Composition for simultaneously bleaching and dyeing keratin fibers and method of using the composition

Abstract

The present invention relates to a composition for simultaneously bleaching and dyeing keratinous fibers, the composition comprising at least one chemical oxidizing agent, at least one (bi)carbonate, at least one silicate, and at least one direct dye, as well as a method for simultaneously bleaching and dyeing keratinous fibers using this composition.

Description

[Technical Field]

[0001] The present invention relates to a composition for simultaneously bleaching and dyeing keratinous fibers, the composition comprising at least one chemical oxidizing agent, at least one (bi)carbonate, at least one silicate, and at least one direct dye, as well as a method for simultaneously bleaching and dyeing keratinous fibers using this composition. [Background technology]

[0002] When it is desired to radically change the color of hair, especially to a color lighter than the original color, it is often necessary to bleach and then dye the hair. There are several methods for accomplishing this.

[0003] The first method involves using a lightening product based on aqueous ammonia and hydrogen peroxide. This product may optionally contain a dye, thereby allowing for simultaneous lightening and dyeing of hair. However, the lightening effect obtained by applying this product remains limited, especially on natural and / or darkly dyed hair.

[0004] The second method involves applying a hair lightening composition based on a peroxide salt such as persulfate and an alkaline agent, with hydrogen peroxide added to the composition at the time of use to enhance lightening. However, these bleaching treatments are generally accompanied by the appearance of an unattractive orange-yellow sheen. To overcome this problem, these compositions may contain direct dyes that allow for simultaneous bleaching and dyeing of hair, with the aim of achieving a more aesthetic color result.

[0005] However, the range of direct dyes that can be used in this composition is still limited, since only stable direct dyes can be used to achieve good color buildup under these conditions and obtain deep, chromatic colors. To solve this stability problem, it has been envisaged to carry out a two-stage process: in a first stage, the hair is bleached using a lightening composition, and then in a second stage, the hair is dyed using a composition containing a direct dye. However, the two-stage process is not satisfactory, as it requires a relatively long time and presents the disadvantages of increased handling procedures and a significant deterioration in the quality of the fibre. Summary of the Invention [Problem to be solved by the invention]

[0006] Therefore, there is a real need to develop a composition for simultaneously bleaching and dyeing keratin fibers, which contains a direct dye and exhibits both good lightening and dyeing properties, especially when applied to dark hair, and which allows for obtaining deep chromatic colors in addition to good color buildup. Furthermore, this type of composition may contain a wide variety of direct dyes, allowing the user to obtain the desired shade. Finally, this type of composition can be used in a one-step method for simultaneously bleaching and dyeing keratin fibers. Such a composition should also be more respectful of the quality of the fibers. [Means for solving the problem]

[0007] Surprisingly, the applicant has found that by using the composition according to the invention, all of these objectives can be achieved.

[0008] According to a first aspect, the subject of the present invention is a composition comprising: i) one or more chemical oxidizing agents selected from hydrogen peroxide, hydrogen peroxide-generating systems other than peroxide salts, and mixtures thereof; ii) one or more compounds selected from carbonates, carbonate-generating systems, bicarbonates, bicarbonate-generating systems, and mixtures thereof; iii) one or more silicates; iv) one or more direct dyes and containing less than 10% by weight of persulfate.

[0009] According to a second aspect, the subject of the present invention is a method for simultaneously bleaching and dyeing keratinous fibers, comprising applying to the keratinous fibers a composition as defined above.

[0010] According to a third aspect, a subject of the invention is the use of a composition as defined above for simultaneously bleaching and dyeing keratinous fibers.

[0011] According to a fourth aspect, the subject of the present invention is a method for producing a pharmaceutical composition comprising: i) a first compartment containing a composition (A) comprising one or more chemical oxidizing agents selected from hydrogen peroxide, hydrogen peroxide-generating systems other than peroxide salts, and mixtures thereof; Composition (B1), ii) one or more compounds selected from carbonates, carbonate-generating systems, bicarbonates, bicarbonate-generating systems, and mixtures thereof; and iii) one or more silicates; and iv) one or more direct dyes a second compartment containing a composition (B1) comprising Contains; or i) a first compartment containing a composition (A) comprising one or more chemical oxidizing agents selected from hydrogen peroxide, hydrogen peroxide-generating systems other than peroxide salts, and mixtures thereof; Composition (B2), ii) one or more compounds selected from carbonates, carbonate-generating systems, bicarbonates, bicarbonate-generating systems, and mixtures thereof; and iii) one or more silicates a second compartment comprising a composition (B2) comprising: iv) a third compartment containing a composition (C) containing one or more direct dyes; A multi-compartment device (kit) comprising: DETAILED DESCRIPTION OF THE INVENTION

[0012] Within the meaning of the present invention, unless otherwise specified: The term "keratinous fibers" is understood to mean fibers of human or animal origin, such as scalp hair, body hair, eyelashes, eyebrows, wool, Angora goat hair, cashmere or fur. According to the invention, the keratinous fibers are preferably human keratinous fibers, more preferentially hair, even more preferentially scalp hair. The term "alkyl group" is understood to mean a saturated, linear or branched hydrocarbon-based group; ·「(C x ~C y The term ") alkyl group" is understood to mean an alkyl group containing x to y carbon atoms; · the term "silicate" is understood to mean silicate; The term "oxidation dyes" is understood to mean oxidation dye precursors selected from oxidation bases and couplers; oxidation bases and couplers are colorless or weakly colored compounds which give colored entities through a condensation reaction in the presence of an oxidizing agent; The term "direct dyes" is understood to mean natural and / or synthetic dyes, including those in the form of extracts, other than oxidation dyes. They are coloring compounds that are superficially distributed on the fiber. They can be ionic or non-ionic, i.e., anionic, cationic, neutral or non-ionic; · The term "chemical oxidant" is understood to mean an oxidant other than atmospheric oxygen; The term "(bi)carbonate" is understood to mean carbonate or bicarbonate.

[0013] Unless otherwise specified, when compounds are referred to in this patent application, this is understood to also mean their optical isomers, their geometric isomers, their tautomers, their salts, their solvates such as hydrates and mixtures thereof.

[0014] The terms "at least one" and "one or more" are synonymous and can be used interchangeably.

[0015] The terms "lightening" and "bleaching" are synonymous and can be used interchangeably.

[0016] composition According to a first aspect, a subject of the present invention is a composition as defined above.

[0017] The Applicant has surprisingly found that the compositions according to the invention stabilize direct dyes and make it possible to obtain a satisfactory level of lightening, as well as better build-up of pigmentation and intense chromatic colors.

[0018] Furthermore, the composition according to the invention has better respect for the quality of the fibres and in particular minimises their degradation.

[0019] Finally, the compositions according to the invention can be used in a single-step process to simultaneously bleach and dye keratinous fibers.

[0020] According to a preferred embodiment, the composition according to the invention comprises: i) hydrogen peroxide; ii) one or more compounds selected from carbonates, bicarbonates and mixtures thereof; iii) one or more silicates; iv) one or more direct dyes and the composition comprises a persulfate content of less than 10% by weight.

[0021] Chemical Oxidizers The compositions according to the present invention comprise i) one or more chemical oxidizing agents selected from hydrogen peroxide, hydrogen peroxide-generating systems other than peroxide salts, and mixtures thereof.

[0022] The hydrogen peroxide generating system other than peroxide salts can be selected from urea hydrogen peroxide, polymer complexes capable of releasing hydrogen peroxide, oxidases and mixtures thereof.

[0023] As examples of polymer complexes capable of releasing hydrogen peroxide, mention may be made of polyvinylpyrrolidone / H2O2, especially in powder form, as well as other polymer complexes described in US Pat. Nos. 5,008,093, 3,376,110 and 5,183,901.

[0024] Oxidases can generate hydrogen peroxide in the presence of an appropriate substrate (eg, glucose in the case of glucose oxidase or uric acid in the case of uricase).

[0025] According to certain embodiments, a hydrogen peroxide-generating system other than hydrogen peroxide and / or peroxide salts can be added immediately before applying the composition according to the invention to keratinous fibers. The intermediate composition containing hydrogen peroxide and / or a hydrogen peroxide-generating system other than hydrogen peroxide and / or peroxide salts can be referred to as an oxidizing composition and can also contain various additional compounds or various adjuvants conventionally used in compositions for dyeing keratinous fibers.

[0026] According to a preferred embodiment, the composition according to the invention comprises hydrogen peroxide as chemical oxidizing agent.

[0027] The chemical oxidizing agents are preferably present in a total content ranging from 1% to 12% by weight, more preferentially from 3% to 9% by weight and even more preferentially from 3.5% to 8.5% by weight relative to the total weight of the composition.

[0028] According to a preferred embodiment, hydrogen peroxide is present in a total content ranging from 1% to 12% by weight, preferably from 3% to 9% by weight and more preferentially from 3.5% to 8.5% by weight relative to the total weight of the composition.

[0029] (B) carbonate and / or (B) carbonate generating system The composition according to the invention additionally comprises ii) one or more compounds selected from carbonates, carbonate-generating systems, bicarbonates, bicarbonate-generating systems and mixtures thereof.

[0030] According to a preferred embodiment, the composition according to the invention additionally comprises ii) one or more compounds chosen from carbonates, bicarbonates and mixtures thereof.

[0031] According to a more preferred embodiment, the composition according to the invention additionally comprises ii) one or more compounds selected from ammonium carbonate, ammonium bicarbonate and mixtures thereof.

[0032] Compounds ii) are preferably present in a total content ranging from 0.01% to 20% by weight, more preferentially from 1% to 15% by weight, even more preferentially from 2% to 15% by weight and most preferentially from 4% to 15% by weight relative to the total weight of the composition.

[0033] Carbonates and / or carbonate generating systems The term "carbonate generating system" is understood to mean a system which generates carbonates in situ, such as, for example, carbon dioxide in water or percarbonate in water.

[0034] Preferably, the carbonate is - alkali metal carbonates; - alkaline earth metal carbonates; - lanthanide carbonates; - transition metal carbonates; - Bismuth carbonate; - cadmium carbonate; - Thallium carbonate; - Zinc carbonate; - Formula(N + R 1 R 2 R 3 R 4 )2CO3 2- (In the formula, R 1 , R 2 , R 3 and R 4 represent, independently of each other, a (C1-C4) alkyl group optionally substituted by a hydrogen atom or a hydroxyl group; - guanidine carbonate; - A mixture of these is selected from.

[0035] More preferentially, the carbonate is selected from sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, magnesium carbonate, calcium carbonate, barium carbonate, strontium carbonate, cerium carbonate, lanthanum carbonate, yttrium carbonate, copper(II) carbonate, manganese carbonate, nickel carbonate, silver carbonate, zirconium carbonate, bismuth carbonate, cadmium carbonate, thallium carbonate, zinc carbonate, ammonium carbonate, guanidine carbonate, tetraethylammonium carbonate and mixtures thereof.

[0036] Even more preferentially, the carbonate is chosen from sodium carbonate, potassium carbonate, cesium carbonate, magnesium carbonate, calcium carbonate, cerium carbonate, manganese carbonate, zinc carbonate, ammonium carbonate, guanidine carbonate and mixtures thereof.

