Composition comprising a direct dye, a particular non-associative polysaccharide, a particular polycarboxylic acid, and a hydroxylated compound

Abstract

Composition comprising a direct dye, a particular non-associative polysaccharide, a particular polycarboxylic acid, and a hydroxylated compound. The invention relates to a composition comprising: - one or more direct dyes, - one or more non-associative polysaccharides chosen from polysaccharides of microbial origin, - one or more polycarboxylic acids of formula (I), - one or more hydroxylated compounds chosen from aromatic alcohols and hydroxylated C2-C6 aliphatic solvents, and mixtures thereof.

Description

Composition comprising a direct dye, a particular non-associative polysaccharide, a particular polycarboxylic acid, and a hydroxylated compound.

[0001] The present invention relates to a composition comprising a direct dye, a particular non-associative polysaccharide, a particular polycarboxylic acid and a hydroxylated compound, and also to a process for dyeing human keratin fibres, notably the hair, using the composition.

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

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

[0004] In general, oxidation bases are chosen fromortho-orpara-phenylenediamines,ortho- orpara-aminophenols and heterocyclic compounds. These oxidation bases are colourless or weakly coloured compounds which, when combined with oxidizing products, can give access to coloured species.

[0005] The shades obtained with these oxidation bases are quite often varied by combining them with one or more couplers, these couplers being chosen in particular from aromaticmeta-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 colours to be obtained. This type of dyeing also makes it possible to obtain permanent colourings.

[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 fibres and which colour 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 fibre and penetrate relatively little into the fibre, 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). The direct dyes may also be natural dyes.

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

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

[0011] There is also a need to obtain a hair dye that is capable of producing good colour 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 fibres such as the hair.

[0012] There is also a need to obtain a hair dye, without using oxidation dye precursors, in natural shades, with a harmonious and natural dyeing result.

[0013] At least one of these aims and others are achieved by the present invention, one subject of which is thus a composition which comprises:- one or more direct dyes,- one or more non-associative polysaccharides chosen from polysaccharides of microbial origin,- one or more polycarboxylic acids of formula (I) below, or salts thereof, optical isomers thereof, geometric isomers thereof, and / or solvates thereof:R1-N-(CH(R2)COOH)2(I)in whichR1represents a hydrogen atom or a -CH(COOH)-(CH2)2-COOH,-CH2CH2OH, -CH(CH3)COOH, -(CH2)2N(COR3)-CH2-COOH or -CH(COOH)-CH2-COOH group; andR2represents a CH2COOH group when R1represents a hydrogen atom, or R2represents a hydrogen atom when R1is other than a hydrogen atom; andR3represents a linear or branched alkyl group comprising from 1 to 4 carbon atoms or cyclic alkyl group comprising from 3 to 30 carbon atoms,- one or more hydroxylated compounds chosen from aromatic alcohols and hydroxylated C2-C6aliphatic solvents, and mixtures thereof.

[0014] The composition according to the invention is preferably a composition for dyeing keratin fibres, preferably human keratin fibres, in particular the hair.

[0015] The invention also relates to a process for dyeing keratin fibres, preferably human keratin fibres, notably the hair, using the composition.

[0016] The invention makes it possible to obtain dyeing of the keratin fibres with good colour build-up, good fastness, notably good persistence to shampoo washing, and improved stability of the composition.

[0017] Other subjects, features, aspects and advantages of the invention will emerge even more clearly on reading the description and the examples that follow.

[0018] In the text that follows, unless otherwise indicated, the limits of a range of values are included within that range, particularly in the expressions “of between” and “ranging from ... to ...”.

[0019] Moreover, the expression “at least one” used in the present description is equivalent to the expression “one or more”.Direct dyes

[0020] The composition according to the invention comprises one or more direct dyes.

[0021] “Direct dye” is understood to mean coloured species. These are dyes which will spread superficially on the fibre. They are different from oxidation dyes.

[0022] The direct dye(s) that can be used according to the invention are chosen from natural direct dyes, synthetic direct dyes, and mixtures thereof.

[0023] Preferably, the direct dye(s) that can 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.

[0024] 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.

[0025] The composition may comprise one or more nonionic direct dyes.

[0026] Among the nonionic direct dyes, mention may be made of neutral nitrobenzene direct dyes, neutral azo direct dyes and neutral anthraquinone dyes.

[0027] The composition may comprise one or more cationic direct dyes.

[0028] “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.

[0029] The cationic direct dye(s) contain at least one quaternized cationic chromophore or at least one chromophore bearing a quaternized or quaternizable cationic group.

[0030] According to a particular embodiment of the invention, the cationic direct dyes comprise at least one quaternized cationic chromophore.

[0031] 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, hemicyanines, 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.

[0032] For the cationic azo dyes, mention may be made particularly of those resulting from the cationic dyes described in the Kirk-Othmer Encyclopedia of Chemical Technology, “Dyes, Azo”, J. Wiley & Sons, updated on 19 April 2010.

[0033] Among the azo dyes that can be used according to the invention, mention may be made of the cationic azo dyes described in patent applications WO 95 / 15144, WO 95 / 01772 and EP 714954.

[0034] Among the azo dyes described in the Colour 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.

[0035] Among the cationic quinone dyes, those mentioned in the abovementioned Colour 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.

[0036] Among the azine dyes that are suitable for use, mention may be made of those listed in the Colour Index International, for example the following dyes:- Basic Blue 17- Basic Red 2.

[0037] Among the cationic triarylmethane dyes that can be used according to the invention, mention may be made, in addition to those listed in the Colour Index, of the following dyes:- Basic Green 1- Basic Violet 3- Basic Violet 14- Basic Blue 7- Basic Blue 26.

[0038] Mention may also be made of the cationic dyes in the documents US 5888252, EP 1133975, WO 03 / 029359, EP 860636, WO 95 / 01772, WO 95 / 15144, 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.

[0039] Preferably, the cationic direct dyes are chosen from those resulting from dyes of azo and hydrazono type.

[0040] 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.

[0041] Preferably, the cationic direct dye(s) comprise a quaternary ammonium group; more preferentially, the cationic charge is endocyclic.

[0042] 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.

