Process for dyeing keratin materials using at least one blue, purple or green dye and at least one disulfide, thiol or protected thiol fluorescent dye

Abstract

The present invention relates to a process for dyeing keratin fibers, in particular human keratin fibers such as the hair, using a) one or more blue, violet or green dyes and b) one or more disulfide, thiol or protected-thiol fluorescent dyes. The present invention also relates to a cosmetic composition comprising the dyes defined above, and also to a multi-compartment device containing said dyes. The present invention also relates to the use of said dyes for dyeing light keratin fibers, notably human keratin fibers such as the hair, in chestnut-brown, dark chestnut-brown, brown, brown with a tint, or even black, without using an additional dye other than those defined above.

Claims

1. A process for dyeing light keratin materials, wherein the process comprises applying to the light keratin materials: a) at least one blue, violet, or green dye chosen from: a1) phenoxazinium, phenothiazinium, or phenazinium dyes; a3) triarylmethane dyes; a4) naphthoquinone or anthraquinone dyes; a5) hydrazone dyes; a6) tetraazapentamethine dyes; a7) nitro dyes; a8) azomethine dyes; a9) self-oxidizing dyes; and/or a10) oxidation dyes; and b) at least one disulfide, thiol, or protected-thiol fluorescent dye; wherein a) the at least one blue, violet, or green dye and b) the at least one disulfide, thiol, or protected-thiol fluorescent dye are applied to said keratin materials jointly or sequentially; wherein a weight ratio of a) the at least one blue, violet, or green dye to b) the at least one disulfide, thiol, or protected-thiol fluorescent dye applied to the light keratin materials ranges from 0.1 to 10; and wherein the process does not comprise using an additional dye other than the dyes a) and b).

2. The process of claim 1, wherein a) the at least one blue, violet or green dye is chosen from direct dyes chosen from: a1) phenoxazinium, phenothiazinium, or phenazinium dyes; a3) triarylmethane dyes; a4) naphthoquinone or anthraquinone dyes; a5) hydrazone dyes; a6) tetraazapentamethine dyes; a7) nitro dyes; and/or a8) azomethine dyes.

3. The process of claim 1, wherein a) the at least one blue, violet, or green dye is chosen from: a1) phenoxazinium, phenothiazinium or phenazinium dyes; a3) triarylmethane dyes; a4) naphthoquinone or anthraquinone dyes; a5) hydrazone dyes; a6) tetraazapentamethine dyes; and/or a7) nitro dyes.

