EP1113779A1

EP1113779A1 - Method for dyeing fibres containing keratin using stable diazonium salts

Info

Publication number: EP1113779A1
Application number: EP99969020A
Authority: EP
Inventors: Hinrich Möller; Horst Höffkes
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1998-09-15
Filing date: 1999-09-04
Publication date: 2001-07-11
Also published as: WO2000015184A1; AU5973399A; DE19842071A1; JP2002524484A

Abstract

The invention relates to a method for dyeing fibres containing keratin, especially human hair. According to said method, the following is applied to the fibres in a one-step process: A) at least one stable diazonium salt of formula (I) wherein R<1>, R<2>, R<3> and R<4> mean, independently of each other, a hydrogen atom, a halogen atom, a (C1-C4)-alkyl group, a (C1-C4)-alkoxy group, a hydroxy-(C1-C4)-alkoxy group, a hydroxy group, a sulfo group, a carboxy group, an amino group which can be substituted by a (C1-C4)-alkyl group, a hydroxyalkyl group, a C1-C4-acyl group or an optionally substituted benzol group or can be part of a heterocycle, or a (C1-C4)-acyl group, and two of the radicals can also form a fused benzol ring and can be an optionally substituted phenyl group or can form a heterocyclic ring with the N-atom, or a physiologically compatible salt thereof; optionally combined with B) a compound chosen from compounds with a primary or secondary amino group, chosen from primary or secondary aromatic amines, nitrogenous heterocyclic compounds and/or aromatic hydroxy compounds and/or CH-active compounds.

Description

"Process for dyeing fibers containing keratin using stable diazonium salts"

The invention relates to a process for dyeing keratin-containing fibers, in particular human hair, in which stable diazonium salts are used as the coloring component.

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 their derivatives are usually used as developer components.

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 and m-aminophenols are generally used as coupler components. Particularly suitable coupler substances are α-naphthol, 1, 5-, 2,7- and 1, 7-dihydroxynaphthaiine, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinomino methyl ether, m-phenylenediamine, 2,4 -diaminophenoxyethanol, 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 and 5-methylresorcinol.

With regard to further conventional dye components, reference is expressly made to the series “Dermatology”, 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 it is possible to achieve intensive dyeings with good fastness properties, but the development of the color generally takes place under the influence of oxidizing agents such as H ₂ O ₂ , which in some cases can damage the fibers. 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 diazonium salts for dyeing fibers containing keratin is known from the prior art and is described, for example, in the publications CH-PS-630 254, DE 27 39 227, FR-PS-78 05441 and DE-OS-27 57 866. CH-PS-630 254 and DE-OS-39 227 use nitrogen-containing heterocycles as coupling components. In FR-PS-78 05441 the coupling component is an arylamide derivative of acetaldehyde. From DE-OS-27 57 866 naphthyl compounds are known as coupling components.

In the publications mentioned in the dianzonium salts are used in the presence of suitable coupling components. The dyeing process is carried out in such a way that the keratin-containing fiber to be dyed is first pretreated with the coupling component by removing some of the coupling component Allows time to act on the fiber. The diazonium salt is then applied in a second step. The two-step process is labor-intensive and time-consuming.

The object of the present invention is to provide dyes for keratin fibers, in particular human hair, which can be applied to the fiber in a few work steps and which are qualitatively at least equivalent to the usual oxidation hair dyes in terms of color depth, gray coverage and fastness properties, but without necessarily to be dependent on oxidizing agents such as H ₂ O ₂ . In addition, the colorants may have no or only a very low sensitization potential.

Surprisingly, it has now been found that the stable diazonium salts shown in the formula I can also be used in one-step processes both as direct dyeing agents and in combination with coupling components for dyeing keratin-containing fibers. Colorings with excellent brilliance and depth of color are obtained. The use of oxidizing agents is not necessary, but should not be excluded in principle.

