Anionic direct dye having a tetraalkylammonium counterion, dyeing composition comprising them and method for dyeing keratinous fibres starting from these dyes

Abstract

The invention relates to the dyeing of human keratinous fibers, in particular the hair, using anionic direct dyes or acid dyes having a tetraalkylammonium counterion of formula (I), with Col.sup.()m, R.sub.1, R.sub.2, R.sub.3, R.sub.4, m, and n as defined in the description. A subject-matter of the invention is a dyeing composition comprising an anionic dye of formula (I) and a method for dyeing keratinous fibers, such as the hair, employing the said composition. A subject-matter of the invention is likewise novel dyes of formula (I) and their uses for the coloring of keratinous fibers. This composition makes it possible to obtain a chromatic, powerful and particularly persistent coloring on keratinous fibers. ##STR00001##

Claims

1. A method for dyeing human keratinous fibers, said method comprising: applying to the fibers a composition comprising at least one anionic dye of formula (I) ##STR00039## and optical isomers, geometric isomers, and solvates thereof, wherein in formula (I): R.sub.1, R.sub.2, R.sub.3 and R.sub.4, which are identical, are chosen from i) linear (C.sub.1-C.sub.6)alkyls; and ii) linear (C.sub.2-C.sub.6)alkenyls; it being possible for the alkyl or alkenyl group of the groups of i) and ii) to be interrupted by at least one identical or different heteroatoms chosen from oxygen, sulphur, and N(R), wherein R is chosen from hydrogen atoms and alkyl groups; Col.sup.()m represents the anionic part of the anionic dye comprising at least one sulphonate group and/or at least one carboxylate group, and wherein m is the anionic charge; wherein m and n, which are identical or different, represent an integer ranging from 1 to 10; wherein: when the anionic part of the anionic dye comprises a sulphonate group or a carboxylate group, then m=n=1; when the anionic part of the anionic dye comprises anionic groups other than a sulphonate or carboxylate group, the anionic part is combined with at least one cationic counterion, organic, inorganic or R.sub.1R.sub.2R.sub.3R.sub.4N.sup.+, making it possible to achieve electrical neutrality of the formula (I); and the at least one anionic dye of formula (I) is chosen from the dyes of formulae (II), (II), (lll), or (III): a) diaryl anionic azo dyes of formula (II) or (II): ##STR00040## wherein in formulae (II) and (II): R.sub.7, R.sub.8, R.sub.9, R.sub.10, R.sub.7, R.sub.8, R.sub.9 and R.sub.10, which are identical or different, are chosen from a hydrogen atom or a group chosen from: alkyl groups; alkoxy groups or alkylthio groups; hydroxyl groups or mercapto groups; nitro groups or nitroso groups; R.sup.C(X)X, R.sup.XC(X), R.sup.XC(X)X, wherein R.sup. is chosen from a hydrogen atom, alkyl groups, or aryl groups; and X, X and X, which are identical or different, are chosen from oxygen atoms, sulphur atoms, or NR, wherein R is chosen from a hydrogen atom or an alkyl group; M.sup.+(O).sub.2S(O.sup.), wherein M.sup.+ is chosen from hydrogen atoms, cationic counterions, or cationic counterions R.sub.1R.sub.2R.sub.3R.sub.4N.sup.+; M.sup.+(O)CO.sup., wherein M.sup.+ is chosen from hydrogen atoms, cationic counterions, or cationic counterions R.sub.1R.sub.2R.sub.3R.sub.4N.sup.+; RS(O).sub.2, wherein R is chosen from hydrogen atoms, or an alkyl, aryl, (di)(alkyl)amino or aryl(alkyl)amino group; RS(O).sub.2X, wherein R is chosen from an alkyl group or an aryl group which is optionally substituted, and X is chosen from oxygen atoms, sulphur atoms, or NR, wherein R is chosen from a hydrogen atom or an alkyl group; (di)(alkyl)amino groups; aryl(alkyl)amino, optionally substituted by at least one group chosen from i) nitro; ii) nitroso; iii) M.sup.