DE102005059935A1 - Cosmetic agent with increased fragrance intensity and persistence - Google Patents

Abstract

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

Description

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

The Controlled release of ingredients in the most diverse preparations, like as "controlled release ", is the subject of numerous publications and patent applications. Of paramount importance is on the In the field of cosmetics the release of fragrances, since both the Product, as well as the treated with the product substrates such as Skin and / or hair should be intensively and long-lasting scented. In addition to the methods of applying fragrances to substrates and the scented carriers to coat or encapsulate fragrances or in compounds to store (for example, cyclodextrin-perfume complexes), exists Possibility, the fragrances chemically on carrier media to bind, with the chemical bond slowly split and the Fragrance is released. This principle is for example the esterification of perfume alcohols, wherein For this group of substances a wide state of the art exists.

in the In the prior art, there are some suggestions that fragrant alcohols do not volatile To bind siloxanes, from which they slowly released by hydrolysis become. Although also to siloxane esters of perfume alcohols wide state of the art exists, occur in the use of said Compounds in cosmetics problems. So are many of the well-known Compounds in watery based or water-containing cosmetics can not be used since They already hydrolyze in the product and the delayed release because of this later no longer occurs.

Monomeric orthosilicic esters of perfume alcohols are described, for example, in US Pat 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 only to oxygen. Oligomeric siloxane esters are not described in this document.

Liquid or pasty soap compositions containing "fragrance-conferring" silicon compounds are disclosed in U.S.P. DE 30 03 494 (Dow Corning). Also in this document, oligomeric Si compounds having more than one perfume alcohol ester group are not described.

Fragrant, non-volatile siloxanes of the general formula M _a M ' _a D _b D' _b T _c T ' _{c *} Q _d with M and M' = R ¹ R ² R ³ SiO _1/2 , D and D '= R ⁴ R ⁵ SiO _2/2 , T and T '= R ⁶ SiO _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 aryloxy 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 DE-A-197 50 706 (General Electric) described. 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 So there was still the task Siloxanester of perfume alcohols be on the one hand so stable to hydrolysis, that they also in watery or incorporate water-containing cosmetics without already in the product excessive hydrolysis on the other hand, but on the other hand, not to hydrolysis are to prevent the consumer during the usual period of application at all no fragrance experience. The substances to be produced should be both the product as well as the substrates treated with the product (eg skin or hair) give a pleasant and long-lasting fragrance. The hydrolysis behavior of the siloxane esters of perfume alcohols can be determined based on the chemical structure of the fragrance alcohols only difficult or hardly predict. Another object of the present invention It was therefore the state of the art with a wider range of perfume alcohol siloxane esters with an application technology enrich suitable hydrolysis behavior.

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, (+) - 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-methoxybenzaldehyde (vanillin), 4 - (4-hydroxyphenyl 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, which meet application-related 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.

Under Hexene-1-ols are (Z) -2-hexen-1-ol, (E) -2-hexen-1-ol, (Z) -3-hexen-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. According to the invention preferred Hexen-1-ols 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 Of these, particularly preferred hexene-1-ols are selected from (Z) -3-hexen-1-ol (leaf alcohol) and (E) -2-hexen-1-ol and mixtures thereof.

enthalten, wobei jeweils mindestens ein Rest R von mindestens einem Alkohol stammt, der ausgewählt ist aus der Gruppe, die gebildet ist von (Z)-2-Hexen-1-ol, (E)-2-Hexen-1-ol, (Z)-3-Hexen-1-ol (Blätteralkohol), (E)-3-Hexen-1-ol, (Z)-4-Hexen-1-ol, (E)-4-Hexen-1-ol, 5-Hexen-1-ol, Zimtalkohol, 3-Phenylpropan-1-ol (Hydrozimtalkohol), 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)-furanon (Furaneol^®), 4-Hydroxy-3-methoxy-benzaldehyd (Vanillin), 4-(4-Hydroxyphenyl)-2-butanon (Himbeerketon), (Z,Z)-3,6-Nonadien-1-ol, 3,7-Dimethyl-7-octen-1-ol (Rhodinol) und (Z)-3-Octen-1-ol, und die anderen Reste R jeweils unabhängig voneinander ausgewählt sind aus der Gruppe, die ein Wasserstoffatom, die geradkettigen oder verzweigten, gesättigten oder ungesättigten, substituierten oder unsubstituierten C_1-6-Kohlenwasserstoffreste und den 2-Phenoxyethyl-Rest enthält, und m Werte aus dem Bereich 1 bis 20 und n Werte aus dem Bereich 2 bis 100 annimmt, sowie Mischungen hiervon.The invention relates to cosmetic compositions for the treatment of the skin and / or the scalp and / or hair and / or oral and dental hygiene, 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-nonadiene-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 consisting of a hydrogen atom, straight-chain or branched , saturated or unsaturated, substituted or unsubstituted C _1-6 hydrocarbon radicals and the 2-phenoxyethyl radical, and m takes values from the range 1 to 20 and n values from the range 2 to 100, and mixtures thereof.

The preparation of the compounds mentioned in claim 1 is possible by simple transesterification of oligosilicic esters of lower C ₁ -C ₄ -alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol and tert-butanol with a) at least one 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-octene-1-ol (rhodinol) and (Z) -3-octene-1-ol, b ) Mixtures of at least two of the abovementioned alcohols or c) mixtures of min at least one alcohol selected from the aforementioned group with other alcohols. Fragrance alcohols other than the group formed by the hexene-1-ols, cinnamyl alcohol, 3-phenylpropan-1-ol (hydrocinnamyl alcohol), 3R (especially suitable as "other alcohols" which may be present in the transesterification mixture -) - 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-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 are abge 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, (+) - 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) and (Z) -3-octen-1-ol, and optionally the fragrance or biocide alcohols other than this group, the alcohols being 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, N. 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 tetraisopropoxide, titanium tetraisopropylate, silicon tetrachloride or basic catalysts or else preparations such as, for example, of 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 quantities of water or other H-acidic compounds are present in the preparation of the silicic acid esters, there is also an exchange of alcohol residues for OH groups. Accordingly, the silicic acid ester mixtures according to the invention usually also contain, as radical R, some hydrogen.

Oligokieselsäureester lower C ₁ -C ₄ alcohols such as methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol and tert-butanol are commercially available, 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. According to the invention, fragrance means those fragrances, essences and aromas which trigger a pleasant sensation of smell in humans and are therefore used in a variety of ways for the perfuming of technical and sanitary articles, soaps, cosmetics, personal care products 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-hexene-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-octene-1-ol (rhodinol), (Z) -3-octene-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 -Decen-1-ol, α-methylbenzyl alcohol, amyl salicylate, benzyl alcohol, benzylsalicycl lat, 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, nonanol, octanol, para- Menthan-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. Other 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 the like 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 biocide alcohols. It is explicitly methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl and tert-butyl alcohol, which are not considered according to the invention as biocide alcohols. 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 group and at least one alkyl group having one hydroxy group bears, to call.

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 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-phenylpropane-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 optionally additionally at least one further perfume alcohol and / or at least one further biocide 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, (+) - 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 (rhodin ol) and (Z) -3-octen-1-ol.

extraordinarily preferred cosmetic according to the invention Compositions are characterized in that at least 10 mol%, preferably at least 20 mol% and especially preferably more as 40 mol% of the radicals R come from at least one alcohol, the selected is from (Z) -3-hexen-1-ol (leaf alcohol).

Since the starting compounds for the preparation of the compounds according to the invention are preferably not pure substances for economic reasons, but technical mixtures of oligosilicic esters of lower C ₁ -C ₄ -alcohols with different degrees of oligomerization, a distribution of the degrees of oligomerization is also found in the esters in the agents according to the invention, which may correspond to the starting material or is modified by the reaction conditions.

Especially preferred cosmetic according to the invention Compositions are characterized by n values in the range of 2 to 50, preferably in the range of 2 to 20 and in particular from the range of 3 to 10 under particular Favoring the values 4, 5, 6, 7 and 8, and taking m values in the range of 2 to 10, with special preference for the values 2 and 3 adopts.

The cosmetic according to the invention Compositions contain the silicic acid ester (s) according to the invention according to one the claims 1 - 3 preferably in total amounts of 0.000001 to 10 wt .-%, preferably from 0.001 to 5% by weight, particularly preferably from 0.01 to 0.5% by weight 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 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 of fragrance alcohols and / or biocide alcohols derived from (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-phenylpropane-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 (Him beerketon), (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 from 0.0001 to 10% by weight, preferably from 0.001 to 5% by weight, particularly preferably from 0.05 to 1.0% by weight 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 containing.

Next the silicic acid ester (s) can the cosmetic according to the invention Compositions contain other fragrances.

As perfume oils or perfumes, according to the invention, individual fragrance compounds, for. As the synthetic products of the ester, ether, aldehydes, ketones, alcohols and hydrocarbons used. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate (DMBCA), phenylethylacetate, benzylacetate, 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 such as the ionone, α-isomethylionone and methyl cedryl ketone, to the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons include mainly the terpenes such as limonene and pinene. Be Preferably, however, mixtures of different fragrances are used, which together produce an appealing scent.

Such Perfume oils can also natural Contain fragrance mixtures, as they are accessible from plant sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are Muscat sage oil, Chamomile oil, Clove oil, Balm oil, mint oil, Cinnamon leaf oil, lime blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil, as well as Orange blossom oil, neroliol, Orange peel oil and sandalwood oil.

By the distribution of the total perfume content in perfume, which silicic esters esterified is, and perfume, which is un-esterified, can be a variety of Realize product characteristics. So it is conceivable, for example and possible, the total part content the agents according to the invention divided into two portions x and y, the proportion x of adherent, i.e. less volatile and the proportion y of more volatile Perfume oil consists.

The general description of the perfumes used (see above) was general the different substance classes of fragrances dar. To perceptible to be, a fragrance must be volatile, besides the nature of the functional groups and the structure the molecular weight of the chemical compound also plays an important role plays. So most perfumes have molecular weights up to about 200 Dalton, while Molar masses of 300 daltons and above rather an exception. Due to the different volatility changed by fragrances the smell of a compound of several fragrances perfumes or perfume during vaporizing, whereby the odor impressions in "top note", "middle note" body) and "base note" (end note or dry divided out). Because the smell perception to a large extent also on the smell intensity is based, the top note of a perfume or fragrance is not alone from volatile Connections while the base note for the most part from less volatile, i.e. adherent Riehcstoffen. When composing perfumes can be easier volatile For example, fragrances can be bound to specific fixatives. which prevents it from evaporating too quickly. At the following Classification of the fragrances in "lighter volatile or "adherent" fragrances So over the smell impression and about it, whether the corresponding perfume perceived as a head or middle note nothing is said.

Tenacious Fragrances that 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, bergamot oil, Champacablütenöl, Edeltannöl, Edeltannenzapfenapfen, Elemiöl, eucalyptus oil, fennel oil, spruce needle oil, galbanum oil, geranium oil, ginger grass oil, guaiac wood oil, Gurjunbalsamöl, Helichrysumöl, Ho oil, Ginger oil, iris oil, cajeput oil, calamus oil, chamomile oil, camphor oil, kanga oil, cardamom oil, cassia oil, pine oil, copaiba balsam, coriander oil, spearmint oil, caraway oil, cumin oil, lavender oil, lemongrass oil, lime oil, tangerine oil, lemon balm oil, musk oil, myrrh oil, clove oil, neroli oil, niaouli oil, Olibanum Oil, Orange Oil, Origanum Oil, Palmarosa Oil, Patchouli Oil, Peru Balsam Oil, Petitgrain Oil, Pepper Oil, Peppermint Oil, Pimento Oil, Pine Oil, Rose Oil, Rosemary Oil, Sandalwood Oil, Celery Oil, Spik Oil, Star Aniseed Oil, Turpentine Oil, Thuja Oil, Thyme Oil, Verbena Oil, Vetiver Oil, Juniper Berry Oil, Vermouth Oil, Wintergreen oil, Ylang-Ylan g oil, hyssop oil, cinnamon oil, cinnamon leaf oil, lemon oil, lemon oil and cypress oil.

But also the higher-boiling ones or solid odoriferous natural or of synthetic origin in the context of the present invention as adherent fragrances or Fragrance mixtures, so fragrances are used. To this Counting connections the following compounds as well as mixtures of these: 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-methyl acetophenone, Methylchavikol, p-methylquinoline, methyl-β-naphthylketone, methyl-n-nonylacetaldehyde, Methyl n-nonyl ketone, Muskon, R-naphthol ethyl ether, β-naphthol methyl ether, Nerol, nitrobenzene, n-nonylaldehyde, nonyl alcohol, n-octylaldehyde, p-oxy-acetophenone, pentadecanolide, β-phenylethyl alcohol, phenylacetaldehyde dimethyacetal, phenylacetic acid, Pulegone, safrol, salicylic acid isoamyl ester, methyl salicylate, Salicylsäurehexylester, Salicylsäurecyclohexylester, Santalol, skatole, terpineol, thymen, thymol, γ-undelactone, vanillin, veratrum aldehyde, Cinnamaldehyde, cinnamyl alcohol, cinnamic acid, cinnamate, Zimtsäurebenzylester.

To the more volatile Scents count especially the lower-boiling fragrances natural or synthetic origin, used alone or in mixtures can be.

Examples for easier 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.

In dependence From the field of application of cosmetic products, these can be a variety of other ingredients included. These are described below. If the term "agent according to the invention" is used below, This always means the cosmetic product.

The Silica esters according to the invention unfold their positive effects, especially in hair treatment. Usually will be at the personal Care for the skin more often As the hair is cleaned, especially because the hair after cleansing is expensive to dry and to style. From a hair care product wishes the consumer therefore a particularly long-lasting care effect. A long-lasting perfume also signals the user a lasting effect of the whole Product.

Especially preferred cosmetic according to the invention Compositions are characterized in that they are a Composition for the treatment of keratin fibers, in particular human Hair, act. As such, in particular shampoos, conditioners, rinses, Hair conditioners, hair tonics, hair lotions, Hair gels, hair sprays, etc. into consideration. Other important representatives this group are the hair dyes, in particular the oxidative hair dyes.

enthalten, wobei jeweils mindestens ein Rest R von mindestens einem Alkohol stammt, der ausgewählt ist aus der Gruppe, die (Z)-2-Hexen-1-ol, (E)-2-Hexen-1-ol, (Z)-3-Hexen-1-ol (Blätteralkohol), (E)-3-Hexen-1-ol, (Z)-4-Hexen-1-ol, (E)-4-Hexen-1-ol, 5-Hexen-1-ol, Zimtalkohol, 3-Phenylpropan-1-ol (Hydrozimtalkohol), 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)-furanon (Furaneol^®), 4-Hydroxy-3-methoxy-benzaldehyd (Vanillin), 4-(4-Hydroxyphenyl)-2-butanon (Himbeerketon), (Z,Z)-3,6-Nonadien-1-ol, 3,7-Dimethyl-7-octen-1-ol (Rhodinol) und (Z)-3-Octen-1-ol enthält, und die anderen Reste R jeweils unabhängig voneinander ausgewählt sind aus der Gruppe, die ein Wasserstoffatom, die geradkettigen oder verzweigten, gesättigten oder ungesättigten, substituierten oder unsubstituierten C_1-6-Kohlenwasserstoffreste und den 2-Phenoxyethyl-Rest enthält, und m Werte aus dem Bereich 1 bis 20 und n Werte aus dem Bereich 2 bis 100 annimmt, sowie Mischungen hiervon, zur Behandlung von Keratinfasern, insbesondere menschlichen Haaren.Another object of the present invention is therefore the use of a cosmetic composition comprising silica esters of the formulas I and / or II and / or III and / or IV in a suitable cosmetic carrier

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-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-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 which is straight-chain or branched, g containing saturated or unsaturated, substituted or unsubstituted C _1-6 hydrocarbon radicals and the 2-phenoxyethyl radical, and m has values in the range 1 to 20 and n values in the range 2 to 100, and mixtures thereof, for the treatment of keratin fibers , especially human hair.

Hair detergent (Shampoos) as well as body cleanser (Shower rooms, Shower gels, bath bath compositions, liquid soaps, syndets) (more or less strong) foaming anionic, zwitterionic, ampholytic and nonionic surfactants contain. Hair rinses, Conditioners and conditioning skin and body cleanser (2-in-1 shower gels) included preferably cationic surfactants and / or water-soluble polymers with quaternary ammonium groups to reduce static chargeability and improve combability of the hair or to improve the skin feel. Hair- and skin cleansers essentially differ only by the amounts of surfactant from each other: due to the lower sensitivity of the hair opposite The skin contains shampoos and the like Compositions usually more surfactants, in particular more cationic surfactants, as a skin cleanser. Skin cleansers are preferred 0 - 2 Wt .-%, particularly preferably 0 - 1 Wt .-% cationic surfactants. Furthermore are preferred in skin cleansers the milder, less degreasing surfactants used. Other hair treatment products included quite additives, the for Skin treatment agents are rather unsuitable. Thus, permanent wave fixatives are preferred Oxidizing agent such. As potassium bromate or hydrogen peroxide. Haarfärbeshampoos contain direct hair dye or oxidation dye precursors. Hair fixatives and hair products as well as other hairstyling preparations usually contain film-forming, in aqueous or aqueous-alcoholic Media soluble Polymers, optionally together with cationic surfactants or cationic polymers.

When Particularly advantageous is the use of surfactants (E) in the agents according to the invention proved. In a further preferred embodiment, the compositions according to the invention contain therefore at least one surfactant. Surfactants are surfactants Understand substances that form adsorptive layers at the interfaces and interfaces or in volume phases to micellar colloids or lyotropic mesophases can aggregate. A distinction is made between anionic surfactants, consisting of a hydrophobic Residue and a negatively charged hydrophilic head group, amphoteric Surfactants that are both a negative and a compensating positive Carry charge, cationic surfactants in addition to a hydrophobic Rest have a positively charged hydrophilic group, and nonionic Surfactants that have no charges but strong dipole moments and in aqueous solution are strongly hydrated.

• – lineare und verzweigte Fettsäuren mit 8 bis 30 C-Atomen (Seifen),
• – Ethercarbonsäuren der Formel R-O-(CH₂-CH₂O)_x-CH₂-COOH, in der R eine lineare Alkylgruppe mit 8 bis 30 C-Atomen und x = 0 oder 1 bis 16 ist,
• – Acylsarcoside mit 8 bis 24 C-Atomen in der Acylgruppe,
• – Acyltauride mit 8 bis 24 C-Atomen in der Acylgruppe,
• – Acylisethionate mit 8 bis 24 C-Atomen in der Acylgruppe,
• – Sulfobernsteinsäuremono- und -dialkylester (Sulfosuccinate) mit 8 bis 24 C-Atomen in der Alkylgruppe und Sulfobernsteinsäuremono-alkylpolyoxyethylester mit 8 bis 24 C-Atomen in der Alkylgruppe und 1 bis 6 Oxyethylgruppen,
• – lineare Alkansulfonate mit 8 bis 24 C-Atomen,
• – lineare Alpha-Olefinsulfonate mit 8 bis 24 C-Atomen,
• – Alpha-Sulfofettsäuremethylester von Fettsäuren mit 8 bis 30 C-Atomen,
• – Alkylsulfate und Alkylpolyglykolethersulfate der Formel R-O(CH₂-CH₂O)_x-OSO₃H, in der R eine bevorzugt lineare Alkylgruppe mit 8 bis 30 C-Atomen und x = 0 oder 1 bis 12 ist,
• – sulfatierte Hydroxyalkylpolyethylen- und/oder Hydroxyalkylenpropylenglykolether
• – Sulfonate ungesättigter Fettsäuren mit 8 bis 24 C-Atomen und 1 bis 6 Doppelbindungen
• – Ester der Weinsäure und Zitronensäure mit Alkoholen, die Anlagerungsprodukte von etwa 2-15 Molekülen Ethylenoxid und/oder Propylenoxid an Fettalkohole mit 8 bis 22 C-Atomen darstellen,
• – Alkyl- und/oder Alkenyletherphosphate der Formel (E1-I), R¹(OCH₂CH₂)_n-O-P(O)(OX)-OR² (E1-I)in der R¹ bevorzugt für einen aliphatischen Kohlenwasserstoffrest mit 8 bis 30 Kohlenstoffatomen, R² für Wasserstoff, einen Rest (CH₂CH₂O)_nR² oder X, n für Zahlen von 1 bis 10 und X für Wasserstoff, ein Alkali- oder Erdalkalimetall oder NR³R⁴R⁵R⁶, mit R³ bis R⁶ unabhängig voneinander stehend für Wasserstoff oder einen C₁ bis C₄ – Kohlenwasserstoffrest, steht,
• – sulfatierte Fettsäurealkylenglykolester der Formel (E1-II) R⁷CO(AlkO)_nSO₃M (E1-II)in der R⁷CO-für einen linearen oder verzweigten, aliphatischen, gesättigten und/oder ungesättigten Acylrest mit 6 bis 22 C-Atomen, Alk für CH₂CH₂, CHCH₃CH₂ und/oder CH₂CHCH₃, n für Zahlen von 0,5 bis 5 und M für ein Kation steht,
• – Monoglyceridsulfate und Monoglyceridethersulfate der Formel (E1-III)
  
  in der R⁸CO für einen linearen oder verzweigten Acylrest mit 6 bis 22 Kohlenstoffatomen, x, y und z in Summe für 0 oder für Zahlen von 1 bis 30, vorzugsweise 2 bis 10, und X für ein Alkali- oder Erdalkalimetall steht. Typische Beispiele für im Sinne der Erfindung geeignete Monoglycerid(ether)sulfate sind die Umsetzungsprodukte von Laurinsäuremonoglycerid, Kokosfettsäuremonoglycerid, Palmitinsäuremonoglycerid, Stearinsäuremonoglycerid, Ölsäuremonoglycerid und Talgfettsäuremonoglycerid sowie deren Ethylenoxidaddukte mit Schwefeltrioxid oder Chlorsulfonsäure in Form ihrer Natriumsalze. Vorzugsweise werden Monoglyceridsulfate der Formel (E1-III) eingesetzt, in der R⁸CO für einen linearen Acylrest mit 8 bis 18 Kohlenstoffatomen steht,
• – Amidethercarbonsäuren,
• – Kondensationsprodukte aus C₈-C₃₀-Fettalkoholen mit Proteinhydrolysaten und/oder Aminosäuren und deren Derivaten, welche dem Fachmann als Eiweissfettsäurekondensate bekannt sind, wie beispielsweise die Lamepon^®-Typen, Gluadin^®-Typen, Hostapon^® KCG oder die Amisoft^®-Typen.

