EP1986598A1 - Capsule de filtre anti-uv contenant une hydroxybenzophenone aminosubstituee - Google Patents

Capsule de filtre anti-uv contenant une hydroxybenzophenone aminosubstituee

Info

Publication number
EP1986598A1
EP1986598A1 EP07702770A EP07702770A EP1986598A1 EP 1986598 A1 EP1986598 A1 EP 1986598A1 EP 07702770 A EP07702770 A EP 07702770A EP 07702770 A EP07702770 A EP 07702770A EP 1986598 A1 EP1986598 A1 EP 1986598A1
Authority
EP
European Patent Office
Prior art keywords
capsule
methylpropyl
methylbutyl
amino
oil
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP07702770A
Other languages
German (de)
English (en)
Inventor
Frank Pfluecker
Hansjuergen Driller
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Merck Patent GmbH
Original Assignee
Merck Patent GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Merck Patent GmbH filed Critical Merck Patent GmbH
Publication of EP1986598A1 publication Critical patent/EP1986598A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier 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
    • A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/11—Encapsulated compositions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/41—Amines
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/41—Amines
    • A61K8/415—Aminophenols
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/44—Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof
    • A61K8/445—Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof aromatic, i.e. the carboxylic acid directly linked to the aromatic ring
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/02—Preparations containing skin colorants, e.g. pigments

Definitions

  • the present invention relates to UV filter capsules, their use for the preparation of cosmetic or dermatological formulations or preformulations and cosmetic or dermatological
  • UVC range rays with a wavelength smaller than 290 nm
  • UVB radiation rays in the range between 290 nm and 320 nm
  • UVA range Radiation in the range between about 320 nm and 400 nm (UVA range) has also been shown to cause damage to the elastic and collagen fibers of the connective tissue, prematurely aging the skin. Furthermore, these rays are the cause of numerous phototoxic and photoallergic reactions. The damaging effect of UVB radiation can be exacerbated by UVA radiation.
  • the UVA radiation may also cause skin damage by damaging the skin's own keratin or elastin. This reduces the elasticity and water retention capacity of the skin, i. The skin becomes less supple and tends to wrinkle. The remarkably high oU
  • UV radiation can also lead to photochemical reactions, in which case the photochemical reaction products intervene in the skin metabolism.
  • UV radiation counts as ionizing radiation.
  • ionic species may also be formed on exposure to UV radiation, which in turn may oxidatively interfere with the biochemical processes.
  • UVA or UVB filters The light protection filters used today in cosmetics and dermatology are therefore also subdivided into UVA or UVB filters.
  • UVB radiation numerous compounds are known, which are mostly derivatives of the 3-benzylidene camphor (e.g., Eusolex® 6300), 4-aminobenzoic acid, cinnamic acid, salicylic acid, benzophenone, as well as 2-phenylbenzimidazole.
  • dibenzoylmethane derivatives are often used, e.g.
  • a first subject of the present invention is therefore a UV filter capsule containing at least one amino-substituted hydroxybenzophenone.
  • Suitable capsules may comprise walls of inorganic or organic polymers.
  • US Pat. No. 6,242,099 B1 describes the preparation of suitable capsules having walls of chitin, chitin derivatives or polyhydroxylated polyamines.
  • Capsules which are particularly preferred for use in accordance with the invention have walls which can be obtained by a SolGel process, as described in applications WO 00/09652, WO 00/72806, WO 00/71084 and WO 03/39510.
  • capsules whose walls are made up of silica gel (silica, undefined silicon oxide hydroxide) are preferred.
  • the production of such capsules is known to the person skilled in the art, for example, from the cited patent applications, the contents of which are expressly also part of the subject of the present application.
  • step a) an oil-in-water emulsion of the hydrophobic solution containing the sol-gel precursor, at least one amino-substituted hydroxybenzophenone and optionally at least a cosmetic oil and / or at least one further UVB filter, prepared in an aqueous solution
  • step b) this emulsion of step a) is mixed to another aqueous solution, so that the condensation polymerization reaction is accelerated and optionally in step c) separating reaction products from the sol-gel precursor.
  • the resulting capsules can be isolated by means which are familiar to the person skilled in the art. For example, they can be centrifuged or filtered. A particularly preferred type of insulation is spray drying.
  • step c a suspension is obtained containing the UV filter capsules according to the invention in a form which can be used directly in cosmetic or dermatological preparations.
  • a re-suspension of the isolated capsules in, for example, deionized water or in another medium is conceivable and suitable for use in the preparations according to the invention.
  • the hydrophobic solution from step a) and also the aqueous solutions from step a) and b) may contain surfactants and / or other additives which can improve this process and / or the product.
  • the sol-gel precursor can be a metal or semimetal alkoxide monomer, a metal ester, a semimetal ester or a partially hydrolyzed and partially condensed polymer, or a mixture thereof.
  • Suitable and preferred sol-gel precursors are also compounds of the formula M (R) n (P) m, where M is a metal or semimetal, preferably Si, R is a hydrolyzable substituent and n is an integer from 2 to 4, P is not polymerizable substituent and m is an integer of 0 to 4 or a partially hydrolyzed or partially condensed polymer thereof or any mixture thereof.
  • tetraethyl orthosilicate or a partially hydrolyzed or partially condensed polymer thereof or a mixture thereof in the method described above.
  • tetraethyl orthosilicate is used as a sol-gel precursor. Further details are disclosed in the embodiments.
  • hydrophilicity of the capsule wall can be adjusted independently of the solubility of the UV filter.
  • hydrophobic UV filters can also be incorporated into purely aqueous formulations.
  • Formulations can thus be provided an improved UV-A protection.
  • the high UVA absorber content in the capsules provide excellent light protection properties for day care products, which are to protect continuously against UV-A radiation.
  • the capsules are so small that they can not be observed with the naked eye. To achieve the o.g. Effects it is still necessary that the capsules are sufficiently stable and donate the encapsulated active ingredient (UV filter) not or only to a small extent to the environment.
