EP3389619A1 - Preparations comprising carnosines - Google Patents

Abstract

The invention relates to a preparation containing at least one compound of formula (I), providing that R1 is H or CH₃ and R2 is H or COOH, or salts thereof, to be used as a drug for preventing and/or treating signs of degeneration and ageing of the skin which are not, or not exclusively, caused by the effect of light.

Description

 PREPARATIONS WITH CARNOSINES

FIELD OF THE INVENTION

 [0001] The invention is in the field of cosmetics or pharmacy and relates to the use of preparations containing carnosine and carnosine derivatives.

STATE OF THE ART

 In the field of cosmetic products, the segment "anti-aging" is certainly the most important, since the trend is still unbroken, especially for consumers to look as young as possible for as long as possible.The cosmetics industry is waiting to satisfy this also economically immensely interesting need with ever new Active ingredients and drug mixtures, some with the promise of sensational results within a short period of time, yet without making it regularly experienced by the consumer.

The serious research knows, however, that hide behind the findings of a slack, rough, damaged and often simply aged skin a variety of causes that - at least so far - can not be alleviated by the use of a single drug at least. Not even active-substance cocktails that tackle the various causes are helpful here, since the substances often interfere with one another in their mechanisms of action.

 There is therefore still the need to find the cosmetic "philosopher's stone", which can uniformly counteract all the above-mentioned complaints - from the damage caused by UV rays to the relaxation of the connective tissue the experts are very doubtful that this will be the case in the near future, even though the daily increase in understanding of the processes that take place in the skin is growing, in this context one would be very pleased to be able to identify a single substance, which addresses at least some skin aging phenomena, even if the severity of the effects is not consistently at the same high level.

[0005] Numerous substances are known from the state of the art to which an effect with regard to the damage to the skin is attributed. Carnosine and its compounds, which are actually typical dietary supplements, have been less widely used for this purpose. With regard to cosmetic applications in general and skin damage in particular, carnosine has so far been associated only with protection against UV rays. From a study by Aruoma et al. For example, it is known from 1989 that carnosine is capable of trapping reactive oxygen species (ROS) [Biochem J. 264 (3), pp. 863-869 (1989)]. Carnosine, according to a report by Babizhayev et al., moreover, intercept alpha-beta-unsaturated aldehydes released in the peroxidation of fatty acids of the cell membrane under oxidative stress [Membran & Cell Biol. 12 (1), pp. 89-99 (1998)].

 Ultimately, however, the properties of carnosine in the field of skin care products based on its property as antioxidants. Reference should also be made in particular to publication WO 2014 128228 A2 (SYM RISE), which shows the suitability of these substances for protection against IR radiation on the basis of the inhibition of M M P expression.

 In addition, from EP 1591105 AI (STADA) cosmetic and pharmaceutical preparations are known which contain an antioxidant that protect the skin from IR radiation. Among the many possible antioxidants, carnosine and arsenic are also mentioned. Furthermore, the topically applied compositions comprise one or more inorganic and / or organic UV filters.

 EP 2545898 A1 (COTY) discloses preparations which protect the skin from damage by I R rays and thereby contain plant extracts, vitamins, ruby powder, mica and titanium dioxide. In section [0026], carnosine is also mentioned as a further suitable excipient, but as radical scavenger.

The subject of EP 2181697 A2 (SHISEIDO) are sunscreen in O / W form, which are characterized by a special cocktail of emulsifiers and sunscreen filters. Table 3-3 discloses two compositions (Examples 22 and 23) containing the combination of carnosine with UV filters.

 WO 2010 124817 A2 (KPSS) relates to conditioning agents based on, inter alia, dipeptides such as carnosine for hair. In the embodiments, there is a disclosure for the combination of carnosine with a UV filter, namely benzophenone-3.

 EP 1310238 A2 (BASF) discloses cosmetic or dermatological light stabilizer formulations which comprise at least one cholesteric liquid-crystalline component reflecting in the infrared wavelength range from 750 nm to 2500 nm, at least one filter substance protecting against radiation in the ultraviolet radiation range from 280 nm to 449 nm, and contain at least one cosmetically acceptable carrier and their use. In addition, antioxidants, e.g. Carnosine be present.

The object of the present invention was therefore to find a substance or a substance class which is particularly suitable for the prevention and treatment of degeneration phenomena, in particular aging phenomena of the skin, which are not or at least not exclusively due to the action of UV or IR radiation. Radiation can be caused. There is a particular interest in substances that stimulate the cellular repair functions and counteract damage to the skin caused by air pollution and aging. DESCRIPTION OF THE INVENTION

 A first subject of the invention relates to a preparation containing at least

Compound of the formula (I)

with the proviso that R 1 is H or CH ₃ and R 2 is H or COOH or salts thereof for use as a medicament for the prevention and / or treatment of degeneration and aging of the skin, which are not or not exclusively caused by the action of light ,

Another object of the invention relates to a preparation containing

 (a) at least one compound of the formula (I)

with the proviso that Rl is H or _CH3 and R2 is H or COOH, or their salts, and

 (b) at least one UV sun protection factor

for use as a medicament for the prevention and / or treatment of degeneration and aging of the skin, which are not or not exclusively caused by the action of light.

[0014] Surprisingly, it has been found that carnosines, of which hitherto only an anti-oxidative effect with regard to the trapping of oxygen radicals was known, are also capable of other processes which take place on the skin surface or in the subcutaneous layer to influence positively. These include, in particular, the stimulation of the formation of the enzyme G6PDH and, consequently, the increase in the production of intracellular DNA, both important parameters for cell protection and skin renewal. It was particularly surprising that the activity was increased by the addition of UV light protection filters could be increased even though these substances alone show no activity.

 Furthermore, it was found that decrease the use of carnosins apoptosis in human cell cultures and the content of free DNA fragments in the cytoplasm and thus the level of destroyed DNA in the nucleus. Other in vitro findings indicate that carnosins cause regenerating and revitalizing activity in human fibroblasts and inhibit both the release of skin damaging elastase and the collagen glycation. ACTIVE SUBSTANCES

In the active ingredients which make up the formula (I), there are basically known compounds which are accessible by the usual methods of organic chemistry. Preferably, this is a group of substances which is formed by carnosine, L-carnosine, D-carnosine, D / L-carnosine, carnicin, carnicin * HCI, anserine, D-anserine, L-anserine and L-anserine * HN0 ₃ and their mixtures.

 Salts of the compounds of the formula (I) are preferably understood according to the invention as salts of the compounds of the formula (I) with mineral acids, and particular preference is given to salts of the formula (I):

where n is 1,2 or 3 and A is HCl or HNO ₃ and R 1 is H or CH ₃ and R ₂ is H or COOH.

 The revitalizing and reactivating activity of carnosine increases, as mentioned above, in particular the activity of G6PDH production and counteracts apoptosis. The use of the substances as protective and restorative medicaments or care agents is possible in principle for all preparations which are used for the prevention of damage or damage to the skin and thus in skin care and prophylaxis. Another use in this field is the application of sensitive, damaged by allergy or other causes skin. The damage to the skin can have a variety of causes.

UV LIGHT PROTECTORS

Mixtures of compounds of formula (I) or their salts with UV sun protection factors leads to a synergistic enhancement of the revitalization of the skin. The UV sun protection factors may be UV-A filters, UV-B filters, pigments or mixtures thereof, which are further explained below.

UV-A and UV-B light protection filters

 Under UV sun protection factors, for example, at room temperature, liquid or crystalline organic substances (sunscreen) to understand that are able to absorb ultraviolet rays and the absorbed energy in the form of long-wave radiation, e.g. Heat again. Usually, the UV sunscreen factors are present in amounts of 0.1 to 5 and preferably 0.2 to 1 wt .-%. UVB filters can be oil-soluble or water-soluble. As oil-soluble substances are e.g. to call:

 3-benzylidene camphor or 3-benzylidene norcamphor and its derivatives, e.g. 3- (4-methylbenzylidene) camphor described;

 4-aminobenzoic acid derivatives, preferably 2-ethylhexyl 4- (dimethylamino) benzoate, 2-octyl 4- (dimethylamino) benzoate and 4- (dimethylamino) benzoic acid amyl ester;

 Esters of cinnamic acid, preferably 4-methoxycinnamic acid 2-ethylhexyl ester, propyl 4-methoxycinnamate, isoamyl 4-methoxycinnamate 2-ethylhexyl 2-cyano-3,3-phenylcinnamate (octocrylene);

 Esters of salicylic acid, preferably 2-ethylhexyl salicylate, 4-isopropylbenzyl salicylate, homomenthyl salicylate;

 Derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone;

Esters of benzalmalonic acid, preferably di-2-ethylhexyl 4-methoxybenzmalonate;

 Triazine derivatives, e.g. 2,4,6-trianilino (p-carbo-2'-ethyl-1-hexyloxy) -l, 3,5-triazine and octyl triazone or dioctyl butamido triazone (Uvasorb® HEB);

 Propane 1,3-diones, e.g. 1- (4-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione;

 Ketotricyclo (5.2.1.0) decane derivatives.

