DE102005015446A1 - Synergists to enhance the effect of repellents - Google Patents

Abstract

The invention relates to the use of at least one cycloaliphatic compound selected from the group cycloaliphatic carboxylic acid, esters of a cycloaliphatic carboxylic acid, amide of a cycloaliphatic carboxylic acid, cycloaliphatic alcohol and cycloaliphatic ketone, as a synergist for enhancing the action of repellents in cosmetic and dermatological formulations for defense and / or quenching arthropods on the skin or surface, and corresponding new preparations and their preparation.

Description

The The present invention relates to the use of cycloaliphatic Carboxylic acids, their esters and / or their amides as synergists to strengthen the Effect of repellents in cosmetic and dermatological formulations for the defense and deterrence of arthropods and corresponding new ones Preparations and their preparation.

A Variety of mosquitoes, Brakes fleas, lice, Bedbugs, as well as ticks and mites, which are part of the arthropod tribe (Arthropods) belong and in the further course also under the biological sense not correctly used generic term insects are addressed, feed themselves from the blood of warm-blooded animals, to which the people count. They drill their skin with their lancing and suction tools Victims until they encounter blood vessels. During the Food intake but they vasodilator and anticoagulants, which cause itching, wheals in the host and allergic reactions can. In particular, in the tropics and subtropics exists beyond the risk of infection with pathogens. For example the malaria by the Anopheles mosquito or the yellow fever by the Yellow fever mosquito transferred. Even in temperate regions there is a risk of infection with insect-borne Pathogens such as those transmitted by tick bites Tick-borne encephalitis.

a Protection against harassment by offering arthropods so-called repellents. This is a series of active substances, which, by their smell, repel insects and spiders. These are usually low-volatility compounds that are slow evaporate on the skin and thus a fragrance bell over the Forming skin that expels the arthropods.

To the usual one Repellents counts N, N-diethyl-3-methylbenzamide ("DEET"), which is active against mosquitoes, and sandflies, brakes, fleas, bugs, Ticks and mites is active. Further, dimethyl phthalate (trade name: Palatinol M, DMP) against mosquitoes, Lice, Ticks and mites used.

Particularly effective is 3- (Nn-butyl-N-acetyl-amino) -propionic acid ethyl ester (under the trade name IR3535 ^® in Fa. Merck available), which can be used for example against mosquitoes, tsetse flies, ticks and brakes. The suitability of further β-alanine derivatives as insect repellents is described in M. Klier, F. Kuhlow, J. Soc. Cos. Chem., 27, pp. 141-153 (1976).

Of the Of course, the prior art knows a variety of different Insect repellent formulations. Disadvantage of this conventional insect repellent is that the known repellents are limited in their duration of action and evaporate too quickly again. Also common is their defense effect not strong enough.

Already in the 40s and 50s of the 20th century was also the Effect of cycloaliphatic carboxylic acids as repellents studied (Carroll N. Smith, M. M. Cole, Elmer A. Jones, J. C. Clark, Journal of Economic Entomology, 42 (1949) 716; Harry K. Gouk, S.A. Hall, Caroll N. Smith, I.H. Gilbert, Journal of Economic Entomology, 50 (1957) 176). You - careful not expressed cosmetic smell as well as their compared to conventional Repellents weak effectiveness have a use in cosmetics but so far prevented.

task Accordingly, the present invention has been a drawback to the prior art overcome the technique and possibilities to provide cosmetic and dermatological insect repellent formulations, the one stronger Show effect as the known repellents.

It was surprising and for the expert in any way foreseeable that the use of cycloaliphatic Carboxylic acids, their esters and their amides, cycloaliphatic alcohols as well cycloaliphatic ketones the disadvantages of the prior art would help and to a reinforcement the effect of repellents in cosmetic and dermatological Formulations for the defense of arthropods leads.

One The first object of the present invention is therefore the use selected from at least one cycloaliphatic compound the group cycloaliphatic carboxylic acid, esters of a cycloaliphatic Carboxylic acid, Amide of a cycloaliphatic carboxylic acid, cycloaliphatic alcohol and / or cycloaliphatic ketone, as a synergist for enhancing the Effect of repellents in cosmetic and dermatological formulations for the defense and / or deterrence of arthropods.

at to ward off the invention and / or quenching arthropods are preferred around flies and / or crawling arthropods, without limitation General public belong to this for example, mosquitoes, Flies, brakes, fleas, Bugs, ticks, mites, lice, Ants, cockroaches and others.

The The principle of deterrence is not on the cosmetic or dermatological prophylaxis of insect bites or bites, but For example, it can also be used in crop protection or in households become.

wobei n = 0 bis 12, vorzugsweise 0 bis 6, ist,
wobei X = COOH oder OH, wobei der cycloaliphatische Ring und/oder die aliphatische Seitenkette substituiert sein können mit

• – geradkettigen oder verzweigten C₁- bis C₁₂-Alkylgruppen, vorzugsweise C₁- bis C₄-Alkylgruppen, und ganz besonders bevorzugt C₁-Alkylgruppen,
• – geradkettigen oder verzweigten C₁- bis C₁₂-Alkenylgruppen und/oder
• – geradkettigen oder verzweigten C₁- bis C₁₂-Hydroxyalkylgruppen, wobei die Hydroxygruppen an ein primäres oder sekundäres Kohlenstoffatom der Kette gebunden sein können

und wobei der cycloaliphatische Ring einfach oder zweifach ungesättigt sein kann und/oder eine exocylcische Doppelbindung aufweisen kann.Preference is given to the use according to the invention of cycloaliphatic carboxylic acids or cycloaliphatic alcohols of the formula (I) and / or of the formula (II)

where n = 0 to 12, preferably 0 to 6,
wherein X = COOH or OH, wherein the cycloaliphatic ring and / or the aliphatic side chain may be substituted with

• Straight-chain or branched C ₁ - to C ₁₂ -alkyl groups, preferably C ₁ - to C ₄ -alkyl groups, and very particularly preferably C ₁ -alkyl groups,
• Straight-chain or branched C ₁ -C ₁₂ -alkenyl groups and / or
• Straight-chain or branched C ₁ - to C ₁₂ -hydroxyalkyl groups, it being possible for the hydroxyl groups to be bonded to a primary or secondary carbon atom of the chain

and wherein the cycloaliphatic ring may be mono- or diunsaturated and / or may have an exocyclic double bond.

It It has been found that such cycloaliphatic carboxylic acids are particularly well suited, in which the alkylene chain 0 to 6 carbon atoms contains i.e. which are selected from cyclohexylcarboxylic acid, cyclohexylacetic, cyclohexylpropionic, cyclohexylbutanoic acid, cyclohexylpentanoic, cyclohexylhexanoic, Cyclopentylcarbonsäure, cyclopentylacetic, cyclopentylpropionic, Cyclopentylbutansäure, Cyclopentylpentansäure, Cyclopentylhexansäure.

Further preferred is the use of esters in which the hydroxy group of the cycloaliphatic carboxylic acid of the formula (I) and / or (II) is replaced by a straight-chain or branched C ₁ - to C ₁₂ -alkoxy group.

Here It has been found that such esters are suitable for the use according to the invention the cycloaliphatic carboxylic acids are particularly suitable in which the ester group 1 to 4 carbon atoms contains i.e. the selected are methyl, ethyl, n-propyl, iso-propyl and n-butyl, iso-butyl and tert-butyl ester.

Further, the use of amides is preferred in which the hydroxy group of the cycloaliphatic carboxylic acid of formula (I) and / or (II) is replaced by an amide group -NR ¹ R ² , wherein R ¹ and R ^{2 may be the} same or different and selected are from straight-chain or branched C ₁ - to C ₁₂ -alkyl groups, preferably C ₁ - to C ₄ -alkyl groups.

Besides is also the use of cycloaliphatic alcohols as synergists preferred in which the side chains contain a carbon atom. For example, these cycloaliphatic alcohols contain one, two three or four methyl groups and one double bond in the ring or a methylene group, via an exocyclic double bond is attached to the ring.

• – α-Necrodol (1,4,4,5-Tetramethyl-3-hydroxymethyl-1-cyclopenten)
• – epi-α-Necrodol
• – β-Necrodol (1,1,2-Trimethyl-3-methylen-5-hydroxymethyl-cyclopentan)
• – epi-β-Necrodol
• – γ-Necrodol (1,1,2,3-Tetramethyl-5-hydroxymethyl-2-cyclopenten)
• – 1,1,2,3-Tetramethyl-4-hydroxymethyl-2-cyclopenten
• – 2,3,4,5-Tetramethyl-2-cyclopenten-1-on
• – 2,3,5,5-Tetramethyl-4-methylen-2-cyclopenten-1-on
• – 2,4,5,5-Tetramethyl-1,3-cyclopentadien-1-carbonsäure
• – 3,4,4-Trimethyl-2-cyclohexen-1-on
• – 3,4,4-Trimethyl-5-cyclohexen-2-on

Without restricting generality, examples of cycloaliphatic alcohols and ketones to be used according to the invention are examples

• Α-Necrodol (1,4,4,5-tetramethyl-3-hydroxymethyl-1-cyclopentene)
• Epi-α-Necrodol
• Β-Necrodol (1,1,2-trimethyl-3-methylene-5-hydroxymethylcyclopentane)
• Epi-β-Necrodol
• Γ-Necrodol (1,1,2,3-tetramethyl-5-hydroxymethyl-2-cyclopentene)
• 1,1,2,3-tetramethyl-4-hydroxymethyl-2-cyclopentene
• 2,3,4,5-tetramethyl-2-cyclopenten-1-one
• 2,3,5,5-tetramethyl-4-methylene-2-cyclopenten-1-one
• 2,4,5,5-tetramethyl-1,3-cyclopentadiene-1-carboxylic acid
• 3,4,4-trimethyl-2-cyclohexene-1-one
• 3,4,4-trimethyl-5-cyclohexene-2-one

• – Cyclopentylessigsäure
• – Cyclopentylpropionsäure
• – Cyclohexylessigsäure
• – Cyclohexylpropionsäure
• – Cyclopentylessigsäureethylester
• – Cyclopentylpropionsäureethylester
• – Cyclohexylessigsäureethylester
• – Cyclohexylpropionsäureethylester

In detail, the compounds enumerated below, individually or in combination, have proved to be particularly suitable for the use according to the invention:

• - cyclopentylacetic acid
• - cyclopentylpropionic acid
• - Cyclohexylacetic acid
• - Cyclohexylpropionic acid
• - cyclopentylacetic acid ethyl ester
• - Cyclopentylpropionic acid ethyl ester
• - Cyclohexylacetic acid ethyl ester
• - Cyclohexylpropionsäureethylester

The used according to the invention cycloaliphatic carboxylic acids, their esters and / or their amides are typically used in amounts of 0.01 to 10 wt .-%, preferably in amounts of 0.1 wt .-% to 2 wt .-% and particularly preferably used in amounts of 0.5 to 1 wt .-%. It prepares the expert no difficulties the quantities dependent from the intended effect of the formulation or preparation select accordingly.

advantageously, So are cycloaliphatic carboxylic acids, their esters and / or their Amides individually or in combinations already in concentrations of under one percent able to effect known repellents For example, they lead to an increase in Duration of action up to approx. 20% and more.

Furthermore to lead cycloaliphatic carboxylic acids, their esters and / or their amides to reduce the viscosity of the formulation. This is especially for their use in sprayable emulsions of advantage.

