WO2002049582A2 - Cosmetic and dermatological light protective formulations containing benzotriazole derivatives and surface active citric acid esters - Google Patents

Cosmetic and dermatological light protective formulations containing benzotriazole derivatives and surface active citric acid esters Download PDF

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Publication number
WO2002049582A2
WO2002049582A2 PCT/EP2001/014931 EP0114931W WO0249582A2 WO 2002049582 A2 WO2002049582 A2 WO 2002049582A2 EP 0114931 W EP0114931 W EP 0114931W WO 0249582 A2 WO0249582 A2 WO 0249582A2
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Prior art keywords
acid
derivatives
preparations
red
skin
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PCT/EP2001/014931
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German (de)
French (fr)
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WO2002049582A3 (en
Inventor
Anja MÜLLER
Beate Uhlmann
Ariane Kranz
Albrecht DÖRSCHNER
Anja Knüppel
Anja Suckert
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Beiersdorf Ag
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Priority to EP01271197A priority Critical patent/EP1377252A2/en
Publication of WO2002049582A2 publication Critical patent/WO2002049582A2/en
Publication of WO2002049582A3 publication Critical patent/WO2002049582A3/en

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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/04Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/34Alcohols
    • A61K8/342Alcohols having more than seven atoms in an unbroken chain
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/37Esters of carboxylic acids
    • A61K8/375Esters of carboxylic acids the alcohol moiety containing more than one hydroxy group
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/494Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
    • A61K8/496Triazoles or their condensed derivatives, e.g. benzotriazoles
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/58Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing atoms other than carbon, hydrogen, halogen, oxygen, nitrogen, sulfur or phosphorus
    • A61K8/585Organosilicon compounds

Definitions

  • Cosmetic and dermatological light protection formulations containing benzotriazole derivatives and surface-active citric acid esters containing benzotriazole derivatives and surface-active citric acid esters
  • 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.
  • 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.
  • 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.
  • 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. It has been proven, among other things, that even UV-A radiation is sufficient under normal everyday conditions to damage collagen and elastin fibers, which are essential for the structure and firmness of the skin, within a short period of time. 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 can have irregular pigmentation Brown spots, keratoses and even carcinomas or malignant melanomas are 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.
  • UV-A radiation 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 majority of UV-A radiation penetrates the living epidermis, while around 70% of UV-B rays are retained by the horny layer.
  • aftersun or apres-soleil preparations are intended to cool the skin after sunbathing and to improve its moisture retention, whereby the imparting of the cooling effect plays a central role.
  • 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.
  • cosmetic or dermatological emulsions which act to protect the sun, characterized in that they (a) one or more partially neutralized esters of monoglycerides and / or diglycerides of saturated fatty acids with citric acid and
  • the emulsions according to the invention are preferably O / W emulsions.
  • 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 distributability 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 sun protection effect, characterized in that they contain synergistic combinations of substances
  • (b) contain at least one benzotriazole derivative, the UV protection performance of these preparations being higher than the same preparations which contain no substances according to (a).
  • a measure of the UV protection performance in the sense of the present invention is, for example, the sun protection factor (SPF or SPF).
  • the cosmetic and dermatological preparations in the sense of the present invention do not leave a greasy or sticky impression on the skin, are extremely skin-friendly and, furthermore, are surprisingly distinguished by the fact that they are sand-repellent.
  • the invention therefore also relates to sand-repellent cosmetic or dermatological sunscreen preparations, characterized in that they
  • (b) contain at least one benzotriazole derivative.
  • a particularly advantageous citric acid ester for the purposes of the present invention is glyceryl stearate citrate.
  • Such citric acid esters are available, for example, from Hüls AG under the product name "IMWITOR® 370".
  • the total amount of one or more citric acid esters according to the invention in the finished cosmetic or dermatological preparations is advantageously selected from the range from 0.1 to 10.0% by weight, preferably 0.5 to 6.0% by weight, based on the Total weight of the preparations.
  • Advantageous further emulsifiers for the purposes of the present invention are, for example, silicone emulsifiers, phosphate emulsifiers and / or ethoxylated emulsifiers.
  • Coemulsifiers which are advantageous according to the invention are fatty alcohols, in particular fatty alcohols with a chain length of 10 to 30 carbon atoms. Cetyl, stearyl and / or cetearyl alcohol are particularly preferred.
  • a particularly advantageous benzotriazole derivative for the purposes of the present invention is 2,2 , -methylene-bis- (6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol) [ INCI: Bisoctyltriazol], which is characterized by the chemical structural formula
  • 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] disiloxanyI] propyl] phenol (CAS no .: 155633-54-8) with the INCI name Drometrizole Trisiloxane, which is characterized by the chemical structural formula
  • 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.
  • 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 as are usually used in such preparations. be applied, e.g. 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.
  • cosmetic auxiliaries e.g. 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
  • Advantageous preservatives for the purposes of the present invention are, for example, formaldehyde releasers (such as, for example, DMDM hydantoin), iodopropylbutyl carbamates (for example those available from Lonza under the trade names Koncyl-L, Koncyl-S and Konkaben LMB), Parabens, phenoxyethanol, ethanol, benzoic acid and the like.
  • the preservation system usually also advantageously comprises preservation aids, such as, for example, octoxyglycerol, glycine soya, etc.
  • compositions are also obtained if antioxidants are used as additives or active ingredients.
  • 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-carnosine, L-carnosine and their derivatives (e.g. anserine), carotenoids, carotenes (e.g. ⁇ -carotene, ß-carotene, lycopene) and their derivatives, lipoic acid and their derivatives (e.g.
  • amino acids e.g. glycine, histidine, tyrosine, tryptophan
  • imidazoles e.g. urocanic acid
  • peptides such as D, L-carnosine, D-carnosine, L-carnosine and their derivatives (e.g. anserine)
  • carotenoids e.g
  • thioglucose e.g. thioredoxin, glutathione, cysteine, cystine, cystamine and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl, and lauryl, palmitoyl, oleyl, ⁇ -linoleyl, cholesteryl and glyceryl esters
  • 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.
  • buthionine sulfoximines in very low tolerable dosages (e.g. B. pmol to ⁇ mol / kg), also (metal) chelators (e.g. ⁇ -hydroxy fatty acids, palmitic acid, Phytic acid, lactoferrin), ⁇ -hydroxy acids (e.g.
  • citric acid citric acid, lactic acid, malic acid
  • humic acid bile acid, bile extracts, bilirubin, biliverdin, EDTA, EGTA and their derivatives
  • unsaturated fatty acids and their derivatives e.g. ⁇ -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, ascorbylacetate
  • tocopherols and derivatives e.g.
  • vitamin E - acetate Vitamin A and derivatives (vitamin A - palmitate) as well as konyferyl benzoate of benzoin, rutinic acid and its derivatives, ferric acid and its derivatives, butylhydroxytoluene, butylhydroxyanisole, nordihydroguajak resin acid, nordihydroguajaretic acid, trihydroxybutyrophenon and urine derivatives, urine their derivatives, zinc and its derivatives (e.g. ZnO, ZnS04) selenium and its derivatives (e.g. selenium methionine), stilbene and their.
  • Derivatives e.g. stilbene oxide, trans-stilbene oxide
  • derivatives salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids
  • water-soluble antioxidants such as vitamins, e.g. B. ascorbic acid and its derivatives.
  • compositions according to the invention 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 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.
  • vitamin E and / or its derivatives represent the antioxidant (s)
  • vitamin A or vitamin A derivatives or carotenes or their derivatives represent the antioxidant or antioxidants, it is advantageous to determine their respective concentrations from the range from 0.001 to 10 wt .-%, based on the total weight of the formulation to choose.
  • the active ingredients can also be selected very advantageously from the group of lipophilic active ingredients, in particular from the following group:
  • 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 ultraviolet radiation on the skin should serve.
  • the preferred NO synthase inhibitor is nitroarginine.
  • the active ingredient (s) are furthermore advantageously selected from the group comprising gate chines 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 understood 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) Also epicatechin ((2R, 3R) -3.3 l , 4 ', 5J-flavanpentaol) is an advantageous active substance in the sense of the present invention.
  • 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 are also advantageous active substances in the sense of the present invention. They are characterized by the following basic structure (substitution positions indicated):
  • flavones usually occur in glycosidated form.
  • the flavonoids are preferably selected from the group of substances of the generic structural formula
  • Zi to Z 7 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 of the mono- and oligoglycoside residues.
  • the flavonoids can also be advantageously selected from the group of substances of the generic structural formula
  • Zi 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 of the mono- and oligoglycoside residues.
  • Such structures can preferably be selected from the group of substances of the generic structural formula
  • 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.
  • 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.
  • Zi 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
  • 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.
  • 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.
  • flavone glycoside (s) from the group ⁇ -glucosyl rutin, ⁇ -glucosyl myrcetin, ⁇ -glucosyl iso-quercitrin, ⁇ -glucosyl iso-quercetin and glucosyl-quercitrin.
  • ⁇ -glucosylrutin is particularly preferred.
  • naringin aurantiin, naringenin-7-rhamnoglucosid
  • hesperidin 3 ⁇ 5J-trihydroxy-4'-methoxyflavanon-7-rutinoside
  • hesperidoside hesperetin-7-O-rutinoside
  • Rutin (3,3 ', 4', 5J-Pentahydroxyflyvon-3-rutinosid, Quercetin-3-rutinosid, Sophorin, Birutan, Rutabion, Taurutin, Phytomelin, Melin), Troxerutin (3,5-Dihydroxy-3 ', 4 ', 7-tris (2-hydroxyethoxy) flavon-3- (6-O- (6-deoxy- ⁇ -L-mannopyranosyl) -ß-D-glucopyranoside)), monoxerutin (3,3', 4 ', 5-tetrahydroxy-7- (2-hydroxyethoxy) flavon-3- (6-O- (6-deoxy- ⁇ -L-mannopyranosyl) -ß-D-glucopyranoside)), dihydrorobinetin (3, 3 ', 4', 5 ', 7-pentahydroxyflavanone), taxifolin (3,3', 4 ', 5,7-pentahydroxyflava
  • the active ingredient (s) from the group of ubiquinones and plastoquinones.
  • Coenzyme Q10 which is characterized by the following structural formula, is particularly advantageous:
  • 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.
  • acyl-carnitine which is selected from the group of substances of the following general structural formula C— R /
  • R is selected from the group of branched and unbranched alkyl radicals having up to 10 carbon atoms are advantageous active substances in the sense of the present invention.
  • Propionylcamitine 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.
  • 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.
  • selected recipes according to the invention are suitable, which e.g. B. known anti-wrinkle active ingredients such as flavone glycosides (especially ⁇ -glycosyl rutin), 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 during skin aging. They are also advantageous against the appearance of dry or rough skin.
  • B. known anti-wrinkle active ingredients such as flavone glycosides (especially ⁇ -glycosyl rutin), 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 during 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":
  • 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:
  • 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, 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 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.
  • 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.
  • 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 laurate, n-decyl oleate, isooctyl stearate, isonononyl stylate ethyl isononylyl stomate 2-octyldodecyl palmitate, stearyl heptanoate, oleyl oleate, olerlerucate, erucyl oleate, erucylerucate, tridecyl stearate, tridecyl trimellitate
  • the oil phase can advantageously be selected from the group of dialkyl ethers and dialkyl carbonates.
  • 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.
  • 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.
  • 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 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
  • 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.
  • phenylmethylpolysiloxanes INCI: phenyl dimethicone, phenyl trimethicone
  • cyclic silicones octamethylcyclotetrasiloxane or decamethylcyciopentasiloxane
  • amino-modified silicones INCI: amodimethethicones, z. 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.
  • other silicone oils can also be used advantageously for the purposes of the present invention, for example cetyldimethicone, hexamethylcyclotrisiloxane, polydimethylsiloxane, poly (methylphenylsiloxane).
  • z. B. natural waxes of animal and vegetable origin such as beeswax, china wax, bumblebee wax and other insect waxes and shea butter.
  • 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 liquid at room temperature as a further phase.
  • 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 He-Iiopan 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:
  • 4-methoxycinnamic acid isopentyl ester isopentyl-4-methoxycinnamate, INCI: isoamyl p-methoxycinnamate
  • isopentyl-4-methoxycinnamate INCI: isoamyl p-methoxycinnamate
  • Neo Heliopan E 1000 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.
  • 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 customary cosmetic auxiliaries, such as, for example, alcohols, in particular those having a low C number, preferably ethanol and / or isopropanol, diols or polyols having 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 consisting of silicon dioxide and aluminum silicates.
  • customary cosmetic auxiliaries such as, for example, alcohols, in particular those having a low C number, preferably ethanol and / or isopropanol, diols or polyols having a low C number
  • 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 reducing the release of moisture from the skin layer (also called trans-epidermal water joss (TEWL)) and / or hydrating the skin after application or distribution on the skin surface To influence the horny layer positively.
  • TEWL trans-epidermal water joss
  • moisturizers in the sense 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 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.
  • 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).
  • 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.
  • 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.
  • cosmetic or topical dermatological compositions in the sense of the present invention can be used, for example, as a skin protection cream, cleansing milk, day or night cream, etc. if 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 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 list below.
  • the Color Index Numbers (CIN) are taken from the Rowe Color Index, 3rd edition, Society ofDyers and Colorists, Bradford, England, 1971.
  • Chlorophyll a and b Copper compounds of chlorophylls and 75810 green,
  • Chromium oxide containing 77289 green
  • Titanium dioxide and its mixtures with mica 77891 white
  • 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-T-phenylazo) -2-hydroxynaphthalene, ceres red, 2- (4-sulfo-1-naphthylazo) -1-naphthol-4-sulfonic acid, calcium salt of 2-hydroxy-1, 2'-azonaphthalenesulfonic 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
  • 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:
  • Natural pearlescent pigments such as. B.
  • Monocrystalline pearlescent pigments such as B. Bismuth oxychloride (BiOCI)
  • 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. Z is particularly advantageous.
  • pearlescent pigment types based on mica / metal oxide are also advantageous:
  • pearlescent pigments available from Merck under the trade names Timiron, Colorona or Dichrona.
  • pearlescent pigments which are advantageous in the sense of the present invention are obtainable in numerous ways known per se.
  • other substrates besides mica can be coated with other metal oxides, such as. B. silica and the like.
  • metal oxides such as. B. silica and the like.
  • Ronaspheren TiO 2 and Fe 2 O 3 coated SiO 2 particles
  • 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.
  • 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% by weight to 30% by weight, preferably from 0.5 to 15% by weight, in particular from 1.0 to 10% by weight, in each case 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.
  • 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.
  • the preparations preferably contain, in addition to one or more UV filter substances according to the invention, at least one further UV-A and / or UV-B filter substance.
  • the formulations may, 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 the oil phase.
  • 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 and mixtures of such oxides.
  • such pigments can advantageously be surface-treated (“coated”), with an amphiphilic or hydrophobic character, for example, being formed or maintained be provided with a hydrophobic layer.
  • z. B titanium dioxide pigments coated with octylsilanol. Suitable titanium dioxide particles are available under the trade name T805 from Degussa. Also particularly advantageous are TiO 2 pigments coated with aluminum stearate, e.g. B. those available under the trade name MT 100 T from TAYCA.
  • Another advantageous coating of the inorganic pigments consists of dimethylpolysiloxane (also: dimethicone), a mixture of fully methylated, linear siloxane polymers which are blocked at the end with trimethylsiloxy units. Zinc oxide pigments which are coated in this way are particularly advantageous for the purposes of the present invention.
  • the inorganic pigments are also advantageous to coat with a mixture of dimethylpolysiloxane, in particular dimethylpolysiloxane with an average chain length of 200 to 350 dimethylsiloxane units, and silica gel, which is also referred to as simethicone. It is particularly advantageous if the inorganic pigments are additionally coated with aluminum hydroxide or aluminum oxide hydrate (also: alumina, CAS no .: 1333-84-2). Titanium dioxides coated with simethicone and alumina are particularly advantageous, the coating also being able to contain water. An example of this is the titanium dioxide available from Merck under the trade name Eusolex T2000.
  • 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 cosmetic
  • 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 cosmetic
  • 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.
  • 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.
  • 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.
  • 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
  • 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
  • benzene-1,4-di (2-oxo-3-bornylidenemethyl-10-sulfonic acid is also called benzene-1,4-di (2-oxo-3-bornylidenemethyl-10-sulfonic acid
  • 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:
  • 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-Chemicals GmbH.
  • Particularly advantageous preparations in the sense 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 4- (tert.
  • UV filter substances which the structural motif
  • UV filter substances for the purposes of the present invention, for example the s-triazine derivatives described in European patent application EP 570 838 A1, the chemical structure of which is given by the generic formula
  • R represents a branched or unbranched C r -C 8 alkyl radical, a C 5 -C 2 cycloalkyl radical, optionally substituted with one or more CC alkyl groups,
  • X represents an oxygen atom or an NH group
  • Ri is a branched or unbranched CrC 8 alkyl radical, a C ⁇ -C ⁇ 2 cycloalkyl radical, optionally substituted with one or more CC alkyl groups, or a hydrogen atom, an alkali metal atom, an ammonium group or a group of the formula
  • 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 dC - alkyl groups
  • R 3 represents a hydrogen atom or a methyl group
  • n is a number from 1 to 10
  • R 2 represents a branched or unbranched C 1 -C 18 -alkyl radical, a C 3 -C 2 -cycloalkyl radical, optionally substituted by one or more CrC - alkyl groups, if X represents the NH group, and a branched or unbranched CrC 18 alkyl radical, a C 5 -C 2 cycloalkyl radical, optionally substituted with one or more dC alkyl groups, or a hydrogen atom, an alkali metal atom, an ammonium group or a group of the formula
  • A represents a branched or unbranched CrCis alkyl radical, a C 5 -C 2 cycloalkyl or aryl radical, optionally substituted by one or more dC 4 alkyl groups
  • R 3 represents a hydrogen atom or a methyl group
  • n is a number from 1 to 10 represents 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
  • 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-triyltriimin ⁇ ) -tris-benzoic acid tris (2- ethylhexyl ester), synonymous: 2,4,6-tris [anilino- (p-carbo-2'-ethyl-T-hexyloxy)] - 1,3,5-triazine (INCI: octyl triazone), which is from from BASF Aktiengesellschaft under the trade name UVINUL® T 150.
