Composition for lightening keratinous fibers and method for lightening keratinous fibers using said composition

Abstract

The present invention relates to a composition for lightening keratinous fibers, comprising at least one chemical oxidizing agent, ammonium carbonate, and at least one silicate, and also to a method for lightening keratinous fibers using this composition.

Description

[Technical Field]

[0001] The present invention relates to a composition for lightening keratinous fibers, comprising at least one chemical oxidizing agent, ammonium carbonate, and at least one silicate, and also to a method for lightening keratinous fibers using this composition. [Background technology]

[0002] When a person wishes to change the color of their hair, especially if they wish to obtain a color lighter than the original color, it is often necessary to lighten or bleach the hair beforehand, and to do this, lightening or bleaching products are used.

[0003] Hair lightening is evaluated by a "tone gradation" that characterizes the degree or level of lightening. The concept of "tone" is based on a gradation of natural shades, where one tone distinguishes the shade immediately before or after it. This definition and gradation of natural shades is well known to hairdressing experts and is published in a book (Non-Patent Document 1). The tone gradation is expressed on a scale from 1 (black) to 10 (very light blonde), with one unit corresponding to one shade, and the higher the number, the lighter the shade.

[0004] It is a known practice to lighten or bleach hair using a lightening or bleaching composition containing at least one chemical oxidizing agent, usually under alkaline pH conditions. The role of the chemical oxidizing agent is to decompose the melanin in the hair, resulting in a more or less pronounced fiber lightening, depending on the nature of the oxidizing agent present and the pH conditions. Therefore, when performing relatively mild lightening, hydrogen peroxide is commonly used as the oxidizing agent. When a greater lightening is desired, especially when the treated hair is dark, persulfate is usually used in the presence of hydrogen peroxide. However, the lightening obtained by the action of such a combination is not always satisfactory, as it leaves the hair with a rather unattractive orange-yellow hue that is significantly different from the natural color, thereby limiting subsequent coloring to the acquisition of warmer shades. Furthermore, lightening compositions based on persulfate can cause deterioration of fiber quality. [Prior art documents] [Non-patent literature]

[0005] [Non-Patent Document 1] Sciences des traitements capillaires [Hair treatment sciences] by Charles Zviak, 1988, published by Masson, pp. 215 and 278 Summary of the Invention [Problem to be solved by the invention]

[0006] Therefore, there is a real need to develop compositions that can effectively lighten keratin fibers, especially dark-colored keratin fibers, to obtain less yellowing and more natural results. Such compositions would also need to pay more attention to the quality of the fibers, in particular to minimize their degradation. [Means for solving the problem]

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

[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) ammonium carbonate; iii) one or more silicates wherein the silicate is present in a total content ranging from 1% by weight to 40% by weight relative to the total weight of the composition.

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

[0010] According to a third aspect, the subject of the invention is the use of a composition as defined above for lightening keratinous fibers, preferably for lightening them while at the same time reducing their yellowness.

[0011] According to a fourth aspect, the subject of the present invention is a multi-compartment device (kit), 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; a second compartment containing a composition (B) comprising ii) ammonium carbonate, and iii) one or more silicates, and optionally iv) one or more bicarbonates and / or one or more bicarbonate-generating systems; A multi-compartment device (kit) comprising: [Brief explanation of the drawings]

[0012] [Figure 1]1 is a graph showing the variation of intensity L* as a function of parameter b* for a composition according to the invention (Example 2) and a comparative composition based on persulfate (Example 1), the L* and b* values ​​being measured in the CIE L*a*b* system. DETAILED DESCRIPTION OF THE INVENTION

[0013] For purposes of this invention, unless otherwise specified: The term "keratinous fibers" means 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" means a linear or branched saturated hydrocarbon-based group; ·「(C x ~C y The term ") alkyl group" means an alkyl group containing x to y carbon atoms; The term "silicate" means silicate; · The term "colorant" means an oxidation dye, a direct dye or a pigment; The term "oxidation dye" refers to an oxidation dye precursor selected from oxidation bases and couplers, which are colorless or weakly colored compounds that undergo a condensation reaction in the presence of an oxidizing agent to give a colored species; The term "direct dyes" means natural and / or synthetic dyes, including those in the form of extracts, other than oxidation dyes; these are colored compounds that are distributed on the surface of the fiber. They may be ionic or non-ionic, i.e., anionic, cationic, neutral or non-ionic; The term "chemical oxidant" means an oxidant other than atmospheric oxygen.

[0014] Unless otherwise specified, when a compound is referred to in this application, this also includes its optical isomers, its geometric isomers, its tautomers, its salts or its solvates (such as hydrates) and mixtures thereof.

[0015] The terms "at least one" and "one or more" are synonymous and can be used interchangeably.

[0016] The expressions "lightening" and "bleaching" are synonymous and can be used interchangeably.

[0017] composition According to a first aspect, a subject of the present invention is a composition as defined above.

[0018] The Applicant has surprisingly found that the compositions according to the invention make it possible to effectively lighten keratinous fibers with less yellowing and more natural results. When comparing the color of keratinous fibers treated with the compositions according to the invention with the color of keratinous fibers treated with lightening compositions known in the prior art, it is observed that the b* values, measured in the CIE L*a*b* system, are lower for the compositions according to the invention than for the lightening compositions known in the prior art, at comparable intensity levels L*.

[0019] Furthermore, the composition according to the invention pays more attention to the quality of the fibers, in particular minimizing their degradation.

[0020] According to one preferred embodiment, the composition according to the invention comprises: i) hydrogen peroxide; ii) ammonium carbonate; iii) one or more silicates wherein the silicates are present in a total content ranging from 1% to 40% by weight relative to the total weight of the composition.

[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 peroxide, polymer complexes capable of releasing hydrogen peroxide, oxidases, and mixtures thereof.

[0023] Examples of polymer complexes capable of releasing hydrogen peroxide include polyvinylpyrrolidone / H2O2, especially in powder form, and other polymer complexes described in U.S. 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 one particular embodiment, 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 the keratin fibers. The intermediate composition comprising 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 lightening keratin fibers.

[0026] According to one 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 one 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] Bicarbonate and / or bicarbonate generating system The composition according to the invention may also comprise iv) one or more bicarbonates and / or one or more bicarbonate-generating systems, preferably iv) one or more bicarbonates.