  • UV filter encapsulated active ingredient
  • compounds of the formula I used as amino-substituted hydroxybenzophenone derivatives are preferably:
  • R 1 and R 2 is hydrogen, Ci-C 20 alkyl, C 2 -C 0 alkenyl, C 3 -C 0 cycloalkyl, C 3 -Cio-cycloalkenyl, wherein the substituents R 1 and R 2 together with the nitrogen atom to which they are attached can form a 5- or 6-membered ring;
  • R 5 to R 7 is hydrogen, Ci-C 20 alkyl, C 2 -C 0 alkenyl, C 3 -C 0 cycloalkyl, C 3 -Cio-cycloalkenyl, - (YO) 0 -Z, aryl;
  • Z is -CH 2 -CH 3 , -CH 2 -CH 2 -CH 3 , -CH 2 -CH 2 -CH 2 -CH 3 ,
  • Alkyl radicals R 1 to R 7 are branched or unbranched C 1 -C 2 0 -alkyl chains, preferably methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1, 1-dimethylethyl , n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1, 1-dimethylpropyl, 1, 2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl , 3-methylpentyl, 4-methylpentyl, 1, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethyl butyl, 2-e
  • Alkenyl radicals R 1 to R 7 are branched or unbranched C2-C 10 - alkenyl, vinyl, propenyl, isopropenyl, 1-butenyl, 2-butenyl, 1-pentenyl, 2-pentenyl, preferably 2-methyl-1-butenyl, 2 Methyl-2-butenyl, 3-methyl-1-butenyl, 1-hexenyl, 2-hexenyl, 1-heptenyl, 2-heptenyl, 1-octenyl or 2-octenyl.
  • R 1 to R 7 are preferably branched or unbranched C 3 -C 10 -cycloalkyl chains such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, 1-methylcyclopropyl, 1-ethylcyclopropyl, 1-propylcyclopropyl, 1-butylcyclopropyl, 1 Pentylcyclopropyl, 1-methyl-1-butylcyclopropyl, 1,2-dimethylcyclopropyl, i-methyl-2-ethylcyclopropyl, cyclooctyl, cyclononyl or cyclodecyl.
  • C 3 -C 10 -cycloalkyl chains such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, 1-methylcyclopropyl, 1-ethylcyclopropy
  • cycloalkenyl radicals R 1 to R 7 are preferably branched or unbranched, C 3 -C 0 cycloalkenyl chains having one or more double bonds such as cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, 1, 3-cyclohexadienyl, 1, 4-cyclohexadienyl , Cycloheptenyl, cycloheptatrienyl, cyclooctenyl, 1,5-cyclooctadienyl, cyclooctatetraenyl, cyclononenyl or cyclodecyl.
  • the cycloalkenyl and cycloalkyl radicals may optionally be substituted by one or more, e.g. B. 1 to 3 radicals such as halogen z. Fluorine, chlorine or bromine, cyano, nitro, amino, Ci-C 4 alkylamino, Ci-C 4 dialkylamino, hydroxy, dC 4 alkyl, dC 4 -alkoxy or other radicals, or contain 1 to 3 hetero atoms such as Sulfur, nitrogen, whose free valences through
  • Hydrogen or C 1 -C 4 alkyl may be saturated or contain oxygen in the ring.
  • Suitable alkoxy radicals for R 3 and R 4 are those having 1 to 12 C atoms, preferably having 1 to 8 C atoms.
  • Alkoxycarbonyl for R 3 and R 4 are z.
  • B esters which contain the abovementioned alkoxy radicals or radicals of higher alcohols, eg. B. with up to 20 C-atoms, such as iso-Ci 5- alcohol, included.
  • Suitable mono- or dialkylamino radicals for R 3 and R 4 are those which contain alkyl radicals having 1 to 12 C atoms, such as, for example, methyl, n-propyl, n-butyl, 2-methylpropyl, 1, 1 Dimethylpropyl, hexyl, heptyl, 2-ethylhexyl, isopropyl, 1-methylpropyl, n -pentyl, 3-methylbutyl, 2, 2-dimethylpropyl, 1-methyl-1-ethylpropyl and octyl ,
  • Aryl is to be understood as meaning aromatic rings or ring systems having 6 to 18 carbon atoms in the ring system, for example phenyl or naphthyl, which may optionally be substituted by one or more radicals, such as halogen, for example. Fluorine, chlorine or bromine, cyano, nitro, amino, Ci-C 4 alkylamino, CrC ⁇ dialkylamino, hydroxy, dC 4 alkyl, -C 4 -alkoxy or other radicals, may be substituted. Preference is given to substituted or unsubstituted phenyl, methoxyphenyl and naphthyl.
  • Heteroaryl radicals are advantageously simple or fused aromatic ring systems having one or more heteroaromatic 3- to 7-membered rings.
  • heteroatoms one or more nitrogen, sulfur and / or oxygen atoms may be contained in the ring or ring system.
  • Hydrophilic that is, the water solubility of the compounds of formula I enabling radicals R 3 and R 4 are, for example, the nitrile group and carboxy ⁇ and sulfoxy and in particular their salts, salts with any physiologically acceptable cations such as alkali metal salts or as the trialkylammonium such as tri- (hydroxyalkyl) ammonium salts or the 2-methylpropane-1 -ol-2-ammonium salts. Also suitable are ammonium radicals, in particular alkylammonium radicals with any physiologically acceptable anions.
  • the substituents R 1 and R 2 may together with the nitrogen atom to which they are attached form a 5- or 6-membered ring, for example a pyrrolidine or piperidine ring.
  • the amino group can be in either ortho, meta or para position, relative to the carbonyl group.
  • the para position is preferred.
  • R 1 and R 2 are hydrogen, Ci-Ci 2 alkyl, wherein the substituents R 1 and R 2 together with the nitrogen atom to which they are attached, can form a 5- or 6-membered ring;
  • R 5 is hydrogen, C r Ci 2 -alkyl, C 3 -C 6 cycloalkyl.
