DE19649381A1 - Use of cyano-((hetero)aryl-amino)-alkenone compounds as UV filters - Google Patents

Abstract

The use of UV filter compounds of formula (I) is claimed in cosmetic products to protect human skin or hair against sunlight, where (I) are used alone or in combination with other UV filters. R1-R3 = H, 1-18C aliphatic or up to 18C cycloaliphatic group; or CR1R2 = a 5-6 membered ring; R4 = H, aliphatic, cycloaliphatic, arylaliphatic or aromatic group containing up to 18C; and R5 = optionally substituted 5-12 membered aromatic or heteroaromatic ring. Also claimed are cosmetic products containing UV filters, including effective amounts of (I), in a suitable carrier to protect the skin or hair against UV light at 280-400 nm. (I) are new when R1-R3 = Me; R4 = H; and R5 = phenyl (optionally substituted by 1-20C alkyl, 1-20C alkoxy, 1-20C alkylaminocarbonyl, 1-20C alkoxycarbonyl, CN, COOH, carboxylate, sulphonate or alkylammonium).

Description

The invention relates to the use of α-acyl, β-arylamino Acrylic nitriles as photostable UV-A filters in cosmetic accessories preparations for the protection of the human epidermis or humans Liche hair against UV radiation, especially in the range from 320 to 400 nm.

The light stabilizers used in cosmetic preparations have the task of preventing the harmful effects of sunlight to prevent the human skin, or at least to prevent it reduce effects. These light stabilizers also serve but also the protection of other ingredients from destruction or Degradation by UV radiation. In hair cosmetic formulations Damage to the keratin fibers from UV rays is reduced will.

The sunlight reaching the surface of the earth has a share to UV-B (280 to 320 nm) and UV-A radiation (<320 nm), which is directly related to the area of visible light connect. The influence on the human skin is making itself felt especially noticeable with UV-B radiation from sunburn. Accordingly, the industry offers a greater number of Substances that absorb UV-B radiation and thus prevent sunburn.

Now dermatological studies have shown that too UV-A radiation can cause skin damage and allergies can cause, for example, the keratin or elastin is harmed. This creates elasticity and water storage reduced capacity of the skin, d. H. the skin is less melted dig and tends to wrinkle. The strikingly high level of skin cancer frequency in areas of strong sunlight shows that apparently also damage to the genetic information in the cells caused by sunlight, especially by UV-A radiation will. All these findings therefore leave the development efficient filter substances for the UV-A range are necessary appear.

There is a growing need for light stabilizers for cosmetic preparations which serve primarily as UV-A filters and their absorption maxima are therefore in the range of approx. Should be 320 to 380 nm. To with the lowest possible Use amount to achieve the desired effect should be the like light protection agents in addition a highly specific extink exhibit. Also need sunscreens for cosmetic Preparations meet a large number of other requirements, for example good solubility in cosmetic oils, high sta emulsions produced with them, toxicological Harmlessness as well as low inherent odor and low inherent coloring.

Another requirement that light stabilizers must meet is is sufficient photostability. But this is with the previously available UV-A absorbing light protection agents are not or only inadequately guaranteed.

In French patent specification No. 2 440 933 this is 4- (1,1-Dimethylethyl) -4'-methoxydibenzoylmethane as a UV-A filter described. It is suggested to use this special UV-A-Fil ter, sold by GIVAUDAN under the name "PAR-SOL 1789 "is sold to com with various UV-B filters amalgamate to the total UV rays with a wavelength of Absorb 280 to 380 nm.

This UV-A filter is, however, when used alone or in combination nation is used with UV-B filters, photochemically not resistant enough to provide lasting protection to the skin during prolonged sunbathing to ensure what repeated Requires applications at regular and short intervals, if you can effectively protect the skin against the whole Want to achieve UV rays.

Therefore, according to EP 0514491, the not enough photo stable UV-A filter through the addition of 2-cyano-3,3-diphenyl Acrylic acid esters are stabilized, even in the UV-B range serve as a filter.

