WO2007068339A1

WO2007068339A1 - Cosmetic agents having increased fragrance intensity and persistence

Info

Publication number: WO2007068339A1
Application number: PCT/EP2006/011342
Authority: WO
Inventors: Bernhard Banowski; Thomas Gerke; Erik Schulze Zur Wiesche; Werner Faber; Wolfgang Lahn; Andreas Bauer
Original assignee: Henkel Ag & Co. Kgaa
Priority date: 2005-12-13
Filing date: 2006-11-27
Publication date: 2007-06-21
Also published as: EP1962792A1; DE102005059935A1; RU2438649C2; RU2438649C9; RU2008128117A

Abstract

The present invention relates to cosmetic compositions for treating the skin and/or the scalp and/or the hair and/or for oral and dental hygiene, in particular deodorant or antitranspirant compositions, which contain certain esters of silicic acid.

Description

"Cosmetic agents with increased fragrance intensity and persistence"

The present invention relates to cosmetic compositions for the treatment of the skin and / or scalp and / or hair and / or oral and dental hygiene, in particular deodorant or antiperspirant compositions containing certain silicic acid esters.

The controlled release of ingredients in a variety of preparations, often referred to as "controlled release", is the subject of numerous publications and patent applications. Of great importance in the field of cosmetics is the release of fragrances, since both the product and the substrates treated with the product, such as the skin and / or hair, are to be intensively and long-lasting scented. In addition to the methods of applying perfumes to substrates and coating the perfumed vehicles, or encapsulating perfumes or incorporating into compounds (eg, cyclodextrin-perfume complexes), there is the possibility of chemically binding the perfumes to carrier media, thereby slowly cleaving the chemical bond and the perfume is released. This principle has been realized, for example, in the esterification of perfume alcohols, with a broad state of the art on this group of substances.

There are some proposals in the prior art to bind fragrant alcohols to nonvolatile siloxanes, from which they are slowly released by hydrolysis. Although there is a broad state-of-the-art for siloxane esters of perfume alcohols, there are problems with the use of said compounds in cosmetics. Thus, many of the known compounds in aqueous-based or water-containing cosmetics can not be used, since they already hydrolyze in the product and the delayed release due to this later no longer occurs.

Monomeric orthosilicic esters of perfume alcohols are described, for example, in US 3,215,719 (Dan River Mills). This document also mentions the delayed release of fragrant alcohols from mixed esters such as bis (eugenoxy) diethoxysilane or bis (cinnamoyloxy) diethoxysilane, where the central Si need not necessarily be bound to oxygen only. Oligomeric siloxane esters are not described in this document.

Liquid or pasty soap compositions containing "fragrance-conferring" silicon compounds are described in GB 2041964 (Dow Corning). Also in this document, oligomeric Si compounds having more than one perfume alcohol ester group are not described. Aroma-giving, non-volatile siloxanes of the general formula M _a M ^_'a D _b ^D' _b T _c T ^_'c Q _d where M and ^M' = R ¹ R ² R ³ SIOI _Z2, D and D ^'= R ⁴ R ⁵ SiO _2Z2 , T and T ^' = R ⁶ Si0 _3/2 and Q = SiO _4/2 , wherein R ¹ to R ^{6 are} independently selected from C _1-40 alkyl or alkoxy and aryl or aryl oxy radicals and the indices a, a ^'are positive and one or more of the indices b, b ^' , c, c ^' and d are positive or 0 are described in GB2319527 (General Electric). Formally fall also oligomeric Si compounds with four perfume alcohol ester groups under the general formula, but only compounds are explicitly disclosed in this document, in which at least two carbon atoms are bonded directly to a Si atom. The use of fragrance-giving siloxanes in cosmetics is also not mentioned in this document.

It was therefore still the task to provide siloxane esters of perfume alcohols, which are on the one hand so hydrolyzed that they can be incorporated into aqueous or water-containing cosmetics, without already be subject in the product excessive hydrolysis, but on the other hand are not too resistant to hydrolysis to prevent the consumer from experiencing any fragrance at all during the normal period of use. The substances to be produced should give both the product and the substrates treated with the product (eg skin or hair) a pleasant and long-lasting fragrance. The hydrolysis behavior of the siloxane esters of perfume alcohols is difficult or impossible to predict based on the chemical structure of the perfume alcohols. A further object of the present invention was therefore to enrich the state of the art with a broader range of perfume alcohol siloxane esters having a hydrolysis behavior which is suitable for use.

It has now been found that silicic acid esters containing at least one alcohol radical of a perfume alcohol selected from the group formed by the hexene-1-ols, cinnamyl alcohol, 3-phenylpropan-1-ol (hydrocinnamyl alcohol), 3R (-) - Linalool, 3S (+) - linalool, (-) - menthol, (+) - neo-menthol, α-terpineol, ß-terpineol, γ-terpineol, δ-terpineol, (-) - bomeol, (+) - isobomeol , (-) - Lavandulol, (Z) -4-hepten-2-ol, eugenol, 2-methoxy-4 - ((Z) -1-propenyl) phenol ((Z) -isoeugenol), 2-meth - oxy-4 - ((e) -1-propenyl) phenol ((e) -Isoeugenol), 4-hydroxy-2,5-dimethyl-3 (2H) -furanone (Fura- neol ^®), 4-hydroxy 3-methoxybenzaldehyde (vanillin), 4- (4-hydroxyphenyl) -2-butanone (raspberry ketone), (Z, Z) -3,6-nonadien-1-ol, 3,7-dimethyl-7-octene 1-ol (rhodinol) and (Z) -3-octen-1-ol, which meet the application-technically necessary requirements. In the investigations of these substances it was further surprisingly found that in combination with customary fragrances they also give the fragrances a longer-lasting effect which is not esterified with the oligosilicic acids. Regardless of the chemical composition of the fragrances, the compounds according to the invention can therefore be used in perfume mixtures in order to give the entire perfume composition a prolonged release of fragrance. According to the invention, hexene-1-ols include (Z) -2-hexene-1-ol, (E) -2-hexene-1-ol, (Z) -3-hexene-1-ol (foliar alcohol), (E) 3-hexen-1-ol, (Z) -4-hexen-1-ol, (E) -4-hexen-1-ol and 5-hexen-1-ol understood. Preferred hexene-1-ols according to the invention are selected from (Z) -3-hexen-1-ol (foliar alcohol), (E) -2-hexen-1-ol, (Z) -2-hexen-1-ol and ( E) -3-hexen-1-ol and mixtures thereof, particularly preferred hexene-1-ols are selected from (Z) -3-hexen-1-ol (leaf alcohol) and (E) -2-hexen-1-ol and mixtures thereof.

The invention relates to cosmetic compositions for the treatment of the skin and / or scalp and / or hair and / or oral and dental hygiene, which in a suitable cosmetic carrier silica esters of the formulas I and / or II and / or III and / or IV

in each case at least one radical R is derived from at least one alcohol selected from the group consisting of (Z) -2-hexen-1-ol, (E) -2-hexen-1-ol, ( Z) -3-hexen-1-ol (leaf alcohol), (E) -3-hexen-1-ol, (Z) -4-hexen-1-ol, (E) -4-hexen-1-ol, 5-hexen-1-ol, cinnamyl alcohol, 3-phenylpropan-1-ol (hydrocinnamyl alcohol), 3R (-) - linalool, 3S (+) - linalool, (-) - menthol, (+) - neomenthol, α-terpineol , β-terpineol, γ-terpineol, δ-terpineol, (-) - borneol, (+) - isoborneol, (-) - lavandulol, (Z) -4-hepten-2-ol, eugenol, 2-methoxy-4 - ((Z) -1-propenyl) phenol ((Z) isoeugenol), 2-methoxy-4 - ((E) -1-propenyl) phenol ((E) -isoeugenol), 4-hydroxy-2,5 dimethyl-3 (2H) -furanone (furaneol ^®), 4-hydroxy-3-methoxy-benzaldehyde (vanillin), 4- (4-hydroxyphenyl) -2-butanone (raspberry ketone), (Z, Z) -3, 6-nonadien-1-ol, 3,7-dimethyl-7-octene-1-ol (rhodinol) and (Z) -3-octene-1-ol, and the other R's are each independently selected from the group representing a hydrogen atom, the straight-chain or v branched, saturated or unsaturated, substituted or unsubstituted C ^ hydrocarbon radicals and the 2-phenoxyethyl radical, and m values from the range 1 to 20 and n values ranging from 2 to 100, and mixtures thereof.

The preparation of the compounds mentioned in claim 1 is possible by simple transesterification of Oligokieselsäureestern lower Ci-C ₄ -AIkOhOIe such as methanol, ethanol, n-propanol, isopropanol, n-butanol, iso-butanol and tert-butanol with a) at least an alcohol selected from the group formed by the hexene-1-ols, cinnamyl alcohol, 3-phenylpropan-1-ol (hydrocinnamyl alcohol), 3R (-) - linalool, 3S (+) - linalool, (-) - Menthol, (+) - neomenthol, α-terpineol, β-terpineol, γ-terpineol, δ-terpineol, (-) - borneol, (+) - isoborneol, (-) - lavandulol, (Z) -4-heptene 2-ol, eugenol, 2-methoxy-4 - ((Z) -1-propenyl) phenol ((Z) isoeugenol), 2-methoxy-4 - ((E) -1-propenyl) phenol (( e) -Isoeugenol), 4-hydroxy-2,5-dimethyl-3 (2H) -furanone (furaneol ^®), 4-hydroxy-3-methoxy- benzaldehyde (vanillin), 4- (4-hydroxyphenyl) -2- butanone (raspberry ketone), (Z, Z) -3,6-nonadien-1-ol, 3,7-dimethyl-7-octen-1-ol (rhodinol) and (Z) -3-octen-1-ol, b) mixtures of at least two of the abovementioned alcohols or c) mixtures of at least one alcohol selected from the aforementioned group with other alcohols. As "other alcohols" which may be present in the transesterification mixture, there are, in particular, perfume alcohols which are different from the group formed by the hexene-1-ols, cinnamyl alcohol, 3-phenylpropan-1-ol (hydrocinnamyl alcohol), 3R (-) - linalool, 3S (+) - linalool, (-) - menthol, (+) - neomenthol, α-terpineol, ß-terpineol, γ-terpineol, δ-terpineol, (-) - borneol, (+ ) -soborneol, (-) - lavandulol, (Z) -4-hepten-2-ol, eugenol, 2-methoxy-4 - ((Z) -1-propenyl) phenol ((Z) -isoeugenol), 2- methoxy-4 - ((e) -1-propenyl) phe nol ((e) -Isoeugenol), 4-hydroxy-2,5-dimethyl-3 (2H) -furanone (furaneol ^®), 4-hydroxy-3 -methoxybenzaldehyde (vanillin), 4- (4-hydroxyphenyl) -2-butanone (raspberry ketone), (Z, Z) -3,6-nonadien-1-ol, 3,7-dimethyl-7-octene-1 -ol (rhodinol) and (Z) -3-octen-1-ol, or biocide alcohols, wherein both individual perfume or biocide alcohols and perfume or Bizidalkoholgemische can be used Depending on the reaction time and conditions, the lower alcohols and an alcohol selected from the group formed by the hexene-1-ols, cinnamyl alcohol, 3-phenylpropan-1-ol (hydrocinnamyl alcohol), 3R (-) - linalool, 3S (+) - linalool, (- ) - Menthol, (+) - neomenthol, α-terpineol, β-terpineol, γ-terpineol, δ-terpineol, (-) - borneol, (+) - isobomoleol, (-) - lavandulol, (Z) -4-heptene 2-ol, eugenol, 2-methoxy-4 - ((Z) -1-propenyl) phenol ((Z) -isoeugenol), 2-methoxy-4 - ((E) -1-propenyl) -phenol ((E) -Isoeugenol), 4-hydroxy-2,5-dimethyl-3 (2H) - furanone (furaneol ^®), 4-hydroxy-3-methoxy-benzaldehyde (vanillin), 4- (4-hydroxyphenyl) -2-butanone non (raspberry ketone), (Z, Z) -3,6-nonadien-1-ol, 3,7-dimethyl-7-octen-1-ol (rhodinol) and (Z) -3-octen-1-ol, and optionally the fragrance or biocide alcohols other than this group, wherein the alcohols are more easily exchanged along Si-O-Si chains or rings than the terminal alcohols. Such transesterifications can be carried out, for example, as described in the publication H. Steinmann, G. Tschernko, H. Hamann, Z. Chem. 3, 1977, pp. 89-92. The content of this publication is expressly considered to be a disclosure of this application for the preparation of silicic acid esters. Usually, the starting materials used are the commercially available silicic acid esters. In particular, the ethanol ester is mentioned here, which can be obtained, for example, from Wacker, Burghausen. The transesterification can be controlled exclusively by increasing the temperature and distilling off the volatile by-products. However, it is preferred if catalysts are used for the transesterification. These are usually Lewis acids, preferably aluminum tetraisopropylate, titanium tetraisopropoxide, silicon tetrachloride or basic catalysts or else preparations such as, for example, aluminum oxide with potassium fluoride. The oligomeric silicic acid esters thus formed then have at least partially perfume alcohol residues and / or biocide alcohol residues or a combination of both. However, the resulting esters usually also contain radicals of lower C 1 -C ₄ -alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol and tert-butanol. As far as small amounts of water or other H-acidic compounds are present in the production of silicic acid esters, an exchange of alcohol residues against OH groups also takes place. Accordingly, the silicic acid ester mixtures according to the invention usually also contain, as radical R, some hydrogen.

Oligokieselsäureester lower C _r C ₄ alcohols such as methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol and tert-butanol are commercially available, with usually methanol, ethanol, n-propanol, iso-propanol , n-butanol, isobutanol and tert-butanol were used for the esterification. The preparation of not completely transesterified oligosilicic ester leads to silicic acid ester mixtures in which a part of the radicals R is selected from the group methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl and tert-butyl. Such compounds are preferred in the context of the present invention.

For the purposes of the present invention, the term "perfume alcohols" is understood as meaning fragrances which have free hydroxyl groups which are esterifiable, regardless of how the molecule is developed further. Salicylic acid esters can also be used as perfume alcohols. Under a perfume according to the invention those fragrances, Understood essences and flavors that cause a pleasant sensation of smell in humans and therefore find a variety of uses for the perfuming of technical and sanitary items, soaps, cosmetics, toiletries and the like. According to the invention, the term "fragrances" is understood to mean uniform, defined chemical compounds having an odor and / or taste, ie all substances or mixtures thereof that are perceived by humans and animals as odor meet certain molecular requirements: low molecular weight (max 300) with correspondingly high vapor pressure, surface activity, minimal water and high lipid solubility and weak polarity A strongly hydrophobic and a weakly polar moiety are sufficient to trigger the sensory activity.Also plays the stereochemistry, ie the spatial configuration of the molecules, for the properties of a substance as a fragrance an important role.From the large group of perfume alcohols may be mentioned preferred representatives, in particular (Z) -2-hexen-1-ol, (E) -2-hexene 1-ol, (Z) -3-hexen-1-ol (leaf alcohol), (E) -3-hexen-1-ol, (Z) -4-hexen-1-ol, (E) -4-hex en-1-ol, 5-hexen-1-ol, cinnamyl alcohol, 3-phenylpropan-1-ol (hydrocinnamyl alcohol), 3R (-) - linalool, 3S (+) - linalool, (-) - menthol, (+) -Nomentothol, α-terpineol, β-terpineol, γ-terpineol, δ-terpineol, (-) - borneol, (+) - isoborneol, (-) - lavandulol, (Z) -4-hepten-2-ol, eugenol , 2-methoxy-4 - ((Z) -1-propenyl) phenol ((Z) isoeugenol), 2-methoxy-4 - ((E) -1-propenyl) -phenol ((E) -isoeugenol), 4-hydroxy-2,5-dimethyl-3 (2H) -furanone (furaneol ^®), 4-hydroxy-3-methoxy-benzaldehyde (vanillin), 4- (4-hydroxyphenyl) -2-butanone (raspberry ketone), ( Z, Z) -3,6-nonadien-1-ol, 3,7-dimethyl-7-octen-1-ol (rhodinol), (Z) -3-octen-1-ol, 10-undecene-1 ol, 2,6-dimethylheptan-2-ol, 2-methylbutanol, 2-methylpentanol, 2-phenoxyethanol, 2-phenyl-propan-1-ol, 2-tert-butycyclohexanol, 3,5,5-trimethylcyclohexanol, 3 Hexanol, 3-methyl-5-phenylpentanol, 3-octanol, 4-heptenol, 4-isopropylcyclohexanol, 4-tert-butylcyclohexanol, 6,8-dimethyl-2-nonanol, 6-nonen-1-ol, 9-decene-1-ol, α-methylbenzyl alcohol, amyl salicylate, benzyl alcohol, Ben cylsalicylate, butyl salicylate, citronellol, cyclohexyl salicylate, decanol, dihydromyrcenol, dimethylbenzylcarbinol, dimethylheptanol, dimethyloctanol, ethyl salicylate, ethylvanillin, farnesol, geraniol, heptanol, hexyl salicylate, isoborneol, isopulegol, menthol, myrtenol, n-hexanol, nerol, nona nol, octanol, para-menthane-7-ol, phenylethyl alcohol, phenol, phenyl salicylate, tetrahydrogeraniol, tetrahydrolinalool, thymol, trans-2-cis-6-nonadienol, trans-2-nonen-1-ol, trans-2-octenol and undecanol.

For the purposes of this invention, biocidal alcohols are understood as meaning all compounds which have at least one alcoholic group and at least inhibit germ growth. For example, alcohols which also function as perfume alcohols may be mentioned here. In particular, these are citronellol, eugenol, farnesol, thymol and geraniol. Further biocide alcohols are phenoxyethanol, 1,2-propylene glycol, glycerol, 2-methyl-1,3-propanediol, butylene glycols such as 1,2-butylene glycol, 1,3-butylene glycol and 1,4-butylene glycol, pentylene glycols such as 1,2-pentanediol and 1, 5-pentanediol, hexanediols such as 1, 6-hexanediol, hexanetriols such as 1, 2,6-hexanetriol, 1, 2-octanediol, 1, 8-octanediol, citric acid and its esters, lactic acid and its esters, salicylic acid and their esters, 2-benzyl-4-chlorophenol and 2,2'-methylenebis (6-bromo-4-chlorophenol). For the purposes of this invention, the lower C 1 -C ₄ -alcohols which have already been mentioned above as customary radicals of the silicic acid esters are not considered to be biocidal alcohols. They are explicitly methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl and tert-butyl alcohol, which are not considered to be biocidal alcohols according to the invention. On the other hand, classical biocides with alcohol functions are expressly regarded as biocide alcohols according to the invention, even if their effect is attributable to other functional groups. For example, various bromphenols and biphenylol, triclosan, chlorothymol, α- (2-ethylhexyl) glycerol ether, 2-methyl-4-phenylbutan-2-ol and quaternary ammonium compounds having at least one long alkyl radical and at least one alkyl radical which is a hydroxy Group bears, to name.

When producing non-fully transesterified oligosilicic acid esters, at least one of R's, other than methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl and tert-butyl, is selected from an alcohol selected is from the group formed by (Z) -2-hexene-1-ol. (E) -2-hexen-1-ol, (Z) -3-hexen-1-ol (leaf alcohol), (E) -3-hexen-1-ol, (Z) -4-hexen-1-ol , (E) -4-hexen-1-ol, 5-hexen-1-ol, cinnamyl alcohol, 3-phenylpropan-1-ol (hydrocinnamyl alcohol), 3R (-) - linalool, 3S (+) - linalool, (- ) -Menthol, (+) - neomenthol, α-terpineol, β-terpineol, γ-terpineol, δ-terpineol, (-) - borneol, (+) - isoborneol, (-) - lavandulol, (Z) -4- Hepten-2-ol, eugenol, 2-methoxy-4 - ((Z) -1-propenyl) phenol ((Z) isoeugenol), 2-methoxy-4 - ((E) -1-propenyl) phenol ((e) -Isoeugenol), 4-hydroxy-2,5-dimethyl-3 (2H) -furanone (furaneol ^®), 4-hydroxy-3-methoxy-benzaldehyde (vanillin), 4- (4-hydroxy phenyl ) -2-butanone (raspberry ketone), (Z, Z) -3,6-nonadien-1-ol, 3,7-dimethyl-7-octene-1-ol (rhodinol) and (Z) -3-octene 1-ol, and optionally additionally of at least one further perfume alcohol and / or of at least one further biocidal alcohol.

Particularly preferred cosmetic compositions according to the invention are characterized in that at least 10 mol%, preferably at least 20 mol% and particularly preferably more than 40 mol% of the radicals R originate from at least one alcohol which is selected from the group which is formed of (Z) -2-hexen-1-ol, (E) -2-hexen-1-ol, (Z) -3-hexen-1-ol (leaf alcohol), (E) -3-hexene-1 ol, (Z) -4-hexen-1-ol, (E) -4-hexen-1-ol, 5-hexen-1-ol, cinnamyl alcohol, 3-phenylpropan-1-ol (hydrocinnamyl alcohol), 3R (- ) -Linalool, 3S (+) - linalool, (-) - menthol, (+) - neemethol, α-terpineol, ß-terpineol, γ-terpineol, δ-terpineol, (-) - borneol, (+) -lsobomeol, (-) - lavandulol, (Z) -4-hepten-2-ol, eugenol, 2-methoxy-4 - ((Z) -1-propenyl) phenol ((Z) -isoeugenol), 2-methoxy -4- ((e) -I propenyl) phenol ((e) -Isoeugenol), 4-hydroxy-2,5-dimethyl-3 (2H) -furanone (furaneol ^®), 4-hydroxy-3-methoxy- benzaldehyde (vanillin), 4- (4-hydroxyphenyl) -2-butanone (raspberry ketone), (Z, Z) -3,6-nonadien-1-ol, 3,7-dimethyl-7-octene-1-ol ( rh odinol) and (Z) -3-octen-1-ol.

Extremely preferred cosmetic compositions according to the invention are characterized in that at least 10 mol%, preferably at least 20 mol% and in particular preferably more than 40 mol% of the radicals R originate from at least one alcohol selected from (Z) -3-hexen-1-ol (foliar alcohol).

Since the starting compounds for the preparation of the compounds of the invention for economic reasons are preferably not pure substances, but technical mixtures of Oligokieselsäureestem lower CrC ₄ alcohols with different degrees of oligomerization, there is a distribution of degrees of oligomerization in the esters in the inventive agents again, the starting material may be matched or modified by the reaction conditions.

Particularly preferred cosmetic compositions according to the invention are characterized in that n values from the range of 2 to 50, preferably from the range of 2 to 20 and in particular from the range of 3 to 10 with particular preference to the values 4, 5, 6, 7 and 8, and m takes values from the range of 2 to 10, with particular preference to the values 2 and 3.

The cosmetic compositions according to the invention contain the silicic acid ester (s) according to one of claims 1 to 3 preferably in total amounts of from 0.000001 to 10% by weight, preferably from 0.001 to 5% by weight, particularly preferably from 0.01 to 0 , 5 wt .-% and in particular from 0.05 to 0.1 wt .-%, each based on the weight of the cosmetic composition.