+(O).sub.2S(O.sup.) or iv) alkoxy groups, wherein M.sup.+ is chosen from hydrogen atoms, cationic counterions, or cationic counterions R.sub.1R.sub.2R.sub.3R.sub.4N.sup.+; optionally substituted heteroaryl groups; cycloalkyl groups; ArNN, wherein Ar is an optionally substituted aryl group; or else two contiguous groups, R.sub.7 with R.sub.8, R.sub.8 with R.sub.9, or R.sub.9 with R.sub.10, together form a fused benzo group A; and R.sub.7 with R.sub.8 or R.sub.8 with R.sub.9 or R.sub.9 with R.sub.10 together form a fused benzo group B; with A and B optionally substituted by one or more groups chosen from i) nitro; ii) nitroso; iii) M.sup.+(O).sub.2S(O.sup.); iv) hydroxyl; v) mercapto; vi) (di)(alkyl)amino; vii) R.sup.C(X)X; viii) R.sup.XC(X); ix) R.sup.XC(X)X; x) ArNN and xi) aryl(alkyl)amino which is optionally substituted, wherein M.sup.+ is chosen from hydrogen atoms, cationic counterions, or cationic counterions R.sub.1R.sub.2R.sub.3R.sub.4N.sup.+; W is chosen from a sigma bond, an oxygen or sulphur atom or a divalent radical i) NR, or ii) methylene C(R.sub.a)(R.sub.b), wherein R.sub.a and R.sub.b, which are identical or different, are chosen from a hydrogen atom or an aryl group, or else R.sub.a and R.sub.b form, together with the carbon atom which carries them, a spirocycloalkyl; with the proviso that the formulae (II) and (II) comprise at least one sulphonate radical R.sub.1R.sub.2R.sub.3R.sub.4N.sup.+(O).sub.2S(O.sup.) or carboxylate radical R.sub.1R.sub.2R.sub.3R.sub.4N.sup.+(O)C(O.sup.) on one of the rings A, A, B, B or C; or b) pyrazolone anionic azo dyes of formulae (III) or (III): ##STR00041## wherein in formulae (III) and (III): R.sub.11, R.sub.12 and R.sub.13, which are identical or different, are chosen from a hydrogen atom, a halogen atom, an alkyl group or an M.sup.+(O).sub.2S(O.sup.) group, wherein M.sup.+ is chosen from hydrogen atoms, cationic counterions, or cationic counterions R.sub.1R.sub.2R.sub.3R.sub.4N.sup.+; R.sub.14 is chosen from a hydrogen atom, an alkyl group or an M.sup.+C(O)O.sup. group, wherein M.sup.+ is chosen from hydrogen atoms, cationic counterions, or cationic counterions R.sub.1R.sub.2R.sub.3R.sub.4N.sup.+; R.sub.15 represents a hydrogen atom; R.sub.16 represents an oxo group, in which case R.sub.16 is absent, or else R.sub.15 with R.sub.16 together form a double bond; R.sub.17 and R.sub.18, which are identical or different, are chosen from a hydrogen atom or a group chosen from: M.sup.+(O).sub.2S(O.sup.), wherein M.sup.+ is chosen from hydrogen atoms, cationic counterions, or cationic counterions R.sub.1R.sub.2R.sub.3R.sub.4N.sup.+; ArOS(O).sub.2, wherein Ar is an optionally substituted aryl group; R.sub.19 and R.sub.20, together form either a double bond or an optionally substituted benzo group D; R.sub.16, R.sub.19 and R.sub.20, which are identical or different, are chosen from a hydrogen atom, an alkyl group, or a hydroxyl group; R.sub.21 is chosen from a hydrogen atom, an alkyl group, or an alkoxy group; R.sub.a and R.sub.b, which are identical or different, are chosen from a hydrogen atom or an aryl group, or else R.sub.a and R.sub.b form, together with the carbon atom which carries them, a spirocycloalkyl; Y is chosen from a hydroxyl group or an oxo group; represents a single bond when Y is an oxo group and represents a double bond when Y represents a hydroxyl group; with the proviso that the formulae (III) and (III) comprise at least one sulphonate group R.sub.1R.sub.2R.sub.3R.sub.4N.sup.+(O).sub.2S(O.sup.) on one of the rings D or E or the formulae (III) and (III) comprise at least one carboxylate group R.sub.1R.sub.2R.sub.3R.sub.4N.sup.+(O)C(O.sup.).

