WO2010060730A1 - Hair colouring method comprising aftertreatment - Google Patents

Abstract

The invention relates to a method for altering the colour of keratin fibres that is kind to said fibres. The method is characterised by a two-stage application and by a combination of specific active ingredients, in particular amino acids containing hydroxyl groups and plant extracts in the colorant preparation and bioquinones in the aftertreatment agent. The invention also relates to a packaging unit comprising colorant preparations of this type and aftertreatment agents. The invention allows significantly improved fibre strength to be achieved in relation to conventional colorants.

Description

 Hair dyeing process with after-treatment

The invention relates to a process for fiber-sparing dyeing of keratin-containing fibers, which is characterized by a two-stage application, wherein in a first step, a dyeing preparation containing a fiber structure-improving agent is applied to the hair, is rinsed out of the hair after a certain exposure time and in a second step, which adjoins the first stage of the process in a timely manner, an aftertreatment agent is applied which contains at least one biochinone active ingredient. Due to the specific combination of active ingredients in the dyeing preparation and after-treatment agent, an unexpected fiber structure improvement is achieved. Furthermore, the present invention relates to a packaging unit which contains a hair dyeing preparation and an aftertreatment agent containing a biochinone active ingredient. The use of the packaging unit makes it possible to achieve an excellent fiber structure improvement, in particular with regard to the fiber thickness.

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. 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 dyeing power, these agents should cause the least possible damage to the hair and protect the fiber structure.

To provide farbve rändernd he cosmetic agents, especially for the skin or keratin fibers, such as human hair, the skilled person knows depending on 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

Intermediates. 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. For temporary dyeings usually dyeing or tinting agents are used, which contain as coloring component so-called substantive dyes (direct drawers). These are dye molecules that attach directly to the substrate and do not require an oxidative process to form the paint.

Another possibility for color change is the use of colorants, which contain so-called Oxofarbstoffvorprodukte, which are divided into two classes. A first class of oxo dye precursors are compounds having at least one reactive carbonyl group. A second class of oxo dye precursors form C, H-acidic compounds and compounds having a primary or secondary amino group or hydroxy group, preferably aromatic compounds. The resulting dyeings have partially color fastness on the keratin-containing fiber, which are comparable to those of the oxidation dyeing, but without relying on oxidizing agent for dye formation.

Finally, another dyeing process has received much attention. In this process, precursors of the natural hair dye melanin are applied to the hair, which then form in the context of oxidative processes in the hair natural analog dyes. 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.

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 particular, oxidative hair dyes are disadvantageous to the user despite their advantageous dyeing properties. In particular, the use of the oxidizing agent for coloration or development of the actual coloration leads to damage in the hair structure and on the hair surface. The hair becomes brittle, its elasticity decreases and its fiber strength decreases.

In the search for hair colorants with improved color stability, oxidation colorants with ubiquinones have been described, as in DE 101 06 745A1. DE 199 26 156 A1 discloses the use of biochinones for improving combability.

The object of the present invention is therefore to lower the mentioned disadvantages of hair dyeing processes. The fiber structure should be spared as possible, so that their Elasticity is as little as possible affected by the color change agent, and that the fibers have the least possible deterioration of the fiber thickness.

It has now been found, in an unpredictable manner, that the fiber structure of keratin-containing fibers in the color-changing process is spared to an unexpectedly great extent when a two-stage process is used for coloring the keratinic fibers, with a first color change step taking place Color change agent additionally contains a fiber-structure-improving agent, and then promptly followed by a step in which an aftertreatment agent containing a biochinone drug is applied to the fiber.

A first subject of the present invention is therefore a process for changing the color of keratinic fibers, wherein a dyeing preparation is applied to the fibers in a first step, is left on the fibers for a contact time T1 and subsequently washed out, and in a second step a post-treatment agent is applied to the keratinic fibers, is left on the fibers for a contact time T2 and is subsequently washed out, characterized in that a) the dyeing preparation in a cosmetic carrier contains at least one color-modifying component and additionally at least one fiber-structure-improving agent, b) the period a maximum of 60 minutes between completion of the first process step and beginning of the second process step, and c) the aftertreatment agent in a cosmetic carrier contains at least one active ingredient selected from biochinones.

Under keratinic fibers or keratin fibers are furs, wool, feathers and especially human hair to understand. Although the compositions according to the invention are primarily suitable for dyeing keratin fibers, in principle there is nothing to prevent their use in other fields as well.

The preparations used in the process according to the invention contain the active ingredients in a cosmetic carrier. For the purposes of the invention, this cosmetic carrier is aqueous, alcoholic or aqueous-alcoholic. 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 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 Total weight of the application mixture, especially ethanol or isopropanol to understand. The compositions according to the invention may additionally contain further 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.

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 the first essential ingredient, the dyeing preparation of the first process step contains at least one color-changing component.

The color-modifying component is selected from at least one (a) oxidation dye precursor and / or (b) direct dye and / or (c) natural dye and / or (d) oxo dye precursor.

In a preferred embodiment of the process according to the invention, the dyeing preparation contains as color-modifying component at least one oxidation dye precursor.

As oxidation dye precursors, the dyeing formulations contain at least one developer component and optionally at least one coupler component. The developer components can form the actual dyes with one another, but preferably with coupler components.

Preferably, therefore, 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 oxidation dye precursors are preferably used in an amount of 0.005 to 20% by weight, preferably from 0.05 to 5% by weight and particularly preferably from 0.1 to 5% by weight, in each case based on the oxidation dye ready for use.

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.

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 may be contained in a molar ratio of 1: 0.5 to 1: 2.