 Suitable water-soluble substances are:

 2-phenylbenzimidazole-5-sulfonic acid and its alkali metal, alkaline earth metal, ammonium, alkylammonium, alkanolammonium and glucammonium salts;

lH-Benzimidazole-4,6-disulfonic acid, 2,2 '- (l, 4-phenylene) bis-, disodium salt (Neo Heliopan AP ^®)

 Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts;

Sulfonic acid derivatives of 3-Benzylidencamphers, such as 4- (2-oxo-3-bornylidenme- thyl) benzenesulfonic acid and 2-methyl-5- (2-oxo-3-bomylidene) sulfonic acid and salts thereof. As a typical UV-A filter, in particular derivatives of benzoylmethane in question, such as L- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-l, 3-dione, 4-tert .- Butyl 4'-methoxy-dibenzoylmethane (Parsol® 1789), 2- (4-diethylamino-2-hydroxybenzoyl) -benzoic acid hexyl ester (Uvinul® A Plus), 1-phenyl-3- (4'-isopropylphenyl) -propane-1, 3-dione and enamine compounds. Of course, the UV-A and UV-B filters can also be used in mixtures. Particularly favorable combinations consist of the derivatives of benzoylmethane, for example 4-tert-butyl-4'-methoxydibenzoylmethane (Parsol® 1789) and 2-cyano-3,3-phenylcinnamic acid 2-ethylhexyl ester (octocrylene) in combination with ester cinnamic acid, preferably 4-methoxycinnamic acid 2-ethylhexyl ester and / or 4-methoxycinnamic acid propyl ester and / or 4-methoxycinnamic acid isoamyl ester. Such combinations are advantageously combined with water-soluble filters such as, for example, 2-phenylbenzimidazole-5-sulfonic acid and its alkali metal, alkaline earth metal, ammonium, alkylammonium, alkanolammonium and glucammonium salts. [0026] Sunscreen pigments

In addition to the soluble substances mentioned, insoluble photoprotective pigments, namely finely dispersed metal oxides or salts, are also suitable for this purpose. Examples of suitable metal oxides are in particular zinc oxide and titanium dioxide and, in addition, oxides of iron, zirconium, silicon, manganese, aluminum and cerium and mixtures thereof. As salts silicates (talc), barium sulfate or zinc stearate can be used. The oxides and salts are used in the form of the pigments for skin-care and skin-protecting emulsions and decorative cosmetics. The particles should have an average diameter of less than 100 nm, preferably between 5 and 50 nm and in particular between 15 and 30 nm. They can have a spherical shape, but it is also possible to use those particles which have an ellipsoidal or otherwise deviating shape from the spherical shape. The pigments can also be surface-treated, ie hydrophilized or hydrophobized. Typical examples are coated titanium dioxides, for example Titandioxid T 805 (Degussa) or Eusolex ^® T2000, Eusolex ^® T, Eusolex ^® T-ECO, Eusolex ^® TS, Eusolex ^® T-Aqua, Eusolex ^® T-45D (all Merck), Uvinul TiO ₂ (BASF). Suitable hydrophobic coating agents are in particular silicones and in particular trialkoxyoctylsilanes or simethicones. I n sunscreen agents are preferably used so-called micro- or nanopigments. Preferably micronized zinc oxide, such as Z-COTE ^® or Z-COTE HP1 ^® is used. CARRIER

Both the medicaments and the cosmetic preparations described below may contain as component (c) carriers or solvents which are selected from the group formed by water, alcohols, esters, butylene glycol, dipropylene glycol, ethanol, ethoxydiglycol , Ethyl acetate, glycerol, propanol, isopropanol, macrogols, propylpropylene glycol (2) methyl ether, propylpropyl-glycol (3) methyl ether, propylene carbonate, propylene glycol, triethylene glycol, isoparaffin, amyl acetate, amyl benzoate, benzyl acetate, butyl acetate, butylene glycol, butyl lactate, butooctyl benzoate, butooctyl salicylate , C10-C13 alkanes, C14-C17 alkanes, C11-C15 cycloalkanes, caprylyl butyrate, isoparaffins, diacetin, triacetin dicaprylyl ethers, dicaprylyl maleate, and mixtures thereof. MEDICAMENTS

 The medicaments according to the invention contain components (a) and (b) preferably in a weight ratio of from about 1:99 to about 99: 1, in particular from about 5:95 to about 20:80 and most preferably from about 10:90 until about 15:85. The synergy is most pronounced when the two components are used approximately in the weight ratio 1: 5.

 [0032] A preferred medicament has the following composition:

 (a) about 0.001 to about 5% by weight, preferably about 0.01 to about 1% by weight, more preferably about 0.05 to 0.5% by weight and in particular 0.1 to 0, 25% by weight of a compound of the formula (I), preferably carnosine,

 (b) 0 or about 0.05 to about 20% by weight, preferably about 0.1 to about 10% by weight, and more preferably about 1 to about 5% by weight of at least one UV sun protection factor;

(c) ad 100% by weight of carrier.

COSMETIC PREPARATIONS

 Another object of the present invention relates to cosmetic compositions for the treatment of degeneration and especially aging of the skin, which are not or not exclusively based on the influence of light, containing

(a) at least one compound of the formula (I)

with the proviso that Rl is H or _CH3 and R2 is H or COOH, or their salts, and

 (B) at least one UV sun protection factor, preferably at least one UV-A and at least one UV-B sun protection factor, and optionally

 (cl) carrier,

 (c2) oil body and / or

 (c3) emulsifiers

contain.

The preparations according to the invention are preferably in the form of creams, lotions, gels, pastes or capsules and in particular are anti-aging agents. Further preferred is that the component (a) based on the total composition in amounts of from 0.001 to about 5 wt .-%, preferably about 0.01 to about 1 wt .-%, more preferably about 0.05 to 0.5 wt .-% and in particular 0.1 to 0.25 wt .-% is present. The proportion of component (b) may exceed that of component (a) by a factor of about 2 to about 20, in particular about 5 to about 15 and in particular about 8 to about 10.

 The compositions according to the invention may contain further typical auxiliaries and additives, such as, for example, mild surfactants, oil particles, emulsifiers, pearlescent waxes, bodying agents, thickeners, superfatting agents, stabilizers, polymers, silicone compounds, fats, waxes, lecithins, phospholipids, humectants, biogenic agents, antioxidants, deodorants, antiperspirants, self-tanning agents, tyrosine inhibitors (depigmentation agents), hydrotropes, solubilizers, preservatives, perfume oils, dyes and the like. Surfactants

As surfactants anionic, nonionic, cationic and / or amphoteric or zwitterionic surfactants may be included, the proportion of the means usually at about 1 to 70, preferably 5 to 50 and especially 10 to 30 wt .-% is. Typical examples of anionic surfactants are soaps, alkylbenzenesulfonates, alkanesulfonates, olefinsulfonates, alkyl ether sulfonates, glycerol ether sulfonates, cc-methyl ester sulfonates, sulfo fatty acids, alkyl sulfates, alkyl ether sulfates, glycerol ether sulfates, fatty acid ether sulfates, hydroxy mixed ether sulfates, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, mono- and dialkylsulfosuccinates, mono- and dialkylsulfosuccinamates, sulfotriglycerides, amide soaps, ethercarboxylic acids and their salts, fatty acid isethionates, fatty acid sarcosates, fatty acid taurides, N-acylamino acids such as acyl lactylates, acyl tartrates, acyl glutamates and acylaspartates, alkyl oligoglucoside sulfates, protein fatty acid condensates (especially vegetable products wheat-based) and alkyl (ether) phosphates. If the anionic surfactants contain polyglycol ether chains, these may have a conventional, but preferably a narrow homolog distribution. Typical examples of nonionic surfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol ethers, fatty amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers, optionally partially oxidized alk (en) yloligoglycosides or glucuronic acid derivatives, fatty acid N-alkylglucamides, protein hydrolysates (in particular wheat-based vegetable products ), Polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates and amine oxides. If the nonionic surfactants contain polyglycol ether chains, these may have a conventional, but preferably a narrow homolog distribution. Typical examples of cationic surfactants are quaternary ammonium compounds, such as dimethyl distearyl ammonium chloride, and ester quats, especially quaternized fatty acid trialkanolamine ester salts. Typical examples of amphoteric or zwitterionic surfactants are alkylbetaines, alkylamidobetaines, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines. The surfactants mentioned are exclusively known compounds. Typical examples of particularly suitable mild, ie particularly skin-compatible, surfactants are fatty alcohol polyglycol ether sulfates, monoglyceride sulfates, mono- and / or dialkyl sulfosuccinates, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, fatty acid tamates, α-olefinsulfonates, ethercarboxylic acids, alkyl oligoglucosides, fatty acid glucamides, alkylamidobetaines, amphoacetals and / or protein fatty acid condensates, the latter preferably based on wheat proteins.

