EP2054016A1 - Agents containing bioquinones and protein hydrolysates - Google Patents

Abstract

The invention relates to cosmetic agents, in particular hair treatment agents, containing at least one protein hydrolysate and at least one bioquinone. Treating the hair with said agents improves the structure of human hair.

Description

 Agent containing biochinones and protein hydrolysates

The invention relates to hair treatment compositions containing at least one biochinone and at least one protein hydrolyzate. The invention further relates to a method for improving the hair structure of human hair using the composition and to the use of the hair structure improver of human hair.

Hair follicle cells undergo a genetically determined cycle of growth, regression, and resting phase. The hair follicle is thus the only organ that constantly renews itself and thus exhibits a unique metabolism, depending on the respective growth phase. The synthesis of structural keratins is also linked to this cycle. This cycle is controlled by a small, highly specialized cell population in the hair bulb, the dermal papilla cells, through a unique, complex system of molecular signals that is specific to each phase of the hair cycle (Botchkarev VA et al. (2003) J Investig Dermatol Symp Proc 8: 46-55).

If the metabolism of these highly specialized cells is to be modulated by the use of a test formulation, it is essential to have a targeted effect on the corresponding mechanisms.

Hepatocyte Growth Factor (HGF) and Keratinocyte Growth Factor (KGF) are important growth factors that are released by the dermal papilla to control the proliferation of hair keratinocytes responsible for the hair keratin synthesis. They are also characteristic markers for the anagen phase, in which keratin synthesis is also maximal. In addition, it should be noted that hair proliferation decreases the proliferation capacity of the hair follicle cells. In a potentially keratin-activating and anti-aging substance HGF and / or KGF should therefore be induced. TGF-ß2 and IGFBP-3 inhibit growth and are characteristic markers for the catagen phase, in which keratin synthesis in the follicle is switched off. These markers should be repremet in a substance that promotes keratin synthesis.

Hair keratins represent the most important structuring part of hair. The importance of hair keratins for the healthy hair fiber is shown by the fact that genetic mutations in the hair keratins hHb6 and hHb1 lead to strong changes, such as hair fiber deformation and hair breakage (Monilethix). In addition, mice with a point mutation of the gene Ha3 show a naked phenotype without a fur coat (nude mice).

In addition to their actual physiological role, such as thermal insulation and light protection, hair has a psychosocial function that should not be underestimated. They serve, among others, as Means of interpersonal communication and represent a sign of their own individuality. Changes, including age-related, in hair growth, hair density or hair structure can lead to a massive impairment of self-confidence of the person concerned.

At present there are hardly any cosmetic preparations on the market which support an improvement of the hair structure by means of synthesis of hair-specific keratins in a biological and thus sustainable way.

The aim of the present invention was therefore to find suitable active ingredients for the preparation of cosmetic preparations which are applied topically to the scalp and there activate keratin synthesis and thus improve the hair structure.

This object has been achieved to a great extent by the provision of an agent, in particular for the treatment of hair, which contains a) at least one biochinone and b) at least one protein hydrolyzate.

Biochinones have been used mainly as an antioxidant in skin cosmetics. In addition, there are a number of applications claiming the use of ubiquinone in hair care products. Thus, the application WO200401095 describes the use of a formulation which, inter alia, may contain ubiquinone as an antioxidant to improve the surface texture of the hair.

Application EP-A-1 059 081 claims the use of ubiquinone for reducing oxidative damage to the hair. Although the applications EP-A-1 059 077 and EP-A-1 059 080 use ubiquinone to improve the hair structure, this is a purely superficial physical effect which is based on improving the combability.

However, none of these applications claim the stimulation of keratin synthesis, which improves the internal structure of the hair.

The application WO2004089326 claims the use of an active ingredient combination of creatinine, creatine and biochinones. In particular, this formulation should be used in inflammatory skin conditions and / or for skin protection. However, this application does not address the effect of ubiquinone on keratin synthesis. A first subject of the invention is therefore an agent, in particular for the treatment of hair, comprising a) at least one protein hydrolyzate and b) at least one biochinone.

It was found that the hair treatment with these agents led to a stimulation of the keratin synthesis of several hair keratins and thus to the improvement of the hair structure.

According to the invention, preference is given to compositions in which the ratio of protein hydrolyzate (s) to the biochinone (s) is in the range from 2: 1 to 1000: 1, preferably in the range from 5: 1 to 500: 1 and in particular in the range from 10 : 1 to 200: 1.

Protein hydrolysates suitable according to the invention are product mixtures which are obtained by acid, basic or enzymatically catalyzed degradation of proteins (proteins). According to the invention, they can be of plant as well as animal origin.

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

The protein hydrolysates of plant origin are, for example, soybean, almond, rice, pea, potato and wheat protein hydrolysates. Such products are, for example, under the trademarks Gluadin ^® (Cognis), diamine ^® (Diamalt) ^® (Inolex) and Crotein ^® (Croda) available.

Particularly preferred according to the invention are the protein hydrolysates of animal origin. In particular, keratin hydrolysates of sheep's wool and collagen hydrolysates are used in the compositions according to the invention.

Also particularly preferred is the use of protein hydrolysates of a size of 400 to 1200 daltons.

Although the use of the protein hydrolysates is preferred as such, amino acid mixtures or individual amino acids obtained otherwise, such as, for example, arginine, lysine, histidine or pyrroglutamic acid, may also be used in their place. Also possible is the use of derivatives of protein hydrolysates, for example in the form of their Fatty acid condensation products. Such products are marketed for example under the names Lamepon ^® (Cognis), Gluadin ^® (Cognis), Lexein ^® (Inolex), Crolastin ^® (Croda) or Crotein ^® (Croda).

Cationized protein hydrolysates can also be used according to the invention, the protein hydrolyzate on which the animal is based, for example from collagen, milk or keratin, from the plant, for example from wheat, maize, rice, potatoes, soy or almonds, from marine life forms, for example from fish collages or algae , or from biotechnologically derived protein hydrolysates, can originate. The protein hydrolyzates on which the cationic derivatives according to the invention are based can be obtained from the corresponding proteins by chemical, in particular alkaline or acid hydrolysis, by enzymatic hydrolysis and / or a combination of both types of hydrolysis. The hydrolysis of proteins usually results in a protein hydrolyzate having a molecular weight distribution of about 100 daltons up to several thousand daltons. Preference is given to those cationic protein hydrolyzates whose underlying protein content has a molecular weight of 100 to 25,000 daltons, preferably 250 to 5000 daltons. Furthermore, cationic protein hydrolyzates are to be understood as meaning quaternized amino acids and mixtures thereof. The quaternization of the protein hydrolysates 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. Furthermore, the cationic protein hydrolysates may also be further derivatized. As typical examples of the cationic protein hydrolysates and derivatives according to the invention, those mentioned 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 Cocodimium Hydroxypropyl Hydrolyzed Collagen, Cocodimopnium Hydroxypropyl Hydrolyzed Casein, Cocodimonium Hydroxypropyl Hydrolyzed Collagen, Cocodimonium Hydroxypropyl Hydrolyzed Hair Keratin, Cocodimonium Hydroxypropyl Hydrolyzed Keratin, Cocodimonium Hydroxypropyl Hydrolyzed Rice Protein, Cocodimonium Hydroxypropyl Hydrolyzed SiCl, Cocodimonium Hydroxypropyl Hydrolyzed Soy Protein, Cocodimonium Hydroxypropyl Hydrolyzed Wheat Protein, Cocodimonium Hydroxypropyl SiCl Amino Acids, Hydroxypropyl Arginine Lauryl / Myristyl Ether HCl, Hydroxypropyltrimonium Gelatin, Hydroxypropyltrimonium Hydrolyzed Case in, Hydroxypropyltrimonium Hydrolyzed Collagen, Hydroxypropyltrimonium Hydrolyzed Conchiolin Protein, Hydroxypropyltrimonium Hydrolyzed Keratin, Hydroxypropyltrimonium Hydrolyzed Rice Bran Protein, Hydroxypropyltrimonium Hydrolyzed SiCl, Hydroxypropyltrimonium Hydrolyzed Soy Protein, Hydroxypropyl Hydrolyzed Vegetable Protein, Hydroxypropyltrimonium Hydrolyzed Wheat Protein, Hydroxypropyltrimonium Hydrolyzed Wheat Protein / Siloxysilicate, Laurdimonium Hydroxypropyl Hydrolyzed Soy Protein, Lauridimonium Hydroxypropyl Hydrolyzed Wheat Protein, Lauridimonium Hydroxypropyl Hydrolyzed Wheat Protein / Siloxysilicate, Lauryldimony Hydroxypropyl Hydrolyzed Casein, Lauryldimonium Hydroxypropyl Hydrolyzed Collagen, Lauryldimonium Hydroxypropyl Hydrolyzed Keratin, Lauryldimonium Hydroxypropyl Hydrolyzed Soy Protein, Lauryldimonium Hydroxypropyl Hydrolyzed Soy Protein, Steardimonium Hydroxypropyl Hydrolyzed Casein, Steardimonium Hydroxypropyl Hydrolyzed Collagen, Steardimonium Hydroxypropyl Hydrolyzed Keratin, Steardimonium Hydroxypropyl Hydrolyzed Rice Protein, Steardimonium Hydroxypropyl Hydrolyzed Sick, 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 Sick, Quaternium-79 Hydrolyzed Soy Protein, Quaternium-79 Hydrolyzed Wheat Protein. Very particular preference is given to the cationic protein hydrolysates and derivatives based on plants.

The agents according to the invention contain the protein hydrolysates and / or their derivatives in amounts of from 0.01 to 10% by weight, based on the total agent. Quantities of 0.05 to 5 wt.%, In particular 0.1 to 3 wt .-%, are very particularly preferred.

In the agents according to the invention, suitable biochinones are understood as meaning one or more ubiquinone (s) and / or plastoquinone (s).

Ubiquinones are the most widely used and best studied biochinones. Depending on the number of isoprene units linked in the side chain, ubiquinones are referred to as Q-1, Q-2, Q-3, etc. or by number of carbon atoms as U -5, U-10, U-15 and so on. They preferably occur with certain chain lengths, eg. B. in some microorganisms and yeasts with n = 6. In most mammals, including humans, Q-10 predominates. Ubiquinones serve the organisms as electron carriers in the respiratory chain. They are located in the mitochondria where they allow the cyclic oxidation and reduction of substrates of the citric acid cycle.

The preferred ubiquinones according to the invention have the following formula:

with n = 6, 7, 8, 9 or 10.

Particularly preferred according to the invention is the ubiquinone of the formula where n = 10, also known as coenzyme Q10.

Plastoquinones have the general structural formula

on. They can be isolated from chloroplasts and play a role as redox substrates in photosynthesis in cyclic and noncyclic electron transport, reversibly converting into the corresponding hydroquinones (plastoquinol). Plastoschinone differ in the number n of isoprene residues and are termed endsprechend, z. Eg PQ-9 (n = 9). There are also other plastoquinones with different substituents on the quinone ring.

The or the biochinone (s) is (are) in the inventive compositions - by weight - in an amount of 0.0000005 to 2%, preferably in an amount of 0.000001 to 1% and in particular in an amount of 0 , 00001 to 0.5% used.

According to a further preferred embodiment of the invention, the agents furthermore contain at least one emulsifier and / or at least one dialkyl ether. The addition of one or more of these substances positively influences the availability of active ingredients in the hair root.

Examples of suitable emulsifiers according to the invention are the following compounds:

Addition products of 4 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide to linear fatty alcohols having 8 to 22 carbon atoms, to fatty acids having 12 to 22 carbon atoms and on

Alkylphenols having 8 to 15 C atoms in the alkyl group,

C ₂ -C ₂₂ -fatty acid mono- and diesters of addition products of 1 to 30 mol

Ethylene oxide onto polyols having 3 to 6 carbon atoms, in particular glycerol, Ethylene oxide and polyglycerol addition products to methyl glucoside fatty acid esters,

Fatty acid alkanolamides and fatty acid glucamides, C ₈ -C ₂₂ -alkylnono- and -oligoglycosides and their ethoxylated analogs, wherein

Oligomerisierungsgrade of 1, 1 to 5, in particular 1, 2 to 2.0, and glucose as

Sugar component are preferred, mixtures of alkyl (oligo) glucosides and fatty alcohols, for example, the commercially available product ^® Montanov 68,

Addition products of 5 to 60 moles of ethylene oxide with castor oil and hydrogenated castor oil, partial esters of polyols having 3-6 carbon atoms with saturated fatty acids having 8 to 22 carbon atoms,

Sterols. Sterols are understood to mean a group of steroids which have a hydroxyl group on C-atom 3 of the steroid skeleton 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. Mushrooms and yeasts are also used to isolate sterols, the so-called mycosterols.

Phospholipids. Of these, especially the glucose phospholipids, e.g. as lecithins or phosphatidylcholines from e.g. Egg yolk or plant seeds (e.g., soybeans) are understood.

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

Polyglycerols and polyglycerol such as polyglycerol poly-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.

Emulsifiers which are particularly suitable according to the invention are polyethylene glycol alkyl ethers having alkyl chain lengths of 6 to 30 carbon atoms, preferably 12 to 22 carbon atoms and a degree of ethoxylation of 1 to 1000, preferably 1 to 500 and in particular 1 to 100.

Particularly preferred polyethylene glycol ethers for the purposes of the invention are the substances known by the INCI name ceteareth-6, ceteareth-9, ceteareth-10, ceteareth-20, ceteareth-30, ceteareth-25, steareth-10 and steareth-20.