Suitable anionic surfactants (E1) in 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 with 8 to 30 carbon atoms (soaps),
• Ether carboxylic acids of the formula RO- (CH ₂ -CH ₂ O) _x -CH ₂ -COOH, in which R is a linear alkyl group having 8 to 30 C atoms and x = 0 or 1 to 16,
• Acylsarcosides having 8 to 24 C atoms in the acyl group,
• Acyltaurides having 8 to 24 carbon atoms in the acyl group,
• Acyl isethionates having 8 to 24 C atoms in the acyl group,
• Sulfosuccinic acid mono- and dialkyl esters (sulfosuccinates) having 8 to 24 C atoms in the alkyl group and sulfosuccinic acid monoalkylpolyoxyethyl esters having 8 to 24 C atoms in the alkyl group and 1 to 6 oxyethyl groups,
• - linear alkanesulfonates having 8 to 24 carbon atoms,
• - linear alpha-olefin sulfonates having 8 to 24 carbon atoms,
• Alpha-sulfofatty acid methyl esters of fatty acids having 8 to 30 C 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 C atoms and x = 0 or 1 to 12,
• - Sulfated Hydroxyalkylpolyethylen- and / or Hydroxyalkylenpropylenglykolether
• - 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 which are adducts of about 2-15 molecules of ethylene oxide and / or propylene oxide with fatty alcohols containing 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 (E1-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 a number from 0.5 to 5 and M is a cation,
• Monoglyceride sulfates and monoglyceride ether sulfates of the formula (E1-III)
  
  in which R ⁸ CO is a linear or branched acyl radical having 6 to 22 carbon atoms, x, y and z are in total 0 or numbers of 1 to 30, preferably 2 to 10, and X is an alkali or alkaline earth metal. Typical examples of monoglyceride (ether) sulfates suitable for the purposes of the invention are the reaction products of lauric acid monoglyceride, coconut fatty acid monoglyceride, palmitic acid monoglyceride, stearic acid monoglyceride, oleic acid monoglyceride and tallow fatty acid monoglyceride and their ethylene oxide adducts with sulfur trioxide or chlorosulfonic acid in the form of their sodium salts. 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 skilled person as protein fatty acid condensates, such as Lamepon ^® grades, Gluadin ^® grades, Hostapon ^® KCG or Amisoft ^® grades ,

preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids with 10 to 18 C atoms in the alkyl group and up to 12 glycol ether groups in the molecule, sulfosuccinic and -dialkylester having 8 to 18 carbon atoms in the alkyl group, Sulfobernsteinsäuremonoalkylpolyoxyethylester having 8 to 18 C atoms in the alkyl group and 1 to 6, preferably 2 - 4 Oxyethylene groups and ethoxylated esters of citric acid alkyl esters and sulfosuccinic acid having 8 to 18 C atoms in the alkyl group and 1 to 6, preferably 3 - 5 Oxyethylene groups, for example disodium PEG-5 lauryl citrate sulfosuccinates, z. Available from Goldschmidt under the name Rewopol SB CS 50 K, furthermore monoglyceride sulfates, alkyl and alkenyl ether phosphates as well as protein fatty acid condensates and amino acid-fatty acid condensates, z. For example, sodium lauroyl glutamates, e.g. Available from Zschimmer & Schwarz the name Protelan AGL 95.

Zwitterionic surfactants (E2) are those surface-active compounds which carry in the molecule at least one quaternary ammonium group and at least one -COO ^(-) or -SO ₃ ^(-) group. Particularly suitable zwitterionic surfactants are the so-called betaines such as N-alkyl-N, N-dimethylammonium glycinates, for example cocoalkyl dimethylammonium glycinate, N-acylaminopropyl N, N-dimethylammonium glycinates, for example cocoacylaminopropyl-dimethylammonium glycinate, and 2-Al Kyl-3-carboxymethyl-3-hydroxyethylimidazoline having in each case 8 to 18 carbon atoms in the alkyl or acyl group and Kokosacylaminoethylhydroxyethylcarboxymethylglycinat. 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.

• – Anlagerungsprodukte von 2 bis 50 Mol Ethylenoxid und/oder 0 bis 5 Mol Propylenoxid an lineare und verzweigte Fettalkohole mit 8 bis 30 C-Atomen, an Fettsäuren mit 8 bis 30 C-Atomen und an Alkylphenole mit 8 bis 15 C-Atomen in der Alkylgruppe,
• – mit einem Methyl- oder C₂–C₆– Alkylrest endgruppenverschlossene Anlagerungsprodukte von 2 bis 50 Mol Ethylenoxid und/oder 0 bis 5 Mol Propylenoxid an lineare und verzweigte Fettalkohole mit 8 bis 30 C-Atomen, an Fettsäuren mit 8 bis 30 C-Atomen und an Alkylphenole mit 8 bis 15 C-Atomen in der Alkylgruppe, wie beispielsweise die unter den Verkaufsbezeichnungen Dehydol^® LS, Dehydol^® LT (Cognis) erhältlichen Typen,
• – C₁₂-C₃₀-Fettsäuremono- und -diester von Anlagerungsprodukten von 1 bis 30 Mol Ethylenoxid an Glycerin,
• – Anlagerungsprodukte von 5 bis 60 Mol Ethylenoxid an Rizinusöl und gehärtetes Rizinusöl,
• – Polyolfettsäureester, wie beispielsweise das Handelsprodukt Hydagen^® HSP (Cognis) oder Sovermol – Typen (Cognis),
• – alkoxylierte Triglyceride,
• – alkoxylierte Fettsäurealkylester der Formel (E4-I) R¹CO-(OCH₂CHR²)_wOR³ (E4-I)in der R¹CO für einen linearen oder verzweigten, gesättigten und/oder ungesättigten Acylrest mit 6 bis 22 Kohlenstoffatomen, R² für Wasserstoff oder Methyl, R³ für lineare oder verzweigte Alkylreste mit 1 bis 4 Kohlenstoffatomen und w für Zahlen von 1 bis 20 steht,
• – Aminoxide,
• – Hydroxymischether,
• – Sorbitanfettsäureester und Anlagerungsprodukte von Ethylenoxid an Sorbitanfettsäureester wie beispielsweise die Polysorbate,
• – Zuckerfettsäureester und Anlagerungsprodukte von Ethylenoxid an Zuckerfettsäureester, beispielsweise die Handelsprodukte Glucate SS, Glucate DO, Glucamate DOE 120 und Glucamate SSE 20,
• – Anlagerungsprodukte von Ethylenoxid an Fettsäurealkanolamide und Fettamine,
• – Zuckertenside vom Typ der Alkyl- und Alkenyloligoglykoside gemäß Formel (E4-II), R⁴O-[G]_p (E4-II)in der R⁴ für einen Alkyl- oder Alkenylrest mit 4 bis 22 Kohlenstoffatomen, G für einen Zuckerrest mit 5 oder 6 Kohlenstoffatomen und p für Zahlen von 1 bis 10 steht. Sie können nach den einschlägigen Verfahren der präparativen organischen Chemie erhalten werden. Die Alkyl- und Alkenyloligoglykoside können sich von Aldosen bzw. Ketosen mit 5 oder 6 Kohlenstoffatomen, vorzugsweise von Glucose, ableiten. Die bevorzugten Alkyl- und/oder Alkenyloligoglycoside sind somit Alkyl- und/oder Alkenyloligoglucoside. Die Indexzahl p in der allgemeinen Formel (E4-II) gibt den Oligomerisierungsgrad (DP), d. h. die Verteilung von Mono- und Oligoglycosiden an und steht für eine Zahl zwischen 1 und 10. Während p im einzelnen Molekül stets ganzzahlig sein muss und hier vor allem die Werte p = 1 bis 6 annehmen kann, ist der Wert p für ein bestimmtes Alkyloligoglycosid eine analytisch ermittelte rechnerische Größe, die meistens eine gebrochene Zahl darstellt. Vorzugsweise werden Alkyl- und/oder Alkenyloligoglycoside mit einem mittleren Oligomerisierungsgrad p von 1,1 bis 3,0 eingesetzt. Aus anwendungstechnischer Sicht sind solche Alkyl- und/oder Alkenyloligoglycoside bevorzugt, deren Oligomerisierungsgrad kleiner als 1,7 ist und insbesondere zwischen 1,2 und 1,4 liegt. Der Alkyl- bzw. Alkenylrest R⁴ kann sich von primären Alkoholen mit 4 bis 11, vorzugsweise 8 bis 10 Kohlenstoffatomen ableiten. Typische Beispiele sind Butanol, Capronalkohol, Caprylalkohol, Caprinalkohol und Undecylalkohol sowie deren technische Mischungen, wie sie beispielsweise bei der Hydrierung von technischen Fettsäuremethylestern oder im Verlauf der Hydrierung von Aldehyden aus der Roelen'schen Oxosynthese erhalten werden. Bevorzugt sind Alkyloligoglucoside der Kettenlänge C₈-C₁₀(DP = 1 bis 3), die als Vorlauf bei der destillativen Auftrennung von technischem C₈-C₁₈-Kokosfettalkohol anfallen und mit einem Anteil von weniger als 6 Gew.-% C₁₂-Alkohol verunreinigt sein können sowie Alkyloligoglucoside auf Basis technischer C_9/11-Oxoalkohole (DP = 1 bis 3). Der Alkyl- bzw. Alkenylrest R¹⁵ kann sich ferner auch von primären Alkoholen mit 12 bis 22, vorzugsweise 12 bis 14 Kohlenstoffatomen ableiten. Typische Beispiele sind Laurylalkohol, Myristylalkohol, Cetylalkohol, Palmitoleylalkohol, Stearylalkohol, Isostearylalkohol, Oleylalkohol, Elaidylalkohol, Petroselinylalkohol, Arachylalkohol, Gadoleylalkohol, Behenylalkohol, Erucylalkohol, Brassidylalkohol sowie deren technische Gemische, die wie oben beschrieben erhalten werden können. Bevorzugt sind Alkyloligoglucoside auf Basis von gehärtetem C_12/14-Kokosalkohol mit einem DP von 1 bis 3.
• – Zuckertenside vom Typ der Fettsäure-N-alkylpolyhydroxyalkylamide, ein nichtionisches Tensid der Formel (E4-III), R⁵CO-NR⁶-[Z] (E4-III) in der R⁵CO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R⁶ für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 12 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Bei den Fettsäure-N-alkylpolyhydroxyalkylamiden handelt es sich um bekannte Stoffe, die üblicherweise durch reduktive Aminierung eines reduzierenden Zuckers mit Ammoniak, einem Alkylamin oder einem Alkanolamin und nachfolgende Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden. Vorzugsweise leiten sich die Fettsäure-N-alkylpolyhydroxyalkylamide von reduzierenden Zuckern mit 5 oder 6 Kohlenstoffatomen, insbesondere von der Glucose ab. Die bevorzugten Fettsäure-N-alkylpolyhydroxyalkylamide stellen daher Fettsäure-N-alkylglucamide dar, wie sie durch die Formel (E4-IV) wiedergegeben werden: R⁷CO-NR⁸-CH₂-(CHOH)₄-CH₂OH (E4-IV)Vorzugsweise werden als Fettsäure-N-alkylpolyhydroxyalkylamide Glucamide der Formel (E4-IV) eingesetzt, in der R⁸ für Wasserstoff oder eine Alkylgruppe steht und R⁷CO für den Acylrest der Capronsäure, Caprylsäure, Caprinsäure, Laurinsäure, Myristinsäure, Palmitinsäure, Palmitoleinsäure, Stearinsäure, Isostearinsäure, Ölsäure, Elaidinsäure, Petroselinsäure, Linolsäure, Linolensäure, Arachinsäure, Gadoleinsäure, Behensäure oder Erucasäure bzw. derer technischer Mischungen steht. Besonders bevorzugt sind Fettsäure-N-alkylglucamide der Formel (E4-IV), die durch reduktive Aminierung von Glucose mit Methylamin und anschließende Acylierung mit Laurinsäure oder C12/14-Kokosfettsäure bzw. einem entsprechenden Derivat erhalten werden. Weiterhin können sich die Polyhydroxyalkylamide auch von Maltose und Palatinose ableiten.

Nonionic surfactants (E4) contain, for example, a polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether group as the hydrophilic group. 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 onto alkylphenols having 8 to 15 carbon atoms in the alkyl group, such as those available under the trade names Dehydol ^® LS, LT Dehydol ^® types (Cognis),
• C ₁₂ -C ₃₀ -fatty acid mono- and diesters of addition products of 1 to 30 mol of ethylene oxide with glycerol,
• Adducts of 5 to 60 moles of ethylene oxide with castor oil and hydrogenated castor oil,
• - polyol, such as the commercially available product ^® Hydagen HSP (Cognis) or Sovermol - types (Cognis),
• - alkoxylated triglycerides,
• Alkoxylated fatty acid alkyl esters of the formula (E4-I) R ¹ CO- (OCH ₂ CHR ² ) _w OR ³ (E4-I) in which R ¹ CO is a linear or branched, saturated and / or unsaturated acyl radical having 6 to 22 carbon atoms, R ² is hydrogen or methyl, R ³ is linear or branched alkyl radicals having 1 to 4 carbon atoms, and w is a number from 1 to 20 stands,
• - amine oxides,
• - hydroxymix ether,
• Sorbitan fatty acid esters and adducts of ethylene oxide with sorbitan fatty acid esters such as the polysorbates,
• Sugar fatty acid esters and addition products of ethylene oxide with sugar fatty acid esters, for example the commercial products Glucate SS, Glucate DO, Glucamate DOE 120 and Glucamate SSE 20,
• Adducts of ethylene oxide with fatty acid alkanolamides and fatty amines,
• Sugar surfactants of the alkyl and alkenyl oligoglycoside type of formula (E4-II), R ⁴ O- [G] _p (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 with 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 a mean degree of oligomerization p of from 1.1 to 3.0. From an application point of view, those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4 are preferred. The alkyl or alkenyl radical R ⁴ may be from primary alcohols having 4 to 11, preferably 8 derive up to 10 carbon atoms. Typical examples are butanol, caproic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and technical mixtures thereof, 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 in a proportion of less than 6% by weight C ₁₂ - Alcohol may be contaminated as well as alkyl oligoglucosides based on technical C _9/11 oxo alcohols (DP = 1 to 3). The alkyl or alkenyl radical R ¹⁵ can also be derived from primary alcohols having 12 to 22, preferably 12 to 14 carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, 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. Preference is given to alkyl oligoglucosides based on hydrogenated C _12/14 coconut alcohol having a DP of 1 to 3.
• Sugar surfactants of the fatty acid N-alkyl polyhydroxyalkylamide 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 (E4-IV): 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, petroselic acid, linoleic acid, linolenic acid, arachidic acid, gadoleic acid, behenic acid or erucic acid or their 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.

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

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

Farther Very particularly preferred nonionic surfactants are the sugar surfactants. these can in the invention used Agents preferably in amounts of 0.1 to 20 wt .-%, based on the entire means, be included. Amounts of 0.5-15% by weight are preferred and most preferred are amounts of from 0.5 to 7.5% by weight.

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

at the surfactants, the adducts of ethylene and / or propylene oxide represent fatty alcohols or derivatives of these addition products, can both products with a "normal" homolog distribution as well as those with a narrow homolog distribution become. Under "normal" homolog distribution are understood to mean mixtures of homologs which are used in the Reaction of fatty alcohol and alkylene oxide using alkali metals, Alkali metal hydroxides or alkali metal alcoholates as catalysts receives. Narrowed homolog distributions are obtained when, for example Hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or - alcoholates be used as catalysts. The use of products with narrow homolog distribution may be preferred.

Usable according to the invention are cationic surfactants of the quaternary ammonium type, the Esterquats and amidoamines. Preferred quaternary ammonium compounds are ammonium halides, especially chlorides and bromides, such as Alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g. Cetyltrimethylammonium chloride, Stearyltrimethylammonium chloride, distearyldimethylammonium chloride, Lauryldimethylammonium chloride, Lauryldimethylbenzylammoniumchlorid and tricetylmethylammonium chloride, as well as those under the INCI names Quaternium 27 and Quaternium-83 known imidazolium compounds. The long alkyl chains The above-mentioned surfactants preferably have 10 to 18 carbon atoms on.

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, for example, under the names Genamin ^® KDMP (Clariant) and Crodazosoft ^® DBQ (Crodauza) are.

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

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

The Cationic surfactants are preferred in amounts in the compositions according to the invention from 0.05 to 10 wt .-%, based on the total agent. Amounts of 0.1 to 5 wt .-% are particularly preferred.

The Surfactants (E) are used in amounts of 0.1-45% by weight, preferably 0.5-25% by weight. and most preferably from 1.0 to 15 wt .-%, based on the entire used in the invention Medium, used.

anionic, nonionic, zwitterionic and / or amphoteric surfactants as well their mixtures can preferred according to the invention be.

wobei jeweils mindestens ein Rest R von mindestens einem Alkohol stammt, der ausgewählt ist aus der Gruppe, die (Z)-2-Hexen-1-ol, (E)-2-Hexen-1-ol, (Z)-3-Hexen-1-ol (Blätteralkohol), (E)-3-Hexen-1-ol, (Z)-4-Hexen-1-ol, (E)-4-Hexen-1-ol, 5-Hexen-1-ol, Zimtalkohol, 3-Phenylpropan-1-ol (Hydrozimtalkohol), 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)-furanon (Furaneol^®), 4-Hydroxy-3-methoxy-benzaldehyd (Vanillin), 4-(4-Hydroxyphenyl)-2-butanon (Himbeerketon), (Z,Z)-3,6-Nonadien-1-ol, 3,7-Dimethyl-7-octen-1-ol (Rhodinol) und (Z)-3-Octen-1-ol enthält, und die anderen Reste R jeweils unabhängig voneinander ausgewählt sind aus der Gruppe, die ein Wasserstoffatom, die geradkettigen oder verzweigten, gesättigten oder ungesättigten, substituierten oder unsubstituierten C_1-6-Kohlenwasserstoffreste und den 2-Phenoxyethyl-Rest enthält, und m Werte aus dem Bereich 1 bis 20 und n Werte aus dem Bereich 2 bis 100 annimmt.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, 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-nonadiene-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 consisting of a hydrogen atom that are straight-chain or branched, saturated or unsaturated, substituted or unsubstituted C _1-6 hydrocarbon radicals and the 2-phenoxyethyl radical, and m takes values from the range 1 to 20 and n assumes values from the range 2 to 100.

wobei jeweils mindestens ein Rest R von mindestens einem Alkohol stammt, der ausgewählt ist aus der Gruppe, die (Z)-2-Hexen-1-ol, (E)-2-Hexen-1-ol, (Z)-3-Hexen-1-ol (Blätteralkohol), (E)-3-Hexen-1-ol, (Z)-4-Hexen-1-ol, (E)-4-Hexen-1-ol, 5-Hexen-1-ol, Zimtalkohol, 3-Phenylpropan-1-ol (Hydrozimtalkohol), 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-prope nyl)phenol ((E)-Isoeugenol), 4-Hydroxy-2,5-dimethyl-3(2H)-furanon (Furaneol^®), 4-Hydroxy-3-methoxy-benzaldehyd (Vanillin), 4-(4-Hydroxyphenyl)-2-butanon (Himbeerketon), (Z,Z)-3,6-Nonadien-1-ol, 3,7-Dimethyl-7-octen-1-ol (Rhodinol) und (Z)-3-Octen-1-ol enthält, und die anderen Reste R jeweils unabhängig voneinander ausgewählt sind aus der Gruppe, die ein Wasserstoffatom, die geradkettigen oder verzweigten, gesättigten oder ungesättigten, substituierten oder unsubstituierten C_1-6-Kohlenwasserstoffreste und den 2-Phenoxyethyl-Rest enthält, und m Werte aus dem Bereich 1 bis 20 und n Werte aus dem Bereich 2 bis 100 annimmt.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, 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 radicals R are each independently selected from the group consisting of Hydrogen atom, the straight-chain or branched, saturated contains n or unsaturated, substituted or unsubstituted C _1-6 -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.

