DE102008060670A1 - Alternative oxidizers - Google Patents

Abstract

The present application relates to compositions for gentle oxidative dyeing of keratinic fibers, in particular human hair, which are produced by mixing a dyeing preparation containing oxidation dye precursors, and an oxidizing agent preparation, wherein the oxidizing agent preparation is characterized in that it contains not as hydrogen peroxide, but sodium chlorite as the oxidizing agent. The use of such human hair dyeing agents results in a significant reduction in fiber damage in the dyeing process over conventional hydrogen peroxide based oxidation dyes with consistent dyeing performance.

Description

object the present application are agents for gentle oxidative Coloring of keratinous fibers, especially human Hairs obtained by mixing a dyeing preparation containing oxidation dye precursors, and an oxidizing agent preparation, wherein the oxidizing agent preparation is characterized by being known as Oxidizing agent no hydrogen peroxide, but sodium chlorite contains. The use of such dyeing agents of human hair causes a significant reduction of Damage to the fibers during the dyeing process conventional, hydrogen peroxide-based oxidation colorants at constant dyeing power.

Changing the shape and color of the hair is an important area of modern cosmetics. This allows the hair's appearance to be adapted to current fashion trends as well as to the individual wishes of the individual. In this case, permanent wave and other hair-changing methods can be used almost independently of the type of hair to be treated. In contrast, dyeing and bleaching processes are limited to certain initial hair colors. For fashionable color design of hairstyles or lamination of gray hair or even white hair with fashionable or natural colors, the consumer accesses to color-changing agents. In addition to the desired staining performance, these agents should cause the least possible damage to the hair. The basics of the dyeing processes are known in the art and in relevant monographs, eg. B. from K. Schrader, Basics and Formulations of Cosmetics, 2nd edition, 1989, Dr. med. Alfred Hüthig Verlag, Heidelberg, or W. Umbach (ed.), Cosmetics, 2nd edition, 1995, Georg Thieme Verlag, Stuttgart, New York , summarized.

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 it has to be a mixture of a larger one 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 off. At, in particular multiple, application of means With 5,6-dihydroxyindoline it is possible to give people with graying Hair to reproduce the natural hair color. The coloration can be done with atmospheric oxygen as the sole oxidant, so that resorted to no further oxidizing agents must become.

Another possibility for color change is the use of colorants containing so-called Oxofarbstoffvorprodukte. A first class of oxo dye precursors are compounds having at least one reactive carbonyl group. Form a second class of oxo dye precursors C, H-acidic compounds and compounds having primary or secondary amino group or hydroxy group, which in turn are selected from compounds of the group formed from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds. The aforementioned components are generally not themselves dyes, and therefore are not suitable alone for dyeing keratinhaltiger fibers alone. In combination, they form dyes in a non-oxidative process of so-called oxo dyeing. The resulting dyeings have partially color fastness on the keratin-containing fiber, which are comparable to those of the oxidation dyeing.

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, second class of oxo dye precursors may also corresponding oxidation dye precursors of the developer and / or Coupler type with or without use of an oxidizing agent Find. Thus, the method of oxo dyeing can be readily combine with the oxidative staining system.

Should Substrates are lightened or even bleached, which become the substrate coloring dyes usually oxidative using appropriate Oxidizing agents, such as hydrogen peroxide, decolorized.

Around To improve the care condition of the fibers, it has long been common the fibers following the color or shape changing Treatment to undergo a special post-treatment. there be, usually in the form of a rinse, the Hair with special ingredients, such as quaternary Ammonium salts or special polymers treated. Through this Treatment will depending on the formulation combability, hold and hair fullness and reduces the split rate. To the effort of the usual multi-stage process, in particular in the direct application by consumers, to reduce Recently, 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.

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

On the one hand the use of the oxidizing agents leads to coloration respectively development of the actual coloring to damage in the hair structure and on the hair surface. on the other hand oxidative dyes usually need one basic pH for coloration, especially between pH 9.0 and pH 10.5. This causes the hair to be brittle becomes, its elasticity wears off and the combability decreases. This damage increases with the duration of application to. Commercially available oxidative dyes must usually over a period of 30 minutes and longer on the hair fiber act. The increase of the exposure time leads to an increased impairment of the hair structure.

Farther the basic pH is often with ammonia as the alkalizing agent adjusted because ammonia-containing colorants additional Possess advantages in terms of dyeing power. For the user owns such a colorant next to one intense, unpleasant smell however the disadvantage that it through Ammonia to irritate the eyes, scalp or mucous membranes can come, causing sensitization or even allergic reactions can be caused.

Even though Dyeing with oxidative hair dyes Dyeing with other colorants, in particular direct dyes, significant advantages in terms their washout behavior and thus the color content own, there is still a need for improvement in terms of Fiber preservation and dyeing performance.

The oxidizing agents contained in these products are usually hydrogen peroxide, which accelerates the formation of the actual dyes from the oxidation dye precursors. Hydrogen peroxide, however, simultaneously damages the fiber structure in the interior. Depending on the severity of the degree of damage, this ranges from rough, brittle and difficult to comb hair over a reduced resistance and tear resistance of the hair to hair breakage. The greater the amount of hydrogen peroxide used, the more severe damage will usually be caused on the keratin fiber. Therefore, there is still a need for oxidative colorants that cause reduced damage to the fiber structure but without sacrificing dyeing performance.

Also if the colorants hitherto on the market usually good dyeing performances show, so can they due to hair damage, long application times and because of the high levels of oxidizing and alkalizing agent possible skin irritation can not be considered optimal.

in the In the context of her investigations, the Applicant has now surprising found that the exchange of hydrogen peroxide for sodium chlorite as oxidant in oxidative colorants positive in terms of reducing fiber damage.

One The first object of the present invention is therefore an agent for the oxidative dyeing of keratin-containing fibers, in particular human hair, which immediately before use by Mixing a dyeing preparation (A), containing in one aqueous, cosmetic carrier at least one Oxidation dye precursor, and an oxidizer formulation (B), characterized in that the oxidizing agent preparation (B) contains in a cosmetic carrier sodium chlorite.

Under keratin-containing or keratinic fibers are inventively furs, Wool, feathers and especially human hair understood. Even though the use according to the invention in the first place for dyeing and / or whitening keratin-containing fibers are suitable, is in principle a use also on others Areas nothing contrary.

The agents of the invention contain the active ingredients in a cosmetic carrier. This cosmetic carrier For the purposes of the invention is aqueous, alcoholic or aqueous-alcoholic or optionally in powder form. For the purpose of hair coloring such carriers are, for example, creams, emulsions, gels or surfactant-containing foaming solutions, such as for example shampoos, foam aerosols or other preparations, which are suitable for use on the hair.

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, 4-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 mandatory ingredient contains the inventive Agent in the dyeing preparation at least one oxidation dye precursor.

In a preferred embodiment, the inventive At least one developer-type oxidation dye precursor and / or coupler type. Preferably, the inventive Colorant at least one oxidation dye precursor of the developer type and at least one 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 p-phenylenediamine, p-toluenediamine, 2-chloro-p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2,6-diethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, N, N-dipropyl-p-phenylenediamine, 4-amino-3-methyl- (N, N-diethyl) -aniline, N, N-bis- (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 salts.

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.

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

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-diamino-propan-2-ol, Bis (2-hydroxy-5-aminophenyl) methane, 1,3-bis- (2,5-diaminophenoxy) -propan-2-ol, N, N'-bis (4-aminophenyl) -1,4-diazacycloheptane, 1,10-bis (2,5-diaminophenyl) -1,4,7,10-tetraoxadecane or one of the physiologically acceptable salts of these compounds.

wobei

• – G13 steht für ein Wasserstoffatom, ein Halogenatom, einen C₁-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-Hydroxyalkoxyrest, 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 radical, a C ₁ -C ₄ -aminoalkyl radical, a hydroxy-C ₁ -C ₄ -alkylamino radical, a C ₁ -C ₄ -hydroxyalkoxy radical, a C ₁ -C ₄ -hydroxyalkyl-C ₁ -C ₄ -ami noalkyl radical or a di- (C ₁ -C ₄ -alkyl) aminoC 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.

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

preferred p-aminophenols of the formula (E3) are in particular p-aminophenol, N-methyl-p-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 2-hydroxymethylamino-4-aminophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2- (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 p-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 -NG21G22 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 tolerated 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 represents a hydroxy 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 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.