[0039] Oil body

Guerbet alcohols based on fatty alcohols having 6 to 18, preferably 8 to 10, carbon atoms, esters of linear C ₆ -C ₂₂ fatty acids with linear or branched C ₆ -C ₂ 2 fatty alcohols or esters of branched alcohols are used as the oil body C ₆ -C ₃ -carboxylic acids with linear or branched C ₆ -C ₂₂ fatty alcohols, such as, for example, myristyl myristate, myristyl palmitate, myristyl stearate, myristyl isostearate, myristyl oleate, myristyl behenate, myristyl erucate, cetyl myristate, cetyl palmitate, cetyl stearate, cetyl isostearate, cetyl oleate, cetyl behenate, cetyl erucate , Stearylmyristat, stearyl palmitate, stearyl stearate, Stearylisostearat, stearyl oleate, stearyl behenate, Stearylerucat, isostearyl, isostearyl palmitate, Isostea- rylstearat, isostearyl isostearate, Isostearyloleat, isostearyl behenate, Isostearyloleat, Oleylmy- ristat, oleyl palmitate, oleyl stearate, oleyl isostearate, oleyl oleate, Oleylbehenat, oleyl erucate, behenyl myristate, behenyl , Behenyl stearate, behenyl isostearate, Behenyl oleate, behenyl behenate, behenyl erucate, erucyl myristate, erucyl palmitate, erucyl stearate, erucyl isostearate, erucyl oleate, erucyl behenate and erucyl erucate. In addition, esters of linear C ₆ -C ₂₂ fatty acids with branched alcohols, in particular 2-ethylhexanol, esters of C ₈ -C ₃₈ -alkylhydroxycarboxylic acids with linear or branched C ₆ -C ₂₂ fatty alcohols, in particular dioctyl malates, are esters of linear and / or branched fatty acids with polyhydric alcohols (for example propylene glycol, dimer diol or trimer triol) and / or Guerbet alcohols, triglycerides based on C ₆ -C ₀ fatty, liquid mono- / di- / triglyceride mixtures based on C ₆ -C ₈ - fatty acids, esters of C ₆ -C ₂₂ fatty alcohols and / or Guerbet alcohols with aromatic carboxylic acids, in particular benzoic acid, esters of C ₂ -C ₂ dicarboxylic acids with linear or branched alcohols having 1 to 22 carbon atoms or polyols having 2 to 10 carbon atoms and 2 to 6 hydroxyl groups, vegetable oils, branched primary alcohols, substituted cyclohexanes, linear and branched C ₆ -C ₂₂ fatty alcohol carbonates, such as dicaprylyl carbonates ( Cetiol ^® CC), Guerbet carbonates based on fatty alcohols having 6 to 18, preferably 8 to 10 carbon atoms, esters of benzoic acid with linear and / or branched C ₆ -C ₂₂ alcohols (such as Finsolv® TN), linear or branched, symmetrical or the unsymmetrical dialkyl ethers having 6 to 22 carbon atoms per alkyl group, such as dicaprylyl ether (Cetiol ^® OE), ring opening products of epoxidized fatty acid esters with polyols, silicone oils (cyclomethicones, silicon methicone types, etc.) and / or aliphatic or naphthenic hydrocarbons, such as squalane Squalene or dialkylcyclohexyls.

Emulsifiers

Suitable emulsifiers are, for example, nonionic surfactants from at least one of the following groups:

Addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide onto linear fatty alcohols having 8 to 22 carbon atoms, to fatty acids having 12 to 22 carbon atoms Atoms, alkylphenols having 8 to 15 carbon atoms in the alkyl group and alkylamines having 8 to 22 carbon atoms in the alkyl radical;

 • alkyl and / or alkenyl oligoglycosides having 8 to 22 carbon atoms in the alk (en) yl radical and their ethoxylated analogs;

Addition products of 1 to 15 moles of ethylene oxide with castor oil and / or hydrogenated castor oil;

 Adducts of 15 to 60 moles of ethylene oxide with castor oil and / or hydrogenated castor oil;

 Partial esters of glycerol and / or sorbitan with unsaturated, linear or saturated, branched fatty acids having 12 to 22 carbon atoms and / or hydroxycarboxylic acids having 3 to 18 carbon atoms and their adducts with 1 to 30 moles of ethylene oxide;

 Partial esters of polyglycerol (average intrinsic condensation degree 2 to 8), polyethylene glycol (molecular weight 400 to 5000), trimethylolpropane, pentaerythritol, sugar alcohols (eg sorbitol), alkylglucosides (eg methylglucoside, butylglucoside, laurylglucoside) and polyglucosides (eg cellulose) saturated and / or unsaturated, linear or branched fatty acids having 12 to 22 carbon atoms and / or hydroxycarboxylic acids having 3 to 18 carbon atoms and their adducts with 1 to 30 moles of ethylene oxide;

Mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohol and / or mixed esters of fatty acids having 6 to 22 carbon atoms, methyl glucose and polyols, preferably glycerol or polyglycerol.

 Mono-, di- and trialkyl phosphates and mono-, di- and / or tri-PEG-alkyl phosphates and their salts;

· Wool wax alcohols;

 Polysiloxane-polyalkyl-polyether copolymers or corresponding derivatives;

 Block copolymers e.g. Polyethylene glycol-30 dipolyhydroxystearates;

• polymeric emulsifiers such as Pemulen grades (TR-L, TR-2) from Goodrich or Cosmedia SP ^® Cognis;

· Polyalkylene glycols as well

 • Glycerine carbonate.

 In the following, particularly suitable emulsifiers are explained in more detail:

Alkoxylates. The addition products of ethylene oxide and / or of propylene oxide with fatty alcohols, alkylphenols or castor oil are known, commercially available products. These are mixtures of homologs whose average alkoxylation degree is the ratio of the molar amounts of ethylene oxide and / or Propylene oxide and substrate, with which the addition reaction is carried out, corresponds. ₂ Ci / i ₈ - fatty acid mono- and diesters of addition products of ethylene oxide onto glycerol are known as refatting agents for cosmetic preparations. Alkyl and / or alkenyl oligoglycoside. Alkyl and / or alkenyl oligoglycosides, their preparation and their use are known from the prior art. In particular, their preparation takes place by reaction of glucose or oligosaccharides with primary alcohols having 8 to 18 carbon atoms. With regard to the glycoside radical, both monoglycosides in which a cyclic sugar residue is glycosidically linked to the fatty alcohol and oligomeric glycosides having a degree of oligomerization of preferably approximately 8 are suitable. The degree of oligomerization is a statistical mean, which is based on a homolog distribution typical for such technical products.

 Partial glycerides. Typical examples of suitable partial glycerides are Hydroxystea- rinsäuremonoglycerid, hydroxystearic acid diglyceride, isostearic acid, Isostea- rinsäurediglycerid, säurediglycerid oleic acid monoglyceride, oleic acid diglyceride, Ricinolsäuremoglycerid, ricinoleic, Linolsäuremonoglycerid, Linolsäurediglycerid, Linolensäuremonoglycerid, Linolensäurediglycerid, Erucasäuremonoglycerid, Erucasäurediglycerid, Weinsäuremonogly- cerid, Weinsäurediglycerid, Citronensäuremonoglycerid, Citronendiglycerid, Malic acid monoglyceride, malic acid diglyceride and their technical mixtures which, subordinated to the production process, may still contain small amounts of triglyceride. Also suitable are addition products of 1 to 30, preferably 5 to 10 moles of ethylene oxide to said Partialglyceride.

 Sorbitan esters. As sorbitan esters sorbitan, sorbitan sesquiisostearat, sorbitan diisostearate, sorbitan triisostearate, sorbitan, sorbitan sesquioleate, sorbitan dioleate, trioleate, Sorbitanmonoerucat, Sorbitansesquierucat, Sorbitandierucat, Sorbitantrierucat, Sorbitanmonoricinoleat, Sorbitansesquiricinoleat, bitandiricinoleat sorting, Sorbitantriricinoleat, Sorbitanmonohydroxystearat, sorbitan sesquihydroxystearat , Sorbitan dihydroxystearate, sorbitan trihydroxystearate, sorbitan mono- tartrate, sorbitan sesquivar tartrate, sorbitan dandristrate, sorbitan tri- tartrate, sorbitan monocitrate, sorbitan siccitrate, sorbitan di-citrate, sorbitan tricitrate, sorbitan monomaleate, sorbitan sesquimaleate, sorbitan dimaleate, sorbitan trimaleate and technical mixtures thereof. Also suitable are addition products of 1 to 30, preferably 5 to 10 moles of ethylene oxide to said sorbitan esters.

Polyglycerolester. Typical examples of suitable polyglycerol esters are polyglyceryl-2 dipolyhydroxystearates (Dehymuls® PGPH), polyglycerol-3-diisostearates (Lameform® TGI), polyglyceryl-4 isostearates (Isolan® Gl 34), polyglyceryl-3 oleates, diisostearoyl polyglyceryl-3 diisostearates (Isolan® PDI), Polyglyceryl-3 Methylglucose Distearate (Tego Care® 450), Polyglyceryl-3 Beeswax (Cera Bellina®), Polyglyceryl-4 Caprate (Polyglycerol Caprate T2010 / 90), Polyglyceryl-3 Cetyl Ether (Chimexane® NL) , Polyglyceryl-3 Distearate (Cromophor® GS 32) and Polyglyceryl Polyricinoleate (Admul® WOL 1403) Polyglyceryl Dimerate Isostearate and mixtures thereof. Examples of other suitable polyol esters are the mono-, di- and triesters of trimethylolpropane or pentaerythritol reacted with 1 to 30 mol of ethylene oxide with lauric acid, coconut fatty acid, tallow fatty acid, palmitic acid, stearic acid, oleic acid, behenic acid and the like.

