EP1416912A2 - Cosmetic and dermatological light protective formulations containing benzotriazole derivatives and latex particles - Google Patents

Abstract

The invention relates to light protecting cosmetic or dermatological emulsions, which are characterized in that said emulsions contain: (a) at least one benzotriazole derivative and (b) at least one grade of latex particles having a mean particle size of 100 to 400 nm. The invention also relates to the use of said formulations.

Description

 description

Cosmetic and dermatological sunscreen formulations containing

Benzotriazole derivatives and latex particles

The present invention relates to cosmetic and dermatological light protection preparations, in particular it relates to sand-repellent cosmetic and dermatological light protection preparations.

The damaging effect of the ultraviolet part of solar radiation on the skin is generally known. Depending on their respective wavelengths, the rays have different effects on the skin organ: The so-called UV-C radiation with a wavelength that is less than 290 nm is absorbed by the ozone layer in the earth's atmosphere and therefore has no physiological significance. In contrast, rays in the range between 290 nm and 320 nm, the so-called UV-B range, cause an erythema, a simple sunburn or even more or less severe burns. The narrower range around 308 nm is given as a maximum of the erythema effectiveness of sunlight.

Numerous compounds are known for protection against UV-B radiation, which are, for example, derivatives of 3-benzylidene camphor, 4-aminobenzoic acid, cinnamic acid, salicylic acid, benzophenone and s-triazine.

It has long been erroneously assumed that long-wave UV-A radiation with a wavelength between 320 nm and 400 nm has only a negligible biological effect. In the meantime, however, numerous studies have shown that UV-A radiation is far more dangerous than UV-B radiation in terms of triggering photodynamic, especially phototoxic reactions and chronic changes in the skin. The damaging influence of UV-B radiation can also be intensified by UV-A radiation.

PAT RS \ 2001 \ 201058.doc Thus, it is proven, inter alia, that even the UV-A radiation sufficient conditions under normal Alltagsbe ^¬ to damage the collagen and elastin fibers within a short time, which are important for the structure and strength of the skin is essential. This leads to chronic light-induced skin changes - the skin "ages" prematurely. The clinical appearance of 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 mild, 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 (e.g. time of year and time of day or latitude), UV-A radiation remains relatively constant day by day, irrespective of the time of year or day or geographical factors. At the same time, the major part of UV-A radiation penetrates the living epidermis, while around 70% of UV-B rays are retained by the horny layer.

It is therefore of fundamental importance that cosmetic and dermatological light protection preparations offer adequate protection against both UV-B and UV-A radiation.

In general, the light absorption behavior of light protection filter substances is very well known and documented, especially since in most industrialized countries there are positive lists for the use of such substances, which apply very strict standards to the documentation.

However, the use concentration of known light protection filter substances known as solids 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. The sunburn or the light erythema are the acute manifestations of the effect of light. In addition to the effects of UV rays already described, the subsequent reaction of the skin also leads to reduced sebum production and drying of the skin. To alleviate and care for these phenomena, the prior art knows products that are used after sunbathing and usually contain special active ingredients, such as, for example

■ regreasing and moisturizing agents,

^■ anti-inflammatory and cooling substances, ^■ locally anesthetic substances and / or

^■ disinfectants to prevent possible skin infections.

These so-called aftersun or apres-soleil preparations are intended to cool the skin after sunbathing and to improve its moisturizing ability, whereby the imparting of the cooling effect plays a central role. However, the state of the art lacks products that protect the skin from drying out during UV radiation and provide sufficient care.

Another disadvantage of the prior art is that conventional light protection formulations leave a mostly sticky film on the skin. This has e.g. B. when using such products on a sandy beach, the result is that the sand sticks to the body, which is perceived by the user as unpleasant and in the worst case can lead to the sunscreen being used too little or not at all. Since there is usually a more or less strong wind at the sea, this disadvantage usually occurs even when the body does not come into direct contact with the sand - for example when sunbathing on a deck chair - because the sand dust whirling around in the wind also occurs adheres to the creamed areas of the skin.

A further object of the present invention was therefore to find light protection formulations which, after use, do not leave any sand stuck to the creamy skin, which are therefore to be described as sand-repellent.

It was surprising and unforeseeable for the person skilled in the art that cosmetic or dermatological emulsions effective in protecting against light, characterized in that they

(a) at least one benzotriazole derivative and

(b) at least one type of latex particle, which has an average particle size of 100 to 400 nm, remedy the disadvantages of the prior art.

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 , Such formulations may preferably also be a microemulsion, a solid emulsion (i.e. an emulsion stabilized by solids, e.g. a Pickering emulsion), a sprayable emulsion or a hydrodispersion.

The emulsions according to the invention are preferably O / W emulsions.

In all respects, the emulsions according to the invention are extremely satisfactory preparations, which are not limited to a restricted selection of raw materials. 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 spreadability on the skin or the ability to be absorbed into the skin, and are furthermore distinguished by very good light protection effectiveness and, 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 (a) at least one benzotriazole derivative and

(b) at least one type of latex particle which has an average particle size of

Have 100 to 400 nm, contain the UV protection performance of these preparations being higher than the same preparations which do not contain any substances according to (b).

The UV protection performance of sunscreens or the UV filters on which they are based is generally determined in biological effectiveness tests under standardized conditions. For the purposes of the present invention, “UV protective power” means both the protective power against UV-A radiation and against UV-B radiation.

A measure of the UV protection power in the sense of the present invention is, for example, the sun protection factor (SPF or SPF) or also IPD values and the like.

The sun protection factor (LSF, often also called SPF (sun protection factor)) indicates the prolongation of sun exposure, which is made possible by using the sunscreen. It is the quotient of erythema threshold time with sunscreen and erythema threshold time without sunscreen.

The IPD method (IPD ≡ immediate pigment darkening) is usually used to test UV-A protection. Similar to the determination of the light protection factor, a value is determined which 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.

Another test method that is established throughout Europe is the Australian standard AS / NZS 2604: 1997. The absorption of the preparation is measured in the UV-A range. In order to meet the standard, the preparation must absorb at least 90% of the UV-A radiation in the range from 320 to 360 nm.

The cosmetic and dermatological preparations in the sense of the present invention do not leave a greasy or sticky impression on the skin, are excellently compatible with the skin and are also surprisingly distinguished by the fact that they are sand-repellent.

The invention therefore also relates to cosmetic or dermatological light protection preparations, characterized in that they

(a) at least one benzotriazole derivative and

(b) contain at least one type of latex particle which has an average particle size of 100 to 400 nm.

Latex particles with an average particle size of 150 to 375 nm, in particular from 190 to 350 nm, are advantageous in the sense of the present invention.

According to the invention, preference is given to latex particles which have a cavity in their interior which, for example, is filled with air. It is particularly advantageous in the sense of the present invention if this cavity is as large as possible, insofar as the manufacturing conditions and the stability of the particles allow. The latex particles according to the invention preferably contain a cavity of 0.1% to 50%, in particular 5% to 50%, in each case based on the volume of the particles.

