Use of polycationic compounds in the dyeing of keratinous fibres
A subject-matter of the present patent application is the use, as direct dye in dyeing compositions for keratinous fibres, in particular human keratinous fibres, such as the hair, or for the manufacture of such compositions, of a specific polycationic compound.
1. A dyeing composition for dyeing keratinous fibres, comprising, in an appropriate dyeing medium, at least one oxidation base and at least one direct dye of formula (I):
wherein:
Xz′ − is chosen from organic and inorganic anions;
z and z′ are such that the overall charge of the molecule is zero;
A is a positively-charged heterocyclic ring chosen from:
substituted and unsubstituted thiazolium, wherein the thiazolium is substituted with at most one alkoxycarbonyl functional group;
substituted and unsubstituted imidazolium;
substituted and unsubstituted benzimidazolium;
substituted and unsubstituted benzothiazolium pyridino;
substituted and unsubstituted naphthothiazolium; and
substituted benzothiazolium;
B is chosen from optionally substituted C 6 -C 30 arylene groups and optionally substituted 5- to 10-membered heterocyclic groups;
L is chosen from substituted and unsubstituted, linear, branched, and cyclic C 1 -C 30 alkylene radicals,
wherein the C 1 -C 30 alkylene radicals are optionally interrupted or terminated by at least one heteroatomic group chosen from O, S, NH or NR, wherein R is chosen from linear and branched C 1 -C 10 alkyl radicals,
wherein the C 1 -C 30 alkylene radicals are optionally interrupted by at least one radical chosen from heterocyclic and nonheterocyclic, aromatic and nonaromatic, cyclic radicals, and
wherein the C 1 -C 30 alkylene radicals optionally carry at least one quaternary cationic charge, and wherein at least one carbon atom of the C 1 -C 30 alkylene radical is optionally replaced by a carbonyl group;
R1, R2 and R3 are independently chosen from:
optionally substituted, linear, branched and cyclic C 1 -C 10 alkyl radicals;
optionally substituted, linear, branched and cyclic C 1 -C 10 arylalkyl radicals;
optionally substituted aryl radicals; and
linear and branched C 1 -C 10 aryloxyalkyl radicals;
wherein at least one of the R1, R2, and R3 radicals may form, with the nitrogen atom carrying it, and optionally with L, an optionally substituted, saturated or unsaturated, 5- to 10-membered heterocycle that optionally comprises at least one additional heteroatom.
2. The dyeing composition according to claim 1 , wherein the keratinous fibres are human keratinous fibres.
3. The dyeing composition according to claim 2 , wherein the human keratinous fibres are human hair.
4. The dyeing composition according to claim 1 , wherein the at least one direct dye of formula (I) is chosen from:
2-[[4-ethyl[2-trimethylammonio)ethyl]amino]phenyl]azo]-4-(methoxycarbonyl)-5-(2-methoxy-2-oxoethyl)-3-methylthiazolium;
2-[[4-[[2-[dimethyl(phenylmethyl)ammonio]ethyl]ethylamino]phenyl]azo-3-methylthiazolium dichloride;
2-[[4-(diethylamino)-2-[[trimethylammonio)acetyl]amino]phenyl]azo]-5-(ethoxycarbonyl)-3-methyl-4-phenylthiazolium;
