WO2005117823A1 - Benzoate de 2-phenylethyle dans des mousses cosmetiques - Google Patents

Benzoate de 2-phenylethyle dans des mousses cosmetiques Download PDF

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Publication number
WO2005117823A1
WO2005117823A1 PCT/EP2005/052333 EP2005052333W WO2005117823A1 WO 2005117823 A1 WO2005117823 A1 WO 2005117823A1 EP 2005052333 W EP2005052333 W EP 2005052333W WO 2005117823 A1 WO2005117823 A1 WO 2005117823A1
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Prior art keywords
foam
preparation
preparations
present
advantageous
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PCT/EP2005/052333
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German (de)
English (en)
Inventor
Claudia Mundt
Andreas Clausen
Kerstin Hoop
Heike Lerg
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Beiersdorf Ag
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Publication of WO2005117823A1 publication Critical patent/WO2005117823A1/fr

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    • 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
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04Dispersions; Emulsions
    • A61K8/046Aerosols; Foams
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04Dispersions; Emulsions
    • A61K8/06Emulsions
    • 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
    • A61K8/4966Triazines or their condensed derivatives
    • 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

Definitions

  • the present invention relates to foam-like or foamable cosmetic preparations containing 2-phenylethylbenzoate and one or more UV filter substances from the group of the triazine derivatives
  • Foams or foam-like preparations belong to the disperse systems.
  • Emulsions are two- or multi-phase systems of two or more liquids which are not or only slightly soluble in one another.
  • the liquids pure or as solutions
  • the liquids are present in an emulsion in a more or less fine distribution, which is generally only of limited stability.
  • Foams are structures made of gas-filled, spherical or polyhedral cells, which are delimited by liquid, semi-liquid, highly viscous or solid cell bridges.
  • the cell bridges connected via so-called nodes, form a coherent framework.
  • the foam lamellae (closed-cell foam) stretch between the cell bars. If the foam lamellae are destroyed or flow back into the cell webs at the end of foam formation, an open-cell foam is obtained.
  • Foams are also thermodynamically unstable, since surface energy can be obtained by reducing the surface. The stability and thus the existence of a foam depends on the extent to which it can prevent its self-destruction.
  • Cosmetic foams are generally dispersed systems composed of liquids and gases, the liquid being the dispersant and the gas the dispersed substance. Foams from low-viscosity liquids are temporarily stabilized by surface-active substances (surfactants, foam stabilizers). Have such surfactant foams due to their large inner surface, a strong adsorption capacity, which is used for example in cleaning and washing processes. Accordingly, cosmetic foams are used in particular in the areas of cleaning, for example as shaving cream, and hair care.
  • surfactants foam stabilizers
  • foaming agents surfactants or other surfactants that besides interfacial activity also possess a certain film-forming ability.
  • Cosmetic foams have the advantage over other cosmetic preparations that they allow a fine distribution of active ingredients on the skin.
  • cosmetic foams can usually only be achieved by using special surfactants, which are also often not very kind to the skin.
  • Post-foaming cosmetic preparations are also known per se. They are first applied to the skin in fluid form from an aerosol container and, after a short delay, develop the actual foam there, for example a shaving foam, under the influence of the post-foaming agent contained. Post-foaming preparations are often in special embodiments such as post-foaming shaving gels or the like.
  • the prior art also knows cosmetic preparations which are already foamed during manufacture and which are inherently sufficiently stable to be packaged, stored and put on the market in the customary manner (see, for example, DE-100 63 340-A1 , DE-100 63 341-A1 and DE-100 63 342-A1).
  • foamable cosmetic emulsions can be prepared according to the prior art without the use of special surfactants not formulate or manufacture technically. This is particularly true for systems ⁇ based on classic emulsifiers. According to the prior art to develop such systems with the addition of propellant, only watery, moist foams that break quickly after application.
  • the object of the present invention was therefore to enrich the prior art and to provide cosmetic self-foaming and / or foam-like preparations which do not have the disadvantages of the prior art.
  • the object is surprisingly achieved by • foam-like or foamable cosmetic preparations containing 2-phenylethylbenzoate and one or more UV filter substances from the group of triazine derivatives, and by
  • foams in the sense of the present invention (in the following for the sake of simplicity also called foams) z.
  • B. represent macroscopically visible dispersed systems from gases dispersed in liquids.
  • the foam character can, for example, only become visible under a (light) microscope.
