USE OF ANTHRAQUINONE DYES AND OF FLUORESCENT DYES FOR DYEING KERATIN FIBRES, DYEING PROCESS AND COMPOSITION

Abstract

Use of anthraquinone dyes and of fluorescent dyes for dyeing keratin fibres, dyeing process and composition. The present invention relates to a process for dyeing keratin fibres, in particular human keratin fibres such as the hair, using a) one or more particular anthraquinone dyes and b) one or more fluorescent direct dyes; to a composition comprising a) and b). The present invention also relates to a multi-compartment device containing the compounds defined above.

Claims

1.-27. (canceled)

28. A process for dyeing keratin fibers, comprising applying to the keratin fibers ingredients (a) and (b) below: (a) at least one anthraquinone dye chosen from the compounds of formulae (I) and/or (II) below, optical isomers thereof, geometrical isomers thereof, tautomers thereof, solvates thereof, or mixtures thereof: ##STR00053## wherein in formula (I) or (II): X.sub.a, which may be identical or different, represents a bond, a heteroatom or a group chosen from an oxygen or sulfur atom, N(R.sub.a), CO, SO, SO.sub.2, or combinations thereof, with R.sub.a representing a hydrogen atom or a (C.sub.1-C.sub.6)alkyl group optionally substituted with one or more hydroxyl groups; 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 (III) below: ##STR00054## 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 a group chosen from: hydrogen; halogen such as bromine and chlorine, 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)alkylcarbonyl, iii) arylsulfonyl such as phenylsulfonyl (—SO.sub.2Ph), iv) Het-ALK-C(O)— with Het representing a heterocycloalkyl group which is optionally substituted 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, 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; a group of formula (a) below:
—N(R.sub.7)—X.sub.1—W.sub.1  (a) wherein in formula (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, sulfur, CO, SO, SO.sub.2, arylene, or combinations thereof; W.sub.1 represents a cationic radical chosen from: ##STR00055## 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; n is an integer ranging from 1 to 3; 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, represent 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; being the part of the bond that is connected to the rest of the molecule; and (b) at least one cationic (poly)methine fluorescent dye; wherein: the anthraquinone dye(s) of formula (I) comprise at least one radical R.sub.1, R.sub.3 or R.sub.4, other than a hydrogen atom, and the anthraquinone dye(s) of formula (II) comprise at least one radical R′.sub.1, R′.sub.2, R′.sub.3 or R′.sub.4 other than a hydrogen atom; (a) the anthraquinone dye(s) of formula (I) or (II) and (b) the fluorescent dye(s) are applied to said keratin fibers together or sequentially; and when the compounds of formula (I) or (II) are cationic and comprise a sulfonate group, then M.sup.+ and An are optionally absent to ensure the electrical neutrality of said molecule.

29. The process according to claim 28, wherein the at least one anthraquinone dye of formulae (I) and/or (II) absorbs light in the blue-violet range.

30. The process according to claim 28, wherein the at least one anthraquinone is chosen from compounds of formula (I) wherein n is equal to 0 or 1.

31. The process according to claim 28, wherein the at least one anthraquinone dye is chosen from compounds of formula (I), wherein R.sub.1 and R.sub.3 represent an atom or group chosen from i) hydroxyl, ii) arylamino or aryl(C.sub.1-C.sub.6)alkylamino with the aryl group representing an optionally substituted aryl group, iii) (di)(hydroxy)(C.sub.1-C.sub.6)(alkyl)amino, iv) (di)(C.sub.1-C.sub.4)(alkyl)amino(C.sub.1-C.sub.6)alkylamino, v) (C.sub.1-C.sub.4)alkylcarbonylamino(C.sub.1-C.sub.6)alkylamino, vi) arylsulfonylamino with the aryl group optionally substituted, vii) (di)halo(C.sub.1-C.sub.4)alkylamino, viii) (di)(hydroxy)(C.sub.1-C.sub.4)alkoxy(C.sub.1-C.sub.4)alkylamino, ix) (di)tri(C.sub.1-C.sub.4)alkylammonium(C.sub.1-C.sub.6)alkylamino, x) heterocycloalkyl(C.sub.1-C.sub.6)alkylamino, heterocycloalkyl(C.sub.1-C.sub.4)alkylcarbonylamino, heterocycloalkyl(C.sub.1-C.sub.4)alkylamino(C.sub.1-C.sub.4)alkylcarbonylamino or heterocycloalkyl(C.sub.1-C.sub.4)alkylcarbonylamino(C.sub.1-C.sub.6)alkylamino, wherein the heterocycloalkyl is optionally cationic, xi) halo(C.sub.1-C.sub.4)alkylcarbonylamino(C.sub.1-C.sub.6)alkylamino, xii) hydroxysulfonyl, xiii) halo, xiv) heteroaryl(C.sub.1-C.sub.6)alkylamino, wherein the heteroaryl is optionally cationic and/or substituted, xv) heteroaryl(C.sub.1-C.sub.4)alkylcarbonylamino(C.sub.1-C.sub.6)alkylamino, wherein the heteroaryl is optionally cationic and/or substituted, xvi) R′R″N— with R′ and R″, which may be identical or different, representing a (halo)(C.sub.1-C.sub.4)alkylcarbonylamino(C.sub.1-C.sub.6)alkyl group, a (halo)(C.sub.1-C.sub.4)alkylaminocarbonyl (C.sub.1-C.sub.6)alkyl group, a (halo)(C.sub.1-C.sub.4)alkylcarbonyl group, a carboxy(C.sub.1-C.sub.6)alkyl group, the alkyl group possibly being substituted with one or more amino or hydroxyl groups, a (poly)hydroxy(C.sub.1-C.sub.6)alkyl group, xvii) (C.sub.1-C.sub.16)alkylaminocarbonylamino(C.sub.1-C.sub.6)alkylamino, xviii) formylamino(C.sub.1-C.sub.6)alkylamino, xix) (hydroxy)(C.sub.1-C.sub.6)alkylamino(C.sub.1-C.sub.6)alkylamino, xix) hydroxysulfonyl(C.sub.1-C.sub.6)alkylamino(C.sub.1-C.sub.6)alkylamino, xx) sulfonato(C.sub.1-C.sub.6)alkyl(di(C.sub.1-C.sub.4)alkyl)ammonium(C.sub.1-C.sub.6)alkylamino, xxi) hydroxysulfonyl(C.sub.1-C.sub.6)alkoxy(C.sub.1-C.sub.6)alkylamino, xxi) heteroaryl(C.sub.1-C.sub.4)alkylcarbonylamino, wherein the heteroaryl is optionally cationic and/or substituted, xxii) heterocycloalkyl(C.sub.1-C.sub.4)alkylcarbonylamino, wherein the heterocycloalkyl is optionally cationic and/or substituted, xxiii) (di)(C.sub.1-C.sub.4)(alkyl)amino(C.sub.1-C.sub.6)alkylamino, wherein the (C.sub.1-C.sub.6)alkyl group is optionally substituted with one or more hydroxyl groups, xxiv) heterocycloalkylamino(C.sub.1-C.sub.6)alkylamino or heterocycloalkylamino, wherein the heterocycloalkyl is optionally cationic and/or substituted, xxv) heteroarylalkylamino(C.sub.1-C.sub.6)alkylamino or heteroarylalkylamino, wherein the heteroaryl is optionally cationic and/or substituted, xxvi) tri(C.sub.1-C.sub.6)alkylammonium(C.sub.1-C.sub.6)alkylamino, xxvii) (C.sub.1-C.sub.4)alkoxycarbonyl(C.sub.1-C.sub.6)alkyl(di(C.sub.1-C.sub.4)alkyl)ammonium(C.sub.1-C.sub.6)alkylamino, xxviii) carboxylato(C.sub.1-C.sub.6)alkyl(di(C.sub.1-C.sub.4)alkyl)ammonium(C.sub.1-C.sub.6)alkylamino, xxix) carboxy(C.sub.1-C.sub.6)alkylamino(C.sub.1-C.sub.6)alkylamino, xxx) aryl(C.sub.1-C.sub.4)alkyl(di(C.sub.1-C.sub.4)alkyl)ammonium(C.sub.1-C.sub.6)alkylamino, xxxi) sulfonic SO.sub.3H or sulfonate SO.sub.3.sup.−, M.sup.+ with M.sup.+ representing a cationic counterion, xxxii) (C.sub.1-C.sub.6)alkyl, xxxiii) hydroxysulfonyl(C.sub.1-C.sub.4)amino, xxxiv) phenylsulfonylamino.

