DE10120606A1 - Oxidation dye composition for dyeing keratinic fibers, especially hair, includes an adenine compound as coupler - Google Patents

Abstract

Oxidation dye composition for dyeing keratinic fibers comprises at least one developer and at least one adenine compound (I). Oxidation dye composition for dyeing keratinic fibers comprises at least one developer and at least one adenine compound of formula (I): R<1>, R<2> = H, 1-4C alkyl, 1-4C hydroxyalkyl, 2-4C dihydroxyalkyl, 1-4C alkoxy, 2-4C alkenyl, 3-5C cycloalkyl, 1-4C aminoalkyl, alkyleneaminoalkyl, halogen or trimethylsilyloxy, provided that at least one is H, alkoxy or halogen.

Description

This invention relates to oxidation colorants for dyeing keratinic fibers which contain as a coupler component adenine derivatives, and their use.

For the dyeing of keratin fibers, especially human hair, play the soge called oxidation colorants because of their intense colors and good fastness properties play a privileged role. Such colorants contain oxidation dye prep products, so-called developer components and coupler components. The developers components form under the influence of oxidizing agents or atmospheric oxygen with each other or under coupling with one or more coupler components the egg natural dyes.

As developer components are usually primary aromatic amines with a further, in the para or ortho position, free or substituted hydroxy or amino group, diaminopyridine derivatives, heterocyclic hydrazones, 4- Aminopyrazolonderivate and 2,4,5,6-tetraaminopyrimidine and its derivatives puts.

Specific representatives are, for example, p-phenylenediamine, p-toluenediamine, 2,4,5,6-Te traaminopyrimidine, p-aminophenol, N, N-bis (2'-hydroxyethyl) -p-phenylenediamine, 2- (2 ', 5'-diaminophenyl) ethanol, 2- (2', 5'-diaminophenoxy) ethanol, 1-phenyl-3- carboxyamido-4-amino-pyrazolone-5,4-amino-3-methylphenol, 2-aminomethyl-4 aminophenol, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triamino-4-hydroxypyrimidine and 1,3-N, N'-bis (2'-hydroxyethyl) -N, N'-bis (4'-bis) aminophenyl) diamino-propane-2-ol.  

As coupler components usually m-phenylenediamine derivatives, naphthols, Re sorcin and resorcinol derivatives, pyrazolones and m-aminophenols. As a coupler Substances which are particularly suitable are 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-pyrazolone-5, 2,4-dichloro-3-aminophenol, 1,3-bis- (2 ', 4'-diaminophenoxy) -propane, 2-chlororesorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3- aminophenol, 2-methylresorcinol, 5-methylresorcur and 2-methyl-4-chloro-5-aminophenol.

Good oxidation dye precursors should fulfill the following conditions in particular:

• - You must in the oxidative coupling the desired color shades in sufficient Train intensity and authenticity.
• - You must also have a good Aufziehvermögen on the fiber, in particular In human hair, there are no noticeable differences between strained and damaged hair freshly grown hair may exist (leveling ability).
• - They should be resistant to light, heat, friction and the influence of chemical Reducing agent, for. B. permanent wave fluids.
• - They should - if used as a hair dye for use - the scalp not sehranfärben.
• - They should harmless especially in toxicological and dermatological terms his.
• - Furthermore, the coloring obtained by bleaching easily ent from the hair ent can be removed if they do not meet the individual wishes of the individual per son and should be reversed.

Alone with a developer component or a special coupler / developer combination As a rule, it is not possible to achieve a shade of color that works naturally on the hair receive. In practice, therefore, usually combinations of different Ent winder and / or coupler components used. There is therefore a constant need for new, improved dye components.  

Object of the present invention was therefore to develop new coupler components which fulfill the requirements imposed on oxidation dye precursors and Allow colorations in a broad color spectrum with good fastness properties.

It has now surprisingly been found that hair dyes containing at least one Developer component and at least one adenine derivative of the formula (I) as a coupler components that solve the tasks in an excellent way.

Therefore, the present invention relates to oxidation colorants for dyeing Keratinfa fibers, in particular human hair, in a suitable for dyeing medium, at least one developer component and at least one adenine derivative of the formula (I)

in which R ¹ and R ² independently of one another are hydrogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -hydroxyalkyl, C ₂ -C ₄ -dihydroxyalkyl, C ₁ -C ₄ -alkoxy, C ₂ -C ₄ - Alkenyl, C ₃ -C ₅ cycloalkyl, in particular C ₅ cycloalkyl, C ₁ -C ₄ aminoalkyl, alkyleneaminoalkyl, halogen or trimethylsilyoxy; and / or one of the physiologically acceptable salts of these compounds; with the proviso that at least one of R ¹ or R ^{2 is} hydrogen, C ₁ - C ₄ alkoxy or halogen.

Under keratin fibers are inventively furs, wool, feathers, hair and in particular special human hair to understand. Although the oxidation of the invention Colorants are primarily suitable for dyeing keratin fibers, is in principle a use in other fields, in particular in color photography, nothing contrary.

Particularly preferred for the purposes of the present invention are oxidation colorants in an aqueous carrier or in powder form.  

Examples of the C ₁ -C ₄ -alkyl groups mentioned as substituents in the compounds according to the invention are the groups methyl, ethyl, propyl, isopropyl and / or butyl. Ethyl and / or methyl are preferred alkyl groups. A preferred C ₁ -C ₄ -alkoxy group according to the invention is, for example, a methoxy and / or an ethoxy group. Wei terhin can be mentioned as preferred examples of a C ₁ -C ₄ hydroxyalkyl Hy droxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl and / or a 4-hydroxybutyl. Particularly preferred C ₂ -C ₄ -dihydroxyalkyl groups are, for example, 1,2-dihydroxyethyl, 1,2-dihydroxypropyl, 1,3-dihydroxypropyl, 2,3-dihydroxypropyl, 1,2-dihydroxybutyl, 1,3- Dihydroxybutyl, 1,4-dihydroxybutyl, 2,3-dihydroxybutyl, 2,4-dihydroxybutyl and / or 3,4-dihydroxybutyl groups. Particularly suitable C ₂ -C ₄ -alkenyl groups are the vinyl, the allyl, 1-propenyl, 1-buteryl, 2-butenyl, 3-butenyl and / or the 2-methylpropenyl group. With regard to the C ₃ C ₅ -Cycloalkyl groups, the Cyclopen tylgruppe is a particularly preferred substituent. Examples of a halogen atom are in accordance with the invention an F, a Cl, a Br and / or an I atom; a Cl atom is most preferred.