[0030] The term "bicarbonate generating system" means a system that produces bicarbonate, for example, in situ from carbon dioxide in water or by buffering carbonate with a mineral or organic acid.

[0031] Preferably, the bicarbonate is selected from: - 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 hydrogen atom or a (C1-C4) alkyl group optionally substituted with a hydroxyl group; - Aminoguanidine bicarbonate; - A mixture of them.

[0032] 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.

[0033] Even more preferentially, the bicarbonate is chosen from sodium bicarbonate, potassium bicarbonate, cesium bicarbonate, calcium bicarbonate, magnesium bicarbonate, ammonium bicarbonate and mixtures thereof.

[0034] Most preferentially, the bicarbonate is chosen from sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate and mixtures thereof.

[0035] According to one particularly preferred embodiment, the bicarbonate contained in the composition is ammonium bicarbonate.

[0036] The bicarbonate may be derived from natural waters, for example spring water from the Vichy basin or spring water from La Roche Posay or Badoit water (see, for example, patent document FR 2 814 943).

[0037] 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.

[0038] According to one 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.

[0039] Silicate The composition according to the present invention also comprises iii) one or more silicates. The silicate is preferably water-soluble. The term "water-soluble silicate" means a silicate having a solubility in water of more than 0.5% by weight, preferably more than 1% by weight, at normal ambient temperature (25°C) and atmospheric pressure (760 mmHg). Preferably, the silicate is selected from alkali metal silicates, alkaline earth metal silicates, aluminum silicate, trimethylammonium silicate, and mixtures thereof. More preferably, the silicate is selected from sodium silicate, potassium silicate, calcium silicate, aluminum silicate, trimethylammonium silicate, and mixtures thereof. Even more preferably, the silicate is selected from sodium silicate. Examples of sodium silicates include compounds with CAS numbers [1344-09-8] and [6834-92-0].

[0040] The silicates are present in a total content ranging from 1% to 40% by weight, preferably from 2% to 35% by weight, more preferentially from 3% to 35% by weight and even more preferentially from 4% to 20% by weight relative to the total weight of the composition.

[0041] ammonium carbonate The composition according to the present invention comprises ii) ammonium carbonate.

[0042] The ammonium carbonate is preferably present in a content ranging from 0.01% to 20% by weight, more preferentially from 1% to 20% by weight and even more preferentially from 1% to 10% by weight relative to the total weight of the composition.

[0043] The mass ratio of the total amount of ammonium carbonate ii) to the total amount of silicates iii) is preferably 0.00025 to 20, more preferentially 0.028 to 10, and even more preferentially 0.028 to 3.4.

[0044] The mass ratio of the total amount of ammonium carbonate ii) / the total amount of chemical oxidizing agent i) is preferably between 0.0008 and 20, more preferentially between 0.1 and 6.6, even more preferentially between 0.1 and 2.9.

[0045] According to one preferred embodiment, the mass ratio of the total amount of ammonium carbonate ii) / the total amount of hydrogen peroxide is between 0.0008 and 20, preferably between 0.1 and 6.6, and more preferentially between 0.1 and 2.9.

[0046] The mass ratio of the total amount of ammonium carbonate ii) to the total amount of bicarbonate and / or bicarbonate generating system iv) is preferably 0.005-2000, more preferentially 0.06-20, and even more preferentially 0.06-5.

[0047] According to a preferred embodiment, the mass ratio of the total amount of ammonium carbonates ii) / the total amount of bicarbonates (iv) is preferably between 0.005 and 2000, more preferentially between 0.06 and 20, and even more preferentially between 0.06 and 5.

[0048] 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.

[0049] According to one particularly preferred embodiment, the composition does not contain magnesium carbonate.

[0050] The composition preferably comprises a total content of persulfates of less than 10% by weight, more preferentially less than 5% by weight, even more preferentially less than 1% by weight, most preferentially less than 0.1% by weight, better still less than 0.01% by weight, and even better still less than 0.001% by weight. According to a particularly preferred embodiment, the composition does not comprise persulfates.

[0051] The composition may comprise one or more colorants selected from direct dyes, oxidative dyes, and mixtures thereof.

[0052] When they are present, the colorants are preferably present in a total content ranging from 0.001% to 10% by weight, preferably from 0.01% to 4% by weight and more preferentially from 0.1% to 1% by weight relative to the total weight of the composition.

[0053] 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).

[0054] Oxidizing bases The composition optionally comprises one or more oxidizing bases, advantageously chosen from those conventionally used for dyeing keratinous fibers.

[0055] 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.

[0056] Among the para-phenylenediamines, 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, 2-amino-N,N-diethyl-3-methylaniline, 4-amino-N,N-bis(β-hydroxyethyl)amino-2-chloroaniline, 2 ...amino-N,N-bis(β-hydroxyethyl)amino-2-chloroaniline, 2-amino-N,N-bis(β-hydroxyethyl)amino-2-chloroaniline, 2-amino-N,N-bis(β-hydroxyethyl)amino-2-chloroaniline, 2-amino-N,N-bis(β-hydroxyethyl)amino-2-chloroaniline, 2-amino-N,N-bis(β-hydroxyethyl)amino-2-chloroaniline, 2-amino-N,N-bis(β 4-aminophenyl)pyrrolidine, 2-thienyl-para-phenylenediamine, 2-beta-hydroxyethylamino-5-aminotoluene and 3-hydroxy-1-(4'-aminophenyl)pyrrolidine, and the corresponding addition salts with acids.

[0057] Among the above-mentioned para-phenylenediamines, para-phenylenediamine, para-toluenediamine, 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 and 2-β-acetylaminoethyloxy-para-phenylenediamine and the corresponding addition salts with acids are particularly preferred.

[0058] Among the bis(phenyl)alkylenediamines, mention may be made, for example, of 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.

[0059] Among the para-aminophenols that may be mentioned, mention may be made, for example, of 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.

[0060] Among the ortho-aminophenols, mention may be made, for example, of 2-aminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol and 5-acetamido-2-aminophenol and the corresponding addition salts.

[0061] Among the heterocyclic bases, mention may be made, for example, of pyridine, pyrimidine and pyrazole derivatives.

[0062] Among pyridine derivatives, mention may be made, for example, of 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.