Latex particles which are advantageous according to the invention consist of several layers and contain at least one inner polymer layer (“core polymer”) and at least one outer polymer layer (“shell polymer”). The core and shell polymer can be produced in a common or in successive polymerization steps.

The latex particles according to the invention are produced with the aid of customary polymerisation reactions, for example with the aid of sequential emulsion polymerisation. Are advantageous for. B. The in U.S. Patents 4,427,836; 4,469,825; 4,594,363; 4,677,003; 4,920,160 and 4,970,241. Further advantageous polymerization processes are further described in the following patent applications or documents: EP-A-267 726, EP-A-331 421 and US 4,910,229 and US 5,157,084.

Advantageous monomers which can be used, for example, in the course of an emulsion polymerization to produce the shell polymer contain one or more nonionic, ethylenic, unsaturated monomers, in particular one or more monoethylenic, unsaturated monomers which carry at least one carboxylic acid group. The monomers from which the shell polymer is produced are advantageously chosen so that the shell polymer has a glass transition temperature in at least one layer which is high enough to support or maintain the cavity in the latex particle. For this purpose, the glass transition temperature is advantageously chosen to be greater than 50 ° C., in particular greater than 60 ° C., very particularly greater than 70 ° C., which can be determined with the aid of a differential thermal analysis (in particular the so-called “differential scanning calorimetry” = DSC).

Advantageous monomers, which can be used, for example, in the context of an emulsion polymerization to produce the core polymer, contain one or more monoethylenic, unsaturated monomers which carry at least one carboxylic acid group. The core polymer advantageously contains at least 5% by weight of one or more monoethylenic, unsaturated monomers which carry at least one carboxylic acid group, based on the total weight of the monomers of the core polymer. The core polymer can be obtained, for example, by emulsion homopolymerization of the monomers mentioned or by copolymerization of two or more such monomers. Particularly advantageous core polymers can be obtained by copolymerizing a monoethylenic, unsaturated monomer with one or more non-ionic, ethylenic, unsaturated monomers.

Advantageous polyethylenic, unsaturated monomers for the purposes of the present invention, which (individually or in mixtures) are present in core and / or shell polymer with a content of 0.1 to 20% by weight, preferably 3 to 20% by weight can include, for example, ethylene glycol di (meth) acrylate, allyl (meth) acrylate, 1,3-butanediol i (meth) acrylate, diethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate or divinylbenzene. Alternatively, the core and / or shell polymer can also contain 0.1 to 60% by weight of butadiene, in each case based on the total weight of the monomers.

Advantageous monoethylenic, unsaturated monomers which carry at least one carboxylic acid group are, for the purposes of the present invention, for. As acrylic acid and methacrylic acid, acryloxypropionic acid, (meth) acryloxypropionic acid, itaconic acid, aconitic acid, maleic acid or anhydride, fumaric acid, crotonic acid, monomethyl maleate, monomethyl fumarate and / or monomethyl itaconate. Acrylic acid and methacrylic acid are particularly preferred.

Suitable non-ionic, ethylenic, unsaturated monomers for the purposes of the present invention are, for. B. styrene, vinyl toloule, ethylene, vinyl acetate, vinyl chloride, vinylidene chloride, acrylonitrile, (meth) acrylamide, d - C ₂₀ - alkyl or C ₃ - C ₂₀ - alkenyl esters of (meth) acrylic acid, such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, lauryl (meth) acrylate, oleyl (meth) acrylate, palmityl (meth) acrylate, and / or stearyl (meth) acrylate, in which the expression “(meth) acrylate” is to be understood generically for both terms “methacrylate” and “acrylate”.

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. Commercial products of this type generally have an active content of 25 to 27% by weight.

The following example is intended to clarify what is to be understood by “active use concentration” or “active content” in the sense of the present invention: B. in the form of a 50% solution (for example, because it is only available in this form on the market), then - at an application concentration of this "raw material solution" of 8.0 wt .-% - only one in the recipe "Active content" of 4.0 wt .-%, based on the total weight of the preparation, realized.

The total amount of one or more latex particles according to the invention in the finished cosmetic or dermatological preparations (the active content) is advantageously in the range from 0.1 to 10.0% by weight, preferably 0.5 to 6.0% by weight. % selected, based on the total weight of the preparations. A particularly advantageous benzotriazole derivative is 2,2'-methylene-bis- (6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol) [INCI: bisoctyltriazole], which is characterized by the chemical structural formula

distinguished and z. B. is available under the trade name Tinosorb® M from CIBA-Chemical GmbH.

Another advantageous benzotriazole derivative 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, which is characterized by the chemical structural formula

is marked.

The UV filter substance (s) according to the invention is / are advantageously incorporated into the water phase - particularly at a pH of more than 4.5 - of the cosmetic or dermatological formulations.

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

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 contain cosmetic auxiliaries, such as are usually used in such preparations, for. B. preservatives, preservation aids, bactericides, perfumes, anti-foaming substances, dyes, pigments that have a coloring effect, thickeners, moisturizing and / or moisturizing substances, fillers that improve the skin feel, fats, oils, waxes or other common Components of a cosmetic or dermatological formulation 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), iodopropyl butyl carbamates (for example those available under the trade names Koncyl-L, Koncyl-S and Konkaben LMB from Lonza), parabens, Phenoxyethanol, ethanol, benzoic acid and the like. According to the invention, the preservation system usually also advantageously comprises preservation aids, such as, for example, octoxyglycerol, glycine soya, etc.

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.

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-Camosin, L-Camosin and their derivatives (e.g. anserine), carotenoids, carotenes (e.g. α-carotene, ß-carotene, lycopene) and their derivatives, lipoic acid and their derivatives (e.g. dihydroliponic acid), aurothioglucose, propylthiouracil and other thiols (e.g. thioredoxin, glutathione, cysteine, cystine, cystamine and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl -, γ-linoleyl, cholesteryl and glyceryl esters) and their salts, dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and their derivatives (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) as well as sulfoximine compounds (e.g. buthioninsulfoximines Homocysteine sulfoximine, buthionine sulfones, penta-, hexa-, heptathionine sulfoximine) in very low tolerable doses (e.g. pmol to μmol / kg), also (metal) chelators (e.g. α-hydroxy fatty acids, palmitic acid, phytic acid, Lactoferrin), α-hydroxy acids (e.g. citric acid, lactic acid, malic acid), humi Acid, bile acid, bile extracts, bilirubin, biliverdin, EDTA, EGTA and their derivatives, unsaturated fatty acids and their derivatives (e.g. B. γ-linolenic acid, linoleic acid, oleic acid), folic acid and its derivatives, ubiquinone and ubiquinol and their derivatives, vitamin C and derivatives (e.g. ascorbyl palmitate, Mg - ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives (e.g. Vitamin E acetate), vitamin A and derivatives (vitamin A palmitate) and konyferyl benzoate of benzoin, rutinic acid and its derivatives, ferric acid and its derivatives, butylhydroxytoluene, butylhydroxyanisole, nordihydroguajak resin acid, nordihydroguajaretic acid, and trihonydroxybutyric acid - derivatives, mannose and their derivatives, zinc and its derivatives (e.g. ZnO, ZnSÜ4) selenium and its derivatives (e.g. selenium methionine), stilbenes and their derivatives (e.g. stilbene oxide, trans-stilbene oxide) and the Derivatives suitable according to the invention (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids) of these active substances mentioned.

