EP1267811A1 - Encymatical colorant - Google Patents

Abstract

The present invention relates to agents for colouring keratinic fibres which contain at least one colorant intermediate product and at least one enzyme of the type of the oxidoreductases in a cosmetically acceptable carrier. Said enzyme is present as a homodimer in a solution under non-denaturing conditions. The inventive agents are characterised by the good colouring ability thereof and by the action thereof which is gentle to the hair.

Description

 "Enzymatic Colorant"

The present invention relates to agents for dyeing keratin fibers which contain at least one enzyme of the oxidoreductase type which is present as a homodimer in solution, to corresponding processes for dyeing keratin fibers and to the use of an enzyme of the oxidoreductase type which is present in solution as a homodimer , for oxidative hair coloring.

Today human hair is treated in a variety of ways with hair cosmetic preparations. These include cleaning the hair with shampoos, care and regeneration with rinses and cures, as well as bleaching, dyeing and shaping the hair with colorants, tinting agents, waving agents and styling preparations. Means for changing or shading the color of the head hair play an outstanding role.

Coloring agents or tinting agents which contain so-called direct draws as the coloring component are usually used for temporary dyeings. These are dye molecules that attach directly to the hair and do not require an oxidative process to form the color. These dyes include, for example, henna, which is known from antiquity for coloring body and hair. These dyeings are generally significantly more sensitive to shampooing than the oxidative dyeings, so that a much undesired shift in nuances or even a visible "discoloration" occurs much more quickly.

So-called oxidation dyes are used for permanent, intensive dyeings with appropriate fastness properties. 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 from atmospheric oxygen with one another or with coupling with one or more coupler components the actual dyes. The oxidation coloring agents are characterized by excellent, long-lasting coloring results. A mixture of a larger number of oxidation dye precursors usually has to be used for natural-looking dyeings; in many cases direct dyes are still used for shading.

In principle, the oxidative development of the coloring can take place with atmospheric oxygen. However, a chemical oxidizing agent is preferably used. Persulfates, chlorites and in particular hydrogen peroxide or their adducts with urea, melamine and sodium borate are suitable as oxidizing agents. An approximately 2-9% aqueous hydrogen peroxide solution is usually used. Under the influence of such high concentrations of oxidizing agent, the keratinic fibers can be damaged, especially if they are already permanently corrugated or bleached, and in rare cases these high concentrations can also cause skin irritation.

A key approach to solving this problem is to reduce the oxidant concentration. In the past, therefore, on the one hand, there was a search for dye precursors which, due to their chemical structure, can already be oxidized by small amounts of hydrogen peroxide or by atmospheric oxygen. On the other hand, the use of enzymes as biocatalysts has been proposed which can catalyze the desired oxidation process with very little or no hydrogen peroxide only in the presence of atmospheric oxygen.

German published patent application DE-OS-21 55 390 describes an enzyme-activated, oxidative hair dyeing process in which small amounts of H ₂ O _{2 are used} in combination with a peroxidase. EP-AI-0 310 675 also discloses enzymatic hair treatment compositions which contain at least one two-electron-reducing oxidase which uses oxygen as an acceptor. EP-B1-0 548 620 describes enzymatic hair colorants in which the oxidation of the dye precursors is catalyzed by using a peroxidase. Finally be EP-A2-0 795 313 describes enzymatic hair colorants 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, poorer results are achieved in particular with regard to the intensity, gloss and fastness properties of the dyeings.

The present invention is therefore based on the object of providing coloring agents for keratin fibers which enable gentle fiber treatment and at the same time ensure excellent dyeing performance.

A first subject of the present invention are therefore agents for dyeing keratin fibers which contain in a cosmetically acceptable carrier at least one dye precursor and at least one enzyme from the class of the oxidoreductases, which is present as a homodimer in solution under non-denaturing conditions.

According to the invention, keratin fibers are to be understood as furs, wool, feathers and in particular human hair.

According to the invention, homodimers are enzymes that consist of two identical subunits. The type of connection between the subunits is of no importance according to the invention. For example, the linkage can be achieved according to the invention by means of hydrogen bonds, disulfide bonds, electrostatic interactions or complex formation with metal ions.

According to the invention, non-denaturing conditions are understood to mean conditions in which the enzyme is present in its native conformation, that is to say as under physiological conditions. According to the invention, oxidoreductases which are present as homodimers in solution under non-denaturing conditions are also the enzymes which, under these conditions, also form agglomerates from more than two subunits, for example from 5 to 8 subunits, in addition to homodimers.

Although in principle all oxidoreductases which are present as homodimers in solution under non-denaturing conditions are suitable according to the invention, the subgroup of the phenol-oxidizing enzymes is particularly preferred.

Furthermore, those enzymes from the class of oxidoreductases which are present as homodimers in aqueous solution under non-denaturing conditions are preferred.

According to the invention, preferred enzymes from the class of the oxidoreductases are the ascorbate oxidases (EC 1.10.3.3). These special phenol oxidases oxidize their substrates by transferring electrons to atmospheric oxygen to form water. This class of enzymes has a high affinity for L-ascorbate, which is oxidized to dehydroascorbate. Ascorbate oxidases occur in various plants and plant cell cultures. The plants with the highest ascorbate oxidase content found so far are the cucumber (Cucumis sativä) and the zucchini (Cucurbita pepo medullosd). In addition, ascorbate oxidases in pumpkins (Cucurbita species), Cucurbita pepo condensa, cabbage (Brassica oleracea), mustard (Sinapis alba), Myrothecium verrucaria, Cucurbita moschata and Cucurbita maxima were detected. Furthermore, it is also preferred according to the invention to use ascorbate oxidases which are obtained from suitable cell culture supernatants.

Ascorbate oxidases are commercially available. For example, Roche-Diagnostics offers an ascorbate oxidase from Cucurbita species. The activity of ascorbate oxidase is defined according to the invention in such a way that one unit [1U] corresponds to the amount of ascorbate oxidase contained in a phosphate buffer solution (KH ₂ PO, 0.1 mol / 1; Na ₂ HPO ₄ , ₄ mmol / l ; EDTA, 0.5mmol / l) catalyzes the oxidation of lμmol L-ascorbic acid within one minute at pH 5.6 and 25 ° C (according to the definition of Commercial products from Röche Diagnostics). The detection is done spectroscopically based on the decrease in absorption at 245 nm.

The enzyme can be incorporated into the colorant itself; but it is preferably made up separately from the dye precursors and added to the colorant only immediately before use.

The enzyme is preferably in an amount of 0.0001-2% by weight, in particular in an amount of 0.0001-1% by weight, very particularly preferably in an amount of 0.0005-1% by weight, each based on the amount of protein in the enzyme and the entire colorant used.

With regard to the dye precursors 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

• contain precursors of nature-analogous dyes, such as indole and indoline derivatives, and mixtures of representatives of these groups.

Primary aromatic amines with a further, in the para or ortho position, free or substituted hydroxy or amino group, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazole derivatives and 2,4,5,6-tetraaminopyrimidine and the like are usually used as developer components Derivatives used.

