EP1434552A1

EP1434552A1 - Method for dyeing keratinous fibres

Info

Publication number: EP1434552A1
Application number: EP02777202A
Authority: EP
Inventors: Doris Oberkobusch; Hinrich Möller; Horst Höffkes
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2001-10-04
Filing date: 2002-09-25
Publication date: 2004-07-07
Also published as: DE10148845A1; WO2003030841A1

Abstract

The invention concerns a method for dyeing keratinous fibres, in particular human hair, which consists in first treating the fibres with an oxidizing agent, then (A) with at least a diazo and/or carbonyl compound of formula I and/or II and optionally (B) applying on the keratinous fibres at least a compound as constituent B, selected from a group consisting of (a) primary or secondary compounds with amino or hydroxy group, selected among primary or secondary aromatic amines, nitrogenous heterocyclic compounds and aromatic hydroxy compounds, (b) amino acids, (c) oligopeptides consisting of 2 to 9 amino acids, (d) CH acid compounds, (e) quaternary ammonium compounds, and, optionally, standard cosmetic constituents, leaving them for some time, usually about 30 minutes, on the fibres to produce their effect, then rinsing or removing with a shampoo. The method enables to obtain wash-resistant dyeing which does not damage the fibres during the dyeing step nor resulting in sensitizing the scalp.

Description

"Process for dyeing fibers containing keratin"

The invention relates to a process for dyeing keratin-containing fibers, in particular human hair, in which the fibers are first treated with an oxidizing agent and then with a reactive 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.

Especially among younger people there is often a desire for particularly fashionable, brilliant colors such as intense shades of red, yellow, orange, green, blue or violet. The desired coloring result can usually only be achieved on very light hair, for which a more or less strong lightening of the natural color tone is necessary. Depending on the strength of the lightening, the lightening can damage the hair or, if the scalp is sensitive, can irritate the scalp. The subsequent coloration should therefore be very mild and still guarantee an improved durability of the dyeing compared to normal hair tints, in order to avoid costly and time-consuming re-dyeing at short intervals.

Two methods for producing intense, fashionable color tones are known from the prior art. In the first process, the coloring is carried out oxidatively by oxidizing agents, such as. B. H ₂ O ₂ , and oxidation dye precursors. A true-to-color coloring is obtained in this process. A disadvantage is the strain on the hair due to the oxidative coloring. in the second process, direct dyes are applied to pre-blond hair. Fashionable shades can be obtained without additional damage to the hair. The washability of the dye is usually unsatisfactory. The object of the present invention is to provide a process for dyeing keratin-containing fibers, by means of which it is possible to apply fashionably intensive colorations to the fibers which show good wash resistance and do not cause strain on the fibers in the actual dyeing step.

Surprisingly, it has now been found that intense, fashionable color tones can be produced on fibers containing keratin if the fibers are first treated with an oxidizing agent and then treated with compounds according to compound A below and, if appropriate, with compounds of component B. Wash-resistant dyeings are obtained which do not strain the fiber in the coloring step and do not sensitize the scalp.

The invention relates to a process for dyeing keratin-containing fibers, in particular human hair, in which the fibers are first treated with an agent 1 containing an oxidizing agent and then an agent 2 containing A. at least one compound A with the formula I,

R ¹

AR -X

(D

in which

• AR stands for benzene, naphthalene, pyridine, furan, quinoline, isoquinoline, quinolizine, pyrimidine, pyrrole, thiophene, indole, indan, imidazole, benzimidazole, benzothiazole, indazole, benzoxazole, quinoxaline, quinazoline, cinnoline, acenaphthene, fluorene, biphenyl Diphenylmethane, benzophenone, diphenyl ether, azobenzene, diphenylamine, stilbene and their partially or fully hydrogenated derivatives,

• R ¹ , R ² and R ³ independently of one another represent a hydrogen atom, a halogen atom, a C ^ alkyl, C ^ alkoxy, C ^ acyl, C ^ hydroxyalkoxy, a hydroxy or nitro group or an amino, C ^ -acylamino, ammonio or a 1-imidazoli (ni) o group, which can be substituted by C ^ alkyl or C ^ hydroxyalkyl groups, and also two of the radicals R ¹ , R ² and R ³ one to AR fused-on saturated or unsaturated, optionally substituted 5-, 6- or 7-ring, which in turn can carry an aromatic, optionally substituted ring, the system AR, depending on the size of the ring, can carry further substituents that have the same May have meaning like R ¹ , R ² and R ³ and • X stands for a group N≡N ⁺ Y ^" , where Y ^{" stands} for a halide, nitrate, 0.5 sulfate, hydrogen sulfate, alkene sulfonate, arene sulfonate or a hydroxy group or a group -QR ⁴ or a group -Q-CO-R ⁴ , wherein Q represents a direct bond, an oxygen atom, a carbonyl group, an optionally substituted methylene, vinylene, 1, 3-butadiene-1, 4-diyl or phenylene group and R ⁴ is a hydrogen atom, a C ^ alkyl, C _2Jr alkenyl, an optionally substituted aryl or heteroaryl group, a group - [CH ₂ CH ₂ O] _z -R ⁵ in which R ^{5 is} a C ^ alkyl -, C ₂ ^ alkenyl, one optionally substituted e means aryl or heteroaryl group and z represents an integer from 1 to 5, or the groups -QR ⁴ or -Q-CO-R ⁴ form with one of the substituents R ¹ , R ² or R ³ a saturated condensed on AR or unsaturated, optionally substituted 5-, 6- or 7-ring, which can also carry a fused-on aliphatic or aromatic, carbocyclic or heterocyclic, optionally substituted ring,

and / or with the formula II

G represents a direct bond, a CrC ^ alkylene group, a C ₂ -C ₄ alkenylene group or a C -C ₆ dialkenylene group,

R ⁶ and R ⁷ independently of one another represent a hydrogen atom, a CrC ₄ alkyl group, or together with the group -C (O) -GC (O) - form an optionally substituted ring, which in turn forms a condensed one may carry an optionally substituted aromatic ring, where the groups R ⁶ and R ⁷ together form a CrC ₄ alkenylene group, a C -C ₆ dialkenylene group or a CC ₄ alkylene group,

B. and optionally at least one compound selected from a group that is formed from

(a) compounds with primary or secondary amino group or hydroxyl group selected from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds,

(b) amino acids,

(c) oligopeptides composed of 2 to 9 amino acids,

(d) CH-acidic compounds,

(e) quaternary ammonium compounds,

and the physiologically tolerable salts of the abovementioned compounds, applied to the keratin-containing fibers, left on the fiber for some time, usually about 30 minutes, and then rinsed out or washed out with a shampoo.

In the first process step, the fibers are treated with an oxidizing agent in a manner known per se. H ₂ O ₂ , H ₂ O ₂ releasing compounds or combinations thereof are preferably used as oxidizing agents, in particular for human hair, these compounds also being able to be applied to an inert carrier. H ₂ O ₂ can e.g. B. in combination with Na, K, NH - peroxodisulfate or the corresponding peroxodiphosphonates, especially in an alkaline environment. The pH is preferably in the range from pH 6 to 11, particularly preferably in the range from pH 8.5 to pH 10.5. The oxidizing agent preparation can also compounds such. B. Magnesium peroxide can be added. H ₂ O can be in the oxidizing agents in free form or bound, e.g. B. be used as sodium carbonate peroxyhydrate, urea peroxide or melamine perhydrate. The oxidizing agents are generally used in an amount of 0.01 to 6% by weight, based on the application solution. The compounds with the formulas I and II and component B used in the second step are to a large extent known from the literature or commercially available or can be prepared by known synthetic processes.

Particularly brilliant wash-out colors can be obtained if the compounds with the formula I are stable diazonium salts, (X = N≡N ⁺ Y ^~ ) onium aldehydes (AR = quaternized pyridine, X = -QR ⁴ with Q = carbonyl, R ⁴ = hydrogen atom ) or isatin or isatin derivatives (AR = benzene, X = Q-CO-R ⁴ with Q = carbonyl, R ³ = NH, R ⁴ = hydrogen, where R ³ and X form a 5-ring fused to AR), or are any mixtures of the above compounds.

Examples of suitable diazonium salts with the formula I are 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 diazonium naphthalene-1,5-disulfonate (Echtrotsalz ^® B), 4-diazo-2,5-dimethoxy-4'-nitroazobenzene chloride-zinc chloride double salt (real black salt ^® K), 2,5-dimethoxy-4 - benzolyaminophenyldiazonium chloride (Real Blue Salt ^® 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-methoxybenzoldiazonium chloride-zinc chloride double salt (Echtrotsalz ^® RC), 4-benzamido-2-methoxy-5-methylbenzoldiazonium 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.

Preferred onium aldehydes are, for example, the benzenesulfonates, p-toluenesulfonates, methanesulfonates, perchlorates, sulfates, chlorides, bromides, iodides and / or tetrachlorozincates of 4-formyl-1-methylpyridinium, 3-formyl-1-methylpyridinium, 2-formyl- 1-methylpyridinium, 4-formyl-1-ethylpyridinium, 2-formyl-1-ethylpyridinium, 4-formyl-1-benzylpyridinium, 2-formyl-1-benzylpyridinium, 4-formyl-1,2-dimethylpyridinium, 4-formyl- 1,3-dimethylpyridinium, 4-formyl-1-methylquininoin, 2-formyl-1-methylquininoinium, 4- (2-formylvinyl) -1-methylquinolium, 4-acetyl-1-methylpyridinium, 2-acetyl-1- methylpyridinium, 4-acetyl-1-methylquininoin and 4- (2-formyl-vinyl) -1-methylpyridinium, 2,6-dichloro-4-formyl-1-methylpryridinium, 2,6-diphenyl-4-formyl-1- methylpyridinium, 4-benzoyl-1-methylpyridinium, 4-propionyl-1-methylpyridinium, 4-pyridinaldehyde-N-oxide and N-methylpyridoxal as well as any mixtures of the above compounds. Examples of isatin derivatives are isatin, isatin-5-sulfonic acid, isatin-4-carboxylic acid and isatin-5-carboxylic acid, N-substituted isatin derivatives, such as N-hydroxymethyl-isatin, N-hydroxyethyl-isatin N- (2'-hydroxypropyl ) isatin, N- (3'-hydroxypropyl) isatin, N- (2 ', 3'-dihydroxypropyl) isatin, N- (2'-sulfoethyl) isatin, N- (3'-sulfopropyl) isatin , N-allylisatin, N- vinylisatin, N-benzylisatin, N- (4'-methoxybenzyl) isatin, N- (4'-carboxybenzyl) isatin, N- (4'-sulfobenzyl) isatin, N- (2nd '-Dimethylaminoethyl) isatin, N- (2'-pyrrolidinoethyl) isatin, N- (2'-piperidinoethyl) isatin, N- (2-furylmethyl) isatin, N- (2-thienylmethyl) isatin, N - (2-pyridylmethyl) isatin, N- (3-pyridylmethyl) isatin, N- (4-pyridylmethyl) isatin, N-allylisatin-5-sulfonic acid, 5-chloro-N- (2'-hydroxyethyl) - isatin, 5-methyl-N- (2'-hydroxyethyl) isatin, 5-chloroisatin, 5-nitroisatin, 5,7-dichloroisatin, 5,7-dichloro-N-allyl isatin, 5-nitro-N-allyl isatin, N -Hydroxymethyl-5-methylisatin, N-hydroxymethyl-5-chloroisatin, N-hydroxymethyl-5- sulfoisatin, N-hydroxymethyl-5-carboxyisatin, N-hydroxymethyl-5-nitroisatin, N-hydroxymethyl-5-bromisatin, N-hydroxymethyl-5-methoxyisatin, N-hydroxymethyl-5,7-dichloroisatin, N-dimethylaminomethylisatin, N- Diethylaminomethylisatin, N- (bis (2'-hydroxyethyl) aminomethyl) isatin, N- (2'-hydroxyethylaminomethyl) isatin, N- (bis- (2'-hydroxypropyi) aminomethyl) isatin, N- ( 2'-pyrrolidino) isatin, N- (2'-piperidino) isatin, N- pyrrolidinomethylisatin, N-piperidinomethylisatin, N-morpholinomethylisatin, N- (2-morphoinoethyl) isatin, N- (1 ', 2', 4'-triazolyl) methylisatin, N- (1-imidazolyl) methylisatin, N-carboxymethylaminomethylisatin, N- (2'-carboxyethylaminomethyl) isatin, N- (3'-carboxypropylaminomethyl) isatin, N- (bis - (2'-hydroxyethyl) aminomethyl) -5-methylisatin, N- piperidinomethyl-5-chloroisatin, N- (2'-sulfoethylamino) isatin, and the alkali metal and optionally ammonium salts of the acidic compounds, quinisatin and their derivatives, such as N-methylquinisatin and the alkali and ammonium salt e of the acidic compounds.

