DE102008046883A1 - Hair treatment with spirulina extract - Google Patents

Abstract

The invention relates to a composition for color and / or permanent change in shape of keratinic fibers, characterized in that it contains in a cosmetic carrier at least one color and / or shape-changing component and a blue-green algae extract.

Description

The The invention relates to a means for color and / or permanent change in shape keratin-containing fibers, in particular human hair, which in a cosmetic carrier at least one color and / or shape-changing compound as well as an extract of a blue-green algae contains. Blue-green algae (or cyanobacterium) it is preferably a freshwater blue algae, most preferably the genus Spirulina. Furthermore the invention relates to a method of such keratin-containing agents Fibers. Moreover, the invention relates to the use the agent for coloring and / or permanent change in shape.

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

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

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

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

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

After all another dyeing process has received a lot of attention found. In this process, precursors of the natural Hair Dye Melanin on the substrate, eg. As hair applied; These then form natural analogues in the course of oxidative processes in the hair Dyes off. At, in particular multiple, application of means With 5,6-dihydroxyindoline it is possible to give people with graying Hair to reproduce the natural hair color. The coloration can be done with atmospheric oxygen as the sole oxidant, so that resorted to no further oxidizing agents must become. In persons with originally mittelblondem to brown hair, indoline can be the sole dye precursor be used. For use with persons with original red and especially dark to black hair color can against it Satisfactory results often only through co-use further dye components, in particular special oxidation dye precursors, be achieved.

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 form CH-acidic compounds and compounds having a primary or secondary amino group or hydroxy group, which in turn are selected from compounds of the group formed from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds. The aforementioned components are generally not themselves dyes, and therefore are not suitable alone for dyeing keratinhaltiger fibers alone. In combination, they form dyes in a non-oxidative process of so-called oxo dyeing. The resulting dyeings have partially color fastness on the keratin-containing fiber, which are comparable to those of the oxidation dyeing.

The Nuance spectrum achievable with gentle oxo staining is very wide and the obtained color often shows an acceptable brilliance and color depth. Under compounds of However, second class of oxo dye precursors may also corresponding oxidation dye precursors of the developer and / or Coupler type with or without use of an oxidizing agent Find. Thus, the method of oxo dyeing can be readily combine with the oxidative staining system.

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

The permanent deformation of keratin fibers usually becomes done so that the fiber is mechanically deformed and determines the deformation by suitable means. Before and / or After this deformation, the fiber is treated with the aqueous Preparation of a keratin-reducing substance and rinses after exposure to water or an aqueous solution Solution. In a second step you then treat the Fiber with the aqueous preparation of an oxidizing agent. After an exposure time, this is also rinsed out and the fiber from the mechanical deformation aids (winder, Papilloten) freed.

The aqueous preparation of the keratin-reducing substance is usually alkaline, so on the one hand a sufficient proportion of the thiol functions is deprotonated and on the other hand the fiber swells and in this way a deep Penetration of the keratin-reducing substance into the fiber allows becomes. The keratin-reducing substance cleaves some of the disulfide bonds of the keratin to -SH groups, causing a loosening of peptide crosslinking and due to the tension of the fiber due to the mechanical deformation comes to a reorientation of Keratingefüges. Under the influence of the oxidizing agent again disulfide bonds knotted, and in this way becomes the Keratinefüge Fixed anew in the given deformation. A well known one Method is the permanent wave treatment of human hair. This can be used both for creating curls and waves in smooth Hair as well as for smoothing ruffled hair be applied.

Around To improve the care condition of the fibers, it has long been common the fibers following the color or shape changing Treatment to undergo a special post-treatment. there be, usually in the form of a rinse, the Hair with special ingredients, such as quaternary Ammonium salts or special polymers treated. Through this Treatment will depending on the formulation combability, hold and fullness of the hair improves and the split rate reduced.

In Recently, so-called combination preparations were also designed to reduce the overhead of the usual multi-stage process, especially when used directly by consumers.

These Preparations contain, in addition to the usual components, for example, for coloring the hair, in addition Active ingredients formerly reserved for hair treatment products were. The consumer thus saves an application step; simultaneously The packaging costs are reduced because one product is less used becomes. Nevertheless, even these funds, especially on heavy leave to be cared for fibers, such as Japanese hair, still some wishes concerning the caring properties open.

The can be used in the context of such combination preparations Active ingredients must be particularly in terms of their stability meet high standards, since the dyeing creams or corrugating usually a high pH and the oxidizer formulations have a low pH. Furthermore, incompatibilities of the various active ingredients to each other and thus a low storage stability avoid.

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

On the one hand the use of the oxidizing agents leads to coloration respectively development of the actual coloring to damage in the hair structure and on the hair surface. The hair becomes brittle, leaves its elasticity after and the combability decreases. This injury increases with the duration of use. Commercially available oxidative Dyes usually need over a period of time of 30 minutes and longer to act on the hair fiber. The increase of the exposure time leads to an increased Impairment of the hair structure.

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

Lots Common dyes also contain one high content of anionic, surface-active compounds. However, such anionic surfactants tend to be the keratinic fiber in their natural moisture affect and dry out the fiber like that.

Farther the basic pH is often with ammonia as the alkalizing agent adjusted because ammonia-containing colorants additional Possess advantages in terms of dyeing power. For However, the user has such a colorant the Disadvantage of ammonia in addition to additional damage to the Hair may cause irritation of the eyes or scalp Sensitization or even allergic reactions caused can be. In addition, such possess Dyes an intense, unpleasant odor that in the worst case also lead to irritation of the nasal mucosa can. In addition, the production and storage of Ammonia-containing colorants with problems regarding Be connected handling and stability.

After all affects in addition to the negative influences of hair dyes Also, the use of other Haarbehandlungsmitttel in unfavorable Point out the hair structure. Frequent hair wash, in particular by the use of anionic surfactants in shampoos, also leads to impairments of the surface and the structure of hair.

Not but last, the hair structure is also characterized by outer Environmental influences affected. These are mechanical and thermal effects, such as combing and Blow dry, count. Likewise, weather influences, like wind, rain and UV rays in sunlight, and extra outside Loads, such as chlorinated swimming pool water or Sweat, to damage the hair structure and the Hair surface at.

One Another disadvantage of the previously used funds lies in the clear Moisture loss of the fibers and the scalp, with the treatment which justifies the fibers and, where appropriate, can damage the scalp in the long term.

There is therefore still a need for care agents for the color and / or shape-changing treatment of fibers, which also avoid the drying of the fibers and the scalp. The object of the present invention is therefore to provide a color and / or shape-changing agent by which the abovementioned disadvantages of conventional color and / or shape-changing agents are lowered. The color and / or shape-changing agents are intended to protect the hair and thus cause a reduced damage to the hair. Just attacked and damaged by external influences hair should experience as little additional damage by staining. In particular, protection against oxidative damage to the hair structure and the hair surface should be achieved by the color and / or shape-changing agents. For this purpose, it is desirable for the color and / or shape-changing agent to have a moisture-regulating and / or structuring effect on hair and skin and at the same time improve the result of the color and / or shape-changing treatment in its properties, such as, for example, the fastness properties. Nursing properties of the compositions are particularly desirable, so that the user can do without the use of additional conditioning and aftertreatment agents. Furthermore, the agents should as far as possible be used in a physiologically less impairing pH range, in particular in a neutral pH range. Finally, it is desirable to change color and / or shape de provide means in which the irritation potential, in particular caused by the addition of ammonia, is as low as possible.

In unpredictable, it has now been found that color and / or shape-modifying agents which, in addition to a color and / or shape-changing component of an extract Blue algae contain the above-mentioned disadvantages. conditioned by the protective effect when using the inventive By means of the hair damage can be minimized thereby or even a hair care can be achieved.

One The first object of the invention is therefore an agent for color and / or Permanent change in shape of keratinous fibers, in particular of human hair, containing in a cosmetic vehicle at least a color and / or shape-changing compound and additionally an extract from a blue-green algae.

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

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

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

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

When essential ingredient contains the inventive Means an extract of a blue-green algae.

Blue-green algae, which are also called cyanobacteria and, together with diatoms, Green algae, gold algae and dinogellate to photoautotrophic Plankton, the phytoplankton, are able to due to a certain complex of phycobilins besides chlorophyll a wider part of the natural light spectrum for to take advantage of photosynthesis, which also causes an occurrence in poorer in light Areas is made possible. Due to different Composition of the phycobilin complex with blue (phycocyanin) or red (phycoerythrin) fractions come alongside blue-green algae eponymous bluish colorations also in reddish, greenish or black forms. Blue algae are Gram-negative and one-to-many-celled. Blue algae come in both Salt as well as in fresh water. Examples of Freshwater blue-green algae are the genera Oscillatoria and spirulina.

extracts blue-green algae are rich in proteins, sugars, vitamins and trace elements, especially sodium, potassium, magnesium, manganese, molybdenum, Aluminum, copper and iron. Such extracts are suitable, the To strengthen hair in its structure, the surface improve and also have a positive, vitalizing effect to exercise the scalp. Thus, by using Extracts of blue-green algae compensate for hair damage during the hair dyeing and / or deformation step possible and maintaining the natural moisture content of hair guaranteed. When incorporating an extract from blue-green algae to the coloring and / or shape-changing Means can therefore be the use of nourishing aftertreatment agents or conditioner become redundant.

Especially In the context of the present invention, extracts are preferred especially in freshwater occurring blue-green algae.

Regarding the manner in which the preparation according to the invention is obtained from the blue-green algae constituents exist in principle no restrictions.

It Preparations may be used by mechanical means and / or chemical techniques from blue-green algae. In a significant step, the preparations in a first embodiment by means of mechanical separation methods are obtained from the blue-green algae constituents that are on exploitation of mechanical forces, such as gravity, Centrifugal force, pressure or vacuum, based. Belong to these for example, decanting, filtration, sedimentation, ultrafiltration and centrifuging.

In another embodiment of the present invention preparations are used which, by means of chemical separation methods, for example, an extraction or a chromatographic process, obtained from the blue-green algae constituents. In the context of this Embodiment extracts are particularly preferred. When Extraction agents for the production of said algae extracts can Water, alcohols and mixtures thereof are used. Under the alcohols are lower alcohols such as ethanol and isopropanol, but especially polyhydric alcohols such as ethylene glycol and propylene glycol, both as sole extractant and in mixture with Water, preferably. Blue-green extracts extracted by means of a water / propylene glycol mixture be recovered, have proven to be particularly suitable. It has proved to be particularly suitable when these extractants in a ratio of 1:10 to 10: 1 are used.

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

As well is possible in the invention Agents as Blue Algae Extract The Aqueous Rearing Culture solution of blue-green algae, which also by specific proteins derived from algae, sugars, vitamins and enriched trace elements. These are the blue algae with a physical separation method, such as filtration or centrifugation separated from the culture solution.

In a particularly preferred embodiment of the present invention Invention, the composition contains an extract of freshwater blue algae of the genus Spirulina.

In a preferred embodiment of the present invention Contains the means for color and / or permanent change in shape Keratinischer fibers to further improve the condition of the keratin fiber additionally contains at least one extract from a plant of the genus Aloe.

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

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

Regarding The nature of the aloe extract is basically unlimited. So can both the leaves and the flowers and seeds of aloe plants as a basis for this preparation serve. Particularly preferred according to the invention Preparations have been made from the leaves the aloe plants are obtained.

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

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

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

In another embodiment of the present invention preparations are used which, by means of chemical separation methods, for example, an extraction or a chromatographic process, be obtained from the plant components. In the context of this Embodiment extracts are particularly preferred. When Extraction agent for the preparation of said plant extracts may be used water, alcohols, esters and mixtures thereof become.

Under the alcohols are lower alcohols such as ethanol and isopropanol, but especially polyhydric alcohols such as ethylene glycol and propylene glycol, both as sole extractant and in mixture with Water, preferably. Plant extracts based on water / propylene glycol have proven to be particularly suitable. It has proved to be proven particularly suitable when these extractants in one Ratio of 1:10 to 10: 1 are used.

Under the esters may be preferred according to the invention Esters of kurtzkettigen carboxylic acids and short-chain alcohols use. These include, for example, ethyl acetate, Isopropyl acetate, ethyl propionate. Further advantageous also esters of long-chain, optionally branched fatty acids are used. Here isopropyl myristate has been found to be particularly suitable.

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

One Particularly preferred extract according to the invention of Aloe-Pfalnzen is from the leaves of Aloe Barbadensis extract obtained in isopropyl myristate. Such an extract will for example under the trade name Aloe Vera Extract in IPM of the company Worlée, Hamburg, distributed.

Especially Advantageously, the extract of Aloe to 0.1 to 8 wt .-%, in particular 0.2 to 5.0 wt .-%, each based on the ready-to-use agent, used.

• (1) aus mindestens einem Oxidationsfarbstoffvorprodukt und/oder
• (2) aus Oxofarbstoffvorprodukten und/oder
• (3) aus mindestens einer Vorstufe naturanaloger Farbstoffe und/oder
• (4) aus mindestens einem direktziehenden Farbstoff und/oder.
• (5) mindestens einem Naturfarbstoff.

The coloring component is preferably selected

• (1) from at least one oxidation dye precursor and / or
• (2) from oxo dye precursors and / or
• (3) from at least one precursor of naturally-colored dyes and / or
• (4) from at least one direct dye and / or.
• (5) at least one natural dye.

In a first embodiment, the color-changing Components selected from oxidation dye precursors.

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

In a preferred embodiment, the inventive At least one developer-type oxidation dye precursor and / or coupler type. Preferably, the inventive Colorant at least one oxidation dye precursor of the developer type and at least one oxidation dye precursor of the coupler type.

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

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

wobei

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

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

in which

• G1 represents a hydrogen atom, a C ₁ -C ₄ -alkyl radical, a C ₁ -C ₄ -monohydroxyalkyl radical, a C ₂ -C ₄ -polyhydroxyalkyl radical, a C ₁ -C ₄ -alkoxy-C ₁ -C ₄ -alkyl radical a 4'-aminophenyl radical or a C ₁ -C ₄ alkyl radical substituted with a nitrogen-containing group, a phenyl or a 4'-aminophenyl radical;
• G _{2 represents} a hydrogen atom, a C ₁ -C ₄ -alkyl radical, a C ₁ -C ₄ -monohydroxyalkyl radical, a C ₂ -C ₄ -polyhydroxyalkyl radical, a C ₁ -C ₄ -alkoxy-C ₁ -C ₄ -alkyl radical or a C ₁ -C ₄ alkyl radical substituted with a nitrogen-containing group;
• G 3 represents a hydrogen atom, a halogen atom, such as a chlorine, bromine, iodine or fluorine atom, a C ₁ -C ₄ -alkyl radical, a C ₁ -C ₄ -monohydroxyalkyl radical, a C ₂ -C ₄ -polyhydroxyalkyl radical, C ₁ -C ₄ -alkoxyalkoxy, C ₁ -C ₄ -alkoxy-C ₁ -C ₄ -alkyl, C ₁ -C ₄ -acetylaminoalkoxy, mesylamino-C ₁ -C ₄ -alkoxy or C ₁ - C ₄ carbamoylaminoalkoxy radical;
• G4 represents a hydrogen atom, a halogen atom, a C ₁ -C ₄ -alkyl radical or a C ₁ -C ₄ -alkoxy-C ₁ -C ₄ -alkyl radical or
• When G3 and G4 are ortho to each other, they may together form a bridging .alpha.,. Omega.-alkylenedioxy group such as, for example, an ethylenedioxy group.

Especially Preferred p-phenylenediamines of formula (E1) are selected one or more compounds of the group that is formed p-phenylenediamine, p-toluenediamine, 2-chloro-p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2,6-diethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, N, N-dipropyl-p-phenylenediamine, 4-amino-3-methyl- (N, N-diethyl) aniline, N, N-bis (2-hydroxyethyl) -p-phenylenediamine, 4-N, N-bis (2-hydroxyethyl) amino-2- methylaniline, 4-N, N-bis- (2-hydroxyethyl) amino-2-chloroaniline, 2- (2-hydroxyethyl) -p-phenylenediamine, 2- (1,2-dihydroxyethyl) -p-phenylenediamine, 2-fluoro-p-phenylenediamine, 2-isopropyl-p-phenylenediamine, N- (2-hydroxypropyl) -p-phenylenediamine, 2-hydroxymethyl-p-phenylenediamine, N, N-dimethyl-3-methyl-p-phenylenediamine, N-ethyl-N-2-hydroxyethyl-p-phenylenediamine, N- (2,3-dihydroxypropyl) -p-phenylenediamine, N- (4'-aminophenyl) -p-phenylenediamine, N-phenyl-p-phenylenediamine, 2- (2-hydroxyethyloxy) -p-phenylenediamine, 2-methoxymethyl-p-phenylenediamine, 2- (2-acetylaminoethyloxy) -p-phenylenediamine, N- (2-methoxyethyl) -p-phenylenediamine, N- (4-amino-3-methylphenyl) - N - [3- (1H -imidazol-1-yl) propyl] amine, 5,8-diaminobenzo-1,4-dioxane and their physiologically acceptable salts.

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

It may be further preferred according to the invention as a developer component to use compounds that at least contain two aromatic nuclei containing amino and / or hydroxyl groups are substituted.

wobei:

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

mit der Maßgabe, dass die Verbindungen der Formel (E2) nur eine Verbrückung Y pro Molekül enthalten.Among the binuclear developer components which can be used in the dyeing compositions according to the invention, mention may be made in particular of the compounds corresponding to the following formula (E2) and their physiologically tolerated salts:

in which:

• - Z1 and Z2 independently of one another represent a hydroxyl or NH ₂ radical which is optionally substituted by a C ₁ -C ₄ -alkyl radical, by a C ₁ -C ₄ -hydroxyalkyl radical and / or by a bridging Y or which is optionally Part of a bridging ring system,
• - The bridge Y is an alkylene group having 1 to 14 carbon atoms, such as a linear or branched alkylene chain or an alkylene ring interrupted or terminated by one or more nitrogen-containing groups and / or one or more heteroatoms such as oxygen, sulfur or nitrogen atoms may be substituted by one or more hydroxyl or C ₁ -C ₈ alkoxy, or a direct bond,
• G5 and G6 independently of one another represent a hydrogen or halogen atom, a C ₁ -C ₄ -alkyl radical, a C ₁ -C ₄ -monohydroxyalkyl radical, a C ₂ -C ₄ -polyhydroxyalkyl radical, a C ₁ -C ₄ -aminoalkyl radical or a direct connection to the bridge Y,
• G7, G8, G9, G10, G11 and G12 independently of one another represent a hydrogen atom, a direct bond to the bridge Y or a C ₁ -C ₄ -alkyl radical,

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

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

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

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

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

wobei:

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

Furthermore, it may be preferred according to the invention to use as the developer component a p-aminophenol derivative or one of its physiologically tolerable salts. Particular preference is given to p-aminophenol derivatives of the formula (E3)

in which:

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

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

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

All particularly preferred compounds of the formula (E3) are p-aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (1,2-dihydroxyethyl) phenol and 4-amino-2- (diethylaminomethyl) phenol.

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

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

worin

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

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

wherein

• G17, G18 and G19 independently of one another represent a hydrogen atom, a hydroxy group, a C ₁ -C ₄ -alkoxy group or an amino group, and
• G20 represents a hydroxy group or a group -NG21G22, in which G21 and G22 independently of one another represent a hydrogen atom, a C ₁ -C ₄ -alkyl group, a C ₁ -C ₄ -monohydroxyalkyl group,

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

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

worin

• – G21, G22, G23 stehen unabhängig voneinander für ein Wasserstoffatom, eine C₁-C₄-Alkylgruppe, eine C₁-C₄-Monohydroxyalkylgruppe, eine C₂-C₄-Polyhydroxyalkylgruppe, eine gegebenenfalls substituierte Arylgruppe oder eine gegebenenfalls substituierte Aryl-C₁-C₄-alkylgruppe, mit der Maßgabe dass, wenn G23 für ein Wasserstoffatom steht, G24 neben den vorgenannten Gruppen zusätzlich für eine Gruppe -NH₂ stehen kann,
• – G24 steht für ein Wasserstoffatom, eine C₁-C₄-Alkylgruppe, eine C₁-C₄-Monohydroxyalkylgruppe oder eine C₂-C₄-Polyhydroxyalkylgruppe und
• – G25 steht für ein Wasserstoffatom, eine gegebenenfalls substituierte Arylgruppe, eine C₁-C₄-Alkylgruppe oder eine C₁-C₄-Monohydroxyalkylgruppe, insbesondere für ein Wasserstoffatom oder eine Methylgruppe.

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

wherein

• G21, G22, G23 independently of one another represent a hydrogen atom, a C ₁ -C ₄ -alkyl group, a C ₁ -C ₄ -monohydroxyalkyl group, a C ₂ -C ₄ -polyhydroxyalkyl group, an optionally substituted aryl group or an optionally substituted aryl group C ₁ -C ₄ -alkyl group, with the proviso that when G 23 is a hydrogen atom, G 24 may additionally be a group -NH _{2 in} addition to the abovementioned groups,
• G24 represents a hydrogen atom, a C ₁ -C ₄ -alkyl group, a C ₁ -C ₄ -monohydroxyalkyl group or a C ₂ -C ₄ -polyhydroxyalkyl group and
• G25 represents a hydrogen atom, an optionally substituted aryl group, a C ₁ -C ₄ -alkyl group or a C ₁ -C ₄ -monohydroxyalkyl group, in particular a hydrogen atom or a methyl group.

Prefers binds in formula (E5) the residue -NG23G24 to the 5 position and the Rest G27 to the 3-position of the pyrazole cycle.