2. The method according to claim 1, wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are identical.

3. The method according to claim 1, wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are independently chosen from linear (C.sub.1-C.sub.6)alkyl groups.

4. The method according to claim 1, wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are independently chosen from methyl, ethyl, propyl or butyl groups.

5. The method according to claim 1, wherein m is equal to n.

6. The method according to claim 1, in which m and n are independently chosen from 1, 2 or 3.

7. The method according to claim 1, wherein Col.sup.().sub.m comprises: at least one sulphonate group and at least one aryl or heteroaryl group, wherein the at least one sulphonate group is directly connected to an aryl or heteroaryl group; and optionally at least one anionic group G.sup., wherein G.sup., which is identical or different, represents an anionic group chosen from alkoxide O.sup., thiolate S.sup., carboxylate or thiocarboxylate C(Q)Q.sup., wherein Q and Q, which are identical or different, are chosen from oxygen or sulphur atoms.

8. The method according to claim 7, wherein G.sup. is a carboxylate.

9. The method according to claim 1, wherein Col.sup.().sub.m comprises at least one carboxylate group and at least one aryl or heteroaryl group, wherein the at least one carboxylate group is directly connected to an aryl or heteroaryl group.

10. The method according to claim 1, wherein the anionic direct dye is chosen from acid azo dyes, each of these dyes having at least one sulphonate or carboxylate group having the cationic counterion R.sub.1R.sub.2R.sub.3R.sub.4N.sup.+.

