DE19932566A1 - Agent for dyeing keratin fibers - Google Patents

Abstract

The invention relates to an agent for dyeing keratin fibres, especially human hair, containing at least one aromatic nitroso compound of formula (I), wherein R<1>, R<2>, R<3> and R<4> can each represent, independently of each other: a hydrogen or halogen atom, a C1-C4-alkyl group, C1-C4-alkoxy group or hydroxy-C1-C4-alkoxy group, a hydroxy group, sulfo group, carboxy group or amino group that can be substituted by C1-C<4>-alkyl, hydroxy-C1-C4-alkyl and/or aryl groups or can be part of a heterocycle. Two of the radicals can also form a fused aromatic or heteroaromatic ring together.

Description

The invention relates to an agent for dyeing keratin fibers, in particular human hair containing aromatic nitroso compounds this aromatic nitroso compounds as a coloring component in hair dyes as well as a method for dyeing keratin fibers, especially human Hair.

For dyeing keratin fibers, e.g. B. hair, wool or furs come in general either direct dyes or oxidation dyes by oxi dative coupling of one or more developer components with each other or with egg ner or more coupler components arise, for use. Coupler and Ent winder components are also referred to as oxidation dye precursors.

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

Special representatives are, for example, p-phenylenediamine, p-toluenediamine, 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- amino-pyrazolon-5, 4-amino-3-methylphenol, 2-aminomethyi-4-aminophenol, 2-hydroxy methyl-4-aminophenol, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopy rimidin and 2,5,6-triamino-4-hydroxypyrimidine.

As coupler components, m-phenylenediamine derivatives, naphthols, Resorcinol and resorcinol derivatives, pyrazolones, m-aminophenols and substituted pyridindenes derivatives used. Suitable coupler substances are, in particular, α-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resor  cinmonomethyl ether, m-phenylenediamine, 2,4-diaminophenoxyethanol, 2-amino-4- (2-hy droxyethylamino) 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, the "The matology ", edited by Ch. Culnan, H. Maibach, published by 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), and the "European inventory of cosmetic raw materials", 1996, published by the Euro pean commission, available in diskette form from the Federal Association of German Industrial and trading company for pharmaceuticals, health products and personal care products e. V., Mannheim, referred to.

With oxidation dyes intensive dyeings with good fastness properties can be achieved, 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 the aromatic nitroso compounds described in more detail below Dyeing fibers containing keratin is not yet known.

The object of the present invention is to provide colorants for keratin fibers, in particular human hair, which are at least equivalent in quality 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 O 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 the aroma shown in the formula I. tical nitroso compounds are also evident in the absence of oxidizing agents excellent for dyeing keratin fibers. They result in discolorations excellent brilliance and depth of color and lead to diverse color nuances. The stake In principle, however, oxidizing agents should not be excluded.

The invention relates to an agent for dyeing keratin fibers, in particular human hair, containing at least one aromatic nitroso compound of the formula I,

in which R ¹ , R ² , R ³ and R ⁴ each independently of one another for a hydrogen or halogen atom, a C ₁ -C ₄ alkyl group, C ₁ -C ₄ alkoxy group or hydroxy-C ₁ -C ₄ alk oxy group, a hydroxyl group, sulfo group, carboxy group, amino group, which can be substituted by C ₁ -C ₄ alkyl, hydroxy-C ₁ -C ₄ alkyl and / or aryl groups or can be part of a heterocycle, where also two the residues can together form a fused aromatic or heteroaromatic ring.

Wool, furs, feathers and especially human fibers are among the fibers containing keratin 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.

Compounds of the formula I are preferably used in which a radical a hydroxyl group or an optionally substituted amino group. As examples for aromatic nitroso compounds, N, N-dimethyl-4-nitrosoaniline, 4-nitrosophene nol, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 1-nitroso-2-naphthol-3,6-disulfonic acid di  sodium salt (Nitroso R salt), 2-nitroso-1-naphthol-4-sulfonic acid, 5-nitroso-8-hydroxy quinoline, 2-nitroso-5-dimethylaminophenol hydrochloride, 4-nitrosodiphenylamine and their arbitrary mixtures are called.

