PROCESS FOR DYEING KERATIN FIBRES USING AT LEAST ONE DIRECT DYE AND AT LEAST ONE DISULFIDE, THIOL OR PROTECTED-THIOL FLUORESCENT DYE

Abstract

The present invention relates to a process for dyeing and/or lightening keratin fibres, in particular human keratin fibres such as the hair, using b) one or more disulfide, thiol or protected-thiol fluorescent direct dyes and a) one or more direct dyes different from b).

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 the dyes a) and b) for dyeing light or dark keratin fibres, without using an additional dye different from those defined above, for giving the fibres very chromatic, particularly visible colours.

Claims

1. Process for dyeing keratin fibres, in particular human keratin fibres such as the hair, consisting in applying to said fibres: a) one or more direct dye(s); and b) one or more disulfide, thiol or protected-thiol direct fluorescent dye(s); it being understood that: the direct dye(s) a) and the disulfide, thiol or protected-thiol fluorescent dye (s) b) are applied to said keratin fibres jointly or sequentially, and the dye(s) a) is (are) different from the dye(s) b).

2. Dyeing process according to the preceding claim, in which the direct dye(s) a) is (are) ionic, i.e. it (they) is (are) positively or negatively charged or is (are) zwitterionic; in particular, the direct dye(s) a) is (are) chosen from cationic direct dyes, particularly which comprise a quaternary ammonium group, the cationic charge preferably being endocyclic, and/or anionic direct dyes.

3. Dyeing process according to either one of the preceding claims, in which the direct dye(s) a) is (are) chosen from the following dyes: acridines; acridones; anthranthrones; anthrapyrimidines; anthraquinones; azines; (poly)azos, hydrazono or hydrazones, in particular arylhydrazones; azomethines; benzanthrones; benzimidazoles; benzimidazolones; benzindoles; benzoxazoles; benzopyrans; benzothiazoles; benzoquinones; bisazines; bis-isoindolines; carboxanilides; coumarins; cyanines, such as azacarbocyanines, diazacarbocyanines, diazahemicyanines, hemicyanines or tetraazacarbocyanines; diazines; diketopyrrolopyrroles; dioxazines; diphenylamines; diphenylmethanes; dithiazines; flavonoids, such as flavanthrones and flavones; fluorindines; formazans; indamines; indanthrones; indigoids and pseudoindigoids; indophenols; indoanilines; isoindolines; isoindolinones; isoviolanthrones; lactones; (poly)methines, such as dimethines of stilbene or styryl types; naphthalimides; naphthanilides; naphtholactams; naphthoquinones; nitro, in particular nitro(hetero)aromatics; oxadiazoles; oxazines; perilones; perinones; perylenes; phenazines; phenoxazines; phenothiazines; phthalocyanines; polyenes/carotenoids; porphyrins; pyranthrones; pyrazolanthrones; pyrazolones; pyrimidinoanthrones; pyronines; quinacridones; quinolines; quinophthalones; squaranes; tetrazoliums; thiazines; thioindigos; thiopyronines; triarylmethanes or xanthenes; preferably chosen from (poly)azo, hydrazono and triarylmethane dyes.

4. Dyeing process according to any one of the preceding claims, in which the direct dye(s) a) is (are) chosen from the following direct dyes: the hydrazono cationic dyes of formulae (II) and (III), the azo dyes of formulae (IV) and (V) below, and also the optical and geometric isomers thereof and tautomers thereof, the salts of organic or mineral acids or bases thereof, and also the solvates thereof such as hydrates: ##STR00056## in which formulae (II) to (V): Het.sup.+ represents a cationic heteroaryl radical, preferentially bearing an endocyclic cationic charge, such as imidazolium, indolium or pyridinium, optionally substituted, preferentially with at least one (C.sub.1-C.sub.8) alkyl group such as methyl; Ar.sup.+ represents an aryl radical, such as phenyl or naphthyl, having an exocyclic cationic charge, preferentially ammonium, particularly tri(C.sub.1-C.sub.8)alkylammonium, such as trimethylammonium; Ar represents an aryl group, especially phenyl, which is optionally substituted, preferentially with one or more electron-donating groups such as i) optionally substituted (C.sub.1-C.sub.8)alkyl, ii) optionally substituted (C.sub.1-C.sub.8)alkoxy, iii) (di)(C.sub.1-C.sub.8)(alkyl)amino optionally substituted on the alkyl group(s) with a hydroxyl group, iv) aryl(C.sub.1-C.sub.8)alkylamino, v) optionally substituted N(C.sub.1-C.sub.8)alkyl-N-aryl(C.sub.1-C.sub.8)alkylamino or alternatively Ar represents a julolidine group; Ar represents an optionally substituted (hetero)aryl group, such as phenyl or pyrazolyl, which are optionally substituted, preferentially by one or more (C.sub.1-C.sub.8)alkyl, hydroxyl, (di)(C.sub.1-C.sub.8)(alkyl)amino, (C.sub.1-C.sub.8)alkoxy or phenyl groups; R.sub.a and R.sub.b, which may be identical or different, represent a hydrogen atom or a (C.sub.1-C.sub.8)alkyl group, which is optionally substituted, preferentially with a hydroxyl group; or else the R.sub.a substituent with a substituent of Het.sup.+ and/or R.sub.b with a substituent of Ar form, together with the atoms that bear them, a (hetero)cycloalkyl; in particular, R.sub.a and R.sub.b represent a hydrogen atom or a (C.sub.1-C.sub.4)alkyl group optionally substituted with a hydroxyl group; Q.sup. represents an organic or mineral anionic counterion, such as a halide or an alkyl sulfate; particularly the direct dyes comprising azo and hydrazono endocyclic cationic charges, of formulae (II) to (V) as defined previously; anionic, cationic or zwitterionic, in particular cationic, triarylmethane dyes, chosen from those of formula (I): ##STR00057## and also the organic or mineral acid or base addition salts thereof, the geometrical isomers, optical isomers and tautomers thereof, and the mesomeric forms thereof, and the solvates such as hydrates; in which formula (I): A, B and C are identical or different, and represent a (hetero)aryl group such as phenyl which is optionally substituted, and represents a single bond or double bond; preferably, the direct dye(s) a) is (are) chosen from the direct dyes (I), (II) and (IV).