Further particularly suitable emulsifiers for the purposes of the invention are C ₂ -C ₂₂ fatty acid mono- and diesters of addition products of from 1 to 30 moles of ethylene oxide onto polyols having from 3 to 6 carbon atoms, in particular to glycerol. Particularly suitable are PEG-20 glyceryl stearates, PEG-7 glyceryl cocoate, PEG-30 glyceryl stearate, PEG-6 caprylic / capric glycerides, polyglyceryl-3-diisostearate and glycereth-2-cocoate. The agents according to the invention preferably contain the emulsifiers in amounts of from 0.01 to 25% by weight, preferably in amounts of from 0.05 to 20% by weight and in particular in amounts of from 0.1 to 10% by weight, based on the entire remedy.

According to the invention suitable dialkyl ethers are di-n-alkyl ethers containing a total of 5 to 50 carbon atoms, preferably 8 and 40 and especially with 12 to 24 carbon atoms, such as di-n-octyl ether (Cetiol ^® OE), 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-ethyldecyl ether, tert-butyl n-octyl ether, iso-pentyl-n-octyl ether, 2-methyl-pentyl n-octyl ether and 1, 3-di- (2-ethyl-hexyl) - cyclohexane (Cetiol ^® S). Particularly suitable according to the invention is dicaprylyl ether.

The agents according to the invention contain the dialkyl ethers preferably in amounts of 0.01-50 wt .-%, preferably in amounts of 0.05 to 20 wt .-% and in particular in amounts of 0.1 to 15 wt .-%, based on the entire remedy.

With regard to the manner in which the active ingredient combination according to the invention is applied to the keratinic fiber, in particular human hair, as well as to the skin, there are no fundamental restrictions. For example, creams, lotions, solutions, waters, emulsions such as W / O, O / W, PIT emulsions (called phase inversion emulsions, PIT), microemulsions and multiple emulsions, coarse, unstable, one or more multi-phase shaking mixtures, gels, sprays, aerosols and foam aerosols suitable. These are usually formulated on an aqueous or aqueous-alcoholic basis. As alcoholic component while lower alkanols and polyols such as propylene glycol and glycerol are used. Ethanol and isopropanol are preferred alcohols. Water and alcohol may be present in the aqueous alcoholic base in a weight ratio of 1:10 to 10: 1. Water and aqueous-alcoholic mixtures which contain up to 50% by weight, in particular up to 25% by weight, of alcohol, based on the mixture of alcohol / water, may be preferred bases according to the invention. The pH of these preparations can in principle be between 2 and 11. It is preferably between 2 and 7, with values of 3 to 5 being particularly preferred. To adjust this pH, virtually any acid or base that can be used for cosmetic purposes can be used. Usually, acids are used as acids. By-acids are understood to mean those acids which are absorbed as part of the usual food intake and have positive effects on the human organism. Eat acids are, for example, acetic acid, lactic acid, tartaric acid, citric acid, malic acid, ascorbic acid and gluconic acid. In the context of the invention, the use of citric acid and lactic acid is particularly preferred. Preferred bases are ammonia, alkali hydroxides, monoethanolamine, triethanolamine and N, N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine.

Preparations remaining on the skin and hair have proven to be particularly effective and may therefore represent preferred embodiments of the teaching according to the invention. Under the skin and the hair remaining according to the invention are understood such preparations that are not in the context of treatment after a period of a few seconds to one hour with the help of water or an aqueous solution again from the skin or rinsed out of the hair , Rather, the preparations remain until the next wash on the skin or hair.

According to a particularly preferred embodiment for use on the hair, the compositions according to the invention are formulated as a hair conditioner, hair tonic, conditioner, hair conditioner, hair setting agent, hair spray or hair gel. The preparations of the invention according to this embodiment can be rinsed with water or an at least predominantly aqueous agent after this exposure time; however, they are preferably left on the hair as stated above. It may be preferred to apply the preparation according to the invention to the hair before the application of a cleansing agent, a waving agent or other hair treatment agents. In this case, the preparation of the invention serves as a color protection for the following applications.

Another preferred embodiment of the agent according to the invention is also a shampoo.

In a particular embodiment of the compositions according to the invention, it may be preferred if the agents are present as a microemulsion. Within the scope of the invention, microemulsions are also understood to be so-called "PIT" emulsions. These emulsions are, in principle, systems with the 3 components water, oil and emulsifier, which are oil-in-water (O / W) at room temperature. When these systems are heated, microemulsions are formed in a certain temperature range (commonly referred to as the phase inversion temperature or "PIT") which, on further heating, convert to water-in-oil (W / O) emulsions O / W emulsions are again formed, but are also present at room temperature as microemulsions having a mean particle diameter of less than 400 nm, in particular having a particle diameter of about 100-300 nm, details of these very stable, low-viscosity systems for which The term "PIT emulsions" has generally prevailed, can be found in a variety of publications for the Deputy the publications in Angew. Chem. 97, 655-669 (1985) and Adv. Colloid Interface, pages 58, 119-149 (1995). According to the invention, preference may be given to those microparticles or "PIT" emulsions which have an average particle diameter of about 200 nm.

The preparation of the microemulsions according to the invention can be carried out, for example, by first determining the phase inversion temperature of the system by heating a sample of the conventionally prepared emulsion and using a conductivity meter to determine the temperature at which the conductivity decreases sharply. The decrease in the specific conductivity of the initially present O / W emulsion generally decreases over a temperature range from 2 to 8 ^° C. from originally more than 1 mS / cm to values below 0.1 mS / cm. This temperature range then corresponds to the phase inversion temperature range. Thus, after the phase inversion temperature range is known, the emulsion of oil component, nonionic emulsifier, at least parts of the water and optionally other components initially prepared as usual can be heated to a temperature which is within or above the phase inversion temperature range, then allowed to cool and optionally add other components as well as the remaining water. Alternatively, the preparation of the microemulsion can be carried out directly at a temperature which is within or above the phase inversion temperature range. The microemulsion thus prepared is then cooled to a temperature below the phase inversion temperature range, usually room temperature.

In a preferred embodiment of the teaching according to the invention, the effect can be further increased with polymers. By polymers are meant both natural and synthetic polymers which may be anionic, cationic, amphoteric or nonionic.

Cationic polymers are polymers which have groups in the main and / or side chain which may be "temporary" or "permanent" cationic. According to the invention, "permanently cationic" refers to those polymers which have a cationic group, irrespective of the pH of the agent. These are usually polymers containing a quaternary nitrogen atom, for example in the form of an ammonium group. Preferred cationic groups are quaternary ammonium groups. In particular, such polymers in which the quaternary ammonium group are bonded via a C-ι- ₄ -hydrocarbon group to a constructed from acrylic acid, methacrylic acid or their derivatives polymer backbone have been found to be particularly suitable.

Homopolymers of the general formula (PI), R 18

- [CH ₂ -CJ _n X ^" (PI)

CO-O- (CH ₂ ) n ⁺ R ¹⁹ R ²⁰ R ²¹

R ¹⁸ = -H or -CH _3, R ^19, R ²⁰ and R ²¹ are independently selected from _d-4 alkyl, alkenyl or hydroxyalkyl groups, m = 1, 2, 3 or 4, n is a natural number and X ^"is a physiologically acceptable organic or inorganic anion, and copolymers consisting essentially of the monomer units listed in formula (III) and nonionic monomer units are particularly preferred cationic polymers. for at least one of the following conditions:

R ¹⁸ is a methyl group

R ¹⁹ , R ²⁰ and R ²¹ are methyl groups m has the value 2.

Suitable physiologically acceptable counter ions X ^"include halide ions, sulfate ions, phosphate ions, methosulfate ions and organic ions such as lactate, citrate, tartrate and acetate ions. Preferred are halide ions, particularly chloride.

A particularly suitable homopolymer is, if desired, crosslinked, poly (methacryloyloxyethyltrimethylammoniumchlorid) with the INCI name Polyquaternium- 37. The crosslinking, if desired, using poly olefinically unsaturated compounds, for example divinylbenzene, tetraallyloxyethane, methylenebisacrylamide, diallyl ether, polyallylpolyglycerylether, or allyl ethers of sugars or Sugar derivatives such as erythritol, pentaerythritol, arabitol, mannitol, sorbitol, sucrose or glucose. Methylenebisacrylamide is a preferred crosslinking agent.

The homopolymer is preferably used in the form of a nonaqueous polymer dispersion which should not have a polymer content of less than 30% by weight. Such polymer dispersions are (under the names Salcare ^® SC 95 about 50% polymer content, additional components: mineral oil (INCI name: Mineral Oil) and tridecyl-polyoxypropylene-polyoxyethylene-ether (INCI name: PPG-1 trideceth-6) ) and Salcare ^® SC 96 (about 50% polymer content, additional components: mixture of diesters of propylene glycol with a mixture of caprylic and capric acid (INCI name: propylene glycol Dicaprylate / Dicaprate) and tridecyl polyoxypropylene-polyoxyethylene-ether (INCI Designation: PPG-1-trideceth-6)) are commercially available. Copolymers with monomer units of the formula (PI) contain, as nonionic monomer units, preferably acrylamide, methacrylamide, acrylic acid C-. _4- alkyl esters and methacrylic acid-C-ι- ₄ -alkyl ester. Among these nonionic monomers, the acrylamide is particularly preferred. These copolymers can also be crosslinked, as described above in the case of the homopolymers. A copolymer preferred 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 92 under the name Salcare ^® SC.

Further preferred cationic polymers are, for example

- quaternized CeIIu lose-derivatives, such as under the trade names Celquat ^® and polymer

^JR® are commercially available. 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 ^®,

- Polysiloxanes with quaternary groups, such as those commercially available

Products Q2-7224 (manufacturer: Dow Corning, a stabilized trimethylsilylamodimethicone), Dow ^Corning® 929 emulsion (containing a hydroxylamino-modified silicone, also referred to as amodimethicone), SM-2059 (manufacturer: General Electric), SLM 55067 (manufacturer: Wacker) and Abil ^® -Quat 3270 and 3272 (manufacturer: Th Goldschmidt; di- quaternary polydimethylsiloxanes, quaternium-80).,

- Dimethyldiallylammoniumsalze polymeric and their copolymers with esters and amides of acrylic acid and methacrylic acid. Under the names 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 diethyl sulfate quaternized vinylpyrrolidone-dimethylaminoethyl methacrylate copolymers. Such compounds are sold under the names Gafquat ^® 734 and Gafquat ^® 755 commercially,

Vinylpyrrolidone-vinyl imidazolium copolymers, such as those offered under the names Luviquat ^® FC 370, FC 550, FC 905 and HM 552, quaternized polyvinyl alcohol, as well as by the names of Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and

Polyquaternium 27 known polymers with quaternary nitrogen atoms in the polymer main chain.

Can be used as cationic polymers are sold under the names Polyquaternium-24 (commercial product z. B. Quatrisoft ^® LM 200), known polymers. , Gaffix ^® VC 713 (manufactured by ISP): Also according to the invention can be used the copolymers of vinylpyrrolidone, such as the commercial products Copolymer 845 (ISP manufacturer) are Gafquat ^® ASCP 1011, Gafquat ^® HS 110, Luviquat ^® 8155 and Luviquat ^® MS 370 available are.

Further cationic polymers according to the invention are the so-called "temporary cationic" polymers. These polymers usually contain an amino group which, at certain pH values, is present as a quaternary ammonium group and thus cationically. For example, chitosan and its derivatives are preferred as Hydagen CMF ^®, Hydagen HCMF ^®, Kytamer ^® PC and Chitolam ^® NB / 101 are freely available commercially, for example under the trade names. Chitosans are deacetylated chitins, which are commercially available in different degrees of deacetylation and different degrees of degradation (molecular weights).

Particularly suitable chitosans have a degree of deacetylation of at least 80% and a molecular weight of 5 10 ⁵ to 5 10 ⁶ (g / mol).

For the production of preparations according to the invention, the chitosan must be converted into the salt form. This can be done by dissolving in dilute aqueous acids. As acids, both mineral acids, e.g. Hydrochloric acid, sulfuric acid and phosphoric acid as well as organic acids, e.g. low molecular weight carboxylic acids, polycarboxylic acids and hydroxycarboxylic acids suitable. Furthermore, higher molecular weight alkyl sulfonic acids or alkyl sulfuric acids or organophosphoric acids can be used, provided that they have the required physiological compatibility. Suitable acids for converting the chitosan into the salt form are e.g. Acetic acid, glycolic acid, tartaric acid, malic acid, citric acid, lactic acid, 2-pyrrolidinone-5-carboxylic acid, benzoic acid or salicylic acid. Preferred are low molecular weight hydroxycarboxylic acids such as e.g. Glycolic acid or lactic acid.

The anionic polymers which can support the action of the active ingredient according to the invention 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 Acrylannido-2-nnethylpropansulfonsäure. The acidic groups may be wholly or partly present 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 can be found to be particularly effective, it being possible for the sulfonic acid group to be wholly or partly present as sodium, potassium, ammonium, mono- or triethanolammonium salt ,

More preferably, the homopolymer of 2-acrylamido-2-methyl propane sulfonic acid, which is available for example under the name Rheothik ^® 11-80 is commercially.

Within this embodiment, it may be preferable 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 esters, methacrylic esters, vinylpyrrolidone, vinyl ethers and vinyl esters.