Further preferred cosmetic compositions according to the invention are characterized in that they contain the silicic acid ester (s) according to any one of claims 1 to 3 in admixture with silicic acid esters of the formulas I and / or II and / or III and / or IV, in each case at least one radical R derived from perfume alcohols and / or biocide alcohols derived from (Z) -2-hexen-1-ol, (E) -2-hexen-1-ol, (Z) -3-hexen-1-ol (folic acid) , (E) -3-hexen-1-ol, (Z) -4-hexen-1-ol, (E) -4-hexen-1-ol, 5-hexen-1-ol, cinnamyl alcohol, 3-phenylpropane -1-ol (hydrocinnamyl alcohol), 3R (-) - linalool, 3S (+) - linalool, (-) - menthol, (+) - neomenthol, α-terpineol, ß-terpineol, γ-terpineol, δ-terpineol, (-) - borneol, (+) - isoborneol, (-) - lavandulol, (Z) -4-hepten-2-ol, eugenol, 2-methoxy-4 - ((Z) -1-propenyl) phenol (( Z) -isoeugenol), 2-methoxy-4 - ((E) -1-propenyl) phenol ((E) -Isoeugenol), 4-hydroxy-2,5-dimethyl-3 (2H) -furanone (furaneol ^® ), 4-hydroxy-3-methoxybenzaldehyde (vanillin), 4- (4-hydroxyphenyl) -2-butanone (Raspberry ketone), (Z, Z) -3,6-nonadien-1-ol, 3,7-dimethyl-7-octene-1-ol (rhodinol) and (Z) -3-octen-1-ol are different , in total amounts of 0.0001 to 10 wt .-%, preferably from 0.001 to 5 wt .-%, particularly preferably from 0.05 to 1, 0 wt .-% and in particular from 0.1, 0.2, 0 , 3, 0.4, 0.5, 0.6, 0.7 or 0.8% by weight, each based on the weight of the cosmetic composition.

In addition to the silicic acid ester (s), the cosmetic compositions according to the invention may contain at least one further fragrance. As perfume oils or perfumes, according to the invention, individual fragrance compounds, for. As the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons are used. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate (DMBCA), phenylethyl acetate, benzyl acetate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate, benzylsalicylate, cyclohexylsalicylate, floramate, melusate and jasmecyclate , The ethers include, for example, benzyl ethyl ether and ambroxane, to the aldehydes, for example, the linear alkanals having 8 - 18 carbon atoms, citral, citronellal, citronellyloxy-acetaldehyde, cyclamen aldehyde, lilial and bourgeonal, to the ketones eg the Jonone, alpha-lsomethyl to the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes such as limonene and pinene. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance.

Such perfume oils may also contain natural fragrance mixtures as are available from vegetable sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are Muskateller sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, lime blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and laudanum oil and orange blossom oil, neroliol, orange peel oil and sandalwood oil.

By dividing the total perfume content in perfume, which is esterified with silicic acid ester, and perfume, which is present without esterification, a variety of product characteristics can be realized. Thus, for example, it is conceivable and possible to divide the total perfume content of the agents according to the invention into two portions x and y, wherein the proportion x of adherent, i. less volatile and the proportion y consists of more volatile perfume oils.

The general description of the perfumes that can be used (see above) generally represents the different substance classes of fragrances. To be perceptible, a perfume must be volatile, wherein besides the nature of the functional groups and the structure of the chemical compound also the molecular weight plays an important role , For example, most odorants have molecular weights up to about 200 daltons, while molecular weights of 300 daltons and above are more of an exception. Due to the different volatility of fragrances, the smell of a perfume or fragrance composed of several fragrances changes during evaporation, whereby the odor impressions in "top note", "middle note or body" As the smell perception is based to a large extent on the odor intensity, the top note of a perfume or fragrance consists not only of volatile compounds, while the base note for the most part from less volatile , ie adherent fragrances stands. For example, in the composition of perfumes, more volatile fragrances can be bound to certain fixatives, preventing them from evaporating too quickly. In the subsequent classification of the fragrances in "more volatile" or "adherent" fragrances so nothing about the olfactory impression and whether the corresponding fragrance is perceived as a head or middle note, nothing said.

Adhesion-resistant fragrances which can be used in the context of the present invention are, for example, the essential oils such as angelica root oil, aniseed oil, arnica blossom oil, basil oil, bay oil, bergamotte oil, Champacablütenöl, Edeltannenöl, Edeltannenzapfen oil, Elemiöl, eucalyptus oil, fennel oil, Fichtennadelöl, galbanum oil, geranium oil, Ginger grass oil, Guajac wood oil, Gurjunbalsam oil, Helichrysum oil, Ho oil, ginger oil, iris oil, cajeput oil, calamus oil, chamomile oil, camphor oil, kananga oil, cardamom oil, cassia oil, pine needle oil, Kopaϊvabalsamöl, coriander oil, spearmint oil, caraway oil, cumin oil, lavender oil, lemongrass oil, lime oil, Tangerine oil, Melissa oil, Musk grain oil, Myrrh oil, Clove oil, Neroli oil, Niaouli oil, Olibanum oil, Orange oil, Origanum oil, Palma pink oil, Patchouli oil, Peru balsam oil, Petitgrain oil, Pepper oil, Peppermint oil, Pimento oil, Pine oil, Rose oil, Rosemary oil, Sandalwood oil, Celery oil, Spiked oil, star aniseed oil, turpentine oil, thuja oil, thymia nöl, verbena oil, vetiver oil, juniper berry oil, wormwood oil, wintergreen oil, ylang-ylang oil, hyssop oil, cinnamon oil, cinnamon oil, lemon oil, lemon oil and cypress oil.

But also the higher-boiling or solid fragrances of natural or synthetic origin can be used in the context of the present invention as adherent fragrances or fragrance mixtures, ie fragrances. These compounds include the following compounds and mixtures thereof: ambrettolide, α-amylcinnamaldehyde, anethole, anisaldehyde, anisalcohol, anisole, methyl anthranilate, acetophenone, benzylacetone, benzaldehyde, ethyl benzoate, benzophenone, benzyl alcohol, benzyl acetate, benzyl benzoate, benzyl formate, benzyl valerate, borneol , Bornyl acetate, α-bromostyrene, n-decyl aldehyde, n-dodecyl aldehyde, eugenol, eugenol methyl ether, eucalyptol, farnesol, fenchone, fenchyl acetate, geranyl acetate, geranyl formate, heliotropin, heptincarboxylic acid methyl ester, heptaldehyde, hydroquinone dimethyl ether, hydroxycinnamaldehyde, hydroxycinnamyl alcohol, indole , Iron, isoeugenol, isoeugenol methyl ether, isosafrole, jasmon, camphor, Karvakrol, Karvon, p-cresol methyl ether, coumarin, p-methoxyacetophenone, methyl n-amyl ketone, methyl anthranilate, p-methylacetophenone, methylchavikol, p-methylquinoline, methyl β-naphthyl ketone, methyl n-nonyl acetaldehyde, methyl n-nonyl ketone, Mu β-naphthol ethyl ether, β-naphthol methyl ether, nerol, nitrobenzene, n-nonyl aldehyde, nonyl alcohol, n-octyl aldehyde, p-oxyacetophenone, pentadecanolide, β-phenylethyl alcohol, phenylacetaldehyde dimethyacetal, phenylacetic acid, pulegone, safrole, salicylic acid. isoamyl ester, salicylic acid methyl ester, hexyl salicylate, cyclohexyl salicylate, santalol, skatole, terpineol, thymes, thymol, γ-undecalactone, vanillin, veratrum aldehyde, cinnamaldehyde, cinnamyl alcohol, cinnamic acid, ethyl cinnamate, cinnamic acid cinnamate. The more volatile fragrances include in particular the lower-boiling fragrances of natural or synthetic origin, which can be used alone or in mixtures. Examples of more readily volatile fragrances are alkyl isothiocyanates (alkyl mustard oils), butanedione, limonene, linalool, linayl acetate and propionate, menthol, menthone, methyl-n-heptenone, phellandrene, phenylacetaldehyde, terpinyl acetate, citral, citronellal.

Depending on the field of application of the cosmetic agents, these may contain a large number of further ingredients. These are described below. If the term "agent according to the invention" is used below, this always means the cosmetic agent.

The silicic acid esters according to the invention have their positive effects, in particular during the hair treatment. Usually, in personal care, the skin is cleaned more often than the hair, especially because the hair is expensive to dry and to clean after cleaning. From a hair care product, the consumer therefore wishes a particularly long-lasting care effect. Long-lasting perfuming also signals to the user a lasting effect of the entire product.

Particularly preferred cosmetic compositions according to the invention are characterized in that they are a composition for the treatment of keratin fibers, in particular human hair. Shampoos, conditioning agents, conditioners, hair conditioners, hair tonics, hair lotions, hair gels, hair sprays, etc. are particularly suitable as such. Other important representatives of this group are the hair dyes, especially the oxidation hair dyes.

A further subject of the present invention is therefore the use of a cosmetic composition which, in a suitable cosmetic carrier, comprises silicic acid esters of the formulas I and / or II and / or III and / or IV

each at least one radical R is derived from at least one alcohol selected from the group consisting of (Z) -2-hexen-1-ol, (E) -2-hexen-1-ol, (Z) - 3-hexen-1-ol (leaf alcohol), (E) -3-hexen-1-ol, (Z) -4-hexen-1-ol, (E) -4-hexen-1-ol, 5-hexene 1-ol, cinnamyl alcohol, 3-phenyl-propan-1-ol (hydrocinnamyl alcohol), 3R (-) - linalool, 3S (+) - linalool, (-) - menthol, (+) - neomenthol, α-terpineol, β-terpineol, γ-terpineol, δ-terpineol, (-) - borneol, (+) - isoborneol, (-) - lavandulol, [Z) -A-hepten-2-ol, eugenol, 2-methoxy-4- ((Z) -1-propenyl) phenol ((Z) isoeugenol), 2-methoxy-4 - ((E) -1-propenyl) phenol ((E) -isoeugenol), 4-hydroxy-2,5- dimethyl-3 (2H) -furanone (furaneol ^®), 4-hydroxy-3-methoxy-benzaldehyde (vanillin), 4- (4-hydroxyphenyl) -2-butanone (raspberry ketone), (Z, Z) -3,6 - Nonadien-1-ol, 3,7-dimethyl-7-octene-1-ol (rhodinol) and (Z) contains 3-octene-1-ol, and the other radicals R are each independently selected from the group which is a hydrogen atom, the straight-chain or verzwei GTEN, saturated or unsaturated, substituted or unsubstituted Ci _-6 contains hydrocarbon radicals and the 2-phenoxyethyl radical, and m assumes values from the range 1 to 20 and na value of 2 to 100, and mixtures thereof, for the treatment of Keratin fibers, especially human hair.

Hair shampoos (shampoos) as well as body cleansers (shower baths, shower gels, bath bath compositions, liquid soaps, syndets) may contain (more or less strongly) foaming anionic, zwitterionic, ampholytic and nonionic surfactants. Hair rinse agents, softeners and conditioning skin and body cleansers (2-in-1 shower gels) preferably contain cationic surfactants and / or water-soluble polymers with quaternary ammonium groups to reduce the static chargeability and to improve the combability of the hair or to improve the feel of the skin. Hair and skin cleansers essentially differ only in the amount of surfactant. Because of the lower sensitivity of the hair to the skin, shampoos and similar compositions usually contain more surfactants, in particular more cation surfactants, as skin cleansers. Skin cleansing agents preferably contain 0-2% by weight, more preferably 0-1% by weight, of cationic surfactants. In addition, the mild, less degreasing surfactants are preferably used in skin cleansers. Other hair treatment products contain additives which are rather unsuitable for skin treatment products. For example, permanent wave fixatives preferably contain oxidizing agents, such as. As potassium bromate or hydrogen peroxide. Hair dye shampoos contain direct hair colorants or oxidation dye precursors. Hair fixatives and hair dressings as well as other hair styling preparations usually contain film-forming polymers which are soluble in aqueous or aqueous-alcoholic media, optionally together with cationic surfactants or cationic polymers.

The use of surfactants (E) in the compositions according to the invention has proved to be particularly advantageous. In a further preferred embodiment, the compositions according to the invention therefore contain at least one surfactant. The term surfactants is understood to mean surface-active substances which form adsorption layers on the upper and boundary surfaces or which can aggregate in volume phases to give micelle colloids or lyotropic mesophases. A distinction is made between anionic surfactants consisting of a hydrophobic radical 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 radical, have a positively charged hydrophilic group, and nonionic surfactants, which have no charges but strong dipole moments and are highly hydrated in aqueous solution.

Suitable anionic surfactants (E1) in the compositions according to the invention are all anionic surfactants suitable for use on the human body. These are characterized by a water-solubilizing, anionic group, such as. Example, a carboxylate, sulfate, sulfonate or phosphate group, and a lipophilic alkyl group having about 8 to 30 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups may be present in the molecule. Examples of suitable anionic surfactants are, in each case in the form of the sodium, potassium and ammonium as well as the mono-, di- and trialkanolammonium salts having 2 to 4 C atoms in the alkanol group, linear and branched fatty acids having 8 to 30 C atoms (Soap), Ethercarbonsäuren the formula RO- (CH ₂ -CH ₂ O) _x -CH ₂ -COOH ₁ in the R is a linear alkyl group having 8 to 30 carbon atoms and x = O or 1 to 16,

Acylsarcosides having 8 to 24 carbon atoms in the acyl group,

Acyltaurides having 8 to 24 carbon atoms in the acyl group,

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

Sulfosuccinic acid mono- and dialkyl esters (sulfosuccinates) having 8 to 24 carbon atoms in the

Alkyl group and sulfosuccinic acid mono-alkylpolyoxyethyl esters having 8 to 24 C atoms in the alkyl group and 1 to 6 oxyethyl groups, linear alkanesulfonates having 8 to 24 C atoms, linear α-olefin sulfonates having 8 to 24 C atoms,

Alpha-sulfofatty acid methyl esters of fatty acids having 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 having 8 to 30 carbon atoms and x = O or 1 to 12, sulfated hydroxyalkylpolyethylene and / or Hydroxyalkylenpropylenglycolether

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

Esters of tartaric acid and citric acid with alcohols containing adducts of about 2-

15 molecules of ethylene oxide and / or propylene oxide to fatty alcohols having 8 to 22 carbon atoms,

Alkyl and / or alkenyl ether phosphates of the formula (E1-I),

R ¹ (OCH ₂ CH ₂ ) _n -OP (O) (OX) -OR ² (E1-I)

in the 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 from 1 to 10 and X is hydrogen, an alkali metal radical or alkaline earth metal or NR ³ R ⁴ R ⁵ R ⁶ , where R ³ to R ⁶ independently of one another represent 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 (EI-II) in the R ⁷ CO- for a linear or branched, aliphatic, saturated and / or unsaturated acyl radical having 6 to 22 C atoms, Alk for CH ₂ CH ₂ , CHCH ₃ CH ₂ and / or CH ₂ CHCH ₃ , n is from 0.5 to 5 and M is a cation, monoglyceride sulfates and monoglyceride ether sulfates of the formula (E1-III) CH ₂ O (CH ₂ CH ₂ O) _x -COR ⁸

CHO (CH ₂ CH ₂ O) _y H (E1-III)

I CH ₂ O (CH ₂ CH ₂ O) _Z SO ₃ X

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

Condensation products of C ₈ - C ₃₀ - fatty alcohols with protein hydrolysates and / or amino acids and their derivatives, which are known to the expert as protein fatty acid condensates, such as Lamepon ^® - types Gluadin ^® - types Hostapon ^® KCG or Amisoft ^® - types.

Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids having 10 to 18 C atoms in the alkyl group and up to 12 glycol ether groups in the molecule, sulfosuccinic acid mono- and dialkyl esters having 8 to 18 C atoms in the alkyl group, sulfosuccinic monoalkylpolyoxyethyl ester with 8 to 18 carbon atoms in the alkyl group and 1 to 6, preferably 2 to 4, oxyethylene groups and ethoxylated esters of alkyl esters of citric acid and sulfosuccinic acid having 8 to 18 carbon atoms in the alkyl group and 1 to 6, preferably 3 to 5, oxyethylene groups, for example disodium PEG- 5 lauryl citrate sulfosuccinates, e.g. B. Goldschmidt under the name Rewopol SB CS 50 K available, further monoglyceride sulfates, alkyl and Alkenyletherphosphate and protein fatty acid condensates and amino acid fatty acid condensates, eg. For example, sodium lauroyl glutamates, e.g. Available from Zschimmer & Schwarz under the name Protelan AGL 95.

Zwitterionic surfactants (E2) are surface-active compounds which contain in the molecule at least one quaternary ammonium group and at least one -COO * ^'' - or -SO ₃ ^'wear' 'group. Particularly suitable zwitterionic surfactants are the so-called betaines such as N-alkyl-N, N-dimethylammonium glycinates, for example cocoalkyl dimethyl ammonium glycinate, N-acylaminopropyl N, N-dimethylammonium glycinates, for example Kokosacylaminopropyl-dimethylammoniumglycinat, and 2-alkyl-3-carboxymethyl-3-hydroxyethyl imidazoline having in each case 8 to 18 carbon atoms in the alkyl or acyl group and cocoacylaminoethylhydroxyethylcarboxymethylglycinat. A preferred zwitterionic surfactant is the fatty acid amide derivative known by the INCI name Cocamidopropyl Betaine.

Ampholytic surfactants (E3) are understood as meaning those surface-active compounds which contain, in addition to a C ₈ -C ₂₄ -alkyl or -acyl group, at least one free amino group and at least one -COOH or -SO ₃ H group in the molecule and for forming internal Salts are capable. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each having about 8 to 24 C Atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C ₁₂ -C ₁₈ acylsarcosine.

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

- Addition products of 2 to 50 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide to linear and branched fatty alcohols having 8 to 30 carbon atoms, to fatty acids having 8 to 30 carbon atoms and to alkylphenols having 8 to 15 carbon atoms in the Alkyl group, with a methyl or C ₂ - C ₆ - alkyl radical end-capped addition products of 2 to 50 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide to linear and branched fatty alcohols having 8 to 30 carbon atoms, to fatty acids having 8 to 30 C. -atoms and with alkylphenols having 8 to 15 carbon atoms in the alkyl group, such as the type available under the commercial names Dehydol ^® LS, Dehydol ^® LT (Cognis), C ₁₂ -C ₃₀ fatty acid monoesters and diesters of addition products of 1 up to 30 moles of ethylene oxide with glycerol,

Addition products of 5 to 60 mol ethylene oxide onto castor oil and hydrogenated castor oil, polyol fatty acid esters, such as the commercially available product ^® Hydagen HSP (Cognis) or Sovermol - types (Cognis), alkoxylated triglycerides, alkoxylated fatty acid alkyl esters of formula (E4-I)

R ¹ CO- (OCH ₂ CHR ² ) _W OR ³ (E4-I) in the R ¹ CO for 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} linear or branched

Alkyl radicals having 1 to 4 carbon atoms and w is from 1 to 20,

Amine oxides,

hydroxy mixed,

Sorbitan fatty acid esters and adducts 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, for example the commercial products Glucate SS, Glucate DO, Glucamate DOE 120 and Glucamate SSE 20,

Addition products of ethylene oxide onto fatty acid alkanolamides and fatty amines, sugar surfactants of the alkyl and alkenyl oligoglycoside type according to formula (E4-II),

in which R ^{4 is} an alkyl or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10. They can be obtained by the relevant methods of preparative organic chemistry. The alkyl and alkenyl oligoglycosides can be derived from aldoses or ketoses having 5 or 6 carbon atoms, preferably 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 integer and here before For all given values p = 1 to 6, the value p for a given alkyloligoglycoside is an analytically determined arithmetic variable, which usually represents a fractional number. Preference is given to using alkyl and / or alkenyl oligoglycosides having an average degree of oligomerization p of from 1.1 to 3.0. From an application point of view, those alkyl and / or alkenyl oligoglycosides are preferred whose degree of oligomerization is less than 1.7, and in particular between 1.2 and 1.4. The alkyl or alkenyl radical R ⁴ can be derived from primary alcohols having 4 to 11, preferably 8 to 10 carbon atoms. Typical examples are butanol, caproic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, as obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the hydrogenation of aldehydes from Roelen's oxo synthesis. Preference is given to alkyl oligoglucosides of the chain length C ₈ -C ₁₀ (DP = 1 to 3), which are obtained as a feedstock in the distillative separation of technical C ₈ -C ₁₈ coconut fatty alcohol and having a fraction of less than 6 wt .-% C. ₁₂ alcohol may be contaminated as well as alkyl oligoglucosides based on technical C _9/11 oxo alcohols (DP = 1 to 3). Of the Alkyl or alkenyl radical R ¹⁵ can furthermore 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, palmitoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol and technical mixtures thereof which can be obtained as described above. Alkyl oligoglucosides based on hydrogenated _{C12 /} i ₄ - coconut alcohol with a DP of 1 to 3

Sugar surfactants of the fatty acid N-alkylpolyhydroxyalkylamide type, a nonionic surfactant of the formula (E4-III),

R ⁵ CO-NR ⁶ - [Z] (E4-III)

R ^{5 is} CO for an aliphatic acyl radical having 6 to 22 carbon atoms, R ^{6 is} hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 12 carbon atoms and 3 to 10 hydroxyl groups stands. The fatty acid N-alkyl polyhydroxyalkylamides are known substances which are usually obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride. Preferably, the fatty acid N-alkylpolyhydroxyalkylamides are derived from reducing sugars having 5 or 6 carbon atoms, especially glucose. The preferred fatty acid N-alkylpolyhydroxyalkylamides are therefore fatty acid N-alkylglucamides as represented by the formula R ⁷ CO-NR ⁸ -CH ₂ - (CHOH) ₄ -CH ₂ OH (E4-IV). Glucamides of the formula (E4-IV) in which R ^{8 is} hydrogen or an alkyl group and R ⁷ CO for the acyl radical of caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, are preferably used as the fatty acid N-alkylpolyhydroxyalkylamides. Stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, arachidic acid, gadoleic acid, behenic acid or erucic acid or those technical mixtures. Particular preference is given to 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 C 12/14 coconut fatty acid or a corresponding derivative. Furthermore, the polyhydroxyalkylamides can also be derived from maltose and palatinose.

The preferred nonionic surfactants are the alkylene oxide addition products of saturated linear fatty alcohols and fatty acids having in each case 2 to 30 moles of ethylene oxide per mole of fatty alcohol or fatty acid. Preparations having excellent properties are also obtained if they contain fatty acid esters of ethoxylated glycerol as nonionic surfactants. These connections are identified by the following parameters. The alkyl radical R contains 6 to 22 carbon atoms and may be both linear and branched. Preference is given to primary linear and methyl-branched in the 2-position aliphatic radicals. Such alkyl radicals are, for example, 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl and 1-stearyl. Particularly preferred are 1-octyl, 1-decyl, 1-lauryl, 1-myristyl. When so-called "oxo-alcohols" are used as starting materials, compounds with an odd number of carbon atoms in the alkyl chain predominate.

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

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

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

Cationic surfactants of the quaternary ammonium compound type, the esterquats and the amidoamines can be used according to the invention. Preferred quaternary ammonium compounds are ammonium halides, in particular chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, eg. For example, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride, as well as the imidazolium compounds known under the INCI names Quaternium-27 and Quaternium-83. The long alkyl chains of the above-mentioned surfactants preferably have 10 to 18 carbon atoms. According to the invention, preference is given to using QAV with behenyl radicals, in particular the substances known under the name of behentrimonium chloride or bromide (docosanyltrimethylammonium chloride or bromide). Other preferred QAV's have at least two behenyl residues, with QAV being particularly preferred, which are two behenyl residues on an imidazolinium backbone. Commercially available, these substances are, for example, under the names Genamin ^® KDMP (Clariant) and Crodazosoft ^® DBQ (Crodauza).

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

The alkylamidoamines are usually prepared by amidation of natural or synthetic fatty acids and fatty acid cuts with dialkylaminoamines. A compound of the invention particularly preferred from this group of substances that available under the designation TEGO amide ^® S 18 commercially stearamidopropyl dimethylamine is.

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

The surfactants (E) are preferably used in amounts of 0.1-45% by weight, more preferably 0.5-25% by weight and most preferably of 1, 0-15% by weight, in each case based on the total agent according to the invention, used.