  • R ⁇ , R 2 and Ai represent a wide variety of 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
  • 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;
  • 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
  • benzophenone preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone
  • Advantageous water-soluble UV-B and / or broadband filter substances are e.g.
  • ⁇ 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.
  • Another light protection filter substance which can 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:
  • 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 cosmetic
  • 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 fat-soluble film formers are e.g. B., the film formers from the group of polymers based on polyvinylpyrrolidone (PVP)
  • 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.

Abstract

The invention relates to light protective cosmetic or dermatological emulsions which are characterised in that they contain (a) one or more partially neutralised esters of monoglycerides and/or diglycerides of saturated fatty acids with acetic acid and (b) at least one benzotriazole derivatives. The invention also relates to the use of said emulsions.

Description

Beschreibung description
Kosmetische und dermatologische Lichtschutzformulierungen mit einem Gehalt an Benzotriazolderivaten und oberflächenaktiven ZitronensäureesternCosmetic and dermatological light protection formulations containing benzotriazole derivatives and surface-active citric acid esters
Die vorliegende Erfindung betrifft kosmetische und dermatologische Lichtschutzzubereitungen, insbesondere betrifft sie sandabweisende kosmetische und dermatologische Lichtschutzzubereitungen.The present invention relates to cosmetic and dermatological light protection preparations, in particular it relates to sand-repellent cosmetic and dermatological light protection preparations.
Die schädigende Wirkung des ultravioletten Teils der Sonnenstrahlung auf die Haut ist allgemein bekannt. In Abhängigkeit von ihrer jeweiligen Wellenlänge haben die Strahlen verschiedene Wirkungen auf das Organ Haut: Die sogenannte UV-C-Strahlung mit einer Wellenlänge, die kleiner als 290 nm ist, wird von der Ozonschicht in der Erdatmosphäre absorbiert und hat daher keine physiologische Bedeutung. Dagegen verursachen Strah- len im Bereich zwischen 290 nm und 320 nm, dem sogenannten UV-B-Bereich, ein Ery- them, einen einfachen Sonnenbrand oder sogar mehr oder weniger starke Verbrennungen. Als ein Maximum der Erythemwirksamkeit des Sonnenlichtes wird der engere Bereich um 308 nm angegeben.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.
Zum Schutz gegen UV-B-Strahlung sind zahlreiche Verbindungen bekannt, bei denen es sich beispielsweise um Derivate des 3-Benzylidencamphers, der 4-Aminobenzoesäure, der Zimtsäure, der Salicylsäure, des Benzophenons sowie des s-Triazins handelt.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.
Man hat lange Zeit fälschlicherweise angenommen, daß die langwellige UV-A-Strahlung mit einer Wellenlänge zwischen 320 nm und 400 nm nur eine vernachlässigbare biologische Wirkung aufweist. Inzwischen ist allerdings durch zahlreiche Studien belegt, daß UV-A-Strahlung im Hinblick auf die Auslösung photodynamischer, speziell phototoxischer Reaktionen und chronischer Veränderungen der Haut weitaus gefährlicher als UV-B- Strahlung ist. Auch kann der schädigende Einfluß der UV-B-Strahlung durch UV-A- Strahlung noch verstärkt werden. So ist es u. a. erwiesen, daß selbst die UV-A-Strahlung unter ganz normalen Alltagsbedingungen ausreicht, um innerhalb kurzer Zeit die Collagen- und Elastinfasern zu schädigen, die für die Struktur und Festigkeit der Haut von wesentlicher Bedeutung sind. Hierdurch kommt es zu chronischen lichtbedingten Hautveränderungen - die Haut „altert" vorzeitig. Zum klinischen Erscheinungsbild der durch Licht gealterten Haut gehören beispielsweise Falten und Fältchen sowie ein unregelmäßiges, zerfurchtes Relief. Ferner können die von lichtbedingter Hautalterung betroffenen Partien eine unregelmäßige Pigmentierung aufweisen. Auch die Bildung von braunen Flecken, Keratosen und sogar Karzinomen bzw. malignen Melanomen ist möglich. Eine durch die alltägliche UV-Belastung vorzeitig gealterte Haut zeichnet sich außerdem durch eine geringere Aktivität der Lan- gerhanszellen und eine leichte, chronische Entzündung aus.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. It has been proven, among other things, that even UV-A radiation is sufficient under normal everyday conditions to damage collagen and elastin fibers, which are essential for the structure and firmness of the skin, within a short period of time. 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 can have irregular pigmentation Brown spots, keratoses and even carcinomas or malignant melanomas are 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.
Etwa 90 % der auf die Erde gelangenden ultravioletten Strahlung besteht aus UV-AStrahlen. Während die UV-B-Strahlung in Abhängigkeit von zahlreichen Faktoren stark variiert (z. B. Jahres- und Tageszeit oder Breitengrad), bleibt die UV-A-Strahlung unabhängig von jahres- und tageszeitlichen oder geographischen Faktoren Tag für Tag relativ konstant. Gleichzeitig dringt der überwiegende Teil der UV-A-Strahlung in die lebende Epidermis ein, während etwa 70 % der UV-B-Strahlen von der Hornschicht zurückgehalten werden.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 majority of UV-A radiation penetrates the living epidermis, while around 70% of UV-B rays are retained by the horny layer.
Es ist daher von grundsätzlicher Wichtigkeit, daß kosmetische und dermatologische Lichtschutzzubereitungen sowohl gegen UV-B- als auch gegen UV-A-Strahlung ausreichenden Schutz bieten.It is therefore of fundamental importance that cosmetic and dermatological light protection preparations offer adequate protection against both UV-B and UV-A radiation.
Im allgemeinen ist das Lichtabsorptionsverhalten von Lichtschutzfiltersubstanzen sehr gut bekannt und dokumentiert, zumal in den meisten Industrieländern Positivlisten für den Einsatz solcher Substanzen existieren, welche recht strenge Maßstäbe an die Dokumentation anlegen.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.
Die Einsatzkonzentration bekannter als Feststoff vorliegender Lichtschutzfiltersubstanzen ist allerdings häufig - gerade in Kombination mit anderen zu lösenden Substanzen - begrenzt. Es bereitet daher gewisse formulierungstechnische Schwierigkeiten, höhere Lichtschutzfaktoren bzw. UV-A-Schutzleistung zu erzielen. Der Sonnenbrand bzw. das Lichterythem sind die akuten Erscheinungsformen der Lichteinwirkung. Neben den bereits beschriebenen Wirkungen der UV-Strahlen kommt es in der Nachreaktion der Haut ferner zu einer verminderten Sebumproduktion und einem Austrocknen der Haut. Zur Linderung und zur Pflege dieser Phänomene kennt der Stand der Technik Produkte, welche nach dem Sonnenbaden angewendet werden und üblicherweise spezielle Wirkstoffe enthalten, wie beispielsweiseHowever, 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
■ Rückfettungs- und Feuchthaltemittel,■ regreasing and moisturizing agents,
■ entzündungslindernde und kühlende Stoffe,■ anti-inflammatory and cooling substances,
■ lokal anaestesierende Stoffe und/oder ■ desinfizierende Stoffe, um mögliche Hautinfektionen zu verhindern.■ locally anesthetic substances and / or ■ disinfectants to prevent possible skin infections.
Diese, sogenannten Aftersun- oder Apres-soleil-Präparate sind dazu bestimmt, die Haut nach dem Sonnenbad zu kühlen und ihr Feuchthaltevermögen zu verbessern, wobei die Vermittlung des Kühleffektes eine zentrale Rolle spielt. Allerdings mangelt es dem Stand der Technik an Produkten, welche die Haut bereits während der UV-Einstrahlung vor dem Austrocknen schützen und sie ausreichend pflegen.These so-called aftersun or apres-soleil preparations are intended to cool the skin after sunbathing and to improve its moisture retention, 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.
Ein weiterer Nachteil des Standes der Technik ist, daß übliche Lichtschutzformulierungen einen meist klebrigen Film auf der Haut hinterlassen. Dies hat z. B. bei der Anwendung solcher Produkte an einem Sandstrand zur Folge, daß der Sand am Körper haften bleibt, was vom Anwender als unangenehm empfunden wird und im schlimmsten Fall dazu führen kann, daß das Sonnenschutzmittel zu wenig oder gar nicht mehr verwendet wird. Da am Meer meist ein mehr oder weniger starker Wind herrscht, tritt dieser Nachteil in der Regel selbst dann auf, wenn der Körper gar nicht direkt mit dem Sand in Berührung kommt - beispielsweise beim Sonnenbaden auf einem Liegestuhl - da auch der im Wind herumwirbelnde Sandstaub auf den eingecremten Hautpartien haften bleibt.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.
Eine weitere Aufgabe der vorliegenden Erfindung war daher, Lichtschutzformulierungen zu finden, nach deren Anwendung kein Sand auf der eingecremten Haut kleben bleibt, die also dementsprechend als sandabweisend zu bezeichnen sind.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.
Es war überraschend und für den Fachmann nicht vorauszusehen, daß lichtschutzwirksame kosmetische oder dermatologische Emulsionen, dadurch gekennzeichnet, daß sie (a) einen oder mehrere partiell neutralisierte Ester von Monoglyceriden und/oder Di- glyceriden gesättigter Fettsäuren mit Zitronensäure undIt was surprising and unforeseeable for the person skilled in the art that cosmetic or dermatological emulsions which act to protect the sun, characterized in that they (a) one or more partially neutralized esters of monoglycerides and / or diglycerides of saturated fatty acids with citric acid and
(b) mindestens ein Benzotriazolderivat enthalten, den Nachteilen des Standes der Technik abhelfen.(b) contain at least one benzotriazole derivative which remedies the disadvantages of the prior art.
Bevorzugt stellen die erfindungsgemäßen Emulsionen O/W-Emulsionen dar.The emulsions according to the invention are preferably O / W emulsions.
Die erfindungsgemäßen Emulsionen stellen in jeglicher Hinsicht überaus befriedigende Präparate dar, welche nicht auf eine eingeschränkte Rohstoffauswahl begrenzt sind. Dementsprechend eignen sie sich ganz besonders, um als Grundlage für Zubereitungsformen mit vielfältigen Anwendungszwecken zu dienen. Die erfindungsgemäßen Zubereitungen zeigen sehr gute sensorische und kosmetische Eigenschaften, wie beispielsweise die Verteilbarkeit auf der Haut oder das Einzugsvermögen in die Haut, und zeich- nen sich ferner durch eine sehr gute Lichtschutzeffektivität bei gleichzeitig hervorragenden Hautpflegedaten aus.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 distributability 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.
Gegenstand der Erfindung sind daher auch lichtschutzwirksame kosmetische oder dermatologische Zubereitungen, dadurch ge- kennzeichnet, daß sie synergistische Stoffkombinationen vonThe invention therefore also relates to cosmetic or dermatological preparations which have a sun protection effect, characterized in that they contain synergistic combinations of substances
(a) einem oder mehreren partiell neutralisierten Estern von Monoglyceriden und/oder Diglyceriden gesättigter Fettsäuren mit Zitronensäure und(a) one or more partially neutralized esters of monoglycerides and / or diglycerides of saturated fatty acids with citric acid and
(b) mindestens einem Benzotriazolderivat enthalten, wobei die UV-Schutzleistung dieser Zubereitungen höher ist als die gleicher Zubereitungen, welche keine Substanzen gemäß (a) enthalten.(b) contain at least one benzotriazole derivative, the UV protection performance of these preparations being higher than the same preparations which contain no substances according to (a).
Ein Maß für die UV-Schutzleistung stellt im Sinne der vorliegenden Erfindung beispielsweise der Lichtschutzfaktor (LSF bzw. SPF) dar.A measure of the UV protection performance in the sense of the present invention is, for example, the sun protection factor (SPF or SPF).
Die kosmetischen und dermatologischen Zubereitungen im Sinne der vorliegenden Erfindung hinterlassen auf der Haut keinen schmierigen oder klebrigen Eindruck, sind ausgezeichnet hautverträglich und zeichnen sich ferner überraschender Weise dadurch aus, daß sie sandabweisend sind. Gegenstand der Erfindung sind daher auch sandabweisende kosmetische oder dermatologische Lichtschutzzubereitungen, dadurch gekennzeichnet, daß sieThe cosmetic and dermatological preparations in the sense of the present invention do not leave a greasy or sticky impression on the skin, are extremely skin-friendly and, furthermore, are surprisingly distinguished by the fact that they are sand-repellent. The invention therefore also relates to sand-repellent cosmetic or dermatological sunscreen preparations, characterized in that they
(a) einen oder mehrere partiell neutralisierte Ester von Monoglyceriden und/oder Di- glyceriden gesättigter Fettsäuren mit Zitronensäure und(a) one or more partially neutralized esters of monoglycerides and / or diglycerides of saturated fatty acids with citric acid and
(b) mindestens ein Benzotriazolderivat enthalten.(b) contain at least one benzotriazole derivative.
Ein besonders vorteilhafter Zitronensäureester im Sinne der vorliegenden Erfindung ist das Glycerylstearatcitrat. Solche Zitronensäureester sind beispielsweise unter der Produktbezeichnung „IMWITOR® 370" bei der Hüls AG erhältlich.A particularly advantageous citric acid ester for the purposes of the present invention is glyceryl stearate citrate. Such citric acid esters are available, for example, from Hüls AG under the product name "IMWITOR® 370".
Die Gesamtmenge an einem oder mehreren erfindungsgemäßen Zitronensäureestern in den fertigen kosmetischen oder dermatologischen Zubereitungen wird vorteilhaft aus dem Bereich von 0,1 bis 10,0 Gew.-%, bevorzugt 0,5 bis 6,0 Gew.-% gewählt, bezogen auf das Gesamtgewicht der Zubereitungen.The total amount of one or more citric acid esters according to the invention in the finished cosmetic or dermatological preparations is advantageously selected from the range from 0.1 to 10.0% by weight, preferably 0.5 to 6.0% by weight, based on the Total weight of the preparations.
Es kann gegebenenfalls von Vorteil sein, weitere Emulgatoren bzw. Coemulgatoren in die erfindungsgemäßen kosmetischen oder dermatologischen Zubereitungen einzuarbeiten, beispielsweise um die Stabilität der Zubereitungen weiter zu verbessern.It may be advantageous to incorporate further emulsifiers or co-emulsifiers into the cosmetic or dermatological preparations according to the invention, for example in order to further improve the stability of the preparations.
Vorteilhafte weitere Emulgatoren im Sinne der vorliegenden Erfindung sind beispielsweise Siliconemulgatoren, Phosphatemulgatoren und/oder ethoxylierte Emulgatoren.Advantageous further emulsifiers for the purposes of the present invention are, for example, silicone emulsifiers, phosphate emulsifiers and / or ethoxylated emulsifiers.
Erfindungsgemäß vorteilhafte Coemulgatoren sind Fettalkohole, insbesondere Fettalkohole mit einer Kettenlänge von 10 bis 30 Kohlenstoffatomen. Besonders bevorzugt sind Cetyl-, Stearyl- und/oder Cetearylalkohol.Coemulsifiers which are advantageous according to the invention are fatty alcohols, in particular fatty alcohols with a chain length of 10 to 30 carbon atoms. Cetyl, stearyl and / or cetearyl alcohol are particularly preferred.
Ein besonders vorteilhaftes Benzotriazolderivat im Sinne der vorliegenden Erfindung ist das 2,2,-Methylen-bis-(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)-phenol) [INCI: Bisoctyltriazol], welches sich durch die chemische Strukturformel A particularly advantageous benzotriazole derivative for the purposes of the present invention is 2,2 , -methylene-bis- (6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol) [ INCI: Bisoctyltriazol], which is characterized by the chemical structural formula
Figure imgf000007_0001
auszeichnet und z. B. unter der Handelsbezeichnung Tinosorb® M bei der CIBA-Che- mikalien GmbH erhältlich ist.
Figure imgf000007_0001
distinguished and z. B. is available under the trade name Tinosorb® M from CIBA-Chemical GmbH.
Vorteilhaftes Benzotriazolderivat im Sinne der vorliegenden Erfindung ist femer das 2- (2H-benzotriazol-2-yl)-4-methyl-6-[2-methyl-3-[1 ,3,3,3-tetramethyl-1-[(trimethylsilyl)oxy]di- siloxanyI]propyl]-phenol (CAS-Nr.: 155633-54-8) mit der INCI-Bezeichnung Drometrizole Trisiloxane, welches durch die chemische StrukturformelAnother 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] disiloxanyI] propyl] phenol (CAS no .: 155633-54-8) with the INCI name Drometrizole Trisiloxane, which is characterized by the chemical structural formula
Figure imgf000007_0002
gekennzeichnet ist.
Figure imgf000007_0002
is marked.
Die erfindungsgemäßen kosmetischen oder dermatologischen Lichtschutzformulierungen können wie üblich zusammengesetzt sein und dem kosmetischen oder dermatologischen Lichtschutz, ferner zur Behandlung, Pflege und Reinigung der Haut und/oder der Haare und als Schminkprodukt in der dekorativen Kosmetik dienen.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.
