WO2001005359A2

WO2001005359A2 - Agent for coloring keratin fibers that contains at least one quaternary heterocyclic aldehyde or one ketone

Info

Publication number: WO2001005359A2
Application number: PCT/EP2000/006399
Authority: WO
Inventors: Hinrich Möller; Doris Oberkobusch; Horst Höffkes
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1999-07-15
Filing date: 2000-07-06
Publication date: 2001-01-25
Also published as: WO2001005359A3; DE19933187A1; AU6432400A

Abstract

The invention relates to an agent for coloring keratin fibers, especially human hair. The inventive agents contains (A) at least one quaternary heterocyclic aldehyde or one ketone of the general formula (I) in which R1 represents a hydrogen atom, a C¿1?-C4 alkyl group, an aryl or heteroaryl group, R?2, R3, R4¿ represents a hydrogen atom, a halogen atom, a C¿1?-C4 alkyl group, C1-C4 alkoxy or C1-C4 hydroxyalkoxy group, a hydroxy, nitro, amino group that may be substituted by C1-C4 alkyl groups, or a C1-C4 acyl group, whereby two of the residues together may form a fused benzene ring, R?5¿ represents a C¿1?-C4 alkyl group, C1-C4 hydroxyalkyl group, C1-C4 carboxyalkyl group, C1-C4 sulfoalkyl group, an aryl, aralkyl or heteroaryl group or they form an N-oxide unit together with the nitrogen atom that carries them, Q1, Q2, Q3 in total represent two carbon atoms and one nitrogen atom that may be also quaternized, X represents a direct bond or an optionally substituted vinylene group, Y represents a halide, benzene sulfonate, p-toluene sulfonate, methane sulfonate, trifluoromethane sulfonate, perchlorate, sulfate, tetrafluoroborate, perfluoroalkanoate, hydrogen sulfate, tetrachlorozincate or an oxide of an N-oxide, and B) represents at least one compound selected from compounds with a primary or secondary amino group or a hydroxy group, selected from primary or secondary amines, nitrogenous heterocyclic compounds and aromatic hydroxy compounds, and/or CH-active compounds.

Description

"Means for dyeing fibers containing keratin"

The invention relates to an agent for dyeing keratin-containing fibers, in particular human hair, which contains quaternary heterocyclic 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 furs, 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 hydroxyl 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.

Specific representatives are, for example, p-phenylenediamine, p-toluenediamine, 2,4,5,6-tetraaminopyrimidine, p-aminophenol, N, N-bis (2-hydroxyethyl) -p-phenylenediamine, 2- (2.5 Diaminophenyl) ethanol, 2- (2,5-diaminophenoxy) ethanol, 1-phenyl-3-carboxyamido-4-amino-pyrazolon-5, 4-amino-3-methylphenol, 2-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. Suitable coupling substances are, in particular, α-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 2,4-diaminophenoxyethanol , 2-amino-4- (2-hydroxyethylamino) anisole (Lehmanns Blau), 1-phenyl-3-methyl-pyrazolon-5, 2,4-dichloro-3-aminophenol, 1,3-bis- (2, 4-diaminophenoxy) propane, 2-chlororesorcinol, 4- Chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol, 3-amino-6-methoxy-2-methylamino-pyridine and 3,5-diamino-2,6-dimethoxypyridine.

With regard to other conventional dye components, reference is expressly made to the “Dermatology” series, edited by Ch. Culnan, H. Maibach, 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 diskette form from the Federal Association of the German industrial and commercial companies for pharmaceuticals, health products and personal care products eV, 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 quaternary heterocyclic aldehydes and 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 in terms of color depth, gray coverage and fastness properties to the usual oxidation hair colorants, 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 quaternary heterocyclic aldehydes and ketones shown in the formula I, in combination with special developer components, are outstandingly suitable for dyeing even in the absence of oxidizing agents. of 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 A) at least one quaternary heterocyclic aldehyde or a ketone with the formula

(L)

in which R ^{1 represents} a hydrogen atom, a C ^ -C ^ alkyl, an aryl or heteroaryl group