Preferred oxidation dye precursors of the developer type are p-phenylenediamine derivatives. Particularly 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-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-H ydroxyethyloxy) -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- (1 H -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. In particular, 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) ethylene diamine, 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. Very 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-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-tetraoxadecan or one of the physiologically acceptable salts of these compounds.

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-methyl-phenol, 4-amino-3-fluorophenol, 2-hydroxymethylamino-4-aminophenol, 4-amino-3-ol hydroxymethylphenol, 4-amino-2- (2-hydroxyethoxy) phenol, 4-amino-2-methylphenol, A-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethyl-phenol, 4-amino-2-aminomethyl phenol, 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. Very particularly preferred compounds are p-aminophenol, 4-amino-3-methylphenol, 4-amino-2-amino-methylphenol, 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 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-triamino-pyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6-triaminopyrimidine. Preferred pyrazole derivatives are, in particular, the compounds which are selected from 4,5-diamino-1-methylpyrazole, 4,5-diamino-1- (2-hydroxyethyl) pyrazole, 3,4-diaminopyrazole, 4,5- Diamino-1- (4'-chlorobenzyl) pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl- 3-phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazinopyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-t-butyl-1-methylpyrazole, 4,5-diamino-1-t-butyl-3-methylpyrazole, 4,5-diamino-1- (2-hydroxyethyl) -3-methylpyrazole, 4,5-diamino-1-ethyl-3- methylpyrazole, 4,5-diamino-1-ethyl-3- (4-methoxyphenyl) pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-1-methylpyrazole , 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4,5-diamino-3-methyl-1-isopropylpyrazole, A-amino-5- (2-aminoethyl) amino-1,3-dimethylpyrazole, and their physiologically acceptable salts, but in particular 4,5-diamino-1- (2-hydroxyethyl) pyrazole. Among the pyrazolo [1,5-a] pyrimidines, particular preference is given to 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-amino pyrazolo [1,5-a] pyrimidin-5-ol, 2- (3-aminopyrazolo [1,5-a] pyrimidin-7-ylamino) ethanol, 2- (J-aminopyrazolo [1,5-a] pyrimidine 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 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-hydroxyethyl) -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-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, A - Hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, and their physiologically acceptable salts. Very particularly preferred developer components are p-toluenediamine, 2- (2-hydroxyethyl) -p-phenylenediamine, 2-methoxymethyl-p-phenylenediamine, N- (4-amino-3-methylphenyl) -N- [3- (1H -imidazol-1-yl) propyl] amine, and / or 4,5-diamino-1- (2-hydroxyethyl) pyrazole and their physiologically acceptable salts.

The developer components are preferably used in an amount of 0.0001 to 10 wt .-%, preferably 0.001 to 5 wt .-%, each based on the ready-to-use agent.

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 allow 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. Couplers are preferably cyclic compounds which carry at least two groups on the cycle, selected from (i) optionally substituted amino groups and / or (ii) hydroxyl groups. When the cyclic compound is a six-membered ring (preferably aromatic), so the said groups are preferably in ortho position or meta position to each other.

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 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 selected from the group consisting of 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 compounds mentioned above.

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-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-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 the physiologically acceptable salts of all of the aforementioned compounds.

Preferred di- or trihydroxybenzenes and derivatives thereof are selected from at least one compound of the group formed from resorcinol, resorcinol monoethyl ether, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2-chlororesorcinol, A-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-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-methoxy-pyridine, 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 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-morpholine-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-methoxypyridi n, 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 their physiologically acceptable salts. Resorcinol, 2-methylresorcinol, 5-amino-2-methylphenol, 3-aminophenol, 2- (2,4-diaminophenoxy) ethanol, 1, 3-bis (2,4-diaminophenoxy) propane, very particular preference is given thereto. Methoxy-2-amino-4- (2'-hydroxyethylamino) benzene, 2-amino-3-hydroxypyridine and 1-naphthol and one of their physiologically acceptable salts.

The coupler components are preferably used in an amount of 0.0001 to 10 wt .-%, preferably 0.001 to 5 wt .-%, each based on the ready-to-use agent.

Furthermore, the agents according to the invention may 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 0.001 to 20 wt .-%, in particular from 0.05 to 5 wt .-%, each based on the total application preparation. The total amount of substantive dyes is preferably at most 20% by weight.

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 direct 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 very particularly preferred cationic substantive

Dyes of group (c).

The cationic direct dyes, which are sold under the trademark Arianor ^®, according to the invention are also very particularly preferred cationic direct dyes.

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, 4-ethylamino-3-nitrobenzoic acid acid 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, in minor amounts even more Contain components, as far as they do not adversely affect the staining result or for other reasons, such as 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.

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 dyestuff precursors of naturally-analogous dyes are preferably indoles and indolines which have at least two groups selected from hydroxy and / or amino groups, preferably as a substituent on the six-membered ring. These groups may carry further substituents, e.g. Example in the form of etherification or esterification of the hydroxy group or alkylation of the amino group. In a further embodiment, the colorants contain at least one indole and / or indoline derivative. Compositions according to the invention which comprise precursors of naturally-analogous dyes are preferably used as air-oxidative colorants. Consequently, in this embodiment said compositions are not added with an additional oxidizing agent.

The dye precursors of naturally-analogous dyes are each preferably used in an amount of from 0.001 to 5% by weight, based on the total application preparation. The total amount of substantive dyes is preferably at most 3% by weight.

Particularly suitable as precursors of natural-analogous hair dyes are derivatives of 5,6-dihydroxyindoline. Particularly preferred derivatives of indoline are 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6 dihydroxyindoline and 5,6-dihydroxyindoline-2-carboxylic acid, especially 5,6-dihydroxyindoline.

