DE102006062434A1 - Product for dyeing keratinic fibers, especially human hair, comprises an aldehyde, a cyclic onium compound and an inorganic oxide - Google Patents

Abstract

Product for dyeing keratinic fibers comprises an aldehyde, a cyclic onium compound and an inorganic oxide. Product for dyeing keratinic fibers comprises an aldehyde of formula (ia-1), a cyclic onium compound of formula (ib-1 and an inorganic oxide. R1>-R3>H, halo, 1-6C alkyl, 2-6C alkenyl, CHO, OH, 1-6C alkoxy, 1-6C dialkylamino, di(2-6C hydroxyalkyl)amino, di((1-6C)alkoxy(1-6C)alkyl)amino, 1-6C hydroxyalkoxy, sulfonyl, COOH, SO3H, sulfonamide, CONH2, 2-6C acyl or NO2; Z' : a direct bond or vinylene; R4>, R5>H or together form a 5- or 6-membered aromatic or alicyclic ring; R6>1-6C (cyclo)alkyl, 2-6C alkenyl, optionally substituted (hetero)aryl, aryl(1-6C)alkyl, 1-6C hydroxyalkyl, 2-6C polyhydroxyalkyl, (1-6C)alkoxy(1-6C)alkyl or (CH2)mNR'R"; R', R" : H, 1-4C alkyl, 1-4C hydroxyalkyl or aryl(1-6C)alkyl, or NR'R" is a 5- to 7-membered ring; m : 2-6; R7>1-6C alkyl; X : an anion. An independent claim is also included for reducing scalp staining during hair dyeing by optionally applying a product comprising an inorganic oxide in a cosmetic carrier and rinsing it off, and applying a product as above and rinsing it off. [Image].

Description

The The invention relates to an agent for dyeing hair, which the skin staining minimizes a method of reducing skin staining in the Frame of a staining procedure and the use of silicates to reduce skin staining, in particular while the hair coloring.

human Hair is becoming more diverse today Treated with hair cosmetic preparations. These include about Cleaning hair with shampoos, care and regeneration with rinses and Cures and bleaching, dyeing and deforming the hair with colorants, Tints, Wells and styling preparations. There are funds for change or nuancing the color of the head hair a prominent role.

For temporary dyeings become common dyeing or tinting agent used as dyeing Component so-called direct pullers included. This is it about dye molecules, which grow directly on the hair and no oxidative process to the formation of the color need. Belongs to these dyes for example, that from ancient times to the coloring of body and hairs known henna.

For lasting, intense colors with corresponding fastness properties become so-called oxidation colorants used. Such colorants usually contain Oxidation dye precursors, so-called developer components and coupler components. The developer components form under the influence of oxidants or of atmospheric oxygen with one another or by coupling with one or more coupler components the actual Dyes off. The oxidation colorants are characterized by excellent, long-lasting staining results out.

Finally has further dyeing process size Attention found. In this process, precursors of the natural Hair dye melanin applied to the hair; these form then in the context of oxidative processes in the hair natural analog dyes. Such a process with 5,6-dihydroxyindoline as dye precursor has been described in EP-B1-530 229. In, in particular multiple, use of agents with 5,6-dihydroxyindoline Is it possible, To give people with graying hair the natural hair color. The coloration can be done with atmospheric oxygen as the sole oxidant, so that no further oxidizing agents must be used. For persons with originally Medium-blond to brown hair, indoline can be the sole dye precursor be used. For the application in persons with originally red and in particular Dark to black hair color, on the other hand, can be satisfying Results frequently only by the concomitant use of other dye components, in particular special oxidation dye precursors can be achieved.

• A reaktive Carbonylverbindungen, d.h. Verbindungen, mit mindestens einer reaktiven Carbonylgruppe, und Komponente
• B mindestens eine CH-acide Verbindung

enthalten. Die Komponenten A und B werden im Folgenden als Oxofarbstoffvorprodukte bezeichnet.Another recently developed possibility to stain keratin-containing fibers is the use of stains containing a combination of component

• A reactive carbonyl compounds, ie compounds having at least one reactive carbonyl group, and component
• B at least one CH-acidic compound

contain. Components A and B are referred to below as Oxofarbstoffvorprodukte.

The The aforementioned oxo dye precursors are generally themselves no dyes and are therefore not taken alone alone for coloring keratin-containing fibers. Only in combination do they form after expiration a condensation reaction dyes out. For dye formation needed the oxo dye system in advance, no oxidation of a dye precursor, as it from the oxidative hair coloring is known. The lack of an oxidizing agent favors a fiber-sparing coloring.

In German Patent Application DE-A1-102 41 076 1,2-dihydro-2-oxo-pyrimidinium derivatives in combination with reactive carbonyl compounds as a coloring agent Keratin fibers proposed.

In the case of hair dyeing using oxo dyeing, the coloring of the scalp, which is frequently associated with the coloring of the hair and is perceived as disturbing and unacceptable, remains problematic in view of the prior art. Especially with the non-routine consumer who wants to dye the hair even at home, this problem occurs more. But even the experienced hairdresser, especially with intensive and deep colorations, often can not avoid a scaling of the scalp Leads customers to dissatisfaction.

It is therefore the need for a remedy or a procedure that is easily applied can and with the staining the scalp as part of hair coloring prevented or at least reduced.

Out DE-A1-100 28 723 a hair dyeing method is known in which the scalp and hair contour area to reduce the scalp staining initially with based on a water-in-oil emulsion an oil component and a nonionic emulsifier. Subsequently, will the hair dye product applied to the hair. After a usual for hair coloring exposure time is the hair thoroughly washed.

These Method for protecting the scalp from staining is sufficient in particular for the Dyeing not according to oxo dyeing out. The non-oxidative color-forming mechanism of the oxo staining represents new requirements for the protection of the skin from unwanted Coloring.

• (i) als Oxofarbstoffvorprodukte mindestens eine Kombination der Komponenten (ia) und (ib) enthält,
• (ia) mindestens eine reaktive Carbonylverbindung ausgewählt aus mindestens einer Verbindung gemäß Formel (ia-1),
  
  worin
• – R¹, R² und R³ stehen unabhängig voneinander für ein Wasserstoffatom, ein Halogenatom, eine C₁-C₆-Alkylgruppe, eine (C₂ bis C₆)-Alkenylgruppe, eine Formylgruppe, eine Hydroxygruppe, eine C₁-C₆-Alkoxygruppe, eine C₁-C₆-Dialkylaminogruppe, eine Di(C₂-C₆-hydroxyalkyl)aminogruppe, eine Di(C₁-C₆-alkoxy-C₁-C₆-alkyl)aminoguppe, eine C₁-C₆-Hydroxyalkyloxygruppe, eine Sulfonylgruppe, eine Carboxylgruppe, eine Sulfonsäuregruppe, eine Sulfonamidgruppe, eine Carbamoylgruppe, eine C₂-C₆-Acylgruppe, eine Acetylgruppe oder eine Nitrogruppe,
• – Z' steht für eine direkte Bindung oder eine Vinylengruppe,
• – R⁴ und R⁵ stehen für ein Wasserstoffatom oder bilden gemeinsam, zusammen mit dem Restmolekül einen 5- oder 6-gliederigen aromatischen oder aliphatischen Ring,
• (ib) mindestens eine CH-acide Verbindung mit einem aromatischen oder aliphatischen, heterozyklischen Grundkörper, die ausgewählt wird aus zyklischen Oniumverbindungen mit der Struktureinheit der Formel (ib-1),
  
  worin
• – R⁶ steht für eine lineare oder cyclische C₁-C₆-Alkylgruppe, eine C₂-C₆-Alkenylgruppe, eine gegebenenfalls substituierte Arylgruppe, eine gegebenenfalls substituierte Heteroarylgruppe, eine Aryl-C₁-C₆-alkylgruppe, eine C₁-C₆-Hydroxyalkylgruppe, eine C₂-C₆-Polyhydroxyalkylgruppe, eine C₁-C₆-Alkoxy-C₁-C₆-alkylgruppe, eine Gruppe R^IR^IIN-(CH₂)_m-, worin R^I und R^II stehen unabhängig voneinander für ein Wasserstoffatom, eine C₁-C₄-Alkylgruppe, eine C₁-C₄-Hydroxyalkylgruppe oder eine Aryl-C₁-C₆-alkylgruppe, wobei R^I und R^II gemeinsam mit dem Stickstoffatom einen 5-, 6- oder 7-gliedrigen Ring bilden können und m steht für eine Zahl 2, 3, 4, 5 oder 6,
• – R⁷ steht für eine (C₁ bis C₆)-Alkylgruppe, insbesondere für eine Methylgruppe,
• – X^- steht für ein physiologisch verträgliches Anion,
• – der Zyklus repräsentiert alle Ringstrukturen, die zusätzlich weitere Heteroatome wie Stickstoff, Sauerstoff oder Schwefel enthalten können und ferner ankondensierte Ringstrukturen tragen können, wobei alle diese Ringsstrukturen zusätzliche Substituenten tragen können, und
• (ii) mindestens eine mineralisch oxidische Verbindung enthält.

The first subject of this application is an agent for dyeing keratin-containing fibers, in particular human hair, in a cosmetic carrier

• (i) contains as oxo dye precursors at least one combination of components (ia) and (ib),
• (ia) at least one reactive carbonyl compound selected from at least one compound according to formula (ia-1),
  
  wherein
• - R ¹ , R ² and R ³ independently represent a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a (C ₂ to C ₆ ) alkenyl group, a formyl group, a hydroxy group, a C ₁ -C ₆ alkoxy group, a C ₁ -C ₆ dialkylamino group, a di (C ₂ -C ₆ hydroxyalkyl) amino group, a di (C ₁ -C ₆ alkoxy-C ₁ -C ₆ alkyl) amino group, a C ₁ -C ₆ -hydroxyalkyloxy group, sulfonyl group, carboxyl group, sulfonic acid group, sulfonamide group, carbamoyl group, C ₂ -C ₆ acyl group, acetyl group or nitro group,
• Z 'is a direct bond or a vinylene group,
• R ⁴ and R ⁵ represent a hydrogen atom or together form, together with the remainder of the molecule, a 5- or 6-membered aromatic or aliphatic ring,
• (ib) at least one CH-acidic compound having an aromatic or aliphatic heterocyclic skeleton selected from cyclic onium compounds having the structural unit of the formula (Ib-1),
  
  wherein
• R ⁶ represents a linear or cyclic C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, an aryl-C ₁ -C ₆ -alkyl group, a C ₁ -C ₆ -hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a C ₁ -C ₆ alkoxy-C ₁ -C ₆ alkyl group, a group R ^I R ^II N- (CH ₂ ) _m -, wherein R ^I and R ^II independently represent a hydrogen atom, a C ₁ -C ₄ -alkyl group, a C ₁ -C ₄ -hydroxyalkyl group or an aryl-C ₁ -C ₆ -alkyl group, wherein R ^I and R ^II together with the nitrogen atom 5-, 6- or 7-membered ring can form and m is a number 2, 3, 4, 5 or 6,
• R ⁷ is a (C ₁ to C ₆ ) -alkyl group, in particular a methyl group,
• - X ^- represents a physiologically acceptable anion,
• The cycle represents all ring structures which may additionally contain further heteroatoms such as nitrogen, oxygen or sulfur and may further carry fused ring structures, all of which ring structures may carry additional substituents, and
• (ii) contains at least one mineral oxide compound.

The Application of the agents according to the invention leads to a strong reduction of scalp colouration in very intense shades and even a complete one Prevention of scalp staining in less intense shades.

When cosmetic carriers are particularly suitable according to the invention Creams, emulsions, gels or surfactant-containing foaming solutions, such as shampoos, foam aerosols or other preparations, especially for the application on the hair are suitable. But it is also conceivable the ingredients in a powdered or tablet-like formulation which is dissolved in water before use.

The cosmetic according to the invention carrier are preferably aqueous or watery-alcoholic.

One aqueous cosmetic carrier contains at least 50% by weight of water.

For the purposes of the present invention, aqueous-alcoholic cosmetic carriers are to be understood as meaning aqueous solutions containing 3 to 70% by weight of a C ₁ -C ₄ -alcohol, in particular 1,2-propylene glycol, ethanol or isopropanol. A preferred aqueous-alcoholic base has an alcohol content of up to 15% by weight, based on the amount of water. The compositions of the invention may additionally contain other organic solvents, such as methoxybutanol, benzyl alcohol or ethyl diglycol. Preference is given to all water-soluble organic solvents.

• a) von Aminen und deren Derivate unter Bildung von Iminen oder Oximen als Additionsverbindung
• b) von Alkoholen unter Bildung von Acetalen oder Ketalen als Additionsverbindung
• c) von Wasser unter Bildung von Hydraten als Additionsverbindung (Komponente (ia) leitet sich in diesem Fall c) von einem Aldehyd ab,

an das Kohlenstoffatom der Carbonylgruppe der reaktiven Carbonylverbindung.Reactive carbonyl compounds as component (Ia-1) in the context of the invention have at least one carbonyl group as a reactive group which reacts with the CH-acidic compound of component (Ib-1) to form a carbon-carbon bond. Preferred reactive carbonyl compounds are aldehydes and ketones. Furthermore, those compounds according to the invention are also suitable as component (ia-1) in which the reactive carbonyl group is derivatized or masked in such a way that the reactivity of the carbon atom of the derivatized carbonyl group with the CH-acidic compounds is always present. These derivatives are preferably addition compounds

• a) amines and derivatives thereof to form imines or oximes as addition compound
• b) of alcohols to form acetals or ketals as addition compound
• c) of water with formation of hydrates as addition compound (component (ia) is derived in this case c) from an aldehyde,

to the carbon atom of the carbonyl group of the reactive carbonyl compound.