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

in which

G ¹ represents a hydrogen atom, a Ci to C ₄ alkyl radical, a Ci to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a (Ci to C ₄ ) alkoxy (C! - to C ₄ ) -alkyl radical, a 4'-aminophenyl radical or a C 1 -C ₄ -alkyl radical which is substituted by a nitrogen-containing group, a phenyl or a 4'-aminophenyl radical;

G ² represents a hydrogen atom, a Cr to C ₄ alkyl radical, a Cp to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a (Cr to C ₄ ) alkoxy- (Cι- to C ₄ ) -alkyl radical or a C 1 -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 to C ₄ alkyl radical, a Ci to C ₄ -Monohydroxyalkylradikal, a CJ to C ₄ -Hydroxyalkoxyradikal, a C to C ₄ -acetylaminoalkoxy radical, a C to C mesylaminoalkoxy radical or a Cr to C ₄ carbamoylaminoalkoxy radical; G ⁴ represents a hydrogen atom, a halogen atom or a Cr to C ₄ -

Alkyl radicals or when G ³ and G ^{4 are} in the ortho position to one another, they can together form a bridging α, ω-alkylenedioxo group, such as, for example, an ethylenedioxy group.

Examples of the d- to C-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. Cr to C ₄ alkoxy radicals preferred according to the invention are, for example, a methoxy or an ethoxy group. Furthermore, as preferred examples of a Cr to C ₄ hydroxyalkyl group, a hydroxy methyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group. A 2-hydroxyalkyl group is particularly preferred. 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 (II) are, in particular, the amino groups, Cr to C ₄ monoalkylamino groups, Cj to C ₄ dialkylamino groups, Cr to C ₄ trialkylammonium groups, Cr to C monohydroxyalkylamino groups, imidazolinium and ammonium.

Particularly preferred p-phenylenediamines of the formula (I) 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- (ß-hydroxyethyl) -p-phenylenediamine, 4-N, N-bis- (ß-hydroxyethyl) amino-2- methylaniline, 4-N, N-bis (ß-hydroxyethyl) amino-2-chloroaniline, 2- (ß-hydroxyethyl) -p-phenylenediamine, 2-fluoro-p-phenylenediamine, 2-isopropyl-p-phenylenediamine, N - (ß-hydroxypropyl) -p-phenylenediamine, 2-hydroxymethyl-p-phenylenediamine, N, N-dimethyl-3-methyl-p-phenylenediamine, N, N- (ethyl, -ß-hydroxyethyl) -p-phenylenediamine, N- (ß, γ-dihydroxypropyl) -p-phenylenediamine, N- (4'-aminophenyl) -p-phenylenediamine, N-phenyl-p-phenylenediamine, 2- (ß-hydroxyethyloxy) -p-phenylenediamine, 2- ( ß

Acetylaminoethyloxy) -p-phenylenediamine, N- (ß-methoxyethyl) -p-phenylenediamine and 5,8-diaminobenzo-l, 4-dioxane and their physiologically tolerable salts.

P-Phenylenediamine derivatives of the formula (I) which are particularly preferred according to the invention are p-phenylenediamine, p-toluenediamine, 2- (β-hydroxyethyl) -p-phenylenediamine and N, N-bis- (β-hydroxyethyl) -p-phenylenediamine.

It can further be preferred according to the invention to use as developer component compounds which contain at least two aromatic nuclei which are substituted with amino and / or hydroxyl groups. 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 (II) 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 Cr to C ₄ alkyl radical, by a Cr to C ₄ hydroxyalkyl radical and / or by a bridge Y, 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 may be interrupted or terminated by one or more nitrogen-containing groups and / or one or more heteroatoms such as oxygen, sulfur or nitrogen atoms and possibly can be substituted by one or more hydroxyl or Cr to C ₈ alkoxy radicals, G ⁵ and G ⁶ independently represent a hydrogen or halogen atom, a Cr to C alkyl radical, a Cr to C monohydroxyalkyl radical, a C ₂ - to C ₄ - polyhydroxyalkyl radical, a Cr to C ₄ aminoalkyl radical or a direct connection to the bridging 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 Cr to C ₄ alkyl radical, with the proviso that the compounds of the formula (II) contain only one bridging Y per molecule. According to the invention, the substituents used in formula (II) are defined analogously to the above statements.

Preferred dinuclear developer components of the formula (II) are in particular: N, N'-bis (ß-hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diamino-propanol, N, N ' -bis- (ß-hydroxyethyl) -N, N'-bis- (4'-aminophenyl) -ethylenediamine, N, N'-bis- (4-aminophenyl) -tetramethylene-diamine, N, N'-bis- (ß- Hydroxyethyl) -N, N'-bis (4-aminophenyl) tetramethylene diamine, N, N'-bis (4-methylaminophenyl) tetramethylene diamine, N, N'-bis (ethyl) -N, N ' -bis (4'-amino, 3 ^, -methylphenyl) -ethylenediamine, 1,8-bis- (2,5-diamino-phenoxy) -3,5-dioxaoctane, bis- (2-hydroxy-5-aminophenyl) - methane, 1, 4-bis (4-aminophenyl) diaza cycloheptane and l, 10-bis (2,5-diaminophenyl) -1, 4,7,10-tetraoxadecane and their physiologically tolerable salts.

Very particularly preferred dinuclear developer components of the formula (II) are N, N'-bis- (β-hydroxyethyl) -N, N'-bis- (4 ^, -aminophenyl) -1,3-diamino-propanol, bis- (2nd - hydroxy-5-aminophenyl) methane, N, N'-bis (4-aminophenyl) -l, 4-diazacycloheptane and l, 10-bis (2,5-diaminophenyl) -l, 4,7,10 -tetraoxadecan or one of its physiologically acceptable salts.

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 (III) are particularly preferred

in which:

G ¹³ represents a hydrogen atom, a halogen atom, a Cr to C ₄ alkyl radical, a Cr to C monohydroxyalkyl radical, a (Cr to C) alkoxy (Cr to C) alkyl radical, a Cr to C ₄ aminoalkyl radical, a hydroxy (Cr to C) alkyl amino radical, a Cr to C ₄ hydroxyalkoxy radical, a Cr to C ₄ -

Hydroxyalkyl- (Cι-to C ₄ ) aminoalkyl radical or a (Di-Cr to C -

Alkylamino) - (Cr to C ₄ ) -alkyl radical, and

G ¹⁴ represents a hydrogen or halogen atom, a Cr to C ₄ alkyl radical

Cr to C monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a (Cr to C ₄ ) alkoxy (Cr to C ₄ ) alkyl radical, a Cr to C ₄ -

Aminoalkyl radical or a Cr to C ₄ cyanoalkyl radical,

G ¹⁵ represents hydrogen, a Cr to C ₄ alkyl radical, a Cr to C monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a phenyl radical or a benzyl radical, and

G ¹⁶ represents hydrogen or a halogen atom.

According to the invention, the substituents used in formula (III) are defined analogously to the above statements.

Preferred p-aminophenols of the formula (III) are in particular p-aminophenol, N-methyl-p-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 2-hydroxymethylamino-4 -amino-phenol, 4-amino-3-hydroxymethylphenol, 4-amino-2- (2-hydroxyethoxy) phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2 -methoxymethyl-phenol, 4-amino-2-aminomethylphenol, 4-amino-2- (ß-hydroxyethyl-aminomethyl) -phenol, 4-amino-2-fluorophenol, 4-amino-2-chlorophenol, 2,6-dichloro -4- aminophenol, 4-amino-2 - ((diethylamino) methyl) phenol and their physiologically tolerable salts.

