PROCESS FOR DYEING KERATIN FIBRES USING AT LEAST ONE PARTICULAR AZINIUM DYE AND AT LEAST ONE FLUORESCENT DYE

Abstract

The present invention relates to a process for dyeing keratin fibres, in particular human keratin fibres such as the hair, using one or more particular azinium dyes and one or more fluorescent dyes. The present invention also relates to a cosmetic composition comprising the dyes defined above, and also to a multi-compartment device containing said dyes. The present invention also relates to the use of said dyes for dyeing light keratin fibres, especially human keratin fibres such as the hair, in chestnut-brown, dark chestnut-brown, brown, brown with a glint, or even black, without using an additional dye other than those defined above.

Claims

1. Process for dyeing keratin fibres, in particular human keratin fibres such as the hair, comprising the application to said keratin fibres of the following ingredients: (a) one or more azinium dyes chosen from the compounds of formula (I) below, the optical isomers thereof, the geometrical isomers thereof, the tautomers thereof, the organic or mineral, acid or base salts thereof, the solvates thereof such as hydrates, and mixtures thereof, ##STR00041## in which formula (I): X represents an oxygen atom, NR.sub.2 or a cationic radical N.sup.+R.sub.2R.sub.3; G represents an oxygen atom, a sulfur atom or a radical NR.sub.6; R.sub.2, R.sub.3, R.sub.2 and R.sub.3, which may be identical or different, represent, independently of each other: a hydrogen atom, a phenyl radical which is optionally substituted, especially with one or more halogen atoms, or a linear or branched C.sub.1 to C.sub.20, preferably C.sub.1 to C.sub.10 and more preferentially C.sub.1 to C.sub.6 alkyl radical, optionally substituted especially with one or more groups chosen from hydroxyl, (di)(C.sub.1-C.sub.4)(alkyl)amino, amino NH.sub.2, (di)(C.sub.1-C.sub.4)(alkyl)aminocarbonyl, aminocarbonyl C(O)NH.sub.2, and 5- or 6-membered heterocycloalkyl, which is preferably saturated, such as morpholino, piperazino or piperidino, and/or optionally interrupted with one or more heteroatoms and/or with one or more groups comprising at least one heteroatom, preferably chosen from oxygen, sulfur, N(R.sub.6), C(O), S(O), S(O.sub.2) or combinations thereof, preferably O, N(R.sub.6), N(R.sub.6)C(O), C(O)N(R.sub.6), with R.sub.6 representing a hydrogen atom or a (C.sub.1-C.sub.4)alkyl group; R.sub.5 and R.sub.5, which may be identical or different, represent: a hydrogen atom, a linear or branched C.sub.1 to C.sub.6 alkyl radical, an optionally substituted phenyl radical, a hydroxycarbonyl radical C(O)OH, a carboxylate radical C(O)O, a (di)(C.sub.1-C.sub.6)(alkyl)aminocarbonyl radical, an aminocarbonyl radical C(O)NH.sub.2, a (di)(C.sub.1-C.sub.6)(alkyl)amino radical, or an amino radical NH.sub.2; R.sub.1, R.sub.4, R.sub.1 and R.sub.4, which may be identical or different, represent, independently of each other: a hydrogen atom, a C.sub.1 to C.sub.4 and preferably C.sub.1 to C.sub.2 alkyl radical, a C.sub.1 to C.sub.4 and preferably C.sub.1 to C.sub.2 alkoxy radical, a hydroxyl radical, or an amino radical R.sub.7R.sub.8N with R.sub.7 and R.sub.8, which may be identical or different, representing a hydrogen atom, a (C.sub.1-C.sub.4)alkyl group, or a phenyl radical which is optionally substituted, especially with one or more halogen atoms or one or more nitro(so) groups, or a nitro(so) radical; or alternatively R.sub.4 forms with one of the substituents R.sub.2 or R.sub.3 a saturated or unsaturated, preferably saturated 5- or 6-membered, optionally substituted heterocycle, preferably morpholinyl, piperazinyl or piperidinyl; R.sub.6 represents a phenyl radical which is optionally substituted, especially with a (di)(C.sub.1-C.sub.4)(alkyl)amino radical and/or a linear or branched C.sub.1 to C.sub.6 alkyl radical; and when the compound of formula (I) is cationic, it optionally comprises one or more anions Y.sup. and optionally one or more cations M.sup.+ to ensure the electrical neutrality of the molecule, with Y.sup. represents an anionic counterion or a mixture of organic or mineral anions; M.sup.+ represents an organic or mineral cationic counterion, preferably an alkali metal or alkaline-earth metal such as sodium, potassium or calcium, or ammonium; and (b) one or more fluorescent dyes; said fluorescent dyes being direct dyes chosen from cyanin dyes, styryl/hemicyanin dyes, naphthalimide dyes, and mixtures thereof; it being understood that the azinium dye(s) (a) and the fluorescent dye(s) (b) are applied to said keratin fibres together or sequentially.

2. Process according to claim 1, characterized in that R.sub.2, R.sub.3, R.sub.2 and R.sub.3, which may be identical or different, represent, independently of each other: a hydrogen atom, a phenyl radical, or an optionally substituted, linear or branched C.sub.1 to C.sub.10 and preferably C.sub.1 to C.sub.6 alkyl radical, one or more radicals chosen from the following radicals: hydroxyl, amino NH.sub.2, aminocarbonyl C(O)NH.sub.2, and saturated 5- or 6-membered heterocycloalkyl.