[0043] 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:

[0044] Het+-C(Ra)=N-N(Rb)-Ar, Q-(C-II)

[0045] Het+-N(Ra)-N=C(Rb)-Ar, Q-(C-III)

[0046] Het+-N=N-Ar, Q-(C-IV)

[0047] Ar+-N=N-Ar’’, Q-(C-V),

[0048] in which formulae (C-II) to (C-V):* Het+represents a cationic heteroaryl radical, preferentially bearing an endocyclic cationic charge, such as imidazolium, indolium or pyridinium, which is optionally substituted, preferentially with at least one (C1-C8)alkyl group such as methyl;* Ar+represents an aryl radical, such as phenyl or naphthyl, bearing an exocyclic cationic charge, preferentially ammonium, particularly tri(C1-C8)alkylammonium, such as trimethylammonium;* Ar represents an aryl group, notably phenyl, which is optionally substituted, preferentially with one or more electron-donating groups such as i) optionally substituted (C1-C8)alkyl, ii) optionally substituted (C1-C8)alkoxy, iii) (di)(C1-C8)(alkyl)amino optionally substituted on the alkyl group(s) with a hydroxyl group, iv) aryl(C1-C8)alkylamino, v) optionally substituted N-(C1-C8)alkyl-N-aryl(C1-C8)alkylamino or alternatively Ar represents a julolidine group;* Ar’’ represents an optionally substituted (hetero)aryl group, such as phenyl or pyrazolyl, which are optionally substituted, preferentially with 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 with a hydroxyl group;* or else the substituent Ra with a substituent of Het+and / or Rb with a substituent of Ar form, together with the atoms that bear them, a (hetero)cycloalkyl; in particular, Ra and Rb represent a hydrogen atom or a (C1-C4)alkyl group optionally substituted with a hydroxyl group;* Q-represents an organic or mineral anionic counterion, such as a halide or an alkyl sulfate.

[0049] 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.

[0050] Preferentially, mention may be made of the following direct dyes: (C-II-1), (C-IV-1),

[0051] in which formulae (C-II-1) and (C-IV-1):- R1represents a (C1-C4)alkyl group such as methyl;- R2and R3, which may be 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) with 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 previously, in particular a halide, such as chloride, or an alkyl sulfate, such as methyl sulfate or mesyl.

[0052] 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:

[0053] Basic Red 51

[0054] Basic Orange 31

[0055] Basic Yellow 87,with Q’ being an anionic counterion as defined above, particularly a halide, such as chloride, or an alkyl sulfate, such as methyl sulfate or mesyl.

[0056] According to a particular embodiment of the invention, the direct dyes are fluorescent, i.e. they contain at least one fluorescent chromophore as defined previously.

[0057] 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.

[0058] Mention may also be made of the fluorescent dyes described in EP 1133975, WO 03 / 029359, EP 860636, WO 95 / 01772, WO 95 / 15144 and EP 714954 and those listed in the encyclopaedia “The Chemistry of Synthetic Dyes” by K. Venkataraman, 1952, Academic Press, volumes 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.

[0059] 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, the tautomers thereof, the organic or mineral acid or base salts thereof, and also the solvates thereof such as hydrates:

[0060] W+–[C(Rc)=C(Rd)]m’–Ar, Q-(C-VI),

[0061] in which formula (C-VI):* W+represents a cationic heterocyclic or heteroaryl group, particularly comprising a quaternary ammonium optionally substituted with one or more (C1-C8)alkyl groups, optionally substituted notably with one or more hydroxyl groups;* Ar representing an aryl group such as phenyl or naphthyl, optionally substituted preferentially with i) one or more halogen atoms such as chlorine or fluorine; ii) one or more (C1-C8)alkyl groups, preferably a C1-C4alkyl group 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 with one or more hydroxyl groups, such as (di)hydroxyethylamino, vii) one or more acylamino groups; viii) one or more heterocycloalkyl groups such as piperazinyl, piperidyl or 5- or 6-membered heteroaryl such as pyrrolidinyl, pyridyl and imidazolinyl;* m’ represents an integer between 1 and 4 inclusive, and in particular m is 1 or 2; more preferentially 1;* Rcand Rd, which may be identical or different, represent a hydrogen atom or an optionally substituted (C1-C8)alkyl group, preferentially a C1-C4alkyl group, or alternatively Rccontiguous with W+and / or Rdcontiguous with Ar form, with the atoms that bear them, a (hetero)cycloalkyl; in particular, Rcis contiguous with W+and they form a (hetero)cycloalkyl such as cyclohexyl;* Q-is an organic or mineral anionic counterion as defined previously.

[0062] Among the cationic direct dyes, mention may also be made of triarylmethane cationic dyes.

[0063] 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’),

[0064] 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:

[0065] in which preceding formulae (C-VII) and (C-VII’):* R1, R2, R3and R4, which may be identical or different, represent a hydrogen atom or group from among: (C1-C6)alkyl which is optionally substituted, preferably with a hydroxyl group; aryl such as phenyl, aryl(C1-C4)alkyl such as benzyl, heteroaryl, heteroaryl(C1-C4)alkyl, or else two groups R1and R2, and / or R3and R4, 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, R15and R16, which may be identical or different, represent a hydrogen or 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 a 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 with 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 or 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 R16form, together with the carbon atoms which bear them, an aryl or heteroaryl, preferably benzo, 6-membered fused ring, said ring possibly also being optionally 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.

[0066] 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.

[0067] 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 relative to the phenyl group.

[0068] 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.

[0069] Among the cationic direct dyes, mention may also be made of anthraquinone cationic dyes.

[0070] The anthraquinone cationic direct dye(s) that can be used in the composition of the invention comprise a quaternary ammonium group.

[0071] 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.

[0072] Preferably, the cationic charge is exocyclic.

[0073] Among the anthraquinone cationic direct dyes, those of formula (C-VIII) having an exocyclic cationic charge are preferred: (C-VIII)

[0074] 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.

[0075] 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.

[0076] More preferentially, in formula (C-VIII):- 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.

[0077] 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’’)

[0078] with Q-being an anionic counterion, particularly a halide, such as bromide or chloride, or an alkyl sulfate, such as methyl sulfate or mesyl. Preferably, Q-is a halide, better still a bromide.

[0079] The term “anionic counterion” means 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 methanesulfonate or mesylate and ethanesulfonate; 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; xvi) borates, such as tetrafluoroborate, and xvii) disulfate (O=)2S(O-)2or SO42-and monosulfate HSO4-.

[0080] One particularly preferred dye of formula (C-VIII’) is HC Blue 17.

[0081] One particularly preferred dye of formula (C-VIII’’) is HC Blue 16 (1-methylamino-4-(3’-dimethylpropylammoniumpropylamino)anthraquinone bromide).

[0082] Preferentially, the anthraquinone cationic direct dye(s) are chosen from the dyes of formulae (C-VIII’) and (C-VIII’’), and more preferentially from the dyes of formula (C-VIII’’), better still from HC Blue 16.

