EP1458340A1

EP1458340A1 - Cosmetic and dermatological light-protective formulations comprising bis-resorcinyltriazine derivatives and benzoxazole derivatives

Info

Publication number: EP1458340A1
Application number: EP02793027A
Authority: EP
Inventors: Anja Göppel; Jens Schulz; Kerstin Hoop
Original assignee: Beiersdorf AG
Current assignee: Beiersdorf AG
Priority date: 2001-12-20
Filing date: 2002-12-16
Publication date: 2004-09-22
Also published as: WO2003053389A1; JP2005513089A; DE10162844A1; US20050013782A1

Abstract

The invention relates to cosmetic or dermatological preparations effective as light-protectives, characterised in comprising (a) at least one bis-resorcinyltriazine derivative and (b) at least one benzoxazole derivative.

Description

description

Cosmetic and dermatological light protection formulations containing bis-resorcinyltriazine derivatives and benzoxazole derivatives

The present invention relates to cosmetic and dermatological light protection preparations, in particular it relates to cosmetic and dermatological formulations with increased UV-A protection.

The damaging effect of the ultraviolet part of solar radiation on the skin is generally known. Depending on their wavelength, the rays have different effects on the skin organ:

The so-called UV-C radiation with a wavelength between 100 and 280 nm is absorbed by the ozone layer in the earth's atmosphere and is therefore not found in the solar spectrum. It is therefore of no physiological importance when sunbathing.

The so-called UV-B range is between 290 nm and 320 nm. UV-B rays are essential for long-lasting tanning of the skin, but can also cause erythema, simple sunburn or even more or less severe burns. Chronic light damage, photodermatosis and herpes solaris can also be caused by UV-B radiation.

It has long been incorrectly assumed that the long-wave UV-A radiation with a wavelength between 320 nm and 400 nm only a negligible biological ^¬ specific effect and in that, accordingly, the UV-B rays responsible for most of photodamage in human skin are. However, numerous studies have now shown that UV-A radiation is pho- todynamic, especially phototoxic reactions and chronic changes in the skin is far more dangerous than UV-B radiation. The damaging influence of UV-B radiation can also be intensified by UV-A radiation.

So it is u. a. proved that even UV-A radiation under normal everyday conditions is sufficient to quickly damage the collagen and elastin fibers, which are essential for the structure and firmness of the skin. This leads to chronic light-induced skin changes - the skin "ages" prematurely. The clinical appearance of the skin aged by light includes, for example, wrinkles and fine lines as well as an irregular, furrowed relief. Furthermore, the areas affected by light-induced skin aging may have irregular pigmentation. Brown spots, keratoses and even carcinomas or malignant melanomas are also possible, and skin that has aged prematurely due to everyday UV exposure is also characterized by less activity of the Langerhans cells and a slight, chronic inflammation.

About 90% of the ultraviolet radiation reaching the earth consists of UV-A rays. While UV-B radiation varies greatly depending on numerous factors (eg time of year and time of day or latitude), UV-A radiation remains relatively constant day by day, irrespective of the time of year, day or geographical factors , At the same time, the majority of UV-A radiation penetrates the living epidermis, while around 70% of UV-B rays are retained by the horny layer.

The more recent findings on the effect of UV-A rays on the skin have led to increased attention being paid to protective measures for this radiation area. Virtually no sun protection product can do without an effective UV-A filter effect, pure UV-B filter preparations are rare.

When applying a sunscreen to the skin, the ultraviolet Strah ^¬ can len be attenuated by two effects: firstly, by reflection and scattering of rays on the surface of powdery solids (physical light ^¬ protection) and on the other by absorption of chemical substances (chemical sunscreen ). It differs depending on which wavelength range is absorbed between UV-B filters (absorption range 280 to 320 nm), UV-A filters (absorption range 320 to 400 nm) and broadband filters (absorption range 290 to approx. 380 nm).

Numerous compounds are known for protection against UV-B radiation, and their absorption maximum should be around 308 nm, since this is where the greatest erythema activity of solar radiation is present. Typical UV-B filters are e.g. B. derivatives of 3-benzylidene camphor, 4-aminobenzoic acid, cinnamic acid, salicylic acid, benzophenone and also 2-phenylbenzimidazole.

Some compounds are also known for protection against UV-A radiation, such as, in particular, dibenzoylmethane derivatives. However, dibenzoylmethane derivatives are generally not photostable, which is why cosmetic or dermatological preparations containing this substance should expediently also contain certain UV stabilizers. Other known UV-A filter substances are certain water-soluble, sulfonated UV filter substances, such as. B. phenylene-1,4-bis (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid and its salts.

In addition to the pure UV-A or UV-B filters, there are substances that cover both areas. This group of broadband filters includes, for example, asymmetrically substituted s-triazine compounds, such as. B. 2,4-bis - {[4- (2-ethylhexyloxy) -2-hydroxy] phenyl} -6- (4-methoxyphenyl) -1,3,5-triazine (INCI: bis -Ethylhexyloxylphenol methoxy-phenyl triazine), certain benzophenones, such as. B. the 2-hydroxy-4-methoxy-benzophenone (INCI: Benzophenone 3) or the 2,2'-methylene-bis- (6- (2H-benzotriazol-2-yl) -4- (1, 1 , 3,3-tetramethylbutyl) phenol) (INCI: Methylene Bis-Benzotriazolyl Tetramethylene-butylphenol).

In general, the light absorption behavior of light protection filter substances is very well known and documented, especially since most industrialized countries have positive lists for the use of such substances, which create very strict standards on the documentation ^¬ mentation. Since not only the position of the absorption maximum, but above all the absorption range is important for the characterization of a filter substance, absorption spectra of each substance are recorded. For the dosage of the substances in the finished formulations, however, the extinction values can at best be an orientation offer assistance because interactions with ingredients of the skin or the surface of the skin itself can cause uncertainties. Furthermore, it is generally difficult to estimate in advance how evenly and in what layer thickness the filter substance is distributed in and on the hom layer of the skin.

The IPD method (IPD ≡ immediate pigment darkening) is usually used to test UV-A protection. Similar to the determination of the sun protection factor, a value is determined that indicates how much longer the skin protected with the light protection agent can be irradiated with UV-A radiation until the same pigmentation occurs as for the unprotected skin.

However, the use concentration of known light protection filter substances which are present as a solid and which also have a high filter effect, particularly in the UV-A range, is often limited, especially in combination with other substances to be dissolved. It therefore presents certain formulation difficulties to achieve higher sun protection factors or UV-A protection performance.

Since light protection filter substances are generally expensive and since some light protection filter substances are also difficult to incorporate in higher concentrations in cosmetic or dermatological preparations, it was the object of the invention to obtain preparations in a simple and inexpensive manner which, at unusually low concentrations, of conventional UV -A light protection filter substances nevertheless achieve an acceptable or even high UV-A protection performance.

It was surprising and unforeseeable for the person skilled in the art that cosmetic or dermatological preparations which have a light protection ^{effect are} characterized by the fact that they

(a) at least one bis-resorcinyltriazine derivative and

(b) contain at least one benzoxazole derivative which would remedy the disadvantages of the prior art.

The compositions of the invention provide in every respect very befriedi ^¬ constricting preparations is that not restricted to a limited selection of raw materials are. Accordingly, they are particularly suitable to serve as the basis for forms of preparation with a variety of uses. The preparations according to the invention show very good sensory and cosmetic properties, such as, for example, the distributability on the skin or the ability to be absorbed into the skin, and are also notable for very good light protection effectiveness, an extremely high UV-A protection performance and excellent skin compatibility at the same time excellent skin care data.

The invention therefore also relates to cosmetic or dermatological preparations which have a light protection effect, characterized in that they contain synergistic combinations of substances

(a) at least one bis-resorcinyltriazine derivative and ^"

(b) contain at least one benzoxazole derivative, the UV protection, in particular the UV-A protection, of these preparations being increased disproportionately.

The combinations of substances according to the invention are surprisingly synergistic, that is to say superadditive in relation to the individual components. They are photostable without further additives and show a surprisingly high protection performance in the UV-A range.