[0037] Most preferentially, the carbonate is chosen from sodium carbonate, potassium carbonate, magnesium carbonate, calcium carbonate, ammonium carbonate and mixtures thereof.

[0038] According to a particularly preferred embodiment, the carbonate contained in the composition is ammonium carbonate.

[0039] The carbonate and / or carbonate-generating system is preferably present in a total content ranging from 0.01% to 20% by weight, more preferentially from 1% to 15% by weight, even more preferentially from 2% to 15% by weight and most preferentially from 4% to 15% by weight relative to the total weight of the composition.

[0040] According to a preferred embodiment, the carbonates are present in a total content ranging from 0.01% to 20% by weight, preferably from 1% to 15% by weight, more preferentially from 2% to 15% by weight and even more preferentially from 4% to 15% by weight relative to the total weight of the composition.

[0041] According to a preferred embodiment, compound ii) is selected from carbonates, carbonate-generating systems and mixtures thereof, preferably carbonates.

[0042] Bicarbonate and / or bicarbonate generating system The term "bicarbonate generating system" is understood to mean a system in which bicarbonate is generated in situ, for example by buffering carbonate with carbon dioxide in water or with inorganic or organic acids.

[0043] Preferably, the bicarbonate is - alkali metal bicarbonates; - alkaline earth metal bicarbonates; - Formula N + R 1 R 2 R 3 R 4 HCO3 - (In the formula, R 1 , R 2 , R 3 and R 4 represent, independently of each other, a (C1-C4) alkyl group optionally substituted by a hydrogen atom or a hydroxyl group; - Aminoguanidine bicarbonate; - A mixture of these is selected from.

[0044] More preferentially, the bicarbonate is chosen from sodium bicarbonate, potassium bicarbonate, lithium bicarbonate, cesium bicarbonate, calcium bicarbonate, magnesium bicarbonate, ammonium bicarbonate, choline bicarbonate, triethylammonium bicarbonate, aminoguanidine bicarbonate and mixtures thereof.

[0045] Even more preferentially, the bicarbonate is chosen from sodium bicarbonate, potassium bicarbonate, cesium bicarbonate, calcium bicarbonate, magnesium bicarbonate, ammonium bicarbonate and mixtures thereof.

[0046] Most preferentially, the bicarbonate is chosen from sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate and mixtures thereof.

[0047] According to a particularly preferred embodiment, the bicarbonate contained in the composition is ammonium bicarbonate.

[0048] The bicarbonate may be derived from natural waters, such as spring waters from the Vichy Basin or La Roche Posay, or waters from Badoit.

[0049] The bicarbonate and / or bicarbonate-generating system is preferably present in a total content ranging from 0.01% to 20% by weight, more preferentially from 1% to 15% by weight, even more preferentially from 2% to 15% by weight and most preferentially from 4% to 15% by weight relative to the total weight of the composition.

[0050] According to a preferred embodiment, the bicarbonate is present in a total content ranging from 0.01% to 20% by weight, preferably from 1% to 15% by weight, more preferentially from 2% to 15% by weight and even more preferentially from 4% to 15% by weight relative to the total weight of the composition.

[0051] According to a preferred embodiment, compound ii) is selected from bicarbonates, bicarbonate-generating systems and mixtures thereof, preferably bicarbonates.

[0052] Silicate The composition according to the invention additionally comprises iii) one or more silicates.

[0053] The silicate is preferably water-soluble.

[0054] The term "water-soluble silicate" is understood to mean a silicate which exhibits a solubility in water at normal ambient temperature (25°C) and atmospheric pressure (760 mmHg) of more than 0.5% by weight, preferably more than 1% by weight.

[0055] Preferably, the silicate is selected from alkali metal silicates, alkaline earth metal silicates, aluminum silicate, trimethylammonium silicate and mixtures thereof.

[0056] More preferentially, the silicate is chosen from sodium silicate, potassium silicate, calcium silicate, aluminum silicate, trimethylammonium silicate and mixtures thereof.

[0057] More preferentially, the silicates are chosen from sodium silicates, examples of which may include compounds with CAS numbers: [1344-09-8] and [6834-92-0].

[0058] The silicates are preferably present in a total content ranging from 1% to 40% by weight, more preferentially from 2% to 35% by weight, even more preferentially from 3% to 35% by weight and most preferentially from 4% to 20% by weight relative to the total weight of the composition.

[0059] The mass ratio of the total amount of (bi)carbonates and / or (bi)carbonate-generating systems ii) to the total amount of silicates iii) is preferably 0.00025 to 2000, more preferentially 0.06 to 15, and even more preferentially 1 to 7.5.

[0060] According to a preferred embodiment, the mass ratio of the total amount of (bi)carbonates ii) / the total amount of silicates iii) is between 0.00025 and 2000, preferably between 0.06 and 15, and more preferentially between 1 and 7.5.

[0061] The mass ratio of the total amount of (bi)carbonates and / or (bi)carbonate-generating systems ii) to the total amount of chemical oxidizing agents i) is preferably 0.0008 to 20, more preferentially 0.1 to 5, and even more preferentially 0.2 to 4.3.

[0062] According to a preferred embodiment, the mass ratio of the total amount of (bi)carbonates ii) / the total amount of chemical oxidizing agents i) is between 0.0008 and 20, preferably between 0.1 and 5, and more preferentially between 0.2 and 4.3.

[0063] According to a more preferred embodiment, the mass ratio of the total amount of (bi)carbonates ii) to the total amount of hydrogen peroxide is 0.0008 to 20, preferably 0.1 to 5, and more preferably 0.2 to 4.3.

[0064] The mass ratio of the total amount of carbonates and / or carbonate-generating systems to the total amount of bicarbonates and / or bicarbonate-generating systems is preferably 0.01 to 100, more preferentially 0.01 to 1, even more preferentially 0.01 to 0.75.

[0065] According to a preferred embodiment, the mass ratio of total amount of carbonates / total amount of bicarbonates is between 0.01 and 100, preferably between 0.01 and 1, and more preferentially between 0.01 and 0.75.

[0066] The composition preferably comprises a total content of magnesium carbonate of less than 5% by weight, more preferentially less than 1% by weight, even more preferentially less than 0.1% by weight, most preferentially less than 0.01% by weight and even better less than 0.001% by weight.

[0067] According to a particularly preferred embodiment, the composition does not contain magnesium carbonate.

[0068] The composition comprises a total content of persulfates of less than 10% by weight, preferably less than 5% by weight, more preferentially less than 1% by weight, even more preferentially less than 0.1% by weight, most preferentially less than 0.01% by weight and even better less than 0.001% by weight.

[0069] According to a particularly preferred embodiment, the composition is persulfate-free.

[0070] direct dye The composition according to the invention comprises iv) one or more direct dyes.

[0071] The direct dyes may be selected from neutral, cationic or anionic direct dyes and mixtures thereof.

[0072] Direct dyes include acridines, acridones, anthranthrones, anthrapyrimidines, anthraquinones, azines, (poly)azo or azo, hydrazono or hydrazones, especially arylhydrazones, azomethines, benzanthrones, benzimidazoles, benzimidazolones, benzindoles, benzoxazoles, benzopyrans, benzothiazoles, benzoquinones, bis-isoindolines, carboxanilides, coumarins, cyanines such as (di)azacarbocyanines, (di)azahemicyanines, hemicyanines or tetraazacarbocyanines, (di)azines, bis-azines, (di)oxazines, (di)thiazines, (di)phenylamines, (di)phenylmethanes, (di)ketopyrrolopyrroles, flavonoids such as flavanthrones and flavones, fluorindins, formazans, indamines, indanthrones, The dye may be a neutral, cationic or anionic direct dye selected from indigoids, thioindigoids and pseudoindigoids; indophenols; indoanilines; isoindolines; isoindolinones; isoviolanthrone; lactones; (poly)methines such as stilbene or styryl-type dimethines; naphthalimides; naphthanilides; naphtholactams; naphthoquinones; nitro, especially nitro(hetero)aromatics; oxadiazoles; oxazines; perylones; perinones; perylenes; phenazines; phenoxazines; phenothiazines; phthalocyanines; polyenes / carotenoids; porphyrins; pyranthrones; pyrazoloanthrones; pyrazolones; pyrimidinoanthrones; pyronines; quinacridones; quinolines; quinophthalones; squalanes; tetrazolines; thiazines; thiopyronines; triarylmethanes; or xanthenes; and natural direct dyes. Preferably, the direct dyes are chosen from anthraquinones, (poly)azos, azomethines and stilbenes, more preferentially anthraquinones.

[0073] The direct dyes may be selected in particular from neutral, cationic or anionic nitrobenzene direct dyes, neutral, cationic or anionic azo direct dyes, neutral, cationic or anionic tetraazapentamethine dyes, cationic or anionic quinone dyes, in particular neutral, cationic or anionic anthraquinone dyes, neutral, cationic or anionic azine direct dyes, neutral, cationic or anionic triarylmethane direct dyes, neutral, cationic or anionic azomethine direct dyes and natural direct dyes. Preferably, the direct dyes are selected from neutral or anionic anthraquinone dyes and stilbenes.

[0074] Neutral, anionic or cationic direct dyes which can be used in the present invention include the following dyes: acridines, acridones, anthranthrones, anthrapyrimidines, anthraquinones, azines, (poly)azos, hydrazonos or hydrazones, in particular arylhydrazones, azomethines, benzanthrones, benzimidazoles, benzimidazolones, benzindoles, benzoxazoles, benzopyrans, benzothiazoles, benzoquinones, bisazines, bis-isoindolines, carboxanilides, coumarins, cyanines such as azacarbocyanines, diazacarbocyanines, diazahemicyanines, hemicyanines or tetraazacarbocyanines, diazines, diketopyrrolopyrroles, dioxazines, diphenylamines, diphenylmethanes, dithiaazines, flavonoids such as flavanthrones and flavones, fluorines Examples of suitable compounds include dimethines, formazans, indamines, indanthrones, indigoids and pseudoindigoids, indophenols, indoanilines, isoindolines, isoindolinones, isoviolanthrones, lactones, (poly)methines such as stilbene or styryl-type dimethines, naphthalimides, naphthanilides, naphtholactams, naphthoquinones, nitro, especially nitro(hetero)aromatics, oxadiazoles, oxazines, perylones, perinones, perylenes, phenazines, phenoxazines, phenothiazines, phthalocyanines, polyenes / carotenoids, porphyrins, pyranthrones, pyrazoloanthrones, pyrazolones, pyrimidinoanthrones, pyronines, quinacridones, quinolines, quinophthalones, squalanes, tetrazoles, thiazines, thioindigo, thiopyronines, triarylmethanes, or xanthenes.