5. Dyeing process according to any one of the preceding claims, in which a) the direct dye(s) a) is (are) chosen from the following direct dyes: the cationic azo and hydrazono dyes of formulae (II-1) and (IV-1): ##STR00058## and also the organic or mineral acid or base addition salts thereof, the geometrical isomers, optical isomers and tautomers thereof, and the mesomeric forms thereof, and the solvates such as hydrates; in which formulae (II-1) and (IV-1): R.sup.1 represents a (C.sub.1-C.sub.4)alkyl group such as methyl; R.sup.2 and R.sup.3, which may be identical or different, represent a hydrogen atom or a (C.sub.1-C.sub.4)alkyl group, such as methyl; and R.sup.4 represents a hydrogen atom or an electron-donating group such as optionally substituted (C.sub.1-C.sub.8)alkyl, optionally substituted (C.sub.1-C.sub.8)alkoxy, or (di)(C.sub.1-C.sub.8)(alkyl)amino optionally substituted on the alkyl group(s) with a hydroxyl group; particularly, R.sup.4 is a hydrogen atom, Z represents a CH group or a nitrogen atom, preferentially CH, Q.sup. is an anionic counterion as defined above, in particular a halide, such as chloride, or an alkyl sulfate, such as methyl sulfate or mesityl; ; and the cationic triarylmethanes dyes of formulae (IIa) and (IIa) below: ##STR00059## and also the organic or mineral acid or base addition salts thereof, the geometrical isomers, optical isomers and tautomers thereof, and the mesomeric forms thereof, and the solvates thereof such as hydrates: in which formulae (IIa) and (IIa) below: R.sub.1, R.sub.2, R.sub.3 and R.sub.4, which may be identical or different, represent a hydrogen atom or one of the following groups: (C.sub.1-C.sub.6)alkyl which is optionally substituted, preferably with a hydroxyl group; aryl such as phenyl, aryl(C.sub.1-C.sub.4)alkyl such as benzyl, heteroaryl, heteroaryl(C.sub.1-C.sub.4)alkyl, or else two groups R.sub.1, and R.sub.2, and/or R.sub.3 and R.sub.4, borne by the same nitrogen atom form, together with the nitrogen atom which bears them, an optionally substituted heterocycloalkyl group such as morpholino, piperazino or piperidino, preferably 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 group; R.sub.5, R.sub.6, R.sub.7, R.sub.8, R.sub.9, R.sub.10, R.sub.11, R.sub.12, R.sub.13, R.sub.14, R.sub.15, and R.sub.16, which may be identical or different, represent a hydrogen or halogen atom, or a group chosen from i) hydroxyl, ii) thiol, iii) amino iv) (di)(C.sub.1-C.sub.4)(alkyl)amino, v) (di)arylamino such as (di)phenylamino, vi) nitro, vii) acylamino (NRC(O)R) in which the R radical is a hydrogen atom, a C.sub.1-C.sub.4 alkyl radical optionally bearing at least one hydroxyl group and the R radical is a C.sub.1-C.sub.2 alkyl radical; viii) carbamoyl ((R).sub.2NC(O)) in which the R radicals, which may be identical or different, represent a hydrogen atom or a C.sub.1-C.sub.4 alkyl radical optionally bearing at least one hydroxyl group; ix) carboxylic acid or ester, (OC(O)R) or (C(O)OR), in which the R radical is a hydrogen atom or a C.sub.1-C.sub.4 alkyl radical optionally bearing at least one hydroxyl group and the R radical is a C.sub.1-C.sub.2 alkyl radical; x) alkyl which is optionally substituted, in particular with a hydroxyl group; xi) alkylsulfonylamino (RSO.sub.2NR) in which the R radical represents a hydrogen atom or a C.sub.1-C.sub.4 alkyl radical optionally bearing at least one hydroxyl group and the R radical represents a C.sub.1-C.sub.4 alkyl radical, a phenyl radical; xii) aminosulfonyl ((R).sub.2NSO.sub.2) in which the R radicals, which may be identical or different, represent a hydrogen atom or a C.sub.1-C.sub.4 alkyl radical optionally bearing at least one hydroxyl group; xiii) (C.sub.1-C.sub.4)alkoxy; and xiv) (C.sub.1-C.sub.4)alkylthio; or else two radicals borne by two contiguous carbon atoms R.sub.5 and R.sub.6 and/or R.sub.7 and R.sub.8 and/or R.sub.9 and R.sub.10 and/or R.sub.11 and R.sub.12 and/or R.sub.13 and R.sub.14 and/or R.sub.15 and R.sub.16 form, together with the carbon atoms which bear them, an aryl or heteroaryl, preferably benzo, 6-membered fused ring, said ring possibly also being optionally substituted, preferably an unsubstituted benzo ring; Q.sup. represents an anionic counterion as defined previously, for achieving electron neutrality of the molecule, preferably chosen from halides such as chloride or bromide, and phosphate; when the catatonic dye comprises one or more anionic substituents such as COOR or SO.sub.3R with R denoting a hydrogen or a cation, it is understood that there are then more cationic substituents than anionic substituents, such that the overall resulting charge of the triarylmethane structure is cationic, counterbalanced by Q.sup.; preferably the direct dye(s) a) of formulae (IIa) and (IIa) are HC Blue 15; preferably, the direct dye(s) a) is (are) chosen from the direct dyes (II-1) and (IV-1), and more particularly chosen from Basic Red 51, Basic Yellow 87 and Basic Orange 31: ##STR00060## and also the solvates thereof such as hydrates; with Q being an anionic counterion as defined in the preceding claim, in particular a halide, such as chloride, or an alkyl sulfate, such as methyl sulfate or mesityl.

