MX2007004402A - Colouring agents containing cationic indazoline-thiazolazo dyes- - Google Patents

Abstract

The invention relates to keratin fibre colouring agents containing cationic indazoline-thiazolazo dyes of general formula (I).

Description

COLORING AGENTS CONTAINING CATIÓN DYES OF INDAZOLINA TIAZOLAZO FIELD OF THE INVENTION The present invention relates to certain dyes containing indazoline thiazolazo cationic dyes for keratin fibers, such as hair, wool or fur.

BACKGROUND OF THE INVENTION In general, oxidative dyes produced by the oxidative coupling of one or more developer components with one or more coupling components or direct penetration dyes are used to color keratin-containing fibers. If necessary, direct penetration dyes stable to oxidation can be added to obtain particular color effects. Direct penetration dyes are incorporated into suitable carrier mixtures that are then applied to the fiber. This process generally known as staining is simple to use, particularly benign and is distinguished by causing little damage to the keratin fiber since no ammonia or peroxide is added. However, the dyes used in this process must meet some requirements. They must be toxicologically and dermatologically safe and allow the obtaining of colors of the intensity and brightness desired. In addition, the colors obtained should have adequate resistance to light and also to friction and should be resistant to shampoo or hair care products. Normally it is necessary to use a combination of different non-oxidative dyes in a non-oxidative direct penetration dye for keratin fibers in order to obtain certain shades. There remains a great need for these types of dyes since the amount of dyes that satisfactorily fulfill the mentioned requirements is limited. Another very interesting application of direct penetration dyes is to use them in agents intended to clarify and color simultaneously. In the case of these dyes, which may contain a greater amount of oxidizing agents, the dyes used must fulfill a much greater amount of requirements, in particular with respect to the adequate resistance to the oxidizing agents used. So far, only a few dyes have been identified that meet the above requirements and which at the same time provide satisfactory coloring results. Accordingly, the object of the present invention is to provide direct penetration dyes for coloring keratin fibers, in particular human hair, that meet these requirements. Surprisingly, it has now been found that the indazoline thiazolazo cationic dyes of the general formula (I) can be very easily applied to keratin fibers as direct penetration dyes in color mixtures without adding an oxidizing agent. These dyes can also be used in clarifying dyes containing oxidizing agents, for example, peroxides or persulfates, since they are stable in relation to oxidizing agents.