Furthermore, compounds are preferred in which each one of the substituents R ¹ or R ^{2 is} hydrogen.

Particular preference is given to compounds in which the substituents R ¹ and R ^{2 are} film hydrogen.

With the coupler components according to the invention, dyeings in the blonde Brown area are generated, in particular by their increased washing and light authenticity. Thus, these coupler components provide a valuable loading enriching the oxidation dye precursors.

The preparation of the coupler according to the invention can by means of conventional synthesis Verfah be done.

All statements of this document and accordingly the claimed scope both on the present in free form adenine derivatives according to formula (I) and on  their water-soluble, physiologically acceptable salts. Examples of such salts are the Hydrochlorides, hydrobromides, sulfates, phosiphates, acetates, propionates, the citrates and the lactates.

The oxidation colorants according to the invention contain in principle at least one Coupler component according to formula (I) and at least one developer component.

It may be preferred according to the invention to use as the developer component a p-phenylenediamine derivative or one of its physiologically acceptable salts. Particular preference is given to p-phenylenediamine derivatives of the formula (E1)

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 radical, a 4'-aminophenyl radical and / or a C ₁ - to 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 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 and / 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 -Monohydroxyalkylradikal, a C ₁ - to C ₄ -Hydroxyalkoxyradikal, a C ₁ - to C ₄ -Acetylaminoalkoxyradikal, a C ₁ - to C ₄ -Mesylaminoalkoxyradikal and / or a C ₁ - to C ₄ -Carbamoylaminoalkoxyradikal;
• G ⁴ represents a hydrogen atom, a halogen atom and / or a C ₁ to C ₄ alkyl radical or
• when G ³ and G ⁴ are ortho to each other, they may together form a bridging α, ω-alkylenedioxy group, such as, for example, an ethylenedioxy group.

Examples of the mentioned as substituents in the compounds of the invention, C ₁ - to C ₄ -alkyl radicals are the groups methyl, ethyl, propyl, isopropyl and / or Bu tyl. Ethyl and methyl are preferred alkyl radicals. C ₁ -C ₄ -alkoxy radicals which are preferred according to the invention are, for example, a methoxy and / or an ethoxy group. Wei terhin can be mentioned as preferred examples of a C ₁ - to C ₄ hydroxyalkyl Hy droxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl and / or a 4-hydroxybutyl. A 2-hydroxyethyl group is particularly preferred. Examples of halogen atoms are according to the invention F, Cl and / or Br atoms, Cl atoms are very particularly preferred. The other terms used are derived according to the invention from the definitions given here. Examples of nitrogen-containing groups of the formula (II) 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 monohydroxyakylamino groups, Imidazolinium and / or 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- methylaniline, 4-N, N-bis- (β-hydroxyethyl) amino-2-cliloraniline, 2- (β-hydroxyethyl) -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, 4,4'-di  aminodiphenylamine and / or 5,8-diaminobenzo-1,4-diioxane and their physiological compatible salts.

Very particularly preferred p-phenylenediamine derivatives of the formula (E1) according to the invention are p-phenylenediamine, p-toluenediamine, 2- (β-hydroxyethyl) -p-phenylenediamine, 4,4'- Diaminodiphenylamine, N, N-bis (β-hydroxyethyl) -p-phenylenediamine and / or their phy biologically compatible salts.

It may further be preferred according to the invention, alis developer component verbin use at least two aromatic nuclei containing amino acids and / or hydroxyl groups are substituted.

Among the binuclear developer components which can be used in the dyeing compositions according to the invention, mention may be made, in particular, of the compounds which correspond to the following formula (E2) and their physiologically tolerated salts:

in which:

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

The substituents used in formula (E2) are analogous to the above according to the invention Executions defined.

Preferred binuclear 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) - tetramethylenediamine, N, N'-bis (β-hydroxyethyl) -N, N'-bis (4-aminophenyl) - tetramethylenediamine, N, N'-bis (4-methyl-aminophenyl) -tetramethylenediamine, N, N'-bis- (Ethyl) -N, N'-bis (4'-amino-3'-methylphenyl) ethylenediamine, bis (2-hydroxy-5- aminophenyl) methane, 1,4-bis- (4'-aminophenyl) -diazacycloheptane, N, N'-bis- (2-hydroxy-) 5-aminobenzyl) -piperazine, N- (4'-aminophenyl) -p-phenylenediamine and 1,10-bis- (2 ', 5'- diaminophenyl) -1,4,7,10-tetraoxadecane and / or their physiologically acceptable salts.

Very 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, N, N'-bis (4'-aminophenyl) -1,4-diazacycloheptane and / or 1,10-bis (2 ', 5'-diaminophenyl) -1,4,7,10-tetraoxadecane and / or one of its phy biologically compatible salts.  

Furthermore, it may be preferred according to the invention to use as the developer component a p-aminophenol derivative and / or one of its physiologically tolerable salts. Particular preference is given to p-aminophenol derivatives of the formula (E3)

in which:

• G ¹³ represents a hydrogen atom, a halogen atom, a C ₁ -C ₄ -alkyl radical, a C ₁ -C ₄ -monohydroxyalkyl radical, a C ₁ -C ₄ -alkoxy- (C ₁ -C ₄ ) alkyl radical, a C ₁ - to C ₄ -aminoalkyl radical, a hydroxy (C ₁ - to C ₄₎ -alkylaminoradikal, a C ₁ - to C ₄ -Hydroxyalkoxyradikal, a C ₁ - to C ₄ hydroxyalkyl (C ₁ - to C ₄ ) -aminoalkylradical and / or a (di-C ₁ - to C ₄ -alkylamino) - (C ₁ - to C ₄ ) -alkyl radical;
• G ¹⁴ is 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 and / or a C ₁ to C ₄ cyanoalkyl radical;
• G ¹⁵ is 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 and / or a benzyl radical; and or
• G ¹⁶ is hydrogen and / or a halogen atom.

The substituents used in formula (E3) are analogous to the above according to the invention Executions defined.

Preferred p-aminophenols of the formula (E3) are in particular p-aminophenol, N- Methyl-p-aminophenol, 4-amino-3-methyl-phenol, 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- (β hydroxyethyl-aminomethyl) phenol, 4-amino-2-fluorophenol, 4-amino-2-chlorophenol,  2,6-dichloro-4-aminophenol, 4-amino-2 - ((diethylamino) methyl) phenol and their physio logically compatible salts.

