WO2000044340A1

WO2000044340A1 - Cosmetic and/or pharmaceutical preparations

Info

Publication number: WO2000044340A1
Application number: PCT/EP2000/000382
Authority: WO
Inventors: Rolf Kawa; Bernd Fabry
Original assignee: Cognis Deutschland Gmbh
Priority date: 1999-01-28
Filing date: 2000-01-19
Publication date: 2000-08-03
Also published as: DE19904329A1; AU2438400A

Abstract

The invention relates to cosmetic and/or pharmaceutical preparations containing (a) UV-A filters having an enamine structure, and (b) oil components and/or emulsifiers with a polarity of between 1.0 and 4.0 Debye. The above compositions are characterized in that they are especially photostable.

Description

Cosmetic and / or pharmaceutical preparations

Field of the Invention

The invention is in the field of sunscreens and relates to new preparations which contain UV-A filters of the enamine type together with oil bodies and / or emulsifiers of a defined polarity.

State of the art

The cosmetic sun protection products not only protect human skin from the direct consequences of UV-A and UV-B radiation, i.e. against sunburn, but also against the indirect consequences in the form of skin aging and skin cancer. For this reason, organic filter substances are generally used which, due to their chemical structure, are able to absorb ultraviolet light. The absorption of UV radiation causes electrons in the filter molecule to be excited. The energy absorbed is then released again in the form of heat radiation, with photostable molecules returning to their energetic ground state, while a photo-unstable filter undergoes a chemical change, such as isomerization or radical degradation.

Protection against UV-A radiation in particular is becoming increasingly important, since this form of radiation penetrates into the deeper layers of the skin and can trigger phototoxic and photoallergic reactions that damage the cells. The latest studies have shown, for example, that irreversible light damage in the form of connective tissue degeneration, skin carcinomas and spinalomas are possible. A particularly effective UV-A filter on the market is the butyl methoxydibenzoylmethane, which however has only a low photostability. To date, 12 degradation products have been known for this molecule, although there is as yet no reliable knowledge of the phototoxic potential of these substances. For the user of sunscreens, the existence of a certain sensitization potential cannot be ruled out.

An interesting alternative to butyl methoxydibenzoylmethane are enamine derivatives, as are described, for example, in German patent application DE 19712033 A1 (BASF). Although these substances have a high level of photostability, they do not reach the 100% mark required by the cosmetics industry. Accordingly, the task of the present invention It consisted in making available new preparations based on the filters mentioned, which have a photostability greater than 98%.

Description of the invention

The invention relates to cosmetic and / or pharmaceutical preparations containing

(a) Enamine type UV-A filter and

(b) Oil components and / or emulsifiers with a polarity in the range from 1 to 4, preferably 1.5 to 3.5 Debye.

Surprisingly, it was found that the combination of the special UV-A filters with cosmetic ingredients of a defined polarity inhibits the photo degradation, while when mixed with substances, for example of a lower polarity, the photostability is further reduced.

UV-A filter

The UV-A filters with enamine structure to be used as component (a) are known substances which are described, for example, in the German patent application DE 19712033 A1 already mentioned at the beginning. The filters preferably follow the formula (I)

(I)

in which the double bond is in the E or Z configuration and R ¹ for COOR ⁵ , COR ⁵ , CONR5R6, CN, 0 = S (-R5) = 0, 0 = S (-OR5) = 0,

R ² for COOR ⁶ , COR ⁶ , CONR ⁵ R ⁶ , CN, 0 = S (-R ⁶ ) = 0, 0 = S (-OR ⁶ ) = 0, R ⁸ 0-P (-OR ⁷ ) = 0 R ³ for hydrogen, an optionally substituted aliphatic, cycloaliphatic, araliphatic or aromatic radical each having up to 18 carbon atoms, R ⁴ for an optionally substituted aromatic or heteroaromatic radical having 5 to 12 ring atoms, and R ⁵ to R ⁸ independently of one another hydrogen, are an open-chain or branched aliphatic, araliphatic, cycloaliphatic or optionally substituted aromatic radical each having up to 18 carbon atoms, the radicals R ³ to R ^{8 being} among one another, in each case together with the carbon atoms to which they are attached. are bound, can together form a 5- or 6-ring, which can optionally be fused further.