[0063] Other pyridine-based 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 2 801 308. Examples that may be mentioned include: pyrazolo[1,5-a]pyrid-3-ylamine, 2-acetylaminopyrazolo[1,5-a]pyrid-3-ylamine, 2-(morpholin-4-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) ...2-(morpholin-4-yl)pyrazolo[1,5-a]pyrid-3-ylamine, 2-(morpholin-4-yl)pyrazolo[1,5-a]pyrid-3-ylamine, 2-(morpholin-4-yl)pyrazolo[1,5-a]pyrid-3-ylamine, 2-(morpholin-4-yl)pyrazolo[1,5-a]pyrid-3-ylamine, 2-(morph 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]pyrid-3-yl ...3-aminopyrazolo[1,5-a]pyrid-3-ylamine, 2-[(3-aminopyrazolo[1,5-a]pyrid-7-yl)(2-hydroxyethyl)amino]ethanol, 3-aminopyrazolo[1,5-a]pyrid-3-ylamine, 2-[(3-aminopyrazolo[1,5-a]pyrid-5-yl)(2-hydroxyethyl)amino]ethanol, 3-aminopyrazolo[1,5-a]pyrid-3-ylamine, 2-[(3-aminopyrazolo[1, nopyrazolo[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.

[0064] More particularly, the oxidizing bases useful in the present invention are selected from 3-aminopyrazolo[1,5-a]pyridines, preferably at carbon atom 2: a) (di)(C1-C6)(alkyl)amino groups, which may be substituted with at least one hydroxyl group, amino group 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.

[0065] Among pyrimidine derivatives, mention may be made, for example, of the compounds described in German Patent No. 2359399; Japanese Patent No. 88-169571; Japanese Patent Publication No. 05-63124; European Patent No. 0770375 or patent application WO 96 / 15765, such as 2,4,5,6-tetraaminopyridimine, 4-hydroxy-2,5,6-triaminopyridimine, 2-hydroxy-4,5,6-triaminopyridimine, 2,4-dihydroxy-5,6-diaminopyridimine, 2,5,6-triaminopyrimidine and addition salts thereof, as well as tautomers thereof when tautomeric equilibrium exists.

[0066] Among pyrazole derivatives, compounds described in patents DE 3843892 and 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-hydroxymethyl-1 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, and 3,5-diamino-4-(β-hydroxyethyl)amino-1-methylpyrazole, as well as the corresponding addition salts. 4,5-Diamino-1-(β-methoxyethyl)pyrazole can also be used.

[0067] Preferably, 4,5-diaminopyrazole will be used, and even more preferentially 4,5-diamino-1-(β-hydroxyethyl)pyrazole and / or the corresponding salts.

[0068] Furthermore, pyrazole derivatives include diamino-N,N-dihydropyrazolopyrazolones, in particular those described in patent application FR-A-2 886 136, such as the following compounds and corresponding addition salts: 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, 2-amino-3-ethyl ... 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-bis(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-pyrida Mention may also be made of dino[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.

[0069] Preferably, 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one and / or the corresponding salts will be used.

[0070] Preferably used heterocyclic bases are 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 the corresponding salts.

[0071] Coupling Agent The composition may optionally contain one or more coupling agents, advantageously chosen from those conventionally used for dyeing keratinous fibers.

[0072] Among these coupling agents, mention may be made in particular of meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalene-based coupling agents and heterocyclic coupling agents, as well as the corresponding addition salts.

[0073] 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-di Mention may be made of methoxypyridine, 1-N-(β-hydroxyethyl)amino-3,4-methylenedioxybenzene, 2,6-bis(β-hydroxyethylamino)toluene, 6-hydroxyindoline, 2,6-dihydroxy-4-methylpyridine, 1-H-3-methylpyrazol-5-one, 1-phenyl-3-methylpyrazol-5-one, 2,6-dimethylpyrazolo[1,5-b]-1,2,4-triazole, 2,6-dimethyl[3,2-c]-1,2,4-triazole and 6-methylpyrazolo[1,5-a]benzimidazole, 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.

[0074] 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.

[0075] The oxidizing bases each advantageously represent from 0.001% to 10% by weight relative to the total weight of the composition, preferably ranging from 0.005% to 5% by weight relative to the total weight of the composition.

[0076] When coupling agents are present, they 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.

[0077] direct dye The composition may also include one or more direct dyes.

[0078] The direct dyes may be neutral, cationic or anionic direct dyes, preferably neutral or cationic direct dyes.

[0079] 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, isopropyl alcohols, propyl methyl ... The dyes may be neutral, cationic or anionic direct dyes selected from indigoids, thioindigoids 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; 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.

[0080] 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.

[0081] 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)azones, 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, flavones such as flavanthrones and flavones. Nodoids; fluorindines; formazans; indamines; indanthrones; indigoids and pseudoindigoids; indophenols; indoanilines; isoindolines; isoindolinones; isoviolanthrone; lactones; (poly)methines such as stilbene or styryl 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.

[0082] 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 formulae (IIIa), (III'a), (IVa), (IV'a), (IV''a), (Va), (VIa) and (VI'a), Ar represents an aryl group, such as phenyl or naphthyl, substituted with at least one electron-donating group, such as i) optionally substituted (C1-C8) alkyl, ii) optionally substituted (C1-C8) alkoxy, iii) (di)(C1-C8)(alkyl)amino, wherein the alkyl group is optionally substituted with a hydroxyl group, iv) aryl(C1-C8) alkylamino, v) 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, preferably with one or more (C1-C8) alkyl, hydroxyl or (C1-C8) alkoxy groups; Ar″ represents a (hetero)aryl group, preferably optionally substituted with 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) hydroxyl, iv) (C1-C6)alkoxy; in particular (hetero)aryl is selected from imidazolyl, triazolyl, indolyl or pyridyl or phenyl optionally substituted with at least one group selected from nitro, nitroso and amino, preferably substituted in the para position of the phenyl group; X, X' and X'' may be 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 may be identical 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 may be the same or different and represent a hydrogen atom or a (C1-C8) alkyl group optionally substituted with a preferably hydroxyl group; or As a variant, 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' may be 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')- (wherein 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 may be the same or different and are hydrogen or halogen atoms, 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 may be the same or different and are a hydrogen atom, or - (C1-C6) alkyl; - polyhydroxy(C1-C6) alkyl, such as hydroxyethyl; - aryl optionally substituted with 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) 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 may be 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