32. The process according to claim 28, wherein the at least one anthraquinone dye is chosen from dyes of formula (I), wherein R.sub.2 and R.sub.4, which may be identical or different, represent a hydrogen atom or a group chosen from: hydroxyl, (di)(C.sub.1-C.sub.4)(alkyl)amino, (C.sub.1-C.sub.4)alkoxy, heterocycloalkyl(C.sub.1-C.sub.6)alkylamino, wherein the heterocycloalkyl is optionally cationic and/or substituted, arylamino or aryl(C.sub.1-C.sub.6)alkylamino wherein the aryl group is an optionally substituted aryl group, aryl(C.sub.1-C.sub.4)alkyl(di(C.sub.1-C.sub.4)alkyl)ammonium(C.sub.1-C.sub.6)alkylamino, (di)(C.sub.1-C.sub.4)(alkyl)amino(C.sub.1-C.sub.6)alkylamino, or hydroxy(C.sub.1-C.sub.4)(alkyl)amino(C.sub.1-C.sub.6)alkylamino.

33. The process according to claim 28, wherein the at least one anthraquinone dye is chosen from dyes of formula (I), and R.sub.2 and R.sub.4 represent a hydrogen atom.

34. The process according to claim 28, wherein the at least one anthraquinone dye of formulae (I) and/or (II) is chosen from dyes of formula (I) with R.sub.2 and R.sub.3 representing a hydrogen atom, and R.sub.1 and R.sub.4 are chosen from: halogen, (di)(C.sub.1-C.sub.4)(alkyl)amino, (C.sub.1-C.sub.4)alkylcarbonylamino, heterocycloalkyl(C.sub.1-C.sub.6)alkylamino, heterocycloalkyl(C.sub.1-C.sub.4)alkylcarbonylamino or heterocycloalkyl(C.sub.1-C.sub.4)alkylamino(C.sub.1-C.sub.4)alkylcarbonylamino, wherein the heterocycloalkyl is optionally cationic and/or substituted, tri(C.sub.1-C.sub.4)alkylammonium(C.sub.1-C.sub.6)alkylamino, arylamino or aryl(C.sub.1-C.sub.6)alkylamino wherein the aryl group si an optionally substituted aryl group, (di)(C.sub.1-C.sub.4)(alkyl)amino(C.sub.1-C.sub.6)alkylamino, or (C.sub.1-C.sub.4)alkylcarbonylamino(C.sub.1-C.sub.6)alkylamino.

35. The process according to claim 28 wherein the anthraquinone dye(s) of formulae (I) and/or (II) are dyes of formula (I) with R.sub.3 and R.sub.4 representing a hydrogen atom, and R.sub.1 and R.sub.2 are in positions 8 and 1, respectively, and R.sub.1 and R.sub.2 are chosen from: (di)(hydroxy)(C.sub.1-C.sub.4)(alkyl)amino, (di)(hydroxy)(C.sub.1-C.sub.4)(alkyl)amino(C.sub.1-C.sub.6)alkylamino, tri(C.sub.1-C.sub.6)alkylammonium(C.sub.1-C.sub.6)alkylammonium, tri(C.sub.1-C.sub.6)alkylammonium(C.sub.1-C.sub.6)alkylamino, heterocycloalkyl(C.sub.1-C.sub.6)alkylamino, said heterocycloalkyl possibly being optionally cationic and/or substituted especially with one or more (C.sub.1-C.sub.4) alkyl or benzyl groups and arylamino or aryl(C.sub.1-C.sub.6)alkylamino with the aryl group representing an optionally substituted aryl group, in particular a phenyl group optionally substituted with one or more groups chosen from (C.sub.1-C.sub.4)alkyl, (di)(hydroxy)(C.sub.1-C.sub.4)(alkyl)amino, (C.sub.1-C.sub.4)alkoxy, tri(C.sub.1-C.sub.4)alkylammonium.

36. The process according to claim 28, wherein the at least one anthraquinone dye is chosen from dyes of formula (I) with R.sub.1 and R.sub.3 representing a hydrogen atom and n is equal to 2, and R.sub.2 and R.sub.4 are chosen from: (C.sub.1-C.sub.6)alkyl, (di)(hydroxy)(C.sub.1-C.sub.4)(alkyl)amino, SO.sub.3H or SO.sub.3.sup.−M.sup.+, (di)(hydroxy)(C.sub.1-C.sub.4)(alkyl)amino(C.sub.1-C.sub.6)alkylamino, tri(C.sub.1-C.sub.4)alkylammonium(C.sub.1-C.sub.6)alkylamino, and heterocycloalkyl(C.sub.1-C.sub.6)alkylamino, wherein the heterocycloalkyl si optionally cationic and/or substituted, or arylamino or aryl(C.sub.1-C.sub.6)alkylamino with the aryl group representing an optionally substituted aryl group.

