Agent for coloring keratin fibers
View Patent ↗The present invention has for an object agents for dyeing keratin fibers, characterized in that they contain at least one thiazoliumazo dye of general formula (I).
1. A method for dyeing hair comprising the steps of:
(i) applying to hair an amount of hair colorant comprising at least one thiazolium azo dye of general formula (I) sufficient for dying the hair;
(ii) leaving the hair colorant on the hair at a temperature of 15C. to 50C. for a period of 1 to 60 minutes;
(iii) rinsing the hair with water; and
(iv) drying the hair;
wherein:
R1 stands for a saturated or unsaturated (C 1 -C 12 )-alkyl group, a halogen atom-substituted (C 1 -C 12 )-alkyl group, a hydroxy-(C 1 -C 12 )-alkyl group, a (C 1 -C 6 )-alkoxy-(C 1 -C 12 )-alkyl group, an amino-(C 1 -C 12 )-alkyl group, a (C 1 -C 6 )-alkylamino-(C 1 -C 12 )-alkyl group, a di(C 1 -C 6 )-alkyl-amino-(C 1 -C 12 )-alkyl group, a cyano-(C 1 -C 12 )-alkyl group, a substituted or unsubstituted phenyl group or a substituted or unsubstituted benzyl group;
R2 and R3 can be equal or different and, independently of each other, stand for hydrogen, a halogen atom, a saturated or unsaturated (C 1 -C 12 )-alkyl group, (C 1 -C 12 )-alkoxy group, a nitro group, an amino group, a (C 1 -C 12 )-alkylamino group, a di(C 1 -C 12 )-alkylamino group, a (C 1 -C 12 )-hydroxyalkylamino group, a di(C 1 -C 12 )-hydroxyalkylamino group, a substituted or unsubstituted phenyl group or a substituted or unsubstituted heteroaryl group;
R4 stands for hydrogen, a saturated or unsaturated (C 1 -C 12 )-alkyl group, a halogen atom-substituted (C 1 -C 12 )-alkyl group, a hydroxy-(C 1 -C 12 )-alkyl group, an amino-(C 1 -C 12 )-alkyl group or a benzyl group;
R5 and R6 can be equal or different and, independently of each other, stand for hydrogen, a halogen atom, a saturated or unsaturated (C 1 -C 12 )-alkyl group, a hydroxyl group, a (C 1 -C 12 )-alkoxy group, a cyano group, a nitro group, an amino group, a (C 1 -C 12 )-alkylamino group or a di(C 1 -C 12 )-alkylamino group, and A − stands for an anion of an organic or inorganic acid.
2. The method according to claim 1 , wherein R1 is a saturated or unsaturated (C 1 -C 12 )-alkyl group.
3. The method according to claim 2 , wherein R4 is a saturated or unsaturated (C 1 -C 12 )-alkyl group.
4. The method according to claim 1 , wherein A − is a chloride, bro-mide, iodide, hydrogen sulfate, sulfate, toluenesulfonate, benzenesulfonate, monomethyl-sulfate, hexafluorophosphate, hexafluoroantimonate, tetrafluoroborate, tetraphenyborate, formate, acetate or propionate anion.
