WO2006029657A1 - Caring hair colouring agent - Google Patents

Abstract

The inventive hair colouring agent comprises the fluid preparation of oxidising colorant intermediate products (A) and an oxidation agent preparation (B), wherein said preparations are mixed just prior to the application thereof to the hairs, thereby obtaining a colouring batch. The preparation of oxidising colorant intermediate products (A) and the oxidation agent preparation (B) contain at least one conditioner and the hair colouring agent exhibits an improved caring effect.

Description

 nourishing hair dye "

The invention relates to hair dyes which give the hair treated with them more care.

The cosmetic treatment of skin and hair is an important part of human body care. So today human hair is treated in many ways with hair cosmetic preparations. These include cleaning the hair with shampoos, care and regeneration with rinses and cures, as well as bleaching, dyeing and shaping the hair with dyes, tinting agents, waving agents and styling preparations. Means for changing or shading the color of the head hair play an outstanding role. Apart from the bleaching agents, which bring about an oxidative brightening of the hair by breaking down the natural hair dyes, there are essentially three types of hair dye in the area of hair coloring:

So-called oxidation dyes are used for permanent, intensive dyeings with appropriate fastness properties. Such colorants usually contain oxidation dye precursors, so-called developer components and coupler components. The developer components form the actual dyes under the influence of oxidizing agents or atmospheric oxygen with one another or under coupling with one or more coupler components. The oxidation coloring agents are characterized by excellent, long-lasting coloring results. For natural-looking dyeings, however, a mixture of a larger number of oxidation dye precursors usually has to be used; in many cases direct dyes are still used for shading. Assign them in Color fastnesses formed or directly used in the course of color formation have clearly different fastness properties (e.g. UV stability, fastness to perspiration, fastness to washing, etc.), so that over time a recognizable and therefore undesirable color shift can occur. This phenomenon increases when the hairstyle has hair or hair zones with different degrees of damage. An example of this is long hair, in which the hair tips, which have been exposed to all possible environmental influences for a long time, are as a rule significantly more damaged than the relatively freshly regrown hair zones.

Coloring agents or tinting agents which contain so-called direct draws as the coloring component are usually used for temporary dyeings. These are dye molecules that attach directly to the hair and do not require an oxidative process to form the color. These dyes include, for example, henna, which is known from antiquity for coloring body and hair. These dyeings are generally significantly more sensitive to shampooing than the oxidative dyeings, so that a much undesirable shift in nuances or even a visible "discoloration" occurs much more quickly.

After all, a novel dyeing process has received great attention recently. In this process, precursors of the natural hair dye melanin are applied to the hair; These then form naturally analogous dyes in the hair as part of oxidative processes. In such processes, for example, 5,6-dihydroxyindoline is used as a dye precursor. When using agents with 5,6-dihydroxyindoline, in particular several times, it is possible for people with gray hair to reproduce the natural hair color. The coloring can take place with atmospheric oxygen as the only oxidizing agent, so that no further oxidizing agents have to be used. For people with originally medium blonde to brown hair, indoline can be used as the sole dye precursor. For use with people with originally red and in particular dark to black hair color, on the other hand, satisfactory results can often only be achieved by The use of further dye components, in particular special oxidation dye precursors, can be achieved.

Not least because of the heavy stress on the hair, for example through dyeing or perming, as well as through cleaning the hair with shampoos and environmental pollution, the importance of care products with long-lasting effects is increasing. Care products of this type influence the natural structure and properties of the hair. After such treatments, for example, the wet and dry combability of the hair, the hold and the fullness of the hair can be optimized or the hair can be protected from increased split ends.

It has therefore long been customary to subject the hair to a special after-treatment. Here, usually in the form of a rinse, the hair is treated with special active ingredients, for example quaternary ammonium salts or special polymers. Depending on the formulation, this treatment improves the combability, hold and fullness of the hair and reduces the split rate.

In addition, so-called combination preparations have recently been developed in order to reduce the complexity of the conventional multi-stage processes, in particular when used directly by consumers.

In addition to the usual components, for example for cleaning the hair, these preparations additionally contain active ingredients which were formerly reserved for the hair aftertreatment agents. The consumer thus saves one application step; At the same time, the packaging effort is reduced because one product is used less.

The active substances available both for separate aftertreatment agents and for combination preparations generally act preferentially on the hair surface. Active substances are known which give the hair shine, Give hold, fullness, better wet or dry combability or prevent the split ends. However, just as important as the external appearance of the hair is the internal structural cohesion of the hair fibers, which can be greatly influenced in particular in oxidative and reductive processes such as coloring and perms.

However, the known active ingredients cannot adequately cover all needs. There is therefore still a need for active ingredients or combinations of active ingredients for cosmetic compositions with good care properties and good biodegradability. In particular in formulations containing dyes and / or electrolytes, there is a need for additional caring active ingredients which can be incorporated into known formulations without problems.

The object of the present invention was to provide hair colorants which are distinguished by special nourishing properties. On the one hand, it should be possible to dispense with the increased use of nourishing substances and the associated costs, on the other hand, the agents should improve the properties of the treated hair, in particular wet and dry combability, and the feel of wet and dry hair.

It has now been found that the distribution of the care substances over the individual components of hair dye has a decisive influence on the care performance.

The present invention relates to hair colorants, consisting of a flowable preparation of oxidation dye precursors (A) and a flowable, oxidizer preparation (B), which are mixed with one another immediately before application to the hair to form a dye mixture, the preparation of oxidation dye precursors (A) and the oxidizing agent preparation (B) each contain at least one care substance. Compared to agents that contain the same amount of care substance only in one of the two compositions, the agents according to the invention are distinguished by a significantly improved care effect. In particular, the wet and dry combability have been significantly improved. In addition, the hair treated with the agent according to the invention was distinguished by an improved grip in wet and dry hair.

The care substance is preferably contained both in the flowable preparation of oxidation dye precursors (A) and in the flowable preparation of oxidizing agent (B) in certain amounts. Agents according to the invention are preferred here in which the preparation of oxidation dye precursors (A) and the oxidant preparation (B) the care substance (s) in amounts of 0.1 to 5 wt .-%, preferably from 0.25 to 2.5 Wt .-% and in particular from 0.5 to 2 wt .-%, based on the respective total composition.

The selection of the care substances in the individual preparations is not subject to any restrictions. However, the proportions of the care substances in the preparations are particularly advantageously in a defined ratio to one another. Agents according to the invention are preferred in which the quotient of the% by weight of the care substance (s) in the preparation of oxidation dye precursors (A) and the oxidant preparation (B) is 5: 1 to 1: 5, preferably 2: 1 to 1: 2 and in particular 1: 1.

Accordingly, if the preparation of oxidation dye precursors (A), based on their weight, contains 5% by weight of care substance (s), in preferred embodiments of the present invention, the oxidant preparation (B) contains 1% by weight of care substance, based on its weight (e) [(A) to (B) = 5: 1] to 25% by weight of care substance (e) [(A) to (B) = 1: 5]. The oxidizing agent preparation (B) particularly preferably contains, based on its weight, 2.5% by weight of care substance (s) [(A) to (B) = 2: 1] to 10% by weight of care substance (s) [( A) to (B) = 1: 2] and in particular in this example the oxidizing agent preparation (B) contains, based on its weight, 5% by weight of care substance (s) [(A) to (B) = 1: 1].

One or more care substances can be contained in the individual preparations. In particularly preferred embodiments, the preparations each contain the same care substance or - in the case of several care substances - the same care substances. Hair colorants according to the invention in which the preparation of oxidation dye precursors (A) and the oxidizing agent preparation (B) contain the same care substance are preferred.

The agents according to the invention can contain a large number of compounds as care substances. For example, substances from the group of vitamins and provitamins, proteins and protein hydrolyzates or metal ions with nourishing properties (especially copper) can be used. Care substances from the group of quaternary ammonium compounds and / or silicones are particularly preferred.

In a preferred embodiment of the present invention, the hair colorants according to the invention are characterized in that the preparation of oxidizing dye precursors (A) and / or the oxidizing agent preparation (B) as a care substance comprises at least one quaternary ammonium compound, preferably at least one cationic surfactant and / or at least one cationic or amphoteric polymer

These preferred agents according to the invention contain at least one quaternary ammonium compound, ie a compound which also has a positively charged nitrogen atom. QAVs which have four (optionally substituted) hydrocarbon radicals are particularly preferred. Among the large number of possible compounds, the compound classes of the cationic surfactants and the cationic or amphoteric polymers are particularly preferred. Cationic surfactants of the type of the quaternary ammonium compounds, the esterquats and the amidoamines can be used according to the invention. Preferred quaternary ammonium compounds are ammonium halides, in particular chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g. B. cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride, as well as the compounds known under the INCI names Quatemium-27 and Quaternium-83 compounds imidazolium. The long alkyl chains of the above-mentioned surfactants preferably have 10 to 18 carbon atoms.

According to the invention, QAV with behenyl residues can be used with particular preference, in particular the substances known under the name behentrimonium chloride or bromide (docosanyltrimethylammonium chloride or bromide). Other preferred QAV have at least two behenyl residues, with QAV, which two behenyl residues on an imidazolinium backbone are particularly preferred. Commercially available, these substances are, for example, under the names Genamin ^® KDMP (Clariant) and Crodazosoft ^® DBQ (Crodauza).

Ester quats 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 sold, for example, under the trademarks Stepantex ^® , Dehyquart ^® and Armocare ^® . The products Armocare ^® VGH-70, an N, N-bis (2-palmitoyloxyethyl) dimethylammonium chloride, as well as Dehyquart ^® F-75, Dehyquart ^® C-4046, Dehyquart ^® L80 and Dehyquart ^® AU-35 are examples of such esterquats. The alkylamidoamines are usually produced by amidation of natural or synthetic fatty acids and fatty acid cuts with dialkylaminoamines. An inventively particularly suitable compound from this group is that available under the name Tegoamid ^® S 18 commercially stearamidopropyl.

The cationic surfactants are preferably present in the agents according to the invention in amounts of 0.05 to 10% by weight, based on the total agent. Amounts of 0.1 to 5% by weight are particularly preferred. In the context of the present invention, “based on the total agent” means “based on the mixture of the preparation of oxidation dye precursors (A) and the oxidizing agent preparation (B).

Cationic or amphoteric polymers can also be used according to the invention as QAV with particular advantage. Cationic or amphoteric polymers are understood to mean polymers which have a group in the main and / or side chain which can be “temporary” or “permanent” cationic. According to the invention, polymers which have a cationic group irrespective of the pH of the composition are referred to as "permanently cationic". These are usually polymers that contain a quaternary nitrogen atom, for example in the form of an ammonium group. Preferred cationic groups are quaternary ammonium groups. In particular, those polymers in which the quaternary ammonium group is bonded via a C1-4 hydrocarbon group to a main polymer chain composed of acrylic acid, methacrylic acid or their derivatives have proven to be particularly suitable. Homopolymers of the general formula (G1-I),

R ¹

- [CH ₂ -CI _n X ^" (G1-I)

I CO-O- (CH ₂ ) _m -N ⁺ R ² R ³ R ⁴

in which R ¹ = -H or -CH ₃ , R ² , R ³ and R ^{4 are} independently selected from C1-4 alkyl, alkenyl or hydroxyalkyl groups, m = 1, 2, 3 or 4, n is a natural number and X ^"is a physiologically compatible organic or inorganic anion, and copolymers consisting essentially of the monomer units listed in formula (G1-I) and nonionic monomer units are particularly preferred cationic polymers. Within the scope of these polymers, those are according to the invention preferred, for which at least one of the following conditions applies:

- R ¹ represents a methyl group

- R ² , R ³ and R ⁴ represent methyl groups

- m has the value 2.

Suitable physiologically compatible counterions X ^' are, for example, halide ions, sulfate ions, phosphate ions, methosulfate ions and organic ions such as lactate, citrate, tartrate and acetate ions. Halide ions, in particular chloride, are preferred.

A particularly suitable homopolymer is, if desired crosslinked, poly (methacryloyloxyethyltrimethylammonium chloride) with the INCI name Polyquatemium-37. Such products are available, for example under the names Rheocare ^® CTH (Cosmetic Rheologies) and Synthalen® ^® CR (Ethnichem) in trade. If desired, the crosslinking can be carried out with the aid of polyolefinically unsaturated compounds, for example Divinylbenzene, tetraailyloxyethane, methylenebisacrylamide, diallyl ether, polyallylpolyglyceryl ether, or allyl ether of sugars or sugar derivatives such as erythritol, pentaerythritol, arabitol, mannitol, sorbitol, sucrose or glucose. Methylene bisacrylamide is a preferred crosslinking agent.

The homopolymer is preferably used in the form of a non-aqueous polymer dispersion which should not have a polymer content below 30% by weight. Such polymer dispersions are available under the names Salcare ^® SC 95 (approx. 50% polymer content, further components: mineral oil (I NCI name: mineral oil) and tridecyl-polyoxypropylene-polyoxyethylene ether (INCI name: PPG-1-Trideceth-6 )) and Salcare ^® SC 96 (approx. 50% polymer content, further components: mixture of diester of propylene glycol with a mixture of caprylic and capric acid (INCI name: Propylene glycol dicaprylate / dicaprate) and tridecyl polyoxypropylene) polyoxyethylene ether (INCI name: PPG-1-Trideceth-6)) commercially available.

Copolymers containing monomer units according to formula (G 1-1) as non-ionic monomer, preferably acrylamide, methacrylamide, acrylic acid alkyl esters and methacrylic acid CI_ ₄ CI_ ₄ -alkyl. Among these nonionic monomers, acrylamide is particularly preferred. As in the case of the homopolymers described above, these copolymers can also be crosslinked. A preferred copolymer according to the invention is the crosslinked acrylamide-methacryloyloxyethyltrimethylammonium chloride copolymer. Such copolymers in which the monomers are present in a weight ratio of about 20:80, are commercially available as approximately 50% non-aqueous polymer dispersion of the drawing Be¬ Salcare ^® SC 92 available.

Other preferred cationic polymers are, for example

- Quaternized cellulose derivatives, as are commercially available under the names Celquat ^® and Polymer JR ^® . The compounds Celquat ^® H 100, Celquat ^® L 200 and Polymer JR ^® 400 are preferred quaternized cellulose derivatives,

cationic alkyl polyglycosides according to DE-PS 44 13 686,

cationized honey, for example the commercial product Honeyquat ^® 50,

cationic guar derivatives, such as, in particular, the products sold under the trade names Cosmedia ^® Guar and Jaguar ^® ,

- Polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid. The products available under the Bezeich¬ voltages Merquat ^® 100 (Poly (dimethyldiallylammonium chloride)) and Merquat ^® 550 (dimethyldiallylammonium chloride-acrylamide copolymer) are examples of such cationic polymers,

- Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoalkyl acrylate and methacrylate, such as, for example, vinylpyrrolidone-dimethylaminoethyl methacrylate copolymers quaternized with diethyl sulfate. Such compounds are commercially available under the names Gafquat ^® 734 and Gafquat ^® 755,

Vinylpyrrolidone-vinylimidazolium methochloride copolymers, as are offered under the names Luviquat ^® FC 370, FC 550, FC 905 and HM 552,

- quaternized polyvinyl alcohol,

- And the known under the names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27 polymers with quaternary nitrogen atoms in the main polymer chain.

Can be used as cationic polymers (. B. commercial product, Quatrisoft ^® LM 200) under the designations Polyquaternium-24, known polymers. Likewise usable according to the invention are the copolymers of vinyl pyrrolidone, such as those available as commercial products Copolymer 845 (manufacturer: ISP), Gaffix ^® VC 713 (manufacturer: ISP), Gafquat ^® ASCP 1011, Gafquat ^® HS 110, Luviquat ^® 8155 and Luviquat ^® MS 370 are. Further cationic polymers that can be used in the agents according to the invention are the so-called “temporarily cationic” polymers. These polymers usually contain an amino group which is present as a quaternary ammonium group at certain pH values and is therefore cationic. Preferably, for example, are chitosan and its derivatives, such as, for example, under the trade designations Hydagen CMF ^® ₁ Hydagen HCMF ^®, Kytamer ^® PC and Chitolam ^® NB / 101 are freely available commercially.

According to the invention preferred cationic polymers are cationic cellulose Defivate and chitosan and its derivatives, in particular the commercial products Polymer ^® JR 400, Hydagen ^® HCMF and Kytamer ^® PC, cationic guar derivatives, cationic honey derivatives, in particular the commercial product Honeyquat ^® 50, cationic alkyl polyglycosides according to DE-PS 44 13 686 and polymers of the type Polyquaternium-37.