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

wobei:

• – G26, G27 und G28, G29 unabhängig voneinander stehen für ein Wasserstoffatom, einen C₁-C₄-Alkylrest, einen Aryl-Rest, einen C₁-C₄-Monohydroxyalkylrest, einen C₂-C₄-Polyhydroxyalkylrest, einen C₁-C₄-Alkoxy-C₁-C₄-alkylrest, einen C₁-C₄-Aminoalkylrest, der gegebenenfalls durch ein Acetyl-Ureid- oder einen Sulfonyl-Rest geschützt sein kann, einen C₁-C₄-Alkylamino-C₁-C₄-alkylrest, einen Di-(C₁-C₄-alkyl)amino-C₁-C₄-alkylrest, wobei die Dialkyl-Reste gegebenenfalls einen Kohlenstoffcyclus oder einen Heterocyclus mit 5 oder 6 Kettengliedern bilden, einen C₁-C₄-Monohydroxyalkyl- oder einen Bis-(C₁-C₄-Hydroxyalkyl)amino-C₁-C₄-alkylrest,
• – die X-Reste stehen unabhängig voneinander für ein Wasserstoffatom, einen C₁-C₄-Alkylrest, einen Aryl-Rest, einen C₁-C₄-Monohydroxyalkylrest, einen C₂-C₄-Polyhydroxyalkylrest, einen C₁-C₄-Aminoalkylrest, einen C₁-C₄-Alkylamino-C₁-C₄-alkylrest, einen Di-(C₁-C₄-alkyl)amino-C₁-C₄-alkylrest, wobei die Dialkyl-Reste gegebenenfalls einen Kohlenstoffcyclus oder einen Heterocyclus mit 5 oder 6 Kettengliedern bilden, einen C₁-C₄-Hydroxyalkyl- oder einen Di-(C₁-C₄-hydroxyalkyl)amino-C₁-C₄-alkylrest, einen Aminorest, einen C₁-C₄-Alkylaminorest, einen Di-(C₁-C₄-alkyl)aminorest, C₁-C₄-hydroxyalkylaminorest oder einen Di-(C₁-C₄-hydroxyalkyl)aminorest, ein Halogenatom, eine Carboxylsäuregruppe oder eine Sulfonsäuregruppe,
• – i hat den Wert 0, 1, 2 oder 3,
• – p hat den Wert 0 oder 1,
• – q hat den Wert 0 oder 1 und
• – n hat den Wert 0 oder 1, mit der Maßgabe, dass
• – die Summe aus p + q ungleich 0 ist,
• – wenn p + q gleich 2 ist, n den Wert 0 hat, und die Gruppen NG26G27 und NG28G29 belegen die Positionen (2,3); (5,6); (6,7); (3,5) oder (3,7);
• – wenn p + q gleich 1 ist, n den Wert 1 hat, und die Gruppen NG26G27 (oder NG28G29) und die Gruppe OH belegen die Positionen (2,3); (5,6); (6,7); (3,5) oder (3,7);

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

in which:

• - G26, G27 and G28, G29 independently of one another represent a hydrogen atom, a C ₁ -C ₄ -alkyl radical, an aryl radical, a C ₁ -C ₄ -monohydroxyalkyl radical, a C ₂ -C ₄ -polyhydroxyalkyl radical, a C ₁ C ₄ -C ₄ alkoxy-C ₁ -C ₄ alkyl, C ₁ -C ₄ aminoalkyl which may be optionally protected by an acetyl-ureide or a sulfonyl radical, a C ₁ -C ₄ -alkylamino-C C ₁ -C ₄ -alkyl radical, a di (C ₁ -C ₄ -alkyl) amino-C ₁ -C ₄ -alkyl radical, where the dialkyl radicals optionally form a carbon cycle or a heterocycle having 5 or 6 chain members, a C ₁ C ₄ monohydroxyalkyl or a bis (C ₁ -C ₄ hydroxyalkyl) amino C ₁ -C ₄ alkyl radical,
• - The X radicals independently of one another represent a hydrogen atom, a C ₁ -C ₄ -alkyl radical, an aryl radical, a C ₁ -C ₄ -monohydroxyalkyl radical, a C ₂ -C ₄ -polyhydroxyalkyl radical, a C ₁ -C ₄ aminoalkyl, C ₁ -C ₄ alkylamino-C ₁ -C ₄ alkyl group, a di (C ₁ -C ₄ alkyl) amino-C ₁ -C ₄ alkyl group, wherein the dialkyl residues optionally a Kohlenstoffcyclus or form a heterocycle with 5 or 6 chain links, a C ₁ -C ₄ hydroxyalkyl or a di- (C ₁ -C ₄ hydroxyalkyl) amino-C ₁ -C ₄ alkyl group, an amino group, a C ₁ -C _4- alkylamino radical, a di (C ₁ -C ₄ -alkyl) amino radical, C ₁ -C ₄ -hydroxyalkylamino radical or a di- (C ₁ -C ₄ -hydroxyalkyl) amino radical, a halogen atom, a carboxylic acid group or a sulfonic acid group,
• - i has the value 0, 1, 2 or 3,
• - p has the value 0 or 1,
• - q has the value 0 or 1 and
• - n has the value 0 or 1, with the proviso that
• The sum of p + q is not equal to 0,
• If p + q is 2, n is 0, and groups NG26G27 and NG28G29 occupy the positions (2, 3); (5,6); (6,7); (3,5) or (3,7);
• If p + q is 1, n is 1, and the groups NG26G27 (or NG28G29) and the group OH occupy the positions (2, 3); (5,6); (6,7); (3,5) or (3,7);

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

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

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

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

• - pyrazolo [1,5-a] pyrimidine-3,7-diamine;
• 2,5-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine;
• - pyrazolo [1,5-a] pyrimidine-3,5-diamine;
• 2,7-dimethylpyrazolo [1,5-a] pyrimidine-3,5-diamine;
• 3-aminopyrazolo [1,5-a] pyrimidin-7-ol;
• 3-aminopyrazolo [1,5-a] pyrimidin-5-ol;
• 2- (3-aminopyrazolo [1,5-a] pyrimidin-7-ylamino) ethanol;
• - 2- (7-aminopyrazolo [1,5-a] pyrimidin-3-ylamino) ethanol;
• - 2 - [(3-aminopyrazolo [1,5-a] pyrimidin-7-yl) - (2-hydroxy-ethyl) -amino] -ethanol;
• - 2 - [(7-aminopyrazolo [1,5-a] pyrimidin-3-yl) - (2-hydroxy-ethyl) -amino] -ethanol;
• 5,6-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine;
• - 2,6-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine;
• 3-amino-7-dimethylamino-2,5-dimethylpyrazolo [1,5-a] pyrimidine;

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

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

The following are examples of the radicals mentioned as substituents of the compounds of the formulas (E1) to (E6): Examples of C ₁ -C ₄ -alkyl radicals are the groups CH ₃ , CH ₂ CH ₃ , CH ₂ CH ₂ CH ₃ , CH (CH _{3) 2,} CH ₂ CH ₂ CH ₂ CH _3, CH ₂ CH (CH _{3) 2,} CH (CH ₃₎ CH ₂ CH _3, C (CH _{3). 3}

Examples of C ₁ -C ₄ -alkoxy radicals according to the invention are OCH ₃ , OCH ₂ CH ₃ , OCH ₂ CH ₂ CH ₃ , OCH (CH ₃ ) ₂ , OCH ₂ CH ₂ CH ₂ CH ₃ , OCH ₂ CH (CH ₃ ) ₂ , OCH (CH ₃ ) CH ₂ CH ₃ , OC (CH ₃ ) ₃ , in particular a methoxy or an ethoxy group.

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

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

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

Examples of nitrogen-containing groups are in particular NH ₂ , C ₁ -C ₄ -monoalkylamino groups, di (C ₁ -C ₄ -alkyl) amino groups, tri (C ₁ -C ₄ -alkyl) ammonium groups, C ₁ -C ₄ -monohydroxyalkylamino groups , Imidazolinium and NH ₃ ⁺ .

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

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

Examples of tri (C ₁ -C ₄ alkyl) ammonium groups are N ⁺ (CH ₃ ) ₃ , N ⁺ (CH ₃ ) ₂ (CH ₂ CH ₃ ), N ⁺ (CH ₃ ) (CH ₂ CH ₃ ) ₂ ,

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

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

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

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

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

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

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

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

Examples of di- (C ₁ -C ₄ -hydroxyalkyl) aminoC ₁ -C ₄ -alkyl radicals are CH ₂ CH ₂ N (CH ₂ CH ₂ OH) ₂ , CH ₂ CH ₂ CH ₂ N (CH ₂ CH ₂ OH ) ₂ , CH ₂ CH ₂ N (CH ₂ CH ₂ CH ₂ OH) ₂ , CH ₂ CH ₂ CH ₂ N (CH ₂ CH ₂ CH ₂ OH) ₂ . An example of an aryl group is the phenyl group.

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

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

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

Coupler components do not form significant staining in the course of oxidative staining 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.

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

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

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.

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

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

Especially preferred m-aminophenol coupler components are selected from at least one compound from the group that is formed from m-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-methylaminobenzene, 3-ethylamino-4-methylphenol, 2,4-dichloro-3-aminophenol and the physiologically acceptable Salts of all the above compounds.

worin
G5, G6, G7 und G8 unabhängig voneinander stehen für ein Wasserstoffatom, eine C₁-C₄-Alkylgruppe, eine C₃-C₆-Cycloalkylgruppe, eine C₁₂-C₄-Alkenylgruppe, eine C₁-C₄-Monohydroxyalkylgruppe, eine C₂-C₄-Polyhydroxyalkylgruppe, eine C₁-C₄-Alkoxy-C₁-C₄-alkylgruppe, eine Aryl-C₁-C₄-alkylgruppe, eine Heteroaryl-C₁-C₄-alkylgruppe, eine C₂-C₄-Perfluoracylgruppe, oder gemeinsam mit dem Stickstoffatom einen fünfgliedrigen oder sechsgliedrigen Heterocyclus bilden
G9 und G10 unabhängig voneinander stehen für ein Wasserstoffatom, ein Halogenatom, eine C₁-C₄-Alkylgruppe, eine ω-(2,4-Diaminophenyl)-C₁-C₄-alkylgruppe, eine ω-(2,4-Diaminophenyloxy)-C₁-C₄-alkoxygruppe, eine C₁-C₄-Alkoxygruppe, eine Hydroxygruppe, eine C₁-C₄-Alkoxy-C₂-C₄-alkoxygruppe, eine Arylgruppe, eine Heteroarylgruppe, eine C₁-C₄-Monohydroxyalkylgruppe, eine C₂-C₄-Polyhydroxyalkylgruppe, eine Hydroxy-C₁-C₄-alkoxygruppe.The m-diaminobenzenes or their derivatives which can be used according to the invention are preferably selected selected from at least one compound of the formula (K2) and / or from at least one physiologically tolerable salt of a compound according to formula (K2),

wherein
G5, G6, G7 and G8 independently of one another represent a hydrogen atom, a C ₁ -C ₄ -alkyl group, a C ₃ -C ₆ -cycloalkyl group, a C ₁₂ -C ₄ -alkenyl group, a C ₁ -C ₄ -monohydroxyalkyl group, a C ₂ -C ₄ polyhydroxyalkyl group, a C ₁ -C ₄ alkoxy C ₁ -C ₄ alkyl group, an aryl C ₁ -C ₄ alkyl group, a heteroaryl C ₁ -C ₄ alkyl group, a C ₂ -C ₄ perfluoroacyl group, or together with the nitrogen atom form a five-membered or six-membered heterocycle
G9 and G10 independently represent a hydrogen atom, a halogen atom, a C ₁ -C ₄ alkyl group, a ω- (2,4-diaminophenyl) C ₁ -C ₄ alkyl group, an ω- (2,4-diaminophenyloxy ) C ₁ -C ₄ alkoxy group, a C ₁ -C ₄ alkoxy group, a hydroxy group, a C ₁ -C ₄ alkoxy C ₂ -C ₄ alkoxy group, an aryl group, a heteroaryl group, a C ₁ -C ₄ monohydroxyalkyl group, a C ₂ -C ₄ polyhydroxyalkyl group, a hydroxy C ₁ -C ₄ alkoxy group.

Especially preferred m-diaminobenzene coupler components are selected from at least one compound from the group that is formed from m-phenylenediamine, 2- (2,4-diaminophenoxy) ethanol, 1,3-bis (2,4-diaminophenoxy) propane, 1-Methoxy-2-amino-4- (2'-hydroxyethylamino) benzene, 1,3-bis (2,4-diaminophenyl) propane, 2,6-bis (2'-hydroxyethylamino) -1-methylbenzene, 2- ({3 - [(2-hydroxyethyl) amino] -4-methoxy-5-methylphenyl} amino) ethanol, 2 - ({3 - [(2-hydroxyethyl) amino] -2-methoxy-5-methylphenyl} amino) ethanol, 2 - ({3 - [(2-hydroxyethyl) amino] -4,5-dimethylphenyl} amino) ethanol, 2- [3-morpholin-4-yl-phenyl) -amino] -ethanol, 3-amino-4- (2-methoxy-ethoxy) -5-methyl-phenylamine, 1-amino-3-bis- (2'-hydroxyethyl) aminobenzene and the physiological compatible salts of all the compounds mentioned above.

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

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

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

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

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

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

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

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

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

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

wherein
G23 represents a hydrogen atom, a C ₁ -C ₄ -alkyl group, a C ₃ -C ₆ -cycloalkyl group, a C ₂ -C ₄ -alkenyl group, a C ₁ -C ₄ -monohydroxyalkyl group, a C ₂ -C ₄ -polyhydroxyalkyl group , an aryl-C ₁ -C ₄ -alkyl group,
G24 represents a hydroxy group or a group NG26G27, wherein G26 and G27 are each independently hydrogen, C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl, C ₂ -C ₄ alkenyl, C C ₁ -C ₄ monohydroxyalkyl group, a C ₂ -C ₄ polyhydroxyalkyl group,
G25 is a hydrogen atom, a halogen atom or a C ₁ -C ₄ -alkyl group,
with the proviso that G ²⁴ binds in the meta position or ortho position to the structural fragment NG23 of the formula.

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

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

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

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

preferred Pyrimidine derivatives are selected from at least one Compound of the group formed from 4,6-diaminopyrimidine, 4-amino-2,6-dihydroxypyrimidine, 2,4-diamino-6-hydroxypyrimidine, 2,4,6-trihydroxypyrimidine, 2-amino-4-methylpyrimidine, 2-amino-4-hydroxy-6-methylpyrimidine and 4,6-dihydroxy-2-methylpyrimidine and the physiologically acceptable Salts of the aforementioned compounds.

The following are examples of the radicals mentioned as substituents of the compounds of the formulas (K1) to (K6): Examples of C ₁ -C ₄ -alkyl radicals are the groups CH ₃ , CH ₂ CH ₃ , CH ₂ CH ₂ CH ₃ , CH (CH _{3) 2,} CH ₂ CH ₂ CH ₂ CH _3, CH ₂ CH (CH _{3) 2,} CH (CH ₃₎ CH ₂ CH _3, C (CH _{3). 3}

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

Examples of C ₁ -C ₄ -alkoxy radicals according to the invention are OCH ₃ , OCH ₂ CH ₃ , OCH ₂ CH ₂ CH ₃ , CH (CH ₃ ) ₂ , OCH ₂ CH ₂ CH ₂ CH ₃ , OCH ₂ CH (CH ₃ ) ₂ , OCH (CH ₃ ) CH ₂ CH ₃ , OC (CH ₃ ) ₃ , in particular a methoxy or an ethoxy group.

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

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

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

Examples of nitrogen-containing groups are in particular NH ₂ , C ₁ -C ₄ -monoalkylamino groups, di (C ₁ -C ₄ -alkyl) amino groups, tri (C ₁ -C ₄ -alkyl) ammonium groups, (C ₁ -C ₄ - Monohydroxyalkyl) amino groups, imidazolinium and NH ₃ ⁺ .

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

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

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

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

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

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

An example of an aryl group is the phenyl group, which may also be substituted. Examples of aryl-C ₁ -C ₄ -alkyl groups are the benzyl group and the 2-phenylethyl group.

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

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

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

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

eingesetzt.As a color-modifying component according to the invention, oxo dye precursors can also be used in a further embodiment. 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) CH-acidic compounds and / or from (oxo2b) compounds having a primary or secondary amino group or hydroxy group selected from at least one compound of the group formed from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds

used.

• a) von Aminen und deren Derivate unter Bildung von Iminen oder Oximen als Additionsverbindung
• b) von Alkoholen unter Bildung von Acetalen oder Ketalen als Additionsverbindung
• c) von Wasser unter Bildung von Hydraten als Additionsverbindung (Komponente (Oxo1) leitet sich in diesem Fall c) von einem Aldehyd ab)

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

• a) amines and derivatives thereof to form imines or oximes as addition compound
• b) of alcohols to form acetals or ketals as addition compound
• c) of water to form hydrates as addition compound (component (Oxo1) is derived in the case c) of an aldehyde)

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

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

worin

• • R1, R2 und R3 stehen unabhängig voneinander für ein Wasserstoffatom, ein Halogenatom, eine C₁-C₆-Alkylgruppe, eine C₂-C₆-Alkenylgruppe, eine Formylgruppe, eine Hydroxygruppe, eine C₁-C₆-Alkoxygruppe, eine C₁-C₆-Dialkylaminogruppe, eine Di-(C₂-C₆-hydroxyalkyl)aminogruppe, eine Di-(C₁-C₆-alkoxy-C₁-C₆-alkyl)aminoguppe, eine C₁-C₆-Hydroxyalkyloxygruppe, eine Sulfonylgruppe, eine Carboxylgruppe, eine Sulfonsäuregruppe, eine Sulfonamidgruppe, eine Carbamoylgruppe, eine C₂-C₆-Acylgruppe, eine Acetylgruppe oder eine Nitrogruppe,
• • Z' steht für eine direkte Bindung oder eine Vinylengruppe,
• • R4 und R5 stehen für ein Wasserstoffatom oder bilden gemeinsam, zusammen mit dem Restmolekül einen 5- oder 6-gliederigen aromatischen oder aliphatischen Ring.

Benzaldehyde and / or cinnamaldehyde and / or naphthaldehyde and / or at least one derivative of these abovementioned aldehydes, which in particular carry one or more hydroxyl, alkoxy or amino substituents, are very particularly preferably used as the reactive carbonyl component in the oxo dyeing. In this case, preference is again given to the reactive carbonyl compound of the component (oxo1) selected from at least one compound of the formula (AC-1),

wherein

• R _1, R _{2 and} R 3 are each independently hydrogen, halogen, C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, formyl, hydroxy, C ₁ -C ₆ alkoxy, C ₁ -C ₆ -dialkylamino group, a di- (C ₂ -C ₆ -hydroxyalkyl) amino group, a di (C ₁ -C ₆ -alkoxy-C ₁ -C ₆ -alkyl) amino group, a C ₁ -C ₆ Hydroxyalkyloxy group, sulfonyl group, carboxyl group, sulfonic acid group, sulfonamide group, carbamoyl group, C ₂ -C ₆ acyl group, acetyl group or nitro group,
• Z 'is a direct bond or a vinylene group,
• • R4 and R5 represent a hydrogen atom or together form, together with the remainder of the molecule, a 5- or 6-membered aromatic or aliphatic ring.

The derivatives of benzaldehydes, naphthaldehydes or cinnamaldehydes of the reactive carbonyl compound according to component (Oxo1) are preferably selected from at least one compound of the group consisting of 4-hydroxy-3-methoxybenzaldehyde, 3,5-dimethoxy-4-hydroxybenzaldehyde, 4-hydroxy 1-naphthaldehyde, 4-hydroxy-2-methoxybenzaldehyde, 3,4-dihydroxy-5-methoxybenzaldehyde, 3,4,5-trihydroxybenzaldehyde, 3,5-dibromo-4-hydroxybenzaldehyde, 4-hydroxy-3-nitrobenzaldehyde, 3 Bromo-4-hydroxybenzaldehyde, 4-hydroxy-3-methylbenzaldehyde, 3,5-dimethyl-4-hydroxybenzaldehyde, 5-bromo-4-hydroxy-3-methoxybenzaldehyde, 4-diethylamino-2-hydroxybenzaldehyde, 4-dimethylamino-2 -methoxybenzaldehyd, 2-methoxybenzaldehyde, 3-methoxybenzaldehyde, 4-methoxybenzaldehyde, 2-ethoxybenzaldehyde, 3-ethoxybenzaldehyde, 4-ethoxybenzaldehyde, 4-hydroxy-2,3-dimethoxybenzaldehyde, 4-hydroxy-2,5-dimethoxybenzaldehyde, 4-hydroxy-2, 6-dimethoxybenzaldehyde, 4-hydroxy-2-methylbenzaldehyde, 4-hydroxy-2,3-dimethylbenzaldehyde, 4-hydroxy-2,5-dimethylbenzaldehyde, 4-hydroxy-2,6-dimethylbenzaldehyde, 3,5-diethoxy-4- hydroxybenzaldehyde, 2,6-diethoxy-4-hydroxybenzaldehyde, 3-hydroxy-4-methoxybenzaldehyde, 2-hydroxy-4-methoxybenzaldehyde, 2-ethoxy-4-hydroxybenzaldehyde, 3-ethoxy-4-hydroxybenzaldehyde, 4-ethoxy-2 -hydroxybenzaldehyde, 4-ethoxy-3-hydroxybenzaldehyde, 2,3-dimethoxybenzaldehyde, 2,4-dimethoxybenzaldehyde, 2,5-dimethoxybenzaldehyde, 2,6-dimethoxybenzaldehyde, 3,4-dimethoxybenzaldehyde, 3,5-dimethoxybenzaldehyde, 2,3 , 4-trimethoxybenzaldehyde, 2,3,5-trimethoxybenzaldehyde, 2,3,6-trimethoxybenzaldehyde, 2,4,6-trimethoxybenzaldehyde, 2,4,5-trimethoxybenzaldehyde, 2,5,6-trimethoxybenzaldehyde, 2-hydroxybenzaldehyde, 3 -Hydroxybenzald ehyd, 4-hydroxybenzaldehyde, 2,3-dihydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 2,4-dihydroxy-3-methylbenzaldehyde, 2,4-dihydroxy-5-methylbenzaldehyde, 2,4-dihydroxy-6-methylbenzaldehyde, 2,4-dihydroxy-3-methoxybenzaldehyde, 2,4-dihydroxy-5-methoxybenzaldehyde, 2,4-dihydroxy-6-methoxybenzaldehyde, 2,5-dihydroxybenzaldehyde, 2,6-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde, 3, 4-Dihydroxy-2-methylbenzaldehyde, 3,4-dihydroxy-5-methylbenzaldehyde, 3,4-dihydroxy-6-methylbenzaldehyde, 3,4-dihydroxy-2-methoxybenzaldehyde, 3,5-dihydroxybenzaldehyde, 2,3,4- Trihydroxybenzaldehyde, 2,3,5-trihydroxybenzaldehyde, 2,3,6-trihydroxybenzaldehyde, 2,4,6-trihydroxybenzaldehyde, 2,4,5-trihydroxybenzaldehyde, 2,5,6-trihydroxybenzaldehyde, 4-dimethylaminobenzaldehyde, 4-diethylaminobenzaldehyde, 4-Dimethylamino-2-hydroxybenzaldehyde, 4-pyrrolidinobenzaldehyde, 4-morpholinobenzaldehyde, 2-morpholinobenzaldehyde, 4-piperidinobenzaldehyde, 3,5-dichloro-4-hydroxybenzaldehyde, 4-hydroxy-3,5-diiodobenzaldehyde, 3-chloro-4- hydroxybenzaldehy d, 5-chloro-3,4-dihydroxybenzaldehyde, 5-bromo-3,4-dihydroxybenzaldehyde, 3-chloro-4-hydroxy-5-methoxybenzaldehyde, 4-hydroxy-3-iodo-5-methoxybenzaldehyde, 2-methoxy 1-naphthaldehyde, 4-methoxy-1-naphthaldehyde, 2-hydroxy-1-naphthaldehyde, 2,4-dihydroxy-1-naphthaldehyde, 4-hydroxy-3-methoxy-1-naphthaldehyde, 2-hydroxy-4-methoxy 1-naphthaldehyde, 3-hydroxy-4-methoxy-1-naphthaldehyde, 2,4-dimethoxy-1-naphthaldehyde, 3,4-dimethoxy-1-naphthaldehyde, 4-dimethylamino-1-naphthaldehyde, 3-hydroxy-4- nitrobenzaldehyde, 2-hydroxy-3-methoxy-5-nitrobenzaldehyde, 5-nitrovanillin, 2,5-dinitrosalicylaldehyde, 5-bromo-3-nitrosalicylaldehyde, 2-dimethylaminobenzaldehyde, 2-chloro-4-dimethylaminobenzaldehyde, 4-dimethylamino-2- methylbenzaldehyde, 4-diethylaminocinnamaldehyde, 4-dibutylaminobenzaldehyde, 3-carboxy-4-hydroxybenzaldehyde, 5-carboxyvanillin, 3-carboxy-4-hydroxy-5-methylbenzaldehyde, 3-carboxy-5-ethoxy-4-hydroxybenzaldehyde, 3 Carboxy-4-hydroxybenzaldehyde, 5-carboxyvanillin, 3-carboxy-4-hydroxy-5-methylbenzaldehyde, 3-carboxy 5-ethoxy-4-hydroxybenzaldehyde, 3-allyl-4-hydroxybenzaldehyde, 3-allyl-4-hydroxy-5-methoxybenzaldehyde, 3-allyl-4-hydroxy-5-methylbenzaldehyde, 3-allyl-5-bromo-4- hydroxybenzaldehyde, 3,5-diallyl-4-hydroxybenzaldehyde, 3-allyl-5-carboxy-4-hydroxybenzaldehyde and 3-allyl-4-hydroxy-5-formylbenzaldehyde.

