EP2355905A2 - Alternative oxidizing agents - Google Patents

Abstract

The present application relates to agents for the gentle oxidative coloration of keratinous fibers, in particular human hair, which are manufactured by mixing a colorant preparation containing oxidizing colorant pre-products and an oxidizing agent preparation, wherein the oxidizing agent preparation is characterized in that, instead of hydrogen peroxide, it contains sodium chlorite as the oxidizing agent. The use of such agents for coloring human hair causes a significant reduction in the fiber damage during the coloring process as compared with conventional oxidizing coloring agents based on hydrogen peroxide, with the coloring performance remaining the same.

Description

 "Alternative Oxidants"

The present application relates to compositions for gentle oxidative dyeing of keratinic fibers, in particular human hair, which are prepared 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 causes a significant reduction in fiber damage in the dyeing process over conventional hydrogen peroxide-based oxidation colorants with consistent dyeing performance.

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 the fashionable color design of hairstyles or for lamination of gray or even white hair with fashionable or natural shades, the consumer takes to color-changing agents. In addition to the desired staining performance, these agents should cause the least possible damage to the hair. The principles of the dyeing process are known in the art and in relevant monographs, eg. B. by K. Schrader, Foundations and formulations of cosmetics, 2nd edition, 1989, Dr. med. Alfred Hüthig Verlag, Heidelberg, or W. Limbach (ed.), Cosmetics, 2nd edition, 1995, Georg Thieme Verlag, Stuttgart, New York, described in summary.

To provide color-changing cosmetic agents, in particular for the skin or keratin-containing fibers such as human hair, the skilled person knows various dyeing systems depending on the requirements of the dyeing.

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 of atmospheric oxygen with one another or with coupling with one or more coupler components, the actual dyes. The oxidation dyes are characterized by excellent, long-lasting dyeing results. For naturally acting dyeings, however, usually a mixture of a larger number of oxidation dye precursors must be used; In many cases, direct dyes are still used for shading. The developer components used are usually primary aromatic amines having a further, in the para or ortho position, free or substituted hydroxy or amino group, heterocyclic hydrazones, diaminopyrazole derivatives and 2,4,5,6-tetraaminopyrimidine and its derivatives. As coupler components m-phenylenediamine derivatives, naphthols, pyridine derivatives, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenols are generally used.

For temporary dyeings usually dyeing or tinting agents are used which contain so-called direct drawers as a coloring component. These are dye molecules that attach directly to the substrate and do not require an oxidative process to form the paint. These dyes include, for example, the henna already known from antiquity for coloring body and hair. These dyeings are generally much more sensitive to shampooing than the oxidative dyeings, so that a much more undesirable change in shade or even a visible, homogeneous color loss occurs much more quickly.

Finally, another dyeing process has received much attention. In this method, precursors of the natural hair dye melanin are applied to the substrate, e.g. As hair applied; These then form naturally-analogous dyes in the course of oxidative processes in the hair. In particular, multiple use of agents with 5,6-dihydroxyindoline, it is possible to reproduce natural hair color to people with graying hair. The coloration can be done with atmospheric oxygen as the sole oxidant, so that no further oxidizing agents must be used.

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. A second class of oxo dye precursors are C, H-acidic compounds and primary or secondary amino group or hydroxy group compounds, which in turn are selected from the group consisting of 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 Nuancenspektrum achievable with the gentle oxo staining is very broad and the color obtained often has an acceptable brilliance and color depth. However, corresponding compounds of the second class of the oxo dye precursors may also contain corresponding developer and / or coupler-type oxidation dye precursors with or without the use of an oxidation catalyst. find by use. Thus, the method of oxo staining can be readily combined with the oxidative staining system.

If substrates are to be lightened or even bleached, the dyes coloring the substrate are usually decolorized oxidatively using appropriate oxidizing agents, for example hydrogen peroxide.

In order to improve the care condition of the fibers, it has long been customary to subject the fibers to a special aftertreatment following the dyeing or shape-changing treatment. In this case, the hair is treated with special active ingredients, for example quaternary ammonium salts or special polymers, usually in the form of a rinse. Depending on the formulation, this treatment improves combability, hold and fullness of the hair and reduces the split rate. In order to reduce the expense of the usual multi-stage process, especially in the direct application by consumers, so-called combination preparations have recently been developed. In addition to the customary components, for example for dyeing the hair, these preparations additionally contain active ingredients which were formerly reserved for hair aftertreatment agents. The consumer thus saves an application step; At the same time, packaging costs are reduced because one product is less needed. Nevertheless, these agents, in particular on fibers that are difficult to care for, still leave some wishes as to the care properties.

In particular, oxidative hair dyes are disadvantageous to the user despite their advantageous dyeing properties.

On the one hand, the use of the oxidizing agent for coloration or development of the actual dyeing leads to damage in the hair structure and on the hair surface. On the other hand, oxidative colorants usually require a basic pH for coloration, in particular between pH 9.0 and pH 10.5. This causes the hair to become brittle, lose its elasticity and decrease combability. This damage increases with the duration of use. Commercially available oxidative colorants usually have to act on the hair fiber for a period of 30 minutes and longer. The increase in the exposure time leads to an increased impairment of the hair structure.

Furthermore, the basic pH is often adjusted with ammonia as an alkalizing agent, since ammonia-containing colorants have additional advantages in terms of dyeing performance. For the user, however, such a colorant in addition to an intense, unpleasant odor has the disadvantage that ammonia can cause irritation of the eyes, scalp or mucous membranes, which sensitization or even allergic reactions can be caused. Although dyeings with oxidative hair dyes compared to dyeings with other dyes, especially direct dyes, have significant advantages in terms of their washout and thus with respect to the color content, there is still a need for improvement in terms of fiber 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 is usually 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.

