WO2010072577A2

WO2010072577A2 - Hair colour with care properties

Info

Publication number: WO2010072577A2
Application number: PCT/EP2009/066833
Authority: WO
Inventors: Maureen Rippe; Astrid Kleen; Mustafa Akram; Stephan Schwartz
Original assignee: Henkel Ag & Co. Kgaa
Priority date: 2008-12-15
Filing date: 2009-12-10
Publication date: 2010-07-01
Also published as: WO2010072577A3; DE102008061861A1

Abstract

The invention relates to a colouring composition for keratinous fibres for colorations that have shine and care properties. This colouring composition comprises, in a cosmetic vehicle, not only a colouring component but also a care combination comprising at least one cationized protein hydrolysate and at least one active plant extract. The combination in question is preferably the combination of a cationized casein hydrolysate and an active extract from aloe vera. The addition of this care combination proves to be particularly advantageous in oxidative colouring compositions. The invention further relates to the use of the said composition for improving the moisture content and the care condition, more particularly shine and wet combability, of keratin-type fibres, more particularly human hair, when colouring.

Description

"Nourishing hair color"

The invention relates to a coloring agent for keratin-containing fibers for glossy and nourishing dyeings. This colorant contains in a cosmetic carrier in addition to a coloring component a care combination of at least one cationized protein hydrolyzate and at least one active plant extract. It is preferably the combination of a cationized casein hydrolyzate and an effective extract of aloe vera. Particularly advantageous is the addition of this care combination proves to oxidative colorants. Moreover, the invention relates to the use of said agent for improving the moisture content and condition, in particular gloss and wet combability, of keratinic fibers, in particular human hair, in the dyeing.

Changing the shape and color of the hair is an important area of modern cosmetics. This allows the hair's appearance to be adapted to current fashion trends as well as to the individual wishes of the individual. For the fashionable color design of hairstyles or for lamination of gray or even white hair with fashionable or natural shades, the consumer takes to farbve rändernden resources. In addition to the desired dyeing power, these agents should cause the least possible damage to the hair and preferably even have additional care properties.

To provide farbve rändernd he cosmetic agents, especially for the skin or keratin fibers such as human hair, the skilled person knows depending on the requirements of the coloring various dyeing systems.

In particular, oxidative hair dyes are disadvantageous to the user despite their advantageous dyeing properties. First, the use of the oxidizing agent for coloration or development of the actual dyeing leads to damage in the hair structure and on the hair surface. The hair becomes brittle, its elasticity decreases and the combability decreases. This damage increases with the duration of use. Commercially available oxidative colorants usually have to act on the hair fiber for a period of 30 minutes and longer. However, it is also obvious for reasons of convenience of use that there is a need among users of such hair dyeing to reduce this exposure time. Second, oxidative stains typically require a basic pH for staining, especially between pH 9.0 and pH 11.5. These pH values are necessary to ensure an opening of the outer cuticle (cuticle) and to allow a penetration of the active species (dye precursors and / or hydrogen peroxide) into the hair. However, the basic environment is another cause of damage to the hair and its structure, which is also gaining in importance with increased application time. The spreading of 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. As a result, there is an increased need for the consumer to use additional aftertreatment agents such as conditioning agents.

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

In order to save the additional post-treatment step, it has therefore not lacked attempts to incorporate suitable care substances in the hair dye. Usually, oxidative hair dyes are prepared immediately prior to use from a dyeing preparation and a so-called developer preparation. As a rule, the dyeing preparation has a strongly basic pH in order to stabilize the oxidation dye precursors contained therein, while the developer preparation contains a weakly acidic pH, but contains the oxidizing agents necessary for dye formation. Both additions thus do not represent an advantageous environment for containing a chemically sensitive care product without decomposition. There is therefore still a need for suitable, stable care substances which can be incorporated into oxidative colorants and thus be able to minimize damage already occurring during the dyeing process.

Object of the present invention is therefore to lower the above-mentioned disadvantages of oxidative hair dyes. The dyes are intended to protect the hair and thus cause a reduced damage to the hair. In particular, the agent should be used to improve the moisture content in the fiber, which gives the hair increased elasticity and smoothness, as well as improved gloss. Nursing properties of the compositions are particularly desirable, so that the user can do without the use of additional aftertreatment agents. Furthermore, an effective protection against oxidative damage to the hair structure and the hair surface by the hair dye is to be achieved. However, the reduction of hair damage during staining should not be achieved at the expense of reduced staining performance of the compositions.

In an unpredictable manner has now been found that the addition of a care combination of at least one cationized protein hydrolyzate and at least one effective Plant extract in coloring agents for keratinic fibers advantages over conventional ones

Dyes causes gloss and care of the fibers.

A first subject of the invention is therefore an agent for coloring keratin-containing fibers, in particular human hair, containing in a cosmetic carrier at least one coloring component, characterized in that the agent contains a care combination of at least one cationized protein hydrolyzate and at least one active plant extract.

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

The agents according to the invention contain the active ingredients in a cosmetic carrier. For the purposes of the invention, this cosmetic carrier is aqueous, alcoholic or aqueous-alcoholic. For the purpose of hair coloring such carriers are, for example, creams, emulsions, gels or surfactant-containing foaming solutions, such as shampoos, foam aerosols or other preparations which are suitable for use on the hair. For the purposes of the present invention, aqueous-alcoholic carriers are water-containing compositions containing 3 to 70% by weight of a C 1 -C ₄ -alcohol, based on the total weight of the application mixture, in particular ethanol or isopropanol. The compositions of the invention may additionally contain other organic solvents such as methoxybutanol, ethyldiglycol, 1, 2-propylene glycol, n-propanol, n-butanol, n-butylene glycol, glycerol, diethylene glycol monoethyl ether, and diethylene glycol mono-n-butyl ether. Preference is given to all water-soluble organic solvents. For the purposes of the invention, an aqueous carrier contains at least 30% by weight, in particular at least 50% by weight, of water, based on the total weight of the application mixture.

As a first essential ingredient, the composition according to the invention contains as a care substance a care combination of at least one cationized protein hydrolyzate and at least one active plant extract. This care combination of at least one cationized protein hydrolyzate and at least one active plant extract has the advantage over other care substances to have sufficient stability in the colorant, especially against different pH values, and so to be able to develop its conditioning effect even under the harsh conditions of an oxidative hair treatment can ,

The care combination according to the invention contains at least one cationized protein hydrolyzate and at least one active plant extract. The first obligatory ingredient of the agent according to the invention is a cationized, ie a cationically derivatized, protein hydrolyzate. With regard to the nature and the origin of the protein hydrolyzate, according to the invention initially there are no restrictions.

In a particular embodiment of the present invention, cationized protein hydrolysates are used which

From animal proteins, for example from elastin, collagen, silk, milk or

Keratin,

From vegetable proteins, for example wheat, maize, rice, potatoes, soya or almonds,

From marine life forms, such as fish collages or algae, or

• - or can be obtained biotechnologically.

The protein hydrolyzates on which the cationized derivatives according to the invention are based can be obtained from the corresponding proteins themselves or one of their degradation products, such as gelatin, by chemical, in particular alkaline or acid hydrolysis, by enzymatic hydrolysis and / or a combination of both types of hydrolysis. For the enzymatic degradation all hydrolytic enzymes are suitable, such as. B. alkaline proteases. The hydrolysis of proteins usually results in a protein hydrolyzate having a molecular weight distribution of about 75 daltons to several thousand daltons. Preference is given to those cationized protein hydrolyzates whose underlying protein content has a molecular weight of 75 to 25,000 daltons, preferably 150 to 5000 daltons. In the context of the present invention, cationized total hydrolyzates of proteins have also proved to be preferred. Overviews on the preparation and use of protein hydrolysates are described, for example, by G. Schuster and A. Domsch in Soaps Oils Fette Wachse 108, (1982) 177 and Cosm.Toil, respectively. 99, (1984) 63, by H.W. Steisslinger in Parf.Kosm. 72, (1991) 556 and F. Aurich et al. in Tens.Surf.Det. 29, (1992) 389 appeared.

Further examples of protein hydrolysates and protein hydrolyzate derivatives falling within the scope of the present invention are described in CTFA 1997 International Buyers' Guide, John A. Wenninger et al. (Ed.), The Cosmetic, Toiletry and Fragrance Association, Washington DC 1997, 686-688.