One Another object of the present invention are preparations, the at least one cycloaliphatic compound selected from the group cycloaliphatic carboxylic acid, esters of a cycloaliphatic Carboxylic acid, Amide of a cycloaliphatic carboxylic acid, cycloaliphatic alcohol and / or cycloaliphatic ketone, and at least one active substance their effect due to the presence of the cycloaliphatic Strengthened connection becomes.

at The preparations are usually topically applicable Preparations, for example cosmetic or dermatological formulations. The preparations in this case contain a cosmetic or dermatologically suitable carrier and depending on the desired Property profile optional further suitable ingredients.

wobei n = 0 bis 12, vorzugsweise 0 bis 6, ist,
wobei X = COOH oder OH,
wobei der cycloaliphatische Ring und/oder die aliphatische Seitenkette substituiert sein können mit

• – geradkettigen oder verzweigten C₁- bis C₁₂-Alkylgruppen, vorzugsweise C₁- bis C₄-Alkylgruppen, und ganz besonders bevorzugt C₁-Alkylgruppen,
• – geradkettigen oder verzweigten C₁- bis C₁₂-Alkenylgruppen und/oder
• – geradkettigen oder verzweigten C₁- bis C₁₂-Hydroxyalkylgruppen, wobei die Hydroxygruppen an ein primäres oder sekundäres Kohlenstoffatom der Kette gebunden sein können

und wobei der cycloaliphatische Ring einfach oder zweifach ungesättigt sein kann und/oder eine exocylcische Doppelbindung aufweisen kann.The cycloaliphatic carboxylic acids or the cycloaliphatic alcohols of the preparations according to the invention are preferably compounds of the formula (I) and / or of the formula (II)

where n = 0 to 12, preferably 0 to 6,
where X = COOH or OH,
wherein the cycloaliphatic ring and / or the aliphatic side chain may be substituted with

• Straight-chain or branched C ₁ - to C ₁₂ -alkyl groups, preferably C ₁ - to C ₄ -alkyl groups, and very particularly preferably C ₁ -alkyl groups,
• Straight-chain or branched C ₁ -C ₁₂ -alkenyl groups and / or
• Straight-chain or branched C ₁ - to C ₁₂ -hydroxyalkyl groups, it being possible for the hydroxyl groups to be bonded to a primary or secondary carbon atom of the chain

and wherein the cycloaliphatic ring may be mono- or diunsaturated and / or may have an exocyclic double bond.

In the case of the esters of the cycloaliphatic carboxylic acids of the preparations according to the invention, preference is given to those in which the hydroxy group of the cycloaliphatic carboxylic acid of the formula (I) and / or (II) is replaced by a straight-chain or branched C ₁ to C ₁₂ alkoxy group, preferably C ₁ to C ₄ alkoxy group is replaced.

Preferred among the amides of the cycloaliphatic carboxylic acids of the preparations according to the invention are those in which the hydroxy group of the cycloaliphatic carboxylic acid of the formula (I) and / or (II) is replaced by an amide group -NR ¹ R ² , where R ¹ and R ^{2 are} identical or may be different and are selected from straight-chain or branched C ₁ - to C ₁₂ -alkyl groups, preferably C ₁ - to C ₄ -alkyl groups.

The cycloaliphatic carboxylic acid, their esters and / or their amide are used in the preparations according to the invention typically in amounts of from 0.01 to 10% by weight, preferably in amounts from 0.1% to 2% by weight and most preferably in amounts from 0.5 to 1 wt .-% used. It prepares the expert no difficulty the quantities depending on the intended Select the effect of the preparation accordingly.

One Another object of the present invention is a method for the preparation of a preparation according to the invention, in which the at least one cycloaliphatic carboxylic acid, its ester and / or its Amide and at least one active substance, preferably a repellent, with a cosmetically or dermatologically suitable carrier as well other suitable substances are mixed.

Furthermore The object of the present invention is the use of a preparation according to the invention for topical application or for application on a surface.

To the invention to be used Count active ingredients so-called repellents, in particular insect repellents. Furthermore can the preparation of the invention preferably also other active substances, such as UV filters, Fiavon derivatives, chromone derivatives, aryloximes and parabens included.

The most repellent agents belong the classes of amides, alcohols, esters and ethers. Repellent - active ingredients usually meet the following conditions: they may do not evaporate too quickly and do not penetrate the skin. she allowed to on the skin neither primary irritating nor sensitizing and should also not be toxic. Their effectiveness must also be under the action of skin fluid and / or UV radiation.

Accordingly can the invention as synergists used here by supporting the Extend the duration of action of the repellents on the skin and / or by the Increase the effect of the repellents and thus allow the use of lower repellent amounts in the formulation.

It is therefore preferred for the preparation according to the invention or the formulation to be used according to the invention to contain at least one repellent, the repellent preferably being selected from N, N-diethyl-3-methylbenzamide, ethyl 3- (acetyl-butyl-amino) -propionate, Dimethyl phthalate, butopyronoxyl, 2,3,4,5-bis (2-butylene) -tetrahydro-2-furaldehyde, N, N-caprylic acid diethylamide, N, N-diethylbenzamide, o-chloro-N, N-diethylbenzamide, N- (2-ethylhexyl) -8,9,10-trinorborn-5-ene-2,3-dicarboximide, dimethylcarbate, di-n-propylisocinchomeronate, (R) -p-mentha-1,8-diol, 2-ethylhexane 1,3-diol, N-octyl-bicyclohepetendiecarboximid, piperonyl butoxide, 1- (2-methylpropyloxycarbonyl) -2- (hydroxyethyl) -piperidine (Bayrepel ^®; Bayer). or mixtures thereof, more preferably selected from N, N-diethyl-3-methylbenzamide, ethyl 3- (acetyl-butyl-amino) -propionate, 1- (2-methylpropyloxycarbonyl) -2- (hydroxyethyl) -piperidine or mixtures thereof.

at the invention to be used Preparations containing repellents are included preferably insect repellents. Become insect repellent preferably in the form of solutions, Gels, pens, rollers, pump sprays and aerosol sprays offered, being solutions and sprays form the bulk of commercially available products. Base for this Both product forms are usually alcoholic or aqueous-alcoholic solutions with the addition of fatty substances and slight perfuming. It may in the preparations of the invention but especially emulsions, gels, creams, ointments and the like act, the additional active ingredients or their main purpose in another application, for example the sunscreen or day care.

Next the repellents, in particular insect repellents, the preparation of the invention also other active substances, such as UV filters, flavone derivatives, Containing chromone derivatives, aryloximes and parabens.

parabens are 4-hydroxybenzoic acid esters, in free form or as sodium salts for the preservation of preparations used in the field of food, cosmetics and medicines become. The effect of the ester is directly proportional to the chain length of the On the other hand, the solubility decreases with increasing chain length. As non-dissociating compounds, the esters are broad pH-independent and act in a pH range of 3.0-8.0. The antimicrobial Mechanism of action is based on damage to microbial membranes by the surface activity of the PHB esters as well as on protein denaturation. In addition, interactions with coenzymes occur. The effect is aimed against fungi, yeasts and bacteria. The as preservatives the most important parabens are 4-hydroxybenzoic acid methyl ester, 4-hydroxybenzoic acid ethyl ester, 4-hydroxybenzoate, 4-hydroxybenzoate.

Among the aryl oximes, 2-hydroxy-5-methyllaurophenone oxime, which is also referred to as HMLO, LPO or F5, is preferably used. Its suitability for use in cosmetic products, for example, from the German patent application DE 41 16 123 known. Preparations containing 2-hydroxy-5-methyllaurophenone oxime are accordingly suitable for the treatment of skin diseases which are associated with inflammation. It is known that such preparations can be used, for example, for the therapy of psoriasis, different forms of eczema, irritative and toxic dermatitis, UV dermatitis and other allergic and / or inflammatory diseases of the skin and the skin appendages. Compositions according to the invention which, in addition to the compounds mentioned, additionally contain an aryloxime, preferably 2-hydroxy-5-methyllaurophenone oxime, show surprising antiinflammatory suitability. The preparations preferably contain from 0.01 to 10% by weight of the aryloxime, and it is particularly preferred if the preparation contains from 0.05 to 5% by weight of aryloxime.

When Flavone derivatives according to the invention are flavonoids and coumaranones Understood. Flavonoids according to the invention are the glycosides of flavanones, Flavones, 3-hydroxyflavones (= flavonols), aurones, isoflavones and redoids [Römpp Chemie Lexikon, Vol. 9, 1993]. In the context of the present invention however, the aglycones, i. the sugar-free Ingredients, and understood the derivatives of flavonoids and aglycones. Furthermore, in the context of the present invention, the term Flavonoid also understood anthocyanidin (cyanidin). As part of the Coumaranones of the present invention are also derivatives thereof Understood.

preferred Flavonoids are derived from flavanones, flavones, 3-hydroxyflavones, Aurones and isoflavones, in particular flavanones, flavones, 3-hydroxyflavones and Auronen, from.

The Flavonoids are preferably selected from the following compounds: 4,6,3 ', 4'-tetrahydroxyaurone, Quercetin, rutin, isoquercetin, eriodictyol, taxifolin, luteolin, Trishydroxyethyl quercetin (Troxequercetin), Trishydroxyethylrutin (Troxerutin), trishydroxyethylisoquercetin (troxeisoquercetin), Trishydroxyethylluteolin (troxeluteolin), α-glycosylrutin, tiliroside as well their sulphates and phosphates. Among the flavonoids are as active ingredients according to the invention in particular rutin, tiliroside, α-glycosylrutin and troxerutin preferred.

Under the coumaranones is 4,6,3 ', 4'-tetrahydroxybenzylcoumaranone-3 prefers.

wobei
R¹ und R² gleich oder verschieden sein können und ausgewählt sind aus

• – H, -C(=O)-R⁷, -C(=O)-OR⁷,
• – geradkettigen oder verzweigten C₁- bis C₂₀-Alkylgruppen,
• – geradkettigen oder verzweigten C₃- bis C₂₀-Alkenylgruppen, geradkettigen oder verzweigten C₁- bis C₂₀-Hydroxyalkylgruppen, wobei die Hydroxygruppe an ein primäres oder sekundäres Kohlenstoffatom der Kette gebunden sein kann und weiter die Alkylkette auch durch Sauerstoff unterbrochen sein kann, und/oder
• – C₃- bis C₁₀-Cycloalkylgruppen und/oder C₃- bis C₁₂-Cycloalkenylgruppen, wobei die Ringe jeweils auch durch -(CH₂)_n-Gruppen mit n = 1 bis 3 überbrückt sein können, R³ steht für H oder geradkettige oder verzweigte C₁- bis C₂₀-Alkylgruppen, R⁴ steht für H oder OR⁸, R⁵ und R⁶ gleich oder verschieden sein können und ausgewählt sind aus
• – -H, -OH,
• – geradkettigen oder verzweigten C₁- bis C₂₀-Alkylgruppen,
• – geradkettigen oder verzweigten C₃- bis C₂₀-Alkenylgruppen,
• – geradkettigen oder verzweigten C₁- bis C₂₀-Hydroxyalkylgruppen, wobei die Hydroxygruppe an ein primäres oder sekundäres Kohlenstoffatom der Kette gebunden sein kann und weiter die Alkylkette auch durch Sauerstoff unterbrochen sein kann und R⁷ steht für H, geradkettige oder verzweigte C₁- bis C₂₀-Alkylgruppen, eine Polyhydroxy-Verbindung, wie vorzugsweise einen Ascorbinsäurerest oder glycosidische Reste und R⁸ steht für H oder geradkettige oder verzweigte C₁- bis C₂₀-Alkylgruppen, wobei mindestens 2 der Substituenten R¹, R², R⁴-R⁶ verschieden von H sind oder mindestens ein Substituent aus R¹ und R² für -C(=O)-R⁷ oder -C(=O)-OR⁷ steht.

