WO2000038636A1

WO2000038636A1 - Agent for dying keratin fibers

Info

Publication number: WO2000038636A1
Application number: PCT/EP1999/009998
Authority: WO
Inventors: Hinrich Möller; Doris Oberkobusch; Horst Höffkes
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1998-12-23
Filing date: 1999-12-16
Publication date: 2000-07-06
Also published as: DE19859723A1; AU1980600A

Abstract

The invention relates to an agent for dying keratin fibers, especially human hair, containing; A) nitroisatins with formula (I), in which R1 represents hydrogen, a C¿1?-C4-alkyl group, C1-C4-alkenyl group, C1-C4-alkoxy group, hydroxy-C1-C4-alkyl group, amino-C1-C4-alkyl group, which can be substituted on the nitrogen, an optionally substituted aryl-C1-C4-alkyl group; R?2 and R3¿ represent hydrogen, halogen, C¿1?-C14-alkyl group, C1-C4-alkenyl group, C1-C4-alkoxy group, hydroxy-C1-C4-alkyl group, a hydroxy group, carboxy group, sulfo group, nitro group or amino group, which can be substituted by one or two C1-C4-alkyl group(s), or a C1-C4-acyl group, whereby two of the radicals, together, can also form a fused, aromatic ring; and B) at least one compound selected from compounds with a primary or secondary amino group or hydroxy group, selected from primary or secondary aliphatic or aromatic amines, nitrogenous, heterocyclic compounds, amino acids, oligopeptides constructed from 2 to 9 amino acids and aromatic hydroxy compounds, and/or from CH-active compounds.

Description

"Means for dyeing fibers containing keratin"

The invention relates to an agent for dyeing keratin-containing fibers, in particular human hair, which contains nitroisatine in combination with oxidation dye precursors, the use of this combination as a coloring system in hair dye compositions and a process for dyeing keratin-containing fibers, in particular human hair.

For dyeing keratin fibers, e.g. B. hair, wool or fur, generally either direct dyes or oxidation dyes, which are formed by oxidative coupling of one or more developer components with one another or with one or more coupler components, are used. Coupler and developer components are also referred to as oxidation dye precursors.

Primary aromatic amines with a further free or substituted hydroxy or amino group in the para or ortho position, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazoIone derivatives and 2,4,5,6-tetraaminopyrimidine and their derivatives are usually used as developer components.

Specific representatives are, for example, p-phenylenediamine, p-toluenediamine, 2,4,5,6-tetraaminopyrimidine, p-aminophenol, N, N-bis- (2-hydroxyethyl) -p-phenylenediamine, 2- (2.5 -Diaminophenyl) -ethanol, 2- (2,5-diaminophenoxy) -ethanol, 1-phenyl-3-carboxyamido-4-amino-pyrazolon-5, 4-amino-3-methylphenol, 2-amino-methyl-4- aminophenol, 2-hydroxymethyl-4-aminophenol, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6-triamino-4-hydroxypyrimidine. M-Phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones, m-aminophenols and substituted pyridine derivatives are generally used as coupler components. 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, m-phenylenediamine, 2,4-diaminophenoxyethanol , 2-Amino-4- (2-hydroxyethylamino) anisole (Lehmanns Blau), 1-phenyl-3-methyl-pyrazolon-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 conventional dye components, reference is expressly made to the "Dermatology" series, edited by Ch. Culnan, H. Maibach, Marcel Dekker Inc., New York, Basel, 1986, Vol. 7, Ch. Zviak, The Science of Hair Care, Cape. 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 the European Commission, available in disk form from the Federal Association of German Industrial and Commercial Enterprises for Medicines, Health Care Products and Personal Care Products, Mannheim .

With oxidation dyes intensive dyeings can be achieved with good fastness properties, but the development of the color is usually done under the influence of oxidizing agents such. 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 gentler conditions, but their disadvantage is that the dyeings often have inadequate fastness properties. The use of isatin in combination with oxidation dye precursors is known from the prior art. European patent application 497 697 describes a process for dyeing keratin-containing fibers, in which a combination of isatin and indole derivatives is used as the coloring component.

European patent applications 502 783 and 502 784 describe processes for dyeing keratin-containing fibers, in which a combination of isatin and pyridine derivatives or aniline derivatives are used as coloring components.

International patent application WO94 / 24988 discloses agents for dyeing keratin-containing fibers which, as the coloring component, contain isatin or any derivative according to the general formula shown in combination with certain primary aliphatic amines, heterocyclic aromatic compounds, aromatic carboxylic and sulfonic acids, aniline derivatives, Contain dianiline derivatives or amino sugars. However, the use of the nitroisatins described in more detail below in combination with oxidation dye precursors for dyeing fibers containing keratin is not explicitly described.