5. The method according to claim 1 , wherein the compound of formula (I) is selected from among 3-methyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]-azo}thiazolium chloride, 3-methyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium bromide, 3-methyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium mono-methylsulfate, 3-methyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium acetate, 3,4-dimethyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium chloride, 3,4-dimethyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium bromide, 3,4-dimethyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium monomethylsulfate, 3,4-dimethyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium acetate, 3,5-dimethyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium chloride, 3,5-dimethyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium bromide, 3,5-dimethyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium monomethylsulfate, 3,5-dimethyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium acetate, 3,4,5-trimethyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium chloride, 3,4,5-trimethyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium bromide, 3,4,5-trimethyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium monomethylsulfate, 3,4,5-trimethyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium acetate, 5-bromo-3-methyl-2-[(4-[methyl(phenylmethyl)amino]-phenyl]azo]thiazolium chloride, 5-bromo-3-methyl-2-[(4-[methyl(phenylmethyl)amino]phenyl]azo]thiazolium bromide, 5-bromo-3-methyl-2-[(4-[methyl(phenylmethyl)amino]phenyl]azo]thiazolium monomethylsulfate, 5-bromo-3-methyl-2-[(4-[methyl(phenylmethyl)amino]phenyl]azo]thiazolium acetate, 5-methoxy-3-methyl-2-[(4-[methyl(phenylmethyl)amino]phenyl]azo]thiazolium chloride, 5-methoxy-3-methyl-2-[(4-[methyl(phenylmethyl)amino]phenyl]azo]thiazolium bromide, 5-methoxy-3-methyl-2-[(4-[methyl(phenylmethyl)amino]phenyl]azo]thiazolium monomethylsulfate, 5-methoxy-3-methyl-2-[(4-[methyl(phenylmethyl)amino]phenyl]azo]thiazolium acetate, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3-methylthiazolium chloride, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3-methylthiazolium bromide, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3-methylthiazolium monomethylsulfate, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3-methylthiazolium acetate, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3,4-dimethylthiazolium chloride, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3,4-dimethylthiazolium bromide, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3,4-dimethylthiazolium monomethylsulfate, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3,4-dimethylthiazolium acetate, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3,5-dimethylthiazolium chloride, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3,5-dimethylthiazolium bromide, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3,5-dimethylthiazolium monomethylsulfate, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3,5-dimethylthiazolium acetate, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3,4,5-trimethylthiazolium chloride, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3,4,5-trimethylthiazolium bromide, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3,4,5-trimethylthiazolium monomethylsulfate, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3,4,5-trimethylthiazolium acetate, 5-bromo-2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3-methylthiazolium chloride, 5-bromo-2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3-methylthiazolium bromide, 5-bromo-2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3-methylthiazolium monomethylsulfate, 5-bromo-2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3-methylthiazolium acetate, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-5-methoxy-3-methylthiazolium chloride, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-5-methoxy-3-methylthiazolium bromide, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-5-methoxy-3-methylthiazolium monomethylsulfate and 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-5-methoxy-3-methylthiazolium acetate.
6. The method according to claim 1 , wherein the hair colorant contains the compound of formula (I) in an amount from 0.01 to 10 weight percent.
7. The method according to claim 1 , wherein the hair is washed with a shampoo before drying.
8. A method for simultaneously dyeing and setting hair comprising the steps of:
(i) wetting the hair with an agent comprising at least one natural or synthetic polymer or modified polymer of natural origin customary for cosmetic agents and at least one thiazolium azo dye of general formula (I);
(ii) styling the hair; and
(iii) drying the hair;
wherein:
R1 stands for a saturated or unsaturated (C 1 -C 12 )-alkyl group, a halogen atom-substituted (C 1 -C 12 )-alkyl group, a hydroxy-(C 1 -C 12 )-alkyl group, a (C 1 -C 6 )-alkoxy-(C 1 -C 12 )-alkyl group, an amino-(C 1 -C 12 )-alkyl group, a (C 1 -C 6 )-alkylamino-(C 1 -C 12 )-alkyl group, a di(C 1 -C 6 )-alkyl-amino-(C 1 -C 12 )-alkyl group, a cyano-(C 1 -C 12 )-alkyl group, a substituted or unsubstituted phenyl group or a substituted or unsubstituted benzyl group;
R2 and R3 can be equal or different and, independently of each other, stand for hydrogen, a halogen atom, a saturated or unsaturated (C 1 -C 12 )-alkyl group, (C 1 -C 12 )-alkoxy group, a nitro group, an amino group, a (C 1 -C 12 )-alkylamino group, a di(C 1 -C 12 )-alkylamino group, a (C 1 -C 12 )-hydroxyalkylamino group, a di(C 1 -C 12 )-hydroxyalkylamino group, a substituted or unsubstituted phenyl group or a substituted or unsubstituted heteroaryl group;
R4 stands for hydrogen, a saturated or unsaturated (C 1 -C 12 )-alkyl group, a halogen atom-substituted (C 1 -C 12 )-alkyl group, a hydroxy-(C 1 -C 12 )-alkyl group, an amino-(C 1 -C 12 )-alkyl group or a benzyl group;
R5 and R6 can be equal or different and, independently of each other, stand for hydrogen, a halogen atom, a saturated or unsaturated (C 1 -C 12 )-alkyl group, a hydroxyl group, a (C 1 -C 12 )-alkoxy group, a cyano group, a nitro group, an amino group, a (C 1 -C 12 )-alkylamino group or a di(C 1 -C 12 )-alkylamino group, and
A − stands for an anion of an organic or inorganic acid.