Although the colorants hitherto on the market generally show good dyeing performances, they can not be regarded as optimal due to hair damage, long application times and the possible skin irritation due to the high concentrations of oxidizing and alkalizing agents.

In the course of its investigations, the Applicant has now surprisingly found that the exchange of hydrogen peroxide for sodium chlorite as an oxidant in oxidative colorants has a positive effect on reducing fiber damage.

A first subject of the present invention is therefore an agent for the oxidative coloring of keratin-containing fibers, in particular human hair, which is mixed 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). is prepared, characterized in that the oxidizing agent preparation (B) in a cosmetic carrier contains sodium chlorite.

According to the invention, keratin-containing or keratinic fibers are understood to mean furs, wool, feathers and, in particular, human hair. Although the use according to the invention is primarily suitable for dyeing and / or whitening keratin-containing fibers, in principle there is no obstacle to their use in other fields as well.

The agents according to the invention contain the active ingredients in a cosmetic carrier. This cosmetic carrier according to the invention is aqueous, alcoholic or aqueous-alcoholic or optionally powdery. For the purpose of hair coloring such carriers are, for example, creams, emulsions, gels or surfactant-containing foaming solutions, such as shampoos, foam aerosols or other preparations suitable for use on the hair are suitable. For the purposes of the present invention, aqueous-alcoholic carriers are to be understood as meaning water-containing compositions containing from 3 to 70% by weight of a C ₁ -C ₄ -alkoHO, based on the total weight of the application mixture, in particular ethanol or isopropanol. The compositions of the invention may additionally contain other organic solvents such as 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. For the purposes of the invention, an aqueous carrier contains at least 30% by weight, in particular at least 50% by weight, of water, based on the total weight of the application mixture.

As a mandatory constituent, the agent according to the invention in the dyeing preparation contains at least one oxidation dye precursor.

In a preferred embodiment, the compositions according to the invention contain at least one oxidation dye precursor of the developer type and / or coupler type. Preferably, the colorants of the present invention contain at least one developer type oxidation dye precursor and at least one coupler type oxidation dye precursor.

The developer and coupler components are usually used in free form. In the case of substances having amino groups, however, it may be preferable to use them in salt form, in particular in the form of the hydrochlorides and hydrobromides or the sulfates.

Preferred p-phenylenediamines are selected from one or more compounds of the group formed from p-phenylenediamine, p-toluenediamine, 2-chloro-p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine, 2,6-dimethyl -p-phenylenediamine, 2,6-diethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, N, N-dipropyl -p-phenylenediamine, 4-amino-3-methyl- (N, N-diethyl) -aniline, N, N-bis (2-hydroxyethyl) -p-phenylenediamine, 4-N, N-bis (2-hydroxy) 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. Particularly preferred p-phenylenediamine derivatives according to the invention 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 their physiologically acceptable salts. It may further be preferred according to the invention to use as developer component compounds which contain at least two aromatic nuclei which are substituted by amino and / or hydroxyl groups. Preferred binuclear developer components are selected from at least one of the following compounds: N, N'-bis (2-hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diaminopropan-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 and their physiologically acceptable salts. Particularly preferred binuclear developer components are selected from N, N'-bis (2-hydroxyethyl) -N, N'-bis (4-aminophenyl) -1,3-diamino-propan-2-ol, bis (2-hydroxy) 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 their physiologically acceptable salts.

Furthermore, it may be preferred according to the invention to use as the developer component a p-amino phenol derivative or one of its physiologically tolerable salts. Particularly preferred p-aminophenols are p-aminophenol, N-methyl-p-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 2-hydroxymethylamino-4-aminophenol, 4-amino-3-ol hydroxymethylphenol, 4-amino-2- (2-hydroxyethoxy) phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethyl-phenol, 4-amino-2-aminomethylphenol, A- 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. Particularly preferred compounds 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, the developer component may be selected from o-aminophenol and its derivatives such as 2-amino-4-methylphenol, 2-amino-5-methylphenol or 2-amino-4-chlorophenol.

Furthermore, the developer component may be selected from heterocyclic developer components, such as pyrimidine derivatives, pyrazole derivatives, pyrazolopyrimidine derivatives or their physiologically acceptable salts. Preferred pyrimidine derivatives are 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. Preferred pyrazole derivatives are, in particular, the compounds 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-aminoethyl) amino-1, 3-dimethylpyrazole, and their physiologically acceptable salts. Among the pyrazolo [1, 5-a] pyrimidines may be mentioned in particular: pyrazolo [1,5-a] pyrimidine-3,7-diamine, 2,5-dimethyl-pyrazolo [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-amino-pyrazolo [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-amino-pyrazolo [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-dimethyl-pyrazolo [1, 5-a] pyrimidine and their physiologically acceptable salts and their tautomeric forms when tautomeric equilibrium is present.

Particularly preferred developer components are selected from at least one compound from the group formed from p-phenylenediamine, p-toluenediamine, 2- (2-hydroxyethyl) -p-phenylenediamine, 2- (1,2-dihydroxyethyl) -p-phenylenediamine , N, N-bis (2-hydroxy-ethyl) -p-phenylenediamine, 2-methoxymethyl-p-phenylenediamine, N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazole) 1-yl) propyl] amine, 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-tetraoxadic, 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, as well as the physiologically acceptable salts of this Ve rbindungen.