In a preferred embodiment of the invention, the agents contain UV-A filters of the formula (I) in which, R ³ for hydrogen, R ¹ for CN, COOR ⁵ and COR ⁵ and R ² for CN, COOR ⁶ and COR ⁶ stand, wherein R ⁵ and R ⁶ independently of one another are open-chain or branched aliphatic or optionally substituted aromatic radicals having up to 8 carbon atoms. Particularly preferred are compounds of formula (I) in which R ^{3 is} hydrogen, R ^{1 is} CN, COOR ⁵ and COR ⁵ and R ^{2 is} CN, COOR ⁶ and COR ⁶ , where R ⁵ and R ⁶ are independently open-chain or are branched aliphatic or optionally substituted aromatic radicals having up to 8 carbon atoms and R ^{4 is} an optionally substituted aromatic or heteroaromatic radical having up to 10 carbon atoms in the ring, in particular a substituted phenyl, thienyl, furyl, pyridyl, indolyl or naphthylene and particularly preferably represents an optionally substituted phenyl or thienyl radical. Both lipophilic and hydrophilic substituents with, for example, up to 20 carbon atoms are suitable as substituents. Lipophilic, ie the oil-solubility of the compounds of the formula (I) enhancing residues are, for example, aliphatic or cycloaliphatic residues, in particular alkyl residues with 1 to 18 carbon atoms, alkoxy, mono- and dialkylamino, alkoxycarbonyl, mono- and dialkylaminocarbonyl, mono - and Dialkylaminosulfonylreste, also cyano, nitro, bromine, chlorine, iodine or fluorine substituents. Hydrophilic, ie the water-solubility of the compounds of the formula (I) are, for example, carboxy and sulfoxy radicals and in particular their salts with any physiologically compatible cations, such as the alkali metal salts or as the trialkylammonium salts, such as tri (hydroxyalkyl) ammonium salts or the 2-methylpropane -1-ol-2-ammonium salts. Alkyl ammonium residues with any physiologically compatible anions are also suitable. Suitable alkoxy radicals are those having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms. For example, the following residues should be mentioned:

• methoxy isopropoxy

N-propoxy-1-methylpropoxy-

N-butoxy-n-pentoxy-

• 2-methylpropoxy- 3-methylbutoxy-

1,1-dimethylpropoxy- 2,2-dimethylpropoxy-

Hexoxy-1-methyl-1-ethylpropoxy-

• heptoxy- octoxy-

• 2-ethylhexoxy

Examples of suitable mono- or dialkylamino radicals are those which contain alkyl radicals having 1 to 8 carbon atoms, such as methyl, n-propyl, n-butyl, 2-methylpropyl, 1, 1-dimethylpropyl, Hexyl, heptyl, 2-ethylhexyl, isopropyl, 1-methylpropyl, n-pentyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-methyl-1-ethylpropyl and octyl. These residues are contained equally in the mono- and dialkylaminocarbonyi and sulfonyl residues. Alkoxycarbonyl radicals are, for example, esters which contain the abovementioned alkoxy radicals or radicals of higher alcohols, for example having up to 20 carbon atoms, such as iso-Ci5 alcohol.

Oil components and emulsifiers

With regard to the selection of the oil components and emulsifiers, their polarity is the decisive criterion. The dipole moment of the substances in question can be determined, for example, by the formula from Onsager [cf. Soap-oil-fat waxes, 115, 459-61 (1989)] can be calculated.

Guerbet alcohols based on fatty alcohols having 6 to 18, preferably 8 to 10 carbon atoms, esters of branched C6-Ci3 carboxylic acids with linear C6-C22 fatty alcohols, esters of linear C6-C22 fatty acids with branched come in particular as oil components of the required polarity Alcohols, in particular 2-ethylhexanol, esters of hydroxycarboxylic acids with linear or branched C6-C22 fatty alcohols, especially dioctyl malates, esters of linear and / or branched fatty acids with polyhydric alcohols (such as propylene glycol, dimer diol or trimer triol) and / or Guerbet alcohols , liquid mono- / di- / triglyceride mixtures based on Cε-Ciβ fatty acids, esters of C6-C22 fatty alcohols and / or Guerbet alcohols with aromatic carboxylic acids, in particular benzoic acid, esters of C∑-Ci D dicarboxylic acids with linear or branched alcohols with 1 to 22 carbon atoms or polyols with 2 to 10 carbon atoms and 2 to 6 hydroxyl groups primary alcohols, substituted cyclohexanes, linear and branched C6-C22 fatty alcohol carbonates, Guerbet carbonates, esters of benzoic acid with linear and / or branched C6-C22 alcohols (e.g. Finsolv® TN), linear or branched, symmetrical or asymmetrical dialkyl ethers with 6 to 22 carbon atoms per alkyl group, ring opening products of epoxidized fatty acid esters with polyols.

