DE10240757A1 - Cosmetic composition used for cleaning and/or caring for skin and hair comprises sericin and fibroin and/or their hydrolyzates and/or derivatives - Google Patents

Abstract

Cosmetic composition comprises sericin and/or its hydrolyzate and/or derivatives and fibroin and/or its hydrolyzate and/or its derivatives.

Description

The invention relates to cosmetic compositions containing a synergistically effective Combination of silk proteins and the use of these agents for cleaning and / or skin and hair care.

The cosmetic treatment of skin and hair is an important part of human body care. So today human hair is treated in many ways with hair cosmetic preparations. These include cleaning the hair with shampoos, care and regeneration with rinses and cures, as well as bleaching, dyeing and shaping the hair with colorants, tinting agents, waving agents and styling preparations. Means for changing or shading the color of the head hair play an outstanding role. Apart from the bleaching agents, which bring about an oxidative brightening of the hair by breaking down the natural hair dyes, there are essentially three types of hair dye in the area of hair coloring:
So-called oxidation dyes are used for permanent, intensive dyeings with appropriate fastness properties. Such colorants usually contain oxidation dye precursors, so-called developer components and coupler components. The developer components form the actual dyes under the influence of oxidizing agents or of atmospheric oxygen with one another or under coupling with one or more coupler components. The oxidation coloring agents are characterized by excellent, long-lasting coloring results. For natural-looking dyeings, however, a mixture of a larger number of oxidation dye precursors usually has to be used; in many cases direct dyes are still used for shading. If the dyes formed or used directly in the course of the color formation have distinctly different fastness properties (e.g. UV stability, fastness to perspiration, fastness to washing, etc.), a recognizable and therefore undesirable color shift can occur over time. This phenomenon increases when the hairstyle has hair or hair zones with different degrees of damage. An example of this is long hair, in which the hair tips, which have been exposed to all possible environmental influences for a long time, are generally significantly more damaged than the relatively freshly regrown hair zones.

For temporary coloring, colorants or tints are usually used contain so-called direct draw as a coloring component. This is Dye molecules that pull directly onto the hair and do not have an oxidative process Need training of color. This already belongs to these dyes, for example Henna known from antiquity for coloring body and hair. These stains are generally much more sensitive to shampooing than the oxidative ones Colorings, so that a much undesirable shift in shades or much faster there is even a visible "discoloration".

After all, a novel dyeing process has received great attention recently. In this process, precursors of the natural hair dye melanin are applied to the Hair applied; these then form natural analogues in the course of oxidative processes in the hair Dyes. Such a process with 5,6-dihydroxyindoline as a dye precursor was described in EP-B1-530 229. With, in particular multiple, application of With 5,6-dihydroxyindoline, it is possible for people with gray hair reproduce natural hair color. The coloring can be done with atmospheric oxygen only oxidizing agent so that no further oxidizing agents are used must become. In people with originally medium blonde to brown hair, this can Indoline can be used as the sole dye precursor. For use with people against it with originally red and in particular dark to black hair color satisfactory results often only through the use of additional ones Dye components, especially special oxidation dye precursors, can be achieved.

Not least because of the heavy stress on the hair, for example by dyeing or perms as well as by cleaning your hair with shampoos and through Environmental pollution, takes the importance of care products with as much as possible long-lasting effect. Such care products affect the natural structure and Properties of the hair. For example, following such treatments Wet and dry combability of the hair optimizes the hold and fullness of the hair his hair or be protected from increased split ends.

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

Furthermore, so-called combination preparations have recently been developed to Effort of the usual multi-stage process, especially with direct application by consumers.

In addition to the usual components, these preparations contain, for example, cleaning of hair, additional active ingredients that were previously reserved for hair after-treatment agents were. The consumer thus saves one application step; at the same time the Reduced packaging effort because one product is used less.

The active ingredients available for both separate aftertreatment agents for combination products, too, generally act preferentially on the hair surface. So active ingredients are known which give the hair shine, hold, fullness, better wet or Give dry combability or prevent the split ends. As important as that external appearance of the hair is, however, the internal structural cohesion of the Hair fibers, particularly in oxidative and reductive processes such as coloring and Perms can be greatly affected.

However, the known active ingredients cannot adequately meet all needs cover. There is therefore still a need for active substances or Active ingredient combinations for cosmetic products with good nourishing properties and good ones biodegradability. Especially in those containing dyes and / or electrolytes There is a need for additional nourishing active ingredients that formulate can be easily incorporated into known formulations.

Protein hydrolyzates, which are found in the Are able to significantly increase the internal structure of fibers, particularly keratin fibers restructure. Under structural strengthening, ie restructuring within the meaning of the invention a reduction in the damage caused by various influences to understand keratin fibers. Here, for example, the restoration of natural strength play an essential role. Restructured fibers stand out for example by an improved gloss or by an improved grip or due to easier combability. In addition, they have an optimized strength and Elasticity. A successful restructuring can be considered physically Evidence of an increase in melting point compared to the damaged fiber. The higher the The melting point of the hair is, the firmer the structure of the fiber. A detailed description of the A method for determining the melting range of hair can be found in DE 196 17 395 A1.

Protein hydrolyzates have been known for a long time and are often used in cosmetics Funds used. Please refer to the relevant specialist literature, for example in A. Domsch, "The cosmetic preparations", Volume II, page 205 and following, publisher for the chemical industry, H. Ziolkowsky. However, it is not an indication of one Restructuring, which is characterized by increased strength and elasticity.

It has long been known to use proteins or modified proteins in cosmetic preparations Use proteins to achieve nourishing effects. For this purpose either water-soluble proteins or by chemical and / or by enzymatic Reactions modified, i.e. water-solubilized proteins used. Especially with the Implementations to achieve sufficient water solubility is with fiber proteins Often such extensive degradation is required that the cosmetic effectiveness is not is more sufficient.

A cosmetically very interesting fiber protein is silk. Silk is that Fibers of the mulberry silkworm cocoon (Bombyx mori L.). The raw silk fiber consists of a double thread fibroin. Sericin holds this double thread as cement compound together. Silk consists of 70-80% by weight of fibroin, 19-28% by weight of sericin, 0.5-1% by weight from fat and 0.5-1% by weight from dyes and mineral components.

The essential components of the Sericin are with approx. 46% by weight hydroxy amino acids. The sericin consists of a group of 5 to 6 proteins. The essential amino acids des Sericines are serine (Ser, 37% by weight), aspartate (Asp, 26% by weight), glycine (Gly, 17% by weight), Alanine (Ala), Leucine (Leu) and Tyrosine (Tyr).

The water-insoluble fibroin is one of the scleroproteins with a long-chain molecular structure to count. The main components of fibroin are glycine (44% by weight), alanine (26% by weight), and tyrosine (13% by weight). Another essential structural feature of Fibroines is that Hexapeptide sequence Ser-Gly-Ala-Gly-Ala-Gly.

Technically, it is possible in a simple way, the two silk proteins separate from each other. So it is not surprising that both sericin and fibroin are considered Raw materials for use in cosmetic products are known individually. Furthermore, protein hydrolyzates and derivatives are based on the individual Silk proteins known raw materials in cosmetic products. For example Sericin as such from Pentapharm Ltd. as a commercial product with the Description Sericin Code 303-02 distributed. Fibroin is much more common than Protein hydrolyzate with different molecular weights offered in the market. This Hydrolyzates are understood in particular as "silk hydroylsates". So will for example under the trade name Promois® Silk with hydrolyzed fibroin average molecular weights between 350 and 1000 sold. DE 31 39 438 A1 describes colloidal fibroin solutions as an additive in cosmetic products.

The positive properties of the silk protein derivatives from sericin and fibroin are in each case known per se in the literature. This is how the company's sales brochure describes Pentapharm the cosmetic effects of Sericine on the skin as an anti-irritant, hydrating and film-forming. The properties of a shampoo containing Sericin as nourishing component are in the "medical cosmetology 17, 91-110 (1987)" by W. Engel et al. referenced. The effect of a fibroin derivative is described, for example, in DE 31 39 438 A1 described as nourishing and conditioning for the hair. None of the cited However, there is even the slightest hint of a synergistic font Increasing the positive effects of silk proteins and their derivatives in a simultaneous use of sericin and fibroin or their derivatives and / or Hydrolysates.

It has now surprisingly been found that the use of sericin and Fibroin and / or its derivatives the properties of skin and hair, which with Preparations were treated that contain such a combination of active ingredients, can be significantly increased.

A first subject of the present invention is therefore cosmetic preparations containing an active ingredient complex A consisting of the active ingredient A1 selected from Sericin, sericin hydrolyzates and derivatives, and mixtures thereof, and one Active ingredient A2 selected from fibroin, and / or fibroin hydrolyzates and / or derivatives and / or mixtures thereof.

The active ingredient complex A used according to the invention improves significantly in synergistically the essential inner and outer previously presented Structural features and the strength and elasticity of human hair.

• - natives Sericin,
• - hydrolysiertes und/oder weiter derivatisiertes Sericin, wie beispielsweise Handelsprodukte mit den INCI-Bezeichnungen Sericin, Hydrolyzed Sericin, oder Hydrolyzed Silk,
• - eine Mischung aus den Aminosäuren Serin, Aspartat und Glycin und/oder deren Methyl, Propyl, iso-Propyl, Butyl, iso-Butylestern, deren Salze wie beispielsweise Hydrochloride, Sulfate, Acetate, Citrate, Tartrate, wobei in dieser Mischung das Serin und/oder dessen Derivate zu 20 bis 60 Gew.%, das Aspartat und/oder dessen Derivate zu 10-40 Gew.% und das Glycin und/oder dessen Derivate zu 5 bis 30 Gew.% enthalten sind, mit der Maßgabe, daß sich die Mengen dieser Aminosäuren und/oder deren Derivate vorzugsweise zu 100 Gew.% ergänzen,
• - sowie deren Mischungen.

According to the invention, the following can be used as active substances A1 in the active substance complex A:

• - native sericin,
• hydrolyzed and / or further derivatized sericin, such as, for example, commercial products with the INCI names Sericin, Hydrolyzed Sericin, or Hydrolyzed Silk,
• - A mixture of the amino acids serine, aspartate and glycine and / or their methyl, propyl, iso-propyl, butyl, iso-butyl esters, their salts such as hydrochloride, sulfates, acetates, citrates, tartrates, in which mixture the serine and / or 20 to 60% by weight of its derivatives, 10-40% by weight of aspartate and / or its derivatives and 5 to 30% by weight of glycine and / or its derivatives, with the proviso that preferably add 100% by weight of the amounts of these amino acids and / or their derivatives,
• - and their mixtures.

• - natives, in eine lösliche Form überführtes Fibroin,
• - hydrolysiertes und/oder weiter derivatisiertes Fibroin, besonders teilhydrolisiertes Fibroin, welches als Hauptbestandteil die Aminosäuresequenz Ser-Gly-Ala-Gly-Ala- Gly enthält,
• - die Aminosäuresequenz Ser-Gly-Ala-Gly-Ala-Gly,
• - eine Mischung der Aminosäuren Glycin, Alanin und Tyrosin und/oder deren Methyl, Propyl, iso-Propyl, Butyl, iso-Butylestern, deren Salze wie beispielsweise Hydrochloride, Sulfate, Acetate, Citrate, Tartrate, wobei in dieser Mischung das Glycin und/oder dessen Derivate in Mengen von 20-60 Gew.%, das Alanin und dessen Derivate in Mengen von 10-40 Gew.% und das Tyrosin und dessen Derivate in Mengen von 0 bis 25 Gew.% enthalten sind, mit der Maßgabe, daß sich die Mengen dieser Aminosäuren und/oder deren Derivate vorzugsweise zu 100 Gew.% ergänzen,
• - sowie deren Mischungen.

According to the invention, the following can be used as active ingredients A2 in the active ingredient complex A:

• - native fibroin converted to a soluble form,
• hydrolyzed and / or further derivatized fibroin, especially partially hydrolyzed fibroin, which contains the amino acid sequence Ser-Gly-Ala-Gly-Ala- Gly as the main component,
• the amino acid sequence Ser-Gly-Ala-Gly-Ala-Gly,
• a mixture of the amino acids glycine, alanine and tyrosine and / or their methyl, propyl, isopropyl, butyl, isobutyl esters, their salts such as hydrochloride, sulfates, acetates, citrates, tartrates, in which mixture the glycine and / or its derivatives in amounts of 20-60% by weight, the alanine and its derivatives in amounts of 10-40% by weight and the tyrosine and its derivatives in amounts of 0 to 25% by weight, with the proviso that the amounts of these amino acids and / or their derivatives preferably add up to 100% by weight,
• - and their mixtures.

It may be preferred according to the invention that one of the two active ingredient components of the Active ingredient complex A used in the native or at most solubilized form becomes. According to the invention, it is also possible to use a mixture of several active ingredients (A) use.

It can be preferred according to the invention that the two active ingredients A1 and A2 in Ratio of 10:90 to 70:30, in particular 15:85 to 50:50 and very particularly 20:80 to 40:60 based on their respective active ingredient content in the Preparations according to the invention are used.

The derivatives of the hydrolysates of sericin and fibroin include both anionic and cationized protein hydrolyzates. The protein hydrolysates of sericin and fibroin according to the invention and the derivatives produced therefrom can be obtained from the corresponding proteins by chemical, in particular alkaline or acidic hydrolysis, by enzymatic hydrolysis and / or a combination of both types of hydrolysis. The hydrolysis of proteins usually results in a protein hydrolyzate with a molecular weight distribution of approximately 100 daltons up to several thousand daltons. Preferred protein hydrolyzates of sericin and fibroin and / or their derivatives, the underlying protein portion of which has a molecular weight of 100 to 25,000 daltons, preferably 250 to 10,000 daltons. Cationic protein hydrolyzates of sericin and fibroin also include quaternized amino acids and their mixtures. The quaternization of the protein hydrolyzates or the amino acids is often carried out using quaternary ammonium salts such as, for example, N, N-dimethyl-N- (n-alkyl) -N- (2-hydroxy-3-chloro-n-propyl) ammonium halides. Furthermore, the cationic protein hydrolyzates can also be further derivatized. As typical examples of the inventive cationic protein hydrolysates and derivatives are the ^th under the INCI names in the "International Cosmetic Ingredient Dictionary and Handbook" (seventh edition 1997, The Cosmetic, Toiletry, and Fragrance Association 1101 17 Street, NW, Suite 300 , Washington, DC 20036-4702) and commercially available products: Cocodimonium Hydroxypropyl Hydrolyzed Silk, Cocodimonium Hydroxypropyl Silk Amino Acids, Hydroxyproypltrimonium Hydrolyzed Silk, Lauryldimonium Hydroxypropyl Hydrolyzed Silk, Steardimonium Hydroxypropyl Hydrolyzed Silk, Quaternium-79 Hydrolyzed Silk. As typical examples of the invention anionic protein hydrolysates and derivatives are the ^th under the INCI names in the "International Cosmetic Ingredient Dictionary and Handbook" (seventh edition 1997, The Cosmetic, Toiletry, and Fragrance Association 1101 17 Street, NW, Suite 300 , Washington, DC 20036-4702) and commercially available products: Potassium Cocoyl Hydrolyzed Silk, Sodium Lauroyl Hydrolyzed Silk or Sodium Stearoyl Hydrolyzed Silk. Finally, typical examples of the derivatives of sericin and fibroin which can be used according to the invention are the products which are commercially available under the INCI names: ethyl ester of hydrolyzed silk and hydrolyzed silk PG-propyl methylsilanediol. Also usable according to the invention, although not necessarily preferred, are the commercially available products with the INCI names palmitoyl oligopeptide, palmitoyl pentapeptide-3, palmitoyl pentapeptide-2, acetyl hexapeptide-1, acetyl hexapeptide-3, copper tripeptide-1, hexapeptide-1 , Hexapeptide-2, MEA-Hydrolyzed Silk.

In the agents used according to the invention, the active ingredient complex A is in amounts of Contain 0.001-10 wt .-% based on the total agent. Quantities from 0.005 to 5, in particular 0.01 to 3% by weight, are very particularly preferred.

According to the invention, keratin fibers include furs, wool, feathers and especially understood human hair.

In a preferred embodiment of the invention, the effect of active ingredient complex (A) according to the invention can be further increased by fatty substances (D). Fats are understood to mean fatty acids, fatty alcohols, natural and synthetic Waxes which are present both in solid form and in liquid form in aqueous dispersion can understand and natural and synthetic cosmetic oil components.

Linear and / or branched, saturated ones can be used as fatty acids (D1) and / or unsaturated fatty acids with 6-30 carbon atoms. Fatty acids are preferred with 10-22 carbon atoms. These include, for example Isostearic acids, such as the commercial products Emersol® 871 and Emersol® 875, and isopalmitic acids like the commercial product Edenor® IP 95, as well as all others under the Trade names Edenor® (Cognis) sold fatty acids. Other typical examples of such Fatty acids are caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, Isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, Isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, Arachic acid, gadoleic acid, behenic acid and erucic acid and their technical Mixtures, e.g. B. in the pressure splitting of natural fats and oils, in the Oxidation of aldehydes from Roelen's oxosynthesis or the dimerization of unsaturated fatty acids. Those are usually particularly preferred Fatty acid cuts available from coconut oil or palm oil; is particularly preferred in the Usually the use of stearic acid.

