₂ , optionally interrupted by at least one phenyl or substituted or unsubstituted naphthyl group, optionally interrupted by at least one saturated, unsaturated or aromatic heterocycle, condensed or not with a phenyl ring, said heterocycle comprising at least one quaternized nitrogen atom engaged in said cycle and optionally at least one other heteroatom, such as oxygen, nitrogen or sulfur, optionally interrupted by at least one quaternary ammonium group substituted with two C 1 -C 15 alkyl groups, the linker not comprising nitro, nitroso or peroxo grouping.

If the heterocycles or aromatic rings are substituted, they are, for example, substituted by one or more C 1 -C 6 alkyl radicals optionally substituted by a hydroxyl, C 1 -C ₂ alkoxy or C ₂ -C ₄ hydroxyalkoxy, acetylamino or amino group substituted by a or two identical or different C 1 -C 4 alkyl radicals, optionally carrying a hydroxyl group, or the two radicals which can form, with the nitrogen atom to which they are attached, a 5- or 6-membered heterocycle, optionally comprising a another heteroatom identical to or different from nitrogen, a halogen atom, a hydroxyl group, a C1-C2 alkoxy radical, a C2-C4 hydroxyalkoxy radical, an amino radical, an amino radical substituted by one or two alkyl radicals , identical or different, C1-C4 optionally carrying a hydroxyl group.

The link between the linker and each chromophore is usually by means of a heteroatom substituting the nucleus phenyl or naphthyl, or by means of the quaternized nitrogen atom of the cationic heterocycle.

Among the azo, azomethine, methine or tetraazapentamethine monochromophoric direct dyes that may be used according to the invention, mention may be made of the cationic dyes described in patent applications WO 95/15144, WO 95/01772 and EP 714954, FR 2189006, FR 2285851, FR -2140205, EP 1378544, EP 1674073.

Thus, mention may in particular be made of the cationic direct dyes corresponding to the following formulas:

in which :

D represents a nitrogen atom or the group -CH,

R 1 and R ₂ , which may be identical or different, represent a hydrogen atom or a C ₁ -C ₄ alkyl radical which may be substituted by a -CN, -OH or -NH ₂ radical or form, with a carbon atom of the ring benzene, an optionally oxygenated or nitrogen heterocycle, which may be substituted by one or more C ₁ -C ₄ alkyl radicals, a 4'-aminophenyl radical,

R3 and R ' ₃ , which may be identical or different, represent a hydrogen or halogen atom chosen from chlorine, bromine, iodine and fluorine, a cyano, a C ₁ -C ₄ alkyl or a C ₁ -C ₄ alkoxy radical; ₁ -C ₄ or acetyloxy,

X ^" represents an anion, preferably chosen from chloride, methyl sulfate and acetate,

A represents a group selected from the following structures:

in which R ₄ represents a C ₁ -C ₄ alkyl radical which may be substituted with a hydroxyl radical,

in which :

R ₅ represents a hydrogen atom, a C 1 -C ₄ alkoxy radical, a halogen atom such as bromine, chlorine, iodine or fluorine,

R ₆ represents a hydrogen atom, a C ₁ -C ₄ alkyl radical or forms, with a carbon atom of the benzene ring, a heterocycle optionally oxygenated and / or substituted with one or more C ₁ -C ₄ alkyl groups,

R ₇ represents a hydrogen or halogen atom such as bromine, chlorine, iodine or fluorine,

Di and D ₂ , which may be identical or different, represent a nitrogen atom or the group -CH,

m = 0 or 1,

X ^" represents a cosmetically acceptable anion, and preferably chosen from chloride, methyl sulfate and acetate,

E represents a group chosen by the following structures:

wherein R 'represents an alkyl radical Ci-C _4.

When m = 0 and Di represents a nitrogen atom, then E can also designate a group of following structure:

in which R 'represents a C1-C4 alkyl radical.

Among the abovementioned compounds, the following compounds are especially used:

Among the tetraazapentamethine type dyes that may be used according to the invention, the following compounds appearing in the table below may be mentioned:

X ^" represents an anion, preferably selected from chloride, hard, methylsulfate, ethylsulfate, acetate.

The dye composition may also comprise one or more oxidation dye precursors, more particularly one or more oxidation bases, optionally combined with one or more couplers.

By way of example, the oxidation bases are chosen from para-phenylenediamines, bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols, heterocyclic bases, and their addition salts.

Among the paraphenylenediamines, there may be mentioned, for example, para-phenylenediamine, paratoluylenediamine, 2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, diethyl-para-phenylenediamine, 2,5-dimethyl-para-phenylenediamine, Ν, Ν-dimethyl-para-phenylenediamine, N, N-diethyl-para-phenylenediamine, N, N-dipropyl-para-phenylenediamine, 4-amino N, N-diethyl- 3-methylaniline, N, N-bis- (-hydroxyethyl) -paraphenylenediamine, 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) -paraphenylenediamine, 2-hydroxymethyl- paraphenylenediamine, N, N-dimethyl-3-methyl-para-phenylenediamine, N, N- (ethyl, -hydroxyethyl) -paraphenylenediamine, N- (4-dihydroxypropyl) -paraphenylenediamine, N- (4'-aminophenyl) para-phenylenediamine, N-phenyl-para-phenylenediamine, 2-hydroxyethyloxy-para-phenylenediamine, 2-acetylaminoethyloxy-para-phenylenediamine, N- (methoxyethyl) -paraphenylene diamine, 4-aminophenylpyrrolidine, 2-thienyl para-phenylenediamine, 2-hydroxyethylamino-5-aminotoluene, 3-hydroxy-1- (4'-aminophenyl) pyrrolidine, and their addition salts with an acid.

Among the paraphenylenediamines mentioned above, para-phenylenediamine, paratoluylenediamine, 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) -paraphenylenediamine, 2-chloro-para-phenylenediamine,

2- -acetylaminoethyloxy-para-phenylenediamine, and their addition salts with an acid, are particularly preferred.