4. The process of claim 1, wherein a) the at least one blue, violet, or green dye is chosen from: a1) phenoxazinium, phenothiazinium, or phenazinium dyes of formula (Ia) below, organic or mineral acid or base salts thereof, optical isomers thereof, geometrical isomers thereof, tautomers thereof, solvates thereof, or mixtures thereof: ##STR00080## wherein formula (Ia): X represents an oxygen atom, a sulfur atom, NR′.sub.2, or an ammonium radical N.sup.+R′.sub.2R′.sub.3; G represents an oxygen atom, a sulfur atom or a radical NR.sub.6; R.sub.2, R.sub.3, R′.sub.2 and R′.sub.3, which may be identical or different, represent, independently of each other: a hydrogen atom, a phenyl radical which is optionally substituted with one or more halogen atoms, or a linear or branched C.sub.1 to C.sub.20 alkyl radical, wherein the alkyl radical is: optionally substituted with one or more groups chosen from hydroxyl, (di)(C.sub.1-C.sub.4)(alkyl)amino, amino —NH.sub.2, (di)(C.sub.1-C.sub.4)(alkyl)aminocarbonyl, aminocarbonyl —C(O)NH.sub.2, and 5- or 6-membered heterocycloalkyl, optionally interrupted with one or more heteroatoms or with one or more groups comprising at least one heteroatom; R.sub.5 and R′.sub.5, which may be identical or different, represent: a hydrogen atom, a linear or branched C.sub.1 to C.sub.6 alkyl radical, an optionally substituted phenyl radical, a hydroxycarbonyl or carboxyl radical —C(O)—OH, a carboxylate radical —C(O)—O.sup.−, a (di)(C.sub.1-C.sub.6)(alkyl)aminocarbonyl radical, an aminocarbonyl radical —C(O)NH.sub.2, a (di)(C.sub.1-C.sub.6)(alkyl)amino radical, or an amino radical, R.sub.1, R.sub.4, R′.sub.1 and R′.sub.4, which may be identical or different, represent, independently of each other: a hydrogen atom, a C.sub.1 to C.sub.4 alkyl radical, a C.sub.1 to C.sub.4 alkoxy radical, a hydroxyl radical, an amino radical R.sub.7R.sub.8N— with R.sub.7 and R.sub.8, which may be identical or different, representing a hydrogen atom, a (C.sub.1-C.sub.4)alkyl group, or a phenyl radical which is optionally substituted with one or more halogen atoms or nitro(so) groups, or a nitro(so) radical; or alternatively R.sub.4 forms, with one of the substituents R.sub.2 or R.sub.3, a saturated or unsaturated, optionally substituted heterocycle; R.sub.6 represents a phenyl radical which is optionally substituted with a (di)(C.sub.1-C.sub.4)(alkyl)amino radical and/or a linear or branched C.sub.1 to C.sub.6 alkyl radical; wherein when the compound of formula (Ia) is cationic, it optionally comprises one or more anions Y.sup.− and optionally one or more cations M.sup.+to ensure the electrical neutrality of the molecule, with Y.sup.− represents an anionic counterion or a mixture of organic or mineral anions; M.sup.+ represents an organic or mineral cationic counterion; a3) the triarylmethane dyes chosen from the compounds of formula (IVa) below, optical isomers thereof, geometrical isomers thereof, tautomers thereof, organic or mineral, acid or base salts thereof, solvates thereof, or mixtures thereof: ##STR00081## in which formula (IVa), R.sub.1, R.sub.2, R′.sub.1 and R′.sub.2, which may be identical or different, represent: a hydrogen atom, a linear or branched C.sub.1 to C.sub.20 alkyl radical, that is optionally substituted and/or optionally interrupted with one or more heteroatoms, or a benzyl radical optionally substituted with one or more SO.sub.3.sup.− or SO.sub.3H groups; R.sub.3 and R′.sub.3, which may be identical or different, represent, independently of each other: a linear or branched C.sub.1 to C.sub.6 alkyl radical, a sulfonate group SO.sub.3.sup.−, or a sulfonic group SO.sub.3H; n and m, which may be identical or different, represent two integers ranging from 0 to 4; the radicals R.sub.4, which may be identical or different, represent, independently of each other: a linear or branched C.sub.1 to C.sub.6 alkyl radical, a hydroxyl radical, an SO.sub.3.sup.− group, an SO.sub.3H group, a halogen atom, or alternatively two adjacent radicals R.sub.4 together form an unsaturated 6-membered ring, optionally substituted with one or more SO.sub.3.sup.− or SO.sub.3H; q is an integer ranging from 0 to 4; R.sub.5 represents: a hydrogen atom, a halogen atom, an amino radical, a hydroxyl radical, a group which is electron-withdrawing via the mesomeric effect, or a radical —NR.sub.6R.sub.7, in which R.sub.6 and R.sub.7, which may be identical or different, represent, independently of each other: a hydrogen atom, a linear or branched C.sub.1 to C.sub.6 alkyl radical; wherein: the radical R.sub.2 is present or absent, symbolized by the dashed bond, when R.sub.2 is present, the nitrogen atom that bears it is in cationic ammonium form, when R.sub.2 is absent, the nitrogen atom that bears it is not charged, (+) is not present, and the compound of formula (IVa) optionally comprises one or more anions An.sup.− and optionally one or more cations M.sup.+to ensure the electrical neutrality of the molecule; with: An.sup.− representing an anionic counterion; and M.sup.+ representing a cationic counterion; a4) naphthoquinone or anthraquinone dyes chosen from the compounds of formula (Va) to (VI′a) below, optical isomers thereof, the geometrical isomers thereof, tautomers thereof, the organic or mineral, acid or base salts thereof the solvates thereof, or mixtures thereof: ##STR00082## wherein in formulae (Va), (VIa), and (VI′a): X.sub.a represents an oxygen atom or a group N—R with R representing a hydrogen atom or a group from among (C.sub.1-C.sub.6)alkyl, optionally substituted (hetero)aryl or (hetero)aryl(C.sub.1-C.sub.6)alkyl; Y represents: i) a hydrogen atom; ii) an alkali metal; iii) an alkaline-earth metal; iv) an ammonium group: N.sup.+R.sup.aR.sup.bR.sup.gR.sup.d or a phosphonium group: P.sup.+R.sup.aR.sup.bR.sup.gR.sup.d with R.sup.a, R.sup.b, R.sup.g and R.sup.d, which may be identical or different, representing a hydrogen atom or a (C.sub.1-C.sub.4)alkyl group; or v) a thiol-function protecting group; or vi) the group (b) below: ##STR00083## R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.1′, R.sub.2′, R.sub.3′ and R.sub.4′, which may be identical or different, represent an atom or group chosen from: hydrogen; halogen, hydroxyl, C.sub.1-C.sub.4 alkoxy, hydroxysulfonyl (˜SO.sub.3H) or sulfonate (˜SO.sub.3.sup.−, M.sup.+), with M.sup.+ representing a cationic counterion, optionally substituted C.sub.1-C.sub.6 alkyl, —NR.sub.5R.sub.6 in which R.sub.5 and R.sub.6, which may be identical or different, represent an atom or radical chosen from: i) hydrogen, ii) (C.sub.1-C.sub.4), iii) arylsulfonyl, iv) Het-ALK-C(O)— with Het representing a heterocycloalkyl group which is optionally substituted with one or more (C.sub.1-C.sub.4)alkyl groups and ALK represents a (C.sub.1-C.sub.6)alkylene group optionally substituted with one or more hydroxyl or (di)(hydroxy)(C.sub.1-C.sub.4)(alkyl)amino groups; v) optionally substituted aryl, optionally substituted with at least one radical chosen from a) C.sub.1-C.sub.6 alkyl, b) hydroxyl, c) hydroxysulfonyl, d) C.sub.1-C.sub.4 alkoxy, e) carboxyl (—COOH), f) (C.sub.1-C.sub.4)alkoxycarbonyl, g) amino, h) (di)(C.sub.1-C.sub.4)alkylamino, one of the alkyl radicals optionally substituted with a hydroxyl or hydroxysulfonyl radical —SO.sub.3H, or —OSO.sub.3H, vi) optionally substituted aryl(C.sub.1-C.sub.4)alkyl, viii) optionally substituted C.sub.1-C.sub.20 alkyl, optionally interrupted with one or more heteroatoms and/or with one or more groups comprising at least one heteroatom, when said alkyl radical is substituted, it is substituted with one or more atoms or groups chosen from: a) halogens, b) hydroxyl, c) (C.sub.1-C.sub.6)alkylcarbonylamino, d) 5- or 6-membered heterocycloalkyl e) (di)(C.sub.1-C.sub.4)(alkyl)amino, f) hydroxysulfonyl(C.sub.1-C.sub.4)alkylamino, or hydroxysulfonyloxy(C.sub.1-C.sub.4)alkylamino, g) (di)(hydroxy)(C.sub.1-C.sub.4)(alkyl)amino, h) 5- or 6-membered heteroaryl, and i) formylamino (˜NHCOH); group (a): —N(R.sub.7)—X.sub.1—W.sub.1 (a) wherein in group (a): R.sub.7 represents a hydrogen or a C.sub.1-C.sub.4 alkyl radical, X.sub.1 represents a divalent radical chosen from C.sub.1-C.sub.20 alkylene optionally interrupted with one or more heteroatoms or groups chosen from oxygen, nitrogen and sulfur, CO, SO, SO.sub.2, arylene, or combinations thereof; W.sub.1 represents a cationic radical chosen from: ##STR00084## with R.sub.8, R.sub.9, R.sub.10 and R.sub.11, which may be identical or different, representing a C.sub.1-C.sub.6 alkyl group, a benzyl radical, a C.sub.1-C.sub.6 alkyl sulfonate radical; the radicals R.sub.8 and R.sub.9 optionally form, with the nitrogen atom to which they are attached, a saturated or unsaturated, optionally substituted 5- to 7-membered heterocycle, optionally comprising another non-nitrogen heteroatom, An.sup.− represents an anionic counterion; T.sub.1 represents a linear or branched divalent hydrocarbon-based chain comprising from 1 to 20 carbon atoms, optionally interrupted with one or more heteroatoms or groups, or combinations thereof, chosen from oxygen, sulfur, N(R.sub.b), C(O), —N.sup.+(R.sub.8)(R.sub.9)-An, optionally cationic and optionally substituted heteroaryl, An with R.sub.8 and R.sub.9, which may be identical or different, representing a C.sub.1-C.sub.6 alkyl radical; R.sub.b representing a hydrogen atom or a (hydroxy)(C.sub.1-C.sub.4)alkyl group; n is an integer ranging from 1 to 3; ##STR00085## being the part of the bond that is connected to the rest of the molecule; wherein: the naphthoquinone and anthraquinone dye(s) of formula (Va), (VIa) or (VI′a) include at least one radical R.sub.1, R.sub.3, R.sub.4, R.sub.1′, R.sub.3′, or R.sub.4′, other than a hydrogen atom; and when the compounds of formula (Va), (VIa) or (VI′a) are cationic, they comprise an anionic counterion An or An.sup.− to ensure the electrical neutrality, or they comprise a sulfonate group, and M.sup.+ and An or An.sup.