Furthermore, cationized protein hydrolyzates are to be counted among the cationic polymers, the underlying protein hydrolyzate being derived from animals, for example from collagen, milk or keratin, from plants, for example from wheat, corn, rice, potatoes, soy or almonds, from marine life forms, for example from fish collagen or algae, or biotechnologically obtained protein hydrolyzates. The protein hydrolysates on which the cationic derivatives according to the invention are based can be obtained from the corresponding proteins by chemical, in particular alkaline or acidic hydrolysis, by enzymatic hydrolysis and / or a combination of both types of hydrolysis. The hydrolysis of proteins usually results in a protein hydrolyzate with a molecular weight distribution of approximately 100 daltons up to several thousand daltons. Preferred cationic protein hydrolyzates are those whose underlying protein content has a molecular weight of 100 to 25,000 Daltons, preferably 250 to 5000 Daltons. Cationic protein hydrolyzates also include quaternized amino acids and their mixtures. The quaternization of protein hydrolyzates or amino acids is often carried out using quaternary Ammonium salts such as N, N-dimethyl-N- (n-alkyl) -N- (2-hydroxy-3-chloro-n-propyl) ammonium halides performed. Furthermore, the cationic protein hydrolyzates can also be further derivatized. As typical examples of the inventive cationic protein hydrolysates and - derivatives are under the INCI - names in the "International Cosmetic Ingredient Dictionary and Handbook" (seventh edition 1997, The Cosmetic, Toiletry, and Fragrance Association 1101 17 ^th Street, NW, Suite 300 , Washington, DC 20036-4702) mentioned and commercially available products: Cocodimonium Hydroxypropyl Hydrolyzed Collagen, Cocodimopnium Hydroxypropyl Hydrolyzed Casein, Cocodimonium Hydroxypropyl Hydrolyzed Collagen, Cocodimonium Hydroxypropyl Hydrolyzed Hair Keratin, Cocodimonium Hydroxypropyl Hydrolyzed Keratin, Cocodimonium Hydroxypropyl Hydrolyzed Hydrolyzed Soy Protein, Cocodimonium Hydroxypropyl Hydrolyzed Wheat Protein, 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, Hydroxypropyltrimonium Hydrolyzed Soy Protein, Hydroxypropyl Hydrolyzed Vegetable Protein, Hydroxypropyltrimonium Hydrolyzedoxysiloxydehydrogenated Soy Protein, Laurdimonium Hydroxypropyl Hydrolyzed Wheat Protein, Laurdimonium Hydroxypropyl Hydrolyzed Wheat Protein / Siloxysilicate, Lauryldimonium Hydroxypropyl Hydrolyzed Casein, Lauryldimonium Hydroxypropyl Hydrolyzed Collagen, Lauryldimonium Hydroxypropyl Hydrolyzed Keratin, Lauryldimonium Hydroxypropyl Hydrolydicated Casoyne Protein, Stearyl Hydrolyzed Keratin, Steardimonium Hydroxypropyl Hydrolyzed Ric e Protein, 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 Keratin, Quaternium-79 Hydrolyzed Milk Protein, Quaternium-79 Hydrolyzed Soy Protein, Quaternium-79 Hydrolyzed Wheat Protein.

The cationic protein hydrolysates and derivatives based on plants are very particularly preferred.

In addition to cationic polymers or in their place, the agents according to the invention can also contain amphoteric polymers. These additionally have at least one negatively charged group in the molecule and are also referred to as zwitterionic polymers. In the context of the present invention, zwitterionic polymers that can preferably be used essentially consist of one another

A) monomers with quaternary ammonium groups of the general formula (Z-I),

R ¹ -CH = CR ² -CO-Z- (C _n H _2n ) -N ( ⁺ ) R ³ R ⁴ R ⁵ A ( ^" ) ( ^Z ~ ')

In which R ¹ and R ² independently of one another represent hydrogen or a

Methyl group and R ^, R ⁴ and R ⁵ independently of one another for alkyl groups with 1 to 4 carbon atoms, Z is an NH group or an oxygen atom, n is an integer from 2 to 5 and A ( ^" ) is the anion of an organic or inorganic Is acid

and

B) monomeric carboxylic acids of the general formula (Z-II),

R ⁶ -CH = CR ⁷ -COOH (II) in which R ⁶ and R ^{7 are} independently hydrogen or methyl groups.

Suitable starting monomers are e.g. B. dimethylaminoethyl acrylamide, dimethylaminoethyl methacrylamide, dimethylaminopropylacrylamide,

Dimethylaminopropyl methacrylamide and diethylaminoethyl acrylamide, if Z represents an NH group or dimethylaminoethyl acrylate,

Dimethylaminoethyl methacrylate and diethylaminoethyl acrylate when Z is an oxygen atom.

The monomers containing a tertiary amino group are then quaternized in a known manner, methyl chloride, dimethyl sulfate or diethyl sulfate being particularly suitable as alkylating reagents. The quaternization reaction can be carried out in aqueous solution or in the solvent.

Monomers of the formula (ZI) which are derivatives of acrylamide or methacrylamide are advantageously used. Also preferred are those monomers which contain halide, methoxysulfate or ethoxysulfate ions as counterions. Also preferred are those monomers of the formula (ZI) in which R ³ , R ⁴ and R ^ are methyl groups.

Acrylamidopropyltrimethylammonium chloride is a very particularly preferred monomer of the formula (Z-I).

Acrylic acid, methacrylic acid, crotonic acid and 2-methyl-crotonic acid are suitable as monomeric carboxylic acids of the formula (Z-II). Acrylic or methacrylic acid, in particular acrylic acid, are preferably used.

The zwitterionic polymers which can be used according to the invention are prepared from monomers of the formulas (ZI) and (Z-Il) by known polymerization processes. The polymerization can be carried out either in aqueous or aqueous-alcoholic solution. Alcohols with 1 to 4 Carbon atoms, preferably isopropanol, are used, which also serve as polymerization regulators. However, other components can also be added to the monomer solution as regulators, e.g. B. formic acid or mercaptans, such as thioethanol and thioglycolic acid. The polymerization is initiated with the aid of radical-forming substances. For this purpose, redox systems and / or thermally disintegrating radical formers of the azo compound type, such as, for. B. azoisobutyronitrile, azo-bis (cyanopentanoic acid) or azo-bis (amidinopropane) dihydrochloride can be used. As redox systems are, for. B. Combinations of hydrogen peroxide, potassium or ammonium peroxodisulfate and tertiary butyl hydroperoxide with sodium sulfite, sodium dithionite or hydroxylamine hydrochloride as a reduction component.

The polymerization can be carried out isothermally or under adiabatic conditions, with the temperature range for the course of the reaction being able to fluctuate between 20 and 200 ^° C. depending on the concentration ratios as a result of the heat of polymerization being released, and the reaction possibly having to be carried out under the excess pressure which arises. The reaction temperature is preferably between 20 and 100 ^° C.

The pH during the copolymerization can vary within a wide range. Polymerization is advantageously carried out at low pH values; however, pH values above the neutral point are also possible. After the polymerization, an aqueous base, e.g. B. sodium hydroxide solution, potassium hydroxide solution or ammonia, adjusted to a pH between 5 and 10, preferably 6 to 8. Further information on the polymerization process can be found in the examples.

Polymers in which the monomers of the formula (ZI) were present in excess over the monomers of the formula (Z-II) have proven to be particularly effective. It is therefore preferred according to the invention to use those polymers which consist of monomers of the formula (ZI) and the monomers of the formula (Z-Il) in a molar ratio of from 60:40 to 95: 5, in particular from 75:25 to 95 : 5, exist. The cationic or amphoteric polymers are preferably present in the agents according to the invention in amounts of 0.05 to 10% by weight, based on the total agent. Amounts of 0.1 to 5% by weight are particularly preferred.

In summary, agents according to the invention are preferred which, based on the weight of the agent, 0.1 to 10% by weight, preferably 0.5 to 8% by weight, particularly preferably 0.75 to 7.5% by weight and in particular 1, Contain 0 to 5.0% by weight of quaternary ammonium compound (s).

Silicones represent a further care component which can preferably be used according to the invention. Here, hair colorants according to the invention are preferred, which are characterized in that the preparation of oxidation dye precursors (A) and / or the oxidant preparation (B) contains at least one silicone, preferably a silicone, as a care substance is selected from:

(i) polyalkylsiloxanes, polyarylsiloxanes, polyalkylarylsiloxanes which are volatile or non-volatile, straight-chain, branched or cyclic, cross-linked or non-cross-linked;

(ii) polysiloxanes which contain in their general structure one or more organofunctional groups which are 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; I) sulfonic acid groups; and m) sulfate or thiosulfate groups;

(iii) linear polysiloxane (A) - polyoxyalkylene (B) - block copolymers of the type (AB) _n with n>3;

(iv) grafted silicone polymers with a non-silicone-containing organic backbone, which consist of an organic main chain which is formed from organic monomers which contain no silicone, onto which at least one polysiloxane macromer has been grafted in the chain and, if appropriate, at least one chain end;

(v) grafted silicone polymers with a polysiloxane backbone onto which non-silicone-containing organic monomers having a polysiloxane backbone have been grafted, onto which at least one organic macromer which contains no silicone has been grafted in the chain and optionally at at least one of its ends ;

(vi) or mixtures thereof.

Particularly preferred agents according to the invention contain one or more amino-functional silicones as a care substance. Such silicones can e.g. through the formula

M (RaQbSiO ₍ 4-ab) / 2) x (RcSiO _(4-c) / 2) yM

Will be described, wherein in the above formula R is a hydrocarbon or a hydrocarbon radical having 1 to about 6 carbon atoms, Q is a polar radical of the general formula -R ¹ HZ, wherein R ^{1 is} a divalent connecting group which is attached to hydrogen and the Radical Z is bonded, composed of carbon and hydrogen atoms, carbon, hydrogen and oxygen atoms or carbon, hydrogen and nitrogen atoms, and Z is an organic, amino-functional radical which contains at least one amino-functional group; "a" takes values in the range from about 0 to about 2, "b" takes values in the range from about 1 to about 3, "a" + "b" is less than or equal to 3, and "c" is a number in the range from about 1 to about 3, and x is a number in the range 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 in the range from about 20 to about 10,000, preferably from about 125 to about 10,000 and am most preferred is from about 150 to about 1,000 and M is a suitable silicone end group as is known in the art, preferably trimethylsiloxy. Non-limiting examples of the radicals represented by R include alkyl radicals such as methyl, ethyl, propyl, isopropyl, isopropyl, butyl, isobutyl, amyl, isoamyl, hexyl, isohexyl and the like; Alkenyl radicals, such as vinyl, halovinyl, alkylvinyl, allyl, haloallyl, alkylallyl; Cycloalkyl radicals such as cyclobutyl, cyclopentyl, cyclohexyl and the like; Phenyl residues, benzyl residues, halogenated hydrocarbon residues such as 3-chloropropyl, 4-bromobutyl, 3,3,3-trifluoropropyl, chlorocyclohexyl, bromophenyl, chlorophenyl and the like, and sulfur-containing residues such as mercaptoethyl, mercaptopropyl, mercaptohexyl, mercaptophenyl and the like; preferably R is an alkyl group containing 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 CC (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 - a.

Z is an organic, amino-functional radical containing at least one functional amino group. A possible formula for Z is NH (CH ₂ ) ₂ NH ₂ , where z is 1 or more. Another possible formula for Z is -NH (CH ₂ ) _Z (CH ₂ ) _Z2 NH, where both z and zz are independently 1 or more, which structure includes diamino ring structures such as piperazinyl. Z is most preferably a - NHCH ₂ CH ₂ NH ₂ residue. Another possible formula for Z is - N (CH ₂ ) _Z (CH ₂ ) _Z2 NX ₂ or -NX ₂ , where 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 is 0.

Q 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 formulas, "a" takes values in the range of about 0 to about 2, "b" takes values in the range of about 2 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. the molar ratio of R ₃ Qb SiO (4 _-a- by ₂ units to the R ₀ SiO _{(4-c) / 2} - units 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. If one or more silicones of the above formula are used, the various variable substituents in the above formula can be used for the various silicone components contained in the silicone mixture are present to be different.

Preferred agents according to the invention are characterized in that the

Preparation of oxidation dye precursors (A) and / or the

Oxidizing agent preparation (B) as a care substance, at least an amino-functional silicone of formula (I)

R ^ G _3-3 -Si (OSiG ₂ ) n- (OSiG _b R ' _2- 0 ^ -0-SiG _3-3 -Ra (I),

contains, in which means:

G is -H, a phenyl group, -OH, -0-CH ₃ , -CH ₃ , -CH ₂ CH ₃ , -

CH ₂ CH ₂ CH ₃ , -CH (CHs) ₂ , -CH ₂ CH ₂ CH ₂ H ₃ , -CH ₂ CH (CH ₃ ) ₂ , -

CH (CH ₃ ) CH ₂ CH ₃ , -C (CHa) ₃ ; a stands for 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, n being preferred

Assumes 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 o -N (R ") - CH ₂ -CH ₂ - N (R") ₂ o -N (R ") ₂ o -N ⁺ (R") ₃ A- o -N ⁺ H (R ") ₂ A ^' o -N ⁺ H ₂ (R") A- o -N (R ") - CH ₂ -CH ₂ -N ⁺ RΗ ₂ A-, each R" for identical or different radicals from the group - H, -phenyl, -benzyl, the Ci_ ₂ o-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 (CHs) 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.

Particularly preferred agents according to the invention are characterized in that the preparation of oxidation dye precursors (A) and / or the oxidizing agent preparation (B) as a care substance is at least an amino-functional silicone of the formula (II)

(CH ₃ ) ₃ Si- [O-Si (CH ₃ ) ₂ ] n [OSi (CH ₃ )] _m -OSi (CH ₃ ) 3 (II),

I CH ₂ CH (CH ₃ ) CH ₂ NH (CH ₂ ) ₂ NH ₂

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

According to the INCI declaration, these silicones are called trimethylsilylamodimethicones. .

Also particularly preferred are agents according to the invention which are characterized in that the preparation of oxidation dye precursors (A) and / or the oxidizing agent preparation (B) as a care substance is at least one amino-functional silicone of the formula (III) R- [Si (CH ₃ ) 2-O] _n1 [Si (R) -O] _m - [Si (CH ₃ ) 2] n2-R (III),

contains, wherein R is -OH, -0-CH ₃ or a -CH ₃ group and m, n1 and n2 are numbers, the sum (m + n1 + n2) of 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 having values from 1 to 2000, in particular from 1 to 10.

According to the INCI declaration, these silicones are referred to as amodimethicones.

Regardless of which amino-functional silicones are used, agents according to the invention are preferred in which the amino-functional silicone has an 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 gram of the amino-functional silicone. It can be determined by titration and can also be specified in the unit mg KOH / g.

Agents preferred according to the invention contain, based on the weight of the flowable preparation of oxidation dye precursors (A) and / or based on the weight of the flowable oxidizing agent preparation (B), 0.01 to 10% by weight, preferably 0.1 to 8% by weight, particularly preferably 0.25 to 7.5% by weight and in particular 0.5 to 5% by weight of amino-functional silicone (s).

In addition to the substances mentioned, the agents according to the invention can contain further care substances. These are, for example, vitamins, provitamins or vitamin precursors with particular preference, so that agents preferred according to the invention are characterized in that they additionally contain at least one substance from the group of vitamins, provitamins and vitamin precursors and their derivatives, vitamins, pro-vitamins and Pre-vitamins are preferred which are assigned to groups A, B, C, E, F and H.

The group of substances called vitamin A includes retinol (vitamin Ai) and 3,4-didehydroretinol (vitamin A ₂ ). The ß-carotene is the provitamin of retinol. According to the invention, vitamin A acid and its esters, vitamin A aldehyde and vitamin A alcohol and its esters such as palmitate and acetate come into consideration as vitamin A components. The agents according to the invention preferably contain the vitamin A component in amounts of 0.05-1% by weight, based on the entire preparation.

The vitamin B group or the vitamin B complex include u. a.

- Vitamin B ₁ (thiamine)

- Vitamin B ₂ (riboflavin)

- Vitamin B ₃ . ^" The compounds nicotinic acid and nicotinic acid amide (niacinamide) are often referred to under this name. Nicotinic acid amide, which is contained in the agents used according to the invention preferably in amounts of 0.05 to 1% by weight, based on the total agent, is preferred according to the invention .

- Vitamin B ₅ (pantothenic acid, panthenol and pantolactone). Within this group, panthenol and / or pantolactone is preferably used. Derivatives of panthenol which can be used according to the invention are, in particular, the esters and ethers of panthenol and cationically derivatized panthenols. Individual representatives are, for example, panthenol triacetate, panthenol monoethyl ether and its monoacetate and the cationic panthenol derivatives disclosed in WO 92/13829. The compounds of the vitamin Bs type mentioned are preferably present in the agents according to the invention in amounts of 0.05-10% by weight, based on the total agent. Amounts of 0.1-5% by weight are particularly preferred.