Derivatives of 5,6-dihydroxyindole are also outstandingly suitable as precursors of naturally-analogous hair dyes. Particularly preferred derivatives of indole are 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6- dihydroxyindole, 5,6-dihydroxyindole-2-carboxylic acid, especially the 5,6-dihydroxyindole. 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. This first class is called a component (Oxo1). 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 compounds of the group formed from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds. This second class is called a component (Oxo2). The aforementioned components (oxo1) and (oxo2) are generally not themselves dyes, and therefore are not in themselves suitable for coloring keratin-containing fibers. 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, it is also possible to use corresponding developer and / or coupler-type oxidation dye precursors with or without the use of an oxidizing agent in compounds of the component (oxo2). Thus, the method of oxo staining can be readily combined with the oxidative staining system.

Therefore, in a further embodiment, oxo dye precursors can also be used as the color-modifying component according to the invention. Oxofarbstoffvorprodukte are preferred as a combination of at least one compound containing at least one reactive carbonyl group (component (Oxo1)) with at least one compound (component Oxo2) compounds selected from (Oxo2a) C, H-acidic compounds and / or from

(Oxo2b) Compounds having primary or secondary amino group or hydroxy group selected from at least one compound of the group formed from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds.

The above-mentioned compounds of the component (Oxo1) as well as the component (Oxo2), when used, are each preferably in an amount of 0.001 to 10 wt .-%, in particular from 0.01 to 5 wt .-%, each based on the total weight of the ready-to-use agent used.

Oxidative dyeing of the fibers can in principle be carried out with atmospheric oxygen in the presence of oxidation dye precursors. However, preference is given to using a chemical oxidizing agent, especially if, in addition to the coloring, a lightening effect on human hair is desired. This lightening effect may be desired regardless of the staining method. Suitable oxidizing agents are persulfates, peroxodisulfates, chlorites, hypochlorites and, in particular, hydrogen peroxide or its addition products of urea, melamine and sodium borate.

A preferred embodiment of the process according to the invention is therefore characterized in that the dyeing preparation additionally contains at least one oxidizing agent selected from hydrogen peroxide and / or one of its addition products of organic or inorganic compounds.

Preferred addition products are the addition products of hydrogen peroxide to urea, melamine and sodium borate.

However, hydrogen peroxide is preferably used as the oxidizing agent. The amount of hydrogen peroxide in the ready-to-use agent is preferably from 0.5 to 12% by weight, preferably from 1 to 8% by weight, in each case based on the ready-to-use agent.

Such oxidizing agent preparations are preferably aqueous, flowable oxidizing agent preparations. Preferred preparations are characterized in that the flowable oxidizing agent preparation - based on their weight - 40 to 90 wt .-%, preferably 50 to 85 wt .-%, particularly preferably 55 to 80 wt .-%, more preferably 60 to 77, 5 wt .-% and in particular 65 to 75 wt .-% water.

However, according to the invention, the oxidation colorant can also be applied to the hair together with a catalyst which promotes the oxidation of the dye precursors, e.g. by atmospheric oxygen, activated. Such catalysts are z. For example, certain enzymes, iodides, quinones or metal ions.

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 of, for example, at least 10% by weight of acrylic acid lower alkyl ester, 25 to 70% by weight of methacrylic acid and optionally up to 40% by weight of a further comonomer, polymers of acrylic acid and optionally lower alkyl acrylates, Copolymers of 50 to 75 wt .-% ethyl acrylate, 25 to 35 wt .-% acrylic acid and

0 to 25 wt .-% of other comonomers, and

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. According to the invention, these anionic polymers are not covered by the definition of the amphoteric polymers according to the invention.

The anionic acrylic acid and / or methacrylic acid polymers or copolymers are preferred in the inventive compositions in an amount of 0.1 to 10 wt .-%, particularly preferably from 0.5 to 5 wt .-%, each based on the Total weight of the dye preparation, included.

When using additional oxidizing agents, the actual dyeing preparation is expediently prepared immediately before use by mixing a preparation according to the invention containing at least one color-modifying component and at least one fiber-structure-improving active ingredient, and a preparation containing the additional oxidizing agent, in particular hydrogen peroxide.

In a preferred embodiment, the method according to the invention is characterized in that the dyeing preparation contains as fiber-structure-improving active ingredient at least one active ingredient selected from hydroxyl-containing amino acids and / or plant extracts.

Preferred methods are characterized in that the dyeing preparation contains, as a fiber-structure-improving active substance, serine and / or an extract of the seeds of Moringa oleifera.

Preferably, the fiber-structure-improving active ingredient is selected from hydroxyl-containing amino acids. As hydroxyl-containing amino acid in the context of the invention, an organic compound which contains in its structure at least one protonatable amino group and at least one -COOH or -SO ₃ H group and at least one hydroxyl group. Preferably, the hydroxyl group is bonded to an aliphatic radical.

Preferred hydroxyl-containing amino acids are aminocarboxylic acids, in particular α-aminocarboxylic acids and ω-aminocarboxylic acids. Among the α-aminocarboxylic acids, in turn, threonine, 4-hydroxyproline and, in particular, serine are preferred.

Processes which are particularly preferred according to the invention are characterized in that the dyeing preparation contains serine as fiber-structure-improving active substance. α-aminocarboxylic acids usually contain at least one asymmetric carbon atom. In the context of the present invention, both possible enantiomers can be used equally as a specific compound or else mixtures thereof, in particular as racemates. However, it is particularly advantageous to use the naturally preferred isomeric form, usually in L configuration.

The dyestuff preparation particularly preferably contains L-serine, D-serine or D / L-serine as the fiber-structure-improving active substance, but most preferably L-serine.