R ² , R ³ , R ^{4 is} a hydrogen, halogen atom, a C _r C ₄ alkyl, C ^ C ^ alkoxy or

is a hydroxyl, nitro, amino group which can be substituted by C 1 -C 4 alkyl groups or CrO _t -acyl group, where two of the radicals together can form a fused-on benzene ring

R ^{5 is} a C ₁ -C ₄ alkyl, C _r C ₄ hydroxyalkyl, C ₁ -C ₄ carboxyalkyl, C _r C ₄ sulfoalkyl, an aryl, aralkyl or heteroaryl group or else forms an N-oxide unit together with the nitrogen atom carrying it. Q ,, Q ₂ , Q ₃ in total represent two carbon atoms and one nitrogen atom, which can also be quaternized

X represents a direct bond or an optionally substituted vinylene group,

Y means halide, benzenesulfonate, p-toluenesulfonate, methanesulfonate, trifluoromethanesulfonate, perchlorate, sulfate, tetrafluoroborate, perchlorate, perfluoroalkanoate, hydrogen sulfate, tetrachlorozincate or oxide of an N-oxide, and B) at least one compound 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.

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 having the formula I are preferably selected from 4-formyl-1-methylpyrimidinium, 4-formyl-3-methylpyrimidinium, 2-formyl-1-methylpyrimidinium, 2-formyl-3-methylpyrimidinium, 4- Acetyl-1-methylpyrimidinium-, 4-acetyl-3-methylpyrimidinium-, 2-acetyl-1-methylpyrimidinium-, 2-acetyl-3-methylpyrimidinium-, 5-formyl-1-methylpyrimidinium-, 2,4-dimethoxy -5-formyl-2,4-dimethoxy-1-methylpyrimidinium-, 2,4-dimethoxy-5-formyl-2,4-dimethoxy-3-methylpyrimidinium-, 1,2,4-trimethyl-5-acetylpyrimidi - nium-, 2,3,4-trimethyl-5-acetylpyrimidinium, 2-formyl-1-methylquinoxylinium, 2-formyl, 4-methylquinoxylinium, 2-formylpyrazinium, 2-acetyl-1-methy! -pyrazinium-, 2-acetyl-4-methyl-pyrazinium-, 2-acetyl-3,4-dimethylpyrazinium-, 2-acetyl-1, 3-dimethylpyrazinium-, 4-formyl-1-methylpyrazinium-, 4-formyl 2-methylpyrazinium, 2-formyl-1-methylquinoxalinium, 2-formyl-4-methylquinoxalinium, 2-formyl-1-methylquinazolinium, 4-formyl-1-methylquinazolinium, 2-formyl-3-methylch inazolinium, 4-formyl-3-methylquinazolinium salts, especially the trifluoromethanesulfonates,

Benzenesulfonates, p-toluenesulfonates, methanesulfonates, perchlorates, sulfates, chlorides, bromides, iodides, tetrachlorozincates, tetrafluoroborates and 2-acetyl-3-methyl-quinoxaline-1,4-dioxide, as well as any mixtures thereof.

The majority of these substances are known from the literature or are commercially available or can be prepared by known synthetic processes, as described, for example, in Organikum, VEB deutscher Verlag der Wissenschaften, Berlin 1981, p. 260. The above-mentioned quaternary heterocyclic aldehydes and ketones with the formula I and the compounds of component B are preferably used in the agents according to the invention in an amount of 0.03 to 65 mmol, in particular 1 to 40 mmol, based on 100 g of the entire colorant. used. They can be used as substantive colorants or in the presence of customary oxidation dye precursors.

Coloring agents which contain the quaternary heterocyclic aldehydes and ketones with the formula I in combination with component B as the coloring component result in colorations over a wide range of shades from orange-brown, red-brown to violet-brown.