Very particularly preferred compounds of the formula (III) are p-aminophenol, 4-amino-3-methylphenol, 4-amino-2-chlorophenol, 4-amino-2,6-dichlorophenol, 4-amino-2-aminomethylphenol and 4- amino-2 - ((diethylamino) methyl) phenol.

Furthermore, the developer component can be selected from o-aminophenol and its derivatives, such as, for example, 2-amino-4-methylphenol or 2-amino-4-chlorophenol. Furthermore, the developer component can be selected from heterocyclic developer components, such as, for example, the pyridine, pyrimidine, pyrazole, pyrazole-pyrimidine derivatives and their physiologically tolerable salts.

Preferred pyridine derivatives are, in particular, the compounds described in patents GB 1 026 978 and GB 1 153 196, such as 2,5-diamino-pyridine, 2- (4-methoxyphenyl) amino-3-aminopyridine, 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 German patent DE 23 59 399, Japanese laid-open patent publication JP-A2-02 / 019576 or in published patent application WO 96/15765, 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 38 43 892, DE 41 33 957 and published publications WO 94/08969, WO 94/08970, EP 0 740 931 and DE 195 43 988, such as 4.5 -Diamino-l-methylpyrazole, 4,5-diamino-l- (ß-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, l-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-l-methylpyrazole, 4,5-diamino-1-tert.-butyl-3-methylpyrazole, 4, 5-diamino-1 - (ß-hydroxyethyl) -3-methylpyrazole, 4,5-diamino-l-ethyl-3-methylpyrazole, 4,5-diamino-l-ethyl-3- (4'-methoxyphenyι) -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-l-isopropylpyrazole, 4-amino-5- (2'- amJnoethyl) amino- l, 3-dimethylpyrazole, 3,4,5-triaminopyrazole, 1-methyl-3, 4,5-triaminopyrazole, 3,5-diamino-l-methyl-4-methylaminopyrazole and 3,5-diamino-4 (ß- hydroxyethyl) amino-1-methylpyrazole. Preferred pyrazole-pyrimidine derivatives are, in particular, the derivatives of pyrazole- [1,5-a] -pyrimidine of the following formula (IV) and its tautomeric forms, provided that there is a tautomeric equilibrium:

in which:

G, 17,, G-, 1 ¹ 8 ⁰ ,, G-, 1 ^ι 9 ^y . and G ²⁰ independently represent a hydrogen atom, a C 1 to C ₄ alkyl radical, an aryl radical, a Cr to C ₄ hydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical a (Cr to C ₄ ) alkoxy - (C 1 -C ₄ ) -alkyl radical, a C to C ₄ -aminoalkyl radical which can optionally be protected by an acetyl-ureide or sulfonyl radical, a (Cr to C) -alkylamino- (Cr to C ₄ ) -alkyl radical, a di - [(Cr to C ₄ ) alkyl] - (Cr to C) aminoalkyl radical, where the dialkyl radicals optionally form a carbon cycle or a heterocycle with 5 or 6 chain links, a Cr to C ₄ - hydroxyalkyl - or a di- (Cr to C ₄ ) - [hydroxyalkyl] - (Cr to C ₄ ) aminoalkyl radical, the X radicals independently of one another represent a hydrogen atom, a Cr bis

C ₄ - alkyl radical, an aryl radical, a Cr to C -Hydroxyalkyladikal, a C ₂ - to C - Polyhydroxyalkylradikal, a Cr to C ₄ - aminoalkyl radical, a (Cr to _C4) -Alls lamino- (Cr-C) -alkyl radical, a di - [(Cr to C ₄ ) alkyl] - (C \ - to C ₄ ) aminoalkyl radical, the dialkyl radicals optionally forming a carbon cycle or a heterocycle with 5 or 6 chain links, a Cr to C ₄ -Hydroxyalkyl- or a di- (Cj- to C ₄ -hydroxyalkyl) - aminoalkyl radical, an amino radical, a Cr to C ₄ alkyl or di- (Cr 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 is 0 and the groups NG ¹⁷ G ¹⁸ and NG ¹⁹ G ²⁰ occupy the positions (2,3); (5,6); (6,7); (3.5) or (3.7); if p + q is 1, n is 1, and the groups NG ^I7 G ¹⁸ (or

NG ¹⁹ G ²⁰ ) and the group OH occupy positions (2,3); (5,6); (6,7); (3.5) or

(3.7);

According to the invention, the substituents used in formula (IV) are defined analogously to the above statements.

If the pyrazole- [1,5-a] pyrimidine of the formula (IV) above contains a hydroxyl 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:

Among the pyrazole- [1,5-a] -pyrimidines of the above formula (IV) one can mention in particular:

Pyrazole- [1,5-a] pyrimidine-3,7-diamine;

2,5-dimethyl pyrazole- [1,5-a] pyrimidine-3,7-diamine;

Pyrazole (l, 5-a] pyrimidine-3,5-diamine;

2,7-dimethyl pyrazole- [1,5-a] pyrimidine-3,5-diamine;

3-amino pyrazol- [1,5-a] pyrimidin-7-ol;

3-amino pyrazol- [1,5-a] pyrimidin-5-ol;

2- (3-amino-pyrazole- [1,5-a] -pyrirnidm-7-ylamino) -ethanol; 2- (7-amino pyrazol- [1,5-a] pyrimidin-3-ylamino) ethanol;

2 - [(3-amino pyrazol- [l, 5-a] pyrimidin-7-yl) - (2-hydroxyethyl) amino] ethanol;

2 - [(7-amino pyrazol- [l, 5-a] pyrimidin-3-yl) - (2-hydroxyethyl) amino] ethanol;

5,6-dimethyl pyrazole- [1,5-a] pyrimidine-3,7-diamine;

2,6-dimethyl pyrazole- [1,5-a] pyrimidine-3,7-diamine;

2,5, N7, N7-tetramethylpyrazole- [1,5-a] -pyrimidine-3,7-diamine; as well as their physiologically acceptable salts and their tautomeric forms when a tautomeric equilibrium is present.

The pyrazole [1,5-a] pyrimidines of the above formula (IV) can be prepared as described in the literature by cyclization starting from an aminopyrazole or from hydrazine.

M-Phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenol derivatives are generally used as coupler components. Suitable coupler substances are, in particular, 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxy-naphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, l -Phenyl-3-methyl-pyrazolone-5, 2,4-dichloro-3-aminophenol, 1,3-bis (2,4-diaminophenoxy) propane, 2-chloro-resorcinol, 4-chloro-resorcinol, 2 -Chlor-6-methy 1-3 -aminophenol, 2-amino-3-hydroxypyridine, 2-methylresorcinol, 5-methylresorcinol and 2-methyl-4-chloro-5-aminophenol.

