WO2001030312A1 - Means for colouring keratin containing fibres - Google Patents

Abstract

A means for colouring keratin containing fibres, in particular human hair, is disclosed, comprising at least one carbazolaldehyde and/or a carbazoleketone of formula (I) in which R1 = H, C¿1-4? alkyl or aryl; R?2, R3, R4 and R5¿ = H, halogen, C¿1-4? alkyl, C1-4 alkoxy or C1-4 hydroxyalkoxy, OH, NO2, NH2, optionally substituted with C1-4 alkyl, or C1-4 acyl and two of the residues together can also form a condensed aromatic ring and R?6¿ = C¿1-4? alkyl, C1-4 hydroxyalkyl, C1-4 carboxyalkyl, C1-4 sulphoalkyl, aryl, aralkyl- or heteroaryl.

Description

 "Means for dyeing fibers containing keratin"

The invention relates to an agent for dyeing keratin-containing fibers, in particular human hair, which contains carbazole aldehydes and ketones, and to a method for dyeing keratin-containing fibers, in particular human hair.

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

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

Special representatives are, for example, p-phenylenediamine, p-toluenediamine, 2,4,5,6-tetraaminopyrimidine, p-aminophenol, N, N-bis (2-hydroxyethyl) -p-phenylenediamine, 2- (2.5 Diaminophenyl) ethanol, 2- (2,5-diaminophenoxy) ethanol, 1-phenyl-3-carboxyamido-4-amino-pyrazolon-5, 4-amino-3-methylphenol, 2-aminomethyl-4-aminophenol, 2-hydroxymethyl-4-aminophenol, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6-triamino-4-hydroxypyrimidine.

M-Phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones, m-aminophenols and substituted pyridine derivatives are generally used as coupler components. Particularly suitable coupler substances are α-naphthol, 1, 5-, 2,7- and 1, 7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, p-phenylenediamine, 2,4-diaminophenoxyethanol , 2-Amino-4- (2-hydroxyethylamino) anisole (Lehmanns Blau), 1-phenyl-3-methyl-pyrazolon-5, 2,4-di-chloro-3-aminophenol, 1, 3-bis- ( 2,4-diaminophenoxy) propane, 2-chlororesorcinol, 4-chloro- sorcinol, 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 further customary dye components, reference is expressly made to the “Dermatology” series, edited by Ch. Culnan, H. Maibach, publisher 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 disk form from the Federal Association of German Industrial and Commercial Enterprises for Medicines, Health Care Products and Personal Care Products, Mannheim ,

With oxidation dyes intensive dyeings can be achieved with good fastness properties, but the development of the color is usually done under the influence of oxidizing agents such. B. H ₂ O ₂ , which in some cases can damage the fiber. Furthermore, some oxidation dye precursors or certain mixtures of oxidation dye precursors can sometimes have a sensitizing effect on people with sensitive skin. Direct dyes are applied under gentler conditions, but their disadvantage is that the dyeings often have inadequate fastness properties.

The use of the carbazole aldehyde or ketone described below for dyeing keratin-containing fibers is not yet known.

The object of the present invention is to provide colorants for keratin fibers, in particular human hair, which are qualitatively at least equivalent to the usual oxidation hair colorants in terms of color depth, gray coverage and fastness properties, but without necessarily relying on oxidizing agents such as e.g. B. H ₂ 0 _{2 to be} instructed. In addition, the colorants may have no or only a very low sensitization potential.

Surprisingly, it has now been found that the carbazole aldehydes or ketones shown in the formula I are outstandingly suitable for dyeing keratin-containing fibers even in the absence of oxidizing agents. They give color with excellent brilliance and depth of color and lead to diverse color nuances. However, the use of oxidizing agents should not be excluded in principle.

The invention relates to an agent for dyeing keratin-containing fibers, in particular human hair, containing at least one carbazolaldehyde and / or a carbazole ketone with the formula I,

in which R ^{1 is} a hydrogen atom, a C _1-4 alkyl or an aryi radical,

R ² , R ³ , R ⁴ and R ^{5 represent} a hydrogen, halogen atom, a C _1-4 alkyl, C _1-4 alkoxy or C _1-4 hydroxyalkoxy group, a hydroxy, nitro, amino group, by C ^

₄ alkyl groups can be substituted, or C ^ acyl group and two of

Residues can also together form a fused aromatic ring and

R ^{6 is} a C alkyl, C _1-4 hydroxyalkyl, C _1-4 carboxyalkyl, C _1-4 sulfoalkyl, a

Aryl, aralkyl or heteroaryl group means.