Furthermore, it has already been proposed according to EP 251 398, UV-A and UV-B radiation absorbing chromophores through a link in to unite a molecule. This has the disadvantage that on the one hand no free combination of UV-A and UV-B filters in the cosme table preparation is more possible and that difficulties arise the chemical linkage of the chromophores only certain combinations allow nations.

The object was therefore to find light stabilizers for cosmetic Propose purposes that are in the UV-A region with high absorbance absorb, which are photostable, have a low intrinsic color d. H. have a sharp band structure and, depending on the substituent, in oil or water soluble.

This object was achieved according to the invention by using compounds of the formula I.

in which R ¹ , R ² and R ³ denote hydrogen or aliphatic or cycloali phatic radicals each having up to 18 carbon atoms, two of the radicals R ¹ , R ² and R ³ together being able to form a 5- or 6-membered ring , R ^{4 is} an aliphatic, cycloaliphatic, araliphatic or aromatic radical with up to 18 carbon atoms and R ^{5 is} an optionally substituted aromatic or heteroaromatic radical with 5 to 12 ring atoms and R ^{4 can} additionally represent hydrogen, as a UV filter , in particular UV-A filters, in cosmetic preparations for protecting human skin against sun rays, alone or together with compounds that are known per se for cosmetic preparations and absorb in the UV range.

Those compounds of the formula I are preferred in which R ^{4 is} hydrogen and R ¹ , R ² and R ^{3 are} low molecular weight alkyl radicals.

It is particularly preferred to use compounds of the formula I in which R ^{4 is} hydrogen, R ¹ , R ² and R ^{3 have} low molecular weight alkyl radicals, e.g. B. with 1 to 4 carbon atoms and R ⁵ for an optionally substituted aromatic or heteroaromatic radical with up to 10 carbon atoms in the ring, in particular a substituted phenyl, thienyl, furyl, pyridyl, indolyl or Naphthylene radical and particularly preferably represents an optionally substituted phenyl or thienyl radical.

Both lipophilic and hydrophilic can be used as substituents Substituents with e.g. B. possible up to 20 carbon atoms. Lipophilic d. H. the oil solubility of the compounds of formula I enhancing Remnants are z. B. aliphatic or cycloaliphatic radicals ins special alkyl radicals with 1 to 18 carbon atoms, alkoxy, mono- and Dialkylamino, alkoxycarbonyl, mono- and dialkylaminocarbonyl, Mono- and dialkylaminosulfonyl radicals, also cyano, nitro, bromine, Chlorine, iodine or fluorine substituents.

Hydrophilic d. H. the water solubility of the compounds of the formula I enabling residues are z. B. carboxy and sulfoxy radicals and in particular their salts are physiologically compatible with any Union cations, such as the alkali salts or the trialkyl ammonium salts, such as tri (hydroxyalkyl) ammonium salts or the 2-methylpropan-1-ol-2-ammonium salts. There are also alkylammonium residues with any physiologically compatible anions in Consideration.

The alkoxy radicals are preferably those with 1 to 12 carbon atoms with 1 to 8 carbon atoms.

Examples include:

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, for. B. those into consideration, contain the 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-ethyl propyl and octyl into consideration. These remnants are equally in contain the mono- and dialkylaminocarbonyl and sulfonyl radicals.

Alkoxycarbonyl radicals are, for. B. esters containing the above alkoxy radicals or radicals of higher alcohols z. B. with up to 20 carbon atoms, such as iso-C ₁₅ alcohol.

The invention also relates to the new compounds of the formula II

in which R ⁶ denotes a phenyl radical, which optionally consists of one or more alkyl, alkoxy, alkylaminocarbonyl, alkoxy carbonyl, each with up to 20 carbon atoms or cyano or carboxy radicals or radicals selected from the group which make water solubilizing is substituted from carboxylate, sulfonate or alkyl ammonium radicals. Such residues are e.g. B. alkali carboxylate or carbonyloxy-tri- (hydroxyethyl) ammonium or sulfonyloxy-tri- (hydroxyethyl) ammonium radicals.

