DE19962880A1 - Color for coloring keratinous fibers, e.g. hair, wool or fur, especially human hair, contains halogen-substituted benzofurazan or N-oxide compound(s) - Google Patents

Abstract

Color for keratinous fibers, especially human hair, contains halogen-substituted benzofurazan(s) (I) or their N-oxide(s) as colorant. Color for keratinous fibers, especially human hair, contains halogen-substituted benzofurazan(s) of formula (I) or their N-oxide(s) as colorant. R<1> = hydrogen (H) or halogen; R<2> = H or a nitro, sulfo, sulfonate or sulfonamido group, in which the nitrogen (N) may be substituted by 1-4 carbon (C) (hydroxy)alkyl groups, which may form a heterocycle with the N atom; R<3>, R<4> = H, halogen, 1-4 C (hydroxy)alkyl, 1-4 C alkoxy, hydroxyl (OH), nitro, amino (optionally substituted by 1-4 C alkyl) or 1-4 C acyl or together form a condensed aromatic ring; at least one of R<1-4> = halogen. Independent claims are also included for: (a) the use of (I) or their N-oxides as coloring component in oxidation hair colors; (b) a method of coloring keratinous fibers, especially human hair, with a color containing (I) or N-oxide and other ingredients.

Description

The invention relates to an agent for dyeing keratin-containing fibers, in particular human hair, which contains benzofurazans or their N-oxides, as well as a Process for dyeing keratin-containing fibers, in particular human hair.

For dyeing keratin-containing fibers, e.g. B. hair, wool or fur, come in generally either substantive dyes or oxidation dyes, which by oxidative coupling of one or more developer components with one another or with one or more coupler components arise for the application. Coupler and ent Winding components are also known as oxidation dye precursors.

Primary aromatic amines with a further, in the para or ortho position, free or substituted hydroxy or Amino group, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyra zolone derivatives and 2,4,5,6-tetraaminopyrimidine and its derivatives are used.

Special representatives are, for example, p-phenylenediamine, p-tolylenediamine, 2,4,5,6-Te traaminopyrimidine, p-aminophenol, N, N-bis (2-hydroxyethyl) -p-phenylenediamine, 2- (2,5-di aminophenyl) ethanol, 2- (2,5-diaminophenoxy) ethanol, 1-phenyl-3-carboxyamido-4-ami no-pyrazolone-5, 4-amino-3-methylphenol, 2-aminomethyl-4-aminophenol, 2-hydroxy methyl-4-aminophenol, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopy rimidine and 2,5,6-triamino-4-hydroxypyrimidine.

As a rule, m-phenylenediamine derivatives, naphthols, Resorcinol and resorcinol derivatives, pyrazolones, m-aminophenols and substituted pyridine derivatives used. Particularly suitable coupler substances are α-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, Resorcinol monomethyl ether, p-phenylenediamine, 2,4-diaminophenoxyethanol, 2-amino-4- (2-hydroxyethylamino) anisole (Lehmann's blue), 1-phenyl-3-methyl-pyrazolone-5, 2,4-dichloro 3-aminophenol, 1,3-bis- (2,4-diaminophenoxy) -propane, 2-chlororesorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol, 3-amino-6-methoxy-2-methylamino-pyridine and 3,5-diamino-2,6-dimethoxypyridine.

With regard to other customary dye components, reference is expressly made to the series "Der matology ", edited by Ch. Culnan, H. Maibach, Marcel Dekker Inc., New York, Basel, 1986, vol. 7, Ch. Zviak, The Science of Hair Care, chap. 7, pages 248-250 (Direct dyes), and Chap. 8, pages 264-267 (oxidation dyes), as well as the "European Inventory of Cosmetic Raw Materials", 1996, published by Euro European Commission, available in diskette form from the Federation of German Industrial and trading company for pharmaceuticals, health foods and personal care products e.V., Mannheim.

Oxidation dyes can be used to achieve intense colorations with good fastness properties. B. H ₂ O ₂ , which in some cases can damage the fiber. Furthermore, some oxidation dye precursors or certain mixtures of oxidation dye precursors can sometimes have a sensitizing effect on people with sensitive skin. Direct dyes are applied under more gentle conditions, but their disadvantage is that the dyeings often only have inadequate fastness properties.

The use of the benzofurazans described in more detail below for dyeing Keratin-containing fibers is not yet known.

The object of the present invention is to provide coloring agents for keratin fibers, in particular human hair, which are qualitatively at least equivalent to the usual oxidation hair dyes in terms of depth of color, gray coverage and fastness properties, but without necessarily relying on oxidants such as. B. H ₂ O _{2 to be} instructed. In addition, the colorants must have no or only a very low sensitization potential.

Surprisingly, it has now been found that those shown in the formula I. Benzofurazans are excellent for working even in the absence of oxidizing agents Dyeing of keratin-containing fibers is suitable. They give colorations with excellent Brilliance and depth of color and lead to a variety of color nuances. The use of oxi In principle, however, the acting agents should not be excluded.

The invention relates to an agent for dyeing keratin-containing fibers, in particular human hair, containing at least one benzofurazan with the formula I or its N-oxide,

in the
R ^{1 is} a hydrogen atom or a halogen atom,
R ^{2 is} a hydrogen atom, a nitro, sulfo, sulfonate or sulfonamide group in which the nitrogen _{can be substituted by C 1-4} alkyl or hydroxyalkyl groups, which together with the nitrogen atom can also form a heterocyclic ring,
R ³ and R ^{4 represent} a hydrogen, halogen atom, a C _1-4 -alkyl, C _1-4 -alkoxy or hydroxy-C _1-4 -alkyl group, a hydroxy, nitro, amino group which is represented by C _{1 -4} alkyl groups can be substituted, or C _1-4 acyl groups, both of which can also jointly form a fused aromatic ring, with the proviso that at least one of the radicals R ¹ to R ^{4 is} a halogen atom.

Keratin-containing fibers include wool, fur, feathers, and especially human Understand hair. In principle, however, the colorants according to the invention can also for dyeing other natural fibers, such as B. cotton, jute, sisal, linen or silk, modified natural fibers, such as. B. regenerated cellulose, nitro, alkyl or hydroxyalkyl or acetyl cellulose and synthetic fibers, such as. B. polyamide, polyacrylonitrile, poly urethane and polyester fibers are used.

Most of the compounds of the formula I are known from the literature and are commercially available obtainable or can be prepared by known synthesis processes. The N-oxides of the Benzofurazans with the formula I are also referred to as benzofuroxans.

The compounds with the formula I are preferably selected from 7-chloro-4-nitro benzofurazan, 7-fluoro-4-nitrobenzofurazan, 7-chloro-benzofurazan-4-sulfonic acid, Ammonium salt, 7-fluoro-benzofurazan-4-sulfonic acid, ammonium salt, 7-chloro benzofurazan-4-sulfonamide, 7-chloro-4-morpholinosulfonyl-, 7-chloro-4- dimethylaminosulfonyl-, 7-fluoro-4-dimethylaminosulfonylbenzofurazan, 5-fluoro-benzofuroxan, 5-chloro-benzofuroxan, 7-chloro-benzofuroxan, 4,6-dichlorobenzofuroxan, 5-chloro-benzofurazan and any mixtures thereof.

The aforementioned benzofurazans or their N-oxides with the formula I are preferably in the agents according to the invention in an amount of 0.03 to 65 mmol, in particular from 1 to 40 mmol, based on 100 g of the total colorant, ver turns. They can be used as substantive colorants or in the presence of usual Oxidation dye precursors are used.

