DE10007017A1 - Sunlight protection composition with 4,4-diarylbutadiene UV-A filter solubilized and stabilized by presence of polar cosmetic oil and/or non-alkoxylated polyglycerol compound as nonionic emulsifier - Google Patents

Abstract

Agents protecting against the sun contain 4,4-diarylbutadiene UV-A filters together with cosmetic oils and/or non-alkoxylated polyglycerol compounds. Agents protecting against the sun contain: (A) 4,4-diarylbutadiene UV-A filters; together with (B) cosmetic oils; and/or (C) non-alkoxylated polyglycerol compounds.

Description

Field of the Invention

The invention is in the field of sun cosmetics and relates to new preparations holding special UV light protection filters in combination with selected emulsifiers and / or cosmetics oils.

State of the art

For the stability and effectiveness of sun protection products, it is necessary that the UV filters, especially if they have a crystalline structure, completely dissolve in the oil phase and also with Tempe rature storage remain solved, because with the crystallization the risk of instability of the formulation and a decrease in the sun protection factor over time is associated. The most interesting light Protection factors of the market currently include 4,4-diarylbutadiene, which is characterized by high effectiveness and very good photostability. However, its high recrystallization potential is disadvantageous. The according to the object of the present invention was to provide sunscreen formulations using 4,4-diarylbutadiene, which is also available under temperature storage are permanently protected against crystallization.

Description of the invention

The invention relates to sunscreens containing

• a) 4,4-Diarylbutadiene and
• b) cosmetic oils and / or
• c) non-alkoxylated polyglycerol compounds.

Another object of the invention is the use of the agents according to the invention in suns preservatives.  

Surprisingly, it was found that selected nonionic emulsifiers, namely alkyl enoxide-free polyglycerol compounds and / or selected cosmetic oils with a polarity in the Range from 1 to 4 Debye, preferably 1.5 to 3.5 Debye, the solubility of the special UV Sun protection filters in cosmetic oils are significantly improved and recrystallization is reliably prevented is prevented. Preparations which contain typical nonionic, ethylene oxide-containing emulsifiers such as, for. B. contain ethoxylated polyglycerol esters and / or cosmetic oils with inappropriate polarity, on the other hand, prove to be insufficiently stable.

4.4 diarylbutadienes

4,4 Diarylbutadienes are known photostable UV-A filters, which are sold by the company BASF. According to the invention, 4,4-diarylbutadienes of the formula (I) are used

in which R ¹ , R ² independently of one another are H, a 1-20C alkyl, 2-10C alkenyl, 3-10C cycloalkyl, 3-10C cycloalkenyl, 1-12C alkoxy, 1-20C alkoxycarbonyl, 1 -12C alkylamino, 1-12C dialkylamino, aryl or heteroaryl, R ³ for H, COOR ⁵ , COR ⁵ , CONR ⁵ , R ⁶ for CN, O = S (R ⁵ ) = O or O = S (OR ⁵ ) = O, R ⁷ for OP (OR ⁸ ) = O, a 1-20C alkyl, 2-10C alkenyl, 3-10C cycloalkyl, 3-10C cycloalkenyl, 1-12C alkoxy, 1-20C Alkoxycarbonyl, 1-12C alkylamino, 1-12C dialkylamino, aryl or heteroaryl; R ⁴ for COOR ⁶ , COR ⁶ , CONR ⁵ , R ⁶ , CN, O = S (R ⁶ ) = O, O = S (OR ⁶ ) = O, R ⁷ OP (OR ⁸ ) = O, 1-20C an alkyl, 2-10C alkenyl, 3-10C cycloalkyl, 7-10C bicycloalkyl, 3-10C cycloalkenyl, 7-10C bicycloalkenyl, aryl or heteroaryl radical, R ⁵ -R ⁸ for H, a 1- 20C alkyl, 2-10C alkenyl, 3-10C cycloalkyl, 7-10C bicycloalkyl, 3-10C cycloalkenyl, 7-10C bicycloalkenyl, aryl or heteroaryl and n is 1 to 3, where the variables R ³ -R ⁸ together, 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 annilated. Further possible embodiments are described in the German patent application DE 197 55 649 A1. The preparations according to the invention can contain the 4,4-diarylbutadiene in amounts of 0.1 to 5, preferably 0.3 to 3 and in particular 0.5 to 2% by weight, based on the preparations.

