Process for dyeing the hair using a lightening composition and a dyeing composition comprising a direct dye, an aromatic compound and a hydroxylated aliphatic solvent

Abstract

Process for dyeing the hair using a lightening composition and a dyeing composition comprising a direct dye, an aromatic compound and a hydroxylated aliphatic solvent. The invention relates to a process for dyeing keratin fibers, in particular human keratin fibers such as the hair, comprising the application to said keratin fibers of a lightening composition, and of a dyeing 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, and X, which may be identical or different, represents a C1-C4 alkyl radical or a halogen, - one or more hydroxylated aliphatic solvent(s) comprising from 2 to 6 carbon atoms.

Description

Process for dyeing the hair using a lightening composition and a dyeing composition comprising a direct dye, an aromatic compound and a hydroxylated aliphatic solvent.

[0001] The present invention relates to a process for dyeing human keratin fibers, in particular the hair, using a lightening composition and a dyeing composition comprising a direct dye, an aromatic compound and a hydroxylated aliphatic solvent, and to a device with several compartments containing the compositions.

[0002] Two major methods for dyeing human keratin fibers, and in particular the hair, are known.

[0003] One of these two methods is oxidation dyeing or permanent dyeing. This dyeing method uses one or more oxidation dye precursors and usually one or more oxidation bases optionally combined with one or more couplers.

[0004] In general, oxidation bases are chosen from 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 products, can give access to colored species.

[0005] The shades obtained with these oxidation bases are quite often varied by combining them with one or more couplers, these couplers being notably chosen from aromatic meta-diamines, meta-aminophenols, meta-diphenols and certain heterocyclic compounds such as indole compounds.

[0006] The variety of molecules used as oxidation bases and couplers allows a wide range of colors to be obtained. This type of dyeing also makes it possible to obtain permanent colorings.

[0007] The second dyeing method, known as direct dyeing or semi-permanent dyeing, comprises the application of direct dyes, which are molecules with affinity for the fibers and which color even in the absence of an oxidizing agent added to the compositions containing them. Given the nature of the molecules used, they tend rather to remain on the surface of the fiber and penetrate relatively little into the fiber, when compared with the small molecules of oxidation dye precursors.

[0008] The direct dyes generally used are chosen from nitrobenzene, anthraquinone, nitropyridine, azo, methine, azomethine, xanthene, acridine, azine or triarylmethane direct dyes. The chemical species used may be nonionic, anionic (acidic dyes) or cationic (basic dyes). Direct dyes may 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 coloring, and are then rinsed out.

[0010] However, the colorings resulting therefrom are colorings that are particularly chromatic, but which are temporary or semi-permanent since their desorption from the surface and / or the core of the fiber is responsible for their weak dyeing power and their poor persistence to washing.

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

[0012] There is also a need to obtain a hair dye that is capable of producing good color build-up, intensity and chromaticity, while having low selectivity and good fastness, notably good persistence to shampoo washing, and that is capable of delivering good dyeing performance, even after a period of storage, while having good usage qualities and retaining good sensory performance notably in terms of sheen, softness, suppleness, smoothness and disentangling of keratin fibers such as the hair.

[0013] This aim and others are achieved by the present invention, a subject of which is thus a process for dyeing keratin fibers, in particular human keratin fibers such as the hair, comprising the application to said keratin fibers:i) of a lightening composition comprising:- one or more oxidizing agent(s),- one or more alkaline agent(s); andii) of a dyeing composition comprising:- one or more direct dye(s),- one or more compound(s) of formula (I): (I)in which Y represents a C1-C4hydroxyalkyl group or a C1-C4hydroxyalkyloxy radical, n denotes an integer ranging from 0 to 5, and X, which may be identical or different, represents a C1-C4alkyl radical or a halogen,- one or more hydroxylated aliphatic solvent(s) comprising from 2 to 6 carbon atoms.

[0014] The invention also relates to a device with at least three compartments, for the dyeing of keratin fibers, comprising at least a first compartment containing a dyeing composition comprising one or more direct dye(s), one or more compound(s) of formula (I) as defined above and one or more hydroxylated aliphatic 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 compound(s).

[0015] The invention makes it possible to obtain keratin fiber colorings having good fastness, notably good persistence to shampoo washing, in natural shades, without using oxidation dyes such as bases and couplers, with a harmonious and natural dyeing result, that is to say without a helmet effect, while providing sheen.

[0016] Other subjects, features, aspects and advantages of the invention will become even more clearly apparent from reading the description and the examples which follow and from examining the appended drawing, in which:

[0017] In the text hereinbelow, unless otherwise indicated, the limits of a range of values are included in that range, notably in the expressions “between” and “ranging from ... to ...”.

[0018] Moreover, the expression “at least one” used in the present description is equivalent to the expression “one or more”.

[0019] As indicated above, the dyeing process uses a lightening composition and a dyeing composition.Lightening composition

[0020] The terms “lightening” and “bleaching” are synonymous and may 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 used in the process according to the invention comprises one or more chemical oxidizing agent(s).

[0023] “Chemical oxidizing agent” is understood to mean an oxidizing agent other than the 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 metal or alkaline-earth metal persulfates, perborates and percarbonates, and peracids and precursors thereof.

[0025] Preferably, the lightening composition does not comprise any peroxygenated salts such as alkali metal or alkaline-earth metal persulfates, perborates and percarbonates.

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

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

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

[0029] For the purposes of the present invention, the terms “alkaline agent” and “basifying agent” are used without distinction.

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

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

[0032] “Alkanolamine” is understood to mean an organic amine comprising a primary, secondary or tertiary amine function, and one or more linear or branched C1-C8alkyl groups bearing one or more hydroxyl radicals.

[0033] Organic amines chosen from alkanolamines such as monoalkanolamines, dialkanolamines or trialkanolamines, comprising one to three identical or different C1-C4hydroxyalkyl radicals, are in particular suitable for implementing the invention.

[0034] In particular, the alkanolamine(s) are chosen from monoethanolamine (MEA), diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, N,N-dimethylethanolamine, 2-amino-2-methyl-1-propanol, triisopropanolamine, 2-amino-2-methyl-1,3-propanediol, 3-amino-1,2-propanediol, 3-dimethylamino-1,2-propanediol, tris(hydroxymethyl)aminomethane, 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, ornithine and citrulline.

[0036] The organic amine may also be chosen from organic amines of heterocyclic type. Besides histidine that has already been mentioned in the amino acids, mention may in particular be made of pyridine, piperidine, imidazole, triazole, tetrazole and benzimidazole. The organic amine may also be chosen from amino acid dipeptides. As amino acid dipeptides that may be used in the present invention, mention may in particular be made of carnosine, anserine and balenine. The organic amine may also be chosen from compounds comprising a guanidine function. As amines of this type different from arginine that may be used in the present invention, mention may in particular be made of creatine, creatinine, 1,1-dimethylguanidine, 1,1-diethylguanidine, glycocyamine, metformin, agmatine, n-amidoalanine, 3-guanidinopropionic acid, 4-guanidinobutyric acid and 2-([amino(imino)methyl]amino)ethane-1-sulfonic acid.

[0037] As hybrid compounds, use may in particular be made of guanidine carbonate or monoethanolamine hydrochloride.

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

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

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

[0041] According to a particular embodiment, the total content of alkanolamine, preferably of monoethanolamine, preferably ranges from 0.1% to 40% by weight, more preferentially from 1% to 30% by weight, better still from 2% to 25% by weight, even better still 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 used in the process according to the invention may also comprise one or more fatty acids.

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

[0044] “Fatty acid” is understood to mean 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 preferentially comprise from 10 to 30 carbon atoms and better still from 12 to 22 carbon atoms. They may optionally be hydroxylated.

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

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

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

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

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

[0050] The fatty acids may be chosen from solid fatty acids, liquid fatty acids, and mixtures thereof.

[0051] For the purposes of the present invention, “solid fatty acid” is understood to mean a fatty acid having a melting point of greater than 25°C, preferably greater than or equal to 28°C, more preferentially greater than or equal to 30°C at atmospheric pressure (1.013×105 Pa).

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

[0053] Particularly preferably, the solid fatty acid(s) are chosen from lauric acid, myristic acid, cetylic acid and stearic acid.

[0054] For the purposes of the present invention, “liquid fatty acid” is understood to mean 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 may be chosen from oleic acid, linoleic acid, arachidonic acid, isostearic acid, isopalmitic acid, and mixtures thereof, preferentially oleic acid.

[0056] Preferably, the lightening composition comprises one or more solid fatty acid(s), preferably chosen from lauric acid, myristic acid, cetylic 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% and preferentially from 1% to 5% by weight, relative to the total weight of the lightening composition.Fatty substances different from fatty acids

[0058] The lightening composition used in the process according to the invention may also comprise one or more fatty substances different from fatty acids.

[0059] Preferably, the lightening composition used in the process according to the invention comprises one or more fatty substances different from fatty acids.

[0060] “Fatty substance” is understood to mean an organic compound that is insoluble in water at 25°C and at atmospheric pressure (1.013×105 Pa) (solubility of less than 5% by weight, and preferably less than 1% by weight, even more preferentially less than 0.1% by weight). They bear in their structure at least one hydrocarbon-based chain including at least 6 carbon atoms and / or a sequence of at least two siloxane groups. In addition, the fatty substances are generally soluble in organic solvents under the same temperature and pressure conditions, for instance chloroform, dichloromethane, carbon tetrachloride, ethanol, benzene, toluene, tetrahydrofuran (THF), liquid petroleum jelly or decamethylcyclopentasiloxane.

[0061] Advantageously, the fatty substances that may be used in the present invention are neither (poly)oxyalkylenated nor (poly)glycerolated.

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

[0063] “Non-silicone fatty substance” is understood to mean a fatty substance not containing any Si-O bonds and “silicone fatty substance” is understood to mean a fatty substance containing at least one Si-O bond.

[0064] The fatty substances useful according to the invention may be liquid fatty substances (or oils) and / or solid fatty substances. “Liquid fatty substance” is understood to mean a fatty substance having a melting point of less than or equal to 25°C at atmospheric pressure (1.013×105 Pa). “Solid fatty substance” is understood to mean a fatty substance having a melting point of greater than 25°C at atmospheric pressure (1.013×105 Pa).

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

[0066] More particularly, the liquid fatty substance(s) according to the invention are chosen from C6to C16liquid hydrocarbons, liquid hydrocarbons comprising more than 16 carbon atoms, non-silicone oils of animal origin, oils of triglyceride type of plant or synthetic origin, fluoro oils, liquid fatty alcohols, liquid esters of a fatty acid and / or of a fatty alcohol different from triglycerides, and silicone oils, and mixtures thereof.

[0067] It is recalled that the fatty alcohols, esters and acids more particularly have at least one saturated or unsaturated, linear or branched hydrocarbon-based group comprising from 6 to 40, better still from 8 to 30, carbon atoms, which is optionally 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 conjugated or non-conjugated carbon-carbon double bonds.

[0068] As regards the C6to C16liquid hydrocarbons, the latter may be linear, branched, or optionally cyclic, and are preferably chosen from alkanes. Examples that may be mentioned include hexane, cyclohexane, undecane, dodecane, isododecane, tridecane or isoparaffins, such as isohexadecane or isodecane, and mixtures thereof.

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

[0070] A hydrocarbon-based oil of animal origin that may be mentioned is perhydrosqualene.

[0071] The triglyceride oils of plant or synthetic origin are preferably chosen from liquid fatty acid triglycerides including from 6 to 30 carbon atoms such as heptanoic or octanoic acid triglycerides or alternatively for example, sunflower oil, corn oil, soybean oil, marrow oil, grapeseed oil, sesame seed oil, hazelnut oil, apricot oil, macadamia oil, arara oil, sunflower oil, castor oil, avocado oil, caprylic / capric acid triglycerides such as those sold by the company Stéarinerie Dubois or those sold under the names Miglyol® 810, 812 and 818 by the company Dynamit Nobel, shea butter oil, and mixtures thereof.

[0072] As regards the fluoro oils, they may be chosen from perfluoromethylcyclopentane and perfluoro-1,3-dimethylcyclohexane, sold under the names Flutec® PC1 and Flutec® PC3 by the company BNFL Fluorochemicals; perfluoro-1,2-dimethylcyclobutane; perfluoroalkanes such as dodecafluoropentane and tetradecafluorohexane, sold under the names PF 5050® and PF 5060® by the company 3M, or bromoperfluorooctyl sold under the name Foralkyl® by the company Atochem; nonafluoromethoxybutane and nonafluoroethoxyisobutane; perfluoromorpholine derivatives such as 4-trifluoromethylperfluoromorpholine sold under the name PF 5052® by the company 3M.