37. The process according to claim 28, wherein the at least one anthraquinone dye is chosen from dyes of formula (II′): ##STR00056## wherein X.sub.a represents an N(R.sub.a), R′.sub.2 and R′.sub.4 represent a hydrogen atom and; T.sub.1 represents a saturated linear divalent hydrocarbon-based chain comprising from 1 to 20 carbon atoms, optionally interrupted with one or more groups chosen from N(R.sub.b), C(O), —N.sup.+(R.sub.8)(R.sub.9)-An, cationic heteroaryl, An, or combinations thereof, 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 (C.sub.1-C.sub.4)alkyl group.

38. The process according to claim 37, wherein the at least one anthraquinone dye is chosen from the dyes of formula (II″): ##STR00057##

39. The process according to claim 28, wherein the at least one anthraquinone dye of formulae (I) and/or (II) is chosen from the following compounds, optical isomers thereof, geometrical isomers thereof, tautomers thereof, solvates thereof, or mixtures thereof: ##STR00058## ##STR00059## ##STR00060## ##STR00061## ##STR00062## ##STR00063## ##STR00064## ##STR00065## ##STR00066## ##STR00067## ##STR00068## ##STR00069## ##STR00070## ##STR00071## ##STR00072## ##STR00073## ##STR00074## ##STR00075## ##STR00076## ##STR00077## ##STR00078## wherein An, which may be identical or different, represents an anionic counterion chosen from mesylate, tosylate, or halide.

40. The process according to claim 28, wherein the at least one cationic (poly)methine fluorescent dye is chosen from direct dyes chosen from cyanin dyes, styryl/hemicyanin dyes, naphthalimide dyes, or mixtures thereof.

41. The process according to claim 28, wherein the at least one cationic (poly)methine fluorescent dye is chosen from dyes which absorb light in the yellow, orange and red range.

42. The process according to claim 28, wherein the at least one cationic (poly)methine fluorescent dye is chosen from dyes which bear at least one cationic chromophore chosen from formulae (III), (IV), (IIIa), or (IVa) below:
W.sup.+—[C(R.sup.c)═C(R.sup.d)].sub.m′—Ar′-(*)Q.sup.−  (I)
Ar—[C(R.sup.d)═C(R.sup.c)].sub.m′—W′.sup.+-(*)Q.sup.−  (IV), wherein in formulae (III) and (IV): W.sup.+ represents a cationic heteroaryl group comprising a quaternary ammonium optionally substituted with one or more (C.sub.1-C.sub.8)alkyl groups optionally substituted with one or more hydroxyl groups; W′.sup.+ represents a divalent heteroaryl radical as defined for W.sup.+; Ar represents an aryl group, optionally substituted with i) one or more halogen atoms such as chlorine or fluorine; ii) one or more (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) with one or more acylamino groups; viii) one or more heterocycloalkyl groups; Ar′ is a divalent aryl radical; m′ represents an integer between 1 and 4 inclusive; R.sup.c and R.sup.d, which may be identical or different, represent a hydrogen atom or optionally a substituted (C.sub.1-C.sub.8)alkyl, or alternatively R.sup.c is contiguous with W or W′ and/or R.sup.d is contiguous with Ar or Ar′ and form, with the atoms that bear them, a (hetero)cycloalkyl; Q.sup.− is an organic or mineral anionic counterion; (*) represents the part of the fluorescent chromophore that is bonded to the rest of the dye, ##STR00079## wherein in formulae (IIIa) and (IVa) 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.