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

worin

• • R6 steht für eine lineare oder cyclische C₁-C₆-Alkylgruppe, eine C₂-C₆-Alkenylgruppe, eine gegebenenfalls substituierte Arylgruppe, eine gegebenenfalls substituierte Heteroarylgruppe, eine Aryl-C₁-C₆-alkylgruppe, eine C₁-C₆-Hydroxyalkylgruppe, eine C₂-C₆-Polyhydroxyalkylgruppe, eine C₁-C₆-Alkoxy-C₁-C₆-alkylgruppe, eine Gruppe R^IR^IIN-(CH₂)_m-, worin R^I und R^II stehen unabhängig voneinander für ein Wasserstoffatom, eine C₁-C₄-Alkylgruppe, eine C₁-C₄-Hydroxyalkylgruppe oder eine Aryl-C₁-C₆-alkylgruppe, wobei R^I und R^II gemeinsam mit dem Stickstoffatom einen 5-, 6- oder 7-gliedrigen Ring bilden können und m steht für eine Zahl 2, 3, 4, 5 oder 6,
• • R⁷ steht für eine C₁-C₆-Alkylgruppe, insbesondere für eine Methylgruppe,
• • X^– steht für ein physiologisch verträgliches Anion,
• • der Cyclus der Formel (CH-1) repräsentiert alle Ringstrukturen, die zusätzlich weitere Heteroatome wie Stickstoff, Sauerstoff oder Schwefel enthalten können und ferner ankondensierte Ringstrukturen tragen können, wobei alle diese Ringsstrukturen zusätzliche Substituenten tragen können,
• • Het steht für einen gegebenenfalls substituierten Heteroaromaten,
• • X¹ steht für eine direkte Bindung oder eine Carbonylgruppe.

Very particular preference is given to using as component (oxo2a) at least one CH-acidic compound having an aromatic or aliphatic, heterocyclic main body which is selected from cyclic onium compounds having the structural unit of the formula (CH-1) and / or compounds of the formula (CH-) 2)

wherein

• R ₆ is a linear or cyclic C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, an aryl-C ₁ -C ₆ -alkyl group, a C ₁ - C ₆ hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a C ₁ -C ₆ alkoxy C ₁ -C ₆ alkyl group, a group R ^I R ^II N- (CH ₂ ) _m -, wherein R ^I and R ^II independently of one another represent a hydrogen atom, a C ₁ -C ₄ -alkyl group, a C ₁ -C ₄ -hydroxyalkyl group or an aryl-C ₁ -C ₆ -alkyl group, where R ^I and R ^{II are} ge together with the nitrogen atom may form a 5-, 6- or 7-membered ring and m is a number 2, 3, 4, 5 or 6,
• R ⁷ is a C ₁ -C ₆ -alkyl group, in particular a methyl group,
• • X ^- is a physiologically acceptable anion,
• The cycle of the formula (CH-1) represents all ring structures which may additionally contain further heteroatoms such as nitrogen, oxygen or sulfur and may further carry fused ring structures, all of these ring structures being able to carry additional substituents,
• Het is an optionally substituted heteroaromatic,
• • X ¹ represents a direct bond or a carbonyl group.

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

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

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

worin

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

The CH-acidic compounds of the oxo dye precursors of the component (oxo2a) are preferably selected from at least one compound of the formula (CH-3),

wherein

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

At least one group R 10 or R 12 according to formula (CH-3) necessarily stands for a C ₁ -C ₆ -alkyl group. This alkyl group preferably carries at least two hydrogen atoms on its α-carbon atom. Particularly preferred alkyl groups are the methyl, ethyl, propyl, n-butyl, i-butyl, n-pentyl, neo-pentyl, n-hexyl group. Most preferably, R 10 and R 12 are each independently hydrogen or a methyl group, wherein at least one group R 10 or R 12 represents a methyl group.

In In a preferred embodiment, Y is of the formula (CH-3) for an oxygen or a sulfur atom, more preferred for an oxygen atom.

The radical R 8 of the formula (CH-3) is preferably selected from a C ₁ -C ₆ -alkyl group (particularly preferably a methyl group), a C ₂ -C ₆ -alkenyl group (in particular an allyl group), a C ₂ -C ₆ - Hydroxyalkyl group (especially a 2-hydroxyethyl group) or an optionally substituted benzyl group.

R11 of the formula (CH-3) is preferably a hydrogen atom.

Particularly preferred in formula (CH-3) are the radicals R9, R10 and R12 is a methyl group, the radical R11 is a hydrogen atom, Y is an oxygen or sulfur atom and the radical R ⁸ is selected from a C ₁ -C ₆ Alkyl group (particularly preferably a methyl group), a C ₂ -C ₆ alkenyl group (especially an allyl group), a C ₂ -C ₆ hydroxyalkyl group (especially a 2-hydroxyethyl group) or an optionally substituted benzyl group.

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

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

X ^- in the formulas (CH-1) and (CH-3), as well as in the above lists preferably halide, Benzolsul fonate, p-toluenesulfonate, (C ₁ -C ₄ -alkane) sulfonate, trifluoromethanesulfonate, perchlorate, 0.5 sulfate, hydrogensulfate, tetrafluoroborate, hexafluorophosphate or tetrachlorozincate. The anions chloride, bromide, iodide, hydrogensulfate or p-toluenesulfonate are particularly preferably used as X ^- .

links of the formula (CH-3) according to the invention are particularly preferably used.

The CH-acidic compounds of the oxo dye precursors of the component (Oxo2a) are most preferably selected from at least one compound of the group consisting of 2- (2-furoyl) acetonitrile, 2- (5-bromo-2-furoyl) acetonitrile, 3- (2,5-dimethyl-3-furyl) -3-oxopropanitrile, 2- (2-thenoyl) acetonitrile, 2- (3-thenoyl) acetonitrile, 2- (5-fluoro-2-thenoyl) acetonitrile, 2- (5-chloro-2-thenoyl) acetonitrile, 2- (5-bromo-2-thenoyl) acetonitrile, 2- (5-methyl-2-thenoyl) acetonitrile, 2- (2,5-dimethypyrrol-3-oyl) acetonitrile, 2- (1,2,5-trimethylpyrrol-3-oyl) acetonitrile, 1H-benzimidazol-2-ylacetonitrile, 1H-benzothiazol-2-ylacetonitrile, 2- (pyrid-2-yl) acetonitrile, 2,6-bis (cyanomethyl) pyridine, 2- (indol-3-oyl) acetonitrile, 2- (2-methylindol-3-oyl) acetonitrile, 2- (6-Hydroxy-4,7-dimethoxy-1-benzofuran-5-oyl) acetonitrile, 1,2,3,3-tetramethyl-3H-indolium Iodide, 1,2,3,3-tetramethyl-3H-indolium p-toluenesulfonate, 1,2,3,3-tetramethyl-3H-indolium Methanesulfonate, 2,3-dimethyl-benzothiazolium iodide, 2,3-dimethyl-benzothiazolium p-toluenesulfonate, 1,4-dimethylquinolinium iodide, 1,2-dimethylquinolinium Iodide, 3-ethyl-2-methylbenzoxazolium iodide, 3-ethyl-2-methyl-benzothiazolium Iodide, 1-ethyl-4-methyl-quinolinium iodide, 1-ethyl-2-methylquinolinium Iodide, 1,2,3-trimethylquinoxalinium iodide, 3-ethyl-2-methyl-benzoxazolium p-toluenesulfonate, 3-ethyl-2-methylbenzothiazolium p-toluenesulfonate, 1-ethyl-4-methylquinolinium p-toluenesulfonate, 1-ethyl-2-methylquinolinium p-toluenesulfonate, 1,2,3-trimethylquinoxalinium p-toluenesulfonate, 1-allyl-1,2-dihydro-3,4,6-trimethyl-2-oxopyrimidinium Bromide, 1,2-dihydro-1- (2-hydroxyethyl) -3,4,6-trimethyl-2-oxopyrimidinium p-toluenesulfonate, 1,2-dihydro-1,3,4,6-tetramethyl-2-oxopyrimidinium Chloride, 1,2-dihydro-1,3-diethyl-4,6-dimethyl-2-oxopyrimidinium Chloride, 1,2-dihydro-1,3-dipropyl-4,6-dimethyl-2-oxopyrimidinium Chloride, 1-allyl-1,2-dihydro-3,4,6-trimethyl-2-oxopyrimidinium bisulfate, 1,2-dihydro-1- (2-hydroxyethyl) -3,4,6-trimethyl-2-oxopyrimidinium Hydrogen sulfate, 1,2-dihydro-1,3,4,6-tetramethyl-2-oxopyrimidinium Hydrogen sulfate, 1,2-dihydro-1,3-diethyl-4,6-dimethyl-2-oxopyrimidinium Hydrogen sulfate, 1,2-dihydro-1,3-dipropyl-4,6-dimethyl-2-oxopyrimidinium Hydrogen sulfate, 1,2-dihydro-1,3,4-trimethyl-2-oxopyrimidinium chloride, 1,2-dihydro-1,3,4-trimethyl-2-oxo-pyrimidinium bisulfate, 1,2-dihydro-1,3-diethyl-4-methyl-2-oxo-pyrimidinium chloride, 1,2-dihydro-1,3-diethyl-4-methyl-2-oxo-pyrimidinium bisulfate, 1,2-dihydro-1,3-dipropyl-4-methyl-2-oxo-pyrimidinium chloride, 1,2-dihydro-1,3-dipropyl-4-methyl-2-oxo-pyrimidinium Hydrogen sulfate, 1,2-dihydro-1,3,4,6-tetramethyl-2-thioxo-pyrimidinium Chloride, 1,2-dihydro-1,3-diethyl-4,6-dimethyl-2-thioxopyrimidinium Chloride, 1,2-dihydro-1,3-dipropyl-4,6-dimethyl-2-thioxo-pyrimidinium Chloride, 1,2-dihydro-1,3,4,6-tetramethyl-2-thioxopyrimidinium bisulphate, 1,2-dihydro-1,3-dipropyl-4,6-dimethyl-2-thioxopyrimidinium bisulphate, 1,2-dihydro-1,3,4-trimethyl-2-thioxopyrimidinium chloride, 1,2-dihydro-1,3,4-trimethyl-2-thioxopyrimidinium Hydrogen sulfate, 1,2-dihydro-1,3-diethyl-4-methyl-2-thioxopyrimidinium Chloride, 1,2-dihydro-1,3-diethyl-4-methyl-2-thioxopyrimidinium bisulfate, 1,2-dihydro-1,3-dipropyl-4-methyl-2-thioxopyrimidinium chloride and 1,2-dihydro-1,3-dipropyl-4-methyl-2-thioxopyrimidinium bisulfate.

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

The above-mentioned compounds of the component (Oxo1) and of the component (Oxo2), if they are used, respectively preferably in an amount of 0.03 to 65 mmol, in particular of 1 to 40 mmol, based on 100 g of the total agent used.

Farther can the agents of the invention as Color-modifying component at least one substantive Dye included. These are dyes that directly put on hair and no oxidative process for training need the color. Direct dyes are usually nitrophenylenediamines, Nitroaminophenols, azo dyes, anthraquinones or indophenols.

The substantive dyes are each preferably in an amount from 0.001 to 20% by weight, based on the total application preparation, used. The total amount of substantive dyes is preferably at most 20% by weight.

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

When anionic substantive dyes are in particular 6-hydroxy-5 - [(4-sulfophenyl) azo] -2-naphthalenesulfonic acid Disodium salt (C. I. 15.855, Food Yellow No. 3, FD & C Yellow No. 6), 2,4-dinitro-1-naphthol-7-sulfonic acid disodium salt (C.I. 10.316; Acid Yellow 1; Food Yellow No. 1), 2- (indan-1,3-dione-2-yl) quinoline-x, x-sulfonic acid (Mixture of mono- and disulfonic acid) (C.I. 47,005; D & C Yellow No. 10; Food Yellow No. 13; Acid Yellow 3, Yellow 10), 4 - ((4-amino-3-sulfophenyl) azo) benzenesulfonic acid Disodium salt (C.I. 13,015, Acid Yellow 9), 5-hydroxy-1- (4-sulfophenyl) -4 - [(4-sulfophenyl) azo] pyrazole-3-carboxylic acid trisodium salt (C.I. 19, 140; Food Yellow No. 4; Acid Yellow 23), 3 - [(4-phenylamino) phenyl] azobenzenesulfonic acid Sodium salt (C.I. 13.065; Ki406; Acid Yellow 36), 9- (2-carboxyphenyl) -6-hydroxy-3H-xanthen-3-one (C.I. 45, 350; Acid Yellow 73; D & C Yellow No. 8), 5 - [(2,4-dinitrophenyl) amino] -2-phenylaminobenzenesulfonic acid Sodium salt (C.I. 10, 385; Acid Orange 3), 4 - [(2,4-dihydroxyphenyl) azo] benzenesulfonic acid Sodium salt (C.I. 14,270; Acid Orange 6), 4 - [(2-hydroxynaphth-1-yl) azo] benzenesulfonic acid Sodium salt (C.I. 15.510; Acid Orange 7), 4 - [(2,4-dihydroxy-3 - [(2,4-dimethylphenyl) azo] -phenyl) azo] benzenesulfonic acid Sodium salt (C.I. 20, 170; Acid Orange 24), 4-hydroxy-3 - [(2-methoxyphenyl) azo] -1-naphthalenesulfonic acid Sodium salt (C.I. 14.710; Acid Red 4), 4-hydroxy-3 - [(4-sulfonaphth-1-yl) azo] -1-naphthalenesulfonic acid Disodium salt (C.I. 14,720; Acid Red No. 14), 6-hydroxy-5 - [(4-sulfonaphth-1-yl) azo] -2,4-naphthalenedisulfonic acid Trisodium salt (C. I. 16,255; Ponceau 4R; Acid Red 18), 3-hydroxy-4 - [(4-sulfonaphth-1-yl) azo] -2,7-naphthalenedisulfonic acid Trisodium salt (C. I. 16,185; Acid Red 27), 8-amino-1-hydroxy-2- (phenylazo) -3,6-naphthalenedisulfonic acid Disodium salt (C.I. 17,200; Acid Red 33; Red 33), 5- (acetylamino) -4-hydroxy-3 - [(2-methylphenyl) azo] -2,7-naphthalenedisulfonic acid Disodium salt (C.I. 18.065; Acid Red 35), 2- (3-hydroxy-2,4,5,7-tetraiodo-dibenzopyran-6-one-9-yl) benzoic acid Disodium salt (C.I. 45,430; Acid Red 51), N- [6- (diethylamino) -9- (2,4-disulfophenyl) -3H-xanthen-3-ylidene] -N-ethyl-urethonium Hydroxide, inner salt, sodium salt (C. I. 45, 100; Acid Red 52), 8 - [(4- (phenylazo) phenyl) azo] -7-naphthol-1,3-disulfonic acid Disodium salt (CI 27.290, Acid Red 73), 2 ', 4', 5 ', 7'-tetrabromo-3', 6'-dihydroxyspiro [isobenzofuran-1 (3H), 9 '- [9H] xanthene] -3- on Disodium salt (CI 45.380; Acid Red 87), 2,4,5 ', 7'-tetrabromo-4,5,6,7-tetrachloro-3', 6'-dihydroxyspiro [isobenzofuran-1 (3H), 9 '[ 9H] xanthene] -3-one Disodium salt (C.I. 45.410; Acid Red 92), 3 ', 6'-dihydroxy-4', 5'-diiodospiro [isobenzofuran-1 (3H), 9 '(9H) -xanthene] -3-one disodium salt (C.I. 45425; Acid Red 95), 2-hydroxy-3 - ((2-hydroxynaphth-1-yl) azo) -5-nitrobenzenesulfonic acid sodium salt (C.I. 15.685; Acid Red 184), 3-hydroxy-4- (3-methyl-5-oxo-1-phenyl-4,5-dihydro-1H-pyrazol-4-ylazo) naphthalene-1-sulfonic acid Sodium salt, chromium complex (Acid Red 195), 3-hydroxy-4 - [(4-methyl-2-sulfonphenyl) azo] -2-naphthalenecarboxylic acid Calcium salt (C.I. 15,850: 1; Pigment Red 57: 1), 3 - [(2,4-dimethyl-5-sulfophenyl) azo] -4-hydroxy-1-naphthalenesulfonic acid Disodium salt (C.I. 14,700, Food Red No. 1, Ponceau SX, FD & C Red No. 4), 1,4-bis (2-sulfo-4-methylphenyl) amino] -9,10-anthraquinone disodium salt (C.I. 61,570; Acid Green 25), bis (4-dimethylaminophenyl) - (3,7-disulfo-2-hydroxynaphth-1-yl) carbenium inner Salt, sodium salt (C. I. 44,090, Food Green No. 4, Acid Green 50), Bis [4- (diethylamino) -phenyl] - (2,4-disulfophenyl) carbenium inner Salt, sodium salt (2: 1) (C. I. 42,045; Food Blue No. 3; Acid Blue 1), bis [4- (diethylamino) phenyl] - (5-hydroxy-2,4-disulfophenyl) carbenium, inner salt, calcium salt (2: 1) (CI 42.051, Acid Blue 3), N- [4 - [(2,4-disulfophenyl) [4- [ethyl (phenylmethyl) amino) phenyl] methylene] -2,5- cyclohexadien-1 ylidene] -N-ethylbenzolmethanaminium hydroxide, inner salt, sodium salt (C. I. 42,080, Acid Blue 7), (2-sulfophenyl) di [4- (ethyl ((4-sulfophenyl) methyl) amino) phenyl] carbenium Disodium salt betaine (C. I. 42,090, Acid Blue 9, FD & C Blue No. 1), 1-amino-4- (phenylamino) -9,10-anthraquinone-2-sulfonic acid (C.I., 62,055; Acid Blue 25), 1-amino-4- (cyclohexylamino) -9,10-anthraquinone-2-sulfonic acid Sodium salt (CI 62045; Acid Blue 62), 2- (1,3-dihydro-3-oxo-5-sulfo-2H-indol-2-ylidene) -2,3-dihydro-3-oxo-1H-indole 5-sulfonic acid Disodium salt (C.I. 73.015; Acid Blue 74), 9- (2-carboxyphenyl) -3 - [(2-methylphenyl) amino] -6 - [(2-methyl-4-sulfophenyl) amino] xanthylium, internal salt, sodium salt (C.I. 45.190; Acid Violet 9), 1-hydroxy-4 - [(4-methyl-2-sulfophenyl) amino] -9,10-anthraquinone Sodium salt (C.I. 60,730; D & C Violet No. 2; Acid Violet 43), bis [3-nitro-4 - [(4-phenylamino) -3-sulfophenylamino] -phenyl] sulfone (C.I. 10.410; Acid Brown 13), 5-amino-4-hydroxy-6 - [(4-nitrophenyl) -azo] -3- (phenylazo) -2,7-naphthalenedisulfonic acid Disodium salt (C.I. 20,470; Acid Black 1), 3-hydroxy-4 - [(2-hydroxynaphth-1-yl) azo] -7-nitro-1-naphthalenesulfonic acid Chromium complex (3: 2) (CI 15,711, Acid Black 52), 4- (acetylamino) -5-hydroxy-6 - [(7-sulfo-4 - [(4-sulfophenyl) azo] naphth-1-yl) azo ] -1,7-naphthalene disulfonic acid Tetrasodium salt (C.I. 28,440, Food Black No. 1), 3 ', 3 ", 5', 5" -tetrabromophenolsulfonephthalein (Bromophenol blue).

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

Particularly suitable cationic direct dyes are 9- (dimethylamino) -benzo [a] phenoxazine-7-ium chloride (CI 51.175; Basic Blue 6), di- [4- (diethylamino) phenyl] [4- (ethylamino) naphthyl]. carbenium chloride (CI 42,595; Basic Blue 7), di (4- (dimethylamino) phenyl) - (4- (methylphenylamino) -naphthalen-1-yl) carbenium chloride (CI 42,563, Basic Blue 8), 3, 7-di (dimethylamino) phenothiazine-5-ium chloride (CI 52.015 Basic Blue 9), di- [4- (dimethylamino) phenyl] [4- (phenylamino) naphthyl] carbenium chloride (CI 44.045, Basic Blue 26), 2 - [(4- (ethyl (2-hydroxyethyl) amino) phenyl) azo] -6-methoxy-3-methyl-benzothiazolium methylsulfate (CI 11.154, Basic Blue 41), 8-amino-2-bromo-5-hydroxy-4-imino-6 - [(3- (trimethylammonio) -phenyl ) amino] -1 (4H) -naphthalenone chloride (CI 56.059, Basic Blue No. 99), bis [4- (dimethylamino) phenyl] - [4- (methylamino) phenyl] carbenium chloride (CI 42.535, Basic Violet 1 Tri- (4-amino-3-methylphenyl) carbenium chloride (CI 42,520, Basic Violet 2), tri- [4- (dimethylamino) -phenyl] carbenium chloride (CI 42,555, Basic Violet 3), 2- [3 , 6- (Diethylamino) dibenzopyranium-9-yl] benzoic acid chloride (CI 45.170, Basic Violet 10), di (4-aminophenyl) (4-amino-3-methylphenyl) carbenium chloride (CI 42.510 Basic Violet 14), 1 , 3-Bis - [(2,4-diamino-5-methylphenyl) azo] -3-methylbenzene (CI 21.010; Basic Brown 4), 1 - [(4-aminophenyl) azo] -7- (trimethylammonio) -2 -naphthol chloride (CI 12.250, Basic Brown 16), 1 - [(4-amino-2-ni trophenypazo] -7- (trimethylammonio) -2-naphthol chloride, 1 - [(4-amino-3-nitrophenyl) azo] -7- (trimethylammonio) -2-naphthol chloride (CI 12.251; Basic Brown 17), 3 - [(4-amino-2,5-dimethoxyphenyl) azo] -N, N, N-trimethylbenzylaminium chloride (CI 12,605, Basic Orange 69), 3,7-diamino-2,8-dimethyl 5-phenylphenazinium chloride (CI 50.240, Basic Red 2), 1,4-dimethyl-5 - [(4-dimethylaminophenyl) azo] -1,2,4-triazolium chloride (CI 11.055, Basic Red 22), 2- Hydroxy-1 - [(2-methoxyphenyl) azo] -7- (trimethylammonio) naphthalene chloride (CI 12.245; Basic Red 76), di- [4-dimethylaminophenyl] iminomethane chloride (CI 41,000, Basic Yellow 2), 2- [ 2- (2,4-dimethoxyphenylamino) ethenyl] -1,3,3-trimethyl-3H-indol-1-ium chloride (CI 48.055, Basic Yellow 11), 3-methyl-1-phenyl-4 - [(3 -trimethylammoniophenyl) azo] pyrazol-5-one chloride (CI 12,719, Basic Yellow 57), bis [4-diethylaminophenyl] phenylcarbenium hydrogensulfate (1: 1) (CI 42,040, Basic Green 1), di (4-dimethylaminophenyl) phenylmethanol (CI 42,000, Basic Green 4), 1- (2-morpholiniumpropylamino) -4-hydroxy-9,10-anthraquinone methylsulfate, 1 - [(3- (dimethylpropylaminium) -propyl) amino] -4-methylamino -9,10-anthraquinone chloride and substantive dyes containing a heterocycle having at least one quaternary nitrogen atom.