− may be absent to ensure the electrical neutrality of the molecule; and/or a5) hydrazone dyes, chosen from the compounds of formula (Vila) below, the geometrical isomers thereof, the tautomers thereof, the organic or mineral, acid or base salts thereof, the solvates thereof, and mixtures thereof: ##STR00086## in which formula (VIIa): R.sub.1, which may be identical or different, represent: an optionally substituted C.sub.1-C.sub.20 alkyl radical, optionally interrupted with one or more heteroatoms and/or with one or more groups comprising at least one heteroatom; a C.sub.1-C.sub.4 trialkylsilyl radical; an optionally substituted phenyl radical; an optionally substituted benzyl radical; R′.sub.1, which may be identical or different, represents: a halogen atom; an optionally substituted C.sub.1-C.sub.16 alkyl radical; a hydroxyl radical; a C.sub.1-C.sub.4 alkoxy radical; an amino radical optionally substituted with one or two identical or different C.sub.1-C.sub.4 alkyl radicals, optionally bearing at least one hydroxyl group; an alkylcarbonylamino radical (RCO—NR′—) in which the radical R represents a C.sub.1-C.sub.4 alkyl radical and R′ represents a hydrogen or a C.sub.1-C.sub.4 alkyl radical; an alkylcarbonylamino group (RSO.sub.2—NR′—) in which the radical R represents a C.sub.1-C.sub.4 alkyl radical and the radical R′ represents a hydrogen atom or a C.sub.1-C.sub.4 alkyl radical; two adjacent radicals R′1 may form, together with the carbon atoms to which they are attached, a saturated or unsaturated, substituted or unsubstituted 5- or 6-membered aromatic or non-aromatic (hetero)cyclic radical; p is an integer between 0 and 4; R.sub.2, which may be identical or different, represents: a hydrogen atom, an optionally substituted (hetero)aryl radical; an optionally substituted C.sub.1-C.sub.16 alkyl radical; two adjacent radicals R.sub.2 may form an optionally substituted, saturated or unsaturated, 5- to 7-membered (hetero)cycle, optionally fused to another aromatic nucleus, optionally comprising another nitrogen or non-nitrogen heteroatom; is an integer equal to 0, 1, 2, 3, or 4; n is an integer equal to 1 or 2; R.sub.3 represents: a hydrogen; an optionally substituted C.sub.1-C.sub.20 alkyl radical; a halogen atom; a hydroxyl group; a C.sub.1-C.sub.4 alkoxy group; an alkoxycarbonyl group (RO—CO—) in which R represents a C.sub.1-C.sub.4 alkyl radical; an alkylcarbonyl radical (RCO—O—) in which R represents a C.sub.1-C.sub.4 alkyl radical; an optionally substituted aryloxy group; a group NR′.sub.3R″.sub.3 in which R′.sub.3 and R″.sub.3 represent, independently of each other: i) a hydrogen atom, ii) a C.sub.1-C.sub.4 alkyl radical, optionally bearing at least one hydroxyl or C.sub.1-C.sub.2 group, said alkyl radicals optionally forming, with the nitrogen atom to which they are attached, and optionally aromatic, optionally substituted, saturated or unsaturated, 5- or 7-membered heterocycle, optionally comprising another nitrogen or non-nitrogen heteroatom; a phenylamino radical; an aminophenylamino radical; a 4-N,N-diethylaminophenylamino radical; a methoxyphenylamino radical; an alkylcarbonylamino group (RCO—NR′—) in which the radical R represents a C.sub.1-C.sub.4 alkyl radical and the radical R′ represents a hydrogen atom or a C.sub.1-C.sub.4 alkyl radical; a ureido group (N(R).sub.2—CO—NR′—) in which the radicals R and R′, independently of each other, represent a hydrogen atom or a C.sub.1-C.sub.4 alkyl radical; an alkylthio radical (R—S—) in which the group R represents a C.sub.1-C.sub.4 alkyl radical; two adjacent radicals R.sub.3 may form, together with the carbon atoms to which they are attached, a substituted or unsubstituted 5- or 6-membered aromatic or non-aromatic (hetero)cyclic radical; q is an integer between 0 and 5; and one of the radicals R′.sub.3 or R″.sub.3 optionally forms, with the nitrogen atom to which it is attached and with a carbon atom of the aromatic nucleus located ortho to the NR′.sub.3R″.sub.3 group, a substituted or unsubstituted, 5- or 6-membered saturated or unsaturated heterocycle; An represents an anionic counterion or a mixture of organic or inorganic anions which ensure the electrical neutrality of the compounds of formula (VIIa); a6) tetraazapentamethine dyes, chosen from the compounds of formula (VIIIa) and/or (IXa) below, geometrical isomers thereof, tautomers thereof, organic or mineral, acid or base salts thereof, solvates thereof, or mixtures thereof: ##STR00087## in which formulae (VIIIa) and (IXa): R.sub.4 and R′.sub.4, which may be identical or different, represent: a linear or branched C.sub.1-C.sub.8 alkyl radical optionally substituted with one to three radicals chosen from hydroxyl, C.sub.1-C.sub.2 alkoxy, C.sub.2-C.sub.4 (poly)hydroxyalkoxy, amino, C.sub.1-C.sub.2 (di)alkylamino, or carboxyl radicals; R.sub.5, R′.sub.5, R.sub.6 and R′.sub.6, which may be identical or different, represent: a hydrogen atom, a linear or branched C.sub.1-C.sub.16 hydrocarbon-based chain, this chain optionally being saturated or unsaturated with 1 to 3 unsaturations, this chain being unsubstituted or substituted with one to 3 radicals chosen from hydroxyl, C.sub.1-C.sub.2 alkoxy, (poly)hydroxy(C.sub.2-C.sub.4)alkoxy, amino, C.sub.1-C.sub.2 (di)alkylamino, carboxyl, sulfonylamino, (poly)hydroxy(C.sub.2-C.sub.4)alkylamino or a halogen atom; a phenyl radical optionally substituted with one to three radicals chosen from hydroxyl, C.sub.1-C.sub.2 alkoxy, (poly)hydroxy(C.sub.2-C.sub.4)alkoxy, amino and C.sub.1-C.sub.2 (di)alkylamino, carboxyl, sulfonylamino and (poly)hydroxy(C.sub.2-C.sub.4)alkylamino radicals, or a halogen atom; a heteroaryl radical chosen from pyrazolyl, pyrrolyl, imidazolyl, thiazolyl, oxazolyl, triazolyl, pyridyl, pyrimidinyl, triazinyl, pyrazinyl, or pyridazinyl radicals, wherein the hydrocarbon-based chain is optionally interrupted with one or two oxygen, nitrogen or sulfur atoms or with an SO2 radical, it being understood that R.sub.5, R′.sub.5, R.sub.6 and R′.sub.6 do not include any peroxide bonds, or any diazo or nitroso radicals, An represents an anionic counterion or a mixture of organic or inorganic anions which ensure the electrical neutrality of the compounds of formula (VIIIa) or (IXa); a7) nitro dyes, chosen from the compounds of formula (Xa) below, geometrical isomers thereof, tautomers thereof, organic or mineral, acid or base salts thereof, solvates thereof, or mixtures thereof: ##STR00088## in which formula (Xa): R.sub.7, R′.sub.7, R.sub.8 and R′.sub.8, which may be identical or different, represent: a hydrogen atom, a linear or branched C.sub.1-C.sub.18 hydrocarbon-based chain, this chain optionally being saturated or unsaturated with one to four unsaturations, this chain being unsubstituted or substituted with one to three radicals chosen from hydroxyl, C.sub.1-C.sub.2 alkoxy, (poly)hydroxy(C.sub.2-C.sub.4)alkoxy, amino, C.sub.1-C.sub.2 (di)alkylamino, carboxyl, sulfonylamino, (poly)hydroxy(C.sub.2-C.sub.4)alkylamino or a halogen atom, hydroxycarbonyl, hydroxysulfonyl, aminocarbonylmethyl, piperidyl, carbonylamino, aminocarbonylamino, chloromethylcarbonylamino, (C.sub.1-C.sub.2)alkoxycarbonyl, imidazolyl; a phenyl radical optionally substituted with one to three radicals chosen from hydroxyl, C.sub.1-C.sub.2 alkoxy, (poly)hydroxy(C.sub.2-C.sub.4)alkoxy, amino, C.sub.1-C.sub.2 (di)alkylamino, carboxyl, sulfonylamino and (poly)hydroxy(C.sub.2-C.sub.4)alkylamino radicals, or a halogen atom; R.sub.9 represents: a hydrogen; an optionally substituted C.sub.1-C.sub.20 alkyl radical; a halogen atom; a C.sub.1-C.sub.4 alkoxy group; an alkylcarbonyl radical (RCO—O—) in which R represents a C.sub.1-C.sub.4 alkyl radical; a phenyl radical; a8) azomethine dyes and the leuco forms thereof, chosen from the compounds of formula (XIa) and/or (XIIa) below, geometrical isomers thereof, tautomers thereof, organic or mineral, acid or base salts thereof, solvates thereof, and mixtures thereof: ##STR00089## in which formulae (XIa) and (XIIa): Z.sub.1 and Z′.sub.1, which may be identical or different, represent: a covalent single bond, an oxygen atom, a radical —NR.sub.12(R.sub.13)p-, with p being equal to 0 or 1, and when p is equal to 0 then R.sub.12 represents a hydrogen atom or a C.sub.1-C.sub.6 alkyl radical, or R.sub.12, with Rio, form, together with the nitrogen atom to which they are attached, a substituted or unsubstituted, saturated or unsaturated, aromatic or nonaromatic, 5- to 8-membered heterocycle, optionally containing one or more heteroatoms or groups chosen from N, O, S, SO.sub.2 and —CO—, and when p is equal to 1, —NR.sub.12R.sub.13— is a cationic radical in which R.sub.12 and R.sub.13 independently represent an alkyl radical, Z.sub.1 and/or Z′.sub.1 may also represent a divalent radical —S—, —SO— or —SO.sub.2— when R.sub.1 is a methyl radical; R.sub.10 and R′.sub.10 represent, independently of each other: a hydrogen; an optionally substituted C.sub.1-C.sub.1 alkyl radical optionally interrupted with a heteroatom or a group chosen from O, N, Si, S, SO and SO.sub.2, a C.sub.1-C.sub.1 alkyl radical substituted and/or interrupted with a cationic radical, a halogen; an SO.sub.3H radical, a substituted or unsubstituted, saturated, unsaturated or aromatic, 5- to 8-membered ring, optionally containing one or more heteroatoms or groups chosen from N, O, S, S(O).sub.2 and —CO—, the ring optionally being cationic and/or substituted with a cationic radical, when Z.sub.1 and/or Z′.sub.1 represent a covalent bond, then R.sub.1 may also represent a radical: 1) optionally substituted C.sub.1-C.sub.6 alkylcarbonyl —O—C(O)—R, —C(O)—O—R, —N(R)—C(O)—R′ or —C(O)—NRR′ in which R and R′ independently represent a hydrogen atom or ii) an optionally substituted C.sub.1-C.sub.6 alkyl radical; R.sub.9 and R′.sub.9, which may be identical or different, represent: a hydrogen atom, a hydroxyl radical; a C.sub.1-C.sub.6 alkoxy radical, a C.sub.1-C.sub.6 alkylthio radical; an amino radical; a monoalkylamino radical; a C.sub.1-C.sub.6 dialkylamino radical in which the alkyl radicals optionally form, with the nitrogen atom to which they are attached, a saturated or unsaturated, aromatic or nonaromatic, 5- to 8-membered heterocycle, which optionally contains one or more heteroatoms or groups chosen from N, O, S, SO.sub.2 and CO; an optionally substituted C.sub.1-C.sub.6 alkylcarbonyl radical; a radical —O—C(O)—R, —C(O)—O—R, N(R)—C(O)—R′ or —C(O)—NRR′ with R and R′ as defined previously; a halogen; an —NHSO.sub.3H radical; an optionally substituted C.sub.1-C.sub.4 alkyl radical; a saturated, unsaturated or aromatic, optionally substituted carbon-based ring; or two radicals R.sub.9, and/or two radicals R′9 may form in pairs a saturated or unsaturated ring, m and m′ are integers ranging from 0 to 4, n and n′ are integers ranging from 0 to 4 when U and/or U′ represent a carbon atom and from 0 to 3 when U and/or U′ represent(s) a nitrogen atom U and/or U′ represent a carbon atom substituted with a radical R.sub.11 and/or R′.sub.11, X and/or X′ represent: an oxygen atom; an NH radical; the radicals R.sub.11 and/or R′.sub.11, which may be identical or different, represent, independently of each other: a hydrogen; an amino radical; a linear or branched C.sub.1-C.sub.4 alkyl radical; an alkoxy radical —OR in which R represents a C.sub.1-C.sub.4 alkyl radical optionally substituted with a hydroxyl; a halogen chosen from chlorine, fluorine and bromine; a radical —NR.sub.13 in which R.sub.13 represents a linear C.sub.1-C.sub.4 alkyl optionally substituted with a hydroxyl, with a di(C.sub.1-C.sub.3)alkylamino or with a tri(C.sub.1-C.sub.3)alkylammonium.