Among chromone derivatives are preferably certain chromene-2-one derivatives, which are useful as active ingredients for the preventive treatment of human skin and human hair against aging processes se and damaging environmental influences are suitable, understood. At the same time they show a low irritation potential for the skin, positively influence the water binding in the skin, maintain or increase the elasticity of the skin and thus promote a smoothing of the skin. These compounds preferably correspond to the following formula

in which
R ¹ and R ^{2 may be the} same or different and are selected from

• - H, -C (= O) -R ⁷ , -C (= O) -OR ⁷ ,
• Straight-chain or branched C ₁ - to C ₂₀ -alkyl groups,
• Straight-chain or branched C ₃ - to C ₂₀ -alkenyl groups, straight-chain or branched C ₁ - to C ₂₀ -hydroxyalkyl groups, where the hydroxy group may be bonded to a primary or secondary carbon atom of the chain and furthermore the alkyl chain may also be interrupted by oxygen, and or
• - C ₃ - to C ₁₀ -cycloalkyl groups and / or C ₃ - to C ₁₂ -cycloalkenyl groups, wherein the rings may each be bridged by - (CH ₂ ) _n groups with n = 1 to 3, R ³ is H or straight-chain or branched C ₁ - to C ₂₀ -alkyl groups, R ⁴ is H or OR ⁸ , R ⁵ and R ^{6 may be} identical or different and are selected from
• - -H, -OH,
• Straight-chain or branched C ₁ - to C ₂₀ -alkyl groups,
• Straight-chain or branched C ₃ -C ₂₀ -alkenyl groups,
• Straight-chain or branched C ₁ - to C ₂₀ -hydroxyalkyl groups, where the hydroxy group may be bonded to a primary or secondary carbon atom of the chain and furthermore the alkyl chain may also be interrupted by oxygen and R ⁷ is H, straight-chain or branched C ₁ - to C ₂₀ -alkyl groups, a polyhydroxy compound, such as preferably an ascorbic acid residue or glycosidic radicals and R ⁸ is H or straight-chain or branched C ₁ - to C ₂₀ -alkyl groups, where at least 2 of the substituents R ¹ , R ² , R ⁴ R ^{6 are} different from H or at least one substituent of R ¹ and R ^{2 is} -C (= O) -R ⁷ or -C (= O) -OR ⁷ .

Of the Proportion of one or more compounds selected from Flavonoids, Cromon derivatives and Coumaranonen in the preparation according to the invention is preferably from 0.001 to 5% by weight, more preferably from 0.01 up to 2% by weight, based on the total preparation.

The protective Effect of preparations according to the invention against oxidative stress or against the action of radicals can be improved if the preparations have one or more Contain antioxidants, the expert does not encounter any difficulties prepares suitable fast or delayed-acting antioxidants select.

In a preferred embodiment The present invention is therefore in the preparation according to the invention to a preparation for the protection of body cells against oxidative Stress, in particular to reduce skin aging, thereby in that they contain, in addition to the cycloaliphatic carboxylic acids, their Esters and / or their amides and the repellents and, where appropriate other ingredients contains one or more antioxidants.

There are many known and proven substances known from the literature which can be used as antioxidants, eg amino acids (eg glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles, (eg urocaninic acid) and their derivatives, peptides such as D, L- Carnosine, D-carnosine, L-carnosine and their derivatives (eg anserine), carotenoids, carotenes (eg α-carotene, β-carotene, lycopene) and their derivatives, chlorogenic acid and its derivatives, lipoic acid and derivatives thereof (eg dihydrolipoic acid), Aurothioglucose, propylthiouracil and other thiols (eg thioredoxin, glutathione, cysteine, cystine, cystamine and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl , γ-linoleyl, cholesteryl and Glyceryl esters) and their salts, dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and derivatives thereof (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) and sulfoximine compounds (eg buthionine sulfoximines, homocysteinesulfoximine, buthionine sulfones, penta, hexa, heptathionine sulfoximine) in very small amounts tolerated dosages (eg pmol to μmol / kg), (metal) chelators, (eg α-hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin), α-hydroxy acids (eg citric acid, lactic acid, malic acid), humic acid, bile acid, bile extracts, bilirubin , Biliverdin, EDTA, EGTA and their derivatives, unsaturated fatty acids and their derivatives, vitamin C and derivatives (eg ascorbyl palmitate, magnesium ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives (eg vitamin E acetate), vitamin A and derivatives (eg -A palmitate) and benzylic benzylic resin, rutinic acid and derivatives thereof, α-glycosylrutin, ferulic acid, furfuryl idenglucitol, carnosine, butylhydroxytoluene, butylhydroxyanisole, nordohydroguajaretic acid, trihydroxybutyrophenone, quercitin, uric acid and its derivatives, mannose and its derivatives, zinc and its derivatives (eg ZnO, ZnSO ₄ ), selenium and its derivatives (eg selenomethionine), stilbenes and their derivatives ( eg stilbene oxide, trans-stilbene oxide).

Mixtures of antioxidants are also suitable for use in the cosmetic preparations according to the invention. Known and commercial mixtures mixtures are, for example comprising, as active ingredients, lecithin, L - (+) - ascorbyl palmitate and citric acid (for example (for example Oxynex ^® AP), natural tocopherols, L - (+) - ascorbyl palmitate, L - (+) - ascorbic acid and citric acid (for example Oxynex ^® K LIQUID), tocopherol extracts from natural sources, L - (+) - ascorbyl palmitate, L - (+) - ascorbic acid and citric acid (for example Oxynex ^® L LIQUID), DL-α-tocopherol, L - (+) -Ascorbylpalmitat, citric acid and lecithin (for example Oxynex ^® LM) or butylhydroxytoluene (BHT), L - (+) -. ascorbyl palmitate and citric acid antioxidants (for example Oxynex ^® 2004) with the inventive compounds in such compositions is typically in proportions in the range of 1000: 1 to 1: 1000, preferably used in amounts of 100: 1 to 1: 100.

The preparations to be used according to the invention may contain vitamins as further ingredients. Preference is given to vitamins and vitamin derivatives selected from vitamin A, vitamin A propionate, vitamin A palmitate, vitamin A acetate, retinol, vitamin B, thiamin chloride hydrochloride (vitamin B ₁ ), riboflavin (vitamin B ₂ ), nicotinamide , Vitamin C (ascorbic acid), Vitamin D, Ergocalciferol (Vitamin D ₂ ), Vitamin E, DL-α-Tocopherol, Tocopherol E-acetate, Tocopherol hydrogen succinate, Vitamin K ₁ , Esculin (Vitamin P active ingredient), Thiamine (Vitamin B ₁ ), nicotinic acid (niacin), pyridoxine, pyridoxal, pyridoxamine, (vitamin B ₆ ), pantothenic acid, biotin, folic acid and cobalamin (vitamin B ₁₂ ) in the cosmetic preparations according to the invention, particularly preferably vitamin A palmitate, vitamin C and its derivatives, DL-α-tocopherol, tocopherol-E-acetate, nicotinic acid, pantothenic acid and biotin. Vitamins are usually used with the compounds according to the invention in such compositions in ratios in the range from 1000: 1 to 1: 1000, preferably in amounts of 100: 1 to 1: 100.

Under the phenols with antioxidant effect are partially as natural substances occurring polyphenols for Applications in the pharmaceutical, cosmetic or nutritional field especially interesting. For example, the mainly as Plant dyes commonly known flavonoids or bioflavonoids antioxidant potential. With effects of the substitution pattern mono- and dihydoxy flavones are dealt with by K. Lemanska, H. Szymusiak, B. Tyrakowska, R. Zielinski, I.M.C.M. Rietjens; Current Topics in Biophysics 2000, 24 (2), 101-108. It is observed there that Dihydroxyflavones with an OH group adjacent to the keto function or OH groups in 3'4'- or 6,7- or 7,8-position have antioxidant properties while others Mono- and Dihydroxyflavone partially no antioxidant properties exhibit.

Frequently becomes Quercetin (cyanidanol, cyanidolone 1522, meletin, sophoretine, ericin, 3,3 ', 4', 5,7-pentahydroxyflavone) mentioned as a particularly effective antioxidant (e.g., C. A. Rice-Evans, N.J. Miller, G. Paganga, Trends in Plant Science 1997, 2 (4), 152-159). K. Lemanska, H. Szymusiak, B. Tyrakowska, R. Zielinski, A.E.M.F. Soffers and I.M.C.M. Rietjens (Free Radical Biology & Medicine 2001, 31 (7), 869-881 investigate the pH dependence of antioxidants Effect of Hydoxyflavones. about Quercetin shows the highest activity of the whole pH range Structures.

wobei R¹ bis R¹⁰ gleich oder verschieden sein können und ausgewählt sind aus

• – H
• – OR11
• – geradkettigen oder verzweigten C₁- bis C₂₀-Alkylgruppen, geradkettigen oder verzweigten C₃- bis C₂₀-Alkenylgruppen, geradkettigen oder verzweigten C₁- bis C₂₀-Hydroxyalkylgruppen, wobei die Hydroxygruppe an ein primäres oder sekundäres Kohlenstoffatom der Kette gebunden sein kann und weiter die Alkylkette auch durch Sauerstoff unterbrochen sein kann, und/oder
• – C₃- bis C₁₀-Cycloalkylgruppen und/oder C₃- bis C₁₂-Cycloalkenylgruppen, wobei die Ringe jeweils auch durch -(CH₂)_n-Gruppen mit n = 1 bis 3 überbrückt sein können,
• – wobei alle OR¹¹ unabhängig voneinander stehen für
• – OH
• – geradkettige oder verzweigte C₁- bis C₂₀-Alkyloxygruppen,
• – geradkettigen oder verzweigten C₃- bis C₂₀-Alkenyloxygruppen,
• – geradkettigen oder verzweigten C₁- bis C₂₀-Hydroxyalkoxygruppen, wobei die Hydroxygruppe(n) an ein primäre oder sekundäre Kohlenstoffatome der Kette gebunden sein können und weiter die Alkylkette auch durch Sauerstoff unterbrochen sein kann, und/oder
• – C₃- bis C₁₀-Cycloalkyloxygruppen und/oder C₃- bis C₁₂-Cycloalkenyloxygruppen, wobei die Ringe jeweils auch durch -(CH₂)_n-Gruppen mit n = 1 bis 3 überbrückt sein können und/oder,
• – Mono- und/oder Oligoglycosylreste, mit der Maßgabe, dass mindestens 4 Reste aus R¹ bis R⁷ stehen für OH und dass im Molekül mindestens 2 Paare benachbarter Gruppen -OH vorliegen,
• – oder R², R⁵ und R⁶ für OH und die Reste R¹, R³, R⁴ und R^7-10 für H stehen,

wie sie in der Deutschen Patentanmeldung DE-A-102 44 282 beschrieben sind.Suitable antioxidants are furthermore compounds of the formula (III)

wherein R ¹ to R ^{10 may be the} same or different and are selected from

• - H
• - OR11
• Straight-chain or branched C ₁ -C ₂₀ -alkyl groups, straight-chain or branched C ₃ -C ₂₀ -alkenyl groups, straight-chain or branched C ₁ -C ₂₀ -hydroxyalkyl groups, the hydroxy group being bonded to a primary or secondary carbon atom of the chain and the alkyl chain can also be interrupted by oxygen, and / or
• C ₃ - to C ₁₀ -cycloalkyl groups and / or C ₃ - to C ₁₂ -cycloalkenyl groups, it also being possible for the rings to be bridged by - (CH ₂ ) _n groups where n = 1 to 3,
• Where all OR ^{11 are} independent of each other
• - OH
• Straight-chain or branched C ₁ -C ₂₀ -alkyloxy groups,
• Straight-chain or branched C ₃ - to C ₂₀ -alkenyloxy groups,
• Straight-chain or branched C ₁ - to C ₂₀ -hydroxyalkoxy groups, where the hydroxy group (s) may be bonded to a primary or secondary carbon atom of the chain and furthermore the alkyl chain may also be interrupted by oxygen, and / or
• C ₃ - to C ₁₀ -cycloalkyloxy groups and / or C ₃ - to C ₁₂ -cycloalkenyloxy groups, it also being possible for the rings to be bridged by - (CH ₂ ) _n groups where n = 1 to 3 and / or
• Mono- and / or oligoglycosyl radicals, with the proviso that at least 4 radicals from R ¹ to R ⁷ are OH and that at least 2 pairs of adjacent groups -OH are present in the molecule,
• Or R ² , R ⁵ and R ^{6 are} OH and the radicals R ¹ , R ³ , R ⁴ and R ^{7-10 are} H,

as described in the German patent application DE-A-102 44 282.

