DE10219433A1 - Sunscreen preparations using acrylonitrile derivatives - Google Patents

Abstract

Cosmetic preparations that contain acrylonitrile derivatives protect human skin and hair from UV radiation.

Description

The invention relates to cosmetic preparations for protecting human Skin and human hair from the damaging effects of ultraviolet Solar radiation, the new acrylonitrile derivatives contained in these preparations and their use as UV absorbers.

UV absorbers are compounds with a pronounced absorption capacity for the ultraviolet radiation. They are used in particular as a sunscreen cosmetic and pharmaceutical preparations, but also to improve Lightfastness of technical products such as paints, varnishes, plastics, Textiles, polymers such as B. polymers and copolymers of mono- and diolefins, Polystyrenes, polyurethanes, polyamides, polyesters, polyureas and polycarbonates, Packaging materials and rubbers used.

Depending on the wavelength, UV rays are converted into UV-A rays (320-400 nm, UV-A-I: 340-400 nm, UV-A-II: 320-340 nm) or UV-B rays (280-320 nm).

UV rays can cause acute and chronic skin damage, the Type of damage depends on the wavelength of the radiation. So the UV-B Radiation a sunburn (erythema) up to severe skin burns cause. Reductions in enzyme activities, weakening of the Immune system, disorders of the DNA structure and changes to the cell membrane as damaging effects of UV-B rays are known. The UV-A rays penetrate into deeper layers of the skin and there the aging process of the skin accelerate. The shorter-wave UV-A-II radiation additionally increases the formation from sunburn. In addition, UV-A radiation can be phototoxic or trigger photo-allergic skin reactions.

Very frequent and unprotected exposure of the skin to sunlight leads to a Loss of skin elasticity and increased wrinkling. In extreme cases pathological skin changes up to skin cancer are observed.

Depending on the location of their absorption maxima, UV absorbers are converted into UV-A and UV-B absorber classified; is both UV-A and UV absorber UV-B absorbed, in this case one speaks of a UV-A / B broadband absorber.

The number of suitable UV-A absorbers is very limited and they have significant shortcomings:
The filter 4-tert-butyl-4'-methoxy-dibenzoylmethane (absorption maximum at 357 nm), which is frequently used in particular for protection against UV-AI radiation, is not photostable. In combination with the UV-B filters p-methoxycinnamic acid 2-ethylhexyl or isoamyl ester, photoreactions are also observed. In addition, it has only a limited solubility in cosmetic oils, which can lead to problems in the formulation of cosmetic preparations. Furthermore, sun protection products containing dibenzoylmethane derivative can leave stains that are extremely difficult to wash out on textiles.

• - Kompatibilität mit anderen UV-Absorbern unter Lichteinwirkung
• - bei kristallinen UV-Absorbern gute Löslichkeit in kosmetischen Lösungsmitteln und flüssigen, öllöslichen UV-Aborbern, wie z. B. p-Methoxyzimtsäure-ethyl-, -isoamyl- und -isooctylester, Ethylhexylsalicylat; Homomenthylsalicylat, Menthylanthranilat, p-Aminobenzoesäureethylhexylester, 3,3-Diphenyl-2-cyanoacrylsäure-ethyl- und -ethylhexylester;
• - flüssige, öllösliche UV-Absorber sollten mit anderen UV-Absorbern bzw. kosmetischen Ölkomponenten gut mischbar sein;
• - wasserresistenter UV-Schutz;
• - problemlose Verarbeitbarkeit in kosmetischen Formulierungen und Stabilität unter Anwendungsbedingungen;
• - Verträglichkeit mit kosmetischen Grundstoffen;
• - pH-Stabilität;
• - Thermostabilität;
• - keine oder problemlos auswaschbare Verfärbung von Textilien;
• - Farblosigkeit und Geruchsneutralität;
• - leicht bioabbaubar;
• - nicht wassergefährdend;
• - geringe Hautpenetration;
• - Brechungsindex > 1,5, um eine verbesserte Transparenz von Emulsionen zu erreichen.

There is therefore a further need for UV stabilizers for light stabilizers for use in cosmetic and pharmaceutical preparations. We are looking for light-stable UV-A absorbers with strong absorption so that they effectively protect against the damage caused by UV rays. Furthermore, the aim is that these UV absorbers also meet the following criteria for use in cosmetic sunscreens:

• - Compatibility with other UV absorbers under the influence of light
• - With crystalline UV absorbers good solubility in cosmetic solvents and liquid, oil-soluble UV absorbers, such as. B. ethyl p-methoxycinnamic acid, isoamyl and isooctyl ester, ethylhexyl salicylate; Homomenthyl salicylate, menthyl anthranilate, ethylhexyl p-aminobenzoate, ethyl and ethylhexyl 3,3-diphenyl-2-cyanoacrylate;
• - Liquid, oil-soluble UV absorbers should be readily miscible with other UV absorbers or cosmetic oil components;
• - water resistant UV protection;
• - easy processing in cosmetic formulations and stability under conditions of use;
• - compatibility with cosmetic raw materials;
• - pH stability;
• - thermal stability;
• - no or easily washable discoloration of textiles;
• - colorless and odorless;
• - easily biodegradable;
• - not hazardous to water;
• - low skin penetration;
• - Refractive index> 1.5 in order to achieve improved transparency of emulsions.

The invention relates to light protection preparations containing acrylonitrile derivatives of the formula (I) in which the C = C double bond is in the E or Z configuration,


wherein
R ^{1 can} denote hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₆ -C ₁₂ aryl,
R ² COOR ¹³ , COR ¹³ , CONR ¹³ R ¹⁴ , CN, where R ¹³ -R ^{14 is} hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl or C ₂ -C ₂₀ alkynyl, C ₆ -C ₁₂ aryl, C ₃ -C ₁₅ cycloalkyl, C ₅ -C ₁₂ heteroaryl, which may optionally be substituted by amino, hydroxy, acetoxy, carboxy, carbalkoxy, carbamoyl, a group W or interrupted by ether oxygen .
R ³ -R ^{12 have} the meaning given under R ¹ or also C ₃ -C ₁₅ cycloalkyl, C ₅ -C ₁₂ heteroaryl, C ₁ -C ₁₆ alkoxy, C ₆ -C ₁₉ aryloxy, amino, hydroxy, Mean acetoxy, carboxy, carbalkoxy, carbamoyl, where they can be substituted by a group W or interrupted by ether oxygen,
with the proviso that two substituents of R ³ -R ¹² on adjacent C atoms together can mean an optionally substituted C ₁ -C ₄ alkylene group, it being possible for a methylene group to be replaced by -O-, -S- or NH- .
z 0, 1 or 2
W silanes, oligosilanes and polysiloxanes of the general formulas W ^I to W ^III
W ^I SiR ¹⁵ _a (OSiR ¹⁵ ₃ ) _b
a 0, 1, 2 or 3
b 3, 2, 1 or 0
a + b 3



A is a bond to the neighboring atom
c 1-10
R ^{15 is} an open-chain or branched aliphatic, araliphatic, cycloaliphatic or optionally substituted aromatic radical, each having up to 18 carbon atoms
mean.

Examples of alkyl radicals are methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl-, 2-methylpropyl, 1,1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2- Dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2- methylpropyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl and n- Called dodecyl.

Examples of alkoxy radicals are methoxy, ethoxy, iso-propoxy, n-propoxy, 1-methylpropoxy, n-butoxy, n-pentoxy, 2-methylpropoxy, 3-methylbutoxy, 1,1-dimethylpropoxy, 2,2-dimethylpropoxy, hexoxy, heptoxy, octoxy call.

Compounds of the formula (IA) are preferred


wherein
R ^{1 can be} hydrogen, C ₁ -C ₁₂ alkyl, C ₂ -C ₁₂ alkenyl, C ₂ -C ₁₂ alkynyl, phenyl,
R ² COOR ¹³ , COR ¹³ ,
where R ^{13 represents} hydrogen, C ₁ -C ₁₂ alkyl, C ₂ -C ₁₂ alkenyl, C ₂ -C ₁₂ alkynyl or C ₆ -C ₁₂ aryl, which may be replaced by amino, hydroxy, acetoxy, carboxy, Carbalkoxy, carbamoyl, a group W substituted or interrupted by ether oxygen,
R ³ -R ^{12 have} the meaning given under R ¹ or also C ₃ -C ₁₅ cycloalkyl, C ₅ -C ₁₂ heteroaryl, C ₁ -C ₁₆ alkoxy, C ₆ -C ₁₂ aryloxy, amino, hydroxy, Mean acetoxy, carboxy, carbalkoxy, carbamoyl, where they can be substituted by a group W or interrupted by ether oxygen,
with the proviso that two substituents of R ³ -R ¹² on adjacent C atoms together can mean an optionally substituted C ₁ -C ₄ alkylene group, and
z means 0, 1 or 2.

Compounds of the formula (IB) are particularly preferred


wherein
R ¹ can denote hydrogen, C ₁ -C ₆ alkyl, phenyl,
R ³ -R ^{12 can} denote hydrogen, C ₁₂ alkyl, C ₂ -C ₁₂ alkenyl, C ₂ -C ₁₂ alkynyl, phenyl, C ₁ -C ₁₂ alkoxy, hydroxy, acetoxy, carboxy, carbalkoxy, carbamoyl, where they can be substituted by a group W or interrupted by ether oxygen,
with the proviso that two substituents of R ³ -R ⁸ on adjacent C atoms together can mean an optionally substituted C ₁ -C ₄ alkylene group,
R ¹⁶ -R ¹⁸ independently of one another can be hydrogen, C ₁ -C ₁₂ alkyl, C ₂ -C ₁₂ alkenyl, C ₂ -C ₁₂ alkynyl, these with C ₁ -C ₁₂ alkoxy, hydroxy, acetoxy , Carboxy, carbalkoxy, carbamoyl, a group W substituted or interrupted by ether oxygen,
z 0, 1 or 2
means.

3-Oxo-4,4-dimethyl-pentanenitrile (compounds of the formula (IB) with R ¹⁶ -R ¹⁸ = CH ₃ ) are very particularly preferred.

