DE102008061342A1 - Hair color with cocoa butter - Google Patents

Abstract

The invention relates to a coloring agent for keratin-containing fibers for glossy and nourishing dyeings. This colorant contains in a cosmetic carrier in addition to a coloring component as a care ingredient cocoa butter. Particularly advantageous is the addition of cocoa butter in oxidative colorants. Moreover, the invention relates to the use of said agent for improving the general care state, in particular of gloss and wet combability, of keratinic fibers, in particular human hair, in the dyeing.

Description

The The invention relates to a coloring agent for keratin-containing Fibers for shiny and nourishing dyeings. This Colorant contains in a cosmetic carrier In addition to a coloring component as a care ingredient cocoa butter. Particularly advantageous is the addition of cocoa butter in oxidative colorants. In addition, concerns the invention the use of said means for improvement general care condition, in particular gloss and wet combability, of keratinic fibers, especially human hair the coloring.

The Changing the shape and color of the hair represents an important one The field of modern cosmetics dar. This can change the appearance the hair both current fashion trends and the individual wishes of the individual person to be adjusted. For the fashionable color design of hairstyles or for laminating gray or even white hair with fashionable or natural Shades the consumer uses color changing Means. These agents should in addition to the desired dyeing power cause as little damage to the hair as possible and preferably even have additional care properties.

to Provision of color-changing cosmetic preparations, in particular for the skin or keratin fibers such as human hair, the expert knows the requirements of the Coloring various dyeing systems.

For permanent, intensive colorations with corresponding fastness properties so-called oxidation colorants are used. Such Colorants usually contain oxidation dye precursors, so-called developer components and coupler components. The developer components form under the influence of oxidizing agents or atmospheric oxygen with each other or under coupling with one or more coupler components the actual dyes. The oxidation colorants Although distinguished by excellent, long-lasting staining results out. For natural-looking dyeings but usually has to be a mixture of a larger Number of oxidation dye precursors are used; in many Cases continue to be substantive dyes for shading used.

When Developer components usually become primary aromatic amines with another, in para or ortho position free or substituted hydroxy or amino group, heterocyclic hydrazones, diaminopyrazole derivatives and 2,4,5,6-tetraaminopyrimidine and its derivatives used. As coupler components are in usually m-phenylenediamine derivatives, naphthols, pyridine derivatives, Resorcinol and resorcinol derivatives, pyrazolones and m-aminophenols.

For temporary stains become common Dyeing or toning agents used as coloring Component so-called direct pullers included. This is it around dye molecules that are directly on the substrate raise and no oxidative process to form the color need. These dyes include, for example that already from the antiquity to the coloring of body and hairs known henna. These dyes are against shampooing usually much more sensitive than oxidative stains, so much faster then a much undesirable Shade shift or even a visible homogeneous color loss entry.

After all another dyeing process has received a lot of attention found. In this process, precursors of the natural Hair Dye Melanin on the substrate, eg. As hair applied; These then form natural analogues in the course of oxidative processes in the hair Dyes, in particular with 5,6-dihydroxyindoline, from. The coloration can be done with atmospheric oxygen as the sole oxidant, so that resorted to no further oxidizing agents must become.

A offers further possibility for color change the use of colorants, which are so-called Oxofarbstoffvorprodukte contain. A first class of oxo dye precursors are compounds with at least one reactive carbonyl group. A second class of Oxo dye precursors form C, H-acidic compounds and compounds with primary or secondary amino group or Hydroxy group. The aforementioned components are generally themselves no dyes, and are therefore each individually taken alone not for coloring keratinhaltiger fibers. In combination, they form the so-called non-oxidative process Oxo dyeing dyes off. The resulting dyeings have partial color fastness on the keratin-containing fiber, which are comparable to those of oxidation staining. The method of oxo dyeing can also be without further combine with the oxidative dyeing system.

Especially oxidative hair dyes are despite their beneficial Dyeing properties for the user with disadvantages afflicted.

First the use of the oxidizing agents leads to coloration or development of the actual coloration too Damage in the hair structure and on the hair surface. The hair becomes brittle, leaves its elasticity after and the combability decreases. This injury increases with the duration of use. Commercially available oxidative Dyes usually need over a period of time of 30 minutes and longer to act on the hair fiber. However, it is also close for convenience of use lying, that among users of such hair dye there is a need to reduce this exposure time.

Secondly oxidative dyes usually need one basic pH for coloration, especially between pH 9.0 and pH 10.5. These pH levels are necessary to get an opening to ensure the outer cuticle (cuticle) and a penetration of the active species (dye precursors and / or Hydrogen peroxide) in the hair. The basic However, milieu is another cause of injury for the hair and its structure, which also with Increased application time gains in importance. The spread the outer cuticle layer also leads to an unpleasant surface sensation of the hair and thus to a deteriorated combability in the wet and Dry state. This provides the consumer with a increased need for additional aftertreatment use as conditioner.

Around To improve the care condition of the fibers, it has long been common the fibers following the color-changing treatment to undergo a special after-treatment. It will, usually in the form of a conditioner, the hair with special ingredients treated. Depending on the formulation, this treatment results in combability, Stop and fullness of the hair improves and the split rate reduced. In order to avoid the expense of the usual multi-stage procedures, especially when used directly by consumers, have recently become so-called combination preparations developed. These preparations contain in addition to the usual Components, for example, for coloring the hair, in addition Active ingredients formerly reserved for hair treatment products were. The consumer thus saves an application step; simultaneously The packaging costs are reduced because one product is less used becomes. Nevertheless, even these funds, especially on heavy leave to care fibers still some wishes regarding the caring properties open.

Around to save the additional post-treatment step has It is therefore not lacking in attempts to use suitable care substances in to incorporate the hair dye. Usually Be oxidative hair dye immediately before use from a dyeing preparation and a so-called developer preparation produced. As a rule, has the dyeing preparation a strongly basic pH to the oxidation dye precursors contained therein stabilize while the developer preparation a weakly acidic pH, but that for dye formation contains necessary oxidizing agent. Set both options thus not an advantageous environment, a chemically sensitive To include care without decomposition. It therefore persists a need for suitable, stable caring substances that can be oxidative Incorporate colorant and so already during the dyeing process occurring damage minimize assets.

task Therefore, it is the object of the present invention to overcome the above disadvantages lower oxidative hair dye. The colorants should protect the hair and thus a reduced damage of the hair. In particular, protection against oxidative damage The hair structure and the hair surface should be through the Hair dyes are achieved. Especially desirable are nourishing properties of the funds, allowing the user to refrain from using additional conditioning agents can. The reduction of hair damage during However, the coloring should not be at the expense of a reduced Coloring capacity of the funds can be achieved. Especially the colorant is supposed to improve the shine and shine the wet combability compared to conventional Achieve colorants.

In unpredictable way has now been found that the addition of Cocoa butter as a conditioner in colorants for Keratinic fibers have advantages over conventional ones Dyes causes gloss and care of the fibers.

One The first object of the invention is therefore a dyeing agent keratin-containing fibers, in particular human hair, containing in a cosmetic carrier at least one coloring Component, characterized in that the agent cocoa butter contains.

Under keratin fibers or keratin fibers are furs, wool, To understand feathers and especially human hair. Although the agents according to the invention primarily for dyeing are suitable for keratin fibers, is in principle a use also in other areas nothing contrary.

The agents of the invention contain the active ingredients in a cosmetic carrier. This cosmetic carrier is within the meaning of the invention is aqueous, alcoholic or aqueous-alcoholic.

To the For purposes of hair coloring are such carriers, for example Creams, emulsions, gels or surfactant-containing foaming Solutions, such as shampoos, foam aerosols or other preparations for use on the hair are suitable.

For the purposes of the present invention, aqueous-alcoholic carriers are water-containing compositions containing 3 to 70% by weight of a C ₁ -C ₄ -alcohol, based on the total weight of the application mixture, in particular ethanol or isopropanol. The compositions according to the invention may additionally contain other organic solvents, such as, for example, methoxybutanol, ethyldiglycol, 1,2-propylene glycol, n-propanol, n-butanol, n-butylene glycol, glycerol, diethylene glycol monoethyl ether, and diethylene glycol mono-n-butyl ether. Preference is given to all water-soluble organic solvents.

One aqueous carrier contains in the sense of Invention at least 30% by weight, in particular at least 50% by weight Water, based on the total weight of the application mixture.

When first essential ingredient contains the inventive Means as a care cocoa butter. Cocoa butter possesses the Advantage over other care substances, a sufficient To have stability in the colorant, in particular against different pH values.

cocoa butter becomes from the beans of the cocoa tree in the course of the cocoa processing (Theobroma cacao, Sterculiaceae). The yellowish fat is isolated in cocoa bean storage cotyledons and is after fermentation, roasting, peeling and Cleaning the cocoa cores by squeezing the resulting cocoa mass receive.

Cocoa butter consists of about 97% of triglycerides of fatty acids, which consist on average of 25% palmitic acid (C ₁₆ ), 37% stearic acid (C ₁₈ ), 34% oleic acid ((9Z) -C ₁₈ ) and 3% linoleic acid (( 9Z, 12Z) -C18). Cocoa butter is characterized by a narrow fatty acid profile. A characteristic feature is a high content (about 72-87%) of symmetrical, monounsaturated triacylglycerides, which is responsible for many of the properties of cocoa butter. Symmetrically, monounsaturated triglycerides are understood to mean those triglycerides which carry an ester with an unsaturated fatty acid at position 2 of the glycerol and an ester with a saturated fatty acid at the positions 1 and 3. Examples of such triglycerides are 2-oleodipalmitin (POP), palmito-2-oleostearin (POS), 2-oleodistearin (SOS). In contrast, symmetric, diunsaturated triglycerides, such as 2-palmito-diolein (OPO), and unsymmetrical, diunsaturated triglycerides, such as 1-palmito-diolein (POO), are only present in minor proportions (approximately 12-25%). ) contain. Cocoa butter is waxy to firm at room temperature and melts at 17 to 37 ° C, depending on the crystal form.

One Particularly preferred according to the invention agent characterized in that it contains cocoa butter in a proportion of 0.01 to 10 wt .-%, preferably from 0.05 to 5 wt .-% and in particular from 0.1 to 3 wt .-%, each based on the total weight of ready to use agent.

• (a) Oxidationsfarbstoffvorprodukten und/oder
• (b) naturanalogen Farbstoffen und/oder
• (c) Oxofarbstoffvorprodukten und/oder
• (d) direktziehenden Farbstoffen.

The agent according to the invention also contains at least one coloring component. Preferred compounds are characterized in that they contain as the coloring component at least one compound which is selected from

• (a) oxidation dye precursors and / or
• (b) naturally-analogous dyes and / or
• (c) oxo dye precursors and / or
• (d) direct dyes.

In a preferred embodiment of the present invention, the agent contains as a coloring Component at least one oxidation dye precursor.

Oxidation dye precursors because of their responsiveness in two categories be divided, so-called developer components and coupler components.

developer components can form with themselves the actual dye. They can therefore be used as sole, color-changing Contain compounds in the composition according to the invention be. In a preferred embodiment, the agents according to the invention at least one oxidation dye precursor of the developer type and / or coupler type. Preferably, the contain Colorants according to the invention at least a developer-type oxidation dye precursor and at least an oxidation dye precursor of the coupler type.

The Developer and coupler components usually become used in free form. For substances with amino groups can However, it may be preferred to use them in salt form, in particular in the form of Hydrochloride and hydrobromide or sulfates use.

following become developer components according to the invention presented in more detail.

wobei

• – G1 steht für ein Wasserstoffatom, einen C₁-C₄-Alkylrest, einen C₁-C₄-Monohydroxyalkylrest, einen C₂-C₄-Polyhydroxyalkylrest, einen C₁-C₄-Alkoxy-C₁-C₄-alkylrest, einen 4'-Aminophenylrest oder einen C₁-C₄-Alkylrest, der mit einer stickstoffhaltigen Gruppe, einem Phenyl- oder einem 4'-Aminophenylrest substituiert ist;
• – G2 steht für ein Wasserstoffatom, einen C₁-C₄-Alkylrest, einen C₁-C₄-Monohydroxyalkylrest, einen C₂-C₄-Polyhydroxyalkylrest, einen C₁-C₄-Alkoxy-C₁-C₄-alkylrest oder einen C₁-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-C₄-Alkylrest, einen C₁-C₄-Monohydroxyalkylrest, einen C₂-C₄-Polyhydroxyalkylrest, einen C₁-C₄-Hydroxyalkoxyrest, einen C₁-C₄-Alkoxy-C₁-C₄-alkylrest, einen C₁-C₄-Acetylaminoalkoxyrest, einen Mesylamino-C₁-C₄-alkoxyrest oder einen C₁-C₄-Carbamoylaminoalkoxyrest;
• – G4 steht für ein Wasserstoffatom, ein Halogenatom, einen C₁-C₄-Alkylrest oder einen C₁-C₄-Alkoxy-C₁-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.

Particular preference is given to p-phenylenediamine derivatives of the formula (E1)

in which

• G1 represents a hydrogen atom, a C ₁ -C ₄ -alkyl radical, a C ₁ -C ₄ -monohydroxyalkyl radical, a C ₂ -C ₄ -polyhydroxyalkyl radical, a C ₁ -C ₄ -alkoxy-C ₁ -C ₄ -alkyl radical a 4'-aminophenyl radical or a C ₁ -C ₄ alkyl radical substituted with a nitrogen-containing group, a phenyl or a 4'-aminophenyl radical;
• G _{2 represents} a hydrogen atom, a C ₁ -C ₄ -alkyl radical, a C ₁ -C ₄ -monohydroxyalkyl radical, a C ₂ -C ₄ -polyhydroxyalkyl radical, a C ₁ -C ₄ -alkoxy-C ₁ -C ₄ -alkyl radical or a C ₁ -C ₄ alkyl radical 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 -C ₄ -alkyl radical, a C ₁ -C ₄ -monohydroxyalkyl radical, a C ₂ -C ₄ -polyhydroxyalkyl radical, C ₁ -C ₄ -alkoxyalkoxy, C ₁ -C ₄ -alkoxy-C ₁ -C ₄ -alkyl, C ₁ -C ₄ -acetylaminoalkoxy, mesylamino-C ₁ -C ₄ -alkoxy or C ₁ - C ₄ carbamoylaminoalkoxy radical;
• G4 represents a hydrogen atom, a halogen atom, a C ₁ -C ₄ -alkyl radical or a C ₁ -C ₄ -alkoxy-C ₁ -C ₄ -alkyl radical or
• When G3 and G4 are ortho to each other, they may together form a bridging .alpha.,. Omega.-alkylenedioxy group such as, for example, an ethylenedioxy group.

Especially Preferred p-phenylenediamines of formula (E1) are selected one or more compounds of the group that is formed from 1,4-diaminobenzene (p-phenylenediamine), 1,4-diamino-2-methylbenzene (p-toluenediamine), 1,4-diamino-2-chlorobenzene (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 (2-hydroxyethyl) -p-phenylenediamine, 4-N, N-bis (2-hydroxyethyl) amino-2-methylaniline, 4-N, N-bis- (2-hydroxyethyl) amino-2-chloroaniline, 2- (2-hydroxyethyl) -p-phenylenediamine, 2- (1,2-dihydroxyethyl) -p-phenylenediamine, 2-fluoro-p-phenylenediamine, 2-isopropyl-p-phenylenediamine, N- (2-hydroxypropyl) -p-phenylenediamine, 2-hydroxymethyl-p-phenylenediamine, N, N-dimethyl-3-methyl-p-phenylenediamine, N-ethyl-N-2-hydroxyethyl-p-phenylenediamine, N- (2,3-dihydroxypropyl) -p-phenylenediamine, N- (4'-aminophenyl) -p-phenylenediamine, N-phenyl-p-phenylenediamine, 2- (2-hydroxyethyloxy) -p-phenylenediamine, 2-methoxymethyl-p-phenylenediamine, 2- (2-acetylaminoethyloxy) -p-phenylenediamine, N- (2-methoxyethyl) -p-phenylenediamine, N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazol-1-yl) propyl] amine, 5,8-Diaminobenzo-1,4-dioxane and their physiologically acceptable Salt.

Completely according to the invention Particularly preferred p-phenylenediamine derivatives of the formula (E1) are selected from at least one compound of the group p-phenylenediamine, p-toluenediamine, 2- (2-hydroxyethyl) -p-phenylenediamine, 2- (1,2-dihydroxyethyl) -p-phenylenediamine, N, N-bis (2-hydroxyethyl) -p-phenylenediamine, N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazol-1-yl) propyl] amine, 2-methoxymethyl-p-phenylenediamine and the physiologically acceptable Salts of these compounds.

It may be further preferred according to the invention as a developer component to use compounds that at least contain two aromatic nuclei containing 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-C₄-Alkylrest, durch einen C₁-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-C₈-Alkoxyreste substituiert sein kann, oder eine direkte Bindung,
• – G5 und G6 stehen unabhängig voneinander für ein Wasserstoff- oder Halogenatom, einen C₁-C₄-Alkylrest, einen C₁-C₄-Monohydroxyalkylrest, einen C₂-C₄-Polyhydroxyalkylrest, einen C₁-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-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

• - Z1 and Z2 independently of one another represent a hydroxyl or NH ₂ radical which is optionally substituted by a C ₁ -C ₄ -alkyl radical, by a C ₁ -C ₄ -hydroxyalkyl radical and / or by a bridging Y 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 -C ₈ alkoxy, or a direct bond,
• G5 and G6 independently of one another represent a hydrogen or halogen atom, a C ₁ -C ₄ -alkyl radical, a C ₁ -C ₄ -monohydroxyalkyl radical, a C ₂ -C ₄ -polyhydroxyalkyl radical, a C ₁ -C ₄ -aminoalkyl radical or a direct connection to the bridge Y,
• G7, G8, G9, G10, G11 and G12 independently of one another represent a hydrogen atom, a direct bond to the bridge Y or a C ₁ -C ₄ -alkyl radical,

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

preferred binuclear developer components of the formula (E2) are especially selected from at least one of the following: N, N'-bis (2-hydroxyethyl) -N, N'-bis- (4'-aminophenyl) -1,3-diaminopropane-2-ol, N, N'-bis (2-hydroxyethyl) -N, N'-bis (4'-aminophenyl) ethylenediamine, N, N'-bis (4'-aminophenyl) tetramethylenediamine, N, N'-bis (2-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 acceptable salts.

All particularly preferred binuclear developer components of the formula (E2) are selected from N, N'-bis (2-hydroxyethyl) -N, N'-bis (4-aminophenyl) -1,3-diaminopropan-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-C₄-Alkylrest, einen C₁-C₄-Monohydroxyalkylrest, einen C₂-C₄-Polyhydroxyalkylrest, einen C₁-C₄-Alkoxy-C₁-C₄-alkylrest, einen C₁-C₄-Aminoalkylrest, einen Hydroxy-C₁-C₄-alkylaminorest, einen C₁-C₄-Hydroxy alkoxyrest, einen C₁-C₄-Hydroxyalkyl-C₁-C₄-aminoalkylrest oder einen Di-(C₁-C₄-alkyl)amino-C₁-C₄-alkylrest, und
• – G14 steht für ein Wasserstoff- oder Halogenatom, einen C₁-C₄-Alkylrest, einen C₁-C₄-Monohydroxyalkylrest, einen C₂-C₄-Polyhydroxyalkylrest, einen C₁-C₄-Alkoxy-C₁-C₄-alkylrest, einen C₁-C₄-Aminoalkylrest oder einen C₁-C₄-Cyanoalkylrest,
• – G15 steht für Wasserstoff, einen C₁-C₄-Alkylrest, einen C₁-C₄-Monohydroxyalkylrest, einen C₂-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

• G13 represents a hydrogen atom, a halogen atom, a C ₁ -C ₄ -alkyl radical, a C ₁ -C ₄ -monohydroxyalkyl radical, a C ₂ -C ₄ -polyhydroxyalkyl radical, a C ₁ -C ₄ -alkoxy-C ₁ -C ₄ alkyl, a C ₁ -C ₄ aminoalkyl, a hydroxy-C ₁ -C ₄ alkylamino, a C ₁ -C ₄ hydroxy alkoxy, a C ₁ -C ₄ hydroxyalkyl C ₁ -C ₄ aminoalkyl or a di (C ₁ -C ₄ alkyl) amino C ₁ -C ₄ alkyl radical, and
• - G14 represents a hydrogen or halogen atom, a C ₁ -C ₄ -alkyl radical, a C ₁ -C ₄ -monohydroxyalkyl radical, a C ₂ -C ₄ -polyhydroxyalkyl radical, a C ₁ -C ₄ -alkoxy-C ₁ -C _4- alkyl radical, a C ₁ -C ₄ -aminoalkyl radical or a C ₁ -C ₄ -cyanoalkyl radical,
• G15 represents hydrogen, a C ₁ -C ₄ -alkyl radical, a C ₁ -C ₄ -monohydroxyalkyl radical, a C ₂ -C ₄ -polyhydroxyalkyl radical, a phenyl radical or a benzyl radical, and
• - G16 is hydrogen or a halogen atom.

preferred p-aminophenols of the formula (E3) are in particular 4-aminophenol, N-methyl-4-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 2-hydroxymethylamino-4-aminophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2- (2-hydroxyethoxy) phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (2-hydroxyethylaminomethyl) phenol, 4-amino-2- (1,2-dihydroxyethyl) phenol, 4-amino-2-fluorophenol, 4-amino-2-chlorophenol, 4-amino-2,6-dichlorophenol, 4-amino-2- (diethylaminomethyl) phenol and their physiologically acceptable salts.

All particularly preferred compounds of the formula (E3) are 4-aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (1,2-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 compatible salts.

worin

• – G17, G18 und G19 unabhängig voneinander für ein Wasserstoffatom, eine Hydroxygruppe, eine C₁-C₄-Alkoxygruppe oder eine Aminogruppe steht und
• – G20 für eine Hydroxygruppe oder eine Gruppe -NG21 G22 steht, worin G21 und G22 unabhängig voneinander stehen für ein Wasserstoffatom, eine C₁-C₄-Alkylgruppe, eine C₁-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 tolerable salts,

wherein

• G17, G18 and G19 independently of one another represent a hydrogen atom, a hydroxy group, a C ₁ -C ₄ -alkoxy group or an amino group, and
• G20 is a hydroxy group or a group -NG21 G22, in which G21 and G22 independently of one another represent a hydrogen atom, a C ₁ -C ₄ -alkyl group, a C ₁ -C ₄ -monohydroxyalkyl group,

with the proviso that at most two of the groups of G17, G18, G19 and G20 represent a hydroxy group and at most two of the radicals G17, G18 and G19 represent a hydrogen atom. In this case, it is again preferred if, according to formula (E4), at least two groups from G17, G18, G19 and G20 represent a group -NG21G22 and at most two groups from G17, G18, G19 and G20 represent a hydroxy group.

Particularly preferred pyrimidine derivatives are in particular the compounds 2,4,5,6-tetraaminopy rimidine, 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-C₄-Alkylgruppe, eine C₁-C₄-Monohydroxyalkylgruppe, eine C₂-C₄-Polyhydroxyalkylgruppe, eine gegebenenfalls substituierte Arylgruppe oder eine gegebenenfalls substituierte Aryl-C₁-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-C₄-Alkylgruppe, eine C₁-C₄-Monohydroxyalkylgruppe oder eine C₂-C₄-Polyhydroxyalkylgruppe und
• – G27 steht für ein Wasserstoffatom, eine gegebenenfalls substituierte Arylgruppe, eine C₁-C₄-Alkylgruppe oder eine C₁-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

• G23, G24, G25 independently of one another represent a hydrogen atom, a C ₁ -C ₄ -alkyl group, a C ₁ -C ₄ -monohydroxyalkyl group, a C ₂ -C ₄ -polyhydroxyalkyl group, an optionally substituted aryl group or an optionally substituted aryl group C ₁ -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,
• G26 represents a hydrogen atom, a C ₁ -C ₄ -alkyl group, a C ₁ -C ₄ -monohydroxyalkyl group or a C ₂ -C ₄ -polyhydroxyalkyl group and
• G27 represents a hydrogen atom, an optionally substituted aryl group, a C ₁ -C ₄ -alkyl group or a C ₁ -C ₄ -monohydroxyalkyl group, in particular a hydrogen atom or a methyl group.

Prefers binds in formula (E5) the residue -NG25G26 to the 5 position and the Rest G27 to the 3-position of the pyrazole cycle.