2-[[4-(diethylamino)-2-[[(trimethylammonio)acetyl]oxy]phenyl]azo]-5-(ethoxycarbonyl)-3,4-dimethylthiazolium bis[tetrafluoroborate(1-)];
2-[[4-(diethylamino)-2-[[(trimethylammonio)acetyl]oxy]phenyl]azo]-5-(ethoxycarbonyl)-3,4-dimethylthiazolium;
2-[[4-ethyl[2-[(2-hydroxypropyl)dimethylammonio]ethyl]amino]-2-methylphenyl]azo]-3-methylthiazolium dichloride;
2-[[4-[ethyl(2-(trimethylammonio)ethyl]amino]phenyl]azo]-3-methylthiazolium dichloride;
2-[[4-[ethyl[2-(trimethylammonio)ethyl]amino]phenyl]azo]-3-methyl-4-phenylthiazolium bis[tetrafluoroborate(1-)];
2-[[4-[ethyl[2-(trimethylammonio)ethyl]amino]phenyl]azo]-3-methyl-4-phenylthiazolium;
1-(2-{(4-methoxyphenyl)-[3-methyl-4-(thiazol-3-ium-2-ylazo)phenyl]amino}ethyl)-4-methylpyridinium chloride;
1-(2-{phenyl-[5-ethoxycarbonyl-3,4-dimethyl-4-(thiazol-3-ium-2-ylazo)phenyl]amino}ethyl)pyridinium chlorozincate;
1-(2-{(4-methoxyphenyl)[5-ethoxycarbonyl-3,4-dimethyl-4-(thiazol-3-ium-2-ylazo)phenyl]amino}ethyl)-4-methylpyridinium chloride;
4-dimethylamino-1-(2-{[4-(5-ethoxycarbonyl-3,4-dimethyl-4-(thiazol-3-ium-2-ylazo)phenyl](p-tolyl)amino}ethyl)pyridinium chlorozincate;
1-{2-[[4-(5-acetyl-3,4-dimethyl-4-(thiazol-3-ium-2-ylazo)phenyl](4-methoxyphenyl)amino]ethyl}pyridinium chloride;
1-(3-{[4-(5-ethoxycarbonyl-3,4-dimethyl-4-(thiazol-3-ium-2-ylazo)phenyl](phenyl)amino}-2-hydroxypropyl)-pyridinium chlorozincate;
1-{3-[[4-(5-ethoxycarbonyl-3,4-dimethyl-4-(thiazol-3-ium-2-ylazo)phenyl](4-methoxyphenyl)amino]-2-hydroxypropyl}-4-methylpyridinium chloride;
4-[4-[(1,3-dimethyl-1H-imidazolium-2-yl)azo]phenyl]-1,1-dimethylpiperazinium diiodide;
2-[[4-[ethyl[2-[[(trimethylammonio)acetyl]amino]ethyl]amino]-2-methylphenyl]azo]-1,3-dimethyl-1H-imidazolium diiodide;
2-[[4-[[3-(diethylmethylammonio)-2-hydroxypropyl]ethylamino]-2-methylphenyl]azo]-1,3-dimethyl-1H-imidazolium diiodide;
2-[[4-[[2-(diethylmethylammonio)ethyl]ethylamino]-2-methylphenyl]azo]-1,3-dimethyl-1H-imidazolium diiodide;
2-[[4-[ethyl[2-(trimethylammonio)ethyl]amino]phenyl]azo]-1,3-dimethyl-1H-imidazolium diiodide;
2-[[4-[[2-(diethylmethylammonio)ethyl]ethylamino]-phenyl]azo]-1,3-dimethyl-1H-imidazolium diiodide;
2-[[4-[ethyl[2-(trimethylammonio)ethyl]amino]phenyl]azo]-3-methylnapththo[2,1-d]thiazolium dichloride;
2-[[4-anilino-2-(ethylamino)-6-[[3-(trimethylammonio)propyl]amino]-5-pyrimidinyl]azo]-6-methoxy-3-methyl benzothiazolium bis(methylsulphate);
2-[[2-(ethylamino)-4-(phenylamino)-6-[[3-(trimethylammonio)propyl]amino]-5-pyrimidinyl]azo]-6-methoxy-3-methylbenzothiazolium;
2-[[4-[ethyl[2-(trimethylammonio)ethyl]amino]phenyl]azo]-6-methoxy-3-methylbenzothiazolium sulphate;
2-[[4-[ethyl[2-(trimethylammonio)ethyl]amino]phenyl]azo]-6-methoxy-3-methylbenzothiazolium diacetate;
2-[[4-[ethyl[2-(trimethylammonio)ethyl]amino]phenyl]azo]-6-methoxy-3-methylbenzothiazolium bis(methylsulphate);
2-[[4-[ethyl[2-(trimethylammonio)ethyl]amino]phenyl]azo]-6-methoxy-3-methylbenzothiazolium;
6-ethoxy-2-[[4-[ethyl[2-hydroxy-3-(trimethylammonio)propyl]amino]-2-methylphenyl]azo]-3-methylbenzothiazolium bis[tetrafluoroborate(1-)];
6-ethoxy-2-[[4-[ethyl[2-hydroxy-3-(trimethylammonio)propyl]amino]-2-methylphenyl]azo]-3-methylbenzothiazolium;