DESCRIPTION OF THE INVENTION Accordingly, the object of the present invention is to obtain: (a) An agent for the non-oxidative coloring of keratin fibers, in particular human hair; (b) an agent for simultaneously lightening and coloring the keratin fibers containing an oxidizing agent in addition to the dye of the formula (I); and (c) an oxidative dye of keratin fibers based on at least one oxidative dye precursor, wherein agents (a), (b) and (c) are characterized in that each contains at least one indazoline thiazolazo cationic dye. of the general formula (I); wherein: R1 represents a hydrogen atom, an alkylamino group of CrCe, a tert-butyl group, an isopropyl group, an alkyl group of CrC6, an alkyloxy group of CrC6, a hydroxyalkyl group of Ci-C6, an alkylcarboxylic acid group of Ci-C6, an ester group of alkylcarboxylic acid of CrC6, an alkylsulfonic acid group of CrC6 and an ester group of alkylsulfonic acid of CrCe; R2 represents a group of the general formulas (II) to (VI); di) (IV) (V) (i ") R3 represents an alkyl group of CrC6, a hydroxyalkyl group of C2-C4 or a polyhydroxyalkyl group of C4-C6; R4 and R5, independently of each other, are hydrogen, an alkylamino group of C C6, a?,? - dialkylamino group of C Ce, an alkyl cyano group of C C6, a methoxymethyl group, a tert-butyl group, an isopropyl group, an alkyl group of CrC6, an alkyloxy group of C Ce, a hydroxyalkyl group of CrC6, an alkylcarboxylic acid group of C Ce, an alkylcarboxylic acid ester group of Ci-C6, an amide group of alkylcarboxylic acid of Ci-C6l, an alkylsulfonic acid group of C Ce, an ester group of alkylsulfonic acid of C C6, an amide group of alkylsulfonic acid of Ci-C6, a benzyl group or a phenyl group, R6 and R7, independently of each other, are hydrogen, an amino group, an alkylamino group of C C6, a group?,? - C C6 dialkylamino, a N, N- (dihydroxyalkyl) amino group of CrC6, a halogen atom (fluorine, chlorine, brom oo iodo), a cyano group, an alkyl cyano group of C Ce, a methoxymethyl group, a tert-butyl group, an isopropyl group, an alkyl group of C Ce, an alkyloxy group of C & C, a hydroxyalkyl group of C C6, a hydroxyalkyloxy group of C Ce, an alkylcarboxylic acid group of Ci-C6, an ester group of C1-C6 alkylcarboxylic acid, an alkylcarboxylic acid amide group of C Ce, an alkylsulfonic acid group of CrC6, an ester group of Ci-C6 alkylsulfonic acid, an alkylsulfonic acid amide group of CrC6, a phenyl group or a sulfonic acid group; R8 is hydrogen, an alkylamino group of C ^ Ce, a?,? - dialkylamino group of Ci-C6, an alkyl cyano group of CrCe, a methoxymethyl group, a tert-butyl group, an isopropyl group, an alkyl group of CrC6 , an alkyloxy group of CrCe, a hydroxyalkyl group of C] -C6, an alkylcarboxylic acid group of C ^ Ce, an ester group of C6 alkylcarboxylic acid, an amide group of Ci-C6 alkylcarboxylic acid, an alkylsulfonic acid group of C Ce, an alkylsulfonic acid ester group of C Ce, an alkylsulfonic acid group of C C6 or a phenyl group; R9 is a hydrogen atom, an amino group, an alkylamino group of Ci-C6) a?,? - dialkylamino group of C C6, an alkyl cyano group of C ^ C6, a hydroxyl group, a nitro group, a methoxymethyl group , a tert-butyl group, an isopropyl group, an Ci-C6 alkyl group, a C6 alkyloxy group, a hydroxy alkyl group of CrC6, an alkylcarboxylic acid group of C Ce, an ester alkylcarboxylic acid group of C Ce, an alkylsulfonic acid group of Ci-C6, an ester group of alkylsulfonic acid of C ^ Ce or a carboxylic acid group (-COOH); wherein the alkyl groups may be branched or linear, R 'represents hydrogen or a nitro group; Hal indicates a hydrogen atom or a halogen atom (F, Br, Cl, I), especially in the case of a bromine or chlorine atom; and X "represents an anion, preferably a sulfate anion, a phosphate anion, an acid phosphate anion, an oxalate anion, a formate anion, an acetate anion, a citrate anion, a tartrate anion, a malonate anion, a pyruvate anion, an iodide anion, a chloride anion, a bromide anion or a methyl sulfate anion, wherein chloride anion, bromide anion and methyl sulfate anion are especially preferred The following dyes may be mentioned as suitable cationic direct dyes of the general formula (I): 6- methylsulfate. { (£) - [4- (dimethylamino) phenyl] diazenyl} -7-methyl-1 H- [1, 3] thiazolo [5,4-] indazol-7- io, 7-methyl-6- methylsulfate. { (£) - [4- (methylamino) phenyl] diazenil} -1 H- [1, 3] thiazolo [5,4 - /] - indazol-7- ¡o, 6- methylsulfate. { (£) - [4- (ethylamino) phenyl] diazenyl} -7-methyl-1 H- [1, 3] thiazolo [5,4-) -indazol-7 6- methylsulfate. { (£) - [4- (diethylamino) phenyl] diazenl} -7-methyl-1, 3] táazolo [5,4-] -ndazol-7- ¡o, 6 - ((£) -. {4 - [(2-hydroxyethyl) amino] phenyl] diazenyl) -7-methyl-1,3] thiazolo [5,4-] indazol-7-io-methylsulfate, 6 - ((£) -. {4- [bis (2-hydroxyethyl) amino] phenyl] diazyl) -7-methyl-1 H- [1, 3] thiazolo methyl sulfate [5,4- /] indazol-7-io, 2-hydroxyethyl methylsulfate. { 4 - [(£) - (7-methyl-1 H- [1,3] thiazolo [5,4-flindazol-7-io-6-yl] diazenyl] phenyl} cyanamide, 6 - ((E) -. {4- [bis (2-hydroxyethyl) (methyl) amino] phenyl] diazenyl) -7-methyl-1 H- [1, 3] thiazol methyl ester [5,4 - /] ndazol-7-io, 6 - ((£) -. {4- [ethyl (2-hydroxyethyl) amino] phenyl] diazenyl) -7-methyl-1,3] thiazolo [5.4-] indazole-7-io methyl sulfate , 6- { (£) - [4- (dimethylamino) phenyl] diazenyl} -1, 7-dimethyl-1 H- [1, 3] thiazolo [5,4- 6- methylsulfate. { (£) - [4- (dimethylamino) phenyl] d aazenyl} -1- (2-hydroxyethyl) -7-methyl-1 H- [1,3] thiazolo [5,4 - /] indazol-7-p, 6- methylsulfate. { (£) - [4- (diethylamino) phenyl] diazenil} -1- (2-hydroxyethyl) -7-methyl-1 H- [1,3] thiazolo [5,4- / | indazol-7-io, 6 - ((£) -. {4- [bis (2-hydroxyethyl) amino] phenyl] diazenyl) -1 - (2-hydroxyethyl) -7-methyl-1 H- methyl ester] [1,3] thiazolo [5,4 - /] indazol-7-io, 6 - ((£) -. {4- [bis (2-hydroxyethyl) amino] phenyl] diazyl) -1,7-dimethyl-1 H- [1,3] thiazolo methyl ester [5, 4- | indazol-7-io, or "\? ' or 6 - [(£) - (4-hydroxyphenyl) diazenyl] -1,7-dimethyl-1 H- [1. Sthiazolo] -flindazole, 6 - [(£) - (4-hydroxyphenyl) diazenyl] -7-methyl-1 H - [3] thiazolo [5,4-] indazol-7-io methylsulfate, 6 - [(£) - (4-methoxyphenyl) diazenyl] -7-methyl-1, 3] thiazolo [5,4-] indazol-7-io methylsulfate, 6 - [(£) - (4-methoxyphenyl) diazenyl] -1,7-dimethyl-1 H- [1,3] thiazolo [5,4-] indazol-7-io methylsulfate, 6 - [(£) - (3,4-dimethoxyphenyl) d, azole] -1, 7-dimethyl-1 H- [1,3] thiazolo [5,4-] -indazole-7-methyl ester; or, 6 - [(£) - (3,4-dimethoxyphenyl) diazenyl] -7-methyl-1 H- [1,3] thiazolo [5,4-] indazol-7-yl methylsulfate. Particularly preferred compounds of the general formula (I) are: 6- methylsulfate. { (£) - [4- (dimethylamino) phenyl] diazenyl} -7-methyl-1 H- [1, 3] thiazolo [5,4-indazol-7- io, 7-methyl-6-methylsulfate. { (£) - [4- (methylamino) phenyl] -diazenil} -1 H- [1, 3] t azolo [5,4-indazole-7-o, 6- methylsulfate. { (£) - [4- (ethylamino) phenyl] -diazenil} -7-methyl-1 H- [1, 3] t azolo [5,4-] indazole-7-io, 6- methylsulfate. { (£) - [4- (diethylamino) phenyl] diazenil} -7-methyl-1 H- [1, 3] thiazolo [5,4 - /] - indazol-7-io, 6 - ((£) -. {4 - [(2-hydroxyethyl) methylsulfate) -amino] phenyl.}. -diazenyl) -7-methyl-1 H- [1,3] thiazolo [5,4-] indazol-7-yl 6 - ((£) -. bis (2-hydroxyethyl) amino] phenyl] diazinyl) -7-methyl-1 H- [1,3] thiazolo [5.4 - /] indazol-7-io, 2-hydroxyethyl methylsulfate. { 4 - [(£) - (7-methy1-H- [1, 3] thiazolo [5,4 - /] indazol-7-io-6-yl) diazene] phenyl} cyanamide, 6 - ((£) -. {4 - [(2-hydroxyethyl) (methyl) amino] phenyl} diazenyl) -7-methyl-1 H- [1, 3] thiazolo methyl sulfate 5,4-f] indazol-7-io and 6 - ((£) -. {4- [ethyl (2-hydroxyethyl) amino] phenyl] diazenyl) -7-methyl-1 H- \ methyl ester , 3] thiazolo [5,4-] indazol-7-io. The dye derivatives of the general formula (I) according to the present invention are obtained from commercially available components or which can be produced easily by means of standard operations (Tarabasanu-mihaila, C. et al., Revue Roumaine de Chimie, 1973, 18 (5), 889-898). Accordingly, the indazoline thiazolazo dyes of the formula (I) can be produced, for example, by means of a two-step synthetic process in which, in a first step, the thiazolazo indazoline compounds of the formula (Ia) can produced with activated aromatics through the azo coupling of 2-aminoindazole thiazoline (eg, 2-amino-thiazolo [4,5-f] indazole) (Diagram 1); and then in a second step, the indazoline thiazolazo cationic dyes of the corresponding formula (la) can be obtained by converting the compounds of the formula (la) with suitable alkylating agents (for example, DMS = dimethylsulfate) (Diagram 2).