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

(1) Adducts of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide with linear fatty alcohols with 8 to 22 C atoms, with fatty acids with 12 to 22 C atoms and with alkylphenols with 8 to 15 C atoms in the Alkyl group;

(2) Ci2.i8 fatty acid monoesters and diesters of addition products of 1 to 30 moles of ethylene oxide with glycerol; (3) sorbitan mono- and diesters of saturated and unsaturated fatty acids having 6 to 22 carbon atoms and their ethylene oxide addition products;

(4) alkyl mono- and oligoglycosides with 8 to 22 carbon atoms in the alkyl radical and their ethoxylated analogs;

(5) polyglycerol esters, e.g. Polyglycerol polyyricinoleate, polyglycerol poly-12-hydroxystearate or polyglycerol dimer isostearate. Mixtures of compounds from several of these classes of substances are also suitable;

(6) partial esters based on linear, branched, unsaturated or saturated C6 / 22 fatty acids, ricinoleic acid and 12-hydroxystearic acid and glycerin, polyglycerin, sugar alcohols (e.g. sorbitol), alkyl glucosides (e.g. methyl glucoside, butyl glucoside, lauryl glucoside) and polyglucoside ( eg cellulose);

(7) mono-, di- and trialkyl phosphates as well as mono-, di- and / or tri-PEG-alkyl phosphates and their salts;

(8) wool wax alcohols;

(9) polyalkylene glycols and

(10) glycerine carbonate.

The adducts of ethylene oxide and / or of propylene oxide with fatty alcohols, fatty acids, alkylphenols, glycerol mono- and diesters and sorbitan mono- and diesters of fatty acids or with castor oil are known, commercially available products. These are mixtures of homologs, the middle of which Degree of alkoxylation corresponds to the ratio of the amounts of ethylene oxide and / or propylene oxide and substrate with which the addition reaction is carried out. Ci2 / i8 fatty acid monoesters and diesters of adducts of ethylene oxide with glycerol are known from DE 2024051 PS as refatting agents for cosmetic preparations.

Cβ / 18 alkyl mono- and oligoglycosides, their preparation and their use are known from the prior art. They are produced in particular by reacting glucose or oligosaccharides with primary alcohols with 8 to 18 carbon atoms. Regarding the glycoside residue, both monoglycosides in which a cyclic sugar residue is glycosidically bonded to the fatty alcohol and oligomeric glycosides with a degree of oligomerization of up to about 8 are suitable. The degree of oligomerization is a statistical mean value which is based on a homolog distribution customary for such technical products.

Zwitterionic surfactants can also be used as emulsifiers. Zwitterionic surfactants are surface-active compounds that contain 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- dimethylammonium glycinate, for example the cocoalkyldimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammoniumglycinate, for example the coconutacyaminopropyldimethylammonium glycinate, and 2-alkyl-3-carboxylmethyl-3-hydroxyethylimidazolines each with 8 to 18 carbon atoms in the 8 to 18 carbon atom group as well as the coconut acylaminoethyl hydroxyethyl carboxymethyl glycinate. The fatty acid amide derivative known under the CTFA name of Cocamidopropyl Betaine is particularly preferred. Suitable emulsifiers are ampholytic surfactants. Ampholytic surfactants are surface-active compounds which, in addition to a Cβ / .β-alkyl or acyl group, contain at least one free amino group and at least one -COOH or -Sθ3H group in the molecule and are capable of forming internal salts. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylamino acetic acids, each with about 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylamino propionate and Ci∑ / iβ-acylsarcosine. In addition to the ampholytic emulsifiers, quaternary emulsifiers are also suitable, those of the ester quat type, preferably methyl-quaternized di-fatty acid triethanolamine ester salts, being particularly preferred.

Industrial applicability

In a preferred embodiment of the invention, the cosmetic and / or pharmaceutical preparations contain

(a) 0.1 to 5, preferably 1 to 3 wt .-% UV-A filter with enamine structure and

(b) 0.5 to 50, preferably 5 to 25% by weight of oil components and / or emulsifiers with a polarity in the range from 1.0 to 4.0, preferably 1.5 to 3.5 Debye,

with the proviso that the quantities given add up to 100% by weight with water and possibly other auxiliaries and additives.

Cosmetic and / or pharmaceutical preparations

The agents according to the invention, such as, for example, creams, gels, lotions, alcoholic and aqueous / alcoholic solutions, emulsions, wax / fat compositions, stick preparations, powders or ointments, can also be used as further auxiliaries and additives, mild surfactants, superfatting agents, pearlescent agents. waxes, consistency agents, thickeners, polymers, silicone compounds, fats, waxes, stabilizers, biogenic agents, deodorant agents, antidandruff agents, film formers, swelling agents, other UV light protection factors, antioxidants, hydrotropes, preservatives, insect repellents, self-tanners, solubilizers, perfume oils, dyes contain germicides and the like.