Several different quaternary heterocyclic aldehydes and 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 quaternary heterocyclic aldehydes and ketones of the formula I with the compounds of component B mentioned, as substantive colorants. Such reaction products can e.g. B. can be obtained by briefly heating the two components in stoichiometric amounts in an aqueous neutral to weakly alkaline medium, where 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-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, 3-methyl-4-amino, 2-methyl-5- (2-hydroxyoxyamino) -, 6-methyl-3-amino-2-chloro , 2-methyl-5-amino-4-chloro, 3,4-methylenedioxy, 5- (2-hydroxyethylamino) -4-methoxy-2-methyl, 4-amino-2-hydroxymethylphenol,

1, 3-diamino-2,4-dimethoxybenzene, 2-, 3-, 4-aminobenzoic acid, -phenylacetic acid, 2,3-,

2,4-, 2,5-, 3,4-, 3,5-diaminobenzoic acid, 4-, 5-aminosalicylic acid, 3-amino-4-hydroxy-,

4-amino-3-hydroxy-benzoic acid, 2-, 3-, 4-aminobenzenesulfonic acid, 3-amino-4-hydroxybenzenesulfonic acid, 4-amino-3-hydroxynaphthaiine-1-sulfonic acid, 6-amino-7-hydroxynaphthalene-2- sulfonic acid, 7-amino-4-hydroxynaphthalene-2-sulfonic acid, 4-amino

5-hydroxynaphthalene-2,7-disulfonic acid, 3-amino-2-naphthoic acid, 3-aminophthalic acid,

5-aminoisophthalic acid, 1, 3,5-, 1, 2,4-triaminobenzene, 1, 2,4,5-tetraaminobenzene, 2,4,5-

Triaminophenol, pentaaminobenzene, hexaaminobenzene, 2,4,6-triaminoresorcinol, 4,5-

Diaminobrenzcatechin, 4,6-Diaminopyrogallol, 3,5-Diamino-4-hydroxybrenzcatechin, aromatic nitrites, anilines, especially anilines containing nitro groups, such as 4-nitroaniline,

4-nitro-1,3-phenylenediamine, 2-nitro-4-amino-1- (2-hydroxyethylamino) benzene, 2-nitro-1-amino-4- [bis- (2-hydroxyethyl) amino] - benzene, 4-amino-2-nitrodiphenylamine-2'-carboxylic acid, 2-amino-6-chloro-4-nitrophenol, 1-amino-5-chloro-4- (2-hydroxyethylamino) -2-nitrobenzene, aromatic Anilines or phenols with a further aromatic radical, as in the

Formula II are shown

(II)

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

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

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

Q 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 having the formula

Z- (CH ₂ -Y-CH ₂ -Z ') ₀ (III)

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

Z and Z independently of one another for an oxygen atom, an NR ² group in which R ^{12 is} hydrogen, a C _1-4 alkyl or a hydroxyC _1-4 alkyl group, the group O- (CH ₂ ) _p - NH or NH- (CH ₂ ) _p '-O, where p and p' are 2 or 3, and o 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, S.SΑ ^ - tetraaminodiphenyl, 3,3 ', 4,4'-tetraamino-benzophenone, 1, 3-bis- (2nd , 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 as well as indole and indoline derivatives such as 4-, 5-, 6-, 7-aminoindole, 5,6-dihydroxyindole, 5,6-dihy- droxyindoline and 4-hydroxyindoline. The aforementioned compounds can 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, hydroxy hydroquinone, 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- naphthalene sulfonic acid.

Examples of CH-active compounds which may be mentioned are 1, 2,3,3-tetramethyl-3H-indolium iodide, 1, 2,3,3-tetramethyl-3H-indolium-p-toluenesulfonate, 1, 2,3,3-tetramethyl - 3H-indolium methanesulfonate, Fischer's base (1,3,3-trimethyl-2-methyleneindoline), 2,3-dimethyl-benzothiazolium iodide, 2,3-dimethyl-benzothiazolium-p-toluenesulfonate, rhodanine, rhodanine-3-acetic acid , 1-methyl-2-quinaldinium iodide, 1-ethyl-2-quinaldinium iodide, 1, 4-dimethylquinolinium iodide, barbituric acid, thiobarbituric acid, 1, 3-dimethylthiobarbituric acid, 1, 3-diethylthiobarbituric acid, diethylthiobarbituric acid , 3-indoxy acetate, coumaranone and 1-methyl-3-phenyl-2-pyrazolinone.