[0083] The composition according to the invention may comprise one or more anionic direct dyes.

[0084] The anionic direct dyes of the invention are dyes commonly referred to as “acid” direct dyes on account of their affinity for alkaline substances. The term “anionic direct dye” means 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.

[0085] 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:

[0086] a) the diaryl anionic azo dyes of formula (A-II) or (A-II’): (A-II) (A-II’),

[0087] 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;- hydroxy, 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 previously;- 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 previously;- (di)(alkyl)amino;- aryl(alkyl)amino optionally substituted with 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 with one or more alkyl, (O)2S(O-)-, M+or phenylamino groups;- or alternatively 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 with 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 aryl(alkyl)amino which is optionally substituted; with M+, R°, X, X’, X’’ and Ar as defined above;* W represents a sigma bond σ, an oxygen or sulfur atom, or a divalent radical i) –NR- with R as defined previously, 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 alternatively Ra and Rb form, together with the carbon atom that 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.

[0088] 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;

[0089] and, as examples of dyes of formula (A-II’), mention may be made of: Acid Red 111, Acid Red 134, Acid Yellow 38;

[0090] b) the pyrazolone anionic azo dyes of formulae (A-III) and (A-III’): (A-III) (A-III’),

[0091] 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 previously;* R14represents a hydrogen atom, an alkyl group or a group -C(O)O-, M+with M+as defined previously;* R15represents a hydrogen atom;* R16represents an oxo group, in which case R’16is absent, or alternatively 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 previously;- Ar-O-S(O)2- with Ar representing an optionally substituted aryl group; preferentially a phenyl optionally substituted with 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 previously; 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;

[0092] c) the anthraquinone dyes of formulae (A-IV) and (A-IV’): (A-IV), (A-IV’)

[0093] in which formulae (A-IV) and (A-IV’):

[0094] * R22, R23, R24, R25, R26and R27, which may be identical or different, represent a hydrogen or halogen atom, or a group chosen from:- alkyl;- hydroxy, mercapto;- alkoxy, alkylthio;- optionally substituted aryloxy or arylthio, preferentially substituted with one or more groups chosen from alkyl and (O)2S(O-)-, M+with M+as defined previously;- aryl(alkyl)amino optionally substituted with one or more groups chosen from alkyl and (O)2S(O-)-, M+with M+as defined previously;- (di)(alkyl)amino;- (di)(hydroxyalkyl)amino;- (O)2S(O-)-, M+with M+as defined previously;* 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 with one or more groups, particularly i) alkyl such as methyl, n-dodecyl, n-butyl; ii) (O)2S(O-)-, M+with M+as defined previously; iii) R°-C(X)-X’-, R°-X’-C(X)-, R°-X’-C(X)-X’’- with R°, X, X’ and X’’ as defined previously, 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 previously;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;

[0095] d) the nitro dyes of formulae (A-V) and (A-V’): (A-V) (A-V’)

[0096] 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 with one or more hydroxyl groups, alkylthio optionally substituted with one or more hydroxyl groups;- hydroxy, mercapto;- nitro, nitroso;- polyhaloalkyl;- R°-C(X)-X’-, R°-X’-C(X)-, R°-X’-C(X)-X’’- with R°, X, X’ and X’’ as defined previously;- (O)2S(O-)-, M+with M+as defined previously;- (O)CO--, M+with M+as defined previously;- (di)(alkyl)amino;

[0097] - (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 previously; W particularly represents an –NH– group;* ALK represents a linear or branched divalent C1-C6alkylene group; in particular, ALK represents a -CH2-CH2- group;* n is 1 or 2;* p represents an integer inclusively between 1 and 5;* q represents an integer inclusively between 1 and 4;* u is 0 or 1;* when n is 1, J represents a nitro or nitroso group; particularly nitro;* when n is 2, J represents an oxygen or sulfur atom, or a divalent radical –S(O)m– with m representing an integer 1 or 2; preferentially, J represents an –SO2– radical;* M’ represents a hydrogen atom or a cationic counterion;

[0098] * , which may be present or absent, represents a benzo group,optionally substituted with one or more groups R30as defined previously;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.

[0099] 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;

[0100] e) the triarylmethane dyes of formula (A-VI): (A-VI)

[0101] 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 with a group (O)mS(O-)-, M+with M+and m as defined previously;* 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;- hydroxy, 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 previously;- or alternatively two contiguous groups R41with R42or R42with R43or R43with R44together form a fused benzo group: I’; with I’ optionally substituted with 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’ and X’’ as defined previously;in particular, R37to R40represent a hydrogen atom, and R41to R44, which may be identical or different, represent a hydroxyl group or (O)2S(O-)-, M+; and when R43with R44together form a benzo group, it is preferentially substituted with 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;

[0102] f) the xanthene-based dyes of formula (A-VII): (A-VII)

[0103] 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;- hydroxy, mercapto;- nitro, nitroso;- (O)2S(O-)-, M+with M+representing a hydrogen atom or a cationic counterion;- (O)CO--, M+with M+as defined previously;particularly, R53, R54, R55and R48represent a hydrogen or halogen atom;* G represents an oxygen or sulfur atom or an NR group 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 previously; 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 with one or more alkyl or (O)mS(O-)-, M+groups with m and M+as defined previously;* Q and Q’, which may be identical or different, represent an oxygen or sulfur atom; particularly, Q and Q’ represent an oxygen atom;* M+is as defined previously.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;

[0104] g) the indole-based dyes of formula (A-VIII): (A-VIII),

[0105] 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;- hydroxy, 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 previously;* G represents an oxygen or sulfur atom or an NR group 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.

[0106] As examples of dyes of formula (A-VIII), mention may be made of: Acid Blue 74.

[0107] h) the quinoline-based dyes of formula (A-IX): (A-IX),

[0108] 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 a group (O)2S(O-)-, M+with M+representing a hydrogen atom or a cationic counterion;* or alternatively R61with R62, or R61with R64, together form a benzo group optionally substituted with one or more groups (O)2S(O-)-, M+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.

[0109] As examples of dyes of formula (A-IX), mention may be made of: Acid Yellow 2, Acid Yellow 3 and Acid Yellow 5.