Very particularly preferred compounds of the formula (E3) are p-aminophenol, Amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4-amino-2-chlorophenol, 4- Amino-2 - ((diethylamino) methyl) phenol and / or their physiologically acceptable salts.

Further, the developer component may be selected from o-aminophenol and its Derivatives such as 2-amino-4-methylphenol, 2-amino-5-methylphenol and / or 2-amino-4-chlorophenol and / or their physiologically acceptable salts.

Furthermore, the developer component may be selected from heterocyclic Ent components such as the pyridine, pyrimidine, pyrazole, pyrazole Pyrimidine derivatives and / or their physiologically acceptable salts.

Preferred pyridine derivatives are in particular the compounds disclosed in the patents GB 1 026 978 and GB 1 153 196, such as 2,5-diaminopyridine, 2- (4- Methoxyphenyl) amino-3-amino-pyridine, 2,3-diamino-6-methoxy-pyridine, 2- (β- Methoxyethyl) amino-3-amino-6-methoxy-pyridine, 3,4-diamino-pyridine and / or their phy biologically compatible salts.

Preferred pyrimidine derivatives are in particular the compounds described in the German Patent DE 23 59 399, Japanese Patent Laid-Open Publication JP 02019576 A2 and / or in the Offenlegungsschrift 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, 2,5,6- Triaminopyrimidine and / or their physiologically acceptable salts.

Preferred pyrazole derivatives are in particular the compounds described in the patents DE 38 43 892, DE 41 33 957 and / or patent applications WO 94/08969, WO 94/08970, EP- 740931 and DE 195 43 988, such as 4,5-diamino-1-methylpyrazole, 4,5- Diamino-1- (β-hydroxyethyl) pyrazole, 3,4-diaminopyrazole, 4,5-diamino-1- (4'-dihydroxy) 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- hydrazino pyrazole, 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- (2'-methyl) aminoethyl) amino-1,3-dimethylpyrazole, 3,4,5-triaminopyrazole, 1-methyl-3,4,5- triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole, 3,5-diamino-4 (β-hydroxy ethyl) amino-1-methylpyrazole, 1-phenyl-3-carboxyamido-4-amino-pyrazolone-5 and / or their physiologically acceptable salts.

Preferred pyrazole-pyrimidine derivatives are in particular the derivatives of the pyrazolo [1,5-a] -pyrimidine of the following formula (E4) and their tautomeric forms, provided that a tauto meres equilibrium exists:

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 polyhydroxyalkyl radical a (C ₁ to C ₄ ) alkoxy (C ₁ to C ₄ ) alkyl radical, a C ₁ to C ₄ aminoalkyl radical optionally protected by an acetyl-ureide or sulfonyl radical may 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, wherein the dialkyl radicals optionally form a carbon cycle or a heterocycle having 5 or 6 chain members, a C ₁ - to C ₄ -hydroxyalkyl- and / 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 radical, 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 radicals, where the dialkyl radicals optionally form a carbon cycle or a heterocycle having 5 or 6 chain members, a C ₁ - to C ₄ -hydroxyalkyl- and / 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 and / 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,
• - n has the value 0 or 1,

with the proviso that

• - the sum of p + q is not equal to 0;
• if p + q equals 2, n has the value 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 ¹⁷ G ¹⁸ (or NG ¹⁹ G ²⁰ ) and the group OH occupy the positions (2, 3); (5, 6); (6, 7); (3, 5) or (3, 7).

The substituents used in formula (E4) are according to the invention analogous to the above Executions defined.

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

Among the pyrazolo [1,5-a] -pyrimidines of the above formula (E4) can be called in particular special:

• - pyrazole [1,5-a] pyrimidine-3,7-diamine;  
• 2,5-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine;
• - pyrazole [1,5-a] pyrimidine-3,5-diamine;
• 2,7-dimethylpyrazolo [1,5-a] -pyrimidine-3,5-diamine;
• 3-amino-pyrazolo [1,5-a] -pyrimidin-7-ol;
• 3-amino-pyrazolo [1,5-a] -pyrimidin-5-ol;
• - 2- (3-amino-pyrazolo [1,5-a] -pyrimidin-7-ylamino) -ethanol;
• - 2- (7-amino-pyrazolo [1,5-a] -pyrimidin-3-ylamino) -ethanol;
• - 2 - [(3-amino-pyrazolo [1,5-a] -pyrimidin-7-yl) - (2-hydroxy-ethyl) -amino] -ethanol;
• - 2 - [(7-amino-pyrazolo [1,5-a] -pyrimidin-3-yl) - (2-hydroxy-ethyl) -amino] -ethanol;
• 5,6-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine;
• 2,6-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine;
• 2,5, N7, N7-tetramethylpyrazolo [1,5-a] -pyrimidine-3,7-diamine;

and their physiologically acceptable salts and their tautomeric forms when a tau Tomeric equilibrium is present.

The pyrazolo [1,5-a] -pyrimidines of the above formula (E4) can be used as in the literature described by cyclization starting from an aminopyrazole or hydrazine getting produced.

For shading purposes, the colorants according to the invention may contain, in addition to the novel adenine derivatives, further coupler components. Before ferred coupler components according to the invention are:

• M-aminophenol and its derivatives such as 5-amino-2-methylphenol, 5- (3-hydroxypropylamino) -2-methylphenol, 3-amino-2-chloro-6-methylphenol, 2- Hydroxy-4-aminophenoxyethanol, 3-amino-6-methoxy-2-methylaminophenol, 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-bis) hydroxyethylamino) -1-methylbenzene and 1-amino-3-bis (2'-hydroxyethyl) - aminobenzene,
• - o-diaminobenzene and its derivatives such as 3,4-diaminobenzoic acid and 2,3-diamino-1-methylbenzene,
• - Di- or trihydroxybenzene derivatives such as resorcinol, Re sorcin 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-hydroxy methyl-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-amino-benzo morpholine,
• 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, as well
• Methylenedioxybenzene derivatives such as 3,4-methylenedioxyphenol, 1- Hydroxy-3,4-methylenedioxybenzene, 1-amino-3,4-methylenedioxybenzene and 1- (2 ' Hydroxyethyl) amino-3,4-methylenedioxybenzene.