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

Preferred cationic substantive dyes are included

• (a) cationic triphenylmethane dyes such as Basic Blue 7, Basic Blue 26, Basic Violet 2 and Basic Violet 14,
• (b) aromatic systems substituted with a quaternary nitrogen group, such as Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 and Basic Brown 17, as well as
• (C) direct dyes containing a heterocycle having at least one quaternary nitrogen atom, as described for example in the EP-A2-998 908 to be named.

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

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

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

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

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

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

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

Suitable quinone dyes are in particular:
1,4-Di - [(2,3-dihydroxypropyl) amino] -9,10-anthraquinone, 1,4-di - [(2-hydroxyethyl) amino] -9,10-anthraquinone (CI 61.545, Disperse Blue 23 ), 1 - [(2-hydroxyethyl) amino] -4-methylamino-9,10-anthraquinone (CI 61,505, Disperse Blue 3), 2 - [(2-aminoethyl) amino] -9,10-anthraquinone (HC Orange 5), 1-amino-4-hydroxy-9,10-anthraquinone (CI 60.710, Disperse Red 15), 1-hydroxy-4 - [(4-methyl-2-sulfophenyl) amino] -9,10-anthraquinone, 7-β-D-glucopyranosyl-9,10-dihydro-1-methyl-9,10-dioxo-3,5,6,8-tetrahydroxy-2-anthracenecarboxylic acid (CI 75,470, Natural Red 4), 1 - [( 3-aminopropyl) amino] -4-methylamino-9,10-anthraquinone (HC Blue 8), 1 - [(3-aminopropyl) amino] -9,10-anthraquinone (HC Red 8), 1,4-diamino 2-methoxy-9,10-anthraquinone (CI 62.015, Disperse Red 11, Solvent Violet No. 26), 1,4-dihydroxy-5,8-bis [(2-hydroxyethyl) amino] -9,10-anthraquinone (CI 62,500, Disperse Blue 7, Solvent Blue No. 69), 1,4-diamino-9,10-anthraquinone (CI 61.100, Disperse Violet 1), 1-amino-4- (methylamino) -9,10-anthraquinone (CI 61,105, Dispense Viole t 4, Solvent Violet No. 12), 2-hydroxy-3-methoxy-1,4-naphthoquinone, 2,5-dihydroxy-1,4-naphthoquinone, 2-hydroxy-3-methyl-1,4-naphthoquinone, N- {6 - [( 3-Chloro-4- (methylamino) phenyl) imino] -4-methyl-3-oxo-1,4-cyclohexadien-1-yl} urea (HC Red 9), 2 - {{4- [di (2 -hydroxyethyl) amino] phenyl} amino} -5 - [(2-hydroxyethyl) amino] -2,5-cyclohexadiene-1,4-dione (HC Green 1), 5-hydroxy-1,4-naphthoquinone (CI 75,500 , Natural Brown 7), 2-hydroxy-1,4-naphthoquinone (CI 75,480, Natural Orange 6), 1,2-dihydro-2- (1,3-dihydro-3-oxo-2H-indol-2-ylidene) -3H-indol-3-one (CI 73,000), 4- { {5 - [(2-hydroxyethyl) amino] -1-methyl-1H-pyrazol-4-yl} imino} -4,5-dihydro-5 - [(2-hydroxyethyl) imino] -1-methyl-1H- pyrazole sulfate (1: 1), hydrate (1: 1).

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

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

Farther can as direct dyes and natural dyes be used. As natural dyes in the context of the invention Understanding dyes derived from parts of plants. For this purpose, preferably different parts of plants are suitable, depending on desired dye. It is understood, however, that a Dye can be obtained from more than one plant part. The preferred plant parts for the production of natural dyes are contained in the group, which is formed from root, stems, Bark, heartwood, resin, blossom, leaf, fruit and sap.

in the According to the invention, it is still for natural dyes It is not necessary that the extracted from the plant parts Means are dyes as such, but that they may be also represent dye precursors, which are characterized by subsequent chemical Reactions form the actual dye. Called here in particular the oxidation with atmospheric oxygen to form the Chromophore.

It is in particular for the purposes of the invention not required that the dyes or dye precursors in each case uniform Represent connections. Due to different, not uniform Extraction methods such as different extraction or fermentation conditions or by using different, regional subspecies and various plant parts or partially also from culture-historical tradition contain some mentioned Natural dyes deliberately no uniform compounds, but Mixtures of dyes, dye precursors and other components, especially tannins.

For the purposes of the invention, a natural dye is, of course, also understood to mean a discrete colorant compound isolated from such a mixture or optionally also a plurality of discrete colorant compounds isolated from such a mixture. Detailed descriptions of the natural dyes can be found, inter alia, in the handbook of natural dyes known to the person skilled in the art: Occurrence, use, detection, H. Schweppe, ecomed publishing company, 1993, Landsberg / Lech ,

• a) Diaryloylmethanfarbstoffe, wie beispielsweise in Kurkuma (Gelbwurzel) enthalten (C.I. Natural Yellow 3) – Curcuma domestica mit den färbenden Inhaltsstoffen Curcumin (C.I. 75300), Demethoxycurcumin und Bisdemethoxycurcumin.
  
• b) Naphthochinonfarbstoffe, wie beispielsweise in Henna, rot (C.I. Natural Orange 6) aus den Blättern des Hennastrauchs – Lawsonia inermis L. mit dem färbenden Inhaltsstoff Lawson (C.I. 75480):
  
  in Fruchtschalen und Blättern (C.I. Natural Brown 7) des Walnussbaums – Juglus regia L. mit dem färbenden Inhaltsstoff Juglon (C.I. 75500):
  
  in Alkannawurzel oder Shikoninwurzel (C.I. Natural Red 20) – Alkanna tinctoria beziehungsweise Lithospermum erythrorhizon mit dem färbenden Inhaltsstoffen Alkannan (C.I. 75520) und Alkannin (C.I. 75530) beziehungsweise Shikonin (C.I. 75535):
  
  in Lapachoholz von Tecoma ipé, Tecoma lapacho, Tecoma leucoxylon oder Tecoma achracea (C.I. Natural Yellow 16) mit dem färbenden Inhaltsstoffen Lapachol (C.I. 75490), sowie untergeordnet Desoxylapachol, ☐-Lapachon, ☐-Lapachon, Melchinon I, Lapachonon und Dehydro-☐-lapachon:
  
• c) Anthrachinonfarbstoffe, wie beispielsweise in Krapp-Wurzeln (C.I. Natural Red 8) – Rubia peregrina und Rubia tinctorum mit den färbenden Inhaltsstoffen Purpurin (C.I. 75410), Pseudopurpurin (C.I. 75420; C.I. 58220-snythetisch), Alizarin (C.I. 75330), Rubiadin (C.I. 75350) und Munjistin (C.I. 75370):
  
  in den Wurzeln und Stengeln des Indischen Krapp (C.I. Natural Red 16) – Rubia cordifolia und Rubia sikkimensis mit den färbenden Inhaltsstoffen Purpurin (C.I. 75410), Pseudopurpurin (C.I. 75420; C.I. 58220-snythetisch), Alizarin (C.I. 75330), und Munjistin (C.I. 75370) sowie Nordamnacanthal, Physcion und Purpuroxanthin (C.I. 75340):
  
  in Rharbarber-Wurzeln – Rheum undulatum L. Rheum palmatum L. und weitere Rheum-Spezies mit den färbenden Inhaltsstoffen Emodin, Chrystophanol (C.I. 75400; C.I. Natural Yellow 23), Aloe-emodin, Physcion, Rhéin, den Heterodianthronen Rhéidin A, B, C, Palmidin A, B, C, D und Sennidin C sowie davon abgeleitete Anthra- und Diglykoside:
  
  in den Wurzeln des Echten Labkraut – Galium verum L., Gemeinen Labkraut – Galium mollugo L., Klebkraut – Galium aparine L., Waldmeister – Galium odoratum (C.I. Natural Red 14) mit den färbenden Inhaltsstoffen Purpurin (C.I. 75410), Pseudopurpurin (C.I. 75420; C.I. 58220-snythetisch), Alizarin (C.I. 75330), Rubiadin (C.I. 75350), Purpuroxanthin (C.I. 75340), Lucidin, Alizarin-1-methylether, Alizarin-2-methylether, 2-Hydroxyanthrachinon und 1-Hydroxy-2-methylanthrachinon:
  
  in Färbermeisterwurzel (C.I. Natural Red 13) – Asperula tinctoria mit den färbenden Inhaltsstoffen Purpurin (C.I. 75410), Pseudopurpurin (C.I. 75420; C.I. 58220-snythetisch) und Alizarin (C.I. 75330), in Rinde des Faulbaum – Rhamnus fragula L. tinctoria mit den färbenden Inhaltsstoffen Emodin, 4 Emodin-Glukoside: Glucofragulin A, Glucofrangulin B, Frangulin A, Frangulin B, Physcion und Chrysophanol (C.I. 75400):
  
• d) Indigoide Farbstoffe, wie beispielsweise in den Blättern und teilweise Stengeln des Indischem Indigo – Indigofera tinctoria (Indigofera argentea), Färberwaid – Isatis tinctoria, Färberoleander – Wrightia tinctoria und Wildem Indigo – Baptisia tinctoria (C.I. Natural Blue 1) mit den Farbstoffvorprodukten Isatan B und Indican, welche durch einen Gärungsprozess oxidativ in den eigentlichen Farbstoff Indigo (C.I. 75780; C.I. 73000) sowie untergeordnet Indirubin (C.I. 75790; C.I. 73200) und Isatin überführt werden:
  
  unter anderem unter den Namen Indigofera folium oder Henna, schwarz als Handelsprodukt, zumeist in Kombination mit Extrakten von Lawsonia Inermis, erhältlich,
• e) Flavonoidfarbstoffe, wie beispielsweise in den Blütenköpfen von Römischer Kamille – Chamaemelum nobile (C.I. Natural Yellow 1) und Deutscher Kamille – Chamomilla recutica mit den färbenden Inhaltsstoffen Apigenin (C.I. 75580; C.I. Natural Yellow 1,2), Rutin (C.I. 75730; Natural Yellow 10), sowie untergeordnet Luteolin (C.I. 75590), Kämpferol (C.I. 75460, C.I. Natural Yellow 13, 10) und Quercetin (C.I. 75670; C.I. Natural Yellow 10,13; C.I. Natural Red 1) und davon abgeleitete Glukoside:
  
  in den Blättern und Stengeln von Salbei – Salvia tribola L. mit den färbenden Inhaltsstoffen Luteolin (C.I. 75590) und Salvigenin:
  
  in den Blättern und Stengeln von Rosmarin – Rosmarinus Officinalis mit den färbenden Inhaltsstoffen Luteolin (C.I. 75590) und Apigenin (C.I. 75580; C.I. Natural Yellow 1,2) sowie weiteren Flavonoiden,
• f) Neoflavanoidfarbstoffe, wie beispielsweise in Blauholz (C.I. Natural Black 1), Kernholz von Haematoxylum campechianum L. mit dem färbenden Flavinoid Quercetin und dem Farbstoffvorprodukt Hämatoxylin, welches oxidativ in den Farbstoff Hämatein (C.I. 75290, C.I. Natural Black 1 und 2) umgewandelt wird:
  
  in Sappanholz – Caesalpinia sappan L., Brazilienholz – Caesalpinia brasiliensis L., Nicaraguaholz – Caesalpinia echinata, Pernambunkholz – Caesalpinia crista L., Brasilietteholz – Haematoxylum braziletto, jeweils als Kernholz (C.I. Natural Red 24), mit dem Farbstoffvorprodukt Brasilin, welches oxidativ in den Farbstoff Brasilein (C.I. 75280, C.I. Natural Red 24) umgewandelt wird:
  
• g) unlösliche Rotholz-Farbstoffe, wie beispielsweise in Rotem Sandelholz, Kernholz von Pterocarpus santalinus L., Narraholz – Pterocarpus indicus L., Barholz – Pterocarpus soyauxii L., Camholz – Bahia nitida (C.I. Natural Red 22) mit den färbenden Inhaltsstoffen Santalin A, Santalin B, Tetra-O-methylsantarubin, Hompterocarpin, Pterocarpin, Maackiain, den Isoflavioniden Formononetin und Santal, sowie dem Chalkon Isoliquiritigenin und dem Flavon Liquiritigenin:
  
• h) Betalainfarbstoffe wie beispielsweise in Rote Beete Wurzeln – Beta vulgaris mit den färbenden Hauptinhaltsstoffen Betanidin und Praebetanin sowie untergeordnet weiteren Betacyaninen, Betaxanthinen, Vulgaxanthinen, Anthocyanen und Eisen- und Kupfer-Komplexen:
  
• i) Gallotanninfarbstoffe wie beispielsweise in der Rinde von Stiel- oder Sommereiche – Quercus robur L. mit den färbenden Hauptinhaltsstoffen aus der Gruppe der Gallotannine und Ellagentannine (Glykoside der Gallussäure beziehungsweise der Ellagsäure; C.I. 75270):
  
• j) Farbstoffe aus kondensierten Gerbstoffen, wie beispielsweise in Catechu (C.I. Natural Brown 3), eine Mischung aus Extrakten von Färbepflanzen, vorzugsweise Acacia catechu, Areca catechu und Uncaria gambier, mit einem hohen Anteil von kondensierten Gerbstoffen (,Proanthocyanidine') vom Catechin-Typ:
  
  wie in den Blättern von grünem und schwarzem (= fermentiertem grünen) Tee – Camellia sinensis, mit den Inhaltsstoffen Gallussäure, m-Digallussäure, Catechin, Glykosiden von Flavonoiden wie, unter anderen, Luteolin, Apigenin, Kämpferol, Quercetin, Myriecetin, sowie Thearubingenine (,Proanthocyanidine'), Theaflavin und Isotheaflavin:
  

The following classes of natural dyes are preferred in the cosmetic compositions according to the invention as colorants for keratinic fibers:

• a) Diaryloylmethanfarbstoffe, such as in turmeric (Goldenseal) (CI Natural Yellow 3) - Curcuma domestica with the coloring ingredients curcumin (CI 75300), demethoxycurcumin and bisdemethoxycurcumin.
  
• b) naphthoquinone dyes, as in henna, red (CI Natural Orange 6) from the leaves of henna - Lawsonia inermis L. with the coloring ingredient Lawson (CI 75480):
  
  in fruit peel and leaves (CI Natural Brown 7) of the walnut tree - Juglus regia L. with the coloring ingredient Juglon (CI 75500):
  
  in alkana root or shikonin root (CI Natural Red 20) - Alkanna tinctoria or Lithospermum erythrorhizon with the coloring ingredients alkannane (CI 75520) and alkanine (CI 75530) or shikonin (CI 75535):
  
  in Lapacho wood of Tecoma ipé, Tecoma lapacho, Tecoma leucoxylon or Tecoma achracea (CI Natural Yellow 16) with the coloring ingredients lapachol (CI 75490), as well as subordinate deoxylapachol, ☐-lapachone, ☐-lapachone, melchinone I, lapachonone and dehydro-□ lapachone:
  
• c) anthraquinone dyes, such as in madder roots (CI Natural Red 8) - Rubia peregrina and Rubia tinctorum with the coloring ingredients purpurin (CI 75410), pseudopurpurine (CI 75420, CI 58220-synthetic), alizarin (CI 75330), rubiadin (CI 75350) and Munjistine (CI 75370):
  
  in the roots and stems of Indian madder (CI Natural Red 16) - Rubia cordifolia and Rubia sikkimensis with the coloring ingredients purpurin (CI 75410), pseudopurpurine (CI 75420, CI 58220-synthetic), alizarin (CI 75330), and munjistine ( CI 75370) as well as Nordamnacanthal, Physcion and Purpuroxanthin (CI 75340):
  
  in Rharbarber roots - Rheum undulatum L. Rheum palmatum L. and other Rheum species with the coloring constituents Emodin, Chrystophanol (CI 75400, CI Natural Yellow 23), Aloe-emodin, Physcion, Rhéin, the heterodianthrones Rhéidine A, B, C, palmidin A, B, C, D and sennidine C as well as derived anthra- and diglycosides:
  
  in the roots of the genus Labium - Galium verum L., common labweed - Galium mollugo L., Catchstraw - Galium aparine L., Woodruff - Galium odoratum (CI Natural Red 14) with the coloring ingredients purpurin (CI 75410), pseudopurpurine (CI CI 58220-snythetic), alizarin (CI 75330), rubiadin (CI 75350), purpuroxanthin (CI 75340), lucidin, alizarin 1-methyl ether, alizarin 2-methyl ether, 2-hydroxyanthraquinone and 1-hydroxy-2- methylanthraquinone:
  
  in Dyer's master's root (CI Natural Red 13) - Asperula tinctoria with the coloring ingredients purpurin (CI 75410), pseudopurpurine (CI 75420, CI 58220-synthetic) and alizarin (CI 75330), in bark of the decoy - Rhamnus fragula L. tinctoria with the coloring ingredients Emodin, 4 Emodin-Glucosides: Glucofragulin A, Glucofrangulin B, Frangulin A, Frangulin B, Physcion and Chrysophanol (CI 75400):
  
• d) Indigoid dyes, such as in the leaves and partial stems of Indian Indigo Indigo Farmera (Indigofera argentea), Fawnwort - Isatis tinctoria, Dyer 's Soleander - Wrightia tinctoria and Wild Indigo - Bap tisia tinctoria (CI Natural Blue 1) with the dye precursors Isatan B and Indican, which are oxidatively converted by a fermentation process into the actual dye indigo (CI 75780; CI 73000) and subordinated indirubin (CI 75790; CI 73200) and isatin:
  
  under the names Indigofera folium or Henna, black as a commercial product, mostly in combination with extracts from Lawsonia Inermis, available,
• e) flavonoid dyes, such as, for example, in the flower heads of Roman chamomile - Chamaemelum nobile (CI Natural Yellow 1) and German chamomile - Chamomilla recutica with the coloring ingredients apigenin (CI 75580, CI Natural Yellow 1.2), rutin (CI 75730, Natural Yellow 10), as well as subordinated luteolin (CI 75590), kaempferol (CI 75460, CI Natural Yellow 13, 10) and quercetin (CI 75670, CI Natural Yellow 10, 13; CI Natural Red 1) and glucosides derived therefrom:
  
  in the leaves and stems of sage - Salvia tribola L. with the coloring ingredients luteolin (CI 75590) and salvigenin:
  
  in the leaves and stems of rosemary - Rosmarinus officinalis with the coloring ingredients luteolin (CI 75590) and apigenin (CI 75580; CI Natural Yellow 1,2) and other flavonoids,
• f) Neoflavanoidfarbstoffe, such as in wood (CI Natural Black 1), heartwood of Haematoxylum campechianum L. with the coloring flavinoid quercetin and the dye precursor hematoxylin, which is converted oxidatively into hematin dye (CI 75290, CI Natural Black 1 and 2) :
  
  in sappan wood - Caesalpinia sappan L., brazil wood - Caesalpinia brasiliensis L., Nicaraguan wood - Caesalpinia echinata, pernambunk wood - Caesalpinia crista L., braziliette wood - Haematoxylum braziletto, each as heartwood (CI Natural Red 24), with the dye precursor Brasilin, which oxidatively in the colorant is Brasilein (CI 75280, CI Natural Red 24) is converted:
  
• g) insoluble redwood dyes, such as in red sandalwood, heartwood of Pterocarpus santalinus L., Narrawood - Pterocarpus indicus L., Barwood - Pterocarpus soyauxii L., Camwood - Bahia nitida (CI Natural Red 22) with the coloring ingredients Santalin A , Santalin B, tetra-O-methylsantarubin, hompterocarpine, pterocarpine, maackiain, the isoflavionides formononetin and santal, and the chalcone isoliquiritigenin and the flavone liquiritigenin:
  
• h) Betaine dyes such as beetroot roots - Beta vulgaris containing the main coloring constituents betanidine and prebetanine and subordinate further betacyanines, betaxanthines, vulgaxanthines, anthocyanins and iron and copper complexes:
  
• i) Gallotannin dyes, for example in the bark of stalk or summer areas - Quercus robur L. with the main coloring constituents from the group of gallotannins and ellagannins (glycosides of gallic acid or ellagic acid, CI 75270):
  
• j) condensed tannin dyes, such as in Catechu (CI Natural Brown 3), a mixture of extracts of staining plants, preferably Acacia catechu, Areca catechu and Uncaria gambier, with a high proportion of condensed tannins ('proanthocyanidins') from catechin Type:
  
  as in the leaves of green and black (= fermented green) tea - Camellia sinensis, with the ingredients gallic acid, m-digallic acid, catechin, glycosides of flavonoids such as, among others, luteolin, apigenin, kaempferol, quercetin, myriecetine, and thearubingenins ( Proanthocyanidins), theaflavin and isotheaflavin:
  

Especially contain the cosmetic compositions of the invention at least one natural dye selected from the group comprising diaryloylmethane dyes, naphthoquinone dyes, Flavonoid dyes, anthraquinone dyes, betalain dyes, Gallotannin dyes and indigoid dyes.