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

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 can be used as fatty alcohols (D2). For example, decanol, octanol, octenol, dodecenol, decenol, octadienol, dodecadienol, decadienol, oleyl alcohol, eruca alcohol, ricinol alcohol, stearyl alcohol, isostearyl alcohol, cetyl alcohol, lauryl alcohol, myristyl alcohol, capryl alcohol, arachidyl alcohol, arachidyl alcohol, arachidyl alcohol, arachidyl alcohol, arachidyl alcohol, arachidyl alcohol , as well as their Guerbet alcohols, this list is intended to be exemplary and not limiting. The fatty alcohols, however, derive from preferably natural fatty acids, and it can usually be assumed that the esters of the fatty acids are obtained by reduction. Also suitable according to the invention are those fatty alcohol cuts which are produced by reducing naturally occurring triglycerides such as beef tallow, palm oil, peanut oil, 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®, e.g. B. Stenol® 1618 or Lanette®, e.g. B. Lanette® O or Lorol®, e.g. B. Lorol® C8, Lorol® C14, Lorol® C18, Lorol® C8-18, HD-Ocenol®, Crodacol®, e.g. B. Crodacol® CS, Novol®, Eutanol® G, Guerbitol® 16, Guerbitol® 18, Guerbitol® 20, Isofol® 12, Isofol® 16, Isofol® 24, Isofol® 36, Isocarb® 12, Isocarb® 16 or Isocarb ® 24 available for purchase. Of course, according to the invention, wool wax alcohols, such as are commercially available under the names Corona®, White Swan®, Coronet® or Fluilan®, can also be used. The fatty alcohols are used in amounts of 0.1-30% by weight, based on the entire preparation, preferably in amounts of 0.1-20% by weight.

According to the invention, natural or synthetic waxes (D3) can be used solid paraffins or isoparaffins, carnauba waxes, beeswaxes, candelilla waxes, Ozokerite, Ceresin, Walrat, Sunflower wax, fruit waxes such as Apple wax or citrus wax, microwaxes made of PE or PP. Such waxes are available, for example, from Kahl & Co., Trittau.

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

• - pflanzliche Öle. Beispiele für solche Öle sind Sonnenblumenöl, Olivenöl, Sojaöl, Rapsöl, Mandelöl, Jojobaöl, Orangenöl, Weizenkeimöl, Pfirsichkernöl und die flüssigen Anteile des Kokosöls. Geeignet sind aber auch andere Triglyceridöle wie die flüssigen Anteile des Rindertalgs sowie synthetische Triglyceridöle.
• - flüssige Paraffinöle, Isoparaffinöle und synthetische Kohlenwasserstoffe sowie Di-n- alkylether mit insgesamt zwischen 12 bis 36 C-Atomen, insbesondere 12 bis 24 C- Atomen, wie beispielsweise Di-n-octylether, Di-n-decylether, Di-n-nonylether, Di-n- undecylether, Di-n-dodecylether, n-Hexyl-n-octylether, n-Octyl-n-decylether, n-Decyl- n-undecylether, n-Undecyl-n-dodecylether und n-Hexyl-n-Undecylether sowie Di-tert- butylether, Di-iso-pentylether, Di-3-ethyldecylether, tert.-Butyl-n-octylether, iso- Pentyl-n-octylether und 2-Methyl-pentyl-n-octylether. Die als Handelsprodukte erhältlichen Verbindungen 1,3-Di-(2-ethyl-hexyl)-cyclohexan (Cetiol® S) und Di-n-octylether (Cetiol® OE) können bevorzugt sein.
• - Esteröle. Unter Esterölen sind zu verstehen die Ester von C₆-C₃₀-Fettsäuren mit C₂- C₃₀-Fettalkoholen. Bevorzugt sind die Monoester der Fettsäuren mit Alkoholen mit 2 bis 24 C-Atomen. Beispiele für eingesetzte Fettsäurenanteile in den Estern sind Capronsäure, Caprylsäure, 2-Ethylhexansäure, Caprinsäure, Laurinsäure, Isotridecansäure, Myristinsäure, Palmitinsäure, Palmitoleinsäure, Stearinsäure, Isostearinsäure, Ölsäure, Elaidinsäure, Petroselinsäure, Linolsäure, Linolensäure, Elaeostearinsäure, Arachinsäure, Gadoleinsäure, Behensäure und Erucasäure sowie deren technische Mischungen, die z. B. bei der Druckspaltung von natürlichen Fetten und Ölen, bei der Oxidation von Aldehyden aus der Roelen'schen Oxosynthese oder der Dimerisierung von ungesättigten Fettsäuren anfallen. Beispiele für die Fettalkoholanteile in den Esterölen sind Isopropylalkohol, Capronalkohol, Caprylalkohol, 2-Ethylhexylalkohol, Caprinalkohol, Laurylalkohol, Isotridecylalkohol, Myristylalkohol, Cetylalkohol, Palmoleylalkohol, Stearylalkohol, Isostearylalkohol, Oleylalkohol, Elaidylalkohol, Petroselinylalkohol, Linolylalkohol, Linolenylalkohol, Elaeostearylalkohol, Arachylalkohol, Gadoleylalkohol, Behenylalkohol, Erucylalkohol und Brassidylalkohol sowie deren technische Mischungen, die z. B. bei der Hochdruckhydrierung von technischen Methylestern auf Basis von Fetten und Ölen oder Aldehyden aus der Roelen'schen Oxosynthese sowie als Monomerfraktion bei der Dimerisierung von ungesättigten Fettalkoholen anfallen. Erfindungsgemäß besonders bevorzugt sind Isopropylmyristat (Rilanit® IPM), Isononansäure-C16-18-alkylester (Cetiol® SN), 2-Ethylhexylpalmitat (Cegesoft® 24), Stearinsäure-2-ethylhexylester (Cetiol® 868), Cetyloleat, Glycerintricaprylat, Kokosfettalkohol-caprinat/-caprylat (Cetiol® LC), n-Butylstearat, Oleylerucat (Cetiol® J 600), Isopropylpalmitat (Rilanit® IPP), Oleyl Oleate (Cetiol®), Laurinsäurehexylester (Cetiol® A), Di-n-butyladipat (Cetiol® B), Myristylmyristat (Cetiol® MM), Cetearyl Isononanoate (Cetiol® SN), Ölsäuredecylester (Cetiol® V).
• - Dicarbonsäureester wie Di-n-butyladipat, Di-(2-ethylhexyl)-adipat, Di-(2-ethylhexyl)- succinat und Di-isotridecylacelaat sowie Diolester wie Ethylenglykol-dioleat, Ethylenglykol-di-isotridecanoat, Propylenglykol-di(2-ethylhexanoat), Propylenglykol- di-isostearat, Propylenglykol-di-pelargonat, Butandiol-di-isostearat, Neopentylglykol- dicaprylat,
• - symmetrische, unsymmetrische oder cyclische Ester der Kohlensäure mit Fettalkoholen, beispielsweise beschrieben in der DE-OS 197 56 454, Glycerincarbonat oder Dicaprylylcarbonat (Cetiol® CC),
• - Trifettsäureester von gesättigten und/oder ungesättigten linearen und/oder verzweigten Fettsäuren mit Glycerin,
• - Fettsäurepartialglyceride, das sind Monoglyceride, Diglyceride und deren technische Gemische. Bei der Verwendung technischer Produkte können herstellungsbedingt noch geringe Mengen Triglyceride enthalten sein. Die Partialglyceride folgen vorzugsweise der Formel (D4-I),
  
  
  in der R¹, R² und R³ unabhängig voneinander für Wasserstoff oder für einen linearen oder verzweigten, gesättigten und/oder ungesättigten Acylrest mit 6 bis 22, vorzugsweise 12 bis 18, Kohlenstoffatomen stehen mit der Maßgabe, daß mindestens eine dieser Gruppen für einen Acylrest und mindestens eine dieser Gruppen für Wasserstoff steht. Die Summe (m + n + q) steht für 0 oder Zahlen von 1 bis 100, vorzugsweise für 0 oder 5 bis 25. Bevorzugt steht R¹ für einen Acylrest und R² und R³ für Wasserstoff und die Summe (m + n + q) ist 0. Typische Beispiele sind Mono- und/oder Diglyceride auf Basis von Capronsäure, Caprylsäure, 2-Ethylhexansäure, Caprinsäure, Laurinsäure, Isotridecansäure, Myristinsäure, Palmitinsäure, Palmoleinsäure, Stearinsäure, Isostearinsäure, Ölsäure, Elaidinsäure, Petroselinsäure, Linolsäure, Linolensäure, Elaeostearinsäure, Arachinsäure, Gadoleinsäure, Behensäure und Erucasäure sowie deren technische Mischungen. Vorzugsweise werden Ölsäuremonoglyceride eingesetzt.

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

• - vegetable oils. Examples of such oils are sunflower oil, olive oil, soybean oil, rapeseed oil, almond oil, jojoba oil, orange oil, wheat germ oil, peach seed oil and the liquid components of coconut oil. Other triglyceride oils such as the liquid portions of beef tallow and synthetic triglyceride oils are also suitable.
• - Liquid paraffin oils, isoparaffin oils and synthetic hydrocarbons and di-n-alkyl ethers with a total of between 12 to 36 carbon atoms, in particular 12 to 24 carbon atoms, such as, for example, di-n-octyl ether, di-n-decyl ether, di-n- nonyl ether, di-n-undecyl ether, di-n-dodecyl ether, n-hexyl-n-octyl ether, n-octyl-n-decyl ether, n-decyl-n-undecyl ether, n-undecyl-n-dodecyl ether and n-hexyl n-Undecyl ether and di-tert-butyl ether, di-isopentyl ether, di-3-ethyldecyl ether, tert-butyl-n-octyl ether, isopentyl-n-octyl ether and 2-methyl-pentyl-n-octyl ether. The compounds 1,3-di- (2-ethyl-hexyl) -cyclohexane (Cetiol® S) and di-n-octyl ether (Cetiol® OE) available as commercial products can be preferred.
• - ester oils. Are Esterölen to understand the esters of C ₆ -C ₃₀ fatty acids with C ₂ - C ₃₀ fatty alcohols. The monoesters of fatty acids with alcohols having 2 to 24 carbon atoms are preferred. Examples of fatty acid constituents used in the esters are caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linoleic acid, arenachic acid, araoleic acid, araoleic acid, araoleic acid, araelostic acid, elaostelic acid, elaoleic acid, elaostic acid, elaostic acid Erucic acid and its technical mixtures, the z. B. in the pressure splitting of natural fats and oils, in the oxidation of aldehydes from Roelen's oxosynthesis or the dimerization of unsaturated fatty acids. Examples of the fatty alcohol fractions in the ester oils are isopropyl alcohol, capron alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaololeyl alcohol, elaolyl alcohol Behenyl alcohol, erucyl alcohol and brassidyl alcohol and their technical mixtures, which, for. B. in the high pressure hydrogenation of technical methyl esters based on fats and oils or aldehydes from Roelen's oxosynthesis and as a monomer fraction in the dimerization of unsaturated fatty alcohols. According to the invention, particular preference is given to isopropyl myristate (Rilanit® IPM), isononanoic acid C16-18 alkyl ester (Cetiol® SN), 2-ethylhexyl palmitate (Cegesoft® 24), stearic acid 2-ethylhexyl ester (Cetiol® 868), cetyl oleate, glycerol tricaprylate caprinate / caprylate (Cetiol® LC), n-butyl stearate, olerlerucate (Cetiol® J 600), isopropyl palmitate (Rilanit® IPP), oleyl oleates (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-isotridecylacelate as well as diol esters such as ethylene glycol dioleate, ethylene glycol di-isotridecanoate, propylene glycol di (2 -ethylhexanoate), propylene glycol di-isostearate, propylene glycol di-pelargonate, butanediol di-isostearate, neopentyl glycol dicaprylate,
• symmetrical, asymmetrical or cyclic esters of carbonic acid with fatty alcohols, for example described in DE-OS 197 56 454, glycerol carbonate or dicaprylyl carbonate (Cetiol® CC),
• Trifatty acid esters of saturated and / or unsaturated linear and / or branched fatty acids with glycerol,
• - Fatty acid partial glycerides are monoglycerides, diglycerides and their technical mixtures. When using technical products, small quantities of triglycerides may still be present due to the manufacturing process. The partial glycerides preferably follow the formula (D4-I),
  
  
  in which R ¹ , R ² and R ³ independently of one another represent hydrogen or a linear or branched, saturated and / or unsaturated acyl radical having 6 to 22, preferably 12 to 18, carbon atoms, with the proviso that at least one of these groups represents a Acyl radical and at least one of these groups represents hydrogen. The sum (m + n + q) represents 0 or numbers from 1 to 100, preferably 0 or 5 to 25. R ¹ preferably represents an acyl radical and R ² and R ^{3 represents} hydrogen and the sum (m + n + q) is 0. Typical examples are mono- and / or diglycerides based on caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linoleic acid , Elaeostearic acid, arachic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures. Oleic acid monoglycerides are preferably used.

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

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

The combination of the active ingredient complex (A) with has proven to be particularly advantageous Proven surfactants (E). In a further preferred embodiment, the Agents used according to the invention surfactants. Under the term surfactants surface-active substances, the adsorption layers on surfaces and interfaces form or aggregate in volume phases to micelle colloids or lyotropic mesophases can understand. A distinction is made between anionic surfactants consisting of a hydrophobic Rest and a negatively charged hydrophilic head group, amphoteric surfactants, which carry both a negative and a compensating positive charge, cationic Surfactants which, in addition to a hydrophobic residue, have a positively charged hydrophilic group and nonionic surfactants, which are not charges but strong Have dipole moments and are highly hydrated in aqueous solution. further Definitions and properties of surfactants can be found in "H.-D. Dörfler, Grenz- and Kolloidchemie, VCH Verlagsgesellschaft mbH. Weinheim, 1994 ". The previous ones reproduced definition can be found from p. 190 in this publication.

• - lineare und verzweigte Fettsäuren mit 8 bis 30 C-Atomen (Seifen),
• - Ethercarbonsäuren der Formel R-O-(CH₂-CH₂O)_x-CH₂-COOH, in der R eine lineare Alkylgruppe mit 8 bis 30 C-Atomen und x = 0 oder 1 bis 16 ist,
• - Acylsarcoside mit 8 bis 24 C-Atomen in der Acylgruppe,
• - Acyltauride mit 8 bis 24 C-Atomen in der Acylgruppe,
• - Acylisethionate mit 8 bis 24 C-Atomen in der Acylgruppe,
• - Sulfobernsteinsäuremono- und -dialkylester mit 8 bis 24 C-Atomen in der Alkylgruppe und Sulfobernsteinsäuremono-alkylpolyoxyethylester mit 8 bis 24 C-Atomen in der Alkylgruppe und 1 bis 6 Oxyethylgruppen,
• - lineare Alkansulfonate mit 8 bis 24 C-Atomen,
• - lineare Alpha-Olefinsulfonate mit 8 bis 24 C-Atomen,
• - Alpha-Sulfofettsäuremethylester von Fettsäuren mit 8 bis 30 C-Atomen,
• - Alkylsulfate und Alkylpolyglykolethersulfate der Formel R-O(CH₂-CH₂O)_x-OSO₃H, in der R eine bevorzugt lineare Alkylgruppe mit 8 bis 30 C-Atomen und x = 0 oder 1 bis 12 ist,
• - Gemische oberflächenaktiver Hydroxysulfonate gemäß DE-A-37 25 030,
• - sulfatierte Hydroxyalkylpolyethylen- und/oder Hydroxyalkylenpropylenglykolether gemäß DE-A-37 23 354,
• - Sulfonate ungesättigter Fettsäuren mit 8 bis 24 C-Atomen und 1 bis 6 Doppelbindungen gemäß DE-A-39 26 344,
• - Ester der Weinsäure und Zitronensäure mit Alkoholen, die Anlagerungsprodukte von etwa 2-15 Molekülen Ethylenoxid und/oder Propylenoxid an Fettalkohole mit 8 bis 22 C-Atomen darstellen,
• - Alkyl- und/oder Alkenyletherphosphate der Formel (E1-I),
  
  
  
• - in der R¹ bevorzugt für einen aliphatischen Kohlenwasserstoffrest mit 8 bis 30 Kohlenstoffatomen, R² für Wasserstoff, einen Rest (CH₂CH₂O)_nR² oder X, n für Zahlen von 1 bis 10 und X für Wasserstoff, ein Alkali- oder Erdalkalimetall oder NR³R⁴R⁵R⁶, mit R³ bis R⁶ unabhängig voneinander stehend für Wasserstoff oder einen C₁ bis C₄ -Kohlenwasserstoffrest, steht,
• - sulfatierte Fettsäurealkylenglykolester der Formel (E1-II)
  
  R⁷CO(AlkO)_nSO₃M (E1-II)
  
  in der R⁷CO- für einen linearen oder verzweigten, aliphatischen, gesättigten und/oder ungesättigten Acylrest mit 6 bis 22 C-Atomen, Alk für CH₂CH₂, CHCH₃CH₂ und/oder CH₂CHCH₃, n für Zahlen von 0,5 bis 5 und M für ein Kation steht, wie sie in der DE-OS 197 36 906.5 beschrieben sind,
• - Monoglyceridsulfate und Monoglyceridethersulfate der Formel (E1-III)
  
  
  in der R⁸CO für einen linearen oder verzweigten Acylrest mit 6 bis 22 Kohlenstoffatomen, x, y und z in Summe für 0 oder für Zahlen von 1 bis 30, vorzugsweise 2 bis 10, und X für ein Alkali- oder Erdalkalimetall steht. Typische Beispiele für im Sinne der Erfindung geeignete Monoglycerid(ether)sulfate sind die Umsetzungsprodukte von Laurinsäuremonoglycerid, Kokosfettsäuremonoglycerid, Palmitinsäuremonoglycerid, Stearinsäuremonoglycerid, Ölsäuremonoglycerid und Talgfettsäuremonoglycerid sowie deren Ethylenoxidaddukte mit Schwefeltrioxid oder Chlorsulfonsäure in Form ihrer Natriumsalze. Vorzugsweise werden Monoglyceridsulfate der Formel (E1-III) eingesetzt, in der R⁸CO für einen linearen Acylrest mit 8 bis 18 Kohlenstoffatomen steht, wie sie beispielsweise in der EP-B1 0 561 825, der EP-B1 0 561 999, der DE-A1 42 04 700 oder von A. K. Biswas et al. in J. Am. Oil. Chem. Soc. 37, 171 (1960) und F. U. Ahmed in J. Am. Oil. Chem. Soc. 67, 8 (1990) beschrieben worden sind,
• - Amidethercarbonsäuren wie sie in der EP 0 690 044 beschrieben sind,
• - Kondensationsprodukte aus C₈-C₃₀-Fettalkoholen mit Proteinhydrolysaten und/oder Aminosäuren und deren Derivaten, welche dem Fachmann als Eiweissfettsäurekondensate bekannt sind, wie beispielsweise die Lamepon®-Typen, Gluadin®-Typen, Hostapon® KCG oder die Amisoft®-Typen.