6. Process according to any one of the claims 1 to 3, in which the direct dye(s) a) is (are) chosen from anionic dyes; preferably selected from those of formulae (VII), (VII), (VIII), (VIII), (IX), (IX), (X), (X), (XI), (XII), (XII), (XIII), and (XIV) below: c3a) the diaryl anionic azo dyes of formula (VII) or (VII): ##STR00061## in which formulae (VII) and (VII): R.sub.7, R.sub.8, R.sub.9, R.sub.10, R.sub.7, R.sub.8, R.sub.9 and R.sub.10, which may be identical or different, represent a hydrogen atom or a group chosen from: i) alkyl, ii) alkoxy, iii) alkylthio, iv) hydroxyl, v) mercapto, vi) nitro, vii) R.sup.oC(X)X, R.sup.oXC(X), R.sup.oXC(X)X with R.sup.o representing a hydrogen atom or an alkyl or aryl group; X, X and X, which may be identical or different, representing an oxygen or sulfur atom or NR with R representing a hydrogen atom or an alkyl group; viii) (O).sub.2S(O.sup.), M.sup.+ with M.sup.+ represents a cationic counterion as defined previously; ix) (O)CO.sup., M.sup.+ with M.sup.+ represents an organic or mineral cationic counterion preferably chosen from alkali metal or alkaline-earth metal cations such as Na.sup.+ or K.sup.+; x) RS(O).sub.2, with R representing a hydrogen atom, an alkyl group, an aryl, (di)(alkyl)amino or aryl(alkyl)amino group; preferentially a phenylamino or phenyl group; xi) RS(O).sub.2X with R representing an optionally substituted alkyl or aryl group, X as defined previously; xii) (di)(alkyl)amino; xiii) aryl(alkyl)amino optionally substituted with one or more groups chosen from nitro; nitroso; (O).sub.2S(O.sup.), M.sup.+ and alkoxy with M.sup.+ as defined previously; xiv) optionally substituted heteroaryl; preferentially a benzo thiazolyl group; xv) cycloalkyl; especially cyclohexyl, xvi) ArNN with Ar representing an optionally substituted aryl group; preferentially a phenyl optionally substituted with one or more alkyl groups, (O).sub.2S(O.sup.), M.sup.+ or phenylamino; or alternatively two contiguous groups R.sub.7 with R.sub.8 or R.sub.8 with R.sub.9 or R.sub.9 with R.sub.10 together form a fused benzo group A; and R.sub.7 with R.sub.8 or R.sub.8 with R.sub.9 or R.sub.9 with R.sub.10 together form a fused benzo group B; with A and B optionally substituted with one or more groups chosen from i) nitro; ii) nitroso; iii) (O).sub.2S(O.sup.), M.sup.+; iv) hydroxyl; v) mercapto; vi) (di)(alkyl)amino; vii) R.sup.oC(X)X; viii) R.sup.oXC(X); ix) R.sup.oXC(X)X; x) ArNN and xi) optionally substituted aryl(alkyl)amino; with M.sup.+, R.sup.o, X, X, X and Ar as defined previously; W represents a sigma bond , an oxygen or sulfur atom, or a divalent radical i) N(R) with R as defined previously, or ii) methylene C(R.sub.a)(R.sub.b) with R.sub.a and R.sub.b, which may be identical or different, representing a hydrogen atom or an aryl group, or alternatively R.sub.a and R.sub.b form, together with the carbon atom that bears them, a spiro cycloalkyl; preferentially, W represents a sulfur atom or R.sub.a and R.sub.b together form a cyclohexyl; it being understood that formulae (VII) and (VII) comprise at least one sulfonate (O).sub.2S(O.sup.), Q.sup.+ or carboxylate (O)C(O.sup.), Q.sup.+ radical on one of the rings A, A, B, B or C with R.sub.1R.sub.2R.sub.3R.sub.4 as defined previously; Q.sup.+ represents an organic or mineral cationic counterion preferably chosen from alkali metal or alkaline-earth metal cations such as Na.sup.+ or K.sup.+; c3b) the pyrazolone anionic azo dyes of formulae (VIII) and (VIII): ##STR00062## in which formulae (VIII) and (VIII): R.sub.11, R.sub.12 and R.sub.13, which may be identical or different, represent a hydrogen or halogen atom, an alkyl group or (O).sub.2S(O.sup.), M.sup.+ with M.sup.+ as defined previously; R.sub.14 represents a hydrogen atom, an alkyl group or a group C(O)O, M.sup.+ with M.sup.+ as defined previously; R.sub.15 represents a hydrogen atom; R.sub.16 represents an oxo group, in which case R.sub.16 is absent, or alternatively R.sub.15 with R.sub.16 together form a double bond; R.sub.17 and R.sub.18, which may be identical or different, represent a hydrogen atom or a group chosen from: (O).sub.2S(O.sup.), M.sup.+ with M.sup.+ as defined previously; ArOS(O).sub.2.sup. with Ar representing an optionally substituted aryl group, preferentially a phenyl optionally substituted with one or more alkyl groups; R.sub.19 and R.sub.20 together form either a double bond, or a benzo group D, which is optionally substituted; R.sub.16, R.sub.19 and R.sub.20, which may be identical or different, represent a hydrogen atom or an alkyl or hydroxyl group; R.sub.21 represents a hydrogen atom or an alkyl or alkoxy group; R.sub.a and R.sub.b, which may be identical or different, are as defined previously, preferentially R.sub.a represents a hydrogen atom and R.sub.b represents an aryl group; Y represents either a hydroxyl group or an oxo group; - - - represents a single bond when Y is an oxo group; and represents a double bond when Y represents a hydroxyl group; it being understood that formulae (VIII) and (VIII) comprise at least one sulfonate group (O).sub.2S(O.sup.), Q.sup.+ on one of the rings D or E or formulae (VIII) and (VIII) comprise at least one carbon/late group (O)C(O.sup.), Q.sup.+ with Q.sup.+ as defined previously; preferentially comprise at least one sulfonate group (O).sub.2S(O.sup.), Q.sup.+ on one of the rings D or E and more particularly sulfonate; c3c) the anthraquinone dyes of formulae (IX) and (IX): ##STR00063## in which formulae (IX) and (IX): R.sub.22, R.sub.23, R.sub.24, R.sub.25, R.sub.26 and R.sub.27, which may be identical or different, represent a hydrogen or halogen atom or a group chosen from i) alkyl, ii) hydroxyl, iii) mercapto, iv) alkoxy, v) alkylthio, vi) aryloxy or arylthio which is optionally substituted, preferentially substituted with one or more groups chosen from alkyl and (O).sub.2S(O.sup.), M.sup.+ with M.sup.+ as defined previously, vii) aryl(alkyl)amino optionally substituted with one or more groups chosen from alkyl and (O).sub.2S(O.sup.), M.sup.+ with M.sup.+ as defined previously, viii) (di)(alkyl)amino, ix) (di)(hydroxyalkyl)amino, x) (O).sub.2S(O.sup.), M.sup.+ with M.sup.+ as defined previously; Z represents a hydrogen atom or a group NR.sub.28R.sub.29 with R.sub.28 and R.sub.29, which may be identical or different, representing a hydrogen atom or a group chosen from i) alkyl, ii) polyhydroxyalkyl such as hydroxyethyl, iii) aryl optionally substituted with one or more groups, particularly alkyl, such as methyl, n-dodecyl, n-butyl; (O).sub.2S(O.sup.), M.sup.+ with M.sup.+ as defined previously; R.sup.oC(X)X, R.sup.oXC(X), R.sup.oXC(X)X with R.sup.o, X, X and X as defined previously, preferentially R.sup.o represents an alkyl group, iv) cycloakyl; especially cyclohexyl; Z represents a group chosen from hydroxyl and NR.sub.28R.sub.29 with R.sub.28 and R.sub.29, which may be identical or different, representing the same atoms or groups as R.sub.28 and R.sub.29 as defined previously; it being understood that formulae (IX) and (IX) comprise at least one sulfonate group (O).sub.2S(O.sup.), Q.sup.