Particularly according to the invention preferred natural dyes are those obtained from a plant, which is selected from the group that is formed Indigofera tinctoria, Curcuma longa, Lawsonia inermis, Chamomilla recutita, Quercus robur, Rosmarinus officinalis, Rheum undulatum and Beta vulgaris.

All in this case, the group which is formed is particularly preferred Diaryloylmethane dyes, naphthoquinone dyes and indigoids Dyes.

Very particular preference is given in the cosmetic compositions according to the invention to natural dyes of plants which are selected from the group consisting of Curcuma longa (turmeric, CI Natural Yellow 3), Lawsonia inermis (Henna, red, CI Natural Orange 6) and Indigofera tinctoria ( Henna, black; CI Natural Blue 1).

The Natural dyes are each preferably in an amount of 0.001 to 20 wt .-%, based on the total application preparation used. The total amount of natural dyes is preferably at most 20% by weight.

In another embodiment of the present invention becomes the color-changing component of dye precursors natural analog dyes selected.

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

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

in der unabhängig voneinander

• – R1 steht für Wasserstoff, eine C₁-C₄-Alkylgruppe oder eine C₁-C₄-Hydroxy-alkylgruppe,
• – R2 steht für Wasserstoff oder eine -COOH-Gruppe, wobei die -COOH-Gruppe auch als Salz mit einem physiologisch verträglichen Kation vorliegen kann,
• – R3 steht für Wasserstoff oder eine C₁-C₄-Alkylgruppe,
• – R4 steht für Wasserstoff, eine C₁-C₄-Alkylgruppe oder eine Gruppe -C(O)R6, in der R6 steht für eine C₁-C₄-Alkylgruppe, und
• – R5 steht unabhängig voneinander für eine der unter R4 genannten Gruppen,

sowie physiologisch verträgliche Salze dieser Verbindungen mit einer organischen oder anorganischen Säure.Particularly suitable precursors of naturally-analogous hair dyes are derivatives of 5,6-dihydroxyindoline of the formula (RN1),

in the independently of each other

• R ₁ is hydrogen, a C ₁ -C ₄ -alkyl group or a C ₁ -C ₄ -hydroxy-alkyl group,
• R 2 is hydrogen or a -COOH group, where the -COOH group may also be present as a salt with a physiologically compatible cation,
• R 3 is hydrogen or a C ₁ -C ₄ -alkyl group,
• R ₄ is hydrogen, a C ₁ -C ₄ alkyl group or a group -C (O) R 6, in which R 6 is a C ₁ -C ₄ alkyl group, and
• R5 is independently one of the groups mentioned under R4,

and physiologically acceptable salts of these compounds with an organic or inorganic acid.

Especially preferred derivatives of indoline are the 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline and 5,6-dihydroxyindoline-2-carboxylic acid.

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

in der unabhängig voneinander

• – R1 steht für Wasserstoff, eine C₁-C₄-Alkylgruppe oder eine C₁-C₄-Hydroxyalkylgruppe,
• – R2 steht für Wasserstoff oder eine -COOH-Gruppe, wobei die -COOH-Gruppe auch als Salz mit einem physiologisch verträglichen Kation vorliegen kann,
• – R3 steht für Wasserstoff oder eine C₁-C₄-Alkylgruppe,
• – R4 steht für Wasserstoff, eine C₁-C₄-Alkylgruppe oder eine Gruppe -C(O)R6, in der R6 steht für eine C₁-C₄-Alkylgruppe, und
• – R5 steht unabhängig voneinander für eine der unter R4 genannten Gruppen,
• – sowie physiologisch verträgliche Salze dieser Verbindungen mit einer organischen oder anorganischen Säure.

Also suitable as precursors of naturally-analogous hair dyes are derivatives of the 5,6-dihydroxyindole of the formula (RN2),

in the independently of each other

• R ₁ is hydrogen, a C ₁ -C ₄ -alkyl group or a C ₁ -C ₄ -hydroxyalkyl group,
• R 2 is hydrogen or a -COOH group, where the -COOH group may also be present as a salt with a physiologically compatible cation,
• R 3 is hydrogen or a C ₁ -C ₄ -alkyl group,
• R ₄ is hydrogen, a C ₁ -C ₄ alkyl group or a group -C (O) R 6, in which R 6 is a C ₁ -C ₄ alkyl group, and
• R5 is independently one of the groups mentioned under R4,
• - As well as physiologically acceptable salts of these compounds with an organic or inorganic acid.

Especially 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.

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

It it is not necessary that oxidation dye precursors, oxo dye precursors, direct dyes or natural analog dyes each uniform Represent connections. Rather, can, due to the production processes for the individual dyes, be contained in minor amounts still other components as far as they do not adversely affect the staining result or for other reasons, e.g. B. toxicological, excluded Need to become.

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

Prefers is used as the oxidizing agent hydrogen peroxide. Prefers is the amount of hydrogen peroxide in the ready to use Average 0.5 to 12 wt .-%, preferably 0.8 to 6 wt .-%, each based to the ready to use means.

Such Oxidizing agent preparations are preferably aqueous, flowable oxidizing agent preparations. there preferred formulations are characterized in that the flowable Oxidizing agent preparation - based on its weight - 40 to 90% by weight, preferably 50 to 85% by weight, more preferably 55 to 80 wt .-%, more preferably 60 to 77.5 wt .-% and in particular 65 to 75 wt .-% water.

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

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

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

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

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

The actual hair dye is conveniently immediately before use by mixing the preparation of the Oxidizing agent with the preparation containing the dye precursors as well as the active compounds according to the invention. The resulting ready-to-use hair dye preparation should preferably have a pH in the range of 6 to 12. Especially the application of the hair dye is preferred in one weak alkaline environment. The application temperatures can in a range between 15 and 40 ° C. After a Exposure time of 5 to 45 minutes, the hair dye through Rinse away from the hair to be dyed. The washing with a shampoo is eliminated if a strong surfactant-containing carrier, for. B. a dyeing shampoo, has been used.

The agents according to the invention can additionally also bleach and / or bleach containing and thus as an agent be provided simultaneously coloring and whitening Act. Such agents are hereinafter referred to as "colorants", as "lightening colorants" or as "dyeing and lightening agent ".

For the strong lightening of very dark hair is the sole use of hydrogen peroxide or its addition products to organic or inorganic compounds often insufficient. In these cases, a combination is usually made Hydrogen peroxide and persulfates or peroxodisulfates used, resulting in an increase in the brightening power of the funds results.

Therefore It may, the consumer should desire a very strong Feeling bleaching, in another embodiment be preferred when the dyeing agent of the invention additionally at least one inorganic persulfate salt or Peroxodisulfate salt in the agent for lightening the keratinic fibers contains.

preferred Peroxodisulfate salts are ammonium peroxodisulfate, potassium peroxodisulfate and sodium peroxodisulfate.

The Peroxodisulfate salts may be present in an amount of 0.1 to 25 Wt .-%, in particular in an amount of 0.5 to 15 wt .-%, based on the total weight of the ready-to-use agent be.

Of the Use of persulfate salts or peroxodisulfate salts takes place in usually in the form of an optionally dedusted powder or a molded body molded in shape.

at an application of additional oxidants the actual dyeing and / or brightening expediently immediately before use by mixing a novel Preparation containing in a cosmetic carrier at least an oxidation dye precursor, and a preparation containing the additional oxidizing agent, in particular hydrogen peroxide, produced. The agent according to the invention can while a blue-green extract in the preparation with oxidation dye precursors and / or in the oxidizing agent preparation. Prefers contains the preparation with oxidation dye precursors the blue-green algae extract.

Becomes a strong brightening desired, it is preferred according to the invention, if additionally a bleaching preparation containing at least an inorganic persulfate salt or peroxodisulfate salt, the oxidizing agent preparation before mixing with the dyeing preparation according to the invention is added.

Especially with hair that is difficult to dye, the preparation with the dye precursors can also be applied to the hair without prior mixing with the oxidation component. After an exposure time of 20 to 30 minutes, the oxidation component is then applied, if appropriate after an intermediate rinse. After a further exposure time of 10 to 20 minutes is then rinsed and nachshampooniert if desired. In this embodiment, according to a first variant, in which the previous application of the dye precursors is to bring about a better penetration into the hair, the appropriate means adjusted to a pH of about 4 to 7. According to a second variant, an air oxidation is initially desired, wherein the applied agent preferably has a pH of 7 to 10. In the subsequent accelerated post-oxidation, the use of acidified peroxodisulfate solutions may be preferred as the oxidizing agent.

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

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

common and in the context of the present invention, preferred chelate complexing agents For example, polyoxycarboxylic acids, polyamines, ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA) and hydroxyethanediphosphonic acids or their alkali metal salts. Also complexing polymers, ie polymers, either in the main chain itself or side by side to carry functional groups that can act as ligands and with suitable metal atoms usually under formation of Chelate complexes react, can be used according to the invention. The polymer-bound ligands of the resulting metal complexes can come from only one macromolecule or belong to different polymer chains. The latter leads to the networking of the material, provided that the complexing Polymers have not previously been crosslinked via covalent bonds were.

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

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

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

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

Preferred complexing agents according to the invention are nitrogen-containing polycarboxylic acids, in particular EDTA, and phosphonates, preferably hydroxyalkane or aminoalkane phosphonates and in particular 1-hydroxyethane-1,1-diphosphonate (HEDP) or its di- or tetrasodium salt and / or ethylenediamine tetramethylene phosphonate (EDTMP) or its hexasodium salt and / or diethylene triamine pentamethylene phosphonate (DTPMP) or its hepta or octa sodium salt.

The Formulation of the colorants of the invention is in principle subject to no restrictions. Usually the agents according to the invention are used as 1-component agents if necessary, immediately before use with a second preparation containing, for example, an oxidizing agent, be mixed. It has, however, in some cases as well proved to be preferred when the product is a 2-component agent is made up. In a preferred embodiment the agents according to the invention are therefore such Assembled that one of the components essential to the invention separately is packed. It plays according to the invention first no matter which of the three invention Components are packed separately; but it may be preferable the preparation (B) containing an extract of a blue-green algae pack separately until application.

The Oxidizing agent preparation contains in addition to the actual Oxidizing agents other auxiliaries and additives. That's how it is According to the invention proved to be preferred when the Oxidant preparation contains at least one thickener. With regard to these thickeners there are no principal Restrictions. It can be both organic and also purely inorganic thickening agents are used.

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

Examples for anionic monomers that make up the polymeric anionic Thickeners may consist of acrylic acid, Methacrylic acid, crotonic acid, itaconic acid, Maleic anhydride and 2-acrylamido-2-methylpropanesulfonic acid. The acidic groups can be used in whole or in part as Sodium, potassium, ammonium, mono- or triethanolammonium salt available. Preferred monomers are maleic anhydride and in particular 2-acrylamido-2-methylpropanesulfonic acid and acrylic acid.

Preferred anionic homopolymers are uncrosslinked and crosslinked polyacrylic acids. Allyl ethers of pentaerythritol, sucrose and propylene may be preferred crosslinking agents. Such compounds are for example available under the trade drawing Carbopol ^® commercially. Also preferred is the homopolymer of 2-acrylamido-2-methyl propane sulfonic acid, which is available for example under the name Rheothik ^® 11-80 is commercially.

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

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

Preferred anionic copolymers are, for example, copolymers of acrylic acid, methacrylic acid or their C ₁ -C ₆ -alkyl esters, as sold under the INCI declaration Acrylates Copolymers. A preferred commercial product is, for example, Aculyn ^® 33 from Rohm & Haas. However, preference is also given to copolymers of acrylic acid, methacrylic acid or their C ₁ -C ₆ -alkyl esters and the esters of an ethylenically unsaturated acid and an alkoxylated fatty alcohol. Suitable ethylenically unsaturated acids are, in particular, acrylic acid, methacrylic acid and itaconic acid; suitable alkoxylated fatty alcohols are in particular steareth-20 or ceteth-20. Such copolymers are sold by Rohm & Haas under the trade name Aculyn ^® 22 and by National Starch under the trade names Structure ^® Structure 2001 ^® 3,001th

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 mole percent acrylamide and 30 to 45 mole percent 2-acrylamido-2-methylpro pansulfonic acid, wherein the sulfonic acid group is wholly or partly present as sodium, potassium, ammonium, mono- or triethanolammonium salt. 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 (C ₁₃ -C ₁₄ isoparaffin or Isohexadecan) and a nonionic emulsifier (Laureth-7 or polysorbate-80), has proved to be particularly advantageous in the context of the teaching of the invention.

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

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

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

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

In a second embodiment, the thickener is a cationic synthetic polymer. Preferred cationic groups are quaternary ammonium groups. In particular, those polymers in which the quaternary ammonium group is bonded via a C ₁ -C ₄ -hydrocarbon group to a polymer main chain constructed from acrylic acid, methacrylic acid or derivatives thereof have proven to be particularly suitable.

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

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

Homopolymers of the general formula (I),

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

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

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

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

The homopolymer is preferably in the form of a non-aqueous polymer dispersion which is a polyme ranteil not less than 30 wt .-% should have used. Such polymer dispersions are (under the names Salcare ^® SC 95 50% polymer content, an additional component: Mineral oil (INCI name: Mineral Oil) and tridecyl-polyoxypropylene-polyoxyethylene-ether (INCI name: PPG-1 trideceth-6) ) and Salcare ^® SC 96 (about 50% polymer content, additional 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, acrylic acid-C ₁ -C ₄ -alkyl esters and methacrylic acid-C ₁ -C ₄ -alkyl esters. Among these nonionic monomers, the acrylamide is particularly preferred. These copolymers can also be crosslinked, as described above for the homopolymers. A preferred copolymer according to the invention is the crosslinked acrylamide-methacryloxyethyltrimethylammonium chloride copolymer. Such copolymers in which the monomers are present in a weight ratio of about 20:80, commercially available as about 50% non-aqueous polymer dispersion under the name Salcare ^® SC 92nd

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 marketed under the trade name Jaguar ^® C from Rhone Poulenc. Modified guar gums preferred according to the invention contain C ₁ -C ₆ -hydroxyalkyl groups. Preferably, the groups are hydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxybutyl. Such modified guar gums are known in the art and can be prepared, for example, by reaction of the guar gums with alkylene oxides. The degree of hydroxyalkylation, which corresponds to the number of alkylene oxide molecules consumed in relation to the number of guar gum free hydroxy groups, is preferably between 0.4 and 1.2. Such modified guar gums are available under the trade names Jaguar ^® HP8, Jaguar ^® HP60, Jaguar ^® HP120, Jaguar DC 293 and Jaguar ^{® ®} HP105 Rhone Poulenc.

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

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

Preferred hydroxyalkylcelluloses are, in particular, the hydroxyethylcelluloses sold under the names Cellosize ^® Amerchol and Natrosol ^® Hercules. Suitable carboxyalkyl are especially the carboxymethylcelluloses as sold under the names Blanose ^® by Aqualon, Aquasorb ^® and ambergum ^® from Hercules and Cellgon ^® from Montello.

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

The Formulation of the colorants of the invention is in principle subject to no restrictions. Usually the agents according to the invention are used as 1-component agents if necessary, immediately before use with a second preparation containing, for example, an oxidizing agent, be mixed. It has, however, in some cases as well proved to be preferred when the product is a 2-component agent is made up. In a preferred embodiment the agents according to the invention are therefore such Assembled that one of the components essential to the invention separately is packed.

• – ”Wellmittel” für die wässrige Zubereitung der keratinreduzierenden Substanz,
• – ”Zwischenspülung” für die erste Spülung und
• – ”Fixiermittel” für die wässrige Zubereitung des Oxidationsmittels.

Within the scope of a preferred embodiment, the agents according to the invention are permanently shape-changing agents. These agents usually consist of two or three preparations, which are successively applied to the fibers. The following terms are used below:

• "Corrugating agent" for the aqueous preparation of the keratin-reducing substance,
• - "intermediate rinse" for the first rinse and
• - "Fixer" for the aqueous preparation of the oxidizing agent.

Even though the blue-green extract according to the invention in principle can be used in any of the said preparations it is particularly preferred according to the invention proven, if it is contained in the Wellmittel.

The Waving agents according to the invention necessarily contain at least one keratin-reducing substance as form-changing Component, preferably mercaptans. Such compounds are, for example Thioglycolic acid, thiolactic acid, thiomalic acid, Mercaptoethanesulfonic acid and its salts and esters, cysteamine, Cysteine, colored salts and salts of sulphurous acid. Prefers suitable as shape-changing components are the alkali metal or ammonium salts of thioglycolic acid and / or thiolactic acid as well as the free acids. These are in the corrugated medium preferably in concentrations of 0.5 to 1.0 mol / kg at a pH from 5 to 12, especially from 7 to 9.5 used. To adjustment this pH value contain the inventive Waving agents usually alkalizing agents such as ammonia, Alkali and ammonium carbonates and bicarbonates or organic Amines such as monoethanolamine.

• • heterocyclische Verbindungen wie Imidazol, Pyrrolidin, Piperidin, Dioxolan, Dioxan, Morpholin und Piperazin sowie Derivate dieser Verbindungen wie beispielsweise die C₁-C₄-Alkyl-Derivate, C₁-C₄-Hydroxyalkyl-Derivate und C₁-C₄-Aminoalkyl-Derivate. Bevorzugte Substituenten, die sowohl an Kohlenstoffatomen als auch an Stickstoffatomen der heterocyclischen Ringsysteme positioniert sein können, sind Methyl-, Ethyl-, 2-Hydroxyethyl- und 2-Aminoethyl-Gruppen. Erfindungsgemäß bevorzugte Derivate heterocyclischer Verbindungen sind beispielsweise 1-Methylimidazol, 2-Methylimidazol, 4(5)-Methylimidazol, 1,2-Dimethylimidazol, 2-Ethylimidazol, 2-Isopropylimidazol, N-Methylpyrrolidon, 1-Methylpiperidin, 4-Methylpiperidin, 2-Ethylpiperidin, 4-Methylmorpholin, 4-(2-Hydroxyethyl)morpholin, 1-Ethylpiperazin, 1-(2-Hydroxyethyl)piperazin, 1-(2-Aminoethyl)piperazin. Weiterhin erfindungsgemäß bevorzugte Imidazolderivate sind Biotin, Hydantoin und Benzimidazol. Ganz besonders bevorzugt ist das Imidazol.
• • Aminosäuren wie insbesondere Arginin, Citrullin, Histidin, Ornithin und Lysin. Die Aminosäuren können sowohl als freie Aminosäure als auch als Salze, z. B. als HydroChloride, eingesetzt werden. Weiterhin haben sich auch Oligopeptide aus durchschnittlich 2–3 Aminosäuren, die einen hohen Anteil (> 50%, insbesondere > 70%) an den genannten Aminosäuren haben, als erfindungsgemäß einsetzbar erwiesen. Erfindungsgemäß besonders bevorzugt sind Arginin sowie dessen Salze und Arginin-reiche Oligopeptide.
• • Diole wie beispielsweise 2-Ethyl-1,3-hexandiol, 1,3-Butandiol, 1,4-Butandiol, 1,2-Propandiol, 1,3-Propandiol, Neopentylglykol und Ethylenglykol. 1,3-Diole, insbesondere 2-Ethyl-1,3-hexandiol und 1,3-Butandiol, haben sich als besonders gut geeignet erwiesen.

Furthermore, the Wellothen invention may contain components that enhance the power, such as

• Heterocyclic compounds, such as imidazole, pyrrolidine, piperidine, dioxolane, dioxane, morpholine and piperazine, and also derivatives of these compounds, such as, for example, the C ₁ -C ₄ -alkyl derivatives, C ₁ -C ₄ -hydroxyalkyl derivatives and C ₁ -C ₄ - aminoalkyl derivatives. Preferred substituents which may be positioned on both carbon atoms and nitrogen atoms of the heterocyclic ring systems are methyl, ethyl, 2-hydroxyethyl and 2-aminoethyl groups. Preferred derivatives of heterocyclic compounds according to the invention are, for example, 1-methylimidazole, 2-methylimidazole, 4 (5) -methylimidazole, 1,2-dimethylimidazole, 2-ethylimidazole, 2-isopropylimidazole, N-methylpyrrolidone, 1-methylpiperidine, 4-methylpiperidine, 2 Ethyl piperidine, 4-methylmorpholine, 4- (2-hydroxyethyl) morpholine, 1-ethylpiperazine, 1- (2-hydroxyethyl) piperazine, 1- (2-aminoethyl) piperazine. Further preferred imidazole derivatives according to the invention are biotin, hydantoin and benzimidazole. Most preferably, the imidazole.
• • Amino acids such as in particular arginine, citrulline, histidine, ornithine and lysine. The amino acids can be used both as free amino acid and as salts, eg. B. as HydroChloride used. Furthermore, oligopeptides of on average 2-3 amino acids, which have a high proportion (> 50%, in particular> 70%) of the amino acids mentioned, have proven to be usable according to the invention. Particularly preferred according to the invention are arginine and its salts and arginine-rich oligopeptides.
• Diols such as 2-ethyl-1,3-hexanediol, 1,3-butanediol, 1,4-butanediol, 1,2-propanediol, 1,3-propanediol, neopentyl glycol and ethylene glycol. 1,3-diols, in particular 2-ethyl-1,3-hexanediol and 1,3-butanediol, have proven to be particularly suitable.

For more information on such Wellkraftverstärkenden components is to the publications DE-OS 44 36 065 and EP-B1-363 057 referenced, the contents of which are expressly incorporated by reference.

The Wellkraftverstärkenden connections can in the corrugated lotions according to the invention in amounts of 0.5 to 5 wt .-%, based on the total wave lotion included be. Amounts of 1 to 4 wt .-%, in the case of diols from 0.5 to 3 wt .-%, have been found to be sufficient, which is why these quantities are particularly preferred.

Mandatory component of the fixing agents according to the invention are oxidizing agents, for. For example, sodium bromate, potassium bromate, hydrogen peroxide, and the usual stabilizers for stabilizing aqueous hydrogen peroxide stabilizers. The pH of such aqueous H ₂ O ₂ preparations, which usually contain about 0.5 to 15% by weight, usually about 0.5 to 3% by weight, of H ₂ O ₂ , is preferably included 2 to 6, in particular 2 to 4; it is adjusted by inorganic acids, preferably phosphoric acid. Bromate-based fixatives are usually used in concentrations of from 1 to 10% by weight and the pH of the solutions is adjusted to 4 to 7. Likewise suitable are enzymatic-based fixatives (for example peroxidases) which contain no or only small amounts of oxidizing agents, in particular H ₂ O ₂ .

The corrugating agent or fixing agent according to the invention are usually formulated in a single phase, including of this term are systems that have a continuous Phase, such as pure oil-in-water or water-in-oil emulsions.

• • eine wässrige Phase und eine nichtwässrige Phase, die separat voneinander vorliegen
• • eine wässrige Phase und zwei nichtwässrige, miteinander nicht mischbare Phasen, die jeweils separat vorliegen
• • eine Öl-in-Wasser-Emulsion und eine davon separiert vorliegende nichtwässrige Phase
• • eine Wasser-in-Öl-Emulsion und eine davon separiert vorliegende wässrige Phase.