Especially preferred pyrazole derivatives are in particular the compounds which are selected from 4,5-diamino-1-methylpyrazole, 4,5-diamino-1- (2-hydroxyethyl) pyrazole, 3,4-diaminopyrazole, 4,5-diamino-1- (4'-chlorobenzyl) pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazinopyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-t-butyl-1-methylpyrazole, 4,5-diamino-1-t-butyl-3-methylpyrazole, 4,5-diamino-1- (2-hydroxyethyl) -3-methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-3- (4-methoxyphenyl) pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-1-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4,5-diamino-3-methyl-1-isopropylpyrazole, 4-amino-5- (2-aminoethyl) amino-1,3-dimethylpyrazole, and their physiologically acceptable salts, but especially 4,5-diamino-1- (2-hydroxyethyl) pyrazole.

wobei:

• – G28, G29 und G30, G31 unabhängig voneinander stehen für ein Wasserstoffatom, einen C₁-C₄-Alkylrest, einen Aryl-Rest, einen C₁-C₄-Monohydroxyalkylrest, einen C₂-C₄-Polyhydroxyalkylrest, einen C₁-C₄-Alkoxy-C₁-C₄-alkylrest, einen C₁-C₄-Aminoalkylrest, der gegebenenfalls durch ein Acetyl-Ureid- oder einen Sulfonyl-Rest geschützt sein kann, einen C₁-C₄-Alkylamino-C₁-C₄-alkylrest, einen Di-(C₁-C₄-alkyl)amino-C₁-C₄-alkylrest, wobei die Dialkyl-Reste gegebenenfalls einen Kohlenstoffcyclus oder einen Heterocyclus mit 5 oder 6 Kettengliedern bilden, einen C₁-C₄-Monohydroxyalkyl- oder einen Bis-(C₁-C₄-Hydroxyalkylamino-C₁-C₄-alkylrest,
• – die X-Reste stehen unabhängig voneinander für ein Wasserstoffatom, einen C₁-C₄-Alkylrest, einen Aryl-Rest, einen C₁-C₄-Monohydroxyalkylrest, einen C₂-C₄-Polyhydroxyalkylrest, einen C₁-C₄-Aminoalkylrest, einen C₁-C₄-Alkylamino-C₁-C₄-alkylrest, einen Di-(C₁-C₄-alkyl)amino-C₁-C₄-alkylrest, wobei die Dialkyl-Reste gegebenenfalls einen Kohlenstoffcyclus oder einen Heterocyclus mit 5 oder 6 Kettengliedern bilden, einen C₁-C₄-Hydroxyalkyl- oder einen Di-(C₁-C₄-Hydroxyalkyl)amino-C₁-C₄-alkylrest, einen Aminorest, einen C₁-C₄-Alkylaminorest, einen Di-(C₁-C₄-alkyl)aminorest, C₁-C₄-hydroxyalkylaminorest oder einen Di-(C₁-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:

• - G28, G29 and G30, G31 independently of one another represent a hydrogen atom, a C ₁ -C ₄ -alkyl radical, an aryl radical, a C ₁ -C ₄ -monohydroxyalkyl radical, a C ₂ -C ₄ -polyhydroxyalkyl radical, a C ₁ C ₄ -C ₄ alkoxy-C ₁ -C ₄ alkyl, C ₁ -C ₄ aminoalkyl which may be optionally protected by an acetyl-ureide or a sulfonyl radical, a C ₁ -C ₄ -alkylamino-C C ₁ -C ₄ -alkyl radical, a di (C ₁ -C ₄ -alkyl) amino-C ₁ -C ₄ -alkyl radical, where the dialkyl radicals optionally form a carbon cycle or a heterocycle having 5 or 6 chain members, a C ₁ C ₄ -monohydroxyalkyl or a bis- (C ₁ -C ₄ -hydroxyalkylamino-C ₁ -C ₄ -alkyl radical,
• - The X radicals independently of one another represent a hydrogen atom, a C ₁ -C ₄ -alkyl radical, an aryl radical, a C ₁ -C ₄ -monohydroxyalkyl radical, a C ₂ -C ₄ -polyhydroxyalkyl radical, a C ₁ -C ₄ -Aminoalkylrest, a C ₁ -C ₄ alkylamino-C ₁ -C ₄ alkyl radical, a di (C ₁ -C ₄ alkyl) amino-C ₁ -C ₄ alkyl radical, wherein the dial kyl radicals optionally form a carbon cycle or a heterocycle having 5 or 6 chain members, a C ₁ -C ₄ -hydroxyalkyl or a di- (C ₁ -C ₄ -hydroxyalkyl) amino-C ₁ -C ₄ -alkyl radical, an amino radical a C ₁ -C ₄ alkylamino, a di (C ₁ -C ₄ alkyl) amino, C ₁ -C ₄ hydroxyalkylamino or a di (C ₁ -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 is 2, n is 0, and groups NG28G29 and NG30G31 occupy the positions (2, 3); (5,6); (6,7); (3,5) or (3,7);
• When p + q is 1, n is 1, and the groups NG28G29 (or NG30G31) and the group OH occupy the positions (2, 3); (5,6); (6,7); (3,5) or (3,7);

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:

Under the pyrazolo [1,5-a] pyrimidines of the above formula (E7) in particular: 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-ethylamino] ethanol, 2 - [(7-aminopyrazolo [1,5-a] pyrimidin-3-yl) - (2-hydroxyethyl) 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 as well their physiologically acceptable salts and their tautomers Shapes when there is a tautomeric equilibrium.

The following are examples of the radicals mentioned as substituents of the compounds of the formulas (E1) to (E6): Examples of C ₁ -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 -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, preferred examples of a C ₁ -C ₄ monohydroxyalkyl group are 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, wherein the Group CH ₂ CH ₂ OH is preferred.

A particularly preferred example of a C ₂ -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 -C ₄ -monoalkylamino groups, di (C ₁ -C ₄ -alkyl) amino groups, tri (C ₁ -C ₄ -alkyl) ammonium groups, C ₁ -C ₄ -monohydroxyalkylamino groups , Imidazolinium and NH ₃ ⁺ .

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

Examples of di (C ₁ -C ₄ alkyl) amino group are N (CH ₃ ) ₂ , N (CH ₂ CH ₃ ) ₂ .

Examples of tri (C ₁ -C ₄ alkyl) ammonium groups 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 -C ₄ -hydroxyalkylamino radicals are NHCH ₂ CH ₂ OH, NHCH ₂ CH ₂ OH, NHCH ₂ CH ₂ CH ₂ OH, NHCH ₂ CH ₂ CH ₂ OH.

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

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

Examples of C ₁ -C ₄ -acetylaminoalkoxy radicals are OCH ₂ NHC (O) CH ₃ , OCH ₂ CH ₂ NHC (O) CH ₃ , OCH ₂ CH ₂ CH ₂ NHC (O) CH ₃ , OCH ₂ CH (NHC (O ) CH ₃₎ CH _3, OCH ₂ CH ₂ CH ₂ CH ₂ NHC (O) CH _3.

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

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

Examples of C ₁ -C ₄ -hydroxyalkylamino-C ₁ -C ₄ -alkyl radicals are CH ₂ CH ₂ NHCH ₂ CH ₂ OH, CH ₂ CH ₂ CH ₂ NHCH ₂ CH ₂ OH, CH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ OH, CH ₂ CH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ OH.

Examples of di- (C ₁ -C ₄ -hydroxyalkyl) aminoC ₁ -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 An example of an aryl group is the phenyl group.

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

Especially preferred developer components are selected from at least one compound from the group that is formed from p-phenylenediamine, p-toluenediamine, 2- (2-hydroxyethyl) -p-phenylenediamine, 2- (1,2-dihydroxyethyl) -p-phenylenediamine, N, N-bis (2-hydroxyethyl) -p-phenylenediamine, 2-methoxymethyl-p-phenylenediamine, N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazol-1-yl) -propyl] amine, N, N'-bis (2-hydroxyethyl) -N, N'-bis- (4-aminophenyl) -1,3-diaminopropane-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, p-aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (1,2-dihydroxyethyl) phenol and 4-amino-2- (diethylaminomethyl) phenol, 4,5-diamino-1- (2-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.

All Particularly preferred developer components are p-toluenediamine, 2- (2-hydroxyethyl) -p-phenylenediamine, 2-methoxymethyl-p-phenylenediamine, N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazol-1-yl) propyl] amine, and / or 4,5-diamino-1- (2-hydroxyethyl) pyrazole and its physiological compatible salts.

The Developer components are preferred in an amount of 0.005 to 20 wt .-%, preferably 0.1 to 5 wt .-%, each based on the ready-to-use oxidation colorant.

Kupplerkomponenten do not form a significant part of the oxidative staining alone Coloring, but always need the present of developer components. Therefore, it is preferred according to the invention that when using at least one coupler component in addition at least one developer component is used.

Coupler components according to the invention allow at least one substitution of a chemi residue of the coupler by the oxidized form of the developer component. This forms a covalent bond between the coupler and the developer component. Couplers are preferably cyclic compounds which carry at least two groups on the cycle, selected from (i) optionally substituted amino groups and / or (ii) hydroxyl groups. When the cyclic compound is a six-membered ring (preferably aromatic), said groups are preferably in ortho position or meta position to each other.

• – 3-Aminophenol (m-Aminophenol) und/oder dessen Derivate,
• – 3-Aminoanilin (m-Diaminobenzol) und/oder dessen Derivate,
• – 2-Aminoanilin (1,2-Diaminobenzol; o-Diaminobenzol) und/oder dessen Derivate,
• – 2-Aminophenol (o-Aminophenol) und/oder dessen Derivate,
• – Naphthalinderivate mit mindestens einer Hydroxygruppe,
• – Di- beziehungsweise Trihydroxybenzol und/oder deren Derivate,
• – Pyridinderivate,
• – Pyrimidinderivate,
• – Monohydroxyindol-Derivate und/oder Monoaminoindol-Derivate,
• – Monohydroxyindolin-Derivate und/oder Monoaminoindolin-Derivate,
• – Pyrazolonderivate, wie beispielsweise 1-Phenyl-3-methylpyrazol-5-on,
• – Morpholinderivate, wie beispielsweise 6-Hydroxybenzomorpholin oder 6-Aminobenzomorpholin,
• – Chinoxalinderivate, wie beispielsweise 6-Methyl-1,2,3,4-tetrahydrochinoxalin,

Gemische aus zwei oder mehreren Verbindungen aus einer oder mehreren dieser Klassen sind im Rahmen dieser Ausführungsform ebenso erfindungsgemäß.Coupler components according to the invention are preferably selected as at least one compound from one of the following classes:

• 3-aminophenol (m-aminophenol) and / or its derivatives,
• 3-aminoaniline (m-diaminobenzene) and / or its derivatives,
• 2-aminoaniline (1,2-diaminobenzene, o-diaminobenzene) and / or its derivatives,
• 2-aminophenol (o-aminophenol) and / or derivatives thereof,
• Naphthalene derivatives having at least one hydroxy group,
• Di- or trihydroxybenzene and / or derivatives thereof,
• - pyridine derivatives,
• - pyrimidine derivatives,
• Monohydroxyindole derivatives and / or monoamine indole derivatives,
• Monohydroxyindoline derivatives and / or monoaminoindoline derivatives,
• Pyrazolone derivatives such as 1-phenyl-3-methylpyrazol-5-one,
• Morpholine derivatives, such as, for example, 6-hydroxybenzomorpholine or 6-aminobenzomorpholine,
• Quinoxaline derivatives such as 6-methyl-1,2,3,4-tetrahydroquinoxaline,

Mixtures of two or more compounds from one or more of these classes are also within the scope of this embodiment according to the invention.

worin
G1 und G2 unabhängig voneinander stehen für ein Wasserstoffatom, eine C₁-C₄-Alkylgruppe, eine C₃-C₆-Cycloalkylgruppe, eine C₂-C₄-Alkenylgruppe, eine C₁-C₄-Monohydroxyalkylgruppe, eine C₂-C₄-Polyhydroxyalkylgruppe, eine C₂-C₄-Perfluoracylgruppe, eine Aryl-C₁-C₆-alkylgruppe, eine Amino-C₁-C₆-alkylgruppe, eine Di-(C₁-C₆-alkyl)amino-C₁-C₆-alkylgruppe oder eine C₁-C₆-Alkoxy-C₁-C₆-alkylgruppe, wobei G1 und G2 gemeinsam mit dem Stickstoffatom einen fünfgliedrigen, sechsgliedrigen oder siebengliedrigen Ring bilden können,
G3 und G4 unabhängig voneinander stehen für ein Wasserstoffatom, ein Halogenatom, eine C₁-C₄-Alkylgruppe, eine C₁-C₄-Alkoxygruppe, eine Hydroxygruppe, eine C₁-C₄-Monohydroxyalkylgruppe, eine C₂-C₄-Polyhydroxyalkylgruppe, eine Hydroxy-C₁-C₄-alkoxy gruppe, eine C₁-C₆-Alkyoxy-C₂-C₆-alkoxygruppe, eine Arylgruppe oder eine Heteroarylgruppe.The inventively used 3-aminophenols (m-aminophenols) or derivatives thereof are preferably selected from at least one compound of formula (K1) and / or at least one physiologically acceptable salt of a compound according to formula (K1),

wherein
G1 and G2 independently of one another represent a hydrogen atom, a C ₁ -C ₄ -alkyl group, a C ₃ -C ₆ -cycloalkyl group, a C ₂ -C ₄ -alkenyl group, a C ₁ -C ₄ -monohydroxyalkyl group, a C ₂ - C ₄ polyhydroxyalkyl group, a C ₂ -C ₄ perfluoroacyl group, an aryl C ₁ -C ₆ alkyl group, an amino C ₁ -C ₆ alkyl group, a di (C ₁ -C ₆ alkyl) amino C ₁ -C ₆ -alkyl group or a C ₁ -C ₆ -alkoxy-C ₁ -C ₆ -alkyl group, where G ₁ and G 2 together with the nitrogen atom can form a five-membered, six-membered or seven-membered ring,
G3 and G4 independently of one another represent a hydrogen atom, a halogen atom, a C ₁ -C ₄ -alkyl group, a C ₁ -C ₄ -alkoxy group, a hydroxy group, a C ₁ -C ₄ -monohydroxyalkyl group, a C ₂ -C ₄ - Polyhydroxyalkyl group, a hydroxyC ₁ -C ₄ alkoxy group, a C ₁ -C ₆ alkoxy-C ₂ -C ₆ alkoxy group, an aryl group or a heteroaryl group.

Especially preferred 3-aminophenol coupler components are selected from at least one compound from the group that is formed from 3-aminophenol, 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-diethylaminophenol, N-cyclopentyl-3-aminophenol, 1,3-dihydroxy-5- (methylamino) benzene, 3-ethylamino-4-methylphenol, 2,4-dichloro-3-aminophenol and the physiologically acceptable Salts of all the above compounds.

worin
G5, G6, G7 und G8 unabhängig voneinander stehen für ein Wasserstoffatom, eine C₁-C₄-Alkylgruppe, eine C₃-C₆-Cycloalkylgruppe, eine C₂-C₄-Alkenylgruppe, eine C₁-C₄-Monohydroxyalkylgruppe, eine C₂-C₄-Polyhydroxyalkylgruppe, eine C₁-C₄-Alkoxy-C₁-C₄-alkylgruppe, eine Aryl-C₁-C₄-alkylgruppe, eine Heteroaryl-C₁-C₄-alkylgruppe, eine C₂-C₄-Perfluoracylgruppe, oder gemeinsam mit dem Stickstoffatom einen fünfgliedrigen oder sechsgliedrigen Heterocyclus bilden
G9 und G10 unabhängig voneinander stehen für ein Wasserstoffatom, ein Halogenatom, eine C₁-C₄-Alkylgruppe, eine ω-(2,4-Diaminophenyl)-C₁-C₄-alkylgruppe, eine ω-(2,4-Diaminophenyloxy)-C₁-C₄-alkoxygruppe, eine C₁-C₄-Alkoxygruppe, eine Hydroxygruppe, eine C₁-C₄-Alkoxy-C₂-C₄-alkoxygruppe, eine Arylgruppe, eine Heteroarylgruppe, eine C₁-C₄-Monohydroxyalkylgruppe, eine C₂-C₄-Polyhydroxyalkylgruppe, eine Hydroxy-C₁-C₄-alkoxygruppe.The 3-diaminobenzenes or derivatives thereof which can be used according to the invention are preferably selected from at least one compound of the formula (K2) and / or from at least one physiologically tolerated salt of a compound of the formula (K2),

wherein
G5, G6, G7 and G8 independently of one another represent a hydrogen atom, a C ₁ -C ₄ -alkyl group, a C ₃ -C ₆ -cycloalkyl group, a C ₂ -C ₄ -alkenyl group, a C ₁ -C ₄ -monohydroxyalkyl group, a C ₂ -C ₄ polyhydroxyalkyl group, a C ₁ -C ₄ alkoxy C ₁ -C ₄ alkyl group, an aryl C ₁ -C ₄ alkyl group, a heteroaryl C ₁ -C ₄ alkyl group, a C ₂ -C ₄ perfluoroacyl group, or together with the nitrogen atom form a five-membered or six-membered heterocycle
G9 and G10 independently represent a hydrogen atom, a halogen atom, a C ₁ -C ₄ alkyl group, a ω- (2,4-diaminophenyl) C ₁ -C ₄ alkyl group, an ω- (2,4-diaminophenyloxy ) C ₁ -C ₄ alkoxy group, a C ₁ -C ₄ alkoxy group, a hydroxy group, a C ₁ -C ₄ alkoxy C ₂ -C ₄ alkoxy group, an aryl group, a heteroaryl group, a C ₁ -C ₄ monohydroxyalkyl group, a C ₂ -C ₄ polyhydroxyalkyl group, a hydroxy C ₁ -C ₄ alkoxy group.

Especially preferred 3-diaminobenzene coupler components are selected from at least one compound from the group that is formed from 3-aminoaniline (m-phenylenediamine), 2- (2,4-diaminophenoxy) ethanol, 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, 2- ({3 - [(2-hydroxyethyl) amino] -4-methoxy-5-methylphenyl} amino) ethanol, 2 - ({3 - [(2-hydroxyethyl) amino] -2-methoxy-5-methylphenyl} amino) ethanol, 2 - ({3 - [(2-hydroxyethyl) amino] -4,5-dimethylphenyl} amino) ethanol, 2- [3-morpholin-4-yl-phenyl) -amino] -ethanol, 3-amino-4- (2-methoxy-ethoxy) -5-methyl-phenylamine, 1-amino-3-bis- (2'-hydroxyethyl) aminobenzene and the physiological compatible salts of all the compounds mentioned above.

worin
G11, G12, G13 und G14 unabhängig voneinander stehen für ein Wasserstoffatom, eine C₁-C₄-Alkylgruppe, eine C₃-C₆-Cycloalkylgruppe, eine C₂-C₄-Alkenylgruppe, eine C₁-C₄-Monohydroxyalkylgruppe, eine C₂-C₄-Polyhydroxyalkylgruppe, eine C₁-C₄-Alkoxy-C₁-C₄-alkylgruppe, eine Aryl-C₁-C₄-alkylgruppe, eine Heteroaryl-C₁-C₄-alkylgruppe, eine C₂-C₄-Perfluoracylgruppe, oder gemeinsam mit dem Stickstoffatom einen fünfgliedrigen oder sechsgliedrigen Heterocyclus bilden
G15 und G16 unabhängig voneinander stehen für ein Wasserstoffatom, ein Halogenatom, eine Carboxylgruppe, eine C₁-C₄-Alkylgruppe, eine C₁-C₄-Alkoxygruppe, eine Hydroxygruppe, eine C₁-C₄-Monohydroxyalkylgruppe, eine C₂-C₄-Polyhydroxyalkylgruppe, eine Hydroxy-C₁-C₄-alkoxygruppe.The 1,2-diaminobenzenes or derivatives thereof which can be used according to the invention are preferably selected from at least one compound of the formula (K3) and / or from at least one physiologically tolerated salt of a compound of the formula (K3),

wherein
G11, G12, G13 and G14 independently of one another represent a hydrogen atom, a C ₁ -C ₄ -alkyl group, a C ₃ -C ₆ -cycloalkyl group, a C ₂ -C ₄ -alkenyl group, a C ₁ -C ₄ -monohydroxyalkyl group, a C ₂ -C ₄ polyhydroxyalkyl group, a C ₁ -C ₄ alkoxy C ₁ -C ₄ alkyl group, an aryl C ₁ -C ₄ alkyl group, a heteroaryl C ₁ -C ₄ alkyl group, a C ₂ -C ₄ perfluoroacyl group, or together with the nitrogen atom form a five-membered or six-membered heterocycle
G15 and G16 independently of one another represent a hydrogen atom, a halogen atom, a carboxyl group, a C ₁ -C ₄ -alkyl group, a C ₁ -C ₄ -alkoxy group, a hydroxy group, a C ₁ -C ₄ -monohydroxyalkyl group, a C ₂ - C ₄ polyhydroxyalkyl group, a hydroxy C ₁ -C ₄ alkoxy group.

Especially preferred 1,2-diaminobenzene coupler components are selected from at least one compound from the group that is formed from 3,4-diaminobenzoic acid and 2,3-diamino-1-methylbenzene and the physiologically acceptable salts of all above mentioned compounds.

preferred Di- or trihydroxybenzenes and their derivatives selected from at least one compound of the group, which is formed from resorcinol, resorcinol monomethyl ether, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2-chlororesorcinol, 4-chlororesorcinol, Pyrogallol and 1,2,4-trihydroxybenzene.

worin
G17 und G18 stehen unabhängig voneinander für eine Hydroxygruppe oder eine Gruppe -NG21G22,
worin G21 und G22 unabhängig voneinander stehen für ein Wasserstoffatom, eine C₁-C₄-Alkylgruppe, eine C₃-C₆-Cycloalkylgruppe, eine C₂-C₄-Alkenylgruppe, eine Arylgruppe, eine C₁-C₄-Monohydroxyalkylgruppe, eine C₂-C₄-Polyhydroxyalkylgruppe, eine C₁-C₄-Alkoxy-C₁-C₄-alkylgruppe, eine Aryl-C₁-C₄-alkylgruppe, eine Heteroaryl-C₁-C₄-alkylgruppe,
G19 und G20 stehen unabhängig voneinander für ein Wasserstoffatom, ein Halogenatom, eine C₁-C₄-Alkylgruppe oder eine C₁-C₄-Alkoxygruppe.The pyridine derivatives which can be used according to the invention are preferably selected from at least a compound of the formula (K4) and / or of at least one physiologically tolerable salt of a compound of the formula (K4),

wherein
G17 and G18 independently of one another represent a hydroxyl group or a group -NG21G22,
in which G21 and G22 independently of one another represent a hydrogen atom, a C ₁ -C ₄ -alkyl group, a C ₃ -C ₆ -cycloalkyl group, a C ₂ -C ₄ -alkenyl group, an aryl group, a C ₁ -C ₄ -monohydroxyalkyl group, a C ₂ -C ₄ -polyhydroxyalkyl group, a C ₁ -C ₄ -alkoxy-C ₁ -C ₄ -alkyl group, an aryl-C ₁ -C ₄ -alkyl group, a heteroaryl-C ₁ -C ₄ -alkyl group,
G19 and G20 independently of one another represent a hydrogen atom, a halogen atom, a C ₁ -C ₄ -alkyl group or a C ₁ -C ₄ -alkoxy group.

It is preferred when according to formula (K4) the radicals G17 and G18 are in ortho position or in meta position to each other.

Especially preferred pyridine derivatives are selected from at least a compound of the group formed from 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, 3,5-diamino-2,6-dimethoxypyridine, 3,4-diaminopyridine, 2- (2-methoxyethyl) amino-3-amino-6-methoxypyridine, 2- (4'-methoxyphenyl) amino-3-aminopyridine, and the physiological acceptable salts of the aforementioned compounds.

preferred Naphthalene derivatives having at least one hydroxy group are selected from at least one compound of the group that is formed from 1-naphthol, 2-methyl-1-naphthol, 2-hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1,3-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and 2,3-dihydroxynaphthalene.

worin
G23 steht für ein Wasserstoffatom, eine C₁-C₄-Alkylgruppe, eine C₃-C₆-Cycloalkylgruppe, eine C₂-C₄-Alkenylgruppe, eine C₁-C₄-Monohydroxyalkylgruppe, eine C₂-C₄-Polyhydroxyalkylgruppe, eine Aryl-C₁-C₄-alkylgruppe,
G24 steht für eine Hydroxygruppe oder eine Gruppe NG26G27, worin G26 und G27 unabhängig voneinander stehen für ein Wasserstoffatom, eine C₁-C₄-Alkylgruppe, eine C₃-C₆-Cycloalkylgruppe, eine C₂-C₄-Alkenylgruppe, eine C₁-C₄-Monohydroxyalkylgruppe, eine C₂-C₄-Polyhydroxyalkylgruppe,
G25 Wasserstoffatom, ein Halogenatom oder eine C₁-C₄-Alkylgruppe,
mit der Maßgabe, dass G24 in meta-Position oder ortho-Position zum Strukturfragment NG23 der Formel bindet.The indole derivatives which can be used according to the invention are preferably selected from at least one compound of the formula (K5) and / or from at least one physiologically tolerated salt of a compound of the formula (K5),

wherein
G23 represents a hydrogen atom, a C ₁ -C ₄ -alkyl group, a C ₃ -C ₆ -cycloalkyl group, a C ₂ -C ₄ -alkenyl group, a C ₁ -C ₄ -monohydroxyalkyl group, a C ₂ -C ₄ -polyhydroxyalkyl group , an aryl-C ₁ -C ₄ -alkyl group,
G24 represents a hydroxy group or a group NG26G27, wherein G26 and G27 are each independently hydrogen, C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl, C ₂ -C ₄ alkenyl, C C ₁ -C ₄ monohydroxyalkyl group, a C ₂ -C ₄ polyhydroxyalkyl group,
G25 is a hydrogen atom, a halogen atom or a C ₁ -C ₄ -alkyl group,
with the proviso that G24 binds in the meta position or ortho position to the structural fragment NG23 of the formula.