Further compounds of formula I used with preference are 5- (4'-dimethylaminophenyl) penta-2,4-dienal, 5- (4'-diethylaminophenyl) penta-2,4-dialenal, 5- (4 ' -Methoxyphenyl) -penta-2,4-dienal, 5- (3 ', 4'-dimethoxyphenyl) -penta-2,4-dienal, 5- (2', 4'-dimethoxyphenyl) -penta-2,4- dienal, 5- (4'-piperidinophenyl) penta-2,4-dienal, 5- (4'-morpholinophenyl) penta-2,4-dienal, 5- (4'-pyrrolidinophenyl) penta-2,4 -dienal, 6- (4'-dimethylaminophenyl) -hexa-2,4-dien-2-one, 6- (4'-diethylaminophenyl) -hexa-2,4-dien-2-one, 6- (4 ' -Methoxyphenyl) hexa-2,4-dien-2-one, 6- (3 ', 4'-dimethoxyphenyl) hexa-2,4-dien-2-one, 6- (2', 4'-dimethoxyphenyl ) -hexa-2,4-dien-2-one, 6- (4'-piperidinophenyl) -hexa-2,4- dien-2-one, 6- (4'-morpholinophenyl) hexa-2,4-dien-2-one, 6- (4'-pyrrolidinophenyl) hexa- 2,4-dien-2-one, 5- (4'-Dimethylamino-1-naphthyl) penta-2,4-dienal, 2-nitro-piperonal, 5-nitro-piperonal, 6-nitro-piperonal, 5-hydroxy-2-nitro-piperonal, 2-hydroxy -5-nitro-piperonal, 2-chloro-6-nitro-piperonaI, 5-chloro-2-nitro-piperonal, 2,6-di-nitro-piperonal,

2-nitrobenzaldehyde, 3-nitrobenzaldehyde, 4-nitrobenzaldehyde, 6-nitrobenzaldehyde, 4-methyl-3-nitrobenzaldehyde, 3-hydroxy-4-nitrobenzaldehyde, 4-hydroxy-3- nitrobenzaldehyde, 5-hydroxy-2-nitrobenzaldehyde, 2-hydroxy-5-nitrobenzaldehyde, 2-hydroxy-3-nitrobenzaldehyde, 2-fluoro-3-nitrobenzaldehyde, 3-methoxy- 2-nitro-benzaldehyde, 4-chloro-3-nitro-benzaldehyde, 2-chloro-6-nitro-benzaldehyde, 5-chloro-2-nitro-benzaldehyde, 4-chloro-2-nitro-benzaldehyde, 2,4- Dinitrobenzaldehyde, 2,6-dinitrobenzaldehyde, 2-hydroxy-3-methoxy-5-nitrobenzaldehyde, 4,5-dimethoxy-2-nitrobenzaldehyde, 5-nitrovanillin, 3,5-dinitrosalicylaldehyde, 5-bromo-3-nitrosalicylaldehyde, 3-nitro-4-formylbenzenesulfonic acid, 4-nitro-1-naphthaldehyde, 2-nitrocinnamaldehyde, 3-nitrocinnamaldehyde, 4-nitrocinnamaldehyde,

Carbazolaldehydes or carbazole ketones, especially 9-methyl-3-carbazolaldehyde, 9-ethyl-3-carbazolaldehyde, 3-acetylcarbazole, 3,6-diacetyl-9-ethylcarbazole, 3-acetyl-9-methylcarbazole, 1, 4-dimethyl-3 -carbazolaldehyde, 1, 4,9-trimethyl-3-carbazolaldehyde, 4-trimethylammoniobenzaldehyde, 4-benzyldimethylammoniobenzaldehyde, 4-trimethylammoniozimtaldehyde, 4-trimethylammonionaphthaldehyde, 2-methoxy-4-trimethylammonobaldehyde (4'-acetylphenyl) trimethylammonium, 4- (N, N-diethyl) -N-methylammonio) benzaldehyde, N- (4'-benzoylphenyl) trimethylammonium, N- (4'-benzoylphenyl) -N, N-diethylmethylammonium-, N- (4'-formylphenyl) -N-methylpyrrolidinium-, N- (4'-formylphenyl) -N-methylpiperidinium-, N- (4'-formylphenyl) -N-methylmorpholinium- N - (4'-Acetylphenyl-N-methylmorpholinium-, N- (4'-benzoylphenyl) -N-methylmorpholinium-, 3-formyl-N-ethyl-N-methylcarbazolium-, 3-formyl-9,9-dimethylcarbazolium-, 1- (4'-Acetylphenyl) -3-methylimidazolium-, 1 - (4'-Acetylphenyl) -3-methyl-2-imidazolinium-, 1 - (4 ' - Benzoylphenyl) -3-methylimidazolium, 5-acetyl-1, 3-diethyl-2-methylbenzimidazolium, 5-trimethylammonio-1-indanone salts, especially the benzenesulfonates, p-toluenesulfonates, methanesulfonates, ethanesulfonates, propanesulfonates, Perchlorates, sulfates, chlorides, bromides, iodides, tetrachlorozincates, methyl sulfates, trifluoromethanesulfonates, hexafluorophosphates, tetrafluoroborates,

Cinnamaldehyde, salicylaldehyde, vanillin, 4-hydroxy-3-methoxycinnamaldehyde

(Coniferylaldehyde), 2,4-dihydroxybenzaldehyde, 4-dimethylaminobenzaldehyde, 4-diethylaminobenzaldehyde, 4-dimethylamino-2-hydroxybenzaldehyde, 4-pyrrolidino benzaldehyde, 4-morpholinobenzaldehyde, 4-piperidinobenzaldehyde, 4-dimethylaminoacetophenone, 4-hydroxynaphthaldehyde, 4-dimethylaminonaphthaldehyde, 4-

Dimethylaminobenzylidene acetone, 4-dimethylaminocinnamaldehyde, 2-

Dimethylaminobenzaldehyde, 2-chloro-4-dimethylaminobenzaldehyde, 4-dimethylamino-2-methylbenzaldehyde, trans-4-diethylamino-cinnamaldehyde, 4- (dibutylamino) benzaldehyde, 4-diphenylaminobenzaldehyde, 2,3,6,7-tetrahydro-1H, 5H-benzo [ij] quinolizine-9-carboxaldehyde, 4-dimethylamino-2-methoxybenzaldehyde, 2,3,6,7-tetrahydro-8-hydroxy-1 H, 5H-benzo [ij] quinolizine-9-carboxaldehyde, 4 - (1-Imidazolyl) benzaldehyde, 2-morpholino-benzaldehyde, indole-3-carboxaldehyde, 1-methylindole-3-carboxaldehyde, N-ethylcarbazole-3-carboxaldehyde, 2-formylmethylene-1,3,3-trimethylindoline (tribases Aldehyde), 1,3-diacetylbenzene, 1,4-diacetylbenzene, 1,3,5-triacetylbenzene, 2-benzoyl-acetophenone, 2- (4'-methoxybenzoyl) -acetophenone, 2- (2'-furoyl) -acetophenone , 2- (2'-pyridoyl) acetophenone, 2- (3'-pyridoyl) acetophenone,

1-phenyl-1,2-propanedione, 1-phenyl-1,2-butanedione, 1-chlorophenyl-1,2-propanedione, 1-phenyl-3,3-dimethyl-1,2-butanedione, benzil, anisil, Salicil, 5,5'-dibromosalicil, 2,2'-FuryI, 2,2'-thienyl, 2,2'-, 4,4'-pyridil, 6,6'-dimethyl-4,4'-pyridil, 4-hydroxy-, 4-methoxy-, 4-chloro-, 4-methyl-, 4-dimethylamino-, 4,4'-dihydroxy-, -dimethyl-, -dibromo-, -dichloro-, -Bis-dimethylamino- , 2,4-dihydroxy-, 3,3'-dimethoxy, 2'-chloro-3,4-dimethoxy-, 3,4,5,3 ', 4', 5'-hexamethoxy-benzil,

Acetophenone, propiophenone, 2-hydroxyacetophenone, 3-hydroxyacetophenone, 4-hydroxyacetophenone, 2-hydroxypropiophenone, 3-hydroxypropiophenone, 4-hydroxypropiophenone, 2-hydroxybutyrophenone, 3-hydroxybutyrophenon, 4-hydroxyophenone, 4-hydroxybone 2,5-dihydroxyacetophenone, 2,6-dihydroxyacetophenone, 2,3,4-trihydroxyacetophenone, 3,4,5-trihydroxyacetophenone, 2,4,6-trihydroxyacetophenone, 2,4,6-trimethoxyacetophenone, 3,4, 5-trimethoxyacetophenone, 3,4,5-tri-methoxy-acetophenone-diethyl ketal, 4-hydroxy-3-methoxy-acetophenone, 3,5-dimethoxy-4-hydroxy-acetophenone, 4-amino-acetophenone, 4-dimethylamino acetophenone, 4-morpholino-acetophenone, 4-piperidino-acetophenone, 4-imidazolino-acetophenone, 2-hydroxy-5-bromo-acetophenone, 4-hydroxy-3-nitroacetophenone, acetophenone-2-carboxylic acid, acetophenone-4- carboxylic acid, benzophenone, 4-hydroxy-benzophenone, 2-amino-benzophenone, 4,4'-dihydroxy-benzophenone, 2,4-dihydroxy-benzophenone, 2,4,4'-trihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2 Hydroxy-1-acetonaphthone, 1-hydroxy-2-acetonaphthone, Chromon, Chromon-2-carboxylic acid, Flavon, 3-Hydroxyflavon, 3,5,7-Trihydroxyflavon, 4 ', 5,7-Trihydroxyflavon, 5,6,7 -Trihydroxyflavon, Quercetin, Indanon, 9-Fluorenon, 3-Hydroxyfluorenon, Anthron, 1, 8-Dihydroxyanthron, heterocyclic carbonyl compounds, such as 2-indolaldehyde, 3-indolaldehyde, 1-methylindole-3-aldehyde, 2-methylindole-3-aldehyde, 1-acetylindole-3-aldehyde, 3-acetylindole, 1-methyl-3-acetylindole, 2- (1 ', 3', 3'-trimethyl-2'-indolinylidene) acetaldehyde, 1-methylpyrrole-2-aldehyde, 1-methyl-2-acetylpyrrole, 1-pyridine aldehyde, 2-pyridine aldehyde, 3-pyridine aldehyde, 1-acetylpyridine, 2-acetylpyridine, 3-acetylpyridine, pyridoxal, quinoline-3-aldehyde, quinoline-4-aldehyde, antipyrin-4-aldehyde, furfural, 5-nitrofurfural, 2-thenoyl-trifluoroacetone, chromon-3- aldehyde, 3- (5'-nitro-2'-furyl) acrolein, 3- (2'-furyl) acrolein, imidazole-2-aldehyde,

Indanone derivatives, such as. B. 1,2-indandione, 2-oximo-1-indanone, indan-1,2,3-trione-2-oxime, 5-methoxy-indan-1, 2,3-thon-2-oxime, 2- Nitro-1,3-indanedione, quaternized azafluorenones, such as the trifluoromethanesulfonates, benzenesulfonates, p-toluenesulfonates, methanesulfonates, perchlorates, sulfates, chlorides, bromides, iodides, tetrachlorozincates, hexafluorophosphates tetrafluoroborates [1-methyl-5-indeno 1,2-b] pyridinium- (4'-methyl-4'-azonio-9'-fluorenone), 1-ethyl-5-oxo-indeno [1, 2-b] pyridinium, 1-benzyl-5-oxo -indeno [1, 2-b] pyridinium, 2-methyl-5-oxo-indeno [1, 2-c] pyridinium, 2-methyl-9-oxo-indeno [2,1-c] pyridinium. 1-methyl-9-oxo-indeno [2,1-b] pyridinium,

Carbonyl compounds according to formula II which are preferably used according to the invention are glutacondialdehyde, fumaraldehyde, glyoxal, malondialdehyde, amber dialdehyde, mucondialdehyde, 1, 2-naphthoquinone, 4-sulfonic acid-1,2-naphthoquinone, 1,2-benzoquinone, 1,4-benzoquinone, 2, 3-dimethoxy-5-methyl-1,4-benzoquinone (juglone), 1,4-naphthoquinone, spinulosin, atromentin, aurentioglyocladin, 5-hydroxy-1, 4-naphthoquinone, 2,5-dihydroxy-6-methylbenzoquinone, 2 Hydroxy-3-methyl-6-methoxy-1,4-benzoquinone, 2,5-dihydroxy-3,6-diphenyl-1,4-benzoquinone, 2,5-dihydroxy-6-isopropyl-1,4-benzoquinone , 4,5-dimethoxy-1,2-benzoquinone, 2-hydroxy-1,4,4

Naphthoquinone, fafiolin, 5,8-dihydroxy-1,4-naphthoquinone, naphthopurpurin, 2-hydroxy-3- (3'-methyl-2'-butenyl) -1, 4-naphthoquinone, plumbagin, 3,5-dihydroxy- 2-methyl-1, 4-naphthoquinone, 2-hydroxy-3-methyl-1, 4-naphthoquinone, 3,5-dihydroxy-1, 4-naphthoquinone, 2,5-dihydroxy-1, 4-naphthoquinone, 2- Methoxy-5-hydroxy-1, 4-naphthoquinone, 3-methoxy-5-hydroxy-1,4-naphthoquinone and 9,10-phenanthrenequinone.

The compounds of component B are, on the one hand, compounds which, on their own, only give weakly colored keratin-containing fibers and only give brilliant colors together with the compounds of the formulas I and / or II. On the other hand, there are also compounds that are already used as oxidation dye precursors or direct pullers.