11. The method according to claim 1, wherein the at least one anionic dye of formula (I) is chosen from the diaryl anionic azo dyes of formula (II): ##STR00042## wherein: R.sub.7, R.sub.8, R.sub.9, R.sub.10, R.sub.7, R.sub.8, R.sub.9 and R.sub.10, which are identical or different, are chosen from a hydrogen atom or a group chosen from: alkyl groups; alkoxy groups, alkylthio groups; hydroxyl groups, mercapto groups; nitro groups, nitroso groups; R.sup.C(X)X, R.sup.XC(X), R.sup.XC(X)X, wherein R.sup. is chosen from hydrogen atoms alkyl groups, or aryl groups; and X, X and X, which are identical or different, are chosen from oxygen atoms, sulphur atoms, or NR, wherein R is chosen from hydrogen atoms or alkyl groups; M.sup.+(O).sub.2S(O.sup.), wherein M.sup.+ is chosen from hydrogen atoms, cationic counterions, or ammonium cationic counterions R.sub.1R.sub.2R.sub.3R.sub.4N.sup.+; M.sup.+(O)CO.sup., wherein M.sup.+ is chosen from hydrogen atoms, cationic counterions, or ammonium cationic counterions R.sub.1R.sub.2R.sub.3R.sub.4N.sup.+; RS(O).sub.2, wherein R is chosen from hydrogen atoms or alkyl, aryl, (di)(alkyl)amino or aryl(alkyl)amino groups; RS(O).sub.2X, wherein R is chosen from alkyl groups or aryl groups, optionally substituted, and X is chosen from oxygen atoms, sulphur atoms, or NR, wherein R is chosen from hydrogen atoms or alkyl groups; (di)(alkyl)amino groups; aryl(alkyl)amino groups, optionally substituted by at least one group chosen from nitro, nitroso, M.sup.+(O).sub.2S(O.sup.), or alkoxy groups; optionally substituted heteroaryl groups; cycloalkyl groups; ArNN, wherein Ar is an optionally substituted aryl group; or two contiguous groups, R.sub.7 with R.sub.8, R.sub.8 with R.sub.9, R.sub.9 with R.sub.10, which together form a fused benzo group A; and R.sub.7 with R.sub.8 or R.sub.8 with R.sub.9 or R.sub.9 with R.sub.10 together form a fused benzo group B; wherein A and B are optionally substituted by at least one group chosen from nitro; nitroso; M.sup.+(O).sub.2S(O.sup.); hydroxyl; mercapto; (di)(alkyl)amino; R.sup.C(X)X; R.sup.XC(X); R.sup.XC(X)X; ArNN; or aryl(alkyl)amino which is optionally substituted; wherein the diaryl anionic azo dye of formula (II) comprises at least one sulphonate radical R.sub.1R.sub.2R.sub.3R.sub.4N.sup.+(O).sub.2S(O.sup.) or carboxylate radical R.sub.1R.sub.2R.sub.3R.sub.4N.sup.+(O)C(O.sup.) on one of the rings A, A, B, or B.

12. The method according to claim 1, wherein the at least one anionic dye of formula (I) is chosen from formulae (IIa): ##STR00043## wherein in formula (IIa): R.sub.7, R.sub.8, R.sub.9, R.sub.10, R.sub.7, R.sub.8, R.sub.9 and R.sub.10, which are identical or different, are chosen from hydrogen atoms or groups chosen from: hydroxyl; nitro, nitroso; (di)(alkyl)amino; M.sup.+(O).sub.2S(O.sup.), wherein M.sup.+ is chosen from hydrogen atoms, cationic counterions, or ammonium cationic counterions R.sub.1R.sub.2R.sub.3R.sub.4N.sup.+; or ArNN, wherein Ar is an optionally substituted aryl group; two contiguous groups chosen from R.sub.7 with R.sub.8, R.sub.8 with R.sub.9, or R.sub.9 with R.sub.10, that together form a fused benzo group A; and two contiguous groups chosen from R.sub.7 with R.sub.8, R.sub.8 with R.sub.9, or R.sub.9 with R.sub.10, that together form a fused benzo group B; wherein A and B are optionally substituted by at least one group chosen from M.sup.+(O).sub.2S(O.sup.); hydroxyl; or ArNN; wherein the formula (IIa) comprises at least one sulphonate radical R.sub.1R.sub.2R.sub.3R.sub.4N.sup.+(O).sub.2S(O.sup.) or carboxylate radical R.sub.1R.sub.2R.sub.3R.sub.4N.sup.+(O)C(O.sup.) on one of the rings A, A, B, or B.

13. The method according to claim 1, wherein the at least one anionic dye of formula (I) is chosen from: ##STR00044## wherein M+, which is identical or different, is chosen from hydrogen atoms, cationic counterions, or ammonium cationic counterions R.sub.1R.sub.2R.sub.3R.sub.4N.sup.+, wherein at least one of the cationic counterions is a cationic counterion R.sub.1R.sub.2R.sub.3R.sub.4N.sup.+.