Especially Preferred indole derivatives are selected from at least a compound of the group formed from 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole and the physiologically acceptable Salts of the aforementioned compounds.

worin
G28 steht für ein Wasserstoffatom, eine C₁-C₄-Alkylgruppe, eine C₃-C₆-Cycloalkylgruppe, eine C₂-C₄-Alkenylgruppe, eine C₁-C₄-Monohydroxyalkylgruppe, eine C₂-C₄-Polyhydroxyalkylgruppe, eine Aryl-C₁-C₄-alkylgruppe,
G29 steht für eine Hydroxygruppe oder eine Gruppe NG31G32, worin G31 und G32 unabhängig voneinander stehen für ein Wasserstoffatom, eine C₁-C₄-Alkylgruppe, eine C₃-C₆-Cyclo alkylgruppe, eine C₂-C₄-Alkenylgruppe, eine C₁-C₄-Monohydroxyalkylgruppe, eine C₂-C₄-Polyhydroxyalkylgruppe,
G30 Wasserstoffatom, ein Halogenatom oder eine C₁-C₄-Alkylgruppe,
mit der Maßgabe, dass G29 in meta-Position oder ortho-Position zum Strukturfragment NG28 der Formel bindet.The indoline derivatives which can be used according to the invention are preferably selected from at least one compound of the formula (K6) and / or from at least one physiologically tolerable salt of a compound of the formula (K6),

wherein
G28 represents a hydrogen atom, a C ₁ -C ₄ -alkyl group, a C ₃ -C ₆ -cycloalkyl group, a C ₂ -C ₄ -alkenyl group, a C ₁ -C ₄ -monohydroxyalkyl group, a C ₂ -C ₄ -polyhydroxyalkyl group , an aryl-C ₁ -C ₄ -alkyl group,
G29 represents a hydroxy group or a group NG31G32 in which G31 and G32 independently of one another represent a hydrogen atom, a C ₁ -C ₄ -alkyl group, a C ₃ -C ₆ -cycloalkyl group, a C ₂ -C ₄ -alkenyl group, a C ₁ -C ₄ monohydroxyalkyl group, a C ₂ -C ₄ polyhydroxyalkyl group,
G30 is a hydrogen atom, a halogen atom or a C ₁ -C ₄ -alkyl group,
with the proviso that G29 binds in the meta position or ortho position to the structural fragment NG28 of the formula.

Especially preferred indoline derivatives are selected from at least a compound of the group formed from 4-hydroxyindoline, 6-hydroxyindoline and 7-hydroxyindoline and the physiologically acceptable Salts of the aforementioned compounds.

preferred Pyrimidine derivatives are selected from at least one Compound of the group formed from 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 and the physiologically acceptable Salts of the aforementioned compounds.

The following are examples of the radicals mentioned as substituents of the compounds of the formulas (K1) to (K6): Examples of C ₁ -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}

Inventive examples of C ₃ -C ₆ cycloalkyl groups are cyclopropyl, cyclopentyl and cyclohexyl.

Examples of C ₁ -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 -C ₄ monohydroxyalkyl group, CH ₂ OH, CH ₂ CH ₂ OH, CH ₂ CH ₂ CH ₂ OH, CH ₂ CH (OH) CH ₃ , CH ₂ CH ₂ CH ₂ CH ₂ OH be mentioned, wherein the group CH ₂ CH ₂ OH is preferred.

A particularly preferred example of a C ₂ -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 -C ₄ -monoalkylamino groups, di- (C ₁ -C ₄ -alkyl) amino groups, tri- (C ₁ -C ₄ -alkylammonium groups, mono- (C ₁ -C ₄ -) hydroxyalkyl) amino groups, imidazolinium and NH ₃ ⁺ .

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

Examples of a di (C ₁ -C ₄ alkyl) amino group are N (CH ₃ ) ₂ , N (CH ₂ CH ₃ ) ₂ .

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

Examples of C ₁ -C ₄ -alkoxy-C ₁ -C ₄ -alkoxy groups are OCH ₂ CH ₂ OCH ₃ , OCH ₂ CH ₂ CH ₂ OCH ₃ , OCH ₂ CH ₂ OCH ₂ CH ₃ , OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₃ , OCH ₂ CH ₂ OCH (CH ₃ ) ₂ , OCH ₂ CH ₂ CH ₂ OCH (CH ₃ ) ₂ .

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

Examples of C ₁ -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 .

One An example of an aryl group is the phenyl group, which may also be substituted.

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

Particularly according to the invention preferred coupler components are selected from 3-aminophenol, 5-amino-2-methylphenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 5-amino-4-chloro-2-methylphenol, 5- (2-hydroxyethyl) amino-2-methylphenol, 2,4-dichloro-3-aminophenol, 2-aminophenol, 3-phenylenediamine, 2- (2,4-diaminophenoxy) ethanol, 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, 2 - ({3 - [(2-hydroxyethyl) amino] -4-methoxy-5-methylphenyl} amino) ethanol, 2 - ({3 - [(2-hydroxyethyl) amino] -2-methoxy-5-methylphenyl} amino) ethanol, 2 - ({3 - [(2-hydroxyethyl) amino] -4,5-dimethylphenyl} amino) ethanol, 2- [3-morpholin-4-yl-phenyl) -amino] -ethanol, 3-amino-4- (2-methoxy-ethoxy) -5-methyl-phenylamine, 1-amino-3-bis (2-hydroxyethyl) aminobenzene, resorcinol, 2-methylresorcinol, 4-chlororesorcinol, 1,2,4-trihydroxybenzene, 2-amino-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine, 2,6-dihydroxy-3,4-dimethylpyridine, 3,5-diamino-2,6-dimethoxypyridine, 1-phenyl-3-methylpyrazol-5-one, 1-naphthol, 1,5-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 4-hydroxyindole, 6-hydroxyindole, 7-hydroxyindole, 4-hydroxyindoline, 6-hydroxyindoline, 7-hydroxyindoline or mixtures these compounds or the physiologically acceptable Salts of the aforementioned compounds.

All particularly preferred is resorcinol, 2-methylresorcinol, 5-amino-2-methylphenol, 3-aminophenol, 2- (2,4-diaminophenoxy) ethanol, 1,3-bis (2,4-diaminophenoxy) propane, 1-Methoxy-2-amino-4- (2'-hydroxyethylamino) benzene, 2-amino-3-hydroxypyridine and 1-naphthol and a physiologically acceptable one thereof Salts.

The Coupler components are preferably present in an amount of 0.005 to 20 wt .-%, preferably 0.1 to 5 wt .-%, each based on the ready-to-use oxidation colorants.

In the context of the present invention, the following combinations of oxidation dye precursors of the developer type and of the coupler type are particularly preferred. However, further dye precursors can also be combined with the oxidation dye precursors mentioned as a combination:
p-toluenediamine / resorcinol;
p-toluenediamine / 2-methylresorcinol;
p-toluenediamine / 5-amino-2-methyl phenol;
p-toluenediamine / 3-aminophenol;
p-toluenediamine / 2- (2,4-diaminophenoxy) ethanol;
p-toluenediamine / 1,3-bis (2,4-diaminophenoxy) propane;
p-toluenediamine / 1-methoxy-2-amino-4- (2-hydroxyethylamino) benzene;
p-toluenediamine / 2-amino-3-hydroxypyridine;
p-toluenediamine / 1-naphthol;
2- (2-hydroxyethyl) -p-phenylenediamine / resorcinol;
2- (2-hydroxyethyl) -p-phenylenediamine / 2-methylresorcinol;
2- (2-hydroxyethyl) -p-phenylenediamine / 5-amino-2-methyl phenol;
2- (2-hydroxyethyl) -p-phenylenediamine / 3-aminophenol;
2- (2-hydroxyethyl) -p-phenylenediamine / 2- (2,4-diaminophenoxy) ethanol;
2- (2-hydroxyethyl) -p-phenylenediamine / 1,3-bis (2,4-diaminophenoxy) propane;
2- (2-hydroxyethyl) -p-phenylenediamine / 1-methoxy-2-amino-4- (2-hydroxyethylamino) benzene;
2- (2-hydroxyethyl) -p-phenylenediamine / 2-amino-3-hydroxypyridine;
2- (2-hydroxyethyl) -p-phenylenediamine / 1-naphthol;
2-methoxymethyl-p-phenylenediamine / resorcinol;
2-methoxymethyl-p-phenylenediamine / 2-methylresorcinol;
2-methoxymethyl-p-phenylenediamine / 5-amino-2-methyl phenol;
2-methoxymethyl-p-phenylene diamine / 3-aminophenol;
2-methoxymethyl-p-phenylenediamine / 2- (2,4-diaminophenoxy) ethanol;
2-methoxymethyl-p-phenylene diamine / 1,3-bis (2,4-diaminophenoxy) propane;
2-methoxymethyl-p-phenylenediamine / 1-methoxy-2-amino-4- (2-hydroxyethylamino) benzene;
2-methoxymethyl-p-phenylenediamine / 2-amino-3-hydroxypyridine;
2-methoxymethyl-p-phenylenediamine / 1-naphthol;
N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazol-1-yl) propyl] amine / resorcinol;
N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazol-1-yl) propyl] amine / 2-methylresorcinol;
N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazol-1-yl) propyl] amine / 5-amino-2-methyl phenol;
N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazol-1-yl) propyl] amine / 3-aminophenol;
N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazol-1-yl) propyl] amine / 2- (2,4-diaminophenoxy) ethanol;
N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazol-1-yl) propyl] amine / 1,3-bis (2,4-diaminophenoxy) propane;
N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazol-1-yl) propyl] amine / 1-methoxy-2-amino-4- (2-hydroxyethylamino) benzene;
N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazol-1-yl) propyl] amine / 2-amino-3-hydroxypyridine;
N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazol-1-yl) propyl] amine / 1-naphthol;
4,5-diamino-1- (2-hydroxyethyl) pyrazole / resorcinol;
4,5-diamino-1- (2-hydroxyethyl) pyrazole / 2-methylresorcinol;
4,5-diamino-1- (2-hydroxyethyl) pyrazole / 5-amino-2-methyl phenol;
4,5-diamino-1- (2-hydroxyethyl) pyrazole / 3-aminophenol;
4,5-diamino-1- (2-hydroxyethyl) pyrazole / 2- (2,4-diaminophenoxy) ethanol;
4,5-diamino-1- (2-hydroxyethyl) pyrazole / 1,3-bis (2,4-diaminophenoxy) propane;
4,5-diamino-1- (2-hydroxyethyl) pyrazole / 1-methoxy-2-amino-4- (2-hydroxyethylamino) benzene;
4,5-diamino-1- (2-hydroxyethyl) pyrazole / 2-amino-3-hydroxypyridine;
4,5-diamino-1- (2-hydroxyethyl) pyrazole / 1-naphthol.

Around to achieve a balanced and subtle nuance training is it is advantageous according to the invention if further coloring Contain components in the composition according to the invention are.

In In another embodiment, the inventive Agents contain at least one substantive dye. there are dyes that raise directly on the hair and do not need an oxidative process to form the paint. Direct dyes are usually nitrophenylenediamines, Nitroaminophenols, azo dyes, anthraquinones or indophenols.

The substantive dyes are each preferably in an amount from 0.001 to 20 wt .-%, in particular from 0.05 to 5 wt .-%, respectively based on the entire application preparation used. The total amount of substantive dyes is preferably at most 3% by weight.

Substantive Dyes can be anionic, cationic and nonionic substantive dyes are subdivided.

Anionic substantive dyes:
Particularly suitable anionic direct dyes are the following dyes named after the CI: CI 15.985 (Fond Yellow No. 3, FD & C Yellow No. 6), CI 10.316 (Acid Yellow 1, Food Yellow No. 1), CI 47.005 (D. & C Yellow No. 10, Food Yellow No. 13, Acid Yellow 3, Yellow 10); CI 13,015 (Acid Yellow 9), CI 19,140 (Food Yellow No. 4, Acid Yellow 23), CI 13,065 (Ki406; Acid Yellow 36), CI 45,350 (Acid Yellow 73, D & C Yellow No. 8), CI 10,385 (Acid Orange 3), CI 14,270 (Acid Orange 6), CI 15,510 (Acid Orange 7), CI 20,170 (Acid Orange 24), CI 14,710 (Acid Red 4), CI 14,720 (Acid Red No. 14), CI 16,255 (Ponceau 4R, Acid Red 18), CI 16.185 (Acid Red 27), CI 17,200 (Acid Red 33, Red 33), CI 18.065 (Acid Red 35), CI 45.430 (Acid Red 51), CI 45.100 (Acid Red 52 ), CI 27,290 (Acid Red 73), CI 45,380 (Acid Red 87), CI 45,410 (Acid Red 92), CI 45425 (Acid Red 95), CI 15,685 (Acid Red 184), Acid Red 195, CI 15,850: 1 (Pigment Red 57: 1), CI 14,700 (Food Red No. 1, Ponceau SX, FD & C Red No. 4), CI 61,570 (Acid Green 25), CI 44,090 (Food Green No. 4; Acid Green 50). , CI 42.045 (Food Blue No. 3, Acid Blue 1), CI 42.051 (Acid Blue 3), CI 42.080 (Acid Blue 7), CI 42.090 (Acid Blue 9, FD & C Blue No. 1), CI 62.055 ( Acid Blue 25), CI 62045 (Acid Blue 62), CI 73.015 (Acid Blue 74 ), CI 45.190 (Acid Violet 9), CI 60.730 (D & C Violet no. 2; Acid Violet 43), CI 10.410 (Acid Brown 13), CI 20.470 (Acid Black 1), CI 15.711 (Acid Black 52), CI 28.440 (Food Black No. 1), 3 ', 3 ", 5', 5 '' -Tetrabromophenolsulfonphthalein (bromophenol blue) and 3,3 ', 3'',4,5,5', 5 '', 6-Octabromphenolsulfonphthalein (tetrabromophenol blue).

preferred anionic substantive dyes are among the international ones Designations or trade names Acid Yellow 1, Yellow 10, Acid Yellow 23, Acid Yellow 36, Acid Orange 7, Acid Red 33, Acid Red 52, Pigment Red 57: 1, Acid Blue 7, Acid Green 50, Acid Violet 43, Acid Black 1, acid black 52 and tetrabromophenol blue known compounds.

When cationic substantive dyes are particularly suitable C. 51,175 (Basic Blue 6), C.I. 42,595 (Basic Blue 7), C.I. (Basic Blue 8), C.I. 52.015 (Basic Blue 9), C. I. 44.045 (Basic Blue 26), C.I. 11,154 (Basic Blue 41), C.I. 56,059 (Basic Blue No. 99), C.I. 42,535 (Basic Violet 1), C.I. 42,520 (Basic Violet 2), C.I. 42,555 (Basic Violet 3), C.I. 45,170 (Basic Violet 10), C.I. 42.510 (Basic Violet 14), C.I. 21.010 (Basic Brown 4), C. I. 12,250 (Basic Brown 16), C.I. 12,251 (Basic Brown 17), 30.1. 12,605 (Basic Orange 69), C.I. 50,240 (Basic Red 2), C.I. 11,055 (Basic Red 22), C.I. 12,245 (Basic Red 76), C.I. 41,000 (Basic Yellow 2), C.I. 48,055 (Basic Yellow 11), C.I. 12,719 (Basic Yellow 57), C.I. 42,040 (Basic Green 1), C.I. 42,000 (Basic Green 4), 1- (2-Morpholiniumpropylamino) -4-hydroxy-anthraquinone, 9,10-methyl sulfate, 1 - [(3- (Dimethylpropylaminium) propyl) amino] -4- (methylamino) -9,10-anthraquinone-chloride and substantive dyes containing a heterocycle, which has at least one quaternary nitrogen atom.

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

Preferred cationic substantive dyes are included

• (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 described for example in the EP-A2-998 908 to which reference is made at this point, are called in the claims 6 to 11.

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

The Compounds of the formulas (DZ1), (DZ3) and (DZ5), which are also available under the terms Basic Yellow 87, Basic Orange 31 and Basic Red 51 are very particularly preferred cationic substantive Dyes of group (c).

The cationic direct dyes, under the trademark Arianor are also according to the invention very particularly preferred cationic substantive dyes.

When Nonionic substantive dyes are particularly suitable nonionic nitro and quinone dyes and neutral azo dyes.

Suitable blue nitro dyes are in particular:
1,4-bis - [(2-hydroxyethyl) amino] -2-nitrobenzene, 1- (2-hydroxyethyl) amino-2-nitro-4- [di (2-hydroxyethyl) amino] benzene (HC Blue 2), 1-Methylamino-4- [methyl- (2,3-dihydroxypropyl) amino] -2-nitrobenzene (HC Blue 6), 1 - [(2,3-dihydroxypropyl) amino] -4- [ethyl- (2- hydroxyethyl) amino] -2-nitrobenzene hydrochloride (HC Blue 9), 1 - [(2,3-dihydroxypropyl) amino] -4- [methyl (2-hydroxyethyl) amino] -2-nitrobenzene (HC Blue 10) , 4- [di (2-hydroxyethyl) amino] -1 - [(2-methoxyethyl) amino] -2-nitrobenzene (HC Blue 11), 4- [ethyl- (2-hydroxyethyl) amino] -1- [ (2-hydroxyethyl) amino] -2-nitrobenzene hydrochloride (HC Blue 12), 2 - ((4-amino-2-nitrophenyl) amino) -5-dimethylaminobenzoic acid (HC Blue 13), 1-amino-3-methyl 4 - [(2-hydroxyethyl) amino] -6-nitrobenzene (HC Violet 1), 1- (3-hydroxypropylamino) -4- [di (2-hydroxyethyl) amino] -2-nitrobenzene (HC Violet 2), 1- (2-aminoethylamino) -4- [di (2-hydroxyethyl) amino] -2-nitrobenzene, 4- (di- (2-hydroxyethyl) amino) -2-nitro-1-phenylaminobenzene.

Suitable red nitro dyes are in particular:
1-Amino-4 - [(2-hydroxyethyl) amino] -2-nitrobenzene (HC Red 7), 2-amino-4,6-dinitrophenol (picramic acid) and its salts, 1,4-diamino-2-nitrobenzene ( CI 76,070), 4-amino-2-nitro-diphenylamine (HC Red 1), 1-amino-4- [di (2-hydroxyethyl) amino] -2-nitrobenzene hydrochloride (HC Red 13), 1-amino- 4 - [(2-hydroxyethyl) amino] -5-chloro-2-nitrobenzene, 4-amino-1 - [(2-hydroxyethyl) amino] -2-nitrobenzene (HC Red 3), 4 - [(2- Hydroxyethyl) methylamino] -1- (methylamino) -2-nitrobenzene, 1-amino-4 - [(2,3-dihydroxypropyl) amino] -5-methyl-2-nitrobenzene, 1-amino-4- (methylamino) - 2-nitrobenzene, 4-amino-2-nitro-1 - [(prop-2-en-1-yl) amino] benzene, 4-amino-3-nitrophenol, 4 - [(2-hydroxyethyl) amino] -3 nitrophenol, 4 - [(2-nitrophenyl) amino] phenol (HC Orange 1), 1 - [(2-aminoethyl) amino] -4- (2-hydroxyethoxy) -2-nitrobenzene (HC Orange 2), 4- (2,3-dihydroxypropoxy) -1 - [(2-hydroxyethyl) amino] -2-nitrobenzene (HC Orange 3), 1-amino-5-chloro-4 - [(2,3-dihydroxypropyl) amino] -2 -nitrobenzene (HC Red 10), 5-chloro-1,4- [di (2,3-dihydroxypropyl) amino] -2-nitrobenzo 1 (HC Red 11), 2 - [(2-hydroxyethyl) amino] -4,6-dinitrophenol, 4-ethylamino-3-nitrobenzoic acid, 2 - [(4-amino-2-nitrophenyl) amino] benzoic acid, 2- Chloro-6-ethylamino-4-nitrophenol, 2-amino-6-chloro-4-nitrophenol, 4 - [(3-hydroxypropyl) amino] -3-nitrophenol (HC Red BN), 2,5-diamino-6- nitropyridine, 6-amino-3 - [(2-hydroxyethyl) amino] -2-nitropyridine, 3-amino-6 - [(2-hydroxyethyl) amino] -2-nitropyridine, 3-amino-6- (ethylamino) - 2-nitropyridine, 3 - [(2-hydroxyethyl) amino] -6- (methylamino) -2-nitropyridine, 3-amino-6- (methylamino) -2-nitropyridine, 6- (ethylamino) -3 - [(2 -hydroxyethyl) amino] -2-nitropyridine, 1,2,3,4-tetrahydro-6-nitroquinoxaline, 7-amino-3,4-dihydro-6-nitro-2H-1,4-benzoxazine (HC Red 14) ,

Suitable yellow nitro dyes are in particular:
1,2-diamino-4-nitrobenzene (CI 76,020), 1 - [(2-hydroxyethyl) amino] -2-nitrobenzene (HC Yellow 2), 1- (2-hydroxyethoxy) -2 - [(2-hydroxyethyl) amino] -5-nitrobenzene (HC Yellow 4), 1-amino-2 - [(2-hydroxyethyl) amino] -5-nitrobenzene (HC Yellow 5), 4 - [(2,3-dihydroxypropyl) amino] -3 -nitro-1-trifluoromethylbenzene (HC Yellow 6), 2- [di (2-hydroxyethyl) amino] -5-nitrophenol, 2 - [(2-hydroxyethyl) amino] -1-methoxy-5-nitrobenzene, 2 -Amino-3-nitrophenol, 2-amino-4-nitrophenol, 1-amino-2-methyl-6-nitrobenzene, 1- (2-hydroxyethoxy) -3-methylamino-4-nitrobenzene, 2,3- (dihydroxypropoxy) 3-methylamino-4-nitrobenzene, 3 - [(2-aminoethyl) amino] -1-methoxy-4-nitrobenzene hydrochloride (HC Yellow 9), 1-chloro-2,4-bis [(2-hydroxyethyl) amino] -5-nitrobenzene (HC Yellow 10), 2 - [(2-hydroxyethyl) amino] -5-nitrophenol (HC Yellow 11), 1 - [(2'-ureidoethyl) amino] -4-nitrobenzene, 1- Amino-4 - [(2-aminoethyl) amino] -5-methyl-2-nitrobenzene, 4 - [(2-hydroxyethyl) amino] -3-nitro-1-methylbenzene, 1-chloro-4 - [(2- hydroxyethyl) amino] -3-nitrobenzene (HC Yellow 12), 4 - [(2 -Hydroxyethyl) amino] -3-nitro-1-trifluoromethylbenzene (HC Yellow 13), 4 - [(2-hydroxyethyl) amino] -3-nitrobenzonitrile (HC Yellow 14), 4 - [(2-hydroxyethyl) amino ] -3-nitrobenzamide (HC Yellow 15) 3 - [(2-hydroxyethyl) amino] -4-methyl-1-nitrobenzene, 4-chloro-3 - [(2-hydroxyethyl) amino] -1-nitrobenzene.

Suitable quinone dyes are in particular:
1,4-Di - [(2,3-dihydroxypropyl) amino] -9,10-anthraquinone, CI 61.545 (Disperse Blue 23), CI 61.505 (Disperse Blue 3), 2 - [(2-aminoethyl) amino] 9,10-anthraquinone (HC Orange 5), CI 60.710 (Disperse Red 15), 1-hydroxy-4 - [(4-methyl-2-sulfophenyl) amino] -9,10-anthraquinone, CI 75.470 (Natural Red 4 ), 1 - [(3-aminopropyl) ami no] -4-methylamino-9,10-anthraquinone (HC Blue 8), 1 - [(3-aminopropyl) amino] -9,10-anthraquinone (HC Red 8), CI 62.015 (Disperse Red 11, Solvent Violet No 26), CI 62,500 (Disperse Blue 7, Solvent Blue No. 69), CI 61,100 (Disperse Violet 1), CI 61,105 (Disperse Violet 4, Solvent Violet No. 12), 2-hydroxy-3-methoxy-1, 4-naphthoquinone, 2,5-dihydroxy-1,4-naphthoquinone, 2-hydroxy-3-methyl-1,4-naphthoquinone, N- {6 - [(3-chloro-4- (methylamino) phenyl) imino] 4-methyl-3-oxo-1,4-cyclohexadien-1-yl} urea (HC Red 9), 2 - {{4- [di (2-hydroxyethyl) amino] phenyl} amino} -5- [ (2-hydroxyethylamino] -2,5-cyclohexadiene-1,4-dione (HC Green 1), CI 75,500 (Natural Brown 7), CI 75,480 (Natural Orange 6), CI 73,000, 4 - {{5 - [( 2-hydroxyethyl) amino] -1-methyl-1H-pyrazol-4-yl} imino} -4,5-dihydro-5 - [(2-hydroxyethyl) imino] -1-methyl-1H-pyrazol-sulfate (1 : 1) Hydrate (1: 1).