Cosmetic oils

Cosmetic oils according to the invention are, for example, 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 ₂₂ fatty alcohols or esters of branched C ₆ -C ₁₃ carboxylic acids with linear or branched C ₆ -C ₂₂ fatty alcohols, such as. B. myristyl myristate, myristyl palmitate, Myristylstea rat, myristyl, tylstearat Myristylisostearat Myristylbehenat, Myristylerucat, cetyl myristate, cetyl palmitate, Ce, Cetylisostearat, cetyl oleate, cetyl behenate, Cetylerucat, rylstearat Stearylmyristat, stearyl, Stea, Stearylisostearat, stearyl oleate, stearyl behenate, Stearylerucat, isostearyl, Isostearyl palmitate, nylmyristat Isostearylstearat, isostearyl isostearate, Isostearyloleat, isostearyl behenate, Isostearyloleat, oleyl myristate, oleyl palmitate, oleyl stearate, oleyl isostearate, oleyl oleate, Oleylbehenat, oleyl erucate, Behe, behenyl palmitate, behenyl, Behenylisostearat, behenyl oleate, behenyl behenate, Behe nylerucat, erucyl myristate, erucyl, erucyl, erucyl, Erucyl oleate, erucyl behenate and erucylerucate. In addition, esters of linear C ₆ -C ₂₂ fatty acids with branched alcohols, in particular 2-ethylhexanol, esters of C ₁₈ -C ₃₈ alkylhydroxycarboxylic acids with linear or branched C ₆ -C ₂₂ fatty alcohols are suitable (cf. DE 197 56 377 A1), in particular 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, triglycerides based on C ₆ -C ₁₀ fatty acids, liquid mono- / Get di- / triglyceride mixtures based on C ₆ -C ₁₈ fatty acids (cf. EP 97/00434), get esters of C ₆ -C ₂₂ fatty alcohol 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 hydroxyl groups, vegetable oils, branched primary alcohols, substituted cyclohexanes, linear and branched C ₆ -C ₂₂ fat talc carbonates, Guerbet carbonates based on fatty alcohols with 6 to 18, preferably 8 to 10 C atoms, 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 dialkyl ethers having 6 to 22 carbon atoms per alkyl group, ring opening products of epoxidized fatty acid esters with polyols, silicone oils (cyclomethi cone, silicon methicone types, etc.) and / or aliphatic or naphthenic hydrocarbons, such as . B. as squalane, squalene or dialkylcyclohexane. The preparations according to the invention can contain the oils in quantities of 1 to 99.8 and preferably 10 to 50% by weight, based on the preparations.

Non-alkoxylated polyglycerol compounds

The alkylene oxide-free polyglycerol compounds, which act as nonionic emulsifiers or dispersants are preferably selected from the group formed by polyglyceryl-2 Dipolyhydroxystearate (Dehymuls® PGPH), Polyglycerin-3-Diisostearate (Lameform® TGI), Polyglyceryl-4  Isostearate (Isolan® GI 34), Polyglyceryl-3 Oleate, Diisostearoyl Polyglyceryl-3 Diisostearate (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 (Cremophor® GS 32) and Polyglyceryl Polyricinoleate (Admul® WOL 1403) and their mixtures. The preparations according to the invention can Polyglycerol compounds in amounts of 0.5 to 15 and preferably 1 to 8 wt .-% - based on the preparations - included.

