WO2001089460A2

WO2001089460A2 - Colorant for fibres containing keratin

Info

Publication number: WO2001089460A2
Application number: PCT/EP2001/005497
Authority: WO
Inventors: Hinrich Möller; Doris Oberkobusch; Horst Höffkes
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 2000-05-24
Filing date: 2001-05-15
Publication date: 2001-11-29
Also published as: WO2001089460A3; AU6596001A; DE10025672A1

Abstract

The invention relates to a colorant for fibres containing keratin, in particular human hair. Said colorant contains at least one quaternised heteroaromatic aldehyde and/or a quaternised heteroaromatic ketone of formula (I), wherein R1 represents a hydrogen atom, a C¿1?-C4 alkyl group, C1-C4 sulfoalkyl group, C1-C4 carboxyalkyl group, aryl group or heteroaryl group, R?2 and R3¿ represent a hydrogen atom, halogen atom, a C¿1?-C4 alkyl group, a C1-C4 alkoxy group, a C1-C4 hydroxyalkoxy group, a C1-C4 hydroxyalkyl group, a hydroxy group, a nitro group or an amino group, which can be substituted by C1-C4 alkyl groups that can also form a heterocyclic ring together with the nitrogen atom, whereby the two groups R?2 and R3¿ can together form a condensed aromatic ring, R4 represents a C¿1?-C4 alkyl group, C2-C4 alkenyl group, aryl group, aralkyl group, C1-C4 carboxyalkyl group or C1-C4 sulfoalkyl group, Y represents an NR?5¿ group, whereby R5 is a C¿1?-C4 alkyl group, aralkyl group or aryl group, an oxygen atom, sulphur atom or an optionally substituted methylene group, and Z?-¿ represents an anion, in particular halide, benzene sulphonate, p-toluene sulphonate, methane sulphonate, methyl sulphate, ethyl sulphate, trifluoromethane sulphonate, perchlorate, sulphate, hydrogen sulphate, tetrafluoroborate or tetrachlorozincate. The compounds of formula (I) can also be present as acetals or oximes.

Description

"Means for dyeing fibers containing keratin"

The invention relates to an agent for dyeing keratin-containing fibers, in particular human hair, which contains quaternized heteroaromatic aldehydes and / or ketones, the use of these compounds as a coloring component in oxidation hair dyeing compositions and a process for dyeing keratin-containing fibers, in particular human hair.

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

Primary aromatic amines with a further free or substituted hydroxy or amino group in the para or ortho position, diaminopyridine derivatives, heterocyclic hydrazones, 4-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-dichloro-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 with good fastness properties can be achieved, but the development of the color is usually done under the influence of oxidizing agents such. B. H ₂ O ₂ , which in some cases can damage the fiber. Furthermore, some oxidation dye precursors or certain mixtures of oxidation dye precursors can sometimes have a sensitizing effect on people with sensitive skin. Direct dyes are applied under gentler conditions, but their disadvantage is that the dyeings often have inadequate fastness properties.

The use of the quaternized heteroaromatic aldehydes and / or ketones described in more detail below for dyeing keratin-containing fibers has hitherto not been 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 O _{2 to be} instructed. In addition, the colorants may have no or only a very low sensitization potential.

Surprisingly, it has now been found that the quaternized heteroaromatic aldehydes and / or ketones shown in the formula I can also be found in the absence of oxidizing agents are ideal for dyeing keratin fibers. They result in colors with excellent brilliance and depth of color and lead to a wide range of shades. However, the use of oxidizing agents should not be excluded in principle.

The invention relates to an agent for dyeing keratin fibers, in particular human hair, containing at least one quaternized heteroaromatic aldehyde and / or quaternized.es heteroaromatic ketone with the formula I,

in the mean

R ^{1 is} a hydrogen atom, a CC ₄ alkyl group, C., - C ₄ sulfoalkyl group, C, -C ₄ -

Carboxyalkyl group, aryl group or heteroaryl group,

R ² and R ^{3 represent} a hydrogen atom, halogen atom, a C ₁ -C ₄ alkyl group, a C, -C ₄ -

Alkoxy group, a C _r C ₄ hydroxyalkoxy group, a C, -C ₄ hydroxyalkyl group, a

Hydroxy group, a nitro group or an amino group, which by CC ₄ -

Alkyl groups can be substituted, which can also form a heterocyclic ring together with the nitrogen atom, wherein the two radicals R ² and R ³ can also form a fused aromatic ring together,

R ^{4 is} a CrC ₄ alkyl group, C ₂ -C ₄ alkenyl group, aryl group, aralkyl group, C _r C ₄ -

Carboxyalkyl group or C _r C ₄ sulfoalkyl group,

Y is a group NR ⁵ , where R ^{5 represents} a C _r C ₄ alkyl group, aralkyl group or aryl group, an oxygen atom, a sulfur atom or an optionally substituted one

Methylene group, and

Z ^" an anion, in particular halide, benzenesulfonate, p-toluenesulfonate, methanesulfonate,

Methyl sulfate, ethyl sulfate, trifluoromethane sulfonate, perchlorate, sulfate, hydrogen sulfate,

Tetrafluoroborate or tetrachlorozincate, where the compounds of the formula I can also be present as acetals or oximes. 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 with the formula I are largely known from the literature, are commercially available or can be prepared by known synthetic processes.