Advantages of the compositions according to the invention containing at least one antioxidant are, in addition to the abovementioned advantages, in particular the antioxidant action and good skin tolerance. Of particular advantage is the particular profile of action of the compounds of formula (III), which in the DPPH assay in a high capacity to catch radicals (EC ₅₀ ), a time-delayed action (T _EC50 > 20 min) and thus a medium to high anti-radical Efficiency (AE). In addition, the compounds of formula (III) combine in the molecule antioxidant properties with UV absorption in the UV-A and / or B range. Preference is therefore also given to preparations comprising at least one compound of the formula (III) which is characterized in that at least two adjacent radicals of the radicals R ¹ to R ⁴ are OH and at least two adjacent radicals of the radicals R ⁵ to R ⁷ are OH , Particularly preferred preparations comprise at least one compound of the formula (III), which is characterized in that at least three adjacent radicals of the radicals R ¹ to R ^{4 are} OH, wherein preferably the radicals R ¹ to R ^{3 are} OH.

In particular according to the invention preferred preparations can also serve the sunscreen and then contain next to the cycloaliphatic Carboxylic acids, their esters and / or their amides and the repellents and, where appropriate other ingredients also UV filters.

in principle come all UV filters for a combination with the effect pigments to be used according to the invention and repellents in question. Particularly preferred are such UV filters, their physiological harmlessness has already been proven. As well as UVA as well as UVB filters, there are many known from the literature and proven Substances, e.g.

• – 2-Cyano-3,3-diphenylacrylsäure-2-ethylhexylester (z.B. Eusolex^® OCR),
• – 3,3'-(1,4-Phenylendimethylen)-bis-(7,7-dimethyl-2-oxobicyclo-[2.2.1]hept-1-ylmethansulfonsäure sowie ihre Salze (z.B. Mexoryl^® SX) und
• – 2,4,6-Trianilino-(p-carbo-2'-ethylhexyl-1'-oxi)-1,3,5-triazin (z.B. Uvinul^® T 150)
• – 2-(4-Diethylamino-2-hydroxy-benzoyl)-benzoesäure hexylester (z.B. Uvinul^®UVA Plus, Fa. BASF).

Benzylidenecamphor derivatives, such as 3- (4'-methylbenzylidene) -dl-camphor (for example Eusolex ^® 6300), 3-benzylidenecamphor (for example Mexoryl ^® SD), polymers of N - {(2 and 4) - [(2-oxoborn-3- ylidene) methyl] benzyl} acrylamide (for example Mexoryl ^® SW), N, N, N-trimethyl-4- (2-oxoborn-3-ylidenemethyl) anilinium methylsulfate (for example Mexoryl ^® SK) or (2-oxoborn-3-ylidene) toluene-4-sulfonic acid ( for example Mexoryl SL ^®), benzoyl or dibenzoylmethanes, such as 1- (4-tert-butylphenyl) -3- (4-methoxyphenyl) propane-1,3-dione (for example Eusolex ^® 9020) or 4-isopropyl dibenzoylmethane (such as Eusolex ^® 8020),
Benzophenones such as 2-hydroxy-4-methoxybenzophenone (for example Eusolex ^® 4360) or 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its sodium salt (for example Uvinul ^® MS-40),
Methoxycinnamate such as octyl methoxycinnamate (for example Eusolex ^® 2292), 4-methoxycinnamate, for example as a mixture of isomers (for example Neo Heliopan E 1000 ^®)
Salicylate derivatives such as 2-ethylhexyl salicylate (for example Eusolex ^® OS), 4-isopropylbenzyl salicylate (for example Megasol ^®) or 3,3,5-trimethylcyclohexyl salicylate (for example Eusolex ^® HMS), 4-aminobenzoic acid and derivatives, such as 4-aminobenzoic acid, 4- (dimethylamino) benzoic acid 2-ethylhexyl ester (for example Eusolex ^® 6007), ethoxylated ethyl 4-aminobenzoate (for example Uvinul ^® P25),
Phenylbenzimidazolesulfonic acids, such as 2-phenylbenzimidazole-5-sulfonic acid and potassium, sodium and triethanolamine salts thereof (for example Eusolex ^® 232), 2,2- (1,4-phenylene) -bisbenzimidazol-4,6-disulfonic acid and salts thereof ( for example Neoheliopan ^® AP) or 2,2- (1,4-phenylene) -bisbenzimidazol-6-sulfonic acid;
and other substances like

• - 2-cyano-3,3-diphenylacrylate, 2-ethylhexyl (for example Eusolex ^® OCR),
• - 3,3 '- (1,4-phenylenedimethylene) bis (7,7-dimethyl-2-oxobicyclo- [2.2.1] hept-1-ylmethanesulfonic acid and salts thereof (for example Mexoryl SX ^®) and
• - 2,4,6-trianilino- (p-carbo-2'-ethylhexyl-1'-oxi) -1,3,5-triazine (for example Uvinul ^® T 150)
• - 2- (4-diethylamino-2-hydroxy-benzoyl) -benzoic acid hexyl ester (Uvinul ^® example UVA Plus, BASF.).

The listed in the list Links are to be considered as examples only. Of course you can too other UV filters are used.

These Organic UV filters are usually in an amount of 0.5 to 10% by weight, preferably 1-8%, in the formulations incorporated.

• – 2-(2N-Benzotriazol-2-yl)-4-methyl-6-(2-methyl-3-(1,3,3,3-tetramethyl-1-(trimethylsilyloxy)disiloxanyi)propyl)phenol (z.B. Silatrizole^®),
• – 4,4'-[(6-[4-((1,1-Dimethylethyl)aminocarbonyl)phenylamino]-1,3,5-triazin-2,4-diyl)diimino]bis(benzoesäure-2-ethylhexylester) (z.B. Uvasorb^® HEB),
• – α-(Trimeihylsilyl)-ω-[trimethylsilyl)oxy]poly[oxy(dimethyl [und ca. 6% methyl[2-[p-[2,2-bis(ethoxycarbonyl]vinyl]phenoxy]-1-methylenethyl] und ca. 1,5 methyl[3-[p-[2,2-bis(ethoxycarbonyl)vinyl)phenoxy)-propenyl) und 0,1 bis 0,4% (methylhydrogen]silylen]] (n ≈ 60) (CAS-Nr. 207 574-74-1)
• – 2,2'-Methylen-bis-(6-(2H-benzotriazoi-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol) (CAS-Nr. 103 597-45-1)
• – 2,2'-(1,4-Phenylen)bis-(1H-benzimidazol-4,6-disulfonsäure, Mononatriumsalz) (CAS-Nr. 180 898-37-7) und
• – 2,4-bis-{[4-(2-Ethyl-hexyloxy)-2-hydroxyl]-phenyl}-6-(4-methoxyphenyi)-1,3,5-triazin (CAS-Nr. 103 597-45-, 187 393-00-6).
• – 4,4'-[(6-[4-((1,1-Dimethylethyl)aminocarbonyl)phenylamino]-1,3,5-triazin-2,4-diyl)diimino]bis(benzoesäure-2-ethylhexylester) (z.B. Uvasorb^® HEB), Weitere geeignete UV-Filter sind auch Methoxyflavone ensprechend der älteren Deutschen Patentanmeldung DE-A-10232595.

Other suitable organic UV filters are, for example

• 2- (2N-Benzotriazol-2-yl) -4-methyl-6- (2-methyl-3- (1,3,3,3-tetramethyl-1- (trimethylsilyloxy) disiloxanyi) propyl) phenol (eg silatrizole ^® ),
• 4,4 '- [(6- [4 - ((1,1-dimethylethyl) aminocarbonyl) phenylamino] -1,3,5-triazine-2,4-diyl) diimino] bis (benzoic acid 2-ethylhexyl ester) (for example Uvasorb HEB ^®),
• Α- (trimethylsilyl) -ω- [trimethylsilyl) oxy] poly [oxy (dimethyl] and about 6% methyl [2- [p- [2,2-bis (ethoxycarbonyl) vinyl] phenoxy] -1-methylenethyl] and about 1.5 methyl [3- [p- [2,2-bis (ethoxycarbonyl) vinyl] phenoxy) propenyl) and 0.1 to 0.4% (methylhydrogen] silylene]] (n≈60) ( CAS No. 207 574-74-1)
• 2,2'-methylenebis (6- (2H-benzotriazoi-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol) (CAS No. 103 597-45-1)
• 2,2'- (1,4-phenylene) bis (1H-benzimidazole-4,6-disulfonic acid, monosodium salt) (CAS No. 180 898-37-7) and
• 2,4-bis - {[4- (2-ethyl-hexyloxy) -2-hydroxyl] -phenyl} -6- (4-methoxyphenyl) -1,3,5-triazine (CAS No. 103 597- 45-, 187 393-00-6).
• 4,4 '- [(6- [4 - ((1,1-dimethylethyl) aminocarbonyl) phenylamino] -1,3,5-triazine-2,4-diyl) diimino] bis (benzoic acid 2-ethylhexyl ester) (for example Uvasorb HEB ^®), Further suitable UV filters are also methoxyflavones corresponding to the earlier German patent application DE-A-10232595th

organic UV filters are typically used in an amount of 0.5 to 20% by weight, preferably 1 - 15%, incorporated in cosmetic formulations.

In order to ensure optimized UV protection, it is further preferred if preparations with light protection properties also contain inorganic UV filters. As inorganic UV filters are those from the group of titanium dioxides such as coated titanium dioxide (eg Eusolex ^® T-2000, Eusolex ^® T-AQUA, Eusolex ^® T-AVO), zinc oxides (eg Sachtotec ^® ), iron oxides or cerium oxides conceivable. These inorganic UV filters are usually incorporated in an amount of 0.5 to 20 weight percent, preferably 2-10%, in cosmetic preparations.

preferred Compounds with UV-filtering properties are 3- (4'-methylbenzylidene) dl-camphor, 1- (4-tert-butylphenyl) -3- (4-methoxy-phenyl) -propane-1,3-dione, 4-isopropyldibenzoylmethane, 2-hydroxy-4-methoxybenzophenone, octyl methoxycinnamate, 3,3,5-trimethyl-cyclo-hexyl-salicylate, 4- (dimethylamino) benzoic acid 2-ethylhexyl ester, 2-cyano-3,3-di-phenyl-acrylic acid 2-ethylhexyl ester, 2-phenyl-benzimidazole-5-sulfonic acid and their potassium, sodium and triethanol amine salts.

By Combination of one or more of said compounds with UV filter action can protect against harmful Effects of UV radiation be optimized.

optimized Compositions can For example, the combination of organic UV filters 4'-methoxy-6-hydroxyflavone with 1- (4-tert-butylphenyl) -3- (4-methoxyphenyl) propane-1,3-dione and 3- (4'-methylbenzylidene) dl camphor contain. This combination results in broadband protection, by the addition of inorganic UV filters, such as titanium dioxide microparticles still added can be.