The object of the present invention is to provide colorants for keratin fibers, in particular human hair, which are qualitatively at least equivalent to the usual oxidation hair colorants in terms of color depth, gray coverage and fastness properties, but without necessarily relying on oxidizing agents such as e.g. B. H ₂ 0 _{2 to be} instructed. In addition, the colorants may have no or only a very low sensitization potential. Surprisingly, it has now been found that a combination of the nitroisatins and oxidation dye precursors shown in the formula I is particularly suitable for dyeing keratin-containing fibers, even in the absence of oxidizing agents. They result in colors with excellent brilliance and depth of color and lead to a wide range of shades. However, the use of oxidizing agents should not be excluded in principle. It was also found that the colorations are significantly more intense compared to the unsubstituted isatin.

The invention relates to an agent for dyeing keratin-containing fibers, in particular human hair, comprising A) nitroisatine with the formula I,

in which R ^{1 is} hydrogen, a CC ₄ -alkyl group, C ₁ -C ₄ -alkenyl group, CC ₄ -alkoxy group, hydroxy-C C ₄ -alkyl group, amino-C C ₄ -alkyl group, which can be substituted on nitrogen, a optionally substituted AryI-C C ₄ alkyl group, R ² and R ^{3 represent} hydrogen, halogen, CrC ^ alkyl group, C _r C ₄ alkenyl group, CC ₄ alkoxy group, hydroxy-C ₁ -C ₄ alkyl group, a hydroxyl, carboxy, sulfo, nitro or amino group, which can be substituted by one or two C ₁ -C ₄ alkyl group (s), or a C.-O, - acyl group, with two of the radicals can together form a fused aromatic ring, and B) at least one compound selected from compounds having a primary or secondary amino group or a hydroxy group selected from primary or secondary aliphatic or aromatic amines, nitrogen-containing heterocyclic compounds, amino acids, oligopeptides and aromatic hydroxy compounds composed of 2 to 9 amino acids, and / or CH-active compounds.

Keratin-containing fibers are wool, furs, feathers and in particular human hair. In principle, the colorants according to the invention can also be used for dyeing other natural fibers, such as, As 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, polyurethane and polyester fibers can be used.

The compounds having the formula I are preferably selected from the group of the following nitroisatins: 5-nitroisatin, 1-methyl-5-nitroisatin, 1-benzyl-5-nitroisatin, 1- (4-chlorobenzyl) -5-nitroisatin, 7-chlorine -5-nitroisatin, 5-chloro-7-nitroisatin, 5-bromo-5-nitroisatin, 5-methoxy-7-nitroisatin, 5,7-dinitroisatin, 6-nitroisatin and any mixtures thereof.

These substances are known from the literature or are commercially available.

The compounds of component B are, on the one hand, compounds which, on their own, only weakly dye keratin-containing fibers and only give brilliant colorations together with the nitroisatins of the formula I. On the other hand, there are also compounds that are already used as oxidation dye precursors.

The above-mentioned nitroisatins with the formula I and the compounds of component B are preferably used in the agents according to the invention in each case in an amount of 0.03 to 65 mmol, in particular from 1 to 40 mmol, based on 100 g of the total colorant. Coloring agents which contain a combination of nitroisatins with the formula I and the compounds of component B as the coloring component are preferably used for dyeings in the range of shades from reddish brown, brown red, brown orange, black brown, dark purple, blue violet to black.

Several different nitroisatins of the formula I can also be used together in all colorants; Likewise, several different compounds of component B can also be used together. The subject of the present invention also includes the use of such substances which are reaction products of nitroisatins of the formula I with the compounds of component B mentioned as direct colorants.

Suitable compounds with primary or secondary amino group as component B are e.g. B. primary aromatic amines such as N, N-dimethyl, N, N-diethyl, N- (2-hydroxyethyl) -N-ethyl, N, N-bis (2-hydroxyethyl) -, N- (2nd -Methoxye- ethyl-), 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-toluenediamine, 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'-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) -, 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-hydroxy-benzoic 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-triamino-benzene, 1, 2.4 , 5-tetraaminobenzene, 2,4,5-triaminophenol, pentaaminobenzene, hexaaminobenzene, 2,4,6-triaminoresorcinol, 4,5-diamino-catechol, 4,6-diaminopyrogallol, 3,5-diamino-4-hydroxy-catechol, aromatic Nitriles, anilines, in particular anilines containing nitro groups, such as 4-nitroaniline, 4-nitro-1,3-phenylenediamine, 2-nitro-4-amino-1- (2-hydroxyethylamino) benzene, 2-nitro-1-ami - no-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-hydroxyethylamino) -2-nitrobenzene, 4-amino-4 '- [bis- (2-hydroxyethyl) amino] - azobenzene, aromatic anilines or phenols with another aromatic Rest, as shown in Formula II

in which R ^{4 represents} a hydroxyl or an amino group which may be substituted by C _1-4 alkyl, C _1-4 hydroxy alkyl, C _1-4 alkoxy or C _1-4 alkoxy-C _1-4 alkyl groups ,