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

Coupler components do not form a significant color within the framework of the oxidative dyeing alone, but always require the presence of developer components. Therefore, it is preferred according to the invention that at least one developer component is additionally used when using at least one coupler component.

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,

Quinoxaline derivatives such as 6-methyl-1,2,3,4-tetrahydroquinoxaline,

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

Preferred m-aminophenol coupler components are selected from at least one compound from the group 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 their physiologically acceptable salts.

Preferred m-diaminobenzene coupler components are selected from at least one compound from the group 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-methyl- benzene, 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-ylphenyl) amino] ethanol, 3-amino 4- (2-methoxyethoxy) -5-methylphenylamine, 1-amino-3-bis (2'-hydroxyethyl) aminobenzene and their physiologically acceptable salts.

Preferred o-diaminobenzene coupler components are selected from at least one compound selected from the group consisting of 3,4-diaminobenzoic acid and 2,3-diamino-1-methylbenzene and their physiologically acceptable salts.

Preferred di- or trihydroxybenzenes and their derivatives are selected from at least one compound of the group which is formed from resorcinol, resorcinomonomethyl- ethers, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2-chlororesorcinol, 4-chlororesorcinol, pyrogallol and 1,2,4-trihydroxybenzene.

Preferred pyridine derivatives are selected from at least one compound of the group formed from 2,6-dihydroxypyridine, 2-amino-3-hydroxypyridine, 2-amino-5-chloro-3-hydroxy-pyridine, 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-di-methoxypyridine, 3,4-diaminopyridine, 2- (2-methoxyethyl) amino-3-amino-6-methoxypyridine, 2- (4'-methoxyphenyl) amino-3-aminopyridine, and the physiologically 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 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.

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

Preferred indoline derivatives are selected from at least one 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.

Particularly preferred coupler components according to the invention are selected from 3-aminophenol, 5-amino-2-methylphenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 5-amino-4-chloro-2 -methylphenol, 5- (2-hydroxyethyl) amino-2-methylphenol, 2,4-dichloro-3-aminophenol, 2-aminophenol, 3-phenylenediamine, 2- (2,4-diaminophenoxy) ethanol, 1, 3-bis (2,4-diaminophenoxy) propane, 1-methoxy-2-amino-4- (2-hydroxyethylamino) benzene, 1, 3-bis (2,4-diaminophenyl) propane, 2,6-bis (2'-hydroxyethylamino ) -1-methylbenzene, 2 - ({3 - [(2-hydroxyethyl) amino] -4-methoxy-5-methylphenyl} amino) ethanol, 2 - ({3 - [(2-hydroxyethyl) amino] -2 -methoxy-5-methylphenyl} amino) ethanol, 2- ({3 - [(2-hydroxyethyl) amino] -4,5-dimethylphenyl} amino) ethanol, 2- [3-morpholin-4-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-tri- hydroxybenzene, 2-amino-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine, 2,6-dihydroxy-3,4-dimethylpyridine, 3,5-diamino-2,6-dimethoxypyridine, 1 Phenyl-3-methylpyrazol-5-one, 1-naphthol, 1, 5-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1, 7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 4-hydroxyindole, 6-hydroxyindole, 7 Hydroxyindole, 4-hydroxyindoline, 6-hydroxyindoline, 7-hydroxyindoline or mixtures of these compounds or the physiologically acceptable salts of the aforementioned compounds.

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

The oxidation dye precursors are in the context of 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 .-%, each based on the ready-to-use oxidation colorants.

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

The agents according to the invention furthermore comprise compulsorily in the oxidizing agent preparation (B) in a cosmetic carrier sodium chlorite (NaCIO ₂ ) as oxidizing agent, preferably in place of hydrogen peroxide. Particularly preferred agents are characterized by being free of hydrogen peroxide.

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

Suitable powdered carriers include, for example, silicates or other mineral carriers as well as celluloses and other 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 ⁰ C, in particular of at most 30 ⁰ C, and / or at least one C _1o -C ₃ o-fatty acid having at least one additional hydroxy group and / or a derivative thereof. Esters of non-hydroxylated Ce-Cso-alkylmonocarboxylic 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, isotric decanoic 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, which are obtained, for example, in the pressure splitting of natural fats and oils, in the oxidation of aldehydes from Roelen's oxo synthesis or the dimerization of unsaturated fatty acids. Examples of the fatty alcohol components in the esters are isopropyl alcohol, caproic alcohol, caprylic 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, for example, 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 in the dimerization of unsaturated fatty alcohols incurred. Particular preference is given according to the invention to isopropyl myristate (Rilanit IPM), C 16-18 alkylsonone (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).

Agents preferred according to the invention 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 wt .-% and in particular from 0.5 to 6 wt .-%, in each case based on the total weight of the ready-to-use agent contains.

As has already been indicated, the replacement of hydrogen peroxide in favor of sodium chlorite as the oxidant in the colorant also causes damage to the keratinic fiber. Usually, damage to the keratinic fiber caused by oxidative staining may be detected on the cysteine content in the fiber. In the course of the oxidative treatment, disulfide bridges within the fiber are cleaved and the resulting thiol functionalities of the cysteine are converted into cysteic acid units. The resulting cysteine content in the keratinic fiber can be measured by near-infrared spectroscopy (NIR) and can thus be used to quantify fiber damage.

Oxidizing agent preparations (B) according to the invention are preferably aqueous, flowable oxidizing agent preparations. In this case, preferred preparations are characterized that the flowable oxidizing agent preparation - based on their weight - 40 to 98 wt .-%, preferably 60 to 95 wt .-%, particularly preferably 65 to 90 wt .-% water.