[0083] The direct dye of formula (IV''a) preferably has the formula (IV'''a): [ka] (In formula (IV'''a), ·R 1 and R 3 may be the same or different, preferably the same, and represent a hydrogen atom, a (C1-C4) alkyl group such as methyl, or a sugar such as glucosyl, preferably a hydrogen atom; ·R 2 and R 4 may be identical or different, preferably identical, and represent a hydrogen atom, a (C1-C4) alkyl or (C1-C4) alkoxy group or an -O-sugar group such as -O-glucosyl, preferably (C1-C4) alkoxy such as methoxy; X may be identical or different, preferably identical, and represent an oxygen or sulfur atom or NR, where R represents a hydrogen atom or any group, preferably an oxygen atom; ALK represents a (C1-C4) alkylene group such as methylene or ethylene, preferably methylene. It is of the type.

[0084] The direct dyes of formula (IV''a) can be derived from curcumin, demethoxycurcumin and bisdemethoxycurcumin.

[0085] Preferably, the direct dye is selected from the direct dyes of formula (IV''a) and (IV'''a) defined above and mixtures thereof.

[0086] According to one particularly preferred embodiment, the direct dye is one of the following compounds (A) to (G): [ka] and mixtures thereof, preferably the compounds (E), (F) and (G) and mixtures thereof, more preferentially the compounds (E) and (G) and mixtures thereof.

[0087] Cationic Direct Dyes The direct dyes can be selected from those which are cationic or have an affinity for acidic substances and are therefore commonly referred to as "basic dyes", in particular those which contain at least one endocyclic or exocyclic cationic or cationizable group in their structure.

[0088] Cationic azo dyes that can be used in the present invention include, in particular, the cationic dyes described in the Kirk-Othmer Encyclopedia of Chemical Technology, "Dyes, Azo," J. Wiley & Sons, revised April 19, 2010.

[0089] Mention may also be made of the cationic azo dyes described in patent applications WO 95 / 15144, WO 95 / 01772 and EP 714954.

[0090] Mention may also 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; Basic Brown 17.

[0091] Among the cationic quinone dyes, those described in the Color Index International, 3rd edition are suitable, among which the following dyes may be mentioned in particular: Basic Blue 22; Basic Blue 99.

[0092] Among suitable azine dyes, mention may be made of those listed in the Colour Index International, 3rd edition, such as the following dyes: Basic Blue 17, Basic Red 2.

[0093] Among the cationic triarylmethane dyes that can be used according to the invention, mention may be made of the following dyes, in addition to those listed in the Color Index International, 3rd edition: Basic Green 1, Basic Violet 3, Basic Violet 14, Basic Blue 7, Basic Blue 26.

[0094] Mention may also be made of the direct dyes described in the documents US 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.

[0095] Mention may also be made of those listed in the encyclopedia "The Chemistry of Synthetic Dyes" by K. Venkataraman, 1952, Academic Press, vol. 1-7; the chapter "Dyes and Dye Intermediates" in "Kirk-Othmer's Encyclopedia of Chemical Technology," 1993, Wiley and Sons; and various chapters in "Ullmann's Encyclopedia of Industrial Chemistry," 7th edition, Wiley and Sons.

[0096] Preferably, the cationic direct dyes are chosen from those derived from the azo and hydrazono type dyes.

[0097] 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 No. 2538363, French Patent 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 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.

[0098] Preferably, the cationic direct dye comprises a quaternary ammonium group; more preferentially, the cationic charge is in a ring. This cationic group can be, for example, - a cationic group having an exocyclic (di / tri)(C1-C8) alkylammonium charge; or cationic groups with an intracyclic charge, such as acridinium, benzimidazolium, benzobistriazolium, benzopyrazolium, benzopyridazinium, benzoquinolium, benzothiazolium, benzotriazolium, benzoxazolium, bipyridinium, bis-tetrazolium, dihydrothiazolium, imidazopyridinium, imidazolium, indolium, isoquinolium, naphthimidazolium, naphthoxazolium, naphthopyrazolium, oxadiazolium, a cationic group having an endocyclic charge, comprising a cationic heteroaryl group selected from oxazolium, oxazolopyridinium, oxonium, phenazinium, phenoxazolium, pyrazinium, pyrazolium, pyrazoyltriazolium, pyridinium, pyridinoimidazolium, pyrrolium, pyrylium, quinolium, tetrazolium, thiadiazolium, thiazolium, thiazolopyridinium, thiazoylimidazolium, thiopyrylium, triazolium, or xanthylium; is.

[0099] Mention may also be made of the hydrazonocationic direct dyes of the formulae (IIb) and (IIIb) and the azo dyes of the formulae (IVb) and (Vb): Het + -C(R a )=NN(R b )-Ar,Q(IIb) - ; Het+-N(Ra )-N=C(R b )-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, optionally substituted, preferably with at least one (C1-C8) alkyl group, such as methyl, and preferentially carrying a cationic charge in the ring; ·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 represents an aryl group, in particular phenyl, optionally substituted with 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 with 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 optionally substituted with one or more (C1-C8)alkyl, hydroxyl, (di)(C1-C8)(alkyl)amino, (C1-C8)alkoxy or phenyl groups; ·R a and R b may be identical or different and represent a hydrogen atom or a (C1-C8) alkyl group optionally substituted, preferentially with a hydroxyl group; or otherwise, the substituent R aHet + 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 (C1-C4) alkyl group optionally substituted with a hydrogen atom or a hydroxyl group; Q - represents an anionic counterion such as a halide, alkyl sulfate, or alkyl sulfonate.

[0100] Mention may in particular be made of the azo and hydrazono direct dyes of formulae (IIb) to (Vb) having an internal cationic charge as defined above, more particularly the cationic direct dyes of formulae (IIb) to (Vb) having an internal cationic charge as described in WO 95 / 15144, WO 95 / 01772 and EP 714954.

[0101] 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 may be 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.

[0102] 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.

[0103] fluorescent dye The direct dye may be selected from fluorescent direct dyes.

[0104] 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, xanthenes.