UV light protection factors

In addition to the obligatory 4,4-diarylbutadiene, which forms component (a), the preparations may contain further UV light protection factors. UV light protection factors include, for example, liquid or crystalline organic substances (light protection filters) at room temperature, which are able to absorb ultraviolet rays and absorb the energy in the form of longer-wave radiation, e.g. B. to release heat again. UV-B 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 0693471 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 zone as described in EP 0818450 A1 or dioctyl butamido triazone (Uvasorb® HEB);
• 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-bornylidenemethyl) benzene sulfonic acid and 2-methyl-5- (2-oxo-3-bornylidene) 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'-methoxy-dibenzoyl methane (Parsol 1789), 1-phenyl-3- (4'-isopropylphenyl) propane-1,3-dione and enamine compounds, as described in DE 197 12 033 A1 (BASF). The UV-A and UV-B filters can of course can also be used in mixtures. Particularly favorable combinations consist of the deri data of benzoylmethane, e.g. B. 4-tert-butyl-4'-methoxydibenzoylmethane (Parsol 1789) and 2-cyano- 3,3-phenylcinnamic acid-2-ethylhexyl ester (octocrylene) in combination with ester of cinnamic acid, preferably 2-ethylhexyl 4-methoxycinnamate and / or propyl 4-methoxycinnamate and / or 4- Methoxy cinnamic acid isoamyl ester. Such combinations with water-soluble filters are advantageous such as B. 2-phenylbenzimidazole-5-sulfonic acid and its alkali, alkaline earth, ammonium, alkylammoni um, alkanolammonium and glucammonium salts combined.

In addition to the soluble substances mentioned, insoluble light protection pig are also used for this purpose ment, namely finely dispersed metal oxides 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, Man goose, aluminum and cerium and their mixtures. Silicates (talc), barium sulfate or Zinc stearate can be used. The oxides and salts are in the form of the pigments for skin care and skin-protecting emulsions and decorative cosmetics. The particles should be one average diameter of less than 100 nm, preferably between 5 and 50 nm and in particular re between 15 and 30 nm. They can have a spherical shape, but they can Also such particles are used which are ellipsoidal or otherwise spherical shape differ. The pigments can also be surface treated, i.e. H. are hydrophilized or hydrophobized. Typical examples are coated titanium dioxide, such as. B. Titanium dioxide T 805 (Degussa) or Eusolex® T2000 (Merck). Come as a hydrophobic coating agent Silicones in particular, and trialkoxyoctylsilanes or simethicones in particular. In suns Protective agents are preferably used in the form of so-called micro or nanopigments. Preferably micronized zinc oxide is used. Further suitable UV light protection filters can be found in the overview from P. Finkel in SÖFW-Journal 122, 543 (1996) and Perfumery and Cosmetics 3 (1999), page 11ff remove.

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-carnosine, 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), Auro thioglucose, 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. buthioninsulfoxim , Homocysteine sulfoximine, Butionin sulfone, Penta-, Hexa-, Heptathioninsulfoxim in) in very low tolerable doses (e.g. B. pmol to µmol / kg), further (metal) chelators (e.g. α-hydroxy fatty acids, palmitic acid, phytic acid, lac toferrin), α-hydroxy acids (e.g. citric acid, lactic acid, malic acid), humic acid, bile acid , Biliary 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 its 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, ferulic acid, furfurylidene glucitol, carnosine, butylated hydroxytoluene, butylated hydroxyanisole, nordihydroguajak resin acid, nordihydroguajaretic acid, trihydroxybutyrophenone, uric acid and its derivatives, man nose and its derivatives, superoxide dismutase, zinc vate (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. The preparations according to the invention can contain the sun protection factors in amounts of 0 to 10 and preferably 1 to 5% by weight, based on the preparations.