Suitable anionic surfactants (E1) in preparations according to the invention are all anionic surface-active substances suitable for use on the human body. These are characterized by a water-solubilizing, anionic group such as. B. a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group with about 8 to 30 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups can be contained in the molecule. Examples of suitable anionic surfactants are, in each case in the form of the sodium, potassium and ammonium as well as the mono-, di- and trialkanolammonium salts with 2 to 4 carbon atoms in the alkanol group,

• - linear and branched fatty acids with 8 to 30 carbon atoms (soaps),
• Ether carboxylic acids of the formula RO- (CH ₂ -CH ₂ O) _x -CH ₂ -COOH, in which R is a linear alkyl group with 8 to 30 C atoms and x = 0 or 1 to 16,
• Acyl sarcosides with 8 to 24 carbon atoms in the acyl group,
• Acyl taurides with 8 to 24 carbon atoms in the acyl group,
• Acyl isethionates with 8 to 24 carbon atoms in the acyl group,
• Monosulfonic acid and dialkyl sulfosuccinates with 8 to 24 carbon atoms in the alkyl group and mono-alkyl polyoxyethyl sulfosuccinates with 8 to 24 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups,
• linear alkanesulfonates with 8 to 24 carbon atoms,
• - linear alpha olefin sulfonates with 8 to 24 carbon atoms,
• - Alpha-sulfofatty acid methyl esters of fatty acids with 8 to 30 carbon atoms,
• Alkyl sulfates and alkyl polyglycol ether sulfates of the formula RO (CH ₂ -CH ₂ O) _x -OSO ₃ H, in which R is a preferably linear alkyl group with 8 to 30 C atoms and x = 0 or 1 to 12,
• Mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030,
• sulfated hydroxyalkyl polyethylene and / or hydroxyalkylene propylene glycol ethers according to DE-A-37 23 354,
• Sulfonates of unsaturated fatty acids with 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 adducts of about 2-15 molecules of ethylene oxide and / or propylene oxide with fatty alcohols having 8 to 22 carbon atoms,
• Alkyl and / or alkenyl ether phosphates of the formula (E1-I),
  
  
  
• - In which R ^{1 is} preferably an aliphatic hydrocarbon radical having 8 to 30 carbon atoms, R ^{2 is} hydrogen, a radical (CH ₂ CH ₂ O) _n R ² or X, n is a number from 1 to 10 and X is hydrogen, an alkali - or alkaline earth metal or NR ³ R ⁴ R ⁵ R ⁶ , with R ³ to R ⁶ independently of one another being hydrogen or a C ₁ to C ₄ hydrocarbon radical,
• sulfated fatty acid alkylene glycol esters of the formula (E1-II)
  
  R ⁷ CO (AlkO) _n SO ₃ M (E1-II)
  
  in the R ⁷ CO- for a linear or branched, aliphatic, saturated and / or unsaturated acyl radical having 6 to 22 carbon 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 stands for a cation as described in DE-OS 197 36 906.5,
• - Monoglyceride sulfates and monoglyceride ether sulfates of the formula (E1-III)
  
  
  in which R ⁸ CO stands for a linear or branched acyl radical with 6 to 22 carbon atoms, x, y and z in total for 0 or for numbers from 1 to 30, preferably 2 to 10, and X stands for an alkali or alkaline earth metal. Typical examples of monoglyceride (ether) sulfates suitable for the purposes of the invention are the reaction products of lauric acid monoglyceride, coconut fatty acid monoglyceride, palmitic acid monoglyceride, stearic acid monoglyceride, oleic acid monoglyceride and tallow fatty acid monoglyceride as well as their ethylene oxide adducts or their formulated with sulfuric acid trioxide. Monoglyceride sulfates of the formula (E1-III) are preferably used, in which R ⁸ CO represents a linear acyl radical having 8 to 18 carbon atoms, as described, for example, in EP-B1 0 561 825, EP-B1 0 561 999, DE -A1 42 04 700 or from AK Biswas et al. in J. Am. Oil. Chem. Soc. 37, 171 (1960) and FU Ahmed in J. Am. Oil. Chem. Soc. 67, 8 (1990),
• Amidether carboxylic acids as described in EP 0 690 044,
• - Condensation products from C ₈ -C ₃₀ fatty alcohols with protein hydrolyzates and / or amino acids and their derivatives, which are known to the person skilled in the art as protein fatty acid condensates, such as the Lamepon® types, Gluadin® types, Hostapon® KCG or the Amisoft® types ,

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

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

Ampholytic surfactants (E3) are understood to mean those surface-active compounds which, in addition to a C ₈ -C ₂₄ -alkyl or -acyl group, contain at least one free amino group and at least one -COOH or -SO ₃ H group in the molecule and for the formation of internal ones Salts are capable. Examples of suitable ampholytic surfactants are N-alkylglycine, N-alkylpropionic acid, N-alkylaminobutyric acid, N-alkyliminodipropionic acid, N-hydroxyethyl-N-alkylamidopropylglycine, N-alkyltaurine, N-alkyl sarcosine, 2-alkylaminopropionic acid and alkylaminoacetic acid each with about 8 to 24 C. Atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C ₁₂ -C ₁₈ acyl sarcosine.

• - Anlagerungsprodukte von 2 bis 50 Mol Ethylenoxid und/oder 0 bis 5 Mol Propylenoxid an lineare und verzweigte Fettalkohole mit 8 bis 30 C-Atomen, an Fettsäuren mit 8 bis 30 C-Atomen und an Alkylphenole mit 8 bis 15 C-Atomen in der Alkylgruppe,
• - mit einem Methyl- oder C₂-C₆-Alkylrest endgruppenverschlossene Anlagerungsprodukte von 2 bis 50 Mol Ethylenoxid und/oder 0 bis 5 Mol Propylenoxid an lineare und verzweigte Fettalkohole mit 8 bis 30 C-Atomen, an Fettsäuren mit 8 bis 30 C-Atomen und an Alkylphenole mit 8 bis 15 C-Atomen in der Alkylgruppe, wie beispielsweise die unter den Verkaufsbezeichnungen Dehydol® LS, Dehydol® LT (Cognis) erhältlichen Typen,
• - C₁₂-C₃₀-Fettsäuremono- und -diester von Anlagerungsprodukten von 1 bis 30 Mol Ethylenoxid an Glycerin,
• - Anlagerungsprodukte von 5 bis 60 Mol Ethylenoxid an Rizinusöl und gehärtetes Rizinusöl,
• - Polyolfettsäureester, wie beispielsweise das Handelsprodukt Hydagen® HSP (Cognis) oder Sovermol-Typen (Cognis),
• - alkoxilierte Triglyceride,
• - alkoxilierte Fettsäurealkylester der Formel (E4-I)
  
  R¹CO-(OCH₂CHR²)_wOR³ (E4-I)
  
  in der R¹CO für einen linearen oder verzweigten, gesättigten und/oder ungesättigten Acylrest mit 6 bis 22 Kohlenstoffatomen, R² für Wasserstoff oder Methyl, R³ für lineare oder verzweigte Alkylreste mit 1 bis 4 Kohlenstoffatomen und w für Zahlen von 1 bis 20 steht,
• - Aminoxide,
• - Hydroxymischether, wie sie beipielsweise in der DE-OS 197 38 866 beschrieben sind,
• - Sorbitanfeusäureester und Anlagerungeprodukte von Ethylenoxid an Sorbitanfettsäureester wie beispielsweise die Polysorbate,
• - Zuckerfettsäureester und Anlagerungsprodukte von Ethylenoxid an Zuckerfettsäureester,
• - Anlagerungsprodukte von Ethylenoxid an Fettsäurealkanolamide und Fettamine,
• - Zuckertenside vom Typ der Alkyl- und Alkenyloligoglykoside gemäß Formel (E4-II),
  
  R⁴O-[G]_p (E4-II)
  
  in der R⁴ für einen Alkyl- oder Alkenylrest mit 4 bis 22 Kohlenstoffatomen, G für einen Zuckerrest mit 5 oder 6 Kohlenstoffatomen und p für Zahlen von 1 bis 10 steht. Sie können nach den einschlägigen Verfahren der präparativen organischen Chemie erhalten werden. Stellvertretend für das umfangreiche Schrifttum sei hier auf die Übersichtsarbeit von Biermann et al. in Starch/Stärke 45, 281 (1993), B. Salka in Cosm. Toil. 108, 89 (1993) sowie J. Kahre et al. in SÖFW-Journal Heft 8, 598 (1995) verwiesen.
  Die Alkyl- und Alkenyloligoglykoside können sich von Aldosen bzw. Ketosen mit 5 oder 6 Kohlenstoffatomen, vorzugsweise von Glucose, ableiten. Die bevorzugten Alkyl- und/oder Alkenyloligoglykoside sind somit Alkyl- und/oder Alkenyloligoglucoside. Die Indexzahl p in der allgemeinen Formel (E4-II) gibt den Oligomerisierungsgrad (DP), d. h. die Verteilung von Mono- und Oligoglykosiden an und steht für eine Zahl zwischen 1 und 10. Während p im einzelnen Molekül stets ganzzahlig sein muß und hier vor allem die Werte p = 1 bis 6 annehmen kann, ist der Wert p für ein bestimmtes Alkyloligoglykosid eine analytisch ermittelte rechnerische Größe, die meistens eine gebrochene Zahl darstellt. Vorzugsweise werden Alkyl- und/oder Alkenyloligoglykoside mit einem mittleren Oligomerisierungsgrad p von 1,1 bis 3,0 eingesetzt. Aus anwendungstechnischer Sicht sind solche Alkyl- und/oder Alkenyloligoglykoside bevorzugt, deren Oligomerisierungsgrad kleiner als 1,7 ist und insbesondere zwischen 1,2 und 1,4 liegt. Der Alkyl- bzw. Alkenylrest R⁴ kann sich von primären Alkoholen mit 4 bis 11, vorzugsweise 8 bis 10 Kohlenstoffatomen ableiten. Typische Beispiele sind Butanol, Capronalkohol, Caprylalkohol, Caprinalkohol und Undecylalkohol sowie deren technische Mischungen, wie sie beispielsweise bei der Hydrierung von technischen Fettsäuremethylestern oder im Verlauf der Hydrierung von Aldehyden aus der Roelen'schen Oxosynthese erhalten werden. Bevorzugt sind Alkyloligoglucoside der Kettenlänge C₈-C₁₀ (DP = 1 bis 3), die als Vorlauf bei der destillativen Auftrennung von technischem C₈-C₁₈-Kokosfettalkohol anfallen und mit einem Anteil von weniger als 6 Gew.-% C₁₂-Alkohol verunreinigt sein können sowie Alkyloligoglucoside auf Basis technischer C_9/11-Oxoalkohole (DP = 1 bis 3). Der Alkyl- bzw. Alkenylrest R¹⁵ kann sich ferner auch von primären Alkoholen mit 12 bis 22, vorzugsweise 12 bis 14 Kohlenstoffatomen ableiten. Typische Beispiele sind Laurylalkohol, Myristylalkohol, Cetylalkohol, Palmoleylalkohol, Stearylalkohol, Isostearylalkohol, Oleylalkohol, Elaidylalkohol, Petroselinylalkohol, Arachylalkohol, Gadoleylalkohol, Behenylalkohol, Erucylalkohol, Brassidylalkohol sowie deren technische Gemische, die wie oben beschrieben erhalten werden können. Bevorzugt sind Alkyloligoglucoside auf Basis von gehärtetem C_12/14-Kokosalkohol mit einem DP von 1 bis 3.
• - Zuckertenside vom Typ der Fettsäure-N-alkylpolyhydroxyalkylamide, ein nichtionisches Tensid der Formel (E4-III),
  
  R⁵CO-NR⁶-[Z] (E4-III)
  
  in der R⁵CO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R⁶ für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 12 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Bei den Fettsäure-N-alkylpolyhydroxyalkylamiden handelt es sich um bekannte Stoffe, die üblicherweise durch reduktive Aminierung eines reduzierenden Zuckers mit Ammoniak, einem Alkylamin oder einem Alkanolamin und nachfolgende Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können. Hinsichtlich der Verfahren zu ihrer Herstellung sei auf die US-Patentschriften US 1,985,424, US 2,016,962 und US 2,703,798 sowie die Internationale Patentanmeldung WO 92/06984 verwiesen. Eine Übersicht zu diesem Thema von H. Kelkenberg findet sich in Tens. Surf. Det. 25, 8 (1988). Vorzugsweise leiten sich die Fettsäure-N-alkylpolyhydroxyalkylamide von reduzierenden Zuckern mit 5 oder 6 Kohlenstoffatomen, insbesondere von der Glucose ab. Die bevorzugten Fettsäure-N-alkylpolyhydroxyalkylamide stellen daher Fettsäure- N-alkylglucamide dar, wie sie durch die Formel (E4-IV) wiedergegeben werden:
  
  R⁷CO-NR⁸-CH₂-(CHOH)₄-CH₂OH (E4-IV)
  
  Vorzugsweise werden als Fettsäure-N-alkylpolyhydroxyalkylamide Glucamide der Formel (E4-IV) eingesetzt, in der R⁸ für Wasserstoff oder eine Alkylgruppe steht und R⁷CO für den Acylrest der Capronsäure, Caprylsäure, Caprinsäure, Laurinsäure, Myristinsäure, Palmitinsäure, Palmoleinsäure, Stearinsäure, Isostearinsäure, Ölsäure, Elaidinsäure, Petroselinsäure, Linolsäure, Linolensäure, Arachinsäure, Gadoleinsäure, Behensäure oder Erucasäure bzw. derer technischer Mischungen steht. Besonders bevorzugt sind Fettsäure-N-alkylglucamide der Formel (E4-IV), die durch reduktive Aminierung von Glucose mit Methylamin und anschließende Acylierung mit Laurinsäure oder C12/14-Kokosfettsäure bzw. einem entsprechenden Derivat erhalten werden. Weiterhin können sich die Polyhydroxyalkylamide auch von Maltose und Palatinose ableiten.

Nonionic surfactants (E4) contain z as hydrophilic group. B. a polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether group. Such connections are, for example

• - Adducts of 2 to 50 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide with linear and branched fatty alcohols with 8 to 30 C atoms, with fatty acids with 8 to 30 C atoms and with alkylphenols with 8 to 15 C atoms in the alkyl group,
• addition products of 2 to 50 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide end-capped with a methyl or C ₂ -C ₆ -alkyl radical to linear and branched fatty alcohols having 8 to 30 C atoms, to fatty acids having 8 to 30 C atoms Atoms and on alkylphenols with 8 to 15 carbon atoms in the alkyl group, such as, for example, the types available under the sales names Dehydol® LS, Dehydol® LT (Cognis),
• C ₁₂ -C ₃₀ fatty acid monoesters and diesters of adducts of 1 to 30 moles of ethylene oxide with glycerol,
• - adducts of 5 to 60 moles of ethylene oxide with castor oil and hardened castor oil,
• Polyol 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 (E4-I)
  
  R ¹ CO- (OCH ₂ CHR ² ) _w OR ³ (E4-I)
  
  in which R ¹ CO is a linear or branched, saturated and / or unsaturated acyl radical having 6 to 22 carbon atoms, R ^{2 is} hydrogen or methyl, R ^{3 is a} linear or branched alkyl radical having 1 to 4 carbon atoms and w is a number from 1 to 20 stands,
• Amine oxides,
• - Hydroxy mixed ethers as described, for example, in DE-OS 197 38 866,
• Sorbitan feusic acid esters and addition products of ethylene oxide with sorbitan fatty acid esters such as the polysorbates,
• - sugar fatty acid esters and adducts of ethylene oxide with sugar fatty acid esters,
• - adducts of ethylene oxide with fatty acid alkanolamides and fatty amines,
• Sugar surfactants of the alkyl and alkenyl oligoglycoside type according to formula (E4-II),
  
  R ⁴ O- [G] _p (E4-II)
  
  in which R ^{4 represents} an alkyl or alkenyl radical having 4 to 22 carbon atoms, G represents a sugar radical having 5 or 6 carbon atoms and p represents numbers from 1 to 10. They can be obtained according to the relevant procedures in preparative organic chemistry. Representative of the extensive literature here is the review by Biermann et al. in Starch /force 45, 281 (1993), B. Salka in Cosm. Toil. 108, 89 (1993) and J. Kahre et al. in SÖFW-Journal issue 8, 598 (1995).
  The alkyl and alkenyl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably from glucose. The preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides. The index number p in the general formula (E4-II) indicates the degree of oligomerization (DP), ie the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10. While p in the individual molecule must always be an integer and here can assume all the values p = 1 to 6, the value p for a certain alkyl oligoglycoside is an analytically determined arithmetic parameter, which usually represents a fractional number. Alkyl and / or alkenyl oligoglycosides with an average degree of oligomerization p of 1.1 to 3.0 are preferably used. From an application point of view, preference is given to those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and is in particular between 1.2 and 1.4. The alkyl or alkenyl radical R ⁴ can be derived from primary alcohols having 4 to 11, preferably 8 to 10, carbon atoms. Typical examples are butanol, capronic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as are obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis. Alkyl oligoglucosides of chain length C ₈ -C ₁₀ (DP = 1 to 3) are preferred, which are obtained as a preliminary step in the separation of technical C ₈ -C ₁₈ coconut fatty alcohol by distillation and with a proportion of less than 6% by weight of C ₁₂ - Alcohol can be contaminated and alkyl oligoglucosides based on technical C _9/11 oxo alcohols (DP = 1 to 3). The alkyl or alkenyl radical R ¹⁵ can also be derived from primary alcohols having 12 to 22, preferably 12 to 14, carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol and their technical mixtures, which can be obtained as described above. Alkyl oligoglucosides based on hardened C _12/14 coconut alcohol with a DP of 1 to 3 are preferred.
• Sugar surfactants of the fatty acid N-alkyl polyhydroxyalkyl amide type, a nonionic surfactant of the formula (E4-III),
  
  R ⁵ CO-NR ⁶ - [Z] (E4-III)
  
  in which R ⁵ CO for an aliphatic acyl radical having 6 to 22 carbon atoms, R ⁶ for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 12 carbon atoms and 3 to 10 hydroxyl groups stands. The fatty acid N-alkyl polyhydroxyalkylamides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride. With regard to the processes for their production, reference is made to US Pat. Nos. 1,985,424, 2,016,962 and 2,703,798 and international patent application WO 92/06984. An overview of this topic by H. Kelkenberg can be found in Tens. Surf. Det. 25, 8 (1988). The fatty acid N-alkylpolyhydroxyalkylamides are preferably derived from reducing sugars having 5 or 6 carbon atoms, in particular from glucose. The preferred fatty acid N-alkylpolyhydroxyalkylamides are therefore fatty acid N-alkylglucamides as represented by the formula (E4-IV):
  
  R ⁷ CO-NR ⁸ -CH ₂ - (CHOH) ₄ -CH ₂ OH (E4-IV)
  
  The preferred fatty acid N-alkylpolyhydroxyalkylamides used are glucamides of the formula (E4-IV) in which R ^{8 is} hydrogen or an alkyl group and R ⁷ CO is the acyl radical of caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmoleic acid Stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, arachic acid, gadoleic acid, behenic acid or erucic acid or their technical mixtures. Fatty acid N-alkylglucamides of the formula (E4-IV) which are obtained by reductive amination of glucose with methylamine and subsequent acylation with lauric acid or C12 / 14 coconut fatty acid or a corresponding derivative are particularly preferred. Furthermore, the polyhydroxyalkylamides can also be derived from maltose and palatinose.