14. A method for dyeing and lightening dark human keratinous fibers having a height of tone of less than or equal to 6, comprising: applying to the fibers, a composition comprising at least one fluorescent anionic dye of formula (I) ##STR00045## and optical isomers, geometric isomers, and solvates thereof, wherein in formula (I): R.sub.1, R.sub.2, R.sub.3 and R.sub.4, which are identical, are chosen from i) linear (C.sub.1-C.sub.6)alkyls; and ii) linear (C.sub.2-C.sub.6)alkenyls; it being possible for the alkyl or alkenyl group of the groups of i) and ii) to be interrupted by at least one identical or different heteroatoms chosen from oxygen, sulphur, and N(R), wherein R is chosen from hydrogen atoms and alkyl groups; Col.sup.().sub.m represents the anionic part of the anionic dye comprising at least one sulphonate group and/or at least one carboxylate group, and wherein m is the anionic charges; wherein m and n, which are identical or different, represent an integer ranging from 1 to 10; wherein when the anionic part of the anionic dye comprises a sulphonate group or a carboxylate group, then m=n=1; wherein when the anionic part of the anionic dye comprises anionic groups other than a sulphonate or carboxylate group, the anionic part is combined with at least one cationic counterion, organic, inorganic or R.sub.1R.sub.2R.sub.3R.sub.4N+, making it possible to achieve electrical neutrality of the formula (I); and the at least one anionic dye of formula (I) is chosen from the dyes of formulae (II), (II), (III), or (III): a) diaryl anionic azo dyes of formula (II) or (II): ##STR00046## wherein in formulae (II) and (II): R.sub.7, R.sub.8, R.sub.9, R.sub.10, R.sub.7, R.sub.8, R.sub.9 and R.sub.10, which are identical or different, are chosen from a hydrogen atom or a group chosen from: alkyl groups; alkoxy groups or alkylthio groups; hydroxyl groups or mercapto groups; nitro groups or nitroso groups; R.sup.C(X)X, R.sup.XC(X), R.sup.XC(X)X, wherein R.sup. is chosen from a hydrogen atom, alkyl groups, or aryl groups; and X, X and X, which are identical or different, are chosen from oxygen atoms, sulphur atoms, or NR, wherein R is chosen from a hydrogen atom or an alkyl group; M.sup.+(O).sub.2S(O.sup.), wherein M.sup.+ is chosen from hydrogen atoms, cationic counterions, or cationic counterions R.sub.1R.sub.2R.sub.3R.sub.4N.sup.+; M.sup.+(O)CO.sup., wherein M.sup.+ is chosen from hydrogen atoms, cationic counterions, or cationic counterions R.sub.1R.sub.2R.sub.3R.sub.4N.sup.+; RS(O).sub.2, wherein R is chosen from hydrogen atoms, or an alkyl, aryl, (di)(alkyl)amino or aryl(alkyl)amino group; RS(O).sub.2X, wherein R is chosen from an alkyl group or an aryl group which is optionally substituted, and X is chosen from oxygen atoms, sulphur atoms, or NR, wherein R is chosen from a hydrogen atom or an alkyl group; (di)(alkyl)amino groups; aryl(alkyl)amino, optionally substituted by at least one group chosen from i) nitro; ii) nitroso; iii) M.sup.+(O).sub.2S(O.sup.) or iv) alkoxy groups, wherein M.sup.+ is chosen from hydrogen atoms, cationic counterions, or cationic counterions R.sub.1R.sub.2R.sub.3R.sub.4N.sup.+; optionally substituted heteroaryl groups; cycloalkyl groups; ArNN, wherein Ar is an optionally substituted aryl group; or else two contiguous groups, R.sub.7 with R.sub.8, R.sub.8 with R.sub.9, or R.sub.9 with R.sub.10, together form a fused benzo group A; and R.sub.7 with R.sub.8 or R.sub.8 with R.sub.9 or R.sub.9 with R.sub.10 together form a fused benzo group B; with A and B optionally substituted by one or more groups chosen from i) nitro; ii) nitroso; iii) M.sup.+(O).sub.2S(O.sup.); iv) hydroxyl; v) mercapto; vi) (di)(alkyl)amino; vii) R.sup.C(X)X; viii) R.sup.XC(X); ix) R.sup.XC(X)X; x) ArNN and xi) aryl(alkyl)amino which is optionally substituted, wherein M.sup.+ is chosen from hydrogen atoms, cationic counterions, or cationic counterions R.sub.1R.sub.2R.sub.3R.sub.4N.sup.+; W is chosen from a sigma bond, an oxygen or sulphur atom or a divalent radical i) NR, or ii) methylene C(R.sub.a)(R.sub.b), wherein R.sub.a and R.sub.b, which are identical or different, are chosen from a hydrogen atom or an aryl group, or else R.sub.a and R.sub.b form, together with the carbon atom which carries them, a spirocycloalkyl; with the proviso that the formulae (II) and (II) comprise at least one sulphonate radical R.sub.1R.sub.2R.sub.3R.sub.4N.sup.+(O).sub.2S(O.sup.) or carboxylate radical R.sub.1R.sub.2R.sub.3R.sub.4N.sup.+(O)C(O.sup.) on one of the rings A, A, B, B or C; or b) pyrazolone anionic azo dyes of formulae (III) or (III): ##STR00047## wherein in formulae (III) and (III): R.sub.11, R.sub.12 and R.sub.13, which are identical or different, are chosen from a hydrogen atom, a halogen atom, an alkyl group or an M.sup.+(O).sub.2S(O.sup.) group, wherein M.sup.+ is chosen from hydrogen atoms, cationic counterions, or cationic counterions R.sub.1R.sub.2R.sub.3R.sub.4N.sup.+; R.sub.14 is chosen from a hydrogen atom, an alkyl group or an M.sup.+C(O)O.sup. group, wherein M.sup.+ is chosen from hydrogen atoms, cationic counterions, or cationic counterions R.sub.1R.sub.2R.sub.3R.sub.4N.sup.+; R.sub.15 represents a hydrogen atom; R.sub.16 represents an oxo group, in which case R.sub.16 is absent, or else R.sub.15 with R.sub.16 together form a double bond; R.sub.17 and R.sub.18, which are identical or different, are chosen from a hydrogen atom or a group chosen from: M.sup.+(O).sub.2S(O.sup.), wherein M.sup.+ is chosen from hydrogen atoms, cationic counterions, or cationic counterions R.sub.1R.sub.2R.sub.3R.sub.4N.sup.+; ArOS(O).sub.2, wherein Ar is an optionally substituted aryl group; R.sub.19 and R.sub.20, together form either a double bond or an optionally substituted benzo group D; R.sub.16, R.sub.19 and R.sub.20, which are identical or different, are chosen from a hydrogen atom, an alkyl group, or a hydroxyl group; R.sub.21 is chosen from a hydrogen atom, an alkyl group, or an alkoxy group; R.sub.a and R.sub.b, which are identical or different, are chosen from a hydrogen atom or an aryl group, or else R.sub.a and R.sub.b form, together with the carbon atom which carries them, a spirocycloalkyl; Y is chosen from a hydroxyl group or an oxo group; represents a single bond when Y is an oxo group and represents a double bond when Y represents a hydroxyl group; with the proviso that the formulae (III) and (III) comprise at least one sulphonate group R.sub.1R.sub.2R.sub.3R.sub.4N.sup.+(O).sub.2S(O.sup.) on one of the rings D or E or the formulae (III) and (III) comprise at least one carboxylate group R.sub.1R.sub.2R.sub.3R.sub.4N.sup.+(O)C(O.sup.).