The following are particularly preferred 3-oxo-4,4-dimethyl-pentanenitriles:
2 - [(2,3-dihydro-1H-indol-1-yl) methylene] -4,4-dimethyl-3-oxopentanenitrile, 2 - [(2,3-dihydro-2-methyl-1H-indole -1-yl) methylene] -4,4-dimethyl-3-oxopentanenitrile, 2 - [(2,3-dihydro-5-methyl-1H-indol-1-yl) methylene] -4,4-dimethyl -3-oxopentanenitrile, 2 - [(2,3-dihydro-2,3-dimethyl-1H-indol-1-yl) methylene] -4,4-dimethyl-3-oxopentanenitrile, 2 - [( 2,3-dihydro-2,5-dimethyl-1H-indol-1-yl) methylene] -4,4-dimethyl-3-oxopentanenitrile,
2 - [(2,3-dihydro-2,3,3-trimethyl-1H-indol-1-yl) methylene] -4,4-dimethyl-3-oxopentanenitrile,
2 - [(2,3-Dihydro-5-methoxy-1H-indol-1-yl) methylene] -4,4-dimethyl-3-oxopentanenitrile, 2 - [(2,3-dihydro-2-methyl -5-methoxy-1H-indol-1-yl) methylene] -4,4-dimethyl-3-oxopentanenitrile, 2 - [(2,3-dihydro-2,3,3-trimethyl-5-methoxy- 1H-indol-1-yl) methylene] -4,4-dimethyl-3-oxopentanenitrile,
2- [1- (2,3-dihydro-2-methyl-1H-indol-1-yl) ethylidene] -4,4-dimethyl-3-oxopentanenitrile,
2- [1- (3,4-dihydro-1 (2H) -quinolinyl) ethylidene] -4,4-dimethyl-3-oxopentanenitrile and
2 - [(1,2,3,4,10,11-Hexahydro-9H-carbazol-9-yl) methylene] -4,4-dimethyl-3-oxopentanenitrile.

The compounds of the formula (I) can be prepared by processes known per se be prepared, for example by heating NH heterocycles together with orthocarboxylic acid esters and CH-acidic compounds. As NH heterocycles can, for example, indoline, 2-methyl-indoline, 2,3,3-trimethylindoline, 2,3,3- Trimethyl-5-methoxy-indoline, 5-methoxy-indoline, 1,2,3,4,5,10,11-hexahydrocarbazole and 1,2,3,4-tetrahydroquinoline can be used. Possible Orthocarboxylic acid esters are exemplified by trimethyl orthoformate, Triethyl orthoformate, triethyl orthoacetate, triethyl orthopropionate, Orthobenzoesäuretrimethylester. As CH-acidic compounds, for example Ethyl cyanoacetate, 3-methylbutyl cyanoacetate, 2- cyanoacetic acid ethylhexyl ester, malononitrile or pivaloylacetonitrile can be used.

The higher alkyl esters of the formula (I) can also be obtained from the methyl or ethyl esters can be obtained by transesterification with higher alcohols.

The use of acrylonitrile derivatives of the general formula (I) as UV filters to protect technical products such as B. of plastics is from DE-A 15 68 541 known. Cosmetic and pharmaceutical sunscreen preparations using acrylonitrile derivatives of the formula (I) as UV-A filters however, not previously described.

The sulfonated acrylonitriles claimed in WO 97/14680 are not for everyone Suitable for applications. Due to the extreme water solubility of these compounds For example, it is difficult to make waterproof cosmetic with these compounds To achieve preparations.

The oil-soluble acrylonitrile derivatives of the formula (I) are notable for being strong Absorption in the UV-A range and also have an excellent Lightfastness.

They are photostable and have good solubility in cosmetics Solvents and in liquid oil-soluble UV absorbers. With these Compounds can easily be stable cosmetic in any way Preparations are made.

In particular with the very particularly preferred 3-oxo-4,4-dimethyl-pentanenitriles due to its strong absorption in the UV-A-I range, it can provide good protection from the longer-wave UV-A radiation can be achieved.

The acrylonitrile derivatives of the formula (I) can therefore be used as UV absorbers in cosmetic products, in particular for protection against acute (sunburn) as well chronic (early skin aging) skin damage especially in Sunscreens, day care products and hair care products are used.

The acrylonitrile derivatives of the formula (I) also result in cosmetic preparations for the photostabilization of UV absorbers with lower UV light stability (cf. Tab. 2).

In particular, they stabilize the very light-unstable UV-A Absorber 4-tert-butyl-4'-methoxydibenzoylmethane.

Although the absorption maximum of the acrylonitrile derivatives of the formula (I) in UV-A-I range, is surprisingly with these acrylonitrile derivatives also an improvement in photostability z. B. the UV-B filter p-Methoxycinnamic acid 2-ethylhexyl or isoamyl ester reached.

A combination of the UV filters p-methoxy-cinnamic acid-2-ethylhexyl or isoamyl ester with 4-tert-butyl-4'-methoxy-dibenzoylmethane in cosmetic Preparations stabilized by the acrylonitrile derivatives of the formula (I).

Sunscreen preparations with improved photostability are achieved by Use of 0.1-10% by weight, preferably 1-10% by weight, p-methoxycinnamic acid 2-ethylhexyl ester, p-methoxycinnamic acid isoamyl ester or 4-tert-butyl-4'-methoxy-dibenzoylmethane with 0.1-10% by weight of a compound of formula (I).

Cosmetic formulations with increased light stability can also be produced through a combination of three of dibenzoylmethane derivatives and p-Methoxyzimzäureestern with acrylonitrile derivatives of the formula (I) by using z. B. 0.1-5% by weight 4-tert-butyl-4'-methoxy-dibenzoylmethane, preferably 1-3% by weight, 0.1-10% by weight of 2-ethylhexyl p-methoxycinnamate, preferably 1.0-7.5% by weight, and at least 0.2% by weight of a compound of the formula (I), preferably 1.0-6.0% by weight, preferably in the ratio 1 part of dibenzoylmethane derivative, 2 parts p-methoxycinnamic acid ester and 2 parts of the compound of formula (I).

It is also advantageous to add one or more to this combination of three photostable UV absorbers, such as B. methylbenzylidene camphor, 2-ethylhexyl-2- cyano-3,3'-diphenyl acrylate, octyltriazon, Uvasorb®HEB, Tinosorb®S, Tinosorb®M, Ethylhexyl salicylate, homomenthyl salicylate and phenylene benzimidazole sulfonic acid or phenylene-bis-benzimidazole-tetrasulfonic acid disodium salt, Mexoryl®SX, Mexoryl®XL or Parsol®SLX.

Furthermore, in cosmetic preparations, surprisingly, by Use of acrylonitrile derivatives of the formula (I) in combination with others UV filters achieved a synergistic increase in the sun protection factor. Examples for a synergistic increase in the sun protection factor are cosmetic Emulsions containing both a compound of formula (I) and Ethylhexyl methoxycinnamate or octocrylene, or a combination of compound of formula (I) with ethylhexyl methoxycinnamate and 2-phenylbenzimidazole sulfonic acid, or Ethylhexyl methoxycinnamate and methylbenzylidene camphor, or Ethylhexyl methoxycinnamate and 4-t-butyl-4'-methoxy-dibenzoylmethane, or Neo Heliopan® AP and ethyl hexyl methoxycinnamate, or a combination of the compound Formula (I) with octocrylene, methylbenzylidene camphor and zinc oxide contains. Combinations of compound of the formula (I) with dibenzoylmethanes also have Methylbenzylidene camphor, 2-phenylbenzimidazole sulfonic acid, Neo Heliopan®AP, Mexoryl®SX, Mexoryl®XL, Parsol®SLX, Tinosorb®S, Tinosorb®M, Uvinul®T150, Uvasorb®HEB and microfine pigments, zinc oxide and titanium dioxide, synergistic increases in the sun protection factor. The UV filter mentioned Combinations are given as examples and not on the above Combinations to understand limited. So can all of the above particularly suitable UV absorber as well as all in the monographs or Positive lists (USA, Europe, Japan, Australia, South Africa and other countries) approved UV filter with compounds of formula (I) or the like combinations individually or in any mixtures, combined. Usually is a synergistic increase of the UV sun protection factor achieved.

The combination of compounds of formula (I) with UV-A absorbers, especially UV-A-II absorbers provide comprehensive protection against UV-A radiation (320-400 nm). In particular a combination of compounds of formula (I) with Neo Heliopan®AP (UV-AII absorber) is for a broad UV-A protection performance too call. Further UV-A filters which, in combination with compounds of the formula (I) alone or in combination of compounds of formula (I) and Neo Heliopan®AP are preferred are Mexoryl SX, Mexoryl®XL, Tinosorb®M, Tinosorb®S, Benzophenone-3, Benzophenone-4, Neo Heliopan®357 and Neo Heliopan®MA.

For optimal broadband protection performance against UV-A and UV-B radiation aforementioned combinations with all UV-B filters and mixtures of these Combine filters (see above particularly suitable UV absorbers). Neo Heliopan®AV, Neo Heliopan®E1000, Neo are particularly suitable Heliopan®Hydro, Neo Heliopan®MBC, Neo Heliopan®303, Neo Heliopan®OS, Neo Heliopan®HMS, Uvinul®T150, Uvasorb®HEB and Dimethylaminobenzoesäureethylhexylester.

By combining compounds of formula (I) with Neo Heliopan®AP and a UV-B filter, e.g. B. ethylhexyl methoxycinnamate or UV-B filter mixtures and coated or uncoated finely dispersed metal oxides such. B. zinc oxide, titanium dioxide is a UV broadband protection _performance with a critical wavelength λ _crit. ≍ 380 nm achieved (see also Diffey in Int. J. Cosm. Science 16, 47 (1994)).

Synergies of the acrylonitrile derivatives of the formula (I) with other non-UV light absorbent components for improved protection against UV Light is expected.

Sun protection products should be waterproof so that they have sufficient UV protection for the user, especially children, after swimming or bathing is guaranteed. The UV absorbers of the formula (I) meet these requirements on the basis of of their hydrophobic character to a particular extent and are therefore suitable especially for the formulation of water-resistant sun protection products. Furthermore, the water resistance of sun protection products with water-soluble, single or multiple sulfonated UV filters such as B. Neo Heliopan®AP, Mexoryl®SX, Benzophenon-4, Neo Heliopan®Hydro and those already mentioned above particularly suitable oil-soluble UV absorbers by combination with Compounds of formula (I) can be significantly increased.