Colorants that contain benzofurazans with the formula I or their N- Containing oxides alone are preferably used for lighter colors. Staining with even greater brilliance and improved fastness properties (light fastness, washing fastness, rubbing fastness) over a wide range of shades from brown-yellow brown-orange, brown-red, light brown, medium brown, dark brown, dark purple up to blue-black and black are achieved when those used according to the invention Compounds with the formula I together with at least one further component (hereinafter called component B), selected from compounds with primary or secondary amino group or hydroxy group selected from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds, amino acids, built up from 2 to 9 amino acids Oligopeptides and / or CH-active compounds can be used. these are on the one hand, compounds that only stain keratin-containing fibers weakly and only give brilliant colorations together with the compounds of formula I. On the other hand, it also includes compounds that are already used as oxidation color Material precursors are used.

Several different carbazole aldehydes and / or -ketones of the formula I are used together; several ver different compounds of component B can be used together.

The embodiment described above also includes the use of such substances, the reaction products of benzofurazans of the formula I or their Represent N-oxides with the compounds mentioned of component B, as substantive dyes. Such reaction products can, for. B. by short Warm the two components in stoichiometric amounts in aqueous neutral to weakly alkaline medium can be obtained, either as a solid from the Solution precipitate or be isolated from it by evaporating the solution. the Reaction products can also be used in combination with other dyes or Dye precursors are used.

Suitable compounds with a primary or secondary amino group as component B are, for. B. primary aromatic amines such as N, N-dimethyl-, N, N-diethyl-, N- (2-hydroxyethyl) -N-ethyl-, N, N-bis- (2-hydroxyethyl) -, N- ( 2-methoxyethyl-), 2,3-, 2,4-, 2,5-dichloro-p-phenylenediamine, 2-chloro-p-phenylenediamine, 2,5-dihydroxy-4-morpholinoaniline dihydrobromide, 2-, 3-, 4-aminophenol, 2-aminomethyl-4-aminophenol, 2-hydroxymethyl-4-aminophenol, o-, p-phenylenediamine, o-tolylenediamine, 2,5-diaminotoluene, -phenol, -phenethol, 4-amino -3-methylphenol, 2- (2,5-diaminophenyl) -ethanol, 2,4-diaminophenoxyethanol, 2- (2,5-diaminophenoxy) -ethanol, 4-methylamino-, 3-amino-4- (2 ' -hydroxy ethyloxy), 3,4-methylenediamino, 3,4-methylenedioxyaniline, 3-amino-2,4-dichloro, 4-methylamino, 2-methyl-5-amino-, 3-methyl-4 -amino-, 2-methyl-5- (2-hydroxyethylamino) -, 6-methyl-3-amino-2-chloro-, 2-methyl-5-amino-4-chloro-, 3,4-methylenedioxy-, 5- (2-Hydroxyethylamino) -4-methoxy-2-methyl-, 4-amino-2-hydroxymethylphenol, 1,3-diamino-2,4-dimethoxybenzene, 2-, 3-, 4-aminobenzoic acid, - phenylacetic acid, 2,3-, 2,4-, 2,5-, 3, 4-, 3,5-diaminobenzoic acid, 4-, 5-aminosalicylic acid, 3-amino-4-hydroxy-, 4-amino-3-hydroxybenzoic acid, 2-, 3-, 4-aminobenzenesulfonic acid, 3-amino-4- hydroxybenzenesulfonic acid, 4-amino-3-hydroxynaphthalene-1-sulfonic acid, 6-amino-7-hydroxynaphthalene-2-sulfonic acid, 7-amino-4-hydroxynaphthalene-2-sulfonic acid, 4-amino-5-hydroxynaphthalene-2,7- disulfonic acid, 3-amino-2-naphthoic acid, 3-aminophthalic acid, 5-aminoisophthalic acid, 1,3,5-, 1,2,4-triaminobenzene, 1,2,4,5-tetraaminobenzene, 2,4,5- Triaminophenol, pentaamino benzene, hexaaminobenzene, 2,4,6-triaminoresorcinol, 4,5-diaminobrenzcatechol, 4,6-diamino pyrogallol, 3,5-diamino-4-hydroxy-pyrocatechol, aromatic nitriles, amino compounds containing nitro groups, such as 3-amino -6-methylamino-2-nitro-pyridine, picric acid, 1- (2 (3) -nitro-4-amino) -phenylazo-2-hydroxy-7-trimethylammoniumnaphthalene chloride, 1-hydroxy-2-amino-4, 6-dinitro-benzene, 1-amino-2-nitro-4-bis- (2-hydroxyethyl) -amino-benzene, 1-amino-2- (2-hydroxyethyl) -amino-5-nitro-benzene (HC Yellow No. 5), 1-Amino-2-nitro-4- (2-hydroxyethyl) -aminobenzene (HC Red No. 7), 2-chloro-5-nitro-N-hydroxyethyl-1,4-phenylenediamine, 1- (2-hydroxyethyl ) -amino-2-nitro-4-amino-benzene (HC Red No. 3), 4-amino-3-nitrophenol, 4-amino-2-nitrophenol, 6-nitro-o-toluidine, 1-amino-3 -methyl-4- (2-hydroxyethyl) -amino-6-nitrobenzene (HC Violet No. 1), 1-amino-2-nitro-4- (2,3-dihydroxypropyl) -amino-5-chlorobenzene an (HC Red No. 10), 4-amino-2-nitrodiphenyl amino-2'-carboxylic acid (2- (4-amino-2-nitroanilino) benzoic acid), 6-nitro-2,5-diaminopyridine, 2-amino-6 -chloro-4-nitrophenol, 2-amino-6-chloro-4-nitrophenol, 1-amino- 2- (3-nitrophenylazo) -7-phenylazo-8-naphthol-3,6-disulfonic acid, disodium salt (Acid blue No. . 29), 1-Amino-2- (2-hydroxy-4-nitrophenylazo) -8-naphthol-3,6-disulfonic acid, disodium salt (Palatinchrome green), 1-amino-2- (3-chloro-2-hydroxy -5-nitrophenylazo) -8- naphthol-3,6-disulfonic acid, disodium salt (gallion), 4-amino-4'-nitrostilbene-2,2'-disulfonic acid, disodium salt, 2,4-diamino-3 ', 5 '-dinitro-2'-hydroxy -5-methyl-azobenzene (Mordant brown 4), 4'-amino-4-nitrodiphenylamine-2-sulfonic acid, 4'-amino-3'-nitro benzophenone-2-carboxylic acid, 1-amino-4-nitro-2- (2-nitrobenzylideneamino) -benzene, 2- [2- (diethylamino) -ethylamino] -5-nitroaniline, 3-amino-4-hydroxy-5-nitrobenzenesulfonic acid, (hydrate), 3-amino-3'-nitrobiphenyl, 3 -Amino-4-nitro-acenaphthene, 2-amino-1-nitronaphthalene, 5-amino-6-nitrobenzo-1,3-dioxole, anilines, in particular anilines containing nitro groups, such as 4-nitroaniline, 2-nitroaniline, 1 , 4-diamino-2-nitrobenzene, 1,2-diamino-4-nitrobenzene, 1-amino-2-methyl-6-nitrobenzene, 4-nitro-1,3-phenylenediamine, 2-nitro-4-amino-1 - (2-hydroxyethylamino) benzene, 2-nitro-1-amino-4- [bis (2-hydroxyethyl) amino] benzene, 4-amino-2-nitrodiphenylamine-2'-carboxylic acid, 2-amino 6-chloro-4-nitrophenol, 1-amino-5-chloro-4- (2-hydroyethylamino) -2-nitrobenzene, aromatic anilines or phenols with another aromatic radical, as shown in formula II

in the
R ^{5 represents} a hydroxy or an amino group which is _{substituted by C 1-4} -alkyl, C _1-4 -hydroxyalkyl, C _1-4 -alkoxy or C _1-4 -alkoxy-C _1-4 -alkyl groups can be substituted, stands,
R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ stand for hydrogen, a hydroxy or an amino group which is represented by C _1-4 -alkyl-, C _1-4 -hydroxyalkyl, C _1-4 -alkoxy-, C _1-4 -aminoalkyl or C _1-4 -alkoxy-C _1-4 -alkyl groups can be substituted, and
P stands for a direct bond, a saturated or unsaturated carbon chain with 1 to 4 carbon atoms, optionally substituted by hydroxyl groups, a carbonyl, sulfonyl or imino group, an oxygen or sulfur atom, or a group with the formula III