+; c3d) the nitro dyes of formulae (X) and (X): ##STR00064## in which formulae (X) and (X): R.sub.30, R.sub.31 and R.sub.32, which may be identical or different, represent a hydrogen or halogen atom or a group chosen from i) alkyl, ii) alkoxy optionally substituted with one or more hydroxyl groups, iii) alkylthio optionally substituted with one or more hydroxyl groups, iv) hydroxyl, mercapto, v) nitro, nitroso, vi) (poly)haloalkyl, vii) R.sup.oC(X)X, R.sup.oXC(X), R.sup.oXC(X)X with R.sup.o; X, X and X as defined previously, viii) (O).sub.2S(O.sup.), M.sup.+ with M.sup.+ as defined previously, ix) (O)CO.sup., M.sup.+ with M.sup.+ as defined previously, x) (di)(alkyl)amino, xi) (di)(hydroxyalkyl)amino, xii) heterocycloalkyl such as piperidino, piperazino or morpholino; in particular, R.sub.30, R.sub.31 and R.sub.32 represent a hydrogen atom; R.sub.c and R.sub.d, which may be identical or different, represent a hydrogen atom or an alkyl group; W is as defined previously; W particularly represents a group NH; ALK represents a linear or branched divalent C.sub.1-C.sub.6 alkylene group; in particular, ALK represents a group CH.sub.2CH.sub.2; n is 1 or 2; p represents an integer between 1 and 5 inclusive; q represents an integer between 1 and 4 inclusive; u is 0 or 1; when n is 1, J represents a nitro or nitroso group; particularly nitro group; when n is 2, J represents an oxygen or sulfur atom, or a divalent radical S(O).sub.m with m representing an integer 1 or 2; preferentially J represents a radical SO.sub.2; M is as defined previously for M.sup.+; ##STR00065## which may be present or absent, represents a benzo group optionally substituted with one or more groups R.sub.30 as defined previously; it being understood that formulae (X) and (X) comprise at least one sulfonate group (O).sub.2S(O.sup.), Q.sup.+ or carboxylate group (O)C(O.sup.), Q.sup.+; c3e) the triarylmethane dyes of formula (XI): ##STR00066## in which formula (XI): R.sub.33, R.sub.34, R.sub.35 and R.sub.36, which may be identical or different, represent a hydrogen atom or a group chosen from alkyl, optionally substituted aryl and optionally substituted arylalkyl; particularly an alkyl group and benzyl optionally substituted with a group (O).sub.mS(O.sup.), M.sup.+ with M.sup.+ and m as defined previously; R.sub.37, R.sub.38, R.sub.30, R.sub.40, R.sub.41, R.sub.42, R.sub.43 and R.sub.44, which may be identical or different, represent a hydrogen atom or a group chosen from: i) alkyl; ii) alkoxy, alkylthio; iii) (di)(alkyl)amino; iv) hydroxyl, mercapto; v) nitro, nitroso; vii) R.sup.oXC(X), R.sup.oXC(X)X with R.sup.o representing a hydrogen atom or an alkyl or aryl group; X, X and X, which may be identical or different, representing an oxygen or sulfur atom or NR with R representing a hydrogen atom or an alkyl group; viii) (O)2S(O), M+ with M+ representing a hydrogen atom or a cationic counterion; ix) O)CO.sup., M.sup.+ with M.sup.+ as defined previously; or alternatively two contiguous groups R.sub.41 with R.sub.42 or R.sub.42 with R.sub.43 or R.sub.43 with R.sub.44 together form a fused benzo group: I; with I optionally substituted with one or more groups chosen from i) nitro; ii) nitroso; iii) (O).sub.2S(O.sup.), M.sup.+; iv) hydroxyl; v) mercapto; vi) (di)(alkyl)amino; vii) R.sup.oC(X)X; viii) R.sup.oXC(X); and ix) R.sup.oXC(X)X; with M, R.sup.o, X, X and X as defined previously; particularly, R.sub.37 to R.sub.40 represent a hydrogen atom, and R.sub.41 to R.sub.44, which may be identical or different, represent a hydroxyl group or (O).sub.2S(O.sup.), M.sup.+; and when R.sub.43 with R.sub.44 together form a benzo group, it is preferentially substituted with a group (O).sub.2S(O.sup.); it being understood that at least one of the rings G, H, I or I comprises at least one sulfonate (O).sub.2S(O.sup.), Q.sup.+ or carboxylate (O)C(O.sup.), Q.sup.+ group; c3f) the xanthene-based dyes of formula (XII) or (XII): ##STR00067## in which formula (XII) or (XII): R.sub.45, R.sub.46, R.sub.47 and R.sub.48, which may be identical or different, represent a hydrogen or halogen atom; R.sub.49, R.sub.50, R.sub.51 and R.sub.52, which may be identical or different, represent a hydrogen or halogen atom or a group chosen from i) alkyl; ii) alkoxy, alkylthio; iii) hydroxyl, mercapto; iv) nitro, nitroso; v) (O).sub.2S(O.sup.), M.sup.+ with M.sup.+ representing a hydrogen atom or a cationic counterion; vi) (O)CO.sup., M.sup.+ with M.sup.+ as defined previously; particularly, R.sub.53, R.sub.54, R.sub.55 and R.sub.48 represent a hydrogen or halogen atom; G represents an oxygen or sulfur atom or a group NR.sub.e with R.sub.e as defined previously; particularly, G represents an oxygen atom; L represents an alkoxide O.sup., M.sup.+; a thioalkoxide S.sup., M.sup.+ or a group NR.sub.f, with R.sub.f representing a hydrogen atom or an alkyl group and M.sup.+ as defined previously; M.sup.+ is particularly Na.sup.+ or K.sup.+; L represents an oxygen or sulfur atom or an ammonium group: N.sup.+R.sub.fR.sub.g, with R.sub.f and R.sub.g, which may be identical or different, representing a hydrogen atom, an alkyl group or optionally substituted aryl; L represents particularly an oxygen atom or a phenylamino group optionally substituted with one or more alkyl or (O).sub.mS(O.sup.), M.sup.+ groups with m and M.sup.+ as defined previously; Q and Q, which may be identical or different, represent an oxygen or sulfur atom; particularly Q and Q represent an oxygen atom; M.sup.+ is as defined previously; it being understood that formula (XII) comprises at least one sulfonate group (O).sub.2S(O.sup.), Q.sup.+ or carbon/late group (O)C(O.sup.), Q.sup.+ with Q.sup.+ as defined previously; c3g) the indigoid dyes of formula (XIII): ##STR00068## in which formula (XIII): R.sub.53, R.sub.54, R.sub.55, R.sub.56, R.sub.57, R.sub.58, R.sub.59 and R.sub.60, which may be identical or different, represent a hydrogen atom or a group chosen from: i) alkyl; ii) alkoxy, alkylthio; iii) hydroxyl, mercapto; iv) nitro, nitroso; v) R.sup.oC(X)X, R.sup.oXC(X), R.sup.oXC(X)X with R.sup.o representing a hydrogen atom or an alkyl or aryl group; X, X and X, which may be identical or different, representing an oxygen or sulfur atom or NR with R representing a hydrogen atom or an alkyl group; vi) (O).sub.2S(O.sup.), M.sup.+ with M.sup.+ as defined previously; vii) (O)CO, M+ with M+ as defined previously; G represents an oxygen or sulfur atom or a group NR.sub.e with R.sub.e as defined previously; particularly, G represents an oxygen atom; R.sub.i and R.sub.h, which may be identical or different, represent a hydrogen atom or an alkyl group; it being understood that formula (XIII) comprises at least one sulfonate group (O).sub.2S(O.sup.), Q.sup.+ or carboxylate group (O)C(O.sup.), Q.sup.+ with Q.sup.+ as defined previously; c3h) the quinoline-based dyes of formula (XIV): ##STR00069## R.sub.61 represents a hydrogen or halogen atom or an alkyl group; R.sub.62, R.sub.63 and R.sub.64, which may be identical or different, represent a hydrogen atom or a group (O).sub.2S(O.sup.), M.sup.+ with M.sup.+ as defined previously; or alternatively R.sub.61 with R.sub.62, or R.sub.61 with R.sub.64, together form a benzo group optionally substituted with one or more groups (O).sub.2S(O.sup.), M.sup.+ with M.sup.+ representing a hydrogen atom or a cationic counterion; it being understood that formula (IX) comprises at least one sulfonate group (O).sub.2S(O.sup.), Q.sup.+ with Q.sup.+ as defined previously; more preferably the anionic direct dye(s) are chosen from those of formulae (XII) such as Acid Red 51.

