DE10260876A1 - Cosmetic and/or dermatological emulsion sunscreens containing zinc oxide particles also contain UV filters which are liquid at 20oC - Google Patents

Abstract

Cosmetic and/or dermatological emulsions contain by wt. (a) zinc oxide particles (0.5-20%); (b) UV filters which are liquid at 20degreesC (0.5- 20%); and optionally also (c) further cosmetic and/or dermatological ingredients. An Independent claim is also included for production of the emulsions by (1) heating the oil phase with the liquid UV filter to 80degreesC; (2) dispersing the zinc oxide-containing pigment phase in the clear, heated oil phase; and (3) adding the aqueous phase heated to 75degreesC and cooling the mixture

Description

The present invention relates to cosmetic and / or dermatological UV light protection emulsions containing zinc oxide particles in an amount of 0.5 to 20% by weight, at 20 ° C liquid UV light protection filter in a concentration of 0.5 to 20% by weight, each based on the total weight of the emulsion, in addition to any other cosmetic ones and / or dermatological active ingredients, auxiliaries and additives, the method for the preparation of these emulsions and their use.

The trend away from the paleness for "healthy, athletic brown skin "is unbroken for years. To achieve this, people bet their skin from the sun's rays, as this causes pigment formation in the sense of melanin formation. The ultraviolet radiation However, sunlight also has a damaging effect on the skin: In addition to the acute damage (Sunburn) long-term damage occur like an elevated one Risk of skin cancer from excessive exposure to light from the UVB range (wavelength: 280-320 nm). The excessive exposure UVB and UVA radiation (wavelength: 320–400 nm) also leads to a weakening of the elastic and collagen fibers of the connective tissue. This leads to numerous phototoxic and photoallergic reactions and has a premature Skin aging.

To protect the skin were therefore developed a range of light protection filters used in cosmetic preparations can be used. These UVA and UVB filters are in shape in most industrialized countries summarized by positive lists such as Appendix 7 of the Cosmetics Ordinance.

In order to be able to estimate the effectiveness of the sun protection filters for the skin, the sun protection factor (SPF or LF) or sun protection factor (SF, narrowly called sun protection factor SPF) was introduced by Schulze in the 1950s. It is defined as follows:

In addition to liquid or at room temperature solid water or oil soluble organic carbon based UV filters are also used particulate UV filters, usually metal oxides such as titanium dioxide or zinc oxide, used in cosmetic UV light protection preparations. Your mode of action is based on a slowdown solar radiation through reflection, scattering and absorption. The UV light protection effect of the solid zinc oxide is dependent on the particle size. The smaller the particles are the higher is the absorption capacity (in contrast to light scattering). Also zinc oxide preparations only if the particle size is below 300 nm transparent. Has microfine zinc oxide for the sun protection area therefore usually a particle size of 10 to 100 nm. The UV light protection filter effect extends over the entire UV range from UV-A, UV-B and UV-C radiation. Also if the UV light protection effect is less than, for example, titanium dioxide particles Zinc oxide likes to be pigmented Light protection filter used because the connection, unlike Titanium dioxide is largely photostable, so the particles are not surface treated ("Coated"). One Surface treatment, e.g. with silicones, at most to facilitate dispersibility of zinc oxide particles in oil phases.

Zinc oxide becomes metallic via oxidation Zinc vapor at increased Temperature produced (G. Kindl, W. Raab: Licht und Haut, Govi-Verlag, Eschborn, 4th edition).

The disadvantages of zinc oxide in UV light protection emulsions are based on its physicochemical properties: So the solubility increases while reducing the UV protection effect at a pH below 6. Also zinc oxide reacts with a A range of emulsifiers (e.g. to form zinc stearate) and sulfonic acid groups contained organic UV light protection filter substances. Form further the zinc oxide particles in the emulsions easily agglomerate. Because their UV filter performance but dependent is from the particle size the agglomerate formation leads to losses in the UV light protection filter effect.

It was therefore the task of the present one Invention the disadvantages of the prior art as much as possible eliminate and develop stable, zinc oxide-containing UV light protection filter emulsions, which is characterized by a high UV light protection filter performance distinguished. Furthermore, organic should be in these UV light protection filter emulsions UV light protection filter with sulfonic acid groups can be included without sacrificing with stability and the UV light protection filter effect or precipitations of poorly soluble Zinc sulfonic acid complexes comes.

• a) Zinkoxidpartikel in einer Menge von 0,5 bis 20 Gewichts-%,
• b) ein oder mehrere bei 20 °C flüssige UV-Lichtschutzfilter in einer Gesamtkonzentration von 0,5 bis 20 Gewichts-%, jeweils bezogen auf das Gesamtgewicht der Emulsion, neben gegebenenfalls weiteren kosmetischen und/oder dermatologischen Wirk-, Hilfs- und Zusatzstoffen.

Surprisingly, the object is achieved by containing cosmetic and / or dermatological UV light protection emulsions

• a) zinc oxide particles in an amount of 0.5 to 20% by weight,
• b) one or more UV light protection filters which are liquid at 20 ° C. in a total concentration of 0.5 to 20% by weight, in each case based on the total weight of the emulsion, in addition to any further cosmetic and / or dermatological active ingredients, auxiliaries and additives.