Z- (CH ₂ -Y-CH ₂ -Z ') _o (III)

in which Y is a direct bond, a CH ₂ or CHOH group,
Z and Z 'independently represent an oxygen atom, an NR ¹¹ group, in which
R ¹¹ denotes hydrogen, a C _1-4 -alkyl or a hydroxy-C _1-4 -alkyl group, the group O- (CH ₂ ) _p -NH or NH- (CH ₂ ) _p '-O, in which p and p 'are 2 or 3, stand and
o means a number from 1 to 4,
such as 4,4'-diaminostilbene and its hydrochloride, 4,4'-diaminostilbene-2,2'-disulfonic acid mono- or di-Na salt, 4-amino-4'-dimethylaminostilbene and its hydrochloride, 4 , 4'-diaminodiphenylmethane, -sulfide, -sulfoxide, -amine, 4,4-diaminodiphenylamine-2-sulfonic acid, 4,4'-diaminobenzophenone, -diphenylether, 3,3 ', 4,4'-tetraamino diphenyl, 3 , 3 ', 4,4'-tetraamino-benzophenone, 1,3-bis- (2,4-diaminophenoxy) -propane, 1,8-bis- (2,5-diaminophenoxy) -3,6-dioxaoctane, 1 , 3-bis- (4-aminophenylamino) propane, -2-pro panol, 1,3-bis- [N- (4-aminophenyl) -2-hydroxyethylamino] -2-propanol, N, N-bis- [2 - (4-aminophenoxy) -ethyl] -methylamine, N-phenyl-1,4-phenylenediamine.

The aforementioned compounds can be used both in free form and in the form of their physiologically compatible salts, especially as salts of inorganic acids, such as Hydrochloric or sulfuric acid can be used.

Suitable nitrogen-containing heterocyclic compounds are, for. B. 2-, 3-, 4-amino-, 2- Amina-3-hydroxy, 2,6-diamino, 2,5-diamino, 2,3-diamino, 2-dimethylamino-5-amino, 2-methylamino-3-amino-6-methoxy, 2,3-diamino-6-methoxy, 2,6-dimethoxy-3,5-dia mino-, 2,4,5-triamino-, 2,6-dihydroxy-3,4-dimethylpyridine, 2,4-dihydroxy-5,6-diamino, 4,5,6-triamino, 4-hydroxy-2,5,6-triamino, 2-hydroxy-4,5,6-triamino, 2,4,5,6-tetraamino, 2-methylamino-4,5,6-triamino, 2,4-, 4,5-diamino, 2-amino-4-methoxy-6-methyl-pyrimi din, 3,5-diaminopyrazole, -1,2,4-triazole, 3-amino-, 3-amino-5-hydroxypyrazole, 2-, 3-, 8- Aminoquinoline, 4-aminoquinoline, 2-, 6-aminonicotinic acid, 5-aminoisoquinoline, 5-, 6- Aminoindazole, 5-, 7-aminobenzimidazole, -benzothiazole, 2,5-dihydroxy-4-morpholinoaniline as well as indole and indoline derivatives such as 4-, 5-, 6-, 7-aminoindole, 5,6-dihydroxyindole, 5,6-dihydroxyindoline and 4-hydroxyindoline. Furthermore, as heterocyclic compounds can, according to the invention, the hydroxypyrimidines disclosed in DE-U1-299 08 573 can be used. The aforementioned compounds can be used both in free form also in the form of their physiologically acceptable salts, e.g. B. as salts more inorganic Acids, such as hydrochloric or sulfuric acid, can be used.

Suitable aromatic hydroxy compounds are, for. B. 2-, 4-, 5-methylresorcinol, 2,5-Di methylresorcinol, resorcinol, 3-methoxyphenol, catechol, hydroquinone, pyrogallol, Phloroglucinol, hydroxyhydroquinone, 2-, 3-, 4-methoxy-, 3-dimethylamino-, 2- (2-hydroxy ethyl) -, 3,4-methylenedioxyphenol, 2,4-, 3,4-dihydroxybenzoic acid, -phenylacetic acid, Gallic acid, 2,4,6-trihydroxybenzoic acid, -acetophenone, 2-, 4-chlororesorcinol, 1-naph thol, 1,5-, 2,3-, 2,7-dihydroxynaphthalene, 6-dimethylamino-4-hydroxy-2-naphthalenesulfone acid, 3,6-dihydroxy-2,7-naphthalenesulfonic acid.

Preferred amino acids are all naturally occurring and synthetic α- Amino acids in question, e.g. B. by hydrolysis from vegetable or animal Proteins, e.g. B. collagen, keratin, casein, elastin, soy protein, wheat gluten or Almond protein accessible amino acids. It can be acidic as well as alkaline reactive amino acids are used. Preferred amino acids are arginine, Histidine, tyrosine, phenylalanine, DOPA (dihydroxyphenylalanine), ornithine, lysine and Tryptophan. But also other amino acids, such as. B. 6-aminocaproic acid, can can be used.

The oligopeptides can be naturally occurring or synthetic oligopeptides, but also the oligopeptides contained in polypeptide or protein hydrolysates, see above if they are more than sufficient for use in the colorants according to the invention de water solubility. Examples are e.g. B. Glutathione or those in the Hydrolysates of collagen, keratin, casein, elastin, soy protein, wheat gluten or man Delprotein containing oligopeptides should be mentioned. The use here is preferred together with compounds with primary or secondary amino groups or with aromati c hydroxy compounds.

As CH-active compounds, 1,2,3,3-tetramethyl-3H-yne can be mentioned by way of example dolium iodide, 1,2,3,3-tetramethyl-3H-indolium-p-toluenesulfonate, 1,2,3,3-tetramethyl-3H-yne dolium methanesulfonate, Fischer's base (1,3,3-trimethyl-2-methyleneindoline), 2,3-di methyl benzothiazolium iodide, 2,3-dimethyl benzothiazolium p-toluenesulfonate, 1,2-dimethyl naphtho [1,2-d] thiazolium-p-toluenesulfonate, 1-ethyl-2-methyl-naphtho [1,2-d] thiazolium-p- toluenesulfonate, rhodanine, rhodanine-3-acetic acid, 1-methyl-2-quinaldinium iodide, 1-ethyl 2-quinaldinium iodide, 1,4-dimethylquinolinium iodide, barbituric acid, thiobarbituric acid, 1,3-dimethylthiobarbituric acid, 1,3-diethylthiobarbituric acid, diethylthiobarbituric acid, oxindole, 3-indoxylacetate, coumaranone and 1-methyl-3-phenyl-2-pyrazolinone.

The compounds of component B are particularly preferably selected from Group consisting of N- (2-hydroxyethyl) -N-ethyl-, 2-chloro-p-phenylenediamine, N, N-bis- (2-hydroxyethyl) -p-phenylenediamine, 4-aminophenol, p-phenylenediamine, 2- (2,5-diamino phenyl) ethanol, 2,5-diaminotoluene, 3,4-methylenedioxyaniline, 2-amino-4- (2-hydroxyethyl amino) anisole, 2- (2,4-diaminophenoxy) ethanol, 3-amino-2,4-dichloro, 2-methyl-5-amino, 3-methyl-4-amino-, 2-methyl-5- (2-hydroxyethylamino) -, 2-methyl-5-amino-4-chloro-, 6-Me ethyl 3-amino-2-chloro-, 2-aminomethyl-4-aminophenol, 2-diethylaminomethyl-4-amino phenol, 2-dimethylaminomethyl-4-aminophenol, 2,6-dichloro-4-aminophenol, 2-hydroxy methyl-4-aminophenol, 3,4-methylenedioxyphenol, 3,4-diaminobenzoic acid, 2,5-diamino, 2-dimethylamino-5-amino, 3-amino-2-methylamino-6-methoxy, 2,3-diamino-6-methoxy, 3,5-diamino-2,6-dimethoxy-, 2,6-dihydroxy-3,4-dimethylpyridine, 2-hydroxy-4,5,6-triamino-, 4-hydroxy-2,5,6-triamino-, 2,4,5,6-tetraamino-, 2-methylamino-4,5,6-triamino-pyrimidine, 3,5-diaminopyrazole, 3-amino-5-hydroxypyrazole, 5,6-dihydroxyindole and 5,6-dihydroxyyne dolin, β-alanine, L-proline, L-lysine, DL-tyrosine and their preferably inorganic ones Physiologically acceptable salts formed by acids.