Diagram 1: (the) Diagram 2: The dyes according to the present invention containing the indazoline thiazolazo cationic dyes of the general formula (I) make it possible to obtain a uniform coloration of the keratin fibers, particularly human hair, with adequate stability against light, sweat and washing with shampoo, where bright and intense colors are maintained when the conditions are not aggressive. The indazoline thiazolazo cationic dyes of the general formula (I) are present in the dyes according to the present invention preferably in a total amount of 0.01 to 10 weight percent, but in particular from 0.1 to 8 weight percent. The dye according to the present invention (a) may contain, in addition to the dyes of the general formula (I), other known direct dye dyes, alone or mixed together, from the group consisting of nitro dyes, azo dyes, anthraquinone dyes , and triphenylmethane dyes, such as, for example, 1,4-bis [(2-hydroxyethyl) amino] -2-nitrobenzene, 1- (2-hydroxyethyl) amino-2-nitro-4- [di (2-hydroxyethyl) amino] ] -benzene, (HC blue No. 2), 1-amino-3-methyl-4 - [(2-hydroxyethyl) amino] -6-nitrobenzene, (HC violet No. 1), 4- [ethyl] -hydrochloride (2-hydroxyethyl) amino] -1 - [(2-hydroxyethyl) amino] -2-nitrobenzene (HC blue No. 12), 1 - [(2,3-dihydroxypropyl) amino] -4- [methyl- (2 -hydroxyethyl) amino] -2-nitrobenzene (HC blue No. 10), 1 - [(2,3-dihydroxy-propyl) amino] -4- [ethyl- (2-hydroxyethyl) amino] -2-nitrobenzene hydrochloride (HC blue No. 9), 1- (3-hydroxypropylamino) -4- [di (2-hydroxyethyl) amino] -2-nitrobenzene, (HC violet No. 2); 1-amino-4 - [(2-hydroxyethyl) amino] -2-nitrobenzene (red HC # 7), 2-amino-4,6-dinitrophenol, 1,4-diamino-2- nitrobenzene (CI76070), 4-amino-2-nitrodiphenylamine (red HC # 1), 1-amino-4- [di (2-hydroxyethyl) amino] -2-nitrobenzene hydrochloride (red HC # 13), 1 -amino-5-chloro-4 - [(2-hydroxyethyl) amino] -2-nitrobenzene, 4-amino-1 - [(2-hydroxyethyl) amino] -2-nitrobenzene (red HC # 3), 4- amino-2-nitro-1 - ((prop-2-en-1-yl) amino) -benzene, 4-amino-3-nitrophenol, 4 - [(2-hydroxyethyl) amino] -3-nitrophenol, 4- [(2-nitrophenyl) amino] phenol (orange HC # 1), 1 - [(2-amino-ethyl) amino] -4- (2-hydroxyethoxy) -2-nitrobenzene (orange HC # 2), 4 - (2,3-dihydroxypropoxy) -1 - [(2-hydroxyethyl) amino] -2-nitrobenzene, (orange HC # 3), 1-amino-5-chloro-4 - [(2,3-dihydroxypropyl) amino] -2-nitrobenzene (red HC # 10), 5-chloro-1, 4- [di (2,3-dihydroxypropyl) amino] -2-nitrobenzene (red HC # 1 1), 2 - [( 2-hydroxyethyl) amino] -4,6-dinitrophenol, 4-ethylamino-3-nitro benzoic acid, 2 - [(4-amin o-2-nitrophenyl) amino] -benzoic acid, 2-chloro-6-ethylamino-4-nitrophenol, 2-amino-6-chloro-4-nitrophenol, 4 - [(3-hydroxy-propyl) amino] - 3-nitrophenol, 2,5-diamino-6-nitropyridine, 3-amino-6- (methylamino) -2-nitropyridine, 1, 2,3,4-tetrahydro-6-nitroquinoxaline, 7-amino-3,4- dihydro-6-nitro-2H-1,4-benzoxazine (HC red no. 14), 1,2-diamino-4-nitrobenzene (CI76020), 1-amino-2 - [(2-hydroxyethyl) amino] -5-nitrobenzene (yellow HC No. 5), 1- (2-hydroxyethoxy) - 2 - [(2-hydroxyethyl) amino] -5-nitrobenzene, (yellow HC # 4), 1 - [(2-hydroxyethyl) amino] -2-nitrobenzene (yellow HC # 2), 2 - [(2 -hydroxyethyl) amino] -1-methoxy-5-nitrobenzene, 2-amino-3-nitrophenol, 1-amino-2-methyl-6-nitrobenzene, 1- (2-hydroxyethoxy) -3-methylamino-4-nitrobenzene, 2,3- (dihydroxypropoxy) -3-methylamino-4-nitrobenzene, 2- [(2-Hydroxyethyl) amino] -5-nitrophenol (yellow HC # 11), 3 - [(2-aminoethyl) amino] -1-methoxy-4-nitrobenzene hydrochloride, (yellow HC no. 9), 1 - [(2-ureidoethyl) amino] -4-nitrobenzene, 4 - [(2,3-dihydroxypropyl) -amino] -3-nitro-1-trifluoromethyl benzene, (yellow HC # 6), 1 -chloro-2,4-bis [(2-hydroxyethyl) amino] -5-nitrobenzene (yellow HC # 10), 4 - [(2-hydroxyethyl) -amino] -3-nitro-1-methyl benzene, 1 -chloro-4 - [(2-hydroxyethyl) amino] -3-nitrobenzene (yellow HC no. 12), 4 - [(2-hydroxyethyl) amino] -3-nitro-1-trifluoromethyl benzene, (yellow HC no. 13), 4 - [(2-hydroxyethyl) amino] -3-n-benzonitrile (yellow HC no. 14), 4 - [(2-hydroxyethyl) amino] -3-nitro benzamide (yellow HC no. 15), 2,4-dinitro-1-hydroxy naphthalene, 1,4-di [(2,3-dihydroxy-propyl) amino] -9,10-anthraquinone, 1,4-di [(2-hydroxyethyl)] amino] -9,10-anthraquinone (CI61545, Dispersed Blue 23), 1-amino-4-hydroxy-9,10-anthraquinone (CI60710, Dispersed Red 15), 1-hydroxy-4 - [(4-methyl-2 -sulfophenyl) amino] -9,10-anthraquinone, 7-beta-D-glucopyranosyl-9,10-dihydro-1-methyl-9,10-dioxo-3,5,6,8-tetrahydroxy-2-anthracene acid carboxylic acid (CI75470, Natural red 4), 1 - [(3-aminopropyl) amino] -9,10-anthraquinone (red HC # 8), 1,4-diamino-9,10-anthraquinone (CI61100, Violet dispersed no. 1), 1-amino-4- (methylamino) -9,10-anthraquinone (CI61105, Dispersed Violet No. 4, Solvent Violet No. 12), N- (6 - ((3-chloro-4- (methylamino) ) phenol) imino) -4-methyl-3-oxo-1,4-cyclohexadiene-1-yl) urea (red HC # 9), 2 - ((4- (di (2-hydroxyethyl) amino) phenyl) amino) -5 - ((2-hydroxyethyl) amino) -2,5-cyclohexadien o-1, 4-dione (green HC no. 1), 2-hydroxy-1,4-naphthoquinone (CI75480, natural Orange number 6), 1,2-dihydro-2- (1,3-dihydro-3-oxo-2H-indol-2-ylidene) - 3H-indol-3-one (CI73000), 1,3-bis (dicyanomethylene) indan, di [4- (diethylamino) phenyl] [4- (ethylamino) naphthyl] carbenium chloride (CI42595; Basic blue No. 7) , di [4- (dimethylamino) phenyl] [4- (phenylamino) naphthyl] -carbenium chloride (CI44045; Basic blue No. 26), Basic blue no. 77, 8-amino-2-bromo-5-hydroxy-4-imino-6 - [(3- (trimethylammonium) phenyl) amino] -1 (4H) -naphthalenone chloride (CI56059; Basic blue No. 99), tri (4-amino-3-methylphenyl) carbenium chloride (CI42520; Basic violet No. 2), di (4-aminophenyl) (4-amino-3-methylphenyl) carbenium chloride (CI42510; Basic violet No. 14) , 1 - [(4-aminophenyl) azo] -7- (trimethylammonium) -2-naphthol chloride (CU 2250; Basic brown No. 16), 3 - [(4-amino-2,5-dimethoxyphenyl) chloride] -azo] -N, N, N-trimethylbenzene aminium (CU 12605, basic Orange No. 69), 1 - [(4-amino-2-nitrophenyl) azo] -7- (trimethylammonium) -2-naphthol chloride ( Basic brown No. 17), 1 - [(4-amino-3-nitrophenyl) azo] -7- (trimethylammonium) -2-naphthol chloride (CU 2251; Basic brown No. 17), 2 - (( 4-aminophenyl) azo) -1, 3-dimethyl-1 H-imidazol-3-io (basic orange No. 31), 3,7-diamino-2,8-dimethyl-5-phenylphenazinium chloride (CI50240; basic No. 2), 1,4-dimethyl-5 - [(4- (dimethylamine) phenyl) azo] -1,4,4-triazolium chloride (CU 1055; basic No. 22), 1,3-dimethyl-2 - ((4-dimethylamino) phenyl) azo-1 H-imidazol-3-io chloride (Basic red no. 51), 2-hydroxy-1 - [(2-methoxyphenyl) azo] -7- (trimethylammonio) naphthalene chloride (CU 2245; Basic red No. 76), 3-methyl-1-phenyl-4- chloride [] (3- (trimethylammonium) phenyl) azo] -pyrazol-5-one (CU 2719; Basic Yellow No. 57), 1-methyl-4 - ((methyl-phenyl-hydrazono) methyl) pyridinium methylsulfate (Basic yellow no. 87), 1- (2-morpholinium propylamino) -4-hydroxy-9, 10-anthraquinone methyl sulfate, 1 - [(3- (dimethyl-propylamino) propyl) amino] -4- (methylamino) -methyl chloride 9,10-anthraquinone, 1- [Di (2-hydroxyethyl) amino] -3-methyl-4 - [(4-nitrophenyl) -azojbenzene (CU 1210, Dispersed Red No. 17), 1- [di ( 2-hydroxyethyl) amino] -4 - [(4-nitrophenyl) azo] benzene, (Dispersed Black No. 9), 4 - [(4-aminophenyl) azo] -1- [di (2-hydroxyethyl) amino] - 3-methylbenzene, (yellow HC # 7), 2,6-diamino-3 - [(pyridin-3-yl) azo] pyridine and 2 - ((4- (ethyl (2-hydroxyethyl) -amino) -2 -methylphenyl) azo) -5-nitro-1,3-thiazole (CU 1 1935; Dispersed Blue No. 106). The dye (b) according to the present invention, which differs by the content comprises an oxidizing agent, preferably hydrogen peroxide or its addition compounds with urea, melmin, sodium borate or sodium carbonate, and may also contain, in addition to the dyes of the general formula, other oxidation-stable direct dye dyes, for example, 3- (2 ', 6'-diaminopyridyl-3'-azo) pyridine (= 2,6-diamino-3 - ((pyridin-3-yl) azo) pyridine, 2 - ((4- (ethyl (2-hydroxyethyl) -amino) -2-methylphenyl) azo-5-nitro-1,3-thiazole (Dispersed blue 106), N, N-di (2-hydroxyethyl) -3 -methyl-4 - ((4-nitrophenyl) azo) aniline (Dispersed Red 17, Cl 1 1210), 3-diethylamino-7- (4-dimethylaminophenylazo) -5-phenyl-phenazinium chloride (Cl 1 1050), salt Sodium 4- (2-thiazolylazo) resorcinol, 4 - (((4-phenylamino) azo) benzosulfonic acid (Orange IV), 1 - ((3-aminopropyl) amino) -9,10-anthracenedione (red HC no. 8), 3 ') 3", 4,5,5', 5", 6,7-octabromo phenol sulfonphthalein (Tetrabromfenol blue), 1 - ((4-amino-3,5-dimethylphenyl) - ( 2,6-dichlorophenol) -methylene) -3,5-d-rrn-l-4-imino-2,5-cyclohexadine phosphoric acid (1: 1) (basic Blue 77), 3 ', 3", 5', disodium salt, 5"-tetrabromo-m-cresolsulfonphthalein, 2,4-dinitro-1-naphthol-7-sulfonic acid (acid yellow 1, Cl 10316), sodium salt of 4- [2'-hydroxy-1'-naphthyl) azo] benzosulfonic acid (Orange acid 7, Cl 15510), disodium salt of 3 ', 6'-dihydroxy-2', 4 ', 5', 7'-tetraiodospiro- [isobenzo-furan-1 (3H), 9 '(9H) -xanten] -3-one (Acid red 51, Cl 45430), 6-hydroxy-5 - ((2-methoxy-5-methyl-4-sulfophenyl) azo) -2-naphthalene sulphonic acid disodium salt (FD &; Red C 40, Cl 16035), sodium salt of 2,4-dinitro-1-naphthol (acid yellow 24; Cl 10315), disodium salt of 2 ', 4', 5 ', 7'-tetrabromo-4,5 , 6,7-tetrachloro-3 ', 6'-dihydroxy-spiro (isobenzofuran-1 (3H), 9' [9H] xanten] -3-one (Acid red 92; Cl 45410), sodium salt of 4-acid (2-hydroxy-1-naphthylazo) -3-methylbenzenesulfonic acid (Orange acid 8, Cl 15575), 2-amino-1,4-naphthalenedione, dithizone (1,5-diphenylthiocarbazone), N- (2-hydroxyethyl)) -2-nitro-4-trifluoromethyl) aniline (Yellow HC 13), N- (2-hydroxyethyl) -4-nitro-aniline and 4-chloro-N- (2,3-dihydroxypropyl) -2-nitroaniline. The direct penetration dyes mentioned above may be present in a total amount of about 0.01 to 4 weight percent, wherein the total dye content in the dye according to the present invention is preferably from about 0.01 to 10 percent. by weight, in particular from 0.1 to 5 weight percent. The oxidation dye (c) according to the present invention which is mixed with an oxidizing agent (in particular hydrogen peroxide or addition compounds thereof) -alternatively, oxidation can also be produced by means of atmospheric oxygen, with the use of suitable enzymes as needed - contains additional oxidative dye precursors, in addition to the dyes of the general formula (I). The following developer substances and coupling substances and also the self-coupling compounds, for example, can be mentioned as suitable oxidative dye precursors (i) Developer substances: 1,4-diamino benzene (p-phenylenediamine), 1, 4-diamino-2-methylbenzene (p-toluylenediamine), 1,4-diamino-2,6-xylene, 1,4-diamino-3,5-diethylbenzene, 1,4-diamino-2,5-xylene, 1 , 4-diamino-2,3-xylene, 2-chloro-1,4-diaminobenzene, 1, 4-diamino-2- (thiophen-2-yl) benzene, 1,4-diamino-2- (thiophen-3-yl) benzene, 1,4-diamino-2- (pyridin-3-yl) benzene , 2,5-diamino biphenyl, 1,4-diamino-2-methoxymethyl benzene, 1,4-diamino-2-aminomethyl benzene, 1,4-diamino-2-hydroxymethyl benzene, 1,4-diamino-2- ( 2-hydroxyethoxy) benzene, 2- (2- (acetylamino) ethoxy) -1,4-diamino benzene, 4-phenylaminoaniline, 4-dimethylaminoaniline, 4-diethylaminoaniline, 4-dipropylaminoaniline, 4- [ethyl (2 -hydroxyethyl) -amino] aniline, 4- [di (2-hydroxyethyl) amino] aniline, 4- [di (2-hydroxyethyl) amino] -2-methylaniline, 4 - [(2-methoxyethyl) amino] aniline, 4 - [(3-hydroxypropyl) amino] aniline, 4 - [(2,3-dihydroxypropyl) amino] aniline, 1,4-diamino-2- (2-hydroxyethyl) benzene, 1,4-d-amino-2- (1-Methylethyl) benzene, 1,3-bis [(4-aminophenyl) (2-hydroxyethyl) amino] -2-propanol, 1,4-bis [(4-aminophenyl) amino] butane, 1,8-bis (2,5-diaminophenoxy) -3,6-dioxaoctane, 4-aminophenol, 4-amino-3-methylphenol, 4-amino-3- (hydroxymethyl) phenol, 4-amino-3-fluorophenol, 4-methylaminophenol, 4 -amino-2- (aminomethyl) phenol, 4-a Mino-2- (hydroxymethyl) phenol, 4-amino-2-fluorophenol, 4-amino-2 - [(2-hydroxyethyl) -amino] methylphenol, 4-amino-2-methylphenol, 4-amino-2- (methoxymethyl) ) phenol, 4-amino-2- (2-hydroxyethyl) phenol, 5-amino salicylic acid, 2,5-diamino pyridine, 2,4,5,6-tetraamino pyrimidine, 2,5,6-triamino-4- (1 H) -pyrimidone, 4,5-diamino-1- (2-hydroxyethyl) -1 H-pyrazole, 4,5-diamino-1- (1-methyl-ethyl) -1 H-pyrazole, 4,5-diamino -1 - [(4-methylphenyl) -methyl] -1 H-pyrazole, 1 - [(4-chlorophenyl) methyl] -4,5-diamino-1 H-pyrazole, 4,5-diamino-1-methyl- 1 H-pyrazole, 2-aminophenol, 2-amino-6-methylphenol, 2-amino-5-methylphenol, alone or mixed together. (I) Coupling substances: N- (3-dimethylamphenyl) urea, 2,6-diaminopyridine, 2-amino-4 - [(2-hydroxyethyl) amino] anisole, 2,4-diamino -1-Fluoro-5-methylbenzene, 2,4-diamino-1-methoxy-5-methylbenzene, 2,4-diamino-1-ethoxy-5-methylbenzene, 2,4-diamino-1 - (2-hydroxyethoxy) -5-methylbenzene, 2,4-di [(2-hydroxyethyl) amino] -1,5-dimethoxybenzene, 2,3-diamino-6-methoxypyridine, 3-amino-6-methoxy-2- (methylamino) pyridine, 2,6-diamino-3,5-dimethoxypyridine, 3,5-diamino-2,6-dimethoxypyridine, 1,3-diaminobenzene, 2,4-diamino-1- (2-hydroxyethoxy) benzene, 1,3-diamino-4- (2,3-dihydroxypropoxy) benzene, 2,4-diamino-1,5-di (2-hydroxyethoxy) benzene, 1 - (2-aminoethoxy) -2,4-diaminobenzene, 2-amino-1- (2-hydroxyethoxy) -4-methylaminobenzene, 2,4-diaminophenoxy acetic acid, 3- [di (2-hydroxyethyl) amino] aniline , 4-amino-2-di [(2-hydroxyethyl) amino] -1-ethoxybenzene, 5-methyl-2- (1-methylethyl) phenol, 3 - [(2-hydroxyethyl) amino] aniline, 3 - [( 2-aminoethyl) -amino] aniline, 1,3-di (2,4-diaminophenoxy) propane, di (2,4-diamino phenoxy) methane, 1,3-diamino-2,4-dimethoxybenzene, 2,6- bis (2-hydroxyethyl) aminotoluene, 4-hydroxyindole, 3-dimethylaminophenol, 3-diethylaminophenol, 5-amino-2-methylphenol, 5-amino-4-fluoro-2-methylphenol, 5-amino-4-methoxy-2- methylphenol, 5-amino-4-ethoxy-2-methylphenol, 3-amino-2,4-dichlorophenol, 5-amino-2,4-dichlorophenol, 3-amino-2-methylphenol, 3-amino-2-chloro- 6-methylphenol, 3-aminophenol, 2 - [(3-hydroxyphenyl) amino] acetamide, - [(2-hydroxyethyl) amino] -4-methoxy-2-methylphenol, 5 - [(2-hydroxyethyl) amino] -2-methylphenol, 3 - [(2-hydroxyethyl) amino] phenol, 