A hair coloring process using a composition comprising a direct dye that is recirculated over the hair

Abstract

Hair coloring process employing a composition comprising a direct dye that is recirculated over the hair. The invention relates to a process for coloring keratin fibers, in particular human keratin fibers such as hair, comprising i) applying a coloring composition (A) comprising one or more direct dye(s) and optionally water to said keratin fibers, ii) recovering at least a portion of the coloring composition (A) after application to the keratin fibers, iii) applying the coloring composition (A) recovered in step ii) to the keratin fibers, iv) optionally rinsing the keratin fibers with water. Figure for the abstract: Figure 1

Description

Title of the invention: A hair coloring process employing a composition comprising a direct dye that is recirculated over the hair

[0001] The present invention relates to a method for coloring human keratin fibers, in particular hair, using a coloring composition comprising a direct dye which is recirculated over the hair.

[0002] It is known to dye keratin fibers and in particular human hair, with compositions containing direct dyes, namely molecules having an affinity for fibers and coloring even in the absence of oxidizing agent added to the compositions containing them.

[0003] 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, anionic (acid dyes), or cationic (basic dyes). The direct dyes may also be natural dyes.

[0004] Compositions containing one or more direct dyes are applied to the keratin fibers for a time necessary to obtain the desired color, then rinsed.

[0005] These direct keratin fiber coloring compositions generally contain direct dyes combined with surfactants and / or thickeners to improve their performance qualities.

[0006] However, the presence of certain ingredients in the compositions may reduce the effectiveness of the colorants, thus requiring the use of a large quantity of colorants.

[0007] Furthermore, the formulation of environmentally friendly cosmetic products, that is, products whose design and development take environmental issues into account, is becoming a major concern in order to help address global challenges. It is therefore essential to offer more sustainable compositions and coloring processes that can thus meet these environmental challenges.

[0008] In this context, it is important to develop new hair coloring processes that require a reduced amount of compounds to obtain satisfactory coloring, in particular to limit the amount of compounds present in rinsing water.

[0009] There is therefore a real need to develop a process for coloring keratin fibers using direct dyes which makes it possible to reduce the quantity of direct dyes used, in particular to limit the quantity of dyes present in the rinsing waters, while obtaining a good rise in color, intense and chromatic colors, and good persistence to shampoos.

[0010] This objective and others are achieved by the present invention, which therefore relates to a process for coloring keratin fibers, in particular human keratin fibers such as hair, comprising: i) the application to said keratin fibers of a coloring composition (A) comprising one or more direct dye(s) and optionally water, ii) the recovery of at least a portion of the coloring composition (A) after application to the keratin fibers, iii) the application of the staining composition (A) recovered in step ii) to the keratin fibers, iv) possibly, rinsing the keratin fibers with water.

[0011] The invention makes it possible to significantly reduce the amount of dye needed to obtain satisfactory coloring, in particular good color rise, intensity and chromaticity as well as uniform coloring.

[0012] Combining direct dyes with application by a recirculation system makes it possible both to increase the coloring power and to reduce the compounds in the rinse water.

[0013] 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:

[0014] - [Fig. 1] schematically represents a distribution device putting in implements the process of the invention.

[0015] 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 ...".

[0016] Furthermore, the expression "at least one" used in this description is equivalent to the expression "one or more".

[0017] The process of the invention implements a coloring composition (A), optionally a pretreatment composition (B) and optionally a posttreatment composition (C). Colouring composition (A)

[0018] The colouring composition (A) implemented in the process of the invention comprises one or more direct colour(s).

[0019] By "direct dye," we mean a natural and / or synthetic dye, including in the form of extract(s), other than oxidation dyes. These are colored compounds that diffuse superficially onto the fiber. They can be ionic or non-ionic, i.e., anionic, cationic, amphoteric, or non-ionic.

[0020] The colouring composition (A) implemented in the process of the invention comprises one or more direct colour(s).

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

[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 colouring composition (A) may comprise one or more non-ionic direct dyes.

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

[0027] The colouring composition (A) 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 nitro(hetero)aromatics; 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 embodiment, the direct dyes are cationic azoic dyes, described in EP 850636, FR 2788433, EP 920856, WO 9948465, FR 2757385, EP 850673, WO 850638, WO 9948433 9744004, FR 2570946, FR 2285851, DE 2538363, FR 2189006, FR 1560664, FR 1540423, FR 1567219, FR 1516943, FR 1212, 228 DE 4137005, WO 0166646, US 5708151, WO 9501772, WO 515144, GB 1195386, US 3524842, US 5879413, EP 1062940, EP 113938, DE 61387, DE 2527638, FR 2275462, GB 1974-27645, Acta Histochem. (1978), 61(1), 48-52 ; Cytology (1968), 10(3), 403-5 ; Zh. Obshch. Khim. (1970), 40(1), 195-202 ; Ann. Say. (Rome) (1975), 65(5-6), 305-14 ; Journal of the Chinese Chemical Society (Taipei) (1998), 45(1), 209-211 ; Rev. Rome. Say. (1988), 33(4), 377-83 ; Text. Nothing. J. (1984), 54(2), 105-7 ; Say. Ind. (Milan) (1974), 56(9), 600-3 ; Khim. Technol. (1979), 22(5), 548-53 ; Word. Monatsh. Chem. (1975), 106(3), 643-8 ; MRL Bull. Nothing. Dev.(1992), 6(2), 21-7; Lihua Jianyan, Huaxue Fence (1993), 29(4), 233-4; Dyes Pigm. (1992), 19(1), 69-79; Dyes Pigm. (1989), 11(3), 163-72. .

[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 - with an endocyclic charge such as comprising a cationic heteroaryl group selected from: acridinium, benzimidazolium, benzobistriazolium, benzopyrazolium, benzopyridazinium, benzoquinolium, benzothiazolium, benzotriazolium, benzoxazolium, bi-pyridinium, bis-tetrazolium, dihydrothiazolium, imidazopyridinium, imidazolium, indolium, isoquinolium, naphthoimidazolium, naphthooxazolium, 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] 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 (Ci-C8)alkyl group such as methyl; * Ar+ represents an aryl radical, such as phenyl or naphthyl, with an exocyclic cationic charge, preferably ammonium, particularly tri(Ci-C8)alkyl-ammonium such as trimethylammonium; * Ar represents an aryl group, in particular phenyl, possibly substituted, preferably by one or more electron-donating groups such as i) (CrC8)alkyl possibly substituted, ii) (Ci-C8)alkoxy possibly substituted, iii) (di) (Ci-C8)(alkyl)amino possibly substituted on the alkyl group(s) by a hydroxyl group, iv) aryl(Ci-C8)alkylamino, v) N-(Ci-C8)alkyl-N-aryl(Ci-C8)alkylamino possibly substituted or else Ar represents a julolidine group; * Ar” represents a (hetero)aryl group possibly substituted such as phenyl or pyrazolyl possibly substituted, preferably by one or more (CrC8)alkyl, hydroxyl, (di)(Ci-C8)(alkyl)amino, (CrC8)alkoxy or phenyl groups; * Ra and Rb, identical or different, representing a hydrogen atom or a (CrC8)alkyl group possibly substituted, preferably by a hydroxyl group; * or the substituent Ra with a substituent of Het+ and / or Rb with a substituent of Ar together form with the atoms that bear them a (hetero)cycloalkyl; particularly Ra and Rb, representing a hydrogen atom or a (Cr C4)alkyl group possibly substituted by a hydroxyl group; * Q represents an organic or mineral anionic counter-ion such as a halide or alkyl sulfate.

[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: R* (C-II-1), (C-IV-1),

[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 (Ci-C8)alkyl possibly substituted, (Ci-C8)alkoxy possibly substituted, (di)(Ci-C8)(alkyl)amino possibly substituted on the alkyl group(s) by a hydroxyl group; particularly R4 is a hydrogen atom, - Z represents a CH group or a nitrogen atom, preferably CH, - Q is an anionic counterion as defined previously particularly a halide such as chloride or an alkyl sulfate such as methyl sulfate or mesytyl.

[0052] In particular, colorants of formula (C-II-1) and (C-IV-1) are selected from Basic Red 51, Basic Yellow 87 and Basic Orange 31 or their derivatives: Basic Yellow 87,

[0053] 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.

[0054] 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.

[0055] 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.

[0056] 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 vol 1 to 7, in the "Kirk-Othmer" encyclopedia "Chemical technology", chapter "Dyes and Dye intermediate", 1993, Wiley and sons, and in various chapters of the encyclopedia "ULLMANN's ENCYCLOPEDIA of Industrial chemistry" 7th edition, Wiley and sons, in The Handbook — A Guide to Fluorescent Probes and Labeling Technologies, 1st Ed Molecular Probes / Invitrogen - Oregon 2005 distributed by the Internet or in previous printed editions.

