Coloring agents for keratin fibers
View Patent ↗The present invention relates to agents for coloring keratin fibers which comprise at least one cationic azodye of the general formula (I).
1. An agent for the simultaneous lightening and coloring of keratin fibers, comprising at least one oxidizing agent, characterized by comprising at least one azodye of the general formula (I);
wherein
X is selected from the group consisting of oxygen, sulfur, N—R3 and C—R4;
Y is selected from the group consisting of C—R5, nitrogen, N—R6, sulfur and oxygen;
Z is C—R7 or nitrogen;
wherein the heterocycle of the formula (I) comprises at least two and at most three heteroatoms, where the heterocycle comprises at most one sulfur atom or one oxygen atom;
n is an integer from 1 to 6;
R1 is selected from the group consisting of hydrogen, a saturated or unsaturated (C 1 -C 12 )-alkyl group, a (C 1 -C 12 )-alkyl group substituted by a halogen atom, a hydroxy-(C 2 -C 12 )-alkyl group, an amino-(C 1 -C 12 )-alkyl group, a substituted or unsubstituted phenyl group and a substituted or unsubstituted benzyl group;
R2, R4, R5, and R7 may be identical or different and, independently of one another, are selected from the group consisting of hydrogen, a halogen atom, a saturated or unsaturated (C 1 -C 12 )-alkyl group, a (C 1 -C 12 )-alkyl group substituted by a halogen atom, a hydroxyl group, a hydroxy-(C 1 -C 12 )-alkyl group, a (C 1 -C 12 )-alkoxy group, a (C 1 -C 12 )-thioalkyl group, a cyano group, a nitro group, an amino group, a (C 1 -C 12 )-alkylamino group, a (C 1 -C 12 )-dialkylamino group, a carboxylic acid group, a C(O)O—(C 1 -C 12 )-alkyl group, a substituted or unsubstituted C(O)O—phenyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group and a substituted or unsubstituted heteroaryl group;
or if Y and Z are C—R5 and C—R7, the radical groups R5 and R7, together with the remaining molecule, can form a heterocyclic or carbocyclic, saturated or unsaturated, substituted or unsubstituted ring system;
or if X and Y are C—R4 and C—R5, the radical groups R4 and R5, together with the remaining molecule, can form a heterocyclic or carbocyclic, saturated or unsaturated, substituted or unsubstituted ring system;
R3 and R6 may be identical or different and, independently of one another, are selected from the group consisting of a saturated or unsaturated (C 1 -C 12 )-alkyl group, a (C 1 -C 12 )-alkyl group substituted by a halogen atom (F, Cl, Br, I), a hydroxy-(C 2 -C 12 )-alkyl group, an amino-(C 1 -C 12 )-alkyl group, a substituted or unsubstituted phenyl group and a substituted or unsubstituted benzyl group;
Q+ represents a quaternary monoalkylammonium, dialkylammonium or trialkylammonium group, where the alkylgroups may be identical or different and, independently of one another, are a saturated or unsaturated (C 1 -C 12 )-alkyl group;
wherein when Q+ represents a tri(C 1 -C 4 )alkylammonium group, and X is sulfur and Y is nitrogen or a CH group, Z is not a C—R5 residue with R5 representing hydrogen, a halogen atom, a nitro group or an alkylgroup;
or Q+ represents a quaternary mononoarylammonium, diarylammonium or triarylammonium group, where the arylgroups may be identical or different and, independently of one another, are an unsubstituted or substitued phenylgroup;
or Q+ represents a quaternary alkylarylammonium group, where the alkylgroups may be identical or different and, independently of one another, are a saturated or unsaturated (C 1 -C 12 )-alkyl group, and the arylgroups may be identical or different and, independently of one another, are an unsubstituted or substitued phenylgroup; the anion An— is an organic or inorganic acid anion.