43. The process according to claim 28, wherein the at least one cationic (poly)methine fluorescent dye is chosen from the dyes of formulae (V), (VI), or (VII): ##STR00080## organic or mineral acid or base salts thereof, optical isomers, geometrical isomers thereof, tautomers thereof, or solvates thereof; wherein: R.sub.1 and R.sub.2, which may be identical or different, represent a hydrogen atom or a C.sub.1-C.sub.6 alkyl group; G.sub.1 represents a hydrogen atom or a group chosen from NH.sub.2 and OH; R.sub.a, R′.sub.a, R″.sub.a, R′″.sub.a, R.sub.b, R′.sub.b, R″.sub.b, and R′″.sub.b, which may be identical or different, represent a) a hydrogen atom, b) a halogen atom, a group chosen from: c) amino, d) (C.sub.1-C.sub.4)alkylamino, e) (C.sub.1-C.sub.4)dialkylamino, f) cyano, g) carboxyl —C(O)OH or carboxylate —C(O)O.sup.−, Q.sup.+, h) hydroxy —OH or alkoxide —O.sup.−Q.sup.+, i) (poly)halo(C.sub.1-C.sub.6)alkyl j) acylamino, k) (C.sub.1-C.sub.6)alkoxy, l) (C.sub.1-C.sub.6)alkylthio, m) (poly)hydroxy(C.sub.2-C.sub.4)alkoxy, n) (C.sub.1-C.sub.6)alkylcarbonyloxy, o) (C.sub.1-C.sub.6)alkoxycarbonyl, p) (C.sub.1-C.sub.6)alkylcarbonylamino, q) acylamino, r) carbamoyl, s) (C.sub.1-C.sub.6)alkylsulfonylamino, t) aminosulfonyl, u) —SO.sub.3H or sulfonate —SO.sub.3.sup.−, Q.sup.+ or v) (C.sub.1-C.sub.6)alkyl optionally substituted with a group chosen from (C.sub.1-C.sub.6)alkoxy, hydroxyl, cyano, carboxyl, amino, (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; or alternatively two groups R.sub.a and R′.sub.a; R.sub.b and R′.sub.b, 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.1-C.sub.4)alkoxy, (C.sub.1-C.sub.4)alkylcarbonyloxy, (C.sub.1-C.sub.4)alkoxycarbonyl or (C.sub.1-C.sub.4)alkylcarbonylamino radical, an acylamino, carbamoyl or alkoxyalkylsulfonylamino radical, an aminosulfonyl radical, or a (C.sub.1-C.sub.6)alkyl radical optionally substituted with: a group chosen from (C.sub.1-C.sub.6)alkoxy, hydroxyl, cyano, carboxyl, amino, (C.sub.1-C.sub.4)alkylamino, or (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.i and R.sub.a; and/or a group R′.sub.i and R′.sub.a together form a fused (hetero)cycloalkyl; R.sub.g represents a hydrogen atom, a (hetero)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.e represents a covalent bond, a linear or branched, optionally substituted (C.sub.1-C.sub.8)alkylene or (C.sub.2-C.sub.8)alkenylene hydrocarbon-based chain R.sub.f represents a hydrogen atom, a (C.sub.1-C.sub.4)alkoxy group, an amino group R.sub.3R.sub.4N—, a quaternary ammonium group M′, R.sub.3R.sub.4R.sub.5N.sup.+— in which R.sub.3, R.sub.4 and R.sub.5, which may be identical or different, represent a hydrogen atom or a (C.sub.1-C.sub.4)alkyl group or R.sub.3R.sub.4N— represents an optionally substituted heteroaryl group, or alternatively M′, R.sub.3R.sub.4R.sub.5N.sup.+— represents an optionally substituted cationic heteroaryl group; G represents a group i) —NR.sub.cR.sub.d, ii) —OR with R representing a) a hydrogen atom, b) an optionally substituted, preferentially unsubstituted (C.sub.1-C.sub.6)alkyl group, c) an optionally substituted (hetero)aryl group, d) an optionally substituted (hetero)aryl(C.sub.1-C.sub.6)alkyl group such as benzyl, e) optionally substituted (hetero)cycloalkyl group, f) optionally substituted (hetero)cycloalkyl(C.sub.1-C.sub.6)alkyl group; or alternatively when G represents —NR.sub.cR.sub.d, two groups R.sub.c and R′.sub.a and/or R.sub.d and R.sub.a together form a saturated heteroaryl or heterocycle, optionally substituted with one or more (C.sub.1-C.sub.6)alkyl groups; R.sub.c and R.sub.d, which may be identical or different, represent a hydrogen atom or a group chosen from: a) optionally substituted (hetero)aryl, b) optionally substituted (hetero)aryl(C.sub.1-C.sub.4)alkyl, c) optionally substituted (hetero)cycloalkyl, d) optionally substituted (hetero)cycloalkyl(C.sub.1-C.sub.4)alkyl, f) (C.sub.2-C.sub.5)alkyl, or g) (C.sub.1-C.sub.8)alkyl which is optionally substituted; or alternatively two adjacent radicals R.sub.c and R.sub.d borne by the same nitrogen atom together form an optionally substituted heterocyclic or optionally substituted heteroaryl group; 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; ##STR00081##  represents a (hetero)aryl group fused to the phenyl ring; or alternatively is absent from the phenyl; m represents an integer between 1 and 18 inclusive; M′ represents 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; Q.sup.+ represents a cationic 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 such as alkali metal, alkaline-earth metal or ammonium; wherein when the molecule comprises a carboxylate, sulfonate or alkoxide group, then M′ and Q.sup.+ may be absent to ensure the electrical neutrality of said molecule.

44. The process according to claim 28, wherein the at least one cationic (poly)methine fluorescent dye is chosen from styryl dyes of formula (VIII) below: ##STR00082## organic or mineral acid or base salts thereof, optical isomers thereof, geometrical isomers thereof, tautomers thereof, or solvates thereof; wherein R.sub.1 and R.sub.2, which may be identical or different, represent a hydrogen atom; 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.a, R′.sub.a and R″.sub.a, which may be identical or different, represent a hydrogen atom, a halogen atom, or an —OH, —O.sup.−Q.sup.+, (C.sub.1-C.sub.6)alkoxy, nitro, or cyano group, wherein Q.sup.+ represents a cationic 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; R.sub.b, R′.sub.b and R″.sub.b, which may be identical or different, represent a hydrogen atom or a (C.sub.1-C.sub.6)alkyl group; or alternatively two contiguous radicals R.sub.b and R′.sub.b form, together with the carbon atoms that bear them, a benzo group that is condensed or fused to the pyridinium group, said benzo group optionally substituted; G represents a group —NR.sub.cR.sub.d or (C.sub.1-C.sub.6)alkoxy group which is optionally substituted; G.sub.1 represents a hydrogen atom or an OH or NH.sub.2 group; 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; ##STR00083##  represents an aryl or heteroaryl group fused to the phenyl ring; or alternatively is absent from the phenyl ring; m represents an integer between 1 and 18 inclusive; R.sub.c and R.sub.d, which may be identical or different, represent a hydrogen atom, a (C.sub.2-C.sub.4)alkyl group or a substituted (C.sub.1-C.sub.8)alkyl group; and M′ represents 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; wherein when the molecule comprises an alkoxide group, then M′ and Q.sup.+ are optionally absent to ensure the electrical neutrality of said molecule.

45. The process according to claim 28, wherein the at least one cationic (poly)methine fluorescent dye is chosen from the dyes of the compounds of formulae (X), (XI), (XII), or (XIII) below: ##STR00084## organic or mineral acid salts thereof, optical isomers thereof, geometrical isomers thereof, tautomers thereof, or solvates thereof; wherein in formula (X), (XI), (XIII), or (XIII): R.sup.1, R.sup.2, R.sup.3 and R.sup.4, which may be identical or different, represent a hydrogen atom or a (C.sub.1-C.sub.6)alkyl group; R.sup.5, R.sup.6, R.sup.7, R.sup.8 and R.sup.9, which may be identical or different, represent i) a hydrogen atom or ii) a halogen atom, iii) a group OR in which R represents a hydrogen atom or Q.sup.+ represents a cationic 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, or a (C.sub.1-C.sub.3)alkyl group, iv) aryl, v) an aryl(C.sub.1-C.sub.3)alkyl group, vi) cyano, vii) nitro, viii) (C.sub.1-C.sub.3)alkylthio, ix) amino NR.sup.10R.sup.11 with R.sup.10 and R.sup.11, which may be identical or different, representing a) a hydrogen atom, b) a (C.sub.2-C.sub.4)alkyl group or c) a substituted (C.sub.1-C.sub.8)alkyl group: cyano, (C.sub.1-C.sub.3)alkoxy, hydroxyl, and (C.sub.1-C.sub.3)alkylcarbonyl; m represents an integer between 1 and 18 inclusive; M′ represents 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; wherein when the molecule comprises an alkoxide group, then M′ and Q.sup.+ are optionally absent to ensure the electrical neutrality of the molecule.