Among the bis-phenylalkylenediamines, mention may be made, 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 N, N'-bis- (4-aminophenyl) -tetramethylenediamine, N, N'-bis- (4-methylaminophenyl) tetramethylenediamine, N, N'-bis-bis (-hydroxyethyl) -N, N'-bis (4-aminophenyl) -tetramethylenediamine; (ethyl) -N, N'-bis- (4'-amino, 3'-methylphenyl) ethylenediamine, 1,8-bis (2,5-diaminophenoxy) -3,6-dioxaoctane, and their addition salts.

Among the para-aminophenols, there may be mentioned, for example, para-aminophenol, 4-amino-3-methylphenol, 4-aminophenol,

3-fluorophenol, 4-amino-3-chlorophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2 methoxymethylphenol, the

4-amino-2-aminomethylphenol, 4-amino-2- (-hydroxyethyl) aminomethyl) -phenol, 4-amino-2-fluorophenol, and their addition salts with an acid.

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

Among the heterocyclic bases that may be mentioned, for example, pyridine derivatives, pyrimidine derivatives and pyrazole derivatives.

Among the pyridine derivatives, mention may be made of the compounds described for example in patents GB 1 026 978 and GB 1 153 196, such as 2,5-diaminopyridine, 2- (4-methoxyphenyl) amino-3-aminopyridine, 3 , 4-diaminopyridine, and their addition salts.

Other pyridinic oxidation bases useful in the present invention are the 3-amino-pyrazolo [1,5-a] pyridines oxidation bases and their addition salts described, for example, in the patent application. FR 2801308. By way of example, mention may be made of pyrazolo [1,5-a] pyridin-3-ylamine, 2-acetylamino pyrazolo [1,5-a] pyridin-3-ylamine, 2-morpholine 4-yl-pyrazolo [1,5-a] pyridin-3-ylamine, 3-amino-pyrazolo [1,5-a] pyridin-2-carboxylic acid, 2-methoxy-pyrazolo [1.5] a) pyridin-3-ylamino, (3-aminopyrazolo [1,5-a] pyridin-7-yl) -methanol, 2- (3-aminopyrazolo [1,5-a] pyridine; 5-yl) -ethanol, 2- (3-amino-pyrazolo [1,5-a] pyridin-7-yl) ethanol, (3-amino-pyrazolo [1,5-a] pyridine-2- yl) -methanol, 3,6-diamino-pyrazolo [1,5-a] pyridine, 3,4-diamino-pyrazolo [1,5-a] pyridine, pyrazolo [1,5-a] pyridine-3, 7-diamine, 7-morpholin-4-yl-pyrazolo [1,5-a] pyridin-3-ylamine, pyrazolo [1,5-a] pyridine-3,5-diamine, 5-morpholin-4 yl-pyrazolo [1, 5-a] pyridin-3-ylamine, 2 - [(3-amino-pyrazolo [1,5-a] pyridin-5-yl) - (2-hydroxyethyl) amino] ethanol, 2 [(3-amino-pyrazolo [1,5-a] pyridin-7-yl) - (2-hydroxyethyl) amino] ethanol, 3-amino-pyrazolo [1,5-a] pyridine-5- 3-amino-pyrazolo [1,5-a] pyridin-4-ol, 3-amino-pyrazolo [1,5-a] pyridin-6-ol, 3-amino-pyrazolo [1, 5 a] pyridine-7-ol, as well as their addition salts. Among the pyrimidine derivatives, mention may be made of the compounds described, for example, in DE 2359399, JP 88-169571, JP 05-63124, EP 0770375 and the 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-tri -triaminopyrimidine, their addition salts and their tautomeric forms, when there is a tautomeric equilibrium.

Among the pyrazole derivatives, mention may be made of the compounds described in DE 3843892, DE 4133957 and the patent applications WO 94/08969, WO 94/08970, FR-A-2 733 749 and DE 195 43988, such as 4, 5-diamino-1-methylpyrazole, 4,5-diamino-1- (β-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-tert-butyl-1-methylpyrazole, 4,5-diamino-1-tert-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- (-hydroxyethyl) amino-1-methylpyrazole, and their addition salts. 4-5-Diamino-1- (methoxyethyl) pyrazole may also be used.

As pyrazole derivatives, mention may also be made of diamino-N, N-dihydropyrazolopyrazolones and in particular those described in patent application FR 2886136, such as the following compounds and their addition salts: 2,3-diamino-6,7- dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one, 2-amino-3-ethylamino-6,7-dihydro- 1H, 5H-pyrazolo [1,2-a] pyrazol-1-one, 2-amino-3-isopropylamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one, 2-amino-3- (pyrrolidin

1-yl) -6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one, 4,5-diamino-

1,2-dimethyl-1,2-dihydro-pyrazol-3-one, 4,5-diamino-1,2-diethyl-1,2-dihydro-pyrazol-3-one, 4,5-diamino-1, 2- di- (2-hydroxyethyl) -1,2-dihydro-pyrazol-3-one, 2-amino-3- (2-hydroxyethyl) amino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] ] pyrazol-1-one, 2-amino-3-dimethylamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one, 2,3-diamino-5,6,7 8-tetrahydro-1H, 6H-pyridazino [1,2-a] pyrazol-1-one, 4-amino-1,2-diethyl-5- (pyrrolidin-1-yl) -1,2-dihydro-pyrazole 3-one, 4-amino-5- (3-dimethylamino-pyrrolidin-1-yl) -1,2-diethyl-1,2-dihydro-pyrazol-3-one, 2,3-diamino-6-hydroxy 6,6-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one.

As heterocyclic bases, 4,5-diamino-1- (p-hydroxyethyl) pyrazole and / or 2,3-diamino-6,7-dihydro-1H, 5H-pyrazolo [1,2,4] will preferably be used. ] pyrazol-1-one, and their addition salts.

The composition according to the invention may optionally comprise one or more couplers advantageously chosen from those conventionally used for dyeing keratinous fibers.

Among these couplers, mention may in particular be made of meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalenic couplers, heterocyclic couplers, as well as their addition salts.