Most of these substances are known from the literature or are commercially available or can be produced by known synthetic processes.

The aforementioned aromatic nitroso compounds 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 turns. They can be used as direct colorants or in the presence of customary oxi dation dye precursors are used.

Coloring agent, which as the coloring component, the aromatic nitroso compounds with the Containing formula I alone, are preferably used for coloring in the yellow range. Colorings with even greater brilliance and improved fastness properties (light fastness, fastness to washing, fastness to rubbing) over a wide range of shades from yellow to yellow brown, orange, brown orange, medium brown, dark brown, violet, dark violet up to blue-black and black are achieved if the ver bonds with the formula I together with at least one further component (in called the following component B), selected from compounds with primary or se secondary amino group or hydroxy group selected from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromati 's hydroxy compounds, and / or CH-active compounds can be used.

On the one hand, these are compounds that, on their own, only have weak keratin fibers color and only together with the aromatic nitroso compounds of formula I bril lante colorations result. On the other hand, there are also connections that already exist be used as oxidation dye precursors.

The above Compound B compounds 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 whole colorant can be used.  

Several different aromatic nitroso compounds can also be used in all colorants gen I formula are used together; Likewise, several ver different compounds of component B are used together.

The embodiment described above also includes the use of such substances, the reaction products of aromatic nitroso compounds Represent formula I with the compounds of component B mentioned as direct dyes. Such reaction products can e.g. B. by briefly heating the both components in stoichiometric amounts in aqueous neutral to weak alkaline environment can be obtained, either as a solid from solution precipitate or be isolated therefrom by evaporation of the solution. The reaction pro Products can also be used in combination with other dyes or dye precursors be used.

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- ( 2-methoxyethyl-), 2,3-, 2,4-, 2,5-dichloro-p-phenylenediamine, 2-chloro-p-phenylenediamine, 2,5-dihydroxy-4-morpholinoaniline-dihydrobro mid, 2-, 3 -, 4-aminophenol, 2-aminomethyl-4-aminophenol, 2-hydroxymethyl-4-amino phenol, 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-meth oxy-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-hydroxy naphthalene-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, Pentaaminobenzol, Hexaaminoben zol, 2,4,6-Triaminoresorcin, 4,5-Diaminobrenzcatechin, 4,6-Diaminopyrogallol, 3,5-Dia mino-4-hydroxybrenzcatechin, 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- (2nd -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, aromatic anilines or phenols with a further aromatic radical, as shown in formula II

in the R ⁵ for a hydroxy or an amino group, which 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,
R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ^{10 represent} hydrogen, a hydroxyl or an amino group which is substituted 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
Q for a direct bond, a saturated or unsaturated carbon chain with 1 to 4 carbon atoms optionally substituted by hydroxy 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 of one another for an oxygen atom, an NR ¹¹ group, wherein
R ¹¹ is hydrogen, a C _1-4 alkyl or a hydroxy-C _1-4 alkyl group, _{p is} the group O- (CH _{2) p} NH or NH- (CH ₂₎ '-O where p and p' 2 or 3 are, 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 hydrochlorind, 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, 1,3-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 aforementioned compounds can be used both in free form and in the form of their physiologically acceptable salts, in particular as salts of inorganic acids, such as Hydrochloric or sulfuric acid can be used.

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-diami no-, 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-amino quinoline, 4-aminoquinine din, 2-, 6-aminonicotinic acid, 5-aminoisoquinoline, 5-, 6-amino noindazole, 5-, 7-aminobenzimidazole, -benzothiazole, 2,5-dihydroxy-4-morpholinoaniline so such as indole and indoline derivatives, such as 4-, 5-, 6-, 7-aminoindole, 5,6-dihydroxyindole, 5,6-dihy droxyindoline and 4-hydroxyindoline. The aforementioned compounds can both in free form as well as in the form of their physiologically acceptable salts, e.g. B. as salts anor ganic acids such as hydrochloric or sulfuric acid can be used.

