FR3083100A1 - DYEING COMPOSITION COMPRISING A DIRECT DYE, A PEROXYGEN SALT AND A CYCLODEXTRIN, AND METHOD USING THE SAME - Google Patents

Abstract

The present invention relates to a composition for dyeing keratin fibers, in particular human keratin fibers such as the hair, comprising at least one peroxygenated salt, at least one direct dye, and at least one cyclodextrin. The invention also relates to a process for dyeing keratin fibers, in particular human keratin fibers such as the hair, using said dye composition, to the use of said composition for dyeing keratin fibers, as well as a process for simultaneous bleaching and coloring of keratin fibers comprising the application of said coloring composition and of an aqueous oxidizing composition to the keratin fibers. The invention also relates to a device with several compartments containing said coloring composition and an aqueous oxidizing composition.

Description

© COLORING COMPOSITION COMPRISING A DIRECT DYE, A PEROXYGEN SALT AND A CYCLODEXTRIN, AND METHOD USING THIS COMPOSITION.

The present invention relates to a composition for coloring keratin fibers, in particular human keratin fibers such as the hair, comprising at least one peroxygenated salt, at least one direct dye, and at least one cyclodextrin.

The invention also relates to a process for dyeing keratin fibers, in particular human keratin fibers such as the hair, using said dye composition, to the use of said composition for dyeing keratin fibers, as well as a process for simultaneous bleaching and coloring of keratin fibers comprising the application of said coloring composition and of an aqueous oxidizing composition to the keratin fibers.

The invention also relates to a device with several compartments containing said coloring composition and an aqueous oxidizing composition.

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Coloring composition comprising a direct dye, a peroxygenated salt and a cyclodextrin, and process using this composition

The present invention relates to a composition for dyeing keratin fibers, in particular human keratin fibers such as the hair, comprising at least one peroxygenated salt, at least one direct dye, and at least one cyclodextrin.

The invention also relates to a process for dyeing keratin fibers, in particular human keratin fibers such as the hair, using said dye composition, to the use of said composition for dyeing keratin fibers, as well as to a process for simultaneous bleaching and coloring of keratin fibers comprising the application of said coloring composition and of an oxidizing composition to the keratin fibers.

The invention also relates to a device with several compartments containing said coloring composition and an oxidizing composition.

Many people have long sought to change the color of their hair, and in particular to lighten their hair.

It is known to dye keratin fibers with dye compositions containing direct dyes. These compounds are colored and coloring molecules with an affinity for fibers. It is known, for example, to use direct dyes of the benzene nitro type, anthraquinone dyes, nitropyridines, dyes of the azo, xanthene, acridine, azine or triarylmethane type.

Usually, these dyes are applied to the fibers, possibly in the presence of a chemical oxidizing agent, if it is desired to obtain a simultaneous lightening effect on the fibers. Once the exposure time has elapsed, the fibers are rinsed, possibly washed and dried.

It is also known to lighten hair in the presence of parsley (also called peroxygenated salt), in particular persulfate, alkaline agent and hydrogen peroxide when it is desired to achieve higher levels of lightening. However, these discoloration treatments are generally accompanied by the appearance of unsightly yellow-orange reflections.

Direct dyes can then be introduced into the bleaching compositions to obtain a more aesthetic color rendering.

However, direct dyes have little or no resistance to chemical oxidizing agents. This low stability of direct dyes to oxidation has in particular the effect of obtaining hair dyes having a slight increase in color and a low level of lightening of the keratin fibers.

There is thus a real need to develop coloring and / or lightening compositions comprising at least one dye and at least one chemical oxidizing agent, having good stability over time, and making it possible to obtain colorations with varied, powerful, chromatic shades. , aesthetic, not very selective and / or resistant well to the various aggressions that the hair can undergo such as shampoos, light, sweat and permanent deformation, while having good performance in lightening.

In particular, one of the aims of the present invention is to provide coloring compositions having a better rise in color and a better level of lightening of the keratin fibers.

These aims are achieved by the present invention, which relates in particular to a composition for dyeing keratin fibers, in particular human keratin fibers, such as the hair, comprising:

- at least one peroxygenated salt, preferably a persulfate,

- at least one direct dye, and

- at least one cyclodextrin.

It is found that the coloring composition according to the invention has better stability over time compared to conventional coloring compositions based on peroxygenated salts, in particular persulfates, in particular good stability during the pause time on the hair.

The better stability of these direct dyes results in particular in a less variation in color of the mixture with the peroxygenated salts, in particular the persulfates, which makes it possible to lead to improved dyeing properties. It has in particular been observed that the colorations of the keratin fibers obtained with the compositions according to the invention exhibit a better rise in color as well as a good level of lightening of the keratin fibers.

The invention also relates to a process for dyeing keratin fibers, in particular human keratin fibers such as the hair, comprising at least one step of applying to said fibers a dye composition as defined above.

The invention also relates to the use of the coloring composition as defined above, for coloring keratin fibers.

Another object of the invention relates to a process for simultaneous bleaching / coloring of keratin fibers, in particular human keratin fibers such as the hair, comprising at least one step of application to said fibers:

- a coloring composition as described above, and

- an oxidizing composition distinct from the coloring composition comprising one or more chemical oxidizing agents, preferably different from the peroxygenated salts, more preferably chosen from hydrogen peroxide.

The invention also relates to a device comprising at least two compartments, a first compartment containing a coloring composition as defined above; a second compartment containing an aqueous oxidizing composition comprising one or more chemical oxidizing agents.

The invention also relates to a device comprising at least three compartments, a first compartment containing a composition C1 containing one or more peroxygenated salts, preferably one or more persulfates; a second compartment comprising a composition C2 comprising one or more direct dyes and one or more cyclodextrins; a third compartment containing an oxidizing composition comprising one or more chemical oxidizing agents different from the peroxygenated salts.

Other objects, characteristics, aspects and advantages of the invention will appear even more clearly on reading the description and the example which follows.

In this description, and unless otherwise indicated:

- the expression at least one is equivalent to the expression one or more and may be substituted for it;

- the expression included between is equivalent to the expression going from and can be substituted for it, and implies that the limits are included.

- By "keratin fibers" according to the present application, is meant human keratin fibers and more particularly the hair.

Peroxygenated salts

The coloring composition according to the invention comprises one or more peroxygenated salts.

Preferably, the peroxygenated salts are chosen from persulfates; perborates; percarbonates of alkali metals, alkaline earth metals, or ammonium; magnesium peroxide; and their mixtures.

More preferably, the coloring composition according to the present invention comprises at least one persulfate.

Persulfates, also called peroxysulfates, correspond, within the meaning of the invention, to SOs ² 'anions (anion peroxomonosulfate) or S2O8 ² · (anion peroxodisulfate) or to compounds comprising at least one of these anions.

Preferably, the persulfates according to the invention are chosen from peroxodisulfates.

According to a preferred embodiment of the invention, the coloring composition according to the invention comprises at least one peroxygenated salt chosen from persulfates; preferably from alkali metal persulfates, alkaline earth metal persulfates, ammonium persulfates, and mixtures thereof; more preferably from (bis) tetrabutylammonium persulfate, barium persulfate, magnesium persulfate, calcium persulfate, sodium persulfate, potassium persulfate, ammonium persulfate, and mixtures thereof; even more preferably from sodium persulfate, potassium persulfate, ammonium persulfate, and mixtures thereof; even better the coloring composition comprises potassium persulfate.

Preferably, the total content of peroxygenated salt (s) present in the coloring composition according to the invention is between 1 and 30% by weight, more preferably between 3 and 25% by weight, more preferably still between 4 and 20% by weight, and even better between 5 and 18% by weight, relative to the total weight of the coloring composition.

Preferably, the total content of persulfate present in the coloring composition according to the invention is between 1 and 30% by weight, more preferably between 3 and 25% by weight, more preferably still between 4 and 20% by weight. weight, and even better between 5 and 18% by weight, relative to the total weight of the coloring composition.

Direct dyes

The coloring composition according to the present invention comprises at least one direct dye.

The direct dye (s) which can be used according to the invention are chosen from natural direct dyes, synthetic direct dyes and their mixtures.

Preferably, the direct dye or dyes which can be used according to the invention are chosen from ionic direct dyes and non-ionic direct dyes, more particularly from cationic direct dyes, non-ionic direct dyes, anionic direct dyes and their mixtures; more preferably from cationic direct dyes, anionic direct dyes, and mixtures thereof.

The direct dyes are, for example, chosen from neutral, acidic or cationic benzene nitro direct dyes, neutral (nonionic), acidic (anionic) or cationic direct dyes, tetraazapentamethine dyes, quinone dyes and in particular neutral anthraquinone dyes, acids or cationic, azine direct dyes, triarylmethane direct dyes, azomethine direct dyes and natural direct dyes.

The cationic direct dye (s) contain at least one quaternized cationic chromophore or at least one chromophore carrying a quaternized or quaternizable cationic group.

According to a particular embodiment of the invention, the cationic direct dyes comprise at least one quaternized cationic chromophore.

Mention may be made, as cationic direct dyes according to the invention, of acridine dyes; acridones; anthranthrones; anthrapyrimidines; anthraquinones; azines; (poly) azo, hydrazono or hydrazones, in particular arylhydrazones; azomethines; benzanthrones; benzimidazoles; benzimidazolones; benzindoles; benzoxazoles; benzopyranes; benzothiazoles; benzoquinones; bisazines; bis isoindolines; carboxanilides; coumarins; cyanines such as azacarbocyanines, diazacarbocyanines, diazahémicyanines, hemicyanines, or tétraazacarbocyanines; diazines; diketopyrrolopyrroles; dioxazines; diphenylamines; diphenylmethanes; dithiazines; flavonoids such as flavanthrones and flavones; fluorindines; formazans; indamines; indanthrones; indigoids and pseudoindigoids; indophenols; indoanilines; isoindolines; isoindolinones; isoviolanthrones; lactones; (poly) methines such as dimethines of stilbene or styryl types; naphthalimides; naphthhanilides; naphtholactams; naphthoquinones; nitro, especially aromatic nitro (hetero); oxadiazoles; oxazines; perilones; perinones; perylenes; phenazines; phenoxazine; phenothiazines; phthalocyanine; polyenes / carotenoids; porphyrins; pyranthrones;

pyrazolanthrones; pyrazolones; pyrimidinoanthrones; pyronines; quinacridones; quinolines; quinophthalones;

squaranes; tetrazoliums; thiazines, thioindigo; thiopyronines; triarylmethanes, or xanthenes.

For cationic azo dyes, mention may be made especially of those derived from cationic dyes described in the Kirk-Othmer Encyclopedia of Chemical Technology, “Dyes, Azo”, J. Wiley & sons, updated on 19/04/2010.