Liquid acrylonitrile derivatives of the formula (I) are also suitable as solvents for Fixed UV filters, for the following but not limiting examples are mentioned: camphor derivatives (e.g. benzylidene camphor and Methylbenzylidene camphor), triazine derivatives (e.g. octyltriazine, dioctylbutamide triazine, Bis (ethylhexyloxy, hydroxy) phenyl, methoxyphenyltriazine), benzophenone derivatives (e.g. Oxybenzone), dibenzoylmethane derivatives (e.g. butylmethoxydibenzoylmethane). The Solution properties of the acrylonitrile derivatives according to formula (I) can be increased if they are mixed with other liquid components of cosmetic preparations, including other liquid UV filters. Are listed exemplary but not restrictive: ethylhexyl p-methoxycinnamate, isoamyl p- methoxycinnamate, ethylhexyl salicylate, octocrylene, menthylanthanolate, Fatty alcohol esters, fatty acid esters, alkyl benzoates, etc.

Crystalline acrylonitriles of the formula (I) must be sufficiently dissolved in cosmetic preparations in order to avoid the problem of recrystallization after a long storage period. A sufficient amount of the oil components usually used in cosmetic preparations, liquid oil-soluble UV absorbers or alcohols, e.g. B. ethanol, isopropanol or 1-butanol is necessary to avoid recrystallization. The use of the following oil components and / or UV absorbers is particularly preferred in order to achieve sufficient solubility of the acrylonitrile derivatives:
Ethylhexyl methoxycinnamate, isoamyl methoxycinnamate, octocrylene, ethylhexyl salicylate, homosalate, menthyl anthranilate, Padimate O, diisopropyl adipate, C _12-15 - alkyl benzoate (Witconol TN), butylene glycol dicaprylate, cocylglycerol (33) dicaprylate (33) dicaplylate (33) dicaprylate (33) dicaprylate (33) /capr.-triglyceride (Miglyol 812), cetearyl-isononanate (Cetiol SN), PVP / hexadecene copolymer (Unimer U151), adipic acid / diethylene glycol / isononanoic acid copolymer (Lexorez 100), propylene glycol dicaprylate / dicaprate (myritolur PC) (Cetiol A), dicapryl ether (Cetiol OE), diethylhexyl naphthalate (Hallbrite®TQ), butyloctylsalicylate (Hallbrite®BHB), dibutyl adipate (Cetiol B), triethyl citrate (Hydagen CAT), propylene glycol dibcenzoate (Finsolvutylate 22), finsolvutylate (Finsolvutylate) Dioctyl malate (Ceraphyl 45), dipropylene glycol dibenzoate (Benzoflex 245), acetyl tributyl citrate (Citroflex A-4), acetyl triethyl citrate (Citroflex A-2). The list of the oils mentioned, which can be used in the sense of the present invention, should of course not be limiting.

It is very disadvantageous if UV absorbers are no longer on clothing leave washable stains. In particular is from the UV-A absorber tert-Butylmethoxydibenzoylmethan known that he stains no longer washable Textiles. The acrylonitriles according to the invention do not have this disadvantage, because staining on textiles is very easy to wash out.

The present invention also relates to new acrylonitrile derivatives according to formula (IB) and their use as UV absorbers, especially in cosmetic preparations.

The following new acrylonitrile derivatives of the formula (IB) are particularly preferred:
2 - [(2,3-dihydro-1H-indol-1-yl) methylene] -4,4-dimethyl-3-oxo-pentanenitrile
2 - [(2,3-dihydro-2-methyl-1H-indol-1-yl) methylene] -4,4-dimethyl-3-oxo-pentanenitrile
2 - [(2,3-dihydro-5-methyl-1H-indol-1-yl) methylene] -4,4-dimethyl-3-oxo-pentanenitrile
2 - [(2,3-Dihydro-2,3-dimethyl-1H-indol-1-yl) methylene] -4,4-dimethyl-3-oxopentanenitrile
2 - [(2,3-Dihydro-2,5-dimethyl-1H-indol-1-yl) methylene] -4,4-dimethyl-3-oxopentanenitrile
2 - [(2,3-Dihydro-2,3,3-trimethyl-1H-indol-1-yl) methylene] -4,4-dimethyl-3-oxopentanenitrile
2 - [(2,3-Dihydro-5-methoxy-1H-indol-1-yl) methylene] -4,4-dimethyl-3-oxopentanenitrile
2 - [(2,3-Dihydro-2-methyl-5-methoxy-1H-indol-1-yl) methylene] -4,4-dimethyl-3-oxopentanenitrile
2 - [(2,3-Dihydro-2,3,3-trimethyl-5-methoxy-1H-indol-1-yl) methylene] -4,4-dimethyl-3-oxopentanenitrile
2- [1- (2,3-dihydro-1H-indol-1-yl) ethylidene] -4,4-dimethyl-3-oxo-pentanenitrile
2- [1- (2,3-Dihydro-2-methyl-1H-indol-1-yl) ethylidene] -4,4-dimethyl-3-oxopentanenitrile
2- [1- (3,4-dihydro-1 (2H) -quinolinyl) ethylidene] -4,4-dimethyl-3-oxo-pentanenitrile
2 - [(1,2,3,4,10,11-Hexahydro-9H-carbazol-9-yl) methylene] -4,4-dimethyl-3-oxopentanenitrile.

The UV absorbers of the formula (I) prevent use in cosmetic or pharmaceutical preparations the passage of UV rays through the applied film of the preparation.

Cosmetic and dermatological formulations in the sense of this invention contain one or more conventional UV-A, UV-B and / or broadband filters as Individual substances or in any mixtures with each other, in the lipid phase and / or in the aqueous phase. They are satisfactory in every way Products that are surprisingly characterized by high UV-A protection performance or distinguish a high sun protection factor.

This is generally the case when the preparations are 0.5 to 15, preferably 1 to 10, in particular 2 to 7 wt .-% (based on the total weight of the Preparation) contain a compound of formula (I).

The cosmetic and / or dermatological formulations according to the invention can be composed as usual and the cosmetic and / or dermatological light protection, also for the treatment, care and cleaning of the Skin and / or hair and as a make-up product in decorative cosmetics serve.

These protect the skin and hair from UV radiation Cosmetic and pharmaceutical preparations can usually be found in the application forms used, d. H. as oil-in-water, water-in-oil or mixed emulsion, as milk, as a lotion or cream, aerosol, hydrodispersion or oil gel (emulsifier free), spray, foam, solution, powder, stick preparation or as any other common cosmetic or pharmaceutical preparation. For the Protection of the hair from UV rays are preferred preparations as shampoo, Conditioner, cure, gel, lotion, spray or cream used.

Accordingly, the preparations according to the invention, depending on their structure, used for example as skin protection cream, cleansing milk, Sunscreen lotion, nutrient cream, day or night cream, etc. It may be possible and advantageous, the preparations according to the invention as a basis for to use pharmaceutical formulations. Those are particularly preferred cosmetic and dermatological preparations in the form of a Skin care or make-up product available.

The cosmetic and dermatological agents according to the invention are used Preparations on skin and / or hair in the manner customary for cosmetics applied in sufficient quantity. Such cosmetic ones are particularly preferred and dermatological preparations in the form of a sunscreen available.

The cosmetic and dermatological preparations according to the invention can contain cosmetic auxiliaries, as are usually used in such preparations. z. B .:
Emulsifiers, surface-active compounds, lanolin, petroleum jelly, water, fats (e.g. triglycerides of fatty acids), polyethylene glycols, fatty alcohols, ethoxylated fatty alcohols, fatty acid esters (e.g. isopropyl palmitate, isooctyl stearate, diisopropyl adipate, etc.), natural or synthetic oils Waxes, pigments (e.g. titanium dioxide, zinc oxide, pearlescent pigments, color pigments), thickeners (e.g. hydroxyethyl cellulose, carboxymethyl cellulose, bentonite etc.), foam stabilizers, film formers, dyes, electrolytes, pH regulators, preservatives, bactericides, moisturizers , Vitamins and biogenic active substances (e.g. plant extracts and protein hydrolyzates), silicone derivatives, alcohols and polyols (e.g. ethyl alcohol, isopropanol, glycerin), perfume oils, polymers such as B. polyacrylates, polyurethanes, polyglycerides, polyvinyls, alkene and alkyne polymers, polysaccharides, polyvinylpyrrolidone, substances for preventing foaming, antioxidants, electrolytes, organic solvents, complexing agents, repellents, glycerides and radical scavengers such as. B. HALS (= "Hindered Amine Light Stabilizers") or phenol derivatives.

The following are suitable as nonionic emulsifiers or dispersants: which is formed from polyglyceryl-2-dipolyhydroxystearate (Dehymuls®PGPH), Polyglyceryl-3-diiso-stearate (Lameform®TGI), polyglyceryl-4-isostearate (Isolan®GI 34), polyglyceryl-3-oleates, diisostearyl-polyglyceryl-3-diisostearate (Isolan®PDI), Polyglyceryl-3-methylglucose distearate (Tego Carey®450), Polyglyceryl-3-beeswax (Cera Bellina®), Polyglyceryl-4-caprate (Polyglycerol caprate T2010 / 90), Polyglyceryl-3-cetylether (Chimexane®NL), Polyglyceryl-3-distearate (Cremophor®GS 32), polyglyceryl-2-stearate (Hostacerin®DGMS) and Polyglycerylpolyricineoleate (Admul®WOL 1403) and their mixtures.

• - Mineralöle, Mineralwachse;
• - Öle, wie Triglyceride der Caprin- oder der Caprylsäure, ferner natürliche Öle wie z. B. Rizinusöl;
• - Fette, Wachse und andere natürliche und synthetische Fettkörper, vorzugsweise Ester von Fettsäuren mit Alkoholen niedriger C-Zahl, z. B. mit Isopropanol, Propylenglykol oder Glycerin, oder Ester von Fettalkoholen mit Alkansäuren niedriger C-Zahl oder mit Fettsäuren;
• - Alkylbenzoate;
• - Silikonöle wie Dimethylpolysiloxane, Diethylpolysiloxane, Diphenylpolysiloxane sowie Mischformen daraus.