7. Dyeing process according to any one of the preceding claims, in which a) the direct dye(s) a) is (are) neither a direct dye bearing at least one disulfide function, nor a direct dye bearing at least one thiol function, nor a direct dye bearing at least one protected-thiol function.

8. Dyeing process according to any one of the preceding claims, in which the direct dye(s) a) is (are) in a cosmetic composition, in a total amount of between 0.0001% and 30% inclusive, relative to the total weight of the composition which contains it (them), in particular the total amount of direct dye(s) a) as defined in any one of the preceding claims is between 0.002% and 5% by weight inclusive, relative to the total weight of the composition which contains it (them), preferentially in a total amount of between 0.005% and 2% inclusive, relative to the total weight of the composition which comprises it (them).

9. Process according to any one of the preceding claims, in which the disulfide, thiol or protected-thiol dye(s) b) is (are) chosen from dyes which absorb light in the yellow, orange and red, particularly red, range, preferably in the absorption wavelength .sub.abs between 400 nm and 500 nm inclusive.

10. Process according to either one of the preceding claims, in which the disulfide, thiol or protected-thiol fluorescent dye(s) b) is (are) chosen from those of formula (Ib): A-(X).sub.pC.sub.satSU and also the organic or mineral acid or base salts thereof, the optical and geometric isomers and tautomers thereof and the solvates thereof such as hydrates, in which formula (Ib): U represents a radical chosen from: a) SC.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, in particular hydrogen; 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; preferably, the dyes (Ib) are disulfide dyes, i.e. for which U represents the following radical a) SC.sub.sat(X).sub.p-A, and more particularly the dyes of formula (Ib) are symmetrical i.e. are such that A=A, C.sub.satC.sub.sat, XX and p=p.

11. Process according to any one of the preceding claims, in which the fluorescent dye(s) of formula (Ib) are dyes which, 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- said 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); in which: 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, preferentially monocyclic heterocycloalkyl or heteroaryl radical, preferentially containing two heteroatoms (more preferentially two nitrogen atoms) and preferentially being 5- to 7-membered, more preferentially imidazolium; 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 and the aryl radical is preferably C.sub.6, 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.

12. Process according to either one of claims 10 and 11, in which the disulfide, thiol or protected-thiol fluorescent dye(s) (Ib) is (are) such that A and/or A is (are) chosen from chromophores derived from (poly)methine or naphthalimide fluorescent dyes; and preferably chosen from those: of formulae (IIb) and (IIIb) below: ##STR00070## with, in formula (IIb) or (IIIb): W.sup.+ representing a cationic heterocyclic or heteroaryl group, particularly comprising a quaternary ammonium optionally substituted with one or more (C.sub.1-C.sub.8)alkyl groups optionally substituted especially with one or more hydroxyl groups; W.sup.+ representing a divalent heterocyclic or heteroaryl radical as defined for W.sup.+; Ar Ar representing an aryl group such as phenyl or naphthyl, optionally substituted preferentially with i) one or more halogen atoms such as chlorine or fluorine; ii) one or more groups (C.sub.1-C.sub.8)alkyl, preferably of C.sub.1-C.sub.4 such as methyl; iii) one or more hydroxyl groups; iv) one or more (C.sub.1-C.sub.8)alkoxy groups such as methoxy; v) one or more hydroxy(C.sub.1-C.sub.8)alkyl groups such as hydroxyethyl, vi) one or more amino or (di)(C.sub.1-C.sub.8)alkylamino groups, preferably with the C.sub.1-C.sub.4 alkyl part optionally substituted with one or more hydroxyl groups, such as (di)hydroxyethylamino, vii) with one or more acylamino groups; viii) one or more heterocycloalkyl groups such as piperazinyl, piperidinyl or 5- or 6-membered heteroaryl such as pyrrolidinyl, pyridinyl and imidazolinyl; Ar is an arylene radical, i.e. divalent aryl radical, as defined for Ar; m represents an integer between 1 and 4 inclusive, and in particular m has the value 1 or 2; more preferentially 1; R.sup.c, R.sup.d, which may be identical or different, represent a hydrogen atom or an optionally substituted group (C.sub.1-C.sub.8)alkyl, preferentially of C.sub.1-C.sub.4, or alternatively R.sup.c contiguous with W.sup.+ or W.sup.+ and/or R.sup.d contiguous with Ar or Ar form, with the atoms that bear them, a (hetero)cycloalkyl, particularly R.sup.c is contiguous with W.sup.+ or W.sup.+ and forms a (hetero)cycloalkyl such as cyclohexyl; Q.sup. is an organic or mineral anionic counterion as defined previously; (*) represents the part of the chromophore bonded to the rest of formula (Ib); preferably, W.sup.+ or W.sup.+ is an imidazolium, pyridinium, benzimidazolium, pyrazolium, benzothiazolium or quinolinium radical optionally substituted with one or more identical or different C.sub.1-C.sub.4 alkyl radicals; preferably, the fluorescent chromophore(s) are chosen from those with m=1, Ar representing a phenyl group substituted para to the styryl group C(R.sup.d)C(R.sup.c) with a (di)(hydroxy)(C.sub.1-C.sub.6)(alkyhamino group such as dihydroxy(C.sub.1-C.sub.4)alkylamino, and W.sup.+ representing an imidazolium or pyridinium group, preferably ortho- or para-pyridinium; of formula (IVb) or (Vb): ##STR00071## in which 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, preferentially with a di(C.sub.1-C6)alkylamino or tri(C.sub.1-C.sub.6)alkylammonium group such as trimethylammonium; ##STR00072## 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 else via C.sub.sat or C.sub.sat if p=0 or p=0.