3 - [( 2-methoxyethyl) amino] phenol, 5-amino-2-ethylphenol, 5-amino-2-methoxyphenol, 2- (4-amino-2-hydroxyphenoxy) ethanol, 5 - [(3-hydroxypropyl) amino] -2- methylphenol, 3 - [(2,3-dihydroxypropyl) amino] -2-methylphenol, 3 - [(2-hydroxyethyl) -amino] -2-methylphenol, 2-amino-3-hydroxypyridine, 5-amino-4-chloro -2-methylphenol, 1-naphthol, 2-methyl-1-naphthol, 1,5-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2-methyl-1-naphthyl acetate, 1,3-dihydroxybenzene, 1-chloro-2,4-dihydroxybenzene, 2-chloro-1,3-dihydroxybenzene, 1,2-dichloro-3,5-dihydroxy-4-methylbenzene, 1,5-dichloro-2, 4-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene, 3,4-methylenedioxyphenol, 3,4-methylenedioxyaniline, 5 - [(2-hydroxyethyl) amino] -1,3-benzodioxole, 6-bromo-1-hydroxy -3,4-methylenedioxybenzene, 3,4-diamino benzoic acid, 3,4-dihydro-6-hydroxy-1,4 (2H) -benzoxazine, 6-amino-3,4-dihydro-1,4 (2H) -benzoxa zina, 3-methyl-1-phenyl-5-pyrazolone, 5,6-dihydroxyindole, 5,6-dihydroxyindoline, 5-hydroxyindole, 6-hydroxyindole, 7-hydroxyindole, 2,3-indoline dione, alone or in combination with each other. (iii) Self-coupling compounds: 2-amino-5-methylphenol, 2-amino-6-methylphenol, 2-amino-5-ethoxyphenol or 2-propylamino-5-aminopyridine. The total amount of the oxidative dye precursors contained in the dye (c) according to the present invention is from about 0.01 to 12 weight percent, in particular from about 0.2 to 6 weight percent. The dye (a), (b) or (c) according to the present invention can also contain all the traditional additives known for these types of preparations, for example, essential oils, chelating agents, waxes, preservatives, thickeners, antioxidants, alginates, guar gum, hair conditioning substances, for example, cationic polymers or lanolin derivatives, or anionic, nonionic, amphoteric or cationic surfactants. Preferably, the following are used: amphoteric or non-ionic surfactants, for example betaine surfactants, propionates and glycinates, such as cocoanfoglycinates or cocoanfodiglycinates, surfactants ethoxylated with 1 to 1000 ethylene oxide units, preferably with 1 to 300 oxide units of ethylene, such as glyceride alkoxylates, for example, with 25 ethylene oxide units of an ethoxylated castor oil, polyglycol amides, ethoxylated alcohols and ethoxylated fatty alcohols (fatty alcohol oxylates) and also esters of fatty acids with ethoxylated sugars, in particular, esters of fatty acids with ethoxylated sorbitan. The components mentioned above are used in the usual amounts for these purposes, for example, surfactants are used at a concentration of 0.1 to 30 weight percent and conditioning agents at a concentration of 0.1 to 5 weight percent. The dye (a), (b) or (c) according to the present invention, particularly if it is a hair colorant, can be present in the form of a powder or granulate which is dissolved in an aqueous preparation or alcohol- aqueous before the application, or in the form of an aqueous or alcohol-aqueous solution, a cream, a gel, an emulsion or an aerosol foam, wherein the hair colorant can be manufactured in series in the form of a preparation of a single component or in the form of a multi-component composition, for example, with which the specific dye derivatives of the general formulas (I) and (II) are packaged separately from the other components, and the hair colorant Ready to use is not formed by mixing the two components until immediately before use. The dye (a), (b) or (c) according to the present invention usually has a pH of about 2 to 11, preferably about 5 to 10, and in particular a neutral to basic pH value of about 7. to 10. To obtain the pH value according to the present invention, any organic or inorganic acid can be used. In particular, the following acids can be mentioned as the suitable acids: α-hydroxycarboxylic acids, such as glycolic acid, lactic acid, tartaric acid, citric acid or malic acid, ascorbic acid, gluconic acid lactone, acetic acid, hydrochloric acid or phosphoric acid , and also mixtures of these acids. The following bases can be mentioned, in particular, as the suitable bases: sodium carbonate, sodium bicarbonate, alkanolamines, for example, monoethanolamine or triethanolamine, ammonia, aminomethylpropanol and sodium hydroxide, and also mixtures thereof. Depending on the specific application envisaged, the dye according to the present invention can be used with one or more oxidizing agents (oxidative dye, clarifying agent) or without an oxidizing agent (non-oxidative dye). The colorant according to the present invention is normally used by applying to the hair an amount of colorant sufficient to color the hair, wherein that amount is about 30 to 120 grams (1.05 ounce to 4.23 ounces) based on the length of the hair, such that the dye acts on the hair at about 15 ° C to 45 ° C (59 ° F) at 1 13 ° F) for about 1 to 60 minutes, preferably 5 to 30 minutes, thoroughly rinsing the hair with water, and if necessary, washing it with shampoo and / or treating it with a hair conditioner and then drying it. If necessary, the agent is mixed with an oxidizing agent before application. As long as an oxidizing agent is not added to the color mixture, the dye described above may also contain natural or synthetic polymers commonly used for cosmetic agents or modified natural polymers, by means of which hair coloring occurs at the same time. time is fortified. These agents are generally characterized as staining or color enhancers. In industry it is known to use the following synthetic polymers for the above purpose: polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol or polyacrylic compounds such as polyacrylic acid or polymethacrylic acid, basic polymers of polyacrylic acid esters, polymethylacrylic acid, and alkanolamines, example, salts of these or quaternization products, polyacrylic nitrile, polyvinyl acetates, and also copolymers of these types of compounds, for example, polyvinyl pyrrolidone vinylacetate; while, for example, chitosan (deacetylated chitin) or chitosan derivatives can be used as natural polymers or modified natural polymers. The polymers mentioned above may be present in the dye (a) according to the present invention in the usual amounts for those agents, in particular, in an amount of about 1 to 5 weight percent. The pH value of the dye or color fortifier according to the present invention is preferably from about 6 to 9. The hair dye with the additional fortifier is applied in the known and customary manner by moistening the hair with the fortifier and then modeling the hair. hair in the desired way and finally, drying it. The dyes (a), (b) and (c) allow the uniform, intensive and permanent coloring of keratin fibers (for example, human hair, wool or fur) without significantly coloring the skin or the scalp, where this coloration hard, when using the dye (a), five or more hair washes without loss of color is perceived. The following examples are included to extend the explanation of the object of the present invention without limiting the invention to these examples.