Zur Anwendung werden die kosmetischen und dermatologischen Zubereitungen in der für Kosmetika üblichen Weise auf die Haut und/oder die Haare in ausreichender Menge aufgebracht.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.
Die kosmetischen und dermatologischen Zubereitungen gemäß der Erfindung können kosmetische Hilfsstoffe enthalten, wie sie üblicherweise in solchen Zubereitungen ver- wendet werden, z. B. Konservierungsmittel, Konservierungshelfer, Bakterizide, Parfüme, Substanzen zum Verhindern des Schäumens, Farbstoffe, Pigmente, die eine färbende Wirkung haben, Verdickungsmittel, anfeuchtende und/oder feuchthaltende Substanzen, Füllstoffe, die das Hautgefühl verbessern, Fette, Öle, Wachse oder andere übliche Be- standteile einer kosmetischen oder dermatologischen Formulierung wie Alkohole, Poly- ole, Polymere, Schaumstabilisatoren, Elektrolyte, organische Lösungsmittel oder Silikonderivate.The cosmetic and dermatological preparations according to the invention can contain cosmetic auxiliaries as are usually used in such preparations. be applied, e.g. 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.
((
Vorteilhafte Konservierungsmittel im Sinne der vorliegenden Erfindung sind beispiels- weise Formaldehydabspalter (wie z. B. DMDM Hydantoin), lodopropylbutylcarbamate (z. B. die unter den Handelsbezeichnungen Koncyl-L, Koncyl-S und Konkaben LMB von der Fa. Lonza erhältlichen), Parabene, Phenoxyethanol, Ethanol, Benzoesäure und dergleichen mehr. Üblicherweise umfaßt das Konservierungssystem erfindungsgemäß ferner vorteilhaft auch Konservierungshelfer, wie beispielsweise Octoxyglycerin, Glycine Soja etc.Advantageous preservatives for the purposes of the present invention are, for example, formaldehyde releasers (such as, for example, DMDM hydantoin), iodopropylbutyl carbamates (for example those available from Lonza under the trade names Koncyl-L, Koncyl-S and Konkaben LMB), 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.
Besonders vorteilhafte Zubereitungen werden ferner erhalten, wenn als Zusatz- oder Wirkstoffe Antioxidantien eingesetzt werden. Erfindungsgemäß enthalten die Zubereitungen vorteilhaft eines oder mehrere Antioxidantien. Als günstige, aber dennoch fakultativ zu verwendende Antioxidantien können alle für kosmetische und/oder dermatologische Anwendungen geeigneten oder gebräuchlichen Antioxidantien verwendet werden.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.
Vorteilhaft werden die Antioxidantien gewählt aus der Gruppe bestehend aus Aminosäuren (z. B. Glycin, Histidin, Tyrosin, Tryptophan) und deren Derivate, Imidazole (z. B. Uro- caninsäure) und deren Derivate, Peptide wie D,L-Carnosin, D-Carnosin, L-Carnosin und deren Derivate (z. B. Anserin), Carotinoide, Carotine (z. B. α-Carotin, ß-Carotin, Lycopin) und deren Derivate, Liponsäure und deren Derivate (z. B. Dihydroliponsäure), Aurothio- glucose, Propylthiouracil und andere Thiole (z. B. Thioredoxin, Glutathion, Cystein, Cy- stin, Cystamin und deren Glycosyl-, N-Acetyl-, Methyl-, Ethyl-, Propyl-, Amyl-, Butyl- und Lauryl-, Palmitoyl-, Oleyl-, γ -Linoleyl-, Cholesteryl - und Glycerylester) sowie deren Salze, Dilaurylthiodipropionat, Distearylthiodipropionat, Thiodipropionsäure und deren Derivate (Ester, Ether, Peptide, Lipide, Nukleotide, Nukleoside und Salze) sowie Sulfoximin- verbindungen (z. B. Buthioninsulfoximine, Homocysteinsulfoximin, Buthioninsulfone, Pen- ta-, Hexa-, Heptathioninsulfoximin) in sehr geringen verträglichen Dosierungen (z. B. pmol bis μmol/kg), ferner (Metall)-Chelatoren (z. B. α-Hydroxyfettsäuren, Palmitinsäure, Phytinsäure, Lactoferrin), α-Hydroxysäuren (z. B. Zitronensäure, Milchsäure, Apfelsäure), Huminsäure, Gallensäure, Gallenextrakte, Bilirubin, Biliverdin, EDTA, EGTA und deren Derivate, ungesättigte Fettsäuren und deren Derivate (z. B. γ-Linolensäure, Linolsäure, Ölsäure), Folsäure und deren Derivate, Ubichinon und Ubichinol und deren Derivate, Vi- tamin C und Derivate (z. B. Ascorbylpalmitat, Mg - Ascorbylphosphat, Ascorbylacetat), Tocopherole und Derivate (z. B. Vitamin E - acetat), Vitamin A und Derivate (Vitamin A - palmitat) sowie Konyferylbenzoat des Benzoeharzes, Rutinsäure und deren Derivate, Fe- rulasäure und deren Derivate, Butylhydroxytoluol, Butylhydroxyanisol, Nordihydroguajak- harzsäure, Nordihydroguajaretsäure, Trihydroxybutyrophenon, Harnsäure und deren De- rivate, Mannose und deren Derivate, Zink und dessen Derivate (z. B. ZnO, ZnS04) Selen und dessen Derivate (z. B. Selenmethionin), Stilbene und deren. Derivate (z. B. Stilbenoxid, Trans-Stilbenoxid) und die erfindungsgemäß geeigneten Derivate (Salze, Ester, Ether, Zucker, Nukleotide, Nukleoside, Peptide und Lipide) dieser genannten Wirkstoffe.The antioxidants are advantageously selected from the group consisting of amino acids (e.g. glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles (e.g. urocanic acid) and their derivatives, peptides such as D, L-carnosine, D-carnosine, L-carnosine and their derivatives (e.g. anserine), carotenoids, carotenes (e.g. 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) as well as 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. buthionine sulfoximines, homocysteine sulfoximine, buthionine sulfones, penta-, hexa-, hept athioninsulfoximin) in very low tolerable dosages (e.g. B. 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), humic acid, bile acid, bile extracts, bilirubin, biliverdin, EDTA, EGTA and their derivatives, unsaturated fatty acids and their derivatives (e.g. γ-linolenic acid , Linoleic acid, oleic acid), folic acid and its derivatives, ubiquinone and ubiquinol and their derivatives, vitamin C and derivatives (e.g. ascorbyl palmitate, Mg - ascorbyl phosphate, ascorbylacetate), tocopherols and derivatives (e.g. vitamin E - acetate ), Vitamin A and derivatives (vitamin A - palmitate) as well as konyferyl benzoate of benzoin, rutinic acid and its derivatives, ferric acid and its derivatives, butylhydroxytoluene, butylhydroxyanisole, nordihydroguajak resin acid, nordihydroguajaretic acid, trihydroxybutyrophenon and urine derivatives, urine their derivatives, zinc and its derivatives (e.g. ZnO, ZnS04) selenium and its derivatives (e.g. selenium methionine), stilbene and their. Derivatives (e.g. stilbene oxide, trans-stilbene oxide) and the derivatives (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids) of these active substances which are suitable according to the invention.
Besonders vorteilhaft im Sinne der vorliegenden Erfindung können wasserlösliche Antioxidantien eingesetzt werden, wie beispielsweise Vitamine, z. B. Ascorbinsäure und deren Derivate.For the purposes of the present invention, water-soluble antioxidants, such as vitamins, e.g. B. ascorbic acid and its derivatives.
Eine erstaunliche Eigenschaft der erfindungsgemäßen Zubereitungen ist, daß diese sehr gute Vehikel für kosmetische oder dermatologische Wirkstoffe in die Haut sind, wobei bevorzugte Wirkstoffe Antioxidantien sind, welche die Haut vor oxidativer Beanspruchung schützen können. Bevorzugte Antioxidantien sind dabei Vitamin E und dessen Derivate sowie Vitamin A und dessen Derivate.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.
Die Menge der Antioxidantien (eine oder mehrere Verbindungen) in den Zubereitungen beträgt vorzugsweise 0,001 bis 30 Gew.-%, besonders bevorzugt 0,05 bis 20 Gew.-%, insbesondere 0,1 bis 10 Gew.-%, bezogen auf das Gesamtgewicht der Zubereitung.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.
Sofern Vitamin E und/oder dessen Derivate das oder die Antioxidantien darstellen, ist vorteilhaft, deren jeweilige Konzentrationen aus dem Bereich von 0,001 bis 10 Gew.-%, bezogen auf das Gesamtgewicht der Formulierung, zu wählen.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.
Sofern Vitamin A bzw. Vitamin-A-Derivate, bzw. Carotine bzw. deren Derivate das oder die Antioxidantien darstellen, ist vorteilhaft, deren jeweilige Konzentrationen aus dem Be- reich von 0,001 bis 10 Gew.-%, bezogen auf das Gesamtgewicht der Formulierung, zu wählen.If vitamin A or vitamin A derivatives or carotenes or their derivatives represent the antioxidant or antioxidants, it is advantageous to determine their respective concentrations from the range from 0.001 to 10 wt .-%, based on the total weight of the formulation to choose.
Erfindungsgemäß können die Wirkstoffe (eine oder mehrere Verbindungen) auch sehr vorteilhaft gewählt werden aus der Gruppe der lipophilen Wirkstoffe, insbesondere aus folgender Gruppe: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:
Acetylsalicylsäure, Atropin, Azulen, Hydrocortison und dessen Derivaten, z. B. Hydrocor- tison-17-valerat, Vitamine der B- und D-Reihe, sehr günstig das Vitamin Bi, das Vitamin Bι2 das Vitamin Di, aber auch Bisabolol, ungesättigte Fettsäuren, namentlich die essentiellen Fettsäuren (oft auch Vitamin F genannt), insbesondere die gamma-Linolensäure, Ölsäure, Eicosapentaensäure, Docosahexaensäure und deren Derivate, Chlorampheni- col, Coffein, Prostaglandine, Thymol, Campher, Extrakte oder andere Produkte pflanzlicher und tierischer Herkunft, z. B. Nachtkerzenöl, Borretschöl oder Johannisbeerkernöl, Fischöle, Lebertran aber auch Ceramide und ceramidähnliche Verbindungen und so weiter.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 Bi, the vitamin Bι 2, the vitamin Di, but also bisabolol, unsaturated fatty acids, especially the essential fatty acids (often called vitamin F) ), in particular gamma-linolenic acid, oleic acid, eicosapentaenoic acid, docosahexaenoic acid and its derivatives, chloramphenicol, caffeine, prostaglandins, thymol, camphor, extracts or other products of plant and animal origin, e.g. 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.
Vorteilhaft ist es auch, die Wirkstoffe aus der Gruppe der rückfettenden Substanzen zu wählen, beispielsweise Purcellinöl, Eucerit und Neocerit .It is also advantageous to select the active substances from the group of refatting substances, for example purcellin oil, Eucerit and Neocerit.
Besonders vorteilhaft werden der oder die Wirkstoffe ferner gewählt aus der Gruppe der NO-Synthasehemmer, insbesondere wenn die erfindungsgemäßen Zubereitungen zur Behandlung und Prophylaxe der Symptome der intrinsischen und/oder extrinsischen Hautalterung sowie zur Behandlung und Prophylaxe der schädlichen Auswirkungen ultra- violetter Strahlung auf die Haut dienen sollen.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 ultraviolet radiation on the skin should serve.
Bevorzugter NO-Synthasehemmer ist das Nitroarginin.The preferred NO synthase inhibitor is nitroarginine.
Weiter vorteilhaft werden der oder die Wirkstoffe gewählt aus der Gruppe, welche Gate- chine und Gallensäureester von Catechinen und wäßrige bzw. organische Extrakte aus Pflanzen oder Pflanzenteilen umfaßt, die einen Gehalt an Catechinen oder Gallensäure- estem von Catechinen aufweisen, wie beispielsweise den Blättern der Pflanzenfamilie Theaceae, insbesondere der Spezies Camellia sinensis (grüner Tee). Insbesondere vorteilhaft sind deren typische Inhaltsstoffe (wie z. B. Polyphenole bzw. Catechine, Coffein, Vitamine, Zucker, Mineralien, Aminosäuren, Lipide). Catechine stellen eine Gruppe von Verbindungen dar, die als hydrierte Flavone oder An- thocyanidine aufzufassen sind und Derivate des „Catechins" (Catechol, 3,3',4',5,7-Fla- vanpentaol, 2-(3,4-Dihydroxyphenyl)-chroman-3,5,7-triol) darstellen. Auch Epicatechin ((2R,3R)-3,3l,4',5J-Flavanpentaol) ist ein vorteilhafter Wirkstoff im Sinne der vorliegenden Erfindung.The active ingredient (s) are furthermore advantageously selected from the group comprising gate chines 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 understood 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) Also epicatechin ((2R, 3R) -3.3 l , 4 ', 5J-flavanpentaol) is an advantageous active substance in the sense of the present invention.
Vorteilhaft sind ferner pflanzliche Auszüge mit einem Gehalt an Catechinen, insbesondere Extrakte des grünen Tees, wie z. B. Extrakte aus Blättern der Pflanzen der Spezies Camellia spec, ganz besonders der Teesorten Camellia sinenis, C. assamica, C. talien- sis bzw. C. irrawadiensis und Kreuzungen aus diesen mit beispielsweise Camellia japo- nica.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.
Bevorzugte Wirkstoffe sind ferner Polyphenole bzw. Catechine aus der Gruppe (-)-Cate- chin, (+)-Catechin, (-)-Catechingallat, (-)-Gallocatechingallat, (+)-Epicatechin, (-)-Epicate- chin, (-)-Epicatechin Gallat, (-)-Epigallocatechin, (-)-Epigallocatechingallat.Preferred active ingredients are also polyphenols or catechins from the group (-) - catechol, (+) - catechin, (-) - catechin gallate, (-) - gallocatechin gallate, (+) - epicatechin, (-) - epicatechin , (-) - epicatechin gallate, (-) - epigallocatechin, (-) - epigallocatechin gallate.
Auch Flavon und seine Derivate (oft auch kollektiv „Flavone" genannt) sind vorteilhafte Wirkstoffe im Sinne der vorliegenden Erfindung. Sie sind durch folgende Grundstruktur gekennzeichnet (Substitutionspositionen angegeben):Flavon and its derivatives (often also collectively called "flavones") are also advantageous active substances in the sense of the present invention. They are characterized by the following basic structure (substitution positions indicated):
Figure imgf000011_0001
Figure imgf000011_0001
Einige der wichtigeren Flavone, welche auch bevorzugt in erfindungsgemäßen Zubereitungen eingesetzt werden können, sind in der nachstehenden Tabelle aufgeführt:Some of the more important flavones, which can also preferably be used in preparations according to the invention, are listed in the table below:
Figure imgf000011_0002
Figure imgf000011_0002
Figure imgf000012_0002
Figure imgf000012_0002
In der Natur kommen Flavone in der Regel in glycosidierter Form vor.In nature, flavones usually occur in glycosidated form.
Erfindungsgemäß werden die Flavonoide bevorzugt gewählt aus der Gruppe der Substanzen der generischen StrukturformelAccording to the invention, the flavonoids are preferably selected from the group of substances of the generic structural formula
Figure imgf000012_0001
wobei Zi bis Z7 unabhängig voneinander gewählt werden aus der Gruppe H, OH, Alkoxy- sowie Hydroxyalkoxy-, wobei die Alkoxy- bzw. Hydroxyalkoxygruppen verzweigt und unverzweigt sein und 1 bis 18 C-Atome aufweisen können, und wobei Gly gewählt wird aus der Gruppe der Mono- und Oligoglycosidreste.
Figure imgf000012_0001
where Zi to Z 7 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 of the mono- and oligoglycoside residues.
Erfindungsgemäß können die Flavonoide aber auch vorteilhaft gewählt werden aus der Gruppe der Substanzen der generischen Strukturformel According to the invention, the flavonoids can also be advantageously selected from the group of substances of the generic structural formula
Figure imgf000013_0001
wobei Zi bis Z6 unabhängig voneinander gewählt werden aus der Gruppe H, OH, Alkoxy- sowie Hydroxyalkoxy-, wobei die Alkoxy- bzw. Hydroxyalkoxygruppen verzweigt und unverzweigt sein und 1 bis 18 C-Atome aufweisen können, und wobei Gly gewählt wird aus der Gruppe der Mono- und Oligoglycosidreste.
Figure imgf000013_0001
where Zi 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 of the mono- and oligoglycoside residues.
Bevorzugt können solche Strukturen gewählt werden aus der Gruppe der Substanzen der generischen StrukturformelSuch structures can preferably be selected from the group of substances of the generic structural formula
Figure imgf000013_0002
wobei Glyi, Gly2 und Gly3 unabhängig voneinander Mönoglycosidreste oder darstellen. Gly2 bzw. Gly3 können auch einzeln oder gemeinsam Absättigungen durch Wasserstoffatome darstellen.
Figure imgf000013_0002
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.
Bevorzugt werden Glyi, Gly2 und Gly3 unabhängig voneinander gewählt aus der Gruppe der Hexosylreste, insbesondere der Rhamnosylreste und Glucosylreste. Aber auch andere Hexosylreste, beispielsweise Allosyl, Altrosyl, Galactosyl, Gulosyl, Idosyl, Mannosyl und Talosyl sind gegebenenfalls vorteilhaft zu verwenden. Es kann auch erfindungsgemäß vorteilhaft sein, Pentosylreste zu verwenden.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.