5. The process of claim 4, wherein a) the at least one blue, violet, or green dye is chosen from the following dyes: ##STR00090## ##STR00091## wherein An represents a halide, and M.sup.+ represents a cationic counterion.

6. The process of claim 1, wherein a) the at least one blue, violet or green dye is chosen from a9) self-oxidizing dyes of formulae (I′a) to (IV′a) below: ##STR00092## and organic or mineral acid or base salts thereof, optical isomers, geometrical isomers and tautomers thereof, or solvates thereof; wherein in formulae (I′a) to (IV′a): represents a single bond or a double bond; X represents i) an amino radical, ii) a C.sub.1-C.sub.6 (di)alkylamino radical which may optionally be substituted with one or more hydroxyl, C.sub.1-C.sub.6 alkoxy, amino, C.sub.1-C.sub.6 alkylamino, carboxylic (—CO.sub.2H) or sulfonic (—SO.sub.3H) radicals; iii) a hydroxyl radical; R.sub.1 represents a radical covalently bonded to a carbon atom, chosen from: i) hydroxyl, ii) thiol —SH, iii) (di)(C.sub.1-C.sub.12 alkyl)amino the alkyl groups of which may optionally be substituted with one or more radicals from among: a) hydroxyl, b) C.sub.1-C.sub.6 alkoxy, c) amino, d) amide (—CONH.sub.2), e) C.sub.1-C.sub.6 (di)alkylamino, f) carboxylic (—CO.sub.2H), g) sulfonic (—SO.sub.3H), h) piperidine, i) pyridine, j) pyrrolidine, k) morpholine, l) C.sub.1-C.sub.6 N-alkyl piperazino, m) benzene, n) halogen, o) nitrile, p) tetrahydrofuran, q) C.sub.1-C.sub.6 N-alkyl pyrrolidine, r) imidazole, s) C.sub.1-C.sub.6 trialkylammonium, t) C.sub.1-C.sub.6 N-alkylimidazolium, u) C.sub.1-C.sub.6 N,N dialkylpiperazinium, v) C.sub.1-C.sub.6 N,N dialkylpiperazinium, w) C.sub.1-C.sub.6 N-alkyl,N′-alkyl piperazinium, x) C.sub.1-C.sub.6 N-alkylpiperidinium, y) C.sub.1-C.sub.6 N-alkylmorpholinium, z) C.sub.1-C.sub.6 N-alkylpyrrolidinium, aa) C.sub.1-C.sub.6 N-alkylpyridinium, ab) C.sub.1-C.sub.6 (di)alkylacetamido, ac) NHSO.sub.2R.sub.2, ad) C.sub.1-C.sub.6 alkylcarbonyl, ae) urea (—NHCONH.sub.2), af) acetamido CH.sub.3CONH—, ag) -aminocarbonyl —CONH.sub.2, iv) C.sub.1-C.sub.6 alkyl which may be optionally substituted with one or more radicals a) to ag) as defined for iii) above; v) C.sub.1-C.sub.6 alkyloxy are optionally substituted with one or more radicals a) to ag) as defined for iii) above, the alkyl chain of the alkoxy optionally being interrupted with one or more oxygen atoms; vi) C.sub.1-C.sub.6 alkylthio are optionally substituted with one or more radicals a) to ag) as defined for iii) above; vii) halogen; viii) —NHPh; ix) arylthio —S-Ph; x) aryloxy; xi) —NHCOR.sub.2; xii) —OCOR.sub.2; xiii) —SCOR.sub.2; xiv) —NHCONHR.sub.2; xv) —NHCSNHR.sub.2; xvi) —NHSO.sub.2R.sub.2; xvii) —OSO.sub.2R.sub.2; xviii) —SOR.sub.2; xix) —SO.sub.2R.sub.2; xx) —SO.sub.2NHR.sub.2; xxi) piperidino which may be functionalized with one or more —CONH.sub.2, C.sub.1-C.sub.6 alkyl which is optionally functionalized with a hydroxyl or C.sub.1-C.sub.6 N-alkylimidazolium radical; a pyrrolidino radical which is optionally functionalized with one or more hydroxyl, C.sub.1-C.sub.6 alkyl, —NHR.sub.2, amino, C.sub.1-C.sub.6 trialkylammonium, C.sub.1-C.sub.6 N-alkylimidazolium or (di)(C.sub.1-C.sub.6)alkylamino radicals; xxii) piperazino which may be functionalized with one or more C.sub.1-C.sub.6 alkyl radicals; xxiii) C.sub.1-C.sub.6 N,N-dialkylpiperazinium; xxiv) diazepane; xxv) morpholino; xxvi) azepane; xxvii) —CO.sub.2R.sub.2; xxviii) —SO.sub.3R.sub.2; xxix) —CONHR.sub.2; xxx) nitrile (—CN); xxxi) —NHCO.sub.2R.sub.2; xxxii) —COR.sub.2; xxxiii) —NHCNHNH.sub.2; a phenyl radical; R.sub.2 represents i) a hydrogen atom, ii) a C.sub.1-C.sub.12 alkyl radical, iii) a phenyl radical, or iv) a 4-methylphenyl radical; n represents an integer between 1 and 6; Y represents a carbon or a nitrogen atom; Z represents i) a carbon atom, ii) an oxygen atom, iii) a nitrogen atom, iv) a radical —NR.sub.3 in which R.sub.3 represents: a hydrogen atom; a C.sub.1-C.sub.6 alkyl radical which is optionally substituted with one or more hydroxyl, C.sub.1-C.sub.6 alkoxy, amino, C.sub.1-C.sub.6 alkylamino, carboxylic (—CO.sub.2H) or sulfonic (—SO.sub.3H) radicals; wherein: when n is greater than or equal to two, the radicals R.sub.1 are identical or different; when the compounds of formulae (I′a) to (IV′a) comprise a cationic group, it is combined with an anionic counterion to achieve the electrical neutrality of the molecule, the compounds of formula (I′a) contain at least three substituents chosen from X and R.sub.1 which are electron-donating via the mesomeric effect (+M); the compounds of formula (II′a) or (III′a) contain at least two substituents chosen from X and R.sub.1 which are electron-donating via the mesomeric effect (+M); for formula (II′a), X or R.sub.1 are bonded to the carbon atoms 1 to 4 or 6 to 9; for formula (III′a) or (IV′a), X or R.sub.1 are bonded to the carbon atoms 1, 2 and 5 to 8 or to a carbon or nitrogen atom 3.

7. The process of claim 1, wherein the at least one blue, violet, or green dye a) is chosen from a10) oxidation dyes chosen from one or more oxidation bases chosen from para-phenylenediamines, bis(phenyl)alkylenediamines, ortho-aminophenols, heterocyclic bases, or the corresponding addition salts, and optionally combined with one or more coupling agents.

8. The process of claim 1, wherein b) the at least one disulfide, thiol, or protected-thiol fluorescent dye is chosen from those of formula (Ib):
A-(X).sub.p—C.sub.sat—S—U, organic or mineral acid or base salts thereof, optical and geometric isomers thereof, tautomers thereof, or solvates thereof, wherein in formula (Ib): U represents a radical chosen from: a) —S—C′.sub.sat—(X′).sub.p′-A′; and b) —Y; A and A′, which may be identical or different, represent a radical containing at least one quaternized cationic fluorescent chromophore or at least one fluorescent chromophore bearing a quaternized or quaternizable cationic group; Y represents i) a hydrogen atom; or ii) a thiol-function-protecting group; X and X′, which may be identical or different, represent a linear or branched, saturated or unsaturated divalent C.sub.1-C.sub.30 hydrocarbon-based chain, optionally interrupted and/or optionally terminated at one or both of its ends with one or more divalent groups or combinations thereof chosen from: —N(R)—, —N.sup.+(R)(R)—, —O—, —S—, —C(O)—, —S(O)— and —SO.sub.2—, with R, which may be identical or different, chosen from a hydrogen and a C.sub.1-C.sub.4 alkyl, hydroxyalkyl, or aminoalkyl radical; an aromatic or non-aromatic, saturated or unsaturated, fused or non-fused (hetero)cyclic radical optionally comprising one or more identical or different, optionally substituted heteroatoms; p and p′, which may be identical or different, are equal to 0 or 1; C.sub.sat and C′.sub.sat, which may be identical or different, represent an optionally substituted linear or branched, or cyclic, C.sub.1-C.sub.18 alkylene chain.