The derivatives of benzaldehydes, naphthaldehydes or cinnamaldehydes of the reactive carbonyl compound according to component (ia-1) are preferably selected from at least one compound of the group consisting of 4-hydroxy-3-methoxybenzaldehyde, 3,5-dimethoxy-4-hydroxybenzaldehyde, 4 -Hydroxy-1-naphthaldehyde, 4-hydroxy-2-methoxybenzaldehyde, 3,4-dihydroxy-5-methoxybenzaldehyde, 3,4,5-trihydroxybenzaldehyde, 3,5-dibromo-4-hydroxybenzaldehyde, 4-hydroxy-3-nitrobenzaldehyde , 3-bromo-4-hydroxybenzaldehyde, 4-hydroxy-3-methylbenzaldehyde, 3,5-dimethyl-4-hydroxybenzaldehyde, 5-bromo-4-hydroxy-3-methoxybenzaldehyde, 4-diethylamino-2-hydroxybenzaldehyde, 4 Dimethylamino-2-methoxybenzaldehyde, 2-methoxybenzaldehyde, 3-methoxybenzaldehyde, 4-methoxybenzaldehyde, 2-ethoxybenzaldehyde, 3-ethoxybenzaldehyde, 4-ethoxybenzaldehyde, 4-hydroxy-2,3-dimethoxy-benzaldehyde, 4-hydroxy-2,5 dimethoxybenzaldehyde, 4-hydroxy-2,6-dimethoxybenzaldehyde, 4-hydroxy-2-methylbenzaldehyde, 4-hydroxy-2,3-dimethylbenzaldehyde, 4-hydroxy-2,5-dim ethylbenzaldehyde, 4-hydroxy-2,6-dimethylbenzaldehyde, 3,5-diethoxy-4-hydroxybenzaldehyde, 2,6-diethoxy-4-hydroxybenzaldehyde, 3-hydroxy-4-methoxybenzaldehyde, 2-hydroxy-4-methoxybenzaldehyde, 2-ethoxy-4-hydroxybenzaldehyde, 3-ethoxy-4-hydroxybenzaldehyde, 4-ethoxy-2-hydroxybenzaldehyde, 4-ethoxy-3-hydroxybenzaldehyde, 2,3-dimethoxybenzaldehyde, 2,4-dimethoxybenzaldehyde, 2,5-dimethoxybenzaldehyde, 2,6-dimethoxybenzaldehyde, 3,4-dimethoxybenzaldehyde, 3,5-dimethoxybenzaldehyde, 2,3,4-trimethoxybenzaldehyde, 2,3,5- Trimethoxybenzaldehyde, 2,3,6-trimethoxybenzaldehyde, 2,4,6-tri methoxybenzaldehyde, 2,4,5-trimethoxybenzaldehyde, 2,5,6-trimethoxybenzaldehyde, 2-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 2,3-dihydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 2,4-dihydroxy-3- methyl-benzaldehyde, 2,4-dihydroxy-5-methyl-benzaldehyde, 2,4-dihydroxy-6-methylbenzaldehyde, 2,4-dihydroxy-3-methoxy-benzaldehyde, 2,4-dihydroxy-5-methoxy benzaldehyde, 2,4-dihydroxy-6-methoxybenzaldehyde, 2,5-dihydroxybenzaldehyde, 2,6-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde, 3,4-dihydroxy-2-methylbenzaldehyde, 3,4-dihydroxybenzaldehyde 5-methylbenzaldehyde, 3,4-dihydroxy-6-methylbenzaldehyde, 3,4-dihydroxy-2-methoxybenzaldehyde, 3,5-dihydroxybenzaldehyde, 2,3,4-trihydroxybenzaldehyde, 2,3,5- Trihydroxybenzaldehyde, 2,3,6-trihydroxybenzaldehyde, 2,4,6-trihydroxybenzaldehyde, 2,4,5-trihydroxybenzaldehyde, 2,5,6-trihydroxybenzaldehyde, 4-dimethylaminobenzaldehyde, 4-diethylaminobenzaldehyde, 4-dimethylamino-2-hydroxybenzaldehyde, 4-pyrrolidinobenzaldehyde, 4-morpholinobenzaldehyde, 2-morpholinobenzal dehydrode, 4-piperidinobenzaldehyde, 3,5-dichloro-4-hydroxybenzaldehyde, 4-hydroxy-3,5-diiodobenzaldehyde, 3-chloro-4-hydroxybenzaldehyde, 5-chloro-3,4-dihydroxybenzaldehyde, 5-bromo- 3,4-dihydroxybenzaldehyde, 3-chloro-4-hydroxy-5-methoxybenzaldehyde, 4-hydroxy-3-iodo-5-methoxybenzaldehyde, 2-methoxy-1-naphthaldehyde, 4-methoxy-1-naphthaldehyde, 2-hydroxy 1-naphthaldehyde, 2,4-dihydroxy-1-naphthaldehyde, 4-hydroxy-3-methoxy-1-naphthaldehyde, 2-hydroxy-4-methoxy-1-naphthaldehyde, 3-hydroxy-4-methoxy-1-naphthaldehyde, 2,4-dimethoxy-1-naphthaldehyde, 3,4-dimethoxy-1-naphthaldehyde, 4-dimethylamino-1-naphthaldehyde, 3-hydroxy-4-nitrobenzaldehyde, 2-hydroxy-3-methoxy-5-nitrobenzaldehyde, 5- Nitrovanillin, 2,5-dinitrosalicylaldehyde, 5-bromo-3-nitrosalicylaldehyde, 2-dimethylaminobenzaldehyde, 2-chloro-4-dimethylaminobenzaldehyde, 4-dimethylamino-2-methylbenzaldehyde, 4-diethylamino-cinnamaldehyde, 4-dibutylaminobenzaldehyde, 3 Carboxy-4-hydroxybenzaldehyde, 5-carboxyvanillin, 3-carboxy-4-hydroxy-5-methylbenzaldehyde, 3-carboxy-5-eth oxy-4-hydroxybenzaldehyde, 3-carboxy-4-hydroxybenzaldehyde, 5-carboxyvanillin, 3-carboxy-4-hydroxy-5-methylbenzaldehyde, 3-carboxy-5-ethoxy-4-hydroxybenzaldehyde, 3-allyl-4-hydroxybenzaldehyde, 3-allyl-4-hydroxy-5-methoxybenzaldehyde, 3-allyl-4-hydroxy-5-methylbenzaldehyde, 3-allyl-5-bromo-4-hydroxybenzaldehyde, 3,5-diallyl-4-hydroxybenzaldehyde, 3-allyl 5-carboxy-4-hydroxybenzaldehyde (3-allyl-5-formyl-2-hydroxybenzoic acid), 3-allyl-4-hydroxy-5-formylbenzaldehyde (5-allyl-4-hydroxyisophthalaldehyde) and piperonal.

When CH-acidic compounds generally become such compounds which is bound to an aliphatic carbon atom Carrying hydrogen atom, due to electron-withdrawing Substituents activation of the corresponding carbon-hydrogen bond is effected. In principle, there are no limits to the choice of CH-acidic compounds as long as after condensation with the reactive carbonyl compounds the component (ia-1) a for the human eye is visibly colored. It is preferred according to the invention to those CH-acidic compounds which an aromatic and / or contain a heterocyclic radical. The heterocyclic radical can again be aliphatic or aromatic. Particularly preferred the CH-acidic compounds selected from cationic, heterocyclic Links.

preferred Ring Structures Carrying the Structural Unit of Formula (Ib-1) are preferred according to the invention selected from 3H indolium, benzothiazolium, benzxoazolium, 1,2-dihydro-2-oxopyrimidinium, 1,2-dihydro-2-thioxopyrimidinium, Quinolinium, quinoxaline or pyridinium.

worin

• – R⁸ und R⁹ stehen unabhängig voneinander für eine lineare oder cyclische C₁-C₆-Alkylgruppe, eine C₂-C₆-Alkenylgruppe, eine gegebenenfalls substituierte Arylgruppe, eine gegebenenfalls substituierte Heteroarylgruppe, eine Aryl-C₁-C₆-alkylgruppe, eine C₁-C₆-Hydroxyalkylgruppe, eine C₂-C₆-Polyhydroxyalkylgruppe, eine C₁-C₆-Alkoxy-C₁-C₆-alkylgruppe, eine Gruppe R^IR^IIN-(CH₂)_m-, worin R^I und R^II stehen unabhängig voneinander für ein Wasserstoffatom, eine C₁-C₄-Alkylgruppe, eine C₁-C₄-Hydroxyalkylgruppe oder eine Aryl-C₁-C₆-alkylgruppe, wobei R^I und R^II gemeinsam mit dem Stickstoffatom einen 5-, 6- oder 7-gliedrigen Ring bilden können und m steht für eine Zahl 2, 3, 4, 5 oder 6,
• – R¹⁰ und R¹² stehen unabhängig voneinander für ein Wasserstoffatom oder eine C₁-C₆-Alkylgruppe, wobei mindestens einer der Reste R¹⁰ und R¹² eine C₁-C₆-Alkylgruppe bedeutet,
• – R¹¹ steht für ein Wasserstoffatom, eine C₁-C₆-Alkylgruppe, eine C₁-C₆-Hydroxyalkylgruppe, eine C₂-C₆-Polyhydroxyalkylgruppe, eine C₁-C₆-Alkoxygruppe, eine C₁-C₆-Hydroxyalkoxygruppe, eine Gruppe R^IIIR^IVN-(CH₂)_q-, worin R^III und R^IV stehen unabhängig voneinander für ein Wasserstoffatom, eine C₁-C₆-Alkylgruppe, eine C₁-C₆-Hydroxyalkylgruppe oder eine Aryl-C₁-C₆-alkylgruppe und q steht für eine Zahl 1, 2, 3, 4, 5 oder 6, wobei der Rest R¹¹ zusammen mit einem der Reste R¹⁰ oder R¹² einen 5- oder 6-gliedrigen aromatischen Ring bilden kann, der gegebenenfalls mit einem Halogenatom, einer C₁-C₆-Alkylgruppe, einer C₁-C₆-Hydroxyalkylgruppe, einer C₂-C₆-Polyhydroxyalkylgruppe, einer C₁-C₆-Alkoxygruppe, einer C₁-C₆-Hydroxyalkoxygruppe, einer Nitrogruppe, einer Hydroxygruppe, einer Gruppe R^VR^VIN-(CH₂)_s-, worin R^V und R^VI stehen unabhängig voneinander für ein Wasserstoffatom, eine C₁-C₆-Alkylgruppe, eine C₁-C₆-Hydroxyalkylgruppe oder eine Aryl-C₁-C₆-alkylgruppe und s steht für eine Zahl 0, 1, 2, 3, 4, 5 oder 6 substituiert sein kann,
• – Y steht für ein Sauerstoffatom, ein Schwefelatom oder eine Gruppe NR^VII, worin R^VII steht für ein Wasserstoffatom, eine Arylgruppe, eine Heteroarylgruppe, eine C₁-C₆-Alkylgruppe oder eine C₁-C₆-Arylalkylgruppe,
• – X^- steht für ein physiologisch verträgliches Anion.

The CH-acidic compounds of the oxo dye precursors of component (Ib) are preferably selected from at least one compound of formula (Ib-2)

wherein

• R ⁸ and R ⁹ independently of one another represent a linear or cyclic C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, an aryl-C ₁ -C ₆ - alkyl group, a C ₁ -C ₆ hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a C ₁ -C ₆ alkoxy-C ₁ -C ₆ alkyl group, a group R ^I R ^II N- (CH ₂ ) _m in which R ^I and R ^II independently of one another represent a hydrogen atom, a C ₁ -C ₄ -alkyl group, a C ₁ -C ₄ -hydroxyalkyl group or an aryl-C ₁ -C ₆ -alkyl group, where R ^I and R ^II together with the nitrogen atom can form a 5-, 6- or 7-membered ring and m is a number 2, 3, 4, 5 or 6,
• - R ¹⁰ and R ¹² independently represent a hydrogen atom or a C ₁ -C ₆ alkyl group, wherein at least one of R ¹⁰ and R ^{12 is} a C ₁ -C ₆ -alkyl group,
• R ¹¹ represents a hydrogen atom, a C ₁ -C ₆ -alkyl group, a C ₁ -C ₆ -hydroxyalkyl group, a C ₂ -C ₆ -polyhydroxyalkyl group, a C ₁ -C ₆ -alkoxy group, a C ₁ -C ₆ -Hydroxyalkoxygruppe, a group R ^III R ^IV N- (CH ₂ ) _q -, wherein R ^III and R ^IV independently represent a hydrogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ hydroxyalkyl group or a Aryl-C ₁ -C ₆ -alkyl group and q is a number 1, 2, 3, 4, 5 or 6, wherein the radical R ¹¹ together with one of the radicals R ¹⁰ or R ^{12 is} a 5- or 6-membered aromatic Ring optionally containing a halogen atom, a C ₁ -C ₆ -alkyl group, a C ₁ -C ₆ -hydroxyalkyl group, a C ₂ -C ₆ -polyhydroxyalkyl group, a C ₁ -C ₆ -alkoxy group, a C ₁ - C ₆ -hydroxyalkoxy group, a nitro group, a hydroxy group, a group R ^V R ^VI N- (CH ₂ ) _s -, wherein R ^V and R ^VI independently of one another represent a hydrogen atom, a C ₁ -C ₆ -alkyl group, a C ₁ -C ₆ -hydroxyalkyl group or an aryl-C ₁ -C ₆ -alkyl group and s is a number 0, 1, 2, 3, 4, 5 or 6 may be substituted,
• Y is an oxygen atom, a sulfur atom or a group NR ^VII , in which R ^VII represents a hydrogen atom, an aryl group, a heteroaryl group, a C ₁ -C ₆ -alkyl group or a C ₁ -C ₆ -arylalkyl group,
• - X ^- stands for a physiologically compatible anion.

At least one group R ¹⁰ or R ¹² according to formula (Ib-2) is necessarily a C ₁ -C ₆ -alkyl group. This alkyl group preferably carries at least two hydrogen atoms on its α-carbon atom. Particularly preferred alkyl groups are the methyl, ethyl, propyl, n-butyl, iso-butyl, n-pentyl, neo-pentyl, n-hexyl group. Most preferably, R ¹⁰ and R ¹² are each independently hydrogen or a methyl group, wherein at least one group R ¹⁰ or R ^{12 is} a methyl group.