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

Particularly preferred compositions according to the invention, in particular hair and / or skin cleansing compositions, are characterized in that they contain a combination of at least one anionic surfactant, more preferably an alkyl ether sulfate, and at least one zwitterionic surfactant, more preferably cocamidopropyl betaine, and at least one silicic acid ester of the formulas I and / or II and / or III and / or IV,

each at least one radical R is derived from at least one alcohol selected from the group consisting of (Z) -2-hexen-1-ol, (E) -2-hexen-1-ol, (Z) -3- Hexene-1-ol (leaf alcohol), (E) -3-hexen-1-ol, (Z) -4-hexen-1-ol, (E) -4-hexen-1-ol, 5-hexene-1 -ol, cinnamyl alcohol, 3-phenylpropan-1-ol (hydrocinnamyl alcohol), 3R (-) - linalool, 3S (+) - linalool, (-) - menthol, (+) - neomenthol, α-terpineol, ß-terpineol, γ-terpineol, δ-terpineol, (-) - borneol, (+) - isoborneol, (-) - lavandulol, (Z) -4-hepten-2-ol, eugenol, 2-methoxy-4 - ((Z) 1-propenyl) phenol ((Z) isoeugenol), 2-methoxy-4 - ((E) -1-propenyl) phenol ((E) -Isoeugenol), 4-hydroxy-2,5-dimethyl- 3 (2H) -furanone (furaneol ^®), 4-hydroxy-3-methoxy- benzaldehyde (vanillin), 4- (4-hydroxyphenyl) -2-butanone (raspberry ketone), (Z, Z) -3,6-nonadiene 1-ol, 3,7-dimethyl-7-octene-1-ol (rhodinol) and (Z) -3-octene-1-ol, and the other radicals R are each independently selected from the group consisting of a hydrogen atom, the straight-chain or branched, sat temperate or unsaturated, substituted or the unsubstituted th Ci- ₆ hydrocarbon radicals and the 2-phenoxyethyl radical contains, and m assumes values from the range 1 to 20 and na value of the range 2 to 100th Further particularly preferred compositions according to the invention, in particular hair and / or skin cleansing compositions, are characterized in that they contain a combination of at least one anionic surfactant, more preferably an alkyl ether sulfate, and at least one ampholytic surfactant, more preferably an amphoacetate or amphodiacetate, and at least one silicic acid ester of the formulas I and / or II and / or III and / or IV,

each at least one radical R is derived from at least one alcohol selected from the group consisting of (Z) -2-hexen-1-ol, (E) -2-hexen-1-ol, (Z) -3- Hexene-1-ol (leaf alcohol), (E) -3-hexen-1-ol, (Z) -4-hexen-1-ol, (E) -4-hexen-1-ol, 5-hexene-1 -ol, cinnamyl alcohol, 3-phenylpropan-1-ol (hydrocinnamyl alcohol), 3R (-) - linalool, 3S (+) - linalool, (-) - menthol, (+) - neomenthol, α-terpineol, ß-terpineol, γ-terpineol, δ-terpineol, (-) - borneol, (+) - isoborneol, (-) - lavandulol, (Z) -4-hepten-2-ol, eugenol, 2-methoxy-4 - ((Z) 1-propenyl) phenol ((Z) isoeugenol), 2-methoxy-4 - ((E) -1-propenyl) phenol ((E) -Isoeugenol), 4-hydroxy-2,5-dimethyl- 3 (2H) -furanone (furaneol ^®), 4-hydroxy-3-methoxy- benzaldehyde (vanillin), 4- (4-hydroxyphenyl) -2-butanone (raspberry ketone), (Z, Z) -3,6-nonadien-1-ol, 3,7-dimethyl-7-octene-1-ol ( Rhodinol) and (Z) -3-octen-1-ol, and the other radicals R are each independently selected from the group comprising one hydrogen atom, the straight-chain or branched, saturated or unsaturated, substituted or unsubstituted Contains _6- hydrocarbon radicals and the 2-phenoxyethyl radical, and m assumes values from the range 1 to 20 and n values from the range 2 to 100.

In a further preferred embodiment, the agents according to the invention can contain emulsifiers (F). Emulators cause at the phase interface the formation of water- or oil-stable adsorption layers, which protect the dispersed droplets against coalescence and thus stabilize the emulsion. Emulsifiers are therefore constructed like surfactants from 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 meaning a droplet-like distribution (dispersion) of a liquid in another liquid under the expense of energy in order to create stabilizing phase interfaces by means of surfactants. The selection of these emulsifying surfactants or emulsifiers depends on the substances to be dispersed and the respective outer phase and the fineness of the emulsion. Emulsifiers which can be used according to the invention are, for example

Addition products of from 1 to 100, preferably from 4 to 30, moles of ethylene oxide and / or from 0 to 5 moles of propylene oxide to linear fatty alcohols containing from 8 to 22 carbon atoms, to fatty acids containing from 12 to 22 carbon atoms and to alkylphenols having from 8 to 15 carbon atoms Atoms in the alkyl group, C ₂ -C ₂₂ -fatty acid mono- and diesters of addition products of from 1 to 30 mol of ethylene oxide onto polyols having 3 to 6 carbon atoms, in particular to glycerol,

Ethylene oxide and polyglycerol addition products to methyl glucoside fatty acid esters, fatty acid alkanolamides and fatty acid glucamides,

C ₈ -C ₂₂ -alkylmono- and -oligoglycosides and their ethoxylated analogues, preference being given to degrees of oligomerization of from 1.1 to 5, in particular from 1.2 to 2.0, and glucose as the sugar component,

Mixtures of alkyl (oligo) glucosides and fatty alcohols, for example the products commercially available ^® Montanov 68, Montanov ^® L and Montanov ^® 202

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

Sterols. Sterols are understood to mean a group of steroids which have a hydroxyl group on C-atom 3 of the steroid skeleton and are isolated both from animal tissue (zoosterols) and from vegetable fats (phytosterols). Examples of zoosterols are cholesterol and lanosterol. Examples of suitable phytosterols are ergosterol, masterin and sitosterol. Mushrooms and yeasts are also used to isolate sterols, the so-called mycot- rines.

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

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

Ethylene oxide with sugar fatty acid esters, for example the commercial products Glucate SS,

Glucate DO, Glucamate DOE 120 and Glucamate SSE 20,

Polyglycerols and polyglycerol derivatives such as polyglycerol poly-12-hydroxystearate

(Dehymuls ^® PGPH commercial product)

Linear and branched fatty acids with 8 to 30 C atoms and their Na, K, ammonium,

Ca, Mg and Zn salts.

The compositions according to the invention preferably contain the emulsifiers in amounts of from 0.1 to 25% by weight, more preferably 0.5 to 15% by weight and most preferably 1 to 5% by weight, based in each case on the total composition.

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

Furthermore, it may be preferable to use the aforementioned nonionic emulsifiers as skin care substances or skin and hair conditioning substances. Particularly preferred emulsifiers of this type are PEG-7 glyceryl cocoate (z. B. available as Cetiol ^® HE) or the commercial product Lamesoft ^® PO 65 which is an aqueous preparation of cocoglucoside, and glyceryl monooleate.

As further advantageous, it has been shown that polymers (G) are included in the inventive compositions. In a preferred embodiment, the agents used according to the invention which contain at least one silicic acid ester of the formulas I and / or II and / or III and / or IV,

each at least one radical R is derived from at least one alcohol selected from the group consisting of (Z) -2-hexen-1-ol, (E) -2-hexen-1-ol, (Z) -3- Hexene-1-ol (leaf alcohol), (E) -3-hexen-1-ol, (Z) -4-hexen-1-ol, (E) -4-hexen-1-ol, 5-hexene-1 -ol, cinnamyl alcohol, 3-phenylpropan-1-ol (hydrocinnamyl alcohol), 3R (-) - linalool, 3S (+) - linalool, (-) - menthol, (+) - neomenthol, α-terpineol, ß-terpineol, γ-terpineol, δ-terpineol, (-) - borneol, (+) - isoborneol, (-) - lavandulol, (Z) -4-hepten-2-ol, eugenol, 2-methoxy-4 - ((Z) 1-propenyl) phenol ((Z) isoeugenol), 2-methoxy-4 - ((E) -1-propenyl) phenol ((E) -Isoeugenol), 4-hydroxy-2,5-dimethyl- 3 (2H) -furanone (furaneol ^®), 4-hydroxy-3-methoxy- benzaldehyde (vanillin), 4- (4-hydroxyphenyl) -2-butanone (raspberry ketone), (Z, Z) -3,6-nonadiene 1-ol, 3,7-dimethyl-7-octene-1-ol (rhodinol) and (Z) -3-octene-1-ol, and the other radicals R are each independently selected from the group consisting of a hydrogen atom, the straight-chain or branched, sat contains m or unsaturated, substituted or unsubstituted Ci- ₆ -hydrocarbon radicals and the 2-phenoxyethyl radical, and m assumes values from the range 1 to 20 and n assumes values from the range 2 to 100, and mixtures thereof, therefore at least one Polymer added, with both cationic, anionic, amphoteric and nonionic polymers have been found to be effective. Without wishing to be bound by this theory, it is believed that the presence of a polymer further improves the adhesion of the silicic acid esters on the treated surface or positively influences the fragrance release by another mechanism. Cationic or amphoteric polymers are to be understood as meaning polymers which have a group in the main and / or side chain which may be "temporary" or "permanent" cationic. According to the invention, "permanently cationic" refers to those polymers which have a cationic group, irrespective of the pH of the agent. These are usually polymers containing a quaternary nitrogen atom, for example in the form of an ammonium group. Preferred cationic groups are quaternary ammonium groups. In particular, those polymers in which the quaternary ammonium group is bonded via a C ₁ -C ₄ -hydrocarbon group to a polymer main chain composed of acrylic acid, methacrylic acid or derivatives thereof have proven to be particularly suitable.

Homopolymers of the general formula (G1-I),

R ¹

I - [CH ₂ -CJ _n X ^" (G1-I)

I CO-O- (CH ₂ ) _m -N ⁺ R ² R ³ R ⁴

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

R ¹ is a methyl group

R ² , R ³ and R ⁴ are methyl groups m has the value 2.

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

A particularly suitable homopolymer is, if desired crosslinked, poly (methacryloyl oxyethyltrimethylammoniurnchlorid) with the INCI name Polyquaternium-37. Such products are available, for example under the names Rheocare ^® CTH (Cosmetic Rheologies) and Synthalen® ^® CR (Ethnichem) in trade. If desired, the crosslinking can be carried out with the aid of multiply olefinically unsaturated compounds, for example divinylbenzene, tetraallyloxyethane, Methylenebisacrylamide, diallyl ether, polyallylpolyglycerylether, or allyl ethers of sugars or sugar derivatives such as erythritol, pentaerythritol, arabitol, mannitol, sorbitol, sucrose or glucose. Methylenebisacrylamide is a preferred crosslinking agent.

The homopolymer is preferably used in the form of a non-aqueous polymer dispersion which should not have a polymer content of less than 30% by weight. Such polymer dispersions are available under the names Salcare ^® SC 95 (about 50% polymer content, additional components: mineral oil (INCI name: Mineral Oil) and tridecyl-polyoxypropylene-polyoxyethylene-ether (INCI name: PPG-1 trideceth-6) ) and Salcare ^® SC 96 (about 50% polymer content, additional components: mixture of diesters of propylene glycol with a mixture of caprylic and capric acid (INCI name: Propylene glycol Dicaprylate / Dicaprate) and tridecyl polyoxypropylene-polyoxyethylene-ether (INCI name: PPG-1-Trideceth-6)) commercially available.

Copolymers with monomer units of the formula (G1-I) contain, as nonionic monomer units, preferably acrylamide, methacrylamide,

and methacrylic acid-Ci. _4- alkyl esters. Among these nonionic monomers, the acrylamide is particularly preferred. These copolymers can also be crosslinked, as described above in the case of the homopolymers. A preferred copolymer according to the invention is the crosslinked acrylamide-methacryloyl-oxyethyltrimethylammonium chloride copolymer. Such copolymers in which the monomers are present in a weight ratio of about 20:80, commercially available as about 50% non-aqueous polymer dispersion under the name Salcare ^® SC 92nd

Further preferred cationic polymers are, for example

- Quaternized cellulose derivatives, such as those under the names Celquat ^® and Polymer JR ^® commercially available. The commercial products Celquat ^® H 100, Celquat L 200 and Polymer JR ^® ^® 400 or compounds with the INCI names Polyquaternium-10 or Polyquaternium-24 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, in particular those sold under the tradename Cosmedia ^® guar and Jaguar ^® products, polymeric dimethyldiallylammonium salts and their copolymers with esters and Amides of

Acrylic acid and methacrylic acid. Under the names Merquat ^® 100 (Poly (dimethyldi- allylammonium chloride)) and Merquat ^® 550 (dimethyldiallylammonium chloride-acrylamide

Copolymer) are commercially available products having the INCI name Polyquaternium-7

Examples of such preferred cationic polymers,

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

Vinylpyrrolidone-vinyl imidazolium copolymers, such as those offered under the names Luviquat ^® FC 370, FC 550, FC 905 and HM 552, - quaternized polyvinyl alcohol, as well as those known under the designations Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27 polymers having quaternary nitrogen atoms in the polymer backbone.

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

Further cationic polymers preferred in the compositions according to the invention are the so-called "temporary cationic" polymers. These polymers usually contain an amino group which, at certain pH values, is present as quaternary ammonium group and thus cationic. Preferably, for example, are chitosan and its derivatives, such as 101 are commercially available for example under the trade names Hydagen CMF ^®, Hydagen HCMF ^®, Kytamer ^® PC and Chitolam ^® NB /.

According to the invention preferred cationic polymers are cationic cellulose derivatives and chitosan and its derivatives, in particular the commercial products Polymer ^® JR 400, Hydagen ^® HCMF and Kytamer ^® PC, cationic guar derivatives, cationic honey derivatives, in particular the commercial product Honeyquat ^® 50, cationic alkyl polyglycosides according to US5773595 and polymers of the type Polyquaternium-37.

Furthermore, cationized protein hydrolysates are to be counted among the cationic polymers, wherein the underlying protein hydrolyzate from the animal, for example from collagen, milk or keratin, from the plant, for example from wheat, corn, rice, potatoes, soy or almonds, marine life forms, for example from fish collagen or algae, or biotechnologically derived protein hydrolysates. The protein hydrolyzates on which the cationic derivatives according to the invention are based can be obtained from the corresponding proteins by chemical, in particular alkaline or acid hydrolysis, by enzymatic hydrolysis and / or a combination of both types of hydrolysis. The hydrolysis of proteins usually results in a protein hydrolyzate having a molecular weight distribution of about 100 daltons up to several thousand daltons. Preferred are such cationic Protein hydrolysates whose underlying protein content has a molecular weight of 100 to 25,000 daltons, preferably 250 to 5000 daltons. Furthermore, cationic protein hydrolyzates are to be understood as meaning quaternized amino acids and mixtures thereof. The quaternization of the protein hydrolyzates or of the amino acids is frequently carried out by means of quaternary ammonium salts, for example N, N-dimethyl-N- (n-alkyl) -N- (2-hydroxy-3-chloro-n-propyl) -ammonium halides. Furthermore, the cationic protein hydrolysates can also be further derivatized. As typical examples of the cationic protein hydrolyzates and derivatives according to the invention, those mentioned under the INCI names in the "International Cosmetic Ingredient Dictionary and Handbook", (seventh edition 1997, The Cosmetic, Toiletry and Fragrance Association, Washington, DC) Cocodimony Hydroxypropyl Hydrolyzed Collagen, Cocodimium Hydroxypropyl Hydrolyzed Collagen, Cocodimonium Hydroxypropyl Hydrolyzed Hair Keratin, Cocodimonium Hydroxypropyl Hydrolyzed Keratin, Cocodimonium Hydroxypropyl Hydrolyzed Rice Protein, Cocodimonium Hydroxypropyl Hydrolyzed Soy Protein, Cocodimonium Hydroxypropyl Hydrolyzed Wheat Protein, Hydroxypropyl Arginine Lauryl / Myristyl Ether HCl, Hydroxypropyltrimonium Gelatin, Hydroxypropyltrimonium Hydrolyzed Casein, Hydroxypropyltrimonium Hydrolyzed Collagen, Hydroxypropyltrimonium Hydrolyzed Conchiolin Protein, Hydroxypropyltrimonium Hydro Lyzed Keratin, Hydroxypropyltrimonium Hydrolyzed Rice Bran Protein, Hydroxypropyltrimonium Hydrolyzed Soy Protein, Hydroxypropyl Hydrolyzed Vegetable Protein, Hydroxypropyltrimonium Hydrolyzed Wheat Protein, Hydroxypropyltrimonium Hydrolyzed Wheat Protein / Siloxysilicate, Lauridimonium Hydroxypropyl Hydrolyzed Soy Protein, Lauridimonium Hydroxypropyl Hydrolyzed Wheat Protein, Lauridimonium Hydroxypropyl Hydrolyzed Wheat Protein / Siloxysil - Cate, Lauryldimony Hydroxypropyl Hydrolyzed Casein, Lauryldimonium Hydroxypropyl Hydrolyzed Keratin, Lauryldimonium Hydroxypropyl Hydrolyzed Soy Protein, Steardimonium Hydroxypropyl Hydrolyzed Casein, Steardimonium Hydroxypropyl Hydrolyzed Collagen, Steardimonium Hydroxypropyl Hydrolyzed Keratin, Steardimonium Hydroxypropyl Hydrolyzed Rice Protein, Steardimonium Hydroxypropyl Hydrolyzed Soy Protein , Steardimonium Hydroxypropyl Hydrolyzed Vegetable Protein, Steardimonium Hydroxypropyl Hydrolyzed Wheat P Rotein, Steartrimonium Hydroxyethyl Hydrolyzed Collagen, Quaternium-76 Hydrolyzed Collagen, Quaternium-79 Hydrolyzed Collagen, Quaternium-79 Hydrolyzed Keratin, Quaternium-79 Hydrolyzed Milk Protein, Quaternium-79 Hydrolyzed Soy Protein, Quaternium-79 Hydrolyzed Wheat Protein.

Very particular preference is given to the optionally cationized protein hydrolysates and derivatives based on plants.

In addition to cationic polymers or in their place, the agents according to the invention can also contain amphoteric polymers. These additionally have at least one negatively charged group in the molecule and are also referred to as zwitterionic polymers. in the Zwitterionic polymers preferably usable according to the present invention are composed essentially together

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

R ¹ -CH = CR ² -CO-Z- (C _n H _2n ) -N ( ⁺ ) R ³ R ⁴ R ⁵ A ^) (ZI) in which R ¹ and R ² independently of one another represent hydrogen or a methyl group and

R ³ .

R and R ^ independently represent alkyl groups having 1 to 4 carbon atoms, Z a

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 (Z-II),

R ⁶ -CH = CR ⁷ -COOH (II) in which R ° and R independently of one another are hydrogen or methyl groups.

Suitable starting monomers are, for. Dimethylaminoethylacrylamide, dimethylaminoethylmethacrylamide, dimethylaminopropylacrylamide, dimethylaminopropylmethacrylamide and diethylaminoethylacrylamide when Z is an NH group or dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate and diethylaminoethyl acrylate when Z is an oxygen atom.

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

Advantageously, those monomers of the formula (ZI) which are derivatives of the acrylamide or methacrylamide are used. Preference is furthermore given to those monomers which contain halide, methoxysulfate or ethoxysulfate ions as counterions. Also preferred are those monomers of the formula (ZI) in which R ³ , R ^ and R ^ are methyl groups.

The acrylamidopropyltrimethylammonium chloride is a most preferred monomer of formula (Z-I).

Suitable monomeric carboxylic acids of the formula (Z-II) are acrylic acid, methacrylic acid, crotonic acid and 2-methylcrotonic acid. Preference is given to using acrylic or methacrylic acid, in particular acrylic acid.

The zwitterionic polymers which can be used according to the invention are prepared from monomers of the formulas (ZI) and (Z-II) by polymerization processes known per se. The poly- The polymerization can be carried out either in aqueous or aqueous-alcoholic solution. The alcohols used are alcohols having 1 to 4 carbon atoms, preferably isopropanol, which simultaneously serve as polymerization regulators. However, other components than regulators may also be added to the monomer solution, eg. For example, formic acid or mercaptans, such as thioethanol and thioglycolic acid. The initiation of the polymerization takes place with the aid of free-radical-forming substances. For this purpose, redox systems and / or thermally decomposing radical formers of the azo compound type, such. As azoisobutyronitrile, azo-bis (cyanopentanoic acid) or azo-bis (amidinopropane) dihydrochloride can be used. As redox systems are z. B. Combinations of hydrogen peroxide, potassium or ammonium peroxodisulfate and tertiary Butylhydro peroxide with sodium sulfite, sodium dithionite or hydroxylamine hydrochloride as a reduction component.

Particularly effective polymers have proven to be in which the monomers of the formula (Z-I) over the monomers of formula (Z-II) were present in excess. It is therefore preferred according to the invention to use those polymers which consist of monomers of the formula (ZI) and the monomers of the formula (Z-II) in a molar ratio of 60:40 to 95: 5, in particular from 75:25 to 95: 5 , consist.

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

The anionic polymers (G2) are anionic polymers which have carboxylate and / or sulfonate groups. Examples of anionic monomers from which such polymers may consist are acrylic acid, methacrylic acid, crotonic acid, maleic anhydride and 2-acrylamido-2-methylpropanesulfonic acid. The acidic groups may be wholly or partly present as sodium, potassium, ammonium, mono- or triethanolammonium salt. Preferred monomers are 2-acrylamido-2-methylpropanesulfonic acid and acrylic acid. Anionic polymers which contain 2-acrylamido-2-methylpropanesulfonic acid as the sole or co-monomer can be found to be particularly effective, it being possible for all or part of the sulfonic acid group to be in the form of sodium, potassium, ammonium, mono- or triethanolammonium salt ,

More preferably, the homopolymer of 2-acrylamido-2-methyl propane sulfonic acid, which is (crosslinked), for example under the name Rheothik ^® 11-80 or sold under the name Hostacerin AMPS is commercially.

Within this embodiment, it may be preferable to use copolymers of at least one anionic monomer and at least one nonionic monomer. With regard to the anionic monomers, reference is made to the substances listed above. Preferred nonionic monomers are acrylamide, methacrylamide, acrylic esters, methacrylic esters, vinylpyrrolidone, vinyl ethers and vinyl esters. Preferred anionic copolymers are acrylic acid-acrylamide copolymers and in particular polyacrylamide copolymers with sulfonic acid-containing monomers. A particularly preferred anionic copolymer consists of 70 to 55 mol% of acrylamide and 30 to 45 mol% of 2-acrylamido-2-methylpropanesulfonic acid, where the sulfonic acid group is wholly or partly prepared as sodium, potassium, ammonium, mono- or triethanolammonium Salt is present. This copolymer may also be crosslinked, with crosslinking agents preferably polyolefinically unsaturated compounds such as tetraallyloxyethane, allylsucrose, allylpentaerythritol and methylenebisacrylamide are used. Such a polymer is contained in the commercial product Sepigel ^® 305 from SEPPIC. The use of this compound, which contains a hydrocarbon mixture (C ₁₃ -C ₁₄ isoparaffin) and a nonionic emulsifier (laureth-7) in addition to the polymer component, has proven to be particularly advantageous within the scope of the teaching according to the invention.

Also, the NS under the designations Simulgel ^® 600, Simulgel ^®, Simulgel ^® EC and Simulgel ^® EPG as a compound with an oil component selected from isohexadecane, polyisobutane and squalane, and with a O / W-emulsifier selected from polysorbate-80 and Caprylyl / Caprylglucosid distributed Natriumacryloyldimethyltaurat copolymers with a comonomer, selected from acrylamide, hydroxyethyl acrylate and sodium acrylate, have shown to be particularly effective according to the invention.

Likewise preferred anionic homopolymers are uncrosslinked and crosslinked polyacrylic acids. Allyl ethers of pentaerythritol, sucrose and propylene may be preferred crosslinking agents. Such compounds are commercially available, for example, under the trademark Carbopol ^® .