The hydroxyl-containing amino acids may preferably be added to the inventive compositions in free form. In a number of cases, however, it is also advantageous to use the amino acids in salt form. Preferred salts are then the compounds with hydrohalic acids or sulfuric acid, in particular the hydrochlorides, the hydrobromides and the sulfates.

An inventively particularly preferred hydroxyl-containing amino acid is L-serine, especially in free form, but also used as the hydrochloride.

The hydroxyl-containing amino acid is preferably present in the dyeing formulations according to the invention in amounts of from 0.01 to 10% by weight, in particular from 0.05 to 5% by weight, based on the total weight of the application mixture.

Furthermore, it may be preferred according to the invention if the dyeing preparation contains a plant extract as fiber-structure-improving active substance, provided that this plant extract has the fiber-structure-improving properties. The plant extracts according to the invention can be obtained from all parts of the plants. The plant extracts are preferably obtained by extraction with organic solvents (such as, for example, ethanol, isopropanol, diethyl ether, benzene, benzene, chloroform) or by steam distillation. Preferred plant extracts are, for example, extracts of flowers, stems and leaves, fruits, fruit peel, roots, woods, herbs and grasses, needles and twigs, resins and balsams, and the seeds.

A plant extract which is particularly preferred according to the invention is the extract of the seeds of Moringa oleifera (Moringa pterygosperma).

A method preferred according to the invention is therefore characterized in that the dyeing preparation contains as fiber-structure-improving active ingredient an extract from the seeds of Moringa oleifera (Moringa pterygosperma). Moringa growths, in particular Moringa oleifera (Moringa pterygosperma), Moringa drouhardii, Moringa concanensis or Moringa peregrin, better known by their common name "miracle tree", are preferably native to tropical regions The various parts of this plant genus have been used since ancient times especially for medical purposes The protein is obtained from the seeds of the Moringa growths by gentle extraction with water and glycerol, this protein having a molecular weight of 500 to 50,000 daltons Preferred is a protein extract having a molecular weight of 3,000 to 30,000 daltons, more preferably 5,000 to 15,000 The extracted extract is obtained from the plant Moringa oleifera.Of course, the extract according to the invention contains water and glycerol on the basis of the extraction.The content of extracted protein in the extract is from 0.01 to 20% by weight , 01 up to 10 wt .-% is here prefers. Particularly preferred is an extract with a protein content of 0.01 to 5 wt .-%. Furthermore, the extract contains at least 30% by weight of glycerol. Finally, water is contained in the extract according to the invention.

In the cosmetic compositions, the above-described protein extract from the seeds of the Moringa growths is contained in an amount of at least 0.001 to 20% by weight. Preferably, amounts of the extract of 0.001 to 10 wt .-%, most preferably amounts of 0.001 to 5 wt .-%, each based on the total preparation used.

In the first step of the process according to the invention, a dyeing preparation is applied to the keratinic fibers and left in the hair for a certain exposure time. The application of the dyeing preparation is usually done by hand by the user. Personal protective clothing is preferably worn here, in particular suitable protective gloves, for example made of plastic or latex for single use (disposable gloves) and optionally an apron. But it is also possible to apply the dyeing preparation with an application aid on the keratinic fibers. Particularly suitable as application aids are comb, brush, brush, mascara brush or applicette.

An applicette is understood to be a broad brush, on the end of which there is a tip which allows and simplifies the division of bundles of fibers from the total amount of fibers. The application and the contact temperature of the dye preparation is room temperature up to 45 ° C. Optionally, the effect of the dyeing preparation can be enhanced by external heat input, such as by means of a heat hood. The preferred exposure time T1 of the dyeing preparation to the keratinic fiber is 2 to 45 minutes, preferably 5 to 35 minutes. After completion of the exposure time T1, the remaining dyeing preparation of the keratinic fibers with Washed out the help of a cleaning preparation. As a cleaning preparation in this case is preferably warm water, which optionally additionally contains surface-active additives (surfactants). Such surfactants are described below. The preferred application temperature of the cleaning preparation is in particular at 25 ° C to 60 ⁰ C, preferably at 30 ⁰ C to 55 ° C. After washing with the cleaning preparation, the keratin fibers are optionally dried with a towel or a hot air blower (hair dryer).

It has been found that the desired small reduction in the fiber structure thickness can only be achieved if the second process step is followed as soon as possible after completion of the first process step. If the second process step is only carried out with a delay of a few hours or even days, then no significant positive effect with respect to the fiber structure strength is more recognizable.

The period of time after the end of the first process step until the beginning of the second process step is therefore not more than 60 minutes, preferably not more than 30 minutes and particularly preferably not more than 10 minutes. It may be preferable to start the second method step immediately after the completion of the first method step.

In a second method step according to the present invention, aftertreatment agent comprising, in a cosmetic carrier, at least one active ingredient selected from biochinones, applied to the keratinic fibers is left on the fibers for a contact time T2 and subsequently washed out.

An inventively preferred embodiment of the present invention is given by the fact that the aftertreatment agent in a cosmetic carrier contains as biochinone active ingredient at least one active ingredient from the group consisting of mitoquinones and plastoquinones. According to the invention, biochinone active substances are natural, prenylated quinones which, as a common structural feature, carry a quinone according to formula (B) and differ in the substituents R 1, R 2 and R 3 and the degree of prenylation n:

(BC) wherein R 1, R 2 and R 3 are each independently hydrogen, a C 1 -C 6 alkoxy group or a C 1 -C 6 alkyl group, and n is a number between 1 and 30. According to the invention preferred biochinones are mitochinonones or coenzyme Q. These have as a common structural feature a compound according to formula (BC), wherein R1 is a methyl group and R2 and R3 are each a methoxy group. The degree of prenylation is given by the number n and is at the same time giving the name of the mitochinones (ubiquinone 5n or coenzyme Q _n ). For example, therefore, the representative with n = 1 is called ubiquinone 5 or coenzyme Q ₁ , while the compound with n = 3 is called ubiquinone 15 or coenzyme Q ₃ . Preferred mitoquinones have a degree of prenylation of 1 to 15.