Further preferred coupler components according to the invention are 3-dimethylamino phenol, 2,4-dihydroxyaniline, 8-amino-6-methoxy-quinoline, 2-amino-5-naphthol-1,7-  disulfonic acid, 3-amino-1-phenyl-5-pyrazolone, 3,5-diaminobenzamide, 3 Methylsulfonylamino-2-methylaniline, 5,6-dihydroxybenzimidazole, 2,2'- Dihydroxybenzylamine, 3,5,3 ', 5'-tetra-amino-2,2'-dimethoxy-diphenyl, 3,5-diamino-p- chlorobenzotrifluoride, 4-methyl-3-aminophenol, 2,4-diamino-3-chlorophenol, 1-amino-3-di- (2-hydroxyethylamino) -4-ethoxybenzene, 2,4-dimethylresorcinol, bis (2 ', 4'- diaminophenoxy) methane, 2,6-bis (2'-hydroxyethyl) pyridine, 4-hydroxy-3- methoxybenzyl alcohol, 8-hydroxyquinoline, 4-hydroxy-3-methoxy-benzylamine, 4- Ethyl resorcinol, 2-methylthio-5-aminophenol, 5 - [(3'-hydroxypropyl) amino] -2- methylphenol, 2,6-dimethoxy-3-aminophenol and 2,6-diamino-3-methylthiotoluene.

Particularly preferred coupler components within the meaning of the invention are 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridine, Resorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5- Methylresorcinol, 2,5-dimethylresorcinol, 2,6-dihydroxy-3,4-dimethylpyridine, 6-methyl- 1,2,3,4-tetrahydroquinoxaline, m-aminophenol, o-aminophenol and 2-chlororesorcinol.

These developer and coupler components are usually incorporated in free form puts. In the case of substances with amino groups, however, it may be preferable to use them in the form of theirs physiologically acceptable salts, in particular in the form of the hydrochlorides and sulfates, use.

The hair colorants of the invention contain both the developer components as also the coupler components in an amount of 0.005 to 20 wt .-%, preferably 0.01 up to 15% by weight, more preferably 0.1 to 10% by weight, particularly preferably 0.3 to 5% by weight, most preferably 0.5 to 3% by weight, e.g. B. 1 and / or 2 wt .-%, and Kupplerkompo nenten in an amount of 0.005 to 20 wt .-%, preferably 0.01 to 15 wt .-%, more preferably 0.1 to 10 wt .-%, particularly preferably 0.3 to 5 wt%, most before zugt 0.5 to 3 wt .-%, z. B. 1 and / or 2 wt .-%, each based on the total Oxida tionsfärbemittel.

In this case, developer components and coupler components are generally approximately equimolar amounts used to each other. Even if the equimolar use as has proved expedient, so is a certain excess of individual oxidation  dye precursors not disadvantageous, so that developer components and Kupplerkompo nenten in a molar ratio of 1: 0.5 to 1: 3, in particular 1: 1 to 1: 2, be contained can.

In a preferred embodiment, the hair colorants according to the invention contain for further modification of the color shades in addition to the oxidation dye precursors in addition usual substantive dyes. Direct dyes are common Nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophe nole. Preferred substantive dyes are those under the international name 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 and 1,4-bis (β-hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- (β-hydroxyethyl) aminophenol, 4-amino-2-nitrodiphenylamine-2'-carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4-naphthoquinone, hydroxyethyl-2- nitro-toluidine, 1- (2'-hydroxyethyl) amino-4-methyl-2-n-tetrobenzene, picramic acid, 2- Amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6- ethylamino-1-hydroxy-4-nitrobenzene. The cationic substantive dyes that are sold under the trademark Arianor®, particularly preferred are direct drawing dyes.

Furthermore, the agents of the invention may also occur in nature color Henna red, Henna neutral, Henna black, Chamomile flower, San delholz, black tea, buckthorn bark, sage, bluewood, madder root, catechu, sedre and alkano root included.

The agents according to the invention according to this embodiment contain the direct draw the dyes preferably in an amount of 0.005 to 20 wt .-%, preferably 0.01 to 15 Wt .-%, more preferably 0.1 to 10 wt .-%, particularly preferably 0.3 to 5 wt .-%, am most preferably 0.5 to 3% by weight, e.g. B. 1 and / or 2 wt .-%, based on the total An oxidation.  

Further dye components contained in the colorants according to the invention are passed itself from a precursor of melanin, selected from the derivatives of indole and Indolins, and their physiologically acceptable salts. In the context of the present Invention, under "precursors of melanin", such derivatives of indole and of In understood dolines that are capable of melanin as part of an oxidative process form dyes or corresponding melanin dye derivatives.

According to the invention, in the context of this embodiment, indoles and indolines are preferred, the at least one hydroxy and / or amino group, preferably as a substituent on the six ring, exhibit. These groups may carry further substituents, e.g. B. in the form of a Etherification or esterification of the hydroxy group or alkylation of the amino group pe. Indoles and indolines with two of these groups, in particular two hydroxy groups, of one or both of which may be etherified or esterified are particularly preferred.

Particular preference according to the invention is given to derivatives of indoline, such as the 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, 5-hydroxyindoline, 6-hydroxyindoline, 5-aminoindoline, 6-aminoindoline and / or 4-aminoindoline.

Very particular preference is given to derivatives of 5,6-dihydroxyindoline of the formula (IIa)

in the independently of each other
R ¹ is hydrogen, a C ₁ -C ₄ -alkyl group, a C ₁ -C ₄ -hydroxyalkyl group or a C ₃ -C ₆ -cycloalkyl group;
R ² is hydrogen or a -COOH group, wherein the -COOH group may also be present as a salt with a physiologically compatible cation;
R ³ is hydrogen or a C ₁ -C ₄ alkyl group;
R ⁴ is hydrogen, a C ₁ -C ₄ alkyl group or a group -CO-R ⁶ , in which R ⁶ is a C ₁ -C ₄ alkyl group or an optionally substituted phenyl group, and / or
R ⁵ is one of the groups mentioned under R ⁴ .

Representatives preferred according to the invention are 5,6-dihydroxyindoline, N-methyl-5,6-dihydro xyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-di hydroxyindoline. The main body, 5,6-dihydroxyindoline, is particularly imminent Trains t.

Indoles preferred according to the invention, of which the group X is derived, are 5,6-dihy droxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-di hydroxyindole, N-butyl-5,6-dihydroxyindole, 5,6-dihydroxyindole-2-carboxylic acid, 5- Hydroxyindole, 6-hydroxyindole, 5-aminoindole, 6-aminoindole and 4-aminoindole.