The cationization of the protein hydrolysates is usually carried out by means of quaternary ammonium salts such as, for example, N, N-dimethyl-N- (n-alkyl) -N- (2-hydroxy-3-chloro-n-propyl) ammonium halides. In particular, the methyl group and alkyl chains derived from fatty acids are suitable as the n-alkyl chain. In addition, the cationic protein hydrolysates may also be further derivatized. As typical examples of the cationized protein hydrolyzates and derivatives according to the invention, those listed under the INCI names in the International Cosmetic Ingredient Dictionary and Handbook, (7th edition 1997, The Cosmetic, Toiletry and Fragrance Association 1101 17 ^th Street, NW, Suite 300 , Washington, DC 20036- 4702) and commercially available products: cocodimonium hydroxypropyl

Hydrolyzed Collagen, Cocodimonium Hydroxypropyl Hydrolyzed Casein, Cocodimonium Hydroxypropyl Hydrolyzed Hair Keratin, Cocodimonium Hydroxypropyl Hydrolyzed Keratin, Cocodimonium Hydroxypropyl Hydrolyzed Rice Protein, Cocodimonium Hydroxypropyl Hydrolyzed SiCl, Cocodimonium Hydroxypropyl Hydrolyzed Soy Protein, Cocodimonium Hydroxypropyl Hydrolyzed Wheat Protein, Cocodimonium Hydroxypropyl SiIk Amino Acids, Hydroxypropyl Arginine Lauryl / Myristyl Ether HCl, Hydroxypropyltrimonium Gelatin, Hydroxypropyltrimonium Hydrolyzed Casein, Hydroxypropyltrimonium Hydrolyzed Collagen, Hydroxypropyltrimonium Hydrolyzed Conchiolin Protein, Hydroxypropyltrimonium Hydrolyzed keratin, Hydroxypropyltrimonium Hydrolyzed Rice Bran Protein, Hydroxyproypltrimonium Hydrolyzed SiCl, Hydroxypropyltrimonium Hydrolyzed Soy Protein, Hydroxypropyl Hydrolyzed Vegetable Protein , Hydroxypropyltrimonium Hydrolyzed Wheat Protein, Hydroxypropyltrimonium Hydrolyzed Wheat Pro Lauryldimonium Hydroxypropyl Hydrolyzed Soy Protein, Lauryldimony Hydroxypropyl Hydrolyzed Wheat Protein, Lauryldimony Hydroxypropyl Hydrolyzed Wheat Protein / Siloxysilicate, Lauryldimony Hydroxypropyl Hydrolyzed Casein, Lauryldimonium Hydroxypropyl Hydrolyzed Collagen, Lauryldimonium Hydroxypropyl Hydrolyzed Keratin, Lauryldimonium Hydroxypropyl Hydrolyzed SiIc, Lauryldimonium Hydroxypropyl Hydrolyzed Soy Protein, Steardimonium Hydroxypropyl Hydrolyzed Casein, Steardimonium Hydroxypropyl Hydrolyzed Collagen, Steardimonium Hydroxypropyl Hydrolyzed Keratin, Steardimonium Hydroxypropyl Hydrolyzed Rice Protein, Steardimonium Hydroxypropyl Hydrolyzed SiIk, Steardimonium Hydroxypropyl Hydrolyzed Soy Protein, Steardimonium Hydroxypropyl Hydrolyzed Vegetable Protein, Steardimonium Hydroxypropyl Hydrolyzed Wheat Protein, Steartrimonium Hydroxyethyl Hydrolyzed Collagen , Quaternium-76 Hydrolyzed Collagen, Quaternium-79 Hydrolyzed Collagen, Quaternium-79 Hydrolyzed K Eratin, Quaternium-79 Hydrolyzed Milk Protein, Quaternium-79 Hydrolyzed Sick, Quaternium-79 Hydrolyzed Soy Protein, Quaternium-79 Hydrolyzed Wheat Protein.

Preferred agents contain a cationized protein hydrolyzate which is selected from cationized protein hydrolysates of animal origin, in particular from collagen, keratin and milk.

Very particularly preferred agents are characterized in that the cationized protein hydrolyzate is a cationized milk protein hydrolyzate, in particular a cationized casein hydrolyzate. Particularly preferred hydroxypropyltrimonium Hydrolyzed Casein, as it is commercially available, for example, under the trade name Promois MiIk-Q from Seiwa Kasei.

According to preferred means for dyeing keratinic fibers are characterized in that they - based on their weight - 0.05 to 7.5 wt .-%, preferably 0.1 to 5 Wt .-%, particularly preferably 0.2 to 3.5 wt .-% and in particular 0.25 to 1, 5 wt .-% cationized protein hydrolyzate (s) included.

The second obligatory ingredient of the agent according to the invention is an effective plant extract. The term "effective" in the context of the invention means that the addition of this plant extract on average supports and promotes the desired properties of the composition with regard to moisture control in the fiber and gloss improvement.

Plant extracts are usually prepared by extraction of the entire plant, but in some cases also exclusively from flowers and / or leaves and / or seeds and / or other parts of plants. According to the invention, especially the extracts from the meristem, so the divisible educated tissue of the plants, and special plants such as green tea, witch hazel, chamomile, marigold, pansy, Paeonie, aloe vera, horse chestnut, sage, willow bark, cinnamon tree (cinnamon tree), chrysanthemums , Oak bark, stinging nettle, hops, burdock root, horsetail, hawthorn, lime blossom, almonds, spruce needles, sandalwood, juniper, coconut, kiwi, guava, lime, mango, apricot, wheat, melon, orange, grapefruit, avocado, rosemary, birch, beech shoots , Mallow, Meadowfoam, Yarrow, Quender, Thyme, Melissa, Grasshoppers, Marshmallow (Althaea), Mallow (Malva sylvestris), Violet, Blackcurrant Leaves, Coltsfoot, Fennelwort, Ginseng, Ginger Root and Sweet Potato are preferred. Algae extracts can also be used to advantage. The algae extracts used according to the invention are derived from green algae, brown algae, red algae or blue-green algae (cyanobacteria). The algae used for extraction can be obtained both from natural sources as well as by biotechnological processes and, if desired, be modified from the natural form. The alteration of the organisms may be by genetic engineering, by breeding or by cultivation in media enriched with selected nutrients. Preferred algae extracts are from seaweed, blue-green algae, from the green alga Codium tomentosum and from the brown algae Fucus vesiculosus. A particularly preferred algae extract is derived from blue-green algae of the species Spirulina, which were cultured in a magnesium-enriched medium.

The extracts of spirulina, green tea, aloe vera, meristem, witch hazel, apricot, calendula, guava, sweet potato, lime, mango, kiwi, cucumber, mallow, marshmallow and violet are preferred. The compositions according to the invention may also contain mixtures of several, especially two, different plant extracts.

Preferred active plants extra kte are in particular extracts of flowers (lime blossom, chamomile, lily, lavender, roses, jasmine, neroli, ylang-ylang), stems and leaves (aloe, 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, angelica, 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 balsams (galbanum, elemi, benzoin, myrrh, olibanum, opoponax).

The active plant extracts are more preferably selected from at least one extract from the group aloe (aloe barbadensis), witch hazel (hamamelis virginiana L.), vine leaves (Vitis vinifera L.), roses (Rosa gallica L.), sandalwood (Pterocarpus santalinus), Rooibos (Aspalathus linearis), horse chestnut (Aesculus Hippocastanum L.), clover (especially red clover, Trifolium pratense), cinnamon (Cinnamomum zeylanicum nees) and cassis (especially from Cassis leaves, Ribes nigrum L.).

As an extractant for the preparation of said plant extracts u. a. Water, alcohols and mixtures thereof are used. Among the alcohols are lower alcohols such as ethanol and isopropanol, but especially polyhydric alcohols such as ethylene glycol, propylene glycol and butylene glycol both as sole extractant and in admixture with water, are preferred. Plant extracts based on water / propylene glycol in a ratio of 1:10 to 10: 1 have proven to be particularly suitable. The steam distillation according to the invention falls under the preferred extraction method.

The active plant extracts according to the invention can be used both in pure and in diluted form. If they are used in diluted form, they usually contain about 0.1 to 80 wt .-% of active substance and as a solvent used in their extraction agent or extractant mixture. Depending on the choice of extractants, it may be preferable to stabilize the plant extract by adding a solubilizer. Suitable solubilizers are, for. B. Ethoxylation products of optionally hydrogenated vegetable and animal oils. Preferred solubilizing agents are ethoxylated mono-, di- and triglycerides of C _{_8-22} fatty acids with 4 to 50 ethylene oxide units, for example. Hydrogenated ethoxylated castor oil, olive oil ethoxylate, almond oil ethoxylate, mink oil ethoxylate, polyoxyethylene glycol caprylic / capric acid glycerides, polyoxyethylene glycerol monolaurate and polyoxyethylene glycol coconut fatty acid glycerides.