[0075] neutral direct dye The direct dyes may preferably be neutral direct dyes selected from hydrazono dyes of the following formulae (IIIa) and (III'a), azo and styryl dyes (IVa), diazo and distyryl dyes (IV'a) and (IV''a), anthraquinone dyes (Va) and azomethine dyes (VIa) and (VI'a), and mixtures thereof: [ka] In formulas (IIIa), (III'a), (IVa), (IV'a), (IV''a), (Va), (VIa) and (VI'a), Ar represents i) optionally substituted (C1-C8) alkyl, ii) optionally substituted (C1-C8) alkoxy, iii) (di)(C1-C8)(alkyl)amino in which the alkyl group is optionally substituted by a hydroxyl group, iv) aryl(C1-C8) alkylamino, v) an aryl group substituted by at least one electron-donating group, such as phenyl or naphthyl, such as optionally substituted N—(C1-C8) alkyl-N-aryl(C1-C8) alkylamino, or Ar represents a julolidine group; Ar' represents an optionally substituted divalent (hetero)arylene group, such as phenylene, in particular paraphenylene or naphthalene, optionally substituted by one or more (C1-C8) alkyl, hydroxyl or (C1-C8) alkoxy groups; Ar″ preferably represents a (hetero)aryl group optionally substituted by at least i) an electron-withdrawing group such as nitro, nitroso, -C(X)-X′-R′, or ii) a (di)(C1-C6)(alkyl)amino group, iii) a hydroxyl group, or iv) a (C1-C6)alkoxy group; in particular, (hetero)aryl is selected from imidazolyl, triazolyl, indolyl or pyridyl, or phenyl optionally substituted by at least one group selected from nitro, nitroso and amino, preferably substituted in the para position of the phenyl group; X, X' and X'' are identical or different and represent an oxygen or sulfur atom or an NR'' group, preferably an oxygen atom; ·R 1 , R 2 , R 3 and R 4 are the same or different and represent a hydrogen or halogen atom or a group selected from hydroxyl, thiol, (C1-C4) alkyl, (C1-C4) alkoxy, (di)(C1-C4) (alkyl) amino, nitro and nitroso; R' and R'' represent a (C1-C4) alkyl group; ·R a and R b are the same or different and represent a hydrogen atom or a (C1-C8) alkyl group optionally substituted, preferably by a hydroxyl group; or In an alternative embodiment, the substituent R a is a substituent of Ar″, and / or R b is a substituent of Ar, and / or R a R b and together with the atoms carrying them form a (hetero)cycloalkyl; In particular, R a and R b represents a (C1-C4) alkyl group optionally substituted with a hydrogen atom or a hydroxyl group; T and T' are the same or different, and C(R a ) group or N, preferably N; L represents the divalent group -ALK-, -C(X)-ALK-, -ALK-C(X)-, or -C(X)-ALK-C(X')-, where ALK represents a linear or branched (C1-C6) alkylene group such as methylene, and X and X' are as defined above; ·R 22 , R 23 , R 24 , R 25 , R 26 and R 27 are the same or different and represent a hydrogen or halogen atom, or - (C1-C6) alkyl; - hydroxyl, mercapto; - (C1-C6)alkoxy, (C1-C6)alkylthio; - aryloxy or arylthio; - aryl(C1-C6)(alkyl)amino; - (di)(C1-C6)(alkyl)amino; - (Di)(hydroxy(C1-C6)alkyl)amino represents a group selected from: Z' is a hydrogen atom or NR28 R 29 group (in the formula, R 28 and R 29 are the same or different and represent a hydrogen atom, or - (C1-C6) alkyl; - polyhydroxy(C1-C6) alkyl, such as hydroxyethyl; - one or more groups, in particular i) (C1-C6) alkyl; iii) R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X''- (wherein R° represents a (C1-C6) alkyl group and X, X' and X'' are as defined above); iv) aryl optionally substituted by sulfonate; - cycloalkyl, especially cyclohexyl represents a group selected from: Z is hydroxyl and NR' 28 R' 29 (In the formula, R' 28 and R' 29 are the same or different and are R as defined above 28 and R 29 represents the same atom or group as represents a group selected from

[0076] The direct dye of formula (IV''a) preferably has the formula (IV'''a): [ka] (In formula (IV'''a), ·R 1 and R 3 are the same or different, preferably the same, and represent a hydrogen atom, a (C1-C4) alkyl group such as methyl, or a sugar group such as glucosyl, preferably a hydrogen atom; ·R 2 and R 4 are the same or different, preferably the same, and represent a hydrogen atom, a (C1-C4) alkyl or (C1-C4) alkoxy group, or an -O-sugar group such as -O-glucosyl, preferably a (C1-C4) alkoxy such as methoxy; X are identical or different, preferably identical, and represent an oxygen or sulfur atom or NR, where R represents a hydrogen atom or a group, preferably an oxygen atom; ALK represents a (C1-C4) alkylene group such as methylene or ethylene, preferably methylene. It is of the type.

[0077] The direct dyes of formula (IV''a) can be obtained from curcumin, demethoxycurcumin and bisdemethoxycurcumin.

[0078] Preferably, the direct dye is selected from the direct dyes of formula (IV''a) and (IV'''a) as defined above, and mixtures thereof.

[0079] According to a particularly preferred embodiment, the direct dye is selected from the following compounds (A) to (G) and mixtures thereof: [ka] , preferably selected from compounds (E), (F) and (G) and mixtures thereof, more preferentially from compounds (E) and (G) and mixtures thereof.

[0080] Cationic Direct Dyes The direct dyes can be selected from those commonly referred to as "basic dyes" because they are cationic or have an affinity for acidic substances, and in particular those direct dyes that contain at least one endocyclic or exocyclic cationic or cationizable group in their structure.

[0081] In particular, cationic azo dyes that can be used in the present invention include those described in the Kirk-Othmer Encyclopedia of Chemical Technology, "Dyes, Azo", J. Wiley & Sons, revised 19 / 04 / 2010.

[0082] Mention may also be made of the cationic azo dyes described in patent applications WO 95 / 15144, WO 95 / 01772 and EP 714954.

[0083] Mention may be made of the cationic azo dyes described in the Colour Index International, 3rd Edition, in particular the following compounds: Basic Red 22, Basic Red 76, Basic Yellow 57, Basic Brown 16 and Basic Brown 17.

[0084] Among the cationic quinone dyes, those mentioned in the Colour Index International, 3rd Edition, are suitable, and among these, the following dyes may especially be mentioned: Basic Blue 22 and Basic Blue 99.

[0085] Suitable azine dyes may include those listed in the Colour Index International, 3rd Edition, such as the following dyes: Basic Blue 17 and Basic Red 2.

[0086] As cationic triarylmethane dyes that can be used in accordance with the present invention, mention may be made of the following dyes in addition to those mentioned in the Colour Index International, 3rd Edition: Basic Green 1, Basic Violet 3, Basic Violet 14, Basic Blue 7 and Basic Blue 26.

[0087] Mention may also be made of the direct dyes described in the documents U.S. Pat. No. 5,888,252, EP 1,133,975, WO 03 / 029359, EP 860,636, WO 95 / 01772, WO 95 / 15144 and EP 714,954.

[0088] Mention may also be made of those listed in various chapters of the encyclopedia "The Chemistry of Synthetic Dyes" by K. Venkataraman, 1952, Academic Press, Vol. 1-7, "Kirk-Othmer Encyclopedia of Chemical Technology", chapter "Dyes and Dye Intermediates", 1993, Wiley & Sons, and "Ullmann's Encyclopedia of Industrial Chemistry", 7th edition, Wiley & Sons.

[0089] Preferably, the cationic direct dyes are chosen from those derived from the azo and hydrazono type dyes.

[0090] Cationic direct dyes are described in European Patent No. 850636, French Patent No. 2788433, European Patent No. 920856, International Publication No. WO 99 / 48465, French Patent No. 2757385, European Patent No. 850637, European Patent No. 918053, International Publication No. WO 97 / 44004, French Patent No. 2570946, French Patent No. 2285851, German Patent Application Publication No. 2538363, French Patent Application Publication No. 2189006, French Patent Application Publication No. 1560664, French Patent Application Publication No. 1540423, French Patent Application Publication No. 1567219, French Patent Application Publication No. 1516943 Documents, French Patent Application Publication No. 1221122, German Patent No. 4220388, German Patent No. 4137005, International Publication No. 01 / 66646, U.S. Patent No. 5708151, International Publication No. 95 / 01772, International Publication No. 515144, British Patent Application Publication No. 1195386, U.S. Patent No. 3524842, U.S. Patent No. 5879413, European Patent No. 1062940, European Patent No. 1133976, British Patent No. 738585, German Patent Application Publication No. 2527638, French Patent No. 2275462, British Patent Application Publication No. 1974-27645, Acta Histochem, (1978), 61(1), 48-52; Tsitologiya (1968), 10 (3), 403-5; Zh. Obshch. Khim., (1970), 40 (1), 195-202; Ann. Chim. 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.

[0091] Preferably, the cationic direct dyes contain a quaternary ammonium group; more preferentially, the cationic charge is in the ring. These cationic groups are, for example: - carrying an exocyclic (di / tri)(C1-C8) alkylammonium charge, or cationic groups with an endocyclic charge, which contain a cationic heteroaryl group selected from acridinium, benzimidazolium, benzobistriazolium, benzopyrazolium, benzopyridazinium, benzoquinolium, benzothiazolium, benzotriazolium, benzoxazolium, bipyridinium, bis-tetrazolium, dihydrothiazolium, imidazopyridinium, imidazolium, indolium, isoquinolium, naphthimidazolium, naphthoxazolium, naphthopyrazolium, oxadiazolium, oxazolium, oxazolopyridinium, oxonium, phenazinium, phenoxazolium, pyrazinium, pyrazolium, pyrazoyltriazolium, pyridinium, pyridinoimidazolium, pyrrolium, pyrylium, quinolium, tetrazolium, thiadiazolium, thiazolium, thiazolopyridinium, thiazoylimidazolium, thiopyrylium, triazolium or xanthylium;

[0092] Mention may also be made of the cationic hydrazono direct dyes of the following formulae (IIb) and (IIIb) and the cationic azo direct dyes of the following formulae (IVb) and (Vb). Het + -C(R a )=NN(R b )-Ar,Q - (IIb); Het + -N(R a )-N=C(Rb )-Ar,Q - (IIIb); Het + -N=N-Ar,Q - (IVb); Ar + -N=N-Ar'',Q - (Vb); In formulas (IIb) to (Vb), Het + represents a cationic heteroaryl group such as imidazolium, indolium or pyridinium, preferentially having a cationic charge in the ring and preferentially optionally substituted with at least one (C1-C8) alkyl group such as methyl; ·Ar + represents an aryl group such as phenyl or naphthyl bearing an exocyclic cationic charge, preferentially ammonium, in particular tri(C1-C8)alkylammonium such as trimethylammonium; Ar preferentially represents an aryl group, in particular phenyl, optionally substituted by one or more electron-donating groups, such as i) optionally substituted (C1-C8) alkyl, ii) optionally substituted (C1-C8) alkoxy, iii) (di)(C1-C8)(alkyl)amino, in which the alkyl group is optionally substituted by a hydroxyl group, iv) aryl(C1-C8) alkylamino, v) optionally substituted N—(C1-C8) alkyl-N-aryl(C1-C8) alkylamino, or alternatively, Ar represents a julolidine group; Ar'' represents an optionally substituted (hetero)aryl group, such as phenyl or pyrazolyl, preferentially substituted by one or more (C1-C8)alkyl, hydroxyl, (di)(C1-C8)(alkyl)amino, (C1-C8)alkoxy or phenyl groups; ·R a and R b are identical or different and represent a hydrogen atom or a (C1-C8) alkyl group optionally substituted, preferentially by a hydroxyl group; or otherwise, the substituent Ra Het + and / or R b is a substituent of Ar, and / or R a R b together with the atoms carrying them form a (hetero)cycloalkyl; in particular R a and R b represents a hydrogen atom or a (C1-C4) alkyl group optionally substituted with a hydroxyl group; Q - represents an anionic counterion such as a halide, alkyl sulfate, or alkyl sulfonate.