  • foams according to the present invention - especially when the gas bubbles are too small to be recognized under a light microscope - can also be recognized from the strong increase in volume of the system.
  • the invention makes it possible for the first time to obtain a substantial, compact cream foam (“mousse”) which is distinguished by a long storage period and by an extraordinarily high stability and a compact appearance.
  • Compositions according to the invention develop during their production - for example while stirring or during the homogenization - to fine-bubble foams.
  • fine-bubble, rich foams of excellent cosmetic elegance are available.
  • skin-compatible preparations are also available, and valuable ingredients can be distributed particularly well on the skin.
  • the invention further relates to the use of 2-phenylethylbenzoate for reducing the bubble size of self-foaming, foam-like, post-foaming or foamable cosmetic preparations.
  • Foam reinforcement also means that the stability of the foamed preparations (the “foam stability”) is significantly improved compared to otherwise identical preparations which do not contain any UV filter substances according to the invention; H. breaking the foams is delayed by the use according to the invention.
  • “foam reinforcement” in the sense of the present invention means that the cosmetic properties of the foams according to the invention are also significantly improved in comparison to preparations which do not contain UV filter substances according to the invention: rich, solid foams are obtained by the use according to the invention ("Foam creams") which, despite their compactness and richness, are easy to distribute and are quickly absorbed.
  • “foam reinforcement” in the sense of the present invention means that the bubble size of the foams according to the invention is smaller in comparison to preparations which do not contain UV filter substances according to the invention. In contrast, the number of bubbles in the same volume is increased.
  • bubbles mean the gas bubbles
  • bubble size means the diameter of the gas bubbles accordingly.
  • a microscopic foam examination can be carried out, for example, at a constant temperature of 21 ° C as follows:, • The cosmetic preparation to be examined is made into a sample from the container at three different locations (eg top, middle, bottom) using a spatula taken (corresponding to three samples per preparation). (Aerosol foams are sprayed into a reservoir or onto cellulose and the samples are taken from the reservoir.)
  • Advantageous preparations for the purposes of the present invention have an average bubble size of 0.005 to 0.5 mm 2 , advantageously 0.005 to 0.2 mm 2 , particularly advantageously 0.005 to 0.1 mm 2 and a number of bubbles from 100 to 4000, advantageously of 500 to 3000, particularly advantageously from 1000 to 3000, in each case based on the examined image section (see above).
  • the preparation according to the invention also has further surprising advantages over the preparations of the prior art. •
  • the use of the 2-phenylethylbenzoate according to the invention leads to a particularly pleasant velvety-silky skin feel, so that the use of cyclomethicones can be dispensed with in the preparations.
  • Cyclomethicone-free cosmetic preparations are therefore advantageous according to the invention.
  • the 2-phenylethylbenzoate according to the invention By using the 2-phenylethylbenzoate according to the invention, surprisingly large amounts of UV filter substances from the group of triazine derivatives can be incorporated (dissolved) in the preparation. As a result, the total amount of oil components in the preparation can be significantly reduced without sacrificing the UV protection performance of the preparation. Particularly low-fat ("light”) and less sticky preparations with high UV protection can thus be produced, which are particularly suitable for face care.
  • the use of the 2-phenylethylbenzoate according to the invention reduces the use concentration of preservatives in the preparation.
  • the preparation according to the invention and the uses according to the invention are advantageously characterized according to the invention in that they contain 2-phenylethylbenzoate in a concentration of 0.5 to 20% by weight and preferably 2 to 10% by weight, based in each case on the total weight of the preparation ,
  • the 2-phenylethylbenzoate (INCI: 2-phenylethyl benzoate) according to the invention has the following structure
  • the preparation according to the invention or uses according to the invention are advantageously characterized according to the invention in that the preparation contains one or several UV filter substances from the group of triazine derivatives selected from the group of compounds • 2,4-bis - ⁇ [4- (2-ethylhexyloxy) -2-hydroxy] phenyl ⁇ -6- (4-methoxyphenyl) - 1,3,5-triazine (INCI: Aniso triazine, available under the trade name Tinosorb S), • dioctylbutylamidotriazon (INCI: dioctylbutamidotriazone), • 2,4-bis- [5-1 (dimethylpropyl) benzoxazol-2-yl- ( 4-phenyl) -imino] -6- (2-ethylhexyl) -imino- 1, 3,5-triazine with the (CAS No.
  • triazine derivatives which are advantageous according to the invention also include bis-resorcinyltriazine derivatives. They are characterized by the following structural formula:
  • 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 represent a single hydrogen atom.
  • 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 represent a single hydrogen atom.
  • Ethylhexyloxylpheno! Methoxyphenyl triazine which is available under the trade name Tinosorb® S from CIBA-Chemicals GmbH.
  • Another preferred bis- Resorcinyltriazine derivative is the 2- [4,6-bis (2,4-dimethylphenyl) -1, 3,5-triazin-2-yl] -5- (octyloxy) phenol (CAS No .: 2725-22-6 ).
  • the total amount of one or more bis-resorcinyltriazine derivatives in the finished cosmetic preparations is advantageously chosen from the range from 0.01% by weight to 20% by weight, preferably from 0.1 to 10% by weight, based in each case on the Total weight of the preparations.
  • Embodiments of the present invention which are advantageous according to the invention are characterized in that they contain UV filter substances from the group of the triazine derivatives in a concentration of 0.01 to 20% by weight, based on the total weight of the preparation.
  • the preparation or use according to the present invention contains further UV filter substances.
  • UV filter substances for the purposes of the present invention are those mentioned below, which can be present in the water and / or the oil phase.
  • UV filter substances which are liquid at room temperature for the purposes of the present invention are 2-ethylhexyl-2-cyano-3,3-diphenylacrylate (INCI: octocrylene) and esters of cinnamic acid, preferably 4-methoxycinnamic acid (2-ethylhexyl) ester (2- Ethylhexyl-4-methoxycinnamate, INCI: octyl methoxycinnamate) and 4-methoxycinnamate, isopentyl ester (isopentyl-4-methoxycinnamate, INCI: isoamyl p-methoxycinnamate), 3- (4- (2,2-bis-ethoxycarbonylvinyl) phenoxy) propenoxane methoxysiloxane / Dimethylsiloxane - copolymer which is available, for example, from Hoffmann La Röche under the trade name Parsol® SLX.
  • UV-A filter substances for the purposes of the present invention are dibenzoyl methane derivatives, in particular 4- (tert-butyl) -4'-methoxydibenzoylmethane (CAS No. 70356-09-1), which is available from Givaudan under the Parsol brand ® 1789 and is sold by Merck under the trade name Eusolex® 9020.
  • dibenzoyl methane derivatives in particular 4- (tert-butyl) -4'-methoxydibenzoylmethane (CAS No. 70356-09-1), which is available from Givaudan under the Parsol brand ® 1789 and is sold by Merck under the trade name Eusolex® 9020.
  • UV-A filter substances in the sense of the present invention are hydroxybenzophenones, which are characterized by the following structural formula:
  • R 1 and R 2 are independently hydrogen, CC 2 o-alkyl, C 3 -C 10 cycloalkyl or C 3 -C ⁇ 0 -
  • Nitrogen atom to which they are attached can form a 5- or 6-ring and
  • R 3 represents a CC 2 o-alkyl radical.
  • a particularly advantageous hydroxybenzophenone in the context of the present invention is 2- (4'-diethylamino-2'-hydoxybenzoyl) benzoic acid hexyl ester (also: aminobenzophenone), which is distinguished by the following structure:
  • UV filter substances in the sense of the present invention are sulfonated, water-soluble UV filters, such as. B .: • Phenylene-1,4-bis (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid and its salts, especially the corresponding sodium, potassium or triethanolammonium salts, in particular phenylene-1,4 -bis- (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid bis-sodium salt with the INCI name bisimidazylate (CAS no .: 180898-37-7), which, for example, under the trade name Neo Heliopan AP is available from Haarmann &Reimer;
  • Sulfonic acid derivatives of 3-benzylidene camphor such as. B. 4- (2-oxo-3-bornylidene methyl) benzenesulfonic acid, 2-methyl-5- (2-oxo-3-bomylidene methyl) sulfonic acid and salts thereof.
  • 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.
  • An advantageous broadband filter for the purposes of the present invention is also 2,2'-methylene-bis- (6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol ), which is available under the trade name Tinosorb® M from CIBA-Chemicals GmbH.
  • Another advantageous broadband filter for the purposes of the present invention is 2- (2H-benzotriazol-2-yl) -4-methyl-6- [2-methyl-3- [1,3,3,3-tetramethyl-1- [(trimethylsilyl) oxy] disiloxa- nyl] propyl] phenol (CAS No .: 155633-54-8) with the INCI name Drometrizole Trisiloxane.
  • the other UV filter substances can be oil-soluble or water-soluble.
  • Advantageous oil-soluble filter substances are e.g.
  • 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; Dioctylbutylamidotriazon (INCI: Diefhylhexyl Butamido Triazone), which is available under the trade name UVASORB HEB from Sigma 3V;
  • Esters of cinnamic acid preferably 4-methoxycinnamic acid (2-ethylhexyl) ester, 4-methoxycinnamic acid isopentyl ester;
  • Derivatives of benzophenone preferably 4- (
  • UV filter substances are: phenylene-1,4-bis (2-benzimidazyl) -3,3'-5,5 ' ⁇ tetrasulfonic acid bis-sodium salt (INCI: bisimidazylate, trade name: Neoheliopan AP), dioctylbutylamidotriazon (INCI : Diethylhexyl Butamido Triazone, trade name: Uvasorb HEB), 2- (4'-Diethylamino-2'-hydoxybenzoyl) -benzoic acid hexyl ester (also: aminobenzophenone) (INCI: Diethylamino Hydroxybenzoyl Hexyl Benzoate, trade name: Uvinul A plus), (3Z) - (3Z) - 1, 7,7-trimethyl-3- (4-methylbenzylidene) bicyclo [2.2.1] heptan-2-one (INCI: 4-methylbenzylidene camphor, trade name: Eusole