Plastochinones which are advantageous according to the invention are characterized in that the radicals R 2 and R 3 in compounds of the formula (BC) are each methyl, while the substituent R 1 is hydrogen. The degree of prenylation is likewise given by the number n and is preferably between a value of 1 and 20, in particular 1 to 15. A particularly preferred embodiment is characterized in that the preparation for the aftertreatment of the keratinic fibers as the active ingredient ubiquinone-50 (coenzyme Q ₁₀ ) contains.

The biochinone active substances are preferably present in the preparation for the after-treatment in an amount of 0.001 to 5% by weight, in particular 0.005 to 0.5% by weight, in each case based on the weight of the entire preparation.

It has been found that the effect of the method according to the invention can be increased, in particular, if the aftertreatment agent is a combination of the biochinone active ingredient according to the invention and at least one further active ingredient selected from the group comprising amides of pantoic acid, in particular panthenol and / or pantothenic acid , and pantolactone, contains.

The additional active ingredient of the aftertreatment agent is preferably selected from amides of pantoic acid ((2R) -2,4-dihydroxy-3,3-dimethylbutanoic acid) according to formula (PA):

wherein R is an optionally substituted alkyl chain, wherein R as substituent contains a halogen, an amino group, a hydroxyl group, a carboxyl group, and / or a carbamoyl group, and R 'is hydrogen or a methyl group.

Particularly preferred aftertreatment agents according to the invention comprise, as amides of pantoic acid, a compound according to formula (PA) in which R 'is hydrogen and R 3-hydroxypropyl (panthenol) or 3-hydroxy-3-oxopropyl (pantothenic acid). The additional active ingredient selected from the group comprising amides of pantoic acid, in particular panthenol and / or pantothenic acid, and pantolactone is preferably present in the after-treatment agent in an amount of 0.005 to 5% by weight, in particular 0.01 to 2% by weight. -%, in each case based on the weight of the total preparation included.

A particularly preferred embodiment of the method according to the invention is therefore given when the aftertreatment agent additionally contains panthenol.

Most preferably, the aftertreatment agent of the second process step contains an active ingredient combination of a biochinone and of panthenol, in particular of ubiquinone-50 and panthenol.

In the second step of the method according to the invention, an aftertreatment agent is applied to the keratinic fibers and left in the hair for a certain exposure time T2. The application and the contact temperature of the aftertreatment agent is room temperature up to 45 ° C. Optionally, the effect of the post-treatment agent can be enhanced by external heat, such as by means of a heat hood. The preferred exposure time T2 of the aftertreatment agent to the keratinic fibers is 0.5 to 15 minutes, preferably 1 to 5 minutes. After completion of the exposure time T2, the remaining aftertreatment agent is washed out of the keratinic fibers with the aid of a cleaning preparation. As a cleaning preparation in this case is preferably warm water, which optionally additionally contains surface-active additives (surfactants). Such surfactants are described below. The preferred application temperature of the cleaning preparation is in particular at 25 ° C to 60 ⁰ C, preferably at 30 ⁰ C to 55 ° C.

After washing, the keratinic fibers are optionally dried with a towel or a hot air blower.

In the context of the process according to the invention, the ready-to-use preparations for color change and after-treatment preferably comprise flowable preparations. Preferably, the flowable preparations additionally contain as surface-active substance an emulsifier or a surfactant, surface-active substances being referred to as surfactants or as emulsifiers depending on the field of application anionic, cationic, zwitterionic and nonionic surfactants and emulsifiers are selected. These substances will be described in detail below.

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 for example, a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group having 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. Preferred anionic surfactants 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.

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 N-alkyl-N, N-dimethylammonium glycinates, for example cocoalkyl dimethylammonium glycinate, N-acylaminopropyl N, N-dimethylammonium glycinates, for example cocoacylaminopropyl-dimethylammonium glycinate, and Alkyl 3-carboxymethyl-3-hydroxyethyl-imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and Kokosacylaminoethylhydroxyethylcarboxymethylglycinat. A preferred zwitterionic surfactant is the fatty acid amide derivative known by the INCI name Cocamidopropyl Betaine.

Furthermore, it has proved to be advantageous if the brightening agents according to the invention contain nonionic surfactants. Nonionic surfactants contain as hydrophilic group z. A polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether groups. Suitable nonionic surfactants are, in particular, C ₈ -C ₂₂ -alkyl mono- and -oligoglycosides and their ethoxylated analogs. In particular, the nonethoxylated compounds have been found to be particularly suitable. As further preferred nonionic surfactants, the alkylene oxide adducts have been found to be saturated linear fatty alcohols and fatty acids each having 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 anionic, nonionic or zwitterionic 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, especially chlorides and bromides, e.g. As cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethyl ammonium chloride, lauryldimethylammonium chloride, Lauryldimethylbenzylammoniumchlorid and tricetylmethylammonium chloride, as well as under the INCI names quaternium-27 and quaternium-83 known imidazolium compounds. The long alkyl chains of The surfactants mentioned above preferably have 10 to 18 carbon atoms. Further according to the invention useful cationic surfactants are the quaternized protein hydrolyzates. A according to the invention particularly suitable compound from substance group of the amidoamine is sold under the name Tegoamid ^® S 18 stearamidopropyldimethylamine commercially available. Preferred esterquats are quaternized Estersalze of fatty acids with triethanolamine, quaternized Estersalze of fatty acids with diethanolalkylamines and quaternized ester salts of fatty acids with 1,2-dihydroxypropyldialkylamines. Such products are marketed under the trade names Stepantex® ^{®, ®} and Dehyquart® Armocare® ^®.

