DE10361276A1 - Use of manganese oxidase enzyme for oxidation dyeing of keratinic fibers, especially human hair - Google Patents

Abstract

Manganese oxidase enzyme is used for oxidation dyeing of keratinic fibers. Independent claims are also included for: (1) composition for dyeing keratinic fibers, comprising a dye precursor, a manganese oxidase enzyme and a compound containing manganese ions; and (2) dyeing keratinic fibers by applying the composition, allowing it to act and then rinsing it off.

Description

The The present invention relates to agents for dyeing keratin fibers, which contain at least one enzyme of the manganese oxidase type corresponding procedure for dyeing keratin fibers and the use of an enzyme of the type Manganese oxidases for oxidative hair coloring.

Human Hair is becoming more diverse today Treated with hair cosmetic preparations. These include, for example cleaning the hair with shampoos, care and regeneration with douches and cures as well as bleaching, dyeing and shaping the hair with colorants, Tints, Corrugating agents and styling preparations. Thereby, means to change play or nuance of the color of the scalp hair plays a prominent role.

For temporary stains are common dyeing or tinting agents used that as a coloring Component so-called direct pull included. This is what it is about are dye molecules, which pull directly on the hair and no oxidative process for training need the color. One of these dyes for example that from antiquity for coloring body and hair known henna. These colors are against shampooing usually significantly more sensitive than the oxidative stains, so that a much undesirable shift in nuances is achieved much more quickly or even a visible "discoloration" occurs.

For permanent, intense colors So-called oxidation dyes are used with appropriate fastness properties used. Such colorants usually contain Oxidation dye precursors, so-called developer components and coupler components. The developer components form under the influence of oxidizing agents or of atmospheric oxygen among themselves or the actual ones under coupling with one or more coupler components Dyes. The oxidation colorants are characterized by excellent, long-lasting dyeing results out. For Naturally effective colorings usually has to Mix of a larger number of oxidation dye precursors are used; in many make direct dyes are still used for shading.

The oxidative color development can basically done with atmospheric oxygen. However, a chemical one is preferred Oxidizing agents used. Persulfates come as oxidizing agents, Chlorites and especially hydrogen peroxide or its addition products of urea, melamine and sodium borate in question. Usually becomes a 2-9% aqueous hydrogen peroxide solution used. Under the influence of such high concentrations of oxidizing agents can the keratin fibers, especially if they are already permanently waved or are bleached become, and in rare cases can these high concentrations also cause skin irritation.

On essential solution this problem arises from the reduction of the oxidizing agent concentration out. In the past, it was therefore used on the one hand for dye precursors wanted, due to their chemical structure already by lower Amounts of hydrogen peroxide or oxidized by atmospheric oxygen can. On the other hand, the use of enzymes as biocatalysts suggested that the desired Oxidation process with very little or no hydrogen peroxide can only catalyze in the presence of atmospheric oxygen.

In the German patent application DE-OS-21 55 390 describes an enzyme-activated, oxidative hair coloring process in which small amounts of H ₂ O _{2 are used} in combination with a peroxidase. Also in the EP-A1-0 310 675 enzymatic hair treatment agents are disclosed which contain at least one two-electron reducing oxidase which uses oxygen as an acceptor. In the EP-B1-0 548 620 enzymatic hair dyes are described in which the oxidation of the dye precursors is catalyzed by using a peroxidase. Finally, in the EP-A2-0 795 313 enzymatic hair colorants are described which contain an oxygen-oxidoreductase / substrate system and a peroxidase and, as coupler components, an m-phenylenediamine derivative. However, all of these dyes cannot yet be completely convincing with regard to the dyeing performance that can be achieved (intensity, shade, gloss, fastness properties).

The technique of easily oxidizable dye precursors, like the enzymatic color development described so far, has the disadvantage that compared to the conventional processes, in particular with regard to the intensity, the gloss and the fastness properties of the dyeings, poorer results be achieved.

The The present invention is therefore based on the task of coloring agents for keratin Fibers available to provide a gentle fiber treatment while ensuring excellent dyeing performance.

• (a) mindestens ein Farbstoffvorprodukt,
• (b) mindestens ein Enzym vom Typ der Manganoxidasen sowie
• (c) mindestens eine Verbindung, die Mn-Ionen enthält,

enthalten.A first object of the present invention are therefore agents for dyeing keratin fibers in a cosmetically acceptable carrier

• (a) at least one dye precursor,
• (b) at least one enzyme of the manganese oxidase type and
• (c) at least one compound containing Mn ions,

contain.

Under the term "keratinic Fibers "are included furs according to the invention, To understand wool, feathers and especially human hair.

According to the invention, the term “manganese oxidases” means those oxidases which directly oxidize manganese or manganese ions and transfer the electrons obtained in the process to oxygen. Those manganese oxidases which can oxidize Mn ²⁺ cations to Mn ³⁺ cations are preferred according to the invention. Furthermore, the manganese oxidases can be preferred which contain copper ions as reactive centers. Examples of manganese oxidases according to the invention are the enzymes obtained from Leptothrix discophora and Bacillus SG-1, the coding genes of which have already been cloned and sequenced (Corstjens et al. (1997) Geomicrobiol. Journal, Vol. 14, p. 91-108 and van Waasbergen et al. (1996) Journal of Bacteriology, vol. 178 (12), p. 3517-3530). Both genes code for proteins which contain the copper-binding sequence motifs known from "blue copper" oxidases and whose manganese oxidase activity is increased by adding copper.

The enzymes according to the invention can be obtained, for example, from known microorganisms. For example, they are caused by the microorganisms Leptothrix discophora, Bacillus SG-1 and Pseudomonas sp. (Nealson et al. (1989) Beveridge & Doyle (eds.) Metal ions and bacteria, John wiley and sons, Inc., New York, p: 383-411) educated. Can continue for example in microorganisms in which the manganese oxidase is stored in the spore, such as Bacillus SG-1, the isolated spores are also used according to the invention as an enzyme source become.

to Obtaining the enzyme must the respective microorganisms under the conditions under which they form manganese oxidases. As manganese oxidases can mechanically according to the invention, enzymatically or chemically digested cell preparations of the complete manganese oxidase-containing Microorganisms are used. However, it is also possible to contain manganese oxidase Culture supernatants or to use isolated manganese oxidases.

It can manganese oxidases can also be used, which are produced using recombinant production processes were. Recombinant production processes include everyone To understand processes in which the coding for manganese oxidases Genes from the natural Producers are isolated and then converted into suitable ones using known methods Production strains which are also the original enzyme producers can have been introduced.

Regarding the conditions under which manganese oxidase can be obtained at this point explicitly on the explanations in the international Laid-open publication WO-A1-00 / 52257, to which hereby explicitly Reference is made.

According to the invention manganese oxidases with a molecular weight above 130 kDalton as proven preferred. The manganese oxidases are particularly preferred with a molecular weight of 170 to 190 kDalton.

In the colorants of the invention the enzyme is preferably used in an amount of 0.0001mg and 500mg active manganese oxidase used per 100g application preparation. An amount of 0.1 mg to 50 mg active manganese oxidase per 100 g application preparation is particularly preferred.

The Manganese oxidase is preferably in granular form, as a solution, as Suspension or with a carrier material in the coloring cream brought in. The manganese oxidase is particularly preferred in the form a suspension containing between 0.5 and 50 weight percent enzyme contains in a nonionic detergent, in the coloring cream brought in. The manganese oxidase is particularly preferred in one Suspension containing between 1 and 5 wt .-% enzyme in a nonionic Contains detergent, used. As a particularly preferred nonionic detergents have sorbitan fatty acid esters and adducts of ethylene oxide with sorbitan fatty acid esters such as the polysorbates. A particularly preferred one Nonionic detergent is for example under the trade name Tween 20 (INCI name: Polysorbate 20) from Uniqema distributed. Aqueous enzyme solutions are also particularly preferred a surfactant content of 1 to 5% by weight.

The Enzyme preparation preferably has a pH between 6.5 and 10.5, especially between 6.5 and 8. In a preferred one embodiment becomes the pH the enzyme preparation with the help of a buffer system. Preferred according to the invention Buffer systems are, for example, the Tris / HCl buffer (approx. PH 6.5), the sodium phosphate buffer (suitable up to about pH 8.5) and a HEPES buffer (4- (2-hydroxyethyl) piperazine-1-ethanesulfonic acid; for example for sale at Sigma; pH range approximately from 6.8 to 8.2). Buffer systems have been particularly suitable with a molarity proven from 50 to 150mM. In the case of the HEPES buffer, the molarity is 10mM particularly preferred.

The agents according to the invention contain as component (c) at least one compound, the manganese ions contains. According to the invention, these compounds serve as mediators for the manganese oxidases. Although the reaction mechanism has not yet been fully clarified, according to the invention following mechanism is assumed, without the invention on this limited shall be.

The Mediator, (the manganese ion in the oxidized form) takes one (or several) electrons) from the dye precursor to be oxidized on. This oxidizes the dye precursor and the manganese ion itself reduced. The manganese ion in its reduced form is from the Manganese oxidase is oxidized again to its initial oxidation state. The manganese oxidase serves as an oxidizing agent and atmospheric oxygen thus as a terminal electron acceptor.

in principle can Manganese ions are used in any oxidation state become. According to the invention particularly however, manganese ions with oxidation states +2 or +3 proven.

manganese oxidation level +2 is preferred in the form of its simple salts used. As special according to the invention sulfate, chloride, carbonate, phosphate, the acetate and lactate of manganese (II) proved. Manganese (II) sulfate or manganese (II) chloride are very particularly preferred according to the invention Manganese compounds with the oxidation state +2.

manganese Oxidation level +3 is preferably used in the form of soluble manganese complexes. Preferred according to the invention examples for such manganese complexes are manganese / formate, manganese / lactate, manganese / oxalate, Manganese / lactate and manganese / mannolate.

The manganese ions of oxidation levels +2 or +3 can also be generated in situ from manganese ions of other oxidation levels, such as Mn ^{4 +} or Mn ⁷⁺ .

On the most preferred mediator is the manganese ion of the oxidation state +2.

The Mediators are preferred according to the invention used in such amounts that the resulting application preparation has a manganese ion concentration of 0.005 mM to 50 mM. Manganese ion concentrations from 0.05 mM to 5 mM, in particular from 0.1 mM and 1 mM, are special according to the invention prefers.

In a preferred embodiment of the present invention, the colorant further contains at least one complexing agent for the manganese ion. Compounds which can complex and thus stabilize Mn ³⁺ cations are preferably suitable as complexing agents.

preferred According to the invention, complexing agents are, for example, formate anion, the lactate anion, the malonate anion or the oxalate anion. Another more preferred according to the invention The complexing agent is ethylenediaminetetraacetic acid (EDTA).

The Complexing agents mentioned are preferably in a concentration from 1 mM to 500 mM, particularly preferably from 5 mM to 100 mM, whole used particularly preferably from 10 mM to 50 mM.

• – Oxidationsfarbstoffvorprodukte vom Entwickler- und/oder Kuppler-Typ, und
• – Vorstufen naturanaloger Farbstoffe, wie Indol- und Indolin-Derivate,

sowie Mischungen von Vertretern dieser Gruppen enthalten.With regard to the further dye precursors which can be used in the colorants according to the invention, the present invention is not subject to any restrictions. The colorants according to the invention can be used as dye precursors

• - Oxidation dye precursors of the developer and / or coupler type, and
• Precursors of nature-analogous dyes, such as indole and indoline derivatives,

as well as mixtures of representatives of these groups.

As Developer components are commonly used primary aromatic amines with another, in para or ortho position located, free or substituted hydroxyl or amino group, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazole derivatives and 2,4,5,6-tetraaminopyrimidine and its derivatives used.

wobei

• – G¹ steht für ein Wasserstoffatom, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen (C₁- bis C₄)-Alkoxy- (C₁- bis C₄)-alkylrest, einen 4'-Aminophenylrest oder einen C₁- bis C₄-Alkylrest, der mit einer stickstoffhaltigen Gruppe, einem Phenyl- oder einem 4'-Aminophenylrest substituiert ist;
• – G² steht für ein Wasserstoffatom, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen (C₁- bis C₄)-Alkoxy- (C₁- bis C₄)-alkylrest oder einen C₁- bis C₄-Alkylrest, der mit einer stickstoffhaltigen Gruppe substituiert ist;
• – G³ steht für ein Wasserstoffatom, ein Halogenatom, wie ein Chlor-, Brom-, Iod- oder Fluoratom, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen C₁- bis C₄-Hydroxyalkoxyrest, einen C₁- bis C₄-Acetylaminoalkoxyrest, einen C₁- bis C₄- Mesylaminoalkoxyrest oder einen C₁- bis C₄-Carbamoylaminoalkoxyrest;
• – G⁴ steht für ein Wasserstoffatom, ein Halogenatom oder einen C₁- bis C₄-Alkylrest oder
• – wenn G³ und G⁴ in ortho-Stellung zueinander stehen, können sie gemeinsam eine verbrückende α,ω-Alkylendioxogruppe, wie beispielsweise eine Ethylendioxygruppe bilden.