Among the azo dyes which can be used according to the invention, mention may be made of the cationic azo dyes described in patent applications WO 95/15144, WO 95/01772 and EP-714954.

According to a preferred embodiment of the invention, the direct dye (s) are chosen from cationic dyes called "basic dyes".

Mention may be made, among the azo dyes described in the Color Index International 3rd edition, and in particular the following compounds:

-Basic Red 22

-Basic Red 76

-Basic Yellow 57

-Basic Brown 16

-Basic Brown 17

Among the cationic quinone dyes those mentioned in the abovementioned Color Index International are suitable, and among these, the following dyes may be mentioned, among others:

-Basic Blue 22

-Basic Blue 99

Among the azine dyes which are suitable, mention may be made of those listed in the International Color Index and for example the following dyes:

-Basic Blue 17

-Basic Red 2.

Among the cationic triarylmethane dyes which can be used according to the invention, there may be mentioned, in addition to those listed in the Color Index, the following dyes:

-Basic Green 1

-Basic Violet 3

-Basic Violet 14

-Basic Blue 7

-Basic Blue 26.

Mention may also be made of cationic dyes in documents US 5888252, EP 1 133975, WO 03/029359, EP 860636, WO 95/01772, WO 95/15144, EP 714954. We can also cite those listed in the encyclopedia The chemistry of synthetic dye by K. VENKATARAMAN, 1952, Academic press vol 1 to 7, in the encyclopedia Kirk-Othmer Chemical technology, chapter Dyes and Dye intermediate, 1993, Wiley and sons, and in various chapters of the encyclopedia ULLMANN's ENCYCLOPEDIA of Industrial chemistry 7th edition, Wiley and sons.

Preferably, the cationic direct dyes are chosen from those derived from dyes of the azo type, and hydrazono.

According to a particular embodiment, the direct dyes are cationic azo, described in EP 850636, FR 2788433, EP 920856, WO 9948465, FR 2757385, EP 850637, EP 918053, WO 9744004, FR 2570946, FR 2285851, DE 2538363, FR 2189006, FR 1560664, FR 1540423, FR 1567219, FR 1516943, FR 1221122,

DE 4220388, DE 4137005, WO 0166646, US 5708151, WO 9501772,

WO 515144, GB 1 195386, US 3524842, US 5879413, EP 1062940,

EP 1133976, GB 738585, DE 2527638, FR 2275462, GB 1974-27645,

Acta Histochem. (1978), 61 (1), 48-52; Tsitologiya (1968), 10 (3), 4035; Zh. Obshch. Khim. (1970), 40 (1), 195-202; Ann. Chim. (Rome) (1975), 65 (5-6), 305-14; Journal of the Chinese Chemical Society (Taipei) (1998), 45 (1), 209-211; Rev. Roum. Chim. (1988), 33 (4), 377-83; Text. Res. J. (1984), 54 (2), 105-7; Chim. Ind. (Milan) (1974), 56 (9), 600-3; Khim. Tekhnol. (1979), 22 (5), 548-53; Ger. Monatsh. Chem. (1975), 106 (3), 643-8; MRL Bull. Res. Dev. (1992), 6 (2), 21-7; Lihua Jianyan, Huaxue Fence (1993), 29 (4), 233-4; Dyes Pigm. (1992), 19 (1), 69-79; Dyes Pigm. (1989), 11 (3), 163-72.

Preferably, the cationic direct dye (s) comprise a quaternary ammonium group, more preferably the cationic charge is endocyclic.

These cationic radicals are for example a cationic radical:

- with exocyclic charge (di / tri) (Ci-C8) alkylammonium, or

- with an endocyclic charge such as comprising a cationic heteroaryl group chosen from: acridinium, benzimidazolium, benzobistriazolium, benzopyrazolium, benzopyridazinium, benzoquinolium, benzothiazolium, benzotriazolium, benzoxazolium, bi-pyridinium, bis-tetrazolidiumidolidolidolidolidolidinidolidinolidinolidinolidinolidinolidinolidinolidinolidinolidinolidinolidinolidinolidinolidinolidium naphthoimidazolium, naphthooxazolium, naphthopyrazolium, oxadiazolium, oxazolium, oxazolopyridinium, oxonium, phenazinium, phénooxazolium, pyrazinium, pyrazolium, pyrazoyltriazolium, pyridinium pyridinoimidazolium, pyrrolium, pyrylium, quinolium, tetrazolium, thiadiazolium, thiazolium, thiazolopyridinium, thiazoylimidazolium, thiopyrylium, triazolium or xanthylium.

Mention may be made of the hydrazono cationic dyes of formula (C-II) and (C-III), the azo compounds of formulas (C-IV) and (CV) below, as well as their optical, geometric, tautomeric isomers, their salts. acids or bases, organic or mineral, as well as their solvates such as hydrates:

Hét ⁺ -C (Ra) = NN (Rb) -Ar, Q 'Hét ⁺ -N (Ra) -N = C (R _b ) -Ar, Q' (C-II) (C-III)

Hét ⁺ -N = N-Ar, Q 'Ar ⁺ -N = N-Ar ”, Q' (C-IV) (CV) formulas (C-II) to (CV) in which:

• Hét ⁺ represents a cationic heteroaryl radical, preferably with an endocyclic cationic charge such as imidazolium, indolium, or pyridinium, optionally preferentially substituted by at least one (Ci-Cs) alkyl group such as methyl;

• Ar ⁺ represents an aryl radical, such as phenyl or naphthyl, with an exocyclic cationic charge preferably ammonium, particularly tri (Ci-C8) alkyl-ammonium such as trimethylammonium;

• Ar represents an aryl group, in particular phenyl, optionally substituted, preferably by one or more electron donor groups such as i) (Ci-Cs) optionally substituted alkyl, ii) (Ci-Cs) optionally substituted alkoxy, iii) (di) ( Ci-C8) (alkyl) amino optionally substituted on the alkyl group or groups by a hydroxyl group, iv) aryl (Ci-Cs) alkylamino, v) N- (Ci-C8) alkyl-N-aryl (Ci-C8) optionally substituted alkylamino or then Ar represents a julolidine group;

• Ar ”represents an optionally substituted (hetero) aryl group such as phenyl or pyrazolyl optionally substituted, preferably by one or more (Ci-Cs) alkyl, hydroxyl, (di) (Ci-C8) (alkyl) amino, (Ci -Csjalcoxy or phenyl;

• R _a and Rb, identical or different, representing a hydrogen atom or a group (Ci-Csjalkyle optionally substituted, preferably by a hydroxyl group;

• or the substituent R _a with a substituent of Het ⁺ and / or Rb with a substituent of Ar form together with the atoms which carry them a (hetero) cycloalkyl; particularly R _a and Rb, representing a hydrogen atom or a (CiC ₄ ) alkyl group optionally substituted by a hydroxyl group;

• Q ’represents an organic or mineral anionic counterion such as a halide or an alkyl sulphate.

In particular, mention may be made of direct dyes with azo and hydrazono endocyclic cationic charges of formula (C-II) to (C-V) as defined above; more particularly the cationic direct dyes of formula (C-II) to (C-V) with cationic endocyclic charge described in patent applications WO 95/15144, WO 95/01772 and EP-714954.

Preferably, the following direct dyes can be mentioned:

(C-IV-1) formulas (C-II-1) and (C-IV-1) in which:

- R ¹ represents a group (Ci-C ₄ ) alkyl such as methyl;

- R ² and R ³ , identical or different, represent a hydrogen atom or a (Ci-C ₄ ) alkyl group such as methyl; and

- R ⁴ represents a hydrogen atom or an electron donor group such as (Ci-Csjalkyle optionally substituted, (Ci

Cs) optionally substituted alkoxy, (di) (Ci-C8) (alkyl) amino optionally substituted on the alkyl group or groups by a hydroxyl group; particularly R ⁴ is a hydrogen atom,

- Z represents a CH group or a nitrogen atom, preferably CH,

- Q is an anionic counter ion as defined above, particularly halide such as chloride or an alkyl sulphate such as methyl sulphate or mesytyl.

In particular, the dyes of formula (C-II-1) and (C-IV-1) are chosen from Basic Red 51, Basic Yellow 87 and Basic Orange 3 1 or their derivatives:

Basic Red 51

Basic Orange 3 1

Basic Yellow 87 with Q ’an anionic counter ion as defined above, particularly a halide such as chloride or an alkyl sulfate such as methyl sulfate or mesytyl.

According to a particular embodiment of the invention, the direct dyes are fluorescent, that is to say that they contain at least one fluorescent chromophore as defined above.

As fluorescent dyes, mention may be made of the radicals derived from acridine dyes, acridones, benzanthrones, benzimidazoles, benzimidazolones, benzindoles, benzoxazoles, benzopyranes, benzothiazoles, coumarins, difluoro {2 - [(2H-pyrrol-2ylidene-kN) methyl] - IH-pyrrolato-kN] bores (BOD IP Y ®), dikétopyrrolo-pyrroles, fluorindines, (poly) methines (in particular cyanines and styryles / hemicyanines), naphthalimides, naphthhanilides, naphthylamine (like dansyles), oxadiazoles, oxazines , perinones, perylenes, polyenes / carotenoids, squaranes, stilbenes, xanthenes.

Mention may also be made of the fluorescent dyes described in documents EP 1 133975, WO 03/029359, EP 860636, WO 95/01772, WO 95/15144, EP 714954 and those listed in the encyclopedia The chemistry of synthetic dye by K. VENKATARAMAN, 1952, Academic press vol 1 to 7, in the Kirk-Othmer Chemical technology encyclopedia, chapter Dyes and Dye intermediate, 1993, Wiley and sons, and in various chapters of the ULLMANN's encyclopedia of ENCYCLOPEDIA of Industrial chemistry 7th edition, Wiley and sons, in The Handbook - A Guide to Fluorescent Probes and Labeling Technologies, 10th Ed Molecular Probes / Invitrogen Oregon 2005 published on the Internet or in previous printed editions.