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

An astonishing property of the preparations according to the invention is that they are very good vehicles for cosmetic or dermatological active ingredients in the skin, preferred active ingredients being antioxidants which can protect the skin against oxidative stress. Preferred antioxidants are 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.

According to the invention, the active ingredients (one or more compounds) can also be selected very advantageously from the group of lipophilic active ingredients, in particular from the following group:

Acetylsalicylic acid, atropine, azulene, hydrocortisone and its derivatives, e.g. B. hydrocortisone-17-valerate, vitamins of the B and D series, very cheap the vitamin B ^, the vitamin Bι _2, the vitamin D ^ but also bisabolol, unsaturated fatty acids, especially the essential fatty acids (often also vitamin F called), in particular gamma-linolenic acid, oleic acid, eicosapentaenoic acid, docosahexaenoic acid and their derivatives, chloramphenicol, caffeine, prostaglandins, thymol, camphor, extracts or other products of plant and animal origin, eg. B. evening primrose oil, borage oil or currant seed oil, fish oils, cod liver oil but also ceramides and ceramide-like compounds and so on.

It is also advantageous to select the active substances from the group of refatting substances, for example purcellin oil, Eucerit and Neocerit.

The active ingredient (s) are particularly advantageously selected from the group of NO synthase inhibitors, in particular if the preparations according to the invention for the treatment and prophylaxis of the symptoms of intrinsic and / or extrinsic skin aging and for the treatment and prophylaxis of the harmful effects of ultra- to serve violet radiation to the skin.

The preferred NO synthase inhibitor is nitroarginine.

The active ingredient (s) are also advantageously selected from the group comprising catechins and bile esters of catechins and aqueous or organic extracts from plants or parts of plants which contain catechins or bile esters of catechins, such as, for example, the leaves of Plant family Theaceae, especially the species Camellia sinensis (green tea). Their typical ingredients (such as polyphenols or catechins, caffeine, vitamins, sugar, minerals, amino acids, lipids) are particularly advantageous.

Catechins are a group of compounds which are to be regarded as hydrogenated flavones or anthocyanidins and derivatives of "catechins" (catechol, 3,3 ', 4', 5,7-flavanpentaol, 2- (3,4- Dihydroxyphenyl) -chroman-3,5,7-triol) Epicatechin ((2R, 3R) -3,3 ', 4', 5,7-flavanpentaol) is also an advantageous active substance in the sense of the present invention.

Also advantageous are plant extracts containing catechins, in particular extracts of green tea, such as. B. extracts from leaves of the plants of the species Camellia spec, especially the teas Camellia sinenis, C. assamica, C. talien- sis or C. irrawadiensis and crosses of these with, for example, Camellia japonica.

Preferred active ingredients are also polyphenols or catechins from the group (-) - catechol, (+) - catechin, (-) - catechin gallate, (-) - gallocatechin gallate, (+) - epicatechin, (-) - epicatechin , (-) - epicatechin gallate, (-) - epigallocatechin, (-) - epigallocatechin gallate.

Flavon and its derivatives (often also collectively called "flavones") are advantageous active substances in the sense of the present invention. They are characterized by the following basic structure (substitution positions specified):

Some of the more important flavones, which can also preferably be used in preparations according to the invention, are listed in the table below:

In nature, flavones usually occur in glycosidated form.

According to the invention, the flavonoids are preferably chosen from the group of substances of the generic structural formula

where Z, to Z ₇ are selected independently of one another from the group H, OH, alkoxy and hydroxyalkoxy, where the alkoxy or hydroxyalkoxy groups can be branched and unbranched and can have 1 to 18 C atoms, and wherein Gly is selected from the group of mono- and oligoglycoside residues.

According to the invention, the flavonoids can also be advantageously selected from the group of substances of the generic structural formula

where Z to Z _{6 are} independently selected from the group H, OH, alkoxy and hydroxyalkoxy, where the alkoxy or hydroxyalkoxy groups can be branched and unbranched and can have 1 to 18 carbon atoms, and wherein Gly is selected from the group Group of the mono- and oligoglycoside residues.

Such structures can preferably be selected from the group of substances of the generic structural formula

wherein Glyi, Gly ₂ and Gly ₃ independently of one another represent monoglycoside residues or. Gly ₂ or Gly ₃ can also represent, individually or together, saturations by hydrogen atoms.

Glyi, Gly ₂ and Gly ₃ are preferably selected independently of one another from the group of the hexosyl radicals, in particular the rhamnosyl radicals and glucosyl radicals. However, other hexosyl radicals, for example allosyl, altrosyl, galactosyl, gulosyl, idosyl, mannosyl and talosyl, may also be used advantageously. It can also be advantageous according to the invention to use pentosyl residues.

Z ^ to Z ₅ are advantageously selected independently of one another from the group H, OH, methoxy, ethoxy and 2-hydroxyethoxy, and the flavone glycosides have the structure

The flavone glycosides according to the invention from the group which are represented by the following structure are particularly advantageous:

wherein Glyi, Gly ₂ and Gly ₃ independently of one another represent monoglycoside residues or. Gly ₂ or Gly ₃ can also represent, individually or together, saturations by hydrogen atoms.

Gly ^ Gly ₂ and Gly ₃ are preferably selected independently of one another from the group of the hexosyl residues, in particular the rhamnosyl residues and glucosyl residues. However, other hexosyl radicals, for example allosyl, altrosyl, galactosyl, gulosyl, idosyl, mannosyl and talosyl, may also be used advantageously. It can also be advantageous according to the invention to use pentosyl residues.

For the purposes of the present invention, it is particularly advantageous to choose the flavone glycosides from the group α-glucosyl rutin, α-glucosyl myrcetin, α-glucosyl iso-quercitrin, α-glucosyl iso-quercetin and α-glucosyl-quercitrin.

According to the invention, α-glucosylrutin is particularly preferred.

Also advantageous according to the invention are naringin (aurantiin, naringenin-7-rhamnoglucosid), hesperidin (3 ', 5,7-trihydroxy-4'-methoxyflavanon-7-rutinoside, hesperidoside, hesperetin-7-O-rutinoside). Rutin (3,3 ', 4', 5,7-pentahydroxyflyvon-3-rutinoside, quercetin-3-rutinoside, sophorin, birutan, rutabion, taurutin, phytomelin, melin), troxerutin (3,5-dihydroxy-3 ', 4', 7-tris (2-hydroxyethoxy) flavon-3- (6-O- (6-deoxy-α-L-mannopyranosyl) -ß-D-glucopyranoside)), monoxerutin (3.3 ', 4', 5-tetrahydroxy-7- (2-hydroxyethoxy) flavon-3- (6-O- (6-deoxy-α-L-mannopyranosyl) -ß-D-glucopyranoside)), dihydrorobinetin ( 3,3 ', 4', 5 ', 7-pentahydroxyflavanone), taxifolin (3,3', 4 ', 5,7-pentahydroxyflavanone), eriodictyol-7-glucoside (S''.δ-tetrahydroxyflavanone ^ - glucoside), Flavanomareϊn (3 ', 4', 7,8-tetrahydroxyflava- non-7-glucoside) and isoquercetin (3,3 ', 4', 5,7-pentahydroxyflavanon-3- (ß-D-glucopyranosid).