  • these additional UV filter substances can advantageously be present in a total concentration of 0.01 to 20% by weight and preferably in accordance with the invention in a total concentration of 0.5 to 10% by weight, in each case based on the total weight of the preparation.
  • the one or more emulsifiers A are preferably selected from the group of fatty acids which are wholly or partly neutral with customary alkalis (such as sodium and / or potassium hydroxide, sodium and / or potassium carbonate and mono- and / or triethanolamine) - are listed.
  • customary alkalis such as sodium and / or potassium hydroxide, sodium and / or potassium carbonate and mono- and / or triethanolamine
  • stearic acid and stearates, isostearic acid and isostearates, palmitic acid and palmitates, and myristic acid and myristates are particularly advantageous.
  • the emulsifier (s) B are preferably selected from the following group: PEG-9 stearate, PEG-8 distearate, PEG-20 stearate, PEG-8 stearate, PEG-8 oleate, PEG-25 glyceryl trioleate, PEG- 40-sorbitan lanolate, PEG-15 glyceryl ricinoleate, PEG-20 glyceryl stearate, PEG-20 glyceryl isostearate, PEG-20 glyceryl oleate, PEG-20 stearate, PEG-20 methylgiucose sesquistearate, PEG-30 glyceryl isostearate, PEG 20-glyceryl laurate, PEG-30 stearate, PEG-30 glyceryl stearate, PEG-40 stearate, PEG-30 glyceryl laurate, PEG-50 stearate, PEG-100 stearate, PEG-150 laurate. Polye
  • the co-emulsifier (s) C are preferably selected from the following group: behenyl alcohol (C 22 H 45 OH), cetearyl alcohol [a mixture of cetyl alcohol (C 16 H 33 OH) and stearyl alcohol (C 18 H 37 OH)], lanolin alcohols (wool wax alcohols , which represent the unsaponifiable alcohol fraction of the wool wax which is obtained after the saponification of wool wax). Cetyl and cetyl stearyl alcohol are particularly preferred.
  • weight ratios of emulsifier A to emulsifier B to coemulsifier C (A: B: C) as a: b: c, where a, b and c independently of one another are rational numbers from 1 to 5, preferably from 1 can represent up to 3.
  • a weight ratio of approximately 1: 1: 1 is particularly preferred.
  • the total amount of emulsifiers A and B and of coemulsifier C is advantageous for the total amount of emulsifiers A and B and of coemulsifier C to be in the range from 2 to 20% by weight, advantageously from 5 to 15% by weight, in particular from 7 to 13% by weight. %, based on the total weight of the formulation.
  • the formulations according to the present invention contain further emulsifiers.
  • Those emulsifiers which are suitable for the preparation of W / O emulsions are preferably to be used, these being able to be present both individually and in any combination with one another.
  • the further emulsifier or emulsifiers are preferably selected from the group of the hydrophilic emulsifiers.
  • Mono-, di-, trifatty acid esters of sorbitan are particularly preferred according to the invention.
  • the total amount of the further emulsifiers is advantageously chosen to be less than 5% by weight, based on the total weight of the formulation.
  • Particularly advantageous preparations in the sense of the present invention are free of mono- or diglyceryl fatty acid esters.
  • Preparations according to the invention which contain no glyceryl stearate, glyceryl isostearate, glyceryl di isostearate, glyceryl oleate, glyceryl palmitate, glyceryl myristate, glyceryl alcoholate and / or glyceryl laurate are particularly preferred.
  • the oil phase of the preparations according to the invention is advantageously selected from the group of polar lipids with a polarity ⁇ 35 mN / m.
  • Particularly advantageous lipids in the sense of the present invention are all native lipids, such as, for example, B. 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, corn oil, avocado oil and the like and those listed below.
  • UV filter substances for foam enhancement of self-foaming, foam-like, post-foaming or foamable cosmetic preparations which contain butylene glycol caprylates / caprates, C12-15 alkyl benzoates and / or D ⁇ -C12 / 13 alkyl tartrates included.
  • paraffin oil in particular and other hydrogenated polyolefins such as hydrogenated polyisobutenes, squalane and squalene are to be used advantageously for the purposes of the present invention.
  • the content of the lipids is advantageously chosen to be less than 50% by weight, preferably between 1 and 40% by weight, particularly preferably between 5 and 15% by weight, in each case based on the total weight of the foamable preparation.
  • oil upkJphase contains UV-UV-free substances
  • the oil phase of the preparations also contains nonpolar lipids in the sense of the present invention.
  • the cosmetic preparations according to the invention can be composed as usual. Preparations for skin care are particularly advantageous for the purposes of the present invention: they can be used for cosmetic sun protection, for cleaning or care of the skin and / or hair and as a make-up product in decorative cosmetics.
  • a further advantageous embodiment of the present invention consists of After-Sun products.
  • cosmetic compositions in the sense of the present invention can be used, for example, as skin protection creams, day or night creams, etc. It may be possible and advantageous to use the compositions according to the invention as the basis for pharmaceutical formulations.