The lipid phase of the preparations can advantageously be selected from the following group of substances:

• - mineral oils, mineral waxes;
• - Oils, such as triglycerides of capric or caprylic acid, as well as natural oils such. B. castor oil;
• - Fats, waxes and other natural and synthetic fat bodies, preferably esters of fatty acids with alcohols of low C number, e.g. B. with isopropanol, propylene glycol or glycerol, or esters of fatty alcohols with low C number alkanoic acids or with fatty acids;
• - alkyl benzoates;
• - Silicone oils such as dimethylpolysiloxanes, diethylpolysiloxanes, diphenylpolysiloxanes and mixed forms thereof.

The oil phase of the emulsions, oleogels or hydrodispersions or Lipodispersions in the sense of the present invention are advantageously selected from the group the ester of saturated and / or unsaturated, branched and / or unbranched alkane carboxylic acids with a chain length of 3 to 30 carbon atoms and saturated and / or unsaturated, branched and / or unbranched alcohols Chain length from 3 to 30 carbon atoms, from the group of aromatic esters Carboxylic acids and saturated and / or unsaturated, branched and / or unbranched alcohols with a chain length of 3 to 30 carbon atoms. Such ester oils can then advantageously be selected from the group of isopropyl myristate, Isopropyl palmitate, isopropyl stearate, isopropyl oleate, n-butyl stearate, n-hexyl laurate, n- Decyl oleate, isooctyl stearate, isononyl stearate, isononyl isononanoate, 2-ethylhexyl palmitate, 2-ethylhexyl laurate, 2-hexyldecyl stearate, 2-octyldodecyl palmitate, Oleyl oleate, Oleylerucat, Erucyloleat, Erucylerucat as well as synthetic, semi-synthetic and natural mixtures of such esters, e.g. B. Jojoba oil.

Furthermore, the oil phase can advantageously be selected from the group of the branched ones and unbranched hydrocarbons and waxes, the silicone oils, the dialkyl ethers, the group of saturated or unsaturated, branched or unbranched Alcohols, as well as the fatty acid triglycerides, especially the triglycerol esters saturated and / or unsaturated, branched and / or unbranched alkane carboxylic acids Chain length of 8 to 24, especially 12 to 18 carbon atoms. The Fatty acid triglycerides can, for example, advantageously be selected from the group of synthetic, semi-synthetic and natural oils, e.g. B. olive oil, Sunflower oil, soybean oil, peanut oil, rapeseed oil, almond oil, palm oil, coconut oil, palm kernel oil and the like more.

Any mixtures of such oil and wax components are also advantageous use in the sense of the present invention. It can also if necessary be advantageous, as waxes, for example beeswax and its derivatives use only lipid component of the oil phase.

The oil phase is advantageously selected from the group consisting of 2-ethylhexyl isostearate, octyldodecanol, isotridecyl isononanoate, isoeicosane, 2-ethylhexyl cocoate, C _12-15 alkyl benzoate, caprylic capric acid triglyceride and dicaprylyl ether.

Mixtures of C _12-15 alkyl benzoate and 2-ethylhexyl isostearate, mixtures of C _12-15 alkyl benzoate and isotridecyl isononanoate and mixtures of C _12-15 alkyl benzoate, 2-ethyl hexyl isostearate and isotridecyl isononanoate are particularly advantageous.

Of the hydrocarbons, paraffin oil, squalane and squalene are advantageous in To use sense of the present invention.

The oil phase can also advantageously have a cyclic or linear content Have silicone oils or consist entirely of such oils, although an additional content is preferred in addition to the silicone oil or the silicone oils to be used on other oil phase components.

Cyclomethicone (octamethylcyclotetrasiloxane) is advantageous as according to the invention silicone oil to be used. But other silicone oils are also beneficial to use in the sense of the present invention, for example Hexamethylcyclotrisiloxane, polydimethylsiloxane, poly (methylphenylsiloxane).

Mixtures of cyclomethicone and Isotridecyl isononanoate as well as from cyclomethicone and 2-ethylhexyl isostearate.

• - Alkohole, Diole oder Polyole niedriger C-Zahl sowie deren Ether, vorzugsweise Ethanol, Isopropanol, Propylenglykol, Glycerin. Ethylenglykol, Ethylenglykolmonoethyl- oder -monobutylether, Propylenglykolmonomethyl, -mono-ethyl- oder -monobutylether, Diethylenglykolmonomethyl- oder -monoethylether und analoge Produkte, ferner Alkohole niedriger C-Zahl, z. B. Ethanol, Isopropanol, 1,2-Propandiol, Glycerin sowie insbesondere ein oder mehrere Verdickungsmittel, welches oder welche vorteilhaft gewählt werden können aus der Gruppe Siliciumdioxid, Aluminiumsilikate, Polysaccharide bzw. deren Derivate, z. B. Hyaluronsäure, Xanthangummi, Hydroxypropylmethylcellulose, besonders vorteilhaft aus der Gruppe der Polyacrylate, bevorzugt ein Polyacrylat aus der Gruppe der sogenannten Carbopole, beispielsweise Carbopole der Typen 980, 981, 1382. 2984, 5984, jeweils einzeln oder in Kombination.

The aqueous phase of the preparations according to the invention advantageously advantageously contains:

• - Alcohols, diols or polyols of low C number and their ethers, preferably ethanol, isopropanol, propylene glycol, glycerin. Ethylene glycol, ethylene glycol monoethyl or monobutyl ether, propylene glycol monomethyl, mono ethyl or monobutyl ether, diethylene glycol monomethyl or monoethyl ether and similar products, furthermore alcohols of low C number, e.g. As ethanol, isopropanol, 1,2-propanediol, glycerol and in particular one or more thickeners, which or which can advantageously be selected from the group consisting of silicon dioxide, aluminum silicates, polysaccharides or their derivatives, e.g. B. hyaluronic acid, xanthan gum, hydroxypropylmethyl cellulose, particularly advantageously from the group of polyacrylates, preferably a polyacrylate from the group of so-called carbopoles, for example carbopoles of types 980, 981, 1382, 2984, 5984, each individually or in combination.

The cosmetic and dermatological preparations according to the invention advantageously contain, in addition to the UV-A, UV-B and / or broadband filters used, although not absolutely, inorganic pigments based on metal oxides and / or other metal compounds which are sparingly soluble or insoluble in water, in particular the oxides of Titanium (TiO ₂ ), zinc (ZnO), iron (e.g. Fe ₂ O ₃ ), zirconium (ZrO ₂ ), silicon (SiO ₂ ), manganese (e.g. MnO), aluminum (Al ₂ O ₃ ), Cers (e.g. Ce ₂ O ₃ ), mixed oxides of the corresponding metals and mixtures of such oxides. These pigments are X-ray amorphous or non-X-ray amorphous. Pigments based on TiO _{2 are} particularly preferred.

X-ray amorphous oxide pigments are metal oxides or semimetal oxides, which contribute to X-ray diffraction experiments no or no discernible crystal structure reveal. Such pigments are often obtainable by flame reaction, for example in that a metal or semimetal halide with hydrogen and air (or pure oxygen) is reacted in a flame.

In cosmetic, dermatological or pharmaceutical formulations X-ray amorphous oxide pigments as thickening and thixotropic agents, Flow aid for stabilizing emulsions and dispersions and as a carrier (for example to increase the volume of finely divided powders or powders) used.

Well-known and often in cosmetic or dermatological galenics X-ray amorphous oxide pigments used are the silicon oxides of the type Aerosil® (CAS- No. 7631-85-9). Aerosile® available from DEGUSSA company stand out by small particle size (e.g. between 5 and 40 nm), the particles being spherical particles of very uniform dimensions can be seen. macroscopic Aerosile® are recognizable as loose, white powder. In the sense of the present X-ray amorphous silicon dioxide pigments are particularly advantageous, and among these, those of the Aerosil® type are preferred.

Advantageous Aerosil® types are, for example, Aerosil® 0X50, Aerosil® 130, Aerosil® 150, Aerosil® 200, Aerosil® 300, Aerosil® 380, Aerosil® MQX 80, Aerosil® MOX 170, Aerosil® COK 84, Aerosil® R 202, Aerosil® R 805, Aerosil® R 812, Aerosil® R 972, Aerosil® R 974 and Aerosil® R976.

According to the invention contain cosmetic or dermatological Sunscreen preparations 0.1 to 20% by weight, advantageously 0.5 to 10% by weight, very particularly preferably 1 to 5% by weight of X-ray amorphous oxide pigments.

The non-X-ray amorphous inorganic pigments are in accordance with the invention advantageously in hydrophobic form, d. that is, it's superficial water-repellent are treated. This surface treatment can consist of the Pigments according to known methods with a thin hydrophobic layer be provided. For example, shown in analogy to DE-A 33 14 742 Hydrophobized pigments are an advantage.

Advantageous TiO ₂ pigments are available, for example, under the trade name T 805, advantageous TiO ₂ / Fe ₂ O ₃ mixed oxides under the trade name T 817 from Degussa.

The total amount of inorganic pigments, especially hydrophilic and hydrophobic inorganic micropigments in the finished cosmetic or dermatological preparations is advantageous from the range of 0.1-30% by weight, preferably 0.1-10.0, in particular 0.5-6.0% by weight, selected on the total weight of the preparations.

An additional content of antioxidants in the cosmetic according to the invention and dermatological preparations are generally preferred. According to the invention, all of the cosmetic and / or dermatological applications suitable or customary antioxidants used become.