9. The method according to claim 8 wherein R1 is a saturated or unsaturated C 1 -C 12 )-alkyl group.
10. The method according to claim 8 wherein R4 is a saturated or unsaturated C 1 -C 12 )-alkyl group.
11. The method according to claim 8 wherein A − is a chloride, bro-mide, iodide, hydrogen sulfate, sulfate, toluenesulfonate, benzenesulfonate, monomethyl-sulfate, hexafluorophosphate, hexafluoroantimonate, tetrafluoroborate, tetraphenyborate, formate, acetate or propionate anion.
12. The method according to claim 8 wherein the compound of formula (I) is selected from the group consisting of 3-methyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium chloride, 3-methyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium bromide, 3-methyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium mono-methylsulfate, 3-methyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo)thiazolium ace-tate, 3,4-dimethyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo)thiazolium chloride, 3,4-dimethyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium bromide, 3,4-dimethyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium monomethylsulfate, 3,4-dimethyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium acetate, 3,5-dimethyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium chloride, 3,5-dimethyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium bromide, 3,5-dimethyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium monomethylsulfate, 3,5-dimethyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium acetate, 3,4,5-trimethyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium chloride, 3,4,5-trimethyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium bromide, 3,4,5-trimethyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium monomethylsulfate, 3,4,5-trimethyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium acetate, 5-bromo-3-methyl-2-[(4-[methyl(phenylmethyl)amino]phenyl]azo}thazolium chloride, 5-bromo-3-methyl-2-[(4-[methyl(phenylmethyl)amino]phenyl]azo]thiazolium bromide, 5-bromo-3-methyl-2-[(4-[methyl(phenylmethyl)amino]phenyl]azo]thiazolium monomethylsulfate, 5-bromo-3-methyl-2-[(4-[methyl(phenylmethyl)amino]phenyl]azo]thiazolium acetate, 5-methoxy-3-methyl-2-[(4-[methyl(phenylmethyl)amino]phenyl]azo]thiazolium chloride, 5-methoxy-3-methyl-2-[(4-[methyl(phenylmethyl)amino]phenyl]azo]thiazolium bromide, 5-methoxy-3-methyl-2-[(4-[methyl(phenylmethyl)amino]phenyl]azo]thiazolium monomethylsulfate, 5-methoxy-3-methyl-2-[(4-[methyl(phenylmethyl)amino]phenyl]azo]thiazolium acetate, 2-{[4-[ethyl-(phenylmethyl)amino]-2-methylphenyl]azo}-3-methylthiazolium chloride, 2-{[4-[ethyl-(phenylmethyl)amino]-2-methylphenyl]azo}-3-methylthiazolium bromide, 2-{[4-[ethyl-(phenylmethyl)amino]-2-methylphenyl]azo}-3-methylthiazolium monomethylsulfate, 2-{[4-[ethyl-(phenylmethyl)amino]-2-methylphenyl]azo}-3-methylthiazolium acetate, 2-{[4-[ethyl-(phenylmethyl)amino]-2-methylphenyl]azo}-3,4-dimethylthiazolium chloride, 2-{[4-[ethyl-(phenylmethyl)amino]-2-methylphenyl]azo}-3,4-dimethylthiazolium bromide, 2-{[4-[ethyl-(phenylmethyl)amino]-2-methylphenyl]azo}-3,4-dimethylthiazolium monomethylsulfate, 2-{[4-[ethyl-(phenylmethyl)amino]-2-methylphenyl]azo}-3,4-dimethylthiazolium acetate, 2-{[4-[ethyl-(phenylmethyl)amino]-2-methylphenyl]azo}-3,5-dimethylthiazolium chloride, 2-{[4-[ethyl-(phenylmethyl)amino]-2-methylphenyl]azo}-3,5-dimethyithiazolium bromide, 2-{[4-[ethyl-(phenylmethyl)amino]-2-methylphenyl]azo}-3,5-dimethylthiazolium monomethylsulfate, 2-{[4-[ethyl-(phenylmethyl)amino]-2-methylphenyl]azo}-3,5-dimethylthiazolium