The above-mentioned compounds of component B can be used in an amount from 0.03 to 65, in particular 1 to 40 mmol, in each case based on 100 g of the ge velvet dye, can be used. Furthermore, according to the invention, it can particularly be preferred, the compound of formula I and the compound of component B im molar quantitative ratio of 2: 1 to 1: 2, in particular approximately equimolar, to be used. When using compounds of component B that contain one or more amino groups contain, the compounds of formula I on the one hand and the compounds of Component B, on the other hand, is preferably used in proportions such that the sum of the number of carbonyl groups of the compounds of the formula I and the sum the number of amino groups of the compounds of component B in a ratio of 2: 1 to Stand 1: 2.

To achieve further and more intense colors, the inventive Agents also contain color enhancers. The color enhancers are preferred selected from the group consisting of piperidine, piperidine-2-carboxylic acid, Piperidine-3-carboxylic acid, piperidine-4-carboxylic acid, pyridine, 2-hydroxypyridine, 3-hydroxypyridine, 4-hydroxypyridine, imidazole, 1-methylimidazole, histidine, pyrrolidine, proline, pyrrolidone, pyrroli don-5-carboxylic acid, pyrazole, 1,2,4-triazole, piperazidine, their derivatives and their phy siologically compatible salts.

The color enhancers mentioned above can each be used in an amount of 0.03 to 65, in particular 1 to 40 mmol, each based on 100 g of the total colorant, can be used.

For the presence of oxidizing agents, e.g. B. H ₂ O ₂ , can be dispensed with. However, under certain circumstances it may be desirable to add hydrogen peroxide or other oxidizing agents to the agents according to the invention in order to achieve shades which are lighter than the keratin-containing fibers to be dyed. Oxidizing agents are generally used in an amount of 0.01 to 6% by weight, based on the application solution. A preferred oxidizing agent for human hair is H ₂ O ₂ .

In a preferred embodiment, the colorants according to the invention contain for further modification of the color nuances in addition to the compounds contained according to the invention applications additionally usual substantive dyes, z. B. from the group of nitropheny lendiamine, nitroaminophenols, anthraquinones or indophenols, such as. B. under the international names or trade names HC Yellow 2, HC Yellow 4, HC Yellow 6, Basic Yellow 57, Disperse Orange 3, HC Red 3, HC Red BN, Basic Red 76, HC Blue 2, Disperse Blue 3, Basic Blue 99, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9, Basic Brown 16 and Basic Brown 17 known compounds as well Picramic acid 2-amino-6-chloro-4-nitrophenol, 4-amino-2-nitrodiphenylamine-2'-carbon acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 4-N-ethyl-1,4-bis- (2'-hydroxyethylamino) -2-ni trobenzene hydrochloride and 1-methyl-3-nitro-4- (2'-hydroxyethyl) aminobenzene. the Agents according to the invention according to this embodiment contain the substantive Dyes preferably in an amount of 0.01 to 20% by weight, based on the total Colorants.

Furthermore, the preparations according to the invention can also occur naturally Dyes such as red henna, neutral henna, black henna, chamomile blossom, Sandalwood, black tea, buckthorn bark, sage, blue wood, madder root, catechu, Contains sedre and alkanna root.

It is not necessary that the oxidation dye precursors or the optional contain ten substantive dyes each represent uniform compounds. Much more can in the colorants according to the invention, due to the manufacturing process for the individual dyes and other components in minor amounts be included, provided that they do not adversely affect the dyeing result or off their reasons, e.g. B. toxicological, must be excluded.

The colorants according to the invention result in physiologically compatible ones Temperatures below 45 ° C, intense colorations. They are therefore particularly suitable for coloring human hair. For use on human hair The colorants can usually be incorporated into a water-containing cosmetic carrier to be worked. Suitable aqueous cosmetic carriers are, for. B. Creams, Emulsions, gels or surfactant-containing foaming solutions such. B. Shampoos or other preparations suitable for use on the keratin-containing fibers are suitable. If necessary it is also possible to use the dye in anhydrous carrier to incorporate.

Furthermore, the colorants according to the invention can all be used in such preparations contain known active ingredients, additives and auxiliaries. In many cases contain the dye medium at least one surfactant, whereby in principle both anionic and zwitterionic, Ampholytic, nonionic and cationic surfactants are suitable. In many cases it has but it has proven to be advantageous to use the surfactants from anionic, zwitterionic or select nonionic surfactants.

Suitable anionic surfactants in preparations according to the invention are all anionic surface-active substances suitable for use on the human body. These are characterized by a water-solubilizing, anionic group such as. B. a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group with about 10 to 22 carbon atoms. In addition, the molecule can contain glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups. Examples of suitable anionic surfactants are, in each case in the form of the sodium, potassium and ammonium as well as the mono-, di- and trialkanolammonium salts with 2 or 3 carbon atoms in the alkanol group,

• - linear fatty acids with 10 to 22 carbon atoms (soaps),
• - Ethercarboxylic acids of the formula RO- (CH ₂ -CH ₂ O) _x -CH ₂ -COOH, in which R is a linear alkyl group with 10 to 22 carbon atoms and x = 0 or 1 to 16,
• - acyl sarcosides with 10 to 18 carbon atoms in the acyl group,
• - acyl taurides with 10 to 18 carbon atoms in the acyl group,
• - acyl isethionates with 10 to 18 carbon atoms in the acyl group,
• - Sulphosuccinic acid mono- and dialkyl esters with 8 to 18 carbon atoms in the alkyl group and sulfosuccinic acid mono-alkyl polyoxyethyl esters with 8 to 18 carbon atoms in the Alkyl group and 1 to 6 oxyethyl groups,
• - linear alkanesulfonates with 12 to 18 carbon atoms,
• - linear alpha-olefin sulfonates with 12 to 18 carbon atoms,
• - Alpha-sulfofatty acid methyl esters of fatty acids with 12 to 18 carbon atoms,
• - Alkyl sulfates and alkyl polyglycol ether sulfates of the formula RO (CH ₂ -CH ₂ O) _x -SO ₃ H, in which R is a preferably linear alkyl group with 10 to 18 carbon atoms and x = 0 or 1 to 12,
• - Mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030,
• - sulfated hydroxyalkyl polyethylene and / or hydroxyalkylene propylene glycol ethers according to DE-A-37 23 354,
• - Sulphonates of unsaturated fatty acids with 12 to 24 carbon atoms and 1 to 6 double bonds applications according to DE-A-39 26 344,
• - Esters of tartaric acid and citric acid with alcohols, the addition products of about 2 to 15 molecules of ethylene oxide and / or propylene oxide on fatty alcohols with 8 to Represent 22 carbon atoms.

Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids with 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule and, in particular, salts of saturated and, in particular, unsaturated C ₈ -C ₂₂ carboxylic acids, such as oleic acid, stearic acid, isostearic acid and Palmitic acid.

Zwitterionic surfactants are surface-active compounds which have at least one quaternary ammonium group and at least one —COO ^(-) or —SO ₃ ^(-) group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinates, for example cocoalkyl-dimethylammonium glycinate, N-acyl-aminopropyl-N, N-dimethylammoniumglycinate, for example cocoacylaminopropyl-dimethylammonium glycinate, and 2-alkyl 3-carboxymethyl-3-hydroxyethyl-imidazolines, each with 8 to 18 carbon atoms in the alkyl or acyl group, and cocoacylaminoethylhydroxyethylcarboxymethyl glycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known under the CTFA name Cocamidopropyl Betaine.