The compounds having the formula I are preferably selected from 1,3-dimethyl-2-formylbenzimidazolinium, 2-diethoxymethyl-1,3-dimethylbenzimidazolium, 2-acetyl-1,3-dimethylbenzimidazolium, 2-benzoyl-1,3 -dimethylimidazolium-, 1, 3-dimethyl-2-formyl-imidazolium-, 2-formyl-3-methylbenzothiazolium-, 2-acetyl-3-methyl-benzothiazolium-, 2-formyl-3-methylbenzoxazolium-, 5-chloro 2-formyl-3-methylbenzothiazolium, 2-formyl

3-methylbenzoxazolium-, 2-acetyl-3-methylbenzoxazolium-, 3-ethyl-2-formylbenzoxazolium-, 3,5-dimethyl-2-formylbenzothiazolium-, 2-formyl-4,9-dihydro-3-methyl- 4,9-dioxonaphtho [2,3-d] thiazolium-, 2-benzoyl-3,4-dimethylthiazolium-, 2-hydroxyiminomethyl-1, 3,3-trimethyl-3H-indolium-, 2-hydroxyiminomethyl-5 nitro-1, 3,3-trimethyl-3H-indolium, 5-chloro-2-hydroxyiminomethyl-1,3,3-trimethyl-3H-indolium methanesulfonate, methyl sulfate, ethyl sulfate, p-toluenesulfonate, trifluoromethanesulfonate , -tetrafluoroborate, - perchlorate, -benzenesulfonate, iodide, -bromide, -chloride, -nitrate, -phosphate, -pyrophosphate, - trifluoroacetate and any mixtures thereof.

The above-mentioned quaternized heteroaromatic aldehydes and / or 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 quaternized heteroaromatic aldehydes and / or ketones with the formula I alone as the coloring component are preferably used for lighter colors. Colorings with even greater brilliance and improved Fastness properties (light fastness, wash fastness, fastness to rubbing) over a wide range of shades of brown and red are achieved if the compounds of the formula I used according to the invention are used together with at least one further component (hereinafter referred to as component B), selected from compounds with primary or secondary Amino group or hydroxy group selected from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds, amino acids, from 2 to 9 amino acids and oligopeptides 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 quaternized heteroaromatic aldehydes 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.