- Vitamin B ₆ (pyridoxine, pyridoxamine and pyridoxal). Vitamin C (ascorbic acid). Vitamin C is used in the agents according to the invention preferably in amounts of 0.1 to 3 wt. Use in the form of the palmitic acid ester, the glucosides or phosphates can be preferred. Use in combination with tocopherols may also be preferred.

Vitamin E (tocopherols, especially α-tocopherol). Tocopherol and its derivatives, which include in particular the esters such as acetate, nicotinate, phosphate and succinate, are preferably present in the agents according to the invention in amounts of 0.05-1% by weight, based on the total agent.

Vitamin F. The term "vitamin F" usually means essential fatty acids, in particular linoleic acid, linolenic acid and arachidonic acid.

Vitamin H. Vitamin H is the compound (3aS, 4S, 6aR) -2-oxohexahydrothienol [3,4-d] imidazole-4-valeric acid, for which the trivial name biotin has now become established. Biotin is contained in the agents according to the invention preferably in amounts of 0.0001 to 1.0% by weight, in particular in amounts of 0.001 to 0.01% by weight.

The agents according to the invention preferably contain vitamins, provitamins and vitamin precursors from groups A, B, E and H. Panthenol, pantolactone, pyridoxine and its derivatives as well as nicotinamide and biotin are particularly preferred.

Another group of care substances that can be contained in the agents according to the invention are the protein hydrolyzates and their derivatives (P). Protein hydrolyzates are product mixtures that are obtained by acidic, basic or enzymatically catalyzed breakdown of proteins (proteins). According to the invention, the term protein hydrolyzates also includes total hydrolyzates and individual amino acids and their derivatives as well Mixtures of different amino acids understood. Furthermore, according to the invention, polymers constructed from amino acids and amino acid derivatives are understood to be protein hydrolyzates. The latter include, for example, polyalanine, polyasparagine, polyserine, etc. Further examples of compounds which can be used according to the invention are L-alanyl-L-proline, polyglycine, glycyl-L-glutamine or D / L-methionine-S-methylsulfonium chloride. Of course, ß-amino acids and their derivatives such as ß-alanine, anthranilic acid or hippuric acid can also be used according to the invention. The molecular weight of the protein hydrolyzates which can be used according to the invention is between 75, the molecular weight for glycine, and 200,000, preferably the molecular weight is 75 to 50,000 and very particularly preferably 75 to 20,000 daltons.

According to the invention, protein hydrolyzates of plant, animal, marine or synthetic origin can be used.

Animal protein hydrolyzates are, for example, elastin, collagen, keratin and milk protein protein hydrolyzates, which can also be in the form of salts. Such products are, for example, under the trademarks Dehylan ^® (Cognis), Promois ^® (Interorgana), Collapuron ^® (Cognis), Nutrilan ^® (Cognis), Gelita-Sol ^® (Deutsche Gelatine Fabriken Stoess & Co), Lexein ^® (Inolex) and Kerasol ^® (Croda) sold.

According to the invention, the use of protein hydrolysates of plant origin, e.g. B. soy, almond, pea, potato and wheat protein hydrolyzates. Such products are, for example, under the trademarks Gluadin ^® (Cognis), DiaMin ^® (Diamalt), Lexein ^® (Inolex), Hydrosoy ^® (Croda), Hydrolupin ^® (Croda), Hydrosesame ^® (Croda), Hydrotritium ^® (Croda) and Crotein ^® (Croda) available.

Although the use of the protein hydrolyzates as such is preferred, amino acid mixtures obtained in some other way can optionally be used in their place. It is also possible to use derivatives of the pro teinhydrolysate, for example in the form of their fatty acid condensation products. Such products are sold for example under the names Lamepon® ^® (Cognis), Lexein ^® (Inolex), Crolastin ^® (Croda) or crotein ^® (Croda).

Of course, the teaching according to the invention includes all isomeric forms, such as eis-trans isomers, diastereomers and chiral isomers.

According to the invention, it is also possible to use a mixture of several protein hydrolyzates (P).

The protein hydrolyzates (P) are in the compositions in concentrations of 0.01% by weight to 20% by weight, preferably from 0.05% by weight to 15% by weight and very particularly preferably in amounts of 0.05% by weight .% contain up to 5% by weight.

In addition to the care substance (s), the flowable preparation of oxidation dye precursors (A) and the flowable oxidation agent preparation (B) contain further ingredients. The flowable preparation of oxidation dye precursors (A) contains at least one

Oxidation dye intermediate. These are described below.

Conventional hair dyes usually consist of at least one developer and at least one coupler substance and may also contain direct dyes (= hair dyes) as nuances. Coupler and developer components are also referred to as oxidation dye precursors.

Primary aromatic amines with a further free or substituted hydroxy or amino group in the para or ortho position, diaminopyridine derivatives, heteroeyclic hydrazones, 4-aminopyrazolone derivatives and 2,4,5,6-tetraaminopyrimidine and derivatives thereof are usually used as developer components used. Specific representatives are, for example, p-phenylenediamine, p-toluenediamine, 2,4,5,6-tetraaminopyrimidine, p-aminophenol, N, N-bis- (2-hydroxyethyl) -p-phenylenediamine, 2- (2.5 -Diaminophenyl) -ethanol, 2- (2,5-diaminophenoxy) -ethanol, 1-phenyl-3-carboxyamido-4-amino-pyrazol-5-one, 4-amino-3-methylphenol, 2-aminomethyl-4- aminophenol, 2-hydroxymethyl-4-aminophenol, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6-triamino-4-hydroxypyrimidine.

M-Phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones, m-aminophenols and substituted pyridine derivatives are generally used as coupler components. Suitable coupler substances are in particular α-naphthol, 1, 5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 2 , 4-diaminophenoxyethanol, 2-amino-4- (2-hydroxyethylamino) anisole (Lehmanns Blau), 1-phenyl-3-methyl-pyrazol-5-one, 2,4-dichloro-3-aminophenol, 1, 3 - bis (2,4-diaminophenoxy) propane, 2-chlororesorcin, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methyiresorcinol, 5-methylresorcinol, 3-amino-6-methoxy-2 -methyl- mino-pyridine and 3,5-diamino-2,6-dimethoxypyridine.

As already mentioned, the agents according to the invention can contain one or more dye precursors. Agents according to the invention which contain at least one oxidation dye precursor of the developer type and / if appropriate at least one oxidation dye precursor of the coupler type are preferred.

With regard to the dye precursors that can be used in the agents according to the invention, the present invention is not subject to any restrictions. The agents according to the invention can be used as further dye precursors

- Oxidation dye precursors of the developer and / or coupler type, and

- Contain precursors of nature-analogous dyes, such as indole and indoline derivatives, and mixtures of representatives of these groups. In a first preferred embodiment, the agents according to the invention contain at least one developer component. Primary aromatic amines with a further, in the para or ortho position, free or substituted hydroxy or amino group, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazole derivatives and 2,4,5,6-tetraaminopyrimidine and the like are usually used as developer components Derivatives used.

It can be preferred according to the invention to use a p-phenylenediamine derivative or one of its physiologically tolerable salts as the developer component. P-Phenylenediamine derivatives of the formula (E1) are particularly preferred

in which

G ¹ represents a hydrogen atom, a Ci to C ₄ alkyl, a d- to C ₄ - monohydroxyalkyl radical, a C ₂ - to C ₄ polyhydroxyalkyl radical, a (Cr to _C4) alkoxy (d- to C ₄ ) -alkyl radical, a 4'-aminophenyl radical or a Cr to C ₄ -alkyl radical which is substituted by a nitrogen-containing group, a phenyl or a 4'-aminophenyl radical;

G ² represents a hydrogen atom, a C ₁ to C ₄ alkyl radical, a Cr to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a (Cr to C ₄ ) alkoxy (Cr to C ₄ ) alkyl radical or a C ₁ to C ₄ alkyl radical which is substituted by 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 to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ -Polyhydroxyalkylrest, a C ₁ - bis C ₄ hydroxyalkoxy, a C ₁ to C4 acetylaminoalkoxy, a Cr to C ₄ mesylaminoalkoxy or a Cr to C ₄ carbamoylaminoalkoxy; G ⁴ represents a hydrogen atom, a halogen atom or a Cr to C ₄ alkyl radical or if G ³ and G ^{4 are} in the ortho position to one another, they can together form a bridging α, ω-alkylenedioxo group, such as, for example, an ethylenedioxy group.

Examples of the C 1 -C ₄ -alkyl radicals mentioned as substituents in the compounds according to the invention are the groups methyl, ethyl, propyl, isopropyl and butyl. Ethyl and methyl are preferred alkyl radicals. Cr to C ₄ -alkoxy radicals preferred according to the invention are, for example, a methoxy or an ethoxy group. Further preferred examples of a C ₁ to C ₄ hydroxyalkyl group are a hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group. A 2-hydroxyethyl group is particularly preferred. A particularly preferred C ₂ - to C ₄ -polyhydroxyalkyl group is the 1, 2-dihydroxyethyl. Examples of halogen atoms according to the invention are F, Cl or Br atoms, Cl atoms are very particularly preferred. According to the invention, the other terms used are derived from the definitions given here. Examples of nitrogen-containing groups of the formula (E1) are in particular the amino groups, C ₁ to C ₄ monoalkylamino groups, C ₁ to C ₄ dialkylamino groups, C ₁ to C ₄ trialkylammonium groups, Cr to C ₄ monohydroxyalkylamino groups, imidazolinium and Ammonium.

Particularly preferred p-phenylenediamines of the formula (E1) are selected from p-phenylenediamine, p-toluenediamine, 2-chloro-p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2 , 6-diethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, NN-dipropyl-p-phenylenediamine, 4-amino -3-methyl- (N, N-diethyl) aniline, N, N-bis- (β-hydroxyethyl) -p-phenylenediamine, 4-N, N-bis- (β-hydroxyethyl) amino-2-methylaniline, 4-N, N-bis (β-hydroxyethyl) amino-2- chloraniline, 2- (ß-hydroxyethyl) -p-phenylenediamine, 2- (α, ß-dihydroxyethyl) -p-phenylenediamine, 2-fluoro-p-phenylenediamine, 2-isopropyl-p-phenylenediamine, N- (ß-hydroxypropyl ) -p-phenylenediamine, 2-hydroxymethyl-p-phenylenediamine, N, N-dimethyl-3-methyl-p-phenylenediamine, N, N- (ethyl, ß-hydroxyethyl) -p-phenylenediamine, N- (ß, γ -Dihydroxypropyl) -p-phenylenediamine, N- (4'-aminophenyl) - p-phenylenediamine, N-phenyl-p-phenylenediamine, 2- (ß-hydroxyethyloxy) -p-phenylenediamine, 2- (ß-acetylaminoethyloxy) -p -phenylenediamine, N- (ß-

Methoxyethyl) -p-phenylenediamine and 5,8-diaminobenzo-1,4-dioxane and their physiologically tolerable salts.

P-Phenylenediamine derivatives of the formula (E 1) which are very particularly preferred according to the invention are p-phenylenediamine, p-toluenediamine, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- (α, β-dihydroxyethyl) -p-phenylenediamine and N, N-bis (ß-hydroxyethyl) -p-phenylenediamine.

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

Among the binuclear developer components which can be used in the agents according to the invention, one can name in particular the compounds which correspond to the following formula (E2) and their physiologically tolerable salts:

in which: Z ¹ and Z ² independently of one another represent a hydroxyl or NH ₂ radical which is optionally substituted by a Cr to C ₄ alkyl radical, by a Cj to C ₄ hydroxyalkyl radical and / or by a bridging Y or which is optionally Is part of a bridging ring system, the bridging Y represents an alkylene group having 1 to 14 carbon atoms, such as, for example, a linear or branched alkylene chain or an alkylene ring which is composed of one or more nitrogen-containing groups and / or one or more heteroatoms such as oxygen, sulfur or nitrogen atoms can be interrupted or terminated and possibly substituted by one or more hydroxyl or C ₁ - to Cs-alkoxy radicals, or a direct bond, G ⁵ and G ⁶ independently of one another represent a hydrogen or halogen atom, a Cr bis C ₄ alkyl radical, a Cr to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a Cr to C ₄ aminoalkyl radical or he has a direct connection to the bridge Y,

- G ⁷ , G ⁸ , G ⁹ , G ¹⁰ , G ¹¹ and G ¹² independently of one another represent a hydrogen atom, a direct bond to the bridge Y or a Cr to C ₄ alkyl radical, with the provisos that

- The compounds of formula (E2) contain only one bridging Y per molecule and

- The compounds of formula (E2) contain at least one amino group which carries at least one hydrogen atom.

According to the invention, the substituents used in formula (E2) are defined analogously to the above statements.

Preferred dinuclear developer components of the formula (E2) are in particular: N, N'-bis (β-hydroxyethyl) -N, N'-bis (4 ⁱ -aminophenyl) -1, 3-diamino-propan-2-ol, N, N'-bis (ß-hydroxyethyl) -N, N'-bis- (4 ¹ -aminophenyl) -ethylenediamine, N, N'-bis- (4-aminophenyl) -tetramethylene-diamine, N, N'-bis - (ß-hydroxyethyl) -N, N'- bis (4-aminophenyl) tetramethylene diamine, N, N'-bis (4-methyl-aminophenyl) - tetramethylenediamine, N, N ^I -diethyl-N, N ^I -bis- (4'-amino-3'-methylphenyl) - ethylenediamine, bis- (2-hydroxy-5-aminophenyl) methane, 1, 3-bis- (2,5-diaminophenoxy) propan-2-ol, N.N'-bis - ^ '- aminophenyO-i ^ -diazacycloheptane, N, N'-bis (2-hydroxy-5-aminobenzyl) piperazine, N- (4'-aminophenyl) -p-phenylenediamine and I .IO-bis- ^ δ'-diaminophenyO-I ^ J.IO-tetraoxadecane and their physiologically acceptable salts.

Very particularly preferred dual-core developer components of the formula (E2) are N, N'-bis (β-hydroxyethyl) -N, N ^l -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 and 1 J0-bis- (2 \ 5'-diaminophenyl) -1, 4,7,10-tetraoxadecane or one of their physiologically acceptable salts.

Furthermore, it can be preferred according to the invention to use a p-aminophenol derivative or one of its physiologically tolerable salts as developer component. P-Aminophenol derivatives of the formula (E3) are particularly preferred

in which:

G ¹³ stands for a hydrogen atom, a halogen atom, a Cr to C ₄ alkyl radical, a Cr to C ₄ ionohydroxyalkyl radical, a C _∑ to C ₄ polyhydroxyalkyl radical, a (C ₁ to C ₄ ) alkoxy (Cr to C ^ alkyl radical, a Cr to C ₄ aminoalkyl radical, a hydroxy (Cr to C ₄ ) alkylamino radical, a Cr to C ₄ hydroxyalkoxy radical, a Cr to C ₄ hydroxyalkyl (Crbis C ₄ ) aminoalkyl radical or a (di-Cr to C ₄ alkylamino) - (Cr to C4) alkyl radical, and G ¹⁴ represents a hydrogen or halogen atom, a d- to C ₄ -alkyl radical, a Cr to C4-monohydroxyalkyl radical, a C- ₂ - to C ₄ -polyhydroxyalkyl radical, a (C ₁ - to C ₄ J-alkoxy-( C ₁ - to C ₄ ) -alkyl radical, a Cr to C4-aminoalkyl radical or a Cr to C ₄ -cyanoalkyl radical,

G ¹⁵ represents hydrogen, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a phenyl radical or a benzyl radical, and

G ¹⁶ represents hydrogen or a halogen atom.

According to the invention, the substituents used in formula (E3) are defined analogously to the above statements.

Preferred p-aminophenols of the formula (E3) are in particular p-aminophenol, N-methyl-p-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 2-hydroxymethylamino-4-aminophenol, 4 -Amino-3-hydroxymethylphenol, 4-amino- 2- (D-hydroxyethoxy) phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethyl-phenol, 4-amino -2- aminomethylphenol, 4-amino-2- (ß-hydroxyethyl-aminomethyl) phenol, 4-amino-2- (α, ß-dihydroxyethyl) phenol, 4-amino-2-fluorophenol, 4-amino-2 -chlorophenol, 4-amino-2,6-dichlorophenol, 4-amino-2- (diethyl-aminomethyl) -phenol and their physiologically tolerable salts.

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

Furthermore, the developer component can be selected from o-aminophenol and its derivatives, such as, for example, 2-amino-4-methylphenol, 2-amino-5-methylphenol or 2-amino-4-chlorophenol. Furthermore, the developer component can be selected from heterocyclic developer components, such as, for example, the pyridine, pyrimidine, pyrazole, pyrazole-pyrimidine derivatives and their physiologically tolerable salts.

Preferred pyridine derivatives are in particular the compounds 2,5-diamino-pyridine, 2- (4'-methoxyphenyl) amino-3-amino-pyridine, 2,3-diamino-6-methoxy-pyridine, 2- (β-methoxyethyl ) amino-3-amino-6-methoxy-pyridine and 3,4-diamino-pyridine.