Advantageous benzoxazole derivatives in the sense of the present invention are distinguished by the following structural formula,

wherein R ¹ , R ² and R ^{3 are} independently selected from the group of branched or unbranched, saturated or unsaturated alkyl radicals having 1 to 10 carbon atoms. It is particularly advantageous according to the invention to choose the radicals R ¹ and R ^{2 the} same, in particular from the group of the branched alkyl radicals having 3 to 5 carbon atoms. It is furthermore particularly advantageous for the purposes of the present invention if R ^{3 is} an unbranched or branched alkyl radical having 8 carbon atoms, in particular the 2-ethylhexyl radical.

Benzoxazole derivative which is particularly preferred according to the invention is 2,4-bis- [5-1 (dimethylpropyl) benzoxazol-2-yl- (4-phenyl) -imino] -6- (2-ethylhexyl) -imino-1, 3,5-triazine with CAS No. 288254-16-0, which is characterized by the structural formula

distinguished and is available from 3V Sigma under the trade name Uvasorb® K2A.

The benzoxazole derivative or derivatives are advantageously present in dissolved form in the cosmetic preparations according to the invention. It may also be advantageous, if necessary, but when the or benzoxazole derivatives in pigmentary, ie undissolved form - at ^¬ play nm in particle sizes of 10 nm up to 300 - are present.

The total amount of one or more of benzoxazole derivatives in the finished kos ^¬ metic or dermatological preparations is advantageously 0.01 wt .-% to 20 wt .-%, preferably of 0.1 selected from the range to 10 wt .-%, each be ^¬ subjected to the total weight of the preparations. Bis-resorcinyltriazine derivatives in the sense of the present invention are distinguished by the following structural formula:

where R ¹ , R ² and R ^{3 are} independently selected from the group of branched and unbranched alkyl groups having 1 to 10 carbon atoms or a single hydrogen atom. According to the invention, 2,4-bis - {[4- (2-ethyl-hexyloxy) -2-hydroxy] phenyl} -6- (4-methoxypheηyl) -1, 3,5-triazine (INCI: bis -Ethylhexyloxylphenol Methoxyphenyl Triazin), which is available under the trade name Tinosorb® S from CIBA-Chemicals GmbH. Another preferred bis-resorcinyltriazine derivative is the 2- [4,6-bis (2,4-dimethylphenyl) -1, 3,5-triazin-2-yl] -5- (octyloxy) phenol (CAS No .: 2725- 22-6).

The total amount of one or more bis-resorcinyltriazine derivatives in the finished cosmetic or dermatological preparations is advantageously chosen in each case from the range from 0.01% by weight to 20% by weight, preferably from 0.1 to 10% by weight on the total weight of the preparations.

It is particularly advantageous to adjust the weight ratios of the benzoxazole derivative (s) to the bis-resorcinyltriazine derivative (s) such as 30: 1 to 1:30, preferably as 10: 1 to 1:10, particularly preferably as 5: 1 to 1 : 5 to choose.

For the purposes of the present invention, the preparations can preferably contain, in addition to one or more oil phases, one or more water phases and, for example, in the form of W / O, O / W, W / O / W or O / W / O emulsions , Sol- Before formulations, microemulsions, sticks, foams (so-called mousse), solid emulsions (ie emulsions which are stabilized by solids, eg Pickering emulsions), sprayable emulsions or hydrodispersions can preferably also be. Furthermore, the preparations can advantageously also be oil-free and / or aqueous / alcoholic solutions.

Sprayable emulsions, especially microemulsions

Sprayable O / W emulsions, in particular O / W microemulsions, are particularly advantageous for the purposes of the present invention.

The droplet diameters of the usual “simple”, that is to say non-multiple, emulsions are in the range from approx. 1 μm to approx. 50 μm. Such “macroemulsions” are colored milky white and opaque without further coloring additives. Finer "macroemulsions", whose droplet diameters are in the range from approximately 0.5 μm to approximately 1 μm, are again blue-white in color and opaque, without coloring additives. Such “macroemulsions” usually have a high viscosity.

The droplet diameter of microemulsions in the context of the present invention, on the other hand, is in the range from about 50 to about 500 nm. Such microemulsions are colored bluish white to translucent and mostly of low viscosity. The viscosity of many O / W type microemulsions is comparable to that of water.

The advantage of microemulsions is that in the dispersed phase ingredients much more finely dispersed form can be present as in the disperse phase of "macroemulsions". A is white ^¬ more excellent advantage that they can be sprayed due to their low viscosity. If Mi ^¬ kroemulsionen used as cosmetics, Corresponding products are characterized by high cosmetic elegance.

According to the invention advantageous are, in particular O / W microemulsions, which are obtained with the aid of so-called phase inversion temperature technology and minde ^¬ least contain an emulsifier (emulsifier A), which is selected from the group of emulsifiers having the following properties: their lipophilicity depends on the temperature, such that the lipophilicity increases by increasing the temperature and the lipophilicity of the emulsifier decreases by lowering the temperature. Advantageous emulsifiers A are e.g. B. polyethoxylated fatty acids (PEG-100 stearate, PEG-20 stearate, PEG-150 laurath, PEG-8 distearate and the like) and / or polyethoxylated fatty alcohols (cetearath-12, cetearath-20, isoceteth-20, beheneth-20, Lau - reth-9 etc.) and / or alkyl polyglycosides (cetearyl glycoside, stearyl glycoside, palmityl glycoside etc.).

If the phase inversion is initiated essentially by varying the temperature, O / W emulsions, in particular O / W microemulsions, are available, the size of the oil droplets being essentially determined by the concentration of the emulsifier (s) used, such that a higher one Emulsifier concentration causes smaller droplets and lower emulsifier concentration leads to larger droplets. The droplet sizes are usually between 20 and 500 nm.

In the sense of the present invention, it may be advantageous to use further W / O and / or O / W emulsifiers not falling under the definition of emulsifier A, for example to increase the water resistance of the preparations according to the invention. Here z. B. alkyl methicon copolyols and / or alkyl dimethicone copolyols (in particular cetyl dimethicone copolyol, lauryl methicone copolyol), W / O emulsifiers (such as sorbitan stearate, glyceryl stearate, glycerol stearate, sorbitan oleate, lecithin, glyceryl isostearate 3-polygly , polyglyceryl-3 diisostearate, PEG-7 hydrogenated castor oil, polyglyceryl-4 isostearate, acrylates / C _10th ₃₀ alkyl crosspolymer, sorbitan isostearate, poloxamer 101, polyglyceryl-2-dipolyhydroxystearate, polyglyceryl-3 diisostearate , Polyglyceryl-4-dipolyhydroxystearate, PEG-30-dipolyhydroxystearate, diisostearoyl-polyglyceryl-3-diisostearate, glycol distearate, polyglyceryl-3-dipolyhydroxystearate) and / or fatty acid esters of sulfuric or phosphoric acid (cetyl phosphate, trilaureth-4-8 phosphate -Phosphate, stearyl phosphate, cetearyl sulfate etc.) can be used.

Further advantageous sprayable O / W emulsions for the purposes of the present invention are low-viscosity cosmetic or dermatological hydrodispersions which contain at least one oil phase and at least one water phase, the preparations tion is stabilized by at least one gel former and need not necessarily contain emulsifiers, but may contain one or more emulsifiers.

Advantageous gel formers for such preparations are, for example, copolymers of C ₁₀ . ₃₀ alkyl acrylates and one or more monomers of acrylic acid, methacrylic acid or their esters. The INCI name for such compounds is "Acrylates / C 10-30 Alkyl Acrylate Crosspolymer". The Pemulen® types TR 1, TR 2 and TRZ from Goodrich (Noveon) are particularly advantageous.

Carbopole are also advantageous gel formers for such preparations. Carbopols are polymers of acrylic acid, especially also acrylate-alkyl acrylate copolymers. Advantageous carbopoles are, for example, types 907, 910, 934, 940, 941, 951, 954, 980, 981, 1342, 1382, 2984 and 5984. ETD types 2020, 2050 and Carbopol Ultrez 10 are also further advantageous gel formers for such Preparations are xanthan gum, cellulose derivatives and locust bean gum.

Possible (optional) emulsifiers which can be used are ethoxylated fatty alcohols or ethoxylated fatty acids (in particular PEG-100 stearate, ceteareth-20) and / or other nonionic surface-active substances.