By way of example, mention may be made 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, 1,1-hydroxyethylamino-3,4-methylenedioxybenzene, α-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-N- (3-hydroxyethyl) amino-3,4- methylenedioxybenzene, 2,6-bis- (β-hydroxyethylamino) toluene, 6-hydroxyindoline, 2,6-dihydroxy-4-methylpyridine, 1-H-3-methylpyrazol-5-one, 1-phenyl 3-methylpyrazone-5-one, 2,6-dimethylpyrazolo [1,5-b] -1,2,4-triazole, 2,6-dimethyl- [3,2-c] -1, 2,4-triazole, 6-methylpyrazo-1- [1,5-a] benzimidazole, their acid addition salts, and mixtures thereof.

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

The oxidation base or bases, when they are present in the composition, advantageously represent from 0.0001 to 10% by weight relative to the weight of the composition, and preferably from 0.005 to 5% by weight relative to the weight of the composition. the composition.

The coupler (s), if present, advantageously represent from 0.0001 to 10% by weight relative to the weight of the composition, and preferably from 0.005 to 5% by weight relative to the weight of the composition.

When present, the additional dye or dyes represent from 0.01 to 10% by weight and preferably from 0.5 to 5% by weight relative to the weight of the composition.

The dyeing composition used in stage b) of the process according to the invention may also comprise one or more conditioning agents.

By way of example, mention may be made of linear, cyclic, branched or unbranched, volatile or non-volatile silicones. These silicones may be in the form of oils, resins or gums, they may in particular be polyorganosiloxanes which can be inosoluble in the cosmetically acceptable medium.

Organopolysiloxanes are further defined in Walter Noll's "Chemistry and Technology of Silicones" (1968) Academy 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.

As a conditioning agent, cationic polymers such as polyquaterniums 22, 6, 10, 11, 35 and 37 and hexadimethrin chloride can also be used.

The concentration of conditioning agent (s) in the composition (s) useful in the invention may vary from 0.01% to 10% by weight relative to the total weight of the composition, preferably from 0.05% to 5% by weight. preferentially still from 0.1 to 3%.

The composition according to the invention may also comprise one or more organic thickeners.

The organic thickening agents may be selected from fatty acid amides, such as coconut diethanol or monoethanol amide and oxyethylenated alkyl ether carboxylic acid monoethanolamide, polymeric thickeners such as cellulosic thickeners, in particular hydroxyethylcellulose, hydroxypropylcellulose and carboxymethylcellulose, guar gum and its derivatives such as hydroxypropylguar, gums of microbial origin such as xanthan gum and scleroglucan gum, crosslinked homopolymers of acid. acrylic or acrylamidopropanesulfonic acid and the associative polymers, that is to say polymers comprising hydrophilic zones, and fatty-chain hydrophobic zones capable, in an aqueous medium, of reversibly associating with one another or with other mo lules.

According to a particular embodiment, the thickener is polymeric and selected from cellulose thickeners such as hydroxyethylcellulose, hydroxypropylcellulose and carboxymethylcellulose, guar gum and its derivatives such as hydroxypropylguar, gums of origin microbials such as xanthan gum and scleroglucan gum, crosslinked homopolymers of acrylic acid or acrylamidopropanesulfonic acid. With regard to the associative thickeners, it is possible to use one or more polymers of nonionic or ionic nature, preferably anionic or cationic.

Their chemical structure more particularly comprises at least one hydrophilic zone and at least one hydrophobic zone. By "hydrophobic group" is meant a linear or branched, saturated or unsaturated hydrocarbon-based radical or polymer comprising at least 8 carbon atoms, preferably from 10 to 30 carbon atoms, in particular from 12 to 30 carbon atoms. carbon and more preferably from 18 to 30 carbon atoms.

Preferably, the hydrocarbon group comes from a mono-functional 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 can also denote a hydrocarbon polymer, such as for example polybutadiene.

Among the anionic amphiphilic polymers having at least one fatty or hydrophobic chain, mention may be made of:

(I) polymers comprising at least one hydrophilic unit, and at least one fatty-chain allyl ether unit, more particularly those whose hydrophilic unit consists of an ethylenic unsaturated anionic monomer, advantageously a vinyl carboxylic acid and any particularly with an acrylic acid or a methacrylic acid, and mixtures thereof, and whose fatty chain allyl ether unit corresponds to the following monomer of formula (D):

CH ₂ = CR 'CH ₂ OB _n R (D) wherein R' denotes H or CH _3, B denotes the ethyleneoxy radical, n is zero or denotes an integer ranging from 1 to 100, R denotes a hydrocarbon radical chosen from alkyl, arylalkyl, aryl, alkylaryl, cycloalkyl radicals comprising from 8 to 30 carbon atoms, preferably 10 to 24, and even more particularly from 12 to 18 carbon atoms. A pattern of formula (D) plus particularly preferred is a unit in which R 'denotes H, n is equal to 10, and R denotes a C ₁₈ stearyl radical.

Of these anionic fatty-chain polymers, polymers formed from 20 to 60% by weight of acrylic acid and / or methacrylic acid, from 5 to 60% by weight of lower alkyl (meth) acrylates are preferred. from 2 to 50% by weight of fatty-chain allyl ether of formula (D), and from 0 to 1% by weight of a crosslinking agent which is a well-known copolymerizable polyethylenic unsaturated monomer, such as diallyl, allyl (meth) acrylate, divinylbenzene, (poly) ethylene glycol dimethacrylate, and methylene-bis-acrylamide.

Among these, the crosslinked terpolymers of methacrylic acid, ethyl acrylate, polyethylene glycol (10 EO) stearyl alcohol, such as Steareth 10, especially those sold by the company ALLIED COLLOIDS, are particularly preferred. the names Salcare SC 80 and Salcare SC90, which are aqueous 30% emulsions of a crosslinked terpolymer of methacrylic acid, ethyl acrylate and steareth-10-allyl ether (40/50/10).

(II) polymers comprising at least one hydrophilic unit of unsaturated olefinic carboxylic acid type, and at least one hydrophobic unit of C10-C30 alkyl ester type of unsaturated carboxylic acid.