Preferred pyrimidine derivatives are in particular 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2-dimethylamino-4,5,6- triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6-triaminopyrimidine.

Preferred pyrazole derivatives are in particular 4,5-diamino-1-methylpyrazole, 4,5-diamino-1 - (ß-hydroxyethyl) -pyrazole, 3,4-diaminopyrazole, 4,5-diamino-1 - (4 ¹ - 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-teιt-butyl-1-methyl pyrazole, 4,5-diamino-1-tert. -butyl-3-methylpyrazole, 4,5-diamino-1 - (ß-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-methyl pyrazole, 4,5-diamino-3-hydroxymethyl-i -isopropylpyrazole, 4,5-diamino-3-methyl-1-isopropylpyrazole, 4-amino-5- (D-aminoethyl) amino-1, 3-dimethylpyrazole, 3,4,5-triaminopyrazole, 1-methyl-3, 4,5-triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole and 3,5-diamino-4- (β-hydroxyethyl) amino-1-methylpyrazole.

Preferred pyrazole-pyrimidine derivatives are in particular the derivatives of pyrazole- [1,5-a] -pyrimidine of the following formula (E4) and its tautomeric forms, provided that there is a tautomeric equilibrium:

in which:

"17 G" 18, G and G "20 independently of one another represent a hydrogen atom, a Cr to C ₄ alkyl radical, an aryl radical, a Ci to C ₄ hydroxyalkyl radical, a C ₂ to C 4 polyhydroxyalkyl radical a (Ci to C ₄₎ - AIkOXy- (C ₁ - to C ₄₎ alkyl group a Ci to C ₄ -aminoalkyl radical, which may be optionally protected by an acetyl ureide or a sulfonyl residue, a (Cr to C- ₄ ) alkylamino- (Cr to C-4) alkyl radical, a di - [(Cr to C ₄ ) alkyl] - (Cr to C ₄ ) aminoalkyl radical, the dialkyl radicals optionally having one Form a carbon cycle or a heterocycle with 5 or 6 chain links, a Cr to C ₄ hydroxyalkyl or a di (Cr to C ₄ ) - [hydroxyalkyl] - (Cr to C4) aminoalkyl radical, the X radicals independently of one another a hydrogen atom, a Cr to C ₄ alkyl radical, an aryl radical, a Cr to C ₄ hydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a Cr to C ₄ aminoalkyl radical, a (Cr to C ₄ ) -Alkylamino- (Cr to C4) -a alkyl radical, a di - [(Cr to C ₄ ) alkyl] - (Cr to C ₄ ) aminoalkyl radical, the dialkyl radicals optionally forming a carbon cycle or a heterocycle with 5 or 6 chain links, a Cr to C ₄ hydroxyalkyl- or a di- (Cr to C ₄ -hydroxyalkyl) aminoalkyl radical, an amino radical, a Cr to C ₄ -alkyl or di- (Cr to 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 is - if p + q is 2, n has the value O, and the groups NG ¹⁷ G ¹⁸ and NG ¹⁹ G ²⁰ occupy positions (2,3); (5.6); (6.7); (3.5) or (3.7); if p + q is 1, n is 1, and the groups NG ¹⁷ G ¹⁸ (or NG ¹⁹ G ²⁰ ) and the group OH occupy positions (2,3); (5.6); (6.7); (3.5) or (3.7);

According to the invention, the substituents used in formula (E4) are defined analogously to the above statements.

If the pyrazole [1, 5-a] pyrimidine of the above formula (E4) contains a hydroxyl group at one of the positions 2, 5 or 7 of the ring system, there is a tautomeric equilibrium, which is illustrated, for example, in the following scheme:

Among the pyrazole [1, 5-a] pyrimidines of the above formula (E4), one can mention in particular:

Pyrazole- [1,5-a] pyrimidine-3,7-diamine;

2,5-dimethylpyrazole- [1,5-a] pyrimidine-3,7-diamine;

Pyrazole- [1,5-a] pyrimidine-3,5-diamine;

2,7-dimethylpyrazole- [1,5-a] pyrimidine-3,5-diamine;

3-aminopyrazole- [1,5-a] pyrimidin-7-ol;

3-aminopyrazole- [1,5-a] pyrimidin-5-ol;

2- (3-aminopyrazole- [1,5-a] pyrimidin-7-ylamino) ethanol;

2- (7-aminopyrazole- [1,5-a] pyrimidin-3-ylamino) ethanol;

2 - [(3-aminopyrazole- [1,5-a] pyrimidin-7-yl) - (2-hydroxyethyl) amino] ethanol;

2 - [(7-aminopyrazol- [1,5-a] pyrimidin-3-yl) - (2-hydroxyethyl) amino] ethanol; 5,6-dimethylpyrazole- [1,5-a] pyrimiclin-3,7-diamine;

2,6-dimethylpyrazole- [1,5-a] pyrimidine-3,7-diamine;

3-amino-7-dimethylamino-2,5-dimethylpyrazole- [1,5-a] pyrimidine; as well as their physiologically acceptable salts and their tautomeric forms when there is a tautomeric equilibrium.

The pyrazole- [1,5-a] pyrimidines of the above formula (E4) can be prepared as described in the literature by cyclization starting from an aminopyrazole or from hydrazine.

In a further preferred embodiment, the agents according to the invention contain at least one coupler component.

M-Phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenol derivatives are generally used as coupler components. Suitable coupler substances are in particular 1-naphthol, 1, 5-, 2,7- and 1, 7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 1-phenyl-3 -methyl-pyrazolone-5, 2,4-dichloro-3-aminophenol, 1, 3-bis- (2 ', 4 ^I -diaminophenoxy) -propane, 2-chloro-resorcinol, 4-chloro-resorcinol, 2-chloro -6-methyl-3-aminophenol, 2-amino-3-hydroxypyridine, 2-methylresorcinol, 5-methylresorcinol and 2-methyl-4-chloro-5-aminophenol.

Coupler components preferred according to the invention are

- m-Aminophenol and its derivatives such as 5-amino-2-methylphenol, N-cyclopentyl-3-aminophenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 2,6-dimethyl -3-aminophenol, S-trifluoroacetylamino ^ -chlor-e-methylphenol, 5-amino-4-chloro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol, 5- (2'-

Hydroxyethyl) amino-2-methylphenol, 3- (diethylamino) phenol, N-cyclopentyl-3-aminophenol, 1, 3-dihydroxy-5- (methylamino) benzene, 3-ethylamino-4-methylphenol and 2,4- Dichloro-3-aminophenol, o-aminophenol and its derivatives, m-diaminobenzene and its derivatives such as, for example, 2,4-diaminophenoxyethanol, 1, 3-bis (2 ¹ , 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 and 1-amino-3-bis - (2'-hydroxyethyl) aminobenzene,

o-diamino benzene and its derivatives such as 3,4-diamino benzoic acid and 2,3-diamino-1-methylbenzene,

Di- or trihydroxybenzene derivatives such as resorcinol,

Resorcinol monomethyl ether, 2-methylresorcinol, 5-methylresorcinol, 2,5-

Dimethylresorcinol, 2-chlororesorcinol, 4-chlororesorcinol, pyrogallol and 1, 2,4-

Trihydroxybenzene,

Pyridine derivatives such as 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 and 3,5-

Diamino-2,6-dimethoxypyridine,

Naphthalene derivatives such as 1-naphthol, 2-methyl-1-naphthol, 2-

Hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1, 5-

Dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 1, 7-dihydroxynaphthalene, 1, 8-

Dihydroxynaphthalene, 2,7-dihydroxynaphthalene and 2,3-dihydroxynaphthalene,

Morpholine derivatives such as 6-hydroxybenzomorpholine and 6-

Amino-benzomorpholine,

Quinoxaline derivatives such as 6-methyl-1, 2,3,4-tetrahydroquinoxaline, pyrazole derivatives such as 1-phenyl-3-methylpyrazol-5-one, indole derivatives such as 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole,

- Pyrimidine derivatives, such as 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-methy! Pyrimidine, or Methylenedioxybenzene derivatives such as 1-hydroxy-3,4-methylenedioxybenzene, 1-amino-3,4-methylenedioxybenzene and 1- (2'-hydroxyethyi) amino-3,4-methylenedioxybenzene.

Coupler components which are particularly preferred according to the invention are 1-naphthol, 1, 5-, 2,7- and 1, 7-dihydroxynaphthalene, 3-aminophene, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridine, resorcinol, 4-chlororesorcinol , 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol and 2,6-dihydroxy-3,4-dimethylpyridine.

Indoles and indolines which have at least one hydroxyl or amino group, preferably as a substituent on the six-membered ring, are preferably used as precursors of nature-analogous dyes. These groups can carry further substituents, e.g. B. in the form of etherification or esterification of the hydroxy group or an alkylation of the amino group. In a second preferred embodiment, the agents contain at least one indole and / or indoline derivative.

Derivatives of 5,6-dihydroxyindoline of the formula (purple) are particularly suitable as precursors of natural hair dyes,

in the independently of each other

R ¹ represents hydrogen, a CrC ₄ alkyl group or a Ci-C ₄ hydroxyalkyl group,

R ² stands for hydrogen or a -COOH group, where the -COOH group can also be present as a salt with a physiologically compatible cation, - R ³ stands for hydrogen or a CrC4-alkyl group, - R ⁴ stands for hydrogen, a C _r C ₄ alkyl group or a group -CO-R ⁶ , in which R ⁶ stands for a C 1 -C ₄ alkyl group, and

R ⁵ stands for one of the groups mentioned under R ⁴ , as well as physiologically tolerable salts of these compounds with an organic or inorganic acid.

Particularly preferred derivatives of indoline are 5,6-dihydroxyindoline, N-

Methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline,

N-butyl-5,6-dihydroxyindoline, 5,6-dihydroxyindoline-2-carboxylic acid and the 6-

Hydroxyindoline, the 6-aminoindoline and the 4-aminoindoline.

Of particular note 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 especially 5 6-dihydroxyindoline.

Derivatives of 5,6-dihydroxyindole of the formula (UIb) are also particularly suitable as precursors of naturally analogous hair dyes,

in the independently of each other

R ¹ represents hydrogen, a C ¹ -C ₄ -alkyl group or a C 1 -C ₄ -hydroxyalkyl group,

R ² stands for hydrogen or a -COOH group, where the -COOH group can also be present as a salt with a physiologically compatible cation,

R ³ represents hydrogen or a C 1 -C ₄ -alkyl group,

R ⁴ stands for hydrogen, a CjC ₄ alkyl group or a group -CO-R ⁶ , in which R ⁶ stands for a CrC ₄ alkyl group, and

R ⁵ represents one of the groups mentioned under R ⁴ , - And physiologically tolerable salts of these compounds with an organic or inorganic acid.

Particularly preferred derivatives of indole are 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6- dihydroxyindole, 5,6-dihydroxyindole-2-carboxylic acid, 6-hydroxyindole, 6-aminoindole and 4-aminoindole.

Within this group, particular mention should be made of N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole and in particular 5.6 -Dihydroxyindole.

The indoline and indole derivatives can be used in the agents used in the process according to the invention both as free bases and in the form of their physiologically tolerable salts with inorganic or organic acids, for. B. the hydrochloride, sulfates and hydrobromides, are used. The indole or indoline derivatives are usually contained in these in amounts of 0.05-10% by weight, preferably 0.2-5% by weight.

In a further embodiment it can be preferred according to the invention to use the indoline or indole derivative in hair colorants in combination with at least one amino acid or an oligopeptide. The amino acid is advantageously an α-amino acid; very particularly preferred α-amino acids are arginine, ornithine, lysine, serine and histidine, in particular arginine.

Preferred agents according to the invention are characterized in that they contain at least one dye precursor from the groups of the aromatic and heteroaromatic diamines, aminophenols, naphthols, polyphenols, CH-acidic coupler components and their derivatives in amounts of 0.01 to 25% by weight, preferably of 0.5 up to 10% by weight, in particular from 1 to 5% by weight, in each case based on the total composition. In addition to the oxidation dye precursor (s), the preparation (A) for shading can contain one or more substantive dyes. Direct dyes are usually nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols. Preferred direct dyes are those with the international names or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, Acid Yellow 1, Acid Yellow 10, Acid Yellow 23, Acid Yellow 36, HC Orange 1, Disperse Orange 3, Acid Orange 7, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, Acid Red 33, Acid Red 52, HC Red BN, Pigment Red 57: 1, HC Blue 2, HC Blue 12, Disperse Blue 3, Acid Blue 7, Acid Green 50, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Acid Violet 43, Disperse Black 9, Acid Black 1, and Acid Black 52 known compounds and 1 , 4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1, 4-bis- (ß-hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- (ß-hydroxyethyl) aminophenol, 2- ( 2'-hydroxyethyl) amino-4,6-dinitrophenol, 1- (2'-hydroxyethyl) amino-4-methyl-2-nitrobenzene, 1-amino-4- (2'-hydroxyethyl) amino-5-chloro-2 -nitrobenzene, 4-amino-3-nitrophenol, 1 - (2'-ureidoethyl) amino-4-nitrobenzene, 4-amino-2-nitrodiphenylamine-2'-carboxylic acid 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-1-hydroxy-4-nitrobenzene.

Corresponding agents according to the invention, which are characterized in that they contain at least one direct dye from the group of the cationic (basic) dyes, preferably Basic Blue 6, CI -No. 51, 175; Basic Blue 7, Cl-No. 42,595; Basic Blue 9, Cl-No. 52.015; Basic Blue 26, Cl-No. 44,045; Basic Blue 41, Cl-No. 11, 154; Basic Blue 99, Cl-No. 56,059; Basic Brown 4, Cl-No. 21, 010; Basic Brown 16, Cl-No. 12,250; Basic Brown 17, Cl-No. 12,251; Basic Green 1, Cl-No. 42,040; Basic Orange 31; Basic Red 2, Cl-No. 50,240; Basic Red 22, Cl-No. 11, 055; Basic Red 46; Basic Red 51; Basic Red 76, Cl-No. 12.245; Basic Violet 1, Cl-No. 42,535; Basic Violet 2; Basic Violet 3, Cl-No. 42,555; Basic Violet 10, Cl-No. 45,170; Basic Violet 14, Cl-No. 42,510; Basic Yellow 57, Cl-No. 12.719; Basic Yellow 87 and / or the anionic (acidic) dyes, and / or the nonionic dyes, preferably Acid Black 1, Cl-No. 20,470; Acid Black 52; Acid Blue 7; Acid Blue 9, Cl-No. 42,090; Acid Blue 74, Cl-No. 73.015, Acid Red 18, Cl-No. 16.255; Acid Red 23; Acid Red 27, Cl-No. 16.185; Acid Red 33; Acid Red 52; Acid Red 87, Cl-No. 45,380; Acid Red 92, Cl-No. 45.410; Acid Orange 3; Acid Orange 7; Acid Violet 43, Cl-No. 60.730; Acid Yellow 1, Cl-No. 10.316; Acid Yellow 10; Acid Yellow 23, Cl-No. 19.140; Acid Yellow 3, Cl-No. 47.005; Acid Yellow 36; D&C Brown No. 1, Cl-No. 20.170 (Acid Orange 24); D&C Green No. 5, Cl-No. 61, 570 (Acid Green G); D&C Orange No. 4, Cl-No. 15.510 (Acid Orange II); D&C Orange No. 10, CI-No. 45.425: 1 (Solvent Red 73); D&C Orange No. 11, Cl-No. 45.425 (Acid Red 95); D&C Red No. 21, Cl-No. 45.380: 2 (Solvent Red 43); D&C Red No. 27, Cl-No. 45.410: 1 (Solvent Red 48); D&C Red No. 33, Cl-No. 17,200 (Acid Red 2A, Acid Red B); D&C Yellow No. 7, CI- No. 45.350: 1 (Solvent Yellow 94); D&C Yellow No. 8, Cl-No. 45,350 (Acid Yellow 73); FD & C Red No. 4, Cl-No. 14,700 (Food Red 4); FD&C Yellow No. 6, Cl-No. 15.985 (Food Yellow 3); Food green 3; Pigment Red 57-1; Disperse Black 9; Disperse Blue 1; Disperse Blue 3; Disperse Violet 1; Disperse Violet 4; HC Orange 1; HC Red 1; HC Red 3; HC Red 13; HC Yellow 2; HC Yellow 4; Na Picramat; 1,4-bis (2'-hydroxyethyl) amino-2-nitro-p-phenylenediamine; HC Yellow 5; HC Blue 2; HC Blue 12; 4-amino-3-nitrophenol; HC Yellow 6; HC Yellow 12; 2-nitro-1- (2 ^' hydroxyethyl) amino-4-methylbenzene; 2-nitro-4-amino-diphenylamine-2 - carboxylic acid; 2-amino-6-chloro-4-nitrophenol; HC Red BN; 6-nitro-1, 2,3,4-tetranitroquinoxaline; o-nitro-p-phenylenediamine; p-nitro-m-phenylenediamine; HC Red B 54; HC Red 10; HC Red 11; HC Red 13; 2- (2 ^' -hydroxyethyl) amino-1-hydroxy-4,6-dinitrobenzene; 4-ethylamino-3-nitrobenzoic acid; 2-chloro-6-ethylamino-4-nitrophenol; 2-hydroxy-1,4-napthoquinone; 1-propene- (4-amino-2-nitrophenyl) amine; isatin; N-methylylisatin; HC Violet 1; HC Violet 2; 4-Nitrophenylaminoethylurea in amounts of 0.01 to 25% by weight, preferably 0.5 to 10% by weight, in particular 1 to 5% by weight, in each case based on the total composition, are preferred embodiments of the present invention. Among the dyes mentioned above, some representatives are particularly preferred, which is why further preferred agents according to the invention, which are characterized in that they have at least one direct agent selected from Basic Blue 7, Basic Blue 99, Basic Violet 14, Basic Brown 16, Basic Brown 17, Basic Orange 31, Basic Red 46, Basic Red 51, Basic Red 76, Basic Yellow 57, Basic Yellow 87, Acid Black 1, Acid Blue 7, Acid Violet 43, Acid Red 23, Acid Red 52, Acid Orange 7, Acid Yellow 1, Acid Yellow 10, Acid Yellow 36, Food Green 3, Pigment Red 57-1, Disperse Black 9, Disperse Blue 1, Disperse Blue 3, Disperse Violet 1, Disperse Violet 4, HC Orange 1, HC Red 1, HC Red 3, HC Red 13, HC Yellow 2, HC Yellow 4, Na-Pikramat, 1, 4-bis (2 ^{'-hydroxyethyl)} amino-2-nitro-p-phenylenediamine, HC Yellow 5, HC Blue 2, HC Blue 12, 4-amino-3-nitrophenol, HC Yellow 6, HC Yellow 12, 2-nitro-1- (2 ^' hydroxyethyl) amino-4-methylbenzene, 2-nitro-4-amino-diphenylamine-2-carboxylic acid, 2 -Amino-6-chlorine- 4-nitrophenol, HC Red BN; 6-nitro-1, 2,3,4-tetranitroquinoxaline, o-nitro-p-phenylenediamine, p-nitro-m-phenylenediamine, HC Red B 54, HC Red 10, HC Red 11, HC Red 13, 2- ( 2 ^' - Hydroxyethyl) amino-1-hydroxy-4,6-dinitrobenzene, 4-ethylamino-3-nitrobenzoic acid, 2-chloro-6-ethylamino-4-nitrophenol, 2-hydroxy-1, 4-napthoquinone, 1-propene - (4-amino-2-nitrophenyl) amine, isatin, N-methylylisatin, HC Violet 1, HC Violet 2, 4-nitrophenylaminoethyl urea in amounts of 0.01 to 25% by weight, preferably 0.5 to 10 % By weight, in particular from 1 to 5% by weight, in each case based on the total composition, are preferred.