3. Process according claim 1, characterized in that R.sub.5 and R.sub.5, which may be identical or different, represent a hydrogen atom, a linear or branched C.sub.1 to C.sub.6 and more preferentially C.sub.1 to C.sub.4 alkyl radical, such as a methyl, a (di)(C.sub.1-C.sub.6)(alkyl)amino radical, an amino radical NH.sub.2, a hydroxycarbonyl radical C(O)OH or an aminocarbonyl radical C(O)NH.sub.2.

4. Process according to claim 1, characterized in that the azinium dye(s) (a) are chosen from the following compounds, the optical isomers thereof, the geometrical isomers thereof, the tautomers thereof, the organic or mineral, acid or base salts thereof, the solvates thereof such as hydrates, and mixtures thereof: ##STR00042## ##STR00043## ##STR00044## ##STR00045## ##STR00046## wherein Y.sup. represents an anionic counterion or a mixture of organic or mineral anions.

5. Process according to claim 1, characterized in that X represents an oxygen atom.

6. Process according to claim 1, characterized in that X represents a cationic radical N.sup.+R.sub.2R.sub.3, in which R.sub.2 and R.sub.3 are as defined previously, preferably R.sub.2 and R.sub.3, which may be identical or different, represent, independently of each other, a hydrogen atom or a linear or branched C.sub.1 to C.sub.10 and more preferentially C.sub.1 to C.sub.6 alkyl radical, optionally substituted with one or more radicals chosen from the following radicals: hydroxyl, amino, optionally substituted with one or two identical or different C.sub.1-C.sub.4 alkyl radicals, said alkyl radicals possibly forming, with the nitrogen atom that bears them, a 5- to 7-membered heterocycle, or carbamoyl ((R).sub.2NC(O)), in which R, which may be identical or different, represent a hydrogen atom or a C.sub.1 to C.sub.4 alkyl radical.

7. Process according to claim 1, characterized in that the fluorescent dye(s) (b) are direct and cationic and are chosen from styryl or hemicyanin cationic dyes.

8. Process according to claim 1, characterized in that the fluorescent dye(s) (b) are dyes which absorb light in the yellow, orange and red range, preferably in the absorption wavelength .sub.abs between 400 nm and 500 nm inclusive.

9. Process according to claim 1, characterized in that the fluorescent dye(s) (b) are dyes which bear at least one cationic chromophore chosen from formulae (III), (IV), (IIIa) and (IVa) below:
W.sup.+[C(R.sup.c)C(R.sub.d)].sub.mAr-(*)Q.sup.(III)
Ar[C(R.sup.d)C(R.sup.c)].sub.mW.sup.+-(*)Q.sup.(IV), in which formulae (III) and (IV): W.sup.+ represents a cationic heteroaryl group, in particular comprising a quaternary ammonium optionally substituted with one or more (C.sub.1-C.sub.8)alkyl groups optionally substituted in particular with one or more hydroxyl groups; W.sup.+ represents a divalent heteroaryl radical as defined for W.sup.+; Ar represents an aryl group such as phenyl or naphthyl, optionally substituted preferably with i) one or more halogen atoms such as chlorine or fluorine; ii) one or more (C.sub.1-C.sub.8)alkyl and preferably C.sub.1-C.sub.4 alkyl groups 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, piperidyl or 5- or 6-membered heteroaryl such as pyrrolidinyl, pyridyl and imidazolinyl; Ar is a divalent aryl radical as defined for Ar; m represents an integer between 1 and 4 inclusive, in particular, m is 1 or 2; better still 1; 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 and preferably C.sub.1-C.sub.4 alkyl group, 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; in particular, R 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; (*) represents the part of the fluorescent chromophore that is bonded to the rest of the dye; 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)(alkyl)amino 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; ##STR00047## where represents the bond with the dye in which 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, preferentially with a di(C.sub.1-C.sub.6)alkylamino or tri(C.sub.1-C.sub.6)alkylammonium group such as trimethylammonium.