Furthermore, it has proven to be advantageous if the oxidizing agent preparation (B) additionally contains at least one stabilizer selected from phosphonic acids.

In the context of the present invention, preference is given to stabilizers which contain a phosphonic acid unit as a common chemical group. They are preferably used individually or in admixture with one another: a) geminal diphosphonic acids, such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP), whose higher homologues have up to 8 carbon atoms and hydroxyl- or amino-containing derivatives thereof and 1-aminoethane. 1,1-diphosphonic acid, its higher homologues having up to 8 carbon atoms and derivatives containing hydroxy or amino groups, and b) aminophosphonic acids such as ethylenediaminetetra (methylenephosphonic acid) (EDTMP), diethylenetriaminepenta (methylenephosphonic acid) (DTPMP) and their higher homologs , or nitrilotri (methylenephosphonic acid).

In the case of the alkaline pH values of the treatment solutions required according to the invention, these stabilizers are at least partially present as anions. It is irrelevant whether they are introduced in the form of acids or in the form of salts. In the case of use as salts, alkali metal, ammonium or alkylammonium salts, in particular sodium salts, are preferred.

Stabilizers which are preferred according to the invention 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 diethylene triamine pentamethylene phosphonate (DTPMP ) or its hepta- or octasodium salt.

Furthermore, it has been found that it is inventively preferred if the oxidation preparation (B) additionally contains at least one polymeric thickener.

Both organic and purely inorganic, polymeric thickeners can be used.

In a particularly preferred embodiment, 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-acrylamido-2-methylpropanesulfonic acid. The acidic groups can be completely or partly example, be 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 preferred polymeric thickeners according to the invention are characterized in that the polymeric thickener is selected from anionic polymers which contain at least one acrylic acid and / or one methacrylic acid unit as the monomer building block.

Preferred anionic homopolymers are uncrosslinked and crosslinked polyacrylic acids. Allyl ethers of pentaerythritol, sucrose and propylene may be 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, which is commercially available, for example, under the name Rheothiki 1-80.

Within this embodiment, it may further be preferred to use copolymers of at least one anionic monomer and at least one nonionic monomer. With regard to the anionic monomers, reference is made to the substances listed above. Preferred nonionic monomers are acrylamide, methacrylamide, acrylic acid 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 compositions preferably in an amount of 0.1 to 10 wt .-%, particularly 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-i-Cβ-alkyl esters, as sold under the INCI declaration Acrylates Copolymers. An especially preferred commercial product is, for example, Aculyn 33 from Rohm & Haas. But also preferred are copolymers of acrylic acid, methacrylic acid or their C-i-Cβ-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 if the anionic copolymers contain acrylic acid esters with longer-chain alkyl radicals as a monomer. Such copolymers are sold, for example, under the INCI name Acrylat.es/C10-30Allkylacrylate Crosspolymer. Exemplary commercial products of such copolymers are Carbopol ETD 2020, Carbopol Ultrez 20 and Pemulen TR-1 or 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 Sepigel 305 and Simulgel 600 from SEPPIC. The use of these compounds, which in addition to the polymer component, a hydrocarbon mixture (Ci ₃ -C ₁₄ - isoparaffin or Isohexadecan) and a nonionic emulsifier (Laureth-7 or polysorbate-80), has been found in the teaching of the invention to be particularly advantageous.

Further preferred anionic copolymers with sulfonic acid-containing 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 esters, such as beheneth-25 methacrylate, sold under the trade name Aristoflex AVC or Aristoflex HMB by Clariant to be expelled.

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

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, e.g. 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 from 50 to 75% by weight of ethyl acrylate, from 25 to 35% by weight. % Acrylic acid and 0 to 25 wt .-% of other comonomers known. Suitable dispersions of this type are commercially available, e.g. 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, such polymers in which the quaternary ammonium group over a C 1 -C ₄ -hydrocarbyl group are bonded to a built-up of acrylic acid, methacrylic acid or their derivatives polymer backbone have been found to be particularly suitable.

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 a 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 are methyl groups m is 2,

Suitable physiologically tolerated counterions X ^" are, for example, halide ions, sulfate ions, phosphate ions, methosulfate ions and organic ions such as lactate, citrate, tartrate and acetate ions, preference being given to halide ions, in particular chloride.

A particularly suitable homopolymer is the, if desired crosslinked, poly (methacryloxy-ethyltrimethylammonium chloride) with the INCI name Polyquaternium-37. If desired, the crosslinking can be carried out with the aid of poly olefinically unsaturated compounds, for example divinylbenzene, tetraallyloxyethane, methylenebisacrylamide, diallyl ether, polyallylpolyglyceryl 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 used in the form of a non-aqueous polymer dispersion which should not have a polymer content of less than 30% by weight. 50% polymer content, further component: mineral oil (INCI name: Mineral OiI) and tridecyl polyoxypropylene polyoxyethylene ether (INCI name: PPG-1-Trideceth-6)). and Salcare SC 96 (about 50% polymer content, further 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 Designation: PPG-1-trideceth-6) commercially available. Copolymers with monomer units of the formula (I) contain, as nonionic monomer units, preferably acrylamide, methacrylamide, and methacrylic acid C-rC ₄ alkyl esters. Among these nonionic monomers, the acrylamide is particularly preferred. These copolymers can also be crosslinked, as described above for the homopolymers. A preferred copolymer according to the invention is the crosslinked acrylamide-methacroyl-oxyethyltrimethylammonium chloride copolymer. Such copolymers in which the monomers are present in a weight ratio of about 20:80 are commercially available as an approximately 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 gums of 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.

