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

Abstract

Composition comprising a direct dye, a 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; one or more polycarboxylic acids of formula (I); one or more hydroxylated compounds selected from aromatic alcohols, C2-C6 aliphatic hydroxylated solvents, and mixtures thereof.

Description

Title of the invention: Composition comprising a direct dye, a non-associative polysaccharide, a particular polycarboxylic acid, and a hydroxylated compound.

[0001] The present invention relates to a composition comprising a direct dye, a non-associative polysaccharide, a particular polycarboxylic acid and a hydroxylated compound, as well as a process for coloring human keratin fibers, in particular hair, implementing the composition.

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

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

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

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

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

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

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

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

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

[0011] There is also a need to obtain a hair colour that is capable of leading to a good rise, intensity and chromaticity of the colour, while having low selectivity and good tenacity, in particular good persistence to shampoos, which is capable of leading to these good dyeing performances even after a period of storage, while having good qualities of use and maintaining good sensory performance in particular in terms of shine, softness, suppleness, smoothness, detangling of keratin fibers such as hair.

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

[0013] At least one of these objectives and others are achieved by the present invention, which therefore relates to a composition comprising: - one or more direct colorant(s) - one or more non-associative polysaccharide(s), - one or more polycarboxylic acid(s) of the following formula (I), or their salts, optical isomers, geometric isomers and / or solvates: R₁₂-N-(CH(R₂)COOH)₂ (I) in which Ri represents a hydrogen atom or a group -CH(COOH)-(CH2)2-COOH, -CH2CH2OH, -CH(CH3)COOH, -(CH2)2N(COR3)-CH2-COOH, or -CH(COOH)-CH2-COOH; and Represents a CH2COOH group when Ri represents a hydrogen atom or R2 represents a hydrogen atom when Ri is not a hydrogen atom; and R3 represents an alkyl group, linear or branched with 1 to 4 carbon atoms, or cyclic with 3 to 30 carbon atoms, - one or more hydroxylated compound(s) selected from aromatic alcohols, C2-C6 aliphatic hydroxylated solvents and mixtures thereof.

[0014] The composition according to the invention is preferably a keratin fiber coloring composition, preferably human keratin fibers, in particular hair.

[0015] The invention also relates to a method for coloring keratin fibers, preferably human keratin fibers, in particular hair, using the composition.

[0016] The invention makes it possible to obtain keratin fiber colorings with good color rise, good tenacity, in particular good persistence to shampoos, as well as improved composition stability.

[0017] Other objects, features, aspects and advantages of the invention will become even clearer upon reading the description and examples that follow and upon examination of the accompanying drawing, on which:

[0018] In what follows, and unless otherwise indicated, the bounds of a range of values ​​are included in that range, in particular in the expressions "between" and "ranging from ... to ...".

[0019] Furthermore, the expression "at least one" used in this description is equivalent to the expression "one or more". Direct dyes

[0020] The composition according to the invention comprises one or more direct colorant(s).

[0021] By "direct dye," we mean colored species. These are dyes that diffuse superficially onto the fiber. They are different from oxidation dyes.

[0022] The direct dye(s) usable according to the invention are chosen from natural direct dyes, synthetic direct dyes, and their mixtures.

[0023] Preferably, the direct dye(s) usable according to the invention are chosen from among ionic direct dyes and non-ionic direct dyes, more particularly from among cationic direct dyes, amphoteric direct dyes, anionic direct dyes, non-ionic direct dyes, and mixtures thereof.

[0024] Direct dyes are for example chosen from among benzene nitrate direct dyes, azo direct dyes, tetraazapentamethinic dyes, quinonic dyes and in particular anthraquinone dyes, azinic direct dyes, triarylmethanic direct dyes, azomethine direct dyes and natural direct dyes.

[0025] The composition may include one or more non-ionic direct dyes.

[0026] Among the non-ionic direct dyes, we can mention neutral benzene nitro direct dyes, neutral azo direct dyes, neutral anthraquinone dyes.

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

[0028] By "cationic direct dye" is meant any dye other than oxidation dyes, commonly called "basic" direct dyes or "basic dyes". They are called basic because of their affinity for acidic substances, having in their structure at least one endo- or exocyclic cationic or cationizable group.

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

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

[0031] Examples of cationic direct dyes according to the invention include acridines; acridones; anthranthrones; anthrapyrimidines; anthraquinones; azines; (poly)azoic, hydrazono or hydrazones, in particular arylhydrazones; azomethines; benzantrones; benzimidazoles; benzimidazolones; benzindoles; benzoxazoles; benzopyrans; benzothiazoles; benzoquinones; bisazines; bisisoindolines; carboxanilides; coumarins; cyanines such as azacarbocyanines, diazacarbocyanines, diazahemicyanines, hemicyanines, or tetraazacarbocyanines; diazines; diketopyrrolopyrroles; dioxazines; diphenylamines; diphenylmethanes; dithiazines; flavonoids such as flavanthones and flavones; fluorindines; formazans; indamines; indanthrones; indigoids and pseudo-indigoids; indophenols; indoanilines; isoindolines; isoindolinones; isoviolanthones; lactones; (Poly)methines such as stilbene or styryl-type dimethines; naphthalimides; naphthanilides; naphtholactams; naphthoquinones; nitro, including (hetero)aromatic nitro; oxadiazoles; oxazines; perilones; perinones; perylenes; phenazines; phenoxazine; phenothiazines; phthalocyanine; polyenes / carotenoids; porphyrins; pyrantrones; pyrazolantrones; pyrazolones; pyrimidinoantrones; pyronines; quinacridones; quinolines; quinophthalones; squaranes; tetrazoliums; thiazines, thioindigo; thiopyronines; triarylmethanes, or xanthenes.

[0032] For cationic azo dyes, particular mention can be made of those derived from the cationic dyes described in the Kirk-Othmer Encyclopedia of Chemical Technology, “Dyes, Azo”, J. Wiley & sons, updated on 19 / 04 / 2010.

[0033] Among the azo dyes that can be used according to the invention, we can mention 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, the following compounds may be cited, in particular: -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 aforementioned Colour Index International are suitable, and among these, the following dyes may be cited, among others: -Basic Blue 22 -Basic Blue 99.

[0036] Among the suitable azinic dyes, those listed in the Colour Index International may be cited, 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, in addition to those listed in the Colour Index, the following dyes may be mentioned: -Basic Green 1 -Basic Violet 3 -Basic Violet 14 -Basic Blue 7 -Basic Blue 26.

[0038] Cationic dyes can also be cited in documents US 5888252, EP 1133975, WO 03 / 029359, EP 860636, WO 95 / 01772, WO 95 / 15144, EP 714954. Also cited are those listed in the encyclopedia "The chemistry of synthetic dye" by K. VENKATARAMAN, 1952, Academy Press, volumes 1 to 7, in the "Kirk-Othmer" encyclopedia "Chemical technology", chapter "Dyes and Dye intermediate", 1993, Wiley and Sons, and in various chapters of the encyclopedia "ULLMANN'S ENCYCLOPEDIA of Industrial Chemistry", 7th edition, Wiley and Sons.

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

[0040] According to a particular manufacturing method, the direct colorants are cationic azoïques, 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. Chem. (Rome) (1975), 65(5-6), 305-14 ; Journal of the Chinese Chemical Society (Taipei) (1998), 45(1), 209-211 ; Rev. Roum. Chem. (1988), 33(4), 377-83 ; Text. Res. J. (1984), 54(2), 105-7; Chem. 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 preferably the cationic charge is endocyclic.

[0042] These cationic radicals are, for example, a cationic radical: - with an exocyclic charge (di / tri)(Ci-C8)alkylammonium, or - à charge endocyclique tels que comprenant un groupe hétéroaryle cationique choisi parmi : acridinium, benzimidazolium, benzobistriazolium, benzopyrazolium, benzopyridazinium, benzoquinolium, benzothiazolium, benzotriazolium, benzoxazolium, bi-pyridinium, bis-tétrazolium, dihydrothiazolium, imidazopyridinium, imidazolium, indolium, isoquinolium, naphthoimidazolium, naphthooxazolium, naphthopyrazolium, oxadiazolium, oxazolium, oxazolopyridinium, oxonium, phénazinium, phénooxazolium, pyrazinium, pyrazolium, pyrazoyltriazolium, pyridinium, pyridinoimidazolium, pyrrolium, pyrylium, quinolium, tétrazolium, thiadiazolium, thiazolium, thiazolopyridinium, thiazoylimidazolium, thiopyrylium, triazolium ou xanthylium.

[0043] Examples include hydrazono cationic dyes of formula (C-II) and (C-III), azo dyes of formulas (C-IV) and (C-V), as well as their optical, geometric, tautomeric isomers, their salts of organic or mineral acids or bases, and their solvates such as hydrates:

[0044] Hét+-C(Ra)=NN(Rb)-Ar, Q (C-II)

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

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

[0047] Ar+-N=N-Ar”, Q (CV),

[0048] formulas (C-II) to (CV) wherein: * Het+ represents a cationic heteroaryl radical, preferably with endocyclic cationic charge such as imidazolium, indolium, or pyridinium, possibly preferentially substituted by at least one (CrC8)alkyl group such as methyl; * Ar+ represents an aryl radical, such as phenyl or naphthyl, with an exocyclic cationic charge, preferably ammonium, particularly tri(Ci-C8)alkyl-ammonium such as trimethylammonium; * Ar represents an aryl group, particularly phenyl, possibly substituted, preferably by one or more electron-donating groups such as i) (Cr C8)alkyl possibly substituted, ii) (Cr C8)alkoxy possibly substituted, iii) (di)(Ci-C8)(alkyl)amino possibly substituted on the alkyl group(s) by a hydroxyl group, iv) aryl(Ci-C8)alkylamino, v) N-(CrC8)alkyl-N-aryl(Ci-C8)alkylamino possibly substituted or Ar represents a julolidine group; * Ar” represents a (hetero)aryl group possibly substituted such as phenyl or pyrazolyl possibly substituted, preferably by one or more (CrC8)alkyl, hydroxyl, (di)(Ci-C8)(alkyl)amino, (Cr C8)alkoxy or phenyl groups; * Ra and Rb, identical or different, representing a hydrogen atom or a (CrC8)alkyl group possibly substituted, preferably by a hydroxyl group; * or the substituent Ra with a substituent of Het+ and / or Rb with a substituent of Ar together form with the atoms that bear them a (hetero)cycloalkyl; particularly Ra and Rb, representing a hydrogen atom or a (Cr C4)alkyl group possibly substituted by a hydroxyl group; * Q represents an organic or mineral anionic counter-ion such as a halide or alkyl sulfate.