R ⁴ , R ⁶ , R ⁷ , R ⁸ and R ^{9 represent} hydrogen, a hydroxy or an amino group,

C ^ alkyl, C ^^ hydroxyalkyl, C ^^ alkoxy, C ^^ aminoalkyl or C ^ alkoxy-O, ^ - alkyl groups may be substituted, and

X for a direct bond, a saturated or unsaturated, possibly through

Hydroxy group-substituted carbon chain with 1 to 4 carbon atoms, 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 ') ₀ (III)

in which Y is a direct bond, a CH ₂ or CHOH group,

Z and Z 'independently of one another for an oxygen atom, an NR ¹⁰ group, wherein R ^{10 is} hydrogen, a C 1-4 alkyl or a hydroxy-C ,. ₄ - alkyl group means the group O- (CH ₂ ) _p -NH or NH- (CH ₂ ) _p '-O, where p and p' are 2 or 3, and o is a number from 1 to 4, such as for example 4,4'-diaminostilbene and its hydrochloride, 4,4'-diamino-stilbene-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, -diphenyl ether, 3,3 ', 4,4'-tetraaminodiphenyl, 3, 3 ', 4,4'-tetraamino-benzophenone, 1,3-bis (2,4-diaminophenoxy) propane, 1,8-bis (2,5-diaminophenoxy) -3,6-dioxaoctane, 1,1 3-bis- (4-aminophenylamino) propane, -2-propanol, 1,3-bis- [N- (4-aminophenyl) -2-hydroxyethylamino] -2-propanol, N, N-bis- [2- ( 4-aminophenoxy) ethyl] methylamine, N-phenyl-1,4-phenylenediamine.

The abovementioned compounds can be used both in free form and in the form of their physiologically tolerable salts, in particular as salts of inorganic acids, such as hydrochloric or sulfuric acid.

Suitable nitrogen-containing heterocyclic compounds are e.g. B. 2-, 3-, 4-amino, 2-amino-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-diamino-, 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-pyrimidine, 3,5-diaminopyrazole, -1, 2,4-triazole, 3-amino, 3-amino-5-hydroxypyrazole, 2-, 3-, 8-aminoquinoline, 4-aminoquinidine, 2-, 6-aminonicotinic acid, 5-aminoisoquinoline, 5- , 6-aminoindazole, 5-, 7-aminobenzimidazole, -benzothiazole, 2,5-dihydroxy-4-morpholinoaniline and indole and indoline derivatives, such as 4-, 5-, 6-, 7-aminoindole, 5,6-dihydroxyindole, 5,6-dihydroxyindoline and 4-hydroxyindoline. The aforementioned compounds can be used both in free form and in the form of their physiologically tolerable salts, e.g. B. as salts of inorganic acids such as hydrochloric or sulfuric acid.

Suitable aromatic hydroxy compounds are e.g. B. 2-, 4-, 5-methylresorcinol, 2,5-dimethylresorcinol, resorcinol, 3-methoxyphenol, pyrocatechol, hydroquinone, pyrogallol, phloroglucin, 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, -acetophenone, 2-, 4-chlororesorcinol , 1-naphthol, 1, 5-, 2,3-, 2,7-dihydroxynaphthalene, 6-dimethylamino-4-hydroxy-2-naphthalenesulfonic acid, 3,6-dihydroxy-2,7-naphthalenesulfonic acid.

Examples of CH-active compounds which may be mentioned are 1, 2,3,3-tetramethyl-3H-indolium iodide, 1, 2,3,3-tetramethyl-3H-indolium-p-toluenesulfonate, 1, 2,3,3-tetramethyl -3H-indolium methanesulfonate, Fischer's base (1,3,3-trimethyl-2-methyleneindoline), 2,3-dimethyl-benzothiazolium iodide, 2,3-dimethyl-benzothiazolium-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-diethylthibarbituric acid, diethylthiobarbituric acid , 3-indoxy acetate, coumaranone and 1-methyl-3-phenyl-2-pyrazoiinone.

Preferred amino acids are all naturally occurring and synthetic α-amino acids, e.g. B. by hydrolysis of vegetable or animal proteins, e.g. B. collagen, keratin, casein, elastin, soy protein, wheat gluten or almond protein, accessible amino acids. Both acidic and alkaline amino acids can be be set. 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 be used.

The oligopeptides can be naturally occurring or synthetic oligopeptides, but also the oligopeptides contained in polypeptide or protein hydrolyzates, provided that they have sufficient water solubility for use in the colorants according to the invention. As examples are e.g. B. Glutathione and the oligopeptides contained in the hydrolyzates of collagen, keratin, casein, elastin, soy protein, wheat gluten or almond protein. Agents which contain the compounds of the formula I together with compounds having a primary or secondary amino group or with aromatic hydroxy compounds are preferred.