However, it is also possible to use preparations which are obtained from the plant by means of mechanical and / or chemical techniques. For this purpose, the plant components can be mechanically comminuted in an optional first step. Examples of mechanical comminuting methods include, for example, slicing, pureeing and crushing.

In the second essential step, the preparations can then be obtained in a first embodiment by means of mechanical separation methods from the plant components, which are based on the utilization of mechanical forces, such as gravity, centrifugal force, pressure or vacuum. These include, for example, decanting, filtration, sedimentation, ultrafiltration and centrifugation. In a further embodiment of the present invention, preparations are used which are obtained from the plant constituents by means of chemical separation methods, for example an extraction or a chromatographic method. In the context of this embodiment, extracts are particularly preferred. As extraction agent for the preparation of said plant extracts water, alcohols and mixtures thereof can be used. Among 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 admixture with water, are preferred. Plant extracts derived from water-propylene glycol mixtures have proven to be particularly suitable. It has proven to be particularly suitable if these extractants are used in a ratio of 1:10 to 10: 1.

Furthermore, it may be preferred according to the invention to use extracts which have been at least partially decolorized before use. This can be done for example by using activated carbon.

The plant extracts are contained in the agent according to the invention preferably in an amount of 0.0005 to 15 wt .-%, in particular 0.001 to 10 wt .-%, each based on the weight of the total composition.

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

In a particularly preferred embodiment of the present invention, the agent for coloring keratinic fibers as active plants extra kt contains an extract of aloe barbadensis.

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

Particularly preferred according to the invention are preparations which are obtained from Aloe capensis or Aloe barbadensis. Very particularly preferred according to the invention are obtained from Aloe barbadensis, the so-called genuine aloe or aloe vera.

Both the leaves and the flowers and seeds of the aloe plants can serve as a basis for this preparation. Preparations which are obtained from the leaves of the Aloe plants have proved to be particularly preferred according to the invention.

Also with regard to the manner in which the preparation according to the invention is obtained from the plant constituents, in principle there are no restrictions. For example, the gel contained in the plants can be used directly in the form in which it occurs in violation of the aloe leaves.

The effectiveness of an extract of aloe can be attributed directly to its characteristic composition of ingredients. This composition may differ in parts by weight and ingredients depending on the type of aloe, on growth conditions, on the part of the plant used and on its method of production. An effective extract comprises, in addition to water, an organic solvent optionally used in the extraction, vitamins and vitamin precursor compounds, essential oils, minerals and trace elements, in particular characteristic agents of aloe.

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

The main constituent of the characteristic active ingredients of an Aloe extract is Aloein (also Aloin, Aloein A or Barbaloin), a Anthrachinonglycosid with the following structure:

Aloein A (1,8-dihydroxy-3-hydroxymethyl-10 - (/ 3) -D- (glucopyranosyl) anthrone). As monosaccharides are usually arabinose, galactose, glucose, mannose and xylose in the extract, as polysaccharide ingredients at least one glucomannan, and are also essential β-linked mannose polymers such as acemannan (ß-1, 4-acetylated mannan) , Active extracts of the Aloe vera preferred according to the invention therefore contain at least aloe.

Extracts of the Aloe vera which are particularly preferred according to the invention can be obtained by extraction from stems and / or leaves of Aloe barbadensis with a mixture of water and propylene glycol as extractant.

Particularly preferred agents are characterized in that the agent comprises the effective extract of Aloe barbadensis in a proportion of 0.01 to 10 wt .-%, preferably from 0.05 to 5 wt .-% and in particular from 0.1 to 3 wt .-%, in each case based on the total weight of the ready-to-use agent contains.

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

(a) oxidation dye precursors and / or

(b) naturally-analogous dyes and / or

(c) oxo dye precursors and / or

(d) direct dyes.

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

Due to their reaction behavior, oxidation dye precursors can be divided into two categories, so-called developer components and coupler components. Developer components can form the actual dye with themselves. They may therefore be contained as sole, color-changing compounds in the composition according to the invention. In a preferred embodiment, the compositions of the invention contain at least one developer type and / or type of coupler oxidation dye precursor. Preferably, the colorants of the present invention contain at least one developer type oxidation dye precursor and at least one coupler type oxidation dye precursor.

The developer and coupler components are usually used in free form. In the case of substances having amino groups, however, it may be preferable to use them in salt form, in particular in the form of the hydrochlorides and hydrobromides or the sulfates. Particularly preferred p-phenylenediamines are selected from one or more

Compounds of the group formed from 1, 4-diaminobenzene (p-phenylenediamine), 1, 4-diamino-2-methylbenzene (p-toluenediamine), 1, 4-diamino-2-chlorobenzene (2-chloro -p-phenylenediamine), 2,3-dimethyl-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2,6-diethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, N, N-dipropyl-p-phenylenediamine, 4-amino-3-methyl- (N, N-diethyl) aniline, N , N-bis (2-hydroxyethyl) -p-phenylenediamine, 4-N, N-bis (2-hydroxyethyl) amino-2-methylaniline, 4-N, N-bis (2-hydroxyethyl ) amino-2-chloroaniline, 2- (2-hydroxyethyl) -p-phenylenediamine, 2- (1,2-dihydroxyethyl) -p-phenylenediamine, 2-fluoro-p-phenylenediamine, 2-isopropyl-p-phenylenediamine, N - (2-hydroxypropyl) p-phenylenediamine, 2-hydroxymethyl-p-phenylenediamine, N, N-dimethyl-3-methyl-p-phenylenediamine, N-ethyl-N-2-hydroxyethyl-p-phenylenediamine, N- ( 2,3-dihydroxypropyl) -p-phenylenediamine, N- (4'-aminophenyl) -p-phenylenediamine, N-phenyl-p-phenylenediamine, 2- (2-hyd roxyethyloxy) -p-phenylenediamine, 2-methoxymethyl-p-phenylenediamine, 2- (2-acetylaminoethyloxy) -p-phenylenediamine, N- (2-methoxyethyl) -p-phenylenediamine, N- (4-amino-3- methylphenyl) -N- [3- (1H-imidazol-1-yl) propyl] amine, 5,8-diaminobenzo-1, 4-dioxane and their physiologically acceptable salts. Particularly preferred p-phenylenediamine derivatives according to the invention are selected from at least one compound of the group p-phenylenediamine, p-toluenediamine, 2- (2-hydroxyethyl) -p-phenylenediamine, 2- (1, 2-dihydroxyethyl) -p-phenylenediamine, N, N-bis (2-hydroxyethyl) -p-phenylenediamine, N- (4-amino-3-methylphenyl) -N- [3- (1 H -imidazol-1-yl) propyl] amine, 2-methoxymethyl p-phenylenediamine and their physiologically acceptable salts. It may further be preferred according to the invention to use as developer component compounds which contain at least two aromatic nuclei which are substituted by amino and / or hydroxyl groups. In particular, preferred binuclear developer components are selected from at least one of the following compounds: N, N'-bis (2-hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diaminopropan-2-ol, N, N'-bis (2-hydroxyethyl) -N, N'-bis (4'-aminophenyl) ethylenediamine, N, N'-bis (4'-aminophenyl) tetramethylenediamine, N, N'-bis 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-di - azacycloheptane, N, N'-bis (2-hydroxy-5-aminobenzyl) piperazine, N- (4'-aminophenyl) -p-phenylenediamine and 1, 10-bis- (2 ', 5'-diaminophenyl ) -1, 4,7,10-tetraoxadecane and their physiologically acceptable salts. Particularly preferred binuclear developer components are selected from N, N'-bis (2-hydroxyethyl) -N, N'-bis (4-aminophenyl) -1,3-diaminopropan-2-ol, bis (2-hydroxybenzoyl) 5-aminophenyl) methane, 1, 3-bis (2,5-diaminophenoxy) propan-2-ol, N, N'-bis (4-aminophenyl) -1, 4-diazacycloheptane, 1, 10-bis- (2,5-diaminophenyl) -1, 4,7,10-tetraoxadecane or one of their physiologically acceptable salts. Furthermore, it may be preferred according to the invention to use as the developer component a p-aminophenol derivative or one of its physiologically tolerable salts. Preferred p-aminophenols are 4-aminophenol, N-methyl-4-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 2-hydroxymethylamino-4-aminophenol, 4-amino-3-hydroxymethylphenol, 4 -Amino-2- (2-hydroxyethoxy) phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, A-amino-2- (2-hydroxyethylaminomethyl) phenol, 4-amino-2- (1,2-dihydroxyethyl) phenol, 4-amino-2- fluorophenol, 4-amino-2-chlorophenol, 4-amino-2,6-dichlorophenol, 4-amino-2- (diethylaminomethyl) phenol and their physiologically acceptable salts. Particularly preferred compounds are A-aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (1, 2-dihydroxyethyl) phenol and 4-amino-2- (diethylaminomethyl) phenol. Further, the developer component may be selected from o-aminophenol and its derivatives such as 2-amino-4-methylphenol, 2-amino-5-methylphenol or 2-amino-4-chlorophenol. Furthermore, the developer component may be selected from heterocyclic developer components, such as pyrimidine derivatives, pyrazole derivatives, pyrazolopyrimidine derivatives or their physiologically acceptable salts. Particularly preferred pyrimidine derivatives are the compounds 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2-dimethylamino-4,5,6- triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6-triaminopyrimidine. Preferred pyrazole derivatives are the compounds selected from 4,5-diamino-1-methylpyrazole, 4,5-diamino-1- (2-hydroxyethyl) pyrazole, 3,4-diamino-pyrazole, 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 tolerated salts, but in particular 4,5 diamino-1- (2-hydroxyethyl) pyrazole. The pyrazolo [1,5-a] pyrimidines may be mentioned in particular: pyrazolo [1,5-a] pyrimidine-3,7-diamine, 2,5-dimethylpyrazolo [1,5-a] pyrimidine-3,7- diamine, pyrazolo [1,5-a] pyrimidine-3,5-diamine, 2,7-dimethylpyrazolo [1,5-a] pyrimidine-3,5-diamine, 3-aminopyrazolo [1,5-a] pyrimidine 7-ol, 3-aminopyrazolo [1,5-a] pyrimidin-5-ol, 2- (3-aminopyrazolo- [1,5-a] pyrimidin-7-ylamino) ethanol, 2- (7-aminopyrazolo [1 , 5-a] pyrimidin-3-ylamino) ethanol, 2 - [(3-aminopyrazolo [1,5-a] pyrimidin-7-yl) - (2-hydroxyethyl) amino] ethanol, 2 - [(7-aminopyrazolo [1, 5-a] pyrimidin-3-yl) (2-hydroxyethyl) amino] ethanol, 5,6-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine, 2,6-dimethylpyrazolo [ 1, 5-a] pyrimidine-3,7-diamine, 3-amino-7-dimethylamino-2,5-dimethylpyrazolo [1, 5-a] pyrimidine and their physiologically acceptable salts and their tautomeric forms when in tautomeric equilibrium is available.