[0049] In particular, one can cite the endocyclic cationic direct dyes of azo and hydrazono of formula (C-II) to (CV) as defined above; more particularly the endocyclic cationic direct dyes of formula (C-II) to (CV) described in patent applications WO 95 / 15144, WO 95 / 01772 and EP-714954.

[0050] Preferably, the following direct dyes may be mentioned:

[0051] formulas (C-II-1) and (C-IV-1) wherein: - R1 represents an (Ci-C4)alkyl group such as methyl; - R2 and R3, whether identical or different, represent a hydrogen atom or an (CrC4)alkyl group such as methyl; and - R4 represents a hydrogen atom or an electron-donating group such as (Cr C8)alkyl possibly substituted, (Ci-C8)alkoxy possibly substituted, (di)(Cr C8)(alkyl)amino optionally substituted on the alkyl group(s) by a hydroxyl group; particularly R4 is a hydrogen atom, - Z represents a CH group or a nitrogen atom, preferably CH, - Q is an anionic counterion as defined above, particularly a halide such as chloride or an alkyl sulfate such as methyl sulfate or mesytyl.

[0052] Particularly, dyes of formula (C-II-1) and (C-IV-1) are selected from the Basic Red 51, Basic Yellow 87 and Basic Orange 31 or their derivatives: Basic Red 51 Basic Orange 31 Ch Basic Yellow 87, with Q' an anionic counter ion as defined above, particularly a halide such as chloride or an alkyl sulfate such as methyl sulfate or mesytyl.

[0053] According to a particular embodiment of the invention, the direct dyes are fluorescent, that is to say they contain at least one fluorescent chromophore as defined above.

[0054] Examples of fluorescent dyes include radicals derived from the dyes acridines, acridones, benzantrones, benzimidazoles, benzimidazolones, benzindoles, benzoxazoles, benzopyranes, benzothiazoles, coumarins, difluoro{2-[(2H-pyrrol-2-ylidene-kN)methyl]-1H-pyrrolato-kN}bores (BODIPY®), diketopyrrolo-pyrroles, fluorindines, (poly)methines (in particular cyanines and styryls / hemicyanines), naphthalimides, naphthanilides, naphthylamine (such as dansyls), oxadiazoles, oxazines, perilones, perinones, perylenes, polyenes / carotenoids, squaranes, stilbenes, xanthenes.

[0055] Reference may also be made to the fluorescent dyes described in documents EP 1133975, WO 03 / 029359, EP 860636, WO 95 / 01772, WO 95 / 15144, EP 714954 and those listed in the encyclopedia "The Chemistry of Synthetic Dye" by K. Venkataraman, 1952, Academy Press, vols. 1-7, in the Kirk-Othmer Encyclopedia "Chemical Technology", chapter "Dyes and Dye Intermediate", 1993, Wiley and Sons, and in various chapters of the encyclopedia "Ullmann's Encyclopedia of Industrial Chemistry", 7th edition, Wiley and Sons, and in The Handbook — A Guide to Fluorescent Probes and Labeling Technologies, 1st ed. Molecular Probes / Invitrogen - Oregon 2005 distributed via the Internet or in previous printed editions.

[0056] According to one embodiment of the invention, the cationic dye(s) are fluorescent and comprise at least one quaternary ammonium radical such as those of the following (C-VI) formula, as well as their optical, geometric, tautomeric isomers, their salts of organic or mineral acids or bases, and their solvates such as hydrates:

[0057] W+-[C(Rc)=C(Rd)]m'-Ar, Q (C-VI),

[0058] formula (C-VI) wherein: * W+ represents a cationic heterocyclic or heteroaryl group, particularly comprising a quaternary ammonium possibly substituted by one or more (CrC8)alkyl groups possibly substituted in particular by one or more hydroxyl groups; * Ar representing an aryl group such as phenyl or naphthyl, possibly substituted preferably by i) one or more halogen atoms, such as chlorine, fluorine; ii) one or more (Ci-C8)alkyl groups, preferably Cr C4 such as methyl; iii) one or more hydroxyl groups; iv) one or more (CrC8)alkoxy groups such as methoxy; v) one or more (Ci-C8)hydroxyalkyl groups such as hydroxyethyl; vi) one or more amino or (di)(Ci-C8)alkylamino groups, preferably with the alkyl portion at Ci-C4 possibly substituted by one or more hydroxyl groups such as (di)hydroxyethylamino; vii) by one or more acylamino groups; viü) one or more heterocycloalkyl groups such as pyperazinyl, pyperidinyl or 5 or 6-membered heteroaryl groups such as pyrrolidinyl, pyridinyl and imidazolinyl; * m' represents an integer between 1 and 4 inclusive, particularly m is 1 or 2; more preferably 1; * Rc, Rd, identical or different, represent a hydrogen atom or a (Ci-C8)alkyl group possibly substituted, preferably in Ci-C4, or else Rc contiguous to W+ and / or Rd contiguous to Ar form with the atoms that bear them a (hetero)cycloalkyl, particularly Rc is contiguous to W+ and form a (hetero)cycloalkyl such as cyclohexyl; * Q is an organic or mineral anionic counter-ion as defined previously.

[0059] Among cationic direct dyes, triarylmethane cationic dyes can also be mentioned.

[0060] Preferably, the triarylmethane cationic direct dye(s) according to the invention are chosen from the following cationic dyes of formulas (C-VII) and (C-VII'): (C-VII),

[0061] as well as its addition salts with an acid or a base, organic or mineral, its geometric, optical, tautomeric isomers, and its mesomeric forms, its solvates such as hydrates,

[0062] preceding formulas (C-VII) and (C-VII') in which: * Ri, R2, R3 and R4, whether identical or different, represent a hydrogen atom or a (Ci-C6)alkyl group, possibly substituted, preferably by a hydroxyl group; aryl such as phenyl, aryl(Ci-C4)alkyl such as benzyl, heteroaryl, heteroaryl(Ci-C4)alkyl, or two groups Ri and R2, and / or R3 and Ri, on the same nitrogen atom, together with the nitrogen atom on which they are based, form a heterocycloalkyl group, possibly substituted, such as morpholino, piparazino, piperidino, preferably RB. R2, R3 and Ri, whether identical or different, represent a hydrogen atom or a (CrC4)alkyl group, * R5, R6, R7, R8, R9, Rio, Ru, R12, R13, Ru, Rb and Ri6, identical or different, represent a hydrogen atom, a halogen, or a group chosen from i) hydroxy, ii) thiol, iii) amino iv) (di)(Ci-C4)(alkyl)amino, v) (di)arylamino such as (di)phenylamino, vi) nitro, vii) acylamino (-NR-C(O)R') in which the radical R is a hydrogen atom, a Ci-C4 alkyl radical possibly bearing at least one hydroxyl group and the radical R' is a CrC2 alkyl radical; viii) carbamoyl ((R)2N-C(O)-) in which the radicals R, identical or not, represent a hydrogen atom, a Ci-C4 alkyl radical possibly bearing at least one hydroxyl group; ix) carboxylic acid or ester, (-OC(O)R') or (-C(O)OR'), in which the radical R' is a hydrogen atom, or alkyl in CrC4 possibly bearing at least one hydroxyl group and the radical R' is an alkyl radical in CrC2; x) alkyl possibly substituted in particular by a hydroxy group;xi) alkylsulfonylamino (R'SO2-NR-) in which the radical R represents a hydrogen atom, a CrC4 alkyl radical possibly bearing at least one hydroxyl group and the radical R' represents a CrC4 alkyl radical, a phenyl radical; xii) aminosulfonyl ((R)2N-SO2 ) in which the radicals R, identical or not, represent a hydrogen atom, a CrC4 alkyl radical possibly bearing at least one hydroxyl group, xiii) (Ci-C4)alkoxy, and xiv) (Ci-C4)alkylthio; ; * Or two radicals carried by two contiguous carbon atoms R5 and R6 and / or R7 and R8, and / or R9 and Rio and / or Ru and R[2 and / or Rn and R[4 and / or Ri5 and Ri6 together with the carbon atoms which carry them a condensed ring with 6 aryl or heteroaryl links, preferably benzo, said ring being able to be further optionally substituted, preferably an unsubstituted benzo ring; * Q represents an anionic counter ion to achieve electroneutrality, preferably chosen from halides such as chloride, bromide, and phosphate.

[0063] When the cationic dye includes one or more anionic substituents such as COOR or SO3R with R denoting a hydrogen or a cation, it is understood that there are then more cationic substituents than anionic substituents, so that the overall resulting charge of the triarylmethane structure is cationic.

[0064] According to a preferred embodiment, the triarylmethane dye(s) is / are selected from those of formula (C-VII) or (C-VII'), wherein, taken together or separately, - Rb R2, R3 and R4 represent a hydrogen atom or an (Ci-C4)alkyl group such as methyl or ethyl, - R5, R6, R7, R8, R9, Rio, Ru, R12, Rb, Ru, Ris and Ri6, represent a hydrogen atom, a halogen such as chlorine, or a (Ci-C4)alkyl group such as methyl or ethyl, an amino group, a (di)(Ci-C4)(alkyl)amino group and, preferably, at least one of the groups R9, R10, Rn or R12 represents a hydrogen atom, a halogen (Cl), or an amino group, or a (Ci-C4)(alkyl)amino or (di)(CrC4) (alkyl)amino group, preferably in the para position of the phenyl group.

[0065] Preferably, the direct triarylmethane structure dye(s) are chosen from Basic Violet 1, Basic Violet 2, Basic Violet 3, Basic Violet 4, Basic Violet 14, Basic Blue 1, Basic Blue 7, Basic Blue 26, Basic green 1, Basic Blue 77 (also called HC Blue 15), and mixtures thereof.

[0066] Among cationic direct dyes, anthraquinone cationic dyes can also be mentioned.