The compounds of component B are particularly preferably 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-methylenedioxyaniline, 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-hydroxyethylamino) -, 2-methyl -5-amino-4-chloro, 6-methyl-3-amino-2-chloro, 2-aminomethyl-4-aminophenol, 2-hydroxymethyl-4-aminophenol, 3,4-methylenedioxyphenol, 3,4 -Diamino benzoic 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-hydroxy-pyrazole, 5,6-dihydroxyindole and 5,6-dihydroxyindoline as well as their physiologically compatible salts formed with preferably inorganic acids. On the presence of oxidizing agents, e.g. B. H ₂ O _2l can be omitted. However, it can It may be desirable to add hydrogen peroxide or other oxidizing agents to the agents according to the invention to achieve the shades which are lighter than the keratin-containing fiber to be colored. 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, in addition to the compounds contained according to the invention, customary direct dyes, for example, for further modification of the color shades. B. from the group of nitrophenylenediamines, 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 as picramic acid 2-amino-6-chloro-4-nitrophenol, 4-amino-2-nitrodiphe - nylamine-2'-carboxylic acid, 6-nitro-1, 2,3,4-tetrahydroquinoxaline, 4-N-ethyl-1, 4- bis (2'-hydroxyethylamino) -2-nitrobenzene hydrochloride and 1-methyl- 3-nitro-4- (2'-hydroxyethyl) aminobenzene. The agents according to the invention in accordance with this embodiment preferably contain the substantive dyes in an amount of 0.01 to 20% by weight, based on the total colorant.

Furthermore, the preparations according to the invention can also contain naturally occurring dyes such as, for example, henna red, henna neutral, henna black, chamomile flowers, sandalwood, black tea, rotten bark, sage, blue wood, madder root, catechu, sedre and alkanna root. It is not necessary that the oxidation dye precursors or the optional direct dyes each represent uniform compounds. Rather, in the colorants according to the invention, due to the production process for the individual dyes, further components may be present in minor amounts, provided that these do not adversely affect the coloring result or for other reasons, e.g. B. toxicological, must be excluded.

The colorants according to the invention produce intensive colorations even at physiologically tolerable temperatures of below 45 ° C. They are therefore particularly suitable for dyeing human hair. For use on human hair, the colorants can usually be incorporated into a water-containing cosmetic carrier. Suitable water-containing cosmetic carriers are e.g. B. creams, emulsions, gels or surfactant-containing foaming solutions such. B. shampoos or other preparations that are suitable for use on the keratin fibers. If necessary, it is also possible to incorporate the colorants into anhydrous carriers.

Furthermore, the colorants according to the invention can contain all active ingredients, additives and auxiliaries known in such preparations. In many cases, the colorants contain at least one surfactant, both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants being suitable in principle. In many cases, however, it has proven advantageous to select the surfactants from anionic, zwitterionic or 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),

Ether carboxylic acids of the formula R-0- (CH ₂ -CH ₂ O) _x -CH ₂ -COOH, in which R is a linear alkyl group with 10 to 22 C atoms and x = 0 or 1 to 16, acyl sarcosides with 10 to 18 C atoms in the acyl group, acyl taurides with 10 to 18 C atoms in the acyl group, acyl isethionates with 10 to 18 C atoms in the acyl group, sulfosuccinic acid and dialkyl esters with 8 to 18 C atoms in the alkyl group and sulfosuccinic acid mono-alkyl polyoxyethyl ester 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, methyl alpha-sulfofatty acid 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 0) _x - SO ₃ H, in which R is a preferably linear alkyl group with 10 to 18 C 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,

Sulfonates of unsaturated fatty acids with 12 to 24 carbon atoms and 1 to 6 double bonds 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 to fatty alcohols with 8 to 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 that contain 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 glycinate, for example the cocoalkyl-dimethylammonium glycinate, N-acyl-aminopropyl-N, N-dimethylammonium glycinate, for example the cocoacylaminopropyl-dimethylammonium glycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethyl-imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group, and also the cocoacylaminoethylhydroxyethylcarboxymethylglycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known under the CTFA name Cocamidopropyl Betaine.

Ampholytic surfactants are understood to mean those surface-active compounds which, in addition to a C ₈ . ₁₈ -alkyl or -acyl group in the molecule contain at least one free amino group and at least one -COOH or -S0 ₃ H group and are capable of forming internal salts. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylamino-butyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkyl sarcosines, 2-alkylaminopropionic acids and alkylamino acetic acids each about 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-coconut alkyl aminopropionate, coconut acylaminoethyl aminopropionate and C _12-18 acyl sarcosine. Nonionic surfactants contain z as a hydrophilic group. 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 with linear fatty alcohols with 8 to 22 carbon atoms, with fatty acids with 12 to 22 carbon atoms and with alkylphenols with 8 to 15 carbon atoms in the alkyl group,

C ₁₂ _ ₂₂ fatty acid monoesters and diesters of adducts of 1 to 30 moles of ethylene oxide with glycerol,

C ₈ . ₂₂ alkyl mono- and oligoglycosides and their ethoxylated analogues, addition products of 5 to 60 mol ethylene oxide onto castor oil and hardened castor oil,

Addition products of ethylene oxide with sorbitan fatty acid esters Addition products of ethylene oxide with fatty acid alkanolamides.