It can be preferred according to the invention to use a p-phenylenediamine derivative or one of its physiologically tolerable salts as developer component. P-Phenylenediamine derivatives of the formula (E1) are particularly preferred

in which

• G ¹ represents a hydrogen atom, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a (C ₁ to C ₄ ) alkoxy radical (C ₁ to C ₄ ) alkyl, a 4'-aminophenyl group or a C ₁ to C ₄ alkyl group which is substituted by a nitrogen-containing group, a phenyl or a 4'-aminophenyl group;
• G ² represents a hydrogen atom, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a (C ₁ to C ₄ ) alkoxy radical (C ₁ - to C ₄ ) -alkyl radical or a C ₁ - to C ₄ -alkyl radical which is substituted by a nitrogen-containing group;
• G ³ represents a hydrogen atom, a halogen atom, such as a chlorine, bromine, iodine or fluorine atom, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C _4- polyhydroxyalkyl, a C ₁ to C ₄ hydroxyalkoxy, a C ₁ to C ₄ acetylaminoalkoxy, a C ₁ to C ₄ mesylaminoalkoxy or a C ₁ to C ₄ carbamoylaminoalkoxy;
• - G ⁴ represents a hydrogen atom, a halogen atom or a C ₁ - to C ₄ -alkyl radical or
• - If G ³ and G ⁴ are ortho to each other, they can together form a bridging α, ω-alkylenedioxo group, such as an ethylenedioxy group.

Examples of the C ₁ to C ₄ alkyl radicals mentioned as substituents in the compounds according to the invention are the groups methyl, ethyl, propyl, isopropyl and butyl. Ethyl and methyl are preferred alkyl radicals. C ₁ to C ₄ alkoxy radicals preferred according to the invention are, for example, a methoxy or an ethoxy group. Further preferred examples of a C ₁ to C ₄ hydroxyalkyl group are a hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group. A 2-hydroxyethyl group is particularly preferred. A particularly preferred C ₂ - to C ₄ -polyhydroxyalkyl group is the 1,2-dihydroxyethyl group. Examples of halogen atoms according to the invention are F, Cl or Br atoms, Cl atoms are very particularly preferred. According to the invention, the other terms used are derived from the definitions given here. Examples of nitrogen-containing groups of the formula (E1) are in particular the amino groups, C ₁ - to C ₄ -monoalkylamino groups, C ₁ - to C ₄ -dialkylamino groups, C ₁ - to C ₄ -trialkylammonium groups, C ₁ - to C ₄ -monohydroxyalkylamino groups, Imidazolinium and ammonium.

Particularly preferred p-phenylenediamines of the formula (E1) are selected from p-phenylenediamine, p-toluenediamine, 2-chloro-p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2 , 6-diethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, N, N-dipropyl-p-phenylenediamine, 4 -Amino-3-methyl- (N, N-diethyl) aniline, N, N-bis- (β-hydroxyethyl) -p-phenylenediamine, 4-N, N-bis- (β-hydroxyethyl) -amino-2 -methylanilin, 4-N, N-bis- (β-hydroxyethyl) amino-2-chloroaniline, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- (α, β-dihydroxyethyl) -p-phenylenediamine, 2-fluoro p-phenylenediamine, 2-isopropyl-p-phenylenediamine, N- (β-hydroxypropyl) -p-phenylenediamine, 2-hydroxymethyl-p-phenylenediamine, N, N-dimethyl-3-methyl-p-phenylenediamine, N, N- (Ethyl, β-hydroxyethyl) -p-phenylenediamine, N- (β, γ-dihydroxypropyl) -p-phenylenediamine, N- (4'-aminophenyl) -p-phenylenediamine, N-phenyl-p-phenylenediamine, 2- ( β-Hydroxyethyloxy) -p-phenylenediamine, 2- (β-acetylaminoethyloxy) -p-phenylenediamine, N- (β-methoxyethyl) -p-phenylenediamine and 5,8-diaminobenzo-1,4-dioxane and their physiologically acceptable salts.

According to the invention very particularly preferred p-phenylenediamine derivatives of the formula (E1) are p-phenylenediamine, p-toluenediamine, 2 - ((3-hydroxyethyl) -p-phenylenediamine, 2- (α, β-dihydroxyethyl) -p-phenylenediamine and N, N-bis (β-hydroxyethyl) -p-phenylenediamine.

It can continue according to the invention be preferred to use compounds as developer components, that contain at least two aromatic nuclei that are and / or hydroxyl groups are substituted.

wobei:

• – Z¹ und Z² stehen unabhängig voneinander für einen Hydroxyl- oder NH₂-Rest, der gegebenenfalls durch einen C₁- bis C₄-Alkylrest, durch einen C₁- bis C₄-Hydroxyalkylrest und/oder durch eine Verbrückung Y substituiert ist oder der gegebenenfalls Teil eines verbrückenden Ringsystems ist,
• – die Verbrückung Y steht für eine Alkylengruppe mit 1 bis 14 Kohlenstoffatomen, wie beispielsweise eine lineare oder verzweigte Alkylenkette oder einen Alkylenring, die von einer oder mehreren stickstoffhaltigen Gruppen und/oder einem oder mehreren Heteroatomen wie Sauerstoff-, Schwefel- oder Stickstoffatomen unterbrochen oder beendet sein kann und eventuell durch einen oder mehrere Hydroxyl- oder C₁- bis C₈-Alkoxyreste substituiert sein kann, oder eine direkte Bindung,
• – G⁵ und G⁶ stehen unabhängig voneinander für ein Wasserstoff- oder Halogenatom, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen C₁- bis C₄-Aminoalkylrest oder eine direkte Verbindung zur Verbrückung Y,
• – G⁷, G⁸, G⁹, G¹⁰, G¹¹ und G¹² stehen unabhängig voneinander für ein Wasserstoffatom, eine direkte Bindung zur Verbrückung Y oder einen C₁- bis C₄-Alkylrest, mit den Maßgaben, dass
• – die Verbindungen der Formel (E2) nur eine Verbrückung Y pro Molekül enthalten und
• – die Verbindungen der Formel (E2) mindestens eine Aminogruppe enthalten, die mindestens ein Wasserstoffatom trägt.

Among the binuclear developer components which can be used in the coloring compositions according to the invention, one can name in particular the compounds which correspond to the following formula (E2) and their physiologically tolerable salts:

in which:

• Z ¹ and Z ² independently of one another represent a hydroxyl or NH ₂ radical which is optionally substituted by a C ₁ to C ₄ alkyl radical, by a C ₁ to C ₄ hydroxyalkyl radical and / or by a bridging Y. is or is possibly part of a bridging ring system,
• - The bridge Y stands for an alkylene group with 1 to 14 carbon atoms, such as a linear or branched alkylene chain or an alkylene ring which is interrupted or terminated by one or more nitrogen-containing groups and / or one or more heteroatoms such as oxygen, sulfur or nitrogen atoms and may be substituted by one or more hydroxyl or C ₁ to C ₈ alkoxy radicals, or a direct bond,
• G ⁵ and G ⁶ independently of one another represent a hydrogen or halogen atom, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a C ₁ to C ₄ aminoalkyl radical or a direct connection to the bridge Y,
• - G ⁷ , G ⁸ , G ⁹ , G ¹⁰ , G ¹¹ and G ¹² independently of one another represent a hydrogen atom, a direct bond to the bridge Y or a C ₁ - to C ₄ -alkyl radical, with the provisos that
• - The compounds of formula (E2) contain only one bridging Y per molecule and
• - The compounds of formula (E2) contain at least one amino group which carries at least one hydrogen atom.

The Substituents used in formula (E2) are analogous according to the invention to the above statements Are defined.

Preferred dinuclear developer components of the formula (E2) are in particular:
N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diamino-propan-2-ol, N, N'-bis (β-hydroxyethyl ) -N, N'-bis (4'-aminophenyl) ethylenediamine, N, N'-bis (4-aminophenyl) tetramethylene diamine, N, N'-bis (β-hydroxyethyl) -N, N ' bis (4-aminophenyl) tetramethylene diamine, N, N'-bis (4-methylaminophenyl) tetramethylene diamine, N, N'-diethyl-N, N'-bis (4'-amino-3 ' -methylphenyl) -ethylenediamine, bis- (2-hydroxy-5-aminophenyl) -methane, 1,3-bis- (2,5-diaminophenoxy) -propan-2-ol, N, N'-bis- (4 ' -aminophenyl) -1,4-diazacycloheptane, N, N'-bis (2-hydroxy-5-aminobenzyl) piperazine, N- (4'-aminophenyl) -p-phenylenediamine and 1,10-bis- (2nd ', 5'-dia minophenyl) -1,4,7,10-tetraoxadecane and its physiologically tolerable salts.

All particularly preferred binuclear developer components of the formula (E2) are N, N'-bis- (β-hydroxyethyl) -N, N'-bis- (4'-aminophenyl) -1,3-diamino-propan-2-ol, Bis- (2-hydroxy-5-aminophenyl) methane, 1,3-bis (2,5-diaminophenoxy) propan-2-ol, N, N'-bis (4'-aminophenyl) -1,4-diazacycloheptane and 1,10-bis (2 ', 5'-diaminophenyl) -1,4,7,10-tetraoxadecane or one of their physiologically tolerable Salts.

wobei:

• – G¹³ steht für ein Wasserstoffatom, ein Halogenatom, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen (C₁- bis C₄)-Alkoxy-(C₁- bis C₄)-alkylrest, einen C₁- bis C₄-Aminoalkylrest, einen Hydroxy-(C₁- bis C₄)-alkylaminorest, einen C₁- bis C₄-Hydroxyalkoxyrest, einen C₁- bis C₄-Hydroxyalkyl- (C₁- bis C₄)-aminoalkylrest oder einen (Di-C₁- bis C₄-Alkylamino)-(C₁- bis C₄)-alkylrest, und
• – G^{1 4} steht für ein Wasserstoff- oder Halogenatom, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen (C₁- bis C₄)-Alkoxy-(C₁- bis C₄)-alkylrest, einen C₁- bis C₄-Aminoalkylrest oder einen C₁- bis C₄-Cyanoalkylrest,
• – G^{1 5} steht für Wasserstoff, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen Phenylrest oder einen Benzylrest, und
• – G^{1 6} steht für Wasserstoff oder ein Halogenatom.

Furthermore, it can be preferred according to the invention to use a p-aminophenol derivative or one of its physiologically tolerable salts as developer component. P-Aminophenol derivatives of the formula (E3) are particularly preferred

in which:

• G ¹³ represents a hydrogen atom, a halogen atom, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a (C ₁ to C ₄ ) Alkoxy- (C ₁ - to C ₄ ) -alkyl radical, a C ₁ - to C ₄ -aminoalkyl radical, a hydroxy- (C ₁ - to C ₄ ) -alkylamino radical, a C ₁ - to C ₄ -hydroxyalkoxy radical, a C ₁ - to C ₄ -hydroxyalkyl- (C ₁ - to C ₄ ) -aminoalkyl or a (di-C ₁ - to C ₄ -alkylamino) - (C ₁ - to C ₄ ) -alkyl radical, and
• G ^{1 4} represents a hydrogen or halogen atom, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a (C ₁ to C ₄ ) Alkoxy- (C ₁ - to C ₄ ) -alkyl radical, a C ₁ - to C ₄ -aminoalkyl radical or a C ₁ - to C ₄ -cyanoalkyl radical,
• G ^{1 5} represents hydrogen, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a phenyl radical or a benzyl radical, and
• - G ^{1 6} represents hydrogen or a halogen atom.

The Substituents used in formula (E3) are analogous according to the invention to the above statements Are defined.

preferred p-aminophenols of the formula (E3) are in particular p-aminophenol, N-methyl-p-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 2-hydroxymethylamino-4-aminophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2- (β-hydroxyethoxy) phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (β-hydroxyethyl-aminomethyl) phenol, 4-amino-2- (α, β-dihydroxyethyl) phenol, 4-amino-2-fluorophenol, 4-amino-2-chlorophenol, 4-amino-2,6-dichlorophenol, 4-amino-2- (diethylaminomethyl) phenol as well as their physiologically tolerable Salts.

All particularly preferred compounds of the formula (E3) are p-aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (α, β-dihydroxyethyl) phenol and 4-amino-2- (diethyl-aminomethyl) phenol.

Further the developer component can be selected from o-aminophenol and its derivatives, such as 2-amino-4-methylphenol, 2-amino-5-methylphenol or 2-amino-4-chlorophenol.