Ampholytic surfactants are surface-active compounds which, in addition to a C _8-18 alkyl or acyl group, contain at least one free amino group and at least one -COOH or -SO ₃ H group and are capable of forming internal salts are. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids, each with about 8 bis acetic acids 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkyl aminopropionate, cocoacylaminoethylaminopropionate and C _12-18 acyl sarcosine.

Nonionic surfactants contain z. B. a polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether group. Such connections are for example

• - Addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide to linear fatty alcohols with 8 to 22 carbon atoms, to fatty acids with 12 to 22 carbon atoms and to alkylphenols with 8 to 15 carbon atoms in the alkyl group,
• - C _12-22 fatty acid mono- and diesters of addition products of 1 to 30 mol of ethylene oxide with glycerol,
• - C _{8-22 -alkyl} mono- and oligoglycosides and their ethoxylated analogues,
• - Addition products of 5 to 60 moles of ethylene oxide with castor oil and hydrogenated Castor oil,
• - Addition products of ethylene oxide with sorbitan fatty acid esters
• - Addition products of ethylene oxide with fatty acid alkanolamides.

Examples of the cat which can be used in the hair treatment compositions according to the invention ionic surfactants are, in particular, quaternary ammonium compounds. Are preferred Ammonium halides such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g. B. Cetyltrimethylammonium chloride, Stea ryltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethyl ammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride. Further cationic surfactants which can be used according to the invention are the quaterni represented protein hydrolysates.

Also suitable according to the invention are cationic silicone oils such as, for example, those im Commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized Tri methylsilylamodimethicone), Dow Corning 929 emulsion (containing a hydroxyl-amino modified silicone, also known as amodimethicone), SM-2059 (Manuf ler: General Electric), SLM-55067 (manufacturer: Wacker) and Abil®-Quat 3270 and 3272 (Manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxane, Quaternium-80).

Alkylamidoamines, especially fatty acid amidoamines like that under the name Tego Amid®S 18 available stearylamidopropyldimethylamine, stand out next to one good conditioning effect, especially due to their good biodegradability.

Quaternary ester compounds, so-called, are also very readily biodegradable "Esterquats" such as the methylhydroxy sold under the Stepantex® trademark alkyl dialkoyloxyalkylammonium methosulfates.

An example of a quaternary sugar derivative that can be used as a cationic surfactant is provided the commercial product Glucquat®100 is, according to the CTFA nomenclature a "Lauryl Methyl" Gluceth-10 Hydroxypropyl Dimonium Chloride ".

The compounds with alkyl groups used as surfactants can each be act uniform substances. However, it is usually preferred in manufacturing these substances are based on native vegetable or animal raw materials, so that one substance mixtures with different, depending on the respective raw material Maintains alkyl chain lengths.

In the case of surfactants, the addition products of ethylene and / or propylene oxide Fatty alcohols or derivatives of these addition products can be both Pro products with a "normal" homolog distribution as well as those with a narrowed Homolog distribution can be used. Are under "normal" homolog distribution this understood mixtures of homologues that one in the implementation of Fettal alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or Alkali metal alcoholates obtained as catalysts. Narrowed homolog distributions who on the other hand, if, for example, hydrotalcites, alkaline earth metal salts of Ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates as catalysts be used. The use of products with a narrow homolog distribution may be preferred.

Further active ingredients, auxiliaries and additives are, for example

• - nonionic polymers such as vinyl pyrrolidone / vinyl acrylate copolymers, Polyvinylpyrrolidone and vinylpyrrolidone / vinyl acetate copolymers and polysiloxanes,
• - Cationic polymers such as quaternized cellulose ethers, polysiloxanes with quaternary Groups, dimethyldiallylammonium chloride polymers, acrylamide-dimethyldiallyl ammonium chloride copolymers, dimethylaminoethyl quaternized with diethyl sulfate methacrylate-vinylpyrrolidone copolymers, Vinyl pyrrolidone imidazolinium methochloride copolymers and quaternized polyvinyl alcohol,
• - zwitterionic and amphoteric polymers such as acrylamidopropyl-tri methylammonium chloride / acrylate copolymers and octylacrylamide / methyl methacryl lat / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers,
• - anionic polymers such as polyacrylic acids, crosslinked polyacrylic acids, Vinyl acetate / crotonic acid copolymers, vinyl pyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhy drid copolymers and acrylic acid / ethyl acrylate / N-tert.-butyl acrylamide terpolymers,
• - Thickeners such as agar-agar, guar gum, alginates, xanthan gum, gum ara bicum, karaya gum, locust bean gum, linseed gums, dextrans, cel lulose derivatives, e.g. Methyl cellulose, hydroxyalkyl cellulose and carboxymethyl cellulose lulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such as B. bentonite or fully synthetic hydrocolloids such. B. polyvinyl alcohol,
• - structurants such as glucose and maleic acid,
• - hair conditioning compounds such as phospholipids, e.g. soy lecithin, Egg lecithin and cephalins, as well as silicone oils,
• - Protein hydrolysates, in particular elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolysates, their condensation products with fatty acids as well as quaternized protein hydrolysates,
• - perfume oils, dimethyl isosorbide and cyclodextrins,
• - Solubilizers such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerine and diethylene glycol,
• - Anti-dandruff ingredients such as Piroctone Olamine and Zinc Omadine,
• - other substances to adjust the pH value,
• - Active ingredients such as panthenol, pantothenic acid, allantoin, pyrrolidone carboxylic acids and their salts, plant extracts and vitamins,
• - cholesterol,
• - light stabilizers,
• - Consistency factors such as sugar esters, polyol esters or polyol alkyl ethers,
• - Fats and waxes such as whale rat, beeswax, montan wax, paraffins, fatty alcohols and fatty acid esters,
• - fatty acid alkanolamides,
• - complexing agents such as EDTA, NTA and phosphonic acids,
• - Swelling and penetration substances such as glycerine, propylene glycol monoethyl ether, carbo nate, bicarbonates, guanidines, ureas as well as primary, secondary and ter tiary phosphates, imidazoles, tannins, pyrrole,
• - opacifiers such as latex,
• - pearlescent agents such as ethylene glycol mono- and distearate,
• - Propellants such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air as well
• - antioxidants.

The components of the water-containing carrier are used to produce the erfindungsge moderate colorants are used in the amounts customary for this purpose; z. B. Emul greasing agents in concentrations of 0.5 to 30% by weight and thickening agents in concentrations Trations of 0.1 to 25 wt .-% of the total colorant used.

For the coloring result, it can be advantageous to use ammonium or metal as the coloring agent add salts. Suitable metal salts are e.g. B. formates, carbonates, halides, Sulfates, butyrates, valenates, capronates, acetates, lactates, glycolates, tartrates, citrates, Gluconates, propionates, phosphates and phosphonates of alkali metals, such as potassium, Sodium or lithium, alkaline earth metals such as magnesium, calcium, strontium or barium, or of aluminum, manganese, iron, cobalt, copper or zinc, with sodium acetate, Lithium bromide, calcium bromide, calcium gluconate, zinc chloride, zinc sulfate, magnesium chloride, magnesium sulfate, ammonium carbonate, chloride and acetate are preferred. These Salts are preferably in an amount from 0.03 to 65, in particular from 1 to 40 mmol based on 100 g of the total colorant.

The pH value of the ready-to-use coloring preparations is usually between 2 and 11, preferably between 5 and 10.