acetate, 2-{[4-[ethyl-(phenylmethyl)amino]-2-methylphenyl]azo}-3,4,5-trimethyithiazolium chloride, 2-{[4-[ethyl-(phenylmethyl)amino]-2-methylphenyl]azo}-3,4,5-trimethyithiazolium bromide, 2-{[4-[ethyl-(phenylmethyl)amino]-2-methylphenyl]azo}-3,4,5-trimethyithiazolium monomethylsulfate, 2-{[4-[ethyl-(phenylmethyl)amino]-2-methylphenyl]azo}-3,4,5-trimethylthazolium acetate, 5-bromo-2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3-methylthiazolium chloride, 5-bromo-2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3-methylthiazolium bromide, 5-bromo-2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3-methylthiazolium monomethylsulfate, 5-bromo-2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3-methylthiazolium acetate, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-5-methoxy-3-methylthiazolium chloride, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-5-methoxy-3-methylthiazolium bromide, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-5-methoxy-3-methylthiazolium monomethylsulfate and 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-5-methoxy-3-methylthiazolium acetate.
13. The method according to claim 8 wherein the hair colorant contains the compound of formula (I) in an amount from 0.01 to 10 weight percent.
14. An agent for dyeing keratin fibers comprising at least one thiazolium azo dye of general formula (I) and at least one additional direct dye,
wherein:
R1 stands for a saturated or unsaturated (C 1 -C 12 )-alkyl group, a halogen atom-substituted (C 1 -C 12 )-alkyl group, a hydroxy-(C 1 -C 12 )-alkyl group, a (C 1 -C 6 )-alkoxy-(C 1 -C 12 )-alkyl group, an amino-(C 1 -C 12 )-alkyl group, a (C 1 -C 6 )-alkylamino-(C 1 -C 12 )-alkyl group, a di(C 1 -C 6 )-alkyl-amino-(C 1 -C 12 )-alkyl group, a cyano-(C 1 -C 12 )-alkyl group, a substituted or unsubstituted phenyl group or a substituted or unsubstituted benzyl group;
R2 and R3 can be equal or different and, independently of each other, stand for hydrogen, a halogen atom, a saturated or unsaturated (C 1 -C 12 )-alkyl group, (C 1 -C 12 )-alkoxy group, a nitro group, an amino group, a (C 1 -C 12 )-alkylamino group, a di(C 1 -C 12 )-alkylamino group, a (C 1 -C 12 )-hydroxyalkylamino group, a di(C 1 -C 12 )-hydroxyalkylamino group, a substituted or unsubstituted phenyl group or a substituted or unsubstituted heteroaryl group;
R4 stands for hydrogen, a saturated or unsaturated (C 1 -C 12 )-alkyl group, a halogen atom-substituted (C 1 -C 12 )-alkyl group, a hydroxy-(C 1 -C 12 )-alkyl group, an amino-(C 1 -C 12 )-alkyl group or a benzyl group;
R5 and R6 can be equal or different and, independently of each other, stand for hydrogen, a halogen atom, a saturated or unsaturated (C 1 -C 12 )-alkyl group, a hydroxyl group, a (C 1 -C 12 )-alkoxy group, a cyano group, a nitro group, an amino group, a (C 1 -C 12 )-alkylamino group or a di(C 1 -C 12 )-alkylamino group, and
A − stands for an anion of an organic or inorganic acid.
15. The agent as defined in claim 14 , wherein the agent contains the additional direct dye in a total amount from 0.01 to 4 weight percent.
16. The agent as defined in claim 14 , wherein R1 is a saturated or unsaturated (C 1 -C 12 )-alkyl group.
17. The agent as defined in claim 16 , wherein R4 is a saturated or unsaturated (C 1 -C 12 )-alkyl group.
18. The agent as defined in claim 14 , wherein A − is a chloride, bro-mide, iodide, hydrogen sulfate, sulfate, toluenesulfonate, benzenesulfonate, monomethyl-sulfate, hexafluorophosphate, hexafluoroantimonate, tetrafluoroborate, tetraphenyborate, formate, acetate or propionate anion.