The compounds of component B are particularly preferably selected from the group consisting of N- (2-hydroxyethyl) -N-ethyl-, 2-chloro-p-phenylenediamine, N, N- bis (2-hydroxyethyl) -p-phenylenediamine, 4-aminophenol, p-phenylenediamine, 2- (2,5-diaminophenyl) ethanol, 2,5-diaminotoluene, 3,4-methylenedioxyaniline, 2-amino-4- (2-hydroxyethylamino) anisole, 2- (2,4-diaminophenoxy) ethanol, 3-amino-2,4-dichloro, 2-methyl-5-amino, 3-methyl-4-amino, 2-methyl-5- (2- hydroxyethylamino) -, 2-methyl-5-amino-4-chloro, 6-methyl-3-amino-2-chloro, 2-aminomethyl-4-aminophenol, 2-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 and their physiologically tolerable salts formed with preferably inorganic acids.

On the presence of oxidizing agents, e.g. B. H ₂ O ₂ , can be omitted. However, it can It may be desirable to add hydrogen peroxide or other oxidizing agents to the agents according to the invention to achieve the shades that are lighter than the keratin-containing fiber to be colored. Oxidizing agents are generally used in an amount of 0.01 to 6% by weight, based on the application solution. A preferred oxidizing agent for human hair is H ₂ O ₂ .

In a preferred embodiment, the colorants according to the invention contain, in addition to the compounds according to the invention, customary direct dyes, for example, for further modification of the color shades. B. from the group of nitro-phenylenediamines, 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) aminobenzene. The agents according to the invention in accordance with this embodiment preferably contain the substantive dyes in an amount of 0.01 to 20% by weight, based on the total colorant.

Furthermore, the preparations according to the invention can also contain naturally occurring dyes such as, for example, henna red, henna neutral, henna black, chamomile flowers, sandalwood, black tea, 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, still in minor amounts Other components may be included, provided they 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 one

Alkyl group with 10 to 22 carbon 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 having 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule, and in particular salts of saturated and in particular unsaturated C ₈ -C ₂₂ carboxylic acids, such as oleic acid, stearic acid , Isostearic acid and palmitic acid.

Zwitterionic surfactants are those surface-active compounds which carry at least one quaternary ammonium group and at least one -COO ⁰ - or -SOs ^ 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 cocoacylaminoethylhydroxyethylcarboxymethyl giycinat. 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 1-4 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-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-coconut alkylaminopropionate, coconut acylaminoethylaminopropionate and C ₁₂ . ₁₈ - acyl sarcosine.

Nonionic surfactants contain z as a hydrophilic group. B. a Potyolgruppe, a Polyalkylenglykolethergruppe or a combination of Polyol- and Polyglykol- ethergruppe. 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 analogues,

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 nium 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 polydimethylsiioxane, Quatemium-80).

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

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

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

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

In the case of the surfactants, which are addition products of ethylene and / or propylene oxide with 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. Under "normal" homolog distribution Mixtures of homologs understood that are obtained in the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alkoxides as catalysts. 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, for example, vinylpyrrolidone / vinyl acrylate copolymers, polyvinylpyrrolidone and vinylpyrrolidone / vinyl acetate copolymers and polysiloxanes, cationic polymers such as quaternized cellulose ethers, polysiloxanes with quaternary groups, dimethyldiallydiallyl ammonium - ammonium chloride copolymers, dimethylaminoethyl methacrylate-vinylpyrrolidone copolymers quaternized with diethyl sulfate, vinylpyrrolidone-

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

Thickeners such as agar agar, guar gum, alginates, xanthan gum, gum arabic cum, karaya gum, locust bean gum, linseed gums, dextrans, cellulose derivatives, e.g. B. methyl cellulose, hydroxyalkyl cellulose and carboxymethyl cellulose, starch fractions and derivatives such as amylose, amyiopectin 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 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 trium or lithium, alkaline earth metals, such as magnesium, calcium, strontium or barium, or of aluminum, manganese, iron, cobalt, copper or zinc, where sodium acetate, lithium bromide, calcium bromide, calcium gluconate, zinc chloride, zinc sulfate, magnesium chloride, magnesium sulfate, ammonium carbonate, chloride and acetate are 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 3 and 11, preferably between 5 and 10.