  • R 1 , R 2 and R 5 are branched or unbranched C r Ci 2 alkyl chains, preferably methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1, 1 -Dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2, 2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1, 1-dimethylpropyl, 1, 2-dimethylpropyl, 1-methylpentyl, 2 Methylpentyl, 3-methylpentyl, 4-methylpentyl,
  • alkyl radicals for R 1 , R 2 and R 5 are methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1, 1-dimethylethyl, n-pentyl, 1 Methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 2-ethylhexyl.
  • R 5 is particularly preferable for R 5 to be cyclopropyl
  • compounds of the formula Ib have particular photostable properties in which the substituents R 1 , R 2 and R 5 are present in the combination mentioned in the following table.
  • H is H, 1, 1-dimethylethyl
  • H is cyclopropyl
  • H is cyclopentyl
  • the invention also relates to amino-substituted hydroxybenzophenones of the formula Ic,
  • R 1 and R 2 are hydrogen, C r C 8 alkyl, wherein the substituents R 1 and R 2 together with the nitrogen atom to which they are attached can form a 5- or 6-membered ring;
  • R 5 is C 2 -C 2 alkyl, C 5 -C 6 cycloalkyl
  • R 6 and R 7 is hydrogen, C r Ci 2 -alkyl, C 5 -C 6 cycloalkyl.
  • R 1 and R 2 are branched or unbranched C 1 -C 8 -alkyl chains, preferably methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1, 1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2, 2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1, 1 -Dimethylpropyl, 1, 2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2,2-dimethylbutyl, 2 , 3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethyl, 2-e
  • Ethyl 1-methylpropyl, 1-ethyl-2-methylpropyl, n-heptyl, n-octyl or 2-ethylhexyl.
  • Alkyl radicals R 5 are branched or unbranched C 2 -C 2 -alkyl, preferably ethyl, n-propyl, 1-methylethyl, n-butyl, 1 -Methylpropyl-,
  • alkyl radicals R 6 and R 7 are branched or unbranched
  • C 2 -C 2 alkyl chains preferably methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1, 1-dimethylethyl, n-pentyl, 1-methylbutyl, 2- Methyl-butyl, 3-methylbutyl, 2, 2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1, 1-dimethylpropyl, 1, 2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 1-dimethylbutyl, 1, 2-dimethylbutyl,
  • Preferred cycloalkyl radicals for R 5 to R 7 are branched or unbranched C 5 -C 6 -cycloalkyl chains, such as cyclopentyl or cyclohexyl.
  • Preferred are compounds of formula Ic, 8 -alkyl where, independently, R 1 and R 2 C r C 4 alkyl, R 5 is C 3 -C 8 alkyl and R 6 and R 7 C r C.
  • R 1 and R 2 are ethyl
  • R 5 is C 5 -C 8 alkyl
  • Particularly preferred in accordance with the invention is the use of hexyl 2- (4-diethylamino-2-hydroxybenzoyl) benzoate.
  • the compounds of the formula I to be used according to the invention are either commercially available or can be prepared as described in EP-A-1 046 391.
  • the UV filter capsules usually consist of 1 to 99 wt .-%, preferably 5 to 55 wt .-% and particularly preferably 20 to 40 wt .-% of amino-substituted hydroxybenzophenone.
  • the capsule also contains at least one cosmetic oil in addition to the amino-substituted hydroxybenzophenone.
  • This oil is preferably conventional cosmetic oils or hydrophobic UV filters that are liquid at room temperature. The choice of suitable cosmetic oils on the solubility of the selected hydroxybenzophenone compound and optionally the desired absorption spectrum prepares the skilled artisan no difficulties.
  • oils may preferably be used here (INCI names): octocrylenes, ethylhexyl methoxycinnamates, dibutyl adipates, C12-15 alkyl benzoates, C12-13 alkyl lactates, propylene glycol dicaprylates / dicaprate, diethylhexyl adipate, PEG-7 glyceryl cocoate , Caprylic / Capric Triglycerides, Ethylhexyl Ethylhexanoate, Isopropyl Alcohol, PPG-3 Myristyl Ether, Di-CI 2-13 Alkyl Tartrate, Ethanol, Hexyl Laurate, PEG-7 Hydrogenated Castor OiI, Di-CI 2-13 Alkyl Malate, Isopropyl Stearate.
  • the oil is an ester of saturated and / or unsaturated, branched and / or unbranched
  • Alkan carboxylic acids having a chain length of 3 to 30 carbon atoms and saturated and / or unsaturated, branched and / or unbranched alkylene glycols having a chain length of 2 to 30 carbon atoms.
  • the capsules in addition to the UV-A filter, also contain at least one UV-B filter, which is preferably selected from methoxycinnamic acid derivatives, salicylic acid derivatives or diphenylacrylate derivatives.
  • Suitable methoxycinnamic acid compounds include, for example, esters such as ethylhexyl methoxycinnamate (e.g., Eusolex® 2292), isopentyl 4-methoxycinnamate, e.g. as a mixture of isomers (e.g., Neo Heliopan® E 1000), and mixtures thereof.
  • esters such as ethylhexyl methoxycinnamate (e.g., Eusolex® 2292), isopentyl 4-methoxycinnamate, e.g. as a mixture of isomers (e.g., Neo Heliopan® E 1000), and mixtures thereof.
  • Suitable salicylic acid derivatives include, for example, 2-ethylhexyl salicylate (e.g., Eusolex® OS), 4-isopropylbenzyl salicylate (e.g., Megasol®), or S.S. ⁇ -trimethylcyclohexyl salicylate (e.g., Eusolex® HMS).