[0073] The liquid fatty alcohols that are suitable for use in the invention are more particularly chosen from linear or branched, saturated or unsaturated, preferably unsaturated or branched, alcohols including from 6 to 40 carbon atoms, preferably from 8 to 30 carbon atoms. Examples that may be mentioned include octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol, isostearyl alcohol, oleyl alcohol, linolenyl alcohol, ricinoleyl alcohol, undecylenyl alcohol and linoleyl alcohol, and mixtures thereof.

[0074] As regards the liquid esters of fatty acids and / or of fatty alcohols different from triglycerides, mentioned previously, mention may in particular be made of esters of saturated or unsaturated, linear C1to C26or branched C3to C26aliphatic monoacids or polyacids and of saturated or unsaturated, linear C1to C26or branched C3to C26aliphatic monoalcohols or polyalcohols, the total carbon number of the esters being greater than or equal to 6, more advantageously greater than or equal to 10.

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

[0076] Among the monoesters, mention may be made of 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 isononanoate; octyldodecyl erucate; oleyl erucate; ethyl and isopropyl palmitates, such as 2-ethylhexyl palmitate, 2-octyldecyl palmitate; alkyl myristates such as isopropyl myristate; isobutyl stearate; 2-hexyldecyl laurate, and mixtures thereof.

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

[0078] Still within the context of this variant, esters of C4to C22dicarboxylic or tricarboxylic acids and of C1to C22alcohols and esters of mono-, di- or tricarboxylic acids and of C2to C26di-, tri-, tetra- or pentahydroxy alcohols may also be used.

[0079] Mention may in particular be made of: diethyl sebacate; diisopropyl sebacate; diisopropyl adipate; di-n-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; triisostearyl citrate; glyceryl trilactate; glyceryl trioctanoate; trioctyldodecyl citrate; trioleyl citrate; propylene glycol dioctanoate; neopentyl glycol diheptanoate; diethylene glycol diisononanoate; and polyethylene glycol distearates, and mixtures thereof.

[0080] The compositions may also comprise, as fatty ester, sugar esters and diesters of C6to C30, preferably C12to C22, fatty acids. It is recalled that “sugar” is understood to mean oxygen-bearing hydrocarbon-based compounds bearing several alcohol functions, with or without aldehyde or ketone functions, and which include at least 4 carbon atoms. These sugars may be monosaccharides, oligosaccharides or polysaccharides.

[0081] Examples of suitable sugars that may be mentioned include sucrose (or saccharose), glucose, galactose, ribose, fucose, maltose, fructose, mannose, arabinose, xylose and lactose, and derivatives thereof, notably alkyl derivatives, such as methyl derivatives, for instance methylglucose.

[0082] The esters of sugars and of fatty acids may be notably chosen from the group comprising the esters or mixtures of esters of sugars described previously and of linear or branched, saturated or unsaturated C6to C30, preferably C12to C22, fatty acids. If they are unsaturated, these compounds may comprise one to three conjugated or non-conjugated carbon-carbon double bonds.

[0083] The esters according to this variant may also be chosen from mono-, di-, tri- and tetraesters, polyesters, and mixtures thereof.

[0084] These esters may be, for example, oleates, laurates, palmitates, myristates, behenates, cocoates, stearates, linoleates, linolenates, caprates, arachidonates, or mixtures thereof such as notably the mixed oleo-palmitate, oleo-stearate and palmito-stearate esters.

[0085] More particularly, use is made of monoesters and diesters and notably sucrose, glucose or methylglucose mono- or dioleates, -stearates, -behenates, -oleopalmitates, -linoleates, -linolenates and -oleostearates, and mixtures thereof.

[0086] An example that may be mentioned is the product sold under the name Glucate® DO by the company Amerchol, which is a methylglucose dioleate.

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

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

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

[0090] “Fatty alcohol” is understood to mean 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 oxyalkylenated nor glycerolated.

[0091] The solid fatty alcohols may be saturated or unsaturated, and linear or branched, and include from 8 to 40 carbon atoms, preferably from 10 to 30 carbon atoms. Preferably, the 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, preferentially from 10 to 30, carbon atoms, better still from 10 to 30, or even from 12 to 24, atoms, even better still from 14 to 22 carbon atoms.

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

[0093] The solid fatty alcohols that may be used may be chosen, alone or as a mixture, from: 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); montanyl alcohol (or 1-octacosanol); myricyl alcohol (or 1-triacontanol).

[0094] Preferentially, the solid fatty alcohol is chosen from cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, arachidyl alcohol, and mixtures thereof, such as cetylstearyl alcohol or cetearyl alcohol. Particularly preferably, the solid fatty alcohol is chosen from cetylstearyl or cetearyl alcohol and cetyl alcohol.

[0095] The solid esters of a fatty acid and / or of a fatty alcohol that may be used are preferably chosen from esters derived from a C9-C26carboxylic fatty acid and / or from a C9-C26fatty alcohol.

[0096] Preferably, these solid fatty esters are esters of a linear or branched, saturated carboxylic acid including at least 10 carbon atoms, preferably from 10 to 30 carbon atoms and more particularly from 12 to 24 carbon atoms, and of a linear or branched, saturated monoalcohol including 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] Use may also be made of the esters of C4-C22di- or tricarboxylic acids and of C1-C22alcohols and the esters of mono-, di- or tricarboxylic acids and of C2-C26di-, tri-, tetra- or pentahydroxy alcohols.

[0098] Mention may in particular be made of octyldodecyl behenate, isocetyl behenate, cetyl lactate, stearyl octanoate, octyl octanoate, cetyl octanoate, decyl oleate, hexyl stearate, octyl stearate, myristyl stearate, cetyl stearate, stearyl stearate, octyl pelargonate, cetyl myristate, myristyl myristate, stearyl myristate, diethyl sebacate, diisopropyl sebacate, diisopropyl adipate, di-n-propyl adipate, dioctyl adipate, dioctyl maleate, octyl palmitate, myristyl palmitate, cetyl palmitate, stearyl palmitate, and mixtures thereof.

[0099] Preferably, the solid esters of a fatty acid and / or of a fatty alcohol are chosen from C9-C26alkyl palmitates, particularly myristyl palmitate, cetyl palmitate and stearyl palmitate; C9-C26alkyl myristates, such as cetyl myristate, stearyl myristate and myristyl myristate; C9-C26alkyl stearates, particularly myristyl stearate, cetyl stearate and stearyl stearate; and mixtures thereof.

[0100] For the purposes of the present invention, a wax is a lipophilic compound, which is solid at 25°C and atmospheric pressure, with a reversible solid / liquid change of state, having a melting point that is greater than about 40°C and may be up to 200°C, and having anisotropic crystal organization in the solid state. In general, the size of the wax crystals is such that the crystals diffract and / or scatter light, giving the composition that comprises them a more or less opaque cloudy appearance. 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 on returning the temperature of the mixture to room temperature, recrystallization of the wax, which is microscopically and macroscopically detectable (opalescence), is obtained.

[0101] In particular, the waxes that are suitable for use in the invention may be chosen from waxes of animal, plant or mineral origin, non-silicone synthetic waxes, and mixtures thereof.

[0102] Mention may in particular be made of hydrocarbon-based waxes, such as beeswax, notably of biological origin, lanolin wax, and Chinese insect waxes; rice bran wax, carnauba wax, candelilla wax, ouricury wax, esparto grass wax, berry wax, shellac wax, Japan wax and sumac wax; montan wax, orange wax and lemon wax, microcrystalline waxes, paraffins and ozokerite; polyethylene waxes, the waxes obtained by Fischer-Tropsch synthesis and waxy copolymers, and also esters thereof.

[0103] Mention may further be made of C20to C60microcrystalline waxes, such as Microwax HW.

[0104] Mention may also be made of the MW 500 polyethylene wax sold under the reference Permalen 50-L Polyethylene.

[0105] Mention may also be made of the waxes obtained by catalytic hydrogenation of animal or plant oils having linear or branched C8to C32fatty chains. Among these waxes, mention may in particular be made of isomerized jojoba oil, such as trans-isomerized partially hydrogenated jojoba oil, particularly the product manufactured or sold by the company Desert Whale under the commercial reference Iso-Jojoba-50®, hydrogenated sunflower oil, hydrogenated castor oil, hydrogenated coconut oil, hydrogenated lanolin oil, and bis(1,1,1-trimethylolpropane) tetrastearate, particularly the product sold under the name Hest 2T-4S®by the company Heterene.

[0106] Use may also be made of the waxes obtained by hydrogenation of castor oil esterified with cetyl alcohol, such as those sold under the names Phytowax Castor 16L64®and 22L73®by the company Sophim.

[0107] A wax that may also be used is a C20to C40alkyl (hydroxystearyloxy)stearate (the alkyl group comprising from 20 to 40 carbon atoms), alone or as 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; mention may in particular be made of carnauba microwaxes, such as the product sold under the name MicroCare 350®by the company Micro Powders, synthetic-wax microwaxes, such as the product sold under the name MicroEase 114S®by the company Micro Powders, microwaxes constituted of a mixture of carnauba wax and of polyethylene wax, such as the products sold under the names Micro Care 300®and 310®by the company Micro Powders, microwaxes constituted of a mixture of carnauba wax and of synthetic wax, such as the product sold under the name Micro Care 325®by the company Micro Powders, polyethylene microwaxes, such as the products sold under the names Micropoly 200®, 220®, 220L®and 250S®by the company Micro Powders, and polytetrafluoroethylene microwaxes, such as the products sold under the names Microslip 519®and 519 L®by the company Micro Powders.

[0109] The waxes are preferably chosen from mineral waxes, such as paraffin wax, petroleum jelly wax, lignite wax or ozokerite; plant waxes, such as cocoa butter or cork fiber or sugar cane waxes, olive tree wax, rice wax, hydrogenated jojoba wax, ouricury wax, carnauba wax, candelilla wax, esparto grass wax, or absolute waxes of flowers, such as the essential wax of blackcurrant blossom sold by the company Bertin (France); waxes of animal origin, such as beeswaxes or modified beeswaxes (cera bellina), spermaceti, lanolin wax and lanolin derivatives; microcrystalline waxes; and mixtures thereof.

[0110] The ceramides or ceramide analogues, such as glycoceramides, that may be used in the compositions according to the invention, are known; mention may in particular be made of ceramides of classes I, II, III and V according to the Dawning classification.

[0111] The ceramides or analogues thereof that may be used preferably correspond to the following formula: R3CH(OH)CH(CH2OR2)(NHCOR1), in which:R1denotes a linear or branched, saturated or unsaturated alkyl group, derived from C14-C30fatty acids, it being possible for this group to be substituted by a hydroxyl group in the alpha position, or a hydroxyl group in the omega position esterified with a saturated or unsaturated C16-C30fatty acid;R2denotes a hydrogen atom, a (glycosyl)n group, a (galactosyl)m group or a sulfogalactosyl group, in which n is an integer ranging from 1 to 4 and m is an integer ranging from 1 to 8;R3denotes a C15-C26hydrocarbon-based group saturated or unsaturated in the alpha position, it being possible for this group to be substituted by one or more C1-C14alkyl groups; it being understood that in the case of natural ceramides or glycoceramides, R3may also denote a C15-C26α-hydroxyalkyl group, the hydroxyl group being optionally esterified with a C16-C30α-hydroxy acid.

[0112] The ceramides that are more particularly preferred are the compounds for which R1denotes a saturated or unsaturated alkyl derived from C16-C22fatty acids; R2denotes a hydrogen atom and R3denotes a saturated linear C15group.

[0113] Preferentially, use is made of ceramides for which R1denotes a saturated or unsaturated alkyl group derived from C14-C30fatty acids; R2denotes a galactosyl or sulfogalactosyl group; and R3denotes a -CH=CH-(CH2)12-CH3group.

[0114] Use may also be made of the compounds for which R1denotes a saturated or unsaturated alkyl radical derived from C12-C22fatty acids; R2denotes a galactosyl or sulfogalactosyl radical; and R3denotes a saturated or unsaturated C12-C22hydrocarbon-based radical and preferably a -CH=CH-(CH2)12-CH3group.

[0115] As compounds that are particularly preferred, mention may also be made of 2-N-linoleoylaminooctadecane-1,3-diol; 2-N-oleoylaminooctadecane-1,3-diol; 2-N-palmitoylaminooctadecane-1,3-diol; 2-N-stearoylaminooctadecane-1,3-diol; 2-N-behenoylaminooctadecane-1,3-diol; 2-N-[2-hydroxypalmitoyl]aminooctadecane-1,3-diol; 2-N-stearoylaminooctadecane-1,3,4-triol and in particular N-stearoylphytosphingosine, 2-N-palmitoylaminohexadecane-1,3-diol, N-linoleoyldihydrosphingosine, N-oleoyldihydrosphingosine, N-palmitoyldihydrosphingosine, N-stearoyldihydrosphingosine, and N-behenoyldihydrosphingosine, N-docosanoyl-N-methyl-D-glucamine, cetylic acid N-(2-hydroxyethyl)-N-(3-cetyloxy-2-hydroxypropyl)amide and bis(N-hydroxyethyl-N-cetyl)malonamide; and mixtures thereof. N-Oleoyldihydrosphingosine will preferably be used.