According to a variant of the invention, the cationic dye (s) are fluorescent and comprise at least one quaternary ammonium radical such as those of formula (C-VI) below, as well as their optical, geometric, tautomeric isomers, their acid salts or bases, organic or mineral, as well as their solvates such as hydrates:

W ⁺ - [C (R _c ) = C (Rd)] m'-Ar, Q '(C-VI) formula (C-VI) in which:

• W ⁺ represents a cationic heterocyclic or heteroaryl group, particularly comprising a quaternary ammonium optionally substituted by one or more alkyl groups (CiCs) optionally substituted in particular by one or more hydroxyl groups;

• Ar representing an aryl group such as phenyl or naphthyl, optionally preferably substituted by i) one or more halogen atoms, such as chlorine, fluorine; ii) one or more (Ci-Cs) alkyl groups, preferably C1-C4 such as methyl; iii) one or more hydroxyl groups; iv) one or more (Ci-Cs) alkoxy groups such as methoxy; v) one or more hydroxy (Ci-C8) alkyl groups such as hydroxyethyl, vi) one or more amino or (di) (CiCsjalkylamino) groups, preferably with the C1-C4 alkyl part optionally substituted by one or more hydroxyl such as (di) hydroxyethylamino, vii) by one or more acylamino groups; viii) one or more heterocycloalkyl groups such as piperazinyl, pyperidinyl or 5- or 6-membered heteroaryl such as pyrrolidinyl, pyridinyl and imidazolinyl;

• m 'represents an integer inclusive between 1 and 4, particularly m is 1 or 2; more preferably 1;

• R _c , Ra, identical or different, represent a hydrogen atom or a group (Ci-Csjalkyle optionally substituted, preferentially in C1-C4, or then R _c contiguous to W ⁺ and / or Ra contiguous to Ar form with the atoms carrying them a (hetero) cycloalkyl, particularly R _c is contiguous to W ⁺ and forms a (hetero) cycloalkyl such as cyclohexyl;

• Q ’is an organic or mineral anionic counterion as defined above.

Among the cationic direct dyes, mention may also be made of cationic triarylmethane dyes.

Preferably, the cationic direct dye (s) triarylmethane according to the invention are chosen from the cationic dyes of formulas (C-VII) and (C-VII ’) below:

(C-νΐΓ) as well as its addition salts with an acid or a base, organic or mineral, its geometric, optical isomers, tautomers, and its mesomeric forms, its solvates such as hydrates:

Formulas (C-VII) and (C-VII ’) above in which:

* Ri, R2, R3 and R4, identical or different, represent a hydrogen atom or a (Ci-C6) alkyl group optionally substituted, preferably by a hydroxy group; aryl such as phenyl, aryl (Ci-C4) alkyl such as benzyl, heteroaryl, heteroaryl (Ci-C4) alkyl, or then two groups Ri and R2, and / or R3 and R4, carried by the same nitrogen atom form together with the nitrogen atom which carry them an optionally substituted heterocycloalkyl group such as morpholino, piparazino, piperidino, preferably Ri, R2, R3 and R4, identical or different, represents a hydrogen atom or a group (Ci-C ₄ ) alkyl * R5, Rô, R7, Rs, R9, Rio, Ru, R12, R13, R14, R15 and R16, identical or different, represent a hydrogen atom, halogen, or a group chosen from i) hydroxy, ii) thiol, iii) amino iv) (di) (Ci-C4) (alkyl) amino, v) (di) arylamino such as (di) phenylamino, vi) nitro, vii) acylamino (-NR-C ( O) R ') in which the radical R is a hydrogen atom, an alkyl radical in C1-C4 optionally carrying at least one hydroxyl group and the radical R' is an alkyl radical in C1-C2; viii) carbamoyl ((R) 2N-C (O) -) in which the radicals R, which may or may not be identical, represent a hydrogen atom, a C1-C4 alkyl radical optionally carrying at least one hydroxyl group; ix) carboxylic acid or ester, (-OC (O) R ') or (-C (O) OR'), in which the radical R 'is a hydrogen atom, or C1-C4 alkyl optionally bearing at least one hydroxyl group and the radical R 'is a C1-C2 alkyl radical; x) alkyl optionally substituted in particular by a hydroxy group; xi) alkylsulfonylamino (R'SCh-NR-) in which the radical R represents a hydrogen atom, an alkyl radical in C1-C4 optionally carrying at least one hydroxyl group and the radical R 'represents an alkyl radical in C1 -C4, a phenyl radical; xii) aminosulfonyl ((R) 2N-SO2-) in which the radicals R, which may or may not be identical, represent a hydrogen atom, a C1-C4 alkyl radical optionally carrying at least one hydroxyl group, xiii) (Ci -C4) alkoxy, and xiv) (CiC4) alkylthio;

* Or then two radicals carried by two contiguous carbon atoms R5 and Rô and / or R7 and Rs, and / or R9 and Rio and / or Ru and R12 and / or R13 and R14 and / or R15 and Rie form together with the carbon atoms which carry them a condensed 6-membered aryl or heteroaryl ring, preferably benzo, said ring possibly being optionally substituted, preferably an unsubstituted benzo ring;

* Q- represents an anionic counter ion to achieve electroneutrality, preferably chosen from halides such as chloride, bromide, and phosphate.

When the cationic dye comprises one or more anionic substituents such as COOR or SO3R with R denoting a hydrogen or a cation, it is understood that there are then more cationic substituents than anionic substituents, so that the overall resulting charge of the triarylmethane structure is cationic.

According to a preferred embodiment, the triarylmethane dye (s) of the invention is / are chosen from those of formula (C-VII) or (C-VIL), in which, taken together or separately,

-Ri, R2, R3 and R4 represent a hydrogen atom or a (Ci-C4) alkyl group such as methyl or ethyl,

-Rs, Rô, R ?, Rs, R9, Rio, Ru, R12, R13, R14, R15, and R16 represent a hydrogen, halogen atom, such as chlorine, or a (Ci-C4) alkyl group such as methyl or ethyl, an amino group, a (di) (Ci-C4) (alkyl) amino group and, preferably, at least one of the groups R9, Rio, Ru or R12 represents a hydrogen atom, halogen (Cl), or an amino group, or a (CiC4) (alkyl) amino or (di) (Ci-C4) (alkyl) amino group, preferably in the para position of the phenyl group.

Preferably, the direct dye (s) of triarylmethane structure are chosen from Basic Violet 1, Basic Violet 2, Basic Violet 3, Basic Violet 4, Basic Violet 14, Basic Blue 1, Basic Blue 7, Basic Blue 26, Basic green 1, Basic Blue 77 (also called HC Blue 15), and their mixtures.

Preferably, when the composition according to the invention comprises one or more cationic direct dyes, the total content of cationic direct dye (s) present in the coloring composition according to the invention is between 0.001 to 20% by weight, more preferably between 0.005 and 10% by weight, more preferably still between 0.01 and 5% by weight, relative to the total weight of the coloring composition according to the invention.

The composition according to the invention can comprise one or more anionic direct dyes. The anionic direct dyes of the invention are dyes commonly known as "acid" direct dyes for their affinity with alkaline substances. The term “anionic direct dyes” means any direct dye comprising in its structure at least one CO2R or SO3R substituent with R denoting a hydrogen atom or a cation originating from a metal or an amine, or an ammonium ion. The anionic dyes can be chosen from acid nitro direct dyes, acid azo dyes, acid azine dyes, acid triarylmethane dyes, acid indoamine dyes, acid anthraquinone dyes, indigoids and natural acid dyes.

According to the invention, the anionic direct dye (s) can be chosen, alone or as a mixture, from anionic direct dyes of formulas (A-II), (A-ΙΓ), (A-III), (A-ΙΙΓ) , (A-IV), (AIV '), (AV), (A-V'), (A-VI), (A-VII), (A-VIII) and (A-IX):

a) the diaryl anionic azo dyes of formula (A-II) or (Α-

Π '):

formula (A-II) and (A-ΙΓ) in which:

R7, Rs, R9, Rio, R’7, R’s, R’9 and R’10, identical or different, represent a hydrogen atom or a group chosen from:

alkyl;

alkoxy, alkylthio;

hydroxy, mercapto;

nitro, nitroso;

- R ° -C (X) -X'-, R ° -X'-C (X) -, R ° -X'-C (X) -X ”- with R ° representing a hydrogen atom, a alkyl or aryl group; X, X ’and X”, identical or different, representing an oxygen, sulfur or NR atom with R representing a hydrogen atom or an alkyl group;

(O) 2S (O ') -, M ⁺ with M ⁺ representing a hydrogen atom or a cationic counterion;

(O) CO'-, M ⁺ with M ⁺ as defined above;

R ”-S (O) 2-, with R” representing a hydrogen atom, an alkyl group, an aryl group, (di) (alkyl) amino, aryl (alkyl) amino; preferably a phenylamino or phenyl group;

R ”’ - S (O) 2-X’- with R ’” representing an optionally substituted alkyl or aryl group, X ’as defined above;

(di) (alkyl) amino;

aryl (alkyl) amino optionally substituted by one or more groups chosen from i) nitro; ii) nitroso; iii) (0) 18 (0), M ⁺ and iv) alkoxy with M ⁺ as defined above; optionally substituted heteroaryl; preferably a benzothiazolyl group;

cycloalkyl; in particular cyclohexyl,

Ar-N = N- with Ar representing an optionally substituted aryl group; preferably a phenyl optionally substituted by one or more alkyl, (O) 2S (O) -, M ⁺ or phenylamino groups;

or then two contiguous groupings R? with Rs or Rs with R9 or R9 with Rio together form a benzo fused group A '; and R'7 with R's or R's with R'9 or R'9 with R'10 together form a benzo fused group B '; with A 'and B' optionally substituted by one or more groups chosen from i) nitro; ii) nitroso; iii) (O) 2S (O) -, M ⁺ ; iv) hydroxy; v) mercapto; vi) (di) (alkyl) amino; vii) R ° C (X) -X'-; viii) R ° -X'-C (X) -; ix) R ° -X'-C (X) -X ”-; x) ArN = N- and xi) aryl (alkyl) amino optionally substituted; with M ⁺ , R °, X, X ', X ”and Ar as defined above;

W represents a sigma s bond, an oxygen or sulfur atom, or a divalent radical i) -NR- with R as defined above, or ii) methylene -C (R _a ) (Rb) - with R _a and Rb identical or different, representing a hydrogen atom or an aryl group, or else R _a and Rb form together with the carbon atom which carries them a cycloalkyl spiro; preferably W represents a sulfur atom or R _a and Rb together form a cyclohexyl;

it being understood that the formulas (A-II) and (A-ΙΓ) comprise at least one sulfonate radical (O) 2S (O) -, M ⁺ or a carboxylate radical (O) CO'-, M ⁺ over one of the rings A, A ', B, B' or C; preferably sodium sulfonate;

Examples of dyes of formula (A-II) that may be mentioned: Acid Red 1, Acid Red 4, Acid Red 13, Acid Red 14, Acid Red18,