Preferably, these polymers are chosen from those whose hydrophilic unit of unsaturated olefinic carboxylic acid type corresponds to the following monomer of formula (E):

CH ^~ C- C- OH

I II

Ri O _(E) wherein, R denotes H or CH ₃ or C ₂ H _5, that is to say acrylic acid, methacrylic acid or ethacrylic acid units, and whose hydrophobic unit of alkyl ester in C10-C30 acid unsaturated carboxylic acid corresponds to the monomer of the following formula:

CH ^~ C- C- OR,

I II FL O

2 (F) in which, R ₂ denotes H or CH ₃ or C ₂ H ₅ , that is to say acrylate, methacrylate or ethacrylate units, and preferably H, that is to say acrylate units or CH _3, that is to say, methacrylate units, R ₃ denoting a C ₁ -C ₃ alkyl radical, and preferably a C ₂ -C ₂₂ alkyl radical.

The C ₁₀ -C ₃₀ alkyl esters of unsaturated carboxylic acids are, for example, lauryl acrylate, stearyl acrylate, decyl acrylate, isodecyl acrylate, dodecyl, and the corresponding methacrylates, such as lauryl methacrylate, stearyl methacrylate, decyl methacrylate, isodecyl methacrylate and dodecyl methacrylate.

Among this type of fatty-chain anionic polymers, polymers formed from a monomer mixture comprising:

(i) essentially acrylic acid,

(ii) an ester of formula (F) described above and in which R ₂ denotes H or CH ₃ , R ₃ denoting an alkyl radical having from 12 to 22 carbon atoms,

(iii) and a crosslinking agent, which is a well-known copolymerizable polyethylenic unsaturated monomer, such as diallyl phthalate, allyl (meth) acrylate, divinylbenzene, (poly) ethylene glycol dimethacrylate, and methylene-bis- acrylamide.

Among this type of anionic fatty-chain polymers, use will be made more particularly of those consisting of 95 to 60% by weight of acrylic acid, which corresponds to the hydrophilic unit, of 4 to 40% by weight of C 10 alkyl acrylate. C ₃ o, which corresponds to the hydrophobic unit, and 0 to 6% by weight of polymerizable crosslinking monomer, or those consisting of 98 to 96% by weight of acid acrylic, which corresponds to the hydrophilic unit, from 1 to 4% by weight of C 10 -C 30 alkyl acrylate, which corresponds to the hydrophobic unit, and from 0.1 to 0.6% by weight of crosslinking polymerizable monomer, such as than those previously described.

Among the above polymers, the products sold by the company GOODRICH under the trade names Pemulen TRI, Pemulen TR2, Carbopol 1382, and even more preferably Pemulen TRI, and the product sold by the company, are particularly preferred according to the present invention. SEPPIC company under the name Coatex SX.

(III) terpolymers of maleic anhydride / α-C30-C30 olefin alkyl maleate, such as the maleic anhydride / C3-C3 olefin copolymer isopropyl nialeate sold under the name Performa V 1608 by the company NEWPHASE TECHNOLOGIES.

- (IV) acrylic terpolymers comprising:

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

(b) from 20 to 80% by weight of a non-surfactant α, β-monoethylenically unsaturated monomer different from (a),

(c) from 0.5 to 60% by weight of a nonionic monourethane, which is the reaction product of a monohydric surfactant with a monoethylenically unsaturated monoisocyanate, such as those described in the EP-A patent application -0173109 and more particularly a methacrylic acid / methyl acrylate / dimethyl metaisopropenyl benzyl isocyanate terpolymer of ethoxylated behenyl alcohol (40OE) in a 25% aqueous dispersion.

(V) copolymers comprising, among their monomers, an α, mon -monoethylenically unsaturated carboxylic acid and an α, mon-monoethylenically unsaturated carboxylic acid ester and an oxyalkylenated fatty alcohol (Cs-C3o).

Preferably, these compounds also comprise, as monomer, a carboxylic acid ester with α, β-monoethylenic unsaturation and C 1 -C 4 alcohol. As an example of this type of compound, mention may be made of Aculyn 22 sold by the company Rohm & Haas, which is a methacrylic acid / ethyl acrylate / stearyl methacrylate oxyalkylenated terpolymer.

The nonionic amphiphilic polymers with a fatty or hydrophobic chain are preferably chosen from:

- (1) celluloses modified with groups comprising at least one fatty chain, such as in particular:

hydroxyethylcelluloses modified with groups comprising at least one fatty chain, such as alkyl, arylalkyl or alkylaryl groups, and mixtures thereof, and in which the alkyl groups are preferably C8-C22, such as the product Natrosol Plus Grade 330 CS , comprising C ₁₆ alkyls, sold by AQUALON, or Bremocoll Ehm 100 sold by the company BEROL NOBEL,

those modified with polyalkylene glycol ether alkyl phenol groups, such as the product Amercell Polymer HM-1500, which is a nonyl phenol polyethylene glycol (15) ether sold by the company Amerchol,

(2) hydroxypropyl guars modified with groups comprising at least one fatty chain, such as the product Esaflor HM 22, comprising a C22 alkyl chain, sold by LAMBERTI, the RE210-18 products, comprising a C14 alkyl chain; , and RE205-1 comprising a C20 alkyl chain, sold by the company Rhone Poulenc,

(3) vinyl pyrrolidone copolymers and hydrophobic fatty-chain monomers, for example:

the products Aataron V216 and Ganex V216, which are vinylpyrrolidone / hexadecene copolymers, sold by the company I.S.P.,

the products Antaron V220 and Ganex V220, which are vinylpyrrolidone / eicosene copolymers, sold by the company I.S.P.,

(4) copolymers of methacrylates or of C ₁ -C ₆ alkyl acrylates and of amphiphilic monomers comprising at least one fatty chain, such as, for example, the oxyethylenated methyl acrylate / stearyl acrylate copolymer sold by GOLDSCHMIDT under the name Antil 208,

(5) copolymers of hydrophilic methacrylates or acrylates and of hydrophobic monomers comprising at least one fatty chain, such as, for example, polyethylene glycol methacrylate / lauryl methacrylate copolymer,

(6) polymers having an aminoplast ether skeleton having at least one fatty chain, such as Pure Thix compounds proposed by SUD-CHEMIE,

(7) polyether polyurethanes comprising in their chain, both hydrophilic sequences of mostly polyoxyethylenated nature and hydrophobic sequences which may be aliphatic sequences alone and / or cycloaliphatic and / or aromatic sequences.