• – Die Hydrophilie der Kapselwand kann unabhängig von der Löslichkeit des UV-Filters eingestellt werden. So können beispielsweise auch hydrophobe UV-Filter in rein wässrige Zubereitungen eingearbeitet werden. Zudem wird der häufig als unangenehm empfundene ölige Eindruck beim Auftragen der hydrophobe UV-Filter enthaltenden Zubereitung unterbunden.
• – Bestimmte UV-Filter, insbesondere Dibenzoylmethanderivate, zeigen in kosmetischen Zubereitungen nur eine verminderte Photostabilität. Durch Verkapselung dieser Filter oder von Verbindungen, die die Photostabilität dieser Filter beeinträchtigen, wie beispielsweise Zimtsäurederivate, kann die Photostabilität der gesamten Zubereitung erhöht werden.
• – In der Literatur wird immer wieder die Hautpenetration durch organische UV-Filter und das damit verbundene Reizpotential beim direkten Auftragen auf die menschliche Haut diskutiert. Durch die hier vorgeschlagene Verkapselung der entsprechenden Substanzen wird dieser Effekt unterbunden.
• – Allgemein können durch Verkapselung einzelner UV-Filter oder anderer Inhaltstoffe Zubereitungsprobleme, die durch Wechselwirkung einzelner Zubereitungsbestandteile untereinander entstehen, wie Kristallisationsvorgänge, Ausfällungen und Agglomeratbildung vermieden werden, da die Wechselwirkung unterbunden wird.

All mentioned UV filters can also be used in encapsulated form. In particular, it is advantageous to use organic UV filters in encapsulated form. In detail, there are the following advantages:

• - The hydrophilicity of the capsule wall can be adjusted independently of the solubility of the UV filter. For example, hydrophobic UV filters can also be incorporated into purely aqueous preparations. In addition, the often perceived as unpleasant oily impression when applying the hydrophobic UV filter containing preparation is suppressed.
• Certain UV filters, in particular dibenzoylmethane derivatives, show only reduced photostability in cosmetic preparations. By encapsulating these filters or compounds that affect the photostability of these filters, such as cinnamic acid derivatives, the photostability of the entire formulation can be increased.
• In the literature, the skin penetration through organic UV filters and the associated irritation potential during direct application to the human skin is discussed again and again. The encapsulation of the corresponding substances proposed here prevents this effect.
• - Generally, by encapsulation of individual UV filters or other ingredients preparation problems caused by interaction of individual preparation components with each other, such as crystallization processes, precipitation and agglomeration can be avoided because the interaction is prevented.

Therefore is it preferred according to the invention if one or more of the above UV filters are encapsulated in Form present. It is advantageous if the capsules so small are they with the naked eye can not be observed. To achieve the o.g. Effects it is still required that the capsules are sufficiently stable and the encapsulated drug (UV filter) not or only to a small extent to the environment.

Suitable capsules may have walls of inorganic or organic polymers. For example, in US 6,242,099 B1 describe the preparation of suitable capsules with walls of chitin, chitin derivatives or polyhydroxylated polyamines. Capsules which are particularly preferred for use in accordance with the invention have walls which can be obtained by a SoIGeI process as described in applications WO 00/09652, WO 00/72806 and WO 00/71084. Again, capsules whose walls are made up of silica gel (silica, undefined silicon oxide hydroxide) are preferred. The production of such capsules is known to the skilled worker, for example, from the cited patent applications, whose contents are expressly also part of the subject of the present application.

there the capsules are in formulations to be used according to the invention preferably contained in such amounts, which ensure that the encapsulated UV filters in the amounts specified above in the Preparation present.

The used according to the invention Preparations can about that addition, more usual skin-friendly or skin-care active ingredients. This can be done in principle all agents known to those skilled in the art.

Particularly preferred active ingredients are, for example, also so-called compatible solutes. These are substances that are involved in the osmoregulation of plants or microorganisms and can be isolated from these organisms. Under the generic term compatible solutes also the described in the German patent application DE-A-10133202 osmolytes are taken. Suitable osmolytes are, for example, the polyols, methylamine compounds and amino acids and in each case their precursors. Within the meaning of the German patent application DE-A-10133202, osmolytes are understood as meaning, in particular, substances from the group of polyols, such as, for example, myo-inositol, mannitol or sorbitol and / or one or more of the osmolytically active substances mentioned below: taurine, choline, betaine, Phosphorylcholine, glycerophosphorylcholine, glutamine, glycine, α-alanine, glutamate, aspartate, proline, and taurine. Precursors of these substances are, for example, glucose, glucose polymers, phosphatidylcholine, phosphatidylino sitol, inorganic phosphates, proteins, peptides and polyamic acids. Precursors are z. B. Compounds that are converted to osmolytes by metabolic steps.

Preferably are according to the invention as compatible Solute substances chosen from the group consisting of pyrimidinecarboxylic acids (such as ectoine and hydroxyectoine), Proline, betaine, glutamine, cyclic diphosphoglycerate, N. acetylornithine, trimethylamine N-oxide Di-myo-inositol phosphate (DIP), cyclic 2,3-diphosphoglycerate (cDPG), 1,1-Diglycerol Phosphate (DGP), β-Mannosylglycerate (Firoin), β-Mannosylglyceramide (Firoin-A) and / or dimannosyl-di-inositol phosphate (DMIP) or an optical Isomer, derivative, e.g. an acid, a salt or ester of these compounds or combinations thereof used.

there are among the pyrimidinecarboxylic acids in particular ectoine ((S) -1,4,5,6-tetrahydro-2-methyl-4-pyrimidinecarboxylic acid) and Hydroxyectoine ((S, S) -1,4,5,6-tetrahydro-5-hydroxy-2-methyl-4-pyrimidinecarboxylic acid) and to name their derivatives. These compounds stabilize enzymes and other biomolecules in aqueous solutions and organic solvents. Furthermore, they stabilize especially enzymes against denaturing Conditions such as salts, extreme pH, surfactants, urea, guanidinium chloride and other connections.

Ectoin and ectoine derivatives such as hydroxyectoine may be beneficial in pharmaceuticals be used. In particular, hydroxyectoine for the production a drug used to treat skin diseases become. Other uses of hydroxyectoine and other ectoin derivatives typically in areas where e.g. Trehalose as an additive is used. So can Ectoin derivatives, such as hydroxyectoine, as a protective substance in dried Yeast and bacterial cells find use. Also pharmaceutical Products such as non-glycosylated, pharmaceutically active peptides and proteins e.g. t-PA can protected with Ectoin or its derivatives.

Under The cosmetic applications in particular is the use of Ectoin and ectoin derivatives for the care of aged, dry or call irritated skin. Thus, in the European patent application EP-A-0 671 161 specifically describes that ectoine and hydroxyectoine in cosmetic preparations such as powders, soaps, surfactant-containing Cleansing products, lipsticks, blushes, make-up, skin care creams and sunscreen preparations be used.

worin R¹ ein Rest H oder C1-8-Alkyl, R² ein Rest H oder C1-4-Alkyl und R³, R⁴, R⁵ sowie R⁶ jeweils unabhängig voneinander ein Rest aus der Gruppe H, OH, NH₂ und C1-4-Alkyl sind. Bevorzugt werden Pyrimidincarbonsäuren eingesetzt, bei denen R² eine Methyl- oder eine Ethylgruppe ist und R¹ bzw. R⁵ und R⁶ H sind. Insbesondere bevorzugt werden die Pyrimidincarbonsäuren Ectoin ((S)-1,4,5,6-Tetrahydro-2-methyl-4-pyrimidin-carbonsäure) und Hydroxyectoin ((S,S)-1,4,5,6-Tetrahydro-5-hydroxy-2-methyl-4-pyrimidin-carbonsäure) eingesetzt. Dabei enthalten die erfindungsgemäß einzusetzenden Zubereitungen derartige Pyrimidincarbonsäuren vorzugsweise in Mengen bis zu 15 Gew.-%.In this case, a pyrimidinecarboxylic acid according to the following formula is preferably used,

wherein R ^{1 is} a radical H or C 1-8 -alkyl, R ^{2 is} a radical H or C 1-4 -alkyl and R ³ , R ⁴ , R ⁵ and R ^{6 are} each independently a radical from the group H, OH, NH ₂ and C1-4 alkyl. Preference is given to using pyrimidinecarboxylic acids in which R ^{2 is} a methyl or an ethyl group and R ¹ or R ⁵ and R ^{6 are} H. Particular preference is given to the pyrimidinecarboxylic acids ectoine ((S) -1,4,5,6-tetrahydro-2-methyl-4-pyrimidinecarboxylic acid) and hydroxyectoine ((S, S) -1,4,5,6-tetrahydrocarboxylic acid). 5-hydroxy-2-methyl-4-pyrimidine-carboxylic acid). In this case, the preparations to be used according to the invention preferably contain such pyrimidinecarboxylic acids in amounts of up to 15% by weight.

In particular according to the invention it is preferred if the compatible solutes are selected Di-myo-inositol phosphate (DIP), cyclic 2,3-diphosphoglycerate (cDPG), 1,1-diglycerol phosphate (DGP), β-mannosylglycerate (Firoin), β-mannosylglyceramide (Firoin-A) or / and di-mannosyl-diinositol phosphate (DMIP), ectoine, Hydroxyectoine or mixtures thereof.

Among the aryl oximes also preferably used is preferably 2-hydroxy-5-methyllaurophenonoxim, which is also referred to as HMLO, LPO or F5 used. Its suitability for use in cosmetic products is known for example from the German patent application DE-A-41 16 123. Preparations containing 2-hydroxy-5-methyllaurophenone oxime are accordingly suitable for the treatment of skin diseases which are associated with inflammation. It is known that such preparations, for example, for the treatment of psoriasis, different eczema forms, irritative and toxic dermatitis, UV dermatitis and other allergic and / or inflammatory diseases of the skin and the Hautanhangsgebil can be used. Compositions according to the invention which additionally contain an aryloxime, preferably 2-hydroxy-5-methyllaurophenone oxime, show surprising antiinflammatory suitability. The preparations preferably contain from 0.01 to 10% by weight of the aryloxime, and it is particularly preferred if the preparation contains from 0.05 to 5% by weight of aryloxime.

In another also preferred embodiment of the present invention Invention contains the preparation according to the invention at least one self-tanner.

As advantageous self-tanner may be used, inter alia:

5-Hydroxy-1,4-naphtochinon (Juglon) sowie das in den Henna-Blättern vorkommende 2-Hydroxy-1,4-naphtochinon (Lawson).Further, 5-hydroxy-1,4-naphthoquinone (juglone), which is extracted from the shells of fresh walnuts

5-hydroxy-1,4-naphthoquinone (juglone) and the 2-hydroxy-1,4-naphthoquinone (Lawson) found in henna leaves.

2-Hydroxy-1,4-naphtochinon (Lawson)

2-Hydroxy-1,4-naphthoquinone (Lawson)

All particularly preferred is 1,3-dihydroxyacetone (DHA), one in the human body occurring trivalent sugar and its derivatives.

1,3-Dihydroxyaceton (DHA)

1,3-dihydroxyacetone (DHA)

All Compounds or components used in the preparations can be are either known and commercially available acquirable or can be synthesized by known methods.

The cycloaliphatic carboxylic acids, their esters and / or their amides, which act as synergists, as well the repellents and, where appropriate, further active ingredients can be used in the usual Way incorporated into cosmetic or dermatological preparations become. Suitable preparations for external use, for example as a cream, lotion, gel, or as a solution that can be sprayed on the skin. For one internal use are administration formulas such as capsules, dragees, Powder, tablet solutions or solutions suitable.

When Use of the invention to be used Preparations are e.g. called: solutions, suspensions, emulsions, PIT emulsions, pastes, ointments, gels, creams, lotions, powders, soaps, surfactant-containing Cleaning preparations, oils, aerosols and sprays. Other applications are e.g. Sticks, shampoos and shower rooms. The preparation can any usual Carriers, Additives and optionally other active ingredients may be added.

preferable Excipients come from the group of preservatives, antioxidants, Stabilizers, solubilizers, Vitamins, colorants, Odor.

Anoint, Pastes, creams and gels can the usual excipients contained, e.g. animal and vegetable fats, waxes, paraffins, Strength, Tragacanth, cellulose derivatives, polyethylene glycols, silicones, bentonites, silica, Talc and zinc oxide or mixtures of these substances.

powder and sprays can the usual excipients contained, e.g. Lactose, talc, silicic acid, aluminum hydroxide, calcium silicate and polyamide powder or mixtures of these substances. Sprays can also use the usual Propellant, e.g. Chlorofluorocarbons, propane / butane or Dimethyl ether.