• – Anlagerungsprodukte von 1 bis 100, bevorzugt 4 bis 30 Mol Ethylenoxid und/oder 0 bis 5 Mol Propylenoxid an lineare Fettalkohole mit 8 bis 22 C-Atomen, an Fettsäuren mit 12 bis 22 C-Atomen und an Alkylphenole mit 8 bis 15 C-Atomen in der Alkylgruppe,
• – C₁₂-C₂₂-Fettsäuremono- und -diester von Anlagerungsprodukten von 1 bis 30 Mol Ethylenoxid an Polyole mit 3 bis 6 Kohlenstoffatomen, insbesondere an Glycerin,
• – Ethylenoxid- und Polyglycerin-Anlagerungsprodukte an Methylglucosid-Fettsäureester, Fettsäurealkanolamide und Fettsäureglucamide,
• – C₈-C₂₂-Alkylmono- und -oligoglycoside und deren ethoxylierte Analoga, wobei Oligomerisierungsgrade von 1,1 bis 5, insbesondere 1,2 bis 2,0, und Glucose als Zuckerkomponente bevorzugt sind,
• – Gemische aus Alkyl-(oligo)-glucosiden und Fettalkoholen, zum Beispiel die im Handel erhältlichen Produkte Montanov^®68, Montanov^®L und Montanov^®202,
• – Anlagerungsprodukte von 5 bis 60 Mol Ethylenoxid an Rizinusöl und gehärtetes Rizinusöl,
• – Partialester von Polyolen mit 3-6 Kohlenstoffatomen mit gesättigten Fettsäuren mit 8 bis 22 C-Atomen,
• – Sterine. Als Sterine wird eine Gruppe von Steroiden verstanden, die am C-Atom 3 des Steroid-Gerüstes eine Hydroxylgruppe tragen und sowohl aus tierischem Gewebe (Zoosterine) wie auch aus pflanzlichen Fetten (Phytosterine) isoliert werden. Beispiele für Zoosterine sind das Cholesterin und das Lanosterin. Beispiele geeigneter Phytosterine sind Ergosterin, Stigmasterin und Sitosterin. Auch aus Pilzen und Hefen werden Sterine, die sogenannten Mykosterine, isoliert.
• – Phospholipide. Hierunter werden vor allem die Glucose-Phospolipide, die z.B. als Lecithine bzw. Phosphatidylcholine aus z.B. Eidotter oder Pflanzensamen (z.B. Sojabohnen) gewonnen werden, verstanden.
• – Fettsäureester von Zuckern und Zuckeralkoholen, wie Sorbit, und Anlagerungsprodukte von Ethylenoxid an Zuckertettsäureester, beispielsweise die Handelsprodukte Glucate SS, Glucate DO, Glucamate DOE 120 und Glucamate SSE 20,
• – Polyglycerine und Polyglycerinderivate wie beispielsweise Polyglycerinpoly-12-hydroxystearat (Handelsprodukt Dehymuls^® PGPH),
• – Lineare und verzweigte Fettsäuren mit 8 bis 30 C-Atomen und deren Na-, K-, Ammonium-, Ca-, Mg- und Zn-Salze.

In a further preferred embodiment, the agents according to the invention may contain emulsifiers (F). Emulsifiers effect 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 1 to 100, preferably 4 to 30, moles of ethylene oxide and / or 0 to 5 moles of propylene oxide onto linear fatty alcohols containing 8 to 22 carbon atoms, to fatty acids containing 12 to 22 carbon atoms and to alkylphenols having 8 to 15 carbon atoms Atoms in the alkyl group,
• - C ₁₂ -C ₂₂ fatty acid mono- and diesters of addition products of 1 to 30 moles of ethylene oxide onto polyols having 3 to 6 carbon atoms, in particular glycerol,
• Ethylene oxide and polyglycerol addition products to methyl glucoside fatty acid esters, fatty acid alkanolamides and fatty acid glucamides,
• C ₈ -C ₂₂ -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, such as the commercially available products Montanov® ^® 68, Montanov® ^® L and Montanov® ^® 202
• Adducts of 5 to 60 moles of ethylene oxide with castor oil and hydrogenated castor oil,
• Partial esters of polyols having 3-6 carbon atoms with saturated fatty acids having 8 to 22 C atoms,
• - sterols. Sterols are understood to mean a group of steroids which have a hydroxyl group on C-atom 3 of the steroid skeleton and are isolated both from animal tissue (zoosterols) and from vegetable fats (phytosterols). Examples of zoosterols are cholesterol and lanosterol. Examples of suitable phytosterols are ergosterol, stigmasterol and sitosterol. Mushrooms and yeasts are also used to isolate sterols, the so-called mycosterols.
• - Phospholipids. These include, in particular, the glucose phospholipids which are obtained, for example, as lecithins or phosphatidylcholines from, for example, egg yolks or plant seeds (for example soybeans).
• Fatty acid esters of sugars and sugar alcohols, such as sorbitol, 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,
• - polyglycerols and polyglycerol derivatives such as polyglycerol poly-12-hydroxystearate (commercial product Dehymuls ^® PGPH),
• - Linear and branched fatty acids with 8 to 30 carbon atoms and their Na, K, ammonium, Ca, Mg and Zn salts.

The Compositions of the invention contain the emulsifiers preferably in amounts of 0.1 to 25 wt .-%, particularly preferably 0.5-15 Wt .-% and extraordinary preferably 1 - 5 Wt .-%, each based on the total composition.

Prefers can the compositions of the invention at least one nonionic emulsifier having an HLB value of 8 to 18 included. Nonionic emulsifiers with an HLB value from 10 - 15 can particularly according to the invention be preferred.

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.

wobei jeweils mindestens ein Rest R von mindestens einem Alkohol stammt, der ausgewählt ist aus der Gruppe, die (Z)-2-Hexen-1-ol, (E)-2-Hexen-1-ol, (Z)-3-Hexen-1-ol (Blätteralkohol), (E)-3-Hexen-1-ol, (Z)-4-Hexen-1-ol, (E)-4-Hexen-1-ol, 5-Hexen-1-ol, Zimtalkohol, 3-Phenylpropan-1-ol (Hydrozimtalkohol), 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)-furanon (Furaneol^®), 4-Hydroxy-3-methoxy-benzaldehyd (Vanillin), 4-(4-Hydroxyphenyl)-2-butanon (Himbeerketon), (Z,Z)-3,6-Nonadien-1-ol, 3,7-Dimethyl-7-octen-1-ol (Rhodinol) und (Z)-3-Octen-1-ol enthält, und die anderen Reste R jeweils unabhängig voneinander ausgewählt sind aus der Gruppe, die ein Wasserstoffatom, die geradkettigen oder verzweigten, gesättigten oder ungesättigten, substituierten oder unsubstituierten C_1-6-Kohlenwasserstoffreste und den 2-Phenoxyethyl-Rest enthält, und m Werte aus dem Bereich 1 bis 20 und n Werte aus dem Bereich 2 bis 100 annimmt, sowie Mischungen hiervon, daher mindestens ein Polymer zugesetzt, wobei sich sowohl kationische, anionische, amphotere als auch nichtionische Polymere als wirksam erwiesen haben. Ohne an diese Theorie gebunden sein zu wollen, wird vermutet, dass die Gegenwart eines Polymers die Anhaftung der Kieselsäureester auf der behandelten Oberfläche weiter verbessert oder aber die Duftfreisetzung nach einem anderen Mechanismus positiv beeinflusst.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 comprise 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, 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-nonadiene-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 consisting of a hydrogen atom that are straight-chain or branched, saturated or unsaturated, substituted or unsubstituted C _1-6 hydrocarbon radicals and the 2-phenoxyethyl radical, and m takes 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 Both cationic, anionic, amphoteric and nonionic polymers have proven 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 quartenary 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 synthesized from acrylic acid, methacrylic acid or derivatives thereof, polymer backbone have been found to be particularly suitable.

in der R¹= -H oder -CH₃ ist, R², R³ und R⁴ unabhängig voneinander ausgewählt sind aus C_1-4-Alkyl-, -Alkenyl- oder -Hydroxyalkylgruppen, m = 1, 2, 3 oder 4, n eine natürliche Zahl und X^- ein physiologisch verträgliches organisches oder anorganisches Anion ist, sowie Copolymere, bestehend im wesentlichen aus den in Formel (G1-I) aufgeführten Monomereinheiten sowie nichtionogenen Monomereinheiten, sind besonders bevorzugte kationische Polymere. Im Rahmen dieser Polymere sind diejenigen erfindungsgemäß bevorzugt, für die mindestens eine der folgenden Bedingungen gilt:

• – R¹ steht für eine Methylgruppe
• – R², R³ und R⁴ stehen für Methylgruppen
• – m hat den Wert 2.

Homopolymers of the general formula (G1-I),

wherein 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 acceptable 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 (methacryloyloxyethyltrimethylammonium chloride) 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 poly olefinically unsaturated compounds, for example divinylbenzene, tetraallyloxyethane, methylenebisacrylamide, diallyl ether, polyallylpolyglyceryl ethers, 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 (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 Tridecylpolyoxypropylen polyoxyethylene ether (INCI name : PPG-1-trideceth-6)) are commercially available.

Copolymers having monomer units of the formula (G1-I) contain as nonionic monomer units preferably acrylamide, methacrylamide, acrylic acid-C _1-4 -alkyl esters and methacrylic acid-C _1-4 -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 copolymer preferred according to the invention is the crosslinked acrylamide-methacryloyloxyethyltrimethylammonium chloride copolymer. Such copolymers in which the monomers are present in a weight ratio of about 20:80, are commercially available as approximately 50% non-aqueous polymer dispersion 92 under the name Salcare ^® SC.

• – quaternisierte Cellulose-Derivate, wie sie unter den Bezeichnungen Celquat^® und Polymer JR^® im Handel erhältlich sind. Die Handelsprodukte Celquat^® H 100, Celquat^® L 200 und Polymer JR^®400 bzw. Verbindungen mit den INCI-Bezeichnungen Polyquaternium-10 oder Polyquaternium-24 sind bevorzugte quaternierte Cellulose-Derivate,
• – kationische Alkylpolyglycoside gemäß der DE-PS 44 13 686,
• – kationiserter Honig, beispielsweise das Handelsprodukt Honeyquat^® 50,
• – kationische Guar-Derivate, wie insbesondere die unter den Handelsnamen Cosmedia^®Guar und Jaguar^® vertriebenen Produkte,
• – polymere Dimethyldiallylammoniumsalze und deren Copolymere mit Estern und Amiden von Acrylsäure und Methacrylsäure. Die unter den Bezeichnungen Merquat^®100 (Poly(dimethyldiallylammoniumchlorid)) und Merquat^®550 (Dimethyldiallylammoniumchlorid-Acrylamid-Copolymer) im Handel erhältlichen Produkte mit der INCI-Bezeichnung Polyquaternium-7 sind Beispiele für solche bevorzugten kationischen Polymere,
• – Copolymere des Vinylpyrrolidons mit quaternierten Derivaten des Dialkylaminoalkylacrylats und -methacrylats, wie beispielsweise mit Diethylsulfat quaternierte Vinylpyrrolidon-Dimethylaminoethylmethacrylat-Copolymere. Solche Verbindungen sind unter den Bezeichnungen Gafquat^®734 und Gafquat^®755 im Handel erhältlich,
• – Vinylpyrrolidon-Vinylimidazoliummethochlorid-Copolymere, wie sie unter den Bezeichnungen Luviquat^® FC 370, FC 550, FC 905 und HM 552 angeboten werden,
• – quaternierter Polyvinylalkohol,
• – sowie die unter den Bezeichnungen Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 und Polyquaternium 27 bekannten Polymeren mit quartären Stickstoffatomen in der Polymerhauptkette.

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, such as in particular the products sold under the trade names Cosmedia® ^® Guar and Jaguar ^®,
• - Dimethyldiallylammoniumsalze polymeric and their copolymers with esters and amides of acrylic acid and methacrylic acid. Under the names Merquat ^® 100 (Poly (dimethyldiallylammonium chloride)) and Merquat ^® 550 (dimethyldiallylammonium chloride-acrylamide copolymer) commercially available products with the INCI name Polyquaternium-7 are examples of such preferred cationic polymers,
• - Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoalkyl acrylate and methacrylate, such as diethyl sulfate quaternized vinylpyrrolidone-dimethylaminoethyl methacrylate copolymers. Such compounds are sold under the names Gafquat ^® 734 and Gafquat ^® 755 commercially,
• - vinylpyrrolidone vinylimidazoliummethochloride copolymers, such as those offered under the names Luviquat.RTM ^® FC 370, FC 550, FC 905 and HM 552,
• - quaternized polyvinyl alcohol,
• - as well as the polymers known under the names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27 with quaternary nitrogen atoms in the polymer main chain.

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

Further cationic polymers 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. For example, chitosan and its derivatives are preferred as Hydagen CMF ^®, Hydagen HCMF ^®, Kytamer ^® PC and Chitolam ^® NB / 101, for example, under the trade names commercially available.

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 Alkylpolyglycodside according to DE-PS 44 13 686 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. Preference is given to those cationic protein hydrolyzates whose underlying protein content has a molecular weight of 100 to 25,000 daltons, preferably 250 to 5000 daltons. Furthermore, cationic protein hydrolyzates are to be understood as meaning quaternized amino acids and mixtures thereof. The quaternization of the protein hydrolyzates or amino acids is often carried out using quaternary ammonium salts such as N, N-dimethyl-N- (n-alkyl) -N- (2-hydroxy-3-chloro-n-propyl) ammonium halides. Furthermore, the cationic protein hydrolysates may also be further derivatized. As typical examples of the cationic protein hydrolyzates and derivatives of the present invention, those listed under the INCI names in the International Cosmetic Ingredient Dictionary and Handbook, (seventh edition 1997, The Cosmetic, Toiletry, and Fragrance Association, Washington, DC) are commercially available Products Available: Cocodimony Hydroxypropyl Hydrolyzed Collagen, Cocodimopnium Hydroxypropyl Hydrolyzed Casein, Cocodimonium Hydroxypropyl Hydrolyzed Collagen, Cocodimonium Hydroxypropyl Hydrolyzed Hair Keratin, Cocodimonium Hydroxypropyl Hydrolyzed Keratin, Cocodimonium Hydroxypropyl Hydrolyzed Rice Protein, Cocodimonium Hydroxypropyl Hydrolyzed Soy Protein, Cocodimonium Hydroxypropyl Hydrolyzed Wheat Protein, Hydroxypropyl Arginine Lauryl / Myristyl Ether HCl, Hydroxypropyltrimonium Gelatin, Hydroxypropyltrimonium Hydrolyzed Casein, Hydroxypropyltrimonium Hydrolyzed Collagen, Hydroxypropyltrimonium Hydrolyzed Conchiolin Protein, Hydroxypropyltrimonium Hydrolyzed Keratin, Hydroxypropyltrimonium Hydrolyzed Rice Bran Protein, Hydroxypropyltrimonium Hydrolyzed Soy Protein, Hydroxypropyl Hydrolyzed Vegetable Protein, Hydroxypropyltrimonium Hydrolyzed Wheat Protein, Hydroxypropyltrimonium Hydrolyzed Wheat Protein / Siloxysilicate, Lauridimonium Hydroxypropyl Hydrolyzed Soy Protein, Lauridimonium Hydroxypropyl Hydrolyzed Wheat Protein, Lauridimonium Hydroxypropyl Hydrolyzed Wheat Protein / Siloxysilicate, Lauryldimony Hydroxypropyl Hydrolyzed Casein, Lauryldimonium Hydroxypropyl Hydrolyzed Collagen, Lauryldimonium Hydroxypropyl Hydrolyzed Keratin, Lauryldimonium Hydroxypropyl Hydrolyzed Soy Protein, 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 Protein, Steartrimonium Hydroxyethyl Hydrolyzed Collagen, Quaternium-76 Hydrolyzed Collagen, Quaternium-79 Hydrolyzed Collagen, Quaternium-79 Hydrolyzed Keratin, Quaternium-79 Hydrolyzed Milk Protein, Quaternium-79 Hydrolyzed Soy Protein, Quaternium-79 Hydrolyzed Wheat Protein.

All particularly preferred are the optionally cationized protein hydrolysates and plant-based derivatives.

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

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

• A) monomers having quaternary ammonium groups of the general formula (ZI), 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 are hydrogen or a methyl group and R ³ , R ⁴ and R ⁵ are each independently alkyl groups having 1 to 4 carbon atoms, Z is an NH group or an oxygen atom, n is an integer of 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 (Z-II) in which R ⁶ and R ^{7 are} independently hydrogen or methyl groups.

suitable Starting monomers are z. Dimethylaminoethylacrylamide, dimethylaminoethylmethacrylamide, Dimethylaminopropylacrylamide, dimethylaminopropylmethacrylamide and Diethylaminoethylacrylamid, if Z is an NH group or Dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate and diethylaminoethyl acrylate, when Z is an oxygen atom.

The a tertiary Amino-containing monomers are then in a known manner quaternized, wherein as alkylating reagents methyl chloride, dimethyl sulfate or diethyl sulfate are particularly suitable. The quaternization reaction can in aqueous solution or in the solvent respectively.

Advantageously, those monomers of formula (ZI) are used which are derivatives of acrylamide or methacrylamide. 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 ⁴ and R ^{5 are} methyl groups.

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

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

The can be used according to the invention zwitterionic polymers are prepared from monomers of the formulas (Z-I) and (Z-II) according to known polymerization. The polymerization can be either in aqueous or aqueous-alcoholic solution respectively. Alcohols are alcohols having 1 to 4 carbon atoms, preferably isopropanol, used simultaneously as a polymerization regulator serve. The monomer solution can but other components are added as a regulator, z. B. formic acid or mercaptans, such as thioethanol and thioglycolic acid. The initiation of the polymerization takes place with the help of radical-forming substances. For this purpose, redox systems and / or thermally decomposing radical formers of the azo compound type, such as Azoisobutyronitrile, Azobis (cyanopentanoic acid) or azo-bis (amidinopropane) dihydrochloride be used. As redox systems are z. B. Combinations from hydrogen peroxide, potassium or ammonium peroxodisulfate as well tertiary Butyl hydroperoxide with sodium sulfite, sodium dithionite or hydroxylamine hydrochloride as a reduction component.

When Such polymers have proven particularly effective in which the monomers of the formula (Z-I) over the monomers of the formula (Z-II) in excess templates. It is therefore preferred according to the invention, such polymers to be used, consisting of monomers of the formula (Z-I) 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.

The cationic or amphoteric polymers are in the inventive compositions preferably in amounts of 0.05 to 10 wt .-%, based on the total Means, included. Amounts of 0.1 to 5 wt .-% are particularly preferred.

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

When anionic polymers have proven to be particularly effective containing as sole or co-monomer 2-acrylamido-2-methylpropanesulfonic acid, wherein the sulfonic acid group wholly or partly as sodium, potassium, ammonium, mono- or Triethanolammonium salt may be present.