Sunscreen

In a particular embodiment of the invention, the agents contain

• a) 0.01 to 10, preferably 0.1 to 5 and in particular 1 to 4% by weight of 4.4 diarylbutadienes and
• b) 0 to 99.8, preferably 1 to 50 and in particular 10 to 20% by weight of cosmetic oils and / or
• c) 0 to 30, preferably 0.01 to 20 and in particular 0.1 to 10% by weight of non-alkoxylated polygly cerine compounds and optionally
• d) 0 to 30, preferably 1 to 15% by weight of further UV light protection factors

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

Industrial applicability

The preparations according to the invention are notable for special storage stability. Typi cal designs are creams, gels, lotions, oils, alcoholic and aqueous / alcoholic solutions gene, emulsions or stick preparations. These agents can also be used as additional auxiliaries and additives mild surfactants, co-emulsifiers, pearlescent waxes, consistency agents, thickeners, over-greasing medium, stabilizers, polymers, silicone compounds, fats, waxes, lecithins, phospholipids, biogenic Active ingredients, antioxidants, film formers, swelling agents, insect repellents, self-tanners, hydrotropes, Contain solubilizers, preservatives, perfume oils, dyes and the like.

Surfactants

Anionic, nonionic, cationic and / or amphoteric or Amphoteric surfactants may be included, the proportion of which is usually around 1 to 70 is preferably 5 to 50 and in particular 10 to 30 wt .-%. Typical examples of anionic Surfactants are soaps, alkylbenzenesulfonates, alkanesulfonates, olefinsulfonates, alkylethersulfonates, glyce rinethersulfonates, α-methyl ester sulfonates, sulfofatty acids, alkyl sulfates, fatty alcohol ether sulfates, glyce rinether sulfates, fatty acid ether sulfates, hydroxy mixed ether sulfates, monoglyceride (ether) sulfates, fatty acid reamid (ether) sulfates, mono- and dialkyl sulfosuccinates, mono- and dialkyl sulfosuccinamates, Sulfotri glycerides, amide soaps, ether carboxylic acids and their salts, fatty acid isethionates, fatty acid sarcosi nates, fatty acid taurides, N-acylamino acids, such as acyl lactylates, acyl tartrates, acyl gluta mate and acyl aspartate, alkyl oligoglucoside sulfate, protein fatty acid condensate (especially plant products based on wheat) and alkyl (ether) phosphates. If the anionic surfactants Polygly contain colether chains, these can be a conventional Ho, but preferably a restricted Ho have molog distribution. Typical examples of nonionic surfactants are fatty alcohols holpolyglycol ether, alkylphenol polyglycol ether, fatty acid polyglycol ester, fatty acid amide polyglycol ether, Fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers or mixed formals, optionally parti ell oxidized alk (en) yl oligoglycosides or glucoronic acid derivatives, fatty acid N-alkyl glucamides, protein hydrolysates (especially vegetable products based on wheat), polyol fatty acid esters, sugar esters, Sorbitan esters, polysorbates and amine oxides. If the nonionic surfactants are polyglycol ether chains contain, these can be a conventional, but preferably a narrow, homolog distribution have lung. Typical examples of cationic surfactants are quaternary ammonium compounds, such as for example dimethyldistearylammonium chloride, and ester quats, especially quaternized  Fatty acid trialkanolamine ester salts. Typical examples of amphoteric or zwitterionic surfactants are Alkyl betaines, alkyl amido betaines, aminopropionates, aminoglycinates, imidazolinium betaines and sulfo betaine. The surfactants mentioned are exclusively known compounds. There Visible structure and production of these substances is for example on relevant reviews J. Falbe (ed.), "Surfactants in Consumer Products", Springer Verlag, Berlin, 1987, pp. 54-124 or J. Falbe (ed.), "Catalysts, surfactants and mineral oil additives", Thieme Verlag, Stuttgart, 1978, p. 123-217. Typical examples of particularly suitable mild, i.e. H. particularly skin-friendly 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 glutamates, α- Olefin sulfonates, ether carboxylic acids, alkyl oligoglucosides, fatty acid glucamides, alkyl amido betaines, Am phoacetal and / or protein fatty acid condensates, the latter preferably based on wheat protein nen.