These emulsions are characterized by high stability as well as a super-additive, synergistic UV light protection filter effect compared to UV light protection filter effect of the individual UV filter components. Furthermore, the agglomerate formation the zinc oxide particles and the formation of poorly soluble zinc oxide complexes effectively suppressed.

The method is also according to the invention for the production of cosmetic and / or dermatological UV light protection emulsions, which is characterized in that first the oil phase with the liquid UV filters to 80 ° C be heated, containing the pigment phase in the clear, heated oil phase Zinc oxide is dispersed and then heated to 75 ° C Water phase added and cooled becomes.

It is preferred according to the invention use the following procedure to prepare the light protection emulsion: The fat phase containing oils, one or more emulsifiers, the emulsifier combination consisting of Glycerol monostearate (INCI: Glyceryl Stearate SE) and polyoxyethylene (20) cetylstearyl ether (INCI: Ceteareth-20) is particularly preferred according to the invention, one or more UV light protection filters that are liquid at room temperature and if necessary consistency agents are heated (approx. 80 ° C) and so long stirred, until a clear solution arose. Subsequently the pigment phase containing zinc oxide and preferred according to the invention Titanium dioxide for a clear solution Fat phase given and dispersed. Then the water phase, which is advantageous according to the invention Lactic acid buffer and one or more further emulsifiers, preferred according to the invention chosen from the group Cetostearyl Alcohol (INCI: Cetearyl Alcohol), PEG-40 Castor Oil (INCI: PEG-40 Castor Oil) and sodium cetostearyl sulfate (INCI: Sodium Cetearyl Sulphate), to approx. 75 ° C heated and the oil phase added. The combination of oil phase and Submitted pigment phase and the water phase are added as also presented the water phase and the combination of oil phase and Pigment phase are added. Then at lower temperatures during the cooling process or advantageously another at room temperature according to the invention Part of the aqueous phase, containing phenylbenzimidazyl filter, preservative or Preservation aid and / or perfume added to the emulsion.

The zinc oxide according to the invention can be surface-treated (coated) or untreated (uncoated). The surface treatment can be that the zinc oxide particles according to known Procedure with a thin hydrophilic or hydrophobic inorganic or organic layer be provided. The various surface coatings can be in According to the present invention also contain water. Through the surface treatment receives the zinc oxide has a hydrophilic, amphiphilic or hydrophobic character.

Inorganic surface coatings in the sense of the present invention can consist of aluminum oxide (Al ₂ O ₃ ), aluminum hydroxide Al (OH) ₃ , or aluminum oxide hydrate (also: alumina, CAS no .: 1333-84-2), sodium hexametaphosphate (NaPO ₃ ) ₆ , sodium metaphosphate (NaPO ₃ ) _n , silicon dioxide (SiO ₂ ) (also: silica, CAS No .: 7631-86-9), or iron oxide (Fe ₂ O ₃ ). These inorganic surface coatings can occur alone, in combination and / or in combination with organic coating materials.

Organic surface coatings in the sense of the present invention consist of vegetable or animal aluminum stearate, vegetable or animal stearic acid, Lauric acid, Dimethylpolysiloxane (also: Dimethicone), methylpolysiloxane (Methicone), Simethicone (a mixture of dimethylpolysiloxane with an average chain length from 200 to 350 dimethylsiloxane units and silica gel) or alginic acid. This organic surface coatings can alone, in combination and / or in combination with inorganic Coating materials occur.

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

Zinc oxide particularly preferred according to the invention is not surface treated, such as the products with the trade name Z-Cote (BASF) or zinc oxide neutral (Haarmann & Reimer).

It is special according to the invention advantageous zinc oxide particles in an amount of 0.5 to 10 and in particular from 0.5 to 8% by weight based on the total weight of the emulsion use.

The cosmetic and / or dermatological invention UV light protection emulsions advantageously contain zinc oxide particles with a particle size of 10 nm to 300 nm and in particular from 20 nm to 200 nm.

It is also special according to the invention advantageous at 20 ° C liquid UV light protection filters in a concentration of 0.5 to 20% by weight and in particular use in a concentration of 0.5 to 15% by weight.

According to the invention, it is advantageous in the cosmetic and / or dermatological UV light protection emulsions the weight ratio of Zinc oxide too at 20 ° C liquid UV light protection filters from 0.1: 1 to 20: 1 and in particular from 0.25: 1 to 10: 1.

The UV light protection filters preferred at 20 ° C. according to the invention are homomenthyl salicylate (INCI: homosalate), 2-ethylhexyl-2-cyano-3,3-diphenylacrylate (INCI: octocrylene), 2-ethylhexyl-2-hydroxybenzoate (2-ethylhexyl salicylate, Octyl salicylate, INCI: octyl salicylate) and esters of cinnamic acid, preferably 4-methoxycinnamic acid (2-ethylhexyl) ester (2-ethylhexyl-4-methoxycinnamate, INCI: octyl methoxycinnamate) and 4-methoxycinnamate (isopentyl 4-methoxycinnamate, INCI: Isoamyl p-methoxycinnamate). 2-ethylhexyl 2-cyano-3,3-diphenyl (INCI: octocrylene) and ethylhexyl methoxycinnamate, preferably 4-methoxycinnamic acid (2-ethylhexyl) ester (2-ethylhexyl 4-methoxycinnamate, INCI: octyl methoxycinnamate) are particularly preferred.