Preferred anionic copolymers are acrylic acid-acrylamide copolymers and in particular polyacrylamide copolymers with sulfonic acid-containing monomers. A particularly preferred anionic copolymer consists of 70 to 55 mol% of acrylamide and 30 to 45 mol% of 2-acrylamido-2-methylpropanesulfonic acid, wherein the sulfonic acid group is wholly or partly in the form of sodium, potassium, ammonium, mono- or triethanolammonium Salt is present. This copolymer may also be crosslinked, with crosslinking agents preferably polyolefinically unsaturated compounds such as tetraallyloxyethane, allylsucrose, allylpentaerythritol and methylenebisacrylamide are used. 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 (C ₁₃ -C ₄ -lsoparaffin) and a non-ionic emulsifier (laureth-7), has proved to be particularly advantageous within the scope of the teaching according to the invention.

Also sold under the name Simulgel ^® 600 as a compound with isohexadecane and polysorbate 80 Natriumacryloyldimethyltaurat copolymers have proven to be particularly effective according to the invention.

Likewise preferred anionic homopolymers are uncrosslinked and crosslinked polyacrylic acids. Allyl ethers of pentaerythritol, sucrose and propylene may be preferred crosslinking agents. Such compounds are for example available under the trademark Carbopol ^® commercially. Copolymers of maleic anhydride and methyl vinyl ether, especially those with crosslinks, are also color-retaining polymers. A 1, 9-decadiene crosslinked maleic acid-methyl vinyl ether copolymer is available under the name ^® Stabileze QM.

Furthermore, amphoteric polymers can be used as constituents as polymers for increasing the action of the active ingredient combination according to the invention. The term amphoteric polymers includes both those polymers which contain in the molecule both free amino groups and free -COOH or SO ₃ H groups and are capable of forming internal salts, as well as zwitterionic polymers which in the molecule have quaternary ammonium groups and -COO or -SO ₃ ^~ groups, and those polymers comprising -COOH or SO ₃ H groups and quaternary ammonium groups.

An example for an inventive amphopolymer is the acrylic resin commercially available as Amphomer ^®, which is a copolymer of tert-butylaminoethyl methacrylate, N- (1, 1, 3,3-tetramethylbutyl) -acrylamide and two or more monomers from the group acrylic acid, methacrylic and their simple esters.

Preferably used amphoteric polymers are those polymers which are composed essentially

(a) monomers having quaternary ammonium groups of the general formula (PII),

R ²² -CH = CR ²³ -CO-Z- (C _n H _2n ) -N ⁽⁺⁾ R ²⁴ R ²⁵ R ²⁶ A ⁽⁾ (PII)

in which R ²² and R ²³ independently of one another are hydrogen or a methyl group and R ²⁴ , R ²⁵ and R ²⁶ independently of one another are alkyl groups having 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 (PNI),

R ²⁷ -CH = CR ²⁸ -COOH (PNI)

in which R ²⁷ and R ^{28 are} independently hydrogen or methyl groups.

These compounds can be used both directly and in salt form, which is obtained by neutralization of the polymers, for example with an alkali metal hydroxide, according to the invention become. With regard to the details of the preparation of these polymers is expressly made to the content of German Patent Application 39 29 973 reference. Very particular preference is given to those polymers in which monomers of the type (a) are used in which R ²⁴ , R ²⁵ and R ^{26 are} methyl groups, Z is an NH group and A ^{() is} a halide, methoxysulfate or ethoxysulfate ion is; Acrylamidopropyl trimethyl ammonium chloride is a particularly preferred monomer (a). Acrylic acid is preferably used as monomer (b) for the stated polymers.

In a third variant, the agents according to the invention may furthermore contain nonionogenic polymers.

Suitable nonionic polymers are, for example:

VinylpyrrolidonΛ ynyl ester copolymers, such as for example, under the trade name 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

Methylhydroxypropylcellulose, as for example sold under the trademarks Culminal ^® and Benecel ^® (AQUALON). shellac

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

Siloxanes. These siloxanes can be both water-soluble and water-insoluble. Both volatile and nonvolatile siloxanes are suitable, nonvolatile siloxanes being understood as meaning those compounds whose boiling point is above 200 ^° C. under normal pressure. 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 according to EP 0612759 B1.

It is also possible according to the invention that the preparations comprise a plurality of, in particular two, different polymers of the same charge and / or in each case an ionic and an amphoteric and / or nonionic polymer.

According to the invention, the term polymer also means special preparations of polymers, such as spherical polymer powders. Various methods are known for producing such microspheres from different monomers, for example by special polymerization processes or by dissolving the polymer in a solvent and spraying it into a medium in which the solvent evaporates or from the particles can diffuse out. Such a method is known, for example, from EP 466 986 B1. Suitable polymers are, for example, polycarbonates, polyurethanes, polyacrylates, polyolefins, polyesters or polyamides. Particularly suitable are those spherical polymer powders whose primary particle diameter is less than 1 micron. Such products based on a polymethacrylate copolymer are, for example, under the trademark Polytrap ^® Q5-6603 (Dow Corning) in the trade. Other polymer powders, for example based on polyamides (nylon 6, nylon 12) having a particle size of 2 - (10 microns (90%) and a specific surface area of about 10 m ² / g under the trade name Orgasol ^® 2002 DU Nat Cos Atochem SA, Paris). Further spherical polymer powders which are suitable for the purpose according to the invention are, for example, the polymethacrylates (Micropearl M) from SEPPIC or (Plastic Powder A) from NIKKOL, the styrene-divinylbenzene copolymers (Plastic Powder FP) from NIKKOL, the polyethylene and polypropylene AKZO powder (ACCUREL EP 400) or silicone polymers (Silicone Powder X2-1605) from Dow Corning or spherical cellulose powders.

The polymers are contained in the agents according to the invention preferably in amounts of from 0.01 to 10% by weight, based on the total agent. Amounts of 0.05 to 5 wt .-%, in particular from 0.1 to 3 wt .-%, are particularly preferred.

In a further preferred embodiment, the agents according to the invention contain surfactants. The term surfactants is understood to mean surface-active substances which carry an anionic or cationic charge in the molecule. Also, both anionic and cationic charge may be present in the molecule. These zwitterionic or amphoteric surface-active substances can also be used according to the invention. Furthermore, the surface-active substances may also be non-ionic.

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

linear and branched fatty acids with 8 to 30 carbon atoms (soaps),

Ethercarbonsäuren the formula RO- (CH2 "CH2θ) _χ -CH2-COOH, in which R is a linear

Alkyl group having 8 to 30 C atoms and x = 0 or 1 to 16, acylsarcosides having 8 to 24 C atoms in the acyl group, Acyltaurides having 8 to 24 C atoms in the acyl group, acyl isethionates having 8 to 24 C atoms in the acyl group,

Sulfobernsteinsäuremono- and -dialkylester having 8 to 24 carbon atoms in the alkyl group and sulfosuccinic monoalkylpolyoxyethylester with 8 to 24 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups, linear alkanesulfonates having 8 to 24 carbon atoms, linear alpha-olefinsulfonates with 8 to 24 carbon atoms, alpha-sulfofatty acid methyl esters of fatty acids having 8 to 30 carbon atoms, alkyl sulfates and Alkylpolyglykolethersulfate the formula RO (CH ₂ -CH ₂ O) _x -OSO ₃ H, in the R is a preferably linear alkyl group with 8 bis 30 C-atoms and x = 0 or 1 to 12, mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030, sulfated hydroxyalkylpolyethylene and / or hydroxyalkylene-propylene glycol ethers according to DE-A-37 23 354,

Sulfonates of unsaturated fatty acids having 8 to 24 carbon atoms and 1 to 6 double bonds according to DE-A-39 26 344,

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 C atoms, alkyl and / or alkenyl ether phosphates of the formula (Tl),

O

R29 (OCH2CH2) _n - O - P - OR30 (TI)

OX

in the R ^{29 is} preferably an aliphatic hydrocarbon radical having 8 to 30 carbon atoms, R ^{30 is} hydrogen, a radical (CH ₂ CH ₂ O) _n R ²⁹ or X, n is from 1 to 10 and X is hydrogen, an alkali metal radical or alkaline earth metal or NR ³¹ R ³² R ³³ R ³⁴ , with R ³¹ to R ³⁴ independently of one another represents a C 1 to C ₄ hydrocarbon radical, is a sulfated fatty acid alkylene glycol ester of the formula (TII)

R ³⁵ CO (AIkO) _n SO ₃ M (TII)

in the R ³⁵ CO- for a linear or branched, aliphatic, saturated and / or unsaturated acyl radical having 6 to 22 C atoms, Alk for CH ₂ CH ₂ , CHCH ₃ CH ₂ and / or CH ₂ CHCH ₃ , n for numbers from 0.5 to 5 and M is a cation, as described in DE-OS 197 36 906.5, monoglyceride sulfates and monoglyceride ether sulfates of the formula (TIN),

CH 2 θ (CH 2 CH 2 θ) _χ - COR 36 CHO (CH 2 CH 2 θ) _y H (TIN) in which R ³⁶ CO is a linear or branched acyl radical having 6 to 22 carbon atoms, x, y and z are in total 0 or numbers of 1 to 30, preferably 2 to 10, and X is an alkali or alkaline earth metal. Typical examples of monoglyceride (ether) sulfates suitable for the purposes of the invention are the reaction products of lauric acid monoglyceride, coconut fatty acid monoglyceride, palmitic acid monoglyceride, stearic acid monoglyceride, oleic acid monoglyceride and tallow fatty acid monoglyceride and their ethylene oxide adducts with sulfur trioxide or chlorosulfonic acid in the form of their sodium salts. Monoglyceride sulfates of the formula (TIN) in which R ³⁶ CO is a linear acyl radical having 8 to 18 carbon atoms are preferably used. Monoglyceride sulfates and monoglyceride ether sulfates are described for example in EP-B1 0 561 825, EP-B1 0 561 999, DE-A1 42 04 700 or AKBiswas et al. in J.Am.Oil. Chem. Soc. 37, 171 (1960) and FUAhmed in J.Am.Oil.Chem.Soc. 67, 8 (1990).

Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids having 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule and sulfosuccinic acid mono- and dialkyl esters having 8 to 18 carbon atoms in the alkyl group and sulfosuccinic monoalkylpolyoxyethyl ester having 8 to 18 C atoms in the alkyl group and 1 to 6 oxyethyl groups.

Zwitterionic surfactants are those surface-active compounds which carry at least one quaternary ammonium group and at least one -COO ⁽⁾ or -SO ₃ '^"' group in the molecule Particularly suitable zwitterionic surfactants are the so-called betaines such as N-alkyl-N , N-dimethylammonium glycinates, for example cocoalkyldimethylammoniumglycinate, N-acylaminopropyl-N, N-dimethylammoniumglycinates, for example cocoacylaminopropyl-dimethylammonium glycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethylimidazolines A preferred zwitterionic surfactant is the fatty acid amide derivative known by the INCI name cocamidopropyl betaine.

Ampholytic surfactants are understood as meaning those surface-active compounds which, apart from a C _{8 -C 2Λ} -alkyl or acyl group in the molecule, contain at least one free amino group and at least one -COOH or -SO ₃ H group and which are capable of forming internal salts , Examples of suitable 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 having about 8 to 24 C atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and the C ₂ - C ₈ - sarcosine. Nonionic surfactants contain as hydrophilic group z. A polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether groups. Such compounds are, for example

Addition products of 2 to 50 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide to linear and branched fatty alcohols having 8 to 30 carbon atoms, to fatty acids having 8 to 30 carbon atoms and alkylphenols having 8 to 15 carbon atoms in the alkyl group , end-capped adducts of 2 to 50 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide with linear or branched fatty alcohols containing 8 to 30 carbon atoms, with fatty acids containing 8 to 30 carbon atoms, with a methyl or C ₂ -C ₆ -alkyl radical. atoms and onto alkylphenols having 8 to 15 carbon atoms in the alkyl group, such as those available under the trade names Dehydol ^® LS, Dehydol ^® LT types (Cognis), C ₂ -C ₃ o-fatty acid mono- and diesters of addition products of 1 up to 30 moles of ethylene oxide with glycerol,

Addition products of 5 to 60 mol ethylene oxide onto castor oil and hydrogenated castor oil, polyol fatty acid esters, such as the commercial product Hydagen ^® HSP (Cognis) or Sovermol - types (Cognis), alkoxylated triglycerides, - alkoxylated fatty acid alkyl esters of the formula R ³⁷ CO- (OCH ₂ CHR ³⁸ ) _W OR ³⁹ , (IX) in which R ^{37 is} CO for a linear or branched, saturated and / or unsaturated acyl radical having 6 to 22 carbon atoms, R ^{38 is} hydrogen or methyl, R ^{39 is} linear or branched alkyl radicals having 1 to 4 Carbon atoms and w is numbers from 1 to 20,

Amine oxides,

Hydroxymix ethers, as described for example in DE-OS 19738866,

Sorbitan fatty acid esters and adducts of ethylene oxide with sorbitan fatty acid esters such as the polysorbates,

Sugar fatty acid esters and addition products of ethylene oxide with sugar fatty acid esters,

Addition products of ethylene oxide to fatty acid alkanolamides and fatty amines,

Fatty acid N-alkyl glucamides,

Alkyl polyglycosides corresponding to the general formula RO- (Z) _x where R is alkyl, Z is for

Sugar and x represents the number of sugar units. The inventively usable

Alkyl polyglycosides can only contain one particular alkyl radical R. Usually, however, these compounds are starting from natural fats and oils or

Mineral oils produced. In this case, the alkyl radicals R are mixtures corresponding to

Starting compounds or according to the respective workup of these compounds.