  • the preparations according to the invention can also be “cleansing foams”, which are used, for example, to remove make-up and / or make-up or as a mild wash foam - possibly also for impure skin
  • cleaning foams can advantageously also be used as so-called “rinse-off” preparations which are rinsed off the skin after use
  • the cosmetic preparations according to the invention can also advantageously be in the form of a foam for the care of the hair or the scalp, in particular a foam for inserting the hair, a foam which is used for blow-drying the hair, a hairdressing foam.
  • cosmetic preparations whose main purpose is not protection against sunlight, but which nevertheless contain UV protection substances.
  • UV protection substances like antioxidants and, if desired, preservatives, also provide effective protection for the preparations themselves against spoilage.
  • Cosmetic preparations which are in the form of a sunscreen are also favorable.
  • the cosmetic preparations according to the invention are applied to the skin and / or the hair in a sufficient amount in the manner customary for cosmetics.
  • Aerosol containers according to the invention are spray devices with a filling of the liquid or pulp-like substances which are under the pressure of a propellant (compressed gas or aerosol packs).
  • propellant compressed gas or aerosol packs
  • Such containers can be equipped with valves of very different designs, which allow the contents to be removed as foam.
  • the preparations according to the present invention can furthermore advantageously be taken from propellant gas-free, mechanically operated pump atomizers (pump dispensers).
  • pump dispensers Particularly advantageous in the sense of the present invention are pump systems that work without compressed gas, but with a filter that causes special turbulence.
  • the cosmetic preparations according to the invention can also preferably be taken, for example, from two-chamber aerosol containers and applied to the skin.
  • Packaging materials which are advantageous according to the invention are containers in which there is a chamber with a filling of the liquid or slurry-like preparations under the pressure of a standing primary blowing agent located in a second chamber.
  • Such containers can be equipped with valves of very different designs, which make it possible to remove the contents of the first chamber as an emulsion or gel in any position - even with the valve downwards.
  • An advantageous embodiment are BiCan @ aerosol containers, in which the product is enclosed in a flexible bag made of metal or plastic inside the can.
  • Post-foaming compositions according to the invention are non-foamed, that is to say immediately after emerging from an aerosol container, two- or multi-phase systems - as a rule emulsions. They can already be rubbed lightly, for example in the hands or when applied and rubbed on the skin, but also by Stirring or other foaming processes can be designed into foams.
  • hydrocarbons or their mixtures with 4 or 5 carbon atoms in particular isobutane, n-pentane and isopentane, are used as (secondary) blowing agents, it is possible to delay the self-foaming after they have left the pressure packaging.
  • the pressure gas containers used are primarily cylindrical vessels made of metal (aluminum, tinplate, content ⁇ 1000 mL), protected or non-splintering glass or plastic (content ⁇ 220 mL) or splintering glass or plastic (content ⁇ 150 mL) in question, in the selection of compressive and fracture resistance, corrosion resistance, easy fillability, possibly sterilizability etc., but also aesthetic aspects, handiness, printability etc. play a role.
  • the maximum permissible operating pressure of spray cans made of metal at 50 ° C is 12 bar and the maximum filling volume at this temperature is approx. 90% of the total volume.
  • lower values for the operating pressure apply, depending on the container size and the propellant (whether liquefied, compressed or dissolved gas).
  • Cans made of tinplate, aluminum and glass are particularly advantageous for the purposes of the present invention.
  • metal cans can be painted inside (silver or gold painted), for which all commercially available interior protective paints are suitable.
  • Polyester, epoxyphenol and polyamideimide lacquers are preferred for the purposes of the present invention.
  • film laminations made of polyethylene (PE), polypropylene (PP) and / or polyethylene terephthalate (PET) inside the cans are advantageous, especially for cans made of tinplate.
  • the compressed gas containers are usually one or two, but usually three-part cylindrical, conical or other shape. If plastics are used as spray container material, they should be resistant to chemicals and sterilization temperatures, gas-tight, impact-resistant and stable against internal pressures above 12 bar. Polyacetals and polyamides are principally suitable for spray container purposes.
  • the internal structure of the spray cans and the valve construction are dependent on the intended use and the physical nature of the content - e.g. B. whether as a two-phase or three-phase system - very varied and can be determined by a person skilled in the art by simply trying out without inventive step.
  • suitable embodiments reference is made to the "Aerosol Technology Manual for Aersosol Packaging" (Wolfgang Tauscher, Melcher Verlag GmbH Heidelberg / Kunststoff, 1996).