Particular preference is given to derivatives of the 5,6-dihydroxyindole of the formula (IIb)

in the independently of each other
R ¹ is hydrogen, a C ₁ -C ₄ -alkyl group, a C ₁ -C ₄ -hydroxyalkyl group or a C ₃ -C ₆ -cycloalkyl group,
R ² is hydrogen or a -COOH group, wherein the -COOH group may also be present as a salt with a physiologically compatible cation,
R ³ is hydrogen, a C ₁ -C ₄ -alkyl group or a group -CH ₂ -NR ⁷ R ⁸ , in which R ⁷ and R ⁸ independently of one another represent hydrogen or a C ₁ -C ₄ -alkyl group,
R ⁴ is hydrogen, a C ₁ -C ₄ alkyl group or a group -CO-R ⁶ , in which R ⁶ is a C ₁ -C ₄ alkyl group or an optionally substituted phenyl group, and
R ⁵ is one of the groups mentioned under R ⁴ .

Representatives preferred according to the invention are 5,6-dihydroxyindole, N-methyl-5,6-dihy droxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihy droxyindol. The main body, 5,6-dihydroxyindole, is most preferred.

The agents according to the invention according to this embodiment contain these precursors of the melanin preferably in an amount of 0.005 to 20 wt .-%, preferably 0.01 to 15 wt .-%, more preferably 0.1 to 10 wt .-%, particularly preferably 0.3 to 5 wt .-%, am most preferably 0.5 to 3% by weight, e.g. B. 1 and / or 2 wt .-%, based on the total An oxidation.

It is not necessary that the oxidation dye precursors, developers, couplers, Indoles / indolines or substantive dyes are each unitary compounds put. Rather, in the hair colorants according to the invention, due to the Production process for the individual dyes, in minor amounts still white Tere components may be included, as far as this does not adversely affect the dyeing result flow or for other reasons, such as As toxicological, must be excluded.

With regard to the hair dyeing and tinting compositions according to the invention can be used Dyes is still expressly referred 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 series "Dermato logy "(ed .: Ch. Culnan and H. Maibach), published by Marcel Dekker Inc., New York, Basel, 1986, as well as the "European Inventory of Cosmetic Raw Materials", published by the European Community, available in disk form from the Bundesverband Deutscher Industrial and commercial enterprise for pharmaceuticals, health products and personal care tel e. V., Mannheim.  

To prepare the colorants of the invention, the oxidation dye precursors are incorporated into a suitable aqueous carrier. Such Trä ger are for the purpose of hair coloring z. As creams, emulsions, gels or th also containing foaming solutions, eg. As shampoos, foam aerosols or other Zuberei which are suitable for use on the hair.

The colorants of the invention may further be all for such preparations be knew active ingredients, additives and excipients included. In many cases, the colorants contain at least one surfactant, wherein in principle both anionic and zwitterionic, am phytic, nonionic and cationic surfactants are suitable. In many cases it has However, proved to be advantageous, the surfactants from anionic, zwitterionic or select nonionic surfactants.

The compositions according to the invention according to this embodiment contain surfactants in one Amount of 0.1 to 30 wt .-%, preferably 1 to 20 wt .-% and particularly preferably 2 to 10% by weight.

Suitable anionic surfactants in preparations according to the invention are all anionic surfactants suitable for use on the human body. The se are characterized by a water-solubilizing, anionic group such as. Example, a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group having about 10 to 22 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups may 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 C atoms in the alkanol group,

• Linear and / or branched fatty acids with 8 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 having 10 to 22 C atoms and x = 0 or 1 to 16,
• Acylsarcosides having 10 to 18 C atoms in the acyl group,
• Acyltaurides having 10 to 18 C atoms in the acyl group,
• Acyl isethionates having 10 to 18 C atoms in the acyl group,  
• - Sulfobernsteinsäuremono- and -dialkylester having 8 to 18 carbon atoms in the alkyl group and sulfosuccinic acid mono-alkylpolyoxyethylester having 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups,
• Linear alkanesulfonates having 12 to 18 C atoms,
• - linear alpha-olefin sulfonates having 12 to 18 C atoms,
• Alpha-sulfofatty acid methyl esters of fatty acids containing 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 having 10 to 18 C atoms and x = 0 or 1 to 12,
• Mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030,
• - Sulfated Hydroxyalkylpolyethylen- and / or Hydroxyalkylenpropylenglykolether according to DE-A-37 23 354,
• - Sulfonates of unsaturated fatty acids with 12 to 24 carbon atoms and 1 to 6 doublebin according to DE-A-39 26 344,
• - esters of tartaric acid and citric acid with alcohols, the addition products from about 2-15 molecules of ethylene oxide and / or propylene oxide to fatty alcohols having 8 to 22 Represent C atoms.

Preferred anionic surfactants are alkyl sulfates, Alkylpolyglykolethersulfate and ether carboxylic acids having 10 to 18 carbon atoms in the alkyl group and up to 12 Glykolethergrup groups in the molecule and in particular salts of saturated and especially unsaturated C ₈ -C ₂₂ carboxylic acids, such as oleic acid, stearic acid, isostearic acid and palmitic acid. The compositions according to the invention according to this embodiment contain anionic Tensi de in an amount of 0.5 to 30 wt .-%, preferably 1 to 20 wt .-%.

Zwitterionic surfactants are surface-active compounds which carry 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 N-alkyl-N, N-dimethylammoniumglycinate, for example, the cocoalkyl dimethylammoniumglycinat, N-acyl-aminopropyl-N, N-dimethylammonium glycinate, for example Kokosacylaminopropyl-dimethylammoniumglycinat, and 2-alkyl 3-carboxymethyl-3-hydroxyethyl-imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and cocoacylaminoethylhydroxyethylcarboxymethylgly cinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known by the INCI name Coca midopropyl betaine.

The agents according to the invention according to this embodiment contain zwitterionic Surfactants in an amount of 0.1 to 20 wt .-%, preferably 1 to 10 wt .-%.

Ampholytic surfactants are understood to mean those surface-active compounds which, apart from a C _8-18 -alkyl or -acyl group in the molecule, contain at least one free amino group and at least one -COOH or -SO ₃ H group and which 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 having about 8 to 18 C-Ato men in the alkyl group. Particularly preferred ampholytic surfactants are N-coco alkylaminopropionate, Kokosacylaminoethylaminopropionat and the C _12-18 acylsar cosine.

The agents according to the invention according to this embodiment contain ampholytic Surfactants in an amount of 0.1 to 20 wt .-%, preferably 1 to 10 wt .-%.