Suitable aromatic hydroxy compounds are e.g. B. 2-, 4-, 5-methylresorcinol, 2,5-di methylresorcinol, resorcinol, 3-methoxyphenol, pyrocatechol, hydroquinone, pyrogallol, Phloroglucin, 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-naphth thol, 1,5-, 2,3-, 2,7-dihydroxynaphthalene, 6-dimethylamino-4-hydroxy-2-naphthalenesulfone acid, 3,6-dihydroxy-2,7-naphthalenesulfonic acid.

Examples of CH-active compounds which can 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-di methyl 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-dimethylthiobarbitur acid, 1,3-diethylthiobarbituric acid, diethylthiobarbituric acid, oxindole, 3-indoxy acetate, Coumaranone and 1-methyl-3-phenyl-2-pyrazolinone.

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-diami nophenyl) ethanol, 2,5-diaminotoluene, 3,4-methylenedioxyaniline, 2-amino-4- (2-hydroxy ethylamino) 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-diethylaminomethyl-4- aminophenol, 2-dimethylaminomethyl-4-aminophenol, 2,6-dichloro-4-aminophenol, 2-Hy droxymethyl-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 those formed with preferably inorganic acids physiologically acceptable salts.

To achieve further and more intense colorations, the inventive Agents can additionally contain color enhancers, which are referred to below as component C be designated. The color enhancers are preferably 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, pyrrolidone-5-carboxylic acid, pyrazole, 1,2,4-triazole, piperazidine, their derivatives and their physiologically tolerable salts, components B and C being different.

On the presence of oxidizing agents, e.g. B. H ₂ O ₂ , 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 that 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 further modification of the color shades in addition to the verbin contained according to the invention additionally conventional direct dyes, z. B. from the group of nitropheny lendiamine, nitroaminophenols, anthraquinones or indophenols, such as. B. the among 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 invent Agents according to the invention according to this embodiment contain the directives Dyes preferably in an amount of 0.01 to 20 wt .-%, based on the total Colorants.

Furthermore, the preparations according to the invention can also occur in nature Dyes such as henna red, henna neutral, henna black, chamomile flower, Sandalwood, black tea, rotten tree bark, sage, blue wood, madder root, catechu, Contain sedre and alkanna root.

It is not necessary that the oxidation dye precursors or contain them optionally direct substantive dyes each represent uniform compounds. Much more can in the colorants of the invention, due to the manufacturing process for the individual dyes, additional components in minor amounts must be kept, as long as they do not adversely affect the coloring result or on their reasons, e.g. B. toxicological, must be excluded.

The colorants according to the invention already result in those which are physiologically compatible Temperatures below 45 ° C intense coloring. They are therefore particularly suitable for coloring human hair. For use on human hair the colorants can usually be in a water-containing cosmetic carrier  be worked. Suitable water-containing cosmetic carriers are e.g. B. creams, Emulsions, gels or surfactant-containing foaming solutions such. B. shampoos or other preparations suitable for use on the keratin fibers are not. If necessary, it is also possible to put the colorants in anhydrous carriers to work.

Furthermore, the colorants according to the invention can all be in such preparations Known active ingredients, additives and auxiliaries. In many cases, the colorants contain at least one surfactant, in principle both anionic and zwitterionic, am pholytic, nonionic and cationic surfactants are suitable. In many cases it has but proved to be advantageous, 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, glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups can be contained in the molecule. 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 3C atoms in the alkanol group,

• - linear fatty acids with 10 to 22 carbon atoms (soaps),
• Ether carboxylic 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 C 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,
• - Monosulfonic succinate 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 C atoms and x = 0 or 1 to 12,
• Mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030,
• - Sulphated 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 bin solutions 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 having 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 coconut alkyl dimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammonium glycinate, for example the coconut acylaminopropyl dimethylammonium glycinate, and 2-alkyl -3-carboxymethyl-3-hydroxyethyl-imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and the cocoacylaminoethylhydroxyethylcarboxymethylglycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known under the CTFA name Cocamidopropyl Betaine.