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

Within this embodiment For example, it may be preferable to use copolymers of at least one anionic Use monomer and at least one nonionic monomer. In terms of The anionic monomers are based on the substances listed above directed. Preferred nonionic monomers are acrylamide, methacrylamide, acrylate, methacrylates, Vinyl pyrrolidone, vinyl ethers and vinyl esters.

Preferred anionic copolymers are acrylic acid-acrylamide copolymers and in particular polyacrylamide copolymers with sulfonic acid-containing monomers. A particularly preferred anionic copolymer consists of 70 to 55 mol% of acrylamide and 30 to 45 mol% of 2-acrylamido-2-methylpropanesulfonic acid, wherein the sulfonic acid group is wholly or partly in the form of sodium, potassium, ammonium, mono- or triethanolammonium Salt is present. This copolymer may also be crosslinked, with crosslinking agents preferably polyolefinically unsaturated compounds such as tetraallyloxyethane, allylsucrose, allylpentaerythritol and methylene-bisacrylamide are used. Such a polymer is contained in the commercial product Sepigel ^® 305 from SEPPIC. The use of this compound, which in addition to the polymer component contains a hydrocarbon mixture (C ₁₃ -C ₁₄ isoparaffin) and a nonionic emulsifier (laureth-7), has proved 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 / Caprylglucoside marketed sodium acryloyldimethyltaurate copolymers with a comonomer selected from acrylamide, hydroxyethyl acrylate and sodium acrylate have been found to be particularly effective according to the invention.

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

Copolymers of maleic anhydride and methyl vinyl ether, especially those with crosslinks, are also color-retaining polymers. A with 1,9-decadiene crosslinked maleic acid-methyl vinyl ether copolymer is commercially 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 are capable of forming internal salts, as well as zwitterionic polymers which in the molecule have quaternary ammonium groups and -COO '- or -SO _3' containing groups, and combined such polymers containing -COOH or _SO3H groups and quaternary ammonium groups.

An example of the present invention amphopolymer suitable is the acrylic resin commercially available as Amphomer ^® 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, Represents methacrylic acid and its simple esters.

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

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 ^(-) (G ³ -I) in which R ¹ and R ² independently of one another are hydrogen or a methyl group and R ³ , R ⁴ and R ⁵ are each independently alkyl groups having 1 to 4 carbon atoms, Z is an NH group or an oxygen atom, n is an integer from 2 to 5 and A is the anion of an organic or inorganic acid, and
• (b) monomeric carboxylic acids of the general formula (G3-II), R ⁶ -CH = CR ⁷ -COOH (G3-II) in which R ⁶ and R ^{7 are} independently hydrogen or methyl groups.

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 ^{(-) is} a halide, methoxysulfate or ethoxysulfate Ion is; Acrylamidopropyl trimethyl ammonium chloride is a particularly preferred monomer (a). Acrylic acid is preferably used as monomer (b) for the stated polymers.

The agents according to the invention can in a further embodiment non-ionic polymers (G4).

• – Vinylpyrrolidon/Vinylester-Copolymere, wie sie beispielsweise unter dem Warenzeichen Luviskol^® (BASF) vertrieben werden. Luviskol^® VA 64 und Luviskol^® VA 73, jeweils Vinylpyrrolidon/Vinylacetat-Copolymere, sind ebenfalls bevorzugte nichtionische Polymere.
• – Celluloseether, wie Hydroxypropylcellulose, Hydroxyethylcellulose und Methylhydroxypropylcellulose, wie sie beispielsweise unter den Warenzeichen Culminal^® und Benecel^® (AQUALON) und Natrosol^®-Typen (Hercules) vertrieben werden.
• – Stärke und deren Derivate, insbesondere Stärkeether, beispielsweise Structure^® XL (National Starch), eine multifunktionelle, salztolerante Stärke;
• – Schellack
• – Polyvinylpyrrolidone, wie sie beispielsweise unter der Bezeichnung Luviskol^® (BASF) vertrieben werden.
• – Siloxane. Diese Siloxane können sowohl wasserlöslich als auch wasserunlöslich sein. Geeignet sind sowohl flüchtige als auch nichtflüchtige Siloxane, wobei als nichtflüchtige Siloxane solche Verbindungen verstanden werden, deren Siedepunkt bei Normaldruck oberhalb von 200 °C liegt. Bevorzugte Siloxane sind Polydialkylsiloxane, wie beispielsweise Polydimethylsiloxan, Polyalkylarylsiloxane, wie beispielsweise Polyphenylmethylsiloxan, ethoxylierte Polydialkylsiloxane sowie Polydialkylsiloxane, die Amin- und/oder Hydroxy-Gruppen enthalten.
• – glycosidisch substituierte Silicone.

Preferred nonionic polymers are, for example:

• - Vinylpyrrolidone / vinyl ester copolymers, such as those sold 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, as for example under the trademark Culminal® ^® and Benecel ^® (AQUALON) and Natrosol ^® grades (Hercules) are distributed.
• - starch and its derivatives, in particular starch, such as Structure XL ^® (National Starch), a multifunctional, salt-tolerant starch;
• - shellac
• - polyvinylpyrrolidones, as 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 According to the invention it is also possible that the preparations used several, in particular two different Polymers of the same charge and / or one ionic and one each containing amphoteric and / or nonionic polymer.

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

Further preferred compositions according to the invention are characterized in that they contain at least one UV filter substance. The inventively preferred UV filters are subject There are no general limitations to their structure and physical properties. On the contrary, all UV filters which can be used in the cosmetics sector and whose absorption maximum lies in the UVA (315-400 nm), in the UVB (280-315 nm) or in the UVC (<280 nm) range are suitable. UV filters with an absorption maximum in the UVB range, in particular in the range from about 280 to about 300 nm, are particularly preferred.

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, monomeric and oligomeric 4,4-Diarylbutadiencarboxylic acid esters and -carbonsäureamiden, Ketotricyclo (5.2.1.0) decane, Benzalmalonsäureestern, benzoxazole and any mixtures of the above components. 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'-methylbenzylidene) -D, L-camphor, 4- (dimethylamino) benzoic acid 2-ethylhexyl ester, 4- (dimethylamino) benzoic acid 2-octyl ester, 4 - (dimethylamino) benzoate, 4-methoxycinnamic acid 2-ethylhexyl ester, propyl 4-methoxycinnamate, isopentyl 4-methoxycinnamate, 2-cyano-3,3-phenylcinnamic acid 2-ethylhexyl ester (octocrylene), 2-ethylhexyl salicylate, salicylic acid-4 isopropylbenzyl ester, salicylic acid homomenthyl ester (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-ethylhexyl ester, to polymers ge bound UV filters, 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- (2N -benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol) [Tinosorb M (Ciba)], 2,2'-methyl-bis- [6 (2H-benzotriazol-2-yl ) -4- (methyl) phenol] (MIXXIM BB / 200 from Fairmount Chemical), 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) benzotriazole (CAS No .: 025973-551 ), 2- (2'-hydroxy-5'-octylphenyl) benzotr iazole (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-hexyloxy) -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-ethylhexyloxy) -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- (4- ethylcarboxyl) -phenylamino] -1,3,5-triazine, 2,4-bis - {[4- (2-ethylhexyloxy) -2-hydroxy] -phenyl} -6- (1-methylpyrrol-2-yl ) 1,3,5-tri azine, 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 ', 3', 5 ', 5', 5'-heptamethylsiloxy-2-methyl-propyloxy) -2-hydroxy] -phenyl} -6- (4-methoxyphenyl) -1,3,5-triazine and mixtures of mentioned 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 Glucammoniumsalze, in particular 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 Neo Heliopan Hydro available from Symrise and the phenylene-1,4-bis (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid bis-sodium salt having the INCI name Disodium Phenyl dibenzimidazole tetrasulfonates (CAS No .: 180898-37-7), which is available, for example, under the trade name Neo Heliopan AP from Symrise, 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-bionylidenemethyl) 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 trade name Mexoryl SX from Chimex).

Some of the oil-soluble UV filters can themselves serve as solvents or solubilizers for other UV filters. Thus, solutions of the UV-A-filter 1 can be, for example, (4-tert-butylphenyl) -3- (4'methoxyphenyl) propane-1,3-dione (z. B. 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 2-ethoxycinnamate, 2-ethylhexyl 2-cyano-3,3-phenylcinnamate, 2-ethylhexyl salicylate and 3,3,5-trimethylcyclohexylsalicylate. 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 nanopigments. They may have a spherical shape, but it is also possible to use those particles which have an ellipsoidal or otherwise deviating shape from the spherical 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 agents according to the invention also contain plant extracts (L). Usually these extracts produced by extraction of the entire plant. But it can in some cases too be preferred, the extracts exclusively from flowers and / or Scroll to produce the plant.

According to the invention are available especially the extracts of green Tea, Oak bark, Stinging nettle, Hamamelis, Hops, Henna, Chamomile, Burdock root, horsetail, hawthorn, lime blossom, almond, Aloe vera, spruce needle, horse chestnut, Sandalwood, juniper, coconut, Mango, Apricot, Lime, Wheat, Kiwi, Melon, Orange, Grapefruit, Sage, Rosemary, Birch, Mallow, Meadowfoam, Quendel, Yarrow, Thyme, melissa, hominy, coltsfoot, marshmallow, meristem, ginseng and ginger root preferred.

As extraction agent for the preparation of said plant extracts water, alcohols and mixtures thereof can be used. Among the alcohols are lower alcohols such as ethanol and isopropanol, but especially polyhydric alcohols such as ethylene glycol and propylene glycol, both as sole extractant and in admixture with water, are preferred. Plant extracts based on water / propylene glycol in a ratio of 1:10 to 10: 1 have proven to be particularly suitable. Further particularly preferred extractants are cosmetic oils, in particular the esters of linear or branched C _6-30 fatty acids with linear or branched C _2-30 fatty alcohols, such as isopropyl palmitate, furthermore hydroxycarboxylic acid alkyl esters 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 according to the invention both in pure as well as in diluted Form are used. If used in dilute form, they usually contain about 2 - 80 Wt .-% of active substance and as a solvent the extractant or extractant mixture used in their extraction. Furthermore, it may be preferred in the inventive compositions Mixtures of several, especially two, different plant extracts use.

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-hydroxyethyl urea), guanidine and its derivatives, arginine and its derivatives, water glass, imidazole and its derivatives, histidine and its Derivatives, benzyl alcohol, glycerol, glycol and glycol ethers, propylene glycol and propylene glycol ethers, for example propylene glycol monoethyl ether, carbonates, bicarbonates, diols and triols, and in particular 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.

Advantageous in the sense of the invention additionally short-chain carboxylic acids (N) the active substance complex (A) - from at least one apolar ingredient and at least one protein complexed trace element from the Support group Zn, Mg, Cu, Mn, Si, K, Fe. Under short-chain carboxylic acids and their derivatives in the context of the invention are understood to mean carboxylic acids, which is saturated or unsaturated and / or straight-chain or branched or cyclic and / or aromatic and / or may be heterocyclic and have a molecular weight less than 750. Preferred in the sense of the invention saturated or unsaturated straight-chain or branched carboxylic acids having a chain length of 1 to 16 carbon atoms in the chain, most preferably are those with a chain length from 1 to 12 C atoms in the chain.

The short-chain carboxylic acids in the sense of the invention have one, two, three or more carboxy groups. Preferred in Purpose of the invention are carboxylic acids with several carboxy groups, in particular di- and tricarboxylic acids. The Carboxy groups can in whole or in part as ester, acid anhydride, lactone, Amide, imidic acid, Lactam, lactim, dicarboximide, carbohydrazide, hydrazone, hydroxam, Hydroxime, amidine, amidoxime, nitrile, phosphonic or phosphate ester available. The carboxylic acids according to the invention may of course along be substituted the carbon chain or the ring skeleton. To the substituents of the carboxylic acids according to the invention are, for example, too counting C1-C8-alkyl, C2-C8-alkenyl, aryl, aralkyl and aralkenyl, hydroxymethyl, C2-C8-hydroxyalkyl, C2-C8-hydroxyalkenyl, aminomethyl, C2-C8-aminoalkyl-, Cyano, formyl, oxo, thioxo, hydroxy, mercapto, amino, carboxy or imino groups. Preferred substituents are 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 is optionally substituted by alkyl, Aryl, aralkyl and / or alkenyl radicals may be further substituted. Furthermore, also preferred carboxylic acid derivatives are the phosphonic and Phosphatester.

in der Z steht für eine lineare oder verzweigte Alkyl- oder Alkenylgruppe mit 4 bis 12 Kohlenstoffatomen, n für eine Zahl von 4 bis 12 sowie eine der beiden Gruppen X und Y für eine COOH-Gruppe und die andere für Wasserstoff oder einen Methyl- oder Ethylrest, Dicarbonsäuren der allgemeinen Formel (N-I), die zusätzlich noch 1 bis 3 Methyl- oder Ethylsubstituenten am Cyclohexenring tragen sowie Dicarbonsäuren, die aus den Dicarbonsäuren gemäß Formel (N-I) formal durch Anlagerung eines Moleküls Wasser an die Doppelbindung im Cyclohexenring entstehen.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, isocrotonic acid , Elaidic, maleic, fumaric, muconic, citraconic, mesaconic, camphoric, benzoic, o, m, p-phthalic, naphthoic, toluoic, hydratropic, atropic, cinnamic, isonicotinic, nicotinic, bicarbamic, 4,4'-dicyano-6, 6'-binicotinic acid, 8-carbamoyloctanoic acid, 1,2,4-pentanetricarboxylic acid, 2-pyrrolecarboxylic acid, 1,2,4,6,7-naphthalenepentaacetic acid, malonaldehyde acid, 4-hydroxy-phthalamic acid, 1-pyrazolecarboxylic acid, gallic acid or propane tricarboxylic acid, a Dicarboxylic acid selected from the group formed by compounds d he general formula (NI),

in the Z is 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 formally from the dicarboxylic acids according to formula (NI) by addition of a molecule of water to the double bond in the cyclohexene ring.

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

The dicarboxylic acids of the formula (NI) can be prepared, for example, by reacting polyunsaturated dicarboxylic acids with unsaturated monocarboxylic acids in the form of a Diels-Alder cyclization become. Usually one will assume a polyunsaturated fatty acid as the dicarboxylic acid component. Preferred is the linoleic acid obtainable from natural fats and oils. Acrylic acid, but also, for example, methacrylic acid and crotonic acid are particularly preferred as the monocarboxylic acid component. 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.

Usable according to the invention in addition to the preferred dicarboxylic acids according to formula (N-I) are also dicarboxylic acids, from the compounds of the formula (N-I) by 1 to 3 differentiate methyl or ethyl substituents on the cyclohexyl ring or formally from these compounds by addition of one molecule of water be formed on the double formation of the cyclohexene ring.

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).

Next the example listed above short-chain according to the invention carboxylic acids yourself can also their physiologically compatible Salts used according to the invention become. examples for such salts are the alkali, alkaline earth, zinc salts and ammonium salts, Within the scope of the present application, the mono-, di- and trimethyl, ethyl and hydroxyethyl ammonium salts to be understood. Very particularly preferred within the scope of the invention but with alkaline amino acids, such as arginine, Lysine, ornithine and histidine, neutralized acids are used. Furthermore, can it for formulation reasons be preferred, the carboxylic acid from the water-soluble Representatives, in particular the water-soluble salts.

Furthermore, it is preferred according to the invention, hydroxycarboxylic acids and here again in particular the dihydroxy, trihydroxy and polyhydroxycarboxylic acids and the dihydroxy, trihydroxy and polyhydroxy di-, tri- and polycarboxylic acids together with the active ingredient (A) -einsetzen. 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 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 C atoms, ie, for example, fatty alcohols or synthetic fatty alcohols. The esters of C ₁₂ -C ₁₅ fatty alcohols are particularly preferred. Esters of this type are commercially available, eg under the trademark Cosmacol® ^® EniChem, Augusta Industriale.

The Use amount of Hydroxycarbonsäureester is thereby 0,1 - 15 Wt .-% based on the average, preferably 0.1 to 10 wt .-% and very particularly preferably 0.1-5 Wt .-%.

According to one another preferred embodiment contain the agents of the invention furthermore at least one fatty substance, in particular at least one fatty substance Fat in nanoparticulate Shape. Such a nanoparticulate Fatty is, for example, nanoparticulate hydrogenated castor oil. The middle Size of the nanoparticles is preferably about 100 nm or below, based on the particle diameter.

Additionally preferred cosmetic preparations according to the invention additionally contain silicone (s). 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 from finally) in deodorant or antiperspirant compositions), particularly preferably 0.2-10% by weight, preferably 0.25-7% by weight and in particular 0.5-5% by weight, in each case based on the total agent, contain.

The preferred amount of silicones depends on the

• (i) Polyalkylsiloxanen, Polyarylsiloxanen, Polyalkylarylsiloxanen, die flüchtig oder nicht flüchtig, geradkettig, verzweigt oder cyclisch, vernetzt oder nicht vernetzt sind;
• (ii) Polysiloxanen, die in ihrer allgemeinen Struktur eine oder mehrere organofunktionelle Gruppen enthalten, die ausgewählt sind unter: a) substituierten oder unsubstituierten aminierten Gruppen; b) (per)fluorierten Gruppen; c) Thiolgruppen; d) Carboxylatgruppen; e) hydroxylierten Gruppen; f) alkoxylierten Gruppen; g) Acyloxyalkylgruppen; h) amphoteren Gruppen; i) Bisulfitgruppen; j) Hydroxyacylaminogruppen; k) Carboxygruppen; l) Sulfonsäuregruppen; und m) Sulfat- oder Thiosulfatgruppen;
• (iii) linearen Polysiloxan(A)- Polyoxyalkylen(B)- Blockcopoylmeren vom Typ (A-B)_n mit n > 3;
• (iv) gepfropften Siliconpolymeren mit nicht siliconhaltigem, organischen Grundgerüst, die aus einer organischen Hauptkette bestehen, welche aus organischen Monomeren gebildet wird, die kein Silicon enthalten, auf die in der Kette sowie gegebenenfalls an mindestens einem Kettenende mindestens ein Polysiloxanmakromer gepfropft wurde;
• (v) gepfropften Siliconpolymeren mit Polysiloxan- Grundgerüst, auf das nicht siliconhaltige, organische Monomere gepfropft wurden, die eine Polysiloxan-Hauptkette aufweisen, auf die in derKette sowie gegebenenfalls an mindestens einem ihrer Enden mindestens ein organisches Makromer gepfropft wurde, das kein Silicon enthält;
• (vi) oder deren Gemischen.

Particular preference is given to cosmetic preparations according to the invention which comprise at least one silicone selected from:

• (i) polyalkyl siloxanes, polyaryl siloxanes, polyalkylaryl siloxanes which are volatile or nonvolatile, straight chain, branched or cyclic, crosslinked or uncrosslinked;
• (ii) polysiloxanes containing in their general structure one or more organofunctional 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; l) 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 not containing silicone has been grafted in the chain and optionally at least at one of its ends;
• (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 [-Si (CH ₃ ) ₂ ] _x -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 above formula I. 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-Si (CH ₃ ) ₃
(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 [O- (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 (CH ₃ ) 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 you can too Mixtures of the above Silicones in the compositions according to the invention be included.

Preferred silicones which can be used according to the invention have viscosities of from 0.2 to 2 mm ² s ^-1 at 20 ° C., silicones having viscosities of from 0.5 to 1 mm ² s ^{-1 being} particularly preferred.

Particularly preferred agents according to the invention contain one or more amino-functional silicones. Such silicones may, for example, be represented by the formula M (R _a Q _b SiO _{(4-ab) / 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, halohydrocarbon radicals such as 3-chloropropyl, 4-bromobutyl, 3,3,3-trifluoropropyl, chlorocyclohexyl, bromophenyl, chlorophenyl and the like, and sulfur containing radicals such as mercaptoethyl, mercaptopropyl, mercaptohexyl, mercaptophenyl and the like; preferably R 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 ) ₃ CC (O) OCH ₂ CH ₂ -, C ₆ H ₄ C ₆ H ₄ -, -C ₆ H ₄ CH ₂ C ₆ H ₂ -; and - (CH ₂ ) ₃ C (O) SCH ₂ CH ₂ -.

Z is an organic, amino-functional radical containing at least one functional amino group. A possible formula for Z is NH (CH ₂ ) _z NH ₂ , wherein z is 1 or more. Another possible formula for Z is -NH (CH ₂ ) _z (CH ₂ ) _zz NH, wherein both z and zz are independently 1 or more, which structure includes diamino ring structures, such as piperazinyl. Z is most preferably a -NHCH ₂ CH ₂ NH ₂ radical. Another possible formula for Z is - N (CH ₂ ) _z (CH ₂ ) _zz NX ₂ or -NX ₂ , wherein each X of X _{2 is} independently selected from the group consisting of hydrogen and alkyl groups of 1 to 12 carbon atoms, and zz is 0.