[0057] 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:

[0058] W+-[C(Rc)=C(Rd)]m'-Ar, Q (C-VI),

[0059] formula (C-VI) wherein: * W+ represents a cationic heterocyclic or heteroaryl group, particularly comprising a quaternary ammonium possibly substituted by one or more (CrC8)alkyl groups possibly substituted in particular by one or more hydroxyl groups; * Ar representing an aryl group such as phenyl or naphthyl, possibly substituted preferably by i) one or more halogen atoms, such as chlorine, fluorine; ii) one or more (Ci-C8)alkyl groups, preferably in Ci-C4 such as methyl; iii) one or more hydroxyl groups; iv) one or more (CrC8)alkoxy groups such as methoxy; v) one or more hydroxy(Ci-C8)alkyl groups such as hydroxyethyl; vi) one or more amino or (di)(Ci-C8)alkylamino groups, preferably with the alkyl portion in Ci-C4 possibly substituted by one or more hydroxyl groups such as (di)hydroxyethylamino; vii) by one or more acylamino groups; viii) one or more heterocycloalkyl groups such as pyperazinyl, pyperidinyl or 5 or 6-membered heteroaryl groups such as pyrrolidinyl, pyridinyl and imidazolinyl; * m' represents an integer between 1 and 4 inclusive, particularly m is 1 or 2; more preferably 1; * Rc, Rd, identical or different, represent a hydrogen atom or a (Ci-C8)alkyl group possibly substituted, preferably at C1-C4, or else Rc contiguous to W+ and / or Rd contiguous to Ar form with the atoms that bear them a (hetero)cycloalkyl, particularly Rc is contiguous to W+ and form a (hetero)cycloalkyl such as cyclohexyl; * Q is an organic or mineral anionic counter-ion as defined previously.

[0060] Among cationic direct dyes, triarylmethane cationic dyes can also be mentioned.

[0061] 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), (c-vir),

[0062] 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,

[0063] preceding formulas (C-VII) and (C-VII') in which: * Rb R2, R3 and R4, 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, borne by the same nitrogen atom, together with the nitrogen atom bearing them form a heterocycloalkyl group, possibly substituted, such as morpholino, piparazino, piperidino, preferably RH. R2, R3 and Ri, identical or different, represent a hydrogen atom or a (CrC4)alkyl group, * R5, R6, R7, Rs, R9, Rio, Ru, R12, Ri3, Ru, Rb and Ri6, whether identical or different, represent a hydrogen atom, a halogen atom, or a group chosen from i) hydroxyl, ii) thiol, iii) amino, iv) (di)(Ci-C4)(alkyl)amino, v) (di)arylamino such that (di)phenylamino, vi) nitro, vü) acylamino (-NR-C(O)R') in which the R radical is a hydrogen atom, a C1-C4 alkyl radical possibly bearing at least one hydroxyl group, and the R' radical is a C1-C2 alkyl radical; viii) carbamoyl ((R)2N-C(O)-) in which the R radicals, whether identical or not, represent a hydrogen atom, a C1-C4 alkyl radical possibly bearing at least one hydroxyl group; ix) carboxylic acid or ester, (-OC(O)R') or

[0064] (-C(O)OR'), wherein the radical R' is a hydrogen atom, or an alkyl in Ci -C4 possibly bearing at least one hydroxyl group and the radical R' is a Ci-C2 alkyl radical; x) alkyl possibly substituted in particular by a hydroxy group; xi) alkylsulfonylamino (R'SO2-NR-) in which the radical R represents a hydrogen atom, an alkyl radical in CrC4 possibly bearing at least one hydroxyl group and the radical R' represents an alkyl radical in CrC4, a phenyl radical; xii) aminosulfonyl ((R)2N-SO2 ) in which the radicals R, identical or not, represent a hydrogen atom, an alkyl radical in CrC4 possibly bearing at least one hydroxyl group, xiii) (CrC4)alkoxy, and xiv) (Ci-C4)alkylthio;* Or, two radicals carried by two adjacent carbon atoms R5 and R6 and / or R7 and R8, and / or R9 and Rio and / or Ru and R[2 and / or Rn and R[4 and / or R15 and Ri6 together with the carbon atoms that support them form a condensed 6-membered aryl or heteroaryl ring, preferably benzo, said ring possibly being further substituted, preferably an unsubstituted benzo ring; ; * Q represents an anionic counter ion to achieve electroneutrality, preferably chosen from halides such as chloride, bromide, and phosphate.

[0065] 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.

[0066] 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, - Ri, 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, R11, R12, Ri3, 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 Rn represents a hydrogen atom, a halogen (Cl), or an amino group, or a (Ci-C4)(alkyl)amino or (di)(Ci-C4) (alkyl)amino group, preferably in the para position of the phenyl group.

[0067] 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.

[0068] Among cationic direct dyes, anthraquinone cationic dyes can also be mentioned.

[0069] The anthraquinone cationic direct dye(s) usable in the coloring composition (A) of the invention comprise a quaternary ammonium group.

[0070] 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.

[0071] De préférence, la charge cationique est exocyclique.

[0072] Parmi les colorants directs cationiques anthraquinoniques, on préfère ceux de formule (C-VIII) ayant une charge cationique exocyclique : (c-vm)

[0073] in which: - R1, R2 and R3, identical or different, representing a hydrogen atom or a (CrC8)alkyl group possibly substituted; - R4 representing a hydrogen atom or a (CrC8)alkyl group possibly substituted; - R5 represents a hydrogen atom, a (Ci-C8)alkyl group (possibly substituted), a (CrC8)alkylene group (possibly substituted), a halogen, a hydroxyl group, or a (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.

[0074] 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 (CrC8)alkyl group, possibly substituted, - n representing a number between 1 and 6; - Q representing a halide or an alkyl sulfate.

[0075] 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.

[0076] Among the dyes of formula (C-VIII), the following dyes of formula (C-VIII') or formula (C-VIII”) may be used in particular: Ô NK (C-VIII') (c-vm”)

[0077] 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.

[0078] 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. ;

[0079] A dye of formula (C-VIII') particularly preferred is HC Blue 17.

[0080] A dye of formula (C-VIII”) that is particularly preferred is HC Blue 16 (l-methylamino-4-(3'-dimethylpropylammoniumpropylamino)antraquinone bromide).

[0081] 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.

[0082] The colouring composition (A) according to the invention may comprise one or more anionic direct dyes.

[0083] The anionic direct dyes of the invention are dyes commonly referred to as "acid" direct dyes because of their affinity for alkaline substances. By Anionic direct dyes are defined as any direct dye containing in its structure at least one CO2R or SO3R substituent, where R designates a hydrogen atom, a cation from a metal or amine, or an ammonium ion. Anionic dyes can be selected from among acidic nitro dyes, acidic azo dyes, acidic azinic dyes, acidic triarylmethanic dyes, acidic indoamine dyes, acidic anthraquinone dyes, acidic indigoid dyes, and acidic natural dyes.

[0084] According to the invention, the anionic direct dye(s) can be chosen, alone or in mixture, from among 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):

[0085] a) Diaryl anionic azo dyes of formula (A-II) or (A-II'):

[0086] 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 bearing them form a spiro cycloalkyl; preferably W represents a sulfur atom or Ra and Rb together form a cyclohexyl; provided that formulas (A-II) and (A-II') comprise at least one sulfonate radical (O)2S(O )-, M+ or one carboxylate radical (O)CO -, M+ on one of the rings A, A', B, B' or C; preferably sodium sulfonate;

[0087] 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 Bine 113, Acid Bine 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;

[0088] et à titre d’exemple de colorants de formule (A-IF), on peut citer : Acid Red 111, Acid Red 134, Acid yellow 38 ;

[0089] b) les colorants azo anioniques pyrrazolone de formule (A-III) et (A-IIF) :

[0090] formulas (A-III) and (A-III') wherein: * Ru, Rn and Rn, identical or different, represent a hydrogen atom, a halogen, an alkyl group or -(O)2S(O), M+ with M+ as defined previously; * Ru represents a hydrogen atom, an alkyl group or a -C(O)O group, M+ with M+ as defined previously; * Rb represents a hydrogen atom; * Ri6 represents an oxo group in which case R'i6 is absent, or else R[5 with R[6 together form a double bond; * Rn and Ri8, whether identical or different, represent a hydrogen atom, or a group chosen from: - (O)2S(O )-, M+ with M+ as defined previously; - Ar-OS(O)2- with Ar representing an aryl group possibly substituted; preferably a phenyl possibly substituted by one or more alkyl groups; * R19 and R2q together form either a double bond or a benzo D' group, possibly substituted; * R'16, R'19 and R'20, identical or different, represent a hydrogen atony 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;