46. The process according to claim 28, wherein the at least one cationic (poly)methine fluorescent dye is chosen from those of formulae (XIV) or (XV) below: ##STR00085## wherein: R.sup.5 and R.sup.8, which may be identical or different, represent a hydrogen atom or a (C.sub.1-C.sub.4)alkoxy group; R.sup.7 represents a (C.sub.1-C.sub.4)alkoxy group or NR.sup.10R.sup.11 with R.sup.10 and R.sup.11, which may be identical or different, representing a) a hydrogen atom, or b) a (C.sub.1-C.sub.8)alkyl group optionally substituted with one or more groups chosen from i) hydroxyl, ii) R—Z—C(X)—Y— with X, Y and Z representing an oxygen or sulfur atom or N(R′), or alternatively X and/or Z represent a bond, R and R′, which may be identical or different, represent a hydrogen atom or a (C.sub.1-C.sub.6)alkyl group, iii) sulfonic SO.sub.3H, iv) sulfonate SO.sub.3.sup.−, Q.sup.+, v) carboxylate C(O)O.sup.−, Q.sup.+ with Q.sup.+ representing a cationic counterion; m represents an integer between 1 and 18 inclusive; and M′ represents 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; wherein when the molecule comprises an alkoxide group, then M′ and Q.sup.+ are optionally absent to ensure the electrical neutrality of said molecule.