In a preferred embodiment Y stands for the formula (ib-2) an oxygen or sulfur atom, more preferably an oxygen atom.

The radical R ^{8 of} the formula (Ib-2) is preferably selected from a (C ₁ -C ₆ ) -alkyl group (particularly preferably a methyl group), a C ₂ -C ₆ -alkenyl group (in particular an allyl group), a hydroxy- ( C ₂ to C ₆ ) alkyl group or an optionally substituted benzyl group.

R ^{11 of} the formula (Ib-2) is preferably a hydrogen atom.

Particularly preferred in formula (Ib-2) are the radicals R ⁹ , R ¹⁰ and R ^{12 is} a methyl group, the radical R ^{11 is} a hydrogen atom, Y is an oxygen or sulfur atom and the radical R ⁸ is selected from a ( C ₁ -C ₆ ) -alkyl group (particularly preferably a methyl group), a C ₂ -C ₆ -alkenyl group (in particular an allyl group), a hydroxy (C ₂ - to C ₆ ) -alkyl group or an optionally substituted benzyl group.

Preferably, the compounds of the formula (Ib-2) are selected from one or more compounds of the group of salts with physiologically acceptable counterion X ^- , which is formed from salts of
1,2-dihydro-1,3,4,6 tetramethyl-2-oxo-pyrimidiniums,
1,2-dihydro-1,3-diethyl-4,6-dimethyl-2-oxo-pyrimidiniums,
1,2-dihydro-1,3-dipropyl-4,6-dimethyl-2-oxo-pyrimidiniums,
1,2-dihydro-1,3-di (2-hydroxyethyl) -4,6-dimethyl-2-oxo-pyrimidiniums,
1,2-dihydro-1,3-diphenyl-4,6-dimethyl-2-oxo-pyrimidiniums,
1,2-dihydro-1,3,4-trimethyl-2-oxo-pyrimidiniums,
1,2-dihydro-1,3-diethyl-4-methyl-2-oxo-pyrimidiniums,
1,2-dihydro-1,3-dipropyl-4-methyl-2-oxo-pyrimidiniums,
1,2-dihydro-1,3-di (2-hydroxyethyl) -4-methyl-2-oxo-pyrimidiniums,
1,2-dihydro-1,3-diphenyl-4-methyl-2-oxo-pyrimidiniums,
1-allyl-1,2-dihydro-3,4,6-trimethyl-2-oxo-pyrimidiniums,
1,2-dihydro-1- (2-hydroxyethyl) -3,4,6-trimethyl-2-oxo-pyrimidiniums,
1,2-dihydro-1,3,4,6-tetramethyl-2-thioxo-pyrimidiniums,
1,2-dihydro-1,3-diethyl-4,6-dimethyl-2-thioxo-pyrimidiniums,
1,2-dihydro-1,3-dipropyl-4,6-dimethyl-2-thioxo-pyrimidiniums,
1,2-dihydro-1,3-di (2-hydroxyethyl) -4,6-dimethyl-2-thioxo-pyrimidiniums,
1,2-dihydro-1,3-diphenyl-4,6-dimethyl-2-thioxo-pyrimidiniums,
1,2-dihydro-1,3,4-trimethyl-2-thioxo-pyrimidiniums,
1,2-dihydro-1,3-diethyl-4-methyl-2-thioxo-pyrimidiniums,
1,2-dihydro-1,3-dipropyl-4-methyl-2-thioxo-pyrimidiniums,
1,2-dihydro-1,3-di (2-hydroxyethyl) -4-methyl-2-thioxo-pyrimidiniums,
1,2-dihydro-1,3-diphenyl-4-methyl-2-thioxo-pyrimidiniums,
1,2-dihydro-3,4-dimethyl-2-oxo-quinazolinium and
1,2-dihydro-3,4-dimethyl-2-thioxo-chinazoliniums.

Very particularly preferred compounds of the formula (Ib-2) are selected from one or more compounds of the group of salts with physiologically tolerable counterion X ^- , which is formed from salts of
1,2-dihydro-1,3,4,6 tetramethyl-2-oxo-pyrimidiniums,
1,2-dihydro-1,3,4-trimethyl-2-oxo-pyrimidiniums,
1-allyl-1,2-dihydro-3,4,6-trimethyl-2-oxo-pyrimidiniums,
1,2-dihydro-1- (2-hydroxyethyl) -3,4,6-trimethyl-2-oxopyrimidinium and
1,2-dihydro-1,3,4,6-tetramethyl-2-thioxo-pyrimidiniums.

X ^- in the formulas (Ib-1) and (Ib-2) and in the above lists is preferably halide, benzenesulfonate, p-toluenesulfonate, C ₁ -C ₄ -alkanesulfonate, trifluoromethanesulfonate, perchlorate, 0.5 sulfate, hydrogensulfate, tetrafluoroborate, Hexafluorophosphate or tetrachlorozincate. The anions chloride, bromide, iodide, hydrogensulfate or p-toluenesulfonate are particularly preferably used as X.

The CH-acidic compounds (ib) and the reactive carbonyl compounds (ia) are each preferably in an amount of 0.03 to 65 mmol, in particular from 1 to 40 mmol, based on 100 g of the total colorant used.

Mineral oxidic compounds in the context of the invention (at 25 ° C and 1 atm Pressure) solid, crystalline or amorphous, and inorganic metalloid or metal oxides including their derivatives. They are in the agents according to the invention in particulate Form before. The mineral oxide compounds are in the cosmetic carrier the agent according to the invention preferably dispersed or form therein a gel structure.

The suitable according to the invention mineral oxide compounds are preferred in an amount of 1 to 20 wt .-%, particularly preferably from 2 to 10 wt .-%, respectively based on the weight of the agent according to the invention.

Mineral oxide compounds which can be used according to the invention preferably have a BET specific surface area of from 40 to 4000 m ² / g, in particular from 100 to 1000 m ² / g (determined in each case according to DIN ISO 9277: 2003-05).

preferred mineral according to the invention Oxide compounds have pores, especially mesopores and / or Micropores and / or macropores. A pore size of at least 0.4 nm a preferably suitable pore size.

The mineral oxide compounds preferably have an average pore volume of from 0.01 to 5.0 cm ³ / g, in particular from 0.1 to 4 cm ³ / g.

The in the invention used dye contained mineral oxide compounds have preferred a particle diameter less than 800 microns, preferably less than 300 microns.

The usable according to the invention mineral oxide compounds can be hydrophilic or hydrophobic be.

Hydrophilic mineral oxidic compounds are easily homogeneous in water dispersible. they have hydrophilic groups on the surface, such as. Hydroxy groups or organic groups with cationic or anionic charge.

hydrophobic Mineral oxide compounds preferably carry on their surface hydrophobic, organic Radicals, in particular silicone chains and / or hydrocarbon radicals, which preferably each over Ion interactions or covalently attached to the surface of the mineral oxide compound are bound.

The hydrophobic, organic radicals are preferred according to the invention a water solubility from less than 0.1 mg to 1000 g of water at 20 ° C. The water solubility of the hydrophobic organic radical is determined by those organic Compound determined by substitution of the mineral oxide compound or its surface is obtained by a hydrogen atom.

preferred Hydrophobic mineral oxide compounds have been treated with at least a hydrophobic organic residue on the surface by means of corresponding silicon-organic radicals silylated.

-NH-C(O)O-Me, -NH-C(O)O-Et, -NH-(CH₂)₃-Si(O(C₁-C₆)alykl)₃
R' eine (C₁-C₂₀)Alkylgruppe bedeutet und
R'' eine (C₁-C₂₀)Alkylgruppe oder eine Vinylgruppe bedeutet.A preferred hydrophobic, mineral oxide compound in the sense of the invention has been silylated with at least one of the following radicals:
R'Si
R'R''Si
R ' ₂ Si
R '[R- (CH ₂ ) _n ] Si
R ' _{(y + 1)} [R- (CH ₂ ) _n ] _(2-y) Si
[R- (CH ₂ ) _n ] ₃ Si
wherein
y is a number 0, 1, or 2,
n is an integer from 1 to 20 and
R stands for a rest
(C ₁ -C ₁₀ ) alkyl, aryl, (C ₁ -C ₆ ) perfluoroalkyl, -NH ₂ , -N ₃ , -SCN, -CH = CH ₂ , -O (O) CC (CH ₃ ) = CH ₂ , -OCH ₂ -CH = CH ₂ ,

-NH-C (O) O-Me, -NH-C (O) O-Et, -NH- (CH ₂ ) ₃ -Si (O (C ₁ -C ₆ ) alkyl) ₃
R 'is a (C ₁ -C ₂₀ ) alkyl group and
R '' is a (C ₁ -C ₂₀₎ alkyl group or a vinyl group.

The vierbindige silicon atom of the formulas given above forms the saturation the remaining bonds to the surface of the mineral oxide Connection off.

The surface-modified mineral oxide compound is preferred by the following method receive. The mineral oxide compound is at least a silylating agent, wherein the silylating agent carries at least one hydrophobic organic radical, which forms the hydrophobic, organic surface modification.

It is preferred according to the invention, the mineral oxide compound and the silylating agent in this process in a weight ratio of 95: 5 to 99: 1.

When Silylating agent is preferably at least one member of the group selected, which is formed from silanes, halosilanes, alkoxysilanes and Silazanes.

Preferred representatives from the group of silanes are hexa (C ₁ -C ₂₀ ) alkyldisilanes, in particular hexamethyldisilane.

-NH-C(O)O-Me, -NH-C(O)O-Et, -NH-(CH₂)₃-Si(O(C₁-C₆)alkyl)₃.When a halosilane is used as the silylating agent, as the preferred halosilane, at least one compound selected from the group consisting of the compounds is selected
[(C ₁ -C ₂₀ ) alkyl] _z SiX _{(4-z ')}
X ₃ Si [(CH _{2) n} -R]
X _z [(C ₁ -C ₂₀₎ alkyl] Si (CH _{2) n} -R
[(C ₁ -C ₂₀ ) alkyl] _{(y '+ 1)} [R- (CH ₂ ) _n ] _(2-y') SiX
wherein
X represents a chlorine, bromine or iodine atom,
z 'is a number 1, 2 or 3,
y 'is a number 0, 1 or 2
n is an integer from 1 to 20 and
R stands for a rest
(C ₁ -C ₁₀ ) alkyl, aryl, (C ₁ -C ₆ ) perfluoroalkyl, -NH ₂ , -N ₃ , -SCN, -CH = CH ₂ , -O (O) CC (CH ₃ ) = CH ₂ , -OCH ₂ -CH = CH ₂ ,

-NH-C (O) O-Me, -NH-C (O) O-Et, -NH- (CH ₂ ) ₃ -Si (O (C ₁ -C ₆ ) alkyl) ₃ .

-NH-C(O)O-Me, -NH-C(O)O-Et, -NH-(CH₂)₃-Si(O(C₁-C₆)alkyl)₃.When an alkoxysilane is used as the silylating agent, as the preferred alkoxysilane, at least one compound selected from the group consisting of the compounds is selected
[(C ₁ -C ₂₀ ) alkylO] _z Si (C ₁ -C ₂₀ ) alkyl _(4-z)
[(C ₁ -C ₂₀ ) alkyl O] _z Si [(CH ₂ ) _n -R] _(4-z)
[(C ₁ -C ₂₀ ) alkylO] ₂ [(C ₁ -C ₂₀ ) alkyl] Si (CH ₂ ) _n -R
[(C ₁ -C ₂₀₎ alkylO] [(C ₁ -C ₂₀₎ alkyl] ₂ Si (CH _{2) n} -R
[(C ₁ -C ₂₀ ) alkylO] [(C ₁ -C ₂₀ ) alkyl] Si [(CH ₂ ) _n -R] ₂
(C ₁ -C ₂₀ alkyl) ₃ SiO-C (CH ₃ ) = N-Si (C ₁ -C ₂₀ ) alkyl ₃ , in which
n is an integer from 1 to 20 and
z is a number 1, 2, or 3
R stands for a rest
(C ₁ -C ₂₀ ) alkyl, aryl, (C ₁ -C ₆ ) perfluoroalkyl, -NH ₂ , -N ₃ , -SCN, -CH = CH ₂ , -O (O) CC (CH ₃ ) = CH ₂ , -OCH ₂ -CH = CH ₂ ,

-NH-C (O) O-Me, -NH-C (O) O-Et, -NH- (CH ₂ ) ₃ -Si (O (C ₁ -C ₆ ) alkyl) ₃ .

As a preferred silazane is at least one compound from the class of disilazanes, in particular at least one compound of disilazanes of the formula
R ' ₂ R "Si-NH-SiR' ₂ R"
selected in which
R 'is a (C ₁ -C ₂₀ ) alkyl group and
R '' is a (C ₁ -C ₂₀ ) alkyl group or a vinyl group. A particularly preferred silazane is hexamethyldisilazane.

All of the above alkyl groups, whether (C ₁ -C ₆ ) alkyl, (C ₁ -C ₁₀ ) alkyl or (C ₁ -C ₂₀ ) alkyl, may be both cyclic and linear or branched. Examples of alkyl groups which can be used according to the invention are methyl, ethyl, n-propyl, isopropyl, n-butyl, cyclopentyl, cyclohexyl, n-decyl, lauryl, myristyl, cetyl, stearyl, isostearyl and behenyl.

One example for an aryl group according to the invention is the phenyl group.

Examples of a (C ₁ -C ₆ ) perfluoroalkyl group according to the invention are trifluoromethyl, perfluoroethyl, perfluoropropyl and perfluorohexyl.

In the agents according to the invention preferably usable mineral oxide compounds selected from at least one representative from the group that is formed from aluminates, silicates and titanium dioxide, in particular formed is made of aluminates, aluminum silicates and polysilicic acids. As well According to the invention are mixtures these preferred mineral oxide compounds. The special ones Representatives from the above group can be hydrophilic or hydrophobic.