Vorteilhaft werden Zi bis Z5 unabhängig voneinander gewählt aus der Gruppe H, OH, Methoxy-, Ethoxy- sowie 2-Hydroxyethoxy-, und die Flavonglycoside haben die Struktur Zi 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
Figure imgf000014_0001
Figure imgf000014_0001
Besonders vorteilhaft werden die erfindungsgemäßen Flavonglycoside aus der Gruppe, welche durch die folgende Struktur wiedergegeben werden:The flavone glycosides according to the invention from the group which are represented by the following structure are particularly advantageous:
Figure imgf000014_0002
wobei Glyi, Gly2 und Gly3 unabhängig voneinander Monoglycosidreste oder darstellen. Gly2 bzw. Gly3 können auch einzeln oder gemeinsam Absättigungen durch Wasserstoffatome darstellen.
Figure imgf000014_0002
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.
Bevorzugt werden Gly^ Gly2 und Gly3 unabhängig voneinander gewählt aus der Gruppe der Hexosylreste, insbesondere der Rhamnosylreste und Glucosylreste. Aber auch andere Hexosylreste, beispielsweise Allosyl, Altrosyl, Galactosyl, Gulosyl, Idosyl, Mannosyl und Talosyl sind gegebenenfalls vorteilhaft zu verwenden. Es kann auch erfindungsgemäß vorteilhaft sein, Pentosylreste zu verwenden.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.
Besonders vorteilhaft im Sinne der vorliegenden Erfindung ist, das oder die Flavonglycoside zu wählen aus der Gruppe α-Glucosylrutin, α-Glucosylmyricetin, α-Glucosyliso- quercitrin, α-Glucosylisoquercetin und -Glucosylquercitrin.For the purposes of the present invention, it is particularly advantageous to select the flavone glycoside (s) from the group α-glucosyl rutin, α-glucosyl myrcetin, α-glucosyl iso-quercitrin, α-glucosyl iso-quercetin and glucosyl-quercitrin.
Erfindungsgemäß besonders bevorzugt ist α-Glucosylrutin. Erfindungsgemäß vorteilhaft sind auch Naringin (Aurantiin, Naringenin-7-rhamnogluco- sid), Hesperidin (3\5J-Trihydroxy-4'-methoxyflavanon-7-rutinosid, Hesperidosid, Hespe- retin-7-O-rutinosid). Rutin (3,3',4',5J-Pentahydroxyflyvon-3-rutinosid, Quercetin-3-rutino- sid, 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-glucopy- ranosid)), Monoxerutin (3,3',4',5-Tetrahydroxy-7-(2-hydroxyethoxy)-flavon-3-(6-O-(6-de- oxy-α-L-mannopyranosyl)-ß-D-glucopyranosid)), Dihydrorobinetin (3,3',4',5',7-Penta- hydroxyflavanon), Taxifolin (3,3',4',5,7-Pentahydroxyflavanon), Eriodictyol-7-glucosid (3',4',5J-Tetrahydroxyflavanon-7-glucosid), Flavanomareϊn (3',4'J,8-Tetrahydroxyflava- non-7-glucosid) und Isoquercetin (3,3',4',5J-Pentahydroxyflavanon-3-(ß-D-Glucopyrano- sid). .According to the invention, α-glucosylrutin is particularly preferred. Also advantageous according to the invention are naringin (aurantiin, naringenin-7-rhamnoglucosid), hesperidin (3 \ 5J-trihydroxy-4'-methoxyflavanon-7-rutinoside, hesperidoside, hesperetin-7-O-rutinoside). Rutin (3,3 ', 4', 5J-Pentahydroxyflyvon-3-rutinosid, Quercetin-3-rutinosid, 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 (3', 4 ', 5J-tetrahydroxyflavanone-7 -glucoside), flavanomareϊn (3 ', 4'J, 8-tetrahydroxyflava-non-7-glucoside) and isoquercetin (3,3', 4 ', 5J-pentahydroxyflavanon-3- (ß-D-glucopyrano-sid). ,
Vorteilhaft ist es auch, dem oder die Wirkstoffe aus der Gruppe der Ubichinone und Plastochinone zu wählen.It is also advantageous to choose the active ingredient (s) from the group of ubiquinones and plastoquinones.
Ubichinone zeichnen sich durch die StrukturformelUbiquinones are characterized by the structural formula
Figure imgf000015_0001
Figure imgf000015_0001
aus und stellen die am weitesten verbreiteten und damit am besten untersuchten Biochi- none dar. Ubichinone werden je nach Zahl der in der Seitenkette verknüpften Isopren- Einheiten als Q-1, Q-2, Q-3 usw. oder nach Anzahl der C-Atome als U-5, U-10, U-15 usw. bezeichnet. Sie treten bevorzugt mit bestimmten Kettenlängen auf, z. B. in einigen Mikroorganismen und Hefen mit n=6. Bei den meisten Säugetieren einschließlich des Menschen überwiegt Q10.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.
Besonders vorteilhaft ist Coenzym Q10, welches durch folgende Strukturformel gekennzeichnet ist:
Figure imgf000016_0001
Coenzyme Q10, which is characterized by the following structural formula, is particularly advantageous:
Figure imgf000016_0001
Plastochinone weisen die allgemeine StrukturformelPlastoquinones have the general structural formula
Figure imgf000016_0002
auf. Plastoschinone unterscheiden sich in der Anzahl n der Isopren-Reste und werden endsprechend bezeichnet, z. B. PQ-9 (n=9). Ferner existieren andere Plastochinone mit unterschiedlichen Substituenten am Chinon-Ring.
Figure imgf000016_0002
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.
Auch Kreatin und/oder Kreatinderivate sind bevorzugte Wirkstoffe im Sinne der vorliegenden Erfindung. Kreatin zeichnet sich durch folgende Struktur aus:Creatine and / or creatine derivatives are also preferred active substances for the purposes of the present invention. Creatine is characterized by the following structure:
Figure imgf000016_0003
Figure imgf000016_0003
Bevorzugte Derivate sind Kreatinphosphat sowie Kreatinsulfat, Kreatinacetat, Kreatin- ascorbat und die an der Carboxylgruppe mit mono- oder polyfunktionalen Alkoholen ver- esterten Derivate.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.
Ein weiterer vorteilhafter Wirkstoff ist L-Carnitin [3-Hydroxy-4-(trimethylammonio)-butter- säurebetain]. Auch Acyl-Carnitine, welche gewählt aus der Gruppe der Substanzen der folgenden allgemeinen Strukturformel C— R /Another advantageous active ingredient is L-carnitine [3-hydroxy-4- (trimethylammonio) -butter-acid-betaine]. Also acyl-carnitine, which is selected from the group of substances of the following general structural formula C— R /
OO
+ I+ I
(H3C)3N— CH2— C— CH2— COO-(H 3 C) 3 N - CH 2 - C - CH 2 - COO-
H wobei R gewählt wird aus der Gruppe der verzweigten und unverzweigten Alkylreste mit bis zu 10 Kohlenstoffatomen sind vorteilhafte Wirkstoffe im Sinne der vorliegenden Erfindung. Bevorzugt sind Propionylcamitin und insbesondere Acetylcarnitin. Beide Entantio- mere (D- und L-Form) sind vorteilhaft im Sinne der vorliegenden Erfindung zu verwenden. Es kann auch von Vorteil sein, beliebige Enantiomerengemische, beispielsweise ein Racemat aus D- und L-Form, zu verwenden.H where R is selected from the group of branched and unbranched alkyl radicals having up to 10 carbon atoms are advantageous active substances in the sense of the present invention. Propionylcamitine 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.
Weitere vorteilhafte Wirkstoffe sind Sericosid, Pyridoxol, Vitamin K, Biotin und Aroma- Stoffe.Other advantageous active ingredients are sericoside, pyridoxol, vitamin K, biotin and flavorings.
Die Liste der genannten Wirkstoffe bzw. Wirkstoffkombinationen, die in den erfindungsgemäßen Zubereitungen verwendet werden können, soll selbstverständlich nicht limitierend sein. Die Wirkstoffe können einzelnen oder in beliebigen Kombinationen miteinander verwendet werden.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.
Darüber hinaus eignen sich ausgewählte erfindungsgemäße Rezepturen, welche z. B. bekannte Antifaltenwirkstoffe wie Flavonglycoside (insbesondere α-GIycosyl rutin), Coen- zym Q10, Vitamin E und/oder Derivate und dergleichen enthalten, insbesondere vorteil- haft zur Prophylaxe und Behandlung kosmetischer oder dermatologischer Hautveränderungen, wie sie z. B. bei der Hautalterung auftreten. Weiterhin vorteilhaft eignen sie sich gegen das Erscheinungsbild der trockenen bzw. rauhen Haut.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-glycosyl rutin), 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 during skin aging. They are also advantageous against the appearance of dry or rough skin.
Hautalterung wird z. B. durch endogene, genetisch determinierte Faktoren verursacht. In Epidermis und Dermis kommt es alterungsbedingt z. B. zu folgenden Strukturschäden und Funktionsstörungen, die auch unter den Begriff „Senile Xerosis" fallen können: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) Trockenheit, Rauhigkeit und Ausbildung von (Trockenheits-) Fältchen, b) Juckreiz und c) verminderte Rückfettung durch Talgdrüsen (z. B. nach dem Waschen). Exogene Faktoren, wie UV-Licht und chemische Noxen, können kumulativ wirksam sein und z. B. die endogenen Alterungsprozesse beschleunigen bzw. sie ergänzen. In Epidermis und Dermis kommt es insbesondere durch exogene Faktoren z. B. zu folgenden Strukturschäden- und Funktionsstörungen in der Haut, die über Maß und Qualität der Schäden bei chronologischer Alterung hinausgehen: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) Sichtbare Gefäßerweiterungen (Teleangiektasien, Cuperosis); e) Schlaffheit und Ausbildung von Falten; f) lokale Hyper-, Hypo- und Fehlpigmentierungen (z. B. Altersflecken) und g) vergrößerte Anfälligkeit gegenüber mechanischem Stress (z. B. Rissigkeit).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 einer besonderen Ausführungsform betrifft die vorliegende Erfindung insbesondere Produkte zur Pflege der auf natürliche Weise gealterten Haut, sowie zur Behandlung der Folgeschäden der Lichtalterung, insbesondere der unter a) bis g) aufgeführten Phänomene.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).
Die Ölphase der erfindungsgemäßen Formulierungen wird vorteilhaft gewählt aus der Gruppe der polaren Öle, beispielsweise aus der Gruppe der Lecithine und der Fettsäure- triglyceride, namentlich der Triglycerinester gesättigter und/oder ungesättigter, verzweigter und/oder unverzweigter Alkancarbonsäuren einer Kettenlänge von 8 bis 24, insbesondere 12 bis 18 C-Atomen. Die Fettsäuretriglyceride können beispielsweise vorteilhaft gewählt werden aus der Gruppe der synthetischen, halbsynthetischen und natürlichen Öle, wie z. B. Cocoglycerid, Olivenöl, Sonnenblumenöl, Sojaöl, Erdnußöl, Rapsöl, Man- delöl, Palmöl, Kokosöl, Rizinusöl, Weizenkeimöl, Traubenkernöl, Distelöl, Nachtkerzenöl, Macadamianußöl und dergleichen mehr.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 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.
Weitere vorteilhafte polare Ölkomponenten können im Sinne der vorliegenden Erfindung ferner gewählt werden aus der Gruppe der Ester aus gesättigten und/oder ungesättigten, verzweigten und/oder unverzweigten Alkancarbonsäuren einer Kettenlänge von 3 bis 30 C-Atomen und gesättigten und/oder ungesättigten, verzweigten und/oder unverzweigten Alkoholen einer Kettenlänge von 3 bis 30 C-Atomen sowie aus der Gruppe der Ester aus aromatischen Carbonsäuren und gesättigten und/oder ungesättigten, verzweigten und/oder unverzweigten Alkoholen einer Kettenlänge von 3 bis 30 C-Atomen. Solche Esteröle können dann vorteilhaft gewählt werden aus der Gruppe Octylpalmitat, Octylco- coat, Octylisostearat, Octyldodeceylmyristat, Cetearylisononanoat, Isopropylmyristat, Iso- propylpalmitat, Isopropylstearat, Isopropyloleat, n-Butylstearat, n-Hexyllaurat, n-Decyl- oleat, Isooctylstearat, Isononylstearat, Isononylisononanoat, 2-EthyIhexylpalmitat, 2- Ethylhexyllaurat, 2-HexyldecyIstearat, 2-Octyldodecylpalmitat, Stearylheptanoat, Oleyl- oleat, Oleylerucat, Erucyloleat, Erucylerucat, Tridecylstearat, Tridecyltrimellitat, sowie synthetische, halbsynthetische und natürliche Gemische solcher Ester, wie z. B. Jojobaöl.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 laurate, n-decyl oleate, isooctyl stearate, isonononyl stylate ethyl isononylyl stomate 2-octyldodecyl palmitate, stearyl heptanoate, oleyl oleate, olerlerucate, erucyl oleate, erucylerucate, tridecyl stearate, tridecyl trimellitate, and synthetic, semisynthetic and natural mixtures of such esters, such as, for. B. Jojoba oil.
Ferner kann die Ölphase vorteilhaft gewählt werden aus der Gruppe der Dialkylether und Dialkylcarbonate, vorteilhaft sind z. B. Dicaprylylether (Cetiol OE) und/oder Dicaprylyl- carbonat, beispielsweise das unter der Handelsbezeichnung Cetiol CC bei der Fa. Cognis erhältliche.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.
Es ist ferner bevorzugt, das oder die Ölkomponenten aus der Gruppe Isoeikosan, Neo- pentylglykoldiheptanoat, Propylenglykoldicaprylat/dicaprat, Caprylic/Capric/Diglyceryl- succinat, Butylenglykol Caprylat/Caprat, C 23-Alkyllactat, Di-Cι23-Alkyltartrat, Triisostea- rin, Dipentaerythrityl Hexacaprylat/Hexacaprat, Propylenglykolmonoisostearat, Tricapry- lin, Dimethylisosorbid. Es ist insbesondere vorteilhaft, wenn die Ölphase der erfindungsgemäßen Formulierungen einen Gehalt an Cι2.15-Alkylbenzoat aufweist oder vollständig aus diesem besteht.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 caprylate / caprate, C 23 alkyl lactate, di-Cι 23 -Alkyl tartrate, triisostearin, dipentaerythrityl hexacaprylate / hexacaprate, propylene glycol monoisostearate, tricapryline, dimethyl isosorbide. It is particularly advantageous if the oil phase of the formulations according to the invention contains C 2 . 15 alkyl benzoate or consists entirely of this.
Auch beliebige Abmischungen solcher Öl- und Wachskomponenten sind vorteilhaft im Sinne der vorliegenden Erfindung einzusetzen.Any mixtures of such oil and wax components can also be used advantageously for the purposes of the present invention.
Ferner kann die Ölphase ebenfalls vorteilhaft auch unpolare Öle enthalten, beispiels- weise solche, welche gewählt werden aus der Gruppe der verzweigten und unverzweigten Kohlenwasserstoffe und -wachse, insbesondere Mineralöl, Vaseline (Petrolatum), Paraffinöl, Squalan und Squalen, Polyolefine, hydrogenierte Polyisobutene und Isohexa- decan. Unter den Polyolefinen sind Polydecene die bevorzugten Substanzen.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.
Vorteilhaft kann die Ölphase femer einen Gehalt an cyclischen oder linearen Silikonölen aufweisen oder vollständig aus solchen Ölen bestehen, wobei allerdings bevorzugt wird, außer dem Silikonöl oder den Silikonölen einen zusätzlichen Gehalt an anderen Ölpha- senkomponenten zu verwenden. Silikonöle sind hochmolekulare synthetische polymere Verbindungen, in denen Silicium- Atome über Sauerstoff-Atome ketten- und/oder netzartig verknüpft und die restlichen Valenzen des Siliciums durch Kohlenwasserstoff-Reste (meist Methyl-, seltener Ethyl-, Propyl-, Phenyl-Gruppen u. a.) abgesättigt sind. Systematisch werden die Silikonöle als Polyorganosiloxane bezeichnet. Die methylsubstituierten Polyorganosiloxane, welche die mengenmäßig bedeutendsten Verbindungen dieser Gruppe darstellen und sich durch die folgende Strukturformel auszeichnenThe 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 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
Figure imgf000020_0001
werden auch als Polydimethylsiloxan bzw. Dimethicon (INCI) bezeichnet. Dimethicone gibt es in verschiedenen Kettenlängen bzw. mit verschiedenen Molekulargewichten.
Figure imgf000020_0001
are also known as polydimethylsiloxane or dimethicone (INCI). Dimethicone is available in different chain lengths or with different molecular weights.
Besonders vorteilhafte Polyorganosiloxane im Sinne der vorliegenden Erfindung sind beispielsweise Dimethylpolysiloxane [Poly(dimethylsiloxan)], welche beispielsweise unter den Handelsbezeichnungen Abil 10 bis 10000 bei Th. Goldschmidt erhältlich sind. Fer- ner vorteilhaft sind Phenylmethylpolysiloxane (INCI: Phenyl Dimethicone, Phenyl Tri- methicone), cyclische Silikone (Octamethylcyclotetrasiloxan bzw. Decamethylcyciopenta- siloxan), welche nach INCI auch als Cyclomethicone bezeichnet werden, aminomodifi- zierte Silikone (INCI: Amodimethicone) und Silikonwachse, z. B. Polysiloxan-Polyalkylen- Copolymere (INCI: Stearyl Dimethicone und Cetyl Dimethicone) und Dialkoxydimethyl- polysiloxane (Stearoxy Dimethicone und Behenoxy Stearyl Dimethicone), welche als verschiedene Abil-Wax-Typen bei Th. Goldschmidt erhältlich sind. Aber auch andere Silikonöle sind vorteilhaft im Sinne der vorliegenden Erfindung zu verwenden, beispielsweise Cetyldimethicon, Hexamethylcyclotrisiloxan, Polydimethylsiloxan, Poly(methylphenyl- siloxan).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 decamethylcyciopentasiloxane), which according to INCI are also called cyclomethicones, amino-modified silicones (INCI: amodimethethicones, z. 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).