Furthermore, the very low viscosity to sprayable emulsions can also be W / O or water-in-silicone oil (W / S) emulsions. W / O or W / S emulsions which contain at least one silicone emulsifier (W / S) with an HLB value <8 and / or at least one W / O emulsifier with an HLB value <7 are particularly advantageous and contain at least one O / W emulsifier with an HLB value> 10. Such preparations also contain at least 20% by weight of lipids, the lipid phase advantageously also containing silicone oils or even consisting entirely of such oils.

The one or more silicone emulsifiers can advantageously polyols from the group of Alkylmethiconco ^¬ and / or alkyldimethicone copolyols is chosen (such. As dimethicone which from Goldschmidt AG under the trade designations ABIL® B 8842, ABIL® B 8843, ABIL® B 8847 , ABIL® B 8851, ABIL® B 8852, ABIL® B 8863, ABIL® B 8873 and ABIL® B 88183 are sold, cetyl dimethicone copolyol [Goldschmidt AG / ABIL® EM 90], cyclomethicone dimethicone copolyol [Goldschmidt AG / ABIL® EM 97], lauryl methicone copolyol [Dow Corning Ltd. / Dow Corning® 5200 Formulation Aid], octyl dimethicone ethoxy glucoside [from Wacker].

The one or more W / O emulsifiers with an HLB value <7 can advantageously be selected from the following group: sorbitan stearate, sorbitan oleate, lecithin, glyceryl alcoholate, lanolin, hydrogenated castor oil, glyceryl isostearate, polyglyceryl-3-oleate, pentaerythrithyl isostearate, methylglucose dioleate Mixture with hydroxy stearate and beeswax, PEG-7 hydrogenated castor oil, polyglyceryl 4-isostearate, hexyl laurate, acrylate / C ₁₀ . ₃₀ - alkyl acrylate cross-polymer, sorbitan isostearate, poloxamer 101, polyglyceryl-2-dipolyhydroxystearate, polyglyceryl-3-diisostearate, PEG-30-dipolyhydroxystearate, diisostearoyi-polyglyceryl-3-diisostearate, polyglyceryl-3-dipolyhydroxystearate - hydroxystearate, polyglyceryl-3-dioleate.

The O / W emulsifier (s) with an HLB value> 10 can advantageously be selected from the following group: glyceryl stearate in a mixture with ceteareth-20, ceteareth-25, ceteareth-6 in a mixture with stearyl alcohol, cetylstearyl alcohol in a mixture with PEG-40 - Castor oil and sodium cetyl stearyl sulfate, triceteareth-4 phosphate, glyceryl stearate, sodium cetyl stearyl sulfate, lecithin trilaureth-4 phosphate, laureth-4 phosphate, stearic acid, propylene glycol stearate SE, PEG-9 stearate, PEG-20 stearate, PEG -40- stearate, PEG-100 stearate, ceteth-2, ceteth-20, polysorbate-20, polysorbate-60, polysorbate-65, polysorbate-100, glyceryl stearate in a mixture with PEG-100 stearate, ceteareth- 3, isostearylglyceryl ether, cetylstearyl alcohol in a mixture with sodium cetylstearyl sulfate, PEG-40 stearate, glycol distearate, PEG-22-dodecyl glycol copolymer, polyglyceryl-2-PEG-4 stearate, ceteareth-12, ceteareth-20, Ceteareth-30, methyl glucose sesquistearate, steareth-10, PEG-20 stearate, steareth-21, stea reth-20, isosteareth-20, PEG-45 / dodecylglycol copolymer, methoxy-PEG-22 / dodecylglycol copolymer, glyceryl stearate SE, ceteth-20, PEG-20-methylglucose sesquistearate, glyceryl stearate citrate, cetylphosphate, sorbitol sulfate, cetorbyl sulfate Triceteareth-4-phosphate, trilaureth-4-phosphate, polyglyceryl-methyl glucose distearate, potassium cetyl phosphate, isosteareth-10, poly-glyceryl-2-sesquiisostearate, ceteth-10, isoceteth-20, glyceryl stearate in a mixture with ceteareth 20 12, cetyl stearyl alcohol and cetyl palmitate, PEG-30 stearate, PEG-40 stearate, PEG-100 stearate. Aqueous-alcoholic solutions are also advantageous. They can contain from 0% by weight to 90% by weight of ethanol. For the purposes of the present invention, aqueous alcoholic solutions can advantageously also contain solubilizers, such as. B. PEG-40 or PEG-60 hydrogenated.es castor oil.

The preparations according to the invention can advantageously also be used as cosmetic or dermatological impregnation solutions, with which in particular water-insoluble substrates - such as, for. B. woven or non-woven cloths - are moistened. Such impregnation solutions are preferably low-viscosity, in particular sprayable (such as, for example, PIT emulsions, hydrodispersions, W / O emulsions, oils (see below), aqueous solutions etc.) and preferably have a viscosity of less than 2000 mPa s, in particular less than 1,500 mPa-s (measuring device: Haake Viscotester VT-02 at 25 ° C). With their help, for example, cosmetic sun protection wipes, care wipes and the like are available, which represent the combination of a soft, water-insoluble material with the low-viscosity cosmetic and dermatological impregnation solution.

Ole

The preparations according to the invention can advantageously also be present as anhydrous oils or oil gels or pastes. Advantageous oils are e.g. B. synthetic, semi-synthetic or natural oils such as rapeseed oil, rice oil, avocado oil, olive oil, mineral oil, cocoglycerides, butylene glycol dicaprylate / dicaprate, C ₁₂ . ₁₅ alkyl benzoate, dicaprylyl carbonate, octyl dodecanol and the like. Various waxes with a melting point> 25 ° C can be used as oil gel formers. Gel formers from the group of aerosils, alkylgalactomannans (for example N-Hance AG 200 and N-Hance AG 50 from Hercules) and polyethylene derivatives are also advantageous.

foams

Particularly advantageous for the purposes of the present invention are also self-foaming ^¬ de, foam-like, after-foaming or foamable cosmetic and dermatologi ^¬ cal preparations. “Self-foaming”, “foam-like”, “post-foaming” or “foamable” are understood to mean preparations from which foams - be it already during the manufacturing process, be it in use by the consumer or in some other way - by entering one or several gases can be produced in principle. In such foams, the gas bubbles are (arbitrarily) distributed in one (or more) liquid phase (s), the (foamed) preparations not necessarily having to have the appearance of a foam macroscopically. (Foamed) cosmetic or dermatological preparations according to the invention (hereinafter also referred to simply as foams for the sake of simplicity) can, for. B. represent macroscopically visible dispersed systems from gases dispersed in liquids. The foam character can, for example, only become visible under a (light) microscope. In addition, foams according to the invention - especially when the gas bubbles are too small to be recognized under a light microscope - can also be recognized from the large increase in volume of the system.

For the purposes of the present invention, such preparations advantageously contain an emulsifier system which consists of

A. at least one emulsifier A, selected from the group of fully, partially or not neutralized, branched and / or unbranched, saturated and / or unsaturated fatty acids with a chain length of 10 to 40 carbon atoms,

B. at least one emulsifier B, selected from the group of polyethoxylated fatty acid esters with a chain length of 10 to 40 carbon atoms and with a degree of ethoxylation of 5 to 100 and

C. at least one co-emulsifier C, selected from the group consisting of saturated and / or unsaturated, branched and / or unbranched fatty alcohols with a chain length of 10 to 40 carbon atoms.

The emulsifier or emulsifiers A are preferably selected from the group of ren Fettsäu ^¬ which hydroxide wholly or partially with customary alkalis (such. As sodium and / or potassium, sodium and / or potassium carbonate, and mono- and / or Triethanolamine) are neutralized. For example, stearic acid and stearates, isostearic acid and isostearates, palmitic acid and palmitates, and myristic acid and myristates are particularly advantageous. The emulsifier (s) B are preferably selected from the following group: PEG-9 stearate, PEG-8 distearate, PEG-20 stearate, PEG-8 stearate, PEG-8 oleate, PEG-25 glyceryl trioleate, PEG- 40-sorbitan lanolate, PEG-15 glyceryl ricinoleate, PEG-20 glyceryl stearate, PEG-20 glyceryl isostearate, PEG-20 glyceryl oleate, PEG-20 stearate, PEG-20 methyl glucose sesquistearate, PEG-30 glyceryl isostearate, PEG Glyceryl laurate, PEG-30 stearate, PEG-30 glyceryl stearate, PEG-40 stearate, PEG-30 glyceryl laurate, PEG-50 stearate, PEG-100 stearate, PEG-150 laurate. Polyethoxylated stearic acid esters, for example, are particularly advantageous.

