DE19859810A1 - Preparations for coloring keratinous fibers - Google Patents

Abstract

The invention relates to an agent for dying keratin fibers, especially human hair, containing aromatic nitroaldehydes with formula (I), in which R<1>, R<2> and R<3>, independent of one another, represent hydrogen atoms, halogen atoms, C1-C4-alkyl groups, C1-C4-hydroxyalkyl groups, amino-C1-C4-alkyl groups, C1-C4-alkoxy groups, C1-C4-acyl groups, hydroxy groups, nitro groups, carboxy groups, C1-C4-acyl amino groups, sulfo groups or amino groups, which can be substituted by C1-C4-alkyl groups or C2-C4-hydroxyalkyl groups, whereby two of the radicals, together, can form a fused aromatic ring; and n represents 0, 1, or 2.

Description

The invention relates to an agent for dyeing keratin-containing fibers, especially human hair that contains aromatic nitroaldehydes, the Use of these nitroaldehydes as a coloring component in hair dyes and a method for dyeing keratin-containing fibers, in particular human hair.

For dyeing keratin-containing fibers, e.g. B. hair, wool or fur, in general either substantive dyes or Oxidation dyes obtained by oxidative coupling of one or more Developer components with one another or with one or more Coupler components arise for the application. Coupler and developer compo nents are also referred to as oxidation dye precursors.

Primary aromatic amines are usually used as developer components another free or substituted one in the para or ortho position Hydroxy or amino group, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazolone derivatives and 2,4,5,6-tetraaminopyrimidine and its Derivatives used.

Special representatives are, for example, p-phenylenediamine, p-tolylenediamine, 2,4,5,6-tetraaminopyrimidine, p-aminophenol, N, N-bis- (2-hydroxyethyl) -p-pheny lenediamine, 2- (2,5-diaminophenyl) -ethanol, 2- (2,5-diaminophenoxy) -ethanol, 1- Phenyl-3-carboxyamido-4-amino-pyrazolone-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.

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

With regard to other customary dye components, reference is expressly made to the series "Dermatology", edited by Ch. Culnan, H. Maibach, Marcel Dekker Inc., New York, Basel, 1986, vol. 7, Ch. Zviak, The Science of Hair Care, chap. 7, Pages 248-250 (direct dyes), and chap. 8, pages 264-267 (Oxidation dyes), as well as the "European inventory of cosmetic raw materials", 1996, published by the European Commission, available in Diskette form from the Federal Association of German Industry and Trading company for pharmaceuticals, health foods and personal care products e. V., Mannheim, referred to.

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

From the German patent application 196 30 275 the use of Benz- or cinnamaldehydes in combination with oxidation dye precursors. The use of the aromatic nitroaldehydes described in more detail below for Dyeing of keratin-containing fibers has not yet been explicitly described.

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 depth of color, gray coverage and fastness properties, but without necessarily relying on oxidants such as. B. H ₂ O _{2 to be} instructed. In addition, the colorants must have no or only a very low sensitization potential.

Surprisingly, it has now been found that those shown in the formula I. aromatic nitroaldehydes are also found in the absence of oxidizing agents excellent for dyeing fibers containing keratin. You surrender Coloring with excellent brilliance and depth of color and lead to diverse Color nuances. However, the use of oxidizing agents should not be used be excluded. It was also found that the discoloration with aromatic nitroaldehydes compared to the prior art used aldehydes are significantly more intense.

The invention relates to an agent for dyeing keratin-containing fibers, in particular human hair, containing aromatic nitroaldehydes of the formula I,

in which R ¹ , R ² and R ³ independently of one another represent hydrogen atoms, halogen atoms, C ₁ -C ₄ -alkyl-, C ₁ -C ₄ -hydroxyalkyl-, amino-C ₁ -C ₄ -alkyl-, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -acyl, hydroxy, nitro, carboxy, C ₁ -C ₄ -acylamino, sulfo or amino groups, which are replaced by C ₁ -C ₄ -alkyl or C ₂ -C ₄ -hydroxyalkyl groups can be substituted, two of the radicals can also together form a fused aromatic ring, and
n is 0, 1 or 2.

Among keratinous fibers are wool, furs, and feathers in particular understand human hair. The colorants according to the invention can but in principle 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, polyurethane and polyester fibers are used will.