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

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

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

[0119] The lightening composition used in the process according to the invention may also comprise one or more surfactants different from fatty acids.

[0120] Preferably, the lightening composition used in the process according to the invention comprises one or more surfactants different from fatty acids.

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

[0122] Preferably, the lightening composition used in the process according to the invention comprises one or more nonionic surfactants.

[0123] The nonionic surfactant(s) that may be used in the lightening composition used in the process of the present invention are notably described, for example, in “Handbook of Surfactants” by M.R. Porter, published by Blackie & Son (Glasgow and London), 1991, pp. 116-178.

[0124] Examples of nonionic surfactants that may be mentioned include the following compounds, alone or as a mixture:- oxyalkylenated (C8-C24)alkylphenols;- saturated or unsaturated, linear or branched, oxyalkylenated or glycerolated C8to C40alcohols, preferably including one or two fatty chains;- saturated or unsaturated, linear or branched, oxyalkylenated C8to C30fatty acid amides;- esters of saturated or unsaturated, linear or branched, C8to C30acids and of polyethylene glycols;- fatty acid esters of sucrose;- esters of saturated or unsaturated, linear or branched, C8to C30acids and of sorbitol, which are preferably oxyethylenated;- esters of saturated or unsaturated, linear or branched, C8-C30fatty acids and of glycerol;- C8-C30fatty acid esters of sorbitan;- C8-C30fatty acid esters of polyoxyethylenated sorbitan;- (C8-C30)alkyl(poly)glucosides, (C8-C30)alkenyl(poly)glucosides, which are optionally oxyalkylenated (0 to 10 oxyalkylene units) and comprising from 1 to 15 glucose units, (C8-C30)alkyl(poly)glucoside esters;- saturated or unsaturated oxyethylenated plant oils;- condensates of ethylene oxide and / or of propylene oxide;-N-(C8-C30)alkylglucamine andN-(C8-C30)acylmethylglucamine derivatives;- amine oxides.

[0125] They are notably chosen from alcohols, α-diols and (C1-C20)alkylphenols, 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, it being possible for the number of ethylene oxide or propylene oxide groups to range notably from 1 to 200 and the number of glycerol groups to range notably from 1 to 30.

[0126] Mention may also be made of condensates of ethylene oxide and of propylene oxide with fatty alcohols; ethoxylated fatty amides preferably having from 1 to 30 ethylene oxide units, polyglycerolated fatty amides comprising on average from 1 to 5, and in particular from 1.5 to 4, glycerol groups, fatty acid esters of sucrose, fatty acid esters of polyethylene glycol, oxyethylenated plant oils, N-(C6-C24alkyl)glucamine derivatives, amine oxides such as (C10-C14alkyl)amine oxides or N-(C10-C14acyl)aminopropylmorpholine oxides.

[0127] The C8-C30, preferably C12-C22, fatty acid esters (notably mono-, di- and triesters) of sorbitan may be chosen 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; and sorbitan tristearate.

[0128] The C8-C30fatty acid esters (notably mono-, di- and triesters) of polyoxyethylenated sorbitan are preferably chosen from C8-C30fatty acid ester(s) of oxyethylenated sorbitan having from 1 to 30 ethylene oxide units, preferably from 2 to 20 ethylene oxide units, more preferably from 2 to 10 ethylene oxide units.

[0129] Preferentially, the C8-C30fatty acid ester(s) of oxyethylenated sorbitan is / are chosen from C12-C18fatty acid esters of oxyethylenated sorbitan, in particular from oxyethylenated esters of lauric acid, of myristic acid, of cetylic acid and of stearic acid and of sorbitan.

[0130] Preferably, the C8-C30fatty acid ester(s) of oxyethylenated sorbitan is / are chosen from oxyethylenated (4 EO) sorbitan monolaurate (Polysorbate-21), oxyethylenated (20 EO) sorbitan monolaurate (Polysorbate-20), oxyethylenated (20 EO) sorbitan monopalmitate (Polysorbate-40), oxyethylenated (20 EO) sorbitan monostearate (Polysorbate-60), oxyethylenated (4 EO) sorbitan monostearate (Polysorbate-61), oxyethylenated (20 EO) sorbitan monooleate (Polysorbate-80), oxyethylenated (5 EO) sorbitan monooleate (Polysorbate-81), oxyethylenated (20 EO) sorbitan tristearate (Polysorbate-65), oxyethylenated (20 EO) sorbitan trioleate (Polysorbate-85).

[0131] The nonionic surfactant(s) are preferably chosen from ethoxylated C8-C24fatty alcohols comprising from 1 to 200 ethylene oxide groups, preferably from 1 to 50 ethylene oxide groups, (C6-C24alkyl)polyglycosides, esters of saturated or unsaturated, linear or branched, C8-C30fatty acids and of glycerol, C8-C30fatty acid esters of oxyethylenated sorbitan, and mixtures thereof, preferentially from ethoxylated C8-C24fatty alcohols comprising from 1 to 50 ethylene oxide groups, (C6-C24alkyl)polyglycosides, esters of saturated or unsaturated, linear or branched, C8-C30fatty acids and of glycerol.

[0132] More preferentially, the nonionic surfactant(s) are chosen from ethoxylated C8-C24fatty alcohols comprising from 1 to 200 ethylene oxide groups, preferably from 1 to 50 ethylene oxide groups.

[0133] Preferably, the lightening composition used in the process according to the invention comprises one or more ethoxylated C8-C24fatty alcohols comprising from 1 to 200 ethylene oxide groups, preferably from 1 to 50 ethylene oxide groups.

[0134] When they are present, the surfactant(s) different from fatty acids are preferably present in the lightening composition used in the process according to the invention in a total content ranging from 0.01% to 20% by weight, more preferentially from 0.1% to 15% by weight, better still from 0.5% to 10% by weight, relative to the total weight of the composition containing said surfactant(s).

[0135] When they are present, the nonionic and / or anionic surfactant(s) different from 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 preferentially from 0.5% to 15% by weight, better still from 1% to 12% by weight, relative to the total weight of the composition containing said surfactant(s).

[0136] When they are present, the nonionic 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 preferentially from 0.5% to 15% by weight, better still from 1% to 12% by weight, relative to the total weight of the composition containing said surfactant(s).Organic solvent

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

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

[0139] Examples of organic solvents that may be mentioned include linear or branched C2to C4alkanols, 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 monomethyl ether and monoethyl ether, and also aromatic alcohols or ethers, such as benzyl alcohol or phenoxyethanol, and mixtures thereof.

[0140] When they are present, the organic solvent(s) are preferably present in the lightening composition at a total content ranging from 0.01% to 30% by weight, preferably ranging from 0.05% to 15% by weight, preferentially from 0.1% to 10% by weight, relative to the total weight of the lightening 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 more advantageously still 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, better still from 50% to 85% by weight, relative to the total weight of the lightening composition.

[0142] Preferably, the pH of the lightening 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 comprise one or more additives, among which mention may be made of anionic, nonionic, amphoteric and cationic polymers or mixtures thereof, mineral thickening agents, antidandruff agents, anti-seborrhoeic agents, agents for preventing hair loss and / or for promoting hair regrowth, vitamins and provitamins including panthenol, sunscreens, mineral or organic pigments, plasticizers, solubilizers, opacifiers or pearlescent agents, antioxidants, sequestrants, fragrances, and preservatives.

[0144] Needless to say, those skilled in the art will take care to choose this or these optional additional compounds such that the advantageous properties intrinsically associated with the lightening composition are not, or are not substantially, adversely affected by the envisaged addition(s).

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

[0146] Preferably, the lightening composition that has just been 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 comprise one or more fatty substances as defined above, preferably chosen from fatty alcohols, one or more surfactants as defined above, preferably chosen from nonionic surfactants, and one or more solvent(s) as defined above.

[0149] The oxidizing composition also preferably comprises one or more acidifying agents. Among the acidifying agents, mention may be made, by way of example, of mineral or organic acids, such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid or 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 more advantageously still 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, better still 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, preferentially between 1.5 and 4.5. This pH may be adjusted to the desired value by using one or more acidifying agents, which may notably be chosen from those described previously.

[0152] Alkaline composition

[0153] In addition to the alkaline agent(s) described above, the alkaline composition may comprise one or more fatty acids as defined previously, one or more fatty substances as defined previously, preferably chosen from solid fatty alcohols, solid esters of fatty acids and / or of fatty alcohols, and mixtures thereof, one or more surfactants as defined previously, preferably chosen from nonionic surfactants, and 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 still from 20% to 50% by weight, relative to the total weight of the alkaline composition.

[0155] The pH of the alkaline composition, when it is aqueous, preferably ranges from 8 to 12, preferentially from 9 to 11, better still from 10 to 11.Dyeing compositionDirect dyes

[0156] The dyeing composition used in the process of the invention comprises one or more direct dye(s).

[0157] “Direct dye” is understood to mean colored species. These are dyes which will spread superficially on the fiber.

[0158] The direct dye(s) that may be used according to the invention are chosen from natural direct dyes, synthetic direct dyes, and mixtures thereof.

[0159] Preferably, the direct dye(s) that may be used according to the invention are chosen from ionic direct dyes and nonionic direct dyes, more particularly from cationic direct dyes, amphoteric direct dyes, anionic direct dyes, nonionic direct dyes, and mixtures thereof.

[0160] The direct dyes are chosen, for example, from nitrobenzene direct dyes, azo direct dyes, tetraazapentamethine dyes, quinone and in particular anthraquinone dyes, azine direct dyes, triarylmethane direct dyes, azomethine direct dyes and natural direct dyes.

[0161] The dyeing composition may comprise one or more nonionic direct dyes.

[0162] Among the nonionic direct dyes, mention may be made of neutral nitrobenzene direct dyes, neutral azo direct dyes and neutral anthraquinone dyes.

[0163] The dyeing composition may comprise one or more cationic direct dyes.

[0164] “Cationic direct dye” is understood to mean any dye different from oxidation dyes, commonly referred to as “basic” direct dyes or “basic dyes”. They are referred to as “basic” because of their affinity for acidic substances, notably comprising at least one cationic or cationizable endocyclic or exocyclic group within their structure.

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

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

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

[0168] For the cationic azo dyes, mention may be made particularly of those resulting from the cationic dyes described in Kirk-Othmer Encyclopedia of Chemical Technology, “Dyes, Azo”, J. Wiley & Sons, updated on 19 April 2010.

[0169] Among the azo dyes that may be used according to the invention, mention may be made of the cationic azo dyes described in patent applications WO 95 / 15144, WO 95 / 01772 and EP714954.

[0170] Among the azo dyes described in the Color Index International 3rd edition, mention may be made notably of the following compounds:-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 abovementioned Color Index International are suitable for use and, among these, mention may be made, inter alia, of the following dyes:-Basic Blue 22-Basic Blue 99.

[0172] Among the azine dyes that are suitable for use, mention may be made of those listed in the Color Index International, for example the following dyes:-Basic Blue 17-Basic Red 2.

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

[0174] Mention may also be made of the cationic dyes described in US 5888252, EP 1133975, WO 03 / 029359, EP 860636, WO 95 / 01772, WO 95 / 15144 and EP 714954. Mention may also be made of those listed in the encyclopaedia “The Chemistry of Synthetic Dyes” by K. Venkataraman, 1952, Academic Press, vol. 1 to 7, in the “Kirk-Othmer Encyclopedia of Chemical Technology”, in the 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.

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

[0176] According to a particular embodiment, the direct dyes are cationic azo dyes, described in EP 850636, FR 2788433, EP 920856, WO 9948465, FR 2757385, EP 850637, EP 918053, WO 9744004, FR 2570946, FR 2285851, DE 2538363, FR 2189006, FR 1560664, FR 1540423, FR 1567219, FR 1516943, FR 1221122, DE 4220388, DE 4137005, WO 0166646, US 5708151, WO 9501772, WO 515144, GB 1195386, US 3524842, US 5879413, EP 1062940, EP 1133976, GB 738585, DE 2527638, FR 2275462, GB 1974-27645, Acta Histochem. (1978), 61(1), 48-52; Tsitologiya (1968), 10(3), 403-5; Zh. Obshch. Khim. (1970), 40(1), 195-202; Ann. Chim. (Rome) (1975), 65(5-6), 305-14; Journal of the Chinese Chemical Society (Taipei) (1998), 45(1), 209-211; Rev. Roum. Chim. (1988), 33(4), 377-83; Text. Res. J. (1984), 54(2), 105-7; Chim. Ind. (Milan) (1974), 56(9), 600-3; Khim. Tekhnol. (1979), 22(5), 548-53; Ger. Monatsh. Chem. (1975), 106(3), 643-8; MRL Bull. Res. Dev. (1992), 6(2), 21-7; Lihua Jianyan, Huaxue Fence (1993), 29(4), 233-4; Dyes Pigm. (1992), 19(1), 69-79; Dyes Pigm. (1989), 11(3), 163-72.