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

A) at least one quaternary heterocyclic aldehyde and a ketone with the formula I,

(I)

in which R ^{1 represents} a hydrogen atom, a C ₁ -C ₄ alkyl, an aryl or heteroaryl group

R ² , R ³ , R ^{4 is} a hydrogen, halogen atom, a C _r C ₄ alkyl, C _r C ₄ alkoxy or C _r C ₄ hydroxyalkoxy group, a hydroxyl, nitro, amino group which is formed by CrC -Alkyl groups can be substituted, or C _r C ₄ -acyl group, where two of the radicals together can form a fused-on benzene ring

R ^{5 is} a C _r C ₄ alkyl, C _r C ₄ hydroxyalkyl, dC-carboxyalkyl, dC ^ sulfoalkyl, an aryl, aralkyl or heteroaryl group or together with the nitrogen atom carrying them an N -Oxide unit forms means Q _1f Q ₂ , Q ₃ in total represent two carbon atoms and one nitrogen atom, which can also be quaternized

X for a direct bond or an optionally substituted one

Vinylene group stands,

Y means halide, benzenesulfonate, p-toluenesulfonate, methanesulfonate, trifluoromethanesulfonate, perchlorate, sulfate, tetrafluoroborate, perchlorate, perfluoroalkanoate, hydrogen sulfate, tetrachlorozincate or oxide of an N-oxide, and B) at least one compound having a primary or secondary amine 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, applied to the keratin-containing fibers, for some time, usually about 30 minutes , leave on the fiber and then rinsed out or washed out with a shampoo.

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

The quaternary heterocyclic aldehydes and 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 example

2-formyl-4 (1) -methylchinoxalinium trifluoromethanesulfonate

5.0 g (32 mmol) of quinoxaline-2-carboxaldehyde and 5.3 g (32 mmol) of trifluoromethanesulfonic acid methyl ester were dissolved in 30 ml of toluene and heated to 60 ° C. with stirring for 16 hours, cooled to room temperature, with warm toluene washed out and dried in an oil pump vacuum. 9.7 g (94% of theory) of 2-formyl-4 (1) -methylquinoxaline trifluoromethanesulfonate were obtained as hygroscopic crystals (1 H-NMR spectrum).

colorations

Preparation of a coloring solution

A slurry of 5 mmol of an aromatic nitroso compound with the formula I, if appropriate 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. were prepared. The slurries were mixed together after cooling to 30 ° C and adjusted to pH 6 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. rbtiefe 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 3-formyl-1-methyl-quinoxalinium trifluoromethanesulfonate

Table 2

Colorings with 2-acetyl-3 methylquinoxaline-1,4-dioxide

Claims

claims

1. Containing compositions for dyeing keratin fibers, in particular human hair

A. at least one quaternary heterocyclic aldehyde or a ketone with the formula I,

(I)

in which R ^{1 represents} a hydrogen atom, a dd-alkyl, an aryl or heteroaryl group

R ² , R ³ , R ^{4 is} a hydrogen, halogen atom, a dd-aikyl, C _r C ₄ -alkoxy or C ^ C ^ hydroxyalkoxy group, a hydroxy, nitro, amino group by dd-alkyl groups may be substituted, or CC ₄ -acyl group, where two of the radicals together can form a fused benzene ring, R ^{5 is} a dd-alkyl, dd-hydroxyalkyl, C _r C ₄ carboxyalkyl, C _r C ₄ - sulfoalkyl -, an aryl, aralkyl or heteroaryl group or together with the nitrogen atom carrying them forms an N-oxide unit

Q ,, Q _2l Q ₃ _{mean a} total of two carbon atoms and one nitrogen atom, which can also be quaternized

X represents a direct bond or an optionally substituted vinylene group,

Y means halide, benzenesulfonate, p-toluenesulfonate, methanesulfonate, trifluoromethanesulfonate, perchlorate, sulfate, tetrafluoroborate, perchlorate, perfluoroalkanoate, hydrogen sulfate, tetrachlorozincate or oxide of an N-oxide, and B at least one compound with primary or secondary amino group or hydroxy group, selected from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds, and / or at least one CH-active compound.