Suitable neutral azo dyes are in particular:
CI 11.210 (Disperse Red 17), 1- [di (2-hydroxyethyl) amino] -4 - [(4-nitrophenyl) azo] benzene (Disperse Black 9), 4 - [(4-aminophenyl) azo] -1- [di (2-hydroxyethyl) amino] -3-methylbenzene (HC Yellow 7), 2,6-diamino-3 - [(pyridin-3-yl) azo] pyridine, CI 11855 (Disperse Yellow 3), CI 11.005 ( Disperse Orange 3).

preferred Nonionic direct dyes are among the international ones Designations or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, HC Orange 1, Disperse Orange 3, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, HC Red BN, HC Blue 2, HC Blue 11, HC Blue 12, Disperse Blue 3, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9 known compounds, and 1,4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis (2-hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- (2-hydroxyethyl) aminophenol, 2- (2-hydroxyethyl) amino-4,6-dinitrophenol, 4 - [(2-hydroxyethyl) amino] -3-nitro-1-methylbenzene, 1-amino-4- (2-hydroxyethyl) amino-5-chloro-2-nitrobenzene, 4-amino-3-nitrophenol, 1- (2'-ureidoethyl) amino-4-nitrobenzene, 2 - [(4-amino-2-nitrophenyl) amino] benzoic 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-4-nitrophenol.

It is not required that the directly contained Dyes each represent uniform compounds. Much more may, due to the manufacturing process for the individual dyes, in subordinate quantities even more Components are included, as far as these are not the dyeing result adversely affect or for other reasons, eg. B. toxicological, must be excluded.

Farther can also be used as direct dyes in nature occurring dyes are used, as for example in henna red, henna neutral, henna black, chamomile flower, Sandalwood, black tea, walnut, buckthorn bark, sage, bluewood, Madder root, catechu and alkano root are included.

A another possibility for coloring offers the use of colorants, which are so-called Oxofarbstoffvorprodukte contain. A first class of oxo dye precursors are compounds with at least one reactive carbonyl group. This first class is referred to as component (Oxo1). A second class of oxo dye precursors form C, H-acidic compounds and compounds with primary or secondary amino group or hydroxy group, which in turn are selected from compounds of the group that formed is made from primary or secondary aromatic Amines, nitrogen-containing heterocyclic compounds and aromatic Hydroxy compounds. This second class is called Component (Oxo2) designated. The aforementioned components (Oxo1) and (Oxo2) are generally themselves no dyes, and are therefore suitable for each taken alone, not for coloring keratin-containing Fibers. In combination, they form in a non-oxidative process the so-called oxo dyeing dyes. The resulting Dyeings have partial color fastness on the keratin-containing Fiber comparable to those of oxidation staining are.

The Nuance spectrum achievable with gentle oxo staining is very wide and the obtained color often shows an acceptable brilliance and color depth. Under compounds of However, component (Oxo2) can also be corresponding Developing and / or coupling agent oxidation dye precursors with or use without the use of an oxidizing agent. Consequently the method of oxo staining can be easily determined combine with the oxidative dyeing system.

• – mindestens einer Verbindung, die mindestens eine reaktive Carbonylgruppe enthält (Komponente (Oxo1)) mit mindestens einer Verbindung (Komponente Oxo2)
• – Verbindungen, ausgewählt aus (Oxo2a) C,H-aciden Verbindungen und/oder aus (Oxo2b) Verbindungen mit primärer oder sekundärer Aminogruppe oder Hydroxygruppe, ausgewählt aus mindestens einer Verbindung der Gruppe, die gebildet wird aus primären oder sekundären aromatischen Aminen, stickstoffhaltigen heterocyclischen Verbindungen und aromatischen Hydroxyverbindungen

eingesetzt.As a color-modifying component according to the invention, it is therefore also possible in a further embodiment to use oxo dye precursors. Oxofarbstoffvorprodukte are preferred as a combination of

• - At least one compound containing at least one reactive carbonyl group (component (Oxo1)) with at least one compound (component Oxo2)
• Compounds selected from (oxo2a) C, H-acidic compounds and / or from (oxo2b) compounds having a primary or secondary amino group or hydroxy group selected from at least one compound of the group formed from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds Compounds and aromatic hydroxy compounds

used.

• 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 (Oxo1) leitet sich in diesem Fall c) von einem Aldehyd ab)

an das Kohlenstoffatom der Carbonylgruppe der reaktiven Carbonylverbindung.Reactive carbonyl compounds as component (oxo1) have in the context of the invention at least one carbonyl group as a reactive group which reacts with the component (oxo2) to form a covalent bond. Preferred reactive carbonyl compounds are selected from compounds which carry at least one formyl group and / or at least one keto group, in particular at least one formyl group. Furthermore, those compounds according to the invention are also suitable as component (Oxo1) in which the reactive carbonyl group is derivatized or masked such that the reactivity of the carbon atom of the derivatized carbonyl group with respect to the component (Oxo2) 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 (oxo1) is derived in this case c) from an aldehyde)

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

preferred reactive carbonyl compounds of the component (oxo1) are selected from the group consisting of benzaldehyde and its derivatives, Naphthaldehyde and its derivatives, cinnamaldehyde and its derivatives, 2-formylmethylene-1,3,3-trimethylindoline (Fischer's aldehyde or tribas Aldehyde), 2-indolealdehyde, 3-indolealdehyde, 1-methylindole-3-aldehyde, 2-methylindole-3-aldehyde, 2- (1 ', 3', 3'-trimethyl-2-indolinylidene) acetaldehyde, 1-methylpyrrole-2-aldehyde, pyridoxal, antipyrin-4-aldehyde, furfural, 5-nitrofurfural, chromon-3-aldehyde, 3- (5'-nitro-2'-furyl) acrolein, 3- (2'-furyl) acrolein and imidazole-2-aldehyde, 5- (4-dimethylaminophenyl) penta-2,4-dienal, 5- (4-diethylaminophenyl) penta-2,4-dienal, 5- (4-methoxyphenyl) penta-2,4-dienal, 5- (3,4-dimethoxyphenyl) penta-2,4-dienal, 5- (2,4-dimethoxyphenyl) penta-2,4-dienal, 5- (4-piperidinophenyl) penta-2,4-dienal, 5- (4-morpholinophenyl) penta-2,4-dienal, 5- (4-pyrrolidinophenyl) penta-2,4-dienal, 5- (4-dimethylamino-1-naphthyl) penta-3,5-dienal, Piperonal, 6-nitropiperonal, 2-nitropiperonal, 5-nitrovanillin, 2,5-dinitrosalicylaldehyde, 5-bromo-3-nitrosalicylaldehyde, 3-nitro-4-formylbenzenesulfonic acid, Salts whose cationic component is 4-formyl-1-methylpyridinium, 2-formyl-1-methylpyridinium, 4-formyl-1-ethylpyridinium, 2-formyl-1-ethylpyridinium, 4-formyl-1-benzylpyridinium, 2-formyl-1-benzylpyridinium, 4-formyl-1,2-dimethylpyridinium, 4-formyl-1,3-dimethylpyridinium, 4-formyl-1-methylquinolinium, 2-formyl-1-methylquinolinium, 5-formyl-1-methylquinolinium, 6-formyl-1-methylquinolinium, 7-formyl-1-methylquinolinium, 8-formyl-1-methylquinolinium, 5-formyl-1-ethylquinolinium, 6-formyl-1-ethylquinolinium, 7-formyl-1-ethylquinolinium, 8-formyl-1-ethylquinolinium, 5-formyl-1-benzylquinolinium, 6-formyl-1-benzyl-quinolinium, 7-formyl-1-benzyl-quinolinium, 8-formyl-1-benzyl-quinolinium, 5-formyl-1-allyl-quinolinium, 6-formyl-1-allyl-quinolinium, 7-formyl-1-allyl-quinolinium or 8-formyl-1-allylquinolinium and their anionic counterion selected from benzenesulfonate, p-toluenesulfonate, methanesulfonate, Perchlorate, sulfate, chloride, bromide, iodide, tetrachlorozincate, methylsulfate, Trifluoromethanesulfonate or tetrafluoroborate, isatin, 1-methylisatin, 1-allylisatin, 1-hydroxymethylisatin, 5-chloroisatin, 5-methoxyisatin, 5-nitroisatin, 6-nitroisatin, 5-sulfoisatin, 5-carboxyisatin, quinisatin, 1-Methylchinisatin, and any mixtures of the preceding Links.

The preferred derivatives of benzaldehydes, naphthaldehydes or cinnamaldehydes of the reactive carbonyl compound according to component (Oxo1) 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-dimethoxybenzaldehyde, 4-hydroxy-2,5-dimethoxybenzaldehyde, 4- Hydroxy-2,6-dimethoxybenzaldehyde, 4-hydroxy-2-methylbenzaldehyde, 4-hydroxy-2,3-dimethyl benzaldehyde, 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-methoxybenzaldehyde, 2,4-dihydroxy-5-methoxybenzaldehyde, 2,4-dihydroxy-6-methoxybenzaldehy d, 2,5-dihydroxybenzaldehyde, 2,6-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde, 3,4-dihydroxy-2-methylbenzaldehyde, 3,4-dihydroxy-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-morpholinobenzaldehyde, 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 ehyd, 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-dibutylaminobenzaldehyde, 3-carboxy-4-hydroxy-benzaldehyde, 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 and 3-allyl-4-hydroxy-5-formylbenzaldehy d.

When C, H-acidic compounds generally become such compounds which is bound to an aliphatic carbon atom Carrying hydrogen atom, due to electron-withdrawing Substituents an activation of the corresponding carbon-hydrogen bond is effected. In principle, the choice of C, H-acidic compounds no limits, as long as after condensation with the reactive Carbonyl compounds of the component (Oxo1) one for the human eye visible colored compound is obtained. It deals According to the invention preferably to such C, H-acid Compounds which contain an aromatic and / or a heterocyclic Rest included. The heterocyclic radical may in turn be aliphatic or be aromatic. Particularly preferred are the C, H-acids Compounds selected from heterocyclic compounds, in particular cationic, heterocyclic compounds.

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-C₄-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 Aryl-C₁-C₆-alkylgruppe,
• • X^– steht für ein physiologisch verträgliches Anion,
• • Het steht für einen gegebenenfalls substituierten Heteroaromaten,
• • X¹ steht für eine direkte Bindung oder eine Carbonylgruppe.

Very particular preference is given to using as component (Oxo2a) at least one C, H-acidic compound having an aromatic or aliphatic, heterocyclic main body which is selected from cyclic onium compounds having the structural unit of the formula (CH-1) and / or compounds of the formula ( CH-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 -, 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 ₄ -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 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 the radicals R 10 and R 12 denotes a C ₁ -C ₆ -alkyl group,
• R 11 is 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 an 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 can form a 5- or 6-membered aromatic ring, optionally with 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 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 an aryl-C ₁ -C ₆ -alkyl group,
• • X ^- is a physiologically acceptable anion,
• Het is an optionally substituted heteroaromatic,
• • X ¹ represents a direct bond or a carbonyl group.

At least one group R 10 or R 12 according to formula (CH-1) necessarily stands for 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, i-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 represents a methyl group.

In In a preferred embodiment, Y is of the formula (CH-1) for an oxygen or a sulfur atom, more preferred for an oxygen atom.

The radical R 8 of the formula (CH-1) 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 C ₂ -C ₆ - Hydroxyalkyl group (especially a 2-hydroxyethyl group) or an optionally substituted benzyl group.

R11 of the formula (CH-1) is preferably a hydrogen atom.

Particularly preferred in formula (CH-1) are the radicals R9, R10 and R12 is a methyl group, the radical R11 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 (especially an allyl group), a C ₂ -C ₆ hydroxyalkyl group (especially a 2-hydroxyethyl group) or an optionally substituted benzyl group.

Preferably, the compounds according to formula (CH-1) are selected from one or more compounds of the group of salts with physiologically compatible counterion X ^- which is formed from salts of 1,2-dihydro-1,3,4,6-tetramethyl- 2-oxo-pyrimidinium, 1,2-dihydro-1,3-diethyl-4,6-dimethyl-2-oxo-pyrimidinium, 1,2-dihydro-1,3-dipropyl-4,6-dimethyl-2 oxo-pyrimidinium, 1,2-dihydro-1,3-di- (2-hydroxyethyl) -4,6-dimethyl-2-oxo-pyrimidinium, 1,2-dihydro-1,3-diphenyl-4,6- dimethyl-2-oxopyrimidinium, 1,2-dihydro-1,3,4-trimethyl-2-oxopyrimidinium, 1,2-dihydro-1,3-diethyl-4-methyl-2-oxopyrimidinium, 1,2-Dihydro-1,3-dipropyl-4-methyl-2-oxopyrimidinium, 1,2-dihydro-1,3-di (2-hydroxyethyl) -4-methyl-2-oxopyrimidinium, 1 , 2-dihydro-1,3-diphenyl-4-methyl-2-oxopyrimidinium, 1-allyl-1,2-dihydro-3,4,6-trimethyl-2-oxopyrimidinium, 1,2-dihydro -1- (2-hydroxyethyl) -3,4,6-trimethyl-2-oxopyrimidinium, 1,2-dihydro-1,3,4,6-tetramethyl-2-thioxopyrimidinium, 1,2-dihydro -1,3-diethyl-4,6-dim ethyl 2-thioxopyrimidinium, 1,2-dihydro-1,3-dipropyl-4,6-dimethyl-2-thioxopyrimidinium, 1,2-dihydro-1,3-di (2-hydroxyethyl) -4 , 6-dimethyl-2-thioxopyrimidiniums, 1,2-dihydro-1,3-diphenyl-4,6-dimethyl-2-thioxopyrimidiniums, 1,2-dihydro-1,3,4-trimethyl-2 -thioxo-pyrimidinium, 1,2-dihydro-1,3-diethyl-4-methyl-2-thioxopyrimidinium, 1,2-dihydro-1,3-dipropyl-4-methyl-2-thioxopyrimidinium, 1,2-dihydro 1,3-di- (2-hydroxyethyl) -4-methyl-2-thioxo-pyrimidinium, 1,2-dihydro-1,3-diphenyl-4-methyl-2-thioxo-pyrimidinium, 1,2-dihydro 3,4-dimethyl-2-oxo-quinazolinium and 1,2-dihydro-3,4-dimethyl-2-thioxoquinazolinium.

Very particularly preferred compounds according to formula (CH-1) 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-pyrimidinium, 1,2-dihydro-1,3,4-trimethyl-2-oxo-pyrimidinium, 1-allyl-1,2-dihydro-3,4,6-trimethyl-2-oxo-pyrimidinium , 1,2-dihydro-1- (2-hydroxyethyl) -3,4,6-trimethyl-2-oxopyrimidinium and 1,2-dihydro-1,3,4,6-tetramethyl-2-thioxo-pyrimidinium ,

X ^- is in the formulas (CH-1) and in the above lists preferably for halide, benzenesulfonate, p-toluenesulfonate, (C ₁ -C ₄ -alkane) sulfonate, trifluoromethanesulfonate, perchlorate, ½Sulfate, hydrogen sulfate, tetrafluoroborate, hexafluorophosphate or Tetrachlorozinkat. The anions chloride, bromide, iodide, hydrogensulfate or p-toluenesulfonate are particularly preferably used as X-.

preferred Ring structures bearing the structural unit of the formula (CH-1), are preferably selected according to the invention from 3H indolium, benzothiazolium, benzoxazolium, 1,2-dihydro-2-oxopyrimidinium, Quinolinium, quinoxaline or pyridinium.

According to the invention, particularly suitable compounds of the formula (CH-2) are those in which the radical Het according to formula (CH-2) is derived from one of the heteroaromatic compounds furan, thiophene, pyrrole, isoxazole, isothiazole, imidazole, oxazole, thiazole, Pyridine, pyridazine, pyrimidine, pyrazine, 1,2,3-triazine, 1,2,4-triazine, 1,3,5-triazine, benzopyrrole, benzofuran, benzothiophene, benzimidazole, benzothiazole, benzoxazole, indazole, benzoisoxazole, benzoisothiazole, Indole, quinoline, isoquinoline, cinnoline, phthalazine, quinazoline, quinoxaline, acridine, benzoquinoline, benzoisoquinoline, phenazine, benzocinnoline, benzoquinazoline, benzoquinoxaline, phenoxazine, phenothiazine, nephthyridine, phenanthroline, indolizine, quinolizine, carboline, purine, pteridine or coumarin; aforementioned heteroaromatic compounds having at least one group selected from a halogen atom, a nitro group, a mercapto group, a mercapto-C ₁ -C ₆ alkyl group, a heteroaryl group, an aryl group, a C ₁ -C ₆ Alkyl group, a C ₁ -C ₆ alkoxy group, a hydroxy group, a C ₂ -C ₆ hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a C ₁ -C ₆ alkoxy-C ₁ -C ₆ alkyl group , an aryl-C ₁ -C ₆ -alkyl group, an amino group, a mono- (C ₁ -C ₆ -alkyl) amino group, a di (C ₁ -C ₆ -alkyl) amino group, a dialkylaminoalkyl group - (CH ₂ ) -NR'R ", wherein n is an integer of 2 and 6 and R 'and R" independently represent a linear or branched alkyl group which may optionally together form a ring may be substituted.

Preferably the compounds according to formula (CH-2) are selected at least one compound of the group consisting of 2- (2-furoyl) acetonitrile, 2- (5-bromo-2-furoyl) acetonitrile, 3- (2,5-dimethyl-3-furyl) -3-oxopropanitrile, 2- (2-thenoyl) acetonitrile, 2- (3-thenoyl) acetonitrile, 2- (5-fluoro-2-thenoyl) acetonitrile, 2- (5-chloro-2-thenoyl) acetonitrile, 2- (5-bromo-2-thenoyl) acetonitrile, 2- (5-methyl-2-thenoyl) acetonitrile, 2- (2,5-dimethylpyrrol-3-oyl) acetonitrile, 2- (1,2,5-trimethylpyrrol-3-oyl) acetonitrile, 1H-benzimidazol-2-ylacetonitrile, 1H-benzothiazol-2-ylacetonitrile, 2- (pyrid-2-yl) acetonitrile, 2,6-bis (cyanomethyl) pyridine, 2- (indol-3-oyl) acetonitrile, 2- (2-methylindol-3-oyl) acetonitrile and 2- (6-hydroxy-4,7-dimethoxy-1-benzofuran-5-oyl) acetonitrile, in particular 1H-benzimidazol-2-ylacetonitrile.

The C, H-acidic compounds of the oxo dye precursors of the component (oxo2a) are most preferably selected from at least one compound of the group consisting of 2- (2-furoyl) acetonitrile, 2- (5-bromo-2-furoyl) acetonitrile, 3- (2,5-dimethyl-3-furyl) -3-oxopropanitrile, 2- (2-thenoyl) acetonitrile, 2- (3-thenoyl) acetonitrile, 2- (5-fluoro-2-thenoyl) acetonitrile, 2 - (5-chloro-2-thenoyl) acetonitrile, 2- (5-bromo-2-thenoyl) acetonitrile, 2- (5-methyl-2-thenoyl) acetonitrile, 2- (2,5-dimethylpyrrol-3-oyl ) acetonitrile, 2- (1,2,5-trimethylpyrrol-3-oyl) acetonitrile, 1H-benzimidazol-2-ylacetonitrile, 1H-benzothiazol-2-ylacetonitrile, 2- (pyrid-2-yl) acetonitrile, 2.6 Bis (cyanomethyl) pyridine, 2- (indol-3-oyl) acetonitrile, 2- (2-methyl-indol-3-oyl) acetonitrile, 2- (6-hydroxy-4,7-dimethoxy-1-benzofuran -5-oyl) acetonitrile, 1,2,3,3-tetramethyl-3H-indolium iodide, 1,2,3,3-tetramethyl-3H-indolium p-toluenesulfonate, 1,2,3,3-tetramethyl-3H -indolium methanesulfonate, 2,3-dimethyl-benzothiazolium iodide, 2,3-dimethyl-benzothiazoli p-Toluenesulfonate, 1,4-dimethylquinolinium iodide, 1,2-dimethylquinolinium iodide, 3-ethyl-2-methylbenzoxazolium iodide, 3-ethyl-2-methylbenzothiazolium iodide, 1-ethyl-4-methylquinolinium iodide, 1- Ethyl 2-methylquinolinium iodide, 1,2,3-trimethylquinoxalinium iodide, 3-ethyl-2-methylbenzoxazolium p-toluenesulfonate, 3-ethyl-2-methylbenzothiazolium p-toluenesulfonate, 1-ethyl-4-methylquinolinium p -toluenesulfonate, 1 Ethyl 2-methylquinolinium p-toluenesulfonate, 1,2,3-trimethylquinoxaluminum p-toluenesulfonate, 1-allyl-1,2-dihydro-3,4,6-trimethyl-2-oxopyrimidinium bromide, 1,2-dihydroxy 1- (2-hydroxyethyl) -3,4,6-trimethyl-2-oxopyrimidinium p-toluenesulfonate, 1,2-dihydro-1,3,4,6-tetramethyl-2-oxopyrimidinium chloride, 1,2-dihydro- 1,3-diethyl-4,6-dimethyl-2-oxopyrimidinium chloride, 1,2-dihydro-1,3-dipropyl-4,6-dimethyl-2-oxopyrimidinium chloride, 1-allyl-1,2-dihydro- 3,4,6-trimethyl-2-oxopyrimidinium hydrogensulfate, 1,2-dihydro-1- (2-hydroxyethyl) -3,4,6-trimethyl-2-oxopyrimidinium bisulfate, 1,2-dihydro- 1,3,4,6-tetramethyl-2-oxopyrimidinium bisulphate, 1,2-dihydro-1,3-diethyl-4,6-dimethyl-2-oxopyrimidinium bisulphate, 1,2-dihydro-1,3-dipropyl 4,6-di methyl-2-oxopyrimidinium bisulfate, 1,2-dihydro-1,3,4-trimethyl-2-oxopyrimidinium chloride, 1,2-dihydro-1,3,4-trimethyl-2-oxopyrimidinium bisulfate, 1,2-dihydro 1,3-diethyl-4-methyl-2-oxopyrimidinium chloride, 1,2-dihydro-1,3-diethyl-4-methyl-2-oxopyrimidinium hydrogensulfate, 1,2-dihydro-1,3-dipropyl-4 -methyl-2-oxopyrimidinium chloride, 1,2-dihydro-1,3-dipropyl-4-methyl-2-oxopyrimidinium hydrogensulfate, 1,2-dihydro-1,3,4,6-tetramethyl-2-thioxopyrimidinium chloride, 1,2-Dihydro-1,3-diethyl-4,6-dimethyl-2-thioxopyrimidinium chloride, 1,2-dihydro-1,3-dipropyl-4,6-dimethyl-2-thioxopyrimidinium chloride, 1,2- Dihydro-1,3,4,6-tetramethyl-2-thioxopyrimidinium bisulphate, 1,2-dihydro-1,3-dipropyl-4,6-dimethyl-2-thioxopyrimidinium bisulphate, 1,2-dihydro-1,3, 4-trimethyl-2-thioxopyrimidinium chloride, 1,2-dihydro-1,3,4-trimethyl-2-thioxopyrimidinium hydrogensulfate, 1,2-dihydro-1,3-diethyl-4-methyl-2-thioxopyrimidinium chloride, 1 , 2-Dihydro-1,3-diethyl-4-methyl-2-thioxopyrimidinium Hydro gensulfat, 1,2-dihydro-1,3-dipropyl-4-methyl-2-thioxopyrimidinium chloride and 1,2-dihydro-1,3-dipropyl-4-methyl-2-thioxopyrimidinium hydrogen sulfate.

Of Furthermore, as component (Oxo2b) at least one oxidation dye precursor with at least one primary or secondary Amino group and / or at least one hydroxy group can be used. Preferred suitable representatives can be found under the execution the oxidation dye precursors. However, it is preferred according to the invention when the compounds of the component (Oxo2) only under C, H-acidic Connections are selected.

The above-mentioned compounds of the component (Oxo1) and of the component (Oxo2), if they are used, respectively preferably in an amount of 0.001 to 10 wt .-%, in particular from 0.01 to 5 wt .-%, each based on the total weight of the ready for use Means, used.