Farther the developer component can be selected from heterocyclic Developer components, such as the pyridine, pyrimidine, Pyrazole, pyrazole-pyrimidine derivatives and their physiologically tolerable Salt.

Preferred pyridine derivatives are in particular the compounds described in the patents GB 1 026 978 and GB 1 153 196 are described, such as 2,5-diamino-pyridine, 2- (4'-methoxyphenyl) amino-3-amino-pyridine, 2,3-diamino-6-methoxy-pyridine, 2- (β-methoxyethyl) amino -3-amino-6-methoxy-pyridine and 3,4-diamino-pyridine.

Preferred pyrimidine derivatives are in particular the compounds described in the German patent DE 2 359 399 , the Japanese laid-open patent JP 02019576 A2 or in the published patent application WO 96/15765 be described, such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2-dimethylamino-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6-triaminopyrimidine.

Preferred pyrazole derivatives are in particular the compounds described in the patents DE 3 843 892 . DE 4 133 957 and patent applications WO 94/08969, WO 94/08970, EP-740 931 and DE 195 43 988 are described, such as 4,5-diamino-1-methylpyrazole, 4,5-diamino-1- (β-hydroxyethyl) pyrazole, 3,4-diaminopyrazole, 4,5-diamino-1- (4'-chlorobenzyl) -pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3 -dimethyl-5-hydrazinopyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1-methylpyrazole, 4,5-diamino-1-tert-butyl -3-methylpyrazole, 4,5-diamino-1- (β-hydroxyethyl) -3-methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-3- ( 4'-methoxyphenyl) pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-1-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4,5-diamino-3-methyl-1-isopropylpyrazole, 4-amino-5- (β-aminoethyl) amino-1,3-dimethylpyrazole, 3,4,5-triaminopyrazole, 1-methyl-3,4, 5-triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole and 3,5-diamino-4- (β-hydroxyethyl) amino-1-methylpyrazole.

wobei:

• – G¹⁷, G¹⁸, G¹⁹ und G²⁰ unabhängig voneinander stehen für ein Wasserstoffatom, einen C₁- bis C₄-Alkylrest, einen Aryl-Rest, einen C₁- bis C₄-Hydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest einen (C₁- bis C₄)-Alkoxy-(C₁- bis C₄)-alkylrest, einen C₁- bis C₄-Aminoalkylrest, der gegebenenfalls durch ein Acetyl-Ureid- oder einen Sulfonyl-Rest geschützt sein kann, einen (C₁- bis C₄)-Alkylamino-(C₁- bis C₄)-alkylrest, einen Di-[(C₁- bis C₄)-alkyl]-(C₁- bis C₄)-aminoalkylrest, wobei die Dialkyl-Reste gegebenenfalls einen Kohlenstoffzyklus oder einen Heterozyklus mit 5 oder 6 Kettengliedern bilden, einen C₁- bis C₄-Hydroxyalkyl- oder einen Di-(C₁- bis C₄)-[Hydroxyalkyl]-(C₁- bis C₄)-aminoalkylrest,
• – die X-Reste stehen unabhängig voneinander für ein Wasserstoffatom, einen C₁- bis C₄-Alkylrest, einen Aryl-Rest, einen C₁- bis C₄-Hydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen C₁- bis C₄-Aminoalkylrest, einen (C₁- bis C₄)-Alkylamino-(C₁- bis C₄)-alkylrest, einen Di-[(C₁- bis C₄)alkyl]- (C₁- bis C₄)-aminoalkylrest, wobei die Dialkyl-Reste gegebenenfalls einen Kohlenstoffzyklus oder einen Heterozyklus mit 5 oder 6 Kettengliedern bilden, einen C₁- bis C₄-Hydroxyalkyl- oder einen Di-(C₁- bis C₄-hydroxyalkyl)-aminoalkylrest, einen Aminorest, einen C₁- bis C₄-Alkyl- oder Di-(C₁- bis C₄-hydroxyalkyl)-aminorest, ein Halogenatom, eine Carboxylsäuregruppe oder eine Sulfonsäuregruppe,
• – i hat den Wert 0, 1, 2 oder 3,
• – p hat den Wert 0 oder 1,
• – q hat den Wert 0 oder 1 und
• – n hat den Wert 0 oder 1, mit der Maßgabe, dass
• – die Summe aus p + q ungleich 0 ist,
• – wenn p + q gleich 2 ist, n den Wert 0 hat, und die Gruppen NG¹⁷G¹⁸ und NG^{1 9}G²⁰ belegen die Positionen (2,3); (5,6); (6,7); (3,5) oder (3,7);
• – wenn p + q gleich 1 ist, n den Wert 1 hat, und die Gruppen NG¹⁷G^{1 8} (oder NG¹⁹G²⁰) und die Gruppe OH belegen die Positionen (2,3); (5,6); (6,7); (3,5) oder (3,7);

Preferred pyrazole-pyrimidine derivatives are, in particular, the derivatives of pyrazole- [1,5-a] pyrimidine of the following formula (E4) and its tautomeric forms, provided there is a tautomeric equilibrium:

in which:

• - G ¹⁷ , G ¹⁸ , G ¹⁹ and G ²⁰ independently represent a hydrogen atom, a C ₁ - to C ₄ -alkyl radical, an aryl radical, a C ₁ - to C ₄ -hydroxyalkyl radical, a C ₂ - to C ₄ -Polyhydroxyalkylrest a (C ₁ - to C ₄ ) -alkoxy- (C ₁ - to C ₄ ) -alkyl residue, a C ₁ - to C ₄ -aminoalkyl residue, optionally protected by an acetyl-ureide or a sulfonyl residue can be a (C ₁ - to C ₄ ) -alkylamino- (C ₁ - to C ₄ ) -alkyl radical, a di - [(C ₁ - to C ₄ ) -alkyl] - (C ₁ - to C ₄ ) aminoalkyl radical, where the dialkyl radicals optionally form a carbon cycle or a heterocycle with 5 or 6 chain links, a C ₁ - to C ₄ -hydroxyalkyl- or a di- (C ₁ - to C ₄ ) - [hydroxyalkyl] - (C ₁ - to C ₄ ) -aminoalkyl radical,
• - The X radicals independently of one another represent a hydrogen atom, a C ₁ - to C ₄ -alkyl radical, an aryl radical, a C ₁ - to C ₄ -hydroxyalkyl radical, a C ₂ - to C ₄ -polyhydroxyalkyl radical, a C ₁ - to C ₄ -aminoalkyl, a (C ₁ - to C ₄ ) -alkylamino- (C ₁ - to C ₄ ) -alkyl, a di - [(C ₁ - to C ₄ ) alkyl] - (C ₁ - bis C ₄ ) aminoalkyl radical, where the dialkyl radicals optionally form a carbon cycle or a heterocycle with 5 or 6 chain links, a C ₁ - to C ₄ -hydroxyalkyl or a di- (C ₁ - to C ₄ -hydroxyalkyl) aminoalkyl radical , an amino radical, a C ₁ to C ₄ alkyl or di (C ₁ to C ₄ hydroxyalkyl) amino radical, a halogen atom, a carboxylic acid group or a sulfonic acid group,
• - i has the value 0, 1, 2 or 3,
• - p has the value 0 or 1,
• - q has the value 0 or 1 and
• - n has the value 0 or 1, with the proviso that
• - the sum of p + q is not equal to 0,
• - if p + q is 2, n has the value 0, and the groups NG ¹⁷ G ¹⁸ and NG ^{1 9} G ²⁰ occupy positions (2,3); (5,6); (6,7); (3.5) or (3.7);
• - if p + q is 1, n is 1, and the groups NG ¹⁷ G ^{1 8} (or NG ¹⁹ G ²⁰ ) and the group OH occupy positions (2,3); (5,6); (6,7); (3.5) or (3.7);

The Substituents used in formula (E4) are analogous according to the invention to the above statements Are defined.

If the pyrazole [1,5-a] pyrimidine of the formula (E4) above contains a hydroxy group at one of the positions 2, 5 or 7 of the ring system, there is a tautomeric equilibrium, which is illustrated, for example, in the following scheme:

• – Pyrazol-[1,5-a]-pyrimidin-3,7-diamin;
• – 2,5-Dimethyl-pyrazol-[1,5-a]-pyrimidin-3,7-diamin;
• – Pyrazol-[1,5-a]-pyrimidin-3,5-diamin;
• – 2,7-Dimethyl-pyrazol-[1,5-a]-pyrimidin-3,5-diamin;
• – 3-Aminopyrazol-[1,5-a]-pyrimidin-7-ol;
• – 3-Aminopyrazol-[1,5-a]-pyrimidin-5-ol;
• – 2-(3-Aminopyrazol-[1,5-a]-pyrimidin-7-ylamino)-ethanol;
• – 2-(7-Aminopyrazol-[1,5-a]-pyrimidin-3-ylamino)-ethanol;
• – 2-[(3-Aminopyrazol-[1,5-a]-pyrimidin-7-yl)-(2-hydroxy-ethyl)-amino]-ethanol;
• – 2-[(7-Aminopyrazol-[1,5-a]-pyrimidin-3-yl)-(2-hydroxy-ethyl)-amino]-ethanol;
• – 5,6-Dimethylpyrazol-[1,5-a]-pyrimidin-3,7-diamin;
• – 2,6-Dimethylpyrazol-[1,5-a]-pyrimidin-3,7-diamin;
• – 3-Amino-7-dimethylamino-2,5-dimethylpyrazol-[1,5-a]-pyrimidin;

sowie ihre physiologisch verträglichen Salze und ihre tautomeren Formen, wenn ein tautomers Gleichgewicht vorhanden ist.Among the pyrazole- [1,5-a] pyrimidines of the above formula (E4), one can mention in particular:

• - pyrazole- [1,5-a] pyrimidine-3,7-diamine;
• - 2,5-dimethylpyrazole- [1,5-a] pyrimidine-3,7-diamine;
• - pyrazole- [1,5-a] pyrimidine-3,5-diamine;
• - 2,7-dimethylpyrazole- [1,5-a] pyrimidine-3,5-diamine;
• - 3-aminopyrazole- [1,5-a] pyrimidin-7-ol;
• - 3-aminopyrazole- [1,5-a] pyrimidin-5-ol;
• - 2- (3-aminopyrazole- [1,5-a] pyrimidin-7-ylamino) ethanol;
• - 2- (7-aminopyrazole- [1,5-a] pyrimidin-3-ylamino) ethanol;
• - 2 - [(3-aminopyrazole- [1,5-a] pyrimidin-7-yl) - (2-hydroxyethyl) amino] ethanol;
• - 2 - [(7-aminopyrazole- [1,5-a] pyrimidin-3-yl) - (2-hydroxyethyl) amino] ethanol;
• - 5,6-dimethylpyrazole- [1,5-a] pyrimidine-3,7-diamine;
• - 2,6-dimethylpyrazole- [1,5-a] pyrimidine-3,7-diamine;
• - 3-amino-7-dimethylamino-2,5-dimethylpyrazole [1,5-a] pyrimidine;

as well as their physiologically acceptable salts and their tautomeric forms when there is a tautomeric equilibrium.

The Pyrazole- [1,5-a] pyrimidines of the above formula (E4) can be as described in the literature by cyclization starting from one Aminopyrazole or be made by hydrazine.

As Coupler components are usually m-phenylenediamine derivatives, Naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenol derivatives used. Suitable coupler substances are in particular 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 1-phenyl-3-methyl-pyrazolon-5, 2,4-dichloro-3-aminophenol, 1,3-bis (2 ', 4'-diaminophenoxy) propane, 2-chloro-resorcinol, 4-chloro-resorcinol, 2-chloro-6-methyl-3-aminophenol, 2-amino-3-hydroxypyridine, 2-methylresorcinol, 5-methylresorcinol and 2-methyl-4-chloro-5-aminophenol.