[0067] The anthraquinone cationic direct dye(s) usable in the composition of the invention comprise a quaternary ammonium group.

[0068] These cationic radicals are, for example, a cationic radical: - with an exocyclic charge (Ci-C8)alkylammonium, or - à charge endocyclique tels que comprenant un groupe hétéroaryle cationique choisi parmi : acridinium, benzimidazolium, benzobistriazolium, benzopyrazolium, benzopyridazinium, benzoquinolium, benzothiazolium, benzotriazolium, benzoxazolium, bi-pyridinium, bis-tétrazolium, dihydrothiazolium, imidazopyridinium, imidazolium, indolium, isoquinolium, naphthoimidazolium, naphthooxazolium, naphthopyrazolium, oxadiazolium, oxazolium, oxazolopyridinium, oxonium, phénazinium, phénooxazolium, pyrazinium, pyrazolium, pyrazoyltriazolium, pyridinium, pyridinoimidazolium, pyrrolium, pyrylium , quinolium, tétrazolium, thiadiazolium, thiazolium, thiazolopyridinium, thiazoylimidazolium, thiopyrylium, triazolium ou xanthylium.

[0069] De préférence, la charge cationique est exocyclique.

[0070] Parmi les colorants directs cationiques anthraquinoniques, on préfère ceux de formule (C-VIII) ayant une charge cationique exocyclique : (c-vm)

[0071] in which: - R1, R2 and R3, identical or different, representing a hydrogen atom or a (Ci-C8)alkyl group possibly substituted; - R4 representing a hydrogen atom or a (CrC8)alkyl group possibly substituted; - R5 representing a hydrogen atom, a (CrC8)alkyl group (possibly substituted), a (Ci-C8)alkylene group (possibly substituted), a halogen, a hydroxyl group, or a (CrC8)alkoxy group - n representing a number between 1 and 8; - Q represents an organic or mineral anionic counter-ion such as a halide or an alkyl sulfate.

[0072] Preferably, in formula (C-VIII): - R1, R2 and R3, identical or different, representing a (Ci-C6)alkyl group possibly substituted; - R4 representing a hydrogen atom or possibly substituted (Ci-C6)alkyl group; - R5 representing a hydrogen atom or a (Ci-C8)alkyl group, possibly substituted, - n representing a number between 1 and 6; - Q representing a halide or an alkyl sulfate.

[0073] More preferably, in formula (CVIII): - R1, R2 and R3, identical or different, representing a (Ci-C3)alkyl group possibly substituted; - R4 representing a hydrogen atom or a methyl group; preferably a methyl group - R5 representing a hydrogen atom or a methyl group, preferably a hydrogen atom; - n representing a number between 2 and 4; - Q representing a halide or an alkyl sulfate, preferably a halide.

[0074] Among the dyes of formula (C-VIII), the following dyes of formula (C-VIII') or formula (C-VIII”) may be used in particular:

[0075] with Q an anionic counter ion, particularly a halide such as bromide or chloride, or an alkyl sulfate such as methyl sulfate or mesytyl. Preferably Q is a halide, better, a bromide.

[0076] By "anionic counter-ion" is meant an anion or anionic group derived from a salt of an organic or mineral acid that counterbalances the cationic charge of the dye; more particularly, the anionic counter-ion is chosen from i) halides such as chloride, bromide; ii) nitrates; iii) sulfonates, including Ci-C6 alkylsulfonates: Alk-S(O)2O- such as methylsulfonate or mesylate and ethylsulfonate; iv) arylsulfonates: Ar-S(O)2O- such as benzenesulfonate and toluenesulfonate or tosylate; v) citrate; vi) succinate; vii) tartrate; viii) lactate; ix) alkyl sulfates: Alk-OS(O)O- such as methysulfate and ethylsulfate; x) arylsulfates: Ar-OS(O)O- such as benzene sulfate and toluene sulfate; xi) alkoxysulfates: Alk-OS(O)2O- such as methoxy sulfate and ethoxysulfate;xii) aryloxysulfates: Ar-OS(O)2O-, xiii) phosphates O=P(OH)2-O-, O=P(O-)2-OH O=P(O-)3, HO-[P(O)(O-)]wP(O)(O-)2 with w being an integer; xiv) acetate; xv) triflate; and xvi) borates such as tetrafluoroborate, xvii) disulfate (O=)2S(O-)2 or SO42 and monosulfate HSO4. ;

[0077] A dye of formula (C-VIII') particularly preferred is HC Blue 17.

[0078] A dye of formula (C-VIII”) that is particularly preferred is HC Blue 16 (l-methylamino-4-(3'-dimethylpropylammoniumpropylamino)antraquinone bromide).

[0079] Preferably, the anthraquinone cationic direct dye(s) are chosen from dyes of formula (C-VIII') and (C-VIII”), and more preferably from dyes of formula (C-VIII”), better from HC Blue 16.

[0080] The composition according to the invention may comprise one or more anionic direct dyes.

[0081] The anionic direct dyes of the invention are dyes commonly called "acid" direct dyes because of their affinity for alkali substances. Anionic direct dyes are understood to mean any direct dye having in its structure at least one CO2R or SO3R substituent, where R designates a hydrogen atom or a cation from a metal or an amine, or an ammonium ion. Anionic dyes can be selected from among acidic nitro direct dyes, acidic azo dyes, acidic azinic dyes, acidic triarylmethanic dyes, acidic indoamine dyes, acidic anthraquinone dyes, acidic indigoid dyes, and acidic natural dyes.

[0082] According to the invention, the anionic direct dye(s) can be chosen, alone or in mixture, from the following anionic direct dyes of formulas (A-II), (A-II'), (A-III), (A-m'), (A-IV), (A-IV'), (AV), (A-V'), (A-VI), (A-VII), (A-VIII) and (A-IX):

[0083] a) Diaryl anionic azo dyes of formula (A-II) or (A-II'): (A-II'),

[0084] formulas (A-II) and (A-II') in which: * R7, R8, R9, Rio, R'7, R'8, R'9 and R'1O, whether identical or different, represent a hydrogen atom or a group chosen from: - alkyl; - alkoxy, alkylthio; - hydroxy, mercapto; - nitro, nitroso; - R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X”- with R° representing a hydrogen atom, an alkyl or aryl group; X, X' and X”, identical or different, representing an oxygen, sulfur or NR atom with R representing a hydrogen atom or an alkyl group; - (O)2S(O )-, M+ with M+ representing a hydrogen atom or a cationic counter-ion; - (O)CO -, M+ with M+ as defined previously; - R”-S(O)2-, with R” representing a hydrogen atom, an alkyl group, an aryl group, (di)(alkyl)amino, aryl(alkyl)amino; preferably a phenylamino or phenyl group; - R”'-S(O)2-X'- with R'” representing an alkyl group, possibly substituted aryl, X' as defined previously; - (di)(alkyl)amino; - aryl(alkyl)amino possibly substituted by one or more groups chosen from i) nitro; ii) nitroso; iii) (O)2S(O-)-, M+ and iv) alkoxy with M+ as defined above; - heteroaryl possibly substituted; preferably a benzothiazolyl group; - cycloalkyl; in particular cyclohexyl, - Ar N=N with Ar representing an aryl group possibly substituted; preferably a phenyl possibly substituted by one or more alkyl groups, (O)2S(O )-, M+ or phenylamino; - or two contiguous groups R7 with R8 or R8 with R9 or R9 with R10 together form a fused group benzo A'; and R'7 with R'8 or R'8 with R'9 or R'9 with R'10 together form a fused group benzo B'; with A' and B' possibly substituted by one or more groups chosen from i) nitro; ii) nitroso; iii) (O)2S(O-)-, M+; iv) hydroxy; v) mercapto; vi) (di)(alkyl)amino; vii) R°-C(X)-X'- ; viii) R°-X'-C(X)- ; ix) R°-X'-C(X)-X”- ; x) Ar-N=N- and xi) aryl(alkyl)amino possibly substituted; with M+, R°, X, X', X” and Ar as defined above; * W represents a sigma bond, an oxygen atom, a sulfur atom, or a divalent radical i) -NR- with R as defined previously, or ii) methylene -C(Ra)(Rb)- with Ra and Rb, identical or different, representing a hydrogen atom or an aryl group, or Ra and Rb together with the carbon atom that binds them carries a spiro cycloalkyl; preferably W represents a sulfur atom or Ra and Rb together form a cyclohexyl; provided that formulas (A-II) and (A-II') comprise at least one sulfonate radical (O)2S(O )-, M+ or one carboxylate radical (O)CO -, M+ on one of the rings A, A', B, B' or C; preferably sodium sulfonate;

[0085] A titre d’exemple de colorants de formule (A-II), on peut citer : Acid Red 1, Acid Red 4, Acid Red 13, Acid Red 14, Acid Red 18, Acid Red 27, Acid Red 28, Acid Red 32, Acid Red 33, Acid Red 35, Acid Red 37, Acid Red 40, Acid Red 41, Acid Red 42, Acid Red 44, Pigment red 57, Acid Red 68, Acid Red 73, Acid Red 135, Acid Red 138, Acid Red 184, Food Red 1, Food Red 13, Acid Orange 6, Acid Orange 7, Acid Orange 10, Acid Orange 19, Acid Orange 20, Acid Orange 24, Yellow 6, Acid Yellow 9, Acid Yellow 36, Acid Yellow 199, Food Yellow 3; Acid Violet 7, Acid Violet 14, Acid Blue 113, Acid Blue 117, Acid Black 1, Acid Brown 4, Acid Brown 20, Acid Black 26, Acid Black 52, Food Black 1, Food Black 2 ; Food yellow 3 ou sunset yellow;

[0086] et à titre d’exemple de colorants de formule (A-IF), on peut citer : Acid Red 111, Acid Red 134, Acid yellow 38 ;

[0087] b) les colorants azo anioniques pyrrazolone de formule (A-III) et (A-IIF) : (A-III) (A-III'),