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

Further preferred compositions according to the invention are characterized in that they contain at least one amphoteric polymer (G3). The term amphoteric polymers includes both those polymers which contain in the molecule both free amino groups and free -COOH or -SO ₃ H groups and which are capable of forming internal salts, as well as zwitterionic polymers which contain quaternary ammonium groups in the molecule and COO ^' - or -SO ₃ ^" - groups, and summarized those polymers containing -COOH or SO ₃ H groups and quaternary ammonium groups.

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

Preferably used amphoteric polymers are those polymers which are composed essentially

(a) monomers having 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 ^H (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 represent alkyl groups having 1 to 4 carbon atoms, Z represents an NH 4

A 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.

These compounds can be used both directly and in salt form, which is obtained by neutralization of the polymers, for example with an alkali metal hydroxide, according to the invention. Very particular preference is given to those polymers in which monomers of the type (a) are used in which R ³ , R ⁴ and R ^{5 are} methyl groups, Z is an NH group and A ^(- 'a halide, methoxysulfate or ethoxy sulfate Ion is acrylamidopropyltrimethylammonium chloride is a particularly preferred monomer (a) As the monomer (b) for the polymers mentioned acrylic acid is preferably used.

In another embodiment, the agents according to the invention may contain nonionic polymers (G4).

Preferred nonionic polymers are, for example:

Vinylpyrrolidone / vinyl ester copolymers, as 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 methylhydroxypropyl cellulose, such as are for example sold under the trademark Culminal® ^® and Benecel ^® (AQUA LON) and Natrosol ^® grades (Hercules). Starch and its derivatives, in particular starch ethers, for example Structure XL (National Starch), a multifunctional, salt-tolerant starch;

shellac

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

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

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

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

Further preferred compositions according to the invention are characterized in that they contain at least one UV filter substance. The UV filters preferred according to the invention are not subject to any general restrictions with regard to their structure and their physical properties. On the contrary, all UV filters which can be used in the cosmetics sector and whose absorption maximum is in the UVA (315-400 nm), in the UVB (280-315 nm) or in the UVC (<280 nm) range are suitable. UV filters with an absorption maximum in the UVB range, in particular in the range from about 280 to about 300 nm, are particularly preferred.

The UV filter substances are substances which are liquid or crystalline at room temperature and which are capable of absorbing ultraviolet rays and of absorbing the absorbed energy in the form of longer-wave radiation, eg. B. to give off heat again. One differentiates between UVA filters and UVB filters. The UVA and UVB filters can be used individually or in mixtures. The use of filter mixtures is preferred according to the invention.

The organic UV filters used according to the invention are selected from the derivatives of dibenzoylmethane, cinnamic acid esters, diphenylacrylic acid esters, benzophenone, camphor, p-aminobenzoic acid esters, o-aminobenzoic acid esters, salicylic acid esters, benzimidazoles, symmetrically or asymmetrically substituted 1,3,5-triazines, monomers and oligomeric 4,4-diarylbutadiene carboxylic acid esters and carboxamides, ketotricyclo (5.2.1.0) decane, benzaldehyde malonates, benzoxazole and any mixtures of the components mentioned. The organic UV filters can be oil-soluble or water-soluble. The benzoxazole derivatives are advantageously present in dissolved form in the cosmetic preparations according to the invention. However, it may also be advantageous if the benzoxazole derivatives are present in a pigmentary, ie undissolved form, for example in particle sizes of from 10 nm to 300 nm. According to the invention particularly preferred oil-soluble UV filters are 1- (4-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1, 3-dione (Parsol ^® 1789), 1-phenyl-3- (4 '-isopropylphenyl) propane-1, 3-dione, 3- ^(4' -Methylbenzy- liden) -D, L-camphor, 4- (dimethylamino) benzoic acid 2-ethylhexyl ester, 4- (dimethylamino) benzoic acid 2-octyl ester, 4- (dimethylamino) benzoic acid ester, 4-methoxycinnamic acid 2-ethylhexyl ester, 4-methoxycinnamic acid propyl ester, 4-methoxycinnamic acid isopentyl ester, 2-cyano-3,3-phenylcinnamic acid 2-ethylhexyl ester (octocrylene), salicylic acid 2-ethylhexyl ester, 4-isopropylbenzyl salicylate, homomenthyl salicylate (3,3,5-trimethylcyclohexylsalicylate), 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy 4-methoxybenzophenone, 2- (4'-diethylamino-2'-hydroxybenzoyl) -benzoic acid hexyl ester (also: aminobenzophenone, available under the name Uvinul A Plus from BASF), 4-methoxybenzmalonic acid di-2-ethylhexyleste r, bound to polymers UV filter, z. B. 3- (4- (2,2-bis-ethoxycarbonylvinyl) phenoxy) propenyl) -methoxysiloxan / dimethylsiloxane copolymer with the INCI name Dimethicodiethylbenzal malonate (CAS no. 207574-74-1, Parsol ^® SLX) , Triazine derivatives, such as. B. 2,4-bis - {[4- (2-ethyl-hexyloxy) -2-hydroxy] -phenyl} -6- (4-methoxyphenyl) -1,3,5-triazine (INCI: bis-ethylhexyloxyphenol methoxyphenyl triazine, available) under the name Tinosorb S from CIBA, dioctylbutylamidotriazone (INCI: Diethylhexyl Butamido Triazone, available) under the name Uvasorb HEB from Sigma 3V ^®, 2,4,6-trianilino- (p-carbo-2'-ethyl- 1'-hexyloxy) - 1, 3,5-triazine (ethylhexyl triazone, Uvinul ^® T 150), 2- [4,6-bis (2,4-dimethylphenyl) -1, 3,5-triazin-2-yl ] -5- (octyloxy) phenol (CAS No .: 2725-22-6), 2,4-bis [5-1 (di-methylpropyl) benzoxazol-2-yl (4-phenyl) -imino ] -6- (2-ethylhexyl) imino-1, 3,5-triazine (CAS no. 288254-16-0, Uvasorb K2A ^® from 3V Sigma), the benzotriazole derivatives of 2,2'-methylene-bis- (6 - (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) -phenol) [Tinosorb M (Ciba)], 2,2'-methyl-bis- [6 (2H benzotriazole-2-yl) -4- (methyl) - phenol] (MIXXIM BB / 200 from Fairmount Chemical), 2- (2'-hydroxy-3 ', 5 ¹ -di-t-amylphenyl) benzotriazol (CAS No .: 025973-551), 2- (2'-hydroxy-5 ' octylphenyl) benzotriazole (CAS no. 003147-75-9), 2- (2'-hydroxy-5'-methylphenyl) benzotriazole (CAS No. 2440-22-4), 2- (2H-benzotriazol-2-yl) -4-methyl-6 - [2-methyl-3- [1,3,3,3-tetramethyl-1 - ((trimethylsilyl) oxy] disiloxanyl) propyl] phenol (CAS No .: 155633-54-8) with the INCI name Drometrizole Trisiloxanes, 2,4-bis - {[4- (2-ethyl-hexyl-oxy) -2-hydroxy] -phenyl} -6- (4-methoxyphenyl) -1, 3,5-triazine (INCI: Bis -Ethylhexyloxyphenol methoxyphenyl triazine or Aniso triazine, available as Tinosorb S from CIBA ^®), 2,4-bis - {[4- (3-sulfonato) -2-hydroxy-propyloxy) -2-hydroxy] phenyl} -6 - (4-methoxyphenyl) -1, 3,5-triazine sodium salt, 2,4-bis - {[4- (3- (2-propyloxy) -2-hydroxy-propyloxy) -2-hydroxy] - phenyl} -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis - {[4- (2-ethyl-hexyloxy) -2-hydroxy] -phenyl} -6- [4- (2-methoxyethylcarboxyl) -phenylamino] -1, 3,5-triazine, 2,4-bis - {[4- (3- (2-propyloxy) -2-hydroxy-propyloxy) -2-hydroxy] - phenyl} -6- [4- (ethylcarboxyl) -phenylamino] -1,3,5-triazine, 2,4-bis - {[4- (2-ethylhexyloxy) -2-hydroxy] -phenyl} -6- (1-methylpyrrole-2) yl) -1, 3,5-triazine, 2,4-bis {[4-tris (trimethylsiloxy-silylpropyloxy) -2-hydroxy] -phenyl} - 6- (4-methoxyphenyl) -1, 3.5- triazine, 2,4-bis - {[4- (2-methylpropenyloxy) -2-hydroxy] -phenyl} -6- (4-methoxyphenyl) -1, 3,5-triazine, 2,4-bis - {[ 4- (1 ', 1', 1 ^l , 3 ^l , 5 ', 5', 5'-heptamethylsiloxy-2-methyl-propyloxy) -2-hydroxy] -phenyl} -6- (4-methoxyphenyl) -1 , 3,5-triazine and mixtures of the above components.

Preferred water-soluble UV filters are 2-phenylbenzimidazole-5-sulfonic acid, phenylene-1,4-bis (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid and their alkali metal, alkaline earth metal, ammonium, Alkylammonium, alkanolammonium and glucammonium salts, especially the sulfonic acid itself with the INCI name phenylbenzimidazole sulfonic acid (CAS No. 27503-81-7), for example, under the trade name Eusolex 232 at Merck or under Neo Heliopan Hydro at Symrise is available, and the phenylene-1,4-bis (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid bis-sodium salt with the INCI name Disodium Phenyl Dibenzimidazole Tetrasulfonate (CAS No .: 180898-37- 7), which is available, for example, from Symrise under the trade name Neo Heliopan AP, sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts, sulfonic acid derivatives of the 3-benzylidene camphor, such as B. 4- (2-oxo-3-bornylidenemethyl) benzenesulfonic acid and 2-methyl-5- (2-oxo-3-bomylidene) sulfonic acid and its salts with the INCI name Terephthalydene Dicampher Sulfonic Acid (CAS. 90457-82-2, available under the tradename Mexoryl SX from Chimex).

Some of the oil-soluble UV filters can themselves serve as solvents or solubilizers for other UV filters. Thus, the UV-A-filter 1 can be, for example, solutions - (4-tert-butylphenyl) -3- (4'methoxyphenyl) propane-1, 3-dione (. Eg Parsol ^® 1789) in various UV-B - Make filters. Therefore, in a further preferred embodiment, the compositions according to the invention contain 1- (4-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione in combination with at least one UV-B filter selected from 4 2-ethylhexyl methoxy cinnamate, 2-ethylhexyl 2-cyano-3,3-phenylcinnamate, 2-ethylhexyl salicylate and 3,3,5-trimethyl cyclohexyl salicylate. In these combinations, the weight ratio of UV-B filter to 1- (4-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione is between 1: 1 and 10: 1, preferably between 2: 1 and 8: 1, the molar ratio is between 0.3 and 3.8, preferably between 0.7 and 3.0.

The inventively preferred inorganic photoprotective pigments are finely dispersed or colloidally disperse metal oxides and metal salts, for example titanium dioxide, zinc oxide, iron oxide, aluminum oxide, cerium oxide, zirconium oxide, silicates (talc) and barium sulfate. The particles should have an average diameter of less than 100 nm, preferably between 5 and 50 nm and in particular between 15 and 30 nm, so-called nano-pigments. They can have a spherical shape, but it can also be such particles are used, which have an ellipsoidal or otherwise deviating from the spherical shape shape. The pigments can also be surface-treated, ie hydrophilized or hydrophobized. Typical examples are coated titanium dioxides, such as. Example, titanium dioxide T 805 (Degussa) or Eusolex ^® T2000 (Merck). Suitable hydrophobic coating agents are in particular silicones and in particular trialkoxyoctylsilanes or simethicones. Particularly preferred are titanium dioxide and zinc oxide.

Finally, the compositions according to the invention may also contain plant extracts (L). Usually these extracts are produced by extraction of the whole plant. However, in individual cases it may also be preferred to prepare the extracts exclusively from flowers and / or leaves of the plant.

The extracts of green tea, oak bark, stinging nettle, witch hazel, hops, henna, chamomile, burdock root, horsetail, hawthorn, linden, almond, aloe vera, spruce needle, horse chestnut, sandalwood, juniper, coconut, mango, apricot, lime , Wheat, kiwi, melon, orange, grapefruit, sage, rosemary, birch, mallow, meadowfoam, quenelle, yarrow, thyme, lemon balm, toadstool, coltsfoot, marshmallow, meristem, ginseng and ginger root.

As extraction agent for the preparation of said plant extracts water, alcohols and mixtures thereof can be used. Among the alcohols are lower alcohols such as ethanol and isopropanol, but especially polyhydric alcohols such as ethylene glycol and propylene glycol, both as the sole extractant and in admixture with water, are preferred. Plant extracts based on water / propylene glycol in a ratio of 1:10 to 10: 1 have proven to be particularly suitable. Further particularly preferred are extractant cosmetic oils, in particular the esters of linear or branched C ₆ - ₃ o-fatty acids with linear or branched C ₂ - ₃ o-fatty alcohols, such as isopropyl palmitate, further hydroxycarboxylic bonsäurealkylester and dicarboxylic acid esters such as di-n-butyl adipate and diol esters such as ethylene glycol dioleate or propylene glycol di (2-ethylhexanoate).

The plant extracts can be used according to the invention both in pure and in diluted form. If they are used in diluted form, they usually contain about 2 to 80 wt .-% of active substance and as a solvent used in their extraction agent or extractant mixture. Furthermore, it may be preferred to use in the compositions according to the invention mixtures of several, especially two, different plant extracts.

Further particularly preferred compositions according to the invention are characterized in that they contain at least one penetration assistant and / or at least one swelling agent (M). These include, for example, urea and urea derivatives, bis-N, N '- (2-hydroxyethylurea), guanidine and its derivatives, arginine and its derivatives, water glass, imide azole and its derivatives, histidine and its derivatives, benzyl alcohol, glycerol, glycol and glycol ethers, propylene glycol and propylene glycol ethers, for example propylene glycol monoethyl ether, carbonates, bicarbonates, diols and triols, and especially 1, 2-diols and 1, omega-diols such as 1,2-propanediol, 1,2-pentanediol, 1,2-hexanediol, 1,2-dodecanediol, 1,3-propanediol, 1,6-hexanediol, 1,5-pentanediol and 1,4-butanediol.

Advantageously in the context of the invention, short-chain carboxylic acids (N) may additionally support the active substance complex (A) from at least one apolar ingredient and at least one protein-complexed trace element from the group Zn, Mg, Cu, Mn, Si, K, Fe. Short-chain carboxylic acids and their derivatives in the context of the invention are understood to mean carboxylic acids which may be saturated or unsaturated and / or straight-chain or branched or cyclic and / or aromatic and / or heterocyclic and have a molecular weight of less than 750. For the purposes of the invention, preference may be given to saturated or unsaturated straight-chain or branched carboxylic acids having a chain length of from 1 to 16 C atoms in the chain, very particular preference being given to those having a chain length of from 1 to 12 C atoms in the chain.

The short-chain carboxylic acids according to the invention may have one, two, three or more carboxy groups. Preferred within the meaning of the invention are carboxylic acids having a plurality of carboxy groups, in particular di- and tricarboxylic acids. The carboxy groups may be wholly or partly present as esters, acid anhydride, lactone, amide, imidic acid, lactam, lactim, dicarboximide, carbohydrazide, hydrazone, hydroxam, hydroxime, amidine, amidoxime, nitrile, phosphonic or phosphate ester. The carboxylic acids according to the invention may of course be substituted along the carbon chain or the ring skeleton. The substituents of the carboxylic acids according to the invention are, for example, C 1 -C 8 -alkyl, C 2 -C 8 -alkenyl, aryl, aralkyl and aralkenyl, hydroxymethyl, C 2 -C 8 -hydroxyalkyl, C 2 -C 8 -hydroxyalkenyl, Amino methyl, C 2 -C 8 aminoalkyl, cyano, formyl, oxo, thioxo, hydroxy, mercapto, amino, carboxy or imino groups. Preferred substituents are C 1 -C 8 alkyl, hydroxymethyl, hydroxy, amino and carboxy groups. Particularly preferred are substituents in α - position. Very particularly preferred substituents are hydroxy, alkoxy and amino groups, where the amino function may optionally be further substituted by alkyl, aryl, aralkyl and / or alkenyl radicals. Furthermore, preferred carboxylic acid derivatives are the phosphonic and phosphate esters.

Examples of carboxylic acids according to the invention include formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, glyceric acid, glyoxylic acid, adipic acid, pimelic acid, suberic acid, sebacic acid, propiolic acid, crotonic acid, isocroton acid, elaidic acid, maleic acid, fumaric acid, muconic acid, citraconic acid, mesaconic acid, camphoric acid, benzoic acid, o, m, p-phthalic acid, naphthoic acid, toluoic acid, hydratropa acid, atropic acid, cinnamic acid, isonicotinic acid, nicotinic acid, Bicarbaminsäure, 4,4 ^'-Dicyano- ^6,6' -binicotinsäure, 8-Carbamoyloctansäure, 1, 2,4-pentanetricarboxylic acid, 2-pyrrolecarboxylic acid, 1, 2,4,6, 7-naphthalenepentaacetic acid, malonaldehyde acid, 4-hydroxyphthalamic acid, 1-pyrazolecarboxylic acid, gallic acid or propanetricarboxylic acid, a dicarboxylic acid selected from the group formed by compounds of general formula (NI),

(N-I)

in the Z represents a linear or branched alkyl or alkenyl group having 4 to 12 carbon atoms, n is a number from 4 to 12 and one of the two groups X and Y is a COOH group and the other is 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 formed from the dicarboxylic acids according to formula (NI) formally by addition of a molecule of water to the double bond in the cyclohexene ring. Dicarboxylic acids of the formula (N-I) are known in the literature. The dicarboxylic acids of the formula (N-I) can be prepared, for example, by reacting polyunsaturated dicarboxylic acids with unsaturated monocarboxylic acids in the form of a Diels-Alder cyclization. Usually one will assume a polyunsaturated fatty acid as the dicarboxylic acid component. Preferred is the linoleic acid obtainable from natural fats and oils. As the monocarboxylic acid component, in particular acrylic acid, but also, for example, Methacrylic acid and crotonic acid are preferred. Normally, in the case of reactions according to Diels-Alder, mixtures of isomers are formed in which one component is present in excess. These isomer mixtures can be used according to the invention as well as the pure compounds.

In addition to the preferred dicarboxylic acids according to formula (NI), those dicarboxylic acids which differ from the compounds according to formula (NI) by 1 to 3 methyl or ethyl substituents on the cyclohexyl ring or formally from these compounds by addition of one molecule of water are also usable according to the invention be formed on the double formation of Cyclohexen- rings. The dicarboxylic acid (mixture), which is obtained by reacting linoleic acid with acrylic acid, has proved to be particularly effective according to the invention. It is a mixture of 5- and 6-carboxy-4-hexyl-2-cyclohexene-1-octanoic acid. Such compounds are commercially available under the designations Westvaco Diacid 1550 Westvaco Diacid ^® ^® 1595 (manufacturer: Westvaco).

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

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

Furthermore, it has been shown that the effect of the agents according to the invention can be increased if they contain hydroxycarboxylic acid esters. Preferred hydroxycarboxylic acid esters are full esters of glycolic acid, lactic acid, malic acid, tartaric acid or citric acid. Further basically suitable hydroxycarboxylic esters are esters of β-hydroxypropionic acid, tartronic acid, D-gluconic acid, sugar acid, mucic acid or glucuronic acid. Suitable alcohol components of these esters are primary, linear or branched aliphatic alcohols having 8-22 carbon atoms, for example fatty alcohols or synthetic fatty alcohols. The esters of C _{12 are} C ₁₅ fatty alcohols are particularly preferred. Esters of this type are commercially available, eg under the trademark Cosmacol® ^® EniChem, Augusta Industriale.

The amount of hydroxycarboxylic acid ester used is 0.1-15% by weight, based on the agent, preferably 0.1-10% by weight, and very particularly preferably 0.1-5% by weight.

According to a further preferred embodiment, the agents according to the invention furthermore contain at least one fatty substance, in particular at least one fatty substance in nanoparticulate form. Such a nanoparticulate fatty substance is, for example, nanoparticulate hydrogenated castor oil. The average size of the nanoparticles is preferably about 100 nm or less, based on the particle diameter.

Particularly preferred cosmetic preparations according to the invention additionally comprise silicone (e). Here, particularly preferred cosmetic preparations according to the invention are characterized in that they additionally contain silicone (s), preferably in amounts of from 0.1 to 50% by weight (especially, but not exclusively, in deodorant or antiperspirant compositions), particularly preferably 0.2 - 10 wt .-%, preferably 0.25 to 7 wt .-% and in particular 0.5 to 5 wt .-%, each based on the total agent included. The preferred amount of silicone used depends on the

Particular preference is given to cosmetic preparations according to the invention which contain at least one

Silicon included, which is selected at:

(i) polyalkyl siloxanes, polyaryl siloxanes, polyalkylaryl siloxanes which are volatile or nonvolatile, straight chain, branched or cyclic, crosslinked or uncrosslinked; (ii) Polysiloxanes having one or more organofunctional in their general structure

Contain groups selected from: a) substituted or unsubstituted aminated groups; b) (per) fluorinated groups; c) thiol groups; d) carboxylate groups; e) hydroxylated groups; f) alkoxylated groups; g) acyloxyalkyl groups; h) amphoteric groups; i) bisulfite groups; j) hydroxyacylamino groups; k) carboxy groups;

I) sulfonic acid groups; and m) sulfate or thiosulfate groups; (iii) linear polysiloxane (A) - polyoxyalkylene (B) - block copolymers of the type (AB) _n with n>3;

(iv) grafted silicone polymers having a non-silicone organic backbone consisting of an organic backbone formed from organic monomers containing no silicone grafted with at least one polysiloxane macromer in the chain and optionally at least one chain end;

(v) grafted polysiloxane backbone silicone polymers having grafted thereto non-silicone organic monomers having a polysiloxane backbone to which at least one organic macromer other than silicone has been grafted in the chain and optionally at least at one of its ends contains;

(vi) or mixtures thereof.

Particularly preferred cosmetic preparations according to the invention are characterized in that they contain at least one silicone of the formula I

(CH ₃ ) ₃ Si [O-Si (CH ₃ ) 2] χ-O-Si (CH 3) 3 (I),

in which x is a number from 0 to 100, preferably from 0 to 50, more preferably from 0 to 20 and in particular 0 to 10.