Anionic emulsifiers. Typical anionic emulsifiers are aliphatic fatty acids having 12 to 22 carbon atoms, such as palmitic acid, stearic acid or behenic acid, and dicarboxylic acids having 12 to 22 carbon atoms, such as azelaic acid or sebacic acid. Amphoteric and cationic emulsifiers. Furthermore, zwitterionic surfactants can be used as emulsifiers. Zwitterionic surfactants are those surface-active compounds which carry at least one quaternary ammonium group and at least one carboxylate and one sulfonate group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammoniumglycinate, for example Kokosalkyldimethylammoniumglycinat, N-acylaminopropyl-N, N-dimethylammoniumglycinate, for example Kokosacyl- aminopropyldimethyl-ammoniumglycinat, and 2-alkyl-3-carboxylmethyl 3-hydroxyethylimidazolines having in each case 8 to 18 C atoms in the alkyl or acyl group, and the cocoacylaminoethylhydroxyethylcarboxymethylglycinate. Particularly preferred is the fatty acid amide derivative known by the CTFA name Cocamidopropyl Betaine. Also suitable emulsifiers are ampholytic surfactants. Ampholytic surfactants are surface-active compounds which, in addition to a _C8 / i ₈ alkyl or acyl group, contain at least one free amino group and at least one -COOH or -S0 ₃ H group and capable of forming inner salts. Examples of suitable phytochemical surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each having about 8 up to 18 carbon atoms in the alkyl group. Particularly preferred on the pholytic surfactants are N-cocoalkylaminopropionate, Kokosacylaminoethylaminopropionat and the Ci ₂ / i ₈ acylsarcosine. Finally, cationic surfactants may also be used as emulsifiers, particular preference being given to those of the esterquat type, preferably methyl-quaternized difatty acid diethanolamine ester salts. Fats and waxes

Typical examples of fats are glycerides, ie solid or liquid vegetable or animal products, which consist essentially of mixed glycerol esters of higher fatty acids, waxes include natural waxes, such as candelilla wax, carnauba wax, Japan wax, esparto wax, cork wax, Guaruma wax, rice germ oil wax, sugar cane wax, ouricury wax, montan wax, beeswax, shellac wax, spermaceti, lanolin (wool wax), crepe fat, ceresin, ozokerite (groundwax), petrolatum, paraffin waxes, microwaxes; chemically modified waxes (hard waxes), such as montan ester waxes, Sasol waxes, hydrogenated jojoba waxes and synthetic waxes, such as polyalkylene waxes and polyethylene glycol waxes in question. In addition to the fats come as additives and fat-like substances such as lecithins and phospholipids in question. By the term lecithin, those skilled in the art will understand those glycerophospholipids which are formed from fatty acids, glycerol, phosphoric acid and choline by esterification. Lecithins are therefore often referred to in the art as Phosphatidylcholine (PC). Examples of natural lecithins include the cephalins, which are also referred to as phosphatidic acids and represent derivatives of l, 2-diacyl-sn-glycerol-3-phosphoric acids. On the other hand, phospholipids are usually understood as meaning mono- and preferably diesters of phosphoric acid with glycerol (glycerol phosphates), which are generally regarded as fats. In addition, sphingosines or sphingolipids are also suitable. Pearlescent waxes

 Examples of suitable pearlescent waxes are: alkylene glycol esters, especially ethylene glycol distearate; Fatty acid alkanolamides, especially coconut fatty acid diethanolamide; Partial glycerides, especially stearic acid monoglyceride; Esters of polybasic, optionally hydroxy-substituted carboxylic acids with fatty alcohols having 6 to 22 carbon atoms, especially long-chain esters of tartaric acid; Fatty substances, such as, for example, fatty alcohols, fatty ketones, fatty aldehydes, fatty ethers and fatty carbonates, which in total have at least 24 carbon atoms, especially laurone and distearyl ether; Fatty acids such as stearic acid, hydroxystearic acid or behenic acid, ring-opening products of olefin epoxides having 12 to 22 carbon atoms with fatty alcohols having 12 to 22 carbon atoms and / or polyols having 2 to 15 carbon atoms and 2 to 10 hydroxyl groups and mixtures thereof

[0055] Coolants

Coolants are compounds that produce a feeling of coldness on the skin. As a rule, these are menthol compounds which - in addition to the parent menthol itself - for example selected from the group formed by menthol methyl ether, menthone glyceryl acetal (FEMA GRAS ¹ 3807), menthone glyceryl ketal (FEMA GRAS 3808) , Menthyl Lactate (FEMA GRAS 3748), Menthol Ethylene Glycol Carbonate (FEMA GRAS 3805), Menthol Propylene Glycol Carbonate (FEMA GRAS 3806), Menthyl N-Ethyloxamate, Monomethyl Succinate (FEMA GRAS 3810), Monomenthyl Glutamate (FEMA GRAS 4006) , Menthoxy-1,2-propanediol (FEMA GRAS 3784), menthoxy-2-methyl-1,2-propanediol (FEMA GRAS 3849) and the menthane carboxylic acid esters and amides WS-3, WS-4, WS-5, WS- 12, WS-14 and WS-30 and their mixtures.

 A first important representative of these substances is the monomenthyl succinate (FEMA GRAS 3810). Both the succinate and the analogous monomenthyl glutarate (FEMA GRAS 4006) are important representatives of monomenthyl esters based on di- and polycarboxylic acids:

¹ FEMA stands for "Flavor and Extracts Manufacturers Association" and GRAS is defined as "Generally Regarded Äs Safe", a FEMA GRAS designation means that the substance identified in this way is tested according to the standard method and considered to be toxicologically harmless. Examples of applications of these substances can be found for example in the publications WO 2003 043431 (Unilever) or EP 1332772 AI (IFF).

[0059] The next major group of the purposes of the invention, preferred menthol compounds comprising carbonate ester of menthol and polyols, such as glycols, glycerol, or carbohydrates, such as menthol ethylene glycol carbonate (FEMA GRAS 3805 = Frescolat ^® MGC), menthol propylene glycol carbonate (FEMA GRAS 3784 = Frescolat ^® M PC), menthol 2-methyl-l, 2-propanediol carbonates (FEMA GRAS 3849) or the corresponding sugar derivatives. Also preferred are the compounds menthol MeN thyl Lactate (FEMA GRAS 3748 = Frescolat ^® ML) and in particular the Menthone glyceryl acetal (FEMA GRAS 3807) or Menthone glyceryl ketal (FEMA GRAS 3808), which is marketed under the name Frescolat ^® MGA are. As ga nz particularly advantageous in these materials menthones glyceryl acetal / ketal and the Menthyl Lactate and Menthol Ethylene Glycol carbonates or menthol Propylene Glycol Carbonatw have proven that the Applicant under the names Frescolat ^® MGA, Frescolat ^® ML, Frecolat ^® MGC and Frescolat ^® M PC distributes.

 In the 1970s, menthol compounds were first developed which have a C-C bond in the 3-position and from which a number of representatives can likewise be used. These substances are generally referred to as WS types. Base is a menthol derivative in which the hydroxyl is replaced by a carboxyl group (WS-1). From this structure, all other types of WS are derived, such as the preferred species WS-3, WS-4, WS-5, WS-12, WS-14 and WS-30.

Bodying agent and thickener

As consistency factors are primarily fatty alcohols or hydroxy fatty alcohols having 12 to 22 and preferably 16 to 18 carbon atoms and in addition partial glycerides, fatty acids or hydroxy fatty acids into consideration. Preference is given to a combination of these substances with alkyl oligoglucosides and / or fatty acid N-methylglucamides of the same chain length and / or polyglycerol poly-12-hydroxystearates. Suitable thickening agents are, for example, Aerosil types (hydrophilic silicas), polysaccharides, in particular xanthan gum, guar guar, agar agar, alginates and Tylose, carboxymethylcellulose and hydroxyethyl and hydroxypropylcellulose, and also higher molecular weight polyethylene glycol mono- and diesters fatty acids, polyacrylates, (eg Carbopole® and Pemulen types from Goodrich, Synthalene® from Sigma, Keltrol types from Kelco, sepiolite types from Seppic, Salcare types from Allied Colloids), polyacrylamides, polymers, polyvinyl alcohol and polyvinylpyrrolidone. As a particularly effective bentonites, such as Bentone ^® Gel VS-5PC (Rheox) have shown which is torit to a mixture of cyclopentasiloxane, disteardimonium HEC and is propylene carbonate. Also suitable are surfactants, such as, for example, ethoxylated fatty acid glycerides, esters of fatty acids with polyols, such as pentaerythritol or trimethylolpropane, fatty alcohol ethoxylates with narrow homolog distribution or alkyl oligoglucosides, and electrolytes, such as common salt and ammonium chloride. Superfatting agents and stabilizers

 Superfatting agents which can be used are substances such as, for example, lanolin and lecithin, as well as polyethoxylated or acylated lanolin and lecithin derivatives, polyol fatty acid esters, monoglycerides and fatty acid alkanolamides, the latter simultaneously serving as foam stabilizers.