Coupler components preferred according to the invention are: m-aminophenol and its derivatives such as 5-amino-2-methylphenol, 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-cyclopenty 1-3 -aminophenol, 1,3-dihydroxy-5- (methylamino) -benzene, 3- (ethylamino) -4-methylphenol and 2,4-dichloro -3- aminophenol, o-aminophenol and its derivatives, m-diamino benzene and its derivatives such as 2,4-diaminophenoxyethanol, 1,3-bis- (2,4-diaminophenoxy) propane, 1-methoxy-2-amino-4- (2'-hydroxyethylamino) benzoI, 1, 3-bis (2,4-diaminophenyI) propane, 2,6-bis (2-hydroxyethylamino) - 1-methylbenzene and 1 - amino-3-bis- (2'-hydroxyethyl ) -aminobenzo 1, o-diaminobenzene and its derivatives such as 3,4-diaminobenzoic acid and 2,3-diamino-l-methylbenzene,

Di- or trihydroxybenzene derivatives such as 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-dimethoxy,

Naphthalene derivatives such as 1-naphthol, 2-methyl-1-naphthol, 2-hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxy naphthalene, 1.7 -Dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,7-dihydroxy-naphthalene and 2,3-dihydroxynaphthalene,

Morpholine derivatives such as 6-hydroxybenzomorpholine and 6-aminobenzomorpholine,

Quinoxaline derivatives such as 6-methyl-l, 2,3,4-tetrahydroquinoxaline,

Pyrazole derivatives such as, for example, l-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, for example, l-hydroxy-3,4-methylenedioxybenzene, l-amino-3,4-methylenedioxybenzene and l- (2'-hydroxyemyl) amino-3,4-methylenedioxybenzene, Particularly preferred coupler components are 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxy naphthalene, 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.

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

With regard to the dyes which can be used in the hair dyeing and tinting agents according to the invention, reference is also expressly made to the monograph Ch. Zviak, The Science of Hair Care, chapter 7 (pages 248-250; direct dyes) and chapter 8, pages 264-267; Oxidation dye precursors), published as Volume 7 of the "Dermatology" series (ed .: Ch., Culnan and H. Maibach), Marcel Dekker Inc., New York, Basel, 1986, and the "European inventory of cosmetic raw materials ", published by the European Community, available in diskette form from the Federal Association of German Industry and Commerce for Medicinal Products, Health Care Products and Personal Care Products, Mannheim.

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

Those indoles and indolines which have at least one hydroxyl or amino group, preferably as a substituent on the six-membered ring, are preferably used as precursors of nature-analogous dyes. These groups can carry further substituents, e.g. B. in the form of etherification or esterification of the hydroxy group or an alkylation of the amino group. Derivatives of 5,6-dihydroxyindoline of the formula (Va) are particularly suitable as precursors of naturally analogous hair dyes,

in the independently of each other

R ¹ represents hydrogen, a CrC ₄ alkyl group or a CrC hydroxy alkyl 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 CrC ₄ alkyl group,

- R ⁴ stands for hydrogen, a CrC ₄ alkyl group or a group -CO-R ⁶ , in which R ⁶ stands for a CrC 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. Particularly preferred derivatives of indoline are 5,6-dihydroxyindoline, Ν-methyl-5, 6-dihydroxyindoline, Ν-ethyl-5, 6-dihydroxyindoline, N-propyl-5, 6-dihydroxyindoline, N-butyl-5,6 dihydroxyindoline, 5,6-dihydroxyindoline-2-carboxylic acid and 6-hydroxyindoline, 6-aminoindoline and 4-aminoindoline.

Of particular note within this group are N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline and in particular the 5,6-dihydroxyindoline.

Derivatives of 5,6-dihydroxyindole of the formula (Vb) are also outstandingly suitable as precursors of natural hair dyes,

in the independently of each other

R ¹ represents hydrogen, a CrC 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 CrC alkyl group,

- R ⁴ stands for hydrogen, a CrC 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 tolerable salts of these compounds with an organic or inorganic acid.

Particularly 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 this group, particular mention should be made of 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 -Dihydroxyindol.

The indoline and indole derivatives can be used in the colorants used in the process according to the invention both as free bases and in the form of their physiologically tolerable salts with inorganic or organic acids, for. B. the hydrochloride, sulfates and hydrobromides can be used. The indole or indoline derivatives are usually contained 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 to use the indoline or indole derivative in hair colorants in combination with at least one amino acid or an oligopeptide. The amino acid is advantageously an α-amino acid; very particularly preferred α-amino acids are arginine, ornithine, lysine, serine and histidine, in particular arginine.

In addition to the dye precursors, the colorants according to the invention can contain substantive dyes for further shading. These are usually selected from nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols. Preferred substantive dyes are those with the international names or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, Basic Yellow 57, HC Orange 1, Disperse Orange 3, HC Red 1, HC Red 3, HC Red 13, HC Red BN, Basic Red 76, HC Blue 2, HC Blue 12, Disperse Blue 3, Basic Blue 7, Basic Blue 26, Basic Blue 99, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Basic Violet 2, Basic Violet 14, Acid Violet 43, Disperse Black 9, Acid Black 52, Basic Brown 16 and Basic Brown 17 known compounds as well as 1,4-bis (ß-hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- (β-hydroxyethyl) aminophenol, 4-amino-2-nitrodiphenylamine-2 '-carboxylic acid, 6-nitro-l, 2,3,4-tetrahydroquinoxaline, 2-hydroxy-l, 4-naphthoquinone, hydroxyethyl-2-nitro -toluidine, picramic acid, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene. The agents according to the invention according to this embodiment preferably contain the substantive dyes in an amount of 0.01 to 20% by weight, based on the total colorant.

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

In addition to the enzyme system according to the invention, the colorants according to the invention can also contain further enzymes, such as, for example, laccases, tyrosinases, peroxidases or 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. Within the scope of this embodiment, agents are particularly preferred which, in addition to the enzyme according to the invention, also contain uricase, glucose oxidase and / or xanthine oxidase and their respective substrates.

To prepare the colorants according to the invention, the dye precursors can be incorporated into a suitable water-containing carrier. For the purpose of hair coloring, such carriers are e.g. Creams, emulsions, gels or also surfactant-containing foaming solutions, e.g. Shampoos, aerosols or other preparations that are suitable for use on the hair.

The colorants according to the invention can furthermore contain all active substances, additives and auxiliaries known for such preparations. In many cases, the colorants contain at least one surfactant, both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants being suitable in principle. The person skilled in the art can check a possible influence of the various surfactants on the activity of the enzyme system according to the invention if necessary by simple preliminary tests.

In a preferred embodiment of the present invention, a combination of anionic and nonionic surfactants or a combination of anionic and amphoteric surfactants is used in the agents for coloring keratin fibers. In individual cases, however, it has proven to be advantageous to select the surfactants from amphoteric or nonionic surfactants, since these generally have less influence on the dyeing process according to the invention.