47. The process according to claim 46, wherein: the at least one cationic (poly)methine fluorescent dye is chosen from compounds of formula (X), wherein: TABLE-US-00014 R.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.5 R.sup.6 R.sup.7 R.sup.8 R.sup.9 m H H H H H H H H H 1 H H H H H t-Bu OH t-Bu H 5 H H H H H t-Bu OH t-Bu H 5 H H H H H H NH.sub.2 H H 1 H H H H H H NH.sub.2 H OCH.sub.3 1 H H H H H H OH Br H 5 H H H H H OCH.sub.3 OH OCH.sub.3 H 5 H H H H Cl H OH H Cl 5 H H H H H H OH H H 10 H H H H H OCH.sub.3 OH OCH.sub.3 H 10 H H H H H t-Bu OH t-Bu H 10 H H H H H H N(CH.sub.2CH.sub.3).sub.2 H H 1 H H H H H H N(CH.sub.2CH.sub.3).sub.2 H H 1 H H H H H H N(CH.sub.2CH.sub.3).sub.2 H H 1 H H H H H t-Bu OH t-Bu H 10 H H H H H H N(CH.sub.2CH.sub.3)CH.sub.2CH.sub.2OH H H 1 H H H H H H N(CH.sub.2CH.sub.3).sub.2 H H 1 H H H H H H N(CH.sub.2CH.sub.3).sub.2 H H 1 H H H H H H N(CH.sub.2CH.sub.3).sub.2 H H 1 H H H H H H N(CH.sub.2CH.sub.3).sub.2 H H 1 H H H H H H N(CH.sub.2CH.sub.3).sub.2 H H 1 H H H H H H N(CH.sub.2CH.sub.3).sub.2 H H 1 H H H H H H N(CH.sub.2CH.sub.3).sub.2 H H 1 H H H H H H N(CH.sub.2CH.sub.3).sub.2 H H 1 H H H H H H N(CH.sub.2CH.sub.3).sub.2 H H 1 H H H H H H n-C.sub.6H.sub.13 H H 1 H H H H H H N(CH.sub.2CH.sub.2OH).sub.2 H H 2 H H H H H H N(n-Bu).sub.2 H H 2 H H H H H OCH.sub.3 OH H H 10 H H H H H H OC.sub.2H.sub.5OH H H 1 H H H H H H OH H H 1 H H benzo H H H H H 1 H H benzo H H N(CH.sub.2CH.sub.2OH).sub.2 H H 1 H H benzo H H N(CH.sub.2CH.sub.2OH).sub.2 H H 1 organic or mineral acid or base salts thereof, optical isomers, geometrical isomers thereof, tautomers thereof, or solvates thereof; cationic (poly)methine fluorescent dyes of formula (XI), wherein: TABLE-US-00015 R.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.5 R.sup.6 R.sup.7 R.sup.8 R.sup.9 m CH.sub.3 H H H OH H OCH.sub.3 H H 2 CH.sub.3 H H H H H OCH.sub.3 OCH.sub.2—Ph H 2 CH.sub.3 H H H H H H H OCH.sub.3 2 CH.sub.3 H H H F H H H H 2 CH.sub.3 H H H H H H OPh H 2 CH.sub.3 H H H H H N(CH.sub.2CH.sub.2OAc).sub.2 H H 2 CH.sub.3 H H H OCH.sub.3 H OCH.sub.3 OCH.sub.3 H 2 CH.sub.3 H H H H H H CH.sub.3 H 2 CH.sub.3 H H H H H OH H H 2 CH.sub.3 H H H H OCH.sub.3 OCH.sub.3 OCH.sub.3 H 2 CH.sub.3 H H H H OCH.sub.3 OH OH H 2 CH.sub.3 H H H H H OCH.sub.3 OCH.sub.3 OCH.sub.3 2 CH.sub.3 H H H H H H OCH.sub.3 OH 2 CH.sub.3 H H H H H N(n-butyl).sub.2 H H 2 CH.sub.3 H H H H OCH.sub.3 OCH.sub.3 H H 2 CH.sub.3 H H H H H H H H 2 CH.sub.3 H H H H H i-propyl H H 2 H H H H H H OH H H 6 H H H H H OCH.sub.3 OCH.sub.3 OCH.sub.3 H 6 H H H H OH H OCH.sub.3 H H 2 H H H H OCH.sub.3 H H OCH.sub.3 OCH.sub.3 2 H H H H H H H H Br 2 H H H H H H OH H H 2 H H H H OCH.sub.3 OCH.sub.3 OCH.sub.3 H H 6 H H H H OH OCH.sub.3 H H H 6 H H H H H OCH.sub.3 OCH.sub.3 H H 6 H H H H H OCH.sub.3 OCH.sub.3 H H 2 H H H H H H C(O)—OH H H 6 H H H H H H C(O)—OH H H 2 H H H H H H i-propyl H H 2 H H H H H H N(CH.sub.3)CH.sub.2CH.sub.2CN H H 2 H H H H H H OCH.sub.3 OCH.sub.2Ph H 2 H H H H H H H OPh H 2 H H H H H H N(CH.sub.2CH.sub.2C(O)CH.sub.3).sub.2 H H 2 H H H H OH H OCH.sub.3 H H 6 H H H H H OCH.sub.3 OCH.sub.3 OCH.sub.3 H 2 H H H H OCH.sub.3 H OCH.sub.3 OCH.sub.3 H 6 H H H H H H H CH.sub.3 H 2 H H H H H H N(CH.sub.3)CH.sub.2CH.sub.2OH H H 2 organic or mineral acid or base salts thereof, geometrical isomers thereof, tautomers thereof, or solvates thereof; cationic (poly)methine fluorescent dyes of formulae (X′) or (XI′): ##STR00086## wherein TABLE-US-00016 R.sup.5 R.sup.7 R.sup.8 m R.sup.5 R.sup.7 R.sup.8 M H N(CH.sub.2CH.sub.2OH).sub.2 H 2 and OCH.sub.3 OCH.sub.3 OCH.sub.3 2 H N(CH.sub.2CH.sub.2OH).sub.2 H 3 OCH.sub.3 OCH.sub.3 OCH.sub.3 3 H N(CH.sub.2CH.sub.2OH).sub.2 H 4 OCH.sub.3 OCH.sub.3 OCH.sub.3 3 H N(CH.sub.2CH.sub.2OH).sub.2 H 5 OCH.sub.3 OCH.sub.3 OCH.sub.3 4 H N(CH.sub.2CH.sub.2OH).sub.2 H 6 OCH.sub.3 OCH.sub.3 OCH.sub.3 5 H N(CH.sub.2CH.sub.2OH).sub.2 H 8 OCH.sub.3 OCH.sub.3 OCH.sub.3 8 H N(CH.sub.2CH.sub.2OH).sub.2 H 10 OCH.sub.3 OCH.sub.3 OCH.sub.3 10 H N(CH.sub.2CH.sub.2OH).sub.2 H 12 OCH.sub.3 OCH.sub.3 OCH.sub.3 12 H N(CH.sub.2CH.sub.2OH).sub.2 H 14 OCH.sub.3 OCH.sub.3 OCH.sub.3 14 H N(CH.sub.2CH.sub.2OH).sub.2 H 16 OCH.sub.3 OCH.sub.3 OCH.sub.3 16 H CH.sub.3CH.sub.2N(CH.sub.2CH.sub.2OH) H 2 H CH.sub.3CH.sub.2N(CH.sub.2CH.sub.2OH) H 4 organic or mineral acid or base salts thereof, geometrical isomers thereof, tautomers thereof, or solvates thereof; cationic (poly)methine fluorescent dyes of formula (XII) wherein: TABLE-US-00017 R.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.5 R.sup.6 R.sup.7 R.sup.8 R.sup.9 m H H H H H H OCH.sub.3 OCH.sub.3 OCH.sub.3 2 H H H H OH OCH.sub.3 H H H 2 H H H H H H H H H 2 H H H H H OCH.sub.3 OCH.sub.3 H H 2 H H H H OH H OH H H 6 H H H H OCH.sub.3 H OCH.sub.3 OCH.sub.3 H 6 H H H H H H OH H H 6 H H H H OCH.sub.3 H H H F 2 H H H H H H C(O)—OH H H 2 H H H H H H Isopropyl H H 2 H H H H H H N(CH.sub.2CH.sub.2C(O)CH.sub.3).sub.2 H H 2 H H H H OH H OCH.sub.3 H H 2 H H H H H H OH H H 2 H H H H H OCH.sub.3 OH OH H 2 H H H H H CH.sub.3 OCH.sub.2Ph CH.sub.3 H 2 H H H H H OCH.sub.3 OCH.sub.3 OCH.sub.3 H 2 H H H H H OCH.sub.3 OCH.sub.3 OCH.sub.3 H 6 H H H H H H N(CH.sub.3).sub.2 H H 6 H H H H H H OCH.sub.3 OCH.sub.3 OCH.sub.3 6 H H H H H H Phenyl H H 6 H H H H H OCH.sub.3 OCH.sub.3 H H 6 H H H H H H C(O)—OH H H 6 H H H H H H N(n-Butyl).sub.2 H H 2 H H H H H H OCH.sub.3 OCH.sub.3 H 3 H H H H H H OCH.sub.3 OCH.sub.3 H 2 H H H H H H OCH.sub.3 OCH.sub.3 H 5 H H H H H H OCH.sub.3 H H 3 H H H H H H N(CH.sub.3).sub.2 H H 3 H H H H H H H H H 3 organic or mineral acid or base salts thereof, optical isomers thereof, geometrical isomers thereof, tautomers thereof, or solvates thereof; cationic (poly)methine fluorescent dyes of formula (XIII), wherein: TABLE-US-00018 R.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.5 R.sup.6 R.sup.7 R.sup.8 R.sup.9 m CH.sub.3 H H H OH H OCH.sub.3 H H 2 CH.sub.3 H H H H H OCH.sub.3 OCH.sub.2—Ph H 2 CH.sub.3 H H H H H H H OCH.sub.3 2 CH.sub.3 H H H F H H H H 2 CH.sub.3 H H H H H H OPh H 2 CH.sub.3 H H H H H N(CH.sub.2CH.sub.2OAc).sub.2 H H 2 CH.sub.3 H H H OCH.sub.3 H OCH.sub.3 OCH.sub.3 H 2 CH.sub.3 H H H H H H CH.sub.3 H 2 CH.sub.3 H H H H H OH H H 2 CH.sub.3 H H H H OCH.sub.3 OCH.sub.3 OCH.sub.3 H 2 CH.sub.3 H H H H OCH.sub.3 OH OH H 2 CH.sub.3 H H H H H OCH.sub.3 OCH.sub.3 OCH.sub.3 2 CH.sub.3 H H H H H H OCH.sub.3 OH 2 CH.sub.3 H H H H H N(n-butyl).sub.2 H H 2 CH.sub.3 H H H H OCH.sub.3 OCH.sub.3 H H 2 CH.sub.3 H H H H H H H H 2 CH.sub.3 H H H H H i-propyl H H 2 H H H H H H OH H H 6 H H H H H OCH.sub.3 OCH.sub.3 OCH.sub.3 H 6 H H H H OH H OCH.sub.3 H H 2 H H H H OCH.sub.3 H H OCH.sub.3 OCH.sub.3 2 H H H H H H H H Br 2 H H H H H H OH H H 2 H H H H H H N(CH.sub.3).sub.2 H H 6 H H H H OCH.sub.3 OCH.sub.3 OCH.sub.3 H H 6 H H H H OH OCH.sub.3 H H H 6 H H H H H OCH.sub.3 OCH.sub.3 H H 6 H H H H H OCH.sub.3 OCH.sub.3 H H 2 H H H H H H C(O)—OH H H 6 H H H H H H C(O)—OH H H 2 H H H H H H i-propyl H H 2 H H H H H H N(CH.sub.3)CH.sub.2CH.sub.2CN H H 2 H H H H H H OCH.sub.3 OCH.sub.2Ph H 2 H H H H H H H OPh H 2 H H H H H H N(CH.sub.2CH.sub.2C(O)CH.sub.3).sub.2 H H 2 H H H H OH H OCH.sub.3 H H 6 H H H H H OCH.sub.3 OCH.sub.3 OCH.sub.3 H 2 H H H H OCH.sub.3 H OCH.sub.3 OCH.sub.3 H 6 H H H H H H H CH.sub.3 H 2 H H H H H H N(CH.sub.3)CH.sub.2CH.sub.2OH H H 2 CH.sub.3 H H H H H N(CH.sub.3).sub.2 H H 2 organic or mineral acid or base salts thereof, geometrical isomers thereof, tautomers thereof, or the solvates thereof; cationic (poly)methine fluorescent dyes of formulae (XII′) or (XIII′) below: ##STR00087## wherein: TABLE-US-00019 R.sup.5 R.sup.7 R.sup.8 m R.sup.5 R.sup.7 R.sup.8 m H N(CH.sub.2CH.sub.2OH).sub.2 H 2 and OCH.sub.3 OCH.sub.3 OCH.sub.3 2 H N(CH.sub.2CH.sub.2OH).sub.2 H 3 OCH.sub.3 OCH.sub.3 OCH.sub.3 3 H N(CH.sub.2CH.sub.2OH).sub.2 H 4 OCH.sub.3 OCH.sub.3 OCH.sub.3 3 H N(CH.sub.2CH.sub.2OH).sub.2 H 5 OCH.sub.3 OCH.sub.3 OCH.sub.3 4 H N(CH.sub.2CH.sub.2OH).sub.2 H 6 OCH.sub.3 OCH.sub.3 OCH.sub.3 5 H N(CH.sub.2CH.sub.2OH).sub.2 H 8 OCH.sub.3 OCH.sub.3 OCH.sub.3 8 H N(CH.sub.2CH.sub.2OH).sub.2 H 10 OCH.sub.3 OCH.sub.3 OCH.sub.3 10 H N(CH.sub.2CH.sub.2OH).sub.2 H 12 OCH.sub.3 OCH.sub.3 OCH.sub.3 12 H N(CH.sub.2CH.sub.2OH).sub.2 H 14 OCH.sub.3 OCH.sub.3 OCH.sub.3 14 H N(CH.sub.2CH.sub.2OH).sub.2 H 16 OCH.sub.3 OCH.sub.3 OCH.sub.3 16 organic or mineral acid or base salts thereof, geometrical isomers thereof, tautomers thereof, or solvates thereof; cationic (poly)methine fluorescent dyes chosen from the following compounds: ##STR00088## organic or mineral acid or base salts thereof, geometrical isomers thereof, tautomers thereof, or the solvates thereof.