10. Process according to claim 1, characterized in that the fluorescent dye(s) (b) are chosen from the dyes of formulae (V), (VI) and (VII) and also the organic or mineral acid or base salts thereof, the optical isomers, geometrical isomers and tautomers thereof, and the solvates thereof such as hydrates: ##STR00048## in which formulae (V), (VI) and (VII): 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; preferentially a hydrogen atom; 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 from among: 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, Q.sup.+, h) hydroxyl OH or alkoxide O.sup.Q.sup.+, i) (poly)halo(C.sub.1-C.sub.6)alkyl such as trifluoromethyl, 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; in particular, 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 represent a hydrogen or halogen atom or a (C.sub.1-C.sub.4)alkyl group, preferably a hydrogen atom; 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 and (C.sub.1-C.sub.4)dialkylamino, or alternatively the two alkyl radicals borne by the nitrogen atom of the amino group form a 5- to 7-membered heterocycle optionally comprising another nitrogen or non-nitrogen heteroatom; preferentially, R.sub.a and R.sub.a together form a benzo group; 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, preferentially cycloalkyl such as cyclohexyl; 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; preferentially, R.sub.b represents a hydrogen atom or a (C.sub.1-C.sub.3)alkyl or benzyl group; R.sub.e represents a covalent bond, a linear or branched, optionally substituted (C.sub.1-C.sub.5)alkylene or (C.sub.2-C.sub.8)alkenylene hydrocarbon-based chain, preferably R.sub.e represents an unsubstituted (C.sub.1-C.sub.6)alkylene; 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.8, which may be identical or different, represent a (C.sub.1-C.sub.4)alkyl group or R.sub.3R.sub.4N represents an optionally substituted heteroaryl group, preferentially an optionally substituted imidazolyl group, or alternatively M, R.sub.3R.sub.4R.sub.5N.sup.+ represents an optionally substituted cationic heteroaryl group, preferentially an imidazolinium group optionally substituted with a (C.sub.1-C.sub.3)alkyl group; G represents i) a group 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, f) optionally substituted (hetero)cycloalkyl(C.sub.1-C.sub.6)alkyl; according to a particular embodiment, G represents a group NR.sub.cR.sub.d, according to another particular embodiment, G represents a (C.sub.1-C.sub.6)alkoxy 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, 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, piperidyl and pyrrolidinyl groups; R.sub.c and R.sub.d, which may be identical or different, represent a hydrogen atom or a group from among: a) optionally substituted (hetero)aryl such as phenyl, 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.8)alkyl or g) (C.sub.1-C.sub.8)alkyl which is optionally substituted, preferably optionally substituted with a hydroxyl, carboxyl, carboxylate, sulfate or sulfonate group; 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; ##STR00049## represents a (hetero)aryl group fused to the phenyl ring; or alternatively is absent from the phenyl; preferentially, when the ring is present, the ring is a benzo; m represents an integer between 1 and 18 inclusive, particularly an integer between 1 and 14 inclusive; preferentially an integer between 2 and 10 inclusive; more preferentially an integer between 3 and 8; more particularly an integer between 4 and 6; 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 dye; 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 dye such as alkali metal, alkaline-earth metal or ammonium; it being understood that when the dye comprises a carboxylate, sulfonate or alkoxide group, then M and Q.sup.+ may be absent to ensure the electrical neutrality of said dye.

11. Process according to claim 1, characterized in that the fluorescent dye(s) (b) are chosen from the styryl dyes of formula (VIII) below, and also the organic or mineral acid or base salts thereof, the optical isomers, geometrical isomers and tautomers thereof, and the solvates thereof such as hydrates: ##STR00050## in which formula (VIII): 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, preferably hydrogen; R.sub.a, R.sub.a and R.sub.a, which may be identical or different, represent a hydrogen atom, a halogen atom such as fluorine, or an OH, O.sup.Q.sup.+, (C.sub.1-C.sub.6)alkoxy, nitro, or cyano group, with Q.sup.+ as defined in the preceding claim; 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 possibly being substituted; preferably, said benzo group is unsubstituted; G represents a group NR.sub.cR.sub.d or a (C.sub.1-C.sub.6)alkoxy group which is optionally substituted, preferentially unsubstituted; according to a particular embodiment, G represents a group NR.sub.cR.sub.d, according to another particular embodiment, G represents a (C.sub.1-C.sub.6)alkoxy 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; ##STR00051## represents an aryl or heteroaryl group fused to the phenyl ring; or alternatively is absent from the phenyl ring; preferentially, when the ring is present, the ring is a benzo; m represents an integer between 1 and 18 inclusive; particularly an integer between 2 and 16 inclusive; preferentially an integer between 3 and 10; more preferentially an integer between 4 and 6; 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, preferably (C.sub.2-C.sub.4)alkyl substituted in particular with one or more groups chosen from i) cyano, ii) (C.sub.1-C.sub.3)alkoxy, iii) hydroxyl and iv) (C.sub.1-C.sub.3)alkylcarbonyl, preferably with one or more hydroxyl groups; 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 dye; it being understood that when the dye comprises an alkoxide group, then M and Q.sup.+ may be absent to ensure the electrical neutrality of said dye.

12. Process according to claim 1, characterized in that the fluorescent dye(s) (b) are chosen from the styryl dyes of formula (IX) below, and the organic or mineral acid or base salts thereof, the optical isomers, geometrical isomers and tautomers thereof, and the solvates thereof such as hydrates: ##STR00052## in which formula (IX) 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.b, and R.sub.b, which may be identical or different, represent a) a hydrogen atom, b) a halogen atom, a group from among: 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) hydroxyl OH or alkoxide O.sup.Q.sup.+, i) (poly)halo(C.sub.1-C.sub.6)alkyl such as trifluoromethyl, 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; and m represents an integer between 1 and 18 inclusive.