3-[4-(6-methoxy-3-methylbenzothiazol-3-ium)phenyl]-3-aza-6-azoniaspiro[5.5]undecane dichloride;
diethyl(2-{ethyl[4-(3-methylbenzothiazol-2-ylazo)phenyl]amino}ethyl)(2-phenoxyethyl)ammonium dichloride;
1-(2-{ethyl[4-(6-methoxy-3-methylbenzothiazolium-2-ylazo)phenyl]amino}ethyl)pyridinium tetrafluoroborate;
(2-{ethyl[4-(1,2,3-trimethyl-1H-benzoimidazolium-5-ylazo)phenyl]amino}ethyl)trimethylammonium chlorozincate;
diethylmethyl{2-[3-methyl[4-(1,2,3-trimethyl-1H-benzoimidazolium-5-ylazo)phenylamino]ethyl}ammonium chlorozincate;
(2-{propyl[4-(1,2,3-trimethyl-1H-benzoimidazolium-5-ylazo)phenyl]amino}ethyl)trimethylammonium chlorozincate;
4-(2-{[4-(6-chloro-1,3-dimethyl-3H-benzoimidazolium-4-ylazo)phenyl]ethylamino}ethyl)-1-methylpyridinium tetrafluoroborate; and
(2-{4-[5-(3-ethylbenzothiazolium-2-yl)-6-hydroxy-1-methyl-2-oxo-1,2-dihydropyridin-3-ylazo]phenyl}-2-oxoethyl)trimethylammonium methyl sulphate.
5. The dyeing composition according to claim 1 , wherein the at least one direct dye of formula (I) is present in an amount ranging from 0.001% to 20% by weight, with respect to the total weight of the composition.
6. The dyeing composition according to claim 5 , wherein the at least one direct dye of formula (I) is present in an amount ranging from 0.1% to 5% by weight, with respect to the total weight of the composition.
7. The dyeing composition according to claim 1 , wherein the at least one oxidation base is chosen from para-phenylenediamines, bisphenylalkylenediamines, para-aminophenols, ortho-aminophenols, heterocyclic bases, and addition salts thereof.
8. The dyeing composition according to claim 1 , wherein the at least one oxidation base is present in an amount ranging from 0.001% to 20% by weight, relative to the total weight of the composition.
9. The dyeing composition according to claim 8 , wherein the at least one oxidation base is present in an amount ranging from 0.005% to 6% by weight, relative to the total weight of the composition.
10. The dyeing composition according to claim 1 , further comprising at least one additional direct dye.
11. The dyeing composition according to claim 1 , further comprising at least one oxidation dye precursor chosen from couplers.
12. The dyeing composition according to claim 11 , wherein the at least one coupler is chosen from meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalene couplers, heterocyclic couplers, and addition salts thereof.
13. The dyeing composition according to claim 12 , wherein the at least one coupler is chosen from 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene, 4-chloro-1,3-dihydroxybenzene, 2,4-diamino-1-(β-hydroxyethyloxy)benzene, 2-amino-4-(β-hydroxyethylamino)-1-methoxybenzene, 1,3-diaminobenzene, 1,3-bis(2,4-diaminophenoxy)propane, 3-ureidoaniline, 3-ureido-1-(dimethylamino)benzene, sesamol, 1-(β-hydroxyethylamino)-3,4-methylenedioxybenzene, α-naphthol, 2-methyl-1-naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole, 2-amino-3-hydroxypyridine, 6-hydroxybenzomorpholine, 3,5-diamino-2,6-dimethoxypyridine, 1-N-(β-hydroxyethyl)amino-3,4-methylenedioxybenzene, 2,6-bis(β-hydroxyethylamino)toluene, and addition salts thereof.