Typical examples of suitable mild, i.e. Surfactants that are particularly compatible with the skin are fatty alcohol polyglycol ether sulfates, monoglyceride sulfates, mono- and / or dialkyl sulfosuccinates, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, fatty acid glutamates, α-olefin sulfonates, ether carboxylic acids, alkyl oligoglamidoblettides, fatty acid / alkyl oligoglobucosides, fatty acids / fatty acids / fatty acids and / or fatty acids, fatty acids / fatty acids, fatty acids, fatty acids, fatty acids, fatty acids, fatty acids, fatty acids, fatty acids, fatty acids, fatty acids, fatty acids, fatty acids, fatty acids, fatty acids, fatty acids, fatty acids, fatty acids Wheat proteins.

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

Pearlescent waxes, for example, are: alkylene glycol esters, especially ethylene glycol distearate; Fatty acid alkanolamides, especially coconut fatty acid diethanoiamide; Partial glycerides, especially stearic acid monoglyceride; Esters of polyvalent, 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 have a total of at least 24 carbon atoms, especially lauron and distearyl ether; Fatty acids such as stearic acid, hydroxystearic acid or behenic acid, ring opening products of olefin epoxides with 12 to 22 carbon atoms with fatty alcohols with 12 to 22 carbon atoms and / or polyols with 2 to 15 carbon atoms and 2 to 10 hydroxyl groups and mixtures thereof.

Suitable consistency agents are primarily fatty alcohols or hydroxy fatty alcohols with 12 to 22 and preferably 16 to 18 carbon atoms and, in addition, partial glycerides, fatty acids or hydroxy fatty acids. A combination of these substances with alkyl oligoglucosides and / or fatty acid N-methyl glucamides of the same chain length and / or polyglycerol poly-12-hydroxystearates is preferred. Suitable thickeners are, for example, Aerosil types (hydrophilic silicas), polysaccharides, in particular xanthan gum, guar guar, agar agar, alginates and tyloses, carboxymethyl cellulose and hydroxyethyl cellulose, and also higher molecular weight polyethylene glycol mono- and diesters of fatty acids, Polyacrylates (e.g. Carbopole® from Goodrich or Synthalene® from Sigma), poly-acrylamides, polyvinyl alcohol and polyvinyl pyrrolidone, surfactants such as for example ethoxylated fatty acid glycerides, esters of fatty acids with polyols such as pentaerythritol or trimethylolpropane, fatty alcohol ethoxylates with a narrow homolog distribution or alkyl oligoglucosides and electrolytes such as sodium chloride and ammonium chloride.

Suitable cationic polymers are, for example, cationic cellulose derivatives, e.g. a quaternized hydroxyethyl cellulose available under the name Polymer JR 400® from Amerchol, cationic starch, copolymers of diallylammonium salts and acrylamides, quaternized vinylpyrrolidone / vinylimidazole polymers such as e.g. Luviquat® (BASF), condensation products of polyglycols and amines, quaternized collagen polypeptides, such as lauryldimonium hydroxypropyl hydrolyzed collagen (Lamequat®L / Grünau), quaternized wheat polypeptides, polyethyleneimine, cationic silicone polymers, e.g. Amidomethicones, copolymers of adipic acid and dimethylaminohydroxypropyldiethylenetriamine (Cartaretine® / Sandoz), copolymers of acrylic acid with dimethyldiallylammonium chloride (Merquat® 550 / Chemviron), polyamino polyamides, e.g. described in FR 2252840 A and its crosslinked water-soluble polymers, cationic chitin derivatives such as, for example, quaternized chitosan, optionally microcrystalline, condensation products from dihaloalkylene, such as e.g. Dibromobutane with bisdialkylamines, 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 esters thereof, uncrosslinked and polyol-crosslinked polyacrylic acids, acrylamidopropyl - Trimethylammonium chloride / acrylate copolymers, octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxyproyl methacrylate copolymers, polyvinylpyrrolidone, vinylpyrrolidone / vinyl acetate copolymers, vinylpyrrolidone / dimethylaminoethyl methamylate and copolymerized vinylpolymer as well as vinylpolysulfate and also polyvinyl acrylate and polyacrylate as well as derivatives of vinylpolymers as well as vinylpolysulfate as well as derivatized vinylpolysulfate as well as derivatized vinylpolymers and copolymers.

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 can be both liquid and resinous at room temperature. Simethicones, which are mixtures of dimethicones with an average chain length of 200 to 300 dimethylsiloxane units and hydrogenated silicates, are also suitable. A detailed overview of suitable volatile silicones can also be found by Todd et al. in Cosm.Toil. 91, 27 (1976). Typical examples of fats are glycerides; waxes include beeswax, carnauba wax, candelilla wax, montan wax, paraffin wax, hydrogenated castor oils, fatty acid esters or microwaxes which are solid at room temperature, optionally in combination with hydrophilic waxes, for example cetylstearyl alcohol or partial glycerides. Metal salts of fatty acids such as magnesium, aluminum and / or zinc stearate or ricinoleate can be used as stabilizers.