  • 2-ethylhexyl salicylate e.g., Eusolex® OS
  • 4-isopropylbenzyl salicylate e.g., Megasol®
  • S.S. ⁇ -trimethylcyclohexyl salicylate e.g., Eusolex® HMS
  • diphenylacrylate is 2-cyano-3,3-diphenylacrylate
  • 2-ethylhexyl acrylate for example Eusolex OCR ®; Octocrylene
  • UV filter capsule is amino-substituted
  • capsule compositions - A) capsule containing 5 to 42 wt .-% of amino-substituted hydroxybenzophenone and 58 to 95 wt .-% cinnamic acid derivative;
  • B) capsule comprising 5 to 44% by weight of amino-substituted hydroxybenzophenone and 56 to 95% by weight of diphenylacrylate derivative
  • the capsules with a high UV-A filter content, in particular 1 ⁇ , are suitable for use in the area of day care
  • A) amino-substituted hydroxybenzophenone to cinnamic acid derivative in a weight percent ratio of> 1: 1, 5 contain, preferably in a weight percent ratio of about 1: 1; respectively.
  • B) contain amino-substituted hydroxybenzophenone to diphenyl acrylate derivative in a weight percent ratio ⁇ 4: 1, preferably in a weight percent ratio of about 3: 1 included.
  • Another object of the present invention relates to the use of the capsules for the preparation of a cosmetic or dermatological preparation with photoprotective properties and formulations containing at least one amino-substituted
  • Q ⁇ hydroxybenzophenone and at least one carrier suitable for topical use characterized in that at least part of the amino-substituted hydroxybenzophenones is present in the form of a capsule according to the invention.
  • the preparation may comprise or contain, consist essentially of or consist of the said necessary or optional constituents or ingredients. Any compounds or components which may be used in the compositions are either known and are commercially available or may be synthesized by known or described methods.
  • the formulations may be an aqueous dispersion of the capsules which preferably contains 5 to 80% by weight of capsules, particularly preferably 30 to 50% by weight of capsules.
  • the preparations may be predispersions which, on the one hand, are suitable directly as a cosmetic or dermatological preparation and, on the other hand, the preparation of such preparations
  • Formulations for the preparation of a cosmetic or dermatological preparation with photoprotective properties is therefore also an object of the present application.
  • Corresponding formulations may preferably be aqueous preparations, in particular gels or oil-in-water emulsions (O / W emulsion).
  • a erfindungeashes method for producing a cosmetic or dermatological preparation with light protection properties characterized in that a capsule according to the invention is mixed with other ingredients.
  • Light protection properties are characterized in that the formulation described above is emulsified with an oil when the cosmetic or dermatological preparation is an oil-in-water emulsion (O / W emulsion).
  • the capsules in formulations according to the invention are preferably present in amounts which ensure that the encapsulated UV filters are present in the formulation in effective amounts.
  • the formulation according to the invention consists of the stated ingredients, i. it is the formulation to the above preformulation.
  • Another object of the present invention is the use of a formulation according to the invention for the preparation of a cosmetic or dermatological preparation with
  • the cosmetic or dermatological preparation having light-shielding properties may be in various forms.
  • the cosmetic or dermatological preparation is an aqueous preparation, in particular a gel, or an emulsion, in particular an oil-in-water emulsion (O / W emulsion), since in the preparation such preparations, the advantages of the formulations of the invention in a special way to advantage.
  • Another object of the present invention is accordingly also a process for the preparation of a cosmetic or dermatological preparation with light-protection properties, characterized in that a formulation according to the invention is mixed with other ingredients.
  • a formulation according to the invention is mixed with other ingredients.
  • an oil phase is emulsified into the formulation to produce an oil-in-water emulsion (O / W emulsion).
  • Emulsions containing the above-described formulation of the invention in or as the water phase are therefore a further subject of the present invention.
  • Particularly preferred are oil-in-water emulsion (O / W emulsion).
  • Emulsions of the invention are advantageous and contain z.
  • mineral oils mineral waxes - Oils such as triglycerides of capric or caprylic, further natural oils such. Castor oil;
  • Fats, waxes and other natural and synthetic fats preferably esters of fatty acids with lower C-number alcohols, e.g. with isopropanol, propylene glycol or glycerol, or esters of fatty alcohols with low C-alkanoic acids or with fatty acids;
  • Silicone oils such as dimethylpolysiloxanes, diethylpolysiloxanes, diphenylpolysiloxanes and mixed forms thereof.
  • the oil phase of the emulsions, oleogels or hydrodispersions or lipodispersions in the context of the present invention is advantageously selected from the group of esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids having a chain length of 3 to 30 carbon atoms and saturated and / or unsaturated, branched and / or unbranched alcohols having a chain length of from 3 to 30 carbon atoms, from the group of esters of aromatic carboxylic acid and saturated and / or unsaturated, branched and / or unbranched alcohols having a chain length of from 3 to 30 carbon atoms. atoms.
  • ester oils can then advantageously be selected from the group consisting of 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-hexadecyl stearate, 2-octyldodecyl palmitate, oleyl oleate, oleyl erucate, erucyl oleate, erucyl erucate and synthetic, semisynthetic and natural mixtures of such esters, eg. B. jojoba oil.
  • the oil phase can advantageously be selected from the group of branched and unbranched hydrocarbons and waxes, silicone oils, dialkyl ethers, the group of saturated or unsaturated, branched or unbranched alcohols, and fatty acid triglycerides, in particular the triglycerol esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids of one chain length from 8 to 24, in particular 12-18 C atoms.
  • the fatty acid triglycerides can be selected, for example, advantageously from the group of synthetic, semi-synthetic and natural oils, for. Olive oil, sunflower oil, soybean oil, peanut oil, rapeseed oil, almond oil, palm oil, coconut oil, palm kernel oil and the like.
  • any mixtures of such oil and wax components are also advantageous to use in the context of the present invention. It may also be advantageous, if appropriate, to use waxes, for example cetyl palmitate, as the sole lipid component of the oil phase.
  • the oil phase selected from the group 2-ethylhexyl isostearate, octyldodecanol, isotridecyl isononanoate, isoeicosane, 2-ethyl hexylcocoat, C 2 -i 5 alkyl benzoate, caprylic-capric acid triglyceride, Dicap- rylether.