Suitable compounds with primary or secondary amino group as component B are e.g. B. primary and secondary aromatic amines such as N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, N- (2-hydroxyethyl) -N-ethyl-p-phenylenediamine, N, N-bis- (2-hydroxyethyl) -p-phenylene diamine, N- (2-methoxyethyl) -p-phenylene diamine, 2,3-dichloro-p-phenylene diamine, 2,4-dichloro-p-phenylene diamine, 2,5-dichloro-p- phenylenediamine, 2-chloro-p-phenylenediamine, 2,5-dihydroxy-4-morpholinoaniline, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminomethyl-4-aminophenol, 2-hydroxymethyl-4-aminophenol, o- Phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,5-diaminotoluene, 2,5, -diaminophenol, 2,5-diaminoanisole, 2,5, diaminophenethole, 4-amino-3-methylphenol, 2- (2, 5-diaminophenyl) ethanol, 2,4-diaminophenoxyethanol, 2- (2,5-diaminophenoxy) ethanol, 3-amino-4- (2-hydroxyethyloxy) phenol, 3,4-methylenedioxyphenol, 3,4- Methylenedioxyaniline, 3-amino-2,4-dichlorophenol, 4-methylaminophenol, 2-methyl-5-aminophenol, 3-methyl-4-aminophenol, 2-methyl-5- (2-hydroxyethylamino) phenol, 3 amino-2-chloro-6-methylph enol, 2-methyl-5-amino-4-chlorophenol, 5- (2-hydroxyethylamino) -4-methoxy-2-methylphenol, 4-amino-2-hydroxymethylphenol, 2- (diethylaminomethyl) -4-aminophenol, 4- Amino-1-hydroxy-2- (2-hydroxyethylaminomethyl) benzene, 1-hydroxy-2-amino-5-methyl-benzene, 1-hydroxy-2-amino-6-methyl-benzene, 2-amino-5- acetamidophenol, 1,3-dimethyl-2,5-diaminobenzene, 5- (3-hydroxypropylamino) 2-methylphenol, 5-amino-4-methoxy-2-methylphenol, N, N-dimethyl-3-aminophenol, N-cyclopentyl-3-aminophenol, 5-amino-4-fluoro-2-methylphenol, 2,4-diamino-5-fluorotoluene, 2,4-diamino-5- (2-hydroxyethoxy) toluene, 2,4- Diamino-5-methylphenetol, 3,5-diamino-2-methoxy-1-methylbenzene, 2-amino-4- (2-hydroxyethylamino) anisole, 2,6-bis (2-hydroxyethylamino) -1-methylbenzene, 1,3-diamino-2,4-dimethoxybenzene, 3,5-diamino-2-methoxy-toluene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 2-aminophenylacetic acid, 3-aminophenylacetic acid, 4- Aminophenylacetic acid, 2,3-diaminobenzoic acid, 2,4-diaminobenzoic acid, 2, 5-diamino benzoic acid, 3,4-diamino benzoic acid, 3,5-diamino-benzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 3-amino-4-hydroxy-benzoic acid, 4-amino-3-hydroxy-benzoic acid, 2-aminobenzenesulfonic acid, 3 -Ami- nobenzenesulfonic acid, 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-di- sulfonic acid, 3-amino-2-naphthoic acid, 3-aminophthalic acid, 5-aminoisophthalic acid, 1,3,5-triaminobenzene, 1,2,4-triaminobenzene, 1,2,4,5-tetraaminobenzene, 2,4,5- Triamino-phenol, pentaaminobenzene, hexaaminobenzene, 2,4,6-triaminoresorcinol, 4,5-diamino-catechol, 4,6-diaminopyrogallol, 1- (2-hydroxy-5-aminobenzyl) -2-imidazolidinone, 4-amino- 2 - ((4 - [(5-amino-2-hydroxyphenyl) methyl] piperazinyl) methyl) phenol, 3,5-diamino-4-hydroxy-catechol, 1,4-bis (4-aminophenyl) -1,4 diazacycloheptane, aromatic nitriles, such as 2-amino-4-hydroxybenzonitrile, 4-amino-2-hydroxybenzonitrile, 4-aminobenzonitrile, 2,4-diaminobenzonitrile, nitro group-containing amino compounds, such as 3-amino-6-methylamino-2-nitro -pyridine, picramic acid, [8 - [(4-amino-2-nitrophenyl) -azo] - 7-hydroxy-naphth-2-yl] -trimethylammonium chloride, [8 - ((4-amino-3-nitrophenyl) -azo ) -7-hydroxy-naphth-2-yl] trimethylammonium chloride (Basic Brown 17), 1-hydroxy-2-amino-4,6-dinitrobenzene, 1-amino-2-nitro-4- [bis- (2- hydroxyethyl) amino] -benzene, 1-Amino-2 - [(2-hydroxyethyl) amino] -5-nitrobenzene (HC Yellow No. 5), 1-Amino-2-nitro-4 - [(2-hydroxyethyl) amino] benzene (HC Red No. 7), 1-amino-4- (2-hydroxyethylamino) -5-chloro-2-nitrobenzene, 4-amino-2-nitro-diphenylamine (HC Red No. 1), 1 - [(2-hydroxyethyl) amino] -2-nitro-4-amino-benzene (HC Red No. 3), 4-amino-3-nitrophenol, 4-amino-2-nitrophenol, 6-nitro -o-toluidine, 1-amino-3-methyl-4 - [(2-hydroxyethyl) amino] -6-nitrobenzene (HC Violet No. 1), 1-amino-2-nitro-4 - [(2,3 -dihydroxypropyl) amino] -5-chloro-benzene (HC Red No. 10), 2- (4-amino-2-nitroanilino) -benzoic acid, 6-nitro-2,5-diaminopyridine, 2-amino-6-chloro -4-nitrophenol, 1-amino-2- (3-nitrophenylazo) -7-phenylazo-8-naphthol-3,6-disulfonic acid disodium salt (Acid blue No. 29), 1-amino-2- (2-hydroxy- 4-nitrophenylazo) -8-naphthol-3,6-disulfonic acid disodium salt (Palatinchrome green), 1-amino-2- (3-chloro-2-hydroxy-5-nitrophenylazo) -8-naphthol-3,6-disulfonic acid disodium salt (Gallion), 4-amino-4'-nitrostilbene-2,2'-disulfonic acid disodium salt, 2,4-diamino-3 ', 5'-dinitro-2'-hydroxy-5-methyl-azobenzene (Mordant brown 4) , 4'-amino-4-nitrodiphenylamine-2-sulfonic acid, 4'-amino-3'-nitrobenzophenone-2-carboxylic acid, 1-amino-4-nitro-2- (2-nitrobenzylideneamino) benzene, 2- [2 - (diethyl amino) ethylamino] -5-nitroaniline, 3-amino-4-hydroxy-5-nitrobenzenesulfonic acid, 3-amino-3'-nitrobiphenyl, 3-amino-4-nitro-acenaphthene, 2-amino-1-nitronaphthalene, 5- Amino-6-nitrobenzo-1,3-dioxole, anilines, in particular anilines containing nitro groups, such as 4-nitroaniline, 2-nitroaniline, 1,4-diamino-2-nitrobenzene, 1,2-diamino-4-nitrobenzene, 1 -Amino-2-methyl-6-nitrobenzene, 4-nitro-1,3-phenylenediamine, 2-nitro-4-amino-1- (2-hydroxyethylamino) benzene, 2-nitro-1-amino-4- [ bis- (2-hydroxyethyl) amino] benzene, 4-amino-2-nitrodiphenylamine-2'-carboxylic acid, 1-amino-5-chloro-4- (2-hydroxyethylamino) -2-nitrobenzene, aromatic anilines or phenols with a further aromatic radical, as shown in formula III

(III)

in the

R ⁸ represents 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 1-4 alkoxy-C 1-4 alkyl groups,

R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ independently of one another represent a hydrogen atom, a hydroxy or an amino group which can be substituted by C ^ alkyl, C ^ hydroxyalkyl, C ^ alkoxy, C ^ aminoalkyl or C ^ alkoxy-C ^ alkyl groups can be substituted,

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

-Z ² - (CH ₂ -Z -CH ₂ -Z ³ ) ₀ - (IV)

in the

Z ⁴ denotes a direct bond, a CH ₂ or CHOH group,

Z ² and Z ³ independently of one another for an oxygen atom, an NR ¹⁴ group, in which R ^{14 is} hydrogen, a C 1-4 alkyl or a hydroxyC 1-4 alkyl group, both groups together with the rest of the molecule also being a 5-, Can form 6 or 7 ring means the group O- (CH ₂ ) _p -NH or NH- (CH ₂ ) _p '-O, where p and p' are 2 or 3, and

O is a number from 1 to 4,

such as 4,4'-diaminostilbene and its hydrochloride, 4,4'-diaminostilbene-2,2'-disulfonic acid mono- or di-Na salt, 4-amino-4'-dimethylaminostilbene and its hydrochloride, 4, 4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl isulfide, 4,4'- Diaminodiphenyl sulfoxide, 4,4'-diaminodiphenylamine, 4,4'-diaminodiphenylamine-2-sulfonic acid, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenyl ether, 3,3 ', 4,4'-tetraaminodiphenyl, S.S '^^' - tetraamino-benzophenone, 1,3-bis (2,4-diaminophenoxy) propane, 1,8-bis (2,5-diaminophenoxy) -3,6-dioxaoctane, 1, 3-bis- (4-aminophenylamino) propane, 1,3-bis- (4-aminophenylamino) -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 and bis- (5-amino-2-hydroxyphenyl) methane.

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-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-amino-3-hydroxy-pyridine, 2,6-diamino-pyridine. 2,5-diamino-pyridine, 2- (aminoethylamino) -5-aminopyridine, 2,3-diamino-pyridine, 2-dimethylamino-5-amino-pyridine, 2-methylamino-3-amino-6-methoxy- pyridine, 2,3-diamino-6-methoxy-pyridine, 2,6-dimethoxy-3,5-diamino-pyridine, 2,4,5-triamino-pyridine, 2,6-dihydroxy-3,4- dimethylpyridine, N- [2- (2,4-diaminophenyl) aminoethyl] -N- (5-amino-2-pyridyl) amine, N- [2- (4-aminophenyl) aminoethyl] -N- (5-amino -2-pyridyl) amine, 2,4-dihydroxy-5,6-diaminopyrimidine, 4,5,6-triaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5, 6-triaminopyrimidine, 2,4,5,6-tetraaminopyrimidine, 2-methylamino-4,5,6-triaminopyrimidine, 2,4-diaminopyrimidine, 4,5-diaminopyrimidine, 2-amino-4-methoxy-6- methyl pyrimidine, 3,5-diaminopyrazole, 3,5-diamino-1, 2,4-triazole, 3-aminopyrazole, 3-amino-5-hydroxypyrazole, 1-phenyl-4,5-diaminopyrazole, 1- (2nd -Hydroxyethyl) -4,5-diaminopyrazole, 1-phenyl-3-methyl-4,5-diaminopyrazole, 4-amino-2,3-dimethyl-1-phenyl-3-pyrazolin-5-one (4-aminoantipyrine) , 1-phenyl-3-methylpyrazol-5-one, 2-aminoc hinolin, 3-aminoquinoline, 8-aminoquinoline, 4-aminoquinoline, 2-aminonicotinic acid, 6-aminonicotinic acid, 5-aminoisoquinoline, 5-aminoindazole, 6-aminoindazole, 5-aminobenzimidazole, 7-amino nobenzimidazole, 5-aminobenzothiazole, 7-aminobenzothiazole, 2,5-dihydroxy-4-morpholino-aniline and indoi- and indoline derivatives, such as 4-aminoindole, 5-aminoindole, 6-aminoindole, 7-aminoindole, 5,6-dihydroxyindole, 5,6-dihydroxyindoline and 4-hydroxyindoline. According to the invention, the hydroxypyrimidines disclosed in DE-U 1-299 08 573 can also be used as heterocyclic compounds. The aforementioned compounds can be used both in free form and in the form of their physiologically salts in question, e.g. B. as salts of inorganic acids such as hydrochloric or sulfuric acid.

Suitable aromatic hydroxy compounds are e.g. B. 2-methylresorcinol, 4-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, resorcinol, 3-methoxyphenol, pyrocatechol, hydroquinone, pyrogallol, phloroglucinol, hydroxyhydroquinone, 2-methoxyphenol, 3-methoxyphenol, 4-methoxyphenol, 3- Dimethylaminophenol, 2- (2-hydroxyethyl) phenol, 3,4-methylenedioxyphenol, 2,4-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 2,4-dihydroxyphenylacetic acid, 3,4-dihydroxyphenylacetic acid, gallic acid, 2 , 4,6-trihydroxybenzoic acid, 2,4,6-trihydroxyacetophenone, 2-chlororesorcinol, 4-chlororesorcinol, 1-naphthol, 1, 5-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 6-dimethylamino -4-hydroxy-2-naphthalenesulfonic acid and 3,6-dihydroxy-2,7-naphthalenesulfonic acid.

Preferred amino acids are all naturally occurring and synthetic α-amino acids, e.g. obtained by hydrolysis from vegetable or animal proteins, e.g. Collagen, keratin, casein, elastin, soy protein, wheat gluten or almond protein accessible amino acids. Both acidic and alkaline amino acids can be used. Preferred amino acids are arginine, histidine, tyrosine, phenylalanine, DOPA (dihydroxyphenylalanine), omithin, proline, lysine and tryptophan. But also other amino acids, e.g. 6-aminocaproic acid and β-alanine can be used.