Biogenic active substances are, for example, tocopherol, tocopherol acetate, tocopherol palmitate, ascorbic acid, deoxyribonucleic acid, retinol, bisabolol, allantoin, phytantriol, panthenol, AHA acids, amino acids, ceramides, pseudoceramides, essential oils, plant extracts and vitamin complexes.

Antiperspirants such as aluminum chlorohydates are suitable as deodorant active ingredients. These are colorless, hygroscopic crystals that easily dissolve in the air and arise when aqueous aluminum chloride solutions are evaporated. Aluminum chlorohydrate is used in the manufacture of antiperspirant and deodorant preparations and is likely to act by partially occluding the sweat glands through protein and / or polysaccharide precipitation [cf. J. Soc. Cosm.Chem. 24, 281 (1973)]. For example, an aluminum chlorohydrate that corresponds to the formula [Al2 (OH) 5CI] * 2.5 H2O and whose use is particularly preferred is commercially available under the brand Locron® from Hoechst AG, Frankfurt / FRG [cf. J.Pharm.Pharmacol. 26, 531 (1975)]. In addition to the chlorohydrates, aluminum hydroxyl octates and acidic aluminum / zirconium salts can also be used. Esterase inhibitors can be added as further deodorant active ingredients. These are preferably trialkyl citrates such as trimethyl citrate, tripropyl citrate, triisopropyl citrate, tributyl citrate and in particular triethyl citrate (Hydagen® CAT, Henkel KGaA, Düsseldorf / FRG). The substances inhibit enzyme activity and thereby reduce odor. The cleavage of the citric acid ester probably releases the free acid, which lowers the pH value on the skin to such an extent that the enzymes are inhibited. Other substances which can be considered as esterase inhibitors are sterol sulfates or phosphates, such as, for example, lanosterol, cholesterol, campesterin, stigmasterol and sitosterol sulfate or phosphate, dicarboxylic acids and their esters, such as, for example, glutaric acid, glutaric acid monoethyl ester, glutaric acid diethyl ester, Adipic acid, adipic acid monoethyl ester, adipic acid diethyl ester, malonic acid and malonic acid diethyl ester, hydroxycarboxylic acids and their esters such as citric acid, malic acid, tartaric acid or tartaric acid diethyl ester. Antibacterial agents that influence the bacterial flora and kill sweat-killing bacteria or inhibit their growth can also be contained in the stick preparations. Examples include chitosan, phenoxyethanol and chlorhexidine gluco- nat. 5-Chloro-2- (2,4-dichlorophen-oxy) phenol, which is sold under the Irgasan® brand by Ciba-Geigy, Basel / CH, has also proven to be particularly effective.

Climbazole, octopirox and zinc pyrethione can be used as antidandruff agents. Common film formers are, for example, chitosan, microcrystalline chitosan, quaternized chitosan, polyvinyl ipyrrolidone, vinyl pyrrolidone / vinyl acetate copolymers, polymers of the acrylic acid series, quaternary cellulose derivatives, collagen, hyaluronic acid or its salts and similar compounds. Montmorillonites, clay minerals, pemulene and alkyl-modified carbopol types (Goodrich) can serve as swelling agents for aqueous phases. Further suitable polymers or swelling agents can be found in the overview by R. Lochhead in Cosm.Toil. 108, 95 (1993).

UV light protection factors are understood to mean, for example, organic substances (light protection filters) which are liquid or crystalline at room temperature and which are able to absorb ultraviolet rays and absorb the energy absorbed in the form of longer-wave radiation, e.g. To give off heat again. UVB filters can be oil-soluble or water-soluble. As oil-soluble substances e.g. to call:

3-benzylidene camphor or 3-benzylidene norcampher and its derivatives, e.g. 3- (4-methylbenzylidene) camphor as described in EP 0693471 B1;

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

• esters of cinnamic acid, preferably 2-ethylhexyl 4-methoxycinnamate, propyl 4-methoxycinnamate, isoamyl 4-methoxycinnamate 2-ethyl-2-cyano-3,3-phenylcinnamate (octocrylene);

• esters of salicylic acid, preferably 2-ethylhexyl salicylate, 4-isopropylbenzyl salicylate, homomethyl salicylic acid;

• 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) -1, 3,5-triazine and octyl triazone, as described in EP 0818450 A1;

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

• Ketotricyclo (5.2.1.0) decane derivatives, as described in EP 0694521 B1.

Possible water-soluble substances are: • 2-phenylbenzimidazole-5-sulfonic acid and its alkali, alkaline earth, ammonium, alkylammonium, alkanolammonium and glucammonium salts;

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

Sulfonic acid derivatives of 3-benzylidene camphor, e.g. 4- (2-oxo-3-bomylidene methyl) benzenesulfonic acid and 2-methyl-5- (2-oxo-3-bomylidene) sulfonic acid and their salts.