The antioxidants are advantageously selected from the group consisting of 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. a-carotene, b-carotene, lycopene) and their derivatives, chlorogenic acid and its derivatives, lipoic acid and its derivatives (e.g. B. dihydrolipoic acid), aurothioglucose, propylthiouracil and other ihiols (e.g. thioredoxin, glutathione, cysteine, cystine, cystamine and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and Lauryl, palmitoyl, oleyl, y-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), phenolic acid amides phenolic acid amines phenolic (e.g. homovanillic acid, 3,4-dihydroxyphenylessi gic acid, ferulic acid, sinapic acid, caffeic acid, dihydroferulic acid, dihydrocaffeic acid, vanillomandelic acid or 3,4-dihydroxymandelic acid amides of 3,4-dihydroxybenzyl-, 2,3,4-trihydroxy-benzyl- or 3,4, 5-trihydroxybenzylamine) and sulfoximine compounds (e.g. B. Buthioninsulfoximine, Homocysteinsulfoximin, Buthioninsulfone, Penta-, Hexa-, Heptathioninsulfoximin) in very low tolerable doses, further (metal) chelators (z. B. α-hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin), α-hydroxy acids (z. B. 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-glycosyl rutin, ferulic acid, furfurylidene glucitol, carnosine, butylated hydroxytoluene, butylated hydroxyanisole, nordihydroguajak resin acid, nordihydroguajaretic acid, T. rihydroxybutyrophenone, uric acid and its derivatives, mannose and its derivatives, zinc and its derivatives (e.g. B. ZnO, ZnSO ₄ ), selenium and its derivatives (z. B. selenomethionine), stilbenes and their derivatives (z , Nucleosides, peptides and lipids) of these active ingredients.

The amount of the aforementioned antioxidants (one or more compounds) in the preparations according to the invention are preferably 0.001 to 30% by weight, particularly preferably 0.05-20% by weight, in particular 1-10% by weight, based on the Total weight of the preparation.

If vitamin E and / or its derivatives represent the antioxidant (s), it is advantageous to have their respective concentrations in the range of 0.001-10 wt .-%, based on the total weight of the formulation to choose.

If vitamin A, or vitamin A derivatives, or carotenes or their derivatives, the or the antioxidants are advantageous, their respective concentrations from the range of 0.001-10% by weight, based on the total weight of the Wording to choose.

In addition, skin lightening agents can also be used in the cosmetic preparations be used. Benzaldoximes can preferably be used as skin lightening agents with at least one aromatic hydroxy or alkoxy group, benzo-condensed or heterocyclically fused 2-hydrazino-1,3-thiazoles, 2-thio-1,3,4-heterodiazoles, their anionic or cationic salts and mixtures thereof, Kojic acid, kojic acid derivatives, ascorbic acid, ascorbic acid derivatives, hydroquinone, Hydroquinone derivatives, sulfur-containing molecules (e.g. glutathione or cysteine) or other synthetic or natural skin lightening agents arrive, the latter also in the form of an extract from plants (e.g. tocopherols and derivatives, arbutin [e.g. B. from Bearberry extract], Aloesin [z. B. from aloe extract], Grapefruit extract and rice extract) can be used.

The cosmetic and dermatological preparations also include complexing agents (e.g. from the class of Amino-polycarboxylic acids, aromatic hydroxy and amino derivatives, enolates).

In addition, the cosmetic and dermatological preparations can also have inflammatory agents which consist of the compound classes of salicylic, Acetic and propionic acid derivatives, the pyrazoles, fenams and oxicams come.

Furthermore, the cosmetic and dermatological preparations can contain adjuvants Cooling and refreshing effect, such as B. menthol and derivatives derived therefrom, contain.

A comprehensive description of the raw and used in cosmetic products Active ingredients are shown in DE-A 199 19 630.

The amounts of cosmetic or dermatological auxiliary and carriers and perfume can vary depending on the type of each Product can be easily determined by a specialist simply by trying it out.

• - p-Aminobenzoesäure
• - p-Aminobenzoesäureethylester
• - p-Dimethylaminobenzoesäure-2-ethylhexylester
• - p-Aminobenzoesäureethylester
• - p-Aminobenzoesäureglycerinester
• - Salicylsäure-homomenthylester (Homosalate) (Neo Heliopan®HMS)
• - Salicylsäure-2-ethylhexylester (Neo Heliopan®OS)
• - Triethanolaminsalicylat
• - 4-Isopropylbenzylsalicylat
• - Anthranilsäurementhylester (Neo Heliopan®MA)
• - Diisopropylzimtsäureethylester
• - p-Methoxyzimtsäure-2-ethylhexylester (Neo Heliopan®AV)
• - Diisopropylzimtsäuremethylester
• - p-Methoxyzimtsäureisoamylester (Neo Heliopan®E 1000)
• - p-Methoxyzimtsäure-diethanolaminsalz
• - p-Methoxyzimtsäure-isopropylester
• - 2-Ethylhexyl-2-cyano-3,3-diphenylacrylat (Neo Heliopan®303)
• - Ethyl-2-cyano-3,3'-diphenylacrylat
• - 2-Phenylbenzimidazolsulfonsäure und Salze (Neo Heliopan®Hydro)
• - 3-(4'-Trimethylammonium)-benzyliden-bornan-2-on-methylsulfat
• - Terephthalyliden-dibornansulfonsäure und Salze (Mexoryl®SX)
• - 4-t-Butyl-4'-methoxy-dibenzoylmethan (Avobenzon)/(Neo Heliopan®357)
• - β-Imidazol-4(5)-acrylsäure (Urocaninsäure)
• - 2-Hydroxy-4-methoxybenzophenon (Neo Heliopan®BB)
• - 2-Hydroxy-4-methoxybenzophenon-5-sulfonsäure
• - Dihydroxy-4-methoxybenzophenon
• - 2,4-Dihydroxybenzophenon
• - Tetrahydroxybenzophenon
• - 2,2'-Dihydroxy-4,4'-dimethoxybenzophenon
• - 2-Hydroxy-4-n-octoxybenzophenon
• - 2-Hydroxy-4-methoxy-4'-methylbenzophenon
• - 3-(4'-Sulfo)benzyliden-bornan-2-on und Salze
• - 3-(4'-Methylbenzyliden)-d,l-campher (Neo Heliopan®MBC)
• - 3-Benzyliden-d,l-campher
• - 4-Isopropyldibenzoylmethan
• - 2,4,6-Trianilino-(p-carbo-2'-ethylhexyl-1'-oxy)-1,3,5-triazin
• - Phenylen-bis-benzimidazyl-tetrasulfonsäure-dinatriumsalz (Neo Heliopan®AP)
• - 2,2'-(1,4-Phenylen)-bis-(1H-benzimidazol-4,6-disulfonsäure), Mononatriumsalz
• - N-[(2 und 4)-[2-(oxoborn-3-yliden)methyl]benzyl]-acrylamid-Polymer
• - Phenol, 2-(2H-benzotriazol-2-yl)-4-methyl-6-(2-methyl-3(1,3,3,3-tetramethyl-1- (trimethylsilyl)-oxy)-disiloxyanyl)-propyl), (Mexoryl®XL)
• - 4,4'-[(6-[4-(1,1-Dimethyl)-aminocarbonyl)-phenylamino]-1,3,5-triazin-2,4- diyl)diimino]-bis-(benzoesäure-2-ethylhexylester) (Uvasorb®HEB)
• - 2,2'-Methylen-bis-(6-(2H-benztriazol-2-yl)-4-1,1,3,3-tetramethylbutyl)-phenol), (Tinosorb®M)
• - 2,4-bis-[4-(2-ethylhexyloxy)-2-hydroxyphenyl]-1,3,5-triazin
• - Benzylidenmalonat-Polysiloxan (Parsol®SLX)
• - Glyceryl-ethylhexanoat-dimethoxycinnamat
• - Dinatrium-2,2'-dihydroxy-4,4'-dimethoxy-5,5'-disulfo-benzophenon
• - Dipropylenglykolsalicylat
• - Natrium-hydroxymethoxybenzophenon-sulfonat
• - 4,4',4-(1,3,5-Triazin-2,4,6-triyltriimino)-tris-benzoesäure-tris(2-ethylhexylester) (Uvinul®T150)
• - 2,4-Bis-[{(4-(2-Ethyl-hexyloxy)-2-hydroxy}-phenyl]-6-(4-methoxyphenyl)-1,3,5- triazin, (Tinosorb®S)
• - 2,4-Bis-[{(4-(3-sulfonato)-2-hydroxy-propyloxy)-2-hydroxy}-phenyl]-6-(4-methoxyphenyl)-1,3,5-triazin-Natriumsalz
• - 2,4-Bis-[{(3-(2-Propyloxy)-2-hydroxy-propyloxy)-2-hydroxy}-phenyl]-6-(4- methoxy-phenyl)-1,3,5-triazin
• - 2,4-Bis-[{4-(2-Ethyl-hexyloxy)-2-hydroxy}-phenyl]-6-[4-(2-methoxyethylcarbonyl)-phenylamino]-1,3,5-triazin
• - 2,4-Bis-[{4-(3-(2-propyloxy)-2-hydroxy-propyloxy)-2-hydroxy}-phenyl]-6-[4-(2- ethylcarboxyl)-phenylamino]-1,3,5-triazin
• - 2,4-Bis-[{4-(2-Ethyl-hexyloxy)-2-hydroxy}-phenyl]-6-(1-methyl-pyrrol-2-yl-)- 1,3,5-triazin
• - 2,4-Bis-[{4-tris-(trimethylsiloxy-silylpropyloxy)-2-hydroxy}-phenyl]-6-(4-methoxyphenyl)-1,3,5-triazin
• - 2,4-Bis-[{4-(2"-Methylpropenyloxy)-2-hydroxy}-phenyl]-6-(4-methoxyphenyl)- 1,3,5-triazin
• - 2,4-Bis-[{4-(1',1',1',3'5',5',5'-Heptamethylsiloxy-2"-methyl-propyloxy)-2-hydroxy}-phenyl]-6-(4-methoxyphenyl)-1,3,5-triazin

The acrylonitrile derivatives of the formula (I) can be used individually or as a mixture in the corresponding preparations; they can also be used in combination with UV absorbers of other substance classes or with these in any mixtures with one another. The list of UV absorbers mentioned below, which can be used for the purposes of the present invention, is of course not intended to be limiting.