Ampholytic surfactants are those 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 in the molecule and are capable of forming internal salts are. Examples of suitable ampholytic surfactants are N-alkylglycine, N-alkylpropionic acid, N-alkylaminobutyric acid, N-alkyliminodipropionic acid, N-hydroxyethyl-N-alkylamidopropylglycine, N-alkyltaurine, N-alkyl sarcosine, 2-AI alkylaminopropionic acid and alkylaminoacetic acid each with about 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are the N-cocoalkyl aminopropionate, the cocoacylaminoethylaminopropionate and the C _12-18 acyl sarcosine.

Nonionic surfactants contain z as a hydrophilic group. B. a polyol group, a Po lyalkylenglykolethergruppe or a combination of polyol and polyglycol ether group. Such connections are, for example

• - Adducts 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 Atoms and on 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 analogs,
• - Addition products of 5 to 60 moles of ethylene oxide with castor oil and hardened rizi nut oil,
• - Addition products of ethylene oxide with sorbitan fatty acid esters
• - Addition products of ethylene oxide with fatty acid alkanolamides.

Examples of the cat usable in the hair treatment compositions according to the invention Ionic surfactants are especially quaternary ammonium compounds. Are preferred Ammonium halides such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chloride and trialkylmethyl ammonium chloride, e.g. B. Cetyltrimethylammonium chloride, stea ryltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammo nium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride. Other quaternized cationic surfactants that can be used according to the invention are the quaternized ones Protein hydrolyzates.

Also suitable according to the invention are cationic silicone oils such as those in the Commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trim thylsilylamodimethicone), Dow Corning 929 emulsion (containing a hydroxylamino mo differentiated silicone, also called amodimethicone), SM-2059 (manufacturer:  General Electric), SLM-55067 (manufacturer: Wacker) and Abil®-Quat 3270 and 3272 (manufacturer Steller: Th. Goldschmidt; diquaternary polydimethylsiloxanes, Quaternium-80).

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

Quaternary ester compounds are also very readily biodegradable "Esterquats", such as the methylhydroxyal sold under the trademark Stepantex® kyldialkoyloxyalkylammonium methosulfates.

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

The compounds with alkyl groups used as surfactants can in each case be act uniform substances. However, it is usually preferred in the manufacture these substances are based on natural vegetable or animal raw materials, so that mixtures of substances 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 with fat Alcohols or derivatives of these addition products can represent both products with a "normal" homolog distribution as well as those with a narrow homo log distribution can be used. Under "normal" homolog distribution Mixtures of homologues understood, which one in the implementation of fatty alcohol and Alkylene oxide using alkali metals, alkali metal hydroxides or alkali tall alcoholates obtained as catalysts. Narrow homolog distributions are there against obtained when, for example, hydrotalcites, alkaline earth metal salts of ether carbon acids, alkaline earth metal oxides, hydroxides or alcoholates used as catalysts become. The use of products with a narrow homolog distribution can be to be preferred.