  • Valves advantageous according to the invention can be designed with or without a riser pipe.
  • the individual parts from which valves according to the invention are usually constructed preferably consist of the following materials:
  • tinplate bare, gold or clear lacquered, foil laminated (PE, PP or PET) aluminum: bare, silver or gold lacquered, different lacquer variants, stoner mudge version
  • Seal natural or synthetic elastomers or thermoplastic (SIeeve-Gaskets, foil-laminated from PE or PP) inner and outer seals, e.g. B. from Perbunan, Buna, neoprene, butyl, CLB, LDPE, Viton, EPDM, chlorobutyl, bromobutyl and / or various compounds
  • Taper PA, POM, brass and various special materials, standard bores (e.g. 0.25 to 0.70 mm or 2 x 0.45 to 2 x 1.00 mm), different shaft diameters
  • Spring metal, particularly preferably V2A, stainless steel; Plastic and also elastomer
  • Advantageous spray heads for the purposes of the present invention are, for example, foam heads for upright use (holding the can vertically) or foam heads for overhead use with one or more channels.
  • the usual "classic" volatile, liquefied propellants such as dimethyl ether (DME) and / or linear or branched-chain hydrocarbons with two to five carbon atoms (such as, in particular, ethane, propane, butane, isobutane and / or pentane) are suitable as blowing agents, which alone or can be used in a mixture with one another.
  • DME dimethyl ether
  • hydrocarbons with two to five carbon atoms such as, in particular, ethane, propane, butane, isobutane and / or pentane
  • Compressed air and other pressurized gases such as air, oxygen, nitrogen, hydrogen, helium, krypton, xenon, radon, argon, laughing gas (N 2 0) and carbon dioxide (C0 2 ) are also advantageous as propellants in the sense of the present invention (both to be used individually as in any mixtures with one another).
  • the gases mentioned can be used individually or in any mixtures with one another.
  • the volume fraction of propellant gas is advantageously selected from the range from 0.1 to 30% by volume, based on the total volume of the filling material and propellant gas (corresponding to a volume fraction of 70 to 99.9% by volume filling material) ,
  • a particularly preferred propellant in the sense of the present invention is carbon dioxide. Foams obtainable from preparations according to the invention which contain carbon dioxide as one or the active ingredient are particularly advantageous.
  • foams according to the invention are foamed using linear or branched-chain, halogenated or non-halogenated hydrocarbons.
  • Very particularly advantageous foams can be obtained by foaming the preparations according to the invention with carbon dioxide, oxygen, compressed air, helium, krypton, xenon, radon, argon and / or nitrogen (both individually and in any mixtures with one another).
  • the cosmetic preparations according to the invention can contain cosmetic auxiliaries as are usually used in such preparations, e.g. B. preservatives, preservation aids, complexing agents, bactericides, perfumes, substances to prevent or increase foaming, dyes, pigments that have a coloring effect, thickeners , moisturizing and / or moisturizing substances, fillers that improve the feeling on the skin, fats, Oils, waxes or other common components of a cosmetic formulation such as alcohols, polyols, polymers, foam stabilizers, electrolytes, organic solvents or silicone derivatives.
  • cosmetic auxiliaries e.g. B. preservatives, preservation aids, complexing agents, bactericides, perfumes, substances to prevent or increase foaming, dyes, pigments that have a coloring effect, thickeners , moisturizing and / or moisturizing substances, fillers that improve the feeling on the skin, fats, Oils, waxes or other common components of a cosmetic 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, which is available, for example, from Lonza under the trade name Glydant TM), iodopropyl butyl carbamates (for example those under the trade names Glycacil-L, Glycacil -S available from Lonza and / or Dekaben LMB from Jan Dekker), parabens (ie alkyl p-hydroxybenzoate such as methyl, ethyl, propyl and / or butyl paraben), phenoxyethanol, ethanol, benzoic acid and the like ,
  • the preservation system usually also advantageously includes preservation aids, such as, for example, ethylhexylglycerol, glycine soya, etc.
  • Advantageous complexing agents for the purposes of the present invention are, for example, EDTA, [S, S] -ethylenediamine disuccinate (EDDS), which is available, for example, from Octel under the trade name Octaquest, pentasodium-ethylenediaminetetramethylenephosphonate, which, for. B. is available under the trade name Dequest 2046 from Monsanto and / or iminodisuccinic acid, which is available from Bayer AG under the trade names Iminodisuccinat VP OC 370 (approx. 30% solution) and Baypure CX 100.
  • EDDS EDTA
  • [S, S] -ethylenediamine disuccinate (EDDS) which is available, for example, from Octel under the trade name Octaquest
  • pentasodium-ethylenediaminetetramethylenephosphonate which, for. B.
  • Dequest 2046 from Monsanto
  • iminodisuccinic acid which is available from Bayer
  • 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 applications can be used as inexpensive but nevertheless optional antioxidants.