The compounds with the formula I are preferably selected from the group the following aromatic nitroaldehydes: 2-nitrobenzaldehyde, 3-nitrobenzaldehyde, 4-nitrobenzaldehyde, 4-methyl-3-nitrobenzaldehyde, 3-hydroxy-4-nitrobenzaldehyde, 4-hydroxy-3-nitrobenzaldehyde, 5-hydroxy-2-nitrobenzaldehyde, 2-hydroxy-5- nitrobenzaldehyde, 2-hydroxy-3-nitrobenzaldehyde, 2-fluoro-3-nitrobenzaldehyde, 3- Methoxy-2-nitrobenzaldehyde, 4-chloro-3-nitrobenzaldehyde, 2-chloro-6- nitrobenzaldehyde, 5-chloro-2-nitrobenzaldehyde, 4-chloro-2-nitrobenzaldehyde, 2,4- Dinitrobenzaldehyde, 2,6-dinitrobenzaldehyde, 2-hydroxy-3-methoxy-5- nitrobenzaldehyde, 4,5-dimethoxy-2-nitrobenzaldehyde, 6-nitropiperonal, 2- Nitropiperonal, 5-nitrovanillin, 2,5-dinitrosalicylaldehyde, 5-bromo-3- nitrosalicylaldehyde, 3-nitro-4-formylbenzenesulfonic acid, 4-nitro-1-naphthaldehyde, 2-nitrocinnamaldehyde, 3-nitrocinnamaldehyde, 4-nitrocinnamaldehyde and their any mixtures.

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

The above-mentioned aromatic nitroaldehydes 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, is used. They can be used as a substantive colorant or in The presence of customary oxidation dye precursors can be used.

Coloring agent which, as a coloring component, combines the aromatic nitroaldehydes with the Formula I alone are preferred for yellow and orange colorations richly employed. Colorations with even higher brilliance and improved Fastness properties (light fastness, wash fastness, rub fastness) over one wide range of nuances from yellow to yellow-brown, orange, brown-orange, medium brown, olive green, dark brown, violet, dark purple to blue black and black are achieved when those used according to the invention Compounds with the formula I together with at least one other Component (hereinafter referred to as component B) selected from Compounds with primary or secondary amino groups or hydroxyl groups, selected from primary or secondary aliphatic or aromatic Amines, nitrogen-containing heterocyclic compounds, amino acids, from 2 up to 9 amino acids built up oligopeptides and aromatic hydroxyver bonds, and / or CH-active compounds, can be used. these are on the one hand, connections that for themselves only contain keratin fibers only weakly color and only together with the aromatic nitroaldehydes of the formula I. result in brilliant colors. On the other hand, it also includes connections which are already used as oxidation dye precursors.

The abovementioned compounds of component B can be used in one Amount of 0.03 to 65, in particular 1 to 40 mmol, each based on 100 g of the total colorant can be used.

All dyes can contain several different aromatic substances Nitroaldehydes of the formula I are used together; also can also several different compounds of component B together ver be turned.

Use also falls under the embodiment described above of such substances, the reaction products of aromatic Nitroaldehydes of the formula I with the compounds of component B mentioned represent, as substantive colorants. Such reaction products can, for. B. by briefly heating the two components in stoichiometric Quantities are obtained in an aqueous neutral to weakly alkaline medium, they either precipitate out of solution as a solid or by evaporation the solution can be isolated therefrom. The reaction products can also be used in Used in combination with other dyes or dye precursors will.

Suitable compounds with a primary or secondary amino group as component B are, for. B. primary aromatic amines such as N, N-dimethyl-, N, N-diethyl-, N- (2-hydroxyethyl) -N-ethyl-, N, N-bis- (2-hydroxyethyl) -, N- (2 -Methoxye thyl-), 2,3-, 2,4-, 2,5-dichloro-p-phenylenediamine, 2-chloro-p-phenylenediamine, 2,5-dihydroxy-4-morpholinoaniline-dihydrobromide, 2-, 3 -, 4-aminophenol, 2-Ami nomethyl-4-aminophenol, 2-hydroxymethyl-4-aminophenol, o-, p-phenylenediamine, o-tolylenediamine, 2,5-diaminotoluene, -phenol, -phenethol, 4-amino- 3-methylphenol, 2- (2,5-diaminophenyl) -ethanol, 2,4-diaminophenoxyethanol, 2- (2,5-diaminophenoxy) -ethanol, 4-methylamino-, 3-amino-4- (2'- 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-diaminobrenzcatechol, 4,6-diamino pyrogallol, 3,5-diamino-4-hydroxypyrogallol, aromatic 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-nitrophenol, 1-amino-5-chloro-4- (2-hydroyethylamino) - 2- nitrobenzene, aromatic anilines or phenols with a further aromatic radical, as shown in formula II