13. Process according to claim 1, characterized in that the fluorescent dye(s) (b) are chosen from the compounds of formulae (X), (XI), (XII) and (XIII) below, and also the organic or mineral acid or base salts thereof, the optical isomers, geometrical isomers and tautomers thereof, and the solvates thereof such as hydrates: ##STR00053## in which formulae (X), (XI), (XII) and (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; preferably, R.sub.2 and R.sup.3 represent a hydrogen atom and R.sup.1 and R.sup.4, which may be identical or different, represent a hydrogen atom or a (C.sub.1-C.sub.4)alkyl group; R.sup.5, R.sup.6, R.sup.7, R.sup.8 and R.sub.9, which may be identical or different, represent i) a hydrogen atom or ii) a halogen atom such as Cl, Br or F, iii) a group OR in which R represents a hydrogen atom or Q.sup.+ as defined in claim 11, or a (C.sub.1-C.sub.3)alkyl group, a group from among iv) aryl such as benzene, v) aryl(C.sub.1-C.sub.3)alkyl such as benzyl, 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, preferably (C.sub.2-C.sub.4)alkyl optionally substituted with one or more groups chosen from: cyano, (C.sub.1-C.sub.3)alkoxy, hydroxyl, and (C.sub.1-C.sub.3)alkylcarbonyl; in particular, R.sup.10 and R.sup.11, which may be identical or different, represent a hydrogen atom or a (C.sub.1-C.sub.6)alkyl group substituted with one or more hydroxyl, cyano or (C.sub.1-C.sub.3)alkylcarbonyl groups such as hydroxyethyl; m represents an integer between 1 and 18 inclusive; particularly an integer between 2 and 16 inclusive; preferentially an integer between 3 and 10; more preferentially an integer between 4 and 6; 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 dye; it being understood that when the dye comprises an alkoxide group, then M and Q.sup.+ may be absent to ensure the electrical neutrality of said dye.

14. Process according to claim 1, characterized in that the fluorescent dye(s) (b) of the invention are chosen from those of formulae (XIV) and (XV) below: ##STR00054## in which formulae (XIV) and (XV): 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 such as methoxy, preferably, R.sup.5 and R.sup.8 represent a hydrogen atom; 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) RZC(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, preferably, X represents an oxygen atom, 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 such as an alkali metal or alkaline-earth metal; in particular, R.sup.7 represents a group 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.6)alkyl group optionally substituted with one or more groups chosen from i) hydroxyl, ii) carboxyl, iii) carboxylate, iv) sulfonic, and v) sulfonate, more particularly chosen from identical or different groups representing a) a hydrogen atom, or b) a (C.sub.1-C.sub.6)alkyl group optionally substituted with one or more groups chosen from i) hydroxyl, ii) carboxyl, and iii) carboxylate; m represents an integer between 1 and 18 inclusive; particularly an integer between 1 and 6 inclusive; preferentially an integer between 1 and 4; more preferentially an integer between 1 and 2; 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 dye; it being understood that when the dye comprises an alkoxide group, then M and Q.sup.+ may be absent to ensure the electrical neutrality of said dye.