9. The process of claim 8, wherein the at least one fluorescent dye of formula (Ib) is such that, when p and/or p′ is equal to 1, X and/or X′, which may be identical or different, represent the following sequence: -(T).sub.t-(Z).sub.z-(T′).sub.t′-, the sequence being bonded in formula (Ib) symmetrically as follows:—C.sub.sat (or C′.sub.sat)-(T).sub.t-(Z).sub.z-(A or A′); wherein: T and T′, which may be identical or different, represent one or more radicals or combinations thereof chosen from: —O—; —S—; —N(R)—; —N.sup.+(R)(R.sup.o)—; —S(O)—; —S(O).sub.2—; —C(O)—; with R, R.sup.o, which may be identical or different, representing a hydrogen atom, a C.sub.1-C.sub.4 alkyl radical, C.sub.1-C.sub.4 hydroxyalkyl radical or an aryl(C.sub.1-C.sub.4)alkyl radical; and a cationic or non-cationic heterocycloalkyl or heteroaryl radical; the indices t and t′, which may be identical or different, are equal to 0 or 1; Z represents: —(CH.sub.2).sub.m— with m an integer between 1 and 8; —(CH.sub.2CH.sub.2O).sub.q— or —(OCH.sub.2CH.sub.2).sub.q— in which q is an integer between 1 and 5 inclusive; an aryl, alkylaryl or arylalkyl radical in which the alkyl radical is C.sub.1-C.sub.4, being optionally substituted with at least one group SO.sub.3M with M representing a hydrogen atom, an alkali metal or an ammonium group substituted with one or more identical or different, linear or branched C.sub.1-C.sub.18 alkyl radicals optionally bearing at least one hydroxyl; z is equal to 0 or 1.

10. The process of claim 8, wherein the at least one disulfide, thiol, or protected-thiol fluorescent dye of formula (Ib) is such that A and/or A′ are chosen from chromophores derived from acridine, acridone, benzanthrone, benzimidazole, benzimidazolone, benzindole, benzoxazole, benzopyran, benzothiazole, coumarin, difluoro{2-[(2H-pyrrol-2-ylidene-kN)methyl]-1H-pyrrolato-kN}boron (BODIPY®), diketopyrrolopyrrole, fluorindine, (poly)methine, naphthalimide, naphthanilide, naphthylamine, oxadiazole, oxazine, perilone, perinone, perylene, polyene/carotenoid, squarane, stilbene and xanthene fluorescent dyes; wherein (poly)methine or naphthalimides are chosen from: formulae (IIb) and (IIIb) below:
W.sup.+-[C(R.sup.c)═C(R.sup.d)].sub.m′-Ar′-(*)Q.sup.−  (IIb)
Ar-[C(R.sup.d)═C(R.sup.c)].sub.m′—W′.sup.+-(*)Q.sup.−  (IIIb) with, in formula (IIb) or (IIIb): W.sup.+ representing a cationic heterocyclic or heteroaryl group; W′.sup.+ representing a divalent heterocyclic or heteroaryl radical as defined for W.sup.+; Ar representing an aryl group, optionally substituted with i) one or more halogen atoms; ii) one or more groups (C.sub.1-C.sub.8)alkyl; iii) one or more hydroxyl groups; iv) one or more (C.sub.1-C.sub.8)alkoxy groups; v) one or more hydroxy(C.sub.1-C.sub.8)alkyl groups, vi) one or more amino or (di)(C.sub.1-C.sub.8)alkylamino groups, vii) one or more acylamino groups; viii) one or more heterocycloalkyl groups; Ar′ is a divalent aryl radical as defined for Ar; m′ represents an integer between 1 and 4 inclusive; R.sup.c, R.sup.d, which may be identical or different, represent a hydrogen atom or an optionally substituted (C.sub.1-C.sub.8)alkyl group, por alternatively R.sup.c contiguous with W.sup.+or W′+ and/or R.sup.d contiguous with Ar or Ar″ form, with the atoms that bear them, a (hetero)cycloalkyl; Q.sup.− is an organic or mineral anionic counterion; (*) represents the part of the chromophore bonded to the rest of formula (Ib); or formula (IVb) or (Vb): ##STR00093## wherein formulae (IVb) and (Vb): R.sup.e, R.sup.f, R.sup.g and R.sup.h, which may be identical or different, represent a hydrogen atom or a C.sub.1-C.sub.6 alkyl group which is optionally substituted; ##STR00094## representing the bond which bonds the naphthalimidyl radical to the rest of the molecule via X or X′, if p=1, or p′=1; or via C.sub.sat or C.sub.sat′, if p=0 or p′=0.