Keratin-containing fibers are wool, furs, feathers and in particular human hair. In principle, however, the colorants according to the invention can also be used for dyeing other natural fibers, such as, for. As cotton, jute, sisal, linen or silk, modified natural fibers, such as. B. regenerated cellulose, nitro, alkyl or hydroxyalkyl or acetyl cellulose and synthetic fibers such as. B. polyamide, polyacrylonitrile, polyurethane and polyester fibers can be used.

The compounds of the formula I are preferably selected from 9-methyl-3-carbazolaldehyde, 9-ethyl-3-carbazolaldehyde, 3-acetylcarbazole, 3,6-diacetyl-9-ethylcarbazole, 3-acetyl-9-methylcarbazole, 1, 4-dimethyl-3-carbazolaldehyde, 1, 4,9-trimethyl-3-carbazolaldehyde and any mixtures thereof. Most of these substances are known from the literature or are commercially available or can be prepared by known synthetic processes.

The aforementioned carbazolaldehydes and ketones with the formula I are preferably used 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. They can be used as substantive colorants or in the presence of customary oxidation dye precursors.

Coloring agents which contain the carbazolaldehydes and / or ketones with the formula I alone as the coloring component are preferably used for lighter colors. Colorings with an even higher brilliance and improved fastness properties (light fastness, wash fastness, rub fastness) over a wide range of shades from yellow-brown to orange, brown-orange, medium brown, dark brown, olive green to blue-black and black are achieved if the compounds of formula I used according to the invention together with at least one further component (hereinafter referred to as component B), selected from compounds having a 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 CH-active compounds. On the one hand, these are compounds which, on their own, only weakly dye keratin-containing fibers and only give brilliant colors together with the compounds of the formula I. On the other hand, there are also compounds that are already used as oxidation dye precursors.

Several different carbazolaldehydes and / or ketones of the formula I can also be used together in all colorants; Likewise, several different compounds of component B can also be used together.

The embodiment described above also includes the use of those substances which are reaction products of carbazolaldehydes and / or ketones of the formula I with the compounds of component B mentioned as direct colorants. Such reaction products can e.g. B. by short Heating the two components in stoichiometric amounts in an aqueous neutral to weakly alkaline medium can be obtained, in which case they either precipitate out of the solution as a solid or are isolated therefrom by evaporation of the solution. The reaction products can also be used in combination with other dyes or dye precursors.

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-morphoiinoaniiine dihydrobromide, 2 -, 3-, 4-aminophenol, 2-aminomethyl-4-aminophenol, 2-hydroxymethyl-4-aminophenol, o-, p-phenylenediamine, o-toluenediamine, 2,5-diaminotoluene, -phenol, - phenethole, 4- Amino-3-methylphenol, 2- (2,5-diaminophenyl) -ethanol, 2,4-diaminophen-oxyethanol, 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-, 3rd -Methyl-4-amino-, 2-methyl-5- (2-hydroxyethylamino) -, 6-methyl-3-amino-2-chloro, 2-methyl-5-amino-4-chloro, 3,4 -Methylene dioxy-, 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-, 3rd -, 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-hydroxynaphthaiine-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, pentaaminobenzene, hexaaminobenzene, 2,4,6-triaminoresorcinol, 4,5-diaminobenzate catechin, 4,6-diaminopyrogallol, 3,5-diamino -4-hydroxycatechol, aromatic nitriles, anilines, in particular nitro group-containing anilines, such as 4-nitroaniline, 4-nitro-1,3-phenylenediamine, 2-nitro-4-amino-1- (2-hydroxyethylamino) benzene , 2-nitro-1-amino-4- [bis- (2-hydroxyethyl) amino] benzene, 4-amino-2-nitrodiphenylamine-2'-carboxylic acid, 2-amino-6-chloro-4-nitrophenol, 1-amino-5-chloro-4 - (2-hydroxyethylamino) -2-nitrobenzene, aromatic anilines or phenols with a further aromatic radical, as represented in formula II

in the R ⁷ for a hydroxyl or an amino group which can be substituted by C _1-4 alkyl, C ^ hydroxyalyl, C _1-4 alkoxy or C ^ alkoxy-C ^ alkyl groups , stands,