[0105] Fluorescent dyes described in EP 1133975, WO 03 / 029359, EP 860636, WO 95 / 01772, WO 95 / 15144 and EP 714954, as well as in the encyclopedia "The Chemistry of Synthetic Dyes" by K. Venkataraman, 1952, Academic Press, vol. 1-7, the chapter "Dyes and Dye Intermediates" in the "Kirk-Othmer Encyclopedia of Chemical Technology", 1993, Wiley and Sons, various chapters in "Ullmann's Encyclopedia of Industrial Chemistry", 7th edition, Wiley and Sons, and the handbook "A Guide to Fluorescent Probes and Labeling Technologies", 10th Ed., Molecular Probes / Invitrogen-Oregon, circulated on the Internet or in advance print. 2005 can also be mentioned.

[0106] According to a preferred variant, 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’ -Ar,Q - In formula (Vb), ·W + represents a cationic heterocyclic or heteroaryl group, in particular including a quaternary ammonium, which is optionally substituted, in particular with one or more (C1-C8) alkyl groups optionally substituted with one or more hydroxyl groups; Ar is an aryl group such as phenyl or naphthyl, optionally and preferentially substituted with 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, preferably (di)hydroxyethylamino, in which one or more amino groups or the C1-C4 alkyl moieties thereof are optionally substituted with one or more hydroxyl groups; vii) one or more acylamino groups; viii) one or more aryl groups substituted with 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 may be identical or different and represent a hydrogen atom or an optionally substituted (C1-C8) alkyl group, preferentially an optionally substituted (C1-C4) alkyl group, or 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 as defined above.

[0107] 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.

[0108] The term "anionic direct dye" is intended to mean any direct dye containing 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.

[0109] Preferably, the anionic direct dye is an acidic anthraquinone.

[0110] The direct dye may preferably be an anionic direct dye selected from dyes of formula (III), (III'), (IV), (IV'), (V), (V'), (VI), (VI'), (VII), (VIII), (IX) and (X) shown below, and mixtures thereof.

[0111] 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 may be the same or different and are 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'' may be 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); - (O)2S(O - )-,M + (In the formula, M + represents a hydrogen atom or a cationic counterion); - (O)CO - -,M + (In the formula, M + is as defined above); - R"-S(O)2- (wherein R" represents a hydrogen atom, an alkyl or aryl, (di)(C1-C6)(alkyl)amino or aryl(C1-C6)(alkyl)amino group; preferentially a phenylamino or phenyl group); - R'''-S(O)2-X'-, where 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) (O)2S(O - )-,M + (In the formula, 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- (wherein Ar is an optionally substituted aryl group; preferentially one or more alkyl, (O)S(O - )-,M + 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) (O)S(O- )-,M + 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, wherein M+, R°, X, X', X'' and Ar are as defined above; W is a sigma bond σ, 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 may be the same or different and represent a hydrogen atom or an aryl group, or 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 (O)2S(O - )-,M' + group (in the formula, M' + represents a cationic counterion); or - at least one (O)CO - -,M' + group (in the formula, M' + represents a cationic counterion); Preferably at least one sodium sulfonate group It is understood that this includes:

[0112] 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 the dye of formula (III′) include Acid Red 111, Acid Red 134, and Acid Yellow 38.

[0113] b) Anionic pyrazolone azo dyes of formula (IV) or (IV'): [ka] In formulas (IV) and (IV'), ·R 11 , R 12 and R 13 may be the same or different and are hydrogen or halogen atoms, (C1-C6) alkyl or -(O)2S(O - ),M +group (in the formula, M + is as defined above); ·R 14 represents a hydrogen atom, a (C1-C6) alkyl group, or -C(O)O - ,M + 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 is 15 is R 16 together to form a double bond; ·R 17 and R 18 may be the same or different and are a hydrogen atom, or - (O)2S(O - )-,M + (In the formula, 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 may be the same or different and represent a hydrogen atom or a (C1-C6) alkyl group or a hydroxyl group; ·R 21 represents a hydrogen atom or a (C1-C6) alkyl or (C1-C6) alkoxy group; ·R a and R b may be 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; and 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 (O)2S(O - )-,M' + group (in the formula, M' + represents a cationic counterion); or - at least one (O)CO - -,M' + group (in the formula, M' + represents a cationic counterion); Preferably at least one sodium sulfonate group It is understood that this includes:

[0114] Examples of dyes of formula (IV) include Acid Red 195, Acid Yellow 23, Acid Yellow 27, and Acid Yellow 76, and an example of dyes of formula (IV') includes Acid Yellow 17.

[0115] 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 may be the same or different and are hydrogen or halogen atoms, or - (C1-C6) alkyl; - hydroxyl, mercapto; - (C1-C6)alkoxy, (C1-C6)alkylthio; optionally substituted aryloxy or arylthio, preferentially alkyl and (O)S(O - )-,M+ + wherein M+ is as defined above; - Alkyl and (O)2S(O - )-,M + (In the formula, M + is as defined above); - (di)(C1-C6)(alkyl)amino; - (di)(hydroxy(C1-C6)alkyl)amino; - (O)2S(O - )-,M + (In the formula, 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 may be the same or different and are 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, n-butyl; ii) (O)2S(O - )-,M + (In the formula, 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, in particular cyclohexyl; Z is hydroxyl and NR' 28 R' 29 (In the formula, R' 28 and R'29 may be 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: Formulas (V) and (V') are - at least one (O)2S(O - )-,M' + group (in the formula, M' + represents a cationic counterion); or - at least one (O)CO - -,M' + group (in the formula, M' + represents a cationic counterion); Preferably at least one sodium sulfonate group It is understood that this includes:

[0116] 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; EXT violet No. 2; and an example of a dye of formula (V') is Acid Black 48.