The cationic surfactants are contained in the compositions according to the invention preferably in amounts of 0.05 to 10 wt .-%, based on the total agent. Amounts of 0.1 to 5 wt .-% are particularly preferred.

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

In a further preferred embodiment, the effect of the active ingredient according to the invention can be increased by emulsifiers. Such emulsifiers are, for example, addition products of 4 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide to linear fatty alcohols having 8 to 22 carbon atoms, to fatty acids having 12 to 22 carbon atoms and to alkylphenols having 8 to 15 carbon atoms in the alkyl group; C ₂ -C ₂₂ -fatty acid mono- and diesters of addition products of 1 to 30 moles of ethylene oxide onto polyols having 3 to 6 carbon atoms, in particular to glycerol, ethylene oxide and polyglycerol addition products of methylglucoside fatty acid esters, fatty acid alkanolamides and fatty acid glucamides; C ₈ -C ₂₂ alkyl mono- and oligoglycosides and their ethoxylated analogs, with glucose being preferred as the sugar component; Mixtures of alkyl (oligo) glucosides and fatty alcohols; Addition products of 5 to 60 moles of ethylene oxide with castor oil and hydrogenated castor oil; Partial esters of polyols having 3 to 6 carbon atoms with saturated fatty acids having 8 to 22 carbon atoms; Sterols (zoosterols, phytosterols, mycosts); Phospholipids, especially glucose phospholipids; Fatty acid esters of sugars and sugar alcohols, such as sorbitol; Polyglycerols and polyglycerol (e.g., commercial product Dehymuls ^® PGPH); Linear and branched fatty acids with 8 to 30 carbon atoms and their Na, K, ammonium, Ca, Mg and Zn salts.

The agents according to the invention preferably contain the emulsifiers in amounts of from 0.1 to 25% by weight, in particular from 0.5 to 15% by weight, based on the total amount of the ready-to-use agent. The preparations according to the invention may preferably contain at least one nonionic emulsifier 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 with an HLB value of 10-15 may be particularly preferred according to the invention.

Among the emulsifier types mentioned, the emulsifiers which contain no ethylene oxide and / or propylene oxide in the molecule are very particularly preferred

Furthermore, the agents according to the invention may contain further active ingredients, auxiliaries and additives, for example nonionic polymers (such as vinylpyrrolidinone / vinyl acrylate copolymers, polyvinylpyrrolidinone, vinylpyrrolidinone / vinyl acetate copolymers, polyethylene glycols and polysiloxanes), cationic polymers (such as quaternized cellulose ethers, polysiloxanes with quaternary groups, dimethyldiallylammonium chloride polymers, acrylamide-dimethyldiallylammonium chloride copolymers, diethyl sulfate-quaternized dimethylaminoethylmethacrylate-vinylpyrrolidinone copolymers, vinylpyrrolidinone-imidazolinium methochloride copolymers and quaternized polyvinyl alcohol), zwitterionic and amphoteric polymers ( such as acrylamidopropyltrimethylammonium chloride / acrylate copolymers and octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers), anionic polymers (such as 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), thickening agents (such as agar-agar, guar gum). Gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, flax gums, dextrans, cellulose derivatives, e.g. For example, methylcellulose, hydroxyalkylcellulose and carboxymethylcellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such. B. bentonite or fully synthetic hydrocolloids such as polyvinyl alcohol), structurants such as (glucose, maleic acid and lactic acid), hair conditioning compounds (such as phospholipids, such as soybean lecithin, egg lecithin and cephalins and silicone oils), protein hydrolysates of plant or animal origin (especially elastin, collagen -, keratin, milk protein, soy protein and wheat protein hydrolysates, their condensation products with fatty acids and quaternized protein hydrolysates), perfume oils, dimethyl isosorbide and cyclodextrins, defoamers (such as silicones, preferably dimethicone), dyes for staining the agent, anti-dandruff agents (such as Piroctone Olamine, zinc Omadine and climbazole), sunscreens (especially derivatized benzophenones, cinnamic acid derivatives and triazines), active ingredients (such as allantoin, Pyrrolidinoncarbonsäuren and their salts and bisabolol), vitamins, provitamins and vitamin precursors (especially those of groups A, B ₃ , B ₅ , B ₆ , C, E, F and H), plant extracts (such as extracts of green tea, oak bark, nettle, witch hazel, hops, chamomile, burdock root, horsetail, lime blossom, almond, aloe vera, spruce needle, horse chestnut, sandalwood, Juniper, Coconut, Mango, Apricot, Lime, Litchi, Wheat, Kiwi, Melon, Orange, Grapefruit, Sage, Rosemary, Birch, Mallow, Meadowfoam, Quenelle, Yarrow, Thyme, Melissa, Hominy, Coltsfoot, Marshmallow, Meristem, Ginseng and Ginger root), vegetable oils (such as macadamia nut oil, kukui nut oil, palm oil, amaranth seed oil, peach kernel oil, avocado oil, olive oil, coconut oil, rapeseed oil, sesame oil, jojoba oil, soybean oil, peanut oil, evening primrose oil and tea tree oil), cholesterol, fats and waxes (such as 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, stabilizers for hydrogen peroxide and other oxidants, Tre ibmittel (such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air) and antioxidants.

The selection of these further substances will be made by the person skilled in the art according to the desired properties of the preparations. The preparations used according to the invention contain the other active ingredients, auxiliaries and additives, preferably in amounts of from 0.1 to 25% by weight, in particular from 0.5 to 15% by weight, based on the total amount of the ready-to-use agent.