It is also advantageous to choose the active ingredient (s) from the group of ubiquinones and plastoquinones.

Ubiquinones are characterized by the structural formula

and represent the most widespread and thus best studied biochinones. Depending on the number of isoprene units linked in the side chain, ubiquinones are classified as Q-1, Q-2, Q-3 etc. or according to the number of C- Atoms referred to as U-5, U-10, U-15, etc. They preferably occur with certain chain lengths, e.g. B. in some microorganisms and yeasts with n = 6. Q10 predominates in most mammals, including humans.

Coenzyme Q10, which is characterized by the following structural formula, is particularly advantageous:

Plastoquinones have the general structural formula

on. Plastoquinones differ in the number n of isoprene residues and are named accordingly, e.g. B. PQ-9 (n = 9). There are also other plastoquinones with different substituents on the quinone ring.

Creatine and / or creatine derivatives are also preferred active substances for the purposes of the present invention. Creatine is characterized by the following structure:

Preferred derivatives are creatine phosphate and creatine sulfate, creatine acetate, creatine ascorbate and the derivatives esterified on the carboxyl group with mono- or polyfunctional alcohols.

Another advantageous active ingredient is L-camitin [3-hydroxy-4- (trimethylammonio) -butter-acid-betaine]. Also acyl-carnitine, which is selected from the group of substances of the following general structural formula

W C - R

/

(H ₃ C) ₃ N-CH ₂ -C- -CHo-COO ^' H where R is selected from the group of branched and unbranched alkyl radicals with up to 10 carbon atoms are advantageous active substances in the sense of the present invention. Propionylcarnitine and in particular acetylcarnitine are preferred. Both entantiomers (D- and L-form) can be used advantageously for the purposes of the present invention. It can also be advantageous to use any mixture of enantiomers, for example a racemate of D and L form. Other advantageous active ingredients are sericoside, pyridoxol, vitamin K, biotin and flavorings.

The list of the active substances or combinations of active substances mentioned which can be used in the preparations according to the invention is of course not intended to be limiting. The active ingredients can be used individually or in any combination with one another.

In addition, selected recipes according to the invention are suitable, which e.g. B. known anti-wrinkle active ingredients such as flavone glycosides (especially α-glycosylrutin), coenzyme Q10, vitamin E and / or derivatives and the like, particularly advantageous for the prophylaxis and treatment of cosmetic or dermatological skin changes, such as z. B. occur in skin aging. They are also advantageous against the appearance of dry or rough skin.

Skin aging is e.g. B. caused by endogenous, genetically determined factors. In the epidermis and dermis it occurs due to aging e.g. B. the following structural damage and malfunctions, which may also fall under the term "senile xerosis":

a) dryness, roughness and formation of (dryness) wrinkles, b) itching and c) reduced regreasing by sebum glands (e.g. after washing).

Exogenous factors, such as UV light and chemical pollutants, can be cumulatively effective and e.g. B. accelerate or complement the endogenous aging processes. In the epidermis and dermis, it is caused in particular by exogenous factors, e.g. B. the following structural damage and functional disorders in the skin, which go beyond the extent and quality of the damage with chronological aging:

d) visible vasodilation (telangiectasia, cuperosis); e) flaccidity and wrinkling; f) local hyper, hypo and incorrect pigmentation (e.g. age spots) and g) increased susceptibility to mechanical stress (e.g. cracking). In a particular embodiment, the present invention relates in particular to products for the care of the naturally aged skin and for the treatment of the consequential damage caused by light aging, in particular the phenomena listed under a) to g).

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, especially 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 12 to 18 carbon atoms. The fatty acid triglycerides can for example be advantageously 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.

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, cetearyl isononanoate, isopropyl myristate, isopropyl palmitate, isopropyl stearate, isopropyl oleate, n-butyl stearate, n-hexyl lauron stearate, n-hexyl lauronate, n Isononyl isononanoate, 2-ethylhexyl palmitate, 2-ethylhexyl laurate, 2-hexyldecyl stearate, 2-octyldodecyl palmitate, stearylheptanoate, oleyl oleate, olerlerucate, erucyl oleate, erucylerucate, tridecyl stearate, synthetic and natural tridecyl, synthetic tridecylate 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 that the oil component (s) from the group isoeikosan, neopentyl glycol diheptanoate, propylene glycol dicaprylate / dicaprate, caprylic / capric / diglyceryl succinate, butylene glycol dicaprylate / dicaprate, C-ι ₂ . ₁₃ alkyl lactate, di-Cι _2- ι ₃ alkyl tartrate, tri-isostearin, dipentaerythrityl hexacaprylate hexacaprate, propylene glycol monoisostearate, tricaprylin, dimethyl isosorbide. It is particularly advantageous if the oil phase of the formulations according to the invention has a content of C _12-15 alkyl benzoate or consists entirely of this.

Advantageous oil components are also e.g. B. butyl octyl salicylate (for example that available under the trade name Hallbrite BHB from CP Hall), hexadecyl benzoate and butyl octyl benzoate and mixtures thereof (Hallstar AB) and / or diethylhexyl naphthalate (Hallbrite TQ).

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 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 isohexa- decane. 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 manner via oxygen atoms and the remaining valences of silicon by hydrocarbon residues (mostly methyl, more rarely ethyl, propyl, phenyl groups etc.) are saturated. The silicone oils are systematically considered Designated 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, from Th. Goldschmidt under the trade names Abil 10 to 10,000. Also advantageous are phenylmethylpolysiloxanes (INCI: phenyl dimethicone, phenyl trimethicone), cyclic silicones (octamethylcyclotetrasiloxane or decamethylcyclopentasiloxane), which according to INCI are also called cyclomethicones, amino-modified silicones (INCI: amodimethicone and silicone). B. polysiloxane-polyalkylene copolymers (INCI: stearyl dimethicone and cetyl dimethicone) and dialkoxydimethyl polysiloxanes (stearoxy dimethicone and behenoxy stearyl dimethicone), which are available as different Abil-Wax types from Th. Goldschmidt. However, other silicone oils can also be used advantageously for the purposes of the present invention, for example cetyldimethicone, hexamethylcyclotrisiloxane, polydimethylsiloxane, poly (methylphenylsiloxane).

According to the invention, z. B. natural waxes of animal and vegetable origin, such as beeswax, china wax, bumblebee wax and other insect waxes and shea butter.