[0091] c) the anthraquinone dyes of formula (A-IV) and (A-IV'):

[0092] formulas (A-IV) and (A-IV) in which: * R22, R23, R24, R25, R26 and R27, whether identical or different, represent a hydrogen atom, a halogen atom, or a group chosen from: - alkyl; - hydroxy, mercapto; - alkoxy, alkylthio; - aryloxy or arylthio possibly substituted, preferably substituted by one or more groups chosen from alkyl and (O)2S(O )-, M+ with M+ as defined above; - aryl(alkyl)amino possibly substituted by one or more groups chosen from alkyl and (O)2S(O )-, M+ with M+ as defined previously; - (di)(alkyl)amino; - (di)(hydroxyalkyl)amino - (O)2S(O )-, M+ with M+ as defined previously; * Z' represents a hydrogen atom or a group NR28R29 where R28 and R29, identical or different, represent a hydrogen atom or a group chosen from: - alkyl; - polyhydroxyalkyl such as hydroxyethyl; - aryl possibly substituted by one or more particularly i) alkyl groups such as methyl, n-dodecyl, n-butyl; ii) (O)2S(O )-, M+ with M+ as defined previously; iii) R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X”- with R°, X, X' and X” as defined previously, preferably R° represents an alkyl group; - cycloalkyl; in particular cyclohexyl; * Z, represents a group chosen from hydroxy and NR'28R'29 with R'28 and R'29, identical or different, represent the same atoms or groups as R28 and R29 as defined previously; provided that formulas (A-IV) and (A-IV') comprise at least one sulfonate radical (O)2S(O )-, M+ or one carboxylate radical -C(O)O, M+; preferably sodium sulfonate; As an example of dyes of formula (A-IV), we can cite: Acid Blue 25, Acid Blue 43, Acid Blue 62, Acid Blue 78, Acid Blue 129, Acid Blue 138, Acid Blue 140, Acid Blue 251, Acid Green 25, Acid Green 41, Acid Violet 42, Acid Violet 43, Mordant Red 3; EXT purple No. 2; and as an example of dyes of formula (A-IV') we can cite: Acid Black 48;

[0093] d) the nitro dyes of formula (AV), and (A-V'): (AV) NO?

[0094] 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;

[0095] - (di)(hydroxyalkyl)amino; - heterocycloalkyl such as piperidino, piperazino or morpholino; in particular R30, R3i and R32 represent a hydrogen atom; * Rc and Rd, whether identical or different, represent a hydrogen atom or an alkyl group; * W is as defined previously; W particularly represents a -NH- group; * ALK represents a divalent alkylene group, linear or branched, in Ci-C6; particularly ALK represents a -CH2-CH2- group; * n equals 1 or 2; * p represents an integer between 1 and 5 inclusive; * q represents an integer between 1 and 4 inclusive; * u is equal to 0 or 1; * when n equals 1, J represents a nitro, or nitroso, group; particularly nitro; * when n equals 2, J represents an oxygen atom, a sulfur atom, or a divalent radical -S(O)m- with m representing an integer 1 or 2; preferably J represents a radical -SO2-; * M' represents a hydrogen atom or a cationic counter-ion; * -- The presence or absence of x 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;

[0096] As an example of colorants of formula (AV) we can mention: Acid Brown 13; Acid Orange 3; examples of colorants 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;

[0097] e) triarylmethane dyes of formula (A-VI): U R. *2 ru.

[0098] 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 R44, whether identical or different, represent a hydrogen atom or a group chosen from: - alkyl; - alkoxy, alkylthio; - (di)(alkyl)amino; - hydroxy, mercapto; - nitro, nitroso; - R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X”- with R° representing a hydrogen atom, an alkyl or aryl group; X, X' and X”, identical or different, representing an oxygen, sulfur or NR atom with R representing a hydrogen atom or an alkyl group; - (O)2S(O )-, M+ with M+ representing a hydrogen atom or a cationic counter-ion; - (O)CO -, M+ with M+ as defined previously; - or two contiguous groups R4[ with R42 or R2 with R41 or R43 with R44 together form a fused benzo group: I'; with I' possibly substituted by one or more groups chosen from i) nitro; ii) nitroso; iii) (O)2S(O )-, M+; iv) hydroxy; v) mercapto; vi) (di)(alkyl)amino; vii) R°-C(X)-X'-; viii) R°-X'-C(X)-; ix) R°-X'-C(X)-X”-; with M+, R°, X, X', X” as defined previously; particularly R37 at Rio represent a hydrogen atom, and Ri at IR, identical or different represent a hydroxy group or (O)2S(O )-, M+; and when R3 with R4 together form a benzo group, it is preferentially substituted by an (O)2S(O )- group; provided that at least one of the rings G, H, I, or I' comprises at least one sulfonate radical (O)2S(O)- or one carboxylate radical -C(O)O; preferably sulfonate. Examples of dyes with the formula (A-VI) include: Acid Blue 1; Acid Blue 3; Acid Blue 7; Acid Blue 9; Acid Violet 49; Acid Green 3; Acid Green 5; Acid Green 50;

[0099] f) xanthene-derived dyes of formula (A-VII): % R (A-VII) fR R \ R,

[0100] formula (A-VII) in which: * R5, R46, R7 and R48, whether identical or different, represent a hydrogen atom or a halogen atom; * R9, R50, R51 and R52, whether identical or different, represent a hydrogen atom, a halogen atom, or a group chosen from: - alkyl; - alkoxy, alkylthio; - hydroxy, mercapto; - nitro, nitroso; - (O)2S(O )-, M+ with M+ representing a hydrogen atom or a cationic counter-ion; - (O)CO -, M+ with M+ as defined previously; in particular R53, R54, R55 and R48 represent a hydrogen or halogen atom; * G represents an oxygen atom, sulfur atom or an NR group with R representing a hydrogen atom or an alkyl group; particularly G represents an oxygen atom; * L represents an alkoxide O M+; a thioalkoxide S , M+ or an NRf group, with Rf representing a hydrogen atom or an alkyl group, and M+ as defined previously; M+ is particularly sodium or potassium; * L' represents an oxygen atom, sulfur atom or ammonium group: N+ RfRg, with Rf and Rg, identical or different, representing a hydrogen atom, an alkyl group, aryl group possibly substituted; L' particularly represents an oxygen atom or a phenylamino group possibly substituted by one or more alkyl groups or (O)mS(O )-, M+ with m and M+ as defined previously; * Q and Q', whether identical or different, represent an oxygen or sulfur atom; particularly Q and Q' represent an oxygen atom; * M+ is as defined previously.

[0101] As an example of colorants of formula (A-VII), we can mention: Acid Yellow 73; Acid Red 51; Acid Red 52, Acid Red 87; Acid Red 92; Acid Red 95; Acid Violet 9;

[0102] g) dyes derived from indole of formula (A-VIII): (A-vni)

[0103] 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;

[0104] - R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X”- with R° representing atony hydrogen, an alkyl or aryl group; X, X' and X”, identical or different, representing an oxygen, sulfur or NR atom with R representing a hydrogen atom or an alkyl group; - (O)2S(O )-, M+ with M+ representing a hydrogen atom or a cationic counter-ion; - (O)CO -, M+ with M+ as defined previously; * G represents an oxygen atom, sulfur atom or an NR group with R representing a hydrogen atom or an alkyl group; particularly G represents an oxygen atom; * Ri and Rh, whether identical or different, represent a hydrogen atom or an alkyl group; provided that the formula (A-VIII) comprises at least one sulfonate radical (O)2 S(O )-, M+ or one carboxylate radical -C(O)O, M+; preferably sodium sulfonate;

[0105] As an example of colorants of formula (A-VIII), we can cite: Acid Blue 74.

[0106] h) quinoline-derived dyes of formula (A-IX):

[0107] formula (A-IX) wherein: * R6i represents a hydrogen atom, halogen or alkyl group; * R62, R63, 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.

[0108] Examples of colorants of formula (A-IX) include: Acid Yellow 2, Acid Yellow 3 and Acid Yellow 5.