[0088] formulas (A-III) and (A-III') wherein: * Ru, R12 and Rn, whether identical or different, represent a hydrogen atom, a halogen atom, an alkyl group or -(O)2S(O), M+ with M+ as defined previously; * Ru represents a hydrogen atom, an alkyl group or a -C(O)O group, M+ with M+ as defined previously; * Rb represents a hydrogen atom; * Rie represents an oxo group in which case R'i6 is absent, or else Ri5 with Ri6 together form a double bond; * Rn and Ri8, whether identical or different, represent a hydrogen atom, or a group chosen from: - (O)2S(O )-, M+ with M+ as defined previously; - Ar-OS(O)2- with Ar representing an aryl group possibly substituted; preferably a phenyl possibly substituted by one or more alkyl groups; * R19 and R20 together form either a double bond or a benzo D' group, possibly substituted; * R'16, R'19 and R'2O, whether identical or different, represent a hydrogen atom or an alkyl or hydroxy group; * R2i represents a hydrogen atom, an alkyl group, or alkoxy; * Ra and Rb, identical or different, are as defined previously, preferably Ra represents a hydrogen atom and Rb represents an aryl group; * Y represents either a hydroxy group or an oxo group; * represents a single bond when Y is an oxo group; and represents a double bond when Y represents a hydroxy group; provided that formulas (A-III) and (A-III') comprise at least one sulfonate radical (O)2S(O )-, M+ or one carboxylate radical -C(O)O-, M+ on one of the rings D or E; preferably sodium sulfonate; Examples of colorants with formula (A-III) include: Acid Red 195, Acid Yellow 23, Acid Yellow 27, Acid Yellow 76, and examples of colorants with formula (A-III') include: Acid Yellow 17;

[0089] c) the anthraquinone dyes of formula (A-IV) and (A-IV'): (A-IV')

[0090] formulas (A-IV) and (A-IV1) wherein: * R22, R23, R24, R25, R26 and R27, whether identical or different, represent a hydrogen atom, a halogen atom, or a group chosen from: - alkyl; - hydroxy, mercapto; - alkoxy, alkylthio; - aryloxy or arylthio possibly substituted, preferably substituted by one or more groups chosen from alkyl and (O)2S(O )-, M+ with M+ as defined above; - aryl(alkyl)amino possibly substituted by one or more groups chosen from alkyl and (O)2S(O )-, M+ with M+ as defined previously; - (di)(alkyl)amino; - (di)(hydroxyalkyl)amino - (O)2S(O )-, M+ with M+ as defined previously; * Z' represents a hydrogen atom or a group NR28R29 where R2s and R29, identical or different, represent a hydrogen atom or a group chosen from: - alkyl; - polyhydroxyalkyl such as hydroxyethyl; - aryl possibly substituted by one or more particularly i) alkyl groups such as methyl, n-dodecyl, n-butyl; ii) (O)2S(O )-, M+ with M+ as defined previously; iii) R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X”- with R°, X, X' and X” as defined previously, preferably R° represents an alkyl group; - cycloalkyl; in particular cyclohexyl; * Z, represents a group chosen from hydroxy and NR'28R'29 with R'28 and R'29, identical or different, represent the same atoms or groups as R28 and R29 as defined previously; provided that formulas (A-IV) and (A-IV') comprise at least one sulfonate radical (O)2S(O )-, M+ or one carboxylate radical -C(O)O, M+; preferably sodium sulfonate; As an example of dyes of formula (A-IV), we can cite: Acid Blue 25, Acid Blue 43, Acid Blue 62, Acid Blue 78, Acid Blue 129, Acid Blue 138, Acid Blue 140, Acid Blue 251, Acid Green 25, Acid Green 41, Acid Violet 42, Acid Violet 43, Mordant Red 3; EXT purple No. 2; and as an example of dyes of formula (A-IV') we can cite: Acid Black 48;

[0091] d) the nitro dyes of formula (AV), and (A-V'): (AV) no2

[0092] formulas (AV) and (A-V') wherein: * R3o, R3i and R32, whether identical or different, represent a hydrogen atom, a halogen atom, or a group chosen from: - alkyl; - alkoxy possibly substituted by one or more hydroxy groups, alkylthio possibly substituted by one or more hydroxy groups; - hydroxy, mercapto; - nitro, nitroso; - polyhalogenoalkyl; - R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X”- with R° ; X, X' and X” as defined previously; - (O)2S(O )-, M+ with M+ as defined previously; - (O)CO -, M+ with M+ as defined previously; - (di)(alkyl)amino;

[0093] - (di)(hydroxyalkyl)amino; - heterocycloalkyl such as piperidino, piperazino or morpholino; particularly R30, R3[ and R32 represent a hydrogen atom; * Rc and Rd, whether identical or different, represent a hydrogen atom or an alkyl group; * W is as defined previously; W particularly represents a -NH- group; * ALK represents a divalent alkylene group, linear or branched, in Ci-C6; particularly ALK represents a -CH2-CH2- group; * n equals 1 or 2; * p represents an integer between 1 and 5 inclusive; * q represents an integer between 1 and 4 inclusive; * u is equal to 0 or 1; * when n equals 1, J represents a nitro, or nitroso, group; particularly nitro; * when n equals 2, J represents an oxygen atom, a sulfur atom, or a divalent radical -S(O)m- with m representing an integer 1 or 2; preferably J represents a radical -SO2-; * M' represents a hydrogen atom or a cationic counter-ion; * - - present or absent represents a benzo group, possibly substituted by one or more R30 groupings as defined above; provided that the formulas (AV) and (A-V') include at least one sulfonate radical (O)2S(O )-, M+ or one carboxylate radical -C(O)O-, M+; preferably sodium sulfonate;

[0094] As an example of colorants of formula (AV) we can cite: Acid Brown 13; Acid Orange 3; examples of dyes with the formula (A-V') include: Acid Yellow 1, Sodium salt of 2,4-dinitro-l-naphthol-7-sulfonic acid, 2-piperidino-5-nitrobenzenesulfonic acid, 2(4'-N,N(2"-hydroxyethyl)amino-2'-nitro)aniline ethanesulfonic acid, 4-β-hydroxyethylamino-3-nitrobenzenesulfonic acid; EXT D&C yellow 7;

[0095] e) triarylmethane dyes of formula (A-VI):

[0096] formula (A-VI) in which: * R33, R34, R35 and R36, identical or different, represent a hydrogen atom or a group chosen from alkyl, possibly substituted aryl and possibly substituted arylalkyl; particularly an alkyl and benzyl group possibly substituted by an (O)mS(O )-, M+ group with M+ and m as defined above; * R37, R38, R39, R40, R41, R42, R43 and R^, whether identical or different, represent a hydrogen atom or a group chosen from: - alkyl; - alkoxy, alkylthio; - (di)(alkyl)amino; - hydroxy, mercapto; - nitro, nitroso; - R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X”- with R° representing a hydrogen atom, an alkyl or aryl group; X, X' and X”, identical or different, representing an oxygen, sulfur or NR atom with R representing a hydrogen atom or an alkyl group; - (O)2S(O )-, M+ with M+ representing a hydrogen atom or a cationic counter-ion; - (O)CO -, M+ with M+ as defined previously; - or two contiguous groups R4[ with R42 or R42 with R41 or R43 with R^ together form a fused benzo group: I'; with I' possibly substituted by one or more groups chosen from i) nitro; ii) nitroso; iii) (O)2S(O )-, M+; iv) hydroxy; v) mercapto; vi) (di)(alkyl)amino; vii) R°-C(X)-X'-; viii) R°-X'-C(X)-; ix) R°-X'-C(X)-X”-; with M+, R°, X, X', X” as defined above; particularly R37 to R40 represent a hydrogen atom, and R4| to R^, identical or different, represent a hydroxy group or (O)2S(O )-, M+; and when R43 with R^ together form a benzo group, it is preferentially substituted by an (O)2S(O )- group; provided that at least one of the rings G, H, I, or I' comprises at least one sulfonate radical (O)2S(O)- or one carboxylate radical -C(O)O; preferably sulfonate. Examples of dyes with the formula (A-VI) include: Acid Blue 1; Acid Blue 3; Acid Blue 7; Acid Blue 9; Acid Violet 49; Acid Green 3; Acid Green 5; Acid Green 50;

[0097] f) xanthene-derived dyes of formula (A-VII): % (A-VII) Rs;

[0098] formula (A-VII) wherein: * R45, R46, R47 and R48, whether identical or different, represent a hydrogen atom or a halogen atom; * R49, R50, R51 and R52, whether identical or different, represent a hydrogen atom, a halogen atom, or a group chosen from: - alkyl; - alkoxy, alkylthio; - hydroxy, mercapto; - nitro, nitroso; - (O)2S(O )-, M+ with M+ representing a hydrogen atom or a cationic counter-ion; - (O)CO -, M+ with M+ as defined previously; in particular R53, R54, R55 and R48 represent a hydrogen or halogen atom; * G represents an oxygen atom, sulfur atom or an NR group with R representing a hydrogen atom or an alkyl group; particularly G represents an oxygen atom; * L represents an alkoxide O M+; a thioalkoxide S , M+ or an NRf group, with Rf representing a hydrogen atom or an alkyl group, and M+ as defined previously; M+ is particularly sodium or potassium; * The ' represents an oxygen atom, sulfur or an ammonium group: N+RfRg, with Rf and Rg, identical or different, representing a hydrogen atom, an alkyl group, aryl possibly substituted; The ' particularly represents an oxygen atom or a phenylamino group possibly substituted by one or more alkyl groups or (O)mS(O )-, M+ with m and M+ as defined previously; * Q and Q', whether identical or different, represent an oxygen or sulfur atom; particularly Q and Q' represent an oxygen atom; * M+ is as defined previously.

[0099] Examples of colorants of formula (A-VII) include: Acid Yellow 73; Acid Red 51; Acid Red 52; Acid Red 87; Acid Red 92; Acid Red 95; Acid Violet 9;

[0100] g) dyes derived from indole of formula (A-VIII): (A-vni)

[0101] formula (A-VIII) wherein: * R53, R54, R55, R56, R57, Rss, R59 and R6o, whether identical or different, represent a hydrogen atom or a group chosen from: - alkyl; - alkoxy, alkylthio; - hydroxy, mercapto; - nitro, nitroso;

[0102] - R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X”- with R° representing an atom of hydrogen, an alkyl or aryl group; X, X' and X”, identical or different, representing an oxygen, sulfur or NR atom with R representing a hydrogen atom or an alkyl group; - (O)2S(O )-, M+ with M+ representing a hydrogen atom or a cationic counter-ion; - (O)CO -, M+ with M+ as defined previously; * G represents an oxygen atom, sulfur atom or an NR group with R representing a hydrogen atom or an alkyl group; particularly G represents an oxygen atom; * Ri and Rh, whether identical or different, represent a hydrogen atom or an alkyl group; provided that the formula (A-VIII) comprises at least one sulfonate radical (O)2S(O )-, M+ or one carboxylate radical -C(O)O , M+; preferably sodium sulfonate;

[0103] As an example of colorants of formula (A-VIII), we can cite: Acid Blue 74.

