DE19904329A1 - Cosmetic and / or pharmaceutical preparations - Google Patents

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

Field of the Invention

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

State of the art

The cosmetic sun protection products not only protect human skin from the direct ones Consequences of UV-A and UV-B radiation, i.e. before sunburn, but also before the indirect consequences in the form of skin aging and skin cancer. That is why organic filter substances are usually used used, which due to their chemical structure are able to absorb ultraviolet light. By absorbing the UV radiation, electrons are excited into the filter molecule stood staggered. The energy absorbed is then in the form of heat radiation which releases, with photostable molecules returning to their energetic ground state In the case of photo-unstable filters, a chemical change occurs, such as an isomer or a radical breakdown.

Protection against UV-A radiation in particular is becoming increasingly important as this form the radiation penetrates into the deeper skin layers and thereby cell-damaging phototoxic so how photoallergic reactions can trigger. The latest studies show, for example, that irreversible light damage in the form of connective tissue degeneration, skin carcinomas and spinalomas possible are. A particularly effective UV-A filter on the market is the butyl methoxydibenzoyl methane, which however has only a low photostability. So far, 12 Ab known construction products, but so far no secured about the phototoxic potential of these substances Knowledge is available. For the user of sunscreen is therefore the existence of a ge know not to exclude sensitization potential.  

An interesting alternative to butyl methoxydibenzoylmethane are enamine derivatives like them can be described for example in German patent application DE 197 12 033 A1 (BASF).

Although these substances have a high level of photostability, they do not achieve that of the cosmetician industry demanded 100% mark. Accordingly, the object of the present invention is therein were able to provide new preparations based on the filters mentioned, which are a photo have a stability 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 filter with cosmetic Ingredients of a defined polarity inhibit the photo degradation, while mixed with For example, substances with a lower polarity further reduce the photostability.

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 aforementioned German patent application DE 197 12 033 A1. The filters preferably follow the formula (I)

in which the double bond is in the E or Z configuration and R ¹ for COOR ⁵ , COR ⁵ , CONR ⁵ R ⁶ , CN, O = S (-R ⁵ ) = O, O = S (-OR ⁵ ) = O, R ⁸ OP (-OR ⁷ ) = O, R ² for COOR ⁵ , COR ⁶ , CONR ⁵ R ⁶ , CN, O = S (-R ⁶ ) = O, O = S (-OR ⁶ ) = O , R ⁸ OP (-OR ⁷ ) = O, 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 rings 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 one another, in each case together with the carbon atoms, to which they are attached 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 is} hydrogen, R ^{1 is} CN, COOR ⁵ and COR ⁵ and R ^{2 is} 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 the 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 branched aliphatic or optionally substituted aromatic radicals having up to 8 carbon atoms and R ⁴ for 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 z. B. up to 20 carbon atoms. Lipophilic, ie the oil solubility of the compounds of formula (I) enhancing radicals are e.g. B. aliphatic or cycloaliphatic radicals, in particular alkyl radicals having 1 to 18 carbon atoms, alkoxy, mono- and dialkylamino, alkoxycarbonyl, mono- and dialkylaminocarbonyl, mono- and dialkylaminosulfonyl radicals, furthermore cyano, nitro, bromine, chlorine , Iodine or fluorine substituents. Hydrophilic, ie the water solubility of the compounds of formula (I) enabling residues are such. B. carboxy and sulfoxy radicals and especially their salts with any physiologically compatible cations, such as the alkali salts or as the trialkylammonium salts, such as tri- (hydroxyalkyl) ammonium salts or the 2-methylpropan-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

As mono- or dialkylamino come z. B. those that contain alkyl radicals with 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 dialkylaminocar bonyl and sulfonyl residues. Alkoxycarbonyl radicals are e.g. B. esters, the above Al koxy or residues of higher alcohols such. B. with up to 20 carbon atoms, such as iso-C ₁₅ alcohol.

