Hair coloring process employing a lightening composition and a coloring composition comprising a direct dye, an aromatic compound and a hydroxylated aliphatic solvent.

Abstract

A hair coloring process employing a lightening composition and a coloring composition comprising a direct dye, an aromatic compound, and a hydroxylated aliphatic solvent. The invention relates to a process for coloring keratin fibers, in particular human keratin fibers such as hair, comprising the application to said keratin fibers of a lightening composition and a coloring composition comprising: - one or more direct dye(s), - one or more compounds of formula (I): (I) in which Y represents a C1-C4 hydroxyalkyl group or a C1-C4 hydroxyalkyloxy radical, n denotes an integer ranging from 0 to 5, X, identical or different, represents a C1-C4 alkyl radical or a halogen, - one or more aliphatic hydroxylated solvent(s) comprising from 2 to 6 carbon atoms.

Description

Title of the invention: Hair coloring process employing a lightening composition and a coloring composition comprising a direct dye, an aromatic compound and a hydroxylated aliphatic solvent.

[0001] The present invention relates to a method for coloring human keratin fibers, in particular hair, using a lightening composition and a coloring composition comprising a direct dye, an aromatic compound and a hydroxylated aliphatic solvent as well as a multi-compartment device containing the compositions.

[0002] Two main modes of coloring of human keratin fibers, and in particular of hair, are known.

[0003] One of these two methods is oxidation or permanent coloring. This coloring method uses one or more oxidation dye precursors, usually one or more oxidation bases possibly associated with one or more couplers.

[0004] In general, oxidation bases are chosen from among ortho- or para-phenylenediamines, ortho- or para-aminophenols, and heterocyclic compounds. These oxidation bases are colorless or weakly colored compounds which, when combined with oxidizing agents, allow the formation of colored species.

[0005] Often, the nuances obtained with these oxidation bases are varied by associating them with one or more couplers, the latter being chosen in particular from among the aromatic meta-diamines, the meta-aminophenols, the meta-diphenols and certain heterocyclic compounds, such as indolic compounds.

[0006] The variety of molecules involved in the oxidation bases and couplers allows for a rich palette of colors. This type of coloring also allows for the production of permanent colors.

[0007] The second coloring method, called direct or semi-permanent coloring, involves the application of direct dyes, which are molecules with an affinity for fibers and which remain colored even in the absence of an oxidizing agent added to the compositions containing them. Given the nature of the molecules used, these remain mostly on the surface of the fiber and penetrate relatively little into the fiber, compared to the small precursor molecules of oxidation dyes.

[0008] The direct dyes generally used are chosen from among the benzene, anthraquinone, nitropyridine, azo, and methicillin direct dyes. Azomethine, xanthenic, acridinic, azinic, or triarylmethanic dyes. The chemical species used can be nonionic, anionic (acidic dyes), or cationic (basic dyes). Direct dyes can also be natural dyes.

[0009] Compositions containing one or more direct dyes are applied to the keratin fibers for a time necessary to obtain the desired color, then rinsed.

[0010] However, the resulting colours are particularly chromatic but temporary or semi-permanent colours because their desorption from the surface and / or the core of the fibre is responsible for their lack of dyeing power and their poor resistance to washing.

[0011] There is a need to obtain a permanent hair colour, without oxidation dyes such as bases and couplers, in natural shades, with a harmonious and natural colouring result.

[0012] There is also a need to obtain a hair colour that is capable of leading to a good rise, intensity and chromaticity of the colour, while having low selectivity and good tenacity, in particular good persistence to shampoos, and that is capable of leading to good dyeing performance, even after a period of storage, while having good qualities of use and maintaining good sensory performance in particular in terms of shine, softness, suppleness, smoothness, detangling of keratin fibers such as hair.

[0013] This and other objectives are achieved by the present invention, which therefore relates to a method for coloring keratin fibers, in particular human keratin fibers such as hair, comprising the application to said keratin fibers: i) a lightening composition comprising: - one or more oxidizing agent(s), - one or more alkali agent(s); and ii) a coloring composition comprising: - one or more direct dye(s), - one or more compound(s) of formula (I): (X)n in which Y represents a C1-C4 hydroxyalkyl group or a C1-C4 hydroxyalkyloxy radical, n denotes an integer ranging from 0 to 5, X, whether the same or different, represents a C1-C4 alkyl radical or a halogen, - one or more aliphatic hydroxylated solvent(s) comprising 2 to 6 carbon atoms.

[0014] The invention also relates to a device with at least three compartments, for the staining of keratin fibers, comprising at least a first compartment containing a staining composition comprising one or more direct dye(s), one or more compound(s) of formula (I) as defined above and one or more aliphatic hydroxylated solvent(s) comprising from 2 to 6 carbon atoms, at least a second compartment containing an alkaline composition comprising one or more alkaline agent(s), and at least a third compartment containing an oxidizing composition comprising one or more chemical oxidizing agent(s).

[0015] The invention makes it possible to obtain colours of keratin fibres with good tenacity, in particular good persistence to shampoos, in natural shades, without using oxidation dyes such as bases and couplers, with a harmonious, natural colouring result, i.e. without helmet effect, while providing shine.

[0016] Other objects, features, aspects and advantages of the invention will become even clearer upon reading the description and examples that follow and upon examination of the accompanying drawing, on which:

[0017] In what follows, and unless otherwise indicated, the bounds of a domain of values ​​are included in that domain, in particular in the expressions "between" and "ranging from ... to ...".

[0018] Furthermore, the expression "at least one" used in this description is equivalent to the expression "one or more".

[0019] As previously stated, the coloring process employs a lightening composition and a coloring composition. Lightening composition

[0020] The expressions "lightening" and "bleaching" are synonymous and can be used interchangeably.

[0021] The lightening composition comprises one or more chemical oxidizing agent(s) and one or more alkaline agent(s). Chemical oxidizing agent

[0022] The lightening composition implemented in the process according to the invention comprises one or more chemical oxidizing agent(s).

[0023] A chemical oxidizing agent is understood to be an oxidizing agent other than oxygen from the air.

[0024] The chemical oxidizing agent(s) are chosen from hydrogen peroxide, urea peroxide, alkali metal bromates or ferricyanides, peroxygenated salts such as alkali or alkaline-earth metal persulfates, perborates and percarbonates, and peracids and their precursors.

[0025] Preferably, the brightening composition does not include peroxygenated salts such as persulfates, perborates and percarbonates of alkali or alkaline earth metals.

[0026] More preferably the composition according to the invention comprises hydrogen peroxide.

[0027] The total content of the chemical oxidizing agent(s) varies preferably from 1 to 40% by weight, more preferably from 2 to 30% by weight, better from 3 to 20% by weight relative to the total weight of the lightening composition. Alkaline agent

[0028] The lightening composition implemented in the process according to the invention comprises one or more alkaline agents which may be mineral, organic or hybrid alkaline agents.

[0029] For the purposes of the present invention, the terms "alkaline agent" and "alkalinizing agents" are used interchangeably.

[0030] The mineral alkalizing agent(s) are preferably chosen among ammonia, alkali carbonates or bicarbonates such as sodium (hydrogen)carbonate and potassium (hydrogen)carbonate, alkali or alkaline earth metal phosphates such as sodium phosphates or potassium phosphates, sodium or potassium hydroxides, alkali or alkaline earth metal silicates or metasilicates such as sodium metasilicate and mixtures thereof.

[0031] The organic alkalizing agent(s) are preferably chosen from alkanolamines, amino acids, organic amines other than alkanolamines, oxyethylenated and / or oxypropylenated ethylenediamines, 1,3-diaminopropane, spermine, spermidine and mixtures thereof.

[0032] Alkanolamine means an organic amine comprising a primary, secondary or tertiary amine function, and one or more linear or branched alkyl groups, in Ci-C8 bearing one or more hydroxyl radicals.

[0033] Organic amines selected from among alkanolamines such as mono-, di- or tri-alkanolamines, comprising one to three hydroxyalkyl radicals, identical or not, in Ci-C4, are particularly suitable for carrying out the invention.

[0034] In particular, the alkanolamine(s) are chosen from monoethanolamine (MEA), diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, N,N-dimethylethanolamine, 2-amino-2-methyl-l-propanol, triisopropanolamine, 2-amino-2-methyl-l,3-propanediol, 3-amino-l,2-propanediol, 3-dimethylamino-l,2-propanediol, tris-hydroxymethylamino-methane and mixtures thereof.

[0035] Advantageously, the amino acids are basic amino acids comprising an additional amine function. Such basic amino acids are preferably chosen from histidine, lysine, arginine, omithine, and citrulline.

[0036] The organic amine can also be chosen from among heterocyclic organic amines. In particular, in addition to histidine already mentioned among amino acids, examples include pyridine, piperidine, imidazole, triazole, tetrazole, and benzimidazole. The organic amine can also be chosen from amino acid dipeptides. Examples of amino acid dipeptides usable in the present invention include carnosine, anserine, and balenine. The organic amine can also be chosen from compounds containing a guanidine functional group. Examples of amines of this type other than arginine that can be used in the present invention include creatine, creatinine, 1,1-dimethylguanidine, 1,1-diethylguanidine, glycocyamine, metformin, agmatine, n-amidinoalanine, 3-guanidinopropionic acid, 4-guanidinobutyric acid and 2-([amino(imino)methyl]amino)ethane-1-sulfonic acid.)

[0037] In particular, guanidine carbonate or monoethanolamine hydrochloride can be used as hybrid compounds.

[0038] The useful alkali agent(s) according to the invention is / are preferably chosen from alkanolamines such as monoethanolamine, diethanolamine, triethanolamine; ammonia, carbonates or bicarbonates such as sodium (hydrogen)carbonate and potassium (hydrogen)carbonates, alkali or alkaline earth metal silicates or metasilicates such as sodium metasilicate and mixtures thereof, more preferably from alkanolamines and ammonia, better from alkanolamines, even better, monoethanolamine.

[0039] In a particular embodiment, the brightening composition used in the process according to the invention is free of ammonia.

[0040] The total content of the alkaline agent(s) varies preferably from 0.1 to 40% by weight, more preferably from 1 to 30% by weight, better from 2 to 25% by weight, even better from 4 to 20% by weight relative to the total weight of the lightening composition.

[0041] According to a particular embodiment, the total alkanolamine content, preferably monoethanolamine, varies preferably from 0.1 to 40% by weight, more preferably from 1 to 30% by weight, better from 2 to 25% by weight, even better from 4 to 20% by weight, or even from 5 to 15% by weight relative to the total weight of the lightening composition. Fatty acid

[0042] The lightening composition implemented in the process according to the invention may further comprise one or more fatty acids.

[0043] Preferably, the lightening composition implemented in the process according to the invention comprises one or more fatty acid(s).

[0044] By "fatty acids" is meant a long-chain carboxylic acid comprising at least 6 carbon atoms, in particular from 6 to 40 carbon atoms, preferably from 8 to 30 carbon atoms. The fatty acids according to the invention preferably comprise from 10 to 30 carbon atoms and more preferably from 12 to 22 carbon atoms. They may optionally be hydroxylated.

[0045] Preferably, the fatty acids comprise at least one carboxylic acid group and an alkyl chain, linear or branched, saturated or unsaturated, in particular unsaturated, comprising from 6 to 40 carbon atoms, preferably from 8 to 30 carbon atoms, more preferably from 10 to 30 carbon atoms and better from 12 to 22 carbon atoms.

[0046] Preferably, the fatty acids comprise at least one carboxylic acid group and an alkyl chain, linear or branched, saturated or unsaturated, in particular unsaturated, comprising from 10 to 30 carbon atoms, in particular from 12 to 22 carbon atoms.

[0047] Preferably, the fatty acids comprise at least one carboxylic acid group and an unsaturated linear or branched alkyl chain comprising 12 to 22 carbon atoms.

[0048] More preferably, the fatty acids according to the invention are chosen from compounds of RC(O)OH structure in which R represents an alkyl group, linear or branched, saturated or unsaturated, comprising from 6 to 40 carbon atoms, preferably from 8 to 30 carbon atoms, preferably from 10 to 24 carbon atoms, better from 12 to 20 carbon atoms.

[0049] For the purposes of the present invention, the fatty acids present in the composition are neither oxyalkylated nor glycerolated.

[0050] Fatty acids can be chosen from solid fatty acids, liquid fatty acids and mixtures thereof.

[0051] For the purposes of this invention, "solid fatty acid" means a fatty acid having a melting point above 25°C, preferably above or equal to 28°C, more preferably above or equal to 30°C at atmospheric pressure (1.013.105 Pa).

[0052] The solid fatty acids used in the present invention are in particular selected from myristic acid, cetyl acid, arachidic acid, stearic acid, lauric acid, behenic acid, 12-hydroxystearic acid and mixtures thereof.

[0053] In a particularly preferred manner, the solid fatty acid(s) are chosen from lauric acid, myristic acid, cetyl acid, stearic acid.

[0054] For the purposes of this invention, "liquid fatty acid" means a fatty acid having a melting point of less than or equal to 25°C, preferably less than or equal to 20°C at atmospheric pressure (1.013.105 Pa).

[0055] The liquid fatty acid(s) according to the invention can be chosen from oleic acid, linoleic acid, arachidonic acid, isostearic acid, isopalmitic acid, and mixtures thereof, preferably oleic acid.

[0056] Preferably, the lightening composition comprises one or more solid fatty acid(s), preferably selected from lauric acid, myristic acid, cetyl acid, stearic acid and mixtures thereof.

[0057] Advantageously, the fatty acid(s) are present in a total content ranging from 0.1 to 15% by weight, preferably from 0.5 to 10%, preferably from 1 to 5% by weight relative to the total weight of the lightening composition. Fats different from fatty acids

[0058] The lightening composition implemented in the process according to the invention may further comprise one or more fats other than fatty acids.

[0059] Preferably, the lightening composition implemented in the process according to the invention comprises one or more fats other than fatty acids.

[0060] The term "fatty substance" refers to an organic compound insoluble in water at 25°C and atmospheric pressure (1.013 x 10⁵ Pa) (solubility less than 5% by weight, and preferably less than 1% by weight, even more preferably less than 0.1% by weight). Its structure includes at least one hydrocarbon chain comprising at least 6 carbon atoms and / or a chain of at least two siloxane groups. Furthermore, fatty substances are generally soluble in organic solvents under the same temperature and pressure conditions, such as chloroform, dichloromethane, carbon tetrachloride, ethanol, benzene, toluene, tetrahydrofuran (THF), petrolatum, or decamethylcyclopentasiloxane.

[0061] Advantageously, the fats usable in the present invention are neither (poly)oxyalkylated nor (poly)glycerolated.

[0062] Preferably the useful fatty substances according to the invention are non-siliconized.

[0063] The term "non-siliconized fat" means a fat that does not contain Si-O bonds and the term "siliconized fat" means a fat that contains at least one Si-O bond.