[0109] More specifically, the coloring composition (A) comprises one or more anionic direct dyes selected, alone or in mixture, from the following anionic direct dyes:

[0110] [Tables 1] (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-sufonatoazo)-naphtalène-4-sulfonique / Food Red 1 (A-II) (C.L 14720) Acid Red 14 / Food Red 3 / Mordant Blue 79 (A-II) (C. 1. 14805) Sel de sodium de l’acide 4-hydroxy-3-[(2-métoxy-5-. nitrophényl) diaza]-6-(phénylamino)naphtalène-2-sulfonique / Acid Brown 4 ( A-II) (C.L 15510) Acid Orange 7 / Pigment Orange 17 / Solvent Orange 49 (A-II) (C.L 15985) Food Yellow 3 / Pigment Yellow 104 (A-II) (C.L 16185) Acid Red 27 / Food Red 9 (A-II) (C.L 16230) Acid Orange 10 / Food Orange 4 (A-II) (C.L 16250) Acid Red 44 (A-II) (C.L 17200) Acid Red 33 / Food Red 12 (A-II) (C.L 15685) Acid Red 184 (A-II) (C.L 19125) Acid Violet 3 (A-II) (CL 18055) Sodium salt of l-hydroxy-2-(4'-acetamidophenylazo)-8-acetamido-naphthalene-3,6-disulfonic acid / Acid Violet 7 / Food Red 11 (A-II) (CL 18130) Acid Red 135 (A-II) (CL 19130) Acid Yellow 27(A-III) (CL 19140) Acid Yellow 23 / Food Yellow 4 (A-III) . (CL 20170) 4'-(sulfonato-2,4'-dimethyl)-bis-(2,6-phenylazo)-1,3-dihydroxybenzene / Acid Orange 24 (A-II) (Cl 20470) Sodium salt of l-amino-2-(4'-nitrophenylazo)-7-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 111 (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-anthraquinone 2-sulfonic acid / Acid Blue 62 (A-IV) (Cl 62105) Acid Blue 78 (A-IV) (Cl14710) 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)-l-naphthalene sulfonic acid / Acid Red 4 (A-II) .

[0111] 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.

[0112] The anionic colorants most particularly preferred are the colorants designated in the Color Index under the code CI 58005 (monosodium salt of 1,2-dihydroxy-9,10-anthraquinone-3-sulfonic acid), CI 60730 (monosodium salt of 2-[(9,10-dihydro-4-hydroxy-9,10-dioxo-l-anthracenyl)-amino]-5-methylbenzenesulfonic acid), CI 15510 (monosodium salt of 4-[(2-hydroxy-l-naphthalenyl)-azo]-benzenesulfonic acid), CI 15985 (disodium salt of 6-hydroxy-5-[(4-sulfophenyl)-azo]-2-naphthalenesulfonic acid), CI 17200 (disodium salt of 5-amino-4-hydroxy-3-(phenylazo)-2,7-naphthalene disulfonic acid), CI 20470 (disodium salt of l-amino-2-(4'-nitrophenylazo)-7-phenylazo-8-hydroxy-3,6-naphthalene disulfonic acid), CI 42090 (disodium salt of N-ethyl-N-[4-[[4-[ethyl[3-sulfophenyl]-methyl]-amino]-phenyl](2-sulfophenyl)-methylene]-2,5-cyclohexadien-l-ylidene]-3-sulfobenzenemethanaminium hydroxide, internal salt), CI61570 (disodium salt of 2,2'-[(9,10-dihydro-9,10-dioxo-l,4-anthracenediyl)-diimino]-bis-[5-methyl]-benzenesulfonic acid. .

[0113] Compounds corresponding to the mesomeric, tautomeric forms of (A-II) to (A-IX) structures can also be used.

[0114] 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.

[0115] Preferably, the colouring composition (A) implemented in the process of the invention comprises one or more cationic direct colour(s).

[0116] Preferably, the colouring composition (A) implemented in the process of the invention comprises one or more cationic direct dye(s) selected from azo cationic direct dyes, hydrazono cationic direct dyes, anthraquinone cationic direct dyes, triarylmethane cationic direct dyes and mixtures thereof.

[0117] Preferably, the coloring composition (A) implemented in the process of the invention comprises one or more anionic direct dye(s), preferably chosen from acidic azo direct dyes, acidic azinic direct dyes, acidic triarylmethanic direct dyes, acidic indoamine direct dyes, acidic anthraquinone direct dyes, acidic indigoid direct dyes, acidic natural direct dyes, and mixtures thereof.

[0118] Advantageously, the total content of the direct colorant(s) in the coloring composition (A) applied in step i) ranges from 0.001 to 10%, preferably from 0.005 to 5% by weight, more preferably from 0.01 to 2% by weight, better from 0.02 to 1% by weight, relative to the total weight of the coloring composition (A).

[0119] The colouring composition (A) according to the invention may include water.

[0120] Preferably, the colouring composition (A) comprises water.

[0121] Preferably, the coloring composition (A) applied in step i) comprises water in a content of 60 to 99.999% by weight, preferably 65 to 99.995% by weight, preferably still 70 to 99.99% by weight, more preferably 75% to 99.98% by weight relative to the total weight of the colouring composition (A).

[0122] Preferably, when applied in step i) with the dispensing device 10, the colouring composition (A), preferably liquid, applied in step i) comprises water in a content of 80 to 99.999% by weight, preferably 85 to 99.995% by weight, preferably still 90 to 99.99% by weight, more preferably 95% to 99.98% by weight relative to the total weight of the colouring composition (A).

[0123] The colouring composition (A) may also include one or more organic solvents selected from aromatic alcohols and alkylene carbonates.

[0124] Preferably, the colouring composition (A) comprises one or more organic solvents selected from aromatic alcohols and alkylene carbonates.

[0125] Preferably, the organic solvent(s) are chosen from benzyl alcohol, phenethyl alcohol, cinnamic alcohol, phenylpropyl alcohol, l-phenoxy-2-propanol, phenyl diglycol, α-methylbenzyl alcohol, dimethylbenzylcarbinol, benzyloxyethanol, phenoxyethanol, phenoxyisopropanol, p-anisyl alcohol, ethylene carbonate and propylene carbonate.

[0126] Even more preferably, the organic solvent(s) are chosen from benzyl alcohol, ethylene carbonate and propylene carbonate.

[0127] When it includes them, the colouring composition (A) applied in step i) includes one or more organic solvents selected from aromatic alcohols and alkylene carbonates in a content ranging from 0.1 to 20% by weight, preferably from 0.5 to 15% by weight, more preferably from 1 to 13% by weight relative to the total weight of the composition (A).

[0128] The coloring composition (A) used in the process of the invention may also contain various additives conventionally used in hair coloring compositions, such as surfactants, in particular anionic, cationic, non-ionic, amphoteric or zwitterionic surfactants; polymers, in particular anionic, cationic, amphoteric, zwitterionic polymers or non-ionic; mineral or organic thickening agents; antioxidants, sequestering agents, perfumes, buffers, dispersing agents, ceramides, preservatives, opacifying agents.

[0129] Of course, a person skilled in the art will take care to choose this or these possible complementary compounds in such a way that the advantageous properties intrinsically attached to the colouring composition (A) are not, or substantially not, altered by the envisaged addition(s).

[0130] Since the composition is applied using a distribution device, the process according to the invention makes it possible to eliminate various compounds conventionally contained in coloring compositions, thus limiting the quantity of compounds present in the rinsing water.

[0131] Preferably, the colouring composition (A) applied in step i) comprises less than 1%, preferably less than 0.5% by weight relative to the total weight of the composition (A), better does not contain any fat.

[0132] The term "fatty substance" means an organic compound insoluble in water at 25°C and atmospheric pressure (1.013 x 10⁵ Pa) (solubility less than 5% by weight, and preferably less than 1% by weight, and even more preferably less than 0.1% by weight). Its structure includes at least one hydrocarbon chain comprising at least 6 carbon atoms and / or a chain of at least two siloxane groups. Furthermore, fatty substances are generally soluble in organic solvents under the same temperature and pressure conditions, such as chloroform, dichloromethane, carbon tetrachloride, ethanol, benzene, toluene, tetrahydrofuran (THF), petrolatum, or decamethylcyclopentasiloxane.

[0133] Preferably, the coloring composition (A) applied in step i) comprises less than 1%, preferably less than 0.5% by weight relative to the total weight of composition (A), better does not contain any thickening agent.

[0134] For the purposes of this invention, "thickening agent" means an agent which, when introduced at 1% by weight into an aqueous or hydroalcoholic solution of 30% ethanol, and at pH = 7, makes it possible to achieve a viscosity of at least 100 cps (centipoise), in particular at least 200 cps, preferably at least 500 cps, measured at 25 °C and at a shear rate of 1 s1. This viscosity can be measured using a cone / plate viscometer (Haake R600 rheometer or similar).

[0135] Preferably, the colouring composition (A) applied in step i) comprises less than 1%, preferably less than 0.5% by weight relative to the total weight of composition (A), better does not contain thickening polymer.

[0136] Preferably, the colouring composition (A) applied in step i) comprises less than 1%, preferably less than 0.5% by weight relative to the total weight of composition (A), better does not contain any mineral thickening agent.