 As stabilizers, metal salts of fatty acids, e.g. Magnesium, aluminum and / or zinc stearate or ricinoleate can be used.

Polymers

 Suitable cationic polymers are, for example, cationic cellulose derivatives, e.g. a quaternized hydroxyethylcellulose available under the name Polymer JR 400® from Amerchol, cationic starch, copolymers of diallylammonium salts and acrylamides, quaternized vinylpyrrolidone / vinylimidazole polymers, e.g. Lucvivat® (BASF), condensation products of polyglycols and amines, quaternized collagen polypeptides, such as lauryldimonium hydroxypropyl hydrolyzed collagen (Lamequat®L / Grünau), quaternized wheat polypeptides, polyethylenimine, cationic silicone polymers, e.g. Amodimethicones, copolymers of adipic acid and dimethylaminohydroxypropyldiethylenetriamine (Cartaretine® / Sandoz), copolymers of acrylic acid with dimethyldiallylammonium chloride (Merquat® 550 / Chemviron), polyamino-polyamides and their crosslinked water-soluble polymers, cationic chitin derivatives such as quaternized chitosan, optionally microcrystalline, condensation products from dihaloalkylene, such as Dibromobutane with bis-dialkylamines, e.g. Bis-dimethylamino-1,3-propane, cationic guar gum, e.g. Jaguar® CBS, Jaguar® C-17, Jaguar® C-16 from Celanese, quaternized ammonium salt polymers, e.g. Mirapol® A-15, Mirapol® AD-1, Mirapol® AZ-1 from Miranol.

 Suitable anionic, zwitterionic, amphoteric and nonionic polymers are, for example, vinyl acetate / crotonic acid copolymers, vinylpyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and their esters, uncrosslinked and polyols crosslinked polyacrylic acids, acrylamidopropyltrimethylammonium chloride / acrylate copolymers, octylacrylamide / methyl methacrylate / tert.butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers, polyvinylpyrrolidone, vinylpyrrolidone / vinyl acetate copolymers, vinylpyrrolidone / dimethylaminoethyl methacrylate / vinylcaprolactam Terpolymers and optionally derivatized cellulose ethers and silicones in question.

Silicone compounds

Suitable silicone compounds are, for example, dimethylpolysiloxanes, methylphenylpolysiloxanes, cyclic silicones and amino, fatty acid, alcohol, polyether, epoxy, fluorine, glycoside and / or alkyl-modified silicone compounds which are both liquid and resin-form at room temperature may be present. Also suitable are simethicones, which are mixtures of dimethicones having an average chain length of from 200 to 300 dimethylsiloxane units and hydrogenated silicates.

Humectants

Humectants serve to further optimize the sensory properties of the composition and to regulate the moisture of the skin. At the same time, the low-temperature stability of the preparations according to the invention, in particular in the case of emulsions, is increased. The humectants are usually contained in an amount of 0.1 to 15% by weight, preferably 1 to 10% by weight, and more preferably 5 to 10% by weight.

According to the invention, u.a. Amino acids, pyrrolidonecarboxylic acid, lactic acid and its salts, lactitol, urea and urea derivatives, uric acid, glucosamine, creatinine, cleavage products of collagen, chitosan or chitosan salts / derivatives, and in particular polyols and polyol derivatives (eg glycerol, diglycerol, triglycerol, ethylene glycol, Propylene glycol, butylene glycol, erythritol, 1,2,6-hexanetriol, polyethylene glycols such as PEG-4, PEG-6, PEG-7, PEG-8, PEG-9, PEG-10, PEG-12, PEG-14, PEG-16, PEG-18, PEG-20), sugars and sugar derivatives (including fructose, glucose, maltose, maltitol, mannitol, inositol, sorbitol, sorbitylsilanediol, sucrose, trehalose, xylose, xylitol, glucuronic acid and their salts), ethoxylated sorbitol (Sorbeth-6, sorbeth-20, sorbeth-30, sorbeth-40), honey and hardened honey, hardened starch hydrolysates and mixtures of hardened wheat protein and PEG-20 acetate copolymer. Preferably suitable as humectants according to the invention are glycerol, diglycerol, triglycerol and butylene glycol.

Biogenic agents and antioxidants

 Examples of biogenic active substances include tocopherol, tocopherol acetate, tocopherol palmitate, ascorbic acid, (deoxy) ribonucleic acid and their fragmentation products, β-glucans, retinol, bisabolol, allantoin, phytantriol, panthenol, AHA acids, amino acids, ceramides, pseudoceramides, essential oils , Plant extracts, such as Prunus extract, Bambaranussextrakt and vitamin complexes to understand.

Antioxidants interrupt the photochemical reaction chain, which is triggered when UV radiation penetrates into the skin. Typical examples are amino acids (eg glycine, histidine, tyrosine, tryptophan) and their derivatives, midazoles (eg urocaninic acid) and their derivatives, peptides such as D, L-carnosine, D-carnosine, L-carnosine and their derivatives ( eg anserine), carotenoids, carotenes (eg carotene, β-carotene, lycopene) and their derivatives, chlorogenic acid and its derivatives, lipoic acid and its derivatives (eg dihydrolipropylic acid), aurothioglucose, propylthiouracil and other thiols (eg thioredoxin, gluta- thion, 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, bithine sulfones, penta, hexa, heptathionine sulfoximine) very small tolerated dosages (eg pmol to μιηοΙ / kg), also (metal) chelators (eg cc-hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin), cc-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 (eg γ-linolenic acid, linoleic acid, oleic acid), folic acid and its derivatives, ubiquinone and ubiquinol and their derivatives, vitamin C and derivatives ( eg Ascorbylpa faux, Mg ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives (eg vitamin E acetate), vitamin A and derivatives (vitamin A palmitate) as well as coniferylbenzoate of the benzoin, rutinic acid and its derivatives, cc-glycosylrutin, Ferulic acid, furfurylidene glucitol, carnosine, butylhydroxytoluene, butylhydroxyanisole, nordihydroguaiacetic acid, nordihydroguaiaretic acid, trihydroxybutyrophenone, uric acid and its derivatives, mannose and its derivatives, superoxide dismutase, zinc and its derivatives (eg ZnO, ZnS0 ₄ ) selenium and its derivatives (eg selenium Methionine), stilbenes and their derivatives (eg stilbene oxide, trans-stilbene oxide) and the derivatives suitable according to the invention (salts, esters, ethers, Sugars, nucleotides, nucleosides, peptides and lipids) of said active substances. Deodorants and germ repellents

 Cosmetic deodorants (deodorants) counteract, cover or eliminate body odors. Body odors are caused by the action of skin bacteria on apocrine sweat, forming unpleasant-smelling degradation products. Accordingly, deodorants contain active substances which act as antimicrobials, enzyme inhibitors, odor absorbers or odor maskers.

Anti-sprouting agents. As germ-inhibiting agents are basically all effective against Gram-positive bacteria substances such. B. 4-hydroxybenzoic acid and its salts and esters, N- (4-chlorophenyl) -N ^'- (3,4-dichlorophenyl) urea, ^{2,4,4'-trichloro-2'} - hydroxy-diphenyl ether (Triclosan) 4-chloro-3,5-dimethyl-phenol, 2,2 ^{'-methylene-bis} (6-bromo-4-chlorophenol), 3-methyl-4- (l-methylethyl) phenol, 2-benzyl-4- chlorophenol, 3- (4-chlorophenoxy) -l, 2-propanediol, 3-iodo-2-propynyl butylcarbamate, chlorhexidine, 3,4,4 ^'- trichlorocarbanilide (TTC), antibacterial fragrances, thymol, thyme oil, eugenol, clove oil, menthol , Mint oil, farnesol, phenoxyethanol, glycerol monocaprinate, glycerol monocaprylate, glycerol monolaurate (GML), diglycerol monocaprinate (DMC), salicylic acid N-alkylamides such as. Salicylic acid n-octylamide or salicylic acid n-decylamide.