[0064] The fats used according to the invention may be liquid fats (or oils) and / or solid fats. Liquid fats are defined as fats having a melting point of 25°C or lower at atmospheric pressure (1.013 x 10⁵ Pa). Solid fats are defined as fats having a melting point above 25°C at atmospheric pressure (1.013 x 10⁵ Pa).

[0065] For the purposes of the present invention, the melting point corresponds to the temperature of the most endothermic peak observed in thermal analysis (differential scanning calorimetry or DSC) as described in ISO 11357-3; 1999. The melting point can be measured using a differential scanning calorimeter (DSC), for example, the calorimeter sold under the name "MDSC 2920" by TA Instruments. In the present application, all melting points are determined at atmospheric pressure (1.013 x 10⁵ Pa).

[0066] More particularly, the liquid fat(s) according to the invention are chosen from liquid hydrocarbons in C6 to Ci6, liquid hydrocarbons comprising more than 16 carbon atoms, non-siliconized oils of animal origin, triglyceride-type oils of vegetable or synthetic origin, fluorinated oils, liquid fatty alcohols, liquid esters of fatty acids and / or fatty alcohols other than triglycerides, silicone oils, and mixtures thereof.

[0067] It is recalled that alcohols, esters and fatty acids more particularly have at least one hydrocarbon group, linear or branched, saturated or unsaturated, comprising from 6 to 40, preferably from 8 to 30 carbon atoms, possibly substituted, in particular by one or more hydroxyl groups (in particular 1 to 4). If they are unsaturated, these compounds may comprise one to three carbon-carbon double bonds, conjugated or not.

[0068] As regards liquid hydrocarbons in the C6 to C16 range, these can be linear, branched, possibly cyclic, and are preferably chosen from among the alkanes. By way of example, hexane, cyclohexane, undecane, dodecane, isododecane, tridecane, isoparaffins such as isohexadecane, isodecane, and mixtures thereof may be cited.

[0069] Liquid hydrocarbons comprising more than 16 carbon atoms may be linear or branched, of mineral or synthetic origin, and are preferably chosen from paraffin or petroleum jelly oils (INCI name ore oil or paraffinum liquidum), polydecenes, hydrogenated polyisobutene such as Parleam®, and mixtures thereof.

[0070] Perhydrosqualene can be cited as an example of hydrocarbon oils of animal origin.

[0071] Triglyceride oils of vegetable or synthetic origin are preferably chosen from among liquid triglycerides of fatty acids comprising 6 to 30 carbon atoms such as triglycerides of heptanoic or octanoic acid or, for example sunflower, corn, soybean, pumpkin, grapeseed, sesame, hazelnut, apricot, macadamia, arara, sunflower, castor, avocado oils, caprylic / capric acid triglycerides such as those sold by Stearineries Dubois or those sold under the names Miglyol® 810, 812 and 818 by Dynamit Nobel, shea butter oil, and mixtures thereof.

[0072] As regards fluorinated oils, these can be chosen from perfluoromethylcyclopentane and perfluoro-1,3 dimethylcyclohexane, sold under the names "FLUTEC® PCI" and "FLUTEC® PC3" by BNFL Fluorochemicals; perfluoro-1,2-dimethylcyclobutane; perfluoroalkanes such as dodecafluoropentane and tetradecafluorohexane, sold under the names "PF 5050®" and "PF 5060®" by 3M, or bromoperfluorooctyl sold under the name "FORALKYL®" by Atochem; nonafluoromethoxybutane and nonafluoroethoxyisobutane; perfluoromorpholine derivatives, such as 4-trifluoromethyl perfluoromorpholine sold under the name "PF 5052®" by 3M.

[0073] Liquid fatty alcohols suitable for implementing the invention are particularly chosen from saturated or unsaturated, linear or branched alcohols, preferably unsaturated or branched, comprising from 6 to 40 carbon atoms, preferably from 8 to 30 carbon atoms. Examples include octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol, isostearyl alcohol, oleic alcohol, linolenic alcohol, ricinoleic alcohol, undecylenic alcohol or linoleic alcohol, and mixtures thereof.

[0074] With regard to liquid esters of fatty acids and / or fatty alcohols, other than the triglycerides mentioned above, we may mention in particular the esters of saturated or unsaturated mono- or poly-aliphatic acids, linear in C1 to C26 or branched in C3 to C26 and of saturated or unsaturated mono- or poly-aliphatic alcohols, linear in C1 to C26 or branched in C3 to C26, the total number of carbons of the esters being greater than or equal to 6, more advantageously greater than or equal to 10.

[0075] Preferably, for monoalcohol esters, at least one of the alcohol or acid from which the esters of the invention are derived is branched.

[0076] Among the monoesters, the following may be mentioned: dihydroabietyl behenate; octyldodecyl behenate; isocetyl behenate; isostearyl lactate; lauryl lactate; linoleyl lactate; oleyl lactate; isostearyl octanoate; isocetyl octanoate; octyl octanoate; decyl oleate; isocetyl isostearate; isocetyl laurate; isocetyl stearate; isodecyl octanoate; isodecyl oleate; isononyl isononanoate; isostearyl palmitate; methyl acetyl ricinoleate; octyl isononanoate; 2-ethylhexyl isononate; octyldodecyl erucate; oleyl erucate; ethyl and isopropyl palmitates, such as ethyl-2-hexyl palmitate, 2-octyldecyl palmitate; alkyl myristates such as isopropyl myristate; isobutyl stearate; 2-hexyldecyl laurate, and mixtures thereof.

[0077] Preferably among monoesters of monoacids and monoalcohols, ethyl and isopropyl palmitates, alkyl myristates such as isopropyl or ethyl myristate, isocetyl stearate, ethyl-2-hexyl isononanoate, isodecyl neopentanoate, isostearyl neopentanoate, and mixtures thereof will be used.

[0078] Still within the framework of this variant, one can also use the esters of di- or tricarboxylic acids in C4 to C22 and of alcohols in C1 to C22 and the esters of mono-, di-, or tricarboxylic acids and di-, tri-, tetra- or pentahydroxy alcohols in C2 to C26-

[0079] Examples include: diethyl sebacate; diisopropyl sebacate; diisopropyl adipate; din-propyl adipate; dioctyl adipate; diisostearyl adipate; dioctyl maleate; glyceryl undecylenate; octyldodecyl stearoyl stearate; pentaerythrityl monoricinoleate; pentaerythrityl tetraisononanoate; pentaerythrityl tetrapelargonate; pentaerythrityl tetraisostearate; pentaerythrityl tetraoctanoate; propylene glycol dicaprylate; propylene glycol dicaprate; tridecyl erucate; triisopropyl citrate; triisotearyl citrate; glyceryl trilactate; glyceryl trioctanoate; trioctyldodecyl citrate; trioleyl citrate; propylene glycol dioctanoate; neopentyl glycol diheptanoate; diethylene glycol diisanonate; polyethylene glycol distearates, and mixtures thereof.

[0080] The compositions may also include, as fatty acid esters, esters and diesters of C6 to C30 fatty acid sugars, preferably C12 to C22. It is recalled that the term "sugar" means oxygenated hydrocarbon compounds possessing several alcohol functional groups, with or without aldehyde or ketone functional groups, and comprising at least four carbon atoms. These sugars may be monosaccharides, oligosaccharides, or polysaccharides.

[0081] Suitable sugars may be cited for example sucrose (or saccharose), glucose, galactose, ribose, fucose, maltose, fructose, mannose, arabinose, xylose, lactose, and their derivatives in particular alkylated, such as methylated derivatives like methylglucose.

[0082] Sugar and fatty acid esters may be selected in particular from the group comprising the esters or mixtures of sugar esters described above and fatty acids in the range of C6 to C30, preferably C12 to C22, linear or branched, saturated or unsaturated. If unsaturated, these compounds may comprise one to three carbon-carbon double bonds, conjugated or not.

[0083] The esters according to this variant can also be chosen from mono-, di-, tri- and tetra-esters, polyesters and their mixtures.

[0084] These esters can be, for example, oleate, laurate, palmitate, myristate, behenate, cocoate, stearate, linoleate, linolenate, caprate, arachidonate, or mixtures thereof, such as mixed oleo-palmitate, oleo-stearate, palmito-stearate esters.

[0085] More particularly, mono- and di- esters are used, and in particular mono- or di- oleate, stearate, behenate, oleopalmitate, linoleate, linolenate, oleostearate, of sucrose, glucose or methylglucose, and mixtures thereof.

[0086] One can cite as an example the product sold under the name Glucate® DO by the company Amerchol, which is a methylglucose dioleate.

[0087] Preferably, a liquid ester of monoacid and monoalcohol will be used.

[0088] The solid fats according to the invention preferably have a viscosity greater than 2 Pa.s, measured at 25°C and at a shear rate of 1 s *.

[0089] The solid fat(s) are preferably chosen from solid fatty alcohols, solid esters of fatty acids and / or fatty alcohols, waxes, ceramides, and mixtures thereof.

[0090] By "fatty alcohol" is meant a long-chain aliphatic alcohol comprising from 6 to 40 carbon atoms, preferably from 8 to 30 carbon atoms, and comprising at least one hydroxyl group OH. These fatty alcohols are neither oxyalkylated nor glycerolated.

[0091] Solid fatty alcohols can be saturated or unsaturated, linear or branched, and comprise from 8 to 40 carbon atoms, preferably from 10 to 30 carbon atoms. Preferably, solid fatty alcohols have the structure R-OH with R denoting a linear alkyl group, optionally substituted by one or more hydroxyl groups, comprising from 8 to 40, preferably from 10 to 30 carbon atoms, better from 10 to 30, or even from 12 to 24 atoms, even better from 14 to 22 carbon atoms.

[0092] The solid fatty alcohols that can be used are preferably chosen from saturated or unsaturated, linear or branched (mono)alcohols, preferably linear and saturated, comprising 8 to 40 carbon atoms, better 10 to 30, or even 12 to 24 atoms, even better 14 to 22 carbon atoms.

[0093] The solid fatty alcohols that may be used may be chosen from, alone or in mixture: myristic or myristyl alcohol (or 1-tetradecanol); cetyl alcohol (or 1-hexadecanol); stearyl alcohol (or 1-octadecanol); arachidyl alcohol (or 1-eicosanol); behenyl alcohol (or 1-docosanol); lignoceryl alcohol (or 1-tetracosanol); ceryl alcohol (or 1-hexacosanol); montanyyl alcohol (or 1-octacosanol); myricyl alcohol (or 1-triacontanol).

[0094] Preferably, the solid fatty alcohol is selected from cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, arachidic alcohol, and mixtures thereof, such as cetylstearyl or cetearyl alcohol. Particularly preferred, the solid fatty alcohol is selected from cetylstearyl or cetearyl alcohol and cetyl alcohol.

[0095] The solid fatty acid and / or fatty alcohol esters that may be used are preferably chosen from esters derived from C9-C26 carboxylic fatty acids and / or C9-C26 fatty alcohols.

[0096] Preferably, these solid fatty acid esters are esters of saturated linear or branched carboxylic acids comprising at least 10 carbon atoms, preferably from 10 to 30 carbon atoms and more particularly from 12 to 24 carbon atoms, and of saturated linear or branched monoalcohols comprising at least 10 carbon atoms, preferably from 10 to 30 carbon atoms and more particularly from 12 to 24 carbon atoms. The saturated carboxylic acids may optionally be hydroxylated, and are preferably monocarboxylic acids.

[0097] Esters of di- or tricarboxylic acids in C4-C22 and of alcohols in Ci-C22 and esters of mono-, di- or tricarboxylic acids and of di-, tri-, tetra- or pentahydroxylated alcohols in C2-C26 can also be used.

[0098] Examples include octyldodecyl behenate, isocetyl behenate, cetyl lactate, stearyl octanoate, octyl octanoate, cetyl octanoate, decyl oleate, hexyl stearate, octyl stearate, myristyle stearate, cetyl stearate, stearyl stearate, octyl pelargonate, cetyl myristate, myristyle myristate, stearyl myristate, diethyl sebacate, diisopropyl sebacate, diisopropyl adipate, din-propyl adipate, dioctyl adipate, maleate dioctyl, octyl palmitate, myristyle palmitate, cetyl palmitate, stearyl palmitate, and mixtures thereof.

[0099] Preferably, the solid fatty acid and / or fatty alcohol esters are selected from C9-C26 alkyl palmitates, in particular myristyle, cetyl, stearyl palmitates; C9-C26 alkyl myristates such as cetyl myristate, stearyl myristate and myristyle myristate; C9-C26 alkyl stearates, in particular myristyle, cetyl and stearyl stearates; and mixtures thereof.

[0100] A wax, as defined in the present invention, is a lipophilic compound, solid at 25°C and atmospheric pressure, with a reversible solid / liquid phase change, a melting point above approximately 40°C and up to 200°C, and exhibiting an anisotropic crystalline structure in the solid state. Generally, the size of the wax crystals is such that they diffract and / or scatter light, giving the composition a cloudy appearance. more or less opaque. By bringing the wax to its melting point, it is possible to make it miscible with oils and to form a microscopically homogeneous mixture, but by bringing the temperature of the mixture back to room temperature, we obtain a recrystallization of the wax, detectable microscopically and macroscopically (opalescence).

[0101] In particular, the waxes suitable for the invention can be chosen from waxes of animal, vegetable, mineral origin, non-siliconized synthetic waxes and their mixtures.

[0102] Examples include hydrocarbon waxes, such as beeswax, particularly of biological origin, lanolin wax, and Chinese insect waxes; rice bran wax, Camauba wax, Candellila wax, Ouricury wax, Alfa wax, Berry wax, Shellac wax, Japanese wax and sumac wax; Montan wax, orange and lemon waxes, microcrystalline waxes, paraffins and ozokerite; polyethylene waxes, waxes obtained by Fisher-Tropsch synthesis and waxy copolymers, as well as their esters.

[0103] We can also mention microcrystalline waxes in C2o to C60, such as Microwax HW.

[0104] We can also mention PM 500 polyethylene wax marketed under the reference Permalen 50-L polyethylene.

[0105] We can also mention waxes obtained by catalytic hydrogenation of animal or vegetable oils having linear or branched fatty chains, in C8 to C32. Among these, we can mention in particular isomerized jojoba oil, such as trans isomerized partially hydrogenated jojoba oil, in particular that manufactured or marketed by the company Desert Whale under the trade reference Iso-Jojoba-50®, hydrogenated sunflower oil, hydrogenated castor oil, hydrogenated coconut oil, hydrogenated lanolin oil, and di-(trimethyloi-1,1,1 propane tetrastearate), in particular that sold under the name Hest 2T-4S® by the company HETERENE.

[0106] Waxes obtained by hydrogenation of esterified castor oil with cetyl alcohol can also be used, such as those sold under the names Phytowax ricin 16L64® and 22L73® by the company SOPHIM.