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

[0178] These cationic radicals are, for example, a cationic radical:- bearing a (di / tri)(C1-C8)alkylammonium exocyclic charge, or- bearing an endocyclic charge, such as comprising a cationic heteroaryl group chosen from: acridinium, benzimidazolium, benzobistriazolium, benzopyrazolium, benzopyridazinium, benzoquinolium, benzothiazolium, benzotriazolium, benzoxazolium, bipyridinium, bistetrazolium, dihydrothiazolium, imidazopyridinium, imidazolium, indolium, isoquinolium, naphthoimidazolium, naphthoxazolium, naphthopyrazolium, oxadiazolium, oxazolium, oxazolopyridinium, oxonium, phenazinium, phenooxazolium, pyrazinium, pyrazolium, pyrazoyltriazolium, pyridinium, pyridinoimidazolium, pyrrolium, pyrylium, quinolium, tetrazolium, thiadiazolium, thiazolium, thiazolopyridinium, thiazoylimidazolium, thiopyrylium, triazolium or xanthylium.

[0179] Mention may be made of the hydrazono cationic dyes of formulae (C-II) and (C-III), the azo dyes of formulae (C-IV) and (C-V) below, and also the optical and geometric isomers thereof and tautomers thereof, the organic or mineral acid or base salts thereof, and also the solvates thereof such as hydrates:

[0180] Het+-C(Ra)=N-N(Rb)-Ar, Q-(C-II)

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

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

[0183] Ar+-N=N-Ar’’, Q-(C-V),

[0184] in which formulae (C-II) to (C-V):* Het+represents a cationic heteroaryl radical, preferentially having an endocyclic cationic charge, such as imidazolium, indolium or pyridinium, which is optionally substituted, preferentially by at least one (C1-C8)alkyl group, such as methyl;* Ar+represents an aryl radical, such as phenyl or naphthyl, having an exocyclic cationic charge, preferentially ammonium, particularly tri(C1-C8)alkylammonium, such as trimethylammonium;* Ar represents an aryl group, in particular phenyl, which is optionally substituted, preferentially by one or more electron-donating groups, such as i) optionally substituted (C1-C8)alkyl, ii) optionally substituted (C1-C8)alcoxy, iii) (di)(C1-C8)(alkyl)amino optionally substituted on the alkyl group(s) by a hydroxyl group, iv) aryl(C1-C8)alkylamino, v) optionally substituted N-(C1-C8)alkyl-N-aryl(C1-C8)alkylamino or else Ar represents a julolidine group;* Ar” represents an optionally substituted (hetero)aryl group, such as phenyl or pyrazolyl, which are optionally substituted, preferentially by one or more (C1-C8)alkyl, hydroxyl, (di)(C1-C8)(alkyl)amino, (C1-C8)alkoxy or phenyl groups;* Ra and Rb, which may be identical or different, represent a hydrogen atom or a (C1-C8)alkyl group which is optionally substituted, preferentially by a hydroxyl group;* or else the substituent Ra with a Het+substituent and / or Rb with an Ar substituent form, together with the atoms which bear them, a (hetero)cycloalkyl; in particular, Ra and Rb represent a hydrogen atom or a (C1-C4)alkyl group optionally substituted by a hydroxyl group;* Q-represents an organic or mineral anionic counterion, such as a halide or an alkyl sulfate.

[0185] In particular, mention may be made of the azo and hydrazono direct dyes bearing endocyclic cationic charges, of formulae (C-II) to (C-V) as defined previously; more particularly the cationic direct dyes of formulae (C-II) to (C-V) bearing endocyclic cationic charges described in patent applications WO 95 / 15144, WO 95 / 01772 and EP-714954.

[0186] Preferentially, mention may be made of the following direct dyes: (C-II-1), (C-IV-1),

[0187] in which formulae (C-II-1) and (C-IV-1):- R1represents a (C1-C4)alkyl group, such as methyl;- R2and R3, which are identical or different, represent a hydrogen atom or a (C1-C4)alkyl group, such as methyl; and- R4represents a hydrogen atom or an electron-donating group, such as optionally substituted (C1-C8)alkyl, optionally substituted (C1-C8)alkoxy, or (di)(C1-C8)(alkyl)amino optionally substituted on the alkyl group(s) by a hydroxyl group; in particular, R4is a hydrogen atom,- Z represents a CH group or a nitrogen atom, preferentially CH,- Q-is an anionic counterion as defined above, particularly a halide, such as chloride, or an alkyl sulfate, such as methyl sulfate or mesityl.

[0188] In particular, the dyes of formulae (C-II-1) and (C-IV-1) are chosen from Basic Red 51, Basic Yellow 87 and Basic Orange 31 or derivatives thereof: Basic Red 51 Basic Orange 31 Basic Yellow 87,

[0189] with Q’ being an anionic counterion as defined above, particularly a halide, such as chloride, or an alkyl sulfate, such as methyl sulfate or mesityl.

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

[0191] Fluorescent dyes that may be mentioned include the radicals resulting from the following dyes: acridines, acridones, benzanthrones, benzimidazoles, benzimidazolones, benzindoles, benzoxazoles, benzopyrans, benzothiazoles, coumarins, difluoro{2-[(2H-pyrrol-2-ylidene-kN)methyl]-1H-pyrrolato-kN}borons (BODIPY®), diketopyrrolopyrroles, fluorindines, (poly)methines (notably cyanines and styryls / hemicyanines), naphthalimides, naphthanilides, naphthylamines (such as dansyls), oxadiazoles, oxazines, perilones, perinones, perylenes, polyenes / carotenoids, squaranes, stilbenes and xanthenes.

[0192] Mention may also be made of the fluorescent dyes described in the documents EP 1133975, WO 03 / 029359, EP 860636, WO 95 / 01772, WO 95 / 15144, EP 714954 and those listed in the encyclopaedia “The Chemistry of Synthetic Dyes” by K. Venkataraman, 1952, Academic Press, vol. 1 to 7, in the “Kirk-Othmer Encyclopedia of Chemical Technology”, in the 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", 10th Ed., Molecular Probes / Invitrogen – Oregon 2005, circulated on the Internet or in the preceding printed editions.

[0193] According to one variant of the invention, the cationic dye(s) are fluorescent and comprise at least one quaternary ammonium radical such as those of formula (C-VI) below, and also the optical and geometric isomers thereof and tautomers thereof, the organic or mineral acid or base salts thereof, and also the solvates thereof such as hydrates:

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

[0195] in which formula (C-VI):* W+represents a cationic heterocyclic or heteroaryl group, particularly comprising a quaternary ammonium optionally substituted by one or more (C1-C8)alkyl groups optionally substituted notably by one or more hydroxyl groups;* Ar represents an aryl group, such as phenyl or naphthyl, which are optionally substituted, preferentially by i) one or more halogen atoms, such as chlorine or fluorine; ii) one or more (C1-C8)alkyl, preferably (C1-C4)alkyl, groups, such as methyl; iii) one or more hydroxyl groups; iv) one or more (C1-C8)alkoxy groups, such as methoxy; v) one or more hydroxy(C1-C8)alkyl groups, such as hydroxyethyl, vi) one or more amino or (di)(C1-C8)alkylamino groups, preferably with the C1-C4alkyl part optionally 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 piperazinyl, piperidinyl or 5- or 6-membered heteroaryl, such as pyrrolidinyl, pyridinyl and imidazolinyl;* m' represents an integer between 1 and 4 inclusive; in particular, m is equal to 1 or 2; more preferentially 1;* Rc and Rd, which may be identical or different, represent a hydrogen atom or an optionally substituted (C1-C8)alkyl group, preferentially an optionally substituted (C1-C4)alkyl group, or else Rc contiguous with W+and / or Rd contiguous with Ar form, with the atoms which bear them, a (hetero)cycloalkyl; in particular, Rc is contiguous with W+and they form a (hetero)cycloalkyl, such as cyclohexyl;* Q-is an organic or mineral anionic counterion as defined above.

[0196] Among the cationic direct dyes, mention may also be made of triarylmethane cationic dyes.

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

[0198] and also the organic or mineral acid or base addition salts thereof, the optical and geometric isomers thereof and tautomers thereof, and the mesomeric forms thereof, and the solvates thereof such as hydrates:

[0199] in which formulae (C-VII) and (C-VII’):* R1, R2, R3and R4, which may be identical or different, represent a hydrogen atom or a group from among: (C1-C6)alkyl which is optionally substituted, preferably by a hydroxyl group; aryl, such as phenyl, aryl(C1-C4)alkyl, such as benzyl, heteroaryl or heteroaryl(C1-C4)alkyl, or else two R1and R2and / or R3and R4groups, borne by the same nitrogen atom, form, together with the nitrogen atom which bears them, an optionally substituted heterocycloalkyl group, such as morpholino, piperazino or piperidino; preferably, R1, R2, R3and R4, which may be identical or different, represent a hydrogen atom or a (C1-C4)alkyl group,* R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, and R16, which may be identical or different, represent a hydrogen atom, a halogen atom, or a group chosen from i) hydroxyl, ii) thiol, iii) amino, iv) (di)(C1-C4)(alkyl)amino, v) (di)arylamino, such as (di)phenylamino, vi) nitro, vii) acylamino (-NR-C(O)R’), in which the R radical is a hydrogen atom or a C1-C4alkyl radical optionally bearing at least one hydroxyl group and the R’ radical is a C1-C2alkyl radical; viii) carbamoyl ((R)2N-C(O)-), in which the R radicals, which may be identical or different, represent a hydrogen atom or a C1-C4alkyl radical optionally bearing at least one hydroxyl group; ix) carboxylic acid or ester, (-O-C(O)R’) or (-C(O)OR’), in which the R’ radical is a hydrogen atom or C1-C4alkyl optionally bearing at least one hydroxyl group and the R’ radical is a C1-C2alkyl radical; x) alkyl which is optionally substituted, notably by a hydroxyl group; xi) alkylsulfonylamino (R’SO2-NR-), in which the R radical represents a hydrogen atom or a C1-C4alkyl radical optionally bearing at least one hydroxyl group and the R’ radical represents a C1-C4alkyl radical, a phenyl radical; xii) aminosulfonyl ((R)2N-SO2-), in which the R radicals, which may be identical or different, represent a hydrogen atom or a C1-C4alkyl radical optionally bearing at least one hydroxyl group; xiii) (C1-C4)alkoxy; and xiv) (C1-C4)alkylthio;* or else two radicals borne by two contiguous carbon atoms, R5and R6and / or R7and R8and / or R9and R10and / or R11and R12and / or R13and R14and / or R15and R16, form, together with the carbon atoms which bear them, a fused 6-membered aryl or heteroaryl, preferably benzo, ring, it being possible for said ring in addition to optionally be substituted, preferably an unsubstituted benzo ring;* Q-represents an anionic counterion for achieving electrical neutrality, preferably chosen from halides, such as chloride or bromide, and phosphate.

[0200] When the cationic dye comprises one or more anionic substituents such as COOR or SO3R with R denoting a hydrogen or a cation, it is understood that there are then more cationic substituents than anionic substituents, such that the overall resulting charge of the triarylmethane structure is cationic.

[0201] According to a preferred embodiment, the triarylmethane dye(s) is / are chosen from those of formula (C-VII) or (C-VII’), in which, taken together or separately,- R1, R2, R3and R4represent a hydrogen atom or a (C1-C4)alkyl group, such as methyl or ethyl,- R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15and R16represent a hydrogen atom, a halogen atom, such as chlorine, or a (C1-C4)alkyl group, such as methyl or ethyl, an amino group, a (di)(C1-C4)(alkyl)amino group and, preferably, at least one of the groups R9, R10, R11or R12represents a hydrogen atom, a halogen atom (Cl), or an amino group, or a (C1-C4)(alkyl)amino or (di)(C1-C4)(alkyl)amino group, preferably in the para position on the phenyl group.