When Dye precursors of naturally-analogous dyes are preferably those Indoles and indolines were used, which selected at least two groups from hydroxy and / or or amino groups, preferably as a substituent at the six-ring, exhibit. These groups may have additional substituents wear, z. B. in the form of etherification or esterification of the hydroxy group or an alkylation of the amino group. In a further embodiment the colorants contain at least one indole and / or Indoline. Compositions according to the invention, contain the precursors of natural dyes, are preferred used as air-oxidative coloring agents. In this embodiment Therefore, the said compositions will not be associated with an additional Oxidizing agent added.

The Dye precursors of naturally-analogous dyes are preferred in each case in an amount of 0.001 to 5 wt .-%, based on the total application preparation, used.

Especially Suitable as precursors of natural-analogous hair dyes are derivatives of 5,6-dihydroxyindoline, in particular 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline and 5,6-dihydroxyindoline-2-carboxylic acid.

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

When Precursors of natural-analogous hair dyes are outstandingly suitable furthermore derivatives of 5,6-dihydroxyindole, in particular 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole, 5,6-dihydroxyindole-2-carboxylic acid.

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

In a preferred embodiment of the present invention contains the agent for coloring keratinous fibers additionally a plant extract.

Plant extracts are usually prepared by extraction of the entire plant, but in some cases also exclusively from flowers and / or leaves and / or seeds and / or other parts of plants. According to the invention, especially the extracts from the meristem, so the divisible educated tissue of the plants, and special plants such as green tea, witch hazel, chamomile, marigold, pansy, Paeonie, aloe vera, horse chestnut, sage, willow bark, cinnamon tree (cinnamon tree), chrysanthemums , Oak bark, Nettle, Hops, Burdock root, Horsetail, Hawthorn, Lime blossom, Almonds, Spruce needles, Sandalwood, Juniper, Coconut, Kiwi, Guava, Lime, Mango, Apricot, Wheat, Melon, Orange, Grapefruit, avocado, rosemary, birch, beech sprouts, mallow, meadowfoam, yarrow, quenelle, thyme, lemon balm, toadstool, marshmallow (Althaea), mallow (Malva sylvestris), violets, blackcurrant leaves, coltsfoot, finned cabbage, ginseng, ginger root and Sweet potato preferred. Algae extracts can also be used to advantage. The algae extracts used according to the invention are derived from green algae, brown algae, red algae or blue-green algae (cyanobacteria). The algae used for extraction can be obtained both from natural sources as well as by biotechnological processes and, if desired, be modified from the natural form. The alteration of the organisms may be by genetic engineering, by breeding or by cultivation in media enriched with selected nutrients. Preferred algae extracts are from seaweed, blue-green algae, from the green alga Codium tomentosum and from the brown algae Fucus vesiculosus. A particularly preferred algae extract is derived from blue-green algae of the species Spirulina, which were cultured in a magnesium-enriched medium.

Especially preferred are the extracts of spirulina, green tea, Aloe Vera, Meristem, Hamamelis, Apricot, Marigold, Guava, Sweet Potato, Lime, mango, kiwi, cucumber, mallow, marshmallow and violet. The invention Means may also be mixtures of several, in particular from two different plant extracts included.

When Extraction agent for the preparation of said plant extracts can u. a. Water, alcohols and mixtures used become. Among the alcohols are lower alcohols such as ethanol and isopropanol, but especially polyhydric alcohols such as ethylene glycol, Propylene glycol and butylene glycol, both as sole Extracting agent as well as in admixture with water, preferred. Plant extracts on Base of water / propylene glycol in the ratio 1:10 to 10: 1 have proven to be particularly suitable. The steam distillation falls according to the invention among the preferred Extraction process.

The plant extracts can be used according to the invention both in pure and in diluted form. If they are used in dilute form, they usually contain about 2 to 80 wt .-% of active substance and as a solvent used in their extraction agent or extractant mixture. Depending on the choice of extractants, it may be preferable to stabilize the plant extract by adding a solubilizer. Suitable solubilizers are, for. B. Ethoxylation products of optionally hydrogenated vegetable and animal oils. Preferred solubilizers are ethoxylated mono-, di- and triglycerides of C _8-22 fatty acids having from 4 to 50 ethylene oxide units, e.g. Hydrogenated ethoxylated castor oil, olive oil ethoxylate, almond oil ethoxylate, mink oil ethoxylate, polyoxyethylene glycol caprylic / capric acid glycerides, polyoxyethylene glycerol monolaurate, and polyoxyethylene glycol coconut fatty acid glycerides.

preferred Plant extracts are, for example, extracts of flowers (Lime blossom, camomile, lily, lavender, roses, jasmine, Neroli, ylang-ylang), stems and leaves (aloe, Cassis, Horse Chestnut, Rooibos, Birch, Melissa, Clover, Grape Leaves, Geranium, patchouli, petitgrain), fruits (anise, cassis, Coriander, caraway, juniper), fruit peel (bergamot, Lemon, oranges, litchi), roots (macis, angelica, celery, cardamom, Costus, Iris, Calmus), Woods (Pine, Sandal, Guajac, Cedar, rosewood), herbs and grasses (tarragon, Lemongrass, sage, thyme, rosemary), needles and twigs (spruce, Fir, pine, pines, sandalwood), resins and balms (galbanum, Elemi, Benzoe, Myrrh, Olibanum, Opoponax).

Especially Preferably, the plant extracts are selected from at least an extract from the group aloe (aloe barbadensis), witch hazel (Hamamelis virginiana L.), vine leaves (Vitis vinifera L.), Roses (Rosa gallica L.), Sandalwood (Pterocarpus Santalinus), Rooibos (Aspalathus linearis), horse chestnut (Aesculus Hippocastanum L.), clover (especially red clover, Trifolium pratense), cinnamon (Cinnamomum zeylanicum nees) and cassis (especially from cassis leaves, Ribes nigrum L.).

Such Preferred extracts are used under the names Herbasol marketed by the company Cosmetochem or Extrapon by the company Symrise.

In a particularly preferred embodiment of the present invention Invention contains the agent for coloring keratinischer Fibers as an additional plant extract an extract Aloe Barbadensis.

In principle, according to the invention, all naturally occurring plants belonging to the genus Aloe can be used. The literature currently describes over 300 different plant species. Preferred species include aloe mutabilis, aloe melanocantha, aloe manchii, aloe pearsonii, aloe comptonii, aloe mitriformis, aloe distans, aloe arenicola, aloe volkensii, aloe petrophylla, aloe ferox, aloe africana, aloe globiligemma, aloe perry, aloe viscensii, aloe vera, aloe lettyae, aloe capensis, aloe barbadensis, aloe socetriis, aloe curacao, aloe candelabrum, aloe excelsa, aloe cameronii, aloe sessiliflora, aloe reitzii, Aloe aculeate, aloe marlothii, aloe utyhei sensis, aloe dolomitica, aloe castanea, aloe vanlabemii, aloe alooides, aloe gerstueri and aloe petricola.

Particularly according to the invention preferred are preparations made from aloe capensis or aloe barbadensis be won. Very particular according to the invention preferred are preparations made from aloe barbadensis, the so-called Real aloe or even aloe vera, to be won.

Either the leaves as well as the flowers and seeds of the Aloe plants can be used as the basis for this preparation serve. Particularly preferred according to the invention Preparations have been made from the leaves the aloe plants are obtained.

Also in terms of the way in which the invention Preparation is derived from the plant constituents consist in principle no restrictions. So, for example the gel contained in the plants used directly in the mold in which it occurs in violation of aloe leaves.

It but can also be used preparations that by means of mechanical and / or chemical techniques derived from the plant become. For this purpose, the plant components in an optional first step are mechanically crushed. As examples of mechanical comminuting methods is for example cutting, Purée and crushing called.

in the second essential step, the preparations can then in a first embodiment by means of mechanical separation methods be extracted from the plant components that are based on the exploitation of mechanical forces, such as gravity, centrifugal force, Pressure or vacuum. These include, for example Decanting, filtration, sedimentation, ultrafiltration and centrifugation.

In another embodiment of the present invention preparations are used which, by means of chemical separation methods, for example, an extraction or a chromatographic process, be obtained from the plant components. In the context of this Embodiment extracts are particularly preferred. When Extraction agent for the preparation of said plant extracts may be used water, alcohols and mixtures thereof become. Among the alcohols are lower alcohols such as ethanol and isopropanol, but especially polyhydric alcohols such as ethylene glycol and propylene glycol, both as the sole extractant also in mixture with water, preferred. Based on water-propylene glycol mixtures recovered plant extracts have proven to be particularly suitable. It has proven to be particularly suitable if these extraction agents in a ratio of 1:10 to 10: 1 are used.

The Effectiveness of an extract of aloe can be immediate attributed to its characteristic composition of ingredients. This composition may be in parts by weight and ingredients depending on the type of aloe, according to growth conditions, after used Part of the plant and its production process. An effective extract includes, in addition to water, an optional one organic solvent used in the extraction, Vitamins and vitamin precursors, essential oils, Minerals and trace elements in particular characteristic Active ingredients of aloe.

Among these characteristic active ingredients are in particular mono- and polysaccharides, as the main constituent aloein (barbaloin) and also in a lesser amount of emodin (1,3,8-trihydroxy-6-methylanthraquinone), aloe-emodin (1,8-dihydroxy-) 3- (hydroxymethyl) anthraquinone) and its glycosidic derivatives (so-called Glyco-Aloeemodine-Anthorne), nataloine, homonataloine, isobarbaloin, aloesin and thereof derived by glycosidic linkages Aloeinoside (A and B), chrysophanol (1,8-dihydroxy-3 -methyl-anthraquinone) and special resins. A compilation of the most important aloe ingredients is for example in Current Organic Chemistry 2000, 4 (10), pp. 1055-1078 (24) by E. Dagne et al. to find.

Aloein A (1,8-Dihydroxy-3-hydroxymethyl-10-(β)-D-(glucopyranosyl)anthron).The main constituent of the characteristic active ingredients of an aloe extract is aloe (also aloin, aloe A or barbaloin) is an anthraquinone glycoside having the following structure:

Aloein A (1,8-dihydroxy-3-hydroxymethyl-10- (β) -D- (glucopyranosyl) anthrone).

When Monosaccharides are usually arabinose, galactose, glucose, Mannose and xylose in the extract, as polysaccharide ingredients at least one glucomannan, and of further importance are β-linked Mannose polymers such as acemannan (β-1,4-acetylated mannan).

According to the invention preferred effective extracts of aloe vera therefore contain at least aloe.

Particularly according to the invention preferred extracts of aloe vera can be obtained by extraction from stems and / or leaves of aloe barbadensis with a mixture obtained from water and propylene glycol as extractant.

Farther it may be preferred according to the invention, extracts use that at least partially decolorized before use were. This can be done for example by using activated carbon.

The Plant extracts are in the invention Agent preferably in an amount of 0.0005 to 5 wt .-%, in particular 0.001 to 2 wt .-%, each based on the weight of the total By means of, included.

In a further preferred embodiment the means for dyeing keratinous fibers in addition at least one protein derivative as the active ingredient selected is from amino acids, oligopeptides or protein hydrolysates.

Under The term "protein derivative" are in the sense the invention as the active ingredient amino acids themselves and their over peptical bonds linked oligo- and polymers, in particular To understand oligopeptides and protein hydrolysates. As an amino acid For the purposes of the invention, an organic compound which is in its structure at least one protonatable amino group and at least one carboxylic acid or a sulfonic acid group. preferred Amino acids are aminocarboxylic acids, in particular α-aminocarboxylic acids and ω-aminocarboxylic acids, wherein α-aminocarboxylic acids are preferred.

Amino acids, Oligopeptides and protein hydrolysates usually contain in their structure asymmetric centers, in particular carbon atoms as chiral centers. In the context of the present invention, amino acids, Oligopeptides and / or protein hydrolysates as chiral substances or also as enantiomer and / or diastereomer mixtures. In particular, racemic mixtures, ie mixtures in which both Enantiomers of a compound are contained in equal proportions, may be preferred. In nature usually prevails an enantiomeric form. It may therefore also be preferred to use amino acids, Oligopeptides and / or protein hydrolysates in their natural state occurring or even just in their unnatural configuration use.

oligopeptides are either from natural sources or through targeted Synthesis available. The person skilled in the art knows these methods and will know how to select the appropriate one as needed. Preferred oligopeptides are dimers, trimers and tetramers of amino acids, preferably α-aminocarboxylic acids. Especially preferred Oligopeptides are the dimers of serine (Ser-Ser), in particular of L-serine, and threonine and serine (Thr-Ser and / or Ser-Thr).

According to the invention Protein hydrolysates of both vegetable and animal origin be used. The proteins are produced by hydrolysis of peptic Bindings broken down into low molecular weight fractions. It can Both alkaline, acidic or enzymatic hydrolysis methods used which provide structurally different hydrolysates and be used depending on the requirements of the hydrolysates. The expert these methods are common.

animal Protein hydrolysates are, for example, elastin, collagen, keratin, Silk and milk protein protein hydrolysates, which are also available in Form of salts may be present. Such products will be for example, under the trademarks Keratin DEC (Vincience), Dehylan (Cognis), Promois (Interorgana), Collapuron (Cognis), Nutrilan (Cognis), Gelita-Sol (German Gelatine factories Stoess & Co), Lexein (Inolex) and Kerasol (Croda) distributed.

According to the invention preferred is the use of protein hydrolysates of plant origin, z. Soybean, almond, rice, pea, potato and wheat protein hydrolysates. Such products are, for example, under the trademark Gluadin (Cognis), Diahin (Diamalt), Lexein (Inolex) and Crotein (Croda) available.

Also possible is the use of derivatives of protein hydrolysates, for example in the form of their fatty acid condensation products. Such products are for example under the names Lamepon (Cognis), Gluadin (Cognis), Lexein (Inolex), Crolastin (Croda) or Crotein (Croda) distributed.

ever after preparation or recovery process can oligopeptides and protein hydrolysates as mixtures of different components with different numbers of peptic bonds, different Amino acid sequences and different molecular weights occur and in the inventive compositions be used.

It may be advantageous according to the invention, mixtures of amino acids, oligopeptides and / or protein hydrolysates to use, either by manufacturing process as a mixture incurred or by specific combination of different protein derivatives, such as the combination of several amino acids, to be obtained. In a preferred embodiment of Invention amino acids are considered predominant Pure substances used.

The Amino acids, oligopeptides and / or protein hydrolysates can the agents according to the invention preferably in free Form are added. In a number of cases it is but also advantageous, in particular the amino acids in Use salt form. Preferred salts are then the compounds with hydrohalic acids or sulfuric acid, in particular the hydrochlorides, the hydrobromides and the sulfates.

Particularly according to the invention advantageous color-modifying agents are included as additional Active ingredient at least one amino acid selected is made up of L-serine, D-serine, D / L-serine (racemate), L-homoserine, D-homoserine, D / L homoserine, L-threonine, D-threonine, D / L-threonine, 4-hydroxy-proline, 5-hydroxy-lysine, L-arginine, D-arginine, D / L-arginine, L-lysine, D-lysine, D / L-lysine, L-ornithine, D-ornithine, D / L-ornithine, L-histidine, D-histidine and D / L-histidine and / or one of its physiologically acceptable Salts. Very particularly preferred according to the invention is L-serine, especially in free form, but also as hydrochloride used.

A particularly preferred embodiment of the present invention is characterized in that the means for coloring keratinic fibers contains L-serine.

Of the additional active ingredient selected from at least an amino acid, an oligopeptide or a protein hydrolyzate, is preferred in the agents according to the invention in amounts of from 0.01 to 10% by weight, in particular from 0.05 to 5% by weight, based on the total weight of the application mixture.

After all it has been found that in particular the addition of cocoa butter in combination with an additional care substance selected from cationized phosphate esters, in coloring agents keratinic fibers a particularly advantageous care effect generated.

A another preferred embodiment of the present invention is therefore characterized in that the agent additionally a conditioner selected from cationized phosphate esters, contains.

worin
y für eine ganze Zahl von 0 bis 2 steht und
x für eine ganze Zahl von 1 bis 3 steht,
mit der Maßgabe, dass die Summe aus x und y gleich 3 ist.A cationized phosphate ester in the context of the present invention is understood as meaning a surfactant of the formula (I)

wherein
y is an integer from 0 to 2 and
x is an integer from 1 to 3,
with the proviso that the sum of x and y is equal to 3.

In the surfactants to be used according to the invention also M is hydrogen, one equivalent of an alkali metal or alkaline earth metal cations, an ammonium cation or an alkyl radical having 1 to 4 carbon atoms, optionally with one or a plurality of hydroxy group (s) is substituted. Especially preferred are compounds in which M stands for a sodium cation.

Farther B in the formula (I) is the invention to be used Surfactants for one equivalent of a physiological compatible anion. As anion z. Chloride, Bromide, iodide, sulfate, perchlorate, tetrafluoroborate, tetraphenylborate and tetrachlorozincate. Preference is given to chloride.

worin
z für eine ganze Zahl von 1 bis 4, insbesondere für 3, steht,
R1 und R2 unabhängig voneinander für einen C₁-C₄-Alkylrest stehen, der gegebenenfalls mit einer oder mehreren Hydroxygruppe(n) oder einer Acylgruppe substituiert ist, und
A für eine der Einheiten -OCH₂CH₂CH₂-, -OCH₂CH₂- oder -OCH₂CH(OH)CH₂- steht, wobei die Einheit -OCH₂CH(OH)CH₂- erfindungsgemäß besonders bevorzugt ist.R in the surfactants of the formula (I) according to the invention is a radical of the formula (II)

wherein
z is an integer from 1 to 4, in particular 3,
R _{1 and} R 2 independently of one another are a C ₁ -C ₄ -alkyl radical which is optionally substituted by one or more hydroxy group (s) or an acyl group, and
A is one of the moieties -OCH ₂ CH ₂ CH ₂ -, -OCH ₂ CH ₂ - or -OCH ₂ CH (OH) CH ₂ -, wherein the moiety -OCH ₂ CH (OH) CH ₂ - is particularly preferred according to the invention ,

• (a) einen verzweigten oder unverzweigten, gesättigten C₈-C₁₈-Acylrest oder
• (b) einen verzweigten oder unverzweigten, einfach oder mehrfach ungesättigten C₈-C₁₈-Acylrest.

The rest R3 stands for

• (a) a branched or unbranched, saturated C ₈ -C ₁₈ acyl radical or
• (B) a branched or unbranched, mono- or polyunsaturated C ₈ -C ₁₈ acyl radical.

Especially Preferred saturated radicals R3 are derived from the acyl radical the stearic acid as well as the acyl radicals of the mixture of coconut fatty acids. A particularly preferred unsaturated Acyl residue R3 is derived from linoleic acid.

It It has been found that compounds of the formula (I) in which R3 is the acyl residue of linoleic acid, through a higher Label compatibility with the emulsifier system. This means that these substances are easier in the formulations work in. Furthermore, formulations with compounds of formula (I) wherein R3 is the remainder of linoleic acid stands, a significantly higher care effect in comparison to compounds with saturated fatty acid residues on.

Examples of the C ₁ - to C ₄ -alkyl groups mentioned as substituents in the compounds according to the invention are the groups methyl, ethyl, propyl, isopropyl and butyl. Ethyl and methyl groups are preferred alkyl groups. Very particular preference is given to methyl groups.

Compounds of the formula (I) are already known. So be in the EP-A1-13713 the surfactant properties of these compounds are generally described. Furthermore, from the DE-A1-44 08 506 the use of a compound of formula (I) in hair dyes already known. However, these references are not indicative of the synergistic increase in the care effect of the active compound combinations according to the invention.

All Particularly preferred cationized phosphate esters of the formula (I) are those under the INCI names Linoleamidopropyl PG-Dimonium Chloride Phosphate, Cocamidopropyl PG-Dimonium Chloride Phosphate and Stearamidopropyl PG-Dimonium Chloride Phosphate known substances. These are for example from the company Mona under the trade names Phospholipid EFA, phospholipid PTC and phospholipid SV.

According to the invention the compounds of the formula (I) in amounts of from 0.01 to 5% by weight, especially in amounts of 0.05 to 2 wt .-%, each based on the entire remedy, used in the claimed means.

worin
die Reste R1, R2, R3 und R4 unabhängig voneinander für ein Wasserstoffatom, eine C₁-C₄-Alkylgruppe, eine C₂-C₆-Alkenylgruppe oder eine C₂-C₆-Hydroxyalkylgruppe mit mindestens einer Hydroxygruppe steht,
mit der Maßgabe, dass mindestens einer der besagten Reste eine C₂-C₆Hydroxyalkylgruppe mit mindestens einer Hydroxygruppe bedeutet.In a further, preferred embodiment of the present invention, the agents according to the invention additionally comprise at least one urea derivative. According to the invention, the urea derivative is selected from compounds according to formula (I),

wherein
R _1, R _2, R 3 and R ₄ independently of one another represent a hydrogen atom, a C ₁ -C ₄ -alkyl group, a C ₂ -C ₆ -alkenyl group or a C ₂ -C ₆ -hydroxyalkyl group having at least one hydroxyl group,
with the proviso that at least one of said radicals is a C ₂ -C ₆ hydroxyalkyl group having at least one hydroxy group.

Preferred urea derivatives of the formula (I) which are suitable are those which contain at least one C ₂ -C ₆ -hydroxyalkyl group having at least one hydroxyl group which consists of at least one member selected from the group consisting of 2-hydroxyethyl, 2-hydroxy-2-methylprop-2 -yl, 1,3-dihydroxy-2-methylprop-2-yl, 1,3-dihydroxyprop-2-yl, tris (hydroxymethyl) methyl, 1,3-dihydroxy-2-hydroxymethylprop-2-yl, 2.3 Dihydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 4-hydroxybutyl, 1-hydroxy-2-methylprop-2-yl, 2,3,4,5,6-pentahydroxyhexyl and 1,3,4,5,6-pentahydroxyhex -2-yl is selected.

It is preferred according to the invention to use those urea derivatives of the formula (I) which satisfy the preferred proviso of the formula (I) in that at least one of the radicals R _{1 to} R ₄ denotes a C ₂ -C ₆ -hydroxyalkyl group having at least one hydroxyl group. With particular preference, in each case two radicals of R _1, R _2, R _{3 and} R _{4 represent} a C ₂ -C ₆ -hydroxyalkyl group having at least one hydroxyl group. Particularly preferably, the two radicals of R _1, R _2, R _{3 and} R _{4 are} a C ₂ -C ₆ -hydroxyalkyl group having at least one hydroxyl group, these two radicals being positioned at different nitrogen atoms of the urea (N, N 'position).

Examples of C ₁ -C ₄ -alkyl groups which can be used according to the invention in compounds of the formula (I) are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl.

Examples of C ₂ -C ₆ -alkenyl groups which can be used according to the invention in compounds of the formula (I) are vinyl, 2-propen-1-yl (allyl) or 3-buten-1-yl.

Particular preference is given to at least one compound from the group comprising the representatives N- (2-hydroxyethyl) urea, N, N-bis (2-hydroxyethyl) urea, N, N'-bis (2-hydroxyethyl) urea, N- (3-hydroxypropyl) urea, N, N-bis (3-hydroxypropyl) urea, N, N'-bis (3-hydroxypropyl) urea, N- (2-hydroxypropyl) urea, N, N-bis ( 2-hydroxypropylurea, N, N'-bis (2-hydroxypropyl) urea, N- (2-hydroxy-2-methyl-prop-2-yl) urea, N, N-bis- (2-hydroxy-2-) methyl-prop-2-yl) urea, N, N'-bis (2-hydroxy-2-methyl-prop-2-yl) urea, N- (1,3-dihydroxy-2-methyl-prop-2 -yl) urea, N, N-bis (1,3-dihydroxy-2-methyl-prop-2-yl) urea, N, N'-bis (1,3-dihydroxy-2-methyl-propyl) 2-yl) urea, N- (1,3-dihydroxy-2-hydroxymethyl-prop-2-yl) urea, N, N-bis- (1,3-dihydroxy-2-hydroxymethyl-prop-2-yl) urea and N, N'-bis- (1,3-dihydroxy-2-hydroxymethylprop-2-yl) urea, very particularly preferably N- (2-hydroxyethyl) urea and N, N'-bis (2-hydroxy) hydroxyethyl) urea, available, for example as a commercial product Hydro Vance ^® by National Starch.

According to the invention preferred Means are characterized in that the agent is the urea derivative in an amount of 0.01 to 10% by weight, preferably 0.05 to 8 wt .-% and in particular from 0.1 to 5 wt .-%, each based on the total weight of the ready-to-use agent.

in the Case of oxidative staining, the development of the Color should always be done with atmospheric oxygen. Prefers However, a chemical oxidizing agent is used, especially when, in addition to the coloring, a whitening effect on human Hair is desired. This whitening effect can be independent be desired from the staining method. As oxidizing agent come persulfates, peroxodisulfates, chlorites, hypochlorites and in particular Hydrogen peroxide or and / or one of its solid addition products to organic or inorganic compounds in question.