[0110] More particularly, the composition comprises one or more anionic direct dyes chosen, alone or as a mixture, from the following anionic direct dyes:

[0111] (C.I. 45380)Acid Red 87 (A-VII)(C.I. 10316)Sodium salt of 2,4-dinitro-1-naphthol-7-sulfonic acid (A-V’)(C.I. 10383)Acid Orange 3 (A-V)(C.I. 13015)Acid Yellow 9 / Food Yellow 2 (A-II)(C.I. 14780)Direct Red 45 / Food Red 13 (A-II)(C.I. 13711)Acid Black 52 (A-II)(C.I. 13065)Acid Yellow 36 (A-II)(C.I. 14700)Sodium salt of 1-hydroxy-2-(2’,4’-xylyl-5-sulfonatoazo)naphthalene-4-sulfonic acid / Food Red 1 (A-II)(C.I. 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.I. 15510)Acid Orange 7 / Pigment Orange 17 / Solvent Orange 49 (A-II)(C.I. 15985)Food Yellow 3 / Pigment Yellow 104 (A-II)(C.I. 16185)Acid Red 27 / Food Red 9 (A-II)(C.I. 16230)Acid Orange 10 / Food Orange 4 (A-II)(C.I. 16250)Acid Red 44 (A-II)(C.I. 17200)Acid Red 33 / Food Red 12 (A-II)(C.I. 15685)Acid Red 184 (A-II)(C.I. 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.I. 18130)Acid Red 135 (A-II)(C.I. 19130)Acid Yellow 27 (A-III)(C.I. 19140)Acid Yellow 23 / Food Yellow 4 (A-III)(C.I. 20170)4’-(Sulfonato-2’’,4’’-dimethyl)bis(2,6-phenylazo)-1,3-dihydroxybenzene / Acid Orange 24 (A-II)(C.I. 20470)Sodium salt of 1-amino-2-(4’-nitrophenylazo)-7-phenylazo-8-hydroxynaphthalene-3,6-disulfonic acid / Acid Black 1 (A-II)(C.I. 23266)(4-((4-Methylphenyl)sulfonyloxy)phenylazo)-2,2’-dimethyl-4-((2-hydroxy-5,8-disulfonato)naphthylazo)biphenyl / Acid Red 111 (A-II’)(C.I. 27755)Food Black 2 (A-II)(C.I. 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.I. 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)

[0112] Most of these dyes are described in particular in the Colour Index published by The Society of Dyers and Colourists, P.O. Box 244, Perkin House, 82 Grattan Road, Bradford, Yorkshire, BD1 2JB, England.

[0113] The anionic dyes which are more particularly preferred are the dyes designated in the Colour 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).

[0114] Use may also be made of compounds corresponding to the mesomeric or tautomeric forms of structures (A-II) to (A-IX).

[0115] 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.

[0116] Preferably, the composition according to the invention comprises one or more direct dyes chosen from anionic direct dyes, cationic direct dye(s) and mixtures thereof.

[0117] According to a first, preferred embodiment, the composition according to the invention comprises one or more cationic direct dyes.

[0118] More preferably, the composition according to the invention comprises one or more cationic direct dyes chosen from azo cationic direct dyes, hydrazono cationic direct dyes, anthraquinone cationic direct dyes, triarylmethane cationic direct dyes, and mixtures thereof.

[0119] According to another preferred embodiment, the composition according to the invention comprises one or more anionic direct dyes, preferably chosen from acid azo direct dyes, acid azine direct dyes, acid triarylmethane direct dyes, acid indoamine direct dyes, acid anthraquinone direct dyes, acid indigoid direct dyes, acid natural direct dyes, and mixtures thereof.

[0120] Preferably, 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 and even better still from 0.1% to 3% by weight, relative to the total weight of the composition.

[0121] More preferably, the total content of the cationic 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 and even better still from 0.1% to 3% by weight, relative to the total weight of the composition.

[0122] More preferably, the total content of the anionic 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 and even better still from 0.1% to 3% by weight, relative to the total weight of the composition.Non-associative polysaccharide

[0123] The composition according to the invention comprises one or more non-associative polysaccharides chosen from polysaccharides of microbial origin.

[0124] 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.

[0125] 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.

[0126] For the purposes of the present invention, the term “associative polymer” means an amphiphilic polymer that is capable, in an aqueous medium, of reversibly combining with itself or with other molecules. It generally includes, in its chemical structure, at least one hydrophilic region or group and at least one hydrophobic region or group.

[0127] The term “hydrophobic region or group” is intended to mean a hydrocarbon group or a polymer comprising a saturated or unsaturated, linear or branched hydrocarbon chain. When it denotes a hydrocarbon group, the hydrophobic group contains at least 8 carbon atoms, preferably from 8 to 30 carbon atoms, in particular from 8 to 24 carbon atoms and preferentially from 10 to 24 carbon atoms.

[0128] Preferably, the non-associative polysaccharides do not comprise any hydrocarbon groups containing from 10 to 30 carbon atoms and preferably do not comprise any hydrocarbon-based groups containing from 8 to 30 carbon atoms.

[0129] Non-associative polysaccharides chosen from polysaccharides of microbial origin that may notably be mentioned include the following polymers, alone or as a mixture:- 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).

[0130] Preferably, the non-associative polysaccharide(s) chosen from polysaccharides of microbial origin are chosen from scleroglucan gums, xanthan gums, gellan gums, and mixtures thereof, more preferentially from scleroglucan gums, xanthan gums, and mixtures thereof.

[0131] More preferentially, the non-associative polysaccharide chosen from polysaccharides of microbial origin is scleroglucan gum.

[0132] Preferably, the composition according to the invention comprises one or more non-associative polysaccharide(s) chosen from polysaccharides of microbial origin chosen from scleroglucan gums, xanthan gums, gellan gums, and mixtures thereof, more preferentially from scleroglucan gums, xanthan gums, and mixtures thereof, even more preferentially, is scleroglucan gum.

[0133] The non-associative polysaccharide(s) chosen from polysaccharides of microbial origin used in the composition of the invention are preferably present in a total content ranging from 0.01% to 20% by weight, preferably ranging from 0.1% to 15% by weight, preferentially from 0.5% to 10% by weight, better still from 1% to 5% by weight, relative to the weight of the composition.

[0134] Preferably, the non-associative polysaccharides chosen from polysaccharides of microbial origin are chosen from scleroglucan gums, xanthan gums and mixtures thereof and they are present in a total content ranging from 0.01% to 20% by weight, preferably ranging from 0.1% to 15% by weight, preferentially from 0.5% to 10% by weight, better still from 1% to 5% by weight, relative to the weight of the composition.

[0135] More preferentially, the non-associative polysaccharide chosen from polysaccharides of microbial origin is scleroglucan gum, present in a total content ranging from 0.01% to 20% by weight, preferably ranging from 0.1% to 15% by weight, preferentially from 0.5% to 10% by weight, better still from 1% to 5% by weight, relative to the weight of the composition.