Erfindungsgemäß vorteilhaft sind ferner z. B. natürliche Wachse tierischen und pflanzlichen Ursprungs, wie beispielsweise Bienenwachs, Chinawachs, Hummelwachs und andere Insektenwachse sowie Sheabutter.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.
Ferner können die erfindungsgemäßen Zubereitungen vorteilhaft auch in Form von sogenannten ölfreien kosmetischen oder dermatologischen Emulsionen vorliegen, welche eine Wasserphase und mindestens eine bei Raumtemperatur flüssige UV-Filtersubstanz als weitere Phase enthalten. '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 liquid at room temperature as a further phase. '
Besonders vorteilhafte bei Raumtemperatur flüssige UV-Filtersubstanzen im Sinne der vorliegenden Erfindung sind Homomenthylsalicylat, 2-Ethylhexyl-2-cyano-3,3-diphenyl- acrylat, 2-Ethylhexyl-2-hydroxybenzoat und Ester der Zimtsäure, vorzugsweise 4-Meth- oxyzimtsäure(2-ethylhexyl)ester und 4-Methoxyzimtsäureisopentylester.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.
Homomenthylsalicylat (INCI: Homosalate) zeichnet sich durch die folgende Struktur aus:Homomenthyl salicylate (INCI: Homosalate) is characterized by the following structure:
Figure imgf000021_0001
Figure imgf000021_0001
2-Ethylhexyl-2-cyano-3,3-diphenylacrylat (INCI: Octocrylene) ist von BASF unter der Bezeichnung Uvinul® N 539 erhältlich und zeichnet sich durch folgende Struktur aus: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:
Figure imgf000021_0002
Figure imgf000021_0002
2-EthyIhexyl-2-hydroxybenzoat (2-Ethylhexylsalicylat, Octylsalicylat, INCI: Octyl Salicy- late) ist beispielsweise bei Haarmann & Reimer unter der Handelsbezeichnung Neo He- Iiopan OS erhältlich und zeichnet sich durch die folgende Struktur aus:2-Ethylhexyl-2-hydroxybenzoate (2-ethylhexyl salicylate, octyl salicylate, INCI: octyl salicylate) is available, for example, from Haarmann & Reimer under the trade name Neo He-Iiopan OS and is characterized by the following structure:
Figure imgf000021_0003
Figure imgf000021_0003
4-Methoxyzimtsäure(2-ethylhexyl)ester (2-EthyIhexyl-4-methoxycinnamat, INCI: Octyl Methoxycinnamate) ist beispielsweise bei Hoffmann-La Röche unter der Handelsbezeichnung Parsol MCX erhältlich und zeichnet sich durch die folgende Struktur aus:
Figure imgf000022_0001
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:
Figure imgf000022_0001
4-MethoxyzimtsäureisopentyIester (lsopentyl-4-methoxycinnamat, INCI: Isoamyl p-Meth- oxycinnamate) ist beispielsweise bei Haarmann & Reimer unter der Handelsbezeichnung Neo Heliopan E 1000 erhältlich und zeichnet sich durch die folgende Struktur aus:4-methoxycinnamic acid isopentyl ester (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:
Figure imgf000022_0002
Figure imgf000022_0002
Die Gesamtmenge an einer oder mehreren bei Raumtemperatur flüssigen UV-Filtersubstanzen in den fertigen kosmetischen oder dermatologischen Zubereitungen wird vorteilhaft aus dem Bereich 0,1 Gew.-% bis 30 Gew.-%, vorzugsweise von 0,5 bis 20 Gew.-% gewählt, jeweils bezogen auf das Gesamtgewicht der Zubereitungen.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.
Solche ölfreien Emulsionen können im Sinne der vorliegenden Erfindung ferner vorteilhaft, wenngleich nicht zwingend, auch Silikonöle und/oder Silikonwachse enthalten, insbesondere die obengenannten.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.
Die Wasserphase der erfindungsgemäßen Zubereitungen kann vorteilhaft übliche kosmetische Hilfsstoffe enthalten, wie beispielsweise Alkohole, insbesondere solche niedriger C-Zahl, vorzugsweise Ethanol und/oder Isopropanol, Diole oder Polyole niedriger C- Zahl sowie deren Ether, vorzugsweise Propylenglykol, Glycerin, Ethylenglykol, Ethylen- glykolmonoethyl- oder -monobutylether, Propylenglykolmonomethyl, -monoethyl- oder - monobutylether, Diethylenglykolmonomethyl- oder -monoethylether und analoge Produkte, Polymere, Schaumstabilisatoren, Elektrolyte sowie insbesondere ein oder mehrere Verdickungsmittel, welches oder welche vorteilhaft gewählt werden können aus der Gruppe Siliciumdioxid, Aluminiumsilikate, Polysaccharide bzw. deren Derivate, z. B. Hy- aluronsäure, Xanthangummi, Hydroxypropylmethylcellulose, besonders vorteilhaft aus der Gruppe der Polyacrylate, bevorzugt ein Polyacrylat aus der Gruppe der sogenannten Carbopole, beispielsweise Carbopole der Typen 980, 981, 1382, 2984, 5984, jeweils einzeln oder in Kombination. Auch Moisturizer können bevorzugt verwendet werden. Als Moisturizer werden Stoffe oder Stoffgemische bezeichnet, welche kosmetischen oder dermatologischen Zubereitungen die Eigenschaft verleihen, nach dem Auftragen bzw. Verteilen auf der Hautoberfläche die Feuchtigkeitsabgabe der Homschicht (auch trans- epidermal water Joss (TEWL) genannt) zu reduzieren und/oder die Hydratation der Horn- schicht positiv zu beeinflussen.The water phase of the preparations according to the invention can advantageously contain customary cosmetic auxiliaries, such as, for example, alcohols, in particular those having a low C number, preferably ethanol and / or isopropanol, diols or polyols having 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 consisting of silicon dioxide and 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 reducing the release of moisture from the skin layer (also called trans-epidermal water joss (TEWL)) and / or hydrating the skin after application or distribution on the skin surface To influence the horny layer positively.
Vorteilhafte Moisturizer im Sinne der voriiegenden Erfindung sind beispielsweise Glyce- rin, Milchsäure, Pyrrolidoncarbonsäure und Harnstoff. Ferner ist es insbesondere von Vorteil, polymere Moisturizer aus der Gruppe der wasserlöslichen und/oder in Wasser quellbaren und/oder mit Hilfe von Wasser gelierbaren Polysaccharide zu verwenden. Insbesondere vorteilhaft sind beispielsweise Hyaluronsäure, Chitosan und/oder ein fuco- sereiches Polysaccharid, welches in den Chemical Abstracts unter der Registraturnummer 178463-23-5 abgelegt und z. B. unter der Bezeichnung Fucogel®1000 von der Gesellschaft SOLABIA S.A. erhältlich ist.Advantageous moisturizers in the sense 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 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.
Die erfindungsgemäßen kosmetischen oder dermatologischen Zubereitungen können ferner vorteilhaft, wenngleich nicht zwingend, Füllstoffe enthalten, welche z. B. die sensorischen und kosmetischen Eigenschaften der Formulierungen weiter verbessern und beispielsweise ein samtiges oder seidiges Hautgefühl hervorrufen oder verstärken. Vorteil- hafte Füllstoffe im Sinne der vorliegenden Erfindung sind Stärke und Stärkederivate (wie z. B. Tapiocastärke, Distärkephosphat, Aluminium- bzw. Natrium-Stärke Octenylsuccinat und dergleichen), Pigmente, die weder hauptsächlich UV-Filter- noch färbende Wirkung haben (wie z. B. Bornitrid etc.) und/oder Aerosile® (CAS-Nr. 7631-86-9).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).
Aerosile®, die bei der DEGUSSA AG/Frankfurt erhältlich sind, sind Siliciumoxide und zeichnen sich durch eine geringe Partikelgröße (z.B. zwischen 5 und 40 nm) aus, wobei die Partikel als kugelförmige Teilchen sehr einheitlicher Abmessung anzusehen sind. Makroskopisch sind Aerosile® als lockere, weiße Pulver erkenntlich. Vorteilhafte Aerosil®- Typen sind beispielsweise Aerosil® OX50, Aerosil® 130, Aerosil® 150, Aerosil® 200, Aero- sil® 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.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.
Entsprechend ihrem Aufbau können kosmetische oder topische dermatologische Zusammensetzungen im Sinne der vorliegenden Erfindung, beispielsweise verwendet werden als Hautschutzcreme, Reinigungsmilch, Tages- oder Nachtcreme usw. Es ist gegebenen- falls möglich und vorteilhaft, die erfindungsgemäßen Zusammensetzungen als Grundlage für pharmazeutische Formulierungen zu verwenden.Depending on their structure, cosmetic or topical dermatological compositions in the sense of the present invention can be used, for example, as a skin protection cream, cleansing milk, day or night cream, etc. if possible and advantageous, to use the compositions according to the invention as the basis for pharmaceutical formulations.
Die erfindungsgemäßen kosmetischen und dermatologischen Zubereitungen können Farbstoffe und/oder Farbpigmente enthalten, insbesondere wenn sie in Form von dekorativen Kosmetika vorliegen. Die Farbstoffe und -pigmente können aus der entsprechenden Positivliste der Kosmetikverordnung bzw. der EG-Liste kosmetischer Färbemittel ausgewählt werden. In den meisten Fällen sind sie mit den für Lebensmittel zugelassenen Farbstoffen identisch. Vorteilhafte Farbpigmente sind beispielsweise Titandioxid, Glimmer, Eisenoxide (z. B. Fe2O3, Fe3O4, FeO(OH)) und/oder Zinnoxid. Vorteilhafte Farbstoffe sind beispielsweise Carmin, Berliner Blau, Chromoxidgrün, Ultramarinblau und/oder Manganviolett. Es ist insbesondere vorteilhaft, die Farbstoffe und/oder Farbpigmente aus der folgenden Liste zu wählen. Die Colour Index Nummern (CIN) sind dem Rowe Colour Index, 3. Auflage, Society ofDyers and Colourists, Bradford, England, 1971 entnommen.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 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 list below. The Color Index Numbers (CIN) are taken from the Rowe Color Index, 3rd edition, Society ofDyers and Colorists, Bradford, England, 1971.
Chemische oder sonstige Bezeichnung CIN FarbeChemical or other name CIN color
Pigment Green 10006 grünPigment Green 10006 green
Acid Green 1 10020 grünAcid Green 1 10020 green
2,4-Dinitrohydroxynaphthalin-7-sulfosäure 10316 gelb2,4-dinitrohydroxynaphthalene-7-sulfonic acid 10316 yellow
Pigment Yellow 1 11680 gelbPigment Yellow 1 11680 yellow
Pigment Yellow 3 11710 gelbPigment Yellow 3 11710 yellow
Pigment Orange 1 1725 orangePigment Orange 1 1725 orange
2,4-Dihydroxyazobenzol 11920 orange2,4-dihydroxyazobenzene 11920 orange
Solvent Red 3 12010 rotSolvent Red 3 12010 red
1-(2'-Chlor-4'-nitro-1'-phenylazo)-2-hydroxynaphthalin 12085 rot1- (2'-chloro-4'-nitro-1'-phenylazo) -2-hydroxynaphthalene 12085 red
Pigment Red 3 12120 rotPigment Red 3 12120 red
Ceresrot; Sudanrot; Fettrot G 12150 rotCeresrot; Sudan Red; Fat red G 12150 red
Pigment Red 112 12370 rotPigment Red 112 12370 red
Pigment Red 7 12420 rotPigment Red 7 12420 red
Pigment Brown 1 12480 braunPigment Brown 1 12480 brown
4-(2'-Methoxy-5'-sulfosäurediethylamid-1'-phenylazo)-3-hydroxy-5"- 12490 rot chloro-2",4"-dimethoxy-2-naphthoesäureanilid4- (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 gelb Chemische oder sonstige Bezeichnung CIN FarbeDisperse Yellow 16 12700 yellow Chemical or other name CIN color
1-(4-Sulfo-1-phenylazo)-4-amino-benzol-5-sulfosäure 13015 gelb1- (4-Sulfo-1-phenylazo) -4-amino-benzene-5-sulfonic acid 13015 yellow
2,4-Dihydroxy-azobenzol-4'-sulfosäure 14270 orange2,4-Dihydroxy-azobenzene-4'-sulfonic acid 14270 orange
2-(2,4-Dimethylphenylazo-5-sulfosäure)-1-hydroxynaphthalin-4-sul- 14700 rot fosäure2- (2,4-Dimethylphenylazo-5-sulfonic acid) -1-hydroxynaphthalene-4-sulfo-14700 red foic acid
2-(4-Sulfo-1-naphthylazo)-1-naphthol-4-sulfosäure 14720 rot2- (4-sulfo-1-naphthylazo) -1-naphthol-4-sulfonic acid 14720 red
2-(6-Sulfo-2,4-xylylazo)-1-naphthol-5-sulfosäure 14815 rot2- (6-sulfo-2,4-xylylazo) -1-naphthol-5-sulfonic acid 14815 red
1-(4'-Sulfophenylazo)-2-hydroxynaphthalin 15510 orange1- (4'-Sulfophenylazo) -2-hydroxynaphthalene 15510 orange
1-(2-Sulfosäure-4-chlor-5-carbonsäure-1-phenylazo)-2-hydroxy- 15525 rot naphthalin1- (2-sulfonic acid-4-chloro-5-carboxylic acid-1-phenylazo) -2-hydroxy- 15525 red naphthalene
1-(3-Methyl-phenylazo-4-sulfρsäure)-2-hydroxynaphthalin 15580 rot1- (3-methyl-phenylazo-4-sulphuric acid) -2-hydroxynaphthalene 15580 red
1-(4',(8')-Sulfosäurenaphthylazo)-2-hydroxynaphthalin 15620 rot1- (4 ', (8') - sulfonic acid naphthylazo) -2-hydroxynaphthalene 15620 red
2-Hydroxy-1,2'-azonaphthalin-1'-sulfosäure 15630 rot2-hydroxy-1,2'-azonaphthalene-1'-sulfonic acid 15630 red
3-Hydroxy-4-phenylazo-2-naphthylcarbonsäure 15800 rot3-hydroxy-4-phenylazo-2-naphthylcarboxylic acid 15800 red
1-(2-Sulfo-4-methyl-1-phenylazo)-2-naphthylcarbonsäure 15850 rot1- (2-sulfo-4-methyl-1-phenylazo) -2-naphthylcarboxylic acid 15850 red
1-(2-Sulfo-4-methyl-5-chlor-1-phenylazo)-2-hydroxy-naphthalin-3- 15865 rot carbonsäure1- (2-sulfo-4-methyl-5-chloro-1-phenylazo) -2-hydroxy-naphthalene-3- 15865 red carboxylic acid
1-(2-Sulfo-1-naphthylazo)-2-hydroxynaphthalin-3-carbonsäure 15880 rot1- (2-sulfo-1-naphthylazo) -2-hydroxynaphthalene-3-carboxylic acid 15880 red
1-(3-Sulfo-1-phenylazo)-2-naphthol-6-sulfosäure 15980 orange1- (3-Sulfo-1-phenylazo) -2-naphthol-6-sulfonic acid 15980 orange
1-(4-Sulfo-1-phenylazo)-2-naphthol-6-sulfosäure 15985 gelb1- (4-Sulfo-1-phenylazo) -2-naphthol-6-sulfonic acid 15985 yellow
Allura Red 16035 rotAllura Red 16035 red
1-(4-Sulfo-1-naphthylazo)-2-naphthol-3,6-disulfosäure 16185 rot1- (4-Sulfo-1-naphthylazo) -2-naphthol-3,6-disulfonic acid 16185 red