Preferably, the polyether polyurethanes comprise at least two hydrocarbonaceous fatty chains having from 8 to 30 carbon atoms, separated by a hydrophilic sequence, the hydrocarbon chains possibly being pendant chains or chains at the end of the hydrophilic sequence.

By way of examples of nonionic fatty-chain polyether polyurethanes which can be used in the invention, use may be made of the urea-functional Rheeo late 205 sold by the company Rheox or the Rheolates 208, 204 and 212, as well as the Acryso l RM 84, Aculyn, Acryso l 44 and 46 from Rohm & Haas, Aculyn 46 being a polycondensate of polyethylene glycol at 150 or 180 moles of ethylene oxide, stearyl alcohol and methylene bis (4-cyclohexylisocyanate) (SMDI) at 15% by weight in a matrix of maltodextrin (4%) and water (8 1%), Aculyn 44 being a polyethylene glycol polycondensate. 150 or 1,80 moles of ethylene oxide, decyl alcohol and methylene bis (4-cyclohexylisocyanate) (SMDI), 35% by weight in a mixture of propylene glycol (39%) and water (26%). %). Mention may also be made of the product Elfacos T210 with a C 12 -C 14 alkyl chain and the product Elfacos T212 with a C ₁₈ alkyl chain from AKZO, as well as the product DW 1206B from ROHM & HAAS with a C20 alkyl chain and with urethane bond, proposed at 20% dry matter in water.

It is also possible to use solutions or dispersions of these polymers, especially in water or in a hydroalcoholic medium. By way of example of such polymers, mention may be made of Rheo late 255, Rheo late 278 and Rheolate 244 sold by Rheox. It is also possible to use the product DW 1206F and the DW 1206J proposed by the company Rohm & Haas.

The po lyurethanes polyethers used according to the invention are in particular those described in the article of G. Fonnum, J. Bakke and Fk. Hansen - Co lloid Polym. Sci 271, 380.389 (1993).

The cationic amphiphilic polymers having at least one fatty or hydrophobic chain used can in particular be chosen from quaternized cellulose derivatives, cationic polyurethanes, cationic polyvinyllactams, and preferably from quaternized cellulose derivatives.

By way of example of polymers of this type, mention may be made in particular of:

quaternized celluloses modified with groups comprising at least one fatty chain, such as alkyl, arylalkyl or alkylaryl groups containing at least 8 carbon atoms, and mixtures thereof,

the quaternized hydroxyethylcelluloes modified with groups comprising at least one fatty chain, such as alkyl, arylalkyl or alkylaryl groups containing at least 8 carbon atoms, and mixtures thereof.

The alkyl radicals carried by the cellulos or the quaternized hydroxyethylcelluloses above preferably contain from 8 to 30 carbon atoms. The aryl radicals preferably denote phenyl, benzyl, naphthyl or anthryl groups. Examples of C ₈ -C ₃₀ fatty chain quaternized alkylhydroxyethylcellulos are Quatrisoft LM 200, Quatriso ft LM-X 529-18a, Quatriso ft LM-X 529-18B (alkyl). in C 1 2) and Quatriso ft LM-X 529-8 (C ₁₈ alkyl) marketed by AMERCHOL and Crodacel QM products, Crodacel QL (C _{1 2} alkyl) and Crodacel QS (C 1 8 alkyl) ) marketed by the company CRODA.

The content of thickening polymers, if present, usually ranges from 0.05% to 5% by weight, based on the weight of the coloring composition.

According to a particularly advantageous embodiment, the dye composition according to the invention comprises one or more surfactants. The latter can be indifferently chosen, alone or as a mixture, from anionic, amphoteric, nonionic, zwitterionic and cationic surfactants.

With regard to the anionic surfactants, the salts, in particular the alkali metal salts such as the sodium salts, the ammonium salts, the amine salts, the aminoalcohol salts and the metal salts, are usually used. alkaline earth metals such as magnesium, and the salts of the following compounds, alone or as a mixture:

alkylsulphates, alkylethersulphates, alkylamidoethersulphates, alkylarylpolyethersulphates,

alkylsulfonates, alkylamidesulfonates, alkylarylsulphonates,

alkylsulfo succinates, alkylethersulfosuccinates, alkylamidesulfosuccinates,

the alkylsulphoacetates,

the acylsarconisates,

acylglutamates,

alkyl esters of polyglycoside carboxylic acids such as alkyl glucoside citrates, alkyl polyglycoside tartrates and alkyl polyglycoside sulfosuccinates,

alkylsulphosuccinamates,

acylisethionates, N-acyltaurates, acyllactylates, alkyl-D-galactoside uronic acids,

polyoxyalkylenated alkyl ether carboxylic acids, polyoxyalkylenated alkylarylether carboxylic acids, polyoxyalkylenated alkylamidoether carboxylic acids,

the alkyl or acyl group (RCO-) of these compounds containing from 10 to 24 carbon atoms and the aryl group preferably denoting a phenyl or benzyl group, the number of oxyalkylenated and preferably oxyethylenated groups is between 2 and 50; .

With regard to the nonionic surfactants, the latter may advantageously be chosen from the following compounds, alone or as a mixture:

polyethoxylated, polypropoxylated and polyglycerolated fatty alcohols,

polyethoxylated, polypropoxylated and polyglycerolated alpha-diols;

the number of ethylene oxide or propylene oxide groups ranging from 2 to 50, the number of glycerol groups ranging from 2 to 30,

condensates of ethylene oxide and of propylene oxide on fatty alcohols,

polyethoxylated fatty amides having from 2 to 30 moles of ethylene oxide,

polyglycerolated fatty amides containing from 1 to 5 glycerol groups,

polyethoxylated fatty amines containing from 2 to 30 mol of ethylene oxide,

the ethoxylated esters of sorbitan fatty acids having from 2 to 30 mol of ethylene oxide, the fatty acid esters of sucrose,

alkylpolyglucosides, N-alkylglucamine derivatives, these compounds comprising at least one alkyl or alkenyl chain comprising 10 to 24 carbon atoms.

copolymers of ethylene oxide and of propylene oxide. The cationic surfactants used in the composition according to the invention may in particular be chosen from the following compounds, alone or as a mixture:

the primary, secondary or tertiary fatty amines optionally polyethoxylated (2 to 30 mol of ethylene oxide) and their salts,

quaternary ammonium salts, such as tetraalkylammonium, alkylamidoalkyltrialkylammonium, trialkylbenzylammonium, trialkylhydroxyalkylammonium, alkylpyridinium chlorides and bromides,

the alkylimidazoline derivatives,

these compounds comprising at least one alkyl chain comprising 10 to 24 carbon atoms.