  • 2-ethylhexyl isostearate mixtures of C 2 -1 5 alkyl benzoate and isotridecyl isononanoate and mixtures of C 12 -i 5 alkyl benzoate, 2-ethylhexyl isostearate and isotridecyl isononanoate.
  • hydrocarbons paraffin oil, squalane and squalene are to be used advantageously in the context of the present invention.
  • the oil phase may also have a content of cyclic or linear silicone oils or consist entirely of such oils, although it is preferred to use an additional content of other oil phase components in addition to the silicone oil or silicone oils.
  • cyclomethicone octamethylcyclotetrasiloxane
  • silicone oil to be used according to the invention.
  • Silicone oils are to be used advantageously in the context of the present invention, for example hexamethylcyclotrisiloxane, polydimethylsiloxane, poly (methylphenylsiloxane).
  • mixtures of cyclomethicone and Iso tridecylisononanoat from cyclomethicone and 2-Ethylhexylisostearat.
  • the aqueous phase of the preparations according to the invention advantageously contains alcohols, diols or polyols of low C number, and their ethers, preferably ethanol, isopropanol, propylene glycol, glycerol, ethylene glycol, ethylene glycol monoethyl or monobutyl ether, propylene glycol monomethyl, monoethyl or monobutyl ether, diethylene - Glykolmonomethyl- or -monoethylether and analogous products, also low C-number alcohols, z.
  • alcohols, diols or polyols of low C number, and their ethers preferably ethanol, isopropanol, propylene glycol, glycerol, ethylene glycol, ethylene glycol monoethyl or monobutyl ether, propylene glycol monomethyl, monoethyl or monobutyl ether, diethylene - Glykolmonomethyl- or -monoeth
  • isopropanol, 1, 2-propanediol, glycerol and in particular one or more thickening agents which or which can be advantageously selected from the group of silica, aluminum silicates, polysaccharides or their derivatives, e.g. Hyaluronic acid, xanthan gum, hydroxypropylmethylcellulose, particularly advantageous from the group of polyacrylates, preferably a polyacrylate from the group of so-called Carbopols, for example Carbopols types 980, 981, 1382, 2984, 5984, each individually or in combination.
  • Carbopols for example Carbopols types 980, 981, 1382, 2984, 5984, each individually or in combination.
  • mixtures of the abovementioned solvents are used.
  • alcoholic solvents water can be another ingredient.
  • Emulsions according to the invention are advantageous and contain, for example, the abovementioned fats, oils, waxes and other fatty substances, as well as water and an emulsifier, as customarily used for such a type of formulation.
  • emulsifiers for example, the known W / O and O / W emulsifiers can be used. It is advantageous to use further customary co-emulsifiers in the preferred O / W emulsions according to the invention.
  • O / W emulsifiers selected, primarily from the group of substances with HLB values of 11-16, very particularly advantageous with HLB values of 14.5-15.5, provided that the O / W emulsifiers saturated R and R ' ⁇ have. If the O / W emulsifiers have unsaturated radicals R and / or R ', or if isoalkyl derivatives are present, the preferred HLB value of such emulsifiers may also be lower or higher.
  • fatty alcohol ethoxylates from the group of ethoxylated stearyl alcohols, cetyl alcohols, cetyl stearyl alcohols (cetearyl alcohols). Particularly preferred are: polyethylene glycol (13) stearyl ether (steareth-13), polyethylene glycol (14) stearyl ether (steareth-14), polyethylene glycol (15) stearyl ether (steareth-15),
  • stearyl ether (steareth-20), polyethylene glycol (12) isostearyl ether 5 (isosteareth-12), polyethylene glycol (13) isostearyl ether (isosteareth-13), polyethylene glycol (14) isostearyl ether (isosteareth-14), polyethylene glycol (15) isostearyl ether (isosteareth -15), polyethylene glycol (16) - isostearyl ether (isosteareth-16), polyethylene glycol (17) isostearyl ether 0 (isosteareth-17), polyethylene glycol (18) isostearyl ether (isosteareth-18), polyethylene glycol (19) isostearyl ether (isosteareth-19), Polyethylene glycol (20) isostearyl ether (isosteareth-20), polyethylene glycol (13) cetyl ether (ceteth-13), polyethylene glycol (14) cetyl ether (ceteth-14), polyethylene glycol (15) cetyl ether (cet
  • Polyethylene glycol (24) isostearate, polyethylene glycol (25) isostearate, Polyethylene glycol (12) oleate, polyethylene glycol (13) oleate, polyethylene glycol (14) oleate, polyethylene glycol (15) oleate, polyethylene glycol (16) oleate, polyethylene glycol (17) oleate, polyethylene glycol (18) oleate, polyethylene glycol (19) oleate, polyethylene glycol ( 20) oleate,
  • the sodium laureth-11-carboxylate can be advantageously used.
  • the alkyl ether sulfate sodium laureth-4 sulfate can be advantageously used.
  • polyethylene glycol (30) cholesteryl ether can be advantageously used.
  • polyethylene glycol (25) soybean oil has been proven.
  • polyethylene glycol glycerol fatty acid esters from the group consisting of polyethylene glycol (20) glyceryl laurate, polyethylene glycol (21) glyceryl laurate, polyethylene glycol (22) glyceryl laurate, polyethylene glycol (23) glyceryl laurate, polyethylene glycol (6) glyceryl caprate / citrate, polyethylene glycol (20 ) glyceryl oleate, polyethylene glycol (20) glyceryl isostearate, polyethylene glycol (18) glyceryl oleate (cocoate).
  • polyethylene glycol (20) glyceryl laurate polyethylene glycol (21) glyceryl laurate
  • polyethylene glycol (22) glyceryl laurate polyethylene glycol (23) glyceryl laurate
  • polyethylene glycol (6) glyceryl caprate / citrate polyethylene glycol (20 ) glyceryl oleate
  • sorbitan esters from the group of polyethylene glycol (20) sorbitan monolaurate, polyethylene glycol (20) sorbitan monostearate, polyethylene glycol (20) sorbitan monoisostearate, polyethylene glycol (20) sorbitan monopalmitate, polyethylene glycol (20) sorbitan monooleate.