[0093] Mention may in particular be made of the azo and hydrazono direct dyes of formulae (IIb) to (Vb) with an internal cationic charge as defined above, and more particularly the cationic direct dyes of formulae (IIb) to (Vb) with an internal cationic charge as described in patent applications WO 95 / 15144, WO 95 / 01772 and EP 714954.

[0094] Preferred examples of direct dyes include the following: [ka] In formulas (II-1) and (IV-1), ·R 1 represents a (C1-C4) alkyl group such as methyl; ·R 2 and R 3 are the same or different and represent a hydrogen atom or a (C1-C4) alkyl group such as methyl; ·R 4 represents a hydrogen atom or an electron donating group, such as an optionally substituted (C1-C8) alkyl, an optionally substituted (C1-C8) alkoxy or a (di)(C1-C8)(alkyl)amino, wherein the alkyl group is optionally substituted with a hydroxyl group; in particular, R 4 is a hydrogen atom; Z represents a CH group or a nitrogen atom, preferentially CH; Q - is an anionic counterion as defined above, especially a halide such as chloride or an alkyl sulfate such as methyl sulfate or mesityl.

[0095] In particular, the dyes of formulae (II-1) and (IV-1) are selected from Basic Red 51, Basic Yellow 87 and Basic Orange 31 or derivatives thereof. [ka] wherein Q' is an anionic counterion as defined above, in particular a halide, such as chloride, or an alkyl sulfate, such as methyl sulfate or mesityl.

[0096] fluorescent dye The direct dye may be selected from fluorescent direct dyes.

[0097] Examples of fluorescent dyes that can be used in the present invention include neutral, anionic or cationic dyes selected from the following dyes: acridine, acridone, benzanthrone, benzimidazole, benzimidazolone, benzindole, benzoxazole, benzopyran, benzothiazole, coumarin, difluoro{2-[(2H-pyrrol-2-ylidene-kN)methyl]-1H-pyrrolato-kN}boron (BODIPY®), diketopyrrolopyrrole, fluorindine, (poly)methines (especially cyanines and styryl / hemicyanines), naphthalimides, naphthanilides, naphthylamines (such as dansyl), oxadiazoles, oxazines, perylones, perinones, perylenes, polyenes / carotenoids, squalanes, stilbenes and xanthenes.

[0098] Fluorescent dyes are described in the documents EP 1 133 975, WO 03 / 029359, EP 860 636, WO 95 / 01772, WO 95 / 15144 and EP 714 954, as well as in the encyclopedia "The Chemistry of Synthetic Dyes" by K. Venkataraman, 1952, Academic Press, Vol. 1-7, "Kirk-Othmer Encyclopedia of Chemical Technology", chapter "Dyes and Dye Intermediates", 1993, Wiley & Sons, and various chapters in "Ullmann's Encyclopedia of Industrial Chemistry", 7th edition, Wiley & Sons, and in the handbook - "A Guide to Fluorescent Probes and Labeling Technologies", 10th Ed., Molecular Probes / Invitrogen-Oregon. 2005, available on the Internet or in the preceding printed edition.

[0099] According to a preferred alternative, the fluorescent dye is a cationic polymethine comprising at least one quaternary ammonium group, such as that of formula (Vb) below: W + -[C(R c )=C(R d )] m’ -ArQ - In the formula (Vb), ·W + represents a cationic heterocyclic or heteroaryl group, in particular containing a quaternary ammonium group, which is optionally substituted, in particular with one or more (C1-C8) alkyl groups, which are optionally substituted with one or more hydroxyl groups; Ar is an aryl group, such as phenyl or naphthyl, optionally and preferentially substituted by i) one or more halogen atoms, such as chlorine or fluorine; ii) one or more (C1-C8) alkyl, preferably (C1-C4) alkyl, groups, such as methyl; iii) one or more hydroxyl groups; iv) one or more (C1-C8) alkoxy groups, such as methoxy; v) one or more hydroxy(C1-C8) alkyl groups, such as hydroxyethyl; vi) one or more (di)(C1-C8) alkylamino groups, in which one or more amino groups or the C1-C4 alkyl moieties thereof are preferably optionally substituted with one or more hydroxyl groups, such as (di)hydroxyethylamino; vii) one or more acylamino groups; viii) one or more aryl groups, substituted by one or more heterocycloalkyl groups, such as piperazinyl, piperidyl or 5- or 6-membered heteroaryl, such as pyrrolidinyl, pyridyl and imidazolinyl; m' represents an integer ranging from 1 to 4, preferably m' is 1 or 2; more preferentially m'=1; ·R c and R d are the same or different and represent a hydrogen atom or an optionally substituted (C1-C8) alkyl group, preferably an optionally substituted (C1-C4) alkyl group, or alternatively, W + and adjacent R c and / or R adjacent to Ar d together with the atoms which carry them form a (hetero)cycloalkyl; in particular, R c is W + and adjacent to each other, which form a (hetero)cycloalkyl such as cyclohexyl; Q - is the anionic counterion defined above.

[0100] Anionic dyes The direct dyes can be selected from anionic direct dyes or dyes commonly referred to as "acid" direct dyes because of their affinity for alkaline materials.

[0101] The term "anionic direct dye" is understood to mean any direct dye which contains in its structure at least one CO2R or SO3R substituent, where R represents a hydrogen atom or a cation or ammonium ion derived from a metal or an amine. The anionic dye may be chosen from acid nitro direct dyes, acid azo dyes, acid azine dyes, acid triarylmethane dyes, acid indoamine dyes, acid anthraquinone dyes, indigoids and acid natural dyes.

[0102] Preferably, the anionic direct dye is an acidic anthraquinone.

[0103] The direct dye may preferably be an anionic direct dye selected from the following formulae (III), (III'), (IV), (IV'), (V), (V'), (VI), (VI'), (VII), (VIII), (IX) and (X) and mixtures thereof:

[0104] a) diaryl anionic azo dyes of formula (III) or (III'): [ka] In formulas (III) and (III'), R7, R8, R9, R 10 , R'7, R'8, R'9 and R' 10 are the same or different and represent a hydrogen atom, or - (C1-C6) alkyl; - (C1-C6)alkoxy, (C1-C6)alkylthio; - hydroxyl, mercapto; - Nitro, nitroso; - R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X''- (wherein R° represents a hydrogen atom or a (C1-C6) alkyl group or an aryl group such as phenyl; X, X' and X'' are the same or different and represent an oxygen or sulfur atom or NR (wherein R represents a hydrogen atom or a (C1-C6) alkyl group)); -M+ (O)2S(O - )-(in the formula, M + represents a hydrogen atom or a cationic counterion); -M + (O)CO - -(in the formula, M + is as defined above); - R"-S(O)2- (wherein R" represents a hydrogen atom or an alkyl, aryl, (di)(C1-C6)(alkyl)amino or aryl(C1-C6)(alkyl)amino group; preferentially a phenylamino or phenyl group); - R'''-S(O)2-X'- (wherein R''' represents an optionally substituted (C1-C6) alkyl or aryl group, and X' is as defined above); - (di)(C1-C6)(alkyl)amino; - i) Nitro; ii) Nitroso; iii) M + (O)2S(O - )-,(where M + is as defined above), and iv) aryl(C1-C6)(alkyl)amino optionally substituted with one or more groups selected from (C1-C6)alkoxy; - optionally substituted heteroaryl; preferentially a benzothiazolyl group; - cycloalkyl, in particular cyclohexyl; - Ar-N=N-, where Ar represents an optionally substituted aryl group; preferentially one or more alkyl, M + (O)2S(O - )- or phenyl optionally substituted with a phenylamino group) or represents a group selected from otherwise, two adjacent groups R7 and R8, or R8 and R9, or R9 and R 10 together form a fused benzo group A'; R'7 and R'8, or R'8 and R'9, or R'9 and R' 10 together form a fused benzo group B'; A' and B' are i) nitro; ii) nitroso; iii) M+ (O)2S(O - )-; iv) hydroxyl; v) mercapto; vi) (di)(alkyl)amino; vii) R°-C(X)-X'-; viii) R°-X'-C(X)-; ix) R°-X'-C(X)-X''-; x) Ar-N=N-; and xi) optionally substituted aryl(C1-C6)(alkyl)amino; M + , R°, X, X′, X″ and Ar are as defined above; W is a sigma σ bond, an oxygen or sulfur atom, or a divalent group i) —NR— (wherein R is as defined above) or ii) methylene-C(R a )(R b )-(wherein, R a and R b are the same or different and represent a hydrogen atom or an aryl group, or else R a and R b together with the carbon atoms which carry them form a spirocycloalkyl); preferentially, W represents a sulfur atom or R a and R b together to form cyclohexyl; Formulas (III) and (III') are those in which in one of rings A, A', B, B' or C: - at least one M' + (O)2S(O - )-group (wherein, M' + represents a cationic counterion); or - at least one M' + (O)CO - - group (in the formula, M' + represents a cationic counterion); Preferably at least one sodium sulfonate group It is understood that this includes:

[0105] Examples of dyes of formula (III) are Acid Red 1, Acid Red 4, Acid Red 13, Acid Red 14, Acid Red 18, Acid Red 27, Acid Red 28, Acid Red 32, Acid Red 33, Acid Red 35, Acid Red 37, Acid Red 40, Acid Red 41, Acid Red 42, Acid Red 44, 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 36, Acid Yellow 199, Food Yellow Examples of dyes of formula (III′) include Acid Red 111, Acid Red 134, and Yellow 38.

[0106] b) Anionic pyrazolone azo dyes of formula (IV) or (IV'): [ka] In formulas (IV) and (IV'), ·R 11 , R 12 and R 13 are the same or different and are a hydrogen atom, a halogen atom, a (C1-C6) alkyl group, or M + (O)2S(O - )-group (wherein, M+ is as defined above); ·R 14 is a hydrogen atom, a (C1-C6) alkyl group, or M + C(O)O - - group (in the formula, M + is as defined above); ·R 15 represents a hydrogen atom; ·R 16 represents an oxo group, in which case R' 16 does not exist, or else R 15 is R 16 together to form a double bond; ·R 17 and R 18 are the same or different and represent a hydrogen atom, or -M + (O)2S(O - )-(wherein, M + is as defined above); - Ar-OS(O)2-, where Ar represents an optionally substituted aryl group, preferentially phenyl optionally substituted with one or more alkyl groups. represents a group selected from: ·R 19 and R 20 together form either a double bond or an optionally substituted benzo group D'; R' 16 , R' 19 and R' 20 are the same or different and represent a hydrogen atom, a (C1-C6) alkyl group, or a hydroxyl group; ·R 21 represents a hydrogen atom, a (C1-C6) alkyl group, or a (C1-C6) alkoxy group; ·R a and R b are identical or different and are as defined above; preferentially, R a represents a hydrogen atom, and R b represents an aryl group such as phenyl; Y represents either a hydroxyl group or an oxo group; · [ka] represents a single bond when Y is an oxo group; represents a double bond when Y is a hydroxyl group; Formulas (IV) and (IV') may have, in one of rings D or E, - at least one M' + (O)2S(O - )-group (wherein, M' + represents a cationic counterion); or - at least one M' + (O)CO - - group (in the formula, M' + represents a cationic counterion); Preferably at least one sodium sulfonate group It is understood that this includes:

[0107] Examples of dyes of formula (IV) include Acid Red 195, Acid Yellow 23, Acid Yellow 27, and Acid Yellow 76; examples of dyes of formula (IV') include Acid Yellow 17.