Finally, the amphoteric surfactants may be chosen from the following compounds, alone or as a mixture:

derivatives of secondary or tertiary aliphatic amines, in which the aliphatic group is a linear or branched chain containing from 10 to 24 carbon atoms and comprising at least one water-soluble anionic group such as, for example, a carboxylate, sulphonate group, sulphate, phosphate or phosphonate,

- alkylbetaines, sulphobetaines, alkylamidoalkyl _(C6-C8) alkylbetaines, alkylamidoalkyl (C ₆ -C ₈₎ sulphobetaines,

these compounds comprising at least one alkyl chain comprising from 10 to 24 carbon atoms.

Preferably, the surfactants are nonionic, anionic or amphoteric and even more preferably nonionic.

Usually, the surfactants represent from 0.01 to 50% by weight, preferably from 0.1 to 25% by weight relative to the weight of the composition.

The dyeing composition according to the invention may also comprise various adjuvants conventionally used in compositions for dyeing hair, such as, for example, cationic, anionic, nonionic, amphoteric or zwitterionic polymers other than the thickeners mentioned above, and mixtures thereof, mineral thickening agents such as clays, antioxidants such as, for example, ascorbic acid, erythorbic acid, reducing agents different from the aforementioned compounds (I) such as, inter alia, erythorbic acid, reducing sugars, penetrating agents, sequestering agents such as ethylenediamine tetraacetic and its salts, perfumes, mattifying agents with, for example, titanium oxides, buffers, dispersing agents, film-forming agents, ceramides and agents preservatives.

The adjuvants above are generally present in an amount for each of them between 0.0 1 and 20% by weight relative to the weight of the dye composition.

The dye composition used according to the invention as well as the composition used in step a) may also comprise a cosmetically acceptable medium.

The cosmetically acceptable medium, which is a suitable medium for the staining of human keratinous fibers, preferably comprises water and optionally one or more additional solvents different from the organic compounds (II) having a value of Hansen's δΗ parameter. lubilité

1/2

less than or equal to 16 MPa and molecular weight less than 250 g / mol and different from the compounds (I) mentioned above.

Examples of such organic solvents are, for example, C 2 -C 4 linear or branched alkanols, such as ethanol and isopropanol, polyols and polyol ethers, such as butoxyethanol, hexylene glycol, propylene glycol, dipropylene glycol, glycerol and mixtures thereof.

The additional solvent (s) other than the organic compounds present in the dyeing composition defined above may be present in proportions ranging preferably from 1 to 40% by weight relative to the total weight of the dye composition, and even more preferably from at 30% by weight. The amount of water in the dye composition used according to the invention is preferably greater than 10% by weight relative to the weight of the composition, and more advantageously greater than or equal to 25% by weight. Preferably, the water content is between 25 and 98% by weight relative to the weight of the composition.

The pH of the dye composition used according to the invention may be between 2 and 12 inclusive. Preferably, the pH of the dyeing composition is between 8 and 12 inclusive.

It can be adjusted to the desired value by means of one or more acidifying agents or one or more alkalinizing agents usually used in the field.

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

Among the alkalinizing agents, mention may be made, for example, of alkaline carbonates, alkanolamines such as mono-, di- and triethanolamines and their derivatives, sodium or potassium hydroxides and compounds of the following formula:

^Rx \ ^Rz

_/ N WN

Ry ^N Rt

wherein W is a propylene residue optionally substituted with a hydroxyl group or a C ₁ -C ₆ alkyl radical; Rx, Ry, Rz and Rt, which are identical or different, represent a hydrogen atom, an alkyl radical Ci-C ₆ hydroxyalkyl or Ci-C _6.

The dye composition used according to the invention may also comprise one or more oxidizing agents.

In particular, the composition with oxidant is obtained by extemporaneous mixing before the application of a previously described composition, with at least one composition comprising one or more oxidizing agents. The oxidizing agent is preferably chosen from hydrogen peroxide, urea peroxide, alkali metal bromates or ferricyanides, peroxygenated salts, for example alkali or alkaline earth metal persulfates, perborates and percarbonates. like sodium, potassium, magnesium.

The use of hydrogen peroxide is particularly preferred.

This oxidizing agent is advantageously constituted by hydrogen peroxide in aqueous solution (hydrogen peroxide), the titre of which may vary, more particularly, from 1 to 40 volumes, and even more preferably from 5 to 40 volumes.

The dyeing compositions used according to the invention may result from the extemporaneous mixing of several compositions.

According to a first embodiment, the composition applied does not comprise an oxidizing agent. This embodiment is appropriate especially in the case where the composition does not include oxidation dye precursor (bases, couplers).

According to a second embodiment, the composition is applied in the presence of at least one oxidizing agent.

This embodiment can be implemented if the composition comprises, as dyestuffs, only direct dyes (dye (s) with a hydrophobic nature, and optionally one or more additional direct dyes) or even if the composition comprises a dye (s). or a plurality of hydrophobic compounds, optionally one or more synthetic and / or natural direct dyes, combined with one or more oxidation dye precursors (bases and couplers).

According to a first variant of this second embodiment, the composition which has just been detailed and which is obtained by extemporaneous mixing before application of a dyeing composition used according to the invention, is applied to the fibers in step b). invention without an oxidizing agent with an oxidizing composition. According to a second variant of this second embodiment, step b) is applied to the dye composition used according to the invention without an oxidizing agent, and to an oxidizing composition, successively and without intermediate rinsing.