[0104] h) quinoline-derived dyes of formula (A-IX): * R6i represents a hydrogen atom, halogen or alkyl group; * R62, Res, and Rm, whether identical or different, represent a hydrogen atom or a (O)2S(O )- group, M+ with M+ representing a hydrogen atom or a cationic counter-ion; * or R6i with R62, or R6i with R64, together form a benzo group possibly substituted by one or more (O)2S(O )- groups, M+ with M+ representing a hydrogen atom or a cationic counter-ion; it being understood that the formula (A-IX) includes at least one sulfonate radical (O)2S(O )-, M+ preferably sodium sulfonate.

[0106] Examples of colorants of formula (A-IX) include: Acid Yellow 2, Acid Yellow 3 and Acid Yellow 5.

[0107] More specifically, the composition comprises one or more anionic direct dyes selected, alone or in mixture, from the following anionic direct dyes:

[0108] [Tables] (C.L 45380) Acid Red 87 (A-VII) (C.L 10316) Sel de sodium de l’acide 2,4-dinitro-l-naphtol-7-sulfonique (A- V’) (C.l. 10383) Acid Orange 3 (A-V) (C.l. 13015) Acid Yellow 9 / Food Yellow 2 (A-II) (C.l. 14780) / Direct Red 45 / Food Red 13 (A-II) (C.l. 13711) Acid Black 52 (A-II) (C.l. 13065) Acid Yellow 36 (A-II) (C.l. 14700) Sel de sodium de l’acide l-hydroxy-2-(2',4'-xylyl-5-sufonatoa zo)-naphtalène-4-sulfonique / Food Red 1 (A-II) (C.l. 14720) Acid Red 14 / Food Red 3 / Mordant Blue 79 (A-II) (C. 1. 14805) Sel de sodium de l’acide 4-hydroxy-3-[(2-métoxy-5-. nitrophény l)diaza]-6-(phénylamino)naphtalène-2-sulfonique / Acid Brown 4 (A-II) (C.l. 15510) Acid Orange 7 / Pigment Orange 17 / Solvent Orange 49 (A-II) (C.l. 15985) Food Yellow 3 / Pigment Yellow 104 (A-II) (C.l. 16185) Acid Red 27 / Food Red 9 (A-II) (C.l. 16230) Acid Orange 10 / Food Orange 4 (A-II) (C.l. 16250) Acid Red 44 (A-II) (C.l. 17200) Acid Red 33 / Food Red 12 (A-II) (C.l. 15685) Acid Red 184 (A-II) (C.l.19125) Acid Violet 3 (A-II) (Cl 18055) Sodium salt of l-hydroxy-2-(4'-acetamidophenylaz o)-8-acetamido-naphthalene-3,6-disulfonic acid / Acid Violet 7 / Food Red 11 (A-II) (Cl 18130) Acid Red 135 (A-II) (Cl 19130) Acid Yellow 27(A-III) (Cl 19140) Acid Yellow 23 / Food Yellow 4 (A-III) (Cl 20170) 4'-(sulfonato-2,4"-dimethyl)-bis-(2,6-phenylazo)-l,3-dihydroxybenzene / Acid Orange 24 (A-II) . (CL 20470) Sodium salt of l-amino-2-(4'-nitrophenylazo)-7-phenylazo-8-hydroxy-naphthalene-3,6-disulfonic acid / Acid Black 1 (A-II) (CL 23266) (4-((4-methylphenyl)sulfonyloxy)-phenylazo)2,2'-dimethyl-4-((2-hydroxy-5,8-disulfonato)naphtylazo)biphenyl / Acid Red 1 (A-II) (CL 27755) Food Black 2 (A-II) (CL 25440) l-(4'-sulfonatophenylazo)-4-((2"-hydroxy-3"-acetylamino-6", 8"-disulfonato)naphtylazo)-6-sulfonatonaphthalene (tetrasodium salt) / Food Black 1 (A-II) (CL 42090) Acid Blue 9 (A-VI) (CL 60730) Acid Violet 43 (A-IV) (CL 61570) Acid Green 25 (A-IV) (CL 62045) Sodium salt of l-amino-4-cyclohexylamino-9,10-ant hraquinone 2-sulfonic acid / Acid Blue 62 (A-IV) (CL 62105) Acid Blue 78 (A-IV) (C.L 14710) Sodium salt of 4-hydroxy-3((2-methoxyphenyl)-azo)-1-naphthalene sulfonic acid / Acid Red 4 (A-II) 2-piperidino-5-nitrobenzene sulfonic acid (V') 2(4'-N,N(2"-hydroxyethyl)amino-2'-nitro)aniline ethane sulfonic acid (A-V') 4-[3-hydroxyethylamino-3-nitrobenzene sulfonic acid (A-V') (CL 42640) Acid Violet 49 (A-VI) (CL 42080) Acid Blue 7 (A-VI) (CL 58005) Sodium salt of 1,2-dihydroxy-3-sulfo-anthraquinone / Mordant Red 3 (A-IV) (CL 62055) Sodium salt of acid l-amino-9,10-dihydro-9,10-dioxo-4-(phenylamino) 2-anthracene sulfonic acid / Acid Blue 25 (A-IV) (CL 14710) Sodium salt of 4-hydroxy-3-((2-methoxyphenyl)-azo)-1-naphthalene sulfonic acid / Acid Red 4 (A-II) .

[0109] Most of these dyes are described in particular in the Color Index published by The Society of Dyers and Colorists, PO Box 244, Perkin House, 82 Grattan Road, Bradford, Yorkshire, BD1 2JBN England.

[0110] The anionic colorants most particularly preferred are the colorants designated in the Color Index under the code CI 58005 (monosodium salt of 1,2-dihydroxy-9,10-anthraquinone-3-sulfonic acid), CI 60730 (monosodium salt of 2-[(9,10-dihydro-4-hydroxy-9,10-dioxo-l-anthracenyl)-amino]-5-methylbenzenesulfonic acid), CI 15510 (monosodium salt of 4-[(2-hydroxy-l-naphthalenyl)-azo]-benzenesulfonic acid), CI 15985 (disodium salt of 6-hydroxy-5-[(4-sulfophenyl)-azo]-2-naphthalenesulfonic acid), CI 17200 (disodium salt of 5-amino-4-hydroxy-3-(phenylazo)-2,7-naphthalene disulfonic acid), CI 20470 (disodium salt of l-amino-2-(4'-nitrophenylazo)-7-phenylazo-8-hydroxy-3,6-naphthalene disulfonic acid), CI 42090 (disodium salt of N-ethyl-N-[4-[[4-[ethyl[3-sulfophenyl]-methyl]-amino]-phenyl](2-sulfophenyl)-methylene]-2,5-cyclohexadien-1-ylidene]-3-sulfobenzenemethanaminium hydroxide, internal salt), CI61570 (disodium salt of 2,2'-[(9,10-dihydro-9,10-dioxo-l,4-anthracenediyl)-diimino]-bis-[5-methyl]-benzenesulfonic acid. .

[0111] Compounds corresponding to the mesomeric, tautomeric forms of (A-II) to (A-IX) structures can also be used.

[0112] Among the natural direct dyes that can be used according to the invention, mention may be made of hennotannic acid, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, protocatechaldehyde, indigo, isatin, curcumin, spinulosin, apigenidine, and orcein. Extracts or decoctions containing these natural dyes, and in particular henna-based poultices or extracts, may also be used.

[0113] Preferably, the composition according to the invention comprises one or more direct dye(s) selected from anionic direct dyes, cationic direct dye(s) and mixtures thereof.

[0114] According to a first preferred embodiment, the composition according to the invention comprises one or more cationic direct dye(s).

[0115] Preferably, the composition according to the invention comprises one or more cationic direct dye(s) selected from azo cationic direct dyes, hydrazono cationic direct dyes, anthraquinone cationic direct dyes, triarylmethanic cationic direct dyes, and mixtures thereof.

[0116] According to another preferred embodiment, the composition according to the invention comprises one or more anionic direct dye(s), preferably chosen from acidic azo direct dyes, acidic azinic direct dyes, acid triarylmethanic direct dyes, acid indoamine direct dyes, acid anthraquinone direct dyes, acid indigoid direct dyes, acid natural direct dyes, and mixtures thereof.

[0117] Preferably, the total content of the direct colorant(s) ranges from 0.001 to 20% by weight, preferably from 0.005 to 15% by weight, more preferably from 0.01 to 10% by weight, better from 0.05 to 5% by weight, even better from 0.1 to 3% by weight, relative to the total weight of the composition.

[0118] Preferably, the total content of the cationic direct colorant(s) ranges from 0.001 to 20% by weight, preferably from 0.005 to 15% by weight, more preferably from 0.01 to 10% by weight, better from 0.05 to 5% by weight, even better from 0.1 to 3% by weight, relative to the total weight of the composition.

[0119] Preferably, the total content of the direct anionic colorant(s) ranges from 0.001 to 20% by weight, preferably from 0.005 to 15% by weight, more preferably from 0.01 to 10% by weight, better from 0.05 to 5% by weight, even better from 0.1 to 3% by weight, relative to the total weight of the composition. Non-associative polysaccharide

[0120] The composition according to the invention comprises one or more non-associative polysaccharide(s).

[0121] In the present invention, "polysaccharide" means a polymer composed of sugar units. "Sugar unit" means an oxygenated hydrocarbon compound possessing several alcohol functional groups, with or without aldehyde or ketone functional groups, and comprising at least four carbon atoms. The sugar units may optionally be modified by substitution, and / or by oxidation, and / or by dehydration.

[0122] The sugar motifs 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.

[0123] For the purposes of the present invention, "associative polymer" means an amphiphilic polymer capable, in an aqueous medium, of reversibly associating with itself or with other molecules. It generally comprises in its chemical structure at least one hydrophilic region or group and at least one hydrophobic region or group.