  • W / O emulsifiers can be used:
  • W / O emulsifiers are glyceryl monostearate,
  • Glyceryl monoisostearate glyceryl monomyristate, glyceryl monooleate, diglyceryl monostearate, Diglycerylmonoisostearat, propylene glycol monostearate, propylene glycol monoisostearate alcohol, propylene glycol monocaprylate, propylene glycol monolaurate, sorbitan monoisostearate, sorbitan monolaurate, sorbitan monocaprylate, Sorbitanmonoisooleat, sucrose distearate, cetyl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol, Isobehenyl- alcohol, selachyl alcohol, chimyl alcohol, polyethylene glycol ( 2) stearyl ether (steareth-2), glyceryl monolaurate, glyceryl monocaprinate, glyceryl mono- caprylate or PEG-30 dipolyhydroxystearate.
  • Cosmetic and dermatological preparations to be prepared according to the invention also advantageously, but not necessarily, contain inorganic pigments based on metal oxides and / or other sparingly soluble or insoluble metal compounds, in particular the oxides of titanium (TiO 2 ), zinc (ZnO), iron (eg
  • the cosmetic and / or dermatological sunscreen formulations may be composed as usual and serve for cosmetic and / or dermatological sunscreen, furthermore for the treatment, care and cleansing of the skin and / or the hair and as a make-up product in decorative cosmetics.
  • Particularly preferred according to the invention are those cosmetic and dermatological preparations which are in the form of a sunscreen.
  • these may additionally contain at least one further UVA filter and / or at least one further UVB filter and / or at least one inorganic pigment, preferably hydrophobic inorganic micropigments.
  • UV filters whose physiological harmlessness has already been demonstrated.
  • UV-A and UVB filters there are substances known in the literature, e.g.
  • Benzylidenecamphor derivatives such as 3- (4'-methylbenzylidene) -dl-camphor (for example Eusolex 6300), 3-benzylidenecamphor (for example Mexoryl® SD), polymers of N - ⁇ (2 and 4) - [(2-oxoborn-3- ylidene) methyl] benzyl ⁇ -acrylamide (eg Mexoryl® SW), N, N, N-trimethyl-4- (2-oxoborn-3-ylidenemethyl) anilinium methylsulfate (eg Mexoryl® SK) or (2-oxobrom-3-yl) yliden) toluene-4-sulfonic acid (eg Mexoryl® SL),
  • 3- (4'-methylbenzylidene) -dl-camphor for example Eusolex 6300
  • 3-benzylidenecamphor for example Mexoryl® SD
  • Benzoyl or dibenzoylmethanes such as 1- (4-tert-butylphenyl) -3- (4-methoxyphenyl) propane-1,3-dione (eg Eusolex® 9020) or 4-isopropyldibenzoylmethane (eg Eusolex® 8020),
  • Benzophenones such as 2-hydroxy-4-methoxybenzophenone (eg Eusolex® 4360) or 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its sodium salt (eg Uvinul® MS-40),
  • Methoxycinnamic acid esters such as octyl methoxycinnamate (e.g., Eusolex® 2292), isopentyl 4-methoxycinnamate, e.g. as a mixture of isomers
  • Neo Heliopan® E 1000 e.g., Neo Heliopan® E 1000
  • Salicylate derivatives such as 2-ethylhexyl salicylate (e.g., Eusolex® OS), A-isopropylbenzyl salicylate (e.g., Megasol®), or 3,3,5-trimethylcyclohexyl salicylate (e.g., Eusolex® HMS),
  • 4-aminobenzoic acid and derivatives such as 4-aminobenzoic acid, 2-ethylhexyl A- (dimethylamino) benzoate (e.g., Eusolex® 6007), ethoxylated 4-aminobenzoic acid ethyl ester (e.g., Uvinul® P25),
  • Phenylbenzimidazole sulfonic acids such as 2-phenylbenzimidazole-5-sulfonic acid and its potassium, sodium and triethanolamine salts (eg Eusolex® 232), 2,2- (1,4-phenylene) bisbenzimidazole-4,6-disulfonic acid or salts thereof (eg Neoheliopan® AP) or 2,2- (1,4-phenylene) bisbenzimidazole-6-sulfonic acid;
  • 2-cyano-3,3-diphenylacrylic acid 2-ethylhexyl ester e.g., Eusolex® OCR
  • Hexyl 2- (4-diethylamino-2-hydroxybenzoyl) benzoate e.g., Uvinul® UVA Plus, BASF.
  • UV filters can be used. These organic UV filters are usually incorporated in an amount of 0.5 to 10 weight percent, preferably 1-8 wt .-%, in cosmetic formulations.
  • organic UV filters are e.g. 2- (2H-Benzotriazol-2-yl) -4-methyl-6- (2-methyl-3- (1,3,3,3-tetramethyl) -
  • UV filters are also Methoxyflavone enschreibend the German patent application DE 10232595th
  • Organic UV filters are usually incorporated in an amount of 0.5 to 20 percent by weight, preferably 1 to 15 wt .-%, in cosmetic formulations.
  • inorganic UV filters are those from the group of titanium dioxides such as coated titanium dioxide (eg Eusolex® T-2000, Eusolex ® T-AQUA, Eusolex® T-AVO,), zinc oxides (eg Sachtotec®), iron oxides or cerium oxides conceivable , These inorganic UV filters are usually incorporated in an amount of 0.5 to 20 weight percent, preferably 2-10 wt .-%, in cosmetic preparations.
  • coated titanium dioxide eg Eusolex® T-2000, Eusolex ® T-AQUA, Eusolex® T-AVO,
  • zinc oxides eg Sachtotec®
  • iron oxides or cerium oxides conceivable
  • These inorganic UV filters are usually incorporated in an amount of 0.5 to 20 weight percent, preferably 2-10 wt .-%, in cosmetic preparations.