15. The method according to claim 14, wherein the keratinous fibers have a height of tone of less than or equal to 4.

16. The method according to claim 14, wherein the at least one fluorescent anionic dye is within the range of the orangey colors.

17. An anionic dye for dyeing human keratinous fibers of formula (I): ##STR00048## and optical isomers, geometric isomers, and solvates thereof, wherein in formula (I): R.sub.1, R.sub.2, R.sub.3 and R.sub.4, which are identical, are chosen from i) linear (C.sub.1-C.sub.6)alkyls; and ii) linear (C.sub.2-C.sub.6)alkenyls; it being possible for the alkyl or alkenyl group of the groups of i) and ii) to be interrupted by at least one identical or different heteroatoms chosen from oxygen, sulphur, and N(R), wherein R is chosen from hydrogen atoms and alkyl groups; Col.sup.().sub.m represents the anionic part of the anionic dye comprising at least one sulphonate group and/or at least one carboxylate group and wherein m is the anionic charges; wherein m and n, which are identical or different, represent an integer ranging from 1 to 10; wherein: when the anionic part of the anionic dye comprises a sulphonate group or a carboxylate group, then m=n=1; when the anionic part of the anionic dye comprises anionic groups other than a sulphonate or carboxylate group, the anionic part is combined with at least one cationic counterion, organic, inorganic or R.sub.1R.sub.2R.sub.3R.sub.4N.sup.+, making it possible to achieve electrical neutrality of the formula (I), the at least one anionic dye of formula (I) is chosen from the dyes of formulae (II), (II), (III), or (III): a) diaryl anionic azo dyes of formula (II) or (II): ##STR00049## wherein in formulae (II) and (II): R.sub.7, R.sub.8, R.sub.9, R.sub.10, R.sub.7, R.sub.8, R.sub.9 and R.sub.10, which are identical or different, are chosen from a hydrogen atom or a group chosen from: alkyl groups; alkoxy groups or alkylthio groups; hydroxyl groups or mercapto groups; nitro groups or nitroso groups; R.sup.C(X)X, R.sup.XC(X), R.sup.XC(X)X, wherein R.sup. is chosen from a hydrogen atom, alkyl groups, or aryl groups; and X, X and X, which are identical or different, are chosen from oxygen atoms, sulphur atoms, or NR, wherein R is chosen from a hydrogen atom or an alkyl group; M.sup.+(O).sub.2S(O.sup.), wherein M.sup.+ is chosen from hydrogen atoms, cationic counterions, or cationic counterions R.sub.1R.sub.2R.sub.3R.sub.4N.sup.+; M.sup.+(O)CO.sup., wherein M.sup.+ is chosen from hydrogen atoms, cationic counterions, or cationic counterions R.sub.1R.sub.2R.sub.3R.sub.4N.sup.+; RS(O).sub.2, wherein R is chosen from hydrogen atoms, or an alkyl, aryl, (di)(alkyl)amino or aryl(alkyl)amino group; RS(O).sub.2X, wherein R is chosen from an alkyl group or an aryl group which is optionally substituted, and X is chosen from oxygen atoms, sulphur atoms, or NR, wherein R is chosen from a hydrogen atom or an alkyl group; (di)(alkyl)amino groups; aryl(alkyl)amino, optionally substituted by at least one group chosen from i) nitro; ii) nitroso; iii) M.sup.+(O).sub.2S(O.sup.) or iv) alkoxy groups, wherein M.sup.+ is chosen from hydrogen atoms, cationic counterions, or cationic counterions R.sub.1R.sub.2R.sub.3R.sub.4N.sup.+; optionally substituted heteroaryl groups; cycloalkyl groups; ArNN, wherein Ar is an optionally substituted aryl group; or else two contiguous groups, R.sub.7 with R.sub.8, R.sub.8 with R.sub.9, or R.sub.9 with R.sub.10, together form a fused benzo group A; and R.sub.7 with R.sub.8 or R.sub.8 with R.sub.9 or R.sub.9 with R.sub.10 together form a fused benzo group B; with A and B optionally substituted by one or more groups chosen from i) nitro; ii) nitroso; iii) M.sup.+(O).sub.2S(O.sup.); iv) hydroxyl; v) mercapto; vi) (di)(alkyl)amino; vii) R.sup.C(X)X; viii) R.sup.XC(X); ix) R.sup.XC(X)X; x) ArNN and xi) aryl(alkyl)amino which is optionally substituted, wherein M.sup.+ is chosen from hydrogen atoms, cationic counterions, or cationic counterions R.sub.1R.sub.2R.sub.3R.sub.4N.sup.+; W is chosen from a sigma a bond, an oxygen or sulphur atom or a divalent radical i) NR, or ii) methylene C(R.sub.a)(R.sub.b), wherein R.sub.a and R.sub.b, which are identical or different, are chosen from a hydrogen atom or an aryl group, or else R.sub.a and R.sub.b form, together with the carbon atom which carries them, a spirocycloalkyl; with the proviso that the formulae (II) and (II) comprise at least one sulphonate radical R.sub.1R.sub.2R.sub.3R.sub.4N.sup.+(O).sub.2S(O.sup.) or carboxylate radical R.sub.1R.sub.2R.sub.3R.sub.4N.sup.+(O)C(O.sup.) on one of the rings A, A, B, B or C; or b) pyrazolone anionic azo dyes of formulae (III) or (III): ##STR00050## wherein in formulae (III) and (III): R.sub.11, R.sub.12 and R.sub.13, which are identical or different, are chosen from a hydrogen atom, a halogen atom, an alkyl group or an M.sup.+(O).sub.2S(O.sup.) group, wherein M.sup.+ is chosen from hydrogen atoms, cationic counterions, or cationic counterions R.sub.1R.sub.2R.sub.3R.sub.4N.sup.+; R.sub.14 is chosen from a hydrogen atom, an alkyl group or an M.sup.+C(O)O.sup. group, wherein M.sup.+ is chosen from hydrogen atoms, cationic counterions, or cationic counterions R.sub.1R.sub.2R.sub.3R.sub.4N.sup.+; R.sub.15 represents a hydrogen atom; R.sub.16 represents an oxo group, in which case R.sub.16 is absent, or else R.sub.15 with R.sub.16 together form a double bond; R.sub.17 and R.sub.18, which are identical or different, are chosen from a hydrogen atom or a group chosen from: M.sup.+(O).sub.2S(O.sup.), wherein M.sup.+ is chosen from hydrogen atoms, cationic counterions, or cationic counterions R.sub.1R.sub.2R.sub.3R.sub.4N.sup.+; ArOS(O).sub.2, wherein Ar is an optionally substituted aryl group; R.sub.19 and R.sub.20, together form either a double bond or an optionally substituted benzo group D; R.sub.16, R.sub.19 and R.sub.20, which are identical or different, are chosen from a hydrogen atom, an alkyl group, or a hydroxyl group; R.sub.21 is chosen from a hydrogen atom, an alkyl group, or an alkoxy group; R.sub.a and R.sub.b, which are identical or different, are chosen from a hydrogen atom or an aryl group, or else R.sub.a and R.sub.b form, together with the carbon atom which carries them, a spirocycloalkyl; Y is chosen from a hydroxyl group or an oxo group; represents a single bond when Y is an oxo group and represents a double bond when Y represents a hydroxyl group; with the proviso that the formulae (III) and (III) comprise at least one sulphonate group R.sub.1R.sub.2R.sub.3R.sub.4N.sup.+(O).sub.2S(O.sup.) on one of the rings D or E or the formulae (III) and (III) comprise at least one carboxylate group R.sub.1R.sub.2R.sub.3R.sub.4N.sup.+(O)C(O.sup.); wherein the anionic dye of formula (I) is different from the dyes of formulae (a) to (u): ##STR00051## ##STR00052## ##STR00053## ##STR00054## ##STR00055##