The dyeing formulations of the process according to the invention preferably have a pH in the range from 4 to 12. In the case of oxidation colorants, the use of the colorants takes place in a mildly alkaline medium, preferably at a pH in the range of 8.0 to 10.5. The inventively preferred pH of the aftertreatment agent is in a pH range of pH 3 to 5, preferably 3 to 4. The pH values in the context of the present invention are pH values, which at a temperature of 22 ⁰ C were measured.

For the adjustment of the pH, common acidifying and alkalizing agents are known to the person skilled in the art. 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.

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 monoethanolamine and triethanolamine. Can be used according to the invention, Organic alkalizing agents are 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. Very particular preference is given to sodium hydroxide and / or potassium hydroxide. The basic amino acids which can be used as alkalizing agents according to the invention are preferably selected from the group formed from L-arginine, D-arginine, D / L-arginine, L-lysine, D-lysine, D / L-lysine, particularly preferably L-arginine. Arginine, D-arginine, D / L-arginine used as an alkalizing agent according to the invention. Finally, another preferred alkalizing agent is ammonia.

The acidifying agents and the alkalizing agents are preferably used in each case in an amount of from 0.05 to 15% by weight, in particular from 0.5 to 10% by weight, based in each case on the total weight of the ready-to-use preparation.

A second subject of the present invention is a kit of parts which, packaged separately, comprises at least one container A containing a dyeing preparation and at least one container C containing an aftertreatment agent, characterized in that a) the Dye preparation in a cosmetic carrier at least one color-changing component and at least one fiber-structure-improving agent, and that b) the aftertreatment agent in a cosmetic carrier at least one active ingredient selected from the biochinones.

The term "container" hereby signifies a receptacle, irrespective of its shape, material or closure, which includes the possibility of containing substances or mixtures of substances, and the term "container" therefore includes, but is not limited to, the interior of a tube Bag or bag, a canister, a can, a tub, a bottle, a jar or a package, a box, a box, an envelope or other container. The components of the dyeing preparation may be contained in a single container, but it is also possible, and optionally preferred, to divide them into different containers and to guide the consumer to mix them together before use.

The preferred embodiments of the first subject of the invention apply mutatis mutandis for the packaging unit according to the invention of the second subject of the invention. A preferred embodiment of the second subject of the invention is a packaging unit which is characterized in that it also comprises at least one separate container B containing at least one oxidizing agent, and that the dyeing preparation of the container A contains as color-modifying component at least one oxidation dye precursor.

In a particularly preferred embodiment, the packaging unit of the second subject of the invention is characterized in that it comprises at least one additional component selected from the group consisting of personal protective clothing such as disposable gloves, apron, application aid such as comb, brush, brush or applicette, and Contains instructions for use. The instructions for use contain in particular information and instructions for the consumer (m / f) for the application of the means from the containers of the packaging unit in a method according to the first subject of the invention.

Another object of the invention is the use of biochinones following the color change with dyeing formulations containing at least one fiber-structure-improving agent, keratinic fibers to protect the fiber structure. By sparing the fiber structure, a reduced damage to the fiber structure is to be understood in the sense of the invention.

Another object of the invention is finally the use of biochinones following the color change of keratinous fibers with dyeing formulations containing at least one fiber-structure-improving agent to obtain the fiber strength. For the purposes of the invention, obtaining the fiber strength means the lowest possible reduction of the fiber strength. Fiber strength can be determined by conventional tensile stress experiments well known to those skilled in the art. An example of such an experiment is described below.

With regard to further preferred embodiments of the uses according to the invention, mutatis mutandis, what has been said about the process according to the invention applies.

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

1. preparations

1.1 Preparation of the Dyeing Preparation

From the components listed (in% by weight), coloring creams were prepared as follows:

Oxidative dye precursor mixture, containing in each case by weight, 66.7% by weight of p-toluenediamine sulfate, 4.5% by weight of 3-aminophenol, 16.7% by weight of resorcinol and 12.1% by weight of 4- chlororesorcinol.

Lanette ^® D INCI name: Cetearyl alcohol (Cognis) Lorol® ^® tech. INCI name: Coconut alcohol (Cognis) Eumulgin ^® B2 INCI name: Ceteareth-20 (Cognis) Eumulgin ^® B1 INCI name: Ceteareth-12 (Cognis) Lamesoft ^® PO 65 INCI name: Coco-Glucoside, Glyceryl Oleate, Aqua

(Cognis)

Akypo ^® Soft 45HP INCI name: Sodium Laureth-6 Carboxylate, Aqua (KAO) Texapon ^® K14 S Special INCI name: Sodium Myreth Sulfate, Aqua (Cognis) product W 37194 INCI name: Acrylamidopropyltrimonium Chloride / Acrylates

Copolymer, Aqua (Stockhausen)

Sodium silicate 40/42 Soda water glass Puricare ^® LS 9658 INCI name: Aqua, Glycerine, Meringa Pterygosperma Seed

Extract (Cognis) Lanette D, Lorol, Eumulgin B1, Eumulgin B2 and Lamesoft PO 65 were melted together at 80 ⁰ C and dispersed with a portion of the amount of water. Subsequently, the remaining recipe ingredients were incorporated with stirring in order. It was then made up to 100% by weight with water and the formulation was stirred cold.

The formulations E1 and E2 are examples according to the invention. The formulation V1 is a comparative formulation not according to the invention without fiber-structure-improving active ingredient, the formulation V2 with panthenol as active ingredient is a non-inventive dyeing preparation.

1.2. Mixing with the developer dispersion EW

Each staining cream was applied to the strands immediately before application

Weight ratio 1: 1 mixed with a developer dispersion composed as follows.