The alkylene oxide addition products have proven to be preferred nonionic surfactants saturated linear fatty alcohols and fatty acids each with 2 to 30 moles of ethylene oxide per Mole of fatty alcohol or fatty acid has been proven. Preparations with excellent Properties are also obtained if they are fatty acid esters of nonionic surfactants contain ethoxylated glycerin.

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

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

The compounds with alkyl groups used as surfactant can in each case be act uniform substances. However, it is usually preferred in manufacturing these substances from natural vegetable or animal raw materials, so that one Mixtures of substances with different, depending on the respective raw material Maintains alkyl chain lengths.

In the case of surfactants, the addition products of ethylene and / or propylene oxide Fatty alcohols or derivatives of these adducts can represent both Products with a "normal" homolog distribution as well as those with a narrow Homolog distribution can be used. Under "normal" homolog distribution understood mixtures of homologues that are used in the implementation of Fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or Alkali metal alcoholates obtained as catalysts. Narrow homolog distributions are obtained when, for example, hydrotalcites, alkaline earth metal salts of Ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates as catalysts be used. The use of products with a narrow homolog distribution can be preferred.

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

Cationic surfactants (Es) of the type of can also be used according to the invention quaternary ammonium compounds, the esterquats and the amidoamines. preferred quaternary ammonium compounds are ammonium halides, especially chlorides and Bromides such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and Trialkylmethylammoniumchloride, e.g. B. cetyltrimethylammonium chloride, Stearyltrimethylammonium chloride, distearyldimethylammonium chloride, Lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and Tricetylmethylammonium chloride, as well as those under the INCI names Quaternium-27 and Quaternium-83 known imidazolium compounds. The long alkyl chains of the above surfactants preferably have 10 to 18 carbon atoms.

Esterquats are known substances that both have at least one Contain ester function as well as 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-dihydroxypropyl dialkylamines. Such products will be for example under the trademarks Stepantex®, Dehyquart® and Armocare® distributed. The products Armocare® VGH-70, a N, N-bis (2-palmitoyloxyethyl) dimethylammonium chloride, and Dehyquart® F-75, Dehyquart® C-4046, Dehyquart® L80 and Dehyquart® AU-35 are examples of such esterquats.

The alkylamidoamines are usually made more natural or by amidation synthetic fatty acids and fatty acid cuts with dialkylaminoamines. A According to the invention, this compound is particularly suitable from this group of substances the name Tegoamid® S 18 commercially available stearamidopropyl-dimethylamine represents.

The cationic surfactants (E5) are in the agents used according to the invention preferably contained in amounts of 0.05 to 10 wt .-%, based on the total agent. Amounts of 0.1 to 5% by weight are particularly preferred.

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

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

In a further preferred embodiment, the action of the active ingredient complex (A) according to the invention can be increased by emulsifiers (F). Emulsifiers cause water or oil-stable adsorption layers to form at the phase interface, which protect the dispersed droplets against coalescence and thus stabilize the emulsion. Like surfactants, emulsifiers are therefore made up of a hydrophobic and a hydrophilic part of the molecule. Hydrophilic emulsifiers preferably form O / W emulsions and hydrophobic emulsifiers preferably form W / O emulsions. An emulsion is to be understood as a droplet-like distribution (dispersion) of a liquid in another liquid with the use of energy to create stabilizing phase interfaces by means of surfactants. The selection of these emulsifying surfactants or emulsifiers is based on the substances to be dispersed and the particular external phase as well as the fine particle size of the emulsion. Further definitions and properties of emulsifiers can be found in "H.-D. Dörfler, interfacial and colloid chemistry, VCH Verlagsgesellschaft mbH. Weinheim, 1994". Emulsifiers which can be used according to the invention are, for example

• Addition products of 4 to 30 mol of ethylene oxide and / or 0 to 5 mol of propylene oxide with linear fatty alcohols with 8 to 22 C atoms, with fatty acids with 12 to 22 C atoms and with alkylphenols with 8 to 15 C atoms in the alkyl group,
• C ₁₂ -C ₂₂ fatty acid monoesters and diesters of adducts of 1 to 30 mol of ethylene oxide with polyols having 3 to 6 carbon atoms, in particular with glycerol,
• - Ethylene oxide and polyglycerol adducts with methyl glucoside fatty acid esters, fatty acid alkanolamides and fatty acid glucamides,
• C ₈ -C ₂₂ alkyl mono- and oligoglycosides and their ethoxylated analogs, degrees of oligomerization from 1.1 to 5, in particular 1.2 to 2.0, and glucose as the sugar component being preferred,
• Mixtures of alkyl (oligo) glucosides and fatty alcohols, for example the commercially available product Montanov®68,
• - adducts of 5 to 60 moles of ethylene oxide with castor oil and hardened castor oil,
• Partial esters of polyols with 3-6 carbon atoms with saturated fatty acids with 8 to 22 C atoms,
• - sterols. Sterols are understood to be a group of steroids which carry a hydroxyl group on the C atom 3 of the steroid structure and are isolated both from animal tissue (zoosterols) and from vegetable fats (phytosterols). Examples of zoosterols are cholesterol and lanosterol. Examples of suitable phytosterols are ergosterol, stigmasterol and sitosterol. Sterols, the so-called mycosterols, are also isolated from mushrooms and yeasts.
• - phospholipids. These include mainly the glucose phospholipids, which, for. B. as lecithins or phosphatidylcholines from z. B. egg yolk or plant seeds (z. B. soybeans) can be understood.
• Fatty acid esters of sugars and sugar alcohols, such as sorbitol,
• Polyglycerols and polyglycerol derivatives such as, for example, polyglycerol poly-12-hydroxystearate (commercial product Dehymuls® PGPH),
• - Linear and branched fatty acids with 8 to 30 carbon atoms and their Na, K, ammonium, Ca, Mg and Zn salts.

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

The compositions according to the invention can preferably contain at least one non-ionic emulsifier with an HLB value of 8 to 18, according to those in the Römpp lexicon Chemistry (Ed. 3. Falbe, M. Regitz), 10th edition, Georg Thieme Verlag Stuttgart, New York, (1997), page 1764, contain the definitions listed. Nonionic emulsifiers with an HLB value of 10-15 can be particularly preferred according to the invention.

It has also been shown to be advantageous that polymers (G) have the effect of Can support active ingredient complex (A) according to the invention. In a preferred one The agents used according to the invention are therefore embodied in polymers added, both cationic, anionic, amphoteric and nonionic Polymers have proven effective.

Cationic polymers (G1) are understood to mean polymers which are mainly and / or side chain have a group which is "temporary" or "permanent" can be cationic. According to the invention, such are considered to be “permanently cationic” Polymers refers to a cationic group regardless of the pH of the agent exhibit. These are usually polymers that have a quaternary nitrogen atom, for example in the form of an ammonium group. Preferred cationic groups are quaternary Ammonium groups. In particular those polymers in which the quaternary Ammonium group via a C1-4 hydrocarbon group to one of acrylic acid, methacrylic acid or whose derivatives are attached to the main polymer chain, have proven to be proven particularly suitable.

Homopolymers of the general formula (G1-I),


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

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

A particularly suitable homopolymer is, if desired crosslinked, Poly (methacryloyloxyethyltrimethylammonium chloride) with the INCI name Polyquaternium-37. If desired, the crosslinking can be carried out with multiple olefinic means unsaturated compounds, for example divinylbenzene, tetraallyloxyethane, Methylenebisacrylamide, diallyl ether, polyallyl polyglyceryl ether, or allyl ethers of sugars or Sugar derivatives such as erythritol, pentaerythritol, arabitol, mannitol, sorbitol, sucrose or Glucose take place. Methylene bisacrylamide is a preferred crosslinking agent.

The homopolymer is preferably in the form of a non-aqueous polymer dispersion which should not have a polymer content below 30% by weight. Such Polymer dispersions are available under the names Salcare® SC 95 (approx. 50% polymer, Other components: mineral oil (INCI name: Mineral Oil) and Tridecyl-polyoxypropylene-polyoxyethylene ether (INCI name: PPG-1-Trideceth-6)) and Salcare® SC 96 (approx. 50% polymer content, other 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- Name: PPG-1-Trideceth-6)) commercially available.

Copolymers with monomer units of the formula (G1-I) as the non-ionic monomer, preferably acrylamide, methacrylamide, acrylic acid C _1-4 alkyl esters and methacrylic acid C _1-4 alkyl ester. Among these nonionic monomers, acrylamide is particularly preferred. As in the case of the homopolymers described above, these copolymers can also be crosslinked. A preferred copolymer according to the invention is the crosslinked acrylamide-methacryloyloxyethyltrimethylammonium chloride copolymer. Such copolymers, in which the monomers are present in a weight ratio of approximately 20:80, are commercially available as an approximately 50% non-aqueous polymer dispersion under the name Salcare® SC 92.

• - quaternisierte Cellulose-Derivate, wie sie unter den Bezeichnungen Celquat® und Polymer JR® im Handel erhältlich sind. Die Verbindungen Celquat® H 100, Celquat® L 200 und Polymer JR®400 sind bevorzugte quaternierte Cellulose-Derivate,
• - kationische Alkylpolyglycoside gemäß der DE-PS 44 13 686,
• - kationiserter Honig, beispielsweise das Handelsprodukt Honeyquat® 50,
• - kationische Guar-Derivate, wie insbesondere die unter den Handelsnamen Cosmedia®Guar und Jaguar® vertriebenen Produkte,
• - Polysiloxane mit quaternären Gruppen, wie beispielsweise die im Handel erhältlichen Produkte Q2-7224 (Hersteller: Dow Corning; ein stabilisiertes Trimethylsilylamodimethicon), Dow Corning® 929 Emulsion (enthaltend ein hydroxyl-amino-modifiziertes Silicon, das auch als Amodimethicone bezeichnet wird), SM-2059 (Hersteller: General Electric), SLM-55067 (Hersteller: Wacker) sowie Abil®-Quat 3270 und 3272 (Hersteller: Th. Goldschmidt), diquaternäre Polydimethylsiloxane, Quaternium-80),
• - polymere Dimethyldiallylammoniumsalze und deren Copolymere mit Estern und Amiden von Acrylsäure und Methacrylsäure. Die unter den Bezeichnungen Merquat®100 (Poly(dimethyldiallylammoniumchlorid)) und Merquat®550 (Dimethyldiallylammoniumchlorid-Acrylamid-Copolymer) im Handel erhältlichen Produkte sind Beispiele für solche kationischen Polymere,
• - Copolymere des Vinylpyrrolidons mit quaternierten Derivaten des Dialkylaminoalkylacrylats und -methacrylats, wie beispielsweise mit Diethylsulfat quaternierte Vinylpyrrolidon-Dimethylaminoethylmethacrylat-Copolymere. Solche Verbindungen sind unter den Bezeichnungen Gafquat®734 und Gafquat®755 im Handel erhältlich,
• - Vinylpyrrolidon-Vinylimidazoliummethochlorid-Copolymere, wie sie unter den Bezeichnungen Luviquat® FC 370, FC 550, FC 905 und HM 552 angeboten werden,
• - quaternierter Polyvinylalkohol,
• - sowie die unter den Bezeichnungen Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 und Polyquaternium 27 bekannten Polymeren mit quartären Stickstoffatomen in der Polymerhauptkette.

Other preferred cationic polymers are, for example

• - Quaternized cellulose derivatives, as are commercially available under the names Celquat® and Polymer JR®. The compounds Celquat® H 100, Celquat® L 200 and Polymer JR®400 are preferred quaternized cellulose derivatives,
• cationic alkyl polyglycosides according to DE-PS 44 13 686,
• cationized honey, for example the commercial product Honeyquat® 50,
• - cationic guar derivatives, such as in particular the products sold under the trade names Cosmedia®Guar and Jaguar®,
• Polysiloxanes with quaternary groups, such as, for example, the commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethylsilylamodimethicone), Dow Corning® 929 emulsion (containing a hydroxylamino-modified silicone, which is also referred to as amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil®-Quat 3270 and 3272 (manufacturer: Th. Goldschmidt), diquaternary polydimethylsiloxanes, Quaternium-80),
• - Polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid. The products commercially available 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, for example, vinylpyrrolidone-dimethylaminoethyl methacrylate copolymers quaternized with diethyl sulfate. Such compounds are commercially available under the names Gafquat®734 and Gafquat®755,
• Vinylpyrrolidone-vinylimidazolium methochloride copolymers, as are offered under the names Luviquat® FC 370, FC 550, FC 905 and HM 552,
• - quaternized polyvinyl alcohol,
• - And the known under the names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27 polymers with quaternary nitrogen atoms in the main polymer chain.

Can also be used as cationic polymers under the Designations Polyquaternium-24 (commercial product e.g. Quatrisoft® LM 200), known Polymers. The copolymers of vinyl pyrrolidone can also be used according to the invention, as they are as commercial products Copolymer 845 (manufacturer: ISP), Gaffix® VC 713 (manufacturer: ISP), Gafquat®ASCP 1011, Gafquat®HS 110, Luviquat®8155 and Luviquat® MS 370 are available.

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 as a quaternary ammonium group and is therefore cationic. For example, chitosan and its derivatives, such as those among the Trade names Hydagen® CMF, Hydagen® HCMF, Kytamer® PC and Chitolam® NB / 101 are freely available in stores.

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

Furthermore, cationized protein hydrolyzates are to be counted among the cationic polymers, the underlying protein hydrolyzate being derived from animals, for example from collagen, milk or keratin, from plants, for example from wheat, corn, rice, potatoes, soy or almonds, from marine life forms, for example from fish collagen or algae, or biotechnologically obtained protein hydrolyzates. The protein hydrolysates on which the cationic derivatives according to the invention are based can be obtained from the corresponding proteins by chemical, in particular alkaline or acidic hydrolysis, by enzymatic hydrolysis and / or a combination of both types of hydrolysis. The hydrolysis of proteins usually results in a protein hydrolyzate with a molecular weight distribution of approximately 100 daltons up to several thousand daltons. Preferred cationic protein hydrolyzates are those whose underlying protein content has a molecular weight of 100 to 25,000 Daltons, preferably 250 to 5000 Daltons. Cationic protein hydrolyzates also include quaternized amino acids and their mixtures. The quaternization of the protein hydrolyzates or the amino acids is often carried out using quaternary ammonium salts such as, for example, N, N-dimethyl-N- (n-alkyl) -N- (2-hydroxy-3-chloro-n-propyl) ammonium halides. Furthermore, the cationic protein hydrolyzates can also be further derivatized. As typical examples of the inventive cationic protein hydrolysates and derivatives are the ^th under the INCI names in the "International Cosmetic Ingredient Dictionary and Handbook" (seventh edition 1997, The Cosmetic, Toiletry, and Fragrance Association 1101 17 Street, NW, Suite 300 , Washington, DC 20036-4702) and commercially available products: Cocodimonium hydroxypropyl hydrolyzed collagen, Cocodimopnium hydroxypropyl hydrolyzed casein, Cocodimonium hydroxypropyl hydrolyzed collagen, Cocodimonium hydroxypropyl hydrolyzed hair keratin, Cocodimonium hydroxypropyl hydrolyzed keratin, Cocodimonium hydroxypropyl hydrolyzed hydroxypropyl hydrolyzed Hydrolyzed Soy Protein, Cocodimonium Hydroxypropyl Hydrolyzed Wheat Protein, Hydroxypropyl Arginine Lauryl / Myristyl Ether HCl, Hydroxypropyltrimonium Gelatin, Hydroxypropyltrimonium Hydrolyzed Casein, Hydroxypropyltrimonium Hydrolyzed Collagen, Hydroxypropyltrimonium Hydrolyzed Conchioli n Protein, Hydroxypropyltrimonium Hydrolyzed Keratin, Hydroxypropyltrimonium Hydrolyzed Rice Bran Protein, Hydroxypropyltrimonium Hydrolyzed Soy Protein, Hydroxypropyl Hydrolyzed Vegetable Protein, Hydroxypropyltrimonium Hydrolyzed Wheat Protein, Hydroxypropyltrimonium Hydrolyzed Wheat Protein / Siloxysilicate, Laurdimonium Hydroxypropyl Hydrolyzedhydrogenated Protein Wheat Protein / Siloxysilicate, Lauryldimonium Hydroxypropyl Hydrolyzed Casein, Lauryldimonium Hydroxypropyl Hydrolyzed Collagen, Lauryldimonium Hydroxypropyl Hydrolyzed Keratin, Lauryldimonium Hydroxypropyl Hydrolyzed Casein, Steardimonium Hydroxypropyl Hydrolyzedium Hydroxyne Soy Protein, Steardimonium Hydroxypropyl Hydrolyzed Vegetable Protein, Steardimon ium Hydroxypropyl Hydrolyzed Wheat Protein, Steartrimonium Hydroxyethyl Hydrolyzed Collagen, Quaternium-76 Hydrolyzed Collagen, Quaternium-79 Hydrolyzed Collagen, Quaternium-79 Hydrolyzed Keratin, Quaternium-79 Hydrolyzed Milk Protein, Quaternium-79 Hydrolyzed Soy Protein, Quaterneatium-79 Hydrolyzed

The cationic protein hydrolyzates and derivatives are very particularly preferred vegetable based.