• - p-aminobenzoic acid
• - ethyl p-aminobenzoate
• - 2-ethylhexyl p-dimethylaminobenzoate
• - ethyl p-aminobenzoate
• p-aminobenzoic acid glycerol ester
• - Salicylic acid homomethyl ester (homosalates) (Neo Heliopan®HMS)
• - 2-ethylhexyl salicylic acid (Neo Heliopan®OS)
• - triethanolamine salicylate
• - 4-isopropylbenzyl salicylate
• - Anthranile acid ethyl ester (Neo Heliopan®MA)
• - Ethyl diisopropyl cinnamate
• - 2-ethylhexyl p-methoxycinnamate (Neo Heliopan®AV)
• - methyl diisopropyl cinnamate
• - p-methoxycinnamic acid isoamyl ester (Neo Heliopan®E 1000)
• p-methoxycinnamic acid diethanolamine salt
• - Isopropyl p-methoxycinnamate
• - 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate (Neo Heliopan®303)
• - ethyl 2-cyano-3,3'-diphenyl acrylate
• - 2-phenylbenzimidazole sulfonic acid and salts (Neo Heliopan®Hydro)
• - 3- (4'-Trimethylammonium) benzylidene-bornan-2-one methyl sulfate
• - Terephthalylidene-dibornanesulfonic acid and salts (Mexoryl®SX)
• - 4-t-Butyl-4'-methoxy-dibenzoylmethane (Avobenzon) / (Neo Heliopan®357)
• - β-imidazole-4 (5) -acrylic acid (urocanic acid)
• - 2-hydroxy-4-methoxybenzophenone (Neo Heliopan®BB)
• - 2-Hydroxy-4-methoxybenzophenone-5-sulfonic acid
• - Dihydroxy-4-methoxybenzophenone
• - 2,4-dihydroxybenzophenone
• - tetrahydroxybenzophenone
• - 2,2'-dihydroxy-4,4'-dimethoxybenzophenone
• - 2-Hydroxy-4-n-octoxybenzophenone
• - 2-Hydroxy-4-methoxy-4'-methylbenzophenone
• - 3- (4'-Sulfo) benzylidene-bornan-2-one and salts
• - 3- (4'-Methylbenzyliden) -d, l-camphor (Neo Heliopan®MBC)
• - 3-benzylidene-d, l-camphor
• - 4-isopropyldibenzoylmethane
• - 2,4,6-trianilino- (p-carbo-2'-ethylhexyl-1'-oxy) -1,3,5-triazine
• - Phenylene-bis-benzimidazyl-tetrasulfonic acid disodium salt (Neo Heliopan®AP)
• - 2,2 '- (1,4-phenylene) bis (1H-benzimidazole-4,6-disulfonic acid), monosodium salt
• - N - [(2 and 4) - [2- (oxoborn-3-ylidene) methyl] benzyl] acrylamide polymer
• Phenol, 2- (2H-benzotriazol-2-yl) -4-methyl-6- (2-methyl-3 (1,3,3,3-tetramethyl-1- (trimethylsilyl) -oxy) -disiloxyanyl) - propyl), (Mexoryl®XL)
• - 4,4 '- [(6- [4- (1,1-dimethyl) aminocarbonyl) phenylamino] -1,3,5-triazine-2,4-diyl) diimino] bis (benzoic acid-2 -ethylhexyl ester) (Uvasorb®HEB)
• - 2,2'-methylene-bis- (6- (2H-benzotriazol-2-yl) -4-1,1,3,3-tetramethylbutyl) phenol), (Tinosorb®M)
• - 2,4-bis- [4- (2-ethylhexyloxy) -2-hydroxyphenyl] -1,3,5-triazine
• - benzylidene malonate polysiloxane (Parsol®SLX)
• Glyceryl ethylhexanoate dimethoxycinnamate
• Disodium 2,2'-dihydroxy-4,4'-dimethoxy-5,5'-disulfo-benzophenone
• - Dipropylene glycol salicylate
• Sodium hydroxymethoxybenzophenone sulfonate
• - 4,4 ', 4- (1,3,5-triazine-2,4,6-triyltriimino) tris-benzoic acid tris (2-ethylhexyl ester) (Uvinul®T150)
• - 2,4-bis - [{(4- (2-ethylhexyloxy) -2-hydroxy} phenyl] -6- (4-methoxyphenyl) -1,3,5- triazine, (Tinosorb®S)
• - 2,4-bis - [{(4- (3-sulfonato) -2-hydroxypropyloxy) -2-hydroxy} phenyl] -6- (4-methoxyphenyl) -1,3,5-triazine sodium salt
• - 2,4-bis - [{(3- (2-propyloxy) -2-hydroxypropyloxy) -2-hydroxy} phenyl] -6- (4-methoxyphenyl) -1,3,5-triazine
• - 2,4-bis - [{4- (2-ethylhexyloxy) -2-hydroxy} phenyl] -6- [4- (2-methoxyethylcarbonyl) phenylamino] -1,3,5-triazine
• - 2,4-bis - [{4- (3- (2-propyloxy) -2-hydroxypropyloxy) -2-hydroxy} phenyl] -6- [4- (2-ethylcarboxyl) phenylamino] -1 , 3,5-triazine
• - 2,4-bis - [{4- (2-ethylhexyloxy) -2-hydroxy} phenyl] -6- (1-methyl-pyrrol-2-yl -) - 1,3,5-triazine
• - 2,4-bis - [{4-tris (trimethylsiloxysilylpropyloxy) -2-hydroxy} phenyl] -6- (4-methoxyphenyl) -1,3,5-triazine
• - 2,4-bis - [{4- (2 "-methylpropenyloxy) -2-hydroxy} phenyl] -6- (4-methoxyphenyl) - 1,3,5-triazine
• - 2,4-bis - [{4- (1 ', 1', 1 ', 3'5', 5 ', 5'-heptamethylsiloxy-2 "-methyl-propyloxy) -2-hydroxy} phenyl] - 6- (4-methoxyphenyl) -1,3,5-triazine

• - p-Aminobenzoesäure
• - 3-(4'-Trimethylammonium)-benzyliden-bornan-2-on-methylsulfat
• - Salicylsäure-homomenthylester (Neo Heliopan®HMS)
• - 2-Hydroxy-4-methoxy-benzophenon (Neo Heliopan®BB)
• - 2-Phenylbenzimidazolsulfonsäure (Neo Heliopan®Hydro)
• - Terephthalyliden-dibornansulfonsäure und Salze (Mexoryl®SX)
• - 4-tert.-Butyl-4'-methoxydibenzoylmethan (Neo Heliopan®357)
• - 3-(4'-Sulfo)benzyliden-bornan-2-on und Salze
• - 2-Ethylhexyl-2-cyano-3,3-diphenylacrylat (Neo Heliopan®303)
• - N-[(2 und 4)-[2-(oxoborn-3-yliden)methyl]benzyl]-acrylamid-Polymer
• - p-Methoxyzimtsäure-2-ethylhexylester (Neo Heliopan®AV)
• - p-Aminobenzoesäure-ethylester
• - p-Methoxyzimtsäure-isoamylester (Neo Heliopan®E1000)
• - 2,4,6-Trianilino-(p-carbo-2'-ethylhexyl-1'-oxy)-1,3,5-triazin (Uvinul®T150)
• - Phenol, 2-(2H-benzotriazol-2-yl)-4-methyl-6-(2-methyl-3(1,3,3,3-tetramethyl-1- (trimethylsilyl)-oxy)-disiloxyanyl)-propyl), (Mexoryl®XL)
• - 4,4'-[(6-[4-(1,1-Dimethyl)-aminocarbonyl)-phenylamino]-1,3,5-triazin-2,4-diyl)- diimino]-bis-(benzoesäure-2-ethylhexylester), (UvasorbHEB)
• - 3-(4'-Methylbenzyliden)-d,l-campher (Neo Helipan®MBC)
• - 3-Benzylidencampher
• - Salicylsäure-2-ethylhexylester (Neo Helipan®OS)
• - 4-Dimethylaminobenzoesäure-2-ethylhexylester (Padimate O)
• - Hydroxy-4-methoxy-benzophenon-5-sulfonsäure und Na-Salz
• - 2,2'-Methylen-bis-(6-(2H-benztriazol-2-yl)-4-1,1,3,3-tetramethylbutyl)-phenol), (Tinosorb®M)
• - Phenylen-bis-benzimidazyl-tetrasulfonsäure-dinatriumsalz (Neo Heliopan®AP)
• - 2,4-Bis-[{(4-(2-Ethyl-hexyloxy)-2-hydroxy}-phenyl]-6-(4-methoxyphenyl)-1,3,5- triazin, (Tinosorb®S)
• - Benzylidenmalonat-Polysiloxan (Parsol®SLX)
• - Menthylanthranilat (Neo Heliopan®MA).

Particularly suitable UV absorbers are:

• - p-aminobenzoic acid
• - 3- (4'-Trimethylammonium) benzylidene-bornan-2-one methyl sulfate
• - Salicylic acid homomethyl ester (Neo Heliopan®HMS)
• - 2-hydroxy-4-methoxy-benzophenone (Neo Heliopan®BB)
• - 2-phenylbenzimidazole sulfonic acid (Neo Heliopan®Hydro)
• - Terephthalylidene-dibornanesulfonic acid and salts (Mexoryl®SX)
• - 4-tert-butyl-4'-methoxydibenzoylmethane (Neo Heliopan®357)
• - 3- (4'-Sulfo) benzylidene-bornan-2-one and salts
• - 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate (Neo Heliopan®303)
• - N - [(2 and 4) - [2- (oxoborn-3-ylidene) methyl] benzyl] acrylamide polymer
• - 2-ethylhexyl p-methoxycinnamate (Neo Heliopan®AV)
• - ethyl p-aminobenzoate
• - p-methoxycinnamic acid isoamyl ester (Neo Heliopan®E1000)
• - 2,4,6-trianilino- (p-carbo-2'-ethylhexyl-1'-oxy) -1,3,5-triazine (Uvinul®T150)
• Phenol, 2- (2H-benzotriazol-2-yl) -4-methyl-6- (2-methyl-3 (1,3,3,3-tetramethyl-1- (trimethylsilyl) -oxy) -disiloxyanyl) - propyl), (Mexoryl®XL)
• - 4,4 '- [(6- [4- (1,1-dimethyl) aminocarbonyl) phenylamino] -1,3,5-triazine-2,4-diyl) - diimino] -bis- (benzoic acid- 2-ethylhexyl ester), (UvasorbHEB)
• - 3- (4'-methylbenzylidene) -d, l-camphor (Neo Helipan®MBC)
• - 3-benzylidene camphor
• - 2-ethylhexyl salicylic acid (Neo Helipan®OS)
• 2-ethylhexyl 4-dimethylaminobenzoate (Padimate O)
• - Hydroxy-4-methoxy-benzophenone-5-sulfonic acid and Na salt
• - 2,2'-methylene-bis- (6- (2H-benzotriazol-2-yl) -4-1,1,3,3-tetramethylbutyl) phenol), (Tinosorb®M)
• - Phenylene-bis-benzimidazyl-tetrasulfonic acid disodium salt (Neo Heliopan®AP)
• - 2,4-bis - [{(4- (2-ethylhexyloxy) -2-hydroxy} phenyl] -6- (4-methoxyphenyl) -1,3,5- triazine, (Tinosorb®S)
• - benzylidene malonate polysiloxane (Parsol®SLX)
• - menthyl anthranilate (Neo Heliopan®MA).