R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ^{12 represent} hydrogen, a hydroxy or an amino group through

C ^ alkyl, C _1-4 hydroxyalkyl, C ^ alkoxy, C _1-4 aminoalkyl or C ^ alkoxy-C ^ alkyl groups may be substituted, and

P 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

Z- (CH ₂ -Y-CH ₂ -Z ') ₀ (IM)

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 ¹³ group in which R ^{13 is} 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 '-0, where p and p' are 2 or 3, and o is 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-prop panol, 1,3-bis- [N- (4-aminophenyl) -2-hydroxyethylaminoj-2-propanol, N, N-bis- [2- (4-aminophenoxy) ethyl] methylamine, N-phenyl-1 , 4-phenylenediamine. The abovementioned compounds can be used both in free form and in the form of their physiologically tolerable salts, in particular as salts of inorganic acids, such as hydrochloric or sulfuric acid.

Suitable nitrogen-containing heterocyclic compounds are e.g. B. 2-, 3-, 4-amino, 2-amino-3-hydroxy, 2,6-diamino, 2,5-diamino, 2,3-diamino, 2-dimethylamino-5-amino -, 2-methylamino-3-amino-6-methoxy-, 2,3-diamino-6-methoxy-, 2,6-dimethoxy-3,5-diamine-, 2,4,5-triamino-, 2,6-dihydroxy-3,4-dimethylpyridine, 2,4-dihydroxy-5,6-diamino, 4,5,6-triamino, 4-hydroxy-2,5,6-triamino, 2-hydroxy -4,5,6-triamino-, 2,4,5,6-tetraamino-, 2-methylamino-4,5,6-triamino-, 2,4-, 4,5-diamino-, 2- Amino-4-methoxy-6-methyl-pyrimidine, 3,5-diaminopyrazole, -1, 2,4-triazole, 3-amino, 3-amino-5-hydroxypyrazole, 2-, 3-, 8- Aminoquinoline, 4-aminoquininaldine, 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. According to the invention, the hydroxypyrimidines disclosed in DE-U1-299 08 573 can also be used as heterocyclic compounds. The aforementioned compounds can be used both in free form and in the form of their physiologically tolerable salts, e.g. B. as salts of inorganic acids such as hydrochloric or sulfuric acid.

Suitable aromatic hydroxy compounds are e.g. B. 2-, 4-, 5-methylsorcinol, 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 -Chlorresorcin, 1-naphthol, 1, 5-, 2,3-, 2,7-dihydroxynaphthalene, 6-dimethylamino-4-hydroxy-2-naphthalenesulfonic acid, 3,6-dihydroxy-2,7-naphthalenesulfonic acid ,