To a premature, unwanted reaction of the oxidation dye precursors by the oxidation To prevent medium, oxidation dye precursors and oxidizing agents themselves are expediently made up separately and brought into contact only immediately before use.

In another embodiment of the present invention Therefore, agents are preferred which are characterized that they are mixed immediately before use by mixing at least two preparations is produced, wherein the at least two Preparations in at least two separate prefabricated containers and wherein a container (I) is a dyeing preparation (A), which in a cosmetic carrier at least one Contains oxidation dye precursor, and another Container (II) an oxidizing agent preparation (B) containing at least one oxidizing agent, wherein at least a preparation (A) and / or (B) contains cocoa butter.

According to the invention preferred contains the dye preparation (A) as another Ingredient Cocoa butter.

Prefers Contains the oxidizing agent preparation (B) as an oxidizing agent Hydrogen peroxide and / or one of its solid addition products to organic or inorganic compounds, such as urea, melamine and sodium borate.

The amount of oxidizing agent in the ready-to-use agent is preferably from 0.5 to 12% by weight, preferably from 2 to 10% by weight, more preferably from 3 to 6% by weight (calculated as 100% H ₂ O ₂ ), in each case based on the ready-to-use means.

Such Oxidizing agent preparations are preferably aqueous, flowable oxidizing agent preparations. there preferred formulations are characterized in that the flowable Oxidizing agent preparation - based on its weight - 40 to 95% by weight, preferably 50 to 90% by weight, more preferably 55 to 85 wt .-%, more preferably 60 to 80 wt .-% and in particular 65 to 75 wt .-% water.

According to the invention but also the oxidation dye along with one Catalyst can be applied to the hair, the oxidation of the Dye precursors, eg. B. by atmospheric oxygen activated. Such Catalysts are z. As certain enzymes, iodides, quinones or Metal ions.

• – Pyranose-Oxidase und z. B. D-Glucose oder Galactose,
• – Glucose-Oxidase und D-Glucose,
• – Glycerin-Oxidase und Glycerin,
• – Pyruvat-Oxidase und Benztraubensäure oder deren Salze,
• – Alkohol-Oxidase und Alkohol (MeOH, EtOH),
• – Lactat-Oxidase und Milchsäure und deren Salze,
• – Tyrosinase-Oxidase und Tyrosin,
• – Uricase und Harnsäure oder deren Salze,
• – Cholinoxidase und Cholin,
• – Aminosäure-Oxidase und Aminosäuren.

Suitable enzymes are z. As peroxidases, which can significantly increase the effect of small amounts of hydrogen peroxide. Furthermore, such enzymes are suitable according to the invention which directly oxidize the oxidation dye precursors with the aid of atmospheric oxygen, such as, for example, the laccases, or generate small amounts of hydrogen peroxide in situ and thus biocatalytically activate the oxidation of the dye precursors. Particularly suitable catalysts for the oxidation of the dye precursors are the so-called 2-electron oxidoreductases in combination with the specific substrates, for. B.

• - pyranose oxidase and z. D-glucose or galactose,
• Glucose oxidase and D-glucose,
• - glycerol oxidase and glycerin,
• Pyruvate oxidase and pyruvic acid or its salts,
• Alcohol oxidase and alcohol (MeOH, EtOH),
• Lactate oxidase and lactic acid and their salts,
• Tyrosinase oxidase and tyrosine,
• Uricase and uric acid or their salts,
• - choline oxidase and choline,
• - amino acid oxidase and amino acids.

Use of certain metal ions or complexes may also be preferred to obtain intense, long-lasting colorations. Suitable metal ions are, for example, Zn ²⁺ , Cu ²⁺ , Fe ²⁺ , Fe ³⁺ , Mn ²⁺ , Mn ⁴⁺ , Li ⁺ , Mg ²⁺ , Ca ²⁺ , Ce ⁴⁺ , V ³⁺ , Co ²⁺ , Ru ³⁺ and Al ³⁺ . Particularly suitable are Zn ²⁺ , Cu ²⁺ and Mn ²⁺ . The metal ions can in principle be used in the form of any physiologically acceptable salt or in the form of a complex compound. Preferred salts are the acetates, sulfates, halides, lactates, citrates and tartrates. By using these metal salts, both the formation of the dyeing can be accelerated and the color shade can be specifically influenced. Particularly preferred agents contain these metal ions to 0.0001 to 2.5 wt .-%, preferably 0.001 to 1 wt .-%, based on the total weight of the composition according to the invention.

Furthermore, it has proven to be advantageous if the oxidizing agent preparations contain at least one stabilizer or complexing agent. Particularly preferred stabilizers are phenacetin, alkali benzoate (sodium benzoate) and salicylic acid.

According to the invention preferred is also the use of so-called complexing agents. Complex images are Substances that can complex metal ions. preferred Complexing agents are so-called chelate complexing agents, ie substances, which form cyclic compounds with metal ions, wherein a single Ligand occupies more than one coordination site on a central atom, d. H. at least "bidentate". The Number of bound ligands depends on the coordination number of the central ion.

• a) Polycarbonsäuren, bei denen die Summe der Carboxyl- und gegebenenfalls Hydroxylgruppen mindestens 5 beträgt wie Gluconsäure,
• b) stickstoffhaltige Mono- oder Polycarbonsäuren wie Ethylendiamintetraessigsäure (EDTA), N-Hydroxyethylethylendiamintriessigsäure, Diethylentriaminpentaessigsäure (DTPA), Ethylendiamindibernsteinsäure (EDDS), Hydroxyethyliminodiessigsäure, Nitridodiessigsäure-3-propionsäure, Isoserindiessigsäure, N,N-Di-(2-hydroxyethyl)glycin, N-(1,2-Dicarboxy-2-hydroxyethyl)glycin, N-(1,2-Dicarboxy-2-hydroxyethyl)asparaginsäure oder Nitrilotriessigsäure (NTA), Ethylendiamindiglutarsäure (EDGA), 2-Hydroxypropylendiamindibernsteinsäure (HPDS), Glycinamid-N,N'-dibernsteinsäure (GADS), Ethylendiamin-N-N'-diglutarsäure (EDDG), 2-Hydroxypropylendiamin-N-N'-dibernsteinsäure (HPDDS), Diaminoalkyldi(sulfobernsteinsäure) (DOS), Ethylendicysteinsäure (EDC), Ethylendiamin-N-N'-bis(orthohydroxyphenyl)essigsäure (EDDHA), N-2-Hydroxyethylamin-N,N-diessigsäure, Glyceryliminodiessigsäure, Iminodiessigsäure-N-2-hydroxypropylsulfonsäure, Asparaginsäure-N-carboxymethyl-N-2,5-hydroxypropyl-3-sulfonsäure,β-Alanin-N,N'-diessigsäure, Asparaginsäure-N,N'-diessigsäure, Asparaginsäure-N-monoessigsäure, Dipicolinsäure, sowie deren Salze und/oder Derivate
• c) geminale Diphosphonsäuren wie 1-Hydroxyethan-1,1-diphosphonsäure (HEDP), deren höhere Homologe mit bis zu 8 Kohlenstoffatomen sowie Hydroxy- oder Aminogruppenhaltige Derivate hiervon und 1-Aminoethan-1,1-diphosphonsäure, deren höhere Homologe mit bis zu 8 Kohlenstoffatomen sowie Hydroxy- oder Aminogruppen-haltige Derivate
• d) Aminophosphonsäuren wie Ethylendiamintetra(methylenphosphonsäure) (EDTMP), Diethylen-triaminpenta(methylenphosphonsäure) (DTPMP) sowie deren höhere Homologe, oder Nitrilotri(methylenphosphonsäure),
• e) Phosphonopolycarbonsäuren wie 2-Phosphonobutan-1,2,4-tricarbonsäure,
• f) Cyclodextrine, sowie
• g) Alkalistannate (Natriumstannat), Alkalipyrophosphate (Tetranatriumpyrophosphat, Dinatriumpyrophosphat), Alkaliphosphate (Natriumphosphat), und Phosphorsäure.

In the context of the present invention, all complexing agents of the prior art can be used. These can belong to different chemical groups. Preferably, used individually or in admixture with each other:

• a) polycarboxylic acids in which the sum of the carboxyl and optionally hydroxyl groups is at least 5, such as gluconic acid,
• b) nitrogen-containing mono- or polycarboxylic acids such as ethylenediaminetetraacetic acid (EDTA), N-hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid (DTPA), ethylenediamine disuccinic acid (EDDS), hydroxyethyliminodiacetic acid, nitridodiacetic acid-3-propionic acid, isoserinediacetic acid, N, N-di (2-hydroxyethyl) glycine, N- (1,2-dicarboxy-2-hydroxyethyl) glycine, N- (1,2-dicarboxy-2-hydroxyethyl) aspartic acid or nitrilotriacetic acid (NTA), ethylenediaminediglutaric acid (EDGA), 2-hydroxypropylenediamine disuccinic acid (HPDS), glycinamide-N , N'-disuccinic acid (GADS), ethylenediamine-N-N'-diglutaric acid (EDDG), 2-hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS), diaminoalkyldi (sulfosuccinic acid) (DOS), ethylenedicysteic acid (EDC), ethylenediamine N-N'-bis (orthohydroxyphenyl) acetic acid (EDDHA), N-2-hydroxyethylamine-N, N-diacetic acid, glyceryliminodiacetic acid, iminodiacetic acid N-2-hydroxypropylsulfonic acid, aspartic acid-N-carboxymethyl-N-2,5-hydroxypropyl- 3-sulfo acid, β-alanine-N, N'-diacetic acid, aspartic acid-N, N'-diacetic acid, aspartic acid-N-monoacetic acid, dipicolinic acid, and their salts and / or derivatives
• c) geminal diphosphonic acids such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP), their higher homologues having up to 8 carbon atoms and hydroxy- or amino-containing derivatives thereof and 1-aminoethane-1,1-diphosphonic acid, their higher homologues with up to 8 carbon atoms and hydroxy- or amino-containing derivatives
• d) aminophosphonic acids such as ethylenediaminetetra (methylenephosphonic acid) (EDTMP), diethylenetriaminepenta (methylenephosphonic acid) (DTPMP) and their higher homologs, or nitrilotri (methylenephosphonic acid),
• e) phosphonopolycarboxylic acids such as 2-phosphonobutane-1,2,4-tricarboxylic acid,
• f) cyclodextrins, as well
• g) alkali stannates (sodium stannate), alkali pyrophosphates (tetrasodium pyrophosphate, disodium pyrophosphate), alkali phosphates (sodium phosphate), and phosphoric acid.

at the alkaline required according to the invention pH values of the treatment solutions are these complexing agents at least partially as anions. It does not matter if they are introduced in the form of acids or in the form of salts become. In the case of use as salts, alkali metal, ammonium or alkylammonium salts, especially sodium salts.

According to the invention preferred Complexing agents are nitrogen-containing polycarboxylic acids, especially EDTA, and phosphonates, preferably hydroxyalkane or Aminoalkane phosphonates and in particular 1-hydroxyethane-1,1-diphosphonate (HEDP) or its di- or tetrasodium salt and / or ethylenediamine tetramethylenephosphonate (EDTMP) or its hexasodium salt and / or Diethylentriaminpentamethylenphosphonat (DTPMP) or its hepta- or octasodium salt.

The Dyeing preparation and optionally oxidizing agent preparation contain other auxiliaries and additives. So it has according to the invention as preferred when the dyeing preparation and / or the Oxidant preparation contains at least one thickener. With regard to these thickeners there are no principal Restrictions. It can be both organic and also purely inorganic thickening agents are used.

According to one The first preferred embodiment is the thickener is an anionic, synthetic polymer. Preferred anionic groups are the carboxylate and sulfonate groups.

Examples of anionic monomers from which the polymeric anionic thickeners may consist are acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic anhydride and 2-acryla mido-2-methyl propane sulfonic acid. The acidic groups may be wholly or partly present as sodium, potassium, ammonium, mono- or triethanolammonium salt. Preferred monomers are maleic anhydride and in particular 2-acrylamido-2-methylpropanesulfonic acid and acrylic acid.

preferred anionic homopolymers are uncrosslinked and crosslinked polyacrylic acids. Allyl ethers of pentaerythritol, of sucrose and propylene preferred crosslinking agents. Such compounds are commercially available, for example, under the trademark Carbopol. Also preferred is the homopolymer of 2-acrylamido-2-methylpropanesulfonic acid, for example, under the name Rheothik 11-80 is commercially available.

Within This first embodiment may further be preferred be, copolymers of at least one anionic monomer and at least to use a nonionic monomer. Regarding the anionic monomers is added to the substances listed above directed. Preferred nonionic monomers are acrylamide, methacrylamide, Acrylic acid esters, methacrylic esters, itaconic acid mono- and diesters, vinylpyrrolidinone, vinyl ethers and vinyl esters.

The anionic acrylic acid and / or methacrylic acid polymers or copolymers are in the inventive Preferably, in an amount of 0.1 to 10 wt .-%, especially preferably from 1 to 5 wt .-%, each based on the weight of By means of, included.

Preferred anionic copolymers are, for example, copolymers of acrylic acid, methacrylic acid or their C ₁ -C ₆ -alkyl esters, as sold under the INCI declaration Acrylates Copolymers. A preferred commercial product is, for example, Aculyn 33 from Rohm & Haas. However, preference is also given to copolymers of acrylic acid, methacrylic acid or their C ₁ -C ₆ -alkyl esters and the esters of an ethylenically unsaturated acid and an alkoxylated fatty alcohol. Suitable ethylenically unsaturated acids are, in particular, acrylic acid, methacrylic acid and itaconic acid; suitable alkoxylated fatty alcohols are in particular steareth-20 or ceteth-20. Such copolymers are sold by Rohm & Haas under the tradename Aculyn 22 and by National Starch under the tradenames Structure 2001 and Structure 3001.

Preferred anionic copolymers are also acrylic acid-acrylamide copolymers and in particular polyacrylamide copolymers with sulfonic acid-containing monomers. A particularly preferred anionic copolymer consists of 70 to 55 mol% of acrylamide and 30 to 45 mol% of 2-acrylamido-2-methylpropanesulfonic acid, wherein the sulfonic acid group is wholly or partly in the form of sodium, potassium, ammonium, mono- or triethanolammonium Salt is present. This copolymer can also be present in crosslinked form, with crosslinking agents preferably being polyolefinically unsaturated compounds such as tetraallyloxythane, allylsucrose, allylpentaerythritol and methylenebisacrylamide. Such a polymer is contained in the commercial products Seeigel 305 and Simulgel 600 from SEPPIC. The use of these compounds which, in addition to the polymer component, a hydrocarbon mixture (C ₁₃ -C ₁₄ isoparaffin or Isohexadecan) and a nonionic emulsifier (Laureth-7 or polysorbate-80), has proved to be particularly advantageous in the context of the teaching of the invention.

Also Polymers of maleic anhydride and methyl vinyl ether, especially those with crosslinks are preferred thickeners. A 1,9-decadiene crosslinked maleic acid-methyl vinyl ether copolymer is commercially available under the name Stabileze QM.

• – Polymerisate z. B. aus wenigstens 10 Gew.-% Acrylsäure-Niedrigalkylester, 25 bis 70 Gew.-% Methacrylsäure und ggf. bis zu 40 Gew.-% eines weiteren Comonomeren,
• – Mischpolymerisate aus 50 bis 75 Gew.-% Ethylacrylat, 25 bis 35 Gew.-% Acrylsäure und 0 bis 25 Gew.-% anderer Comonomeren bekannt. Geeignete Dispersionen dieser Art sind im Handel erhältlich, z. B. unter der Handelsbezeichnung Latekoll D (BASF).
• – Copolymerisate aus 50 bis 60 Gew.-% Ethylacrylat, 30 bis 40 Gew.-% Methacrylsäure und 5 bis 15 Gew.-% Acrylsäure, vernetzt mit Ethylenglycoldimethacrylat.

The agent according to the invention may additionally comprise at least one anionic acrylic acid and / or methacrylic acid polymer or copolymer. Preferred polymers of this type are:

• - Polymers z. From at least 10% by weight of acrylic acid lower alkyl ester, from 25 to 70% by weight of methacrylic acid and optionally up to 40% by weight of a further comonomer,
• - Copolymers of 50 to 75 wt .-% ethyl acrylate, 25 to 35 wt .-% acrylic acid and 0 to 25 wt .-% of other comonomers known. Suitable dispersions of this type are commercially available, for. B. under the trade name Latekoll D (BASF).
• Copolymers of 50 to 60% by weight of ethyl acrylate, 30 to 40% by weight of methacrylic acid and 5 to 15% by weight of acrylic acid, crosslinked with ethylene glycol dimethacrylate.

In another embodiment, the thickener is a cationic synthetic polymer. Preferred cationic groups are quaternary ammonium groups. In particular, those polymers in which the quaternary ammonium group is bonded via a C ₁ -C ₄ hydrocarbon group to a polymer main chain composed of acrylic acid, methacrylic acid or derivatives thereof, ha ben proved to be particularly suitable.

in der R1 = -H oder -CH₃ ist, R2, R3 und R4 unabhängig voneinander ausgewählt sind aus C₁-C₄-Alkyl-, -Alkenyl- oder -Hydroxyalkylgruppen, m = 1, 2, 3 oder 4, n eine natürliche Zahl und X^– ein physiologisch verträgliches organisches oder anorganisches Anion ist, sowie Copolymere, bestehend im wesentlichen aus den in Formel (HP-1) aufgeführten Monomereinheiten sowie nichtionogenen Monomereinheiten, sind besonders bevorzugte kationische polymere Gelbildner. Im Rahmen dieser Polymeren sind diejenigen erfindungsgemäß bevorzugt, für die mindestens eine der folgenden Bedingungen gilt:

• – R1 steht für eine Methylgruppe
• – R2, R3 und R4 stehen für Methylgruppen
• – m hat den Wert 2,

Homopolymers of the general formula (HP-1),

wherein R ₁ is -H or -CH ₃ , R 2, R 3 and R ₄ are independently selected from C ₁ -C ₄ -alkyl, -alkenyl or -hydroxyalkyl groups, m = 1, 2, 3 or 4, n is one natural number and X ^{- is} a physiologically acceptable organic or inorganic anion, as well as copolymers consisting essentially of the monomer units listed in formula (HP-1) and nonionic monomer units, are particularly preferred cationic polymeric gelling agents. In the context of these polymers, preference is given to those according to the invention for which at least one of the following conditions applies:

• R1 is a methyl group
• - R2, R3 and R4 stand for methyl groups
• - m has the value 2,

Suitable physiologically tolerated counterions X ^- include, for example, halide ions, sulfate ions, phosphate ions, methosulfate ions and organic ions such as lactate, citrate, tartrate and acetate ions. Preference is given to halide ions, in particular chloride.

One particularly suitable homopolymer is, if desired crosslinked, poly (methacryloxyethyltrimethylammonium chloride) with the INCI name Polyquaternium-37. The crosslinking can, if desired with the help of multiply olefinically unsaturated compounds, for example divinylbenzene, tetraallyloxyethane, methylenebisacrylamide, Diallyl ethers, polyallyl polyglyceryl ethers, or allyl ethers of sugars or sugar derivatives such as erythritol, pentaerythritol, arabitol, Mannitol, sorbitol, sucrose or glucose. methylenebisacrylamide is a preferred crosslinking agent.

The Homopolymer is preferably in the form of a non-aqueous Polymer dispersion having a polymer content of not less than 30% by weight should be used. Such polymer dispersions are under the terms Salcare SC 95 (about 50% polymer content, more Component: Mineral oil (INCI name: Mineral Oil) and Tridecyl polyoxypropylene polyoxyethylene ether (INCI name: PPG-1-trideceth-6)) and Salcare SC 96 (about 50% polymer content, more Components: mixture of diesters of propylene glycol with a Mixture of caprylic and capric acid (INCI name: Propylene glycol dicaprylate / dicaprate) and tridecyl polyoxypropylene polyoxyethylene ether (INCI name: PPG-1-Trideceth-6) commercially available.

Copolymers with monomer units of the formula (HP-1) contain as nonionic monomer units preferably acrylamide, methacrylamide, acrylic acid-C ₁ -C ₄ -alkyl esters and methacrylic acid-C ₁ -C ₄ -alkyl esters. Among these nonionic monomers, the acrylamide is particularly preferred. These copolymers can also be crosslinked, as described above for the homopolymers. A preferred copolymer according to the invention is the crosslinked acrylamide-methacryloxyethyltrimethylammonium chloride copolymer. Such copolymers in which the monomers are present in a weight ratio of about 20:80 are commercially available as an about 50% non-aqueous polymer dispersion under the name Salcare SC 92.

In a further preferred embodiment, naturally occurring thickeners are used. Preferred thickening agents of this embodiment are, for example, nonionic guar gum. According to the invention, both modified and unmodified guar gums can be used. Unmodified guar gums are sold, for example, under the trade name Jaguar C by Rhone Poulenc. Modified guar gums preferred according to the invention contain C ₁ -C ₆ -hydroxyalkyl groups. Preferably, the groups are hydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxybutyl. Such modified guar gums are known in the art and can be prepared, for example, by reaction of the guar gums with alkylene oxides. The degree of hydroxyalkylation, which corresponds to the number of alkylene oxide molecules consumed in relation to the number of guar gum free hydroxy groups, is preferably between 0.4 and 1.2. Such modified guar gums are commercially available under the trade names Jaguar HP8, Jaguar HP60, Jaguar HP120, Jaguar DC 293 and Jaguar HP105 from Rhone Poulenc.

Farther suitable natural thickeners are also already known from the prior art.

According to this Embodiment preferred are still Biosaccharidgums of microbial origin, such as the scleroglucangum or xanthan gum, Gums from plant exudates, such as gum arabic, Ghatti gum, karaya gum, gum tragacanth, carrageenan gum, agar agar, Locust bean gum, pectins, alginates, starch fractions and derivatives such as amylose, amylopectin and dextrins, cellulose derivatives, such as methylcellulose, carboxyalkylcelluloses and hydroxyalkylcelluloses.

preferred Hydroxyalkylcelluloses are in particular the hydroxyethylcelluloses, under the names Cellosize the company Amerchol and Natrosol the company Hercules are sold. Suitable carboxyalkylcelluloses In particular, the carboxymethylcelluloses, as they are among the Designations Blanose from Aqualon, Aquasorb and Ambergum sold by the company Hercules and Cellgon by the company Montello become.

Starch and its derivatives are also preferred. Starch is a storage material of plants, which occurs mainly in tubers and roots, in grain seeds and in fruits and can be obtained from a variety of plants in high yield. The polysaccharide which is insoluble in cold water and forms a colloidal solution in boiling water may be, for example, potatoes, cassava, maranta, maize, cereals, rice, legumes such as peas and beans, bananas or the pulp of certain types of palms (e.g. the sago palm). Natural, plant-derived starches and / or chemically or physically modified starches can be used according to the invention. Modification can be achieved, for example, by introducing different functional groups on one or more of the hydroxyl groups of the starch. Usually, they are esters, ethers or amides of starch with optionally substituted C ₁ -C ₄₀ radicals. Particularly advantageous is a corn starch which has been etherified with a 2-hydroxypropyl group and is marketed, for example, by the company National Starch under the trade name Amaze.

But also nonionic, fully synthetic polymers, such as Polyvinyl alcohol or polyvinylpyrrolidinone are as inventive Thickener used. Preferred nonionic, fully synthetic Polymers are for example from BASF under the trade name Luviskol distributed. Enable such nonionic polymers besides their excellent thickening properties, also one significant improvement of the sensory feeling of the resulting Preparations.

When inorganic thickeners have phyllosilicates (polymers, crystalline sodium disilicates) are particularly suitable in the sense of present invention. In particular clays, in particular Magnesium aluminum silicates, such as bentonite, especially Smectites, such as montmorillonite or hectorite, which may also be present may be suitably modified, and synthetic sheet silicates, such as that of the company Süd Chemie under the Trade name Optigel distributed magnesium layer silicate, are preferred.

To further increase the performance of the oxidizing agent preparation, at least one optionally hydrated SiO ₂ compound may additionally be added to the composition according to the invention. It may be preferred according to the invention, the optionally hydrated SiO ₂ compounds in amounts of 0.05 wt .-% to 15 wt .-%, particularly preferably in amounts of 0.15 wt .-% to 10 wt .-% and completely particularly preferably used in amounts of from 0.2 wt .-% to 5 wt .-%, each based on the anhydrous composition according to the invention. The amounts given in each case the content of the SiO ₂ compounds (without their water content) in the funds again.

With regard to the optionally hydrated SiO ₂ compounds, the present invention is in principle subject to no restrictions. Preference is given to silicic acids, their oligomers and polymers and their salts. Preferred salts are the alkali salts, especially the potassium and sodium salts. The sodium salts are very particularly preferred.

The optionally hydrated SiO ₂ compounds can be present in various forms. According to the invention, the SiO ₂ compounds are preferably used in the form of silica gels (silica gel) or particularly preferably as water glass. These SiO ₂ compounds may be partially present in aqueous solution.