48. The process according to claim 28, wherein the process further comprises applying to said keratin fibers a cosmetic composition comprising c) one or more reducing agents.

49. The process according to claim 28, wherein the process does not use any reducing agent.

50. The process according to claim 28, wherein the at least one anthraquinone compound and the at least one cationic (poly)methine fluorescent direct dye are applied together to the keratin fibers.

51. The process according to claim 28, wherein the process comprises at least two successive steps: a step of applying to the keratin fibers a cosmetic composition comprising (b) at least one cationic (poly)methine fluorescent dye, followed by, a step of applying to the keratin fibers a cosmetic composition comprising (a) at least one or more anthraquinone dye of formula (I) and/or (II).

52. The process according to claim 28, wherein the process comprises at least two successive steps: a step of applying to the fibers a cosmetic composition comprising (a) at least one anthraquinone dye of formula (I) and/or (II), followed by a step of applying to the keratin fibers a cosmetic composition comprising (b) at least one cationic (poly)methine fluorescent dye.

53. The process according to claim 28, wherein the pH of the cosmetic composition is between 6 and 11 inclusive.

54. A cosmetic composition comprising (a) at least one anthraquinone dye chosen from the compounds of formulae (I) and/or (II) below, optical isomers thereof, geometrical isomers thereof, tautomers thereof, solvates thereof, or mixtures thereof: ##STR00089## wherein in formula (I) and/or (II): X.sub.a, which may be identical or different, represents a bond, a heteroatom or a group chosen from an oxygen or sulfur atom, N(R.sub.a), CO, SO, SO.sub.2, or combinations thereof, with R.sub.a representing a hydrogen atom or a (C.sub.1-C.sub.6)alkyl group optionally substituted with one or more hydroxyl groups; 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.aR.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 (III) below: ##STR00090## 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 a group chosen from: hydrogen; halogen such as bromine and chlorine, 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)alkylcarbonyl, iii) arylsulfonyl such as phenylsulfonyl (—SO.sub.2Ph), iv) Het-ALK-C(O)— with Het representing a heterocycloalkyl group which is optionally substituted 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, 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; a group of formula (a) below:
—N(R.sub.7)—X.sub.1—W.sub.1  (a) wherein in formula (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, sulfur, CO, SO, SO.sub.2, arylene, or combinations thereof; W.sub.1 represents a cationic radical chosen from: ##STR00091## 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; n is an integer ranging from 1 to 3; 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, represent 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; being the part of the bond that is connected to the rest of the molecule; and (b) at least one cationic (poly)methine fluorescent dye.