Furthermore, the preparations according to the invention can advantageously also 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, 2-ethylhexyl-2-cyano-3,3-diphenyl-acrylate, 2-ethylhexyl-2-hydroxybenzoate and esters of cinnamic acid, preferably 4-methoxycinnamic acid (2-ethylhexyl) ester and 4-methoxycinnamic acid isopentyl ester.

Homomenthyl salicylate (INCI: Homosalate) is characterized by the following structure:

2-Ethylhexyl-2-cyano-3,3-diphenylacrylate (INCI: Octocrylene) is available from BASF under the name Uvinul ^® N 539 and is characterized by the following structure:

2-ethylhexyl-2-hydroxybenzoate (2-ethylhexyl salicylate, octyl salicylate, INCI: octyl salicylate) is available, for example, from Haarmann & Reimer under the trade name Neo Heliopan OS and is characterized by the following structure:

4-methoxycinnamic acid (2-ethylhexyl) ester (2-ethylhexyl-4-methoxycinnamate, INCI: octyl methoxycinnamate) is available, for example, from Hoffmann-La Röche under the trade name Parsol MCX and is characterized by the following structure:

Isopentyl 4-methoxycinnamate (isopentyl-4-methoxycinnamate, INCI: isoamyl p-methoxycinnamate) is available, for example, from Haarmann & Reimer under the trade name Neo Heliopan E 1000 and is characterized by the following structure:

The total amount of one or more UV filter substances which are liquid at room temperature in the finished cosmetic or dermatological preparations is advantageously selected from the range from 0.1% by weight to 30% by weight, preferably from 0.5 to 20% by weight , each based on the total weight of the preparations.

For the purposes of the present invention, such oil-free emulsions can furthermore, although not necessarily, also contain silicone oils and / or silicone waxes, in particular the abovementioned ones.

The water phase of the preparations according to the invention can advantageously contain conventional 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, 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 selected 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, for example carbopoles of types 980, 981, 1382, 2984, 5984, each individually or in combination. Moisturizers can also be used with preference.

Moisturizers are substances or mixtures of substances that give cosmetic or dermatological preparations the property of releasing the moisture from the horny 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, 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 high-fucose 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.

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, create 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 mainly UV filter nor coloring effects (such as e.g. B. boron nitride etc.) and / or Aerosile ^® (CAS No. 7631-86-9).

Aerosile ^® , which are available from DEGUSSA AG / Frankfurt, are silicon oxides and are characterized by a small particle size (eg between 5 and 40 nm), the particles being spherical particles of very uniform dimensions. Aerosile ^® are macroscopically recognizable as loose, white powders. Advantageous Aerosil ^® - grades are, for example, Aerosil ^® OX50, Aerosil ^® 130, Aerosil ^® 150, Aerosil ^® 200, Aerosil ^® 300, Aerosil ^® 380, Aerosil ^® MOX 80 Aerosil ^® MOX 170 Aerosil ^® COK 84, Aerosil ^® R 202, Aerosil ^® R 805, Aerosil ^® R 812, Aerosil ^® R 974, Aerosil ^® R976.

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. 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 (for example Fe ₂ O ₃ , Fe ₃ O, 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 list below. The Color Index Numbers (CIN) are taken from the Rowe Color Index, 3rd edition, Society of Dyers and Colorists, Bradford, England, 1971.

Chemical or other name CIN color

Pigment Green 10006 green

Acid Green 1 10020 green

2,4-dinitrohydroxynaphthalene-7-sulfonic acid 10316 yellow

Pigment Yellow 1 11680 yellow

Pigment Yellow 3 11710 yellow

Pigment Orange 1 11725 orange

2,4-dihydroxyazobenzene 11920 orange

Solvent Red 3 12010 red

1 - (2'-chloro-4'-nitro-1 '-phenylazo) -2-hydroxynaphthalene 12085 red

Pigment Red 3 12120 red

Ceresrot; Sudan Red; Fat red G 12150 red

Pigment Red 112 12370 red

Pigment Red 7 12420 red

Pigment Brown 1 12480 brown

4- (2'-methoxy-5'-sulfonic acid diethylamide-1 ^, -phenylazo) -3-hydroxy-5 "- 12490 red chloro-2", 4 "-dimethoxy-2-naphthoic acid anilide

Disperse Yellow 16 12700 yellow

1 - (4-Sulfo-1-phenylazo) -4-amino-benzene-5-sulfonic acid 13015 yellow

2,4-Dihydroxy-azobenzene-4'-sulfonic acid 14270 orange Chemical or other name CIN color

2- (2,4-Dimethylphenylazo-5-sulfonic acid) -1-hydroxynaphthalene-4-sulfo-14700 red foic acid

2- (4-sulfo-1-naphthylazo) -1 -naphthol-4-sulfonic acid 14720 red

2- (6-sulfo-2,4-xylylazo) -1-naphthol-5-sulfonic acid 14815 red

1- (4'-Sulfophenylazo) -2-hydroxynaphthalene 15510 orange

1- (2-sulfonic acid-4-chloro-5-carboxylic acid-1-phenylazo) -2-hydroxy- 15525 red naphthalene

1- (3-methyl-phenylazo-4-sulfonic acid) -2-hydroxynaphthalene 15580 red

1- (4 ', (8') - sulfonic acid naphthylazo) -2-hydroxynaphthalene 15620 red

2-hydroxy-1, 2'-azonaphthalene-1 'sulfo acid 15630 red

3-hydroxy-4-phenylazo-2-naphthylcarboxylic acid 15800 red

1 - (2-sulfo-4-methyl-1-phenylazo) -2-naphthylcarboxylic acid 15850 red

1- (2-sulfo-4-methyl-5-chloro-1-phenylazo) -2-hydroxy-naphthalene-3- 15865 red carboxylic acid

1 - (2-sulfo-1-naphthylazo) -2-hydroxynaphthalene-3-carboxylic acid 15880 red

1 - (3-Sulfo-1-phenylazo) -2-naphthol-6-sulfonic acid 15980 orange

1 - (4-Sulfo-1-phenylazo) -2-naphthol-6-sulfonic acid 15985 yellow

Allura Red 16035 red

1 - (4-Sulfo-1-naphthylazo) -2-naphthol-3,6-disulfonic acid 16185 red

Acid Orange 10 16230 orange

1 - (4-Sulfo-1-naphthylazo) -2-naphthol-6,8-disulfonic acid 16255 red

1 - (4-Sulfo-1-naphthylazo) -2-naphthol-3,6,8-trisulfonic acid 16290 red

8-amino-2-phenylazo-1-naphthol-3,6-disulfonic acid 17200 red

Acid Red 1 18050 red

Acid Red 155 18 130 red

Acid Yellow 121 18690 yellow

Acid Red 180 18736 red

Acid Yellow 11 18820 yellow

Acid Yellow 17 18965 yellow

4- (4-Sulfo-1-phenylazo) -1- (4-sulfophenyl) -5-hydroxy-pyrazolon-3- 19140 yellow carboxylic acid