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 z. B. a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group with about 10 to 22 carbon atoms. In addition, the molecule can contain glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups. Examples of suitable anionic surfactants are, in each case in the form of the sodium, potassium and ammonium and the mono-, di- and trialkanolammonium salts with 2 or 3 carbon atoms in the alkanol group, linear fatty acids with 10 to 22 carbon atoms (soaps )

Ether carboxylic acids of the formula RO- (CH ₂ -CH ₂ O) _x -CH ₂ -COOH, in which R is a linear alkyl group with 10 to 22 C atoms and x = 0 or 1 to 16, acyl sarcosides with 10 to 18 C- Atoms in the acyl group, acyl taurides with 10 to 18 C atoms in the acyl group, acyl isethionates with 10 to 18 C atoms in the acyl group,

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

Mixtures of surface-active hydroxysulfonates according to DE-A-3725 030, sulfated hydroxyalkyl polyethylene and / or hydroxyalkylene propylene glycol ethers according to DE-A-3723 354,

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

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

C ₈ -C ₂₂ alkyl mono- and oligoglycosides and their ethoxylated analogues and addition products 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 O- (Z) _χ . These compounds are, for example, under the trade name Plantacare ^® from

Henkel available and 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. Alkylpolyglycosides in which R ¹ consists essentially of C ₈ and C ₁₀ alkyl groups, essentially consists of C ₁₂ and C ₁₄ alkyl groups, essentially consists of C ₈ to C 6 alkyl groups or essentially of C ₁₂ are particularly preferred - C ₁₆ alkyl groups.

Any mono- or oligosaccharides can be used as sugar building block Z. Sugar with 5 or 6 carbon atoms and the corresponding oligosaccharides are usually used. Examples of such sugars are glucose, fructose, galactose, arabinose, ribose, xylose, lyxose, allose, old rose, mannose, gulose, idose, talose and sucrose. Preferred sugar units are glucose, fructose, galactose, arabinose and sucrose; Glucose is particularly preferred.

The alkyl polyglycosides which can be used according to the invention 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 is 1.1 to 1.4 are very particularly preferred.

In addition to their surfactant action, the alkyl glycosides can also serve to improve the fixation of fragrance components on the hair. In the event that an effect of the perfume oil on the hair beyond the duration of the hair treatment is desired, the person skilled in the art will preferably resort to this substance class as a further ingredient of the preparations according to the invention. An inventively particularly preferred alkyl glucoside is the commercial product Plantacare® ^® 1200G.

The alkoxylated homologs of the alkyl polyglycosides mentioned can also be used according to the invention. These homologues can contain an average of up to 10 ethylene oxide and / or propylene oxide units per alkyl glycoside unit. Furthermore, zwitterionic surfactants can be used, in particular as co-surfactants. Zwitterionic surfactants are those surface-active compounds which carry at least one quaternary ammonium group and at least one -COO ^w or -SO ₃ ^{w group in the} molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinates, for example the cocoalkyl-dimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammonium glycinate, for example the cocoacylaminopropyldimethylammonium glycinate, and 2-alkyl-3-carboxylmethyl-3-hydroxyethyl-imidazolines each with 8 to 18 C. -Atoms in the alkyl or acyl group and the cocoacylaminoethylhydroxyethyl carboxymethylglycinate. 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 are. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each with about 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethyl aminopropionate and C12 ₁ 8- sarcosine.

According to the invention, the cationic surfactants used are, in particular, those of the quaternary ammonium compound, esterquat and amidoamine type.

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 the compounds known under the INCI names quaternium-27 and quaternium-83 compounds imidazolium. The long alkyl chains of the above-mentioned surfactants preferably have 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, and 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. A compound from this group of substances which is particularly suitable according to the invention is the stearamidopropyldirnethylamine commercially available under the name Tegoamid ^® S 18.

The quaternized protein hydrolyzates are further cationic surfactants which can be used according to the invention.

Also suitable according to the invention are cationic silicone oils such as, for example, the commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethylsilylamodimethicone), Dow Corning 929 emulsion (containing a hydroxylamino-modified silicone, which is also referred to as amodimethicone), SM-2059 (Manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ^® - Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxanes, Quateπιium-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 substance mixtures with different alkyl chain lengths depending on the respective raw material are obtained.

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

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

Furthermore, the colorants according to the invention can preferably also contain a conditioning agent selected from the group formed by cationic surfactants, cationic polymers, alkylamidoamines, paraffin oils, vegetable oils and synthetic oils. With regard to the cationic surfactants, reference is made to the above statements.

Cationic polymers can be preferred as conditioning agents. These are usually polymers that contain a quaternary nitrogen atom, for example in the form of an ammonium group. Preferred cationic polymers are, for example quaternized cellulose derivatives, as are commercially available under the names Celquat ^® and Polymer JR ^® . The compounds Celquat ^® H 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 vinyl pyrrolidone with quaternized derivatives of dialkylamino acrylate and methacrylate, such as, for example, vinyl pyrrolidone-dimethylaminomethacrylate copolymers quaternized with diethyl sulfate. Such compounds are commercially available under the names Gafquat ^® 734 and Gafquat ^® 755. Vinylpyrrolidone methoimidazolinium chloride copolymers such as those sold under the name Luviquat ^®, quaternized polyvinyl alcohol and under the designations 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 AUcylarylsiloxane, such as dimethylpolysiloxane and methylphenylpolysiloxane, as well as their alkoxylated and quaternized analogues. Examples for 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).

Paraffin oils, synthetically produced oligomeric alkenes and vegetable oils such as jojoba oil, sunflower oil, orange oil, almond oil, wheat germ oil and peach seed oil can also be used as conditioning agents.

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

Furthermore, the preparations used according to the invention preferably contain at least one oil component.

Oil components suitable according to the invention are in principle all water-insoluble oils and fatty substances as well as their mixtures with solid paraffins and waxes. According to the invention, such substances are defined as water-insoluble if 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 are at room temperature, i.e. H. are liquid below 25 ° C, can be particularly preferred according to the invention. When using several oil and fat components and possibly solid paraffins and waxes, it is usually also sufficient if the mixture of the oil and fat components as well as any paraffins and waxes meets these conditions.

A preferred group of oil components are vegetable oils. Examples of such oils are sunflower oil, olive oil, soybean oil, rapeseed oil, almond oil, jojoba oil, orange oil, wheat germ oil, peach seed oil and the liquid components of coconut oil. However, other triglyceride oils such as the liquid portions of beef tallow and synthetic triglyceride oils are also suitable.

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-iso-pentyl ether, di-3-ethyl decyl ether, tert-butyl-n-octyl ether, iso-pentyl-n-octyl ether and 2-methyl-pentyl-n-octyl ether. The compounds are available as commercial products l, 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 oxosynthesis or the dimerization of unsaturated fatty acids, with alcohols such as isopropyl alcohol, capron 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, technical alcohol, gadoleyl alcohol, mixtures thereof, gadoleyl alcohol, brassucyl alcohol alcohol, gadoleyl alcohol, mixtures thereof, eradyl alcohol alcohol, gadoleyl alcohol, mixtures thereof, alcohol, gadoleyl alcohol, mixtures thereof, gadoleyl alcohol, mixtures of them with alcohol, gadoleyl alcohol, brassole, alcoholic alcohol, gadoleyl alcohol, mixtures thereof, alcohol, gadoleyl alcohol, brass mixtures, gadoleyl alcohol; B. in the high-pressure hydrogenation of technical methyl esters based on fats and oils or aldehydes from Roelen's oxo synthesis 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.