[0137] Preferably, the coloring composition (A) applied in step i) comprises less than 1%, preferably less than 0.5% by weight relative to the total weight of composition (A), better does not contain any surfactant.

[0138] Preferably, the colouring composition (A) is in the form of an aqueous solution.

[0139] The colouring composition (A) is preferably liquid.

[0140] By liquid composition is meant a composition of viscosity less than 50 mPa.s measured at 25°C and at a shear rate of 1s 1; this viscosity can be determined by means of a Thermo Haake RS600 rotary rheometer, equipped with a plane-plane geometry 0 35 mm with an air gap of 1 mm.

[0141] Preferably, the colouring composition (A) has a viscosity less than or equal to 50 mPa.s, preferably less than or equal to 20 mPa.s, better less than or equal to 10 mPa.s, measured at 25°C and at a shear rate of 1s; this viscosity can be determined using a Thermo Haake RS600 rotary rheometer, equipped with a 0-35 mm plane-plane geometry with a 1 mm air gap.

[0142] The pH of the colouring composition (A) implemented in the process according to the invention is preferably between 2.5 and 10. It can be adjusted to the desired value by means of acidifying or alkalizing agents commonly used in dyeing keratinous fibres or by means of conventional buffer systems.

[0143] 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.

[0144] Examples of alkalizing agents include ammonia, alkali carbonates, alkanolamines such as mono-, di- and triethanolamines and their derivatives, sodium or potassium hydroxides and compounds of the following formula: NWN R ( X

[0145] wherein W is a propylene residue 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 Ci-C4 alkyl radical or a Ci-C4 hydroxyalkyl radical.

[0146] In particular, when the colouring composition (A) comprises anionic direct dyes, the pH of the colouring composition (A) is less than 7, preferably from 2 to 5, the pH being able to be adjusted by means of a carboxylic acid.

[0147] When the color composition (A) includes cationic direct dyes, and preferably when it does not include anionic direct dyes, the pH of the color composition (A) ranges from 6 to 12, preferably from 7 to 11. Pretreatment composition (B)

[0148] Before step i) of applying the coloring composition (A) to the keratin fibers, the process according to the invention may include a step of applying to the keratin fibers a pretreatment composition (B) comprising one or more reducing agents.

[0149] Preferably, the process according to the invention includes a step of applying a pretreatment composition (B) comprising one or more reducing agents to the keratin fibers before step i) of applying the coloring composition (A).

[0150] Preferably, the reducing agent(s) are chosen from thiolated reducing agents, non-thiolated reducing agents and mixtures thereof.

[0151] For the purposes of the present invention, "thiol" and "thiolated" mean any molecule bearing an -SH group or a group capable of generating a thiol by a simple chemical or photochemical reaction (hydrolysis, for example). Thus, for the purposes of the present invention, compounds bearing protected thiol groups as defined, for example, in "Protective Groups in Organic Synthesis," T. W. Greene and PGM Wuts, Second Edition, Protection of the Thiol Groups, are considered to be compounds bearing -SH thiol groups. For the purposes of the present invention, "non-thiolated reducing agent" means a reducing agent that does not contain any thiol group.

[0152] The thiolated reducing agent(s) according to the invention can be chosen from organic compounds comprising one or more -SH groups, and optionally at least one other function chosen from carboxylic acid, amine, amide, ester and alcohol functions and mixtures thereof.

[0153] Preferably, the thiolated reducing agent(s) are chosen from among the reducing agents of formula (i-1) following, their mineral and / or organic salts and their mixtures: Fb-SH (i-1) formula (i-1) in which: ■ RI represents: - a (Cl-C8)alkyl group, preferably (Cl-C6)alkyl, possibly substituted by one or more groups selected from carboxyl C(O)OH, (di)(Cl-C4)(alkyl)amino, hydroxyl -OH, thiol -SH or -C(O)-NH-CH2-C(O)OH and / or possibly interrupted by one or more heteroatoms or groups selected from -O-, and -S-, -N(R”')-, C(O) or their combinations such as -OC(O)-, -C(O)-O-, -C(O)-OR*, -N(R”')-C(O)-, or -C(O)-N(R’”)- ; with R”' representing a hydrogen atom or a (Cl-C6)alkyl group; R* representing a (Cl-C6)alkyl group possibly substituted by one or more hydroxyl -OH, thiol -SH or amino -NH2 groups; or - a (hetero)aryl group possibly substituted by one or more hydroxyl, thiol or carboxyl groups; ■ R' and R”, identical or different, represent a (Cl-C8)alkyl group, preferably (Cl-C6)alkyl, substituted by one or more groups chosen from hydroxyl, thiol, and carboxyl or their combinations; or else R' and R" together with the sulfur atom which bears them form a heterocyclic group, comprising 5 to 7 links, preferably saturated, comprising 1 to 3 heteroatoms, possibly substituted by one or more (Cl-C6)alkyl groups possibly substituted by one or more hydroxyl, thiol or carboxyl groups, more preferably the heterocyclic group is a dithiolane group possibly substituted by a (Cl-C6)alkyl group possibly substituted by one or more carboxyl groups.

[0154] According to a preferred embodiment of the invention, the thiolated reducing agent(s) of formula (i-1) are chosen from those in which Ri represents a (Cl-C8)alkyl group, preferably (Cl-C6)alkyl, - substituted by one or more groups chosen from carboxyl C(O)OH, amino, hydroxyl -OH, thiol -SH; and / or - possibly interrupted by one or more heteroatoms or groups chosen from -O-, -N(R'”)-, C(O) or their combinations such as -OC(O)-, -C(O)-O-, -N(R'”)-C(O)-, or -C(O)-N(R'”)-; with R'” representing a hydrogen atom or a (Cl-C6)alkyl group.

[0155] According to a more preferred embodiment of the invention, the thiolated reducing agent(s) of formula (i-1) are chosen from those in which Ri represents an uninterrupted (Cl-C8)alkyl group, preferably (Cl-C6)alkyl, substituted by one or more groups chosen from carboxyl C(O)OH, amino, hydroxyl -OH, thiol -SH.

[0156] According to another embodiment of the invention, the thiolated reducing agent(s) of formula (i-1) are chosen from those in which Ri represents:

[0157] - a phenyl group optionally substituted by one or more selected groups among carboxyl C(O)OH, amino, hydroxyl -OH, thiol -SH; or

[0158] - a heteroaryl group comprising 5 to 10 links, preferably bicyclic with 9 or 10 links, comprising 1 to 4 heteroatoms chosen from O, S or N, preferably N, possibly substituted by one or more hydroxyl or thiol groups.

[0159] The thiolated reducing agent(s) according to the invention may, in particular, be used in the form of mineral and / or organic salts, especially alkali metal salts such as sodium and potassium salts, alkaline earth metal salts, for example magnesium, calcium, and strontium salts, hydrated or not, ammonium salts, hydrochloric acid salts, amine salts, and amino alcohol salts, for example, ethanolamine salts. Ammonium thioglycolate, cysteine ​​hydrochloride, or ethanolamine thioglycolate may thus be used as a thiolated reducing agent.

[0160] Preferably, the thiolated reducing agent(s) are chosen from thioglycolic acid, thiolactic acid, cysteine, cysteamine, N-acetylcysteamine, N-propionylcysteamine, cysteine, homocysteine, glutathione, thioglycerol, thiomalic acid, 3-mercaptopropionic acid, panthetheine, dimercaptosuccinic acid, thiosulfuric acid derivatives, 2-mercaptoethanol, dithiothreitol, thiosalicylic acid, thiodiglycolic acid, N-acetylcysteine, esters and amides of thioglycolic or thiolactic acids, in particular glycerol monothioglycolate, their mineral and / or organic salts, and mixtures thereof.

[0161] More preferably, the thiolated reducing agent(s) are chosen from the group consisting of thioglycolic acid, thiolactic acid, cysteine, cysteamine, N-acetylcysteamine, glycerol monothioglycolate, thiosulfuric acid derivatives, their mineral and / or organic salts, and mixtures thereof.

[0162] Even more preferably, the thiolated reducing agent(s) may be chosen from thioglycolic acid, thiolactic acid, cysteine, their mineral and / or organic salts, such as cysteine ​​hydrochloride and mixtures thereof, preferably from thioglycolic acid, its mineral and / or organic salts and mixtures thereof.

[0163] The non-thiolated reducing agent(s) according to the invention can be chosen from among sulfites, bisulfites, sulfinates, phosphines, reducing sugars, and mixtures thereof.

[0164] Among the non-thiolated reducing agents selected from sulfites and bisulfites, particular examples include ammonium sulfites and bisulfites, as well as sulfites and Metal bisulfites, including alkali metal or alkaline earth metal sulfites and bisulfites, such as sodium sulfites and bisulfites.