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-methoxyethyI-), 2,3-, 2,4-, 2,5-dichloro-p-phenylenediamine, 2-chloro-p-phenylenediamine, 2,5-dihydroxy-4-morpholinoaniline dihydrobromide, 2 -, 3-, 4-aminophenol, 2-aminomethyl-4-aminophenol, 2-hydroxymethyl-4-aminophenol, o-, p-phenylenediamine, o-toluenediamine, 2,5-diaminotoluene, -phenol, - 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-sul- fonic acid, 7-amino-4-hydroxynaphthalene-2-sulfonic acid, 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid, 3-amino-2-naphthoic acid, 3-aminophthalic acid, 5-aminoisophthalic acid, 1, 3, 5-, 1, 2,4-triaminobenzene, 1,2,4,5-tetraaminobenzene, 2,4,5-triaminophenol, pentaaminobenzene, hexaaminobenzene, 2,4,6-triaminoresorcinol, 4,5-diaminobenzate catequin, 4 , 6-diaminopyrogallol, 3,5-diamino-4-hydroxycatechol, aromatic nitriles, nitro group-containing amino compounds such as 3-amino-6-methylarnino-2-nitro-pyridine, picramic acid, 1 - (2 (3) -nitro- 4-amino) -phenylazo-2-hydroxy-7-trimethylammoniumnaphthalene chloride, 1-hydroxy-2-amino-4,6-dinitro-benzene, 1-amino-2-nitro-4-bis- (2-hydroxyethyl) -amino-benzene, 1-amino-2- (2-hydroxyethyl) -amino-5-nitro-benzene (HC Yellow No. 5), 1-amino-2-nitro-4- (2-hydroxyethyl) -aminobenzene ( HC Red No. 7), 2-chloro-5-nitro-N-hydroxyethyl-1,4-phenylenediamine, 1- (2-hydroxyethyl) amino-2-nitro-4-amino-benzene (HC Red No. 3 ), 4-amino-3-nitrophenol, 4-amino-2-nitrophenol, 6-Ni tro-o-toluidine, 1-amino-3-methyl-4- (2-hydroxyethyl) amino-6-nitrobenzene (HC Violet No. 1), 1-amino-2-nitro-4- (2,3- dihydroxypropyl) amino-5-chlorobenzene an (HC Red No. 10), 4-amino-2-nitrodiphenylamino-2'-carboxylic acid (2- (4-amino-2-nitroanilino) -benzoic acid), 6 -Nitro-2,5-diaminopyridine, 2-amino-6-chloro-4-nitrophenol, 2-amino-6-chloro-4-nitrophenol, 1-amino-2- (3-nitrophenylazo) -7-phenylazo-8 -naphthol-3,6-disulfonic acid, disodium salt (Acid blue No. 29), 1-amino-2- (2-hydroxy-4-nitrophenylazo) - 8-naphthol-3,6-disulfonic acid, disodium salt (Palatinchrome green), 1-Amino-2- (3-chloro-2-hydroxy-5-nitrophenylazo) -8-naphthol-3,6-disulfonic acid, disodium salt (gallion), 4-amino-4'-nitrostilbene-2,2'-disulfonic acid , Disodium salt, 2,4-diamino-3 ', 5'-dinitro-2'-hydroxy-5-methyl-azobenzene (Mordant brown 4), 4'-amino-4-nitrodiphenylamine-2-sulfonic acid, 4'-amino -3'-nitrobenzophenone-2-carboxylic acid, 1-amino-4-nitro-2- (2-nitrobenzylidenamino) benzene, 2- [2- (diethylamino) ethylamino] -5-nitroanili n, 3-amino-4-hydroxy-5-nitrobenzenesulfonic acid, 3-amino-3'-nitrobiphenyl, 3-amino-4-nitro-acenaphthene, 2-amino-1-nitronaphthalene, 5-amino-6-nitrobenzo-1 , 3-dioxole, anilines, in particular anilines containing nitro groups, such as 4-nitroaniline, 2-nitroaniline, 1, 4-diamino-2-nitrobenzene, 1, 2-diamino-4-nitrobenzene, 1-amino-2-methyl 6-nitrobenzene, 4-nitro-1,3-phenylenediamine, 2-nitro-4-amino-1- (2-hydroxyethylamino) benzene, 2-nitro-1-amino-4- [bis- (2-hydroxyethyl) -amino] -benzene, 4-amino-2-nitrodiphenylamine-2'-carboxylic acid, 2-amino-6-chloro-4-nitrophenol, 1-amino-5-chloro-4- (2-hydroxyethylamino) -2-nitrobenzoI , aromatic anilines or phenols with a further aromatic radical, as shown in formula II

in the R ⁶ for a hydroxy or an amino group which is substituted by C _1-4 alkyl, C _1-4 hydroxyalkyl, C _1-4 alkoxy or C ^ alkoxy-C ^ alkyl groups can be stands

R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ^{11 represent} hydrogen, a hydroxy or an amino group through

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, stand, 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 -Q-CH ₂ -Z ') ₀ (III)

in which Q denotes a direct bond, a CH ₂ or CHOH group,

Z and Z 'independently of one another for an oxygen atom, an NR ¹² group in which R ^{12 is} hydrogen, a C _1-4 -alkyl or a hydroxy-C _-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 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 hydrochloride, 4,4'-diaminodiphenylmethane, -sulfide, -sulfoxide, -amine, 4, 4'-diaminodiphenylamine-2-sulfonic acid, 4,4'-diaminobenzophenone, diphenyl ether, 3,3 ', 4,4'-tetraaminodiphenyl, 3,3', 4,4'-tetraamino-benzophenone, 1 , 3-bis (2,4-diaminophenoxy) propane, 1,8-bis (2,5-diaminophenoxy) -3,6-dioxaoctane, 1,3-bis (4-aminophenylamino) propane, -2 -propanol, 1,3-bis- [N- (4-aminophenyl) -2-hydroxyethylamino] -2-propanol, N, N-bis- [2- (4-aminophenoxy) ethyl] methylamine, N -Phenyl-1,4-phenylenediamine. The abovementioned compounds can be used both in free form and in the form of their physiologically tolerable salts, in particular as salts of inorganic acids, such as hydrochloric or sulfuric acid.

Suitable nitrogen-containing heterocyclic compounds are e.g. B. 2-, 3-, 4-amino, 2-amino-3-hydroxy, 2,6-diamino, 2,5-diamino, 2,3-diamino, 2-dimethylamino-5-amino -, 2-methylamino-3-amino-6-methoxy-, 2,3-diamino-6-methoxy-, 2,6-dimethoxy-3,5-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-U 1-299 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-methylresorcinol, 2,5-dimethylresorcinol, resorcinol, 3-methoxyphenol, pyrocatechol, hydroquinone, pyrogallol, phloroglucin, hydroxyhydroquinone, 2-, 3-, 4-methoxy-, 3-dimethylamino -, 2- (2-hydroxyethyl) -, 3,4-methylenedioxyphenol, 2,4-, 3,4-dihydroxybenzoic acid, -phenylacetic acid, gallic acid, 2,4,6-trihydroxybenzoic acid, -acetophenone, 2-, 4 -Chlorresorcin, 1-naphthol, 1, 5-, 2,3-, 2,7-dihydroxynaphthalene, 6-dimethylamino-4-hydroxy-2-naphthalenesulfonic acid, 3,6-dihydroxy-2,7-naphthalenesulfonic acid ,