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

Z- (CH ₂ -Y-CH ₂ -Z ') _o (III)

in which Y is a direct bond, a CH ₂ or CHOH group,
Z and Z 'independently of one another represent an oxygen atom, an NR ¹⁰ group, in which R ¹⁰ denotes hydrogen, a C _1-4 -alkyl or a hydroxy-C _1-4 -alkyl group, the group O- (CH ₂ ) _p -NH or NH- (CH ₂ ) _p '-O, where p and p' are 2 or 3, and
o means a number from 1 to 4,
such as 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, -diphenylether, 3,3 ', 4,4'-tetraaminodiphenyl, 3 , 3 ', 4,4'-tetraamino benzophenone, 1,3-bis (2,4-diaminophenoxy) propane, 1,8-bis (2,5-diaminophen oxy) -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 their physiologically acceptable salts, especially as salts of inorganic compounds Acids, such as hydrochloric or sulfuric acid, can be used.

Suitable nitrogen-containing heterocyclic compounds are, for. 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-tri amino-, 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-aminoquinoline, 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 both in free form and in the form of their physiological compatible salts, e.g. B. as salts of inorganic acids, such as salt or Sulfuric acid.

Suitable aromatic hydroxy compounds are, for. B. 2-, 4-, 5-methylresorcinol, 2,5-dimethylresorcinol, resorcinol, 3-methoxyphenol, catechol, hydroquinone, Pyrogallol, phloroglucinol, hydroxyhydroquinone, 2-, 3-, 4-methoxy-, 3- Dimethylamino-, 2- (2-hydroxyethyl) -, 3,4-methylenedioxyphenol, 2,4-, 3,4- Dihydroxybenzoic acid, phenylacetic acid, gallic acid, 2,4,6-trihy droxybenzoic 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.

As CH-active compounds can be named 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, Fischersche 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-methyl-2- quinaldinium iodide, 1-ethyl-2-quinaldinium iodide, 1,4-dimethylquinolinium iodide, Barbituric acid, thiobarbituric acid, 1,3-dimethylthiobarbituric acid, 1,3-diethylthio barbituric acid, diethylthiobarbituric acid, oxindole, 3-indoxylacetate, coumaranone and 1-methyl-3-phenyl-2-pyrazolinone.

Preferred amino acids are all naturally occurring and synthetic α-amino acids in question, e.g. B. by hydrolysis from vegetable or animal proteins, e.g. B. collagen, keratin, casein, elastin, soy protein, Wheat gluten or almond protein, accessible amino acids. Here you can both acidic and alkaline reacting amino acids are used. Preferred amino acids are arginine, histidine, tyrosine, phenylalanine, DOPA (Di hydroxyphenylalanine), 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 those contained in polypeptide or protein hydrolysates Be oligopeptides, provided they have one for use in the Colorants according to the invention have sufficient water solubility. as Examples are B. Glutathione and those in the hydrolyzates of collagen, keratin, Casein, elastin, soy protein, wheat gluten or almond protein contain oli to name gopeptide.

Preference is given to agents which the compounds of the formula I together with Compounds with primary or secondary amino groups or with aromatic Contain hydroxy compounds. 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) etha nol, 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-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-hydroxy pyrazole, 5,6-dihydroxyindole and 5,6-dihydroxyindoline and their with physiologically compatible formed preferably inorganic acids Salts.

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

In a preferred embodiment, the Fär according to the invention contain means for further modifying the color nuances in addition to those according to the invention compounds contained in addition usual substantive dyes, z. B. off the group of nitrophenylenediamines, nitroaminophenols, anthraquinones or In dophenols, such as B. those under the international names or Han delsnames 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 Pikramin acid 2-amino-6-chloro-4-nitrophenol, 4-amino-2-nitrodiphenylamine-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 according to this Embodiment contain the substantive dyes preferably in one Amount from 0.01 to 20% by weight, based on the total colorant.

Furthermore, the preparations according to the invention can also occur in nature occurring dyes such as henna red, henna neutral, henna black, chamomile blossom, sandalwood, black tea, buckthorn bark, sage, Contains logwood, madder root, catechu, sedre and alkanna root.