Especially preferred aluminates are selected from active alumina, alpha alumina, beta alumina, gamma alumina, and mixtures thereof.

preferred suitable silicates are selected from the aluminum silicates and / or the Selected polysilicic acids.

Especially preferred aluminum silicates (also called aluminosilicates) are selected among phyllosilicates, Tectosilikaten and their mixtures.

Prefers suitable phyllosilicates are selected from kaolins (here in particular kaolinite, dickite, hallosite and nacrite), serpentine, talc, Pyrophyllite, bentonite, mica (here in particular under illite, muscovite, Paragonite, phlogopite, biotite, lepidolite, margarite, smectite (here especially montmorillonite, saponite, nontronite, hectorite)) and mixtures thereof.

Prefers suitable tectosilicates are selected from feldspar minerals (especially albite, orthoclase, anorthite, leucite, sodalite, hauyne, Labradorite, lasurite, nosean, nepheline), zeolites, quartz, as well as mixtures it.

Zeolites are natural or synthetic crystalline aluminum silicates of alkali or alkaline earth metals. Zeolites consist of SiO ₄ and AlO ₄ tetrahedra, which are replaced by four, six, eight or twelve oxygen fabric rings are formed, whereby cavities are formed which extend through the entire zeolite crystal. Among the preferred zeolites are the zeolites of the type A, K, L, PL, O, T, X, Y and Ω and mixtures thereof. Particularly preferred zeolites are selected in particular under zeolite A (here in particular under Na ₁₂ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ]), Ca ₅ Na ₅ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ], [K ₁₂ (AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ]), zeolite X (here in particular under Na ₈₆ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ]). Ca ₄₀ Na ₆ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ]]. Sr ₂₁ Ba ₂₂ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ]). Zeolite Y (here especially Na ₅₆ [(AlO ₂ ) ₅₆ (SiO ₂ ) ₁₃₆ ], Na ₅₆ [(AlO ₂ ) ₅₆ (SiO ₂ ) ₁₃₆ ]), ZSM-5 (here in particular Na ₃ [(AlO ₂ ) ₃ (SiO ₂ ) ₉₃ ]), mordenite, silicalite (SiO ₂ ) ₉₆ and mixtures thereof

Polysilicic acids are preferably selected from amorphous compounds of the formula (SiO ₂ ) _n m H ₂ O, where m and n are each independently positive integers. Depending on the nature of their production, a distinction is made between precipitated silicas and fumed silicas.

The Precipitated silicas from aqueous Alkali silicate solutions by precipitation made with mineral acids. The resulting colloidal primary particles agglomerate with progressive reaction and fused into aggregates.

The pyrogenic silicas are produced from silicon tetrachloride in the presence of oxyhydrogen in a oxyhydrogen flame or in the arc:

When mineral oxide compound is particularly preferred at least a fumed silica, which may be modified hydrophilic or hydrophobic, in the agent according to the invention used.

Preferably, suitable commercial products are those sold under the trade name Aerosil ^® from Degussa fumed silicas such as Aerosil 200 (hydrophilic fumed silica having a particle diameter of 12 nm and a BET surface area of 200 m ² / g), Aerosil 300 (hydrophilic fumed silica having a particle diameter of 7 μm and a BET surface area of 300 m ² / g), Aerosil 380 (hydrophilic fumed silica having a particle diameter of 7 μm and a BET surface area of 380 m ² / g), Aerosil R 104 (hydrophobicized with octamethylcyclotetrasiloxane fumed silica having a particle diameter of 12 nm and a BET surface area of 150 m ² / g), Aerosil R 805 (fumed silica hydrophobicized with trimethoxyoxtylsilane with a particle diameter of 12 nm and a BET surface area of 150 m ² / g), Aerosil R 812 (with hexamethyldisilazane hydrophobized fumed silica having a particle diameter of 7 microns and a BET Oberflä 220 m ² / g (INCI name: Silica Silylate), Aerosil R 972 (with dimethyldichlorosilane hydrophobized fumed silica having a particle diameter of 16 nm and a BET surface area of 110 m ² / g (INCI name: Silica Dimethyl Silylate ), Aerosil R 974 (with dimethyldichlorosilane hydrophobized fumed silica having a particle diameter of 12 nm and a BET surface area of 150 to 190 m ² / g (INCI name: Silica Dimethyl Silylate).

• (iiia) mindestens einem Silikonderivat, welches einen Siedepunkt von weniger als 300 °C bei einem Druck von 1 atm besitzt, mit
• (iiib) mindestens einem Silikon, welches einen Siedepunkt von mindestens 300 °C bei einem Druck von 1 atm besitzt

enthält.The effect according to the invention is further enhanced if the composition according to the invention additionally comprises a combination of

• (iiia) at least one silicone derivative having a boiling point of less than 300 ° C at a pressure of 1 atm
• (iiib) at least one silicone which has a boiling point of at least 300 ° C at a pressure of 1 atm

contains.

worin
n steht für 3, 4, 5, 6 oder 7,
R¹³ oder R¹⁴ stehen für jedes einzelne Fragment der n Fragmente unabhängig voneinander für eine (C₁ bis C₆)-Alkylgruppe, eine Arylgruppe, eine (C₁ bis C₆)-Alkoxygruppe.The silicones of component (iiia) are preferably selected from at least one silicone having the formula (Si-1) and / or hexamethyldisiloxane,

wherein
n stands for 3, 4, 5, 6 or 7,
R ¹³ or R ¹⁴ independently represent for each fragment of the n fragments a (C ₁ to C ₆ ) -alkyl group, an aryl group, a (C ₁ to C ₆ ) -alkoxy group.

The Silicones of component (iiia) are more preferably selected from at least one silicone having the above formula (Si-1).

In formula (Si-1) n is preferably 4 or 5 and R ¹³ and R ^{14 are} a methyl group. In this case, it is again preferable if, as compounds of the formula (Si-1), a mixture of cyclotetrasiloxane and cyclopentasiloxane is present in the agents according to the invention. The weight ratio of cyclotetrasiloxane to cyclopentasiloxane with one another is in this case preferably 1: 2 to 1: 1, more preferably 1: 1.7 to 1: 1.2.

The Silicones of component (iiia) are preferably in an amount of 0.4 to 8.0 wt .-% based on the weight of the total composition in the agent according to the invention contain.

worin unabhängig voneinander
m steht für eine ganze Zahl von 200 bis 10000, insbesondere von 400 bis 2000,
R¹⁵ oder R¹⁶ stehen für jedes einzelne Fragment der m Fragmente unabhängig voneinander für eine (C₁ bis C₆)-Alkylgruppe, eine Arylgruppe, eine (C₁ bis C₆)-Alkoxygruppe.The silicones of component (iiib) are preferably selected from at least one silicone from the group which is formed from silicones of the formula (Si-2a) and silicones of the formula (Si-2b)

wherein independently of one another
m stands for an integer from 200 to 10,000, in particular from 400 to 2000,
R ¹⁵ or R ¹⁶ independently represent for each fragment of the m fragments a (C ₁ to C ₆ ) -alkyl group, an aryl group, a (C ₁ to C ₆ ) -alkoxy group.

It is preferable that, in the formulas (Si-2a) and (Si-2b), R ¹⁵ and R ^{16 represent} a methyl group.

It is preferred according to the invention, if they are liquid silicones of the formulas (Si-2a) or (Si-2b) at 20 ° C.

The Silicones of component (iiib) are preferably in an amount of 0.1 to 2.0 wt .-% based on the weight of the total composition in the agent according to the invention contain.

In a particularly preferred embodiment The invention is a combination of (iiia) and (iiib) a solution of at least one compound of the formula (Si-2a) and / or (Si-2b) in a solvent from at least one compound (Si-1) used.

there it is preferred if for the preparation of this solution at most 30 wt .-% compounds of the formula (Si-2a) and / or (Si-2b) in at most 70% by weight of compounds of the formula (Si-1), especially at most 20% by weight of the formula (Si-2a) and / or (Si-2b) in at most 80 wt .-% compounds of formula (Si-1) are dissolved.

there it is again preferred if, as compounds of the formula (Si-1) a mixture of cyclotetrasiloxane and cyclopentasiloxane as solvent is used. The weight ratio Cyclotetrasiloxane to cyclopentasiloxane with each other here is preferably 1 to 2 to 1 to 1, more preferably 1 to 1.7 to 1 to 1,2.

The above-described solutions of (Si-2a) and / or (Si-2b) in (Si-1) preferably have a viscosity of 6000 mm ² / s at 25 ° C.

The previously described as a combination (iiia) and (iiib) silicone-in-silicone solutions described according to the invention again preferably a water solubility at most 0.1 mg to 1 L of water.

A preferred commercial product is Dow Corning 1401 as a solution of 13% by weight of a dimethiconol of formula (Si-2a) in a mixture of 50% by weight of cyclopentasiloxane and 37% by weight of cyclo tetrasiloxane.

The previously described solutions the compounds of formula (Si-2a) and / or (Si-2b) in compounds of the formula (Si-1) are preferably in a range of 0.5% by weight to 10 wt .-%, in particular from 1.0 wt .-% to 7.0 wt .-%, very particularly preferably from 2 wt .-% to 5 wt .-%, each based on the weight of the ready-to-use agent.

• – natürlichen oder synthetischen Direktfarbstoffen und
• – Oxidationsfarbstoffvorprodukten vom Entwickler- und Kupplertyp,

sowie aus Mischungen von Vertretern einer oder mehrerer dieser Gruppen, enthalten sein.In addition to the coloring components (ia-1) and (ib-1) contained in the agents according to the invention, at least one further coloring component can be selected from

• Natural or synthetic direct dyes and
• Developer and coupler type oxidation dye precursors,

and mixtures of representatives of one or more of these groups.

The in the inventive compositions additionally contained direct dyes as a coloring component are usually Nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols. Preferred direct dyes are those among the international names or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, Acid Yellow 1, Acid Yellow 10, Acid Yellow 23, Acid Yellow 36, HC Orange 1, Disperse Orange 3, Acid Orange 7, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, Acid Red 33, Acid Red 52, HC Red BN, Pigment Red 57: 1, HC Blue 2, HC Blue 12, Disperse Blue 3, Acid Blue 7, Acid Green 50, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Acid Violet 43, Disperse Black 9, Acid Black 1 and Acid Black 52 known compounds and 1,4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis (β-hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- (β-hydroxyethyl) aminophenol, 2- (2'-hydroxyethyl) amino-4,6-dinitrophenol, 1- (2'-hydroxyethyl) amino-4-methyl-2-nitrobenzene, 1-amino-4- (2'-hydroxyethyl) amino-5-chloro-2-nitrobenzene, 4-amino-3-nitrophenol, 1- (2'-ureidoethyl) amino-4-nitrobenzene, 4-amino-2-nitrodiphenylamine-2'-carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4-naphthoquinone, picramic acid and its salts, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene.

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

Furthermore, the compositions according to the invention can contain as direct dye a cationic substantive dye. Particularly preferred are

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

Preferred cationic direct dyes of the group © are in particular the following compounds:

The compounds of the formulas (DZ1), (DZ3) and (DZ5) are very particularly preferred cationic direct dyes of the group ^© . The cationic direct dyes, which are sold under the trademark Arianor ^®, according to the invention are particularly preferred direct dyes.

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

wobei

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

It 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 (C ₁ to C ₄ ) alkyl, 4'-aminophenyl or (C ₁ to C ₄ ) alkyl substituted with a nitrogen-containing group, a phenyl or a 4'-aminophenyl;
• 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 (C ₁ to C ₄ ) alkyl or (C ₁ to C ₄ ) alkyl substituted with a nitrogen-containing group;
• G ³ represents a hydrogen atom, a halogen atom, such as a chlorine, bromine, iodine or fluorine atom, a (C ₁ to C ₄ ) -alkyl radical, a (C ₁ to C ₄ ) -monohydroxyalkyl radical, a (C ₂ to C ₄ ) - polyhydroxyalkyl radical, a (C ₁ to C ₄ ) -hydroxyalkoxy radical, a (C ₁ to C ₄ ) -acetylaminoalkoxy radical, a mesylamino (C ₁ to C ₄ ) -alkoxy radical or a (C ₁ to C ₄ ) -Carbamoylaminoalkoxyrest;
• G ⁴ represents a hydrogen atom, a halogen atom 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.

Particularly preferred p-phenylenediamines of formula (E1) are selected from one or more compounds of the group formed 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-chloroaniline, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- ( α, β-dihydroxyethyl) -p-phenylenediamine, 2-fluoro-p-phenylenediamine, 2-isopropyl-p-phenylenediamine, N- (β-hydroxypropyl) -p-phenylenediamine, 2-hydroxymethyl-p-phenylenediamine, N, N Dimethyl 3-methyl-p-phenylenediamine, N, N- (ethyl, β-hydroxyethyl) -p-phenylenediamine, N- (β, γ-dihydroxypropyl) -p-phenylenediamine, N- (4'-aminophenyl) - p-phenylenediamine, N-phenyl-p-phenyle ndiamine, 2- (β-hydroxyethyloxy) -p-phenylenediamine, 2- (β-acetylaminoethyloxy) -p-phenylenediamine, N- (β-methoxyethyl) -p-phenylenediamine, N- (4-amino-3-methylphenyl) - N- [3- (1H-imidazol-1-yl) propyl] amine, 5,8-diaminobenzo-1,4-dioxane and ih physiologically compatible salts.

Very particular according to the invention Preferred p-phenylenediamine derivatives of the formula (E1) are selected from at least one compound of the group p-phenylenediamine, p-toluenediamine, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- (α, β-dihydroxyethyl) -p-phenylenediamine, N, N-bis (β-hydroxyethyl) -p-phenylenediamine, N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazol-1-yl) propyl] amine, as well as the physiologically acceptable salts of these connections.