[0165] Among the non-thiolated reducing agents selected from among the sulfinates, mention may be made of sulfinic acid salts and benzenesulfonic acid salts such as sodium salts thereof. The sulfinic acid derivatives described in document FR-A-2814948 may also be used. Preferably, the non-thiolated reducing agent selected from among the sulfinates is the disodium salt of 2-hydroxy-2-sulfinatoacetic acid.

[0166] Among the non-thiolated reducing agents selected from among the phosphines, one can mention monophosphines and diphosphines, as described in document FR-A-2870119.

[0167] According to a preferred embodiment, phosphines have the following formula (i-2), their salts, their solvates, and their mixtures:

[0168] P(R41)(R42) (R43) (i-2)

[0169] Formula (i-2) in which:

[0170] R41, R42, R43 independently designating a (Cl-C6)alkyl group possibly substituted by one or more groups chosen from OH, COOH.

[0171] Preferably R41, R42 and R43 designate a group selected from C1-C6 hydroxyalkyl, preferably C1-C4 hydroxyalkyl such as hydroxymethyl or hydroxypropyl such as 3-hydroxypropyl; C1-C6 carboxyalkyl, preferably C1-C4 carboxyalkyl such as 2-carboxyethyl.

[0172] According to a particularly preferred embodiment, the phosphines are chosen from among the phosphines of formula (i-2) and R41, R42 and R43 are identical.

[0173] According to a particularly preferred embodiment, the phosphines are selected from Tris(hydroxymethyl)phosphine, Tris(hydroxypropyl)phosphine, Tris(2-carboxyethyl)phosphine, and mixtures thereof.

[0174] According to a preferred embodiment of the invention, the phosphine(s) usable in the context of the invention is / are soluble in a cosmetically acceptable medium. Preferably, the phosphine(s) usable in the context of the invention is / are soluble in water.

[0175] In the context of the present invention, the term "water soluble" means any phosphine whose solubility in water is greater than 0.01% by weight at 20°C.

[0176] Preferably, phosphine is tris(2-carboxyethyl)phosphine or its mineral and / or organic salts.

[0177] Among the non-thiolated reducing agents selected from reducing sugars, one can mention glucose, fructose, maltose, ribose, galactose, lactose, and xylose.

[0178] Advantageously, the reducing agent(s) are chosen from among thiol reducing agents, sulfites, bisulfites, sulfinates, phosphines, reducing sugars, their mineral and / or organic salts, and mixtures thereof, preferably thiol reducing agents, their mineral and / or organic salts and mixtures thereof, more preferably thiol reducing agents, their mineral and / or organic salts and mixtures thereof.

[0179] Preferably, the reducing agent(s) as defined above is / are present in a content ranging from 0.1% to 10% by weight, preferably from 0.5% to 8% by weight, preferably from 1% to 7% by weight relative to the total weight of the pretreatment composition (B) according to the invention.

[0180] The pretreatment composition (B) may include water.

[0181] Preferably, the pretreatment composition (B) comprises water, preferably in a content of 90 to 99.5% by weight relative to the total weight of the pretreatment composition (B).

[0182] The pretreatment composition (B) preferably has a basic pH.

[0183] According to a preferred embodiment of the invention, the pH of the pretreatment composition (B) is greater than 7, preferably from 8 to 12, more preferably from 9 to 11, better from 9.5 to 10.5.

[0184] The pH can be adjusted to the desired value using alkalizing agents commonly used in dyeing keratin fibers such as those described above or using conventional buffer systems. Post-processing composition (C)

[0185] After step iii) or after the possible rinsing step iv), the process according to the invention may include a step of applying a post-treatment composition (C) comprising one or more chemical oxidizing agents.

[0186] Preferably, the process according to the invention includes a step of applying a post-treatment composition (C) comprising one or more chemical oxidizing agents.

[0187] A chemical oxidizing agent is understood to be an oxidizing agent other than oxygen from the air.

[0188] The chemical oxidizing agent(s) are chosen from hydrogen peroxide, urea peroxide, alkali metal bromates or ferricyanides, peroxygenated salts such as alkali or alkaline-earth metal persulfates, perborates and percarbonates, and peracids and their precursors.

[0189] More preferably the post-treatment composition (C) comprises hydrogen peroxide.

[0190] The total content of the chemical oxidizing agent(s) varies preferably from 1 to 20% by weight, more preferably from 1.5 to 15% by weight, better from 2 to 10% by weight relative to the total weight of the post-treatment composition (C).

[0191] The post-treatment composition (C) preferably comprises water. In particular, it comprises more than 10% by weight of water, preferably more than 30% by weight. water weight, and even more advantageously more than 50% water weight. Preferably the post-treatment composition (C) comprises water in a content of 10% to 95% by weight, preferably 30% to 93% by weight, better 50% to 92% by weight relative to the total weight of the post-treatment composition (C).

[0192] The pH of the post-treatment composition (C) is preferably less than 7, preferably between 1 and 5, preferably between 1.5 and 4.5.

[0193] This pH can be adjusted to the desired value by the use of one or more acidifying agents.

[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. Coloring process

[0195] The process for coloring keratin fibers according to the invention comprises: (i) the application to said keratin fibers of a coloring composition (A) as defined above, ii) the recovery of at least part of the coloring composition (A) after application to the keratin fibers, iii) the application of the staining composition (A) recovered in step ii) onto the keratin fibers.

[0196] The coloring composition (A) can be applied in step i) to dry or wet keratin fibers.

[0197] Preferably, the staining composition (A), preferably liquid, is applied in step i) to the keratin fibers using the dispensing device 10 as described below.

[0198] Alternatively, the coloring composition (A) can be applied in step i) by hand to the keratin fibers, for example using a brush or a hot water bottle, in the conventional manner. An aqueous solution, preferably water, is then applied to the keratin fibers.

[0199] At least part of the coloring composition (A) is recovered in step ii), preferably in a reservoir, after application to the keratin fibers.

[0200] The portion of the staining composition (A) recovered in step ii) is then reapplied to the keratin fibers in step iii), preferably using the dispensing device 10.

[0201] Preferably, steps ii) and iii) are repeated at least once, preferably several times. More preferably, steps ii) and iii) are carried out continuously, in particular by means of the distribution device 10.

[0202] The colouring composition (A), preferably in liquid form, is thus distributed over the hair in a continuous flow.

[0203] According to the process of the invention, the coloring composition (A) is recycled and redistributed onto the keratin fibers. The keratin fibers are thus subjected to several passes of the coloring composition (A), allowing the fixation of a greater quantity of direct dyes onto the keratin fibers.

[0204] Preferably, steps i) to iii) of the coloring process according to the invention are carried out for a period of 1 to 45 minutes, preferably 5 to 30 minutes.

[0205] At the end of the coloring treatment, the keratin fibers are preferably rinsed with water during a rinsing step iv).

[0206] Preferably, the keratin fibres can then be washed with shampoo and rinsed with water, before possibly being wrung out, dried or left to dry.

[0207] According to a preferred embodiment, prior to step i) of applying the coloring composition (A), the process according to the invention includes a step of applying a pretreatment composition (B) as described above comprising one or more reducing agents.

[0208] The pretreatment composition (B) is preferably applied by hand to the keratin fibers using a brush, spray, or pipette, depending on the texture of the composition. It is preferably left on the keratin fibers for a period of 1 to 15 minutes, preferably 2 to 10 minutes, and preferably 3 to 8 minutes.

[0209] The keratin fibers are then preferably rinsed with water before the application of the coloring composition (A).

[0210] According to another preferred embodiment, the coloring process according to the invention includes after step iii) or after the optional rinsing step iv), a step v) of application of a post-treatment composition (C) as described above, comprising one or more chemical oxidizing agents.

[0211] The post-treatment composition (C) can be applied to the keratin fibers using a brush. It is preferably left on the keratin fibers for a period of 1 to 15 minutes, preferably 2 to 10 minutes, better 3 to 8 minutes.

[0212] The keratin fibers can then be rinsed with water in a rinsing step, and then optionally dried or left to dry. Distribution device

[0213] To implement the coloring process according to the invention which has just been described, a distribution device is used.

[0214] This distribution device may include, in particular, all or part of the following characteristics:

[0215] - the dispensing device includes a dispensing nozzle comprising at minus one outlet;

[0216] - the distribution device includes a pump for supplying under pressure the dispensing nozzle;

[0217] - the dispensing device comprises at least one reservoir and at least one piping to draw the contents of this tank and recycle them to the dispensing nozzle;

[0218] - the liquid flow rate dispensed by the dispensing nozzle ranges from 0.01 to 20 l / min, from preferably from 0.05 to 15 l / min, more preferably from 0.1 to 10 l / min.