According to the invention, the co-emulsifier (s) C are preferably selected from the following group: behenyl alcohol (C ₂₂ H ₅ OH), cetearyl alcohol [a mixture of cetyl alcohol (C ₁₆ H ₃₃ OH) and stearyl alcohol (C ₁₈ H ₃₇ OH)], lanolin alcohols (wool wax alcohols) , which represent the unsaponifiable alcohol fraction of the wool wax which is obtained after the saponification of wool wax). Cetyl and cetyl stearyl alcohol are particularly preferred.

It is advantageous according to the invention to choose the weight ratios of emulsifier A to emulsifier B to coemulsifier C (A: B: C) as a: b: c, where a, b and c independently of one another are rational numbers from 1 to 5, preferably from 1 can represent up to 3. A weight ratio of approximately 1: 1: 1 is particularly preferred.

For the purposes of the present invention, it is advantageous for the total amount of emulsifiers A and B and of coemulsifier C to be in the range from 2 to 20% by weight, advantageously from 5 to 15% by weight, in particular from 7 to 13% by weight. %, each based on the total weight of the formulation.

Pickering / solid stabilized emulsions

Cosmetic or dermatological preparations which are only stabilized by finely divided solid particles are also particularly advantageous in the sense of the present invention. Such “emulsifier-free” emulsions are also referred to as Pickering emulsions. In Pickering emulsions, the solid material accumulates at the oil / water phase boundary in the form of a layer, which prevents the disperse phases from flowing together. The surface properties of the solid particles, which should show both hydrophilic and lipophilic properties, are of particular importance.

The stabilizing solid particles can also advantageously be surface-treated ("coated"), whereby an amphiphilic character of these solid particles is to be formed or retained. The surface treatment can consist in that the solid particles are treated with a thin hydrophobic by methods known per se or hydrophilic layer.

The average particle diameter of the microfine solid particles used as a stabilizer is preferably chosen to be less than 100 μm, particularly advantageously less than 50 μm. It is essentially irrelevant in which form (platelets, rods, beads, etc.) or modification the solid particles used are present.

The microfine solid particles are preferably selected from the group of the amphiphilic metal oxide pigments. The following are particularly advantageous: • Titanium dioxides (coated and uncoated): z. B. Eusolex T-2000 from Merck, titanium dioxide MT-100 Z from Tayca Corporation

• zinc oxides z. B. Z-Cote and Z-Cote HP1 from BASF AG, MZ-300, MZ-500 and MZ-505M from Tayca Corporation

• Iron oxides It is also advantageous if the microfine solid particles are selected from the following group: boron nitrides, starch derivatives (tapioca starch, sodium com starch octynyl succinate etc.), talc, latex particles.

It is according to the invention advantageous if the solids-stabilized emulsions significantly less than 0.5 wt .-% of one or more emulsifiers or even Gänz are ^¬ Lich emulsifier. pencils

Preparations in the form of pens are also advantageous for the purposes of the invention. From a technical point of view, most stick formulations are water-free fat mixtures made from solid or semi-solid waxes and liquid oils, with highly purified paraffin oils and waxes being the stick base.

Conventional base materials for stick preparations are, for example, liquid oils (such as. For example, paraffin oils, castor oil, isopropyl myristate, _C12. ₁₅ alkyl benzoate) (for. Example, petroleum jelly, lanolin), semi-solid components, solid components (eg. For example, beeswax, ceresin and microcrystalline waxes or ozokerite) and / or high-melting waxes (eg carnauba wax, candelilla wax). Water-containing stick-like preparations are also known per se, although these can also be in the form of W / O emulsions.

The cosmetic or dermatological light protection formulations according to the invention can be composed as usual and can be used for cosmetic 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.

Depending on their structure, cosmetic or topical dermatological compositions can be used for the purposes of the present invention, for example as skin protection cream, cleansing milk, day or night cream, etc. It may be possible and advantageous to use the compositions according to the invention as the basis for pharmaceutical formulations.

For use, the cosmetic and dermatological preparations are applied to the skin and / or the hair in a sufficient amount in the manner customary for cosmetics.

The cosmetic and dermatological preparations according to the invention can comprise cosmetic auxiliaries such as are usually applies in such preparations ver ^¬ be such. B. preservatives, preservation aids, complexing agents, bactericides, perfumes, substances to prevent or increase foaming, dyes, pigments that have a coloring effect, thickeners, moisturizing and / or moisturizing substances, fillers that improve the feeling on the skin, fats, oils, Waxes or other common components of a cosmetic or dermatological see formulations such as alcohols, polyols, polymers, foam stabilizers, electrolytes, organic solvents or silicone derivatives.

Advantageous preservatives for the purposes of the present invention are, for example, formaldehyde releasers (such as, for example, DMDM hydantoin, which is available, for example, from Lonza under the trade name Glydant ™), iodopropylbutylcarbamate (for example those under the trade names Glycacil -L, Glycacil-S available from Lonza and / or Dekaben LMB from Jan Dekker), parabens (ie alkyl p-hydroxybenzoate, such as methyl, ethyl, propyl and / or butyl paraben), phenoxyethanol, Ethanol, benzoic acid and the like. According to the invention, the preservation system usually also advantageously includes preservation aids, such as, for example, octoxyglycerol, glycine soy, etc.

Advantageous complexing agents for the purposes of the present invention are, for example, EDTA, [S, S] -ethylenediamine disuccinate (EDDS), which is available, for example, from Octel under the trade name Octaquest, pentasodium-ethylenediaminetetramethylenephosphonate, which, for. B. is available under the trade name Dequest 2046 from Monsanto and / or iminodisuccinic acid, which u. a. is firmly available from Bayer AG under the trade names Iminodisuccinat VP OC 370 (approx. 30% solution) and Baypure CX 100.

Particularly advantageous preparations are also obtained if antioxidants are used as additives or active ingredients. According to the invention, the preparations advantageously contain one or more antioxidants. All of the antioxidants suitable or customary for cosmetic and / or dermatological applications can be used as inexpensive, but nevertheless optional, antioxidants.

For the purposes of the present invention, water-soluble antioxidants, such as vitamins, e.g. B. ascorbic acid and its derivatives.

Preferred antioxidants are also vitamin E and its derivatives and vitamin A and its derivatives. The amount of the antioxidants (one or more compounds) in the preparations is preferably 0.001 to 30% by weight, particularly preferably 0.05 to 20% by weight, in particular 0.1 to 10% by weight, based on the total weight the preparation.

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

If vitamin A or vitamin A derivatives or carotenes or their derivatives represent the antioxidant or antioxidants, it is advantageous to add their respective concentrations in the range from 0.001 to 10% by weight, based on the total weight of the formulation choose.

It is particularly advantageous if the cosmetic preparations according to the present invention contain cosmetic or dermatological active ingredients, preferred active ingredients being antioxidants which can protect the skin from oxidative stress.

Further advantageous active substances in the sense of the present invention are natural active substances and / or their derivatives, such as. B. alpha-lipoic acid, phytoene, D-biotin, coenzyme Q10, alpha-glucosylrutin, camitin, carnosine, natural and / or synthetic isoflavonoids, creatine, taurine and / or ß-alanine and 8-hexadecene-1, 16- dicarboxylic acid (Dioic acid, CAS number 20701 -68-2; provisional INCI name Octadecendioic acid).

Recipes according to the invention, which, for. B. known anti-wrinkle agents such as flavone glycosides (especially α-glycosylrutin), coenzyme Q10, vitamin E and / or derivatives and the like, are particularly advantageous for the prophylaxis and treatment of cosmetic or dermatological skin changes such as z. B. occur with skin aging (such as dryness, roughness and formation of dry lines, itching, reduced re-greasing (e.g. after washing), visible vasodilation (telangiectasias, cuperosis), flaccidity and formation of wrinkles and fine lines, local hyper- , Hypo and incorrect pigmentation (e.g. age spots), increased susceptibility to mechanical stress (e.g. cracking) and the like). They are also advantageous against the appearance of the dry chapped or rough skin.