Preferred amino acids are all naturally occurring and synthetic α-amino acids, for example the amino acids accessible by hydrolysis from vegetable or animal proteins, for example collagen, keratin, casein, elastin, soy protein, wheat gluten or almond protein. Both acidic and alkaline amino acids can be used. Preferred amino acids are arginine, histidine, tyrosine, phenylalanine, DOPA (dihydroxyphenylalanine), ornithine, lysine and tryptophan. However, other amino acids, such as 6-aminocaproic acid, can also be used.

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

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-toluosulfonate, 1-ethyl-2-methyl-naphtho [1, 2-d] thiazolium p-toluenesulfonate, rhodanine, rhodanine-3-acetic acid, 1-methyl-2 -chinaldinium iodide, 1-ethyl-2-quinaldinium iodide, 1, 4-dimethylquinolinium iodide, barbituric acid, thiobarbituric acid, 1, 3-dimethylthiobarbituric acid, 1, 3-diethylthiobarbituric acid, diethylthiobarbitol, oxychloride -Indoxy acetate, coumaranone and 1-methyl-3-phenyl-2-pyrazoIinon.

The compounds of component B are particularly preferably selected from the group consisting of N- (2-hydroxyethyl) -N-ethyl-, 2-chloro-p-phenylenediamine, N, N-bis- (2-hydroxyethyl) -p-phenylenediamine , 4-aminophenol, p-phenylenediamine, 2- (2,5-diaminophenyl) ethanol, 2,5-diaminotoluene, 3,4-methylenedioxyaniline, 2-amino-4- (2-hydroxyethyl-amino) anisole , 2- (2,4-diaminophenoxy) ethanol, 3-amino-2,4-dichloro, 2-methyl-5-amino, 3-methyl-4-amino, 2-methyl-5- (2nd -hydroxyethylamino) -, 2-methyl-5-amino-4-chloro, 6-methyl-3-amino-2-chloro, 2-aminomethyl-4-aminophenol, 2-diethylaminomethyl-4-aminophenol , 2-dimethylaminomethyl-4-aminophenol, 2,6-dichloro-4-aminophenol, 2-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-methyla mino-4,5,6-triamino pyrimidine, 3,5-diaminopyrazole, 3-amino-5-hydroxypyrazole, 5,6-dihydroxyindole and 5,6-dihydroxyindoline, ß-alanine, L-proline, L-lysine, DL-tyrosine and those formed with preferably inorganic acids physiologically acceptable salts.

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 proportions such 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 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 O ₂ , can be omitted. However, it can It may be desirable to add hydrogen peroxide or other oxidizing agents to the agents according to the invention to achieve the shades which are lighter than the keratin-containing fiber to be colored. Oxidizing agents are generally used in an amount of 0.01 to 6% by weight, based on the application solution. A preferred oxidizing agent for human hair is H ₂ O ₂ . In a preferred embodiment, the colorants according to the invention contain, in addition to the compounds contained according to the invention, customary direct dyes, for example, for further modification of the color shades. B. from the group of nitrophenylenediamines, nitroaminophenols, anthraquinones or indophenols, such as. B. under the international names or trade names HC Yellow 2, HC Yellow 4, HC Yellow 6, Basic Yellow 57, Disperse Orange 3, HC Red 3, HC Red BN, Basic Red 76, HC Blue 2, Disperse Blue 3, Basic Blue 99, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9, Basic Brown 16 and Basic Brown 17 known compounds as well as picramic acid 2-amino-6-chloro-4-nitrophenol, 4-amino-2-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) -aminobenzoI. The agents according to the invention in accordance with this embodiment preferably contain the substantive dyes in an amount of 0.01 to 20% by weight, based on the total colorant.

Furthermore, the preparations according to the invention can also contain naturally occurring dyes such as, for example, henna red, henna neutral, henna black, chamomile flowers, sandalwood, black tea, sapwood, sage, blue wood, madder root, catechu, sedre and alkanna root.

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

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

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

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

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

Ether carboxylic acids of the formula RO- (CH ₂ -CH ₂ O) _x -CH ₂ -COOH, in which R is a linear alkyl group with 10 to 22 C atoms and x = 0 or 1 to 16, acyl sarcosides with 10 to 18 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-3723 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 -SO ₃ ^(_) group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinate, for example the coconut alkyl dimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammonium glycinate, for example the coconut acylaminopropyl dimethylammonium glycinate, and 2 -Alkyl-3-carboxymethyl-3-hydroxyethyl-imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and the cocoacylaminoethylhydroxyethylcarboxymethylglycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known under the CTFA name Cocamidopropyl Betaine.