It is not necessary that the oxidation dye precursors or the optional Substantive dyes contained in each case represent uniform compounds place. Rather, in the colorants according to the invention, due to the manufacturing process for the individual dyes, in subordinate Amounts of other components may also be included, if these do not Adversely affect the dyeing result or for other reasons, e.g. B. toxicolo gisch, must be excluded.

The colorants according to the invention already result in physiological tolerable temperatures below 45 ° C intensive colorations. You are suitable therefore especially for coloring human hair. To apply to the human hair, the colorants can usually in one aqueous cosmetic carriers are incorporated. Suitable what cosmetic carriers containing serum are z. B. creams, emulsions, or gels Surfactant-containing foaming solutions such as B. shampoos or others Preparations suitable for use on the keratin-containing fibers are. If necessary it is also possible to use the dye in anhydrous carrier to incorporate.

Furthermore, the colorants according to the invention can all be used in such preparations known active ingredients, additives and auxiliaries. In many cases ent hold the colorants at least one surfactant, in principle both anionic as well as zwitterionic, ampholytic, nonionic and cationic surfactants are suitable. In many cases, however, it has been found to be beneficial to the Surfactants made from anionic, zwitterionic or nonionic surfactants to select.

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

• - linear fatty acids with 10 to 22 carbon atoms (soaps),
• - Ethercarboxylic acids of the formula RO- (CH ₂ -CH ₂ O) _x -CH ₂ -COOH, in which R is a linear alkyl group with 10 to 22 carbon atoms and x = 0 or 1 to 16,
• - acyl sarcosides with 10 to 18 carbon atoms in the acyl group,
• - acyl taurides with 10 to 18 carbon atoms in the acyl group,
• - acyl isethionates with 10 to 18 carbon atoms in the acyl group,
• - Sulphosuccinic acid mono- and dialkyl esters with 8 to 18 carbon atoms in the Al alkyl group and sulfosuccinic acid mono-alkyl polyoxyethyl ester with 8 to 18 C atoms in the alkyl group and 1 to 6 oxyethyl groups,
• - linear alkanesulfonates with 12 to 18 carbon atoms,
• - linear alpha-olefin sulfonates with 12 to 18 carbon atoms,
• - Alpha-sulfofatty acid methyl esters of fatty acids with 12 to 18 carbon atoms,
• - Alkyl sulfates and alkyl polyglycol ether sulfates of the formula RO (CH ₂ -CH ₂ O) _x -SO ₃ H, in which R is a preferably linear alkyl group with 10 to 18 carbon atoms and x = 0 or 1 to 12,
• - Mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030,
• - sulfated hydroxyalkyl polyethylene and / or hydroxyalkylene propylene glycol ether according to DE-A-37 23 354,
• - Sulphonates 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 Represent 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 especially unsaturated C ₈ -C ₂₂ carboxylic acids, such as oleic acid, stearic acid, isostearic acid and palmitic acid .

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

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

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

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

Examples of those used in the hair treatment compositions according to the invention Cationic surfactants are especially quaternary ammonium compounds. Ammonium halides such as alkyltrimethylammonium chlorides are preferred, Dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g. B. Cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distea ryldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethyl benzylammonium chloride and tricetylmethylammonium chloride. Further invention according to usable cationic surfactants represent the quaternized Protein hydrolysates.

Cationic silicone oils such as, for example, are also suitable according to the invention instruct the commercially available products Q2-7224 (manufacturer: Dow Corning; stabilized trimethylsilylamodimethicone), Dow Corning 929 emulsion (contains a hydroxyl-amino-modified silicone, also known as Amodime thicone), SM-2059 (manufacturer: General Electric), SLM-55067 (Manufacturer: Wacker) and Abil®-Quat 3270 and 3272 (manufacturer: Th. Gold schmidt; diquaternary polydimethylsiloxanes, Quaternium-80).

Alkylamidoamines, especially fatty acid amidoamines such as that under the designation Tego Amid®S 18 available stearylamidopropyldimethylamine stand out in addition to a good conditioning effect, especially due to their good biological properties Degradability.

Quaternary ester compounds, so-called called "Esterquats" such as those sold under the Stepantex® trademark Methyl hydroxyalkyl dialkoyloxyalkyl ammonium methosulfates.