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

Finally, fatty alcohols with 8 to 22 carbon atoms can also be used as oil components acting according to the invention. The fatty alcohols can be saturated or unsaturated and linear or branched. For the purposes of the invention, for example, decanol, octanol, octenol, dodecenol, decenol, octadienol, dodecadienol, decadienol, oleyl alcohol, eruca alcohol, ricinol alcohol, stearyl alcohol, isostearyl alcohol, linoleic alcohol, capyl alcohol, caprolyl alcohol, caprolyl alcohol, caprolyl alcohol, arachol alcohol, arachol alcohol, arachol alcohol and behenyl alcohol, and their Guerbet alcohols, this list being intended to be exemplary and not limiting. However, the fatty alcohols are derived 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, rape 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 preferably used in amounts of 0.05 to 10% by weight, in particular 0.1 to 2% by weight, in the colorants according to the invention. In a preferred embodiment of the present invention, a gel forms when the colorants are dissolved in water. For this purpose, the colorant thickeners such as agar-agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, linseed gums, dextrans, acrylates, for example cellulose derivatives, for. B. methyl cellulose, hydroxyalkyl cellulose and carboxy methyl cellulose, starch fractions and derivatives such as amylose, A ylopectin and dextrins, clays such as. B. bentonite or fully synthetic hydrocolloids such as polyvinyl alcohol. 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 Cr to C ₆ -alkyl esters, as are sold under the LNCI declaration Acrylates Copolymers. A preferred commercial product is, for example, Aculyn ^® 33 from Rohm & Haas. However, copolymers of acrylic acid, methacrylic acid or their Cr to Co 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

Other active ingredients, hoofs and additives are, for example, zwitterionic and amphoteric polymers such as, for example, acrylamidopropyl-trimethylammonium chloride / acrylate copolymers and octylacrylamide / methyl-memacrylate / tert-bulylammoemylmemacrylate / 2-hydroxypropyl methacrylate copolymers, anionic polymers such as, for example, polyacrylic acids, cross-linked polyacrylic acids,

Vinyl acetate / crotonic acid copolymers, vinyl pyrrolidone / vinyl acrylate copolymers,

Vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic acid anhydride copolymers and acrylic acid / ethyl acrylate / N-tert-butyl-acrylamide terpolymers,

Structurants such as maleic acid and lactic acid,.

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,

Solvents and intermediates such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol, active substances which improve fiber structure, in particular mono-, di- and oligosaccharides such as, for example, glucose, galactose, fructose, fructose and lactose, quaternized amines such as methyl-l-alkylamidoethyl -2-alkylimidazolinium methosulfate defoamers such as silicones, dyes for coloring the agent,

Anti-dandruff agents such as piroctone olamine, zinc omadine and climbazole, 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 AUantoin, pyrrolidone carboxylic acids and their salts, as well as bisabolol, vitamins, provitamins and vitamin precursors, in particular those from 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, squirrel, coltsfoot, marshmallow, meristem, ginseng and ginger root, cholesterol,

Consistency generators such as sugar esters, polyol esters or polyol alkyl ethers, fats and waxes such as walrus, beeswax, montan wax and paraffins, fatty acid,

Complexing agents such as EDTA, NTA, ß-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, blowing agents 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.

With regard to further optional components and the amounts of these components used, reference is expressly made to the relevant manuals known to the person skilled in the art, e.g. B. Kh. Schrader, Fundamentals and Recipes for Cosmetics, 2nd edition, Hüthig Buch Verlag, Heidelberg, 1989.

The enzyme preparation is expediently mixed with the preparation from the dye precursors immediately before hair coloring. The application temperatures can be in a range between 10 and 50 ° C, preferably between 20 and 35 ° C. After an exposure time of approx. 30 minutes, the hair dye is removed from the hair to be colored by rinsing. Washing with a shampoo is not necessary if a carrier with a high surfactant content, e.g. B. a coloring shampoo was used.

In a further embodiment of the present invention, it may be preferred to formulate the agents, in particular the separately prepared enzyme preparation, free of antioxidants and / or complexing agents, since these can block the action of the enzymes. A second object of the present invention is a process for dyeing keratin fibers, characterized in that an agent containing at least one dye precursor and at least one enzyme of the oxidoductase type, which is present as a homodimer in solution under non-denaturing conditions, is used.

A third object of the present invention is the use of a phenol oxidizing enzyme, which is present in aqueous solution under non-denaturing conditions as a homodimer, for the oxidative coloring of keratin fibers.

The following exemplary embodiments are intended to explain the subject matter of the invention in more detail.

embodiments

The following colorants were produced (all quantities are parts by weight, unless stated otherwise).

For all examples, ascorbate oxidase from Cucurbita species (Röche Diagnostics, Lot. No. 85264733 -3) was used, which has an activity against L-ascorbic acid under the above-mentioned conditions of 250U per mg lyophilisate.

example 1

1. Preparation of the coloring cream cream base (partial mixture A)

Hydrenol ^® D ¹ 8.50 g

Lorol ^® techn. ² 2.00g

Eumulgin ^® B2 ³ 0.75g

Texapon ^® NSO ⁴ 20.00g

Dehyton ^® K ⁵ 12.50g

Water 30.00g

_ö - ^ - fatty alcohol (INCI name: Cetearyl alcohol) (Cognis) C _12-18 fatty alcohol (INCI name: Coconut alcohol) (Cognis) Cetylstearyl alcohol with approx. 20 EO units (INCI name: Ceteareth-20) (Cognis)

Lauryl ether sulfate, sodium salt (approx. 27.5% active substance; INCI name: Sodium Laureth Sulfate) (Cognis)

N, N-dimethyl-N- (. C _{8 18} -kokosamidopropyl) ammoniumacetobetain (ca. 30% active substance; INCI name: Aqua (Water), Cocamidopropyl Betaine) (Cognis)

The substances Hydrenol D, Lorol and Eumulgin B2 were melted at 80 ° C, mixed with the 80 ° C hot water containing Texapon NSO and Dehyton K, and emulsified with vigorous stirring. The emulsion was then cooled with gentle stirring. Dyeing preparation (partial mixture BL)

4-aminophenol 0.27g (0.0025mol)

5-amino-2-methylphenol 0.31g (0.0025mol)

Ammonium hydroxide ⁶ ad pH 7.0

Water 20ml

⁶ A commercial ammonium hydroxide solution from Sigma with a

30% ammonia in a ratio of 1:10 mixed with double-distilled water.

The dye precursors were dissolved in 20 ml of water and the pH of the solution was adjusted with ammonium hydroxide.

The dye preparation (partial mixture B1) was added to 25 g of the cream base melted at 80 ° C. (partial mixture A) and the pH was adjusted to pH 7 with an aqueous HCl solution or with ammonium hydroxide. The cream was made up to 50 g with water and cooled to 30 ° C. with stirring (coloring cream).

2. Colorings and results

Creation of the coloring systems

Test A: 8 g of pure coloring cream are mixed with 8 ml of water

Test B: 8 g of coloring cream are mixed with 8 ml of a 2% aqueous hydrogen peroxide solution

Experiment C: 8 g of coloring cream are mixed with 8 ml of an aqueous solution of ascorbate oxidase (20 mg of dissolved lyophilisate)

Experiment D: 8 g of coloring cream are mixed with 8 ml of an aqueous solution of ascorbate oxidase (40 mg of dissolved lyophilisate)

Experiment E: 8 g of coloring cream are mixed with 8 ml of an aqueous solution of ascorbate oxidase (100 mg of dissolved lyophilisate)

A strand of hair weighing 0.5 g and 6 cm (natural white) was immersed in these dyeing systems for 10 minutes. The dyeing was then continued on a 35 min Petri dish further developed in air. The hair was rinsed with lukewarm water, shampooed and air dried.