Oil components and emulsifiers

With regard to the selection of the oil components and emulsifiers, their polarity is the decisive factor Criterion represents. The dipole moment of the substances in question can, for example, according to the formula by 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 C ₆ -C ₁₃ carboxylic acids with linear C ₆ -C ₂₂ fatty alcohols, esters of linear C ₆ -C ₄ come in particular as oil components of the required polarity ₂₂ fatty acids with branched alcohols, especially 2-ethylhexanol, esters of hydroxycarboxylic acids with linear or branched C ₆ -C ₂₂ 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 C ₆ -C ₁₈ fatty acids, esters of C ₆ -C ₂₂ fatty alcohols and / or Guerbet alcohols with aromatic carboxylic acids, especially benzoic acid, Esters of C ₂ -C ₁₂ 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 hyd roxyl groups, branched primary alcohols, substituted cyclohexanes, linear and branched C ₆ -C ₂₂ fatty alcohol carbonates, Guerbet carbonates, esters of benzoic acid with linear and / or branched C ₆ -C ₂₂ alcohols (e.g. B. Finsolv® TN), linear or branched, symmetrical or asymmetrical dialkyls ther with 6 to 22 carbon atoms per alkyl group, ring opening products of epoxidized fatty acid reesters with polyols.

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

• 1. Addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide to 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;
• 2. C _12/18 fatty acid _monoesters and diesters of adducts of 1 to 30 moles of ethylene oxide with glycerol;
• 3. Sorbitan mono- and diesters of saturated and unsaturated fatty acids with 6 to 22 carbons atoms of matter and their ethylene oxide addition products;  
• 4. Alkyl mono- and oligoglycosides with 8 to 22 carbon atoms in the alkyl radical and their ethoxy analogs;
• 5. Polyglycerol esters, such as. B. polyglycerol polyricinoleate, polyglycerol poly-12-hydroxystearate or Polyglycerol dimer isostearate. Mixtures of compounds of meh are also suitable reren of these substance classes;
• 6. Partial esters based on linear, branched, unsaturated or saturated C _6/22 fatty acids, ricinoleic acid and 12-hydroxystearic acid and glycerol, polyglycerol, sugar alcohols (e.g. sorbitol), alkyl glucosides (e.g. methyl glucoside, butyl glucoside, lauryl glucoside ) and polyglucosides (e.g. cellulose);
• 7. mono-, di- and trialkyl phosphates and mono-, di- and / or tri-PEG-alkyl phosphates and their Salts;
• 8. wool wax alcohols;
• 9. Polyalkylene glycols as well (10) glycerine carbonate.

The adducts of ethylene oxide and / or of propylene oxide with fatty alcohols, fatty acids, alkylphenols, glycerol mono- and diesters as well as sorbitan mono- and diesters with fatty acids or with castor oil are known, commercially available products. These are homologue mixtures whose average 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. C _12/18 - fatty acid monoesters and diesters of adducts of ethylene oxide with glycerol are known from DE 20 24 051 PS as refatting agents for cosmetic preparations.

C _8/18 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 ten-side means 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-dimethylam monium glycinate, for example the cocoalkyldimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammonium glycinate, for example the cocoacylaminopropyldimethylammonium glycinate, and 2-alkyl-3-carboxylate -hydroxyethylimidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and the cocoacylaminoethydroxyethylcarboxymethylglycinate. The fatty acid amide derivative known under the CTFA name of Cocamidopropyl Betaine is particularly preferred. Suitable emulsifiers are also ampholytic surfactants. Ampholytic surfactants are surface-active compounds which, in addition to a C _8/18 alkyl or acyl group, contain at least one free amino group and at least one -COOH or -SO ₃ H group in the molecule and are capable of forming internal salts are. Examples of suitable ampholytic surfactants are N-alkylglycine, N-alkylpropionic acid, N-alkylaminobutyric acid, N-alkyliminodipropionic acid, N-hydroxyethyl-N-alkylamidopropylglycine, N-alkyltaurine, N-alkyl sarcosine, 2-alkylaminopropionic acid and alkylaminoacetic acid each with about 8 to 18 C atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-coconut alkylaminopropionate, coconut acylaminoethylaminopropionate and C _12/18 acyl sarcosine. In addition to the ampholytic emulsifiers, quaternary emulsifiers are also suitable, those of the esterquat type, preferably methyl-quaternized difatty 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 wt .-% oil components and / or emulsifiers with a pola rity in the range of 1.0 to 4.0, preferably 1.5 to 3.5 debye,

with the proviso that the quantities indicated with water and possibly other auxiliary and Add additives to 100% by weight.