Furthermore, the agents according to the invention can contain a cationic direct dye. Are particularly preferred

(a) cationic triphenylmethane dyes, such as, for example, Basic Blue 7, Basic Blue 26, Basic Violet 2 and Basic Violet 14,

(b) aromatic systems which are substituted with a quaternary nitrogen group, such as, for example, Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 and Basic Brown 17, and (C) direct dyes which contain a heterocycle which has at least one quaternary nitrogen atom, as are mentioned, for example, in EP-A2-998 908, to which reference is expressly made here, in claims 6 to 11.

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

CH ₃ SO ₄ ^"

Cf

The compounds of formulas (DZ1), (DZ3) and (DZ5), also known as Basic Yellow 87, Basic Orange 31 and Basic Red 51 are very particularly preferred cationic direct dyes of group (c).

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

The agents according to the invention according to this embodiment preferably contain the substantive dyes in an amount of 0.01 to 20% by weight, based on the total agent.

Furthermore, the preparations according to the invention can also contain naturally occurring dyes, such as those contained in henna red, henna neutral, henna black, chamomile flowers, sandalwood, black tea, rotten bark, sage, blue wood, madder root, catechu, sedre and alkanna root.

It is not necessary that the oxidation dye precursors or the substantive dyes each represent uniform compounds. Rather, in the agents according to the invention, due to the manufacturing process for the individual dyes, further components may be contained in minor amounts, provided that these do not adversely affect the coloring result or for other reasons, e.g. toxicological, must be excluded.

With regard to the dyes which can be used in the hair dyeing and tinting agents according to the invention, reference is also expressly made to the monograph Ch. Zviak, The Science of Hair Gare, chapter 7 (pages 248-250; direct dyes) and chapter 8, pages 264-267; Oxidation dye precursors), published as Volume 7 of the "Dermatology" series (ed .: Ch., Culnan and H. Maibach), Marcel Dekker Inc., New York, Basel, 1986, and the "European inventory of cosmetic raw materials", published by the European Community, available in diskette form from the Federal Association of German Industry and Commerce for Medicinal Products, Health Care Products and Personal Care Products, Mannheim.

The flowable oxidizing agent preparation (B) contains at least one oxidizing agent. Persulfates, chlorites and in particular hydrogen peroxide or their adducts with urea, melamine and sodium borate or sodium carbonate are suitable as oxidizing agents.

According to the invention, however, the oxidation coloring agent can also be applied to the hair together with a catalyst which oxidizes the dye precursors, e.g. activated by atmospheric oxygen. Such catalysts are e.g. Metal ions, iodides, quinones or certain enzymes.

Suitable metal ions are, for example, Zn ²⁺ , Cu ²⁺ , Fe ²⁺ , Fe ³⁺ , Mn ²⁺ , Mn ⁴⁺ , Li ⁺ , Mg ²⁺ , Ca ²⁺ and Al ³⁺ . Zn ²⁺ , Cu ²⁺ and Mn ²⁺ are particularly suitable. In principle, the metal ions can 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 and tartrates. By using these metal salts, the formation of the coloring can be accelerated and the shade can be influenced in a targeted manner.

Suitable enzymes are e.g. Peroxidases, which can significantly increase the effects of small amounts of hydrogen peroxide. Furthermore, such enzymes are suitable according to the invention which directly oxidize the oxidation dye precursors with the help of atmospheric oxygen, such as for example the laccases, or generate small amounts of hydrogen peroxide in situ and in this way activate the oxidation of the dye precursors biocatalytically. Particularly suitable catalysts for the oxidation of the dye precursors are the so-called 2-electron oxidoreductases in combination with the substrates specific for this, e.g.

Pyranose oxidase and, for example, D-glucose or galactose, Glucose oxidase and D-glucose,

Glycerin oxidase and glycerin,

- pyruvate oxidase and benzene acid or their salts,

- alcohol oxidase and alcohol (MeOH, EtOH),

Lactate oxidase and lactic acid and their salts,

Tyrosinase oxidase and tyrosine,

Uricase and uric acid or its salts,

Choline oxidase and choline,

- Amino acid oxidase and amino acids.

In a preferred embodiment of the invention, the care effect of the agents according to the invention can be further increased by fatty substances (D). Fat substances are to be understood as meaning fatty acids, fatty alcohols, natural and synthetic waxes, which can be present both in solid form and in liquid form in aqueous dispersion, and natural and synthetic cosmetic oil components.

Linear and / or branched, saturated and / or unsaturated fatty acids having 6 to 30 carbon atoms can be used as fatty acids (D1). Fatty acids with 10-22 carbon atoms are preferred. Among these were, for example, to name the isostearic as the commercial products Emersol ^® 871 and Emersol ^® 875, and isopalmitic acids such as the commercial product Edenor ^® IP 95, and all other products sold under the trade names Edenor ^® (Cognis) fatty acids. Other typical examples of such fatty acids are caprylic acid, 2-ethylhexanoic, capric acid, lauric acid, isotridecanoic, myristic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, elaidic, Petroselin acid, linoleic acid, linolenic acid, arachidic acid, Gadoleinsäure, behenic acid and erucic acid and their technical mixtures, which are used, for example, in the pressure splitting of natural fats and oils, in the oxidation of aldehydes from Roelen's oxosynthesis or in the dimerization of unsaturated fatty acids attack. The fatty acid cuts which are obtainable from coconut oil or palm oil are usually particularly preferred; the use of stearic acid is generally particularly preferred.

The amount used is 0.1-15% by weight, based on the total agent. The amount is preferably 0.5-10% by weight, with amounts of 1-5% by weight being very particularly advantageous.

The fatty alcohols (D2) which can be used are saturated, mono- or polyunsaturated, branched or unbranched fatty alcohols with C ₆ -C ₃₀ , preferably C ₁₀ -C ₂ and very particularly preferably C12 -C ₂ carbon atoms. For the purposes of the invention, for example, decanol, octanol, octenol, dodecenol, decenol, octadienol, dodecadienol, decadienol, oleyl alcohol, eruca alcohol, ricinol alcohol, stearyl alcohol, isostearyl alcohol, cetyl alcohol, lauryl alcohol, myristyl alcohol, capryl alcohol, arachidyl alcohol, arachidyl alcohol, arachidyl alcohol, arachidyl alcohol , as well as their Guerbet alcohols, whereby this list is meant to be exemplary and not limiting. However, the fatty alcohols are derived from preferably natural fatty acids, and it can usually be assumed that they are obtained from the esters of the fatty acids by reduction. Also suitable according to the invention are those fatty alcohol cuts which are produced by reducing naturally occurring triglycerides such as beef tallow, palm oil, peanut oil, rape oil, cottonseed oil, soybean oil, sunflower oil and linseed oil or fatty acid esters formed from their transesterification products with corresponding alcohols, and thus represent a mixture of different fatty alcohols. Such substances are, for example, under the names Stenol ^® , for example Stenol ^® 1618 or Lanette ^® , for example Lanette ^® O or Lorol ^® , for example Lorol ^® C8, Lorol ^® C14, Lorol ^® C18, Lorol ^® C8-18, HD-Ocenol ^® , Crodacol ^® , e.g. Crodacol ^® CS, Novol ^® , Eutanol ^® G, Guerbitol ^® 16, Guerbitol ^® 18, Guerbitol ^® 20, Isofol ^® 12, Isofol ^® 16, Isofol ^® 24, Isofol ^® 36, Isocarb ^® 12, Isocarb ^® 16 or to buy Isocarb ^® 24. Of course, according to the invention, wool wax alcohols, such as those listed under the Drawings Corona ^® , White Swan ^® , Coronet ^® or Fluilan ^{® are} available for purchase. The fatty alcohols are used in amounts of 0.1-30% by weight, based on the entire preparation, preferably in amounts of 0.1

- 20 wt .-% used.

Solid paraffins or isoparaffins, carnauba waxes, beeswaxes, candelilla waxes, ozokerites, ceresin, walnut, sunflower wax, fruit waxes such as apple wax or citrus wax, microwaxes made of PE or PP can be used according to the invention as natural or synthetic waxes (D3). Such waxes are available, for example, from Kahl & Co., Trittau.

The amount used is 0.1-50% by weight, based on the total composition, preferably 0.1-20% by weight and particularly preferably 0.1-15% by weight, based on the overall composition.

The natural and synthetic cosmetic oil bodies (D4) which can increase the effect of the active ingredient complex (A) according to the invention include, for example:

- vegetable oils. Examples of such oils are sunflower oil, olive oil, soybean oil, rapeseed oil, almond oil, jojoba oil, orange oil, wheat germ oil, peach seed oil and the liquid components of coconut oil. Other triglyceride oils such as the liquid portions of beef tallow and synthetic triglyceride oils are also suitable.

liquid paraffin oils, isoparaffin oils and synthetic hydrocarbons and di-n-alkyl ethers with a total of between 12 to 36 carbon atoms, in particular 12 to 24 carbon atoms, such as, for example, di-n-octyl ether, di-n-decyl ether, di-n- nonyl ether, di-n-undecyl ether, di-n-dodecyl ether, n-hexyl-n-octyl ether, n-octyl-n-decyl ether, n-decyl-n-undecyl ether, n-undecyl-n-dodecyl ether and n-hexyl n-Undecyl ether and di-tert-butyl ether, di-iso-pentyl ether, di-3-ethyl decyl ether, tert-butyl-n-octyl ether, iso-pentyl-n-octyl ether and 2-methyl-pentyl-n-octyl ether. The compounds 1, 3- available as commercial products Di- (2-ethyl-hexyi) -cyclohexane (Cetiol ^® S), and di-n-octyl ether (Cetiol ^® OE) may be preferred. Ester oils. Ester oils are understood to be the esters of Ce - C ₃₀ fatty acids with C ₂ - C ₃₀ fatty alcohols. The monoesters of fatty acids with alcohols having 2 to 24 carbon atoms are preferred. Examples of fatty acid constituents used in the esters are caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linoleic acid, linoleic acid, linoleic acid, linostolic acid , Behenic acid and erucic acid and their technical mixtures, which are obtained, for example, in the pressure splitting of natural fats and oils, in the oxidation of aldehydes from Roelen's oxosynthesis or in the dimerization of unsaturated fatty acids. Examples of the fatty alcohol components in the ester oils are isopropyl alcohol, capron alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidolyl alcohol, elaidolyl alcohol, elaidol alcohol alcohol, elaidol alcohol alcohol Gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and their technical mixtures, which are obtained, for example, in the high-pressure hydrogenation of technical methyl esters based on fats and oils or aldehydes from Roelen's oxosynthesis and as a monomer fraction in the dimerization of unsaturated fatty alcohols. According to the invention, particular preference is given to isopropyl myristate (Rilanit ^® IPM), isononanoic acid C16-18 alkyl ester (Cetiol ^® SN), 2-ethylhexyl palmitate (Cegesoft ^® 24), stearic acid 2-ethylhexyl ester (Cetiol ^® 868), cetyl oleate, glycerol tricaprylate caprinate / caprylate (Cetiol ^® LC), n-butyl stearate, olerlerucate (Cetiol ^® J 600), isopropyl palmitate (Rilanit ^® IPP), oleyl oleat (Cetiol ^® ), lauric acid hexyl ester (Cetiol ^® A), di-n-butyl adipate (Cetiol ^® B), myristyl myristate (Cetiol ^® MM), cetearyl isononanoate (Cetiol ^® SN), oleic acid decyl ester (Cetiol ^® V). - Dicarboxylic acid esters such as di-n-butyl adipate, di- (2-ethylhexyl) adipate, di- (2-ethylhexyl) succinate and di-isotridecyl acelate as well as diol esters such as ethylene glycol dioleate, ethylene glycol di-isotridecanoate, propylene glycol di (2 ethylhexanoate), propylene glycol di-isostearate, propylene glycol di-pelargonate, butanediol di-isostearate, neopentyl glycol dicaprylate,

symmetrical, asymmetrical or cyclic esters of carbonic acid with fatty alcohols, for example described in DE-OS 197 56 454, glycerol carbonate or dicaprylyl carbonate (Cetiol ^® CC),

Trifatty acid esters of saturated and / or unsaturated linear and / or branched fatty acids with glycerol,

- Fatty acid partial glycerides are monoglycerides, diglycerides and their technical mixtures. When using technical products, small quantities of triglycerides may still be present due to the manufacturing process. The partial glycerides preferably follow the formula (D4-I),

CH ₂ O (CH ₂ CH ₂ O) _m R ¹

I CHO (CH ₂ CH ₂ O) _n R ² (D4-I)

I CH ₂ O (CH ₂ CH ₂ O) _q R ³

in which R ¹ , R ² and R ³ independently of one another represent hydrogen or a linear or branched, saturated and / or unsaturated acyl radical having 6 to 22, preferably 12 to 18, carbon atoms, with the proviso that at least one of these groups represents a Acyl radical and at least one of these groups represents hydrogen. The sum (m + n + q) represents 0 or numbers from 1 to 100, preferably 0 or 5 to 25. R ¹ preferably represents an acyl radical and R ² and R ^{3 represents} hydrogen and the sum (m + n + q) is 0. Typical examples are mono- and / or diglycerides based on caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, Linolenic acid, elaeostearic acid, arachic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures. Oleic acid monoglycerides are preferably used.

The amount of natural and synthetic cosmetic oil bodies used in the agents according to the invention is usually 0.1-30% by weight, based on the total agent, preferably 0.1-20% by weight, and in particular 0.1-15% by weight. %.

The total amount of oil and fat components in the agents according to the invention is usually 0.5-75% by weight, based on the total agent. Quantities of 0.5-35% by weight are preferred according to the invention.