Texapon ^® NSO INCI name: Sodium Laureth Sulfate (Cognis)

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

Dow Corning ^® DB 110 A INCI name: dimethicone (Dow Corning)

1.3. aftertreatment agent

Cutina GMS ^® V-INCI name: Glyceryl Stearate (Cognis) Dehyquart ^® F 75 INCI name: Distearoylethyl hydroxyethylmonium methosulfate, cetearyl alcohol (Cognis)

Varisoft ^® W 75 PG INCI name: Quaternium-27, Propylene Glycol (Evonik) Cosmedia ^® CTH INCI name: Polyquaternium-37, Propylene Glycol Dicaprylate / Dicaprate, PPG-1 Trideceth-6 (Cognis)

Hydrotriticum ^® WQ INCI name: Aqua, Hydroxypropyltrimonium hydrolyzed wheat protein (Croda)

Marine Hydrolyzed Collagen INCI name: Aqua, hydrolyzed collagen (ISP)

2. Application

For the staining was applied to strands of 50 fibers (codes: Alkinco (New York), 6634, of course, dark European hair) of about 13 cm in length (divided into 2 areas) each applied 4 times the amount of the finished application mixture. After staining for 30 minutes at 32 ° C, the strands were washed with warm water (32 ° C). Immediately thereafter, 0.5 g of the post-treatment agent K1 was applied to the tresses, allowed to act for 2 minutes and then washed with warm water (32 ° C) and dried with a hair dryer.

The dyeing and after-treatment process was repeated three times.

3. Fiber strength (tension-tension measurements)

3.1 Young module

The Young's modulus (also known as Young's modulus) is defined by the ratio of stress to strain in the Hookeian region of a fiber. The Young's modulus is a measure of the strength of a fiber (the higher the value, the stronger the fiber).

According to Hooke's law on elasticity, the deformation of a body under tension is linearly dependent on the force that causes this deformation (tension). For wet hair the Hooke region of the linear dependence is in an expansion under tension of about 0 to 2%.

3.2 test conditions

The measurements were carried out in water at room temperature.

The hair fibers were soaked in water for 1 h before being measured at a constant rate of 10 mm-min ^-1 in the Hooke region (0-1, 5% elongation) by means of a tension-tension system Diastron (UK), and then the Young's modulus was calculated from the applied force.

3.3 Results

After applying usual statistical methods, a highly significant difference was determined for all measured values.

A small difference between the Young's modulus of untreated fibers versus the Young's modulus of treated fibers means little fiber weakening.

From the greatly reduced fiber weakening for the process according to the invention with fiber-structure-improving active compounds (E1 and E2) according to the invention, the technical advantages over the process according to the invention (with V1 and V2) are clear.

Claims

Patent claims

1. A process for color-changing keratinous fibers, wherein a dyeing preparation is applied to the fibers in a first step, is left on the fibers for a contact time T1 and subsequently washed out, and in a second step a post-treatment agent is applied to the keratinic fibers, is left on the fibers for an exposure time T2 and is subsequently washed out, characterized in that a) the dyeing preparation in a cosmetic carrier contains at least one color-modifying component and additionally at least one fiber-structure-improving active agent, b) the period between completion of the first method step and beginning of the second process step is maximally 60 minutes, and c) the aftertreatment agent in a cosmetic carrier contains at least one active ingredient selected from biochinones.

2. The method according to claim 1, characterized in that the dyeing preparation contains as color-modifying component at least one oxidation dye precursor.

3. The method according to any one of claims 1 or 2, characterized in that the dyeing preparation additionally contains at least one oxidizing agent selected from hydrogen peroxide and / or one of its addition products of organic or inorganic compounds.

4. The method according to any one of claims 1 to 3, characterized in that the dyeing preparation contains as fiber-structure-improving active ingredient at least one active ingredient selected from hydroxyl-containing amino acids and / or plant extracts.

5. The method according to claim 4, characterized in that the dyeing preparation contains as fiber-structure-improving agent serine.

6. The method according to claim 4, characterized in that the dyeing preparation contains an extract from the seeds of Moringa Oleifera (Moringa pterygosperma) as fiber-structure-improving active ingredient.

7. The method according to any one of claims 1 to 6, characterized in that the aftertreatment agent contains as biochinone active ingredient at least one active ingredient from the group consisting of mitoquinones and plastoquinones.

8. The method according to any one of claims 1 to 7, characterized in that the aftertreatment agent contains as biochinone active ingredient ubiquinone-50.

9. The method according to any one of claims 1 to 8, characterized in that the aftertreatment agent additionally contains panthenol.

10. Packaging unit (kit-of-parts) which, packaged separately, comprises at least one container A containing a dyeing preparation and at least one container C containing an aftertreatment agent, characterized in that a) the dyeing preparation in a cosmetic carrier at least one color-changing component and at least one fiber-structure-improving active ingredient, and that b) the aftertreatment agent in a cosmetic carrier contains at least one active ingredient selected from biochinones.

11. Packing unit (kit-of-parts) according to claim 10, characterized in that it additionally packaged, at least one container B containing at least one oxidizing agent comprises, and that the dyeing preparation of the container A as a color-changing component contains at least one oxidation dye precursor ,

12. Packaging unit according to claim 10 or 11, characterized in that it contains at least one additional component selected from the group consisting of personal protective clothing, such as disposable gloves, apron, application aid, such as comb, brush, brush or Applicette, and instructions for use contains ,

13. Use of biochinones following the color change of keratinic fibers with dyeing formulations containing fiber-structure-improving active ingredients to protect the fiber structure.

14. Use of biochinones following the color change of keratinic fibers with dyeing formulations containing fiber-structure-improving active ingredients to obtain the fiber strength.