Cosmetic and / or pharmaceutical preparations

The agents according to the invention, such as creams, gels, lotions, alcoholic and aq rig / alcoholic solutions, emulsions, wax / fat masses, stick preparations, powder or ointments, can as further auxiliaries and additives, mild surfactants, superfatting agents, pearlescent waxes, Consistency agents, thickeners, polymers, silicone compounds, fats, waxes, stabilizers, biogenic agents, deodorant agents, anti-dandruff agents, film formers, swelling agents, other UV light protection factors, antioxidants, hydrotropes, preservatives, insect repellents, self-tanners, Contain solubilizers, perfume oils, dyes, germ inhibitors and the like.  

Typical examples of suitable mild, i.e. H. Surfactants that are particularly compatible with the skin are fatty alcohol poly glycol 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 oligoglucosides, fatty acid glucamides, alkyl amido betaines and / or protein fatty acid condensates, the latter preferably based on wheat proteins.

Substances such as lanolin and lecithin and polyethoxy can be used as superfatting agents lated or acylated lanolin and lecithin derivatives, polyol fatty acid esters, monoglycerides and fatty acid al kanolamides are used, the latter also serving as foam stabilizers.

Pearlescent waxes, for example, are: alkylene glycol esters, especially ethylene glycol di stearate; Fatty acid alkanolamides, especially coconut fatty acid diethanolamide; Partial glycerides, especially stea rinic acid monoglyceride; Esters of polyvalent, optionally hydroxy-substituted carboxylic acids Fatty alcohols with 6 to 22 carbon atoms, especially long-chain esters of tartaric acid; Fatty substances like for example fatty alcohols, fatty ketones, fatty aldehydes, fatty ethers and fatty carbonates, which in total min have at least 24 carbon atoms, especially lauron and distearyl ether; Fatty acids such as stearin 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.

The main consistency agents are 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 fat acids into consideration. A combination of these substances with alkyl oligoglucosides and / or is preferred Fatty acid N-methylglucamides of the same chain length and / or polyglycerol poly-12-hydroxystearates. Suitable thickeners are, for example, Aerosil types (hydrophilic silicas), Polysac charide, especially xanthan gum, guar guar, agar agar, alginates and tyloses, carboxyme ethyl cellulose and hydroxyethyl cellulose, further 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 ethoxylated fatty acid reglycerides, esters of fatty acids with polyols such as pentaerythritol or trimethylolpropane, Fatty alcohol ethoxylates with a narrow homolog distribution or alkyl oligoglucosides as well as electrolytes like table salt and ammonium chloride.

Suitable cationic polymers are, for example, cationic cellulose derivatives, such as. Legs quaternized hydroxyethyl cellulose obtained from Amerchol under the name Polymer JR 400® Lich, cationic starch, copolymers of diallylammonium salts and acrylamides, quaternized Vinyl pyrrolidone / vinyl imidazole polymers, such as. B. Luviquat® (BASF), condensation products from Poly glycols and amines, quaternized collagen polypeptides such as lauryldimonium hydroxy  propyl hydrolyzed collagen (Lamequat®L / Grünau), quaternized wheat polypeptides, polyethyleneimine, cationic silicone polymers, such as. B. amidomethicones, copolymers of adipic acid and dimethyla minohydroxypropyldiethylenetrlamin (Cartaretine® / Sandoz), copolymers of acrylic acid with dimethyl diallylammonium chloride (Merquat® 550 / Chemviron), polyaminopolyamides, e.g. B. described in the FR 2252840 A and its crosslinked water-soluble polymers, cationic chitin derivatives as in for example, quaternized chitosan, optionally microcrystalline, condensation products Dihaloalkylene, such as. B. dibromobutane with bisdialkylamines, such as. B. bis-dimethylamino-1,3-propane, cationic guar gum, such as B. Jaguar® CBS, Jaguar® C-17, Jaguar® C-16 from Celanese, quaternized ammonium salt polymers, such as. B. Mirapol® A-15, Mirapol® AD-1, Mirapol® A2-1 der Miranol company.

Examples of anionic, zwitterionic, amphoteric and nonionic polymers are Vinyl acetate / crotonic acid copolymers, vinyl pyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / Isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and their esters, un cross-linked and polyols cross-linked 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, if appropriate, derivatized Cellulose ethers and silicones in question.

Suitable silicone compounds are, for example, dimethylpolysiloxanes, methylphenylpolysiloxanes, cyclic silicones as well as amino, fatty acid, alcohol, polyether, epoxy, fluorine, glycoside and / or al alkyl modified silicone compounds that are both liquid and resinous at room temperature can lie. Simethicones, which are mixtures of Dimethico, are also suitable nen with an average chain length of 200 to 300 dimethylsiloxane units and hydrogenated Silicates. A detailed overview of suitable volatile silicones can also be found at Todd et al. in Cosm.Toil. 91, 27 (1976).