The cosmetic and / or dermatological invention UV light protection emulsions can advantageously contain further UV light protection filters. So water-soluble UV light protection filters, in particular UV light protection filter with sulfonic acid groups and / or their salts are used.

• – Phenylen-1,4-bis-(2-benzimidazyl)-3,3'-5,5'-tetrasulfonsäure und ihre Salze, besonders die entsprechenden Natrium-, Kalium- oder Triethanolammonium-Salze, insbesondere das Phenylen-1,4-bis-(2-benzimidazyl)-3,3'-5,5'-tetrasulfonsäure-bis-natriumsalz mit der INCI-Bezeichnung Bisimidazylate (CAS-Nr.: 180898-37-7), welches beispielsweise unter der Handelsbezeichnung Neo Heliopan AP bei Haarmann & Reimer erhältlich ist;
• – Salze der 2-Phenylbenzimidazol-5-sulfonsäure, wie ihr Natrium-, Kalium- oder ihr Triethanolammonium-Salz sowie die Sulfonsäure selbst mit der INCI Bezeichnung Phenylbenzimidazole Sulfonsäure (CAS.-Nr. 27503-81-7), welches beispielsweise unter der Handelsbezeichnung Eusolex 232 bei Merck oder unter Neo Heliopan Hydro bei Haarmann & Reimer erhältlich ist;
• – 1,4-di(2-oxo-10-Sulfo-3-bornylidenmethyl)-Benzol (auch: 3,3'-(1,4-Phenylendimethylene)-bis-(7,7-dimethyl-2-oxo-bicyclo-[2.2.1]hept-1-ylmethan Sulfonsäure) und dessen Salze (besonders die entprechenden 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. Benzol-1,4- di(2-oxo-3-bornylidenmethyl-10-sulfonsäure) hat die INCI-Bezeichnung Terephtalidene Dicampher Sulfonsäure (CAS.-Nr.: 90457-82-2) und ist beispielsweise unter dem Handelsnamen Mexoryl SX von der Fa. Chimex erhältlich;
• – Sulfonsäure-Derivate des 3-Benzylidencamphers, wie z. B. 4-(2-Oxo-3-bornylidenmethyl)benzolsulfonsäure, 2-Methyl-5-(2-oxo-3-bornylidenmethyl)sulfonsäure und deren Salze.

Advantageous water-soluble UV filter substances in the sense of the present invention are e.g. B .:

• - Phenylene-1,4-bis (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid and its salts, especially the corresponding sodium, potassium or triethanolammonium salts, especially the phenylene-1,4 -bis- (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid bis-sodium salt with the INCI name bisimidazylate (CAS no .: 180898-37-7), which, for example, under the trade name Neo Heliopan AP is available from Haarmann &Reimer;
• - Salts of 2-phenylbenzimidazole-5-sulfonic acid, such as its sodium, potassium or triethanolammonium salt and the sulfonic acid itself with the INCI name phenylbenzimidazole sulfonic acid (CAS No. 27503-81-7), which, for example, under the Trade name Eusolex 232 is available from Merck or under Neo Heliopan Hydro from Haarmann &Reimer;
• - 1,4-di (2-oxo-10-sulfo-3-bornylidenemethyl) -benzene (also: 3,3 '- (1,4-phenylenedimethylene) -bis- (7,7-dimethyl-2-oxo- bicyclo- [2.2.1] hept-1-ylmethane sulfonic acid) and its salts (especially the corresponding 10-sulfato compounds, especially the corresponding sodium, potassium or triethanolammonium salt), which is also called benzene-1,4- di (2-oxo-3-bornylidenemethyl-10-sulfonic acid) Benzene-1,4-di (2-oxo-3-bornylidenemethyl-10-sulfonic acid) has the INCI name Terephtalidene Dicampher Sulfonic Acid (CAS no .: 90457-82-2) and is available, for example, under the trade name Mexoryl SX from Chimex;
• - Sulfonic acid derivatives of 3-benzylidene camphor, such as. B. 4- (2-oxo-3-bornylidene methyl) benzenesulfonic acid, 2-methyl-5- (2-oxo-3-bornylidene methyl) sulfonic acid and salts thereof.

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

Another advantageous broadband filter for the purposes of the present invention is 2- (2H-benzotriazol-2-yl) -4-methyl-6- [2-methyl-3- [1,3,3,3-tetramethyl-1 - [( trimethylsilyl) oxy] disiloxanyl] propyl] phenol (CAS no .: 155633-54-8) with the INCI name Drometrizole Trisiloxane, which is available under the trade name Mexoryl ^® XL from Chimex.

• – 3-Benzylidencampher-Derivate, vorzugsweise 3-(4-Methylbenzyliden)campher, 3-Benzylidencampher;
• – 4-Aminobenzoesäure-Derivate, vorzugsweise 4-(Dimethylamino)-benzoesäure(2-ethylhexyl)ester, 4-(Dimethylamino)benzoesäureamylester;
• – Derivate des Benzophenons, vorzugsweise 2-Hydroxy-4-methoxybenzophenon, 2-Hydroxy-4-methoxy-4'-methylbenzophenon, 2,2'-Dihydroxy-4-methoxybenzophenon
• – sowie an Polymere gebundene UV-Filter.
• – 3-(4-(2,2-bis Ethoxycarbonylvinyl)-phenoxy)propenyl)-methoxysiloxan/Dimethylsiloxan -Copolymer welches beispielsweise unter der Handelsbezeichnung Parsol^® SLX bei Hoffmann La Roche erhältlich ist.