Ampholytic surfactants are surface-active compounds which, in addition to a C _8-18 alkyl or acyl group, contain at least one free amino group and at least one -COOH or -SO ₃ H group in the molecule and are capable of forming internal salts. Examples of suitable ampholytic surfactants are N-alkylglycine, N-alkylpropionic acid, N-alkylaminobutyric acid, N-alkyliminodipropion acids, N-hydroxyethyl-N-alkylamidopropylglycine, N-alkyltaurine, N-alkyl sarcosine, 2-alkylaminopropionic acid and alkylaminoacetic acid, each with about 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocosalkylaminopropionate, cocoacylaminoethylaminopropionate and C _12-18 acylsarcosine.

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

Addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide with linear fatty alcohols with 8 to 22 carbon atoms, with fatty acids with 12 to 22 carbon atoms.

Atoms and on alkylphenols with 8 to 15 carbon atoms in the alkyl group,

C _12-22 fatty acid monoesters and diesters of adducts from 1 to 30 mol

Ethylene oxide on glycerol,

C _{8-22 alkyl} mono- and oligoglycosides and their ethoxylated analogs,

Addition products of 5 to 60 moles of ethylene oxide with castor oil and hardened

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 ler: 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 trademark Stepantex ^® methylhydroxy-.

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

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

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

Other active ingredients, auxiliaries and additives are, for example nonionic polymers such as vinylpyrrolidone / vinyl acrylate copolymers, polyvinylpyrrolidone and vinylpyrrolidone-vinyl acetate copolymers and polysiloxanes, cationic polymers such as quaternized cellulose ethers, polysiloxanes having quaternä- ren groups, dimethyldiallylammonium chloride polymers, dimethyldiallylammonium chloride-acrylamide copolymers, quaternized dimethylaminoethyl methacrylate with diethyl Vinylpyrrolidone copolymers, vinylpyrrolidone-imidazolinium methochloride copolymers and quaternized polyvinyl alcohol, zwitterionic and amphoteric polymers such as, for example, acrylamidopropyl-trimethylammonium chloride / acrylate copolymers and octylacrylamide / methyl methacrylate / tert-butylamino-2-methyl acrylate / hydroxyl-butylamino Polymers such as polyacrylic acids, cross-linked polyacrylic acids, vinyl acetate / crotonic acid copolymers, vinyl pyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyls ether / maleic anhydride copolymers and acrylic acid / ethyl acrylate / N-tert-butylacrylamide terpolymers,

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

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

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

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

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

Active ingredients such as panthenol, pantothenic acid, allantoin, pyrrolidone carboxylic acids and their salts, plant extracts and vitamins, Cholesterol, sunscreen,

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 O, dimethyl ether, CO ₂ and air as well as antioxidants.

The constituents of the water-containing carrier are used to produce the colorants according to the invention in amounts customary for this purpose; z. For example, emulsifiers are used 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 quaternized heteroaromatic aldehydes and / or ketones of the formula I,

in which R ¹ , R ² , R ³ , R ⁴ , Y and Z ^"are as defined above, as a coloring component in oxidation hair colorants.

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

A) at least one quaternized heteroaromatic aldehyde and / or quaternized heteroaromatic ketone with the formula I,

in which R ¹ , R ² , R ³ , R ⁴ , Y and Z ^"are as defined above and

B) at least one compound with primary or secondary amino group or hydroxy group, selected from primary or secondary aliphatic or aromatic amines, nitrogen-containing heterocyclic compounds, aromatic hydroxy compounds, amino acids, from 2 to 9 amino acids built oligopeptides and / or at least one CH- active compound, as well as usual cosmetic ingredients, applied to the keratin fibers, left on the fibers for some time, usually about 30 minutes, and then rinsed out or washed out with a shampoo.

The quaternized heteroaromatic aldehydes and / or ketones of the formula I and the compounds of component B can either be applied simultaneously to the hair. be brought or one after the other, it is 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 quaternized heteroaromatic aldehydes and / 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

1,3-dimethyl-2-formyl-benzϊmidazolium methanesulfonate

1.98 g (18 mmol) of methyl methanesulfonate were added to the solution of 2.3 g (14 mmol) of 2-formyl-1-methylbenzimidazole in 25 ml of toluene with stirring and the mixture was heated to 80 ° C. for 24 hours. After cooling to room temperature, the precipitate was decanted off, washed several times with warm toluene and then dried in an oil pump vacuum. 1.6 g (42.1% of theory) of a yellowish product with a melting point of 147 ° C. were obtained.