Emulsifiers

Examples of suitable emulsifiers are 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 to linear Fatty alcohols with 8 to 22 carbon atoms, with fatty acids with 12 to 22 carbon atoms, with alkylphenols with 8 up to 15 carbon atoms in the alkyl group and alkylamines with 8 to 22 carbon atoms in the alkyl radical;
• - Alkyl and / or alkenyl oligoglycosides with 8 to 22 carbon atoms in the alk (en) yl radical and their ethoxylated analogs;
• - Adducts 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 hardened castor oil;
• - Partial esters of glycerol and / or sorbitan with unsaturated, linear or saturated, branched ten fatty acids with 12 to 22 carbon atoms and / or hydroxycarboxylic acids with 3 to 18 Koh lenstoffatomen and their adducts with 1 to 30 mol of ethylene oxide;
• - Partial esters of polyglycerin (average degree of self-condensation 2 to 8), polyethylene gly col (molecular weight 400 to 5000), trimethylolpropane, pentaerythritol, sugar alcohols (e.g. Sor bit), alkyl glucosides (e.g. methyl glucoside, butyl glucoside, lauryl glucoside) and polyglucosides (e.g. Cellulose) with saturated and / or unsaturated, linear or branched fatty acids with 12 to 22 carbon atoms and / or hydroxycarboxylic acids with 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 according to DE 11 65 574 PS and / or mixed esters of fatty acids with 6 to 22 carbon atoms, methyl glucose and polyols, preferably glycerin or polyglycerin.  
• - Mono-, di- and trialkyl phosphates as well as 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. B. Polyethylene glycol 30 dipolyhydroxystearate;
• - polymer emulsifiers, e.g. B. Pemulen types (TR-1, TR-2) from Goodrich;
• - Polyalkylene glycols as well
• - glycerine carbonate.

The adducts of ethylene oxide and / or of propylene oxide with fatty alcohols, fatty acids, alkylphenols or with castor oil are known, commercially available products. These are homolog mixtures whose average degree of alkoxylation is 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.

Alkyl and / or alkenyl oligoglycosides, their preparation and their use are known from the prior art Technology known. They are produced in particular by reacting glucose or oligosac charidene with primary alcohols with 8 to 18 carbon atoms. Regarding the glycoside residue that Both monoglycosides, in which a cyclic sugar residue is glycosidically bound to the fatty alcohol is suitable, as well as oligomeric glycosides with a degree of oligomerization up to preferably about 8 are. The degree of oligomerization is a statistical mean, one for such technical Products based on the usual homolog distribution.

Typical examples of suitable partial glycerides are hydroxystearic acid monoglyceride, hydroxy stearic acid diglyceride, isostearic acid monoglyceride, isostearic acid diglyceride, oleic acid monoglyceride, Oleic acid diglyceride, ricinoleic acid moglyceride, ricinoleic acid diglyceride, linoleic acid monoglyceride, linoleic acid diglyceride, linolenic acid monoglyceride, linolenic acid diglyceride, erucic acid monoglyceride, erucic acid diglyceride, tartaric acid monoglyceride, tartaric acid diglyceride, citric acid monoglyceride, citric diglyce rid, malic acid monoglyceride, malic acid diglyceride and their technical mixtures, the subordinate may still contain small amounts of triglyceride from the manufacturing process. Also suitable are addition products of 1 to 30, preferably 5 to 10, moles of ethylene oxide onto the par tialglycerides.