[0136] The composition according to the invention can comprise one or more additional non-associative polysaccharides different from non-associative polysaccharides of microbial origin.

[0137] Non-associative polysaccharides different from polysaccharides of microbial origin that may notably be mentioned include the following polymers, alone or as a mixture:a) tree or shrub exudates, including:- acacia gum (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 of glucuronic acid);- carrageenans and furcellerans (polymers of galactose sulfate and of 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) polymers extracted from plants, including:- celluloses (glucose polymers);- starches (glucose polymers) and- inulin.

[0138] 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.

[0139] In particular, the guar gums, locust bean gums, starches and celluloses may be modified / treated.

[0140] The guar gums that may be used according to the invention may be modified with (poly)hydroxy(C1-C6)alkyl groups. Among the (poly)hydroxy(C1-C6)alkyl 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.

[0141] Such guar gums optionally modified with hydroxyalkyl groups are sold, for example, under the trade names Jaguar HP8, Jaguar HP60 and Jaguar HP120 by Rhodia Chimie.

[0142] 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 hydrolysates of the starches mentioned above. The starch is preferably derived from potato.

[0143] 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 Avebe, or Structure Zea from National Starch (gelatinized corn distarch phosphate).

[0144] 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.

[0145] The additional non-associative polysaccharides that may be used according to the invention may be cellulose-based polymers.

[0146] 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.

[0147] Cellulose-based polymers are also known as celluloses.

[0148] 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.

[0149] Among these cellulose-based polymers, a distinction is made between cellulose ethers, cellulose esters and cellulose ether esters.

[0150] 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.

[0151] 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.

[0152] 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 Aqualon) and carboxymethylhydroxyethylcelluloses, and the sodium salts thereof.

[0153] 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)alkylcelluloses, 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 National Starch.Polycarboxylic acids

[0154] The composition according to the invention comprises at least one polycarboxylic acid of formula (I) below, or a salt thereof, an optical isomer thereof, a geometric isomer thereof, and / or a solvate thereof:R1-N-(CH(R2)COOH)2(I)in whichR1represents a hydrogen atom or a -CH(COOH)-(CH2)2-COOH,-CH2CH2OH, -CH(CH3)COOH, -(CH2)2N(COR3)-CH2-COOH or -CH(COOH)-CH2-COOH group; andR2represents a CH2COOH group when R1represents a hydrogen atom, or R2represents a hydrogen atom when R1is other than a hydrogen atom; andR3represents a linear or branched alkyl group comprising from 1 to 4 carbon atoms or cyclic alkyl group comprising from 3 to 30 carbon atoms,

[0155] For the purposes of the present invention, the “solvates” represent hydrates and also the combination with linear or branched C1-C4alcohols such as ethanol, isopropanol or n-propanol.

[0156] More precisely, the polycarboxylic acids of formula (I) correspond to:- compounds comprising four carboxylic acid functions, when R1represents a hydrogen atom and R2represents a -CH2-COOH group, or when R1represents the -CH(COOH)-(CH2)2-COOH group and R2represents a hydrogen atom or when R1represents the -CH(COOH)-CH2-COOH group and R2represents a hydrogen atom;- compounds comprising three carboxylic acid functions, when R1represents the -CH(CH3)-COOH group and R2represents a hydrogen atom, or when R1represents a -(CH2)2-N(COR3)-CH2-COOH group and R2represents a hydrogen atom; and to- compounds comprising two carboxylic acid functions, when R1represents the -CH2CH2OH group and R2represents a hydrogen atom.

[0157] Preferably, R1represents a -CH(COOH)-(CH2)2-COOH group and R2represents a hydrogen atom.

[0158] The polycarboxylic acids of formula (I) may be in the form of pure enantiomers, preferably of L configuration, or in the form of mixtures, notably racemic mixtures.

[0159] The salts of the polycarboxylic acid(s) of formula (I) are preferably chosen from alkali metal salts, alkaline-earth metal salts, transition metal salts, organic amine salts, the ammonium and substituted ammonium salts thereof, and mixtures thereof.

[0160] As examples of alkali metal salts, mention may notably be made of the sodium (Na+) and potassium (K+) salts, whereas as examples of alkaline-earth metal salts, mention may notably be made of the calcium (Ca2+) and magnesium (Mg2+) salts.

[0161] For the purposes of the present invention, the term "transition metal" means a metal having an incomplete d sub-shell, more particularly in oxidation state II, such as cobalt (Co2+), iron (Fe2+), manganese (Mn2+), zinc (Zn2+) and copper (Cu2+).

[0162] As regards the salts of organic amines, mention may be made of the salts of primary, secondary or tertiary amines, or alternatively of alkanolamines. Said amines exhibit one or more identical or non-identical radicals, of linear or branched C1to C20alkyl type, optionally comprising a heteroatom such as oxygen.

[0163] Among the salts of these compounds, the alkali metal salts and in particular the sodium or potassium salts are preferred.

[0164] Preferably, said polycarboxylic acid(s) of formula (I) or salts thereof, optical isomers thereof, geometric isomers thereof and / or solvates thereof used in the context of the present invention are chosen from methylglycinediacetic acid, N-lauroyl-ethylenediamine-N,N',N'-triacetic acid, N,N-dicarboxymethylglutamic acid, iminodisuccinic acid, N,N-bis(carboxymethyl)aspartic acid, alkali metal salts thereof, alkaline-earth metal salts thereof, transition metal salts thereof, organic amine salts thereof, ammonium salts thereof, optical isomers thereof, geometric isomers thereof, solvates thereof and mixtures thereof, and more preferentially from N,N-dicarboxymethylglutamic acid, N,N-bis(carboxymethyl)aspartic acid, alkali metal salts thereof, alkaline-earth metal salts thereof, transition metal salts thereof, organic amine salts thereof, ammonium salts thereof, optical isomers thereof, geometric isomers thereof, solvates thereof and mixtures thereof.

[0165] Better still, the polycarboxylic acid(s) of formula (I) or salts thereof, optical isomers thereof, geometric isomers thereof and / or solvates thereof are chosen from N,N-dicarboxymethylglutamic acid, N,N-bis(carboxymethyl)aspartic acid, alkali metal salts thereof, alkaline-earth metal salts thereof, transition metal salts thereof, organic amine salts thereof, ammonium salts thereof, optical isomers thereof, geometric isomers thereof, solvates thereof and mixtures thereof.