[0107] As a wax, a C20 to C40 alkyl (hydroxystearyloxy)stearate (the alkyl group comprising 20 to 40 carbon atoms) can also be used, alone or in a mixture. Such a wax is notably sold under the names "Kester Wax K 82 P®", "Hydroxypolyester K 82 P®" and "Kester Wax K 80 P®" by the company KOSTER KEUNEN.

[0108] It is also possible to use microwaxes in the compositions of the invention;Examples include camauba microwaxes, such as the one marketed under the name MicroCare 350® by MICRO POWDERS; synthetic wax microwaxes, such as the one marketed under the name MicroEase 114S® by MICRO POWDERS; microwaxes made from a mixture of camauba wax and polyethylene wax, such as those marketed under the names Micro Care 300® and 310® by MICRO POWDERS; microwaxes made from a mixture of camauba wax and synthetic wax, such as the one marketed under the name Micro Care 325® by MICRO POWDERS; polyethylene microwaxes, such as those marketed under the names Micropoly 200®, 220®, 220L® and 250S® by MICRO POWDERS; and polytetrafluoroethylene microwaxes, such as those marketed under the names Microslip 519® and 519 L® by the company MICRO POWDERS. ;

[0109] Waxes are preferably chosen from mineral waxes such as paraffin wax, petroleum jelly, lignite or ozokerite; vegetable waxes such as cocoa butter or waxes from cork or sugar cane fibers, olive wax, rice wax, hydrogenated jojoba wax, Ouricoury wax, Camauba wax, Candelila wax, Alfa wax, or absolute flower waxes such as blackcurrant flower essential wax sold by the BERTIN company (France); waxes of animal origin such as beeswax or modified beeswax (cerabellina), spermaceti, lanolin wax and lanolin derivatives; microcrystalline waxes; and mixtures thereof.

[0110] Ceramides or ceramide analogues such as glycoceramides, which can be used in compositions according to the invention, are known; in particular, ceramides of classes I, II, III and V according to the DAWNING classification may be mentioned.

[0111] Ceramides or their analogues that may be used preferably correspond to the following formula: R3CH(OH)CH(CH2OR2)(NHCORi), in which: Ri designates an alkyl group, linear or branched, saturated or unsaturated, derived from fatty acids in Ci4-C30, this group being able to be substituted by a hydroxyl group in the alpha position, or a hydroxyl group in the omega position esterified by a saturated or unsaturated fatty acid in Ci6-C30; R2 denotes a hydrogen atom, a (glycosyl)n group, a (galactosyl)m group or a sulfogalactosyl group, where n is an integer ranging from 1 to 4 and m is an integer ranging from 1 to 8; R3 designates a hydrocarbon group in Ci5-C26, saturated or unsaturated in the alpha position, this group being able to be substituted by one or more alkyl groups in CrCi4; it being understood that in the case of natural ceramides or glycoceramides, R3 can also designate an alpha-hydroxyalkyl group in Ci5-C26, the hydroxyl group possibly being esterified by an alpha-hydroxy acid in Ci6-C30.

[0112] The ceramides most particularly preferred are the compounds for which Ri denotes a saturated or unsaturated alkyl derived from fatty acids in Ci6-C22; R2 denotes a hydrogen atom and R3 denotes a linear group saturated in Ci5.

[0113] Preferably, ceramides are used in which Ri designates a saturated or unsaturated alkyl group derived from fatty acids in Ci4-C30; R2 designates a galactosyl or sulfogalactosyl group; and R3 designates a -CH=CH-(CH2)i2-CH3 group.

[0114] Compounds can also be used in which Ri designates a saturated or unsaturated alkyl radical derived from fatty acids in C[2-C22]; R2 designates a galactosyl or sulfogalactosyl radical and R3 designates a hydrocarbon radical in Ci2-C22, saturated or unsaturated and preferably a -CH=CH-(CH2)i2-CH3 group.

[0115] As particularly preferred compounds, we may also mention 2-N-linoleoylamino-octadecane-l,3-diol; 2-N-oleoylamino-octadecane-l,3-diol; 2-N-palmitoylamino-octadecane-l,3-diol; 2-N-stearoylamino-octadecane-l,3-diol; 2-N-behenoylamino-octadecane-l,3-diol; 2-N-[2-hydroxy-palmitoyl]-amino-octadecane-l,3-diol; 2-N-stearoyl amino-octadecane-1,3,4-triol, and in particular N-stearoyl phytosphingosine, 2-N-palmitoylamino-hexadecane-1,3-diol, N-linoleoyldihydrosphingosine, N-oleoyldihydrosphingosine, N-palmitoyldihydrosphingosine, N-stearoyldihydrosphingosine, and N-behenoyldihydrosphingosine, N-docosanoyl N-methyl-D-glucamine, cetyl acid N-(2-hydroxyethyl)-N-(3-cetyloxy-2-hydroxypropyl)amide, and bis-(N-hydroxyethyl N-cetyl)malonamide; and mixtures thereof. Preferably, N-oleoyldihydrosphingosine shall be used.

[0116] Solid fats are preferably chosen from solid fatty alcohols, solid esters of fatty acids and / or fatty alcohols and mixtures thereof.

[0117] According to a preferred embodiment, the lightening composition implemented in the process according to the invention comprises at least one solid fat, preferably chosen from solid fatty alcohols, solid esters of fatty acids and / or fatty alcohols and mixtures thereof.

[0118] When present, the fat(s) other than fatty acids are preferably present in the lightening composition in a total content of 2 to 40% by weight, preferably 3 to 35% by weight, more preferably 4 to 30% by weight, better 5 to 25% by weight, relative to the total weight of the lightening composition. Surfactants different from fatty acids

[0119] The lightening composition implemented in the process according to the invention may further comprise one or more surfactants other than fatty acids.

[0120] Preferably, the lightening composition implemented in the process according to the invention comprises one or more surfactants other than fatty acids.

[0121] These may preferably be chosen from anionic surfactants, amphoteric surfactants, non-ionic surfactants, cationic surfactants and / or mixtures thereof, more preferably from anionic surfactants, non-ionic surfactants and / or mixtures thereof.

[0122] Preferably, the lightening composition implemented in the process according to the invention comprises one or more non-ionic surfactants.

[0123] The non-ionic surfactant(s) usable in the lightening composition implemented in the process of the present invention are described in particular, for example, in "Handbook of Surfactants" by MR PORTER, Blackie & Son (Glasgow and London), 1991, pp. 116-178.

[0124] Examples of non-ionic surfactants include the following compounds, alone or in mixtures: - alkyl(C8-C24)oxyalkylened phenols; - alcohols in the C8 to C40 range, saturated or unsaturated, linear or branched, oxyalkylated or glycerolated, preferably include one or two fatty chains; - C8 to C30 fatty acid amides, saturated or unsaturated, linear or branched, oxyalkylated; - esters of C8 to C30 acids, saturated or unsaturated, linear or branched, and of polyethylene glycols; - fatty acid and sucrose esters, - esters of C8 to C30 acids, saturated or unsaturated, linear or branched, and of sorbitol, preferably oxygenated; - C8-C30 fatty acid esters, saturated or unsaturated, linear or branched, and glycerol; - C8-C30 fatty acid esters and sorbitan, - C8-C30 fatty acid esters and polyoxyethylenated sorbitan, - alkyl(C8-C3O)(poly)glucosides, alkenyl(C8-C3O)(poly)glucosides, possibly oxyalkylated (0 to 10 oxyalkylated motifs) and comprising 1 to 15 glucose motifs, alkyl (C8-C3O)(poly)glucoside esters, - oxyethylenated vegetable oils, saturated or unsaturated; - ethylene oxide and / or propylene oxide condensates; - A-alkyl(C8-C30)glucamine and A-acyl(C8-C30)-methylglucamine derivatives; - amine oxides.

[0125] They are chosen, in particular, from among alcohols, alpha-diols, alkyl(CrC 2o)phenols, these compounds being ethoxylated, propoxylated or glycerolated, and having at least one fatty chain comprising, for example, from 8 to 24 carbon atoms, preferably from 8 to 18 carbon atoms, the number of ethylene oxide or propylene oxide groups being able to range in particular from 1 to 200 and the number of glycerol groups being able to range in particular from 1 to 30.

[0126] Other examples include ethylene oxide and propylene oxide condensates on fatty alcohols; ethoxylated fatty amides preferably having 1 to 30 ethylene oxide motifs; polyglycerol fatty amides having on average 1 to 5 glycerol groups and in particular 1.5 to 4; fatty acid esters of sucrose; fatty acid esters of polyethylene glycol; oxyethylenated vegetable oils; N-(C6-C24 alkyl)glucamine derivatives; amine oxides such as (C10-C14 alkyl)amine oxides or N-(C10-C14 acyl)aminopropylmorpholine oxides.

[0127] Esters (in particular mono, di, tri esters) of C8-C30 fatty acids, preferably C12-C22, and of sorbitan may be selected from: Sorbitan Caprylate; Sorbitan Cocoate; Sorbitan Isostearate; Sorbitan Laurate; Sorbitan Oleate; Sorbitan Palmitate; Sorbitan Stearate; Sorbitan Diisostearate; Sorbitan Dioleate; Sorbitan Distearate; Sorbitan Sesquicaprylate; Sorbitan Sesquiisostearate; Sorbitan Sesquioleate; Sorbitan Sesquistearate; Sorbitan Triisostearate; Sorbitan Trioleate; Sorbitan Tristearate.

[0128] Esters (in particular mono, di, tri esters) of C8-C30 fatty acids and polyoxyethylenated sorbitan are preferably selected from C8-C30 fatty acid and oxyethylenated sorbitan ester(s) having 1 to 30 ethylene oxide motifs, preferably 2 to 20 ethylene oxide motifs, preferably still 2 to 10 ethylene oxide motifs.

[0129] Preferably, the C8-C30 fatty acid and oxyethylenated sorbitan ester(s) is / are selected from Ci2-Ci8 fatty acid and oxyethylenated sorbitan esters, in particular from oxyethylenated lauric acid, myristic acid, cetyl acid and stearic acid and sorbitan esters.

[0130] Preferably, the C8-C30 fatty acid ester(s) and oxyethylenated sorbitan is / are selected from oxyethylenated sorbitan monolaurate (4 EO) (POLYSORBATE-21), oxyethylenated sorbitan monolaurate (20 EO) (POLYSORBATE-20), oxyethylenated sorbitan monopalmitate (20 EO) (POLYSORBATE-40), oxyethylenated sorbitan monostearate (20 EO) (POLYSORBATE-60), oxyethylenated sorbitan monostearate (4 EO) (POLYSORBATE-61), oxyethylenated sorbitan monooleate (20 OE) (POLYSORBATE-80), oxyethylenated sorbitan monooleate (5 OE) (POLYSORBATE-81), oxyethylenated sorbitan tristearate (20 OE) (POLYSORBATE-65), oxyethylenated sorbitan trioleate (20 OE) (POLYSORBATE-85).

[0131] The non-ionic surfactant(s) are preferably selected from C8-C24 ethoxylated fatty alcohols comprising from 1 to 200 ethylene oxide groups, preferably from 1 to 50 ethylene oxide groups, C6-C24 (alkyl) polyglycosides, C8-C30 fatty acid esters, saturated or unsaturated, linear or branched, and of glycerol, C8-C30 fatty acid esters and of oxyethylenated sorbitan, and mixtures thereof, preferably from C8-C24 ethoxylated fatty alcohols comprising from 1 to 50 ethylene oxide groups, C6-C24 (alkyl) polyglycosides, C8-C30 fatty acid esters, saturated or unsaturated, linear or branched, and of glycerol.

[0132] More preferably, the non-ionic surfactant(s) are chosen from C8-C24 ethoxylated fatty alcohols comprising from 1 to 200 ethylene oxide groups, preferably from 1 to 50 ethylene oxide groups.

[0133] Preferably, the brightening composition implemented in the process according to the invention comprises one or more C8-C24 ethoxylated fatty alcohols comprising from 1 to 200 ethylene oxide groups, preferably from 1 to 50 ethylene oxide groups.

[0134] When present, the surfactant(s) other than fatty acids are preferably present in the lightening composition implemented in the process according to the invention in a total content ranging from 0.01 to 20% by weight, more preferably from 0.1 to 15% by weight, better from 0.5 to 10% by weight relative to the total weight of the composition which contains them.

[0135] When present, the non-ionic and / or anionic surfactant(s) other than fatty acids are preferably present in the composition(s) according to the invention in a total content ranging from 0.1 to 20% by weight, more preferably from 0.5 to 15% by weight, better from 1 to 12% by weight relative to the total weight of the composition which contains them.

[0136] When present, the non-ionic surfactant(s) are preferably present in the composition(s) according to the invention in a total content ranging from 0.1 to 20% by weight, more preferably from 0.5 to 15% by weight, better from 1 to 12% by weight relative to the total weight of the composition which contains them. Organic solvent

[0137] The brightening composition implemented in the process according to the invention may comprise one or more organic solvent(s).

[0138] Preferably, the brightening composition implemented in the process according to the invention comprises one or more organic solvent(s).

[0139] Examples of organic solvents include linear or branched C2-C4 alkanols such as ethanol and isopropanol; polyols and polyol ethers such as glycerol, 2-butoxyethanol, propylene glycol, dipropylene glycol, propane-1,3-diol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, as well as aromatic alcohols or ethers such as benzyl alcohol or phenoxyethanol, and mixtures thereof.

[0140] When present, the organic solvent(s) are preferably present in the brightening composition in a total content of 0.01 to 30% by weight, preferably of 0.05 to 15% by weight, preferably of 0.1 to 10% by weight relative to the total weight of the brightening composition.

[0141] The lightening composition is preferably an aqueous composition. In particular, it comprises more than 10% by weight of water, preferably more than 30% by weight of water, and even more advantageously more than 50% by weight of water. Preferably, the lightening composition comprises water in a content ranging from 10% to 95% by weight, preferably from 30% to 90% by weight, and more preferably from 50% to 85% by weight relative to the total weight of the lightening composition.

[0142] Preferably, the pH of the brightening composition used in the process of the invention is between 8 and 13, preferably between 9 and 12.

[0143] The lightening composition according to the invention may optionally include one or more additives, among which may be mentioned anionic, non-ionic, amphoteric, cationic polymers or mixtures thereof, mineral thickening agents, anti-dandruff agents, anti-seborrheic agents, anti-hair loss and / or regrowth agents, vitamins and pro-vitamins including panthenol, sunscreens, mineral or organic pigments, plasticizers, solubilizing agents, opacifying or pearlescent agents, antioxidants, sequestering agents, perfumes, preservatives.

[0144] Of course, the person skilled in the art will take care to choose this or these possible complementary compounds in such a way that the advantageous properties intrinsically attached to the lightening composition are not, or substantially not, altered by the envisaged addition(s).