Preparation of a coloring solution

A slurry of 5 mmol each of a quaternized heteroaromatic aldehyde and 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% strength 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

Discolorations with 1,3-dimethyl-2-formyl-benzimidazolium methanesulfonate

Claims

claims

1. agent for dyeing keratin-containing fibers, in particular human hair, containing at least one quaternized heteroaromatic aldehyde and / or a quaternized heteroaromatic ketone with the formula I as the coloring component,

in the mean

R ^{1 is} a hydrogen atom, a C, -C ₄ alkyl group, C _r C ₄ sulfoalkyl group, C, -C ₄ -

Carboxyalkyl group, aryl group or heteroaryl group,

R ² and R ^{3 represent} a hydrogen atom, a halogen atom, a CrOcalkyl group, a C _r C ₄ -

Alkoxy group, a C _r C ₄ -hydroxyalkyl group, a CC ₄ -hydroxyalkoxy group, a hydroxy group, a nitro group or an amino group which is represented by C ^ Or

R ⁴ is a C, -. _C4 alkyl group, C ₂ -C ₄ alkenyl group, aryl group, aralkyl group, C, -C ₄ -

Carboxyalkyl group or C, -C ₄ sulfoalkyl group,

Y is a group NR ⁵ , where R ^{5 is} a C ^ C ^ alkyl group, aralkyl group or

Aryl group, an oxygen atom, sulfur atom or an optionally substituted methylene group, and

Z ^" an anion, especially halide, benzenesulfonate, p-toluenesulfonate,

Methanesulfonate, methyl sulfate, ethyl sulfate, trifluoromethanesulfonate, perchlorate, sulfate,

Hydrogen sulfate, tetrafluoroborate or tetrachlorozincate, where the compounds of the formula I can also be present as acetals or oximes.

2. Composition according to claim 1, characterized in that as compounds with the formula I 1, 3-dimethyl-2-formylbenzimidazolinium, 2-diethoxymethyl 1-1, 3-dimethylbenzimidazolium, 2-acetyl-1, 3-dimethylbenzimidazolium , 2-benzoyl-1, 3-dimethylimidazolium, 1, 3-dimethyl-2-formylimidazolium, 2-formyl-3-methylbenzothiazolium, 2-acetyl-3-methyl-benzothiazolium, 2-formyl-3-methylbenzoxazolium -, 5-chloro-2-formyl-3-methylbenzothiazolium-, 2-formyl-3-methylbenzoxazolium-, 2-acetyl-3-methylbenzoxazolium-, 3-ethyl-2-formylbenzoxazolium-, 3,5-dimethyl-2- formylbenzothiazolium-, 2-formyl-4,9-dihydro-3-methyl-4,9-dioxo-naphtho [2,3-d] thiazolium-, 2-benzoyl-3,4-dimethylthiazolium-, 2-hydroxyiminomethyl-1 , 3,3-trimethyl-3H-indolium-, 2-hydroxyiminomethyl-5-nitro-1, 3,3-trimethyl-3H-indolium-, 5-chloro-2-hydroxyiminomethyl-1, 3,3-trimethyl-3H -indoliuim-methanesulfonate, -methylsulfate, -p- toluenesulfonate, -trifluoromethanesulfonate, -tetrafluoroborate, -perchlorate, -benzenesulfonate, iodide, -bromide , Chloride, nitrate, phosphate, pyrophosphate, trifluoroacetate and any mixtures thereof.