Furthermore, the emulsions according to the invention can contain oil-soluble UV filter substances. Advantageous oil-soluble UV-B and / or broadband filter substances in the sense of the present invention 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;
• - Derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone
• - As well as UV filters bound to polymers.
• - 3- (4- (2,2-bis ethoxycarbonylvinyl) phenoxy) propenyl) -methoxysiloxan / dimethylsiloxane copolymer which is obtainable for example from Hoffmann La Roche under the trade name Parsol ^® SLX.

Advantageous emulsions in the sense the present invention, which is characterized by a high or very high UV-A and / or UV-B protection, contain UV-A and / or Broadband filters, especially 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, the 1,4-di (2-oxo-10-sulfo-3-bornylidenemethyl) benzene and / or its salts, each individually or in any combination together.

Further UV filters advantageous according to the invention have the basic structure of triazine, such as the symmetrically substituted 4,4 ', 4 "- (1,3,5-triazine-2,4,6-triyltrümino) tris-benzoic acid tris (2-ethylhexyl ester) ), synonymous: 2,4,6-tris- [anilino- (p-garbo-2'-ethyl-1'-hexyloxy)] - 1,3,5-triazine. [UVINUL T 150 (BASF)], asymmetrical substituted s-triazine derivatives, for example those as in the EP-A-570 838 be described, Diethylhexylbutylamidotriazon (INCI: Diethylhexyl Butamido Triazone) [UVASORB HEB (Sigma 3V)], 2,4-bis - {[4- (2-ethyl-hexyloxy) -2-hydroxy] phenyl} -6- ( 4-methoxyphenyl) -1,3,5-triazine (INCI: bis-ethylhexyloxyphenol methoxyphenyl triazine or also aniso triazine) [Tinosorb ^® S (CIBA-Chemicals GmbH)], 2,4-bis - {[4- (3- sulfonato) -2-hydroxypropyloxy) -2-hydroxy] phenyl} -6- (4-methoxyphenyl) -1,3,5-triazine sodium salt, with 2,4-bis - {[4- (3- ( 2-propyloxy) -2-hydroxypropyloxy) -2-hydroxy] phenyl} -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis - {[4- (2-ethyl -hexyloxy) -2-hydroxy] phenyl} -6- [4- (2-methoxyethylcarboxyl) phenylamino] -1,3,5-triazine, 2,4-bis - {[4- (3- (2- propyloxy) -2-hydroxy-propyloxy) -2-hydroxy] phenyl} -6- [4- (ethylcarboxyl) phenylamino] -1,3,5-triazine, 2,4-bis - {[4- (2nd -ethylhexyloxy) -2-hydroxy] phenyl} -6- (1-methyl-pyrrol-2-yl) -1,3,5-triazine, 2,4-bis - {[4-tris (trimethylsiloxysilylpropyloxy) -2-hydroxy] phenyl} -6- (4-methoxyphenyl) -1,3,5-triazine, and 2,4-bis - {[4- (2-methylpropenyloxy ) -2-hydroxy] phenyl} -6- (4-methoxyphenyl) -1,3,5-triazine, filters 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.

Other advantageous according to the invention UV filters contain the structural element of benzotriazole, for example 2,2'-methylene-bis- (6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) -phenol) [Tinosorb M (Ciba)], 2,2'-methyl-bis- [6 (2H-benzotriazol-2-yl) -4- (methyl) phenol] (MIXXIM BB / 200 from Fairmount Chemical), 2- (2'-hydroxy-3 ', 5'-di-tamylphenyl) benzotriazole (CAS No .: 025973-551), 2- (2'-hydroxy-5'-octylphenyl) benzotriazole (CAS No .: 003147-75-9) or 2- (2'-hydroxy-5'methylphenyl) benzotriazole (CAS No .: 2440-22-4) and 2- (2H-benzotriazol-2-yl) -4-methyl-6- [2-methyl-3- [1,3,3,3-tetramethyl-1 - [(trimethylsilyl) oxy] disiloxanyl] propyl] phenol (CAS No .: 155633-54-8) [Mexoryl XL (Chimex)] with the INCI name Drometrizole Trisiloxane.

worin R¹, R² und R³ unabhängig voneinander gewählt werden aus der Gruppe der verzweigten oder unverzweigten, gesättigten oder ungesättigten Alkylreste mit 1 bis 10 Kohlenstoffatomen. Es ist erfindungsgemäß besonders vorteilhaft, die Reste R¹ und R² gleich zu wählen, insbesondere aus der Gruppe der verzweigten Alkylreste mit 3 bis 5 Kohlenstoffatomen. Es ist ferner besonders vorteilhaft im Sinne der vorliegenden Erfindung, wenn R³ einen unverzweigten oder verzweigten Alkylrest mit 8 Kohlenstoffatomen, insbesondere den 2-Ethylhexylrest darstellt.Advantageous UV-A filters of the benzoxazole derivative type in the sense of the present invention are distinguished by the following structural formula,