Sorbitan monoisostearate, sorbitan sesquiisostearate, sorbitan diisostearate, Sorbitan triisostearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan dioleate, sorbitan trioleate, Sorbi tanmonoerucate, sorbitan sesquierucate, sorbitan dierucate, sorbitan trierucate, sorbitan monoricinoleate, Sor bitansesquiricinoleate, sorbitan diricinoleate, sorbitan triricinoleate, sorbitan monohydroxystearate, sorbitan sesquihydroxystearate,  Sorbitan dihydroxystearate, sorbitan trihydroxystearate, sorbitan monotartrate, Sor bitansesquitartrate, sorbitan ditartrate, sorbitan tritartrate, sorbitan monocitrate, sorbitan sesquicitrate, sorbi tandicitrate, sorbitan tricitrate, sorbitan monomaleate, sorbitan sesquimaleate, sorbitan dimaleate, sorbitan tri maleate and their technical mixtures into question. Addition products from 1 are also suitable to 30, preferably 5 to 10 moles of ethylene oxide to the sorbitan esters mentioned.

Typical examples of suitable polyglycerol esters are polyglyceryl-2 dipolyhydroxystearate (Dehy muls® PGPH), polyglycerol-3-diisostearate (Lameform® TGI), polyglyceryl-4 isostearate (Isolan® GI 34), Polyglyceryl-3 Oleate, Diisostearoyl Polyglyceryl-3 Diisostearate (Isolan® PDI), Polyglyceryl-3 Methyl glucose 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 (Cremophor® GS 32) and Polyglyceryl Polyricinoleate (Admul® WOL 1403) Polyglyceryl Dimerate isostearates and their mixtures. Examples of other suitable polyol esters are the ge optionally mono-, di- and triesters of trimethylolpropane reacted with 1 to 30 mol of ethylene oxide or pentaerythritol with lauric acid, coconut fatty acid, tallow fatty acid, palmitic acid, stearic acid, oleic acid re, behenic acid and the like.

Zwitterionic surfactants can also be used as emulsifiers. Zwitterionic ten-side refers to those surface-active compounds which have 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-carboxyl -hydroxyethylimidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and the cocoacylaminoethylhydroxyethylcarboxymethylglycinate. 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. Finally, cationic surfactants are also suitable as emulsifiers, those of the esterquat type, preferably methylquaternized difatty acid triethanolamine ester salts, being particularly preferred.

Fats and waxes

Typical examples of fats are glycerides, ie solid or liquid vegetable or animal products which essentially consist of mixed glycerol esters of higher fatty acids. Natural waxes, such as, for example, B. candelilla wax, carnauba wax, japan wax, esparto grass wax, cork wax, guaruma wax, rice germ oil wax, sugar cane wax, ouricury wax, montan wax, beeswax, shellac wax, walnut, lanolin (wool wax), pretzel fat, ceresin, ozokerite (earth wax), petrolatum, paraffin wax; chemically modified waxes (hard waxes), such as. B. Montanester waxes, Sasol waxes, hydrogenated jojoba waxes and synthetic waxes, such as. B. Po lyalkylene waxes and polyethylene glycol waxes in question. In addition to fats, fat-like substances such as lecithins and phospholipids can also be used as additives. The person skilled in the art understands the term lecitol into those glycerophospholipids which are formed from fatty acids, glycerol, phosphoric acid and choline by esterification. Lecithins are therefore often referred to in the professional world as phosphatidylcholines (PC) and follow the general formula,

where R typically for linear aliphatic hydrocarbon radicals with 15 to 17 carbon atoms men and up to 4 cis double bonds. The cephalins are examples of natural lecithins called, which are also called phosphatidic acids and derivatives of 1,2-diacyl-sn-glycerol-3- represent phosphoric acids. In contrast, phospholipids are usually understood to be mono- and preferably diesters of phosphoric acid with glycerin (glycerol phosphates), which are generally related to the fet ten can be expected. In addition, sphingosines or sphingolipids are also suitable.

Pearlescent waxes

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.