The invention relates to a process for dyeing keratin fibers, in particular human hair, in which

A) in which at least one stable diazonium salt with the formula I or its physiologically compatible salt,

in which R ¹ , R ² , R ³ and R ⁴ independently of one another are a hydrogen atom, a halogen atom, a (C ₁ -C ₄ ) alkyl group, a (C _r C ₄ ) alkoxy group, a hydroxy (C ₁ -C ₄ ) -alkoxy group, a hydroxy group, a sulfo group, a carboxy group, an amino group, which is replaced by a (C, ^) - alkyl group, hydroxyalkyl group, a C _r C ₄ acyl group or a optionally substituted benzene group can be substituted or part of a heterocycle, or a (C ₁ -C ₄ ) acyl group, where two of the radicals can also form a fused-on benzene ring and can be an optionally substituted phenyl group, or together with the N atom one form heterocyclic ring, mean, B) optionally in combination with a compound selected from compounds with primary or secondary amino group, selected from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds, and / or aromatic hydroxy compounds and / or CH-active compounds, in a one-step process is applied to the fibers.

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 to dye other natural fibers, such as Cotton, jute, sisal, linen or silk, modified natural fibers, e.g. Regenerated cellulose, nitro, alkyl or hydroxyalkyl or acetyl cellulose and synthetic fibers such as e.g. Polyamide, polyacrylonitrile, polyurethane and polyester fibers can be used.

The stable diazonium salts of formula I used according to the invention are preferably selected from the group consisting of 4-diazo-phenylamine sulfate (Variamin blue salt RT), 4-diazo-4'-methoxydiphenylamine chloride (Variamine blue salt B), 4-diazo-3,2'-dimethylazobenzenesulfate (Real garnet salt GBC), 2-methoxy-4-nitrobenzene diazoniumnaphthalene-1, 5-disulfonate, 4-diazo-2,5-dimethoxy-4'-nitroazobenzene chloride-zinc chloride double salt (real black acid K), 2,5-dimethoxy-4- benzoylaminophenyldiazonium chloride (real blue salt RR), 2-methoxy-4-nitrobenzene diazonium 1, 5-naphthalenedisulfonate (real red salt B), 4-chloro-2-nitrobenzene diazonium chloride-zinc chloride, double salt (real red chlorine 3 GL 2), 5 -methoxybenzene-diazonium chloride-zinc chloride double salt (real red salt RC), 4-benzamido-2-methoxy-5-methylbenzoidiazonium chloride-zinc chloride double salt (real violet salt B), 2-diazo-1-naphthol-4-sulfonic acid, Na Salt of 2-diazo-1-naphthol-5-sulfonic acid and any mixtures thereof.

These substances are known from the literature or are commercially available. The above-mentioned stable diazonium salts with the formula I are preferably used in the process according to the invention in an amount of 0.03 to 65 mmole, in particular 1 to 40 mmol, based on 100 g of the total colorant. _-.

If the stable diazonium salts with the formula I are used as the only colorant in the process according to the invention, colorations in the brown range are obtained. Colorings with an even higher brilliance and improved fastness properties (light fastness, wash fastness, fastness to rubbing), especially in the yellow, orange, brown and black range, are achieved if the compounds of the formula I are used together with the compounds referred to as component B. On the one hand, these are compounds which, in their own right, only weakly dye keratin-containing fibers and only produce brilliant colorations together with the diazonium salts of the formula I. On the other hand, there are also compounds that are already used as oxidation dye precursors.

The 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.

Several different stable diazonium salts of the formula I can also be used together in the process according to the invention; Likewise, several different compounds of component B can also be used together. This embodiment also includes the use of those substances which are reaction products of stable diazonium salts of the formula I with the compounds of component B mentioned. The compounds of formula I and the optionally used compounds of component B are applied to the fiber according to the invention in a one-step process. This means that the components are applied simultaneously without the pretreatment of the fiber with one of the component components being necessary.

Suitable compounds with a primary or secondary amino group as component B are, for example, 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, - phenethol, 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-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-, 3-, 4-aminobenzenesulfonic acid, 3-amino-4-hydroxybenzenesulfonic acid, 4-amino-3-hydroxynaphthalene-1 -sulfonic acid, 6-amino-7- hydroxynaphthalene-2-sulfonic acid, 7-amino-4-hydroxynaphthalene-2-sulfonic acid, 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid, 3-amino-2-naphthoic acid, 3-aminophthalic acid, 5-aminoisophthalic acid, 1, 3,5-, 1, 2,4-thaminobenzene, 1, 2,4,5-tetraaminobenzene, 2,4,5-triaminophenol, 2,4,6-triaminoresorcinol, 4,5-diaminobenzate catechol, 4,6-diaminopyro - Gallol, 3,5-diamino-4-hydroxy-catechol, aromatic nitriles, anilines, in particular 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] - benzoi, 4-amino-2-nitrodiphenylamine-2'-carboxylic acid, 2-amino-6- chloro-4-nitrophenol, 1-amino-5-chloro-4- (2-hydroyethyiamino) -2-nitrobenzene, aromatic anilines or phenols with a further aromatic radical, as described in Formula II are shown

in the R ⁵ for a hydroxy or an amino group, which can be substituted by C ^ alkyl, C _M - hydroxyalkyl, C _1-4 alkoxy or C _1-4 alkoxy-C _1-4 alkyl groups , stands, R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ^{10 represent} hydrogen, a hydroxy or an amino group,