The compounds of the formula I or II to be used according to the invention can be prepared according to the equation

be prepared by condensation, where R ¹ to R ^{5 have} the meanings given above.

For example, the reaction of pivaloylacetonitrile results with m-toluidine and triethyl orthoformate and a catalyst, preferably a Lewis acid catalyst α-pivaloyl-β- (m- toluidino) acrylonitrile.

The cosmetic preparations containing light stabilizers are usually on the basis of a carrier who at least contains an oil phase. But there are also preparations alone water-based when using compounds with hydrophilic Substituents possible. Accordingly, oils, oil-in-water and Water-in-oil emulsions, creams and pastes, lip protection sticks bulk or fat-free gels into consideration.

Such sunscreen preparations can accordingly be liquid, pasty in water or solid form, for example as water-in-oil Creams, oil-in-water creams and lotions, aerosol foam creams, Gels, oils, grease pencils, powders, sprays or alcoholic-watery ones Lotions.

Common oil components in cosmetics are, for example, paraf fin oil, glyceryl stearate, isopropyl myristate, diisopropyl adipate, 2-ethylhexanoic acid cetylstearyl ester, hydrogenated polyisobutene, Vaseline, caprylic acid / capric acid triglycerides, microcrystalline Wax, lanolin and stearic acid.

Usual cosmetic auxiliaries that can be used as additives can come, are z. B. co-emulsifiers, fats and waxes, stabilizers lizers, thickeners, biogenic agents, film formers, Fragrances, dyes, pearlescent agents, preservatives, Pigments, electrolytes (e.g. magnesium sulfate) and pH regulators. Known W / O and in addition are preferably used as co-emulsifiers also O / W emulsifiers such as polyglycerol esters, sorbitan esters or partially esterified glycerides. Typical examples of Fats are glycerides; as waxes are inter alia. Beeswax, paraffin wax or micro waxes, optionally in combination with hydro phile waxes. Metal salts can be used as stabilizers of fatty acids such as B. magnesium, aluminum and / or zinc stearate can be used. Suitable thickeners are for example crosslinked polyacrylic acids and their derivatives, Polysaccharides, in particular xanthan gum, guar guar, agar agar, Alginates and tylose, carboxymethyl cellulose and hydroxyethyl cellulose, also fatty alcohols, monoglycerides and fatty acids, Polycrylates, polyvinyl alcohol and polyvinyl pyrrolidone. Under bio Genetic active ingredients are, for example, plant extracts, protein To understand hydrolysates and vitamin complexes. Usual film Formers are, for example, hydrocolloids such as chitosan, micro crystalline chitosan or quaternized chitosan, polyvinyl pyrrolidone, vinylpyrrolidone-vinyl acetate copolymers, polymers the acrylic acid series, quaternary cellulose derivatives and the like Links. Examples of suitable preservatives are Formaldehyde solution, p-hydroxybenzoate or sorbic acid. As pearl Gloss agents come, for example, glycol distearic acid esters such as Ethylene glycol distearate, but also fatty acids and fatty acid mono glycol ester into consideration. The dyes used for kosmeti Appropriate and approved substances are used for specific purposes as they are, for example, in the publication "Cosmetic Dye "of the dye committee of the German research community, published by Verlag Chemie, Weinheim, 1984, are put together. These dyes are commonly used in Concentration from 0.001 to 0.1% by weight based on the total Mixture, used.

The total amount of auxiliaries and additives can be 1 to 80, preferably 6 to 40% by weight and the non-aqueous portion ("Active substance") 20 to 80, preferably 30 to 70 wt .-% - in relation to the means - amount. The making of the means can in a manner known per se, d. H. for example by hot, Cold, hot-hot / cold or PIT emulsification take place. Here it is a purely mechanical process, a chemi cal reaction does not take place.