Particularly preferred are those alkyl polyglycosides in which R consisting essentially of C ₈ and do-alkyl groups, consisting essentially of C ₁₂ and C ₁₄ alkyl groups, consisting essentially of C ₈ - to C ₁₆ -alkyl groups or substantially of C ₁₂ - to C ₁₆ -alkyl groups or essentially of C ₁₆ to C ₁₈ alkyl groups.

As sugar building block Z it is possible to use any desired mono- or oligosaccharides. Usually, sugars with 5 or 6 carbon atoms and the corresponding oligosaccharides are used. Such sugars are, for example, glucose, fructose, galactose, arabinose, ribose, xylose, lyxose, allose, altrose, mannose, gulose, idose, talose and sucrose. Preferred sugar building blocks are glucose, fructose, galactose, arabinose and sucrose; Glucose is particularly preferred.

The alkylpolyglycosides according to the invention contain on average 1, 1 to 5 sugar units. Alkyl polyglycosides having x values of 1.1 to 2.0 are preferred. Very particular preference is given to alkyl glycosides in which x is 1: 1 to 1, 8.

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

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

These connections are identified by the following parameters. The alkyl radical R contains 6 to 22 carbon atoms and may be both linear and branched. Preference is given to primary linear and methyl-branched in the 2-position aliphatic radicals. Such alkyl radicals are, for example, 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl and 1-stearyl. Particularly preferred are 1-octyl, 1-decyl, 1-lauryl, 1-myristyl. When using so-called "oxo-alcohols" as starting materials, compounds with an odd number of carbon atoms in the alkyl chain predominate.

The compounds used as surfactant with alkyl groups may each be uniform substances. However, it is usually preferred to start with the production of these substances from native plant or animal raw materials, so that one Substance mixtures with different, depending on the particular raw material alkyl chain lengths obtained.

In the case of the surfactants which are adducts of ethylene oxide and / or propylene oxide with fatty alcohols or derivatives of these addition products, both products with a "normal" homolog distribution and those with a narrow homolog distribution can be used. By "normal" homolog distribution are meant mixtures of homologs obtained in the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates as catalysts. Narrowed homolog distributions are obtained when, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alkoxides are used as catalysts. The use of products with narrow homolog distribution may be preferred.

These surfactants are used in amounts of from 0.1 to 45% by weight, preferably 0.5 to 30% by weight and very particularly preferably from 1 to 15% by weight, based on the total agent.

Also usable according to the invention are cationic surfactants of the quaternary ammonium compound type, the esterquats and the amidoamines. Preferred quaternary ammonium compounds are ammonium halides, in particular chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkyl methylammonium chlorides, eg. For example, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride, as well as the imidazolium compounds known under the INCI names Quaternium-27 and Quaternium-83. The long alkyl chains of the above-mentioned surfactants preferably have 10 to 18 carbon atoms.

Esterquats are known substances which contain both at least one ester function and at least one quaternary ammonium group as a structural element. Preferred ester quats are quaternized ester salts of fatty acids with triethanolamine, quaternized ester salts of fatty acids with diethanolalkylamines and quaternized ester salts of fatty acids with 1,2-dihydroxypropyldialkylamines. Such products are marketed under the trade names Stepantex® ^{®, ®} and Dehyquart® Armocare® ^®. The products Armocare ^® VGH-70, a N, N-bis (2-palmitoyloxyethyl) dimethylammonium chloride, as well as Dehyquart ^® F-75, Dehyquart ^® C-4046, Dehyquart ^® L80 and Dehyquart ^® AU-35 are examples of such esterquats.

The alkylamidoamines are usually prepared by amidation of natural or synthetic fatty acids and fatty acid cuts with dialkylaminoamines. An invention Particularly suitable compound from this group of substances is the commercially available under the name Tegoamid ^® S 18 stearamidopropyl-dimethylamine.

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

In a further preferred embodiment of the invention, the effect of the active ingredient combination according to the invention can be further optimized by fatty substances. Fatty substances are to be understood as meaning fatty acids, fatty alcohols, natural and synthetic waxes, which can be in solid form as well as liquid in aqueous dispersion, and natural and synthetic cosmetic oil components.

The fatty acids used can be linear and / or branched, saturated and / or unsaturated fatty acids having 6 to 30 carbon atoms. Preference is given to fatty acids having 10 to 22 carbon atoms. Among these could be mentioned, for example, 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. Further typical examples of such fatty acids are caproic, caprylic, 2-ethylhexanoic, capric, lauric, isotridecanoic, myristic, palmitic, palmitoleic, stearic, isostearic, oleic, elaidic, petroselic, linoleic, linoleic and erucic acid and their technical mixtures, the z. As in the pressure splitting of natural fats and oils, in the oxidation of aldehydes from the Roelen oxo synthesis or the dimerization of unsaturated fatty acids. Particularly preferred are usually the fatty acid cuttings obtainable from coconut oil or palm oil; In particular, the use of stearic acid is usually preferred.

The amount used is 0.1 - 15 wt.%, Based on the total mean. In a preferred embodiment, the amount is 0.5-10% by weight, very particularly preferably amounts of 1-5% by weight.

As fatty alcohols it is possible to use saturated, mono- or polyunsaturated, branched or unbranched fatty alcohols with C ₆ -C ₃₀ -, preferably C ₁₀ -C ₂₂ - and very particularly preferably C ₁₂ -C ₂₂ -carbon atoms. Decanols, octanols, dodecadienol, decadienol, oleyl alcohol, eruca alcohol, ricinoleic alcohol, stearyl alcohol, isostearyl alcohol, cetyl alcohol, lauryl alcohol, myristyl alcohol, arachidyl alcohol, caprylic alcohol, capric alcohol, linoleyl alcohol, linolenyl alcohol and behenyl alcohol are, for example, decanol, octanolol, dodecadienol, decadienol , as well as their Guerbet alcohols, these being List should have exemplary and non-limiting character. However, the fatty alcohols are derived from preferably natural fatty acids, which can usually be based on recovery from the esters of fatty acids by reduction. Also usable 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, rapeseed 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 ^® such as Stenol ^® 1618 or Lanette ^® such as Lanette ^® O or Lorol ^®, for example, Lorol ^® C8, Lorol C14 ^®, Lorol C18 ^{®, ®} Lorol C8-18, HD-Ocenol ^®, Crodacol ^® such as Crodacol ^® CS, Novol ^®, Eutanol ^® G, Guerbitol ^® 16, Guerbitol ^® 18, Guerbitol ^® 20, Isofol ^® 12, Isofol ^® 16, Isofol ^® 24, Isofol ^® 36, Isocarb ^® 12, Isocarb ^® 16 or acquire Isocarb® ^® 24 for sale. Of course, wool wax alcohols, as are commercially available, for example under the names of Corona ^®, White Swan ^®, Coronet ^® or Fluilan ^® can be used according to the invention. The fatty alcohols are used in amounts of from 0.1 to 20% by weight, based on the total preparation, preferably in amounts of from 0.1 to 10% by weight.

The natural or synthetic waxes used according to the invention are solid paraffins or isoparaffins, carnauba waxes, beeswaxes, candelilla waxes, ozokerites, ceresin, spermaceti, sunflower wax, fruit waxes such as apple wax or citrus wax, microwaxes of PE or PP. Such waxes are available, for example, from Kahl & Co., Trittau.

The natural and synthetic cosmetic oil bodies which can increase the action of the active ingredient 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 kernel oil and the liquid portions of coconut oil. Also suitable, however, are other triglyceride oils such as the liquid portions of beef tallow as well as synthetic triglyceride oils. liquid paraffin oils, isoparaffin oils and synthetic hydrocarbons. Esteröle. Ester oils are to be understood as meaning the esters of C ₆ - C ₃₀ fatty acids with C ₂ - C ₃₀ fatty alcohols. The monoesters of the fatty acids with alcohols having 2 to 24 carbon atoms are preferred. Examples of fatty acid components used in the esters are caproic, caprylic, 2-ethylhexanoic, capric, lauric, isotridecanoic, myristic, palmitic, palmitoleic, stearic, isostearic, oleic, elaidic, petroselic, linoleic, linolenic Behenic acid and erucic acid and their technical mixtures which are obtained, for example, in the pressure splitting of natural fats and oils, in the oxidation of aldehydes from Roelen's oxo synthesis or the dimerization of unsaturated fatty acids. Examples of the fatty alcohol components in the ester oils are isopropyl alcohol, caproic alcohol, capryl alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachyl alcohol, Gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and their technical mixtures, for example, in the high-pressure hydrogenation of technical methyl esters based on fats and oils or aldehydes from the Roelen oxo synthesis and as a monomer fraction in the dimerization of unsaturated fatty alcohols incurred. According to the invention, particularly preferred are isopropyl myristate (IPM Rilanit ^®), isononanoic acid C16-18 alkyl ester (Cetiol ^® SN), 2-ethylhexyl palmitate (Cegesoft ^® 24), stearic acid-2-ethylhexyl ester (Cetiol ^® 868), cetyl oleate, glycerol tricaprylate, Kokosfettalkohol- caprate / caprylate (Cetiol ^® LC), n-butyl stearate, oleyl erucate (Cetiol ^® J 600), isopropyl palmitate (IPP Rilanit ^®), oleyl Oleate (Cetiol ^®), hexyl laurate (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, and diol esters such as ethylene glycol dioleate, ethylene glycol diisotridecanoate, propylene glycol di (2- ethylhexanoate), propylene glycol diisostearate,

Propylene glycol di-pelargonat, butanediol di-isostearate, Neopentylglykoldicaprylat, symmetrical, asymmetric 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),

Mono, - di- and trifatty acid esters of saturated and / or unsaturated linear and / or branched fatty acids with glycerol such as Monomuls 90-018 ^®, Monomuls 90 L12 ^® or Cutina ^® MD.

The amount used is 0.1-50 wt.%, Based on the total mean. Preference is given to 0.1 to 20% by weight and more preferably 0.1 to 15% by weight.

The total amount of oil and fat components in the compositions according to the invention is usually from 6 to 45% by weight, based on the total agent. Amounts of 10-35% by weight are preferred according to the invention.

Furthermore, it has been shown that the effect of the combination of active substances according to the invention can be increased if it is combined with hydroxycarboxylic acid esters. Preferred hydroxycarboxylic acid esters are full esters of glycolic acid, lactic acid, malic acid, tartaric acid or citric acid. Further basically suitable hydroxycarboxylic acid esters are esters of β-hydroxypropionic acid, tartronic acid, D-gluconic acid, sugar acid, mucic acid or glucuronic acid. As the alcohol component of these esters are primary, linear or branched aliphatic alcohols having 8-22 C atoms, ie, for example, fatty alcohols or synthetic fatty alcohols. The esters of C ₁₂ -C ₅ fatty alcohols are particularly preferred. Esters of this type are commercially available, eg under the trademark Cosmacol® ^® EniChem, Augusta Industriale. The amount of hydroxycarboxylic acid ester used is 0.1-15% by weight, based on the agent, preferably 0.1-10% by weight, and very particularly preferably 0.1-5% by weight.

Also advantageous has proved to be the combination of the combination of active ingredients with vitamins, provitamins and vitamin precursors and their derivatives.

According to the invention, such vitamins, pro-vitamins and vitamin precursors are preferred, which are usually assigned to groups A, B, C, E, F and H.

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

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

• Vitamin B ₁ (thiamine)

• Vitamin B ₂ (riboflavin)

• Vitamin B ₃ . Under this name, the compounds nicotinic acid and nicotinamide (niacinamide) are often performed. Preferred according to the invention is the nicotinic acid amide which is contained in the agents used according to the invention preferably in amounts of from 0.05 to 1% by weight, based on the total agent.

• Vitamin B ₅ (pantothenic acid and panthenol). Within this group the panthenol is preferred. Derivatives of panthenol which can be used according to the invention are, in particular, the esters and ethers of panthenol and also cationically derivatized panthenols. Individual representatives are, for example, the panthenol triacetate, the panthenol monoethyl ether and its monoacetate and also the cationic panthenol derivatives disclosed in WO 92/13829. The said compounds of the vitamin B ₅ type are preferably contained 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 wt .-% are particularly preferred.

• Vitamin B ₆ (pyridoxine and 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 .-%, based on the total agent. The use in Form of palmitic acid ester, glucosides or phosphates may be preferred. The 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 the acetate, the nicotinate, the phosphate and the 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" is usually understood as meaning 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, however, meanwhile, the trivial name biotin has prevailed. Biotin is preferably present in the compositions according to the invention in amounts of from 0.0001 to 1.0% by weight, in particular in amounts of from 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 and its derivatives as well as nicotinic acid amide and biotin are particularly preferred.

A very particularly preferred group of further active ingredients are the silicone oils (S). Therefore, they are particularly preferably used in the compositions of the invention. Silicone oils cause a wide variety of effects. For example, they simultaneously affect the grip of dry and wet skin as well as the shine. The skin is generally described as pleasantly silky and supple without the skin having an unpleasant greasy shine. In addition to the combination of active substances used according to the invention, the advantages of the combination of active substances according to the invention and the silicone oils complement one another in an outstanding manner. Therefore, the use of silicone oils together with the combination of active substances according to the invention is very particularly preferred. The term silicone oils is understood by the person skilled in the art to mean several structures of organosilicon compounds. Initially, these are understood to mean the dimethiconols (S1).