15. Process according to claim 13, characterized in that the fluorescent dye(s) (b) are chosen from: the fluorescent dyes of formula (X) with: TABLE-US-00021 R* 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 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-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(OH.sub.2OH.sub.2OH).sub.2 H H 1 TABLE-US-00022 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 and also the organic or mineral acid or base salts thereof, the optical isomers, geometrical isomers and tautomers thereof, and the solvates thereof such as hydrates; the fluorescent dyes of formula (XI) with: TABLE-US-00023 R* 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.2Ph 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 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 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 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 OH H OCH.sub.3 H H 2 CH.sub.3 H H H H H OCH.sub.3 OCH.sub.2Ph 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 and also the organic or mineral acid or base salts thereof, the geometrical isomers and tautomers thereof, and the solvates thereof such as hydrates; the fluorescent dyes of formulae (X) and (XI): ##STR00055## wherein 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 dye; and TABLE-US-00024 R.sup.5 R.sup.7 R.sup.8 m H N(CH.sub.2CH.sub.2OH).sub.2 H 2 H N(CH.sub.2CH.sub.2OH).sub.2 H 3 H N(CH.sub.2CH.sub.2OH).sub.2 H 4 H N(CH.sub.2CH.sub.2OH).sub.2 H 5 H N(CH.sub.2CH.sub.2OH).sub.2 H 6 H N(CH.sub.2CH.sub.2OH).sub.2 H 8 H N(CH.sub.2CH.sub.2OH).sub.2 H 10 H N(CH.sub.2CH.sub.2OH).sub.2 H 12 H N(CH.sub.2CH.sub.2OH).sub.2 H 14 H N(CH.sub.2CH.sub.2OH).sub.2 H 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 TABLE-US-00025 R.sup.5 R.sup.7 R.sup.8 m OCH.sub.3 OCH.sub.3 OCH.sub.3 2 OCH.sub.3 OCH.sub.3 OCH.sub.3 3 OCH.sub.3 OCH.sub.3 OCH.sub.3 3 OCH.sub.3 OCH.sub.3 OCH.sub.3 4 OCH.sub.3 OCH.sub.3 OCH.sub.3 5 OCH.sub.3 OCH.sub.3 OCH.sub.3 8 OCH.sub.3 OCH.sub.3 OCH.sub.3 10 OCH.sub.3 OCH.sub.3 OCH.sub.3 12 OCH.sub.3 OCH.sub.3 OCH.sub.3 14 OCH.sub.3 OCH.sub.3 OCH.sub.3 16 and TABLE-US-00026 R.sup.5 R.sup.7 R.sup.8 m H N(CH.sub.2CH.sub.2OH).sub.2 H 2 H N(CH.sub.2CH.sub.2OH).sub.2 H 3 H N(CH.sub.2CH.sub.2OH).sub.2 H 4 H N(CH.sub.2CH.sub.2OH).sub.2 H 5 H N(CH.sub.2CH.sub.2OH).sub.2 H 6 H N(CH.sub.2CH.sub.2OH).sub.2 H 8 H N(CH.sub.2CH.sub.2OH).sub.2 H 10 H N(CH.sub.2CH.sub.2OH).sub.2 H 12 H N(CH.sub.2CH.sub.2OH).sub.2 H 14 H N(CH.sub.2CH.sub.2OH).sub.2 H 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 TABLE-US-00027 R.sup.5 R.sup.7 R.sup.8 m OCH.sub.3 OCH.sub.3 OCH.sub.3 2 OCH.sub.3 OCH.sub.3 OCH.sub.3 3 OCH.sub.3 OCH.sub.3 OCH.sub.3 3 OCH.sub.3 OCH.sub.3 OCH.sub.3 4 OCH.sub.3 OCH.sub.3 OCH.sub.3 5 OCH.sub.3 OCH.sub.3 OCH.sub.3 8 OCH.sub.3 OCH.sub.3 OCH.sub.3 10 OCH.sub.3 OCH.sub.3 OCH.sub.3 12 OCH.sub.3 OCH.sub.3 OCH.sub.3 14 OCH.sub.3 OCH.sub.3 OCH.sub.3 16 and and also the organic or mineral acid or base salts thereof, the geometrical isomers and tautomers thereof, and the solvates thereof such as hydrates; the fluorescent dyes of formula (XIII) with: TABLE-US-00028 R* 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 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 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 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)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 and also the organic or mineral acid or base salts thereof, the optical isomers, geometrical isomers and tautomers thereof, and the solvates thereof such as hydrates; the fluorescent dyes of formula (XIII) with: TABLE-US-00029 R* 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.2Ph H 2 CH.sub.3 H H H H H H H OCH.sub.3 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 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 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 TABLE-US-00030 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.2Ph 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 and also the organic or mineral acid or base salts thereof, the geometrical isomers and tautomers thereof, and the solvates thereof such as hydrates; and the fluorescent dyes of formulae (XII) and (XIII) below: ##STR00056## with: TABLE-US-00031 R.sup.5 R.sup.7 R.sup.8 m H N(CH.sub.2CH.sub.2OH).sub.2 H 2 H N(CH.sub.2CH.sub.2OH).sub.2 H 3 H N(CH.sub.2CH.sub.2OH).sub.2 H 4 H N(CH.sub.2CH.sub.2OH).sub.2 H 5 H N(CH.sub.2CH.sub.2OH).sub.2 H 6 H N(CH.sub.2CH.sub.2OH).sub.2 H 8 H N(CH.sub.2CH.sub.2OH).sub.2 H 10 H N(CH.sub.2CH.sub.2OH).sub.2 H 12 H N(CH.sub.2CH.sub.2OH).sub.2 H 14 H N(CH.sub.2CH.sub.2OH).sub.2 H 16 and TABLE-US-00032 R.sup.5 R.sup.7 R.sup.8 m OCH.sub.3 OCH.sub.3 OCH.sub.3 2 OCH.sub.3 OCH.sub.3 OCH.sub.3 3 OCH.sub.3 OCH.sub.3 OCH.sub.3 3 OCH.sub.3 OCH.sub.3 OCH.sub.3 4 OCH.sub.3 OCH.sub.3 OCH.sub.3 5 OCH.sub.3 OCH.sub.3 OCH.sub.3 8 OCH.sub.3 OCH.sub.3 OCH.sub.3 10 OCH.sub.3 OCH.sub.3 OCH.sub.3 12 OCH.sub.3 OCH.sub.3 OCH.sub.3 14 OCH.sub.3 OCH.sub.3 OCH.sub.3 16 TABLE-US-00033 R.sup.5 R.sup.7 R.sup.8 m H N(CH.sub.2CH.sub.2OH).sub.2 H 2 H N(CH.sub.2CH.sub.2OH).sub.2 H 3 H N(CH.sub.2CH.sub.2OH).sub.2 H 4 H N(CH.sub.2CH.sub.2OH).sub.2 H 5 H N(CH.sub.2CH.sub.2OH).sub.2 H 6 H N(CH.sub.2CH.sub.2OH).sub.2 H 8 H N(CH.sub.2CH.sub.2OH).sub.2 H 10 H N(CH.sub.2CH.sub.2OH).sub.2 H 12 H N(CH.sub.2CH.sub.2OH).sub.2 H 14 H N(CH.sub.2CH.sub.2OH).sub.2 H 16 and TABLE-US-00034 R.sup.5 R.sup.7 R.sup.8 m OCH.sub.3 OCH.sub.3 OCH.sub.3 2 OCH.sub.3 OCH.sub.3 OCH.sub.3 3 OCH.sub.3 OCH.sub.3 OCH.sub.3 3 OCH.sub.3 OCH.sub.3 OCH.sub.3 4 OCH.sub.3 OCH.sub.3 OCH.sub.3 5 OCH.sub.3 OCH.sub.3 OCH.sub.3 8 OCH.sub.3 OCH.sub.3 OCH.sub.3 10 OCH.sub.3 OCH.sub.3 OCH.sub.3 12 OCH.sub.3 OCH.sub.3 OCH.sub.3 14 OCH.sub.3 OCH.sub.3 OCH.sub.3 16 and also the organic or mineral acid or base salts thereof, the geometrical isomers and tautomers thereof, and the solvates thereof such as hydrates; and preferably, the fluorescent dye(s) (b) are chosen from the following compounds: ##STR00057## ##STR00058## and also the organic or mineral acid or base salts thereof, the geometrical isomers and tautomers thereof, and the solvates thereof such as hydrates; wherein 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 dye; and 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 dye such as alkali metal, alkaline-earth metal or ammonium; it being understood that when the dye comprises an alkoxide group, then M and Q.sup.+ may be absent to ensure the electrical neutrality of said dye.