The water phase of the preparations according to the invention can advantageously contain customary cosmetic auxiliaries, such as, for example, alcohols, in particular those with a low C number, preferably ethanol and / or isopropanol, diols or polyols with a low C number, and their ethers, preferably propylene glycol, glycerol, butylene glycol, Ethylene glycol, ethylene glycol monoethyl or monobutyl ether, propylene glycol monomethyl, monoethyl or monobutyl ether, diethylene glycol monomethyl or monoethyl ether and analog products, polymers, foam stabilizers, electrolytes and in particular one or more thickeners, which one or more can advantageously be chosen from the group 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 [from Bf. Goodrich], for example carbopoles of types 980, 981, 1382, 2984, 5984, ETD 2020, ETD 2050, Ultrez 10, each individually or in combination.

The preparations according to the invention can also advantageously contain self-tanning substances, such as, for example, dihydroxyacteon and / or melanin derivatives in concentrations of 1% by weight to 8% by weight, based on the total weight of the preparation.

The preparations according to the invention can also advantageously contain repellents for protection against mosquitoes, ticks and spiders and the like. Are advantageous for. B. N, N-diethyl-3-methylbenzamide (trade name: Meta-delphene, "DEET"), dimethyl phthalate (trade name: Palatinol M, DMP) and in particular 3- (Nn-butyl-N-acetylamino) - ethyl propionate (available under the trade name Insekt Repellent® 3535 from Merck) The repellents can be used both individually and in combination.

Moisturizers are substances or mixtures of substances that give cosmetic or dermatological preparations the property that after application or distribution on the surface of the skin, the release of moisture from the home layer (also trans- reduce epidermal water loss (called TEWL) and / or have a positive effect on the hydration of the horny layer.

Advantageous moisturizers for the purposes of the present invention are, for example, glycerin, lactic acid and / or lactates, in particular sodium lactate, butylene glycol, propylene glycol, biosaccaride gum-1, glycine soya, ethylhexyloxyglycerol, pyrrolidone carboxylic acid and urea. Furthermore, it is particularly advantageous to use polymeric moisturizers from the group of water-soluble and / or water-swellable and / or water-gelable polysaccharides. Particularly advantageous are, for example, hyaluronic acid, chitosan and / or a fucose-rich polysaccharide, which is filed in the Chemical Abstracts under the registration number 178463-23-5 and z. B. under the name Fucogel®1000 from the company SOLABIA S.A. is available. Moisturizers can also advantageously be used as anti-wrinkle active ingredients for the prophylaxis and treatment of cosmetic or dermatological skin changes, such as those described for. B. occur in skin aging, are used.

The cosmetic or dermatological preparations according to the invention can furthermore advantageously, although not necessarily, contain fillers which, for. B. further improve the sensory and cosmetic properties of the formulations and, for example, cause or intensify a velvety or silky feeling on the skin. Advantageous fillers for the purposes of the present invention are starch and starch derivatives (such as tapioca starch, distarch phosphate, aluminum or sodium starch, octenyl succinate and the like), pigments which have neither primarily UV filter nor coloring effects (such as e.g. boron nitride etc.) and / or Aerosile ^® (CAS No. 7631-86-9).

The oil phase of the formulations according to the invention is advantageously selected from the group of polar oils, for example from the group of lecithins and fatty acid triglycerides, in particular the triglycerol esters of saturated and / or unsaturated, branched and / or unbranched alkane carboxylic acids with a chain length of 8 to 24, in particular ^¬ other 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, such as. B. cocoglyceride, olive oil, sunflower oil, soybean oil, peanut oil, rapeseed oil, almond oil, palm oil, coconut oil, castor oil, wheat germ oil, grape seed oil, safflower oil, evening primrose oil, macadamia nut oil and the like. According to the invention, z. B. natural waxes of animal and vegetable origin, such as beeswax and other insect waxes and berry wax, shea butter and / or lanolin (wool wax).

For the purposes of the present invention, further advantageous polar oil components can also be selected from the group of esters from saturated and / or unsaturated, branched and / or unbranched alkane carboxylic acids having a chain length of 3 to 30 carbon atoms and saturated and / or unsaturated, branched and / or unbranched alcohols with a chain length of 3 to 30 C atoms and from the group of esters from aromatic carboxylic acids and saturated and / or unsaturated, branched and / or unbranched alcohols with a chain length of 3 to 30 C atoms. Such ester oils can then advantageously be selected from the group octyl palmitate, octyl co-coat, octyl isostearate, octyl dodeceyl myristate, octyl dodecanol, cetearyl isononanoate, isopropyl myristate, isopropyl palmitate, isopropyl stearate, isopropyl oleate, n-butyl stearate, n-stonolate, n-stonolate, n-stonyl-n-stonate, 2-ethylhexyl palmitate, 2-ethylhexyl laurate, 2-hexyldecyl stearate, 2-octyldodecyl palmitate, stearyl heptanoate, oleyl oleate, olerlerucate, erucyl oleate, erucylerucate, tridecyl stearate, tridecyltrimetic halosynthesis, as well as synthetic, such as. B. Jojoba oil.

Furthermore, the oil phase can advantageously be selected from the group of dialkyl ethers and dialkyl carbonates. B. dicaprylyl ether (Cetiol OE) and / or dicaprylyl carbonate, for example that available under the trade name Cetiol CC from Cognis.

It is further preferred pentylglykoldiheptanoat the one or more oil components from the group consisting of isoeicosane, neopentyl, propylene glycol dicaprylate / dicaprate, caprylic / capric / Diglyceryl- succinate, butylene glycol dicaprylate dicaprate, C ₁₂ ₃ -ι alkyl lactate, di-C ₁₂ .ι ₃ - Alkyl tartrate, triisostearin, dipentaerythrityl hexacaprylate / hexacaprate, propylene glycol monoisostearate, tri-caprylin, dimethylisosorbide. It is particularly advantageous if the oil phase of the formulations OF INVENTION ^¬ to the invention has a content of C _12th ₁₅ alkyl benzoate or completely ^¬ consists of this. Advantageous oil components are also e.g. B. butyl octyl salicylate (for example that available under the Hallbrite BHB trade name from CP Hall), hexadecyl benzoate and butyl octyl benzoate and mixtures thereof (Hallstar AB) and / or diethyl hexyl naphthalate (Hallbrite TQ or Corapan TQ from H&R).

Any mixtures of such oil and wax components can also be used advantageously for the purposes of the present invention.

Furthermore, the oil phase can also advantageously also contain non-polar oils, for example those which are selected from the group of branched and unbranched hydrocarbons and waxes, in particular mineral oil, petroleum jelly (petrolatum), paraffin oil, squalane and squalene, polyolefins, hydrogenated polyisobutenes and Isohexadecane. Among the polyolefins, polydecenes are the preferred substances.

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

Silicone oils are high-molecular synthetic polymeric compounds in which silicon atoms are linked in a chain and / or network-like manner via oxygen atoms and the remaining valences of silicon by hydrocarbon residues (mostly methyl, more rarely ethyl, propyl, phenyl groups) are saturated). The silicone oils are systematically referred to as polyorganosiloxanes. The methyl-substituted polyorganosiloxanes, which are the most important compounds of this group in terms of quantity and are characterized by the following structural formula

are also known as polydimethylsiloxane or dimethicone (INCI). Dimethicone is available in different chain lengths or with different molecular weights. Particularly advantageous polyorganosiloxanes for the purposes of the present invention are, for example, dimethylpolysiloxanes [poly (dimethylsiloxane)], which are available, for example, under the trade names Abil 10 to 10,000 from Th. Goldschmidt. Phenylmethylpolysiloxanes (INCI: phenyl dimethicone, phenyl trimethicone), cyclic silicones (octamethylcyclotetrasiloxane or decamethylcyclopentasiloxane), which according to INCI are also referred to as cyclomethicones, are also advantageous, amino-modified silicones (INCI: amodimethicone and silicone wax). B. polysiloxane-polyalkylene copolymers (INCI: stearyl dimethicone and cetyl dimethicone) and dialkoxydimethyl polysiloxanes (stearoxy dimethicone and behenoxy stearyl dimethicone), which are available from Th. Goldschmidt as different types of abil wax. However, other silicone oils can also be used advantageously for the purposes of the present invention, for example cetyldimethicone, hexamethylcyclotrisiloxane, polydimethylsiloxane, poly (methylphenylsiloxane).