[0202] Preferably, the direct dye(s) of triarylmethane structure are chosen from Basic Violet 1, Basic Violet 2, Basic Violet 3, Basic Violet 4, Basic Violet 14, Basic Blue 1, Basic Blue 7, Basic Blue 26, Basic Green 1, Basic Blue 77 (also known as HC Blue 15), and mixtures thereof.

[0203] Among the cationic direct dyes, mention may also be made of anthraquinone cationic dyes.

[0204] The anthraquinone cationic direct dye(s) that may be used in the dyeing composition of the invention comprise a quaternary ammonium group.

[0205] These cationic radicals are, for example, a cationic radical:- bearing a (C1-C8)alkylammonium exocyclic charge, or- bearing an endocyclic charge, such as comprising a cationic heteroaryl group chosen from: acridinium, benzimidazolium, benzobistriazolium, benzopyrazolium, benzopyridazinium, benzoquinolium, benzothiazolium, benzotriazolium, benzoxazolium, bipyridinium, bistetrazolium, dihydrothiazolium, imidazopyridinium, imidazolium, indolium, isoquinolium, naphthoimidazolium, naphthoxazolium, naphthopyrazolium, oxadiazolium, oxazolium, oxazolopyridinium, oxonium, phenazinium, phenooxazolium, pyrazinium, pyrazolium, pyrazoyltriazolium, pyridinium, pyridinoimidazolium, pyrrolium, pyrylium, quinolium, tetrazolium, thiadiazolium, thiazolium, thiazolopyridinium, thiazoylimidazolium, thiopyrylium, triazolium or xanthylium.

[0206] Preferably, the cationic charge is exocyclic.

[0207] Among the anthraquinone cationic direct dyes, those of formula (C-VIII) having an exocyclic cationic charge are preferred: (C-VIII)

[0208] in which:- R1, R2and R3, which may be identical or different, represent a hydrogen atom or an optionally substituted (C1-C8)alkyl group;- R4represents a hydrogen atom or an optionally substituted (C1-C8)alkyl group;- R5represents a hydrogen atom, an optionally substituted (C1-C8)alkyl group, an optionally substituted (C1-C8)alkylene group, a halogen, a hydroxyl group or a (C1-C8)alkoxy group;- n represents a number between 1 and 8;- Q-represents an organic or mineral anionic counterion, such as a halide or an alkyl sulfate.

[0209] Preferably, in formula (C-VIII):- R1, R2and R3, which may be identical or different, represent an optionally substituted (C1-C6)alkyl group;- R4represents a hydrogen atom or an optionally substituted (C1-C6)alkyl group;- R5represents a hydrogen atom or an optionally substituted (C1-C8)alkyl group,- n represents a number between 1 and 6;- Q-represents a halide or an alkyl sulfate.

[0210] More preferentially, in formula (CVIII):- R1, R2and R3, which may be identical or different, represent an optionally substituted (C1-C3)alkyl group;- R4represents a hydrogen atom or a methyl, preferably a methyl;- R5represents a hydrogen atom or a methyl, preferably a hydrogen atom;- n represents a number between 2 and 4;- Q-represents a halide or an alkyl sulfate, preferably a halide.

[0211] Among the dyes of formula (C-VIII), use may in particular be made of the dyes of formula (C-VIII’) or of formula (C-VIII’’) below: (C-VIII’) (C-VIII’’)

[0212] with Q’ being an anionic counterion, particularly a halide, such as bromide or chloride, or an alkyl sulfate, such as methyl sulfate or mesityl. Preferably, Q-is a halide, better still a bromide.

[0213] “Anionic counterion” is understood to mean an anion or an anionic group derived from an organic or mineral acid salt which counterbalances the cationic charge of the dye; more particularly, the anionic counterion is chosen from i) halides, such as chloride or bromide; ii) nitrates; iii) sulfonates, including C1-C6alkylsulfonates: 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-O-S(O)O-, such as methyl sulfate and ethyl sulfate; x) aryl sulfates: Ar-O-S(O)O-, such as benzene sulfate and toluene sulfate; xi) alkoxy sulfates: Alk-O-S(O)2O-, such as methoxy sulfate and ethoxy sulfate; xii) aryloxy sulfates: Ar-O-S(O)2O-, xiii) phosphates O=P(OH)2-O-, O=P(O-)2-OH O=P(O-)3, HO-[P(O)(O-)]w-P(O)(O-)2with w being an integer; xiv) acetate; xv) triflate; and xvi) borates such as tetrafluoroborate, xvii) disulfate (O=)2S(O-)2or SO42-and monosulfate HSO4-.

[0214] One particularly preferred dye of formula (C-VIII’) is HC Blue 17.

[0215] One particularly preferred dye of formula (C-VIII’’) is HC Blue 16 (1-methylamino-4-(3'-dimethylpropylammoniumpropylamino)anthraquinone bromide).

[0216] Preferentially, the anthraquinone cationic direct dye(s) are chosen from the dyes of formula (C-VIII’) and (C-VIII’’), and more preferentially from the dyes of formula (C-VIII’’), better still from HC Blue 16.

[0217] The dyeing composition according to the invention may comprise one or more anionic direct dyes.

[0218] The anionic direct dyes of the invention are dyes commonly referred to as “acid” direct dyes owing to their affinity for alkaline substances. “Anionic direct dye” is understood to mean any direct dye including in its structure at least one CO2R or SO3R substituent with R denoting a hydrogen atom or a cation originating from a metal or an amine, or an ammonium ion. The anionic dyes may be chosen from direct nitro acid dyes, azo acid dyes, azine acid dyes, triarylmethane acid dyes, indoamine acid dyes, anthraquinone acid dyes, indigoid acid dyes and natural acid dyes.

[0219] According to the invention, the anionic direct dye(s) may be chosen, alone or as a mixture, from the anionic direct dyes of formulae (A-II), (A-II’), (A-III), (A-III’), (A-IV), (A-IV’), (A-V), (A-V’), (A-VI), (A-VII), (A-VIII) and (A-IX) below:

[0220] a) the diaryl anionic azo dyes of formula (A-II) or (A-II’): (A-II) (A-II’),

[0221] in which formulae (A-II) and (A-II’):* R7, R8, R9, R10, R’7, R’8, R’9and R’10, which may be identical or different, represent a hydrogen atom or a group chosen from:- alkyl;- alkoxy, alkylthio;- hydroxyl, mercapto;- nitro, nitroso;- R°-C(X)-X’-, R°-X’-C(X)-, R°-X’-C(X)-X’’- with R° representing a hydrogen atom or an alkyl or aryl group; X, X’ and X’’, which may be identical or different, representing an oxygen or sulfur atom, or NR with R representing a hydrogen atom or an alkyl group;- (O)2S(O-)-, M+with M+representing a hydrogen atom or a cationic counterion;- (O)CO--, M+with M+as defined above;- R’’-S(O)2-, with R’’ representing a hydrogen atom or an alkyl group, an aryl, (di)(alkyl)amino or aryl(alkyl)amino group; preferentially a phenylamino or phenyl group;- R’’’-S(O)2-X’- with R’’’ representing an optionally substituted alkyl or aryl group, X’ as defined above;- (di)(alkyl)amino;- aryl(alkyl)amino optionally substituted by one or more groups chosen from i) nitro; ii) nitroso; iii) (O)2S(O-)-, M+and iv) alkoxy with M+as defined above;- optionally substituted heteroaryl; preferentially a benzothiazolyl group;- cycloalkyl; notably cyclohexyl;- Ar-N=N-with Ar representing an optionally substituted aryl group; preferentially a phenyl optionally substituted by one or more alkyl, (O)2S(O-)-, M+or phenylamino groups;- or else two contiguous groups R7with R8or R8with R9or R9with R10together form a fused benzo group A’; and R’7with R’8or R’8with R’9or R’9with R’10together form a fused benzo group B’; with A’ and B’ optionally substituted by one or more groups chosen from i) nitro; ii) nitroso; iii) (O)2S(O-)-, M+; iv) hydroxyl; v) mercapto; vi) (di)(alkyl)amino; vii) R°-C(X)-X’-; viii) R°-X’-C(X)-; ix) R°-X’-C(X)-X’’-; x) Ar-N=N- and xi) optionally substituted aryl(alkyl)amino; with M+, R°, X, X’, X’’ and Ar as defined above;* W represents a sigma bond s, an oxygen or sulfur atom, or a divalent radical i) –NR- with R as defined above, or ii) methylene -C(Ra)(Rb)- with Ra and Rb, which may be identical or different, representing a hydrogen atom or an aryl group, or else Ra and Rb together form, with the carbon atom which bears them, a spiro cycloalkyl; preferentially, W represents a sulfur atom or Ra and Rb together form a cyclohexyl;it being understood that formulae (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; preferentially sodium sulfonate.

[0222] As examples of dyes of formula (A-II), mention may be made of: 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 or Sunset Yellow;

[0223] and, as examples of dyes of formula (A-II’), mention may be made of: Acid Red 111, Acid Red 134, Acid Yellow 38;

[0224] b) the pyrazolone anionic azo dyes of formulae (A-III) and (A-III’): (A-III) (A-III’),

[0225] in which formulae (A-III) and (A-III’):* R11, R12and R13, which may be identical or different, represent a hydrogen or halogen atom, an alkyl group or -(O)2S(O-), M+with M+as defined above;* R14represents a hydrogen atom, an alkyl group or a group -C(O)O-, M+with M+as defined above;* R15represents a hydrogen atom;* R16represents an oxo group, in which case R’16is absent, or else R15with R16together form a double bond;* R17and R18, which may be identical or different, represent a hydrogen atom, or a group chosen from:- (O)2S(O-)-, M+with M+as defined above;- Ar-O-S(O)2- with Ar representing an optionally substituted aryl group; preferentially a phenyl optionally substituted by one or more alkyl groups;* R19and R20together form either a double bond, or a benzo group D’, which is optionally substituted;* R’16, R’19and R’20, which may be identical or different, represent a hydrogen atom or an alkyl or hydroxyl group;* R21represents a hydrogen atom or an alkyl or alkoxy group;* Ra and Rb, which may be identical or different, are as defined above; preferentially, Ra represents a hydrogen atom and Rb represents an aryl group;* Y represents either a hydroxyl group or an oxo group;* represents a single bond when Y is an oxo group; and represents a double bond when Y represents a hydroxyl group;it being understood that formulae (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; preferentially sodium sulfonate;As examples of dyes of formula (A-III), mention may be made of: Acid Red 195, Acid Yellow 23, Acid Yellow 27, Acid Yellow 76, and, as examples of dyes of formula (A-III’), mention may be made of: Acid Yellow 17;

[0226] c) the anthraquinone dyes of formulae (A-IV) and (A-IV’): (A-IV), (A-IV’)

[0227] in which formulae (A-IV) and (A-IV’):* R22, R23, R24, R25, R26and R27, which may be identical or different, represent a hydrogen or halogen atom, or a group chosen from:- alkyl;- hydroxyl, mercapto;- alkoxy, alkylthio;- optionally substituted aryloxy or arylthio, preferentially substituted by one or more groups chosen from alkyl and (O)2S(O-)-, M+with M+as defined above;- aryl(alkyl)amino optionally substituted by one or more groups chosen from alkyl and (O)2S(O-)-, M+with M+as defined above;- (di)(alkyl)amino;- (di)(hydroxyalkyl)amino;- (O)2S(O-)-, M+with M+as defined above;* Z’ represents a hydrogen atom or a group NR28R29with R28and R29, which may be identical or different, representing a hydrogen atom or a group chosen from:- alkyl;- polyhydroxyalkyl such as hydroxyethyl;- aryl optionally substituted by one or more groups, particularly i) alkyl, such as methyl, n-dodecyl, n-butyl; ii) (O)2S(O-)-, M+with M+as defined above; iii) R°-C(X)-X’-, R°-X’-C(X)-, R°-X’-C(X)-X’’- with R°, X, X’ et X’’ as defined above, preferentially R° represents an alkyl group;- cycloalkyl, notably cyclohexyl;* Z represents a group chosen from hydroxyl and NR’28R’29with R’28and R’29, which may be identical or different, representing the same atoms or groups as R28and R29as defined above;it being understood that formulae (A-IV) and (A-IV’) comprise at least one sulfonate radical (O)2S(O-)-, M+or one carboxylate radical -C(O)O-, M+; preferentially sodium sulfonate;As examples of dyes of formula (A-IV), mention may be made of: Acid Blue 25, Acid Blue 43, Acid Blue 62, Acid Blue 78, Acid Blue 129, Acid Blue 138, Acid Blue 140, Acid Blue 251, Acid Green 25, Acid Green 41, Acid Violet 42, Acid Violet 43, Mordant Red 3; EXT Violet No. 2;and, as examples of dyes of formula (A-IV’), mention may be made of: Acid Black 48;

[0228] d) the nitro dyes of formulae (A-V) and (A-V’): (A-V) (A-V’)