Especially preferred pyrimidine derivatives are in particular the compounds 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2-dimethylamino-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6-triaminopyrimidine.

worin

• – G21, G22, G23 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 G23 für ein Wasserstoffatom steht, G24 neben den vorgenannten Gruppen zusätzlich für eine Gruppe -NH₂ stehen kann,
• – G24 steht für ein Wasserstoffatom, eine C₁-C₄-Alkylgruppe, eine C₁-C₄-Monohydroxyalkylgruppe oder eine C₂-C₄-Polyhydroxyalkylgruppe und
• – G25 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

• G21, G22, G23 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 23 is a hydrogen atom, G 24 may additionally be a group -NH _{2 in} addition to the abovementioned groups,
• G24 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
• G25 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 -NG23G24 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-tert-butyl-1-methylpyrazole, 4,5-diamino-1-tert-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-aminoethylamino-1,3-dimethylpyrazole, and its physiological compatible salts.

wobei

• – G26, G27 und G28, G29 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-Hydroxyalkyl)amino-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 NG26G27 und NG28G29 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 NG26G27 (oder NG28G29) 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

• - G26, G27 and G28, G29 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 hydroxyalkyl) amino 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 dialkyl radicals optionally 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) aminoC ₁ -C ₄ -alkyl radical, an amino radical, a C ₁ -C _4- alkylamino radical, a di (C ₁ -C ₄ -alkyl) amino radical, C ₁ -C ₄ -hydroxyalkylamino radical or a di- (C ₁ -C ₄ -hydroxyalkyl) amino radical, a halogen atom, a carboxylic acid group or a sulfonic acid group,
• - i has the value 0, 1, 2 or 3,
• - p has the value 0 or 1,
• - q has the value 0 or 1 and
• - n has the value 0 or 1,

with the proviso that

• The sum of p + q is not equal to 0,
• If p + q is 2, n is 0, and groups NG26G27 and NG28G29 occupy the positions (2, 3); (5,6); (6,7); (3,5) or (3,7);
• If p + q is 1, n is 1, and the groups NG26G27 (or NG28G29) and the group OH occupy the positions (2, 3); (5,6); (6,7); (3,5) or (3,7);

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

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) can 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-hydroxyethyl) amino] 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 tautomeric forms, if a tautomeric equilibrium exists.

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, 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, 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.

All particularly 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.

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.

Kupplerkomponenten For the purposes of the invention, at least one substitution of a chemical residue of the coupler by the oxidized form of the developer component. This forms a covalent bond between the coupler and the developer component out. Couplers are preferably cyclic compounds which are cyclic at least two groups selected from (i) optionally substituted amino groups and / or (ii) hydroxyl groups. If the cyclic compound is a six-membered ring (preferably aromatic), so the said groups are preferably in the ortho position or meta-position to each other.

• – m-Aminophenol und/oder dessen Derivate,
• – m-Diaminobenzol und/oder dessen Derivate,
• – o-Diaminobenzol und/oder dessen Derivate,
• – o-Aminophenolderivate, wie beispielsweise o-Aminophenol,
• – 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 mehrer Verbindungen aus einer oder mehrerer 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:

• M-aminophenol and / or its derivatives,
• M-diaminobenzene and / or its derivatives,
• O-diaminobenzene and / or its derivatives,
• O-aminophenol derivatives, such as o-aminophenol,
• 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,
• - Chinoxalinderivate, 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-alkoxygruppe, eine C₁-C₆-Alkyoxy-C₂-C₆-alkoxygruppe, eine Arylgruppe oder eine Heteroarylgruppe.The m-aminophenols or derivatives thereof which can be used according to the invention are preferably selected from at least one compound of the formula (K1) and / or from at least one physiologically tolerated salt of a compound of the 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 m-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 m-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 m-diaminobenzene coupler components are selected from at least one compound from the group that is formed from 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 o-diaminobenzenes or their derivatives 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 o-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 one compound of the formula (K4) and / or from 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 hydrogen atom, a halogen atom or a C ₁ -C ₄ alkyl group, with the proviso that G24 bind in meta-position or ortho-position to the structural fragment of formula NG23.

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 NG31 G32, worin G31 und G32 unabhängig voneinander stehen für ein Wasserstoffatom, eine C₁-C₄-Alkylgruppe, eine C₃-C₆-Cycloalkyl gruppe, 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 NG31 G32, 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 -alkyl) ammonium groups, and 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 .

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 preferred coupler components according to the invention are selected from 3-amino phenol, 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-hydroxyethynamino] -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-ylphenyl) amino] ethanol, 3-amino-4- (2-methoxyethoxy) -5 -methylphenylamine, 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-naph thiol, 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 of these compounds or the physiologically acceptable salts of the aforementioned compounds.

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.

The Oxidation dye precursors are used in the present Invention preferably in an amount of 0.005 to 20 wt .-%, preferably from 0.05 to 5 wt .-% and particularly preferably from 0.1 to 5 wt .-%, in each case based on the ready-to-use oxidation colorant, used.

there become developer components and coupler components in general used in about molar amounts to each other. If also the molar use has proved to be useful, so is a certain excess of individual oxidation dye precursors not detrimental, leaving developer components and coupler components in a molar ratio of 1 to 0.5 to 1 to 3, in particular 1 to 1 to 1 to 2, can stand.

The compositions according to the invention furthermore comprise compulsorily in the oxidizing agent preparation (B) in a cosmetic carrier sodium chlorite (NaClO ₂ ) as oxidizing agent, preferably in place of hydrogen peroxide.

Especially preferred agents are characterized by being free of Are hydrogen peroxide.

It may be preferred in the context of the present invention that the cosmetic Carrier of the oxidizing agent preparation (B) aqueous, alcoholic or watery-alcoholic. In another preferred embodiment is the cosmetic carrier but a powdered carrier, preferably Dedusted, so that the oxidizing agent preparation (B) as a powder or formulated as an anhydrous paste.

suitable powdery carriers are, for example, silicates or other mineral carriers as well as celluloses and others polysaccharide polymers.

In the case of the formulation as an anhydrous paste, it has proved to be particularly preferred when the preparation is C at least one non-hydroxylated fatty acid ester having a melting point of at most 50 ° C, in particular of at most 30 ° C, and / or at least one C ₁₀ -C ₃₀ Fatty acid having at least one additional hydroxy group and / or a derivative thereof.

Esters of non-hydroxylated C ₆ -C ₃₀ -alkyl monocarboxylic acids with C ₂ -C ₃₀ -monoalcohols are preferably suitable according to the invention as fatty acid esters. The monoesters of the fatty acids with monoalcohols having 2 to 24 carbon atoms are preferred. Examples of fatty acid components used in the esters are caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic acid and Erucic acid and their technical mixtures, the z. As in the pressure splitting of natural fats and oils, obtained in the oxidation of aldehydes from the Roelen oxo synthesis or the dimerization of unsaturated fatty acids. Examples of the fatty alcohol moieties in the esters are isopropyl alcohol, caproic alcohol, capryl alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachyl alcohol, gadoleyl alcohol, Behenyl alcohol, erucyl alcohol and brassidyl alcohol and their technical mixtures, the z. As in the high-pressure hydrogenation of technical methyl esters based on fats and oils or aldehydes from the Roelen oxo synthesis and as a monomer fraction the dimerization of unsaturated fatty alcohols incurred. Especially preferred according to the invention are isopropyl myristate (Rilanit IPM), isononanoic acid C16-18-alkyl ester (Cetiol SN), 2-ethylhexyl palmitate (Cegesoft 24), stearic acid 2-ethylhexyl ester (Cetiol 868), cetyl oleate, coconut fatty alcohol caprinate / caprylate (Cetiol LC), n-butyl stearate, oleyl erucate (Cetiol J 600), isopropyl palmitate (Rilanit IPP), oleyl oleate (Cetiol), lauric acid hexyl ester (Cetiol A), myristyl myristate (Cetiol MM), cetearyl isononanoate (Cetiol SN), oleic acid decyl ester (Cetiol V).

According to the invention preferred Means are characterized in that the oxidizing agent preparation (B) Sodium chlorite in a proportion of 0.05 to 15 wt .-%, preferably from 0.1 to 10% by weight, and more preferably from 0.5 to 6% by weight, respectively based on the total weight of the ready-to-use agent.

As has already been suggested, goes through the exchange of hydrogen peroxide in favor of sodium chlorite as the oxidizing agent in the colorant also the damage to the keratin fiber back. Usually, the oxidative Dye caused damage to the keratin Fiber can be detected at the cysteinic acid fraction in the fiber. In the course of oxidative treatment, disulfide bridges become split within the fiber and the resulting thiol functionalities of the cysteine is converted into cysteic acid units. Of the Resulting cysteine in the keratinic fiber is measurable by means of near-infrared spectroscopy (NIR) and can be so be used to quantify the fiber damage.

invention Oxidizing agent preparations (B) are preferably aqueous, flowable oxidizing agent preparations. there preferred preparations are characterized in that the flowable oxidizing agent - related on their weight - 40 to 98 wt .-%, preferably 60 to 95 wt .-%, particularly preferably 65 to 90 wt .-% water.