Very particularly preferred according to the invention are water glasses which consist of a silicate of the formula (SiO ₂ ) _n (Na ₂ O) _m (K ₂ O) _p where n stands for a positive rational number and m and p independently represent a positive rational number or 0, with the provisos that at least one of the parameters m or p is different from 0 and the ratio between n and the sum of m and p is between 1: 4 and 4: 1.

Next the components described by the molecular formula the water glasses in small quantities still further additives, such as phosphates or magnesium salts.

Particularly according to the invention preferred water glasses are among others from the company Henkel under the designations Ferrosil 119, soda water glass 40/42, Portil A, Portil AW and Portil W and from Akzo under the Designation Britesil C20 sold.

Preferably are the preparation (A) and / or optionally the oxidizing agent preparation (B) formulated as flowable preparations.

Preferably is the flowable preparations (A) and / or (B) further added an emulsifier or a surfactant, wherein surface-active Substances depending on the field of application as surfactants or as emulsifiers and anionic, cationic, zwitterionic, amphoteric and nonionic surfactants and emulsifiers selected are.

• – lineare und verzweigte Fettsäuren mit 8 bis 30 C-Atomen (Seifen),
• – Ethercarbonsäuren der Formel RO(CH₂CH₂O)_xCH₂COOH, in der R eine lineare Alkylgruppe mit 8 bis 30 C-Atomen und x = 0 oder 1 bis 16 ist,
• – Acylsarcoside mit 8 bis 24 C-Atomen in der Acylgruppe,
• – Acyltauride mit 8 bis 24 C-Atomen in der Acylgruppe,
• – Acylisethionate mit 8 bis 24 C-Atomen in der Acylgruppe,
• – Sulfobernsteinsäuremono- und -dialkylester mit 8 bis 24 C-Atomen in der Alkylgruppe und Sulfobernsteinsäuremono-alkylpolyoxyethylester mit 8 bis 24 C-Atomen in der Alkylgruppe und 1 bis 6 Oxyethylgruppen,
• – lineare Alkansulfonate mit 8 bis 24 C-Atomen,
• – lineare α-Olefinsulfonate mit 8 bis 24 C-Atomen,
• – Sulfonate ungesättigter Fettsäuren mit 8 bis 24 C-Atomen und 1 bis 6 Doppelbindungen,
• – α-Sulfofettsäuremethylester von Fettsäuren mit 8 bis 30 C-Atomen,
• – Alkylsulfate und Alkylethersulfate der Formel RO(CH₂CH₂O)_xSO₃H, in der R eine bevorzugt lineare Alkylgruppe mit 8 bis 30 C-Atomen und x = 0 oder 1 bis 12 ist,
• – Gemische oberflächenaktiver Hydroxysulfonate,
• – sulfatierte Hydroxyalkylpolyethylen- und/oder Hydroxyalkylenpropylenglykolether,
• – Ester der Weinsäure und Zitronensäure mit Alkoholen, die Anlagerungsprodukte von etwa 2–15 Molekülen Ethylenoxid und/oder Propylenoxid an Fettalkohole mit 8 bis 22 C-Atomen darstellen,
• – Alkyl- und/oder Alkenyletherphosphate der Formel
  
  in der R bevorzugt für einen aliphatischen, gegebenenfalls ungesättigten Kohlenwasserstoffrest mit 8 bis 30 Kohlenstoffatomen, R' für Wasserstoff, einen Rest (CH₂CH₂O)_yR und x und y unabhängig voneinander für eine Zahl von 1 bis 10 steht,
• – sulfatierte Fettsäurealkylenglykolester der Formel RC(O)O(alkO)_nSO₃H, in der R für einen linearen oder verzweigten, aliphatischen, gesättigten und/oder ungesättigten Alkylrest mit 6 bis 22 C-Atomen, alk für CH₂CH₂, CHCH₃CH₂ und/oder CH₂CHCH₃ und n für eine Zahl von 0,5 bis 5 steht,
• – Monoglyceridsulfate und Monoglyceridethersulfate der Formel (MGS)
  
  in der R für einen linearen oder verzweigten Alkylrest mit 6 bis 22 Kohlenstoffatomen, und x, y und z in Summe für 0 oder für Zahlen von 1 bis 30, vorzugsweise 2 bis 10 stehen. Typische Beispiele für im Sinne der Erfindung geeignete Monoglycerid(ether)sulfate sind die Umsetzungsprodukte von Laurinsäuremonoglycerid, Kokosfettsäuremonoglycerid, Palmitinsäuremonoglycerid, Stearinsäuremonoglycerid, Ölsäuremonoglycerid und Talgfettsäure monoglycerid sowie deren Ethylenoxidaddukte mit Schwefeltrioxid oder Chlorsulfonsäure in Form ihrer Natriumsalze. Vorzugsweise werden Monoglyceridsulfate der Formel (MGS) eingesetzt, in der R für einen linearen Alkylrest mit 8 bis 18 Kohlenstoffatomen steht.

Suitable anionic surfactants in preparations according to the invention are all anionic surfactants suitable for use on the human body. These are characterized by a water-solubilizing, anionic group such as a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group of about 8 to 30 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups may be present in the molecule. Examples of suitable anionic surfactants are, in each case in the form of the sodium, potassium and ammonium as well as the mono-, di- and trialkanolammonium salts having 2 to 4 C atoms in the alkanol group,

• - linear and branched fatty acids with 8 to 30 carbon atoms (soaps),
• Ether carboxylic acids of the formula RO (CH ₂ CH ₂ O) _x CH ₂ COOH, in which R is a linear alkyl group having 8 to 30 C atoms and x = 0 or 1 to 16,
• Acylsarcosides having 8 to 24 C atoms in the acyl group,
• Acyltaurides having 8 to 24 carbon atoms in the acyl group,
• Acyl isethionates having 8 to 24 C atoms in the acyl group,
• Sulfosuccinic acid mono- and dialkyl esters having 8 to 24 C atoms in the alkyl group and sulfosuccinic acid monoalkyl polyoxyethyl esters having 8 to 24 C atoms in the alkyl group and 1 to 6 oxyethyl groups,
• - linear alkanesulfonates having 8 to 24 carbon atoms,
• Linear α-olefinsulfonates having 8 to 24 C atoms,
• Sulfonates of unsaturated fatty acids having 8 to 24 C atoms and 1 to 6 double bonds,
• Α-sulfofatty acid methyl esters of fatty acids having 8 to 30 carbon atoms,
• Alkyl sulfates and alkyl ether sulfates of the formula RO (CH ₂ CH ₂ O) _x SO ₃ H, in which R is a preferably linear alkyl group having 8 to 30 C atoms and x = 0 or 1 to 12,
• Mixtures of hydroxysulfonates,
• Sulfated hydroxyalkylpolyethylene and / or hydroxyalkylene glycol ethers,
• Esters of tartaric acid and citric acid with alcohols which are adducts of about 2-15 molecules of ethylene oxide and / or propylene oxide with fatty alcohols containing 8 to 22 carbon atoms,
• - Alkyl and / or alkenyl ether of the formula
  
  in which R is an aliphatic, optionally unsaturated hydrocarbon radical having 8 to 30 carbon atoms, R 'is hydrogen, a radical (CH ₂ CH ₂ O) _y R and x and y independently of one another have a number from 1 to 10,
• - sulfated Fettsäurealkylenglykolester of the formula RC (O) O (AlkO) _n SO ₃ H, in which R is a linear or branched, aliphatic, saturated and / or unsaturated alkyl radical having 6 to 22 carbon atoms, Alk is CH ₂ CH ₂ CHCH ₃ CH ₂ and / or CH ₂ CHCH ₃ and n is a number from 0.5 to 5,
• Monoglyceride sulfates and monoglyceride ether sulfates of the formula (MGS)
  
  in which R is a linear or branched alkyl radical having 6 to 22 carbon atoms, and x, y and z are in total 0 or numbers of 1 to 30, preferably 2 to 10. Typical examples of monoglyceride (ether) sulfates suitable for the purposes of the invention are the reaction products of lauric acid monoglyceride, coconut fatty acid monoglyceride, palmitic acid monoglyceride, stearic acid monoglyceride, oleic acid monoglyceride and tallow fatty acid monoglyceride and their ethylene oxide adducts with sulfur trioxide or chlorosulfonic acid in the form of their sodium salts. Preferably, monoglyceride sulfates of the formula (MGS) are used, in which R is a linear alkyl radical having 8 to 18 carbon atoms.

preferred Anionic surfactants are alkyl sulfates, alkyl ether sulfates and ether carboxylic acids with 10 to 18 C atoms in the alkyl group and up to 12 glycol ether groups in the molecule.

When zwitterionic surfactants become such surface active Compounds referred to in the molecule at least one quaternary ammonium group and at least one carboxylate, Sulfonate or sulfate group wear. Particularly suitable zwitterionic Surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinates, for example, the cocoalkyl dimethyl ammonium glycinate, N-acyl aminopropyl N, N-dimethyl ammonium glycinates, for example, the Kokosacylaminopropyl-dimethylammoniumglycinat, and 2-Alkyl-3-carboxymethyl-3-hydroxyethyl-imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and Kokosacylaminoethylhydroxyethylcarboxymethylglycinat. A preferred zwitterionic surfactant is that under the INCI name Cocamidopropyl betaine known fatty acid amide derivative.

Amphoteric surfactants are understood to mean those surface-active compounds which, apart from a C ₈ -C ₂₄ -alkyl or -acyl group in the molecule, contain at least one free amino group and at least one -COOH or -SO ₃ H group and which are capable of forming internal salts , Examples of suitable amphoteric surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each having about 8 to 24 C Atoms in the alkyl group. Particularly preferred amphoteric surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C ₁₂ -C ₁₈ acylsarcosine.

• – Anlagerungsprodukte von 1 bis 50 Mol Ethylenoxid und/oder 0 bis 5 Mol Propylenoxid an lineare und verzweigte Fettalkohole mit 8 bis 30 C-Atomen, wie beispielsweise beispielsweise Lauryl-, Myristyl-, Cetyl-, aber auch Stearyl-, Isostearyl- und Oleylalkohol, an Fettsäuren mit 8 bis 30 C-Atomen und an Alkylphenole mit 8 bis 15 C-Atomen in der Alkylgruppe,
• – mit einem Methyl- oder C₂-C₆-Alkylrest endgruppenverschlossene Anlagerungsprodukte von 1 bis 50 Mol Ethylenoxid und/oder 0 bis 5 Mol Propylenoxid an lineare und verzweigte Fett alkohole mit 8 bis 30 C-Atomen, an Fettsäuren mit 8 bis 30 C-Atomen und an Alkylphenole mit 8 bis 15 C-Atomen in der Alkylgruppe, wie beispielsweise die unter den Verkaufsbezeichnungen Dehydol LS, Dehydol LT (Cognis) erhältlichen Typen,
• – Polyglycerinester und alkoxylierte Polyglycerinester, wie beispielsweise Poly(3)glycerindiisostearat (Handelsprodukt: Lameform TGI (Henkel)) und Poly(2)glycerinpolyhydroxystearat (Handelsprodukt: Dehymuls PGPH (Henkel)).
• – Polyolfettsäureester, wie beispielsweise das Handelsprodukt Hydagen HSP (Cognis) oder Sovermol-Typen (Cognis),
• – höher alkoxylierte, bevorzugt propoxylierte und insbesondere ethoxylierte, Mono-, Di- und Triglyceride, wie beispielsweise Glycerinmonolaurat + 20 Ethylenoxid und Glycerinmonostearat + 20 Ethylenoxid,
• – Aminoxide,
• – Hydroxymischether,
• – Sorbitanfettsäureester und Anlagerungeprodukte von Ethylenoxid an Sorbitanfettsäureester wie beispielsweise die Polysorbate und Sorbitanmonolaurat + 20 Mol Ethylenoxid (EO),
• – Zuckerfettsäureester und Anlagerungsprodukte von Ethylenoxid an Zuckerfettsäureester,
• – Anlagerungsprodukte von Ethylenoxid an Fettsäurealkanolamide und Fettamine,
• – Fettsäure-N-alkylglucamide,
• – Alkylphenole und Alkylphenolalkoxylate mit 6 bis 21, insbesondere 6 bis 15 Kohlenstoffatomen in der Alkylkette und 1 bis 30 Ethylenoxid- und/oder Propylenoxid-Einheiten. Bevorzugte Vertreter dieser Klasse sind beispielsweise Nonylphenol + 9 EO und Octylphenol + 8 EO;
• – Alkylpolyglykoside entsprechend der allgemeinen Formel RO-(Z)_x, wobei R für Alkyl, Z für Zucker sowie x für die Anzahl der Zuckereinheiten steht. Die erfindungsgemäß verwendbaren Alkylpolyglykoside können lediglich einen bestimmten Alkylrest R enthalten. Üblicherweise werden diese Verbindungen aber ausgehend von natürlichen Fetten und Ölen oder Mineralölen hergestellt. In diesem Fall liegen als Alkylreste R Mischungen entsprechend den Ausgangsverbindungen bzw. entsprechend der jeweiligen Aufarbeitung dieser Verbindungen vor.

Furthermore, it has proved to be advantageous if the colorants according to the invention contain further nonionic surfactants. Nonionic surfactants contain as hydrophilic group z. A polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether groups. Such compounds are, for example

• - Addition products of 1 to 50 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide to linear and branched fatty alcohols having 8 to 30 carbon atoms, such as, for example, lauryl, myristyl, cetyl, but also stearyl, isostearyl and oleyl alcohol , fatty acids having 8 to 30 carbon atoms and alkylphenols having 8 to 15 carbon atoms in the alkyl group,
• - With a methyl or C ₂ -C ₆ -alkyl radical endgruppenverschlossene addition products of 1 to 50 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide to linear and branched fatty alcohols having 8 to 30 carbon atoms, of fatty acids with 8 to 30 C. And alkylphenols having 8 to 15 carbon atoms in the alkyl group, such as the types available under the sales names Dehydol LS, Dehydol LT (Cognis),
• Polyglycerol esters and alkoxylated polyglycerol esters, such as poly (3) glycerol diisostearate (commercial product: Lameform TGI (Henkel)) and poly (2) glycerol polyhydroxystearate (commercial product: Dehymuls PGPH (Henkel)).
• Polyol fatty acid esters, such as the commercial product Hydagen HSP (Cognis) or Sovermol types (Cognis),
• Higher alkoxylated, preferably propoxylated and in particular ethoxylated, mono-, di- and triglycerides, such as glycerol monolaurate + 20 ethylene oxide and glycerol monostearate + 20 ethylene oxide,
• - amine oxides,
• - hydroxymix ether,
• Sorbitan fatty acid esters and adducts of ethylene oxide with sorbitan fatty acid esters such as the polysorbates and sorbitan monolaurate + 20 moles of ethylene oxide (EO),
• Sugar fatty acid esters and addition products of ethylene oxide with sugar fatty acid esters,
• Adducts of ethylene oxide with fatty acid alkanolamides and fatty amines,
• Fatty acid N-alkylglucamides,
• - Alkylphenols and Alkylphenolalkoxylate having 6 to 21, in particular 6 to 15 carbon atoms in the alkyl chain and 1 to 30 ethylene oxide and / or propylene oxide units. Preferred representatives of this class are, for example, nonylphenol + 9 EO and octylphenol + 8 EO;
• - Alkylpolyglykoside according to the general formula RO- (Z) _x , wherein R is alkyl, Z is sugar and x is the number of sugar units. The alkyl polyglycosides which can be used according to the invention can only contain one particular alkyl radical R. Usually, however, these compounds are prepared starting from natural fats and oils or mineral oils. In this case, the alkyl radicals R are mixtures corresponding to the starting compounds or corresponding to the particular work-up of these compounds.

Suitable nonionic surfactants are, in particular, C ₈ -C ₂₂ -alkyl mono- and oligoglycosides and their ethoxylated analogs. In particular, the nonethoxylated compounds have been found to be particularly suitable.

• – im Wesentlichen aus C₈- und C₁₀-Alkylgruppen,
• – im Wesentlichen aus C₁₂- und C₁₄-Alkylgruppen,
• – im Wesentlichen aus C₈-C₁₆-Alkylgruppen oder
• – im Wesentlichen aus C₁₂-C₁₆-Alkylgruppen oder
• – im Wesentlichen aus C₁₆-C₁₈-Alkylgruppen besteht.

Particularly preferred are those alkyl polyglycosides of the formula RO- (Z) _x , in which R

• Essentially C ₈ and C ₁₀ alkyl groups,
• Essentially of C ₁₂ and C ₁₄ alkyl groups,
• Essentially of C ₈ -C ₁₆ -alkyl groups or
• Essentially of C ₁₂ -C ₁₆ -alkyl groups or
• - Consists essentially of C ₁₆ -C ₁₈ alkyl groups.

These Compounds are characterized in that as sugar component Z any mono- or oligosaccharides can be used. Usually be sugars with 5 or 6 carbon atoms and the corresponding Used oligosaccharides. Such sugars are, for example, glucose, Fructose, galactose, arabinose, ribose, xylose, lyxose, allose, Altrose, mannose, gulose, idose, talose and sucrose. preferred Sugar building blocks are glucose, fructose, galactose, arabinose and sucrose; Glucose is particularly preferred.

The Alkylpolyglycosides which can be used according to the invention contain on average 1.1 to 5 sugar units. Alkylpolyglykoside with x values of 1.1 to 2.0 are preferred. Very particularly preferred are alkyl glycosides in which x is 1.1 to 1.8.

Also the alkoxylated homologs of said alkyl polyglycosides can used according to the invention. These homologs can average up to 10 ethylene oxide and / or Propylene oxide units per Alkylglykosideinheit included.

When further preferred nonionic surfactants are the alkylene oxide addition products saturated linear fatty alcohols and fatty acids with in each case 2 to 30 mol of ethylene oxide per mole of fatty alcohol or fatty acid proved. Preparations with excellent properties also obtained when they are fatty acid esters as nonionic surfactants of ethoxylated glycerol.

Especially preferred nonionic surfactants are because of the ease of processing substances that are commercially available as solids or liquids in pure form are. The definition of purity refers to this Not related to chemically pure compounds. Rather, especially when it comes to natural products is used, mixtures of different homologues, for example with different alkyl chain lengths, as with products Base of natural fats and oils are obtained. Even with alkoxylated products are usually mixtures different degrees of alkoxylation. The term purity refers in this context rather to the fact that the selected substances are preferably free of solvents, Adjusting agents and other accompanying substances should be.

In the case of the surfactants which are adducts of ethylene oxide and / or propylene oxide with fatty alcohols or derivatives of these addition products, both products with a "normal" homolog distribution and those with a narrow homolog distribution can be used. By "normal" homolog distribution are meant mixtures of homologues which are used in the reaction of Fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates as catalysts. Narrowed homolog distributions, on the other hand, are obtained when, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates are used as catalysts. The use of products with narrow homolog distribution may be preferred.

The anionic, nonionic, zwitterionic or amphoteric surfactants are in amounts of 0.1 to 45 wt .-%, preferably 1 to 30 wt .-% and most preferably from 1 to 15 wt .-%, based on the Total amount of ready-to-use agent used.

According to the invention preferred are also cationic surfactants of the quaternary type Ammonium compounds, the esterquats and the amidoamines. preferred quaternary ammonium compounds are ammonium halides, especially chlorides and bromides, such as alkyltrimethylammonium chlorides, Dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, z. Cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, Distearyldimethylammonium chloride, lauryldimethylammonium chloride, Lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride, as well as those under the INCI names Quaternium-27 and Quaternium-83 known imidazolium compounds. The long alkyl chains of the above Surfactants preferably have 10 to 18 carbon atoms. Further Cationic surfactants which can be used according to the invention represent the quaternized protein hydrolysates.

The Alkylamidoamines are usually natural by amidation or synthetic fatty acids and fatty acid cuts prepared with dialkylaminoamines and are characterized by a good conditioning effect especially by their good biological Degradability. A particularly suitable according to the invention Compound from this group of substances represents that under the name Tegoamide S 18 Commercially available Stearamidopropyl-dimethylamine represents.

Also very well biodegradable are quaternary ester compounds, so-called "esterquats". When Esterquats act these are known substances that have at least one ester function and at least one quaternary ammonium group as a structural element contain. Preferred ester quats are quaternized ester salts of Fatty acids with triethanolamine, quaternized ester salts of fatty acids with diethanolalkylamines and quaternized Ester salts of fatty acids with 1,2-dihydroxypropyldialkylamines. Such products are sold, for example, under the trademarks Stepantex, Dehyquart and Armocare expelled. The products Armocare VGH-70, N, N-bis (2-palmitoyloxyethyl) dimethyl ammonium chloride, and Dehyquart F-75, Dehyquart C-4046, Dehyquart L80 and Dehyquart AU-35 are examples for such esterquats.

The cationic surfactants are used in the invention Agents preferably in amounts of 0.05 to 10 wt .-%, based on the entire remedy, included. Amounts of 0.1 to 5 wt .-% are particularly preferred.

In In a preferred embodiment, non-ionic, zwitterionic and / or amphoteric surfactants and mixtures thereof be preferred.

• – Anlagerungsprodukte von 4 bis 30 Mol Ethylenoxid und/oder 0 bis 5 Mol Propylenoxid an lineare Fettalkohole mit 8 bis 22 C-Atomen, an Fettsäuren mit 12 bis 22 C-Atomen und an Alkylphenole mit 8 bis 15 C-Atomen in der Alkylgruppe,
• – C₁₂-C₂₂-Fettsäuremono- und -diester von Anlagerungsprodukten von 1 bis 30 Mol Ethylenoxid an Polyole mit 3 bis 6 Kohlenstoffatomen, insbesondere an Glycerin,
• – Ethylenoxid- und Polyglycerin-Anlagerungsprodukte an Methylglucosid-Fettsäureester, Fettsäurealkanolamide und Fettsäureglucamide,
• – C₈-C₂₂-Alkylmono- und -oligoglycoside und deren ethoxylierte Analoga, wobei Oligomerisierungsgrade von 1,1 bis 5, insbesondere 1,2 bis 2,0, und Glucose als Zuckerkomponente bevorzugt sind,
• – Gemische aus Alkyl-(oligo-)glucosiden und Fettalkoholen zum Beispiel das im Handel erhältliche Produkt Montanov 68,
• – Anlagerungsprodukte von 5 bis 60 Mol Ethylenoxid an Rizinusöl und gehärtetes Rizinusöl,
• – Partialester von Polyolen mit 3 bis 6 Kohlenstoffatomen mit gesättigten Fettsäuren mit 8 bis 22 C-Atomen,
• – Sterine, wobei als Sterine eine Gruppe von Steroiden verstanden wird, die am C-Atom 3 des Steroid-Gerüstes eine Hydroxylgruppe tragen und aus tierischem Gewebe (Zoosterine; Beispiele: Cholesterin, Lanosterin) aus pflanzlichen Fetten (Phytosterine; Beispiele: Ergosterin, Stigmasterin und Sitosterin) sowie aus Pilzen und Hefen (Mykosterine) isoliert werden können.
• – Phospholipide, vor allem Glucose-Phospolipide, die z. B. als Lecithine bzw. Phosphatidylcholine aus z. B. Eidotter oder Pflanzensamen (z. B. Sojabohnen) gewonnen werden,
• – Fettsäureester von Zuckern und Zuckeralkoholen, wie Sorbit
• – Polyglycerine und Polyglycerinderivate wie beispielsweise Polyglycerinpoly-12-hydroxystearat (Handelsprodukt Dehymuls PGPH)
• – Lineare und verzweigte Fettsäuren mit 8 bis 30 C-Atomen und deren Na-, K-, Ammonium-, Ca-, Mg- und Zn-Salze.

In a further preferred embodiment, the effect of the active ingredient according to the invention can be increased by emulsifiers. Such emulsifiers are, for example

• Addition products of from 4 to 30 mol of ethylene oxide and / or from 0 to 5 mol of propylene oxide onto linear fatty alcohols having from 8 to 22 carbon atoms, to fatty acids containing from 12 to 22 carbon atoms and to alkylphenols having from 8 to 15 carbon atoms in the alkyl group,
• C ₁₂ -C ₂₂ -fatty acid mono- and diesters of addition products of from 1 to 30 mol of ethylene oxide onto polyols having from 3 to 6 carbon atoms, in particular to glycerol,
• Ethylene oxide and polyglycerol addition products to methyl glucoside fatty acid esters, fatty acid alkanolamides and fatty acid glucamides,
• C ₈ -C ₂₂ -alkylmono- and -oligoglycosides and their ethoxylated analogues, preference being given to degrees of oligomerization of from 1.1 to 5, in particular from 1.2 to 2.0, and glucose as the sugar component,
• Mixtures of alkyl- (oligo-) glucosides and fatty alcohols, for example the commercial product Montanov 68,
• Adducts of 5 to 60 moles of ethylene oxide with castor oil and hydrogenated castor oil,
• Partial esters of polyols having 3 to 6 carbon atoms with saturated fatty acids having 8 to 22 C atoms,
• - Sterols, sterols being understood to mean a group of steroids which carry a hydroxyl group on C-atom 3 of the steroid skeleton and of animal tissue (zoosterols, cholesterol, lanosterol) from vegetable fats (phytosterols, examples: ergosterol, stigmasterol and sitosterol) as well as off Mushrooms and yeasts (mycosterines) can be isolated.
• - Phospholipids, especially glucose phospholipids, the z. B. as lecithins or phosphatidylcholines from z. Egg yolks or plant seeds (eg soybeans),
• - fatty acid esters of sugars and sugar alcohols, such as sorbitol
• Polyglycerols and polyglycerol derivatives such as polyglycerol poly-12-hydroxystearate (commercial product Dehymuls PGPH)
• - Linear and branched fatty acids with 8 to 30 carbon atoms and their Na, K, ammonium, Ca, Mg and Zn salts.