Enzyme inhibitors. For example, esterase inhibitors are suitable as enzyme inhibitors. These are preferably trialkyl citrates such as trimethyl citrate, tripropy citrate, triisopropyl citrate, tributyl citrate and in particular triethyl citrate (Hydagen® CAT). The substances inhibit the enzyme activity and thereby reduce odors. Further substances which are suitable as esterase inhibitors are sterol sulfates or phosphates, such as, for example, lanosterol, cholesterol, campesterol, stigmasterol and sitosterol sulfate or phosphate, dicarboxylic acids and their esters, for example glutaric acid, glutaric acid monoethyl ester, glutaric acid diethyl ester, Adipic acid, adipic acid monoethyl ester, diethyl adipate, malonic acid and diethyl malonate, hydroxycarboxylic acids and their esters, for example citric acid, malic acid, tartaric acid or diethyl tartrate, and zinc glycinate. Odor absorber. Suitable odor absorbers are substances that absorb and largely retain odor-forming compounds. They reduce the partial pressure of the individual components and thus also reduce their propagation speed. It is important that perfumes must remain unimpaired. Odor absorbers have no activity against bacteria. They contain, for example, as a main component of a complex zinc salt of ricinoleic acid or special, largely odorless fragrances, which are known in the art as "fixatives", such. B. Extracts of Labdanum or Styrax or certain Abietinsäurederivate. Odor maskers are fragrances or perfume oils which, in addition to their function as odor maskers, give the deodorants their respective scent. Examples of perfume oils are mixtures of natural and synthetic fragrances. Natural fragrances are extracts of flowers, stems and leaves, fruits, fruit peel, roots, woods, herbs and grasses, needles and twigs, as well as resins and balsams. Furthermore, animal raw materials come into question, such as civet and Castoreum. Typical synthetic fragrance compounds are products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons. Fragrance compounds of the ester type are, for example, benzyl acetate, p-tert-butylcyclohexyl acetate, linalyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, allylcyclohexyl propionate, styrallyl propionate and benzyl salicylate. The ethers include, for example, benzyl ethyl ether, to the aldehydes, for example, the linear alkanals having 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones such as the Jonone and Methylcedrylketon to the alcohols anethole, Citronellol, eugenol, isoeugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes and balsams. However, preference is given to using mixtures of different fragrances which together produce an attractive fragrance. Also essential oils of lower volatility, which are mostly used as aroma components, are suitable as perfume oils, eg sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon oil, lime blossom oil, juniper berry oil, vetiver oil, oliban oil, galbanum oil, labdanum oil and lavandin oil. Bergamot oil, dihydromyrcenol, lilial, lyral, citronellol, phenylethyl alcohol, oc-hexylcinnamaldehyde, geraniol, benzylacetone, cyclamenaldehyde, linalool, Boisambrene Forte, Ambroxan, indole, hedione, sandelice, citron oil, tangerine oil, orange oil, allylamylglycolate, cyclovertal, Lavandin oil, m uskatell sage oil, .beta.-damascone, geranium oil bourbon, cyclohexyl salicylate, vertofix coeur, iso-e-super, fixolide NP, evernyl, indaldine gamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, romilate, irotyl and floramate alone or in mixtures, used.

 Antiperspirants. Antiperspirants (antiperspirants) reduce the formation of sweat by influencing the activity of eccrine sweat glands and thus counteract underarm wetness and body odor. Aqueous or anhydrous formulations of antiperspirants typically contain the following ingredients:

· Astringent agents,

 • oil components,

 Nonionic emulsifiers,

 Coemulsifiers,

• bodybuilder, • auxiliaries such as B. thickener or complexing agent and / or

 • non-aqueous solvents such. As ethanol, propylene glycol and / or glycerol.

Salts of aluminum, zirconium or zinc are especially suitable as astringent antiperspirant active ingredients. Such suitable antiperspirant active ingredients are e.g. Aluminum chloride, aluminum chlorohydrate, aluminum dichlorohydrate, aluminum sesquichlorohydrate and their complex compounds, eg. With propylene glycol-1,2. Aluminum hydroxyantoinate, aluminum chloride tartrate, aluminum-zirconium trichlorohydrate, aluminum-zirconium tetrachlorohydrate, aluminum-zirconium-pentachlorohydrate and their complex compounds, eg. With amino acids such as glycine. In addition, antiperspirants may contain customary oil-soluble and water-soluble adjuvants in smaller amounts. Such oil-soluble adjuvants may be e.g. be:

 • anti-inflammatory, skin-protecting or fragrant essential oils,

• synthetic skin-protecting agents and / or

 • oil-soluble perfume oils.

 Usual water-soluble additives are e.g. Preservatives, water-soluble fragrances, pH adjusters, e.g. Buffer mixtures, water-soluble thickeners, e.g. water-soluble natural or synthetic polymers such as e.g. Xanthan gum, hydroxyethylcellulose, polyvinylpyrrolidone or high molecular weight polyethylene oxides.

Hydrotropes

 To improve the flow behavior, it is also possible to use hydrotropes, such as, for example, ethanol, isopropyl alcohol, or polyols; These substances largely correspond to the initially described carriers. Polyols contemplated herein preferably have from 2 to 15 carbon atoms and at least two hydroxyl groups. The polyols may contain other functional groups, in particular amino groups, or be modified with nitrogen. Typical examples are

 • glycerin;

 Alkylene glycols such as ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, hexylene glycol, and polyethylene glycols having an average molecular weight of 100 to 1,000 daltons;

 Technical Oligoglyceringemische with an intrinsic degree of condensation of 1.5 to 10 such as technical Diglyceringemische with a diglycerol content of 40 to 50 wt .-%;

 Methylol compounds, in particular trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol and dipentaerythritol;

 Lower alkyl glucosides, especially those having 1 to 8 carbons in the alkyl radical, such as, for example, methyl and butyl glucoside;

 Sugar alcohols having 5 to 12 carbon atoms, such as sorbitol or mannitol,

• sugars having 5 to 12 carbon atoms, such as glucose or sucrose; • amino sugars, such as glucamine;

 • Dialcoholamines, such as diethanolamine or 2-amino-l, 3-propanediol.

Preservative

Examples of suitable preservatives are phenoxyethanol, formaldehyde solution, parabens, pentanediol or sorbic acid and the silver ^complexes known under the name Surfacine® and the further classes of compounds listed in Appendix 6, Parts A and B of the Cosmetics Regulation. Perfume oils and flavors

As perfume oils may be mentioned mixtures of natural and synthetic fragrances. Natural fragrances are extracts of flowers (lily, lavender, roses, jasmine, neroli, ylang-ylang), stems and leaves (geranium, patchouli, petitgrain), fruits (aniseed, coriander, caraway, juniper), fruit peel (bergamot, lemon, Oranges), roots (mace, angelica, celery, cardamom, costus, iris, caulm), wood (pine, sandal, guaiac, cedar, rosewood), herbs and grasses (tarragon, lemongrass, sage, Thyme), needles and twigs (spruce, fir, pine, pines), resins and balsams (galbanum, elemi, benzoin, myrrh, olibanum, opoponax). Furthermore, animal raw materials come into question, such as civet and Castoreum. Typical synthetic fragrance compounds are ester type products, ethers, aldehydes, ketones, alcohols and hydrocarbons. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzylformate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate and benzylsalicylate. The ethers include, for example, benzyl ethyl ether, to the aldehydes, for example, the linear alkanals having 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and Bourgeonal, to the ketones, for example, the Jonone, -lsomethylionon and Methylcedrylketon, The alcohols include anethole, citronellol, eugenol, isoeugenol, geraniol, linalool, phenylethyl alcohol and terpineol; the hydrocarbons mainly include the terpenes and balms. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance. Essential oils of lower volatility, which are usually used as aroma components, are suitable as perfume oils, for example sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon oil, lime blossom oil, juniper berry oil, vetiver oil, oliban oil, galbanum oil, labolanum oil and lavandin oil. Bergamot oil, dihydromyrcenol, lilial, lyral, citronellol, phenylethyl alcohol, cc- hexylcinnamaldehyde, geraniol, benzylacetone, cyclamenaldehyde, linalool, boisambrene forte, ambroxan, indole, hedione, sandelice, citron oil, mandarin oil, orange oil, allylamylglycate, cyclovertal are preferably used , Lavandin oil, m uskatell sage oil, β-damascone, geranium oil bourbon, cyclohexyl salicylate, vertofix coeur, iso-E-super, fixolide NP, evernyl, inderaline gamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, romilllat, irotyl and floramate alone or in mixtures. Suitable flavors are, for example, peppermint oil, spearmint oil, aniseed oil, star aniseed oil, caraway oil, eucalyptus oil, fennel oil, lemon oil, wintergreen oil, clove oil, menthol and the like. Dyes

 As dyes, the substances suitable and suitable for cosmetic purposes can be used, as they are compiled, for example, in the publication "Cosmetic Colorants" of the Dye Commission of the Deutsche Forschungsgemeinschaft, Verlag Chemie, Weinheim, 1984, pp. 81-106. Examples are Kochillerot A (Cl 16255), Patent Blue V (C.1.42051), Indigotin (C.1.73015), chlorophyllin (C.1.75810), quinoline yellow (C.1.47005), titanium dioxide (C.1.77891), indanthrene blue RS ( Cl 69800) and Krapplack (Cl58000). As a luminescent dye and luminol may be included. These dyes are usually used in concentrations of 0.001 to 0.1 wt .-%, based on the total mixture.

The total amount of auxiliaries and additives may be 1 to 50, preferably 5 to 40 wt .-% - based on the means - amount. The preparation of the agent can be carried out by conventional cold or hot processes; It is preferable to work according to the phase inversion temperature method. INDUSTRIAL APPLICABILITY

 Another object of the invention relates to a non-therapeutic method for the prevention and / or treatment of human skin against signs of degeneration and aging, which are not caused or not exclusively by the influence of light, wherein a preparation according to the first or the second Subject of the invention or a cosmetic agent of the type described above topically applied. It has been found that the topical administration of about 1 to about 5 g of these preparations or agents at least once, better twice a day over a period of at least 7 to 14 days to measurable results, especially as regards the depth of wrinkles leads. The preparations and compositions are particularly effective in female consumers in the range of 35 to 55 years.