The use of surfactants (E) in the agents according to the invention has proven to be particularly advantageous. In a further preferred embodiment, the agents according to the invention therefore contain surfactants. The term surfactants is understood to mean surface-active substances which form adsorption layers on surfaces and interfaces or which can aggregate in volume phases to form micelle colloids or lyotropic mesophases. A distinction is made between anionic surfactants consisting of a hydrophobic residue and a negatively charged hydrophilic head group, amphoteric surfactants, which carry both a negative and a compensating positive charge, cationic surfactants, which in addition to a hydrophobic residue have a positively charged hydrophilic group, and nonionic surfactants, which have no charges but strong dipole moments and are highly hydrated in aqueous solution.

The cationic surfactants have already been described above as a possible care substance. Suitable anionic surfactants (E1) in preparations according to the invention are all anionic surface-active substances suitable for use on the human body. These are characterized by a water-solubilizing, anionic group such as. B. a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group with about 8 to 30 carbon atoms. In addition, the molecule may contain glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups. 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 with 2 to 4 carbon 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 with 8 to 30 C atoms and x = 0 or 1 to 16,

Acyl sarcosides with 8 to 24 carbon atoms in the acyl group,

Acyl taurides with 8 to 24 carbon atoms in the acyl group,

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

Mono-dialkyl sulfosuccinic acid and dialkyl esters with 8 to 24 carbon atoms in the alkyl group and mono-alkyl polyoxyethyl sulfosuccinic acid with 8 to 24 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups,

linear alkanesulfonates with 8 to 24 carbon atoms,

- linear alpha olefin sulfonates with 8 to 24 carbon atoms,

- Alpha-sulfofatty acid methyl esters of fatty acids with 8 to 30 carbon atoms,

Alkyl sulfates and alkyl polyglycol ether sulfates of the formula RO (CH ₂ -CH ₂ O) _x -OSO ₃ H, in which R is a preferably linear alkyl group with 8 to 30 C atoms and x = 0 or 1 to 12,

- Sulphated hydroxyalkyl polyethylene and / or hydroxyalkylene propylene glycol ethers

- Sulfonates of unsaturated fatty acids with 8 to 24 carbon atoms and 1 to 6 double bonds

Esters of tartaric acid and citric acid with alcohols which are addition products of about 2-15 molecules of ethylene oxide and / or propylene oxide onto fatty alcohols having 8 to 22 carbon atoms, Alkyl and / or alkenyl ether phosphates of the formula (E1-I),

R ¹ (OCH ₂ CH ₂ ) _n -OP (O) (OX) -OR ² (EM)

in which R ^{1 is} preferably an aliphatic hydrocarbon radical having 8 to 30 carbon atoms, R ^{2 is} hydrogen, a radical (CH ₂ CH ₂ O) _n R ² or X, n is a number from 1 to 10 and X is hydrogen, an alkali or alkaline earth metal or NR ³ R ⁴ R ⁵ R ⁶ , with R ³ to R ⁶ independently of one another being hydrogen or a C ₁ to C ₄ hydrocarbon radical,

- sulfated fatty acid alkylene glycol esters of the formula (E 1-11) R ⁷ CO (AlkO) _n SO ₃ M (EMI) in the R ⁷ CO- for a linear or branched, aliphatic, saturated and / or unsaturated acyl radical with 6 to 22 C- Atoms, Alk represents CH ₂ CH ₂ , CHCH ₃ CH ₂ and / or CH ₂ CHCH ₃ , n represents numbers from 0.5 to 5 and M represents a cation,

- Monoglyceride sulfates and monoglyceride ether sulfates of the formula (E1-III)

CH ₂ O (CH ₂ CH ₂ O) _x -COR ⁸

I CHO (CH ₂ CH ₂ O) _y H (EMII)

I CH ₂ O (CH ₂ CH ₂ O) _Z SO ₃ X

in which R ⁸ CO stands for a linear or branched acyl radical with 6 to 22 carbon atoms, x, y and z in total for O or for numbers from 1 to 30, preferably 2 to 10, and X stands for an alkali or alkaline earth metal. Typical examples of monoglyceride (ether) sulfates which are suitable for the purposes of the invention are the reaction products of lauric acid monoglyceride, coconut fatty acid monoglyceride, palmitic acid monoglyceride, stearic acid monoglyceride, oleic acid monoglyceride and tallow fatty acid monoglyceride as well as their ethylene oxide adducts with their sulfur trioxide adducts in their sulfuric oxide adducts with sulfuric oxide adducts with their sulfur trioxide adduct in their form of sulfur trioxide. Preferably be Monoglyceride sulfates of the formula (E1-III) used in which R ⁸ CO represents a linear acyl radical having 8 to 18 carbon atoms,

Amidether carboxylic acids,

- Condensation products from C ₈ - C30 fatty alcohols with protein hydrolyzates and / or amino acids and their derivatives, which are known to the person skilled in the art as protein fatty acid condensates, such as, for example, the Lamepon ^® types, Gluadin ^® types, Hostapon ^® KCG or the Amisoft ^® types.

Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids with 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule, sulfosuccinic acid and dialkyl esters with 8 to 18 carbon atoms in the alkyl group and sulfosuccinic acid mono-alkylpolyoxyethyl ester with 8 up to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups, monoglycer disulfates, alkyl and alkenyl ether phosphates as well as protein fatty acid condensates.

Zwitterionic surfactants (E2) are those surface-active compounds which carry at least one quaternary ammonium group and at least one -COO ^("} - or -SO3 ^W group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl N, N-dimethylammonium glycinate, for example the coconut alkyl dimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammonium glycinate, for example the coconut acylaminopropyl dimethylammonium glycinate, and 2-alkyl-3-car-boxymethyl-3-hydroxyethyl imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and cocosacylaminoethylhydroxyethylcarboxymethylglycinate A preferred zwitterionic surfactant is the fatty acid amide derivative known under the INCI name Cocamidopropyl Betaine.

Ampholytic surfactants (E3) are understood to mean those surface-active compounds which, in addition to a C ₈ -C 24 alkyl or acyl group, contain at least one free amino group and at least one -COOH or -SO ₃ H group in the molecule and for training inner salts are capable. examples for Suitable ampholytic 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 with about 8 to 24 C. Atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-coconut alkyl aminopropionate, coconut acylaminoethyl aminopropionate and C12-C- _t β-acyl sarcosine.

Nonionic surfactants (E4) contain e.g. a polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether groups. Such connections are, for example

- Adducts of 2 to 50 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide with linear and branched fatty alcohols with 8 to 30 C atoms, with fatty acids with 8 to 30 C atoms and with alkylphenols with 8 to 15 C atoms in the alkyl group,

- Adducts of 2 to 50 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide which are end group-capped with a methyl or C ₂ -C ₆ -alkyl radical and linear and branched fatty alcohols with 8 to 30 C atoms, and fatty acids with 8 to 30 C- atoms and onto alkylphenols having 8 to 15 C-Ato¬ men in the alkyl group, such as the type available under the commercial names Dehydol ^® LS, Dehydol ^® LT (Cognis),

C ₁₂ -C ₃₀ fatty acid monoesters and diesters of adducts of 1 to 30 moles of ethylene oxide with glycerol,

Adducts of 5 to 60 moles of ethylene oxide with castor oil and hardened castor oil,

- polyol, such as the commercially available product ^® Hydagen HSP (Cognis) or Sovermol - types (Cognis),

- alkoxylated triglycerides,

alkoxylated fatty acid alkyl esters of the formula (E4-I) R ¹ CO- (OCH ₂ CHR ² ) _W OR ³ (E4-I)

in which R ¹ CO represents a linear or branched, saturated and / or unsaturated acyl radical having 6 to 22 carbon atoms, R ^{2 represents} hydrogen or methyl, R ^{3 represents} linear or branched alkyl radicals having 1 to 4

Carbon atoms and w represents numbers from 1 to 20,

Amine oxides,

Hydroxy mixed ether,

Sorbitan fatty acid esters and addition products of ethylene oxide

Sorbitan fatty acid esters such as the polysorbates,

Sugar fatty acid esters and addition products of ethylene oxide

Sugar fatty acid esters,

Addition products of ethylene oxide with fatty acid alkanolamides and

Fatty amines,

Sugar surfactants of the alkyl and alkenyl oligoglycoside type according to the formula

(E4-II),

R ⁴ O- [G] _P (E4-II)

in which R ^{4 represents} an alkyl or alkenyl radical having 4 to 22 carbon atoms, G represents a sugar radical having 5 or 6 carbon atoms and p represents numbers from 1 to 10. They can be obtained according to the relevant procedures in preparative organic chemistry.

The alkyl and alkenyl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably from glucose. The preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides. The index number p in the general formula (E4-II) indicates the degree of oligomerization (DP), ie the distribution of mono- and OH-goglycosides, and stands for a number between 1 and 10. While p in the individual molecule must always be an integer and here can assume the values p = 1 to 6, the value p is for a particular alkyl oligoglycoside an analytically calculated quantity, which usually represents a fractional number. Alkyl and / or alkenyl oligoglycosides with an average degree of oligomerization p of 1.1 to 3.0 are preferably used. From an application point of view, preference is given to those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4. The alkyl or alkenyl radical R ⁴ can be derived from primary alcohols having 4 to 11, preferably 8 to 10, carbon atoms. Typical examples are butanol, capronic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, as are obtained, for example, from hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis. Alkyl oligoglucosides of chain length C ₈ -Ci ₀ (DP = 1 to 3) are preferred, which are obtained as a preliminary step in the separation of technical C ₈ -Ci ₈ coconut fatty alcohol by distillation and with a proportion of less than 6% by weight Ci ₂ -Alcohol may be contaminated and alkyl oligoglucosides based on technical Cg _/ n-oxo alcohols (DP = 1 to 3). The alkyl or alkenyl radical R ¹⁵ can also be derived from primary alcohols having 12 to 22, preferably 12 to 14, carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol and their technical mixtures, which can be obtained as described above. Alkyl oligoglucosides based on hydrogenated C ₂ / i4 coconut alcohol with a DP of 1 to 3. Sugar surfactants of the type preferred are fatty acid-N-alkylpolyhydroxyalkylamides, a nonionic surfactant of formula (E4-III),

R ⁵ CO-NR ⁶ - [Z] (E4-III)

in which R ⁵ CO is an aliphatic acyl radical having 6 to 22 carbon atoms, R ^{6 is} hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 Carbon atoms and [Z] represents a linear or branched polyhydroxyalkyl radical having 3 to 12 carbon atoms and 3 to 10 hydroxyl groups. The fatty acid N-alkylpolyhydroxyalkylamides are known substances which are usually obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride. The fatty acid N-alkylpolyhydroxyalkylamides are preferably derived from reducing sugars with 5 or 6 carbon atoms, in particular from glucose. The preferred fatty acid N-alkylpolyhydroxyalkylamides are therefore fatty acid N-alkylglucamides as represented by the formula (E4-IV):

R ⁷ CO-NR ⁸ -CH ₂ - (CHOH) ₄ -CH ₂ OH (E4-IV)

The fatty acid N-alkylpolyhydroxyalkylamides used are preferably glucamides of the formula (E4-IV) in which R ^{8 is} hydrogen or an alkyl group and R ⁷ CO is the acyl radical of caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmoleic acid, Stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, arachic acid, gadoleic acid, behenic acid or erucic acid or their technical mixtures. Fatty acid N-alkylglucamides of the formula (E4-IV) which are obtained by reductive amination of glucose with methylamine and subsequent acylation with lauric acid or C12 / 14 coconut fatty acid or a corresponding derivative are particularly preferred. Furthermore, the polyhydroxyalkylamides can also be derived from maltose and palatinose.

The alkylene oxide adducts with saturated linear fatty alcohols and fatty acids, each with 2 to 30 moles of ethylene oxide per mole of fatty alcohol or fatty acid, have proven to be preferred nonionic surfactants. Preparations with excellent properties are also obtained if they contain fatty acid esters of ethoxylated glycerol as nonionic surfactants.

These connections are characterized by the following parameters. The alkyl radical R contains 6 to 22 carbon atoms and can be either linear or branched. Primary linear and methyl-branched aliphatic radicals in the 2-position are preferred. Such alkyl radicals are, for example, 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl and 1-stearyl. 1-Octyl, 1-decyl, 1-lauryl, 1-myristyl are particularly preferred. When so-called "oxo alcohols" are used as starting materials, compounds with an odd number of carbon atoms in the alkyl chain predominate.

Furthermore, very particularly preferred nonionic surfactants are the sugar surfactants. These can be present in the agents used according to the invention preferably in amounts of 0.1-20% by weight, based on the total agent. Amounts of 0.5-15% by weight are preferred, and amounts of 0.5-7.5% by weight are very particularly preferred.

The compounds with alkyl groups used as surfactant can each be uniform substances. However, it is generally preferred to start from natural vegetable or animal raw materials in the production of these substances, so that mixtures of substances with different alkyl chain lengths depending on the respective raw material are obtained.

In the case of the surfactants, which are addition products of ethylene and / or propylene oxide onto fatty alcohols or derivatives of these addition products, both products with a "normal" homolog distribution and those with a narrowed homolog distribution can be used. “Normal” homolog distribution is understood to mean mixtures of homologs which are obtained as catalysts when fatty alcohol and alkylene oxide are reacted using alkali metals, alkali metal hydroxides or alkali metal alcoholates. On the other hand, narrow homolog distributions are obtained if for example hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates can be used as catalysts. The use of products with a narrow homolog distribution can be preferred.

The surfactants (E) are used in amounts of 0.1-45% by weight, preferably 0.5-30% by weight and very particularly preferably 0.5-25% by weight, based on the total agent used according to the invention .

Anionic, nonionic, zwitterionic and / or amphoteric surfactants and mixtures thereof can be preferred according to the invention.

In a further preferred embodiment, the agents according to the invention can contain emulsifiers (F). Emulsifiers cause water or oil-stable adsorption layers to form at the phase interface, which protect the dispersed droplets against coalescence and thus stabilize the emulsion. Like surfactants, emulsifiers are therefore made up of a hydrophobic and a hydrophilic part of the molecule. Hydrophilic emulsifiers preferably form O / W emulsions and hydrophobic emulsifiers preferably form W / O emulsions. An emulsion is to be understood as a droplet-like distribution (dispersion) of a liquid in another liquid with the use of energy to create stabilizing phase interfaces by means of surfactants. The selection of these emulsifying surfactants or emulsifiers is based on the substances to be dispersed and the particular external phase as well as the fine particle size of the emulsion. Emulsifiers which can be used according to the invention are, for example

Addition products of 4 to 30 mol of ethylene oxide and / or 0 to 5 mol of propylene oxide with linear fatty alcohols with 8 to 22 C atoms, with fatty acids with 12 to 22 C atoms and with alkylphenols with 8 to 15 C atoms in the alkyl group, Ci2-C22 fatty acid monoesters and diesters of adducts of 1 to 30 moles of ethylene oxide with polyols with 3 to 6 carbon atoms, in particular with glycerol,

- Ethylene oxide and polyglycerol adducts with methyl glucoside fatty acid esters, fatty acid alkanolamides and fatty acid glucamides,

C ₈ -C ₂ 2 -alkyl mono- and oligoglycosides and their ethoxylated analogs, degrees of oligomerization of 1.1 to 5, in particular 1.2 to 2.0, and glucose as the sugar component being preferred,

Mixtures of alkyl (oligo) glucosides and fatty alcohols, for example the commercially available product Montanov ^® 68,

Adducts of 5 to 60 moles of ethylene oxide with castor oil and hardened castor oil,

Partial esters of polyols with 3-6 carbon atoms with saturated fatty acids with 8 to 22 C atoms,

- sterols. Sterols are understood to be a group of steroids which carry a hydroxyl group on the C atom 3 of the steroid structure and are isolated both from animal tissue (zoosterols) and from vegetable fats (phytosterols). Examples of zoosterols are cholesterol and lanosterol. Examples of suitable phytosterols are ergosterol, stigmasterol and sitosterol. Sterols, the so-called mycosterols, are also isolated from mushrooms and yeasts.

- phospholipids. These include primarily the glucose phospholipids, e.g. as lecithins or phosphididylcholines from e.g. Egg yolks or plant seeds (e.g. soybeans) are understood.

Fatty acid esters of sugars and sugar alcohols, such as sorbitol,

- polyglycerols and polyglycerol derivatives such as Polyglycerinpoly- 12-hydroxystearate (commercial product Dehymuls ^® PGPH),

- Linear and branched fatty acids with 8 to 30 C atoms and their Na, K, ammonium, Ca, Mg and Zn salts. The agents according to the invention preferably contain the emulsifiers in amounts of 0.1-25% by weight, in particular 0.5-15% by weight, based on the total agent.

The compositions according to the invention can preferably contain at least one nonionic emulsifier with an HLB value of 8 to 18. Nonionic emulsifiers with an HLB value of 10-15 can be particularly preferred according to the invention.

It has also proven to be advantageous if polymers (G) are present in the agents according to the invention. In a preferred embodiment, polymers are therefore added to the agents used according to the invention, both cationic, anionic, amphoteric and nonionic polymers having proven to be effective.