13. Process according to any one of the preceding claims, in which the disulfide, thiol or protected-thiol fluorescent dye(s) b) is (are) chosen from the dyes of formulae (VIb) to (Xb) below: ##STR00073## ##STR00074## ##STR00075## and also the organic or mineral acid or base salts thereof, the optical and geometric isomers and tautomers thereof, and the solvates thereof such as hydrates; in which 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, preferentially unsubstituted; preferentially, G and G represent a group NR.sub.cR.sub.d or NR.sub.cR.sub.d, respectively; 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 possibly forming, with the nitrogen atom that bears them, a 5- to 7-membered heterocycle, optionally comprising another nitrogen or non-nitrogen heteroatom; preferentially, R.sub.a and R.sub.a represent a C.sub.1-C.sub.3 alkyl group optionally substituted with a hydroxyl group, or a benzyl group; 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; preferentially, R.sub.b and R.sub.b represent a hydrogen atom or a C.sub.1-C.sub.3 alkyl or benzyl group; 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; R.sub.c, R.sub.c, R.sub.d and R.sub.d preferentially represent a hydrogen atom, a hydroxyl, C.sub.1-C.sub.3 alkoxy, amino or C.sub.1-C.sub.3 (di)alkylamino group, or a C.sub.1-C.sub.3 alkyl group that is optionally substituted with i) a hydroxyl group, ii) amino, iii) C.sub.1-C.sub.3 (di)alkylamino, or iv) quaternary ammonium (R)(R)(R)N.sup.+; 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; preferentially, the heterocycle or heteroaryl is monocyclic and 5- to 7-membered; more preferentially, the groups are chosen from imidazolyl and pyrrolidinyl; 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, preferentially an imidazolinium group optionally substituted with a C.sub.1-C.sub.3 alkyl 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 heteroatom identical to or different from that of the nitrogen atom; preferentially, 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 represent a hydrogen or halogen atom or a C.sub.1-C.sub.3 alkyl group; 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 heteroatom identical to or different from that of the nitrogen atom; preferentially, R.sub.g and R.sub.g; R.sub.g and R.sub.g together form a benzo group; or alternatively two groups R.sub.i and R.sub.g; R.sub.i and R.sub.g; R.sub.i and R.sub.h; and/or R.sub.i and R.sub.h together form a fused (hetero)cycloalkyl, preferentially cycloalkyl such as cyclohexyl; 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, preferentially a 5- to 7-membered heterocycle containing one or two heteroatoms chosen from nitrogen and oxygen; more preferentially the heterocycle is chosen from morpholinyl, piperazinyl, piperidinyl and pyrrolidinyl groups; R.sub.1, R.sub.1, R.sub.1, 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, carboxy, amino, C.sub.1-C.sub.4 alkylamino or C.sub.1-C.sub.4 dialkylamino group, said alkyl radicals possibly forming, with the nitrogen atom which bears them, a 5- to 7-membered heterocycle optionally comprising another nitrogen or non-nitrogen heteroatom; preferentially, R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.1, R.sub.3, and R.sub.4 are hydrogen atoms, or a (C.sub.1-C.sub.4)alkyl or amino group; more preferentially, 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 represent a hydrogen atom; 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 radical or a C.sub.1-C.sub.4 hydroxyalkyl; or an aryl(C.sub.1-C.sub.4)alkyl radical; preferentially, T.sub.a is identical to T.sub.b and they represent a covalent bond s or a group chosen from N(R), C(O)N(R), N(R)C(O), OC(O), C(O)O and N.sup.+(R)(R.sup.o), with R and R.sup.o, which may be identical or different, representing a hydrogen atom or a C.sub.1-C.sub.4 alkyl group; more preferentially, T.sub.a and T.sub.b represent a bond s; iii) or a cationic or non-cationic, preferentially monocyclic heterocycloalkyl or heteroaryl radical, which are preferentially identical, preferentially containing two heteroatoms (more preferentially two nitrogen atoms) and preferentially being 5- to 7-membered, such as imidazolium; ##STR00076## which may be identical or different, represent an optionally substituted group; preferentially, the heterocycles are identical, monocyclic and saturated, and comprise in total two nitrogen atoms and from 5 to 8 ring members; ##STR00077## represent an aryl or heteroaryl group fused to the imidazolium or phenyl ring; or alternatively is absent from the imidazolium or phenyl ring; preferentially, when the ring is present, the ring is a benzo; 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, represent an integer between 1 and 10 inclusive; preferentially, m+n=m+n=an integer between 2 and 4 inclusive; more preferentially, m+n=m+n=an integer equal to 2; Y represents a hydrogen atom, or a group chosen from: (C.sub.1-C.sub.4)alkylcarbonyl, for instance methylcarbonyl or ethylcarbonyl; arylcarbonyl such as phenylcarbonyl; (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 such as dimethylaminocarbonyl; (C.sub.1-C.sub.4)(alkyl)arylaminocarbonyl; optionally substituted aryl such as phenyl; 5- or 6-membered monocyclic heteroaryl such as imidazolyl or pyridyl; cationic 5- or 6-membered monocyclic heteroaryl such as pyrylium, pyridinium, pyrimidinium, pyrazinium, pyridazinium, triazinium, imidazolium; these groups being optionally substituted with one or more identical or different (C.sub.1-C.sub.4)alkyl groups such as methyl; cationic 8- to 11-membered bicyclic heteroaryl such as benzimidazolium or benzoxazolium; these groups being optionally substituted with one or more identical or different (C.sub.1-C.sub.4)alkyl groups such as methyl; cationic heterocycle having the following formula: ##STR00078## C(NH.sub.2)N.sup.+H.sub.2; An.sup.; with An.sup. being an anionic counterion as defined previously; C(NH.sub.2)NH; SO.sub.3.sup., M.sup.+ with M.sup.+ representing an alkali metal such as sodium or potassium; 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; in particular, the disulfide, thiol or protected-thiol fluorescent dye(s) are chosen from the dyes of formulae (VIIIb), (VIIIb), (IXb) and (IXb) as defined previously.

14. Process according to any one of the preceding claims, in which b) disulfide, thiol or protected-thiol fluorescent dye(s) are chosen from: the dyes of formula (XVIb) or (XVIb) below: ##STR00079## and also the organic or mineral acid or base salts thereof, the optical and geometric isomers and tautomers thereof, and the solvates thereof such as hydrates; in which formula (XVIb) or (XVIb): R.sub.1 represents a C.sub.1-C.sub.4 alkyl group substituted with one or more hydroxyl groups, particularly with only one hydroxyl group, 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; preferentially, R.sub.1 represents a C.sub.1-C.sub.4 alkyl group substituted with a hydroxyl group; R.sub.2 represents a C.sub.1-C.sub.4 alkyl group optionally substituted with one or more hydroxyl groups, particularly with only one hydroxyl group; more particularly, R.sub.1 and R.sub.2 are identical; R.sub.a, R.sub.b and R.sub.c represents a (C.sub.1-C.sub.6)alkyl group such as methyl, they are in particular in positions 3, 4 and 5, or 2, 4 and 5 or 2, 4 and 6, they are preferably in positions 2, 4 and 5, An.sup. represents an anionic counterion as defined previously; B represent 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; preferentially, R represents a hydrogen atom; n and m, which may be identical or different, represent an integer between 1 and 4 inclusive, preferentially n is equal to 3 and m is equal to 2; Y is as defined previously; it being understood that 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, preferentially at 4; and/or the dyes of formula (XIIb) or (XIIb) below: ##STR00080## and also the organic or mineral acid or base salts thereof, the optical and geometric isomers and tautomers thereof, and the solvates thereof such as hydrates, in which formulae (XIIb) and (XIIb): R and R, which may be identical or different, represent a hydroxyl group, an amino group (NR.sub.aR.sub.b) or an ammonium group (N.sup.+R.sub.aR.sub.bR.sub.c), An.sup.; preferentially hydroxyl; with R.sub.a, R.sub.b and R.sub.c, which may be identical or different, representing a hydrogen atom or a (C.sub.1-C.sub.4)alkyl group; or alternatively two alkyl groups R.sub.a and R.sub.b of the amino or ammonium group form a 5- to 7-membered heterocycle optionally comprising another nitrogen or non-nitrogen heteroatom, such as morpholinyl, piperazinyl, piperidinyl, pyrrolyl, morpholinium, piperazinium, piperidinium or pyrrolinium, and An.sup. representing an anionic counterion; R and R, which may be identical or different, represent a hydrogen atom or a group as defined for R and R respectively; 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 or halogen atom, an amino, (di)(C.sub.1-C.sub.4)alkylamino, cyano, carboxyl, hydroxyl, trifluoromethyl, acylamino, C.sub.1-C.sub.4 alkoxy, C.sub.2-C.sub.4 (poly)hydroxyalkoxy, (C.sub.1-C.sub.4)alkylcarbonyloxy, (C.sub.1-C.sub.4)alkoxycarbonyl, (C.sub.1-C.sub.4)alkylcarbonylamino, acylamino, carbamoyl or (C.sub.1-C.sub.4)alkylsulfonylamino group, 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 and (di)(C.sub.1-C.sub.4)alkylamino, 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; in particular, 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 represent a hydrogen atom or a (C.sub.1-C.sub.4)alkyl group; 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; in particular R.sub.i, R.sub.i, R.sub.i, and R.sub.i represent a hydrogen atom; m, and m, which may be identical or different, represent an integer between 1 and 10 inclusive; in particular, an integer between 2 and 4 inclusive; preferentially m and m are equal to 2; p, p, q and q, which may be identical or different, represent an integer between 1 and 6 inclusive; M representing an anionic counterion; and Y is as defined previously; in particular, R.sub.h, R.sub.h are in the ortho position with respect to the pyridinium group and R.sub.h, R.sub.h represent a hydrogen atom; advantageously the dyes of formulae (XIIb) and (XIlb) possess their ethylene group in the para position with respect to the phenyl bearing the amino group: R(CH.sub.2).sub.gN(CH.sub.2).sub.qR and/or R(CH.sub.2).sub.pN(CH.sub.2).sub.qR, i.e. in position 4, preferentially bear an ethylene or styryl group linking the pyridinium part to the phenyl in the ortho position with respect to the pyridinium, i.e. 2-4.