18. A dyeing composition for dyeing human keratinous fibers, said composition comprising at least one anionic dye of formula (I): ##STR00056## and optical isomers, geometric isomers, and solvates thereof, wherein in formula (I): R.sub.1, R.sub.2, R.sub.3 and R.sub.4, which are identical, are chosen from i) linear (C.sub.1-C.sub.6)alkyls; and ii) linear (C.sub.2-C.sub.6)alkenyls; it being possible for the alkyl or alkenyl group of the groups of i) and ii) to be interrupted by at least one identical or different heteroatoms chosen from oxygen, sulphur, and N(R), wherein R is chosen from hydrogen atoms and alkyl groups; Col.sup.().sub.m represents the anionic part of the anionic dye comprising at least one sulphonate group and/or at least one carboxylate group and wherein m is the anionic charges; wherein m and n, which are identical or different, represent an integer ranging from 1 to 10; wherein: when the anionic part of the anionic dye comprises a sulphonate group or a carboxylate group, then m=n=1; when the anionic part of the anionic dye comprises anionic groups other than a sulphonate or carboxylate group, the anionic part is combined with at least one cationic counterion, organic, inorganic or R.sub.1R.sub.2R.sub.3R.sub.4N.sup.+, making it possible to achieve electrical neutrality of the formula (I), the at least one anionic dye of formula (I) is chosen from the dyes of formulae (II), (II), (III), or (III): a) diaryl anionic azo dyes of formula (II) or (II): ##STR00057## wherein in formulae (II) and (II): R.sub.7, R.sub.8, R.sub.9, R.sub.10, R.sub.7, R.sub.8, R.sub.9 and R.sub.10, which are identical or different, are chosen from a hydrogen atom or a group chosen from: alkyl groups; alkoxy groups or alkylthio groups; hydroxyl groups or mercapto groups; nitro groups or nitroso groups; R.sup.C(X)X, R.sup.XC(X), R.sup.XC(X)X, wherein R.sup. is chosen from a hydrogen atom, alkyl groups, or aryl groups; and X, X and X, which are identical or different, are chosen from oxygen atoms, sulphur atoms, or NR, wherein R is chosen from a hydrogen atom or an alkyl group; M.sup.+(O).sub.2S(O.sup.), wherein M.sup.+ is chosen from hydrogen atoms, cationic counterions, or cationic counterions R.sub.1R.sub.2R.sub.3R.sub.4N.sup.+; M.sup.+(O)CO.sup., wherein M.sup.+ is chosen from hydrogen atoms, cationic counterions, or cationic counterions R.sub.1R.sub.2R.sub.3R.sub.4N.sup.+; RS(O).sub.2, wherein R is chosen from hydrogen atoms, or an alkyl, aryl, (di)(alkyl)amino or aryl(alkyl)amino group; RS(O).sub.2X, wherein R is chosen from an alkyl group or an aryl group which is optionally substituted, and X is chosen from oxygen atoms, sulphur atoms, or NR, wherein R is chosen from a hydrogen atom or an alkyl group; (di)(alkyl)amino groups; aryl(alkyl)amino, optionally substituted by at least one group chosen from i) nitro; ii) nitroso; iii) M.sup.+(O).sub.2S(O.sup.) or iv) alkoxy groups, wherein M.sup.+ is chosen from hydrogen atoms, cationic counterions, or cationic counterions R.sub.1R.sub.2R.sub.3R.sub.4N.sup.+; optionally substituted heteroaryl groups; cycloalkyl groups; ArNN, wherein Ar is an optionally substituted aryl group; or else two contiguous groups, R.sub.7 with R.sub.8, R.sub.8 with R.sub.9, or R.sub.9 with R.sub.10, together form a fused benzo group A; and R.sub.7 with R.sub.8 or R.sub.8 with R.sub.9 or R.sub.9 with R.sub.10 together form a fused benzo group B; with A and B optionally substituted by one or more groups chosen from i) nitro; ii) nitroso; iii) M.sup.+(O).sub.2S(O.sup.); iv) hydroxyl; v) mercapto; vi) (di)(alkyl)amino; vii) R.sup.C(X)X; viii) R.sup.XC(X); ix) R.sup.XC(X)X; x) ArNN and xi) aryl(alkyl)amino which is optionally substituted, wherein M.sup.+ is chosen from hydrogen atoms, cationic counterions, or cationic counterions R.sub.1R.sub.2R.sub.3R.sub.4N.sup.+; W is chosen from a sigma bond, an oxygen or sulphur atom or a divalent radical i) NR, or ii) methylene C(R.sub.a)(R.sub.b), wherein R.sub.a and R.sub.b, which are identical or different, are chosen from a hydrogen atom or an aryl group, or else R.sub.a and R.sub.b form, together with the carbon atom which carries them, a spirocycloalkyl; with the proviso that the formulae (II) and (II) comprise at least one sulphonate radical R.sub.1R.sub.2R.sub.3R.sub.4N.sup.+(O).sub.2S(O.sup.) or carboxylate radical R.sub.1R.sub.2R.sub.3R.sub.4N.sup.+(O)C(O.sup.) on one of the rings A, A, B, B or C; or b) pyrazolone anionic azo dyes of formulae (III) or (III): ##STR00058## wherein in formulae (III) and (III): R.sub.11, R.sub.12 and R.sub.13, which are identical or different, are chosen from a hydrogen atom, a halogen atom, an alkyl group or an M.sup.+(O).sub.2S(O.sup.) group, wherein M.sup.+ is chosen from hydrogen atoms, cationic counterions, or cationic counterions R.sub.1R.sub.2R.sub.3R.sub.4N.sup.+; R.sub.14 is chosen from a hydrogen atom, an alkyl group or an M.sup.+C(O)O.sup. group, wherein M.sup.+ is chosen from hydrogen atoms, cationic counterions, or cationic counterions R.sub.1R.sub.2R.sub.3R.sub.4N.sup.+; R.sub.15 represents a hydrogen atom; R.sub.16 represents an oxo group, in which case R.sub.16 is absent, or else R.sub.15 with R.sub.16 together form a double bond; R.sub.17 and R.sub.18, which are identical or different, are chosen from a hydrogen atom or a group chosen from: M.sup.+(O).sub.2S(O.sup.), wherein M.sup.+ is chosen from hydrogen atoms, cationic counterions, or cationic counterions R.sub.1R.sub.2R.sub.3R.sub.4N.sup.+; ArOS(O).sub.2, wherein Ar is an optionally substituted aryl group; R.sub.19 and R.sub.20, together form either a double bond or an optionally substituted benzo group D; R.sub.16, R.sub.19 and R.sub.20, which are identical or different, are chosen from a hydrogen atom, an alkyl group, or a hydroxyl group; R.sub.21 is chosen from a hydrogen atom, an alkyl group, or an alkoxy group; R.sub.a and R.sub.b, which are identical or different, are chosen from a hydrogen atom or an aryl group, or else R.sub.a and R.sub.b form, together with the carbon atom which carries them, a spirocycloalkyl; Y is chosen from a hydroxyl group or an oxo group; represents a single bond when Y is an oxo group and represents a double bond when Y represents a hydroxyl group; with the proviso that the formulae (III) and (III) comprise at least one sulphonate group R.sub.1R.sub.2R.sub.3R.sub.4N.sup.+(O).sub.2S(O.sup.) on one of the rings D or E or the formulae (III) and (III) comprise at least one carboxylate group R.sub.1R.sub.2R.sub.3R.sub.4N.sup.+(O)C(O.sup.); the anionic dye of formula (I) is different from the dyes of formulae (a) to (u): ##STR00059## ##STR00060## ##STR00061## ##STR00062## ##STR00063##