It has been found that two-phase and multi-phase systems according to the invention are also preferred. These are systems where there are at least two separate, continuous phases. Examples of such systems are preparations which have the following phases:

• An aqueous phase and a nonaqueous phase which are separate from each other
• • one aqueous phase and two non-aqueous, immiscible phases, each of which is separate
• An oil-in-water emulsion and a non-aqueous phase separated therefrom
• A water-in-oil emulsion and an aqueous phase separated therefrom.

According to the invention preferred Means for color and shape change of the hair are characterized characterized in that they have a pH as neutral as possible have. Another preferred embodiment of the present invention Invention is that the ready-to-use means a pH between 4.0 and 9.0, preferably between 5.0 and 8.5, in particular preferably between 6.0 and 8.0.

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

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

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

It but has been within the scope of the investigations of the present invention found that preferred according to the invention characterized in that they additionally an inorganic Contain alkalizing agent. The invention, inorganic alkalizing agent is preferably selected from the group formed from sodium hydroxide, potassium hydroxide, Calcium hydroxide, barium hydroxide, sodium phosphate, potassium phosphate, Sodium silicate, potassium silicate, sodium carbonate and potassium carbonate.

In particular according to the invention preferred alkalizing agents are selected from Group formed from sodium hydroxide, potassium hydroxide, calcium hydroxide, Barium hydroxide, sodium phosphate, potassium phosphate, sodium silicate, Potassium silicate, sodium carbonate, potassium carbonate, 2-aminoethane-1-ol (Monoethanolamine), 1-aminopropan-2-ol and 2-amino-2-methylpropan-1-ol. Very particular preference is given to 2-aminoethane-1-ol, sodium hydroxide and potassium hydroxide.

A preferred embodiment of the present invention characterized in that the agent low ammonia, preferably free of ammonia is.

The Terms "low ammonia" or "ammonia free" in Senses of the invention relate to the agent added Amount of ammonia, the addition of ammonia as well as aqueous, alcoholic, aqueous-alcoholic or other solution as well as by ammonia gas introduction or by the addition of liquefied Ammonia can take place. The addition of ammonia can also by Use of ammonium salts, wherein the ammonium cation depending on the pH of the preparation in equilibrium with its corresponding Base, the ammonia itself, is. The terms "ammonia-free" and "low ammonia" in the Therefore, the invention also relates to agents, the ammonium salts contained in the appropriate quantities.

preferred Low-ammonia agents contain less than 2 wt .-%, in particular less than 0.5% by weight and most preferably less than 0.1% by weight of added ammonia, in each case based on the total weight the application preparation. Ammonia-free in the context of the invention those agents which are free from ammonia by any of those described above Methods was added. Such agents are most preferred.

• c1) Aminosäuren, Oligopeptiden und Proteinhydrolysaten,
• c2) Silikonderivaten,
• c3) Polyphenolen und
• c4) (Pseudo)Ceramiden

In a preferred embodiment of the present invention, the agents additionally contain at least one further active substance which synergistically improves the care properties of the agents. This active ingredient is preferably selected from the group that is formed

• c1) amino acids, oligopeptides and protein hydrolysates,
• c2) silicone derivatives,
• c3) polyphenols and
• c4) (pseudo) ceramides

In a preferred embodiment the agent according to the invention additionally at least another active substance selected from the group which is formed from amino acids, oligopeptides and protein hydrolysates. For the purposes of the invention, the active substance is amino acids and their peptic bonds Oligo- and polymers, in particular oligopeptides and protein hydrolysates to understand. As amino acid in the context of the invention applies an organic compound having in its structure at least one protonatable amino group and at least one carboxylic acid or a sulfonic acid group. preferred Amino acids are aminocarboxylic acids, in particular α-aminocarboxylic acids and ω-aminocarboxylic acids, wherein α-aminocarboxylic acids are preferred.

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

oligopeptides are either from natural sources or through targeted Synthesis available. The person skilled in the art knows these methods and will know how to select the appropriate one as needed. A particularly preferred oligopeptide is the dimer of serine itself (Ser-Ser), especially L-serine, and threonine and serine (Thr-Ser and / or Ser-Thr).

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

Animal protein hydrolysates are, for example, elastin, collagen, keratin, silk and milk protein protein hydrolysates, which may also be present in the form of salts. Such products are, for example, under the trademarks keratin DEC ^® (Vincience) Dehylan ^® (Cognis), Promois® ^® (Interorgana) Collapuron ^® (Cognis), Nutrilan® ^® (Cognis), Gelita-Sol ^® (German Gelatinefabriken Stoess & Co) distributed Lexein ^® (Inolex) and kerasol tm ^® (Croda).

Preferred according to the invention is the use of protein hydrolysates of plant origin, eg. Soybean, almond, rice, pea, potato and wheat protein hydrolysates. Such products are, for example, under the trademarks Gluadin ^® (Cognis), diamine ^® (Diamalt) ^® (Inolex) and Crotein ^® (Croda) available.

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

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

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

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

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

Of the Active ingredient of at least one amino acid, an oligopeptide or a protein hydrolyzate is in the inventive Agents preferably in amounts of 0.01 to 10 wt .-%, in particular from 0.05 to 5% by weight, based on the total weight of the application mixture, contain.

The Silicone derivatives c2), if they are in the inventive Agents are present, preferably in amounts of 0.05 to 5 wt .-%, preferably from 0.2 to 5 wt .-%, each based on the ready-to-use Means, included.

• (i) Polyalkylsiloxanen, Polyarylsiloxanen, Polyalkylarylsiloxanen, die flüchtig oder nicht flüchtig, geradkettig, verzweigt oder cyclisch, vernetzt oder nicht vernetzt sind;
• (ii) Polysiloxanen, die in ihrer allgemeinen Struktur eine oder mehrere organofunktionelle Gruppen enthalten, die ausgewählt sind unter: a) substituierten oder unsubstituierten aminierten Gruppen; b) (per)fluorierten Gruppen; c) Thiolgruppen; d) Carboxylatgruppen; e) hydroxylierten Gruppen; f) alkoxylierten Gruppen; g) Acyloxyalkylgruppen; h) amphoteren Gruppen; i) Bisulfitgruppen; j) Hydroxyacylaminogruppen; k) Carboxygruppen; l) Sulfonsäuregruppen; und m) Sulfat- oder Thiosulfatgruppen;
• (iii) linearen Polysiloxan(A)-Polyoxyalkylen(B)-Blockcopoylmeren vom Typ (A-B)_n mit n > 3;
• (iv) gepfropften Silikonpolymeren mit nicht silikonhaltigem, organischen Grundgerüst, die aus einer organischen Hauptkette bestehen, welche aus organischen Monomeren gebildet wird, die kein Silikon enthalten, auf die in der Kette sowie gegebenenfalls an mindestens einem Kettenende mindestens ein Polysiloxanmakromer gepfropft wurde;
• (v) gepfropften Silikonpolymeren mit Polysiloxan-Grundgerüst, auf das nicht silikonhaltige, organische Monomere gepfropft wurden, die eine Polysiloxan-Hauptkette aufweisen, auf die in der Kette sowie gegebenenfalls an mindestens einem ihrer Enden mindestens ein organisches Makromer gepfropft wurde, das kein Silikon enthält, wie beispielsweise das unter der INCI-Bezeichnung Bis-PEG/PPG-20/20 Dimethicone vertriebene Handelsprodukt Abil B 8832 der Firma Degussa;
• (vi) oder deren Gemischen.

More preferably, the silicones c2) are selected from at least one member of the list formed from:

• (i) polyalkyl siloxanes, polyaryl siloxanes, polyalkylaryl siloxanes which are volatile or nonvolatile, straight chain, branched or cyclic, crosslinked or uncrosslinked;
• (ii) polysiloxanes containing in their general structure one or more organofunctional groups selected from: a) substituted or unsubstituted aminated groups; b) (per) fluorinated groups; c) thiol groups; d) carboxylate groups; e) hydroxylated groups; f) alkoxylated groups; g) acyloxyalkyl groups; h) amphoteric groups; i) bisulfite groups; j) hydroxyacylamino groups; k) carboxy groups; l) sulfonic acid groups; and m) sulfate or thiosulfate groups;
• (iii) linear polysiloxane (A) polyoxyalkylene (B) block copolymers of the (AB) _{n type} with n>3;
• (iv) grafted silicone polymers having a non-silicone-containing organic backbone consisting of an organic backbone formed from organic monomers containing no silicone to which at least one polysiloxane macromer has been grafted in the chain and optionally at least one chain end;
• (v) grafted polysiloxane backbone silicone polymers having grafted thereto non-silicone-containing organic monomers having a polysiloxane backbone to which at least one organic macromer containing no silicone has been grafted in the chain, and optionally at least at one of its ends , such as the commercial product Abil B 8832 from Degussa marketed under the INCI name Bis-PEG / PPG-20/20 dimethicone;
• (vi) or mixtures thereof.

Particularly preferred cosmetic or dermatological preparations according to the invention are characterized in that they contain at least one silicone of the formula (Si-1) (CH ₃ ) ₃ Si [O-Si (CH ₃ ) ₂ ] _x -O-Si (CH ₃ ) ₃ (Si-1), in which x is a number from 0 to 100, preferably from 0 to 50, more preferably from 0 to 20 and in particular 0 to 10.

The inventively preferred cosmetic or dermatological preparations contain a silicone of the above formula (Si-1). These silicones are referred to as dimethicones according to the INCI nomenclature. It is in the context of the present invention as the silicone of the formula (Si-1), preferably the compounds:
(CH ₃ ) ₃ Si-O-Si (CH ₃ ) ₃
(CH ₃ ) ₃ Si-O-Si (CH ₃ ) ₂ -O-Si (CH ₃ ) ₃
(CH ₃ ) ₃ Si [O-Si (CH ₃ ) ₂ ] ₂ -O-Si (CH ₃ ) ₃
(CH ₃ ) ₃ Si [O-Si (CH ₃ ) ₂ ] ₃ -O-Si (CH ₃ ) ₃
(CH ₃ ) ₃ Si [O-Si (CH ₃ ) ₂ ] ₄ -O-Si (CH ₃ ) ₃
(CH ₃ ) ₃ Si [O-Si (CH ₃ ) ₂ ] ₅ -O-Si (CH ₃ ) ₃
(CH ₃ ) ₃ Si [O-Si (CH ₃ ) ₂ ] ₆ -O-Si (CH ₃ ) ₃
(CH ₃ ) ₃ Si [O-Si (CH ₃ ) ₂ ] ₇ -O-Si (CH ₃ ) ₃
(CH ₃ ) ₃ Si [O-Si (CH ₃ ) ₂ ] ₈ -O-Si (CH ₃ ) ₃
(CH ₃ ) ₃ Si [O-Si (CH ₃ ) ₂ ] ₉ -O-Si (CH ₃ ) ₃
(CH ₃ ) ₃ Si [O-Si (CH ₃ ) ₂ ] ₁₀ -O-Si (CH ₃ ) ₃
(CH ₃ ) ₃ Si [O-Si (CH ₃ ) ₂ ] ₁₁ -O-Si (CH ₃ ) ₃
(CH ₃ ) ₃ Si [O-Si (CH ₃ ) ₂ ] ₁₂ -O-Si (CH ₃ ) ₃
(CH ₃ ) ₃ Si [O-Si (CH ₃ ) ₂ ] ₁₃ -O-Si (CH ₃ ) ₃
(CH ₃ ) ₃ Si [O-Si (CH ₃ ) ₂ ] ₁₄ -O-Si (CH ₃ ) ₃
(CH ₃ ) ₃ Si [O-Si (CH ₃ ) ₂ ] ₁₅ -O-Si (CH ₃ ) ₃
(CH ₃ ) ₃ Si [O-Si (CH ₃ ) ₂ ] ₁₆ -O-Si (CH ₃ ) ₃
(CH ₃ ) ₃ Si [O-Si (CH ₃ ) ₂ ] ₁₇ -O-Si (CH ₃ ) ₃
(CH ₃ ) ₃ Si [O-Si (CH ₃ ) ₂ ] ₁₈ -O-Si (CH ₃ ) ₃
(CH ₃ ) ₃ Si [O-Si (CH ₃ ) ₂ ] ₁₉ -O-Si (CH ₃ ) ₃
(CH ₃ ) ₃ Si [O-Si (CH ₃ ) ₂ ] ₂₀ -O-Si (CH ₃ ) ₃
where (CH ₃ ) ₃ SiOSi (CH ₃ ) ₃ , (CH ₃ ) ₃ SiOSi (CH ₃ ) ₂ OSi (CH ₃ ) ₃ and / or (CH ₃ ) ₃ Si [OSi (CH ₃ ) ₂ ] ₂ OSi (CH ₃ ) _{3 are} particularly preferred.

Of course, mixtures of the above-mentioned silicones in the preferred according to the invention be included.

Preferred silicones which can be used according to the invention have viscosities of from 0.2 to 2 mm ² s ^-1 at 20 ° C., silicones having viscosities of from 0.5 to 1 mm ² s ^{-1 being} particularly preferred.

Particularly preferred agents according to the invention contain one or more amino-functional silicones. Such silicones may, for. By the formula (Si-2) M (R _a Q _b SiO _{(4-ab) / 2} ) _x (R _c SiO _{(4-c) / 2} ) _y M (Si-2)

Be described, taking in the above formula
R is hydrocarbon radical having 1 to 8 carbon atoms,
Q is a polar radical of the general formula -R ¹ HZ,
wherein
R ^{1 is} a divalent linking group bonded to hydrogen and the radical Z composed of carbon and hydrogen atoms, carbon, hydrogen and oxygen atoms or carbon, hydrogen and nitrogen atoms, and
Z is an organic, amino-functional group containing at least one amino-functional group;
a assumes values in the range of about 0 to about 2,
b takes values in the range of about 1 to about 3,
a + b is less than or equal to 3, and
c is a number in the range of about 1 to about 3, and
x is a number ranging from 1 to about 2,000, preferably from about 3 to about 50, and most preferably from about 3 to about 25, and
y is a number ranging from about 20 to about 10,000, preferably from about 125 to about 10,000, and most preferably from about 150 to about 1,000, and
M is a suitable silicone end group, as is known in the art, preferably trimethylsiloxy.

Not Restrictive examples of those represented by R in formula (Si-2) Radicals include alkyl radicals such as methyl, ethyl, propyl, Isopropyl, butyl, isobutyl, amyl, isoamyl, hexyl, isohexyl and the like; Alkenyl radicals, such as vinyl, halovinyl, alkylvinyl, allyl, haloallyl, alkyl allyl; Cycloalkyl radicals, such as cyclobutyl, cyclopentyl, cyclohexyl and similar; Phenyl radicals, benzyl radicals, halohydrocarbon radicals, such as 3-chloropropyl, 4-bromobutyl, 3,3,3-trifluoropropyl, chlorocyclohexyl, Bromophenyl, chlorophenyl and the like, as well as sulfur Radicals, such as mercaptoethyl, mercaptopropyl, mercaptohexyl, mercaptophenyl and similar ones; Preferably R is an alkyl radical which 1 to about 6 carbon atoms, and most preferably R is methyl.

Examples of R ¹ include methylene, ethylene, propylene, hexamethylene, decamethylene, CH ₂ CH (CH ₃ ) CH ₂ , phenylene, naphthylene, CH ₂ CH ₂ SCH ₂ CH ₂ , CH ₂ CH ₂ OCH ₂ , OCH ₂ CH ₂ , OCH ₂ CH ₂ CH ₂ , CH ₂ CH (CH ₃ ) C (O) OCH ₂ , (CH ₂ ) ₃ C (O) OCH ₂ CH ₂ , C ₆ H ₄ C ₆ H ₄ , C ₆ H ₄ CH ₂ C ₆ H ₄ ; and (CH ₂ ) ₃ C (O) SCH ₂ CH ₂ .

Z is according to formula (Si-2) an organic, amino-functional radical containing at least one functional amino group. A possible formula for said Z is NH (CH ₂ ) _z NH ₂ , where z is an integer greater than or equal to 1. Another possible formula for Z is NH (CH ₂ ) _z (CH ₂ ) _zz NH, wherein both z and zz are independently of one another an integer greater than or equal to 1, this structure comprising diamino ring structures, such as piperazinyl. Said Z is most preferably a NHCH ₂ CH ₂ NH radical. Another possible formula for said Z is N (CH ₂ ) _z (CH ₂ ) _zz NX ₂ or NX ² , wherein each X of X ^{2 is} independently selected from the group consisting of hydrogen and alkyl groups of 1 to 12 carbon atoms, and zz 0 is.

Q according to formula (Si-2) is most preferably a polar amino-functional radical of the formula CH ₂ CH ₂ CH ₂ NHCH ₂ CH ₂ NH ₂ .

In the formula (Si-2), α assumes values in the range of 0 to 2, b takes values in the range of 2 to 3, a + b is less than or equal to 3, and c is a number in the range of 1 to 3. The molar ratio of the R _a Q _b SiO _{(4-ab) / 2} units to the R _c SiO (4-c) / 2 units in formula (Si-2) is in the range of about 1: 2 to 1:65, preferably from about 1: 5 to about 1:65, and most preferably from about 1:15 to about 1:20. When one or more silicones of the above formula (Si-2) are used, the various variable substituents in the above formula may be different for the various silicone components present in the silicone mixture.

Preferred cosmetic or dermatological preparations according to the invention contain an amino-functional silicone of the formula (Si-3) R _'a G _3-a -Si (OSiG _{2) n} - (OSiG _b R' _{2-b) m} -O-SiG _3-a -R _'a (Si-3), where:
G is H, a phenyl group, OH, OCH ₃ , CH ₃ , OCH ₂ CH ₃ , CH ₂ CH ₃ , OCH ₂ CH ₂ CH ₃ , CH ₂ CH ₂ CH ₃ , OCH (CH ₃ ) ₂ , CH (CH ₃ ) ₂ , OCH ₂ CH ₂ CH ₂ CH ₃ , CH ₂ CH ₂ CH ₂ CH ₃ , OCH ₂ CH (CH ₃ ) ₂ , CH ₂ CH (CH ₃ ) ₂ , OCH (CH ₃ ) CH ₂ CH ₃ , CH (CH ₃ ) CH ₂ CH ₃ , OC (CH ₃ ) ₃ , C (CH ₃ ) ₃ ;
a is a number between 0 and 3, in particular 0;
b stands for a number between 0 and 1, in particular 1,
m and n are numbers whose sum (m + n) is between 1 and 2000, preferably between 50 and 150, where n is preferably values from 0 to 1999 and in particular from 49 to 149 and m preferably values from 1 to 2000, in particular from 1 to 10,
R 'is a monovalent radical selected from
-QN (R ") CH ₂ CH ₂ N (R") ₂
-QN (R '') ₂
-QN ⁺ (R '') ₃ A ^-
-QN ⁺ H (R '') ₂ A ^-
-QN ⁺ H ₂ (R '') A ^-
-QN (R ") CH ₂ CH ₂ N ⁺ R''H ₂ A ^- ,
wherein each Q is a chemical bond, CH ₂ , CH ₂ CH ₂ , CH ₂ CH ₂ CH ₂ , C (CH ₃ ) ₂ , CH ₂ CH ₂ CH ₂ CH ₂ , CH ₂ C (CH ₃ ) ₂ , CH ( CH ₃ ) CH ₂ CH ₂ ,
R '' is identical or different radicals from the group H, phenyl, benzyl, CH ₂ CH (CH ₃ ) Ph, the C ₁ -C ₂₀ -alkyl radicals, preferably CH ₃ , CH ₂ CH ₃ , CH ₂ CH ₂ CH ₃ , CH (CH ₃ ) ₂ , CH ₂ CH ₂ CH ₂ H ₃ , CH ₂ CH (CH ₃ ) ₂ , CH (CH ₃ ) CH ₂ CH ₃ , C (CH ₃ ) ₃ , and A ^{- represents} an anion , which is preferably selected from chloride, bromide, iodide or methosulfate.

Cationic silicone oils, such as the commercially available Dow Corning 929 emulsion (containing a hydroxylamino-modified silicone referred to as amodimethicone), DC 2-2078 (manufactured by Dow Corning, INCI: aminopropyl phenyl trimethicone), DC 5, are suitable according to the invention -7113 (manufacturer Dow Corning, INCI name: Silicone Quaternium 16), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ^® quat 3270 and 3272 (manufacturer: Th Goldschmidt; diquaternary. Polydimethylsiloxanes, quaternium-80).

enthalten, worin m und n Zahlen sind, deren Summe (m + n) zwischen 1 und 2000, vorzugsweise zwischen 50 und 150 beträgt, wobei n vorzugsweise Werte von 0 bis 1999 und insbesondere von 49 bis 149 und m vorzugsweise Werte von 1 bis 2000, insbesondere von 1 bis 10 annimmt.Particularly preferred agents according to the invention are characterized in that they contain at least one amino-functional silicone of the formula (Si 3-a)

in which m and n are numbers whose sum (m + n) is between 1 and 2000, preferably between 50 and 150, where n preferably values of 0 to 1999 and in particular of 49 to 149 and m preferably values of 1 to 2000 , in particular from 1 to 10 assumes.

These Silicones are classified as trimethylsilylamodimethicones according to the INCI declaration and are for example under the name Q2-7224 (Manufacturer: Dow Corning, a stabilized trimethylsilylamodimethicone) available.

enthalten, worin
R für -OH, eine (gegebenenfalls ethoxylierte und/oder propoxylierte) C₁-C₂₀-Alkoxygruppe oder eine -CH₃-Gruppe steht,
R' für -OH, eine C₁-C₂₀-Alkoxygruppe oder eine -CH₃-Gruppe und
m, n1 und n2 Zahlen sind, deren Summe (m + n1 + n2) zwischen 1 und 2000, vorzugsweise zwischen 50 und 150 beträgt, wobei die Summe (n1 + n2) vorzugsweise Werte von 0 bis 1999 und insbesondere von 49 bis 149 und m vorzugsweise Werte von 1 bis 2000, insbesondere von 1 bis 10 annimmt.Particular preference is also given to compositions according to the invention which contain at least one amino-functional silicone of the formula (Si-3b)

contain, in which
R is -OH, an optionally ethoxylated and / or propoxylated C ₁ -C ₂₀ -alkoxy group or a -CH ₃ group,
R 'for -OH, a C ₁ -C ₂₀ alkoxy group or a -CH ₃ group and
m, n1 and n2 are numbers whose sum (m + n1 + n2) is between 1 and 2000, preferably between 50 and 150, the sum (n1 + n2) preferably having values from 0 to 1999 and in particular from 49 to 149 and m preferably assumes values of from 1 to 2000, in particular from 1 to 10.

These Silicones are labeled according to the INCI declaration as Amodimethicone, or as functionalized amodimethicones, such as bis (C13-15 Alkoxy) PG amodimethicones (for example as a commercial product: DC 8500 from Dow Corning), trideceth-9 PG-amodimethicone (For example, as a commercial product Silcare Silicone SEA the company Clariant available).