The color of the strands was assessed according to the color scale in the color catalog (Taschenlexikon der Farben, A. Kornerup and J.H. Wanscher, Muster-Schmidt-Verlag, 3rd unchanged edition, 1981). Furthermore, the coloring of the strands was measured colorimetrically at 4 measuring points using the Datacolor Text Flash device from Data Color International, the measurement results were evaluated using the Data Color Tools QC software in accordance with equation (I) and summarized in the following table. The coloring of the streak of experiment A served as a reference.

^{m = color strength} [ ^% ] ©

With

K = absorption coefficient

S = scattering coefficient

K S = reflection coefficient

In addition, the ΔE value of the CIELAB color system was determined in accordance with equation (II)

Table 1:

Example 2

1. Production of the coloring cream

Dyeing preparation (partial mixture B2)

4- amino-3-methylphenol 0.31g (0.0025mol)

2,4-diaminophenoxyethanol hydrochloride 0.60g (0.0025mol)

Ammonium hydroxide ad pH 7.0

Water 20ml

The dye precursors were dissolved in 20 ml of water and the pH of the solution was adjusted with ammonium hydroxide.

The dye preparation (partial mixture B2) was added to 25 g of the cream base melted at 80 ° C. (partial mixture A of Example 1) and the pH was adjusted to pH 7 with an aqueous HCl solution or with ammonium hydroxide. The cream was made up to 50 g with water and cooled to 30 ° C. with stirring. 2. Colorings and results

Creation of the coloring systems

Experiment F: 8 g of pure coloring cream are mixed with 8 ml of water

Test G: 8 g of coloring cream are mixed with 8 ml of a 2% aqueous hydrogen peroxide solution

Test H: 8 g of coloring cream are mixed with 8 ml of an aqueous solution of ascorbate oxidase (20 mg of dissolved lyophilisate)

Experiment I: 8 g of coloring cream are mixed with 8 ml of an aqueous solution of ascorbate oxidase (40 mg of dissolved lyophilisate)

Experiment J: 8 g of coloring cream are mixed with 8 ml of an aqueous solution of ascorbate oxidase (100 mg of dissolved lyophilisate)

Experiment K: 8 g of coloring cream are mixed with 8 ml of an aqueous solution of ascorbate oxidase (200 mg of dissolved lyophilisate)

Test L: 8 g of coloring cream are mixed with 8 ml of an aqueous solution of ascorbate oxidase (400 mg of dissolved lyophilisate)

A strand of hair weighing 0.5 g and 6 cm (natural white) was immersed in these dyeing systems for 10 minutes. The staining was then further developed in air for 35 minutes on a Petri dish. The hair was rinsed with lukewarm water, shampooed and air dried. The evaluation was carried out analogously to Example 1.

Table 2:

Example 3

12 dyeing formulations were produced (see Tables 3 to 5). These formulations were mixed 1: 1 with an aqueous solution of ascorbate oxidase (2000 U / ml) immediately before use and applied to human hair (Kerling natural white) (4 g of dye mixture on 0.5 g of hair). After an exposure time of 30 minutes at room temperature, the fibers were rinsed well, shampooed and then dried with a hair dryer. The color results are shown in the tables in the last line.

Table 3

Hydroxyethylcellulose (Hercules) Cπ - ^ - fatty alcohol glucoside (approx. 50% active substance; INCI name: Lauryl Glucoside) (COGNIS) 6-chloro-4-nitro-2-aminophenol hydrochloride 1 - (ß-hydroxyethylamino) - 4-methyl-2-nitrobenzene

Table 4

Table 5

In addition, series of tests with different oxidizing agents were carried out for formulations A, D, E and I. The concentration data are based on the ready-to-use dye mixture. The color result without oxidizing agent, that is, the color result of the air-oxidative coloring, was used as a reference for the ΔE value and color strength (calculation as carried out in Example 1). The results are summarized in Table 6.

Table 6

Example 4

The following colorants were also formulated: Colorant 4A

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) phenolic dihydrochloride 2.67

2-amino-3-hydroxypyridine 1.1

Ammonia (25% in water) ad pH 8.5

Water ad 100

Colorant 4B

Fatty alcohol mixture C ₁₂ -Cι 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-aminomethylphenol dihydrochloride 0.002

2-amino-3-hydroxypyridine 0.004

3-methyl-4-aminophenol 0.007 l, 3-bis (2,4-diaminophenoxy) propane tetrahydrochloride 0.0005 p-toluenediamine sulfate 0.06

Resorcinol 0.01

3-amino-2,4-dichlorophenol hydrochloride 0.008 3-aminophenol 0.002

4-chlororesorcinol 0.01

Ammonia (25% in water) ad pH 8.5

Water ad 100

Colorant 4C

Fatty alcohol mixture Cι ₂ -Cι 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-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 -diaminobenzene sulfate 0.7

4-methylresorcinol 0.1

5, 6-dihydroxyindole 0.05

Monoethanolamine ad pH 7

Water ad 100

Colorant 4D

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-aminophenol 0.49

4-amino-3-methylphenol 0.55

2-amino-3-hydroxypyridine 1, 0 p-toluenediamine sulfate 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 ¹¹ 0.03

HC Red I ¹² 0.02 sodium hydroxide ad pH 8.5

Water ad 100 ¹ * 2 - ((2-amino-4-nitrophenyl) amino) ethanol ¹² 4-amino-2-nitrodiphenylamine

Colorant 4E

Fatty alcohol mixture Cι -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-aminomethylphenol dihydrochloride 2.0

2-methylamino-3-amino-6-methoxypyridine 2.25

Arginine ad pH 7.5

Water ad 100

Colorant 4F

Fatty alcohol mixture Cι ₂ -Cι 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-aminomethylphenol dihydrochloride 0.017

2-methylamino-3-amino-6-methoxypyridine 0.002 l- (2'-hydroxyethyl) -2,5-diaminobenzene sulfate 0.03

1-naphthol 0.02

2-methylresorcinol 0.0006

Lysine ad pH 7

Water ad 100

Colorant 4G

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) phenolic dihydrochloride 0.1

2-methylamino-3-amino-6-methoxypyridine 0.002

3-methyl 1-4-aminophenol 0.07

2,4,5,6-tetraaminopyrimidine sulfate 1.0 p-toluenediamine sulfate 1.1

3-aminophenol 0.006

Resorcinol 0.11

2-methylresorcinol 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 4H

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 ¹³ 0.2

5,6-dihydroxyindoline hydrobromide 0.1

Ammonia (25% in water) ad pH 7

Water ad 100 ¹³ 4- (3-hydroxypropyl) amino-3-nitrophenol (Clariant)

Colorant 41

Fatty alcohol mixture C ₁ -Cι 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 - ((diethylamino) methyl) phenolic dihydrochloride 1.25

4-amino-2-aminomethylphenol dihydrochloride 1.0

5-amino-2-methylphenol 1,23 Ammonia (25% in water) ad pH 7

Water ad 100

Colorant 4J

Fatty alcohol mixture C ₁₂ -Cι 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 - ((diethylamino) methyl) phenolic dihydrochloride 0.5