Solutions and Emulsions can the usual excipients like solvents, solubilizers and emulsifiers, e.g. Water, ethanol, isopropanol, ethyl carbonate, Ethyl acetate, benzyl alcohol, benzyl benzoate, propylene glycol, 1,3-butyl glycol, oils, in particular cottonseed, Peanut oil, Corn oil, olive oil, castor oil and sesame oil, glycerol fatty acid esters, Polyethylene glycols and fatty acid esters of sorbitan or mixtures of these substances.

suspensions can the usual excipients like liquid Diluents, e.g. Water, ethanol or propylene glycol, suspending agents, e.g. ethoxylated isostearyl alcohols, polyoxyethylene sorbitol esters and polyoxyethylene sorbitan esters, microcrystalline cellulose, aluminum metahydroxide, bentonite, agar-agar and tragacanth or mixtures of these substances.

Soap can the usual excipients like alkali salts of fatty acids, Salts of fatty acid monoesters, fatty acid protein, Isothionates, lanolin, fatty alcohol, vegetable oils, plant extracts, glycerin, sugar or mixtures of these substances.

surfactant Cleaning products can the usual excipients such as salts of fatty alcohol sulfates, fatty alcohol ether sulfates, sulfosuccinic monoesters, fatty acid protein, Isothionates, imidazolinium derivatives, methyltaurates, sarcosinates, Fettsäureamidethersulfate, Alkylamidobetaines, fatty alcohols, fatty acid glycerides, fatty acid diethanolamides, vegetable and synthetic oils, Lanolin derivatives, ethoxylated glycerol fatty acid esters or mixtures thereof Contain substances.

facial and body oils can be the usual excipients like synthetic oils such as fatty acid esters, fatty alcohols, Silicone oils, natural oils such as vegetable oils and oily vegetable extracts, paraffin oils, lanolin oils or Mixtures of these substances included.

Further typical cosmetic applications are also lipsticks, lip balms, Mascara, eye liner, eye shadow, blush, powder, emulsion and wax make up and sunscreen, pre-sun and after-sun preparations.

To the preferred forms of preparation according to the invention belong in particular also emulsions.

Inventive emulsions are advantageous and contain z. As mentioned fats, oils, waxes and other fat bodies, as well as water and an emulsifier, as usually for one such type of preparation is used.

• – Mineralöle, Mineralwachse
• – Öle, wie Triglyceride der Caprin- oder der Caprylsäure, ferner natürliche Öle wie z. B. Rizinusöl;
• – Fette, Wachse und andere natürliche und synthetische Fettkörper, vorzugsweise Ester von Fettsäuren mit Alkoholen niedriger C-Zahl, z.B. mit Isopropanol, Propylenglykol oder Glycerin, oder Ester von Fettalkoholen mit Alkansäuren niedriger C-Zahl oder mit Fettsäuren;
• – Silikonöle wie Dimethylpolysiloxane, Diethylpolysiloxane, Diphenylpolysiloxane sowie Mischformen daraus.

The lipid phase can advantageously be selected from the following substance group:

• - mineral oils, mineral waxes
• - Oils such as triglycerides of capric or caprylic, further natural oils such. Castor oil;
• Fats, waxes and other natural and synthetic fatty substances, preferably esters of fatty acids with lower C-number alcohols, for example with isopropanol, propylene glycol or glycerol, or esters of fatty alcohols with lower C-number alkanoic acids or with fatty acids;
• - Silicone oils such as dimethylpolysiloxanes, diethylpolysiloxanes, diphenylpolysiloxanes and mixed forms thereof.

The oil phase of Emulsions, oleogels or hydrodispersions or lipodispersions in the context of the present invention is advantageously selected the group of esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids of a chain length of 3 to 30 carbon atoms and saturated and / or unsaturated, branched and / or unbranched alcohols of a chain length of 3 to 30 carbon atoms, from the group of esters of aromatic carboxylic acid and saturated and / or unsaturated, branched and / or unbranched alcohols of a chain length of 3 to 30 carbon atoms. Such ester oils can then chosen advantageous are from the group isopropyl myristate, isopropyl palmitate, isopropyl stearate, Isopropyl oleate, n-butyl stearate, n-hexyl laurate, n-decyl oleate, isooctyl stearate, Isononyl stearate, isononyl isononanoate, 2-ethylhexyl palmitate, 2-ethylhexyl laurate, 2-hexadecyl stearate, 2-octyl dodecyl palmitate, oleyl oleate, oleyl erucate, Erucyl oleate, erucyl erucate and synthetic, semisynthetic and natural Mixtures of such esters, e.g. B. jojoba oil.

Further can the oil phase chosen favorably are from the group of branched and unbranched hydrocarbons and waxes, the silicone oils, the dialkyl ether, the group of saturated or unsaturated, branched or unbranched alcohols, as well as the fatty acid triglycerides, namely the triglycerol esters of saturated and / or unsaturated branched and / or unbranched alkanecarboxylic acids of a chain length of 8 to 24, in particular 12-18 C atoms. The fatty acid triglycerides may be, for example chosen favorably are selected from the group of synthetic, semi-synthetic and natural oils, e.g. B. Olive oil, sunflower oil, soybean oil, peanut oil, rapeseed oil, almond oil, palm oil, coconut oil, palm kernel oil, and the like more.

Also any mixtures of such oil and wax components are advantageous in the sense of the present Use invention. It may also be advantageous if Waxes, for example cetyl palmitate, as the sole lipid component the oil phase use.

The aqueous Phase of the invention to be used Preparations contains optionally advantageous alcohols, diols or polyols lower C number, and their ethers, preferably ethanol, isopropanol, propylene glycol, Glycerol, ethylene glycol, ethylene glycol monoethyl or monobutyl ether, Propylene glycol monomethyl, monoethyl or monobutyl ether, diethylene glycol monomethyl or monoethyl ether and analogous products, furthermore lower alcohols C number, z. As ethanol, isopropanol, 1,2-propanediol, glycerol and in particular one or more thickening agents, which or which chosen favorably can be from the group silicon dioxide, aluminum silicates, polysaccharides or their derivatives, e.g. Hyaluronic acid, xanthan gum, hydroxypropyl methylcellulose, particularly advantageous from the group of polyacrylates, preferably a polyacrylate from the group of the so-called Carbopols, for example Carbopols types 980, 981, 1382, 2984, 5984, each individually or in combination.

In particular, mixtures of the abovementioned solvents are used. For alcoholic Solvents can be another component of water.

Inventive emulsions are advantageous and contain z. As mentioned fats, oils, waxes and other fat bodies, as well as water and an emulsifier, as usually for one such type of formulation is used.

In a preferred embodiment contain the invention to be used Preparations hydrophilic surfactants.

The hydrophilic surfactants are preferably selected from the group of alkylglucosides, acyl lactylates, betaines and cocoamphoacetates.

auszeichnen, wobei R einen verzweigten oder unverzweigten Alkylrest mit 4 bis 24 Kohlenstoffatomen darstellt und wobei DP einen mittleren Glucosylierungsgrad von bis zu 2 bedeutet.The alkylglucosides in turn are advantageously selected from the group of alkylglucosides, which are represented by the structural formula

wherein R is a branched or unbranched alkyl radical having 4 to 24 carbon atoms and wherein DP means a mean degree of glucosylation of up to 2.

The value DP represents the degree of glucosidation of the alkylglucosides used in the invention and is defined as

In this case, p ₁ , p ₂ , p ₃ ... Or p _{i represent} the proportion of the products which are mono-, di-trisubstituted ... times glucosylated in percent by weight. Products having degrees of glucosylation of 1-2, in particular advantageously of, are advantageous according to the invention 1.1 to 1.5, most preferably selected from 1.2 to 1.4, in particular from 1.3.

Of the Value DP carries account for the fact that alkylglucosides are manufactured in usually represent mixtures of mono- and oligoglucosides. According to the invention advantageous is a relatively high content of monoglucosides, typically in of the order of magnitude from 40 to 70% by weight.

Particularly according to the invention Advantageously used alkylglucosides are selected from the group octylglucopyranoside, Nonyl glucopyranoside, decyl glucopyranoside, undecyl glucopyranoside, Dodecylglucopyranoside, tetradecylglucopyranoside and hexadecylglucopyranoside.

It is likewise advantageous to employ natural or synthetic raw materials and assistants or mixtures which are distinguished by an effective content of the active ingredients used according to the invention, for example Plantaren ^® 1200 (Henkel KGaA), Oramix NS ^® 10 (Seppic).

auszeichnen, wobei R¹ einen verzweigten oder unverzweigten Alkylrest mit 1 bis 30 Kohlenstoffatomen bedeutet und M⁺ aus der Gruppe der Alkaliionen sowie der Gruppe der mit einer oder mehreren Alkyl- und/oder mit einer oder mehreren Hydroxyalkylresten substituierten Ammoniumionen gewählt wird bzw. dem halben Äquivalent eines Erdalkalions entspricht.In turn, the acyl lactylates are advantageously selected from the group of substances which are defined by the structural formula

in which R ^{1 is} a branched or unbranched alkyl radical having 1 to 30 carbon atoms and M ^{+ is selected} from the group of the alkali metal ions and the group of ammonium ions substituted by one or more alkyl and / or by one or more hydroxyalkyl radicals or half Equivalent to an alkaline earth metal equivalent.

For example, sodium is advantageous, for example the product Pathionic ^® ISL from the American Ingredients Company.

auszeichnen, wobei R² einen verzweigten oder unverzeigten Alkylrest mit 1 bis 30 Kohlenstoffatomen bedeutet.The betaines are advantageously selected from the group of substances which are defined by the structural formula

characterized in that R ^{2 is} a branched or unbranched alkyl radical having 1 to 30 carbon atoms.

Particularly advantageously, R ^{2 is} a branched or unbranched alkyl radical having 6 to 12 carbon atoms.

Capramidopropylbetaine, for example the product Tego ^® Betaine is advantageous, for example 810 from Th. Goldschmidt AG.

For example, sodium elected cocoamphoacetate invention beneficial as under the name Miranol ^® Ultra C32 from Miranol Chemical Corp. is available.

The used according to the invention Preparations are advantageously characterized in that the or the hydrophilic surfactants in concentrations of 0.01-20% by weight preferably 0.05-10% by weight, particularly preferably 0.1-5% by weight, in each case based on the total weight of the composition, is present or present.

to Application are the cosmetic and dermatological according to the invention Preparations in the for Cosmetics usual Applied to the skin and / or hair in sufficient quantity.

Cosmetic according to the invention and dermatological preparations can come in different forms available. So can they z. A solution, an anhydrous preparation, emulsion or microemulsion from Type water-in-oil (W / O) or of the oil-in-water type (O / W), a multiple emulsion, for example of the water-in-oil-in-water type (W / O / W), a gel, a solid stick, an ointment or even an aerosol represent. It is also beneficial to Ectoine in encapsulated form to give, for. In collagen matrices and other common ones Encapsulating materials, e.g. B. as Celluloseverkapselungen, in Gelatin, wax matrices or liposomally encapsulated. Especially Wax matrices as described in DE-A-43 08 282, have been considered favorable exposed. Preference is given to emulsions. Become O / W emulsifiers particularly preferred. Emulsions, W / O emulsions and O / W emulsions are in usual Way available.

As emulsifiers, for example, the known W / O and O / W emulsifiers can be used the. It is advantageous to use further customary co-emulsifiers in the preferred O / W emulsions according to the invention.

According to the invention advantageous For example, O / W emulsifiers are selected as coemulsifiers, mainly from the group the substances with HLB values from 11-16, most advantageously with HLB values of 14.5-15.5, provided that the O / W emulsifiers saturated Radicals R and R 'have. Do the O / W emulsifiers have unsaturated Radicals R and / or R ', or are Isoalkylderivate, so the preferred HLB value such emulsifiers are also lower or higher.