An example of a quaternary sugar that can be used as a cationic surfactant derivative is 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 vary because they are uniform substances. However, it is usually preferred in the manufacture of these substances from native vegetable or animal Starting with raw materials, so that one substance mixtures with different, receives alkyl chain lengths depending on the respective raw material.

In the case of surfactants, the addition products of ethylene and / or propylene oxide of fatty alcohols or derivatives of these addition products can both products with a "normal" homolog distribution and those with a narrowed homolog distribution can be used. Under "normal" Homolog distribution is understood here to mean mixtures of homologs which one in the implementation of fatty alcohol and alkylene oxide using Alkali metals, alkali metal hydroxides or alkali metal alcoholates as catalysts gates receives. On the other hand, narrowed homolog distributions are obtained if for example hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earths Limetal oxides, hydroxides or alcoholates are used as catalysts. The use of products with a narrow homolog distribution can be be preferable.

Further active ingredients, auxiliaries and additives are, for example

• - Nonionic polymers such as vinylpyrrolidone / vinyl acrylate copo polymers, polyvinylpyrrolidone and vinylpyrrolidone / vinyl acetate copolymers and Polysiloxanes,
• - Cationic polymers such as quaternized cellulose ethers, polysiloxanes with qua ternary groups, dimethyldiallylammonium chloride polymers, acrylamide-di methyldiallylammonium chloride copolymers, di quaternized with diethyl sulfate methylaminoethyl methacrylate vinyl pyrrolidone copolymers, vinyl pyrrolidone Imidazolinium methochloride copolymers and quaternized polyvinyl alcohol,
• - zwitterionic and amphoteric polymers such as acrylamidopro pyl-trimethylammonium chloride / acrylate copolymers and octylacrylamide / Me ethyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate Copolymers,
• - Anionic polymers such as polyacrylic acids, crosslinked polyacrylics acids, vinyl acetate / crotonic acid copolymers, vinyl pyrrolidone / vinyl acrylate Copolymers, vinyl acetate / butyl maleate / sobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and acrylic acid / ethyl acrylate / N- tert-butyl acrylamide terpolymers,
• - Thickening agents such as agar-agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, linseed gums, dex trane, cellulose derivatives, e.g. B. methyl cellulose, hydroxyalkyl cellulose and Carboxymethyl cellulose, starch fractions and derivatives such as amylose, Amylopectin and dextrins, clays such as e.g. B. bentonite or fully synthetic Hydrocolloids such as B. polyvinyl alcohol,
• - structurants such as glucose and maleic acid,
• - Hair conditioning compounds such as phospholipids, for example So jalecithin, egg lecithin and cephalins, as well as silicone oils,
• - Protein hydrolysates, especially elastin, collagen, keratin, milk protein, Soy protein and wheat protein hydrolysates, their condensation products with fatty acids and quaternized protein hydrolysates,
• - perfume oils, dimethyl isosorbide and cyclodextrins,
• - Solubilizers such as ethanol, isopropanol, ethylene glycol, propylene glycol, Glycerine and diethylene glycol,
• - Anti-dandruff ingredients such as Piroctone Olamine and Zinc Omadine,
• - other substances to adjust the pH value,
• - Active ingredients such as panthenol, pantothenic acid, allantoin, pyrrolidone carboxylic acids and their salts, plant extracts and vitamins,
• - cholesterol,
• - light stabilizers,
• - Consistency factors such as sugar esters, polyol esters or polyol alkyl ethers,
• - Fats and waxes such as whale rat, beeswax, montan wax, paraffins, fettal alcohols and fatty acid esters,
• - fatty acid alkanolamides,
• - complexing agents such as EDTA, NTA and phosphonic acids,
• - Swelling and penetration substances such as glycerine, propylene glycol monoethyl ether, Carbonates, hydrogen carbonates, guanidines, ureas and primary, sec dary and tertiary phosphates, imidazoles, tannins, pyrrole,
• - opacifiers such as latex,
• - pearlescent agents such as ethylene glycol mono- and distearate,
• - Propellants such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air as well
• - antioxidants.