2. Composition according to claim 1, characterized in that as compounds with the formula I 4- formyl-1-methylpyrimidinium-, 4-formyl-3-methylpyrimidinium-, 2-formyl-1-methylpyrimidinium-, 2-formyl-3- methylpyrimidinium-, 4-acetyl-1-methylpyrimidinium-, 4-acetyl-3-methylpyrimidinium-, 2-acetyl-1-methylpyrimidinium-, 2-acetyl-3-methylpyrimidinium-, 5-formyl-1-methylpyrimidinium-, 2, 4-dimethoxy-5-formyl-2,4-dimethoxy-1-methylpyrimidinium, 2,4-dimethoxy-5-formyl-2,4-dimethoxy-3-methylpyrimidinium, 1, 2,4-trimethyl-5- acetylpyrimidinium, 2,3,4-trimethyl-5-acetylpyrimidinium, 2-formyl-1-methylquinoxylinium, 2-formyl-4-methylquinoxylinium, 2-formyl-pyrazinium, 2-acetyl-1-methyl-pyrazinium -, 2-Acetyl-4-methyl-pyrazinium, 2-acetyl-3,4-dimethylpyrazinium, 2-acetyl-1, 3-dimethylpyrazinium, 4-formyl-1-methylpyrazinium, 4-formyl-2- methylpyrazinium, 2-formyl-1-methylquinoxalinium, 2-formyl-4-methylquinoxalinium, 2-formyl-1-methylquinazolinium, 4-formyl-1-methylquinazole inium, 2-formyl-3-methylquinazolinium or 4-formyl-3-methylquinazolinium salts, especially the trifluoromethanesulfonates, benzenesulfonates, p-toluenesulfonates, methanesulfonates, perchlorates, sulfates, chlorides, bromides, iodides, tetrachlorozincates, tetrafluoroborates Acetyl-3-methyl-quinoxaline-1,4-dioxide and any mixtures thereof can be used.

3. Composition according to one of claims 1 to 2, characterized in that the quaternary heterocyclic aldehydes and ketones with the formula I and the compounds of component B in an amount of 0.03 to 65 mmol, in particular from 1 to 40 mmol, based to 100 g of the total colorant.

4. Composition according to one of claims 1 to 3, characterized in that the compounds of component B are selected from primary or secondary amines from the group consisting of N- (2-hydroxyethyl) -N-ethyl-, N- (2-methoxyethyl), 2,3-, 2,4-, 2,5-dichloro-p-phenylenediamine, 2-chloro-p-phenylenediamine, N, N-bis- (2-hydroxyethyl) -p-phenylenediamine , 2,5-dihydroxy-4- morpholinoaniline dihydrobromide, 2-, 3-, 4-aminophenol, o-, m-, p-phenylenediamine, 2,4-diaminophenoxyethanol, 2- (2,5-diaminophenyl) ethanol, 2,5-diaminotoluene, - phenol , -phenethol, 4-methylamino-, 3-amino-4- (2'-hydroxyethyloxy) -, 3,4-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-aminomethylphenol, 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, 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, S.S '^^' - tetraaminodiphenyl-tetra-hydrochloride, S. S '^^' - 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-dia mino-, 2-dimethylamino-5-amino-, 3-amino-2-methylamino-6-methoxy-, 2,3-diamino-6-methoxy-, 3,5-diamino-2,6-dimethoxy-, 2nd , 4,5-triamino-, 2,6-dihydroxy-3,4-dimethylpyridine, 4,5,6-triamino-, 2-hydroxy-4,5,6-triamino-, 4-hydroxy-2,5, 6-triamino-, 2,4,5,6-tetraamino-, 2-methylamino-4,5,6-triamino-, 2,4-, 4,5-diamino-, 2-amino-4-methoxy-6 -methyl-pyrimidine, 2,3,4-trimethylpyrrole, 2,4-dimethyl-3-ethyl-pyrrole, 3,5-diaminopyrazole, -1, 2,4-triazole, 3-amino-, 3-amino-5 -hydroxypyrazole, 2-, 3-, 8-aminoquinoline, 4-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 -Dihydroxyindolin and 4-Hydroxyindolin, as well as Is from the physiologically compatible salts of these compounds, preferably formed with inorganic acids, 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-dihydroxynaphthalene, 6-dimethylamino-4- hydroxy-2-naphthainsulfonic acid, 3,6-dihydroxy-2,7-naphthalenesulfonic acid, and