Dimethiconols form the first group of silicones which are particularly preferred according to the invention. The dimethiconols according to the invention can be both linear and branched as well as cyclic or cyclic and branched. Linear dimethiconols can be represented by the following structural formula (S1-I):

(SiOHR ¹ ₂ ) - O - (SiR ² ₂ - O -) _x - (SiOHR ¹ ₂ ) (S1 - I) Branched dimethiconols can be represented by the structural formula (S1-II):

R ²

I (SiOHR ¹ ₂ ) - O - (SiR ² ₂ - O -) _x - Si - O - (SiR ² ₂ - O -) _y - (SiOHR ¹ ₂ )

I (SiR ² ₂ -O-) _z - (SiOHR ¹ ₂ )

The radicals R ¹ and R ² are each independently hydrogen, a methyl radical, a C ² to C 30 linear, saturated or unsaturated hydrocarbon radical, a phenyl radical and / or an aryl radical. Non-limiting examples of the groups represented by R ¹ and R ² include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, neopentyl, 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 radicals, benzyl radicals, halohydrocarbon radicals such as 3-chloropropyl, 4-bromobutyl, 3,3,3-trifluoropropyl, chlorocyclohexyl, bromophenyl, chlorophenyl and the like, and sulfur containing radicals such as mercaptoethyl, mercaptopropyl, mercaptohexyl, mercaptophenyl and the like; Preferably, R ¹ and R ^{2 is} an alkyl radical containing from 1 to about 6 carbon atoms, and most preferably R ¹ and R ^{2 are} 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 -. Preferred as R ¹ and R ² are methyl, phenyl and C ² to C 22 alkyl radicals. Of the C2 to C22 alkyl radicals, lauryl, stearyl and behenyl radicals are particularly preferred. The numbers x, y and z are integers and each run independently from 0 to 50,000. The molecular weights of Dimethicone lie between 1,000 D and 10000000 D. The viscosities are between 100 and 10,000,000 cPs measured at 25 ⁰ C by means of a glass capillary viscometer according to Dow Corning Corporate Test Method CTM 0004 dated 20 July 1970. Preferred viscosities are 1000-5000000 cPs, most preferred viscosities are between 10,000 and 3,000,000 cps. The most preferred range is between 50,000 and 2,000,000 cps.

Of course, the teaching of the invention also includes that the dimethiconols may already be present as an emulsion. In this case, the corresponding emulsion of the dimethiconols can be prepared both after the preparation of the corresponding dimethiconols from these and the usual methods of emulsification known to the person skilled in the art. For this purpose, both cationic, anionic, nonionic or zwitterionic surfactants and emulsifiers can be used as auxiliaries for the preparation of the corresponding emulsions. Of course, the emulsions of the dimethiconols can also be prepared directly by an emulsion polymerization process. Such methods are the Expert well known. For example, reference may be made to the Encyclopedia of Polymer Science and Engineering, Volume 15, Second Edition, pages 204 to 308, John Wiley & Sons, Inc. 1989. This reference is expressly incorporated herein by reference.

When the dimethiconols of the invention are used as an emulsion, the droplet size of the emulsified particles is according to the invention from 0.01 μm to 10000 μm, preferably from 0.01 to 100 μm, very particularly preferably from 0.01 to 20 μm and most preferably from 0.01 to 10 microns. The particle size is determined by the method of light scattering. If branched dimethiconols are used, it is to be understood that the branching is greater than a random branching, which occurs by impurities of the respective monomers randomly. For the purposes of the present invention, branched dimethiconols are therefore to be understood as meaning that the degree of branching is greater than 0.01%. Preferably, a degree of branching is greater than 0.1%, and most preferably greater than 0.5%. The degree of branching is determined from the ratio of unbranched monomers, that is, the amount of monofunctional siloxane, to the branching monomers, that is, the amount of tri- and tetrafunctional siloxanes. According to the invention, both low-branched and highly branched dimethiconols can be very particularly preferred.

Examples of such products include the following commercial products: Botanisil NU-150M (Botanigenics), Dow Coming 1-1254 Fluid, Dow Corning 2-9023 Fluid, Dow Corning 2-9026 Fluid, Ultrapure Dimethiconol (Ultra Chemical), Unisil SF- R (Universal Preserve), X-21-5619 (Shin-Etsu Chemical Co.), Abil OSW 5 (Degussa Care Specialties), ACC DL-9430 Emulsion (Taylor Chemical Company), AEC Dimethiconol & Sodium Dodecylbenzenesulfonate (A & E Connock (Perfumery & Cosmetics) Ltd.), BC Dimethiconol Emulsion 95 (Basildon Chemical Company, Ltd.), Cosmetic Fluid 1401, Cosmetic Fluid 1403, Cosmetic Fluid 1501, Cosmetic Fluid 1401 DC (all aforementioned Chemsil Silicones, Inc.), Dow Corning 1401 Fluid, Dow Corning 1403 Fluid, Dow Corning 1501 Fluid, Dow Corning 1784 HVF Emulsion, Dow Corning 9546 Silicone Elastomer Blend (all aforementioned Dow Corning Corporation), Dub Gel Sl 1400 (Stearinerie Dubois FiIs), HVM 4852 Emulsion (Crompton Corporation), Jeesilc 6056 (Jeen International Corporation), Lubrasil, Lubrasil DS (both Guardian Laboratories), Nonychosine E, Nonychosine V (both exsymol), SanSurf Petrolatum-25, Satin Finish (both Collaborative Laboratories, Inc.), Silatex-D30 (Cosmetic Ingredient Resources), Silsoft 148 , Silsoft E-50, Silsoft E-623 (all aforementioned Crompton Corporation), SM555, SM2725, SM2765, SM2785 (all aforementioned GE Silicones), Taylor T-SiI CD-1, Taylor TME-4050E (all Taylor Chemical Company Wacker-Belsil CM 3092, Wacker-Belsil CM 5040, Wacker-Belsil DM 3096, Wacker-Belsil DM 3112 VP, Wacker-Belsil DM 8005 VP, Wacker-Belsil DM 60081 VP (all Wacker-Chemie GmbH mentioned above). When the dimethiconols (S1) are included in the composition, these compositions contain from 0.01 to 10% by weight, preferably 0.1 to 8% by weight, more preferably 0.25 to 7.5% by weight and especially 0 , 5 to 5 wt.% Dimethiconol based on the composition.

Dimethicones (S2) form the second group of silicones, which are particularly preferred according to the invention. The dimethicones according to the invention can be both linear and branched as well as cyclic or cyclic and branched. Linear dimethicones can be represented by the following structural formula (S2-I):

(SiR ¹ ₃ ) - O - (SiR ² ₂ - O -) _x - (SiR ¹ ₃ ) (S2 - I)

Branched dimethicones can be represented by the structural formula (S2 - II):

R ²

I (SiR ¹ ₃ ) - O - (SiR ² ₂ - O -) _x - Si - O - (SiR ² ₂ - O -) _y - (SiR ¹ ₃ )

I

O - (SiR ² ₂ -O-) _z - (SiR ¹ ₃ )

The radicals R ¹ and R ² are each independently hydrogen, a methyl radical, a C ² to C 30 linear, saturated or unsaturated hydrocarbon radical, a phenyl radical and / or an aryl radical. Non-limiting examples of the groups represented by R ¹ and R ² include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, neopentyl, 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 radicals, benzyl radicals, halohydrocarbon radicals such as 3-chloropropyl, 4-bromobutyl, 3,3,3-trifluoropropyl, chlorocyclohexyl, bromophenyl, chlorophenyl and the like, and sulfur containing radicals such as mercaptoethyl, mercaptopropyl, mercaptohexyl, mercaptophenyl and the like; Preferably, R ¹ and R ^{2 is} an alkyl radical containing from 1 to about 6 carbon atoms, and most preferably R ¹ and R ^{2 are} 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 -. Preferred as R ¹ and R ² are methyl, phenyl and C ² to C 22 alkyl radicals. Of the C2 to C22 alkyl radicals, lauryl, stearyl and behenyl radicals are particularly preferred. The numbers x, y and z are integers and each run independently from 0 to 50,000. The molecular weights of Dimethicone lie between 1,000 D and 10000000 D. The viscosities are between 100 and 10,000,000 cPs measured at 25 ⁰ C by means of a glass capillary viscometer according to Dow Corning Corporate Test Method CTM 0004 dated 20 July 1970. Preferred viscosities are between 1000 and 5000000 cPs, very particularly preferred viscosities are between 10,000 and 3,000,000 cPs. The most preferred range is between 50,000 and 2,000,000 cps.

Of course, the teaching of the invention also includes that the dimethicones may already be present as an emulsion. In this case, the corresponding emulsion of the dimethicones can be prepared both after the preparation of the corresponding dimethicones from these and the usual methods of emulsification known to the person skilled in the art. For this purpose, both cationic, anionic, nonionic or zwitterionic surfactants and emulsifiers can be used as auxiliaries for the preparation of the corresponding emulsions. Of course, the emulsions of dimethicones can also be prepared directly by an emulsion polymerization process. Such methods are also well known to the person skilled in the art. For example, reference may be made to the Encyclopedia of Polymer Science and Engineering, Volume 15, Second Edition, pages 204 to 308, John Wiley & Sons, Inc. 1989. This reference is expressly incorporated herein by reference.

When the dimethicones of the invention are used as an emulsion, the droplet size of the emulsified particles according to the invention is 0.01 μm to 10000 μm, preferably 0.01 to 100 μm, very particularly preferably 0.01 to 20 μm and most preferably 0.01 to 10 microns. The particle size is determined by the method of light scattering. If branched dimethicones are used, it is to be understood that the branching is greater than a random branching, which occurs by impurities of the respective monomers randomly. For the purposes of the present invention, branched dimethicones are therefore to be understood as meaning that the degree of branching is greater than 0.01%. Preferably, a degree of branching is greater than 0.1%, and most preferably greater than 0.5%. The degree of branching is determined from the ratio of unbranched monomers, that is, the amount of monofunctional siloxane, to the branching monomers, that is, the amount of tri- and tetrafunctional siloxanes. According to the invention, both low-branched and highly branched dimethicones can be very particularly preferred.

When the dimethicones (S2) are contained in the composition according to the invention, these compositions contain from 0.01 to 10% by weight, preferably from 0.1 to 8% by weight, particularly preferably from 0.25 to 7.5% by weight, and in particular 0.5 to 5 wt.% Dimethiconol based on the composition.

Dimethicone copolyols (S3) form another group of preferred silicones. Dimethiconols can be represented by the following structural formulas:

(SiR ¹ ₃₎ - O - (SiR ² ₂ - O -) _x - (Sirpe - O -) _y - (SiR ¹ ₃₎ (S3 - I) or by the following structural formula:

PE - (SiR ¹ ₂ ) - O - (SiR ² ₂ - O -) _x - (SiR ¹ ₂ ) - PE (S3 - II)

Branched dimethicone copolyols can be represented by the structural formula (S3-IM):

R ² I PE - (SiR ¹ ₂ ) - O - (SiR ² ₂ - O -) _x - Si - O - (SiR ² ₂ - O -) _y - (SiR ¹ ₂ ) - PE (S3 - III)

I (SiR ² ₂ - O -) _z - (SiR ¹ ₂ ) - PE

or by the structural formula (S3 - IV):

R ² I (SiR ¹ ₃ ) - O - (SiR ² ₂ - O -) _x - Si - O - (SiR ² PE - O -) _y - (SiR ¹ ₃ ) (S3 - IV)

I (SiR ² ₂ -O-) _z - (SiR ¹ ₃ )

The radicals R ¹ and R ² are each independently hydrogen, a methyl radical, a C ² to C 30 linear, saturated or unsaturated hydrocarbon radical, a phenyl radical and / or an aryl radical. Non-limiting examples of the groups represented by R ¹ and R ² include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, neopentyl, 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 radicals, benzyl radicals, halohydrocarbon radicals such as 3-chloropropyl, 4-bromobutyl, 3,3,3-trifluoropropyl, chlorocyclohexyl, bromophenyl, chlorophenyl and the like, and sulfur containing radicals such as mercaptoethyl, mercaptopropyl, mercaptohexyl, mercaptophenyl and the like; Preferably, R ¹ and R ^{2 is} an alkyl radical containing from 1 to about 6 carbon atoms, and most preferably R ¹ and R ^{2 are} 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 -. Preferred as R ¹ and R ² are methyl, phenyl and C ² to C 22 alkyl radicals. Of the C2 to C22 alkyl radicals, lauryl, stearyl and behenyl radicals are particularly preferred. PE stands for a polyoxyalkylene radical. Preferred polyoxyalkylene radicals are derived from ethylene oxide, propylene oxide and glycerol. The numbers x, y and z are integers and each run independently from 0 to 50,000. The molecular weights of dimethicones are D is between 1000 and 10000000 D. The viscosities are between 100 and 10,000,000 cPs measured at 25 ⁰ C by means of a glass capillary viscometer according to Dow Corning Corporate Test Method CTM 0004 dated 20 July 1970. Preferred viscosities are from 1000 to 5,000,000 cps, most preferred Viscosities are between 10,000 and 3,000,000 cps. The most preferred range is between 50,000 and 2,000,000 cps.