[0145] The above additives may generally be present in quantities of each of them between 0 and 20% by weight, relative to the total weight of the lightening composition.

[0146] Preferably, the lightening composition just described is obtained at the time of use, by mixing an oxidizing composition comprising the chemical oxidizing agent(s) with an alkaline composition comprising the alkaline agent(s).

[0147] Oxidizing composition

[0148] In addition to the chemical oxidizing agent(s), the oxidizing composition may include one or more fats as defined above, preferably chosen from fatty alcohols, one or more surfactants as defined above, preferably chosen from non-ionic surfactants, one or more solvent(s) as defined above.

[0149] The oxidizing composition also preferably comprises one or more acidifying agents. Examples of acidifying agents include mineral or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid, and sulfonic acids.

[0150] The oxidizing composition is preferably an aqueous composition. In particular, it comprises more than 10% by weight of water, preferably more than 30% by weight of water, and even more advantageously more than 50% by weight of water. Preferably, the oxidizing composition comprises water in a content ranging from 10% to 95% by weight, preferably from 30% to 93% by weight, and more preferably from 50% to 92% by weight relative to the total weight of the oxidizing composition.

[0151] The pH of the oxidizing composition is preferably less than 7, preferably between 1 and 5, preferably between 1.5 and 4.5. This pH can be adjusted to the desired value by the use of one or more acidifying agents, which can in particular be chosen from those described above.

[0152] Alkaline composition

[0153] In addition to the alkali agent(s) described above, the alkaline composition may include one or more fatty acids as defined above, one or more fats as defined above, preferably chosen from solid fatty alcohols, solid esters of fatty acids and / or fatty alcohols and their mixtures, one or more surfactants as defined above, preferably chosen from non-ionic surfactants, one or more solvent(s) as defined above.

[0154] The alkaline composition is preferably an aqueous composition. In particular, it comprises water in a content ranging from 5% to 80% by weight, preferably from 10% to 70% by weight, better from 20% to 50% by weight relative to the total weight of the alkaline composition.

[0155] The pH of the alkaline composition, when aqueous, is preferably from 8 to 12, preferably from 9 to 11, better from 10 to 11. Coloring composition Direct dyes

[0156] The colouring composition implemented in the process of the invention comprises one or more direct colour(s).

[0157] By "direct dye" we mean colored species. These are dyes that will diffuse superficially onto the fiber.

[0158] The direct dye(s) usable according to the invention are chosen from natural direct dyes, synthetic direct dyes, and their mixtures.

[0159] Preferably, the direct dye(s) usable according to the invention are chosen from among ionic direct dyes and non-ionic direct dyes, more particularly from among cationic direct dyes, amphoteric direct dyes, anionic direct dyes, non-ionic direct dyes, and mixtures thereof.

[0160] Direct dyes are for example chosen from among benzene nitrate direct dyes, azo direct dyes, tetraazapentamethinic dyes, quinonic dyes and in particular anthraquinone dyes, azinic direct dyes, triarylmethanic direct dyes, azomethine direct dyes and natural direct dyes.

[0161] The colouring composition may include one or more non-ionic direct dyes.

[0162] Among the non-ionic direct dyes, we can mention neutral benzene nitro direct dyes, neutral azo direct dyes, neutral anthraquinone dyes.

[0163] The colouring composition may include one or more cationic direct dyes.

[0164] By "cationic direct dye" is meant any dye other than oxidation dyes, commonly called "basic" direct dyes or "basic dyes". They are called basic because of their affinity for acidic substances, having in their structure at least one endo- or exocyclic cationic or cationizable group.

[0165] The cationic direct dye(s) contain at least one quaternized cationic chromophore or at least one chromophore bearing a quatemized or quatemisable cationic group.

[0166] According to a particular embodiment of the invention, the cationic direct dyes comprise at least one quantified cationic chromophore.

[0167] As examples of cationic direct dyes according to the invention, the following may be cited: acridine dyes; acridones; anthranthrones; anthrapyrimidines; anthraquinones; azines; (poly)azoic, hydrazono or hydrazones, in particular arylhydrazones; azomethines; benzantrones; benzimidazoles; benzimidazolones; benzindoles; benzoxazoles; benzopyrans; benzothiazoles; benzoquinones; bisazines; bisisoindolines; carboxanilides; coumarins; cyanines such as azacarbocyanines, diazacarbocyanines, diazahemicyanines, hemicyanines, or tetraazacarbocyanines; diazines; diketopyrrolopyrroles; dioxazines; diphenylamines; diphenylmethanes; dithiazines; flavonoids such as flavanthones and flavones; fluorindines; formazans; indamines; indanthrones; indigoids and pseudo-indigoids; indophenols; indoanilines; isoindolines; isoindolinones; isoviolanthrones; lactones; (Poly)methines such as stilbene or styryl-type dimethines; naphthalimides; naphthanilides; naphtholactams; naphthoquinones; nitro, including (hetero)aromatic nitro; oxadiazoles; oxazines; perilones; perinones; perylenes; phenazines; phenoxazine; phenothiazines; phthalocyanine; polyenes / carotenoids; porphyrins; pyrantrones; pyrazolantrones; pyrazolones; pyrimidinoantrones; pyronines; quinacridones; quinolines; quinophthalones; squaranes; tetrazoliums; thiazines, thioindigo; thiopyronines; triarylmethanes, or xanthenes.

[0168] For cationic azo dyes, particular mention can be made of those derived from the cationic dyes described in the Kirk-Othmer Encyclopedia of Chemical Technology, “Dyes, Azo”, J. Wiley & sons, updated on 19 / 04 / 2010.

[0169] Among the azo dyes that can be used according to the invention, cationic azo dyes described in patent applications WO 95 / 15144, WO 95 / 01772 and EP 714954 can be mentioned.

[0170] The following compounds may be cited among the azo dyes described in the Colour Index International, 3rd edition: -Basic Red 22 -Basic Red 76 -Basic Yellow 57 -Basic Brown 16 -Basic Brown 17.

[0171] Among the cationic quinone dyes, those mentioned in the aforementioned Colour Index International are suitable, and among these, the following dyes may be cited, among others: -Basic Blue 22 -Basic Blue 99.

[0172] Suitable azinic dyes include those listed in the Colour Index International, for example the following dyes: -Basic Blue 17 -Basic Red 2.

[0173] Among the cationic triarylmethane dyes that can be used according to the invention, the following dyes may be mentioned, in addition to those listed in the Colour Index: -Basic Green 1 -Basic Violet 3 -Basic Violet 14 -Basic Blue 7 -Basic Blue 26.

[0174] Cationic dyes can also be cited in documents US 5888252, EP 1133975, WO 03 / 029359, EP 860636, WO 95 / 01772, WO 95 / 15144, EP 714954. Also cited are those listed in the encyclopedia "The chemistry of synthetic dye" by K. VENKATARAMAN, 1952, Academy Press vol 1 to 7, in the "Kirk-Othmer" encyclopedia "Chemical technology", chapter "Dyes and Dye intermediate", 1993, Wiley and sons, and in various chapters of the encyclopedia "ULLMANN's ENCYCLOPEDIA of Industrial chemistry" 7th edition, Wiley and sons.

[0175] Preferably, cationic direct dyes are chosen from those derived from azo and hydrazono type dyes.

[0176] According to a particular embodiment, the direct dyes are cationic azoic dyes, described in EP 850636, FR 2788433, EP 920856, WO 9948465, FR 2757385, EP 85063, WO 850638, WO 9948433 9744004, FR 2570946, FR 2285851, DE 2538363, FR 2189006, FR 1560664, FR 1540423, FR 1567219, FR 1516943, FR 1212, 228 DE 4137005, WO 0166646, US 5708151, WO 9501772, WO 515144, GB 1195386, US 3524842, US 5879413, EP 1062940, EP 113938, DE 61387, DE 2527638, FR 2275462, GB 1974-27645, Acta Histochem. (1978), 61(1), 48-52 ; Cytology (1968), 10(3), 403-5 ; Zh. Obshch. Khim. (1970), 40(1), 195-202 ; Ann. Say. (Rome) (1975), 65(5-6), 305-14 ; Journal of the Chinese Chemical Society (Taipei) (1998), 45(1), 209-211 ; Rev. Rome. Say. (1988), 33(4), 377-83 ; Text. Nothing. J. (1984), 54(2), 105-7 ; Say. Ind. (Milan) (1974), 56(9), 600-3 ; Khim. Technol. (1979), 22(5), 548-53 ; Word. Monatsh. Chem. (1975), 106(3), 643-8 ; MRL Bull. Nothing. 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. .

[0177] Preferably, the cationic direct dye(s) comprise a quaternary ammonium group, more preferably the cationic charge is endocyclic.

[0178] Ces radicaux cationiques sont par exemple un radical cationique : - à charge exocyclique (di / tri)(Ci-C8)alkylammonium, ou - à charge endocyclique tels que comprenant un groupe hétéroaryle cationique choisi parmi : acridinium, benzimidazolium, benzobistriazolium, benzopyrazolium, benzopyridazinium, benzoquinolium, benzothiazolium, benzotriazolium, benzoxazolium, bi-pyridinium, bis-tétrazolium, dihydrothiazolium, imidazopyridinium, imidazolium, indolium, isoquinolium, naphthoimidazolium, naphthooxazolium, naphthopyrazolium, oxadiazolium, oxazolium, oxazolopyridinium, oxonium, phénazinium, phénooxazolium, pyrazinium, pyrazolium, pyrazoyltriazolium, pyridinium, pyridinoimidazolium, pyrrolium, pyrylium, quinolium, tétrazolium, thiadiazolium, thiazolium, thiazolopyridinium, thiazoylimidazolium, thiopyrylium, triazolium ou xanthylium.

[0179] Examples include hydrazono cationic dyes of formula (C-II) and (C-III), azo dyes of formula (C-IV) and (C-V), as well as their optical, geometric, tautomeric isomers, their salts of organic or mineral acids or bases, and their solvates such as hydrates:

[0180] Hét+-C(Ra)=NN(Rb)-Ar, Q (C-II)

[0181] Hét+-N(Ra)-N=C(Rb)-Ar, Q (C-III)

[0182] Het+-N=N-Ar, Q (C-IV)

[0183] Ar+-N=N-Ar”, Q (CV),

[0184] formulas (C-II) to (CV) wherein: * Het+ represents a cationic heteroaryl radical, preferably with endocyclic cationic charge such as imidazolium, indolium, or pyridinium, possibly preferentially substituted by at least one (Ci-C8)alkyl group such as methyl; * Ar+ represents an aryl radical, such as phenyl or naphthyl, with an exocyclic cationic charge, preferably ammonium, particularly tri(Ci-C8)alkyl-ammonium such as trimethylammonium; * Ar represents an aryl group, in particular phenyl, possibly substituted, preferably by one or more electron-donating groups such as i) (CrC8)alkyl possibly substituted, ii) (Ci-C8)alkoxy possibly substituted, iii) (di)(CrC8)(alkyl)amino possibly substituted on the alkyl group(s) by a hydroxyl group, iv) aryl(Ci-C8)alkylamino, v) N-(Ci-C8)alkyl-N-aryl(Ci-C8)alkylamino possibly substituted or else Ar represents a julolidine group; * Ar” represents a (hetero)aryl group possibly substituted such as phenyl or pyrazolyl possibly substituted, preferably by one or more (CrC8)alkyl, hydroxyl, (di)(Ci-C8)(alkyl)amino, (CrC8)alkoxy or phenyl groups; * Ra and Rb, identical or different, representing a hydrogen atom or a (CrC8)alkyl group possibly substituted, preferably by a hydroxyl group; * or the substituent Ra with a substituent of Het+ and / or Rb with a substituent of Ar together form with the atoms that bear them a (hetero)cycloalkyl; particularly Ra and Rb, representing a hydrogen atom or a (Cr C4)alkyl group possibly substituted by a hydroxyl group; * Q represents an organic or mineral anionic counter-ion such as a halide or alkyl sulfate.

[0185] In particular, one may cite the endocyclic cationic direct dyes of azo and hydrazono of formula (C-II) to (CV) as defined above; more particularly the endocyclic cationic direct dyes of formula (C-II) to (CV) described in patent applications WO 95 / 15144, WO 95 / 01772 and EP-714954.

[0186] Preferably, the following direct dyes may be mentioned: R4 (C-II-1),

[0187] formulas (C-II-1) and (C-IV-1) in which: - R1 represents an (Ci-C4)alkyl group such as methyl; - R2 and R3, whether identical or different, represent a hydrogen atom or an (Ci-C4)alkyl group such as methyl; and - R4 represents a hydrogen atom or an electron-donating group such as (Ci-C8)alkyl possibly substituted, (CrC8)alkoxy possibly substituted, (di)(Ci-C8)(alkyl)amino possibly substituted on the alkyl group(s) by a hydroxyl group; particularly R4 is a hydrogen atom, - Z represents a CH group or a nitrogen atom, preferably CH, - Q is an anionic counterion as defined previously particularly a halide such as chloride or an alkyl sulfate such as methyl sulfate or mesytyl.

[0188] In particular, colorants of formula (C-II-1) and (C-IV-1) are selected from Basic Red 51, Basic Yellow 87 and Basic Orange 31 or their derivatives: Basic Red 51 Basic Yellow 87,

[0189] with Q' an anionic counter ion as defined above, particularly a halide such as chloride or an alkyl sulfate such as methyl sulfate or mesytyl.

[0190] According to a particular embodiment of the invention, the direct dyes are fluorescent, that is to say they contain at least one fluorescent chromophore as defined above.

[0191] Examples of fluorescent dyes include radicals derived from the dyes acridines, acridones, benzantrones, benzimidazoles, benzimidazolones, benzindoles, benzoxazoles, benzopyranes, benzothiazoles, coumarins, difluoro{2-[(2H-pyrrol-2-ylidene-kN)methyl]-1H-pyrrolato-kN]bores (BODIPY®), diketopyrrolo-pyrroles, fluorindines, (poly)methines (including cyanines and styryls / hemicyanines), naphthalimides, naphthanilides, naphthylamine (such as dansyls), oxadiazoles, oxazines, perilones, perinones, perylenes, polyenes / carotenoids, squaranes, stilbenes, xanthenes.

[0192] Also noteworthy are the fluorescent dyes described in documents EP 1133975, WO 03 / 029359, EP 860636, WO 95 / 01772, WO 95 / 15144, EP 714954 and those listed in K. Venkataraman's "The Chemistry of Synthetic Dye," 1952, Academy Press, vols. 1-7, in the Kirk-Othmer Encyclopedia "Chemical Technology," chapter "Dyes and Dye Intermediates," 1993, Wiley and Sons, and in various chapters of Ullmann's Encyclopedia of Industrial Chemistry, 7th edition, Wiley and Sons, and in The Handbook — A Guide to Fluorescent Probes and Labeling Technologies, 1st ed. Molecular Probes / Invitrogen - Oregon 2005 distributed via the Internet or in previous printed editions.