16. Process according to claim 1, characterized in that it also comprises the application to said keratin fibres of one or more reducing agents, preferably chosen from i) the reducing agents of formula (XVI) below, and also the addition salts thereof, and mixtures thereof:
H(X).sub.q(R.sub.10).sub.t(XVI) in which formula (XVI): 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 represents a linear or branched, saturated or unsaturated C.sub.1 to C.sub.20 alkyl radical, optionally interrupted with a heteroatom, and/or optionally substituted with one or more radicals chosen from hydroxyl, halo, amine, carboxyl, ((C.sub.1-C.sub.30)alkoxy)carbonyl, amido, ((C.sub.1-C.sub.30)alkyl)aminocarbonyl, ((C.sub.1-C.sub.30)acyl)amino, mono or dialkylamino, and mono or dihydroxylamino radicals; ii) thioglycolic acid, iii) thiolactic acid, iv) glyceryl monothioglycolate, v) cysteamine, vi) N-acetylcysteamine, vii)N-propionylcysteamine, viii) cysteine, ix)N-acetylcysteine, x) thiomalic acid, xi) pantetheine, xii) 2,3-dimercaptosuccinic acid, xiii)N-(mercaptoalkyl)-co-hydroxyalkylamides, xiv)N-mono- or N,N-dialkylmercapto-4-butyramides, xv) aminomercaptoalkylamides, xvi)N-(mercaptoalkyl)succinamic acid derivatives, xvii)N-(mercaptoalkyl)succinimide derivatives, xviii) alkylamino mercaptoalkylamides, xix) the azeotropic mixture of 2-hydroxypropyl thioglyconate and of (2-hydroxy-1-methyl)ethyl thioglycolate, xx) mercaptoalkylaminoamides, xxi)N-mercaptoalkylalkanediamides xxii) formamidinesulfinic acid derivatives, addition salts thereof, and mixtures thereof.

17. Process according to claim 1, characterized in that it does not use any reducing agent.

18. Process according to claim 1, characterized in that the azinium dye(s) (a), and the fluorescent dye(s) (b), are applied together to the keratin fibres; preferably, the process comprises a step of applying to the keratin fibres a cosmetic composition which comprises one or more azinium dyes (a) chosen from the compounds of formula (I), and also the optical isomers thereof, the geometrical isomers thereof, the tautomers thereof, the organic or mineral acid or base salts thereof, the solvates thereof such as hydrates, and mixtures thereof, and one or more fluorescent dyes (b).

19. Process according to claim 1, characterized in that it comprises at least the following two successive steps: a first step of applying to said keratin fibres a cosmetic composition comprising one or more fluorescent dyes (b), followed by, a second step of applying to said fibres a cosmetic composition comprising one or more azinium dyes (a) chosen from the compounds of formula (I), and also the optical isomers thereof, the geometrical isomers thereof, the tautomers thereof, the organic or mineral, acid or base salts thereof, the solvates thereof such as hydrates, and mixtures thereof.

20. Process according to claim 1, characterized in that it comprises at least the following two successive steps: a first step of applying to said keratin fibres a cosmetic composition comprising one or more azinium dyes (a) chosen from the compounds of formula (I), and also the optical isomers thereof, the geometrical isomers thereof, the tautomers thereof, the organic or mineral, acid or base salts thereof, the solvates thereof such as hydrates, and mixtures thereof, followed by a second step of applying to said fibres a cosmetic composition comprising one or more fluorescent dyes (b).

21. Process according to claim 20, characterized in that it comprises at least two successive steps in which the pH of the cosmetic composition(s) is between 6 and 11 inclusive, preferably between 7 and 10, more preferentially between 7.5 and 9.5 and better still between 9 and 9.5.

22. Cosmetic composition comprising one or more azinium dyes (a) chosen from the compounds of formula (I), and also the optical isomers thereof, the geometrical isomers thereof, the tautomers thereof, the organic or mineral acid or base salts thereof, the solvates thereof such as hydrates, and mixtures thereof, and one or more fluorescent dyes (b), said composition optionally having a pH of between 6 and 11 inclusive, preferably between 7 and 10, more preferentially between 7.5 and 9.5 and better still between 9 and 9.5.

23. Multi-compartment device comprising a first compartment containing one or more azinium dyes (a) chosen from the compounds of formula (I), and also the optical isomers thereof, the geometrical isomers thereof, the tautomers thereof, the organic or mineral acid or base salts thereof, the solvates thereof such as hydrates, and mixtures thereof, and a second compartment containing one or more fluorescent dyes (b).

24. Use of one or more fluorescent dye(s) (b), combined with one or more azinium dye(s) (a) chosen from the compounds of formula (I), and also the optical isomers thereof, the geometrical isomers thereof, the tautomers thereof, the organic or mineral acid or base salts thereof, the solvates thereof such as hydrates, and mixtures thereof, for the dyeing of light keratin fibres, especially human keratin fibres such as the hair, in chestnut-brown, dark chestnut-brown, brown, brown with a glint or even black, without using an additional dye other than (a) or (b).