[0229] in which formulae (A-V) and (A-V’):* R30, R31and R32, which may be identical or different, represent a hydrogen or halogen atom, or a group chosen from:- alkyl;- alkoxy optionally substituted by one or more hydroxyl groups, or alkylthio optionally substituted by one or more hydroxyl groups;- hydroxyl, mercapto;- nitro, nitroso;- polyhaloalkyl;- R°-C(X)-X’-, R°-X’-C(X)-, R°-X’-C(X)-X’’- with R°; X, X’ and X’’ as defined above;- (O)2S(O-)-, M+with M+as defined above;- (O)CO--, M+with M+as defined above;- (di)(alkyl)amino;

[0230] - (di)(hydroxyalkyl)amino;- heterocycloalkyl, such as piperidino, piperazino or morpholino;in particular, R30, R31and R32represent a hydrogen atom;* Rc and Rd, which may be identical or different, represent a hydrogen atom or an alkyl group;* W is as defined above; W represents in particular an –NH– group;* ALK represents a linear or branched divalent C1-C6alkylene group; in particular, ALK represents a –CH2-CH2- group;* n has a value of 1 or 2;* p represents an integer between 1 and 5 inclusive;* q represents an integer between 1 and 4 inclusive;* u has a value of 0 or 1;* when n has a value of 1, J represents a nitro or nitroso group; in particular a nitro group;* when n has a value of 2, J represents an oxygen or sulfur atom or a divalent –S(O)m– radical with m representing an integer which is 1 or 2; preferentially, J represents an –SO2– radical;* M’ represents a hydrogen atom or a cationic counterion;* , which may be present or absent, represents a benzo group,optionally substituted by one or more R30groups as defined above;it being understood that formulae (A-V) and (A-V’) comprise at least one sulfonate radical (O)2S(O-)-, M+or one carboxylate radical -C(O)O-, M+; preferentially sodium sulfonate;

[0231] As examples of dyes of formula (A-V), mention may be made of: Acid Brown 13 and Acid Orange 3; as examples of dyes of formula (A-V’), mention may be made of: Acid Yellow 1, the sodium salt of 2,4-dinitro-1-naphthol-7-sulfonic acid, 2-piperidino-5-nitrobenzenesulfonic acid, 2-(4’-N,N-(2”-hydroxyethyl)amino-2’-nitro)anilineethanesulfonic acid, 4-β-hydroxyethylamino-3-nitrobenzenesulfonic acid; EXT D&C Yellow 7;

[0232] e) the triarylmethane dyes of formula (A-VI): (A-VI)

[0233] in which formula (A-VI):* R33, R34, R35and R36, which may be identical or different, represent a hydrogen atom or a group chosen from alkyl, optionally substituted aryl and optionally substituted arylalkyl; particularly an alkyl and benzyl group optionally substituted by an (O)mS(O-)-, M+group, with M+and m as defined above;* R37, R38, R39, R40, R41, R42, R43and R44, which may be identical or different, represent a hydrogen atom or a group chosen from:- alkyl;- alkoxy, alkylthio;- (di)(alkyl)amino;- hydroxyl, 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’’, which may be identical or different, representing an oxygen or sulfur atom or NR with R representing a hydrogen atom or an alkyl group;- (O)2S(O-)-, M+with M+representing a hydrogen atom or a cationic counterion;- (O)CO--, M+with M+as defined above;- or else two contiguous groups, R41with R42or R42with R43or R43with R44, together form a fused benzo group: I’; with I’ optionally substituted by one or more groups chosen from i) nitro; ii) nitroso; iii) (O)2S(O-)-, M+; iv) hydroxyl; v) mercapto; vi) (di)(alkyl)amino; vii) R°-C(X)-X’-; viii) R°-X’-C(X)-; ix) R°-X’-C(X)-X’’-; with M+, R°, X, X’, X’’ as defined above;in particular, R37to R40represent a hydrogen atom, and R41to R44, which may be identical or different, represent a hydroxyl or (O)2S(O-)-, M+group; and, when R43with R44together form a benzo group, it is preferentially substituted by an (O)2S(O-)- group;it being understood 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--; preferentially sulfonate.As examples of dyes of formula (A-VI), mention may be made of: Acid Blue 1; Acid Blue 3; Acid Blue 7, Acid Blue 9; Acid Violet 49; Acid Green 3; Acid Green 5; Acid Green 50;

[0234] f) the xanthene-based dyes of formula (A-VII): (A-VII)

[0235] in which formula (A-VII):* R45, R46, R47and R48, which may be identical or different, represent a hydrogen atom or a halogen atom;* R49, R50, R51and R52, which may be identical or different, represent a hydrogen or halogen atom, or a group chosen from:- alkyl;- alkoxy, alkylthio;- hydroxyl, mercapto;- nitro, nitroso;- (O)2S(O-)-, M+with M+representing a hydrogen atom or a cationic counterion;- (O)CO--, M+with M+as defined above;in particular, R53, R54, R55and R48represent a hydrogen or halogen atom;* G represents an oxygen or sulfur atom or a group NR with R representing a hydrogen atom or an alkyl group; in particular, G represents an oxygen atom;* L represents an alkoxide O-, M+; a thioalkoxide S-, M+or a group NRf, with Rf representing a hydrogen atom or an alkyl group, and M+as defined above; M+is particularly sodium or potassium;* L’ represents an oxygen or sulfur atom or an ammonium group: N+RfRg, with Rf and Rg, which may be identical or different, representing a hydrogen atom or an optionally substituted alkyl or aryl group; L’ particularly represents an oxygen atom or a phenylamino group optionally substituted by one or more alkyl or (O)mS(O-)-, M+groups with m and M+as defined above;* Q and Q’, which may be identical or different, represent an oxygen or sulfur atom; in particular, Q and Q’ represent an oxygen atom;* M+is as defined above.

[0236] As examples of dyes of formula (A-VII), mention may be made of: Acid Yellow 73; Acid Red 51; Acid Red 52; Acid Red 87; Acid Red 92; Acid Red 95; Acid Violet 9;

[0237] g) the indole-based dyes of formula (A-VIII): (A-VIII),

[0238] in which formula (A-VIII):* R53, R54, R55, R56, R57, R58, R59and R60, which may be identical or different, represent a hydrogen atom or a group chosen from:- alkyl;- alkoxy, alkylthio;- hydroxyl, mercapto;- nitro, nitroso;- R°-C(X)-X’-, R°-X’-C(X)-, R°-X’-C(X)-X’’- with R° representing a hydrogen atom or an alkyl or aryl group; X, X’ and X’’, which may be identical or different, representing an oxygen or sulfur atom, or NR with R representing a hydrogen atom or an alkyl group;- (O)2S(O-)-, M+with M+representing a hydrogen atom or a cationic counterion;- (O)CO--, M+with M+as defined above;* G represents an oxygen or sulfur atom or a group NR with R representing a hydrogen atom or an alkyl group; in particular, G represents an oxygen atom;* Ri and Rh, which may be identical or different, represent a hydrogen atom or an alkyl group;it being understood that formula (A-VIII) comprises at least one sulfonate radical (O)2S(O-)-, M+or one carboxylate radical -C(O)O-, M+; preferentially sodium sulfonate;

[0239] As examples of dyes of formula (A-VIII), mention may be made of: Acid Blue 74.

[0240] h) the quinoline-based dyes of formula (A-IX): (A-IX),

[0241] in which formula (A-IX):* R61represents a hydrogen or halogen atom or an alkyl group;* R62, R63and R64, which may be identical or different, represent a hydrogen atom or an (O)2S(O-)-, M+group, with M+representing a hydrogen atom or a cationic counterion;* or else R61with R62, or R61with R64, together form a benzo group optionally substituted by one or more (O)2S(O-)-, M+groups, with M+representing a hydrogen atom or a cationic counterion;it being understood that formula (A-IX) comprises at least one sulfonate radical (O)2S(O-)-, M+, preferentially sodium sulfonate.

[0242] As examples of dyes of formula (A-IX), mention may be made of: Acid Yellow 2, Acid Yellow 3 and Acid Yellow 5.

[0243] More particularly, the dyeing composition comprises one or more anionic direct dyes chosen, alone or as a mixture, from the following anionic direct dyes:

[0244] (C.I. 45380)Acid Red 87 (A-VII)(C.l. 10316)Sodium salt of 2,4-dinitro-1-naphthol-7-sulfonic acid (A-V’)(C.l. 10383)Acid Orange 3 (A-V)(C.l. 13015)Acid Yellow 9 / Food Yellow 2 (A-II)(C.l. 14780) / Direct Red 45 / Food Red 13 (A-II)(C.l. 13711)Acid Black 52 (A-II)(C.l. 13065)Acid Yellow 36 (A-II)(C.l. 14700)Sodium salt of 1-hydroxy-2-(2’,4’-xylyl-5-sulfonatoazo)naphthalene-4-sulfonic acid / Food Red 1 (A-II)(C.l. 14720)Acid Red 14 / Food Red 3 / Mordant Blue 79 (A-II)(C.I. 14805)Sodium salt of 4-hydroxy-3-[(2-methoxy-5-nitrophenyl)diaza]-6-(phenylamino)naphthalene-2-sulfonic acid / 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.I. 18055)Sodium salt of 1-hydroxy-2-(4’-acetamidophenylazo)-8-acetamidonaphthalene-3,6-disulfonic acid / Acid Violet 7 / Food Red 11 (A-II)(C.l. 18130)Acid Red 135 (A-II)(C.l. 19130)Acid Yellow 27 (A-III)(C.l. 19140)Acid Yellow 23 / Food Yellow 4 (A-III)(C.l. 20170)4’-(Sulfonato-2’’,4’’-dimethyl)bis(2,6-phenylazo)-1,3-dihydroxybenzene / Acid Orange 24 (A-II)(C.l. 20470)Sodium salt of 1-amino-2-(4’-nitrophenylazo)-7-phenylazo-8-hydroxynaphthalene-3,6-disulfonic acid / Acid Black 1 (A-II)(C.l. 23266)(4-((4-Methylphenyl)sulfonyloxy)phenylazo)-2,2’-dimethyl-4-((2-hydroxy-5,8-disulfonato)naphthylazo)biphenyl / Acid Red 111 (A-II’)(C.l. 27755)Food Black 2 (A-II)(C.l. 25440)1-(4’-Sulfonatophenylazo)-4-((2’’-hydroxy-3’’-acetylamino-6’’,8’’-disulfonato)naphthylazo)-6-sulfonatonaphthalene (tetrasodium salt) / Food Black 1 (A-II)(C.I. 42090)Acid Blue 9 (A-VI)(C.I. 60730)Acid Violet 43 (A-IV)(C.I. 61570)Acid Green 25 (A-IV)(C.I. 62045)Sodium salt of 1-amino-4-cyclohexylamino-9,10-anthraquinone-2-sulfonic acid / Acid Blue 62 (A-IV)(C.I. 62105)Acid Blue 78 (A-IV)(C.l. 14710)Sodium salt of 4-hydroxy-3-((2-methoxyphenyl)azo)-1-naphthalenesulfonic acid / Acid Red 4 (A-II)2-Piperidino-5-nitrobenzenesulfonic acid (V’)2-(4’-N,N-(2’’-Hydroxyethyl)amino-2’-nitro)anilineethanesulfonic acid (A-V’)4-β-hydroxyethylamino-3-nitrobenzenesulfonic acid (A-V’)(C.I. 42640)Acid Violet 49 (A-VI)(C.I. 42080)Acid Blue 7 (A-VI)(C.I. 58005)Sodium salt of 1,2-dihydroxy-3-sulfoanthraquinone / Mordant Red 3 (A-IV)(C.I. 62055)Sodium salt of 1-amino-9,10-dihydro-9,10-dioxo-4-(phenylamino)-2-anthracenesulfonic acid / Acid Blue 25 (A-IV)(C.I. 14710)Sodium salt of 4-hydroxy-3-((2-methoxyphenyl)azo)-1-naphthalenesulfonic acid / Acid Red 4 (A-II)

[0245] Most of these dyes are described in particular in the Color Index published by The Society of Dyers and Colorists, P.O. Box 244, Perkin House, 82 Grattan Road, Bradford, Yorkshire, BD1 2JBN, England.