Other active ingredients, auxiliaries and additives are, for example

• Non-ionic polymers such as, for example, vinyl pyrrolidone / vinyl acrylate copolymers, Polyvinyl pyrrolidone and vinyl pyrrolidone / 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, vinylpyrrolidone-imidazolinium methochloride Copolymers and quaternized polyvinyl alcohol,
• - zwitterionic and amphoteric polymers such as acrylamidopropyl-tri methylammonium chloride / acrylate copolymers and octylacrylamide / methylmethacry 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 acid drid copolymers and acrylic acid / ethyl acrylate / N-tert-butylacrylamide terpolymers,
• - Thickeners such as agar agar, guar gum, alginates, xanthan gum, gum arabi cum, karaya gum, locust bean gum, linseed gums, dextrans, cellu loose derivatives, e.g. B. methyl cellulose, hydroxyalkyl cellulose and carboxymethyl cellu loose, 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 cephaline, as well as silicone oils,
• - Protein hydrolyzates, especially elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolyzates, their condensation products with fatty acids as well as 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 Zink 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 enhancers 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 glycerin, propylene glycol monoethyl ether, carbo nates, hydrogen carbonates, guanidines, ureas and primary, secondary and ter 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 for the production of the invention moderate colorants used in amounts customary for this purpose; e.g. B. become Emul yaw in concentrations of 0.5 to 30% by weight and thickeners in concentrate tions 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 coloring agents add salts. 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, Na trium or lithium, alkaline earth metals, such as magnesium, calcium, strontium or barium, or of aluminum, manganese, iron, cobalt, copper or zinc, where sodium acetate, Lithium bromide, calcium bromide, cafcium gluconate, zinc chloride, zinc sulfate, magnesium chloride rid, magnesium sulfate, ammonium carbonate, chloride and acetate are preferred. This 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 3 and 11, preferably between 4 and 10.

Another object of the present invention relates to the use of aromatic nitroso compounds with the formula I,

in which R ¹ , R ² , R ³ and R ⁴ each independently of one another for a hydrogen or halogen atom, a C ₁ -C ₄ alkyl group, C ₁ -C ₄ alkoxy group or hydroxy-C ₁ -C ₄ alk oxy group, a hydroxyl group, sulfo group, carboxy group, amino group, which can be substituted by C ₁ -C ₄ alkyl, hydroxy-C ₁ -C ₄ alkyl and / or aryl groups or can be part of a heterocycle, where also two the residues can together form a fused aromatic or heteroaromatic ring,
as a coloring component in oxidation hair dyes.

Yet another object of the present invention relates to a process for dyeing keratin-containing fibers, in particular human hair, in which a dye containing

• A) at least one aromatic nitroso compound with the formula I,
  in which R ¹ , R ² , R ³ and R ⁴ each independently of one another for a hydrogen or halogen atom, a C ₁ -C ₄ alkyl group, C ₁ -C ₄ alkoxy group or hydroxy-C ₁ -C ₄ alkoxy group , a hydroxyl group, sulfo group, carboxy group, amino group, which can be substituted by C ₁ -C ₄ alkyl, hydroxy-C ₁ -C ₄ alkyl, aryl groups or can be part of a heterocycle, with two of the radicals in common sam can form a fused aromatic or heteroaromatic ring, and
• B) at least one compound with primary or secondary amino group or Hy droxy group selected from primary or secondary aliphatic or aromatic amines, nitrogen-containing heterocyclic compounds, aromatic hy droxy compounds, and / or at least one CH-active compound,

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

The aromatic nitroso compounds of the formula I and the compounds of the compo nente B can either be applied to the hair at the same time or else one after the other, it doesn't matter which of the two components is listed first will wear. The optionally contained ammonium or metal salts can be the be added to the first or the second component. Between applying the The first and second components can be up to 30 minutes apart. Also pretreatment of the fibers with the saline solution is possible.

The aromatic nitroso compounds of the formula I and the compounds of the compo nente 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, it should these are largely anhydrous to reduce a reaction of the components. At the separate storage, the reactive components are only immediately before Application intimately mixed together. In dry storage, before Usually a defined amount of warm (30 to 80 ° C) water is added and made a homogeneous mixture.  

Examples Preparation of a coloring solution

A slurry of 5 mmol of an aromatic nitroso compound was used of formula I, optionally 5 mmol of an oxidation dye precursor of component B and 5 mmol sodium acetate and a drop of a 20% fatty alkyl ether sulfate solution in 50 ml of water at 60 ° C. The slurries were after cooling to 30 ° C mixed together and with dilute NaOH or hydrochloric acid to a pH of 9 set.