15. Process according to any one of the preceding claims, in which the disulfide, thiol or protected-thiol fluorescent dye(s) is (are) chosen from the dyes having the following chemical structures: ##STR00081## ##STR00082## ##STR00083## ##STR00084## ##STR00085## ##STR00086## ##STR00087## ##STR00088## ##STR00089## ##STR00090## ##STR00091## ##STR00092## ##STR00093## ##STR00094## ##STR00095## with An.sup. and M, which may be identical or different, particularly identical, representing anionic counterions; more particularly, the anionic counterion is chosen from halides such as chloride, alkyl sulfate such as methyl sulfate, mesylate and (O).sub.2SO.sup.2 or SO.sub.4.sup.2; preferentially 31, 44, 49, 49a 55, 56 and 56a more particularly 44, 56 and 56a.

16. Dyeing process according to any one of the preceding claims, in which the total amount of disulfide, thiol or protected-thiol fluorescent dye(s) is between 0.001% and 30% inclusive, relative to the total weight of the composition which contains it (them), preferably the amount of disulfide, thiol or protected-thiol fluorescent dye(s) is between 0.01% and 5% by weight inclusive, relative to the total weight of the composition, more preferentially in a total amount of between 0.01% and 3% inclusive, better still between 0.05% and 2% inclusive, relative to the total weight of the composition which comprises it (them).

17. Process according to any one of the preceding claims, which also comprises the application to said keratin fibres of one or more reducing agents c), said reducing agent(s) c) possibly being applied before, at the same time as or after the application of the direct dye(s) a) as defined in any one of claims 1 to 8, and/or the disulfide, thiol or protected-thiol fluorescent dye(s) as defined in any one of claims 1 and 9 to 16; or alternatively said reducing agent(s) c) is (are) present with the direct dye(s) a) as defined in any one of claims 1 to 8, and/or the disulfide, thiol or protected-thiol fluorescent dye(s) as defined in any one of claims 1 and 9 to 16; preferably, said reducing agent(s) are chosen from i) the reducing agents of formula (Ic) below, and also the addition salts thereof and mixtures thereof:
H(X).sub.q(R.sub.10).sub.t(Ic) in which 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) pantotheine, xii) 2,3-dimercaptosuccinic acid, xiii) N-(mercaptoalkyl)--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-mercaptoalkylalcanediamides, xii) formamidine sulfinic acid derivatives, the addition salts thereof and mixtures thereof; preferably, the reducing agent(s) c) is (are) in the presence of the direct dye(s) a) as defined in any one of claims 1 to 8, and of the disulfide, thiol or protected-thiol fluorescent dye(s) as defined in any one of claims 1 and 9 to 16, or alternatively the reducing agent(s) c) are applied at the same time as the dye(s) a) as defined in any one of claims 1 to 8, and the disulfide, thiol or protected-thiol fluorescent dye(s) as defined in any one of claims 1 and 9 to 16.

18. Process according to any one of claims 1 to 16, which does not use any reducing agent.

19. Process according to any one of the preceding claims, in which the direct dye(s) a), as defined in any one of claims 1 to 8, and the disulfide, thiol or protected-thiol fluorescent dye(s) b), as defined in any one of claims 1 and 9 to 16, are applied jointly to the keratin fibres; preferably, the process comprises a step of applying to the keratin fibres a cosmetic composition which comprises one or more direct dye(s) a), as defined in any one of claims 1 to 8, and one or more disulfide, thiol or protected-thiol fluorescent dye(s) b) as defined in any one of claims 1 and 9 to 16.

20. Process according to any one of claims 1 to 18, which comprises at least the two successive steps below: a first step of applying to said keratin fibres a cosmetic composition comprising one or more disulfide, thiol or protected-thiol fluorescent dyes b), as defined in any one of claims 1 and 9 to 16, followed by a second step of applying to said fibres a cosmetic composition comprising one or more direct dyes a), as defined in any one of claims 1 to 8; or alternatively a first step of applying to said keratin fibres a cosmetic composition comprising one or more direct dyes a), as defined in any one of claims 1 to 8, followed by a second step of applying to said fibres a cosmetic composition comprising one or more disulfide, thiol or protected-thiol fluorescent dyes b), as defined in any one of claims 1 and 9 to 16.

21. Process according to any one of the preceding claims, which also comprises the application to said keratin fibres of one or more oxidizing agents applied after application of one or more direct dyes a), as defined in any one of claims 1 to 8, and one or more disulfide, thiol or protected-thiol fluorescent dyes b) as defined in any one of claims 1 and 9 to 16.

22. Process according to any one of the preceding claims, in which the pH of the cosmetic composition(s) is between 2 and 12, preferably between 2 and 11 inclusive, preferably between 2.5 and 10.5, more preferentially between 3 and 10.

23. Process according to any one of claims 17 and 19 to 22, in which the composition which comprises the reducing agent(s) c) also comprises at least two alkaline agents different from one another; in particular, one of the alkaline agents is a bicarbonate, more particularly an ammonium bicarbonate; preferentially, the bicarbonate is in the reducing composition comprising in particular thioglycolic acid (TGA) as reducing agent.

24. Cosmetic composition comprising one or more direct dyes a), as defined in any one of claims 1 to 8, and one or more disulfide, thiol or protected-thiol fluorescent dyes b), as defined in any one of claims 1 and 9 to 16, said composition optionally also comprising one or more reducing agents c) as defined in claim 17, and optionally having a pH of between 2 and 12 inclusive, preferably of between 2 and 11 inclusive, preferably between 2.5 and 10.5, more preferentially between 3 and 10.