Derivatives of benzoylmethane, such as 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1, 3-dione, 4-tert-butyl, are particularly suitable as typical UV-A filters -4'-methoxy-dibenzoylmethane (Parsol 1789), or 1-phenyl-3- (4'-isopropylphenyl) propane-1,3-dione. The UV-A and UV-B filters can of course also be used in mixtures. In addition to the soluble substances mentioned, insoluble light protection 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. Silicates (talc), barium sulfate or zinc stearate can be used as salts. 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 particles which have an ellipsoidal shape or shape which differs from the spherical shape in some other way. The pigments can also be surface treated, i.e. are hydrophilized or hydrophobized. Typical examples are coated titanium dioxides, e.g. Titanium dioxide T 805 (Degussa) or Eusolex® T2000 (Merck). Silicones, and in particular trialkoxyoctylsilanes or simethicones, are particularly suitable as hydrophobic coating agents. So-called micro- or nanopigments are preferably used in sunscreens. Micronized zinc oxide is preferably used. Further suitable UV light protection filters can be found in the overview by P.Finkel in SÖFW-Journal 122, 543 (1996).

In addition to the two aforementioned groups of primary light stabilizers, secondary light stabilizers of the antioxidant type can also be used, which interrupt the photochemical reaction chain which is triggered when UV radiation penetrates the skin. Typical examples are amino acids (e.g. glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles (e.g. urocanic acid) and their derivatives, peptides such as DL-carnosine, D-camosine, L-carosene and their derivatives (e.g. anserine) , Carotenoids, carotenes (eg α-carotene, β-carotene, lycopene) and their derivatives, chlorogenic acid and their derivatives, lipoic acid and their derivatives (eg dihydroliponic acid), aurothioglucose, propylthiouracil and other thiols (eg thioredoxin, glu tathione, cysteine, cystine, cystamine and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl, γ-linoleyl, cholesteryl and glyceryl esters ) as well as their salts, dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and their derivatives (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) as well as sulfoximine compounds (e.g. buthioninsulfoximines, homocysteine sulfoximine, butioninsulfones, penta-, hexa- sulfinoxin, heptathione) low tolerable doses (e.g. pmol to μmol / kg), also (metal) chelators (e.g. α-hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin), α-hydroxy acids (e.g. 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 their derivatives, ubiquinone and ubiquinol and their derivatives, vitamin C and derivatives (e.g. ascorbyl palmitate, Mg ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives (e.g. vitamin E acetate), vitamin A and derivatives (vitamin A palmitate) and coniferyl benzoate of benzoin, rutinic acid and their derivatives , α-glycosylrutin,

Ferulic acid, furfurylidene glucitol, carnosine, butylated hydroxytoluene, butylated hydroxyanisole, nordihydrogu ayak resin acid, nordihydroguajaretic acid, trihydroxybutyrophenone, uric acid and its derivatives, mannose and its derivatives, superoxide dismutase, zinc and its derivatives (eg ZnO, selenium and its selenium (eg ZnO selenium, selenium (eg ZnO selenium, Methionine), stilbenes and their derivatives (for example stilbene oxide, trans-stilbene oxide) and the derivatives suitable according to the invention (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids) of these active substances.

Hydrotropes such as ethanol, isopropyl alcohol or polyols can also be used to improve the flow behavior. Polyols that come into consideration here preferably have 2 to 15 carbon atoms and at least two hydroxyl groups. The polyols can also contain further functional groups, in particular amino groups, or be modified with nitrogen. Typical examples are

• glycerin;

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

Technical oligoglycerol mixtures with a degree of self-condensation of 1.5 to 10, such as technical diglycerol mixtures with a diglycerol content of 40 to 50% by weight;

• Methyl compounds, such as, in particular, trimethylolethane, trimethylolpropane, trimethyl-olbutane, pentaerythritol and dipentaerythritol;

• Lower alkyl glucosides, in particular those with 1 to 8 carbons in the alkyl radical, such as methyl and butyl glucoside;

Sugar alcohols with 5 to 12 carbon atoms, such as sorbitol or mannitol, • Sugar with 5 to 12 carbon atoms, such as glucose or sucrose;

Aminosugars, such as glucamine;

• Dialcohol amines, such as diethanolamine or 2-amino-1, 3-propanediol.

Suitable preservatives are, for example, phenoxyethanol, formaldehyde solution, parabens, pentanediol or sorbic acid and the other classes of substances listed in Appendix 6, Parts A and B of the Cosmetics Ordinance. N, N-diethyl-m-toluamide, 1, 2-pentanediol or 3535 insect repellants are suitable as insect repellants, and dihydroxyacetone is suitable as a self-tanning agent.