Component B can also be a CH-acidic compound. Those compounds which carry a hydrogen atom bonded to an aliphatic carbon atom are generally regarded as CH-acidic, activation of the corresponding carbon-hydrogen bond being effected on account of electron-withdrawing substituents. According to the invention, the CH-acidic compounds are preferably selected from compounds according to one of the formulas C1 to C21:

M ¹ - CH ₂ - M ² (C1)

wherein

• M ^{1 is} a group -COM ³ or COOM ³ , in which M ^{3 represents} a hydrogen atom or a CrCe-alkyl group, or a group -C (M ⁴ ) = C (C-≡N) ₂ , in which M ⁴ For represents a hydrogen atom, a CC ^ alkyl group or an aryl group, • M ^{2 has} the same meaning as M ¹ or a cyano group, a substituted or unsubstituted aryl group or aryl-CrC ^ alkyl group, a substituted or unsubstituted, saturated or unsaturated heterocycle,

Compounds with the formula C2

wherein

M ^{5 is} a group -COM ⁷ or COOM ⁷ , in which M ^{7 represents} a hydrogen atom or a d-Ce-alkyl group, or a cyano group, a substituted or unsubstituted aryl group or an aryl-CrC ^ alkyl group, a substituted or unsubstituted, is saturated or unsaturated heterocycle,

• M ^{6 is} a substituted or unsubstituted CrCβ alkyl group, an acetyloxy group, a C ₃ -C ₆ cycloalkyl group, a substituted or unsubstituted aryl group or aryl-dC ^ alkyl group, a substituted or unsubstituted aminoaryl group, a substituted or unsubstituted, saturated or unsaturated heterocycle is

Compounds with the formula C3

wherein

• M ⁸ is a group -COM ¹⁰ or COOM ¹⁰ , where M ^{10 represents} a hydrogen atom or a C ₆ -C ₆ -alkyl group, or a cyano group, a substituted or unsubstituted aryl group or aryl-CrC-alkyl group, a substituted or unsubstituted, is saturated or unsaturated heterocycle,

M ^{9 is} a substituted or unsubstituted aryl group or aryl-C 1 -C ₄ -alkyl group, is a substituted or unsubstituted aminoaryl group, a substituted or unsubstituted, saturated or unsaturated heterocycle,

Pyrazole derivatives (a), which can be selected from the following formulas C4 and C5

wherein

• M ¹¹ and M ¹² independently of one another for a substituted or unsubstituted CC ₆ alkyl group, an acetyloxy group, a C ₃ -C ₆ cycloalkyl group, a substituted or unsubstituted aryl group or aryl-CrC-alkyl group, a substituted or unsubstituted aminoaryl group, a substituted one or unsubstituted, saturated or unsaturated heterocycle,

M ^{13 is} a hydrogen atom or a substituted or unsubstituted C 1 -C 6 -alkyl group,

(b) two pyrazole rings of the formula C4 or C5 bonded via M ¹¹ or M ¹²

Barbituric acid derivatives with the following formula C6

(C6) wherein

M ¹⁴ and M ¹⁵ independently of one another represent a dC ₆ alkyl group, a C ₂ -C ₆ alkenyl group, a C ₃ -C ₆ cycloalkyl group, an aryl-C ₁ -C ₄ -alkyl group, a substituted or unsubstituted aryl group, or a bicyclic bonded via the residues M ¹⁴ or M ¹⁵ ,

X stands for an oxygen or a sulfur atom,

Pyridine derivatives with the formulas C7a and C7b

wherein

M is a substituted or unsubstituted CC ₆ alkyl group or substituted or unsubstituted aryl group,

M ^{7 is} a hydrogen atom, a substituted or unsubstituted CC ₆ alkyl group or a substituted or unsubstituted aryl group,

M ^{18 is} a hydrogen atom, a cyano group, a substituted or unsubstituted d-Ce alkyl group, a group COOM ¹⁹ , in which M ^{19 is} a hydrogen atom or a substituted or unsubstituted dC ₆ alkyl group,

Compounds with the following formula C8

wherein

A stands for an oxygen atom, a sulfur atom, a sulfonyl group or a G Grruuppppee NNMM ^2200aa ,, wwoorriinn MM ^2200aa eeiinn Waasssseerrstoffatom, a substituted or unsubstituted d-Ce alkylene group, M and M ²¹ independently of one another represent a hydrogen, a chlorine, a bromine atom, a hydroxy group, a nitro group, a dC ₆ alkyl group, a C Ce alkoxy, a carboxamide, a sulfonamide, a carboxyl, a -CC -acyl, a cyano group or an amino group -NM ²² M ²³ , in which M ²² and M ²³ independently represent a hydrogen atom or a dC ₆ -alkyl group,

Compounds with the formulas C9 and C10

wherein

A 'represents an oxygen atom, a sulfur atom or a group NM ²⁵ , in which M ^{25 represents} a hydrogen atom or a substituted or unsubstituted dC ₆ alkyl group,

M ²⁴ stands for a hydrogen, a chlorine, a bromine atom, a hydroxyl group, a nitro group, a C Ce alkyl, a dC ₆ alkoxy, a carboxamide, a sulfonamide, a carboxyl, a dC ₄ -Acyl, a cyano group or an amino group -NM ²⁶ M ²⁷ , in which M ²⁶ and M ²⁷ independently of one another represent hydrogen and a CrCe alkyl group

Compounds with the formula C11

wherein

M ^{28 is} a hydrogen atom, a hydroxy group, a substituted or unsubstituted d-Cε-alkyl group or a substituted or unsubstituted aryl or dC ₆ -alkylaryl group; M ²⁹ represents a hydrogen atom or a C 1 -C 8 alkyl group Indanedione derivatives with the formula C12

wherein

M ^{30 is} a hydrogen, a chlorine, a bromine atom, a nitro, a dC ₆ -alkyl, a d-Ce-alkoxy, a carboxamide, a sulfonamide or a cyano group,

Compounds with the formula C13

wherein

Z represents an oxygen atom or a group NM _f -32, where M «32

Represents hydrogen atom or a dC ₆ alkyl group,

Z 'represents a sulfur atom or a group NM ³³ , where M ³³ is

Represents hydrogen atom or a dC ₆ alkyl group,

M ³¹ represents a hydrogen atom, a dC ₆ alkyl group or a C _r C ₄ carboxyalkyl group,

Dioxopyrazole compounds with the formula C14

wherein

M and M independently of one another represent a hydrogen, a chlorine, a bromine atom, a hydroxyl group, a nitro group, a CC ₆ alkyl, a CC ₆ alkoxy, a carboxamide, a sulfonamide, a carboxyl, a C _r C ₄ -acyl, a cyano group or an amino group -NM ³⁶ M ³⁷ , in which M ³⁶ and M ³⁷ independently represent hydrogen or a dC ₆ -alkyl group,

5-oximidazole derivatives with the formula C15

wherein

M and M independently of one another represent a hydrogen, a chlorine, a bromine atom, a hydroxyl group, a nitro group, a CC ₆ alkyl, a dC ₆ alkoxy, a carboxamide, a sulfonamide, a carboxyl, a dd-acyl, a cyano group or an amino group -NM ⁴¹ M ⁴² , in which M ⁴¹ and M ⁴² independently of one another represent a hydrogen atom or a dC ₆ -alkyl group, M ⁴⁰ represents a hydrogen atom or a dC ₆ -alkyl group,

Derivatives of dehydrobutyrolactone with the formula C16

wherein

• M and M «44 independently of one another represent a hydrogen, a chlorine, a bromine atom, a hydroxyl group, a nitro group, a CC ₆ -alkyl, a C -, - C ₆ -alkoxy-, a carboxamide-, one Sulfonamide, a carboxyl, a dd-acyl, a cyano group or an amino group -NM ⁴⁵ M ⁴⁶ , in which M ⁴⁵ and M ⁴⁶ independently represent a hydrogen atom or a dC ₆ alkyl group Compounds with the formula C17

wherein

D ¹ is a fused aromatic or heteroaromatic ring,

D ² is a carbonyl group or a methylene group CD'D ", in which D ¹ or D ¹¹ each have a substituent with a Hammett constant between 0.4 and 2.0 or both substituents in total a Hammett constant between 0, 4 and 2.0;

• D ³ stands for a carbonyl group, an oxygen atom, a sulfur atom, a group NM ⁴⁷ if D ^{2 is} not oxygen, or a group C = S, a group C = NR ⁴⁸ , a sulfinyl group, a sulfonyl group, where R ⁴⁷ and R ⁴⁸ independently of one another represent a hydrogen atom or a CC alkyl radical,

Hydroxypyrimidine derivatives with the formula C18

wherein

M ⁴⁹ and M ⁵⁰ independently of one another are a hydrogen atom or a substituted or unsubstituted CC ₆ alkyl group,

E ^{1 represents} an oxygen, a sulfur atom or a group NH,

E ^{2 represents} a group NH or an oxygen atom,

E ^{3 represents} an amino group or a hydroxy group,

with the proviso that a) when E ¹ and E ^{2 represent} an oxygen atom, E ^{3 is} not a hydroxy group, and b) when E ^{1 is} a sulfur atom and E ^{2 is} an oxygen atom, E ^{3 is} not a hydroxy group,

quaternized nitrogen compounds of formula C19

wherein,

M ⁵¹ and M ⁵² independently of one another represent a hydrogen atom, a halogen atom, a hydroxyl group, a dC -hydroxyalkyl group, a dC ₆ - aminoalkyl group, a dd-dialkylamino-dd-alkyl group, a linear or branched dC ₆ alkyl group, a C ₂ -C ₆ alkenyl group, an optionally substituted aryl group, a sulfonic acid group, a carboxyl group, a formyl group, a nitro group, a cyano group or a group -NM ⁵⁴ M ⁵⁵ , where M ⁵⁴ and M ⁵⁵ independently represent a hydrogen atom, a dC ₆ -Alkyl group, a C ₂ -C ₆ alkenyl group, an aryl-dC ₄ -alkyl group or a dC ₄ -hydroxyalkyl group, where M ⁵¹ and M ⁵² together can form a fused-on 5- or 6-membered, aliphatic or aromatic ring, which is in turn substituted by the radicals M ⁵⁶ and M ⁵⁷ , where M ⁵⁶ and M ⁵⁷ independently of one another represent the radicals which are defined under M ⁵¹ , M ⁵³ represents a hydrogen atom, a dC -hydroxyalkyl group, a dC ₆ - aminoalkyl group, a CrC ₄ -dialkylamino -CC-C -alkyl group, a linear or branched dC ₆ alkyl group, a C ₂ -C ₆ alkenyl group, an optionally substituted aryl group, a sulfonic acid group, a carboxyl group, one Formyl group, a nitro group, a cyano group or a group -NM ⁵⁸ M ⁵⁹ , where M ⁵⁸ and M ⁵⁹ independently represent a hydrogen atom, a dC ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group, an aryl-d-C -alkyl group or a CrC -hydroxyalkyl group,

Y stands for an oxygen atom, a sulfur atom, an optionally substituted methylene group or a group NM ⁶⁰ , where M ⁶⁰ can stand for the same groups which are defined under M ⁵⁵ , A ^" stands for a chloride, bromide, iodide, hexafluorophosphate, tetrachlorozincate, tetrafluoroborate, trifluoromethyl sulfonate, methyl sulfonate or p-toluenesulfonate,

Onium compounds of the formulas C20 and C21

wherein M ⁵¹ , M ⁵² , M ⁵³ and A ^" are selected from the groups defined under Compound C19.

According to the invention, CH-acidic compounds also include enamines which arise from quaternized N-heterocycles with an CH-acidic alkyl group conjugated to the quaternary nitrogen by alkaline treatment. Examples of suitable enamines are compounds with the general formula C22

.162

^M (C22)

wherein

• M ⁶¹ stands for an aromatic radical, in particular for a 5-membered or 6-membered aryl residue, preferably a phenyl residue, or one optionally substituted with a dC ₄ -alkyl, dC ₄ -hydroxyalkyl, hydroxy, methoxy or halogen group 5-membered or 6-membered, fused, aliphatic or aromatic, carbocyclic or heterocyclic ring, preferably a phenyl residue, a quinoline or pyridyl residue,

• M ⁶² stands for a hydrogen atom, a linear or branched dC ₈ -alkyl, a linear or branched dC ₈ -hydroxyalkyl or a dC ₈ -alkoxyalkyl group, where an oxygen atom can sit between the carbon atoms of the alkyl chain, and • M ⁶³ stands for a linear or branched CC ₈ -alkyl group, a -C ₆ -alkoxy-d- C ₆ -alkyl group, a d-Cs-alkylamino-d-Ce-alkyl group, a dC ₆ -alkyl mercapto-d- Ce-alkyl group, a d-Ce-alkoxy-d-Cβ-alkylene group, a CC ₆ -alkylamino-d-Ce-alkylene group, a d-Ce-alkylmercapto-d-Ce-alkylene group, a straight-chain or branched dC ₈ -alkylene group , or is an oxygen atom, a nitrogen atom or a sulfur atom, with the proviso that the radicals M ⁶ and M ⁶³ together with the nitrogen atom and the carbon atom of the basic enamine structure form a cyclic compound if M ⁶³ is a linear or branched dC ₈ - Alkylene group, a dC ₈ -alkoxyalkylene group, a d-Ce-alkylamino-d-Ce-alkylene group, a d-Ce-alkylmercapto-d-Cealkylene group, an oxygen atom, a nitrogen atom or a sulfur atom, preferably M ^{63 being} aromatic M ^{61 is} linked to the carbon which is ortho-substituted to the enamine Carbon stands.

The compounds with the formulas C1, C2 and C3 are preferably selected from malonic acid, malonic acid esters and their derivatives and acetoacetic acid, acetoacetic acid esters and their derivatives.

Examples of compounds with the formula C4 are pyrazol-5-one, 3-methyl-pyrazol-5-one, 1-phenyl-3-methyl-pyrazol-5-one, 1- (β-cyanoethyl) -3-methyl- pyrazol-5-one, 1,3-dimethyl-pyrazol-5-one, 1- (β-acetoxyethyl) -3-methyl-pyrazol-5-one, 1- (2'-chlorophenyl) -3-methyl-pyrazole -5-one, 1-phenyl-3-carbomethoxy-pyrazol-5-one, 1- (3'-aminophenyl-pyrazol-5-one, 1 - (4'-aminophenyl) pyrazol-5-one, 3- Methyl-pyrazol-5-one-1-carboxamides, 1-phenyl-pyrazol-5-one-3-carboxamides, amino-pyrazole, 1-phenyl-5-amino-pyrazole, 1-benzyl-5-amino-pyrazole, 1-cyclohexyl-5-aminoprazole, 1-ethyl-3-methyl-5-aminopyrazole, 1-benzyl-3-phenyl-5-aminopyrazole, 1-isopentyl-5-aminopyrazole, 1 - Furfuryl-5-amino-pyrazole, 2-methyl-4H-pyrazolo (5) - [2,3-a] -benzimidazole, [1- (3'-thia-cyclopentyl) -3-methyl-pyrazol-5-one -S-dioxide], 2-methyl-1 H-3,3a, 8-triaza-cyclopenta [a] indene.