Consistency agents and thickeners

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), polysaccha ride, especially xanthan gum, guar guar, agar agar, alginates and tyloses, carboxymethyl cellulose and hydroxyethyl cellulose, also higher molecular weight polyethylene glycol mono- and diesters of Fatty acids, polyacrylates, (e.g. Carbopole® and Pemulen types from Goodrich; Synthalene® from Sig ma; Keltrol types from Kelco; Seppic Sepigel types; Salcare types from Allied Colloids), Polyacry lamides, polymers, polyvinyl alcohol and polyvinyl pyrrolidone, surfactants such as ethoxylated Fatty acid glycerides, esters of fatty acids with polyols such as pentaerythritol or trimethy lolpropane, fatty alcohol ethoxylates with a narrow homolog distribution or alkyl oligoglucosides as well Electrolytes such as table salt and ammonium chloride.

Overfat

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.

Stabilizers

Metal salts of fatty acids, such as. B. magnesium, aluminum and / or zinc stearate or ricinoleate can be used.

Polymers

Suitable cationic polymers are, for example, cationic cellulose derivatives, such as. B. a qua ternated hydroxyethyl cellulose, available under the name Polymer JR 400® from Amerchol  is, cationic starch, copolymers of diallylammonium salts and acrylamides, quaternized vinyl pyrrolidone / vinylimidazole 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. amodimethicones, copolymers of adipic acid and dimethyla minohydroxypropyldiethylenetriamine (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® AZ-1 der Miranol company.

Vinyla, for example, comes as anionic, zwitterionic, amphoteric and nonionic polymers acetate / crotonic acid copolymers, vinyl pyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / iso bornyl 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. Other suitable polymers and thickeners are in Cos metics & Toiletries Vol. 108, May 1993, page 95ff.

Silicone compounds

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).  

Biogenic agents

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.

Film maker

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.

Swelling agent

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).

Insect repellents

N, N-diethyl-m-toluamide, 1,2-pentanediol or ethyl butylacetyla are used as insect repellents minopropionate in question.

Self-tanners and depigmenting agents

Dihydroxyacetone is suitable as a self-tanner. As tyrosine inhibitors ver the formation of melanin prevent and find application in depigmenting agents, for example arbutin, kojic acid, Coumaric acid and ascorbic acid (vitamin C) in question.  

Hydrotrope

To improve the flow behavior, hydrotropes such as ethanol, isopropyl alcohol or polyols can also be used. 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, 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.

Preservative

Suitable preservatives are, for example, phenoxyethanol, formaldehyde solution, parabens, Pentanediol or sorbic acid and those listed in Appendix 6, Parts A and B of the Cosmetics Ordinance other substance classes.

Perfume oils

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, allyl cyclohexyl 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, α-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, Evernyl, Iraldein gamma, phenylacetic acid acid, geranyl acetate, benzyl acetate, rose oxide, romilllate, irotyl and floramate alone or in mixtures gene, used.

Dyes

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 entire mixture used.

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

Various sun protection preparations have been tested for their shelf life and fine particle size is looking for. The results are summarized in Table 1. Examples 1 to 5 are according to the invention, Examples V1 and V2 are used for comparison.

Table 1

Stability of sunscreen formulations

The emulsions with the emulsifiers from Examples V1 and V2 separated after a storage period from 4 weeks at room temperature; Clear crystal growth was observed in the microscope respect, think highly of. Formulations 1 to 5 according to the invention, however, were stable even after 4 weeks; the microscope picture shows no crystals.

Tables 2 to 5 below contain a number of formulation examples.  

Table 2

Sun protection emulsions of the type O / W with 4,4-diarylbutadiene (part 1 - quantities as% by weight)

Table 3

Sun protection emulsions of the type O / W with 4,4-diarylbutadiene (part 2 - quantities as% by weight)

Table 4

Sun protection emulsions of the type W / O with 4,4-diarylbutadiene (part 1 - quantitative data as% by weight)

Table 5

Sun protection emulsions of the type W / O with 4,4-diarylbutadiene (part 2 - quantitative data as% by weight)

Claims (7)

1. Containing sunscreen

• a) 4,4-Diarylbutadienes and
• b) cosmetic oils and / or
• c) non-alkoxylated polyglycerol compounds.