Nonionic surfactants contain as hydrophilic group z. Example, a polyol group, a poly alkylenglykolethergruppe or a combination of polyol and polyglycol ether group. Such compounds are, for example

• - Addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of Pro pylene oxide to linear fatty alcohols having 8 to 22 C-atoms, to fatty acids having 12 to 22 C atoms and alkylphenols having 8 to 15 C atoms in the alkyl group,
• C _12-22 fatty acid mono- and diesters of addition products of 1 to 30 moles of ethylene oxide with glycerol,
• C _{8-22 alkyl} mono- and oligoglycosides, their ethoxylated analogs and / or their esters, e.g. With tartaric acid and / or citric acid,
• - Addition products of 5 to 60 moles of ethylene oxide with castor oil and hardened Castor oil,  
• - Addition products of ethylene oxide to sorbitan fatty acid esters
• - Addition products of ethylene oxide to fatty acid alkanolamides.

The agents according to the invention according to this embodiment contain nonionic Surfactants in an amount of 0.1 to 30 wt .-%, preferably 1 to 20 wt .-%.

Examples of the usable in the hair treatment compositions according to the invention katio Nischen Tenside are in particular quaternary ammonium compounds. Preferred are Ammonium halides such as alkyltrimethylammonium chlorides, dialkyldimethyl ammonium chlorides and trialkylmethylammonium chlorides, e.g. B. cetyltrimethylammo ammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, Lauryldimethylammonium chloride, Lauryldimethylbenzylammoniumchlorid and tricetyl methyl ammonium chloride. Further cationic surfactants which can be used according to the invention represent the quaternized protein hydrolysates.

Likewise suitable according to the invention are cationic silicone oils, such as those described in US Pat Commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trim thylsilylamodimethicone), Dow Corning 929 emulsion (containing a hydroxyl-amino-mo modified silicone, 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).

Alkylamidoamines, especially fatty acid amidoamines such as that under the name Te go Amid®S 18 available Stearylamidopropyldimethylamin, in addition to a good conditioning effect especially by their good biodegradability. Also very readily biodegradable are quaternary ester compounds, so-called "Esterquats" such as the methyl hydroxyal sold under the trademark Stepantex® kyldialkoyloxyalkyl-ammonium Methosulfate and under the trademark De hyquart® distributed products such as Dehyquart® AU-46.

An example of a cationic surfactant employable quaternary sugar derivative the commercial product Glucquat® 100, according to INCI nomenclature a "Lauryl Methyl Glu ceth-10 hydroxypropyl dimonium chlorides ".  

The compositions according to the invention according to this embodiment contain cationic Ten side in an amount of 0.1 to 20 wt .-%, preferably 1 to 10 wt .-%.

The compounds used as surfactants with alkyl groups may be in each case act uniform substances. However, it is usually preferred in the production These substances are based on native plant or animal raw materials, so that one Substance mixtures with different, dependent on the particular raw alkyl chain ten lengths.

In the case of the surfactants, the addition products of ethylene oxide and / or propylene oxide with fatty al can represent alcohols or derivatives of these addition products, both products with a "normal" homolog distribution as well as those with a narrow homologue distribution can be used. Under "normal" homolog distribution Mi understood by homologues, which are used in the reaction of fatty alcohol and Al alkylene oxide using alkali metals, alkali metal hydroxides or alkali obtained metal alkoxides as catalysts. Narrow homolog distributions become when, for example, hydrotalcites, alkaline earth metal salts of ethercar bonsäuren, alkaline earth metal oxides, hydroxides or alcoholates used as catalysts become. The use of products with restricted homolog distribution can be be preferred.

According to the invention, the use of anionic surfactants in combination with zwitte Rionic surfactants are particularly preferred.

Also preferred according to the invention are those agents which additionally have a cationic Polymer included.

Among the cationic polymers are the permanently cationic polymers before Trains t. According to the invention, "permanently cationic" refers to such polymers, which have a cationic group regardless of the pH of the agent. These are in usually polymers containing a quaternary nitrogen atom, for example in the form of an ammo group.  

Preferred cationic polymers are, for example

• - Quaternized cellulose derivatives, as they are known under the names Celquat® and Po lymer JR® are commercially available. The compounds Celquat® H 100, Celquat® L 200 and Polymer JR®400 are preferred quaternized cellulose derivatives,
• Polysiloxanes with quaternary groups, such as those obtained commercially Q2-7224 (Manufacturer: Dow ConlLing; a stabilized trimethyl silylamodimethicone), Dow Corning® 929 emulsion (containing a hydroxylamino modified silicone, 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),
• - Cationic guar derivatives, such as those under the trade name Cosme dia®Guar and Jaguar® distributed products,
• - Polymers dimethyldiallylammonium salts and their copolymers with esters and Amides of acrylic acid and methacrylic acid. The under the names Mer quat®100 (poly (dimethyldiallylammonium chloride)) and Merquat®550 (dimethyl diallyl ammonium chloride-acrylamide copolymer) commercially available products are examples of such cationic polymers,
• - Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylamino acrylates and methacrylates such as vinyl quaternized with diethyl sulfate pyrrolidone-dimethylaminoethyl methacrylate copolymers. Such compounds are under commercially available under the names Gafquat®734 and Gafquat®755,
• - Vinylpyrrolidone-Vinylimidazoliummethochlorid copolymers, as described in the Be drawings Luviquat® FC 370, FC 550, FC 905 and HM 552 are offered.
• - quaternized polyvinyl alcohol,
• - as well as the names
• - Polyquaternium 2,
• - Polyquaternium 17,
• - Polyquaternium 18 and
• - Polyquaternium 27 known polymers with quaternary nitrogen atoms in the Po lymerhauptkette.

Likewise, as cationic polymers can be used under the name Polyquaternium-24 (commercial product eg Quatrisoft® LM 200), polyquaternium 32, Polyquaternium-35 and Polyquaternium-37 (commercial products eg Salcare® SC 92 and Salcare®SC 95) known polymers. Also usable according to the invention are the Copolymers of vinylpyrrolidone, as used as commercial products Copolymer 845 (Her ISP), Gaffix® VC 713 (manufacturer: ISP), Gafquat®ASCP 1011, Gafquat®HS 110, Luviquat® 8155 and Luviquat® MS 370 are available.

Cationic polymers preferred according to the invention are quaternized cellulose derivatives, polymeric dimethyldiallylammonium salts, Polyquaterniuni-27 and their copolymers so such as Polyquaterniuim-2 type polymers. Cationic cellulose derivatives, in particular the commercial product Polymei JR 400, and polymers of the type Polyquaternium-2, esp especially the commercial product Mirapol® A-15 are very particularly preferred cationic Polymers.

The compositions according to the invention according to this embodiment contain cationic Po in an amount of 0.1 to 10 wt .-%, preferably 0.2 to 5 wt .-%.