Farther it has proved to be advantageous if the oxidizing agent preparation (B) additionally at least one stabilizer selected from phosphonic acids.

• a) geminale Diphosphonsäuren wie 1-Hydroxyethan-1,1-diphosphonsäure (HEDP), deren höhere Homologe mit bis zu 8 Kohlenstoffatomen sowie Hydroxy- oder Aminogruppen-haltige Derivate hiervon und 1-Aminoethan-1,1-diphosphonsäure, deren höhere Homologe mit bis zu 8 Kohlenstoffatomen sowie Hydroxy- oder Aminogruppen-haltige Derivate sowie
• b) Aminophosphonsäuren wie Ethylendiamintetra(methylenphosphonsäure)(EDTMP), Diethylen-triaminpenta(methylenphosphonsäure)(DTPMP) sowie deren höhere Homologe, oder Nitrilotri(methylenphosphonsäure).

In the context of the present invention, preference is given to stabilizers which contain a phosphonic acid unit as a common chemical group. Preferably, they are used individually or in admixture with each other:

• a) 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 whose higher homologues with up to 8 carbon atoms and hydroxy- or amino-containing derivatives and
• b) aminophosphonic acids such as ethylenediaminetetra (methylenephosphonic acid) (EDTMP), diethylenetriaminepenta (methylenephosphonic acid) (DTPMP) and their higher homologs, or nitrilotri (methylenephosphonic acid).

at the alkaline required according to the invention pH values of the treatment solutions are these stabilizers 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 Stabilizers are phosphonates, preferably hydroxyalkane or aminoalkane phosphonates and in particular 1-hydroxyethane-1,1-diphosphonate (HEDP) or its Di- or tetrasodium salt and / or ethylenediamine tetramethylene phosphonate (EDTMP) or its hexasodium salt and / or Diethylentriaminpentamethylenphosphonat (DTPMP) or its hepta- or octasodium salt.

Farther has been found to be preferred according to the invention is, if the oxidation preparation (B) additionally at least contains a polymeric thickener.

It can be both organic and purely inorganic, polymeric Thickening agents are used.

According to one particularly 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.

Particularly according to the invention preferred polymeric thickeners are characterized in that the polymeric thickener is selected from anionic Polymers which contain at least one acrylic acid monomer as building block and / or a methacrylic acid unit.

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 Rheothik11-80 in the trade is available.

Within this embodiment, it may further be preferred 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 non-ionic monomers are acrylamide, methacrylamide, acrylic esters, Methacrylic acid 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. An especially 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.

It may also be preferred according to the invention, when the anionic copolymers as a monomer acrylic ester Contain with longer-chain alkyl radicals. Such copolymers For example, under the INCI name Acrylates / C10-30Allkylacrylate Crosspolymer sold. Exemplary commercial products of such copolymers are Carbopol ETD 2020, Carbopol Ultrez 20 and Pemulen TR-1 and TR-2 from Lubrizol.

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 wholly or partly as 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.

Further preferred anionic copolymers containing sulfonic acid groups Monomers are copolymers with the ammonium salt of 2-acrylamido-2,2-dimethyl-ethylsulfonic acid. Preferred representatives of these copolymers are, for example, the copolymers of ammonium 2-acrylamido-2,2-dimethyl-ethylsulfonate with vinylpyrrolidinone or with ethoxylated fatty alcohol methylacrylic acid esters, as Beheneth-25 methacrylate, under the trade name Aristoflex AVC or Aristoflex HMB are sold by Clariant.

Also polymers of maleic anhydride and methyl vinyl ether, especially those with Vernetzun are preferred thickeners. A 1,9-decadiene cross-linked 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 a second 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 constructed from acrylic acid, methacrylic acid or derivatives thereof have proven 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 (I) aufgeführten Monomereinheiten sowie nicht-ionogenen 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 (I),

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 (I) 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 (I) 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 as in the case of the homopolymers described above, be crosslinked. An inventively preferred copolymer 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 third preferred embodiment, naturally occurring thickening agents 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 available under the trade names Jaguar ^® HP8, Jaguar HP60, Jaguar HP120, Jaguar DC 293 and Jaguar HP105 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.

According to the invention, however, the oxidizing agent preparation can also be used together with a catalyst be applied to the hair, which activates the oxidation of the dye precursors. Such catalysts are for. As certain enzymes, iodides, quinones or metal salts.

In a preferred embodiment of the present invention contains the oxidizing agent preparation (B) in addition at least one salt of a transition metal selected from salts of cerium, vanadium, manganese, iron, cobalt, nickel, copper and zinc.

Suitable transition metal ions are, for example, Zn ²⁺ , Cu ²⁺ , Fe ²⁺ , Fe ³⁺ , Mn ²⁺ , Mn ⁴⁺ , Ce ⁴⁺ , V ³⁺ , Co ²⁺ , and Ni ²⁺ . Particularly suitable are Zn ²⁺ , Fe ²⁺ , Fe ³⁺ , 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, the coloring effect can be specifically influenced. Particularly preferred metal salts are manganese (II) chloride, manganese (II) bromide, copper (II) sulfate, iron (II) sulfate, iron (III) chloride. Particularly preferred compositions contain these metal salts at 0.01 to 10% by weight. , preferably 0.1 to 5 wt .-%, based on the total weight of the ready-to-use agent.

Preferably is the oxidizing agent preparation (B) and / or the dyeing preparation made up as a flowable preparation. The flowable preparations (A) and / or (B) is preferably further added at least one surfactant, wherein the surfactant from anionic, cationic, zwitterionic, amphoteric and nonionic Surfactants, but preferably selected from anionic surfactants is. These substances will be described in detail below.

A preferred embodiment of the present invention Accordingly, characterized in that the oxidizing agent preparation (B) additionally contains at least one anionic surfactant.

• – 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 Talgfettsäuremonoglycerid sowie deren Ethylenoxidaddukte mit Schwefeltrioxid oder Chlorsulfonsäure in Form ihrer Natriumsalze. Vor-zugsweise 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 fatty acid alkylene glycol esters of the formula RC (O) O (alkO) _n SO ₃ H, in the R for a linear or branched, aliphatic, saturated and / or unsaturated alkyl radical having 6 to 22 carbon atoms, alk for 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. Preference is given to using monoglyceride sulfates of the formula (MGS) in which R is a linear alkyl radical having 8 to 18 carbon atoms.

Especially preferred anionic surfactants of the oxidation preparation (B) 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.

A particularly preferred embodiment of the present invention is given when the dyeing preparation (A) additionally contains, as anionic surfactant, at least one ether carboxylic acid of the formula RO (CH ₂ CH ₂ O) _x CH ₂ COOH and / or one of its physiologically tolerable salts, where R is a C ₁₀ -C ₂₀ alkyl chain and x = 0 or a number from 1 to 16.

In the dyeing preparation (A) preferred anionic surfactants of the type of ether carboxylic acids are ether carboxylic acids of the formula RO (CH ₂ CH ₂ O) _x CH ₂ COOH and / or one of their physiologically acceptable salts, wherein R is a C ₁₂ -C ₁₄ alkyl chain and x is a number from 4 to 6. An example of such a preferred ether carboxylic acid is known by the INCI name Sodium Laureth-5 Carboxylate and is sold under the tradename Akypo Soft 45.

The anionic surfactants are in the inventive Agents preferably in amounts of 0.05 to 15 wt .-%, based on the entire ready to use means included. Amounts of 0.1 to 10 wt .-% are particularly preferred.

Furthermore, it has proved to be advantageous if at least the dyeing preparation (A) additionally contains nonionic surfactants selected from C ₈ -C ₂₀ -alkyl glucosides.

A particular embodiment of the present invention is therefore an agent which is characterized in that the dyeing preparation (A) additionally contains at least one nonionic surfactant which is selected from C ₈ -C ₂₀ -alkyl glucosides.

Particularly suitable nonionic C ₈ -C ₂₀ -alkyl glucosides are C ₈ -C ₂₂ -alkyl mono- and oligoglycosides and their ethoxylated analogs. These homologs may contain on average up to 10 ethylene oxide and / or propylene oxide units per alkyl glycoside unit. 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- bis C₁₆-Alkylgruppen oder
• – im Wesentlichen aus C₁₂- bis C₁₆-Alkylgruppen oder
• – im Wesentlichen aus C₁₆ bis C₁₈-Alkylgruppen besteht.

Particular preference is given to those alkylpolyglucosides 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 to C ₁₆ alkyl groups or
• Substantially from C ₁₂ to C ₁₆ alkyl groups or
• - Consists essentially of C ₁₆ to C ₁₈ alkyl groups.