The inventively preferred cosmetic preparations contain a silicone of the formula I above. These silicones are referred to according to the INCI nomenclature as DIMETHICONE. In the context of the present invention, as the silicone of the formula I, the compounds are preferably:

(CH ₃ ) ₃ Si-O- (CH ₃ ) ₂ Si-O-Si (CH ₃ ) ₃

(CH ₃ ) ₃ Si [O- (CH ₃ ) ₂ Si] ₂ -O-Si (CH ₃ ) 3

(CH ₃ ) ₃ Si [O- (CH ₃ ) 2 Si] 3 O-Si (CH ₃ ) 3

(CH ₃ ) ₃ Si-rO- (CH ₃ ) ₂ Si] 4-O-Si (CH ₃ ) 3

(CH ₃ ) ₃ Si [O- (CH ₃ ) ₂ Si] 5-O-Si (CH ₃ ) 3

(CH ₃ ) ₃ Si [O- (CH ₃ ) ₂ Si] ₆ -O-Si (CH ₃ ) 3

(CH ₃ ) ₃ Si - [O- (CH ₃ ) ₂ Si] 7-O-Si (CH ₃ ) 3

(CH ₃ ) ₃ Si [O- (CH ₃ ) ₂ Si] ₈ -O-Si (CH ₃ ) ₃

(CH ₃ ) ₃ Si - [O- (CH ₃ ) ₂ Si] ₉ -O-Si (CH ₃ ) 3

(CH ₃ ) ₃ Si [O- (CH ₃ ) ₂ Si] ₁₀ -O-Si (CH ₃ ) ₃

(CH ₃ ) ₃ Si [O- (CH ₃ ) ₂ Si] ₁₁ -O-Si (CH ₃ ) 3

(CH ₃ ) ₃ Si [O- (CH ₃ ) ₂ Si] ₁₂ -O-Si (CH ₃ ) ₃

(CH ₃ ) ₃ Si [O- (CH ₃ ) ₂ Si] ₁₃ -O-Si (CH ₃ ) ₃ (CH ₃ ) ₃ Si - [O - (CH ₃ ) ₂ Si] ₁₄ - O - Si (CH ₃ ) 3 (CH ₃ ) ₃ Si - [O - (CH ₃ ) ₂ Si] ₁₅ - O - Si (CH 3) 3 (CH ₃₎ 3 Si- [O- (CH 3) 2 Si] ₁₆ -O-Si (CH3) 3 (CH ₃₎ 3 Si- [O- (CH ₃₎ ₂ Si] ₁₇ -O-Si (CH ₃₎ 3 (CH ₃ ) ₃ Si [O- (CH ₃ ) ₂ Si] ₁₈ -O-Si (CH ₃ ) 3 (CH ₃ ) ₃ Si [O- (CH ₃ ) ₂ Si] ₁₉ -O-Si (CH ₃ ) ₃ (CH ₃ ) ₃ Si [O- (CH ₃ ) ₂ Si] ₂₀ -O-Si (CH ₃ ) ₃

where (CH ₃ ) ₃ Si-O-Si (CH ₃ ) ₃ , (CH ₃ ) ₃ Si-O- (CH ₃ ) ₂ Si-O-Si (CH ₃ ) ₃ and / or (CH ₃ ) ₃ Si [O- (CH ₃ ) ₂ Si] ₂ -O-Si (CH ₃ ) _{3 are} particularly preferred.

Of course, mixtures of o.g. Silicone be included in the inventive compositions.

Preferred according to the invention can be used silicones have viscosities at 20 ⁰ C of 0.2 to 2 mmV ^1, wherein silicones are particularly preferably having viscosities of 0.5 to 1 mmV. ¹

Particularly preferred agents according to the invention contain one or more amino-functional silicones. Such silicones may e.g. through the formula

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

Will be described, wherein in the above formula R is a hydrocarbon or a hydrocarbon radical having from 1 to about 6 carbon atoms, Q is a polar radical of the general formula -R ¹ HZ, wherein R ^{1 is} a divalent connecting group attached to hydrogen and the Z is an organic, amino-functional radical containing at least one amino-functional group, carbon and hydrogen atoms, carbon, hydrogen and oxygen atoms or carbon, hydrogen and nitrogen atoms; "a" assumes values in the range of about 0 to about 2, "b" assumes values in the range of about 1 to about 3, "a" + "b" is less than or equal to 3, and "c" is a number in the range from about 1 to about 3, and x is a number ranging from 1 to about 2,000, preferably from about 3 to about 50, and most preferably from about 3 to about 25, and y is a number ranging from about 20 to about 10,000 , preferably from about 125 to about 10,000, and most preferably from about 150 to about 1,000, and M is a suitable silicone end group as known in the art, preferably trimethylsiloxy. Non-limiting examples of the groups represented by R include alkyl groups such as methyl, ethyl, propyl, isopropyl, isopropyl, butyl, isobutyl, amyl, isoamyl, hexyl, isohexyl and the like; Alkenyl radicals such as vinyl, halovinyl, alkylvinyl, allyl, haloallyl, alkylallyl; Cycloalkyl radicals such as cyclobutyl, cyclopentyl, cyclohexyl and the like; Phenyl radicals, benzyl radicals, halogenated hydrocarbon radicals, such as 3-chloropropyl, 4-bromobutyl, 3,3,3-trifluoropropyl, chlorocyclohexyl, bromophenyl, chlorophenyl and the like, and sulfur-containing groups such as mercaptoethyl, mercaptopropyl, mercaptohexyl, mercaptophenyl and the like; preferably R is an alkyl radical containing from 1 to about 6 carbon atoms, and most preferably R is methyl. Examples of R ¹ include methylene, ethylene, propylene, hexamethylene, decamethylene, -CH ₂ CH (CH ₃ ) CH ₂ -, phenylene, naphthylene, -CH ₂ CH ₂ SCH ₂ CH ₂ -, -CH ₂ CH ₂ OCH ₂ - , -OCH ₂ CH ₂ -, -OCH ₂ CH ₂ CH ₂ -, -CH ₂ CH (CH ₃ ) C (O) OCH ₂ -, - (CH ₂ J ₃ CC (O) OCH ₂ CH ₂ -, - C ₆ H ₄ C ₆ H ₄ -, -C ₆ H ₄ CH ₂ C ₆ H ₄ -; and - (CH ₂ ) ₃ C (O) SCH ₂ CH ₂ -.

Z is an organic, amino-functional radical containing at least one functional amino group. A possible formula for Z is NH (CH ₂ ) _Z NH ₂ , wherein z is 1 or more. Another possible formula for Z is -NH (CH ₂ ) _Z (CH ₂ ) zzNH, wherein both z and zz are independently 1 or more, this structure comprising diamino ring structures, such as piperazinyl. Z is most preferably a -NHCH ₂ CH ₂ NH ₂ radical. Another possible formula for Z is -N (CH ₂ ) _Z (CH ₂ ) _Z -NX ₂ or -NX ₂ , wherein each X of X _{2 is} independently selected from the group consisting of hydrogen and alkyl groups having 1 to 12 carbon atoms, and zz is O

Q is most preferably a polar, amine functional group of the formula -CH ₂ CH ₂ CH ₂ NHCH ₂ CH ₂ NH ₂ . In the formulas, "a" assumes values in the range of about 0 to about 2, "b" assumes values in the range of about 2 to about 3, "a" + "b" is less than or equal to 3, and "c "is a number in the range of about 1 to about 3. The molar ratio of the R _a Q _b SiO _(4. _a _{b) / 2} units to the R ₀ SiO _(4. _{c) / 2} units is in the range from about 1: 2 to 1:65, preferably from about 1: 5 to about 1:65, and most preferably from about 1:15 to about 1:20. When one or more silicones of the above formula are used, then the various variables can be used Substituents in the above formula may be different for the various silicone components present in the silicone blend.

Preferred cosmetic preparations according to the invention comprise an amino-functional silicone of the formula (II)

R ¹ _a G ₃ . _a -Si (OSiG ₂ ) _n - (OSiG _b R ' _2, _b ) _m -O-SiG ₃ . _a -R ¹ _a (II),

where:

G is -H, phenyl, -OH, -O-CH ₃ , -CH ₃ , -O-CH ₂ CH ₃ , -CH ₂ CH ₃ , -O-CH ₂ CH ₂ CH ₃₁ -CH ₂ CH ₂ CH ₃ , -O-CH (CH ₃ J ₂ , -CH (CH ₃ J ₂ , -O-CH ₂ CH ₂ CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₂ CH ₃ , -O-CH ₂ CH (CHa ) ₂ , -CH ₂ CH (CH ₃ ); ,, -O-CH (CH ₃ ) CH ₂ CH ₃ , - CH (CH ₃ ) CH ₂ CH ₃ , -O-C (CH ₃ J ₃ , -C (CH ₃ ), a stands for a number between O and 3, in particular O, b stands for a number between O and 1, in particular 1, m and n are numbers whose sum (m + n) is between 1 and 2000, preferably between 50 and 150, where n is preferably values from 0 to 1999 and in particular from 49 to 149 and m preferably values from 1 to 2000, in particular from 1 to 10, R ^' is a monovalent radical selected from o -QN (R ") - CH ₂ -CH ₂ -N (R ⁿ ) ₂ o -QN (R") ₂ o -QN ⁺ (R ") ₃ A. ^" o -QN ⁺ H (R") ₂ A- o -QN ⁺ H ₂ (R ") A- o -QN (R") - CH ₂ -CH ₂ -N ⁺ R "H ₂ A ^" , where each Q represents a chemical bond, -CH ₂ -, -CH ₂ -CH ₂ -, -CH ₂ CH ₂ CH ₂ -, -C (CH ₃ ) ₂ -, -CH ₂ CH ₂ CH ₂ CH ₂ -, -CH ₂ C (CHa) ₂ -, -CH (CH ₃ ) CH ₂ CH ₂ -,

R "is identical or different radicals from the group -H, -phenyl, -benzyl, -CH ₂ -CH (CH ₃ ) Ph, the Ci. ₂₀ -alkyl radicals, preferably -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ J ₂ , -CH ₂ CH ₂ CH ₂ H ₃ , -CH ₂ CH (CH ₃ ) ₂ , -CH (CH ₃ ) CH ₂ CH ₃ , -C (CH ₃ J ₃ , and A represents an anion, which is preferably selected from chloride, bromide, iodide or methosulfate.

Particularly preferred cosmetic preparations according to the invention are characterized in that they contain at least one amino-functional silicone of the formula (IIa)

(CH ₃ ) ₃ Si - [O-Si (CH ₃ ) ₂ ] _n [OSi (CH ₃ )] _m - OSi (CH ₃ ) ₃ (IIa),

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

in which m and n are numbers whose sum (m + n) is between 1 and 2000, preferably between 50 and 150, where n preferably values of 0 to 1999 and in particular of 49 to 149 and m preferably values of 1 to 2000 , in particular from 1 to 10 assumes. These silicones are referred to as trimethylsilylamodimethicones according to the INCI declaration.

Particular preference is also given to cosmetic preparations according to the invention which contain at least one amino-functional silicone of the formula (IIb)

R- [Si (CH ₃ ) ₂ -O] _n ₁ [Si (R) -O] _m - [Si (CH ₃ ) ₂ ] _n ₂ -R (IIb),

I (CH ₂ ) ₃ NH (CH ₂ ) ₂ NH ₂

in which R is -OH, -O-CH ₃ or a -CH ₃ group and m, n1 and n2 are numbers whose sum (m + n1 + n2) is between 1 and 2,000, preferably between 50 and 150 . wherein the sum (n1 + n2) preferably takes values from 0 to 1999 and in particular from 49 to 149 and m preferably values from 1 to 2000, in particular from 1 to 10. These silicones are referred to as amodimethicones according to the INCI declaration.

Regardless of which amino-functional silicones are used, preference is given to cosmetic formulations according to the invention which contain an amino-functional silicone whose amine number is above 0.25 meq / g, preferably above 0.3 meq / g and in particular above 0.4 meq / g is. The amine number stands for the milliequivalents of amine per gram of the amino-functional silicone. It can be determined by titration and also expressed in mg KOH / g.

Cosmetic preparations preferred according to the invention are characterized in that, based on their weight, they contain 0.01 to 10% by weight, preferably 0.1 to 8% by weight, more preferably 0.25 to 7.5% by weight and in particular 0 , 5 to 5 wt.% Of amino-functional silicone (s).

The cyclic dimethicones designated as INCY CYCLOM ETH ICON E are also preferably used according to the invention. Here, cosmetic preparations according to the invention are preferred which contain at least one silicone of the formula III

in which x is a number from 4 to 200, preferably from 5 to 10, more preferably from 6 to 7 and in particular 5, 6, 7, 8 and 9.

The silicones described above have a backbone composed of -Si-O-Si units. Of course, these Si-O-Si units may also be interrupted by carbon chains. Appropriate molecules are accessible by chain extension reactions and are preferably used in the form of silicone-in-water emulsions. These silicone-in-water emulsions which can be used according to the invention can be prepared by known processes, as disclosed, for example, in US Pat. No. 5,998,537. In summary, this method of preparation comprises the emulsifying mixture of components, one of which contains at least one polysiloxane, the other of which contains at least one organosilicone material which reacts with the polysiloxane in a chain extension reaction, with at least one metal ion-containing catalyst for the chain extension reaction, at least one surfactant and water present are. Chain extension reactions with polysiloxanes are known and may include, for example, the hydrosilylation reaction in which an Si-H group having an aliphatically unsaturated group in the presence of a platinum / rhodium catalyst to form polysiloxanes having some Si (C) _P- Si bonds (p = 1-6), the polysiloxanes also being referred to as polysiloxane-polysilalkylene copolymers.

The chain extension reaction may also include the reaction of an Si-OH group (e.g., a hydroxy-terminated polysiloxane) with an alkoxy group (e.g., alkoxysilanes, silicates, or alkoxysiloxanes) in the presence of a metal-containing catalyst to form polysiloxanes.

The polysiloxanes used in the chain extension reaction comprise a substantially linear polymer of the following structure: R-Si (R ₂ JIO-Si (R ₂ Hn-O-SiR ₃

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

The polysiloxanes may be branched to a low degree (for example, <2 mol% of the siloxane units), but the polymers are preferably substantially linear, more preferably completely linear. In addition, the substituents R may be substituted in their own right, for example with N-containing groups (for example amino groups), epoxy groups, S-containing groups, Si-containing groups, O-containing groups, etc. Preferably, at least 80% of the radicals R are alkyl radicals, especially preferably methyl groups.

The organosilicone material that reacts with the polysiloxane in the chain extension reaction can be either a second polysiloxane or a molecule that acts as a ketene extender. When the organosilicon material is a polysiloxane, it has the above-mentioned general structure. In these cases, one polysiloxane in the reaction has (at least) one reactive group, and a second polysiloxane has (at least) a second reactive group that reacts with the first.

If the organosilicone material comprises a chain extender agent, it may be a material such as a silane, a siloxane (e.g. disiloxane or trisiloxane) or a silazane. Thus, for example, a composition comprising a polysiloxane according to the comprising at least one Si-OH group, are chain extended by reacting with an alkoxysilane (for example, a dialkoxysilane or trialkoxysilane) in the presence of tin or titanium-containing catalysts. The metal-containing catalysts in the chain extension reaction are usually specific for a particular reaction. Such catalysts are known in the art and include, for example, metals such as platinum, rhodium, tin, titanium, copper, lead, etc. In a preferred chain extension reaction, a polysiloxane having at least one aliphatically unsaturated group, preferably an end group, is reacted with an organosilicone material Presence of a hydrosilylation catalyst which is a siloxane or polysiloxane having at least one (preferably terminal) Si-H group. The polysiloxane has at least one aliphatically unsaturated group and satisfies the general formula given above in which R and n are as defined above, with an average of between 1 and 2 groups R having one aliphatically unsaturated group per polymer. Representative aliphatic unsaturated groups are, for example, vinyl, allyl, hexenyl and cyclohexenyl or a group R ² CH = CHR ³ in which R ^{2 is} a divalent aliphatic silicon-bonded chain and R ^{3 is} a hydrogen atom or an alkyl group. The organosilicone material having at least one Si-H group preferably has the above-mentioned structure, wherein R and n are as defined above and wherein, on average, between 1 and 2 groups R is hydrogen and n is 0 or a positive integer. This material may be a polymer or a low molecular weight material such as a siloxane (for example, a disiloxane or a trisiloxane). The polysiloxane having at least one aliphatic unsaturated group and the organosilicone material having at least one Si-H group react in the presence of a hydrosilylation catalyst. Such catalysts are known in the art and include, for example, platinum and rhodium-containing materials. The catalysts may take any known form, for example platinum or rhodium coated on support materials (such as silica gel or activated carbon) or other suitable compounds such as platinum chloride, salts of platinum or chloroplatinic acids. Chloroplatinic acid is either a commercially available hexahydrate or in anhydrous form because of the good dispersibility in Organosili- consystemen and the slight color changes preferred catalyst. In a further preferred chain extension reaction, a polysiloxane having at least one Si-OH group, preferably an end group, is reacted with an organosilicone material having at least one alkoxy group, preferably a siloxane having at least one Si-OR group or an alkoxysilane having at least two alkoxy groups. In this case, the catalyst used is again a metal-containing catalyst.

In addition, the silicone-in-water emulsions preferably contain at least one surfactant.

Cosmetic preparations which are likewise preferred according to the invention are characterized in that they contain at least one silicone of the formula IV R ₃ Si [O-SiR ₂ ] χ- (CH ₂ ) _n - [O-SiR ₂ ] _y -O-SiR ₃ (IV),

in which R is identical or different radicals from the group -H, -phenyl, -benzyl, -CH ₂ -CH (CH ₃ ) Ph, the Ci. ₂₀ -alkyl radicals, preferably -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ J ₂ , -CH ₂ CH ₂ CH ₂ H ₃ , -CH ₂ CH (CH ₃ ) ₂ , -CH (CH ₃ ) CH ₂ CH ₃ , -C (CHa) ₃ , x and y is a number from 0 to 200, preferably from 0 to 10, more preferably from 0 to 7 and in particular 0, 1 , 2, 3, 4, 5 or 6, and n is a number from 0 to 10, preferably from 1 to 8 and in particular from 2, 3, 4, 5, 6.

The silicones are preferably water-soluble. Cosmetic preparations preferred according to the invention are characterized in that they additionally contain a water-soluble silicone.

The cosmetic compositions according to the invention can also be formulated as hair colorants. The term dyeing process comprises all processes known to the person skilled in the art in which a colorant is applied to the hair, which may have been moistened, and which is left on the hair either for a period of a few minutes to about 45 minutes and then water or a surfactant-containing Rinse the middle or leave completely on the hair.

As already mentioned above, it is possible within the scope of the teaching according to the invention to incorporate the hexenyl or cinnamyl-silicic acid esters directly into the dyeing or toning agents. The composition of the dyeing or tinting agent is not subject to any fundamental restrictions.

As a dye (precursor) e can

Developer and coupler type oxidation dye precursors,

Natural and synthetic direct dyes and

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

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

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

As coupler components m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones, m-aminophenols and substituted pyridine derivatives are generally used.

In particular α-naphthol, 1, 5, 2,7- and 1, 7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 2,4 are suitable as coupler substances -Diaminophenoxyethanol, 2-amino-4- (2-hydroxyethylamino) -anisole (Lehmann's Blue), 1-phenyl-3-methyl-pyrazol-5-one, 2,4-dichloro-3-aminophenol, 1, 3-bis - (2,4-diamino-phenoxy) -propane, 2-chlororesorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methyl-resorcinol, 5-methylresorcinol, 3-amino-6-methoxy 2-methylaminopyridine and 3,5-diamino-2,6-dimethoxypyridine.

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

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

Developer and / or coupler type oxidation dye precursors, and

Precursors of natural analog dyes, such as indole and indoline derivatives, and mixtures of representatives of these groups.

In a first preferred embodiment, the agents according to the invention contain at least one developer component. The developer components are usually primary aromatic amines having a further, in the para or ortho position, free or substituted hydroxy or amino group, diaminopyridine derivatives, heterocyclic hydrazones, 4-Aminopyr- azolderivate and 2,4,5,6-tetraaminopyrimidine and its Derivatives used.

It may be preferred according to the invention to use as the developer component a p-phenylenediamine derivative or one of its physiologically tolerable salts. Particular preference is given to p-phenylenediamine derivatives of the formula (E1)

in which

G ¹ represents a hydrogen atom, a C ₁ - to C ₄ -alkyl radical, a C ₁ - to C ₄ -monohydroxy- alkyl radical, a C ₂ - to C ₄ -polyhydroxyalkyl radical, a (C ₁ - to C ₄ J -alkoxy - (C ₁ - to C ₄ ) -alkyl radical, a 4'-aminophenyl radical or a C ₁ - to C ₄ -alkyl radical which is substituted by a nitrogen-containing group, a phenyl or a 4'-aminophenyl radical; G ² is a hydrogen atom, a C ₁ - to C ₄ -alkyl radical, a C ₁ - to C ₄ -monohydroxyalkyl radical, a C ₂ - to C ₄ -polyhydroxyalkyl radical, a (C ₁ - to C ₄ -alkyl-) C ₁ - to C ₄ ) -alkyl radical or a C ₁ - to C ₄ -alkyl radical which is substituted by a nitrogen-containing group; G ³ is a hydrogen atom, a halogen atom, such as a chlorine, bromine, iodine radical or fluorine atom, a C ₁ - to C ₄ alkyl, C ₁ - to C ₄ monohydroxyalkyl radical, a C ₂ - to C ₄ - polyhydroxyalkyl radical, a C ₁ - to C ₄ -Hydroxyalkoxyrest, a C ₁ - to C ₄ -Acetylaminoalk- oxyrest, a C ₁ - to C ₄ - Mesylaminoalkoxyrest or a C ₁ - to C ₄ -Carbamoylaminoalk- oxyrest;

G ⁴ represents a hydrogen atom, a halogen atom or a C ₁ - to C ₄ -alkyl radical or when G ³ and G ⁴ are ortho to each other, they may together form a bridging α, ω-alkylenedioxy group, such as, for example, an ethylenedioxy group.

Examples of the C ₁ - to C ₄ -alkyl radicals mentioned as substituents in the compounds according to the invention are the groups methyl, ethyl, propyl, isopropyl and butyl. Ethyl and methyl are preferred alkyl radicals. C ₁ -C ₄ -alkoxy radicals which are preferred according to the invention are, for example, a methoxy or an ethoxy group. Furthermore, as preferred examples of a C ₁ - to C ₄ -hydroxyalkyl group, a hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group may be mentioned. A 2-hydroxyethyl group is particularly preferred. A particularly preferred C ₂ to C ₄ polyhydroxyalkyl group is the 1, 2-dihydroxy ethyl group. Examples of halogen atoms are according to the invention F, Cl or Br atoms, Cl atoms are very particularly preferred. The other terms used are derived according to the invention from the definitions given here. Examples of nitrogen-containing groups of the formula (E1) are in particular the amino groups, C ₁ to C ₄ monoalkylamino groups, C ₁ to C ₄ dialkylamino groups, C ₁ to C ₄ trialkylammonium groups, C ₁ to C ₄ Monohydroxyalkylamino groups, imidazolinium and ammonium. Particularly preferred p-phenylenediamines of the formula (E1) are selected from p-phenylenediamine, p-toluenediamine, 2-chloro-p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine , 2,6-diethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, N, N-dipropyl-p-phenylenediamine, 4 -Amino-3-methyl- (N, N-diethyl) -aniline, N, N-bis- (β-hydroxyethyl) -p-phenylenediamine, 4-N, N-bis (β-hydroxyethyl) amino- 2-methylaniline, 4-N, N-bis (β-hydroxyethyl) amino-2-chloroaniline, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- (α, β-dihydroxyethyl) -p-phenylenediamine, 2 Fluoro-p-phenylenediamine, 2-isopropyl-p-phenylenediamine, N- (β-hydroxypropyl) -p-phenylenediamine, 2-hydroxymethyl-p-phenylenediamine, N, N-dimethyl-3-methyl-p phenylenediamine, N, N- (ethyl, β-hydroxyethyl) -p-phenylenediamine, N- (β, γ-dihydroxypropyl) -p-phenylenediamine, N- (4'-aminophenyl) -p-phenylenediamine, N-phenyl- p-phenylenediamine, 2- (β-hydroxyethyloxy) -p-phenylenediamine, 2- (β-ace tylaminoethyloxy) -p-phenylenediamine, N- (.beta.-methoxyethyl) -p-phenylenediamine and 5,8-diaminobenzo-1, 4-dioxane and their physiologically acceptable salts.

Very particular preferred p-phenylenediamine derivatives of the formula (E1) according to the invention are p-phenylenediamine, p-toluenediamine, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- (α, β-dihydroxyethyl) -p-phenylenediamine and N, N bis (.beta.-hydroxyethyl) -p-phenylenediamine.