The oxidizing composition used comprises one or more oxidizing agents as defined above.

Regarding the organic solvents possibly present in the oxidizing composition, reference may be made to the list indicated previously in the context of the description of the dyeing composition. These organic solvents may also be chosen from organic compounds (II) optionally present in the dyeing composition used according to the invention having a value of

1/2

Hansen parameter δΗ less than or equal to 16 MPa and molecular weight less than 250 g / mol and different from the compounds (I) mentioned above.

The oxidizing composition may be in the form of a solution, an emulsion or a gel.

It may optionally comprise one or more additives conventionally used in the field of the coating of human keratinous fibers, depending on the desired dosage form. We can again refer to the list of additives given above.

Whatever the embodiment chosen (with or without an oxidant), the app composition liquefied on the fibers in step b) is left in place for a duration, in general, of the order of 1 minute to 1 hour. preferably from 10 minutes to 30 minutes.

Step a) and / or step b) of the process according to the invention can be carried out under heat at a temperature ranging from 40 ° C to 210 ° C and preferably from 40 ° C to 120 ° C. The step of heating the hair can be performed by drying the hair and / or by passing a heating tool. In particular, the heating step can be carried out by means of a hair dryer, a helmet, heating curlers, a hair straightener, a curling iron, a crimping iron, a wispy iron, an infra-red lamp, an exothermic system in the composition. Step a) and / or step b) of the process according to the invention may also be followed by rinsing the keratinous fibers.

The method according to the invention may further comprise a keratinous fiber washing step after steps a) and b).

The invention also relates to a multi-compartment device or kit, comprising a first compartment comprising a composition containing one or more organic or inorganic metal salts as defined above, and a second compartment comprising a dye composition as defined above.

The device according to the invention may also comprise a third compartment comprising an oxidizing composition.

The device according to the invention may further comprise a fourth compartment comprising a detergent composition.

The invention is illustrated by the following examples.

Example 1

The following coloring composition A is prepared, the formulation of which is given in Table 1. Composition A is a dye composition used according to the invention.

Table 1

AT

Indigo [1] i g

Alcoholic benzyl 5 g

Ethano l 15 g

Acetoin i g

Sodium hydroxide to

12g

10% aqueous solution

Water qs 100g [1] Indigo, CAS = 482-89-3, sold by Sigma Aldrich The composition is allowed to stir under argon for 2 hours at

40 ° C:

Then, the pH is adjusted to 9.6 with 4 g of 25% ammonia in aqueous solution and 4 g of 90% lactic acid in aqueous solution.

In pairs of strands of hair with 90%> of natural and permuted white hair, an aqueous composition containing zinc sulphate at a rate of 1% by weight of the zinc element relative to the total weight of the aqueous composition is applied ( sold under the name 10888 1 by the company Merck).

The treated locks are then left to pose the helmet for 10 minutes at room temperature (about 25 ° C).

These locks are then dewatered and then applied to them composition A.

Composition A is left for 30 minutes at room temperature.

The locks are then dewatered, rinsed, shampooed and dried.

The results of staining on locks are observed visually and accompanied by colorimetric measurements expressed in ΔΕ rise relative to uncoiled hair.

It is noted that the coloring obtained by the process of the invention is powerful.

These results are confirmed by colorimetric measurements. Colorimetric measurements can be made using the Konica Mino lta CM-2600d spectrocolorimeter in the CIE L * a * b * system. In this system, L * represents the intensity of the coloration obtained, the lower the value of L *, the more intense the coloration obtained. The chromaticity is measured by the values a * and b *, a * indicating the value on the green / red color axis and b * indicating the value on the blue / yellow color axis.

The rise in the coloring can be expressed in ΔΕ from the formula: ΔE = - L ₀ *) ² + (a * - a ₀ *) ² + (b * - b ₀ *) ² in which:

- L *, a * and b *, represent the parameters of colored hair and

- L ₀ *, a ₀ * and bo * represent the parameters of unstained hair.

The results are shown in Table 2.

The power of the coloring is also indicated by the low value of L *.

Table 2

Example 2

A dyeing composition used according to the invention is prepared, the formulation of which is given in Table 3.

Table 3

B

Indirubin [2] ig

Benzyl alcohol 5g

Ethanol 15g

Acetoin ig

Sodium hydroxide to

12g

10% in aqueous solution

Water qs 100g [2] Indirubin, CAS = 479-41-4 (CI75790)

The solution is stirred under argon for 2 h at 40 ° C.

The treated locks are then left to the helmet for 30 minutes under helmet.

These locks are then dewatered, then they are then applied to the composition B according to the method of the invention.

The locks are then dewatered, rinsed, shampooed and dried.

The staining results on locks are visually observed and accompanied by colorimetric measurements expressed in ΔΕ relative to uncolored hair.

Strong, stubborn, vio laced red stains are obtained.

The results are given in Table 4.

Table 4

Mounted on natural hair mounted on permed hair

L * a * b * ΔΕ L * a * b * ΔΕ

/ hair / hair non colored non colored

Hair

no 60.38 0.57 13.09 - 61.38 0.31 12.77 - colored

Hair

colored 40.58 5.64 -5.49 27.62 31.48 6.07 -6.89 36.25 by B Example 3

The following dyeing compositions used according to the invention are prepared, the formulations of which are given in Table 5.

Table 5

[1] Indigo, CAS = 482-89-3, marketed by Sigma Aldrich

The compositions are prepared and applied to pairs of natural and permed locks of hair with 90% white hair, previously treated with zinc sulphate under the same conditions as those of Example 2.

Strong, stubborn blue colors are obtained.

Claims

REVEND ICATI ON S

1. A process for dyeing keratinous fibers, in particular human keratinous fibers, comprising:

a step of applying to said keratinous fibers a composition comprising one or more organic or inorganic metal salts,

b) a step of applying to the keratinous fibers a dye composition comprising one or more hydrophobic direct dyes of logP greater than or equal to 2 and one or more compounds (I) having in their structure a sequence:

with n denoting an integer ranging from 0 to 4, and

- designating a grouping:

step a) being performed before, during or after step b).