  • Preferred compounds having UV-filtering properties are 3- (4 '- methylbenzylidene) -dl-camphor, 1 - (4-tert-butylphenyl) -3- (4-methoxy-phenyl) - pro-pan-1, 3-dione, 4-isopropyldibenzoylmethane, 2-hydroxy-4-methoxy-benzo-phenone, octyl methoxycinnamate, 3,3,5-trimethyl-cyclo-hexyl-salicylate, 4- (Dimethylamino) benzoic acid 2-ethylhexyl ester, 2-cyano-3,3-di-phenyl-2-ethylhexyl acrylate, 2-phenyl-benzimidazole-5-sulfonic acid and their potassium, sodium and triethanol amine salts.
  • UV photoprotective filters can also be used in encapsulated form, wherein the encapsulation techniques described above can be used.
  • the UV photoprotective filters described here can be used alone or naturally also in combination, which is preferred, in sunscreens. They can be treated with UV-B / A chromophores, e.g. combined with all globally approved and known filters to enhance SPF-boosting performance through synergistic effects. They are preferably used in combination with both inorganic and organic UV-A and UV-B filters or mixtures thereof.
  • preparations according to the invention may also contain at least one
  • Photostabilizer preferably according to the formula I.
  • R 1 is selected from -C (O) CH 3 , -CO 2 R 3 , -C (O) NH 2 and -C (O) N (R 4 ) 2 ;
  • X is O or NH;
  • R 2 is a linear or branched C 3 -alkyl radical
  • R 3 represents a linear or branched C 2 o alkyl radical, all R 4 are independently H or linear or branched C 1-8 alkyl
  • R 5 represents H, a linear or branched C 1-8 alkyl radical or a linear or branched -OC 1-8 alkyl radical
  • R 6 represents a Ci- 8 alkyl, wherein the photosensor is particularly preferably 2 - (4-
  • Homocysteine sulfoximine, buthionine sulfone, penta-, hexa-, heptathionin sulfoximine) in very low tolerated dosages for example pmol to ⁇ mol / kg
  • furthermore (metal) chelators for example ⁇ -hydroxyfatty acids, palmitic acid, phytic acid, lactoferrin
  • ⁇ -hydroxy acids for example citric acid, lactic acid, malic acid
  • humic acid for example bile acid, bile extracts, BIII f, ruby, biliverdin, EDTA, EGTA and derivatives thereof, unsaturated fatty acids and derivatives thereof, vitamin C and derivatives (for example ascorbyl palmitate, magnesium ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives (for example vitamin e acetate), vitamin A and derivatives (eg, vitamin A palmitate), and benzylic benzylic resin
  • stilbenes and their derivatives (e.g., stilbene oxide, trans-stilbene oxide).
  • antioxidants are also suitable for use in the cosmetic preparations according to the invention.
  • Known and commercial mixtures are, for example, mixtures comprising, as active ingredients, lecithin, L - (+) - ascorbyl palmitate and citric acid (for example (for example Oxynex ® AP), natural tocopherols, L - (+) - ascorbyl palmitate, L - (+) -
  • Ascorbic acid and citric acid for example Oxynex ® K LIQUID
  • tocopherol extracts from natural sources 25
  • L - (+) - ascorbyl palmitate 25
  • L - (+) - ascorbic acid and citric acid for example Oxynex ® L LIQUID
  • DL- ⁇ - tocopherol L - (+) - ascorbyl palmitate
  • citric acid and lecithin eg Oxynex ® LM
  • BHT butylhydroxytoluene
  • L - (+) - ascorbyl palmitate and citric acid eg 30 Oxynex ® 2004.
  • compositions according to the invention can be used as further ingredients
  • vitamin 35 selected from vitamin A, vitamin A propionate, vitamin A palmitate, vitamin A-acetate, retinol, vitamin B, thiamin chloride hydrochloride (vitamin B 1 ), riboflavin (vitamin B 2 ), nicotinamide, vitamin C (ascorbic acid), vitamin D 1 ergocalciferol (vitamin D 2 ), vitamin E, DL- ⁇ -tocopherol, Tocopherol E acetate, tocopherol hydrogen succinate, vitamin Ki, esculin (vitamin P active ingredient), thiamine (vitamin Bi), nicotinic acid (niacin), pyridoxine, pyridoxal, pyridoxamine, (vitamin B 6 ), pantothenic acid, biotin, folic acid and Cobalamin (vitamin Bi 2 ) in the cosmetic preparations according to the invention, particularly preferably vitamin A palmitate, vitamin C and its derivatives, DL- ⁇ -tocopherol, tocopherol E acetate,
  • the preparations according to the invention may additionally contain further customary skin-sparing or skin-care active substances.
  • these may be all active ingredients known to the person skilled in the art, such as in particular flavone derivatives, chromone derivatives, compatible solutes and other active ingredients.
  • the preparation according to the invention contains at least one repellent, wherein the repellent is preferably selected from N, N-diethyl-3-methylbenzamide, 3- (acetyl-butyl-amino) -propionic acid ethyl ester, dimethyl phthalate, butopyronoxyl, 2.3 , 4,5-bis- (2-butylene) -tetrahydro-2-furaldehyde, N, N-caprylic acid diethylamide, N, N-diethylbenzamide, o-chloro-N, N-diethylbenzamide, dimethyl carboxide, di-n-propyl isocinchomeronate, 2-ethylhexane -1, 3-diol, N-octyl-bicyclohepetie-dicarboximide, piperonyl-butoxide, 1- (2-
  • the preparations according to the invention containing repellents are preferably insect repellents. Insect repellents are offered in the form of solutions, gels, sticks, rollers, pump sprays and aerosol sprays, with solutions and sprays making up the bulk of commercially available products. The basis for these two product forms are usually alcoholic or aqueous-alcoholic solutions with the addition of fatty substances and slight perfuming.
  • flavone derivatives are flavonoids and coumaranones.