The agents according to the invention contain the emulsifiers preferably in amounts of 0.1 to 25 wt .-%, in particular 0.5 to 15% by weight, based on the total amount of ready-to-use agent.

nonionic Emulsifiers or surfactants with an HLB value of 10-15 can Particularly preferred according to the invention. Under the emulsifier types mentioned, the emulsifiers, which is not ethylene oxide and / or propylene oxide in the molecule contain very particularly preferred.

A according to the invention preferred embodiment The present invention is that the ready for use Mean a pH between 7 and 12, in particular between 8 and 11, more preferably between 8.5 and 10.5.

Usually the pH is adjusted with pH adjusters. To adjustment of the pH are common to those skilled in the cosmetics Acidifying and alkalizing agents common. The for adjusting the pH usable alkalizing agent are typically selected from inorganic salts, especially the alkali and alkaline earth metals, organic alkalizing agents, especially amines, basic amino acids and alkanolamines, and ammonia. According to preferred Acidifizierungsmittei are Pleasure acids, such as citric acid, Acetic, malic or tartaric acid, and diluted mineral acids.

at The pH values for the purposes of the present invention are to pH values measured at a temperature of 22 ° C were.

Organic alkalizing agents which can be used according to the invention are preferably selected from alkanolamines of primary, secondary or tertiary amines having a C ₂ -C ₆ -alkyl basic body which carries at least one hydroxyl group. Particularly preferred alkanolamines are selected from the group formed from 2-aminoethan-1-ol (monoethanolamine), 3-aminopropan-1-ol, 4-aminobutan-1-ol, 5-aminopentan-1-ol, 1 -Aminopropan-2-ol (monoisopropanolamine), 1-aminobutan-2-ol, 1-aminopentan-2-ol, 1-aminopentan-3-ol, 1-aminopentan-4-ol, 2-amino-2-methyl- propanol, 2-amino-2-methylbutanol, 3-amino-2-methylpropan-1-ol, 1-amino-2-methylpropan-2-ol, 3-aminopropane-1,2-diol, 2-amino-2-ol methylpropane-1,3-diol, 2-amino-2-ethyl-1,3-propanediol, N, N-dimethylethanolamine, methylglucamine, triethanolamine, diethanolamine and triisopropanolamine. Very particularly preferred alkanolamines according to the invention are selected from the group consisting of 2-aminoethane-1-ol (monoethanolamine), 2-amino-2-methylpropan-1-ol, 2-amino-2-methylpropane-1,3-diol and triethanolamine , Particularly preferred alkanolamines are monoethanolamine and triethanolamine.

It but has been within the scope of the investigations of the present invention pointed out that further preferred according to the invention Means are characterized in that they additionally contain an inorganic alkalizing agent. The invention, inorganic alkalizing agents are preferably selected from the group formed from sodium hydroxide, potassium hydroxide, Calcium hydroxide, barium hydroxide, sodium phosphate, potassium phosphate, Sodium silicate, potassium silicate, sodium carbonate and potassium carbonate. Very particular preference is given to sodium hydroxide and / or potassium hydroxide.

The usable as alkalizing agent according to the invention basic amino acids are preferably selected from the group formed from L-arginine, D-arginine, D / L-arginine, L-lysine, D-lysine, D / L-lysine, more preferably L-arginine, D-arginine, D / L-arginine as an alkalizing agent in the context of the invention used.

After all Another preferred alkalizing agent is ammonia.

Prefers are the alkalizing agents in an amount of 0.05 to 10 wt .-%, in particular from 0.5 to 5 wt .-%, each based on the total weight of the ready-to-use agent.

• – nichtionische Polymere wie beispielsweise Vinylpyrrolidinon/Vinylacrylat-Copolymere, Polyvinylpyrrolidinon und Vinylpyrrolidinon/Vinylacetat-Copolymere, Polyethylenglykole und Polysiloxane,
• – kationische Polymere wie quaternisierte Celluloseether, Polysiloxane mit quaternären Gruppen, Dimethyldiallylammoniumchlorid-Polymere, Acrylamid-Dimethyldiallyl-ammoniumchlorid-Copolymere, mit Diethylsulfat quaternierte Dimethylamino-ethylmethacrylat-Vinylpyrrolidinon-Copolymere, Vinylpyrrolidinon-Imidazolinium-methochlorid-Copolymere und quaternierter Polyvinylalkohol,
• – zwitterionische und amphotere Polymere wie beispielsweise Acrylamidopropyl-trimethylammoniumchlorid/Acrylat-Copolymere und Octylacrylamid/Methyl-methacrylat/t-Butylaminoethylmethacrylat/2-Hydroxypropylmethacrylat-Copolymere,
• – anionische Polymere wie beispielsweise Polyacrylsäuren, vernetzte Polyacrylsäuren, Vinylacetat/Crotonsäure-Copolymere, Vinylpyrrolidinonlinylacrylat-Copolymere, Vinylacetat/Butylmaleat/Isobornylacrylat-Copolymere, Methylvinylether/Malein-säureanhydrid-Copolymere und Acrylsäure/Ethylacrylat/N-t-Butyl-acrylamid-Terpolymere,
• – weitere Verdickungsmittel wie Agar-Agar, Guar-Gum, Alginate, Gummi arabicum, Karaya-Gummi, Johannisbrotkernmehl, Leinsamengummen, Dextrane, Cellulose-Derivate, z. B. Methylcellulose, Hydroxyalkylcellulose und Carboxymethylcellulose, Stärke-Fraktionen und Derivate wie Amylose, Amylopektin und Dextrine, Tone wie z. B. Bentonit oder vollsynthetische Hydrokolloide wie z. B. Polyvinylalkohol,
• – Strukturanten wie Glucose, Maleinsäure und Milchsäure,
• – haarkonditionierende Verbindungen wie Phospholipide, beispielsweise Sojalecithin, Ei-Lecitin und Kephaline sowie Silikonöle,
• – Proteinhydrolysate, insbesondere Elastin-, Kollagen-, Keratin-, Milcheiweiß-, Sojaprotein- und Weizenproteinhydrolysate, deren Kondensationsprodukte mit Fettsäuren sowie quaternisierte Proteinhydrolysate,
• – Parfümöle, Dimethylisosorbid und Cyclodextrine,
• – Lösungsmittel und -vermittler wie Ethanol, Isopropanol, Ethylenglykol, Propylenglykol, Glycerin und Diethylenglykol,
• – faserstrukturverbessernde Wirkstoffe, insbesondere Mono-, Di- und Oligosaccharide wie beispielsweise Glucose, Galactose, Fructose, Fruchtzucker und Lactose,
• – quaternierte Amine wie Methyl-1-alkylamidoethyl-2-alkylimidazolinium-methosulfat
• – Entschäumer wie Silikone, bevorzugt Dimethicon,
• – Farbstoffe zum Anfärben des Mittels,
• – Antischuppenwirkstoffe wie Piroctone Ölamine, Zink Omadine und Climbazol,
• – Lichtschutzmittel beziehungsweise UV-Blocker, insbesondere derivatisierte Benzophenone, Zimtsäure-Derivate und Triazine,
• – Substanzen zur Einstellung des pH-Wertes, wie beispielsweise übliche Säuren, insbesondere Genusssäuren und Basen,
• – Wirkstoffe wie Panthenol, Pantothensäure, Pantolacton, Allantoin, Pyrrolidinoncarbonsäuren und deren Salze sowie Bisabolol,
• – Vitamine, Provitamine und Vitaminvorstufen, insbesondere solche der Gruppen A, B₃, B₅, B₆, C, E, F und H,
• – Cholesterin,
• – Konsistenzgeber wie Zuckerester, Polyolester oder Polyolalkylether,
• – Fette und Wachse wie Walrat, Bienenwachs, Montanwachs und Paraffine,
• – Fettsäurealkanolamide,
• – Quell- und Penetrationsstoffe wie Glycerin, Propylenglykolmonoethylether, Carbonate, Hydrogencarbonate, Guanidine, Harnstoffe sowie primäre, sekundäre und tertiäre Phosphate,
• – Trübungsmittel wie Latex, Styrol/PVP- und Styrol/Acrylamid-Copolymere
• – Perlglanzmittel wie Ethylenglykolmono- und -distearat sowie PEG-3-distearat,
• – Pigmente,
• – Stabilisierungsmittel für Wasserstoffperoxid und andere Oxidationsmittel,
• – Treibmittel wie Propan-Butan-Gemische, N₂O, Dimethylether, CO₂ und Luft,
• – Antioxidantien.

Furthermore, the agents according to the invention may contain other active ingredients, auxiliaries and additives, such as, for example

• Nonionic polymers such as vinylpyrrolidinone / vinyl acrylate copolymers, polyvinylpyrrolidinone and vinylpyrrolidinone / vinyl acetate copolymers, polyethylene glycols and polysiloxanes,
• Cationic polymers such as quaternized cellulose ethers, quaternary group polysiloxanes, dimethyldiallylammonium chloride polymers, acrylamide-dimethyldiallyl-ammonium chloride copolymers, diethyl sulfate quaternized dimethylaminoethylmethacrylate-vinylpyrrolidinone copolymers, vinylpyrrolidinone-imidazolinium methochloride copolymers and quaternized polyvinyl alcohol,
• Zwitterionic and amphoteric polymers such as acrylamidopropyltrimethylammonium chloride / acrylate copolymers and octylacrylamide / methyl methacrylate / t-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers,
• Anionic polymers, for example polyacrylic acids, crosslinked polyacrylic acids, vinyl acetate / crotonic acid copolymers, vinylpyrrolidinonyl-linyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and acrylic acid / ethyl acrylate / n-butyl acrylamide terpolymers,
• - Other thickeners such as agar-agar, guar gum, alginates, gum arabic, karaya gum, locust bean gum, linseed gums, dextrans, cellulose derivatives, eg. For example, methylcellulose, hydroxyalkylcellulose and carboxymethylcellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such. As bentonite or fully synthetic hydrocolloids such. For example, polyvinyl alcohol,
• - structurants such as glucose, maleic acid and lactic acid,
• Hair-conditioning compounds such as phospholipids, for example soybean lecithin, egg lecithin and cephalins and silicone oils,
• Protein hydrolysates, in particular elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolysates, their condensation products with fatty acids and quaternized protein hydrolysates,
• Perfume oils, dimethylisosorbide and cyclodextrins,
• Solvents and mediators such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol,
• Fiber-structure-improving active substances, in particular mono-, di- and oligosaccharides such as, for example, glucose, galactose, fructose, fructose and lactose,
• Quaternized amines such as methyl-1-alkylamidoethyl-2-alkylimidazolinium methosulfate
• Defoamers such as silicones, preferably dimethicone,
• Dyes for staining the agent,
• Antidandruff active ingredients such as Piroctone Ölamine, Zink Omadine and Climbazole,
• Light stabilizers or UV blockers, in particular derivatized benzophenones, cinnamic acid derivatives and triazines,
• Substances for adjusting the pH, for example customary acids, in particular edible acids and bases,
• - active substances such as panthenol, pantothenic acid, pantolactone, allantoin, pyrrolidinonecarboxylic acids and their salts, and bisabolol,
• Vitamins, provitamins and vitamin precursors, in particular those of groups A, B ₃ , B ₅ , B ₆ , C, E, F and H,
• - cholesterol,
• Bodying agents such as sugar esters, polyol esters or polyol alkyl ethers,
• - fats and waxes such as spermaceti, beeswax, montan wax and paraffins,
• Fatty acid alkanolamides,
• - swelling and penetrating substances such as glycerol, propylene glycol monoethyl ether, carbonates, bicarbonates, guanidines, ureas and primary, secondary and tertiary phosphates,
• Opacifiers such as latex, styrene / PVP and styrene / acrylamide copolymers
• Pearlescing agents such as ethylene glycol mono- and distearate and PEG-3-distearate,
• - pigments,
• Stabilizing agent for hydrogen peroxide and other oxidizing agents,
• Propellants such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air,
• - antioxidants.

The Selection of these other substances will be apparent to those skilled in the art according to desired properties of the agents meet.

In terms of additional optional components as well as the quantities used These components are expressly referred to the person skilled in the art known relevant manuals, z. Kh. Schrader, bases and formulations of cosmetics, 2nd edition, Hüthig Buch Verlag, Heidelberg, 1989, referenced.

One second subject of the present invention is a method for dyeing human hair, in which a means of the first Invention is applied to the hair, for a period of 3 to 45 minutes, preferably 5 to 30 minutes in the hair, and then the hair with water and / or a commercial shampoo rinsed becomes.

The Application temperatures in the invention Dyeing can be done in a range between 15 and 45 ° C lie. After the exposure time, the hair dye by rinsing, if necessary with the help of a shampoo, removed from the hair to be dyed. The washing up with a shampoo can be omitted if a carrier with high surfactant content, z. As a dyeing shampoo was used.

While the exposure time of the agent to the fiber may be advantageous to assist the dyeing process by supplying heat. The heat can be supplied by an external heat source, such as B. warm air of a hot air blower, as well, in particular with a hair coloring on living subjects, done by the body temperature of the subject. at The latter option is usually the one to Dyeing lot covered with a hood.

Especially the temperature is between 20 ° C during the exposure time and 40 ° C, especially between 25 ° C and 38 ° C.

The colorants of the invention give already at physiologically compatible temperatures of under 45 ° C intensive dyeings. They are suitable therefore especially for dyeing human hair.

In terms of further preferred embodiments of the invention Method applies mutatis mutandis to the invention Means said.

As already mentioned, the inventive Means also separated directly before the application of two or more packaged preparations are produced. This is particularly suitable to separate incompatible ingredients to a premature one To avoid reaction. A separation into multicomponent systems is particularly suitable where incompatibilities exist the ingredients are to be expected or to be feared. The ready-to-use agent is in such systems by the consumer prepared directly before use by mixing the components. A colorant in which the oxidation dye precursors initially separated from the oxidizing agent preparation, containing preferably hydrogen peroxide, are present, is preferred.

One The third object of the present invention is therefore a packaging unit (Kit-of-Parts), which are made separately from each other at least a container (I) containing an oxidizing agent preparation (B) contained in a cosmetic carrier as an oxidizing agent contains at least hydrogen peroxide, and at least one Container (II) containing a dyeing preparation (A), the in an aqueous-cosmetic carrier at least contains an oxidation dye precursor thereby in that the dyeing preparation (A) additionally Contains cocoa butter. Further preferably contains the multi-component packaging unit (kit-of-parts) in addition a user manual.

About that In addition, it may be preferable, if an application aid, such as a comb or brush, and / or a personal one Protective equipment, such as disposable gloves Kit is attached.

In terms of Further Preferred Embodiments of the Multi-component Packaging Unit (Kit-of-Parts) applies mutatis mutandis to the invention Means said.

One Another object of the invention is the cosmetic, non-therapeutic Use of a coloring agent for keratinische Fibers containing cocoa butter in a cosmetic carrier, to improve the care of keratinic fibers.

One Another object of the invention is the cosmetic, non-therapeutic Use of a coloring agent for keratinische Fibers containing cocoa butter in a cosmetic carrier, for improving the wet combability of the keratinic Fibers.

Another object of the invention is the cosmetic, non-therapeutic use of a coloring agent for keratinic fibers, containing in a cosmetic carrier cocoa butter, for improvement gloss of keratinic fibers.

In terms of further preferred embodiments of the invention Uses applies mutatis mutandis to the invention Means said.

The The following examples are intended to illustrate preferred embodiments illustrate the invention, but without limiting it.

Examples

Preparation of the coloring cream

• * Farbstoffmischung, enthaltend 60,6 Gew.-% p-Toluylendiaminsulfat, 3,4 Gew.-% 3-Aminophenol, 20,8 Gew.-% Resorcin, 3,4 Gew.-% 2-Methylresorcin, 3,4 Gew.-% 2-Amino-3-hydroxypyridin und 8,4 Gew.-% Siliciumdioxid, pyrogen, jeweils bezogen auf das Gesamtgewicht der Farbstoffmischung.

Lanette E, Pulver C₁₆-C₁₈-Fettalkoholsulfat, Natrium-Salz (INCI-Bezeichnung: Sodium Cetearyl Sulfate) (Cognis) Texapon NSF, 27% C₁₂-Fettalkoholsulfat, ethoxyliert (2 EO) Natrium-Salz (INCI-Bezeichnung: Sodium Laureth Sulfate) (Cognis) Cutina GMS SE Stearinsäureglycerylester (INCI-Bezeichnung: Glyceryl Stearate) (Cognis) Cutina AGS Ethylenglycoldistearylester (INCI-Bezeichnung: Glycol Distearate) (Cognis) Eutanol G 2-Octyldodecanol (INCI-Bezeichnung: Octyldodecanol) (Cognis) Hydrenol D C₁₆-C₁₈-Fettalkohol (INCI-Bezeichnung: Cetearyl alcohol) (Cognis) Eumulgin B2 C₁₆-C₁₈-Fettalkohol, ethoxyliert (20 EO) (INCI-Bezeichnung: Ceteareth-20) (Cognis) Phospholipid EFA zwitterionisches Phospholid (INCI-Bezeichnung: Linoleamidopropyl PG-dimonium chloride phosphate) (Uniqema) Kakaobutter, Pellets Kakaobutter (INCI-Bezeichnung: Theobroma Cacao Butter) (Henry Lamotte Oils GmbH) Herbasol Extrakt Aloe, entfärbt Wasser/Propylenglykol-Extrakt aus Aloe Vera (2–4% Aktivsubstanz; INCI-Bezeichnung: Aqua, Propylene Glycol, Aloe Barbadensis) (Cosmetochem) The following coloring creams with the same dye mixture were prepared: raw materials E1 V1 Color powder mixture * 3.0 3.0 Ammonium carbomer, 1% 12.0 12.0 Lanette E, powder 0.6 0.6 Texapon NSF, 27% 3.5 3.5 Potassium oleate, 12.5% 2.4 2.4 Cutina GMS SE 1.6 1.6 Cutina AGS 1.6 1.6 Eutanol G 1.6 1.6 Hydrenol D 9.6 9.6 Eumulgin B2 2.4 2.4 L-serine 0.5 0.5 Phospholipid EFA 0.1 0.1 Na ₄ -EDTA, powder, 87% 0.2 0.2 Cocoa butter, pellets 1.0 - ascorbic acid 0.2 0.2 Sodium sulfite, anhydrous, 96% 0.2 0.2 Herbasol extract aloe, discolored 1.0 1.0 Hydro Vance 2.0 2.0 Ammonia, 25% 9.0 9.0 Perfume qs qs water ad 100 ad 100

• * Dye mixture containing 60.6 wt .-% p-toluenediamine sulfate, 3.4 wt .-% of 3-aminophenol, 20.8 wt .-% resorcinol, 3.4 wt .-% 2-methylresorcinol, 3.4 wt .-% 2-amino-3-hydroxypyridine and 8.4 wt .-% silica, pyrogenic, each based on the total weight of the dye mixture.

Lanette E, powder C ₁₆ -C ₁₈ fatty alcohol sulfate, sodium salt (INCI name: Sodium Cetearyl Sulfate) (Cognis) Texapon NSF, 27% C ₁₂ fatty alcohol sulfate, ethoxylated (2 EO) sodium salt (INCI name: Sodium Laureth Sulfate) (Cognis) Cutina GMS SE Stearic Acid Glyceryl Ester (INCI name: Glyceryl Stearate) (Cognis) Cutina AGS Ethylene glycol distearyl ester (INCI name: Glycol Distearate) (Cognis) Eutanol G 2-octyldodecanol (INCI name: octyldodecanol) (Cognis) Hydrenol D C ₁₆ -C ₁₈ fatty alcohol (INCI name: cetearyl alcohol) (Cognis) Eumulgin B2 C ₁₆ -C ₁₈ fatty alcohol, ethoxylated (20 EO) (INCI name: Ceteareth-20) (Cognis) Phospholipid EFA zwitterionic phospholide (INCI name: Linoleamidopropyl PG-dimonium chloride phosphates) (Uniqema) Cocoa butter, pellets Cocoa butter (INCI name: Theobroma cacao butter) (Henry Lamotte Oils GmbH) Herbasol extract aloe, discolored Aloe Vera water / propylene glycol extract (2-4% active ingredient, INCI name: Aqua, Propylene Glycol, Aloe Barbadensis) (Cosmetochem)

The Fat base was melted together at 80 ° C and dispersed with a portion of the amount of water. Subsequently the remaining recipe ingredients were stirred incorporated in turn. Then, with water to 100 wt .-% filled in and the formulation stirred cold.

at the recipe V1 is a non-inventive Comparison recipe without cocoa butter. The recipe E1 is an inventive Example.

1.2. Mixing with the developer dispersion (EW) and application

Each coloring cream was mixed in a weight ratio of 1: 1 with a developer dispersion composed as follows. raw material Wt .-% Na benzoate 0.04 dipicolinic 0.10 disodiumpyrophosphate 0.19 1,2-propanediol 0.50 HEDP, 60% 0.25 Paraffin Liquidum 0.30 Genamine STAC 0.20 Cetearyl Alcohol 3.00 Eumulgin B2 0.70 Hydrogen peroxide 50% 12.2 Potassium hydroxide, 50% 0.19 water ad 100 Genamine STAC Trimethylstearylammonium chloride (about 80% active ingredient, INCI name: Steartrimonium Chloride) (Clariant)

For the staining was on strands of bleached Buffalo belly hair of about 0.7 g weight 4 times the amount applied to the finished application mixtures. After the strands dyed for 30 minutes at 32 ° C, they were washed with a commercial shampoo and dried with a hair dryer.

1.3 staining results

With Both dyeing formulations achieved a rich brown tone, wherein the with the dyeing preparation according to the invention (E1 + EW) treated strands clearly superior Shine showed.

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• - EP 998908 A2 [0120]
• EP 13713 A1 [0209]
• DE 4408506 A1 [0209]

Cited non-patent literature

• - Current Organic Chemistry 2000, 4 (10), pp. 1055-1078 (24) by E. Dagne et al. [0178]

Claims (13)

Agent for coloring keratin-containing fibers, in particular human hair, containing in a cosmetic carrier at least one coloring component, characterized in that the agent contains cocoa butter. Means according to claim 1, characterized in that the agent cocoa butter in a proportion of 0.01 to 10 wt .-%, preferably from 0.05 to 5 wt .-% and in particular from 0.1 to 3 wt .-%, respectively based on the total weight of the ready-to-use agent. Agent according to one of claims 1 to 2, characterized in that the agent as a coloring component contains at least one oxidation dye precursor. Agent according to one of claims 1 to 3, characterized in that the agent additionally at least contains an effective plant extract. Means according to claim 4, characterized in that the agent as an effective plant extract an extract of aloe Barbadensis contains. Agent according to one of claims 1 to 5, characterized in that the agent additionally at least an amino acid, an oligopeptide or a protein hydrolyzate contains. Means according to claim 6, characterized in that the agent contains L-serine. Agent according to one of claims 1 to 7, characterized in that the agent additionally at least a conditioner selected from cationized phosphate esters, contains. Packing unit (kit of parts), which are separated assembled from each other at least one container (I) containing an oxidizing agent preparation (B) used in a cosmetic Support as an oxidizing agent at least hydrogen peroxide contains, and at least one container (II) containing a dyeing preparation (A) in an aqueous-cosmetic Carrier comprises at least one oxidation dye precursor comprises, characterized in that the dyeing preparation (A) additionally Contains cocoa butter. Method of coloring human hair, wherein an agent according to any one of claims 1 to 8 on the hair applied for a period of 3 to 45 minutes, preferably 5 to 30 minutes in the hair, and then the hair rinsed with water and / or a commercial shampoo becomes. Cosmetic, non-therapeutic use of a Colorant for keratinic fibers containing in a cosmetic carrier cocoa butter, for improvement the care of the keratinic fibers. Cosmetic, non-therapeutic use of a Colorant for keratinic fibers containing in a cosmetic carrier cocoa butter, for improvement the wet combability of the keratinic fibers. Cosmetic, non-therapeutic use of a Colorant for keratinic fibers containing in a cosmetic carrier cocoa butter, for improvement gloss of keratinic fibers.