11. The process of claim 1, wherein b) the at least one disulfide, thiol, or protected-thiol fluorescent dye a) is chosen from the dyes of formulae (VIb) to (Xb′) below: ##STR00095## ##STR00096## organic or mineral acid or base salts thereof, optical and geometric isomers thereof, tautomers thereof, or solvates thereof; wherein in formulae (VIb) to (Xb′): G and G′, which may be identical or different, represent a group —NR.sub.cR.sub.d, —NR′.sub.cR′.sub.d or C.sub.1-C.sub.6 alkoxy which is optionally substituted; R.sub.a and R′.sub.a, which may be identical or different, represent an aryl(C.sub.1-C.sub.4)alkyl group or a C.sub.1-C.sub.6 alkyl group optionally substituted with a hydroxyl or amino, C.sub.1-C.sub.4 alkylamino or C.sub.1-C.sub.4 dialkylamino group, said alkyl radicals optionally forming, with the nitrogen atom that bears them, a 5- to 7-membered heterocycle, optionally comprising another nitrogen or non-nitrogen heteroatom; R.sub.b and R′.sub.b, which may be identical or different, represent a hydrogen atom, an aryl(C.sub.1-C.sub.4)alkyl group, or a C.sub.1-C.sub.6 alkyl group that is optionally substituted; R.sub.c, R′.sub.c, R.sub.d and R′.sub.d, which may be identical or different, represent a hydrogen atom, an aryl(C.sub.1-C.sub.4)alkyl or C.sub.1-C.sub.6 alkoxy group or a C.sub.1-C.sub.6 alkyl group that is optionally substituted; or alternatively two adjacent radicals R.sub.c and R.sub.d, R′.sub.c and R′.sub.d borne by the same nitrogen atom together form a heterocyclic or heteroaryl group; R.sub.e and R′.sub.e, which may be identical or different, represent a linear or branched C.sub.1-C.sub.6 alkylene or C.sub.2-C.sub.6 alkenylene hydrocarbon-based chain; R.sub.f and R′.sub.f, which may be identical or different, represent a group di(C.sub.1-C.sub.4)alkylamino, (R″)(R″′)N— or a quaternary ammonium group (R″)(R″′)(R″″)N.sup.+— in which R″, R″′ and R″″, which may be identical or different, represent a hydrogen atom or a C.sub.1-C.sub.4 alkyl group or alternatively (R″)(R″′)(R″″)N.sup.+— represents an optionally substituted cationic heteroaryl group; R.sub.g, R′.sub.g, R″.sub.g, R″′.sub.g, R.sub.h, R′.sub.h, R″.sub.h and R″′.sub.h, which may be identical or different, represent a hydrogen atom, a halogen atom, an amino, C.sub.1-C.sub.4 alkylamino, C.sub.1-C.sub.4 dialkylamino, cyano, carboxyl, hydroxyl or trifluoromethyl group, an acylamino, C.sub.1-C.sub.4 alkoxy, (poly)hydroxy(C.sub.2-C.sub.4)alkoxy, alkylcarbonyloxy, alkoxycarbonyl or alkylcarbonylamino radical, an acylamino, carbamoyl or alkylsulfonylamino radical, an aminosulfonyl radical, or a C.sub.1-C.sub.16 alkyl radical optionally substituted with a group chosen from C.sub.1-C.sub.12 alkoxy, hydroxyl, cyano, carboxyl, amino, C.sub.1-C.sub.4 alkylamino and C.sub.1-C.sub.4 dialkylamino, or alternatively the two alkyl radicals borne by the nitrogen atom of the amino group form a 5- to 7-membered heterocycle optionally comprising another nitrogen or non-nitrogen heteroatom; or alternatively two groups R.sub.g and R′.sub.g; R″.sub.g and R″′.sub.g; R.sub.h and R′.sub.h; R″.sub.h and R″′.sub.h borne by two adjacent carbon atoms together form a benzo or indeno ring, a fused heterocycloalkyl or fused heteroaryl group; the benzo, indeno, heterocycloalkyl or heteroaryl ring being optionally substituted with a halogen atom, an amino, C.sub.1-C.sub.4 alkylamino, C.sub.1-C.sub.4 dialkylamino, nitro, cyano, carboxyl, hydroxyl or trifluoromethyl group, an acylamino, C.sub.1-C.sub.4 alkoxy, (poly)hydroxy(C.sub.2-C.sub.4)alkoxy, alkylcarbonyloxy, alkoxycarbonyl or alkylcarbonylamino radical, an acylamino, carbamoyl or alkylsulfonylamino radical, an aminosulfonyl radical, or a C.sub.1-C.sub.16 alkyl radical optionally substituted with: a group chosen from C.sub.1-C.sub.12 alkoxy, hydroxyl, cyano, carboxyl, amino, C.sub.1-C.sub.4 alkylamino, C.sub.1-C.sub.4 dialkylamino, or alternatively the two alkyl radicals borne by the nitrogen atom of the amino group form a 5- to 7-membered heterocycle optionally comprising another nitrogen or non-nitrogen heteroatom; or alternatively when G represents —NR.sub.cR.sub.d and G′ represents —NR′.sub.cR′.sub.d, two groups R.sub.c and R′.sub.g; R′.sub.c and R″.sub.g; R.sub.d and R.sub.g; R′.sub.d and R″′.sub.g together form a saturated heteroaryl or heterocycle, optionally substituted with one or more C.sub.1-C.sub.6 alkyl, groups; R.sub.i, R′.sub.i, R″.sub.i, and R″′.sub.i, which may be identical or different, represent a hydrogen atom or a C.sub.1-C.sub.4 alkyl group; R.sub.1, R.sub.2, R.sub.3, R.sub.4, R′.sub.1, R′.sub.2, R′.sub.3 and R′.sub.4, which may be identical or different, represent a hydrogen atom or a C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.12 alkoxy, hydroxyl, cyano, carboxyl, amino, C.sub.1-C.sub.4 alkylamino or C.sub.1-C.sub.4 dialkylamino group, said alkyl radicals optionally forming, with the nitrogen atom which bears them, a 5- to 7-membered heterocycle optionally comprising another nitrogen or non-nitrogen heteroatom; T.sub.a and T.sub.b, which may be identical or different, represent i) either a covalent bond s, ii) or one or more radicals or combinations thereof chosen from —SO.sub.2—, —O—, —S—, —N(R)—, —N.sup.+(R)(R.sup.o)—and —CO—, with R and R.sup.o, which may be identical or different, representing a hydrogen atom, a C.sub.1-C.sub.4 alkyl or a C.sub.1-C.sub.4 hydroxyalkyl radical; or an aryl(C.sub.1-C.sub.4)alkyl radical; ##STR00097## which may be identical or different, represent an optionally substituted heterocyclic group; ##STR00098## represents an aryl or heteroaryl group fused to the imidazolium or phenyl ring; or alternatively is absent from the imidazolium or phenyl ring; m, m′, n and n′, which may be identical or different, represent an integer between 0 and 6 inclusive, with m+n and m′+n′, which may be identical or different, representing an integer between 1 and 10 inclusive; Y represents a hydrogen atom, or a group chosen from: (C.sub.1-C.sub.4)alkylcarbonyl; arylcarbonyl; (C.sub.1-C.sub.4)alkoxycarbonyl; aryloxycarbonyl; aryl(C.sub.1-C.sub.4)alkoxycarbonyl; (di)(C.sub.1-C.sub.4)(alkyl)aminocarbonyl; (C.sub.1-C.sub.4)(alkyl)arylaminocarbonyl; optionally substituted aryl; 5- or 6-membered monocyclic heteroaryl; cationic 5- or 6-membered monocyclic heteroaryl; these groups being optionally substituted with one or more identical or different (C.sub.1-C.sub.4)alkyl groups; cationic 8- to 11-membered bicyclic heteroaryl; these groups being optionally substituted with one or more identical or different (C.sub.1-C.sub.4)alkyl groups; cationic heterocycle having the following formula: ##STR00099## —C(NH.sub.2)═N.sup.+H.sub.2; An″′.sup.−; with An″′.sup.− being an anionic counterion; —C(NH.sub.2)═NH; SO.sub.3.sup.−, M.sup.+ with M.sup.+ representing an alkali metal; and M′ representing an anionic counterion, derived from a salt of an organic or mineral acid, or from an organic or mineral base that ensures the electrical neutrality of the molecule.

12. The process of claim 1, wherein b) the at least one disulfide, thiol, or protected-thiol fluorescent dye is chosen from the dyes of formulae (XVIb) to (XVI″′b) below: ##STR00100## and organic or mineral acid or base salts thereof, optical and geometric isomers and tautomers thereof, or solvates thereof; wherein formula (XVIb) or (XVI″′b): R′.sub.1 represents a C.sub.1-C.sub.4 alkyl group substituted with one or more hydroxyl groups, or —C(O)OR′ with R′ representing a hydrogen atom, a C.sub.1-C.sub.4 alkyl group, or a group —C(O)—O.sup.− and, in the latter case, an anionic counterion An.sup.− is absent; R′.sub.2 represents a C.sub.1-C.sub.4 alkyl group optionally substituted with one or more hydroxyl groups; R.sub.a, R.sub.b and R.sub.c represent a (C.sub.1-C.sub.6)alkyl group, they are in positions 3′, 4′ and 5′, or 2′, 4′ and 5′ or 2′, 4′ and 6′, An.sup.− represents an anionic counterion; B represents a bond or a divalent amido group —C(O)—N(R)- or —N(R)—C(O)—, with R representing a hydrogen atom or a (C.sub.1-C.sub.6)alkyl group; n and m, which may be identical or different, represent an integer between 1 and 4 inclusive; Y represents a hydrogen atom, or a group chosen from: (C.sub.1-C.sub.4)alkylcarbonyl; arylcarbonyl; (C.sub.1-C.sub.4)alkoxycarbonyl; aryloxycarbonyl; aryl(C.sub.1-C.sub.4)alkoxycarbonyl; (di)(C.sub.1-C.sub.4)(alkyl)aminocarbonyl; (C.sub.1-C.sub.4)(alkyl)arylaminocarbonyl; optionally substituted aryl; 5- or 6-membered monocyclic heteroaryl; cationic 5- or 6-membered monocyclic heteroaryl; these groups being optionally substituted with one or more identical or different (C.sub.1-C.sub.4)alkyl groups; cationic 8- to 11-membered bicyclic heteroaryl; these groups being optionally substituted with one or more identical or different (C.sub.1-C.sub.4)alkyl groups; cationic heterocycle having the following formula: ##STR00101## —C(NH.sub.2)═N.sup.+H.sub.2; An″′.sup.−; with An″′.sup.− being an anionic counterion; —C(NH.sub.2)═NH; SO.sub.3.sup.−, M.sup.+ with M.sup.+ representing an alkali metal; wherein the bond between the pyridinium ring and the double bond of the ethylene or styryl group is located in position 2 or 4 of the pyridinium.

13. The process of claim 1, wherein b) the at least one disulfide, thiol, or protected-thiol fluorescent dye is chosen from the dyes having the following chemical structures: ##STR00102## ##STR00103## ##STR00104## ##STR00105## ##STR00106## ##STR00107## ##STR00108## ##STR00109## ##STR00110## ##STR00111## ##STR00112## ##STR00113## ##STR00114## ##STR00115## ##STR00116## with An.sup.− and M′, which may be identical or different, representing anionic counterions.

14. The process of claim 1, further comprising applying to said keratin materials one or more reducing agents c), said reducing agent(s) c) optionally being applied before, at the same time as, or after the application of b) the at least one blue, violet, or green dye, or alternatively the one or more reducing agents c) are present with the at least one blue, violet, or green dye a); wherein the one or more reducing agents are chosen from i) the reducing agents of formula (Ic) below, addition salts thereof, or mixtures thereof:
H(X).sub.q(R.sub.10).sub.t  (Ic) wherein in formula (Ic), X represents P, S or SO.sub.2, q represents an integer equal to 0 or 1, t represents an integer equal to 1 or 2, and R.sub.10 represents a linear or branched, saturated or unsaturated C.sub.1 to C.sub.20 alkyl radical, optionally interrupted with a heteroatom, and/or optionally substituted with one or more radicals chosen from hydroxyl, halo, amine, carboxyl, ((C.sub.1-C.sub.30)alkoxy)carbonyl, amido, ((C.sub.1-C.sub.30)alkyl)aminocarbonyl, ((C.sub.1-C.sub.30)acyl)amino, mono- or dialkylamino, and mono- or dihydroxylamino radicals; ii) thioglycolic acid, iii) thiolactic acid, iv) glyceryl monothioglycolate, v) cysteamine, vi)N-acetylcysteamine, vii)N-propionylcysteamine, viii) cysteine, ix)N-acetylcysteine, x) thiomalic acid, xi) pantetheine, xii) 2,3-dimercaptosuccinic acid, xiii)N-(mercaptoalkyl)-w-hydroxyalkylamides, xiv)N-mono or N,N-dialkylmercapto-4-butyramides, xv) aminomercaptoalkylamides, xvi)N-(mercaptoalkyl)succinamic acid derivatives, xvii)N-(mercaptoalkyl)succinimide acid derivatives, xviii) alkylaminomercaptoalkylamides, ix) an azeotropic mixture of 2-hydroxypropyl thioglyconate and of (2-hydroxy-1-methyl)ethyl thioglycolate, x) mercaptoalkylaminoamides, xi)N-mercaptoalkylalkanediamides, xii) formamidine sulfinic acid derivatives, the addition salts thereof or mixtures thereof.