[0124] By "hydrophobic zone or group" is meant a hydrocarbon group or a hydrocarbon chain polymer, saturated or unsaturated, linear or branched. When it designates a hydrocarbon group, the hydrophobic group comprises at least 8 carbon atoms, preferably from 8 to 30 carbon atoms, in particular from 8 to 24 carbon atoms and preferably from 10 to 24 carbon atoms.

[0125] Preferably, the non-associative polysaccharides do not include a hydrocarbon group comprising 10 to 30 carbon atoms, preferably do not include a hydrocarbon group comprising 8 to 30 carbon atoms.

[0126] The following polymers, alone or in mixtures, may be cited in particular as examples of non-associative polysaccharides: a) exudates from trees or shrubs, including: - gum arabic (branched polymer of galactose, arabinose, rhamnose and glucuronic acid); - Ghatti gum (polymer derived from arabinose, galactose, mannose, xylose and glucuronic acid); - karaya gum (polymer derived from galacturonic acid, galactose, rhamnose and glucuronic acid); - tragacanth gum (or tragacanth) (polymer of galacturonic acid, galactose, fucose, xylose and arabinose); b) gums derived from algae, including: - agar (polymer derived from galactose and anhydrogalactose); - alginates (polymers of mannuronic acid and glucuronic acid); - carrageenans and furcelleranes (polymers of galactose sulfate and anhydrogalactose sulfate); c) gums from seeds or tubers, including: - guar gum (polymer of mannose and galactose); - carob gum (polymer of mannose and galactose); - fenugreek gum (polymer of mannose and galactose); - tamarind gum (polymer of galactose, xylose and glucose); - konjac gum (polymer of glucose and mannose); d) microbial gums, including: - xanthan gum (polymer of glucose, mannose acetate, mannose / pyruvic acid and glucuronic acid); - gellan gum (polymer of partially acylated glucose, rhamnose and glucuronic acid); - scleroglucan gum (glucose polymer); e) polymers extracted from plants, including: - celluloses (polymers of glucose); - starches (polymers of glucose) and - inulin.

[0127] These polymers can be modified physically or chemically. Physical treatments include, in particular, heat treatment. Chemical treatments include esterification and etherification reactions. of amidation, of oxidation. These treatments lead to polymers which can be non-ionic, anionic or amphoteric.

[0128] In particular, guar gums, locust bean gums, starches and celluloses can be modified / treated.

[0129] The guar gums usable according to the invention can be modified by (poly)hydroxylakyl groups in the C1-6 range. Examples of (poly)hydroxyalkyl groups in the C1-6 range include hydroxymethyl, hydroxyethyl, hydroxypropyl, and hydroxybutyl groups. These guar gums are well known in the prior art and can, for example, be prepared by reacting corresponding alkene oxides, such as propylene oxides, with guar gum to obtain guar gum modified by hydroxypropyl groups. The degree of hydroxyalkylation preferably ranges from 0.4 to 1.2 and corresponds to the number of alkylene oxide molecules consumed per number of free hydroxyl groups present on the guar gum.

[0130] Such guar gums possibly modified by hydroxyalkyl groups are for example sold under the trade names JAGUAR HP8, JAGUAR HP60 and JAGUAR HP120 by the company RHODIA CHIMIE.

[0131] The starches usable in the present invention may be of botanical origin from cereals or tubers. Thus, the starches are chosen, for example, from corn, rice, oat, cassava, barley, potato, wheat, sorghum, pea, and tapioca starches. Hydrolysates of the starches mentioned above may also be used. The starch is preferably derived from potato.

[0132] Preferably, starch phosphates will be used, in particular distarch phosphates or compounds rich in distarch phosphate such as the product offered under the references PREJEL VA-70-T AGGL (gelatinized hydroxypropyl cassava distarch phosphate) or PREJEL TK1 (gelatinized cassava distarch phosphate) or PREJEL 200 (gelatinized acetylated cassava distarch phosphate) by the AVEBE Company or STRUCTURE ZEA of NATIONAL STARCH (gelatinized maize distarch phosphate).

[0133] According to the invention, amphoteric starches can also be used; these amphoteric starches comprise one or more anionic groups and one or more cationic groups. The anionic and cationic groups may be linked to the same reactive site of the starch molecule or to different reactive sites; preferably, they are linked to the same reactive site. The anionic groups may be of the carboxylic, phosphate, or sulfate type, and preferably carboxylic. The cationic groups may be of the primary, secondary, tertiary, or quaternary amine type.

[0134] The non-associative polysaccharides that can be used according to the invention can be cellulosic polymers.

[0135] By "cellulosic" polymer, according to the invention, any polysaccharide compound having in its structure chains of glucose residues joined by [3-1,4] bonds; in addition to unsubstituted celluloses, cellulose derivatives can be anionic, cationic, amphoteric or non-ionic.

[0136] Cellulosic polymers are also called celluloses.

[0137] Thus, the cellulosic polymers usable according to the invention can be chosen from unsubstituted celluloses including in microcrystalline form and cellulose ethers.

[0138] Among these cellulosic polymers, we distinguish cellulose ethers, cellulose esters and cellulose ether esters.

[0139] Cellulose esters include inorganic cellulose esters (cellulose nitrates, sulfates, or phosphates), organic cellulose esters (cellulose monoacetates, triacetates, amidopropionates, acetatebutyrates, acetatepropionates, or acetatetrimellitates), and mixed organic / inorganic cellulose esters such as cellulose acetatebutyrates and acetatepropionate sulfates. Examples of cellulose ether esters include hydroxypropylmethylcellulose phthalates and ethylcellulose sulfates.

[0140] Among cellulose ethers, examples include (Ci-C4)alkylcelluloses such as methylcelluloses and ethylcelluloses (e.g., Ethocel Standard 100 Premium from DOW CHEMICAL); (poly)hydroxy(Ci-C4)alkylcelluloses such as hydroxymethylcelluloses, hydroxyethylcelluloses (e.g., Natrosol 250 HHR offered by ASHLAND) and hydroxypropylcelluloses (e.g., Klucel EF from AQUALON); mixed (poly)hydroxy(Ci-C4)alkyl-(Ci-C4)alkylcelluloses such as hydroxypropyl methylcelluloses (e.g., Methocel E4M from DOW CHEMICAL), hydroxyethyl methylcelluloses, hydroxyethyl ethylcelluloses (e.g., Bermocoll E 481 FQ from AKZO NOBEL) and hydroxybutyl methylcelluloses.

[0141] Among the anionic cellulose ethers, mention may be made of (poly)carboxy(Cr C4)alkylcelluloses and their salts. By way of example, mention may be made of carboxymethylcelluloses, carboxymethylmethylcelluloses (for example Blanose 7M from the company AQUALON) and carboxymethylhydroxyethylcelluloses and their sodium salts.

[0142] Among cationic cellulose ethers, cationic cellulose derivatives such as cellulose copolymers or cellulose derivatives grafted with a water-soluble quaternary ammonium monomer may be mentioned, and described in particular in US patent 4131576, such as (poly)hydroxy(Ci-C4)alkyl celluloses, including hydroxymethyl-, hydroxyethyl-, or hydroxypropyl celluloses grafted with, among other things, a salt of methacryloylethyl trimethylammonium, methacrylmidopropyl trimethylammonium, or dimethyl-diallylammonium. The marketed products meeting this definition are, more specifically, those sold under the names "Celquat® L 200" and "Celquat® H 100" by the National Starch Company.

[0143] Preferably, the non-associative polysaccharide(s) are chosen from polysaccharides of microbial origin, guar gums and mixtures thereof.

[0144] Preferably, the non-associative polysaccharide(s) are chosen from scleroglucan gums, xanthan gums, gellan gums, guar gums and mixtures thereof, more preferably from scleroglucan gums, xanthan gums, and mixtures thereof.

[0145] More preferably the non-associative polysaccharide is scleroglucan gum.

[0146] The non-associative polysaccharide(s) useful 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, preferably from 0.5 to 10% by weight, better from 1 to 5% by weight relative to the weight of the composition.

[0147] Preferably, the non-associative polysaccharides are selected from scleroglucan gums, xanthan gums, guar gums and mixtures thereof and are present in a total content of 0.01 to 20% by weight, preferably of 0.1 to 15% by weight, preferably of 0.5 to 10% by weight, better of 1 to 5% by weight relative to the weight of the composition.

[0148] More preferably, the non-associative polysaccharide 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, preferably from 0.5 to 10% by weight, better from 1 to 5% by weight relative to the weight of the composition. Polycarboxylic acids

[0149] The composition according to the invention comprises at least one polycarboxylic acid of the following formula (I), or one of its salts, its optical isomers, its geometric isomers, and / or its solvates: R₁₂-N-(CH(R₂)COOH)₂ (I) in which Ri represents a hydrogen atom or a group -CH(COOH)-(CH2)2-COOH, -CH2CH2OH, -CH(CH3)COOH, -(CH2)2N(COR3)-CH2-COOH, or -CH(COOH)-CH2-COOH; and R2 represents a CH2COOH group when Ri represents a hydrogen atom or R2 represents a hydrogen atom when Ri is not a hydrogen atom; and R3 represents a linear or branched alkyl group with 1 to 4 carbon atoms or a cyclic group with 3 to 30 carbon atoms.

[0150] For the purposes of the present invention, "solvates" represent hydrates as well as the association with C1-C4 linear or branched alcohols such as ethanol, isopropanol, n-propanol.

[0151] More specifically, polycarboxylic acids of formula (I) correspond to: - compounds comprising four carboxylic acid functions, where Ri represents a hydrogen atom and R2 represents a -CH2-COOH group, or where Ri represents the -CH(COOH)-(CH2)2-COOH group and R2 represents a hydrogen atom, or where Ri represents the -CH(COOH)-CH2-COOH group and R2 represents a hydrogen atom; - compounds comprising three carboxylic acid functions, where Ri represents the -CH(CH3)-COOH group and R2 represents a hydrogen atom, or where Ri represents a -(CH2)2-N(COR3)-CH2-COOH group and R2 represents a hydrogen atom; and to - compounds comprising two carboxylic acid functions, where Ri represents the -CH2CH2OH group and R2 represents a hydrogen atom.