25. Multi-compartment device comprising: either a first compartment containing one or more direct dyes a), as defined in any one of claims 1 to 8, and a second compartment containing one or more disulfide, thiol or protected-thiol fluorescent dyes b), as defined in any one of claims 1 and 9 to 16; optionally a third compartment containing one or more reducing agents c), as defined in claim 17, and optionally another compartment containing one or more oxidizing agents d); or a first compartment containing one or more direct dyes a), as defined in any one of claims 1 to 8, and one or more disulfide, thiol or protected-thiol fluorescent dyes b), as defined in any one of claims 1 and 9 to 16; optionally a second compartment containing one or more reducing agents c), as defined in claim 17, and optionally another, third, compartment containing one or more oxidizing agents d).

26. Use of one or more disulfide, thiol or protected-thiol fluorescent dye(s) b), as defined in any one of claims 1 and 9 to 16, combined with one or more direct dye(s) a), as defined in any one of claims 1 to 8, for dyeing keratin materials, in particular human keratin fibres such as the hair, in a chromatic colour, without using an additional dye different from the dyes a) or b).

Description

EXAMPLES

[0571] In the examples that follow, all the amounts are given as weight percentages relative to the total weight of the composition, unless otherwise indicated.

##STR00053##

[0572] The following compositions were prepared, the amounts are expressed in % by weight.

TABLE-US-00002 A1 B1 A2 B2 (inven- (compara- (inven- (compara- Ingredients tion) tive) tion) tive) Basic Orange 31 0.01 0.2 (BO31) Disulfide dye A 0.19 Basic Red 51 (BR51) 0.01 0.3 Disulfide dye B 0.29 Cetrimonium chloride 0.02 0.02 0.02 0.02 Behentrimonium 2.05 2.05 2.05 2.05 chloride Cetyl alcohol 1 1 1 1 Hydroxypropyltrimonium 0.1 0.1 0.1 0.1 guar chloride Isopropyl alcohol or 0.5 0.5 0.5 0.5 isopropanol Cetearyl alcohol 3.75 3.75 3.75 3.75 Amodimethicone 1.15 1.15 1.15 1.15 Hydroxyethylcelluose 0.2 0.2 0.2 0.2 Trideceth-6 0.1 0.1 0.1 0.1 Preservatives qs qs qs qs pH agent qs pH = qs pH = qs pH = qs pH = 3.5 3.5 3.5 3.5 Water qs 100 qs 100 qs 100 qs 100

[0573] The compositions above were applied to locks of light (bleached) hair at a rate of 5 g of composition per 1 g of lock.

[0574] After a leave-on time of 10 min on a thermostated plate at 27 C., the hair is rinsed and dried.

[0575] Spectrocolorimetric Results

[0576] The colour of the locks was evaluated in the L*a*b* system, using a Minolta CM 3600D spectrocolorimeter, (Illuminant D65).

[0577] In this L*a*b* system, L* represents the lightness, a* indicates the green/red colour axis and b* indicates the blue/yellow colour axis. The higher the value of L, the lighter or less intense the colour. Conversely, the lower the value of L, the darker or more intense the colour. The higher the value of a*, the redder the shade, and the higher the value of b*, the yellower the shade.

[0578] The chromaticity is calculated according to the following formula:

C*={square root over ((a*).sup.2+(b*).sup.2)}

[0579] The higher the value of the chromaticity C*, the more chromatic the colour of the treated keratin fibres.

TABLE-US-00003 Composition a* b* C* A1 (invention) 52.04 53.66 74.76 A2 (comparative) 49.26 34.29 60.02 B1 (invention) 50.22 33.94 60.62 B2 (comparative) 37.69 14.61 40.42

[0580] The compositions according to the invention A1 and A2 comprising the direct dye+disulfide dye combination produce values of C* which are higher, and therefore at a significantly greater chromaticity, compared with the comparative compositions B1 and B2, respectively comprising only the direct dyes.

[0581] Fastness with respect to washing: the locks treated with the compositions A1 and A2 were then subjected to a challenge of 5 successive shampooing operations (shp). The fastness with respect to washing is represented by the colour difference E between the locks dyed before and then after the 5-shampooing-operation challenge, according to the following equation:

E={square root over ((L*L.sub.o*).sup.2+(a*a.sub.o*).sup.2+(b*b.sub.o*).sup.2)}

[0582] In this equation, L*, a* and b* represent the values measured after shampooing challenge on the dyed locks, and L.sub.0*, a.sub.0* and b.sub.0* represent the values measured before shampooing challenge on the dyed locks.

[0583] The lower the E value, the better the colour-fastness of the hair with respect to washing.

TABLE-US-00004 Method L* a* b* E A1 before 49.25 52.04 53.66 shp A1 after shp 54.28 47.16 60.35 9.69 A2 before 36.80 49.26 34.29 shp A2 after shp 46.02 48.56 43.11 12.78

[0584] The composition A1 according to the invention exhibits a lower E value, and therefore better fastness with respect to washing, compared with the comparative composition.

Other Examples

[0585] The amounts of the compositions in the tables below are indicated by weight of active material (g per 100 g unless otherwise mentioned).

TABLE-US-00005 HC Blue 15 Acid dye A3 B3 A4 B4 Ingredients (invention) (comparative) (invention) (comparative) [00054] 0.01 0.2 [00055] 0.01 0.3 Dye A 0.19 Dye B 0.29 Behentrimonium chloride 2.05 2.05 2.05 2.05 Isopropylic alcohol or 0.5 0.5 0.5 0.5 isopropanol Cetyl alcohol 1 1 1 1 Hydroxy-propyltrimonium 0.1 0.1 0.1 0.1 chloride guar Cetearyl alcohol 3.75 3.75 3.75 3.75 Amodimehicone 1.15 1.15 1.15 1.15 Trideceth-6 0.1 0.1 0.1 0.1 Cetrimonium chloride 0.02 0.02 0.02 0.02 Hydroxythylcelluose 0.2 0.2 0.2 0.2 Preservatives Qs Qs Qs Qs Alkaline agent (NaOH) Qs pH = 3.5 Qs pH = 3.5 Qs pH = 3.5 Qs pH = 3.5 Water Qs 100 Qs 100 Qs 100 Qs 100

[0586] The compositions above were applied to locks of light (bleached) hair at a rate of 5 g of composition per 1 g of lock.

[0587] After a leave-on time of 10 min on a thermostated plate at 27 C., the hair is rinsed and dried.

[0588] Spectrocolorimetric Results

[0589] The colour of the locks was evaluated in the L*a*b* system, using a Minolta CM 3600D spectrocolorimeter, (Illuminant D65).

TABLE-US-00006 Composition a* b* C* A3 (invention) 19.88 29.36 35.46 B3 (comparative) 2.79 32.69 32.81 A4 (invention) 60.24 47.95 76.99 B4 (comparative) 11.81 28.75 31.08

[0590] The compositions according to the invention A3 and A4 comprising the direct dye+disulfide dye combination produce values of C* which are higher, and therefore at a significantly greater chromaticity, compared with the comparative compositions B3 and B4, respectively comprising only the direct dyes.