Examples Example 1: Hair dye without oxidizing agent 2. 5 mmol of dye of the general formula (I) 5.0 g (0.17 oz) of ethanol 4.0 g (0.14 oz) of decyl polyglucose 0.2 g (0.007 oz) of disodium salt hydrate of ethylenediaminetetraacetic acid cbp 100.0 g (3.527 oz) of water, completely desalinated The color solution is adjusted to a pH value of 7 to 10 by the addition of ammonia.

The hair is colored by applying to the hair an amount of colorant sufficient to color it. After an application time of 30 minutes at 40 ° C (104 ° F), the hair is rinsed with warm water and dried. The results of the coloring are included in the following Table 1.

Table 1 Example 2: Hair dye to clarify and color simultaneously (with oxidizing agent) 2. 5 mm methylsulfate 6-. { (£) - [4- (dimethylamino) phenyl] diazenyl} - mol 7-methyl-1 H- [1.3] thiazolo [5,4-f] indazol-7-io 5.0 g ethanol 4.0 g of decyl polyglucose 0.2 g ethylenediaminetetraacetic acid disodium salt hydrate ad 100.0 water, completely distilled 9 50 g of the above coloring solution are mixed with 50 g of an emulsion with 6% hydrogen peroxide in a homogeneous compound immediately before application. A sufficient amount of hair is applied to the hair. After an application time of 45 minutes at a temperature of 40 ° C (104 ° F), the hair is rinsed with warm water and treated with acidic conditioner, rinsed again and dried. A grayish blue color is obtained. All percentage specifications in the present application represent percentages by weight unless otherwise indicated.

Claims (10)