Pigment Yellow 16 20040 yellow

2,6- (4'-Sulfo-2 ", 4" -dimethyl) bis-phenylazo) 1, 3-dihydroxybenzene 20170 orange Chemical or other name CIN color

Acid Black 1 20470 black

Pigment Yellow 13 21 100 yellow

Pigment Yellow 83 21108 yellow

Solvent Yellow 21230 yellow

Acid Red 163 24790 red

Acid Red 73 27 290 red

2- [4 '- (4 "-Sulfo-1" phenylazo) -7'-sulfo-1' -naphthylazo] -1-hydroxy-7- 27755 black aminonaphthalene-3,6-disulfonic acid

4 '- [(4 "-Sulfo-1" -phenylazo) -7 "-sulfo-1' -naphthylazo] -1 -hydroxy-8- 28440 black acetyl-aminonaphthalene-3,5-disulfonic acid

Direct Orange 34, 39, 44, 46, 60 40215 orange

Food Yellow 40800 orange trans-ß-apo-δ'-carotenaldehyde (C ₃₀ ) 40820 orange trans-apo-δ'-carotenic acid (C ₃₀ ) ethyl ester 40825 orange

Canthaxanthin 40850 orange

Acid Blue 1 42045 blue

2,4-disulfo-5-hydroxy-4'-4 "-bis- (diethylamino) triphenyl-carbinol 42051 blue

4 - [(- 4-N-ethyl-p-sulfobenzylamino) phenyl- (4-hydroxy-2-sulfophe- 42053 green nyl) - (methylene) -1- (N-ethylN-p-sulfobenzyl) -2, 5-cyclohexadienimine]

Acid Blue 7 42080 blue

(N-ethyl-p-sulfobenzylamino) phenyl- (2-sulfophenyl) -methylene- (N- 42090 blue ethyl-Np-sulfo-benzyl) Δ ^2.5 -cyclohexadienimine

Acid Green 9 42 100 green

Diethyl-di-sulfobenzyl-di-4-amino-2-chloro-di-2-methyl-fuchsonim-42170 green monium

Basic Violet 14 42510 violet

Basic Violet 2 42520 violet

2'-Methyl-4 '- (N-ethyl-N-m-sulfobenzyl) amino-4 "- (N-diethyl) amino- 42735 blue

2-methyl-N-ethylN-m-sulfobenzyl-fuchsonimmonium

4 '- (N-Dimethyl) -amino-4 "- (N-phenyl) -aminonaphtho-N-dimethyl-44045 blue foxsonimmonium

2-Hydroxy-3,6-disulfo-4,4'-bis-dimethylaminonaphthofuchsonimmo 44090 green nium Chemical or other name CIN color

Acid Red 52 45 100 red

3- (2'-Methylphenylamino) -6- (2'-methyl-4 ^, -sulfophenylamino) -9- (2 "- 45190 violet carboxyphenyl) xanthenium salt

Acid Red 50 45 220 red

Phenyl-2-oxyfluoron-2-carboxylic acid 45350 yellow

4,5-dibromofluorescein 45370 orange

2,4,5,7-tetrabromofluorescein 45380 red

Solvent Dye 45396 orange

Acid Red 98 45405 red

S '^'. S'.β'-tetrachlor ^^. Δy-tetrabromofluorescein 45410 red

4,5-diiodofluorescein 45425 red

2,4,5,7-tetraiodofluorescein 45430 red

Quinophthalone 47000 yellow

Quinophthalone disulfonic acid 47005 yellow

Acid Violet 50 50325 violet

Acid Black 2 50420 black

Pigment Violet 23 51319 violet

1, 2-dioxyanthraquinone, calcium-aluminum complex 58000 red

3-oxypyrene-5,8, 10-sulfonic acid 59040 green

1-Hydroxy-4-N-phenylaminoanthraquinone 60724 violet

1-Hydroxy-4- (4'-methylphenylamino) anthraquinone 60725 purple

Acid Violet 23 60730 violet

1, 4-Di (4'-methylphenylamino) anthraquinone 61565 green

1,4-bis (o-sulfo-p-toluidino) anthraquinone 61570 green

Acid Blue 80 61585 blue

Acid Blue 62 62045 blue

N, N'-dihydro-1, 2,1 \ 2'-anthraquinonazine 69800 blue

Vat Blue 6; Pigment Blue 64 69825 blue

Vat Orange 7 71105 orange

Indigo 73000 blue

Indigo-disulfonic acid 73015 blue

4,4'-dimethyl-6,6'-dichlorothioindigo 73360 red

5,5'-dichloro-7,7'-dimethylthioindigo 73385 purple Chemical or other name CIN color

Quinacridone Violet 19 73900 violet

Pigment Red 122 73915 red

Pigment Blue 16 74 100 blue

Phthalocyanine 74160 blue

Direct Blue 86 74 180 blue

Chlorinated phthalocyanine 74260 green

Natural Yellow 6.19; Natural Red 1 75 100 yellow

Bixin, Nor-Bixin 75120 orange

Lycopene 75125 yellow trans-alpha, beta or gamma carotene 75130 orange

Keto and / or hydroxyl derivatives of carotene 75135 yellow

Guanine or pearlescent 75170 white

1,7-bis (4-hydroxy-3-methoxyphenyl) 1,6-heptadiene-3,5-dione 75300 yellow

Complex salt (Na, Al, Ca) of carminic acid 75470 red

Chlorophyll a and b; Copper compounds of chlorophyll ld 75810 green

chlorophyllins

Aluminum 77000 white

Alumina hydrate 77002 white

Water-containing aluminum silicate 77004 white

Ultramarine 77007 blue

Pigment Red 101 and 102 77015 red

Barium sulfate 77120 white

Bismuth oxychloride and its mixtures with mica 77163 white

Calcium carbonate 77220 white

Calcium sulfate 77231 white

Carbon 77266 black

Pigment Black 9 77267 black

Carbo medicinalis vegetabilis 77268: 1 black

Chromium oxide 77288 green

Chromium oxide, containing 77289 green

Pigment Blue 28, Pigment Green 14 77346 green

Pigment Metal 2 77400 brown

Gold 77480 brown Chemical or other name CIN color

Iron oxides and hydroxides 77489 orange

Iron oxide 77491 red

Iron oxide hydrate 77492 yellow

Iron oxide 77499 black

Mixtures of iron (II) and iron (III) hexacyanoferrate 77510 blue

Pigment White 18 77713 white

Manganese ammonium diphosphate 77742 violet

Manganese phosphate; Mn ₃ (PO) ₂ ^• 7 H20 77745 red

Silver 77820 white

Titanium dioxide and its mixtures with mica 77891 white

Zinc oxide 77947 white

6,7-dimethyl-9- (1'-D-ribityl) isoalloxazine, lactoflavin yellow

Caramel brown

Capsanthin, Capsorubin orange

Betanine red

Benzopyrylium salts, anthocyanins red

Aluminum, zinc, magnesium and calcium stearate white

Bromothymol blue blue

Bromcresoi green green

Acid Red 195 red

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- (4-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 of 1- (4-sulfo-1-phenylazo) -2-naphthol-6-sulfonic acid, 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-sulfophenyl) -5-hydroxy-pyrazolon-3 -carbonic acid, aluminum and zirconium salts of 4,5-dibromofluorescein, aluminum and zirconium salts of 2,4,5,7-tetrabromofluorescei n, 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. The types of pearlescent pigments listed below are particularly preferred: 1. Natural pearlescent pigments, such as. B.