It is advantageous, the fatty alcohol ethoxylates from the group of ethoxylated Stearyl alcohol, cetyl alcohols, cetylstearyl alcohols (cetearyl alcohols) to choose. Particularly preferred are: polyethylene glycol (13) stearyl ether (steareth-13), Polyethylene glycol (14) stearyl ether (steareth-14), polyethylene glycol (15) stearyl ether (Steareth-15), polyethylene glycol (16) stearyl ether (steareth-16), Polyethylene glycol (17) stearyl ether (steareth-17), polyethylene glycol (18) stearyl ether (Steareth-18), polyethylene glycol (19) stearyl ether (Steareth-19), polyethylene glycol (20) stearyl ether (steareth-20), polyethylene glycol (12) isostearyl ether (Isosteareth-12), polyethylene glycol (13) isostearyl ether (isosteareth-13), Polyethylene glycol (14) -isostearylether (Isosteareth-14), polyethylene glycol (15) isostearyl ether (isosteareth-15), polyethylene glycol (16) isostearyl ether (Isosteareth-16), polyethylene glycol (17) isostearyl ether (isosteareth-17), polyethylene glycol (18) isostearyl ether (Isosteareth-18), Polyethylene glycol (19) isostearyl ether (isosteareth-19), polyethylene glycol (20) isostearyl ether (isosteareth-20), Polyethylene glycol (13) cetyl ether (ceteth-13), polyethylene glycol (14) cetyl ether (Ceteth-14), polyethylene glycol (15) cetyl ether (Ceteth-15), polyethylene glycol (16) cetyl ether (Ceteth-16), polyethylene glycol (17) cetyl ether (ceteth-17), polyethylene glycol (18) cetyl ether (Ceteth-18), polyethylene glycol (19) cetyl ether (Ceteth-19), polyethylene glycol (20) cetyl ether (Ceteth-20), polyethylene glycol (13) isocetyl ether (isoceteth-13), Polyethylene glycol (14) -isocetylether (Isoceteth-14), polyethylene glycol (15) isocetyl ether (isoceteth-15), Polyethylene glycol (16) isocetyl ether (isoceteth-16), polyethylene glycol (17) isocetyl ether (isoceteth-17), Polyethylene glycol (18) isocetyl ether (isoceteth-18), polyethylene glycol (19) isocetyl ether (Isoceteth-19), polyethylene glycol (20) isocetyl ether (Isoceteth-20), polyethylene glycol (12) oleyl ether (Oleth-12), polyethylene glycol (13) oleyl ether (Oleth-13), polyethylene glycol (14) oleyl ether (Oleth-14), polyethylene glycol (15) oleyl ether (Oleth-15), polyethylene glycol (12) lauryl ether (Laureth-12), polyethylene glycol (12) isolauryl ether (Isolaureth-12), polyethylene glycol (13) cetyl stearyl ether (ceteareth-13), Polyethylene glycol (14) cetyl stearyl ether (ceteareth-14), polyethylene glycol (15) cetyl stearyl ether (Ceteareth-15), polyethylene glycol (16) cetyl stearyl ether (ceteareth-16), Polyethylene glycol (17) cetyl stearyl ether (ceteareth-17), polyethylene glycol (18) cetyl stearyl ether (Ceteareth-18), polyethylene glycol (19) cetyl stearyl ether (Ceteareth-19), Polyethylene glycol (20) cetylstearyl ether (Ceteareth-20).

It is also advantageous, the fatty acid ethoxylates following Group to choose: Polyethylene glycol (20) stearate, polyethylene glycol (21) stearate, polyethylene glycol (22) stearate, Polyethylene glycol (23) stearate, polyethylene glycol (24) stearate, polyethylene glycol (25) stearate, Polyethylene glycol (12) isostearate, polyethylene glycol (13) isostearate, Polyethylene glycol (14) isostearate, polyethylene glycol (15) isostearate, Polyethylene glycol (16) isostearate, polyethylene glycol (17) isostearate, Polyethylene glycol (18) isostearate, polyethylene glycol (19) isostearate, Polyethylene glycol (20) isostearate, polyethylene glycol (21) isostearate, Polyethylene glycol (22) isostearate, polyethylene glycol (23) isostearate, Polyethylene glycol (24) isostearate, polyethylene glycol (25) isostearate, Polyethylene glycol (12) oleate, polyethylene glycol (13) oleate, polyethylene glycol (14) oleate, Polyethylene glycol (15) oleate, polyethylene glycol (16) oleate, polyethylene glycol (17) oleate, Polyethylene glycol (18) oleate, polyethylene glycol (19) oleate, polyethylene glycol (20) oleate.

When ethoxylated alkyl ether carboxylic acid or its salt may advantageously be the sodium laureth-11-carboxylate be used. As alkyl ether sulfate sodium Laureth1-4sulfat be used advantageously. As an ethoxylated cholesterol derivative Advantageously, polyethylene glycol (30) cholesteryl ether may be used become. Also polyethylene glycol (25) soybean oil has been proven. When ethoxylated triglycerides can Advantageously, the polyethylene glycol (60) Evening Primrose Glycerides be used (Evening Primrose = evening primrose).

Farther is advantageous, the Polyethylenglycolglycerinfettsäureester from the group polyethylene glycol (20) glyceryl laurate, polyethylene glycol (21) glyceryl laurate, Polyethylene glycol (22) glyceryl laurate, polyethylene glycol (23) glyceryl laurate, Polyethylene glycol (6) glycerylaprate / cprinate, polyethylene glycol (20) glyceryl oleate, polyethylene glycol (20) glyceryl isostearate, Polyethylene glycol (18) glyceryl oleate (cocoate) to choose.

It is also cheap the sorbitan esters from the group polyethylene glycol (20) sorbitan monolaurate, polyethylene glycol (20) sorbitan monostearate, Polyethylene glycol (20) sorbitan monoisostearate, polyethylene glycol (20) sorbitan monopalmitate, Polyethylene glycol (20) to choose sorbitan monooleate.

As optional, but according to the invention optionally advantageous W / O emulsifiers can be used:
Fatty alcohols having 8 to 30 carbon atoms, monoglycerol esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids having a chain length of 8 to 24, in particular 12-18 C atoms, diglycerol esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids of one chain length from 8 to 24, in particular 12-18 C-atoms, monoglycerol ethers of saturated and / or unsaturated, branched and / or unbranched alcohols of a chain length of 8 to 24, in particular 12-18 C-atoms, diglycerol ether of saturated and / or unsaturated, branched and or unbranched alcohols of a chain length of 8 to 24, in particular 12-18 C-atoms, propylene glycol esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids of a chain length of 8 to 24, in particular 12-18 C-atoms and sorbitan esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids of a K ettenlänge of 8 to 24, in particular 12-18 C-atoms.

Especially advantageous W / O emulsifiers are glyceryl monostearate, glyceryl monoisostearate, Glyceryl monomyristate, glyceryl monooleate, diglyceryl monostearate, Diglyceryl monoisostearate, propylene glycol monostearate, propylene glycol monoisostearate, Propylene glycol monocaprylate, propylene glycol monolaurate, sorbitan monoisostearate, Sorbitan monolaurate, sorbitan monocaprylate, sorbitan monoisooleate, Sucrose distearate, cetyl alcohol, stearyl alcohol, arachidyl alcohol, Behenyl alcohol, isobehenyl alcohol, selachyl alcohol, chimyl alcohol, Polyethylene glycol (2) stearyl ether (steareth-2), glyceryl monolaurate, Glyceryl monocaprinate, glyceryl monocaprylate.

According to the invention preferred Preparations are particularly suitable for protecting human skin Aging processes as well as oxidative stress, i. against damage by radicals, as e.g. by sunlight, heat or other influences be generated. She lies in different, for this Application usually used dosage forms. So she can especially as Lotion or emulsion, such as cream or milk (O / W, W / O, O / W / O, W / O / W), in the form of oily-alcoholic, oily-aqueous or aqueous-alcoholic Gels or solutions, be present as solid pins or formulated as an aerosol.

The Preparation may contain cosmetic adjuvants present in this Type of preparations usually can be used, e.g. Thickening agents, softening agents, Humectant, surface-active Agents, emulsifiers, preservatives, antifoaming agents, Perfumes, waxes, lanolin, propellants, dyes and / or pigments, which dye the agent itself or the skin, and others in cosmetics usually used ingredients.

you can as dispersing or solubilizing an oil, wax or other fats, a low monoalcohol or a lower polyol or mixtures use of it. To the particularly preferred monoalcohols or Count polyols Ethanol, i-propanol, propylene glycol, glycerol and sorbitol.

A preferred embodiment The invention is an emulsion which is used as a protective cream or milk is present and, for example, fatty alcohols, fatty acids, fatty acid esters, in particular triglycerides of fatty acids, Lanolin, natural and synthetic oils or waxes and emulsifiers in the presence of water.

Further preferred embodiments make oily Lotions based on natural or synthetic oils and waxes, lanolin, fatty acid esters, in particular triglycerides of fatty acids, or oily-alcoholic lotions Base of a lower alcohol, such as ethanol, or a glycerol, such as propylene glycol, and / or a polyol, such as glycerol, and oils, waxes and fatty acid esters, like triglycerides of fatty acids, represents.

The inventive preparation may also be present as an alcoholic gel containing one or more Lower alcohols or polyols, such as ethanol, propylene glycol or Glycerol, and a thickener such as silica. The oily-alcoholic Gels contain as well natural or synthetic oil or Wax.

The solid pens are made of natural or synthetic waxes and oils, Fatty alcohols, fatty acids, Fettsäureestern, Lanolin and other fatty substances.

is a preparation prepared as an aerosol, is used in the Usually the usual Propellants, such as alkanes, fluoroalkanes and chlorofluoroalkanes, are preferred Alkanes.

The Cosmetic preparation can also protect the hair against photochemical damage used to change of shades, a discoloration or damage mechanical nature. In this case, it is suitable a formulation as a shampoo, lotion, gel or emulsion for rinsing, wherein the respective preparation before or after shampooing, before or after dyeing or decolorizing or before or after the permanent wave is applied. It can also a preparation as a lotion or gel for styling and treating, as a lotion or gel for brushing or laying a water wave, as a hair coat, permanent wave, dyeing or bleach for the hair chosen become. The preparation with photoprotective properties can be different, containing adjuvants used in this type of medium, such as active surface Agents, thickeners, polymers, emollients, preservatives, Foam stabilizers, electrolytes, organic solvents, silicone derivatives, oils, waxes, Antifettmittel, dyes and / or pigments containing the agent itself or dye your hair or others for Hair care usually used ingredients.

The used according to the invention Preparations can In doing so, they are manufactured using techniques that are familiar to those skilled in the art well known.

Also without further explanations It is assumed that a professional has the above description to the fullest extent. The preferred embodiments are therefore only descriptive, not in any way Way limiting disclosure to understand. The complete revelation all applications and publications listed above and below are incorporated by reference into this application.

The in the following examples for the subject invention are for explanation only and by no means limit the present invention in any way one. Furthermore is the described invention throughout the claimed range executable. All compounds or components used in the preparations can be are either known and commercially available available or can be synthesized by known methods. It will be the INCI names of the raw materials used (the INCI names are defined in English Language specified).

Preparation of lotions 1 to 8:

First, be the phases A and B heated separately to 75 ° C. Thereafter, Phase B is under Stir slowly added to phase A and stirred until a homogeneous mixture arises. After homogenization of the emulsion at 40 ° C, the ingredients Phase C added. Subsequently the formulation is stirred until it cools to room temperature.

Formulation 1 (comparative formulation)

The following components are used to make a lotion:

Of the pH of the produced lotion is 6.70 at 23 ° C.

Formulation 2

The following components are used to make a lotion:

Of the pH of the produced lotion is 6.60 at 23 ° C.