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

For the dyeing result, it can be advantageous to add ammonium or add metal salts. Suitable metal salts are e.g. B. Formates, Carbonates, halides, sulfates, butyrates, valemates, capronates, acetates, lactates, Glycolates, tartrates, citrates, gluconates, propionates, phosphates and phosphonates of alkali metals such as potassium, sodium or lithium, alkaline earth metals such as Magnesium, calcium, strontium or barium, or of aluminum, manganese, Iron, cobalt, copper or zinc, with sodium acetate, lithium bromide, calcium bro mid, calcium gluconate, zinc chloride, zinc sulfate, magnesium chloride, magnesium sulfate, ammonium carbonate, chloride and acetate are preferred. These salts are preferably in an amount from 0.03 to 65, in particular from 1 to 40, mmol based on 100 g of the total colorant.

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

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

in which R ¹ , R ² and R ³ independently of one another represent hydrogen atoms, halogen atoms, C ₁ -C ₄ -alkyl-, C ₁ -C ₄ -hydroxyalkyl-, amino-C ₁ -C ₄ -alkyl-, C ₁ - C ₄ alkoxy, C ₁ -C ₄ acyl, hydroxy, nitro, carboxy, C ₁ -C ₄ acylamino, sulfo or amino groups substituted by C ₁ -C ₄ alkyl or C ₂ -C ₄ -hydroxyalkyl groups can be substituted, two of the radicals can also together form a fused aromatic ring, and
n stands for 0, 1 or 2,
as a coloring component in hair dyes.

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

• A) at least one aromatic nitroaldehyde with the formula I,
  in which R ¹ , R ² and R ³ independently of one another represent hydrogen atoms, halogen atoms, C ₁ -C ₄ -alkyl-, C ₁ -C ₄ -hydroxyalkyl-, amino-C ₁ -C ₄ -alkyl-, C ₁ -C ₄ alkoxy, C ₁ -C ₄ acyl, hydroxy, nitro, carboxy, C ₁ -C ₄ acylamino, sulfo or amino groups which are replaced by C ₁ -C ₄ alkyl or C ₂ -C ₄ - hydroxyalkyl groups can be substituted, two of the radicals can also together form a fused aromatic ring, and
  n is 0, 1 or 2, and
• B) at least one compound with 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, and / or at least one CH-active Link,

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

The aromatic nitroaldehydes of the formula I and the compounds of the Com Component B can either be applied to the hair at the same time or but also one after the other, whereby it is irrelevant which of the two Components is applied first. The optionally contained ammonium or metal salts can be of the first or the second component can be added. Between applying the first and the second Components can be up to 30 minutes apart. Also one It is possible to pre-treat the fibers with the salt solution.

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

Examples Preparation of a staining solution

It was a suspension of 5 mmol of a nitroaldehyde with the 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 prepared in 50 ml of water at 80 ° C. The slurries were at 30 ° C mixed together and diluted with hydrochloric acid or sodium hydroxide solution adjusted to a pH of 6.

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

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

The color depth was rated according to the following scale:

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

Table 1

Staining with 5-nitrovanillin

Table 2

Coloration with 2-hydroxy-5-nitrobenzaldehyde

Table 3

Coloration with 4-hydroxy-3-nitrobenzaldehyde

Table 4

Coloration with 4-nitrobenzaldehyde

Table 5

Coloration with 2-nitrocinnamaldehyde

Table 6

Coloration with 4-nitrocinnamaldehyde

Table 7

Coloration with 2,4-dinitrobenzaldehyde

Table 8

Coloring with 3-hydroxy-4-nitrobenzaldehyde

Claims (12)