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

X for a direct bond, a saturated or unsaturated carbon chain with 1 to 4 carbon atoms optionally substituted by hydroxyl groups, a carbonyl, sulfonyl or imino group, an oxygen or sulfur atom, or a group with the formula

III

Z- (CH ₂ -Y-CH ₂ -Z ') 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 ¹³ group, wherein R ^{14 is} hydrogen, a C _1-4 alkyl or a. Hydroxy-C _1-4 -alkyl group means the group 0- (CH ₂ ) _p -NH or NH- (CH ₂ ) _p '-O, where p and p' are 2 or 3, and o is a number of 1 to 4, such as 4,4'-diaminostilbene, 4,4'-diaminostilbene-2,2'-disulfonic acid mono- or di-Na salt, 4-amino-4'-dimethylaminostilbene, 4,4 ' -Diaminodiphenylmethane, -sulfide, -sulfoxide, -amin, 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- (4th aminophenoxy) ethyl] methiamine, N-phenyl-1,4-phenylendiamine.

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, for example, 2-, 3-, 4-amino, 2-amino-3-hydroxy, 2,6-diamino, 2,5-diamino, 2,3-diamino, 2-dimethylamino -5-amino-, 2-methylamino-3-amino-6-methoxy-, 2,3-diamino-6-methoxy-, 2,6-dimethoxy-3,5-diamino-, 2,4,5-triamino -, 2,6-dihydroxy-3,4-dimethylpyridine, 2,4-dihydroxy-5,6-diamino-, 4,5,6-triamino-, 4-hydroxy-2,5,6-triamino-, 2nd -Hydroxy-4,5,6-triamino-, 2,4,5,6-tetraami- no-, 2-methylamino-4,5,6-triamino-, 2,4-, 4,5-diamino-, 2-amino-4-methoxy-6-methylpyrimidine, 3,5-diaminopyrazole, -1 , 2,4-triazole, 3-amino-, 3-amino-5-hydroxypyrazole, 2-, 3-, 8-aminoquinoline, 4-aminoquinidine, 2-, 6-aminoonicotinic acid, 5-aminoisoquinoline, 5-, 6- Aminoindazole, 5-, 7-aminobenzimidazole, -benzothiazole, 2,5-dihydroxy-4-morpholinoaniiin as well as indole and indoline derivatives, such as 4-, 5-, 6-, 7-aminoindole, 5,6-dihydroxyindole, 5,6 -. Dihydroxyindoline and 4-hydroxyindoline. The aforementioned compounds can be 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. 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-thhydroxybenzoic acid, -acetophenone, 2-, 4-chlororesorcinol, 1-naphthol, 1, 5-, 1, 6-, 1, 7-, 2,3-, 2,6-, 2,7-dihydroxynaphthalene, 2-naphthol-3,6-disulfonic acid Na salt, 6-dimethylamino-4 -hydroxy-2-naphthaiinsulfonic acid, 3,6-dihydroxy-2,7-naphthaiinsulfonic 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-ethyl-2-quinaldinium iodide, 1-methyl-2-quinaldinium iodide, barbituric acid, thiobarbituric acid, 1, 3-dimethylthiobarbituric acid, diethylthiobarbituric acid, oxindole, 3-indoxy acetate, coumaranone and 1-methyl-3-phenyl-2-pyrazolinone.