• – m-Aminophenol und dessen Derivate wie beispielsweise 5-Amino-2-methylphenol, N-Cyclopentyl-3-aminophenol, 3-Amino-2-chlor-6-methylphenol, 2-Hydroxy-4-aminophenoxyethanol, 2,6-Dimethyl-3-aminophenol, 3-Trifluoroacetylamino-2-chlor-6-methylphenol, 5-Amino-4-chlor-2-methylphenol, 5-Amino-4-methoxy-2-methylphenol, 5-(2'-Hydroxyethyl)-amino-2-methylphenol, 3-(Diethylamino)-phenol, N-Cyclopentyl-3-aminophenol, 1,3-Dihydroxy-5-(methylamino)-benzol, 3-Ethylamino-4-methylphenol und 2,4-Dichlor-3-aminophenol,
• – o-Aminophenol und dessen Derivate,
• – m-Diaminobenzol und dessen Derivate wie beispielsweise 2,4-Diaminophenoxyethanol, 1,3-Bis-(2',4'-diaminophenoxy)-propan, 1-Methoxy-2-amino-4-(2'-hydroxyethylamino)benzol, 1,3-Bis-(2',4'-diaminophenyl)-propan, 2,6-Bis-(2'-hydroxyethylamino)-1-methylbenzol und 1-Amino-3-bis-(2'-hydroxyethyl)-aminobenzol,
• – o-Diaminobenzol und dessen Derivate wie beispielsweise 3,4-Diaminobenzoesäure und 2,3-Diamino-1-methylbenzol,
• – Di- beziehungsweise Trihydroxybenzolderivate wie beispielsweise Resorcin, Resorcinmonomethylether, 2-Methylresorcin, 5-Methylresorcin, 2,5-Dimethylresorcin, 2-Chlorresorcin, 4-Chlorresorcin, Pyrogallol und 1,2,4-Trihydroxybenzol,
• – Pyridinderivate wie beispielsweise 2,6-Dihydroxypyridin, 2-Amino-3-hydroxypyridin, 2-Amino-5-chlor-3-hydroxypyridin, 3-Amino-2-methylamino-6-methoxypyridin, 2,6-Dihydroxy-3,4-dimethylpyridin, 2,6-Dihydroxy-4-methylpyridin, 2,6-Diaminopyridin, 2,3-Diamino-6-methoxypyridin und 3,5-Diamino-2,6-dimethoxypyridin,
• – Naphthalinderivate wie beispielsweise 1-Naphthol, 2-Methyl-1-naphthol, 2-Hydroxymethyl-1-naphthol, 2-Hydroxyethyl-1-naphthol, 1,5-Dihydroxynaphthalin, 1,6- Dihydroxynaphthalin, 1,7-Dihydroxynaphthalin, 1,8-Dihydroxynaphthalin, 2,7-Dihydroxynaphthalin und 2,3-Dihydroxynaphthalin,
• – Morpholinderivate wie beispielsweise 6-Hydroxybenzomorpholin und 6-Aminobenzomorpholin,
• – Chinoxalinderivate wie beispielsweise 6-Methyl-1,2,3,4-tetrahydrochinoxalin,
• – Pyrazolderivate wie beispielsweise 1-Phenyl-3-methylpyrazol-5-on,
• – Indolderivate wie beispielsweise 4-Hydroxyindol, 6-Hydroxyindol und 7-Hydroxyindol,
• – Pyrimidinderivate, wie beispielsweise 4,6-Diaminopyrimidin, 4-Amino-2,6-dihydroxypyrimidin, 2,4-Diamino-6-hydroxypyrimidin, 2,4,6-Trihydroxypyrimidin, 2-Amino-4-methylpyrimidin, 2-Amino-4-hydroxy-6-methylpyrimidin und 4,6-Dihydroxy-2-methylpyrimidin, oder
• – Methylendioxybenzolderivate wie beispielsweise 1-Hydroxy-3,4-methylendioxybenzol, 1-Amino-3,4-methylendioxybenzol und 1-(2'-Hydroxyethyl)-amino-3,4-methylendioxybenzol.

Coupler components preferred according to the invention are

• - m-Aminophenol and its derivatives such as 5-amino-2-methylphenol, N-cyclopentyl-3-aminophenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 2,6-dimethyl -3-aminophenol, 3-trifluoroacetylamino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol, 5- (2'-hydroxyethyl) - amino-2-methylphenol, 3- (diethylamino) phenol, N-cyclopentyl-3-aminophenol, 1,3-dihydroxy-5- (methylamino) benzene, 3-ethylamino-4-methylphenol and 2,4-dichloro- 3-aminophenol,
• O-aminophenol and its derivatives,
• - m-Diaminobenzene and its derivatives such as 2,4-diaminophenoxyethanol, 1,3-bis (2 ', 4'-diaminophenoxy) propane, 1-methoxy-2-amino-4- (2'-hydroxyethylamino) benzene , 1,3-bis (2 ', 4'-diaminophenyl) propane, 2,6-bis (2'-hydroxyethylamino) -1-methylbenzene and 1-amino-3-bis (2'-hydroxyethyl) aminobenzene,
• O-diamino benzene and its derivatives such as 3,4-diamino benzoic acid and 2,3-diamino-1-methylbenzene,
• Di- or trihydroxybenzene derivatives such as, for example, resorcinol, resorcinol monomethyl ether, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2-chlororesorcinol, 4-chlororesorcinol, pyrogallol and 1,2,4-trihydroxybenzene,
• Pyridine derivatives such as 2,6-dihydroxypyridine, 2-amino-3-hydroxypyridine, 2-amino-5-chloro-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine, 2,6-dihydroxy-3, 4-dimethylpyridine, 2,6-dihydroxy-4-methylpyridine, 2,6-diaminopyridine, 2,3-diamino-6-methoxypyridine and 3,5-diamino-2,6-dimethoxypyridine,
• Naphthalene derivatives such as 1-naphthol, 2-methyl-1-naphthol, 2-hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and 2,3-dihydroxynaphthalene,
• Morpholine derivatives such as 6-hydroxybenzomorpholine and 6-aminobenzomorpholine,
• Quinoxaline derivatives such as 6-methyl-1,2,3,4-tetrahydroquinoxaline,
• Pyrazole derivatives such as 1-phenyl-3-methylpyrazol-5-one,
• Indole derivatives such as 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole,
• Pyrimidine derivatives such as 4,6-diaminopyrimidine, 4-amino-2,6-dihydroxypyrimidine, 2,4-diamino-6-hydroxypyrimidine, 2,4,6-trihydroxypyrimidine, 2-amino-4-methylpyrimidine, 2-amino -4-hydroxy-6-methylpyrimidine and 4,6-dihydroxy-2-methylpyrimidine, or
• - Methylenedioxybenzene derivatives such as 1-hydroxy-3,4-methylenedioxybenzene, 1-amino-3,4-methylenedioxybenzene and 1- (2'-hydroxyethyl) amino-3,4-methylenedioxybenzene.

According to the invention particularly preferred coupler components are 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 3-aminophenol, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridine, resorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol and 2,6-dihydroxy-3,4-dimethylpyridine.

The Oxidation dye precursors are in the agents according to the invention preferably in amounts of 0.01 to 20% by weight, preferably 0.5 to 5 wt .-%, each based on the total agent.

As Such indoles are preferred as precursors of nature-analogous dyes and indolines are used which have at least one hydroxyl or amino group, preferably as a substituent on the six-membered ring. These groups can carry further substituents, e.g. B. in the form of etherification or Esterification of the hydroxyl group or alkylation of the amino group.

in der unabhängig voneinander

• – R¹ steht für Wasserstoff, eine C₁-C₄-Alkylgruppe oder eine C₁-C₄-Hydroxy-alkylgruppe,
• – R² steht für Wasserstoff oder eine -COOH-Gruppe, wobei die -COOH-Gruppe auch als Salz mit einem physiologisch verträglichen Kation vorliegen kann,
• – R³ steht für Wasserstoff oder eine C₁-C₄-Alkylgruppe,
• – R⁴ steht für Wasserstoff, eine C₁-C₄-Alkylgruppe oder eine Gruppe -CO-R⁶, in der R⁶ steht für eine C₁-C₄-Alkylgruppe, und
• – R⁵ steht für eine der unter R⁴ genannten Gruppen,

sowie physiologisch verträgliche Salze dieser Verbindungen mit einer organischen oder anorganischen Säure.Derivatives of 5,6-dihydroxyindoline of the formula (IIa) are particularly suitable as precursors of naturally analogous hair dyes,

in the independently of each other

• R ¹ represents hydrogen, a C ₁ -C ₄ alkyl group or a C ₁ -C ₄ hydroxyalkyl group,
• R ² stands for hydrogen or a -COOH group, where the -COOH group can also be present as a salt with a physiologically compatible cation,
• R ³ represents hydrogen or a C ₁ -C ₄ alkyl group,
• - R ⁴ stands for hydrogen, a C ₁ -C ₄ alkyl group or a group -CO-R ⁶ , in which R ⁶ stands for a C ₁ -C ₄ alkyl group, and
• R ⁵ stands for one of the groups mentioned under R ⁴ ,

as well as physiologically tolerable salts of these compounds with an organic or inorganic acid.

Especially preferred derivatives of indoline are 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline, 5,6-dihydroxyindoline-2-carboxylic acid as well as the 6-hydroxyindoline, the 6-aminoindoline and the 4-aminoindoline.

Especially within this group, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline and especially 5,6-dihydroxyindoline.

in der unabhängig voneinander

• – R¹ steht für Wasserstoff, eine C₁-C₄-Alkylgruppe oder eine C₁-C₄-Hydroxyalkylgruppe,
• – R² steht für Wasserstoff oder eine -COOH-Gruppe, wobei die -COOH-Gruppe auch als Salz mit einem physiologisch verträglichen Kation vorliegen kann,
• – R³ steht für Wasserstoff oder eine C₁-C₄-Alkylgruppe,
• – R⁴ steht für Wasserstoff, eine C₁-C₄-Alkylgruppe oder eine Gruppe -CO-R⁶, in der R⁶ steht für eine C₁-C₄-Alkylgruppe, und
• – R⁵ steht für eine der unter R⁴ genannten Gruppen,
• – sowie physiologisch verträgliche Salze dieser Verbindungen mit einer organischen oder anorganischen Säure.

Derivatives of 5,6-dihydroxyindole of the formula (IIb) are also outstandingly suitable as precursors of nature-analogous hair dyes,

in the independently of each other

• R ¹ represents hydrogen, a C ₁ -C ₄ -alkyl group or a C ₁ -C ₄ -hydroxyalkyl group,
• R ² stands for hydrogen or a -COOH group, where the -COOH group can also be present as a salt with a physiologically compatible cation,
• R ³ represents hydrogen or a C ₁ -C ₄ alkyl group,
• - R ⁴ stands for hydrogen, a C ₁ -C ₄ alkyl group or a group -CO-R ⁶ , in which R ⁶ stands for a C ₁ -C ₄ alkyl group, and
• R ⁵ stands for one of the groups mentioned under R ⁴ ,
• - And physiologically acceptable salts of these compounds with an organic or inorganic acid.

Especially preferred derivatives of indole are 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole, 5,6-dihydroxyindole-2-carboxylic acid, 6-hydroxyindole, 6-aminoindole and 4-aminoindole.

Within of this group are N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole and in particular 5,6-dihydroxyindole.

The Indoline and indole derivatives can used in the process of the invention coloring both as free bases and in the form of their physiologically acceptable Salts with inorganic or organic acids, e.g. B. the hydrochloride, of sulfates and hydrobromides. The indole or Indoline derivatives are common in these in amounts of 0.05-10 % By weight, preferably 0.2-5 % By weight.

In a further embodiment it can be preferred according to the invention be the indoline or Indole derivative in hair dye in combination with at least one amino acid or an oligopeptide use. The amino acid is advantageously an α-amino acid; all are particularly preferred α-amino acids Arginine, ornithine, lysine, serine and histidine, especially arginine.

Next the dye precursors according to the invention can the colorants of the invention Shading contain one or more substantive dyes. Direct dyes are common Nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols. Preferred substantive dyes are under the international names or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, Acid Yellow 1, Acid Yellow 10, Acid Yellow 23, Acid Yellow 36, HC Orange 1, Disperse Orange 3, Acid Orange 7, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, Acid Red 33, Acid Red 52, HC Red BN, pigment Red 57: 1, HC Blue 2, HC Blue 12, Disperse Blue 3, Acid Blue 7, Acid Green 50, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Acid Violet 43, Disperse Black 9, Acid Black 1, and Acid Black 52 are known Compounds and 1,4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis (β-hydroxyethyl) amino-2-nitropenzene, 3-nitro-4- (β-hydroxyethyl) aminophenol, 2- (2'-hydroxyethyl) amino-4,6-dinitrophenol, 1- (2'-hydroxyethyl) amino-4-methyl-2-nitrobenzene, 1-amino-4- (2'-hydroxyethyl) amino-5-chloro-2-nitrobenzene, 4-amino-3-nitrophenol, 1- (2'-ureidoethyl) amino-4-nitrobenzene, 4-amino-2-nitrodiphenylamine-2'-carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4-naphthoquinone, picramic and their salts, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene.

• (a) kationische Triphenylmethanfarbstoffe, wie beispielsweise Basic Blue 7, Basic Blue 26, Basic Violet 2 und Basic Violet 14,
• (b) aromatischen Systeme, die mit einer quaternären Stickstoffgruppe substituiert sind, wie beispielsweise Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 und Basic Brown 17, sowie
• (c) direktziehende Farbstoffe, die einen Heterocyclus enthalten, der mindestens ein quaternäres Stickstoffatom aufweist, wie sie beispielsweise in der EP-A2-998 908 , auf die an dieser Stelle explizit Bezug genommen wird, in den Ansprüchen 6 bis 11 genannt werden.