Further suitable natural thickening agents are also already known from the prior art.

Also preferred according to this embodiment are biosaccharide gums of microbial origin, such as scleroglucan gums or xanthan gums, gums from plant exudates such as gum arabic, ghatti gum, karaya gum, gum tragacanth, carrageenan gum, 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 sold under the names Cellosize by Amerchol and Natrosol by Hercules. Suitable carboxyalkylcelluloses are in particular the carboxymethylcelluloses, as sold under the names Blanose by Aqualon, Aquasorb and Ambergum by Hercules and Cellgon by Montello.

Starch and its derivatives are also preferred. Starch is a storage substance of plants, which occurs mainly in tubers and roots, in grain seeds and in fruits and from one Variety of plants can be obtained 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 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 CrC 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, can be used as thickeners according to the invention. Preferred nonionic, fully synthetic polymers are sold, for example, by BASF under the trade name Luviskol. Such nonionic polymers, in addition to their excellent thickening properties, also allow a significant improvement in the sensory feeling of the resulting preparations.

As inorganic thickeners, phyllosilicates (polymeric, crystalline sodium disilicates) have proven to be particularly suitable in the context of the present invention. In particular clays, in particular magnesium aluminum silicates, such as bentonite, especially smectites, such as montmorillonite or hectorite, which may optionally also be suitably modified, and synthetic sheet silicates, such as the magnesium sheet silicate marketed by the company Süd Chemie under the trade name Optigel, are preferred.

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

In a preferred embodiment of the present invention, the oxidizing agent preparation (B) additionally contains 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 agents contain these metal salts to 0.01 to 10 wt .-%, preferably 0.1 to 5 wt .-%, based on the total weight of the ready-to-use agent.

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

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

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 having 8 to 30 C atoms ( Soap),

Ethercarbonsäuren the formula RO (CH ₂ CH ₂ O) _X CH ₂ COOH, in which R is a linear alkyl group having 8 to 30 carbon atoms and x = 0 or 1 to 16,

Acylsarcosides having 8 to 24 carbon atoms in the acyl group,

Acyltaurides having 8 to 24 carbon atoms in the acyl group,

Acyl isethionates having 8 to 24 carbon atoms in the acyl group,

Sulfobernsteinsäuremono- and -dialkylester having 8 to 24 carbon atoms in the alkyl group and

Sulfosuccinic acid mono-alkyl polyoxyethyl esters having 8 to 24 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups, linear alkanesulfonates having 8 to 24 carbon atoms, linear α-olefin sulfonates having 8 to 24 carbon atoms,

Sulfonates of unsaturated fatty acids having 8 to 24 carbon 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 hydroxysulfonate surfactants, sulfated hydroxyalkyl polyethylene 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 having 8 to 22 carbon atoms, alkyl and / or alkenyl ether phosphates of the formula

O

RO (C ₂ H ₄ O) _r P-OR'OH in the R is preferred for 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 is independently a number from 1 to 10, sulfated fatty acid alkylene glycol esters of the formula RC (O) CKaIkO) _n SO ₃ H, in which R is a linear or branched, aliphatic, saturated and / or unsaturated alkyl radical having 6 to 22 C Atoms, alk is CH ₂ CH ₂ , CHCH ₃ CH ₂ and / or CH ₂ CHCH ₃ and n is a number from 0.5 to 5,

Monoglyceride sulfates and monoglyceride ether sulfates of the formula (MGS)

in which R is a linear or branched alkyl radical having 6 to 22 carbon atoms, and x, y and z are in total 0 or numbers of 1 to 30, preferably 2 to 10. Typical examples of monoglyceride (ether) sulfates suitable for the purposes of the invention are the reaction products of lauric acid monoglyceride, coconut fatty acid monoglyceride, palmitic acid monoglyceride, stearic acid monoglyceride, oleic acid monoglyceride and tallow fatty acid monoglyceride and their ethylene oxide adducts with sulfur trioxide or chlorosulfonic acid in the form of their sodium salts. 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.

Particularly preferred anionic surfactants of the oxidation preparation (B) are alkyl sulfates, alkyl ether sulfates and ether carboxylic acids having 10 to 18 carbon 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 Ci _O -C _2O alkyl chain and x = 0 or a number 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 physiological compatible salts, wherein R is a Ci ₂ -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 preferably present in the agents according to the invention in amounts of from 0.05 to 15% by weight, based on the total ready-to-use agent. 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.

Therefore, a particular embodiment of the present invention is an agent which is characterized in that the dye preparation (A) additionally contains at least one nonionic surfactant which is selected from Cs-C _Σ o-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.

| - and do-alkyl groups essentially of C ₂ - C and particularly preferably those alkylpolyglucosides of formula RO- (Z) _x, in which R consists essentially of C _{8 4-} alkyl groups, consisting essentially of C ₈ - to C ₁₆ -alkyl groups or substantially of C ₁₂ - to C ₁₆ -alkyl groups or substantially 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 from 1.1 to 5 sugar units. Alkyl polyglucosides with x values of 1.1 to 2.0 are preferred. Very particular preference is given to alkylglucosides in which x is 1, 1 to 1, 8. An example of such an alkylpolyglucoside is the compound having the INCI name Lauryl Glucoside, which is marketed under the trade name Plantcare 1200 UP by Cognis.

The agents according to the invention may additionally contain at least one substantive dye. These are dyes that raise directly on the hair and do not require an oxidative process to form the color. Direct dyes are usually nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols.

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

It may be irrelevant whether the substantive dye in the dyeing preparation (A) or the oxidation preparation (B) is incorporated. Preferably, the substantive dye is incorporated in the emulsion preparation (A).