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

1, 2,3,3-tetramethyl-3H-indolium methanesulfonate, Fischer's base (1,3,3-trimethyl-2-methyleneindoline), 2,3-dimethyl-benzothiazolium iodide, 2,3-dimethyl-benzothiazolium-p- toluenesulfonate, rhodanine, rhodanine-3-acetic acid, 1-ethyl-2-quinaldinium iodide, 1, 4-dimethylquinolinium iodide, 1-methyl-2-quinaldinium iodide, 1, 4-dimethylquininoinium iodide, barbituric acid, thiobarbituric acid, 1,3-dimethylthiobarbituric acid, 1,3-diethylthiobarbituric acid, diethylthiobarbituric acid, oxindole, 3-indoxyl acetate, coumaranone and 1-methyl-3-phenyl-2-pyrazolinone.

5. Composition according to claim 4, characterized in that the further compound is selected from the group consisting of N- (2-hydroxyethyl) -N-ethyl-, 2-chloro-p- phenylenediamine, N, N-bis (2-hydroxyethyl) -p-phenylenediamine, 4-aminophenol, p-phenylenediamine, 2- (2,5-diaminophenyl) ethanol, 2,5-diaminotoluene, 3,4-methylenedioxyaniline , 2-Amino-4- (2-hydroxyethylamino) anisole, 2- (2,4-diaminophenoxy) ethanol, 3-amino-2,4-dichloro, 2-methyl-5-amino, 3-methyl -4-amino-, 2-methyl-5- (2-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-methyiamino- 4,5,6- triamino-pyrimidine, 3,5-diaminopyrazole, 3-amino-5-hydroxypyrazole, 5,6-dihydroxyindole and 5,6-dihydroxyindoline and in each case from the physiologically tolerable salts of these compounds which are preferably formed with inorganic acids.

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

7. Composition according to one of claims 1 to 6, characterized in that ammonium or metal salts selected from the group of formates, carbonates, halides, sulfates, butyrates, valerates, capronates, acetates, lactates, glycolates, tartrates, citrates, gluconates, Propionates, phosphates and phosphonates of alkali metals, such as potassium, sodium or lithium, alkaline earth metals, such as magnesium, calcium, strontium or barium, or of aluminum, manganese, iron, cobalt, copper or zinc, will be added.

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

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

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

A) at least one quaternary heterocyclic aldehyde or a ketone with the formula I,

(D in which R ^{1 represents} a hydrogen atom, a CrC ₄ alkyl, an aryl or heteroaryl group

R ² , R ³ , R ^{4 is} a hydrogen, halogen atom, a 0, -C ^ alkyl, CC ₄ -alkoxy or C d-hydroxyalkoxy group, a hydroxy, nitro, amino group by dd-alkyl groups may be substituted, or C _r C ₄ acyl group, where two of the radicals together can form a fused benzene ring

R ^{5 is} a C _r C ₄ alkyl, dd-hydroxyalkyl, CrC-carboxyalkyl, C _r C ₄ sulfoalkyl, an aryl, aralkyl or heteroaryl group or together with the nitrogen atom carrying them an N-oxide Unity means

Q _1f Q ₂ , Q ₃ mean a total of two carbon atoms and one nitrogen atom, which can also be quaternized

X represents a direct bond or an optionally substituted vinylene group,

Y means halide, benzenesulfonate, p-toluenesulfonate, methanesulfonate, trifluoromethanesulfonate, perchlorate, sulfate, tetrafluoroborate, perchlorate, perfluoroalkanoate, hydrogen sulfate, tetrachlorozincate or oxide of an N-oxide, 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 hydroxy compounds, and / or at least one CH-active compound, and also conventional cosmetic ingredients, applied to the keratin-containing fibers, some Time, usually about 30 minutes, is left on the fiber and then rinsed out or washed out with a shampoo.