[0219] In [Fig.1], a dispensing device 10 comprising a dispensing nozzle 11 and a reservoir 12 is shown.

[0220] The reservoir 12 is intended to contain the coloring composition (A), particularly at the beginning of the treatment.

[0221] To color hair with the process according to the invention, a volume of the coloring composition (A) is preferably used, ranging from 0.05 to 5 liters, preferably from 0.1 to 3 liters, better from 0.5 to 2 liters.

[0222] At the beginning of a treatment of a whole head of hair, the initial volume of the coloring composition (A) in the reservoir 12 is for example 1 litre.

[0223] The distribution device 10 further includes a collection tray 13 in fluidic communication with the reservoir 12. The collection tray 13 may be of the same type as those currently used in hairdressing salons, being arranged to receive the user's head and allow the treatment of their hair.

[0224] The dispensing nozzle 11 is in the form of a shower head. It has a handle enabling the user to grasp it with one hand, and a dispensing head with at least one outlet orifice, preferably several outlet orifices.

[0225] The dispensing device 10 includes a pump 14, for example peristaltic, which supplies the dispensing nozzle 11 under pressure by pumping the liquid coloring composition (A) initially present in the reservoir 12. The coloring composition (A) can then be distributed onto the hair with the dispensing nozzle 11.

[0226] The pump 14 allows the coloring composition (A) to be distributed onto the keratin fibers with a flow rate from 0.01 to 20 l / min, preferably from 0.05 to 15 l / min, more preferably from 0.1 to 10 l / min.

[0227] After the application of the coloring composition (A) to the hair, some of this liquid composition flows into the collection tray 13 by gravity, then flows, for example via a pipe, into tank 12 also by gravity. The coloring composition (A) is thus recovered in step ii) in tank 12.

[0228] The colouring composition (A) can be recycled by pumping using the pump 14 to be distributed again onto the hair by the dispensing nozzle 11.

[0229] When the user has obtained a satisfactory colouring, after possible manual rubbing, he can stop the recycling by interrupting the pump.

[0230] The coloring composition (A) is thus applied continuously to the keratin fibers, by means of the distribution device 10.

[0231] Preferably, composition (A) is applied continuously for a period of 1 to 45 minutes, more preferably 5 to 30 minutes.

[0232] At the end of the treatment, the user can drain the remaining colouring composition (A) from the reservoir 12 through a drain hole, in particular a drain plug provided in the reservoir.

[0233] If the user wishes to rinse the keratin fibers with the dispensing nozzle 11, they put water in the reservoir 12 and use the pump 14 again to rinse the hair. They can then repeat this rinsing phase as many times as necessary, emptying the reservoir again, refilling it with water, and repeating the operation of pumping the water from the reservoir 12 to dispense it onto the hair.

[0234] Alternatively, the dispensing nozzle 11 can be configured to receive, in addition to the recycled colouring composition (A), water.

[0235] The distribution nozzle 11 is thus connected, on the one hand, to the pump 14 which ensures recirculation and, on the other hand, to a mains water supply. A system of valves may be provided to allow the supply and the pipe connecting the distribution nozzle 11 to the pump 14 to be opened or closed depending on the operating phase.

[0236] According to one variant, the hairdresser initially applies the coloring composition (A) manually to the hair in step i) for example using a brush or a hot water bottle. The reservoir 12 then contains water which is distributed onto the hair with the dispensing nozzle 11, supplied by the pump 14.

[0237] Part of the colouring composition (A) rinsed with water flows into the tray 13 by gravity, then flows, via a pipe, into the reservoir 12 also by gravity. It can then be recycled in the same way as before.

[0238] The following examples serve to illustrate the invention without, however, being limiting in nature. Examples

[0239] In the following examples, all quantities are given as mass percentage of active material (AM) relative to the total weight of the composition (unless otherwise stated). Compositions

[0240] The colouring (A), pretreatment (B) and posttreatment (C) compositions were prepared from the compounds whose contents are indicated in the tables below:

[0241] Coloring compositions (A)

[0242] [Tables2] Al A2 A3 A4 A5 A5' A6 A6' HC BLUE NO. 16 0.05 BASIC YELLO W87 0.05 BASIC BROW N 17 0.05 ACID YELLO W23 0.05 ACID RED 52 0.05 0.05 ACID VIOLET 43 0.05 0.05 Benzyl alcohol 10 10 pH adjuster Qs pH Qs pH Qs pH Qs pH QspH PH 7 9.5 7.1 2.3 2.4 2.4 2.4 2.4 Water Qs 100 Qs 100 Qs 100 Qs 100 Qs 100 Qs 100 Qs 100 Qs 100

[0243] Pretreatment composition (B)

[0244] [Tables3] B THIOGLYCOLIC ACID 6 AMMONIUM HYDROXIDE Qs pH = 10 + / - 0.3 Water Qs 100

[0245] Post-processing composition (C)

[0246] [Tables4] O HYDROGEN PEROXIDE 2,4 Glycerin 1.5, Behentrimonium Chloride 0.8, Isopropyl Alcohol 0.2, Steareth-2 5.0, Phosphoric Acid Qs pH = 2.5 + / - 0.2, Stabilizing agents, Sequestering agents Qs, Water Qs 100

[0247] Evaluation 1

[0248] The process according to the invention (Protocol 1) comprising the application of a coloring composition by recirculation using the distribution device, was compared to a process in which the same coloring composition is applied statically (Protocol 2) on strands of hair that are 90% naturally white.

[0249] Protocol 1 (invention)

[0250] A distribution device 10 as described in [Fig.1] is used which delivers 400 ml / min.

[0251] 50 ml of staining composition (Al to A6) are introduced into reservoir 12.

[0252] The coloring composition from the reservoir is applied using the nozzle of distribution 11 on a strand of hair.

[0253] Part of the coloring composition is recovered in reservoir 12 and the coloring composition is applied again to the strand.

[0254] The colouring composition is thus recycled and reapplied continuously for 20 minutes, at room temperature.

[0255] After 20 minutes, the strand is rinsed with water, then washed with a standard shampoo, and dried in an oven.

[0256] The remaining colouring composition is evacuated from the reservoir.

[0257] Protocol 2 (comparative)

[0258] A strand of hair is placed in a reservoir containing 50 ml of colouring composition (Al to A6) for 20 minutes, at room temperature.

[0259] After a processing time of 20 minutes, the strand is rinsed with water, then washed with a standard shampoo, and dried in an oven.

[0260] The hair strand colouring was then evaluated.

[0261] The colorimetric measurements were carried out using a spectrocolorimeter KONICA MINOLTA-3600 (illuminant D65, angle 10°, specular component included) in the CIELab system.

[0262] 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.

[0263] The resulting color is evaluated by measuring AE, which is the color change before and after the coloring process, based on the formula: AE -

[0264] 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 hair before coloring. The color intensity increases as the AE is greater.

[0265] Results

[0266] [Tables5] L* a* b* AE Reference BN90 Untreated 60.21 0.38 11.52 A1 Protocol 2 (comparative) 37.4 -6.0 - 12.9 34.0 Protocol 1 (invention) 37.8 -5.1 - 17.6 37.1 A2 Protocol 2 (comparative) 56.81 - 1.89 53.56 42.2 Protocol 1 (invention) 56.56 -0.20 58.58 47.2 A3 Protocol 2 (comparative) 52.21 16.03 9.80 17.7 Protocol 1 (invention) 45.72 11.04 24.08 21.9 A4 Protocol 2 (comparative) 58.74 -0.56 25.98 14.6 Protocol 1 (invention) 60.94 - 1.27 31.21 19.8 A5 Protocol 2 (comparative) 49.45 12.84 - 3.04 22.0 Protocol 1 (invention) 45.92 10.82 - 6.77 25.5 A6 Protocol 2 (comparative) 48.02 0.01 - 5.12 20.6 Protocol 1 (invention) 46.12 0.82 - 7.30 23.5

[0267] The hair strands treated with the recirculating coloring process according to the invention have a higher AE value than those treated with the comparative coloring process without recirculation.

[0268] In other words, the process according to the invention allows for a better rise of the dyes than the comparative process.

[0269] Evaluation 2

[0270] The process according to the invention (Protocol 1) comprising the application of the coloring compositions A'5 and A'6 in recirculation mode, was compared to a process in which the same coloring compositions are applied in static mode (Protocol 2) on other strands of hair that are 90% naturally white.