The compounds of component B are particularly preferably selected from the group consisting of N- (2-hydroxyethyl) -N-ethyl-, 2-chloros-p-phenylenediamine, N, N- bis (2-hydroxyethyl) -p-phenylenediamine, 4-aminophenol, p-phenylenediamine, 2- (2,5-diaminophenyl) ethanol, 2,5-diaminotoluene, 3,4-methylenedioxyaniline, 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-amino, 2-hydroxymethyl-4-amino, 2-amino-4- (2-hydroxyethylamino) -, 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-methylamino-4,5,6-triamino-pyrimidine, 3,5-diaminopyrazole, 3-amino-5-hydroxypyrazole, 5,6-dihydroxyindole, 5, 6-dihydroxyindoiin, 1-naphthol, 1, 5-, 1, 6-, 1, 7-, 2,3-, 2,6-, 2,7-dihydroxynaphthalene and 2-naphthol-3,6-disulfonic acid, Na Salt, as well as their physiologically compatible salts formed with preferably inorganic acids.

The presence of oxidizing agents, for example H ₂ O ₂ , can be dispensed with. However, it may be desirable to add hydrogen peroxide or other oxidizing agents in the process 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, in addition to the compounds contained according to the invention, customary direct dyes, e.g. from the group of nitrophyne diamines, nitroaminophenols, anthraquinones or indophenols, such as e.g. 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-tetrahydroquinoxaiine, 4-N-ethyl-1,4-bis (2'-hydroxyethylamino) -2-nitrobenzene hydrochloride and 1-methyl-3-nitro- 4- (2'-hydroxyethyl) aminobenzene. In the process according to the invention according to this embodiment, the substantive dyes are preferably used in an amount of 0.01 to 20% by weight, based on the colorant used.

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

The method according to the invention already gives intense colorations at physiologically acceptable temperatures of below 45 ° C. It is therefore particularly suitable for coloring human hair. For use on human hair, the individual components are usually incorporated into a water-containing cosmetic carrier. Suitable water-containing cosmetic carriers are e.g. B creams, emulsions, gels or also surfactant-containing foaming solutions such as shampoos or other preparations that are suitable for use on the keratin-containing fibers. If necessary, it is also possible to incorporate the components into anhydrous carriers

Furthermore, all the active ingredients, additives and auxiliaries known in such preparations can be used in the process according to the invention. In many cases at least one surfactant is present, although in principle both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants are suitable. In many cases it has been found but it has proven to be 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, for example, a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group about 10 to 22 carbon atoms In addition, glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups can be contained in the molecule. Examples of suitable anionic surfactants are, in each case in the form of the sodium, potassium and ammonium and Mono-, di- and tπalkanoiammonium 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 carbon atoms in the acyl group, Acyl taurides with 10 to 18 carbon atoms in the acyl group, acyl isethionates with 10 to 18 carbon atoms in the acyl group,

Sulfosuccinic acid mono- and dialkyl esters with 8 to 18 carbon atoms in the alkyl group and sulfosuccinic acid mono-alkyl polyoxyethyl esters with 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups, linear alkane sulfonates with 12 to 18 carbon atoms, linear alpha-olefin sulfonates with 12 to 18 carbon atoms, alpha-sulfofatty acid methyl ester of fatty acids with 12 to 18 carbon atoms, alkyl sulfates and alkyl polyglycol ether sulfates of the formula RO (CH ₂ -CH ₂ O) _x -SO ₃ H, in which R is a preferably linear alkyl group with 10 to 18 C atoms and x = 0 or 1 to 12,

Mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030, sulfated hydroxyalkyl polyethylene and / or hydroxyalkylene propylene glycol ethers according to DE-A-37 23 354,

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

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

Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids with 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule, and in particular salts of saturated and in particular unsaturated C ₈ -C ₂₂ carboxylic acids, such as oleic acid, stearic acid, isostearic acid and palmitic acid.

Zwitterionic surfactants are those surface-active compounds which carry at least one quaternary ammonium group and at least one -COO ^H or -SO ^ 'group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinate, for example coconut alkyl dimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammonium glycinate, for example coconut acylaminopropyl dimethylammonium glycinate, and 2-alkyl -3-carboxymethyl-3-hydroxyethyl-imidazoiine each having 8 to 18 carbon atoms in the alkyl or acyl group and the cocoacylaminoethyl hydroxyethyl carboxymethyl glycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known under the CTFA name Cocamidopropyl Betaine.

Ampholytic surfactants are understood to mean those surface-active compounds which, in addition to a C ₈ . ₁₈ alkyl or acyl group in the molecule contain at least one free amino group and at least one -COOH or -SO ₃ H group and are capable of forming internal salts. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each with about 8 to 18C Atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethyl aminopropionate and C ₁₂ _ι ₈ acyl sarcosine.