Furthermore, the agents according to the invention can contain a cationic direct dye. Are particularly preferred

• (a) cationic triphenylmethane dyes, such as, for example, Basic Blue 7, Basic Blue 26, Basic Violet 2 and Basic Violet 14,
• (b) aromatic systems which are substituted with a quaternary nitrogen group, such as, for example, Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 and Basic Brown 17, and
• (c) direct dyes containing a heterocycle containing at least one quaternary nitrogen atom, as for example in the EP-A2-998 908 , to which reference is expressly made at this point, are mentioned in claims 6 to 11.

Preferred cationic direct dyes of group (c) are in particular the following compounds:

The Compounds of the formulas (DZ1), (DZ3) and (DZ5), which also under Basic Yellow 87, Basic Orange 31 and Basic Red 51 are very particularly preferred cationic direct pulls Group (c) dyes.

The cationic direct dyes, which are sold under the trademark Arianor ^® are, according to the invention also very particularly preferred cationic direct dyes.

The agents according to the invention according to this embodiment contain the substantive dyes preferably in an amount from 0.01 to 20% by weight, based on the total colorant.

Furthermore, the preparations according to the invention can also contain naturally occurring dyes such as those in, for example, henna red, henna neutral, henna black, chamomile flowers, sandalwood and black Tea, rotten tree bark, sage, blue wood, madder root, catechu, sedre and alkanna root are included.

It it is not necessary that the oxidation dye precursors or the direct dyes each have uniform compounds represent. Rather you can in the hair colorants according to the invention through the manufacturing processes for the individual dyes, additional components may be contained in minor quantities, as far as this is not the coloring result adversely affect or for other reasons, e.g. toxicological, must be excluded.

Regarding the in the hair dye and -tönungsmitteln usable dyes will continue to expressly on the monograph Ch. Zviak, The Science of Hair Care, Chapter 7 (pages 248-250; substantive Dyes) and Chapter 8, pages 264-267; Oxidation dye precursors) published as Volume 7 of the series "Dermatology" (Ed .: Ch., Culnan and H. Maibach), Marcel Dekker Inc., New York, Basel, 1986, as well as the "European inventory of cosmetic raw materials " published by the European Community, available in floppy form from the Federal Association of German Industry and Trade Companies for Medicines, Health food and personal care products e.V., Mannheim, referred to.

Next the enzyme system according to the invention can the colorants of the invention also other enzymes, such as laccases, tyrosinases, peroxidases or contain oxidases with their respective substrates. preferred Oxidases are, for example, choline oxidase, glucose oxidase, alcohol oxidase, Pyruvate oxidase, oxalate oxidase, cholesterol oxidase, uricase, lactate oxidase, Xanthine oxidase, pyranose oxidase, glycerol oxidase, bilirubin oxidase, Amino acid oxidases, Glutamate oxidase, monoamine oxidase, sarcosine oxidase and galactose oxidase. In the context of this embodiment agents that are in addition to the enzyme according to the invention are particularly preferred further uricase, glucose oxidase and / or xanthine oxidase and their contain respective substrates.

The colorant according to the invention can continue all for such preparations contain known active ingredients, additives and auxiliaries. In many cases contain the colorants at least one surfactant, in principle both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants are suitable. The expert can have a possible influence of various surfactants on the activity of the enzyme system according to the invention Check if necessary with simple preliminary tests.

In a preferred embodiment The present invention becomes more keratinous in colorants Fibers a combination of anionic and non-ionic surfactants or a combination of anionic and amphoteric surfactants. But in individual cases proved to be advantageous, the surfactants from amphoteric or nonionic Select surfactants, since these generally have less influence on the dyeing process according to the invention.

• – lineare Fettsäuren mit 10 bis 22 C-Atomen (Seifen),
• – Ethercarbonsäuren der Formel R-O-(CH₂-CH₂O)_x-CH₂-COOH, in der R eine lineare Alkylgruppe mit 10 bis 22 C-Atomen und x = 0 oder 1 bis 16 ist,
• – Acylsarcoside mit 10 bis 18 C-Atomen in der Acylgruppe,
• – Acyltauride mit 10 bis 18 C-Atomen in der Acylgruppe,
• – Acylisethionate mit 10 bis 18 C-Atomen in der Acylgruppe,
• – Sulfobernsteinsäuremono- und -dialkylester mit 8 bis 18 C-Atomen in der Alkylgruppe und Sulfobernsteinsäuremono-alkylpolyoxyethylester mit 8 bis 18 C-Atomen in der Alkylgruppe und 1 bis 6 Oxyethylgruppen,
• – lineare Alkansulfonate mit 12 bis 18 C-Atomen,
• – lineare Alpha-Olefinsulfonate mit 12 bis 18 C-Atomen,
• – Alpha-Sulfofettsäuremethylester von Fettsäuren mit 12 bis 18 C-Atomen,
• – Alkylsulfate und Alkylpolyglykolethersulfate der Formel R-O(CH₂-CH₂O)_x-SO₃H, in der R eine bevorzugt lineare Alkylgruppe mit 10 bis 18 C-Atomen und x = 0 oder 1 bis 12 ist,
• – Gemische oberflächenaktiver Hydroxysulfonate gemäß DE-A-37 25 030 ,
• – sulfatierte Hydroxyalkylpolyethylen- und/oder Hydroxyalkylenpropylenglykolether gemäß DE-A-37 23 354 ,
• – Sulfonate ungesättigter Fettsäuren mit 12 bis 24 C-Atomen und 1 bis 6 Doppelbindungen gemäß DE-A-39 26 344 ,
• – Ester der Weinsäure und Zitronensäure mit Alkoholen, die Anlagerungsprodukte von etwa 2–15 Molekülen Ethylenoxid und/oder Propylenoxid an Fettalkohole mit 8 bis 22 C-Atomen darstellen.

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

• - linear fatty acids with 10 to 22 carbon atoms (soaps),
• Ether carboxylic acids of the formula RO- (CH ₂ -CH ₂ O) _x -CH ₂ -COOH, in which R is a linear alkyl group with 10 to 22 C atoms and x = 0 or 1 to 16,
• Acyl sarcosides with 10 to 18 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,
• - Monosulfonic acid and dialkyl sulfosuccinates with 8 to 18 carbon atoms in the alkyl group and mono-alkyl polyoxyethyl sulfosuccinates with 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups,
• Linear alkanesulfonates with 12 to 18 carbon atoms,
• Linear alpha olefin sulfonates with 12 to 18 carbon atoms,
• - Alpha-sulfofatty acid methyl esters of fatty acids with 12 to 18 carbon atoms,
• Alkyl sulfates and alkyl polyglycol ether sulfates of the formula RO (CH ₂ -CH ₂ O) _x -SO ₃ H, in which R is a preferably linear alkyl group with 10 to 18 C atoms and x = 0 or 1 to 12,
• - Mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030 .
• - Sulphated hydroxyalkyl polyethylene and / or hydroxyalkylene propylene glycol ether according to DE-A-37 23 354 .
• - Sulfonates of unsaturated fatty acids with 12 to 24 carbon atoms and 1 to 6 double bonds according to DE-A-39 26 344 .
• - Esters of tartaric acid and citric acid with alcohols, which are adducts of about 2-15 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 ,

• – Anlagerungsprodukte von 2 bis 30 Mol Ethylenoxid und/oder 0 bis 5 Mol Propylenoxid an lineare Fettalkohole mit 8 bis 22 C-Atomen, an Fettsäuren mit 12 bis 22 C-Atomen und an Alkylphenole mit 8 bis 15 C-Atomen in der Alkylgruppe,
• – C₁₂-C₂₂-Fettsäuremono- und -diester von Anlagerungsprodukten von 1 bis 30 Mol Ethylenoxid an Glycerin,
• – C₈-C₂₂-Alkylmono- und -oligoglycoside und deren ethoxylierte Analoga sowie
• – Anlagerungsprodukte von 5 bis 60 Mol Ethylenoxid an Rizinusöl und gehärtetes Rizinusöl.

Non-ionic surfactants contain z. 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 mol of ethylene oxide and / or 0 to 5 mol 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 -C ₂₂ fatty acid monoesters and diesters of addition products of 1 to 30 moles of ethylene oxide with glycerol,
• - C ₈ -C ₂₂ alkyl mono- and oligoglycosides and their ethoxylated analogues as well
• - Adducts of 5 to 60 moles of ethylene oxide with castor oil and hardened castor oil.

Preferred nonionic surfactants are alkyl polyglycosides of the general formula R ¹ O (Z) _x . These connections are characterized by the following parameters.

The alkyl radical R ¹ contains 6 to 22 carbon atoms and can be either linear or branched. Primary linear and methyl-branched aliphatic radicals in the 2-position are preferred. Examples of such alkyl radicals are 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl and 1-stearyl. 1-Octyl, 1-decyl, 1-lauryl, 1-myristyl are particularly preferred. When using so-called "oxo alcohols" as starting materials, compounds with an odd number of carbon atoms in the alkyl chain predominate.

The alkyl polyglycosides which can be used according to the invention can contain, for example, only a certain alkyl radical R ¹ . Usually, however, these compounds are made from natural fats and oils or mineral oils. In this case, the alkyl radicals R are mixtures corresponding to the starting compounds or corresponding to the respective working up of these compounds.

• – im wesentlichen aus C₈- und C₁₀-Alkylgruppen,
• – im wesentlichen aus C₁₂- und C₁₄-Alkylgruppen,
• – im wesentlichen aus C₈- bis C₁₆-Alkylgruppen oder
• – im wesentlichen aus C₁₂- bis C_{1 6}-Alkylgruppen besteht.

Alkylpolyglycosides in which R ¹

• Essentially from C ₈ and C ₁₀ alkyl groups,
• Essentially from C ₁₂ and C ₁₄ alkyl groups,
• - essentially from C ₈ - to C ₁₆ alkyl groups or
• - essentially of C ₁₂ - to C ₆ -alkyl groups is _1.

As Sugar block Z can any mono- or oligosaccharides can be used. Usually will Sugar with 5 or 6 carbon atoms and the corresponding oligosaccharides used. Examples of such sugars are glucose, fructose, Galac tose, arabinose, ribose, xylose, lyxose, allose, old rose, mannose, Gulose, Idose, Talose and Sucrose. Preferred sugar building blocks are Glucose, fructose, galactose, arabinose and sucrose; Is glucose particularly preferred.

The usable according to the invention Alkyl polyglycosides contain an average of 1.1 to 5 sugar units. Alkyl polyglycosides with x values from 1.1 to 1.6 are preferred. Alkyl glycosides in which x 1.1 to Is 1.4.

The Alkyl glycosides can in addition to their surfactant effect also serve to fix fragrance components to improve on the hair. The specialist is therefore in the event that one over the effect of the perfume oil on the duration of the hair treatment the hair desired is preferred to this class of substances as a further ingredient of the preparations according to the invention To fall back on.

Also the alkoxylated homologues of the alkyl polyglycosides mentioned can be used according to the invention become. These homologues can on average up to 10 ethylene oxide and / or propylene oxide units included per alkyl glycoside unit.

Furthermore, zwitterionic surfactants can be used, in particular as co-surfactants. Zwitterionic surfactants are surface-active compounds that contain at least one quaternary ammonium group and at least one -COO ⁽⁾ or -SO ₃ ^(-) group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines, such as the N-alkyl-N, N-dimethylammonium glycinate, for example the cocoalkyl-dimethylammonium glycinate, N-acyl-aminopropyl-N, N-dimethylammonium glycinate, for example the cocoacylaminopropyl-dimethylammonium glycinate, and 2 -Alkyl-3-carboxylmethyl-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 INCI name Cocamidopropyl Betaine.

Ampholytic surfactants are also particularly suitable as co-surfactants. Ampholytic surfactants are surface-active compounds which, in addition to a C ₈ -C ₁₈ -alkyl or acyl group, contain at least one free amino group and at least one -COOH or -SO ₃ H group in the molecule and are capable of forming internal salts. Examples of suitable ampholytic surfactants are N-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 C. Atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethyl aminopropionate and C _{12-1 8} acyl sarcosine.

According to the invention as cationic surfactants, especially those of the quaternary ammonium compound type, the esterquats and the amidoamines used.

preferred quaternary Ammonium compounds are ammonium halides, especially chlorides and Bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g. B. cetyltrimethylammonium chloride, Stearyltrimethylammonium chloride, distearyldimethylammonium chloride, Lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride, as well as those under the INCI names Quaternium-27 and Quaternium-83 known imidazolium compounds. The long alkyl chains of the above surfactants are preferred 10 to 18 carbon atoms.