15. The process of claim 1, wherein the at least one blue, violet or green dyes a), and the at least one disulfide, thiol or protected-thiol fluorescent dyes b), are applied jointly to the keratin materials.

16. The process of claim 1, comprising at least the two successive steps below: a first step of applying to the light keratin materials a cosmetic composition comprising the one or more disulfide, thiol or protected-thiol fluorescent dyes b), followed by a second step of applying to the light keratin materials a cosmetic composition comprising the one or more blue, violet or green dyes a).

17. The process of claim 1, wherein the process comprises at least the two successive steps below: a first step of applying to the light keratin materials a cosmetic composition comprising one or more blue, violet or green dyes a), followed by a second step of applying to the light keratin materials a cosmetic composition comprising one or more disulfide, thiol or protected-thiol fluorescent dyes b).

18. The process of claim 1, wherein the process further comprises applying to the light keratin materials one or more oxidizing agents, which may be applied separately or jointly with one of the ingredients a) or b).

19. The process of claim 17, wherein the pH of the cosmetic composition(s) is between 6 and 11 inclusive.

20. A multi-compartment device comprising a first compartment comprising at least one blue, violet, or green dye a) chosen from: a1) phenoxazinium, phenothiazinium, or phenazinium dyes; a3) triarylmethane dyes; a4) naphthoquinone or anthraquinone dyes; a5) hydrazone dyes; a6) tetraazapentamethine dyes; a7) nitro dyes; a8) azomethine dyes; a9) self-oxidizing dyes; and/or a10) oxidation dyes; a second compartment comprising at least one disulfide, thiol, or protected-thiol fluorescent dye b); optionally a third compartment comprising at least one reducing agent c); and optionally a fourth compartment comprising at least one oxidizing agent d); wherein the multi-compartment device does not contain an additional dye other than the dyes a) and b).

Description

EXAMPLES

(1) In the examples that follow, all the amounts are given as weight percentages relative to the total weight of the composition, unless otherwise indicated.

(2) TABLE-US-00001 Blue dyes structures Dye 1 Dye 2 Dye 3 Dye 4 Dye 7 0 Dye 8 Dye 9 Dye 10 Dye 11 Dye 12 Dye 13 Dye 14 Dye 15 Dye 16 Dye 17 0 Dye 18

(3) TABLE-US-00002 Dye Structure of thiol/protected-thiol/disulfide fluorescent dyes a b

Example 1

(4) The dyes studied were tested at a mass concentration of 0.3 g % of each dye. The solutions are adjusted to pH 9 with aqueous ammonia solution.

(5) Dyes 4 and b; 8 and b are tested on locks of natural hair containing 90% white hairs, as a mixture (1 g), according to two application methods:

(6) The dyes are mixed in identical 1/1 ratios at a concentration of 0.3 g per 100 g of the composition comprising 0.15% of dye 4 and 0.15% of dye b, for example (0.15%/0.15%: g/g).

(7) The dye composition (aqueous dyeing medium) is applied according to two treatment methods: a treatment in reducing medium, i.e. the reducing agent is added to the dye composition. a treatment without reducing medium.
For these two treatments, a fixing phase, containing aqueous hydrogen peroxide solution, is prepared subsequently
As an example of application, the process is performed in the following manner:

(8) Treatment in reducing medium with fixing phase described as follows: 1) application of 10 ml of medium consisting of: 90% dyeing medium+10% reducing medium; leave-on time of 20 minutes; rinsing 2) fixing in oxidizing medium by applying 1 ml of the fixing medium: leave-on time of 5 minutes; rinsing, and then 3) shampooing/rinsing

(9) Aqueous Dyeing Medium

(10) TABLE-US-00003 Ingredients Amount per 100 g of composition Dyes  .sup. 0.3 g Water qs 100 g

(11) Reducing Medium

(12) TABLE-US-00004 Ingredients Amount per 100 g of composition Thioglycolic acid (TGA) 10 Monoethanolamine (MEA) 0.605 Water qs 100 g

(13) Fixing Medium

(14) TABLE-US-00005 Ingredients Amount per 100 g of composition H.sub.2O.sub.2 (50 volumes) 0.48 Antioxidant 0.02 85% Orthophosphoric acid 0.012 Water qs 100 g

(15) In Non-Reducing Medium

(16) Dyeing medium/water (0.15%/0.15% g/g)

(17) TABLE-US-00006 Ingredients Amount per 100 g of composition Dyes  .sup. 0.3 g Water qs 100 g
1) treatment (build-up) in simplex aqueous medium: leave-on time of 25 minutes; rinsing
2) shampooing/rinsing

(18) The light and shampoo resistances are evaluated for the various combinations

(19) Light Resistance

(20) 1) irradiation in an Oriel 1600 W solar simulator—irradiation time: 2 hours 40 minutes

(21) 2) colorimetric reading at the end of the cycle 24 hours later

(22) Shampoo Resistance

(23) 1) 20 shampoo washes broken down into four cycles of five shampoo washes

(24) 2) drying and colorimetric reading after each cycle of five shampoo washes

(25) The hair dyeing results are as follows:

(26) TABLE-US-00007 Blue Fluorescent Color Light Shampoo dye dye Medium obtained resistance resistance Dye 4 Dye b Reducing Matt dark + +++ agent brown Dye 8 Dye b Reducing Black ++ +++ agent Dye 4 Dye b Without Dark brown +++ ++ reducing agent Dye 8 Dye b Without Black +++ +++ reducing agent With +: weak, ++: moderate, +++ strong

Example 2

(27) The dyes 13 (tested at a set mass concentration of 0.2 g %) and b (tested at two mass concentrations in combination with compound 13-0.2 g %/0.5 g %) are combined on locks of natural hair containing 90% white hairs in a one-stage or two-stage process in the presence of reducing agent (for the disulfide fluorescent dye) followed by a fixing phase at the end of application; it should be noted that the blue dye 13 is applied at the spontaneous pH (pH 4.5) or at alkaline pH (pH 8.45) in the two-stage process and at the pH of the combination (pH 8.5) in the one-stage process. The pH adjustment is performed in the presence of MEA.

(28) The following combinations were prepared:

(29) TABLE-US-00008 Test Dye studied 1 Two stages: b (fluorescent) in reducing medium at 0.2% and then 13 (blue) at 0.2% 2 Two stages: b (fluorescent) in reducing medium at 0.5% and then 13 (blue) at 0.2% 3 One stage: 13 (blue) at 0.2% + b (fluorescent) in reducing medium at 0.2% 4 One stage: 13 (blue) at 0.2% + b (fluorescent) in reducing medium at 0.5%

(30) Application Protocol:

(31) Application in Two Stages—Disulfide Fluorescent Dye and then Blue Dye:

(32) 1—Application of the Fluorescent Dye b in Reducing Medium:

(33) The 1-g lock is laid flat in a trough at room temperature. 9 ml of the disulfide fluorescent dye b at 0.5% (or 0.2%)+1 ml of reducing solution at 0.6% at pH 8.5 are then added and maintained in contact with the lock for 20 minutes. The lock is then rinsed with water and then wrung dry between the fingers.

(34) 2—Application of the Blue Dye 13:

(35) The lock is once again laid flat in a trough at room temperature. 10 ml of solution of dye 13 at 0.2% are then added and maintained in contact with the lock for 20 minutes. The lock is then rinsed with water and then wrung dry between the fingers.

(36) 3—Fixing Phase:

(37) The lock is once again laid flat in a trough at room temperature. 9 ml of water+1 ml of oxidizing solution at 0.6% are then added and maintained in contact with the lock for 10 minutes. The lock is then rinsed with water and one shampoo wash is then performed. It is then dried under a hood at 40° C. and the colorimetric measurements are then taken.