Acid Orange 10 16230 orangeAcid Orange 10 16230 orange
1-(4-SuIfo-1-naphthylazo)-2-naphthol-6,8-disulfosäure 16255 rot1- (4-SuIfo-1-naphthylazo) -2-naphthol-6,8-disulfonic acid 16255 red
1-(4-Sulfo-1-naphthylazo)-2-naphthol-3,6,8-trisulfosäure 16290 rot1- (4-Sulfo-1-naphthylazo) -2-naphthol-3,6,8-trisulfonic acid 16290 red
8-Amino-2 -phenylazo- 1 -naphthol-3,6-disulfosäure 17200 rot8-amino-2-phenylazo-1-naphthol-3,6-disulfonic acid 17200 red
Acid Red 1 18050 rotAcid Red 1 18050 red
Acid Red 155 18130 rotAcid Red 155 18 130 red
Acid Yellow 121 18690 gelbAcid Yellow 121 18690 yellow
Acid Red 180 18736 rotAcid Red 180 18736 red
Acid Yellow 11 18820 gelbAcid Yellow 11 18820 yellow
Acid Yellow 17 18965 gelbAcid Yellow 17 18965 yellow
4-(4-Sulfo-1-phenylazo)-1-(4-sulfophenyl)-5-hydroxy-pyrazolon-3- 19140 gelb carbonsäure Chemische oder sonstige Bezeichnung CIN Farbe4- (4-Sulfo-1-phenylazo) -1- (4-sulfophenyl) -5-hydroxy-pyrazolon-3- 19140 yellow carboxylic acid Chemical or other name CIN color
Pigment Yellow 16 20040 gelbPigment Yellow 16 20040 yellow
2,6-(4'-Sulfo-2", 4"-dimethyI)-bis-phenylazo)1,3-dihydroxybenzol 20170 orange2,6- (4'-Sulfo-2 ", 4" -dimethyI) -bis-phenylazo) 1,3-dihydroxybenzene 20170 orange
Acid Black 1 20470 schwarzAcid Black 1 20470 black
Pigment Yellow 13 21100 gelbPigment Yellow 13 21 100 yellow
Pigment Yellow 83 21108 gelbPigment Yellow 83 21108 yellow
Solvent Yellow 21230 gelbSolvent Yellow 21230 yellow
Acid Red 163 24790 rotAcid Red 163 24790 red
Acid Red 73 27290 rotAcid Red 73 27 290 red
2-[4'-(4"-Sulfo-1"-phenylazo)-7,-sulfo-1'-naphthylazo]-1-hydroxy-7- 27755 schwarz aminonaphthalin-3,6-disulfosäure2- [4 '- (4 "-Sulfo-1" -phenylazo) -7 , -sulfo-1'-naphthylazo] -1-hydroxy-7- 27755 black aminonaphthalene-3,6-disulfonic acid
4'-[(4"-Sulfo-1"-phenyIazo)-7'-sulfo-1'-naphthylazo]-1-hydroxy-8- 28440 schwarz acetyl-aminonaphthalin-3,5-disulfosäure4 '- [(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 orangeDirect Orange 34, 39, 44, 46, 60 40215 orange
Food Yellow 40800 orange trans-ß-Apo-8'-Carotinaldehyd (C30) 40820 orange trans-Apo-8'-Carotinsäure (C30)-ethylester 40825 orangeFood Yellow 40800 orange trans-ß-apo-8'-carotenaldehyde (C 30 ) 40820 orange trans-apo-8'-carotenic acid (C 30 ) ethyl ester 40825 orange
Canthaxanthin 40850 orangeCanthaxanthin 40850 orange
Acid Blue 1 42045 blauAcid Blue 1 42045 blue
2,4-Disulfo-5-hydroxy-4'-4"-bis-(diethylamino)triphenyl-carbinol 42051 blau2,4-disulfo-5-hydroxy-4'-4 "-bis- (diethylamino) triphenyl-carbinol 42051 blue
4-[(-4-N-Ethyl-p-sulfobenzylamino)-phenyl-(4-hydroxy-2-sulfophe- 42053 grün nyl)-(methylen)-1-(N-ethylN-p-sulfobenzyl)-2,5-cyclohexadienimin]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 blauAcid Blue 7 42080 blue
(N-Ethyl-p-sulfobenzyl-amino)-phenyl-(2-sulfophenyl)-methylen-(N- 42090 blau ethyl-N-p-su!fo-benzyI)Δ2,5-cyclohexadienimin(N-ethyl-p-sulfobenzyl-amino) -phenyl- (2-sulfophenyl) -methylene- (N- 42090 blue ethyl-Np-su! Fo-benzyI) Δ 2.5 -cyclohexadienimine
Acid Green 9 42100 grünAcid Green 9 42 100 green
Diethyl-di-sulfobenzyl-di-4-amino-2-chIor-di-2-methyl-fuchsonim- 42170 grün moniumDiethyl-di-sulfobenzyl-di-4-amino-2-chloro-di-2-methyl-fuchsonim-42170 green monium
Basic Violet 14 42510 violettBasic Violet 14 42510 violet
Basic Violet 2 42520 violettBasic Violet 2 42520 violet
2'-Methyl-4'-(N-ethyl-N-m-sulfobenzyl)-amino-4"-(N-diethyl)-amino- 42735 blau2'-Methyl-4 '- (N-ethyl-N-m-sulfobenzyl) amino-4 "- (N-diethyl) amino- 42735 blue
2-methyl-N-ethylN-m-suIfobenzyl-fuchsonimmonium2-methyl-N-ethylN-m-suIfobenzyl-fuchsonimmonium
4'-(N-Dimethyl)-amino-4"-(N-phenyl)-aminonaphtho-N-dimethyl- 44045 blau fuchsonimmonium Chemische oder sonstige Bezeichnung CIN Farbe4 '- (N-Dimethyl) -amino-4 "- (N-phenyl) -aminonaphtho-N-dimethyl-44045 blue foxsonimmonium Chemical or other name CIN color
2-Hydroxy-3,6-disulfo-4,4'-bis-dimethylaminonaphthofuchsonimmo- 44090 grün nium2-Hydroxy-3,6-disulfo-4,4'-bis-dimethylaminonaphthofuchsonimmo 44090 green nium
Acid Red 52 45100 rotAcid Red 52 45 100 red
3-(2'-Methylphenylamino)-6-(2'-methyl-4'-suIfophenylamino)-9-(2"- 45190 violett carboxyphenyl)-xantheniumsalz3- (2'-Methylphenylamino) -6- (2'-methyl-4'-suIfophenylamino) -9- (2 "- 45190 violet carboxyphenyl) xanthenium salt
Acid Red 50 45220 rotAcid Red 50 45 220 red
Phenyl-2-oxyfluoron-2-carbonsäure 45350 gelbPhenyl-2-oxyfluoron-2-carboxylic acid 45350 yellow
4,5-Dibromfluorescein 45370 orange4,5-dibromofluorescein 45370 orange
2,4,5,7-Tetrabromfluorescein 45380 rot2,4,5,7-tetrabromofluorescein 45380 red
Solvent Dye 45396 orangeSolvent Dye 45396 orange
Acid Red 98 45405 rotAcid Red 98 45405 red
3',4',5',6'-Tetrachlor-2,4,5J-tetrabromfluorescein 45410 rot3 ', 4', 5 ', 6'-tetrachloro-2,4,5J-tetrabromofluorescein 45410 red
4,5-Diiodfluorescein 45425 rot4,5-diiodofluorescein 45425 red
2,4,5,7-Tetraiodfluorescein 45430 rot2,4,5,7-tetraiodofluorescein 45430 red
Chinophthalon 47000 gelbQuinophthalone 47000 yellow
Chinophthalon-disulfosäure 47005 gelbQuinophthalone disulfonic acid 47005 yellow
Acid Violet 50 50325 violettAcid Violet 50 50325 violet
Acid Black 2 50420 schwarzAcid Black 2 50420 black
Pigment Violet 23 51319 violettPigment Violet 23 51319 violet
1 ,2-Dioxyanthrachinon, Calcium-Aluminiumkomplex 58000 rot1, 2-dioxyanthraquinone, calcium-aluminum complex 58000 red
3-Oxypyren-5, 8, 10-sulfosäure 59040 grün3-oxypyrene-5, 8, 10-sulfonic acid 59040 green
1-Hydroxy-4-N-phenyl-aminoanthrachinon 60724 violett1-Hydroxy-4-N-phenylaminoanthraquinone 60724 violet
1-Hydroxy-4-(4'-methylphenylamino)-anthrachinon 60725 violett1-Hydroxy-4- (4'-methylphenylamino) anthraquinone 60725 purple
Acid Violet 23 60730 violettAcid Violet 23 60730 violet
1,4-Di(4'-methyl-phenylamino)-anthrachinon 61565 grün1,4-Di (4'-methylphenylamino) anthraquinone 61565 green
1,4-Bis-(o-sulfo-p-toluidino)-anthrachinon 61570 grün1,4-bis (o-sulfo-p-toluidino) anthraquinone 61570 green
Acid Blue 80 61585 blauAcid Blue 80 61585 blue
Acid Blue 62 62045 blauAcid Blue 62 62045 blue
N,N'-Dihydro-1,2,1',2'-anthrachinonazin 69800 blauN, N'-dihydro-1,2,1 ', 2'-anthraquinonazine 69800 blue
Vat Blue 6; Pigment Blue 64 69825 blauVat Blue 6; Pigment Blue 64 69825 blue
Vat Orange 7 71105 orangeVat Orange 7 71105 orange
Indigo 73000 blauIndigo 73000 blue
Indigo-disulfosäure 73015 blau Chemische oder sonstige Bezeichnung CIN FarbeIndigo-disulfonic acid 73015 blue Chemical or other name CIN color
4,4'-Dimethyl-6,6'-dichlorthioindigo 73360 rot4,4'-dimethyl-6,6'-dichlorothioindigo 73360 red
5,5'-Dichlor-7J'-dimethylthioindigo 73385 violett5,5'-dichloro-7J'-dimethylthioindigo 73385 purple
Quinacridone Violet 19 73900 violettQuinacridone Violet 19 73900 violet
Pigment Red 122 73915 rotPigment Red 122 73915 red
Pigment Blue 16 74100 blauPigment Blue 16 74 100 blue
Phthalocyanine 74160 blauPhthalocyanine 74160 blue
Direct Blue 86 74180 blauDirect Blue 86 74 180 blue
Chlorierte Phthalocyanine 74260 grünChlorinated phthalocyanine 74260 green
Natural Yellow 6,19; Natural Red 1 75100 gelbNatural Yellow 6.19; Natural Red 1 75 100 yellow
Bixin, Nor-Bixin 75120 orangeBixin, Nor-Bixin 75120 orange
Lycopin 75125 gelb trans-alpha-, beta- bzw. gamma-Carotin 75130 orangeLycopene 75125 yellow trans-alpha, beta or gamma carotene 75130 orange
Keto- und/oder Hydroxylderivate des Carotins 75135 gelbKeto and / or hydroxyl derivatives of carotene 75135 yellow
Guanin oder Perlglanzmittel 75170 weißGuanine or pearlescent 75170 white
1 J-Bis-(4-hydroxy-3-methoxyphenyI)1 ,6-heptadien-3,5-dion 75300 gelb1 J-bis- (4-hydroxy-3-methoxyphenyl) 1,6-heptadiene-3,5-dione 75300 yellow
Komplexsalz (Na, AI, Ca) der Karminsäure 75470 rotComplex salt (Na, Al, Ca) of carminic acid 75470 red
Chlorophyll a und b; Kupferverbindungen der Chlorophylle und 75810 grün ,Chlorophyll a and b; Copper compounds of chlorophylls and 75810 green,
Chlorophyllinechlorophyllins
Aluminium 77000 weißAluminum 77000 white
Tonerdehydrat 77002 weißAlumina hydrate 77002 white
Wasserhaltige Aluminiumsilikate 77004 weißWater-containing aluminum silicate 77004 white
Ultramarin 77007 blauUltramarine 77007 blue
Pigment Red 101 und 102 77015 rotPigment Red 101 and 102 77015 red
Bariumsulfat 77120 weißBarium sulfate 77120 white
Bismutoxychlorid und seine Gemische mit Glimmer 77163 weißBismuth oxychloride and its mixtures with mica 77163 white
Calciumcarbonat 77220 weißCalcium carbonate 77220 white
Calciumsulfat 77231 weißCalcium sulfate 77231 white
Kohlenstoff 77266 schwarzCarbon 77266 black
Pigment Black 9 77267 schwarzPigment Black 9 77267 black
Carbo medicinalis vegetabilis 77268:1 schwarzCarbo medicinalis vegetabilis 77268: 1 black
Chromoxid 77288 grünChromium oxide 77288 green
Chromoxid, wasserhaltig 77289 grünChromium oxide, containing 77289 green
Pigment Blue 28, Pigment Green 14 77346 grün Chemische oder sonstige Bezeichnung CIN FarbePigment Blue 28, Pigment Green 14 77346 green Chemical or other name CIN color
Pigment Metal 2 77400 braunPigment Metal 2 77400 brown
Gold 77480 braunGold 77480 brown
Eisenoxide und -hydoxide 77489 orangeIron oxides and hydroxides 77489 orange
Eisenoxid 77491 rotIron oxide 77491 red
Eisenoxidhydrat 77492 gelbIron oxide hydrate 77492 yellow
Eisenoxid 77499 schwarzIron oxide 77499 black
Mischungen aus Eisen(ll)- und Eisen (lll)-hexacyanoferrat 77510 blauMixtures of iron (II) and iron (III) hexacyanoferrate 77510 blue
Pigment White 18 77713 weißPigment White 18 77713 white
Mangananimoniumdiphosphat 77742 violettManganese ammonium diphosphate 77742 violet
Manganphosphat; Mn3(PO4)2 7 H20 77745 rotManganese phosphate; Mn 3 (PO 4 ) 2 7 H20 77745 red
Silber 77820 weißSilver 77820 white
Titandioxid und seine Gemische mit Glimmer 77891 weißTitanium dioxide and its mixtures with mica 77891 white
Zinkoxid 77947 weißZinc oxide 77947 white
6J-Dimethyl-9-(1 '-D-ribityl)-isoalloxazin, Lactoflavin gelb6J-dimethyl-9- (1 '-D-ribityl) isoalloxazine, lactoflavin yellow
Zucke rkulör braunSugar brown
Capsanthin, Capsorubin orangeCapsanthin, Capsorubin orange
Betanin rotBetanine red
Benzopyryliumsalze, Anthocyane rotBenzopyrylium salts, anthocyanins red
Aluminium-, Zink-, Magnesium- und Calciumstearat weißAluminum, zinc, magnesium and calcium stearate white
Bromthymolblau blauBromothymol blue blue
Bromkresolgrün grünBromocresol green green
Acid Red 195 rotAcid Red 195 red
Sofern die erfindungsgemäßen Formulierungen in Form von Produkten vorliegen, welche im Gesicht angewendet werden, ist es günstig, als Farbstoff eine oder mehrere Substanzen aus der folgenden Gruppe zu wählen: 2,4-Dihydroxyazobenzol, 1-(2'-Chlor-4'-nitro-T- phenylazo)-2-hydroxynaphthalin, Ceresrot, 2-(4-Sulfo-1-naphthylazo)-1-naphthol-4-sulfo- säure, Caiciumsalz der 2-Hydroxy-1 ,2'-azonaphthalin- -sulfosäure, Calcium- und Bariumsalze der 1-(2-Sulfo-4-methyl-1-phenylazo)-2-naphthylcarbonsäure, Caiciumsalz der 1-(2-Sulfo-1-naphthylazo)-2-hydroxynaphthalin-3-carbonsäure, Aluminiumsalz der 1-(4- Sulfo-1-phenylazo)-2-naphthol-6-sulfosäure, Aluminiumsalz der 1-(4-Sulfo-1-naphthyl- azo)-2-naphthol-3,6-disulfosäure, 1-(4-Sulfo-1-naphthylazo)-2-naphthol-6,8-disulfosäure, Aluminiumsalz der 4-(4-Sulfo-1-phenyIazo)-1-(4-sulfophenyl)-5-hydroxy-pyrazolon-3-car- bonsäure, Aluminium- und Zirkoniumsalze von 4,5-Dibromfluorescein, Aluminium- und Zirkoniumsalze von 2,4,5,7-Tetrabromfluorescein, S'^'.δ'.θ'-Tetrachlor^^.δJ- tetrabromfluorescein und sein Aluminiumsalz, Aluminiumsalz von 2,4,5,7-Tetraiodfluores- cein, Aluminiumsalz der Chinophthalon-disulfosäure, Aluminiumsalz der Indigo-disulfo- säure, rotes und schwarzes Eisenoxid (CIN: 77 491 (rot) und 77 499 (schwarz)), Eisen- oxidhydrat (CIN: 77 492), Manganammoniumdiphosphat und Titandioxid.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-T-phenylazo) -2-hydroxynaphthalene, ceres red, 2- (4-sulfo-1-naphthylazo) -1-naphthol-4-sulfonic acid, calcium salt of 2-hydroxy-1, 2'-azonaphthalenesulfonic 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- (4th -Sulfo-1-naphthylazo) -2-naphthol-6,8-disulfonic acid, aluminum salt of 4- (4-sulfo-1-phenyIazo) -1- (4-sulfophenyl) -5-hydroxy-pyrazolon-3-car- bonic acid, aluminum and zirconium salts of 4,5-dibromofluorescein, aluminum and Zirconium salts of 2,4,5,7-tetrabromofluorescein, S '^'. Δ'.θ'-tetrachlor ^^. ΔJ- tetrabromofluorescein and its aluminum salt, aluminum salt of 2,4,5,7-tetraiodofluoresceine, 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.
Ferner vorteilhaft sind öllösliche Naturfarbstoffe, wie z. B. Paprikaextrakte, ß-Carotin oder Cochenille.Also advantageous are oil-soluble natural dyes, such as. B. paprika extracts, ß-carotene or cochineal.
Vorteilhaft im Sinne der vorliegenden Erfindung sind ferner Formulierungen mit einem Gehalt an Perlglanzpigmenten. Bevorzugt sind insbesondere die im folgenden aufgelisteten Arten von Perlglanzpigmenten: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. Natürliche Perlglanzpigmente, wie z. B.1. Natural pearlescent pigments, such as. B.