The barbituric acid derivatives with the formula C6 are preferably selected from barbituric acid, thiobarbituric acid, di-N-ethylthiobarbituric acid, di-N-

Methylthiobarbituric acid, di-n-butyl barbituric acid, di-isobutyl barbituric acid, di-N-amyl barbituric acid, di-iso-amyl barbituric acid, di-n-hexyl barbituric acid, di-benzyl barbituric acid, di- ß-phenylethyl barbituric acid, di-cyclohexyl barbituric acid, di-phenyl barbituric acid, di-p-tolyl barbituric acid, di-p-methoxybenzyl barbituric acid, N-methyl-N'-n-butyl-barbituric acid, N-methyl-N'-benzyl-barbituric acid, N-methy1-N'-ß -phenylethyl-barbituric acid, N-methyl-N'-γ-phenylpropyl-barbituric acid, N-methyl-N'-γ-phenylbutyl-barbituric acid, N-methyl-N'-α-isobutyl-γ-phenylpropyl barbituric acid, N- Methyl-N'-cyclohexyl-barbituric acid, N-methyl-N'-phenyl-barbituric acid, N-methyl-N'-p-toloyl-barbituric acid, N-methyl-N'-norbornylmethyl-barbituric acid and the corresponding N-ethyl and Nn-butyl derivatives of the above compounds.

2,6-Dihydroxy-3-cyano-4-methyl-pyridine, cyanopyridones, aminonitropyridones and aminocyano-pyridones, in particular N-methyl-3-cyano-4-methyl, may be mentioned as preferred examples of the pyridine derivatives having the formula C7 -6-hydroxy-pyridone-2, N-ethyl-3-cyano-4-methyl-6-hydroxy-pyridone-2, N-β-methoxyethyl-3-cyano-4-methyl-6-hydroxy-pyridine-2 -on, N-β-hydroxyethyl-3-cyano-4-methyl-6-hydroxy-pyridin-2-one, N-butyl-3-cyano-4-methyl-6-hydroxy-pyridin-2-one and N -Phenyl-3-cyano-4-methyl-6-hydroxy-pyridin-2-one.

The compounds with the formula C8 can be selected from 6-hydroxybenzofuran (2H) -one and 3-indoxy acetate.

The compounds having the formula C9 can be selected from indol-2-one, 1,3-dihydro-indol-2-one, 3H-benzofuran-2-one, 1-methyl-1,3-dihydro-indol-2- on, 5-methoxy-3H-benzofuran-2-one, 5-nitro-1, 3-dihydro-indol-2-one, 1-methyl-5-nitro-1, 3-dihydro-indol-2-one, 6-methoxy-1,3-dihydro-indol-2-one, 5-chloro-1,3-dihydro-indol-2-one, 5,6-difluoro-1,3-dihydro-indol-2-one, 6-hydroxy-5-methoxy-1,3-dihydro-indol-2-one, 5,6-dimethoxy-1,3-dihydro-indol-2-one and 6-trifluoromethyl-1,3-dihydro-indole- 2-one.

Examples of compounds having the formula C10 are imidazo [1.2-a] pyridin-2-one and 6-bromo-imidazo [1.2-a)] pyridin-2-one.

The compounds with the formula C11 are preferably selected from the derivatives in which in the formula C11 the radicals M ²⁸ and M ²⁹ stand for a hydrogen atom, such as 2,4-dihydroxyquinoline.

A suitable example of an indanedione derivative with the formula C12 is 1,3-indanedione. The compounds with the formula C13 are preferably selected from rhodanine, rhodanine-3-acetic acid and 4-imino-4,5-dihydro-thiazol-2-ylamine.

1,2-Diphenyldioxopyrazole can be mentioned as the preferred compound with the formula C14.

The compounds having the formula C15 are preferably selected from 2-phenyl-3,5-dihydro-imidazol-4-one and 3-methyl-2-p-toloyl-3,5-dihydro-imidazol-4-one.

A preferred example of a compound having the formula C16 is phenyldihydrobutyrolactone.

The compounds having the formula C17 are preferably selected from 1,1-dioxo-1,2-dihydro-11,6-benzo [b] -thiophen-3-one, 1-dicyanomethylene indane, 1,3-

Bis (dicyanomethylene) indane and 2- (1 ', ¹ ^-dioxo-1, ^2-dihydro-1 r, 6'-benzo [b] thiophene-3'-ylidene) malononitrile.

Examples of hydroxypyrimidine derivatives with the formula C18 are 2,4-diamino-6-hydroxy-pyrimidine, 2,6-diamino-4-hydroxypyrimidine, 4-amino-2,6-dihydroxypyrimidine, 4-amino-6-hydroxy-2- sulfanylpyrimidine, 2-amino-4,6-dihydroxypyrimidine, 4,6-dihydroxy-1-mercaptopyrimidine and 2,4,6-trihydroxypyrimidine, with 2,4-diamino-6-hydroxypyhmidine being particularly preferred.

Preferred compounds with the formula C19, C20 or C21 are 1,2-dimethylnaphtho [1,2-d] thiazolium p-toluenesulfonate, 2,3-dimethyl-benzothiazolium iodide, 2,3-dimethyl-benzothiazolium p-toluenesulfonate, 1-ethyl-2-methyl-naphtho [1,2-d] thiazolium p-toluenesulfonate, 1,2,3,3-tetramethyl-3-H-indolium iodide, 1,2,3,3-

Tetramethyl-3H-indolium p-toluenesulfonate, 1-methyl-2-quinaldinium iodide, 1-ethyl-2-quinaldinium iodide and 1,4-dimethylquinolinium iodide.

Preferred enamines having the formula C22 are those in which the radicals M ⁶¹ and M ⁶³ form a cyclic compound together with the nitrogen atom and the carbon atom of the basic enamine structure, the 1,3,3-trimethyl-2-methylene-indoline, the 1- (2-Hydroxyethyl) -3,3-dimethyl-2-methylene indoline and 3-ethyl-2-methylenebenzothiazoline are particularly preferred. The oligopeptides can be naturally occurring or synthetic oligopeptides, but also the oligopeptides contained in polypeptide or protein hydrolyzates, provided that they have sufficient water solubility for use in the colorants according to the invention. Examples include glutathione or the oligopeptides contained in the hydrolyzates of collagen, keratin, casein, elastin, soy protein, wheat gluten or almond protein. Use together with compounds having a primary or secondary amino group or with aromatic hydroxy compounds is preferred.

Examples of quaternary ammonium salts are tetramethyl, tetraethyl, tetrapropyl, tetrabutyl, benzyltrimethylammonium chloride, bromide, iodide, hydrogen sulfate, 0.5 sulfate and the quaternized hydroxyethyl cellulose derivatives (INCI name: Polyquaternium 10).

The compounds of component B are particularly preferably selected from the group consisting of N- (2-hydroxyethyl) -N-ethyl-p-phenylenediamine, 2-chloro-p-phenylenediamine, N, N-bis- (2-hydroxyethyl) ) -p-phenylenediamine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-amino-6-chloro-4-nitrophenol, 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-dichlorophenol, 2-methyl-5- aminophenol, 3-methyl-4-aminophenol, 2-methyl-5- (2-hydroxyoxyamino) phenol, 2-methyl-5-amino-4-chlorophenol, 6-methyl-3-amino-2-chlorophenol, 2 Aminomethyl-4-aminophenol, 2-diethylaminomethyl-4-aminophenol, 2-

Dimethylaminomethyl-4-aminophenol, 2,6-dichloro-4-aminophenol, 2-hydroxymethyl-4-aminophenol, 2,6-bis (2-hydroxyethylamino) -1-methylbenzene, bis- (2-hydroxy-5-aminophenyl) methane, bis (4,5-amino-2-hydroxyphenyl) methane, 1,3-bis (2,4-diaminophenoxy) propane, 1,4-bis (4-aminophenyl) -1, 4-diazacycloheptane, 1 , 8-bis (2,5-diaminophenoxy) -3,6-dioxaoctane, 4,4'-diaminodiphenylamine, 3,4-methylenedioxyphenol, 3,4-diaminobenzoic acid, 2,5-diaminopyridine, 2-dimethylamino-5-aminopyridine , 2-amino-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine, 2,3-diamino-6-methoxypyridine, 3,5-diamino-2,6-dimethoxypyridine, 2,6-dihydroxy -3,4-dimethylpyridine, 2-hydroxy-4,5,6-triaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2,4,5,6-tetraaminopyrimidine, 2-methylamino-4,5 , 6-triamino-pyrimidine, 3,5-diaminopyrazole, 3-amino-5-hydroxypyrazole, 4,5-diamino-1- (2-hydroxyethyl) pyrazole, 5,6-dihydroxyindole, 5,6- Dihydroxyindoline, 4-amino-2,3-dimethyl-1-phenyl-3-pyrazolin-5-one (4-aminoantipyrine), 2,3-dimethylbenzothiazolium p-toluenesulfonate, 1,2,3,3-tetramethyl-3H -Indolinium-p-toluenesulfonate, thiobarbituric acid, rhodanine, 2,3-dimethyl-benzothiazolium-p-toluenesulfonate, 1,2-dimethyl-naphtho [1,2-d] thiazolium-p-toluenesulfonate, 1-methyl-2-quinaldinium p-toluenesulfonate, 1,4-dimethylquinolinium p-toluenesulfonate, ß-alanine, L-proline, L-lysine, DL-tyrosine and their physiologically tolerable salts preferably formed with inorganic acids.

Very particularly preferred compounds of component B according to the invention are N, N-bis (2-hydroxyethyl) p-phenylenediamine, 2,5-diaminotoluene, 2- (2,5-diaminophenyl) ethanol, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminomethyl-4-aminophenol, 2- (diethylaminomethyl) -4-aminophenol, 1-hydroxy-2-amino-5-methyl-benzene, 2,4-diaminophenoxyethanol, 3-amino-2,4- dichlorophenol, 2-methyl-5-aminophenol, 2-methyl-5- (2-hydroxyethylamino) phenol, 6-methyl-3-amino-2-chlorophenol, 2-methyl-5-amino-4-chlorophenol, 3, 4-methylenedioxyaniline, 3,4-diaminobenzoic acid, 3,5-diamino-2-methoxy-1-methylbenzene, 2-amino-4- (2-hydroxyethylamino) anisole, 2,6-bis (2-hydroxyethylamino) -1 methylbenzene, 1,3-bis (2,4-diaminophenoxy) propane, 4,5-diamino-1- (2-hydroxyethyl) pyrazole, 1,4-bis (4-aminophenyl) -1,4-diazacycloheptane, Bis (2-hydroxy-5-aminophenyl) methane, 1,8-bis (2,5-diaminophenoxy) -3,6-dioxaoctane, 4,4'-diaminodiphenylamine, 2-amino-3-hydroxypyridine, 3- Amino-2-methylamino-6-methoxypyridine, 2,6-dihydroxy-3,4 - dimethylpyridine, 5,6-dihydroxyindole, 5,6-dihydroxyindoline, 2,4,5,6-tetraaminopyhmidine, 2-hydroxy-4,5,6-triamino-pyrimidine, 4-hydroxy-2,5,6-triamino -pyrimidine and their physiologically compatible salts formed with preferably inorganic acids.

Components A and B are preferably used in an amount of 0.03 to 65 mmol, in particular 1 to 40 mmol, based on 100 g of the finished coloring agent (agent 2) used.

Color intensifiers can be used in addition to the compounds used as component B in the process according to the invention in order to obtain further and more intensive colorations. The color enhancers are preferably selected from the group consisting of piperidine, piperidine-2-carboxylic acid, piperidine-3-carboxylic acid, piperidine-4-carboxylic acid, pyridine, 2-hydroxypyridine, 3-hydroxypyridine, 4-hydroxypyridine, imidazole, 1- Methyl imidazole, arginine, histidine, pyrrolidine, proline, Pyrrolidone, pyrrolidone-5-carboxylic acid, pyrazole, 1,2,4-triazole, piperazine, methoxybutanol, propylene carbonate, ethylene carbonate, their derivatives and their physiologically tolerable salts.

The aforementioned color enhancers can be used in an amount of 0.03 to 65 mmol, in particular 1 to 40 mmol, in each case based on 100 g of the entire colorant (agent 2). If one of the compounds defined as a color enhancer is used both as a color enhancer and as component B, the amounts of these compounds can exceed the respective upper limits of 65 mmol or 40 mmol. In this embodiment, the upper limits are preferably 130 mmol, in particular 80 mmol.

In all colorants (agent 2), several different compounds with the formulas I and II and component B can also be used; several different color enhancers can also be used together.

In a less preferred embodiment, in addition to the compounds used according to the invention, customary direct dyes, e.g. B. from the group of nitrophenylenediamines, nitroaminophenols, anthraquinones or indophenols, such as. B. under the international names or trade names HC Yellow 2, HC Yellow 4, HC Yellow 6, Basic Yellow 57, Disperse Orange 3, HC Red 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 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'-hydroxyethylamino) benzene. In the process according to the invention, according to this embodiment, the substantive dyes are preferably added in an amount of 0.01 to 20% by weight, based on the components used.

Furthermore, the preparations used according to the invention can also contain naturally occurring dyes, such as those contained in henna red, henna neutral, henna black, chamomile flowers, sandalwood, black tea, rotten tree bark, sage, blue hoot, madder root, catechu, sedre and alkanna root , With regard to further customary dye components, reference is expressly made to the “Dermatology” series, edited by Ch. Culnan, H. Maibach, publisher Marcel Dekker Inc., New York, Basel, 1986, vol. 7, Ch. Zviak, The Science of Hair Care, chap. 7, pages 248 - 250 (direct dyes), and chap. 8, pages 264 - 267 (oxidation dyes), as well as the "European Inventory of Cosmetic Raw Materials", 1996, published by the European Commission, available in disk form from the Federal Association of German Industrial and Commercial Enterprises for Medicines, Health Care Products and Personal Care Products, Mannheim ,

It is not necessary that the compounds according to the invention with the formulas I and II or the optional color enhancers and substantive dyes each represent uniform compounds. Rather, in the colorants used according to the invention (agent 2), due to the production process for the individual dyes, further components may be present in minor amounts, provided that these do not adversely affect the dyeing result or for other reasons, e.g. B. toxicological, must be excluded.