[0166] Preferably, the polycarboxylic acid(s) of formula (I) or salts thereof, optical isomers thereof, geometric isomers thereof and / or solvates thereof used according to the present invention are chosen from N,N-dicarboxymethylglutamic acid, alkali metal salts thereof, optical isomers thereof, geometric isomers thereof, and mixtures thereof; more preferentially from N,N-dicarboxymethylglutamic acid, tetrasodium N,N-bis(carboxymethyl)glutamate, optical isomers thereof and geometric isomers thereof; better still from N,N-dicarboxymethyl-L-glutamic acid, tetrasodium N,N-bis(carboxymethyl)-L-glutamate, and mixtures thereof.

[0167] Very preferentially, use will be made of the compound with the name Tetrasodium Glutamate Diacetate (INCI name), such as Dissolvine GL38 or 47S sold by the company AkzoNobel.

[0168] Preferably, the total content of polycarboxylic acid(s) of formula (I), salts thereof, optical isomers thereof, geometric isomers thereof, and solvates thereof, in the composition is in the range from 0.01% to 20% by weight, preferably from 0.05% to 15%, more preferentially from 0.075% to 10% by weight, better still from 0.1% to 5% by weight, even better still from 0.15% to 3% by weight, and better still yet from 0.2% to 2%, relative to the total weight of the composition according to the invention.

[0169] Preferably, the total content of N,N-dicarboxymethyl-L-glutamic acid and tetrasodium N,N-bis(carboxymethyl)-L-glutamate in the composition is in the range from 0.01% to 20% by weight, preferably from 0.05% to 15%, more preferentially from 0.075% to 10% by weight, better still from 0.1% to 5% by weight, even better still from 0.15% to 3% by weight, and better still yet from 0.2% to 2%, relative to the total weight of the composition according to the invention.

[0170] Preferably, the total content of tetrasodium glutamate diacetate (GLDA) in the composition is in the range from 0.01% to 20% by weight, preferably from 0.05% to 15%, more preferentially from 0.075% to 10% by weight, better still from 0.1% to 5% by weight, even better still from 0.15% to 3% by weight, and better still yet from 0.2% to 2%, relative to the total weight of the composition according to the invention.Hydroxylated compounds

[0171] The composition according to the invention comprises one or more hydroxylated compounds chosen from aromatic alcohols and hydroxylated C2-C6aliphatic solvents, and mixtures thereof.

[0172] Aromatic alcohol

[0173] The composition according to the invention may comprise one or more aromatic alcohols.

[0174] Preferably, the composition according to the invention does comprise one or more aromatic alcohols.

[0175] The expression "aromatic alcohol" means any compound, which is liquid at room temperature and atmospheric pressure, comprising at least one benzene or naphthalene ring and at least one alcohol function (OH) directly bonded to the ring or bonded to at least one substituent on said ring. Preferably, the alcohol function will be on a substituent of the benzene or naphthalene ring.

[0176] More preferably, the composition according to the invention comprises one or more aromatic alcohols of formula (II): (II)

[0177] 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 independently represents a C1-C4 alkyl radical or a halogen. In other words, when n > 1, the various X may be identical or different.

[0178] Preferably, n is equal to 0.

[0179] According to a particular embodiment, Y represents a hydroxymethyl, hydroxyethyl or hydroxyethyloxy radical.

[0180] Examples of aromatic alcohols of formula (II) that may be mentioned include benzyl alcohol, phenylethanol and phenoxyethanol. According to one particular embodiment, the aromatic alcohol of formula (II) is benzyl alcohol.

[0181] The aromatic alcohol(s) may be present in the composition according to the invention in a total content ranging from 0.01% to 10% by weight, preferably from 0.05% to 8% by weight, better still from 0.1% to 5% by weight, and even better still from 1% to 3% by weight, relative to the total weight of the composition.

[0182] Preferably, the aromatic alcohol(s) of formula (II) may be present in the composition according to the invention in a total content ranging from 0.01% to 10% by weight, preferably from 0.05% to 8% by weight, better still from 0.1% to 5% by weight, and even better still from 1% to 3% by weight, relative to the total weight of the composition.

[0183] Preferably, benzyl alcohol may be present in the composition according to the invention in a total content ranging from 0.01% to 10% by weight, preferably from 0.05% to 8% by weight, better still from 0.1% to 5% by weight, and even better still from 1% to 3% by weight, relative to the total weight of the composition.

[0184] Aliphatic solvent

[0185] The composition according to the invention may comprise one or more hydroxylated C2-C6aliphatic solvents.

[0186] Preferably, the composition does comprise one or more hydroxylated C2-C6aliphatic solvents.

[0187] “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.

[0188] 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.

[0189] The hydroxylated aliphatic solvent(s) can be present in the composition in a total content ranging 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, and even better still from 3% to 10% by weight, relative to the weight of the composition.

[0190] Preferably, ethanol may be present in the composition according to the invention in a total content ranging 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, and even better still from 3% to 10% by weight, relative to the weight of the composition.

[0191] Preferentially, the composition comprises one or more aromatic alcohols and one or more aliphatic solvents. The aromatic alcohol(s) / hydroxylated C2-C6aliphatic solvent(s) weight ratio is preferably less than or equal to 1, and preferably ranges from 0.1 to 1, even better still from 0.1 to 0.5.

[0192] Preferably, the composition comprises benzyl alcohol and ethanol. The benzyl alcohol / ethanol weight ratio is preferably less than or equal to 1, and preferably ranges from 0.1 to 1, even better still from 0.1 to 0.5.

[0193] The 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 (II) and than the hydroxylated C2-C6aliphatic solvents such as polyol ethers, for instance dipropylene glycol monomethyl ether.

[0194] Preferably, the composition comprises water, preferably in a content ranging from 20% to 95% by weight, preferably from 30% to 93% by weight, and even more preferentially from 40% to 90% by weight, relative to the total weight of the composition.

[0195] The composition according to 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 non-associative polysaccharides; mineral or organic thickeners; antioxidants; penetrants, fragrances, buffers, dispersants, conditioning agents, film-forming agents, ceramides, preservatives and opacifiers.

[0196] The above adjuvants are generally present in an amount for each of them of between 0.01% and 20% by weight, with respect to the weight of the composition.

[0197] 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 composition are not, or are not substantially, adversely affected by the envisaged addition(s).

[0198] The pH of the composition used in the process in accordance with the invention is generally between 2 and 13 approximately, and preferably 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 fibres, or alternatively using conventional buffer systems.

[0199] 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.