Perfume oils include 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 (anise, coriander, caraway, juniper), fruit peel (bergamot, lemon, Oranges), roots (mace, angelica, celery, cardamom, costus, iris, calmus), wood (pine, sandal, guaiac, cedar, rosewood), herbs and grasses (tarragon, lemongrass, sage, thyme), Needles and twigs (spruce, fir, pine, mountain pine), resins and balms (galbanum, elemi, benzoin, myrrh, olibanum, opoponax). Animal raw materials, such as civet and castoreum, are also suitable. Typical synthetic fragrance compounds are products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methyl phenylglycinate, allylcyclohexylpropylate propylate allyl propylate propionate. The ethers include, for example, benzyl ethyl ether, the aldehydes include, for example, the linear alkanals having 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxy-citronellal, lilial and bourgeonal, and the ketones include, for example, the jonones, oc-isomethyl ionone and methyl cedryl ketone 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 appealing fragrance. Essential oils of low volatility, which are mostly used as aroma components, are also suitable as perfume oils, e.g. sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, oliban oil, galbanum oil, labolanum oil and lavandin oil. Bergamot oil, dihydromyrcenol, lilial, lyral, citronellol, phenylethyl alcohol, α-hexylcinnamaldehyde, geraniol, benzylacetone, cyclamenaldehyde, linalool, boisambrene forte, ambroxan, indole, hedione, sandelice, lemon oil, manidinenlylamine oil, cyclone oil, orange aldol oil, orange glycolate, orange oil, are preferred , Muscatel sage oil, ß-mascone, geranium oil bourbon, cyclohexyl salicylate, Vertofix Coeur, Iso-E-Super, Fixolide NP, Evernyl, Iraldein gamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, Romilllat, Irotyl and Floramat used alone or in mixtures.

The dyes which can be used are those substances which are suitable and approved for cosmetic purposes, as compiled, for example, in the publication "Cosmetic Dyes" by the Dye Commission of the German Research Foundation, Verlag Chemie, Weinheim, 1984, pp. 81-106. These dyes are usually used in concentrations of 0.001 to 0.1% by weight, based on the mixture as a whole.

Typical examples of germ-inhibiting agents are preservatives with a specific action against gram-positive bacteria, such as, for example, 2,4,4'-trichloro-2'-hydroxydiphenyl ether, chlorhexidine (1,6-di- (4-chlorophenyl-biguanido) hexane) or TCC (3,4,4'-trichlorocarbanilide). Numerous fragrances and essential oils also have antimicrobial properties. Typical examples are the active ingredients eugenol, menthol and thymol in clove, mint and thyme oil. An interesting natural deodorant is the terpene alcohol farnesol (3,7, 11-trimethyl-2,6,10-dodecatrien-1 -ol), which is present in linden blossom oil and has a lily of the valley smell. Glycerol monolaurate has also proven itself as a bacteriostatic. The proportion of the additional germ-inhibiting agents is usually about 0.1 to 2% by weight, based on the solids content of the preparations.

The total proportion of auxiliaries and additives can be 1 to 50, preferably 5 to 40,% by weight, based on the composition. The agents can be produced by customary cold or hot processes; the phase inversion temperature method is preferably used.

Examples

The photostability of various UV-A filters, possibly in admixture with different oil components or emulsifiers, was determined by the method published by Merck on the occasion of the APV seminar from September 17-18, 1997 in Fulda. The results are summarized in Table 1. Examples 1 to 6 are according to the invention, examples V1 and V2 serve for comparison.

Table 1 Photostability

A number of formulation examples can be found in Table 2 below. Preparations 1, 3, 5, 9 to 11, 13, 16 and 21 to 22 are creams, all other lotions.

Table 2

Formulation examples (cont.) - quantities as% by weight

Claims

claims

1. Cosmetic and / or pharmaceutical preparations containing

(a) UV-A filter with enamine structure and

(b) Oil components and / or emulsifiers with a polarity in the range from 1.0 to 4.0 Debye.