It can also be advantageous to use polymer-bound or polymeric UV absorbers To use preparations according to the present invention, in particular those as described in WO 92/20690.

The enumeration of the UV filters mentioned in the sense of the present invention of course, should not be limiting.

The total amount of all (single and multiple sulfonated) water-soluble UV Filter substances in the finished cosmetic or dermatological preparations, for example on phenylene-bis-benzimidazyl-tetrasulfonic acid disodium salt or their salts and / or the corresponding disulfonic acid or their salts and / or 2-phenylbenzimidazole-5-sulfonic acid or its salts and / or 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid or its salts and / or 4- (2-oxo-3-bornylidenemethyl) benzenesulfonic acid or its salts and / or 2-methyl-5- (2-oxo-3- bornylidene-methyl) -benzenesulfonic acid or its salts and / or benzene-1,4-di- (2- oxo-3-bornylidenemethyl) -10-sulfonic acid or its salts, is advantageously obtained from the Range from 0.1 to 10.0% by weight, preferably 0.5 to 6.0% by weight, selected on the total weight of the preparations, if the presence of these substances is desired.

The total amount of oil-soluble UV filter substances in the finished cosmetic or dermatological preparations, for example on 4,4 ', 4 "- (1,3,5-triazine 2,4,6-triyltriimino) tris-benzoic acid tris (2-ethylhexyl ester) and / or 4-tert-butyl 4'-methoxy-dibenzoylmethane and / or 4-methylbenzylidene camphor and / or Octyldimethyl-p-aminobenzoic acid and / or Mexoryl®XL and / or Uvasorb®HEB and / or Tinosorb®S and / or benzophenone-3 and / or Parsol®SLX and / or Neo Heliopan®MA is advantageously preferred in the range from 0.1 to 10.0% by weight 0.5 to 6.0% by weight, selected, based on the total weight of the preparations, if the presence of these substances is desired.

The total amount of 2-ethylhexyl-p-methoxy-cinnamate and / or p-Methoxycinnamic acid isoamyl ester in the finished cosmetic or dermatological Preparations from the range from 0.1 to 15.0% by weight are preferred 0.5 to 7.5% by weight, selected, based on the total weight of the preparations, if the presence of these substances is desired.

The total amount of ethylhexyl-2-cyano-3,3-diphenylacrylate in the finished cosmetic or dermatological preparations, if the presence of these Substance is desired, advantageously in the range from 0.1 to 15.0% by weight, preferably 0.5 to 10.0% by weight, selected, based on the total weight of the Preparations.

The total amount of one or more salicylic acid derivatives in the finished Cosmetic or dermatological preparations are advantageous from the field from 0.1 to 15.0% by weight, preferably 0.5 to 10.0% by weight, based on the Total weight of the preparations. If ethylhexyl salicylate is chosen, it is advantageous, the total amount of which ranges from 0.1 to 5.0% by weight choose. If homomenthyl salad is chosen, it is advantageous to Total amount to choose from the range of 0.1 to 10.0 wt .-%.

Furthermore, the acrylonitrile derivatives of the formula (I) according to the invention also with UV absorbers, which are used for technical product protection, combine. Examples of such UV absorbers mainly correspond to compounds from the series of benzotriazoles, benzophenones and malonic esters.

The following examples are intended to illustrate the present invention without restrict them. All quantities, proportions and percentages are so far not otherwise specified, on the weight and the total amount or on the Total weight of the preparations related.

Unless otherwise stated, the separation or cleaning of the Acrylonitrile derivatives by crystallization, distillation or column chromatography Kieselgel 60 (elution with n-hexane / ethyl acetate = (5 - 10): 1).

Examples Examples 1-6 General instructions for the preparation of 2-cyano-2-propenoic acid esters

A mixture of 0.5 moles of orthocarboxylic acid ester, 0.5 moles Alkyl cyanoacetate and 0.5 mol of the corresponding NH heterocyclic compound Heated to 120 ° C for 2-3 hours and the alcohol which split off was distilled off. The accumulating residue is by crystallization, distillation or Column chromatography cleaned.

Examples 7-12 General instructions for the preparation of 3-oxo-4,4-dimethyl-pentanenitriles

A mixture of 0.5 mol of orthocarboxylic acid ester, 0.5 mol of pivaloylacetonitrile and 0.5 mol of the corresponding NH-heterocyclic compound is heated to 120 ° C. for 2-3 hours and the alcohol which is split off is distilled off. The residue obtained is purified by crystallization, distillation or column chromatography. Table 1



Example 13 Sun protection soft cream (O / W), waterproof

Manufacturing process part A: Heat to approx. 85 ° C.
Part B: Weigh raw materials without Carbopol. Disperse Carbopol with Ultra Turrax. Heat to approx. 85 ° C. Add B to A.
Part C: Add immediately to A / B and then homogenize hot (Ultra Turrax).
Let cool while stirring.
Part D: Add and stir. Example 14 Sun Protection Lotion (O / W)

Manufacturing process part A: Heat to approx. 85 ° C.
Part B: Weigh raw materials without Carbopol. Disperse Carbopol with Ultra Turrax. Heat to approx. 85 ° C. Add B to A.
Part C: Add immediately to A / B and then homogenize hot (Ultra Turrax). Let cool while stirring.
Part D: Add and stir. Example 15 Sun protection milk (O / W)

Manufacturing Process Part A: Heat to 80-85 ° C.
Part B: Heat to 80-85 ° C, add Part B to Part A while stirring.
Part C: Disperse Carbopol in the water and neutralize with NaOH while stirring.
Add part C at approx. 60 ° C while stirring. Let cool to RT.
Part D: Add and stir. Example 16 Sun Protection Lotion (O / W)

Manufacturing Process Part A: Heat to 80-85 ° C.
Part B: Heat to 80-85 ° C, add Part B to Part A while stirring.
Part C: Disperse Carbopol in the water and neutralize with NaOH while stirring.
Add part C at approx. 60 ° C while stirring. Let cool to RT.
Part D: Add and stir. Example 17 Sunscreen Lotion (O / W)

Manufacturing process part A: Dissolve UV absorber according to formula 1 in the oils or liquid UV filters (heating up to approx. 70 ° C). Allow to cool to approx. 30 ° C, add the remaining ingredients except Carbopol and Pemulen and mix at room temperature (stir for approx. 5 minutes). Stir in the Carbopol and Pemulen.
Part B: Dissolve Solbrole in phenoxyethanol while heating. Mix with water and glycerin, add to part A while stirring. Approximately Stir for 60 minutes.
Part C: Add to A / B, homogenize with the Ultra Turrax. Example 18 Sun protection cream (W / O), waterproof

Manufacturing process part A: Heat to approx. 85 ° C.
Part B: Heat to approx. 85 ° C (without zinc oxide; disperse zinc oxide with the Ultra Turrax). Add B to A.
Allow to cool with stirring, then homogenize. Example 19 Sun protection soft cream (W / O)

Manufacturing process part A: Heat to approx. 85 ° C.
Part B: Heat to approx. 85 ° C (without zinc oxide; disperse zinc oxide with the Ultra Turrax). Add B to A. Let cool while stirring.
Part C: Add and then homogenize Example 20 Sun protection milk (W / O)

Manufacturing process part A: Heat to approx. 85 ° C.
Part B: Heat to approx. 85 ° C. Add B to A. Let cool while stirring.
Part C: Add and then homogenize. Example 21 Day care cream with UV protection

Manufacturing Process Part A: Heat to 80 ° C.
Part B: Heat to 80 ° C. Add to part A while stirring.
Part C: Disperse Carbopol in water and neutralize with sodium hydroxide solution.
Add to part A / B at approx. 55 ° C.
Part D: Add at RT and homogenize. Example 22 Sunscreen Spray

Manufacturing Process Part A: Dissolve Lara Care A-200 in the other ingredients of Part A while stirring.
Part B: Weigh in all raw materials (without Pemulen) and dissolve the crystalline sub with heating. Disperse the pemules. Add part B to part A and homogenize for 1 minute.
Add part C + D and homogenize again with the Ultra Turrax for 1-2 minutes. Example 23 Sun Protection Hydrodispersion Gel (Balm)

Manufacturing process Part A: Disperse Carbopol in water and neutralize with sodium hydroxide solution.
Part B: Add to Part A while stirring.
Part C: Dissolve crystalline constituents from part C while heating (max. 40 ° C) in the other raw materials and add to part A / B. Mix well and then homogenize (hormocenta). Example 24 Hair Conditioner with UV Filters

Manufacturing Process Part A: Heat to 80 ° C.
Part B: Heat to 80 ° C. Add to part A while stirring.
Part C: Add at 40 ° C and cool to RT.