Ester quats are known substances which contain both at least one ester function and at least one quaternary ammonium group as a structural element. Preferred ester quats are quaternized ester salts of fatty acids with triethanolamine, quaternized ester salts of fatty acids with diethanolalkylamines and quaternized ester salts of fatty acids with 1,2-dihydroxypropyldialkylamines. Such products are sold, for example, under the trademarks Stepantex ^® , Dehyquart ^® and Armocare ^® . The products Armocare ^® VGH-70, an N, N-bis (2-palmitoyloxyethyl) dimethylammonium chloride, as well as Dehyquart ^® F-75 and Dehyquart ^® AU-35 are examples of such esterquats.

The alkylamidoamines are usually produced by amidation of natural or synthetic fatty acids and fatty acid cuts with dialkylaminoamines. An inventively particularly suitable compound from this group is that available under the name Tegoamid ^® S 18 commercially stearamidopropyl.

Further usable according to the invention cationic surfactants are the quaternized protein hydrolyzates represents.

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).

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

The compounds with alkyl groups used as surfactant 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 mixtures of substances with different, depending on because of raw material dependent alkyl chain lengths.

at the surfactants, the adducts of ethylene and / or propylene oxide of fatty alcohols or derivatives of these addition products, can both products with a "normal" homolog distribution as well as those with a narrow homolog distribution become. Under "normal" homolog distribution are understood as mixtures of homologues that are used in the Reaction of fatty alcohol and alkylene oxide using alkali metals, Alkali metal hydroxides or alkali metal alcoholates as catalysts receives. On the other hand, narrow homolog distributions are obtained if, for example Hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates can be used as catalysts. The use of products with a narrow homolog distribution can be preferred.

Farther contain the agents according to the invention preferably at least one alkalizing agent. Preferred alkalizing agents are ammonia, monoethanolamine, sodium hydroxide, potassium hydroxide and especially arginine, lysine and histidine.

Farther can the colorants of the invention preferably a conditioning agent selected from the group of cationic surfactants, cationic polymers, Alkylamidoamines, paraffin oils, vegetable oils and synthetic oils is formed. Regarding the cationic surfactants on the above statements directed.

As conditioning agents can be preferred cationic polymers. These are usually polymers that have a quaternary nitrogen atom, for example in the form of an ammonium group.

• – quaternisierte Cellulose-Derivate, wie sie unter den Bezeichnungen Celquat^® und Polymer JR^® im Handel erhältlich sind. Die Verbindungen Celquat^® N 100, Celquat^® L 200 und Polymer JR^®400 sind bevorzugte quaternierte Cellulose-Derivate.
• – polymere Dimethyldiallylammoniumsalze und deren Copolymere mit Acrylsäure sowie Estern und Amiden von Acrylsäure und Methacrylsäure. Die unter den Bezeichnungen Merquat^®100 (Poly(dimethyldiallylammoniumchlorid)), Merquat^®550 (Dimethyldiallylammoniumchlorid-Acrylamid-Copolymer) und Merquat^® 280 (Dimethyldiallylammoniumchlorid-Acrylsäure-Copolymer im Handel erhältlichen Produkte sind Beispiele für solche kationischen Polymere.
• – Copolymere des Vinylpyrrolidons mit quaternierten Derivaten des Dialkylaminoacrylats und -methacrylats, wie beispielsweise mit Diethylsulfat quaternierte Vinylpyrrolidon-Dimethylaminomethacrylat-Copolymere. Solche Verbindungen sind unter den Bezeichnungen Gafquat^®734 und Gafquat^®755 im Handel erhältlich.
• – Vinylpyrrolidon-Methoimidazoliniumchlorid-Copolymere, wie sie unter der Bezeichnung Luviquat^® angeboten werden.
• – quaternierter Polyvinylalkohol sowie die unter den Bezeichnungen
• – Polyquaternium 2,
• – Polyquaternium 17,
• – Polyquaternium 18 und
• – Polyquaternium 27 bekannten Polymeren mit quartären Stickstoffatomen in der Polymerhauptkette.

Preferred cationic polymers are, for example

• - Quaternized cellulose derivatives, as are commercially available under the names Celquat ^® and Polymer JR ^® . The compounds Celquat ^® N 100, Celquat ^® L 200 and Polymer JR ^® 400 are preferred quaternized cellulose derivatives.
• - polymeric dimethyldiallylammonium salts and their copolymers with acrylic acid and esters and amides of acrylic acid and methacrylic acid. Under the names Merquat ^® 100 (Poly (dimethyldiallylammonium chloride)), Merquat ^® 550 (dimethyldiallylammonium chloride-acrylamide copolymer) and Merquat ^® 280 (dimethyldiallylammonium chloride-acrylic acid copolymer commercially available products are examples of such cationic polymers.
• - Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylate, such as vinylpyrrolidone-dimethylaminomethacrylate copolymers quaternized with diethyl sulfate. Such compounds are commercially available under the names Gafquat ^® 734 and Gafquat ^® 755.
• - Vinylpyrrolidone-methoimidazolinium chloride copolymers, as are offered under the name Luviquat ^® .
• - Quaternized polyvinyl alcohol and those under the names
• - polyquaternium 2,
• - polyquaternium 17,
• - Polyquaternium 18 and
• - Polyquaternium 27 known polymers with quaternary nitrogen atoms in the main polymer chain.

Cationic polymers of the first four groups and polyquaternium-2 are particularly preferred, and polyquaternium-2, polyquaternium-10 and polyquaternium-22 are very particularly preferred. Among known as Polyquaternium-2 compounds, in particular the commercial product Mirapol ^® A-15 is preferred.

Also suitable as conditioning agents are silicone oils, in particular dialkyl and alkylarylsiloxanes, such as dimethylpolysiloxane and methylphenylpolysiloxane, and their alkoxylated and quaternized analogs. Examples of such silicones are the products sold by Dow Corning under the names DC 190, DC 200, DC 344, DC 345 and DC 1401 as well as the commercial products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethylsilylamodimethicone), Dow ^Corning® 929 emulsion (containing a hydroxyl-amino-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).

Likewise Paraffin oils, synthetic, can be used as conditioning agents manufactured oligomeric alkenes as well as vegetable oils such as jojoba oil, sunflower oil, orange oil, almond oil, wheat germ oil and peach seed oil.

Likewise suitable hair conditioning compounds are phospholipids, for example soy lecithin, egg lecithin and cephaline.

Farther contain the used according to the invention Preparations preferably have at least one oil component.

Oil components suitable according to the invention are basically all water-insoluble oils and fats as well their mixtures with solid paraffins and waxes. As become water insoluble according to the invention such Substances defined, their solubility in water at 20 ° C is less than 0.1% by weight. The melting point of the individual oil or fat components is preferably below about 40 ° C. Oil and fat components that at room temperature, d. H. are liquid below 25 ° C, can be particularly inventive be preferred. When using multiple oil and fat components as well however, it is usually also solid paraffins and waxes sufficient if the mixture of oil and fat components as well if necessary, paraffins and waxes meet these conditions.

A preferred group of oil components are vegetable oils. examples for such oils are sunflower oil, Olive oil, Soybean oil, Rapeseed oil, Almond oil, jojoba oil, Orange oil, Wheat germ oil, Peach kernel oil and the liquid Proportions of coconut oil.

Suitable but are also other triglyceride oils such as the liquid components of beef tallow and synthetic triglyceride oils.

Another particularly preferred group of compounds which can be used according to the invention as an oil component are liquid paraffin oils and synthetic hydrocarbons and di-n-alkyl ethers with a total of between 12 to 36 carbon atoms, in particular 12 to 24 carbon atoms, such as, for example, di-n-octyl ether, di -n-decyl ether, di-n-nonyl ether, di-n-undecyl ether, di-n-dodecyl ether, n-hexyl-n-octyl ether, n-octyl-n-decyl ether, n-decyl-n-undecyl ether, n-undecyl -n-dodecyl ether and n-hexyl-n-undecyl ether and di-tert-butyl ether, di-isopentyl ether, di-3-ethyldecyl ether, tert-butyl-n-octyl ether, isopentyl-n-octyl ether and 2- methyl-pentyl-n-octyl ether. The compounds are available as commercial products 1,3-di- (2-ethyl-hexyl) -cyclohexane (Cetiol ^® S), and di-n-octyl ether (Cetiol ^® OE) may be preferred.

Oil components which can likewise be used according to the invention are fatty acid and fatty alcohol esters. The monoesters of the fatty acids with alcohols having 3 to 24 carbon atoms are preferred. This group of substances concerns the products of the esterification of fatty acids with 6 to 24 carbon atoms such as, for example, caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, Petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures, the z. B. in the pressure splitting of natural fats and oils, in the oxidation of aldehydes from Roelen's oxo synthesis or the dimerization of unsaturated fatty acids, with alcohols such as isopropyl alcohol, capronic alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol , Myristyl alcohol, cetyl alcohol, palmitoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and their mixtures and brasside mixtures. B. in the high pressure hydrogenation of technical methyl esters based on fats and oils or aldehydes from Roelen's oxosynthesis and as a monomer fraction in the dimerization of unsaturated fatty alcohols. According to the invention particularly preferably isopropyl myristate, isononanoic acid C16-18 alkyl ester (Cetiol ^® SN), stearic acid-2-ethylhexyl ester (Cetiol ^® 868), cetyl oleate, glycerol tricaprylate, cocofatty alcohol caprate / caprylate and n-butyl stearate.

Farther also make dicarboxylic acid esters such as di-n-butyl adipate, di- (2-ethylhexyl) adipate, di- (2-ethylhexyl) succinate and di-isotridecylacelaate and diol esters such as ethylene glycol dioleate, Ethylene glycol di-isotridecanoate, propylene glycol di (2-ethylhexanoate), Propylene glycol di-isostearate, propylene glycol di-pelargonate, butanediol di-isostearate and neopentyl glycol di-capylate oil components which can be used according to the invention are just as complex esters such. B. the diacetyl glycerol monostearate.

Finally, fatty alcohols with 8 to 22 carbon atoms can also be used as oil compounds according to the invention components are used. The fatty alcohols can be saturated or unsaturated and linear or branched. For example, decanol, octanol, octenol, dodecenol, decenol, octadienol, dodecadienol, decadienol, oleyl alcohol, eruca alcohol, ricinol alcohol, stearyl alcohol, isostearyl alcohol, cetyl alcohol, lauryl alcohol, myristyl alcohol, capryl alcohol, arachidyl alcohol, arachidyl alcohol, arachidyl alcohol, arachidyl alcohol, arachidyl alcohol, arachidyl alcohol , as well as their Guerbet alcohols, this list is intended to be exemplary and not limiting. The fatty alcohols, however, derive from preferably natural fatty acids, and it can usually be assumed that they are obtained from the esters of the fatty acids by reduction. Also suitable according to the invention are those fatty alcohol cuts which are produced by reducing naturally occurring triglycerides such as beef tallow, palm oil, peanut oil, rapeseed oil, cottonseed oil, soybean oil, sunflower oil and linseed oil or fatty acid esters formed from their transesterification products with corresponding alcohols, and thus represent a mixture of different fatty alcohols.

The oil components are preferred in Menden from 0.05 to 10 wt .-%, in particular from 0.1 to 2% by weight used in the colorants according to the invention.

In a preferred embodiment In the present invention, a gel forms when the colorants are dissolved in water. For this, the colorant Thickeners such as agar agar, guar gum, alginates, xanthan gum, Gum arabic, karaya gum, locust bean gum, linseed gums, Dextrans, acrylates, e.g. Cellulose derivatives, e.g. B. methyl cellulose, Hydroxyalkyl cellulose and carboxymethyl cellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such as e.g. B. bentonite or fully synthetic hydrocolloids such as e.g. polyvinyl alcohol added. Particularly preferred thickeners are xanthans, Alginates and highly substituted carboxymethyl celluloses.