Of course, the teaching of the invention also includes that the Dimethiconcopolymere can already be present as an emulsion. In this case, the corresponding emulsion of the dimethicone copolyols can be prepared both after the preparation of the corresponding dimethicone copolyols from these and the usual methods of emulsification known to the person skilled in the art. For this purpose, both cationic, anionic, nonionic or zwitterionic surfactants and emulsifiers can be used as auxiliaries for the preparation of the corresponding emulsions. Of course, the emulsions of dimethicone copolyols can also be prepared directly by an emulsion polymerization process. Such methods are also well known to the person skilled in the art. For example, reference may be made to the Encyclopedia of Polymer Science and Engineering, Volume 15, Second Edition, pages 204 to 308, John Wiley & Sons, Inc. 1989. This reference is expressly incorporated herein by reference.

When the dimethicone copolyols according to the invention are used as emulsion, the droplet size of the emulsified particles according to the invention is 0.01 μm to 10000 μm, preferably 0.01 to 100 μm, very particularly preferably 0.01 to 20 μm and most preferably 0.01 to 10 microns. The particle size is determined by the method of light scattering. If branched dimethicone copolyols are used, it is to be understood that the branching is greater than a random branching, which occurs by impurities of the respective monomers randomly. For the purposes of the present invention, branched dimethicone copolyols are therefore to be understood as meaning that the degree of branching is greater than 0.01%. Preferably, a degree of branching is greater than 0.1%, and most preferably greater than 0.5%. The degree of branching is determined from the ratio of unbranched monomers, that is, the amount of monofunctional siloxane, to the branching monomers, that is, the amount of tri- and tetrafunctional siloxanes. According to the invention, both low-branched and highly branched dimethicone copolyols can be very particularly preferred.

When the dimethicone copolyols (S3) are contained in the composition, these compositions contain from 0.01 to 10% by weight, preferably from 0.1 to 8% by weight, more preferably from 0.25 to 7.5% by weight, and especially from 0 , 5 to 5 wt.% Dimethiconecopolyol based on the composition. Aminofunctional silicones, or also called amodimethicones (S4), are silicones which have at least one (optionally substituted) amino group.

Such silicones may e.g. by the formula (S4-I)

M (R _a Q _b Si0 ₍₄ - _a - _{b) / 2) x} (R _c Si0 ₍₄ - _{c) / 2) y} M (S4-I)

Will be described, wherein in the above formula R is a hydrocarbon or a hydrocarbon radical having from 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 attached to hydrogen and the Z is an organic, amino-functional radical containing at least one amino-functional group, carbon and hydrogen atoms, carbon, hydrogen and oxygen atoms or carbon, hydrogen and nitrogen atoms; "a" assumes values in the range of about 0 to about 2, "b" assumes values in the range of about 1 to about 3, "a" + "b" is less than or equal to 3, and "c" is a number in the range from about 1 to about 3, and x is a number ranging from 1 to about 2,000, preferably from about 3 to about 50, and most preferably from about 3 to about 25, and y is a number ranging from about 20 to about 10,000 , preferably from about 125 to about 10,000, and most preferably from about 150 to about 1,000, and M is a suitable silicone end group as known in the art, preferably trimethylsiloxy. Non-limiting examples of the groups represented by R include alkyl groups 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 radicals, benzyl radicals, halohydrocarbon radicals such as 3-chloropropyl, A-bromobutyl, 3,3,3-trifluoropropyl, chlorocyclohexyl, bromophenyl, chlorophenyl and the like, and sulfur-containing radicals such as mercaptoethyl, mercaptopropyl, mercaptohexyl, mercaptophenyl and the like; preferably R is an alkyl radical containing from 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 -, - (CHz) 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 -.

Z is an organic, amino-functional radical containing at least one functional amino group. A possible formula for Z is NH (CH ₂ ) _Z NH ₂ , wherein z is 1 or more. Another possible formula for Z is -NH (CH ₂ ) _Z (CH ₂ ) _ZZ NH, wherein 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 radical. Another possible formula for Z is - N (CH ₂ ) _Z (CH ₂ ) _ZZ NX ₂ or -NX ₂ , wherein each X of X _{2 is} independently selected from the group consisting of hydrogen and alkyl groups of 1 to 12 carbon atoms, and zz 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" assumes values in the range of about 0 to about 2, "b" assumes 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 the R ₃ Q _b SiO _{(4. a} - _{b) / 2} units to the R ₀ SiO ₍₄ _ _c y ₂ units is in the range of from about 1: 2 to 1:65, preferably from about 1: 5 to about 1:65, and most preferably from about 1: 15 to about 1: 20. When one or more silicones of the above formula are employed, then the various variable substituents in the above formula may be different for the various silicone components present in the silicone blend.

Preferred agents according to the invention are characterized in that they contain an amino-functional silicone of the formula (S4-II)

R _'a G ₃ - _a -Si (OSiG _{2) n} - (OSiG _b R' ₂ _ _{b) m} -O-SiG ₃ - _a -R _'a (S4 - 11)

contain, 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 (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;} a is a number between 0 and 3, in particular 0; b is a number between 0 and 1, in particular 1, m and n are numbers whose sum (m + n) is between 1 and 2000, preferably between 50 and 150, where n preferably values 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, R ^' is a monovalent radical selected from o -N (R ") - CH ₂ -CH ₂ -N (R ¹¹ J ₂ o -N ( R ¹¹ J 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 ⁺ R "H ₂ ^A", wherein each R "represents identical or different radicals from the group -H, - phenyl, -benzyl, C- |. ₂₀ -alkyl, 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. Particularly preferred agents according to the invention are characterized in that they contain an amino-functional silicone of the formula (S4-III)

(CH ₃₎ 3 Si- [OSi (CH 3)] n [OSi (CH3) 2] _m OSi (CH3) ₃ (S4 - III),

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

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

These silicones are referred to as trimethylsilylamodimethicones according to the INCI declaration.

Compositions according to the invention which are characterized in that they contain an amino-functional silicone of the formula (S4-IV) are also particularly preferred.

R- [Si (CH _{3) 2} -O] _n1 [Si (R) -O] _m - [Si (CH _{3) 2] n2} -R (S4 - IV),

I (CH ₂ ) ₃ NH (CH ₂ ) ₂ NH ₂

in which R is -OH, -O-CH ₃ or a -CH ₃ group and m, n1 and n2 are numbers whose sum (m + n1 + n2) is between 1 and 2,000, preferably between 50 and 150 , where the sum (n1 + n2) preferably 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.

These silicones are referred to as amodimethicones according to the INCI declaration.

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 also expressed in mg KOH / g.

When the amodimethicones (S4) are contained in the composition, these compositions contain 0.01 to 10 wt.%, Preferably 0.1 to 8 wt.%, Particularly preferably 0.25 to 7.5 wt.%, And especially 0 , 5 to 5 wt.% Amodimethicone based on the composition. Of course, the invention also encompasses the recognition that a mixture of at least 2 different silicones can be used in the compositions according to the invention. Preferred mixtures of different silicones are, for example, dimethicones and dimethiconols, linear dimethicones and cyclic dimethiconols. Very particularly preferred mixtures of silicones contain at least one cyclic dimethiconol and / or at least one dimethicone, at least one further noncyclic dimethicone and / or at least one further dimethiconol. Most preferred mixtures contain at least one amino-functional silicone and at least one of the mixtures described above. If different silicones are used as a mixture, the mixing ratio is largely variable. Preferably, however, all silicones used for mixing are used in a ratio of 5: 1 to 1: 5 in the case of a binary mixture. A ratio of 3: 1 to 1: 3 is particularly preferred. Very particularly preferred mixtures contain all the silicones contained in the mixture largely in a ratio of about 1: 1, in each case based on the amounts used in wt.%.

When silicone compounds are included in the composition, these compositions contain from 0.01 to 10% by weight, preferably from 0.1 to 8% by weight, more preferably from 0.25 to 7.5% by weight and especially from 0.5 to 5 % By weight of silicone mixture based on the composition.

Furthermore, in a preferred embodiment of the invention, a UV filter (I) can additionally be used. The UV filters to be used according to the invention are not subject to any general restrictions with regard to their structure and their physical properties. On the contrary, all UV filters which can be used in the cosmetics sector and whose absorption maximum lies in the UVA (315-400 nm), in the UVB (280-315 nm) or in the UVC (<280 nm) range are suitable. UV filters with an absorption maximum in the UVB range, in particular in the range from about 280 to about 300 nm, are particularly preferred.

On the one hand, the UV filters serve for product protection. They prevent fading, for example, the colored phases of the fittings. At the same time, the UV protection filters also protect the washed skin. In particular, by the use together with polymers increased deposition of UV filters on the skin during washing is achieved. This leaves after rinsing the skin and an increased amount on the skin, thus leading to an increased effect.

The UV filters 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-aminobenzoic acid, N, N, N-trimethyl-4- (2-oxoborn-3-ylidnenethyl) aniline-n-methylsulfate, SSδ-trinnethylcyclohexylsalicylate (homosalate), 2-hydroxybenzoyl 4-methoxy-benzophenone (benzophenone-3; Uvinul ^® M 40, Uvasorb MET ^{®, ®} Neo Heliopan BB, Eusolex ^® 4360), 2-phenylbenzimidazole-5-sulfonic acid and potassium, sodium and triethanolamine salts (phenylbenzimidazole sulfonic Acid; Parsol ^® HS; Neo Heliopan Hydro ^®), 3,3 '- (1, 4-phenylenedimethylene) bis (7,7-dimethyl-2-oxo-bicyclo [2.2.1] hept-1-yl-methane sulfonic acid) and salts thereof, 1- (4-tert-butylphenyl) -3- (4-methoxyphenyl) propane-1, 3- dione Methoxydibenzoylmethane (butyl; Parsol ^® 1789 Eusolex ^® 9020) α- (2- oxoborn-3-ylidene) - toluene-4-sulfonic acid and salts thereof, ethoxylated 4-aminobenzoic acid ethyl ester (PEG-25 PABA; Uvinul ^® P 25), 4-dimethylaminobenzoic acid 2-ethylhexyl (octyl dimethyl PABA; Uvasorb ^® DMO Escalol® ^® 507, Eusolex ^® 6007), salicylic acid 2-ethylhexyl ester (octyl salicylate; Escalol ^® 587, Neo Heliopan OS ^®, Uvinul ^® 018), 4-methoxycinnamic acid isopentyl (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-lsopro- pylbenzylsalicylat, 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} - acrylamide, 2,4-dihydroxy (benzophenone-1; Uvasorb ^® 20 H, Uvinul ^® 400) 1, 1 '- Diphenylacrylonitrilsäure-2-ethylhexyl ester (Octocrylene; Eusolex ^® OCR, Neo Heliopan ^® Type 303 , Uvinul ^® N 539 SG), o-aminobenzoic acid menthyl ester (menthyl Anthrani late; 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-diphenylacrylate 2'-ethylhexyl. Preference is given to 4-aminobenzoic acid, N, N, N-trimethyl-4- (2-oxoborn-3-ylidenemethyl) aniline methylsulfate, 3,3,5-trimethylcyclohexylsalicylate, 2-hydroxy-4-methoxybenzophenone , 2-phenylbenzimidazole-5-sulfonic acid and its potassium, sodium and triethanolamine salts, 3,3 '- (1, 4-phenylenedimethylene) -bis (7,7-dimethyl-2-oxo-bicyclo- [2.2.1] hept-1-yl-methanesulphonic acid) and its salts, 1- (4-tert-butylphenyl) -3- (4-methoxyphenyl) -propane-1,3-dione, α- (2-oxoborn-3-) yliden) -toluene-4-sulfonic acid and its salts, ethoxylated 4-aminobenzoic acid ethyl ester, 2-ethylhexyl A-dimethylaminobenzoate, 2-ethylhexyl salicylate, A-

Methoxycinnamic acid isopentyl ester, 4-methoxycinnamic acid 2-ethylhexyl ester, 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 the N- {(2 and 4) - [2-oxoborn-3-ylidenemethyl] benzyl} -acrylamide. Very particularly preferred according to the invention are 2-hydroxy-4-methoxybenzophenone, 2-phenylbenzimidazole-5-sulfonic acid and its potassium, sodium and triethanolamine salts, 1- (4-tert-butylphenyl) -3- (4-methoxyphenyl) - propan-1,3-dione, 4-methoxycinnamic acid 2-ethylhexyl ester and 3- (4'-methylbenzylidene) -D, L-camphor.

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

Furthermore, it has been found that structurally similar UV filters in many cases, the water-insoluble compound in the teaching of the invention has the higher effect compared to such water-soluble compounds that differ from it by one or more additional ionic groups. For the purposes of the invention, water-insoluble UV filters are those which dissolve in water at not more than 1% by weight, in particular not more than 0.1% by weight, at 20 ^° C. Furthermore, these compounds should be soluble in the usual cosmetic oil components at room temperature to at least 0.1, in particular at least 1 wt .-%). The use of water-insoluble UV filters may therefore be preferred according to the invention.

According to a further embodiment of the invention, preference is given to those UV filters 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 UV-absorbing group. This group can in principle be derived from the known UV filters which can be used in the cosmetics sector, in which a group, generally a hydrogen atom, of the UV filter is replaced by a cationic group Q, in particular having a quaternary amino function , Compounds from which the structural part U can be derived are, for example, substituted benzophenones, p-aminobenzoic acid esters,

diphenylacrylic,

cinnamic,

salicylic acid,

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 chosen so that the absorption maxima of the UV filter can be both in the UVA (315-400 nm) and in the UVB (280-315 nm) or in the UVC (<280 nm) range. UV filters with an absorption maximum in the UVB range, in particular in the range from about 280 to about 300 nm, are particularly preferred.