 Also claimed is the use of at least one compound of For

with the proviso that R 1 is H or CH ₃ and R 2 is H or COOH, or salts thereof for the prevention and / or treatment of degeneration and aging phenomena of Human skin that is not or not exclusively caused by the influence of light. The use may optionally be in combination with UV sun protection factors.

 In particular, this use also includes

 The stimulation of G6PDH activity and thus the increase in the amount of cellular DNA,

 The inhibition of apoptosis induction,

 Stimulating the production of dermal macromolecules,

 The inhibition of elastase activity as well

 Inhibition of glycation of collagen,

as described in detail in the following examples.

[0096] DERMAL MACROMOLECULES

 The present invention has an impact on the formation of dermal macromolecules, the degradation of which, in turn, is an important cause of skin aging or skin degeneration. The relationships are briefly discussed below.

 For the purposes of the invention, dermal macromolecules are, in principle, to be understood as meaning all macromolecules which can be found directly as constituents of the skin either in the basal membrane between the dermis and the epidermis or in the dermis and epidermis. In particular, the dermal macromolecules are those selected from the group consisting of glycosaminoglycans, in particular chondroitin sulfate, keratan sulfate, dermatan sulfate and hyaluronic acid and its salts, collagen, in particular type II I collagen, elastin, fibronectin, proteoglycans and their salts.

 The glycosaminoglycans are also referred to as mucopolysaccharides. These are negatively charged, long unbranched polysaccharides (glycans), which consist of 1,4-linked units of dissacharides in which one mole of a uronic acid (D-glucuronic acid or, for example, L-iduronic acid) with the 3-position of a N-acetylated amino sugars (glycosamines) are glycosidically linked. The glycosaminoglycans are bound in the tissue to several chains of a core protein (core protein) and thus form the proteoglycans.

The chondrotin sulfate is one of the glycosaminoglycans. It occurs in tissue as chondroitin-4-sulphate or as chondroitin-6-sulphate and consists inter alia of D-glucuronic acid and N-acetyl-D-galactosamine. The molar mass is between 5,000 and 50,000. The non-anticoagulating glycosaminoglycan dermatan sulfate, also known as beta-heparin, consists of L-iduronic acid or D-glucuronic acid, N-acetyl-D-galactosamine and sulfate groups. The molar mass of deramtansulfate is between 15,000 and 40,000. Hyaluronic acid is an acid glycosaminoglycan. The basic building block of hyaluronic acid is an aminodisaccharide composed of D-glucuronic acid and N-acetyl-D-glucosamine in (beta 1-3) glycosidic linkage with the next unit (beta l-4) glycosidically linked. Unlike many other glycosaminoglycans, hyaluronic acid has no sulfate groups and is not protein bound in the tissue. Collagen consists of protein fibers and occurs in human skin in three different types (type I, II I and IV). In collagen, the individual polypeptide chains, each containing much of the amino acid proline and every three residues of glycine, are wrapped around each other in a triple helix. The collagen fibers are synthesized as tropocollagen in the fibroblasts and secreted into the extracellular matrix. The stimulation of the collagen synthesis according to the invention leads to an increase in the production of collagen and thus to an increased intermolecular solidification of the dermis and thereby to a firmer appearing skin. The elastin is also a fibrous protein. These are unstructured covalently cross-linked polypeptide chains that form a rubber-like elastic material. The elastin is released into the extracellular matrix in the skin cells after synthesis. The stimulation according to the invention of the synthesis of the elastin polypeptide chains leads to an increase in the production of elastin and thus to an increase in the elasticity of the skin.

 Fibronectin represents a group of high molecular weight glycoproteins (M R of the dimer ca. 440 000-550 000) found in the extracellular matrix and extracellular fluids. The fibronectin dimer connected by two disulfide bridges, an elongated molecule measuring 600x25 Å, binds by linear combination of three distinct repeating domains and the like. a. Collagens, glycosaminoglycans, proteoglycans, fibrin (ogen), deoxyribonucleic acids, immunoglobulins, plasminogen, plasminogen activator, thrombospondin, cells and microorganisms. Due to these properties it conveys z. The adhesion of connective tissue cells to collagen fibrils or of thrombocytes and fibroblasts to fibrin (contribution to wound healing).

 The proteoglycans, like the glycoproteins, consist of carbohydrates and of proteins, but in proteoglycans, the proportion of polysaccharides predominates. The proteoglycans of the skin contain dermatan sulfate. Approximately 140 such proteoglycans are non-covalently attached to a hyaluronic acid chain to molecular aggregates with an average molar mass of approximately 2 million with the aid of smaller proteins (link proteins). The polyanionic aggregates, which are distinguished by their ability to bind water, can form solid gels which impart elasticity and tensile strength to the supporting tissue (extracellular matrix). In mucus, they protect the epithelia. The inventive stimulation of the synthesis of proteoglycans and hyaluronic acid leads to a greater amount of extracellular matrix and thus to increased elasticity and tensile strength.

Glycation is a non-enzymatic reaction of glucose or other sugars with proteins to glycoproteins. This reaction leads to unintentional changes in the collagen and elastin and thus to changes in the extracellular matrix. The function of collagen and the extracellular matrix are disturbed. The prevention of glycation according to the invention leads to a reduction in the non-enzymatic change in collagen and elastin and thus in the prevention of a reduced function of the extracellular matrix. EXAMPLES

EXAMPLES 1 TO 6, COMPARATIVE EXAMPLES VI AND V2

Effectiveness against skin aging

 Background: The enzyme glucose-6-phosphate dehydrogenase (G6PDH) catalyzes the first step of the so-called "pentose pathway", in which an essential DNA building block, namely the deoxyribose, is formed, whereby glucose-6-phosphate ( G6PDH is converted into 6-phosphatogluconate (6PG) by G6PDH, while the necessary coenzyme NADP is reduced to NADPH2, which in turn can catalyze a variety of other biological reactions, such as the recycling of glutathione or lipid synthesis Glutathione protects many enzymes that have SH groups and cells from oxidative stress, such as UV exposure, making G6PDH an important parameter for cell protection and skin renewal.

Method: The G6PDH activity was determined in vitro on human fibroblasts by the enzymatic method of Okada, the DNA content by the method of Desaulniers. The results are summarized in Table 1. The results are given in each case of 3 series of measurements with triple determination in% -rel compared to a blank.

Table 1

 Stimulation of G6PDH activity (expressed in% rel.)

As the examples show, the administration of carnosines causes both the amount of cellular DNA and G6PDH to increase in a statistically significant manner. This already unexpected effect can be increased even more by combining it with UV light protection filters, although these alone show no effect whatsoever. [00110] EXAMPLES 7 AND 8

Inhibition of apoptosis induction

 Background: In contrast to necrosis, apoptosis is a natural targeted cell death of certain unwanted or damaged cells. It is an active process of cells (suicide on command). Skin aging in particular leads to induced apoptosis of the skin cells due to a lack of growth factors in the skin. In the cells affected by apoptosis, the specific enzyme endonuclease degrades the nuclear DNA and transports the DNA fragments into the cytoplasm.

Method: The ability of carnosines to prevent apoptosis in human skin cells induced by a lack of growth factors was investigated. On human fibroblasts and human keratinocytes, these assays were performed in vitro. The human cells were cultured in a nutrient medium (DMEM = Dulbecco Minimum Essential Medium from Life Technology Sari) with 10% fetal calf serum (from Dutcher). Bromodeoxyuridine (BrdU), which was incorporated into the DNA and later used to detect the DNA fragments in the cytoplasm, was added to this nutrient medium. After two days of incubation, the nutrient medium was changed to nutrient medium (DMEM) without fetal calf serum. The active substance to be tested was added. For comparison, a cell sample without active substance to be tested was incubated.

 After a further incubation period of one or two days at 37 ° C, the cells were recovered by trypsinization by the method of Dunnebacke and Zitcer described in: Cell and tissue culture, eds .: J. Paul, Churchill Livingstone, 1975 , P. 226. After trypsinization, the cells were centrifuged and counted. Subsequently, the content of BrdU in DNA fragments from the cytoplasm was determined by means of the ELISA test (ELISA kit from Roche). The content of BrdU is a measure of the DNA fragments that have been released from the nucleus, the nucleus, into the cytoplasm. The results were expressed in terms of one million cells and expressed as a percentage of the control. The results are summarized in the following Table 2.

Table 2

 Number of cells and content of DNA fragments

The in vitro examples show that the use of carnosines decreases apoptosis in human cell cultures and the content of free DNA fragments in the cytoplasm and thus the level of destroyed DNA in the nucleus. EXAMPLES 9 AND 10

 Stimulating the synthesis of dermal macromolecules (GAG)

 [00117] Background: The aim of these studies is to demonstrate a stimulating activity of carnosines on the synthesis of dermal macromolecules on human fibroblast cultures in vitro. The dermis is composed of cells (fibroblasts and mast cells), tissue components (collagen and elastin) and so-called basic substances. These basic substances include, for example, glycosaminoglycan (GAG), hyaluronic acid, chondroitin sulfate, dermatan sulfate and glycoproteins. Skin aging reduces the intermolecular solidification and elasticity of the dermis and thereby the firmness of the skin. Likewise, the number of skin cells present, in particular the fibroblasts, is reduced in the course of skin aging. The collagen fibers become fragmented over time and the proportion of insoluble to soluble collagen increases. Fine dermal elastic fibers are coarsened and destroyed. The synthesis of GAG (glycosaminoglycan) is reduced. All of these processes contribute to skin aging and its manifestations, such as wrinkles and the lack of firmness of the skin.