It can continue according to the invention be preferred to use as a developer component compounds, which contain at least two aromatic nuclei which are reactive with amino and / or hydroxyl groups are substituted.

wobei:

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

mit der Maßgabe, dass die Verbindungen der Formel (E2) nur eine Verbrückung Y pro Molekül enthalten.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 corresponding to the following formula (E2) and their physiologically tolerated salts:

in which:

• - Z ¹ and Z ² independently of one another are a hydroxyl or NH ₂ radical which is optionally substituted by a (C ₁ to C ₄ ) -alkyl radical, by a (C ₁ to C ₄ ) -hydroxyalkyl radical and / or by a bridge Y is substituted or which is optionally part of a bridging ring system,
• - The bridge Y is an alkylene group having 1 to 14 carbon atoms, such as a linear or branched alkylene chain or an alkylene ring interrupted or terminated by one or more nitrogen-containing groups and / or one or more heteroatoms such as oxygen, sulfur or nitrogen atoms may be substituted by one or more hydroxyl or (C ₁ to C ₈ ) alkoxy, or a direct bond,
• G ⁵ and G ⁶ independently of one another represent a hydrogen or halogen atom, a (C ₁ to C ₄ ) -alkyl radical, a (C ₁ to C ₄ ) -monohydroxyalkyl radical, a (C ₂ to C ₄ ) -polyhydroxyalkyl radical, - (C ₁ to C ₄ ) -aminoalkyl radical or a direct compound for 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 (C ₁ to C ₄ ) -alkyl radical,

with the proviso that the compounds of the formula (E2) contain only one bridge Y per molecule.

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

preferred binuclear developer components of the formula (E2) are especially selected from at least one of the following compounds: 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- (methylamino) phenyl) tetramethylenediamine, N, N'-diethyl-N, N'-bis- (4'-amino-3'-methylphenyl) ethylenediamine, Bis- (2-hydroxy-5-aminophenyl) methane, N, N'-bis (4'-aminophenyl) -1,4-diazacycloheptane, N, N'-bis (2-hydroxy-5-aminobenzyl) piperazine, N- (4'-aminophenyl) -p-phenylenediamine and 1,10-bis (2 ', 5'-diaminophenyl) -1,4,7,10-tetraoxadecane as well as their physiologically tolerable Salts.

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

wobei:

• – G¹³ steht für ein Wasserstoffatom, ein Halogenatom, einen (C₁ bis C₄)-Alkylrest, einen (C₁ bis C₄)-Monohydroxyalkylrest, einen (C₂ bis C₄)-Polyhydroxyalkylrest, einen (C₁ bis C₄)-Alkoxy-(C₁ bis C₄)-alkylrest, einen (C₁ bis C₄)-Aminoalkylrest, einen Hydroxy-(C₁ bis C₄)-alkylaminorest, einen (C₁ bis C₄)-Hydroxyalkoxyrest, einen (C₁ bis C₄)-Hydroxyalkyl-(C₁ bis C₄)-aminoalkylrest oder einen (Di-[(C₁ bis C₄)-alkyl]amino)-(C₁ bis C₄)-alkylrest, und
• – G¹⁴ steht für ein Wasserstoff- oder Halogenatom, einen (C₁ bis C₄)-Alkylrest, einen (C₁ bis C₄)-Monohydroxyalkylrest, einen (C₂ bis C₄)-Polyhydroxyalkylrest, einen (C₁ bis C₄)-Alkoxy-(C₁ bis C₄)-alkylrest, einen (C₁ bis C₄)-Aminoalkylrest oder einen (C₁ bis C₄)-Cyanoalkylrest,
• – G¹⁵ steht für Wasserstoff, einen (C₁ bis C₄)-Alkylrest, einen (C₁ bis C₄)-Monohydroxyalkylrest, einen (C₂ bis C₄)-Polyhydroxyalkylrest, einen Phenylrest oder einen Benzylrest, und
• – G¹⁶ steht für Wasserstoff oder ein Halogenatom.

Furthermore, it may be preferred according to the invention to use as the developer component a p-aminophenol derivative 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 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, (C ₁ to C ₄ ) aminoalkyl, hydroxy (C ₁ to C ₄ ) alkylamino, (C ₁ to C ₄ ) hydroxyalkoxy, a (C ₁ to C ₄ ) hydroxyalkyl (C ₁ to C ₄ ) aminoalkyl radical or a (di - [(C ₁ to C ₄ ) alkyl] amino) - (C ₁ to C ₄ ) alkyl radical, and
• 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 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 or a benzyl radical, and
• - G ¹⁶ is hydrogen or a halogen atom.

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

preferred p-aminophenols of the formula (E3) are in particular p-aminophenol, N-methyl-p-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 2-hydroxymethylamino-4-aminophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2- (β-hydroxyethoxy) phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethyl-phenol, 4-amino-2-aminomethylphenol, 4-amino-2- (β-hydroxyethyl-aminomethyl) phenol, 4-amino-2- (α, β-dihydroxyethyl) -phenol, 4-amino-2-fluorophenol, 4-amino-2-chlorophenol, 4-amino-2,6-dichlorophenol, 4-amino-2- (diethyl-aminomethyl) -phenol and its physiological acceptable Salts.

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

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

Farther For example, the developer component may be selected from heterocyclic Developer components, such as pyrimidine derivatives, Pyrazole derivatives, pyrazolopyrimidine derivatives or their physiological acceptable Salt.

worin

• – G¹⁷, G¹⁸ und G¹⁹ unabhängig voneinander für ein Wasserstoffatom, eine Hydroxygruppe, eine (C₁ bis C₄)-Alkoxygruppe oder eine Aminogruppe steht und
• – G²⁰ für eine Hydroxygruppe oder eine Gruppe -NG²¹G²² steht, worin G²¹ und G²² unabhängig voneinander stehen für ein Wasserstoffatom, eine (C₁ bis C₄)-Alkylgruppe, eine (C₁ bis C₄)-Monohydroxyalkylgruppe,

mit der Maßgabe, dass maximal zwei der Gruppen aus G¹⁷, G¹⁸, G¹⁹ und G²⁰ eine Hydroxygruppe bedeuten und höchstens zwei der Reste G¹⁷, G¹⁸ und G¹⁹ für ein Wasserstoffatom stehen. Dabei ist es wiederum bevorzugt, wenn gemäß Formel (E4) mindestens zwei Gruppen aus G¹⁷, G¹⁸, G¹⁹ und G²⁰ für eine Gruppe -NG²¹G²² stehen und höchstens zwei Gruppen aus G¹⁷, G¹⁸, G¹⁹ und G²⁰ für eine Hydroxygruppe stehen.Preferred pyrimidine derivatives are selected according to the invention from compounds of the formula (E4) or their physiologically tolerated salts,

wherein

• G ¹⁷ , G ¹⁸ and G ¹⁹ independently of one another represent a hydrogen atom, a hydroxy group, a (C ₁ to C ₄ ) alkoxy group or an amino group and
• G ^{20 is} a hydroxy group or a group -NG ²¹ G ²² in which G ²¹ and G ²² independently of one another represent a hydrogen atom, a (C ₁ to C ₄ ) -alkyl group, a (C ₁ to C ₄ ) monohydroxyalkyl group .

with the proviso that a maximum of two of the groups of G ¹⁷ , G ¹⁸ , G ¹⁹ and G ^{20 is} a hydroxy group and at most two of the radicals G ¹⁷ , G ¹⁸ and G ^{19 are} a hydrogen atom. In this case, it is again preferred if, according to formula (E4), at least two groups of G ¹⁷ , G ¹⁸ , G ¹⁹ and G ^{20 represent} a group -NG ²¹ G ²² and at most two groups of G ¹⁷ , G ¹⁸ , G ¹⁹ and G ^{20 represent} a hydroxy group.

Especially preferred pyrimidine derivatives are in particular the compounds 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.

worin

• – G²³, G²⁴, G²⁵ stehen unabhängig voneinander für ein Wasserstoffatom, eine (C₁ bis C₄)-Alkylgruppe, eine (C₁ bis C₄)-Monohydroxyalkylgruppe, eine (C₂ bis C₄)-Polyhydroxyalkylgruppe, eine gegebenenfalls substituierte Arylgruppe oder eine gegebenenfalls substituierte Aryl-(C₁ bis C₄)-alkylgruppe, mit der Maßgabe dass, wenn G²⁵ für ein Wasserstoffatom steht, G²⁶ neben den vorgenannten Gruppen zusätzlich für eine Gruppe -NH₂ stehen kann,
• – G²⁶ steht für ein Wasserstoffatom, eine (C₁ bis C₄)-Alkylgruppe, eine (C₁ bis C₄)-Monohydroxyalkylgruppe oder eine (C₂ bis C₄)-Polyhydroxyalkylgruppe und
• – G²⁷ steht für ein Wasserstoffatom, eine gegebenenfalls substituierte Arylgruppe, eine (C₁ bis C₄)-Alkylgruppe oder eine (C₁ bis C₄)-Monohydroxyalkylgruppe, insbesondere für ein Wasserstoffatom oder eine Methylgruppe.

Preferred pyrazole derivatives are selected according to the invention from compounds of the formula (E5),

wherein

• G ²³ , G ²⁴ , G ²⁵ independently of one another represent a hydrogen atom, a (C ₁ to C ₄ ) -alkyl group, a (C ₁ to C ₄ ) -monohydroxyalkyl group, a (C ₂ to C ₄ ) -polyhydroxyalkyl group, a optionally substituted aryl group or an optionally substituted aryl- (C ₁ to C ₄ ) -alkyl group, with the proviso that when G ^{25 is} a hydrogen atom, G ^{26 may} additionally be a group -NH _{2 in} addition to the abovementioned groups,
• G ²⁶ represents a hydrogen atom, a (C ₁ to C ₄ ) alkyl group, a (C ₁ to C ₄ ) monohydroxyalkyl group or a (C ₂ to C ₄ ) polyhydroxyalkyl group and
• G ²⁷ represents a hydrogen atom, an optionally substituted aryl group, a (C ₁ to C ₄ ) -alkyl group or a (C ₁ to C ₄ ) -monohydroxyalkyl group, in particular a hydrogen atom or a methyl group.

Preferably in formula (E5) the radical -NG ²⁵ G ²⁶ binds to the 5 position and the radical G ²⁷ to the 3 position of the pyrazole cycle.

Especially preferred pyrazole derivatives are in particular the compounds the selected are 4,5-diamino-1-methylpyrazole, 4,5-diamino-1- (β-hydroxyethyl) -pyrazole, 3,4-diaminopyrazole 4,5-diamino-1- (4'-chlorobenzyl) -pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-Amino-1,3-dimethyl-5-hydrazinopyrazol, 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-isopropylpyrazol, 4,5-diamino-3-methyl-1-isopropylpyrazole, 4-amino-5- (β-aminoethyl) amino-1,3-dimethylpyrazole, and their physiologically acceptable Salts.

wobei:

• – G²⁸, G²⁹ und G³⁰, G³¹ unabhängig voneinander stehen für ein Wasserstoffatom, einen (C₁ bis C₄)-Alkylrest, einen Aryl-Rest, einen (C₁ bis C₄)-Monohydroxyalkylrest, einen (C₂ bis C₄)-Polyhydroxyalkylrest einen (C₁ bis C₄)-Alkoxy-(C₁ bis C₄)-alkylrest, einen (C₁ bis C₄)-Aminoalkylrest, der gegebenenfalls durch ein Acetyl-Ureid- oder einen Sulfonyl-Rest geschützt sein kann, einen (C₁ bis C₄)-Alkylamino-(C₁ bis C₄)-alkylrest, einen Di-[(C₁ bis C₄)-alkyl]-(C₁ bis C₄)-aminoalkylrest, wobei die Dialkyl-Reste gegebenenfalls einen Kohlenstoffzyklus oder einen Heterozyklus mit 5 oder 6 Kettengliedern bilden, einen (C₁ bis C₄)-Monohydroxyalkyl- oder einen Di[(C₁ bis C₄)-Hydroxyalkyl]-(C₁ bis C₄)-aminoalkylrest,
• – die X-Reste stehen unabhängig voneinander für ein Wasserstoffatom, einen (C₁ bis C₄)-Alkylrest, einen Aryl-Rest, einen (C₁ bis C₄)-Monohydroxyalkylrest, einen (C₂ bis C₄)-Polyhydroxyalkylrest, einen (C₁ bis C₄)-Aminoalkylrest, einen (C₁ bis C₄)-Alkylamino-(C₁ bis C₄)-alkylrest, einen Di-[(C₁ bis C₄)alkyl]-(C₁ bis C₄)-aminoalkylrest, wobei die Dialkyl-Reste gegebenenfalls einen Kohlenstoffzyklus oder einen Heterozyklus mit 5 oder 6 Kettengliedern bilden, einen (C₁ bis C₄)-Hydroxyalkyl- oder einen Di-[(C₁ bis C₄)-hydroxyalkyl]amino-(C₁ bis C₄)-alkylrest, einen Aminorest, einen (C₁ bis C₄)-Alkyl- oder Di-[(C₁ bis C₄)-hydroxyalkyl]aminorest, ein Halogenatom, eine Carboxylsäuregruppe oder eine Sulfonsäuregruppe,
• – i hat den Wert 0, 1, 2 oder 3,
• – p hat den Wert 0 oder 1,
• – q hat den Wert 0 oder 1 und
• – n hat den Wert 0 oder 1, mit der Maßgabe, dass
• – die Summe aus p + q ungleich 0 ist,
• – wenn p + q gleich 2 ist, n den Wert 0 hat, und die Gruppen NG²⁸G²⁹ und NG³⁰G³¹ belegen die Positionen (2,3); (5,6); (6,7); (3,5) oder (3,7);
• – wenn p + q gleich 1 ist, n den Wert 1 hat, und die Gruppen NG²⁸G²⁹ (oder NG³⁰G³¹) und die Gruppe OH belegen die Positionen (2,3); (5,6); (6,7); (3,5) oder (3,7);

Preferred pyrazolopyrimidine derivatives are, in particular, the derivatives of the pyrazolo [1,5-a] pyrimidine of the following formula (E6) and its tautomeric forms, if a tautomeric equilibrium exists:

in which:

• G ²⁸ , G ²⁹ and G ³⁰ , G ³¹ 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 ) -monohydroxyalkyl radical, a (C ₂ to C ₄ ) -polyhydroxyalkyl radical is a (C ₁ to C ₄ ) -alkoxy- (C ₁ to C ₄ ) -alkyl radical, a (C ₁ to C ₄ ) -aminoalkyl radical which is optionally substituted by an acetyl-ureide or a sulfonyl radical May be protected, 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 ) Monohydroxyalkyl 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 ) monohydroxyalkyl 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 radical, 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 or a di - [(C ₁ to C ₄ ) -hydroxyalkyl] amino (C ₁ to C ₄ ) alkyl, an amino, a (C ₁ to C ₄ ) alkyl or di - [(C ₁ to C ₄ ) hydroxyalkyl] amino, 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 equals 2, n has the value 0, and the groups NG ²⁸ G ²⁹ and NG ³⁰ G ³¹ 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 ²⁸ G ²⁹ (or NG ³⁰ G ³¹ ) and the group OH occupy the positions (2, 3); (5,6); (6,7); (3,5) or (3,7);

The used in formula (E7) substituents are analogous to the invention to the above statements Are defined.