Acid Red 27, Acid Red 28, Acid Red 32, Acid Red 33, Acid Red35,

Acid Red 37, Acid Red 40, Acid Red 41, Acid Red 42, Acid Red44,

Pigment red 57, Acid Red 68, Acid Red 73, Acid Red 135, Acid Red 138, Acid Red 184, Food Red 1, Food Red 13, Acid Orange 6, Acid Orange 7, Acid Orange 10, Acid Orange 19, Acid Orange 20, Acid Orange 24, Yellow 6, Acid Yellow 9, Acid Yellow 36, Acid Yellow 199, Food Yellow 3; Acid Violet 7, Acid Violet 14, Acid Blue 113, Acid Blue 117, Acid Black 1, Acid Brown 4, Acid Brown 20, Acid Black 26, Acid Black 52, Food Black 1, Food Black 2; Food yellow 3 or sunset yellow;

and as examples of dyes of formula (A-ΙΓ) there may be mentioned: Acid Red 111, Acid Red 134, Acid yellow 38;

b) the azo anionic pyrrazolone dyes of formula (A-III) and (AIII ’):

(A-III)

formulas (A-III) and (Α-ΙΙΓ) in which:

Rn, Ri2 and Ri3, identical or different, represent a hydrogen atom, a halogen atom, an alkyl group or - (O) 2S (O), M ⁺ with M ⁺ as defined above;

Rm represents a hydrogen atom, an alkyl group or a group -C (O) O, M ⁺ with M ⁺ as defined above;

Ris represents a hydrogen atom;

Rie represents an oxo group in which case R’iô is absent, or then Ris with Rie together form a double bond;

Ri? and Ris, identical or different, represent a hydrogen atom, or a group chosen from:

(O) 2S (O ') -, M ⁺ with M ⁺ as defined above;

- Ar-O-S (O) 2- with Ar representing an optionally substituted aryl group; preferably a phenyl optionally substituted by one or more alkyl groups;

Ri9 and R20 together form either a double bond or a benzo group D ’, optionally substituted;

R’iô, R’i9 and R’20, identical or different, represent a hydrogen atom or an alkyl or hydroxy group;

R21 represents a hydrogen atom, an alkyl or alkoxy group;

R _a and R _a , identical or different, are as defined above, preferably R _a represents a hydrogen atom and Rb represents an aryl group;

Y represents either a hydroxy group or an oxo group;

------ represents a single bond when Y is an oxo group; and represents a double bond when Y represents a hydroxy group;

it being understood that the formulas (A-III) and (A-ΙΙΓ) comprise at least one sulfonate radical (O) 2S (O) -, M ⁺ or a carboxylate radical C (O) O, M ⁺ on one of the rings D or E; preferably sodium sulfonate;

Examples of dyes of formula (A-III) that may be mentioned: Acid Red 195, Acid Yellow 23, Acid Yellow 27, Acid Yellow 76, and by way of example of dyes of formula (A-ΙΙΓ) on may include: Acid Yellow 17;

c) the anthraquinone dyes of formula (A-IV) and (A-IV ’):

formulas (A-IV) and (A-IV) in which:

R22, R23, R24, R25, R26 and R27, identical or different, represent a hydrogen or halogen atom or a group chosen from:

alkyl;

hydroxy, mercapto;

alkoxy, alkylthio;

aryloxy or arylthio optionally substituted, preferentially substituted by one or more groups chosen from alkyl and (O) 2S (O) -, M ⁺ with M ⁺ as defined above;

aryl (alkyl) amino optionally substituted by one or more groups chosen from alkyl and (O) 2S (O) -, M ⁺ with M ⁺ as defined above;

(di) (alkyl) amino;

(di) (hydroxyalkyl) amino (O) 2S (O ') -, M ⁺ with M ⁺ as defined above;

Z ’represents a hydrogen atom or a group NR28R29 with R28 and R29, identical or different, represent a hydrogen atom or a group chosen from:

alkyl;

polyhydroxyalkyl such as hydroxyethyl;

aryl optionally substituted by one or more groups, in particular i) alkyl such as methyl, n-dodecyl, n-butyl; ii) (O) 2S (O) -, M ⁺ with M ⁺ as defined above; m) R ° -C (X) -X'-, R ° -X'-C (X) -, R ° -X'-C (X) X ”- with R °, X, X 'and X” as defined above, preferably R ° represents an alkyl group; cycloalkyl; especially cyclohexyl;

Z represents a group chosen from hydroxy and NR'2sR'29 with R'28 and R'29, identical or different, represent the same atoms or groups as R28 and R29 as defined above; it being understood that the formulas (A-IV) and (A-IV ') comprise at least one sulfonate radical (O) 2S (O) -, M ⁺ or a carboxylate radical C (O) O, M ⁺ ; preferably sodium sulfonate;

Examples of dyes of formula (A-IV) that may be mentioned: Acid Blue 25, Acid Blue 43, Acid Blue 62, Acid Blue 78, Acid Blue 129, Acid Blue 138, Acid Blue 140, Acid Blue 251, Acid Green 25, Acid Green 41, Acid Violet 42, Acid Violet 43, Mordant Red 3; EXT violet N ° 2;

and by way of example of dyes of formula (A-IV ’) there may be mentioned: Acid Black 48;

d) nitrated dyes of formula (A-V), and (A-V ’):

W — ALK — SO, M '(A-V)

NO.

formulas (A-V) and (A-V ’) in which:

R30, R31 and R32, identical or different, represent a hydrogen atom, a halogen atom, or a group chosen from:

- alkyl;

- alkoxy optionally substituted by one or more hydroxy groups, alkylthio optionally substituted by one or more hydroxy groups;

- hydroxy, mercapto;

- nitro, nitroso;

- polyhaloalkyl;

- R ° -C (X) -X’-, R ° -X’-C (X) -, R ° -X’-C (X) -X ”- with R °; X, X ’and X” as defined above;

- (O) 2S (O ') -, M ⁺ with M ⁺ as defined above;

- (O) CO'-, M ⁺ with M ⁺ as defined above;

(di) (alkyl) amino;

- (di) (hydroxyalkyl) amino;

- heterocycloalkyl such as piperidino, piperazino or morpholino;

particularly R30, R31 and R32 represent a hydrogen atom;

R _c and Ra, identical or different, represent a hydrogen atom or an alkyl group;

W is as defined above; W represents in particular a group -NH-;

ALK represents a divalent linear or branched C 1 -C 6 alkylene group; in particular ALK represents a group -CH2-CH2-;

n is 1 or 2;

p represents an integer inclusive between 1 and 5;

q represents an integer inclusive between 1 and 4;

u is 0 or 1;

when n is 1, J represents a nitro group, or nitroso; particularly nitro;

when n is 2, J represents an oxygen, sulfur atom or a divalent radical -S (O) _m - with m representing an integer 1 or 2; preferably J represents a radical -SO2-;

M ’represents a hydrogen atom or a cationic counterion;

present or absent represents a benzo group, optionally substituted by one or more R30 group as defined above;

it being understood that the formulas (AV) and (A-V ') comprise at least one sulfonate radical (O) 2S (O) -, M ⁺ or a carboxylate radical -C (O) O, M ⁺ ; preferably sodium sulfonate;

Examples of dyes of formula (A-V) that may be mentioned: Acid Brown 13; Acid Orange 3; Examples of dyes of formula (A-V ') that may be mentioned: Acid Yellow 1, Sodium salt of 2,4-dinitro-1-naphthol-7-sulfonic acid, 2-piperidino 5- acid nitro benzene sulfonic, Acid 2 (4'-N, N (2-hydroxyethyl) amino-2'nitro) aniline ethane sulfonic, 4-3-hydroxyethylamino-3nitrobenzene sulfonic acid; EXT D&C yellow 7;

d) triarylmethane dyes (A-VI):

of formula

(A-VI) or different, represent a chosen from alkyl, optionally substituted aryl; and benzyl optionally formula (A-VI) in which:

R33, R34, R35 and R36, identical hydrogen atom or an optionally substituted group and arylalkyl, in particular an alkyl group substituted by a group (O) _m S (O ') -, M ⁺ with M ⁺ and m as defined above ;

R37, R38, R39, R40, R41, R42, R43 and R44, identical or different, represent a hydrogen atom or a group chosen from:

alkyl;

alkoxy, alkylthio; (di) (alkyl) amino;

- hydroxy, mercapto;

nitro, nitroso;

- R ° -C (X) -X'-, R ° -X'-C (X) -, R ° -X'-C (X) -X ”- with R ° representing a hydrogen atom, a alkyl or aryl group; X, X ’and X”, identical or different, representing an oxygen, sulfur or NR atom with R representing a hydrogen atom or an alkyl group;

(O) 2S (O ') -, M ⁺ with M ⁺ representing a hydrogen atom or a cationic counterion;

(O) CO'-, M ⁺ with M ⁺ as defined above;

or then two contiguous groups R41 with R42 or R42 with R43 or R43 with R44 together form a benzo fused group: Γ; with Γ optionally substituted by one or more groups chosen from i) nitro; ii) nitroso; iii) (O) 2S (O) -, M ⁺ ; iv) hydroxy; v) mercapto; vi) (di) (alkyl) amino; vii) R ° C (X) -X'-; viii) R ° -X'-C (X) -; ix) R ° -X'-C (X) -X ”-; with M ⁺ , R °, X, X ', X ”as defined above;

particularly R37 to R40 represent a hydrogen atom, and R41 to R44, identical or different, represent a hydroxy group or (O) 2S (O ') -, M ⁺ ; and when R43 with R44 together form a benzo group, it is preferentially substituted by a group (O) 2S (O) -;

it being understood that at least one of the rings G, H, I or Γ comprise at least one sulfonate radical (O) 2S (O) - or a carboxylate radical C (O) O; preferably sulfonate;

Examples of dyes of formula (A-VI) that may be mentioned: Acid Blue 1; Acid Blue 3; Acid Blue 7, Acid Blue 9; Acid Violet 49; Acid green 3; Acid green 5; Acid Green 50;

e) dyes derived from xanthene of formula (A-VII):

(A-VII) formula (A-VII) in which:

R45, R46, R47 and R48, identical or different, represent a hydrogen atom or a halogen atom;

R-49, Rso, R51 and R52, identical or different, represent a hydrogen atom, a halogen atom, or a group chosen from:

alkyl;

alkoxy, alkylthio;

hydroxy, mercapto;

nitro, nitroso;

(O) 2S (O ') -, M ⁺ with M ⁺ representing a hydrogen atom or a cationic counterion;

(O) CO'-, M ⁺ with M ⁺ as defined above; particularly R53 R54, R55 and R4 represent a hydrogen or halogen atom;

G represents an oxygen or sulfur atom or a group NR _e with R _e as defined above; particularly G represents an oxygen atom;