Examples of CH-active compounds which may be mentioned are 1, 2,3,3-tetramethyl-3H-indolium iodide, 1, 2,3,3-tetramethyl-3H-indolium-p-toluenesulfonate, 1, 2,3,3-tetramethyl - 3H-indolium methanesulfonate, Fischer's base (1,3,3-trimethyl-2-methyleneindoline), 2,3-dimethyl-benzothiazolium iodide, 2,3-dimethyl-benzothiazolium-p-toluenesulfonate, 1,2-dimethyl -naphtho [1,2-d] thiazolium p-toluenesulfonate, 1-ethyl-2-methyl-naphtho [1,2-d] thiazolium p-toluenesulfonate, rhodanine, rhodanine-3-acetic acid, 1-methyl-2 -chinaldinium iodide, 1-E- thyl-2-quinaldinium iodide, 1, 4-dimethylquinolinium iodide, barbituric acid, thiobarbituric acid, 1, 3-dimethylthiobarbituric acid, 1, 3-diethylthiobarbituric acid, diethylthiobarbituric acid, oxindole, 3-indoxyl undethyl acetate, coumaranone 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-hydroxyethy!) - p- phenylenediamine, 4-aminophenol, p-phenylenediamine, 2- (2,5-diamino-phenyl) -ethanol, 2,5-diaminotoluene, 3,4-methylenedioxyaniline, 2-amino-4- (2-hydroxyethylamino) - anisole, 2- (2,4-diaminophenoxy) ethanol, 3-amino-2,4-dichloro, 2-methyl-5-amino, 3-methyl-4-amino, 2-methyl-5- ( 2-hydroxyethylamino) -, 2-methyl-5-amino-4-chloro, 6-methyl-3-amino-2-chloro, 2-aminomethyl-4-aminophenol, 2-diethylaminomethyl-4-amino- phenol, 2-dimethylaminomethyl-4-aminophenol, 2,6-dichloro-4-aminophenol, 2-hydroxymethyl-4-aminophenol, 3,4-methylenedioxyphenol, 3,4-diaminobenzoic acid, 2,5-diamino- , 2-dimethylamino-5-amino-, 3-amino-2-methylamino-6-methoxy-, 2,3-diamino-6-methoxy-, 3,5-diamino-2,6-dimethoxy-, 2nd , 6-dihydroxy-3,4-dimethylpyridine, 2-hydroxy-4,5,6-triamino-, 4-hydroxy-2,5,6-triamino-, 2,4,5,6-tetraamino-, 2- Methyla mino-4,5,6-triamino-pyrimidine, 3,5-diaminopyrazole, 3-amino-5-hydroxypyrazole, 5,6-dihydroxyindole and 5,6-dihydroxyindoline as well as their physiologically compatible salts formed with preferably inorganic acids.

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

Stand 1: 2. In order to obtain further and more intense colorations, the agents according to the invention can additionally contain color enhancers. 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.

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

On the presence of oxidizing agents, e.g. B. H ₂ 0 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, in addition to the compounds contained according to the invention, customary direct dyes, for example, for further modification of the color shades. B. from the group of nitrophenylenediamines, nitroaminophenols, anthraquinones or indophenols, such as. B. under the international names or trade names HC Yellow 2, HC Yellow 4, HC Yellow 6, Basic Yellow 57, Disperse Orange 3, HC Red 3, HC Red BN, Basic Red 76, HC Blue 2, Disperse Blue 3, Basic Blue 99, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9, Basic Brown 16 and Basic Brown 17 known compounds as well as picramic acid 2-amino-6-chloro-4-nitrophenol, 4-amino-2-nitrodiphenylamine -2'-carboxylic acid, 6-nitro-1, 2,3,4-tetrahydroquinoxaline, 4-N-ethyl-1, 4-bis- (2'-hydroxyethyamino) -2-nitrobenzene hydrochloride and 1-methyl -3-nitro-4- (2'-hydroxyethyl) aminobenzene. The inventive agents according to this embodiment preferably contain the substantive dyes in an amount of 0.01 to 20 wt .-%, based on the total colorant. Furthermore, the preparations according to the invention can also contain naturally occurring dyes such as, for example, henna red, henna neutral, henna black, chamomile flowers, sandalwood, black tea, rotten bark, sage, blue wood, madder root, catechu, sedre and alkanna root.

It is not necessary that the oxidation dye precursors or the optional direct dyes each represent uniform compounds. Rather, in the colorants according to the invention, due to the production process for the individual dyes, further components may be present in minor amounts, provided that these do not adversely affect the coloring result or for other reasons, e.g. B. toxicological, must be excluded.

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

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

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

linear fatty acids with 10 to 22 carbon atoms (soaps),

Ether carboxylic acids of the formula RO- (CH ₂ -CH ₂ 0) _x -CH ₂ -COOH, in which R is a linear alkyl group with 10 to 22 C atoms and x = 0 or 1 to 16, acyl sarcosides with 10 to 18 C- Atoms in the acyl group, acyl taurides with 10 to 18 C atoms in the acyl group, acyl isethionates with 10 to 18 C atoms in the acyl group,