When the pyrazolo [1,5-a] pyrimidine of the above formula (E6) contains a hydroxy group at one of the 2, 5 or 7 positions of the ring system, there is a tautomeric equilibrium shown, for example, in the following scheme:

• – Pyrazolo[1,5-a]pyrimidin-3,7-diamin;
• – 2,5-Dimethyl-pyrazolo[1,5-a]pyrimidin-3,7-diamin;
• – Pyrazolo[1,5-a]pyrimidin-3,5-diamin;
• – 2,7-Dimethyl-pyrazolo[1,5-a]pyrimidin-3,5-diamin;
• – 3-Aminopyrazolo[1,5-a]pyrimidin-7-ol;
• – 3-Aminopyrazolo[1,5-a]pyrimidin-5-ol;
• – 2-(3-Aminopyrazolo[1,5-a]pyrimidin-7-ylamino)-ethanol;
• – 2-(7-Aminopyrazolo[1,5-a]pyrimidin-3-ylamino)-ethanol;
• – 2-[(3-Aminopyrazolo[1,5-a]pyrimidin-7-yl)-(2-hydroxy-ethyl)-amino]-ethanol;
• – 2-[(7-Aminopyrazolo[1,5-a]pyrimidin-3-yl)-(2-hydroxy-ethyl)-amino]-ethanol;
• – 5,6-Dimethylpyrazolo[1,5-a]pyrimidin-3,7-diamin;
• – 2,6-Dimethylpyrazolo[1,5-a]pyrimidin-3,7-diamin;
• – 3-Amino-7-dimethylamino-2,5-dimethylpyrazolo[1,5-a]pyrimidin;

sowie ihre physiologisch verträglichen Salze und ihre tautomeren Formen, wenn ein tautomers Gleichgewicht vorhanden ist.In particular, among the pyrazolo [1,5-a] pyrimidines of the above formula (E7):

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

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

The Pyrazolo [1,5-a] pyrimidines of the above formula (E6) can be used as described in the literature by cyclization starting from a Aminopyrazole or produced from hydrazine.

Very particularly preferred developer components are selected from at least one compound from the group formed from p-phenylenediamine, p-toluenediamine, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- (α, β-dihydroxyethyl) -p phenylenediamine, N, N-bis (β-hydroxyethyl) -p-phenylenediamine, N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazol-1-yl) propyl] amine, N , N'-bis (β-hydroxyethyl) -N, N'-bis (4-aminophenyl) -1,3-diamino-propan-2-ol, bis (2-hydroxy-5-aminophenyl) -methane , 1,3-bis- (2,5-diaminopheno xy) -propan-2-ol, N, N'-bis (4-aminophenyl) -1,4-diazacycloheptane, 1,10-bis (2,5-diaminophenyl) -1,4,7,10- tetraoxadecane, p-aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (α, β-dihydroxyethyl) -phenol and 4-amino-2- (diethylaminomethyl) -phenol, 4,5-diamino-1- (β-hydroxyethyl) pyrazole, 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, and the physiologically acceptable salts of these compounds.

The following are examples of the radicals mentioned as substituents of the compounds of the formulas (E1) to (E6): Examples of (C ₁ to C ₄ ) -alkyl radicals are the groups -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ , -CH ₂ CH ₂ CH ₂ CH ₃ , -CH ₂ CH (CH ₃ ) ₂ , -CH (CH ₃ ) CH ₂ CH ₃ , -C (CH ₃ ) ₃ . Examples of (C ₁ to C ₄ ) -alkoxy radicals according to the invention are -OCH ₃ , -OCH ₂ CH ₃ , -OCH ₂ CH ₂ CH ₃ , -OCH (CH ₃ ) ₂ , -OCH ₂ CH ₂ CH ₂ CH ₃ , OCH ₂ CH (CH ₃ ) ₂ , -OCH (CH ₃ ) CH ₂ CH ₃ , -OC (CH ₃ ) ₃ , in particular a methoxy or an ethoxy group.

Furthermore, as preferred examples of a (C ₁ to C ₄ ) monohydroxyalkyl group, -CH ₂ OH, -CH ₂ CH ₂ OH, -CH ₂ CH ₂ CH ₂ OH, -CHCH (OH) CH ₃ , -CH ₂ CH ₂ CH ₂ CH ₂ OH, with the group -CH ₂ CH ₂ OH being preferred.

A particularly preferred example of a (C ₂ to C ₄ ) polyhydroxyalkyl group is the 1,2-dihydroxyethyl group.

Examples for halogen atoms are F, Cl or Br atoms, Cl atoms are very particularly preferred examples.

Examples of nitrogen-containing groups are in particular -NH ₂ , (C ₁ to C ₄ ) -monoalkylamino groups, (C ₁ to C ₄ ) -dialkylamino groups, (C ₁ to C ₄ ) -trialkylammonium groups, (C ₁ to C ₄ ) -monohydroxyalkylamino groups, Imidazolinium and -NH ₃ ⁺ .

Examples of (C ₁ to C ₄ ) monoalkylamino groups are -NHCH ₃ , -NHCH ₂ CH ₃ , -NHCH ₂ CH ₂ CH ₃ , -NHCH (CH ₃ ) ₂ .

Examples of (C ₁ to C ₄ ) -dialkylamino group are -N (CH ₃ ) ₂ , -N (CH ₂ CH ₃ ) ₂ .

Examples of (C ₁ to C ₄₎ -Trialkylammoniumgruppen are -N ⁺ (CH _{3) 3,} -N ⁺ (CH _{3) 2} (CH ₂ CH _3), -N ⁺ (CH ₃₎ (CH ₂ CH _{3) 2} ,

Examples of (C ₁ to C ₄ ) -hydroxyalkylamino radicals are -NH-CH ₂ CH ₂ OH, -NH-CH ₂ CH ₂ OH, -NH-CH ₂ CH ₂ CH ₂ OH, -NH-CH ₂ CH ₂ CH ₂ OH.

Examples of (C ₁ to C ₄ ) alkoxy (C ₁ to C ₄ ) alkyl groups are the groups -CH ₂ CH ₂ -O-CH ₃ , -CH ₂ CH ₂ CH ₂ -O-CH ₃ , -CH ₂ CH ₂ -O-CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₂ -O-CH ₂ CH ₃ , -CH ₂ CH ₂ -O-CH (CH ₃ ), -CH ₂ CH ₂ CH ₂ -O- CH (CH ₃ ).

Examples of hydroxy (C ₁ to C ₄ ) alkoxy radicals are -O-CH ₂ OH, -O-CH ₂ CH ₂ OH, -O-CH ₂ CH ₂ CH ₂ OH, -O-CHCH (OH) CH ₃ , -O-CH ₂ CH ₂ CH ₂ CH ₂ OH.

Examples of (C ₁ to C ₄ ) -acetylaminoalkoxy radicals are -O-CH ₂ NHC (O) CH ₃ , -O-CH ₂ CH ₂ NHC (O) CH ₃ , -O-CH ₂ CH ₂ CH ₂ NHC (O ) CH ₃ , -O-CH ₂ CH (NHC (O) CH ₃ ) CH ₃ , -O-CH ₂ CH ₂ CH ₂ CH ₂ NHC (O) CH ₃ .

Examples of (C ₁ to C ₄ ) -carbamoylaminoalkoxy radicals are -O-CH ₂ CH ₂ -NH-C (O) -NH ₂ , -O-CH ₂ CH ₂ CH ₂ -NH-C (O) -NH ₂ , -O-CH ₂ CH ₂ CH ₂ CH ₂ -NH-C (O) -NH ₂ .

Examples of (C ₁ to C ₄ ) -aminoalkyl radicals are -CH ₂ NH ₂ , -CH ₂ CH ₂ NH ₂ , -CH ₂ CH ₂ CH ₂ NH ₂ , -CH ₂ CH (NH ₂ ) CH ₃ , -CH ₂ CH ₂ CH ₂ CH ₂ NH ₂ .

Examples of (C ₁ to C ₄ ) -cyanoalkyl radicals are -CH ₂ CN, -CH ₂ CH ₂ CN, -CH ₂ CH ₂ CH ₂ CN.

Examples of (C ₁ to C ₄ ) -hydroxyalkylamino (C ₁ to C ₄ ) -alkyl radicals are -CH ₂ CH ₂ NH-CH ₂ CH ₂ OH, -CH ₂ CH ₂ CH ₂ NH-CH ₂ CH ₂ OH, -CH ₂ CH ₂ NH-CH ₂ CH ₂ CH ₂ OH, -CH ₂ CH ₂ CH ₂ NH-CH ₂ CH ₂ CH ₂ OH.

Examples of di [(C ₁ to C ₄ ) -hydroxyalkyl] amino (C ₁ to C ₄ ) -alkyl radicals are -CH ₂ CH ₂ N (CH ₂ CH ₂ OH) ₂ , -CH ₂ CH ₂ CH ₂ N ( CH ₂ CH ₂ OH) ₂ , -CH ₂ CH ₂ N (CH ₂ CH ₂ CH ₂ OH) ₂ , -CH ₂ CH ₂ CH ₂ N (CH ₂ CH ₂ CH ₂ OH) ₂ .

One example for Aryl groups is the phenyl group.

Examples of aryl (C ₁ to C ₄ ) alkyl groups are the benzyl group and the 2-phenylethyl group.

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

According to the invention are preferred coupler type oxidation dye precursors

• - M-aminophenol and its derivatives such as 5-amino-2-methylphenol, N-cyclopentyl-3-aminophenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 2,6-dimethyl 3-aminophenol, 3-trifluoroacetylamino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol, 5- (2'-hydroxyethyl) amino 2-methylphenol, 3- (diethylamino) -phenol, N-cyclopentyl-3-aminophenol, 1,3-dihydroxy-5- (methylamino) -benzene, 3-ethylamino-4-methylphenol and 2,4-dichloro-3 aminophenol,
• O-aminophenol and its derivatives,
• - M-Diaminobenzene and its derivatives such as 2,4-diaminophenoxyethanol, 1,3-bis (2 ', 4'-diaminophenoxy) propane, 1-methoxy-2-amino-4- (2'-hydroxyethylamino) benzene , 1,3-bis (2 ', 4'-diaminophenyl) -propane, 2,6-bis (2'-hydroxyethylamino) -1-methylbenzene and 1-amino-3-bis (2'-hydroxyethyl) aminobenzene,
• O-diaminobenzene and its derivatives such as 3,4-diaminobenzoic acid and 2,3-diamino-1-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-dimethoxypyridine,
• Naphthalene derivatives such as, for example, 1-naphthol, 2-methyl-1-naphthol, 2-hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and 2,3-dihydroxynaphthalene,
• Morpholine derivatives such as 6-hydroxybenzomorpholine and 6-aminobenzomorpholine,
• Quinoxaline derivatives such as 6-methyl-1,2,3,4-tetrahydroquinoxaline,
• Pyrazole derivatives such as 1-phenyl-3-methylpyrazol-5-one,
• Indole derivatives such as 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole,
• Pyrimidine derivatives such as 4,6-diaminopyrimidine, 4-amino-2,6-dihydroxypyrimidine, 2,4-diamino-6-hydroxypyrimidine, 2,4,6-trihydroxypyrimidine, 2-amino-4-methylpyrimidine, 2-amino 4-hydroxy-6-methylpyrimidine and 4,6-dihydroxy-2-methylpyrimidine, or
• - Methylenedioxybenzene derivatives such as 1-hydroxy-3,4-methylenedioxybenzene, 1-amino-3,4-methylenedioxybenzene and 1- (2'-hydroxyethyl) amino-3,4-methylenedioxybenzene.

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

Farther can the agents according to the invention also occurring in nature dyes such as, for example in henna red, henna neutral, henna black, chamomile flower, sandalwood, black tea, buckthorn bark, sage, bluewood, madder root, catechu, Sedre and alkano root are included.

It it is not necessary that the oxidation dye precursors or the direct dyes each represent uniform compounds. Rather, you can in the hair colorants according to the invention, due to the production process for the individual dyes, be contained in minor amounts still other components as far as these are not the dyeing result adversely affect or for other reasons, e.g. toxicological, must be excluded.

Regarding the in the hair dyeing and -tönungsmitteln applicable dyes is still expressly on the monograph Ch. Zviak, The Science of Hair Care, Chapter 7 (pp. 248-250; Dyes) and chapter 8, pages 264-267; Oxidation dye precursors) appeared as volume 7 of the series "Dermatology" (ed. Ch., Culnan and H. Maibach), Marcel Dekker Inc., New York, Basel, 1986, as well as the "European Inventory of cosmetic raw materials ", issued by the European Community, available in diskette form from the German Association of Industrial and Trade Companies for Medicines, Health food and personal care products e.V., Mannheim.