Direct dyes can be subdivided into anionic, cationic and nonionic substantive dyes.

Preferred anionic substantive dyes are those under the international 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.

Preferred cationic substantive dyes are cationic triphenylmethane dyes such as Basic Blue 7, Basic Blue 26, Basic Violet 2 and Basic

Violet 14, 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 substantive dyes containing a heterocycle containing at least one quaternary

Has nitrogen atom, as for example in EP-A2-998 908, which is explicitly referred to at this point, are mentioned in claims 6 to 11. The compounds also known as Basic Yellow 87, Basic Orange 31 and Basic Red 51 are most preferred cationic substantive dyes.

The cationic substantive dyes sold under the trademark Arianor are also very particularly preferred cationic substantive dyes according to the invention. Suitable nonionic substantive dyes are in particular nonionic nitro and quinone dyes and neutral azo dyes. Preferred nonionic substantive dyes are those under the international 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 HC Red 11, HC Red 11, HC Red 11, HC Red 11, HC Blue 2, HC Blue 11, HC Blue 12, Disperse Blue 3, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9 well-known compounds, as well 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, A-ethylamino-3-nitrobenzoic acid e and 2-chloro-6-ethylamino-4-nitrophenol.

It is not necessary that the optionally contained substantive dyes each represent uniform compounds. Rather, due to the production process for the individual dyes, minor amounts of other components may be included, as far as these do not adversely affect the dyeing result or for other reasons, e.g. toxicological, must be excluded.

Furthermore, as direct dyes also occurring in nature dyes are used, as for example in henna red, henna neutral, henna black, chamomile flower, sandalwood, black tea, walnut, buckthorn bark, sage, blue wood, madder root, catechu and alkano root are included.

The ready-to-use colorants of dyeing preparation (A) and oxidizing agent preparation (B) preferably have a pH in the range from 6 to 12. Particularly preferred is the application in an alkaline medium. The application temperatures can be in a range between 15 and 40 ⁰ C. After an exposure time of 2 to 45, preferably 5 to 30 minutes, the colorant is removed by rinsing off the hair. The washing with a shampoo is eliminated if a strong surfactant-containing carrier was used.

Blonding agents for keratinic fibers which are preferred according to the invention are characterized in that they have an alkaline pH. A further preferred embodiment of the present invention is that the ready-to-use agent has a pH of between 7.0 and 12.0, preferably between 8.0 and 11.0, more preferably between 9.0 and 10.5. Usually, the pH is adjusted with pH adjusters. In order to adjust the pH, those skilled in the art are familiar with common acidifying and alkalizing agents. The alkalizing agents which can be used for adjusting the pH are typically selected from inorganic salts, in particular the alkali metals and alkaline earth metals, organic alkalizing agents, in particular amines, basic amino acids and alkanolamines, and ammonia. Acidifying agents which are preferred according to the invention are pleasure acids, such as, for example, citric acid, acetic acid, malic acid or tartaric acid, and also dilute mineral acids. The pH values for the purposes of the present invention are pH values which were measured at a temperature of 22 ^° C.

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-methyl-butanol, 3-amino-2-methyl-propan-1-ol, 1-amino-2-methyl-2-propanol, 3-aminopropane-1,2-diol, 2-amino 2-methylpropane-1, 3-diol, 2-amino-2-ethyl-1, 3-propanediol, N, N-dimethyl-ehanolamine, methylglucamine, triethanolamine, diethanolamine and triisopropanolamine. A particularly preferred alkanolamine is monoethanolamine.

However, it has been found in the context of the investigations of the present invention that preferred according to the invention are characterized in that they additionally contain an inorganic alkalizing agent. The inorganic alkalizing agent of the present invention is preferably selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium phosphate, potassium phosphate, sodium silicate, potassium silicate, sodium carbonate and potassium carbonate.

The compositions according to the invention preferably contain the alkalizing agents in amounts of from 0.2 to 25% by weight, in particular from 0.5 to 10% by weight.

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

Zwitterionic surfactants are surface-active compounds which carry at least one quaternary ammonium group and at least one carboxylate, sulfonate or sulfate group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinates, N-acyl-aminopropyl-N, N-dimethyl-ammoniumglycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethyl-imidazolines with in each case 8 to 18 C atoms in the alkyl or acyl group and the cocoacylaminoethylhydroxyethylcarboxymethylglycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known by the INCI name Cocamidopropyl Betaine. 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 with each about 8 to 24 carbon atoms in the alkyl group. Particularly preferred amphoteric surfactants are N-cocoalkylaminopropionate, cocoacylaminoethyl aminopropionate and C ₂ -C ₁₈ acyl sarcosine.

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. The preferred nonionic surfactants are the alkylene oxide addition products of saturated linear fatty alcohols and fatty acids having in each case 2 to 30 moles of ethylene oxide per mole of fatty alcohol or fatty acid. Preparations having excellent properties are also obtained if they contain fatty acid esters of ethoxylated glycerol as nonionic surfactants.

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

Also preferred according to the invention are cationic surfactants of the quaternary ammonium compound type, the esterquats and the amidoamines. Preferred quaternary ammonium compounds are ammonium halides, in particular chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, as well as the imidazolium compounds known under the INCI names Quaternium-27 and Quaternium-83. The long alkyl chains of the above-mentioned surfactants preferably have 10 to 18 carbon atoms. Further cationic surfactants which can be used according to the invention are the quaternized protein hydrolysates.