19. The agent as defined in claim 14 , wherein the compound of formula (I) is selected from the group consisting of 3-methyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]-azo}thiazolium chloride, 3-methyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium bromide, 3-methyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium mono-methylsulfate, 3-methyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium acetate, 3,4-dimethyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium chloride, 3,4-dimethyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium bromide, 3,4-dimethyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium monomethylsulfate, 3,4-dimethyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium acetate, 3,5-dimethyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium chloride, 3,5-dimethyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium bromide, 3,5-dimethyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium monomethylsulfate, 3,5-dimethyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium acetate, 3,4,5-trimethyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium chloride, 3,4,5-trimethyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium bromide, 3,4,5-trimethyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium monomethylsulfate, 3,4,5-trimethyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium acetate, 5-bromo-3-methyl-2-[(4-[methyl-(phenylmethyl)amino]-phenyl]azo}thiazolium chloride, 5-bromo-3-methyl-2-[(4-[methyl-(phenylmethyl)amino]phenyl]azo]thiazolium bromide, 5-bromo-3-methyl-2-[(4-[methyl-(phenylmethyl)amino]phenyl]azo]thiazolium monomethylsulfate, 5-bromo-3-methyl-2-[(4-[methyl-(phenylmethyl)amino]phenyl]azo]thiazolium acetate, 5-methoxy-3-methyl-2-[(4-[methyl(phenylmethyl)amino]phenyl]azo]thiazolium chloride, 5-methoxy-3-methyl-2-[(4-[methyl(phenylmethyl)amino]phenyl]azo]thiazolium bromide, 5-methoxy-3-methyl-2-[(4-[methyl(phenylmethyl)amino]phenyl]azo]thiazolium monomethylsulfate, 5-methoxy-3-methyl-2-[(4-[methyl(phenylmethyl)amino]phenyl]azo]thlazolium acetate, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3-methylthiazolium chloride, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3-methylthiazolium bromide, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3-methylthiazolium monomethylsulfate, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3-methylthiazolium acetate, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3,4-dimethylthiazolium chloride, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3,4-dimethylthiazolium bromide, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3,4-dimethylthiazolium monomethylsulfate, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3,4-dimethylthiazolium acetate, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3,5-dimethyithiazolium chloride, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3,5-dimethylthiazolium bromide, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3,5-dimethyithiazolium monomethylsulfate, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3,5-dimethylthiazolium acetate, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3,4,5-trimethyithiazolium chloride, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3,4,5-trimethyithiazolium bromide, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3,4,5-trimethylthiazolium monomethylsulfate, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3,4,5-trimethylthiazolium acetate, 5-bromo-2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3-methylthiazolium chloride, 5-bromo-2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3-methylthiazolium bromide, 5-bromo-2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3-methylthiazolium monomethylsulfate, 5-bromo-2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3-methylthiazolium acetate, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-5-methoxy-3-methylthiazolium cloride, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyi]azo}-5-methoxy-3-methylthiazolium bromide, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-5-methoxy-3-methyithiazolium monomethylsulfate and 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-5-methoxy-3-methylthiazolium acetate.
20. The agent as defined in claim 14 , wherein the compound of formula (I) is present in an amount from 0.01 to 10 weight percent.