Cationic polymers have already been described above as a possibility for care substances.

The anionic polymers (G2) are anionic polymers which have carboxylate and / or sulfonate groups. Examples of anionic monomers from which such polymers can consist are acrylic acid, methacrylic acid, crotonic acid, maleic anhydride and 2-acrylamido-2-methylpropanesulfonic acid. The acidic groups can be present in whole or in part as sodium, potassium, ammonium, mono- or triethanolammonium salt. Preferred monomers are 2-acrylamido-2-methylpropanesulfonic acid and acrylic acid.

Anionic polymers which contain 2-acrylamido-2-methylpropanesulfonic acid as the sole or co-monomer have proven to be very particularly effective, the sulfonic acid group being able to be present in whole or in part as the sodium, potassium, ammonium, mono- or triethanolammonium salt . More preferably, the homopolymer of 2-acrylamido-2-methyl propane sulfonic acid is obtainable for example under the name Rheothik ^® 11-80 commercially.

In this embodiment, it may be preferred to use copolymers of at least one anionic monomer and at least one nonionic monomer. With regard to the anionic monomers, reference is made to the substances listed above. Preferred nonionic monomers are acrylamide, methacrylamide, acrylic acid esters, methacrylic acid esters,

Vinyl pyrrolidone, vinyl ether and vinyl ester.

Preferred anionic copolymers are acrylic acid-acrylamide copolymers and in particular polyacrylamide copolymers with monomers containing sulfonic acid groups. A particularly preferred anionic copolymer consists of 70 to 55 mol% of acrylamide and 30 to 45 mol% of 2-acrylamido-2-methylpropanesulfonic acid, the sulfonic acid group being wholly or partly as sodium, potassium, ammonium, mono- or triethanolammonium Salt is present. This copolymer can also be crosslinked, the preferred crosslinking agents being polyolefinically unsaturated compounds such as tetraallyloxyethane, allyl sucrose, allylpentaerythritol and methylene bisacrylamide. Such a polymer is contained in the commercial product Sepigel ^® 305 from SEPPIC. The use of this compound, which in addition to the polymer component contains a hydrocarbon mixture (Ci ₃ -Ci4-isoparaffin) and a nonionic emulsifier (Laureth-7), has proven to be particularly advantageous in the context of the teaching according to the invention.

Also, as a compound with isohexadecane and sold under the name Simulgel ^® 600 Polysorbate-80 sodium acryloyldimethyltaurate copolymers have proven effective as in the present invention particularly.

Also preferred anionic homopolymers are uncrosslinked and crosslinked polyacrylic acids. Allyl ethers of pentaerythritol, sucrose and Propylene may be preferred cross-linking agents. Such compounds are for example available under the trademark Carbopol ^® commercially.

Copolymers of maleic anhydride and methyl vinyl ether, especially those with crosslinks, are also color-preserving polymers. A cross-linked with 1, 9-Decadiene-maleic acid methyl vinyl ether copolymer is available under the name Stabileze® ^® QM.

Furthermore, amphoteric polymers (G3) can be used as polymers to increase the action of the active ingredient complex (A) according to the invention. The term amphoteric polymers includes both those polymers which contain both free amino groups and free --COOH or SO ₃ H groups in the molecule and are capable of forming internal salts, and also zwitterionic polymers which contain quaternary ammonium groups and -COO ^" - or -SO ₃ ^' groups, and summarized those polymers which contain -COOH or SO ₃ H groups and quaternary ammonium groups.

An example of the present invention amphopolymer suitable is that available under the name Amphomer ^® acrylic resin which is a copolymer of tert-butylaminoethyl methacrylate, N- (1, 1, 3,3-tetramethylbutyl) -acrylamide and two or more monomers from the group of acrylic acid, Methacrylic acid and its simple esters.

Amphoteric polymers which are preferably used are those polymers which essentially consist of one another

(a) Monomers with quaternary ammonium groups of the general formula

(G3-I),

R ¹ -CH = CR ² -CO-Z- (C _n H ₂ n) -N ⁽⁺⁾ R ³ R ⁴ R ⁵ A ^H (G3-I) in which R ¹ and R ² independently of one another are hydrogen or a methyl group and R ³ , R ⁴ and R ⁵ independently of one another are alkyl groups with 1 to 4 carbon atoms, Z is an NH group or an oxygen atom, n is an integer from 2 to 5 and A is the anion of an organic or inorganic acid, and

(b) monomeric carboxylic acids of the general formula (G3-II),

R ⁶ -CH = CR ⁷ -COOH (G3-II)

in which R ⁶ and R ^{7 are} independently hydrogen or methyl groups.

According to the invention, these compounds can be used both directly and in salt form, which is obtained by neutralizing the polymers, for example with an alkali metal hydroxide. Those polymers in which monomers of type (a) are used, in which R ³ , R ⁴ and R ^{5 are} methyl groups, Z is an NH group and A ^ is a halide, methoxysulfate or ethoxysulfate ion, are very particularly preferred ; Acrylamidopropyltrimethylammonium chloride is a particularly preferred monomer (a). Acrylic acid is preferably used as monomer (b) for the polymers mentioned.

In a further embodiment, the agents according to the invention can contain nonionic polymers (G4).

Suitable nonionic polymers are for example:

Vinylpyrrolidone / Vinylester copolymers, as are marketed, for example under the trademark Luviskol ^® (BASF). Luviskol ^® VA 64 and Luviskol ^® VA 73, each vinylpyrrolidone / vinyl acetate copolymers, are also preferred nonionic polymers.

Cellulose ethers, such as hydroxypropyl cellulose, hydroxyethyl cellulose and methyl hydroxypropyl cellulose, such as those available under the Culminal ^® and Benecel ^® (AQUALON) and Natrosol ^® types (Hercules).

Starch and its derivatives, in particular starch ethers, for example Structure ^® XL (National Starch), a multifunctional, salt-tolerant starch;

- Shellac

- polyvinylpyrrolidones, as, for example, sold under the name Luviskol ^® (BASF).

- siloxanes. These siloxanes can be both water-soluble and water-insoluble. Both volatile and non-volatile siloxanes are suitable, non-volatile siloxanes being understood to be those compounds whose boiling point at normal pressure is above 200 ^° C. Preferred siloxanes are polydialkylsiloxanes, such as, for example, polydimethylsiloxane, polyalkylarylsiloxanes, such as, for example, polyphenylmethylsiloxane, ethoxylated polydialkylsiloxanes and polydialkylsiloxanes which contain amine and / or hydroxyl groups.

- Glycosidically substituted silicones.

It is also possible according to the invention that the preparations used contain several, in particular two different polymers of the same charge and / or each contain an ionic and an amphoteric and / or non-ionic polymer.

The polymers (G) are preferably present in the agents according to the invention in amounts of 0.05 to 10% by weight, based on the total agent. Amounts from 0.1 to 5, in particular from 0.1 to 3% by weight are particularly preferred.

Furthermore, in a preferred embodiment of the invention, an agent according to the invention can also contain UV filters (I). The structure and physical properties of the UV filters to be used according to the invention are not subject to any general restrictions. Rather, all UV filters that can be used in the cosmetics sector are suitable Absorption maximum in the UVA (315-400 nm) -, in the UVB (280-315nm) - or in the UVC (<280 nm) range. UV filters with an absorption maximum in the UVB range, in particular in the range from approximately 280 to approximately 300 nm, are particularly preferred.

The UV filters used according to the invention can be selected, for example, from substituted benzophenones, p-aminobenzoic acid esters, diphenylacrylic acid esters, cinnamic acid esters, salicylic acid esters, benzimidazoles and o-aminobenzoic acid esters.

Examples of UV filters which can be used according to the invention are 4-amino-benzoic acid, N ₎ N, N-trimethyl-4- (2-oxobom-3-ylidenemethyl) aniline methyl sulfate, 3,3,5-trimethylcyclohexyl salicylate (homosalates), 2-hydroxy-4-methoxy-benzophenone

(Benzophenone-3; Uvinul ^® M 40, Uvasorb ^® MET, Neo Heliopan ^® BB, Eusolex ^® 4360), 2-phenylbenzimidazole-5-sulfonic acid and its potassium, sodium and triethanolamine salts (phenylbenzimidazole sulfonic acid; Parsol ^® HS; Neo Heliopan ^® Hydro), 3,3 '- (1,4-phenylenedimethylene) -bis (7,7-dimethyl-2-oxobicyclo- [2.2.1] hept-1-yl-methanesulfonic acid) and their salts , 1- (4-tert-butylphenyl) -3- (4-methoxyphenyl) propane-1, 3-dione (butyl methoxydi- benzoylmethane; Parsol ^® 1789 Eusolex ^® 9020), α- (2-oxoborn-3 -ylidene) -toluene-4-sulfonic acid and its salts, ethoxylated 4-aminobenzoic acid ethyl ester (PEG-25 PABA; Uvinul ^® P 25), 4-dimethylaminobenzoic acid 2-ethylhexyl ester (octyl dimethyl PABA; Uvasorb ^® DMO, Escalol ^® 507 , Eusolex ^® 6007), 2-ethylhexyl salicylic acid (octyl salicylate; Escalol ^® 587, Neo Heliopan ^® OS, Uvinul ^® O18), isopentyl 4-methoxycinnamate (isoamyl p-methoxycinnamate; Neo Heliopan ^® E 1000), 4-methoxycinnamic acid -2-ethylhexyl ester (octyl methoxycinnamate; Parsol ^® MCX, Escalol ^® 557, Neo Heliopan ^® AV), 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its sodium salt (benzophenone-4; Uvinul ^® MS 40; Uvasorb ^® S 5), 3- (4'-methylbenzylidene) -D, L-camphor (4-methylbenzylidene camphor; Parsol ^® 5000, Eusolex ^® 6300), 3-benzylidene camphor (3-benzylidene camphor), 4 -Isopropylbenzylsalicylat, 2,4,6-trianilino- (p-carbo-2'-ethylhexyl-1'-oxi) -1, 3,5-triazine, 3-imidazol-4-yl-acrylic acid and its ethyl ester, polymers of N - {(2 and 4) - [2-oxoborn-3-ylidenemethyl] benzyl} - acrylamids, 2,4-dihydroxybenzophenone (Benzophenone-1; Uvasorb ^® 20 H, Uvinul ^® 400), 1, 1 '-diphenylacrylonitrile acid 2-θthylhexyl ester (octocrylene; Eusolex ^® OCR, Neo Heliopan ^® Type 303, Uvinul ^® N SG 539), o-aminobenzoic benzoic acid menthyl (menthyl Anthranilate; Neo Heliopan MA ^®), 2,2 ', 4,4'-tetrahydroxy benzophenone (benzophenone-2; Uvinul ^® D-50), 2,2'-dihydroxy -4,4'-dimethoxybenzophenone (Benzophenone-6), 2,2'-dihydroxy-4,4'-dimethoxybenzophenone-5-sodium sulfonate and 2-cyano-3,3-diphenylacrylic acid 2'-ethylhexyl ester. 4-Amino-benzoic acid, N, N, N-trimethyl-4- (2-oxobom-3-ylidenemethyl) aniline-methyl sulfate, 3,3,5-trimethyl-cyclohexylsalicylate, 2-hydroxy-4-methoxy-benzophenone are preferred , 2-phenylbenzimidazole-5-sulfonic acid and its potassium, sodium and triethanolamine salts, 3,3 '- (1,4-phenylenedimethylene) - bis (7,7-dimethyl-2-oxobicyclo- [2.2.1] hept-1-yl-methanesulfonic acid) and their salts, 1- (4-tert-butylphenyl) -3- (4-methoxyphenyl) propane-1,3-dione, α- (2-oxoborn-3- ylidene) -toluene-4-sulfonic acid and its salts, ethoxylated ethyl 4-aminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-ethylhexyl salicylate, isopentyl 4-methoxycinnamate, 4-

2-ethylhexyl methoxycinnamate, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its sodium salt, 3- (4'-methylbenzylidene) -D, L-camphor, 3-benzylidene-camphor, 4-isopropylbenzyl salicylate, 2, 4,6-Trianilino- (p-carbo-2 '~ ethylhexyl-1' -oxy) -1, 3,5-triazine, 3-imidazol-4-yl-acrylic acid and its ethyl ester, polymers of N - {(2nd and 4) - [2-oxoborn-3-ylidenemethyl] benzyl} acrylamide. According to the invention, 2-hydroxy-4-methoxybenzophenone, 2-phenylbenzimidazole-5-sulfonic acid and their potassium, sodium and triethanolamine salts, 1 - (4-tert-butylphenyl) -3- (4- methoxyphenyl) propane-1,3-dione, 4-methoxycinnamic acid-2-ethylhexyl ester and 3- (4'-methylbenzylidene) -D, L-camphor.

Preferred UV filters are those whose molar extinction coefficient at the absorption maximum is above 15,000, in particular above 20,000.

Furthermore, it was found that in structurally similar UV filters, the water-insoluble compound in many cases within the scope of the invention Teaching has the higher effect compared to those water-soluble compounds that differ from it by one or more additional ionic groups. Within the scope of the invention, water-insoluble are UV filters which do not dissolve in water at 20 ^° C. to an extent of more than 1% by weight, in particular not more than 0.1% by weight. Furthermore, these compounds should be at least 0.1, in particular at least 1% by weight soluble in conventional cosmetic oil components at room temperature). The use of water-insoluble UV filters can therefore be preferred according to the invention.

According to a further embodiment of the invention, those UV filters are preferred which have a cationic group, in particular a quaternary ammonium group.

These UV filters have the general structure U - Q.

The structural part U stands for a group that absorbs UV rays. These

In principle, a group can be derived from the known UV filters mentioned above, which can be used in the cosmetics sector, in which a group in which

Usually a hydrogen atom, the UV filter is replaced by a cationic group Q, in particular with a quaternary amino function.

Connections from which the structural part U can be derived are, for example

- substituted benzophenones,

p-aminobenzoic acid ester,

- diphenylacrylic acid ester,

- cinnamic acid esters,

- salicylic acid esters,

- benzimidazoles and

o-aminobenzoic acid esters. Structural parts U which are derived from cinnamic acid amide or from N, N-dimethylaminobenzoic acid amide are preferred according to the invention.

The structural parts U can in principle be selected so that the absorption maximum of the UV filter can be both in the UVA (315-400 nm) - and in the UVB (280-315nm) - or in the UVC (<280 nm) range. UV filters with an absorption maximum in the UVB range, in particular in the range from approximately 280 to approximately 300 nm, are particularly preferred.

Furthermore, the structural part U, also depending on the structural part Q, is preferably selected such that the molar extinction coefficient of the UV filter at the absorption maximum is above 15,000, in particular above 20,000.

The structural part Q preferably contains a quaternary ammonium group as the cationic group. In principle, this quaternary ammonium group can be directly connected to the structural part U, so that the structural part U represents one of the four substituents of the positively charged nitrogen atom. However, one of the four substituents on the positively charged nitrogen atom is preferably a group, in particular an alkylene group having 2 to 6 carbon atoms, which functions as a connection between the structural part U and the positively charged nitrogen atom.

Advantageously, the group Q has the general structure - (CH ₂ ) _X -N ⁺ R ¹ R ² R ³ X ^' , in which x represents an integer from 1 to 4, R ¹ and R ² independently of one another represent Ci ₄ alkyl groups, R ³ represents a Ci. ₂₂ alkyl group or a benzyl group and X ^' for a physiologically acceptable anion. Within the framework of this general structure, x preferably stands for the number 3, R ¹ and R ² each for a methyl group and R ³ either for a methyl group or a saturated or unsaturated, linear or branched hydrocarbon chain with 8 to 22, in particular 10 to 18, Carbon atoms. Physiologically compatible anions are, for example, inorganic anions such as halides, in particular chloride, bromide and fluoride, sulfate ions and phosphate ions, and organic anions such as lactate, citrate, acetate, tartrate, methosulfate and tosylate.

Two preferred UV filters with cationic groups are the commercially obtainable compounds Zimtsäureamidopropyl- trimethylammonium chloride (lncroquat ^® UV-283) and dodecyl tosylate (Escalol ^® HP 610).

Of course, the teaching according to the invention also includes the use of a combination of several UV filters. In the context of this embodiment, the combination of at least one water-insoluble UV filter with at least one UV filter with a cationic group is preferred.

The UV filters (I) are usually contained in the agents used according to the invention in amounts of 0.1-5% by weight, based on the total agent. Amounts of 0.4-2.5% by weight are preferred.

The agents according to the invention can also contain a 2-pyrrolidinone-5-carboxylic acid and its derivatives (J). Preferred are the sodium, potassium, calcium, magnesium or ammonium salts in which the ammonium ion carries one to three d to C ₄ alkyl groups in addition to hydrogen. The sodium salt is very particularly preferred. The amounts used in the agents according to the invention are preferably 0.05 to 10% by weight, based on the total agent, particularly preferably 0.1 to 5, and in particular 0.1 to 3% by weight.