2. Preparations according to claim 1, characterized in that they contain UV-A filters of the formula (I),

IIR ¹ -C = C-NH-R *

(I)

in which the double bond is in the E or Z configuration and R ¹ for COOR ⁵ , COR ⁵ , CONRSR6, CN, 0 = S (-R ⁵ ) = 0, 0 = S (-OR ⁵ ) = 0, R ⁸ 0 -P (-OR ⁷ ) = 0, R2 for COOR ⁶ , COR ⁶ , CONR ⁵ R6, CN, 0 = S (-R ⁶ ) = 0, 0 = S (-OR ⁶ ) = 0, R ⁸ 0- P (-OR ⁷ ) = 0, R ³ for hydrogen, an optionally substituted aliphatic, cycloaliphatic, araliphatic or aromatic radical each having up to 18 carbon atoms, R ⁴ for an optionally substituted aromatic or heteroaromatic radical having 5 to 12 ring atoms, and R ⁵ to R ⁸ independently of one another are hydrogen, an open-chain or branched aliphatic, araliphatic, cycloaliphatic or optionally substituted aromatic radical each having up to 18 carbon atoms, the radicals R ³ to R ^{8 being} among themselves, in each case together with the carbon atoms to which they are attached are, together can form a 5- or 6-ring, which may optionally be fused further.

3. Preparations according to claims 1 and / or 2, characterized in that they contain UV-AFilter of formula (I) in which R ³ for hydrogen, R ¹ for CN, COOR ⁵ and COR ⁵ and R ² for CN, COOR ⁶ and COR ⁶ stand, wherein R ⁵ and R ⁶ independently of one another are open-chain or branched aliphatic or optionally substituted aromatic radicals having up to 8 carbon atoms.

4. Preparations according to at least one of claims 1 to 3, characterized in that they contain UV-A filters of the formula (I) in which R ^{4 represents} phenyl optionally substituted by hydrophilic or lipophilic substituents.

5. Preparations according to claim 4, characterized in that R ^{4 represents} an alkoxyphenyl or alkoxycarbonylphenyl radical.

6. Preparations according to claim 4, characterized in that R ^{4 represents} a phenyl radical which carries water-solubilizing substituents selected from the group consisting of carboxylate, sulfonate or ammonium radicals.

7. Preparations according to at least one of claims 1 to 6, characterized in that they contain oil components which are selected from the group formed by Guerbet alcohols based on fatty alcohols having 6 to 18 carbon atoms, esters of branched C6-Ci3-carboxylic acids with linear C6-C22 fatty alcohols, esters of linear Cδ-C22 fatty acids with branched alcohols, esters of hydroxycarboxylic acids with linear or branched C6-C22 fatty alcohols, esters of linear and / or branched fatty acids with polyhydric alcohols and / or Guerbet alcohols, liquid Mono- / di- / triglyceride mixtures based on C6-Ci8 fatty acids, esters of C6-C22 fatty alcohols and / or Guerbet alcohols with aromatic carboxylic acids, esters of C2-Ci2 dicarboxylic acids with linear or branched alcohols with 1 to 22 carbon atoms or polyols with 2 to 10 carbon atoms and 2 to 6 hydroxyl groups, branched primary alcohols, substituted cyclohex anen, linear and branched C6-C22 fatty alcohol carbonates, Guerbet carbonates, esters of benzoic acid with linear and / or branched C6-C22 alcohols, linear or branched, symmetrical or asymmetrical dialkyl ethers with 6 to 22 carbon atoms per alkyl group and ring opening products of epoxidized fatty acid esters with polyols.

8. Preparations according to at least one of claims 1 to 7, characterized in that they contain nonionic emulsifiers which are selected from the group formed by addition products of 2 to 30 mol of ethylene oxide and / or 0 to 5 mol of propylene oxide with linear fatty alcohols with 8 to 22 carbon atoms, on fatty acids with 12 to 22 carbon atoms and on alkylphenols with 8 to 15 carbon atoms in the alkyl group; Ci2 i8 fatty acid mono- and diesters of adducts of 1 to 30 moles of ethylene oxide with glycerol; Sorbitan mono- and diesters of saturated and unsaturated fatty acids having 6 to 22 carbon atoms and their ethylene oxide addition products; Alkyl mono- and oligoglycosides with 8 to 22 carbon atoms in the alkyl radical and their ethoxylated analogs; Polyglycerol esters, partial esters based on linear, branched, unsaturated or saturated Ce / 22 fatty acids, ricinoleic acid and 12-hydroxystearic acid and glycerol, polyglycerol, sugar alcohols, alkyl glucosides and polyglucosides; Mono-, di- and trialkyl phosphates as well as mono- , Di- and / or tri-PEG-alkyl phosphates and their salts; Wool wax alcohols; Polyalkylene glycols and glycerine carbonate.

9. Preparations according to at least one of claims 1 to 8, characterized in that they contain anionic, cationic and / or zwitterionic emulsifiers.

10. Preparations according to at least one of claims 1 to 9, characterized in that they

(a) 0.1 to 5 wt .-% UV-A filter with enamine structure and

(b) 0.5 to 50% by weight of oil components and / or emulsifiers with a polarity in the range from 1.0 to 4.0 Debye

contain, with the proviso that the amounts with water and optionally other auxiliaries and additives add up to 100 wt .-%.