Finally, others known per se in the UV-A range can be used absorbing substances are used, provided they are in the Overall system of the combination to be used according to the invention UV-B and UV-A filters are stable.

The present invention also relates to cosmetic products Preparations containing 0.1 to 10% by weight, preferably 1 to 7% by weight, based on the total amount of cosmetic Preparation, one or more of the compounds of the formula I together with known per se for cosmetic preparations, Compounds absorbing in the UV-B range as light protection agents contain, the compounds of formula I usually in less amount than the UV-B absorbing compounds be set.

Most of the sunscreens in the to protect the cosmetic preparations used for human epidermis consists of compounds that absorb UV light in the UV-B range i.e. in the range from 280 to 320 nm. For example, the Proportion of the UV-A absorbers to be used according to the invention 10 to 90% by weight, preferably 20 to 50% by weight, based on the total amount of UV-B and UV-A absorbing substances.

Any UV-B filter substances can be used as UV-B filter substances which are used in combination with the compounds of the formula I to be used according to the invention. Examples include:

Finally, micronized pigments such as titanium dioxide and To mention zinc oxide.

The compounds to be used according to the invention are distinguished usually due to a particularly high absorption capacity in the UV-A radiation with a sharp band structure. Furthermore, they are readily soluble in cosmetic oils and leave easily work into cosmetic formulations. the Emulsions prepared with the compounds I stand out especially due to their high stability, the compounds I themselves characterized by their high photostability, and those made with I. Preparations are characterized by their pleasant feeling on the skin.

Examples Example 1 (manufacture) General rule (for the connection of No. 2 of the table)

0.1 mol of m-toluidine, 0.1 mol of pivaloylacetonitrile and 0.1 mol of tri ethyl orthoformate and 1 g of zinc chloride are in 100 ml of diethylene glycol heated to 120 ° C. for 2 h, with ethanol distilling off. To Cooling to 80 ° C is mixed with water and the precipitated Filtered off precipitate. Subsequently, from petroleum ether to crystallized. A-pivaloyl-β- (m- toluidino) acrylonitrile.

Further compounds prepared in this way are given in Table 1.

Table 1

General manufacturing instructions for the manufacture of emulsions for cosmetic purposes

All oil-soluble components are in a stirred tank Heated to 85 ° C. When all components are melted or as If the liquid phase is present, the water phase is homogenized incorporated. The emulsion is removed to approx. 40 ° C. with stirring cools, perfumes, homogenizes and then with constant stirring cooled to 25 ° C.

Preparations Example 2 Composition for lip care

ad 100 Eucerinum anhydricum 10.00 Glycerin 10.00 Titanium dioxide 0.5-10 Connection of Table 1, No. 1 8.00 Octyl methoxycinnamate 5.00 Zinc oxide 4.00 Castor oil 4.00 Pentaerythrithil stearate / caprate / caprylate adipate 3.00 Glyceryl stearate SE 2.00 Beeswax 2.00 Microcrystalline wax 2.00 Quaternium-18 bentonite 1.50 PEG-45 / Dodecyl Glycol Copolymer

Example 3 Composition for sunblock with micropigments

ad 100 water 10.0 Octyl methoxycinnamate 6.00 PEG-7 Hydrogenated Castor Oil 6.00 Titanium dioxide 0.5-10 Connection of Table 1, No. 2 5.00 Mineral oil 5.00 Isoamyl p-methoxycinnamate 5.00 Propylene glycol 3.00 Jojoba oil 3.00 4-methylbenzylidene camphor 2.00 PEG-45 / Dodecyl Glycol Copolymer 1.00 Dimethicone 0.50 PEG-40 Hydrogenated Castor Oil 0.50 Tocopheryl acetate 0.50 Phenoxyethanol 0.20 EDTA