1 . An agent for the non-oxidative coloring of keratin fibers characterized in that it contains at least one indazoline thiazolazo cationic dye of the general formula (I), characterized in that ) R1 represents a hydrogen atom, an alkylamino group of Ci-C6, a tert-butyl group, an isopropyl group, an alkyl group of Ci-C6, an alkyloxy group of CrC6, a hydroxyalkyl group of C6, an alkylcarboxylic acid group of C C6, an ester group of alkylcarboxylic acid of C C6, an alkylsulfonic acid group of C Ce and an ester group of alkylsulfonic acid of Ci-C¿, R2 represents a group of the general formulas (II) to (VI); R3 represents an alkyl group of CrC6, a hydroxyalkyl group of C2-C4 or a polyhydroxyalkyl group of C4-C6; R4 and R5, independently of one another, are hydrogen, an alkylamino group of C-C6, a?,?-Dialkylamino group of Ci-C6, an alkyl cyano group of CrC6, a methoxymethyl group, a tert-butyl group, a group isopropyl, an alkyl group of CrC6, an alkyloxy group of C, - ^, a hydroxyalkyl group of (- C6, an alkylcarboxylic acid group of C 1 -L 6, an ester group of alkylcarboxylic acid of CrC 6, an acid amide group (C6) alkylcarboxylic acid group of C C6, an alkylsulfonic acid ester group of C Ce, an alkylsulfonic acid amide group of CrC6, a benzyl group or a phenyl group, R6 and R7, independently of each other, are hydrogen , an amino group, an alkylamino group of Ci-C6, a?,? - dialkylamino group of CrC6, a N, N- (dihydroxyalkyl) amino group of C C6, a halogen atom, a cyano group, an alkyl cyano group of Ci-C6, a methoxymethyl group, a tert-butyl group, an isopropyl group, a C6 alkyl group, an alkoxy group CrCe uiloxy, a hydroxyalkyl group of CrC6, a hydroxyalkyloxy group of C C &, an alkylcarboxylic acid group of Ci-C6, an ester group of C6 alkylcarboxylic acid, an alkylcarboxylic acid amide group of CrC6, an alkylsulfonic acid group of CrC6, an ester group of alkylsulfonic acid of CrCe, an amide group of alkylsulfonic acid of CrC6, a phenyl group or a sulfonic acid group; R8 is hydrogen, an alkylamino group of C C6, a?,? - dialkylamino group of CrCe, an alkyl cyano group of CrC6, a methoxymethyl group, a tert-butyl group, an isopropyl group, an alkyl group of CrC6, a group CrC6 alkyloxy, a C-hydroxyalkyl group, an d-Ce alkylcarboxylic acid group, an C-C6 alkylcarboxylic acid ester group, an alkylcarboxylic acid amide group of CrC6, an C-alkylsulfonic acid group, an ester group of Ci-C6 alkylsulfonic acid, an alkylsulfonic acid amide group of CrC6 or a phenyl group; R9 is a hydrogen atom, an amino group, an alkylamino group of CrC6, a?,? - dialkylamino group of Ci-C6, an alkyl cyano group of CrC6, a hydroxyl group, a nitro group, a methoxymethyl group, a group tert-butyl, an isopropyl group, a C6 alkyl group, an alkyloxy group of C C6, a hydroxyalkyl group of C C6, an alkylcarboxylic acid group of C C6, an ester group of alkylcarboxylic acid of C ^ Ce, an alkylsulfonic acid group of CrCe, an ester group of alkylsulfonic acid of CrCe or a carboxylic acid group (- COOH); wherein the alkyl groups may be branched or linear, R 'represents hydrogen or a nitro group; Hal indicates a hydrogen atom or a halogen atom (F, Br, Cl, I), especially in the case of a bromine or chlorine atom; and X "represents an anion

2. The agent according to claim 1, further characterized in that it contains at least one natural polymer, synthetic polymer or modified natural polymer commonly used in cosmetic agents, in the form of a dye fortifier or

3. An agent for clarifying and simultaneously coloring keratin fibers, characterized in that it contains (i) an oxidizing agent and also (ii) at least one indazoline thiazolazo cationic dye of the general formula (I), ) wherein R1 represents a hydrogen atom, an alkylamino group of CrC6, a tert-butyl group, an isopropyl group, an alkyl group of CrC6, an alkyloxy group of CrC6, a hydroxyalkyl group of CrC6, an alkylcarboxylic acid group of CrC6 , an ester group of alkylcarboxylic acid of CrC6, an alkylsulfonic acid group of CrC6 and an ester group of alkylsulfonic acid of CrC6; R2 represents a group of the general formulas (II) to (VI); R3 represents an alkyl group of CrC6, a hydroxyalkyl group of C2-C or a polyhydroxyalkyl group of C-C6; R4 and R5, independently of one another, are hydrogen, an alkylamino group of CrC6, a?,? - dialkylamino group of Ci-C6, an alkyl cyano group of CrC6, a methoxymethyl group, a tert-butyl group, an isopropyl group, an alkyl group of CrC6, an alkyloxy group of CrC6, a hydroxyalkyl group of Crds, an alkylcarboxylic acid group of CrC6, an ester group of alkylcarboxylic acid of CrC6, an amide group of alkylcarboxylic acid of Ci-C6, an alkylsulfonic acid group of CrC6, an ester group of C-alkylsulfonic acid, an alkylsulfonic acid amide group of CrCe, a benzyl group or a phenyl group; R6 and R7, independently of one another, are hydrogen, an amino group, an alkylamino group of CrC6, a?,? - dialkylamino group of CrC6, a N, N- (dihydroxyalkyl) amino group of CVC6, a halogen atom, an cyano group, an alkyl cyano group of C ^ -C6, a methoxymethyl group, a tert-butyl group, an isopropyl group, an alkyl group of C6, an alkyloxy group of Ce, a hydroxyalkyl group of C6, a group hydroxyalkyloxy of C-C6, an alkylcarboxylic acid group of C C6, an ester group of alkylcarboxylic acid of CrC6, an amide group of alkylcarboxylic acid of Ci-C6, an alkylsulfonic acid group of CrC ^ an ester group of alkylsulfonic acid of CrC6, an alkylsulfonic acid amide group of C Ce, a phenyl group or a sulfonic acid group; R8 is hydrogen, an alkylamino group of C Ce, a?,? - dialkylamino group of CrC6, an alkyl cyano group of C ^ Ce, a methoxymethyl group, a tert-butyl group, an isopropyl group, an alkyl group of C6 , an alkyloxy group of Ci-C6, a hydroxyalkyl group of CrC6, an alkylcarboxylic acid group of C C6, an ester group of alkylcarboxylic acid of CrC ^, an amide group of alkylcarboxylic acid of d-C6, an alkylsulfonic acid group of C Ce, an ester group of C6 alkylsulfonic acid, an alkylsulfonic acid amide group of C Ce or a phenyl group; R9 is a hydrogen atom, an amino group, an alkylamino group of C Ce, a?,? - dialkylamino group of CrCe, an alkyl cyano group of C C6, a hydroxyl group, a nitro group, a methoxymethyl group, a group tert-butyl, an isopropyl group, an alkyl group of C 6, an alkyloxy group of C C6, a hydroxyalkyl group of C C6, an alkylcarboxylic acid group of CrC6, an ester group of C6 alkylcarboxylic acid, an alkylsulfonic acid group of C C6, an ester group of C-C6 alkylsulfonic acid or a carboxylic acid group (-COOH); wherein the alkyl groups may be branched or linear, R 'represents hydrogen or a nitro group; Hal indicates a hydrogen atom or a halogen atom (F, Br, Cl, I), especially in the case of a bromine or chlorine atom; and X "represents an anion