[0108] c) Anthraquinone dyes of formula (V) or (V'): [ka] In formulas (V) and (V'), ·R 22 , R 23 , R 24 , R 25 , R 26 and R 27 are the same or different and represent a hydrogen atom, a halogen atom, or - (C1-C6) alkyl; - hydroxyl, mercapto; - (C1-C6)alkoxy, (C1-C6)alkylthio; - Preferentially alkyl and M + (O)2S(O - )-(wherein, M + is as defined above); optionally substituted aryloxy or arylthio, substituted with one or more groups selected from - alkyl and M + (O)2S(O - )-(wherein, M + is as defined above); - (di)(C1-C6)(alkyl)amino; - (di)(hydroxy(C1-C6)alkyl)amino; -M + (O)2S(O - )-(wherein, M + is as defined above) represents a group selected from: Z' is a hydrogen atom or NR 28 R 29 group (in the formula, R 28 and R 29 are the same or different and represent a hydrogen atom, or - (C1-C6) alkyl; - polyhydroxy(C1-C6) alkyl, such as hydroxyethyl; one or more groups, in particular i) (C1-C6) alkyl, such as methyl, n-dodecyl or n-butyl; ii) M + (O) 2 S(O - )-(wherein, M + is as defined above; iii) aryl optionally substituted with R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X''- (wherein R°, X, X' and X'' are as defined above and preferentially R° represents a (C1-C6) alkyl group); - cycloalkyl, especially cyclohexyl represents; Z is hydroxyl and NR' 28 R'29 (In the formula, R' 28 and R' 29 are the same or different and are R as defined above 28 and R 29 represents the same atom or group as Formulas (V) and (V') are - at least one M' + (O)2S(O - )-group (wherein, M' + represents a cationic counterion); or - at least one M' + (O)CO - - group (in the formula, M' + represents a cationic counterion); Preferably at least one sodium sulfonate group It is understood that this includes:

[0109] Examples of dyes of formula (V) include 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 or Ext. Violet No. 2; and an example of a dye of formula (V') includes Acid Black 48.

[0110] d) Nitro dyes of formula (VI) or (VI'): [ka] In formulas (VI) and (VI'), ·R 30 , R 31 and R 32 are the same or different and represent a hydrogen atom, a halogen atom, or - (C1-C6) alkyl; - (C1-C6)alkoxy optionally substituted with one or more hydroxyl groups or (C1-C6)alkylthio optionally substituted with one or more hydroxyl groups; - hydroxyl, mercapto; - Nitro, nitroso; - polyhalo(C1-C6)alkyl; - R°-C(X)-X'-, R°-X'-C(X)- or R°-X'-C(X)-X''- (wherein R°, X, X' and X'' are as defined above); -M + (O)2S(O - )-(in the formula, M + is as defined above); -M + (O)CO - -(in the formula, M + is as defined above); - (di)(C1-C6)(alkyl)amino; - (di)(hydroxy(C1-C6)alkyl)amino; heterocycloalkyl, such as piperidino, piperazino or morpholino represents a group selected from: In particular, R 30 , R 31 and R 32 represents a hydrogen atom; ·R c and R d are the same or different and represent a hydrogen atom or a (C1-C6) alkyl group; W is as defined above; W represents in particular the —N(H)— group; ALK represents a linear or branched divalent C1-C6 alkylene group; in particular, ALK represents a -CH2-CH2- group; n has a value of 1 or 2; ·p represents an integer ranging from 1 to 5; q represents an integer ranging from 1 to 4; u has a value of 0 or 1; when n has the value 1, J represents a nitro or nitroso group; in particular a nitro group; When n has a value of 2, J is an oxygen or sulfur atom or a divalent -S(O) m - group, where m represents an integer of 1 or 2; preferentially, J represents a -SO2- group; M″ represents a hydrogen atom or a cationic counterion; · [ka] is present or absent and is one or more R as defined above 30 represents a benzo group optionally substituted by a group; Formulas (VI) and (VI') are - at least one M' + (O)2S(O - )-group (wherein, M' + represents a cationic counterion); or - at least one M' + (O)CO - - group (in the formula, M' + represents a cationic counterion); Preferably at least one sodium sulfonate group It is understood that this includes:

[0111] Examples of dyes of formula (VI) include Acid Brown 13 and Acid Orange 3; examples of dyes of formula (VI') include Acid Yellow 1, the sodium salt of 2,4-dinitro-1-naphthol-7-sulfonic acid, 2-piperidino-5-nitrobenzenesulfonic acid, 2-(4'-N,N-2"-hydroxyethyl)amino-2'-nitro)anilineethanesulfonic acid, 4-β-hydroxyethylamino-3-nitrobenzenesulfonic acid; and Ext. D&C Yellow 7.

[0112] e) Triarylmethane dyes of formula (VII): [ka] In formula (VII), ·R 33 , R 34 , R 35 and R 36 are identical or different and represent a hydrogen atom or a group selected from (C1-C6)alkyl, optionally substituted aryl and optionally substituted aryl(C1-C6)alkyl; in particular (C1-C6)alkyl and optionally M + (O) m S(O - )-group (wherein, M + and m represents a group selected from benzyl groups substituted with (as defined above); ·R 37 , R 38 , R 39 , R 40 , R 41 , R 42 , R 43 and R 44 are the same or different and represent a hydrogen atom, or - (C1-C6) alkyl; - (C1-C6)alkoxy, (C1-C6)alkylthio; - (di)(C1-C6)(alkyl)amino; - hydroxyl, mercapto; - Nitro, nitroso; - R°-C(X)-X'-, R°-X'-C(X)- or R°-X'-C(X)-X''- (wherein R° represents a hydrogen atom, an alkyl group or an aryl group, X, X' and X'' are the same or different and represent an oxygen or sulfur atom or NR, and R represents a hydrogen atom or a (C1-C6) alkyl group); -M + (O)2S(O - )-(wherein, M + represents a hydrogen atom or a cationic counterion); -M + (O)CO - -(in the formula, M + is as defined above) or represents a group selected from - otherwise, two adjacent groups R 41 and R42 , or R 42 and R 43 , or R 43 and R 44 Together, they form i) nitro; ii) nitroso; iii) M + (O)2S(O - )-; iv) hydroxyl; v) mercapto; vi) (di)(C1-C6)(alkyl)amino; vii) R°-C(X)-X'-; viii) R°-X'-C(X)-; ix) R°-X'-C(X)-X''- (wherein M + , R°, X, X′ and X″ are as defined above), forming a fused benzo group optionally substituted with one or more groups selected from; In particular, R 37 ~R 40 represents a hydrogen atom, and R 41 ~R 44 are the same or different and are hydroxyl groups or M + (O)2S(O - )-group (wherein, M + is as defined above); R 43 and R 44 together form a benzo group, this is preferentially (O)S(O - )-group; At least one of rings G, H or I is - at least one M' + (O)2S(O - )-group (wherein, M' + represents a cationic counterion); or - at least one M' + (O)CO - - group (in the formula, M' + represents a cationic counterion); Preferably at least one sodium sulfonate group It is understood that this includes:

[0113] Examples of dyes of formula (VII) include Acid Blue 1, Acid Blue 3, Acid Blue 7, Acid Blue 9, Acid Violet 49, Acid Green 3, Acid Green 5 and Acid Green 50.

[0114] f) Xanthene dyes of formula (VIII): [ka] In formula (VIII), ·R 45 , R 46 , R 47 and R 48 are the same or different and represent a hydrogen atom or a halogen atom; ·R 49 , R 50 , R 51 and R 52 are the same or different and represent a hydrogen atom, a halogen atom, or - (C1-C6) alkyl; - (C1-C6)alkoxy, (C1-C6)alkylthio; - hydroxyl, mercapto; - Nitro, nitroso; -M + (O)2S(O - )-(in the formula, M + represents a hydrogen atom or a cationic counterion); -M + (O)CO - -(in the formula, M + is as defined above) represents a group selected from: In particular, R 53 , R 54 , R 55 and R 48 represents a hydrogen atom or a halogen atom; G is an oxygen or sulfur atom or NR e group (in the formula, R e is as defined above); in particular, G represents an oxygen atom; L is alkoxide M + O - ; Thioalkoxide M + S - or NR f group (in the formula, R f represents a hydrogen atom or a (C1-C6) alkyl group, M + is as defined above; M + is in particular sodium or potassium); L' is an oxygen or sulfur atom or an ammonium group: N + R f R g (In the formula, R f and R g are the same or different and represent a hydrogen atom, a (C1-C6) alkyl group or an optionally substituted aryl group; L' is in particular an oxygen atom or one or more alkyl or M + (O) m S(O - )-group (wherein m and M + represents a phenylamino group optionally substituted with (as defined above); Q and Q' are identical or different and represent an oxygen or sulfur atom; in particular, Q and Q' represent an oxygen atom; M + is as defined above.

[0115] Examples of dyes of formula (VIII) include Acid Yellow 73, Acid Red 51, Acid Red 52; Acid Red 87, Acid Red 92, Acid Red 95 and Acid Violet 9.

[0116] g) Indole dyes of formula (IX): [ka] In formula (IX), ·R 53 , R 54 , R 55 , R 56 , R 57, R 58 , R 59 and R 60 are the same or different and represent a hydrogen atom, or - (C1-C6) alkyl; - (C1-C6)alkoxy, (C1-C6)alkylthio; - hydroxyl, mercapto; - Nitro, nitroso; - R°-C(X)-X'-, R°-X'-C(X)- or R°-X'-C(X)-X''- (wherein R° represents a hydrogen atom, an alkyl group or an aryl group, X, X' and X'' are the same or different and represent an oxygen or sulfur atom or NR, and R represents a hydrogen atom or a (C1-C6) alkyl group); -M + (O)2S(O - )-(in the formula, M + represents a hydrogen atom or a cationic counterion); -M + (O)CO - -(in the formula, M + is as defined above) represents a group selected from: G is an oxygen or sulfur atom or NR e group (in the formula, R e is as defined above); in particular, G represents an oxygen atom; ·R i and R h are the same or different and represent a hydrogen atom or a (C1-C6) alkyl group; Formula (IX) is - at least one M' + (O)2S(O - )-group (wherein, M' + represents a cationic counterion); or - at least one M' + (O)CO - - group (in the formula, M' + represents a cationic counterion); Preferably at least one sodium sulfonate group It is understood that this includes:

[0117] An example of a dye of formula (IX) is Acid Blue 74.