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

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

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

Preferred 3-aminophenol coupler components are selected from at least one compound from the group formed from 3-aminophenol, 5-amino-2-methylphenol, N-cyclopentyl-3-aminophenol, 3-amino-2-chloro 6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 2,6-dimethyl-3-aminophenol, 3-trifluoroacetylamino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5-amino 4-methoxy-2-methylphenol, 5- (2'-hydroxyethyl) amino-2-methylphenol, 3-diethylaminophenol, N-cyclopentyl-3-aminophenol, 1, 3-dihydroxy-5- (methylamino) benzene, 3-ethylamino 4-methylphenol, 2,4-dichloro-3-aminophenol and their physiologically acceptable salts. Preferred 3-diaminobenzene coupler components are selected from at least one compound selected from the group consisting of 3-aminoaniline (m-phenylenediamine), 2- (2,4-diaminophenoxy) ethanol, 1, 3-bis (2,4-diaminophenoxy) diaminophenoxy) propane, 1-methoxy-2-amino-4- (2'-hydroxyethylamino) benzene, 1, 3-bis (2,4-diaminophenyl) propane, 2,6-bis (2'-hydroxyethylamino) -1- methylbenzene, 2 - ({3 - [(2-hydroxyethyl) amino] -4-methoxy-5-methylphenyl} amino) ethanol, 2 - ({3 - [(2-hydroxyethyl) amino] -2-methoxy-5- methylphenyl} amino) ethanol, 2 - ({3 - [(2-hydroxyethyl) amino] -4,5-dimethylphenyl} amino) ethanol, 2- [3-morpholin-4-ylphenyl) amino] ethanol, 3-amino 4- (2-methoxyethoxy) -5-methylphenylamine, 1-amino-3-bis (2'-hydroxyethyl) aminobenzene and their physiologically acceptable salts. Preferred 1, 2-diaminobenzene coupler components are selected from at least one compound from the group formed from 3,4-diaminobenzoic acid and 2,3-diamino-1-methylbenzene and their physiologically acceptable salts. Preferred di- or trihydroxybenzenes and their derivatives are selected from at least one compound of the group formed from resorcinol, resorcinol monomethyl ether, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2-chlororesorcinol, 4-chlororesorcinol, pyrogallol and 1, 2,4-trihydroxybenzene. Preferred pyridine derivatives are selected from at least one compound of the group formed from 2,6-dihydroxypyridine, 2-amino-3-hydroxypyridine, 2-amino-5-chloro-3-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 their physiologically acceptable salts. Preferred naphthalene derivatives having at least one hydroxy group are selected from at least one compound of the group formed from 1-naphthol, 2-methyl-1-naphthol, 2-hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1 , 3-dihydroxynaphthalene, 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 1, 7-dihydroxynaphthalene, 1, 8-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and 2,3-dihydroxynaphthalene. Preferred indole derivatives are selected from at least one compound of the group formed from 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole and their physiologically acceptable salts. Preferred indoline derivatives are selected from at least one compound of the group formed from 4-hydroxyindoline, 6-hydroxyindoline and 7-hydroxyindoline and their physiologically acceptable salts. 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 their physiologically acceptable salts.

Particularly preferred coupler components according to the invention are selected from 3-aminophenol, 5-amino-2-methylphenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 5-amino-4-chloro-2 -methylphenol, 5- (2-hydroxyethyl) amino-2-methylphenol, 2,4-dichloro-3-aminophenol, 2-aminophenol, 3-phenylenediamine, 2- (2,4-diaminophenoxy) ethanol, 1, 3-bis (2,4-diaminophenoxy) propane, 1-methoxy-2-amino-4- (2-hydroxyethylamino) benzene, 1, 3-bis (2,4-diaminophenyl) propane, 2,6-bis (2'-hydroxyethylamino ) -1-methylbenzene, 2 - ({3 - [(2-hydroxyethyl) amino] -4-methoxy-5-methylphenyl} amino) ethanol, 2 - ({3 - [(2-hydroxyethyl) amino] -2 -methoxy-5-methylphenyl} amino) ethanol, 2- ({3 - [(2-hydroxyethyl) amino] -4,5-dimethylphenyl} amino) ethanol, 2- [3-morpholin-4-ylphenyl) amino] ethanol , 3-amino-4- (2-methoxyethoxy) -5-methylphenylamine, 1-amino-3-bis (2-hydroxyethyl) aminobenzene, resorcinol, 2-methylresorcinol, 4-chlororesorcinol, 1, 2,4-tri- hydroxybenzene, 2-amino-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine , 2,6-dihydroxy-3,4-dimethylpyridine, 3,5-diamino-2,6-dimethoxypyridine, 1-phenyl-3-methylpyrazol-5-one, 1-naphthol, 1, 5-dihydroxynaphthalene, 2 , 7-dihydroxynaphthalene, 1, 7-dihydroxynaphthalene, 1, 8-dihydroxynaphthalene, 4-hydroxyindole, 6-hydroxyindole, 7-hydroxyindole, 4-hydroxyindoline, 6-hydroxyindoline, 7-hydroxyindoline or mixtures of these compounds or their physiologically acceptable salts. Very particular preference is given to resorcinol, 2-methylresorcinol, 5-amino-2-methylphenol, 3-aminophenol, 2- (2,4-diaminophenoxy) ethanol, 1,3-bis (2,4-diaminophenoxy) propane, 1 -Methoxy-2-amino-4- (2'-hydroxyethylamino) benzene, 2-amino-3-hydroxypyridine and 1-naphthol and one of their physiologically acceptable salts.