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

Among the binuclear developer components which can be used in the compositions according to the invention, mention may be made in particular of the compounds which correspond to the following formula (E2) and their physiologically tolerated salts:

in which:

Z ¹ and Z ² independently of one another represent a hydroxyl or NH ₂ -ReSt which is optionally substituted by a C 1 -C ₄ -alkyl radical, by a C 1 to C ₄ -hydroxyalkyl radical and / or the bridge Y is an alkylene group having 1 to 14 carbon atoms, such as a linear or branched alkylene chain or an alkylene ring, of one or more nitrogen-containing groups and / or a or a plurality of heteroatoms such as oxygen, sulfur or nitrogen atoms may be interrupted or terminated and may optionally be substituted by one or more hydroxyl or C ₁ - to C ₈ -alkoxy radicals, or a direct bond,

G ⁵ and G ⁶ independently of one another represent a hydrogen or halogen atom, a C ₁ - to C ₄ -alkyl radical, a C ₁ - to C ₄ -monohydroxyalkyl radical, a C ₂ - to C ₄ - polyhydroxyalkyl radical, a C ₁ - to C ₄ -Aminoalkylrest or a direct connection to the bridge Y, G ⁷ , G ⁸ , G ⁹ , G ¹⁰ , G ¹¹ and G ¹² are independently a hydrogen atom, a direct bond to the bridge Y or a C ₁ - C ₄ -Alkylrest, with the provisos that the compounds of formula (E2) contain only one bridge Y per molecule and the compounds of formula (E2) contain at least one amino group which carries at least one hydrogen atom.

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

Preferred binuclear developer components of the formula (E2) are in particular: N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diamino-propan-2-ol, N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) ethylenediamine, N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis - (.beta.-hydroxyethyl) -N, N'-bis (4-aminophenyl) -tetramethylenediamine, N, N'-bis (4-methyl-aminophenyl) -tetramethylenediamine, N, N'-diethyl-N, N ¹ bis (4'-amino-3 ^l -methylphenyl) ethylenediamine ₎ bis (2-hydroxy-5-aminophenyl) -methane, 1, 3-bis- (2,5-diaminophenoxy) -propan-2-ol , N, N'-bis (4'-amino-phenyl) -1, 4-diazacycloheptane, N, N'-bis (2-hydroxy-5-aminobenzyl) -piperazine, N- (4'-aminophenyl) - P-phenylenediamine and 1, 10-bis- (2 ', 5 ^l -diaminophenyl) -1, 4,7,10-tetraoxadecan and their physiologically acceptable salts.

Very particularly preferred binuclear developer components of the formula (E2) are N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diamino-propan-2-ol, Bis (2-hydroxy-5-aminophenyl) methane, 1, 3-bis- (2,5-diaminophenoxy) -propan-2-ol, N, N'-bis (4'-aminophenyl) - 1,4-diazacycloheptane and 1,1'-bis-bis-aminophenyl O-1-aminoethyl-tetraoxadecane or one of their physiologically acceptable salts. Furthermore, it may be preferred according to the invention to use as the developer component a p-aminophenol derivative or one of its physiologically tolerable salts. Particular preference is given to p-aminophenol derivatives of the formula (E3)

in which:

G ¹³ represents a hydrogen atom, a halogen atom, a C ₁ - to C ₄ -alkyl radical, a C ₁ - to C ₄ -monohydroxyalkyl radical, a C ₂ - to C ₄ -polyhydroxyalkyl radical, a (C ₁ - to C ₄ ) -alkoxy radical (C ₁ - to C ₄₎ alkyl group a d- to C ₄ aminoalkyl radical, a hydroxy (Cr to _C4) alkylamino radical, a C ₁ - to C ₄ -Hydroxyalkoxyrest, a C ₁ - to C ₄ -Hydroxyalkyl- (C ₁ -C ₄ ) -aminoalkyl radical or a (di-C ₁ -C ₄ -alkylaminoHCr to C ₄ ) -alkyl radical, and

G ¹⁴ represents a hydrogen or halogen atom, a C ₁ - to C ₄ alkyl, C ₁ - to C ₄ - monohydroxyalkyl radical, a C ₂ - to C ₄ polyhydroxyalkyl radical, a (C ₁ - to C ₄ J- AIkOXy- (C ₁ - to C ₄ ) -alkyl radical, a C ₁ - to C ₄ -Aminoalkylrest or a C ₁ - to C ₄ -Cyanoalkylrest,

G ¹⁵ is hydrogen, C ₁ - to C ₄ -alkyl, C ₁ - to C ₄ -monohydroxyalkyl, C ₂ - to C ₄ -polyhydroxyalkyl, phenyl or benzyl, and

G ¹⁶ is hydrogen or a halogen atom.

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

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

Very particularly preferred compounds of the formula (E3) are p-aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (α, β-dihydroxyethyl) -phenol and 4-amino 2- (diethylaminomethyl) -phenol. Further, the developer component may be selected from o-aminophenol and its derivatives such as 2-amino-4-methylphenol, 2-amino-5-methylphenol or 2-amino-4-chlorophenol.

Further, the developer component may be selected from heterocyclic developer components such as the pyridine, pyrimidine, pyrazole, pyrazole pyrimidine derivatives and their physiologically acceptable salts.

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

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

Preferred pyrazole derivatives are in particular 4,5-diamino-1-methylpyrazole, 4,5-diamino-1- (β-hydroxyethyl) pyrazole, 3,4-diaminopyrazole, 4,5-diamino-1- (4'- chlorobenzyl) pyrazole, 4,5-diamino-1, 3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino 1, 3-dimethyl-5-hydrazinopyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1-methylpyrazole, 4,5-diamino 1-tert-butyl-3-methylpyrazole, 4,5-diamino-1- (β-hydroxyethyl) -3-methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1 ethyl 3- (4'-methoxyphenyl) pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxy-methyl-1-methylpyrazole, 4,5-diamino 3-hydroxymethyl-1-isopropylpyrazole, 4,5-diamino-3-methyl-1-isopropylpyrazole, 4-amino-5- (D-aminoethyl) amino-1,3-dimethylpyrazole, 3,4,5-triaminopyrazole, 1 -Methyl-3,4,5-triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole and 3,5-diamino-4- (β-hydroxyethyl) amino-i-methylpyrazole.

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

D- to C ₄ alkyl radical, an aryl radical, a hydroxyalkyl radical to C _4, a C ₂ - - G ^17, G ^18, G ¹⁹ and G ²⁰ are independently a hydrogen atom, a C ₁ to C ₄ - Polyhydroxyalkylrest a (C ₁ - to C ₄ J-AIkOXy- (C ₁ - to C ₄ ) -alkyl radical, a C ₁ - to C ₄ -Aminoalkylrest, optionally protected by an acetyl-ureide or a sulfonyl radical may be a (C ₁ - to C ₄ ) -alkylamino- (C ₁ - to C ₄ ) -alkyl radical, a di-I (C ₁ - to C ₄ ) -alkyl] - (C ₁ - to C ₄ ) - aminoalkyl radical, wherein the dialkyl radicals optionally form a carbon cycle or a heterocycle having 5 or 6 chain members, a C ₁ - to C ₄ -hydroxyalkyl- or a di- (C ₁ - to C ₄ ) - [hydroxyalkyl] - (Cr to C ₄ ) -aminoalkyl radical, the X radicals independently of one another represent a hydrogen atom, a C ₁ - to C ₄ -alkyl radical, an aryl radical, a C ₁ - to C ₄ -hydroxyalkyl radical, a C ₂ - bis C ₄ - polyhydroxyalkyl radical, a C ₁ - to C ₄ -Aminoalkylr est, a (C ₁ - to C ₄ ) -alkylamino- (C _! - to C ₄ ) -alkyl radical, a di-I (C ₁ - to C ₄ ) alkyl] - (C ₁ - to C ₄ ) -aminoalkyl radical, wherein the dialkyl radicals optionally have a carbon cycle or a heterocycle having 5 or 6 chain members , form a C ₁ - aminoalkyl radical, an amino radical, a C ₁ - to C ₄ hydroxyalkyl or a di- (to C ₄ hydroxyalkyl C ₁₎ - to C ₄ -alkyl- or di- (C ₁ - to C ₄ -hydroxyalkyl) amino, a halogen atom, a carboxylic acid group or a sulfonic acid group, i has the value 0, 1, 2 or 3, p has the value 0 or 1, q has the value 0 or 1 and n has the value 0 or 1 with the proviso that the sum of p + q is not equal to 0 when p + q is 2, n is 0, and the groups NG ¹⁷ G ¹⁸ and NG ¹⁹ G ²⁰ occupy the positions (2,3) ; (5,6); (6,7); (3,5) or (3,7); when p + q is 1, n is 1, and the groups NG ¹⁷ G ¹⁸ (or NG ¹⁹ G ²⁰ ) and the group OH occupy the positions (2, 3); (5,6); (6,7); (3,5) or (3,7);

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

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

Among the pyrazolo [1, 5-a] -pyrimidines of the above formula (E4) may be mentioned in particular:

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

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

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

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

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

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

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

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

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

2 - [(7-aminopyrazolo [1,5-a] pyrimidin-3-yl) - (2-hydroxy-ethyl) amino] -ethanol;

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

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

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

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

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

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

Preferred coupler components according to the invention are m-aminophenol and its derivatives such as, for example, 5-amino-2-methylphenol, N-cyclopentyl-3-aminophenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol,

2,6-dimethyl-3-aminophenol, 3-trifluoroacetylamino-2-chloro-6-methylphenol, 5-amino-4-chloro

2-methylphenol, 5-amino-4-methoxy-2-methylphenol, 5- (2'-hydroxyethyl) amino-2-methylphenol, 3- (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 ^l, 4'-diaminophenoxy) -propane, 1-methoxy-2-amino-4- (2'-hydroxyethylamino) benzene, 1, 3-

Bis- (2 ', 4 ¹ -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, for example, resorcinol, resorcinol monomethyl ether, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2-chlororesorcinol, 4-

Chlororesorcinol, pyrogallol and 1,2,4-trihydroxybenzene,

Pyridine derivatives such as 2,6-dihydroxypyridine, 2-amino-3-hydroxypyridine, 2-amino

5-chloro-3-hydroxypyridine, 3-amino-2-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, for example, 6-hydroxybenzomorpholine and 6-aminobenzomorpholine,

Quinoxaline derivatives such as 6-methyl-1,2,3,4-tetrahydroquinoxaline,

Pyrazole derivatives such as 1-phenyl-3-methylpyrazol-5-one,

Indole derivatives such as 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole,

Pyrimidine derivatives such as 4,6-diaminopyrimidine, 4-amino-2,6-dihydroxypyrimidine,

2,4-diamino-6-hydroxypyrimidine, 2,4,6-trihydroxypyrimidine, 2-amino-4-methylpyrimidine, 2-

Amino-4-hydroxy-6-methylpyrimidine and 4,6-dihydroxy-2-methylpyrimidine, or

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

Amino-3,4-methylenedioxybenzene and 1- (2'-hydroxyethyl) amino-3,4-methylenedioxybenzene. Particularly preferred coupler components according to the invention 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.

As precursors of naturally-analogous dyes such indoles and indolines are preferably used which have at least one hydroxy or amino group, preferably as a substituent on the six-membered ring. These groups may carry further substituents, e.g. Example in the form of etherification or esterification of the hydroxy group or alkylation of the amino group. In a second preferred embodiment, the agents contain at least one indole and / or indoleindehvate.

Particularly suitable precursors of naturally-analogous hair dyes are derivatives of 5,6-dihydroxyindoline of the formula (IIIa),

I ¹ (purple) in the independently

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

R ² is hydrogen or a -COOH group, wherein the -COOH group may also be present as a salt with a physiologically compatible cation,

R ³ is hydrogen or a C _r C ₄ alkyl group,

R ⁴ is hydrogen, a Ci-C ₄ alkyl group or a group -CO-R ⁶ , in which R ⁶ is a CVCj-alkyl group, and

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

Particularly preferred derivatives of indoline are 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxy-indoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5, 6-dihydroxyindoline, 5,6-dihydroxyindoline-2-carboxylic acid and 6-hydroxyindoline, 6-aminoindoline and 4-aminoindoline.

Particularly noteworthy within this group are N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline and especially 5,6 -Dihydroxyindolin. Also suitable as precursors of naturally-analogous hair dyes are derivatives of the 5,6-dihydroxyindole of the formula (IIIIB)

in the independently of each other

R ¹ is hydrogen, a C _r C ₄ alkyl group or a Ci-C ₄ -hydroxyalkyl group,

R ³ is hydrogen or a C ¹ -C 6 alkyl group,

R ⁴ is hydrogen, a C 1 -C 4 alkyl group or a group -CO-R ⁶ , in which R ⁶ is a C 1 -C ₄ alkyl group, and

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

The indoline and indole derivatives can be used in the agents used in the process according to the invention both as free bases and in the form of their physiologically acceptable salts with inorganic or organic acids, eg. As the hydrochlorides, sulfates and hydrobromides are used. The indole or indoline derivatives are contained therein usually in amounts of 0.05-10 wt .-%, preferably 0.2-5 wt .-%.

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

Preferred agents according to the invention are characterized in that they contain at least one dye precursor from the groups of the aromatic and heteroaromatic diamines, aminophenols, naphthols, polyphenols CH-acidic coupler components and their derivatives in quantities from 0.01 to 25 wt.%, Preferably from 0.5 to 10 wt.%, In particular from 1 to 5 wt .-%, each based on the total agent.

In addition to the oxidation dye precursor (s), formulation (A) may contain one or more substantive dyes for shade. Direct dyes are usually nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols. Preferred substantive dyes are those having the international designations or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, Acid Yellow 1, Acid Yellow 10, Acid Yellow 23, Acid Yellow 36, HC Orange Disperse Orange 3, Acid Orange 7, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, Acid Red 33, Acid Red 52, HC Red BN, Pigment Red 57: 1, HC Blue 2, HC Blue 12, Disperse Blue 3, Acid Blue 7, Acid Green 50, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Acid Violet 43, Disperse Black 9, Acid Black 1, and Acid Black 52 known compounds as well as 1 , 4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1, 4-bis (β-hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- (β-hydroxyethyl) aminophenol , 2- (2'-hydroxyethyl) amino-4,6-dinitrophenol, 1- (2'-hydroxyethyl) amino-4-methyl-2-nitrobenzene, 1-amino-4- (2'-hydroxyethyl) amino-5 -chloro-2-nitrobenzene, 4-amino-3-nitro-phenol, 1- (2'-ureidoethyl) amino-4-nitrobenzene, 4-amino-2-nitrodiphenylamine-2'-car bonsäure, 6-nitro-1, 2,3,4-tetrahydroquinoxaline, 2-hydroxy-1, 4-naphthoquinone, picramic acid and its salts, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3 nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene.

Corresponding agents according to the invention, which are characterized in that they contain at least one substantive dye from the group of cationic (basic) dyes, preferably Basic Blue 6, Cl-No. 51, 175; Basic Blue 7, Cl-No. 42.595; Basic Blue 9, Cl-No. 52.015; Basic Blue 26, Cl-No. 44.045; Basic Blue 41, Cl-No. 11, 154; Basic Blue 99, Cl-No. 56.059; Basic Brown 4, Cl-No. 21, 010; Basic Brown 16, Cl-No. 12.250; Basic Brown 17, Cl- No. 12,251; Basic Green 1, Cl-No. 42.040; Basic Orange 31; Basic Red 2, Cl-No. 50.240; Basic Red 22, Cl-No. 11, 055; Basic Red 46; Basic Red 51; Basic Red 76, Cl-No. 12.245; Basic Violet 1, Cl-No. 42.535; Basic Violet 2; Basic Violet 3, Cl-No. 42.555; Basic Violet 10, Cl-No. 45.170; Basic Violet 14, Cl-No. 42.510; Basic Yellow 57, Cl-No. 12.719; Basic Yellow 87 and / or the anionic (acidic) dyes, and / or the nonionic dyes, preferably Acid Black 1, Cl-No. 20.470; Acid Black 52; Acid Blue 7; Acid Blue 9, Cl-No. 42.090; Acid Blue 74, Cl-No. 73.015, Acid Red 18, Cl-No. 16.255; Acid Red 23; Acid Red 27, Cl-No. 16.185; Acid Red 33; Acid Red 52; Acid Red 87, Cl-No. 45,380; Acid Red 92, Cl-No. 45,410; Acid Orange 3; Acid Orange 7; Acid Violet 43, Cl-No. 60.730; Acid Yellow 1, Cl-No. 10.316; Acid Yellow 10; Acid Yellow 23, Cl-No. 19,140; Acid Yellow 3, Cl-No. 47.005; Acid Yellow 36; D & C Brown no. 1, Cl-No. 20.170 (Acid Orange 24); D & C Green no. 5, Cl-No. 61, 570 (Acid Green G); D & C Orange No. 4, Cl-No. 15.510 (Acid Orange II); D & C Orange No. 10, CI-No. 45.425: 1 (Solvent Red 73); D & C Orange No. 11, Cl-No. 45.425 (Acid Red 95); D & C Red No. 21, Cl-No. 45.380: 2 (Solvent Red 43); D & C Red No. 27, Cl-No. 45.410: 1 (Solvent Red 48); D & C Red No. 33, Cl-No. 17,200 (Acid Red 2A, Acid Red B); D & C Yellow No. 7, CI-No. 45.350: 1 (Solvent Yellow 94); D & C Yellow No. 8, Cl-No. 45,350 (Acid Yellow 73); FD & C Red No. 4, Cl-No. 14,700 (Food Red 4); FD & C Yellow No. 6, Cl-No. 15,985 (Food Yellow 3); Food Green 3; Pigment Red 57-1; Disperse Black 9; Disperse Blue 1; Disperse Blue 3; Disperse Violet 1; Disperse Violet 4; HC Orange 1; HC Red 1; HC Red 3; HC Red 13; HC Yellow 2; HC Yellow 4; Na-Pikramat; 1, 4-bis (2 ^{'-hydroxyethyl)} amino-2-nitro-p-phenylenediamine; HC Yellow 5; HC Blue 2; HC Blue 12; 4-amino-3-nitrophenol; HC Yellow 6; HC Yellow 12; 2-Nitro-1- (2 ^{'hydroxyethyl)} amino-4-methyl benzene; 2-nitro-4-amino-diphenylamine-2-carboxylic acid; 2-amino-6-chloro-4-nitrophenol; HC Red BN; 6-nitro-1,2,3,4-tetranitroquinoxaline; o-nitro-p-phenylenediamine; p-nitro-m-phenylenediamine; HC Red B 54; HC Red 10; HC Red 11; HC Red 13; 2- (2 ^{'-hydroxyethyl)} amino-1-hydroxy-4,6-dinitrobenzene; 4-ethylamino-3-nitrobenzoic acid; 2-chloro-6-ethylamino-4-nitrophenol; 2-hydroxy-1,4-naphthoquinone; 1-propene (4-amino-2-nitrophenyl) amine; isatin; N-methylylisatin; HC Violet 1; HC Violet 2; 4-Nitrophenyl-aminoethyl urea in amounts of 0.01 to 25 wt.%, Preferably from 0.5 to 10 wt.%, In particular from 1 to 5 wt .-%, each based on the total agent included, are preferred embodiments of the present invention.

Among the above-mentioned dyes, some representatives are particularly preferred, for which reason further preferred agents according to the invention, characterized in that they comprise at least one direct drawler selected from Basic Blue 7, Basic Blue 99, Basic Violet 14, Basic Brown 16, Basic Brown 17, Basic Orange 31, Basic Red 46, Basic Red 51, Basic Red 76, Basic Yellow 57, Basic Yellow 87, Acid Black 1, Acid Blue 7, Acid Violet 43, Acid Red 23, Acid Red 52, Acid Orange 7, Acid Yellow Disperse Blue 1, Disperse Blue 3, Disperse Violet 1, Disperse Violet 4, HC Orange 1, HC Red 1, HC Red 1, Acid Yellow 10, Acid Yellow 36, Food Green 3, Pigment Red 57-1, Disperse Black 9, Disperse Blue 1 3, HC Red 13, HC Yellow 2, HC Yellow 4, Na-Pikramat, 1, 4-bis (2 ^'- hydroxyethyl) amino-2-nitro-p-phenylenediamine, HC Yellow 5, HC Blue 2, HC Blue 12, 4-amino-3-nitrophenol, HC Yellow 6, HC Yellow 12, 2-nitro-1- (2 ^{'hydroxyethyl)} amino-4-methyl benzene, 2-nitro-4-amino-diphenylamine-2-carboxylic acid, 2 -6- chloro-4-nitrophenol, HC Red BN; 6-nitro-1,2,3,4-tetranitroquinoxaline, o-nitro-p-phenylenediamine, p-nitro-m-phenylenediamine, HC Red B 54, HC Red 10, HC Red 11, HC Red 13, 2- 2 ^{'-hydroxyethyl)} amino-1-hydroxy-4,6-dinitrobenzene, 4-ethylamino-3-nitrobenzoic acid, 2-chloro-6-ethylamino-4-nitrophenol, 2-hydroxy-1, 4-napthochi- non, 1 Propene (4-amino-2-nitrophenyl) amine, Isatin, N-Methylylisatin, HC Violet 1, HC Violet 2, 4-Nitrophenyl-aminoethyl urea in amounts of 0.01 to 25 wt.%, Preferably of 0.5 - 10 wt.%, In particular from 1 to 5 wt .-%, each based on the total agent, contain, are preferred.

Furthermore, the agents according to the invention may contain a cationic substantive dye. Particularly preferred are

(a) cationic triphenylmethane dyes such as Basic Blue 7,

Basic Blue 26, Basic Violet 2 and Basic Violet 14, (b) aromatic systems substituted with a quaternary nitrogen group, such as Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 and Basic Brown 17, as well as

(C) substantive dyes containing a heterocycle having at least one quaternary nitrogen atom, as mentioned for example in EP-A2-998 908, which is explicitly referred to at this point, are claimed in claims 6 to 11.

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

CH ₃ SO ₄

Cl ^"

The compounds of the formulas (DZ1), (DZ3) and (DZ5), which are also known by the names Basic Yellow 87, Basic Orange 31 and Basic Red 51, are very particularly preferred cationic substantive dyes of group (c). The cationic substantive dyes sold under the trademark Arianor are also very particularly preferred cationic substantive dyes according to the invention.

The inventively preferred compositions according to this embodiment, the substantive dyes preferably in an amount of 0.01 to 20 wt .-%, based on the total agent.

Furthermore, the preparations of the invention may also naturally occurring dyes such as henna red, henna neutral, henna black, chamomile, sandalwood, black tea, buckthorn bark, sage, bluewood, madder root, Catechu, Sedre and alkano root are included.

It is not necessary for the oxidation dye precursors or the direct dyes to be in each case homogeneous compounds. Rather, in the inventive compositions, due to the production process for the individual dyes, minor amounts of other components may be included, as far as they do not adversely affect the dyeing result or for other reasons, e.g. toxicological, must be excluded.

With regard to the useful dyes formulated according to the invention as hair dyeing and tinting agents, further explicit reference is made 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), published as volume 7 of the series "Dermatology" (Editor: Ch., Culnan and H. Maibach), published by Marcel Dekker Inc., New York, Basel, 1986.

However, according to the invention, the oxidation colorant can also be applied to the hair together with a catalyst which promotes the oxidation of the dye precursors, e.g. by atmospheric oxygen, activated. Such catalysts are e.g. Metal ions, iodides, quinones or certain enzymes.