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

^■ "mother-of-pearl" (milled mussel shells) 2. Monocrystalline pearlescent pigments such as bismuth oxychloride (BiOCI) 3. Layer-substrate pigments: eg 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 e.g. B. the gloss pigment listed under CIN 77163.

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

Assignment / Layer Thickness Color

Silver-white pearlescent pigments ^! TiO ₂ : 40-60 nm ^' silver interference pigments; TiO ₂ : 60 - 80 nm ^v ϊtT ^"~

TiO ₂ : 80 - 100 nm red TiO ₂ : 100 - 140 nm blue

TiO ₂ : 120-160 nm green

Colored pigments' Fe ₂ O ₃ bronze

; Fe ₂ O ₃ ^' copper. Fe ₂ O ₃ ! red Fe ₂ O ₃ , red violet , _. p ^ Q-

| Red Green

'Fe ₂ O ₃ ! black

Combination pigments TiO ₂ / Fe ₂ 0 ₃ ; golds

, TiO ₂ / Cr ₂ O ₃ , green

, TiO ₂ / Berlin blue deep blue

I TiO ₂ / Carmin ^■ Trot ^'

Particularly preferred are, for example, the pearlescent pigments available from Merck under the trade names Timiron, Colorona or Dichrona. Another preferred pigment is barium sulfate (BaSO ₄ ).

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 completely move to 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 copper 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 the selected 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 protection from sunlight, but which nevertheless contain UV protection substances. So z. For example, UV-A or UV-B filter substances are usually incorporated into day creams or makeup products. 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.

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;> O ₃ ), zirconium (ZrO ₂ ), silicon (SiO ₂ ), manganese (e.g. MnO), aluminum (AI ₂ O ₃ ), cerium (e.g. Ce ₂ O ₃ ), mixed oxides of the corresponding metals and mixtures of such oxides, as well as the sulfate of barium ( BaSO ₄ ).

In the context of the present invention, zinc oxides can also be used in the form of commercially available oily or aqueous predispersions. 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:

Titanium dioxide pigments according to the invention can be present both in the rutile and anatase crystal modification and, in the sense of the present invention, can advantageously be surface-treated (“coated”), with, for example, a hydrophilic, amphiphilic or hydrophobic character being formed or retained. This surface treatment can consist in that the pigments are provided with a thin hydrophilic and / or hydrophobic inorganic and / or organic layer by methods known per se The various surface coatings can also contain water for the purposes 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. Coated and uncoated titanium dioxides according to the invention can 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.

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

Z-oxides of the type Z-Cote HP1 and Z-Cote from BASF and NDM and Neutral from Haarmann and Reimer (H&R) are particularly advantageous for the purposes of the present invention. Furthermore, titanium dioxides of the Eusolex T-2000 type from Merck, T 805 from Degussa and MT-100Z and MT-100TV from Tayca are particularly advantageous for use in light protection emulsions.

Preparations according to the invention advantageously contain substances which absorb UV radiation in the UV-A and / or UV-B range, the total amount of the filter substances, for. B. 0.1 wt .-% to 30 wt .-%, preferably 0.5 to 20 wt .-%, in particular 1.0 to 15.0 wt .-%, based on the total weight of the preparations to kos - To provide metallic preparations that protect the hair or skin from the entire range of ultraviolet radiation. They can also serve as a sunscreen for the hair or skin.

Advantageous further UV-A filter substances for the purposes of the present invention are di-benzoylmethane derivatives, in particular 4- (tert-butyl) -4'-methoxydibenzoylmethane (CAS No. 70356-09-1), which is sold by Givaudan under the brand name Parsol ^® 1789 and is sold by Merck under the trade name Eusolex® 9020.

Other advantageous UV-A filter substances are phenylene-1,4-bis (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid

and their salts, especially the corresponding sodium, potassium or triethanolammonium salts, in particular the phenylene-1,4-bis (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid-bis sodium salt

with the INCI name bisimidazylate, which is available, for example, from Haarmann & Reimer under the trade name Neo Heliopan AP.

Also advantageous are the 1,4-di (2-oxo-10-sulfo-3-bomylidenemethyl) benzene and its salts (especially the corresponding 10-sulfato compounds, especially the corresponding sodium, potassium or triethanolammonium salt) , which is also called benzene-1,4-di (2-oxo-3-bomylidenemethyl-10-sulfonic acid) and is characterized by the following structure:

Advantageous UV filter substances in the sense of the present invention are also so-called broadband filters, i.e. Filter substances that absorb both UV-A and UV-B radiation.

Advantageous broadband filters or UV-B filter substances are, for example, bis-resorcinyltriazine derivatives with the following structure:

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. Particularly preferred are 2,4-bis - {[4- (2-ethylhexyloxy) -2-hydroxy] phenyl} -6- (4-methoxyphenyl) -1,3,5-triazine (INCI: Aniso triazine ), which is available under the trade name Tinosorb® S from CIBA-Chemical GmbH.

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], phenylene-1,4-bis (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid and / or its salts, the 1,4-di (2-oxo- 10-sulfo-3-bornylidenemethyl) benzene and / or its salts and / or the 2,4-bis - {[4- (2-ethylhexyloxy) -2-hydroxy] phenyl} -6- (4- methoxyphenyl) -1,3,5-triazine, in each case individually or in any combination with one another.

Also other UV filter substances, which the structural motif

are advantageous UV filter substances for the purposes of the present invention, for example the s-triazine derivatives described in European patent application EP 570838 A1, the chemical structure of which is given by the generic formula

is reproduced, whereby

R represents a branched or unbranched CrCι ₈ alkyl radical, a C ₅ -C ₁₂ cycloalkyl radical, optionally substituted by one or more C 1 -C ₄ alkyl groups,

X represents an oxygen atom or an NH group, a branched or unbranched CC ₁₈ alkyl radical, a C ₅ -C ₂ cycloalkyl radical, optionally substituted with one or more CC ₄ alkyl groups, or a hydrogen atom, an alkali metal atom, an ammonium group or a group of the formula

means in which

A represents a branched or unbranched C 1 -C ₁₈ alkyl radical, a C ₅ -C ₂ cycloalkyl or aryl radical, optionally substituted by one or more CC ₄ alkyl groups,

R _{3 represents} a hydrogen atom or a methyl group, n represents a number from 1 to 10, a branched or unbranched CC ₁₈ alkyl radical, a C ₅ -C ₂ cycloalkyl radical, optionally substituted by one or more CC ₄ alkyl groups , when X represents the NH group, and a branched or unbranched CC ₁₈ alkyl radical, a C ₅ -C ₁₂ cycloalkyl radical, optionally substituted by one or more CrC alkyl groups, or a hydrogen atom, an alkali metal atom, an ammonium group or a group of the formula

means in which

A is a branched or unbranched C ₁₈ -C ₁₈ alkyl radical, a C ₅ -C- | Represents ₂ -cycloalkyl or aryl radical, optionally substituted with one or more CC ₄ alkyl groups,

R _{3 represents} a hydrogen atom or a methyl group, n represents a number from 1 to 10 when X represents an oxygen atom. A particularly preferred UV filter substance in the sense of the present invention is also an asymmetrically substituted s-triazine, the chemical structure of which is represented by the formula

is reproduced, which is also referred to below as dioctylbutylamidotriazon (INCI: dioctylbutamidotriazone) and is available under the trade name UVASORB HEB from Sigma 3V.