Examples of the cationic surfactants which can be used in the hair treatment compositions according to the invention are, in particular, quaternary ammonium compounds. Ammonium halides such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g. B. cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride. The quaternized protein hydrolyzates are further cationic surfactants which can be used according to the invention.

Also suitable according to the invention are cationic silicone oils such as, for example, the commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethylsilylamodimethicone), Dow Corning 929 emulsion (containing a hydroxylamino-modified silicone, which is also referred to as amodimethicone) , SM-2059 (manufacturer: General Electric), SLM-55067 (Manufacturer: Wacker) and Abil ^® -Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxanes, Quatemium-80).

In addition to a good conditioning effect, alkylamidoamines, especially fatty acid amidoamines such as the ^{stearylamidopropyldimethylamine} available under the name Tego Amid ^® S 18, are notable for their good biodegradability.

Also very good biodegradability are quaternary Esterverbindungen, so-called "esterquats", such as those sold under the trademark Stepantex ^® methylhydroxyalkyldialkoyloxyalkylammonium.

An example of a suitable cationic surfactant quaternary sugar derivative is the commercial product Glucquat ^® 100, according to CTFA nomenclature a "lauryl methyl Gluceth-10 Hydroxypropyl Dimonium Chloride".

The compounds with alkyl groups used as surfactants can each be uniform substances. However, it is generally preferred to start from natural vegetable or animal raw materials in the production of these substances, so that substance mixtures with different alkyl chain lengths depending on the respective raw material are obtained.

In the case of the surfactants, which are addition products of ethylene and / or propylene oxide onto fatty alcohols or derivatives of these addition products, both products with a "normal" homolog distribution and those with a narrowed homolog distribution can be used. “Normal” homolog distribution is understood to mean mixtures of homologues which are obtained as catalysts when fatty alcohol and alkylene oxide are reacted using alkali metals, alkali metal hydroxides or alkali metal alcoholates. By contrast, narrow homolog distributions are obtained if, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids, Alkaline earth metal oxides, hydroxides or alcoholates can be used as catalysts. The use of products with a narrow homolog distribution can be preferred.

Other active ingredients, auxiliaries and additives are, for example, nonionic polymers such as, for example, vinylpyrrolidoneΛ / inylacrylate copolymers, polyvinylpyrrolidone and vinylpyrrolidoneΛ / inylacetate copolymers and polysiloxanes, cationic polymers such as quaternized cellulose ethers, polysiloxanes with quaternary groups, dimethyldiallyl polymers, dimethyldiallyl -Dimethyldiallylammonium chloride copolymers, dimethylaminoethyl methacrylate-vinylpyrrolidone copolymers quaternized with diethyl sulfate,

Vinylpyrrolidone-imidazolinium methochloride copolymers and quaternized polyvinyl alcohol, zwitterionic and amphoteric polymers such as, for example, acrylamidopropyl trimethylammonium chloride / acrylate copolymers and octylacrylamide / methyl methacrylate / tert.-butylaminoethyl methacrylate / 2-hydroxypropyl acrylate polymers, for example polyacrylate, 2-hydroxypropyl acrylate polymers, cross-linked polyacrylic acids, vinyl acetate / crotonic acid copolymers, vinyl pyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and acrylic acid / ethyl acrylate / N-tert.-butylacrylamide terpolymers

Thickeners such as agar agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, linseed gums, dextrans, cellulose derivatives, e.g. As methyl cellulose, hydroxyalkyl cellulose and carboxymethyl cellulose, 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, for example soy lecithin, egg lecithin and cephalins, and silicone oils,

Protein hydrolyzates, in particular elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolyzates, their condensation products with fatty acids and quaternized protein hydrolyzates, perfume oils, dimethyl isosorbide and cyclodextrins,

Solubilizers such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerin and diethylene glycol,

Anti-dandruff agents such as piroctone olamine and zinc omadine, other substances for adjusting 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 generators such as sugar esters, polyol esters or polyol alkyl ethers, fats and waxes such as walrus, 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 glycerol, propylene glycol monoethyl ether, carbonates, hydrogen carbonates, guanidines, ureas and primary, secondary and tertiary phosphates, imidazoles, tannins, pyrrole, opacifiers such as latex,

Pearlescent agents such as ethylene glycol mono- and distearate, blowing agents such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air, and antioxidants.

The constituents of the water-containing carrier are used to produce the colorants according to the invention in amounts customary for this purpose; z. B. are emulsifiers in concentrations of 0.5 to 30 wt .-% and Thickeners are used in concentrations of 0.1 to 25% by weight of the total colorant.