Sulfosuccinic acid mono- and dialkyl esters with 8 to 18 carbon atoms in the alkyl group and sulfosuccinic acid mono-alkyl polyoxyethyl esters with 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups, linear alkane sulfonates with 12 to 18 carbon atoms, linear alpha-olefin sulfonates with 12 to 18 carbon atoms, alpha-sulfofatty acid methyl ester 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, sulfated hydroxyalkyl polyethylene and / or hydroxyalkylene propylene glycol ethers according to DE-A-37 23 354,

Sulfonates of unsaturated fatty acids with 12 to 24 carbon atoms and 1 to 6 double bonds according to DE-A-39 26 344,

Esters of tartaric acid and citric acid with alcohols, the addition products of about 2 to 15 molecules of ethylene oxide and / or propylene oxide to fatty alcohols with 8 to 22 carbon atoms.

Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids with 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule, and in particular salts of saturated and in particular unsaturated C ₈ -C ₂₂ carboxylic acids, such as oleic acid, stearic acid, isostearic acid and Palmitic acid. Zwitterionic surfactants are surface-active compounds that contain at least one quaternary ammonium group and at least one -COO ^H - or -S0 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 surface-active compounds which, apart from a C ₈ .ι ₈ alkyl or acyl group in the molecule at least one free amino group and at least one -COOH or -SO ₃ H group and the formation of internal salts are capable , Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each with about 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocosalkylaminopropionate, cocoacylaminoethylaminopropionate and C ₁₂ . ₁₈ acyl sarcosine.

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

Addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide with linear fatty alcohols with 8 to 22 C atoms, with fatty acids with 12 to 22 C atoms and with alkylphenols with 8 to 15 C atoms in the alkyl group , C _12-22 fatty acid monoesters and diesters of adducts of 1 to 30 moles of ethylene oxide with glycerol,

C _{8-22 alkyl} mono- and oligoglycosides and their ethoxylated analogues, addition products of 5 to 60 mol ethylene oxide onto castor oil and hardened castor oil, Addition products of ethylene oxide with sorbitan fatty acid esters Addition products of ethylene oxide with fatty acid alkanolamides.

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

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

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

Also very good biodegradability are quaternary Esterverbindungen, so-called "esterquats", alkyldialkoyloxyalkylammoniummethosulfate such as those sold under the trade name Stepantex® ^® methylhydroxy-.

An example of a quaternary sugar derivative that can be used as a cationic surfactant is the commercial product Glucquat ^® 100, according to the CTFA no. A "Lauryl Methyl Gluceth-10 Hydroxypropyl Dimonium Chloride".

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

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

Further active ingredients, auxiliaries and additives are, for example, nonionic polymers such as, for example, vinylpyrrolidone / vinyl acrylate copolymers, polyvinylpyrrolidone and vinylpyrrolidone / vinyl acetate copolymers and polysiloxanes, cationic polymers such as quaternized cellulose ethers, polysiloxanes with quaternary acrylamides, dimethyl-dimethyldiallyl groups, dimethyldiallylially - ammonium chloride copolymers, quaternized with diethyl sulfate dimethylaminoethyl methacrylate-vinylpyrrolidone copolymers, vinylpyrrolidone-imidazolidinone niummethochlorid-copolymers to and quaternized polyvinyl alcohol, zwitterionic and amphoteric polymers such as, for example, acrylamidopropyl trimethyl ammonium chloride / acrylate copolymers and octylacrylamide / methyl methacrylate / tert .-Butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers, anionic polymers such as, for example, polyacrylic acids, crosslinked polyacrylic acids, vinyl acetate / crotonic acid copolymers, vinylpyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers,

Thickeners such as agar agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, linseed gums, dextrans, cellulose derivatives, e.g. B. methyl cellulose, hydroxyalkyl cellulose and carboxymethyl cellulose lulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such. B. bentonite or fully synthetic hydrocolloids such. B. polyvinyl alcohol,

Structurants such as glucose and maleic acid, hair-conditioning compounds such as phospholipids, for example soy lecithin, egg lecithin and cephalins, and silicone oils,

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

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

Anti-dandruff agents such as piroctone olamine and zinc omadine, other substances for adjusting the pH value,

Active ingredients such as panthenol, pantothenic acid, allantoin, pyrrolidone carboxylic acids and their salts, plant extracts and vitamins, cholesterol, light stabilizers,

Consistency 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 glycerol, propylene glycol monoethyl ether, carbonates, hydrogen carbonates, guanidines, ureas and primary, secondary and tertiary phosphates, imidazoles, tannins, pyrrole, opacifiers such as latex,

Pearlescent agents such as ethylene glycol mono- and distearate,

Blowing agents such as propane-butane mixtures, N ₂ 0, dimethyl ether, C0 ₂ and air and antioxidants.