4. An agent according to claim 3, further characterized in that the oxidizing agent is selected from hydrogen peroxide or its addition compounds with urea, melmin, sodium borate or sodium carbonate. An agent for the oxidative coloring of keratin fibers based on oxidative dye precursors, characterized in that it contains at least one indazoline thiazolazo cationic dye of the general formula (I), (0 wherein R 1 represents a hydrogen atom, an alkylamino group of C C 6, a tert-butyl group, an isopropyl group, an alkyl group of CrC 6, an alkyloxy group of CrC 6, a hydroxyalkyl group of C C 6, an alkylcarboxylic acid group of CrC6, an ester group of alkylcarboxylic acid of CrC6, an alkylsulfonic acid group of CrC6 and an ester group of alkylsulfonic acid of CrCe; R2 represents a group of the general formulas (II) to (VI); R3 represents an alkyl group of CrC6, a hydroxyalkyl group of C2-C4 or a polyhydroxyalkyl group of C4-C6; R4 and R5, independently of one another, are hydrogen, an alkylamino group of CrC6, a?,? - dialkylamino group of CrC6, an alkyl cyano group of CrC6, a methoxymethyl group, a tert-butyl group, an isopropyl group, a group C-C alkyl, an Ci-C6 alkyloxy group, a hydroxyalkyl group of C Ce, an alkylcarboxylic acid group of CrC6, an alkylcarboxylic acid ester group of CrC6, an alkylcarboxylic acid amide group of CrC6, an alkylsulfonic acid group of CrC6, an ester group of alkylsulfonic acid of CrC6, an amide group of alkylsulfonic acid of CrC6, a benzyl group or a phenyl group; R6 and R7, independently of one another, are hydrogen, an amino group, an alkylamino group of CrC6, a?,? - dialkylamino group of CrC6, a N, N- (dihydroxyalkyl) amino group of CrC6, a halogen atom, a cyano group, an alkyl cyano group of CrC6, a methoxymethyl group, a tert-butyl group, an isopropyl group, an alkyl group of CrC6, an alkyloxy group of CrC6, a hydroxyalkyl group of CrC6, a hydroxyalkyloxy group of CrC6, a group CrC6 alkylcarboxylic acid, an alkylcarboxylic acid ester group of CrC6, an alkylcarboxylic acid amide group of CrC6, an alkylsulfonic acid group of CrC6, an alkylsulfonic acid ester group of CrC6, an alkylsulfonic acid amide group of CrC6, a group phenyl or a sulfonic acid group; R8 is hydrogen, an alkylamino group of CrC6, a?,? - dialkylamino group of CrC6, an alkyl cyano group of CrC6, a methoxymethyl group, a tert-butyl group, an isopropyl group, an alkyl group of CrC6, an alkyloxy group of CrC6, a hydroxyalkyl group of CrC6, an alkylcarboxylic acid group of CrC6, an ester group of alkylcarboxylic acid of C C6, an amide group of alkylcarboxylic acid of Ci-C6, an alkyl sulfonic acid group of Ci-C6, an ester group of alkylsulfonic acid of CVC6, an amide group of alkylsulfonic acid of C C6 or a phenyl group; R9 is a hydrogen atom, an amino group, an alkylamino group of C ^ Ce, a?,? - dialkylamino group of C C6, an alkyl cyano group of C C6, a hydroxyl group, a nitro group, a methoxymethyl group, a tert-butyl group, an isopropyl group, an alkyl group of CrC6, an alkyloxy group of dC6, a hydroxyalkyl group of C, -C6, an alkylcarboxylic acid group of C6, an ester group of alkylcarboxylic acid of CrC6, an alkylsulfonic acid group of d-C6, an ester group of alkylsulfonic acid of C C6 or a carboxylic acid group (-COOH); wherein the alkyl groups may be branched or linear; R 'represents hydrogen or a nitro group; Hal indicates a hydrogen atom or a halogen atom (F, Br, Cl, I), especially in the case of a bromine or chlorine atom; and X "represents an anion 6. An agent according to claim 5, further characterized in that it contains 0.01 to 12 weight percent of at least one oxidative dye precursor 7. An agent according to claim 5 or 6, further characterized in that it is mixed with an oxidizing agent before use 8. The agent according to any of claims 1 to 7, further characterized in that the indazoline thiazolazo cationic dye of the general formula (I) is selected from methyl sulfate. of 6- { (£) - [4- (dimethylamino) phenyl] diazenyl.}. -7-methyl-1 H- [1,3] thiazolo [5,4-f] indazol-7-io, methylsulfate of 7-methyl-6- { (£) - [4- (methylamino) phenyl] diazenyl.} -1 - / - [1, 3] thiazolo [5,4- / | indazol-7-io, 6- ({(£) - [4- (ethylamino) phenyl] d, azole.] .7-methyl-1 H- [1, 3] thiazolo [5,4-] methylsulfate. r] ndazol-7-io, 6-, {(()) - [4- (d-ethalamino) -phenyl] diazenyl} -7-methyl-1 / - - [1,3] methylisulfate. ] thiazolo [5,4- / | indazol-7-io, metisulfate of 6 - ((£) - { 4 - [(2-hydroxyethyl) amino] phenyl} diazenil) -7-methyl-1 H- [1, 3] thiazolo- [5,4-indazol-7-io, 6 - ((E) -. {4- [bis (2-hydroxyethyl) amino] methylisulfate ] phenyl.}. diazenyl) -7-methyl-1 / - - [1,3] thiazolo [5,4-r] indazol-7-io, 2-hydroxyethyl methylisulfate. { 4 - [(£) - (7-methyl-1, 3] thiazolo [5,4-r] indazol-7-io-6-yl) diazenyl] phenyl} cyanamide, 6 - ((£) - { 4 - [(2-hydroxyethyl) (methyl) -amino] phenyl} diazenyl) -7-methyl-1 / - - [1, 3] thiazolo methylisulfate 5,4-1 -indazol-7-io, 6 - ((£) -. {4- [ethyl (2-hydroxyethyl) amino] phenol] diazenyl) -7-methyl-1 H methylisulfate - [1, 3] thiazolo [5 ^ -r] indazol-7-io, metisulfate of 6-. { (£) - [4- (dimethylamino) -phenyl] diazenyl} -1, 7-dimethyl-1 H- [1,3] thiazolo [5,4-r indazol-7-io, metisulfate of 6-. { (£) - [4- (dimethylamino) phenyl] diazenyl} -1- (2-hydroxyethyl) -7-methyl-1 H- [1,3] thiazolo [5,4-f) indazol-7-io, metisulfate of 6-. { (£) - [4- (diethylamino) -phenyl] diazenil} -1- (2-hydroxyethyl) -7-methyl-1 - / - [1, 3] thiazolo [5,4- ^ | indazol-7-o, 6 - ((£) -. {4 - [bis (2-hydroxyethyl) amino] phenyl] diazenyl) -1 - (2-hydroxyethyl) -7-methyl-1,3] thiazolo [5,4-] indazol-7-io, methylisulfate 6 - ((£) - { 4- [bis (2-hydroxyethyl) amino] phenyl] diazenyl) -1,7-dimethyl-1 H- [1,3] thiazolo [5,4-indazole- 7-io, 6 - [(£) - (4-hydroxyphenyl) -diazenyl] -1,7-dimethyl-1 H- [1,3] thiazolo [5.4 - /] indazol-7-io-methylisulfate methiisulfate of 6 - [(£) - (4-hydroxyphenyl) diazenyl] -7-methyl-1 H - [\, 3] thiazolo [5,4 - /] indazol-7-io, metisulfate of 6 - [(£) - (4-methoxyphenyl) diazenyl] -7-methyl-1,3] thiazolo [5,4-r] ndazol-7-yl, 6 - [(=) - (4-methoxyphenyl) -diazenyl] methylisulfate] -1,7-dimethyl-1 H- [1,3] thiazolo [5,4 - /] indazol-7-io, 6 - [(£) - (3,4-dimethoxyphenyl) diazenyl] -1 methylisulfate 7-dimethyl-1 H- [1,3] thiazolo [5,4-r] indazol-7-io and 6 - [(£) - (3,4-dimethoxyphenyl) diazenyl] -7-methyl-1-methylisulfate H- [1, 3] thiazolo [5,4-r] indazol-7-io. The agent according to any one of claims 1 to 8, further characterized in that the cationic dye of indazoline thiazolazo of the general formula (I) is present in a total amount of 0.01 to 10 weight percent. The agent according to any one of claims 1 to 9, further characterized in that the agent is a hair colorant.