The coupler components are preferably used in an amount of 0.005 to 20 wt .-%, preferably 0.1 to 5 wt .-%, each based on the ready-to-use oxidation colorant. In the context of the present invention, the following combinations of oxidation dye precursors of the developer type and of the coupler type are particularly preferred. However, other dye precursors can also be combined with the oxidation dye precursors mentioned as a combination: p-toluenediamine / resorcinol; p-toluenediamine / 2-methylresorcinol; p-toluenediamine / 5-amino-2-methylphenol; p-toluenediamine / 3-aminophenol; p-toluenediamine / 2- (2,4-diaminophenoxy) ethanol; p-toluenediamine / 1,3-bis (2,4-diaminophenoxy) propane; p-toluenediamine / 1-methoxy-2-amino-4- (2-hydroxyethylamino) benzene; p-toluenediamine / 2-amino-3-hydroxypyridine; p-toluenediamine / 1-naphthol; 2- (2-hydroxyethyl) -p-phenylenediamine / resorcinol; 2- (2-hydroxyethyl) -p-phenylenediamine / 2-methylresorcinol; 2- (2-hydroxyethyl) -p-phenylenediamine / 5-amino-2-methylphenol; 2- (2-hydroxyethyl) -p-phenylenediamine / 3-aminophenol; 2- (2-hydroxyethyl) -p-phenylenediamine / 2- (2,4-diaminophenoxy) ethanol; 2- (2-hydroxyethyl) -p-phenylenediamine / 1,3-bis (2,4-diaminophenoxy) propane; 2- (2-hydroxyethyl) -p-phenylenediamine / 1-methoxy-2-amino-4- (2-hydroxyethylamino) benzene; 2- (2-hydroxyethyl) -p-phenylenediamine / 2-amino-3-hydroxypyridine; 2- (2-hydroxyethyl) -p-phenylenediamine / 1-naphthol; 2-methoxymethyl-p-phenylenediamine / resorcinol; 2-methoxymethyl-p-phenylenediamine / 2-methylresorcinol; 2-methoxymethyl-p-phenylenediamine / 5-amino-2-methylphenol; 2-methoxymethyl-p-phenylenediamine / 3-aminophenol; 2-methoxymethyl-p-phenylenediamine / 2- (2,4-diaminophenoxy) ethanol; 2-methoxymethyl-p-phenylenediamine / 1,3-bis (2,4-diaminophenoxy) propane; 2-methoxymethyl-p-phenylenediamine / 1-methoxy-2-amino-4- (2-hydroxyethylamino) benzene; 2-methoxymethyl-p-phenylenediamine / 2-amino-3-hydroxypyridine; 2-methoxymethyl-p-phenylenediamine / 1-naphthol; N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazol-1-yl) -propyl] amine / resorcinol; N- (4-amino-3-methylphenyl) -N- [3- (1 H -imidazol-1-yl) propyl] amine / 2-methylresorcinol; N- (4-amino-3-methylphenyl) -N- [3- (1 H -imidazol-1-yl) propyl] amine / 5-amino-2-methylphenol; N- (4-amino-3-methylphenyl) -N- [3- (1 H -imidazol-1-yl) propyl] amine / 3-aminophenol; N- (4-amino-3-methylphenyl) -N- [3- (1 H -imidazol-1-yl) propyl] amine / 2- (2,4-diamino-phenoxy) -ethanol; N- (4-amino-3-methylphenyl) -N- [3- (1 H -imidazol-1-yl) -propyl] amine / 1, 3-bis (2,4-diaminophenoxy) propane; N- (4-amino-3-methylphenyl) -N- [3- (1 H -imidazol-1-yl) propyl] amine / 1-methoxy-2-amino-4- (2-hydroxyethylamino) benzene; N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazol-1-yl) -propyl] amine / 2-amino-3-hydroxypyridine; N- (4-amino-3-methylphenyl) -N- [3- (1 H -imidazol-1-yl) -propyl] amine / 1-naphthol; 4,5-diamino-1- (2-hydroxyethyl) pyrazole / resorcinol; 4,5-diamino-1- (2-hydroxyethyl) pyrazole / 2-methylresorcinol; 4,5-diamino-1- (2-hydroxyethyl) pyrazole / 5-amino-2-methylphenol; 4,5-diamino-1- (2-hydroxyethyl) pyrazole / 3-aminophenol; 4,5-diamino-1- (2-hydroxyethyl) pyrazole / 2- (2,4-diaminophenoxy) ethanol; 4,5-diamino-1- (2-hydroxyethyl) pyrazole / 1,3-bis (2,4-diaminophenoxy) propane; 4,5-diamino-1- (2-hydroxyethyl) pyrazole / 1-methoxy-2-amino-4- (2-hydroxyethylamino) benzene; 4,5-diamino-1- (2-hydroxyethyl) pyrazole / 2-amino-3-hydroxypyridine; 4,5-diamino-1- (2-hydroxyethyl) pyrazole / 1-naphthol.

In order to achieve a balanced and subtle nuance formation, it is advantageous according to the invention if further coloring components are contained in the composition according to the invention. In a further embodiment, the agents according to the invention may contain at least one substantive dye. These are dyes that raise directly on the hair and do not require an oxidative process to form the color. Direct dyes are usually nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols. Direct dyes can be subdivided into anionic, cationic and nonionic substantive dyes.

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

Preferred anionic substantive dyes are those under the international designations or trade names Acid Yellow 1, Yellow 10, Acid Yellow 23, Acid Yellow 36, Acid Orange 7, Acid Red 33, Acid Red 52, Pigment Red 57: 1, Acid Blue 7, Acid Green 50, Acid Violet 43, Acid Black 1, Acid Black 52 and Tetrabromphenol Blue known compounds.

Preferred cationic substantive dyes are cationic triphenylmethane dyes (such as Basic Blue 7, Basic Blue 26, Basic Violet 2 and Basic Violet 14), aromatic systems which are substituted by a quaternary nitrogen group (such as Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 and Basic Brown 17) as well as substantive dyes containing a heterocycle having at least one quaternary nitrogen atom, as described for example in EP-A2-998 908, which is incorporated herein by reference the claims 6 to 11 are called. The compounds also known as Basic Yellow 87, Basic Orange 31 and Basic Red 51 are most preferred cationic substantive dyes. The cationic substantive dyes sold under the trademark Arianor are also very particularly preferred cationic substantive dyes according to the invention.

Suitable nonionic substantive dyes are in particular nonionic nitro and quinone dyes and neutral azo dyes. Preferred nonionic substantive dyes are those under the international designations or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, HC Orange 1, Disperse Orange 3, HC Red 1, HC Red 3, HC HC Red 11, HC Red 11, HC Red 11, HC Red 11, HC Blue 2, HC Blue 11, HC Blue 12, Disperse Blue 3, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9 well-known compounds, as well 1,4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis (2-hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- (2-hydroxyethyl) aminophenol, 2 - (2-hydroxyethyl) amino-4,6-dinitrophenol, 4 - [(2-hydroxyethyl) amino] -3-nitro-1-methylbenzene, 1-amino-4- (2-hydroxyethyl) amino-5- chloro-2-nitrobenzene, 4-amino-3-nitrophenol, 1- (2'-ureidoethyl) amino-4-nitrobenzene, 2 - [(4-amino-2-nitrophenyl) amino] benzoic acid, 6-nitro-1, 2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4-naphtho quinone, picramic acid and its salts, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-4-nitrophenol.

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

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

Another possibility for coloring offers the use of colorants which contain so-called Oxofarbstoffvorprodukte. A first class of oxo dye precursors are compounds having at least one reactive carbonyl group. This first class is called a component (Oxo1). A second class of oxo dye precursors are C, H-acidic compounds and primary or secondary amino group or hydroxy group compounds, which in turn are selected from compounds of the group formed from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds. This second class is called a component (Oxo2). The aforementioned components (oxo1) and (oxo2) are generally not themselves dyes, and therefore are not in themselves suitable for coloring keratin-containing fibers. In combination, they form dyes in a non-oxidative process of so-called oxo dyeing. The resulting dyeings have partially color fastness on the keratin-containing fiber, which are comparable to those of the oxidation dyeing.

The Nuancenspektrum achievable with the gentle oxo staining is very broad and the color obtained often has an acceptable brilliance and color depth. However, it is also possible to use corresponding developer and / or coupler-type oxidation dye precursors with or without the use of an oxidizing agent in compounds of the component (oxo2). Thus, the method of oxo staining can be readily combined with the oxidative staining system.

As color-changing component according to the invention, it is therefore also possible in a further embodiment to use oxo dye precursors. Oxofarbstoffvorprodukte are preferred as a combination of at least one compound containing at least one reactive carbonyl group

(Component (oxo1)) with at least one compound (component oxo2) Connections selected from

(Oxo2a) C, H-acidic compounds and / or from

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

The above-mentioned compounds of the component (oxo1) and the component (oxo2), when used, are preferably each in an amount of 0.001 to 10 wt .-%, in particular from 0.01 to 5 wt .-%, respectively based on the total weight of the ready-to-use agent used.

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

The dye precursors of naturally-analogous dyes are each preferably used in an amount of from 0.001 to 5% by weight, based on the total application preparation. Derivatives of 5,6-dihydroxyindoline, in particular 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6, are particularly suitable as precursors of naturally-analogous hair dyes dihydroxyindoline, N-butyl-5,6-dihydroxyindoline and 5,6-dihydroxyindoline-2-carboxylic acid, especially 5,6-dihydroxyindoline. Derivatives of 5,6-dihydroxyindole, in particular 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6 are furthermore outstandingly suitable as precursors of naturally-analogous hair dyes dihydroxyindole, N-butyl-5,6-dihydroxyindole, 5,6-dihydroxyindole-2-carboxylic acid, especially 5,6-dihydroxyindole.