The alkylamidoamines are usually prepared by amidation of natural or synthetic fatty acids and fatty acid cuts with dialkylaminoamines. A particularly suitable compound according to the invention from this group of substances is stearamidopropyl-dimethylamine, which is commercially available under the name Tegoamid S 18.

Esterquats are known substances which contain both at least one ester function and at least one quaternary ammonium group as a structural element. Preferred ester quats are quaternized ester salts of fatty acids with triethanolamine, quaternized ester salts of fatty acids with diethanolalkylamines and quaternized ester salts of fatty acids. acids with 1, 2-dihydroxypropyldialkylamines. Such products are sold, for example, under the trademarks Stepantex, Dehyquart and Armocare.

In a preferred embodiment, nonionic, zwitterionic and / or amphoteric surfactants and mixtures thereof may be preferred.

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

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 the Römpp Lexikon Chemie (Hrg. 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 has been found that the addition of ammonium salts of an inorganic or organic acid further improves the positive effect of the agents. 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 if the ammonium salt is added to the agent according to the invention in an amount of from 0.05 to 5% by weight, based on the total weight of the agent according to the invention. A particularly preferred ammonium salt is ammonium sulfate. A particular embodiment of the agent according to the invention is given when the agent additionally contains 0.01 to 3 wt .-%, preferably 0.1 to 1, 0 wt .-%, each based on the total weight of the ready-to-use agent, ammonium sulfate.

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 compositions according to the invention may furthermore contain all active substances, additives and auxiliaries known for such preparations. Further active ingredients, auxiliaries and additives are, for example, 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 Defoamers (such as silicones), dyes for staining the agent, anti-dandruff agents (such as Piroctone Olamine, zinc omadine and climbazole), light stabilizers (in particular derivatized benzophenones, cinnamic acid derivatives and triazines), active ingredients (such as allantoin, pyrrolidinonecarboxylic acids and their salts and bisabolol), cholesterol, bodying agents (such as sugar esters, polyol esters or polyol alkyl ethers), further fats and waxes (such as beeswax, montan wax and paraffins), fatty acid alkanolamides, swelling and penetrating agents (such as glycerine, 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, stabilizers for hydrogen peroxide and other oxidants, propellants (such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air ), Antioxidants.

The choice of these other substances will be made by those skilled in the art according to the desired properties of the agents. The active compounds, auxiliaries and additives are in each case preferably added in an amount of from 0.0001 to 25% by weight, preferably from 0.0005 to 15% by weight, in each case based on the total weight of the composition according to the invention. 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 cosmetics, 2nd edition, Hüthig book publisher, Heidelberg, 1989, referenced.

It has been found that for reasons of storage stability it may be expedient to prepare the ready-to-use colorant only by mixing components immediately before use, in order to prevent potential instabilities.

A preferred dosage form of the agent according to the invention is a packaging unit (kit-of-parts) which, packaged separately, contains at least one container (I) containing an oxidizing agent preparation (B) which contains sodium chlorite in a cosmetic carrier and at least one container (II). composition comprising a dyeing preparation (A) which comprises at least one oxidation dye precursor in an aqueous-cosmetic carrier.

For the purposes of the present invention, containers are understood to mean an envelope which is present in the form of an optionally resealable bottle, a can, a sachet, a sachet or similar wrappings.

It may be preferred if the oxidizing agent preparation (B) is in turn divided into two separate containers (Ia) and (Ib), wherein a container (Ia) comprises a pulverulent preparation (BP), optionally pressed as a shaped body, containing sodium chlorite and optionally further solids , Contains and a container (Ib) contains a flowable aqueous, alcoholic or aqueous-alcoholic preparation. The actual oxidizing agent preparation (B) is prepared by mixing the contents of the containers (Ia) and (Ib). The pulverulent preparation, if appropriate in tablet form, is expediently provided in a bag or sachet-like container, while the container (1b) is preferably a reclosable bottle. This ensures that the contents of the container (Ia) can be added to the contents of the container (Ib) and, after re-closure of the container (Ib), intimate mixing of the two preparations by shaking can be achieved.

Furthermore, it may be particularly advantageous according to the invention if said kit of parts contains at least one further hair treatment agent in a separate container, in particular a conditioning agent.

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

With regard to the preferred embodiments of the dyeing preparation (A) and the oxidizing agent preparation (B), the above statements of the preceding subject matter of the invention apply.

A further subject of the present invention is a process for dyeing human hair, wherein an agent is prepared by mixing at least one oxidation agent preparation (B) containing sodium chlorite and at least one dyeing preparation (A) containing at least one oxidation dye precursor the ready-to-use agent the hair is applied, is left in the hair for a period of 3 to 45 minutes, preferably 5 to 30 minutes, and then the hair is rinsed with water and / or a commercial shampoo.

In the context of this article of the present invention, mutatis mutandis, the above statements apply analogously.

Finally, another object of the present invention is the cosmetic, non-therapeutic use of a keratin fiber coloring agent containing in a cosmetic carrier sodium chlorite as an oxidizing agent for reducing fiber damage in oxidative dyeing.

In the context of this article of the present invention, mutatis mutandis, the above statements apply analogously.

The following examples are intended to illustrate the subject matter of the present invention without limiting it in any way. Examples

1. recipes

1.1 dyeing preparation:

^* 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, respectively based on the total weight of the dyeing powder.