L represents an alcoholate O, M ⁺ ; a thioalcoholate S, M ⁺ or an NRf group, with Rf representing a hydrogen atom or an alkyl group, and M ⁺ as defined above; M ⁺ is particularly sodium or potassium;

L 'represents an oxygen or sulfur atom or an ammonium group: N ⁺ RfR _g , with Rf and R _g , identical or different, representing a hydrogen atom, an optionally substituted alkyl or aryl group; L 'represents in particular an oxygen atom or a phenylamino group optionally substituted by one or more alkyl groups or (O) mS (O') -, M ⁺ with m and M ⁺ as defined above;

Q and Q ’, identical or different, represent an oxygen or sulfur atom; particularly Q and Q ’represent an oxygen atom;

M ⁺ is as defined above;

Examples of dyes of formula (A-VII) that may be mentioned: Acid Yellow 73; Acid Red 51; Acid Red 52, Acid Red 87; Acid Red 92; Acid Red 95; Acid Violet 9;

f) dyes derived from indole of formula (A-VIII):

(A-VIII) formula (A-VIII) in which:

R53, R54, R55, R56, R57, R58, R59 and Rôo, identical or different, represent a hydrogen atom or a group chosen from:

alkyl;

alkoxy, alkylthio;

hydroxy, mercapto;

nitro, nitroso;

- R ° -C (X) -X'-, R ° -X'-C (X) -, R ° -X'-C (X) -X ”- with R ° representing a hydrogen atom, a alkyl or aryl group; X, X ’and X”, identical or different, representing an oxygen, sulfur or NR atom with R representing a hydrogen atom or an alkyl group;

(O) 2S (O ') -, M ⁺ with M ⁺ representing a hydrogen atom or a cationic counterion;

(O) CO'-, M ⁺ with M ⁺ as defined above;

G represents an oxygen or sulfur atom or a group NR _e with R _e as defined above; particularly G represents an oxygen atom;

Ri and Rh, identical or different, represent a hydrogen atom or an alkyl group;

it being understood that the formula (A-VIII) comprises at least one sulfonate radical (O) 2S (O) -, M ⁺ or a carboxylate radical -C (O) O, M ⁺ ; preferably sodium sulfonate

Examples of dyes of formula (A-VIII) that may be mentioned: Acid Blue 74.

g) dyes derived from quinoline of formula (A-IX):

^U (A-IX) hvdrosene. halosene or a ^ ⁶¹

XXI

R ₆₂ f N ^Rf53 HO formula (A-IX) in which:

R.61 represents an alkyl group atom;

Rô2, Rô3, and Rô4, identical or different, represent a hydrogen atom or a group (O) 2S (O) -, M ⁺ with M ⁺ representing a hydrogen atom or a cationic counterion;

or Rôi with Rô2, or Rôi with Rô4, together form a benzo group optionally substituted by one or more (O) 2S (O) - group, M ⁺ with M ⁺ representing a hydrogen atom or a cationic counterion;

it being understood that the formula (A-IX) comprises at least one sulfonate (O) 2S (O) -, M ⁺ radical, preferably sodium sulfonate.

Examples of dyes of formula (A-IX) that may be mentioned: Acid Yellow 2, Acid Yellow 3 and Acid Yellow 5.

More particularly, the coloring composition comprises one or more anionic direct dyes chosen, alone or as a mixture, from the following anionic direct dyes:

(C.I. 45380) Acid Red 87 (A-VII) (C.l. 10316) Sodium salt of 2,4-dinitro-l-naphthol-7sulfonic acid (A-V ’) (C.I. 10383) Acid Orange 3 (A-V) (C.l. 13015) Acid Yellow 9 / Food Yellow 2 (A-II) (C.l. 14780) / Direct Red 45 / Food Red 13 (A-II) (C.l. 13711) Acid Black 52 (A-II) (C.l. 13065) Acid Yellow 36 (A-II) (C.l. 14700) 1-hydroxy-2- (2 ', 4'-xylyl-5sufonatoazo) -naphthalene-4-sulfonic acid / sodium red ifi / Food Red 1 (Α-Π) (C.l. 14720) Acid Red 14 / Food Red 3 / Mordant Blue 79 (A-II)

(C. 1. 14805) Sodium salt of 4-hydroxy-3 - [(2-metoxy-5-, nitrophenyl) diaza] -6- (phenylamino) naphthalene-2sulfonic / Acid Brown 4 (A-II) (C.l. 15510) Acid Orange 7 / Pigment Orange 17 / Solvent Orange 49 (A-II) (C.l. 15985) Food Yellow 3 / Pigment Yellow 104 (A-II) (C.l. 16185) Acid Red 27 / Food Red 9 (A-II) (C.l. 16230) Acid Orange 10 / Food Orange 4 (A-II) (C.l. 16250) Acid Red 44 (A-II) (C.l. 17200) Acid Red 33 / Food Red 12 (A-II) (C.l. 15685) Acid Red 184 (A-II) (C.l. 19125) Acid Violet 3 (A-II) (C.l. 18055) L-hydroxy-2- (4’-acetamido phenyl azo) -8-acetamido-naphthalene-3,6-di sulfonic acid / Sodium sodium sii / Acid Violet 7 / Food Red 11 (A-II) (C.l. 18130) Acid Red 135 (A-II) (C.l. 19130) Acid Yellow 27 (A-III) (C.l. 19140) Acid Yellow 23 / Food Yellow 4 (A-III) (C.l. 20170) 4 '- (sulfonato-2,4-dimethyl) bis (2,6-phenylazo) - 1,3-dihydroxy benzene / Acid Orange 24 (A-II) (C.l. 20470) 1-amino-2- (4'nitrophenylazo) -7-phenylazo-8-hydroxy-naphthalene3,6-disulfonic acid / Acid Black 1 (A-II) sodium sodium (C.l. 23266) (4 - ((4-methylphenyl) sulfonyloxy) -phenylazo) 2,2'dim ethyl 1-4 - ((2-hydroxy-5,8disulfonato) naphthylazo) biphenyl / Acid Red 111 (ΑΠ ’) (C.l. 27755) Food Black 2 (A-II) (C.l. 25440) l- (4'-sulfonatophenylazo) -4 - ((2-hydroxy-3 acetylamino-6,8-disulfonato) naphthylazo) -6sulfonatonaphthalene (tetrasodium salt) / Food Black 1 (A-II) (C.l. 42090) Acid Blue 9 (A-VI)

(C.I. 60730) Acid Violet 43 (A-IV) (C.I. 61570) Acid Green 25 (A-IV) (C.I. 62045) L-amino-4- acid sodium salt cyclohexylamino-9,10-anthraquinone 2-sulfonic / Acid Blue 62 (A-IV) (C.I. 62105) Acid Blue 78 (A-IV) (C.I. 14710) Sodium salt of 4-hydroxy-3 ((2-methoxy phenyl) -azo) -l-naphthalene sulfonic acid / Acid Red 4 (A-H) 2-piperidino 5-nitro benzene sulfonic acid (V ’) 2 (4'-N, N (2-hydroxyethyl) amino-2'- acid nitro) aniline ethane sulfonic (A-V ’) 4-3-hydroxyethylamino-3-nitrobenzene acid Sulfonic (A-V ’) (C.I. 42640) Acid Violet 49 (A-VI) (C.I. 42080) Acid Blue 7 (A-VI) (C.I. 58005) 1,2-dihydroxy-3-sulfoanthraquinone / Mordant Red 3 (A-IV) sodium salt (C.I. 62055) Sodium salt of l-amino-9,10-dihydro-9,10dioxo-4- (phenylamino) 2-anthracene sulfonic / Acid Blue 25 (A-IV) (C.I. 14710) Sodium salt of 4-hydroxy-3 - ((2methoxyphenyl) -azo) -l-naphthalene sulfonic acid / Acid Red 4 (A-H)

Most of these dyes are described in particular in the Color Index published by The Society of Dyers and Colorists, P.O. Box 244, Perkin House, 82 Grattan Road, Bradford, Yorkshire, BD1 2JBN 5 England.

The anionic dyes more particularly preferred are the dyes designated in the Color Index under the code CI 58005 (monosodium salt of l, 2-dihydroxy-9,10-anthraquinone-3sulfonic), CI 60730 (monosodium salt of acid 2 - [(9,10-dihydro10 4-hydroxy-9,10-dioxo-1 - anthracenyl) -amino] -5-methyl-benzene sulfon), CI 15510 (monosodium salt of acid 4 - [(2 -hydroxy-lnaphthalenyl) -azo] -benzene sulfonic), CI 15985 (sei disodium 6-hydroxy-5 - [(4-sulfophenyl) -azo] -2-naphthalene sulfonic), CI 17200 (sei disodium 5-amino-4-hydroxy-3- (phenylazo) 2,7-naphthalene disulfonic acid), CI 20470 (disiodic acid 1 amino-2- (4'-nitrophenylazo) -7-phenylazo-8- hydroxy-3,6-naphthalene disulfonic), CI 42090 (disodium disi of N-ethyl-N- [4 - [[4- [ethyl [3sulfophenyl) -methyl] -amino] -phenyl] (2-sulfophenyl) -methylene ] -2,5cyclohexadien-l-ylidene] -3-sulfobenzenemethanaminium hydroxide, internal salt), CI 61570 (disodium salt of a cide 2,2 '- [(9,10-dihydro9,10-dioxo -1,4-anthracenediyl) -diimino] -bis- [5-methyl] -benzene sulfonic acid.

It is also possible to use compounds corresponding to the mesomeric, tautomeric forms, of the structures (A-II) to (A-IX).

Among the natural direct dyes which can be used according to the invention, mention may be made of hennotannic acid, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, protocatechaldehyde, indigo, isatin, curcumin, spinulosin, apigenidine and orcein. Extracts or decoctions containing these natural dyes and in particular poultices or extracts based on henna can also be used.

Preferably, when the composition according to the invention comprises one or more anionic direct dyes, the total content of anionic direct dye (s) present in the coloring composition according to the invention is between 0.001 to 20% by weight, more preferably between 0.005 and 10% by weight, more preferably still between 0.01 and 5% by weight, relative to the total weight of the coloring composition according to the invention.

The nonionic direct dyes can be chosen from nitrous benzene dyes, azo dyes and anthraquinone dyes.

Preferably, when the composition according to the invention comprises one or more non-ionic direct dyes, the total content of non-ionic direct dye (s) present in the coloring composition according to the invention is between 0.001 to 20% by weight, more preferably between 0.005 and 10% by weight, more preferably still between 0.01 and 5% by weight, relative to the total weight of the coloring composition according to the invention.