[0246] The anionic dyes that are more particularly preferred are the dyes designated in the Color Index under the code C.I. 58005 (monosodium salt of 1,2-dihydroxy-9,10-anthraquinone-3-sulfonic acid), C.I. 60730 (monosodium salt of 2-[(9,10-dihydro-4-hydroxy-9,10-dioxo-1-anthracenyl)amino]-5-methylbenzenesulfonic acid), C.I. 15510 (monosodium salt of 4-[(2-hydroxy-1-naphthalenyl)azo]benzenesulfonic acid), C.I. 15985 (disodium salt of 6-hydroxy-5-[(4-sulfophenyl)azo]-2-naphthalenesulfonic acid), C.I. 17200 (disodium salt of 5-amino-4-hydroxy-3-(phenylazo)-2,7-naphthalenedisulfonic acid), C.I. 20470 (disodium salt of 1-amino-2-(4’-nitrophenylazo)-7-phenylazo-8-hydroxy-3,6-naphthalenedisulfonic acid), C.I. 42090 (disodium salt of N-ethyl-N-[4-[[4-[ethyl[(3-sulfophenyl)methyl]amino]phenyl](2-sulfophenyl)methylene]-2,5-cyclohexadien-1-ylidene]-3-sulfobenzenemethanaminium hydroxide, internal salt), C.I. 61570 (disodium salt of 2,2’-[(9,10-dihydro-9,10-dioxo-1,4-anthracenediyl)diimino]bis[5-methyl]benzenesulfonic acid).

[0247] Use may also be made of compounds corresponding to the mesomeric or tautomeric forms of structures (A-II) to (A-IX).

[0248] Among the natural direct dyes that may 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, apigenidin and orcein. Extracts or decoctions containing these natural dyes and in particular henna-based poultices or extracts may also be used.

[0249] Preferably, the dyeing composition used in the process of the invention comprises one or more cationic direct dye(s).

[0250] More preferably, the dyeing 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.

[0251] Advantageously, the total content of the direct dye(s) ranges from 0.001% to 20% by weight, preferably from 0.005% to 15% by weight, more preferentially from 0.01% to 10% by weight, better still from 0.05% to 5% by weight, even better still from 0.1% to 3% by weight, relative to the total weight of the dyeing composition.Aromatic compound

[0252] The dyeing composition used in the process of the invention comprises at least one compound of formula (I): (I)

[0253] in which Y represents a C1-C4hydroxyalkyl group or a C1-C4hydroxyalkyloxy radical, n denotes an integer ranging from 0 to 5, and X, which may be identical or different, represents a C1-C4alkyl radical or a halogen. Preferably, n is equal to 0. According to a particular embodiment, Y represents a hydroxymethyl, hydroxyethyl or hydroxyethyloxy radical.

[0254] As examples of compounds of formula (I), mention may be made of benzyl alcohol, phenylethanol and phenoxyethanol. According to a particular embodiment, the compound of formula (I) is benzyl alcohol.

[0255] According to a particular embodiment, the amount of compounds of formula (I) ranges from 0.01% to 10% by weight, preferably from 0.05% to 8% by weight, better still from 0.1% to 5% by weight, relative to the total weight of the dyeing composition.Aliphatic solvent

[0256] The dyeing composition used in the process of the invention comprises at least one hydroxylated C2-C6aliphatic solvent.

[0257] “Aliphatic” is understood to mean a compound not containing an aromatic ring. The solvents of this type may be monoalcohols or polyols that are liquid at room temperature (25°C) and at atmospheric pressure (105 Pa). Preferably, these solvents are nonetherified solvents. According to a particular embodiment, these solvents are chosen from ethanol, glycerol, propylene glycol, dipropylene glycol and hexylene glycol. Preferably, the hydroxylated C2-C6aliphatic solvent is ethanol and / or hexylene glycol, preferably ethanol.

[0258] According to one embodiment, the amount of hydroxylated aliphatic solvent ranges from 0.1% to 40% by weight, preferably from 0.5% to 30% by weight, more preferentially from 1% to 20% by weight, better still from 2% to 15% by weight, even better still from 3% to 10% by weight, relative to the weight of the dyeing composition.

[0259] Preferably, the composition comprises benzyl alcohol and ethanol.

[0260] According to a particular embodiment, the compounds of formula (I) / hydroxylated C2-C6aliphatic solvent(s) weight ratio is less than or equal to 1, preferably ranges from 0.1 to 1, better still from 0.1 to 0.5.

[0261] According to a particular embodiment, the benzyl alcohol / ethanol weight ratio is less than or equal to 1, preferably ranges from 0.1 to 1, better still from 0.1 to 0.5.Polysaccharide

[0262] The dyeing composition used in the process of the invention may also comprise one or more polysaccharide(s).

[0263] In the present invention, “polysaccharide” is understood to mean a polymer constituted of sugar units. “Sugar unit” is understood to mean an oxygen-bearing hydrocarbon-based compound containing several alcohol functions, with or without aldehyde or ketone functions, and which includes at least 4 carbon atoms. The sugar units may be optionally modified by substitution, and / or by oxidation and / or by dehydration.

[0264] The sugar units that may 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.

[0265] As polysaccharides, mention may in particular be made of the following polymers, alone or as a mixture:a) tree or shrub exudates, 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);- gum 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 furcellerans (polymers of galactose sulfate and anhydrogalactose sulfate);c) gums derived from seeds or tubers, including:- guar gum (polymer of mannose and galactose);- locust bean 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 (glucose polymers);- starches (glucose polymers) and- inulin.

[0266] These polymers may be physically or chemically modified. As physical treatment, mention may in particular be made of a heat treatment. As chemical treatments, mention may be made of esterification, etherification, amidation and oxidation reactions. These treatments make it possible to produce polymers that may notably be nonionic, anionic or amphoteric.

[0267] In particular, the guar gums, locust bean gums, starches and celluloses may be modified / treated.

[0268] The guar gums that may be used according to the invention may be modified with C1-C6(poly)hydroxyalkyl groups. Among the C1-C6(poly)hydroxyalkyl groups, mention may be made, by way of example, of hydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxybutyl groups. These guar gums are well known in the prior art and may be prepared, for example, by reacting corresponding alkene oxides, for instance propylene oxides, with the guar gum so as to obtain a guar gum modified with hydroxypropyl groups. The degree of hydroxyalkylation preferably ranges from 0.4 to 1.2 and corresponds to the number of alkylene oxide molecules consumed by the number of free hydroxyl functions present on the guar gum.

[0269] Such guar gums optionally modified with hydroxyalkyl groups are sold, for example, under the trade names Jaguar HP8, Jaguar HP60 and Jaguar HP120 by the company Rhodia Chimie.

[0270] The botanical origin of the starches that may be used in the present invention may be cereals or tubers. Thus, the starches are chosen, for example, from corn starch, rice starch, oat starch, cassava starch, barley starch, potato starch, wheat starch, sorghum starch, pea starch and tapioca starch. Use may also be made of the hydrolyzates of the starches mentioned above. The starch is preferably derived from potato.

[0271] Use will preferentially be made of starch phosphates, notably distarch phosphates or compounds rich in distarch phosphate such as the product sold 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 company Avebe, or Structure Zea from National Starch (gelatinized corn distarch phosphate).

[0272] According to the invention, amphoteric starches may also be used, these amphoteric starches comprising one or more anionic groups and one or more cationic groups. The anionic and cationic groups may be bonded to the same reactive site of the starch molecule or to different reactive sites; preferably, they are bonded to the same reactive site. The anionic groups may be of carboxylic, phosphate or sulfate type, preferably carboxylic type. The cationic groups may be of primary, secondary, tertiary or quaternary amine type.

[0273] The polysaccharides that may be used according to the invention may be cellulose-based polymers.

[0274] According to the invention, “cellulose-based” polymer is understood to mean any polysaccharide compound bearing in its structure sequences of glucose residues linked together via β-1,4 bonds; in addition to unsubstituted celluloses, the cellulose derivatives may be anionic, cationic, amphoteric or nonionic.

[0275] Cellulose-based polymers are also known as celluloses.

[0276] Thus, the cellulose-based polymers that may be used according to the invention may be chosen from unsubstituted celluloses, including those in a microcrystalline form, and cellulose ethers.

[0277] Among these cellulose-based polymers, a distinction is made between cellulose ethers, cellulose esters and cellulose ether esters.

[0278] Among the cellulose esters are inorganic cellulose esters (cellulose nitrates, sulfates or phosphates), organic cellulose esters (cellulose monoacetates, triacetates, amidopropionates, acetate butyrates, acetate propionates or acetate trimellitates), and mixed organic / inorganic cellulose esters, such as cellulose acetate butyrate sulfates and cellulose acetate propionate sulfates. Among the cellulose ether esters, mention may be made of hydroxypropylmethylcellulose phthalates and ethylcellulose sulfates.

[0279] Among the cellulose ethers, mention may be made of (C1-C4)alkylcelluloses, such as methylcelluloses and ethylcelluloses (for example Ethocel Standard 100 Premium from Dow Chemical); (poly)hydroxy(C1-C4)alkylcelluloses, such as hydroxymethylcelluloses, hydroxyethylcelluloses (for example Natrosol 250 HHR provided by Ashland) and hydroxypropylcelluloses (for example Klucel EF from Aqualon); (poly)hydroxy(C1-C4)alkyl(C1-C4)alkylcellulose mixed celluloses, such as hydroxypropylmethylcelluloses (for example Methocel E4M from Dow Chemical), hydroxyethylmethylcelluloses, hydroxyethylethylcelluloses (for example Bermocoll E 481 FQ from AkzoNobel) and hydroxybutylmethylcelluloses.

[0280] Among the anionic cellulose ethers, mention may be made of (poly)carboxy(C1-C4)alkylcelluloses and salts thereof. Examples that may be mentioned include carboxymethylcelluloses, carboxymethylmethylcelluloses (for example Blanose 7M from the company Aqualon) and carboxymethylhydroxyethylcelluloses, and the sodium salts thereof.

[0281] Among the cationic cellulose ethers, mention may be made of cationic cellulose derivatives such as cellulose copolymers or cellulose derivatives grafted with a water-soluble quaternary ammonium monomer, and described in particular in patent US4131576, such as (poly)hydroxy(C1-C4)alkyl celluloses, for instance hydroxymethyl-, hydroxyethyl- or hydroxypropylcelluloses grafted notably with a methacryloylethyltrimethylammonium, methacrylamidopropyltrimethylammonium or dimethyldiallylammonium salt. The commercial products corresponding to this definition are more particularly the products sold under the names Celquat® L 200 and Celquat® H 100 by the company National Starch.

[0282] Preferably, the polysaccharide(s) are chosen from scleroglucan gums, cellulose-based polymers, xanthan gums and guar gums, preferentially from scleroglucan gums, guar gums and cellulose-based polymers.

[0283] The polysaccharide(s) may be present in the dyeing composition used 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 more preferentially from 0.05% to 3%, by weight, relative to the total weight of the dyeing composition.

[0284] The dyeing composition according to the invention may comprise water or a mixture of water and optionally one or more solvents other than the compounds of formula (I) and than the hydroxylated C2-C6aliphatic solvents such as polyol ethers, for instance dipropylene glycol monomethyl ether.

[0285] Preferably, the dyeing composition comprises water, preferably in a content ranging from 20% to 95% by weight, preferably from 30% to 80% by weight, and even more preferentially from 40% to 87% by weight, relative to the total weight of the dyeing composition.

[0286] The dyeing composition used in the process of the invention may also contain various adjuvants that are conventionally used in compositions for dyeing the hair, such as anionic, cationic, nonionic, amphoteric or zwitterionic surfactants; anionic, cationic, amphoteric, zwitterionic or nonionic polymers different from polysaccharides; mineral or organic thickeners; antioxidants; penetrants, sequestrants, fragrances, buffers, dispersants, conditioning agents, film-forming agents, ceramides, preservatives and opacifiers.

[0287] The above adjuvants are generally present in an amount, for each of them, of between 0.01% and 20% by weight relative to the weight of the dyeing composition.

[0288] Needless to say, those skilled in the art will take care to choose this or these optional additional compounds such that the advantageous properties intrinsically associated with the dyeing composition are not, or are not substantially, adversely affected by the envisaged addition(s).

[0289] The pH of the dyeing composition used in the process in accordance with 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 may be adjusted to the desired value by means of acidifying or basifying agents that are usually used in the dyeing of keratin fibers, or alternatively using conventional buffer systems.

[0290] Among the acidifying agents, examples that may be mentioned include mineral or organic acids, such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids, such as acetic acid, tartaric acid, citric acid or lactic acid, and sulfonic acids.

[0291] Among the basifying agents, examples that may be mentioned include aqueous ammonia, alkali metal carbonates, alkanolamines, such as monoethanolamine, diethanolamine and triethanolamine and derivatives thereof, sodium hydroxide, potassium hydroxide, and the compounds of the following formula:

[0292] in which W is a propylene residue optionally substituted by a hydroxyl group or a C1-C4alkyl radical; Ra, Rb, Rc and Rd, which may be identical or different, represent a hydrogen atom or a C1-C4alkyl or C1-C4hydroxyalkyl radical.Process

[0293] The process for dyeing keratin fibers according to the invention comprises the application to said keratin fibers of the lightening composition described above, and of the dyeing composition described above.