« „Fischsilber" (Guanin/Hypoxanthin-Mischkristalle aus Fischschuppen) und „Perlmutt" (vermahlene Muschelschalen) " " Fish silver "(guanine / hypoxanthine mixed crystals from fish scales) and " mother-of-pearl "(ground mussel shells)
2. Monokristalline Perlglanzpigmente wie z. B. Bismuthoxychlorid (BiOCI)2. Monocrystalline pearlescent pigments such as B. Bismuth oxychloride (BiOCI)
3. Schicht-Substrat Pigmente: z. B. Glimmer / Metalloxid3. Layer-substrate pigments: e.g. B. mica / metal oxide
Basis für Perlglanzpigmente sind beispielsweise pulverförmige Pigmente oder Ricinusöl- dispersionen von Bismutoxychlorid und/oder Titandioxid sowie Bismutoxychlorid und/oder Titandioxid auf Glimmer. Insbesondere vorteilhaft ist z. B. das unter der CIN 77163 aufgelistete Glanzpigment.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. Z is particularly advantageous. B. the gloss pigment listed under CIN 77163.
Vorteilhaft sind ferner beispielsweise die folgenden Perlglanzpigmentarten auf Basis von Glimmer/Metalloxid:The following pearlescent pigment types based on mica / metal oxide are also advantageous:
Figure imgf000030_0001
Figure imgf000031_0001
Figure imgf000030_0001
Figure imgf000031_0001
Besonders bevorzugt sind z.B. die von der Firma Merck unter den Handelsnamen Timi- ron, Colorona oder Dichrona erhältlichen Perlglanzpigmente.For example, particular preference is given to the pearlescent pigments available from Merck under the trade names Timiron, Colorona or Dichrona.
Die Liste der genannten Perlglanzpigmente soll selbstverständlich nicht limitierend sein. Im Sinne der vorliegenden Erfindung vorteilhafte Perlglanzpigmente sind auf zahlreichen, an sich bekannten Wegen erhältlich. Beispielsweise lassen sich auch andere Substrate außer Glimmer mit weiteren Metalloxiden beschichten, wie z. B. Silica und dergleichen mehr. Vorteilhaft sind z. B. mit TiO2 und Fe2O3 beschichtete SiO2-Partikel („Ronaspheren"), die von der Firma Merck vertrieben werden und sich besonders für die optische Reduktion feiner Fältchen eignen.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.
Es kann darüber hinaus von Vorteil sein, gänzlich auf ein Substrat wie Glimmer zu verzichten. Besonders bevorzugt sind Eisenperlglanzpigmente, welche ohne die Verwendung von Glimmer hergestellt werden. Solche Pigmente sind z. B. unter dem Handelsnamen Sicopearl Kupfer 1000 bei der Firma BASF erhältlich.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 copper 1000 from BASF.
Besonders vorteilhaft sind ferner auch Effektpigmente, welche unter der Handelsbezeichnung Metasomes Standard / Glitter in verschiedenen Farben (yello, red, green, blue) von der Firma Flora Tech erhältlich sind. Die Glitterpartikel liegen hierbei in Gemischen mit verschiedenen Hilfs- und Farbstoffen (wie beispielsweise den Farbstoffen mit den Colour Index (Cl) Nummern 19140, 77007, 77289, 77491) vor.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).
Die Farbstoffe und Pigmente können sowohl einzeln als auch im Gemisch vorliegen so- wie gegenseitig miteinander beschichtet sein, wobei durch unterschiedliche Beschich- tungsdicken im allgemeinen verschiedene Farbeffekte hervorgerufen werden. Die Gesamtmenge der Farbstoffe und farbgebenden Pigmente wird vorteilhaft aus dem Bereich von z. B. 0,1 Gew.-% bis 30 Gew.-%, vorzugsweise von 0,5 bis 15 Gew.-%, insbesondere von 1,0 bis 10 Gew.-% gewählt, jeweils bezogen auf das Gesamtgewicht der Zube- reitungen. Es ist auch vorteilhaft im Sinne der vorliegenden Erfindung, kosmetische und dermatologische Zubereitungen zu erstellen, deren hauptsächlicher Zweck nicht der Schutz vor Sonnenlicht ist, die aber dennoch einen Gehalt an UV-Schutzsubstanzen enthalten. So werden z. B. in Tagescremes oder Makeup-Produkten gewöhnlich UV-A- bzw. UV-B-Fil- tersubstanzen eingearbeitet. Auch stellen UV-Schutzsubstanzen, ebenso wie Antioxidantien und, gewünschtenfalls, Konservierungsstoffe, einen wirksamen Schutz der Zubereitungen selbst gegen Verderb dar. Günstig sind ferner kosmetische und dermatologische Zubereitungen, die in der Form eines Sonnenschutzmittels vorliegen.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% by weight to 30% by weight, preferably from 0.5 to 15% by weight, in particular from 1.0 to 10% by weight, in each case 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.
Dementsprechend enthalten die Zubereitungen im Sinne der vorliegenden Erfindung vorzugsweise neben einer oder mehreren erfindungsgemäßen UV-Filtersubstanzen zusätzlich mindestens eine weitere UV-A- und/oder UV-B-Filtersubstanz. Die Formulierungen können, obgleich nicht notwendig, gegebenenfalls auch ein oder mehrere organische und/oder anorganische Pigmente als UV-Filtersubstanzen enthalten, welche in der Wasser- und/oder der Ölphase vorliegen können.Accordingly, in the sense of the present invention, the preparations preferably contain, in addition to one or more UV filter substances according to the invention, at least one further UV-A and / or UV-B filter substance. The formulations may, 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 the oil phase.
Bevorzugte anorganische Pigmente sind Metalloxide und/oder andere in Wasser schwerlösliche oder unlösliche Metallverbindungen, insbesondere Oxide des Titans (TiO2), Zinks (ZnO), Eisens (z. B. Fe2O3), Zirkoniums (ZrO2), Siliciums (SiO2), Mangans (z. B. MnO), Aluminiums (AI2O3), Cers (z. B. Ce2O3), Mischoxide der entsprechenden Metalle sowie Abmischungen aus solchen Oxiden.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 and mixtures of such oxides.
Solche Pigmente können im Sinne der vorliegenden Erfindung vorteilhaft oberflächlich behandelt („gecoatet") sein, wobei beispielsweise ein amphiphiler oder hydrophober Charakter gebildet werden bzw. erhalten bleiben soll. Diese Oberflächenbehandlung kann darin bestehen, daß die Pigmente nach an sich bekannten Verfahren mit einer dünnen hydrophoben Schicht versehen werden.For the purposes of the present invention, such pigments can advantageously be surface-treated (“coated”), with an amphiphilic or hydrophobic character, for example, being formed or maintained be provided with a hydrophobic layer.
Erfindungsgemäß vorteilhaft sind z. B. Titandioxidpigmente, die mit Octylsilanol beschichtet sind. Geeignete Titandioxidpartikel sind unter der Handelsbezeichnung T805 bei der Firma Degussa erhältlich. Besonders vorteilhaft sind femer mit Aluminiumstearat beschichtete TiO2-Pigmente, z. B. die unter der Handelsbezeichnung MT 100 T bei der Firma TAYCA erhältlichen. Eine weitere vorteilhafte Beschichtung der anorganische Pigmente besteht aus Dimethyl- polysiloxan (auch: Dimethicon), einem Gemisch vollmethylierter, linearer Siloxanpoly- mere, die endständig mit Trimethylsiloxy-Einheiten blockiert sind. Besonders vorteilhaft im Sinne der vorliegenden Erfindung sind Zinkoxid-Pigmente, die auf diese Weise be- schichtet werden.According to the invention, z. B. titanium dioxide pigments coated with octylsilanol. Suitable titanium dioxide particles are available under the trade name T805 from Degussa. Also particularly advantageous are TiO 2 pigments coated with aluminum stearate, e.g. B. those available under the trade name MT 100 T from TAYCA. Another advantageous coating of the inorganic pigments consists of dimethylpolysiloxane (also: dimethicone), a mixture of fully methylated, linear siloxane polymers which are blocked at the end with trimethylsiloxy units. Zinc oxide pigments which are coated in this way are particularly advantageous for the purposes of the present invention.
Vorteilhaft ist ferner eine Beschichtung der anorganischen Pigmente mit einem Gemisch aus Dimethylpolysiloxan, insbesondere Dimethylpolysiloxan mit einer durchschnittlichen Kettenlänge von 200 bis 350 Dimethylsiloxan-Einheiten, und Silicagel, welches auch als Simethicone bezeichnet wird. Es ist insbesondere von Vorteil, wenn die anorganischen Pigmente zusätzlich mit Aluminiumhydroxid bzw. Aluminiumoxidhydrat (auch: Alumina, CAS-Nr.: 1333-84-2) beschichtet sind. Besonders vorteilhaft sind Titandioxide, die mit Simethicone und Alumina beschichtet sind, wobei die Beschichtung auch Wasser enthalten kann. Ein Beispiel hierfür ist das unter dem Handelsnamen Eusolex T2000 bei der Firma Merck erhältliche Titandioxid.It is also advantageous to coat the inorganic pigments with a mixture of dimethylpolysiloxane, in particular dimethylpolysiloxane with an average chain length of 200 to 350 dimethylsiloxane units, and silica gel, which is also referred to as simethicone. It is particularly advantageous if the inorganic pigments are additionally coated with aluminum hydroxide or aluminum oxide hydrate (also: alumina, CAS no .: 1333-84-2). Titanium dioxides coated with simethicone and alumina are particularly advantageous, the coating also being able to contain water. An example of this is the titanium dioxide available from Merck under the trade name Eusolex T2000.
Vorteilhaft enthalten erfindungsgemäße Zubereitungen Substanzen, die UV-Strahlung im UV-A- und/oder UV-B-Bereich absorbieren, wobei die Gesamtmenge der Filtersubstanzen z. B. 0,1 Gew.-% bis 30 Gew.-%, vorzugsweise 0,5 bis 20 Gew.-%, insbesondere 1,0 bis 15,0 Gew.-% beträgt, bezogen auf das Gesamtgewicht der Zubereitungen, um kosmetische Zubereitungen zur Verfügung zu stellen, die das Haar bzw. die Haut vor dem gesamten Bereich der ultravioletten Strahlung schützen. Sie können auch als Sonnenschutzmittel fürs Haar oder die Haut dienen.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 cosmetic To provide 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.
Vorteilhafte weitere UV-A-Filtersubstanzen im Sinne der vorliegenden Erfindung sind Di- benzoylmethanderivate, insbesondere das 4-(tert.-Butyl)-4'-methoxydibenzoylmethan (CAS-Nr. 70356-09-1), welches von Givaudan unter der Marke Parsol® 1789 und von Merck unter der Handelsbezeichnung Eusolex® 9020 verkauft wird.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.
Weitere vorteilhafte UV-A-Filtersubstanzen sind die Phenylen-1,4-bis-(2-benzimidazyl)- 3,3'-5,5'-tetrasulfonsäure
Figure imgf000034_0001
und ihre Salze, besonders die entsprechenden Natrium-, Kalium- oder Triethanolam- monium-Salze, insbesondere das Phenylen-1 ,4-bis-(2-benzimidazyl)-3,3'-5,5'-tetrasul- fonsäure-bis-natriumsalz
Further advantageous UV-A filter substances are phenylene-1,4-bis (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid
Figure imgf000034_0001
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
Figure imgf000034_0002
mit der INCI-Bezeichnung Bisimidazylate, welches beispielsweise unter der Handelsbezeichnung Neo Heliopan AP bei Haarmann & Reimer erhältlich ist.
Figure imgf000034_0002
with the INCI name bisimidazylate, which is available, for example, from Haarmann & Reimer under the trade name Neo Heliopan AP.
Ferner vorteilhaft sind das 1 ,4-di(2-oxo-10-Sulfo-3-bomylidenmethyl)-Benzol und dessen Salze (besonders die entsprechenden 10-Sulfato-verbindungen, insbesondere das entsprechende Natrium-, Kalium- oder Triethanolammonium-Salz), das auch als Benzol-1,4- di(2-oxo-3-bornylidenmethyl-10-sulfonsäure) bezeichnet wird und sich durch die folgende Struktur auszeichnet: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-bornylidenemethyl-10-sulfonic acid) and is characterized by the following structure:
Figure imgf000034_0003
Figure imgf000034_0003
Vorteilhafte UV-Filtersubstanzen im Sinne der vorliegenden Erfindung sind ferner sogenannte Breitbandfilter, d.h. Filtersubstanzen, die sowohl UV-A- als auch UV-B-Strahlung absorbieren.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.
Vorteilhafte Breitbandfilter oder UV-B-Filtersubstanzen sind beispielsweise Bis-Resorci- nyltriazinderivate mit der folgenden Struktur: Advantageous broadband filters or UV-B filter substances are, for example, bis-resorcinyltriazine derivatives with the following structure:
Figure imgf000035_0001
Figure imgf000035_0001
wobei R1, R2 und R3 unabhängig voneinander gewählt werden aus der Gruppe der verzweigten und unverzweigten Alkylgruppen mit 1 bis 10 Kohlenstoffatomen bzw. ein einzelnes Wasserstoffatom darstellen. Insbesondere bevorzugt sind das 2,4-Bis-{[4-(2-Ethyl- hexyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazin (INCI: Aniso Triazin), welches unter der Handelsbezeichnung Tinosorb® S bei der CIBA-Chemikalien GmbH erhältlich ist.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-Chemicals GmbH.
Besonders vorteilhafte Zubereitungen im Sinne der vorliegenden Erfindung, die sich durch einen hohen bzw. sehr hohen UV-A-Schutz auszeichnen, enthalten neben der oder den erfindungsgemäßen Filtersubstanz(en) bevorzugt ferner weitere UV-A- und/oder Breitbandfilter, insbesondere Dibenzoylmethanderivate [beispielsweise das 4-(tert.~Butyl)- 4'-methoxydibenzoylmethan], Phenylen-1,4-bis-(2-benzimidazyl)-3,3'-5,5'-tetrasulfon- säure und/oder ihre Salze, das 1,4-di(2-oxo-10-Sulfo-3-bornylidenmethyl)-Benzol und/oder dessen Salze und/oder das 2,4-Bis-{[4-(2-Ethyl-hexyloxy)-2-hydroxy]-phenyl}-6- (4-methoxyphenyl)-1,3,5-triazin, jeweils einzeln oder in beliebigen Kombinationen miteinander.Particularly advantageous preparations in the sense 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 4- (tert. ~ butyl) - 4'-methoxydibenzoylmethane], phenylene-1,4-bis (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid and / or their salts, 1,4-di (2-oxo-10-sulfo-3-bornylidenemethyl) benzene and / or its salts and / or 2,4-bis - {[4- (2-ethylhexyloxy) -2- hydroxy] -phenyl} -6- (4-methoxyphenyl) -1,3,5-triazine, each individually or in any combination with one another.
Auch andere UV-Filtersubstanzen, welche das Strukturmotiv Also other UV filter substances, which the structural motif
Figure imgf000036_0001
aufweisen, sind vorteilhafte UV-Filtersubstanzen im Sinne der vorliegenden Erfindung, beispielsweise die in der Europäischen Offenlegungsschrift EP 570 838 A1 beschriebenen s-Triazinderivate, deren chemische Struktur durch die generische Formel
Figure imgf000036_0001
are advantageous UV filter substances for the purposes of the present invention, for example the s-triazine derivatives described in European patent application EP 570 838 A1, the chemical structure of which is given by the generic formula
Figure imgf000036_0002
wiedergegeben wird, wobei
Figure imgf000036_0002
is reproduced, whereby
R einen verzweigten oder unverzweigten Cr8-Alkylrest, einen C5-Cι2-Cycloalkyl- rest, gegebenenfalls substituiert mit einer oder mehreren C C - Alkylgruppen, darstellt,R represents a branched or unbranched C r -C 8 alkyl radical, a C 5 -C 2 cycloalkyl radical, optionally substituted with one or more CC alkyl groups,
X ein Sauerstoffatom oder eine NH-Gruppe darstellt,X represents an oxygen atom or an NH group,
Ri einen verzweigten oder unverzweigten CrC 8-Alkylrest, einen Cε-Cι2-Cycloalkyl- rest, gegebenenfalls substituiert mit einer oder mehreren C C - Alkylgruppen, oder ein Wasserstoffatom, ein Alkalimetallatom, eine Ammoniumgruppe oder eine Gruppe der FormelRi is a branched or unbranched CrC 8 alkyl radical, a C ε -Cι 2 cycloalkyl radical, optionally substituted with one or more CC alkyl groups, or a hydrogen atom, an alkali metal atom, an ammonium group or a group of the formula
Figure imgf000036_0003
bedeutet, in welcher
Figure imgf000036_0003
means in which
A einen verzweigten oder unverzweigten Cι-C18-Alkylrest, einen C5-Cι2-Cyclo- alkyl- oder Arylrest darstellt, gegebenenfalls substituiert mit einer oder mehreren d-C - Alkylgruppen, R3 ein Wasserstoff atom oder eine Methylgruppe darstellt, n eine Zahl von 1 bis 10 darstellt, R2 einen verzweigten oder unverzweigten Cι-C18-Alkylrest, einen C3-Cι2-Cycloalkyl- rest, gegebenenfalls substituiert mit einer oder mehreren CrC - Alkylgruppen, darstellt, wenn X die NH-Gruppe darstellt, und einen verzweigten oder unverzweigten CrC18-Alkylrest, einen C5-Cι2-Cycloalkyl- rest, gegebenenfalls substituiert mit einer oder mehreren d-C - Alkylgruppen, oder ein Wasserstoffatom, ein Alkalimetallatom, eine Ammoniumgruppe oder eine Gruppe der FormelA 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 dC - alkyl groups, R 3 represents a hydrogen atom or a methyl group, n is a number from 1 to 10, R 2 represents a branched or unbranched C 1 -C 18 -alkyl radical, a C 3 -C 2 -cycloalkyl radical, optionally substituted by one or more CrC - alkyl groups, if X represents the NH group, and a branched or unbranched CrC 18 alkyl radical, a C 5 -C 2 cycloalkyl radical, optionally substituted with one or more dC alkyl groups, or a hydrogen atom, an alkali metal atom, an ammonium group or a group of the formula
Figure imgf000037_0001
bedeutet, in welcher
Figure imgf000037_0001
means in which
A einen verzweigten oder unverzweigten CrCis-Alkylrest, einen C5-Cι2-CycloaI- kyl- oder Arylrest darstellt, gegebenenfalls substituiert mit einer oder mehreren d-C4- Alkylgruppen, R3 ein Wasserstoffatom oder eine Methylgruppe darstellt, n eine Zahl von 1 bis 10 darstellt, wenn X ein Sauerstoffatom darstellt.A represents a branched or unbranched CrCis alkyl radical, a C 5 -C 2 cycloalkyl or aryl radical, optionally substituted by one or more dC 4 alkyl groups, R 3 represents a hydrogen atom or a methyl group, n is a number from 1 to 10 represents when X represents an oxygen atom.