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

auszeichnet und bei 3V Sigma unter der Handelsbezeichnung Uvasorb^® K2A erhältlich ist.Benzoxazole derivative which is particularly preferred according to the invention is 2,4-bis- [5-1 (dimethylpropyl) benzoxazol-2-yl- (4-phenyl) -imino] -6- (2-ethylhexyl) -imino-1,3, 5-triazine with CAS No. 288254-16-0, which is characterized by the structural formula

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

That or the benzoxazole derivatives are advantageously in dissolved Form in the cosmetic according to the invention Preparations. However, it may also be advantageous if the benzoxazole derivative or derivatives in pigmentary, d. H. undissolved form - for example in particle sizes of 10 nm up to 300 nm.

worin
– R¹ und R² unabhängig voneinander Wasserstoff, C₁-C₂₀-Alkyl, C₃-C₁₀-Cycloalkyl oder C₃-C₁₀-Cycloalkenyl bedeuten, wobei die Substituenten R¹ und R² gemeinsam mit dem Stickstoffatom, an das sie gebunden sind, einen 5- oder 6-Ring bilden können und
– R³ einen C₁-C₂₀-Alkyl Rest bedeutet.Advantageous UV filters of the type hydroxybenzophenone are characterized by the following structural formula:

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

und unter dem Uvinul A Plus bei der Fa. BASF erhältlich ist.A particularly advantageous hydroxybenzophenone in the context of the present invention is 2- (4'-diethylamino-2'-hydoxybenzoyl) benzoic acid hexyl ester (also: aminobenzophenone), which is distinguished by the following structure:

and is available under the Uvinul A Plus from BASF.

Other inorganic UV filter pigments, for example titanium dioxide particles, can also be used advantageously in addition to zinc oxide in the emulsions according to the invention. Suitable titanium dioxide particles and predispersions of titanium dioxide particles are available, for example, under the following trade names from the companies listed:

The combination of inorganic UV filter pigments of titanium dioxide and zinc oxide according to the invention is special according to the invention prefers.

The list of UV filters mentioned, which can be used within the meaning of the present invention Of course not be limiting.

The emulsions according to the invention advantageously contain the substances that UV radiation in the UV-A and / or UV-B range absorb, in a total amount of e.g. B. 0.1% by weight to 30% by weight, preferably 0.1% by weight to 20% by weight, in particular 0.5% by weight to 15.0% by weight, based in each case on the total weight of the emulsions, to provide cosmetic preparations that the hair or the skin in front of the entire range of ultraviolet radiation protect.

According to the invention, the is particularly preferred Use of 2-phenylbenzimidazole-5-sulfonic acid and its sodium, potassium and triethanolammonium salts [Eusolex 232 (Merck), Neo Heliopan Hydro (H&R), Parsol NS (Givaudan)], phenylene-1,4-bis- (2-benzimidazyl) -3,3 ', 5,5'-tetrasulfonic acid and their sodium, potassium and triethanolammoium salts, especially the disodium salt [Neo Heliopan AP (Haarmann & Reimer)] and / or 3,3 '- (1,4-phenylenedimethine) -bis- (7,7-dimethyl-2-oxobicyclo [2.2.1] -heptane 1-methanesulfonic acid and its Salts [Mexoryl SX (Chimex)].

The cosmetic and / or dermatological invention UV light protection emulsions can Contain cosmetic auxiliaries, as is usually the case in such preparations are used, e.g. B. emulsifiers, preservatives, preservation aids, Bactericides, perfumes, skin bleaching agents, self-tanners, substances for preventing foaming, Dyes, pigments that have a coloring Have effect thickeners, moisturizing and / or moisturizing Substances, fillers, which the skin feeling improve fats, oils, Waxes or other usual Components of a cosmetic or dermatological formulation such as alcohols, polyols, polymers, foam stabilizers, electrolytes, organic solvents or silicone derivatives.

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

The water phase of the emulsions according to the invention can be beneficial usual contain cosmetic auxiliaries, such as alcohols, especially those with a low C number, preferably ethanol and / or isopropanol, diols or polyols lower Carbon 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, dihydoxyacetone and in particular one or more Thickening agent, which or which are advantageously chosen can from the group silicon dioxide, aluminum silicates, polysaccharides or their derivatives, e.g. B. hyaluronic acid, xanthan gum, hydroxypropylmethyl cellulose, particularly advantageous from the group of polyacrylates, preferred a polyacrylate from the group of the so-called carbopoles, for example Carbopole types 980, 981, 1382, 2984, 5984, each individually or in combination.

Copolymers of C _10-30 alkyl acrylates and one or more monomers of acrylic acid, methacrylic acid or their esters are also advantageous.

Compounds which have the INCI name “Acrylates / C _10-30 Alkyl Acrylate Crosspoly mer ". Particularly advantageous are those available under the trade names Pemulen TR1 and Pemulen TR2 from the BF Goodrich Company.

Connections that are advantageous the INCI name ammonium acryloyldimethyltaurate / vinyl pyrrolidone copolymers wear.

Advantageously according to the invention, the ammonium acryloyldimethyltaurate / vinylpyrrolidone copolymers have the empirical formula [C ₇ H ₁₆ N ₂ SO ₄ ] _n [C ₆ H ₉ NO] _m , corresponding to a statistical structure as follows

Preferred species for the purposes of the present invention are listed in Chemical Abstracts under the registry numbers 58374-69-9, 13162-05-5 and 88-12-0 stored and available under the trade name Aristoflex ^® AVC from Clariant GmbH.