A tress of 90% was grayed into this dyeing mixture at 30 ° C. for 30 minutes, untreated human hair. The streak was then with 30 sec lukewarm water rinsed, dried with warm air and then combed out.

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

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
+++: strong to very strong intensity

Table 1

Colorings with N, N-dimethyl-4-nitrosoaniline

Table 2

Colorings with 2-nitroso-1-naphthol-4-sulfonic acid

Table 3

Colorings with nitroso-R salt

Table 4

Colorings with 2-nitroso-1-naphthol

Table 5

Colorings with 5-nitroso-8-hydroxyquinoline

Table 6

Colorings with nitroso-R salt

Claims (13)

1. means for dyeing keratin fibers, in particular human hair, containing at least one aromatic nitroso compound of the formula I as the coloring component,
in which R ¹ , R ² , R ³ and R ⁴ each independently of one another represent a hydrogen or halogen atom, a C ₁ -C ₄ alkyl group, C ₁ -C ₄ alkoxy group or hydroxy-C ₁ -C ₄ alkoxy group, a hydroxyl group, sulfo group, carboxy group, amino group, which can be substituted by C ₁ -C ₄ alkyl, hydroxy-C ₁ -C ₄ alkyl, aryl groups or can be part of a heterocycle, where two of the radicals together form one can form fused aromatic or heteroaromatic ring. 2. Composition according to claim 1, characterized in that as compounds with the Formula I N, N-dimethyl-4-nitrosoaniline, 4-nitrosophenol, 1-nitroso-2-naphthol, 2- Nitroso-1-naphthol, 1-nitroso-2-naphthol-3,6-disulfonic acid disodium salt (Nitroso R. Salt), 2-nitroso-1-naphthol-4-sulfonic acid, 5-nitroso-8-hydroxyquinoline, 2-nitroso-5- dimethylaminophenol hydrochloride, 4-nitrosodiphenylamine and any of them Mixtures are used. 3. Composition according to one of claims 1 to 2, characterized in that the aroma table nitroso compounds with the formula I in an amount of 0.03 to 65 mmol, in particular from 1 to 40 mmol, based on 100 g of the total colorant, are included. 4. Agent according to one of claims 1 to 3, characterized in that it 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 hydroxyverbin dungen, and / or at least one CH-active compound. 5. Means according to claim 4, characterized in that the further connection is selected from
primary or secondary amines from the group consisting of N- (2-hydroxyethyl) -N-ethyl-, N- (2-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-mor pholinoaniline dihydrobromide, 2-, 3-, 4-aminophenol, o -, m-, p-phenylenediamine, 2,4-diaminophenoxyethanol, 2- (2,5-diaminophenyl) ethanol, 2,5-diaminotoluene, phenol, phenol, 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-aminomethyl-phenol, 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-diamino benzoic 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-A mino-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-tetraamino nobenzene tetrahydrochloride, 2,4,5 -Triaminophenol trihydrochloride, pentaaminobenzene pentahydrochloride, hexaaminobenzene hexahydrochloride, 2,4,6-triaminoresorcinol trihydrochloride, 4,5-diaminobenzate catechol sulfate, 4,6-diaminopyrogallol dihydrochloride, 3,5-diamino-4-hydroxybrenzate catechol Nitriles, anilines, especially anilines containing nitro groups, 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-ni trophenol, 1-amino-5-chloro-4- (2-hydroyethylamino) -2-nitrobenzene, aromatic anilines or phenols with a further aromatic Remainder such as 4,4'-diaminostilbene dihydrochloride, 4,4'-diaminostilbene-2,2'-disulfonic acid, sodium salt, 4,4'-diaminodiphenylmethane, sulfide, sulfoxide, amine, 4,4 ' -Diaminodiphenylamine-2-sulfonic acid, 4,4'-diaminobenzo phenone, -diphenyl ether, 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-diaminophenoxy) -3,6-dioxaoctane tetrahydrochloride, 1,3-bis (4-amino phenylamino) 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- Dia mino-, 2-dimethylamino-5-amino-, 3-ami no-2-methylaminv-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-aminoquinoline , 4-aminoquinodine, 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-hydroxyin dol, 5,6-dihydroxyindole, 5,6-dihydroxyindoline and 4-hydroxyindoline, and in each case from those with preferably inorganic Acids formed physiologically acceptable salts of these compounds,