Another object of the present invention relates to the use of benzofurazans with the formula I or their N-oxides,

in the
R ^{1 is} a hydrogen atom or a halogen atom,
R ^{2 is} a hydrogen atom, a nitro, sulfo, sulfonate or sulfonamide group in which the nitrogen _{can be substituted by C 1-4} alkyl or hydroxyalkyl groups, which together with the nitrogen atom can also form a heterocyclic ring,
R ³ and R ^{4 represent} a hydrogen, halogen atom, a C _1-4 -alkyl, C _1-4 -alkoxy or hydroxy-C _1-4 -alkyl group, a hydroxy, nitro, amino group which is represented by C _{1 -4} -alkyl groups can be substituted, or C _1-4 -acyl groups, both of which can jointly form a fused aromatic ring, with the proviso that at least one of the radicals R ¹ to R ^{4 is} a halogen atom,
as a coloring component in oxidation hair dyes.

Yet another object of the present invention relates to a method for dyeing keratin-containing fibers, in particular human hair, in which a coloring agent is contained

• A) at least one benzofurazan with the formula I or its N-oxide,
  in the
  R ^{1 is} a hydrogen atom or a halogen atom,
  R ^{2 is} a hydrogen atom, a nitro, sulfo, sulfonate or sulfonamide group in which the nitrogen _{can be substituted by C 1-4} alkyl or hydroxyalkyl groups, which together with the nitrogen atom can also form a heterocyclic ring,
  R ³ and R ^{4 represent} a hydrogen, halogen atom, a C _1-4 -alkyl, C _1-4 -alkoxy or hydroxy-C _1-4 -alkyl group, a hydroxy, nitro, amino group which is represented by C _{1 -4} -alkyl groups can be substituted, or C _1-4 -acyl groups, both of which can also jointly form a fused aromatic ring, with the proviso that at least one of the radicals R ¹ to R ^{4 is} a halogen atom, and
• B) at least one compound with a primary or secondary amino group or Hy hydroxy group selected from primary or secondary aliphatic or aroma tables amines, nitrogen-containing heterocyclic compounds, aromatic Hydroxy compounds, amino acids, oli made up of 2 to 9 amino acids gopeptides and / or at least one CH-active compound,

as well as common cosmetic ingredients applied to the keratin-containing fibers, some Leave time, usually about 30 minutes, on the fiber and then again rinsed or washed out with a shampoo.

The benzofurazans of the formula I or their N-oxides and the compounds of the Com Component B can either be applied to the hair at the same time or else one after the other, regardless of which of the two components comes first is applied. The optionally contained ammonium or metal salts can the first or the second component can be added. Between applying the The first and second components can be up to 30 minutes apart. Even a pretreatment of the fibers with the salt solution is possible.

The benzofurazans of the formula I or their N-oxides and the compounds of the Com Component B can either be stored separately or together, either in one liquid to pasty preparation (aqueous or anhydrous) or as a dry powder. If the components are stored together in a liquid preparation, they should these must be largely anhydrous in order to reduce a reaction of the components. at The reactive components are only immediately before the separate storage Application intimately mixed with one another. When stored in a dry place, the Usually a defined amount of warm (30 to 80 ° C) water is used added and a homogeneous mixture made.

Examples Preparation of a staining solution

In each case, a suspension of 5 mmol of a benzofurazan of the formula I, optionally 5 mmol of an oxidation dye precursor of component B and 5 mmol Sodium acetate and one drop of a 20% fatty alkyl ether sulfate solution in 50 ml Water produced at 50 ° C. The slurries were after cooling to 30 ° C mixed with each other and with dilute NaOH or hydrochloric acid to a pH value of 9 set.

In this dye mixture, a tress turned 90% gray at 30 ° C for 30 minutes, Introduced human hair that has not been pretreated. The tress was then used for 30 sec Rinsed with lukewarm water, dried with warm air and then combed out.

The respective color nuances and depths of color are shown in Table 1 below given.

The color depth was rated according to the following scale:

-: no or very pale coloration (+): weak intensity +: medium intensity + (+): medium to strong intensity ++: strong intensity ++ (+): strong to very strong intensity +++: very strong intensity

Table 1

Coloration with 7-chloro-5-nitrobenzofurazan

Claims (13)