Typical examples of fats are glycerides. a. Beeswax, carnauba wax, Candelilla wax, montan wax, paraffin wax, hydrogenated castor oil, fat that is solid at room temperature acid esters or microwaxes, optionally in combination with hydrophilic waxes, e.g. B. Cetylstea ryl alcohol or partial glycerides in question. Metal salts of fatty acids, such as e.g. B. magnesium, aluminum and / or zinc stearate or ricinoleate can be used.

Examples of biogenic active ingredients are tocopherol, tocopherol acetate, tocopherol palmitate, Ascorbic acid, deoxyribonucleic acid, retinol, bisabolol, allantoin, phytantriol, panthenol, AHA acid ren, amino acids, ceramides, pseudoceramides, essential oils, plant extracts and vitamin complexes to understand.  

As deodorants come e.g. B. antiperspirants such as aluminum chlorohydates in question. These are colorless, hygroscopic crystals that easily melt in the air and occur when vaping aqueous aluminum chloride solutions. Aluminum chlorohydrate is used to manufacture 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)]. An aluminum chlorohydrate, for example, which corresponds to the formula [Al ₂ (OH) ₅ Cl] * 2.5 H ₂ O and whose use is particularly preferred is sold under the trademark Locron® by Hoechst AG, Frankfurt / FRG . 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, campesteric, 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-decomposing bacteria or inhibit their growth can also be contained in the stick preparations. Examples include chitosan, phenoxyethanol and chlorhexidine gluconate. 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. Ge Common film formers are, for example, chitosan, microcrystalline chitosan, quaternized chito san, polyvinylpyrrolidone, vinylpyrrolidone-vinyl acetate copolymers, polymers of the acrylic acid series, quaternary cellulose derivatives, collagen, hyaluronic acid or its salts and similar compounds. Montmorillonite, clay minerals, pemulene and alkyl can be used as swelling agents for aqueous phases modified carbopol types (Goodrich) are used. Other suitable polymers or swelling agents can the overview by R. Lochhead in Cosm.Toil. 108, 95 (1993).

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

• - 3-benzylidene camphor or 3-benzylidene norcampher and its derivatives, e.g. B. 3- (4-Methylbenzy liden) camphor as described in EP 0 693 471 B1;
• - 4-aminobenzoic acid derivatives, preferably 4- (dimethylamino) benzoic acid 2-ethylhexyl ester, 4- 2-octyl (dimethylamino) benzoate and amyl 4- (dimethylamino) benzoate;
• - Esters of cinnamic acid, preferably 2-ethylhexyl 4-methoxycinnamate, 4-methoxycinnamate pro pylester, 4-methoxycinnamic acid isamyl ester 2-cyano-3,3-phenylcinnamic acid 2-ethylhexyl ester (Octo crylene);
• - Esters of salicylic acid, preferably salicylic acid 2-ethylhexyl ester, salicylic acid 4-isopropylbene methyl ester, salicylic acid homomethyl ester;
• - Derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-me thoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone;
• - Esters of benzalmalonic acid, preferably di-2-ethylhexyl 4-methoxybenzmalonate;
• - Triazine derivatives, such as. B. 2,4,6-Trianilino- (p-carbo-2'-ethyl-1'-hexyloxy) -1,3,5-triazine and octyl tria zon as described in EP 0 818 450 A1;
• Propane-1,3-diones, such as e.g. B. 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, such as. B. 4- (2-Oxo-3-bomylidenemethyl) benzene sulfonic acid and 2-methyl-5- (2-oxo-3-bomylidene) sulfonic acid and its salts.