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

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

22 carbon 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 alkylimony 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 processes according to the invention are, in particular, quaternary ammonium compounds. Ammonium halides such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g. B. cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethyl ammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride. The quaternized protein hydrolyzates are further cationic surfactants which can be used according to the invention.

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

In addition to a good conditioning effect, alkylamidoamines, especially fatty acid amidoamines such as the stearylamidopropyldimethylamine available under the name Tego Amid®S 18, are characterized in particular by 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 quaternary sugar derivative that can be used as a cationic surfactant is the commercial product Glucquat®100, according to the CTFA nomenclature a "lauryl methyl gluceth-10 hydroxypropyl dimonium chloride".

The compounds with alkyl groups used as surfactants can 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 narrow homolog distribution can be used. Under "normal" homolog division are understood to mean mixtures of homologs which are obtained in the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates as catalysts. By 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 can be 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-acrylate copolymers,

Polyvinylpyrrolidone and vinylpyrrolidone / vinyl acetate copolymers and polysiloxanes, cationic polymers such as quaternized cellulose ethers, polysiloxanes with quaternary groups, dimethyldiallylammonium chloride polymers, acrylamide-dimethyldiallylammonium chloride copolymers, with diethylsulfate-vinylamethylpyrenolymethylrolidone-methacrylate-methacrylate-methacrylate-methacrylate-methacrylate-methacrylate-methacrylates

Imidazolinium methochloride copolymers and quaternized polyvinyl alcohol, zwitterionic and amphoteric polymers such as, for example, acrylamidopropyltrimethylammonium chloride / acrylate copolymers and octylacrylamide / methyl methacrylate / tert.-butylaminoethyl methacrylate ^ hydroxydyl methacrylate copolymers, for example polyacrylic acids, polyacrylic polymers, anionic polymers, anionic polymers, anionic polymers, 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, 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, amylopectin and

Dextrins, clays such as e.g. B. bentonite or fully synthetic hydrocolloids such as e.g.

Polyvinyl alcohol,

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

Egg lecithin and cephaline, as well as silicone oils, Protein hydrolyzates, especially elastin, collagen, keratin, milk protein,

Soy protein and wheat protein hydrolyzates, their condensation products with

Fatty acids and quaternized protein hydrolyzates,

Perfume oils, dimethyl isosorbide and cyclodextrins,

Solubilizers such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol 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 whale, 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 like latex,

Pearlescent agents such as ethylene glycol mono- and distearate,

Blowing agents such as propane-butane mixtures, N ₂ O, dimethyl ether, C0 ₂ and air as well

Antioxidants.

The constituents of the water-containing carrier are used in the usual amounts for the preparation of the agents used in the process according to the invention, e.g. 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. Suitable metal salts are, for example, 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 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 used.

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

In the method according to the invention, the components and customary cosmetic ingredients are usually applied to the fibers containing keratin, left on the fiber for some time, usually about 30 minutes, and then rinsed out or washed out with a shampoo.

According to the invention, the stable diazonium salts of the formula I and the compounds of component B are applied to the hair in one process step, i.e. the components are applied together or in succession, but without the fiber being present in one of the components. The optionally contained ammonium or metal salts can be added to the first or the second component. Pretreatment of the fibers with the saline solution is not excluded.

The stable diazonium salts of the formula I and the compounds of component B are preferably stored separately, 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 (50 to 80 ° C) water is usually added before use and a homogeneous mixture is produced. Examples

Preparation of a coloring solution

A slurry of 10 mmoles of a stable diazonium salt of Formula I, 10 mmoles of an oxidation dye precursor, 10 mmoles of sodium acetate and a drop of a 20% fatty alkyl ether sulfate solution in 100 ml of water was prepared. The slurry was briefly heated to about 80 ° C and filtered after cooling, the pH was then adjusted to 6.