1. Agent for coloring keratin-containing fibers, in particular human hair, containing at least one benzofurazan with the formula I or its N-oxide as the coloring component,
in the
R ^{1 is} a hydrogen atom or a halogen atom,
R ^{2 is} a hydrogen atom, a nitro, sulfo, sulfonate or sulfonamide group in which the nitrogen _{can be substituted by C 1-4} alkyl or hydroxyalkyl groups, which together with the nitrogen atom can also form a heterocyclic ring,
R ³ and R ^{4 represent} a hydrogen, halogen atom, a C _1-4 -alkyl, C _1-4 -alkoxy or hydroxy-C _1-4 -alkyl group, a hydroxy, nitro, amino group which is represented by C _{1 -4} alkyl groups can be substituted, or C _1-4 acyl groups, both of which can also jointly form a fused aromatic ring, with the proviso that at least one of the radicals R ¹ to R ^{4 is} a halogen atom. 2. Means according to claim 1, characterized in that as connections with the Formula I 7-chloro-4-nitrobenzofurazan, 7-fluoro-4-nitrobenzofurazan, 7-chloro benzofurazan-4-sulfonic acid, ammonium salt, 7-fluoro-benzofurazan-4-sulfonic acid, Ammonium salt, 7-chloro-benzofurazan-4-sulfonamide, 7-chloro-4-morpholinosulfonyl-, 7-chloro-4-dimethylaminosulfonyl-, 7-fluoro-4-dimethylaminosulfonylbenzofurazan, 5-fluoro-benzofuroxan, 5-chloro-benzofuroxan, 7-chloro-benzofuroxan, 4,6-dichlorobenzo furoxan, 5-chlorobenzofurazan and any mixtures thereof can be used. 3. Agent according to one of claims 1 to 2, characterized in that the Benzofurazans of the formula I or their N-oxides in an amount of 0.03 to 65 mmol, in particular from 1 to 40 mmol, based on 100 g of the total dye tels, are included. 4. Agent according to one of claims 1 to 3, characterized in that there is additional Lich at least one compound with a primary or secondary amino group or Hydroxyl group selected from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds compounds, amino acids, oligopeptides constructed from 2 to 9 amino acids and / or contains at least one CH-active compound. 5. Agent according to claim 4, characterized in that the further compound is selected from
primary or secondary amines from the group consisting of N- (2-Hydroxye thyl) -N-ethyl-, N- (2-methoxyethyl-), 2,3-, 2,4-, 2,5-dichloro-p -phenylenediamine, 2-chloro-p-phenylenediamine, N, N-bis- (2-hydroxyethyl) -p-phenylenediamine, 2,5-dihydroxy-4-morpholinoaniline dihydrobromide, 2-, 3-, 4-aminophenol, o-, m-, p-phenylenediamine, 2,4-diaminophenoxyethanol, 2- (2,5-diaminophenyl) -ethanol, 2,5-diaminotoluene, -phenol, -phenethol, 4-methylamino-, 3-amino-4 - (2'-hydroxyethyloxy), 3,4-methylenediamino, 3,4-methylenedioxyaniline, 3-amino-2,4-dichloro, 4-methylamino, 2-methyl-5-amino, 3-methyl -4-amino-, 2-methyl-5- (2-hydroxyethylamino) -, 2-methyl-5-amino-4-chloro-, 6-methyl-3-amino-2-chloro-, 5- (2- Hydroxyethylamino) -4-methoxy-2-methyl-, 4-amino-2-aminomethylphenol, 2-hydroxymethyl-4-aminophenol, 2-diethylaminomethyl-4-aminophenol, 2-dimethylaminomethyl-4-aminophenol, 2,6-dichloro 4-aminophenol, 1,3-diamino-2,4-dimethoxybenzene, 2-, 3-, 4-aminobenzoic acid, -phenylacetic acid, 2,3-, 2,4-, 2,5-, 3,4-, 3 , 5-diami Nobenzoic acid, 4-, 5-aminosalicylic acid, 3-amino-4-hydroxy-, 4-amino-3-hydroxybenzoic acid, 2-, 3-, 4-aminobenzenesulfonic acid, 3-amino-4-hydroxybenzenesulfonic acid, 4-amino-3 hydroxynaphthalene sulfonic acid, 6-amino-7-hydroxynaphthalene-2-sulfonic acid, 7-amino-4-hydroxynaphthalene-2-sulfonic acid, 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid, 3-amino-2-naphthoic acid , 3-Amino phthalic acid, 5-aminoisophthalic acid, 1,3,5-, 1,2,4-triaminobenzene, 1,2,4,5-tetraami nobenzene tetrahydrochloride, 2,4,5-triaminophenol trihydrochloride, pentaaminobenzene pentahydrochloride , Hexaaminobenzene hexahydrochloride, 2,4,6-triaminoresorcinol trihydrochloride, 4,5-diaminobenzcatechol sulfate, 4,6-diaminopyrogallol dihydrochloride, 3,5-diamino-4-hydroxypyrocatechol sulfate, aromatic nitriles, amino compounds containing nitro groups, such as 3-amino-6-methylamino-2-nitro-pyridine, picric acid, 1- (2 (3) -nitro-4-amino) -phenylazo-2-hydroxy-7-trimethylammoniumnaphthalene chloride, 1-hydroxy-2- amino-4,6-dinitro-benzene, 1-amino-2-nitro-4 -bis- (2-hydroxyethyl) -amino benzene, 1-amino-2- (2-hydroxyethyl) -amino-5-nitro-benzene (HC Yellow No. 5), 1-amino-2-nitro-4- ( 2-hydroxyethyl) aminobenzene (HC Red No. 7), 2-chloro-5-nitro-N-hydroxyethyl-1,4-phenylenediamine, 1- (2-hydroxyethyl) -amino-2-nitro-4-amino -benzene (HC Red No. 3), 4-amino-3-nitrophenol, 4-amino-2-nitrophenol, 6-nitro-o-toluidine, 1- amino-3-methyl-4- (2-hydroxyethyl) - amino-6-nitrobenzene (HC Violet No. 1), 1-amino-2-nitro-4- (2,3-dihydroxypropyl) amino-5-chlorobenzene an (HC Red No. 10), 4-amino 2-ni trodiphenylamino-2'-carboxylic acid (2- (4-amino-2-nitroanilino) -benzoic acid), 6-nitro-2,5-diaminopyridine, 2-amino-6-chloro-4-nitrophenol, 2-amino -6-chloro-4-nitro phenol, 1-amino-2- (3-nitrophenylazo) -7-phenylazo-8-naphthol-3,6-disulfonic acid, disodium salt (Acid blue No. 29), 1-amino-2 - (2-hydroxy-4-nitrophenylazo) -8-naphthol-3,6-disulfonic acid, disodium salt (Palatinchrome green), 1-amino-2- (3-chloro-2-hydroxy-5-nitrophenylazo) -8-naphthol -3,6-disulfonic acid, disodium salt (gallion ), 4-Amino-4'-nitrostilbene-2,2'-disulfonic acid, disodium salt, 2,4-diamino-3 ', 5'-dinitro-2'-hydroxy-5-methyl-azobenzene (Mordant brown 4) , 4'-Amino-4-nitrodiphenylamine-2-sulfonic acid, 4'-Amino-3'-nitrobenzophenone-2-carboxylic acid, 1-Amino-4-nitro-2- (2-nitrobenzylideneamino) -benzene, 2- [2 - (Diethylamino) ethylamino] -5-nitroaniline, 3-amino-4-hydroxy-5-nitrobenzenesulfonic acid, (hydrate), 3-amino-3'-nitrobiphenyl, 3-amino-4-nitro-acenaphthene, 2-amino -1-nitronaphthalene, 5-amino-6-nitrobenzo-1,3-dioxole, anilines, in particular anilines containing nitro groups, such as 4-nitroaniline, 2-nitroaniline, 1,4-diamino-2-nitrobenzene, 1,2- Diamino-4-nitrobenzene, 1-amino-2-methyl-6-nitrobenzene, 4-nitro-1,3-phenylenediamine, 2-nitro-4-amino-1- (2-hydroxyethylamino) benzene, 2-nitro 1- amino-4- [bis- (2-hydroxyethyl) -amino] -benzene, 4-amino-2-nitrodiphenylamine-2'-carboxylic acid, 2-amino-6-chloro-4-nitrophenol, 1-amino- 5-chloro-4- (2-hydroyethylamino) -2-nitrobenzene, anilines, in particular anilines containing nitro groups, such as 4-nitroaniline , 2-nitroaniline, 1,4-diamino-2-nitrobenzene, 1,2-diamino-4-nitrobenzene, 1-amino-2-methyl-6-nitrobenzene, 4-nitro-1,3-phenylenediamine, 2-nitro -4-amino-1- (2-hydroxyethylamino) benzene, 2-nitro-1-amino-4- [bis- (2-hydroxyethyl) -amino] -benzene, 4-amino-2-nitrodiphenylamine-2'- carboxylic acid, 2-amino-6-chloro-4-nitrophenol, 1-amino-5-chloro-4- (2-hydroyethylamino) -2-nitrobenzene, aromatic anilines or phenols with a further aromatic radical such as 4,4 ' -Diaminostilbene dihydrochloride, 4,4'-diaminostilbene-2,2'-disulfonic acid, Na salt, 4,4'-diaminodiphenylmethane, sulfide, sulfoxide, amine, 4,4'-diaminodiphenylamine-2-sulfonic acid, 4,4'-diaminobenzophenone, -diphenylether, 3,3 ', 4,4'-tetraaminodiphenyl-tetrahydrochloride, 3,3', 4,4'-tetraamino-benzophenone, 1,3-bis- (2,4-diaminophenoxy ) propane tetrahydrochloride, 1,8-bis (2,5-diaminophen oxy) -3,6-dioxaoctane tetrahydrochloride, 1,3-bis (4-aminophenylamino) propane, -2-propanol, 1 , 3-bis- [N- (4-aminophenyl) -2-hydroxyethylamino] -2-propanol, N, N-bis- [2- (4-aminopheno xy) -ethyl] methylamine trihydrochloride,