2. An agent for oxidative coloring of keratin fibers based on at least one oxidation dye precursor, comprising at least one azodye of the general formula (I);
wherein
X is selected from the group consisting of oxygen, sulfur, N—R3 and C—R4;
Y is selected from the group consisting of C—R5, nitrogen, N—R6, sulfur and oxygen;
Z is C—R7 or nitrogen;
wherein the heterocycle of the formula (I) comprises at least two and at most three heteroatoms, where the heterocycle comprises at most one sulfur atom or one oxygen atom;
n is an integer from 1 to 6;
R1 is selected from the group consisting of hydrogen, a saturated or unsaturated (C 1 -C 12 )-alkyl group, a (C 1 -C 12 )-alkyl group substituted by a halogen atom, a hydroxy-(C 2 -C 12 )-alkyl group, an amino-(C 1 -C 12 )-alkyl group, a substituted or unsubstituted phenyl group and a substituted or unsubstituted benzyl group;
R2, R4, R5, and R7 may be identical or different and, independently of one another, are selected from the group consisting of hydrogen, a halogen atom, a saturated or unsaturated (C 1 -C 12 )-alkyl group, a (C 1 -C 12 )-alkyl group substituted by a halogen atom, a hydroxyl group, a hydroxy-(C 1 -C 12 )-alkyl group, a (C 1 -C 12 )-alkoxy group, a (C 1 -C 12 )-thioalkyl group, a cyano group, a nitro group, an amino group, a (C 1 -C 12 )-alkylamino group, a (C 1 -C 12 )-dialkylamino group, a carboxylic acid group, a C(O)O—(C 1 -C 12 )-alkyl group, a substituted or unsubstituted C(O)O-phenyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group and a substituted or unsubstituted heteroaryl group;
or if Y and Z are C—R5 and C—R7, the radical groups R5 and R7, together with the remaining molecule, can form a heterocyclic or carbocyclic, saturated or unsaturated, substituted or unsubstituted ring system;
or if X and Y are C—R4 and C—R5, the radical groups R4 and R5, together with the remaining molecule, can form a heterocyclic or carbocyclic, saturated or unsaturated, substituted or unsubstituted ring system;
R3 and R6 may be identical or different and, independently of one another, are selected from the group consisting of a saturated or unsaturated (C 1 -C 12 )-alkyl group, a (C 1 -C 12 )-alkyl group substituted by a halogen atom (F, Cl, Br, I), a hydroxy-(C 2 -C 12 )-alkyl group, an amino-(C 1 -C 12 )-alkyl group, a substituted or unsubstituted phenyl group and a substituted or unsubstituted benzyl group;
Q+ represents a quaternary monoalkylammonium, dialkylammonium or trialkylammonium group, where the alkylgroups may be identical or different and, independently of one another, are a saturated or unsaturated (C 1 -C 12 )-alkyl group;
wherein when Q+ represents a tri(C 1 -C 4 )alkylammonium group, and X is sulfur and Y is nitrogen or a CH group, Z is not a C—R5 residue with R5 representing hydrogen, a halogen atom, a nitro group or an alkylgroup;
or Q+ represents a quaternary monoarylammonium, diarylammonium or triarylammonium group, where the arylgroups may be identical or different and, independently of one another, are an unsubstituted or substitued phenylgroup;
or Q+ represents a quaternary alkylarylammonium group, where the alkylgroups may be identical or different and, independently of one another, are a saturated or unsaturated (C 1 -C 12 )-alkyl group, and the arylgroups may be identical or different and, independently of one another, are an unsubstituted or substitued phenylgroup:
the anion An— is an organic or inorganic acid anion.
3. The agent according to claim 2 , wherein the oxidizing agent is chosen from the group consisting of hydrogen peroxide and its addition compounds onto urea, melamine, sodium borate or sodium carbonate.
4. The agent according to claim 1 , wherein the oxidizing agent is selected from the group consisting of hydrogen peroxide and its addition compounds onto urea, melamine, sodium borate or sodium carbonate, and persulfates.