Example 4 Fat-free gel

ad 100 water 8.00 Octyl methoxycinnamate 7.00 Titanium dioxide 0.5-10 Connection of Table 1, No. 3 5.00 Glycerin 5.00 PEG-25 PABA 1.00 4-methylbenzylidene camphor 0.40 Acrylate C10-C30 alkyl acrylate cross polymer 0.30 Imidazolidinyl urea 0.25 Hydroxyethyl cellulose 0.25 Sodium methyl paraben 0.20 Disodium EDTA 0.15 Fragrance 0.15 Sodium propyl paraben 0.10 Sodium hydroxide

Example 5 Sunscreen (SPF 20)

ad 100 water 8.00 Octyl methoxycinnamate 8.00 Titanium dioxide 6.00 PEG-7 Hydrogenated Castor Oil 0.5-10 Connection of Table 1, No. 1 6.00 Mineral oil 5.00 Zinc oxide 5.00 Isopropyl palmitate 5.00 Imidazolidinyl urea 3.00 Jojoba oil 2.00 PEG-45 / Dodecyl Glycol Copolymer 1.00 4-methylbenzylidene camphor 0.60 Magnesium stearate 0.50 Tocopheryl acetate 0.25 Methyl paraben 0.20 Disodium EDTA 0.15 Propyl paraben

Example 6 Waterproof sunscreen

ad 100 water 8.00 Octyl methoxycinnamate 5.00 PEG-7 Hydrogenated Castor Oil 5.00 Propylene glycol 4.00 Isopropyl palmitate 4.00 Caprylic / Capric Triglyceride 0.5-10 Connection according to Table 1, No. 1 4.00 Glycerin 3.00 Jojoba oil 2.00 4-methylbenzylidene camphor 2.00 Titanium dioxide 1.50 PEG-45 / Dodecyl Glycol Copolymer 1.50 Dimethicone 0.70 Magnesium sulfate 0.50 Magnesium stearate 0.15 Fragrance

Example 7 Sun milk (SPF 6)

ad 100 water 10.00 Mineral oil 6.00 PEG-7 Hydrogenated Castor Oil 5.00 Isopropyl palmitate 3.50 Octyl methoxycinnamate 0.5-10 Connection according to Table 1, No. 2 3.00 Caprylic / Capric Triglyceride 3.00 Jojoba oil 2.00 PEG-45 / Dodecyl Glycol Copolymer 0.70 Magnesium sulfate 0.60 Magnesium stearate 0.50 Tocopheryl acetate 0.30 Glycerin 0.25 Methyl paraben 0.15 Propyl paraben 0.05 Tocopherol

Example 8 Waterproof sunscreen

ad 100 water 8.00 Octyl methoxycinnamate 5.00 PEG-7 Hydrogenated Castor Oil 5.00 Propylene glycol 4.00 Isopropyl palmitate 4.00 Caprylic / Capric Triglyceride 0.5-10 Compound Table 1, No. 17 0.5-10 Connection according to Table 1, No. 1 4.00 Glycerin 3.00 Jojoba oil 2.00 4-methylbenzylidene camphor 2.00 Titanium dioxide 1.50 PEG-45 / Dodecyl Glycol Copolymer 1.50 Dimethicone 0.70 Magnesium sulfate 0.50 Magnesium stearate 0.15 Fragrance

Example 9 Suntan lotion

ad 100 water 10.00 Mineral oil 6.00 PEG-7 Hydrogenated Castor Oil 5.00 Isopropyl palmitate 3.50 Octyl methoxycinnamate 0.5-10 Compound Table 1, No. 17 3.00 Caprylic / Capric Triglyceride 3.00 Jojoba oil 2.00 PEG-45 / Dodecyl Glycol Copolymer 0.70 Magnesium sulfate 0.60 Magnesium stearate 0.50 Tocopheryl acetate 0.30 Glycerin 0.25 Methyl paraben 0.15 Propyl paraben 0.05 Tocopherol

Claims (11)