With the anionic polymers (G2), which have the effect of the invention Active ingredient complex (A) can support, are anionic polymers, which Have carboxylate and / or sulfonate groups. Examples of anionic monomers which such polymers can consist of are acrylic acid, methacrylic acid, crotonic acid, Maleic anhydride and 2-acrylamido-2-methylpropanesulfonic acid. The acidic groups in whole or in part as sodium, potassium, ammonium, mono- or Triethanolammonium salt are present. Preferred monomers are 2-acrylamido-2- methyl propanesulfonic acid and acrylic acid.

Anionic polymers have proven to be particularly effective contain alone or co-monomer 2-acrylamido-2-methylpropanesulfonic acid, the Sulphonic acid group in whole or in part as sodium, potassium, ammonium, mono- or Triethanolammonium salt can be present.

The homopolymer of 2-acrylamido-2-methylpropanesulfonic acid is particularly preferred, which is commercially available, for example, under the name Rheothik®11-80.

Within this embodiment, it may be preferred to have copolymers of at least use an anionic monomer and at least one nonionic monomer. With regard to the anionic monomers, reference is made to the substances listed above directed. Preferred nonionic monomers are acrylamide, methacrylamide, Acrylic acid esters, methacrylic acid esters, vinyl pyrrolidone, vinyl ethers and vinyl esters.

Preferred anionic copolymers are acrylic acid-acrylamide copolymers and in particular polyacrylamide copolymers with monomers containing sulfonic acid groups. A particularly preferred anionic copolymer consists of 70 to 55 mol% of acrylamide and 30 to 45 mol% of 2-acrylamido-2-methylpropanesulfonic acid, the sulfonic acid group being wholly or partly as sodium, potassium, ammonium, mono- or triethanolammonium Salt is present. This copolymer can also be crosslinked, with polyolefinically unsaturated compounds such as tetraallyloxyethane, allyl sucrose, allylpentaerythritol and methylenebisacrylamide preferably being used as crosslinking agents. 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 ₁₄ isoparaffin) and a nonionic emulsifier (Laureth-7), has proven to be particularly advantageous in the context of the teaching according to the invention.

Also under the name Simulgel®600 as a compound with isohexadecane and Sodium acryloyldimethyltaurate copolymers sold as Polysorbate-80 have proven to be proven particularly effective according to the invention.

Also preferred anionic homopolymers are uncrosslinked and crosslinked Polyacrylic. Allyl ethers of pentaerythritol, sucrose and propylene preferred networking agents. Such connections are, for example, under the Carbopol® trademark commercially available.

Copolymers of maleic anhydride and methyl vinyl ether, especially those with Cross-links are also color-preserving polymers. A networked with 1,9-decadiene Maleic acid-methyl vinyl ether copolymer is available under the name Stabileze® QM Available commercially.

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

An example of an amphopolymer that can be used according to the invention is that under Description Amphomer® available acrylic resin, which is a copolymer tert-butylaminoethyl methacrylate, N- (1,1,3,3-tetramethylbutyl) acrylamide and two or more Monomers from the group of acrylic acid, methacrylic acid and their simple esters.

Further amphoteric polymers which can be used according to the invention are those in British Laid-open specification 2 104 091, European laid-open specification 47 714, the European Application 217 274, European Application 283 817 and the German patent application 28 17 369 compounds mentioned.

• a) Monomeren mit quartären Ammoniumgruppen der allgemeinen Formel (G3-I),
  
  R¹-CH=CR²-CO-Z-(C_nH_2n)-N⁽⁺⁾R³R⁴R⁵ A^(-) (G3-I)
  
  in der R¹ und R² unabhängig voneinander stehen für Wasserstoff oder eine Methylgruppe und R³, R⁴ und R⁵ unabhängig voneinander für Alkylgruppen mit 1 bis 4 Kohlenstoffatomen, Z eine NH-Gruppe oder ein Sauerstoffatom, n eine ganze Zahl von 2 bis 5 und A^(-) das Anion einer organischen oder anorganischen Säure ist, und
• b) monomeren Carbonsäuren der allgemeinen Formel (G3-II),
  
  R⁶-CH=CR⁷-COOH (G3-II)
  
  in denen R⁶ und R⁷ unabhängig voneinander Wasserstoff oder Methylgruppen sind.

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

• a) monomers with quaternary ammonium groups of the general formula (G3-I),
  
  R ¹ -CH = CR ² -CO-Z- (C _n H _2n ) -N ⁽⁺⁾ R ³ R ⁴ R ⁵ A ^(-) (G3-I)
  
  in which R ¹ and R ² independently of one another represent hydrogen or a methyl group and R ³ , R ⁴ and R ⁵ 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 (G3-II),
  
  R ⁶ -CH = CR ⁷ -COOH (G3-II)
  
  in which R ⁶ and R ^{7 are} independently hydrogen or methyl groups.

According to the invention, these compounds can be used both directly and in salt form, which is obtained by neutralizing the polymers, for example with an alkali metal hydroxide. With regard to the details of the preparation of these polymers, reference is expressly made to the content of German laid-open specification 39 29 973. Those polymers in which monomers of type (a) are used, in which R ³ , R ⁴ and R ^{5 are} methyl groups, Z is an NH group and A ^{(-) is} a halide, methoxysulphate or ethoxysulphate, Ion is; Acrylamidopropyl-trimethyl-ammonium chloride is a particularly preferred monomer (a). Acrylic acid is preferably used as monomer (b) for the polymers mentioned.

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

• - Vinylpyrrolidon/Vinylester-Copolymere, wie sie beispielsweise unter dem Warenzeichen Luviskol® (BASF) vertrieben werden. Luviskol® VA 64 und Luviskol® VA 73, jeweils Vinylpyrrolidon/Vinylacetat-Copolymere, sind ebenfalls bevorzugte nichtionische Polymere.
• - Celluloseether, wie Hydroxypropylcellulose, Hydroxyethylcellulose und Methylhydroxypropylcellulose, wie sie beispielsweise unter den Warenzeichen Culminal® und Benecel® (AQUALON) vertrieben werden.
• - Schellack
• - Polyvinylpyrrolidone, wie sie beispielsweise unter der Bezeichnung Luviskol® (BASF) vertrieben werden.
• - Siloxane. Diese Siloxane können sowohl wasserlöslich als auch wasserunlöslich sein. Geeignet sind sowohl flüchtige als auch nichtflüchtige Siloxane, wobei als nichtflüchtige Siloxane solche Verbindungen verstanden werden, deren Siedepunkt bei Normaldruck oberhalb von 200°C liegt. Bevorzugte Siloxane sind Polydialkylsiloxane, wie beispielsweise Polydimethylsiloxan, Polyalkylarylsiloxane, wie beispielsweise Polyphenylmethylsiloxan, ethoxylierte Polydialkylsiloxane sowie Polydialkylsiloxane, die Amin- und/oder Hydroxy-Gruppen enthalten.
• - Glycosidisch substituierte Silicone gemäß der EP 0612759 B1.

Suitable nonionic polymers are for example:

• - Vinyl pyrrolidone / vinyl ester copolymers, such as those sold, for example, under the trademark Luviskol® (BASF). Luviskol® VA 64 and Luviskol® VA 73, each vinylpyrrolidone / vinyl acetate copolymers, are also preferred nonionic polymers.
• - Cellulose ethers, such as hydroxypropyl cellulose, hydroxyethyl cellulose and methyl hydroxypropyl cellulose, as are sold, for example, under the trademarks Culminal® and Benecel® (AQUALON).
• - Shellac
• - Polyvinylpyrrolidones, such as those sold under the name Luviskol® (BASF).
• - siloxanes. These siloxanes can be both water-soluble and water-insoluble. Both volatile and non-volatile siloxanes are suitable, non-volatile siloxanes being understood to mean those compounds whose boiling point is above 200 ° C. at 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 used contain several in particular two different polymers of the same charge and / or one ionic and contain an amphoteric and / or non-ionic polymer.

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

Furthermore, in a preferred embodiment of the invention, the effect of Active ingredient complex (A) can be increased by UV filter (I). According to the invention UV filters used are subject to their structure and their physical Properties no general restrictions. Rather, all are suitable in UV filters that can be used in the cosmetics sector, their absorption maximum in the UVA (315-400 nm) -, lies in the UVB (280-315 nm) - or in the UVC (<280 nm) range. UV filter with a Absorption maximum in the UVB range, in particular in the range from about 280 to about 300 nm are particularly preferred.

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

Examples of UV filters which can be used according to the invention are 4-aminobenzoic acid, N, N, N- Trimethyl-4- (2-oxoborn-3-ylidenemethyl) aniline methyl sulfate, 3,3,5-trimethylcyclohexyl salicylate (homosalates), 2-hydroxy-4-methoxy-benzophenone (Benzophenone-3; Uvinul®M 40, Uvasorb®MET, Neo Heliopan®BB, Eusolex®4360), 2-phenylbenzimidazole-5-sulfonic acid and its potassium, sodium and triethanolamine salts (phenylbenzimidazoles sulfonic acid; Parsol®HS; Neo Heliopan®Hydro), 3,3 '- (1,4-phenylenedimethylene) -bis (7.7- dimethyl-2-oxobicyclo- [2.2.1] hept-1-yl-methanesulfonic acid) and their salts, 1- (4-tert.- Butylphenyl) -3- (4-methoxyphenyl) propane-1,3-dione (butyl methoxydibenzoylmethane; Parsol®1789, Eusolex®9020), α- (2-oxoborn-3-ylidene) toluene-4-sulfonic acid and their Salts, ethoxylated 4-aminobenzoic acid ethyl esters (PEG-25 PABA; Uvinul®P 25), 4-dimethylaminobenzoic acid 2-ethylhexyl ester (octyl dimethyl PABA; Uvasorb®DMO, Escalol®507, Eusolex®6007), 2-ethylhexyl salicylic acid (octyl salicylate; Escalol®587, Neo Heliopan®OS, Uvinul®O18), 4-methoxycinnamic acid isopentyl ester (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-isopropylbenzyl salicylate, 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- ylidenmethyl] benzyl} acrylamids, 2,4-dihydroxybenzophenone (Benzophenone-1; Uvasorb®20 H, Uvinul®400), 1,1'-Diphenylacrylonitrilsäure-2-ethylhexyl ester (Octocrylene; Eusolex®OCR, Neo Heliopan®Type 303, Uvinul®N 539 SG), menthyl o-aminobenzoate (menthyl anthranilate; Neo Heliopan®MA), 2,2 ', 4,4'-tetrahydroxybenzophenone (Benzophenone-2; Uvinul®D-50), 2,2'-dihydroxy-4,4'-dimethoxybenzophenone (Benzophenone-6), 2,2'-dihydroxy-4,4'-dimethoxybenzophenone-5-sodium sulfonate and 2-cyano-3,3-diphenylacrylic acid 2'-ethylhexyl ester. Are preferred 4-aminobenzoic acid, N, N, N-trimethyl-4- (2-oxoborn-3-ylidenemethyl) aniline methyl sulfate, 3,3,5- Trimethyl cyclohexyl salicylate, 2-hydroxy-4-methoxy-benzophenone, 2-phenylbenzimidazole-5-sulfonic acid and its potassium, sodium and triethanolamine salts, 3,3 '- (1,4- Phenylenedimethylene) -bis (7,7-dimethyl-2-oxobicyclo- [2.2.1] hept-1-yl-methanesulfonic acid) and their salts, 1- (4-tert-butylphenyl) -3- ( 4-methoxyphenyl) propane-1,3-dione, α- (2-Oxoborn-3-ylidene) toluene-4-sulfonic acid and its salts, ethoxylated Ethyl 4-aminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-ethylhexyl salicylic acid, isopentyl 4-methoxycinnamate, 2-ethylhexyl 4-methoxycinnamate, 2- Hydroxy-4-methoxybenzophenone-5-sulfonic acid and its sodium salt, 3- (4'-methylbenzylidene) -D, L-camphor, 3-benzylidene-camphor, 4-isopropylbenzyl salicylate, 2,4,6-trianilino- (p-carbo-2'-ethylhexyl-1'-oxi) -1,3,5-triazine, 3-imidazol-4-yl-acrylic acid and their Ethyl ester, polymers of N - {(2 and 4) - [2-oxoborn-3-ylidenemethyl] benzyl} acrylamide. According to the invention, 2-hydroxy-4-methoxy-benzophenone, 2- Phenylbenzimidazole-5-sulfonic acid and its potassium, sodium and triethanolamine salts, 1- (4-tert-butylphenyl) -3- (4-methoxyphenyl) propane-1,3-dione, 4-methoxycinnamic acid 2- ethylhexyl ester and 3- (4'-methylbenzylidene) -D, L-camphor.

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

Furthermore, it was found that in structurally similar UV filters in many cases water-insoluble compound in the context of the teaching of the invention the higher Has an effect on such water-soluble compounds that differ from it distinguish one or more additional ionic groups. As insoluble in water Within the scope of the invention to understand those UV filters that do not exceed at 20 ° C Dissolve 1% by weight, especially not more than 0.1% by weight, in water. Furthermore, should these compounds in common cosmetic oil components at room temperature be at least 0.1, in particular at least 1% by weight soluble). The usage water-insoluble UV filter can therefore be preferred according to the invention.

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

These UV filters have the general structure U-Q.

The structural part U stands for a group that absorbs UV rays. This group can, in principle, differ from the known ones used in the cosmetics sector, above derived UV filters in which a group, usually a hydrogen atom, of the UV Filters through a cationic group Q, in particular with a quaternary amino function, is replaced.

• - substituierte Benzophenone,
• - p-Aminobenzoesäureester,
• - Diphenylacrylsäureester,
• - Zimtsäureester,
• - Salicylsäureester,
• - Benzimidazole und
• - o-Aminobenzoesäureester.

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

• - substituted benzophenones,
• p-aminobenzoic acid ester,
• - diphenylacrylic acid ester,
• - cinnamic acid esters,
• - salicylic acid esters,
• - benzimidazoles and
• o-aminobenzoic acid esters.

Structural parts U, which differ from the cinnamic acid amide or Deriving N, N-dimethylamino-benzoic acid amide are preferred according to the invention.

The structural parts U can in principle be chosen so that the absorption maximum the UV filter in UVA (315-400 nm) -, as well as in UVB (280-315 nm) - or in UVC (<280 nm) range can be. UV filter with an absorption maximum in the UVB Range, especially in the range of about 280 to about 300 nm, are special prefers.

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

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

The group Q advantageously has the general structure - (CH ₂ ) _x -N ⁺ R ¹ R ² R ³ X ^- , in which x represents an integer from 1 to 4, R ¹ and R ² independently of one another represent C _{1 -4} - alkyl groups, R ³ stands for a C _1-22 alkyl group or a benzyl group and X ^- for a physiologically acceptable anion. Within the framework of this general structure, x preferably represents the number 3, R ¹ and R ² each for a methyl group and R ³ either for a methyl group or a saturated or unsaturated, linear or branched hydrocarbon chain with 8 to 22, in particular 10 to 18, carbon atoms.

Physiologically compatible anions are, for example, inorganic anions such as Halides, especially chloride, bromide and fluoride, sulfate ions and phosphate ions as well organic anions such as lactate, citrate, acetate, tartrate, methosulfate and tosylate.

Two preferred UV filters with cationic groups are those as commercial products available compounds cinnamic acid amidopropyl-trimethylammonium chloride (Incroquat®UV- 283) and dodecyl-dimethylaminobenzamidopropyl-dimethylammonium 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 preferred a cationic group.

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

The activity of the active ingredient complex (A) according to the invention can be further increased by a 2-pyrrolidinone-5-carboxylic acid and its derivatives (J). Another object of the invention is therefore the use of the active ingredient in combination with derivatives of 2-pyrrolidinone-5-carboxylic acid. Preferred are the sodium, potassium, calcium, magnesium or ammonium salts in which the ammonium ion carries one to three C ₁ to C ₄ alkyl groups in addition to hydrogen. The sodium salt is very particularly preferred. The amounts used in the agents according to the invention are 0.05 to 10% by weight, based on the total agent, particularly preferably 0.1 to 5 and in particular 0.1 to 3% by weight.

The combination of the active ingredient complex (A) with has also been found to be advantageous Vitamins, provitamins and vitamin precursors and their derivatives (K) have been proven.