Finally, the agents according to the invention can also contain plant extracts (L). These extracts are usually produced by extracting the entire plant. In individual cases, however, it may also be preferred to produce the extracts exclusively from flowers and / or leaves of the plant.

With regard to the plant extracts which can be used according to the invention, reference is made in particular to the extracts which are listed in the table beginning on page 44 of the 3rd edition of the guide to the declaration of ingredients of cosmetic products, published by the Industry Association for Personal Care and Detergents (IKW), Frankfurt.

According to the invention, the extracts from green tea, oak bark, nettle, witch hazel, hops, henna, chamomile, burdock root, horsetail, hawthorn, linden flowers, almond, aloe vera, spruce needles, horse chestnut, sandalwood, juniper, coconut, mango, apricot, lime , Wheat, kiwi, melon, orange, grapefruit, sage, rosemary, birch, mallow, cuckoo flower, quendel, yarrow, thyme, lemon balm, hake, coltsfoot, marshmallow, meristem, ginseng and ginger root preferred.

The extracts from green tea, oak bark, nettle, witch hazel, hops, chamomile, burdock root, horsetail, linden flowers, almond, aloe vera, coconut, mango, apricot, lime, wheat, kiwi, melon, orange, grapefruit, sage, are particularly preferred. Rosemary, birch, cuckoo flower, quendel, yarrow, harrow, meristem, ginseng and ginger root.

The extracts from green tea, almond, aloe vera, coconut, mango, apricot, lime, wheat, kiwi and melon are particularly suitable for the use according to the invention.

Water, alcohols and mixtures thereof can be used as extractants for the production of the plant extracts mentioned. Among the alcohols are lower alcohols such as ethanol and isopropanol, but in particular polyhydric alcohols such as ethylene glycol and propylene glycol, preferred both as the sole extractant and in a mixture with water. Plant extracts based on water / propylene glycol in a ratio of 1:10 to 10: 1 have proven to be particularly suitable.

According to the invention, the plant extracts can be used both in pure and in diluted form. If they are used in diluted form, they usually contain about 2 to 80% by weight of active substance and, as a solvent, the extractant or mixture of extractants used in their extraction.

Furthermore, it may be preferred to use mixtures of several, in particular two, different plant extracts in the agents according to the invention.

In addition, it can prove to be advantageous if the agents according to the invention contain penetration aids and / or swelling agents (M). These include, for example, urea and urea derivatives, guanidine and its derivatives, arginine and its derivatives, water glass, imidazole and its derivatives, histidine and its derivatives, benzyl alcohol, glycerol, glycol and glycol ethers, propylene glycol and propylene glycol ethers, for example propylene glycol monoethyl ether, carbonates, hydrogen carbonates, Diols and triols, and in particular 1,2-diols and 1,3-diols such as, for example, 1,2-propanediol, 1,2-pentanediol, 1,2-hexanediol, 1,2-dodecanediol, 1,3-propanediol, 1st , 6-hexanediol, 1,5-pentanediol, 1,4-butanediol.

Advantageously in the sense of the invention, short-chain carboxylic acids (N) can additionally support the active ingredient complex (A). Short-chain carboxylic acids and their derivatives for the purposes of the invention are understood to mean carboxylic acids which can be saturated or unsaturated and / or straight-chain or branched or cyclic and / or aromatic and / or heterocyclic and have a molecular weight of less than 750. Saturated or unsaturated straight-chain or branched carboxylic acids can be preferred for the purposes of the invention with a chain length of 1 to 16 carbon atoms in the chain, very particularly preferred are those with a chain length of 1 to 12 carbon atoms in the chain.

The short-chain carboxylic acids in the sense of the invention can have one, two, three or more carboxy groups. For the purposes of the invention, preference is given to carboxylic acids having several carboxy groups, in particular di- and tricarboxylic acids. The carboxy groups can be present in whole or in part as an ester, acid anhydride, lactone, amide, imidic acid, lactam, lactim, dicarboximide, carbohydrazide, hydrazone, hydroxam, hydroxime, amidine, amidoxime, nitrile, phosphonic or phosphate ester. The carboxylic acids according to the invention can of course be substituted along the carbon chain or the ring structure. The substituents of the carboxylic acids according to the invention include, for example, C1-C8-alkyl, C2-C8-alkenyl, aryl, aralkyl and aralkenyl, hydroxymethyl, C2-C8-hydroxyalkyl, C2-C8-hydroxyalkenyl, Aminomethyl, C2-C8 aminoalkyl, cyano, formyl, oxo, thioxo, hydroxyl, mercapto, amino, carboxy or imino groups. Preferred substituents are C1-C8-alkyl, hydroxymethyl, hydroxy, amino and carboxy groups. Substituents in the D position are particularly preferred. Very particularly preferred substituents are hydroxyl, alkoxy and amino groups, where the amino function can optionally be further substituted by alkyl, aryl, aralkyl and / or alkenyl radicals. Furthermore preferred carbonic acid derivatives are the phosphonic and phosphate esters.

Examples of carboxylic acids according to the invention include formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, glyceric acid, glyoxylic acid, adipic acid, pimelic acid, suberic acid, azocanoic acid, sebrotonic acid, sebacic acid , Elaidic acid, maleic acid, fumaric acid, muconic acid, citraconic acid, mesaconic acid, camphoric acid, benzoic acid, o, m, p-phthalic acid, naphthoic acid, toluoyl acid, hydratropic acid, atropic acid, Cinnamic acid, isonicotinic acid, nicotinic acid, Bicarbaminsäure, 4,4 ^{'-Dicyano- 6,6'} -binicotinsäure, 8-Carbamoyloctansäure, 1, 2,4-pentanetricarboxylic acid, 2-pyrrolecarboxylic acid, 1, 2,4,6, 7-Napthalinpentaessigsäure,

Malonaldehyde acid, 4-hydroxy-phthalamic acid, 1-pyrazole carboxylic acid, gallic acid or propane tricarboxylic acid, a dicarboxylic acid selected from the group formed by compounds of the general formula (N-I),

(N-I)

in the Z stands for a linear or branched alkyl or alkenyl group with 4 to 12 carbon atoms, n for a number from 4 to 12 and one of the two groups X and Y for a COOH group and the other for hydrogen or a methyl or Ethyl radical, dicarboxylic acids of the general formula (NI) which additionally carry 1 to 3 methyl or ethyl substituents on the cyclohexene ring and dicarboxylic acids which formally form from the dicarboxylic acids of the formula (NI) by addition of a molecule of water to the double bond in the cyclohexene ring.

Dicarboxylic acids of the formula (N-I) are known in the literature.

The dicarboxylic acids of the formula (NI) can be prepared, for example, by reacting polyunsaturated dicarboxylic acids with unsaturated monocarboxylic acids in the form of a Diels-Alder cyclization. A polyunsaturated fatty acid is usually used as the dicarboxylic acid component. The linoleic acid accessible from natural fats and oils is preferred. Acrylic acid, but also, for example, methacrylic acid and crotonic acid are particularly preferred as the monocarboxylic acid component. Reactions according to Diels-Alder usually result in isomer mixtures in which one component is present in excess. These isomer mixtures can be used according to the invention just like the pure compounds.

In addition to the preferred dicarboxylic acids of the formula (NI), those dicarboxylic acids which differ from the compounds of the formula (NI) by 1 to 3 methyl or ethyl substituents on the cyclohexyl ring or formally by addition of one of these compounds can also be used according to the invention Molecule water is formed on the double formation of the cyclohexene ring.

The dicarboxylic acid (mixture) which results from the reaction of linoleic acid with acrylic acid has proven to be particularly effective according to the invention. It is a mixture of 5- and 6-carboxy-4-hexyl-2-cyclohexen-1-octanoic acid. Such compounds are commercially available under the designations Westvaco Diacid 1550 Westvaco Diacid ^{® ®} 1595 (manufacturer: Westvaco).

In addition to the short-chain carboxylic acids themselves according to the invention, which have been exemplified above, their physiologically tolerable salts can also be used according to the invention. Examples of such salts are the alkali, alkaline earth, zinc and ammonium salts, which in the context of the present application are also to be understood as the mono-, di- and trimethyl-, -ethyl- and - hydroxyethyl-ammonium salts. However, acids which are neutralized with alkaline-reacting amino acids, such as, for example, arginine, lysine, ornithine and histidine, can very particularly preferably be used in the context of the invention. Furthermore, it can for formulation reasons be preferred to select the carboxylic acid from the water-soluble representatives, in particular the water-soluble salts.

Furthermore, it is preferred according to the invention to use hydroxycarboxylic acids and in this case in particular the dihydroxy, trihydroxy and polyhydroxycarboxylic acids as well as the dihydroxy, trihydroxy and polyhydroxydi, tri and polycarboxylic acids together with the active ingredient (A). It has been shown here that, in addition to the hydroxycarboxylic acids, the hydroxycarboxylic acid esters and the mixtures of hydroxycarboxylic acids and their esters as well as polymeric hydroxycarboxylic acids and their esters can be very particularly preferred. Preferred hydroxycarboxylic acid esters are, for example, full esters of glycolic acid, lactic acid, malic acid, tartaric acid or citric acid. Other basically suitable hydroxycarboxylic acid esters are esters of β-hydroxypropionic acid, tartronic acid, D-gluconic acid, sugar acid, mucic acid or glucuronic acid. Suitable alcohol components of these esters are primary, linear or branched aliphatic alcohols with 8-22 C atoms, for example fatty alcohols or synthetic fatty alcohols. The esters of C12-C15 fatty alcohols are particularly preferred. Esters of this type are commercially available, eg under the trademark Cosmacol® ^® EniChem, Augusta Industriale. Particularly preferred polyhydroxy polycarboxylic acids are polylactic acid and poly-tartaric acid and their esters.

Colorants are usually offered as a combination pack that contains a coloring cream and a separately packaged oxidation solution. Shortly before use, both components are mixed together and the prepared mixture is applied to the hair to be colored. The mixing ratio of the two components can be chosen freely. Preferred hair dyes according to the invention are characterized in that the flowable preparation of oxidation dye precursors (A) and the flowable oxidation agent preparation (B) are applied immediately before application the hair in the weight ratio A: B = 1: 5 to 5: 1, preferably 1: 2 to 2: 1 are mixed with one another to form a coloring batch.

The preparation of the oxidizing agent is then expediently mixed with the preparation with the dye precursors immediately before dyeing the hair. The resulting ready-to-use hair dye preparation should preferably have a pH in the range from 6 to 10. It is particularly preferred to use the hair dye in a weakly alkaline environment. The application temperatures can be in a range between 15 and 40 ^° C., preferably at the temperature of the scalp. After an exposure time of about 5 to 45, in particular 15 to 30, minutes, the hair dye is removed from the hair to be dyed by rinsing. Washing with a shampoo is not necessary if a carrier with a high surfactant content, e.g. B. a coloring shampoo was used.

In particular in the case of hair that is difficult to dye, the preparation with the dye precursors can 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 necessary after an intermediate rinse. After a further exposure time of 10 to 20 minutes, rinsing is carried out and, if desired, re-shampooing. In this embodiment, according to a first variant, in which the previous application of the dye precursors is supposed to bring about better penetration into the hair, the corresponding agent is adjusted to a pH of about 4 to 7. According to a second variant, air oxidation is initially aimed for, the agent applied preferably having a pH of 7 to 10. In the subsequent accelerated postoxidation, the use of acidified peroxidisulfate solutions as the oxidizing agent can be preferred.

Claims

Claims:

1. hair dye, consisting of a flowable preparation of oxidation dye precursors (A) and a flowable, oxidizer preparation (B), which are mixed with one another immediately before application to the hair to form a dye, characterized in that the preparation of oxidation dye precursors (A ) and the oxidizing agent preparation (B) each contain at least one care substance.

2. Hair dye according to claim 1, characterized in that the preparation of oxidation dye precursors (A) and the oxidant preparation (B) the care substance (s) in amounts of 0.1 to 5 wt .-%, preferably from 0.25 to 2.5 wt .-% and in particular from 0.5 to 2 wt .-%, based on the respective total composition.

3. Hair dye according to one of claims 1 or 2, characterized in that the quotient of the wt .-% - proportions of the care substance (s) in the preparation of oxidation dye precursors (A) and the oxidizing agent preparation (B) 5: 1 to 1 : 5, preferably 2: 1 to 1: 2 and in particular 1: 1.

4. Hair dye according to one of claims 1 to 3, characterized in that the preparation of oxidation dye precursors (A) and the oxidizing agent preparation (B) contain the same care substance.

5. Hair dye according to one of claims 1 to 4, characterized in that the preparation of oxidation dye precursors (A) and / or the oxidizing agent preparation (B) contain at least one quaternary ammonium compound, preferably at least one cationic surfactant and / or at least one cationic or amphoteric polymer as a care substance.

6. Hair dye according to one of claims 1 to 5, characterized in that the preparation of oxidation dye precursors (A) and / or the oxidizing agent preparation (B) contains at least one silicone, preferably a silicone, as a care substance, which is selected from: (vii) polyalkylsiloxanes , Polyarylsiloxanes, polyalkylarylsiloxanes which are volatile or non-volatile, straight-chain, branched or cyclic, cross-linked or non-cross-linked; (viii) polysiloxanes which contain in their general structure one or more organofunctional groups which are 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; I) sulfonic acid groups; and m) sulfate or thiosulfate groups; (ix) linear polysiloxane (A) - polyoxyalkylene (B) - block copolymers from

Type (AB) _n with n>3;

(x) grafted silicone polymers with a non-silicone organic backbone, which consist of an organic main chain which is formed from organic monomers which do not contain silicone, onto which at least one polysiloxane macromer has been grafted in the chain and optionally at at least one chain end;

(xi) grafted silicone polymers with a polysiloxane backbone onto which non-silicone-containing organic monomers have been grafted, which have a polysiloxane main chain, onto which at least one organic macromer, which contains no silicone, has been grafted in the chain and optionally at at least one of its ends ;

(xii) or mixtures thereof.

7. Hair dye according to one of claims 1 to 6, characterized in that the preparation of oxidation dye precursors (A) and / or the oxidizing agent preparation (B) as a care substance at least it is an amino-functional silicone of the formula (I)

FTaG _3-3 -Si (OSiG ₂ ) n- (OSiG _b R ' ₂ -

(I),

contains, in which means:

G is -H, a phenyl group, -OH, -O-CH ₃ , -CH ₃ , -CH ₂ CH ₃ , -

CH ₂ CH ₂ CH ₃ , -CH (CHs) ₂ , -CH ₂ CH ₂ CH ₂ H ₃ , -CH ₂ CH (CH ₃ ) ₂ , -

CH (CH ₃ ) CH ₂ CH ₃ , -C (CHs) ₃ ; a stands for 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, n being preferred

Assumes 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 o -N (R ") - CH ₂ -CH ₂ - N (R") ₂ o -N (R ") ₂ o -N ⁺ (R") ₃ A ^~ o -N ⁺ H (R ") ₂ A- o -N ⁺ H ₂ (R ") A- o -N (R ¹ O-CH ₂ -CH ₂ -N ⁺ R ¹¹ H ₂ A-, where each R" represents the same or different radicals from the group - H, -Phenyl, -benzyl, the C _1-20 -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.

8. Hair dye according to one of claims 1 to 7, characterized in that the preparation of oxidation dye precursors (A) and / or the oxidizing agent preparation (B) as a care substance at least there is an amino-functional silicone of the formula (II)

(CH ₃ ) ₃ Si- [O-Si (CH ₃ ) ₂ ] n [OSi (CH ₃ )] _m -OSi (CH ₃ ) ₃ (II),

CH ₂ CH (CH ₃ ) CH ₂ NH (CH ₂ ) ₂ NH ₂

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

9. Hair dye according to one of claims 1 to 8, characterized in that the preparation of oxidation dye precursors (A) and / or the oxidizing agent preparation (B) as a care substance, at least it is an amino-functional silicone of the formula (III)

R- [Si (CH ₃ ) ₂ -O] ni [Si (R) -O] _m - [Si (CH ₃ ) ₂ ] _n2 -R (III),

I (CH ₂ ) ₃ NH (CH ₂ ) ₂ NH ₂ contains, wherein R is -OH, -0-CH ₃ or a -CH ₃ group and m, n1 and n2 are numbers, the sum (m + n1 + n2) of 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 having values from 1 to 2000, in particular from 1 to 10.

10. Hair dye according to one of claims 7 to 9, characterized in that the amino-functional silicone has an amine number above 0.25 meq / g, preferably above 0.3 meq / g and in particular above 0.4 meq / g.

11. Hair dye according to one of claims 1 to 10, characterized in that the flowable preparation of oxidation dye precursors (A) and the flowable oxidant preparation (B) immediately before application to the hair in the weight ratio A: B = 1: 5 to 5 : 1, preferably 1: 2 to 2: 1 are mixed together to form a dyeing batch.