These compounds are characterized in that any mono- or oligosaccharides can be used as the sugar unit Z. Usually, sugars with 5 or 6 carbon atoms and the corresponding oligosaccharides are used. 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 Alkyl polyglucosides which can be used according to the invention contain on average 1.1 to 5 sugar units. alkylpolyglucosides with x values of 1.1 to 2.0 are preferred. Very particularly preferred are alkylglucosides in which x is 1.1 to 1.8.

One An example of such an alkylpolyglucoside is the compound with the INCI name Lauryl Glucoside, which under the trade name Plantcare 1200 UP sold by Cognis.

The agents according to the invention can additionally contain at least one substantive dye.

Farther the agents according to the invention can be at least contain a direct dye. This is about Dyes that grow directly on the hair and no oxidative Need process for color training. Substantive Dyes are usually nitrophenylenediamines, nitroaminophenols, Azo dyes, anthraquinones or indophenols.

The substantive dyes are each preferably in an amount from 0.0001 to 0.2% by weight, preferably from 0.001 to 0.1% by weight, respectively based on the entire application preparation used. The total amount of substantive dyes is preferably at most 0.1% by weight.

there it may be irrelevant whether the direct dye in the Dyeing preparation (A) or the oxidation preparation (B) is incorporated. Preference is given to the substantive dye in incorporated the emulsion preparation (A).

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

Anionic substantive dyes:

Particularly suitable anionic direct dyes are 6-hydroxy-5 - [(4-sulfophenyl) azo] -2-naphthalenesulfonic acid disodium salt (CI 15.985, Food Yellow No. 3, FD & C Yellow No. 6), 2,4-dinitro-1 naphthol-7-sulfonic acid disodium salt (CI 10,316, Acid Yellow 1, Food Yellow No. 1), 2- (indan-1,3-dion-2-yl) quinoline-x, x-sulfonic acid (mixture of mono- and di-sodium Disulfonic acid) (CI 47,005, D & C Yellow No. 10, Food Yellow No. 13, Acid Yellow 3, Yellow 10), 4 - ((4-amino-3-sulfophenyl) azo) benzenesulfonic acid disodium salt (CI 13,015, Acid Yellow 9 ), 5-hydroxy-1- (4-sulfophenyl) -4 - [(4-sulfophenyl) azo] pyrazole-3-carboxylic acid trisodium salt (CI 19.140, Food Yellow No. 4, Acid Yellow 23), 3 - [( 4-phenylamino) phenyl] azobenzenesulfonic acid, sodium salt (CI 13.065, Ki406, Acid Yellow 36), 9- (2-carboxyphenyl) -6-hydroxy-3H-xanthen-3-one (CI 45, 350; Acid Yellow 73, D & C Yellow No 8), 5 - [(2,4-dinitrophenyl) amino] -2-phenylaminobenzenesulfonic acid, sodium salt (CI 10,385; Acid Orange 3), 4 - [(2,4-dihydroxyphenyl) azo] ben cosulfonic acid sodium salt (CI 14,270; Acid Orange 6), 4 - [(2-hydroxynaphth-1-yl) azo] benzenesulfonic acid, sodium salt (CI 15.510, Acid Orange 7), 4 - [(2,4-dihydroxy-3 - [(2,4-dimethylphenyl azo] phenyl) azo] benzenesulfonic acid sodium salt (CI 20.170; Acid Orange 24), 4-hydroxy-3 - [(2-methoxyphenyl) azo] -1-naphthalenesulfonic acid, sodium salt (CI 14.710, Acid Red 4), 4-hydroxy- 3 - [(4-sulfonaphth-1-yl) azo] -1-naphthalenesulfonic acid disodium salt (CI 14,720; Acid Red No. 14), 6-hydroxy-5 - [(4-sulfonaphth-1-yl) azo] - 2,4-naphthalenedisulfonic acid trisodium salt (CI 16,255; Ponceau 4R; Acid Red 18), 3-hydroxy-4 - [(4-sulfonaphth-1-yl) azo] -2,7-naphthalenedisulfonic acid trisodium salt (CI 16.185, Acid Red 27), 8-amino-1-hydroxy-2- (phenylazo) -3,6-naphthalenedisulfonic acid disodium salt (CI 17,200, Acid Red 33, Red 33), 5- (acetylamino) -4-hydroxy-3- [ (2-methylphenyl) azo] -2,7-naphthalenedisulfonic acid disodium salt (CI 18.065; Acid Red 35), 2- (3-hydroxy-2,4,5,7-tetraiodo-dibenzopyran-6-one-9-yl ) benzoic acid disodium salt (CI 45.430, Acid Red 51), N- [6- (diethylam ino) -9- (2,4-disulfophenyl) -3H-xanthen-3-ylidene] -N-ethyl-urethane-ammonium hydroxide, inner salt, sodium salt (CI 45, 100; Acid Red 52), 8 - [(4- (phenylazo) phenyl) azo] -7-naphthol-1,3-disulfonic acid disodium salt (CI 27.290; Acid Red 73), 2,4 ', 5', 7 ' Tetrabromo-3 ', 6'-dihydroxyspiro [isobenzofuran-1 (3H), 9' - [9H] xanthene] -3-one disodium salt (CI 45.380, Acid Red 87), 2,4,5 ', 7'- Tetrabromo-4,5,6,7-tetrachloro-3 ', 6'-dihydroxyspiro [isobenzofuran-1 (3H), 9' [9H] xanthene] -3-one disodium salt (CI 45.410, Acid Red 92), 3 ', 6'-dihydroxy-4', 5'-diiodospiro [isobenzofuran-1 (3H), 9 '(9H) xanthene] -3-one disodium salt (CI 45425; Acid Red 95), 2-hydroxy-3- ((2-hydroxynaphth-1-yl) azo) -5-nitrobenzenesulphonic acid sodium salt (CI 15,685; Acid Red 184), 3-hydroxy-4- (3-methyl-5-oxo-1-phenyl-4,5-dihydroxy) 1H-pyrazol-4-ylazo) naphthalene-1-sulfonic acid sodium salt, chromium complex (Acid Red 195), 3-hydroxy-4 - [(4-methyl-2-sulfonphenyl) azo] -2-naphthalenecarboxylic acid calcium salt (CI 15.850: 1, Pigment Red 57: 1), 3 - [(2.4 Dimethyl-5-sulfophenyl) azo] -4-hydroxy-1-naphthalenesulfonic acid disodium salt (CI 14,700, Food Red No. 1, Ponceau SX, FD & C Red No. 4), 1,4-bis - [(2 -sulfo-4-methylphenyl) amino] -9,10-anthraquinone disodium salt (CI 61.570; Acid Green 25), bis [4- (dimethylamino) phenyl] - (3,7-disulfo-2-hydroxynaphth-1) yl) carbenium inner salt, sodium salt (CI 44.090, Food Green No. 4, Acid Green 50), bis- [4- (diethylamino) phenyl] (2,4-disulfophenyl) carbenium inner salt, sodium salt (2: 1 (CI 42.045, Food Blue No. 3, Acid Blue 1), bis [4- (diethylamino) phenyl] (5-hydroxy-2,4-disulfophenyl) carbenium inner salt, calcium salt (2: 1) (CI 42.051; Acid Blue 3), N- [4 - [(2,4-disulfophenyl) - [4- [ethyl (phenylmethyl) amino) phenyl] methylene] -2,5-cyclohexadien-1-ylidene] -N-ethylbenzenemethanamine hydroxide, inner salt, sodium salt (CI 42.080, Acid Blue 7), (2-sulfophenyl) di [4- (ethyl (4-sulfop henyl) methyl) amino) phenyl] carbenium disodium salt betaine (CI 42,090; Acid Blue 9; FD & C Blue No. 1), 1-amino-4- (phenylamino) -9,10-anthraquinone-2-sulfonic acid (CI 62.055, Acid Blue 25), 1-amino-4- (cyclohexylamino) -9,10-anthraquinone-2-sulfonic acid sodium salt (CI 62045; Acid Blue 62), 2- (1,3-dihydro-3-oxo-5-sulfo-2H-indol-2-ylidene) -2,3-dihydro-3-oxo-1H-indole-5 sulfonic acid disodium salt (CI 73.015, Acid Blue 74), 9- (2-carboxyphenyl) -3 - [(2-methylphenyl) amino] -6 - [(2-methyl-4-sulfophenyl) amino] xanthylium inner salt , Sodium salt (CI 45.190; Acid Violet 9), 1-hydroxy-4 - [(4-methyl-2-sulfophenyl) amino] -9,10-anthraquinone sodium salt (CI 60,730, D & C Violet No. 2, Acid Violet 43 ), Bis [3-nitro-4 - [(4-phenylamino) -3-sulfophenylamino] phenyl] sulfone (CI 10.410; Acid Brown 13), 5-amino-4-hydroxy-6 - [(4- nitrophenyl) azo] -3- (phenylazo) -2,7-naphthalenedisulfonic acid disodium salt (CI 20,470, Acid Black 1), 3-hydroxy-4 - [(2-hydroxynaphth-1-yl) azo] -7-nitro 1-naphthalenesulfonic acid-chromium complex (3: 2) (CI 15,711, Acid Black 52), 4- (acetylamino) -5-hydroxy-6 - [(7-sulfo-4 - [(4-sulfophenyl) azo] naphthenyl] 1-yl) azo] - 1,7-naphthalenedisulfonic acid tetrasodium salt (CI 28,440; Food Black no. 1), 3 ', 3 ", 5', 5" -tetrabromophenolsulfonephthalein (bromophenol blue), 3, 3 ', 3 ", 4,5,5', 5", 6-octabromophenolsulfonephthalein (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 and Acid Black 52 known compounds.