[0200] Among the basifying agents, examples that may be mentioned include ammonium hydroxide, alkali metal carbonates, alkanolamines, such as monoethanolamine, diethanolamine and triethanolamine and derivatives thereof, sodium hydroxide, potassium hydroxide, and the compounds of the following formula:

[0201] in which W is a propylene residue optionally substituted by a hydroxyl group or a C1-C4alkyl radical; Ra, Rb, Rcand Rd, which may be identical or different, represent a hydrogen atom or a C1-C4alkyl or C1-C4hydroxyalkyl radical.

[0202] In particular, when the composition comprises anionic direct dyes, the pH of the composition is less than 7, preferably ranges from 2 to 5, it being possible for the pH to be adjusted by means of a carboxylic acid.

[0203] When the composition comprises cationic direct dyes, and preferably when it does not comprise any anionic direct dyes, the pH of the composition ranges from 5 to 12, preferably from 6 to 11.Process

[0204] The invention also relates to a process for dyeing keratin fibres, in particular human keratin fibres such as the hair, which comprises the application to said keratin fibres of the composition described above.

[0205] The composition may be applied to dry or wet keratin fibres.

[0206] The composition is preferably left in place on the fibres for a time ranging from 1 minute to 100 minutes, preferably from 5 minutes to 90 minutes, better still from 10 minutes to 60 minutes.

[0207] On conclusion of the treatment, the keratin fibres are optionally rinsed, preferably with water, optionally washed with a shampoo and then rinsed with water, before being dried or left to dry.

[0208] The dyeing process according to the invention may also comprise, before the step of applying the composition described above, a step of applying to said keratin fibres a composition comprising one or more alkaline agents, and optionally one or more chemical oxidizing agents.

[0209] The examples that follow serve to illustrate the invention without, however, being limiting in nature.EXAMPLES

[0210] In the examples that follow, all the amounts are given as weight percentages of active material (AM) relative to the total weight of the composition (unless otherwise mentioned).Example 1

[0211] The dyeing compositions C1 and C2 were prepared from the compounds of which the contents are indicated in the tables below:

[0212] C1C2Benzyl alcohol2.02.0Ethanol8.08.0RED 33 (CI 17200)0.50.5Scleroglucan gum2.02.0Tetrasodium glutamate diacetate-0.24pH adjusterqs pH = 2.5 ± 0.2qs pH = 2.5 ± 0.2Waterqs 100qs 100

[0213] The dyeing compositions C1 and C2 were applied to a lock of hair containing 90% natural white hairs, in a proportion of 3g /  g of hair.

[0214] After a leave-on time of 15 minutes at 40°C, then 5 minutes at room temperature under an occlusive system on a hot plate, the hair was rinsed with water and then dried in an oven at 60°C.

[0215] Colorimetric measurements were carried out using a Zeiss Interlock T 2.0 / 100 ZF-I 2 Macro lens multispectral camera to evaluate hair colouration in the L*a*b* system.

[0216] In this system, L* represents the lightness and a* and b* represent the chromaticity of the hair, a* representing the red / green axis and b* the yellow / blue axis. The smaller the value of L*, the stronger (more intense) the colouring obtained.

[0217] The colouring obtained is evaluated by measuring ΔE, which is the variation in colour before and after application of the dye, using the formula:

[0218]

[0219] in which L* represents the intensity and a* and b* represent the chromaticity of the dyed hair, and L0* represents the intensity and a0* and b0* represent the chromaticity of the untreated hair. The colour is more intense, the larger the ΔE.

[0220] Results

[0221] L*a*b*ΔEUntreated, reference hair59.460.9511.78Composition C1 (comparative)34.5932.974.4643.68Composition C2 (invention)28.9933.92.347.04

[0222] The locks of hair treated with the dyeing composition according to the invention have a higher ΔE value than those treated with the comparative composition.

[0223] In other words, the composition according to the invention makes it possible to obtain a better uptake of the dye than the comparative composition.

[0224] The locks were subsequently subjected to a shampoo wash test so as to evaluate the fastness (persistence) of the colouring obtained.

[0225] Better persistence of the colour after a shampoo wash is observed visually on the locks treated with the composition according to the invention than on the locks treated with the comparative composition.Example 2

[0226] The dyeing compositions C3 and C4 were prepared from the compounds of which the contents are indicated in the tables below:

[0227] C3C4Benzyl alcohol2.02.0Ethanol8.08.0BASIC RED 76 (CI 12245)2.02.0Scleroglucan gum2.02.0Tetrasodium glutamate diacetate-0.24pH adjusterqs pH = 9 ± 0.2qs pH = 9 ± 0.2Waterqs 100qs 100

[0228] The dyeing compositions C3 and C4 were applied to a lock of hair containing 90% natural white hairs, in a proportion of 3g /  g of hair.

[0229] After a leave-on time of 60 minutes at 27°C under an occlusive system on a hot plate, the hair was rinsed with water and then dried in an oven at 60°C.

[0230] Colorimetric measurements were carried out using a Zeiss Interlock T 2.0 / 100 ZF-I 2 Macro lens multispectral camera to evaluate hair colouration in the L*a*b* system.

[0231] In this system, L* represents the lightness and a* and b* represent the chromaticity of the hair, a* representing the red / green axis and b* the yellow / blue axis. The smaller the value of L*, the stronger (more intense) the colouring obtained.

[0232] The colouring obtained is evaluated by measuring ΔE, which is the variation in colour before and after application of the dye, using the formula:

[0233]

[0234] in which L* represents the intensity and a* and b* represent the chromaticity of the dyed hair, and L0* represents the intensity and a0* and b0* represent the chromaticity of the untreated hair. The colour is more intense, the larger the ΔE.

[0235] Results

[0236] L*a*b*ΔEUntreated, reference hair54.460.9511.78Composition C3 (comparative)36.6538.0925.3745.7Composition C4 (invention)39.5342.3129.6949.3

[0237] The locks of hair treated with the dyeing composition according to the invention have a higher ΔE value than those treated with the comparative composition.

[0238] In other words, the composition according to the invention makes it possible to obtain a better uptake of the dye than the comparative composition.Example 3

[0239] The dyeing compositions C5, C6 and C7 were prepared from the compounds of which the contents are indicated in the tables below:

[0240] C5(invention)C6(comparative)C7(comparative)Benzyl alcohol2.02.02.0Ethanol8.08.08.0BASIC RED 760,350,350,35BASIC YELLOW 570,420,420,42HC BLUE NO.160,520,520,52BASIC BROWN 170,350,350,35Scleroglucan gum2.0--HYDROXYPROPYL GUAR-2,0-HYDROXYETHYLCELLULOSE--2,0Tetrasodium glutamate diacetate0.240.240.24pH adjusterqsqsqsWaterqs 100qs 100qs 100

[0241] The dyeing compositions C5, C6 and C7 were applied to locks of hair containing 90% natural white hairs, previously bleached in a proportion of 3g /  g of hair.