The preparations according to the invention can also advantageously contain one or more substances from the following group of siloxane elastomers, for example in order to increase the water resistance and / or the sun protection factor of the products:

(a) Siloxane elastomers which contain the units R ₂ SiO and RSiO _{| 5} and / or R ₃ SiO ₀ , and / or SiO ₂ , the individual radicals R each independently of one another being hydrogen, ie. ₂₄ -AlI- alkyl (such as methyl, ethyl, propyl) or aryl (such as phenyl or tolyi), alkenyl (such as vinyl) and the weight ratio of the units R ₂ SiO to RSiö _1ι5 in the range from 1: 1 to 30: 1 is selected;

(b) Siloxane elastomers which are insoluble and swellable in silicone oil and which can be obtained by the addition reaction of an organopolysiloxane (1) containing silicon-bonded hydrogen with an organopolysiloxane (2) containing unsaturated aliphatic groups, the proportions used being chosen so that the amount of hydrogen of the organopolysiloxane (1) or the unsaturated aliphatic groups of the organopolysiloxane (2) is in the range of 1 to 20 mol% when the organopolysiloxane is not cyclic and in the range of 1 to 50 mol% when the organopolysiloxane is cyclic. For the purposes of the present invention, the siloxane elastomer or elastomers are advantageously in the form of spherical powders or in the form of gels.

Advantageous siloxane elastomers in the form of spherical powder according to the invention are those with the INCI name Dimethicone / Vinyl Dimethicone Crosspolymer, for example that available from DOW CORNING under the trade names DOW CORNING 9506 Powder.

It is particularly preferred if the siloxane elastomer is used in combination with oils from hydrocarbons of animal and / or vegetable origin, synthetic oils, synthetic esters, synthetic ethers or mixtures thereof.

It is very particularly preferred if the siloxane elastomer is used in combination with unbranched silicone oils which are liquid or pasty at room temperature or cyclic silicone oils or mixtures thereof. Organopolysiloxane elastomers with the INCI name Dimethicone / Polysilicone-11 are particularly advantageous, especially the Gransil types GCM, GCM-5, DMG-6, CSE Gel, PM-Gel, LTX, ININ available from Grant Industries Inc. Gel, AM-18 gel and / or DMCM-5.

It is very exceptionally preferred if the siloxane elastomer is used in the form of a gel composed of siloxane elastomer and a lipid phase, the content of the siloxane elastomer in the gel being 1 to 80% by weight, preferably 0.1 to 60% by weight , each based on the total weight of the gel.

For the purposes of the present invention, it is advantageous for the total amount of the siloxane elastomers (active content) to be in the range from 0.01 to 10% by weight, advantageously from 0.1 to 5% by weight, based in each case on the total weight of the formulation, to choose.

The cosmetic and dermatological preparations according to the invention can contain dyes and / or color pigments, in particular if they are in the form of decorative cosmetics. The dyes and pigments can be selected from the corresponding positive list in the Cosmetics Ordinance or the EC list of cosmetic colorants. In most cases, they are identical to the colorants approved for food. Advantageous color pigments are, for example, titanium dioxide, Mica, iron oxides (e.g. Fe ₂ O ₃ , Fe ₃ O ₄ , FeO (OH)) and / or tin oxide. Advantageous dyes are, for example, carmine, Berlin blue, chrome oxide green, ultramarine blue and / or manganese violet. It is particularly advantageous to choose the dyes and / or color pigments from the Rowe Color Index, 3rd edition, Society of Dyers and Colorists, Bradford, England, 1971.

If the formulations according to the invention are in the form of products which are used on the face, it is advantageous to choose one or more substances from the following group as the dye: 2,4-dihydroxyazobenzene, 1- (2'-chloro-4'- nitro-1'-phenylazo) -2-hydroxynaphthalene, ceres red, 2- (sulfo-1-naphthylazo) -1-naphthol-4-sulfonic acid, calcium salt of 2-hydroxy-1, 2'-azonaphthalene-1'- sulfonic acid, calcium and barium salts of 1- (2-sulfo-4-methyl-1-phenylazo) -2-naphthylcarboxylic acid, calcium salt of 1- (2-sulfo-1-naphthylazo) -2-hydroxynaphthalene-3-carboxylic acid, aluminum salt 1- (4-sulfo-1-phenylazo) -2-naphthol-6-sufofacid, aluminum salt of 1- (4-sulfo-1-naphthyl-azo) -2-naphthol-3,6-disulfonic acid, 1- ( 4-sulfo-1-naphthylazo) -2-naphthol-6,8-disulfonic acid, aluminum salt of 4- (4-sulfo-1-phenylazo) -1 - (4-suifophenyl) -5-hydroxy-pyrazolon-3-car - Bonic acid, aluminum and zirconium salts of 4,5-dibromofluorescein, aluminum and zirconium salts of 2,4,5,7-tetrabromofluoresce in, 3 ', 4', 5 ', 6'-tetrachloro-2,4,5,7-tetrabromofluorescein and its aluminum salt, aluminum salt of 2,4,5, 7-tetraiodofluorescein, aluminum salt of quinophthalone disulfonic acid , Aluminum salt of indigo-disulfonic acid, red and black iron oxide (CIN: 77 491 (red) and 77 499 (black)), iron oxide hydrate (CIN: 77 492), manganese ammonium diphosphate and titanium dioxide.

Also advantageous are oil-soluble natural dyes, such as. B. paprika extracts, ß-carotene or cochineal.

Formulations containing pearlescent pigments are also advantageous for the purposes of the present invention. 1. Natural pearlescent pigments, such as: in particular, the outwitted in following up ^¬ types of pearlescent pigments are preferred. B.

■ "fish silver" (guanine / hypoxanthine mixed crystals from fish scales) and

■ "mother-of-pearl" (ground mussel shells)

2. Monocrystalline pearlescent pigments such as B. Bismuth oxychloride (BiOCI)

3. Layer-substrate pigments: e.g. B. mica / metal oxide Pearlescent pigments are based, for example, on powdered pigments or castor oil dispersions of bismuth oxychloride and / or titanium dioxide and bismuth oxychloride and / or titanium dioxide on mica. Particularly advantageous is z. B. the gloss pigment listed under CIN 77163.

The following pearlescent pigment types based on mica / metal oxide are also advantageous:

Z are particularly preferred. B. the pearlescent pigments available from Merck under the trade names Timiron, Colorona or Dichrona.

The list of the pearlescent pigments mentioned is of course not intended to be limiting. Pearlescent pigments which are advantageous in the sense of the present invention are obtainable in numerous ways known per se. For example, other substrates besides mica can be coated with other metal oxides, such as. B. silica and the like. Are advantageous for. B. with TiO ₂ and Fe ₂ O ₃ coated SiO ₂ particles ("Ronaspheren"), which are sold by Merck and are particularly suitable for the optical reduction of fine wrinkles. It can also be advantageous to do without a substrate such as mica. Iron pearlescent pigments which are produced without the use of mica are particularly preferred. Such pigments are e.g. B. available under the trade name Sicopearl Kupfer 1000 from BASF.

Also particularly advantageous are effect pigments, which are available from Flora Tech under the trade name Metasomes Standard / Glitter in various colors (yello, red, green, blue). The glitter particles are present in mixtures with various auxiliaries and dyes (such as, for example, the dyes with the Color Index (Cl) numbers 19140, 77007, 77289, 77491).

The dyes and pigments can be present both individually and in a mixture and can be mutually coated, different color effects generally being produced by different coating thicknesses. The total amount of dyes and coloring pigments is advantageously from the range of z. B. 0.1 wt .-% to 30 wt .-%, preferably from 0.5 to 15 wt .-%, in particular from 1, 0 to 10 wt .-%, each based on the total weight of the preparations. It is also advantageous for the purposes of the present invention to produce cosmetic and dermatological preparations, the main purpose of which is not to protect against sunlight, but which nevertheless contain other UV protection substances. So z. B. usually incorporated into day creams or makeup products UV-A or UV-B filter substances. UV protection substances, like antioxidants and, if desired, preservatives, also provide effective protection of the preparations themselves against spoilage. Cosmetic and dermatological preparations which are in the form of a sunscreen are also favorable.