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

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

The color depth was rated on the following scale:

no or very pale color

(+) weak intensity

+ medium intensity

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

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

Colorings with 2,5-dimethoxy-4-benzoylaminophenyldiazonium chloride (real blue salt RR)

Table 2

Table 3

Colorings with 4-diazo-diphenylamine sulfate (Variamin blue salt RT)

Table 4

Colorings with 4-diazo-4'-methoxydiphenylamine chloride (Variamin blue salt B)

Table 5

Colorings with 4-diazo-4'-methoxydiphenylamine chloride (Variamin blue salt B)

Table 6

Colorings with 4-diazo-3,2'-dimethylazobenzenesulfate (real garnet salt GBC)

Table 7

Colorings with 2-methoxy-4-nitrobenzene-diazonium-1, 5-naphthalenedisulfonate (true red salt B)

Table 8

Colorings with 4-diazo-2,5-dimethoxy-4'-nitroazobenzene chloride-zinc chloride double salt (real black salt K),

Claims

claims

1. A method for dyeing keratin fibers, especially human hair, wherein

A) at least one stable diazonium salt with the formula I or its physiologically compatible salt,

in which R ¹ , R ² , R ³ and R ⁴ independently of one another represent a hydrogen atom

Halogen atom, a (C _r C ₄ ) alkyl group, a (CC ₄ ) alkoxy group, a hydroxy (C ₁ -C ₄ ) alkoxy group, a hydroxy group, a

Sulfo group, a carboxy group, an amino group which is represented by a

(C ₁ -C ₄ ) alkyl group, hydroxyalkyl group, a or an optionally substituted benzene group which may be substituted or be part of a heterocycle, or a (C.-C ₄ ) -

Acyl group, with two of the residues also fused one

Can form benzene ring and can be an optionally substituted phenyl group, or together with the N atom a heterocyclic

Forming a ring means

B) optionally in combination with a compound selected from compounds having a primary or secondary amino group, selected from primary or secondary aromatic amines, nitrogen-containing heterocyclic

Compounds, and / or aromatic hydroxy compounds and / or CH-active compounds, is applied to the fiber in a one-step process.

2. The method according to claim 1, characterized in that the stable diazonium salt with the formula I is selected from 4-diazo-phenylamine sulfate (Variamin blue salt RT), 4-diazo-4'-methoxydiphenylamine chloride (Variamin blue salt B), 4-diazo-3, 2'-dimethylazobenzenesulfate (real garnet salt GBC), 2-methoxy-4- nitrobenzene diazonium naphthalene-1,5-disulfonate (real red salt B), 4-diazo-2,5-dimethoxy-4'-nitroazobenzene chloride-zinc chloride double salt (real black salt K), 2,5-dimethoxy-4-benzoylaminophenyldiazonium chloride. (Real Blue Saiz RR), 2-methoxy-4-nitrobenzene-diazonium-1, 5-naphthalenedisulfonate, 4-chloro-2-nitrobenzene-diazonium chloride-zinc chloride double salt (Echtrotsalz 3 GL), 5-chloro-2-methoxy-benzenediazonium- chloride-zinc chloride double salt (real red salt RC), 4-benzamido-2-methoxy-5-methylbenzoldiazonium chloride double salt (real violet salt B), 2-diazo-1-naphthol-4-sulfonic acid, sodium salt of 2- Diazo-1-naphthol-5-sulfonic acid and any mixtures of the above.

Method according to one of claims 1 or 2, characterized in that the stable diazonium salts with the formula I are contained in an amount of 0.03 to 65 mmol, in particular 1 to 40 mmol, based on 100 g of the total colorant.

Method according to one of claims 1 to 3, characterized in that component B is selected from primary or secondary amines from the group consisting of N- (2-hydroxyethyl) -N-ethyl-, N- (2-methoxyethyl-) , 2,3-, 2,4-, 2,5-dichloro-p-phenylene diamine, 2-chloro-p-phenylene diamine, N, N-bis- (2-hydroxyethyl) -p-phenylene diamine, 2.5 -Dihydroxy-4-morpholinoaniline dihydrobromide, 2-, 3-, 4- aminophenol, o-, m-, p-phenylenediamine, 2,4-diaminophenoxyethanol, 2- (2,5-diaminophenyl) ethanol, 2.5 Diaminotoluene, phenol,

-phenethol, 4-methylamino-, 3-amino-4- (2'-hydroxyethyloxy) -, 3,4-methylene-diamino-, 3,4-methylenedioxyaniline, 3-amino-2,4-dichloro-, 4- Methylamino-, 2-methyl-5-amino-, 3-methyl-4-amino-, 2-methyl-5- (2-hydroxyethylamino) -, 2-methyl-5-amino-4-chloro-, 6 -Methyl-3-amino-2-chloro, 5- (2-hydroxyethylamino) -4-methoxy- 2-methyl-, 2-amino-4- (2-hydroxyethylamino) -, 4-amino-2-aminomethyl- , 4-amino-2-hydroxymethylphenoi, 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-hydroxybenzoic 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-tetraamino - benzene-tetrahydrochloride, 2,4,5-triaminophenol-trihydrochloride, 2,4,6-