The colorants (agent 2) used 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 (agent 2) can usually be incorporated into an aqueous 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 (agent 2) into anhydrous carriers.

Furthermore, the agents 1 and / or agents 2 used according to the invention can contain all active ingredients, additives and auxiliaries known in such preparations. In many cases, the agents contain at least one surfactant, and in principle both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants are suitable. In many cases, however, it has proven advantageous to select the surfactants from anionic, zwitterionic or nonionic surfactants. Suitable anionic surfactants in preparations used 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 R-0- (CH ₂ -CH ₂ 0) _x -CH ₂ -COOH, in which R is a linear alkyl group with 10 to 22 C atoms and x = 0 or 1 to 16, acyl sarcosides with 10 to 18 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,

Mono and dialkyl sulfosuccinic acid with 8 to 18 carbon atoms in the alkyl group and mono-alkyl polyoxyethyl sulfosuccinate 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 R-0 (CH ₂ -CH ₂ 0) _x -S0 ₃ H, in which R is a preferably linear alkyl group 10 to 18 carbon atoms and x = 0 or 1 to 12,

Mixtures of surface-active hydroxysulfonates according to DE-A-3725030, sulfated hydroxyalkyl polyethylene and / or hydroxyalkylene propylene glycol ethers according to DE-A-3723 354,

Sulfonates of unsaturated fatty acids with 12 to 24 carbon atoms and 1 to 6 double bonds according to DE-A-3926 344,

Esters of tartaric acid and citric acid with alcohols, which are adducts of about 2 to 15 molecules of ethylene oxide and / or propylene oxide with 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 -SOa ^ 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-AcyI-aminopropyl-N, N-dimethylammonium glycinate, for example coconut acylaminopropyl dimethylammonium glycinate, and -AlkyI-3-carboxymethyl-3-hydroxyethyl-imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and the cocoacylaminoethylhydroxyethylcarboxymethylglycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known under the CTFA name Cocamidopropyl Betaine.

Ampholytic surfactants are 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 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C ₁₂ . ₁₈ - acyl sarcosine.

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

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

Ethylene oxide on glycerol,

C ₈ . ₂₂ alkyl mono- and oligoglycosides and their ethoxylated analogs,

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

Castor oil,

Addition products of ethylene oxide with sorbitan fatty acid esters

Addition products of ethylene oxide with fatty acid alkanolamides.

Examples of the cationic surfactants which can be used in the hair treatment compositions according to the invention are, in particular, quaternary ammonium compounds. Ammonium halides such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, for. B. cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, Lau17ldimethy.ammoniumch.orid, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride. The quaternized protein hydrolyzates are further cationic surfactants which can be used according to the invention.

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

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

Also very good biodegradability are quaternary Esterverbindungen, so-called "esterquats", 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 onto fatty alcohols or derivatives of these addition products, both products with a "normal" homolog distribution and those with a narrowed homolog distribution can be used. “Normal” homolog distribution is understood to mean mixtures of homologues which are obtained as catalysts when fatty alcohol and alkylene oxide are reacted using alkali metals, alkali metal hydroxides or alkali metal alcoholates. By contrast, narrow homolog distributions are obtained if, for example, hydrotaicites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates are used as catalysts. The use of products with a narrow homolog distribution can be preferred.

Other active ingredients, auxiliaries and additives are, for example, nonionic polymers such as, for example, vinylpyrrolidone-inylacrylate copolymers, polyvinylpyrrolidone and vinylpyrrolidone / vinyl acetate copolymers and polysiloxanes, cationic polymers such as quaternized cellulose ethers, polysiloxanes with quaternary acrylic groups, dimethyl dimethyldiallyl ammonium chloride copolymers, dimethylaminoethyl methacrylate-vinylpyrrolidone copolymers quaternized with diethyl sulfate, vinylpyrrolidone

Imidazoliniummethochlorid copolymers and quaternized polyvinyl alcohol, zwitterionic and amphoteric polymers such as Acrylamidopropyltri- methyl ammonium chloride / acrylate copolymers and octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers, anionic polymers such as polyacrylic acids, crosslinked polyacrylic acids, vinyl acetate / Crotonic acid copolymers, vinyl pyrrolidone / vinyl acrylate Copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers,

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

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

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

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

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

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

The constituents of the water-containing carrier are used for the production of agents suitable for the process 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 entire preparation.

For the coloring result it can be advantageous to add ammonium or metal salts to the coloring agents (agent 2). Suitable metal salts are e.g. B. formates, carbonates, halides, sulfates, butyrates, valerates, capronates, acetates, lactates, glycolates, tartrates, citrates, gluconates, propionates, phosphates and phosphonates of alkali metals, such as potassium, sodium or lithium, alkaline earth metals, such as magnesium, calcium, Strontium or barium, or of aluminum, manganese, iron, cobalt, copper or zinc, with sodium acetate, lithium bromide, calcium bromide, calcium gluconate, zinc chloride, zinc sulfate, magnesium chloride, magnesium sulfate, ammonium carbonate, chloride and acetate being preferred. These salts are preferably present in an amount of 0.03 to 65 mmol, in particular from 1 to 40 mmol, based on 100 g of the total colorant (agent 2).

The pH of the ready-to-use coloring preparations is usually between 2 and 12, preferably between 4 and 10.

Components A and optionally component B and the color enhancers optionally used can either be stored separately or together, either in a liquid to pasty preparation (aqueous or anhydrous) or as a dry powder. In the case of separate storage, the 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

Dark blonde hair strands from Kerling were bleached once with Poly ^® Blonde Ultra (Schwarzkopf-Henkel). Then one of the dye mixtures A - F listed in Table 1 was applied. After an exposure time of 30 min. at 32 ° C the dye mixture was rinsed out. After drying, the color of the strands was determined using the German Color Atlas. The strands were also measured colorimetrically using the Texflash DC 3881 (Datacolor). The so-called CIE-Lab values were determined, from which the color difference ΔE results according to the following color distance formula:

ΔE = [(ΔL) ² + (Δa) ² + (Δb) ² ] ¹ ' ²

(see also DIN 6174, German standards, Benth Verlag GmbH, Berlin, 1975).

To determine the resistance to washing, the tresses were washed 6 x with the shampoo poly ^® cure Aloe & Mango Balsam Shampoo (Schwarzkopf Henkel) and then measured again colorimetrically. The strand of hair before shampooing was used as the standard for determining the ΔE value (see Table 2).

For comparison, the commercial products Poly ^® Live Töner and Igora ^® Fleur (both based on direct dyes; Schwarzkopf-Henkel) listed in Table 2 were applied to the same ultrabonded starting strands and treated analogously to strands A - F.

All the strands treated with direct drawing showed significantly higher color difference values after washing six times and thus a significantly poorer wash resistance than the strands treated with the dye mixtures A - F according to the invention.

Legend for table 1:

Natrosol ^® 250 HR hydroxyethyl cellulose

(INCI name: Hydroxyethylcellulose) (HERCULES) Texapon ^® NSO lauryl ether sulfate, sodium salt (approx. 27.5% active substance; (INCI name: Sodium Laureth Sulfate) (COGNIS)

Dehyton ^® KN, N-Dimethyl-N- (C ₈ -d ₈ -kokosamidopropyl) ammonium acetobetaine (approx. 30% active substance; INCI name: Aqua (Water), Cocamidopropyl Betaine) (COGNIS)

Hydrenol ^® DC ₁₆ -C ₁₈ fatty alcohol (INCI name: Cetearyl alcohol) (COGNIS) Lorol ^® , techn. C ₁₂ -C ₁₈ fatty alcohol (INCI name: Coconut alcohol) (COGNIS) Eumulgin ^® B 2 cetearylstearyl alcohol with approx. 20 EO units (INCI name: Ceteareth-20) (COGNIS)

Table 1

Table 2

Color results of the dyeings and color retention after six times

shampoo

Schwarzkopf Henkel

Claims

claims

1. A process for dyeing keratin fibers, in particular human hair, wherein the fibers are first treated with an agent 1 containing an oxidizing agent and then an agent 2 containing

A. at least one compound A with the formula

R ¹

R ^z - AR - X

R ³ (I) where

• R ¹ , R ² and R ³ independently of one another represent a hydrogen atom, a halogen atom, a d- ₄ -alkyl-, d- ₄ -alkoxy-, d ^ -acyl- or d- ₄ -hydroxyalkoxy-, hydroxy- or Nitro group or an amino, d- ₄ -acylamino, ammonio or a 1-imidazoli (ni) o group, which can be substituted by d- ₄ -alkyl or d- ₄ -hydroxyalkyl groups, and also two of the radicals R ¹ , R ² and R ^{3 can form} a saturated or unsaturated, optionally substituted 5-, 6- or 7-ring fused to AR, which in turn can carry a fused-on aromatic, optionally substituted ring, the system AR depending on its size can carry further substituents which can have the same meaning as R ¹ , R ² and R ³ and

• X stands for a group N≡N ⁺ Y ^" , where Y ^{" stands} for a halide, nitrate, 0.5 sulfate, hydrogen sulfate, alkene sulfonate, arene sulfonate or a hydroxy group or a group -QR ⁴ or a group -Q-CO- R ⁴ , wherein Q represents a direct bond, an oxygen atom, a carbonyl group, an optionally substituted methylene, vinylene, 1,3-butadiene-1, 4-diyl or phenylene group and R ⁴ is a hydrogen atom, ad- ₄ -alkyl, C _M alkenyl, an optionally substituted aryl or heteroaryl group, a group - [CH ₂ CH ₂ O] _z -R ⁵ in which R ^{5 is} ad- ₄ -alkyl-, C ^ -alkenyl-, an optionally substituted aryl - or heteroaryl group and z is an integer from 1 to 5, or the groups -QR ⁴ or -Q-CO-R ⁴ form with one of the substituents R ¹ , R ² or R ³ a saturated or unsaturated AR condensed on AR optionally substituted 5-, 6- or 7-ring, which can likewise carry a fused-on aliphatic or aromatic, carbocyclic or heterocyclic optionally substituted ring,

and / or with the formula II

in which

G represents a direct bond, a dC ₄ alkylene group, a C ₂ -C ₄ alkenylene group or a C ₄ -C ₆ dialkenylene group,

• R ⁶ and R ⁷ independently of one another represent a hydrogen atom, a dC ₄ - alkyl group, or together with the group -C (O) -GC (O) - form an optionally substituted ring, which in turn carries a condensed optionally substituted aromatic ring where the groups R ⁶ and R ⁷ together form a dd-alkenylene group, a C -C ₆ -dialkenylene group or a dC -alkylene group,

B. and optionally as component B at least one compound selected from a group that is formed from

(a) compounds having a primary or secondary amino group or a hydroxy group selected from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds,

(b) amino acids,

(c) oligopeptides composed of 2 to 9 amino acids,

(d) CH-acidic compounds,

(e) quaternary ammonium compounds,

2. The method according to claim 1, characterized in that in agent 1 as oxidizing agent H ₂ 0 ₂ , H ₂ 0 releasing compounds such as sodium carbonate peroxyhydrate, urea peroxide or melamine perhydrate, or combinations of these, are used.

3. The method according to claim 2, characterized in that the agent 1 contains an additional oxidizing agent, selected from Na, K, NH ₄ peroxodisulfate and the corresponding peroxodiphosphonates.

4. The method according to claim 2 or 3, characterized in that the agent 1 additionally contains magnesium peroxide.

5. The method according to any one of claims 1 to 4, characterized in that the compound A is selected from stable diazonium salts, onium aldehydes and isatin and isatin derivatives of the formula I.

6. The method according to claim 5, characterized in that the compound of formula I is selected from

Diazonium salts such as 4-diazo-phenylamine sulfate, 4-diazo-4'-methoxydiphenylamine chloride, 4-diazo-3,2'-dimethylazobenzenesulfate, 2-methoxy-4-nitrobenzene-diazoniumnaphthalene-1,5-disulfonate, 4-diazo -2,5-dimethoxy-4'-nitroazobenzene chloride, zinc chloride double salt, 2,5-dimethoxy-4-benzolyaminophenyldiazonium chloride, 2-methoxy-4-nitrobenzoI-diazonium-1,5-naphthalenedisulfonate, 4-chloro-2-nitrobenzene- diazonium chloride-zinc chloride double salt, 5-chloro-2-methoxybenzene diazonium chloride-zinc chloride double salt, 4-benzamido-2-methoxy-5 ~ methylbenzene diazonium chloride-zinc chloride double salt, 2-diazo-1-naphthol-4-sulfonic acid, Na salt of 2-di-azo-1-naphthol-5-sulfonic acid,

Onium aldehydes, such as the benzenesulfonates, p-toluenesulfonates, methanesulfonates, perchlorates, sulfates, chlorides, bromides, iodides and / or tetrachlorozincates of 4-formyI-1-methylpyridinium, 3-formyl-1-methylpyridinium, 2-formyl-1-methylpyridinium, 4-formyl-1-ethylpyridinium, 2-formyI-1-ethylpyridinium, 4-formyl-1-benzylpyridinium, 2-formyl-1-benzylpyridinium, 4-formyl-1,2-dimethylpyridinium, 4-formyl-1, 3- dimethylpyridinium, 4-formyl-1-methylquininoinium, 2-formyl-1-methylquinolinium, 4- (2-formylvinyl) -1-methylquinolium, 4-acetyl-1-methylpyridinium, 2-acetyl-1-methylpyridinium, 4- Acetyl-1-methylquinoline and 4- (2-formyl-vinyl) -1-methylpyridinium, 2,6-dichloro-4-formyl-1-methylpryridinium, 2,6-diphenyl-4-formyl-1-methylpyridinium, 4- Benzoyl-1-methylpyridinium, 4-propionyl-1-methylpyridinium, 4-pyridine idehyde-N-oxide and N-methylpyridoxal,