[0193] According to one embodiment of the invention, the cationic dye(s) are fluorescent and comprise at least one quaternary ammonium radical such as those of the following (C-VI) formula, as well as their optical, geometric, tautomeric isomers, their salts of organic or mineral acids or bases, and their solvates such as hydrates:

[0194] W+-[C(Rc)=C(Rd)]m'-Ar, Q (C-VI),

[0195] formula (C-VI) wherein: * W+ represents a cationic heterocyclic or heteroaryl group, particularly comprising a quaternary ammonium possibly substituted by one or more (CrC8)alkyl groups possibly substituted in particular by one or more hydroxyl groups; * Ar representing an aryl group such as phenyl or naphthyl, possibly substituted preferably by i) one or more halogen atoms, such as chlorine, fluorine; ii) one or more (Ci-C8)alkyl groups, preferably in Ci-C4 such as methyl; iii) one or more hydroxyl groups; iv) one or more (CrC8)alkoxy groups such as methoxy; v) one or more hydroxy(Ci-C8)alkyl groups such as hydroxyethyl; vi) one or more amino or (di)(Ci-C8)alkylamino groups, preferably with the alkyl portion in Ci-C4 possibly substituted by one or more hydroxyl groups such as (di)hydroxyethylamino; vii) by one or more acylamino groups; viii) one or more heterocycloalkyl groups such as pyperazinyl, pyperidinyl or 5 or 6-membered heteroaryl groups such as pyrrolidinyl, pyridinyl and imidazolinyl; * m' represents an integer between 1 and 4 inclusive, particularly m is 1 or 2; more preferably 1; * Rc, Rd, identical or different, represent a hydrogen atom or a (Ci-C8)alkyl group possibly substituted, preferably at C1-C4, or else Rc contiguous to W+ and / or Rd contiguous to Ar form with the atoms that bear them a (hetero)cycloalkyl, particularly Rc is contiguous to W+ and form a (hetero)cycloalkyl such as cyclohexyl; * Q is an organic or mineral anionic counterion as defined above.

[0196] Among cationic direct dyes, triarylmethane cationic dyes may also be mentioned.

[0197] Preferably, the triarylmethane cationic direct dye(s) according to the invention are chosen from the following cationic dyes of formulas (C-VII) and (C-VII'): (C-VII),

[0198] as well as its addition salts with an acid or a base, organic or mineral, its geometric, optical, tautomeric isomers, and its mesomeric forms, its solvates such as hydrates,

[0199] preceding formulas (C-VII) and (C-VII') in which: * Ri, R2, Ri and R4, whether identical or different, represent a hydrogen atom or a (Ci-C6)alkyl group, possibly substituted, preferably by a hydroxyl group; aryl such as phenyl, aryl(Ci-C4)alkyl such as benzyl, heteroaryl, heteroaryl(Ci-C4)alkyl, or two groups Ri and R2, and / or R3 and Ri, on the same nitrogen atom, together with the nitrogen atom on which they are based, form a heterocycloalkyl group, possibly substituted, such as morpholino, piparazino, piperidino, preferably RB. R2, R3 and Ri, whether identical or different, represent a hydrogen atom or a (Ci-C4)alkyl group. * R5, R6, R7, R8, R9, Rio, Ru, Ri2, Ri3, Ri4, Rb and R16, identical or different, represent a hydrogen atom, a halogen, or a group chosen from i) hydroxy, ii) thiol, iii) amino iv) (di)(Ci-C4)(alkyl)amino, v) (di)arylamino such as (di)phenylamino, vi) nitro, vii) acylamino (-NR-C(O)R') in which the radical R is a hydrogen atom, a Ci-C4 alkyl radical possibly bearing at least one hydroxyl group and the radical R' is a CrC2 alkyl radical; viii) carbamoyl ((R)2N-C(O)-) in which the radicals R, identical or not, represent a hydrogen atom, a CrC4 alkyl radical possibly bearing at least one hydroxyl group; ix) carboxylic acid or ester, (-OC(O)R') or

[0200] (-C(O)OR'), in which the radical R' is a hydrogen atom, or alkyl in Ci -C4 possibly bearing at least one hydroxyl group and the radical R' is a Ci-C2 alkyl radical; x) alkyl possibly substituted in particular by a hydroxy group; xi) alkylsulfonylamino (R'SO2-NR-) in which the radical R represents a hydrogen atom, a C1-C4 alkyl radical possibly bearing at least one hydroxyl group and the radical R' represents a CrC4 alkyl radical, a phenyl radical; xii) aminosulfonyl ((R)2N-SO2 ) in which the radicals R, identical or not, represent a hydrogen atom, a CrC4 alkyl radical possibly bearing at least one hydroxyl group, xiii) (Ci-C4)alkoxy, and xiv) (Ci-C4)alkylthio;* Or, two radicals carried by two adjacent carbon atoms R5 and R6 and / or R7 and R8, and / or R9 and R10 and / or Ru and Rn and / or Rn and RM and / or Rb and R6 together with the carbon atoms that support them form a condensed 6-membered aryl or heteroaryl ring, preferably benzo, said ring possibly being further substituted, preferably an unsubstituted benzo ring; * Q represents an anionic counter ion to achieve electroneutrality, preferably chosen from halides such as chloride, bromide, and phosphate.

[0201] When the cationic dye includes one or more anionic substituents such as COOR or SO3R with R denoting a hydrogen or a cation, it is understood that there are then more cationic substituents than anionic substituents, so that the overall resulting charge of the triarylmethane structure is cationic.

[0202] According to a preferred embodiment, the triarylmethane dye(s) is / are selected from those of formula (C-VII) or (C-VII'), wherein, taken together or separately, - Rb, R2, R3 and Ri represent a hydrogen atom or an (CrC4)alkyl group such as methyl or ethyl, - R5, R6, R7, R8, R9, Rio, Ru, Ri2, Ri3, Ri4, Rb and R[6, represent a hydrogen atom, a halogen such as chlorine, or a (Ci-C4)alkyl group such as methyl or ethyl, an amino group, a (di)(CrC4)(alkyl)amino group and, preferably, at least one of the groups R9, Rio, Ru or R[2 represents a hydrogen atom, a halogen (Cl), or an amino group, or a (Ci-C4)(alkyl)amino or (di)(Ci-C4) (alkyl)amino group, preferably in the para position of the phenyl group.

[0203] Preferably, the direct triarylmethane structure dye(s) are chosen from Basic Violet 1, Basic Violet 2, Basic Violet 3, Basic Violet 4, Basic Violet 14, Basic Blue 1, Basic Blue 7, Basic Blue 26, Basic green 1, Basic Blue 77 (also called HC Blue 15), and mixtures thereof.

[0204] Among cationic direct dyes, anthraquinone cationic dyes can also be mentioned.

[0205] The anthraquinone cationic direct dye(s) usable in the coloring composition of the invention comprise a quaternary ammonium group.

[0206] These cationic radicals are, for example, a cationic radical: - with an exocyclic charge (Ci-C8)alkylammonium, or - à charge endocyclique tels que comprenant un groupe hétéroaryle cationique choisi parmi : acridinium, benzimidazolium, benzobistriazolium, benzopyrazolium, benzopyridazinium, benzoquinolium, benzothiazolium, benzotriazolium, benzoxazolium, bi-pyridinium, bis-tétrazolium, dihydrothiazolium, imidazopyridinium, imidazolium, indolium, isoquinolium, naphthoimidazolium, naphthooxazolium, naphthopyrazolium, oxadiazolium, oxazolium, oxazolopyridinium, oxonium, phénazinium, phénooxazolium, pyrazinium, pyrazolium, pyrazoyltriazolium, pyridinium, pyridinoimidazolium, pyrrolium, pyrylium , quinolium, tétrazolium, thiadiazolium, thiazolium, thiazolopyridinium, thiazoylimidazolium, thiopyrylium, triazolium ou xanthylium.

[0207] De préférence, la charge cationique est exocyclique.

[0208] Parmi les colorants directs cationiques anthraquinoniques, on préfère ceux de formule (C-VIII) ayant une charge cationique exocyclique : (c-vm)

[0209] in which: - R1, R2 and R3, identical or different, representing a hydrogen atom or a (CrC8)alkyl group possibly substituted; - R4 representing a hydrogen atom or a (CrC8)alkyl group possibly substituted; - R5 represents a hydrogen atom, a (Ci-C8)alkyl group (possibly substituted), a (CrC8)alkylene group (possibly substituted), a halogen, a hydroxyl group, or a (Ci-C8)alkoxy group - n representing a number between 1 and 8; - Q represents an organic or mineral anionic counter-ion such as a halide or an alkyl sulfate.

[0210] Preferably, in formula (C-VIII): - R1, R2 and R3, identical or different, representing a (Ci-C6)alkyl group possibly substituted; - R4 representing a hydrogen atom or possibly substituted (Ci-C6)alkyl group; - R5 representing a hydrogen atom or a (Ci-C8)alkyl group, possibly substituted, - n representing a number between 1 and 6; - Q representing a halide or an alkyl sulfate.

[0211] More preferably, in formula (CVIII): - R1, R2 and R3, identical or different, representing a (Ci-C3)alkyl group possibly substituted; - R4 representing a hydrogen atom or a methyl group; preferably a methyl group - R5 representing a hydrogen atom or a methyl group, preferably a hydrogen atom; - n representing a number between 2 and 4; - Q representing a halide or an alkyl sulfate, preferably a halide.

[0212] Among the dyes of formula (C-VIII), the following dyes of formula (C-VIII') or formula (C-VIII”) may be used in particular:

[0213] with Q an anionic counter ion, particularly a halide such as bromide or chloride, or an alkyl sulfate such as methyl sulfate or mesytyl. Preferably Q is a halide, better, a bromide.

[0214] By "anionic counter-ion" is meant an anion or anionic group derived from a salt of an organic or mineral acid that counterbalances the cationic charge of the dye; more particularly, the anionic counter-ion is selected from i) halides such as chloride, bromide; ii) nitrates; iii) sulfonates, including Ci-C6 alkylsulfonates: Alk-S(O)2O- such as methylsulfonate or mesylate and ethylsulfonate; iv) arylsulfonates: Ar-S(O)2O- such as benzenesulfonate and toluenesulfonate or tosylate; v) citrate; vi) succinate; vii) tartrate; viii) lactate; ix) alkyl sulfates: Alk-OS(O)O- such as methysulfate and ethylsulfate; x) arylsulfates: Ar-OS(O)O- such as benzene sulfate and toluene sulfate; xi) alkoxysulfates: Alk-OS(O)2O- such as methoxy sulfate and ethoxysulfate;xii) aryloxysulfates: Ar-OS(O)2O-, xiii) phosphates O=P(OH)2-O-, O=P(O-)2-OH O=P(O-)3, HO-[P(O)(O-)]wP(O)(O-)2 with w being an integer; xiv) acetate; xv) triflate; and xvi) borates such as tetrafluoroborate, xvii) disulfate (O=)2S(O-)2 or SO42 and monosulfate HSO4. ;

[0215] A dye of formula (C-VIII') particularly preferred is HC Blue 17.

[0216] A dye of formula (C-VIII”) particularly preferred is HC Blue 16 (l-methylamino-4-(3'-dimethylpropylammoniumpropylamino)antraquinone bromide).

[0217] Preferably, the anthraquinone cationic direct dye(s) are chosen from dyes of formula (C-VIII') and (C-VIII”), and more preferably from dyes of formula (C-VIII”), better from HC Blue 16.

[0218] The colouring composition according to the invention may comprise one or more anionic direct dyes.

[0219] The anionic direct dyes of the invention are dyes commonly called "acid" direct dyes because of their affinity for alkali substances. Anionic direct dyes are defined as any direct dye having in its structure at least one CO2R or SO3R substituent, where R designates a hydrogen atom or a cation from a metal or an amine, or an ammonium ion. Anionic dyes can be selected from acidic nitro direct dyes, acidic azo dyes, acidic azinic dyes, acidic triarylmethanic dyes, acidic indoamine dyes, acidic anthraquinone dyes, acidic indigoid dyes, and acidic natural dyes.

[0220]

[0221] According to the invention, the anionic direct dye(s) can be chosen, alone or in mixture, from the following anionic direct dyes of formulas (A-II), (A-II'), (A-III), (A-II'), (A-IV), (A-IV'), (AV), (A-V'), (A-VI), (A-VII), (A-VIII) and (A-IX): a) Diaryl anionic azo dyes of formula (A-II) or (A-II'):

[0222] formulas (A-II) and (A-II') in which: * R7, R8, R9, Rio, R'7, R'8, R'9 and R'i0, whether identical or different, represent a hydrogen atom or a group chosen from: - alkyl; - alkoxy, alkylthio; - hydroxy, mercapto; - nitro, nitroso; - R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X”- with R° representing a hydrogen atom, an alkyl or aryl group; X, X' and X”, identical or different, representing an oxygen, sulfur or NR atom with R representing a hydrogen atom or an alkyl group; - (O)2S(O )-, M+ with M+ representing a hydrogen atom or a cationic counter-ion; - (O)CO -, M+ with M+ as defined previously; - R”-S(O)2-, with R” representing a hydrogen atom, an alkyl group, an aryl group, (di)(alkyl)amino, aryl(alkyl)amino; preferably a phenylamino or phenyl group; - R”'-S(O)2-X'- with R'” representing an alkyl group, possibly substituted aryl, X' as defined previously; - (di)(alkyl)amino; - aryl(alkyl)amino possibly substituted by one or more groups chosen from i) nitro; ii) nitroso; iii) (O)2S(O-)-, M+ and iv) alkoxy with M+ as defined above; - heteroaryl possibly substituted; preferably a benzothiazolyl group; - cycloalkyl; in particular cyclohexyl, - Ar N=N with Ar representing an aryl group possibly substituted; preferably a phenyl possibly substituted by one or more alkyl groups, (O)2S(O )-, M+ or phenylamino; - or two contiguous groups R7 with R8 or R8 with R9 or R9 with Rio together form a fused group benzo A'; and R'7 with R'8 or R'8 with R'9 or R'9 with R'io together form a fused group benzo B'; with A' and B' possibly substituted by one or more groups chosen from i) nitro; ii) nitroso; iii) (O)2S(O-)-, M+; iv) hydroxy; v) mercapto; vi) (di)(alkyl)amino; vii) R°-C(X)-X'-; viii) R°-X'-C(X)-; ix) R°-X'-C(X)-X”-; x) Ar-N=N- and xi) aryl(alkyl)amino possibly substituted; with M+, R°, X, X', X” and Ar as defined above; * W represents a sigma bond, an oxygen atom, a sulfur atom, or a divalent radical i) -NR- with R as defined previously, or ii) methylene -C(Ra)(Rb)- with Ra and Rb, identical or different, representing a hydrogen atom or an aryl group, or Ra and Rb together with the carbon atom bearing them form a spiro cycloalkyl; preferably W represents a sulfur atom or Ra and Rb together form a cyclohexyl; provided that formulas (A-II) and (A-II') comprise at least one sulfonate radical (O)2S(O )-, M+ or one carboxylate radical (O)CO -, M+ on one of the rings A, A', B, B' or C; preferably sodium sulfonate;