Furthermore, the structural part U, also as a function of structural part Q, is preferably selected so 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, as a cationic group, a quaternary ammonium group. This quaternary ammonium group can in principle be connected directly to the structural part U, so that the structural part U represents one of the four substituents of the positively charged nitrogen atom. Preferably, however, one of the four substituents on the positively charged nitrogen atom is a group, especially an alkylene group of 2 to 6 carbon atoms, which functions as a compound between the structural portion U and the positively charged nitrogen atom.

Advantageously, the group Q has the general structure - (CH ₂ ) χ-N ⁺ R ¹ R ² R ³ X ^" , in which x is an integer from 1 to 4, R ¹ and R ² independently of one another represent |. ₄ alkyl groups, R ³ stands for a C |. ₂₂ alkyl group or a benzyl group and X ^"is a physiologically acceptable anion. In the context of this general structure, x preferably represents the number 3, R ¹ and R ² each represent a methyl group and R ^{3 represents} either 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 acceptable 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 available compounds cinnamic acid-trimethylammonium chloride (lncroquat ^® UV-283) and dodecyl tosylate (Escalol ^® HP 610).

Of course, the teaching of 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 contained in the compositions according to the invention usually in amounts of 0.1-5 wt .-%, based on the total agent. Levels of 0.4-2.5 wt .-% are preferred. Finally, the effect of the drug combination can also be increased by the combined use with plant extracts.

Usually these extracts are produced by extraction of the whole plant. However, in individual cases it may also be preferred to prepare 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, particular reference is made to the extracts listed in the table beginning on page 44 of the 3rd edition of the guideline for the ingredient declaration of cosmetic products, published by the Industrial Association for Personal Care and Detergent e.V. (IKW), Frankfurt.

According to the invention are especially the extracts of green tea, oak bark, stinging nettle, witch hazel, hops, chamomile, burdock root, horsetail, hawthorn, linden, almond, aloe vera, spruce needle, horse chestnut, sandalwood, juniper, coconut, mango, apricot, lime, wheat , Kiwi, melon, orange, grapefruit, sage, rosemary, birch, mallow, meadowfoam, quenelle, yarrow, thyme, lemon balm, toadstool, coltsfoot, marshmallow, meristem, ginseng, ginger root, Echinacea purpurea, Olea europea, Foeniculum vulgaris and Apium graveolens prefers.

Particularly preferred are the extracts of green tea, oak bark, stinging nettle, witch hazel, hops, chamomile, burdock root, horsetail, lime blossom, almond, aloe vera, coconut, mango, apricot, lime, wheat, kiwi, melon, orange, grapefruit, sage, Rosemary, birch, meadowfoam, quenelle, yarrow, toadstool, meristem, ginseng and ginger root.

Especially suitable for the composition according to the invention are the extracts of green tea, almond, aloe vera, coconut, mango, apricot, lime, wheat, kiwi and melon.

As extraction agent for the preparation of said plant extracts water, alcohols and mixtures thereof can be used. Among the alcohols are lower alcohols such as ethanol and isopropanol, but especially polyhydric alcohols such as ethylene glycol and propylene glycol, both as sole extractant and in admixture with water, are preferred. Plant extracts based on water / propylene glycol in a ratio of 1:10 to 10: 1 have proven to be particularly suitable.

The plant extracts can be used according to the invention both in pure and in diluted form. If used in diluted form, they usually contain about 2 to 80% by weight of active substance and, as solvent, the extractant or extractant mixture used in its production.

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

It has also been found that the effect of the active ingredient combination according to the invention in cosmetic compositions in combination with substances which contain primary or secondary amino groups, can be further increased. Examples of such amino compounds include ammonia, monoethanolamine, 2-amino-2-methyl-1-propanol, 2-amino-2-methyl-propanediol and basic amino acids such as lysine, arginine or histidine. Of course, these amines can also be used in the form of the corresponding salts with inorganic and / or organic acids, such as, for example, ammonium carbonate, ammonium citrate, ammonium oxalate, ammonium tartrate or lysine hydrochloride. The amines are used together with the active compound according to the invention in ratios of from 1:10 to 10: 1, preferably from 3: 1 to 1: 3, and very particularly preferably in stoichiometric amounts.

The compositions according to the invention can furthermore contain a perfume component, preferably a perfume oil.

As perfume oils are called mixtures of natural and synthetic fragrances. Natural fragrances are extracts of flowers (lily, lavender, roses, jasmine, neroli, ylang-ylang), stems and leaves (geranium, patchouli, petitgrain), fruits (aniseed, coriander, caraway, juniper), fruit peel (bergamot, lemon, Oranges), roots (macis, angelica, celery, cardamom, costus, iris, calmus), wood (pine, sandal, guaiac, cedar, rosewood), herbs and grasses (tarragon, lemongrass, sage, thyme), Needles and twigs (spruce, fir, pine, pines), resins and balsams (galbanum, elemi, benzoin, myrrh, olibanum, opoponax). Furthermore, animal raw materials come into question, such as civet and Castoreum. Typical synthetic fragrance compounds are ester type products, ethers, aldehydes, ketones, alcohols and hydrocarbons. Fragrance compounds of the ester type are known e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate,

Ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate and benzylsalicylate. The ethers include, for example, benzyl ethyl ether, to the aldehydes, for example, the linear alkanals having 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones such as the Jonone, oc- \ somethylionon and Methylcedrylketon to the Alcohols Anethole, citronellol, eugenol, isoeugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include Terpenes and balms. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance. Also essential oils of lower volatility, which are mostly used as flavoring components, are suitable as perfume oils, eg sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon oil, lime blossom oil, juniper berry oil, vetiver oil, oliban oil, galbanum oil, labolanum oil and lavandin oil. Preferably, bergamot oil, dihydromyrcenol, lilial, lyral, citronellol, phenylethyl alcohol, α-hexylcinnamaldehyde, geraniol, benzylacetone, cyclamen aldehyde, linalool, Boisambrene Forte, Ambroxan, indole, hedione, Sandelice, citron oil, tangerine oil, orange oil, Allylamylglycolat, Cyclovertal, Lavandinöl, Muskateller Sage oil, β-damascone, geranium oil Bourbon, cyclohexyl salicylate, Vertofix Coeur, Iso-E-Super, fixolide NP, evernyl, iraldeine gamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, romilllat, irotyl and floramate alone or in mixtures.

The perfume oils are generally added to the composition in an amount of from 0.05 to 5% by weight, preferably from 0.1 to 2.5% by weight and in particular from 0.2 to 1.5% by weight, based on the total composition.

The perfume oils may be added to the composition in liquid form, neat or diluted with a solvent. Suitable solvents for this purpose are, for. For example, ethanol, isopropanol, diethylene glycol monoethyl ether, glycerol, propylene glycol, 1, 2-butylene glycol, dipropylene glycol, diethyl phthalate, triethyl citrate, isopropyl myristate, etc.

In addition to the inventively mandatory combination of active ingredients and the other preferred components mentioned above, the agents according to the invention may in principle contain all other components known to those skilled in the art of such cosmetic compositions.

Further active ingredients, auxiliaries and additives are, for example:

Thickening agents such as gelatin or vegetable gums, for example agar-agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, linseed gums, dextrans, cellulose derivatives, e.g. As methyl cellulose, hydroxyalkyl cellulose and carboxymethyl cellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays and phyllosilicates such. As bentonite or fully synthetic hydrocolloids such. Polyvinyl alcohol, Ca, Mg or Zn soaps, structurants such as maleic acid and lactic acid, perfume oils, dimethyl isosorbide, cyclodextrins,

Solvents and mediators such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol, fiber-structure-improving active ingredients, in particular mono-, di- and oligosaccharides such as, for example, glucose, galactose, fructose, fructose and lactose, quaternized amines such as methyl-1-alkylamidoethyl-2-alkylimidazolinium methosulfate,

Defoamers like silicones,

Dyes for staining the agent,

Anti-dandruff agents such as Piroctone Olamine, Zinc Omadine and Climbazole,

Light stabilizers, in particular derivatized benzophenones, cinnamic acid derivatives and

Triazines, other substances for adjusting the pH, such as α- and β-

hydroxy,

Active ingredients such as allantoin and bisabolol,

Cholesterol,

Complexing agents such as EDTA, NTA, β-alaninediacetic acid and phosphonic acids,

Swelling and penetration substances such as glycerol, propylene glycol monoethyl ether, carbonates,

Hydrogencarbonates, guanidines, ureas and primary, secondary and tertiary phosphates,

Ceramides. Ceramides are understood as meaning N-acylsphingosine (fatty acid amides of sphingosine) or synthetic analogs of such lipids (so-called pseudo-ceramides),

Opacifiers such as latex, styrene / PVP and styrene / acrylamide copolymers,

Pearlescing agents such as ethylene glycol mono- and distearate and PEG-3-distearate,

pigments

Reducing agents such. B. thioglycolic acid and its derivatives, thiolactic acid, cysteamine,

Thiomalic acid and α-mercaptoethanesulfonic acid,

Propellants such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air,

antioxidants

deoxy sugars,

plant glycosides,

Polysaccharides such as fucose or rhamnose.

In a further preferred embodiment of the invention, the active ingredient combination according to the invention is used in agents for dyeing keratinic fibers. In this case, the combination of active substances according to the invention can in principle be added directly to the colorant. Preferably, however, the application of the active ingredient to the dyed keratinic fiber takes place in a separate step either directly after the actual dyeing process or in separate treatments, optionally also days or weeks after the dyeing process.

The term dyeing process comprises all processes known to those skilled in the art, in which a colorant is applied to the hair, which may have been moistened, and left on the hair either for a period of a few minutes to about 45 minutes and then with water or a surfactant-containing agent is rinsed out or completely on the Hair is left. It is in this context explicitly on the known monographs, z. B. Kh. Schrader, bases and formulations of cosmetics, 2nd edition, Hüthig book Verlag, Heidelberg, 1989, referenced that reflect the corresponding knowledge of the expert.

As already mentioned above, it is also possible within the scope of the teaching according to the invention, although less preferably, to incorporate the active substance combination directly into the dyeing or toning agents.

The composition of the dyeing or tinting agent is not subject to any fundamental restrictions. As a dye (precursor) e can

Developer and coupler type oxidation dye precursors,

Natural and synthetic direct dyes and

• Precursors of naturally occurring dyes, such as indole and indoline derivatives, and mixtures of representatives of one or more of these groups are used.

Developer type oxidation dye precursors are typically primary aromatic amines having another 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 its derivatives used. Suitable developer components are, for example, p-phenylenediamine, p-toluenediamine, p-aminophenol, o-aminophenol, 1- (2'-hydroxyethyl) -2,5-diaminobenzene, N, N-bis (2-hydroxy-ethyl) -p phenylenediamine, 2- (2,5-diaminophenoxy) ethanol, 4-amino-3-methylphenol, 2,4,5,6-tetrahydaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 4-hydroxy -2,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2-dimethylamino-4,5,6-triaminopyrimidine, 2-

Hydroxymethylamino-4-amino-phenol, bis (4-aminophenyl) amine, 4-amino-3-fluorophenol, 2-aminomethyl-4-aminophenol, 2-hydroxymethyl-4-aminophenol, 4-amino-2 - ((diethylamino ) - methyl) phenol, bis (2-hydroxy-5-aminophenyl) -methane, 1, 4-bis (4-aminophenyl) -diazacycloheptane, 1, 3-bis (N (2-hydroxyethyl) -N ( 4-aminophenylamino)) - 2-propanol, 4-amino-2- (2-hydroxyethoxy) -phenol, 1, 10-bis (2,5-diaminophenyl) -1, 4,7,10-tetraoxadecane and 4, 5-diaminopyrazole derivatives according to EP 0 740 741 or WO 94/08970, such as, for example, US Pat. B. 4,5-diamino-1- (2'-hydroxyethyl) pyrazole. Particularly advantageous developer components are p-phenylenediamine, p-toluenediamine, p-aminophenol, 1- (2'-hydroxyethyl) -2,5-diaminobenzene, 4-amino-3-methylphenol, 2-aminomethyl-4-aminophenol, 2,4 , 5,6-tetraaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine. As the coupler type oxidation dye precursors, m-phenylenediamine derivatives, naphthols, resorcin and resorcinol derivatives, pyrazolones and m-aminophenol derivatives are usually used. Examples of such coupler components are m-aminophenol and its derivatives such as 5-amino-2-naphthylphenol, 5- (3

Hydroxypropylamino) -2-naphthylphenol, 3-amino-2-chloro-6-naphthylphenol, 2-hydroxy-4-aminophenoxyethanol, 2,6-dimethyl-3-anninophenol, 3-trifluoroacetylamino-2-chloro-6-methylphenol, 5 -Amino-4-chloro-2-naphthylphenol, 5-amino-4-nethoxy-2-naphthylphenol, 5- (2'-

Hydroxyethyl) -amino-2-naphthylphenol, 3- (diethylamino) -phenol, N-cyclopentyl-3-aminophenol, 1, 3-dihydroxy-5- (methylannino) -benzene, 3- (ethylamino) -4-naphthylphenol, and 2 , 4-

Dichloro-3-aminophenol, o-aminophenol and its derivatives, m-diaminobenzene and its derivatives such as 2,4-diaminophenoxyethanol, 1, 3

Bis- (2,4-diaminophenoxy) -propane, 1-methoxy-2-amino-4- (2'-hydroxyethylannino) benzene, 1, 3

Bis (2,4-diaminophenyl) propane, 2,6-bis (2-hydroxyethylamino) -1-methylbenzene and 1-aminobenzene

3-bis (2'-hydroxyethyl) aminobenzene, o-diaminobenzene and its derivatives such as 3,4-diaminobenzoic acid and 2,3-

Diamino-1-nnethylbenzol,

Di- or trihydroxybenzene derivatives such as, for example, 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-methylannino-6-nethoxy-pyridine, 2,6-dihydroxy-3,4-dimethyl-pyridine, 2,6-dihydroxy-4-methyl-pyridine, 2,6-diaminopyridine, 2, 3-diamino-6-methoxypyridine and 3,5-diamino-2,6-dinethoxypyridine,

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, for example, 6-hydroxybenzomorpholine and 6-aminobenzomorpholine,

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,

Methylenedioxybenzene derivatives such as 1-hydroxy-3,4-methylenedioxybenzene, 1-

Amino-3,4-ethylenedioxybenzene and 1- (2'-hydroxyethyl) amino-3,4-ethylenedioxybenzene,

Particularly suitable coupler components are 1-naphthol, 1, 5, 2,7- and 1, 7-dihydroxynaphthalene, 3-aminophenol, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridine, resorcinol, A- Chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol and 2,6-dihydroxy-3,4-dimethylpyridine.