Q is most preferably a polar, amine functional group of formula -CH ₂ CH ₂ CH ₂ NHCH ₂ CH ₂ NH z. 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-ab) / 2} units to the R _c SiO _{(4-c) / 2} units is in the range of about From 1: 2 to 1:65, preferably from about 1: 5 to about 1: 65, and most preferably from about 1: 15 to about 1: 20. When one or more silicones of the above formula are employed then the various variable substituents in the above formula may be different for the various silicone components present in the silicone blend.

• – G ist-H, eine Phenylgruppe, -OH, -O-CH₃, -CH₃, -O-CH₂CH₃, -CH₂CH₃, -O-CH₂CH₂CH₃,-CH₂CH₂CH₃, -O-CH(CH₃)₂, -CH(CH₃)₂, -O-CH₂CH₂CH₂CH₃, -CH₂CH₂CH₂CH₃, -O-CH₂CH(CH₃)₂, -CH₂CH(CH₃)₂, -O-CH(CH₃)CH₂CH₃, -CH(CH₃)CH₂CH₃, -O-C(CH₃)₃, -C(CH₃)₃;
• – a steht für eine Zahl zwischen 0 und 3, insbesondere 0;
• – b steht für eine Zahl zwischen 0 und 1, insbesondere 1,
• – m und n sind Zahlen, deren Summe (m + n) zwischen 1 und 2000, vorzugsweise zwischen 50 und 150 beträgt, wobei n vorzugsweise Werte von 0 bis 1999 und insbesondere von 49 bis 149 und m vorzugsweise Werte von 1 bis 2000, insbesondere von 1 bis 10 annimmt,
• – R' ist ein monovalenter Rest ausgewählt aus • -Q-N(R'')-CH₂-CH₂-N(R'')₂ • -Q-N(R'')₂ • -Q-N⁺(R'')₃A^- • -Q-N⁺H(R'')₂ A • -Q-N⁺H₂(R'')A • -Q-N(R'')-CH₂-CH₂-N⁺R''H₂A^-,

wobei jedes Q für eine chemische Bindung, -CH₂-, -CH₂-CH₂-, -CH₂CH₂CH₂-, -C(CH₃)₂-, -CH₂CH₂CH₂CH₂-, -CH₂C(CH₃)₂-, -CH(CH₃)CH₂CH₂- steht,
R'' für gleiche oder verschiedene Reste aus der Gruppe -H, -Phenyl, -Benzyl, -CH₂-CH(CH₃)Ph, der C_1-20-Alkylreste, vorzugsweise -CH₃, -CH₂CH₃, -CH₂CH₂CH₃, -CH(CH₃)₂, -CH₂CH₂CH₂H₃, -CH₂CH(CH₃)₂, -CH(CH₃)CH₂CH₃, -C(CH₃)₃, steht und A ein Anion repräsentiert, welches vorzugsweise ausgewählt ist aus Chlorid, Bromid, lodid oder Methosulfat.Preferred cosmetic preparations according to the invention comprise an amino-functional silicone of the formula (II) R _'a G _3-a -Si (OSiG _{2) n} - (OSiG _b R' _{2-b) m} -O-SiG _3-a -R _'a (II), where:

• - G is -H, a phenyl group, -OH, -O-CH ₃ , -CH ₃ , -O-CH ₂ CH ₃ , -CH ₂ CH ₃ , -O-CH ₂ CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -O-CH (CH ₃ ) ₂ , -CH (CH ₃ ) ₂ , -O-CH ₂ CH ₂ CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₂ CH ₃ , -O-CH ₂ CH (CH ₃ ) ₂ , -CH ₂ CH (CH ₃ ) ₂ , -O-CH (CH ₃ ) CH ₂ CH ₃ , -CH (CH ₃ ) CH ₂ CH ₃ , -OC (CH ₃ ) ₃ , -C (CH ₃ ) ₃ ;
• A is a number between 0 and 3, in particular 0;
• B is a number between 0 and 1, in particular 1,
• M and n are numbers whose sum (m + n) is between 1 and 2000, preferably between 50 and 150, where n 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 • -QN (R'') - CH ₂ -CH ₂ -N (R'') ₂ • -QN (R'') ₂ • -QN ⁺ (R'') ₃ A ^- • -QN ⁺ H (R '') ₂ A • -QN ⁺ H ₂ (R '') A • -QN (R '') - CH ₂ -CH ₂ -N ⁺ R''H ₂ A ^- .

wherein each Q is 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 (CH ₃ ) ₂ -, -CH (CH ₃ ) CH ₂ CH ₂ -,
R '' is -CH ₂ identical or different radicals from the group -H, -phenyl, -benzyl, -CH (CH ₃₎ Ph, C _1-20 alkyl, preferably -CH _3, -CH ₂ CH _3, -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ , -CH ₂ CH ₂ CH ₂ H ₃ , -CH ₂ CH (CH ₃ ) ₂ , -CH (CH ₃ ) CH ₂ CH ₃ , -C ( CH ₃ ) ₃ , and A represents an anion, which is preferably selected from chloride, bromide, iodide or methosulfate.

enthalten, worin m und n Zahlen sind, deren Summe (m + n) zwischen 1 und 2000, vorzugsweise zwischen 50 und 150 beträgt, wobei n vorzugsweise Werte von 0 bis 1999 und insbesondere von 49 bis 149 und m vorzugsweise Werte von 1 bis 2000, insbesondere von 1 bis 10 annimmt.Particularly preferred cosmetic preparations according to the invention are characterized in that they contain at least one amino-functional silicone of the formula (IIa)

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 classified as trimethylsilylamodimethicones according to the INCI declaration designated.

enthalten, worin R für -OH, -O-CH₃ oder eine -CH₃-Gruppe steht und m, n1 und n2 Zahlen sind, deren Summe (m + n1 + n2) zwischen 1 und 2000, vorzugsweise zwischen 50 und 150 beträgt, wobei die Summe (n1 + n2) vorzugsweise Werte von 0 bis 1999 und insbesondere von 49 bis 149 und m vorzugsweise Werte von 1 bis 2000, insbesondere von 1 bis 10 annimmt.Particular preference is also given to cosmetic preparations according to the invention which contain at least one amino-functional silicone of the formula (IIb)

in which R is -OH, -O-CH ₃ or a -CH ₃ group and m, n1 and n2 are numbers whose sum (m + n1 + n2) is between 1 and 2,000, preferably between 50 and 150 , where the sum (n1 + n2) preferably assumes values from 0 to 1999 and in particular from 49 to 149 and m preferably values from 1 to 2000, in particular from 1 to 10.

These Silicones are called amodimethicones according to the INCI declaration.

Regardless of which amino-functional silicones are used, preference is given to cosmetic preparations 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 lies. The amine number stands for the milliequivalents of amine per gram of the amino-functional silicone. she can determined by titration and also in the unit mg KOH / g.

According to the invention preferred cosmetic preparations are characterized in that they based on their weight, 0.01 to 10 wt .-%, preferably 0.1 to 8 wt .-%, particularly preferably 0.25 to 7.5 wt .-% and in particular 0.5 to 5 wt .-% amino-functional (s) silicones).

enthalten, in der x für eine Zahl von 0 bis 200, vorzugsweise von 0 bis 10, weiter bevorzugt von 0 bis 7 und insbesondere 0, 1, 2, 3, 4, 5 oder 6, steht.The INCI CYCLOMETHICONE designated cyclic dimethicones are inventively used with preference. 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 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 stands.

The silicones described above have a backbone consisting of -Si-O-Si units is constructed. Of course can these Si-O-Si units may also be interrupted by carbon chains. Appropriate molecules are by chain extension reactions accessible and preferably come in the form of silicone-in-water emulsions for use.

The silicone-in-water emulsions which can be used according to the invention can be prepared by known processes, as described, for example, in US Pat US 5,998,537 and EP 0 874 017 A1 are disclosed.

In summary comprises this manufacturing process the emulsifying mixture of components, one of which contains at least one polysiloxane, the other at least contains an organosilicone material, which reacts with the polysiloxane in a chain extension reaction, wherein at least one metal ion-containing catalyst for the chain extension reaction, at least one surfactant and water are present.

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 can also be the reaction of an Si-OH group (for example, a hydroxy-terminated Polysiloxane) having an alkoxy group (for example, alkoxysilanes, Silicates or alkoxysiloxanes) in the presence of a metal-containing Catalyst to form polysiloxanes include.

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

In this structure, each R is independently a hydrocarbon radical having up to 20 Kohlenstaoffatomen, preferably having 1 to 6 C-atoms, such as an alkyl group (for example, methyl, ethyl, propyl or butyl), an aryl group (for example, phenyl), or for the Ketenverlängerungsreakktion required group ("reactive group", such as S-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 In that an average of one to two reactive groups per polymer, n is a positive number> 1. Preferably, a plurality of the reactive groups, more preferably> 90%, and in particular> 98% of the reactive groups, at the terminal Si atoms bound in the siloxane. 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 can branched to a low degree (for example <2 mol% of the siloxane units), However, the polymers are substantially linear, especially preferred Completely linear. In addition, you can the substituents R may be substituted in their case, 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 alkyl radicals, particularly preferably methyl groups.

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

If the organosilicone material comprises a chain extending agent this may be a material such as a silane, a siloxane (For example, disiloxanes or trisiloxane) or a silazane. So For example, a composition comprising a polysiloxane according to the above described general structure, which comprises at least one Si-OH group, chain-extended be prepared by reacting with an alkoxysilane (for example, a dialkoxysilane or trialkoxysilane) in the presence of tin or titanium containing Catalysts is reacted.

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 with 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 can take any known form, for example on support materials (such as silica gel or activated carbon) applied platinum or rhodium or other suitable compounds such as platinum chloride, Salts of platinum or chloroplatinic acids. One because of the good dispersibility in organosilicon systems and the slight color changes preferred catalyst is chloroplatinic acid either as commercial available Hexahydrate or in anhydrous form.

at Another preferred chain extension reaction is a polysiloxane with at least one Si-OH group, preferably an end group, reacted with an organosilicone material which is at least has an alkoxy group, preferably a siloxane having at least a Si-OR group or an alkoxysilane having at least two alkoxy groups. In this case, the catalyst is again a catalyst containing mtall used.

For the reaction an Si-OH group with an Si-OR group, many known in the literature exist Catalysts, for example organometallic compounds such as organotin salts, Titanates or titanium chelates or complexes. Examples include tin octoate, Dibutyltin dilaurate, dibutyltin diacetate, dimethyltin dineodecanoate, Dibutyltin dimethoxide, isobutyltin triceroate, dimethyltin dibutyrate, Dimethyltin dineodecanoate, triethyltin tartrate, tin oleate, tin naphthenate, Tin butyrate, tin acetate, tin benzoate, tin sebacate, tin succinate, Tetrabutyl titanate, tetraisopropyl titanate, tetraphenyltitant, tetraoctadecyl titanate, Titanium naphthanate, ethyl triethanolamine titanate, titanium diisopropyl diethyl acetoacetate, Titanium diisopropoxy-diacetyl-acetonate and titanium-tetra-alkoxides, at where the alkoxide is butoxy or propoxy.

The In addition, silicone-in-water emulsions preferably contain at least a 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 ] _x - (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 C _1-20 -alkyl radicals, preferably -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ , -CH ₂ CH ₂ CH ₂ H ₃ , -CH ₂ CH (CH ₃ ) ₂ , -CH (CH ₃ ) CH ₂ CH ₃ , - C (CH ₃ ) ₃ , x and y are a number from 0 to 200, preferably from 0 to 10, more preferably from 0 to 7 and especially 0, 1, 2, 3, 4, 5 or 6, stand and n is a number from 0 to 10, preferably from 1 to 8 and in particular from 2, 3, 4, 5, 6.

With The silicones are preferably water-soluble. According to the invention preferred Cosmetic preparations are characterized in that they additionally a water-soluble Silicone included.

The cosmetic according to the invention Means can also as hair dye be formulated. The term dyeing includes all methods known to those skilled in the art, in which if necessary moistened, hair is applied a colorant and this either for a time between a few minutes and about 45 minutes on the hair leave and then is rinsed with water or a surfactant-containing agent or left completely on the hair. It will be in this context explicitly on the known monographs, for. Kh.

Schrader, Basics and recipes of cosmetics, 2nd edition, Hüthig book Verlag, Heidelberg, 1989, referenced the relevant knowledge of the professional.

As mentioned earlier it is possible in the context of the teaching of the invention, the hexenyl or cinnamyl-silicic acid esters directly into the dyeing or tinting agent incorporate.

The Composition of the dyeing or tinting agent is not subject to any fundamental restrictions.

• • Oxidationsfarbstoffvorprodukte vom Entwickler- und Kuppler-Typ,
• • natürliche und synthetische direktziehende Farbstoffe und
• • Vorstufen naturanaloger Farbstoffe, wie Indol- und Indolin-Derivate,

sowie Mischungen von Vertretern einer oder mehrerer dieser Gruppen eingesetzt werden.As a dye (precursor) e can

• Developer and coupler type oxidation dye precursors,
• Natural and synthetic direct dyes and
• Precursors of nature-analogous dyes, such as indole and indoline derivatives,

and mixtures of representatives of one or more of these groups.

conventional Hair Dye usually consist of at least one developer and at least a coupler substance and optionally contain direct dyes (= Hair dyes) as Nuanceure. Coupler and developer components are also referred to as oxidation dye precursors.

When Developer components are usually primary aromatic amines with another, in para or ortho position free or substituted hydroxy or amino group, Diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazolone derivatives 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.

When Coupler components are usually m-phenylenediamine derivatives, Naphthols, resorcinol and resorcinol derivatives, pyrazolones, m-aminophenols and substituted pyridine derivatives. As coupler substances Particularly suitable are α-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 2,4-diaminophenoxyethanol, 2-amino-4- (2-hydroxyethylamino) -anisole (Lehmann's Blue), 1-phenyl-3-methyl-pyrazol-5-one, 2,4-dichloro-3-aminophenol, 1,3-bis (2,4-diaminophenoxy) propane, 2-chlororesorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 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. In this context, agents according to the invention which contain at least one oxidation dye precursor of Ent type of wetter and / or optionally at least one coupler type oxidation dye precursor are preferred.

• – Oxidationsfarbstoffvorprodukte vom Entwickler- und/oder Kuppler-Typ, und
• – Vorstufen naturanaloger Farbstoffe, wie Indol- und Indolin-Derivate,

sowie Mischungen von Vertretern dieser Gruppen enthalten.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 nature-analogous dyes, such as indole and indoline derivatives,

and mixtures of representatives of these groups.

In a first preferred embodiment contain the agents of the invention at least one developer component. As developer components become common primary aromatic amines with another, in para or ortho position free or substituted hydroxy or amino group, Diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazole derivatives and 2,4,5,6-tetraaminopyrimidine and its derivatives used.

wobei

• – G¹ steht für ein Wasserstoffatom, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen (C₁- bis C₄)-Alkoxy-(C₁- bis C₄)-alkylrest, einen 4'-Aminophenylrest oder einen C₁- bis C₄-Alkylrest, der mit einer stickstoffhaltigen Gruppe, einem Phenyl- oder einem 4'-Aminophenylrest substituiert ist;
• – G² steht für ein Wasserstoffatom, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen (C₁- bis C₄)-Alkoxy-(C₁- bis C₄)-alkylrest oder einen C₁- bis C₄-Alkylrest, der mit einer stickstoffhaltigen Gruppe substituiert ist;
• – G³ steht für ein Wasserstoffatom, ein Halogenatom, wie ein Chlor-, Brom-, Iod- oder Fluoratom, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen C₁- bis C₄-Hydroxyalkoxyrest, einen C₁- bis C₄-Acetylaminoalkoxyrest, einen C₁- bis C₄- Mesylaminoalkoxyrest oder einen C₁- bis C₄-Carbamoylaminoalkoxyrest;
• – G⁴ steht für ein Wasserstoffatom, ein Halogenatom oder einen C₁- bis C₄-Alkylrest oder
• – wenn G³ und G⁴ in ortho-Stellung zueinander stehen, können sie gemeinsam eine verbrückende α,ω-Alkylendioxogruppe, wie beispielsweise eine Ethylendioxygruppe bilden.

It may be preferred according to the invention to use as the developer component a p-phenylenediamine derivative or one of its physiologically acceptable 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 monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a C ₁ to C ₄ alkoxy radical (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 represents a hydrogen atom, a C ₁ -C ₄ -alkyl radical, a C ₁ -C ₄ -monohydroxyalkyl radical, a C ₂ -C ₄ -polyhydroxyalkyl radical, a C ₁ -C ₄ -alkoxy radical (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 represents a hydrogen atom, a halogen atom, such as a chlorine, bromine, iodine or fluorine atom, a C ₁ - to C ₄ -alkyl radical, a C ₁ - to C ₄ -monohydroxyalkyl radical, a C ₂ - to C ₄ -polyhydroxyalkyl, C ₁ - to C ₄ -hydroxyalkoxy, C ₁ - to C ₄ -acetylaminoalkoxy, C ₁ - to C ₄ -mesylaminoalkoxy or C ₁ - to C ₄ -carbamoylaminoalkoxy;
• - 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 -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 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-dihydroxyethyl 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-acetylaminoethyloxy) p-phenylenediamine, N- (β-methoxyethyl) -p-phenylenediamine and 5,8-diaminobenzo-1,4-dioxane and their physiologically acceptable salts.

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

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

wobei:

• – Z¹ und Z² stehen unabhängig voneinander für einen Hydroxyl- oder NH₂-Rest, der gegebenenfalls durch einen C₁- bis C₄-Alkylrest, durch einen C₁- bis C₄-Hydroxyalkylrest und/oder durch eine Verbrückung Y substituiert ist oder der gegebenenfalls Teil eines verbrückenden Ringsystems ist,
• – die Verbrückung Y steht für eine Alkylengruppe mit 1 bis 14 Kohlenstoffatomen, wie beispielsweise eine lineare oder verzweigte Alkylenkette oder einen Alkylenring, die von einer oder mehreren stickstoffhaltigen Gruppen und/oder einem oder mehreren Heteroatomen wie Sauerstoff-, Schwefel- oder Stickstoffatomen unterbrochen oder beendet sein kann und eventuell durch einen oder mehrere Hydroxyl- oder C₁- bis C₈-Alkoxyreste substituiert sein kann, oder eine direkte Bindung,
• – G⁵ und G⁶ stehen unabhängig voneinander für ein Wasserstoff- oder Halogenatom, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen C₁- bis C₄-Aminoalkylrest oder eine direkte Verbindung zur Verbrückung Y,
• – G⁷, G⁸, G⁹, G¹⁰, G¹¹und G¹² stehen unabhängig voneinander für ein Wasserstoffatom, eine direkte Bindung zur Verbrückung Y oder einen C₁- bis C₄-Alkylrest, mit den Maßgaben, dass
• – die Verbindungen der Formel (E2) nur eine Verbrückung Y pro Molekül enthalten und
• – die Verbindungen der Formel (E2) mindestens eine Aminogruppe enthalten, die mindestens ein Wasserstoffatom trägt.

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 are a hydroxyl or NH ₂ radical which is optionally substituted by a C ₁ - to C ₄ -alkyl radical, by a C ₁ - to C ₄ -hydroxyalkyl radical and / or by a bridge Y. or is optionally part of a bridging ring system,
• - 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 interrupted or terminated by one or more nitrogen-containing groups and / or one or more heteroatoms such as oxygen, sulfur or nitrogen atoms may be and may be substituted by one or more hydroxyl or C ₁ - to C ₈ alkoxy, or a direct bond,
• G ⁵ and G ⁶ independently of one another are 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 -aminoalkyl radical or a direct compound for bridging Y,
• - G ⁷ , G ⁸ , G ⁹ , G ¹⁰ , G ¹¹ and G ¹² are each independently a hydrogen atom, a direct bond to the bridge Y or a C ₁ - to C ₄ alkyl, with the provisos that
• The compounds of the 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 used in formula (E2) substituents are analogous to the invention to the above statements Are defined.

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 - (β-hydroxyethyl) -N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis (4-methylaminophenyl) tetramethylenediamine, N, N'-diethyl-N, N ' bis (4'-amino-3'-methylphenyl) ethylenediamine, bis (2-hydroxy-5-aminophenyl) methane, 1,3-bis (2,5-diaminophenoxy) -propan-2-ol , N, N'-bis (4'-aminophenyl) -1,4-diazacycloheptane, N, N'-bis (2-hydroxy-5-aminobenzyl) piperazine, N- (4'-aminophenyl) -p phenylenediamine and 1,10-bis (2 ', 5'-diaminophe nyl) -1,4,7,10-tetraoxadecane and their physiologically acceptable salts.