Description

EXAMPLES

[0335] In the examples that follow, all the amounts are given as weight percentages relative to the total weight of the composition, unless otherwise indicated.

I. Example 1: Combined Application of Azinium and Fluorescent Dyes in Reducing Medium

a) Preparation of the Compositions

[0336] Composition (A1) comprising an azinium dye of formula (I) according to the invention, was prepared from the ingredients whose contents are mentioned in the table below.

TABLE-US-00009 Composition A1 [00030] 0.5 Monoethanolamine pH = 8.5 Water qs 100 Colour in solution Dark blue

[0337] Compositions (B1) and (B2), comprising a fluorescent dye, were prepared from the ingredients whose contents are mentioned in the table below.

TABLE-US-00010 Composition B1 Composition B2 [00031] 0.5 [00032] 0.5 Monoethanolamine pH = 8.5 pH = 8.5 Water qs 100 qs 100 Colour in solution red red

[0338] The reducing composition was prepared from the ingredients whose contents are mentioned in the table below.

TABLE-US-00011 Reducing composition Thioglycolic acid (TGA) 10 Monoethanolamine 0.605 Water qs 100

[0339] The fixing composition was prepared from the ingredients whose contents are mentioned in the table below.

TABLE-US-00012 Fixing composition H.sub.2O.sub.2 (50% by volume) 0.48 Antioxidant 0.02 Orthophosphoric acid (85%) 0.012 Water qs 100

b) Procedure

[0340] Compositions (A1), (B1), (B2) and the reducing composition, obtained above, were mixed so as to obtain the following mixtures: [0341] (A1)+(B1)+reducing in a 45/45/10 ratio, and [0342] (A1)+(B2)+reducing in a 45/45/10 ratio.

[0343] The mixtures thus obtained were applied to 1 g locks of hair containing 90% white hairs, in a bath ratio equal to 10.

[0344] After a leave-on time of 20 minutes at room temperature, the locks of hair were rinsed with water. The fixing composition was then applied to the locks in a bath ratio equal to 10.

[0345] After a leave-on time of 5 minutes at room temperature, the locks were rinsed with water, washed with a shampoo and rinsed.

[0346] The locks were then subjected to 20 shampoo washes, broken down into four cycles of five shampoo washes. After each shampoo wash cycle, the locks were dried and the colour of the locks was measured using a Minolta CM2600d spectrocolorimeter (specular components included, 10 angle, illuminant D65) in the CIEL*a*b* system.

[0347] In this system, L* represents the intensity of the colour, a* indicates the green/red colour axis and b* the blue/yellow colour axis.

[0348] 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.

c) Results

[0349] The results of the colouring on the locks of hair containing 90% white hairs are given in the table below.

TABLE-US-00013 Azinium Number of shampoo dye washes colour L* A1 1 Blue 18.89 Fluorescent Number of shampoo dye washes Colour L* B1 1 Red 41.02 B1 0 Red 36.37 B2 1 Red 37.50 B2 0 Red 36.38 Number of shampoo Invention washes colour L* a* b* A1 + B1 1 Black 15.89 1.10 1.87 5 Black 16.04 1.06 1.38 20 Black with 16.22 2.20 2.08 a glint A1 + B2 1 Black 18.64 0.50 0.09 20 Black 18.74 0.51 0.47

[0350] The results obtained above show that the simultaneous application of an azinium dye of formula (I) according to the present invention and of a fluorescent dye makes it possible to obtain very intense and chromatic colours.

[0351] These results also show that the process according to the invention, using only two particular direct dyes, an azinium dye of formula (I) combined with a fluorescent dye, makes it possible to obtain black colours, which are persistent even after 20 shampoo washes.

II. Example 2: Combined Application of Azinium and Fluorescent Dyes

a) Preparation of the Compositions

[0352] Composition (A2) comprising an azinium dye of formula (I) according to the invention, was prepared from the ingredients whose contents are mentioned in the table below.

TABLE-US-00014 Composition A2 [00033] 0.5 Water qs 100

[0353] Composition (B3), comprising a fluorescent dye, was prepared from the ingredients whose contents are mentioned in the table below.

TABLE-US-00015 Composition B3 [00034] 0.5 Water qs 100

b) Procedure

[0354] Compositions (A2) and (B3) obtained above were mixed in a 1/1 ratio, before being applied to 1 g locks of hair containing 90% white hairs, in a bath ratio equal to 10.

[0355] After a leave-on time of 25 minutes at room temperature, the locks of hair were rinsed with water, washed with a shampoo and rinsed.

[0356] The locks were then subjected to 20 shampoo washes, broken down into four cycles of five shampoo washes. After each shampoo wash cycle, the locks were dried and the colour of the locks was measured using a Minolta CM2600d spectrocolorimeter (specular components included, 10 angle, illuminant D65) in the CIEL*a*b* system.

[0357] In this system, L* represents the intensity of the colour, a* indicates the green/red colour axis and b* the blue/yellow colour axis.

[0358] 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.

c) Results

[0359] The results of the colouring on the locks of hair containing 90% white hairs are given in the table below.

TABLE-US-00016 Number of shampoo Invention washes colour L* a* b* A2 + B3 1 Black with 15.92 1.09 1.01 a glint 5 Black with 17.07 1.55 0.06 a glint 20 Black with 16.47 2.08 1.18 a glint

[0360] The results obtained above show that the simultaneous application of an azinium dye of formula (I) according to the present invention and of a fluorescent dye makes it possible to obtain very intense and chromatic colours.