When cationic substantive dyes are in particular 9- (dimethylamino) benzo [a] phenoxazine-7-ium chloride (C.I. 51,175; Basic Blue 6), di- [4- (diethylamino) phenyl] [4- (ethylamino) naphthyl] carbenium chloride (C.I. 42,595; Basic Blue 7), di (4- (dimethylamino) phenyl) - (4- (methylphenylamino) naphthalen-1-yl) carbenium chloride (C.I. 42,563; Basic Blue 8), 3,7-di- (dimethylamino) -phenothiazine-5-ium chloride (C.I. 52.015 Basic Blue 9), di- [4- (dimethylamino) phenyl] [4- (phenylamino) naphthyl] carbenium chloride (C.I. 44.045; Basic Blue 26), 2 - [(4- (ethyl (2-hydroxyethylamino) phenyl) azo] -6-methoxy-3-methylbenzothiazolium methylsulfate (C.I. 11,154; Basic Blue 41), 8-amino-2-bromo-5-hydroxy-4-imino-6 - [(3- (trimethylammonio) phenyl) amino] -1 (4H) -naphthalenone chloride (C.I. 56,059; Basic Blue No. 99), bis [4- (dimethylamino) phenyl] - [4- (methylamino) phenyl] carbenium chloride (C.I. 42,535; Basic Violet 1), tri- (4-amino-3-methylphenyl) carbenium chloride (C.I. 42,520, Basic Violet 2), tri- [4- (dimethylamino) -phenyl] carbenium chloride (C.I. 42,555; Basic Violet 3), 2- [3,6- (diethylamino) dibenzopyranium-9-yl] benzoic acid chloride (C.I. 45,170, Basic Violet 10), di- (4-aminophenyl) (4-amino-3-methylphenyl) carbenium chloride (C.I. 42.510 Basic Violet 14), 1,3-bis - [(2,4-diamino-5-methylphenyl) azo] -3-methylbenzene (C.I. 21,010; Basic Brown 4), 1 - [(4-aminophenyl) azo] -7- (trimethylammonio) -2-naphthol chloride (C.I. 12,250, Basic Brown 16), 1 - [(4-amino-2-nitrophenyl) azo] -7- (trimethylammonio) -2-naphthol chloride, 1 - [(4-amino-3-nitrophenyl) azo] -7- (trimethylammonio) -2-naphthol-chloride (C.I. 12,251; Basic Brown 17), 3 - [(4-amino-2,5-dimethoxyphenyl) azo] -N, N, N-trimethylbenzylaminium chloride (C.I. 12.605, Basic Orange 69), 3,7-diamino-2,8-dimethyl-5-phenylphenazinium chloride (C.I. 50,240, Basic Red 2), 1,4-dimethyl-5 - [(4- (dimethylamino) phenyl) azo] -1,2,4-triazolium chloride (C.I. 11,055; Basic Red 22), 2-hydroxy-1 - [(2-methoxyphenyl) azo] -7- (trimethylammonio) naphthalene chloride (C.I. 12,245; Basic Red 76), di- [4- (dimethylamino) phenyl] iminomethane hydrochloride (C.I. 41,000, Basic Yellow 2), 2- [2 - ((2,4-dimethoxyphenyl) amino) ethenyl] -1,3,3-trimethyl-3H-indol-1-ium chloride (C.I., 48,055; Basic Yellow 11), 3-methyl-1-phenyl-4 - [(3- (trimethylammonio) phenyl) azo] pyrazol-5-one chloride (C.I. 12.719; Basic Yellow 57), bis [4- (diethylamino) phenyl] phenylcarbenium hydrogensulfate (1: 1) (C.I., 42.040; Basic Green 1), di (4- (dimethylamino) phenyl) phenylmethanol (C.I. 42,000, Basic Green 4), 1- (2-morpholiniumpropylamino) -4-hydroxy-9,10-anthraquinone methylsulfate, 1 - [(3- (dimethylpropylaminium) propyl) amino] -4- (methylamino) -9,10-anthraquinone chloride and direct dyes containing a heterocycle, the 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-hydro xyethyl) 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, 1,4-di - [(2-hydroxyethyl) amino] -9,10-anthraquinone (CI 61.545, Disperse Blue 23 ), 1 - [(2-hydroxyethyl) amino] -4-methylamino-9,10-anthraquinone (CI 61,505, Disperse Blue 3), 2 - [(2-aminoethyl) amino] -9,10-anthraquinone (HC Orange 5), 1-amino-4-hydroxy-9,10-anthraquinone (CI 60.710, Disperse Red 15), 1-hydroxy-4 - [(4-methyl-2-sulfophenyl) amino] -9,10-anthraquinone, 7-Beta-D-glucopyranosyl-9,10-dihydro-1-methyl-9,10-dioxo-3,5,6,8-tetrahydroxy-2-anthracenecarboxylic acid (CI 75,470, Natural Red 4), 1 - [( 3-aminopropyl) amino] -4-methylamino-9,10-anthraquinone (HC Blue 8), 1 - [(3-aminopropyl) amino] -9,10-anthraquinone (HC Red 8), 1,4-diamino- 2-methoxy-9,10-anthraquinone (CI 62.015, Disperse Red 11, Solvent Violet No. 26), 1,4-dihydroxy-5,8-bis [(2-hydroxyethyl) amino] -9,10-anthraquinone ( CI 62,500, Disperse Blue 7, Solvent Blue No. 69), 1,4-diamino-9,10-anthraquinone (CI 61.100, Disperse Violet 1), 1-amino-4- (methylamino) -9,10-anthraquinone ( CI 61,105, Disperse Viol et 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-hydroxyethyl) amino] -2,5-cyclohexadiene-1,4-dione (HC Green 1), 5-hydroxy-1,4-naphthoquinone (CI 75,500, Natural Brown 7), 2-hydroxy-1,4-naphthoquinone (CI 75,480, Natural Orange 6), 1,2-dihydro-2- (1,3-dihydro-3-oxo-2H-indol-2-ylidene) 3H-indol-3-one (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-pyrazole sulfate (1: 1), hydrate (1: 1).

Suitable neutral azo dyes are in particular:
1- [di (2-hydroxyethyl) amino] -3-methyl-4 - [(4-nitrophenyl) azo] benzene (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, 2 - {[4- (acetylamino) phenyl] azo} -4-methylphenol (CI 11855, Disperse Yellow 3), 4 - [(4-nitrophenyl ) azo] aniline (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.

The ready-to-use colorant from dyeing preparation (A) and oxidizing agent preparation (B) preferably have a pH ranging from 6 to 12. Particularly preferred is the application in an alkaline environment. The application temperatures can in a range between 15 and 40 ° C. After a Acting time of 2 to 45, preferably 5 to 30 minutes is the Dye removed by rinsing off the hair. The washing with a shampoo is eliminated if a strong surfactant-containing carrier was used.

According to the invention preferred Bleaching agents for keratinic fibers are characterized in that they have an alkaline pH. Another preferred Embodiment of the present invention is that the ready-to-use agent has a pH between 7.0 and 12.0, preferably between 8.0 and 11.0, more preferably between 9.0 and 10.5 owns.

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. Acidifying agents preferred according to the invention 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-dimethyl-ethanolamine, 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 and 2-amino-2-methylpropane-1,3-diol. A particularly preferred alkanolamine is monoethanolamine.

It but has been within the scope of the investigations of the present invention found that preferred according to the invention characterized in that they additionally an inorganic Contain alkalizing agent. The invention, inorganic alkalizing agent is 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.

The Contain compositions of the invention the alkalizing agents are preferably used in amounts of from 0.2 to 25% by weight, in particular 0.5 to 10 wt .-%.