[0271] Results

[0272] [Tableauxô] L* a* b* AE Reference BN90 Untreated 63.71 -0.37 12.32 A5' Protocol 2 (comparative) 30.97 37.51 - 17.93 58.5 Protocol 1 (invention) 24.32 29.06 - 23.09 60.6 A6' Protocol 2 (comparative) 43.07 2.36 - 14.17 33.7 Protocol 1 (invention) 24.79 12.58 - 28.76 58.0

[0273] Hair strands treated with the recirculating coloring process according to the invention have a higher AE value than those treated with the comparative coloring process without recirculation.

[0274] In other words, the process according to the invention allows for a better rise of the dyes than the comparative process.

[0275] Evaluation 3

[0276] The process according to the invention (Protocol 1') comprising the application of a colouring composition in recirculation, was compared to a process in which the same colouring composition is applied in static (Protocol 2').

[0277] Protocols 1' and 2' correspond respectively to protocols 1 and 2 with an additional pretreatment step of the strands with the pretreatment composition (B) and a posttreatment step with the posttreatment composition (C).

[0278] Pretreatment step: Composition (B) was taken and applied to a strand of hair using a pipette at a ratio of 2 g of composition (B) per 1 g of hair strand. Composition (B) was distributed over the strand using a brush. Composition (B) was left on the hair for 5 minutes and then rinsed with water.

[0279] The wick was then treated according to protocols 1 and 2 respectively.

[0280] Post-treatment step: The post-treatment composition (C) was applied to the hair strand at a ratio of 2g of composition (C) per 1g of hair strand. Composition (C) was distributed over the strand using a brush. Composition (C) was left on the hair for 5 minutes, then rinsed with water, and the hair was subsequently washed with shampoo.

[0281] The colouring was then evaluated by measuring AE corresponding to the variation in colour before and after the colouring process.

[0282] Results

[0283] [Tables7] L* a* b* AE Reference BN90 Untreated 63.71 -0.37 12.32 A5 Protocol 2' (comparative) 37.23 40.84 - 16.56 56.9 Protocol 1' (invention) 34.05 43.28 - 18.51 61.1 A6 Protocol 2' (comparative) 33.67 7.64 - 24.04 47.8 Protocol 1' (invention) 31.33 9.12 -26.71 51.6

[0284] Hair strands treated with the recirculating coloring process according to the invention have a higher AE value than those treated with the comparative coloring process without recirculation.

[0285] In other words, the process according to the invention allows for a better rise of the dyes than the comparative process.

[0286] Evaluation 4

[0287] Compositions A1 to A6 were also applied to the entire head of hair from a malleable head comprising 90% natural white hair, according to the process of the invention with the distribution device 10 as described in [Fig. 1]. The flow rate of the distribution device 10 is this time 8 l / min.

[0288] One litre of colouring composition (Al to A6) is introduced into the reservoir 12.

[0289] The coloring composition is applied, recovered and reapplied continuously for 10 to 20 minutes depending on the composition, at room temperature.

[0290] A portion of the composition is taken every 5 minutes to visually assess its colour content.

[0291] It is observed that each coloring composition clarifies within the first few minutes. In particular, a clear depletion of coloring is observed between 2 and 15 minutes for each of the compositions A1 to A6.

[0292] In addition, each of the compositions Al to A6 leads to good hair coloring.

[0293] The process according to the invention thus makes it possible to color hair effectively while reducing the amount of dyes in the rinse water.

Claims

Demands

1. A method for coloring keratin fibers, in particular human keratin fibers such as hair, comprising i) applying to said keratin fibers a coloring composition (A) comprising one or more direct dye(s) and optionally water, ii) recovering at least a portion of the coloring composition (A) after application to the keratin fibers, iii) applying the coloring composition (A) recovered in step ii) to the keratin fibers, iv) optionally rinsing the keratin fibers with water.

2. A coloring method according to the preceding claim comprising i) the application to said keratin fibers of a coloring composition (A) comprising one or more direct dye(s) and water.

3. A coloring process according to any one of the preceding claims wherein steps ii) and iii) are repeated at least once, preferably several times, better are carried out continuously, before the optional rinsing step iv).

4. A coloring method according to any one of the preceding claims wherein the application step iii) of the recovered coloring composition (A) is carried out using a dispensing device (10) comprising a pump (14) to supply a dispensing nozzle (11).

5. A coloring method according to the preceding claim in which the application step i) of the coloring composition (A) is carried out using the dispensing device (10) comprising a pump (14) to supply under pressure a dispensing nozzle (H).

6. A method according to any one of the preceding claims wherein composition (A) is recovered in step ii) in a reservoir (12).

7. A coloring process according to any one of claims 2 to 6 employing a volume of the coloring composition (A) from 0.05 to 5 l, preferably from 0.1 to 3 l, better from 0.5 to 2 l.

8. A coloring method according to any one of claims 4 to 7, wherein the coloring composition (A) is applied to the keratin fibers in step iii) and possibly in step i) by the delivery nozzle (11) with a flow rate from 0.011 / min to 20 l / min, preferably from 0.05 l / min to 15 l / min, more preferably from 0.11 / min to 10 l / min.

9. A coloring process according to any one of the preceding claims wherein steps i) to iii) are carried out for a period of 1 to 45 minutes, preferably 5 to 30 minutes.

10. A coloring process according to any one of the preceding claims wherein the total content of the direct colorant(s) in the coloring composition (A) applied in step i) is from 0.001 to 10%, preferably from 0.005 to 5% by weight, more preferably from 0.01 to 2% by weight, better from 0.02 to 1% by weight relative to the total weight of the coloring composition (A).

11. A coloring process according to any one of claims 2 to 10 wherein the total water content in the coloring composition (A) applied in step i) is from 80 to 99.999% by weight, preferably from 85 to 99.995% by weight, more preferably from 90 to 99.99% by weight, more preferably from 95% to 99.98% by weight relative to the total weight of the composition (A).

12. A coloring process according to any one of the preceding claims wherein the direct dye(s) are selected from anionic direct dyes, cationic direct dyes and non-ionic direct dyes.

13. A coloring process according to any one of the preceding claims wherein the direct dye(s) are selected from cationic direct dyes, preferably selected from azo cationic direct dyes, hydrazono cationic direct dyes, anthraquinone cationic direct dyes, triarylmethane cationic direct dyes and mixtures thereof.

14. A coloring process according to any one of claims 1 to 12, wherein the direct dye(s) are selected from anionic direct dyes, preferably from acid azo direct dyes, acid azinic direct dyes, acid triarylmethanic direct dyes, acid indoamine direct dyes, acid anthraquinone direct dyes, dyes direct acid indigoids, natural acid direct dyes, and their mixtures.

15. A coloring process according to any one of the preceding claims wherein the coloring composition (A) comprises one or more organic solvents selected from aromatic alcohols and alkylene carbonates, preferably selected from benzyl alcohol, phenethyl alcohol, cinnamic alcohol, phenylpropyl alcohol, l-phenoxy-2-propanol, phenyl diglycol, α-methylbenzyl alcohol, dimethylbenzylcarbinol, benzyloxyethanol, phenoxyethanol, phenoxyisopropanol, p-anisyl alcohol, ethylene carbonate and propylene carbonate.

16. A coloring process according to the preceding claim wherein the total content of organic solvents selected from aromatic alcohols and alkylene carbonates in the composition (A) applied in step i) ranges from 0.1 to 20% by weight, preferably from 0.5 to 15% by weight, more preferably from 1 to 13% by weight relative to the total weight of the coloring composition (A).

17. A coloring process according to any one of the preceding claims wherein the coloring composition (A) comprises less than 1%, preferably less than 0.5%, better does not contain fats and / or surfactants and / or thickening agents.

18. A coloring process according to any one of the preceding claims comprising, prior to step i) of applying the coloring composition (A), the application of a pretreatment composition (B) comprising one or more reducing agents, preferably selected from thiolated reducing agents, sulfites, bisulfites, sulfinates, phosphines, reducing sugars, their mineral and / or organic salts, and mixtures thereof, preferably thiolated reducing agents, phosphines, their mineral and / or organic salts, and mixtures thereof, and preferably from thiolated reducing agents, their mineral and / or organic salts and mixtures thereof, better from thioglycolic acid, its mineral and / or organic salts, and mixtures thereof.

19. A coloring process according to the preceding claim wherein the pretreatment composition (B) has a pH greater than or equal to 7, preferably from 8 to 12, preferably from 9 to 11, better from 9.5 to 10.

5.

20. A coloring process according to any one of the preceding claims, comprising after step iii) or after the optional rinsing step iv), v) a step of applying a post-treatment composition (C) comprising one or more chemical oxidizing agents, preferably selected from hydrogen peroxide, urea peroxide, alkali metal bromates or ferricyanides, peroxygenated salts such as alkali or alkaline earth metal persulfates, perborates and percarbonates, and peracids and their precursors; the oxidizing agent preferably being hydrogen peroxide.

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