14. The dyeing composition according to claim 11 , wherein the at least one coupler is present in an amount ranging from 0.001% to 20% by weight, relative to the total weight of the composition.
15. The dyeing composition according to claim 14 , wherein the at least one coupler is present in an amount ranging from 0.005% to 6% by weight, relative to the total weight of the composition.
16. The dyeing composition according to claim 1 , further comprising at least one solvent.
17. The dyeing composition according to claim 16 , wherein the at least one solvent is chosen from ethanol, propylene glycol, glycerol, and polyol monoethers.
18. The dyeing composition according to claim 1 , further comprising at least one adjuvant chosen from anionic, cationic, nonionic, amphoteric, and zwitterionic surfactants; anionic, cationic, nonionic, amphoteric, and zwitterionic polymers; inorganic thickening agents; organic thickening agents; antioxidants; penetrating agents; sequestering agents; fragrances; buffers; dispersants; conditioning agents; film-forming agents; ceramides; preservatives; and opacifiers.
19. The dyeing composition according to claim 1 , further comprising at least one oxidizing agent chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts, peracids, and oxidase enzymes.
20. The dyeing composition according to claim 19 , wherein the at least one oxidizing agent is hydrogen peroxide.
21. A process for dyeing keratinous fibres, comprising applying to the keratinous fibres a dyeing composition comprising, in an appropriate dyeing medium, at least one oxidation base and at least one direct dye of formula (I):
wherein:
Xz′ − is chosen from organic and inorganic anions;
z and z′ are such that the overall charge of the molecule is zero;
A is a positively-charged heterocyclic ring chosen from:
substituted and unsubstituted thiazolium, wherein the thiazolium is substituted with at most one alkoxycarbonyl functional group;
substituted and unsubstituted imidazolium;
substituted and unsubstituted benzimidazolium;
substituted and unsubstituted benzothiazolium pyridino;
substituted and unsubstituted naphthothiazolium; and
substituted benzothiazolium;
B is chosen from optionally substituted C 6 -C 30 arylene groups and optionally substituted 5- to 10-membered heterocyclic groups;
L is chosen from substituted and unsubstituted, linear, branched, and cyclic C 1 -C 30 alkylene radicals,
wherein the C 1 -C 30 alkylene radicals are optionally interrupted or terminated by at least one heteroatomic group chosen from O, S, NH or NR, wherein R is chosen from linear and branched C 1 -C 10 alkyl radicals,
wherein the C 1 -C 30 alkylene radicals are optionally interrupted by at least one radical chosen from heterocyclic and nonheterocyclic, aromatic and nonaromatic, cyclic radicals, and
wherein the C 1 -C 30 alkylene radicals optionally carry at least one quaternary cationic charge, and wherein at least one carbon atom of the C 1 -C 30 alkylene radical is optionally replaced by a carbonyl group;
R1, R2 and R3 are independently chosen from:
optionally substituted, linear, branched and cyclic C 1 -C 10 alkyl radicals
optionally substituted, linear, branched and cyclic C 1 -C 10 arylalkyl radicals;
optionally substituted aryl radicals; and
linear and branched C 1 -C 10 aryloxyalkyl radicals;
wherein at least one of the R1, R2, and R3 radicals may form, with the nitrogen atom carrying it, and optionally with L, an optionally substituted, saturated or unsaturated, 5- to 10-membered heterocycle that optionally comprises at least one additional heteroatom; and
leaving the dyeing composition on the fibers for a period of time ranging from 5 minutes to 1 hour.
22. The process of claim 21 , wherein the dyeing composition is left to stand for a period of time ranging from 15 minutes to 1 hour.