nitrogen-containing heterocyclic compounds selected from the group consisting of 2-, 3-, 4-amino, 2-amino-3-hydroxy, 2,6-diamino, 2,5-diamino, 2,3-dia mino-, 2-dimethylamino-5-amino, 3-amino-2-methylamino-6-methoxy, 2,3-diamino-6-methoxy, 3,5-diamino-2,6-dimethoxy, 2 , 4,5-triamino-, 2,6-dihydroxy-3,4-dimethylpyridine, 4,5,6-triamino-, 2-hydroxy-4,5,6-triamino-, 4-hydroxy-2,5 , 6-triamino, 2,4,5,6-tetraamino, 2-methylamino-4,5,6-triamino, 2,4-, 4,5-diamino, 2-amino-4-methoxy 6-methyl-pyrimidine, 2,3,4-trimethylpyrrole, 2,4-dimethyl-3-ethyl-pyrrole, 3,5-diaminopyrazole, -1,2,4-triazole, 3-amino, 3-amino 5-hydroxypyrazole, 2-, 3-, 8-amino quinoline, 4-amino quinaldine, 2-, 6-aminonicotinic acid, 5-aminoisoquinoline, 5-, 6-amino indazole, 5-, 7-aminobenzimidazole, -benzothiazole, 2, 5-dihydroxy-4-morpholinoaniline and indole and indoline derivatives such as 4-, 5-, 6-, 7-aminoindole, 4-, 5-, 6-, 7-hydroxy indole, 5,6-dihydroxyindole, 5,6 -Dihydroxyindoline, 4-hydroxyindoline and those in DE-U1-299 08 573 disclosed hydroxypyrimidines, and in each case from the physiologically compatible salts of these compounds formed with preferably inorganic acids,
aromatic hydroxy compounds selected from the group consisting of 2-, 4-, 5-methylresorcinol, 2,5-dimethylresorcinol, resorcinol, 3-methoxyphenol, pyrocate quin, hydroquinone, pyrogallol, phloroglucinol, hydroxyhydroquinone, 2-, 3-, 4- Methoxy, 3-dimethylamino, 2- (2-hydroxyethyl) -, 3,4-methylenedioxyphenol, 2,4-, 3,4-dihydroxybenzoic acid, phenylacetic acid, gallic acid, 2,4,6-trihydroxybenzoic acid, acetic acid tophenon, 2-, 4-chlororesorcinol, 1-naphthol, 1,5-, 2,3-, 2,7-dihydroxynaphthalene, 6-dimethylamino-4-hydroxy-2-naphthalenesulfonic acid, 3,6-dihydroxy-2,7 -naphthalene sulfonic acid,
Amino acids selected from the group arginine, histidine, tyrosine, phenylalanine, DOPA (dihydroxyphenylalanine), ornithine, lysine and tryptophan,
Oligopeptide selected from glutathione or the oligopeptides contained in the hydrolysates of collagen, keratin, casein, elastin, soy protein, wheat gluten or almond protein
CH-active compounds selected from the group consisting of 1,2,3,3-tetramethyl-3H-indolium iodide, 1,2,3,3-tetramethyl-3H-indolium-p-toluenesulfonate, 1,2,3,3 -Tetramethyl-3H-indolium-methanesulphonate, Fischersche Base (1,3,3-trimethyl-2-methyleneindoline), 2,3-dimethyl-benzothiazolium iodide, 2,3-dimethyl-benzothiazolium-p-toluenesulphonate, 1,2- Dimethylnaphtho [1,2-d] thiazolium-p-toluenesulfonate, 1-ethyl-2-methyl-naphtho [1,2-d] thiazolium-p-toluenesulfonate, rhodanine, rhodanine-3-acetic acid, 1-ethyl-2- quinaldinium iodide, 1,4-dimethylquinolinium iodide, 1-methyl-2-quinaldinium iodide, 1,4-dimethylquinolinium iodide, barbituric acid, thiobarbituric acid, 1,3-dimethyl thiobarbituric acid, 1,3-diethylthiobarbituric acid, diethylthiobindarbituric acid , 3-indoxylacetate, coumaranone and 1-methyl-3-phenyl-2-pyrazolinone. 6. Means according to claim 5, characterized in that the further connection consists of is selected from the group consisting of N- (2-hydroxyethyl) -N-ethyl-, 2-chloro-p-phenylenediamine, N, N-bis- (2-hydroxyethyl) -p-phenylenediamine, 4-aminophenol, p-phenylenediamine, 2- (2,5-diaminophenyl) ethanol, 2,5-diaminotoluene, 3,4-methylenedi oxyaniline, 2-amino-4- (2-hydroxyethylamino) anisole, 2- (2,4-diaminophenoxy) ethanol, 3-amino-2,4-dichloro, 2-methyl-5-amino-, 3-methyl-4-amino-, 2-methyl-5- (2-hydro xyethylamino), 2-methyl-5-amino-4-chloro, 6-methyl-3-amino-2-chloro, 2-amin atoms ethyl-4-aminophenol, 2-diethylaminomethyl-4-aminophenol, 2-dimethylaminomethyl-4- aminophenol, 2,6-dichloro-4-aminophenol, 2-hydroxymethyl-4-aminophenol, 3,4-methylenedioxyphenol, 3,4-diaminobenzoic acid, 2,5-diamino-, 2-dimethylamino-5- amino, 3-amino-2-methylamino-6-methoxy, 2,3-diamino-6-methoxy, 3,5-diamino 2,6-dimethoxy-, 2,6-dihydroxy-3,4-dimethylpyridine, 2-hydroxy-4,5,6-triamino-, 4-Hy hydroxy-2,5,6-triamino-, 2,4,5,6-tetraamino-, 2-methylamino-4,5,6-triamino-pyrimidine, 3,5-diaminopyrazole, 3-amino-5-hydroxypyrazole, 5,6-dihydroxyindole and 5,6-dihy droxyindoline, β-alanine, L-proline, L-lysine, DL-tyrosine and each of the preferred physiologically compatible salts of these formed wisely with inorganic acids Links. 7. Agent according to one of claims 1 to 6, characterized in that it Color enhancer selected from the group consisting of piperidine, piperidine-2-car bonic acid, piperidine-3-carboxylic acid, piperidine-4-carboxylic acid, pyridine, 2-hydroxypyri din, 3-hydroxypyridine, 4-hydroxypyridine, imidazole, 1-methylimidazole, histidine, pyrroli din, proline, pyrrolidone, pyrrolidone-5-carboxylic acid, pyrazole, 1,2,4-triazole, piperazidine or any mixtures thereof. 8. Agent according to one of claims 1 to 7, characterized in that it is directly pulling dyes from the group of nitrophenylenediamines, nitroaminophenols, Anthraquinones or indophenols preferably in an amount from 0.01 to 20% by weight, based on the total colorant. 9. Agent according to one of claims 1 to 8, characterized in that ammo nium or metal salts selected from the group of formates, carbonates, halo genides, sulfates, butyrates, valemates, capronates, acetates, lactates, glycolates, tartrates, Citrates, gluconates, propionates, phosphates and phosphonates of alkali metals such as Potassium, sodium or lithium, alkaline earth metals such as magnesium, calcium, strontium or barium, or of aluminum, manganese, iron, cobalt, copper or zinc, added be practiced. 10. Agent according to one of claims 1 to 9, characterized in that it contains oxidizing agents, in particular H ₂ O ₂ , in an amount of 0.01 to 6% by weight, based on the application solution. 11. Agent according to one of claims 1 to 10, characterized in that it contains anionic, zwitterionic or nonionic surfactants. 12. Use of benzofurazans with the formula I or their N-oxides,
in the
R ^{1 is} a hydrogen atom or a halogen atom,
R ^{2 is} a hydrogen atom, a nitro, sulfo, sulfonate or sulfonamide group in which the nitrogen _{can be substituted by C 1-4} alkyl or hydroxyalkyl groups, which together with the nitrogen atom can also form a heterocyclic ring,
R ₃ and R ^{4 represent} a hydrogen, halogen atom, a C _1-4 -alkyl, C _1-4 -alkoxy or hydroxy-C _1-4 -alkyl group, a hydroxy, nitro, amino group which is represented by C _{1 -4} -alkyl groups can be substituted, or C _1-4 -acyl groups, both of which can jointly form a fused aromatic ring, with the proviso that at least one of the radicals R ¹ to R ^{4 is} a halogen atom,
as a coloring component in oxidation hair dyes. 13. A method for dyeing keratin-containing fibers, in particular human hair, wherein a dye containing

• A) at least one benzofurazan with the formula I or its N-oxide
  in the
  R ^{1 is} a hydrogen atom or a halogen atom,
  R ^{2 is} a hydrogen atom, a nitro, sulfo, sulfonate or sulfonamide group in which the nitrogen _{can be substituted by C 1-4} alkyl or hydroxyalkyl groups, which together with the nitrogen atom can also form a heterocyclic ring,
  R ³ and R ^{4 represent} a hydrogen, halogen atom, a C _1-4 -alkyl, C _1-4 -alkoxy or hydroxy-C _1-4 -alkyl group, a hydroxy, nitro, amino group which is represented by C _{1 -4} -alkyl groups can be substituted, or C _1-4 -acyl groups, both of which can jointly form a fused aromatic ring, with the proviso that at least one of the radicals R ¹ to R ^{4 is} a halogen atom,
  and
• B) at least one compound with a primary or secondary amino group or hydroxy group selected from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds, amino acids, oligopeptides made up of 2 to 9 amino acids and / or at least one CH-active compound,

and customary cosmetic ingredients, applied to the keratin-containing fibers, left on the fibers for some time, usually about 30 minutes, and then rinsed out again or washed out with a shampoo.