Such vitamins, pro-vitamins and vitamin precursors are according to the invention 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 β-carotene is the provitamin of retinol. According to the invention, vitamin A acid and its esters, vitamin A aldehyde and vitamin A alcohol and its esters such as palmitate and acetate come into consideration as vitamin A components. The preparations used according to the invention preferably contain the vitamin A component in amounts of 0.05-1% by weight, based on the entire preparation.

• - Vitamin B₁ (Thiamin)
• - Vitamin B₂ (Riboflavin)
• - Vitamin B₃. Unter dieser Bezeichnung werden häufig die Verbindungen Nicotinsäure und Nicotinsäureamid (Niacinamid) geführt. Erfindungsgemäß bevorzugt ist das Nicotinsäureamid, das in den erfindungsgemäß verwendetenen Mitteln bevorzugt in Mengen von 0,05 bis 1 Gew.-%, bezogen auf das gesamte Mittel, enthalten ist.
• - Vitamin B₅ (Pantothensäure, Panthenol und Pantolacton). Im Rahmen dieser Gruppe wird bevorzugt das Panthenol und/oder Pantolacton eingesetzt. Erfindungsgemäß einsetzbare Derivate des Panthenols sind insbesondere die Ester und Ether des Panthenols sowie kationisch derivatisierte Panthenole. Einzelne Vertreter sind beispielsweise das Panthenoltriacetat, der Panthenolmonoethylether und dessen Monoacetat sowie die in der WO 92/13829 offenbarten kationischen Panthenolderivate. Die genannten Verbindungen des Vitamin B₅-Typs sind in den erfindungsgemäß verwendeten Mitteln bevorzugt in Mengen von 0,05-10 Gew.-%, bezogen auf das gesamte Mittel, enthalten. Mengen von 0,1-5 Gew.-% sind besonders bevorzugt.
• - Vitamin B₆ (Pyridoxin sowie Pyridoxamin und Pyridoxal).

The vitamin B group or the vitamin B complex include

• - Vitamin B ₁ (thiamine)
• - Vitamin B ₂ (riboflavin)
• - Vitamin B ₃ . The compounds nicotinic acid and nicotinamide (niacinamide) are often listed under this name. According to the invention, preference is given to nicotinic acid amide, which is preferably present in the agents used according to the invention in amounts of 0.05 to 1% by weight, based on the total agent.
• - Vitamin B ₅ (pantothenic acid, panthenol and pantolactone). Within this group, panthenol and / or pantolactone is preferably used. Derivatives of panthenol which can be used according to the invention are, in particular, the esters and ethers of panthenol and cationically derivatized panthenols. Individual representatives are, for example, panthenol triacetate, panthenol monoethyl ether and its monoacetate and the cationic panthenol derivatives disclosed in WO 92/13829. The compounds of the vitamin B ₅ type mentioned are preferably present in the agents used according to the invention in amounts of 0.05-10% by weight, based on the total agent. Amounts of 0.1-5% by weight are particularly preferred.
• - Vitamin B ₆ (pyridoxine, pyridoxamine and pyridoxal).

Vitamin C (ascorbic acid). Vitamin C is used in the agents according to the invention preferably used in amounts of 0.1 to 3 wt .-%, based on the total agent. Use in the form of the palmitic acid ester, the glucoside or phosphate be preferred. Use in combination with tocopherols can also be preferred his.

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

Vitamin F. The term "vitamin F" usually includes 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, but for which meanwhile the Trivial name biotin has prevailed. Biotin is used in the invention Agents preferably in amounts of 0.0001 to 1.0% by weight, in particular in amounts of Contain 0.001 to 0.01 wt .-%.

The agents used according to the invention preferably contain vitamins, provitamins and Vitamin precursors from groups A, B, E and H.

Panthenol, pantolactone, pyridoxine and its derivatives as well as nicotinamide and biotin are particularly preferred.

Finally, the effect of the active ingredient complex (A) can also by Increase combined use with plant extracts (L).

These extracts are usually produced by extracting the entire plant. It However, in individual cases it may also be preferred that the extracts exclusively from flowers and / or to produce 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 pointed out in the on page 44 of the 3rd edition of the guide to Ingredient declaration of cosmetic products, issued by the industry association body care and detergents e. V. (IKW), Frankfurt, starting table.

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

The extracts from green tea, oak bark, nettle, Witch hazel, hops, chamomile, burdock root, horsetail, linden flowers, almond, aloe vera, Coconut, mango, apricot, lime, wheat, kiwi, melon, orange, grapefruit, sage, Rosemary, Birch, Cuckoo Flower, Quendel, Yarrow, Hauhechel, Meristem, Ginseng and ginger root.

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

As extracting agents for the production of the plant extracts mentioned, water, Alcohols and their mixtures can be used. Among the alcohols are included lower alcohols such as ethanol and isopropanol, but especially polyhydric alcohols such as Ethylene glycol and propylene glycol, both as the sole extractant and in Mix with water, preferred. Plant extracts based on water / propylene glycol in a ratio of 1:10 to 10: 1 have proven to be particularly suitable.

According to the invention, the plant extracts can be either pure or diluted Form are used. If they are used in diluted form, they contain usually about 2-80 wt .-% active substance and as a solvent that in their Extraction or extractant mixture used.

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

In addition, it can prove to be advantageous if, in addition to the invention Active ingredient complex (A) penetration aids and / or swelling agents (M) are included. These include, for example, urea and urea derivatives, guanidine and its derivatives, arginine and its derivatives, water glass, imidazole and its derivatives, Histidine and its derivatives, benzyl alcohol, glycerin, glycol and glycol ether, Propylene glycol and propylene glycol ether, for example propylene glycol monoethyl ether, Carbonates, hydrogen carbonates, diols and triols, and in particular 1,2-diols and 1,3- Diols such as 1,2-propanediol, 1,2-pentanediol, 1,2-hexanediol, 1,2-dodecanediol, 1,3-propanediol, 1,6-hexanediol, 1,5-pentanediol, 1,4-butanediol.

Short-chain carboxylic acids (N) can also be advantageous for the purposes of the invention Support active ingredient complex (A). Among short chain carboxylic acids and their derivatives For the purposes of the invention, carboxylic acids are understood which are saturated or unsaturated and / or straight-chain or branched or cyclic and / or aromatic and / or can be heterocyclic and have a molecular weight less than 750. Prefers For the purposes of the invention, saturated or unsaturated straight-chain or branched Carboxylic acids with a chain length of 1 up to 16 carbon atoms in the chain, whole those with a chain length of 1 to 12 carbon atoms in the are particularly preferred Chain.

The short-chain carboxylic acids in the sense of the invention can be one, two, three or more Have carboxy groups. For the purposes of the invention, carboxylic acids are preferred several carboxy groups, especially di- and tricarboxylic acids. The carboxy groups can be wholly or partly as an ester, acid anhydride, lactone, amide, imidic acid, lactam, Lactim, dicarboximide, carbohydrazide, hydrazone, hydroxam, hydroxime, amidine, Amidoxime, nitrile, phosphonic or phosphate esters are present. The invention Carboxylic acids can of course along the carbon chain or the ring structure be substituted. Among the substituents of the carboxylic acids according to the invention are examples include C1-C8-alkyl, C2-C8-alkenyl, aryl, aralkyl and aralkenyl, Hydroxymethyl, C2-C8-hydroxyalkyl, C2-C8-hydroxyalkenyl, aminomethyl, C2-C8 Aminoalkyl, cyano, formyl, oxo, thioxo, hydroxy, mercapto, amino, carboxy or imino groups. Preferred substituents are C1-C8-alkyl, hydroxymethyl, Hydroxy, amino and carboxy groups. Substituents in α- Position. Very particularly preferred substituents are hydroxy, alkoxy and Amino groups, where the amino function is optionally by alkyl, aryl, aralkyl and / or Alkenyl radicals can be further substituted. Furthermore, they are also preferred Carboxylic acid derivatives the phosphonic and phosphate esters.

Examples of carboxylic acids according to the invention are formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, glyceric acid, glyoxylic acid, adipic acid, pimelic acid, suberic acid, azocanoic acid, sebrotonic acid, sebacic acid , Elaidic acid, maleic acid, fumaric acid, muconic acid, citraconic acid, mesaconic acid, camphoric acid, benzoic acid, o, m, p-phthalic acid, naphthoic acid, toluoylic acid, hydratropic acid, atropic acid, cinnamic acid, isonicotinic acid, nicotinic acid, bicarbamicanoic acid, 4,4'-dicarboxylic acid, 4,4'-diacid 6'-binicotinic acid, 8-carbamoyloctanoic acid, 1,2,4-pentane tricarboxylic acid, 2-pyrrolecarboxylic acid, 1,2,4,6,7-naphthalene pentaacetic acid, malonaldehyde acid, 4-hydroxy-phthalamic acid, 1-pyrazole carboxylic acid, gallic acid or propane tricarboxylic acid, a Dicarboxylic acid selected from the group formed by compounds the general formula (NI),


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

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

A manufacturing process can be found, for example, in US Pat. No. 3,753,968. German patent 22 50 055 discloses the use of these dicarboxylic acids in liquid soap masses. From German Offenlegungsschrift 28 33 291 are Deodorants known to contain zinc or magnesium salts of these dicarboxylic acids. Finally, from the German laid-open specification 35 03 618 means for washing and Rinsing the hair is known to be noticeable by adding these dicarboxylic acids Improved hair cosmetic effect of the water-soluble ionic contained in the agent Polymers is obtained. Finally, 197 54 053 are from the German published application Known hair treatment agents which have nourishing effects.

The dicarboxylic acids of formula (N-I) can, for example, by reacting polyunsaturated dicarboxylic acids with unsaturated monocarboxylic acids in the form of a Diels-Alder cyclization can be produced. Usually one gets multiple unsaturated fatty acid as a dicarboxylic acid component. The is preferably from Linoleic acid accessible to natural fats and oils. As a monocarboxylic acid component are especially acrylic acid, but also z. B. methacrylic acid and crotonic acid are preferred. Diels-Alder reactions usually produce mixtures of isomers in which there is a component in excess. These mixtures of isomers can according to the invention as well as the pure compounds.

Can be used according to the invention in addition to the preferred dicarboxylic acids of the formula (N-I) are also those dicarboxylic acids which differ from the compounds of the formula (N-I) distinguish by 1 to 3 methyl or ethyl substituents on the cyclohexyl ring these compounds formally by adding one molecule of water to the Double formation of the cyclohexene ring are formed.

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

In addition to the short-chain carboxylic acids according to the invention listed above by way of example themselves, their physiologically tolerable salts can also be used according to the invention become. Examples of such salts are the alkali, alkaline earth, zinc salts as well Ammonium salts, including the mono-, di- and Trimethyl, ethyl and hydroxyethyl ammonium salts are to be understood. Most notably However, within the scope of the invention, preference can be given to alkaline reactions Amino acids such as arginine, lysine, ornithine and histidine, neutralized acids be used. Furthermore, it may be preferred for formulation reasons that Carboxylic acid from the water-soluble representatives, in particular the water-soluble salts, select.

It is also preferred according to the invention to use hydroxycarboxylic acids and again in particular the dihydroxy, trihydroxy and polyhydroxycarboxylic acids and the Dihydroxy-, trihydroxy- and polyhydroxy- di-, tri- and polycarboxylic acids together with the Use active ingredient (A). It has been shown that in addition to the hydroxycarboxylic acids also the hydroxycarboxylic acid esters and the mixtures of hydroxycarboxylic acids and their esters as well as polymeric hydroxycarboxylic acids and their esters very particularly may be preferred. Preferred hydroxycarboxylic acid esters are, for example, full esters glycolic acid, lactic acid, malic acid, tartaric acid or citric acid. Further Hydroxycarboxylic acid esters which are generally suitable are esters of β-hydroxypropionic acid Tartronic acid, D-gluconic acid, sugar acid, mucic acid or Glucuronic. Primary, linear or branched are suitable as alcohol components of these esters aliphatic alcohols with 8-22 carbon atoms, e.g. B. fatty alcohols or synthetic Fatty alcohols. The esters of C12-C15 fatty alcohols are particularly preferred. ester this type are commercially available, e.g. B. under the trademark Cosmacol® EniChem, Augusta Industriale. Polyhydroxypolycarboxylic acids are particularly preferred Polylactic acid and polytartaric acid and their esters.

Ultimately, of course, in addition to Active ingredient complex (A) according to the invention also other protein hydrolyzates and their Use derivatives (P) that are not derived from natural silk. protein are product mixtures that are degraded by acidic, basic or enzymatically catalyzed Proteins (proteins) can be obtained. Under the term protein hydrolyzates total hydrolyzates and individual amino acids and their derivatives according to the invention as well as mixtures of different amino acids understood. Continue to be Polymers constructed according to the invention from amino acids and amino acid derivatives understood the term protein hydrolyzates. The latter include, for example, polyalanine, Polyasparagin, Polyserin etc. to count. Further examples of usable according to the invention Compounds are L-alanyl-L-proline, polyglycine, glycyl-L-glutamine or D / L- Methionine-S-Methylsulfoniumchlorid. Of course, according to the invention, β- Amino acids and their derivatives such as β-alanine, anthranilic acid or hippuric acid be used. The molecular weight of the protein hydrolyzates which can be used according to the invention is between 75, the molecular weight for glycine, and 200000, preferably this is Molecular weight 75 to 50,000 and very particularly preferably 75 to 20,000 daltons.

According to the invention, protein hydrolysates can be either vegetable or animal marine or synthetic origin.

Animal protein hydrolyzates are, for example, elastin, collagen, keratin and Milk protein protein hydrolyzates, which may also be in the form of salts. Such products are, for example, under the trademarks Dehylan® (Cognis), Promois® (Interorgana), Collapuron® (Cognis), Nutrilan® (Cognis), Gelita-Sol® (German gelatin Factories Stoess & Co), Lexein® (Inolex) and Kerasol® (Croda) distributed.

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

Although the use of the protein hydrolyzates as such is preferred, others can If necessary, amino acid mixtures obtained in another way can also be used. It is also possible to use derivatives of the protein hydrolyzates, for example in Form of their fatty acid condensation products. Such products are for example under the names Lamepon® (Cognis), Lexein® (Inolex), Crolastin® (Croda) or Crotein® (Croda) sold.

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

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

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

In principle, the active ingredient complex (A) according to the invention can directly the colorant, the Corrugating agent or fixation are added. The application of the active ingredient complex on the keratinic fiber can also be done in a separate step, either before or following the actual dyeing or corrugation process. Even separate ones Treatments, possibly also days or weeks before or after the hair treatment, for example, by coloring or waves, are based on the teaching of the invention includes. However, the use of the active ingredient complex according to the invention can be preferred after the appropriate hair treatment such as dyeing or waves especially in the appropriate hair treatment agents.

The term dyeing process includes all processes known to the person skilled in the art which a coloring agent is applied to the optionally moistened hair and this either for a time between a few minutes and about 45 minutes on the hair leave and then rinsed with water or a surfactant or left entirely on the hair. It is explicitly referred to in this context the well-known monographs, e.g. B. K. H. Schrader, basics and recipes of Cosmetics, 2nd edition, Hüthig Buch Verlag, Heidelberg, 1989, referenced the reflect appropriate knowledge of the specialist.

The term corrugation includes all methods known to the person skilled in the art, in which a wavy agent on the hair, which may be damp and twisted on curlers is applied and this either for a time between a few minutes and about 45 Leave on the hair for minutes and then with water or a surfactant Medium is rinsed out, then a permanent wave fixation is applied to the hair and this for a time between a few minutes and about 45 minutes on the hair leave and then rinsed with water or a surfactant. In this context, it is expressly referred to the known monographs, e.g. B. K. H. Schrader, basics and formulations of cosmetics, 2nd edition, Hüthig Buch Verlag, Heidelberg, 1989, referenced, which reflect the corresponding knowledge of the expert.

With regard to the manner in which the active ingredient complex according to the invention to the There is no keratin fiber, especially human hair principal restrictions. As the packaging of these preparations are for example creams, lotions, solutions, water, emulsions such as W / O-, O / W-, PIT- Emulsions (emulsions based on the theory of phase inversion, called PIT), Microemulsions and multiple emulsions, gels, sprays, aerosols and foam aerosols suitable. The pH of these preparations can in principle be between 2-11. He is preferably between 5 and 11, values from 6 to 10 being particularly preferred. Virtually any of these can be used for cosmetic purposes to adjust this pH usable acid or base can be used. Preferred bases are ammonia, Alkali hydroxides, monoethanolamine, triethanolamine and N, N, N ', N'-tetrakis (2- hydroxypropyl) -ethylenediamine.

Preparations remaining on the hair have proven to be effective and can therefore represent preferred embodiments of the teaching according to the invention. Under on Remaining hair according to the invention are understood to be those preparations which not within the treatment after a period of a few seconds up to an hour out of the hair with the help of water or an aqueous solution be rinsed out. Rather, the preparations remain until the next hair wash, i.e. H. usually more than 12 hours on the hair.

According to a second preferred embodiment, these preparations are as Hair conditioner or hair conditioner formulated. The preparations according to the invention according to this Embodiment can with water or a after this exposure time at least predominantly water-containing agents are rinsed out; however, they can, as above run, be left on the hair. It may be preferred that Preparation according to the invention before the use of a cleaning agent, a waving agent or other hair treatment products to apply to the hair. In this case, the Preparation according to the invention as structural protection for the subsequent applications.

According to further preferred embodiments, it can be in the inventive However, agents also include cleaning agents such as shampoos, care agents such as conditioners, setting agents such as hair setting agents, foam setting agents, styling gels and Hair dryer waves, permanent shaping agents such as permanent wave and fixing agents and in particular used in the context of a permanent wave process or dyeing process Act pretreatment agent or rinse.