Preferably is the flowable preparations (A) and / or (B) further in addition to those mentioned above Surfactants an emulsifier or a surfactant added, these surface-active substances depending on the field of application referred to as surfactants or as emulsifiers and from cationic, zwitterionic, amphoteric and nonionic Surfactants and emulsifiers are selected. These substances will be described in detail below.

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 the Kokosacyl aminoethylhydroxyethylcarboxymethylglycinat. 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, 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 Fettalkohole 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)glycerinpolyhydroxy-stearat (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 mit Alkoxylierungsgrad von größer als 5, 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 5 bis 30 Ethylenoxid- und/oder Propylenoxid-Einheiten. Bevorzugte Vertreter dieser Klasse sind beispielsweise Nonylphenol + 9 EO und Octylphenol + 8 EO.

Nonionic surfactants in addition to the alkylpolyglucosides already mentioned 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, to fatty acids having 8 to 30 carbon atoms and to 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, to fatty acids having 8 to 30 C Atoms and alkylphenols having 8 to 15 C 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 polyhydroxy stearate (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 with an alkoxylation degree of greater than 5, 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 5 to 30 ethylene oxide and / or propylene oxide units. Preferred representatives of this class are, for example, nonylphenol + 9 EO and octylphenol + 8 EO.

When preferred nonionic surfactants are the alkylene oxide addition products saturated linear fatty alcohols and fatty acids with in each case 2 to 30 moles of ethylene oxide per mole of fatty alcohol or fatty acid. Preparations with excellent properties will also be 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.

at the surfactants, the adducts of ethylene and / or propylene oxide represent fatty alcohols or derivatives of these addition products, can both products with a "normal" homolog distribution as well as those with a narrow homolog distribution become. Under "normal" homolog distribution thereby understood mixtures of homologues, which in the implementation of fatty alcohol and alkylene oxide using alkali metals, Alkali metal hydroxides or alkali metal alcoholates as catalysts receives. Narrow homolog distributions are opposed obtained, for example, when hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or -alkoholate be used as catalysts. The usage of products with restricted homolog distribution may be preferred be.

The nonionic, zwitterionic or amphoteric surfactants in amounts of 0.1 to 45 wt .-%, preferably 1 to 30 wt .-% and completely particularly preferably from 1 to 15% by weight, based on the total amount of the ready-to-use agent.

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 180 and Dehyquart AU-35 are examples for such esterquats.

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

The cationic surfactants are preferred in amounts of from 0.01 to 15% by weight From 0.05 to 10% by weight and most preferably from 0.1 to 5% by weight, based on the total amount of the ready-to-use agent used.

The compositions according to the invention may preferably contain at least one nonionic emulsifier or surfactant having an HLB value of 8 to 18, according to the methods described in US Pat Rompp Lexicon Chemistry (ed. J. Falbe, M. Regitz), 10th edition, Georg Thieme Verlag Stuttgart, New York, (1997), page 1764 , listed definitions. Nonionic emulsifiers or surfactants having an HLB value of 10-15 may be particularly preferred according to the invention.

It It has been found that the addition of ammonium salts of a inorganic or organic acid the positive effect the funds further improved. Such ammonium salts are, for example Ammonium sulfate, ammonium chloride, ammonium bromide, ammonium carbonate, Ammonium carbamate, ammonium formate, ammonium hydrogen citrate, ammonium hydrogen oxalate, ammonium iodide, Ammonium oxalate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, Ammonium sulfamate or ammonium tartrate.

It is preferred when the agent according to the invention the ammonium salt in a proportion of 0.05 to 5 wt .-%, based on the total weight of the agent according to the invention, is added.

One Particularly preferred ammonium salt is ammonium sulfate. A special one Embodiment of the invention By means is given, if the means additionally 0.01 to 3 wt .-%, preferably 0.1 to 1.0 wt .-%, each based on the Total weight of ready-to-use agent containing ammonium sulphate.

Particularly advantageous agents according to the invention contain a care substance for the additional improvement of the hair condition. This additional care substance is preferably selected from vitamins, provitamins and vitamin precursors. Particularly preferred care substances are vitamins, provitamins and vitamin precursors of groups A, B ₃ , B ₅ , B ₆ , C, E, F and H. For reasons of stability, the conditioner is preferably incorporated into the emulsion preparation A.

The agents according to the invention can continue all active substances, additives known to and auxiliaries.

• – nichtionische Polymere wie beispielsweise Vinylpyrrolidinon/Vinylacrylat-Copolymere, Polyvinylpyrrolidinon und Vinylpyrrolidinon/Vinylacetat-Copolymere und Polysiloxane,
• – zwitterionische und amphotere Polymere wie beispielsweise Acrylamidopropyltrimethylammoniumchlorid/Acrylat-Copolymere und Octylacrylamid/Methyl-methacrylat/tert-Butylaminoethylmethacrylat/2-Hydroxypropylmethacrylat-Copolymere,
• – anionische Polymere wie beispielsweise Polyacrylsäuren, vernetzte Polyacrylsäuren, Vinylacetat/Crotonsäure-Copolymere, Vinylpyrrolidinon/Vinylacrylat-Copolymere, Vinylacetat/Butylmaleat/Isobornylacrylat-Copolymere, Methylvinylether/Malein-säureanhydrid-Copolymere und Acrylsäure/Ethylacrylat/N-tert.Butyl-acrylamid-Terpolymere,
• – Verdickungsmittel wie Agar-Agar, Guar-Gum, Alginate, Xanthan-Gum, 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 Maleinsäure und Milchsäure,
• – Proteinhydrolysate, insbesondere Elastin-, Kollagen-, Keratin-, Milcheiweiß-, Sojaprotein- und Weizenproteinhydrolysate, deren Kondensationsprodukte mit Fettsäuren sowie quaternisierte Proteinhydrolysate,
• – Parfümöle,
• – Cyclodextrine,
• – Komplexbildner wie EDTA,
• – Lösungsmittel und -vermittler wie Ethanol, Isopropanol, Ethylenglykol, Propylenglykol, Glycerin, Dimethylisosorbid und Diethylenglykol,
• – Entschäumer wie Silikone,
• – Farbstoffe zum Anfärben des Mittels,
• – Antischuppenwirkstoffe wie Piroctone Ölamine, Zink Omadine und Climbazol,
• – Lichtschutzmittel, insbesondere derivatisierte Benzophenone, Zimtsäure-Derivate und Triazine,
• – Substanzen zur Einstellung des pH-Wertes, wie beispielsweise übliche Säuren, insbesondere Genusssäuren und Basen,
• – Wirkstoffe wie Allantoin, Pyrrolidinoncarbonsäuren und deren Salze sowie Bisabolol,
• – Cholesterin,
• – Konsistenzgeber wie Zuckerester, Polyolester oder Polyolalkylether,
• – weitere 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.

Other active ingredients, auxiliaries and additives are, for example

• Nonionic polymers such as vinylpyrrolidinone / vinyl acrylate copolymers, polyvinylpyrrolidinone and vinylpyrrolidinone / vinyl acetate copolymers and polysiloxanes,
• Zwitterionic and amphoteric polymers, for example acrylamidopropyltrimethylammonium chloride / acrylate copolymers and octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers,
• Anionic polymers such as, for example, polyacrylic acids, crosslinked polyacrylic acids, vinyl acetate / crotonic acid copolymers, vinylpyrrolidinone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers
• Thickeners such as agar-agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, linseed gums, dextrans, cellulose derivatives, e.g. 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 maleic acid and lactic acid,
• 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,
• - cyclodextrins,
• - complexing agents such as EDTA,
• Solvents and mediators, such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol, dimethyl isosorbide and diethylene glycol,
• Defoamers like silicones,
• Dyes for staining the agent,
• Antidandruff active ingredients such as Piroctone Ölamine, Zink Omadine and Climbazole,
• - light stabilizers, 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 allantoin, pyrrolidinonecarboxylic acids and their salts, and bisabolol,
• - cholesterol,
• Bodying agents such as sugar esters, polyol esters or polyol alkyl ethers,
• - other 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.

The Active ingredients, auxiliaries and additives are each preferred in one proportion from 0.0001 to 25% by weight, preferably 0.0005 to 15% by weight, respectively based on the total weight of the invention By means of, is added.

With regard to further optional components and the amounts of these components used, reference is expressly made to the relevant manuals known to the person skilled in the art, eg. B. Kh. Schrader, bases and formulations of the cosmetics, 2nd edition, Hüthig book publishing house, Heidelberg, 1989 , referenced.

It It has been shown to be for reasons of storage stability may be appropriate, the ready-to-use colorant only immediately before use by mixing components to prevent potential instability.

A preferred dosage form of the invention By means of a packaging 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 Carrier contains sodium chlorite, and at least a container (II) containing a dyeing preparation (A) in an aqueous-cosmetic carrier contains at least one oxidation dye precursor.