According to a preferred embodiment of the invention, the coloring composition comprises at least one direct dye chosen from cationic direct dyes; more preferably at least one cationic direct dye chosen from cationic triarylmethane direct dyes, in particular those of formula (CVII) or (C-VII ’) such as HC Blue 15 and / or Basic Violet 2; azo cationic direct dyes, in particular those of formula C-IV-1 such as Basic Red 51 and / or Basic Orange 31; hydrazono cationic direct dyes, in particular those of formula C-II-1 such as Basic Yellow 87; and their mixtures.

Preferably, the total content of direct dye (s) present in the coloring composition according to the invention is between 0.001 and 20% by weight, more preferably between 0.005 and 10% by weight, more preferably still between 0.01 and 5% by weight, relative to the total weight of the coloring composition according to the invention.

Cyclodextrins

The coloring composition according to the present invention comprises at least one cyclodextrin (abbreviated CD).

The cyclodextrins according to the invention can be modified or not.

Cyclodextrins (abbreviated CDs) are cyclic oligosaccharides made up of (a-1,4) α-D-glucopyranose units with a lipophilic central cavity and a hydrophilic external surface (Frômming KH, Szejtli J: "Cyclodextrins in pharmacy", Kluwer Academie Publishers, Dortrecht, 1994). The most abundant natural CDs are a-cyclodextrins (abbreviated a-CDs), β-cyclodextrins (abbreviated β-CDs) and γ-cyclodextrins (abbreviated γ-CDs).

CT-CDs (also known as Schardinger's adextrin, alpha-cyclodextrin, cyclomaltohexaose, cyclohexaglucan, cyclohexaamylose, a-CD, ACD, C6A) include 6 units of glucopyranose. Β-CDs (also known as Schardinger's β-dextrin, beta-cyclodextrin, cyclomaltoheptaose, cycloheptaglucan, cycloheptaamylose, b-CD, BCD, C7A) include 7 units of glucopyranose, and γ-CDs (also known as Schardinger's γ-dextrin, gamma-cyclodextrin, cyclomaltooctaose, cyclooctaglucan, cyclooctaamylose, g-CD, GCD, C8A) include 8 units of glucopyranose.

The cyclodextrins according to the invention are in particular oligosaccharides of formula (V):

Formula (V) in which x represents an integer equal to 4 (corresponding to α-cyclodextrin), to 5 (corresponding to βcyclodextrin) or to 6 (corresponding to γ-cyclodextrin).

One can in particular use a β-CD sold by the company WACKER under the name CAVAMAX W7 and γ-CD sold by the company WACKER under the name CAVAMAX W8.

The derivatives of CDs are also usable in the present invention. In CDs, each unit of glucopyranose has three free hydroxyl groups which differ in their function and reactivity.

By "CD derivative" is meant a CD in which all or part of the hydroxyl groups has been modified by reaction or substitution of the hydroxyl group or groups or of hydrogen atom (s). Mention may in particular be made of derivatives comprising ester, ether, anhydro, deoxy-, acid, basic groups and which can be prepared by chemical or enzymatic reactions, well known to those skilled in the art.

For example, in β-CDs, 21 hydroxyl groups can be modified by substituting the hydrogen atom or the hydroxyl group with a wide variety of groups such as alkyl, hydroxyalkyl, carboxyalkyl, amino-, thio-, tosyl groups. -, glucosyl-, maltosyl-, etc. Among the preferred derivatives, there may be mentioned the derivatives of a-CDs, β-CDs, γ-CDs and in particular the methylated derivatives of CDs such as methyl-3-cyclodextrin sold by the company WACKER under the name CAVASOL W7; TRIMEB (heptakis (2,3,6-trimethyl) -3-cyclodextrin), DIMEB (heptakis (2,6-dimethyl) -3-cyclodextrin) or also RAMEB (Randomly Methylated β-Cyclodextrin); 2-hydroxypropyl-3cyclodextrin (HPCD); 2-hydroxyethyl-3-cyclodextrin; 2hydroxypropyl-y-cyclo-dextrin and 2-hydroxyethyl-y-cyclodextrin.

Mention may also be made of CDs crosslinked with epichlorohydrin (EPC). In particular, mention may be made of the HPCD sold in particular under the name of Kleptose HPB® by the company Roquette and the RAMEB sold by the company Wacker.

Mention may also be made of Wacker's MCT reactive CDs (chlorotriazine functionalized cyclodextrin) β-cyclodextrin (CAVASOL® W7 MCT).

Finally, we can also cite the dimers of CDs or bis-CDs. It is possible to obtain these dimers of CDs or bis-CDs by the conventional methods known to those skilled in the art, for example by chemical reaction between two CDs and a reagent (linker) comprising two groups which can react with the atoms of hydrogen or the hydroxyl groups of each CD (see for example Tetrahedron, 51, 377 (1995); Chem. Rev. 97, 1647-1668 (1997), J. Org. Chem., 64, 7781-7787 (1999)) .

According to a particular embodiment, the CDs are not dimers i.e. the CDs are monomers.

According to a preferred embodiment of the invention, the cyclodextrin or cyclodextrins present in the coloring composition according to the invention are chosen from β-cyclodextrins; more preferably chosen from β-cyclodextrin, methyl-βcyclodextrin, heptakis (2,3,6-trimethyl) ^ - cyclodextrin, heptakis (2,6-dimethyl) ^ - cyclodextrin, 2-hydroxypropyl ^ cyclodextrin, 2-hydroxyethyl ^ -cyclodextrin, and mixtures thereof; even more preferably from β-cyclodextrin, 2hydroxypropyl ^ -cyclodextrin, 2-hydroxyethyl ^ -cyclodextrin, and mixtures thereof; and even better among β-cyclodextrin, 2hydroxypropyl ^ -cyclodextrin and their mixtures. Very particularly preferably, the coloring composition comprises at least 2-hydroxypropyl ^ -cyclodextrin.

Preferably, the total content of cyclodextrin (s) present in the coloring composition according to the invention is between 0.1 and 25% by weight, more preferably between 0.5 and 20% by weight, more preferably still between 1 and 15% by weight, better still between 2 and 10% by weight, relative to the total weight of the coloring composition according to the invention.

Alkaline agents

The coloring composition according to the invention can optionally comprise at least one alkaline agent.

Among the alkaline agent (s) which can be used according to the invention, mention may be made of organic alkaline agents.

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

The organic alkaline agent (s) are for example chosen from alkanolamines, oxyethylenated and / or oxypropylenated ethylenediamines, amino acids and the compounds of formula (G-III) below:

in which W is a C1-C6 alkane radical optionally substituted by a hydroxyl group or a C1-C6 alkyl radical; Rx, Ry, Rz and Rt, identical or different, represent a hydrogen atom, a C1-C6 alkyl radical or a C1-C6 hydroxyalkyl radical, a C1-C6 aminoalkyl radical.

Examples of such amines that may be mentioned include 1,3 diaminopropane, 1,3 diamino 2 propanol, spermine, spermidine.

By alkanolamine is meant an organic amine comprising a primary, secondary or tertiary amine function, and one or more alkyl groups, linear or branched, in Ci-Cs carrying one or more hydroxyl radicals. Particularly suitable for carrying out the invention are alkanolamines such as mono-, diou tri-alkanolamines, comprising one to three hydroxyalkyl radicals, identical or not, C1-C4.

By way of example, mention may be made of monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, N-dimethylaminoethanolamine, 2-amino-2methyl-1-propanol, triisopropanolamine, trishydroxymethyl ami no methane.

Preferably, the alkaline agent (s) are inorganic alkaline agents.

The alkaline agent (s) can, for example, be chosen from dibasic or tribasic ammonium phosphates, water-soluble silicates such as silicates of alkali or alkaline earth metals such as sodium disilicate, sodium silicate (also called disodium salt silicic acid or disodium metasilicate), dibasic or tribasic phosphates of alkali or alkaline earth metals or carbonates of alkali or alkaline earth metals, such as lithium, sodium, potassium, magnesium, calcium, barium , and mixtures thereof.

Preferably, the alkaline agent (s) are chosen from water-soluble silicates such as silicates of alkali or alkaline-earth metals, dibasic or tribasic phosphates of alkali or alkaline-earth metals, carbonates of alkali or alkaline-earth metals, and their mixtures.

Within the meaning of the invention, the term "water-soluble silicate" means a silicate which has a solubility in water at 25 ° C greater than 0.5%, preferably greater than 1% by weight.

These water-soluble silicates differ from aluminum silicates and their derivatives, in particular clays, such as mixed silicates of natural or synthetic origin which are insoluble in water.

According to a preferred embodiment of the invention, the coloring composition comprises at least one alkaline agent; preferably chosen from inorganic alkaline agents; more preferably chosen from dibasic or tribasic ammonium phosphates, water-soluble silicates such as silicates of alkali or alkaline earth metals such as sodium disilicate, sodium silicate, dibasic or tribasic phosphates of alkali or alkaline earth metals or alkali or alkaline earth metal carbonates, and mixtures thereof; more preferably still among the water-soluble silicates such as the silicates of alkali or alkaline-earth metals; better among sodium disilicate, sodium silicate, and mixtures thereof; even better among sodium silicate.

Preferably, when it (s) is (are) present in the coloring composition according to the invention, the total content of alkaline agent (s) is between 0.1 and 40% by weight , more preferably between 0.5 and 30% by weight, more particularly still between 1 and 25% by weight, relative to the total weight of the coloring composition.

The coloring composition according to the invention can be anhydrous or aqueous, preferably aqueous.

By “aqueous coloring composition” according to the present application, is meant a coloring composition in which the total water content is greater than or equal to 10% by weight, relative to the weight of the coloring composition.

When the composition according to the invention is aqueous, preferably, the total water content present in the coloring composition according to the invention is greater than or equal to 20% by weight, more preferably greater than or equal to 30% by weight of water, more preferably still greater than or equal to 40% by weight, better still greater than or equal to 50% by weight, and better still between 50 and 98% by weight, relative to the total weight of the coloring composition.

In addition to water, the composition according to the present invention can optionally comprise one or more organic solvents, or mixtures thereof.

As organic solvent, mention may, for example, be made of alkanols, linear or branched, in C2 to C ₄ , such as ethanol and isopropanol; glycerol; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, hexylene glycol, dipropylene glycol, propylene glycol monomethyl ether, monoethyl ether and monomethyl ether of diethylene glycol, as well as aromatic alcohols or ethers such as benzyl alcohol or phenoxyethanol, and mixtures thereof.