Also advantageous are copolymers / Gross polymers comprising Acryloyldimethyl Taurate such as Simugel® ^® EC or EC Simugel® ^® from Seppic SA

Further advantageous according to the invention Thickeners to be used are also water-soluble or dispersible anionic polyurethanes. Advantageous in the sense of present invention are e.g. B. Polyurethane-1 and / or Polyurethane-4.

Particularly advantageous polyurethanes for the purposes of the present invention are the types available under the trade name Avalure ^™ UR from the BF Goodrich Company, such as, for example, Avalure ^™ UR 445, Avalure ^™ UR 450 and the like. The polyurethane available under the trade name Luviset Pur from BASF is also advantageous in the sense of the present invention.

Moisturizers can also be preferred be used. Substances or mixtures of substances are used as moisturizers denotes which cosmetic or dermatological preparations impart the property after application or distribution the skin surface the release of moisture from the horny layer (also transepidermal waterloss (TEWL)) and / or the hydration of the horny layer to positively influence.

Advantageous moisturizers for the purposes of the present invention are, for example, glycerol, lactic acid and / or lactates, in particular sodium lactate, butylene glycol, propylene glycol, biosaccaride gum-1, glycine soya, ethylhexyloxyglycerol, pyrrolidonecarboxylic 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. is available under the name Fucogel ^® 1000 from the company SOLABIA SA.

The cosmetic and / or dermatological oil-in-water emulsions according to the invention can also advantageous, although not mandatory, contain fillers which z. B. the sensory and cosmetic properties of the formulations further improve and, for example, create a velvety or silky feeling on the skin or reinforce. Favorable fillers In the context of the present invention, starch and starch derivatives (such as tapioca starch, distarch phosphate, Aluminum or

Sodium starch octenylsuccinate and the like), pigments which have neither primarily a UV filter effect nor a coloring effect (such as. For example, boron nitride etc.) and / or Aerosils ^® (CAS no. 7631-86-9).

The oil phase of the cosmetic and / or dermatological UV light protection emulsions according to the invention is advantageously selected from the group of polar oils, for example from the group of lecithins and fatty acid triglycerides, specifically the triglycerol esters of saturated and / or unsaturated, branched and / or unbranched alkane carboxylic acids with a chain length of 8 to 24, especially 12 to 18 carbon atoms. The fatty acid triglycerides can, for example, advantageously be selected from the group of synthetic semi-synthetic and natural oils, such as B. cocoglyceride, olive oil, sunflower oil, soybean oil, peanut oil, rapeseed oil, almond oil, palm oil, coconut oil, castor oil, wheat germ oil, grape seed oil, safflower oil, evening primrose oil, macadamia nut oil and the like.

According to the invention, z. B. natural Waxes of animal and vegetable origin, such as Beeswax and other insect waxes as well as berry wax, shea butter and / or Lanolin (wool wax).

Other advantageous polar oil components can in the sense of the present invention can also be selected from the group of Esters from saturated and / or unsaturated, branched and / or unbranched alkane carboxylic acids with a chain length of 3 to 30 carbon atoms and saturated and / or unsaturated, branched and / or unbranched alcohols with a chain length of 3 to 30 carbon 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 carbon atoms. Such ester oils can then advantageously chosen are selected from the group octyl palmitate, octyl cocoate, octyl isostearate, Octyldodeceyl myristate, octyl dodecanol, cetearyl isononanoate, isopropyl myristate, Isopropyl palmitate, isopropyl stearate, isopropyl oleate, n-butyl stearate, n-hexyl laurate, n-decyl oleate, Isooctyl stearate, isononyl stearate, isononyl isononanoate, 2-ethylhexyl palmitate, 2-ethylhexyl laurate, 2-hexyldecyl stearate, 2-octyldodecyl palmitate, Stearyl heptanoate, oleyl oleate, olerlerucate, erucyl oleate, erucylerucate, Tridecyl stearate, tridecyl trimellitate, as well as synthetic, semi-synthetic and natural Mixtures of such esters, such as. B. Jojoba oil.

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

It is further preferred that the oil component from the group consisting of isoeicosane, neopentyl glycol, propylene glycol dicaprylate / dicaprate, caprylic / capric / diglyceryl succinate, butylene glycol dicaprylate / dicaprate, cocoglycerides (z. B. Myritol ^® 331 from Henkel), C _12-13 alkyl lactate , Di-C _12-13 alkyl tartrate, triisostearin, dipentaerythrityl hexacaprylate / hexacaprate, propylene glycol monoisostearate, tricaprylin, dimethyl isosorbide. It is particularly advantageous if the oil phase of the formulations according to the invention has a content of C _12-15 alkyl benzoate or consists entirely of this.

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

Any mix of such oil and wax components are to be used advantageously for the purposes of the present invention.

Furthermore, the oil phase can also be advantageous also non-polar oils contain, for example those which are selected from the group of branched and unbranched hydrocarbons and waxes, in particular Mineral oil, Vaseline (petrolatum), paraffin oil, Squalane and squalene, polyolefins, hydrogenated polyisobutenes and Isohexadecane. Among the polyolefins, polydecenes are the preferred Substances.