All 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 1,10-bis (2 ', 5'-diaminophenyl) -1,4,7,10-tetraoxadecane or one of its physiologically acceptable salts.

wobei:

• – G¹³ steht für ein Wasserstoffatom, ein Halogenatom, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen (C₁- bis C₄)-Alkoxy-(C₁- bis C₄)-alkylrest, einen C₁- bis C₄-Aminoalkylrest, einen Hydroxy-(C₁- bis C₄)-alkylaminorest, einen C₁- bis C₄-Hydroxyalkoxyrest, einen C₁- bis C₄-Hydroxyalkyl-(C₁-bis C₄)-aminoalkylrest oder einen (Di-C₁- bis C₄-Alkylamino)-(C₁- bis C₄)-alkylrest, und
• – G¹⁴ steht für ein Wasserstoff- oder Halogenatom, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen (C₁- bis C₄)-Alkoxy-(C₁- bis C₄)-alkylrest, einen C₁- bis C₄-Aminoalkylrest oder einen C₁- bis C₄-Cyanoalkylrest,
• – G¹⁵ steht für Wasserstoff, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen Phenylrest oder einen Benzylrest, und
• – G¹⁶ steht für Wasserstoff oder ein Halogenatom.

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, C ₁ - to C ₄ monohydroxyalkyl radical, a C ₂ - to C ₄ polyhydroxyalkyl radical, a (C ₁ - to C ₄₎ Alkoxy (C ₁ to C ₄ ) alkyl, C ₁ to C ₄ aminoalkyl, hydroxy (C ₁ to C ₄ ) alkylamino, C ₁ to C ₄ hydroxyalkoxy, C ₁ - to C ₄ -hydroxyalkyl- (C ₁ -C ₄ ) -aminoalkyl or a (di-C ₁ - to C ₄ -alkylamino) - (C ₁ - to C ₄ ) -alkyl, 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₎ Alkoxy (C ₁ to C ₄ ) alkyl, C ₁ to C ₄ aminoalkyl or C ₁ to C ₄ cyanoalkyl,
• G ¹⁵ is hydrogen, a C ₁ - to C ₄ -alkyl radical, a C ₁ - to C ₄ -monohydroxyalkyl radical, a C ₂ - to C ₄ -polyhydroxyalkyl radical, a phenyl radical or a benzyl radical, and
• - G ¹⁶ is hydrogen or a halogen atom.

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

preferred p-aminophenols of the formula (E3) are in particular p-aminophenol, N-methyl-p-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 2-hydroxymethylamino-4-aminophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2- (□ -hydroxyethoxy) -phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethyl-phenol, 4-amino-2-aminomethylphenol, 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 its physiological acceptable Salts.

All 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 For example, the developer component can be selected from o-aminophenol and its derivatives, such as 2-amino-4-methylphenol, 2-amino-5-methylphenol or 2-amino-4-chlorophenol.

Farther For example, the developer component may be selected from heterocyclic Developer components, such as the pyridine, pyrimidine, Pyrazole, pyrazole pyrimidine derivatives and their physiologically tolerable Salt.

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

preferred Pyrimidine derivatives are in particular 2,4,5,6-tetraaminopyrimidine, 4-Hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2-dimethylamino-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6-triaminopyrimidine.

preferred Pyrazole derivatives are in particular 4,5-diamino-1-methylpyrazole, 4,5-diamino-1- (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-hydroxymethyl-1-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4,5-diamino-3-methyl-1-isopropylpyrazole, 4-amino-5- (α-aminoethyl) amino-1,3-dimethylpyrazole, 3,4,5-triaminopyrazole, 1-Methyl-3,4,5-triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole and 3,5-diamino-4- (β-hydroxyethyl) amino-1-methylpyrazole.

wobei:

• – G¹⁷, G¹⁸, G¹⁹ und G²⁰ unabhängig voneinander stehen für ein Wasserstoffatom, einen C₁- bis C₄-Alkylrest, einen Aryl-Rest, einen C₁- bis C₄-Hydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest einen (C₁- bis C₄)-Alkoxy-(C₁- bis C₄)-alkylrest, einen C₁- bis C₄-Aminoalkylrest, der gegebenenfalls durch ein Acetyl-Ureid- oder einen Sulfonyl-Rest geschützt sein kann, einen (C₁- bis C₄)-Alkylamino-(C₁- bis C₄)-alkylrest, einen Di-[(C₁- bis C₄)-alkyl]-(C₁- bis C₄)-aminoalkylrest, wobei die Dialkyl-Reste gegebenenfalls einen Kohlenstoffzyklus oder einen Heterozyklus mit 5 oder 6 Kettengliedern bilden, einen C₁- bis C₄-Hydroxyalkyl- oder einen Di-(C₁- bis C₄)-[Hydroxyalkyl]-(C₁- bis C₄)-aminoalkylrest,
• – die X-Reste stehen unabhängig voneinander für ein Wasserstoffatom, einen C₁- bis C₄-Alkylrest, einen Aryl-Rest, einen C₁- bis C₄-Hydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen C₁- bis C₄-Aminoalkylrest, einen (C₁- bis C₄)-Alkylamino-(C₁- bis C₄)-alkylrest, einen Di-[(C₁- bis C₄)alkyl]- (C₁- bis C₄)-aminoalkylrest, wobei die Dialkyl-Reste gegebenenfalls einen Kohlenstoffzyklus oder einen Heterozyklus mit 5 oder 6 Kettengliedern bilden, einen C₁- bis C₄-Hydroxyalkyl- oder einen Di-(C₁- bis C₁-hydroxyalkyl)aminoalkylrest, einen Aminorest, einen C₁- bis C₄-Alkyl- oder Di-(C₁- bis C₄-hydroxyalkyl)aminorest, ein Halogenatom, eine Carboxylsäuregruppe oder eine Sulfonsäuregruppe,
• – i hat den Wert 0, 1, 2 oder 3,
• – p hat den Wert 0 oder 1,
• – q hat den Wert 0 oder 1 und
• – n hat den Wert 0 oder 1,

mit der Maßgabe, dass

• – die Summe aus p + q ungleich 0 ist,
• – wenn p + q gleich 2 ist, n den Wert 0 hat, und die Gruppen NG¹⁷G¹⁸ und NG¹⁹G²⁰ belegen die Positionen (2,3); (5,6); (6,7); (3,5) oder (3,7);
• – wenn p + q gleich 1 ist, n den Wert 1 hat, und die Gruppen NG¹⁷G¹⁸ (oder NG¹⁹G²⁰) und die Gruppe OH belegen die Positionen (2,3); (5,6); (6,7); (3,5) oder (3,7);

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

in which:

• - G ¹⁷ , G ¹⁸ , G ¹⁹ and G ²⁰ 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 - to C ₄ -Polyhydroxyalkylrest a (C ₁ - to C ₄ ) alkoxy- (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 - [(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 with 5 or 6 chain members, a C ₁ - to C ₄ -hydroxyalkyl- or a di- (C ₁ - to C ₄ ) - [hydroxyalkyl] - (C ₁ - 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 - to C ₄ -polyhydroxyalkyl radical, a C ₁ - to C ₄ -aminoalkyl, a (C ₁ - to C ₄ ) -alkylamino- (C ₁ - to C ₄ ) -alkyl, a di - [(C ₁ - to C ₄ ) alkyl] - (C ₁ - bis C ₄ ) aminoalkyl radical, where 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 ₁ -hydroxyalkyl) aminoalkyl radical, an amino radical, a C ₁ - to C ₄ -alkyl or di- (C ₁ - to C ₄ -hydroxyalkyl) amino radical, a halogen atom, a carboxylic acid group or a sulfonic acid group,
• - i has the value 0, 1, 2 or 3,
• - p has the value 0 or 1,
• - q has the value 0 or 1 and
• - n has the value 0 or 1,

with the proviso that

• The sum of p + q is not equal to 0,
• If p + q equals 2, n has the value 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 used in formula (E4) substituents are analogous to the invention to the above statements Are defined.

When the pyrazolo [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:

• – Pyrazol-[1,5-a]-pyrimidin-3,7-diamin;
• – 2,5-Dimethyl-pyrazol-[1,5-a]-pyrimidin-3,7-diamin;
• – Pyrazol-[1,5-a]-pyrimidin-3,5-diamin;
• – 2,7-Dimethyl-pyrazol-[1,5-a]-pyrimidin-3,5-diamin;
• – 3-Aminopyrazol-[1,5-a]-pyrimidin-7-ol;
• – 3-Aminopyrazol-[1,5-a]-pyrimidin-5-ol;
• – 2-(3-Aminopyrazol-[1,5-a]-pyrimidin-7-ylamino)-ethanol;
• – 2-(7-Aminopyrazol-[1,5-a]-pyrimidin-3-ylamino)-ethanol;
• – 2-[(3-Aminopyrazol-[1,5-a]-pyrimidin-7-yl)-(2-hydroxy-ethyl)amino]-ethanol;
• – 2-[(7-Aminopyrazol-(1,5-a]-pyrimidin-3-yl)-(2-hydroxy-ethyl)amino]-ethanol;
• – 5,6-Dimethylpyrazol-[1,5-a]-pyrimidin-3,7-diamin;
• – 2,6-Dimethylpyrazol-[1,5-a]-pyrimidin-3,7-diamin;
• – 3-Amino-7-dimethylamino-2,5-dimethylpyrazol-[1,5-a]-pyrimidin;

sowie ihre physiologisch verträglichen Salze und ihre tautomeren Formen, wenn ein tautomers Gleichgewicht vorhanden ist.In particular, among the pyrazolo [1,5-a] -pyrimidines of the above formula (E4):

• - pyrazolo [1,5-a] pyrimidine-3,7-diamine;
• 2,5-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine;
• - pyrazolo [1,5-a] pyrimidine-3,5-diamine;
• 2,7-dimethylpyrazolo [1,5-a] -pyrimidine-3,5-diamine;
• 3-aminopyrazolo [1,5-a] 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-hydroxy-ethyl) amino] -ethanol;
• - 2 - [(7-aminopyrazole- (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 Pyrazole- [1,5-a] -pyrimidines of the above formula (E4) can, as described in the literature by cyclization starting from a Aminopyrazole or produced from hydrazine.

In a further preferred embodiment contain the agents of the invention at least one coupler component.

When Coupler components are usually m-phenylenediamine derivatives, Naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenol derivatives used. Particularly suitable coupling agents are 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, Resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 1-phenyl-3-methyl-pyrazolone-5, 2,4-dichloro-3-aminophenol, 1,3-bis (2 ', 4'-diaminophenoxy) -propane, 2-chlororesorcinol, 4-chloro-resorcinol, 2-chloro-6-methyl-3-aminophenol, 2-amino-3-hydroxypyridine, 2-methylresorcinol, 5-methylresorcinol and 2-methyl-4-chloro-5-aminophenol.

• – m-Aminophenol und dessen Derivate wie beispielsweise 5-Amino-2-methylphenol, N-Cyclopentyl-3-aminophenol, 3-Amino-2-chlor-6-methylphenol, 2-Hydroxy-4-aminophenoxyethanol, 2,6-Dimethyl-3-aminophenol, 3-Trifluoroacetylamino-2-chlor-6-methylphenol, 5-Amino-4-chlor-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)-benzol, 3-Ethylamino-4-methylphenol und 2,4-Dichlor-3-aminophenol,
• – o-Aminophenol und dessen Derivate,
• – m-Diaminobenzol und dessen Derivate wie beispielsweise 2,4-Diaminophenoxyethanol, 1,3-Bis-(2',4'-diaminophenoxy)-propan, 1-Methoxy-2-amino-4-(2'-hydroxyethylamino)benzol, 1,3-Bis-(2',4'-diaminophenyl)-propan, 2,6-Bis-(2'-hydroxyethylamino)-1-methylbenzol und 1-Amino-3-bis-(2'-hydroxyethyl)aminobenzol,
• – o-Diaminobenzol und dessen Derivate wie beispielsweise 3,4-Diaminobenzoesäure und 2,3-Diamino-1-methylbenzol,
• – Di- beziehungsweise Trihydroxybenzolderivate wie beispielsweise Resorcin, Resorcinmonomethylether, 2-Methylresorcin, 5-Methylresorcin, 2,5-Dimethylresorcin, 2-Chlorresorcin, 4-Chlorresorcin, Pyrogallol und 1,2,4-Trihydroxybenzol,
• – Pyridinderivate wie beispielsweise 2,6-Dihydroxypyridin, 2-Amino-3-hydroxypyridin, 2-Amino-5-chlor-3-hydroxypyridin, 3-Amino-2-methylamino-6-methoxypyridin, 2,6-Dihydroxy-3,4-dimethylpyridin, 2,6-Dihydroxy-4-methylpyridin, 2,6-Diaminopyridin, 2,3-Diamino-6-methoxypyridin und 3,5-Diamino-2,6-dimethoxypyridin,
• – Naphthalinderivate wie beispielsweise 1-Naphthol, 2-Methyl-1-naphthol, 2-Hydroxymethyl-1-naphthol, 2-Hydroxyethyl-1-naphthol, 1,5-Dihydroxynaphthalin, 1,6-Dihydroxynaphthalin, 1,7-Dihydroxynaphthalin, 1,8-Dihydroxynaphthalin, 2,7-Dihydroxynaphthalin und 2,3-Dihydroxynaphthalin,
• – Morpholinderivate wie beispielsweise 6-Hydroxybenzomorpholin und 6-Amino-benzomorpholin,
• – Chinoxalinderivate wie beispielsweise 6-Methyl-1,2,3,4-tetrahydrochinoxalin,
• – Pyrazolderivate wie beispielsweise 1-Phenyl-3-methylpyrazol-5-on,
• – Indolderivate wie beispielsweise 4-Hydroxyindol, 6-Hydroxyindol und 7-Hydroxyindol,
• – Pyrimidinderivate, wie beispielsweise 4,6-Diaminopyrimidin, 4-Amino-2,6-dihydroxypyrimidin, 2,4-Diamino-6-hydroxypyrimidin, 2,4,6-Trihydroxypyrimidin, 2-Amino-4-methylpyrimidin, 2-Amino-4-hydroxy-6-methylpyrimidin und 4,6-Dihydroxy-2-methylpyrimidin, oder
• – Methylendioxybenzolderivate wie beispielsweise 1-Hydroxy-3,4-methylendioxybenzol, 1-Amino-3,4-methylendioxybenzol und 1-(2'-Hydroxyethyl)amino-3,4-methylendioxybenzol.

According to preferred coupler components are

• - M-aminophenol and its derivatives such as 5-amino-2-methylphenol, N-cyclopentyl-3-aminophenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 2,6-dimethyl 3-aminophenol, 3-trifluoroacetylamino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol, 5- (2'-hydroxyethyl) amino 2-methylphenol, 3- (diethylamino) -phenol, N-cyclopentyl-3-aminophenol, 1,3-dihydroxy-5- (methylamino) -benzene, 3-ethylamino-4-methylphenol and 2,4-dichloro-3 aminophenol,
• O-aminophenol and its derivatives,
• - M-Diaminobenzene and its derivatives such as 2,4-diaminophenoxyethanol, 1,3-bis (2 ', 4'-diaminophenoxy) propane, 1-methoxy-2-amino-4- (2'-hydroxyethylamino) benzene , 1,3-bis (2 ', 4'-diaminophenyl) -propane, 2,6-bis (2'-hydroxyethylamino) -1-methylbenzene and 1-amino-3-bis (2'-hydroxyethyl) aminobenzene,
• O-diaminobenzene and its derivatives such as 3,4-diaminobenzoic acid and 2,3-diamino-1-methylbenzene,
• Di- or trihydroxybenzene derivatives such as resorcinol, resorcinol monomethyl ether, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2-chlororesorcinol, 4-chlororesorcinol, pyrogallol and 1,2,4-trihydroxybenzene,
• Pyridine derivatives such as 2,6-dihydroxypyridine, 2-amino-3-hydroxypyridine, 2-amino-5-chloro-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine, 2,6-dihydroxy-3, 4-dimethylpyridine, 2,6-dihydroxy-4-methylpyridine, 2,6-diaminopyridine, 2,3-diamino-6-methoxypyridine and 3,5-diami no-2,6-dimethoxy,
• Naphthalene derivatives such as, for example, 1-naphthol, 2-methyl-1-naphthol, 2-hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and 2,3-dihydroxynaphthalene,
• Morpholine derivatives such as 6-hydroxybenzomorpholine and 6-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 according to the invention preferred coupler components are 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 3-aminophenol, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridine, Resorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol and 2,6-dihydroxy-3,4-dimethylpyridine.

When Precursors of naturally-analogous dyes are preferably those indoles and indolives containing at least one hydroxy or amino group, preferably as a substituent on the six-membered ring. These groups can bear further substituents, for. B. in the form of an etherification or Esterification of the hydroxy group or alkylation of the amino group. In a second preferred embodiment, the means include at least one indole and / or indoline derivative.

in der unabhängig voneinander

• – R¹ steht für Wasserstoff, eine C₁-C₄-Alkylgruppe oder eine C₁-C₄-Hydroxy-alkylgruppe,
• – R² steht für Wasserstoff oder eine -COOH-Gruppe, wobei die -COOH-Gruppe auch als Salz mit einem physiologisch verträglichen Kation vorliegen kann,
• – R³ steht für Wasserstoff oder eine C₁-C₄-Alkylgruppe,
• – R⁴ steht für Wasserstoff, eine C₁-C₄-Alkylgruppe oder eine Gruppe -CO-R⁶, in der R⁶ steht für eine C₁-C₄-Alkylgruppe, und
• – R⁵ steht für eine der unter R⁴ genannten Gruppen,

sowie physiologisch verträgliche Salze dieser Verbindungen mit einer organischen oder anorganischen Säure.Particularly suitable precursors of naturally-analogous hair dyes are derivatives of 5,6-dihydroxyindoline of the formula (IIIa),

in the independently of each other

• R ¹ is hydrogen, a C ₁ -C ₄ -alkyl group or a C ₁ -C ₄ -hydroxy-alkyl group,
• R ² is hydrogen or a -COOH group, where the -COOH group may also be present as a salt with a physiologically compatible cation,
• R ³ is hydrogen or a C ₁ -C ₄ -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
• R ⁵ is one of the groups mentioned under R ⁴ ,

and physiologically acceptable salts of these compounds with an organic or inorganic acid.

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

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

in der unabhängig voneinander

• – R¹ steht für Wasserstoff, eine C₁-C₄-Alkylgruppe oder eine C₁-C₄-Hydroxyalkylgruppe,
• – R² steht für Wasserstoff oder eine -COOH-Gruppe, wobei die -COOH-Gruppe auch als Salz mit einem physiologisch verträglichen Kation vorliegen kann,
• – R³ steht für Wasserstoff oder eine C₁-C₄-Alkylgruppe,
• – R⁴ steht für Wasserstoff, eine C₁-C₄-Alkylgruppe oder eine Gruppe -CO-R⁶, in der R⁶ steht für eine C₁-C₄-Alkylgruppe, und
• – R⁵ steht für eine der unter R⁴ genannten Gruppen,
• – sowie physiologisch verträgliche Salze dieser Verbindungen mit einer organischen oder anorganischen Säure.

Also suitable as precursors of naturally-analogous hair dyes are derivatives of the 5,6-dihydroxyindole of the formula (IIIb),

in the independently of each other

• 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, where the -COOH group may also be present as a salt with a physiologically compatible cation,
• R ³ is hydrogen or a C ₁ -C ₄ -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
• 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.

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

Within of this group are N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole and in particular the 5,6-dihydroxyindole.

The Indoline and indole derivatives can in the used in the context of the method according to the invention Means both as free bases and in the form of their physiological acceptable Salts with inorganic or organic acids, e.g. The hydrochlorides, the sulfates and hydrobromides used. The indole or Indoline derivatives are common in these in amounts of 0.05-10 wt .-%, preferably 0.2-5 wt .-%.

In a further embodiment it may be preferred according to the invention be the indoline or Indolderivat in hair dyes in combination with at least one amino acid or an oligopeptide. The amino acid is advantageous an α-amino acid; all particularly preferred α-amino acids Arginine, ornithine, lysine, serine and histidine, especially arginine.

preferred inventive agent are characterized in that they comprise at least one dye precursor the groups of aromatic and heteroaromatic diamines, aminophenols, Naphthols, polyphenols CH-acidic coupler components and their derivatives in amounts of from 0.01 to 25% by weight, preferably from 0.5 to 10% by weight, in particular from 1 to 5 wt .-%, each based on the total Means, included.