[0118] h) Quinoline dyes of formula (X): [ka] In formula (X), ·R 61 represents a hydrogen atom, a halogen atom, or a (C1-C6) alkyl group; ·R 62 , R 63 and R 64 are the same or different and are hydrogen atoms or M + (O)2S(O - )-group (wherein, M + represents a hydrogen atom or a cationic counterion; otherwise R 61 and R 62 or R 61 and R 64 together form one or more M + (O)2S(O - )-group (wherein, M + represents a hydrogen atom or a cationic counterion), forming a benzo group optionally substituted with Formula (X) contains at least one M' + (O) 2 S(O - )-group (wherein, M' + represents a cationic counterion), preferably comprising at least one sodium sulfonate group.

[0119] Examples of dyes of formula (X) include Acid Yellow 2, Acid Yellow 3 and Acid Yellow 5.

[0120] More specifically, the dyes of formulas (III)-(VIII) useful in the present invention are selected from the following: Acid Red 87 (VIII) (CI 45380); the sodium salt of 2,4-dinitro-1-naphthol-7-sulfonic acid (VI') (CI 10316); Acid Orange 3 (VI) (CI 10383); Acid Yellow 9 / Food Yellow 2 (III) (CI 13015); Direct Red 45 / Food Red 13 (III) (CI 14780); Acid Black 52 (III) (CI 13711); Acid Yellow 36 (III) (CI 13065); the sodium salt of 1-hydroxy-2-(2',4'-xylyl-5-sulfonatoazo)naphthalene-4-sulfonic acid / Food Red 1 (III) (CI 14700); Acid Red 14 / Food Red 3 / Mordant Blue. 79(III)(CI 14720);4-hydroxy-3-[(2-methoxy-5-nitrophenyl)diaza]-6-(phenylamino)naphthalene-2-sulfonic acid, sodium salt / Acid Brown 4(III)(CI 14805);Acid Orange 7 / Pigment Orange 17 / Solvent Orange 49(III)(CI 15510);Food Yellow 3 / Pigment Yellow 104(III)(CI 15985);Acid Red 27 / Food Red 9(III)(CI 16185);Acid Orange 10 / Food Orange 4(III)(CI 16230);Acid Red 44(III)(CI 16250);Acid Red 33 / Food Red 12(III)(CI 17200);Acid Red 184(III)(CI 15685);Acid Violet 3(III)(CI 19125); 1-hydroxy-2-(4'-acetamidophenylazo)-8-acetamidonaphthalene-3,6-disulfonic acid sodium salt / Acid Violet 7 / Food Red 11(III)(CI 18055); Acid Red 135(III)(CI18130; Acid Yellow 27(IV)(CI 19130); Acid Yellow 23 / Food Yellow 4(IV)(CI 19140); 4'-(sulfonato-2'',4''-dimethyl)-bis-(2,6-phenylazo)-1,3-dihydroxybenzene / Acid Orange 24(III)(CI 20170); 1-amino-2-(4'-nitrophenylazo)-7-phenylazo-8-hydroxynaphthalene-3,6-disulfonic acid sodium salt / Acid Black 1(III)(CI 20470); (4-((4-methylphenyl)sulfonyloxy)phenylazo)-2,2'-dimethyl-4-((2-hydroxy-5,8-disulfonato)naphthylazo)biphenyl / Acid Red 111(III')(CI 23266); Food Black 2(III) (CI 27755); 1-(4'-sulfonatophenylazo)-4-((2''-hydroxy-3''-acetylamino-6'',8''-disulfonato)naphthylazo)-6-sulfonatonaphthalene (tetrasodium salt) / Food Black 1(III) (CI 25440); Acid Blue 9(VII) (CI 42090); Acid Violet 43(V) (CI 60730); Acid Green 25(V) (CI 61570); 1-amino-4-cyclohexylamino-9,10-anthraquinone-2-sulfonic acid, sodium salt / Acid Blue 62(V) (CI 62045); Acid Blue 78(V) (CI 62105); 4-hydroxy-3-((2-methoxyphenyl)azo)-1-naphthalenesulfonic acid, sodium salt / Acid Red 4(III) (CI 14710); 2-piperidino-5-nitrobenzenesulfonic acid (VI'); 2(4'-N,N(2''-hydroxyethyl)amino-2'-nitro)anilineethanesulfonic acid (VI'); 4-β-hydroxyethylamino-3-nitrobenzenesulfonic acid (VI'); Acid Violet 49(VII) (CI 42640); Acid Blue 7(VII) (CI 42080); 1,2-dihydroxy-3-sulfoanthraquinone sodium salt / Mordant Red 3(V) (CI58005); 1-amino-9,10-dihydro-9,10-dioxo-4-(phenylamino)-2-anthracenesulfonic acid, sodium salt / Acid Blue 25(V)(CI 62055); 4-hydroxy-3-((2-methoxyphenyl)azo)-1-naphthalenesulfonic acid, sodium salt / Acid Red 4(III)(CI 14710).

[0121] Most of these dyes are described in particular in the Colour Index published by The Society of Dyers and Colourists, PO Box 244, Perkin House, 82 Grattan Road, Bradford, Yorkshire, BD12 JBN England.

[0122] These anionic dyes which are most particularly preferred are those designated in the Colour Index by the codes CI 58005 (monosodium salt of 1,2-dihydroxy-9,10-anthraquinone-3-sulfonic acid), CI 60730 (monosodium salt of 2-[(9,10-dihydro-4-hydroxy-9,10-dioxo-1-anthracenyl)amino]-5-methylbenzenesulfonic acid), CI 15510 (monosodium salt of 4-[(2-hydroxy-1-naphthalenyl)azo]benzenesulfonic acid), CI 15985 (disodium salt of 6-hydroxy-5-[(4-sulfophenyl)azo]-2-naphthalenesulfonic acid), CI 17200 (disodium salt of 5-amino-4-hydroxy-3-(phenylazo)-2,7-naphthalenesulfonic acid), It is a dye designated by the following salts: CI 20470 (disodium salt of 1-amino-2-(4'-nitrophenylazo)-7-phenylazo-8-hydroxy-3,6-naphthalenedisulfonic acid), CI 42090 (disodium salt of N-ethyl-N-[4-[[4-[ethyl[3-sulfophenyl)methyl]amino]phenyl](2-sulfophenyl)methylene]-2,5-cyclohexadien-1-ylidene]-3-sulfobenzenemethanaminium hydroxide, inner salt), and CI 61570 (disodium salt of 2,2'-[(9,10-dihydro-9,10-dioxo-1,4-anthracenediyl)diimino]bis[5-methyl]benzenesulfonic acid).

[0123] Compounds corresponding to mesomeric or tautomeric forms of structures (III)-(X) can also be used.

[0124] natural dyes The direct dyes may be selected from natural direct dyes.

[0125] Among the natural direct dyes that can be used according to the invention, mention may be made of lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, protocatechualdehyde, indigo, isatin, curcumin, spinulosin, apigenidin, orcein, brazilin, brazilain, hematein or hematoxylin. It is also possible to use extracts or decoctions containing these natural dyes, in particular poultices or extracts based on henna dye.

[0126] According to one preferred embodiment, the direct dye is selected from the triarylmethane direct dyes of formulae (IIa1) and (IIa2) below, and mixtures thereof: [ka] During the ceremony, R1, R2, R3 and R4 are identical or different and represent a group from the following: hydrogen atom or (C1-C6) alkyl, optionally substituted with a preferably hydroxyl group; aryl, such as phenyl; aryl(C1-C4) alkyl, such as benzyl; heteroaryl or heteroaryl(C1-C4) alkyl, or else two R1 and R2 and / or R3 and R4 groups carried by the same nitrogen atom together with the nitrogen atom carrying them form an optionally substituted heterocycloalkyl group, such as morpholino, piperazino or piperidino, preferably R1, R2, R3 and R4 are identical or different and represent a hydrogen atom or a (C1-C4) alkyl group; R5, R6, R7, R8, R9, R 10 , R 11 , R 12 , R 13 , R 14 , R 15 and R 16are the same or different and represent a hydrogen atom or a halogen atom or a group selected from: i) hydroxyl; ii) thiol; iii) amino; iv) (di)(C1-C4)(alkyl)amino; v) (di)arylamino, such as (di)phenylamino; vi) nitro; vii) acylamino (-NR-C(O)R'), where the R groups are hydrogen atoms, C1-C4 alkyl groups optionally carrying at least one hydroxyl group, and the R' groups are C1-C2 alkyl groups; viii) carbamoyl ((R)2N-C(O)-), where the R groups are the same or different and represent a hydrogen atom or a C1-C4 alkyl group optionally carrying at least one hydroxyl group; ix) carboxylic acids or esters, (-OC(O)R') or (-C(O)OR') wherein the R' group is a hydrogen atom or a C1-C4 alkyl group optionally carrying at least one hydroxyl group, the R' group being a C1-C2 alkyl group; x) alkyl, optionally substituted in particular with a hydroxyl group; xi) alkylsulfonylamino (R'SO2-NR-), wherein the R group represents a hydrogen atom or a C1-C4 alkyl group optionally carrying at least one hydroxyl group, the R' group represents a C1-C4 alkyl group, a phenyl group; xii) aminosulfonyl ((R)2N-SO2-), wherein the R groups are identical or different and represent a hydrogen atom or a C1-C4 alkyl group optionally carrying at least one hydroxyl group; xiii) (C1-C4)alkoxy; and xiv) (C1-C4)alkylthio; or otherwise, two groups R5 and R6, and / or R7 and R8, and / or R9 and R9, carried by two adjacent carbon atoms 10 , and / or R 11 and R 12 , and / or R 13 and R 14 , and / or R 15 and R 16together with the carbon atoms that carry them form a fused 6-membered aryl or heteroaryl, preferably benzo ring, which in addition may also be an optionally substituted, preferably unsubstituted, benzo ring; Q - represents an anionic counterion, preferably selected from halides, such as chloride or bromide, and phosphate, to achieve electroneutrality.

[0127] Preferably, the direct dye is selected from neutral direct dyes, cationic direct dyes and mixtures thereof.

[0128] More preferentially, the direct dye is preferably chosen from Basic Red 51, HC Blue 15 and mixtures thereof.

[0129] The direct dyes may be present in the composition in a total content ranging from 0.001% to 5% by weight, preferably from 0.01% to 3% by weight, more preferentially from 0.1% to 1% by weight and even more preferentially from 0.1% to 0.5% by weight relative to the total weight of the composition.

[0130] The composition may additionally comprise one or more oxidative dyes.

[0131] oxidation dyes Oxidation dyes are generally selected from one or more oxidizing bases optionally combined with one or more coupling agents (also known as couplers).

[0132] Oxidizing bases The composition may optionally contain one or more oxidizing bases, advantageously chosen from those conventionally used for dyeing keratinous fibers.

[0133] By way of example, the oxidizing base is selected from para-phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, ortho-aminophenols and heterocyclic bases and the corresponding addition salts.