The oil phase can also be advantageous have a content of cyclic or linear silicone oils or completely such oils exist, although it is preferred, except the silicone oil or silicone oils one additional Content of other oil phase components to use.

werden auch als Polydimethylsiloxan bzw. Dimethicon (INCI) bezeichnet. Dimethicone gibt es in verschiedenen Kettenlängen bzw. mit verschiedenen Molekulargewichten.Silicone oils are high-molecular synthetic polymeric compounds in which silicon atoms are linked in a chain and / or network-like manner via oxygen atoms and the remaining valences of silicon by hydrocarbon residues (mostly methyl, more rarely ethyl, propyl, phenyl groups, 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

are also known as polydimethylsiloxane or dimethicone (INCI). Dimethicone is available in different chain lengths or with different molecular weights.

Particularly advantageous polyorganosiloxanes for the purposes of the present invention are, for example, dimethylpolysiloxanes [poly (dimethylsiloxane)], which are available, for example, under the trade names Abil 10 to 10,000 from Th. Goldschmidt. Also advantageous are phenylmethylpolysiloxanes (INCI: phenyl dimethicone, phenyl trimethicone), cyclic silicones (octamethylcyclotetrasiloxane or decamethylcyclopentasiloxane), which according to INCI are also called cyclomethicones, amino-modified silicones (INCI: amodimethicone) and silicone waxes. B. Polysiloxane-polyalkylene copolymers (INCI: Stearyl Dimethico ne and Cetyl Dimethicone) and Dialkoxydimethylpolysiloxane (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).

Advantageous preservatives in the sense of the present invention are, for example, formaldehyde releasers (such as, for example, DMDM hydantoin, which is available, for example, from Lonza under the trade name Glydant ^™ ), iodopropyl butyl carbamates (for example those under the trade names Glydant-2000, Glycacil -L, Glycacil-S available from Lonza and / or Dekaben LMB from Jan Dekker), parabens (ie alkyl p-hydroxybenzoates such as methyl, ethyl, propyl and / or butyl paraben), phenoxyethanol, ethanol, benzoic acid and the like more. Usually, the preservation system according to the invention advantageously also includes preservation aids, such as ethylhexyloxyglycerol, glycine soy etc.

Particularly advantageous emulsions are also obtained when antioxidants as additives or active ingredients be used. Included according to the invention the emulsions advantageously one or more antioxidants. As cheap, but still optional antioxidants can all for cosmetic and / or dermatological applications suitable or customary antioxidants used become.

Particularly advantageous in the sense of present invention can water-soluble Antioxidants are used, such as vitamins, e.g. B. ascorbic acid and their derivatives.

Preferred antioxidants are also Vitamin E and its derivatives as well as Vitamin A and its derivatives.

The amount of antioxidants (a 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 wt .-%, based on the total weight of the preparation.

If vitamin E and / or its Derivatives that are antioxidants are advantageous their respective concentrations from the range of 0.001 to 10 % By weight, based on the total weight of the formulation.

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

It is particularly advantageous when the cosmetic preparations according to the present invention contain cosmetic or dermatological active ingredients, preferred Active ingredients are antioxidants that protect the skin from oxidative stress protect can.

Other advantageous active ingredients in For the purposes of the present invention, natural active substances and / or their derivatives, such as. B., alpha-lipoic acid, phytoene, D-biotin, coenzyme Q10, alpha-glucosylrutin, carnitine, carnosine, natural and / or synthetic isoflavonoids, creatine, subtilisin, taurine and / or β-alanine.

Recipes according to the invention, which, for. B. known anti-wrinkle active ingredients such as flavone glycosides (in particular α-glycosyl rutin), Contain coenzyme Q10, vitamin E and / or derivatives and the like, are particularly advantageous for prophylaxis and treatment cosmetic or dermatological skin changes, such as z. B. at skin aging (such as dryness, roughness and formation of dryness wrinkles, Itching, reduced regreasing (e.g. after washing), visible vasodilation (telangiectasia, Cuperosis), flaccidity and formation of wrinkles and fine lines, local hyper, hypo and incorrect pigmentation (e.g. age spots), increased vulnerability across from mechanical stress (e.g. cracking) and the like). Farther they are advantageous against the appearance of dry or rough skin.

Furthermore, it can be from Be advantageous to incorporate film formers into the emulsions according to the invention, for example 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 are suitable or dispersible as well as fat-soluble film formers, in each case individually or in combination with each other.

Advantageous water-soluble or dispersible film formers are e.g. B. Polyurethanes (e.g. the Avalure ^® types from Goodrich), Dimethicone Copolyol Polyacrylate (Silsoft Surface ^® from the Witco Organo Silicones Group), PVP / VA (VA = vinyl acetate) copolymer (Luviscol VA 64 Powder from BASF) etc ,

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

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

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

Depending on their structure, cosmetic or topical dermatological compositions in the sense of the present Invention, used for example as a skin protection cream, Cleansing milk, day or night cream, etc. It may be possible and advantageous, the compositions according to the invention as a basis for pharmaceutical Use wording. In general, the use of UV light protection emulsions according to the invention as an ointment, cream, milk or lotion to protect the skin and / or the skin appendages before UV radiation according to the invention.