3. Composition according to one of claims 1 to 2, characterized in that the quaternized heteroaromatic aldehydes 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. Agent according to one of claims 1 to 3, characterized in that it additionally has at least one compound with primary or secondary amino group or hydroxy group, selected from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds, amino acids, from 2 to 9 amino acids built oligopeptides 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, phenethole, 4-methylamino, 3-amino-4- (2'-hydroxyethyloxy) -, 3rd , 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 le, nitro group-containing amino compounds, such as 3-amino-6-methylamino-2-nitro-pyridine, picramic acid, 1- (2 (3) -nitro-4-amino) -phenylazo-2-hydroxy-7-trimethylammoniumnaphthalene chloride , 1-hydroxy-2-amino-4,6-dinitro-benzene, 1-amino-2-nitro-4-bis- (2-hydroxyethyl) -amino-benzene, 1-amino-2- (2-hydroxyethyl) -amino-5-nitro-benzene (HC Yellow No. 5), 1-amino-2-nitro-4- (2-hydroxyethyl) aminobenzene (HC Red No. 7), 2-chloro-5-nitro-N - hydroxyethyl-1,4-phenylenediamine, 1- (2-hydroxyethyl) amino-2-nitro-4-amino-benzene (HC Red No. 3), 4-amino-3-nitrophenol, 4-amino-2- nitrophenol, 6-nitro-o-toluidine, 1-amino-3-methyl-4- (2-hydroxyethyl) amino-6-nitrobenzene (HC Violet No. 1), 1-amino-2-nitro-4- ( 2,3-dihydroxypropyl) amino-5-chlorobenzene an (HC Red No. 10), 4-amino-2-nitrodiphenyl-amino-2'-carboxylic acid (2- (4-amino-2-nitroanilino) -benzoic acid) , 6-nitro-2,5-diaminopyridine, 2-amino-6-chloro-4-nitrophenol, 2-amino-6-chloro-4-nitrophenol, 1-amino-2- (3-nitrophenylazo) -7 phenylazo-8-naphthol-3,6-disulf onic acid, disodium salt (Acid blue No. 29), 1-amino-2- (2-hydroxy-4-nitrophenylazo) -8-naphthol-3,6-disulfonic acid, disodium salt (Palatinchrome green), 1-amino-2- ( 3-chloro-2-hydroxy-5-nitrophenylazo) -8-naphthol-3,6-disulfonic acid, disodium salt (Gallion), 4-amino-4'-nitrostibene-2,2'-disulfonic acid, disodium salt, 2,4-diamino-3 ', 5'-dinitro-2'-hydroxy-5-methyl-azobenzene (Mordant brown 4th ), 4'-amino-4-nitrodiphenylamine-2-sulfonic acid, 4'-amino-3'-nitrobenzophenone-2-carboxylic acid, 1 - amino-4-nitro-2- (2-nitrobenzylideneamino) benzene, 2- [ 2- (diethylamino) ethylamino] -5-nitroaniline, 3-amino-4-hydroxy-5-nitrobenzenesulfonic acid, 3-amino-3'-nitrobiphenyl, 3-amino-4-nitro-acenaphthene, 2-amino-1- nitronaphthalene, 5-amino-6-nitrobenzo-1,3-dioxole, anilines, in particular nitro group-containing anilines, such as 4-nitroaniline, 2-nitroaniline, 1,4-diamino-2-nitrobenzene, 1,2-diamino-4 -nitrobenzene, 1-amino-2-methyl-6-nitrobenzene, 4-nitro-1, 3-phenylenediamine, 2-nitro-4-amino-1- (2-hydroxyethylamino) benzene, 2-nitro-1-amino -4- [bis- (2-hydroxyethyl) amino] benzene, 4-amino-2-nitrodiphenylamine-2'-carboxylic acid, 2-amino-6-chloro-4-nitrophenol, 1-amino-5-chloro 4- (2-hydroxyethylamino) -2-nitrobenzoI, anilines, in particular nitro group-containing anilines, such as 4- Nitroaniline, 2-nitroaniline, 1,4-diamino-2-nitrobenzene, 1,2-diamino-4-nitrobenzene, 1-amino-2-methyl-6-nitrobenzene, 4-nitro-1,3-phenylenediamine, 2- Nitro-4-amino-1 - (2-hydroxyethylamino) benzene, 2-nitro-1-amino-4- [bis- (2-hydroxyethyl) aminoj-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 such as 4,4'- Diaminostilbene-dihydrochloride, 4,4'-diaminostilbene-2,2'-disulfonic acid, sodium salt, 4,4'-

Diaminodiphenylmethane, sulfide, sulfoxide, amine, 4,4'-diaminodiphenylamine-2-sulfonic acid, 4,4'-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-amino-quinaldine, 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 in DE-U 1-299 08 573 disclosed hydroxypyrimidines, and in each case from the physiologically tolerable salts formed with preferably inorganic acids of these compounds, aromatic hydroxy compounds selected from the group consisting of 2-, 4-, 5-methylresorcinol, 2,5-dimethylresorcinol , Resorcinol, 3-methoxyphenol, pyrocatechol, hydroquinone, pyrogallol, phloroglucin, hydroxyhydroquinone, 2-, 3-, 4-methoxy-, 3-dimethylamino-, 2- (2-hydroxyethyl) -, 3,4-methylenedioxyphenol, 2,4-, 3,4-dihydroxybenzoic acid, phenylacetic acid, gallic acid, 2,4,6-trihydroxybenzoic acid, acetophenone, 2-, 4-chlororesorcinol, 1-naphthol, 1, 5-, 2,3-, 2,7-dihydro xynaphthalene, 6-dimethylamino-4-hydroxy-2-naphthalenesulfonic acid, 3,6-dihydroxy-2,7-naphthalenesulfonic acid,

Amino acids selected from the group arginine, histidine, tyrosine, phenylalanine, DOPA (dihydroxyphenylalanine), omithin, lysine and tryptophan, oligopeptide selected from glutathione or those contained in the hydrolysates of collagen, keratin, casein, elastin, soy protein, wheat gluten or almond protein

CH-active compounds selected from the group consisting of 1, 2,3,3-tetramethyl-3H-indolium iodide, 1, 2,3,3-tetramethyl-3H-indoIium-p-toluoIsuIfonat,