[0134] Para-phenylenediamines that may be mentioned include, for example, para-phenylenediamine, para-toluenediamine, 2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,5-dimethyl-para-phenylenediamine, N,N-dimethyl-para-phenylenediamine, N,N-diethyl-para-phenylenediamine, N,N-dipropyl-para-phenylenediamine, 4-amino-N,N-diethyl-3-methylaniline, N,N-bis(β-hydroxyethyl)-para-phenylenediamine, 4-N,N-bis(β-hydroxyethyl)amino-2-methylaniline, 4-N,N-bis(β-hydroxyethyl)amino-2-chloroaniline, 2-β-hydroxyethyl-para-phenylenediamine, 2-methoxymethyl-para-phenylenediamine, 2-fluoro-para-phenylenediamine amine, 2-isopropyl-para-phenylenediamine, N-(β-hydroxypropyl)-para-phenylenediamine, 2-hydroxymethyl-para-phenylenediamine, N,N-dimethyl-3-methyl-para-phenylenediamine, N-ethyl-N-(β-hydroxyethyl)-para-phenylenediamine, N-(β,γ-dihydroxypropyl)-para-phenylenediamine, N-(4'-aminophenyl)-para-phenylenediamine, N-phenyl-para-phenylenediamine, 2-β-hydroxyethyloxy-para-phenylenediamine, 2-β-acetylaminoethyloxy-para-phenylenediamine, N-(β-methoxyethyl)-para-phenylenediamine, 4-aminophenylpyrrolidine, 2-thienyl-para-phenylenediamine, 2-β-hydroxyethylamino-5-aminotoluene and 3-hydroxy-1-(4'-aminophenyl)pyrrolidine and the corresponding addition salts with acids.

[0135] Among the para-phenylenediamines listed above, para-phenylenediamine, para-toluylenediamine, 2-isopropyl-para-phenylenediamine, 2-β-hydroxyethyl-para-phenylenediamine, 2-β-hydroxyethyloxy-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, N,N-bis(β-hydroxyethyl)-para-phenylenediamine, 2-chloro-para-phenylenediamine, 2-β-acetylaminoethyloxy-para-phenylenediamine, and addition salts thereof with acids are particularly preferred.

[0136] Bis(phenyl)alkylenediamines that may be mentioned include, for example, N,N'-bis(β-hydroxyethyl)-N,N'-bis(4'-aminophenyl)-1,3-diaminopropanol, N,N'-bis(β-hydroxyethyl)-N,N'-bis(4'-aminophenyl)ethylenediamine, N,N'-bis(4-aminophenyl)tetramethylenediamine, N,N'-bis(β-hydroxyethyl)-N,N'-bis(4-aminophenyl)tetramethylenediamine, N,N'-bis(4-methylaminophenyl)tetramethylenediamine, N,N'-bis(ethyl)-N,N'-bis(4'-amino-3'-methylphenyl)ethylenediamine and 1,8-bis(2,5-diaminophenoxy)-3,6-dioxaoctane and the corresponding addition salts.

[0137] Para-aminophenols that may be mentioned include, for example, para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 4-amino-3-chlorophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2-(β-hydroxyethylaminomethyl)phenol and 4-amino-2-fluorophenol and the corresponding addition salts with acids.

[0138] Ortho-aminophenols that may be mentioned include, for example, 2-aminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol and 5-acetamido-2-aminophenol and the corresponding addition salts.

[0139] Heterocyclic bases that may be mentioned include, for example, pyridine, pyrimidine, pyrazole derivatives.

[0140] Pyridine derivatives that may be mentioned include, for example, the compounds described in patents GB 1 026 978 and GB 1 153 196, such as 2,5-diaminopyridine, 2-(4-methoxyphenyl)amino-3-aminopyridine and 3,4-diaminopyridine and the corresponding addition salts.

[0141] Other pyridine oxidizing bases useful in the present invention are, for example, 3-aminopyrazolo[1,5-a]pyridine or the corresponding addition salts, which are oxidizing bases described in patent application FR 2801308. Examples that may be mentioned include pyrazolo[1,5-a]pyrid-3-ylamine, 2-acetylaminopyrazolo[1,5-a]pyrid-3-ylamine, 2-(morpholin-4-yl)pyrazolo[1,5-a]pyrid-3-ylamine, 3-aminopyrazolo[1,5-a]pyridine-2-carboxylic acid, 2-methoxypyrazolo[1,5-a]pyrid-3-ylamine, (3-aminopyrazolo[1,5-a]pyrid-7-yl)methanol, 2-(3-aminopyrazolo[1,5-a]pyrid-5-yl)ethanol, 2-(3-aminopyrazolo[1,5-a]pyrid-7-yl)ethanol, (3-aminopyrazolo[1,5-a]pyrid-2-yl)methanol, 3,6-diaminopyrazolo[1,5-a]pyridine, 3,4-diaminopyrazolo[1,5-a]pyridine, pyrazolo[1,5-a]pyridine-3,7-diamine, 7-(morpholin-4-yl)pyrazolo[ 1,5-a]pyrid-3-ylamine, pyrazolo[1,5-a]pyridine-3,5-diamine, 5-(morpholin-4-yl)pyrazolo[1,5-a]pyrid-3-ylamine, 2-[(3-aminopyrazolo[1,5-a]pyrid-5-yl)(2-hydroxyethyl)amino]ethanol, 2-[(3-aminopyrazolo[1,5-a]pyrid-7-yl)(2-hydroxyethyl)amino]ethanol, 3-aminopyrazolo[ 1,5-a]pyridin-5-ol, 3-aminopyrazolo[1,5-a]pyridin-4-ol, 3-aminopyrazolo[1,5-a]pyridin-6-ol, 3-aminopyrazolo[1,5-a]pyridin-7-ol, 2-β-hydroxyethoxy-3-aminopyrazolo[1,5-a]pyridine and 2-(4-dimethylpiperazinium-1-yl)-3-aminopyrazolo[1,5-a]pyridine and the corresponding addition salts.

[0142] More particularly, the oxidizing bases useful in the present invention preferably have at least two carbon atoms: a) (di)(C1-C6)(alkyl)amino groups, wherein the alkyl groups can be substituted with at least one hydroxyl, amino, or imidazolium group; b) an optionally cationic 5- to 7-membered heterocycloalkyl group containing 1 to 3 heteroatoms, optionally substituted with one or more (C1-C6) alkyl groups, such as a di(C1-C4) alkylpiperazinium group; or c) (C1-C6)alkoxy groups optionally substituted with one or more hydroxyl groups, such as β-hydroxyalkoxy groups and the corresponding addition salts.

[0143] Pyrimidine derivatives that may be mentioned include, for example, the compounds described in patents DE 2359399, JP 88169571, JP 0563124 and EP 0770375 or patent application WO 96 / 15765, such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine and the addition salts thereof, as well as the tautomeric forms thereof (if tautomeric equilibrium exists).

[0144] Pyrazole derivatives that may be mentioned are the compounds described in patents DE 3843892, DE 4133957 and patent applications WO 94 / 08969, WO 94 / 08970, FR-A-2733749 and DE 19543988, 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-(β-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-hydroxy These include methyl-1-isopropylpyrazole, 4,5-diamino-3-methyl-1-isopropylpyrazole, 4-amino-5-(2'-aminoethyl)amino-1,3-dimethylpyrazole, 3,4,5-triaminopyrazole, 1-methyl-3,4,5-triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole, 3,5-diamino-4-(β-hydroxyethyl)amino-1-methylpyrazole, and the corresponding addition salts. 4,5-diamino-1-(β-methoxyethyl)pyrazole can also be used.

[0145] Preferably, 4,5-diaminopyrazole will be used, and even more preferentially 4,5-diamino-1-(β-hydroxyethyl)pyrazole and / or the corresponding salts.

[0146] Among the pyrazole derivatives that may be mentioned are diamino-N,N-dihydropyrazolopyrazolones, in particular those described in patent application FR-A-2 886 136, such as the following compounds and the corresponding 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]pyrazole. -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-dihydropyrazol-3-one, 4,5-diamino-1,2-diethyl-1,2-dihydropyrazol-3-one 4,5-diamino-1,2-di(2-hydroxyethyl)-1,2-dihydropyrazol-3-one, 2-amino-3-(2-hydroxyethyl)amino-6,7-dihydro-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-dihydropyrazol-3-one, 4-amino-5-(3-dimethylaminopyrrolidin-1-yl)-1,2-diethyl-1,2-dihydropyrazol-3-one and 2,3-diamino-6-hydroxy-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one.

[0147] Preferably, 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one and / or the corresponding salts will be used.

[0148] As heterocyclic base it is preferred to use 4,5-diamino-1-(β-hydroxyethyl)pyrazole and / or 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one and / or one of their corresponding salts.

[0149] Coupling Agent The composition may optionally contain one or more coupling agents which may advantageously be chosen from those conventionally used for dyeing keratinous fibers.

[0150] Among the coupling agents, mention may in particular be made of meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalene-based coupling agents and heterocyclic coupling agents, and also the corresponding addition salts.

[0151] For example, 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene, 4-chloro-1,3-dihydroxybenzene, 2,4-diamino-1-(β-hydroxyethyloxy)benzene, 2-amino-4-(β-hydroxyethylamino)-1-methoxybenzene, 1,3-diaminobenzene, 1,3-bis(2,4-diaminophenoxy)propane, 3-ureidoaniline, 3-ureido-1-dimethylaminobenzene, sesamol, 1-β-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 5-N-(β-hydroxyethyl)amino-3,4-methylenedioxybenzene, 2,6-bis(β-hydroxyethylamino)toluene, 6-hydroxyindoline, 2,6-dihydroxy-4-methylpyridine, 1H-3-methylpyrazol-5-one, 1-phenyl-3-methylpyrazol-5-one, 2,6-dimethylpyrazolo[1,5-b]-1,2,4-triazole, 2,6-dimethyl[3,2-c]-1,2,4-triazole, 6-methylpyrazolo[1,5-a]benzimidazole, 2-methyl-5-aminophenol, 5-N-(β-hydroxyethyl)amino-2-methylphenol, 3-aminophenol and 3-amino-2-chloro-6-methylphenol, the corresponding addition salts with acids and the corresponding mixtures may be mentioned.

[0152] In general, the addition salts of oxidizing bases and coupling agents which can be used in connection with the present invention are chosen in particular from addition salts with acids, such as hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates.

[0153] The oxidizing bases each advantageously represent between 0.001% and 10% by weight relative to the total weight of the composition, preferably in the range 0.005% and 5% by weight relative to the total weight of the composition.

[0154] When present, the coupling agents advantageously represent from 0.001% to 10% by weight relative to the total weight of the composition, and preferably from 0.005% to 5% by weight relative to the total weight of the composition.

[0155] Additional basifying agents The composition may also include one or more additional basifying agents other than the carbonates, bicarbonates and silicates defined above.

[0156] According to a preferred embodiment, the composition according to the invention does not contain additional alkaline agents selected from aqueous ammonia and / or alkanolamines.

[0157] Acidifying Agent The composition may additionally comprise one or more acidifying agents.