Independently of which amino-functional silicones are used are cosmetic or dermatological according to the invention Preparations preferred which contain an amino-functional silicone its amine number above 0.25 meq / g, preferably above 0.3 meq / g and in particular above 0.4 meq / g. The amine number stands for the milliequivalents of amine per Grams of amino-functional silicone. It can be done by titration determined and also in the unit mg KOH / g.

According to the invention preferred cosmetic or dermatological preparations are characterized that, based on their weight, 0.01 to 10 wt .-%, preferably 0.1 to 8 wt .-%, particularly preferably 0.25 to 7.5 wt .-% and in particular 0.5 to 5% by weight of amino-functional silicone (s), in each case obtained on the total weight of ready-to-use resources.

enthalten, in der x für eine Zahl von 0 bis 200, vorzugsweise von 0 bis 10, weiter bevorzugt von 0 bis 7 und insbesondere 0, 1, 2, 3, 4, 5 oder 6, steht.The cyclic dimethicones designated as cyclomethicones according to INCI are also preferably used according to the invention. Here, cosmetic or dermatological preparations according to the invention are preferred which contain at least one silicone of the formula (Si-4)

in which x is a number from 0 to 200, preferably from 0 to 10, more preferably from 0 to 7 and in particular 0, 1, 2, 3, 4, 5 or 6 stands.

The silicones described above have a backbone, which is composed of -Si-O-Si units. Of course These Si-O-Si units can also be replaced by carbon chains be interrupted. Corresponding molecules are by chain extension reactions accessible and preferably come in the form of silicone-in-water emulsions for use.

The Silicone-in-water which can be used according to the invention Emulsions can be prepared by known methods become.

In summary For example, this method of preparation comprises the emulsifying mixture of Components, one of which contains at least one polysiloxane, the other of which contains at least one organosilicone material, that with the polysiloxane in a chain extension reaction reacting, wherein at least one metal ion-containing catalyst for the chain extension reaction, at least a surfactant and water are present.

Chain extension reactions with polysiloxanes are known and may include, for example, the hydrosilylation reaction in which an Si-H group having an aliphatically unsaturated group in the counter a platinum / rhodium catalyst to form polysiloxane with some Si (C) _p -Si bonds (p = 1-6) reacts, wherein the polysiloxanes are also referred to as polysiloxane-polysilalkylene copolymers.

The Chain extension reaction can also be the reaction of a Si-OH group (for example, a hydroxy-terminated polysiloxane) with an alkoxy group (for example, alkoxysilanes, silicates or alkoxysiloxanes) in the presence of a metal-containing catalyst to form polysiloxanes.

The polysiloxanes used in the chain extension reaction comprise a substantially linear polymer of the following structure:
R-Si (R) ₂ - [- OSi (R) ₂ -] _n -O-SiR ₃

In this structure, each R independently represents a hydrocarbon radical having up to 20 carbon atoms, preferably having 1 to 6 carbon atoms, such as an alkyl group (for example, methyl, ethyl, propyl or butyl), an aryl group (for example, phenyl), or group required for the chain extension reaction ("reactive group", for example, Si-bonded H atoms, aliphatically unsaturated groups such as vinyl, allyl or hexenyl, hydroxy, alkoxy such as methoxy, ethoxy or propoxy, alkoxy-alkoxy, acetoxy, amino, etc.), with the proviso that on average one to two reactive groups are present per polymer, n is a positive number> 1. Preferably, a plurality of the reactive groups, more preferably> 90%, and especially> 98% of the reactive groups, at the terminal Si -Atomen bound in siloxane. Preferably, n is numbers describing polysiloxanes having viscosities between 1 and 1,000,000 mm ² / s, more preferably viscosities between 1,000 and 100,000 mm ² / s.

The Polysiloxanes can be branched to a low degree (For example, <2 Mol% of the siloxane units), or the polymers are, however, substantial linear, particularly preferably completely linear. In addition, you can the substituents R in turn be substituted, for example with N-containing groups (for example amino groups), epoxy groups, S-containing groups, Si-containing groups, O-containing groups, etc. Preferably At least 80% of the radicals R are alkyl radicals, particularly preferred Methyl groups.

The Organosilicone material that reacts with the polysiloxane in the chain extension reaction may be either a second polysiloxane, or a molecule, which acts as a chain extender. When the organosilicone material is a polysiloxane, it has the generality mentioned above Structure. In these cases, a polysiloxane has in the Reaction (at least) one reactive group, and a second polysiloxane has (at least) a second reactive group with the first responding.

If the organosilicone material is a chain extender agent this may be a material such as a silane, a siloxane (for example, disiloxane or trisiloxane) or a Silazane. For example, a composition that is a polysiloxane according to the general structure described above comprises, which has at least one Si-OH group, chain-extended be prepared by reacting with an alkoxysilane (for example, a dialkoxysilane or trialkoxysilane) in the presence of tin or titanium containing Catalysts is reacted.

The metal-containing catalysts in the chain extension reaction are usually specific for a particular reaction. Such catalysts are known in the art and include, for example, metals such as platinum, rhodium, tin, titanium, copper, lead, etc. In a preferred chain extension reaction, a polysiloxane having at least one aliphatically unsaturated group, preferably an end group, is reacted with an organosilicone material Presence of a hydrosilylation catalyst which is a siloxane or polysiloxane having at least one (preferably terminal) Si-H group. The polysiloxane has at least one aliphatically unsaturated group and satisfies the general formula given above in which R and n are as defined above, with an average of between 1 and 2 groups R having one aliphatically unsaturated group per polymer. Representative aliphatic unsaturated groups are, for example, vinyl, allyl, hexenyl and cyclohexenyl or a group R ² CH = CHR ³ , in which R ^{2 is} a divalent aliphatic silicon-bonded chain and R ^{3 is} a hydrogen atom or an alkyl group. The organosilicone material having at least one Si-H group preferably has the above-mentioned structure, wherein R and n are as defined above and wherein, on average, between 1 and 2 groups R is hydrogen and n is 0 or a positive integer.

This Material may be a polymer or a low molecular weight material such as a siloxane (for example, a disiloxane or a trisiloxane).

The polysiloxane having at least one aliphatic unsaturated group and the organosilicone material with at least one Si-H group react in the presence of a hydrosilylation catalyst. Such catalysts are known in the art and include, for example, platinum and rhodium-containing materials. The catalysts may take any known form, for example platinum or rhodium supported on support materials (such as silica gel or activated carbon) or other suitable compounds such as platinum chloride, salts of platinum or chloroplatinic acids. A preferred catalyst because of good dispersibility in organosilicone systems and low color change is chloroplatinic acid either as a commercially available hexahydrate or in anhydrous form.

at Another preferred chain extension reaction is a polysiloxane with at least one Si-OH group, preferably an end group, reacted with an organosilicone material which is at least has an alkoxy group, preferably a siloxane having at least a Si-OR group or an alkoxysilane having at least two alkoxy groups. In this case, the catalyst again is a metal-containing catalyst used.

For the reaction of an Si-OH group with an Si-OR group exist many literature known catalysts, such as organometallic compounds such as organotin salts, titanates or titanium chelates or complexes. Examples include stannous octoate, dibutyltin dilaurate, dibutyltin diacetate, Dimethyltin dineodecanoate, dibutyltin dimethoxide, isobutyltin triceroate, Dimethyltin dibutyrate, dimethyltin dineodecanoate, triethyltin tartrate, Tin oleate, tin naphthenate, tin butyrate, tin acetate, tin benzoate, Tin sebacate, tin succinate, tetrabutyl titanate, tetraisopropyl titanate, Tetraphenyl titanate, tetraoctadecyl titanate, titanium naphthanate, ethyl triethanolamine titanate, Titani diisopropyl diethyl acetoacetate, titanium diisopropoxy diacetyl acetonate and titanium tetra-alkoxides in which the alkoxide is butoxy or propoxy is.

Agents which are likewise preferred according to the invention are characterized in that they contain at least one silicone of the formula (Si-5) R ₃ Si [O-SiR ₂ ] _x - (CH ₂ ) _n - [O-SiR ₂ ] _y -O-SiR ₃ (Si-5), in which R is identical or different radicals from the group H, phenyl, benzyl, CH ₂ CH (CH ₃ ) Ph, the C ₁ -C ₂₀ -alkyl radicals, preferably CH ₃ , CH ₂ CH ₃ , CH ₂ CH ₂ CH ₃ , CH (CH ₃ ) ₂ , CH ₂ CH ₂ CH ₂ H ₃ , CH ₂ CH (CH ₃ ) ₂ , CH (CH ₃ ) CH ₂ CH ₃ , C (CH ₃ ) ₃ , y is a number from 0 to 200, preferably from 0 to 10, more preferably from 0 to 7 and especially 0, 1, 2, 3, 4, 5 or 6, and n is a number from 0 to 10, preferably from 1 to 8 and especially for 2, 3, 4, 5, 6 stands.

With The silicones are preferably water-soluble. According to the invention preferred Means of the embodiment with a silicone c2) are characterized characterized in that the silicone c2) is water-soluble.

Appropriate hydrophilic silicones are, for example, from the compounds of Formulas (Si-6) and / or (Si-7) selected. Especially preferred water-soluble silicone-based surfactants selected from the group of Dimethiconcopolyole the preferred alkoxylated, in particular polyethoxylated or polypropoxylated are.

worin

• – der Rest R steht für ein Wasserstoffatom, eine Alkylgruppe mit 1 bis 12 C-Atomen, eine Alkoxygruppe mit 1 bis 12 C-Atomen oder eine Hydroxylgruppe,
• – die Reste R' und R'' bedeuten Alkylgruppen mit 1 bis 12 C-Atomen,
• – x steht für eine ganze Zahl von 1 bis 100, bevorzugt von 20 bis 30,
• – y steht für eine ganze Zahl von 1 bis 20, bevorzugt von 2 bis 10 und
• – a und b stehen für ganze Zahlen von 0 bis 50, bevorzugt von 10 bis 30.

Dimethicone copolyols are understood according to the invention as meaning preferably polyoxyalkylene-modified dimethylpolysiloxanes of the general formulas (Si-6) or (Si-7):

wherein

• - The radical R is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group with 1 to 12 C atoms or a hydroxyl group,
• The radicals R 'and R "represent alkyl groups having 1 to 12 C atoms,
• X is an integer from 1 to 100, preferably from 20 to 30,
• Y is an integer from 1 to 20, preferably from 2 to 10 and
• A and b are integers from 0 to 50, preferably from 10 to 30.

Compounds falling within the above formulas are disclosed in the following patent applications, which are incorporated by reference: US-A-4,122,029 ; US-A-4,265,878 ; US-A-4,421,769 and GB-A-2,066,659 ,

Especially Preferred dimethicone copolyols according to the invention are, for example commercially available under the trade name SILWET (Union Carbide Corporation) and DOW CORNING (Dow) distributed products. Particularly according to the invention preferred dimethicone copolyols are Dow Corning 190 and Dow Corning 193 (Dow).

• c3-1) Hydroxyzimtsäuren,
• c3-2) 6,7-Dihydroxycumarine,
• c3-3) Hydroxybenzoesäuren,
• c3-4) Catechine,
• c3-5) Leukoanthocyanidine,
• c3-6) Anthocyanidine,
• c3-7) Flavanone und
• c3-8) Flavone und
• c3-9) Flavonole.

Polyphenols c3) are generally compounds containing more than two phenolic (polyol) or phenolic ether groups belonging to different classes of substances. The polyphenols are preferably selected from at least one member of the group that is formed from:

• c3-1) hydroxycinnamic acids,
• c3-2) 6,7-dihydroxycoumarins,
• c3-3) hydroxybenzoic acids,
• c3-4) catechins,
• c3-5) leucoanthocyanidins,
• c3-6) anthocyanidins,
• c3-7) flavanones and
• c3-8) Flavones and
• c3-9) flavonols.

In In nature, for example, free and etherified polyphenols occur in flower dyes (anthocyanidins, flavones), in tannins (Catechins, tannins), as lichen or fern ingredients (usnic acid, Acylpolyphenols), in lignins and as gallic acid derivatives on. Preferred polyphenols are flavones, catechins, usnic acid, and as tannins the derivatives of gallic acid, digallic acid and digalloylgallic acid. Particularly preferred polyphenols are the monomeric catechins, that is the derivatives of Flavan-3-ols, and leucoanthocyanidins, that is the derivatives the leucoanthocyanidins, which are preferably in the 5,7,3 ', 4', 5 'position carry phenolic hydroxy groups, preferably epicatechin and epigallocatechin, and the resulting by self-condensation tannins. Such tanning agents are preferably not in isolated pure substance, but used as extracts of tannin-rich plant parts, eg. B. extracts Catechu, Quebracho, and Oak Bark, as well as other tree bark, Leaves of green tea (camellia sinensis) and Mate. Also particularly preferred are the tannins.

worin
R1 steht für eine lineare C₁₂-C₃₀-Alkylgruppe oder eine gesättigte oder ungesättigte ω-(C₁₂-C₂₀-Acyloxy)-C₁₂-C₃₀-alkylgruppe (wie bevorzugt Tricosanyl, Heptadecanyl oder ω-(Octadeca-9,12-dien-oyloxy)-nonacosanyl) und
R2 steht für eine gesättigte oder ungesättigte C₁₅-Alkylgruppe oder eine gesättigte oder ungesättigte C₁₅-Hydroxyalkylgruppe (wie beispielsweise Pentadeca-1-en-1-yl, 3-Hydroxypentadeca-1-en-1-yl, 1-Hydroxypentadecanyl).The ceramides c4) used are preferably the sphingolipids of the formula (VI),

wherein
R 1 represents a linear C ₁₂ -C ₃₀ alkyl group or a saturated or unsaturated ω- (C ₁₂ -C ₂₀ acyloxy) C ₁₂ -C ₃₀ alkyl group (preferably tricosanyl, heptadecanyl or ω- (octadeca-9, 12-dienyloxy) -nonacosanyl) and
R 2 represents a saturated or unsaturated C ₁₅ alkyl group or a saturated or unsaturated C ₁₅ hydroxyalkyl group (such as pentadeca-1-en-1-yl, 3-hydroxypentadeca-1-en-1-yl, 1-hydroxypentadecanyl).

According to the invention, the compounds ceramides I, ceramides II, ceramides 1, ceramides 2, ceramides 3, ceramides 5 and ceramides 6 which are known under the INCI names are used as the active compound as preferred compounds according to formula (VI). Mixtures of the compounds of formula (VI) are particularly preferably used, which are obtainable for example under the trade name of SK-Influx ^® and Ceramide III respectively by Degussa Care Specialties, and the commercial product Ceramide TIC-001, marketed by Takasago International Corporation. The compounds of the formula (VI) are preferably used in an amount of from 0.01 to 1.0% by weight, based on the weight of the ready-to-use cosmetic product.

In addition, pseodoceramides, such as, in particular, the pseudoceramide N- (C ₈ -C ₂₂ -acyl) - (C ₈ -C ₂₂ -acyl) hydroxyproline (such as, for example, the cetyl-hydroxyproline palmitamide according to the product Sym Repair 153884 from Symrise) are pseudoceramides c4 according to the invention ).

Preferably the ready-to-use colorants are flowable Preparations.

Prefers contain the flowable preparations in addition as surface-active substance an emulsifier or a surfactant, where surfactants depending on the field of application as surfactants or as emulsifiers and from anionic, cationic, amphoteric, zwitterionic and nonionic surfactants and emulsifiers are selected. These substances will be below described in detail.

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

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

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

typical Examples of suitable for the purposes of the invention monoglyceride (ether) sulfate 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 monoglyceride sulfates of the formula (MGS), in which R is a linear alkyl radical with 8 to 18 carbon atoms.

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

Particularly according to the invention However, preferred agents are characterized in that anionic surfactants in a total content of less than 1.0% by weight, preferably less than 0.5% by weight, based in each case on the total weight of the application preparation, are included.

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

In a further preferred embodiment of the present invention, the agent further contains at least one amphoteric surfactant. Amphoteric surfactants are 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 are capable of forming internal salts , Examples of suitable amphoteric surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each having about 8 to 24 C Atoms in the alkyl group.

Particularly preferred amphoteric surfactants are the INCI name Disodium Cocoamphodipropionate with the trade names Miranol ^® C2M SF conc. (Rhodia), Amphoterge ^® K-2 (Lonza) and Monateric ^® CEM-38 (Unichema) and name Disodium Cocoamphodiacetate with the trade names Dehyton ^® (Cognis), Miranol ^® C2M (Rhodia) and Ampholak ^® XCO 30 (Akzo Nobel) marketed ,

Of the Addition in the inventive agent causes a Excellent finish, especially improved wet combability.

The amphoteric surfactants are in the inventive Agent preferably in an amount of 0.05 to 30 wt .-%, especially preferably from 0.1 to 20 wt .-%, each based on the weight of the agent.

• – Anlagerungsprodukte von 2 bis 50 Mol Ethylenoxid und/oder 0 bis 5 Mol Propylenoxid an lineare und verzweigte Fettalkohole mit 8 bis 30 C-Atomen, an Fettsäuren mit 8 bis 30 C-Atomen und an Alkylphenole mit 8 bis 15 C-Atomen in der Alkylgruppe,
• – mit einem Methyl- oder C₂-C₆-Alkylrest endgruppenverschlossene Anlagerungsprodukte von 2 bis 50 Mol Ethylenoxid und/oder 0 bis 5 Mol Propylenoxid an lineare und verzweigte Fettalkohole mit 8 bis 30 C-Atomen, an Fettsäuren mit 8 bis 30 C-Atomen und an Alkylphenole mit 8 bis 15 C-Atomen in der Alkylgruppe, wie beispielsweise die unter den Verkaufsbezeichnungen Dehydol^® LS, Dehydol^® LT (Cognis) erhältlichen Typen,
• – C₁₂-C₃₀-Fettsäuremono- und -diester von Anlagerungsprodukten von 1 bis 30 Mol Ethylenoxid an Glycerin,
• – Polyglycerinester und alkoxylierte Polyglycerinester, wie beispielsweise Poly(3)glycerindiisostearat (Handelsprodukt: Lameform^®TGI (Henkel)) und Poly(2)glycerinpolyhydroxystearat (Handelsprodukt: Dehymuls^®PGPH (Henkel)).
• – Anlagerungsprodukte von 5 bis 60 Mol Ethylenoxid an Rizinusöl und gehärtetes Rizinusöl,
• – Polyolfettsäureester, wie beispielsweise das Handelsprodukt Hydagen^® HSP (Cognis) oder Sovermol-Typen (Cognis),
• – alkoxylierte, bevorzugt propoxylierte und insbesondere ethoxylierte, Mono-, Di- und Triglyceride, wie beispielsweise Glycerinmonolaurat + 20 Ethylenoxid und Glycerinmonostearat + 20 Ethylenoxid,
• – alkoxylierte Fettsäurealkylester der Formel RC(O)-(OCH₂CH₂)_wOR', in der RC(O)- für einen linearen oder verzweigten, gesättigten und/oder ungesättigten Acylrest mit 6 bis 22 Kohlenstoffatomen, R' für lineare oder verzweigte Alkylreste mit 1 bis 4 Kohlenstoffatomen und w für Zahlen von 1 bis 20 steht,
• – Aminoxide,
• – Hydroxymischether,
• – Sorbitanfettsäureester und Anlagerungeprodukte von Ethylenoxid an Sorbitanfettsäureester wie beispielsweise die Polysorbate, Sorbitanmonolaurat und Sorbitanmonolaurat + 20 Mol Ethylenoxid (EO),
• – Zuckerfettsäureester und Anlagerungsprodukte von Ethylenoxid an Zuckerfettsäureester,
• – Anlagerungsprodukte von Ethylenoxid an Fettsäurealkanolamide und Fettamine,
• – Fettsäure-N-alkylglucamide,
• – Alkylphenole und Alkylphenolalkoxylate mit 6 bis 21, insbesondere 6 bis 15 Kohlenstoffatomen in der Alkylkette und 0 bis 30 Ethylenoxid- und/oder Propylenoxid-Einheiten. Bevorzugte Vertreter dieser Klasse sind beispielsweise Nonylphenol + 4 EO, Nonylphenol + 9 EO, Octylphenol + 3 EO und Octylphenol + 8 EO;
• – Alkylpolyglykoside entsprechend der allgemeinen Formel RO-(Z)_x, wobei R für Alkyl, Z für Zucker sowie x für die Anzahl der Zuckereinheiten steht. Die erfindungsgemäß verwendbaren Alkylpolyglykoside können lediglich einen bestimmten Alkylrest R enthalten. Üblicherweise werden diese Verbindungen aber ausgehend von natürlichen Fetten und Ölen oder Mineralölen hergestellt. In diesem Fall liegen als Alkylreste R Mischungen entsprechend den Ausgangsverbindungen bzw. entsprechend der jeweiligen Aufarbeitung dieser Verbindungen vor.

Furthermore, it has proved to be advantageous if the 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. Such compounds are, for example

• - Addition products of 2 to 50 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide to linear and branched fatty alcohols having 8 to 30 carbon atoms, to fatty acids having 8 to 30 carbon atoms and to alkylphenols having 8 to 15 carbon atoms in the alkyl group,
• - with a methyl or C ₂ -C ₆ alkyl radical end-capped addition products of 2 to 50 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide to linear and branched fatty alcohols having 8 to 30 carbon atoms, to fatty acids having 8 to 30 C atoms and onto alkylphenols having 8 to 15 carbon atoms in the alkyl group, such as those available under the trade names Dehydol ^® LS, LT Dehydol ^® types (Cognis),
• C ₁₂ -C ₃₀ -fatty acid mono- and diesters of addition products of 1 to 30 mol of ethylene oxide with glycerol,
• - polyglycerol esters and alkoxylated polyglycerol esters, such as poly (3) glycerol diisostearate (commercial product: Lameform ^® TGI (Henkel)) and poly (2) glycerinpolyhydroxystearat (commercial product: Dehymuls ^® PGPH (Henkel)).
• Adducts of 5 to 60 moles of ethylene oxide with castor oil and hydrogenated castor oil,
• - polyol, such as the commercially available product ^® Hydagen HSP (Cognis) or Sovermol types (Cognis),
• Alkoxylated, preferably propoxylated and in particular ethoxylated, mono-, di- and triglycerides, such as glycerol monolaurate + 20 ethylene oxide and glycerol monostearate + 20 ethylene oxide,
• - alkoxylated fatty acid alkyl esters of the formula RC (O) - (OCH ₂ CH ₂ ) _w OR ', in which RC (O) - represents a linear or branched, saturated and / or unsaturated acyl radical having 6 to 22 carbon atoms, R' is linear or branched alkyl radicals having 1 to 4 carbon atoms and w is from 1 to 20,
• - amine oxides,
• - hydroxymix ether,
• Sorbitan fatty acid esters and adducts of ethylene oxide with sorbitan fatty acid esters such as the polysorbates, sorbitan monolaurate and sorbitan monolaurate + 20 moles of ethylene oxide (EO),
• Sugar fatty acid esters and addition products of ethylene oxide with sugar fatty acid esters,
• Adducts of ethylene oxide with fatty acid alkanolamides and fatty amines,
• Fatty acid N-alkylglucamides,
• - Alkylphenols and Alkylphenolalkoxylate having 6 to 21, in particular 6 to 15 carbon atoms in the alkyl chain and 0 to 30 ethylene oxide and / or propylene oxide units. Preferred representatives of this class are, for example, nonylphenol + 4 EO, nonylphenol + 9 EO, octylphenol + 3 EO and octylphenol + 8 EO;
• - Alkylpolyglykoside according to the general formula RO- (Z) _x , wherein R is alkyl, Z is sugar and x is the number of sugar units. The alkyl polyglycosides which can be used according to the invention can only contain one particular alkyl radical R. Usually, however, these compounds are prepared starting from natural fats and oils or mineral oils. In this case, the alkyl radicals R are mixtures corresponding to the starting compounds or corresponding to the particular work-up of these compounds.