[0152] Preferably, Ri represents the group -CH(COOH)-(CH2)2-COOH and R2 represents a hydrogen atom.

[0153] Polycarboxylic acids of formula (I) may be in the form of pure enantiomers, preferably of L configuration, or in the form of mixtures, in particular racemic mixtures.

[0154] 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, their ammonium and substituted ammonium salts and mixtures thereof.

[0155] Examples of alkali metal salts include sodium (Na+) and potassium (K+) salts, while examples of alkaline earth metal salts include calcium (Ca2+) and magnesium (Mg2+) salts.

[0156] For the purposes of the present invention, "transition metal" means a metal having an incomplete d subshell; more particularly in oxidation state II, such as cobalt (Co2+), iron (Fe2+), manganese (Mn2+), zinc (Zn2+) and copper (Cu2+).

[0157] With regard to organic amine salts, one can mention primary, secondary or tertiary amine salts, or even alkanolamine salts. These amines have one or more radicals, identical or not, of the alkyl type, linear or branched, in the form of C1 to C2O, possibly including a heteroatom such as oxygen.

[0158] Among the salts of these compounds, alkali metal salts are preferred, and in particular sodium or potassium salts.

[0159] Preferably, the polycarboxylic acid(s) of formula (I) or their salts, their optical isomers, their geometric isomers and / or their solvates used in the context of the present invention are selected from methyl-glycine diacetic acid, N-lauroyl-N,N',N'-triacetic ethylenediamine acid, N,N-dicarboxymethyl glutamic acid, iminodisuccinic acid, N,N-bis(carboxymethyl) aspartic acid, their alkali metal salts, their alkaline earth metal salts, their transition metal salts, their organic amine salts, their ammonium salts, their optical isomers, their geometric isomers, their solvates and their mixtures;and more preferably among N,N-dicarboxymethyl glutamic acid, N,N-bis(carboxymethyl)aspartic acid, their alkali metal salts, their alkaline earth metal salts, their transition metal salts, their organic amine salts, their ammonium salts, their optical isomers, their geometric isomers, their solvates and their mixtures. ;

[0160] Better still, the polycarboxylic acid(s) of formula (I) or their salts, their optical isomers, their geometric isomers and / or their solvates are selected from N,N-dicarboxymethyl glutamic acid, N,N-bis(carboxymethyl) aspartic acid, their alkali metal salts, their alkaline earth metal salts, their transition metal salts, their organic amine salts, their ammonium salts, their optical isomers, their geometric isomers, their solvates and their mixtures.

[0161] Preferably, the polycarboxylic acid(s) of formula (I) or their salts, their optical isomers, their geometric isomers and / or their solvates used according to the present invention are chosen from N,N-dicarboxymethyl glutamic acid, its alkali metal salts, their optical isomers, their geometric isomers, and their mixtures; more preferably from N,N-dicarboxymethyl glutamic acid, tetrasodium N,N-bis(carboxymethyl)-glutamate, their optical isomers, their geometric isomers; better still from N,N-dicarboxymethyl L-glutamic acid, tetrasodium N,N-bis(carboxymethyl)-L-glutamate), and their mixtures.

[0162] Preferably, the compound with the name Tetrasodium Glutamate diacetate (INCI name) will be used, such as Dissolvine GL38 or 47S marketed by Akzo Nobel.

[0163] Preferably, the total content of polycarboxylic acid(s) of formula (I), their salts, their optical isomers, their geometric isomers, and their solvates, in The composition is in the range of 0.01% to 20% by weight; preferably from 0.05% to 15%; more preferably from 0.075% to 10% by weight; better from 0.1% to 5% by weight; even better from 0.15% to 3% by weight, and still better from 0.2% to 2% relative to the total weight of the composition according to the invention.

[0164] 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 of 0.01% to 20% by weight; preferably from 0.05% to 15%; more preferably from 0.075% to 10% by weight; better from 0.1% to 5% by weight; even better from 0.15% to 3% by weight, and even better from 0.2% to 2% relative to the total weight of the composition according to the invention.

[0165] Preferably, the total tetrasodium glutamate diacetate (GLDA) content in the composition is in the range of 0.01% to 20% by weight; preferably from 0.05% to 15%; more preferably from 0.075% to 10% by weight; better still from 0.1% to 5% by weight; even better from 0.15% to 3% by weight; and still better from 0.2% to 2% by weight relative to the total weight of the composition according to the invention. Hydroxylated compounds

[0166] The composition according to the invention comprises one or more hydroxylated compound(s) selected from aromatic alcohols, C2-C6 aliphatic hydroxylated solvents and mixtures thereof.

[0167] Aromatic alcohol

[0168] The composition according to the invention may comprise one or more aromatic alcohol(s).

[0169] Preferably, the composition according to the invention comprises one or more aromatic alcohol(s).

[0170] The term "aromatic alcohol" means any compound that is liquid at room temperature and atmospheric pressure and comprises at least one benzene or naphthalene ring and at least one alcohol (OH) functional group directly attached to the ring or attached to at least one substituent of said ring. Preferably, the alcohol functional group shall be on a substituent of the benzene or naphthalene ring.

[0171] Preferably, the composition according to the invention comprises one or more aromatic alcohol(s) of formula (II):

[0172] in which Y represents a Ci-C4 hydroxyalkyl group or a Ci-C4 hydroxyalkyloxy radical, n denotes an integer ranging from 0 to 5, X represents independently an alkyl radical in CrC4 or a halogen. In other words, when n>l the different X's can be identical or different.

[0173] Preferably, n is equal to 0.

[0174] According to a particular embodiment, Y represents a hydroxymethyl, hydroxyethyl or hydroxyethyloxy radical.

[0175] Examples of aromatic alcohols of formula (II) include benzyl alcohol, phenyl ethanol, and phenoxyethanol. In one particular embodiment, the aromatic alcohol of formula (II) is benzyl alcohol.

[0176] 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 from 0.1 to 5% by weight, better still from 1 to 3% by weight relative to the total weight of the composition

[0177] 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 from 0.1 to 5% by weight, better still from 1 to 3% by weight relative to the total weight of the composition.

[0178] Preferably, benzyl alcohol can 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 from 0.1 to 5% by weight, better still from 1 to 3% by weight relative to the total weight of the composition.

[0179] Aliphatic solvent

[0180] The composition according to the invention may comprise one or more C2-C6 hydroxylated aliphatic solvent(s).

[0181] Preferably, the composition comprises one or more C2-C6 hydroxylated aliphatic solvent(s).

[0182] By aliphatic, we mean a compound not containing an aromatic ring. Solvents of this type may be monoalcohols or polyols that are liquid at room temperature (25°C) and atmospheric pressure (105 Pa). Preferably, these solvents are non-etherified.

[0183] According to a particular embodiment, these solvents are selected from ethanol, glycerol, propylene glycol, dipropylene glycol, and hexylene glycol. Preferably, the C2-C6 hydroxylated aliphatic solvent is ethanol and / or hexylene glycol, preferably ethanol.

[0184] The hydroxylated aliphatic solvent(s) may 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 preferably from 1% to 20% by weight, better from 2% to 15% by weight, even better from 3% to 10% by weight, relative to the weight of the composition.

[0185] Preferably, ethanol can 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 preferably from 1% to 20% by weight, better from 2% to 15% by weight, even better from 3% to 10% by weight, relative to the weight of the composition.

[0186] Preferably, the composition comprises one or more aromatic alcohol(s) and one or more aliphatic solvent(s). The weight ratio of aromatic alcohol(s) to C2-C6 hydroxylated aliphatic solvent(s) is preferably less than or equal to 1, preferably from 0.1 to 1, and even better from 0.1 to 0.5.

[0187] Preferably, the composition comprises benzyl alcohol and ethanol. The weight ratio of benzyl alcohol / ethanol is preferably less than or equal to 1, preferably from 0.1 to 1, and even better from 0.1 to 0.5.

[0188] The composition according to the invention may include water or a mixture of water and optionally one or more solvents other than the compounds of formula (II) and C2-C6 hydroxylated aliphatic solvents such as polyol ethers like dipropylene glycol monomethyl ether.

[0189] Preferably, the composition comprises water, preferably in a content of 20 to 95% by weight, preferably 30 to 93% by weight, and even more preferably 40 to 90% by weight relative to the total weight of the composition.

[0190] The composition according to the invention may also contain various adjuvants conventionally used in hair coloring compositions, such as anionic, cationic, non-ionic, amphoteric or zwitterionic surfactants; anionic, cationic, amphoteric, zwitterionic or non-ionic polymers other than non-associative polysaccharides; mineral or organic thickening agents; antioxidants, penetration agents, perfumes, buffers, dispersing agents, conditioning agents, film-forming agents, ceramides, preservatives, opacifying agents.

[0191] The above adjuvants are generally present in quantities of each of them between 0.01 and 20% by weight relative to the weight of the composition.

[0192] Of course, the person skilled in the art will take care to choose this or these possible complementary compounds in such a way that the advantageous properties intrinsically attached to the composition are not, or substantially not, altered by the envisaged addition(s).

[0193] The pH of the composition used in the process according to the invention is generally between 2 and 13 approximately, preferably between 2.5 and 10. It can be adjusted to the desired value by means of acidifying or alkalizing agents usually used in dyeing keratin fibers or by means of conventional buffer systems.

[0194] Examples of acidifying agents include mineral or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid, and sulfonic acids.

[0195] Examples of alkalizing agents include ammonium hydroxide, alkali carbonates, alkanolamines such as mono-, di- and triethanolamines and their derivatives, sodium or potassium hydroxides and compounds of the following formula: X z R» NWN ZX RR L <4

[0196] in which W is a propylene remnant optionally substituted by a hydroxyl group or a Ci-C4 alkyl radical; Ra, Rb, Rc and Rd, identical or different, represent a hydrogen atom, a CrC4 alkyl radical or a CrC4 hydroxyalkyl radical.

[0197] In particular, when the composition includes anionic direct dyes, the pH of the composition is less than 7, preferably from 2 to 5, the pH being able to be adjusted by means of a carboxylic acid.