Accordingly, the preparations in the sense of the present invention preferably contain at least one further UV-A, UV-B and / or broadband filter substance. The formulations can, although not necessary, optionally also contain one or more organic and / or inorganic pigments as UV filter substances, which may be present in the water and / or oil phase. The preparations according to the invention can also advantageously be in the form of so-called oil-free cosmetic or dermatological emulsions which contain a water phase and at least one UV filter substance which is liquid at room temperature as a further phase.

Particularly advantageous UV filter substances which are liquid at room temperature for the purposes of the present invention are homomenthyl salicylate (INCI: homosalate), 2-ethylhexyl-2-cyano-3,3-diphenylacrylate (INCI: octocrylene), 2-ethylhexyl-2-hydroxybenzoate (2- Ethyl hexyl salicylate, octyl salicylate, INCI: octyl salicylate) and esters of cinnamic acid, preferably 4-methoxycinnamic acid (2-ethylhexyl) ester (2-ethylhexyl 4-methoxycinnamate, INCI: octyl methoxycinnamate) and 4-methoxycinnamate (4-methoxycinnamate) -methoxy-cinnamate, INCI: Isoamyl p-methoxycinnamate), 3- (4- (2,2-bis-ethoxycarbonylvinyl) -phenoxy) propenyl) -methoxysiloxane / Dimethylsi! oxan - copolymer which, for example, under the trade name Parsol® SLX Hoffmann La Röche is available.

Preferred inorganic pigments are metal oxides and / or other metal compounds which are sparingly soluble or insoluble in water, in particular 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 ), cerium (e.g. Ce ₂ O ₃ ), mixed oxides of the corresponding metals as well as mixtures of such oxides and the sulfate of barium (BaSO ₄ ).

For the purposes of the present invention, the pigments can also advantageously be used in the form of commercially available oily or aqueous predispersions. Dispersing aids and / or solubilizing agents can advantageously be added to these predispersions.

According to the invention, the pigments can advantageously be surface-treated (“coated”), with a hydrophilic, amphiphilic or hydrophobic character, for example, being formed or retained. This surface treatment can consist in the pigments being coated with a thin film using methods known per se hydrophilic and / or hydrophobic inorganic and / or organic layer The various surface coatings can also contain water in the sense of the present invention. Inorganic surface coatings in the sense of the present invention can consist of aluminum oxide (Al ₂ O ₃ ), aluminum hydroxide Al (OH) ₃ , or aluminum oxide hydrate (also: alumina, CAS no .: 1333-84-2), sodium hexametaphosphate (NaPO ₃ ) ₆ , sodium metaphosphate (NaPO ₃ ) _n , silicon dioxide (SiO ₂ ) (also: silica, CAS No .: 7631-86-9), or iron oxide (Fe ₂ O ₃ ). These inorganic surface coatings can occur alone, in combination and / or in combination with organic coating materials.

Organic surface coatings in the sense of the present invention can consist of vegetable or animal aluminum stearate, vegetable or animal stearic acid, lauric acid, dimethylpolysiloxane (also: dimethicone), methylpolysiloxane (methicone), simethicone (a mixture of dimethylpolysiloxane with an average chain length of 200 to 350 ^' dimethylsiloxane Units and silica gel) or alginic acid. These organic surface coatings can occur alone, in combination and / or in combination with inorganic coating materials.

Zinc oxide particles and predispersions of zinc oxide particles suitable according to the invention are available under the following trade names from the companies listed:

Suitable titanium dioxide particles and predispersions of titanium dioxide particles are available under the following trade names from the companies listed:

Other advantageous pigments are latex particles. Latex particles which are advantageous according to the invention are those described in the following documents: US Pat. No. 5,663,213 and EP 0 761 201. Particularly advantageous latex particles are those which are formed from water and styrene / acrylate copolymers and, for. B. are available under the trade name "Alliance SunSphere" from Rohm & Haas.

Advantageous UV-A filter substances for the purposes of the present invention are dibenzoylmethane derivatives, in particular 4- (tert-butyl) -4'-methoxydibenzoylmethane (CAS-Nr. 70356-09-1), marketed by Givaudan under the trade name Parsol ^® 1789 and is sold by Merck under the trade name Eusolex® 9020.

Further advantageous UV-A filter substances for the purposes of the present invention are hydroxybenzophenones, which are distinguished by the following structural formula:

wherein

R ¹ and R ² independently of one another are hydrogen, C _r C ₂ o -alkyl, C ₃ -C ₁₀ cycloalkyl or C ₃ -C ₁₀ cycloalkenyl, the substituents R ¹ and R ² together with the nitrogen atom to which they are attached are bound, can form a 5- or 6-ring and R ^{3 is} a CC ₂₀ alkyl radical.

A particularly advantageous hydroxybenzophenone in the context of the present invention is 2- (4'-diethylamino-2'-hydoxybenzoyl) benzoic acid hexyl ester (also: aminobenzophenone), which is distinguished by the following structure: and is available under the Uvinul A Plus from BASF.

Advantageous further UV filter substances in the sense of the present invention are sulfonated, water-soluble UV filters, such as. B .:

^• phenylene-1, 4-bis- (2-benzimidazyl) -3,3'-5,5'-tetrasulphonic acid and its salts, particularly the corresponding sodium, potassium or triethanolammonium salts, in particular phenylene-1, 4 -bis- (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid bis-sodium salt with the INCI name bisimidazylate (CAS No .: 180898-37-7), which, for example, under the trade name Neo Heliopan AP at Haarmann &

Reimer is available;

Salts of 2-phenylbenzimidazole-5-sulfonic acid, such as its sodium, potassium or triethanolammonium salt and the sulfonic acid itself with the INCI name phenylbenzimidazole sulfonic acid (CAS No. 27503-81-7), for example under the trade name Eusolex 232 from Merck or under Neo Heliopan Hydro from

Haarmann & Reimer is available;

1,4-di (2-oxo-10-sulfo-3-bomylidenemethyl) -benzene (also: 3,3 '- (1,4-phenylenedimethylene)) -bis- (7,7-dimethyl-2-oxo -bicyclo- [2.2.1] hept-1-ylmethane sulfonic acid) and its salts (especially the corresponding 10-sulfato compounds, especially the corresponding sodium, potassium or triethanolammonium salt), which is also known as

Benzene-1,4-di (2-oxo-3-bomylidenemethyl-10-su! Fonic acid) is called. Benzene-1,4-di (2-oxo-3-bornylidenemethyl-10-sulfonic acid) has the INCI name terephthalic dicampher sulfonic acid (CAS No. 90457-82-2) and is, for example, under the trade name Mexoryl SX available from Chimex; • Sulfonic acid derivatives of 3-benzylidene camphor, such as. B. 4- (2-oxo-3-bornylidene-methyl) benzenesulfonic acid, 2-methyl-5- (2-oxo-3-bornylidene-methyl) sulfonic acid and salts thereof. Advantageous UV filter substances in the sense of the present invention are also so-called broadband filters, ie filter substances that absorb both UV-A and UV-B radiation.

Advantageous broadband filters or UV-B filter substances are, for example, triazine derivatives, such as. B.

• Dioctylbutylamidotriazon (INCI: Diethylhexyl Butamido Triazone), which is available under the trade name UVASORB HEB from Sigma 3V;

• 4,4 ', 4 "- (1,3,5-triazine-2,4,6-triyltriimino) tris-benzoic acid tris (2-ethylhexyl ester), also: 2,4,6-tris [anilino - (p-carbo-2'-ethyl-1'-hexyloxy)] - 1, 3,5-triazine (INCI: Octyl Triazone), which is sold by BASF Aktiengesellschaft under the trade name UVINUL® T 150.

An advantageous broadband filter for the purposes of the present invention is also 2,2'-methylene-bis- (6- (2H-benzotriazol-2-yl) -4- (1, 1,3,3-tetramethylbutyl) phenol ), which is available under the trade name Tinosorb® M from CIBA-Chemicals GmbH.