Under Container is in the context of the present invention, an envelope understood that in the form of an optionally resealable Bottle, a can, a bag, a sachet or similar Envelopes are present.

It may be preferred if the oxidizing agent preparation (B) in turn is divided into two separate containers (Ia) and (Ib), wherein a container (Ia) a powdery, optionally as Molded pressed preparation (BP) containing sodium chlorite and optionally further solids, and contains Container (Ib) a flowable aqueous, alcoholic or aqueous-alcoholic preparation contains.

The actual oxidizing agent preparation (B) is prepared by mixing the contents of the containers (Ia) and (Ib) produced. Conveniently, the powdered preparation, optionally in tablet form, in provided a bag or sachet-like container, while the container (Ib) is preferably a resealable one Bottle represents. This will ensure that the Content of the container (Ia) added to the contents of the container (Ib) can be and after re-closure of the container (Ib) an intimate Mixing of the two preparations achieved by shaking can be.

Farther it may be particularly advantageous according to the invention when said kit of parts is at least one more hair treatment agent contained in a separate container, in particular a Conditioning.

In addition, the packaging unit application aids, such as combs, brushes or brushes, per personal protective clothing, especially one-way gloves, and optionally include instructions for use.

Regarding the preferred embodiments of the Dyeing preparation (A) and the oxidizing agent preparation (B) apply the above statements of the preceding subject invention.

One Another object of the present invention is a method for coloring human hair, wherein a means by Mixing at least one oxidizing agent preparation (B), containing sodium chlorite, and at least one coloring preparation (A) containing at least one oxidation dye precursor the ready-to-use agent 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 rinsed with water and / or a commercial shampoo becomes.

in the The scope of this article of the present invention apply mutatis mutandis mutandis the above statements analogously.

One Another object of the present invention is finally the cosmetic, non-therapeutic use of a coloring agent for keratinic fibers, containing in a cosmetic Carrier sodium chloride as an oxidizing agent for reduction fiber damage in oxidative staining.

in the The scope of this article of the present invention apply mutatis mutandis mutandis the above statements analogously.

• * enthaltend 1,4 Gew.-% 3-Aminophenol, 5,7 Gew.-% 1,4-Diamino-2-methylbenzolsulfat, 46,7 Gew.-% 1-(2-Hydroxyethyl)-4,5-diaminopyrazolsulfat, 7,7 Gew.-% Bis-(5-Amino-2-hydroxyphenyl)methan Dihydrochlorid, 28,7 Gew.-% 5-Amino-2-methylphenol sowie 9,7 Gew.-% pyrogene Kieselsäure, jeweils bezogen auf das Gesamtgewicht des Färbepulvers.

1.2 Oxidationszubereitungen (B): Rohstoff Gew.-% V1 E1 E2 Kaliumdihydrogenphosphat --- 0,07 0,07 Natriumdihydrogenphosphat --- 0,21 0,21 Ammoniak, 25% 0,65 --- --- Dipicolinsäure 0,10 --- --- Dinatriumpyrophosphat 0,03 --- --- DOW CORNING DB 110 A 0,07 --- --- Turpinal SL 1,50 1,50 1,50 Texapon NSO 2,00 2,00 2,00 Mangan(II)chlorid --- 0,50 0,50 Aculyn 33A 12,00 12,00 12,00 Natriumchlorit --- 3,00 6,00 Wasserstoffperoxid, 50% 12,0 --- --- Wasser ad 100 ad 100 ad 100 Eingesetzte Rohstoffe Lanette D C₁₆-C₁₈-Fettalkohol (INCI-Bezeichnung: Cetearyl alcohol) (Cognis) Lorol tech. C₁₂-C₁₈-Fettalkohol (INCI-Bezeichnung: Coconut alcohol) (Cognis) Eumulgin B1 C₁₆-C₁₈-Fettalkohol, ethoxyliert (12 EO) (INCI-Bezeichnung: Ceteareth- 12) (Cognis) Eumulgin B2 C₁₆-C₁₈-Fettalkohol, ethoxyliert (20 EO) (INCI-Bezeichnug: Ceteareth- 20) (Cognis) Akypo Soft 45HP C₁₂-C₁₄-Alkylether, ethoxyliert (4,5 EO) Carbonsäure, Natriumsalz (ca. 21%, INCI-Bezeichnung: Sodium Laureth-5 Carboxylate, Aqua) (KAO) Texapon K14 S Special C₁₂-C₁₄-Alkylethersulfat, ethoxyliert (3 EO), Natriumsalz (ca. 27%, INCI Bezeichnung: Sodium Myreth Sulfate, Aqua) (Cognis) Plantacare 1200 UP C₁₂-C₁₄-Alkylether glycosid (ca. 50–53% Aktivsubstanz: INCI Bezeichnung: Lauryl Glucoside) (Cognis) Produkt W 37194 Copolymer aus Acrylsäure, Natriumsalz und Trimethylammoniopropyl- acrylamidchlorid (ca. 20%, INCI-Bezeichnung: Acrylamidopropyl- trimonium Chloride/Acrylates Copolymer, Aqua) (Stockhausen) Turpinal SL 1-Hydroxyethan-1,1-diphosphonsäure (ca. 60% Aktivsubstanzgehalt; INCI-Bezeichnung: Etidronic Acid, Aqua) (Solutia) Natriumsilikat 40/42 Natronwasserglas Texapon NSO Laurylethersulfat, Natriumsalz (ca. 27,5% Aktivsubstanz; INCI Bezeichnung: Sodium Laureth Sulfate) (Cognis) Aculyn 33 Acrylpolymer (ca. 28% Festkörper in Wasser; INCI-Bezeichnung: Acrylates Copolymer) (Rohm & Haas) Dow Corning DB 110 A nichtionische Silikonemulsion (INCI-Bezeichnung: Dimethicon) (Dow Corning) The following examples are intended to illustrate the subject matter of the present invention without limiting it in any way. Examples 1. Formulations 1.1 Dyeing preparation: raw materials Wt .-% Lanette D. 5.50 Lorol C12-18 techn. 2.00 Eumulgin B 1 0.60 Eumulgin B 2 0.60 Akypo Soft 45HP 10.00 Plantacare 1200 UP 2.00 Texapon K 14 S Special 70% 2.80 Product W 37194 3.75 coloring powder * 2.57 Ammonium sulfate techn. purely 0.40 ascorbic acid 0.10 Sodium sulfite anhydrous 0.40 Turpinal SL 0.20 Sodium silicate 40/42 0.50 Potassium hydroxide, 50% 1.00 Ammonia, 25% 7.10 Perfume qs Water, demineralized ad 100

• * Containing 1.4% by weight of 3-aminophenol, 5.7% by weight of 1,4-diamino-2-methylbenzenesulfate, 46.7% by weight of 1- (2-hydroxyethyl) -4,5-diaminopyrazole sulfate , 7.7 wt .-% bis (5-amino-2-hydroxyphenyl) methane dihydrochloride, 28.7 wt .-% 5-amino-2-methylphenol and 9.7 wt .-% of fumed silica, each based on the total weight of the dyeing powder.

1.2 Oxidation Preparations (B): raw material Wt .-% V1 E1 E2 potassium --- 0.07 0.07 sodium --- 0.21 0.21 Ammonia, 25% 0.65 --- --- dipicolinic 0.10 --- --- disodiumpyrophosphate 0.03 --- --- DOW CORNING DB 110 A 0.07 --- --- Turpinal SL 1.50 1.50 1.50 Texapon NSO 2.00 2.00 2.00 Manganese (II) chloride --- 0.50 0.50 Aculyn 33A 12,00 12,00 12,00 sodium chlorite --- 3.00 6.00 Hydrogen peroxide, 50% 12.0 --- --- water ad 100 ad 100 ad 100 Used raw materials Lanette D. C ₁₆ -C ₁₈ fatty alcohol (INCI name: cetearyl alcohol) (Cognis) Lorol tech. C ₁₂ -C ₁₈ fatty alcohol (INCI name: Coconut alcohol) (Cognis) Eumulgin B1 C ₁₆ -C ₁₈ -fatty alcohol, ethoxylated (12 EO) (INCI name: Ceteareth- 12) (Cognis) Eumulgin B2 C ₁₆ -C ₁₈ -fatty alcohol, ethoxylated (20 EO) (INCI name: Ceteareth- 20) (Cognis) Akypo Soft 45HP C ₁₂ -C ₁₄ alkyl ethers, ethoxylated (4.5 EO) carboxylic acid, sodium salt (ca. 21%, INCI name: Sodium Laureth-5 Carboxylate, Aqua) (KAO) Texapon K14 S Special C ₁₂ -C ₁₄ alkyl ether sulfate, ethoxylated (3 EO), sodium salt (about 27%, INCI Name: Sodium Myreth Sulfate, Aqua) (Cognis) Plantacare 1200 UP C ₁₂ -C ₁₄ alkyl ether glycoside (about 50-53% active ingredient: INCI Name: Lauryl Glucoside) (Cognis) Product W 37194 Copolymer of acrylic acid, sodium salt and trimethylammoniopropyl acrylamide chloride (about 20%, INCI name: acrylamidopropyl) Trimonium Chloride / Acrylate Copolymer, Aqua) (Stockhausen) Turpinal SL 1-hydroxyethane-1,1-diphosphonic acid (about 60% active ingredient content; INCI name: Etidronic Acid, Aqua) (Solutia) Sodium silicate 40/42 Natronwasserglas Texapon NSO Lauryl ether sulfate, sodium salt (about 27.5% active ingredient, INCI Name: Sodium Laureth Sulfate) (Cognis) Aculyn 33 Acrylic polymer (about 28% solids in water, INCI name: Acrylate copolymer) (Rohm & Haas) Dow Corning DB 110A nonionic silicone emulsion (INCI name: dimethicone) (Dow Corning)

The Dyeing preparation F was in each case in proportion 1: 1 mixed with the oxidation preparations E1, E2 and V1.