The coloring composition according to the present invention may optionally further comprise one or more additives, different from the compounds of the invention and among which mention may be made of cationic, anionic, nonionic, amphoteric or zwitterionic surfactants and their mixtures, the bodies fatty, cationic, anionic, non-ionic, amphoteric polymers or their mixtures, dandruff agents, antiseborrheic agents, vitamins and pro-vitamins including panthenol, sun filters, mineral or organic pigments, sequestering agents, plasticizing agents, solubilizing agents, acidifying agents, mineral or organic thickening agents, in particular polymeric thickening agents, opacifying or pearlescent agents, antioxidants, hydroxy acids, perfumes, preservatives, and ceramides.

Of course, those skilled in the art will take care to choose this or these optional additional compounds in such a way that the advantageous properties intrinsically attached to the composition according to the invention are not, or not substantially, altered by the addition (s) envisaged. .

The above additives can generally be present in an amount for each of them between 0 and 20% by weight, relative to the total weight of the composition.

When the composition is aqueous, the pH of the coloring composition according to the present invention is preferably greater than or equal to 7, and more preferably between 7 and 12; more preferably still between 7.5 and 10.5.

The composition according to the invention is advantageously in the form of a cream, a lotion or a gel.

The invention particularly relates to a process for dyeing keratin fibers, in particular human keratin fibers such as the hair, comprising at least one step of applying to said fibers a composition for dyeing keratin fibers as described above .

According to a preferred embodiment of the coloring process according to the invention, the coloring composition as defined above is prepared less than an hour, more preferably less than 30 minutes, more preferably still less than 15 minutes, even better less 5 minutes, before application to said keratin fibers.

According to a particular embodiment, the coloring method according to the invention uses at least one chemical oxidizing agent different from the peroxygenated salts described above. Preferably, the chemical oxidizing agent is hydrogen peroxide. The chemical oxidizing agent different from the peroxygenated salts may be present in an oxidizing composition (A) which is mixed with the coloring composition as defined above at the time of use.

According to this embodiment, the method according to the invention then implements a ready-to-use coloring composition obtained by extemporaneous mixing of a coloring composition according to the invention and an oxidizing composition (A) comprising minus a chemical oxidizing agent different from the peroxygenated salts, preferably hydrogen peroxide. It is understood in this embodiment that the coloring composition according to the invention then does not comprise chemical oxidizing agents other than peroxygenated salts.

More particularly, by “chemical oxidizing agent” is meant within the meaning of the present invention an oxidizing agent different from the oxygen in the air.

The chemical oxidizing agent (s) included in the oxidizing composition (A) can be chosen from hydrogen peroxide, urea peroxide, peracids and oxidase enzymes (with their possible cofactors) among which mention may be made of peroxidases, 2-electron oxidoreductases such as uricases and 4-electron oxygenases such as laccases, and mixtures thereof; preferably, the chemical oxidizing agent (s) included in the oxidizing composition (A) comprises hydrogen peroxide.

In particular, the coloring composition is applied to dry or wet keratin fibers.

It is usually left in place on the fibers for a duration, in general, from 1 minute to 1 hour and 30 minutes, preferably from 5 minutes to 60 minutes.

The temperature during the coloring process conventionally varies from room temperature (15 to 25 ° C) to 80 ° C, preferably from room temperature to 60 ° C.

According to another preferred embodiment of the dyeing process according to the invention, a step of rinsing the keratin fibers is carried out after the step or steps of application to said fibers of a dye composition according to the invention.

A step for drying the keratin fibers may be provided in the dyeing process according to the invention, in particular using a heating means such as a hair dryer, a straightening iron, a steam iron or a heated helmet; the heating means being able to heat at a temperature ranging from 150 ° C to 230 ° C, preferably from 200 ° C to 220 ° C.

The invention also relates to the use of the coloring composition as defined above, for the coloring of keratin fibers.

The subject of the invention is also a process for simultaneous bleaching / coloring of keratin fibers, in particular human keratin fibers such as the hair, comprising at least one step of application to said fibers:

- a composition for coloring keratin fibers as described above, and

- an oxidizing composition (B) distinct from the coloring composition comprising one or more chemical oxidizing agents preferably different from the peroxygenated salts as described above, more preferably chosen from hydrogen peroxide.

Preferably, the oxidizing composition (B) is aqueous.

By “aqueous oxidizing composition (B)” according to the present application, is meant an oxidizing composition (B) in which the total water content is greater than or equal to 10% by weight, relative to the weight of the aqueous oxidizing composition.

The aqueous oxidizing composition (B) used in the process of simultaneous bleaching / coloring of keratin fibers according to the invention comprises one or more chemical oxidizing agents preferably different from the peroxygenated salts.

Preferably, the chemical oxidizing agent (s) included in the oxidizing composition (B) are chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, in particular the sodium persulfate, potassium persulfate and ammonium persulfate, peracids and oxidase enzymes (with their possible cofactors) such as peroxidases, 2-electron oxidoreductases such as uricases and 4-electron oxygenases such as laccases, and mixtures thereof; preferentially, the oxidizing composition (B) comprises hydrogen peroxide.

Preferably, the total content of chemical oxidizing agent (s), preferably different from the peroxygenated salts, is between 1 and 50% by weight, more preferably between 3 and 30% by weight, more preferably still between 5 and 20% by weight, relative to the total weight of the oxidizing composition (B).

According to a particular embodiment of the process for simultaneous bleaching / coloring of keratin fibers according to the invention, the coloring composition and the oxidizing composition are applied successively to the keratin fibers, dry or wet, without intermediate rinsing. apply the coloring composition then the oxidizing composition or the oxidizing composition then the coloring composition.

According to a preferred embodiment of the process of simultaneous bleaching / coloring of keratin fibers according to the invention, the process of simultaneous bleaching / coloring comprises a step of extemporaneous mixing of said coloring composition according to the invention with said oxidizing composition before or said application steps on said keratin fibers.

According to this preferred embodiment, the extemporaneous mixture of said coloring composition with said oxidizing composition is preferably prepared less than an hour, more preferably less than 30 minutes, more preferably still less than 15 minutes, even better less than 5 minutes, before application to said keratin fibers.

According to another preferred embodiment of the process for simultaneous bleaching / coloring of keratin fibers according to the invention, the coloring composition as defined above is prepared less than an hour, more preferably less than 30 minutes, more preferably still less 15 minutes, better still less than 5 minutes, before application to said keratin fibers.

According to this embodiment, the coloring composition according to the invention is preferably obtained by mixing a composition C1 comprising one or more peroxygenated salts as described above, preferably one or more persulfates, and a composition C2 comprising a or several direct dyes as described above and one or more cyclodextrins as described above.

In addition, independently of the embodiments implemented in the simultaneous bleaching / coloring process, the mixture present on the fibers (resulting either from the extemporaneous mixing of the compositions or from the successive application of these) is left in place for a duration, in general, of the order of 1 minute to 1 hour and 30 minutes, preferably from 5 minutes to 60 minutes.

The temperature during the simultaneous bleaching / coloring process is conventionally between room temperature (between 15 and 25 ° C) and 80 ° C, preferably between room temperature and 60 ° C.

At the end of the treatment, the human keratin fibers are optionally rinsed with water, possibly subjected to washing with a shampoo followed by rinsing with water, before being dried or allowed to dry in the open air.

Preferably, the pH of the oxidizing composition (A) and / or of the oxidizing composition (B), when they are aqueous, is between 3 and 11, in particular between 4 and 10.

The pH of the oxidizing composition (A) and / or the oxidizing composition (B) can be adjusted to the desired value by means of basifying agents or acidifying agents. Among the basifying agents, there may be mentioned ammonia, monoethanolamine, mineral or organic hydroxides. Examples of acidifying agents that may be mentioned include mineral acids such as hydrochloric acid, orthophosphoric acid, or for example acetic acid, tartaric acid, citric acid, lactic acid, sulfonic acids.

The oxidizing composition (B) distinct from the coloring composition used in the process of simultaneous bleaching / coloring of the keratin fibers according to the invention may optionally further comprise one or more additives such as those described above, in the total contents previously described.

The invention also relates to a device comprising at least two compartments, a first compartment containing a composition for coloring keratin fibers as defined above; a second compartment containing an oxidizing composition, preferably aqueous, comprising one or more chemical oxidizing agents preferably different from the peroxygenated salts as described above.

The invention also relates to a device comprising at least three compartments, a first compartment containing a composition C1 comprising one or more peroxygenated salts, preferably one or more persulfates, as described above; a second compartment containing a composition C2 comprising one or more direct dyes and one or more cyclodextrins as described above; a third compartment containing an oxidizing composition comprising one or more chemical oxidizing agents different from the peroxygenated salts as described above.

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

EXAMPLES:

The following compositions A to E are prepared from the ingredients indicated in the table below, the amounts of which are expressed in% by weight of active material (ai).

ingredients Composition A (witness) Composition B (comparative) Composition C (comparative) Composition D (invention) Composition E (invention) Silicate of Sodium 14 14 14 14 14 HC Blue 15 0 0.105 0 0.105 0 Basic Red 51 0 0 0.105 0 0.105 2- HydroxypropylβCyclodextrine 0 0 0 7.86 7.86 Potassium persulfate 12.7 12.7 12.7 12.7 12.7 Water Qsp 100 Qsp 100 Qsp 100 Qsp 100 Qsp 100

Once compositions A to E have been prepared, the mixtures M1 to 10 M5 are then prepared.

The mixture Ml (control) corresponds to a mixture of 10 g of composition A with 10 g of oxidizing composition comprising hydrogen peroxide at 12 g% ai.

The mixture M2 (Comparative) corresponds to a mixture of 10 g 15 of composition B with 10 g of oxidizing composition comprising hydrogen peroxide at 12 g% ai.

The mixture M3 (Comparative) corresponds to a mixture of 10 g of composition C with 10 g of oxidizing composition comprising hydrogen peroxide at 12 g% ai.

The mixture M4 (Invention) corresponds to a mixture of 10 g of composition D with 10 g of oxidizing composition comprising hydrogen peroxide at 12 g% ai.

The mixture M5 (Invention) corresponds to a mixture of 10 g of composition E with 10 g of oxidizing composition comprising hydrogen peroxide at 12 g% ai.

Each mixture Ml to M5 is then applied to a lock of natural hair containing 90% white hairs at the rate of 10 g of mixture for 1 gram of hair.

Each strand of treated hair is then left to stand for 50 minutes on a hot plate at a temperature of 33 ° C.

Spectrocolometric evaluation:

The color of the locks was then evaluated in the CIE L * a * b * system, using a Minolta Spectrophotometer CM3600D colorimeter (illuminant D65, angle 10 °). In this L * a * b * system, the three parameters respectively designate the color intensity (L *), a * indicates the green / red color axis and b * the blue / yellow color axis.