[0242] The locks of hair thus dyed were subsequently subjected to a shampoo washing test so as to evaluate the fastness (persistence) of the coloring obtained, according to the following protocol:

[0243] The locks of hair were subjected to a standard shampoo, then rinsed and dried with a hair dryer.

[0244] Colorimetric measurements were performed using a KONICA MINOLTA-3600 spectrocolorimeter (D65 illuminant, 10° angle, specular component included) in the CIELab system.

[0245] 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.

[0246] The change in colour of the locks before and after washing is measured by ΔE according to the following equation:

[0247] In this equation, L*, a* and b* represent the values measured after washing the dyed hair, and L0*, a0* and b0* represent the values measured before washing the dyed hair.

[0248] The persistence (fastness) of the coloration is evaluated by the color difference ΔE between the dyed hair locks before shampoo, and then after undergoing a shampoo. The lower the ΔE value, the more persistent to shampoo washing the color is.

[0249] Results

[0250] L*a*b*ΔEC5(invention)Before shampoo23,533,426,288,15After shampoo30,34,2110,74C6(Comparative)Before shampoo24,633,26,9210,57After shampoo344,1511,72C7(Comparative)Before shampoo24,483,386,911,03After shampoo34,274,3911,89

[0251] Composition C5 according to the invention leads to significantly lower ΔE values, thus resulting in better persistence of the color after shampoo washing compared to comparative compositions C6 and C7.

[0252] Compared to compositions C6 and C7, composition C5 according to the invention improved the shampoo tenacity of the hair color.

Claims

Composition comprising:- one or more direct dyes,- one or more non-associative polysaccharides chosen from polysaccharides of microbial origin,- one or more polycarboxylic acids of formula (I) below, or salts thereof, optical isomers thereof, geometric isomers thereof, and / or solvates thereof:R1-N-(CH(R2)COOH)2(I)in whichR1represents a hydrogen atom or a -CH(COOH)-(CH2)2-COOH,-CH2CH2OH, -CH(CH3)COOH, -(CH2)2N(COR3)-CH2-COOH or -CH(COOH)-CH2-COOH group; andR2represents a CH2COOH group when R1represents a hydrogen atom, or R2represents a hydrogen atom when R1is other than a hydrogen atom; andR3represents a linear or branched alkyl group comprising from 1 to 4 carbon atoms or cyclic alkyl group comprising from 3 to 30 carbon atoms,- one or more hydroxylated compounds chosen from aromatic alcohols and hydroxylated C2-C6aliphatic solvents, and mixtures thereof.Composition according to Claim 1, which comprises one or more aromatic alcohols.Composition according to either one of Claims 1 and 2, which comprises one or more aromatic alcohols of formula (II):(II)in which Y represents a C1-C4hydroxyalkyl group or a C1-C4hydroxyalkyloxy radical, n denotes an integer ranging from 0 to 5, and X independently represents a C1-C4alkyl radical or a halogen.Composition according to the preceding claim, in which the aromatic alcohol(s) of formula (II) are chosen from benzyl alcohol, phenylethanol and phenoxyethanol, preferably benzyl alcohol.Composition according to any one of the preceding claims, in which the total content of the aromatic alcohol(s) 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, even better still from 1% to 3% by weight, relative to the weight of the composition.Composition according to any one of the preceding claims, which comprises one or more hydroxylated C2-C6aliphatic solvents.Composition according to the preceding claim, 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.Composition according to 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 composition.Composition according to any one of the preceding claims, which comprises one or more aromatic alcohols and one or more hydroxylated C2-C6aliphatic solvents, the aromatic alcohols / hydroxylated C2-C6aliphatic solvent(s) weight ratio is less than or equal to 1, preferably ranges from 0.1 to 1, even better still from 0.1 to 0.5.Composition according to any one of the preceding claims, which comprises one or more cationic direct dyes, preferably chosen from azo cationic direct dyes, hydrazono cationic direct dyes, anthraquinone cationic direct dyes, triarylmethane cationic direct dyes, and mixtures thereof.Composition according to any one of the preceding claims, which comprises one or more anionic direct dyes, preferably chosen from acid azo direct dyes, acid azine direct dyes, acid triarylmethane direct dyes, acid indoamine direct dyes, acid anthraquinone direct dyes, acid indigoid direct dyes, acid natural direct dyes, and mixtures thereof.Composition according to any 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 composition.Composition according to any one of the preceding claims, in which the non-associative polysaccharide(s) chosen from polysaccharides of microbial origin is (or are) chosen from scleroglucan gums, xanthan gums, gellan gums and mixtures thereof, preferably from xanthan gums, scleroglucan gums, and mixtures thereof, more preferentially scleroglucan gum.Composition according to any one of the preceding claims, in which the total content of the non-associative polysaccharide(s) chosen from polysaccharides of microbial origin ranges from 0.01% to 20% by weight, preferably ranging from 0.1% to 15% by weight, preferentially from 0.5% to 10% by weight, better still from 1% to 5% by weight, relative to the weight of the composition.Composition according to any one of the preceding claims, characterized in that the polycarboxylic acid(s) of formula (I) or salts thereof, optical isomers thereof, geometric isomers thereof and / or solvates thereof are chosen from N,N-dicarboxymethylglutamic acid, N,N-bis(carboxymethyl)aspartic acid, alkali metal salts thereof, alkaline-earth metal salts thereof, transition metal salts thereof, organic amine salts thereof, ammonium salts thereof, optical isomers thereof, geometric isomers thereof, solvates thereof and mixtures thereof; preferably chosen from N,N-dicarboxymethylglutamic acid, tetrasodium N,N-bis(carboxymethyl)glutamate, optical isomers thereof, geometric isomers thereof, and mixtures thereof; more preferentially N,N-dicarboxymethyl-L-glutamic acid, tetrasodium N,N-bis(carboxymethyl)-L-glutamate and mixtures thereof; even more preferentially tetrasodium glutamate diacetate.Composition according to any one of the preceding claims, in which the total content of the polycarboxylic acid(s) of formula (I) ranges from 0.01% to 20%, preferably from 0.05% to 15%, by weight, more preferentially from 0.075% to 10% by weight, better still from 0.1% to 5% by weight, even better still from 0.15% to 3% by weight, and better still yet from 0.2% to 2%, relative to the total weight of the composition.Process for dyeing keratin fibres, in particular human keratin fibres such as the hair, which comprises the application to said keratin fibres of a composition according to any one of the preceding claims.

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