The hair colorants according to the invention become common slightly acidic to alkaline, d. H. to pH values in the range of about 5 to 11, set. For this purpose, the colorants contain Alkalizing agent, usually Alkali or alkaline earth hydroxides, ammonia or organic amines. Preferred alkalizing agents are monoethanolamine, monoisopropanolamine, 2-amino-2-methyl-propanol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, 2-amino-2-methylbutanol and triethanolamine and alkali and alkaline earth metal hydroxides. Especially Monoethanolamine, triethanolamine and 2-amino-2-methyl-propanol and 2-amino-2-methyl-1,3-propanediol are within this group prefers. Also, the use of ω-amino acids such as ω-aminocaproic acid as an alkalizing agent is possible.

He follows the training of hair colors in addition to the oxo color in the As part of an oxidative process, so can conventional oxidizing agents, such as in particular hydrogen peroxide or its addition products be used on urea, melamine or sodium borate. Farther Is it possible, to carry out the oxidation with the aid of enzymes, the enzymes both be used for the production of oxidizing per-compounds as well as for reinforcement the effect of a small amount of oxidizing agent present, or also enzymes the electrons from suitable developer components (Reducing agent) transferred to atmospheric oxygen. Preference is given here Oxidases such as tyrosinase, ascorbate oxidase and laccase but also glucose oxidase, Uricase or pyruvate oxidase. Furthermore, the procedure is mentioned, the effect of small amounts (eg 1% and less, based on the total agent) to amplify hydrogen peroxide by peroxidases.

The Oxidation with atmospheric oxygen as the sole oxidant can however, preferred according to the invention be. In a further embodiment are therefore the agents according to the invention free of additional oxidants, in particular free of hydrogen peroxide. Under oxidizing agents In this case, such compounds are understood to be at least one to oxidize the coloring components.

Conveniently, will be the preparation of the oxidant if it is included should, just before dyeing the hair mixed with the preparation with the coloring components. The resulting ready-to-use hair dye preparation should preferably have a pH in the range from 6 to 10. Particularly preferred is the application of Hair Dye in a slightly alkaline environment. The application temperatures can in a range between 15 and 40 ° C, preferably at the temperature of Scalp, lying. After an exposure time of about 5 to 45, in particular 15 to 30 minutes, the hair dye is removed by rinsing to be colored Hair removed. The washing with a shampoo is eliminated, if a strong surfactant-containing carrier, z. B. a dyeing shampoo, has been used.

• – nichtionische Polymere wie beispielsweise Vinylpyrrolidon/Vinylacrylat-Copolymere, Polyvinylpyrrolidon und Vinylpyrrolidon/Vinylacetat-Copolymere,
• – anionische Polymere, wie Polyacryl- und Polymethacrylsäuren in Form ihrer Copolymere mit Acrylsäure- und Methacrylsäureestern und -amiden, Polyoxycarbonsäuren, wie Polyketo- und Polyhydrocarbonsäuren und deren Salze, sowie Polymere und Copolymere der Crotonsäure mit Estern und Amiden der Acryl- und der Methacrylsäure, wie Vinylacetat-Crotonsäure- und Vinylacetat-Vinylpropionat-Crotonsäure-Copolymere,
• – Strukturanten wie Glucose und Maleinsäure,
• – haarkonditionierende Verbindungen wie Phospholipide, beispielsweise Sojalecithin, Ei-Lecithin und Kephaline,
• – Parfümöle,
• – Dimethylisosorbid und Cyclodextrine,
• – Lösungsvermittler, wie Ethanol, Isopropanol, Ethylenglykol, Propylenglykol, Glycerin, Diethylenglykol und ethoxylierte Triglyceride,
• – Wirkstoffe wie Bisabolol, Allantoin, Panthenol, Niacinmid, Tocopherol und Pflanzenextrakte,
• – Lichtschutzmittel,
• – Konsistenzgeber wie Zuckerester, Polyolester oder Polyolalkylether,
• – Fette und Wachse, wie Walrat, Bienenwachs, Montanwachs, Paraffine, Ester, Glyceride und Fettalkohole,
• – Fettsäurealkanolamide,
• – Komplexbildner wie EDTA, NTA, β-Alanindiessigsäure und Phosphonsäuren,
• – Quell- und Penetrationsstoffe wie PCA, Glycerin, Propylenglykolmonoethylether, Carbonate, Hydrogencarbonate, Guanidine, Harnstoffe sowie primäre, sekundäre und tertiäre Phosphate,
• – Trübungsmittel wie Latex oder Styrol/Acrylamid-Copolymere,
• – Perlglanzmittel wie Ethylenglykolmono- und -distearat oder PEG-3-distearat,
• – Weißpigmente,
• – Treibmittel wie Propan-Butan-Gemische, N₂O, Dimethylether, CO₂ und Luft,
• – Konservierungsmittel.

Further optional ingredients of the agents according to the invention are

• Nonionic polymers such as vinyl pyrrolidone / vinyl acrylate copolymers, polyvinyl pyrrolidone and vinyl pyrrolidone / vinyl acetate copolymers,
• Anionic polymers, such as polyacrylic and polymethacrylic acids in the form of their copolymers with acrylic and methacrylic esters and amides, polyoxycarboxylic acids, such as polyketo- and polyhydrocarboxylic acids and their salts, and polymers and copolymers of crotonic acid with esters and amides of acrylic and methacrylic acid, such as vinyl acetate-crotonic acid and vinyl acetate-vinyl-propionate-crotonic acid copolymers,
• - structurants such as glucose and maleic acid,
• Hair conditioning compounds such as phospholipids, for example soya lecithin, egg lecithin and cephalins,
• - perfume oils,
• Dimethylisosorbide and cyclodextrins,
• Solubilizers, such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol, diethylene glycol and ethoxylated triglycerides,
• - active substances such as bisabolol, allantoin, panthenol, niacinmide, tocopherol and plant extracts,
• - sunscreen,
• Bodying agents such as sugar esters, polyol esters or polyol alkyl ethers,
• Fats and waxes, such as spermaceti, beeswax, montan wax, paraffins, esters, glycerides and fatty alcohols,
• Fatty acid alkanolamides,
• Complexing agents such as EDTA, NTA, β-alaninediacetic acid and phosphonic acids,
• - swelling and penetration substances such as PCA, glycerol, propylene glycol monoethyl ether, carbonates, bicarbonates, guanidines, ureas and primary, secondary and tertiary phosphates,
• Opacifiers such as latex or styrene / acrylamide copolymers,
• Pearlescing agents such as ethylene glycol mono- and distearate or PEG-3-distearate,
• - white pigments,
• Propellants such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air,
• - preservative.

• (i) auf die mit Haaren bewachsene Hautpartie und/oder den Haarkonturenbereich gegebenenfalls ein Mittel (M1), enthaltend in einem kosmetischen Träger mindestens eine mineralisch oxidische Verbindung aufgetragen und nach einer Einwirkzeit Z1 abgespült wird,
• (ii) auf die Fasern ein Mittel (M2) gemäß des ersten Gegenstandes der Erfindung aufgetragen und nach einer Einwirkzeit Z2 von den Fasern gespült wird.

A second object of the invention is a method of reducing scalp staining in which

• (i) if appropriate, an agent (M1) containing at least one mineral oxide compound in a cosmetic carrier and rinsed off after a contact time Z1 is applied to the skin-covered area of the hair and / or the hair contour area,
• (ii) a medium (M2) according to the first aspect of the invention is applied to the fibers and rinsed by the fibers after a contact time Z2.

Under A hair contour area is the transition area from a nearly hairless skin in areas of skin with pronounced hair growth to understand. The hair contour area is therefore usually at the head in the region of the hairline on the forehead, the temples, over the Ears and neck or neck, and each covers 1 to 3 cm of the hairy skin and 1 to 3 cm of the glabrous area of the skin. This transition area is in the context of the method according to the invention preferably treated with the agent (M1).

ever after hairstyle can the hairy skin areas have areas where, although Hair growth is present, the skin becomes visible. This is special at the apex or in the center of a so-called vortex hair growth the case. The agent (M1) is preferably applied to such lots.

The Exposure time Z1 is preferably 1 to 60 minutes, more preferably 5 to 45 minutes. The reaction time Z2 is preferably 1 to 60 minutes, more preferably 5 to 45 minutes.

For further, additional Steps taken as part of a staining procedure can be applied expressly to the known monographs, e.g. Kh. Schrader, basics and recipes the cosmetics, 2nd edition, Hüthig Buch Verlag, Heidelberg, 1989, referenced the corresponding Render knowledge of the professional.

For the treatment In the hair contour area, thickened formulations have proven to be extra proven effective, as they adhere well to the skin and not into the eyes of the user. The agent M1 is preferred a viscosity of 5000-50000 mPa · s, particularly preferably a viscosity of (measured at 20 ° C with a Brookfield viscometer, type RVT, spindle # 5 at 4 rpm).

For the application on the scalp are preferably almost water-thin to slightly thickened formulations of the agent (M1) in a viscosity range of 1-500 mPa · s (measured at 20 ° C with a Brookfield viscometer, type RVT, spindle # 1 at 20 rpm) The agent M1 is preferably directly on by means of applicators applied to the hairy skin area or the hair contours. As applicators in the sense of the present inventive method Particularly suitable in the barber area as Applizetten narrow brushes and in particular those used in the home field Bottles with a narrow application tip. Furthermore However, the agent M1 can also be massaged with the help of the hands, for example by get to the site of action. For example, M1 can be used as a shampoo available. The means (M1) is thus according to an embodiment in the form of a shampoo first on the hair fiber and then by rubbing on the hair-covered Skin or hair contours applied.

to Production of the invention thickened Means M1 become these consistency regulators and / or thickeners added.

When Bodying agents are primarily fatty alcohols or hydroxy fatty alcohols with 12 to 30 and preferably 16 to 22 carbon atoms and next to it Partial glycerides, fatty acids or hydroxy fatty acids in Consideration. Preference is given to a combination of these substances with alkyl oligoglucosides and / or fatty acid N-methylglucamides same chain length and / or polyglycerol poly-12-hydroxy stearates.

Suitable thickeners are, for example, polysaccharides, in particular xanthan gum, guar-guar, agar-agar, alginates and tyloses, carboxymethyl cellulose and hydroxyethyl cellulose, also relatively high molecular weight polyethylene glycol mono- and diesters of fatty acids, polyacrylates (for example Carbopol ^® of Goodrich or Synthalens ^® from Sigma), polyacrylamides, polyvinyl alcohol and polyvinylpyrrolidone, surfactants such as example, ethoxylated fatty acid glycerides, esters of fatty acids with polyols such as pentaerythritol or trimethylolpropane, fatty alcohol ethoxylates with narrow homologue distribution or Alkyloligoglucoside and electrolytes such as sodium chloride and ammonium chloride. The thickening agents are preferably present in amounts of from 0.1 to 10% by weight, more preferably from 0.2 to 5% by weight, very particularly preferably from 0.3 to 2% by weight, based in each case on the entire composition.

An example of a formulation of an agent (M1): 1.0 to 10.0% by weight at least one mineral oxide compound, 0.4 to 1.0% by weight hydroxyethyl cellulose, 0.1% by weight salicylic acid, 0.1% by weight sorbic acid, ad 100% by weight Water.

The Pretreatment of the scalp and hair contour area with the Means M1 is especially useful and necessary if the hair to be dyed with color intensive dyes. To prevent the Kopfhautanfärbung can the means but also prophylactically before any hair coloring on the scalp are applied.

In a particularly preferred embodiment the method according to the invention the scalp and hair contour area are submerged especially before hair coloring Obtained a color-intensive hair coloring treated with the agent M1.

A coloring or shade is to be described as intensively colored if, on coloration of the coloring agent on white hair (Kerling, natural white), the color has a ΔL value in the CIE-Lab system of at least 30 by colorimetric determination. The .DELTA.L value is calculated as follows: L _Reference - L _staining (see also DIN 6174, German standards, Benth Verlag GmbH, Berlin, 1975). The reference is the undyed original hair. To determine the CIE Lab values, for example, the measuring device Texflash DC 3881 from Datacolor is suitable.

One third object of the invention is the use of at least one mineral oxidic compound in a cosmetic carrier for Reduction of skin staining by coloring using oxo dye precursors.

The preferred representatives of the mineral oxide compounds already defined in the first subject of the invention.

The The following examples are intended to describe the subject matter of the invention in more detail, without limiting it to him. The indicated contents refer, unless otherwise stated % by weight based on the total weight of the composition.

Examples

The following oxo dyes were provided:

Table 1: Dyeing cream with component (ia)

• 1 C _16-18 fatty alcohol (manufacturer: COGNIS)
• 2 C _12-18 fatty alcohol (manufacturer: COGNIS)
• 3 cetylstearyl alcohol + 20-EO (INCI name: Ceteareth-20) (Manufacturer: COGNIS)

Table 2: Dye cream with component (ib)

The coloring cream 1 contains no the skin staining reducing silicone active ingredient combination and is therefore not according to the invention (comparative coloring cream). The coloring creams 2 and 3 are colorants of the invention.

ever a coloring cream from Table 1 was in a weight ratio of 1 to 1 with the dyeing cream according to the table 2 mixed and this mixture with monoethanolamine to a pH set by 9.5.