1. Agent for coloring keratin-containing fibers, in particular human hair, containing at least one aromatic nitroaldehyde with the formula I as the coloring component,
in which R ¹ , R ² and R ³ independently of one another represent hydrogen atoms, halogen atoms, C ₁ -C ₄ -alkyl-, C ₁ -C ₄ -hydroxyalkyl-, amino-C ₁ -C ₄ -alkyl-, C ₁ -C ₄ alkoxy, C ₁ -C ₄ acyl, hydroxy, nitro, carboxy, C ₁ -C ₄ acylamino, sulfo or amino groups which are replaced by C ₁ -C ₄ alkyl or C ₂ -C ₄ - hydroxyalkyl groups can be substituted, two of the radicals can also together form a fused aromatic ring, and
n is 0, 1 or 2. 2. Means according to claim 1, characterized in that as compounds with of the formula I 2-nitrobenzaldehyde, 3-nitrobenzaldehyde, 4-nitrobenzaldehyde, 4- Methyl-3-nitrobenzaldehyde, 3-hydroxy-4-nitrobenzaldehyde, 4-hydroxy-3- nitrobenzaldehyde, 5-hydroxy-2-nitrobenzaldehyde, 2-hydroxy-5- nitrobenzaldehyde, 2-hydroxy-3-nitrobenzaldehyde, 2-fluoro-3-nitrobenzaldehyde, 3-methoxy-2-nitrobenzaldehyde, 4-chloro-3-nitrobenzaldehyde, 2-chloro-6-ni trobenzaldehyde, 5-chloro-2-nitrobenzaldehyde, 4-chloro-2-nitrobenzaldehyde, 2,4- Dinitrobenzaldehyde, 2,6-dinitrobenzaldehyde, 2-hydroxy-3-methoxy-5- nitrobenzaldehyde, 4,5-dimethoxy-2-nitrabenzaldehyde, 6-nitropiperonal, 2- Nitropiperonal, 5-nitrovanillin, 2,5-dinitrosalicylaldehyde, 5-bromo-3- nitrosalicylaldehyde, 3-nitro-4-formylbenzenesulfonic acid, 4-nitro-1- naphthaldehyde, 2-nitrocinnamaldehyde, 3-nitrocinnamaldehyde, 4-nitrocinnamaldehyde and any mixtures thereof can be used. 3. Means according to one of claims 1 to 2, characterized in that the aromatic nitroaldehyde 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. Means according to one of claims 1 to 3, characterized in that it additionally at least one connection with primary or secondary Amino group or hydroxyl group selected from primary or secondary aliphatic or aromatic amines, nitrogenous heterocyclic compounds, amino acids, from 2 to 9 amino acids built-up oligopeptides and aromatic hydroxy compounds, and / or at least one CH-active compound. 5. Agent according to claim 4, characterized in that the further compound is selected from primary or secondary amines from the group consisting of N- (2-hydroxyethyl) -N-ethyl-, N- (2-methoxyethyl-), 2 , 3-, 2,4-, 2,5-dichloro-p-phenylenediamine, 2-chloro-p-phenylenediamine, N, N-bis (2-hydroxyethyl) -p-phenylenediamine, 2,5-dihydroxy 4-morpholinoaniline dihydrobromide, 2-, 3-, 4- aminophenol, o-, m-, p-phenylenediamine, 2,4-diaminophenoxyethanol, 2- (2,5-diaminophenyl) ethanol, 2,5-diaminotoluene, -phenol, -phenethol, 4-methylamino-, 3-amino-4- (2'-hydroxyethyloxy) -, 3,4-methylenediamino-, 3,4-methylenedioxyaniline, 3-amino-2,4-dichloro- , 4-methylamino-, 2-methyl-5-amino-, 3-methyl-4-amino-, 2-methyl-5- (2-hydroxyethylamino) -, 2-methyl-5-amino-4-chloro, 6-methyl-3-amino-2-chloro-, 5- (2-hydroxyethylamino) -4-methoxy-2-methyl-, 4-amino-2-aminomethyl-phenol, 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 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-triaminophenol trihydrochloride, pentaaminobenzene pentahydrochloride , Hexaaminobenzene hexahydrochloride, 2,4,6-triaminoresorcinol trihydrochloride, 4,5-diaminobenzcatechol sulfate, 4,6-diaminopyrogallol dihydrochloride, 3,5-diamino-4-hydroxypyrocatechol sulfate, aromatic nitriles, anilines, especially those containing nitro groups Anilines, such as 4-nitroaniline, 4-nitro-1, 3-phenylenediamine, 2-nitro-4-amino-1- (2-hydroxyethyl amino) benzene, 2-nitro-1-amino-4- [bis- ( 2-hydroxyethyl) amino] benzene, 4-amino-2-nitrodiphenyl amine-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 such as 4,4'-diaminostilbene dihydrochloride, 4,4'-diaminostilbene-2,2'-disulfonic acid, Na salt, 4,4'-diaminodiphenylmethane, sulfide, sulfoxide, amine, 4,4'-diaminodiphenylamine-2 - sulfonic acid, 4,4'-diaminobenzophenone, -diphenylether, 3,3 ', 4,4'-tetraamino diphenyl-tetrahydrochloride, 3,3', 4,4'-tetraaminobenzophenone, 1,3-bis- (2,4 - diaminophenoxy) 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 ethyl-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-aminobenzimidazole, -benzo thiazole, 2,5- Dihydroxy-4-morpholinoaniline and 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, as well as each from the physiologically compatible salts of these compounds formed with preferably inorganic acids,