[0117] d) Nitro dyes of formula (VI) or (VI'): [ka] In formulas (VI) and (VI'), ·R 30 , R 31 and R 32 may be the same or different and are hydrogen or halogen atoms, 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)-, R°-X'-C(X)-X''- (wherein R°, X, X' and X'' are as defined above); - (O)2S(O - )-,M + (In the formula, M + is as defined above); - (O)CO - -,M + (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 may be the same or different and represent a hydrogen atom or a (C1-C6) alkyl group; W is as defined above; in particular W represents an N(H)- group; ALK represents a linear or branched divalent C1-C6 alkylene group; in particular, ALK represents a -CH2-CH2- group; n is 1 or 2; ·p represents an integer ranging from 1 to 5; q represents an integer ranging from 1 to 4; u is 0 or 1; when n is 1, J represents a nitro or nitroso group; in particular nitro; When n is 2, J is an oxygen or sulfur atom or a divalent radical -S(O) m - (wherein m represents an integer 1 or 2); preferentially, J represents a -SO2- group; M″ represents a hydrogen atom or a cationic counterion; · [ka] is optionally present and may be one or more R 30 represents a benzo group optionally substituted with a group; Formulas (VI) and (VI') are - at least one (O)2S(O - )-,M' + group (in the formula, M' + represents a cationic counterion); or - at least one (O)CO - -,M' + group (in the formula, M' + represents a cationic counterion); Preferably at least one sodium sulfonate group It is understood that this includes:

[0118] 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.

[0119] e) Triarylmethane dyes of formula (VII): [ka] In formula (VII), ·R 33, R 34 , R 35 and R 36 may be identical or different and are 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 groups and optionally (O) m S(O - )-,M + group (in the formula, M + and m represents a group selected from benzyl substituted with (as defined above); ·R 37 , R 38 , R 39 , R 40 , R 41 , R 42 , R 43 and R 44 may be the same or different and are 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)-, R°-X'-C(X)-X''- (wherein R° represents a hydrogen atom or an alkyl or aryl group; X, X' and X'' may be identical or different and represent an oxygen or sulfur atom or NR (wherein R represents a hydrogen atom or a (C1-C6) alkyl group); - (O)2S(O - )-,M + (In the formula, M + represents a hydrogen atom or a cationic counterion); - (O)CO - -,M + (In the formula, M + is as defined above) or represents a group selected from - otherwise, two adjacent groups R 41 and R 42 , or R42 and R 43 , or R 43 and R 44 are taken together to form i) nitro; ii) nitroso; iii) (O)2S(O - )-,M + 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 may be the same or different and are hydroxyl groups or (O)S(O - )-,M + (In the formula, M + is as defined above); 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 (O)2S(O - )-,M' + group (in the formula, M' + represents a cationic counterion); or - at least one (O)CO - -,M' + group (in the formula, M' + represents a cationic counterion); Preferably at least one sodium sulfonate group It is understood that this includes:

[0120] 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.

[0121] f) Xanthene dyes of formula (VIII): [ka] In formula (VIII), ·R 45 , R 46 , R 47 and R 48 may be the same or different and represent a hydrogen atom or a halogen atom; ·R 49 , R 50 , R 51 and R 52 may be the same or different and are hydrogen or halogen atoms, or - (C1-C6) alkyl; - (C1-C6)alkoxy, (C1-C6)alkylthio; - hydroxyl, mercapto; - Nitro, nitroso; - (O)2S(O - )-,M + (In the formula, M + represents a hydrogen atom or a cationic counterion); - (O)CO - -,M + (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 or 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 O - ,M + ; Thioalkoxide S - ,M + ; 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 may be the same or different and represent a hydrogen atom, a (C1-C6) alkyl group or an optionally substituted aryl group; in particular, L' represents an oxygen atom or one or more alkyl or (O) m S(O - )-,M + Groups (wherein m and M + represents a phenylamino group optionally substituted with (as defined above); Q and Q', which may be identical or different, represent an oxygen or sulfur atom; in particular, Q and Q' represent an oxygen atom; M + is as defined above.

[0122] 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.

[0123] g) Indole dyes of formula (IX): [ka] In formula (IX), ·R 53 , R 54 , R 55 , R 56 , R 57 , R58 , R 59 and R 60 may be the same or different and are 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 an alkyl or aryl group; X, X' and X'' may be identical or different and represent an oxygen or sulfur atom or NR (wherein R represents a hydrogen atom or a (C1-C6) alkyl group); - (O)2S(O - )-,M + (In the formula, M + represents a hydrogen atom or a cationic counterion); - (O)CO - -,M + (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 may be the same or different and represent a hydrogen atom or a (C1-C6) alkyl group; Formula (IX) is - at least one (O)2S(O - )-,M' + group (in the formula, M' + represents a cationic counterion); or - at least one (O)CO - -,M' + group (in the formula, M' + represents a cationic counterion); Preferably at least one sodium sulfonate group It is understood that this includes:

[0124] An example of the dye of formula (IX) is Acid Blue 74.

[0125] 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 may be the same or different and are a hydrogen atom or (O)S(O - )-,M + group (in the formula, M + represents a hydrogen atom or a cationic counterion); or otherwise, R 61 and R 62 or R 61 and R 64 together form one or more (O)S(O - )-,M + group (in the formula, M + represents a hydrogen atom or a cationic counterion), forming a benzo group optionally substituted with Formula (X) is a group having at least one (O)S(O - )-,M' + group (in the formula, M' + represents a cationic counterion), preferably comprising at least one sodium sulfonate group.

[0126] Examples of dyes of formula (X) include Acid Yellow 2, Acid Yellow 3 and Acid Yellow 5.

[0127] 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).

[0128] 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.

[0129] 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 (dinatrium-5-amino-4-hydroxy-3-(phenylazo)-2,7-naphthalenesulfonic acid), The dyes designated as CI 20470 (1-amino-2-(4'-nitrophenylazo)-7-phenylazo-8-hydroxy-3,6-naphthalenedisulfonic acid disodium salt), CI 42090 (N-ethyl-N-[4-[[4-[ethyl(3-sulfophenyl)methyl]amino]phenyl](2-sulfophenyl)methylene]-2,5-cyclohexadien-1-ylidene]-3-sulfobenzenemethanaminium hydroxide disodium salt, inner salt), and CI 61570 (2,2'-[(9,10-dihydro-9,10-dioxo-1,4-anthracenediyl)diimino]bis[5-methyl]benzenesulfonic acid disodium salt).

[0130] Compounds corresponding to mesomeric or tautomeric forms of structures (III)-(X) can also be used.

[0131] natural dyes The direct dye can be selected from natural direct dyes. Among the natural direct dyes that can be used according to the present invention, mention can be made of lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, protocatechualdehyde, indigo, isatin, curcumin, spinulosin, apigenidin, orcein, brazilin, brazilain, hematin, and hematoxylin. Extracts or decoctions containing these natural dyes can also be used, in particular henna-based compresses or extracts.