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

For the purposes of the invention, the term "protein derivative" as the active ingredient is amino acids themselves and their oligomers and polymers, which are linked via peptical bonds, in particular oligomers. to understand peptides and protein hydrolysates. An amino acid in the context of the invention is an organic compound which carries in its structure at least one protonatable amino group and at least one carboxylic acid or sulfonic acid group. Preferred amino acids are aminocarboxylic acids, in particular α-aminocarboxylic acids and ω-aminocarboxylic acids, α-aminocarboxylic acids being preferred.

Amino acids, oligopeptides and protein hydrolysates usually contain asymmetric centers in their structure, in particular carbon atoms as chiral centers. In the context of the present invention, it is possible to use amino acids, oligopeptides and / or protein hydrolyzates as chiral pure substances or else as mixtures of enantiomers and / or diastereomers. In particular, racemic mixtures, ie mixtures in which both enantiomers of a compound are contained in equal proportions, may be preferred. In nature, an enantiomeric form usually predominates. It may therefore also be preferred to use amino acids, oligopeptides and / or protein hydrolysates in their naturally occurring or even in their unnatural configuration.

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

According to the invention, protein hydrolysates of both vegetable and animal origin can be used. The proteins are broken down by hydrolysis of peptic bonds into low molecular weight fractions. In this case, both alkaline, acidic or enzymatic hydrolysis methods can be used, which provide structurally different hydrolysates and are applied to the requirements of the hydrolysates. The person skilled in these methods are familiar.

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 sold, for example, under the trademarks Keratin DEC (Vincience), Dehylan (Cognis), Promois (Interorgana), Collapuron (Cognis), Nutrilan (Cognis), Gelita-Sol (German Gelatin factories Stoess & Co), Lexein (Inolex) and Kerasol (Croda) expelled. 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 available, for example, under the trademarks Gluadin (Cognis), DiaMin (Diamalt), Lexein (Inolex) and Crotein (Croda). Also possible is the use of derivatives of protein hydrolysates, for example in the form of their fatty acid condensation products. Such products are sold, for example, under the names Lamepon (Cognis), Gluadin (Cognis), Lexein (Inolex), Crolastin (Croda) or Crotein (Croda). Depending on the preparation or recovery process, oligopeptides and protein hydrolysates can be present as mixtures of different components with different numbers of peptic bonds, different amino acid sequences and different molecular weights and can be used in the agents according to the invention.

It may be advantageous according to the invention to use mixtures of amino acids, oligopeptides and / or protein hydrolysates, which are obtained either as a mixture by the production process or obtained by a specific combination of different protein derivatives, for example the combination of several amino acids. In a preferred embodiment of the invention, amino acids are used as predominant pure substances.

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

According to the invention, particularly advantageous color-altering agents contain as additional active ingredient at least one amino acid which is selected from L-serine, D-serine, D / L-serine (racemate), L-homoserine, D-homoserine, D / L-homoserine, L -Threonin, 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 particular preference according to the invention is L-serine, especially in free form, but also used as hydrochloride.

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

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

Finally, it has been found that, in particular, the addition of a care combination of at least one cationized protein hydrolyzate and at least one active plant extract in combination with an additional care substance selected from cationized phosphate esters in agents for coloring keratinous fibers produces a particularly advantageous care effect. A further preferred embodiment of the present invention is therefore characterized in that the agent additionally contains a care substance selected from cationized phosphate esters. Such compounds are already known. Thus, in EP-A1-13713 the surfactant properties of these compounds are generally described. Furthermore, from DE-A1-44 08 506 the use of a compound of formula (I) in hair dyes already known. However, these references are not indicative of the synergistic increase in the care effect of the active compound combinations according to the invention. Preferred cationized phosphate esters are the substances known under the INCI names Linoleamidopropyl PG-Dimonium Chloride Phosphate, Cocamidopropyl PG-Dimonium Chloride Phosphate and Stearamidopropyl PG-Dimonium Chloride Phosphate. These are sold, for example, by the company Mona under the trade names phospholipid EFA, phospholipid PTC and phospholipid SV. According to the invention, cationic phosphate esters are used in amounts of from 0.01 to 5% by weight, in particular in amounts of from 0.05 to 2% by weight, in each case based on the total agent, in the claimed compositions.

In the case of oxidative dyeings, the development of the color can in principle be done with atmospheric oxygen. Preferably, however, a chemical oxidizing agent is used, especially if, in addition to the coloring, a lightening effect on human hair is desired. This lightening effect may be desired regardless of the staining method. As the oxidizing agent are persulfates, peroxodisulfates, chlorites, hypochlorites and in particular hydrogen peroxide or and / or one of its solid addition products of organic or inorganic compounds in question.

In order to prevent a premature, undesired reaction of the oxidation dye precursors by the oxidizing agent, oxidation dye precursors and oxidizing agents themselves are expediently prepared separately from each other and brought into contact only immediately before use.

In a further embodiment of the present invention, therefore, agents are preferred which are characterized in that they are prepared immediately before use by mixing at least two preparations, wherein the at least two preparations are provided in at least two separate prefabricated containers and wherein a container (I ) a dyeing preparation (A) which contains at least one oxidation dye precursor in a cosmetic carrier, and a further container (II) contains an oxidizing agent preparation (B) containing at least one oxidizing agent, at least one preparation (A) and / or ( B) contains a care combination of at least one cationized protein hydrolyzate and at least one active plant extract.

According to the invention, the dyeing preparation (A) preferably contains as further ingredient a care combination of at least one cationized protein hydrolyzate and at least one active plant extract. The oxidizing agent preparation (B) preferably contains as the oxidizing agent hydrogen peroxide and / or one of its solid addition products of organic or inorganic compounds, such as urea, melamine and sodium borate. The amount of oxidizing agent in the ready-to-use agent is preferably from 0.5 to 12% by weight, preferably from 2 to 10% by weight, more preferably from 3 to 6% by weight (calculated as 100% H ₂ O ₂ ), in each case based on the ready-to-use means. Such oxidizer formulations are preferably aqueous, flowable oxidizer formulations. In this case, preferred formulations are characterized in that the flowable oxidizing agent preparation - based on their weight - 40 to 95 wt .-%, preferably 50 to 90 wt .-%, particularly preferably 55 to 85 wt .-%, more preferably 60 to 80 wt .-% and in particular 65 to 75 wt .-% water.

Furthermore, it has proven to be advantageous if the oxidizing agent preparations contain at least one stabilizer or complexing agent. Particularly preferred stabilizers are phenacetin, alkali benzoates (sodium benzoate) and salicylic acid. Also preferred according to the invention is 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, a single ligand occupying more than one coordination site on a central atom, i. H. at least "bidentate". The number of bound ligands depends on the coordination number of the central ion. 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 tetramethylenephosphonate (EDTMP) or its Hexasodium salt and / or Diethylentriaminpentamethylenphosphonat (DTPMP) or its hepta or Octosatriumsalz.

The dyeing preparation and optionally oxidizing agent preparation contain further auxiliaries and additives. Thus, it has proved to be preferred according to the invention if the dyeing preparation and / or the oxidizing agent preparation contains at least one thickener. With regard to these thickeners, there are no fundamental restrictions. Both organic and purely inorganic thickening agents can be used.

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

SiO ₂ compounds can exist in various forms. According to the invention, the SiO ₂ compounds are preferably used in the form of silica gels (silica gel) or particularly preferably as water glass. These SiO ₂ compounds may be partially present in aqueous solution. Waterglasses which are particularly preferred according to the invention are sold, inter alia, under the names Ferrosil 1 19, soda waterglass 40/42, Portil A, Portil AW and Portil W and by Akzo under the name Britesil C20.

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

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

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. Preferred anionic surfactants are alkyl sulfates, alkyl ether sulfates and ether carboxylic acids having 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule.

Zwitterionic surfactants are surface-active compounds which carry at least one quaternary ammonium group and at least one carboxylate, sulfonate or sulfate group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as N-alkyl-N, N-dimethylammonium glycinates, for example cocoalkyl-dimethylammonium glycinate, N-acyl-aminopropyl-N, N-dimethylammonium glycinates, for example cocoacylaminopropyl-dimethylammonium glycinate, and 2-alkyl 3-carboxymethyl-3-hydroxyethyl imidazolines having in each case 8 to 18 C atoms in the alkyl or acyl group and the coco acylaminoethylhydroxyethylcarboxymethylglycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known by the INCI name Cocamidopropyl Betaine. Amphoteric surfactants are understood to mean those surface-active compounds which, apart from a C ₈ -C ₂₄ -alkyl or -acyl group in the molecule, contain at least one free amino group and at least one -COOH or -SO ₃ H group and which are capable of forming internal salts , Examples of suitable amphoteric surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each having about 8 to 24 C atoms in the alkyl group. Particularly preferred amphoteric surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C ₂ -C ₁₈ -acylsarcosine.