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

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

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

The present invention further relates to the use of carbazolaldehydes and / or ketones having the formula I,

in which R ^{1 is} a hydrogen atom, a C _1-4 alkyl or an aryl radical,

R ² , R ³ , R ⁴ and R ^{5 represent} a hydrogen, halogen atom, a C _1-4 alkyl, C _1-4 alkoxy or C _1-4 hydroxyalkoxy group, a hydroxy, nitro, amino group, which can be replaced by C.,.

₄ alkyl groups may be substituted, or mean C _1-4 acyro group and two of the

Residues can also together form a fused aromatic ring and

R ^{6 is} a C _1-4 alkyl, C ^ hydroxyalkyl, C _1-4 carboxyalkyl, C ^ sulfoalkyl, a

Means aryl, aralkyi or heteroaryl group, 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 carbazolaldehyde and / or a carbazol ketone with the formula I,

in which R ^{1 is} a hydrogen atom, a C 1-4 alkyl or an aryl radical,

R ² , R ³ , R ⁴ and R ^{5 represent} a hydrogen, halogen atom, a C ^ alkyl, C ^ alkoxy or C _1-4 hydroxyalkoxy group, a hydroxy, nitro, amino group which is represented by C _{1 -4} alkyl groups can be substituted, or C _1-4 acyl group and two of the radicals can also together form a fused aromatic ring and

R ^{6 represents} a C _1-4 alkyl, C _1-4 hydroxyalkyl, C ^ carboxyalkyl, C ^ sulfoalkyl, an aryl, aralkyl or heteroaryl group, 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, aromatic hydroxy compounds, and / or at least one CH-active compound, and also conventional cosmetic ingredients, on the keratin-containing compounds Fibers applied, left on the fiber for some time, usually about 30 minutes and then rinsed out or washed out with a shampoo.

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

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

Examples

Preparation of a coloring solution

There was a slurry of 5 mmol of a carbazolaldehyde and / or ketone of the formula I, optionally 5 mmol of an oxidation dye precursor of component B and 5 mmol of sodium acetate and a drop of a 20% fatty alkyl ether sulfate solution in 50 ml of water at 50 ° C. After cooling to 30 ° C., the slurries were mixed with one another and adjusted to a pH of 9 with dilute NaOH or hydrochloric acid.

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

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

The color depth was rated on the following scale:

no or very pale color

(+) weak intensity

+ medium intensity

+ (+) medium to strong intensity ++ strong intensity

++ (+) strong to very strong intensity +++ very strong intensity Table 1

Colorings with 9-ethyl-3-carbazolaldehyde

Claims

claims

1. Agent for dyeing keratin fibers, in particular human hair, containing at least one carbazolaldehyde and / or a carbazole ketone with the formula I as the coloring component,

in which R ^{1 is} a hydrogen atom, a C _1-4 alkyl or an aryl radical,

R ² , R ³ , R ⁴ and R ^{5 represent} a hydrogen, halogen atom, a C ^ alkyl, C _1-4 alkoxy or C ^ hydroxyalkoxy group, a hydroxy, nitro, amino group which is represented by C _{1 -4} alkyl groups may be substituted, or mean C _1-4 acyl group and two of the radicals may together form a fused aromatic ring and

R ^{6 represents} a C _1-4 alkyl, C _1-4 hydroxyalkyl, C _1-4 carboxyalkyl, C _1-4 sulfoalkyl, an aryl, aralkyl or heteroaryl group.

2. Composition according to claim 1, characterized in that as compounds with the formula I 9-methyl-3-carbazolaldehyde, 9-ethyl-3-carbazolaldehyde, 3-acetylcarbazole, 3,6-diacetyl-9-ethylcarbazole, 3-acetyl -9-methylcarbazole, 1, 4-dimethyl-3-carbazole aldehyde, 1, 4,9-trimethyl-3-carbazolaldehyde and mixtures thereof can be used.