[0158] pH of the composition The compositions according to the invention preferably exhibit a pH of 11 or less, preferably 10.5 or less, preferably 10 or less.

[0159] The pH of the composition according to the invention may vary from 8 to 11, preferably from 8 to 10.5 and more preferentially from 8 to 10.

[0160] According to a particularly preferred embodiment, the pH of the composition according to the invention varies from 8.3 to 10.

[0161] Other characteristics of the composition The composition preferably comprises water in a content ranging from 5% to 99% by weight, more preferentially from 5% to 80% by weight, relative to the total weight of the composition.

[0162] The composition may additionally comprise at least one organic solvent.

[0163] The term "organic solvent" is understood to mean an organic substance capable of dissolving other substances without chemically modifying them.

[0164] The compositions according to the invention may be provided in liquid form, in serum form, in thickened form, in particular in gel, cream, wax or paste form, or in foam form.

[0165] The compositions according to the invention may also comprise one or more additional compounds selected from nonionic, anionic, cationic or amphoteric surfactants; cationic, anionic, nonionic or zwitterionic, associative or non-associative thickening polymers of natural or synthetic origin; silicones in the form of oils, gums, resins; or non-silicone oils of vegetable, mineral or synthetic origin; UV filters; fillers such as pearlescent agents and metal oxides such as titanium dioxide, clays; fragrances; deflocculants; vitamins; and preservatives.

[0166] Method for simultaneously bleaching and dyeing keratin fibers According to a second aspect, the subject of the present invention is a method for simultaneously bleaching and dyeing keratinous fibers, comprising applying to the keratinous fibers a composition as defined above.

[0167] In particular, the composition is applied to wet or dry keratinous fibers.

[0168] Preferably, the keratinous fibers are dark colored keratinous fibers.

[0169] The term "dark keratinous fibers" is understood to mean keratinous fibers whose tone level is less than or equal to 6 (dark blond), preferably less than or equal to 4 (chestnut).

[0170] "Hair tone" is a unit known to hair styling experts and is described in the book Science des traitements capillaires [The Science of Hair Care] by Charles Zviak, published by Masson, 1988, pages 215 and 278; hair tone ranges from 1 (black) to 10 (light blonde) according to the European scale, with one unit corresponding to one tone and the higher the number, the lighter the tone.

[0171] The composition may advantageously be applied to the keratinous fibres in an amount ranging from 0.1 g to 20 g of composition per gram of keratinous fibre.

[0172] The composition is allowed to rest on the fibers for a period of time, generally from 1 minute to 1 hour, preferably from 5 minutes to 60 minutes.

[0173] By way of example, the composition may be allowed to sit on the fabric for 50 minutes.

[0174] The composition can be placed on the fibers under an occlusive system, non-limiting examples of which can include wrapper or hair cap type occlusive systems made of aluminum or plastic film, with or without holes.

[0175] The temperature during the simultaneous bleaching and dyeing method is usually from ambient temperature (15°C to 25°C) to 80°C, preferably from ambient temperature to 60°C.

[0176] As an example, the temperature during the simultaneous bleaching and dyeing process is 33°C.

[0177] Once the treatment is complete, the keratinous fibers are optionally rinsed with water, optionally washed with shampoo, then rinsed with water, and then dried or left to dry naturally.

[0178] The drying step can be carried out using absorbent paper, a hair dryer or a styling hood.

[0179] The composition according to the invention is preferably prepared by mixing at least two compositions, preferably by blending the at least two compositions immediately before applying the composition according to the invention to the keratinous fibers.

[0180] According to a preferred embodiment, the composition according to the invention comprises two compositions (A) and (B1): - i) a composition (A) comprising one or more chemical oxidizing agents selected from hydrogen peroxide, hydrogen peroxide-generating systems other than peroxide salts, and mixtures thereof, as defined above; a composition (B1) comprising ii) one or more compounds selected from carbonates, carbonate-generating systems, bicarbonates, bicarbonate-generating systems and mixtures thereof, as defined above; and iii) one or more silicates as defined above; and iv) one or more direct dyes as defined above a composition (B1) comprising or a mixture of the three compositions (A), (B2) and (C): - i) a composition (A) comprising one or more chemical oxidizing agents selected from hydrogen peroxide, hydrogen peroxide-generating systems other than peroxide salts, and mixtures thereof, as defined above; - composition (B2), ii) one or more compounds selected from carbonates, carbonate-generating systems, bicarbonates, bicarbonate-generating systems and mixtures thereof, as defined above; and iii) one or more silicates as defined above a composition (B2) comprising: - iv) a composition (C) comprising one or more direct dyes as defined above; It is obtained from a mixture of

[0181] Preferably, at least one of the compositions (A) or (B1) or at least one of the three compositions (A), (B2) or (C) is aqueous. More preferentially, composition (A) is aqueous.

[0182] According to a particular embodiment, composition (B1) or (B2) is anhydrous.

[0183] The term "aqueous composition" is understood to mean a composition comprising at least 5% by weight of water. Aqueous compositions preferably comprise more than 10% by weight of water, and even more advantageously more than 20% by weight of water.

[0184] According to a more preferred embodiment, the composition according to the invention comprises two compositions (A') and (B1'): i) a composition (A') comprising hydrogen peroxide; composition (B1′), ii) one or more compounds selected from carbonates, bicarbonates and mixtures thereof, as defined above; and iii) one or more silicates as defined above; and iv) one or more direct dyes as defined above a composition (B1') comprising A mixture of three compositions (A'), (B2') and (C'): i) a composition (A') comprising hydrogen peroxide; composition (B2'), ii) one or more compounds selected from carbonates, bicarbonates and mixtures thereof, as defined above; and iii) one or more silicates as defined above a composition (B2') comprising: - iv) a composition (C') comprising one or more direct dyes as defined above, It is obtained from a mixture of

[0185] Preferably, at least one of the compositions (A') or (B1') or at least one of the three compositions (A'), (B2') or (C') is aqueous. More preferentially, composition (A') is aqueous.

[0186] According to a particular embodiment, composition (B1') or (B2') is anhydrous.

[0187] use According to a third aspect, a subject of the invention is the use of a composition as defined above for simultaneously bleaching and dyeing keratinous fibers.

[0188] Multi-compartment device (kit) According to a fourth aspect, the subject of the present invention is a method for producing a pharmaceutical composition comprising: a first compartment comprising the composition (A) defined above; a second compartment containing the composition (B1) defined above; Contains; or a first compartment comprising the composition (A) defined above; a second compartment containing the composition (B2) defined above; a third compartment containing the composition (C) defined above; A multi-compartment device (kit) comprising:

[0189] Preferably, the multi-compartment device comprises: a first compartment comprising the composition (A') defined above; a second compartment comprising the composition (B1') defined above, and Contains; or a first compartment comprising the composition (A') defined above; a second compartment comprising the composition (B2′) defined above; a third compartment containing the composition (C') defined above; Includes. [Example]

[0190] The following examples will enable a better understanding of the invention without showing a limiting nature, in which all amounts are expressed as percentages by weight relative to the total weight of the composition, unless otherwise specified.

[0191] Example 1 The following compositions C1 and C2 were prepared and then applied according to the application procedure described below.

[0192] [Table 1]

[0193] Applicable protocols: 10 g of each of compositions C1 and C2 are applied to two 1 g tresses of dark hair of HT4 Caucasian type on a hot plate maintained at a temperature of 33° C. All is covered with cellophane film for 50 minutes.

[0194] The tresses are then rinsed, washed with a standard shampoo, rinsed again and then dried.

[0195] result

[0196] [Table 2]

[0197] The composition according to the invention makes it possible to simultaneously bleach and dye dark hair in a single step, making it possible to obtain vibrant colors.

Claims

1. 1. A composition comprising: i) one or more chemical oxidizing agents selected from hydrogen peroxide, hydrogen peroxide generating systems other than peroxide salts, and mixtures thereof; ii) ammonium bicarbonate; iii) one or more silicates; iv) one or more direct dyes and a content of persulfates of less than 10% by weight.

2. The composition of claim 1 , wherein the chemical oxidizing agent is hydrogen peroxide.

3. 3. The composition according to claim 1, wherein the chemical oxidizing agent is present in a total content ranging from 1% to 12% by weight relative to the total weight of the composition.

4. 4. The composition according to claim 1, wherein the bicarbonate ii) is present in a total content ranging from 0.01% to 20% by weight relative to the total weight of the composition.

5. 5. The composition of claim 1, wherein the silicate is selected from alkali metal silicates, alkaline earth metal silicates, aluminum silicate, trimethylammonium silicate, and mixtures thereof.

6. The composition according to any one of claims 1 to 5, wherein said silicates are present in a total content ranging from 1% to 40% by weight relative to the total weight of the composition.

7. A composition described in any one of claims 1 to 6, wherein the mass ratio of the total amount of bicarbonate ii) to the total amount of silicate iii) is 0.00025 to 2000.

8. 8. The composition according to claim 1, wherein the weight ratio of the total amount of bicarbonates ii) to the total amount of chemical oxidizing agents i) is from 0.0008 to 20.

9. 9. The composition according to claim 1, comprising a total content of persulfates of less than 5% by weight.

10. The composition according to any one of claims 1 to 9, wherein the pH of the composition varies from 8 to 11.

11. A composition according to any one of claims 1 to 10, wherein the direct dye iv) is chosen from neutral, cationic or anionic direct dyes and mixtures thereof.

12. The composition according to any one of the preceding claims, wherein the direct dyes iv) are present in a total content ranging from 0.001% to 5% by weight relative to the total weight of the composition.

13. A method for simultaneously bleaching and dyeing keratinous fibers, comprising applying a composition according to any one of claims 1 to 12 to said keratinous fibers.

14. The composition according to any one of claims 1 to 12 comprises two compositions (A) and (B1): i) a composition (A) according to claim 1 or 2, comprising one or more chemical oxidizing agents selected from hydrogen peroxide, hydrogen peroxide-generating systems other than peroxide salts, and mixtures thereof; a composition (B1) comprising ii) the ammonium bicarbonate bicarbonate of claim 1; and iii) one or more silicates according to claim 1 or 5; and iv) one or more direct dyes according to claim 1 or 11 A composition (B1) comprising: or a mixture of the three compositions (A), (B2) and (C): i) a composition (A) according to claim 1 or 2, comprising one or more chemical oxidizing agents selected from hydrogen peroxide, hydrogen peroxide-generating systems other than peroxide salts, and mixtures thereof; a composition (B2) comprising ii) the ammonium bicarbonate bicarbonate of claim 1; and iii) one or more silicates according to claim 1 or 5 a composition (B2) comprising: - iv) a composition (C) comprising one or more direct dyes according to claim 1 or 11; 14. The method of claim 13, obtained from the mixing of

15. Use of a composition according to any one of claims 1 to 12 for simultaneously bleaching and dyeing keratin fibres.

16. 1. A multi-compartment device, comprising: a first compartment comprising the composition (A) according to claim 14; a second compartment comprising a composition (B1) according to claim 14; or a first compartment comprising the composition (A) according to claim 14; a second compartment comprising a composition (B2) according to claim 14; a third compartment comprising the composition (C) according to claim 14; Multi-compartment devices, including:

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