Besonders bevorzugte UV-Filtersubstanz im Sinne der vorliegenden Erfindung ist ferner ein unsymmetrisch substituiertes s-Triazin, dessen chemische Struktur durch die Formel 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
Figure imgf000038_0001
wiedergegeben wird, welches im Folgenden auch als Dioctylbutylamidotriazon (INCI: Dioctylbutamidotriazone) bezeichnet wird und unter der Handelsbezeichnung UVASORB HEB bei Sigma 3V erhältlich ist.
Figure imgf000038_0001
is reproduced, which is also referred to below as dioctylbutylamidotriazon (INCI: dioctylbutamidotriazone) and is available under the trade name UVASORB HEB from Sigma 3V.
Vorteilhaft im Sinne der vorliegenden Erfindung ist auch ein symmetrisch substituiertes s- Triazin, das 4,4',4"-(1,3,5-Triazin-2,4,6-triyltriiminσ)-tris-benzoesäure-tris(2-ethylhexyl- ester), synonym: 2,4,6-Tris-[anilino-(p-carbo-2'-ethyl-T-hexyloxy)]-1,3,5-triazin (INCI: Octyl Triazone), welches von der BASF Aktiengesellschaft unter der Warenbezeichnung UVINUL® T 150 vertrieben wird.A symmetrically substituted s-triazine which is 4,4 ', 4 "- (1,3,5-triazine-2,4,6-triyltriiminσ) -tris-benzoic acid tris (2- ethylhexyl ester), synonymous: 2,4,6-tris [anilino- (p-carbo-2'-ethyl-T-hexyloxy)] - 1,3,5-triazine (INCI: octyl triazone), which is from from BASF Aktiengesellschaft under the trade name UVINUL® T 150.
Auch in der Europäischen Offenlegungsschrift 775698 werden bevorzugt einzusetzende Bis-Resorciπyltriazinderivate beschrieben, deren chemische Struktur durch die generi- sehe FormelThe European patent application 775698 also describes bis-resorcyltriazine derivatives which are preferably to be used, the chemical structure of which is shown by the generic formula
Figure imgf000038_0002
wiedergegeben wird, wobei R^ , R2 und Ai verschiedenste organische Reste repräsentieren.
Figure imgf000038_0002
is reproduced, wherein R ^, R 2 and Ai represent a wide variety of organic radicals.
Vorteilhaft im Sinne der vorliegenden Erfindung sind ferner das 2,4-Bis-{[4-(3-sulfonato)- 2-hydroxy-propyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1 ,3,5-triazin Natriumsalz, das 2,4-Bis-{[4-(3-(2-Propyloxy)-2-hydroxy-propyloxy)-2-hydroxy]-phenyl}-6-(4-methoxy- phenyl)-1 ,3,5-triazin, das 2,4-Bis-{[4-(2-ethyl-hexyloxy)-2-hydroxy]-phenyl}-6-[4-(2-meth- oxyethyl-carboxyl)-phenylamino]-1 ,3,5-triazin, das 2,4-Bis-{[4-(3-(2-propyloxy)-2-hydroxy- propyloxy)-2-hydroxy]-phenyl}-6-[4-(2-ethyl-carboxyl)-phenylamino]-1 ,3,5-triazin, das 2,4- Bis-{[4-(2-ethyl-hexyloxy)-2-hydroxy]-phenyl}-6-(1-methyl-pyrrol-2-yI)-1 ,3,5-triazin, das 2,4-Bis-{[4-tris(trimethylsiloxy-silylpropyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)- 1 ,3,5-triazin, das 2,4-Bis-{[4-(2"-methylpropenyloxy)-2-hydroxy]-phenyl}-6-(4-methoxy- phenyl)-1 ,3,5-triazin und das 2,4-Bis-{[4-(1\1\1\3\5\5\5'-Heptamethylsiloxy-2"-methyl- propyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazin.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-ethylcarboxyl) phenylamino] -1, 3,5-triazine, the 2,4-bis - {[4- (2-ethylhexyloxy) -2-hydroxy] phenyl} -6 - (1-methyl-pyrrol-2-yI) -1, 3,5-triazine, the 2,4-bis - {[4-tris (trimethylsiloxysilylpropyloxy) -2-hydroxy] phenyl} -6- ( 4-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 \ 1 \ 1 \ 3 \ 5 \ 5 \ 5'-heptamethylsiloxy-2 "-methyl-propyloxy) -2-hydroxy] phenyl } -6- (4-methoxyphenyl) -1,3,5-triazine.
Die UV-B- und/oder Breitband-Filter können öllöslich oder wasserlöslich sein. Vorteilhafte öllösliche UV-B- und/oder Breitband-Filtersubstanzen sind z. B.: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-Benzylidencampher-Derivate, vorzugsweise 3-(4-Methylbeπzyliden)campher, 3- Benzylidencampher; 4-Aminobenzoesäure-Derivate, vorzugsweise 4-(Dimethylamino)-benzoesäure(2- ethylhexyl)ester, 4-(Dimethylamino)benzoesäureamylester; » 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-triazin; 2,4,6-trianilino- (p-carbo-2'-ethyl-1 '-hexyloxy) -1, 3,5-triazine;
Ester der Benzalmalonsäure, vorzugsweise 4-Methoxybenzalmalonsäuredi(2-ethylhe- xyl)ester; Ester der Zimtsäure, vorzugsweise 4-Methoxyzimtsäure(2-ethylhexyI)ester, 4-Meth- oxyzimtsäureisopentylester; 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;
Derivate des Benzophenons, vorzugsweise 2-Hydroxy-4-methoxybenzophenon, 2- Hydroxy-4-methoxy-4'-methylbenzophenon, 2,2'-Dihydroxy-4-methoxybenzophenon Derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone
sowie an Polymere gebundene UV-Filter. as well as UV filters bound to polymers.
Vorteilhafte wasserlösliche UV-B- und/oder Breitband-Filtersubstanzen sind z. B.: Salze der 2-Phenylbenzimidazol-5-sulfonsäure, wie ihr Natrium-, Kalium- oder ihr Tri- ethanolammonium-Salz, sowie die Sulfonsäure selbst; ■ Sulfonsäure-Derivate des 3-Benzylidencamphers, wie z. B. 4-(2-Oxo-3-bornylidenme~ thyl)benzolsulfonsäure, 2-Methyl-5-(2-oxo-3-bomylidenmethyl)sulfonsäure und deren Salze.Advantageous water-soluble UV-B and / or broadband filter substances are e.g. For example: 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-bornylidenme ~ thyl) benzenesulfonic acid, 2-methyl-5- (2-oxo-3-bomylidenemethyl) sulfonic acid and their salts.
Eine weitere erfindungsgemäß vorteilhaft zu verwendende Lichtschutzfiltersubstanz ist das Ethylhexyl-2-cyano-3,3-diphenylacrylat (Octocrylen), welches von BASF unter der Bezeichnung Uvinul® N 539 erhältlich ist und sich durch folgende Struktur auszeichnet:Another light protection filter substance which can 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:
Figure imgf000040_0001
Figure imgf000040_0001
Es kann auch von erheblichem Vorteil sein, polymergebundene oder polymere UV-Filtersubstanzen in Zubereitungen gemäß der vorliegenden Erfindung zu verwenden, insbesondere solche, wie sie in der WO-A-92/20690 beschrieben werden.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.
Ferner kann es gegebenenfalls von Vorteil sein, erfindungsgemäß weitere UV-A- Und/oder UV-B-Filter in kosmetische oder dermatologische Zubereitungen einzuarbeiten, beispielsweise bestimmte Salicylsäurederivate wie 4-lsopropylbenzylsalicyiat, 2-Ethyl- hexylsalicylat (= Octylsalicylat), Homomenthylsalicylat.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-isopropylbenzylsalicyate, 2-ethylhexylsalicylate (= octylsalicylate), homomenthylsalicylate.
Die Liste der genannten UV-Filter, die im Sinne der vorliegenden Erfindung eingesetzt werden können, soll selbstverständlich nicht limitierend sein.The list of the UV filters mentioned, which can be used in the sense of the present invention, should of course not be limiting.
Vorteilhaft enthalten die erfindungsgemäßen Zubereitungen die Substanzen, die UV- Strahlung im UV-A- und/oder UV-B-Bereich absorbieren, in einer Gesamtmenge von z. B. 0,1 Gew.-% bis 30 Gew.-%, vorzugsweise 0,5 bis 20 Gew.-%, insbesondere 1,0 bis 15,0 Gew.-%, jeweils bezogen auf das Gesamtgewicht der Zubereitungen, um kosmetische Zubereitungen zur Verfügung zu stellen, die das Haar bzw. die Haut vor dem gesamten Bereich der ultravioletten Strahlung schützen. Sie können auch als Sonnenschutzmittel fürs Haar oder die Haut dienen. Ferner kann es gegebenenfalls von Vorteil sein, Filmbildner in die erfindungsgemäßen kosmetischen oder dermatologischen Zubereitungen einzuarbeiten, beispielsweise um die Wasserfestigkeit der Zubereitungen zu verbessern oder die UV-Schutzleistung zu erhöhen (UV-A- und/oder UV-B-Boosting). Geeignet sind sowohl wasserlösliche bzw. dispergierbare als auch fettlösliche Filmbildner, jeweils einzeln oder in Kombination miteinander.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 cosmetic To provide 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. 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.
Vorteilhafte wasserlöslich bzw. dispergierbare Filmbildner sind z. B. Polyurethane (z. B. die Avalure® -Typen von Goodrich), Dimethicone Copolyol Polyacrylate (Silsoft Surface® von der Witco Organo Silicones Group), PVP/VA (VA = Vinylacetat) Copolymer (Luviscol VA 64 Powder der BASF) etc.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 ,
Vorteilhafte fettlösliche Filmbildner sind z. B., die Filmbildner aus der Gruppe der Polymere auf Basis von Polyvinylpyrrolidon (PVP)Advantageous fat-soluble film formers are e.g. B., the film formers from the group of polymers based on polyvinylpyrrolidone (PVP)
Figure imgf000041_0001
Figure imgf000041_0001
Besonders bevorzugt sind Copolymere des Polyvinylpyrrolidons, beispielsweise das PVP Hexadecen Copolymer und das PVP Eicosen Copolymer, welche unter den Handelsbezeichnungen Antaron V216 und Antaron V220 bei der GAF Chemicals Cooperation erhältlich sind, sowie das Tricontayl PVP und dergleichen mehr.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.
Die nachfolgenden Beispiele sollen die vorliegende Erfindung verdeutlichen, ohne sie einzuschränken. Die Zahlenwerte in den Beispielen bedeuten Gewichtsprozente, bezogen auf das Gesamtgewicht der jeweiligen Zubereitungen. 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.
Beispiele:Examples:
Figure imgf000042_0001
Figure imgf000043_0001
Figure imgf000044_0001
Figure imgf000045_0001
Figure imgf000042_0001
Figure imgf000043_0001
Figure imgf000044_0001
Figure imgf000045_0001

Claims

Patentansprüche claims
1. Lichtschutzwirksame kosmetische oder dermatologische Emulsionen, dadurch gekennzeichnet, daß sie (a) einen oder mehrere partiell neutralisierte Ester von Monoglyceriden und/oder Di- glyceriden gesättigter Fettsäuren mit Zitronensäure und (b) mindestens ein Benzotriazolderivat enthalten.1. Sunscreen-effective cosmetic or dermatological emulsions, characterized in that they contain (a) one or more partially neutralized esters of monoglycerides and / or diglycerides saturated fatty acids with citric acid and (b) at least one benzotriazole derivative.
2. Zubereitung nach Anspruch 1, dadurch gekennzeichnet, daß sie sandabweisend ist.2. Preparation according to claim 1, characterized in that it is sand-repellent.
3. Lichtschutzwirksame kosmetische oder dermatologische Zubereitungen, dadurch gekennzeichnet, daß sie synergistische Stoffkombinationen von3. Sunscreen-effective cosmetic or dermatological preparations, characterized in that they contain synergistic combinations of substances
(a) einem oder mehreren partiell neutralisierten Estern von Monoglyceriden und/oder Diglyceriden gesättigter Fettsäuren mit Zitronensäure und(a) one or more partially neutralized esters of monoglycerides and / or diglycerides of saturated fatty acids with citric acid and
(b) mindestens einem Benzotriazolderivat enthalten, wobei die UV-Schutzleistung dieser Zubereitungen höher ist als die gleicher Zubereitungen, welche keine Substanzen gemäß (a) enthalten.(b) contain at least one benzotriazole derivative, the UV protection performance of these preparations being higher than the same preparations which contain no substances according to (a).
4. Zubereitung nach einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, daß als Zitronensäureester Glycerylstearatcitrat gewählt wird.4. Preparation according to one of claims 1 or 2, characterized in that glyceryl stearate citrate is chosen as the citric acid ester.
5. Zubereitung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß sie mindestens eine bei Raumtemperatur flüssige UV-Filtersubstanz enthält.5. 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.
6. Zubereitung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß sie ölfrei ist.6. Preparation according to one of the preceding claims, characterized in that it is oil-free.
7. Zubereitung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß sie mindestens eine weitere UV-Filtersubstanz, gewählt aus der Gruppe Tria- zine, Campherderivate und organische und/oder anorganische Pigmente, enthält.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 triazines, camphor derivatives and organic and / or inorganic pigments.
8. Zubereitung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß sie mindestens eine weitere UV-A-Filtersubstanz und/oder einen Breitbandfilter, gewählt aus der Gruppe Dibenzoylmethanderivate [insbesondere das 4-(tert.-Butyl)- 4'-methoxydibenzoylmethan], Phenylen-1,4-bis-(2-benzimidazyl)-3,3'-5,5'-tetrasulfon- säure und ihre Salze, 1,4-di(2-oxo-10-Sulfo-3-bomylidenmethyl)-Benzol und dessen Salze und 2,4-Bis-{[4-(2-Ethyl-hexyloxy)-2-hydroxy]-phenyI}-6-(4-methoxyphenyl)- 1,3,5-triazin, enthält, wobei die weiteren Filtersubstanzen jeweils einzeln oder in beliebigen Kombinationen miteinander vorliegen können.8. 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 and its salts, 1,4-di (2-oxo-10-sulfo -3-bomylidene-methyl) -benzene and its salts and 2,4-bis - {[4- (2-ethylhexyloxy) -2-hydroxy] phenyI} -6- (4-methoxyphenyl) - 1,3,5 -triazine, contains, where the further filter substances can be present individually or in any combination with one another.
9. Zubereitung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß sie mindestens ein Flavonglycosid, insbesondere α-Glucosylrutin, und/oder Vitamin E und/oder dessen Derivate enthält.9. 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.
10. Verwendung von Zubereitungen nach Anspruch 8 oder 9 zum Schutz der Haut vor vorzeitiger Alterung.10. Use of preparations according to claim 8 or 9 for protecting the skin from premature aging.
11. Zubereitung nach einem der vorhergehenden Ansprüche, welche ein samtiges oder seidiges Hautgefühl hervorruft oder verstärkt, dadurch gekennzeichnet, daß sie mindestens eine Substanz, gewählt aus der Gruppe Stärke und Stärkederivate, insbesondere Distärkephosphat, Aluminium- und/oder Natrium-Stärke Octenylsuccinat, enthält.11. Preparation according to one of the preceding claims, which causes or enhances a velvety or silky skin feeling, characterized in that it contains at least one substance selected from the group starch and starch derivatives, in particular distarch phosphate, aluminum and / or sodium starch octenyl succinate ,
12. Verwendung von Zubereitungen nach einem der vorhergehenden Ansprüche zur Hautbefeuchtung. 12. Use of preparations according to one of the preceding claims for moisturizing the skin.
PCT/EP2001/014931 2000-12-19 2001-12-18 Cosmetic and dermatological light protective formulations containing benzotriazole derivatives and surface active citric acid esters WO2002049582A2 (en)

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DE10226353A1 (en) * 2002-06-13 2003-12-24 Beiersdorf Ag Cosmetic and dermatological light protection preparations containing a synergistic combination of UV absorbers, inorganic pigments and organic dyes
DE102004047285A1 (en) * 2004-09-27 2006-04-20 Beiersdorf Ag Cosmetic sunscreen emulsion containing organic micropigments
DE102005023636A1 (en) * 2005-05-19 2006-11-23 Beiersdorf Ag Active ingredient combinations of glucosylglycerides and creatine and / or creatinine
DE102005023640A1 (en) * 2005-05-19 2006-11-23 Beiersdorf Ag Active substance combination, useful for skin moisturizing and stabilization of skin barrier, comprises glucosylglycerides and partially neutralized esters of monoglyceride and/or diglyceride fatty acids with citronic acids
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