Isatin or isatin derivatives, such as isatin, isatin-5-sulfonic acid, isatin-4-carboxylic acid and isatin-5-carboxylic acid, N-substituted isatin derivatives, such as N-hydroxymethyl-isatin, N-hydroxyethyl-isatin N- (2- Hydroxypropyl) isatin, N- (3-hydroxypropyl) isatin, N- (2,3-dihydroxypropyl) isatin, N- (2-sulfoethyl) isatin, (3-sulfopropyl) isatin, N-allyl isatin, N -Vinylisatin, N-benzylisatin, N- (4-methoxybenzyl) -isatin, N- (4-carboxybenzyl) -isatin, N- (4-sulfobenzyl) -isatin, N- (2-dimethylaminoethyl) -isatin, N- ( 2

Pyrrolidinoethyl) isatin, N- (2-piperidinoethyl) isatin, (2-morpholinoethyl) isatin, N- (2-furylmethyl) isatin, N- (2-thienylmethyl) isatin, N- (2-pyridylmethyl) -isatin, N- (3-pyridylmethyl) -isatin, N- (4-pyridylmethyl) -isatin, N-allylisatin-5-sulfonic acid, 5-chloro-N- (hydroxyethyl) -isatin, 5-methyl-N- ( hydroxyethyl) isatin, 5-chloroisatin, 5-nitroisatin, 5,7-dichloroisatin, 5,7-dichloro-N-allylisatin, 5-nitro-N-allylisatin, N-hydroxymethyl-5-methylisatin, N-hydroxymethyl-5 -chlorisatin, N-hydroxymethyl-5-sulfoisatin, N-hydroxymethyl-5-carboxyisatin, N-hydroxymethyl-5-nitroisatin, N-hydroxymethyl-5-bromisatin, N-hydroxymethyl-5-methoxyisatin, N-hydroxymethyl-5.7 -dichlorisatin, N-dimethylaminomethylisatin, N-diethylaminomethylisatin, N- (bis- (2-hydroxyethyl) aminomethyl) -isatin, N- (2-hydroxyethylaminomethyl) -isatin, N- (bis- (2-hydroxypropyl) aminomethyl) -isatin, N- (2-pyrrolidino) -isatin, N- (2-piperidino) -isatin, N-pyrrolidinomethylisatin, N-piperidinomethylisatin, N-morpholinomethylisatin, N - (2-morpholinoethyl) isatin, N- (1, 2,4-triazolyl) methylisatin, N- (l-imidazolyl) - methylisatin, N-carboxymethylaminomethylisatin, N- (2-carboxyethylaminomethyl) - isatin, N- (3-carboxypropylaminomethyl) isatin, N- (bis- (2-hydroxyethyl) aminomethyl) -5-methylisatin, N-piperidinomethyl-5-chloroisatin, N- (2-

Sulfoethylamino) isatin, and the alkali and optionally ammonium salts of the acidic compounds, quinisatin and their derivatives, such as N-methylquinisatin and the alkali and ammonium salts of the acidic compounds.

7. The method according to any one of claims 1 to 6, characterized in that the compounds of formula II are selected from glutacondialdehyde, fumaraldehyde, glyoxal, malondialdehyde, amber dialdehyde, mucondialdehyde, 1, 2-naphthoquinone, 4-sulfonic acid-1,2-naphthoquinone , 1,2-benzoquinone, 1,4-benzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone (juglone), 1,4-naphthoquinone, spinulosin, atromentin, aurentioglyocladin, 5-hydroxy-1, 4-naphthoquinone, 2,5-dihydroxy-6-methylbenzoquinone, 2-hydroxy-3-methyl-6-methoxy-1, 4-benzoquinone, 2,5-dihydroxy-3,6-diphenyI-1, 4-benzoquinone, 2,5-dihydroxy-6-isopropyl-1, 4-benzoquinone, 4,5-dimethoxy-1, 2-benzoquinone, 2-hydroxy-1, 4-naphthoquinone, fafioline, 5,8-dihydroxy-1,4- Naphthoquinone, naphthopurpurin, 2-hydroxy-3- (3'-methyl-2'-butenyl) -1, 4-naphthoquinone, plumbagin, 3,5-dihydroxy-2-methyl-1, 4-naphthoquinone, 2-hydroxy- 3-methyl-1,4-naphthoquinone, 3,5-dihydroxy-1,4-naphthoquinone, 2,5-dihydroxy-1,4-naphthoquinone, 2-methoxy-5-hydroxy-1,4-naphtho thoquinone, 3-methoxy-5-hydroxy-1,4-naphthoquinone and 9,10-phenanthrenequinone.

8. The method according to any one of claims 1 to 7, characterized in that the compounds with the formulas I and II, and the compounds of component B in each case in an amount of 0.03 to 65 mmol, in particular from 1 to 40 mmol, based to 100 g of the finished coloring agent used (agent 2).

9. The method according to any one of claims 1 to 8, characterized in that component B is selected from N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, N- (2-hydroxyethyl) -N -ethy! -p-phenylenediamine, N, N-bis- (2-hydroxyethyl) -p-phenylenediamine, N- (2-methoxyethyl) -p-phenylenediamine, 2,3-dichloro-p-phenylenediamine, 2,4- Dichloro-p-phenylene diamine, 2,5-dichloro-p-phenylene diamine, 2-chloro-p-phenylene diamine, 2,5-dihydroxy-4-morpholinoaniline, 2-aminophenoi, 3-aminophenol, 4-aminophenol, 2-aminomethyl 4-aminophenol, 2-hydroxymethyl-4- aminophenol, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,5-diamino toluene, 2,5, -diaminophenol, 2,5-diaminoanisole, 2,5, diaminophenethol, 4-amino-3-methylphenol, 2 - (2,5-diaminophenyl) ethanol, 2,4-diaminophenoxyethanol, 2- (2,5-diaminophenoxy) ethanol, 3-amino-4- (2-hydroxyethyloxy) phenol, 3,4-methylenedioxyphenol, 3,4-methylenedioxyaniline, 3-amino-2,4-dichlorophenol, 4-methylaminophenol, 2-methyl-5-aminophenol, 3-methyl-4-aminophenol, 2-methyl-5- (2-hydroxyethylamino ) phenol, 3-amino-2-chloro-6-methylphenol, 2-methyl-5-amino-4-chlorophenol, 5- (2-hydroxyethylamino) -4-methoxy-2-methylphenol, 4-amino-2-hydroxymethylphenol , 2- (diethylaminomethyl) -4-aminophenol, 4-amino-1-hydroxy-2- (2-hydroxyethylaminomethyl) benzene, 1-hydroxy-2-amino-5-methyl-benzene, 1-hydroxy-2-amino -6-methyl-benzoI, 2-amino-5-acetamido-phenol, 1, 3-dimethyl-2,5-diaminobenzene, 5- (3-hydroxypropylamino-) 2-methylphenol, 5-amino-4-methoxy-2 - methylphenol, N, N-dimethyl-3-aminophenol, N-cyclopentyl-3-aminopheno 1,5-amino-4-fluoro-2-methylphenol, 2,4-diamino-5-fluorotoluene, 2,4-diamino-5- (2-hydroxyethoxy) toluene, 2,4-diamino-5-methylphenetol, 3,5-diamino-2-methoxy-1-methylbenzene, 2-amino-4- (2-hydroxyethylamino) anisole, 2,6-bis (2-hydroxyethylamino) -1-methylbenzene, 1,3-diamino- 2,4-dimethoxybenzene, 3,5-diamino-2-methoxy-toluene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 2-aminophenylacetic acid, 3-aminophenylacetic acid, 4-aminophenylacetic acid, 2,3- Diaminobenzoic acid, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,4-diaminobenzoic acid, 3,5-diaminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 3-amino-4-hydroxy-benzoic acid, 4-amino-3-hydroxy -benzoic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4-hydroxybenzenesulfonic acid, 4-amino-3-hydroxy-naphthalene-1-sulfonic acid, 6-amino-7-hydroxynaphthalene-2-sulfonic acid, 7 -Amino-4-hydroxynaphthalene-2-sulfonic acid, 4-amino-5-hydroxynaphthalene-2,7-disulfo acid, 3-amino-2-naphthoic acid, 3-aminophthalic acid, 5-aminoisophthalic acid, 1, 3,5-triaminobenzene, 1, 2,4-triaminobenzene, 1,2,4,5-tetraaminobenzene, 2,4,5- Triamino-phenol, pentaaminobenzene, hexaaminobenzene, 2,4,6-triaminoresorcinol, 4,5-diamino-catechol, 4,6-diaminopyrogallol, 1- (2-hydroxy-5-aminobenzyl) -2- imidazolidinone, 4-amino- 2 - ((4 - [(5-amino-2-hydroxyphenyl) methyl] piperazinyl) methyl) phenol, 3,5-diamino-4-hydroxycatechol, 1,4-bis (4-aminophenyl) -1.4 -diazacycloheptane, aromatic nitriles, such as 2-amino-4-hydroxybenzonitrile, 4-amino-2-hydroxybenzonitrile, 4-aminobenzonitrile, 2,4-

Diaminobenzonitrile, nitro group-containing amino compounds, such as 3-amino-6- methylamino-2-nitro-pyridine, picramic acid, [8 - [(4-amino-2-nitrophenyl) azo] -7-hydroxy-naphth-2-yl] trimethylammonium chloride, [8 - ((4-amino-3 -nitrophenyl) -azo) -7-hydroxy-naphth-2-yl] -trimethylammonium chloride (Basic Brown 17), 1-hydroxy-2-amino-4,6-dinitrobenzene, 1-amino-2-nitro-4- [ bis- (2-hydroxyethyl) amino] benzene, 1-amino-2 - [(2-hydroxyethyl) amino] -5-nitrobenzoI (HC Yellow No. 5), 1-amino-2-nitro-4- [( 2-hydroxyethyl) amino] benzene (HC Red No. 7), 1-amino-4- (2-hydroxyethylamino) -5-chloro-2-nitrobenzene, 4-amino-2-nitro-diphenylamine (HC Red No. 1), 1 - [(2-Hydroxyethyl) amino] -2-nitro-4-amino-benzene (HC Red No. 3), 4-amino-3-nitrophenol, 4-amino-2-nitrophenol, 6-nitro -o-toluidine, 1-amino-3-methyl-4 - [(2-hydroxyethyl) amino] -6-nitrobenzene (HC Violet No. 1), 1-amino-2-nitro-4 - [(2nd , 3-dihydroxypropyl) amino] -5-chloro-benzene (HC Red No. 10), 2- (4-amino-2-nitroaniIino) - benzoic acid, 6-nitro-2,5-diaminopyridine, 2-amino-6 -chloro-4-nitrophenoi, 1-amino-2- (3-nitrophenylazo) -7-phenylazo-8-naphthol- 3,6-disulfonic acid disodium salt (Acid blue No. 29), 1-amino-2- (2-hydroxy-4-nitrophenylazo) -8-naphthol-3,6-disulfonic acid disodium salt (Palatinchrome green), 1-amino-2 - (3-chloro-2-hydroxy-5-nitro-phenylazo) -8-naphthol-3,6-disu! Fonic acid disodium salt (gallion), 4-amino-4'-nitrostilbene-2,2'-disulfonic acid disodium salt, 2,4-diamino-3 ', 5'-dinitro-2'-hydroxy-5-methyl-azobenzene (Mordant brown 4), 4'-amino-4-nitrodiphenylamine-2-sulfonic acid, 4'-amino-3' -nitrobenzophenone-2-carboxylic acid, 1-amino-4-nitro-2- (2-nitro-benzylidenamino) -benzene, 2- [2- (diethylamino) ethylamino] -5-nitroaniline, 3-amino-4-hydroxy- 5-nitrobenzenesulfonic acid, 3-amino-3'-nitrobiphenyl, 3-amino-4-nitro-acenaphthene, 2-amino-1-nitronaphthalene, 5-amino-6-nitrobenzo-1,3-dioxole, anilines, especially nitro groups containing anilines, such as 4-nitroaniline, 2-nitroaniline, 1,4-diamino-2-nitrobenzene, 1,2-diamino-4-nitrobenzene, 1-amino-2-methyl-6-nitrobenzene, 4-nitro-1, 3-phenylenediamine, 2-nitro-4-amino-1- (2-hydroxyethylamino) benzene , 2-nitro-1-amino-4- [bis- (2-hydroxyethyl) amino] benzene, 4-amino-2-nitrodiphenylamine-2'-carboxylic acid, 1-amino-5-chloro-4- (2nd -hydroyethylamino) -2-nitrobenzene, 4,4'-diaminostilbene and its hydrochloride, 4,4'-diaminostilbene-2,2'-disulfonic acid mono- or -di-Na salt, 4-amino-4'-dimethylaminostilbene and its hydrochloride, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfoxide, 4,4'-diaminodiphenylamine, 4,4'-diaminodiphenylamine-2-sulfonic acid, 4,4'- Diaminobenzophenone, 4,4'-diaminodiphenyl 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, 1,3-bis (4-aminophenylamino) -2-propanol, 1,3-bis [N- (4-aminophenyl) -2-hydroxyethyla- mino] -2-propanol, N, N-bis- [2- (4-aminophenoxy) ethyl] methylamine, N-phenyl-1, 4-phenylenediamine and bis- (5-amino-2-hydroxyphenyl) methane ,

10. The method according to any one of claims 1 to 9, characterized in that component B is selected from nitrogen-containing heterocyclic compounds selected from the group consisting of 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-amino-3-hydroxy -pyridine, 2,6-diamino-pyridine, 2,5-diamino-pyridine, 2- (aminoethylamino) -5-aminopyridine, 2,3-diamino-pyridine, 2-dimethylamino-5-aminopyridine, 2-methylamino -3-amino-6-methoxy-pyridine, 2,3-diamino-6-methoxy-pyridine, 2,6-dimethoxy-3,5-diamino-pyridine, 2,4,5-triamino-pyridine, 2,6 -Dihydroxy-3,4-dimethylpyhdin, N- [2- (2,4-diaminophenyl) aminoethyl] -N- (5-amino-2-pyridyl) amine, N- [2- (4-aminophenyl) aminoethyl] -N- (5-amino-2-pyridyl) amine, 2,4-dihydroxy-5,6-diaminopyrimidine, 4,5,6-triaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy -4,5,6-triaminopyrimidine, 2,4,5,6-tetraaminopyrimidine, 2-methylamino-4,5,6-triaminopyrimidine, 2,4-diaminopyrimidine, 4,5-diaminopyrimidine, 2-amino-4-methoxy - 6-methyl-pyrimidine, 3,5-diam inopyrazole, 3,5-diamino-1,2,4-triazole, 3-aminopyrazole, 3-amino-5-hydroxypyrazole, 1-phenyl-4,5-diaminopyrazole, 1- (2-hydroxyethyl) -4,5- diaminopyrazole, 1-phenyl-3-methyl-4,5-diaminopyrazole, 4-amino-2,3-dimethyl-1-phenyl-3-pyrazolin-5-one (4-aminoantipyrine), 1-phenyl-3-methylpyrazole -5-one, 2-aminoquinoline, 3-aminoquinoline, 8-aminoquinoline, 4-aminoquinoline, 2-aminoonicotinic acid, 6-aminoonicotinic acid, 5-aminoisoquinoline, 5-aminoindazole, 6-aminoindazole, 5-amino benzimidazole, 7-amino benzimidazole, 5 -Aminobenzothiazole, 7-aminobenzothiazole, 2,5-dihydroxy-4-morpholino-aniline and indole and indoline derivatives, such as 4-aminoindole, 5-aminoindole, 6-aminoindole, 7-aminoindole, 5,6-dihydroxyindole, 5 , 6-dihydroxyindoline, 4-hydroxyindoline and hydroxypyrimidines, and the physiologically tolerable salts of these compounds.