3. Composition according to one of claims 1 to 2, characterized in that the carbazolaldehydes and / or ketones of 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. Composition according to one of claims 1 to 3, characterized in that it additionally contains at least one compound having a primary or secondary amino group 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.

5. Composition 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-phenylene diamine, 2-chloro-p-phenylene diamine, N, N-bis- (2-hydroxyethyl) -p-phenylene diamine, 2,5-dihydroxy -4- morpholinoaniline dihydrobromide, 2-, 3-, 4-aminophenol, o-, m-, p-phenylenediamine, 2,4-diaminophenoxyethanol, 2- (2,5-diaminophenyl) ethanol, 2,5-diaminotoluene , - phenol, -phenethol, 4-methylamino-, 3-amino-4- (2'-hydroxyethyloxy) -, 3,4-methylene-diamino-, 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-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-diaminobenzate catechol sulfate, 4,6-diaminopyrogallol dihydrochloride, 3,5-diamino-4-hydroxybenzate catechol sulfate, aromatic nitri te, anilines, especially nitro group-containing anilines, such as 4-nitroaniline, 4-nitro-1,3-phenylenediamine, 2-nitro-4-amino-1- (2-hydroxyethylamino) benzene, 2-nitro-1-amino -4- [bis- (2-hydroxyethyl) amino] benzene, 4-amino-2-nitrodiphenylamine-2'-carboxylic acid, 2-amino-6-chloro-4-nitrophenol, 1-amino-5- chloro-4- (2-hydroyethylamino) -2-nitrobenzene, aromatic anilines or phenols with a further aromatic radical such as 4,4'- Diaminostilbene dihydrochloride, 4,4'-diaminostilbene-2,2'-disulfonic acid, Na salt, 4,4'-diaminodiphenylmethane, sulfide, sulfoxide, amine, 4,4'-diaminodiphenylamine-2-sulfonic acid , 4,4'-diaminobenzophenone, diphenyl ether, 3,3 ', 4,4'-tetraaminodiphenyl tetra-hydrochloride, 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-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-methyl-pyrimidine, 2,3,4-trimethylpyrrole, 2,4-dimethyl-3-ethylpyrrole, 3,5-diaminopyrazole, -1, 2,4-triazole, 3-amino-, 3- Amino-5-hydroxypyrazole, 2-, 3-, 8-aminoquinoline, 4-aminoquininaldine, 2-, 6-aminonicotinic acid, 5-aminoisoquinoline, 5-, 6-aminoindazole, 5-, 7-amino-benzimidazole, - benzothiazole, 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, 4-hydroxyindoline and the hydroxypyrimidines disclosed in DE-U 1-299 08 573, and in each case from the physiologically tolerable 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, hydroxyhydroch inone, 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,

1,3,3-tetramethyl-3H-indolium methanesulfonate, Fischer's base (1,3,3-trimethyl thyl-2-methylene indoline), 2,3-dimethyl-benzothiazolium iodide, 2,3-dimethyl-benzothiazolium-p-toluenesulfonate, 1, 2-dimethyl-naphtho [1,2-d] thiazolium-p-toluenesulfonate, 1 - Ethyl 2-methyl-naphtho [1, 2-d] thiazolium p-toluenesulfonate, rhodanine, rhodanine-3-acetic acid, 1-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-diethylthiobarbituric acid, diethylthiobarbituric acid, oxindole, 3-indoxy acetate, coumaranone phenyl and 1-methyl -2-pyrazolinone.