Preferred acrylate-type thickeners according to the invention are, for example, copolymers of acrylic acid, methacrylic acid or their C ₁ - to C ₆ -alkyl esters, as are sold under the INCI declaration Acrylates Copolymers. A preferred commercial product is, for example, Aculyn ^® 33 from Rohm & Haas. However, copolymers of acrylic acid, methacrylic acid or their C ₁ - to C ₆ -alkyl esters and the esters of an ethylenically unsaturated acid and an optionally alkoxylated fatty alcohol are also preferred. Suitable ethylenically unsaturated acids are in particular acrylic acid, methacrylic acid and itaconic acid; Suitable alkoxylated fatty alcohols are, in particular, steareth-20 or ceteth-20. Such copolymers are sold by Rohm & Haas under the trade name Aculyn ^® 22 and by National Starch under the trade names Structure ^® Structure 2001 ^® 3,001th

• – zwitterionische und amphotere Polymere wie beispielsweise Acrylamidopropyl-tri-methylammoniumchlorid/Acrylat-Copolymere und Octylacrylamid/Methyl-methacrylat/tert-Butylaminoethylmethacrylat/2-Hydroxypropylmethacrylat-Copolymere,
• – anionische Polymere wie beispielsweise Polyacrylsäuren, vernetzte Polyacrylsäuren, Vinylacetat/Crotonsäure-Copolymere, Vinylpyrrolidon/Vinylacrylat-Copolymere, Vinylacetat/Butylmaleat/Isobornylacrylat-Copolymere, Methylvinylether/Maleinsäureanhydrid-Copolymere und Acrylsäure/Ethylacrylat/N-tert.Butyl-acrylamid-Terpolymere,
• – Strukturanten wie Maleinsäure und Milchsäure,
• – haarkonditionierende Verbindungen wie Phospholipide, beispielsweise Sojalecithin, Ei-Lecitin und Kephaline,
• – Proteinhydrolysate, insbesondere Elastin-, Kollagen-, Keratin-, Milcheiweiß-, Sojaprotein- und Weizenproteinhydrolysate, deren Kondensationsprodukte mit Fettsäuren sowie quaternisierte Proteinhydrolysate,
• – Parfümöle, Dimethylisosorbid und Cyclodextrine,
• – faserstrukturverbessernde Wirkstoffe, insbesondere Mono-, Di- und Oligosaccharide wie beispielsweise Glucose, Galactose, Fructose, Fruchtzucker und Lactose,
• – quaternierte Amine wie Methyl-1-alkylamidoethyl-2-alkylimidazolinium-methosulfat
• – Entschäumer wie Silikone,
• – Farbstoffe zum Anfärben des Mittels,
• – Antischuppenwirkstoffe wie Piroctone Olamine, Zink Omadine und Climbazol,
• – Lichtschutzmittel, insbesondere derivatisierte Benzophenone, Zimtsäure-Derivate und Triazine,
• – Substanzen zur Einstellung des pH-Wertes, wie beispielsweise übliche Säuren, insbesondere Genußsäuren und Basen,
• – Wirkstoffe wie Allantoin, Pyrrolidoncarbonsäuren und deren Salze sowie Bisabolol,
• – Vitamine, Provitamine und Vitaminvorstufen, insbesondere solche der Gruppen A, B₃, B₅, B₆, C, E, F und H,
• – Pflanzenextrakte wie die Extrakte aus Grünem Tee, Eichenrinde, Brennessel, Hamamelis, Hopfen, Kamille, Klettenwurzel, Schachtelhalm, Weißdorn, Lindenblüten, Mandel, Aloe Vera, Fichtennadel, Roßkastanie, Sandelholz, Wacholder, Kokosnuß, Mango, Aprikose, Limone, Weizen, Kiwi, Melone, Orange, Grapefruit, Salbei, Rosmarin, Birke, Malve, Wiesenschaumkraut, Quendel, Schafgarbe, Thymian, Melisse, Hauhechel, Huflattich, Eibisch, Meristem, Ginseng und Ingwerwurzel,.
• – Cholesterin,
• – Konsistenzgeber wie Zuckerester, Polyolester oder Polyolalkylether,
• – Fette und Wachse wie Walrat, Bienenwachs, Montanwachs und Paraffine,
• – Fettsäurealkanolamide,
• – Komplexbildner wie EDTA, NTA, β-Alanindiessigsäure und Phosphonsäuren,
• – Quell- und Penetrationsstoffe wie Glycerin, Propylenglykolmonoethylether, Carbonate, Hydrogencarbonate, Guanidine, Harnstoffe sowie primäre, sekundäre und tertiäre Phosphate,
• – Trübungsmittel wie Latex, Styrol/PVP- und Styrol/Acrylamid-Copolymere
• – Perlglanzmittel wie Ethylenglykolmono- und -distearat sowie PEG-3-distearat,
• – Pigmente,
• – Stabilisierungsmittel für Wassserstoffperoxid und andere Oxidationsmittel,
• – Treibmittel wie Propan-Butan-Gemische, N₂O, Dimethylether, CO₂ und Luft,
• – Antioxidantien,
• – Konservierungsmittel und
• – Reduktionsmittel, wie Natriumsulfit, Natriumdithionit oder Ascorbinsäure

enthalten.Furthermore, the colorants according to the invention can contain further active ingredients, auxiliaries and additives, such as, for example

• - zwitterionic and amphoteric polymers such as, for example, acrylamidopropyl-trimethylammonium 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, vinylpyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and acrylic acid / ethyl acrylate / N-tert.butyl acrylamide terpolymers,
• - structurants such as maleic acid and lactic acid,
• Hair-conditioning compounds such as phospholipids, for example soy lecithin, egg lecithin and cephalins,
• 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,
• Active ingredients that improve fiber structure, in particular mono-, di- and oligosaccharides such as, for example, glucose, galactose, fructose, fructose and lactose,
• - Quaternized amines such as methyl 1-alkylamidoethyl-2-alkylimidazolinium methosulfate
• - defoamers like silicones,
• Dyes for coloring the agent,
• - anti-dandruff agents such as piroctone olamine, zinc omadine and climbazol,
• Light stabilizers, in particular derivatized benzophenones, cinnamic acid derivatives and triazines,
• Substances for adjusting the pH, such as, for example, customary acids, in particular edible acids and bases,
• Active ingredients such as allantoin, pyrrolidone carboxylic acids and their salts and bisabolol,
• - Vitamins, provitamins and vitamin precursors, in particular those of groups A, B ₃ , B ₅ , B ₆ , C, E, F and H,
• - Plant extracts such as the extracts from green tea, oak bark, nettle, witch hazel, hops, chamomile, burdock root, horsetail, hawthorn, linden flowers, almond, aloe vera, spruce needle, horse chestnut, sandalwood, juniper, coconut, mango, apricot, lime, wheat, Kiwi, melon, orange, grapefruit, sage, rosemary, birch, mallow, cuckoo flower, quendel, yarrow, thyme, lemon balm, hake, coltsfoot, marshmallow, meristem, ginseng and ginger root.
• - cholesterol,
• - consistency enhancers such as sugar esters, polyol esters or polyol alkyl ethers,
• - fats and waxes such as walrus, beeswax, montan wax and paraffins,
• - fatty acid alkanolamides,
• Complexing agents such as EDTA, NTA, β-alaninediacetic acid 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,
• - opacifiers such as latex, styrene / PVP and styrene / acrylamide copolymers
• Pearlescent agents such as ethylene glycol mono- and distearate and PEG-3 distearate,
• - pigments,
• - stabilizing agents for hydrogen peroxide and other oxidizing agents,
• Propellants such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air,
• - antioxidants,
• - preservatives and
• - Reducing agents such as sodium sulfite, sodium dithionite or ascorbic acid

contain.

Regarding others optional components and the amounts of these components used expressly to the relevant manuals known to those skilled in the art, e.g. B. Kh. Schrader, Basics and formulations of cosmetics, 2nd edition, Hüthig Buch Verlag, Heidelberg, 1989.

The agents according to the invention preferably contain the dye precursors in a suitable aqueous alcoholic or aqueous-alcoholic Carrier. For the purpose of coloring hair are such carriers, for example Creams, emulsions, gels or also surfactant-containing foaming solutions, such as shampoos, foam aerosols or other preparations, the for are suitable for use on the hair. But it is also conceivable the dye precursors in a powder or tablet formulation to integrate.

For the purposes of the present invention, aqueous-alcoholic solutions are understood to mean aqueous solutions containing 3 to 70% by weight of a C ₁ -C ₄ alcohol, in particular ethanol or isopropanol. The agents according to the invention can additionally contain other organic solvents, such as methoxybutanol, benzyl alcohol, ethyl diglycol or 1,2-propylene glycol. All water-soluble organic solvents are preferred.

in the Different packaging forms are within the scope of the present invention conceivable.

in the Framework of a first embodiment components (a), (b) and (c) are each in separate preparations assembled and only with each other immediately before use mixed.

in the Framework of a second embodiment can components (a) and (b) are assembled together. In In this case, a preparation is made just before use containing component (c) added.

in the Framework of a third embodiment the present invention, it is also conceivable that the components (b) and (c) are made up together and only immediately component (a) is added before use.

Conveniently, the different preparations are just before hair coloring mixed. The application temperatures can range between 20 and 70 ° C, preferably between 20 and 35 ° C, lie. The application preparation preferably has a pH from 6.5 to 10.5, in particular from 6.5 to 8. After an exposure time of about 30 minutes, the hair dye is rinsed off the one to be colored Hair removed. Washing with a shampoo is not necessary if one high tenside carrier, z. B. a coloring shampoo, was used.

In a further embodiment In the present invention it may be preferred to use the agents, in particular the enzyme preparation, which may be made up separately, is free of, for example, antioxidants, anionic surfactants and / or Formulate reducing agents as this affects the action of the enzymes can block.

• (a) mindestens ein Farbstoffvorprodukt,
• (b) mindestens ein Enzym vom Typ der Manganoxidasen sowie
• (c) mindestens eine Verbindung, die Mn-Ionen enthält, eingesetzt wird.

A second object of the present invention is a process for dyeing keratinous fibers, which comprises an agent

• (a) at least one dye precursor,
• (b) at least one enzyme of the manganese oxidase type and
• (c) at least one compound containing Mn ions is used.

On third object of the present invention is the use of an enzyme of the manganese oxidase type for the oxidative staining of keratin Fibers.