21. The agent as defined in claim 14 , wherein the agent has a pH from 3 to 10.
22. The agent as defined in claim 14 , wherein the agent is a hair colorant.
23. An agent for dyeing keratin fibers comprising at least one thiazolium azo dye of general formula (I) and at least one natural polymer, synthetic polymer, or modified polymer of natural origin customary for cosmetic agents and is in the form of a setting tint or setting color,
wherein:
R1 stands for a saturated or unsaturated (C 1 -C 12 )-alkyl group, a halogen atom-substituted (C 1 -C 12 )-alkyl group, a hydroxy-(C 1 -C 12 )-alkyl group, a (C 1 -C 6 )-alkoxy-(C 1 -C 12 )-alkyl group, an amino-(C 1 -C 12 )-alkyl group, a (C 1 -C 6 )-alkylamino-(C 1 -C 12 )-alkyl group, a di(C 1 -C 6 )-alkyl-amino-(C 1 -C 12 )-alkyl group, a cyano-(C 1 -C 12 )-alkyl group, a substituted or unsubstituted phenyl group or a substituted or unsubstituted benzyl group;
R2 and R3 can be equal or different and, independently of each other, stand for hydrogen, a halogen atom, a saturated or unsaturated (C 1 -C 12 )-alkyl group, (C 1 -C 12 )-alkoxy group, a nitro group, an amino group, a (C 1 -C 12 )-alkylamino group, a di(C 1 -C 12 )-alkylamino group, a (C 1 -C 12 )-hydroxyalkylamino group, a di(C 1 -C 12 )-hydroxyalkylamino group, a substituted or unsubstituted phenyl group or a substituted or unsubstituted heteroaryl group;
R4 stands for hydrogen, a saturated or unsaturated (C 1 -C 12 )-alkyl group, a halogen atom-substituted (C 1 -C 12 )-alkyl group, a hydroxy-(C 1 -C 12 )-alkyl group, an amino-(C 1 -C 12 )-alkyl group or a benzyl group;
R5 and R6 can be equal or different and, independently of each other, stand for hydrogen, a halogen atom, a saturated or unsaturated (C 1 -C 12 )-alkyl group, a hydroxyl group, a (C 1 -C 12 )-alkoxy group, a cyano group, a nitro group, an amino group, a (C 1 -C 12 )-alkylamino group or a di(C 1 -C 12 )-alkylamino group, and
A − stands for an anion of an organic or inorganic acid.
24. The agent as defined in claim 23 , wherein the agent contains the additional direct dye in a total amount from 0.01 to 4 weight percent.
25. The agent as defined in claim 23 , wherein R1 is a saturated or unsaturated (C 1 -C 12 )-alkyl group.
26. The agent as defined in claim 25 , wherein R4 is a saturated or unsaturated (C 1 -C 12 )-alkyl group.
27. The agent as defined in claim 23 , wherein A − is a chloride, bro-mide, iodide, hydrogen sulfate, sulfate, toluenesulfonate, benzenesulfonate, monomethyl-sulfate, hexafluorophosphate, hexafluoroantimonate, tetrafluoroborate, tetraphenyborate, formate, acetate or propionate anion.
28. The agent as defined in claim 23 , wherein the compound of formula (I) is selected from the group consisting of 3-methyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]-azo}thiazolium chloride, 3-methyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium bromide, 3-methyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium mono-methylsulfate, 3-methyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium ace-tate, 3,4-dimethyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium chloride, 3,4-dimethyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium bromide, 3,4-dimethyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium monomethylsulfate, 3,4-dimethyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium acetate, 3,5-dimethyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium chloride, 3,5-dimethyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium bromide, 3,5-dimethyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium monomethylsulfate, 3,5-dimethyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium acetate, 3,4,5-trimethyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium chloride, 3,4,5-trimethyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium bromide, 3,4,5-trimethyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium monomethylsulfate, 3,4,5-trimethyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium acetate, 5-bromo-3-methyl-2-[(4-[methyl(phenylmethyl)amino]phenyl]azo]thiazolium chloride, 5-bromo-3-methyl-2-[(4-[methyl(phenylmethyl)amino]phenyl]azo]thiazolium bromide, 5-bromo-3-methyl-2-[(4-[methyl(phenylmethyl)amino]phenyl]azo]thiazolium monomethylsulfate, 5-bromo-3-methyl-2-[(4-[methyl(phenylmethyl)amino]phenyl]azo]thiazolium acetate, 5-methoxy-3-methyl-2-[(4-[methyl(phenylmethyl)amino]phenyl]azo]thiazolium chloride, 5-methoxy-3-methyl-2-[(4-[methyl(phenylmethyl)amino]phenyl]azo]thiazolium