5. The agent according to claim 1 , wherein the cationic azodye of the formula (I) is selected from the group consisting of 2-[{4-[(4,5-dimethyl-1,3-thiazol-2-yl) diazenyl ]phenyl}(ethyl)amino]-N,N,N-trimethylethanaminium bromide; 2-[{4-[(4,5-dimethyl -1,3-thiazol-2-yl)diazenyl]-3-methylphenyl}(ethyl)-amino]-N,N,N-trimethylethanaminium bromide; 2-[{3-chloro-4-[(4,5-dimethyl-1,3-thiazol-2-yl) diazenyl]phenyl}(ethyl)amino]-N,N,N-trimethylethanaminium bromide; 2-[{4[(4-methyl -1,3-thiazol-2-yl)diazenyl]phenyl}(ethyl)amino]-N,N,N-trimethylethanaminium bromide;
2-[{4(4-methyl-1,3-thiazol-2-yl)diazenyl]-3-methylphenyl}(ethyl)amino]-N,N,N-trimethylethanaminium bromide; 2-[{3-chloro-4-[(4-methyl-1,3-thiazol-2-yl) diazenyl]phenyl}(ethyl)amino]-N,N,N-trimethylethanaminium bromide;
2-[{4-[1,3-benzothiazol-2-yldiazenyl]phenyl}(ethyl)amino]-N,N,N-trimethylethanaminium bromide; 2-(ethyl {4-[(6-nitro-1,3-benzothiazol-2-yl) diazenyl]phenyl}amino)-N,N,N-trimethylethanaminium bromide; 2-[{4-{(5,6-dinitro-1,3-benzothiazol-2-yl)diazenyl]phenyl}(ethyl)amino}-N,N,N-trimethylethanaminium bromide; 2-[{4-[(4,6-dinitro-1,3-benzothiazol-2-yl)diazenyl]phenyl}(ethyl)amino]-N,N,N-trimethylethanaminium bromide; 2-(ethyl{4-[(4-methyl-6-nitro-1,3-benzothiazol-2-yl) diazenyl]phenyl}amino)-N,N,N-trimethylethanaminium bromide; 2-[{4-[(4-chloro-6-nitro-1,3-benzothiazol-2-yl) diazenyl]-phenyl}(ethyl)amino]-N,N,N-trimethylethanaminium bromide; 2-(ethyl{4-[1H-[1,3]thiazolo[5,4-f]indazol-6-yldiazenyl]phenyl}amino)-N,N,N-trimethylethanaminium bromide;
2-[{4-[(5-chloro[1,3]thiazolo[5,4-b]pyridin-2-yl)diazenyl]phenyl}(ethyl)aminol]-N,N,N-trimethylethanaminium bromide; 2-[{4-[(5-methoxy[1,3]thiazolo[5,4-b]pyridin-2-yl) diazenyl]-pheny{(ethyl)amino]-N,N,N-trimethylethanaminium bromide; N,N-diethyl-2-(ethyl{4-[1,3-thiazol-2-yldiazenyl]phenyl}amino)-N-methylethanaminium bromide;
N-[2-(ethyl{4-[1,3-thiazol-2-yldiazenyl]phenyl}amino)ethyl]-N,N-dimethylbenzenaminium bromide; 2-(ethyl{4-[1,2,4-thiadiazol-5-yldiazenyl]phenyl}amino)-N,N,N-trimethylethanaminium bromide; 2-(ethyl{4-[(3-phenyl-1,2,4-thiadiazol-5-yl)diazenyl]phenyl}amino)-N,N,N-trimethylethanaminium bromide; 2-[{4-[(3-chloro-1,2,4-thiadiazol-5-yl)diazenyl]phenyl}(ethyl)aminol-N,N,N-trimethylethanaminium bromide; 2-(ethyl{4-[1H-1,2,4-triazol-5-yldiazenyl]phenyl}-amino) -N,N,N-trimethylethanaminium bromide; 1-[2-(ethyl{4-[(1-methyl-1H-imidazol-2-yl) diazenyl]-phenyl}amino)ethyl]-N,N,N-trimethylethanaminium bromide: and
1-[2-(ethyl{3-methyl-4-[(1-methyl-1H-imidazol-2-yl)diazenyl]phenyl}amino)ethyl]-N,N,N -trimethylethanaminium bromide and 1-{2-[{3-chloro-4-[(1-methyl-1H-imidazol-2-yl) diazeny]phenyl}(ethyl)amino]ethyl}-N,N,N-trimethylethanaminium bromide.