0.5g of each mixture was applied for the test of skin staining on a 3 cm ² area of skin of the forearm of a test person and left there for a period of 30 minutes. Subsequently, the agent was rinsed off the skin area with water. Finally, the staining of the skin was visually assessed and evaluated. On a grading scale of 1 - 5 (1 = no skin staining, 5 = skin staining corresponds to the degree of staining of the staining cream 1), the following grades were subjectively awarded: active substance grade Aerosil 200 (coloring cream 2) 2.0 Aerosil R 972 (coloring cream 3) 2.5

Claims (15)

Agent for dyeing keratin-containing fibers, in particular human hair, containing in a cosmetic carrier (i) as Oxofarbstoffvorprodukte at least one combination of components (ia) and (ib), (ia) at least one reactive carbonyl compound selected from at least one compound according to formula (ia -1),

in which - R ¹ , R ² and R ³ independently of one another represent a hydrogen atom, a halogen atom, a C ₁ -C ₆ -alkyl group, a (C ₂ to C ₆ ) -alkenyl group, a formyl group, a hydroxy group, a C ₁ - C ₆ alkoxy group, a C ₁ -C ₆ dialkylamino group, a di (C ₂ -C ₆ hydroxyalkyl) amino group, a di (C ₁ -C ₆ alkoxy-C ₁ -C ₆ alkyl) amino group, a C C ₁ -C ₆ -hydroxyalkyloxy group, a sulfonyl group, a carboxyl group, a sulfonic acid group, a sulfonamide group, a carbamoyl group, a C ₂ -C ₆ -acyl group, an acetyl group or a nitro group, - Z 'is a direct bond or a vinylene group, R ⁴ and R ⁵ represent a hydrogen atom or together form, together with the remainder of the molecule, a 5- or 6-membered aromatic or aliphatic ring, (ib) at least one CH-acidic compound having an aromatic or aliphatic heterocyclic main body which is selected from cyclic onium compounds with the structure unit of the formula (Ib-1),

R ⁶ represents a linear or cyclic C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, an aryl-C ₁ -C ₆ -alkyl group, a C ₁ -C ₆ -hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a C ₁ -C ₆ alkoxy-C ₁ -C ₆ alkyl group, a group R ^I R ^II N- (CH ₂ ) _m -, wherein R ^I and R ^II independently represent a hydrogen atom, a C ₁ -C ₄ -alkyl group, a C ₁ -C ₄ -hydroxyalkyl group or an aryl-C ₁ -C ₆ -alkyl group, wherein R ^I and R ^II together with the nitrogen atom Can form a 5-, 6- or 7-membered ring and m is a number 2, 3, 4, 5 or 6, - R ⁷ is a (C ₁ to C ₆ ) -alkyl group, in particular a methyl group, - X ^- stands for a physiologically compatible anion, - the cycle represents all ring structures, which can contain additional heteroatoms such as nitrogen, oxygen or sulfur nnen and further may carry fused ring structures, all of these ring structures can carry additional substituents, and (ii) contains at least one mineral oxide compound. Composition according to claim 1, characterized in that the derivatives of the benzaldehydes, naphthaldehydes or cinnamaldehydes of the reactive carbonyl compound according to component (ia) are selected from at least one compound of the group consisting of 4-hydroxy-3-methoxybenzaldehyde, 3,5- Dimethoxy-4-hydroxybenzaldehyde, 4-hydroxy-1-naphthaldehyde, 4-hydroxy-2-methoxybenzaldehyde, 3,4-dihydroxy-5-methoxybenzaldehyde, 3,4,5-trihydroxybenzaldehyde, 3,5-dibromo-4-hydroxybenzaldehyde, 4-hydroxy-3-ni trobenzaldehyde, 3-bromo-4-hydroxybenzaldehyde, 4-hydroxy-3-methylbenzaldehyde, 3,5-dimethyl-4-hydroxybenzaldehyde, 5-bromo-4-hydroxy-3-methoxybenzaldehyde, 4-diethylamino-2-hydroxybenzaldehyde, 4-Dimethylamino-2-methoxybenzaldehyde, 2-methoxybenzaldehyde, 3-methoxybenzaldehyde, 4-methoxybenzaldehyde, 2-ethoxybenzaldehyde, 3-ethoxybenzaldehyde, 4-ethoxybenzaldehyde, 4-hydroxy-2,3-dimethoxy-benzaldehyde, 4-hydroxy-2, 5-dimethoxybenzaldehyde, 4-hydroxy-2,6-dimethoxybenzaldehyde, 4-hydroxy-2-methylbenzaldehyde, 4-hydroxy-2,3-dimethylbenzaldehyde, 4-hydroxy-2,5-dimethylbenzaldehyde, 4-hydroxy-2,6-dimethylbenzaldehyde, 3,5-diethoxy-4-hydroxybenzaldehyde, 2,6-diethoxy-4-hydroxybenzaldehyde, 3-hydroxy-4-methoxybenzaldehyde, 2-hydroxy-4- methoxybenzaldehyde, 2-ethoxy-4-hydroxybenzaldehyde, 3-ethoxy-4-hydroxybenzaldehyde, 4-ethoxy-2-hydroxybenzaldehyde, 4-ethoxy-3-hydroxybenzaldehyde, 2,3-dimethoxybenzaldehyde, 2, 4-dimethoxybenzaldehyde, 2,5-dimethoxybenzaldehyde, 2,6-dimethoxybenzaldehyde, 3,4-dimethoxybenzaldehyde, 3 , 5-Dimethoxybenzaldehyde, 2,3,4-trimethoxybenzaldehyde, 2,3,5-trimethoxybenzaldehyde, 2,3,6-trimethoxybenzaldehyde, 2,4,6-trimethoxybenzaldehyde, 2,4,5-trimethoxybenzaldehyde, 2,5,6 Trimethoxybenzaldehyde, 2-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 2,3-dihydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 2,4-dihydroxy-3-methylbenzaldehyde, 2,4-dihydroxy-5-methylbenzaldehyde , 2,4-dihydroxy-6-methylbenzaldehyde, 2,4-dihydroxy-3-methoxy-benzaldehyde, 2,4-dihydroxy-5-methoxy-benzaldehyde, 2,4-dihydroxy-6-methoxy-benzaldehyde, 2 , 5-dihydroxybenzaldehyde, 2,6-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde, 3,4-dihydroxy-2-methylbenzaldehyde, 3,4-dihydroxy-5-methylbenzaldehyde, 3,4-dihydroxy-6-methyl benzaldehyde, 3,4-dihydroxy-2-methoxybenzaldehyde, 3,5-dihydroxybenzaldehyde, 2,3,4-trihydroxybenzaldehyde, 2,3,5-trihydroxybenzaldehyde, 2,3,6-trihydroxybenzaldehyde, 2,4,6 Trihydroxybenzaldehyde, 2,4,5-trihydroxybenzaldehyde, 2,5,6-trihydroxybenzaldehyde, 4-dimethylaminobenzaldehyde, 4-diethylamine nobenzaldehyde, 4-dimethylamino-2-hydroxybenzaldehyde, 4-pyrrolidinobenzaldehyde, 4-morpholinobenzaldehyde, 2-morpholinobenzaldehyde, 4-piperidinobenzaldehyde, 3,5-dichloro-4-hydroxybenzaldehyde, 4-hydroxy-3,5-diiodo-benzaldehyde, 3- Chloro-4-hydroxybenzaldehyde, 5-chloro-3,4-dihydroxybenzaldehyde, 5-bromo-3,4-dihydroxybenzaldehyde, 3-chloro-4-hydroxy-5-methoxybenzaldehyde, 4-hydroxy-3-iodo-5-methoxybenzaldehyde, 2-methoxy-1-naphthaldehyde, 4-methoxy-1-naphthaldehyde, 2-hydroxy-1-naphthaldehyde, 2,4-dihydroxy-1-naphthaldehyde, 4-hydroxy-3-methoxy-1-naphthaldehyde, 2-hydroxy 4-methoxy-1-naphthaldehyde, 3-hydroxy-4-methoxy-1-naphthaldehyde, 2,4-dimethoxy-1-naphthaldehyde, 3,4-dimethoxy-1-naphthaldehyde, 4-dimethylamino-1-naphthaldehyde, 3- Hydroxy-4-nitrobenzaldehyde, 2-hydroxy-3-methoxy-5-nitrobenzaldehyde, 5-nitrovanillin, 2,5-dinitrosalicylaldehyde, 5-bromo-3-nitrosalicylaldehyde, 2-dimethylaminobenzaldehyde, 2-chloro-4-dimethylaminobenzaldehyde, 4- Dimethylamino-2-methylbenzaldehyde, 4-diethylaminocinnamaldehyde, 4-dibutylamino benzaldehyde, 3-carboxy-4-hydroxybenzaldehyde, 5-carboxyvanillin, 3-carboxy-4-hydroxy-5-methylbenzaldehyde, 3-carboxy-5-ethoxy-4-hydroxybenzaldehyde, 3-carboxy-4-hydroxybenzaldehyde, 5- Carboxyvanillin, 3-carboxy-4-hydroxy-5-methylbenzaldehyde, 3-carboxy-5-ethoxy-4-hydroxybenzaldehyde, 3-allyl-4-hydroxybenzaldehyde, 3-allyl-4-hydroxy-5-methoxybenzaldehyde, 3-allyl 4-hydroxy-5-methylbenzaldehyde, 3-allyl-5-bromo-4-hydroxybenzaldehyde, 3,5-diallyl-4-hydroxybenzaldehyde, 3-allyl-5-carboxy-4-hydroxybenzaldehyde (3-allyl-5-formyl) 2-hydroxybenzoic acid), 3-allyl-4-hydroxy-5-formylbenzaldehyde (5-allyl-4-hydroxyisophthalaldehyde) and piperonal. Agent according to one of claims 1 or 2, characterized in that the CH-acidic compounds of the Oxofarbstoffvorprodukte the component (ib) are selected from at least one compound of formula (ib-2)

wherein - R ⁸ and R ⁹ are independently a linear or cyclic C ₁ -C ₆ alkyl group, a C ₂ -C ₆ alkenyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, an aryl C ₁ -C ₆ alkyl group, a C ₁ -C ₆ hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a C ₁ -C ₆ alkoxy C ₁ -C ₆ alkyl group, a group R ^I R ^II N- (CH ₂ ) _m -, wherein R ^I and R ^II independently of one another represent a hydrogen atom, a C ₁ -C ₄ -alkyl group, a C ₁ -C ₄ -hydroxyalkyl group or an aryl-C ₁ -C ₆ -alkyl group, where R ^I and R ^II together with the nitrogen atom can form a 5-, 6- or 7-membered ring and m stands for a number 2, 3, 4, 5 or 6, - R ¹⁰ and R ¹² independently of one another represent a hydrogen atom or a C ₁ C ₆ alkyl group, where at least one of R ¹⁰ and R ^{12 is} a C ₁ -C ₆ alkyl group, R ¹¹ represents a hydrogen atom, a C ₁ -C ₆ -alkyl group, a C ₁ -C ₆ -hydroxyalkyl group, a C ₂ -C ₆ -polyhydroxyalkyl group, a C ₁ -C ₆ -alkoxy group, a C ₁ -C ₆ -Hydroxyalkoxygruppe, a group R ^III R ^IV N- (CH ₂ ) _q -, wherein R ^III and R ^IV independently represent a hydrogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ hydroxyalkyl group or a Aryl-C ₁ -C ₆ -alkyl group and q is a number 1, 2, 3, 4, 5 or 6, wherein the radical R ¹¹ together with one of the radicals R ¹⁰ or R ^{12 is} a 5- or 6-membered aromatic Ring optionally containing a halogen atom, a C ₁ -C ₆ -alkyl group, a C ₁ -C ₆ -hydroxyalkyl group, a C ₂ -C ₆ -polyhydroxyalkyl group, a C ₁ -C ₆ -alkoxy group, a C ₁ - C ₆ -hydroxyalkoxy group, a nitro group, a hydroxy group, a group R ^V R ^VI N- (CH ₂ ) _s -, wherein R ^V and R ^VI independently of one another represent a hydrogen atom, a C ₁ -C ₆ -alkyl group, a C ₁ -C ₆ -hydroxyalkyl group or an aryl-C ₁ -C ₆ -alkyl group and s is a number 0, 1, 2, 3, 4, 5 or 6 may be substituted, - Y is an oxygen atom, a sulfur atom or a group NR ^VII , wherein R ^VII represents a hydrogen atom, an aryl group, a heteroaryl group, a C ₁ -C ₆ alkyl group or a C ₁ -C ₆ arylalkyl group, - X ^- represents a physiologically acceptable anion. Agent according to one of claims 1 to 3, characterized that the mineral oxide compounds in an amount of 1 to 20 wt .-%, particularly preferably from 2 to 10 wt .-%, respectively based on the weight of the agent according to the invention are included. Agent according to one of Claims 1 to 4, characterized in that the mineral-oxidic compounds have a BET specific surface area of 40 to 4000 m ² / g, in particular of 100 to 1000 m ² / g (in each case determined according to DIN ISO 9277: 2003). 05). Agent according to one of claims 1 to 5, characterized that the mineral oxide compounds have a particle diameter smaller 800 μm, especially smaller than 300 μm, have. Agent according to one of claims 1 to 6, characterized that the mineral oxide compounds are selected from at least one representative from the group that is formed from aluminates, silicates and titanium dioxide, as well as mixtures of these mineral oxide compounds. Agent according to claim 7, characterized in that the aluminates selected under active alumina, alpha alumina, beta alumina, gamma-alumina and mixtures thereof. Agent according to claim 7 or 8, characterized that the Aluminum silicates selected are among phyllosilicates, Tectosilikaten and mixtures thereof. Agent according to one of claims 7 to 9, characterized that the polysilicas selected be among fumed silicas. Method for reducing skin staining in Frame of a hair coloring, in which (i) on the hair-covered area of the skin and / or the hair contour area optionally an agent (M1) containing in a cosmetic carrier at least one mineral oxide compound is applied and rinsed after a contact Z1 becomes, (ii) on the fibers a means (M2) according to a the claims 1 to 10 applied and after a contact Z2 of the fibers rinsed becomes. Method according to claim 11, characterized in that the agent (M1) has a viscosity of 5000-50000 mPa · s (measured at 20 ° C with a Brookfield viscometer, type RVT, spindle # 5 at 4 rpm) has. Method according to one of claims 11 or 12, characterized that the agent (M1) with an applicator directly on the hair overgrown skin area or the hair contours is applied. Method according to one of claims 11 to 13, characterized that the agent (M1) in the form of a shampoo first on the hair fiber and then massage in on the hair-covered area of the skin or the hair contours is applied. Use of at least one mineral oxide A compound in a cosmetic vehicle for reducing skin staining coloring using oxo dye precursors.