In addition to the oxidation dye precursor (s), the preparation (A) - for shading one or more substantive dyes. Direct dyes are common Nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols. Preferred substantive dyes are the under the international names or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, Acid Yellow 1, Acid Yellow 10, Acid Yellow 23, Acid Yellow 36, HC Orange 1, Disperse Orange 3, Acid Orange 7, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, Acid Red 33, Acid Red 52, HC Red BN, Pigment Red 57: 1, HC Blue 2, HC Blue 12, Disperse Blue 3, Acid Blue 7, Acid Green 50, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Acid Violet 43, Disperse Black 9, Acid Black 1, and Acid Black 52 Compounds and 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-nitrophenol, 1- (2'-ureidoethyl) amino-4-nitrobenzene, 4-amino-2-nitrodiphenylamine-2'-carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4-naphthoquinone, picramic acid and its salts, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene.

Corresponding agents according to the invention, which are characterized in that they contain at least ei direct dye from the group of cationic (basic) dyes, preferably Basic Blue 6, CI-No. 51,175; Basic Blue 7, CI-No. 42.595; Basic Blue 9, CI-No. 52.015; Basic Blue 26, CI-No. 44.045; Basic Blue 41, CI-No. 11.154; Basic Blue 99, CI-No. 56.059; Basic Brown 4, CI-No. 21.010; Basic Brown 16, CI-No. 12.250; Basic Brown 17, CI-No. 12.251; Basic Green 1, CI-No. 42.040; Basic Orange 31; Basic Red 2, CI-No. 50.240; Basic Red 22, CI-No. 11.055; Basic Red 46; Basic Red 51; Basic Red 76, CI-No. 12.245; Basic Violet 1, CI-No. 42.535; Basic Violet 2; Basic Violet 3, CI-No. 42.555; Basic Violet 10, CI-No. 45.170; Basic Violet 14, CI-No. 42.510; Basic Yellow 57, CI-No. 12.719; Basic Yellow 87 and / or the anionic (acidic) dyes, and / or the nonionic dyes, preferably Acid Black 1, CI-No. 20.470; Acid Black 52; Acid Blue 7; Acid Blue 9, CI-No. 42.090; Acid Blue 74, CI-No. 73.015, Acid Red 18, CI-No. 16.255; Acid Red 23; Acid Red 27, CI-No. 16.185; Acid Red 33; Acid Red 52; Acid Red 87, CI-No. 45,380; Acid Red 92, CI-No. 45,410; Acid Orange 3; Acid Orange 7; Acid Violet 43, CI-No. 60.730; Acid Yellow 1, CI-No. 10.316; Acid Yellow 10; Acid Yellow 23, CI-No. 19,140; Acid Yellow 3, CI-No. 47.005; Acid Yellow 36; D & C Brown no. 1, CI-No. 20.170 (Acid Orange 24); D & C Green no. 5, CI-No. 61,570 (Acid Green G); D & C Orange No. 4, CI-No. 15.510 (Acid Orange II); D & C Orange No. 10, CI-No. 45.425: 1 (Solvent Red 73); D & C Orange No. 11, CI-No. 45.425 (Acid Red 95); D & C Red No. 21, CI-No. 45.380: 2 (Solvent Red 43); D & C Red No. 27, CI-No. 45.410: 1 (Solvent Red 48); D & C Red No. 33, CI-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, CI-No. 45,350 (Acid Yellow 73); FD & C Red No. 4, CI-No. 14,700 (Food Red 4); FD & C Yellow No. 6, CI-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; Sodium 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-tetranitrochinoxalin; 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; amine-1-propene (4-amino-2-nitrophenyl); isatin; N-methylylisatin; HC Violet 1; HC Violet 2; 4-Nitrophenylaminoethylharnstoff 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.

Under Some of the dyes mentioned above are particular preferred, which is why further preferred agents according to the invention, characterized in that they have at least one direct puller, selected 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 Red 23, Acid Red 52, Acid Orange 7, Acid Yellow 1, Acid Yellow 10, Acid Yellow 36, Food Green 3, Pigment Red 57-1, Disperse Black 9, Disperse Blue 1, Disperse Blue 3, Disperse Violet 1, Disperse Violet 4, HC Orange 1, HC Red 1, HC Red 3, HC Red 13, HC Yellow 2, HC Yellow 4, Na picakrate, 1,4-bis- (2'-hydroxyethyl) amino-2-nitro-p-phenylenediamine, HC Yellow 5, HC Blue 2, HC Blue 12, 4-amino-3-nitrophenol, HC Yellow 6, HC Yellow 12,2-nitro-1- (2'-hydroxyethyl) amino-4-methylbenzene, 2-nitro-4-amino-diphenylamine-2'-carboxylic acid, 2-amino-6-chloro-4-nitrophenol, HC Red BN; 6-nitro-1,2,3,4-tetranitroquinoxaline, o-nitro-p-phenylenediamine, p-nitro-m-phenylenediamine, HC Red B 54, HC Red 10, HC Red 11, HC Red 13,2- (2'-hydroxyethyl) amino-1-hydroxy-4,6-dinitrobenzene, 4-ethylamino-3-nitrobenzoic acid, 2-chloro-6-ethylamino-4-nitrophenol, 2-hydroxy-1,4-naphthoquinone, 1-propene (4-amino-2-nitrophenyl) amine, Isatin, N-Methylylisatin, HC Violet 1, HC Violet 2, 4-Nitrophenylaminoethyl urea in amounts of from 0.01 to 25% by weight, preferably from 0.5 to 10% by weight, in particular from 1 to 5 wt .-%, each based on the total Means, contained, are preferred.

• (a) kationische Triphenylmethanfarbstoffe, wie beispielsweise Basic Blue 7, Basic Blue 26, Basic Violet 2 und Basic Violet 14,
• (b) aromatischen Systeme, die mit einer quaternären Stickstoffgruppe substituiert sind, wie beispielsweise Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 und Basic Brown 17, sowie
• (c) direktziehende Farbstoffe, die einen Heterozyklus enthalten, der mindestens ein quaternäres Stickstoffatom aufweist, wie sie beispielsweise in der EP-A2-998 908, auf die an dieser Stelle explizit Bezug genommen wird, in den Ansprüchen 6 bis 11 genannt werden.

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 incorporated herein by reference, in claims 6 to 11.

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

The Compounds of the formulas (DZ1), (DZ3) and (DZ5), which are also available under the terms Basic Yellow 87, Basic Orange 31 and Basic Red 51 are very particularly preferred cationic substantive Dyes of group (c).

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

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

Farther can the preparations according to the invention also occurring in nature dyes such as, for example in henna red, henna neutral, henna black, chamomile flower, sandalwood, black tea, buckthorn bark, sage, bluewood, madder root, catechu, Sedre and alkano root are included.

It it is not necessary that the oxidation dye precursors or the direct dyes in each case uniform compounds represent. Rather, you can in the agents according to the invention, due to the production process for the individual dyes, be contained in minor amounts still other components as far as these are not the dyeing result adversely affect or for other reasons, e.g. toxicological, must be excluded.

Regarding the in accordance with the invention as a hair dye and -tönungsmittel formuilierten usable dyes is still explicitly on the monograph Ch. Zviak, The Science of Hair Care, chapter 7 (pages 248-250; direct dyes) and chapter 8, pages 264-267; Oxidation dye precursors) appeared as volume 7 of the series "Dermatology (Ed .: Ch., Culnan and H. Maibach), published by Marcel Dekker Inc., New York, Basel, 1986, and the "European Inventory of cosmetic raw materials ", issued by the European Community, available in disk form by the Federal Association of German Industrial and Trading Companies for medicines, Health food and personal care products e.V., Mannheim.

However, according to the invention the oxidation colorant also be applied to the hair together with a catalyst, 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 ²⁺ , Mn ⁴⁺ , 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.

• – Pyranose-Oxidase und z.B. D-Glucose oder Galactose,
• – Glucose-Oxidase und D-Glucose,
• – Glycerin-Oxidase und Glycerin,
• – Pyruvat-Oxidase und Benztraubensäure oder deren Salze,
• – Alkohol-Oxidase und Alkohol (MeOH, EtOH),
• – Lactat-Oxidase und Milchsäure und deren Salze,
• – Tyrosinase-Oxidase und Tyrosin,
• – Uricase und Harnsäure oder deren Salze,
• – Cholinoxidase und Cholin,
• – Aminosäure-Oxidase und Aminosäuren.

Suitable enzymes include peroxidases, which are the effect of small amounts of hydrogen peroxide can significantly increase. 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 eg 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 their salts,
• Tyrosinase oxidase and tyrosine,
• Uricase and uric acid or their salts,
• - choline oxidase and choline,
• - amino acid oxidase and amino acids.

Usually become colorants offered as a combination pack containing a dye cream and a separately packaged oxidation solution include. Just before the application, both components become one with each other mixed, and the prepared mixture is applied to the hair to be dyed applied. The mixing ratio the two components can be chosen freely. Conveniently, the preparation of the oxidizing agent is then immediately before dyeing the hair mixed with the preparation with the dye precursors. The resulting ready-to-use hair dye preparation should preferably have a pH in the range of 6 to 10 have. Particularly preferred the application of hair dye in a weak alkaline environment. The application temperatures can be in a range between 15 and 40 ° C, preferably at the temperature of the scalp, lie. After an exposure time from about 5 to 45, especially 15 to 30, minutes is the hair dye by rinsing of which to be colored Hair removed. The washing with a shampoo is eliminated, if a strong surfactant-containing carrier, z. B. a dyeing shampoo, has been used.

Especially in hard-to-dye Hair can prepare with the dye precursors without prior Mixing with the oxidation component applied to the hair become. After an exposure time of 20 to 30 minutes then - if necessary after an intermediate rinse - the oxidation component applied. After another exposure time of 10 to 20 minutes is then rinsed and if desired shampooed. In this embodiment, according to a first variant, in which the previous application of the dye precursors to effect a better penetration into the hair, the corresponding Medium adjusted to a pH of about 4 to 7. According to one second variant is first a Air oxidation, with the applied agent being preferred has a pH of 7 to 10. At the subsequent accelerated Post-oxidation may be the use of acidified peroxydisulfate solutions as Oxidizing agent may be preferred.

• – nichtionische Polymere wie beispielsweise Vinylpyrrolidon/Vinylacrylat-Copolymere, Polyvinylpyrrolidon und Vinylpyrrolidon/Vinylacetat-Copolymere,
• – anionische Polymere, wie Polyacryl- und Polymethacrylsäuren in Form ihrer Copolymere mit Acrylsäure- und Methacrylsäureestern und -amiden, Polyoxycarbonsäuren, wie Polyketo- und Polyaldehydocarbonsäuren und deren Salze, sowie Polymere und Copolymere der Crotonsäure mit Estern und Amiden der Acryl- und der Methacrylsäure, wie Vinylacetat-Crotonsäure- und Vinylacetat-Vinylpropionat-Crotonsäure-Copolymere,
• – Strukturanten wie Glucose und Maleinsäure,
• – haarkonditionierende Verbindungen wie Phospholipide, beispielsweise Sojalecithin, Ei-Lecithin und Kephaline,
• – Parfümöle, insbesondere solche mit der Duftnote einer Frucht, wie beispielsweise von Apfel, Birne, Erdbeere, Pfirsich, Aprikose, Ananas, Banane, Kirsche, Kiwi, Mango, Kokos, Mandel, Grapefruit, Maracuja, Mandarine und Melone, oder der Duftnote eines Genussmittels, wie beispielsweise von Tabak, Cola, Kaugummi, Guarana, Schokolade, Kakao, Vanille, Sarsaparilla, Pfefferminze und Rum. Dimethylisosorbid und Cyclodextrine,
• – Lösungsvermittler, wie Ethanol, Isopropanol, Ethylenglykol, Propylenglykol, Glycerin, Diethylenglykol und ethoxylierte Triglyceride,
• – Farbstoffe,
• – Antischuppenwirkstoffe wie Climbazol, Piroctone Olamine und Zink Omadine,
• – Wirkstoffe wie Bisabolol, Allantoin, Panthenol, Niacinmid, Tocopherol und Pflanzenextrakte,
• – Lichtschutzmittel,
• – Konsistenzgeber wie Zuckerester, Polyolester oder Polyolalkylether,
• – Fette und Wachse, wie Walrat, Bienenwachs, Montanwachs, Paraffine, Ester, Glyceride und Fettalkohole,
• – Fettsäurealkanolamide,
• – Komplexbildner wie EDTA, NTA, β-Alanindiessigsäure und Phosphonsäuren,
• – Quell- und Penetrationsstoffe wie PCA, Glycerin, Propylenglykolmonoethylether, Carbonate, Hydrogencarbonate, Guanidine, Harnstoffe sowie primäre, sekundäre und tertiäre Phosphate,
• – Trübungsmittel wie Latex oder Styrol/Acrylamid-Copolymere,
• – Perlglanzmittel wie Ethylenglykolmono- und -distearat oder PEG-3-distearat,
• – Weißpigmente
• – Reduktionsmittel wie z.B. Thioglykolsäure und deren Derivate, Thiomilchsäure, Cysteamin, Thioäpfelsäure und α-Mercaptoethansulfonsäure,
• – Oxidationsmittel wie Wasserstoffperoxid, Kaliumbromat und Natriumbromat,
• – Treibmittel wie Propan-Butan-Gemische, N₂O, Dimethylether, CO₂ und Luft sowie
• – Antioxidantien,
• – Bitterstoffe, wie beispielsweise Denatonium Benzoate,
• – Konservierungsmittel.

Further optional ingredients of the agents according to the invention are

• Nonionic polymers such as vinyl pyrrolidone / vinyl acrylate copolymers, polyvinyl pyrrolidone and vinyl pyrrolidone / vinyl acetate copolymers,
• Anionic polymers, such as polyacrylic and polymethacrylic acids in the form of their copolymers with acrylic and methacrylic esters and amides, polyoxycarboxylic acids, such as polyketo- and polyaldehydocarboxylic acids and their salts, and 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, especially 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 Stimulants 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,
• Anti-dandruff agents such as climbazole, piroctone olamine and zinc omadine,
• - active substances such as bisabolol, allantoin, panthenol, niacinmide, tocopherol and plant extracts,
• - sunscreen,
• 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 penetration 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 such as 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.

Regarding the type according to the invention used Active substance or the active compound combinations according to the invention Applied to the hair and / or on the skin, there are none principal restrictions. As a preparation of these preparations, for example, creams, lotions, Solutions, waters, Emulsions such as W / O, O / W, PIT emulsions (Called phase inversion emulsions, called PIT), microemulsions and multiple emulsions, nanoemulsions, coarse, unstable, one or more multiphase shaking mixtures, Gels, sprays, aerosols and foam aerosols. These are in usually on watery or aqueous-alcoholic Basis formulated. The alcoholic component is lower Alkanols and polyols such as propylene glycol and glycerol are used. Ethanol and isopropanol are preferred alcohols. Water and alcohol can in the watery alcoholic base in a weight ratio of 1:10 to 10: 1 available. Water as well as watery-alcoholic Mixtures containing up to 50% by weight, in particular up to 25% by weight, Alcohol, based on the mixture alcohol / water, may contain, according to the invention preferred Be fundamentals. The pH of these preparations can in principle at values of 2-11. It is preferably between 2 and 7, Values of 3 to 6 are particularly preferred. To adjustment this pH can be virtually any for cosmetic use acid or base can be used. Usually be called acids Food acids used. Be under consumption acids such acids understood that under the usual Food intake and positive effects to have the human organism. Exotic acids are, for example, acetic acid, lactic acid, tartaric acid, citric acid, malic acid, ascorbic acid and Gluconic. In the context of the invention is the use of citric acid and lactic acid particularly preferred. Preferred bases are ammonia, alkali hydroxides, Monoethanolamine, triethanolamine and N, N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine.

The agents according to the invention can also be formulated as a cosmetic agent for skin treatment. For example, there are products for body cleansing such as soaps, syndets, Shower gels, bath foams etc. in question. Also inventive products that are on the skin remain like creams, lotions, sunscreens, ointments, gels etc. can be easily formulated.

With Particular preference is given to compositions according to the invention in such a way that that they are used as deodorants or antiperspirants can. These compositions will also be summarized below referred to as compositions for reducing body odor on the skin. Here are cosmetic according to the invention Preferred compositions which are an agent for Influence of body odor or the odor of the hair, especially a deodorant Means, acts.

The cosmetic deodorant or antiperspirant compositions may be described as Powder, in stick form, as aerosol spray, pump spray, liquid and gel Roll on application, cream, gel and impregnated as a 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 based on fatty acid soaps, dibenzylidene sorbitol, N-acyl amino acid amides, 12-hydroxystearic acid and other gelling agents be presented.

Aerosol sprays, Pump sprays, roll on applications and creams can be used as a water-in-oil emulsion, oil-in-water emulsion, Silicone oil-in-water emulsion, Water-in-oil microemulsion, oil-in-water microemulsion, Silicone oil-in-water microemulsion, anhydrous suspension, alcoholic and hydroalcoholic solution, aqueous Gel and as oil available. All said compositions may be thickened, for example based on fatty acid soaps, Dibenzylidene sorbitol, N-acylamino acid amides, 12-hydroxystearic acid, polyacrylates Carbomer and Carbopol type, polyacrylamides and polysaccharides, which can be chemically and / or physically modified.

The Emulsions and microemulsions can be transparent, translucent or opaque.

The cosmetic according to the invention Deodorant or antiperspirant compositions may continue Contain fatty substances. Fatty substances are fatty acids, fatty alcohols, natural and synthetic cosmetic oil components as well as natural and to understand synthetic waxes, both in solid form also liquid in water or oily Dispersion may be present.

As fatty acids can be used linear and / or branched, saturated and / or unsaturated C _8-30 fatty acids. C _10-22 fatty acids are preferred. 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 technical mixtures thereof. Particularly preferred is the use of stearic acid. The fatty acids used can carry one or more hydroxyl groups. Preferred examples thereof are α-hydroxy-C ₁ -C ₈ 8-carboxylic acid and 12-hydroxystearic acid.

The Amount used is thereby 0,1 - 15 Wt .-%, preferably 0.5 - 10 Wt .-%, particularly preferably 1-5 Wt .-%, each based on the total composition.

When Fatty alcohols can saturated, mono- or polyunsaturated, branched or unbranched fatty alcohols having 6 - 30, preferably 10 - 22 and most preferably 12-22 Carbon atoms. Applicable according to the invention are e.g. decanol, Octanol, octenol, dodecenol, decenol, octadienol, dodecadienol, Decadienol, oleyl alcohol, eruca alcohol, ricinoleic alcohol, stearyl alcohol, Isostearyl alcohol, cetyl alcohol, lauryl alcohol, myristyl alcohol, Arachidyl alcohol, caprylic alcohol, capric alcohol, linoleyl alcohol, Linolenyl alcohol and behenyl alcohol, and their Guerbet alcohols.

For pen formulations become common Waxes used. As natural or synthetic waxes can used according to the invention are solid paraffins or isoparaffins, plant waxes such as candelilla wax, Carnauba wax, esparto wax, japan wax, cork wax, sugar cane wax, Ouricury wax, montan wax, sunflower wax, fruit waxes and animal Waxes, such as B. beeswax and other insect waxes, spermaceti, Shellac wax, wool wax and raffia fat, continue mineral waxes, such as. Ceresin and ozokerite or the petrochemical waxes, such as. Petrolatum, paraffin waxes, microwaxes of polyethylene or polypropylene and polyethylene glycol waxes. It may be advantageous to use hydrogenated or hydrogenated waxes. Farther are also chemically modified waxes, especially the hard waxes, z. Montan ester waxes, Sasol waxes and hydrogenated jojoba waxes, used.