  • water-soluble antioxidants such as vitamins, e.g. B. ascorbic acid and its derivatives.
  • Preferred antioxidants are also vitamin E and its derivatives and vitamin A and its derivatives.
  • the amount of the antioxidants (one or more compounds) in the preparations is preferably 0.001 to 30% by weight, particularly preferably 0.05 to 20% by weight, in particular 0.1 to 10% by weight, based on the total weight of 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 add their respective concentrations from the range from 0.001 to 10% by weight, based on the total weight of the formulation choose. It is particularly advantageous if the cosmetic preparations according to the present invention contain cosmetic active ingredients, preferred active ingredients being antioxidants which can protect the skin from oxidative stress.
  • active ingredients in the sense of the present invention are natural active ingredients and / or their derivatives, such as.
  • Licochalcon can advantageously also be used as a component of plant extracts, in particular of aqueous radix Glycyrrhizae inflatae.
  • the cosmetic preparations each contain 0.001 to 10% by weight, in particular 0.05 to 5% by weight, very particularly 0.01 to 2% by weight, of an extract from Radix Glycyrrhizae inflatae on the total weight of the preparation.
  • Recipes according to the invention which, for. B. known anti-wrinkle agents such as flavone Glycoside (especially ⁇ -glycosylrutin), coenzyme Q10, vitamin E and / or derivatives and the like contain, are particularly advantageous for protection against aesthetically unattractive skin changes, such as z. B. occur with skin aging (such as dryness, roughness and formation of dry lines, itching, reduced re-greasing (e.g. after washing), visible vasodilation (telangiectasia, cuperosis), flaccidity and formation of wrinkles and fine lines, local hyper- , Hypo and incorrect pigmentation (e.g. age spots), increased susceptibility to mechanical stress (e.g. cracking) and the like). They are also advantageous against the appearance of dry or rough skin.
  • skin aging such as dryness, roughness and formation of dry lines, itching, reduced re-greasing (e.g. after washing), visible vasodilation (telangiectasia
  • the water phase of the preparations according to the present 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, butylene glycol , Ethylene glycol, ethylene glycol monoethyl or monobutyl ether, propylene glycol monomethyl, monoethyl or monobutyl ether, diethylene glycol monomethyl or monoethyl ether and analogous products, polymers, foam stabilizers, electrolytes and in particular one or more thickeners, which or which can advantageously be chosen from the group silicon dioxide, aluminum silicates, polysaccharides or their derivatives, for.
  • customary cosmetic auxiliaries such as, for example, alcohols, in particular those having a low C number, preferably ethanol and / or isoprop
  • B. hyaluronic acid, xanthan gum, hydroxypropylmethyl cellulose particularly advantageously from the group of polyacrylates, preferably a polyacrylate from the group of so-called carbopoles [from Bf. Goodrich], for example carbopoles of types 980, 981, 1382, 2984, 5984 , ETD 2020, ETD 2050, Ultrez 10, each individually or in combination.
  • the preparations according to the present invention can furthermore advantageously also contain self-tanning substances, such as, for example, dihydroxyacetone and / or melanin derivatives in concentrations of 1% by weight to 8% by weight, based on the total weight of the preparation.
  • self-tanning substances such as, for example, dihydroxyacetone and / or melanin derivatives in concentrations of 1% by weight to 8% by weight, based on the total weight of the preparation.
  • the preparations according to the present invention can also advantageously contain repellents for protection against mosquitoes, ticks and spiders and the like.
  • Z are advantageous.
  • the repellents can be used both individually and in combination.
  • Moisturizers are substances or mixtures of substances that give cosmetic preparations the property of reducing the release of moisture from the horny layer (also called transepidermal water loss (TEWL)) and / or positively influencing the hydration of the horny layer after application or distribution on the skin surface ,
  • TEWL transepidermal water loss
  • 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, methyl propanediol, biosaccaride Gum-1, glycine soya, ethylhexyloxyglycerol, pyrrolidonecarboxylic acid and urea.
  • polymeric moisturizers from the group of water-soluble and / or water-swellable and / or water-gelable polysaccharides.
  • hyaluronic acid chitosan and / or a fucose-rich polysaccharide
  • chitosan and / or a fucose-rich polysaccharide
  • Fucogel®1000 from the company SOLABIA S.A. is available.
  • Moisturizers can also advantageously be used as anti-wrinkle active ingredients to protect cosmetic skin changes, such as those used for. B. occur in skin aging, are used.
  • the cosmetic 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 mainly UV filter nor coloring effects (such as e.g. B. boron nitride etc.) and / or Aerosile ® (CAS No. 7631 -86-9).
  • emulsion I 80-97% by volume of emulsion I are foamed with 3-20% by volume of a suitable gas (for example propane / butane, compressed air, nitrogen).
  • a suitable gas for example propane / butane, compressed air, nitrogen.