Derivatives of benzoylmethane, such as, for example, are particularly suitable as typical UV-A filters wise 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione, 4-tert-butyl-4'-methoxydibenzoyl methane (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 For this purpose, substances also come with insoluble light protection pigments, namely finely dispersed metal oxide or salts in question. 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 as well their mixtures. Silicates (talc), barium sulfate or zinc stearate can be used as salts. The oxides and salts are in the form of the pigments for skin-care and skin-protecting emulsions  and used decorative cosmetics. The particles should have an average diameter of few less than 100 nm, preferably between 5 and 50 nm and in particular between 15 and 30 nm point. They can have a spherical shape, but such particles can also be used come that have an ellipsoidal or otherwise deviating from the spherical shape To have shape. The pigments can also be surface treated, i.e. H. hydrophilized or hydrophobic be present. Typical examples are coated titanium dioxide, such as. B. Titanium dioxide T 805 (Degussa) or Eusolex® T2000 (Merck). Silicones and trialkoxyoctylsilanes or simethicones in particular. Be in sunscreen before so-called micro or nanopigments used. Micronized zinc oxide is preferred used. Other suitable UV light protection filters can be found in P. Finkel's overview in the 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 D, L-camosine, D-carnosine, L-carnosine and their derivatives (e.g. anserine), carotenoids, carotenes (e.g. α-carotene, β-carotene, lycopene) and their derivatives, chlorogenic acid and its derivatives, lipoic acid and its derivatives (e.g. dihydroliponic acid), Au rothioglucose, propylthiouracil and other thiols (e.g. thioredoxin, glutathione, cysteine, cystine, cystamine and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl -, Oleyl, γ-linoleyl, cholesteryl and glyceryl esters) and their salts, dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and their derivatives (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) and sulfoximine compounds (e.g. Buthioninsulfoximine, homocysteine sulfoximine, Bu tioninsulfone, Penta-, Hexa-, Heptathioninsulfoxim in) in very low tolerable doses (e.g. B. 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 (e.g. 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 its derivatives, α -Glycosylrutin, Ferulasäure, Furfurylidenglucitol, Carnosin, Butylhydroxytoluol, Butylhydroxyanisol, Nordihydroguajak resin acid, Nordihydroguajaretsäure, Trihydroxybutyrophenon, Hamsäure and their derivatives, Man nose and their derivatives, Superoxid-Dismutase, zinc and its derivative e (e.g. ZnO, ZnSO ₄ ) selenium and its derivatives (e.g. B. selenium-methionine), stilbenes and their derivatives (z. B. stilbene oxide, trans-style benoxid) and the inventive derivatives (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids) of these active ingredients.

To improve the flow behavior, hydrotropes such as ethanol, isopropyl alcohol or polyols can also be used. Polyols that come into consideration 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 tech niche diglycerin mixtures with a diglycerol content of 40 to 50% by weight;
• Methyl compounds, such as in particular trimethylolethane, trimethylolpropane, trimethylolbutane, Pentaerythritol and dipentaerythritol;
• - Lower alkyl glucosides, especially those with 1 to 8 carbons in the alkyl radical, such as wise 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, para benzene, pentanediol or sorbic acid as well as those in Appendix 6, Parts A and B of the Cosmetics Ordinance led further substance classes. As insect repellents there are N, N-diethyl-m-toluamide, 1,2- Pentanediol or insect repellent 3535 in question, dihydroxyacetone is suitable as a self-tanner.

Perfume oils include mixtures of natural and synthetic fragrances. Natural Fragrance substances are extracts of flowers (lily, lavender, rose, 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), woods (pine, sandal, guaiac, cedar, rosewood), herbs and grasses (tarragon, Lemongrass, sage, thyme), needles and twigs (spruce, fir, pine, mountain pine), resins and bal seeds (galbanum, elemi, benzoin, myrrh, olibanum, opoponax). Furthermore animal raw come substances in question, such as civet and castoreum. Typical synthetic fragrance compounds gen are products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type. Fragrance compounds of the ester type are e.g. B. benzyl acetate, phenoxyethyl isobutyrate, p-tert-Bu tylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, phenylethyl acetate, linalyl benzoate,  Benzyl formate, ethyl methylphenyl glycinate, allcyclohexyl propionate; Styrallyl propionate and benzylsa licylate. The ethers include, for example, benzyl ethyl ether, the aldehydes z. B. the linear Alka nals with 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal, to the ketones z. B. the Jonone, ∝-isomethylionon and Me thylcedryl ketone, to the alcohols anethole, citronellol, eugenol, isoeugenol, geraniol, linalool, pheny ethyl alcohol and terpineol, the hydrocarbons mainly include terpenes and bal same. However, preference is given to using mixtures of different fragrances that work together generate an appealing fragrance. Also essential oils of lower volatility, mostly as an aro Mac components are used as perfume oils, e.g. B. sage oil, chamomile oil, clove oil, Lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, oliban oil, galbanu mole, labolanum oil and lavandin oil. Bergamot oil, dihydromyrcenol, lilial, lyral, Citronellol, phenylethyl alcohol, α-hexyl cinnamaldehyde, geraniol, benzylacetone, cyclamenaldehyde, Lina lool, boisambrene forte, ambroxan, indole, hedione, sandelice, lemon oil, mandarin oil, orange oil, Allylamyl glycolate, cyclover valley, lavandin oil, muscatel sage oil, β-damascone, geranium oil bourbon, Cyclohexyl salicylate, Vertofix Coeur, Iso-E-Super, Fixolide NP, Evemyl, Iraldein gamma, phenylacetic acid acid, geranyl acetate, benzyl acetate, rose oxide, romilllate, irotyl and floramate alone or in mixtures gene, used.