2. Method according to claim 1 characterized in that the one or more metal compounds are selected from organic or inorganic compounds of iron, copper, zinc, tin, aluminum, manganese, copper, silver. .

3. Method according to claim 2 characterized in that the one or more metal compounds are selected from organic or inorganic zinc salts, preferably zinc chloride, zinc sulfate and zinc gluconate.

4. Process according to any one of the preceding claims, characterized in that the metal salt or salts have a molecular weight of less than 500 g / mol, preferably less than 250 g / mol.

5. Process according to any one of the preceding claims, characterized in that the concentration of the organic or inorganic metal salt or salts in the composition containing them varies from 0.01 to 20%, preferably from 0.1 to 10%. more preferably from 0.5 to 5%, expressed as the weight of metal relative to the total weight of the composition containing them.

6. Process according to any one of the preceding claims, characterized in that the hydrophobic direct dye or dyes are chosen from the following compounds: Disperse Red 17, Disperse Violet 1, HC Yellow 7, Disperse Blue 377, Disperse Red 13, Disperse Green 9, Solvent Black 3, Disperse Blue 148, Disperse Violet 63, Disperse Blue 60, Disperse Blue 14, Solvent Orange 15, Solvent Orange 7, Solvent Blue 14, Disperse Yellow 82, Indigo Dyes, and mixtures thereof.

7. Process according to claim 6, characterized in that the hydrophobic direct dye or dyes are chosen from indigo dyes, and preferably from indigo, isoindigo, indirubine, isoindirubin, 4,4'- dibromoindigo, 6,6'-dibromoindigo, 5,5'-dibromoindigo, cis -6,6'-dibromoindigo, 5,5 ', 7,7'-tetrabromoindigo, 4,4 7,7'-tetrachloroindigo, 3H-indol-3-one, 1, 2-dihydro-2- (3-oxobenzo [b] thien-2- (3H) -ylidene), thioindigo, Vat Red 1, cis-thioindigo, 6,6'-dichloro-4,4'-dimethylindigo, 5,5'-dichloro-7,7'-dimethylindigo, 4,4'-7,7'-tetramethylindigo, Thioindigo Scarlet R, 2H-indol-2-one, 1,3-dihydro-3- (3-oxobenzo [b] thien-2 (3H) -ylidene) -, (3E) -, thioindirubin, 2H indol-2-one, 1,3-dihydro-3- (2-oxobenzo [b] thiophen-3 (2H) -ylidene), benzo [b] thiophen-2 (3H) -one, 3- (2) -oxobenzo [b] thiophen-3 (2H) -ylidene.

8. Process according to any one of the preceding claims, characterized in that the hydrophobic direct dye or dyes represent from 0.01 to 20% by weight, preferably from 0.05 to 10% by weight, better still from 0, 1 to 5% by weight of the total weight of the dyeing composition.

9. Method according to any one of the preceding claims characterized in that the compound (s) (I) have in their structure a sequence:

C- CH C = C

^{0 0H} (A) or ^{0H 0H} (B).

10. Process according to any one of the preceding claims, characterized in that the compound (s) (I) correspond to the following formula (C):

R, ^ (CH ₂ K

⁰ (C)

with:

n denoting an integer ranging from 0 to 4, preferably from 0 to 2, and X _TTT ^ Y denoting a grouping:

R 1 and P ₂ represent, independently of one another, a hydrogen atom, a substituted or unsubstituted phenyl radical, a hydroxyl radical, a C 1 -C ₄ alkoxy radical or a linear C 1 -C ₄ alkyl radical; or branched, unsubstituted or substituted with one or two radicals selected from the radicals -OR ', -C (O) R ", -COOR'", with R ', R "and R'" representing, independently of one another a hydrogen atom, a linear or branched C1-C4 alkyl radical, or

R 1 and R ₂ forming, with the carbon chain to which they are attached, an unsubstituted 5- or 6-membered non-aromatic carbon ring,

this or these compounds (I) being preferably chosen from hydroxyacetone, acetoin, glutaroin, adipoin, dihydroxyacetone, glycol aldehyde, benzoin, 2,3-dihydroxyacrylaldehyde, cyclopentanedione, acetonyl acetone, acetyl acetone, diacetyl, dipropionyl, 2-ketoglutaric acid, 3-ketoglutaric acid, pyruvic acid, levulinic acid, acetoacetic acid, propionylacetic acid, acetonylmalonic acid, acetomethyl acetate, acetoethyl acetate, acetopyruvic acid, cyclohexanedione.

11. Process according to any one of the preceding claims, characterized in that the compound or compounds (I) represent from 0.01 to 20% by weight, preferably from 0.05 to 10% by weight, better still from 0.1. at 5% by weight of the total weight of the dyeing composition.

12. Method according to any one of the preceding claims, characterized in that the dye composition comprises one or more organic compounds (II) having a value of

1/2 Hansen δΗ parameter of solubility less than or equal to 16 MPa,

1/2

preferably less than 16 MPa, more preferably ranging from 5 to 15.8 MPa ^1/2 better 8 to 15.8 MPa ^1/2 , and molecular weight less than 250 g / mol, or organic compounds being preferably chosen from alkanols, aliphatic esters, ethers, aromatic alcohols, alkylaryl alcohols, aromatic acids, aliphatic acids, alkylene carbonates, lactones and mixtures thereof, and more preferentially from alkanols, aliphatic esters, ethers, aromatic alcohols or alkylaryl alcohols, aromatic acids, aliphatic acids and mixtures thereof.

13. Process according to any one of the preceding claims, characterized in that the dyeing composition comprises one or more additional dyes other than dyes with a hydrophobic character of log P greater than or equal to 2, chosen from natural dyes and non-natural direct dyes. oxidation dye precursors, or combinations thereof.

14. Method according to any one of the preceding claims, characterized in that step a) and / or step b) are followed by rinsing the keratinous fibers.

15. Multi-compartment device or kit, comprising a first compartment comprising a composition containing one or several organic or inorganic metal salts as defined in any one of claims 1 to 5, and a second compartment comprising a dye composition as defined in claim 1.