1.2 Oxidation Preparations (B):

Commodities used La Nice D INCI name: Cetearyl alcohol (Cognis) Lorol tech. INCI name: Coconut alcohol (Cognis) Eumulgin B1 INCI name: Ceteareth-12 (Cognis) Eumulgin B2 INCI name: Ceteareth-20 (Cognis)

Akypo Soft 45HP INCI name: Sodium Laureth-5 Carboxylate, Aqua (KAO)

Texapon K14 S Special INCI name: Sodium Myreth Sulfate, Aqua (Cognis)

Plantacare 1200 UP INCI name: Lauryl Glucoside (Cognis)

Product W 37194 INCI name: Acrylamidopropyltrimonium Chloride / Acrylates

Copolymer, Aqua (Stockhausen)

Turpinal SL INCI name: Etidronic Acid, Aqua (Solutia)

Sodium silicate 40/42 soda water glass

Texapon NSO INCI name: Sodium Laureth Sulfate (Cognis)

Aculyn 33 INCI name: Acrylates Copolymer (Rohm & Haas)

Dow Corning DB 110 A INCI name: Dimethicone (Dow Corning)

The dyeing preparation F was mixed in each case in the ratio 1: 1 with the oxidation preparations E1, E2 and V1. The pH of the finished application mixture was between 9.8 and 10.2.

2. colorations

The ready-to-use agents were applied to strands of white hair (Kerling, Euronaturhaar, white) of about 0.7 g weight 4 times the amount of the finished application mixture for the bleaching process, for a contact time of 30 min at 32 ⁰ C on the Leave hair, then washed with a commercial shampoo and dried with a hair dryer. In each case, a bright garnet red color was obtained, with no differences in color depth and luminosity between the dyeings of the invention (E1 or E2) and the coloration 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 be damaged by oxidative treatment in colorants. Cystine is a component of human hair. Cystine shows at spectrum at a wavelength of 6200 cm ^"1 - 5500 cm ^{" 1} typical oscillations in the NIR (hJah-] nfra red). The disulfide bridge contained in cystine is oxidatively broken during a hair treatment, and the resulting thiol is converted by further oxidation into 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 covers the wave- length range from 12500 cm ^'1 to 4000 cm ^"1 and is characteristic for harmonic and combination vibrations of eg CH, OH and NH groups For the analysis of the measured NIR spectra, the wavenumber range 8000 cm ^"1 - 4020 cm ^{" 1 is} selected For the chemometric evaluation, the device-independent software package Unscrambler (CAMO, Oslo, Norway) Using a PCA (Principal Compound Analysis), one can recognize the separation of the spectra into so-called "clusters". The larger the distances between the clusters and the untreated patterns, the greater the spectral deviation along with the extent of the hair structure change. In this way, the hair can be classified into clusters after treatment with brighteners and subsequent measurement in the NIR. The strength of the change in the treated hair is immediately recognizable.

Quantitative determination of hair structure damage by means of calibration NIR spectra can also be quantitatively evaluated if reference values are available. Modeling uses a partial least squares (PLS) algorithm to compute a correlation between spectroscopic data and the corresponding concentration values of each component. Reference values are obtained by quantifying samples in the laboratory by another independent analytical procedure. The PLS model is improved by changing the frequency range, mathematical data pre-treatment, selection of the appropriate number of factors and automatic outlier detection.

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

The cysteic acid contents of the hair samples were determined by NIR measurements. The results show for both oxidant preparations according to the invention with sodium chlorite (F + E1 and F + E2) a significantly lower proportion of cysteic acid with the comparison brighteners (F + V1). As a result, the lower hair damage is confirmed by the dyeing preparations according to the invention.

Claims

claims

1. An 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 at least one oxidation dye precursor in an aqueous cosmetic carrier and an oxidizing agent preparation (B) in that the oxidizing agent preparation (B) in a cosmetic carrier contains sodium chlorite.

2. Composition according to claim 1, characterized in that the oxidizing agent preparation (B) sodium chlorite in an amount of 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 the ready-to-use agent contains.

3. Composition according to one of claims 1 or 2, characterized in that the oxidizing agent preparation (B) additionally contains at least one stabilizer selected from phosphonic acids.

4. Composition according to one of claims 1 to 3, characterized in that the oxidizing agent preparation (B) additionally contains at least one polymeric thickener.

5. A composition according to claim 4, characterized in that the polymeric thickener is selected from anionic polymers which contain at least one acrylic acid and / or a methacrylic acid unit as a monomer building block.

6. Composition according to one of claims 1 to 5, characterized in that the oxidizing agent preparation (B) additionally contains at least one salt of a transition metal selected from salts of cerium, vanadium, manganese, iron, cobalt, nickel, copper and zinc.

7. Composition according to one of claims 1 to 6, characterized in that the oxidizing agent preparation (B) additionally contains at least one anionic surfactant.

8. 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 in which R is a C ₁₀ -C ₂₀ -alkyl chain and x = 0 or a number from 1 to 16.

9. Composition 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.

10. Cosmetic, non-therapeutic use of a coloring agent for keratinic fibers, containing in a cosmetic carrier sodium chlorite as an oxidizing agent for reducing fiber damage in oxidative dyeing.

11. A process for dyeing human hair, wherein an agent is prepared by mixing at least one oxidation agent preparation (B) containing sodium chlorite, and at least one dyeing preparation (A) containing at least one oxidation dye precursor, the ready-for-use agent is applied to the hair is left in the hair for a period of 3 to 45 minutes, preferably 5 to 30 minutes, and then the hair is rinsed with water and / or a commercial shampoo.

12. Packing unit (kit-of-parts), which separately packaged at least one container (I) containing an oxidizing agent preparation (B) containing sodium chlorite in a cosmetic carrier, and at least one container (II) containing a dyeing preparation (A ) comprising at least one oxidation dye precursor in an aqueous-cosmetic carrier.