For the coloring result it can be advantageous to add ammonium or metal salts to the coloring agents. Suitable metal salts are e.g. B. formates, carbonates, halides, sulfates, butyrates, valerates, 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 being preferred. These salts are preferably present in an amount of 0.03 to 65, in particular 1 to 40, mmol based on 100 g of the total colorant.

The pH of the ready-to-use coloring preparations is usually between 2 and 11, preferably between 5 and 9.

The present invention further relates to the use of A) one or more nitroisatins of the formula I,

in the R ¹ for hydrogen, a C _r C ₄ alkyl group, C ₁ -C ₄ alkenyl group, C _ϊ -C ^ alkoxy group, hydroxy-C C ₄ alkyl group, amino-C., - C ₄ - alkyl group, the can be substituted on the nitrogen, an optionally substituted aryl-C ₁ -C ₄ -alkyl group, R ² and R ^{3 are} hydrogen, halogen, C _r C ₄ alkyl group, C _r C 4

Alkenyl group, C ₁ -C ₄ alkoxy group, hydroxy-C ₁ -C ₄ alkyl group, a hydroxy, carboxy, sulfo, nitro or amino group, which can be substituted by one or two CC ₄ alkyl group (s) , or a C ^ C ^ acyl group, where two of the radicals together can form a fused aromatic ring, in combination with

B) at least one compound selected from compounds having a primary or secondary amino group or hydroxyl group, selected from primary or secondary aliphatic or aromatic amines, nitrogen-containing heterocyclic compounds, amino acids, oligopeptides and aromatic hydroxy compounds composed of 2 to 9 amino acids, and / or CH-active compounds , as a coloring component in hair dyes.

Yet another object of the present invention relates to a process for dyeing fibers containing keratin, in particular human hair, in which a colorant comprising A) at least one nitroisatin of the formula I,

in the R ¹ for hydrogen, a CC ₄ -alkyl group, C _r C ₄ -alkenyl group, CC ₄ -alkoxy group, hydroxy-C C ₄ -alkyl group, amino-C, - ^ - alkyl group, which may be substituted on the nitrogen, a optionally substituted aryl-C _r C ₄ -alkyl group, R ² and R ³ for hydrogen, halogen, CC ₄ alkyl group, CC ₄ alkenyl group, C _r C ₄ alkoxy group, hydroxy-C C ₄ alkyl group, a hydroxy, carboxy, sulfo, nitro or Amino group, which can be substituted by one or two C ₁ -C ₄ alkyl group (s), or a CC ₄ - acyl group, where two of the radicals together can form a fused aromatic ring, and B) at least one compound selected from Compounds with primary or secondary amino group or hydroxy group, selected from primary or secondary aliphatic or aromatic amines, nitrogen-containing heterocyclic compounds, amino acids, from 2 to 9 amino acids and oligopeptides and aromatic hydroxy compounds, and / or CH-active compounds, as well as usual cosmetic ingredients the keratin fibers applied, left on the fiber for some time, usually about 30 minutes, and then rinsed out again or with a shampoo is washed out.

The nitroisatins of the formula I and the compounds of component B can either be applied to the hair simultaneously or else in succession, it being irrelevant which of the two components is applied first. The optionally contained ammonium or metal salts can be added to the first or the second component. There may be an interval of up to 30 minutes between the application of the first and the second component. Pretreatment of the fibers with the saline solution is also possible.

The nitroisatins of formula I and the compounds of component B can either be stored separately or together, either in a liquid to pasty preparation (aqueous or anhydrous) or as a dry powder. If the components are stored together in a liquid preparation, this should largely reduce the reaction of the components be anhydrous. When stored separately, the reactive components are only intimately mixed with one another immediately before use. In dry storage, a defined amount of warm (30 to 80 ° C) water is usually added before use and a homogeneous mixture is produced.

Examples

Preparation of a coloring solution

A slurry of 5 mmol of nitroisatin with the formula I, 5 mmol of an oxidation dye precursor of component B and 5 mmol of sodium acetate and a drop of a 20% fatty alkyl ether sulfate solution in 50 ml of water at 60 ° C. were prepared. The slurries were mixed together at 30 ° C. and adjusted to a pH of 6 using dilute sodium hydroxide solution or hydrochloric acid.

A strand of 90% gray, untreated human hair was placed in this coloring solution at 30 ° C. for 30 minutes. The tress was then rinsed with lukewarm water for 30 seconds, dried with warm air and then combed out.

The respective color shades and color depths are shown in Table 1 below.