Bis (2-hydroxy-5-aminophenyl) methane 0.4

5-Amino-2-methylphenol 0.55 p-toluenediamine sulfate 0.3 p-phenylenediamine dihydrochloride 0.2

Resorcinol 0.07

2,7-dihydroxynaphthalene 0.09

2-methylresorcinol 0.07 o-aminophenol 0.03

5, 6-dihydroxyindoline hydrobromide 0.05

Ammonia (25% in water) ad pH 8.5

Water ad 100

Colorant 4K

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-tetraaminopyrimidine sulfate 0.8 p-toluenediamine sulfate 0.09

3-aminophenol 0.004

Resorcinol 0.04

2-methylresorcinol 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 4L

Fatty alcohol mixture C ₁₂ -C ₁₈ 5.25

Eumulgin ^® B2 0.4

Plantacare ^® 1200 3.0

Dehyton ^® K 2.5

Sodium sulfite 0.1

Ammonium sulfate 0.5

Natrosol ^® 250 HR 1.0

4-amino-2-aminomethylphenol dihydrochloride 1.06

4-aminophenol 0.55

5-amino-2-methylphenol 0.74

4-hydroxyindole 0.1 l, 3-bis (2,4-diaminophenoxy) propane tetrahydrochloride 0.3

2-methylamino-3-amino-6-methoxy-pyridine-dihydrochloride 0.1 Ammonia (25% in water) ad pH 7

Water ad 100

Colorant 4M

Hydrenol D 8.0 ^®

C12-C18 fatty alcohol 2.0

Akypo Soft ^® 45 NV ¹⁴ 10.0

Eumulgin ^® Bl ¹⁵ 0.5

Eumulgin ^® B2 0.5

5-amino-2-methylphenol 0.02

3 - Amino-2-chloro-6-methylphenol 0.36 l, 3-bis (2 ', 4'-diaminophenoxy) propane-tetrahydrochloride 0.0002

3-methyl 1-4-aminophenol 0.02

4-amino-2-aminomethyl-phenol-dihydrochloride 0.40 p-toluenediamine sulfate 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

¹⁴ C12-14-fatty alcohol-4,5-EO-acetic acid sodium salt (21% active substance in water; INCI name: Sodium Laureth-6 Carboxylate) (KAO)

¹⁵ cetylstearyl alcohol + 12 EO (INCI name: Ceteareth-12) (COGNIS) Colorant 4N

Hydrenol D 8.0 ^®

C12-C18 fatty alcohol 2.0

Akypo Soft ^® 45 NV 10.0

Eumulgin ^® Bl 0.5

Eumulgin ^® B2 0.5m aminophenol 0.005

3-amino-2-methylamino-6-methoxypyridine hydrochloride 0.002

2-amino-3-hydroxypyridine 0.24

2,7-dihydroxynaphthalene 0.02

2-methylresorcinol 0.6 p-toluenediamine sulfate 0.73

Resorcinol 0.13

2,6-dihydroxy-3,4-dimethyl-pyridine 0.1

2,4,5,6-tetraaminopyrimidine 1,3

5-amino-2-methylphenol 0.03

5- (β-hydroxyethyl) amino-2-methylphenol 0.3

2-nitro-4-aminodipheny lamin-2 'carboxylic acid 0.1

Ammonium chloride 0.4

Perfume oil 0.2

Ammonia (25% in water) ad pH 7

Water ad 100

Colorant 40

HydrenoPD 8.0

C12-C18 fatty alcohol 2.0

Akypo Soft ^® 45 NV 10.0

Eumulgin ^® Bl 0.5

Eumulgin ^® B2 0.5

2-methylresorcinol 0.48 p-toluenediamine sulfate 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-tetraaminopyrimidine 3.0

3-methyl 1-4-aminophenol 0.16

3 - Amino-2-chloro-6-methylphenol 0.11

5-amino-2-methylphenol 0.03

1, 5-Dihydroxy naphthalene 0.002

Ammonium chloride 0.2

Mirapol ^® A-15 ¹⁶ 1.5

Perfume oil 0.2

Histidine ad pH 8

Water ad 100

¹⁶ polymeric quaternary ammonium salt (approx. 64% active substance; INCI name

Polyquaternium-2) (RHONE-POULENC)

Colorant 4P

HydrenorD 5.0

C12-C18 fatty alcohol 2.0

Texapon.RTM ^® NSO 3.0

Ammonium sulfate 0.5

5-amino-2-methylphenol 0.56

3-methyl 1-4-aminophenol 0.055 p-toluenediamine sulfate 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-tetrahydroquinoxaline 0.1

Ammonia (25% in water) ad pH 8

Water ad 100 Colorant 4Q

Hydrenol ^® D 5.0

C12-C18 fatty alcohol 2.0

Texapon.RTM ^® NSO 3.0

Ammonium sulfate 0.5 l, 3-bis (2 ', 4'-diaminophenoxy) propane-tetrahydrochloride 0.003 p-toluenediamine sulfate 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

For coloring, 1 part of the colorants described above was mixed with 1 part of an enzyme preparation. The enzyme preparation contained 2000U / ml ascorbate oxidase.

This application preparation was applied to light blonde human hair, left there for 30 minutes and then rinsed out. In all cases, intensive, luminous colorations with excellent fastness properties were obtained.

Claims

claims

1. Agent for dyeing keratin fibers containing in a cosmetically acceptable carrier at least one dye precursor, characterized in that it contains at least one enzyme of the oxidoreductase type, which is present as a homodimer in solution under non-denaturing conditions.

2. Composition according to claim 1, characterized in that it is a phenol oxidizing enzyme.

3. Composition according to one of claims 1 or 2, characterized in that the enzyme is present in aqueous solution under non-denaturing conditions as a homodimer.

4. Composition according to one of claims 1 to 3, characterized in that the enzyme is an ascorbate oxidase.

5. Composition according to claim 4, characterized in that the enzyme is an ascorbate oxidase which can be obtained from Cucurbita species or Cucumis sativa.

6. Agent according to one of claims 1 to 5, characterized in that it contains at least one developer component as the dye precursor.

7. Agent according to one of claims 1 to 6, characterized in that it contains at least one indole and / or indoline derivative as the dye precursor.

8. Agent according to one of claims 1 to 7, characterized in that it contains at least one coupler component.

9. Composition according to one of claims 1 to 8, characterized in that it further contains at least one substantive dye.

10. Composition according to one of claims 1 to 9, characterized in that it further contains at least one surfactant.

11. Composition according to claim 10, characterized in that it contains a nonionic or an amphoteric surfactant.

12. Composition according to one of claims 10 or 11, characterized in that it contains a surfactant combination of at least one anionic surfactant with at least one amphoteric surfactant and / or with at least one nonionic surfactant.

13. Composition according to one of claims 1 to 12, characterized in that it contains an alkalizing agent.

14. A process for dyeing keratin fibers, characterized in that an agent according to one of claims 1 to 13 is used.

15. Use of an enzyme of the oxidoreductase type, which is present as a homodimer in solution under non-denaturing conditions, for the oxidative coloring of keratin fibers.