6. The agent according to claim 2 , wherein the cationic azodye of the formula (I) is selected from the group consisting of 2-[{4-[(4,5-dimethyl-1,3-thiazol-2-yl) diazenyl]phenyl}(ethyl)amino]-N,N,N-trimethylethanaminium bromide; 2-[{4-[(4,5-dimethyl -1,3-thiazol-2-yl)diazenyl]-3-methylphenyl}(ethyl)-amino]-N,N,N-trimethylethanaminium bromide; 2-[{3-chloro-4-[(4,5-dimethyl-1,3-thiazol-2-yl) diazenyl]phenyl}(ethyl)amino]-N,N,N-trimethylethanaminium bromide; 2-[{4-[(4-methyl -1,3-thiazol-2-yl)diazenyl]phenyl}(ethyl)amino]-N,N,N-trimethylethanaminium bromide;
2-[{4-[(4-methyl-1,3-thiazol-2-yl)diazenyl]-3-methylphenyl}(ethyl)amino]-N,N,N-trimethylethanaminium bromide; 2-[{3-chloro-4-[(4-methyl-1,3-thiazol-2-yl) diazenyl]phenyl}(ethyl)amino]-N,N,N-trimethylethanaminium bromide; 2-[{4-[1,3-benzothiazol-2-yldiazenyl]phenyl}(ethyl)amino]-N,N,N-trimethylethanamminium bromide; 2-(ethyl{4-[(6-nitro-1,3-benzothiazol-2-yl) diazenyl]phenyl}amino)-N,N,N-trimethylethanaminium bromide; 2-[{4-[(5,6-dinitro-1,3-benzothiazol-2-yl)diazenyl]phenyl}(ethyl)amino]-N,N,N-trimethylethanaminium bromide; 2-[{4-[(4,6-dinitro-1,3-benzothiazol-2-yl)diazenyl]phenyl}(ethyl)amino]-N,N,N-trimethylethanaminium bromide; 2-(ethyl{4-[(4-methyl-6-nitro-1,3-benzothiazol-2-yl) diazenyl]phenyl}amino)-N,N,N-trimethylethanaminium bromide; 2-[{4-[(4-chloro-6-nitro-1,3-benzothiazol-2-yl)diazenyl]1-phenyl}(ethyl)amino]-N,N,N-trimethylethanaminium bromide; 2-(ethyl{4-[1H-[1,3]thiazolol[5,4-f]indazol-6-yldiazenyl]phenyl}amino)-N,N,N-trimethylethanaminium bromide;
2-[{4-[(5-chloro[1,3]thiazolo[5,4-b]pyridin-2-yl)diazenyl]phenyl}(ethyl)amino]-N,N,N-trimethylethanaminium bromide; 2-[{4-[(5-methoxy[1,3]thiazolo[5,4-b]pyridin-2-yl) diazenyl]-phenyl}(ethyl )amino]-N,N,N-trimethylethanaminium bromide; N,N-diethyl -2-(ethyl{4-[1,3-thiazol-2-yldiazenyl]phenyl}amino)-N-methylethanaminium bromide;
N-[2-(ethyl{4-[1,3-thiazol-2-yldiazenyl]phenyl}amino)ethyl]-N,N-dimethylbenzenaminium bromide; 2-(ethyl{4-[1,2,4-thiadiazol-5-yldiazenyl]phenyl}amino)-N,N,N-trimethylethanaminium bromide; 2-(ethyl{4-[(3-phenyl -1,2,4-thiadiazol-5-yl)diazenyl]phenyl}amino)-N,N,N-trimethylethanaminium bromide; 2-[{4-[(3-chloro-1,2,4-thiadiazol-5-yl)diazenyl]phenyl}(ethyl)amino]-N,N,N-trimethylethanaminium bromide; 2-(ethyl{4-[1H-1,2,4-triazol-5-yldiazenyl]phenyl}-amino) -N,N,N-trimethylethananhinium bromide; 1-[2-(ethyl{4-[(1-methyl-1H-imidazol-2-yl)diazenyl]-phenyl}amino)ethyl]-N,N,N-trimethylethanaminium bromide;
1-[2-(ethyl{3-methyl-4-[(1-methyl-1H-imidazol-2-yl)diazenyl]phenyl}amino)ethyl]-N,N,N-trimethylethanaminium bromide and 1-{2-[{3-chloro-4-[(1-methyl-1H-imidazol-2-yl)diazenyl]phenyl}(ethyl)amino]ethyl}-N,N,N-trimethylethanaminium bromide.
7. The agent according to claim 1 , wherein the agent comprises from 0.01% to 10% by weight of said cationic azodye of said formula (I).
8. The agent according to claim 1 , further comprising at least one additional direct dye which is selected from the group consisting of nitro dyes, azodyes, anthraquinone dyes, triphenylmethane dyes, and basic or acidic dyes.
9. The agent according to claim 1 , wherein the agent is a hair colorant.
10. The agent according to claim 2 , wherein the agent comprises from 0.01% to 10% by weight of said cationic azodye of said formula (I).
11. The agent according to claim 2 , further comprising at least one additional direct dye which is selected from the group consisting of nitro dyes, azodyes, anthraquinone dyes, triphenylmethane dyes, and basic or acidic dyes.
12. The agent according to claim 2 , wherein the agent is a hair colorant.