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Abstract

L'invention concerne des préparations cosmétiques moussantes ou de type mousses, qui contiennent du benzoate de 2-phényléthyle. L'invention concerne également l'utilisation de benzoate de 2-phényléthyle dans des mousses cosmétiques.
PCT/EP2005/052333 2004-06-02 2005-05-20 Benzoate de 2-phenylethyle dans des mousses cosmetiques WO2005117823A1 (fr)

Applications Claiming Priority (2)

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DE200410027475 DE102004027475B4 (de) 2004-06-02 2004-06-02 2-Phenylethylbenzoat in kosmetischen Zubereitungen und die Verwendung zur Schaumverstärkung
DE102004027475.4 2004-06-02

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7364720B2 (en) 2004-07-02 2008-04-29 L'oreal Photostabilization of dibenzoylmethane UV-screening agents with arylalkyl benzoate compounds/amide-based oils and photoprotective compositions comprised thereof
US7368105B2 (en) 2004-07-02 2008-05-06 L'oreal Photostabilization of dibenzoylmethane UV-screening agents with arylalkyl benzoate/bis-resorcinyl triazine compounds and photoprotective compositions comprised thereof
EP1618868B1 (fr) 2004-07-02 2015-11-04 L'Oréal Procédé de photostabilisation d'un dérivé de dibenzoylméthane par un dérivé arylalkyl benzoate et un composé bis-résorcinyl triazine et compositions cosmétiques photoprotectrices
US9717931B2 (en) 2004-07-02 2017-08-01 L'oreal Solubilization of triazine UV-screening agents with arylalkyl benzoate compounds/amide-based oils and photoprotective compositions comprised thereof

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102007055483A1 (de) 2007-11-21 2009-05-28 Evonik Goldschmidt Gmbh Kosmetische und dermatologische Formulierungen enthaltend Isononylbenzoat
DE102008042149A1 (de) 2008-09-17 2010-03-18 Evonik Goldschmidt Gmbh Kosmetische und dermatologische Formulierungen enthaltend Phenoxyalkylester
DE102009002371A1 (de) 2009-04-15 2010-10-21 Evonik Goldschmidt Gmbh Verfahren zur Herstellung von geruchlosen Polyetheralkoholen mittels DMC-Katalysatoren und deren Verwendung in kosmetischen und/oder dermatologischen Zubereitungen
DE102010029499A1 (de) 2010-05-31 2011-12-01 Evonik Goldschmidt Gmbh Polyolpartialester zur Anwendung in Kosmetik
DE102016000349A1 (de) 2016-01-15 2016-03-17 Evonik Degussa Gmbh Ester des Poly-1,3-propandiols in kosmetischen Sonnenschutzformulierungen
EP4274541A1 (fr) 2021-01-06 2023-11-15 Evonik Operations GmbH Sphingolipides hydroxy-substitués
WO2024002746A1 (fr) 2022-07-01 2024-01-04 Evonik Operations Gmbh Compositions comprenant des agents autobronzants et certains sphingolipides et/ou certaines bases sphingoïdes

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996012467A1 (fr) * 1994-10-20 1996-05-02 The Procter & Gamble Company Compositions de soins personnels et/ou compositions cosmetiques contenant un parfum persistant
DE10051351A1 (de) * 2000-10-17 2002-04-18 Cognis Deutschland Gmbh Kosmetische Emulsionen
WO2003039510A1 (fr) * 2001-11-08 2003-05-15 Sol-Gel Technologies Ltd. Compositions contenant des huiles presentant une densite plus elevee que la densite de l'eau
WO2005009341A2 (fr) * 2003-07-11 2005-02-03 Isp Investments Inc. Compositions renfermant des phenethyl aryl esters comme agents de solubilisation destines a des composes actifs organiques

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10063342A1 (de) * 2000-12-19 2002-06-20 Beiersdorf Ag Selbstschäumende oder schaumförmige Zubereitungen
DE10063341A1 (de) * 2000-12-19 2002-06-20 Beiersdorf Ag Selbstschäumende oder schaumförmige Zubereitungen
DE10063340A1 (de) * 2000-12-19 2002-08-29 Beiersdorf Ag Selbstschäumende oder schaumförmige Zubereitungen

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996012467A1 (fr) * 1994-10-20 1996-05-02 The Procter & Gamble Company Compositions de soins personnels et/ou compositions cosmetiques contenant un parfum persistant
DE10051351A1 (de) * 2000-10-17 2002-04-18 Cognis Deutschland Gmbh Kosmetische Emulsionen
WO2003039510A1 (fr) * 2001-11-08 2003-05-15 Sol-Gel Technologies Ltd. Compositions contenant des huiles presentant une densite plus elevee que la densite de l'eau
WO2005009341A2 (fr) * 2003-07-11 2005-02-03 Isp Investments Inc. Compositions renfermant des phenethyl aryl esters comme agents de solubilisation destines a des composes actifs organiques

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7364720B2 (en) 2004-07-02 2008-04-29 L'oreal Photostabilization of dibenzoylmethane UV-screening agents with arylalkyl benzoate compounds/amide-based oils and photoprotective compositions comprised thereof
US7368105B2 (en) 2004-07-02 2008-05-06 L'oreal Photostabilization of dibenzoylmethane UV-screening agents with arylalkyl benzoate/bis-resorcinyl triazine compounds and photoprotective compositions comprised thereof
EP1618868B1 (fr) 2004-07-02 2015-11-04 L'Oréal Procédé de photostabilisation d'un dérivé de dibenzoylméthane par un dérivé arylalkyl benzoate et un composé bis-résorcinyl triazine et compositions cosmétiques photoprotectrices
US9717931B2 (en) 2004-07-02 2017-08-01 L'oreal Solubilization of triazine UV-screening agents with arylalkyl benzoate compounds/amide-based oils and photoprotective compositions comprised thereof

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DE102004027475B4 (de) 2006-08-03

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