Description

EXAMPLES

1. Application Tests Performed:

[0357] The tests were performed: [0358] at a molar concentration of 5×10.sup.−3 mol % of each dye (Example 1) [0359] at a molar concentration of 5×10.sup.−3 mol % of anthraquinone dye and of 1.66×10.sup.−3 mol % of fluorescent dye (Example 2) [0360] The solutions are adjusted to pH 9-9.5 with aqueous ammonia solution.
The compounds tested on a 0.5 g lock of hair containing 90% white hairs are the following:
The violet-blue dyes, of the anthraquinone disulfide series or not, evaluated in the context of the invention are the following:

TABLE-US-00007 Dye (a) Structure of violet-blue dyes Dye 1 [00045] Dye 2 [00046] Dye 3 [00047]
The fluorescent dyes of the styrylpyridinium series evaluated in the context of the invention are the following:

TABLE-US-00008 Dye (b) Structure of the fluorescent dyes Dye a [00048] Dye b [00049]
The combinations of dyeing compounds were prepared on a 0.5 g lock of natural hair containing 90% white hairs as a mixture (NW90) according to 3 application modes:

[0361] In Reducing Medium: [0362] “blue direct dye” then “fluorescent dye” (application sense 1—AS1)

[0363] In Non-Reducing Medium: [0364] “fluorescent dye” then “blue direct dye” (application sense 2—AS2) [0365] “blue direct dye” then “fluorescent dye” (application sense 3—AS3) [0366] “blue direct dye” and “fluorescent dye” as a mixture before application (application sense 4—AS4).
For application sense 1—AS1, the products were applied as follows:
Application condition for the blue direct dye/fluorescent dye:
The amount of a) dye of formula (I) or (II) according to the invention [blue] and of b) fluorescent dyes=5×10.sup.−3 mol % in water [0367] 9 ml of this mixture+1 ml of Dulcia DV2 (bath ratio=5) [0368] 20 minutes at room temperature (RT=25° C.)+rinsing+H.sub.2O.sub.2(0.48 g %) 5 minutes at RT [0369] rinsing+1 shampooing+drying under a hood for 10 minutes per g of hair
For application senses 2 (AS2), 3 (AS3) and 4 (AS4), the products were applied as follows:
Application condition for the blue direct dye of formula (I) or (II): 5×10−3 mol % in water, 30 minutes at RT+rinsing+1 shampooing+drying under a hood for 10 minutes per g of hair.
Application condition for the fluorescent dye: 5×10.sup.−3 mol % in water, 20 minutes at RT+rinsing+1 shampooing+drying under a hood for 10 minutes per g of hair
Application condition for the mixture “blue direct dye of formula (I) or (II)+fluorescent dye”: 5×10.sup.−3 mol % of each of the dyes in water, 45 minutes at RT+rinsing+1 shampooing+drying under a hood for 10 minutes per g of hair

Example 1

[0370] The following hair dyeing results were obtained:

TABLE-US-00009 Blue dye Fluorescent dye Application sense Colour obtained Dye 1 Dye a AS2 Brown with a coppery glint Dye 1 Dye a AS3 Brown with a coppery glint Dye 1 Dye a AS4 Brown with a coppery glint Dye 1 Dye b AS1 Brown with a coppery glint Dye 2 Dye a AS1 Brown with a coppery glint Dye 2 Dye b AS1 Brown with a coppery glint Dye 2 Dye b AS2 Brown with a coppery glint Dye 2 Dye b AS3 Brown with a coppery glint Dye 2 Dye b AS4 Brown with a coppery glint Dye 3 Dye a AS1 Dull brown Dye 3 Dye b AS1 Brown
It is seen that the process of the invention makes it possible to obtain very aesthetic and powerful brown colours just by combining a blue dye and a fluorescent dye.

Comparative Data:

Comparative Experiment

[0371] 3 series of locks (90% natural with hair—90 NW) have been carried out with an equimolar association of a reductive or not medium vs. comparative prior art EP0852943A1.
The tests has been carried out at a molar concentration of 5×10-3 mol % for each dye. The compositions are adjusted to pH 9-9.5 with an ammonia solution. The compounds tested on locks of 0.5 g of natural white hair (90 NWV) are the following:
The blue disulfide anthraquinone dye, and the hemicyanin dyes have been evaluated in the context of the comparison as follows:

TABLE-US-00010 Dye (a) chemical structure of Blue-violet dye Dye 3 [00050]

TABLE-US-00011 Dye (b) chemical structure of hemicyanin fluorescent dyes Dye a EP0852943A1 Comparative [00051] Dye b Invention [00052]

In Reducing Medium:

[0372] “blue disulfide direct dye” and “fluorescent dye” (application sense 1—SA1)
Application condition of the blue disulfide direct dye/fluorescent dye:
The amount of a) dye 3 and b) fluorescent dyes=5.10-3 mol % in water [0373] 9 ml of this mixture+1 ml dulcia DV2 [0374] 20′/TA+rinse+H.sub.2O.sub.2 (0.48 g %) 5′/TA [0375] rinsing+1 shampoo+drying with headphones 10′/g of hair [0376] In a non-reducing medium: [0377] “blue disulfide direct dye” and “fluorescent dye” mixed before application (method 2—SA2).
The method of applying the mixture «blue disulfide direct dye 3+fluorescent dye» 5.10-3 mol % in water, for 45° at room temperature (27° C.)/TA+rinsing+1 shampoo+drying au hair 10′/g of hair

Results

[0378]

TABLE-US-00012 Blue direct dye Fluorescent dye application sense Color after treatment Dye 3 AS1 Blue Dye 3 AS2 Blue Dye a AS1 No coloration Dye a AS2 No coloration Dye b AS1 Red Dye b AS2 Red Dye 3 Dye a AS1 Red Dye 3 Dye b AS1 Brown with shade Dye 3 Dye a AS2 Blue Dye 3 Dye b AS2 Cold brown
After treating keratin fibers with dyes and shampoo locks have been dried and color on the locks has been measured with spectrocolorimeter Minolta CM2600d (angle 10°, illuminant D65) in the CIEL*a*b* system.
In this system, L* represents intensity of the color, a* represents the green/red color axis and b* the blue/yellow color axis.
The lowest L* measured, the most intensive is the color.

TABLE-US-00013 Blue Dye Fluorescent dye Application sense L* a* b* Dye 3 AS1 32.03 −5.72 −19 Dye 3 AS2 35.41 −7.06 −14.56 Dye a AS1 59.86 0.54 15.83 Dye a AS2 61.59 0.65 10.98 Dye b AS1 28.23 38.77 25.94 Dye b AS2 33.27 43.76 31.17 Dye 3 Dye a AS1 32.25 −5.03 −18.65 Dye 3 Dye b AS1 19.29 10.66 8.56 Dye 3 Dye a AS2 35.82 −5.89 −17.44 Dye 3 Dye b AS2 24.3 18.77 16.51
These results of the table show that the method according to the invention, using only two direct fluorescent dyes b), anthraquinone dye of formula (I) and/or (II) of the invention associated with a cationic fluorescent dye, makes it possible to obtain natural brown colors. This is not the case of the combination of an anthraquinone dye of formula (I) and/or (II) of EP0852943A1 combined with a non-cationic fluorescent dye a) for which the color obtained is blue (non natural color).