aromatic hydroxy compounds selected from the group consisting of 2-, 4-, 5-methylresorcinol, 2, 5-dimethylresorcinol, resorcinol, 3-methoxyphenol, pyrocatechin chin, hydroquinone, pyrogallol, phloroglucin, hydroxyhydroquinone, 2-, 3-, 4- Methoxy-, 3-dimethylamino-, 2- (2-hydroxyethyl) -, 3,4-methylenedioxyphenol, 2,4-, 3,4-dihydroxy benzoic acid, -phenylacetic acid, gallic acid, 2,4,6-trihydroxybenzoic acid, -aceto phenone, 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-3-hindolium 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-methylene indoline), 2,3-dimethyl-benzothiazolium iodide, 2,3-dimethyl-benzothiazolium-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-dimethylthiobarbituric acid, 1 , 3-diethylthio barbituric acid, diethylthiobarbituric acid, oxindole, 3-indoxy acetate, coumaranone and 1-methyl-3-phenyl-2-pyrazolinone. 6. Composition according to claim 5, characterized in that the further connection 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-Phe nylenediamine, 2- (2,5-diaminophenyl) ethanol, 2,5-diaminotoluene, 3,4-methylenedioxy aniline, 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-hydroxy ethylamino) -, 2-methyl-5-amino-4-chloro, 6-methyl-3-amino-2-chloro, 2-aminomethyl 4-aminophenol, 2-diethylaminomethyl-4-aminophenol, 2-dimethylaminomethyl-4- aminophenol, 2,6-dichloro-4-aminophenol, 2-hydroxymethyl-4-aminophenol, 3,4-Me thylenedioxyphenol, 3,4-diaminobenzoic acid, 2,5-diamino, 2-dimethylamino-5-ami no-, 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-dihydroxyin dolin and in each case from the phy formed preferably with inorganic acids Siologically acceptable salts of these compounds. 7. Composition 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, pyrrole 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 direct pulling dyes from the group of nitrophenylenediamines, nitroaminophenols, Anthraquinones or indophenols preferably in an amount of 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, 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 be. 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 is anioni contains, zwitterionic or nonionic surfactants. 12. Use of aromatic nitroso compounds with the formula I,
in which R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen or halogen atom, a C ₁ -C ₄ alkyl group, C ₁ -C ₄ alkoxy group or hydroxy-C ₁ - C ₄ alkoxy group, a hydroxy group, sulfo group, carboxy group, amino group which can be substituted by C ₁ -C ₄ alkyl, hydroxy-C ₁ -C ₄ alkyl and / or aryl groups or can be part of a heterocycle, where two of the Residues can together form a fused aromatic or heteroaromatic ring,
as a coloring component in oxidation hair dyes. 13. A method for dyeing keratin fibers, especially human hair, in which a colorant

• A) at least one aromatic nitroso compound with the formula I,
  in which R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen or halogen atom, a C ₁ -C ₄ alkyl group, C ₁ -C ₄ alkoxy group or hydroxy-C ₁ -C ₄ alkoxy group, a hydroxy group, sulfo group, carboxy group, amino group which can be substituted by C ₁ -C ₄ alkyl, hydroxy-C ₁ -C ₄ alkyl and / or aryl groups or can be part of a heterocycle, where two of the Residues together can form a fused aromatic or heteroaromatic ring, and
• B) at least one compound with primary or secondary amino group or hydroxy group, selected from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds, and / or at least one CH-active compound,

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