Determination of photostability

From a 5% solution of the UV filter to be tested or a combination with other commercially available UV absorbers such as OMC (octyl methoxy cinnamate) and / or BMDM (tert-butyl methoxy dibenzoyl methane), 20 µl are uniformly spread over 10 cm ² Glass plate with a roughened surface. After a storage period of 30 minutes in the dark, the sample is irradiated in a Suntest device with a solar standard filter and global sensor for 140 minutes with an irradiance of 765 W / m ² . During the irradiation, the glass plates are on the cooled bottom of the sun tester. A total of 4 glass plates are irradiated at the same time. After the end of irradiation, the samples are rinsed with ethanol from the glass plates into a 25 ml volumetric flask. The content of light stabilizer in the samples thus obtained is determined by means of a photometer or HPLC. In parallel, blank samples are applied to the glass platelets as described above and then rinsed and measured like the irradiated samples. Table 2

Claims (20)

1. light protection preparations containing acrylonitrile derivatives of the formula (I) in which the C = C double bond is in the E or Z configuration,


wherein
R ^{1 can} denote hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₆ -C ₁₂ aryl,
R ² COOR ¹³ , COR ¹³ , CONR ¹³ R ¹⁴ , CN,
where R ¹³ -R ^{14 is} hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl or C ₂ -C ₂₀ alkynyl, C ₆ -C ₁₂ aryl, C ₃ -C ₁₅ cycloalkyl, C ₅ -C ₁₂ heteroaryl, which may optionally be substituted by amino, hydroxy, acetoxy, carboxy, carbalkoxy, carbamoyl, a group W or interrupted by ether oxygen,
R ³ -R ^{12 have} the meaning given under R ¹ or also C ₃ -C ₁₅ cycloalkyl, C ₅ -C ₁₂ heteroaryl, C ₁ -C ₁₆ alkoxy, C ₆ -C ₁₂ aryloxy, amino, hydroxy, Mean acetoxy, carboxy, carbalkoxy, carbamoyl, where they can be substituted by a group W or interrupted by ether oxygen,
with the proviso that two substituents of R ³ -R ¹² on adjacent C atoms together can mean an optionally substituted C ₁ -C ₄ alkylene group, it being possible for a methylene group to be replaced by -O-, -S- or NH- .
z 0, 1 or 2
W silanes, oligosilanes and polysiloxanes of the general formulas W ^I to W ^III
W ^I SiR ¹⁵ _a (OSiR ¹⁵ ₃ ) _b
a 0, 1, 2 or 3
b 3, 2, 1 or 0
a + b 3



A is a bond to the neighboring atom
c 1-10
R ^{15 is} an open-chain or branched aliphatic, araliphatic, cycloaliphatic or optionally substituted aromatic radical, each having up to 18 carbon atoms
mean. 2. Light protection preparations according to claim 1 containing compounds of the formula (IA)


wherein
R ^{1 can be} hydrogen, C ₁ -C ₁₂ alkyl, C ₂ -C ₁₂ alkenyl, C ₂ -C ₁₂ alkynyl, phenyl,
R ² COOR ¹³ , COR ¹³ ,
where R ^{13 is} hydrogen, C ₁ -C ₁₂ alkyl, C ₂ -C ₁₂ alkenyl, C ₂ -C ₁₂ alkynyl or C ₆ -C ₁₂ alkyl, which may be replaced by amino, hydroxy, acetoxy, carboxy, Carbalkoxy, carbamoyl, a group W substituted or interrupted by ether oxygen,
R ³ -R ^{12 have} the meaning given under R ¹ or also C ₃ -C ₁₅ cycloalkyl, C ₅ -C ₁₂ heteroaryl, C ₁ -C ₁₆ alkoxy, C ₆ -C ₁₂ aryloxy, amino, hydroxy, Mean acetoxy, carboxy, carbalkoxy, carbamoyl, where they can be substituted by a group W or interrupted by ether oxygen,
with the proviso that two substituents of R ³ -R ¹² on adjacent C atoms together can mean an optionally substituted C ₁ -C ₄ alkylene group, and
z means 0, 1 or 2. 3. Light protection preparations according to claim 1 or 2 containing compounds of the formula (IB)


wherein
R ¹ can denote hydrogen, C ₁ -C ₆ alkyl, phenyl,
R ³ -R ¹² hydrogen, C ₁ -C ₁₂ alkyl, C ₂ -C ₁₂ alkenyl, C ₂ -C ₁₂ alkynyl, phenyl, C ₁ -C ₁₂ alkoxy, hydroxy, acetoxy, carboxy, carbalkoxy, carbamoyl can mean, where they can be substituted by a group W or interrupted by ether oxygen,
with the proviso that two substituents of R ³ -R ⁸ on adjacent C atoms together can mean an optionally substituted C ₁ -C ₄ alkylene group
R ¹⁶ -R ¹⁸ independently of one another can be hydrogen, C ₁ -C ₁₂ alkyl, C ₂ -C ₁₂ alkenyl, C ₂ -C ₁₂ alkynyl, these with C ₁ -C ₁₂ alkoxy, hydroxy, acetoxy , Carboxy, carbalkoxy, carbamoyl, a group W substituted or interrupted by ether oxygen,
z means 0, 1 or 2. 4. Light protection preparations according to claim 3, characterized in that in the formula (IB) the radicals R ¹⁶ , R ¹⁷ and R ¹⁸ each represent CH ₃ . 5. light protection preparations according to claims 1 to 4 under additional Use of UV-B and UV-A absorbers. 6. light protection preparations according to claim 5 wherein as UV-B and UV-A Absorber compounds from the groups of cinnamates, salicylates, p- Aminobenzoates, benzophenones, diphenyl acrylates, camphor derivatives, Triazines, benzylidene malonates, benzotriazoles, benzimidazoles, Dibenzoylmethane, polymeric filters or silicone filters can be used. 7. light protection preparations according to claim 5 wherein as UV-B and UV-A Absorber p-methoxycinnamic acid 2-ethylhexyl ester, p-methoxycinnamic acid isamyl ester, 4-methylbenzylidene camphor, 2-phenylbenzimidazole sulfonic acid, salicylic acid 2-ethylhexyl ester, 2-ethylhexyl 2-cyano-3,3-diphenyl, 2,2 '- (1,4-phenylene) bis-1H-benzimidazole-4,6-disulfonic acid monosodium salt or 4-tert-butyl-4'-methoxydibenzoylmethane can be used. 8. light protection preparations according to claims 1 to 7 in which additionally coated or non-coated inorganic pigments based on Metal oxides, especially the oxides of titanium, zinc and iron, are included. 9. Use of compounds of formula (I) according to claim 1 for Photo stabilization of other UV filters. 10. Use of compounds of formula (I) according to claim 1 for Photostabilization of UV absorbers of the dibenzoylmethane derivative type and methoxycinnamates. 11. Use of compounds of formula (I) according to claim 1 for Photostabilization of combinations of UV absorbers of the type Methoxycinnamate derivatives with dibenzoylmethane derivatives. 12. Use of compounds of formula (I) according to claim 1 in Combination with one or more other UV absorbers synergistic enhancement of the photo protection effect in cosmetic and pharmaceutical sunscreen preparations. 13. Use of compounds of formula (I) according to claim 1 in Combination with one or more other UV absorbers and coated or non-coated pigments or nanopigments of Metal oxides for synergistic enhancement of the photo protection effect in cosmetic and pharmaceutical sunscreen preparations. 14. Use of compounds of formula (I) according to claim 1 in combination with one or more further UV absorbers and coated or non-coated pigments or nanopigments of metal oxides so that UV broadband _{protection performance} with a critical wavelength λ _crit. ≍ 380 nm results. 15. Light protection preparations according to claims 1 to 8 which continue cosmetic auxiliaries such as fats, emulsifiers, thickeners, emollients, organic solvents, polymers, silicones, antioxidants, perfumes, Preservatives, vitamins, complexing agents, skin lightening agents, Contain plant extracts, dyes and coolants or refreshments. 16. light protection preparations according to claims 1 to 8 as an emulsion, Milk, lotion or cream, aerosol, hydrodispersion or oil gel, spray, Foam, solution, powder, grease stick or as other common cosmetic or pharmaceutical preparation. 17. Sunscreen preparations as claimed in claims 1 to 8 as waterproof Wording available. 18. Compounds of formula (IB) according to claims 3 and 4. 19. Compounds from the group of 3-oxo-4,4-dimethyl-pentanenitriles from the series
2 - [(2,3-Dihydro-1H-indol-1-yl) methylene] -4,4-dimethyl-3-oxopentanenitrile, 2- [(2,3-dihydro-2-methyl-1H-indole -1-yl) methylene] -4,4-dimethyl-3-oxopentanenitrile, 2 - [(2,3-dihydro-5-methyl-1H-indol-1-yl) methylene] -4,4-dimethyl -3- oxo-pentonitrile,
2 - [(2,3-dihydro-2,3-dimethyl-1H-indol-1-yl) methylene] -4,4-dimethyl-3-oxopentanenitrile, 2 - [(2,3-dihydro-2 , 5-dimethyl-1H-indol-1-yl) methylene] -4,4-dimethyl-3-oxopentanenitrile, 2 - [(2,3-dihydro-2,3,3-trimethyl-1H-indole- 1-yl) methylene] -4,4-dimethyl-3-oxopentanenitrile, 2 - [(2,3-dihydro-5-methoxy-1H-indol-1-yl) methylene] -4,4-dimethyl- 3-oxopentanenitrile, 2 - [(2,3-dihydro-2-methyl-5-methoxy-1H-indol-1-yl) methylene] -4,4-dimethyl-3-oxopentanenitrile, 2- [ (2,3-dihydro-2,3,3-trimethyl-5-methoxy-1H-indol-1-yl) methylene] -4,4-dimethyl-3-oxopentanenitrile, 2- [1- (2, 3-dihydro-2-methyl-1H-indol-1-yl) ethylidene] -4,4-dimethyl-3-oxopentanenitrile, 2- [1- (3,4-dihydro-1 (2H) -quinolinyl) methylene] -4,4-dimethyl-3-oxopentanenitrile, 2- [1- (3,4-dihydro-1 (2H) - quinolinyl) ethylidene] -4,4-dimethyl-3-oxopentanenitrile, 2 - [(1,2,3,4,10,11-hexahydro-9H-carbazol-9-yl) methylene] -4,4-dimethyl-3-oxo-pentanenitrile. 20. Use of compounds of formula (IB) according to claims 3 and 4 to protect technical products such as paints, varnishes, Plastics, textiles, polymers, packaging materials and rubbers against the damaging effects of UV radiation.