The color depth was rated on the following scale:

no or very pale color

(+) weak intensity

+ medium intensity

+ (+) medium to strong intensity

++ strong intensity

++ (+) strong to very strong intensity

+++ very strong intensity Table

Staining with 5-nitroisatin

Discolorations with 6-nitroisatin

Staining with 5,7-dinitroisatin

Claims

claims

1. Agent for dyeing keratin fibers, in particular human hair, containing as coloring component A) nitroisatins with the formula I,

in which R ^{1 is} hydrogen, a CC ₄ -alkyl group, CC ₄ -alkenyl group, C ₁ -C ₄ -alkoxy group, hydroxy-C ₁ -C ₄ -alkyl group, amino-C C ₄ -alkyl group which can be substituted on nitrogen, an optionally substituted aryl-C C ₄ alkyl group, R ² and R ³ is hydrogen, halogen, C _r C ₄ alkyl group, CC ₄ - alkenyl group, CC ₄ -alkoxy, hydroxy-C, -C ₄ alkyl group, a hydroxyl, carboxy, sulfo, nitro or amino group, which can be substituted by one or two CC ₄ alkyl group (s), or a C ^ C ^ acyl group, where two of the radicals together form a fused aromatic ring can form, and B) at least one compound selected from compounds having a primary or secondary amino group or hydroxy group, selected from primary or secondary aliphatic or aromatic amines, nitrogen-containing heterocyclic compounds, amino acids, oligopeptides composed of 2 to 9 amino acids and aromatic hydroxy compounds ungen, and / or CH-active compounds.

2. Composition according to claim 1, characterized in that as compounds with the formula I 5-nitroisatin, 1-methyl-5-nitroisatin, 1-benzyl-5-nitroisatin, 1- (4-chlorobenzyl) -5-nitroisatin, 7th Chlorine-5-nitroisatin, 5-chloro-7-nitroisatin, 5-bromo-5-nitroisatin, 5-methoxy-7-nitroisatin, 5,7-dinitroisatin, 6-nitroisatin and any mixtures thereof can be used.

3. Composition according to one of claims 1 to 2, characterized in that the nitroisatins with the formula I and the compounds of component B each in an amount of 0.03 to 65 mmol, in particular from 1 to 40 mmol, based on 100 g of the entire colorant are included.

4. Composition according to one of claims 1 to 3, characterized in that the compounds of component B are selected from primary or secondary amines from the group consisting of N- (2-hydroxyethyl) -N-ethyl-, N- (2nd -Methoxyethyl-), 2,3-, 2,4-, 2,5-dichloro-p-phenylene diamine, 2-chloro-p-phenylene diamine, N, N-bis (2-hydroxyethyl) -p-phenylene diamine , 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, 4-amino-2 - hydroxymethyl-phenol, 1, 3-diamino-2,4-dimethoxybenzene, 2-, 3-, 4-aminobenzoic acid, -phenyless acetic acid, 2,3-, 2,4-, 2,5-, 3,4-, 3,5-diaminobenzoic acid, 4-, 5-aminosalicylic acid, 3-amino-4-hydroxy-, 4-amino- 3-hydroxy-benzoic 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-aminophthalic acid, 5-aminoisophthalic acid, 1, 3,5-, 1, 2,4-triaminobenzene, 1, 2,4,5-tetraaminobenzene-tetrahydrochloride, 2,4,5-triamino-phenol-trihydrochloride, pentaaminobenzene pentahydrochloride,

Hexaaminobenzene hexahydrochloride, 2,4,6-triaminoresorcinol trihydrochloride, 4,5-diaminobenzene catechol sulfate, 4,6-diaminopyrogallol dihydrochloride, 3,5-diamino-4-hydroxybenzate catechol sulfate, aromatic nitriles, anilines, in particular nitro group-containing anilines such as 4-nitroaniline, 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-hydroxyethylamino) -2 -nitrobenzoI, 4-amino-4 '- [bis- (2-hydroxyethyl) amino] - azobenzene, aromatic anilines or phenols with a further aromatic radical such as 4,4'-diaminostilbene dihydrochloride, 4,4'-diamino style ben-2,2'-disulfonic acid, Na salt, 4,4'-diaminodiphenylmethane, sulfide, sulfoxide, amine, 4,4'-diaminodiphenylamine-2-sulfonic acid, 4,4'-diamino-benzophenone, -diphenyl ether, 3,3 \ 4,4'-tetraaminodiphenyl tetrahydrochloride, 3,3 ', 4,4'-tetraamino-benzophenone, 1,3-bis- (2,4-diami nophenoxy) propane tetrahydrochloride, 1,8-bis (2,5-diaminophenoxy) -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-aminophenoxy) -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-diamino, 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-me- thyl-pyrimidine, 2,3,4-trimethylpyrrole, 2,4-dimethyl-3-ethyl-pyrrole, 3,5-diamino-pyrazole, -1, 2,4-triazole, 3-amino-, 3-amino- 5-hydroxypyrazole, 2-, 3-, 8-aminoquinoline, 4-amino-quinaldine, 2-, 6-aminonicotinic acid, 5- Aminoisoquinoline, 5-, 6-aminoindazole, 5-, 7-amino-benzimidazole, -benzo-thiazole, 2,5-dihydroxy-4-morpholinoaniline as well as indole and indoline derivatives, such as 4-, 5-, 6-, 7- Aminoindole, 4-, 5-, 6-, 7-hydroxyindole, 5,6-dihydroxyindole, 5,6-dihydroxyindoline and 4-hydroxyindoline, and in each case selected from the physiologically tolerable salts of these compounds formed with preferably inorganic acids, aromatic hydroxy compounds the group consisting of 2-, 4-, 5-methylresorcinol, 2,5-dimethylresorcinol, resorcinol, 3-methoxyphenol, pyrocatechol, hydroquinone, pyrogallol, phloroglucin, 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, -acetophenone, 2-, 4-chlororesorcinol, 1-naphthol, 1, 5-, 2,3-, 2,7-dihydroxynaphthalene, 6-dimethylamino-4-hydroxy-2-naphthalenesulfonic acid, 3,6-dihydroxy-2,7-naphthalenesulfonic acid, and