A symmetrically substituted s-triazine which is 4,4 ', 4 "- (1,3,5-triazine-2,4,6-triyltriimino) -tris-benzoic acid tris (2- ethylhexyl ester), synonym: 2,4,6-tris [anilino- (p-carbo-2'-ethyl-1'-hexyloxy)] - 1,3,5-triazine (INCI: octyl triazone), which is marketed by BASF Aktiengesellschaft under the trade name UVINUL® T 150.

European laid-open specification 775 698 also describes bis-resorcinyltriazine derivatives which are to be used preferably, the chemical structure of which is given by the generic formula is reproduced, wherein R ^, R ₂ and A ^ represent various organic radicals.

Also advantageous in the sense of the present invention are the 2,4-bis - {[4- (3-sulfonato) - 2-hydroxypropyloxy) -2-hydroxy] phenyl} -6- (4-methoxyphenyl) -1, 3,5-triazine sodium salt, the 2,4-bis - {[4- (3- (2-propyloxy) -2-hydroxypropyloxy) -2-hydroxy] phenyl} -6- (4-methoxyphenyl ) -1, 3,5-triazine, the 2,4-bis - {[4- (2-ethylhexyloxy) -2-hydroxy] phenyl} -6- [4- (2-methoxyethyl carboxyl ) -phenylamino] -1, 3,5-triazine, the 2,4-bis - {[4- (3- (2-propyloxy) -2-hydroxypropyloxy) -2-hydroxy] phenyl} -6- [4- (2-ethyl-carboxyl) phenylamino] -1,3,5-triazine, the 2,4- bis - {[4- (2-ethylhexyloxy) -2-hydroxyj-phenyl} -6- (1-methyl-pyrrol-2-yl) -1, 3,5-triazine, the 2,4-bis - {[4-tris (trimethylsiloxysilylpropyloxy) -2-hydroxy] phenyl} -6- (4th -methoxyphenyl) - 1, 3,5-triazine, the 2,4-bis - {[4- (2 "-methylpropenyloxy) -2-hydroxy] phenyl} -6- (4-methoxyphenyl) -1, 3,5-triazine and the 2,4-bis - {[4- (1 ', r, 1', 3 ', 5', 5 ', 5'-heptamethylsiloxy-2 "-methylpropyloxy) -2- hydroxy] phenyl} -6- (4-methoxyphenyl) -1, 3,5-triazine.

The UV-B and / or broadband filters can be oil-soluble or water-soluble. Advantageous oil-soluble UV-B and / or broadband filter substances are e.g. B .:

■ 3-benzylidene camphor derivatives, preferably 3- (4-methylbenzylidene) camphor, 3-benzylidene camphor;

■ 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 UV-B and / or broadband filter substances are e.g. B .:

■ salts of 2-phenylbenzimidazole-5-sulfonic acid, such as its sodium, potassium or triethanolammonium salt, and the sulfonic acid itself;

■ sulfonic acid derivatives of 3-benzylidene camphor, such as. B. 4- (2-oxo-3-bomylidene methyl) benzenesulfonic acid, 2-methyl-5- (2-oxo-3-bornylidene methyl) sulfonic acid and salts thereof.

A further light protection filter substance to be used advantageously according to the invention is ethylhexyl-2-cyano-3,3-diphenylacrylate (octocrylene), which is available from BASF under the name Uvinul ^® N 539 and is distinguished by the following structure:

It can also be of considerable advantage to use polymer-bound or polymeric UV filter substances in preparations according to the present invention, in particular those as described in WO-A-92/20690.

It may also be advantageous, if appropriate, to incorporate further UV-A and / or UV-B filters into cosmetic or dermatological preparations, for example certain salicylic acid derivatives such as 4-isopropylbenzyl salicylate, 2-ethylhexyl salicylate (= octyl salicylate), homomenthyl salicylate.

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% by weight, based in each case on the total weight of the preparations, in order to provide cosmetic preparations which protect the hair or the skin from the entire range of ultraviolet radiation. They can also serve as a sunscreen for the hair or skin.

It may also be advantageous to incorporate film formers into the cosmetic or dermatological preparations according to the invention, for example in order 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 (Luviscol VA 64 Powder from BASF) 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. Hydrodispersions

Claims

claims

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

(b) contain at least one type of latex particle which has an average particle size of 100 to 400 nm.

2. Preparation according to claim 1, characterized in that it is sand-repellent.

3. Sunscreen-effective cosmetic or dermatological preparations, characterized in that they contain synergistic combinations of (a) at least one benzotriazole derivative and (b) at least one type of latex particles which have an average particle size of 100 to 400 nm, the UV-A Protection performance of these preparations is higher than the same preparations which do not contain any substances according to (b).

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

(a) at least one benzotriazole derivative and

(b) contain at least one type of latex particle which has an average particle size of 100 to 400 nm, the UV-B protection performance of these preparations being higher than the same preparations which do not contain any substances according to (b).

5. Preparation according to one of claims 1 or 2, characterized in that the active content of one or more types of latex particles is selected from the range of 0.5 to 6 wt .-%, based on the total weight of the preparation.

6. Preparation according to one of claims 1, 2 or 5, characterized in that the latex particles have a cavity filled with water and / or air.

7. Preparation according to one of the preceding claims, characterized in that it contains at least one UV filter substance which is liquid at room temperature.

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

9. Preparation according to one of the preceding claims, characterized in that it contains at least one further UV filter substance selected from the group triazines, camphor derivatives and organic and / or inorganic pigments.

10. Preparation according to one of the preceding claims, characterized in that it contains at least one further UV-A filter substance and / or a broadband filter selected from the group of 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, 1,4-di (2-oxo-10-sulfo-3-bornylidenemethyl ) -Benzene and its salts and 2,4-bis - {[4- (2-ethylhexyloxy) -2-hydroxy] phenyl} -6- (4-methoxyphenyl) -1,3,5-triazine , contains, wherein the further filter substances can be present individually or in any combination with one another.

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. Use of preparations according to claim 8 or 9 for protecting the skin from premature aging.

13. Use of preparations according to one of the preceding claims for moisturizing the skin.