In many cases, amphopolymers can also be used as an alternative to the cationic polymers. Amphoteric polymers, ie polymers which contain both free amino groups and free -COOH or -SO ₃ H groups in the molecule and are capable of forming internal salts, are zwitterionic polymers which are quaternary in the molecule Contain ammonium groups and -COO ^- - or -SO ₃ ^- - groups, and summarized those polymers containing -COOH or -SO ₃ H groups and quaternary ammonium groups. An example of an inventively usable amphopolymer is the acrylic resin available under the name Amphomer®, which is a copolymer of tert-butylaminoetthylmethacrylat, N- (1,1,3,3-tetra methylbutyl) acrylamide and two or more monomers from the group Acrylic acid, methacrylic acid and their simple esters. Likewise preferred amphopolymers are composed of unsaturated carboxylic acid (for example acrylic and methacrylic acid), catalytically derivatized unsaturated carboxylic acid (for example acrylamidopropyltrimethylammonium chloride) and, if appropriate, further ionic or nonionic monomers, such as, for example, in German Publication DE 39 29 973 and the cited prior art can be found there. Likewise suitable for use in accordance with the invention are terpolymers of acrylic acid, methyl acrylate and methacrylamidopro pyltrimonium chloride, as are commercially available under the name Merquat®2001 N, and the commercial product Merquat® 280. Particularly preferred polymers are, for example, acrylamidopropyltrimethylammonium chloride / acrylate copolymers and / or octylacrylamide / methyl methacrylate / tert.butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers.

The compositions according to the invention according to this embodiment contain amphopolymers in an amount of 0.1 to 10 wt .-%.

Also preferably, the compositions of the invention contain at least one nonio nogenic or anionic polymer with thickening properties. Preference is given optionally crosslinked, polyacrylic acids, cellulose derivatives, eg. Methylcellulose, Hy hydroxyalkylcellulose and carboxymethylcellulose, and xanthan gum.

The agents according to the invention according to this embodiment contain nonionic and / or anionic polymers in an amount of 0.1 to 25 wt .-%.

Other active ingredients, auxiliaries and additives are, for example

• Nonionic polymers such as vinyl pyrrolidone / vinyl acrylate copolymers, Polyvinylpyrrolidone and vinylpyrrolidone / vinyl acetate copolymers and polysiloxanes,
• Anionic polymers such as, for example, polyacrylic acids, crosslinked polyacrylic acids, Vinyl acetate / crotonic acid copolymers, vinyl pyrrolidone / vinyl acrylate copolymers, Vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic acid anhydride copolymers and acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers
• - Thickeners such as agar-agar, guar gum, alginates, xanthan gum, gum ara bicum, karaya gum, locust bean gum, linseed gums, dextran, cellu loose derivatives, e.g. Methylcellulose, hydroxyalkylcellulose and carboxymethylcel cellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, To ne, such as As bentonite or fully synthetic Hydroholloide such. For example, polyvinyl alcohol,
• - structurants such as glucose and maleic acid,  
• Hair conditioning compounds such as phospholipids, for example soya lecithin, Egg lecithin and cephalins, as well as silicone oils,
• - Protein hydrolysates, in particular elastin, collagen, keratin, milk protein, soybean tein and wheat protein hydrolyzates, their condensation products with fatty acids like this like quaternized protein hydrolysates,
• Perfume oils, dimethylisosorbide and cyclodextrins,
• - Solubilizers such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol,
• Anti-dandruff agents such as Piroctone Olamine and Zinc Omadine,
• - other substances for adjusting the pH,
• - Active substances such as panthenol, pantothenic acid, allantoin, pyrrolidonecarboxylic acids and their salts, plant extracts and vitamins,
• - cholesterol,
• - light stabilizers,
• Bodying agents such as sugar esters, polyol esters or polyol alkyl ethers,
• - Fats and waxes such as spermaceti, beeswax, montan wax, paraffins, fatty alcohols and fatty acid esters,
• - fatty acid,
• - complexing agents such as EDTA, NTA and phosphonic acids,
• - Swelling and penetration substances such as glycerol, propylene glycol monoethyl ether, Carbo nate, bicarbonates, guanidines, ureas and primary, secondary and tertiary phosphates,
• Opacifiers such as latex,
• Pearlescing agents such as ethylene glycol mono- and distearate,
• - Propellants such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air and
• - antioxidants.

The constituents of the water-containing carrier are used for the preparation of the inventive ßen colorants used in customary amounts for this purpose; z. B. become emulsifiers in concentrations of 0.1 to 30 wt .-%, preferably 0.2 to 10 wt .-%, especially preferably 0.3 to 5% by weight, most preferably 0.5 to 3% by weight, and thickening in concentrations of 0.1 to 25 wt .-%, preferably 0.2 to 10 wt .-%, especially preferably 0.3 to 5 wt .-%, most preferably 0.5 to 2 wt .-%, each based on the total amount of the colorant used.  

The oxidative development of the dyeing can in principle be carried out with atmospheric oxygen. Preferably, however, a chemical oxidizing agent is used, especially when in addition to the coloring, a lightening effect on human hair is desired. As oxidation Persulfates, chlorites and in particular hydrogen peroxide or its An Storage products of urea, melamine and sodium borate in question. It continues possible to carry out the oxidation with the aid of enzymes. The enzymes can (Enzyme class 1: oxidoreductases) Electrons from suitable developer components (Reducing agent) transferred to atmospheric oxygen. Oxidases such as tyrosi would be preferred nose and laccase but also glucose oxidase, uricase or pyruvate oxidase. Continue kings the enzymes to enhance the effect of low levels of existing oxidation to serve medium. An example of such an enzymatic process is the procedure the effect of small amounts (eg 1% and less, based on the total mean) To amplify hydrogen peroxide by peroxidases.

Conveniently, the preparation of the oxidizing agent immediately before Haa Refärben mixed with the preparation of the Oxidationsfarbstofffvorprodukte. That there resulting ready-to-use hair dye preparation should have a pH in the range of 6 to 13, preferably in a range of 8 to 12, most preferably in one range from 9 to 11. Particularly preferred is the application of the hair dye in a weak alkaline environment. The application temperatures can be in a Be rich between 15 and 40 ° C lie. After an exposure time of about 30 minutes the hair dye by rinsing away from the hair to be dyed. The after Washing with a shampoo is unnecessary if a strong surfactant-containing carrier, eg. B. a dye beshampoo, was used.

A second object of this invention is the use of the aforesaid means for Dyeing keratinic fibers.