[0132] 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, which may be identical or different, represent one of the following: a hydrogen atom or a (C1-C6) alkyl optionally substituted with a hydroxyl group; an aryl, such as phenyl; an aryl(C1-C4) alkyl, such as benzyl; a heteroaryl; a heteroaryl(C1-C4) alkyl; or two groups R1 and R2 and / or R3 and R4, carried by the same nitrogen atom, together with the nitrogen atom that carries them, form an optionally substituted heterocycloalkyl group, such as morpholino, piperazino or piperidino, preferably R1, R2, R3 and R4, which may be identical or different, 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 16may be the same or different and represent a hydrogen atom or a halogen atom, or 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 may be 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'), where the R' groups 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-), in which 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-), in which the R groups, which may be identical or different, 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 R10, 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 16 together with the carbon atoms that carry them form a 6-membered fused ring that is aryl or heteroaryl, preferably benzo, which may 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.

[0133] The direct dye is preferably selected from Basic Red 51, HC Blue 15 and mixtures thereof.

[0134] The direct dyes may be present 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.

[0135] According to a preferred embodiment, the composition comprises a total content of colorants of less than 0.1% by weight, preferably less than 0.01% by weight and more preferentially less than 0.001% by weight relative to the total weight of the composition. According to a more preferred embodiment, the composition does not comprise colorants.

[0136] Additional basifying agents The composition may also include one or more additional basifying agents other than the carbonates, bicarbonates and silicates defined above.

[0137] According to one preferred embodiment, the composition according to the invention does not comprise additional basifying agents selected from aqueous ammonia and / or alkanolamines.

[0138] Acidifying Agent The composition may also include one or more acidifying agents.

[0139] pH of the composition The compositions according to the invention preferably have a pH of 11 or less, preferably 10.5 or less, preferably 10 or less.

[0140] The pH of the compositions according to the invention may range from 8 to 11, preferably from 8 to 10.5, and more preferentially from 8 to 10. According to one particularly preferred embodiment, the pH of the compositions according to the invention ranges from 8.3 to 10.

[0141] Other characteristics of the composition The composition preferably comprises water in a content ranging from 0.01% to 99% by weight, more preferentially from 0.01% to 80% by weight, relative to the total weight of the composition.

[0142] The composition may also include at least one organic solvent. The term "organic solvent" is intended to mean an organic substance that can dissolve other substances without chemically modifying them.

[0143] The compositions according to the invention may be in liquid form, in serum form, in thickened form, in particular in gel, cream, wax or paste form, or in foam form.

[0144] 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.

[0145] Method for lightening keratin fibers According to a second aspect, the subject of the present invention is a method for lightening keratinous fibers, comprising applying to the keratinous fibers a composition as defined above.

[0146] In particular, the composition is applied to wet or dry keratinous fibers.

[0147] Preferably, the keratinous fibers are dark colored keratinous fibers.

[0148] The term "dark keratinous fibers" is intended to mean keratinous fibers having a shade of less than or equal to 6 (dark blonde), preferably less than or equal to 4 (chestnut brown).

[0149] The "tone scale" is a unit known to hair styling professionals and is listed in the book Science des traitements capillaires [Hair treatment sciences] by Charles Zviak, 1988, published by Masson, pages 215 and 278; the tone scale ranges from 1 (black) to 10 (very light blonde) according to the European scale, with one unit corresponding to one shade and the higher the number, the lighter the shade.

[0150] 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.

[0151] The composition is usually left on the fibers for 1 minute to 1 hour, preferably 5 to 60 minutes. For example, the composition can be left on the fibers for 50 minutes.

[0152] The composition can be left on the fibers under a sealing system. Non-limiting examples of sealing systems that may be mentioned are wrap-type sealing systems made of aluminum or plastic film or perforated or non-perforated hair caps.

[0153] The temperature during the lightening process is usually between ambient temperature (15° C. and 25° C.) and 80° C., preferably between room temperature and 60° C. For example, the temperature during the lightening process is 33° C. After treatment, the keratin fibers are optionally rinsed with water, optionally washed with shampoo, then rinsed with water, and then dried or air-dried.

[0154] The drying step can be carried out using absorbent paper, a hair dryer or a styling hood.

[0155] The composition according to the invention is preferably prepared by mixing at least two compositions, preferably by blending the compositions according to the invention immediately before applying them to the keratinous fibers.

[0156] According to one embodiment, the composition according to the invention comprises at least two compositions, preferably - 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 (B) comprising ii) ammonium carbonate, and iii) one or more silicates as defined above, and optionally iv) one or more bicarbonates and / or one or more bicarbonate-generating systems as defined above; The composition is obtained by mixing two compositions. Preferably, at least one of the compositions (A) or (B) is aqueous. According to a preferred embodiment, the composition (A) is aqueous. According to a particular embodiment, the composition (B) is anhydrous. According to a particular embodiment, the composition (A) is aqueous and the composition (B) is anhydrous.

[0157] The term "aqueous composition" means a composition that contains at least 5% by weight of water. Aqueous compositions preferably contain more than 10% by weight of water, and even more advantageously more than 20% by weight of water.

[0158] According to a more preferred embodiment, the composition according to the invention comprises at least two compositions, preferably - i) a composition (A1) comprising hydrogen peroxide; - a composition (B1) comprising ii) ammonium carbonate, and iii) one or more silicates as defined above, and optionally iv) one or more bicarbonates as defined above; The composition is obtained by mixing two compositions. Preferably, at least one of the compositions (A1) or (B1) is aqueous. According to a particular embodiment, the composition (B1) is anhydrous. According to one particular embodiment, the composition (A1) is aqueous and the composition (B1) is anhydrous.

[0159] The composition used in the method according to the invention makes it possible to obtain a lightening of keratinous fibers characterized by a b* value that is lower, preferably 10% lower, more preferentially 15% lower, than the b* value measured at the same intensity L* on keratinous fibers lightened using a composition containing one or more persulfates, the b* and L* values ​​being measured in the CIE L*a*b* system.

[0160] Preferably, the b* and L* values ​​are measured according to the color evaluation method described in the Examples.