Description

PREPARATION EXAMPLE

(1) General Preparation of the Dyes of the Invention: Counterion Exchange

(2) A known anionic dye comprising the sodium counterion is suspended in dichloromethane. The water saturated with tetrabutylammonium hydrogensulphate is then added (equivalent volume) and then the mixture is stirred at ambient temperature for 3 hours. The organic phase is recovered and then washed several times with distilled water in order to remove the traces of starting dye. The organic phase is subsequently dried with sodium sulphate, filtered and then evaporated to dryness. Powders are obtained. The analyses are in accordance with the expected structures. The dyes synthesized are given below:

(3) TABLE-US-00003 Structure of the dye obtained according to the Starting known dye invention 0
Preparation of Dye 1

(4) ##STR00036##

(5) A mixture of C.I. Acid Orange 7 (17.5 g, 50 mmol), of tetrabutylammonium chloride (16.7 g, 60 mmol), of dichloromethane (200 ml) and of water (150 ml) is stirred for 2 h. The aqueous phase is recovered and washed twice with dichloromethane (2200 ml) and then the three dichloromethane aliquots are combined, washed with water (3200 ml) and then evaporated to dryness. An orange powder (23.1 g) is obtained. M.p.: 156-158 C.

DYEING EXAMPLE

Example 1

Dyeing Method

(6) TABLE-US-00004 Structure of the dye C.I. Acid Orange 7 (comparative) Dye 1 (invention)

(7) Two dyeing compositions were prepared according to the table below: a composition (A) comprising C.I. Acid Orange 7 (comparative) and a composition (B) comprising the dye 1 (invention):

(8) TABLE-US-00005 Compositions (A), comparative (B), invention Benzoic acid 0.5 g 0.5 g Ethanol 15 g 15 g Benzyl alcohol 5 g 5 g C.I. Acid Orange 7 1 10.sup.4 mol (comparative) Dye 1 (invention) 1 10.sup.4 mol Water q.s. for 100 g q.s. for 100 g

(9) Two locks weighing 1 g of hair (90% natural white hairs) originating from the same lock batch are subsequently steeped in 5 g of each dyeing composition (1 lock in the composition (A) and the other lock in the composition (B)). The locks are maintained in (A) and (B) at ambient temperature for 30 minutes. They are subsequently rinsed with water, shampooed once and then dried in air.

(10) Results:

(11) On conclusion of the dyeing, the colour of the locks is measured with a Minolta CM2600d spectrocolorimeter (specular components included, angle 10, illuminant D65) in the C.I.E L*a*b* system. In this system, L* represents the intensity of the colour, a* indicates the green/red colour axis and b* indicates the blue/yellow colour axis. E represents the variation in colour between an uncoloured lock of hair and a coloured lock of hair and is determined from the following formula:

(12) $E=\sqrt{{\left(L^{*}-L_o^{*}\right)}^2+{\left(a^{*}-a_o^{*}\right)}^2+{\left(b^{*}-b_o^{*}\right)}^2}$
in which L*, a* and b* represent the values measured on the coloured lock and L.sub.0*, a.sub.0* and b.sub.0* represent the values measured on the uncoloured lock.

(13) The higher the value of E, the more coloured is the lock. C* represents the chromaticity in the C.I.E L*, a*, b* system, which is calculated according to the following equation:

(14) $C^{*}=\sqrt{a^{*2}+b^{*2}}$
in which a* and b* are as defined above. The higher the value of C*, the greater the chromaticity of the colour.

(15) The colorimetric results obtained are given in the tables below.

(16) TABLE-US-00006 L*(D65) *(D65) b*(D65) Hairs (90% natural white hairs) 54.25 1.64 11.08 Composition A (comparative) 50.15 10.77 18.78 Composition B (invention) 42.4 26.91 35.74

(17) TABLE-US-00007 C* E measured Composition A (comparative) 21.65 10.4 Composition B (invention) 44.74 27.5

(18) It is apparent, from the above tables, that the colouring power of the dyes according to the invention is significantly greater than that of the comparative: The variation in colour of the hair obtained before and after dyeing is significantly greater with the composition B, which comprises the dye 1 according to the invention, than that obtained with the comparative composition, which comprises the known anionic dye C.I. Acid Orange 7 (E=27.5 vs 10.4). The value of L* measured is in addition significantly lower for the colour of the hair obtained after treatment with the composition B than that obtained with the comparative composition (L=42.4 vs. 50.15). The colour of the hair thus appears visually much darker and consequently more powerful and more intense with the composition B according to the invention. The colour obtained with the composition B according to the invention is significantly more chromatic than that obtained with the comparative composition (C*=44.74 vs. 21.65).