Another advantageous broadband filter for the purposes of the present invention is 2- (2H-benzotriazol-2-yl) -4-methyl-6- [2-methyl-3- [1, 3,3,3-tetramethyl-1- [(trimethylsilyl) oxy] disiloxanyl] propyl] phenol (CAS No .: 155633-54-8) with the INCI name Drometrizole Trisiloxane.

The other UV filter substances can be oil-soluble or water-soluble. Advantageous oil-soluble filter substances are e.g. E.g .: • 3-benzylidene camphor derivatives, preferably 3- (4-methylbenzylidene) camphor, 3-

benzylidenecamphor;

4-aminobenzoic acid derivatives, preferably 4- (dimethylamino) benzoic acid (2-ethylhexyl) ester, 4- (dimethylamino) benzoic acid amyl ester;

2,4,6-trianilino- (p-carbo-2'-ethyl-1'-hexyloxy) -1,3,5-triazine; • esters of benzalmalonic acid, preferably 4-methoxybenzalmalonic acid di (2-ethylhexyl) ester;

Esters of cinnamic acid, preferably 4-methoxycinnamic acid (2-ethylhexyl) ester, 4-methoxycinnamic acid isopentyl ester; Derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-

Hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone as well as UV filters bound to polymers.

Advantageous water-soluble filter substances are e.g. B .:

Sulfonic acid derivatives of 3-benzylidene camphor, such as. B. 4- (2-oxo-3-bornylidene methyl) benzenesulfonic acid, 2-methyl-5- (2-oxo-3-bornylidene methyl) sulfonic acid and their

Salts.

A further light protection filter substance according to the invention to be used advantageously is ethylhexyl-2-cyano-3,3-diphenyl acrylate, sold under the name Uvinul ^® N 539 T is available (octocrylene) from BASF.

Particularly advantageous preparations within the meaning of the present invention, which are distinguished by a high or very high UV-A protection, preferably contain, in addition to the filter substance (s) according to the invention, further UV-A and / or broadband filters, in particular dibenzoylmethane derivatives [ for example the 4- (tert-butyl) -4'-methoxydibenzoylmethane] and / or the 2,2'-methylene-bis- (6- (2H-benzotriazol-2-yl) -4- (1, 1 , 3,3-tetramethylbutyi) phenol), each individually or in any combination with one another.

The list of the UV filters mentioned, which can be used in the sense of the present invention, should of course not be limiting.

The preparations according to the invention advantageously contain the substances which absorb UV radiation in the UV-A and / or UV-B range in a total amount of, for. B. 0.1 wt .-% to 30 wt .-%, preferably 0.5 to 20 wt .-%, in particular 1, 0 to 15.0 wt .-%, each based on the total weight of the preparations to cosmetics - see preparations that protect the hair or skin from the entire range of ultraviolet radiation.

Furthermore, it may be advantageous to incorporate film formers into the cosmetic or dermatological preparations according to the invention, for example to to improve the water resistance of the preparations or to increase the UV protection performance (UV-A and / or UV-B boosting). Both water-soluble or dispersible and fat-soluble film formers are suitable, in each case individually or in combination with one another.

Advantageous water-soluble or dispersible film formers are e.g. B. Polyurethanes (e.g. the Avalure® types from Goodrich), Dimethicone Copolyol Polyacrylate (Silsoft Surface® from the Witco Organo Silicones Group), PVP / VA (VA = vinyl acetate) copolymer (Luviseol VA 64 Powder from BASF), C ₂₀ . ₄₀ carboxylic acid with polyethylene (Performacid 350 from New Phase Technologies) etc.

Advantageous fat-soluble film formers are e.g. B., the film formers from the group of polymers based on polyvinylpyrrolidone (PVP)

Particularly preferred are copolymers of polyvinylpyrrolidone, for example the PVP hexadecene copolymer and the PVP eicosen copolymer, which are available under the trade names Antaron V216 and Antaron V220 from GAF Chemicals Cooperation, as well as Tricontayl PVP and the like.

The following examples are intended to illustrate the present invention without restricting it. The numerical values in the examples mean percentages by weight, based on the total weight of the respective preparations.

Examples:

1. O / W sun protection emulsions

2. Foam-shaped O / W emulsions:

Combination of the grease / light protection filter phase heated to 78 ° C with the water / light protection filter phase heated to 75 ° C. Homogenization using a gear rim dispersing machine (rotor-stator principle) at 65 ° C. 45 min stirring in the Becomix while gassing with helium at 1 bar with cooling to 30 ° C. Add the additives at 30 ° C (Perfume). Homogenization using a gear rim dispersion machine (rotor-stator principle) at 23 ° C.

4. Thin to sprayable W / O emulsions

(for use as an impregnation solution, spray or aerosol)

5. W / O sun protection emulsions (creams & lotions)

6. Hydrodispersions (for use as a lotion, impregnation solution or spray)

7. Solid stabilized emulsions

1

Mineral oil 16.00 16.00

Octyldodecanol 9.00 9.00 5.00

Caprylic / Capric triglyceride 9.00 9.00 6.00

C 12-15 alkyl benzoates 5.00 8.00

Butylene Glycol Dicapry- 8.00

8. Oils and oil gels

Claims

claims:

1. Sunscreen-effective cosmetic or dermatological preparations, characterized in that they (a) - at least one bis-resorcinyltriazine derivative and

(b) contain at least one benzoxazole derivative.

2. Sunscreen-effective cosmetic or dermatological preparations, characterized in that they contain synergistic combinations of substances

(a) at least one bis-resorcinyltriazine derivative and

(b) contain at least one benzoxazole derivative.

3. Preparation according to one of claims 1 or 2, characterized in that it is the bis-resorcinyltriazine derivative 2,4-bis - {[4- (2-ethylhexyloxy) -2-hydroxy] phenyl} - 6- ( 4-methoxyphenyl) -1,3,5-triazine contains.

4. Preparation according to one of the preceding claims, characterized in that it is the benzoxazole derivative 2,4-bis- [5-1 (dimethylpropyl) benzoxazol-2-yl- (4-phenyl) imino] -6- ( Contains 2-ethylhexyl) imino-1, 3,5-triazine.

5. Preparation according to one of the preceding claims, characterized in that the ratio of active ingredient a) to active ingredient b) is chosen between 5: 1 and 1: 5.

6. Preparation according to one of the preceding claims, characterized in that it additionally contains at least one further UV-A filter substance and / or at least one further UV-B filter substance.

7. Preparation according to one of the preceding claims, characterized in that it contains at least one further UV filter substance, selected from the group of water-soluble UV filter substances, benzotriazoles and organic and / or inorganic pigments.

8. Preparation according to one of the preceding claims, characterized in that it contains at least one further UV-A, UV-B and / or broadband filter substance, selected from the group dibenzoylmethane derivatives [in particular the 4- (tert-butyl) -4'- methoxydibenzoylmethane], phenylene-1,4-bis (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid bis-sodium salt, 2-phenylbenzimidazole-5-sulfonic acid, 2- (4'-diethylamino Contains -2'- hydoxybenzoyl) benzoic acid hexyl ester and 2,2'-methylene-bis- (6- (2H-benzotriazol-2-yl) -4- (1, 1, 3,3-tetramethylbutyl) phenol), where the further filter substances can be present individually or in any combination with one another.

9. Preparation according to one of the preceding claims, characterized in that it is oil-free.

10. Preparation according to one of the preceding claims, characterized in that it contains at least one further UV filter from the group of UV filters which are liquid at room temperature.

11. Preparation according to one of the preceding claims, characterized in that it contains at least one flavone glycoside, in particular α-glucosylrutin, and / or vitamin E and / or its derivatives.

12. Preparation according to one of the preceding claims, characterized in that at least one self-tanning substance, in particular dihydroxyacteon is included.

13. Use of preparations according to claim 12 as a self-tanning agent or as an agent for accelerating the tanning.

14. Preparation according to one of the preceding claims, characterized in that at least one repellent, in particular the 3- (N-n-butyl-N-acetylamino) propionic acid ethyl ester is contained.

15. Use of preparations according to one of the preceding claims for protection against light-induced skin aging.

16. Use of material combinations from

(a) at least one bis-resorcinyltriazine derivative and

(b) at least one benzoxazole derivative for the preparation of preparations for the prophylaxis and treatment of cosmetic or dermatological skin changes, such as those which occur during skin aging.