[0294] Preferably, the step of applying the dyeing composition is carried out after the step of applying the lightening composition.

[0295] Preferably, the dyeing process comprises, 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.

[0296] This mixing step is preferably performed at the time of use, just before the lightening composition resulting from the mixing is applied to the keratin fibers.

[0297] Preferably, the alkaline and oxidizing compositions are mixed in an alkaline composition / oxidizing composition weight ratio ranging from 0.1 to 2, preferentially from 0.3 to 1.5, better still from 0.5 to 1.

[0298] The lightening composition may be applied to wet or dry keratin fibers.

[0299] 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.

[0300] Preferably, the keratin fibers are then rinsed with water, and optionally washed with a shampoo and then rinsed with water, before being optionally wrung out, dried or left to dry.

[0301] The dyeing composition is then applied to the wet or dry keratin fibers.

[0302] The dyeing 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.

[0303] After the treatment, the keratin fibers are optionally rinsed with water, optionally washed with a shampoo and then rinsed with water, before being dried or left to dry.

[0304] The invention also relates to a process for dyeing keratin fibers, in particular human keratin fibers such as the hair, comprisingthe application to said keratin fibers:i) of a lightening composition comprising:- one or more oxidizing agent(s),- one or more alkaline agent(s); thenii) of a dyeing composition comprising:- one or more direct dye(s),- one or more compound(s) 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, and X, which may be identical or different, represents a C1-C4 alkyl radical or a halogen, preferably chosen from benzyl alcohol, phenylethanol and phenoxyethanol, preferably benzyl alcohol,- one or more hydroxylated aliphatic solvent(s) comprising from 2 to 6 carbon atoms.

[0305] The invention also relates to a process for dyeing keratin fibers, in particular human keratin fibers such as the 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, then2) the application to said keratin fibers:i) of the lightening composition; thenii) of a dyeing composition comprising:- one or more direct dye(s),- one or more compound(s) 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, and X, which may be identical or different, represents a C1-C4 alkyl radical or a halogen, preferably chosen from benzyl alcohol, phenylethanol and phenoxyethanol, preferably benzyl alcohol,- one or more hydroxylated aliphatic solvent(s) comprising from 2 to 6 carbon atoms.Kit

[0306] Another subject of the invention is a device with at least three compartments, for the dyeing of keratin fibers, comprising at least a first compartment containing a dyeing composition comprising one or more direct dye(s), one or more compound(s) of formula (I) as defined above and one or more hydroxylated aliphatic 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 compound(s).

[0307] The compositions of the device according to the invention are packaged in separate compartments, optionally accompanied by suitable application means, which may be identical or different, such as fine brushes, coarse brushes or sponges.

[0308] The device mentioned above may also be equipped with a means for dispensing the desired mixture onto the hair, for instance the devices described in patent FR 2586913.

[0309] The examples that follow serve to illustrate the invention without, however, being limiting in nature.Examples

[0310] In the examples that follow, all the amounts are given as mass percentages of active material (AM) relative to the total weight of the composition (unless otherwise mentioned).Compositions

[0311] Compositions A, C, C1 and O were prepared from the compounds of which the contents are indicated in the tables below:

[0312] Alkaline composition A

[0313] AETHANOLAMINE12.9LAURIC ACID3.0GLYCOL DISTEARATE2.0CETEARYL ALCOHOL11.5PROPYLENE GLYCOL10.0Oxyethylenated fatty alcohols20.0POLYQUATERNIUM-221.5HEXADIMETHRINE CHLORIDE3.0CARBOMER0.4ASCORBIC ACID0.25SODIUM METABISULFITE0.7Sequestrant0.2pH adjusterqs pH = 10.4 ± 0.4Waterqs 100

[0314] Oxidizing composition O

[0315] OHYDROGEN PEROXIDE6.00TRIDECETH-2 CARBOXAMIDE MEA0.82GLYCERIN0.50CETEARYL ALCOHOL2.28CETEARETH-250.57PHOSPHORIC ACIDqs pH = 2.2 ± 0.2Stabilizers, sequestrantsqsWaterqs 100

[0316] Dyeing compositions C, C1

[0317] CC1BENZYL ALCOHOL2.0-BENZYLOXYETHANOL-2.0Ethanol8.08.0BASIC RED 760.50.5BASIC BROWN 170.50.5BASIC YELLOW 570.60.6HC BLUE NO.160.70.7SCLEROTIUM GUM2.02.0Sequestrant0.50.5pH adjusterqs pH = 7 ± 0.2qs pH = 7 ± 0.2Waterqs 100qs 100

[0318] The process according to the invention (Protocol 1) comprising the application of a lightening composition followed by the application of a dyeing composition was compared with a process that only comprises the application of the dyeing composition, without prior application of the lightening composition (Protocol 2).

[0319] Protocol 1 (invention)

[0320] At the time of use, the alkaline composition A was mixed with the oxidizing composition O in a 1+1.5 weight ratio in order to obtain a lightening composition.

[0321] The lightening composition obtained was then applied to a lock of hair containing 90% natural white hair, in a proportion of 5 g of mixture  /  g of hair.

[0322] After a leave-on time of 35 min on a plate thermostatically regulated at 27°C, the hair was rinsed, washed with a standard shampoo, and air-dried.

[0323] The dyeing composition C was then applied to the locks in a proportion of 5 g of mixture  /  g of hair.

[0324] After a leave-on time of 60 min at 27°C under an occlusive cellophane system, the locks were rinsed, then washed and dried using a hairdryer.

[0325] The locks of hair thus dyed were subsequently subjected to a shampoo wash test so as to evaluate the fastness (persistence) of the coloring obtained.

[0326] Protocol 2 (comparative)

[0327] The dyeing composition C was applied to a lock of hair containing 90% natural white hairs, in a proportion of 5 g of mixture  /  g of hair.

[0328] After a leave-on time of 60 min at 27°C under an occlusive cellophane system, the locks were rinsed, then washed and dried using a hairdryer.

[0329] The locks of hair thus dyed were subsequently subjected to a shampoo wash test so as to evaluate the fastness (persistence) of the coloring obtained.Results

[0330] The colorimetric measurements were performed using a Konica Minolta 3600 spectrocolorimeter (illuminant D65, angle 10°, specular component included) in the CIELab system.

[0331] Intensity

[0332] 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 L* value, the darker and more powerful the color.

[0333] L*Protocol 1 (invention)20.65Protocol 2 (comparative)24.19

[0334] The locks of hair treated with the lightening step before the dyeing step according to the invention have a lower L* value than those treated only with the dyeing step according to the comparative process.

[0335] In other words, the process according to the invention makes it possible to obtain a more intense coloring than the comparative process.

[0336] Persistence of the coloring

[0337] The persistence of the coloring is evaluated by the color difference ΔE between the dyed locks before washing, then after washing. The lower the ΔE value, the more persistent the color with respect to shampoo washing. The ΔE value is calculated according to the following equation:

[0338] In this equation, L*a*b* represent the values measured after dyeing the hair and after washing, and L0*a0*b0* represent the values measured after dyeing the hair but before the washing.

[0339] L*a*b*ΔEProtocol 1 (invention)Before washing20.650.152.373.11After washing23.161.793.21Protocol 2 (comparative)Before washing24.192.114.686.25After washing29.672.317.68

[0340] The locks of hair treated with the lightening step preceding the dyeing step according to the invention have a lower ΔE value than those treated only with the dyeing step according to the comparative process.

[0341] In other words, the process according to the invention makes it possible to obtain a better persistence of the color after shampoo washing with respect to the comparative process.

[0342] Color Uptake

[0343] At the time of use, the alkaline composition A was mixed with the oxidizing composition O at a weight ratio of 1:1.5 to obtain a lightening composition.

[0344] The lightening composition obtained was then applied to lock of hair containing 90% natural white hair, in a proportion of 5g of mixture per gram of hair.

[0345] After a leave-on time of 35 minutes on a plate thermostatically regulated at 27°C, the hair was rinsed, washed with a standard shampoo, and air-dried.

[0346] Then, the dyeing compositions C and C1 were independently applied to the locks in a proportion of 5g of mixture per gram of hair.

[0347] After a leave-on time of 15 minutes at 27°C under a cellophane occlusive system, the hair was rinsed, then washed and dried using a hairdryer.

[0348] The color uptake is represented by the color difference between the hair before the application of the coloring routine and after the coloring routine. The greater the difference, the better the color uptake.

[0349] For both dyeing compositions C and C1, good color uptake was observed on the hair treated with the coloring routine, the uptake being even better on the hair treated with the coloring routine implementing the dyeing composition C.

Claims

A process for dyeing keratin fibers, in particular human keratin fibers such as the hair, comprising the application to said keratin fibers:i) of a lightening composition comprising:- one or more oxidizing agent(s),- one or more alkaline agent(s); andii) of a dyeing composition comprising:- one or more direct dye(s),- one or more compound(s) of formula(I):(I)in which Y represents a C1-C4hydroxyalkyl group or a C1-C4hydroxyalkyloxy radical, n denotes an integer ranging from 0 to 5, and X, which may be identical or different, represents a C1-C4alkyl radical or a halogen,- one or more hydroxylated aliphatic solvent(s) comprising from 2 to 6 carbon atoms.The dyeing process as claimed in the preceding claim, in which the dyeing composition comprises one or more cationic direct dye(s), preferably chosen from azo cationic direct dyes, hydrazono cationic direct dyes, anthraquinone cationic direct dyes, and mixtures thereof.The dyeing process as claimed in either one of the preceding claims, in which the total content of the direct dye(s) ranges from 0.001% to 20%, preferably from 0.005% to 15%, by weight, more preferentially from 0.01% to 10% by weight, better still from 0.05% to 5% by weight, even better still from 0.1% to 3% by weight, relative to the total weight of the dyeing composition.The dyeing process as claimed in any one of the preceding claims, in which the compound(s) of formula (I) are chosen from benzyl alcohol, phenylethanol and phenoxyethanol, preferably benzyl alcohol.The dyeing process as claimed in any one of the preceding claims, in which the total content of the compound(s) of formula (I) in the dyeing composition ranges from 0.01% to 10% by weight, preferably from 0.05% to 8% by weight, better still from 0.1% to 5% by weight, relative to the weight of the dyeing composition.The dyeing process as claimed in any one of the preceding claims, in which the hydroxylated C2-C6aliphatic solvent(s) are chosen from ethanol, glycerol, propylene glycol, dipropylene glycol and hexylene glycol, preferably ethanol and / or hexylene glycol, preferably ethanol.The dyeing process as claimed in any one of the preceding claims, in which the total content of the hydroxylated C2-C6aliphatic solvent(s) ranges from 0.1% to 40% by weight, preferably from 0.5% to 30% by weight, more preferentially from 1% to 20% by weight, better still from 2% to 15% by weight, even better still from 3% to 10% by weight, relative to the weight of the dyeing composition.The dyeing process as claimed in any one of the preceding claims, in which the compounds of formula (I) / hydroxylated C2-C6aliphatic solvent(s) weight ratio is less than or equal to 1, preferably ranges from 0.1 to 1, better still from 0.1 to 0.5.The dyeing process as claimed in any one of the preceding claims, in which the chemical oxidizing agent(s) are chosen from hydrogen peroxide, urea peroxide, alkali metal bromates or ferricyanides, peroxygenated salts such as alkali metal or alkaline-earth metal persulfates, perborates and percarbonates, and peracids and precursors thereof; preferably is hydrogen peroxide.The dyeing process as claimed in any one of the preceding claims, in which the lightening composition does not comprise any peroxygenated salts.The dyeing process as claimed in any one of the preceding claims, in which the alkaline agent is chosen from alkanolamines such as monoethanolamine, diethanolamine, triethanolamine; aqueous ammonia, carbonates or bicarbonates such as sodium (hydrogen)carbonate and potassium (hydrogen)carbonates, alkali metal or alkaline-earth metal silicates or metasilicates such as sodium metasilicate, and mixtures thereof, more preferentially from alkanolamines and aqueous ammonia, better still from alkanolamines, even better still monoethanolamine.The dyeing process as claimed in any one of the preceding claims, in which the step of applying the dyeing composition ii) is carried out after the step of applying the lightening composition i).The dyeing process as claimed in any one of the preceding claims, which comprises, 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.The dyeing process as claimed in any one of the preceding claims, which comprises a step of rinsing the keratin fibers between steps i) and ii).A device with at least three compartments, for the dyeing of keratin fibers, comprising at least a first compartment containing a dyeing 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 compound(s) as defined preferably in claim 9.

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