Furthermore, it has proved to be advantageous if the colorants according to the invention contain further nonionic surfactants. Nonionic surfactants contain as hydrophilic group z. A polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether groups. Particularly suitable nonionic surfactants are C ₈ -C ₂₂ -alkyl mono- and oligoglycosides and their ethoxylated analogs. In particular, the non-ethoxylated compounds have been found to be particularly suitable. As further preferred nonionic surfactants, the alkylene oxide addition products have proved to saturated linear fatty alcohols and fatty acids with 2 to 30 moles of ethylene oxide per mole of fatty alcohol or fatty acid. Preparations having excellent properties are also obtained if they contain fatty acid esters of ethoxylated glycerol as nonionic surfactants.

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

Also preferred according to the invention are cationic surfactants of the quaternary ammonium compound type, the esterquats and the amidoamines. Preferred quaternary ammonium compounds are ammonium halides, in particular chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, and the imidazolium compounds known under the INCI names Quaternium-27 and Quaternium-83. The alkylamidoamines are usually prepared by amidation of natural or synthetic fatty acids and fatty acid cuts with dialkylamino amines. A compound of this substance group which is particularly suitable according to the invention is stearamido-propyl-dimethylamine which is commercially available under the name Tegoamid S 18. Esterquats are known substances which contain both at least one ester function and at least one quaternary ammonium group as 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 sold, for example, under the trademarks Stepantex, Dehyquart and Armocare.

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

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

An inventively preferred embodiment of the present invention is that the ready-to-use agent has a pH between 7 and 12, in particular between 8 and 1 1, 5, particularly preferably between 8.5 and 1 1, 5, possesses. The pH values for the purposes of the present invention are pH values which were measured at a temperature of 22 ^° C.

Usually, the pH is adjusted with pH adjusters. In order to adjust the pH, those skilled in the art are familiar with common acidifying and alkalizing agents. The alkalizing agents which can be used for adjusting the pH are typically selected from inorganic salts, in particular the alkali metals and alkaline earth metals, organic alkalizing agents, in particular amines, basic amino acids and alkanolamines, and ammonia. Acidifying agents which are preferred according to the invention are pleasure acids, such as, for example, citric acid, acetic acid, malic acid or tartaric acid, and also dilute mineral acids. 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. Preferred alkanolamines are monoethanolamine and triethanolamine. However, it has been found in the context of the investigations of the present invention that furthermore preferred agents according to the invention are characterized in that they additionally contain an inorganic alkalizing agent. The inorganic alkalizing agent of the present invention is preferably selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium phosphate, potassium phosphate, sodium silicate, potassium silicate, sodium carbonate and potassium carbonate. Very particular preference is given to sodium hydroxide and / or potassium hydroxide. The basic amino acids which can be used as alkalizing agents according to the invention are preferably selected from the group formed from L-arginine, D-arginine, D / L-arginine, L-lysine, D-lysine, D / L-lysine, particularly preferably L-arginine. Arginine, D-arginine, D / L-arginine used as an alkalizing agent according to the invention. Finally, another preferred alkalizing agent is ammonia. The alkalizing agents are preferably contained in an amount of from 0.05 to 10% by weight, in particular from 0.5 to 5% by weight, based in each case on the total weight of the ready-to-use agent.

Furthermore, the agents according to the invention may contain other active ingredients, auxiliaries and additives, for example nonionic polymers (such as vinylpyrrolidinone / vinyl acrylate copolymers, polyvinylpyrrolidinone and vinylpyrrolidinone / vinyl acetate copolymers, polyethylene glycols and polysiloxanes); cationic polymers (such as quaternized cellulose ethers, polysiloxanes with quaternary groups, dimethyldiallylammonium chloride polymers, acrylamide-dimethyldiallyl-ammonium chloride copolymers, diethyl sulfate-quaternized dimethylamino-ethylmethacrylate-vinylpyrrolidinone copolymers, vinylpyrrolidinone-imidazolinium methochloride copolymers and quaternized polyvinylalcohols alcohol); zwitterionic and amphoteric polymers (such as acrylamidopropyltrimethylammonium chloride / acrylate copolymers and octylacrylamide / methyl methacrylate / t-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers); anionic polymers (such as polyacrylic acids, crosslinked polyacrylic acids, vinyl acetate / crotonic acid copolymers, vinylpyrrolidinone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and acrylic acid / ethyl acrylate / Nt-butyl acrylamide terpolymers); other thickening agents (such as agar-agar, guar gum, alginates, gum arabic, karaya gum, locust bean gum, linseed gums, dextrans, cellulose derivatives, eg methylcellulose, hydroxyalkylcellulose and carboxymethylcellulose, starch fractions and derivatives such as amylose Amylopectin and dextrins, clays such as bentonite or fully synthetic hydrocolloids such as polyvinyl alcohol); Structurants (such as glucose, maleic acid and lactic acid); hair conditioning compounds (such as phospholipids, 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; cyclodextrins; fiber-structure-improving active ingredients (in particular mono-, di- and oligosaccharides such as, for example, glucose, galactose, fructose, fructose and lactose); Defoamer (such as silicones, preferably dimethicone); Dyes for staining the agent; Anti-dandruff agents (such as Piroctone Olamine, Zinc Omadine and Climbazole); Light stabilizers or UV blockers (in particular derivatized benzophenones, cinnamic acid derivatives and triazines); Active substances (such as panthenol, pantothenic acid, pantolactone, allantoin, pyrrolidinonecarboxylic acids and their salts, and bisabolol); Vitamins, provitamins and vitamin precursors (especially those of groups A, B ₃ , B ₅ , B ₆ , C, E, F and H); Cholesterol; Bodying agents (such as sugar esters, polyol esters or polyol alkyl ethers); Fats and waxes (such as beeswax, montan wax and paraffins); fatty acid; Swelling and penetration 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; Propellants (such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air) and antioxidants. The choice of these other substances will be made by those skilled in the art according to the desired properties of the agents. With regard to further optional components and the amounts of these components used, reference is expressly made to the relevant manuals known to the person skilled in the art, eg. B. Kh. Schrader, bases and formulations of cosmetics, 2nd edition, Hüthig book publisher, Heidelberg, 1989, referenced.

As already mentioned, the compositions according to the invention can also be prepared directly before use from two or more separately packaged preparations. This is particularly useful for the separation of incompatible ingredients to avoid premature reaction. Separation into multicomponent systems is particularly suitable where incompatibilities of the ingredients are to be expected or to be feared. The ready-to-use agent in such systems is manufactured by the consumer just prior to application by mixing the components. A colorant in which the oxidation dye precursors are initially separate from the oxidant preparation, preferably containing hydrogen peroxide, is preferred.

A second subject of the present invention is therefore a packaging unit (kit of parts) which, packaged separately, comprises at least one container (I) containing an oxidizing agent preparation (B) which contains at least hydrogen peroxide as oxidizing agent in a cosmetic carrier, and at least one Container (II) comprising a dyeing preparation (A) which comprises at least one oxidation dye precursor in an aqueous-cosmetic carrier, characterized in that the dyeing preparation (A) additionally comprises a care combination of at least one cationized protein hydrolyzate and at least one active plant extract contains.

Further preferably, the multi-component packaging unit (kit-of-parts) additionally contains a user conduit. In addition, it may be preferred if an application aid, such as a comb or a brush, and / or personal protective equipment, such as disposable gloves, are also included in the kit. With regard to further preferred embodiments of the multi-component packaging unit (kit-of-parts), what has been said about the agents according to the invention applies mutatis mutandis.

A third aspect of the present invention is a method for dyeing human hair, wherein an agent of the first subject of the invention is applied to the hair, left in the hair for a period of 3 to 45 minutes, preferably 5 to 30 minutes, and then the hair is rinsed with water and / or a commercial shampoo.

The application temperatures in the dyeing process according to the invention can be in a range between 15 and 45 ⁰ C. After the exposure time, the hair dye is removed by rinsing, optionally with the aid of a shampoo, from the hair to be dyed. The washing with a shampoo can be omitted if a strong surfactant-containing carrier, eg. B. a Dyeing shampoo, was used. During the contact time of the agent on the fiber, it may be advantageous to assist the dyeing process by supplying heat. The heat supply can be done by an external heat source, such as warm air of a hot air blower, as well as, especially in a hair dye on living subjects, by the body temperature of the subject. In the latter case, usually the part to be dyed is covered with a hood. In particular, the temperature during the contact time between 20 ⁰ C and 40 ⁰ C, in particular between 25 ⁰ C and 38 ⁰ C. The dyeing compositions according to the invention already at physiologically compatible temperatures of less than 45 ° C intensive colors. They are therefore particularly suitable for dyeing human hair.