1, 2,3,3-tetramethyl-3H-indolium methanesulfonate, Fischer's base (1,3,3-trimethyl-2-methylene indoline), 2,3-dimethyl-benzothiazolium iodide, 2,3-dimethyl-benzothia- zolium-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 and 1-methyl-3-phenyl-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-methylenedioxy aniline, 2-amino-4- (2-hydroxyethylamino) anisole, 2- (2,4-diaminophenoxy ) -ethanol, 3-amino-2,4-dichloro-, 2-methyl-5-amino-, 3-methyl-4-amino-, 2-methyl-5- (2-hydroxyoxyamino) -, 2- Methyl-5-amino-4-chloro, 6-methyl-3-amino-2-chloro, 2-aminomethyl-4-aminophenol, 2-diethylaminomethyl-4-aminophenol, 2-dimethylaminomethyl-4-aminophenol, 2,6-dichloro-4-aminophenol, 2-hydroxymethyl-4-aminophenol, 3,4-methylenedioxyphenol, 3,4-diaminobenzoic acid, 2,5-diamino-, 2-dimethylamino-5-amino-, 3-amino- 2-methylamino-6-methoxy-, 2,3-diamino-6-methoxy-, 3,5-diamino-2,6-dimethoxy-, 2,6-dihydroxy-3,4-dimethylpyridine, 2-hydroxy-4 , 5,6-triamino-, 4-hydroxy-2,5,6-triamino-, 2,4,5,6-tetraamino-, 2-methylamino-4,5,6-triamino-pyrimidine, 3, 5-diaminopyrazole, 3-amino-5-hydroxypyrazole, 5,6-dihydroxyindole and 5,6-dihydroxyindoline, ß-alanine, L-proline, L-lysine, DL-tyrosine and in each case preferably with inorganic acids ure 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. Agent 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 , contains.

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 9, 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 quaternized heteroaromatic aldehydes and / or ketones with the formula I,

in the mean

R ^{1 is} a hydrogen atom, a C _r C ₄ alkyl group, C _r C ₄ sulfoalky group, C _r C ₄ -

Carboxyalkyl group, aryl group or heteroaryl group,

R ² and R ^{3 represent} a hydrogen atom, halogen atom, a CC ₄ alkyl group, a CC ₄ -

Alkoxy group, a CC ₄ -hydroxyalkyl group, a C _r C ₄ -hydroxyalkoxy group, a hydroxy group, a nitro group or an amino group which is represented by CC ₄ -

R ^{4 is} a C ₁ -C ₄ alkyl group, C ₂ -C ₄ alkenyl group, aryl group, aralkyl group, C., - C ₄ -

Carboxyalkyl group or C ^ C ^ sulfoalkyl group,

Y is a group NR ⁵ , where R ^{5 is} a C _r C ₄ alkyl group, aralkyl group or

Z ^" an anion, especially halide, benzenesulfonate, p-toluenesulfonate,

Hydrogen sulfate, tetrafluoroborate or tetrachlorozincate, wherein the compounds of formula I can also be present as acetals or oximes, as a coloring component in oxidation hair colorants.

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

A) at least one quaternized heteroaromatic aldehyde and / or quaterniert.es heteroaromatic ketone with the formula I.

in the mean

R ^{1 is} a hydrogen atom, a C _r C ₄ alkyl group, C, - C ₄ sulfoalkyl group, Cι-C ₄ -

Carboxyalkyl group, aryl group or heteroaryl group,

R ² and R ^{3 represent} a hydrogen atom, halogen atom, a C., - C ₄ alkyl group, a C _r

C ₄ alkoxy group, a C _r C ₄ hydroxyalkoxy group, a C | -C ₄ -

Hydroxyalkyl group, a hydroxy group, a nitro group or one

Amino group which can be substituted by CC ^ alkyl groups, which together with the nitrogen atom can also form a heterocyclic ring, where the two radicals R ² and R ³ together can form a fused aromatic ring,

R ^{4 is} a C, -C ₄ alkyl group, C ₂ -C ₄ alkenyl group, aryl group, aralkyl group, C, -

C ₄ carboxyalkyl group or CrC ^ sulfoalkyl group,

Y is a group NR ⁵ , where R ^{5 is} a CC ₄ alkyl group, aralkyl group or

Z ^" an anion, in particular halide, benzenesulfonate, p-toluo isulfonate,

Methanesulfonate, methyl sulfate, ethyl sulfate, trifluoromethanesulfonate, perchlorate,

Sulfate, hydrogen sulfate, tetrafluoroborate or tetrachlorozincate, where the compounds of the formula I can also be present as acetals or oximes, and B) at least one compound with a primary or secondary amino group or hydroxyl group, selected from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds, amino acids, from 2 to 9 amino acids composed of oligopeptides and / or at least one CH-active compound , and usual cosmetic ingredients, applied to the keratin fibers, left on the fibers for some time, usually about 30 minutes, and then rinsed out or washed out with a shampoo.