Formulation 3

The following components are used to make a lotion:

Of the pH of the produced lotion is 6.60 at 23 ° C.

Formulation 4

The following components are used to make a lotion:

Of the pH of the produced lotion is 6.60 at 23 ° C.

Formulation 5

The following components are used to make a lotion:

Of the pH of the produced lotion is 7.20 at 23 ° C.

Formulation 6

The following components are used to make a lotion:

Of the pH of the produced lotion is 6.70 at 23 ° C.

Formulation 7

The following components are used to make a lotion:

Of the pH of the produced lotion is 6.80 at 23 ° C.

Formulation 8

The following components are used to make a lotion:

Of the pH of the produced lotion is 6.60 at 23 ° C.

1

Merck KGaA / Rona

2

Noveon

3

Uniqema

4

Rhodia GmbH

5

Cognis GmbH

6

Degussa-Goldschmidt AG

7

Dow Corning

8th

ISP

9

Sigma Aldrich

Application / potency test:

The Repellent - effectiveness is judged by the O / W lotions 1 to 8. The experiments will be on hairless mice carried out, by counting the stitches of females of the species Aedes aegypti. The efficacy period will be reviewed over 8 hours.

When Mosquitoes become 4 to 6 day old female Aedes aegypti from one Laboratory colony used, bred since 1992 (origin of the species: ORSTOM / WHO - Type: Bora-Bora). The females will be facing the 24 hours prior to the test starved on blood.

The targets to be protected from the stings are hairless mice that are in a mesh cylinder and have eye protection. The lotion is applied in an amount of 0.5 g to the respective mouse. Then the mouse is placed in a glass cage (50 cm x 50 cm x 50 cm) containing about 50 female mosquitoes. The test lasts 10 minutes, recording the number of stitches and the number of landings (cumulative data). The test is stopped each time more than 5 bites occur. The same procedure is done every 2 hours (or every hour depending on the previous assessment) performed with a new set of insects. In the event that the formulation product is still effective, the test takes 8 hours.

Of the same experiment is performed with an untreated mouse the aggressiveness to check the mosquitoes for their lancing behavior.

Tabelle 1 (Fortsetzung)

• F = Formulierung
• U = unbehandelte Kontrolle
• S = Anzahl der Stiche
• L = Anzahl der Landungen
• Wdg. = Wiederholung
• stop = der Versuch wird abgebrochen, wenn mehr als 5 Stiche auftreten

3 repetitions are performed on 3 mice each, ie 9 individual tests are performed per formulation product. Table 1 shows the results of all tests. Table 1 Number of stitches and landings

Table 1 (continued)

• F = formulation
• U = untreated control
• S = number of stitches
• L = number of landings
• Wdg. = Repetition
• stop = the attempt is aborted if more than 5 stitches occur

Duration of the repellent effect of formulations 1 to 8 compared to Aedes agypti (hairless mice) formulation Duration of action [h] 1 5 2 6 3 6 4 6 5 6 6 5 7 6 8th 5 untreated 0

Claims (23)

Use of at least one cycloaliphatic Connection selected from the group cycloaliphatic carboxylic acid, esters of a cycloaliphatic Carboxylic acid, Amide of a cycloaliphatic carboxylic acid, cycloaliphatic alcohol and cycloaliphatic ketone, as a synergist for enhancing the Effect of repellents in cosmetic and dermatological formulations for the defense and / or deterrence of arthropods. Use according to Claim 1, characterized in that the cycloaliphatic carboxylic acid or the cycloaliphatic alcohol is a compound of the formula (I) and / or of the formula (II)

where n = 0 to 12, preferably 0 to 6, where X = COOH or OH, where the cycloaliphatic ring and / or the aliphatic side chain with - straight or branched C ₁ - to C ₁₂ -alkyl groups, preferably C ₁ - to C _4- alkyl groups, - straight-chain or branched C ₁ - to C ₁₂ -alkenyl groups and / or - straight-chain or branched C ₁ - to C ₁₂ -hydroxyalkyl groups, where the hydroxy groups may be bonded to a primary or secondary carbon atom of the chain, may be substituted and wherein the cycloaliphatic ring may be mono- or diunsaturated and / or may have an exocyclic double bond. Use according to Claim 2, characterized in that the ester of a cycloaliphatic carboxylic acid is a compound in which the hydroxy group of the carboxylic acid of the formula (I) or (II) is a straight-chain or branched C ₁ -C ₁₂ -alkoxy group , preferably C ₁ - to C ₄ alkoxy group, is replaced. Use according to claim 2, characterized in that the amide of a cycloaliphatic carboxylic acid is a compound in which the hydroxy group of the carboxylic acid of the formula (I) or (II) is replaced by an amide group -NR ¹ R ² , where R ¹ and R ^{2 may be the} same or different and are selected from straight-chain or branched C ₁ - to C ₁₂ -alkyl groups, preferably C ₁ - to C ₄ -alkyl groups. Use according to claim 2, characterized in that the cycloaliphatic carboxylic acid is selected from cyclohexylcarboxylic acid, cyclohexylacetic acid, cyclohexylpropionic acid, cyclohexylbutanoic acid, cyclohexylpentanoic acid, cyclohexylhexanoic acid, cyclopentylcarboxylic acid, cyclopentylacetic acid, cyclopentylpropionic acid, cyclopentylbutanoic acid, cyclopentylpentanoic acid, cyclopentylhexanoic acid. Use according to claim 3, characterized that the ester of the cycloaliphatic carboxylic acid is selected from methyl, ethyl, Propyl and butyl esters. Use according to claim 2, characterized that the cycloaliphatic alcohol is a compound in which the side chain contains a carbon atom. Use according to at least one of the preceding Claims, characterized in that the cosmetic or dermatological Formulation of at least one cycloaliphatic carboxylic acid, their Esters and / or their amide in a total amount of from 0.01 to 10% by weight, preferably in an amount of 0.1 to 2 wt .-%, contains. Use according to at least one of the preceding Claims, characterized in that the cosmetic or dermatological Formulation contains at least one repellent. Use according to claim 9, characterized that the repellent is selected is from N, N-diethyl-3-methylbenzamide, 3- (acetyl-butyl-amino) -propionic acid ethyl ester, Dimethyl phthalate, butopyronoxyl, 2,3,4,5-bis (2-butylene) -tetrahydro-2-furaldehyde, N, N-caprylic acid diethylamide, N, N-diethylbenzamide, o-chloro-N, N-diethylbenzamide, Dimethyl carbate, di-n-propyl isocin chomeronate, 2-ethylhexane-1,3-diol, N-octylbicyclohepetane dicarboximide, piperonyl butoxide, 1- (2-methylpropyloxycarbonyl) -2- (hydroxyethyl) piperidine or Mixtures thereof, wherein at least one repellent is particularly preferred selected is from N, N-diethyl-3-methylbenzamide, ethyl 3- (acetyl-butyl-amino) -propionate, 1- (2-methylpropyloxycarbonyl) -2- (hydroxyethyl) piperidine or mixtures from that. Use according to at least one of the preceding Claims, characterized in that the cosmetic or dermatological Formulation contains at least one substance, the UV radiation in the UV-A and / or UV-B range absorbed. Use according to at least one of the preceding Claims, characterized in that the cosmetic or dermatological Formulation inorganic pigments containing as UV filter substances serve. Preparation containing at least one cycloaliphatic Connection selected from the group cycloaliphatic carboxylic acid, esters of a cycloaliphatic Carboxylic acid, Amide of a cycloaliphatic carboxylic acid, cycloaliphatic alcohol and cycloaliphatic ketone, and at least one active substance, their effect by the presence of the cycloaliphatic compound synergetically reinforced becomes. A preparation according to claim 13, characterized in that the cycloaliphatic carboxylic acid or the cycloaliphatic alcohol is a compound of the formula (I) and / or of the formula (II)

where n = 0 to 12, preferably 0 to 6, where X = COOH or OH, where the cycloaliphatic ring and / or the aliphatic side chain with - straight or branched C ₁ - to C ₁₂ alkyl groups, preferably C ₁ - to C _4- alkyl groups, - straight-chain or branched C ₁ - to C ₁₂ -alkenyl groups and / or - straight-chain or branched C ₁ - to C ₁₂ -hydroxyalkyl groups, where the hydroxy groups may be bonded to a primary or secondary carbon atom of the chain, may be substituted and wherein the cycloaliphatic ring may be mono- or diunsaturated and / or may have an exocyclic double bond. Preparation according to claim 14, characterized in that the cycloaliphatic carboxylic acid is selected from cyclohexylcarboxylic acid, cyclohexylacetic acid, cyclohexylpropionic acid, cyclohexylbutanoic acid, cyclohexylpentanoic acid, cyclohexylhexanoic acid, cyclopentylcarboxylic acid, cyclopentylacetic acid, cyclopentylpropionic acid, cyclopentylbutanoic acid, cyclopentylpentanoic acid, cyclopentylhexanoic acid. Preparation of at least one of claims 13 to 15, characterized in that it is at least one Active substance is at least one repellent. Preparation according to Claim 16, characterized that the repellent is selected is from N, N-diethyl-3-methylbenzamide, 3- (acetyl-butylamino) -propionic acid ethyl ester, Dimethyl phthalate, butopyronoxyl, 2,3,4,5-bis (2-butylene) -tetrahydro-2-furaldehyde, N, N-Caprylsäurediethylamid, N, N-diethylbenzamide, o-chloro-N, N-dimethylbenzamide, Dimethyl carbate, di-n-propyl isocin chomeronate, 2-ethylhexane-1,3-diol, N-octylbicyclohepetane dicarboximide, piperonyl butoxide, 1- (2-methylpropyloxycarbonyl) -2- (hydroxyethyl) piperidine or Mixtures thereof, wherein at least one repellent is particularly preferred selected is from N, N-diethyl-3-methylbenzamide, ethyl 3- (acetyl-butyl-amino) -propionate 1- (2-methylpropyloxycarbonyl) -2- (hydroxyethyl) piperidine or mixtures from that. A preparation according to at least one of claims 13 to 17, characterized in that the preparation one or more cycloaliphatic carboxylic acids, their esters and / or their amides in a total amount of 0.01 to 10 wt .-%, preferably in an amount of 0.1 to 2 wt .-%, contains. A preparation according to at least one of claims 13 to 18, characterized in that it comprises further active substances selected from UV filters, flavone derivatives, Chromone derivatives, aryloximes and parabens contains. A preparation according to at least one of claims 13 to 19 for the protection of body cells against oxidative stress, in particular to reduce skin aging, characterized in that it contains one or more further antioxidants and / or vitamins, preferably selected from vitamin A palmitate, Vitamin C and its derivatives, DL-α-tocopherol, tocopherol-E-acetate, nicotinic acid, pantothenic acid and biotin. A preparation according to at least one of claims 13 to 20, wherein the preparation in addition to the at least one cycloaliphatic Carboxylic acid, their ester or their amide and at least one active substance contains one or more UV filters, which are preferably selected from 3- (4'-methylbenzylidene) dl camphor, 1- (4-tert-butylphenyl) -3- (4-methoxyphenyl) propane-1,3-dione, 4-isopropyldibenzoylmethane, 2-hydroxy-4-methoxybenzophenone, methoxycinnamate, 3,3,5-trimethylcyclohexylsalicylate, 4- (dimethylamino) benzoic acid 2-ethylhexylester, 2-cyano-3,3-diphenylacrylate, 2-ethylhexyl, 2-phenylbenzimidazole-5-sulfonic acid and potassium, sodium and triethanolamine salts. Process for the preparation of a preparation according to Claims 13 to 21, characterized in that at least one cycloaliphatic carboxylic acid, their ester and / or their amide and at least one active substance mixed with a cosmetically or dermatologically suitable carrier become. Use of a preparation according to claim 13 to 21 for topical application or for use on a surface.