[0361] These results also show that the process according to the invention, using only two particular direct dyes, an azinium dye of formula (I) combined with a fluorescent dye, makes it possible to obtain black colours, which are persistent even after 20 shampoo washes.

III. Example 3: Combined Application of Azinium Dye and Fluorescent Dye in Reducing Medium

a) Preparation of the Compositions

[0362] Compositions (C1) and (C2) comprising an azinium dye of formula (I) according to the invention and a fluorescent dye, were prepared from the ingredients whose contents are mentioned in the table below.

TABLE-US-00017 Composition C1 Composition C2 [00035] 0.5 0.5 [00036] 0.5 [00037] 0.5 Monoethanolamine pH = 8.5 pH = 8.5 Water qs 100 qs 100

[0363] The reducing composition and the fixing composition were prepared according to Example 1.

b) Procedure

[0364] Compositions (C1) and (C2) and the reducing composition, obtained above, were mixed so as to obtain the following mixtures: [0365] (C1)+reducing in a 90/10 ratio, and [0366] (C2)+reducing in a 90/10 ratio.

[0367] The mixtures thus obtained were applied to 1 g locks of hair containing 90% white hairs, in a bath ratio equal to 10.

[0368] After a leave-on time of 20 minutes at room temperature, the locks of hair were rinsed with water. The fixing composition was then applied to the locks in a bath ratio equal to 10.

[0369] After a leave-on time of 5 minutes at room temperature, the locks were rinsed with water, washed with a shampoo and rinsed.

[0370] The locks were then subjected to 20 shampoo washes, broken down into four cycles of five shampoo washes. After each shampoo wash cycle, the locks were dried and the colour of the locks was measured using a Minolta CM2600d spectrocolorimeter (specular components included, 10 angle, illuminant D65) in the CIEL*a*b* system.

[0371] In this system, L* represents the intensity of the colour, a* indicates the green/red colour axis and b* the blue/yellow colour axis.

[0372] 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.

c) Results

[0373] The results of the colouring on the locks of hair containing 90% white hairs are given in the table below.

TABLE-US-00018 Number of shampoo Invention washes colour L* a* b* C1 0 Black 16.11 1.06 1.83 5 Black 15.43 1.39 0.76 10 Black 16.19 1.27 0.24 20 Black 15.60 1.03 0.14 C2 0 Black with 15.26 2.10 1.19 a glint 5 Black 16.07 1.30 0.86 10 Black 16.03 1.52 0.90 20 Black 16.08 1.42 0.08

[0374] The results obtained above show that the simultaneous application of an azinium dye of formula (I) according to the present invention and of a fluorescent dye makes it possible to obtain very intense and chromatic colours.

[0375] These results also show that the process according to the invention, using only two particular direct dyes, an azinium dye of formula (I) combined with a fluorescent dye, makes it possible to obtain black colours, which are persistent even after 20 shampoo washes, and whose intensity is not significantly different before and after 5, 10 and 20 successive shampoo washes.

IV. Example 4: Combined Application of Azinium Dye and Fluorescent Dye

a) Preparation of the Compositions

[0376] Compositions (D1) and (D2) comprising an azinium dye of formula (I) according to the invention and a fluorescent dye, were prepared from the ingredients whose contents are mentioned in the table below.

TABLE-US-00019 Composition D1 Composition D2 [00038] 0.5 0.5 [00039] 0.5 [00040] 0.5 Monoethanolamine pH = 8.5 pH = 8.5 Water qs 100 qs 100

b) Procedure

[0377] Compositions (D1) and (D2) thus obtained were applied to 1 g locks of hair containing 90% white hairs, in a bath ratio equal to 10.

[0378] After a leave-on time of 25 minutes at room temperature, the locks of hair were rinsed with water, washed with a shampoo and rinsed.

[0379] The locks were then subjected to 20 shampoo washes, broken down into four cycles of five shampoo washes. After each shampoo wash cycle, the locks were dried and the colour of the locks was measured using a Minolta CM2600d spectrocolorimeter (specular components included, 10 angle, illuminant D65) in the CIEL*a*b* system.

[0380] In this system, L* represents the intensity of the colour, a* indicates the green/red colour axis and b* the blue/yellow colour axis.

[0381] 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.

c) Results

[0382] The results of the colouring on the locks of hair containing 90% white hairs are given in the table below.

TABLE-US-00020 Number of shampoo Invention washes colour L* a* b* D1 0 Black 16.25 1.51 0.73 5 Black 16.27 1.56 0.18 10 Black 16.96 1.58 0.78 20 Black 18.31 1.76 0.18 D2 0 Black with 16.15 2.14 0.86 a glint 5 Black with 16.30 1.45 2.48 a glint 10 Black with 16.71 1.26 2.98 a glint 20 Black with 16.76 1.12 2.68 a glint

[0383] The results obtained above show that the simultaneous application of an azinium dye of formula (I) according to the present invention and of a fluorescent dye makes it possible to obtain very intense and chromatic colours.

[0384] These results also show that the process according to the invention, using only two particular direct dyes, an azinium dye of formula (I) combined with a fluorescent dye, makes it possible to obtain black colours, which are persistent even after 20 shampoo washes, and whose intensity is not significantly different before and after 5, 10 and 20 successive shampoo washes.