1. Use of compounds of the formula I.
in which R ¹ , R ² and R ³ denote hydrogen or aliphatic or cyclo-aliphatic radicals each having up to 18 carbon atoms, two of the radicals R ¹ , R ² and R ³ together being able to form a 5- or 6-membered ring , R ^{4 is} an aliphatic, cyclo aliphatic, araliphatic or aromatic radical with up to 18 carbon atoms and R ^{5 is} an optionally substituted aromatic or heteroaromatic radical with 5 to 12 ring atoms and R ^{4 can} also stand for hydrogen, as a UV filter in cosmetic preparations for protecting the human skin or human hair against sun rays, alone or together with compounds which are known per se for cosmetic preparations and which absorb in the UV range. 2. Use of compounds of formula I according to claim 1 as UV-A filter. 3. Use of compounds of the formula I according to claim 1, wherein R ^{4 is} hydrogen and R ¹ , R ² and R ^{3 are} low molecular weight alkyl radicals. 4. Use of compounds of the formula I according to claim 1, wherein R ^{4 is} hydrogen, R ¹ , R ² and R ^{3 are} low molecular weight alkyl radicals and R ^{5 is} phenyl which is optionally substituted by hydrophilic or lipophilic substituents. 5. Use of compounds of the formula I according to claim 1, wherein R ¹ , R ² and R ^{3 are} low molecular weight alkyl radicals, R ^{4 is} hydrogen and R ^{5 is} an alkoxyphenyl or alkoxy carbonylphenyl radical. 6. Use of compounds of the formula I according to claim 1, wherein R ¹ , R ² and R ^{3 are} low molecular weight alkyl radicals, R ^{4 is} hydrogen and R ^{5 is} a phenyl radical which carries water-solubilizing substituents selected from the group consisting of carboxylate , Sulfonate or ammonium residues. 7. Cosmetic preparations containing light stabilizers for protecting the human epidermis or human hair against UV light in the range from 280 to 400 nm, characterized in that they are in a cosmetically suitable carrier, alone or together with known per se for cosmetic preparations in the UV Area absorbing Ver compounds, effective as photostable UV filters amounts of compounds of the formula I.
contain, in which R ¹ , R ² and R ^{3 are} hydrogen or aliphatic or cycloaliphatic radicals each having up to 18 carbon atoms, two of the radicals R ¹ , R ² and R ³ together men a 5- or 6-ring can form and R ^{4 is} an aliphatic, cycloaliphatic, araliphatic or aromatic radical with up to 18 carbon atoms and R ^{5 is} an optionally substituted aromatic or heteroaromatic radical with 5 to 12 ring atoms and R ^{4 can} also represent hydrogen. 8. A light stabilizer according to claim 7, containing compounds of the formula I as UV-A filters, where R ^{4 is} hydrogen and R ¹ , R ² and R ^{3 are} low molecular weight alkyl radicals. 9. A light stabilizer according to claim 7, containing compounds of the formula I as UV-A filters, where R ^{4 is} hydrogen, R ¹ , R ² and R ^{3 are} low molecular weight alkyl radicals and R ^{5 is} phenyl which is optionally substituted by hydrophilic or lipophilic substituents . 10. A light stabilizer according to claim 7, containing compounds of the formula I as UV-A filters, where R ¹ , R ² and R ^{3 are} low molecular weight alkyl radicals, R ^{4 is} hydrogen and R ^{5 is} a phenyl radical which is substituted by alkyl, Alkoxy, alkyl aminocarbonyl, alkoxycarbonyl radicals, each with up to 20 carbon atoms, or with cyano or carboxy radicals, and with water-solubilizing substituents selected from the group consisting of carboxylate, sulfonate or alkylammonium radicals, can be substituted. 11. New compounds of the formula II,
in which R ⁶ denotes a phenyl radical which is replaced by one or more alkyl, alkoxy, alkylaminocarbonyl, alkoxycarbonyl radicals, each having up to 20 carbon atoms or cyano or carboxy radicals, and by water-solubilizing substituents selected from the group consisting of carboxylate, sulfonate or alkylammonium radicals, can be substituted.