bromide, 5-methoxy-3-methyl-2-[(4-[methyl(phenylmethyl)amino]phenyl]azo]thiazolium monomethylsulfate, 5-methoxy-3-methyl-2-[(4-[methyl(phenylmethyl)amino]phenyl]azo]thiazolium acetate, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3-methylthiazolium chloride, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3-methylthiazolium bromide, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3-methylthiazolium monomethylsulfate, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3-methylthiazolium acetate, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3,4-dimethylthiazolium chloride, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3,4-dimethylthiazolium bromide, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3,4-dimethyithiazolium monomethylsulfate, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3,4-dimethyithiazolium acetate, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3,5-dimethylthiazolium chloride, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3,5-dimethylthiazolium bromide, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3,5-dimethylthiazolium monomethylsulfate, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3,5-dimethylthiazolium acetate, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3,4,5-trimethylthiazolium chloride, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3,4,5-trimethylthiazolium bromide, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3,4,5-trimethyithiazolium monomethylsulfate, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3,4,5-trimethyithiazolium acetate, 5-bromo-2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3-methylthiazolium chloride, 5-bromo-2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3-methylthiazolium bromide, 5-bromo-2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3-methylthiazolium monomethylsulfate, 5-bromo-2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3-methylthiazolium acetate, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-5-methoxy-3-methylthiazolium chloride, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-5-methoxy-3-methylthiazolium bromide, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-5-methoxy-3-methylthiazolium monomethylsulfate and 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo)-5-methoxy-3-methylthiazolium acetate.
29. The agent as defined in claim 23 , wherein the compound of formula (I) is present in an amount from 0.01 to 10 weight percent.
30. The agent as defined in claim 23 , wherein the agent has a pH from 3 to 10.
31. The agent as defined in claim 23 , wherein the agent is a hair colorant.
32. An agent for dyeing keratin fibers comprising at least one thiazolium azo dye of general formula (I) and at least one oxidation dye precursor and wherein the agent is mixed prior to use with an oxidizing agent;
wherein:
R1 stands for a saturated or unsaturated (C 1 -C 12 )-alkyl group, a halogen atom-substituted (C 1 -C 12 )-alkyl group, a hydroxy-(C 1 -C 12 )-alkyl group, a (C 1 -C 6 )-alkoxy-(C 1 -C 12 )-alkyl group, an amino-(C 1 -C 12 )-alkyl group, a (C 1 -C 6 )-alkylamino-(C 1 -C 12 )-alkyl group, a di(C 1 -C 6 )-alkyl-amino-(C 1 -C 12 )-alkyl group, a cyano-(C 1 -C 12 )-alkyl group, a substituted or unsubstituted phenyl group or a substituted or unsubstituted benzyl group;
R2 and R3 can be equal or different and, independently of each other, stand for hydrogen, a halogen atom, a saturated or unsaturated (C 1 -C 12 )-alkyl group, (C 1 -C 12 )-alkoxy group, a nitro group, an amino group, a (C 1 -C 12 )-alkylamino group, a di(C 1 -C 12 )-alkylamino group, a (C 1 -C 12 )-hydroxyalkylamino group, a di(C 1 -C 12 )-hydroxyalkylamino group, a substituted or unsubstituted phenyl group or a substituted or unsubstituted heteroaryl group;
R4 stands for hydrogen, a saturated or unsaturated (C 1 -C 12 )-alkyl group, a halogen atom-substituted (C 1 -C 12 )-alkyl group, a hydroxy-(C 1 -C 12 )-alkyl group, an amino-(C 1 -C 12 )-alkyl group or a benzyl group;
R5 and R6 can be equal or different and, independently of each other, stand for hydrogen, a halogen atom, a saturated or unsaturated (C 1 -C 12 )-alkyl group, a hydroxyl group, a (C 1 -C 12 )-alkoxy group, a cyano group, a nitro group, an amino group, a (C 1 -C 12 )-alkylamino group or a di(C 1 -C 12 )-alkylamino group, and
A − stands for an anion of an organic or inorganic acid.
33. The agent as defined in claim 32 , wherein the agent contains the additional direct dye in a total amount from 0.01 to 4 weight percent.