The variation in coloration between the strands of colored hair and the strands of hair only lightened is defined by (ΔΕ *) according to the following equation:

Δ E * = 7 (C * -Z _O *) ² + (a * -a0 *) ² + (b * -b0 *) ²

In this equation, L *, a * and b * represent the values measured on locks of hair treated with the mixtures M2 to M5 and Lo *, ao * and bo * represent the values measured on locks of hair treated with Ml.

The larger the value of ΔΕ *, the greater the color difference.

The results are collated in Table 1 below.

STRANDS OF HAIR L * at* b * ΔΕ * Wick treated with Ml 80.02 2.57 19.25 - Wick treated with M2 76.67 -4.36 14.60 8.99 Wick treated with M3 73.91 11.41 16.78 11.03 Wick treated with M4 74.11 -7.74 11,45 14,21 Wick treated with M5 71.86 16.51 14.99 16,70

It can be seen that the value of ΔΕ * is greater for the mixture M4 according to the invention compared to the comparative mixture M2.

Likewise, the value of ΔΕ * is greater for the mixture M5 according to the invention compared to the comparative mixture M3.

Furthermore, the mixture M4 according to the invention leads to a higher value of L * than the comparative mixture M2, therefore to a more intense coloring.

Likewise, the mixture M5 according to the invention leads to a higher value of L * than the comparative mixture M3, therefore to a more intense coloring.

The mixture according to the invention M4 therefore makes it possible to obtain a dye performance superior to the comparative mixture M2.

The mixture according to the invention M5 therefore makes it possible to obtain a dye performance superior to the comparative mixture M3.

Claims (16)

1. Composition for coloring keratin fibers, in particular human keratin fibers, such as the hair, comprising: at least one peroxygenated salt, at least one direct dye, and at least one cyclodextrin. 2. Composition according to the preceding claim, characterized in that the peroxygenated salt or salts are chosen from persulfates; preferably from alkali metal persulfates, alkaline earth metal persulfates, ammonium persulfates, and mixtures thereof; more preferably from (bis) tetrabutylammonium persulfate, barium persulfate, magnesium persulfate, calcium persulfate, sodium persulfate, potassium persulfate, ammonium persulfate, and mixtures thereof; even more preferably from sodium persulfate, potassium persulfate, ammonium persulfate, and mixtures thereof; even better it includes potassium persulfate. 3. Composition according to any one of the preceding claims, characterized in that the total content of peroxygenated salt (s) is between 1 and 30% by weight, preferably between 3 and 25% by weight, more preferably between 4 and 20% by weight, and more preferably still between 5 and 18% by weight, relative to the total weight of the composition. 4. Composition according to any one of the preceding claims, characterized in that the direct dye (s) are chosen from cationic direct dyes, nonionic direct dyes, anionic direct dyes, and their mixtures. 5. Composition according to any one of the preceding claims, characterized in that the direct dye or dyes are chosen from cationic direct dyes: preferably chosen from cationic direct dyes triarylmethanes, cationic azo direct dyes, cationic direct dyes hydrazono , and mixtures thereof; more preferably from: - the following dyes of formula C-II-1 or C-IV-1: (C-IV-1) formulas (C-II-1) and (C-IV-1) in which: - R ¹ represents a group (Ci-C4) alkyl such as methyl; - R ² and R ³ , identical or different, represent a hydrogen atom or a (Ci-C4) alkyl group such as methyl; and - R ⁴ represents a hydrogen atom or an electron donor group such as (Ci-Cs) optionally substituted alkyl, (CiCs) optionally substituted alkoxy, (di) (Ci-C8) (alkyl) amino optionally substituted on the group or groups alkyl with a hydroxyl group; particularly R ⁴ is a hydrogen atom, - Z represents a CH group or a nitrogen atom, preferably CH, Q is an anionic counter ion as defined above, particularly a halide such as chloride or an alkyl sulphate such as methyl sulphate or mesytyl, - the direct cationic dye (s) triarylmethane of formulas (C-VII) and (C-VH ’): (C-νΐΓ) as well as its addition salts with an acid or a base, organic or mineral, its geometric, optical isomers, tautomers, and its mesomeric forms, its solvates such as hydrates: Formulas (C-VII) and (C-VII ’) above in which: * Ri, R2, R3 and R4, identical or different, represent a hydrogen atom or a (Ci-C6) alkyl group optionally substituted, preferably by a hydroxy group; aryl such as phenyl, aryl (Ci-C4) alkyl such as benzyl, heteroaryl, heteroaryl (Ci-C4) alkyl, or then two groups Ri and R2, and / or R3 and R4, carried by the same nitrogen atom form together with the nitrogen atom which carries them an optionally substituted heterocycloalkyl group such as morpholino, piparazino, piperidino, preferably Ri, R2, R3 and R4, identical or different, represents a hydrogen atom or a group (Ci-C ₄ ) alkyl * R5, Rô, R7, Rs, R9, Rio, Ru, R12, R13, R14, R15 and R16, identical or different, represent a hydrogen atom, halogen, or a group chosen from i) hydroxy, ii) thiol, iii) amino iv) (di) (Ci-C4) (alkyl) amino, v) (di) arylamino such as (di) phenylamino, vi) nitro, vii) acylamino (-NR-C ( O) R ') in which the radical R is a hydrogen atom, an alkyl radical in C1-C4 optionally carrying at least one hydroxyl group and the radical R' is an alkyl radical in C1-C2; viii) carbamoyl ((R) 2N-C (O) -) in which the radicals R, which may or may not be identical, represent a hydrogen atom, a C1-C4 alkyl radical optionally carrying at least one hydroxyl group; ix) carboxylic acid or ester, (-OC (O) R ') or (-C (O) OR'), in which the radical R 'is a hydrogen atom, or C1-C4 alkyl optionally bearing at least one hydroxyl group and the radical R 'is a C1-C2 alkyl radical; x) alkyl optionally substituted in particular by a hydroxy group; xi) alkylsulfonylamino (R'SCh-NR-) in which the radical R represents a hydrogen atom, an alkyl radical in C1-C4 optionally carrying at least one hydroxyl group and the radical R 'represents an alkyl radical in C1 -C4, a phenyl radical; xii) aminosulfonyl ((R) 2N-SO2-) in which the radicals R, which may or may not be identical, represent a hydrogen atom, a C1-C4 alkyl radical optionally carrying at least one hydroxyl group, xiii) (Ci -C4) alkoxy, and xiv) (CiC4) alkylthio; * Or then two radicals carried by two contiguous carbon atoms R5 and Rô and / or R7 and Rs, and / or R9 and Rio and / or Rn and R12 and / or R13 and R14 and / or R15 and Rie form together with the carbon atoms which carry them a condensed 6-membered aryl or heteroaryl ring, preferably benzo, said ring possibly being optionally substituted, preferably an unsubstituted benzo ring; * Q- represents an anionic counter ion to achieve electroneutrality, preferably chosen from halides such as chloride, bromide, and phosphate; it being understood that when the cationic dye comprises one or more anionic substituents such as COOR or SO3R with R denoting a hydrogen or a cation, there are then more cationic substituents than anionic substituents, so that the overall resulting charge of the structure triarylmethane is cationic. 6. Composition according to any one of the preceding claims, characterized in that the total content of direct dye (s) is between 0.001 and 20% by weight, preferably between 0.005 and 10% by weight, more preferably between 0.01 and 5% by weight, relative to the total weight of the coloring composition. 7. Composition according to any one of the preceding claims, characterized in that the cyclodextrin or cyclodextrins are chosen from β-cyclodextrins. 8. Composition according to the preceding claim, characterized in that the cyclodextrin or cyclodextrins are chosen from βcyclodextrin, methyl ^ -cyclodextrin, heptakis (2,3,6-trimethyl) β-cyclodextrin, heptakis (2,6- dimethyl) ^ - cyclodextrin, 2hydroxypropyl ^ -cyclodextrin, 2-hydroxyethyl ^ -cyclodextrine, and mixtures thereof; even more preferably from βcyclodextrin, 2-hydroxypropyl ^ -cyclodextrin, 2-hydroxyethylβ-cyclodextrin, and mixtures thereof; and even better among βcyclodextrin, 2-hydroxypropyl ^ -cyclodextrin and their mixtures. 9. Composition according to any one of the preceding claims, characterized in that the total content of cyclodextrin (s) is between 0.1 and 25% by weight, more preferably between 0.5 and 20% by weight, more preferably still between 1 and 15% by weight, even better between 2 and 10% by weight, relative to the total weight of the coloring composition. 10. Composition according to any one of the preceding claims, characterized in that it comprises at least one alkaline agent; preferably chosen from inorganic alkaline agents, more preferably chosen from dibasic or tribasic ammonium phosphates, water-soluble silicates such as silicates of alkali or alkaline earth metals such as sodium disilicate, sodium silicate, dibasic phosphates or tribasic of alkali or alkaline earth metals or the carbonates of alkali or alkaline earth metals, and mixtures thereof; more preferably still among the water-soluble silicates such as the silicates of alkali or alkaline-earth metals; better among sodium disilicate, sodium silicate, and mixtures thereof; even better among sodium silicate. 11. A process for dyeing keratin fibers, in particular human keratin fibers such as the hair, comprising at least one step of applying to said fibers a dye composition as defined according to any one of claims 1 to 10 . 12. Use of the coloring composition as defined according to any one of claims 1 to 10, for the coloring of keratin fibers. 13. Process for simultaneous bleaching / coloring of keratin fibers, in particular human keratin fibers such as the hair, comprising at least one step of application to said fibers: - a coloring composition as defined according to any one of Claims 1 to 10, and - an oxidizing composition (B) distinct from the coloring composition comprising one or more chemical oxidizing agents, preferably different from peroxygenated salts, more preferably chosen from hydrogen peroxide. 14. Simultaneous bleaching / coloring process according to the preceding claim, characterized in that it comprises a step of extemporaneous mixing of said coloring composition with said oxidizing composition before said step or steps of application to said keratin fibers. 15. Device comprising at least two compartments, a first compartment containing a coloring composition as defined according to any one of claims 1 to 10; a second compartment containing an oxidizing composition comprising one or more chemical oxidizing agents, preferably different from the peroxygenated salts. 16. Device comprising at least three compartments, a first compartment containing a composition C1 comprising one or more peroxygenated salts, preferably one or more persulfates as defined according to any one of claims 5 1 and 2; a second compartment containing a composition C2 comprising one or more direct dyes as defined according to any one of claims 1, 4 or 5, and one or more cyclodextrins, as defined according to any one of claims 1, 7 or 8 ; a third compartment containing an oxidizing composition comprising one or more chemical oxidizing agents other than the peroxygenated salts.