Also suitable are the triglycerides of saturated and optionally hydroxylated C _16-30 fatty acids, such as. As hardened triglyceride fats (hydrogenated palm oil, hydrogenated coconut oil, hydrogenated castor oil), glyceryl tribehenate or glyceryl tri-12-hydroxystearat, also synthetic full esters of fatty acids and glycols (eg Syncrowachs ^® ) or polyols having 2-6 C-atoms, fatty acid monoalkanolamides with a C _12-22 acyl radical and a C _2-4 alkanol radical, 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-hydroxystearic acid) 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, and 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 advantageously, the wax components may be selected from the group of C _16-36 alkyl stearates, C _10-40 alkyl stearates of, the C _2-40 -Alkylisostearate, the C _20-40 dialkyl esters of dimer acids, C ₁₈ - ₃₈ -Alkylhydroxystearoylstearate, C _20-40 alkyl erucates are selected, and C _30-50 alkyl beeswax and cetearyl behenate can also be 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 wax components should be solid at 25 ° C, but melt in the range of 35-95 ° C, with a range of 45-85 ° C being preferred.

natural, chemically modified and synthetic waxes may be used alone or in combination be used. The wax components are preferably in one Amount of from 0.1 to 40% by weight, based on the total composition, preferably 1 to 30 wt .-% and in particular 5 to 15 wt .-%. The Compositions of the invention can furthermore at least one non-polar or polar liquid oil, natural or may be synthetic.

The polar oil component may be selected from vegetable oils, e.g. Example, sunflower oil, olive oil, soybean oil, rapeseed oil, almond oil, jojoba oil and the liquid portions of coconut oil and synthetic triglyceride oils, 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 dicaprylyl carbonate (Cetiol ^® CC), of mono, - di- and tri fatty acid esters of saturated and / or unsaturated linear and / or branched fatty acids with glycerol, for example. 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 having in each case 12-24 carbon atoms, for. 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 _3-20 alkanols such as butanol and glycerol, e.g. 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. As 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 Compositions of the invention to reduce body odor on the skin can furthermore contain at least one water-soluble alcohol. Under water solubility is understood according to the invention that At least 5 wt .-% of the alcohol at 20 ° C clear dissolve or - in the case long-chain or polymeric alcohols - brought by heating the solution to 50 ° C to 60 ° C in solution can be. 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-propanediol. 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 the 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 Mi of these, 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 polyhydric C ₂ -C ₉ -alkanol having 2-6 hydroxyl groups and / or the water-soluble polyethylene glycol consisting of 3-20 ethylene oxide units, in total in amounts of 3-25% by weight, preferably 8- 18% by weight, based on the total composition.

The Amount of the alcohol or alcohol mixture in the compositions of the invention to reduce body odor on the skin amounts to preferably 1-50 Wt .-% and preferably 5-40 Wt .-%, based on the total composition. According to the invention, both an alcohol as well as a mixture of several alcohols are used.

The Compositions of the invention to reduce body odor on the skin can be substantially anhydrous, that is at most 5 wt .-%, preferably contain at most 1 wt .-% water. In aqueous dosage forms is the water content 5 - 98 Wt .-%, preferably 10-90 and more preferably 15-85 Wt .-%, 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, water-solubility is understood to mean that at least 2% by weight of the silicone modified with hydrophilic groups dissolve in water at 20 ° 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 achieve higher consumer 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 Compositions of the invention to reduce body odor on the skin can furthermore at least one water-soluble Containing surfactant. As water-soluble Surfactants are basically suitable all soluble in the system at 1% by weight at 20 ° C and in water at 20 ° C at least 1% by weight of soluble Surfactants. Although the structure and ionogeneity are irrelevant nonionic surfactants, especially those at normal temperature, appear (20 ° C) solid Addition products of ethylene oxide to fatty molecules with at least an alkoxylatable group, preferably to be suitable. Such suitable surfactants are e.g. the addition products of 10 - 40 mol Ethylene oxide with linear fatty alcohols with 16 - 22 C atoms, with fatty acids with 12 - 22 C atoms, of fatty acid alkanolamides, fatty acid monoglycerides, sorbitan fatty acid monoester, fatty acid alkanolamides, fatty acid glycerides, e.g. on hardened Castor oil, on methylglucoside 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. Water solubility according to the invention is understood as meaning a solubility of at least 5 g of active substance per 100 g of solution at 20 ° C. Alum (KAl (SO ₄ ) ₂ .12H ₂ O), aluminum sulfate, aluminum lactate, sodium aluminum chlorhydroxylactate, aluminum chlorohydrate, aluminum chlorohydrate, aluminum sulfocarbolate, aluminum zirconium chlorohydrate, zinc chloride, zinc sulfocarbolate, zinc sulfate, zirconium chlorohydrate, and aluminum are examples of the invention 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 antiperspirants rant agents 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 as Micro Dry ^® Ultrafine from Reheis, as Chlorhydrol ^® sold as Locron ^® L Clariant in activated form as Reach ^® 501 from Reheis and in the form of an aqueous solution. 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 trade is particularly advantageous according to the invention.

According to the invention preferred Deodorising cosmetic compositions are characterized that they are astringent antiperspirant Salts in an amount of 1-40 wt .-% of the composition.

Farther can the compositions of the invention to reduce body odor the skin contain germ-inhibiting or deodorant agents. Particularly suitable are organohalogen compounds and halides, quaternary Ammonium compounds, a range of plant extracts and zinc compounds. Preference is given to chlorhexidine and Chlorhexidingluconat, Benzalkoniumhalogenide and Cetylpyridinium. Furthermore, sodium bicarbonate, sodium phenolsulfonate and zinc phenolsulfonate and z. B. the components of lime blossom oil used.

Further antibacterial deodorants are lantibiotics, Glycoglycerolipids, sphingolipids (ceramides), sterols and others Agents that inhibit bacteria inhibit on the skin, z. As glycosidases, lipases, proteases, Carbohydrates, di- and Oligosaccharidfettsäureester 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. Talc, boron nitride, titanium dioxide, which may if desired be coated, optionally modified starches and starch derivatives, cellulose powders and polymer powders, furthermore plant extracts, protein hydrolysates, vitamins, perfume oils, sebostatics, anti-acne agents and keratolytics.

The cosmetic deodorant or antiperspirant compositions may, as far as they are liquid, on flexible and absorbent carrier applied and offered as deodorant or antiperspirant wipes or sponges become. As flexible and absorbent carrier in the context of the invention are z. As carriers of textile fibers, collagen or polymeric foams. Textile fibers can be both natural fibers and Cellulose (cotton, linen), silk, wool, regenerated cellulose (Rayon, rayon), cellulose derivatives as well as synthetic fibers such as. Polyester, polyacrylonitrile, polyamide or polyolefin fibers or blends of such fibers woven or unwoven. These fibers can too absorbent Cotton pads, nonwovens or woven or knitted fabrics be. Also flexible and absorbent polymeric foams, e.g. As polyurethane foams and polyamide foams are suitable substrates. The substrate can be one, two, three or more have three layers, the individual layers of the same or different materials. Each substrate layer may be a homogeneous or an inhomogeneous structure with, for example have different zones of different density.

When absorbent For the purposes of the invention, such carrier substrates are to be considered, which at 20 ° C at least 10% by weight, based on dry weight, of water can bind adsorptively or capillary. But are preferably those carriers which are at least 100 wt .-% Adsorptive and capillary binding of water.

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 Abquet rule, soaking or simply by injecting the composition of the invention into the carrier substrates.

According to the invention preferred is still the dosage form as an aerosol, wherein the cosmetic composition a propellant, selected from propane, butane, isobutane, pentane, isopentane, dimethyl ether, fluorocarbons and chlorofluorocarbons and mixtures thereof.

in denen jeweils mindestens ein Rest R ausgewählt ist aus -(CH₂)₂-CH=CH-CH₂-CH₃ (Hexenylrest) oder-CH₂-CH=CH-C₆H₅ (Zimtalkoholrest) und die anderen Reste R jeweils unabhängig voneinander ausgewählt sind aus der Gruppe, die ein Wasserstoffatom, die geradkettigen oder verzweigten, gesättigten oder ungesättigten, substituierten oder unsubstituierten C_1-6-Kohlenwasserstoffreste und den 2-Phenoxyethyl-Rest enthält, und m Werte aus dem Bereich 1 bis 20 und n Werte aus dem Bereich 2 bis 100 annimmt, sowie Mischungen hiervon, in kosmetischen Mitteln.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 ) ₂ -CH = CH-CH ₂ -CH ₃ (hexenyl) or -CH ₂ -CH = CH-C ₆ H ₅ (cinnamyl) and the other radicals R each independently selected from the group consisting of a hydrogen atom containing straight or branched chain, 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 values in the range 2 to 100, and mixtures thereof, in cosmetic products.

Especially 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. Thus, regardless of the chemical composition of the fragrances, the compounds according to the invention can be used in perfume mixtures in order to give the entire perfume composition a prolonged release of fragrance. The use according to the invention according to one of claims 9 or 10 is therefore particularly preferred for increasing the fragrance intensity and / or for prolonging the fragrance Fragrance and / or fragrance perception of the cosmetic Agents, in particular deodorants or antiperspirants.

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

in denen jeweils mindestens ein Rest R ausgewählt ist aus -(CH₂)₂-CH=CH-CH₂-CH₃(Hexenylrest) oder -CH₂-CH=CH-C₆H₅ (Zimtalkoholrest) und die anderen Reste R jeweils unabhängig voneinander ausgewählt sind aus der Gruppe, die ein Wasserstoffatom, die geradkettigen oder verzweigten, gesättigten oder ungesättigten, substituierten oder unsubstituierten C_1-6-Kohlenwasserstoffreste und den 2-Phenoxyethyl-Rest enthält, und m Werte aus dem Bereich 1 bis 20 und n Werte aus dem Bereich 2 bis 100 annimmt, auf die Haut, insbesondere auf die Haut der Achselhöhlen, aufgetragen wird.Another object of the present invention is a method for reducing body odor on the skin, wherein a cosmetic deodorant or antiperspirant composition comprising at least one silicic acid ester of the formulas 1 and / or II and / or III and / or IV

in which in each case at least one radical R is selected from - (CH ₂ ) ₂ -CH = CH-CH ₂ -CH ₃ (hexenyl) or -CH ₂ -CH = CH-C ₆ H ₅ (cinnamyl) and the other radicals R each independently selected from the group consisting of a hydrogen atom containing straight or branched chain, 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 values ranging from 2 to 100, applied to the skin, especially to the skin of the underarms.

Also in terms of preferred method according to the invention mutatis mutandis applies what has been said to the compositions of the invention.

Examples:

• Dpg = Dipropylenglycol

Parfüm 2:

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

• Dpg = dipropylene glycol

Perfume 2:

2. Hautcremes:

3. Tagescremes:

4. Tagescremes mit Lichtschutzfaktor:

5. Tagescremes:

Hautcremes auf Basis einer Lipoprotein-Creme

2. Wasser-in-Oel-Emulsion

4. Wasser-in-Silicon-Emulsion

3. Reinigungszubereitungen 1. Gesichtswasser-Zubereitungen:

2. Reinigungsgel:

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:

3rd day creams:

4. Day Creams with SPF:

5th day creams:

Skin creams based on a lipoprotein cream

2. Water-in-oil emulsion

4. Water-in-silicone emulsion

3. Cleaning Preparations 1. Facial Toner Preparations:

2. Cleansing Gel:

Haarspülung: Eumulgin^® B2 0,3 Cetyl/Stearylalkohol 3,3 Isopropylmyristat 0,5 Paraffinöl perliquidum 15 cSt. DAB 9 0,3 Dehyquart^®L 80 0,4 Lamesoft^® PO 65 1,5 Cosmedia Guar^® C 261 1,5 Promois^® Milk-CAQ 3,0 Citronensäure 0,4 Potassium Cocoyl Hydrolyzed Silk 2,0 Caomint 2,0 Hexapeptide-2 0,3 Poly-L-serin 0,5 Phenonip^® 0,8 Parfüm 1 0,15 Wasser ad 100 Haarkur: Dehyquart^® F75 4,0 Cetyl/Stearylalkohol 4,0 Paraffinöl 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-Isoleucin 2,5 Glyoxylsäure 0,5 Amisafe-LMA-60^® 1,0 Gluadin^®VN 20 3,0 Germall^® 115 1,0 Citronensäure 0,15 Phenonip^® 0,8 Parfüm 1 0,15 Wasser ad 100 Haarkur: Dehyquart^® L80 2,0 Cetyl/Stearylalkohol 6,0 Paraffinöl perliquidum 15 cSt DAB 9 2,0 Rewoquat^®W 75 2,0 Cosmedia Guar^® C261 0,5 Lamesoft^® PO 65 0,5 Sepigel^®305 3,5 Honeyquat^® 50 1,0 Gluadin^®W 20 3,0 Calmosensine 2,0 Hydrolyzed Sericin 0,8 L-Glycin 0,4 L-Alanyl-L-prolin 1,0 L-Tyrosin 0,2 Citronensäure 0,15 Phenonip^® 0,8 Parfüm 2 0,15 Wasser ad 100 Haarkur: Dehyquart^® F75 0,3 Salcare^®SC 96 5,0 Gluadin^® WQ 1,5 Lamesoft^® PO 65 0,5 Dow Corning^®200 Fluid, 5 cSt. 1,5 Gafquat^®755N 1,5 Poly-D/L-alanin 1,5 Calmosensine 2,0 Caomint 1,0 Serin 0,1 Glycinmethylester 0,5 Tyrosinmethylester 0,2 Sericin 0,2 Biodocarb^® 0,02 Parfüm 2 0,25 Wasser ad 100 Shampoo: Texapon^® NSO 40,0 Dehyton^® G 6,0 Polymer JR 400^® 0,5 Cetiol^® HE 0,5 Ajide^® NL 50 1,0 Lamesoft^® PO 65 3,0 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 Glutaminsäure 0,2 Citronensäure 0,5 Natriumbenzoat 0,5 Parfüm 2 0,4 NaCl 0,5 Wasser ad 100 Shampoo: Texapon^® NSO 43,0 Dehyton^® K 10,0 Plantacare^® 1200 UP 4,0 Lamesoft^® PO 65 2,5 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 Silk 3,0 Sericin 10,0 Milchsäure 0,5 Äpfelsäure 0,5 Glucamate^®DOE 120 0,5 Natriumchlorid 0,2 Parfüm 1 0,2 Wasser ad 100 Anti-Haarausfall-Haanivasser für Männer:

Haarwasser:

2-Phasen-Wellness-Massagefluid für Körper und Kopfhaut

Massagefluid für empfindliche Kopfhaut

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 3.3 isopropyl 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® ^® Milk-CAQ 3.0 citric acid 0.4 Potassium Cocoyl Hydrolyzed Silk 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 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 0.5 Amisafe LMA-60 ^® 1.0 Gluadin® ^® VN 20 3.0 Germall® ^® 115 1.0 citric acid 0.15 Phenonip ^® 0.8 Perfume 1 0.15 water ad 100 Hair Treatment: Dehyquart® ^® L80 2.0 Cetyl / stearyl 6.0 Paraffin oil perliquidum 15 cSt DAB 9 2.0 Rewoquat ^® W 75 2.0 Cosmedia® guar ^® C261 0.5 Lamesoft ^® PO 65 0.5 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 ^® PO 65 0.5 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 0.5 tyrosine 0.2 sericin 0.2 Biodocarb ^® 0.02 Perfume 2 0.25 water ad 100 Shampoo: Texapon.RTM ^® NSO 40.0 Dehyton ^® G 6.0 Polymer JR ^400® 0.5 Cetiol ^® HE 0.5 Ajide ^® NL 50 1.0 Lamesoft ^® PO 65 3.0 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 ^® PO 65 2.5 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 Silk 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 Haanivasser for Men:

Hair Lotion:

2-phase wellness massage fluid for body and scalp

Massage fluid for sensitive scalp

Duschgel:

Wasserfreie tensidhaltige AT-Stifte (Angaben in Gewichtsteilen)

Sprühfähige, translucente Antitranspirant-Mikroemulsionen (Angaben in Gew.-%)

Seifenhaltige Stifte (Angaben in Gew.-%)

Antitranspirant Roll-on (Angaben in Gew.-%)

Antitranspirant-Spray vom Suspensionstyp (Angaben in Gew.-%)

Transparentseife

Beispiele für Zusammensetzungen zum Tränken von Tüchern

All quantities are, unless otherwise stated, parts by weight. Compact hair spray for normal consolidation: Ultrahold 8 6.0 Amphomer LV-71 4.0 amino methyl propanol 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 O5 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)

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

With these drinker compositions various viscose nonwovens were equipped. There were punched, unperforated, napped, single-ply, two-ply and three-ply fleeces equipped. The towels were both as wet towels as well as dry towels (this means, after equipping were the towels to a residual water content of less than 10 wt .-%, preferably smaller 5% by weight, dried).

example Figure 1 illustrates an impregnation composition for a Lotion and make-up remover cloth.

example Figure 2 illustrates a drenching composition for a Self-cloth represents.

example Figure 3 illustrates a soaking 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, in addition to fragrance 1% by weight of (Z) -3-hexenylsilicic acid ester according to claim 1. A comparison perfume composition P3V was identically composed but contained instead of the (Z) -3-hexenylsilicic ester according to claim 1 dipropylene glycol in an amount of 1% by weight.

Simulation of fragrance adhesion in a humid environment (similar the conditions in the forearm area)

From perfume compositions P3E and P3V were each given equal amounts to a filter paper. The filter paper was then over a about half filled with water Petri dish laid. It was ensured that the filter paper does not sag and not with the liquid in the Petri dish in contact comes. The Petri dish was covered with a glass funnel whose Funnel tube protruded upwards and was closed. Subsequently was the test setup at 37 ° C stored. After every 0, 2, 4, 6 and 24 hours the shutter became Briefly removed from the funnel tube and the smell assessed.

To At test times 2, 4, 6 and 24 hours, one of P3E showed up higher fragrance intensity as for 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 prepared with 0.74 wt .-% P4E or 0.74 wt .-% P4V, further shampoos with 0.5 wt .-% P5E or 0.5 wt .-% P5V, which on 30 subjects were tested. 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 according to 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) applied. 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):

tested on the one hand the smell of the invention and of the comparison products, continue the odor (for the testing personnel) and odor intensity of the hair 24 or 48 hours after the shampoo treatment. This resulted in the smell and the fragrance intensity hair 24 and 48 hours after shampoo treatment a significant Preference of the products according to the invention across from the comparison products.

Claims (14)

Cosmetic composition for the treatment of the skin and / or the scalp and / or the hair and / or for oral and dental hygiene, comprising in a suitable cosmetic carrier at least one silicic acid ester of the formulas 1 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, 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-octen-1-ol, and the other radicals R are each independently selected from the group consisting of which is a hydrogen atom, the straight-chain or v branched, saturated or unsaturated, substituted or unsubstituted C _1-6 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. Cosmetic composition according to claim 1, characterized in that at least 10 mol%, preferably at least 20 mol% and especially 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-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 ) Contains 3-octen-1-ol, and the ande each R 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 values from the range 1 to 20 and n takes values from the range 2 to 100, as well as mixtures thereof. Cosmetic compositions according to any one of claims 1 or 2, characterized in that at least 10 mol%, preferably at least 20 mol%, and more preferably more than 40 mol% of the R radicals R come from at least one alcohol which is selected from (Z) -3-hexene-1-ol (leaf alcohol). Cosmetic composition according to any one of claims 1-3, characterized characterized in that n values are in the range of 2 to 50, preferably from the range of 2 to 20 and especially from the range of 3 to 10 with particular preference to the values 4, 5, 6, 7 and 8, and m values ranging from 2 to 10, under special Favoring the values 2 and 3 assumes. Cosmetic composition according to one of claims 1 to 4, characterized in that it or the silicic acid esters in total amounts of from 0.000001 to 10% by weight, 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 wt .-%, each based on the weight of the cosmetic Composition containing. 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 R is selected from residues of perfume alcohols and biocide alcohols derived from (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-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. Cosmetic composition according to one of claims 1 to 6, characterized in that it astringent antiperspirant Salts in an amount of 1 - 40 Wt .-% of the composition. Cosmetic composition according to one of claims 1 to 7, characterized in that it contains at least one surfactant. 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 a zwitterionic surfactant, more preferably cocamidopropylbetaine, is included. Use of a cosmetic composition according to one of the claims 1 to 9 for the treatment of keratin fibers, in particular human Hair. Non-therapeutic, cosmetic use of a Cosmetic composition according to 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. Use of a cosmetic composition according to one of the claims 1 to 9 to influence the body odor or odor of the hair, especially for deodorization. Use according to one of claims 10 to 12 for increasing the intensity of the scent and / or for extension the fragrance adhesion and / or odor perception of the cosmetic products. 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, (+) - 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 radicals R are each independently selected from the group consisting of Hydrogen atom, the straight-chain or branched, saturated takes ten or unsaturated, substituted or unsubstituted C _1-6 hydrocarbon radicals and includes the 2-phenoxyethyl radical, and m values from the range 1 to 20 and na value of 2 to 100, and mixtures thereof, to the skin, especially on the skin of the armpits, is applied.