23. The process of claim 21 , wherein the keratinous fibres are human keratinous fibres.
24. The process of claim 23 , wherein the human keratinous fibres are human hair.
25. A method of obtaining hair colourings that are substantially resistant to external agents and to shampooing operations, comprising
applying to the keratinous fibres a dyeing composition comprising, in an appropriate dyeing medium, at least one oxidation base and at least one direct dye of formula (I):
wherein:
Xz′ − is chosen from organic and inorganic anions;
z and z′ are such that the overall charge of the molecule is zero;
A is a positively-charged heterocyclic ring chosen from:
substituted and unsubstituted thiazolium, wherein the thiazolium is substituted with at most one alkoxycarbonyl functional group;
substituted and unsubstituted imidazolium;
substituted and unsubstituted benzimidazolium;
substituted and unsubstituted benzothiazolium pyridino;
substituted and unsubstituted naphthothiazolium; and
substituted benzothiazolium;
B is chosen from optionally substituted C 6 -C 30 arylene groups and optionally substituted 5- to 10-membered heterocyclic groups;
L is chosen from substituted and unsubstituted, linear, branched, and cyclic C 1 -C 30 alkylene radicals,
wherein the C 1 -C 30 alkylene radicals are optionally interrupted or terminated by at least one heteroatomic group chosen from O, S, NH or NR, wherein R is chosen from linear and branched C 1 -C 10 alkyl radicals,
wherein the C 1 -C 30 alkylene radicals are optionally interrupted by at least one radical chosen from heterocyclic and nonheterocyclic, aromatic and nonaromatic, cyclic radicals, and
wherein the C 1 -C 30 alkylene radicals optionally carry at least one quaternary cationic charge, and wherein at least one carbon atom of the C 1 -C 30 alkylene radical is optionally replaced by a carbonyl group;
R1, R2 and R3 are independently chosen from:
optionally substituted, linear, branched and cyclic C 1 -C 10 alkyl radicals
optionally substituted, linear, branched and cyclic C 1 -C 10 arylalkyl radicals;
optionally substituted aryl radicals; and
linear and branched C 1 -C 10 aryloxyalkyl radicals;
wherein at least one of the R1, R2, and R3 radicals may form, with the nitrogen atom carrying it, and optionally with L, an optionally substituted, saturated or unsaturated, 5- to 10-membered heterocycle that optionally comprises at least one additional heteroatom.
26. The method of claim 25 , wherein the keratinous fibres are human keratinous fibres.
27. The method of claim 26 , wherein the human keratinous fibres are human hair.
28. A method of manufacturing a dyeing composition for keratinous fibres, comprising adding to a cosmetically acceptable medium at least one direct dye of formula (I):
wherein:
Xz′ − is chosen from organic and inorganic anions;
z and z′ are such that the overall charge of the molecule is zero;
A is a positively-charged heterocyclic ring chosen from:
substituted and unsubstituted thiazolium, wherein the thiazolium is substituted with at most one alkoxycarbonyl functional group;
substituted and unsubstituted imidazolium;
substituted and unsubstituted benzimidazolium;
substituted and unsubstituted benzothiazolium pyridino;
substituted and unsubstituted naphthothiazolium; and
substituted benzothiazolium;
B is chosen from optionally substituted C 6 -C 30 arylene groups and optionally substituted 5- to 10-membered heterocyclic groups;
L is chosen from substituted and unsubstituted, linear, branched, and cyclic C 1 -C 30 alkylene radicals,
wherein the C 1 -C 30 alkylene radicals are optionally interrupted or terminated by at least one heteroatomic group chosen from O, S, NH or NR, wherein R is chosen from linear and branched C 1 -C 10 alkyl radicals,
wherein the C 1 -C 30 alkylene radicals are optionally interrupted by at least one radical chosen from heterocyclic and nonheterocyclic, aromatic and nonaromatic, cyclic radicals, and
wherein the C 1 -C 30 alkylene radicals optionally carry at least one quaternary cationic charge, and wherein at least one carbon atom of the C 1 -C 30 alkylene radical is optionally replaced by a carbonyl group;
R1, R2 and R3 are independently chosen from:
optionally substituted, linear, branched and cyclic C 1 -C 10 alkyl radicals
optionally substituted, linear, branched and cyclic C 1 -C 10 arylalkyl radicals;
optionally substituted aryl radicals; and
linear and branched C 1 -C 10 aryloxyalkyl radicals;
wherein at least one of the R1, R2, and R3 radicals may form, with the nitrogen atom carrying it, and optionally with L, an optionally substituted, saturated or unsaturated, 5- to 10-membered heterocycle that optionally comprises at least one additional heteroatom.