Of the pH of the finished application mixture was between 9.8 and 10.2.

2. colorations

The Ready to use funds were for the Blondierprozess was on strands of white hair (Kerling, Euronaturhaar, white) of about 0.7 g weight 4 times Quantity of finished application mixture applied, for one Leave on the hair for 30 min at 32 ° C, and then with a commercial shampoo washed and dried with a hair dryer.

It each received a bright garnet red color, with no differences in color depth and luminosity between the dyeings of the invention (with E1 or

E2) and staining with the comparative hydrogen peroxide-containing Oxidation preparation V1 were recognizable.

3. Evaluation of hair damage

3.1 Method description for NIR analysis of treated hair

Qualitative determination of hair structure damage by cluster analysis

hair can by oxidative treatment in colorants be damaged.

Cystine is a component of human hair. Cystine exhibits typical oscillations in the NIR (near-infra-red) spectrum at a wavelength of 6200 cm ^{-1 to} 5500 cm ^-1 . The disulfide bridge contained in cystine is broken oxidatively in a hair treatment, and the resulting thiol is converted by further oxidation in the sulfonic acid group of cysteic acid. At the same time, hair changes in cysteic acid content, which increases with increasing oxidative damage. Cysteic acid shows in the NIR spectrum at a wavelength of 5020 cm ^-1 - 4020 cm ^-1 . The decrease in cystine and the increase in cysteic acid is therefore an indicator of the damage to the hair.

The spectra are recorded using a MPATM FT-NIR spectrometer from Bruker Optik GmbH (Ettlingen, Germany). The near-infrared (NIR) range includes the wavenumber range of 12500 cm ^-1 to 4000 cm ^-1 and is suitable for overtone and combination vibrations of e.g. As CH, OH and NH groups characteristic. The samples are measured with the integration sphere module at six different sample positions in diffuse reflection. For the analysis of the measured NIR spectra, the wavenumber range is chosen to be 8000 cm ^{-1 to} 4020 cm ^-1 . For the chemometric evaluation, the device-independent software package Unscrambler (CAMO, Oslo, Norway) is used.

Based In a PCA (Principal Compound Analysis) you can do the separation recognize the spectra in so-called "clusters" The larger the distances between the clusters that of the untreated patterns are the bigger is the spectral deviation along with the extent of the Hair structural change. Let this way the hair after treatment with brighteners and subsequent Divide survey in NIR into clusters. The strength of Change of the treated hair is immediately recognizable.

Quantitative determination of hair structure damage by calibration preparation

NIR spectra can also be quantitatively evaluated if reference values are available are. Modeling is done using a partial least squares (PLS) algorithm a correlation between spectroscopic data and the corresponding concentration values of the individual components calculated. Reference values are obtained by sampling in the Laboratory about another independent analytical Procedure determined quantitatively. The PLS model is being changed frequency range, mathematical data pre-treatment, selection the appropriate number of factors and automatic outlier detection improved.

A detailed description of the method can be found in Evaluation of Physical Properties of Human Hair by Diffuse Reflectance Near-Infrared Spectroscopy, Y. Miyamae, Y. Yamakawa and Y. Ozaki in Applied Spectroscopy, 2007, Vol. 61 (2), p. 212 ff , 3.2 Results Hair sample (Kerling, Euronatur hair, white) NIR analsyne value cysteic acid [mol / 100 mol amino acid] untreated 0.5 colored with F + V1 (3.0% by weight hydrogen peroxide) 2.0 dyed with F + E1 (1.5% by weight sodium chlorite) 0.5 dyed with F + E2 (3.0% by weight sodium chlorite) 1.1

The Cysteic acid levels of hair samples were measured by NIR measurements certainly. The results show for both inventive Oxidizer preparations with sodium chlorite (F + E1 and F + E2) a significantly lower proportion of cysteic acid with the comparison brighteners (F + V1). This will make the lower Hair damage by the invention Dyeing formulations occupied.

QUOTES INCLUDE IN THE DESCRIPTION

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Cited patent literature

• - EP 998908 A2 [0176]

Cited non-patent literature

• - K. Schrader, Basics and Formulations of Cosmetics, 2nd edition, 1989, Dr. med. Alfred Hüthig Verlag, Heidelberg, or W. Umbach (ed.), Kosmetik, 2nd edition, 1995, Georg Thieme Verlag, Stuttgart, New York [0002]
• - Rompp Lexicon Chemistry (ed. J. Falbe, M. Regitz), 10th edition, Georg Thieme Verlag Stuttgart, New York, (1997), page 1764 [0209]
• - Kh. Schrader, bases and formulations of cosmetics, 2nd edition, Hüthig Buch Verlag, Heidelberg, 1989 [0218]
• - Evaluation of Physical Properties of Human Hair by Diffuse Reflectance Near-Infrared Spectroscopy, Y. Miyamae, Y. Yamakawa and Y. Ozaki in Applied Spectroscopy, 2007, Vol. 61 (2), p. 212 ff. [0242]

Claims (12)

Agent for the oxidative dyeing of keratin-containing fibers, in particular human hair, which is prepared immediately before use by mixing a dyeing preparation (A) containing in an aqueous cosmetic carrier at least one oxidation dye precursor, and an oxidizing agent preparation (B), characterized in that the oxidizing agent preparation (B) contains in a cosmetic carrier sodium chlorite. Means according to claim 1, characterized in that the oxidizing agent preparation (B) sodium chlorite in a proportion from 0.05 to 15 wt .-%, preferably from 0.1 to 10 wt .-% and in particular from 0.5 to 6 wt .-%, each based on the total weight of ready to use agent. Agent according to one of claims 1 or 2, characterized in that the oxidizing agent preparation (B) additionally at least one stabilizer selected from phosphonic acids. Agent according to one of claims 1 to 3, characterized in that the oxidizing agent preparation (B) additionally contains at least one polymeric thickener. Means according to claim 4, characterized in that the polymeric thickener is selected from anionic Polymers which contain at least one acrylic acid monomer as building block and / or a methacrylic acid unit. Agent according to one of claims 1 to 5, characterized in that the oxidizing agent preparation (B) additionally at least one salt of a transition metal, selected from salts of cerium, vanadium, manganese, iron, Cobalt, nickel, copper and zinc. Agent according to one of claims 1 to 6, characterized in that the oxidizing agent preparation (B) additionally contains at least one anionic surfactant. Composition according to one of claims 1 to 7, characterized in that the dyeing preparation (A) additionally contains as anionic surfactant at least one ether carboxylic acid of the formula RO (CH ₂ CH ₂ O) _x CH ₂ COOH and / or one of its physiologically acceptable salts, wherein R is a C ₁₀ -C ₂₀ alkyl chain and x = 0 or a number from 1 to 16. Agent according to one of claims 1 to 8, characterized in that the dyeing preparation (A) additionally contains at least one nonionic surfactant which is selected from C ₈ -C ₂₀ alkyl glucosides. Cosmetic, non-therapeutic use of a Colorant for keratinic fibers containing in a cosmetic carrier sodium chlorite as an oxidizing agent to reduce fiber damage in the oxidative Coloring. Method of coloring human hair, wherein an agent is prepared by mixing at least one oxidizing agent preparation (B) containing sodium chlorite and at least one coloring preparation (A) containing at least one oxidation dye precursor the ready-to-use agent 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 rinsed with water and / or a commercial shampoo becomes. 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 Carrier contains sodium chlorite, and at least a container (II) containing a dyeing preparation (A) in an aqueous-cosmetic carrier contains at least one oxidation dye precursor comprises.