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 methanesulfonate, Fischer's base (1,3,3-trimethyl-2-methyleneindoline), 2,3-dimethyl-benzothiazolium iodide, 2,3-dimethyl-benzothiazolium-p-toluenesulfonate, rhodanine, rhodanine-3 -esacetic 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-indoxy acetate, coumaranone and 1-methyl-3-phenyl-2-pyrazolinone.

5. Composition according to claim 4, characterized in that the compounds of component B are 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-methylenedioxyaniline, 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-hydroxyoxyamino) -, 2-methyl-5-amino-4-chloro, 6 -Methyl-3-amino-2-chloro, 2-aminomethyl-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-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-dihydroxyindoline and in each case from the physiologically tolerable salts of these compounds which are preferably formed with inorganic acids.

6. Composition according to one of claims 1 to 5, characterized in that there are direct dyes from the group of nitrophenylenediamines, nitro-aminophenols, anthraquinones or indophenols, preferably in an amount of 0.01 to 20 wt .-%, based on the entire colorant.

7. Composition according to one of claims 1 to 6, characterized in that ammonium or metal salts selected from the group of formates, carbonates, halides, sulfates, butyrates, valerates, 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.

8. Agent according to one of claims 1 to 7, characterized in that it contains oxidizing agents, in particular H ₂ O ₂ , in an amount of 0.01 to 6 wt .-%, based on the application solution.

9. Composition according to one of claims 1 to 8, characterized in that it contains anionic, zwitterionic or nonionic surfactants.

10. Use of a combination of A) nitroisatins with the formula I,

in the R ¹ for hydrogen, a C _r C ₄ alkyl group, CrO _t alkenyl group, C | -C ₄ alkoxy group, hydroxy-C _r C ₄ alkyl group, amino-C _r C ₄ alkyl group which is substituted on nitrogen may be an optionally substituted aryl-C C ₄ alkyl group, R ² and R ³ is hydrogen, halogen, C _r C ₄ alkyl group, C _r C ₄ - alkenyl, C _r C ₄ alkoxy group, hydroxy-C C ₄ alkyl group, a hydroxy, carboxy, sulfo, nitro or amino group, which can be substituted by one or two CC ₄ alkyl group (s), or a C _r C ₄ acyl group, where two of the Residues can together form a fused aromatic ring, and B) at least one compound selected from compounds having a primary or secondary amino group or hydroxyl group, selected from primary or secondary aliphatic or aromatic amines, nitrogen-containing heterocyclic compounds, amino acids, oligopeptides composed of 2 to 9 amino acids and aromatis Chen hydroxy compounds, and / or CH-active compounds, as a coloring component in hair dyes.

1. A process for dyeing keratin-containing fibers, in particular human hair, in which a colorant comprising A) nitroisatine with the formula I,

in the R ¹ for hydrogen, a C, -C ₄ alkyl group, C, -C ₄ alkenyl group, CC ₄ alkoxy group, hydroxy-C ^ C ^ alkyl group, amino-C _r C ₄ - alkyl group, which is substituted on nitrogen can be an optionally substituted aryl-C ^ C ^ alkyl group, R ² and R ^{3 are} hydrogen, halogen, CC ₄ -alkyl group, C _r C ₄ - alkenyl group, CC ₄ -alkoxy group, hydroxy-C, -C ₄ alkyl group, a hydroxyl, carboxy, sulfo, nitro or amino group, which can be substituted by one or two C ₁ -C ₄ -alkyl group (s), or a C, -C ₄ -acyl group, where also two of the radicals can together form a fused aromatic ring, and B) at least one compound with primary or secondary amino group or hydroxy group selected from primary or secondary aliphatic or aromatic amines, nitrogen-containing heterocyclic compounds, amino acids, from 2 to 9 amino acids built oligopeptides and aromatic Hydroxy compounds, and / or at least ens a CH-active compound, as well as usual cosmetic ingredients, applied to the keratin fibers, left on the fiber for some time, usually about 30 minutes, and then rinsed out or washed out with a shampoo.