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

embodiments

The amounts in the examples are in grams unless otherwise stated Information be made.

Preparation of the coloring cream

Hydrenol® D ¹ 8.5 Lorol® techn. ² 2.0 Eumulgin B2 ³ 0.75 Texapon® NSO ⁴ 20.0 Dehyton® K ⁵ 12.5 sodium 0.5 ammonium sulfate 0.5 adenine 6 mmol Developer (see Table 1) 6 mmol Ammonia (25% solution) ad pH = 10.0 propylene glycol 2.0 water ad 100.0 ¹ C _16-18 fatty alcohol (INCI name: Cetearyl alcohol) (Cognis) @ ² C _12-18 fatty alcohol (INCI name: Coconut alcohol) (Cognis) @ ³ cetylstearyl alcohol with approx. 20 EO units (INCI name: Ceteareth-20) (Cognis) @ ⁴ lauryl ether sulfate, sodium salt (about 27.5% active ingredient, INCI name: Sodium Laureth Sulfate) (Cognis) @ ⁵ N, N-dimethyl-N- (C _8-18 -cocoamidopropyl) ammonium acetobetaine (about 30% active ingredient, INCI name: Aqua (Water), Cocamidopropyl Betaine) (Cognis)

The substances Hydrenol® D, Lorol® and Eumulgiri B2 were molten at 80 ° C zen, mixed with the 80 ° C hot water containing Texapon® NSO and Dehyton® K. and emulsified with vigorous stirring. Thereafter, the emulsion was under mild stirring cooled. The adenine was excess in propylene glycol and water at ca. 70 ° C dissolved. To this solution was added sodium sulfite and ammonium sulfate. The Developer components were separately dissolved in water. The two dye solutions  were incorporated successively in the dyeing cream. Subsequently, the pH became adjusted to pH = 10 with ammonia and made up to 100 g with water. It was stirred until it reached room temperature.

Staining of the keratinic fibers

The dyeing cream thus obtained was mixed in a ratio of 1: 1 with a 3% H ₂ O ₂ solution and applied to 5 cm long strands standardized, natural white, not specially treated human hair (Kerling). After 30 min exposure time at 32 ° C wur de the hair was rinsed, washed with a conventional shampoo and then dried.

The dyeings obtained are shown in Table I below.  

Table I

colorations

Claims (12)

1. oxidation dye for dyeing keratinic fibers, characterized in that it comprises at least one developer component and at least one adenine derivative of the formula (I) in a dyeing medium suitable for dyeing
in which R ¹ and R ² independently of one another are hydrogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -hydroxyalkyl, C ₂ -C ₄ -dihydroxyalkyl, C ₁ -C ₄ -alkoxy, C ₂ -C ₄ - Alkenyl, C ₃ -C ₅ -cycloalkyl, in particular C ₅ -cycloalkyl, C ₁ -C ₄ -aminoalkyl, Alkylenaminoalkyl, halogen or trimethylsily loxy and / or one of the physiologically acceptable salts of these compounds ent holds; with the proviso that at least one of R ¹ or R ^{2 is} hydrogen, C ₁ -C ₄ - alkoxy or halogen. 2. Composition according to claim 1, characterized in that one of the radicals R ¹ or R ^{2 of} the compound of formula (I) is hydrogen. 3. Composition according to claim 1, characterized in that the radicals R ¹ and R ^{2 of} the compound of formula (I) are hydrogen. 4. Composition according to one of claims 1 to 3, characterized in that the developer component is selected from the group consisting of p-phenylenediamine, p-toluenediamine, p-aminophenol, 1- (2'- Hydroxyethyl) -2,5-diaminobenzene, 4,4'-diaminodiphenylamine, 4-amino-3-methylphenol, 4-amino-2-chlorophenol, 2-amino-5-methylphenol, 2,4,5,6-tetraaminopyrimidine, 2- Hydroxy-4,5,6-triaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 4,5-diamino-1 (2'-hydroxyethyl) pyrazole, 2-aminomethyl-4-amino-phenol, 2-diethylaminomethyl-4- amino-phenol, N, N-bis- (2'-hydroxyethyl) -p-phenylenediamine, bis- (2-hydroxy-5-  aminophenyl) methane, N, N'-bis (2'-hydroxyethyl) -N, N'-bis (4-aminophenyl) -1,3- diamino-propan-2-ol, o-aminophenol 1,4-bis (4'-aminophenyl) -diazacycloheptane, 1,10- Bis- (2 ', 5'-diaminophenyl) -1,4,7,10-tetraoxadecane and / or their physiologically tolerated salts. 5. Composition according to one of claims 1 to 4, characterized in that it contains at least one further coupler component which is selected from the group consisting of 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxy naphthalene, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridine, resorcinol, 4-chlororesor cin, 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol, 2.5- Dimethylresorcinol, 2,6-dihydroxy-3,4-dimethylpyridine, 6-methyl-1,2,3,4- tetrahydroquinoxaline, m-aminophenol, o-aminophenol and / or 2-chlororesorcinol. 6. Composition according to one of claims 1 to 5, characterized in that developer components in an amount of 0.005 to 20 Wt .-%, preferably 0.01 to 15 wt .-%, more preferably 0.1 to 10 wt .-%, particularly be preferably 0.3 to 5% by weight, most preferably 0.5 to 3% by weight, e.g. B. 1 and / or 2 Wt .-%, and coupler components in an amount of 0.005 to 20 wt .-%, preferably 0.01 to 15 wt .-%, more preferably 0.1 to 10 wt .-%, particularly preferably 0.3 to 5 Wt .-%, most preferably 0.5 to 3 wt .-%, z. B. 1 and / or 2 wt .-%, each bezo conditions on the entire oxidation colorant are included. 7. Composition according to one of claims 1 to 6, characterized in that it further comprises at least one substantive dye contains. 8. Composition according to one of claims 1 to 7, characterized in that it further comprises at least one derivative of indole and / or Indolins as a precursor of melanin contains.   9. Composition according to one of claims 1 to 8, characterized in that it further contains at least one surfactant selected from the group comprising anionic, zwitterionic, ampholytic, cationic and / or nonionic surfactants. 10. Composition according to one of claims 1 to 9, characterized in that it further contains at least one polymer selected from the group comprising cationic, anionic, nonionic and / or ampho Polymers. 11. Composition according to one of claims 1 to 10, characterized in that it contains other active ingredients, auxiliaries and / or additives. 12. Use of agents according to one of claims 1 to 11 for dyeing keratini shear fibers, preferably hair.