Suitable metal ions are, for example, Zn ²⁺ , Cu ²⁺ , Fe ²⁺ , Fe ³⁺ , Mn ²⁺ , Mn ⁴⁺ , Li ⁺ , Mg ²⁺ , Ca ²⁺ and Al ³⁺ . Particularly suitable are Zn ²⁺ , Cu ²⁺ and Mn ²⁺ . The metal ions can in principle be used in the form of any physiologically acceptable salt or in the form of a complex compound. Preferred salts are the acetates, sulfates, halides, lactates and tartrates. By using these metal salts, both the formation of the dyeing can be accelerated and the color shade can be specifically influenced. Suitable enzymes include peroxidases, which can significantly enhance the effect of small amounts of hydrogen peroxide. Furthermore, such enzymes are suitable according to the invention which directly oxidize the oxidation dye precursors with the aid of atmospheric oxygen, such as, for example, the laccases, or generate small amounts of hydrogen peroxide in situ and thus biocatalytically activate the oxidation of the dye precursors. Particularly suitable catalysts for the oxidation of the dye precursors are the so-called 2-electron oxidoreductases in combination with the specific substrates, eg

Pyranose oxidase and e.g. D-glucose or galactose,

Glucose oxidase and D-glucose, glycerol oxidase and glycerin,

Pyruvate oxidase and pyruvic acid or its salts, - alcohol oxidase and alcohol (MeOH, EtOH), lactate oxidase and lactic acid and its salts, tyrosinase oxidase and tyrosine, uricase and uric acid or their salts, choline oxidase and choline, amino acid oxidase and amino acids.

Usually, coloring agents are offered as a combination pack containing a coloring cream and a separately packaged oxidizing solution. Shortly before use, both components are mixed together and the prepared mixture is applied to the hair to be dyed. The mixing ratio of the two components can be chosen freely. Conveniently, the preparation of the oxidizing agent is then mixed with the preparation with the dye precursors immediately prior to dyeing the hair. The resulting ready-to-use hair dye preparation should preferably have a pH in the range of 6 to 10. Particularly preferred is the use of the hair dye in a weakly alkaline medium. The application temperatures may range between 15 and 40 ° C, preferably at the temperature of the scalp. After a contact time of about 5 to 45, especially 15 to 30, minutes, the hair dye is removed by rinsing of the hair to be dyed. The Nachwaschen with a shampoo is omitted if a strong surfactant-containing carrier, eg. As a dyeing shampoo was used.

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

Other optional ingredients of the compositions of the invention are nonionic polymers such as vinylpyrrolidone / vinyl acrylate copolymers, polyvinylpyrrolidone and vinylpyrrolidone / vinyl acetate copolymers, anionic polymers such as polyacrylic and polymethacrylic acids in the form of their copolymers with acrylic and methacrylic acid esters and amides, polyoxycarboxylic acids such as polyketo and polyaldehydocarboxylic acids and their salts, as well as polymers and copolymers of crotonic acid with esters and amides of acrylic and methacrylic acid, such as vinyl acetate-crotonic acid and vinyl acetate-vinyl propionate-crotonic acid copolymers,

Structurants such as glucose and maleic acid, hair conditioning compounds such as phospholipids, for example soya lecithin, egg lecithin and cephalins,

Perfume oils, in particular those with the fragrance of a fruit, such as apple, pear, strawberry, peach, apricot, pineapple, banana, cherry, kiwi, mango, coconut, almond, grapefruit, passion fruit, mandarin and melon, or the fragrance of a stimulant , such as tobacco, cola, chewing gum, guarana, chocolate, cocoa, vanilla, sarsaparilla, peppermint and rum. Dimethylisosorbide and cyclodextrins,

Solubilizers, such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol, diethylene glycol and ethoxylated triglycerides, dyes,

Antidandruff active ingredients such as climbazole, piroctone olamine and zinc omadine, active ingredients such as bisabolol, allantoin, panthenol, niacinmide, tocopherol and plant extracts, light stabilizers,

Bodying agents such as sugar esters, polyol esters or polyol alkyl ethers, fats and waxes, such as spermaceti, beeswax, montan wax, paraffins, esters, glycerides and fatty alcohols, fatty acid alkanolamides,

Complexing agents such as EDTA, NTA, β-alaninediacetic acid and phosphonic acids, swelling and penetrating substances such as PCA, glycerol, propylene glycol monoethyl ether, carbonates, bicarbonates, guanidines, ureas and primary, secondary and tertiary phosphates, Opacifiers such as latex or styrene / acrylamide copolymers, pearlescing agents such as ethylene glycol mono- and distearate or PEG-3-distearate, white pigments

Reducing agents, e.g. Thioglycolic acid and its derivatives, thiolactic acid, cysteamine, thiomalic acid and α-mercaptoethanesulfonic acid,

Oxidizing agents such as hydrogen peroxide, potassium bromate and sodium bromate, propellants such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air and

antioxidants

Bitter substances such as Denatonium Benzoate,

Preservative.

With regard to the manner in which the active ingredient used according to the invention or the active compound combinations according to the invention are applied to the hair and / or to the skin, there are no fundamental restrictions. For example, creams, lotions, solutions, waters, emulsions such as W / O, O / W, PIT emulsions (called phase inversion emulsions, PIT), microemulsions and multiple emulsions, nanoemulsions, coarse, unstable, single or multi-phase shaking mixtures, gels, sprays, aerosols and foam aerosols suitable. These are usually formulated on an aqueous or aqueous-alcoholic basis. As alcoholic component while lower alkanols and polyols such as propylene glycol and glycerol are used. Ethanol and isopro panol are preferred alcohols. Water and alcohol may be present in the aqueous alcoholic base in a weight ratio of 1:10 to 10: 1. Water and aqueous-alcoholic mixtures which contain up to 50% by weight, in particular up to 25% by weight, of alcohol, based on the mixture of alcohol and water, can be preferred bases according to the invention. The pH of these preparations can in principle be between 2 and 11. It is preferably between 2 and 7, values of 3 to 6 being particularly preferred. To adjust this pH, virtually any acid or base that can be used for cosmetic purposes can be used. Usually, acids are used as acids. Acid acids are understood to mean those acids which are absorbed as part of normal food intake and have positive effects on the human organism. Exotic acids are, for example, acetic acid, lactic acid, tartaric acid, citric acid, malic acid, ascorbic acid and gluconic acid. In the context of the invention, the use of citric acid and lactic acid is particularly preferred. Preferred bases are ammonia, alkali hydroxides, monoethanolamine, triethanolamine and N, N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine.

The compositions of the invention may also be formulated as cosmetic skin treatment agents. Here are, for example, products for body cleansing such as soaps, Syndets, shower gels, bath foams, etc. in question. Also, products according to the invention which remain on the skin such as creams, lotions, sunscreens, ointments, gels, etc. can be easily formulated.

With particular preference agents according to the invention are formulated in such a way that they can be used as deodorants or antiperspirants. These compositions are also referred to collectively below as compositions for reducing body odor on the skin. Here, preferred cosmetic compositions according to the invention are those which are a means for influencing the body odor or the smell of the hair, in particular a deodorant.

The cosmetic deodorant or antiperspirant compositions may be in the form of powders, sticks, aerosol spray, pump spray, liquid and gel roll on application, cream, gel, and soaked flexible substrate.

Deodorant or antiperspirant sticks may be in gelled, anhydrous wax base and based on W / O emulsions and O / W emulsions. Gel sticks can be made on the basis of fatty acid soaps, dibenzylidene sorbitol, N-acyl amino acid amides, 12-hydroxystearic acid and other gel formers.

Aerosol sprays, pump sprays, roll on applications and creams can be used as water-in-oil emulsions, oil-in-water emulsions, silicone oil-in-water emulsions, water-in-oil microemulsions, oil-in-water emulsions. Water microemulsion, silicone oil-in-water microemulsion, anhydrous suspension, alcoholic and hydroalcoholic solution, aqueous gel and as an oil. All said compositions may be thickened, for example, based on fatty acid soaps, dibenzylidenesorbitol, N-acylamino acid amides, 12-hydroxystearic acid, carbomer and carbopol type polyacrylates, polyacrylamides and polysaccharides, which may be chemically and / or physically modified. The emulsions and microemulsions may be transparent, translucent or opaque.

The inventively preferred cosmetic deodorant or antiperspirant compositions may further contain fatty substances. Fatty substances are to be understood as meaning fatty acids, fatty alcohols, natural and synthetic cosmetic oil components as well as natural and synthetic waxes, which may be in solid or liquid form in aqueous or oily dispersion.

As fatty acids it is possible to use linear and / or branched, saturated and / or unsaturated C ₈ . ₃ o-fatty acids. Preferred are do- _22- fatty acids. Examples 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, arachidonic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures. Particularly preferred is the use of stearic acid. The fatty acids used can carry one or more hydroxyl groups. Preferred examples are the

as well as 12-hydroxystearic acid. The amount used is 0.1 to 15 wt .-%, preferably 0.5 to 10 wt .-%, particularly preferably 1 to 5 wt .-%, each based on the total composition.

As fatty alcohols it is possible to use saturated, mono- or polyunsaturated, branched or unbranched fatty alcohols having 6 to 30, preferably 10 to 22 and very particularly preferably 12 to 22 carbon atoms. Applicable according to the invention are e.g. Decanol, octanol, dodecadienol, decadienol, oleyl alcohol, eruca alcohol, ricinoleic alcohol, stearyl alcohol, isostearyl alcohol, cetyl alcohol, lauryl alcohol, myristyl alcohol, arachidyl alcohol, capryl alcohol, capric alcohol, linoleyl alcohol, linolenyl alcohol and behenyl alcohol, and the like Guerbet.

For pen formulations waxes are often used. As natural or synthetic waxes can be used according to the invention are solid paraffins or isoparaffins, plant waxes such as candelilla wax, carnauba wax, Espartograswachs, Japan wax, cork wax, sugarcane wax, ouricury wax, montan wax, sunflower wax, fruit waxes and animal waxes such. B. beeswax and other insect waxes, spermaceti, shellac wax, wool wax and raffia fat, continue to mineral waxes such. As ceresin and ozokerite or the petrochemical waxes such. As petrolatum, paraffin waxes, Microwachse of polyethylene or polypropylene and polyethylene glycol waxes. It may be advantageous to use hydrogenated or hardened waxes. Furthermore, chemically modified waxes, especially the hard waxes, z. As montan ester waxes, Sasol waxes and hydrogenated jojoba waxes, can be used.

Also suitable are the triglycerides of saturated and optionally hydroxylated C _1β . ₃ o-fatty acids, such as. B. hydrogenated triglyceride fats (hydrogenated palm oil, hydrogenated coconut oil, hydrogenated castor oil), glyceryl hydroxystearate or glyceryl tri-12-, further (eg Syncrowachs ^®.) Synthetic Vollester of fatty acids and glycols or polyols containing 2 - 6 carbon atoms, fatty acid monoalkanolamides with a C _{_12-22} acyl radical and a C _{_2-4} alkanol, esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids having a chain length of 1 to 80 carbon atoms and saturated and / or unsaturated, branched and / or unbranched alcohols of a chain length of 1 to 80 carbon atoms, including z. Example, synthetic fatty acid fatty alcohol esters such as stearyl stearate or cetyl palmitate, esters of aromatic carboxylic acids, dicarboxylic acids or hydroxycarboxylic acids (eg., 12-Hydroxystearinsäure) and saturated and / or unsaturated, branched and / or unbranched alcohols of a chain length of 1 to 80 C-atoms, lactides of long-chain hydroxycarboxylic acids and full esters of fatty alcohols and di- and tricarboxylic acids, eg. As dicetylsuccinate or dicetyl / stearyl adipate, as well as mixtures of these substances, provided that the individual wax components or their mixture are solid at room temperature.

It is particularly preferred to choose the wax components from the group of esters of saturated, unbranched alkanecarboxylic acids having a chain length of 14 to 44 carbon atoms and saturated, unbranched alcohols of a chain length of 14 to 44 carbon atoms, provided the wax component or the entirety of the wax components are solid at room temperature. Particularly advantageous, the wax components from the group of C ₁₆ . ₃₆ alkyl stearates, C ₁₀ - ₄₀ alkyl stearates, C _2-4 o-alkyl isostearates, C _20-40 dialkyl esters of dimer acids, C _18-38 alkyl hydroxystearoyl stearates, C ₂ o ₄ o alkyl erucates are chosen, furthermore C ₃₀ . ₅₀ alkyl beeswax and Cetearylbehenat used. Silicone waxes, for example stearyltrimethylsilane / stearyl alcohol, may also be advantageous. Particularly preferred wax components are the esters of saturated, monohydric C ₂₀ -C ₆₀ alcohols, and saturated C ₈ -C ₃₀ - monocarboxylic acids, in particular a C ₂₀ -C ₄₀ alkyl preferred, the Keunen under the name ^® Kesterwachs K82H by the company Koster Inc. is available. The wax or the wax components should be solid at 25 ° C, but in the range of 35 - 95 ° C to melt, with a range from 45 to 85 ⁰ C is preferred.

Natural, chemically modified and synthetic waxes may be used alone or in combination. The wax components are preferably contained in an amount of 0.1 to 40 wt .-%, based on the total composition, preferably 1 to 30 wt .-% and in particular 5 - 15 wt .-%. The compositions of the invention may further contain at least one nonpolar or polar liquid oil, which may be natural or synthetic.

The polar oil component may be selected from vegetable oils, e.g. B. sunflower oil, olive oil, soybean oil, rapeseed oil, almond oil, jojoba oil and the liquid portions of coconut oil and synthetic triglyceride oils, from ester oils, that is the esters of C ₆ - ₃₀ fatty acids with C _2-30 - fatty alcohols, from dicarboxylic acid esters such as di- n-butyl adipate, di (2-ethylhexyl) adipate and di (2-ethylhexyl) succinate and diol esters such as ethylene glycol dioleate and propylene glycol di (2-ethylhexanoate), from symmetrical, unsymmetrical or cyclic esters of carbonic acid with fatty alcohols, for example described in DE-OS 197 56 454, glycerol carbonate or Dicapry- lylcarbonat (Cetiol ^® CC), from mono, - di- and tri-fatty acid esters of saturated and / or unsaturated linear and / or branched fatty acids with glycerol, eg. B. Cutina ^® MD, from branched alkanols, eg. B. Guerbet alcohols having a single branch on the carbon atom 2 such as 2-hexyldecanol, 2-octyldodecanol, isotridecanol and isohexadecanol, from alkanediols, eg. B. from Epoxyalkanen with 12 - 24 carbon atoms by ring opening with water available vicinal diols, from ether alcohols, eg. As the monoalkyl ethers of glycerol, ethylene glycol, 1, 2-propylene glycol or 1, 2-butanediol, from dialkyl ethers each having 12 - 24 carbon atoms, eg. Example, the alkyl methyl ethers or di-n-alkyl ethers, each having a total of 12 to 24 carbon atoms, in particular di-n-octyl ether (Cetiol ^® OE ex Cognis), as well as adducts of ethylene oxide and / or propylene oxide to mono- or polyvalent C ₃ . ₂ o-alkanols such as butanol and glycerol, z. PPG-3 myristyl ether (Witconol APM ^®), PPG-14 butyl ether (Ucon Fluid ^® AP) PPG-15 stearyl ether (Arlamol ^® E), PPG-9-butyl ether (Breox B25 ^®) and PPG-10 butanediol (Macol ^® 57).

The non-polar oil component may be selected from liquid paraffin oils, isoparaffin oils, e.g. Isohexadecane and isoeicosane, from synthetic hydrocarbons, e.g. B. 1, 3-di- (2-ethyl-hexyl) -cyclohexane (Cetiol ^® S), as well as volatile and nonvolatile silicone oils, the cyclic, such as. As decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane, or may be linear, for. As linear dimethylpolysiloxane, commercially available z. Example under the name Dow Corning ^® 190, 200, 244, 245, 344 or 345 and Baysilon ^® 350 M.

The skin odor reducing compositions of the present invention may further contain at least one water-soluble alcohol. Water solubility is understood according to the invention that at least 5 wt .-% of the alcohol at 20 ⁰ C clear dissolve or - in the case of long-chain or polymeric alcohols - by heating the solution to 50 ⁰ C to 60 ⁰ C can be brought into solution. Suitable depending on the dosage form monohydric alcohols such. As ethanol, propanol or isopropanol.

Further preferred compositions according to the invention are characterized in that they additionally comprise at least one water-soluble polyhydric C ₂ -C ₉ -alkanol having 2 to 6 hydroxyl groups and / or at least one water-soluble polyethylene glycol consisting of 3 to 20 ethylene oxide units, or mixtures thereof , These components are preferably selected from 1,2-propylene glycol, 2-methyl-1,3-propanediol, glycerol, butanediols such as 1,2-butanediol, 1,3-butanediol and 1,4-butanediol, pentanediols such as 1,2. Pentanediol and 1, 5-pentanediol, hexanediols such as 1, 6-hexanediol, hexanetriols such as 1, 2,6-hexanetriol, 1, 8-octanediol, dipropylene glycol, tripropylene glycol, diglycerol, triglycerol, erythritol, sorbitol and mixtures of aforementioned substances. Suitable water-soluble polyethylene glycols are selected from PEG-3, PEG-4, PEG-6, PEG-7, PEG-8, PEG-9, PEG-10, PEG-12, PEG-14, PEG-16, PEG-18 and PEG-20 and mixtures thereof, with PEG-3 to PEG-8 being preferred. Sugar and certain sugar derivatives such as fructose, glucose, maltose, maltitol, mannitol, inositol, sucrose, trehalose and xylose may also be preferred according to the invention.

The compositions according to the invention contain the water-soluble polyvalent C ₂ -C ₉ -alkanol having 2 to 6 hydroxyl groups and / or the water-soluble polyethylene glycol, consisting of 3 to 20 ethylene oxide units, in total in amounts of 3 to 25% by weight, preferably 8. 18% by weight, based on the total composition. The amount of the alcohol or alcohol mixture in the skin odor reducing compositions of the present invention is preferably 1-50% by weight and preferably 5-40% by weight based on the total composition. According to the invention, both an alcohol and a mixture of several alcohols can be used.

The compositions according to the invention for reducing body odor on the skin can be substantially free of water, that is to say containing not more than 5% by weight, preferably not more than 1% by weight of water. In water-containing administration forms, the water content is 5 to 98% by weight, preferably 10 to 90 and particularly preferably 15 to 85% by weight, based on the total composition.

The skin odor reducing compositions of the present invention may further contain at least one hydrophilically modified silicone. They allow the formulation of highly transparent compositions, reduce the stickiness and leave a fresh feeling on the skin. Hydrophilically modified silicones are understood according to the invention to mean polyorganosiloxanes having hydrophilic substituents which cause the water solubility of the silicones. According to the invention is understood to mean water-solubility that is at least 2 wt .-% resolve the modified with hydrophilic groups silicone in water at 20 ⁰ C. Corresponding hydrophilic substituents are, for example, hydroxy, polyethylene glycol or polyethylene glycol / polypropylene glycol side chains and ethoxylated ester side chains. According to the invention are preferably suitable hydrophilic modified silicone copolyols, in particular dimethicone copolyols, for example, by Wacker-Chemie under the name Belsil ^® DMC 6031, Belsil ^® DMC 6032, Belsil ^® DMC 6038 or Belsil ^® DMC 3071 VP or Dow Corning under the name DC 2501 are commercially available. Particularly preferably suitable is the use of Belsil® ^® DMC 6038, as it allows the formulation of highly transparent compositions that reach the consumer greater acceptance. According to the invention, it is also possible to use any desired mixture of these silicones.

The amount of the hydrophilic modified silicone or the alcohol mixture in the compositions according to the invention is 0.5-10% by weight, preferably 1-8% by weight and more preferably 2-6% by weight, based on the total weight of the Composition.

The skin odor reducing compositions of the present invention may further contain at least one water-soluble surfactant. As water-soluble surfactants are basically all in the system to 1 wt .-% at 20 ^c C soluble and in water at 2O ⁰ C to at least 1 wt .-% of soluble surfactants. Although the structure and ionicity in itself irrelevant, are seem nonionic surfactants, especially the solid at normal temperature (2O ⁰ C) addition products of ethylene oxide with fatty matter molecules having at least one alkoxy- lierbaren group, preferably to be suitable. Such suitable surfactants are, for example, the plant from 10 to 40 mol of ethylene oxide to linear fatty alcohols containing 16 to 22 carbon atoms, to fatty acids having 12 to 22 carbon atoms, to fatty acid alkanolamides, to fatty acid monoglycerides, to sorbitan fatty acid monoesters, to fatty acid alkanolamides, to fatty acid glycerides, for example to hydrogenated castor oil, methylglucoside mono-fatty acid esters and mixtures thereof.

The skin odor reducing compositions of the invention contain at least one antiperspirant active in a preferred embodiment. Suitable antiperspirant active substances are water-soluble astringent metallic salts, in particular inorganic and organic salts of aluminum, zirconium and zinc or any mixtures of these salts. According to the invention has a solubility of at least 5 g active substance per 100 g solution at 20 ⁰ C is understood to mean water solubility. For example, alum (KAl (SO ₄ ) ₂ ^.12H ₂ O), aluminum sulfate, aluminum lactate, sodium aluminum chlorhydroxactate, aluminum chlorohydrate, aluminum chlorohydrate, aluminum sulfocarbolate, aluminum zirconium chlorohydrate, zinc chloride, zinc sulfocarboxylate, zinc sulfate, zirconium chlorohydrate and aluminum-zirconium-chlorohydrate-glycine complexes. The compositions preferably comprise an astringent aluminum salt, in particular aluminum chlorohydrate, and / or an aluminum-zirconium compound. The antiperspirant active ingredients are used in aqueous applications as aqueous solutions. In anhydrous compositions, the antiperspirant active ingredients are used in solid form. They are present in the compositions according to the invention in an amount of 1 to 40% by weight, preferably 5 to 30% by weight and in particular 10 to 25% by weight (based on the amount of active substance in the overall composition). Aluminum chlorohydrates, for example, in powder form sold as Micro Dry ^® Ultrafine from Reheis, as Chlorhydrol ^®, in activated form as Reach ^® 501 from Reheis and in the form of an aqueous solution as Locron ^® L from Clariant. Under the name ^Reach® 301 an aluminum sesquichlorohydrate from Reheis is offered. The use of aluminum zirconium tetrachlorohydrex glycine complexes, which are, for example, by Reheis under the name Rezal ^® 36G commercially, the invention particularly advantageous.

Deodorant cosmetic compositions preferred according to the invention are characterized by containing astringent antiperspirant salts in an amount of 1-40% by weight of the composition.

Furthermore, the compositions according to the invention may contain germ-inhibiting or deodorizing agents for reducing body odor on the skin. Particularly suitable are organohalogen compounds and halides, quaternary ammonium compounds, a number of plant extracts and zinc compounds. Chlorhexidine and chlorhexidine gluconate, benzalkonium halides and cetylpyridinium chloride are preferred. Furthermore are Sodium bicarbonate, sodium phenolsulfonate and zinc phenolsulfonate and z. B. the components of lime blossom oil used.

Other antibacterial deodorant active ingredients are lantibiotics, glycoglycerolipids, sphingolipids (ceramides), sterols and other agents that inhibit bacterial adhesion to the skin, e.g. As glycosidases, lipases, proteases, carbohydrates, di- and Oligosaccharidfett- acid esters and alkylated mono- and oligosaccharides.

Liquid and gelatin dosage forms may contain thickening agents, e.g. As cellulose ethers, such as hydroxypropyl cellulose, hydroxyethyl cellulose and methyl hydroxypropyl cellulose, thickening polymers based on polyacrylates, which may be crosslinked, if desired, for. As the Carbopol types or Pemulen ^® products, or based on polyacrylamides or sulfonic acid-containing polyacrylates, eg. B Sepigel ^® 305 or Simulgel® ^® EG, also inorganic thickeners such. B. Bentonite and Hectorite (Laponite ^®).

The skin odor reducing compositions of the present invention may contain other cosmetically and dermatologically active substances, such as anti-inflammatory substances, solids selected from silicic acids, e.g. As Aerosil ^® types, silica gels, silica, clays, z. B. bentonite or kaolin, magnesium aluminum silicates, z. For example, talc, boron nitride, titanium dioxide, which may optionally be coated, optionally modified starches and starch derivatives, cellulose powders and polymer powders, further plant extracts, protein hydrolysates, vitamins, perfume oils, sebostatics, anti-acne agents and keratolytics.