As dyes, the substances suitable and approved for cosmetic purposes can be used be used, such as the dye in the publication "Cosmetic Colorants" Commission of the German Research Foundation, Verlag Chemie, Weinheim, 1984, pp. 81-106 are put together. 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 effect against gram-positive bacteria such as 2,4,4'-trichloro-2'-hydroxydiphenyl ether, chlorhexidine (1,6-di- (4- chlorphenyl-biguanido) hexane) or TCC (3,4,4'-trichlorocarbonilide). Also numerous fragrances and essential oils have antimicrobial properties. Typical examples are the active ingredients Euge nol, 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 the linden blossom oil is and has a lily of the valley smell. Glycerol monolaurate has also proven to be a bacteriostatic lasts. 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 on the middle - amount. The agents can be produced by customary cold or hot processes gene; the phase inversion temperature method is preferably used.  

Examples

The photostability of various UV-A filters, if necessary in a mixture with different oils Components or emulsifiers were made after the Merck company on the occasion of the APV seminar method published in Fulda from September 17-18, 1997. The results are shown in Table 1 summarized. Examples 1 to 6 are according to the invention, examples V1 and V2 are used for ver equal.

Table 1

Photostability

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

Table 2

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

Table 2

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

Claims (11)

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),
in which the double bond is in the E or Z configuration and R ¹ for COOR ⁵ , COR ⁵ , CONR ⁵ R ⁶ , CN, O = S (-R ⁵ ) = O, O = S (-OR ⁵ ) = O, R ⁸ OP (-OR ⁷ ) = O, R ² for COOR ⁶ , COR ⁶ , CONR ⁵ R ⁶ , CN, O = S (-R ⁶ ) = O, O = S (-OR ⁶ ) = O , R ⁸ OP (-OR ⁷ ) = O, 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 hetero-aromatic 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 one another, in each case together with the Carbon atoms to which they are attached can together form a 5- or 6-ring, which may optionally be further fused. 3. Preparations according to claims 1 and / or 2, characterized in that they 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 , where 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 car boxylate, 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 Guerbetal alcohols based on fatty alcohols having 6 to 18 carbon atoms, esters of branched C ₆ -C _13- carboxylic acids with linear C ₆ -C ₂₂ fatty alcohols, esters of linear C ₆ -C ₂₂ fatty acids with branched alcohols, esters of hydroxycarboxylic acids with linear or branched C ₆ -C ₂₂ fatty alcohols, esters of linear and / or branched fatty acids with polyhydric alcohols and / or Guerbet alcohols, liquid mono- / di- / triglyceride mixtures based on C ₆ -C ₁₈ fatty acids, esters of C ₆ -C ₂₂ fatty alcohols and / or Guerbet alcohols with aromatic carboxylic acids, esters of C ₂ - C ₁₂ 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 alcohol olene, substituted cyclohexanes, linear and branched C ₆ -C ₂₂ fatty alcohol carbonates, Guerbet carbonates, esters of benzoic acid with linear and / or branched C ₆ -C ₂₂ 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; C _12/18 fatty acid _monoesters and diesters of adducts of 1 to 30 moles of ethylene oxide with glycerol; Sorbitan mono- and diesters of saturated and unsaturated fatty acids with 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 C _6/22 fatty acids, ricinoleic acid and 12-hydroxystearic acid and glycerol, polyglycerol, sugar alcohols, alkyl glucosides and polyglucosides; Mono-, di- and trialkyl phosphates and 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 wt .-% oil components and / or emulsifiers with a polarity in the range of 1.0 to 4.0 Debye

included, with the proviso that the quantities with water and possibly wide Ren add additives and additives to 100 wt .-%.