[0223] A titre d’exemple de colorants de formule (A-II), on peut citer : 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 Yellow 36, Acid Yellow 199, Food Yellow 3; Acid Violet 7, Acid Violet 14, Acid Blue 113, Acid Blue 117, Acid Black 1, Acid Brown 4, Acid Brown 20, Acid Black 26, Acid Black 52, Food Black 1, Food Black 2 ; Food yellow 3 ou sunset yellow;

[0224] et à titre d’exemple de colorants de formule (A-IF), on peut citer : Acid Red 111, Acid Red 134, Acid yellow 38 ;

[0225] b) les colorants azo anioniques pyrrazolone de formule (A-III) et (A-IIF) :

[0226] formulas (A-III) and (A-III') in which: * Rn, Rn and Rn, identical or different, represent a hydrogen atom, a halogen, an alkyl group or -(O)2S(O), M+ with M+ as defined previously; * Ru represents a hydrogen atom, an alkyl group or a -C(O)O group, M+ with M+ as defined previously; * R15 represents a hydrogen atom; * Ri6 represents an oxo group in which case R'i6 is absent, or else R[5 with R[6 together form a double bond; * Rn and Ri8, whether identical or different, represent a hydrogen atom, or a group chosen from: - (O)2S(O )-, M+ with M+ as defined previously; - Ar-OS(O)2- with Ar representing an aryl group possibly substituted; preferably a phenyl possibly substituted by one or more alkyl groups; * R19 and R2q together form either a double bond or a benzo D' group, possibly substituted; * R'16, R'19 and R'2O, whether identical or different, represent a hydrogen atom or an alkyl or hydroxy group; * R2i represents a hydrogen atom, an alkyl group, or alkoxy; * Ra and Rb, identical or different, are as defined previously, preferably Ra represents a hydrogen atom and Rb represents an aryl group; * Y represents either a hydroxy group or an oxo group; * represents a single bond when Y is an oxo group; and represents WW JO» •* a double bond when Y represents a hydroxy group; provided that formulas (A-III) and (A-III') comprise at least one sulfonate radical (O)2S(O )-, M+ or one carboxylate radical -C(O)O-, M+ on one of the rings D or E; preferably sodium sulfonate; Examples of colorants with formula (A-III) include: Acid Red 195, Acid Yellow 23, Acid Yellow 27, Acid Yellow 76, and examples of colorants with formula (A-III') include: Acid Yellow 17;

[0227] c) the anthraquinone dyes of formula (A-IV) and (A-IV'):

[0228] formulas (A-IV) and (A-IV) in which: * R22, R23, R24, R25, R26 and R27, whether identical or different, represent a hydrogen atom, a halogen atom, or a group chosen from: - alkyl; - hydroxy, mercapto; - alkoxy, alkylthio; - aryloxy or arylthio possibly substituted, preferably substituted by one or more groups chosen from alkyl and (O)2S(O )-, M+ with M+ as defined above; - aryl(alkyl)amino possibly substituted by one or more groups chosen from alkyl and (O)2S(O )-, M+ with M+ as defined previously; - (di)(alkyl)amino; - (di)(hydroxyalkyl)amino - (0)2S(0 )-, M+ with M+ as defined previously; * Z' represents a hydrogen atom or a group NR28R29 where R28 and R29, identical or different, represent a hydrogen atom or a group chosen from: - alkyl; - polyhydroxyalkyl such as hydroxyethyl; - aryl possibly substituted by one or more particularly i) alkyl groups such as methyl, n-dodecyl, n-butyl; ii) (O)2S(O )-, M+ with M+ as defined previously; iii) R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X”- with R°, X, X' and X” as defined previously, preferably R° represents an alkyl group; - cycloalkyl; in particular cyclohexyl; * Z, represents a group chosen from hydroxy and NR'28R'29 with R'28 and R'29, identical or different, represent the same atoms or groups as R28 and R29 as defined previously; provided that formulas (A-IV) and (A-IV') comprise at least one sulfonate radical (O)2S(O )-, M+ or one carboxylate radical -C(O)O, M+; preferably sodium sulfonate; As an example of dyes of formula (A-IV), we can cite: 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 purple No. 2; and as an example of dyes of formula (A-IV') we can cite: Acid Black 48;

[0229] d) the nitro dyes of formula (AV), and (A-V'):

[0230] formulas (AV) and (A-V') in which: * R3o, R3i and R32, whether identical or different, represent a hydrogen atom, a halogen atom, or a group chosen from: - alkyl; - alkoxy possibly substituted by one or more hydroxy groups, alkylthio possibly substituted by one or more hydroxy groups; - hydroxy, mercapto; - nitro, nitroso; - polyhalogenoalkyl; - R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X”- with R° ; X, X' and X” as defined previously; - (O)2S(O )-, M+ with M+ as defined previously; - (O)CO -, M+ with M+ as defined previously; - (di)(alkyl)amino;

[0231] - (di)(hydroxyalkyl)amino; - heterocycloalkyl such as piperidino, piperazino or morpholino; particularly R30, R3i and R32 represent a hydrogen atom; * Rc and Rd, whether identical or different, represent a hydrogen atom or an alkyl group; * W is as defined previously; W particularly represents a -NH- group; * ALK represents a divalent alkylene group, linear or branched, in Ci-C6; particularly ALK represents a -CH2-CH2- group; * n equals 1 or 2; * p represents an integer between 1 and 5 inclusive; * q represents an integer between 1 and 4 inclusive; * u is equal to 0 or 1; * when n equals 1, J represents a nitro, or nitroso, group; particularly nitro; * when n equals 2, J represents an oxygen atom, a sulfur atom, or a divalent radical -S(O)m- with m representing an integer 1 or 2; preferably J represents a radical -SO2-; * M' represents a hydrogen atom or a cationic counter-ion; * .. present or absent represents a benzo group, possibly substituted by one or more R30 groupings as defined above; provided that the formulas (AV) and (A-V') include at least one sulfonate radical (O)2S(O )-, M+ or one carboxylate radical -C(O)O-, M+; preferably sodium sulfonate;

[0232] Examples of colorants of formula (AV) include: Acid Brown 13; Acid Orange 3; examples of colorants of formula (A-V') include: Acid Yellow 1, 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)aniline ethanesulfonic acid, 4-β-hydroxyethylamino-3-nitrobenzenesulfonic acid; EXT D&C yellow 7;

[0233] e) triarylmethane dyes of formula (A-VI): r;, (A-VI)

[0234] formula (A-VI) in which: * R33, R34, R35 and R36, identical or different, represent a hydrogen atom or a group chosen from alkyl, possibly substituted aryl and possibly substituted arylalkyl; particularly an alkyl and benzyl group possibly substituted by an (O)mS(O )-, M+ group with M+ and m as defined above; * R37, R38, R39, R40, R41, R42, 845 and R44, whether identical or different, represent a hydrogen atom or a group chosen from: - alkyl; - alkoxy, alkylthio; - (di)(alkyl)amino; - hydroxy, mercapto; - nitro, nitroso; - R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X”- with R° representing a hydrogen atom, an alkyl or aryl group; X, X' and X”, identical or different, representing an oxygen, sulfur or NR atom with R representing a hydrogen atom or an alkyl group; - (O)2S(O )-, M+ with M+ representing a hydrogen atom or a cationic counter-ion; - (O)CO -, M+ with M+ as defined previously; - or two contiguous groups R4i with R42 or R2 with R4i or R43 with R44 together form a fused benzo group: I'; with I' possibly substituted by one or more groups chosen from i) nitro; ii) nitroso; iii) (O)2S(O)-, M+; iv) hydroxy; v) mercapto; vi) (di)(alkyl)amino; vii) R°-C(X)-X'-; viii) R°-X'-C(X)-; ix) R°-X'-C(X)-X”-; with M+, R°, X, X', X” as defined previously; particularly R37 at Rio represent a hydrogen atom, and Ri at IR, identical or different represent a hydroxy group or (O)2S(O )-, M+; and when R3 with R4 together form a benzo group, it is preferentially substituted by an (O)2S(O )- group; provided that at least one of the rings G, H, I, or I' comprises at least one sulfonate radical (O)2S(O)- or one carboxylate radical -C(O)O; preferably sulfonate. Examples of dyes with the formula (A-VI) include: Acid Blue 1; Acid Blue 3; Acid Blue 7; Acid Blue 9; Acid Violet 49; Acid Green 3; Acid Green 5; Acid Green 50;

[0235] f) xanthene-derived dyes of formula (A-VII): % % (A-VII) Ri

[0236] formula (A-VII) in which: * R5, R46, R7 and R48, whether identical or different, represent a hydrogen atom or a halogen atom; * R9, R50, R51 and R52, whether identical or different, represent a hydrogen atom, a halogen atom, or a group chosen from: - alkyl; - alkoxy, alkylthio; - hydroxy, mercapto; - nitro, nitroso; - (O)2S(O )-, M+ with M+ representing a hydrogen atom or a cationic counter-ion; - (O)CO -, M+ with M+ as defined previously; in particular R53, R54, R55 and R48 represent a hydrogen or halogen atom; * G represents an oxygen atom, sulfur atom or an NR group with R representing a hydrogen atom or an alkyl group; particularly G represents an oxygen atom; * L represents an alkoxide O M+; a thioalkoxide S, M+ or an NRf group, with Rf representing a hydrogen atom or an alkyl group, and M+ as defined previously; M+ is particularly sodium or potassium; * L' represents an oxygen atom, sulfur atom or ammonium group: N+ RfRg, with Rf and Rg, identical or different, representing a hydrogen atom, an alkyl group, aryl group possibly substituted; L' particularly represents an oxygen atom or a phenylamino group possibly substituted by one or more alkyl groups or (O)mS(O )-, M+ with m and M+ as defined previously; * Q and Q', whether identical or different, represent an oxygen or sulfur atom; particularly Q and Q' represent an oxygen atom; * M+ is as defined previously.

[0237] Examples of colorants of formula (A-VII) include: Acid Yellow 73; Acid Red 51; Acid Red 52, Acid Red 87; Acid Red 92; Acid Red 95; Acid Violet 9;

[0238] g) dyes derived from indole of formula (A-VIII): (A-vni)

[0239] formula (A-VIII) in which: * R53, R54, R55, R56, R57, R58, R59 and R60, whether identical or different, represent a hydrogen atom or a group chosen from: - alkyl; - alkoxy, alkylthio; - hydroxy, mercapto; - nitro, nitroso;

[0240] - R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X' ' - with R° representing an atom hydrogen, an alkyl or aryl group; X, X' and X”, identical or different, representing an oxygen, sulfur or NR atom with R representing a hydrogen atom or an alkyl group; - (O)2S(O )-, M+ with M+ representing a hydrogen atom or a cationic counter-ion; - (O)CO -, M+ with M+ as defined previously; * G represents an oxygen atom, sulfur atom or an NR group with R representing a hydrogen atom or an alkyl group; particularly G represents an oxygen atom; * Ri and Rh, whether identical or different, represent a hydrogen atom or an alkyl group; provided that the formula (A-VIII) comprises at least one sulfonate radical (O)2 S(O )-, M+ or one carboxylate radical -C(O)O, M+; preferably sodium sulfonate;

[0241] By way of example of dyes of formula (A-VIII), mention may be made of: Acid Blue 74.

[0242] h) quinoline-derived dyes of formula (A-IX):

[0243] formula (A-IX) in which: * R6i represents a hydrogen atom, halogen or alkyl group; * R62, Res, and Rm, whether identical or different, represent a hydrogen atom or a (O)2S(O )- group, M+ with M+ representing a hydrogen atom or a cationic counter-ion; * or R6i with R62, or R6i with R64, together form a benzo group possibly substituted by one or more (O)2S(O )- groups, M+ with M+ representing a hydrogen atom or a cationic counter-ion; it being understood that the formula (A-IX) includes at least one sulfonate radical (O)2S(O )-, M+ preferably sodium sulfonate.

[0244] Examples of colorants of formula (A-IX) include: Acid Yellow 2, Acid Yellow 3 and Acid Yellow 5.

[0245] More specifically, the coloring composition comprises one or more anionic direct dyes selected, alone or in mixture, from the following anionic direct dyes:

[0246] [Tables 1] (CI 45380) Acid Red 87 (A-VII) (CI 10316) Sodium salt of 2,4-dinitro-l-naphthol-7-sulfonic acid (A-V') (CI 10383) Acid Orange 3 (AV) (C.L 13015) Acid Yellow 9 / Food Yellow 2 (A-II) (C.l. 14780) / Direct Red 45 / Food Red 13 (A-II) (C.l. 13711) Acid Black 52 (A-II) (C.l. 13065) Acid Yellow 36 (A-II) (C.l. 14700) Sel de sodium de l’acide l-hydroxy-2-(2',4'-xylyl-5-sufonatoazo)-naphtalène-4-sulfonique / Food Red 1 (A-II) (C.l. 14720) Acid Red 14 / Food Red 3 / Mordant Blue 79 (A-II) (C. 1. 14805) Sel de sodium de l’acide 4-hydroxy-3-[(2-métoxy-5-. nitrophényl) diaza]-6-(phénylamino)naphtalène-2-sulfonique / Acid Brown 4 ( A-II) (C.l. 15510) Acid Orange 7 / Pigment Orange 17 / Solvent Orange 49 (A-II) (C.l. 15985) Food Yellow 3 / Pigment Yellow 104 (A-II) (C.l. 16185) Acid Red 27 / Food Red 9 (A-II) (C.l. 16230) Acid Orange 10 / Food Orange 4 (A-II) (C.l. 16250) Acid Red 44 (A-II) (C.l. 17200) Acid Red 33 / Food Red 12 (A-II) (C.l. 15685) Acid Red 184 (A-II) (C.l. 19125) Acid Violet 3 (A-II) (C.l.18055) Sodium salt of l-hydroxy-2-(4'-acetamidophenylazo)-8-acetamido-naphthalene-3,6-disulfonic acid / Acid Violet 7 / Food Red 11 (A-II) (Cl 18130) Acid Red 135 (A-II) (Cl 19130) Acid Yellow 27 (A-III) (Cl 19140) Acid Yellow 23 / Food Yellow 4 (A-III) (Cl 20170) 4'-(sulfonato-2,4"-dimethyl)-bis-(2,6-phenylazo)-1,3-dihydroxybenzene / Acid Orange 24 (A-II) (Cl 20470) Sodium salt of l-amino-2-(4'-nitrophenylazo)-7-phenyla zo-8-hydroxy-naphthalene-3,6-disulfonic / Acid Black 1 (A-II) (Cl 23266) (4-((4-methylphenyl)sulfonyloxy)-phenylazo)2,2'-dimethyl-4-((2-hydroxy-5,8-disulfonato)naphtylazo)biphenyl / Acid Red 111 (A -II') (Cl 27755) Food Black 2 (A-II) . (CI 25440) l-(4'-sulfonatophenylazo)-4-((2"-hydroxy-3"-acetylamino-6,8"-disulfonato)naphtylazo)-6-sulfonatonaphthalene (tetrasodium salt) / Food Black 1 (A-II) (CI 42090) Acid Blue 9 (A-VI) (CI 60730) Acid Violet 43 (A-IV) (CI 61570) Acid Green 25 (A-IV) (CI 62045) Sodium salt of l-amino-4-cyclohexylamino-9,10-anthraquinone 2-sulfonic acid / Acid Blue 62 (A-IV) (CI 62105) Acid Blue 78 (A-IV) (CI 14710) Sodium salt of 4-hydroxy-3((2-methoxy) phenyl)-azo)-l-naphthalene sulfonic acid / Acid Red 4 (A-II) 2-piperidino-5-nitrobenzene sulfonic acid (V') 2(4'-N,N(2'-hydroxyethyl)amino-2'-nitro)aniline ethane sulfonic acid (A-V') 4-[3-hydroxyethylamino-3-nitrobenzene sulfonic acid (A-V') (CI 42640) Acid Violet 49 (A-VI) (CI 42080) Acid Blue 7 (A-VI) (CI 58005) Sodium salt of l,2-dihydroxy-3-sulfo-anthraquinone / Mordant Red 3 (A-IV) (CI62055) Sodium salt of l-amino-9,10-dihydro-9,10-dioxo-4-(phenylamino) 2-anthracene sulfonic acid / Acid Blue 25 (A-IV) (CI 14710) Sodium salt of 4-hydroxy-3-((2-methoxyphenyl)-azo)-l-naphthalene sulfonic acid / Acid Red 4 (A-II) .

[0247] Most of these dyes are described in particular in the Color Index published by The Society of Dyers and Colorists, PO Box 244, Perkin House, 82 Grattan Road, Bradford, Yorkshire, BD1 2JBN England.

[0248] The anionic colorants most particularly preferred are the colorants designated in the Color Index under the code 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-l-anthracenyl)-amino]-5-methylbenzenesulfonic acid), CI 15510 (monosodium salt of 4-[(2-hydroxy-l-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-naphthalene disulfonic acid), CI 20470 (disodium salt of l-amino-2-(4'-nitrophenylazo)-7-phenylazo-8-hydroxy-3,6-naphthalene disulfonic acid), CI 42090 (disodium salt of N-ethyl-N-[4-[[4-[ethyl[3-sulfophenyl)-methyl]-amino]-phenyl](2-sulfophenyl)-methylene]-2,5-cyclohexadien-l-ylidene]-3-sulfobenzenemethanaminium hydroxide, internal salt), CI 61570 (disodium salt of 2,2'-[(9,10-dihydro-9,10-dioxo-l,4-anthracenediyl)-diimino]-bis-[5-methyl]-benzene sulfonic acid.

[0249] Compounds corresponding to the mesomeric, tautomeric forms of (A-II) to (A-IX) structures can also be used.

[0250] Among the natural direct dyes that can be used according to the invention, mention may be made of hennotannic acid, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, protocatechaldehyde, indigo, isatin, curcumin, spinulosin, apigenidine, and orcein. Extracts or decoctions containing these natural dyes, and in particular henna-based poultices or extracts, may also be used.

[0251] Preferably, the colouring composition implemented in the process of the invention comprises one or more cationic direct colour(s).

[0252] Preferably, the colouring composition used in the process of the invention comprises one or more cationic direct dye(s) chosen from azo cationic direct dyes, hydrazono cationic direct dyes, anthraquinone cationic direct dyes, and mixtures thereof.

[0253] Advantageously, the total content of the direct colorant(s) ranges from 0.001 to 20% by weight, preferably from 0.005 to 15% by weight, more preferably from 0.01 to 10% by weight, better from 0.05 to 5% by weight, even better from 0.1 to 3% by weight, relative to the total weight of the coloring composition. Aromatic compound

[0254] The coloring composition implemented in the process of the invention comprises at least one compound of formula (I):

[0255] wherein Y represents a Ci-C4 hydroxyalkyl group or a Ci-C4 hydroxyalkyloxy radical, n denotes an integer from 0 to 5, and X, whether the same or different, represents a CrC4 alkyl radical or a halogen. Preferably, n is equal to 0. In a particular embodiment, Y represents a hydroxymethyl, hydroxyethyl, or hydroxyethyloxy radical.

[0256] Examples of compounds with formula (I) include benzyl alcohol, phenyl ethanol, and phenoxyethanol. In one particular embodiment, the compound with formula (I) is benzyl alcohol.

[0257] According to a particular embodiment, the quantity of compounds of formula (I) varies from 0.01 to 10% by weight, preferably from 0.05 to 8% by weight, better from 0.1 to 5% by weight, relative to the total weight of the coloring composition. Aliphatic solvent

[0258] The colouring composition implemented in the process of the invention comprises at least one C2-C6 hydroxylated aliphatic solvent.

[0259] By aliphatic, we mean a compound not containing an aromatic ring. Solvents of this type may be monoalcohols or polyols that are liquid at room temperature (25°C) and atmospheric pressure (105 Pa). Preferably, these solvents are non-etherified. In a particular embodiment, these solvents are selected from ethanol, glycerol, propylene glycol, dipropylene glycol, and hexylene glycol. Preferably, the C2-C6 hydroxylated aliphatic solvent is ethanol and / or hexylene glycol, preferably ethanol.

[0260] According to one embodiment, the amount of hydroxylated aliphatic solvent varies from 0.1% to 40% by weight, preferably from 0.5% to 30% by weight, more preferably from 1% to 20% by weight, better from 2% to 15% by weight, even better from 3% to 10% by weight, relative to the weight of the coloring composition.

[0261] Preferably, the composition comprises benzyl alcohol and ethanol.

[0262] According to a particular embodiment, the weight ratio of compounds of formula (I) / C2-C6 hydroxylated aliphatic solvent(s) is less than or equal to 1, preferably from 0.1 to 1, better still from 0.1 to 0.5.

[0263] According to a particular embodiment, the weight ratio of benzyl alcohol / ethanol is less than or equal to 1, preferably from 0.1 to 1, better still from 0.1 to 0.5. Polysaccharide

[0264] The colouring composition implemented in the process of the invention may also include one or more polysaccharide(s).

[0265] In the present invention, "polysaccharide" means a polymer composed of sugar units. "Sugar unit" means an oxygenated hydrocarbon compound possessing several alcohol functional groups, with or without aldehyde or ketone functional groups, and comprising at least four carbon atoms. The sugar units may optionally be modified by substitution, and / or by oxidation, and / or by dehydration.

[0266] The sugar motifs that can be included in the composition of the polysaccharides of the invention are preferably derived from the following sugars: glucose; galactose; arabinose; rhamnose; mannose; xylose; fucose; anhydrogalactose; galacturonic acid; glucuronic acid; mannuronic acid; galactose sulfate; anhydrogalactose sulfate and fructose.

[0267] The following polymers, alone or in mixtures, may be cited in particular as examples of polysaccharides: a) exudates from trees or shrubs, including: - gum arabic (branched polymer of galactose, arabinose, rhamnose and glucuronic acid); - Ghatti gum (polymer derived from arabinose, galactose, mannose, xylose and glucuronic acid); - karaya gum (polymer derived from galacturonic acid, galactose, rhamnose and glucuronic acid); - tragacanth gum (or tragacanth) (polymer of galacturonic acid, galactose, fucose, xylose and arabinose); b) gums derived from algae, including: - agar (polymer derived from galactose and anhydrogalactose); - alginates (polymers of mannuronic acid and glucuronic acid); - carrageenans and furcelleranes (galactose sulfate polymers and (anhydrogalactose sulfate); c) gums from seeds or tubers, including: - guar gum (polymer of mannose and galactose); - carob gum (polymer of mannose and galactose); - fenugreek gum (polymer of mannose and galactose); - tamarind gum (polymer of galactose, xylose and glucose); - konjac gum (polymer of glucose and mannose); d) microbial gums, including: - xanthan gum (polymer of glucose, mannose acetate, mannose / pyruvic acid and glucuronic acid); - gellan gum (polymer of partially acylated glucose, rhamnose and glucuronic acid); - scleroglucan gum (glucose polymer); e) polymers extracted from plants, including: - celluloses (polymers of glucose); - starches (polymers of glucose) and - Inulin.

[0268] These polymers can be modified physically or chemically. Physical treatments include, in particular, heat treatment. Chemical treatments include esterification and etherification reactions. of amidation, of oxidation. These treatments lead to polymers which can be non-ionic, anionic or amphoteric.

[0269] In particular, guar gums, locust bean gums, starches and celluloses can be modified / treated.

[0270] The guar gums usable according to the invention can be modified by (poly)hydroxylakyl groups in the C6-C6 range. Examples of (poly)hydroxyalkyl groups in the C6-C6 range include hydroxymethyl, hydroxyethyl, hydroxypropyl, and hydroxybutyl groups. These guar gums are well known in the prior art and can, for example, be prepared by reacting corresponding alkene oxides, such as propylene oxides, with guar gum to obtain guar gum modified by hydroxypropyl groups. The degree of hydroxyalkylation preferably ranges from 0.4 to 1.2 and corresponds to the number of alkylene oxide molecules consumed per number of free hydroxyl groups present on the guar gum.

[0271] Such guar gums possibly modified by hydroxyalkyl groups are for example sold under the trade names JAGUAR HP8, JAGUAR HP60 and JAGUAR HP120 by the company RHODIA CHIMIE.

[0272] The starches usable in the present invention may be of botanical origin from cereals or tubers. Thus, the starches are chosen, for example, from corn, rice, oat, cassava, barley, potato, wheat, sorghum, pea, and tapioca starches. Hydrolysates of the starches mentioned above may also be used. The starch is preferably derived from potato.

[0273] Preferably, starch phosphates will be used, in particular distarch phosphates or compounds rich in distarch phosphate such as the product offered under the references PREJEL VA-70-T AGGL (gelatinized hydroxypropyl cassava distarch phosphate) or PREJEL TK1 (gelatinized cassava distarch phosphate) or PREJEL 200 (gelatinized acetylated cassava distarch phosphate) by the AVEBE Company or STRUCTURE ZEA of NATIONAL STARCH (gelatinized maize distarch phosphate).

[0274] According to the invention, amphoteric starches can also be used; these amphoteric starches comprise one or more anionic groups and one or more cationic groups. The anionic and cationic groups may be linked to the same reactive site of the starch molecule or to different reactive sites; preferably, they are linked to the same reactive site. The anionic groups may be of the carboxylic, phosphate, or sulfate type, and preferably carboxylic. The cationic groups may be of the primary, secondary, tertiary, or quaternary amine type.

[0275] The polysaccharides that can be used according to the invention can be cellulosic polymers.

[0276] By "cellulosic" polymer, according to the invention, any polysaccharide compound having in its structure chains of glucose residues joined by [3-1,4] bonds; in addition to unsubstituted celluloses, cellulose derivatives can be anionic, cationic, amphoteric or non-ionic.

[0277] Cellulosic polymers are also called celluloses.

[0278] Thus, the cellulosic polymers usable according to the invention can be chosen from unsubstituted celluloses including in microcrystalline form and cellulose ethers.

[0279] Among these cellulosic polymers, we distinguish cellulose ethers, cellulose esters and cellulose ether esters.

[0280] Cellulose esters include inorganic cellulose esters (cellulose nitrates, sulfates, or phosphates), organic cellulose esters (cellulose monoacetates, triacetates, amidopropionates, acetatebutyrates, acetatepropionates, or acetatetrimellitates), and mixed organic / inorganic cellulose esters such as cellulose acetatebutyrates and acetatepropionate sulfates. Examples of cellulose ether esters include hydroxypropylmethylcellulose phthalates and ethylcellulose sulfates.

[0281] Among the cellulose ethers, examples include (Ci-C4)alkylcelluloses such as methylcelluloses and ethylcelluloses (for example, Ethocel standard 100 Premium from DOW CHEMICAL); (poly)hydroxy(Ci-C4)alkylcelluloses such as hydroxymethylcelluloses, hydroxyethylcelluloses (for example, Natrosol 250 HHR offered by ASHLAND) and hydroxypropylcelluloses (for example, Klucel EF from AQUALON); mixed (poly)hydroxy(Ci-C4)alkyl-(Ci-C4)alkylcelluloses such as hydroxypropyl-methylcelluloses (for example, Methocel E4M from DOW CHEMICAL), hydroxyethyl-methylcelluloses, hydroxyethyl-ethylcelluloses (for example, Bermocoll E 481 FQ from AKZO NOBEL) and hydroxybutyl-methylcelluloses.

[0282] Among the anionic cellulose ethers, mention may be made of (poly)carboxy(C1-C4)alkylcelluloses and their salts. By way of example, mention may be made of carboxymethylcelluloses, carboxymethylmethylcelluloses (for example Blanose 7M from the company AQUALON) and carboxymethylhydroxyethylcelluloses and their sodium salts.

[0283] Among cationic cellulose ethers, cationic cellulose derivatives such as cellulose copolymers or cellulose derivatives grafted with a water-soluble quaternary ammonium monomer may be mentioned, and described in particular in US patent 4131576, such as (poly)hydroxy(Ci-C4)alkyl celluloses, including hydroxymethyl-, hydroxyethyl-, or hydroxypropyl celluloses grafted with, among other things, a salt of methacryloylethyl trimethylammonium, methacrylmidopropyl trimethylammonium, or dimethyl-diallylammonium. The marketed products meeting this definition are, more specifically, those sold under the names "Celquat® L 200" and "Celquat® H 100" by the National Starch Company.

[0284] Preferably, the polysaccharide(s) are chosen from scleroglucan gums, cellulosic polymers, xanthan gums, guar gums, preferably from scleroglucan gums, guar gums and cellulosic polymers.

[0285] The polysaccharide(s) may be present in the coloring composition implemented in the process according to the invention in a content ranging from 0.001 to 5% by weight and preferably from 0.01 to 4%, and even more preferably from 0.05 to 3% by weight relative to the total weight of the coloring composition.

[0286] The colouring composition according to the invention may comprise water or a mixture of water and optionally one or more solvents other than compounds of formula (I) and C2-C6 hydroxylated aliphatic solvents such as polyol ethers like dipropylene glycol monomethyl ether.