[0198] When the composition includes cationic direct dyes, and preferably when it does not include anionic direct dyes, the pH of the composition ranges from 5 to 12, preferably from 6 to 11. Process

[0199] The invention also relates to a method for coloring keratin fibers, in particular human keratin fibers such as hair, which includes applying to said keratin fibers the composition described above.

[0200] The composition can be applied to dry or moist keratin fibers.

[0201] The composition is preferably left in place on the fibers for a period of 1 minute to 100 minutes, preferably 5 minutes to 90 minutes, better 10 minutes to 60 minutes.

[0202] After treatment, the keratin fibers are optionally rinsed, preferably with water, possibly undergo washing with shampoo followed by rinsing with water, before being dried or left to dry.

[0203] The coloring process according to the invention may also include, before the step of applying the composition described above, a step of applying to said keratin fibers a composition comprising one or more alkaline agent(s), and optionally one or more chemical oxidizing agent(s).

[0204] The following examples serve to illustrate the invention without, however, being limiting in nature. EXAMPLES

[0205] In the following examples, all quantities are given as mass percentage of active material (AM) relative to the total weight of the composition (unless otherwise stated). Example 1

[0206] The Cl and C2 colour compositions were prepared from the compounds whose contents are indicated in the tables below:

[0207] [Tables2] Cl C2 Benzyl alcohol 2.0 2.0 Ethanol 8.0 8.0 RED 33 (CI 17200) 0.5 0.5 Scleroglucan gum 2.0 2.0 Tetrasodium glutamate diacetate - 0.24 pH adjuster qs pH = 2.5 + / - 0.2 qs pH = 2.5 + / - 0.2 Water Qs 100 Qs 100

[0208] The Cl and C2 colour compositions were applied to a strand of hair that was 90% natural white at a rate of 3g / g of hair.

[0209] After 15 minutes of exposure at 40°C, then 5 minutes at room temperature under an occlusive system on a heating plate, the hair was rinsed with water and then dried in an oven at 60°C.

[0210] Colorimetric measurements were carried out using a Zeiss INTERLOCK T 2.0 / 100 ZF-I 2 MACRO objective multispectral camera to evaluate hair colouring in the L*a*b* system.

[0211] In this system, L* represents lightness, a* and b* represent the chromaticity of the hair, a* representing the red / green axis and b* the yellow / blue axis. The lower the value of L*, the more powerful (intense) the resulting color.

[0212] The resulting color is evaluated by measuring AE, which is the color change before and after application of the color from the formula: AE = -Lo *)2 4- (a* - a0 *)2 + (b* -b0 *)2

[0213] in which L* represents the intensity, a* and b* the chromaticity of the colored hair and Lq* represents the intensity and a0* and b0* the chromaticity of the untreated hair. The color is more intense the higher the AE.

[0214] Results

[0215] [Tables3] L* a* b* AE Reference, untreated hair 59.46 0.95 11.78 Composition Cl (comparative) 34.59 32.97 4.46 43.68 Composition C2 (invention) 28.99 33.9 2.3 47.04

[0216] The hair strands treated with the coloring composition according to the invention exhibit a higher AE value than those treated with the comparative composition.

[0217] In other words, the composition according to the invention allows for a better rise in colour than the comparative composition.

[0218] The strands were then subjected to a washing test with shampoo in order to evaluate the tenacity (the persistence) of the color obtained.

[0219] Visually, better color retention is observed after shampooing on the strands treated with the composition according to the invention than on the strands treated with the comparative composition. Example 2

[0220] The C3 and C4 colour compositions were prepared from the compounds whose contents are indicated in the tables below:

[0221] [Tables5] C3 C4 Benzyl alcohol 2.0 2.0 Ethanol 8.0 8.0 BASIC RED 76 (CI 12245) 2.0 2.0 Scleroglucan gum 2.0 2.0 Tetrasodium glutamate diacetate - 0.24 pH adjuster qs pH = 9 + / -0.2 qs pH = 9 + / -0.2 Water Qs 100 Qs 100

[0222] The C3 and C4 colour compositions were applied to a strand of hair that was 90% natural white at a rate of 3g / g of hair.

[0223] After 60 minutes of exposure at 27°C under an occlusive system on a heating plate, the hair was rinsed with water and then dried in an oven at 60°C.

[0224] Colorimetric measurements were carried out using a Zeiss INTERLOCK T 2.0 / 100 ZF-I 2 MACRO objective multispectral camera to evaluate hair colouring in the L*a*b* system.

[0225] In this system, L* represents lightness, a* and b* represent the chromaticity of the hair, a* representing the red / green axis and b* the yellow / blue axis. The lower the value of L*, the more powerful (intense) the resulting color.

[0226] The resulting color is evaluated by measuring AE, which is the color change before and after application of the color from the formula: â E = J

[0227] in which L* represents the intensity, a* and b* the chromaticity of the colored hair and Lq* represents the intensity and a0* and b0* the chromaticity of the untreated hair. The color is more intense the higher the AE.

[0228] Results

[0229] [Tableauxô] L* a* b* AE Reference, untreated hair 54.46 0.95 11.78 Composition C3 (comparative) 36.65 38.09 25.37 45.7 Composition C4 (invention) 39.53 42.31 29.69 49.3

[0230] The hair strands treated with the coloring composition according to the invention exhibit a higher AE value than those treated with the comparative composition.

[0231] In other words, the composition according to the invention allows for a better color rise than the comparative composition.

Claims

Demands

1. Composition comprising: - one or more direct dye(s) - one or more non-associative polysaccharide(s), - one or more polycarboxylic acid(s) of the following formula (I), or their salts, optical isomers, geometric isomers and / or solvates: RrN-(CH(R2)COOH)2 (I) in which Ri represents a hydrogen atom or a group -CH(COOH)-(CH2)2-COOH, -CH2CH2OH, -CH(CH3)COOH, -(CH2)2N(COR3)-CH2-COOH, or -CH(COOH)-CH2-COOH; and Represents a CH2COOH group when Ri represents a hydrogen atom or R2 represents a hydrogen atom when Ri is not a hydrogen atom; and R3 represents an alkyl group, linear or branched comprising 1 to 4 carbon atoms, or cyclic comprising 3 to 30 carbon atoms, - one or more hydroxylated compound(s) chosen from aromatic alcohols, aliphatic hydroxylated solvent(s) in C2-C6 and their mixtures.

2. Composition according to claim 1 comprising one or more aromatic alcohol(s).

3. Composition according to any one of claims 1 or 2 comprising one or more aromatic alcohol(s) of formula (II): (X)ny in which Y represents a Ci-C4 hydroxyalkyl group or a Ci-C4 hydroxyalkyloxy radical, n denotes an integer from 0 to 5, X independently represents a CrC4 alkyl radical or a halogen.

4. Composition according to the preceding claim wherein the aromatic alcohol(s) of formula (II) are selected from the alcohol benzyl, phenyl ethanol, phenoxyethanol, preferably benzyl alcohol.

5. Composition according to any one of the preceding claims wherein 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 from 0.1 to 5% by weight, better still from 1 to 3% by weight, relative to the weight of the composition.

6. Composition according to any one of the preceding claims comprising one or more C2-C6 aliphatic hydroxylated solvent(s).

7. Composition according to the preceding claim wherein the C2-C6 hydroxylated aliphatic solvent(s) are selected from ethanol, glycerol, propylene glycol, dipropylene glycol, hexylene glycol, preferably ethanol and / or hexylene glycol, preferably ethanol.

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

9. Composition according to any one of the preceding claims comprising one or more aromatic alcohol(s) and one or more C2-C6 aliphatic hydroxylated solvent(s), the weight ratio of aromatic alcohols / C2-C6 aliphatic hydroxylated solvent(s) is less than or equal to 1, preferably from 0.1 to 1, better still from 0.1 to 0.

5.

10. Composition according to any one of the preceding claims comprising one or more cationic direct dye(s), preferably selected from azo cationic direct dyes, hydrazono cationic direct dyes, anthraquinone cationic direct dyes, triarylmethanic cationic direct dyes and mixtures thereof.

11. Composition according to any one of the preceding claims comprising one or more anionic direct dye(s), preferably selected from acid azo direct dyes, acid azinic direct dyes, direct dyes triarylmethanic acids, acid indoamine direct dyes, acid anthraquinone direct dyes, acid indigoid direct dyes, acid natural direct dyes, and mixtures thereof.

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

13. Composition according to any one of the preceding claims wherein the non-associative polysaccharide(s) is / are selected from polysaccharides of microbial origin, guar gums and mixtures thereof, preferably from scleroglucan gums, xanthan gums, gellan gums, guar gums and mixtures thereof, preferably from xanthan gums, scleroglucan gums, and mixtures thereof, more preferably scleroglucan gum.

14. Composition according to any one of the preceding claims, wherein the total content of the non-associative polysaccharide(s) ranges from 0.01 to 20% by weight, preferably from 0.1 to 15% by weight, preferably from 0.5 to 10% by weight, better from 1 to 5% by weight relative to the weight of the composition.

15. Composition according to any one of the preceding claims, characterized in that the polycarboxylic acid(s) of formula (I) or their salts, their optical isomers, their geometric isomers and / or their solvates, are selected from N,N-dicarboxymethyl glutamic acid, N,N-bis(carboxymethyl)aspartic acid, their alkali metal salts, their alkaline earth metal salts, their transition metal salts, their organic amine salts, their ammonium salts, their optical isomers, their geometric isomers, their solvates and their mixtures; preferably selected from N,N-dicarboxymethyl glutamic acid, tetrasodium N,N-bis(carboxymethyl)-glutamate, their optical isomers, their geometric isomers, and their mixtures; more preferably N,N-dicarboxymethyl L-glutamic acid, tetrasodium N,N-bis(carboxymethyl)-L-glutamate, and mixtures thereof; more preferably still tetrasodium glutamate diacetate.

16. Composition according to any one of the preceding claims, wherein the total content of the polycarboxylic acid(s) of formula (I) ranges from 0.01% to 20% by weight; preferably from 0.05% to 15%; more preferably from 0.075% to 10% by weight; better from 0.1% to 5% by weight; even better from 0.15% to 3% by weight, and still better from 0.2% to 2% relative to the total weight of the composition.

17. A method for coloring keratin fibers, in particular human keratin fibers such as hair, which comprises applying to the keratin fibers a composition according to any one of the preceding claims.