Triaminoresorcinol trihydrochloride, 4,5-diaminobenzate catechol sulfate, 4,6-

Diaminopyrogallol dihydrochloride, 3,5-diamino-4-hydroxy-catechol sulfate aromatic nitriles, anilines, in particular 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 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 tetrahydrochloride, 3,3', 4,4'-tetraamino-benzophenone, 1,3-bis (2,4-diaminophenoxy) propane -tetrahydrochloride, 1, 8-bis- (2,5-diaminophenoxy) -3,6-dioxaoctane-tetrahydrochloride, 1, 3-bis- (4-aminophenylamino) -propane, -2-propanol, 1, 3-bis- [N- (4-aminophenyl) -2-hydroxyethylamino] -2-propanol, N, N-bis- [2- (4-aminophenoxy) ethyljmethylamine 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-methylpyrimidine, 2,3,4-trimethylpyrrole, 2,4-dimethyl-3-ethyl-pyrrole, 3,5-diamine opyrazole, -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 and 4-hydroxyindoline, and in each case from the physiologically tolerable salts of these compounds formed with preferably inorganic acids, aromatic hydroxy compounds selected from the group consisting of 2-, 4-, 5-methylresorcinol, 2,5-dimethylresorcinol, resorcinol, 3-methoxyphenol, pyrocatechol, hydroquinone, pyrogallol, phloroglucinol, hydroxyhydroquinone, 2-, 3-, 4-methoxy -, 3-Dimethylamino-, 2- (2-hydroxyethyl) -, 3,4-methylenedioxyphenol, 2,4-,

3,4-dihydroxybenzoic acid, -phenylacetic acid, gallic acid, 2,4,6- _ trihydroxybenzoic acid, -acetophenone, 2-,

4-chlororesorcinol, 1-naphthol, 1, 5-, 2,3-, 2,7-dihydroxynaphthalene, 6-dimethylamino-4-hydroxy-2-naphthalenesulfonic acid, 3,6-dihydroxy-2,7-naphthalenesulfonic acid, and

CH-active compounds selected from the group consisting of 1, 2,3,3-tetramethyl-3H-indolinium iodide, 1, 2,3,5-tetramethylindolinium-p-toluenesulfonate, 1, 2,3,5-tetramethylindolinium methanesulfonate , 2,3-dimethyl-benzothiazolium iodide, 2,3-dimethyl-benzothiazolium-p-toluenesulfonate, rhodanine, rhodanine-3-acetic acid, 1-ethyl (methyl) -2-quinaldinium iodide, barbituric acid,

Thiobarbituric acid, 1, 3-dimethyl (ethyl) thiobarbituric acid, oxindole, coumaranone and 1-methyl-3-phenyl-2-pyrazolinone.

5. The method according to claim 4, characterized in that component B 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-methylenedioxyaniline, 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-amino, 2-hydroxymethyl-4-amino, 2-amino-4- (2-hydroxyethylamino) phenol, 3,4-methylenedioxyphenol, 3,4 -Diamino benzoic 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, 5,6-dihydroxyindoline, 1-naphthol , 1, 5-, 1, 6-, 1, 7-, 2,3-, 2,6-, 2,7-dihydroxynaphthaiine and 2-naphthol-3,6-disulfonic acid Na salt, and each from the physiologically tolerable salts of these compounds which are preferably formed with inorganic acids.

6. The method according to any one of claims 1 to 5, characterized in that direct dyes from the group of itrophenylenediamines, nitroamino phenols, anthraquinones or indophenols preferably in an amount of 0.01 to 20 wt .-%, based on the total Colorants are used.

7. The method according to any 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, are to be added.

8. The method according to any one of claims 1 to 7, characterized in that oxidizing agents, in particular H ₂ O ₂ , in an amount of 0.01 to 6 wt .-%, based on the application solution, are used.

9. The method according to any one of claims 1 to 8, characterized in that anionic, zwitterionic or nonionic surfactants are used.

10. The method according to any one of claims 1 to 9, characterized in that components A and optionally B and other conventional cosmetic ingredients applied to the keratin fibers, some time, usually about 30 minutes, left on the fiber and then rinsed out or washed out with a shampoo.