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

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

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

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

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

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

The alkoxylated homologs of said alkylpolyglycosides can also be used according to the invention be set. These homologs may contain on average up to 10 ethylene oxide and / or propylene oxide units per alkyl glycoside unit.

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

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

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

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

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

The alkylamidoamines are usually prepared by amidation of natural or synthetic fatty acids and fatty acid cuts with dialkylaminoamines and are characterized in addition to a good conditioning effect especially by their good biodegradability. An inventively particularly suitable compound from this group of substances under the name Tegoamid ^® S 18 stearamidopropyl commercially represent.

Likewise very readily biodegradable are quaternary ester compounds, so-called "ester quats". 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 with 1,2-dihydroxypropyldialkylamines. Such products are marketed under the trade names Stepantex® ^{®, ®} and Dehyquart® Armocare® ^®. The products Armocare ^® VGH-70, a N, N-bis (2-palmitoyloxyethyl) dimethylammonium chloride, as well as Dehyquart ^® F-75, Dehyquart ^® C-4046, Dehyquart ^® L80 and Dehyquart ^® AU-35 are also examples of such esterquats ,

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 special prefers.

In In a preferred embodiment, means, containing nonionic, zwitterionic and / or cationic Surfactants and mixtures thereof, be preferred.

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

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

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

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

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

Under the emulsifier types mentioned, the emulsifiers, which is not ethylene oxide and / or propylene oxide in the molecule contain very particularly preferred.

Especially preferred are in the inventive compositions additionally proteins and / or protein derivatives of plant or of animal origin, such as pea, soybean, wheat and almond protein hydrolyzate or acacia protein and collagen or keratin hydrolyzate. The agents according to the invention contain the proteins and / or protein derivatives of plant or of animal origin preferably in an amount of 0.1 to 10% by weight, in particular 0.5 to 3 wt .-%, each based on the weight of entire agent.

Farther it is preferred in the agents according to the invention at least one vegetable oil and / or at least one To incorporate plant extract.

The Vegetable oils are preferably obtained by pressing. Preferred vegetable oils are 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.

The vegetable oil is preferred in the composition of the invention in an amount of 0.05 to 5 Wt .-%, in particular 0.1 to 2 wt .-%, each based on the weight of the total composition.

Prefers The plant extracts are obtained by extraction with organic solvents (such as, for example, ethanol, isopropanol, diethyl ether, gasoline, Benzene, chloroform) or by steam distillation. Preferred plant extracts are, for example, extracts of flowers (Lime blossom, camomile, lily, lavender, roses, jasmine, Neroli, ylang-ylang), stems and leaves (Cassis, Horse chestnut, rooibos, birch, melissa, clover, vine leaves, Geranium, patchouli, petitgrain), fruits (anise, cassis, Coriander, caraway, juniper), fruit peel (bergamot, Lemon, Oranges, Litchi), Roots (Macis, Angelics, Celery, Cardamom, Costus, Iris, Calmus), wood (pine, sandal, guaiac, cedar, Rosewood), herbs and grasses (tarragon, lemongrass, Sage, thyme, rosemary), needles and twigs (spruce, fir, pine, Pines, sandalwood), resins and balms (galbanum, elemi, benzoin, Myrrh, olibanum, opoponax).

Especially Preferably, the plant extracts are selected from at least an extract from the group Hamamelis (Hamamelis virginiana L.), Grape leaves (Vitis vinifera L.), roses (Rosa gallica L.), Sandalwood (Pterocarpus Santalinus), Rooibos (Aspalathus linearis), Horse chestnut (Aesculus hippocastanum L.), clover (especially red clover, Trifolium pratense), cinnamon (Cinnamomum zeylanicum nees) and Cassis (especially from Cassis leaves, Ribes nigrum L.).

The Plant extracts are in the invention Agent preferably in an amount of 0.05 to 5 wt .-%, in particular 0.1 to 2 wt .-%, each based on the weight of the total composition, contain.

Farther the agent according to the invention can additionally at least one saccharide as mono-, di-, oligo- and / or polysaccharide contain. Preference is given to mono-, di- and / or oligosaccharides, especially D-glucose, D-galactose, D-mannose, D-fructose, L-arabinose, D-xylose, D-ribose, 2-deoxy-D-ribose, sucrose, Maltose, lactose, galactose, trehalose, cellobiose, gentiobiose and isomaltose.

Especially preferred is a combination of D-glucose and D-fructose. D-glucose and D-fructose can the inventive Each in their isolated form or z. B. as honey or Honey extract can be added.

• – nichtionische Polymere wie beispielsweise Vinylpyrrolidinon/Vinylacrylat-Copolymere, Polyvinylpyrrolidinon, Vinylpyrrolidinon/Vinylacetat-Copolymere, Polyethylenglykole und Polysiloxane,
• – kationische Polymere wie quaternisierte Celluloseether, Polysiloxane mit quaternären Gruppen, Dimethyldiallylammoniumchlorid-Polymere, Acrylamid-Dimethyldiallyl-ammoniumchlorid-Copolymere, mit Diethylsulfat quaternierte Dimethylamino-ethylmethacrylat-Vinylpyrrolidinon-Copolymere, Vinylpyrrolidinon-Imidazolinium-methochlorid-Copolymere und quaternierter Polyvinylalkohol,
• – zwitterionische und amphotere Polymere wie beispielsweise Acrylamidopropyl-trimethylammoniumchlorid/Acrylat-Copolymere und Octylacrylamid/Methyl-methacrylat/tert-Butylaminoethylmethacrylat/2-Hydroxypropylmethacrylat-Copolymere, Diallyldimethylammoniumchlorid/Acrylat-Copolymere, t-Butylaminoethylmethacrylat/N-(1,1,3,3-Tetramethylbutyl)acrylamid/Acrylat(/Methacrylat)-Copolymere,
• – anionische Polymere wie beispielsweise Polyacrylsäuren, vernetzte Polyacrylsäuren, Vinylacetat/Crotonsäure-Copolymere, Vinylpyrrolidinon/Vinylacrylat-Copolymere, Vinylacetat/Butylmaleat/Isobornylacrylat-Copolymere, Methylvinylether/Maleinsäureanhydrid-Copolymere und Acrylsäure/Ethylacrylat/N-t-Butyl-acrylamid-Terpolymere,
• – Verdickungsmittel wie Agar-Agar, Guar-Gum, Alginate, Xanthan-Gum, Gummi arabicum, Karaya-Gummi, Johannisbrotkernmehl, Leinsamengummen, Dextrane, Cellulose-Derivate, z. B. Methylcellulose, Hydroxyalkylcellulose und Carboxymethylcellulose, Stärke-Fraktionen und Derivate wie Amylose, Amylopektin und Dextrine, Tone wie z. B. Bentonit oder vollsynthetische Hydrokolloide wie z. B. Polyvinylalkohol,
• – Strukturanten wie Glucose, Maleinsäure und Milchsäure,
• – haarkonditionierende Verbindungen wie Phospholipide, beispielsweise Sojalecithin, Ei-Lecitin und Kephaline sowie Silikonöle,
• – Proteinhydrolysate, insbesondere Elastin-, Kollagen-, Keratin-, Milcheiweiß-, Sojaprotein- und Weizenproteinhydrolysate, deren Kondensationsprodukte mit Fettsäuren sowie quaternisierte Proteinhydrolysate,
• – Parfümöle, Dimethylisosorbid und Cyclodextrine,
• – Lösungsmittel und -vermittler wie Ethanol, Isopropanol, Ethylenglykol, Propylenglykol, Glycerin und Diethylenglykol,
• – faserstrukturverbessernde Wirkstoffe, insbesondere Mono-, Di- und Oligosaccharide wie beispielsweise Glucose, Galactose, Fructose, Fruchtzucker und Lactose,
• – quaternierte Amine wie Methyl-1-alkylamidoethyl-2-alkylimidazolinium-methosulfat
• – Entschäumer wie Silikone, bevorzugt Dimethicon,
• – Farbstoffe zum Anfärben des Mittels,
• – Antischuppenwirkstoffe wie Piroctone Olamine, Zink Omadine und Climbazol,
• – Lichtschutzmittel, insbesondere derivatisierte Benzophenone, Zimtsäure-Derivate und Triazine,
• – Substanzen zur Einstellung des pH-Wertes, wie beispielsweise übliche Säuren, insbesondere Genusssäuren und Basen,
• – Wirkstoffe wie Panthenol, Pantothensäure, Pantolacton, Allantoin, Pyrrolidinoncarbonsäuren und deren Salze sowie Bisabolol,
• – Vitamine, Provitamine und Vitaminvorstufen, insbesondere solche der Gruppen A, B₃, B₅, B₆, C, E, F und H,
• – Pflanzenextrakte wie die Extrakte aus Grünem Tee, Eichenrinde, Brennnessel, Hamamelis, Hopfen, Kamille, Klettenwurzel, Schachtelhalm, Weißdorn, Lindenblüten, Mandel, Aloe Vera, Fichtennadel, Rosskastanie, Sandelholz, Wacholder, Kokosnuss, Mango, Aprikose, Limone, Litchi, Weizen, Kiwi, Melone, Orange, Grapefruit, Salbei, Rosmarin, Birke, Malve, Wiesen schaumkraut, Quendel, Schafgarbe, Thymian, Melisse, Hauhechel, Huflattich, Eibisch, Meristem, Ginseng und Ingwerwurzel,.
• – Cholesterin,
• – Konsistenzgeber wie Zuckerester, Polyolester oder Polyolalkylether,
• – Fette und Wachse wie Walrat, Bienenwachs, Montanwachs und Paraffine,
• – Fettsäurealkanolamide,
• – Quell- und Penetrationsstoffe wie Glycerin, Propylenglykolmonoethylether, Carbonate, Hydrogencarbonate, Guanidine, Harnstoffe sowie primäre, sekundäre und tertiäre Phosphate,
• – Trübungsmittel wie Latex, Styrol/PVP- und Styrol/Acrylamid-Copolymere
• – Perlglanzmittel wie Ethylenglykolmono- und -distearat sowie PEG-3-distearat,
• – Pigmente,
• – Stabilisierungsmittel für Wasserstoffperoxid und andere Oxidationsmittel,
• – Treibmittel wie Propan-Butan-Gemische, N₂O, Dimethylether, CO₂ und Luft,
• – Antioxidantien.

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

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

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

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

According to the invention preferred Means are characterized in that the agent is immediate before use by mixing at least two preparations is prepared, wherein the at least two preparations in at least two separately prefabricated containers are provided and wherein a container is a colorant which is in a cosmetic carrier at least one oxidation dye precursor and at least one blue-green algae extract, preferably from the genus Spirulina, contains and has a pH between 5.0 and 8.5, preferably between 6.0 and 8.0, contains, and further container an oxidizing agent preparation containing at least one oxidizing agent.

One second subject of the present invention is a method for color and / or permanent change in shape keratinischer Fibers in which an inventive agent according to the above Specifications applied to the hair, for a contact time from 2 to 45 minutes, preferably from 15 to 30 minutes on the hair is left, and then rinsed the hair becomes.

A further preferred embodiment of the invention Method for changing the color of keratinous fibers is when a composition in a cosmetic carrier, containing at least one oxidation dye precursor and at least a blue-green algae extract, preferably from the genus Spirulina, with an oxidizing agent preparation containing hydrogen peroxide, mixed into a homogeneous composition, this on the hair is applied, for an exposure time of 2 to 45 minutes, preferably 15 to 30 minutes on the hair, and then the hair is rinsed out.

The Application temperatures in the inventive Color change of keratinic fibers may occur in range between 15 and 45 ° C. After an exposure time is the hair dye by rinsing of the Hair to be dyed removed. The washing with a shampoo may be omitted if a strong surfactant-containing carrier, eg. As a dyeing shampoo was used.

A further preferred embodiment of the invention Process for permanent change of shape keratinischer Fibers is present when a composition is in a cosmetic Carriers containing at least one keratin-reducing Substance and at least one blue-green algae extract, preferably from the genus Spirulina, is applied to the hair, for a contact time of 2 to 45 minutes, preferably from 15 to 30 minutes on the hair, and then if necessary, the hair is rinsed out. Subsequently is a fixing agent containing at least one oxidizing agent, preferably hydrogen peroxide, and preferably additionally at least one stabilizer or complexing agent, on the hair applied, for a contact time of 2 to 45 minutes, preferably from 15 to 30 minutes left on the hair, and then the hair is rinsed out

The Application temperatures in the inventive Permanent change in the shape of keratinous fibers can in a range between 15 and 45 ° C. After a Contact time is the fixative by rinsing removed from the hair. The washing with a shampoo can be omitted if a strong surfactant-containing carrier was used.

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

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

One The fourth subject of the present invention is therefore a multi-component packaging unit (Kit-of-Parts), containing at least two separately assembled Container, whereby a container at least one container has a color and / or shape-changing compound, as well as at least one Blue-green algae extract, preferably from the genus Spirulina and a container containing an oxidizer composition at least one chemical oxidizing agent, in particular hydrogen peroxide, contains

A preferred embodiment of this subject matter of the present invention Invention is therefore a multi-component packaging unit (kit-of-parts), containing at least two separate prefabricated containers, wherein a container a coloring mixture in a cosmetic Carrier comprising at least one coloring component, in particular, at least one oxidation dye precursor a blue-green algae extract, preferably from the genus Spirulina, and a container an oxidizer composition containing at least a chemical oxidant, especially hydrogen peroxide, contains.

Becomes a particularly strong whitening effect through the use of persulfate salts or peroxodisulfate salts, it is preferred according to the invention this of the multi-component packaging unit according to the invention (Kit-of-Parts) in the form of an optionally dedusted powder or a shaped article pressed in the form of separately packed, add additional component.

A Another preferred embodiment of the subject invention is a multi-component packaging unit (kit-of-parts) containing at least two separately assembled containers, one being a container a shape-change mixture in a cosmetic carrier, containing at least one shape-changing component as well at least one blue-green algae extract, preferably from the genus Spirulina, and a container containing an oxidizer composition at least one chemical oxidizing agent, in particular hydrogen peroxide, contains.

Prefers Contains the multi-component packaging unit (Kit-of-Parts) additionally an instruction manual. Furthermore it may be preferred if an application aid, such as For example, a comb or a brush, and / or a personal Protective equipment, such as disposable gloves attached to the kit.

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

One Another object of the invention is the use of the means of the first subject of the invention for improving the gloss of Hair in the color and / or permanent shape change human hair.

One Another object of the invention is the use of the means of the first subject of the invention for improving the moisture content the hair in the color and / or permanent shape change human hair.

One Another object of the invention is the use of the means of the first subject of the invention for simultaneous protection Damage in the hair structure and on the hair surface in the color and / or permanent change in shape of human Hair.

One Another object of the invention is finally the use the means of the first subject of the invention for color and / or Permanent change in shape of human hair with reduced damage The Hair.

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

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

Examples

• *Farbpulvermischung aus verschiedenen Oxidationsfarbstoffvorprodukten
• ¹Eau Vitale^® d'Algue Bleue Spirulina-Blaualgenextrakt (INCI-Bezeichnung: Water, Plankton extract, Phenoxyethanol) (Soliance)
• ²Emulgade^® F C₁₆-C₁₈-Fettalkohol; ethoxyliertes Rizinusöl (40 EO); C₁₆-C₁₈-Fettalkoholsulfat, Natriumsalz (INCI-Bezeichnung: Cetearyl alcohol, PEG-40 castor oil, Sodium Cetearyl Sulfate) (Cognis)

A coloring cream according to the invention was prepared from the following ingredients (in% by weight): E1 Eau Vitale ¹ 2.0 Carbomer 1.3 Potassium hydroxide (50%) 2.0 Emulgade F ² 3.0 Disodium Cocoamphodiacetate 5.0 Color powder mixture * 2.3 ascorbic acid 0.1 Sodium sulfite, anhydrous, 96% 0.2 phenoxyethanol 1.0 L-serine 1.0 Perfume 0.2 water ad 100

• * Color powder mixture of different oxidation dye precursors
• ¹ Eau Vitale ^® d'Algue Bleue Spirulina Blue Algae Extract (INCI name: Water, Plankton extract, Phenoxyethanol) (Soliance)
• ² Emulgade F ^® C ₁₆ -C ₁₈ fatty alcohol; ethoxylated castor oil (40 EO); C ₁₆ -C ₁₈ fatty alcohol sulfate, sodium salt (INCI name: cetearyl alcohol, PEG-40 castor oil, sodium cetearyl sulfate) (Cognis)

• ¹Genamin^® STAC Trimethylstearylammoniumchlorid (INCI-Bezeichnung: Steartrimonium Chloride) (Clariant)
• ²Eumulgin^® B 2 C₁₆-C₁₈-Fettalkohol, ethoxyliert (20 EO) (INCI-Bezeichnung: Ceteareth-20) (Cognis)

The dyeing cream was mixed in a weight ratio of 1: 1 with a developer dispersion composed as follows. The mixing pH was 7.2. raw material Wt .-% sodium benzoate 0.1 dipicolinic 0.1 disodiumpyrophosphate 0.1 Potassium hydroxide (50%) 0.3 1,2-propanediol 1.5 HEDP, 60% 0.4 Paraffin Liquidum 0.3 Genamine STAC ¹ 0.4 Eumulgin B 2 ² 1.0 Cetearyl Alcohol 3.4 Perfume qs Hydrogen peroxide (50%) 8th water ad 100

• ¹ Genamin ^® STAC trimethylstearylammonium chloride (INCI name: Steartrimonium Chloride) (Clariant)
• ² Eumulgin ^® B 2 C ₁₆ -C ₁₈ fatty alcohol ethoxylated (20 EO) (INCI name: Ceteareth-20) (Cognis)

For the staining was done on strands of human (codes: Kerling ENH 10/0 or Kerling ENH 6/0) of approx. 0.7 g each weight applied 4 times the amount of the finished application mixture. After this the strands for 20 minutes at 32 ° C were dyed, they were mixed with a commercial Washed shampoo and dried with a hair dryer.

QUOTES INCLUDE IN THE DESCRIPTION

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

Cited patent literature

• - EP 998908 A2 [0173]
• - DE 4436065 [0255]
• - EP 363057 B1 [0255]
• - US 4122029 [0323]
• - US 4265878 A [0323]
• US 4421769 A [0323]
• GB 2066659 A [0323]

Cited non-patent literature

• - occurrence, use, detection, H. Schweppe, ecomed Verlagsgesellschaft, 1993, Landsberg / Lech [0187]
• - Rompp Lexicon Chemistry (ed. J. Falbe, M. Regitz), 10th edition, Georg Thieme Verlag Stuttgart, New York, (1997), page 1764 [0358]
• - Kh. Schrader, bases and formulations of cosmetics, 2nd edition, Hüthig Buch Verlag, Heidelberg, 1989 [0371]

Claims (15)

Agent for color and / or permanent change in shape of keratinous fibers, in particular human hair, containing in a cosmetic carrier at least one color and / or shape-changing compound, characterized in that it additionally contains an extract of a blue-green algae. Means according to claim 1, characterized in that the extract of blue algae an extract of a freshwater blue algae of the genus Spirulina. Agent according to one of claims 1 and 2, characterized in that the agent additionally at least contains an extract from a plant of the genus Aloe. Agent according to one of claims 1 to 3, characterized in that the color-modifying component is selected (1) of at least one oxidation dye precursor and or (2) from oxo dye precursors and or (3) from at least a direct dye and or (4) at least a precursor of nature-analogous dyes and or (5) at least a natural dye. Agent according to one of claims 1 to 4, characterized in that it additionally comprises at least one active ingredient contains, which is selected from the group that is formed out c1) amino acids, oligopeptides and protein hydrolysates, c2) silicone derivatives, c3) polyphenols and c4) (pseudo) ceramides Agent according to one of claims 1 to 5, characterized in that it additionally comprises at least one active ingredient contains, which is selected from the group that is formed from amino acids, oligopeptides and protein hydrolysates. Agent according to one of claims 1 to 6, characterized in that it additionally comprises at least one active ingredient which is selected from L-serine, D-serine, D / L-serine, L-homoserine, D-homoserine, D / L-homoserine, L-threonine, D-threonine, D / L-threonine, 4-hydroxy-proline, 5-hydroxy-lysine, L-arginine, D-arginine, D / L-arginine, L-lysine, D-lysine, D / L-lysine, L-ornithine, D-ornithine, D / L-ornithine, L-histidine, D-histidine and D / L-histidine and / or one of its physiologically acceptable salts. Agent according to one of claims 1 to 7, characterized in that the ready to use means a pH between 4.0 and 9.0, preferably between 5.0 and 8.5, in particular preferably between 6.0 and 8.0. Agent according to claims 1 to 8, characterized in that it additionally contains an alkalizing agent contains, selected from the group formed is made of sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, Sodium phosphate, potassium phosphate, sodium silicate, potassium silicate, Sodium carbonate and potassium carbonate. Agent according to one of claims 1 to 9, characterized in that the agent low ammonia, preferably free of ammonia is. Agent according to one of claims 1 to 10, characterized in that immediately before use by Mixing at least two preparations is produced, wherein the at least two preparations in at least two separately formulated Containers are provided and wherein a container is a colorant (a) which in a cosmetic carrier at least one Oxidation dye precursor and an extract of a blue-green algae contains and a pH between 5.0 and 8.5, preferably between 6.0 and 8.0, contains, and another Container an oxidizing agent preparation (b) containing at least an oxidizing agent. Method of treating human hair, in an agent according to any one of claims 1 to 11 to the Hair is applied for a contact time of 2 to 45 Minutes, preferably 15 to 30 minutes on the hair, and then the hair is rinsed out. Use of an agent according to a of claims 1 to 11 for improving the shine of the hair in the color and / or permanent change in shape of human Hair. Use of an agent according to a of claims 1 to 11 for improving the moisture content the hair in the color and / or permanent shape change human hair. Kit of parts, containing at least two separate prefabricated containers, with a container a color and / or shape changing compound according to a of claims 1 to 10 and a container a Oxidizing agent composition containing at least one chemical Oxidizing agent, in particular hydrogen peroxide.