In addition to the active ingredient complex (A) which is mandatory according to the invention and the Further, preferred components mentioned above, these preparations in principle all other known to those skilled in the art for such cosmetic products Components included.

• - nichtionische Polymere wie beispielsweise Vinylpyrrolidon/Vinylacrylat-Copolymere, Polyvinylpyrrolidon und Vinylpyrrolidon/Vinylacetat-Copolymere und Polysiloxane,
• - Verdickungsmittel wie Agar-Agar, Guar-Gum, Alginate, Xanthan-Gum, Gummi arabicum, Karaya-Gummi, Johannisbrotkernmehl, Leinsamengummen, Dextrane, Cellulose-Derivate, z. B. Methylcellulose, Hydroxyalkylcellulose und Carboxymethylcellulose, Stärke-Fraktionen und Derivate wie Amylose, Amylopektin und Dextrine, Tone wie z. B. Bentonit oder vollsynthetische Hydrokolloide wie z. B. Polyvinylalkohol,
• - haarkonditionierende Verbindungen wie Phospholipide, beispielsweise Sojalecithin, Ei-Lecitin und Kephaline, sowie Silikonöle,
• - Parfümöle, Dimethylisosorbid und Cyclodextrine,
• - Lösungsmittel und -vermittler wie Ethanol, Isopropanol, Ethylenglykol, Propylenglykol, Glycerin und Diethylenglykol,
• - symmetrische und unsymmetrische, lineare und verzweigte Dialkylether mit insgesamt zwischen 12 bis 36 C-Atomen, insbesondere 12 bis 24 C-Atomen, wie beispielsweise Di-n-octylether, Di-n-decylether, Di-n-nonylether, Di-n-undecylether und Di-n- dodecylether, n-Hexyl-n-octylether, n-Octyl-n-decylether, n-Decyl-n-undecylether, n- Undecyl-n-dodecylether und n-Hexyl-n-Undecylether sowie Di-tert-butylether, Di-isopentylether, Di-3-ethyldecylether, tert.-Butyl-n-octylether, iso-Pentyl-n-octylether und 2-Methyl-pentyl-n-octylether,
• - Fettalkohole, insbesondere lineare und/oder gesättigte Fettalkohole mit 8 bis 30 C- Atomen,
• - Monoester von C8 bis C30-Fettsäuren mit Alkoholen mit 6 bis 24 C-Atomen,
• - faserstrukturverbessernde Wirkstoffe, insbesondere Mono-, Di- und Oligosaccharide, wie beispielsweise Glucose, Galactose, Fructose, Fruchtzucker und Lactose,
• - konditionierende Wirkstoffe wie Paraffinöle, pflanzliche Öle, z. B. Sonnenblumenöl, Orangenöl, Mandelöl, Weizenkeimöl und Pfirsichkernöl sowie
• - Phospholipide, beispielsweise Sojalecithin, Ei-Lecithin und Kephaline,
• - quaternierte Amine wie Methyl-1-alkylamidoethyl-2-alkylimidazolinium-methosulfat,
• - Entschäumer wie Silikone,
• - Farbstoffe zum Anfärben des Mittels,
• - Antischuppenwirkstoffe wie Piroctone Olamine, Zink Omadine und Climbazol,
• - Wirkstoffe wie Allantoin und Bisabolol,
• - Cholesterin,
• - Konsistenzgeber wie Zuckerester, Polyolester oder Polyolalkylether,
• - Fette und Wachse wie Walrat, Bienenwachs, Montanwachs und Paraffine,
• - Fettsäurealkanolamide,
• - Komplexbildner wie EDTA, NTA, β-Alanindiessigsäure und Phosphonsäuren,
• - Quell- und Penetrationsstoffe wie primäre, sekundäre und tertiäre Phosphate,
• - Trübungsmittel wie Latex, Styrol/PVP- und Styrol/Acrylamid-Copolymere
• - Perlglanzmittel wie Ethylenglykolmono- und -distearat sowie PEG-3-distearat,
• - Pigmente,
• - Reduktionsmittel wie z. B. Thioglykolsäure und deren Derivate, Thiomilchsäure, Cysteamin, Thioäpfelsäure und α-Mercaptoethansulfonsäure,
• - Treibmittel wie Propan-Butan-Gemische, N₂O, Dimethylether, CO₂ und Luft,
• - Antioxidantien.

Other active ingredients, auxiliaries and additives are, for example

• non-ionic polymers such as, for example, vinyl pyrrolidone / vinyl acrylate copolymers, polyvinyl pyrrolidone and vinyl pyrrolidone / vinyl acetate copolymers and polysiloxanes,
• Thickeners such as agar agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, linseed gums, dextrans, cellulose derivatives, e.g. B. methyl cellulose, hydroxyalkyl cellulose and carboxymethyl cellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such. B. bentonite or fully synthetic hydrocolloids such. B. polyvinyl alcohol,
• hair-conditioning compounds such as phospholipids, for example soy lecithin, egg lecithin and cephalins, and silicone oils,
• - perfume oils, dimethyl isosorbide and cyclodextrins,
• Solvents and mediators such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol,
• - Symmetrical and asymmetrical, linear and branched dialkyl ethers with a total of between 12 to 36 carbon atoms, in particular 12 to 24 carbon atoms, such as, for example, di-n-octyl ether, di-n-decyl ether, di-n-nonyl ether, di-n -undecyl ether and 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-isopentyl ether, di-3-ethyl decyl ether, tert-butyl-n-octyl ether, isopentyl-n-octyl ether and 2-methyl-pentyl-n-octyl ether,
• Fatty alcohols, in particular linear and / or saturated fatty alcohols with 8 to 30 carbon atoms,
• - Monoesters of C8 to C30 fatty acids with alcohols with 6 to 24 carbon atoms,
• active ingredients that improve fiber structure, in particular mono-, di- and oligosaccharides, such as, for example, glucose, galactose, fructose, fructose and lactose,
• - conditioning agents such as paraffin oils, vegetable oils, e.g. B. sunflower oil, orange oil, almond oil, wheat germ oil and peach seed oil as well
• Phospholipids, for example soy lecithin, egg lecithin and cephalins,
• quaternized amines such as methyl 1-alkylamidoethyl-2-alkylimidazolinium methosulfate,
• - defoamers like silicones,
• Dyes for coloring the agent,
• - anti-dandruff agents such as piroctone olamine, zinc omadine and climbazol,
• - active ingredients such as allantoin and bisabolol,
• - cholesterol,
• - consistency enhancers such as sugar esters, polyol esters or polyol alkyl ethers,
• - fats and waxes such as walrus, beeswax, montan wax and paraffins,
• - fatty acid alkanolamides,
• Complexing agents such as EDTA, NTA, β-alaninediacetic acid and phosphonic acids,
• Swelling and penetration substances such as primary, secondary and tertiary phosphates,
• - opacifiers such as latex, styrene / PVP and styrene / acrylamide copolymers
• Pearlescent 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, thio malic acid and α-mercaptoethanesulfonic acid,
• Propellants such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air,
• - antioxidants.

Regarding other optional components and the amounts used Components is expressly referred to the relevant manuals known to the expert, z. B. referred to the above monograph by K. H. Schrader.

In a fourth embodiment of the teaching according to the invention, it can be preferred to incorporate the active ingredient complex (A) directly into the coloring or tinting agent, which means the active ingredient complex (A) according to the invention in combination with dyes and / or Use dye precursors.

As such, developer (B1) and coupler type oxidation dye precursors (B2), natural and synthetic substantive dyes (C) and precursors natural dyes, such as indole and indoline derivatives, as well as mixtures of representatives of one or more of these groups can be used.

As oxidation dye precursors of the developer type (B1) are usually primary aromatic amines with a further para or ortho position free or substituted hydroxyl 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-hydroxyethyl) -p-phenylenediamine, 2- (2,5-diaminophenoxy) ethanol, 4-amino-3-methylphenol, 2,4,5,6-tetraaminopyrimidine, 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- aminophenol, 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. 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.

M-Phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenol derivatives are generally used as oxidation dye precursors of the coupler type (B2). Examples of such coupler components are m-aminophenol and its derivatives such as 5-amino-2-methylphenol, 5- (3-hydroxypropylamino) -2-methylphenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4 - aminophenoxyethanol, 2,6-dimethyl-3-aminophenol, 3-trifluoroacetylamino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol, 5 - (2'-Hydroxyethyl) amino-2-methylphenol, 3- (diethylamino) phenol, N-cyclopentyl-3-aminophenol, 1,3-dihydroxy-5- (methylamino) benzene, 3- (ethylamino) - 4-methylphenol and 2,4-dichloro-3-aminophenol, o-aminophenol and its derivatives, m-diaminobenzene and its derivatives such as 2,4-diaminophenoxyethanol, 1,3-bis (2,4-diaminophenoxy) propane , 1-methoxy-2-amino-4- (2'-hydroxyethylamino) benzene, 1,3-bis (2,4-diaminophenyl) propane, 2,6-bis (2-hydroxyethylamino) -1-methylbenzene and 1-amino-3-bis (2'-hydroxyethyl) aminobenzene, o-diaminobenzene and its derivatives such as 3,4-diaminobenzoic acid and 2,3-diamino -1-methylbenzene, di- or trihydroxybenzene derivatives such as resorcinol, resorcinol monomethyl ether, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2-chlororesorcinol, 4-chlororesorcinol, pyrogallol and 1,2,4-trihydroxybenzene,
Pyridine derivatives such as 2,6-dihydroxypyridine, 2-amino-3-hydroxypyridine, 2-amino-5-chloro-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine, 2,6-dihydroxy-3,4 dimethylpyridine, 2,6-dihydroxy-4-methylpyridine, 2,6-diaminopyridine, 2,3-diamino-6-methoxypyridine and 3,5-diamino-2,6-dimethoxypyridine,
Naphthalene derivatives such as 1-naphthol, 2-methyl-1-naphthol, 2-hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1 , 8-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and 2,3-dihydroxynaphthalene, morpholine derivatives such as 6-hydroxybenzomorpholine and 6-amino-benzomorpholine, quinoxaline derivatives such as 6-methyl-1,2,3,4-tetrahydroquinoxaline, pyrazole derivatives such as 1-phenyl-3-methylpyrazol-5-one, indole derivatives such as 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole, methylenedioxybenzene derivatives such as 1-hydroxy-3,4-methylenedioxybenzene, 1-amino-3,4-methylenedioxybenzene and 1- (2'-hydroxyethyl) -amino-3,4-methylenedioxybenzene.

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, 4-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 direct pull Dyes are those under the international names 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 1,4-bis (β-hydroxyethyl) amino-2-nitrobenzene, 4-amino-2-nitrodiphenylamine-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.

Directly occurring dyes occurring in nature are, for example, henna red, henna neutral, chamomile flower, sandalwood, black tea, sapwood, sage, blue wood, Madder root, catechu, sedre and alkanna root included.

It is not necessary that the oxidation dye precursors or the substantive ones Dyes each represent uniform compounds. Rather, in the Hair dyes according to the invention, due to the manufacturing process for the individual Dyes, minor components may be included, so far these do not adversely affect the coloring result or for other reasons, e.g. B. toxicological, must be excluded.

Regarding those that can be used in the hair coloring and tinting agents according to the invention Dyes are further expressly referred to the monograph Ch. Zviak, The Science of Hair Care, Chapter 7 (pages 248-250; direct dyes) and Chapter 8, pages 264-267; Oxidation dye precursors), appeared as Volume 7 of the series "Dermatology" (Ed .: Ch., Culnan and H. Maibach), publisher Marcel Dekker Inc., New York, Basel, 1986, as well as the "European inventory of cosmetic raw materials", published by the European Community, available in disk form from the Federal Association of German Industrial and trading company for pharmaceuticals, health products and Personal care products e. V., Mannheim, referred to.

For example, indoles and indolines as well as whose physiologically acceptable salts are used. Such indoles and Indolines are used which have at least one hydroxyl or amino group, preferably as Have a substituent on the six-membered ring. These groups can carry further substituents, e.g. B. in the form of etherification or esterification of the hydroxy group or an alkylation the amino group. 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 as well as 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.

Of particular note within this group are N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline and in particular 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 process according to the invention Colorants used both as free bases and in the form of their physiological compatible salts with inorganic or organic acids, e.g. B. the hydrochloride, the Sulfates and hydrobromides can be used.

When using indoline or indole type dye precursors it can be preferred, this together with at least one amino acid and / or at least one Use oligopeptide. Preferred amino acids are aminocarboxylic acids, in particular α-aminocarboxylic acids and ω-aminocarboxylic acids. Among the α-aminocarboxylic acids are again arginine, lysine, ornithine and histidine are particularly preferred. A very special one preferred amino acid is arginine, especially in free form, but also as Hydrochloride used.

Both the oxidation dye precursors and the substantive dyes and the precursors of nature-analogous dyes are preferred in the agents according to the invention in amounts of 0.01 to 20 wt .-%, preferably 0.1 to 5 wt .-%, each based on all the means included.

Hair dye, especially if the coloring is oxidative, be it with atmospheric oxygen or other oxidizing agents, such as hydrogen peroxide, usually become weak acidic to alkaline, d. H. set to pH values in the range of about 5 to 11. To this Purpose, the colorants contain alkalizing agents, usually alkali 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 as well as 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 in this group. Even the use of ω-amino acids such as ω-aminocaproic acid are possible as alkalizing agents.

The actual hair colors are developed as part of an oxidative process Process, so can usual oxidizing agents, such as hydrogen peroxide or whose adducts with urea, melamine or sodium borate are used. However, oxidation with atmospheric oxygen as the only oxidizing agent can be preferred his. It is also possible to carry out the oxidation with the aid of enzymes, where the enzymes are used to generate oxidizing per compounds as well as to enhance the effect of a small amount present Oxidizing agents, or also enzymes can be used, the electrons from suitable Transfer developer components (reducing agents) to atmospheric oxygen. Are preferred Oxidases such as tyrosinase, ascorbate oxidase and laccase but also glucose oxidase, uricase or pyruvate oxidase. The procedure should also be mentioned, the effect of small amounts (e.g. 1% and less, based on the total average) of hydrogen peroxide To amplify peroxidases.

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

Especially with hair that is difficult to dye, the preparation can be used with the Dye precursors without prior mixing with the oxidation component on the hair be applied. After an exposure time of 20 to 30 minutes, if necessary after an intermediate rinse - the oxidation component applied. After another The exposure time of 10 to 20 minutes is then rinsed and, if desired shampooed. In this embodiment, according to a first variant, in which the prior application of the dye precursors leads to better penetration into the hair the corresponding agent is adjusted to a pH of about 4 to 7. According to one In the second variant, air oxidation is initially sought, with the applied one Agent preferably has a pH of 7 to 10. In the subsequent accelerated post-oxidation can be adjusted using acidic Peroxidisulfate solutions may be preferred as the oxidizing agent.

Furthermore, the formation of the color 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⁺ . Zn ²⁺ , Cu ²⁺ and Mn ²⁺ are particularly suitable. In principle, the metal ions can be used in the form of any physiologically acceptable salt. Preferred salts are the acetates, sulfates, halides, lactates and tartrates. By using these metal salts, the formation of the coloring can be accelerated and the color shade can be influenced in a targeted manner.

• a) den Wirkstoffkomplex (A)
• b) und eine Verbindung ausgewählt aus der Gruppe der Tenside (E) und/oder der Polymere (G).

A fifth subject of the invention is cosmetic compositions containing:

• a) the active ingredient complex (A)
• b) and a compound selected from the group of surfactants (E) and / or polymers (G).

With regard to further components of these agents, reference is made to what has been said above.

A sixth object of the invention is a method for treating skin or Hair in which an agent with the active ingredient complex (A) according to the invention, as in a of claims 1 to 7 used on the fibers is applied, the agent if desired, rinsed out again after an exposure time of 1 to 45 minutes.

Examples

Unless otherwise noted, all quantities are parts by weight.