The preparations in the sense of the present Invention can preferably one or more water phases in addition to one or more oil phases included and for example in the form of W / O, O / W, W / O / W or O / W / O emulsions are present. Such formulations can preferably also a microemulsion (e.g. a PIT emulsion), a solid emulsions (i.e. an emulsion that is stabilized by solids, z. B. a Pickering emulsion), a sprayable emulsion or a hydrodispersion his. For the preparation of the UV light protection emulsions according to the invention can all for the cosmetics-approved emulsifiers are used. Especially the emulsifiers cetearyl alcohol, sodium cetearyl sulfate, PEG-40 castor oil, Glycerol monostearate (INCI: Glyceryl Stearate SE), polyoxyethylene (20) cetyl stearyl ether (INCI: Ceteareth-20), esters of polyglycerol and sorbitan, sorbitan monooleate, PEG-120 methyl glucose dioleate.

Last but not least, the use according to the invention of UV light protection emulsions according to the invention to increase of stability and the UV light protection filter performance of zinc oxide-containing UV light protection emulsions.

The use of UV light protection emulsions is in accordance with the invention according to one of the preceding claims as an ointment, cream, milk or lotion, spray, foam, aerosol to protect the skin and / or the Skin appendages against UV radiation.

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

Formulation Examples:

1. O / W sun protection emulsions

2. Foam-shaped O / W emulsions:

4. Dünnflüssige bis sprühbare W/O-Emulsionen (zur Verwendung als Tränkungslösung, Spray oder Aerosol)

5. W/O Sonnenschutz Emulsionen (Cremes & Lotions)

6. Hydrodispersionen (zur Verwendung als Lotion, Tränkungslösung oder Spray)

7. Feststoftstablisisierte Emulsionen

Combination of the grease / light protection filter phase heated to 78 ° C with the water / light protection filter phase heated to 75 ° C. Homogenization using a gear rim dispersion machine (rotor-stator principle) at 65 ° C. 45 min stirring in the Becomix while gassing with helium at 1 bar with cooling to 30 ° C. Add the additives at 30 ° C (perfume). Homogenization using a gear rim dispersion machine (rotor-stator principle) at 23 ° C. 3. PIT emulsions (for use as an impregnation solution, spray or aerosol)

4. Low-viscosity to sprayable W / O emulsions (for use as a soaking solution, spray or aerosol)

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

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

7. Solid stabilized emulsions

Claims (10)

Cosmetic and / or dermatological UV light protection emulsions containing a) Zinc oxide particles in an amount of 0.5 to 20 % By weight, b) one or more UV light protection filters that are liquid at 20 ° C. in a total concentration of 0.5 to 20% by weight, each based on the total weight of the emulsion, in addition, if appropriate further cosmetic and / or dermatological active, auxiliary and Additives. Process for the production of cosmetic and / or dermatological UV light protection emulsions according to claim 1, characterized in that first the oil phase with the liquid UV filters to 80 ° C be heated into the clear, heated oil phase containing the pigment phase Zinc oxide is dispersed, then heated to 75 ° C Water phase added and cooled becomes. Cosmetic and / or dermatological UV light protection emulsion according to one of the claims 1 or 2, characterized in that zinc oxide particles with a Particle size of 10 nm to 300 nm can be used. Cosmetic and / or dermatological UV light protection emulsion according to one of the claims 1 to 3, characterized in that the weight ratio of Zinc oxide too at 20 ° C liquid UV light protection filters from 0.1: 1 to 20: 1. Cosmetic and / or dermatological UV light protection emulsion according to one of claims 1 to 4, characterized in that as a UV light protection filter which is liquid at 20 ° C, homomenthyl salicylate (INCI: homosalate), 2-ethylhexyl-2-cyano-3,3-diphenylacrylate ( INCI: octocrylene), 2-ethylhexyl-2-hydroxybenzoate (2-ethyl hexylsalicylate, octylsalicylate, INCI: octyl salicylate) and esters of cinnamic acid, preferably 4-methoxycinnamic acid (2-ethylhexyl) ester (2-ethylhexyl-4-methoxycinnamate, INCI: octyl methoxycinnamate) and / or 4-methoxycinnamate isopentyl isopentyl ester (4-methoxycinnamate) , INCI: Isoamyl p-methoxycinnamate) can be used. Cosmetic and / or dermatological UV light protection emulsion according to one of the claims 1 to 5, characterized in that the UV light protection emulsion contains additional UV light protection filters. Cosmetic and / or dermatological UV light protection emulsion according to one of the claims 1 to 6, characterized in that as a further UV light protection filter Pigments of titanium dioxide are used. Cosmetic and / or dermatological UV light protection emulsion according to one of the claims 1 to 7, characterized in that as a further UV light protection filter Compounds with sulfonic acid groups and / or their salts such as 2-phenylbenzimidazole-5-sulfonic acid and / or their sodium, potassium or triethanolammonium salts, phenylene-1,4-bis (2-benzimidazyl) -3,3 ', 5,5'-tetrasulfonic acid and / or their sodium, Potassium or triethanolammoium salts and / or 3,3 '- (1,4-phenylenedimethine) -bis- (7,7-dimethyl-2-oxobicyclo [2.2.1] -heptane-1-methanesulfonic acid and / or their salts [Mexoryl SX (Chimex)] are used. Use of UV light protection emulsions after one of the preceding claims to increase the stability and the UV light protection filter performance of zinc oxide-containing UV light protection emulsions. Preparation according to one of the preceding claims, characterized characterized in that at least one Repellent, especially the 3- (N-n-butyl-N-acetylamino) propionic acid ethyl ester is included.