2. Composition according to claim 1, characterized in that they contain as component (b) cosmetic oils with a polarity in the range of 1-4 Debye, preferably 1.5 to 3.5 Debye, which are selected from the group formed is from Guerbet alcohols based on fatty alcohols with 6 to 18 carbon atoms, esters of linear C ₆ -C ₂₂ fatty acids with linear C ₆ -C ₂₂ fatty alcohols, 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, Trigly ceriden based on C ₆ -C ₁₀ -fatty acids, 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, vegetable oils, 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, linear or branched, symmetrical or unsymmetrical dialkyl ethers with 6 to 22 carbon atoms per alkyl group, ring opening products of epoxidized fatty acid esters with polyols, silicone oils and aliphatic or naphthenic hydrocarbons. 3. Composition according to claims 1 and / or 2, characterized in that they are used as component (c) Contain non-alkoxylated polyglycerol compounds that are selected from the group consisting of is formed by Polyglyceryl-2 Dipolyhydroxystearate, Polyglycerin-3-Diisostearate, Polyglyceryl- 4 isostearates, polyglyceryl-3 oleates, diisostearoyl polyglyceryl-3 diisostearates, polyglyceryl-3 Methyl glucose distearate, polyglyceryl-3 beeswax, polyglyceryl-4 caprate, polyglyceryl-3 cetyl Ether, Polyglyceryl-3 Distearate and Polyglyceryl Polyricinoleate and their mixtures. 4. Composition according to at least one of claims 1 to 3, characterized in that it contains 4,4-diarylbutadienes of the formula (I) as component (a),
in which R ¹ , R ² independently of one another are H, a 1-20C alkyl, 2-10C alkenyl, 3-10C cycloalkyl- 3-10C cycloalkenyl-, 1-12C alkoxy-, 1-20C alkoxycarbonyl-, 1- 12C alkylamino, 1-12C dialkylamino, aryl or heteroaryl, R ³ for H, COOR ⁵ , COR ⁵ , CONR ⁵ , R ⁶ for CN, O = S (R ⁵ ) = O or O = S (OR ⁵ ) = O, R ⁷ for OP (OR ⁸ ) = O, a 1-20C alkyl, 2-10C alkenyl, 3-10C cycloalkyl, 3-10C cycloalkenyl, 1-12C alkoxy, 1-20C Alkoxycarbonyl, 1-12C alkylamino, 1-12C dialkylamino, aryl or heteroaryl; R ⁴ for COOR ⁶ , COR ⁶ , CONR ⁵ , R ⁶ , CN, O = S (R ⁶ ) = O, O = S (OR ⁶ ) = O, R ⁷ OP (OR ⁸ ) = O, 1-20C an alkyl, 2-10C alkenyl, 3-10C cycloalkyl, 7-10C bicycloalkyl, 3-10C cycloalkenyl, 7-10C bicycloalkenyl, aryl or heteroaryl radical, R ⁵ -R ⁸ for H, a 1- 20C alkyl, 2-10C alkenyl, 3-10C cycloalkyl, 7-10C bicycloalkyl, 3-10C cycloalkenyl, 7-10C bicycloalkenyl, aryl or heteroaryl radical and n is 1 to 3, where the variables R ³ -R ⁸ together, 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 annilated. 5. Composition according to at least one of claims 1 to 4, characterized in that it is as fa cultivative component (d) further solid or liquid, crystalline or non-crystalline at room temperature stalline UV protection factors included. 6. Composition according to at least one of claims 1 to 5, characterized in that it

• a) 0.01 to 10 wt .-% 4.4 diarylbutadienes and
• b) 0 to 99.8% by weight of cosmetic oils and / or
• c) 0 to 30 wt .-% non-alkoxylated polyglycerol compounds and optionally
• d) 0 to 30% by weight of further UV light protection factors

with the proviso that the quantities with water and, if appropriate, further conventional auxiliaries and additives are 100% by weight. 7. Use of the compositions according to claim 1 in sunscreens.