aromatic hydroxy compounds selected from the group consisting of 2-, 4-, 5-methylresorcinol, 2,5-dimethylresorcinol, resorcinol, 3-methoxyphenol, pyrocatechol, hydroquinone, pyrogallol, phloroglucinol, hydroxyhydroquinone, 2-, 3-, 4-methoxy -, 3-dimethylamino, 2- (2-hydroxyethyl) -, 3,4-methylenedioxyphenol, 2,4-, 3,4-dihydroxybenzoic acid, -phenylacetic acid, gallic acid, 2,4,6-trihydroxybenzoic acid, -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 -es acetic acid, 1-methyl-2-quinaldinium iodide, 1-ethyl-2-quinaldinium iodide, 1,4-dimethylquinolinium iodide, barbituric acid, thiobarbituric acid, 1,3-dimethylthiobarbituric acid, 1,3-diethylthiobarbituric acid, diethylthiobarbituric acid , Oxindole, 3-indoxylacetate, coumaranone and 1-methyl-3-phenyl-2-pyrazolinone. 6. Means according to claim 5, characterized in that the further Compound is selected from the group consisting of N- (2- Hydroxyethyl) -N-ethyl-, 2-chloro-p-phenylenediamine, N, N-bis- (2-hydroxyethyl) -p- phenylenediamine, 4-aminophenol, p-phenylenediamine, 2- (2,5-diaminophenyl) - ethanol, 2,5-diaminotoluene, 3,4-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-hydroxyethyl amino), 2-methyl-5-amino-4-chloro, 6-methyl-3-amino-2-chloro, 2-amin atoms ethyl-4-aminophenol, 2-hydroxymethyl-4-aminophenol 3,4- Methylenedioxyphenol, 3,4-diaminobenzoic acid, 2,5-diamino, 2-dimethyl amino-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 as well as each from the physiologically formed, preferably with inorganic acids compatible salts of these compounds. 7. Agent according to one of claims 1 to 6, characterized in that it direct dyes from the group of nitrophenylenediamines, nitro aminophenols, anthraquinones or indophenols, preferably in one Amount from 0.01 to 20 wt .-%, based on the total colorant, contains. 8. Agent according to one of claims 1 to 7, characterized in that Ammonium or metal salts selected from the group of formates, Carbonates, halides, sulfates, butyrates, valemates, capronates, acetates, Lactates, Glycolates, Tartrates, Citrates, Gluconates, Propionates, and Phosphates 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, to be added. 9. Agent according to one of claims 1 to 8, 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. 10. Agent according to one of claims 1 to 9, characterized in that it contains anionic, zwitterionic or nonionic surfactants. 11. Use of aromatic nitroaldehydes with the formula I,
in which R ¹ , R ² and R ³ independently of one another represent hydrogen atoms, halogen atoms, C ₁ -C ₄ -alkyl-, C ₁ -C ₄ -hydroxyalkyl-, amino-C ₁ -C ₄ -alkyl-, C ₁ -C ₄ alkoxy, C ₁ -C ₄ acyl, hydroxy, nitro, carboxy, C ₁ -C ₄ acylamino, sulfo or amino groups which are replaced by C ₁ -C ₄ alkyl or C ₂ -C ₄ - hydroxyalkyl groups can be substituted, two of the radicals can also together form a fused aromatic ring, and
n stands for 0, 1 or 2,
as a coloring component in oxidation hair dyes. 12. A process for dyeing keratin-containing fibers, in particular human hair, in which a coloring agent contains

• A) at least one aromatic nitroaldehyde with the formula I,
  in which R ¹ , R ² and R ³ independently of one another represent hydrogen atoms, halogen atoms, C ₁ -C ₄ -alkyl-, C ₁ -C ₄ -hydroxyalkyl-, amino-C ₁ -C ₄ -alkyl-, C ₁ -C ₄ alkoxy, C ₁ -C ₄ acyl, hydroxy, nitro, carboxy, C ₁ -C ₄ acylamino, sulfo or amino groups which are replaced by C ₁ -C ₄ alkyl or C ₂ -C ₄ -hydroxyalkyl groups can be substituted, it also being possible for two of the radicals together to form a fused aromatic ring,
  n is 0, 1 or 2, and
• B) at least one compound with 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 made up of 2 to 9 amino acids and aromatic hydroxy compounds, and / or at least one CH-active compound,

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