11. The method according to any one of claims 1 to 10, characterized in that component B is selected from aromatic hydroxy compounds selected from the group consisting of 2-methylresorcinol, 4-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, resorcinol, 3-methoxyphenol, pyrocatechol, hydroquinone, pyrogallol, phloroglucin, hydroxyhydroquinone, 2-methoxyphenol, 3-methoxyphenol, 4-methoxyphenol, 3-dimethylaminophenol, 2- (2-hydroxyethyl) phenol, 3,4-methylenedioxyphenol, 2,4 Dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 2,4-dihydroxyphenylacetic acid, 3,4-dihydroxy phenylacetic acid, gallic acid, 2,4,6-trihydroxybenzoic acid, 2,4,6-trihydroxyacetophenone, 2-chlororesorcinol, 4-chlororesorcinol, 1-naphthol, 1,5-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,7- Dihydroxynaphthalene, 6-dimethylamino-4-hydroxy-2-naphthalenesulfonic acid and 3,6-dihydroxy-2,7-naphthalenesulfonic acid.

12. The method according to any one of claims 1 to 11, characterized in that component B is selected from amino acids, selected from the group ß-alanine, arginine, histidine, tyrosine, phenylalanine, DOPA (dihydroxyphenylalanine), ornithine, lysine, proline and tryptophan.

13. The method according to any one of claims 1 to 12, characterized in that component B is selected from oligopeptides selected from glutathione or the oligopeptides contained in the hydrolysates of collagen, keratin, casein, elastin, soy protein, wheat gluten or almond protein.

14. The method according to any one of claims 1 to 13, characterized in that component B is selected from CH-acidic compounds, selected from malonic acid, malonic esters and their derivatives and acetoacetic acid, acetoacetic acid esters and their derivatives, pyrazol-5-one, 3- Methyl-pyrazol-5-one, 1-phenyl-3-methyl-pyrazol-5-one, 1- (ß-cyanoethyl) -3-methyl-pyrazol-5-one, 1, 3-dimethyl-pyrazol-5- on, 1- (β-acetoxyethyl) -3-methyl-pyrazol-5-one, 1 - (2'-chlorophenyl) -3-methyl-pyrazol-5-one, 1-phenyl-3-carbomethoxy-pyrazol-5 -on, 1- (3'-aminophenyl-pyrazol-5-one, 1 - (4'-aminophenyl) -pyrazol-5-one, 3-methyl-pyrazol-5-one-1 - carboxamide, 1-phenyl- pyrazol-5-one-3-carboxamides, amino-pyrazole, 1-phenyl-5-amino-pyrazole, 1-benzyl-5-amino-pyrazole, 1-cyclohexyl-5-amino-pyrazole, 1-ethyl-3- methyl-5-amino-pyrazole, 1-benzyl-3-phenyl-5-amino-pyrazole, 1-isopentyl-5-amino-pyrazole, 1-furfuryl-5-amino-pyrazole, 2-methyl-4H-pyrazolo ( 5) - [2,3-a] benzimidazole, [1 - (3'-thia-cyclopentyl) -3-methy1 -pyrazole- 5-one-S-dioxide], 2-methyl-1 H-3,3a, 8-triazacyclopenta [a] indene, barbituric acid, thiobarbituric acid, di-N-ethylthiobarbituric acid, di-N-methylthiobarbituric acid, di-n- butyl barbituric acid, di-isobutyl barbituric acid, di-N-amyl barbituric acid, di-iso-amyl barbituric acid, di-n-hexyl barbituric acid, di-benzyl barbituric acid, di-ß-phenylethyl barbituric acid, Di-cyclohexyl barbituric acid, di-phenyl barbituric acid, di-p-tolyl barbituric acid, di-p-methoxybenzyl barbituric acid, N-methyl-N'-n-butyl barbituric acid, N-methyl-N'-benzyl- barbituric acid, N-methyl-N'- ß-phenylethyl barbituric acid, N-methyl-N'-γ-phenylpropyl barbituric acid, N-methyl-N ¹ - γ-phenylbutyl barbituric acid, N-methyl-N'-α-isobutyl-γ-phenylpropyl barbituric acid, N-methyl-N'-cyclohexyl barbituric acid, N-methyl-N'-phenyl barbituric acid, N-methyl-N '- p-toloyl-barbituric acid, N-methyl-N'-norbomylmethyl-barbituric acid and the corresponding N-ethyl and Nn-butyl derivatives of the above compounds, 2,6-dihydroxy-3-cyano-4-methyl-pyridine, cyanopyridones , Aminonitropyridone and Aminocyanopyhdone, especially N-methyl-3-cyano-4-methyl-6-hydroxy-pyridon-2, N-ethyl-3-cyano-4-methyl-6-hydroxy-pyridon-2, N-ß- Methoxyethyl-3-cyano-4-methyl-6-hydroxy-pyridin-2-one, 2,6-dihydroxy-3-cyano-4-methyl-pyridine, N-β-hydroxyethyl-3-cyano-4-methyl 6-hydroxy-pyridin-2-one, N-butyl-3-cyano-4-methyl-6-hydroxy-pyridin-2-one and N-phenyl-3-cyano-4-methyl-6-hydroxy-pyridine 2-one, from 6-hydroxy-benzofuran (2H) -one, 3-indoxy acetate, imidazo [1.2-a] pyridin-2-one, 6-bromo-imidazo [1.2-a)] pyridin-2-one, 2,4-dihydroxyquinoline, 1,3-indanedione, rhodanine, rhodanine-3-acetic acid, 4-imino-4,5-d ihydro-thiazol-2-ylamine, 1, 2-

Diphenyldioxopyrazole, 2-phenyl-3,5-dihydro-imidazol-4-one, 3-methyl-2-p-toloyl-3,5-dihydro-imidazol-4-one, phenyldihydrobytyrolactone, 1, 1-dioxo-1, 2-dihydro-11, 6-benzo [b] -thiophene-3-one, 1-dicyanomethylene indane, 1,3-bis (dicyanomethylene) indane, 2- (l'.l'-dioxo-l '^' - dihydro -H'.δ'-benzoIbHhiophen-S'-ylidenJ-malononitrile, 2,4-

Diamino-6-hydroxypyrimidine, 2,6-diamino-4-hydroxypyrimidine, 4-amino-2,6-dihydroxypyrimidine, 4-amino-6-hydroxy-2-suIfanylpyhmidin, 2-amino-4,6-dihydroxypyrimidine, 4, 6-dihydroxy-1-mercaptopyrimidine, 2,4,6-trihydroxypyrimidine, 1, 2-dimethylnaphtho [1, 2-d] thiazolium p-toluenesulfonate, 2,3-dimethylbenzothiazolium iodide, 2,3-dimethylbenzothiazoiumium p-toluenesulfonate, 1-ethyl-2-methyl-naphtho [1, 2-d] thiazolium p-toluenesulfonate, 1, 2,3,3-tetramethyl-3-H-indolium iodide, 1, 2,3,3- Tetramethyl-3H-indolium-p-toluenesulfonate, 1, 4-

Dimethylquinolinium iodide, 1-methyl-2-quinaldinium iodide, 1-ethyl-2-quinaldinium iodide, 1,3,3-trimethyl-2-methyienindoline, 1- (2-hydroxyethyl) -3,3-dimethylI-2-methylene- indoline and 3-ethyl-2-methylenebenzothiazoline.

15. The method according to any one of claims 1 to 14, characterized in that component B is selected from quaternary ammonium compounds selected from tetramethyl, tetraethyl, tetrapropyl, tetrabutyl, benzyltrimethylammonium chloride, bromide, iodide, hydrogen sulfate, 0.5 sulfate and the quaternized hydroxyethyl cellulose derivatives (INCI name: Polyquaternium 10).

16. The method according to any one of claims 1 to 15, characterized in that component B is selected from the group consisting of N- (2-hydroxyethyl) -N-ethyl-p-phenylenediamine, 2-chloro-p-phenylenediamine, N , N-bis- (2-hydroxyethyl) -p-phenylenediamine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-amino-6-chloro-4-nitrophenol, 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 -dichlorophenol, 2-methyl-5-aminophenol, 3-methyl-4-aminophenol, 2-methyl-5- (2-hydroxyethylamino) phenol, 2-methyl-5-amino-4-chlorophenol, 6-methyl-3- amino-2-chlorophenol, 2-aminomethyl-4-aminophenol, 2-diethylaminomethyl-4-aminophenol, 2-dimethylaminomethyl-4-aminophenol, 2,6-dichloro-4-aminophenol, 2-hydroxymethyl-4-aminophenol, 2, 6-bis (2-hydroxyethylamino) -1-methylbenzene, bis (2-hydroxy-5-aminophenyl) methane, bis (4,5-amino-2-hydroxyphenyl) methane, 1, 3-bis (2, 4-diaminophenoxy) propa n, 1,4-bis (4-aminophenyl) -1,4-diazacycloheptane, 1,8-bis (2,5-diaminophenoxy) -3,6-dioxaoctane, 4,4'-diaminodiphenylamine, 3,4-methylenedioxyphenol , 3,4-diamino benzoic acid, 2,5-diaminopyhdine, 2-D | methylamino-5-aminopyridine, 2-amino-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine, 2,3-diamino -6-methoxypyridine, 3,5-diamino-2,6-dimethoxypyridine, 2,6-dihydroxy-3,4-dimethylpyridine, 2-hydroxy-4,5,6-thaminopyrimidine, 4-hydroxy-2,5 , 6-triaminopyrimidine, 2,4,5,6-tetraaminopyrimidine, 2-methylamino-4,5,6-triamino-pyrimidine, 3,5-diaminopyrazole, 3-amino-5-hydroxypyrazole, 4,5-diamino -1 - (2-hydroxyethyl) pyrazole, 5,6-dihydroxyindole, 5,6-dihydroxyindoline, 4-amino-2,3-dimethyl-1-phenyl-3-pyrazolin-5- one (4-aminoantipyrine), 2,3-dimethylbenzothiazolium p-toluenesulfonate, 1,2,3,3-tetramethyl-3H-indolinium p-toluenesulfonate, thiobarbituric acid, rhodanine, 2,3-dimethyl-benzothiazolium p-toluenesulfonate, 1, 2-dimethyl naphtho [1,2-d] thiazolium p-toluenesulfonate, 1-methyl-2-quinaldinium p-toluene olsulfonate, 1, 4-dimethylquinolinium p-toluenesulfonate, ß-alanine, L-proline, L-lysine, DL-tyrosine and their physiologically tolerable salts preferably formed with inorganic acids.

17. The method according to any one of claims 1 to 16, characterized in that further color enhancer selected from the group consisting of piperidine, piperidine-2-carboxylic acid, piperidine-3-carboxylic acid, piperidine-4-carboxylic acid, pyridine, 2-hydroxypyridine, 3rd Hydroxypyridine, 4-hydroxypyridine, imidazole, 1-methylimidazole, arginine, histidine, pyrrolidine, proline, pyrrolidone, pyrrolidone-5-carboxylic acid, pyrazole, 1, 2,4-triazole, piperazine, methoxybutanol, propylene carbonate, ethylene carbonate or any mixtures thereof.

18. The method according to any one of claims 1 to 17, characterized in that substantive 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 (Means 2) can be used.

19. The method according to any one of claims 1 to 18, characterized in that anionic, zwitterionic and / or nonionic surfactants are used in agent 1 and / or agent 2.

20. The method according to any one of claims 1 to 19, characterized in that ammonium or metal salts selected from the group of formates, carbonates, halides, sulfates, butyrates, valerates, capronates, acetates, lactates, glycolates, tartrates, citrates, gluconates, Propionates, phosphates and phosphonates of alkali metals, such as potassium, sodium or lithium, alkaline earth metals, such as magnesium, calcium, strontium or barium, or of aluminum, manganese, iron, cobalt, copper or zinc, can be used.