34. The agent as defined in claim 32 , wherein R1 is a saturated or unsaturated (C 1 -C 12 )-alkyl group.
35. The agent as defined in claim 34 , wherein R4 is a saturated or unsaturated (C 1 -C 12 )-alkyl group.
36. The agent as defined in claim 32 , wherein A − is a chloride, bro-mide, iodide, hydrogen sulfate, sulfate, toluenesulfonate, benzenesulfonate, monomethyl-sulfate, hexafluorophosphate, hexafluoroantimonate, tetrafluoroborate, tetraphenyborate, formate, acetate or propionate anion.
37. The agent as defined in claim 32 , wherein the compound of formula (I) is selected from the group consisting of 3-methyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]-azo}thiazolium chloride, 3-methyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium bromide, 3-methyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium mono-methylsulfate, 3-methyl-2-{[4-[methyl(phenylmethyl)amino[phenyl]azo}thiazolium ace-tate, 3,4-dimethyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium chloride, 3,4-dimethyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium bromide, 3,4-dimethyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium monomethylsulfate, 3,4-dimethyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium acetate, 3,5-dimethyl-2-{[4-[methyl-(phenylmethyl)amino]phenyl]azo}thiazolium chloride, 3,5-dimethyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium bromide, 3,5-dimethyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium monomethylsulfate, 3,5-dimethyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium acetate, 3,4,5-trimethyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium chloride, 3,4,5-trimethyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium bromide, 3,4,5-trimethyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium monomethylsulfate, 3,4,5-trimethyl-2-{[4-[methyl(phenylmethyl)amino]phenyl]azo}thiazolium acetate, 5-bromo-3-methyl-2-[(4-[methyl-(phenylmethyl)amino]-phenyl]azo]thiazolium chloride, 5-bromo-3-methyl-2-[(4-[methyl-(phenylmethyl)amino]phenyl]azo]thiazolium bromide, 5-bromo-3-methyl-2-[(4-[methyl-(phenylmethyl)amino]phenyl]azo]thiazolium monomethylsulfate, 5-bromo-3-methyl-2-[(4-[methyl-(phenylmethyl)amino]phenyl]azo]thiazolium acetate, 5-methoxy-3-methyl-2-[(4-[methyl(phenylmethyl)amino]phenyl]azo]thiazolium chloride, 5-methoxy-3-methyl-2-[(4-[methyl(phenylmethyl)amino]phenyl]azo]thiazolium bromide, 5-methoxy-3-methyl-2-[(4-[methyl(phenylmethyl)amino]phenyl]azo]thiazolium monomethylsulfate, 5-methoxy-3-methyl-2-[(4-[methyl(phenylmethyl)amino]phenyl]azo]thiazolium acetate, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3-methylthiazolium chloride, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3-methylthiazolium bromide, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3-methylthiazolium monomethylsulfate, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3-methylthiazolium acetate, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3,4-dimethylthiazolium chloride, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3,4-dimethylthiazolium bromide, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3,4-dimethylthiazolium monomethylsulfate, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3,4-dimethylthiazolium acetate, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3,5-dimethyithiazolium chloride, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3,5-dimethyithiazolium bromide, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3 5-dimethyithiazolium monomethylsulfate, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3,5-dimethylthiazolium acetate, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3,4,5-trimethylthiazolium chloride, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3,4,5-trimethylthiazolium bromide, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3,4,5-trimethylthiazolium monomethylsulfate, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3,4,5-trimethylthiazolium acetate, 5-bromo-2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3-methylthiazolium chloride, 5-bromo-2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3-methylthiazolium bromide, 5-bromo-2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3-methylthiazolium monomethylsulfate, 5-bromo-2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-3-methylthiazolium acetate, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-5-methoxy-3-methylthiazolium chloride, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-5-methoxy-3-methylthiazolium bromide, 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-5-methoxy-3-methylthiazolium monomethylsulfate and 2-{[4-[ethyl(phenylmethyl)amino]-2-methylphenyl]azo}-5-methoxy-3-methylthiazolium acetate.
38. The agent as defined in claim 32 , wherein the compound of formula (I) is present in an amount from 0.01 to 10 weight percent.
39. The agent as defined in claim 32 , wherein the agent has a pH from 3 to 10.
40. The agent as defined in claim 32 , wherein the agent is a hair colorant.