6. Composition 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- (2nd -Hydroxyethyl) -p-phenylenediamine, 4-aminophenol, p-phenylenediamine, 2- (2,5-diaminophenyl) -ethanol, 2,5-diaminotoluene, 3,4-methylenedi- oxyaniiin, 2-amino-4- (2nd -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- Diethylaminomethyl-4-aminophenol, 2-dimethyaminomethyl-4-aminophenol, 2,6-dichloro-4-aminophenol, 2-hydroxymethyl-4-aminophenol, 3,4-methylenedioxyphenol, 3,4-diaminobenzoic acid, 2,5-diamino- , 2-dimethylamino-5-amino, 3-amino-2-methylamino-6-methoxy, 2,3-diamino-6-methoxy, 3,5-diamino-2,6-dimethoxy-, 2,6 -Dihydroxy-3,4-dimethylpyridine, 2-hydroxy-4,5,6-triamino-, 4-hydroxy-2,5,6-triamino-, 2,4,5,6-Te traamino-, 2-methylamino-4,5,6-triamino-pyrimidine, 3,5-diaminopyrazole, 3-amino-5-hydroxypyrazole, 5,6-dihydroxyindole and 5,6-dihydroxyindoline and in each case preferably from the inorganic acids formed physiologically acceptable salts of these compounds.

7. Composition according to one of claims 1 to 6, characterized in that there are color enhancers selected from the group consisting of piperidine, piperidine-2-carboxylic acid, piperidine-3-carboxylic acid, piperidine-4-carboxylic acid, pyridine, 2-hydroxypyri - contains din, 3-hydroxypyridine, 4-hydroxypyridine, imidazole, 1-methylimidazole, histidine, pyrrolidine, proline, pyrrolidone, pyrrolidone-5-carboxylic acid, pyrazole, 1, 2,4-triazole, piperazidine or any mixtures thereof.

8. Composition according to one of claims 1 to 7, characterized in that there are direct dyes from the group of nitrophenylenediamines, nitroaminophenols, Anthraquinones or indophenols preferably in an amount of 0.01 to 20 wt .-%, based on the total colorant.

9. Composition according to one of claims 1 to 8, characterized in that ammonium or metal salts selected from the group of formates, carbonates, halides, sulfates, butyrates, valerates, capronates, acetates, lactates, glycolates, tartrates, citrates, gluconates, Propionates, phosphates and phosphonates of alkali metals, such as potassium, sodium or lithium, alkaline earth metals, such as magnesium, calcium, strontium or barium, or of aluminum, manganese, iron, cobalt, copper or zinc, can be added.

10. Agent according to one of claims 1 to 6, 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.

11. Agent according to one of claims 1 to 10, characterized in that it contains anionic, zwitterionic or nonionic surfactants.

12. Use of carbazolaldehydes and / or ketones with the formula I,

in which R ^{1 is} a hydrogen atom, a C 1-4 alkyl or an aryl radical,

R ² , R ³ , R ⁴ and R ^{5 represent} a hydrogen, halogen atom, a C _1-4 alkyl, C _1-4 alkoxy or C _1-4 hydroxyalkoxy group, a hydroxy, nitro, amino group, which can be substituted by C _1-4 alkyl groups, or mean C _M acyl group and two of the radicals can also together form a fused aromatic ring and

R ^{6 represents} a C _1-4 alkyl, C ^ hydroxyalkyl, C _1-4 carboxyalkyl, C _1-4 sulfoalkyl, an aryl, aralkyl or heteroaryl group, as a coloring component in oxidation hair dyes.

13. A method for dyeing keratin-containing fibers, in particular human hair, which contains a colorant

A) at least one carbazolaldehyde and / or a carbazol ketone with the formula I,

in which R is a hydrogen atom, a C _1-4 alkyl or an aryl radical,

R ² , R ³ , R ⁴ and R ^{5 represent} a hydrogen, halogen atom, a C _1-4 alkyl, C _M - alkoxy or C _1-4 hydroxyalkoxy group, a hydroxyl, nitro, amino group, which are formed by C ^ alkyl groups can be substituted, or mean C _1-4 acyl group and two of the radicals can also together form a fused aromatic ring and R ^{6 is} a C _1-4 alkyl, C _1-4 hydroxyalkyl, C ^ -Carboxyalkyl-, C _1-4 -sulfoalkyl, an aryl, aralkyl or heteroaryl group, and B) at least one compound having a primary or secondary amino group or hydroxy group selected from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic Hy - Droxy compounds, and / or at least one CH-active compound, as well as usual cosmetic ingredients, applied to the keratin fibers, left on the fiber for some time, usually about 30 minutes, and then rinsed out or washed out with a shampoo.