(38) One-Stage Application

(39) The 1-g lock is laid flat in a trough at room temperature. 5 ml of solution of the blue dye 13 at 0.2% at the spontaneous pH and 5 ml of solution of fluorescent dye 13 at 0.4% (or 1%) at pH 8.45+1 ml of reducing solution at 0.6% at pH 8.5 are then added and maintained in contact with the lock for 20 minutes. The lock is then rinsed with water and then wrung dry between the fingers. It is once again laid flat in a trough at room temperature. 9 ml of water+1 ml of oxidizing solution at 0.6% are then added and maintained in contact with the lock for 10 minutes. The lock is then rinsed with water and one shampoo wash is then performed. It is dried under a hood at 40° C. and the colorimetric measurements are then taken.

(40) The treatment in reducing medium with (or without) a fixing phase described as follows:

(41) Aqueous Dyeing Medium (Two Concentrations Tested)

(42) TABLE-US-00009 Ingredients Amount per 100 g of composition Fluorescent dye 0.5 g/0.2 g Water qs 100 g

(43) Reducing Medium

(44) TABLE-US-00010 Ingredients Amount per 100 g of composition (pH 8.5) TGA 10 MEA 0.605 Water qs 100 g

(45) Fixing Medium

(46) TABLE-US-00011 Ingredient Amount per 100 g of composition H.sub.2O.sub.2 50 volumes 0.48 Water qs 100 g 1—treatment in reducing medium: [90% dyeing medium+10% reducing medium]; leave-on time of 20 minutes; rinsing 2—fixing in oxidizing medium at the end of application of the dyes: leave-on time of 10 minutes; rinsing 3—shampooing/rinsing

(47) The following dyeing results were obtained:

(48) TABLE-US-00012 Blue dye Fluorescent dye Process Color obtained Dye 13 Dye b One stage Dark brown Dye 13 Dye b Two stages Coppery brown

Example 3

(49) The blue dyes (tested depending on the dye at two molar concentrations of 5×10.sup.−3 mol % or 2.5×10.sup.−3 mol %) and the fluorescent dye a (tested at the mass concentration of 0.5 g % in combination with the blue compounds of the example) are combined on locks of natural hair containing 90% white hairs in a two-stage process in the presence of reducing agent (for the fluorescent dye) followed by a fixing step;

(50) The following combinations were prepared:

(51) TABLE-US-00013 Blue dye Disulfide fluorescent dye Dye 1 Dye a Dye 2 Dye a Dye 3 Dye a Dye 4 Dye a Dye 8 Dye a

(52) The dyeing tests are performed on 0.5 g locks of 90% NW Caucasian hair. Irrespective of the application order, the dyes are applied successively in the following manner

(53) Condition for application of the blue/violet direct dyes: dissolution of the dye in water (concentration: 5×10.sup.−3 mol per 100 ml of application water for 30 minutes at room temperature; rinsing with water (temperature 30° C.) and then one shampoo wash is performed; drying is performed under a hood for 10 minutes/gram of hair (temperature: 40° C.)

(54) Aqueous Dyeing Medium

(55) TABLE-US-00014 Ingredient Amount per 100 g of composition Fluorescent dye  .sup. 0.5 g Water qs 100 g

(56) Reducing Medium

(57) TABLE-US-00015 Ingredient Amount per 100 g of composition (pH 8.5) TGA 10 MEA 0.605 Water qs 100 g

(58) Fixing Medium

(59) TABLE-US-00016 Ingredient Amount per 100 g of composition H.sub.2O.sub.2/50 volumes 0.48 Water qs 100 g 1—treatment in reducing medium: [90% dyeing medium+10% reducing medium]; leave-on time of 20 minutes; rinsing 2—fixing in oxidizing medium at the end of application of the dyes: leave-on time of 5 minutes; rinsing 3—shampooing/rinsing/drying under a hood for 10 minutes/gram of hair

(60) Three application orders were evaluated: blue/violet dye and then disulfide fluorescent dye (bf application order) disulfide fluorescent dye and then blue/violet dye (fb application order)

(61) The following dyeing results were obtained:

(62) TABLE-US-00017 Blue dye Application (concentration) Fluorescent dye sense Color obtained Dye 1 Dye a bf Black (5 × 10.sup.−3 mol %) Dye 2 Dye a bf Coppery brown (5 × 10.sup.−3 mol %) Dye 2 Dye a fb Brown (5 × 10.sup.−3 mol %) Dye 3 Dye a bf Brown (5 × 10.sup.−3 mol %) Dye 3 Dye a fb Brown (5 × 10.sup.−3 mol %) Dye 4 Dye a bf Brown with a matt tint (5 × 10.sup.−3 mol %) Dye 4 Dye a fb Brown (5 × 10.sup.−3 mol %) Dye 8 Dye a bf Black (5 × 10.sup.−3 mol %) Dye 8 Dye a bf Black with a matt tint (5 × 10.sup.−3 mol %) Dye 8 Dye a fb Black (5 × 10.sup.−3 mol %) Blue direct dyes: 7 Blue self-oxidizing dye: 15, Oxidation dyes: combination in oxidizing medium leads to a blue color: 16+16′, Blue anthraquinone dyes: 17 and Blue disulfide anthraquinone dyes: 18

(63) The fluorescent dye combined, in a second stage, is the disulfide fluorescent dye b.

(64) In a first stage, the blue dyes are applied to the keratin fibers and a composition comprising the disulfide fluorescent dyes b as defined previously is then applied

(65) TABLE-US-00018 Com- Type of dye pounds Color Structure 15 Self-oxidizing blue 16 Oxidation base + Oxidation coupler 16′ Blue  7 Blue direct 17 Blue direct 18 Blue disulfide

(66) Application Protocol:

(67) The process of the invention and the compositions of the invention were evaluated on NW 90% white Caucasian hair The reducing solution of the process is a composition of thioglycolic acid TGA in water at 0.6% (by mass) brought to pH=8.5 with MEA. The oxidizing solution is an aqueous hydrogen peroxide composition at 0.6% in water. The composition comprising the blue dyes is a composition at 0.5% (by mass) in water. The composition comprising the disulfide fluorescent dyes at 0.5% (by mass) in water.

(68) 1—Application of the Dye in Reducing Medium:

(69) The 1-g lock is laid flat in a trough at room temperature. 9 ml of solution of the dye to be studied at 0.5%+1 ml of reducing composition at 0.6% are then added and maintained in contact with the lock for 20 minutes. The lock is then rinsed with water and then wrung dry between the fingers.

(70) 2—Application of the Fluorescent Dye b in Reducing Medium:

(71) The lock is once again laid flat in a trough at room temperature. 9 ml of composition of the fluorescent dye at 0.5%+1 ml of reducing solution at 0.6% are then added and maintained in contact with the lock for 20 minutes. The lock is then rinsed with water and then wrung dry between the fingers.

(72) 3—Application of the Oxidizing Medium:

(73) The lock is once again laid flat in a trough at room temperature. 9 ml of water+1 ml of oxidizing solution at 0.6% are then added and maintained in contact with the lock for 10 minutes. The lock is then rinsed with water and one shampoo wash is then performed. The lock is then dried with a hairdryer and the colorimetric measurements are then taken.

(74) Results in the L*a*b* System

(75) The color of the locks was evaluated in the L*a*b* system, using a Minolta® CM 3600D spectrocolorimeter, (Illuminant D65).

(76) In this L*a*b* system, L* represents the lightness, a* indicates the green/red color axis and b* indicates the blue/yellow color axis. The higher the value of L, the lighter or less intense the color. Conversely, the lower the value of L, the darker or more intense the color. The higher the value of a*, the redder the shade, and the higher the value of b*, the yellower the shade.

(77) Study on the hair containing 90% white hairs (90 NW):

(78) TABLE-US-00019 Table of results: L, a, b measurements Dyes L* (D65) Associated color Dye alone (comparative)  7 20.31 blue 15 31.91 16 + 16′ 57.67 16 + 16′ pH 9.5 56.75 17 39.86 18 31.37 b + TGA 45.74 red Dye and then fluorescent (invention)  7 + b 19.09 Intense black 15 + b 20.09 Brown-black 18 + b 23.60 Blueish black 17 + b 23.55 Blueish black

(79) The colorimetric data measurements above show that, in a first stage, the treatment in reducing medium of the blue dye affords a significantly greater intensity of coloring than the control without reducing medium. The dyeing combination of blue followed by a dyeing treatment with the disulfide fluorescent dyes of the invention b leads to a change in the color toward browns with coppery or black shades. It should be noted that dye 7 followed by application of the disulfide fluorescent dye b leads to a very intense and luminous black coloring.

(80) TABLE-US-00020 Dyes L* (D65) 16 + 16′ (comparative) 57.67 16 + 16′ pH 9.5 (comparative) 56.75 b + TGA (comparative) 45.74 16 + 16′ + b (invention) 39.93

(81) Moreover, it was shown that for the combination of oxidation dyes 16 and 16′ combined with the disulfide dye b, the intensity was significantly improved by the presence of a fluorescent dye b according to the invention versus the dyes taken alone independently.