The cosmetic deodorant or antiperspirant compositions, as far as they are liquid, can be applied to flexible and absorbent carriers and offered as deodorant or anti-perspirant wipes or sponges. As a flexible and absorbent carrier in the context of the invention, z. As carriers of textile fibers, collagen or polymeric foams. As textile fibers, both natural fibers such as cellulose (cotton, linen), silk, wool, regenerated cellulose (viscose, rayon), cellulose derivatives and synthetic fibers such as polyester, polyacrylonitrile, polyamide or polyolefin fibers or mixtures of such fibers can be woven or unwoven. These fibers may be made into absorbent cotton pads, nonwovens or woven or knitted fabrics. Also flexible and absorbent polymeric foams, z. As polyurethane foams and polyamide foams are suitable substrates. The substrate may have one, two, three and more than three layers, wherein the individual layers may consist of the same or different materials. Each substrate layer may have a homogeneous or an inhomogeneous structure with, for example, different zones of different densities. Absorbent for the purposes of the invention are those support substrates which, at 20 ° C., can bind at least 10% by weight, based on the dry weight, of water adsorptively or capillary. Preferably, however, are those carriers which can bind at least 100 wt .-% water adsorptive and capillary.

The equipment of the carrier substrates takes place in such a way that the absorbent, flexible carrier substrates, preferably of textile fibers, collagen or polymeric foams, are treated or equipped with the compositions according to the invention and optionally dried. In this case, the treatment (equipment) of the carrier substrates by any method, for. B. by spraying, dipping and squeezing, soaking or simply by injecting the composition of the invention into the carrier substrates.

Also preferred according to the invention is the dosage form as an aerosol, the cosmetic composition containing a propellant selected from propane, butane, isobutane, pentane, isopentane, dimethyl ether, fluorohydrocarbons and chlorofluorohydrocarbons and also mixtures thereof.

Another object of the present invention is the use of at least one silicic acid ester of the formulas I and / or II and / or III and / or IV

in which in each case at least one radical R is selected from - (CH ₂ J ₂ -CH = CH-CH ₂ -CH ₃ (hexenyl radical) or -CH ₂ -CH = CH-C ₆ H ₅ (cinnamyl radical) and the others Each R independently selected from the group consisting of a hydrogen atom containing straight-chain or branched, saturated or unsaturated, substituted or unsubstituted C ^ -hydrocarbon radicals and the 2-phenoxyethyl radical, and m ranges from 1 to 20 and n takes values ranging from 2 to 100, and mixtures thereof, in cosmetic products.

Particularly preferred is the use according to the invention in deodorants or antiperspirants.

The use of the hexenyl and / or the cinnamyl-silicic acid esters makes it possible to give a longer-lasting effect both to the fragrances which have been esterified with the oligosilicic acids and to the fragrances which are not esterified with the oligosilicic acids. Regardless of the chemical composition of the fragrances, the compounds according to the invention can therefore be used in perfume mixtures in order to give the entire perfume composition a prolonged release of fragrance

Therefore, the use according to the invention according to one of claims 9 or 10 for increasing the fragrance intensity and / or for prolonging the fragrance adhesion and / or odor perception of the cosmetic agents, in particular the deodorants or antiperspirants, is particularly preferred.

With regard to preferred uses according to the invention, what has been said about the compositions according to the invention applies mutatis mutandis.

A further subject of the present invention is a method for reducing body odor on the skin, in which a cosmetic deodorant or antiperspirant composition comprising at least one silicic acid ester of the formulas I and / or II and / or III and / or IV

in which in each case at least one radical R is selected from - (CH ₂ J ₂ -CI-I = CI-I-CH ₂ -CI-I ₃ (hexenyl radical) or -CH ₂ -CH = CH-C ₆ H ₅ (Zimtalkoholrest) and the other radicals R are each independently selected from the group consisting of a hydrogen atom, the straight-chain or branched, saturated or unsaturated, substituted or unsubstituted Ci. ₆ hydrocarbon radicals and the 2-phenoxyethyl radical, and m values from the range 1 to 20 and n values from the range 2 to 100, is applied to the skin, especially on the skin of the armpits. Also with regard to preferred methods according to the invention, what has been said about the compositions according to the invention applies mutatis mutandis. Examples:

The following perfume compositions were prepared (data in g) Perfume 1:

Dpg = dipropylene glycol

Perfume 2:

These perfume oils were incorporated into cosmetic compositions:

All data are in% by weight.

1. Oil-in-water emulsions 1. Skin creams

2. Skin creams:

5th day creams:

2. Water-in-oil emulsion

4. Water-in-silicone emulsion

3. Cleaning preparations

1. Tonic preparations:

2. Cleansing Gel:

Cleansing gels nos. 2 and 3 contain peeling bodies.

Sprayable, translucent antiperspirant or deodorant microemulsions (in% by weight)

Hair conditioner:

Eumulgin ^® B2 0.3

Cetyl / stearyl alcohol 3,3

Isopropyl myristate 0.5

Paraffin oil perliquidum 15 cSt. DAB 9 0.3

Dehyquart ^® L 80 0.4

Lamesoft ^® PO 65 1, 5

Cosmedia Guar C 261 ^® 1, 5

Promois® ^® MEECH-CAQ 3.0

Citric acid 0.4

Potassium Cocoyl Hydrolyzed SiCl 2.0

Caomint 2.0

Hexapeptide-2 0.3

Poly-L-serine 0.5

Phenonip ^® 0.8

Perfume 1 0.15

Water ad 100

Hair Treatment:

Dehyquart ^® F75 4.0

Cetyl / stearyl alcohol 4.0

Paraffin oil perliquidum 15 cSt DAB 9 1.5 Dehyquart ^® A 4.0

Lamesoft ^® PO 65 1 0

Salcare ^® SC 96 1, 5

Caomint 2.0

Sericin 0.1

D / L isoleucine 2.5

Glyoxylic acid 0.5

Amisafe-LMA-60 ^® 1, 0

Gluadin® ^® W 20 3.0

Germall ^® 115 1 0

Citric acid 0.15

Phenonip ^® 0.8

Perfume 1 0.15 water ad 100

Hair Treatment:

Dehyquart ^® 2.0 L80

Cetyl / stearyl alcohol 6.0

Paraffin oil perliquidum 15 cSt DAB 9 2,0

Rewoquat ^® W 75 2.0

Cosmedia Guar C261 ^® 0.5

Lamesoft ^® 65 0.5 PO

Sepigel ^® 305 3,5

Honeyquat ^® 50 1 0

Gluadin® ^® W 20 3.0

Calmosensine 2.0

Hydrolyzed sericin 0.8

L-Glycine 0.4

L-alanyl-L-proline 1, 0

L-tyrosine 0.2

Citric acid 0.15

Phenonip ^® 0.8

Perfume 2 0.15

Water ad 100 Hair Treatment:

Dehyquart ^® F75 0.3

Salcare ^® SC 96 5.0

Gluadin ^® WQ 1, 5

Lamesoft ^® 65 0.5 PO

Dow ^Corning® 200 Fluid, 5 cSt. 1, 5

Gafquat ^® 755N 1, 5

Poly-D / L-alanine 1, 5

Calmosensine 2.0

Caomint 1, 0

Serine 0.1

Glycine methyl ester 0.5

Tyrosine methyl ester 0.2

Sericin 0.2

Biodocarb ^® 0.02

Perfume 2 0.25

Water ad 100

Shampoo: Texapon ^® NSO 40.0 Dehyton ^® G 6.0 Polymer JR ^® 400 0.5 Cetiol ^® HE 0.5 Ajidew NL ^® 50 1 0 65 3.0 PO Lamesoft® Sericin 0.8 Caomint 1, 0 Gluadin ^® WQT 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 2 0, 4 NaCl 0.5 water ad 100

Shampoo:

Texapon.RTM ^® NSO 43.0

Dehyton ^® K 10.0

Plantacare ^® 1200 UP 4.0

Lamesoft ^® 65 2.5 PO

Euperlan ^® PK 3000 1, 6

Arquad ^® 316 0.8

Polymer ^JR® 400 0.3

Caomint 1, 0

Calmosensine 1, 0

Gluadin WQ ^® 4.0

Sodium Lauroyl Hydrolyzed SiIk 3.0

Sericin 10.0

Lactic acid 0.5

Malic acid 0.5

Glucamate DOE 120 ^® 0.5

Sodium chloride 0.2

Perfume 1 0.2

Water ad 100

Anti-hair loss hair tonic for men:

Hair Lotion:

2-phase wellness massage fluid for body and scalp

Massage fluid for sensitive scalp

All quantities are, unless otherwise stated, parts by weight.

Compact hair spray for normal consolidation:

Ultrahold 8 6.0

Amphomer LV-71 4.0

Aminomethylpropanol 1, 3

Pantolactone 0.3

Uvinul MS 40 0.3

Caomint 1, 0

Ethanol 40.0

Perfume 1 0,5

Water ad 60.0

Dimethyl ether 40.0

Compact hair spray for strong consolidation (wet look)

Gantrez ES-425 10.0

Eumulgin 05 0.5

Triisopropanolamine 1, 0

Dow Corning 200 (0.65 cSt) 0.3

Caomint 1, 0

Surfadone LP 300 0.4

Perfume 2 0,5

Water 7.5

Ethanol ad 60.0

Propane / butane (60/40) 40.0 After Shave Cream:

Shower gel:

Anhydrous surfactant-containing AT-pens (in parts by weight)

1.1 1.2

Silicone oil DC ^® 245 28 28

Eutanol ^® G 16 10 -

Cetiol ^® OE - 10

Ucon Fluid ^® AP 5 5

Cutina ^® HR 6 6

Lorol ^® C 18 20 20

Eumulgin ^® B 3 3 3

Aluminum chlorohydrate 20 20

Talc 8 8

Perfume 1 0,5 -

Perfume 2 - 0.7

Zinc lactate 0.1 -

Ascorbyl glucoside - 1, 0

2-ethylhexyl glycerol ether 1.5 -

Sprayable, translucent antiperspirant microemulsions (in% by weight)

Soap-containing pens (in% by weight)

Antiperspirant roll-on (in% by weight)

Suspension type antiperspirant spray (in% by weight)

transparent soap

Examples of compositions for soaking wipes

Various viscose nonwovens were equipped with these impregnating compositions. Perforated, unperforated, dimpled, single-ply, two-ply and three-ply nonwovens were finished. The wipes were used both as wet wipes and as dry wipes (that is, after finishing, the wipes were dried to a residual water content less than 10 wt%, preferably less than 5 wt%, dried). Example 1 illustrates a lotion composition for a lotion and make-up remover wipe.

Example 2 illustrates a soak composition for a self-tanner cloth.

Example 3 illustrates a soak composition for a sunscreen cloth.

Example 4 illustrates a drenching composition for a facial cleansing and exfoliating wipe.

List of raw materials used

odor tests

For proof of efficacy, a perfume composition P3E was prepared which, in addition to fragrances, contained 1% by weight of (Z) -3-hexenylsilicic acid ester according to claim 1. A comparative perfume composition P3V was identically composed but contained instead of the (Z) -3-hexenylsilicic acid ester according to claim 1 dipropylene glycol in an amount of 1% by weight.

Simulation of fragrance retention in a warm and moist environment (similar to conditions in the forearm)

Equal amounts of each of P3E and P3V perfume compositions were placed on a filter paper. The filter paper was then placed over a half-filled petri dish with water. Care was taken to ensure that the filter paper does not sag and does not come into contact with the liquid in the Petri dish. The Petri dish was covered with a glass funnel, whose funnel tube protruded upwards and was closed. Subsequently, the test set-up at 37 ⁰ C was stored. After every 0, 2, 4, 6 and 24 hours, the cap was briefly removed from the funnel tube and the odor assessed.

At test times 2, 4, 6 and 24 hours, P3E showed a higher fragrance intensity than P3V.

consumer test

Further, deodorant sprays containing either 1% by weight of the perfume composition P3E or P3V were prepared and tested by 50 subjects for 14 days. Test recipe anhydrous deodorant spray (in% by weight)

The final assessment of the deodorant sprays according to a total of 5 criteria is shown in the following table:

Furthermore, subject tests with hair shampoos were carried out. For this purpose, the perfume compositions P4E, P4V, P5E and P5V were prepared:

P4E and P4V were a fragrance composition with a citrus-green perfume profile. P4E also contained (Z) -3-hexenylsilicic acid ester and also citronellylyl silicic acid ester and geranylsilicic acid ester. P4V contained instead of the silicic acid esters an appropriate amount of dipropylene glycol. P5E and P5V were a fragrance composition with a citrus-cosmetic perfume profile. In addition, P5E contained (Z) -3-hexenylsilicic acid ester and also citronellylyl silicic acid ester. P5V contained instead of the silicic acid esters an appropriate amount of dipropylene glycol. Subsequently, shampoos were made with 0.74 wt% P4E or 0.74 wt% P4V, further shampoos with 0.5 wt% P5E or 0.5 wt% P5V tested on 30 subjects , For this purpose, the hairs of the test persons were treated with the test shampoos according to a standardized procedure in the half-side procedure. The hairs of the 30 volunteers were moistened with water and parted to two sides. On the one hand, the formulation of the invention (shampoo with 0.74 wt .-% P4E or shampoo with 0.5 wt.% P5E) and on the other hand, the comparison formulation (shampoo with 0.74 wt .-% P4V or shampoo with 0.5 wt.% P5V). Otherwise, the subjects' hair was treated identically, that is, the shampoos were incorporated into the hair for 1 minute. Then the hair was rinsed thoroughly with water and dried. The assessment was carried out independently by 3 persons of the specialized staff.

Composition of the test shampoo (by weight in% by weight):

Texapon ^® NSO 40.0 40.0

Dehyton ^® G 6.0 6.0

Polymer JR ^400® 0.5 0.5

Cetiol ^® HE 0.5 0.5

Ajidew NL ^® 50 1, 0 1, 0

Lamesoft® PO 65 3.0 3.0

Gluadin ^® WQT 2.5 2.5

Citric acid 0.5 0.5

Sodium benzoate 0.5 0.5

Perfume P4E or P4V 0,74 -

Perfume P5E or P5V - 0.5

NaCl 0.5-0.5

Water ad 100 ad 100

On the one hand, the odor of the invention and of the comparison products was tested, furthermore the odor (for the testing specialist) and the odor intensity of the hair 24 or 48 hours after the shampoo treatment. This revealed a significant preference for the products according to the invention over the comparison products for the odor and the fragrance intensity of the hair 24 and 48 hours after the shampoo treatment.

Claims

claims:

1. A cosmetic composition for the treatment of the skin and / or scalp and / or hair and / or oral and dental hygiene, comprising in a suitable cosmetic carrier at least one silicic acid ester of the formulas I and / or II and / or III and / or IV

characterized in that in each case at least one radical R is derived from at least one alcohol which is selected from the group consisting of (Z) -2-hexen-1-ol, (E) -2-hexen-1-ol, (Z) 3-hexen-1-ol (leaf alcohol), (E) -3-hexen-1-ol, (Z) -4-hexen-1-ol, (E) -4-hexen-1-ol, 5- Hexene-1-ol, cinnamyl alcohol, 3-phenylpropan-1-ol (hydrocinnamyl alcohol), 3R (-) - linalool, 3S (+) - linalool, (-) - menthol, (+) - neomenthol, α-terpineol, ß -Terpineol, γ-terpineol, δ-terpineol, (-) - borneol, (+) - isoborneol, (-) - lavandulol, (Z) -4-hepten-2-ol, eugenol, 2-methoxy-4- ( (Z) -1-propenyl) phenol ((Z) isoeugenol), 2-methoxy-4 - ((E) -1-propenyl) phenol ((E) -isoeugenol), 4-hydroxy-2,5-dimethyl -3 (2H) -furanone (furaneol ^®), 4-hydroxy-3-methoxy-benzaldehyde (vanillin), 4- (4- Hydroxyphenyl) -2-butanone (raspberry ketone), (Z, Z) -3,6-nonadien-1-ol, 3,7-dimethyl-7-octene-1-ol (rhodinol) and (Z) -3-octene 1-ol, and the other radicals R are each independently selected from the group consisting of a hydrogen atom, the straight-chain or branched, saturated or unsaturated, substituted or unsubstituted C ₆ -hydrocarbon radicals and the 2-phenoxyethyl radical and m takes values from the range 1 to 20 and n takes values from the range 2 to 100, as well as mixtures thereof.

2. Cosmetic composition according to claim 1, characterized in that at least 10 mol%, preferably at least 20 mol% and particularly preferably more than 40 mol% of the radicals R originate from at least one alcohol selected from the group consisting of (Z) -2-hexen-1-ol, (E) -2-hexen-1-ol, (Z) -3-hexen-1-ol (leaf alcohol), (E) -3-hexen-1-ol , (Z) -4-hexen-1-ol, (E) -4-hexen-1-ol, 5-hexen-1-ol, cinnamyl alcohol, 3-phenylpropan-1-ol (hydrocinnamyl alcohol), 3R (-) Linalool, 3S (+) - linalool, (-) - menthol, (+) - neomenthol, α-terpinene, β-terpineol, γ-terpineol, δ-terpineol, (-) - borneol, (+) - isoborneol, (-) - lavandulol, (Z) -4-hepten-2-ol, eugenol, 2-methoxy-4 - ((Z) -1-propenyl) phenol ((Z) isoeugenol), 2-methoxy 4- ((e) -I propenyl) phenol ((e) -Isoeugenol), 4-hydroxy-2,5-dimethyl-3 (2H) -furanone (furaneol ^®), 4-hydroxy-3-methoxy-benzaldehyde (Vanillin), 4- (4-hydroxyphenyl) -2-butanone (raspberry ketone), (Z, Z) -3,6-nonadien-1-ol, 3,7-dimethyl-7-octene-1-ol (rhodinol ) and (Z) -3-octen-1-ol, and the other radicals R are each independently selected from the group consisting of a hydrogen atom containing straight-chain or branched, saturated or unsaturated, substituted or unsubstituted Cvβ hydrocarbon radicals and the 2-phenoxyethyl radical, and m values from the range 1 to 20 and n assumes values in the range 2 to 100, as well as mixtures thereof.

3. Cosmetic compositions according to one of claims 1 or 2, characterized in that at least 10 mol%, preferably at least 20 mol% and particularly preferably more than 40 mol% of the radicals R originate from at least one alcohol which is selected from (Z) -3-hexene-1-ol (leaf alcohol).

4. Cosmetic composition according to one of claims 1 - 3, characterized in that n values from the range of 2 to 50, preferably from the range of 2 to 20 and in particular from the range of 3 to 10, with particular preference to the values 4, 5, 6, 7 and 8, and m takes values in the range of 2 to 10, with particular preference given to values 2 and 3.

5. Cosmetic composition according to one of claims 1 to 4, characterized in that it or the silicic acid esters in total amounts of 0.000001 to 10 wt .-%, preferably from 0.001 to 5 wt .-%, particularly preferably from 0, 01 to 0.5 wt .-% and in particular from 0.05 to 0.1% by weight, in each case based on the weight of the cosmetic composition.

6. Cosmetic composition according to one of claims 1 to 5, characterized in that it or the inventive silicic acid esters according to any one of claims 1 - 4 in admixture with silicic acid esters of the formulas I and / or II and / or III and / or IV, wherein in each case at least one radical R is selected from the radicals of perfume alcohols and biocide alcohols, those of (Z) -2-hexen-1-ol, (E) -2-hexen-1-ol, (Z) -3-hexene-1 -ol (leaf alcohol), (E) -3-hexen-1-ol, (Z) -4-hexen-1-ol, (E) -4-hexen-1-ol, 5-hexen-1-ol, Cinnamyl alcohol, 3-phenylpropan-1-ol (hydrocinnamyl alcohol), 3R (-) - linalool, 3S (+) - linalool, (-) - menthol, (+) - neomenthol, α-terpineol, ß-terpineol, γ-terpineol , δ-terpineol, (-) - borneol, (+) - isoborneol, (-) - lavandulol, (Z) -4-hepten-2-ol, eugenol, 2-methoxy-4 - ((Z) - 1-propenyl) phenol ((Z) -iso-eugenol), 2-methoxy-4 - ((E) -1-propenyl) phenol ((E) -isoeugenol), 4-hydroxy-2,5-dimethyl-3 (2H) -furanone (furaneol ^®), 4-hydroxy-3-methoxy-benzaldehyde (vanillin), 4- (4-Hydroxyphe- nyl) - 2-butanone (raspberry ketone), (Z, Z) -3,6-nonadien-1-ol, 3,7-dimethyl-7-octene-1-ol (rhodinol) and (Z) -3-octene-1 ol are different, in total amounts of 0.0001 to 10 wt .-%, preferably from 0.001 to 5 wt .-%, particularly preferably from 0.05 to 1, 0 wt .-% and in particular from 0.1, 0, 2, 0.3, 0.4, 0.5, 0.6, 0.7 or 0.8 wt .-%, each based on the weight of the cosmetic composition contains.

Cosmetic composition according to any one of Claims 1 to 6, characterized in that it contains astringent antiperspirant salts in an amount of 1 to 40% by weight of the composition.

8. Cosmetic composition according to one of claims 1 to 7, characterized in that it contains at least one surfactant.

9. Cosmetic composition according to one of claims 1 to 8, in particular a hair and / or skin cleansing composition, characterized in that a combination of at least one anionic surfactant, more preferably an alkyl ether sulfate, and at least one zwitterionic surfactant, more preferably Cocamidopropylbetain is included ,

10. Use of a cosmetic composition according to any one of claims 1 to 9 for the treatment of keratin fibers, in particular human hair.

11. Non-therapeutic, cosmetic use of a cosmetic composition according to any one of claims 1 to 9 for the treatment of the skin and / or the scalp, in particular for cleaning and / or care and / or perfuming.

12. Use of a cosmetic composition according to any one of claims 1 to 9 for influencing the body odor or odor of the hair, in particular for deodorization.

13. Use according to any one of claims 10 - 12 for increasing the fragrance intensity and / or extending the fragrance adhesion and / or scent perception of the cosmetic products.

14. A method for reducing body odor on the skin, characterized in that a cosmetic deodorant or antiperspirant composition comprising at least one silicic acid ester of the formulas I and / or II and / or III and / or IV

in which in each case at least one radical R is derived from at least one alcohol selected from the group consisting of (Z) -2-hexen-1-ol, (E) -2-hexen-1-ol, (Z) -3 -Hexen-1-ol (leaf alcohol), (E) -3-hexen-1-ol, (Z) -4-hexen-1-ol, (E) -4-hexen-1-ol, 5-hexene 1-ol, cinnamyl alcohol, 3-phenylpropan-1-ol (hydrocinnamyl alcohol), 3R (-) - linalool, 3S (+) - linalool, (-) - menthol, (+) - neo- menthol, α-terpineol, β-terpineol, γ-terpineol, δ-terpineol, (-) - borneol, (+) - isoborneol, (-) - lavandulol, (Z) -4-hepten-2-ol, eugenol, 2-methoxy-4 - ((Z) -1-propenyl) phenol ((Z) isoeu- enol), 2-methoxy-4 - ((E) -1-propenyl) phenol ((E) -isoeugenol), 4-hydroxy-2,5-dimethyl-3 (2H) - furanone (furaneol ^®), 4-hydroxy-3-methoxy-benzaldehyde (vanillin), 4- (4-hydroxyphenyl) -2-butanone (raspberry ketone), ( Z, Z) contains -3,6-nonadien-1-ol, 3,7-dimethyl-7-octene-1-ol (rhodinol) and (Z) -3-octene-1-ol, and the other radicals R each independently selected from the group consisting of a hydrogen atom containing straight-chain or branched, saturated or unsaturated, substituted or unsubstituted C _1-6 -hydrocarbon radicals and the 2-phenoxyethyl radical, and m ranges from 1 to 20 and n assumes values in the range 2 to 100, as well as mixtures thereof, on which skin, in particular on the skin of the armpits, is applied.