 Method: The measurement method is based on a staining of macromolecules in a culture of human fibroblasts, which builds up a collagen gel or collagen lattice fibers with type I collagen. Certain regions of these fibers are quantified by staining reagents on the proportion of said macromolecules.

For this purpose, a suspension of human fibroblasts mixed with a solution of collagen type I (1-2 mg / ml). This mixture was placed in a defined nutrient medium (DM EM = Dulbecco Minimum Essential Medium, Life Technology Sari Company) with 0.5 or 2 wt% fetal calf serum (FCS) at 37 ° C in a 5% C0 ₂ atmosphere in Petri dishes (5 ml per dish) with the addition of various concentrations of the plant extracts to be examined for 14 days incubated.

The kinetics of collagen gel concentration was determined 2 to 3 times a week by measuring two perpendicular diameters on each collagen gel with a microscope with image analysis system. The size of the area is shown in Table 8 in cm ² . After a 14-day incubation, the density of the collagen gel was determined by image analysis with a visible light source by comparing different gray levels. It is a relative determination of the density (0 = clear or white and l = black), which can not be provided with any unit.

 After 7 and after 14 days of incubation biopsies (tissue samples) were taken and obtained histological sections of the collagen gel with human fibroblasts. The synthesis of macromolecules was investigated and characterized by the staining of glycosaminoglycan with PAS-Alcian blue, e.g. from the company SIGMA according to the periodic acid-Schiff method (PAS), described in: Mowry RW, Anal. NY adad. Be. 106 Art. 2, 402, 1963, quantified. The assessment of the stimulation of the synthesis of macromolecules was carried out directly in the environment of fibroblasts. This zone is also referred to as a "perifibroblast surface".

A quantification of the "perifibroblast" secretion or the secretion of fibroblasts into the periphery was performed by means of an image analyzer by means of a microscope. Reactive structures were detected in the "perifibroblast surface" and the different gray levels were determined comparatively. The values of the Grayscale divided from 0 = white to 255 = black. These parameters are directly proportional to the intensity of the synthesis of macromolecules and thus to the GAG fraction of the fibroblasts.

 In the following Table 3 the results of the values of these parameters are shown and can be seen directly as representative values for the synthesis activity of the fibroblasts. The proportion of GAGs is described as the relative value of the gray scale.

Table 3

 Content of GAGs in tissue samples of human fibroblasts with collagen

 * 5% by weight Fetal Calf Serum (FCS)

 From the results of the determination of the proportion of glycosaminoglycan in tissue samples of collagen gel with fibroblasts, especially in the perifibroblast surface, a significant increase in the GAG fraction can be seen after 14 days incubation time compared to the standard with the addition of carnosines to a regenerating and revitalizing activity of carnosins on human fibroblasts.

EXAMPLES 11 AND 12

 [00127] Inhibition of elastase activity

Background: Elastase is a protease secreted by the fibroblasts in inflammatory conditions and is useful for the degradation of dermal macromolecules, e.g. Collagen and elastin and thus responsible for skin aging.

Method: To test the efficacy of the plant extract to inhibit the release of elastase, pancreatic elastase (a serine protease) was assayed and labeled as substrate elastin with a chromogenic synthetic substrate. The system was incubated with the drugs for 30 min at room temperature and then determined after centrifugation, the optical density of the dye at 410 nm. The amount used of the extracts was 0.3 percent by weight. The results are summarized in Table 4. The specification was relative to a control as standard (= 0%), as a standard served al-antitrypsin. [00130] Table 4

Elastase inhibitor

The results illustrate that carnosins are able to inhibit the elastase and especially the pancreatic elastase.

EXAMPLES 13 AND 14

 Inhibition of glycation of collagen.

To demonstrate that carnosines inhibit nonenzymatic glycation of macromolecules, Type I collagen was treated with glucose and the extracts at 45 ° C for a period of 21 days. Subsequently, the suspensions were centrifuged and the content of Schiff bases in the supernatant liquid was determined by fluorescence measurement at 430 nm. The results are summarized in Table 5. The data relate again to the control as standards (without extract and without glucose).

Table 5

 Inhibition of glycation of collagen

The in vitro results indicate that carnosins are able to inhibit the glycation of collagen and thus to slow down the aging process of the dermis by glycation of the collagen fibers.

In the following Table 6 a total of 10 example formulations are given. Table 6

 Skin care products

 (A) W / O Day Cream; (B-D) W / O Care Lotions; (E-G) O / W Care Lotions; (H-J) O / W Care Creams

Claims

1. A preparation comprising at least one compound of the formula (I)

with the proviso that R 1 is H or CH ₃ and R 2 is H or COOH, or salts thereof, for use as a medicament for the prevention and / or treatment of degeneration and aging of the skin, not or not exclusively by the action be caused by light.

 Containing preparation

 (a) at least one compound of the formula (I)

with the proviso that Rl is H or _CH3 and R2 is H or COOH, or their salts, and

 (b) at least one UV sun protection factor

 for use as a medicament for the prevention and / or treatment of degeneration and aging of the skin, which are not or not exclusively caused by the action of light.

Preparation according to Claim 1 or Claim 2, characterized in that the compound of the formula (I) is selected from the group formed by carnosine, L-carnosine, D-carnosine, D / L-carnosine, carnicin, carnicin * HCI, anserine, D-anserine, L-anserine and L-anserine * HN0 ₃ and mixtures thereof.

 Preparation according to claims 2 and / or 3, characterized in that the UV sun protection factors are selected from the group formed by UV filters, UV-B filters and sunscreen pigments.

 A preparation according to claim 4, characterized in that the UV-A filters are selected from the group consisting of benzoylmethane and enamine compounds and mixtures thereof.

 A preparation according to claim 4, characterized in that the UV-B filters are selected from the group formed by 3-Benzylidencampher or 3-Benzylidennorcampher and its derivatives, 4-aminobenzoesäurederivaten, esters of cinnamic acid, esters of salicylic acid, derivatives benzophenone, esters of benzalmalonic acid, triazine derivatives, propane-1,3-diones, ketotricyclo (5.2.1.0) decane derivatives, 2-phenylbenzimidazole-5-sulfonic acid and salts thereof; Sulfonic acid derivatives of benzophenones, sulfonic acid derivatives of the 3-benzylidene camphor and mixtures thereof.

 A preparation according to claim 4, characterized in that the sunscreen pigments are selected from the group formed by zinc oxide, titanium dioxide, iron oxide (s), zirconium oxide, silicon dioxide, manganese oxide, alumina, cerium oxide, silicates, barium sulfate and zinc stearate and mixtures thereof ,

 Preparation according to at least one of claims 1 to 7, characterized in that as optional component (c) carriers are included.

 A preparation according to claim 8, characterized in that the carriers are selected from the group consisting of water, alcohols, esters, butylene glycol, dipropylene glycol, ethanol, ethoxy diglycol, ethyl acetate, glycerol, propanol, isopropanol, macrogols, propyl propylene glycol (2 ) methyl ether, propylpropylene glycol (3) methyl ether, propylene carbonate, propylene glycol, triethylene glycol, isoparaffin, amyl acetate, amyl benzoate, benzyl acetate, butyl acetate, butylene glycol, butyl lactate, butooctyl benzoate, butooctyl salicylate, C10-C13 alkanes, C14-C17 alkanes, C11-C15 cycloalkanes , Caprylyl butyrate, isoparaffins, diacetin, triacetin dicaprylyl ether, dicaprylyl maleate, and mixtures thereof.

 Preparation according to at least one of claims 1 to 9, characterized in that it contains the component in an amount of 0.001 to about 5 wt .-% - based on the preparation.

Cosmetic compositions for the treatment of degeneration and in particular skin aging, which are not or not exclusively based on exposure to light (a) at least one compound of the formula (I)

 (L)

with the proviso that Rl is H or _CH3 and R2 is H or COOH, or their salts, and

 (B) at least one UV sun protection factor, preferably at least one UV-A and at least one UV-B sun protection factor, and optionally

(cl) carrier,

 (c2) oil body and / or

 (c3) emulsifiers

 12. A composition according to claim 11, characterized in that they contain the component (a) based on the total composition in amounts of 0.001 to about 5 wt .-%.

13. A non-therapeutic method for the prevention and / or treatment of human skin against signs of degeneration and aging, which are not or not exclusively caused by the influence of light, wherein a preparation according to claim 1, a preparation according to claim 2 or an agent according to claim 11 topically applied.

 14. The method according to claim 14, characterized in that applying the preparations or compositions once or twice daily over a period of 7 to 14 days.

15. Use of at least one compound of the formula (I)

with the proviso that R 1 is H or CH ₃ and R 2 is H or COOH, or their salts for the prevention and / or treatment of degeneration and aging of the human skin, which are not or not exclusively caused by the influence of light.