[0287] Preferably, the colouring composition comprises water, preferably in a content of 20 to 95% by weight, preferably 30 to 80% by weight, and even more preferably 40 to 87% by weight relative to the total weight of the colouring composition.

[0288] The colouring composition implemented in the process of the invention may also contain various adjuvants conventionally used in compositions for hair colouring, such as anionic, cationic, non-ionic, amphoteric or zwitterionic surfactants; anionic, cationic, amphoteric, zwitterionic or non-ionic polymers other than polysaccharides; mineral or organic thickening agents; antioxidants, penetration agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents, film-forming agents, ceramides, preservatives, opacifying agents.

[0289] The above adjuvants are generally present in quantities of each of them between 0.01 and 20% by weight relative to the weight of the coloring composition.

[0290] Of course, the person skilled in the art will take care to choose this or these possible complementary compounds in such a way that the advantageous properties intrinsically attached to the colouring composition are not, or substantially not, altered by the envisaged addition(s).

[0291] The pH of the coloring composition used in the process according to the invention is generally between 2 and 14 approximately, and preferably greater than 5. According to a particular embodiment, the pH is between 2.5 and 10. It can be adjusted to the desired value by means of acidifying or alkalizing agents commonly used in dyeing keratin fibers or by means of conventional buffer systems.

[0292] Examples of acidifying agents include mineral or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid, and sulfonic acids.

[0293] Examples of alkalizing agents include ammonia, alkali carbonates, alkanolamines such as mono-, di- and triethanolamines and their derivatives, sodium or potassium hydroxides and compounds of the following formula: a \ z D NWN R R. t- U

[0294] in which W is a propylene remnant optionally substituted by a hydroxyl group or a Ci-C4 alkyl radical; Ra, Rb, Rc and Rd, identical or different, represent a hydrogen atom, a CrC4 alkyl radical or a Ci-C4 hydroxyalkyl radical. Process

[0295] The process for coloring keratin fibers according to the invention comprises applying to said keratin fibers the lightening composition described above, and the coloring composition described above.

[0296] Preferably, the step of applying the colouring composition is carried out after the step of applying the lightening composition.

[0297] Preferably, the coloring process includes, before the step of applying the lightening composition to the keratin fibers, a step of mixing an oxidizing composition comprising the chemical oxidizing agent(s) as described above with an alkaline composition comprising the alkaline agent(s) as described above to obtain the lightening composition.

[0298] This mixing step is preferably carried out at the time of use, just before the application of the lightening composition from the mixture to the keratin fibers.

[0299] Preferably, the alkaline and oxidizing compositions are mixed in a weight ratio of alkaline composition / oxidizing composition ranging from 0.1 to 2, preferably from 0.3 to 1.5, better from 0.5 to 1.

[0300] The lightening composition can be applied to dry or moist keratin fibers.

[0301] The lightening composition is left in place on the fibers for a period generally ranging from 1 minute to 1 hour, preferably from 5 minutes to 55 minutes.

[0302] Preferably, the keratin fibers are then rinsed with water, and possibly undergo washing with shampoo followed by rinsing with water, before possibly being wrung out, dried or left to dry.

[0303] The coloring composition is then applied to the dry or wet keratin fibers.

[0304] The coloring composition is left in place on the fibers for a period generally ranging from 1 minute to 100 minutes, preferably from 5 minutes to 80 minutes.

[0305] At the end of the treatment, the keratin fibers are possibly rinsed with water, possibly undergo washing with shampoo followed by rinsing with water, before being dried or left to dry.

[0306] The invention also relates to a method for coloring keratin fibers, in particular human keratin fibers such as hair, comprising applying to said keratin fibers: i) of a lightening composition comprising: - one or more oxidizing agent(s), - one or more alkali agent(s); then ii) a coloring composition comprising: - one or more direct dye(s), - one or more compound(s) of formula (I): in which Y represents a C1-C4 hydroxyalkyl group or a C1-C4 hydroxyalkyloxy radical, n denotes an integer ranging from 0 to 5, X, whether the same or different, represents a C1-C4 alkyl radical or a halogen, - one or more aliphatic hydroxylated solvent(s) comprising 2 to 6 carbon atoms.

[0307] The invention also relates to a method for coloring keratin fibers, in particular human keratin fibers such as hair, comprising: 1) the mixing of an oxidizing composition comprising one or more chemical oxidizing agent(s) with an alkaline composition comprising one or more alkaline agent(s) to obtain a lightening composition, then 2) application to said keratin fibers: i) of the lightening composition; then ii) a coloring composition comprising: - one or more direct dye(s), - one or more compound(s) of formula (I): (X)nv ® in which Y represents a C1-C4 hydroxyalkyl group or a C1-C4 hydroxyalkyloxy radical, n denotes an integer ranging from 0 to 5, X, whether the same or different, represents a C1-C4 alkyl radical or a halogen, - one or more aliphatic hydroxylated solvent(s) comprising 2 to 6 carbon atoms. Kit

[0308] Another object of the invention is a device with at least three compartments, for the staining of keratin fibers, comprising at least a first compartment containing a staining composition comprising one or more direct dye(s), one or more compound(s) of formula (I) as defined above and one or more aliphatic hydroxylated solvent(s) comprising from 2 to 6 carbon atoms, at least a second compartment containing an alkaline composition comprising one or more alkaline agent(s), and at least a third compartment containing an oxidizing composition comprising one or more chemical oxidizing agent(s).

[0309] The compositions of the device according to the invention are packaged in separate compartments, accompanied, optionally, by suitable application means, identical or different, such as brushes, sponges or brushes.

[0310] The device mentioned above can also be equipped with a means for delivering the desired mixture onto the hair, for example such as the devices described in patent FR 2586913.

[0311] The following examples serve to illustrate the invention without, however, being limiting in nature. Examples

[0312] In the following examples, all quantities are given as mass percentage of active material (AM) relative to the total weight of the composition (unless otherwise stated). Compositions

[0313] Compositions A, C and O were prepared from the compounds whose contents are indicated in the tables below:

[0314] Alkaline composition A

[0315] [Tables2] A ETHANOLAMINE 12.9 LAURIC ACID 3.0 GLYCOL DISTEARATE 2.0 CETEARYL ALCOHOL 11.5 PROPYLENE GLYCOL 10.0 Oxyethylenated fatty alcohols 20.0 POLYQUATERNIUM-22 1.5 HEXADIMETHRINE CHLORIDE 3.0 CARBOMER 0.4 ASCORBIC ACID 0.25 SODIUM METABISULFITE 0.7 Sequestering agent 0.2 pH adjuster Qs pH = 10.4 + / - 0.4 Water Qs 100

[0316] Oxidizing composition O

[0317] [Tables3] O HYDROGEN PEROXIDE 6.00 TRIDECETH-2 CARBOXAMIDE MEA 0.82 GLYCERIN 0.50 CETEARYL ALCOHOL 2.28 CETEARETH-25 0.57 Phosphoric acid (Qs) pH = 2.2 + / - 0.2 Stabilizing agents, sequestering agents (Qs) Water (Qs) 100

[0318] Coloring composition C

[0319] [Tables4] C BENZYL ALCOHOL 2.0 ethanol 8.0 BASIC RED 76 0.5 BASIC BROWN 17 0.5 BASIC YELLOW 57 0.6 HC BLUE NO. 16 0.7 SCLEROTIUM GUM 2.0 Sequestering agent 0.5 pH adjuster Qs pH = 7 + / - 0.2 Water Qs 100

[0320] The process according to the invention (Protocol 1) comprising the application of a lightening composition followed by the application of a coloring composition was compared to a process which only includes the application of the coloring composition, without first applying the lightening composition (Protocol 2).

[0321] Protocol 1 (invention)

[0322] At the time of use, the alkaline composition A was mixed with the oxidizing composition O in the weight ratio 1+1.5 to obtain a brightening composition.

[0323] The resulting lightening composition was then applied to a strand of hair that was 90% naturally white at a rate of 5g of mixture / g of hair.

[0324] After 35 minutes of exposure on a plate thermostatically controlled at 27°C, the hair was rinsed, washed with a standard shampoo, and air-dried.

[0325] Colouring composition C was then applied to the strands at a rate of 5g of mixture / g of hair.

[0326] After a processing time of 60 min at 27°C under an occlusive cellophane system, the strands were rinsed, then washed and dried using a hair dryer.

[0327] The hair strands thus coloured were then subjected to a washing test with shampoo in order to evaluate the tenacity (the persistence) of the colour obtained.

[0328] Protocol 2 (comparative)

[0329] Colour composition C was applied to a strand of hair that was 90% natural white at a rate of 5g of mixture / g of hair.

[0330] After a processing time of 60 min at 27°C under an occlusive cellophane system, the strands were rinsed, then washed and dried using a hair dryer.

[0331] The hair strands thus coloured were then subjected to a washing test with shampoo in order to evaluate the tenacity (the persistence) of the colour obtained. Results

[0332] The colorimetric measurements were carried out using a KONICA MINOLTA-3600 spectrocolorimeter (illuminant D65, angle 10°, specular component included) in the CIELab system.

[0333] In this L*a*b* system, L* represents the intensity of the color, a* indicates the green / red color axis, and b* the blue / yellow color axis. The lower the value of L*, the more intense and powerful the color.

[0334] [Tables5] L* Protocol 1 (invention) 20.65 Protocol 2 (comparative) 24.19

[0335] The hair strands treated with the lightening step before the coloring step according to the invention have a lower L* value than those treated only with the coloring step according to the comparator.

[0336] In other words, the process according to the invention makes it possible to obtain a more intense colouring than the comparative process.

[0337] Color persistence.

[0338] The color permanence is evaluated by the color difference AE between the colored strands before washing and then after washing. The lower the AE value, the more the color persists after shampooing. The AE value is calculated according to the following equation: A Ê=J

[0339] In this equation, L*a*b* represent the values ​​measured after hair coloring and after washing, and Lo*ao*bo* represent the values ​​measured after hair coloring but before washing.

[0340] [Tableauxô] L* a* b* AE Protocol 1 (invention) Before washing 20.65 0.15 2.37 3.11 After washing 23.16 1.79 3.21 Protocol 2 (comparative) Before washing 24.19 2.11 4.68 6.25 After washing 29.67 2.31 7.68

[0341] The hair strands treated with the lightening step preceding the coloring step according to the invention have a lower AE value than those treated only with the coloring step according to the comparator.

[0342] In other words, the process according to the invention makes it possible to obtain better color retention after shampooing compared to the comparative process.

Claims

Demands

1. A method for coloring keratin fibers, in particular human keratin fibers such as hair, comprising applying to said keratin fibers: i) a lightening composition comprising: - one or more oxidizing agent(s), - one or more alkaline agent(s); and ii) a colouring composition comprising: - one or more direct colour(s), - one or more compound(s) of formula (I): (X> y ® where Y represents a Ci-C4 hydroxyalkyl group or a Ci-C4 hydroxyalkyloxy radical, n denotes an integer ranging from 0 to 5, X identical or different represents a Ci-C4 alkyl radical or a halogen, the compound(s) of formula (I) being chosen from benzyl alcohol, phenyl ethanol, phenoxyethanol, - one or more aliphatic hydroxylated solvent(s) comprising from 2 to 6 carbon atoms.

2. A coloring process according to the preceding claim, wherein the coloring composition comprises one or more cationic direct dye(s), preferably selected from azo cationic direct dyes, hydrazono cationic direct dyes, anthraquinone cationic direct dyes, and mixtures thereof.

3. A coloring process according to any one of the preceding claims, wherein the total content of the direct colorant(s) is from 0.001 to 20%, preferably from 0.005 to 15% by weight, more preferably from 0.01 to 10% by weight, better from 0.05 to 5% by weight, even better from 0.1 to 3% by weight, relative to the total weight of the coloring composition

4. A coloring process according to any one of the preceding claims wherein the compound(s) of formula (I) are selected from benzyl alcohol.

5. A coloring process according to any one of the preceding claims wherein the total content of the compound(s) of formula (I) in the coloring composition is from 0.01 to 10% by weight, preferably from 0.05 to 8% by weight, better from 0.1 to 5% by weight relative to the weight of the coloring composition.

6. A coloring process according to any one of the preceding claims wherein the C2-C6 hydroxylated aliphatic solvent(s) are selected from ethanol, glycerol, propylene glycol, dipropylene glycol, hexylene glycol, preferably ethanol and / or hexylene glycol, preferably ethanol.

7. A coloring process according to any one of the preceding claims wherein the total content of the C2-C6 hydroxylated aliphatic solvent(s) ranges from 0.1% to 40% by weight, preferably from 0.5% to 30% by weight, more preferably from 1% to 20% by weight, better from 2% to 15% by weight, even better from 3% to 10% by weight, relative to the weight of the coloring composition.

8. A coloring process according to any one of the preceding claims wherein the weight ratio of compounds of formula (I) / C2-C6 hydroxylated aliphatic solvent(s) is less than or equal to 1, preferably from 0.1 to 1, better still from 0.1 to 0.

5.

9. A coloring process according to any one of the preceding claims, wherein the chemical oxidizing agent(s) are selected from hydrogen peroxide, urea peroxide, alkali metal bromates or ferricyanides, peroxygenated salts such as alkali or alkaline earth metal persulfates, perborates and percarbonates, and peracids and their precursors; preferably hydrogen peroxide.

10. A coloring process according to any one of the preceding claims, wherein the lightening composition does not comprise peroxygenated salts.

11. A coloring process according to any one of the preceding claims, wherein the alkali agent is selected from alkanolamines such as monoethanolamine, diethanolamine, triethanolamine; ammonia; carbonates or bicarbonates such as sodium (hydrogen)carbonate and potassium (hydrogen)carbonates; alkali or alkaline earth metal silicates or metasilicates such as sodium metasilicate and mixtures thereof, more preferentially among the alkanolamines and ammonia, better among the alkanolamines, even better, monoethanolamine.

12. A coloring method according to any one of the preceding claims, wherein the step of applying the coloring composition ii) is carried out after the step of applying the lightening composition i).

13. A coloring process according to any one of the preceding claims, which includes, before step i), a step of mixing an oxidizing composition comprising the chemical oxidizing agent(s) with an alkaline composition comprising the alkaline agent(s) to obtain the lightening composition.

14. A coloring process according to any one of the preceding claims comprising a step of rinsing the keratin fibers between steps i) and ii).

15. A device with at least three compartments, for staining keratin fibers, comprising at least a first compartment containing a staining composition as defined in any one of claims 1 to 8, at least a second compartment containing an alkaline composition comprising one or more alkaline agent(s), preferably as defined in claim 11, and at least a third compartment containing an oxidizing composition comprising one or more chemical oxidizing agent(s) as preferably defined in claim 9.