The following formulations are particularly suitable for coloring with the enzyme system according to the invention: Colorant A Fatty alcohol mixture C ₁₂ -C ₁₈ 5.25 Eumulgin ^® B2 0.4 Plantacare ^® 1200 3.0 Dehyton ^® K 2.5 ammonium sulfate 0.5 Natrosol ^® 250 HR 1.0 4-Amino-2 - ((diethylamino) methyl) phenol dihydrochloride 2.67 2-amino-3-hydroxypyridine 1.1 Ammonia (25% in water) ad pH 8.5 water ad 100 Colorant B Fatty alcohol mixture C ₁₂ -C ₁₈ 5.25 Eumulgin ^® B2 0.4 Plantacare ^® 1200 3.0 Dehyton ^® K 2.5 ammonium sulfate 0.5 Natrosol ^® 250 HR 1.0 4-Amino-2-aminomethyl-phenol dihydrochloride 0,002 2-amino-3-hydroxypyridine 0,004 3-methyl-4-aminophenol 0,007 1,3-bis (2,4-diaminophenoxy) -propane tetrahydrochloride 0.0005 p-toluenediamine sulphate 0.06 resorcinol 0.01 3-Amino-2,4-dichlorphenolhydrochlorid 0,008 3-aminophenol 0,002 4-chlororesorcinol 0.01 Ammonia (25% in water) ad pH 8.5 water ad 100 Colorant C Fatty alcohol mixture C _{1 2} -C ₁₈ 5.25 Eumulgin ^® B2 0.4 Plantacare ^® 1200 3.0 Dehyton ^® K 2.5 ammonium sulfate 0.5 Natrosol ^® 250 HR 1.0 4-amino-2-chlorophenol 0.8 2-amino-3-hydroxypyridine 0.1 3-methyl-4-aminophenol 0.3 5-amino-2-methylphenol 0.07 resorcinol 0.2 3-aminophenol 0.2 1- (2'-hydroxyethyl) -2,5-diaminobenzolsulfat 0.7 4-methyl 0.1 5,6-dihydroxyindole 0.05 Monoethanolamine ad pH 7 water ad 100 Colorant D Fatty alcohol mixture C _{1 2} -C ₁₈ 5.25 Eumulgin ^® B2 0.4 Plantacare ^® 1200 3.0 Dehyton ^® K 2.5 ammonium sulfate 0.5 Natrosol ^® 250 HR 1.0 4-amino-phenol 0.49 4-amino-3-methylphenol 0.55 2-amino-3-hydroxypyridine 1.0 p-toluenediamine sulphate 0.2 6-hydroxyindole 0.1 5 - ((2'-hydroxyethyl) amino) -2-methylphenol 0.1 1,2,3,4-tetrahydro-6-nitroquinoxaline 0.05 HC Yellow 5 0.03 HC Red 1 0.02 sodium hydroxide ad pH 8.5 water ad 100 Colorant E Fatty alcohol mixture C ₁₂ -C ₁₈ 5.25 Eumulgin ^® B2 0.4 Plantacare ^® 1200 3.0 Dehyton ^® K 2.5 ammonium sulfate 0.5 Natrosol ^® 250 HR 1.0 4-Amino-2-aminomethyl-phenol dihydrochloride 2.0 2-methylamino-3-amino-6-methoxypyridine 2.25 arginine ad pH 7.5 water ad 100 Colorant F Fatty alcohol mixture C ₁₂ -C _{1 8} 5.25 Eumulgin ^® B2 0.4 Plantacare ^® 1200 3.0 Dehyton ^® K 2.5 ammonium sulfate 0.5 Natrosol ^® 250 HR 1.0 4-Amino-2-aminomethyl-phenol dihydrochloride 0,017 2-methylamino-3-amino-6-methoxypyridine 0,002 1- (2'-hydroxyethyl) -2,5-diaminobenzolsulfat 0.03 1-naphthol 0.02 2-methyl 0.0006 lysine ad pH 7 water ad 100 Colorant G Fatty alcohol mixture C ₁₂ -C ₁₈ 5.25 Eumulgin ^® B2 0.4 Plantacare ^® 1200 3.0 Dehyton ^® K 2.5 ammonium sulfate 0.5 Natrosol ^® 250 HR 1.0 4-Amino-2 - ((diethylamino) methyl) phenol dihydrochloride 0.1 2-methylamino-3-amino-6-methoxypyridine 0,002 3-methyl-4-aminophenol 0.07 2,4,5,6-tetra-sulfate 1.0 p-toluenediamine sulphate 1.1 3-aminophenol 0,006 resorcinol 0.11 2-methyl 0.54 2,7-dihydroxynaphthalene 0.032 2-amino-3-hydroxypyridine 0.4 4-amino-2-nitro-diphenylamine-2'-carboxylic acid 0.1 Ammonia, (25% in water) ad pH 7 water ad 100 Colorant H Fatty alcohol mixture C ₁₂ -C ₁₈ 5.25 Eumulgin ^® B2 0.4 Plantacare ^® 1200 3.0 Dehyton ^® K 2.5 ammonium sulfate 0.5 Natrosol ^® 250 HR 1.0 4-amino-2-chlorophenol dihydrochloride 1.0 2-methylamino-3-amino-6-methoxypyridine 1.7 2-amino-4-nitro-6-chlorophenol 0.05 HC Red BN 0.2 5,6-Dihydroxyindolin hydrobromide 0.1 Ammonia (25% in water) ad pH 7 water ad 100 Colorant I Fatty alcohol mixture C ₁₂ -C ₁₈ 5.25 Eumulgin ^® B2 0.4 Plantacare ^® 1200 3.0 Dehyton ^® K 2.5 ammonium sulfate 0.5 Natrosol ^® 250 HR 1.0 4-Amino-2 - ((diethylamino) methyl) phenol dihydrochloride 1.25 4-Amino-2-aminomethyl-phenol dihydrochloride 1.0 5-amino-2-methyl-phenol 1.23 Ammonia (25% in water) ad pH 7 water ad 100 Colorant J Fatty alcohol mixture C ₁₂ -C ₁₈ 5.25 Eumulgin ^® B2 0.4 Plantacare ^® 1200 3.0 Dehyton ^® K 2.5 ammonium sulfate 0.5 Natrosol ^® 250 HR 1.0 4-Amino-2 - ((diethylamino) methyl) phenol dihydrochloride 0.5 Bis- (2-hydroxy-5-aminophenyl) methane 0.4 5-amino-2-methylphenol 0.55 p-toluenediamine sulphate 0.3 p-Phenylenediamine dihydrochloride 0.2 resorcinol 0.07 2,7-dihydroxynaphthalene 0.09 2-methyl 0.07 o-aminophenol 0.03 5,6-Dihydroxyindolin hydrobromide 0.05 Ammonia (25% in water) ad pH 8.5 water ad 100 Colorant K Fatty alcohol mixture C ₁₂ -C ₁₈ 5.25 Eumulgin ^® B2 0.4 Plantacare ^® 1200 3.0 Dehyton ^® K 2.5 ammonium sulfate 0.5 Natrosol ^® 250 HR 1.0 4-Amino-2-aminomethyl-phenol dihydrochloride 0.02 5-amino-2-methylphenol 0.03 3-methyl-4-aminophenol 0.01 2,4,5,6-tetra-sulfate 0.8 p-toluenediamine sulphate 0.09 3-aminophenol 0,004 resorcinol 0.04 2-methyl 0.22 2,7-dihydroxynaphthalene 0.3 4-amino-2-nitro-diphenylamine-2'-carboxylic acid 0.15 1,2,3,4-tetrahydro-6-nitroquinoxaline 0.25 Ammonia (25% in water) ad pH 7 water ad 100 Colorant L Fatty alcohol mixture C _{1 2} -C ₁₈ 5.25 Eumulgin ^® B2 0.4 Plantacare ^® 1200 3.0 Dehyton ^® K 2.5 sodium 0.1 ammonium sulfate 0.5 Natrosol ^® 250 HR 1.0 4-Amino-2-aminomethyl-phenol dihydrochloride 1.06 4-aminophenol 0.55 5-amino-2-methylphenol 0.74 4-hydroxyindole 0.1 1,3-bis (2,4-diaminophenoxy) -propantetrahydrochlorid 0.3 2-methylamino-3-amino-6-methoxy-pyridine dihydrochloride 0.1 Ammonia (25% in water) ad pH 7 water ad 100 Colorant M Hydrenol ^® D 8.0 C12-C18 fatty alcohol 2.0 Akypo Soft ^® 45 NV 10.0 Eumulgin ^® B1 0.5 Eumulgin ^® B2 0.5 5-amino-2-methylphenol 0.02 3-Amino-2-chloro-6-methylphenol 0.36 1,3-bis (2 ', 4'-diaminophenoxy) propane tetrahydrochloride 0.0002 3-methyl-4-aminophenol 0.02 4-Amino-2-aminomethyl-phenol dihydrochloride 0.40 p-toluenediamine sulphate 0.34 N, N-bis (2-hydroxyethyl) -p-phenylenediamine sulfate 0.48 resorcinol 0.33 m-aminophenol 0.001 2-amino-3-hydroxypyridine 0.009 ammonium chloride 0.3 Ammonia (25% in water) ad pH 7 water ad 100 Colorant N Hydrenol ^® D 8.0 C12-C18 fatty alcohol 2.0 Akypo Soft ^® 45 NV 10.0 Eumulgin ^® B1 0.5 Eumulgin ^® B2 0.5 m-aminophenol 0.005 3-amino-2-methylamino-6-methoxypyridinhydrochlorid 0,002 2-amino-3-hydroxypyridine 0.24 2,7-dihydroxynaphthalene 0.02 2-methyl 0.6 p-toluenediamine sulphate 0.73 resorcinol 0.13 2,6-dihydroxy-3,4-dimethyl-pyridine 0.1 2,4,5,6-tetra 1.3 5-amino-2-methylphenol 0.03 5- (β-hydroxyethyl) amino-2-methylphenol 0.3 2-nitro-4-aminodiphenylamine-2'-carboxylic acid 0.1 ammonium chloride 0.4 perfume oil 0.2 Ammonia (25% in water) ad pH 7 water ad 100 Colorant O Hydrenol ^® D 8.0 C12-C18 fatty alcohol 2.0 Akypo Soft ^® 45 NV 10.0 Eumulgin ^® B1 0.5 Eumulgin ^® B2 0.5 2-methyl 0.48 p-toluenediamine sulphate 0.6 1- (2'-hydroxyethyl) -2,5-diaminobenzene 0.6 resorcinol 0.21 2,6-dihydroxy-3,4-dimethyl-pyridine 0.66 2,4,5,6-tetra 3.0 3-methyl-4-aminophenol 0.16 3-Amino-2-chloro-6-methyl-phenol 0.11 5-amino-2-methylphenol 0.03 1.5 Diyhdroxynaphthalin 0,002 ammonium chloride 0.2 Mirapol ^® A-15 1.5 perfume oil 0.2 histidine ad pH 8 water ad 100 Colorant P Hydrenol ^® D 5.0 C12-C18 fatty alcohol 2.0 Texapon ^® NSO 3.0 ammonium sulfate 0.5 5-amino-2-methylphenol 0.56 3-methyl-4-aminophenol 0,055 p-toluenediamine sulphate 0.65 resorcinol 0.14 4-aminophenol hydrochloride 0.6 4-amino-2-nitro-diphenylamino-2'-carboxylic acid 0.05 6-nitro-1,2,3,4-tetrahydroquinoxalin 0.1 Ammonia (25% in water) ad pH 8 water ad 100 Colorant Q Hydrenol ^® D 5.0 C12-C18 fatty alcohol 2.0 Texapon ^® NSO 3.0 ammonium sulfate 0.5 1,3-bis (2 ', 4'-diaminophenoxy) propane tetrahydrochloride 0,003 p-toluenediamine sulphate 0.033 resorcinol 0.0055 4-aminophenol hydrochloride 0,014 2-amino-3-hydroxypyridine 0.0035 Ammonia (25% in water) ad pH 8 water ad 100

The commercial products used in the examples have the following meanings: Akypo Soft 45 NV ^® Lauryl alcohol-4.5-EO-acetic acid sodium salt (at least 21% active substance content; INCI name: Sodium Laureth-6 carboxylate) (Chem-Y) Dehyton ^® K N, N-Dimethyl-N- (C _8-18 cocosamidopropyl) ammonium acetobetaine (approx. 30% active substance; INCI name: Aqua (Water), Cocamidopropyl Betaine) (Cognis) Eumulgin ^® B1 Cetylstearyl alcohol with approx. 12 EO units (INCI name: Ceteareth-12) (Cognis Eumulgin ^® B2 Cetylstearyl alcohol with approx. 20 EO units (INCI name: Ceteareth-20) (Cognis) HC Red BN 4- (3-hydroxypropyl) amino-3-nitrophenol (Clariant) Hydrenol ^® D C _{16-1 8} fatty alcohol (INCI name: Cetearyl alcohol) (Cognis) Mirapol ^® A 15 Poly [N- (3- (dimethylammonium) propyl] -N '- [3-ethylenoxyethylene dimethylammonium) propyl] urea dichloride (approx. 64% solids in water; INCI name: Polyquaternium-2) (Rhodia) Natrosol ^® 250 HR Hydroxyethylcellulose (INCI name: Hydroxyethylcellulose) (Hercules) Plantacare ^® 1200 C _{12 1 6} 1.4 fatty alcohol-glucoside (approximately 50-53% active substance content; INCI name: Lauryl Glucoside, Aqua (Water)) (Cognis) Texapon ^® NSO Lauryl ether sulfate, sodium salt (approx. 27.5% active substance; INCI name: Sodium Laureth Sulfate) (Cognis)

Claims (18)

Coloring agents keratinic fibers containing in a cosmetically acceptable carrier (A) at least one dye intermediate, (b) at least one enzyme of the manganese oxidase type and (c) at least one connection, which contains Mn ions. Agent according to claim 1, characterized in that the manganese oxidase from a microorganism selected from Leptothrix discophora, Bacillus SG-1 and Pseudomonas sp. can be won. Agent according to one of claims 1 or 2, characterized in that that it is the manganese oxidase in an amount of 0.0001 and 5 milligrams contains active manganese oxidase per 100g application preparation. Agent according to one of claims 1 to 3, characterized in that that it contains compounds as component (c), the manganese ions of the oxidation state Contain +2 or +3. Agent according to claim 4, characterized in that it contains, as component (c) compounds, the manganese ions of the oxidation state +2 included. Agent according to one of claims 1 to 5, characterized in that that it contains component (c) in such amounts that the resulting application preparation has a manganese ion concentration from 0.005 mM to 50 mM. Agent according to one of claims 1 to 6, characterized in that that there is still at least one complexing agent for the manganese ion contains. Agent according to claim 7, characterized in that the complexing agent is selected is from formate anions, lactate anions, malonate anions or the oxalate anions. Agent according to one of claims 1 to 8, characterized in that that there is at least one developer component as a dye precursor contains. Agent according to one of claims 1 to 9, characterized in that that there is at least one coupler component as a dye precursor contains. Agent according to one of claims 1 to 10, characterized in that that there is at least one indole and / or indoline derivative as a dye precursor contains. Agent according to one of claims 1 to 11, characterized in that that it contains at least one substantive dye. Agent according to one of claims 1 to 12, characterized in that that it still contains at least one surfactant. Agent according to claim 13, characterized in that it contains a nonionic or an amphoteric surfactant. Agent according to one of claims 13 or 14, characterized in that that there is a surfactant combination of at least one anionic Surfactant with at least one amphoteric surfactant and / or with at least one contains a nonionic surfactant. Agent according to one of claims 1 to 15, characterized in that that it contains an alkalizing agent. Coloring process keratin fibers, characterized in that an agent after one of the claims 1 to 16 is applied to the fibers and after a contact time rinsed off again becomes. Use of an enzyme of the manganese oxidase type for oxidative coloring keratin fibers.