1. Proof of effectiveness

To carry out the comparative experiments, the test subjects' hair was parted in the middle. On each half of the head, 5-7 ml of the respective active ingredient solutions were added to the towel-damp, i.e. slightly wet hair, and massaged in. The products in Table 1 were tested and assessed in a half-side test on four models, each with different hair quality, by four trained experts. Wet combability, dry combability, grip in wet hair, grip in dry hair, volume and hair gloss were used as criteria for the assessment. Table 1 Formulations of the comparison test

The results are summarized in Table 2. In conclusion, it can be clearly seen that a combination of the active substances A1 and A2 according to the invention to the active substance complex A results in a significant synergistic increase in the effect in comparison with the individual raw materials used in the same amount in relation to the active substance. Table 2 Results of the half-side test

2. Application examples 1. Hair conditioner Eumulgin® B2 ¹ 0.3 Cetyl / stearyl 3.3 sericin 0.3 Promois® Silk-1000 0.7 isopropyl 0.5 Lamesoft® PO 65 ⁴ 0.5 Dehyquart®A-CA ² 2.0 Salcare®SC 96 ⁵ 1.0 citric acid 0.4 Gluadin® ⁶ W40 2.0 pyridoxine 1.0 tartaric acid 0.7 Phenonip® ³ 0.8 water ad 100.0 ¹ cetylstearyl alcohol +20 EO (INCI name: Ceteareth-20) (COGNIS) ² trimethylhexadecylammonium chloride approx. 25% active substance (INCI name: Cetrimonium Chloride) (COGNIS) ³ Hydroxybenzoic acid methyl ester-hydroxybenzoic acid ethyl ester-hydroxybenzoic acid propyl ester-hydroxybenzoic acid butyl ester-phenoxyethanol mixture (approx. 28% active substance; INCI name: phenoxyethanol, methylparaben, ethylparaben, propylparaben, butylparaben) (NIPA) ⁴ Mixture of alkyl polyglycoside and fatty acid monoglyceride (INCI name: Coco-Glucoside (and) Glyceryl Oleate) ⁵ N, N, N-trimethyl-2 [(methyl-1-oxo-2-propenyl) oxy] -ethanaminium chloride homopolymer (50% active substance; INCI name: Polyquaternium-37 (and) propylene glycol dicaprilate dicaprate (and) PPG -1 Trideceth-6) (ALLIED COLLOIDS) ⁶ Wheat protein hydrolyzate approx. 40% active substance (INCI name: Hydrolyzed Wheat Protein) (COGNIS) Eumulgin® B2 0.3 Cetyl / stearyl 3.3 isopropyl 0.5 Paraffin oil perliquidum 15 cSt. DAB 9 0.3 Dehyquart®L 80 ⁷ 0.4 Lamesoft® PO 65 1.5 Cosmedia Guar® C 261 ⁸ 1.5 Promois® Milk-CAQ ⁹ 3.0 citric acid 0.4 Potassium Cocoyl Hydrolyzed Silk 2.0 Hexapeptide-2 0.3 Poly-L-serine 0.5 Phenonip.RTM 0.8 water ad 100.0 ⁷ bis (cocoylethyl) hydroxyethyl methyl ammonium methosulfate (approx. 76% active substance in propylene glycol; INCI name: dicocoylethyl hydroxyethyl monium methosulfate, propylene glycol) (COGNIS) ⁸ guar hydroxypropyltrimethylammonium chloride; INCI name: Guar Hydroxypropyl Trimonium Chloride (COGNIS) ⁹ INCI name: Cocodimonium Hydroxypropyl Hydrolyzed Casein (SEIWA KASEI) Dehyquart® F75 ¹⁰ 4.00 Cetyl / stearyl 4.00 Paraffin oil perliquidum 15 cSt DAB 9 1.50 Dehyquart®A-CA 4.00 Lamesoft® PO 65 1.00 Salcare®SC 96 1.50 sericin 0.10 Promois® Silk 1000 0.40 D / L-isoleucine 2.50 glyoxylic 0.50 Amisafe-LMA-60® ¹¹ 1.00 Gluadin®W 20 ¹² 3.00 Germall® 115 ¹³ 1.00 citric acid 0.15 Phenonip.RTM 0.80 water ad 100.00 ¹⁰ fatty alcohol methyltriethanolammonium methyl sulfate dialkyl ester mixture (INCI name: distearoylethyl hydroxyethylmonium methosulfate, cetearyl alcohol) (COGNIS) ¹¹ INCI name Hydroxypropyl Arginine Lauryl / Myristyl Ether HCl (Ajinomoto) ¹² Wheat protein hydrolyzate (20% active substance in water; INCI name: Aqua (and) Hydrolized Wheat Protein (and) Sodium Benzoate (and) Phenoxyethanol (and) Methylparaben (and) Propylparaben) (COGNIS) ¹³ INCI name: Imidazolidinyl Urea (Sutton Laboratories) Dehyquart® L80 2.00 Cetyl / stearyl 6.00 Paraffin oil perliquidum 15 cSt DAB 9 2.00 Rewoquat®W 75 ¹⁴ 2.00 Cosmedia Guar® C261 0.50 Lamesoft® PO 65 0.50 Sepigel®305 ¹⁵ 3.50 Honeyquat® 50 ¹⁶ 1.00 Gluadin® WQ 2.50 Gluadin®W 20 3.00 Hydrolyzed sericin 0.80 L-glycine 0.40 L-alanyl-L-proline 1.00 L-tyrosine 0.20 citric acid 0.15 Phenonip.RTM 0.80 water ad 100.00 ¹⁴ 1-methyl-2-nortalgalkyl-3-tallow fatty acid amidoethylimidazolinium methosulfate (approx. 75% active substance in propylene glycol; INCI name: Quaternium-27, propylene glycol) (WITCO) ¹⁵ copolymer of acrylamide and 2-acrylamido-2-methylpropanesulfonic acid (INCI name: polyacrylamide (and) C ₁₃ -C ₁₄ isoparaffin (and) Laureth-7) (SEPPIC) ¹⁶ INCI name: Hydroxypropyltrimonium Honey (BROOKS) Dehyquart® F75 0.30 Salcare®SC 96 5.00 Gluadin® WQ 1.50 Lamesoft® PO 65 0.50 Dow Corning®200 Fluid, 5 cSt. ¹⁷ 1.50 Gafquat®755N ¹⁸ 1.50 Poly-D / L-alanine 1.50 serine 0.10 glycine 0.50 tyrosine 0.20 sericin 0.20 Biodocarb® ¹⁹ 0.02 perfume oil 0.25 water ad 100.00 ¹⁷ polydimethylsiloxane (INCI name: Dimethicone) (DOW CORNING) ¹⁸ dimethylaminoethyl methacrylate-vinylpyrrolidone copolymer, quaternized with diethyl sulfate (19% active substance in water; INCI name: Polyquaternium-11) (GAF) ¹⁹ 3-iodo-2-propynyl-n-butyl carbamate (INCI name: iodopropynyl butyl carbamate) (MILKER & GRÜNING) Sepigel®305 5.00 Dow Corning®Q2-5220 ²⁰ 1.50 Promois® Milk Q ²¹ 3.00 Lamesoft® PO 65 0.50 Polymer P1 according to DE 39 29 173 0.60 Genamin®DSAC ²² 0.30 D / L-methionine-S-Methylsulfoniumchlorid 1.80 Hydrolyzed sericin 0.50 Promois® Silk 1000 1.00 Phenonip.RTM 0.80 perfume oil 0.25 water ad 100.00 ²⁰ silicone glycol copolymer (INCI name: Dimethicone Copolyol) (DOW CORNING) ²¹ INCI name Hydroxypropyltrimonium Hydrolyzed Casein approx. 30% active substance (SEIWA KASEI) ²² Dimethyldistearylammonium chloride (INCI name: Distearyldimonium Chloride) (CLARIANT) Texapon® NSO ²³ 40.0 Dehyton® G ²⁴ 6.0 Polymer JR 400® ²⁵ 0.5 Cetiol® HE ²⁶ 0.5 Ajidew® NL 50 ²⁷ 1.0 Lamesoft® PO 65 3.0 sericin 0.8 Promois® Silk 1000 2.0 Gluadin® WQT ²⁸ 2.5 Gluadin® W 20 0.5 Panthenol (50%) 0.3 casein 2.0 Vitamin E. 0.1 Vitamin H 0.1 glutamic acid 0.2 citric acid 0.5 sodium benzoate 0.5 Perfume 0.4 NaCl 0.5 water ad 100.0 ²³ sodium lauryl ether sulfate approx. 28% active substance (INCI name: Sodium Laureth Sulfate) (COGNIS) ²⁴ INCI name: Sodium Cocoamphoacetate, approx. 30% active substance in water) (COGNIS) ²⁵ quaternized hydroxyethyl cellulose (INCI name: Polyquaternium-10) (UNION CARBIDE) ²⁶ polyol fatty acid esters (INCI name: PEG-7 Glyceryl Cocoate) (COGNIS) ²⁷ sodium salt of 2-pyrrolidinone-5-carboxylic acid (50% active substance: INCI name: Sodium PCA) (AJINOMOTO) ²⁸ INCI name: Hydroxypropyltrimonium Hydrolyzed Wheat Protein (COGNIS) Texapon® NSO 43.0 Dehyton® K ²⁹ 10.0 Plantacare® 1200 UP ³⁰ 4.0 Lamesoft® PO 65 2.5 Euperlan®PK 3000 ³¹ 1.6 Arquad®316 ³² 0.8 Polymer JR® 400 0.3 Gluadin® WQ 4.0 Lauryldimopnium hydroxypropyl hydrolyzed silk 3.0 Sodium Lauroyl Hydrolyzed Silk 3.0 sericin 10.0 lactic acid 0.5 Hydrolupin® AA ³³ 0.5 malic acid 0.5 Glucamate®DOE 120 ³³ 0.5 sodium chloride 0.2 water ad 100.0 ²⁹ INCI name: Cocamidopropyl Betaine approx. 30% active substance (COGNIS) ³⁰ C12-C16 fatty alcohol glycoside approx. 50% active substance (INCI name: Lauryl Glucoside) (COGNIS) ³¹ Liquid dispersion of pearlescent substances and amphoteric surfactant (approx. 62% active substance; CTFA name: Glycol Distearate (and) Glycerin (and) Laureth-4 (and) Cocoamidopropyl Betaine) (COGNIS) ³² tri-C ₁₆ alkyl methyl ammonium chloride (AKZO) ³³ amino acid mixture obtained by total hydrolysis of lupine protein, (INCI name Lupine Amino Acids) (CRODA) ³⁴ ethoxylated methyl glucoside dioleate (CTFA name: PEG-120 methyl glucose dioleates) (AMERCHOL) Texapon®N 70 ³⁵ 21.0 Plantacare® 1200 UP 8.0 Lamesoft® PO 65 3.0 Gluadin® WQ 1.5 Promois® Silk 1000 15.0 sericin 10.0 Cutina® EGMS ³⁶ 0.6 Honeyquat® 50 2.0 Ajidew® NL 50 2.8 Antil® 141 ³⁷ 1.3 Crolastin® ³⁸ 1.0 sodium chloride 0.2 magnesium hydroxide ad pH 4.5 water ad 100.0 ³⁵ sodium lauryl ether sulfate with 2 mol EO approx. 70% active substance (INCI name: Sodium Laureth Sulfate) (COGNIS) ³⁶ ethylene glycol monostearate (approx. 25-35% monoester, 60-70% diester; INCI name: glycol stearate) (COGNIS) ³⁷ polyoxyethylene propylene glycol dioleate (40% active substance; INCI name: Propylene Glycol (and) PEG-55 Propylene Glycol Oleate) (GOLDSCHMIDT) ³⁸ Elastin hydrolyzate (INCI name: Hydrolyzed Elastin) (CRODA) Texapon® K 14 S ³⁹ 50.0 Dehyton® K 10.0 Plantacare® 818 UP ⁴⁰ 4.5 Lamesoft® PO 65 2.0 Potassium Cocoyl Hydrolyzed Silk 5.0 Palmitoyl pentapeptide-2 2.5 Polymer P1, according to DE 39 29 973 0.6 Cutina® AGS ⁴¹ 2.0 D-panthenol 0.5 glucose 1.0 Hydrosesame® AA ⁴² 0.8 salicylic acid 0.4 sodium chloride 0.5 Gluadin® WQ 2.0 water ad 100.0 ³⁹ sodium lauryl myristyl ether sulfate approx. 28% active substance (INCI name: Sodium Myreth Sulfate) (COGNIS) ⁴⁰ C8-C16 fatty alcohol glycoside approx. 50% active substance (INCI name: Coco Glucoside) (COGNIS) ⁴¹ ethylene glycol stearate (approx. 5-15% monoester, 85-95% diester; INCI name: Glycol Distearate) (COGNIS) ⁴² INCI name: Water (and) Sesame Amino Acids (CRODA) Celquat® L 200 ⁴³ 0.6 Luviskol® K30 ⁴⁴ 0.2 D-panthenol 0.5 Polymer P1, according to DE 39 29 973 0.6 Dehyquart® A-CA 1.0 Lamesoft® PO 65 0.5 Hydrosoy® 2000 ⁴⁵ 1.0 aspartic acid 0.3 Acetyl Hexapeptide-3 2.0 Promois® Silk 1000 5.0 Gluadin® W 40 1.0 Natrosol® 250 HR ⁴⁶ 1.1 Gluadin® WQ 2.0 water ad 100.0 ⁴³ quaternized cellulose derivative (95% active substance; CTFA name: Polyquaternium-4) (DELFT NATIONAL) ⁴⁴ polyvinylpyrrolidone (95% active substance; CTFA name: PVP) (BASF) ⁴⁵ soy protein hydrolyzate (INCI name: Hydrolyzed Soy Protein) (CRODA) ⁴⁶ hydroxyethyl cellulose (AQUALON) C _12-18 fatty alcohol 1.20 Lanette® O ⁴⁷ 4.00 Eumulgin® B2 0.80 Cutina® KD 16 ⁴⁸ 2.00 Lamesoft® PO 65 4.00 sodium 0.50 L (+) - ascorbic acid 0.50 ammonium sulfate 0.50 1,2-propylene glycol 1.20 Polymer JR®400 0.30 p-aminophenol 0.35 p-toluenediamine 0.85 2-methyl 0.14 6-methyl-m-aminophenol 0.42 Cetiol® OE ⁴⁹ 0.50 Honeyquat® 50 1.00 Ajidew®NL 50 1.20 Gluadin® WQ 1.00 Crosilk Liquid® ⁵⁰ 0.50 Promois® Silk 1000 0.50 sericin 0.30 ammonia 1.50 water ad 100.00 ⁴⁷ Cetylstearyl alcohol (INCI name: Cetearyl Alcohol) (COGNIS) ⁴⁸ Self-emulsifying mixture of mono- / diglycerides of higher saturated fatty acids with potassium stearate (INCI name: Glyceryl Stearate SE) (COGNIS) ⁴⁹ di-n-octyl ether (INCI name: dicaprylyl ether) (COGNIS) ⁵⁰ mixture of amino acids obtained by total hydrolysis of silk protein (INCI name: Silk Amino Acids) (CRODA) Texapon® NSO 2.1 Hydrogen peroxide (50%) 12.0 Turpinal® SL ⁵¹ 1.7 Latekoll® D ⁵² 12.0 Lamesoft® PO 65 2.0 Gluadin® WQ 0.3 Salcare® SC 96 1.0 aspartic acid 0.1 sericin 0.2 Promois® Silk 1000 0.4 Crolastin® 0.8 water ad 100.0 ⁵¹ 1-hydroxyethane-1,1-diphosphonic acid (60% active substance; INCI name: Etidronic Acid) (COGNIS) ⁵² acrylic ester-methacrylic acid copolymer (25% active substance) (BASF) Texapon® N 70 14.00 Dehyton® K 10.00 Akypo® RLM 45 NV ⁵³ 14.70 Plantacare® 1200 UP 4.00 Lamesoft® PO 65 3.00 Polymer P1, according to DE 39 29 973 0.30 Cremophor® RH 40 ⁵⁴ 0.80 Poly-L-serine 0.30 Hydrolyzed sericin 0.30 Hydroxypropyltrimonium Hydrolyzed Silk 3.00 benzoic acid 0.30 Poly-L-proline 0.30 Dye CI 12 719 0.02 Dye CI 12 251 0.02 Dye CI 12 250 0.04 Dye CI 56 059 0.03 preservation 0.25 perfume oil qs Eutanol® G ⁵⁵ 0.30 Gluadin® WQ 1.00 Honeyquat® 50 1.00 Salcare® SC 96 0.50 water ad 100.00 ⁵³ lauryl alcohol +4.5 ethylene oxide-acetic acid sodium salt (20.4% active substance) (CHEM-Y) ⁵⁴ castor oil, hydrogenated +45 ethylene oxide (INCI name: PEG-40 Hydrogenated Castor Oil) (BASF) ⁵⁵ 2-octyldodecanol (Guerbet alcohol) (INCI name: Octyldodecanol) (COGNIS) Well cream Plantacare® 810 UP ⁵⁶ 5.0 thioglycolic 8.0 Turpinal® SL 0.5 Ammonia (25%) 7.3 ammonium carbonate 3.0 Cetyl / stearyl alcohol 5.0 Lamesoft® PO 65 0.5 Guerbet alcohol 4.0 Salcare® SC 96 3.0 Gluadin® WQ 2.0 Hydrolyzed sericin 0.3 Hydroxypropyltrimonium Hydrolyzed Silk 1.0 glutaric 0.2 Hydrotriticum® 2000 ⁵⁷ 0.5 perfume oil qs water ad 100.0 ⁵⁶ C ₈ -C ₁₀ alkyl glucoside with degree of oligomerization 1.6 (approx. 60% active substance) (COGNIS) ⁵⁷ Wheat protein hydrolyzate (INCI name: Hydrolyzed Wheat Protein) (CRODA) Plantacare® 810 UP 5.0 hardened castor oil 2.0 Lamesoft® PO 65 1.0 potassium bromate 3.5 nitrilotriacetic 0.3 citric acid 0.2 Merquat® 550 ⁵⁸ 0.5 Hydagen® HCMF ⁵⁹ 0.5 tartaric acid 0.5 Gluadin® WQ 0.5 Cocodimonium Hydroxypropyl Silk Amino Acids 0.3 Hydrolyzed sericin 0.1 D / L-methionine-S-Methylsulfoniumchlorid 0.3 perfume oil qs water ad 100.0 ⁵⁸ dimethyldiallylammonium chloride-acrylamide copolymer (8% active substance; INCI name: Polyquarternium 7) (MOBIL OIL) ⁵⁹ Chitosan powder (INCI name: Chitosan) (COGNIS)

Claims (8)

1. Cosmetic preparations containing an active ingredient complex A consisting of an active ingredient A1, which is selected from sericin and / or sericin hydrolyzates and / or derivatives and / or mixtures thereof, and an active ingredient A2 which is selected from fibroin and / or its hydrolyzates and / or its derivatives and / or mixtures thereof. 2. Cosmetic preparation according to claim 1, characterized in that at least one of the two active substances A1 or A2 is largely in its native form. 3. Cosmetic preparations according to one of claims 1 or 2, characterized characterized in that a compound selected from the group of surfactants (E) and / or the group of polymers (G) is contained. 4. Cosmetic preparations according to claim 3, characterized in that the surfactant is selected from the group of cationic surfactants. 5. Cosmetic preparations according to claim 3, characterized in that the Polymer is selected from the group of cationic and / or amphoteric Polymers. 6. Use of a preparation according to one of claims 1 to 5 for cleaning and / or skin and hair care. 7. Use of a preparation according to one of claims 1 to 5 for restructuring of keratin fibers, especially human hair. 8. A method of treating skin or hair, in which a preparation according to a of claims 1 to 5 is applied to the fibers, the preparation according to after an exposure time of 1 to 45 minutes.