Direct dyes are usually nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols. Particularly suitable substantive dyes are those under the international designations or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, Basic Yellow 57, Disperse Orange 3, HC Red 3, HC Red BN, Basic Red 76, HC Blue 2, HC Blue 12, Disperse Blue 3, Basic Blue 99, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9, Basic Brown 16 and Basic Brown 17 known compounds as well as 1, 4-bis- (β- hydroxyethyl) amino-2-nitrobenzene, 4-amino-2-nitrodiphenylannin 2'-carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, hydroxyethyl-2-nitro-toluidine, picramic acid, 2-amino 6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene.

Direct dyes found in nature include, for example, henna red, henna neutral, henna black, chamomile flower, sandalwood, black tea, buckthorn bark, sage, sawnwood, madder root, catechu, sedre and alcano root.

It is not necessary that the oxidation dye precursors or the direct dyes each represent uniform compounds. Rather, in the hair colorants according to the invention, due to the production process for the individual dyes, in minor amounts, other components may be included, as far as they do not adversely affect the dyeing result or for other reasons, eg. As toxicological, must be excluded.

For example, indoles and indolines and their physiologically acceptable salts are used as precursors of naturally-analogous dyes. Preferably, such indoles and indolines are used which have at least one hydroxyl or amino group, preferably as a substituent on the six-membered ring. These groups may carry further substituents, e.g. Example in the form of etherification or esterification of the hydroxy group or alkylation of the amino group. Particularly advantageous properties have 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, 6-hydroxyindoline, 6-aminoindoline and 4-aminoindoline and 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.

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

The indoline and indole derivatives in the colorants used in the process according to the invention both as free bases and in the form of their physiologically acceptable salts with inorganic or organic acids, eg. As the hydrochlorides, sulfates and hydrobromides are used.

When using dye precursors of the indoline or indole type, it may be preferable to use them together with at least one amino acid and / or at least one oligopeptide. Preferred amino acids are aminocarboxylic acids, in particular α-aminocarboxylic acids and ω-aminocarboxylic acids. Arginine, lysine, ornithine and histidine are again particularly preferred among the α-aminocarboxylic acids. A very particularly preferred amino acid is arginine, especially in free form, but also used as the hydrochloride.

Hair dyes, especially if the dyeing is oxidative, be it with atmospheric oxygen or other oxidizing agents such as hydrogen peroxide, are usually weakly acidic to alkaline, d. H. adjusted to pH values in the range of about 5 to 1 1. For this purpose, the colorants contain alkalizing agents, usually alkali metal or alkaline earth metal hydroxides, ammonia or organic amines. Preferred alkalizing agents are monoethanolamine, monoisopropanolamine, 2-amino-2-methyl-propanol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, 2-amino-2 -methylbutanol and triethanolamine and alkali and alkaline earth metal hydroxides. In particular, monoethanolamine, triethanolamine and 2-amino-2-methyl-propanol and 2-amino-2-methyl-1, 3-propanediol are preferred within the scope of this group. The use of ω-amino acids such as ω-aminocaproic acid as an alkalizing agent is also possible.

If the formation of the actual hair dyes takes place in the context of an oxidative process, conventional oxidizing agents, in particular hydrogen peroxide or its addition products of urea, melamine or sodium borate can be used. However, oxidation with atmospheric oxygen as the sole oxidant may be preferred. Furthermore, it is possible to carry out the oxidation by means of enzymes, which enzymes are used both for the production of oxidizing per-compounds and for enhancing the effect of a small amount of existing oxidizing agents, or enzymes, the electrons from suitable developer components (reducing agent) Transmitted atmospheric oxygen. Oxidases such as tyrosinase, ascorbate oxidase and laccase but also glucose oxidase, uricase or pyruvate oxidase are preferred. Furthermore, the procedure is called the effect small amounts (e.g., 1% and less, based on total agent) of hydrogen peroxide by peroxidases.

Conveniently, the preparation of the oxidizing agent is then mixed with the preparation with the dye precursors immediately prior to dyeing the hair. The resulting ready-to-use hair dye preparation should preferably have a pH in the range of 6 to 10. Particularly preferred is the use of the hair dye in a weakly alkaline medium. The application temperatures may range between 15 and 40 ^° C., preferably at the temperature of the scalp. After a contact time of about 5 to 45, especially 15 to 30, minutes, the hair dye is removed by rinsing of the hair to be dyed. The Nachwaschen with a shampoo is omitted if a strong surfactant-containing carrier, eg. As a dyeing shampoo was used.

Especially with 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 appropriate after an intermediate rinse. After a further exposure time of 10 to 20 minutes is then rinsed and nachshampooniert if desired. In this embodiment, according to a first variant, in which the previous application of the dye precursors is intended to effect a better penetration into the hair, the corresponding agent is adjusted to a pH of about 4 to 7. According to a second variant, an air oxidation is initially desired, wherein the applied agent preferably has a pH of 7 to 10. In the subsequent accelerated post-oxidation, the use of acidified peroxydisulfate solutions may be preferred as the oxidizing agent.

Furthermore, the formation of the coloration can be supported and increased by adding certain metal ions to the agent. Such 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⁺ . Particularly suitable are Zn ²⁺ , Cu ²⁺ and Mn ²⁺ . The metal ions can in principle be used in the form of any physiologically acceptable salt. Preferred salts are the acetates, sulfates, halides, lactates and tartrates. By using these metal salts, both the formation of the dyeing can be accelerated and the color shade can be specifically influenced.

A second object of the invention is the use of the composition according to the invention for improving the hair structure of human hair.

Particularly preferred according to the invention is the use of the agent for increasing the gene expression of several hair keratins. Particularly preferred according to the invention is the use of the agent for increasing the gene expression of the hair keratins hHa4, hHa3-l, hHa2, hHb6 and the cytokeratins for strengthening the internal structure of human hair.

A third object of the invention is a method for improving the hair structure of human hair, in which the composition according to the invention is applied to the hair or the hairy skin.

Preferred according to the invention is a method for increasing the gene expression of the hair keratins hHa4, hHa3-l, hHa2, hHb6 and the cytokeratins for strengthening the internal structure of human hair.

The following examples illustrate the invention without, however, limiting it to:

All figures are in weight percent (w%).

Examples:

A: shampoo

Designation% by weight

Citric acid 0.5

Laureth sulfate 13

Disodium Cocoamphodiacetate 6

Salicylic acid 0.2

D-panthenol 75% 0.2

Na benzoate 0.5

Euperlan ^{® 1} PK 3000 AM 2.6

Cetiol HE 0.5 ^®2

Hydrogenated Castor OiI 0.1

Keratin hydrolyzate 0.2

Ubiquinone 0.01

Ceteareth-25 0.5

NaCl 0.5

Water ad 100

B: hair conditioner

Designation% by weight

Paraffin Liquidum 1, 5

^®3 Dehyquart F 75 1 5

Isopropyl myristate 1

Varisoft ^{® 4} W 75 PG 1, 5

Cetearyl alcohol 4

Cyclomethicone 0.5

Dimethicone 0.5

Propylparaben 0.2

Ubiquinone 0.01

Cetearath-9 0.8

Stearamidopropyldimethylamines 0.8

Dehyquart ® ⁵ A CA 3

Citric acid 0.4

Methylparaben 0.2 Phenoxyethanol 0.2

Keratin hydrolyzate 0.5

Salcare SC 96 0.5 ^®6

Water ad 100

C: hair conditioner

Designation% by weight

Stenol 1618 ^®7 7

Keratin hydrolyzate 0.5

Genamin KDM-P 1 ^®8, 2

^®3 Dehyquart F 75 1 2

Amodimethicone 0.5

Ubiquinone 0.01

Ceteareth-25 0.8

Cetyl ester 0.5

Methylparaben 0.2

Perfume 0.3

Phenoxyethanol 0.4

Water ad 100

D: Hair Tonic

Designation% by weight

Keratin hydrolyzate 0.1

Allantoin 0.1

Benzophenone-4 0,03

Synthalen® ^®9 K 0.24

Neutral ^®10 TE 0.25

Ethanol 96% DEP denatures 40

Ubiquinone 0.01

Ceteareth-25 0.1

Menthol, of course, 0.03

Water ad 100 the following commercial products are used: INCI name: Aqua, Glycol Distearate, Glycerin, Laureth-4, Cocamidopropyl Betaine, Formic Acid; Active substance: 40% in water; Cognis INCI name: PEG-7 glyceryl cocoate; Cognis INCI name: distearoylethyl hydroxyethylmonium methosulfate, cetearyl alcohol; Active substance: 65 - 72%; Cognis 1-methyl-2-nortallowalkyl-3-tallow fatty acid amidoethylimidazolinium nethanesulfate; INCI name: Quaternium-27, propylene glycol; Active ingredient: 74 - 77%; Goldschmidt-Rewo trimethylhexadecylammonium chloride; INCI name: Aqua, Cetrimonium Chloride; Active ingredient: 24 - 26%; Cognis INCI name: Polyquaternium-37, Propylene Glycol Dicaprylate / Dicaprate PPG-1 Trideceth-6; Active ingredient: 50%; Ciba C16-C18 fatty alcohol, ethoxylated (9 EO) N, N, N-trimethyl-N- (C20-C22-alkyl) ammonium chloride; INCI name: Behentrimonium Chloride; Active substance: 77 - 83%; Clariant polyacrylic acid; INCI name: carbomer; 3V Sigma N, N, N, N-tetrakis (2-hydroxypropyl) ethylenediamine edetol; INCI name: tetrahydroxypropyl ethylene diamine; BASF

Claims

claims:

1. agent, in particular for the treatment of the hair, containing at least one protein hydrolyzate and at least one biochinone.

2. Composition according to claim 1, characterized in that the ratio of protein hydrolyzate (s) to the or the biochinone (s) in the range of 2: 1 to 1000: 1, preferably in the range of 5: 1 to 500: 1 and in particular ranging from 10: 1 to 200: 1.

3. Composition according to one of claims 1 or 2, characterized in that it contains as protein hydrolysates keratin hydrolysates from sheep's wool or Collagenhydrolysate.

4. Composition according to one of claims 1 to 3, characterized in that the protein hydrolyzate has a size of 400 to 1200 daltons.

5. Composition according to one of claims 1 to 4, characterized in that it or the biochinone (s) - based on its weight - in an amount of 0.0000005 to 2%, preferably in an amount of 0.000001 to 1 % and in particular in an amount of 0.00001 to 0.5%.

6. Composition according to one of claims 1 to 5, characterized in that the or the biochinone (s) is (are) selected from ubiquinone (s) and / or plastoquinone (s).

7. Composition according to claim 6, characterized in that the biochinone coenzyme Q-10.

8. Composition according to one of claims 1 to 7, characterized in that it further contains at least one emulsifier and / or at least one dialkyl ether and / or a mixture of these substances.

9. Composition according to one of claims 1 to 8, characterized in that the emulsifier is selected from Polyethylenglycolalkylethern and / or ethoxylated glycerol esters.

10. A composition according to claim 9, characterized in that the Polyethylenglycolalkylether an alkyl chain length of 6 to 30 carbon atoms, preferably from 12 to 22 carbon atoms, and a degree of ethoxylation of 1 to 1000, preferably from 1 to 500 and in particular from 1 to 100, and the ethoxylated glycerol ester is selected from C ₁₂ -C ₂₂ fatty acid mono- and diesters of addition products of from 1 to 30 moles of ethylene oxide onto polyols having from 3 to 6 carbon atoms, in particular to glycerol.

11. Composition according to one of claims 1 to 10, characterized in that it is present as a shampoo, hair conditioner, hair tonic, hair conditioner, hair fixative, hair spray or hair gel.

12. Use of an agent according to any one of claims 1 to 1 1 for improving the hair structure of human hair.

13. Use according to claim 12, characterized in that the gene expression of several hair keratins is increased.

14. Use according to one of claims 12 or 13, characterized in that the gene expression of the hair keratins hHa4, hHa3-l, hHa2, hHb6 and the cytokeratins is increased to strengthen the internal structure of human hair.

15. A method for improving the hair structure of human hair, characterized in that an agent according to any one of claims 1 to 1 1 is applied to the hair or the hairy skin.

16. The method according to claim 15, characterized in that the gene expression of the hair keratins hHa4, hHa3-l, hHa2, hHb6 and the cytokeratins to enhance the internal structure of human hair is increased.