With regard to further preferred embodiments of the method according to the invention, mutatis mutandis the statements made concerning the agents according to the invention apply.

Another object of the invention is the cosmetic, non-therapeutic use of a coloring agent for keratinous fibers, comprising in a cosmetic carrier a care combination of at least one cationized protein hydrolyzate and at least one active plant extract, to improve the care of the keratinic fibers.

Another object of the invention is the cosmetic, non-therapeutic use of a coloring agent for keratin fibers containing in a cosmetic carrier a care combination of at least one cationized protein hydrolyzate and at least one active plant extract, to improve the moisture content of the keratinic fibers.

Another object of the invention is the cosmetic, non-therapeutic use of a coloring agent for keratin fibers containing in a cosmetic carrier a care combination of at least one cationized protein hydrolyzate and at least one active plant extract, to improve the luster of the keratin fibers.

Another object of the invention is the cosmetic, non-therapeutic use of a coloring agent for keratinic fibers, comprising in a cosmetic carrier a care combination of at least one cationized protein hydrolyzate and at least one active plant extract, to improve the wet combability of the keratinic fibers.

With regard to further preferred embodiments of the uses according to the invention, mutatis mutandis, the statements made with regard to the agents according to the invention apply.

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

1.1 The following coloring creams were prepared with the same dye mixture:

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

Raw materials: Lanette E, powder (INCI name: Sodium Cetearyl Sulfate, Cognis); Texapon NSF, 27% (INCI name: Sodium Laureth Sulfate; Cognis); Cutina GMS SE (INCI name: Glyceryl Stearate; Cognis); Cutina AGS (INCI name: Glycol Distearate; Cognis); Eutanol G (INCI name: Octyldodecanol; Cognis); Hydrenol D (INCI name: Cetearyl alcohol; Cognis); Eumulgin B1 (INCI name: Ceteareth-12; Cognis); Eumulgin B2 (INCI name: Ceteareth-20; Cognis); Phospholipid EFA (INCI name: linoleneamidopropyl PG-dimonium chloride phosphate; Uniqema); Herbasol Extract Aloe, discolored (2-4% active ingredient, INCI name: Aqua, Propylene Glycol, Aloe Barbadensis, Cosmetochem); Promois MiIk-Q (INCI name: Hydroxypropyltrimonium hydrolzed casein; Seiwa Kasei Co., Ltd.).

The fat base was melted together at 80 ⁰ C and dispersed with a portion of the amount of water. Subsequently, the remaining recipe ingredients were incorporated with stirring in order. It was then made up to 100% by weight with water and the formulation was stirred cold. The formulation V1 is a comparative formulation not according to the invention without cationized milk protein hydrolyzate. The formulations E1 and E2 are examples according to the invention.

1.2. Mixing with the developer dispersion (EW) and application Each coloring cream was mixed in a weight ratio of 1: 1 with a composition as follows

Developer dispersion mixed.

Genamin STAC (about 80% active ingredient, INCI name: Steartrimonium Chloride, Clariant)

Strands of natural dark European Alkinco 6634 were treated with 10% by weight sodium lauryl ether sulfate solution in an ultrasonic bath for 15 min, then rinsed with lukewarm 10 min. The tresses were air-dried and stored for 24 h at 25 ° C and 40% relative humidity. The zero value was a moisture measurement.

For staining, four times the amount of the finished application mixtures was applied to the strands of about 0.7 g in weight. After streaks were dyed at 32 ^° C. for 30 minutes, they were rinsed with water for 5 minutes and air-dried.

The storage of dyed fibers took place under air conditioning (25 ° C and 40% relative humidity). Wet measurements were taken after 1 day, 2 days, 4 days and 7 days.

1.3 Moisture retention

The measurements clearly show the superiority of the agents according to the invention with respect to the moisture content of the treated strands.

1.4 colorations

Raw materials: Texapon N 25 27% (INCI name: Sodium Laureth Sulfate; Cognis); Edenor C14 (INCI name: Myristic Acid; Cognis); Plantapon LGC Sorb (INCI name: Lauryl Glucose Carboxylate, Lauryl Glucose, Cognis); Lorol C12-18, techn. (INCI name: Coconut Alcohol; Cognis); Eumulgin B1 (INCI name: Ceteareth-12; Cognis); Eumulgin B2 (INCI name: Ceteareth-20; Cognis); Product W37194 (INCI name: Acrylamidopropyltrimonium Chloride Acrylates Copolymer; Stockhausen).

The fat base was melted together at 80 ⁰ C and dispersed with a portion of the amount of water. Subsequently, the remaining recipe ingredients were incorporated with stirring in order. It was then made up to 100% by weight with water and the formulation was stirred cold. The formulation V2 is a comparative formulation not according to the invention without an extract of aloe vera. The recipe E3 is an example according to the invention.

Each dyeing cream was mixed in a ratio by weight of 1: 1 with the developer dispersion described under 1.2. For staining, strands of bleached buffalo belly hair of about 0.7 g in weight were applied with 4 times the amount of the finished application mixtures. After the tresses were dyed for 30 min at 32 ⁰ C, they were washed with a commercial shampoo and dried with a hair dryer.

1.5 staining results

A rich shade of brown was obtained with both dyeing formulations, the strands treated with the dyeing formulations (E1 + EW) or (E2 + EW) according to the invention showing markedly superior gloss compared to the respective comparative formulations.

Claims

Patent claims

1. agent for coloring keratin fibers, in particular human hair, containing in a cosmetic carrier at least one coloring component, characterized in that the agent contains a care combination of at least one cationized protein hydrolyzate and at least one active plant extract.

2. Composition according to claim 1, characterized in that the cationized protein hydrolyzate is selected from cationized protein hydrolysates of animal origin.

3. Composition according to one of claims 1 to 2, characterized in that the cationized protein hydrolyzate is a cationized milk protein hydrolyzate, in particular a cationized casein hydrolyzate.

4. Composition according to one of claims 1 to 3, characterized in that the means the cationized protein hydrolyzate in a proportion of 0.01 to 10 wt .-%, preferably from 0.05 to 5 wt .-% and in particular of 0, 1 to 3 wt .-%, each based on the total weight of the ready-to-use agent contains.

5. Composition according to one of claims 1 to 4, characterized in that the agent contains as an effective plant extract an effective extract of Aloe Barbadensis.

6. Composition according to one of claims 1 to 5, characterized in that the agent the effective extract of Aloe Barbadensis in a proportion of 0.01 to 10 wt .-%, preferably from 0.05 to 5 wt .-% and in particular from 0.1 to 3 wt .-%, each based on the total weight of the ready-to-use agent contains.

7. Composition according to one of claims 1 to 6, characterized in that the agent contains at least one oxidation dye precursor as a coloring component.

8. Composition according to one of claims 1 to 7, characterized in that the agent additionally contains at least one amino acid, an oligopeptide or a protein hydrolyzate.

9. Composition according to claim 8, characterized in that the agent contains L-serine.

10. Composition according to one of claims 1 to 9, characterized in that the agent additionally contains at least one care substance selected from cationized phosphate esters.

11. Packing unit (kit-of-parts) which, packaged separately, contains at least one container (I) containing an oxidizing agent preparation (B) which contains at least hydrogen peroxide as the oxidizing agent in a cosmetic carrier, and min. at least one container (II) comprising a dyeing preparation (A) which contains at least one oxidation dye precursor in an aqueous cosmetic carrier, characterized in that the dyeing preparation (A) additionally comprises a care combination of at least one cationized protein hydrolyzate and at least one active plant extract contains.

12. A process for dyeing human hair, wherein an agent according to any one of claims 1 to 9 is applied to the hair is left for a period of 3 to 45 minutes, preferably 5 to 30 minutes in the hair, and then the hair with water and / or a commercial shampoo is rinsed.

13. Cosmetic, non-therapeutic use of a coloring agent for keratinic fibers, comprising in a cosmetic carrier a care combination of at least one cationized protein hydrolyzate and at least one active plant extract, to improve the care of the keratinic fibers.

14. A cosmetic, non-therapeutic use of a keratin fiber colorant comprising, in a cosmetic carrier, a conditioning combination of at least one cationized protein hydrolyzate and at least one active plant extract to improve the moisture content of the keratinic fibers.