[0161] use According to a third aspect, the subject of the invention is the use of a composition as defined above for lightening keratinous fibers, preferably for lightening them while at the same time reducing their yellowness.

[0162] Multi-compartment device (kit) According to a fourth aspect, the subject of the present invention is a multi-compartment device (kit), comprising: a first compartment containing the composition (A) defined above; a second compartment containing the composition (B) defined above; A multi-compartment device (kit) comprising:

[0163] Preferably, the multi-compartment device comprises: a first compartment containing the composition (A1) defined above; a second compartment containing the composition (B1) defined above; Includes. [Example]

[0164] The following examples will enable a clearer understanding of the present invention, but are not intended to limit the nature of the invention, and in the examples provided below, all amounts are expressed as weight percentages relative to the total weight of the composition, unless otherwise specified.

[0165] How to evaluate color In these examples, the color of the hair tresses was evaluated using a Minolta CM3610A spectrophotometer (illuminant D65) colorimeter in the CIE L*a*b* system, where L* represents the lightness of the color, a* represents the hue along the green / red axis, and b* represents the hue along the blue / yellow axis. The higher the value of L*, the lighter the color. The higher the value of a*, the redder the color, and the higher the value of b*, the yellower the color.

[0166] Example 1 (Comparative) The following compositions C1 to C12 were prepared and then applied according to the application procedures described below.

[0167] [Table 1]

[0168] [Table 2]

[0169] Application procedure 10 g of each composition C1 to C12 is applied to 12 tresses of 1 g of Caucasian HT4 hair on a hot plate maintained at a temperature of 33° C. The whole is covered with cellophane film for 50 minutes, after which the tresses are rinsed, washed with a standard shampoo, rinsed again and dried.

[0170] colorimetric measurement The results of the colorimetric measurements are summarized in the table below.

[0171] [Table 3]

[0172] The results show that the comparative compositions containing persulfate are able to achieve a good level of light color, characterized by relatively high L* values, but the resulting shades have a significant yellow component, characterized by high b* values.

[0173] Example 2 The following compositions C13 to C15 were prepared and then applied according to the application procedures described below.

[0174] [Table 4]

[0175] Application steps: 10 g of each of compositions C13 to C15 is applied to three 1 g tresses of Caucasian HT4 hair on a hot plate maintained at a temperature of 33°C. The whole is covered with cellophane film for 50 minutes. The tresses are then rinsed, washed with a standard shampoo, rinsed again and dried.

[0176] colorimetric measurement The results of the colorimetric measurements are summarized in the table below.

[0177] [Table 5]

[0178] The results show that the compositions according to the invention are capable of obtaining a good level of lightening, characterized by a relatively high L* value. Furthermore, the shade obtained is characterized by a lower b* value for the compositions according to the invention than for the comparative composition based on persulfate of Example 1, at a similar level of intensity L*, as shown in Figure 1.

[0179] Example 3 The following compositions A to C were prepared and then applied according to the application procedures described below.

[0180] [Table 6]

[0181] Application steps: 10 g of each of Compositions A to C is applied to three 1 g tresses of Caucasian HT4 hair on a hot plate maintained at a temperature of 33°C. The whole is covered with cellophane film for 50 minutes. The tresses are then rinsed, washed with a standard shampoo, rinsed again and dried.

[0182] colorimetric measurement The results of the colorimetric measurements are summarized in the table below.

[0183] [Table 7]

[0184] The results show that compositions according to the present invention provide superior levels of lightening, characterized by relatively high L* values.

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 carbonate; iii) one or more silicates Including, the silicates are present in a total content ranging from 1% to 40% by weight relative to the total weight of the composition; The composition is persulfate-free. composition.

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 agents are 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 ammonium carbonate 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. 6. The composition according to claim 1, wherein said silicates are present in a total content ranging from 2% to 35% by weight relative to the total weight of the composition.

7. 7. The composition of any one of claims 1 to 6, wherein the composition also comprises iv) one or more bicarbonates and / or one or more bicarbonate-generating systems.

8. The bicarbonate is alkali metal bicarbonates; alkaline earth metal bicarbonates; - Formula N ＋ R １ R ２ R ３ R ４ , HCO ３ － (In the formula, R １ , R ２ , R ３ and R ４ are each independently optionally substituted with a hydrogen atom or a hydroxyl group (C １ ~C ４ ) a compound of formula (I) wherein: - aminoguanidine bicarbonate; - their mixtures The composition of claim 7, wherein the composition is selected from:

9. 9. The composition according to claim 7, wherein the bicarbonate and / or the bicarbonate-generating system are present in a total content ranging from 0.01% to 20% by weight relative to the total weight of the composition.

10. 10. The composition according to claim 1, wherein the mass ratio of the total amount of ammonium carbonates ii) to the total amount of silicates iii) is from 0.00025 to 20.

11. 11. The composition according to any one of claims 1 to 10, wherein the mass ratio of the total amount of ammonium carbonate ii) to the total amount of chemical oxidizing agent i) is from 0.0008 to 20.

12. 12. The composition according to claim 7, wherein the mass ratio of the total amount of ammonium carbonate ii) to the total amount of bicarbonate and / or bicarbonate-generating system iv) is from 0.005 to 2000.

13. 13. The composition according to any one of claims 1 to 12, wherein the composition comprises a total content of magnesium carbonate of less than 5% by weight.

14. The composition according to any one of claims 1 to 13, wherein the pH of the composition is in the range of 8 to 11.

15. The composition according to any one of the preceding claims, wherein the composition comprises a total content of colorants of less than 0.1% by weight relative to the total weight of the composition.

16. A method for lightening keratinous fibers, comprising applying to said keratinous fibers a composition according to any one of claims 1 to 15.

17. The composition according to any one of claims 1 to 15, comprising at least two compositions: 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; and a composition (B) comprising ii) ammonium carbonate according to claim 1 or 5 and iii) one or more silicates, and optionally iv) one or more bicarbonates and / or one or more bicarbonate-generating systems according to claim 7 or 8; 17. The method of claim 16, obtained from the mixing of

18. Use of a composition according to any one of claims 1 to 15 for lightening keratin fibres.

19. 1. A multi-compartment device, comprising: a first compartment containing the composition (A) according to claim 17; and a second compartment containing the composition (B) according to claim 17; Multi-compartment devices, including:

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