  • the aglycones i. the sugar-free components, and the derivatives of flavonoids and aglycones understood.
  • flavonoid is also understood to mean anthocyanidin (cyanidin).
  • coumaranones are also understood as meaning their derivatives.
  • Preferred flavonoids are derived from flavanones, flavones, 3-hydroxy-flavones, aurones and isoflavones, in particular from flavanones, flavones, 3-hydroxyflavones and aurones.
  • the flavonoids are preferably selected from the following compounds: 4,6,3 ', 4' -Tetrahydroxyauron, quercetin, rutin, isoquercetin, eriodictyol, taxifolin, luteolin, Trishydroxyethylquercetin (Troxequercetin) trishydroxyethylrutin (troxerutin), Trishydroxyethylisoquercetin (Troxeiso- quercetin), Trishydroxyethylluteolin (troxeluteolin), ⁇ -glycosylrutin, tiliroside and their sulfates and phosphates.
  • Rutin, tiliroside, ⁇ -glycosylrutin and troxerutin are particularly preferred as active compounds according to the invention.
  • Quercetin (cyanidanol, cyanidolone 1522, meletin, sophoretine, ericin, 3,3 ', 4', 5,7-pentahydroxyflavone) is often cited as a particularly effective antioxidant (eg, CA Rice-Evans, NJ Miller, G. Paganga, Trends in Plant Science 1997, 2 (4), 152-159).
  • K. Lemanska, H. Szymusiak, B. Tyrakowska, R. Zielinski, A.E. M.F. Soffers, I.M.C.M. Rietjens; Free Radical Biology & Medicine 2001, 31 (7), 869-881 investigate the pH dependence of the antioxidant action of hydroxyflavones. Quercetin shows the highest activity of the investigated structures over the entire pH range.
  • Suitable antioxidants are further compounds of the formula II
  • R 1 to R 10 may be the same or different and are selected from - H
  • Mono- and / or oligoglycosyl radicals with the proviso that at least 4 radicals from R 1 to R 7 are OH and that at least 2 pairs of adjacent groups -OH are present in the molecule,
  • R 1 , R 3 , R 4 and R 7 "10 are H, as described in German Patent Application DE-A-10244282.
  • Chromone derivatives are preferably understood as meaning certain chromene-2-one derivatives which are suitable as active ingredients for the preventive treatment of human skin and hair against aging processes and damaging environmental influences. At the same time they show a low irritation potential for the skin, positively influence the water binding in the skin, maintain or increase the elasticity of the skin and thus promote a smoothing of the skin. These compounds preferably correspond to the formula III
  • R 3 is H or straight-chain or branched C 1 - to C 20 -alkyl groups
  • R 4 is H or OR 8 ,
  • R 5 and R 6 may be the same or different and are selected from -H, -OH,
  • R 7 is H, straight-chain or branched C 1 to C 20 -alkyl groups, a polyhydroxy compound, such as preferably an ascorbic acid residue or glycosidic residues and
  • the proportion of one or more compounds selected from flavonoids, Cromon derivatives and Coumaranonen in the inventive preparation is preferably from 0.001 to 5 Wt .-%, particularly preferably from 0.01 to 2 wt .-% based on the total preparation.
  • Particularly preferred active ingredients are, for example, also so-called compatible solutes. These are substances that are involved in the osmoregulation of plants or microorganisms and can be isolated from these organisms. Under the generic term compatible solutes also the described in the German patent application DE-A-10133202 osmolytes are taken. Suitable osmolytes are, for example, the polyols, methylamine compounds and amino acids and in each case their precursors.
  • osmolytes are understood as meaning, in particular, substances from the group of polyols, such as, for example, myo-inositol, mannitol or sorbitol and / or one or more of the osmolytically active substances mentioned below: taurine, choline, betaine, Phosphorylcholine, glycerophosphorylcholine,
  • Glutamine glycine, ⁇ -alanine, glutamate, aspartate, proline, and taurine.
  • Precursors of these substances are, for example, glucose, glucose polymers,
  • Precursors are e.g. Compounds that are converted into osmolytes by metabolic steps.
  • solute substances are selected from the group consisting of pyrimidinecarboxylic acids (such as ectoine and hydroxyectoine), proline, betaine, glutamine, cyclic diphosphoglycerate, N-acetylornithine, trimethylamine N-oxide di-myo-inositol-phosphate (DIP). , cyclic 2,3-diphosphoglycerate (cDPG), 1,1-diglycerol phosphate (DGP), ⁇ -mannosylglycerate (firoin), ⁇ -mannosylglyceramide (Firoin-A) or / and di-mannosyl-di-inositol phosphate
  • pyrimidinecarboxylic acids such as ectoine and hydroxyectoine
  • proline betaine
  • glutamine cyclic diphosphoglycerate
  • N-acetylornithine trimethylamine N-oxide di-myo-inositol
  • DMIP dimethyl methacrylate
  • optical isomer derivative, e.g. an acid, a salt or
  • esters of these compounds or combinations thereof used are (-, 1 4,5,6-tetrahydro-2-methyl-4-pyrimidinecarboxylic acid (S)) and hydroxyectoine ((S 1 S) -1, 4,5 6-tetrahydro-5
  • the pyrimidinecarboxylic acids ectoine particular These compounds stabilize enzymes and other biomolecules in aqueous solutions and organic solvents, and in particular stabilize enzymes against denaturing conditions such as salts, extreme pH, surfactants, urea , Guanidinium chloride and other compounds.
  • Ectoine and ectoine derivatives such as hydroxyectoine can be used to advantage in medicines.
  • hydroxyectoine can be used for the manufacture of a medicament for the treatment of skin diseases.
  • Other uses of hydroxyectoine and other ectoine derivatives are typically in areas where e.g. Trehalose is used as an additive.
  • ectoine derivatives, such as hydroxyectoine can be used as a protective substance in dried yeast and bacterial cells.
  • pharmaceutical products such as non-glycosylated, pharmaceutically active peptides and proteins e.g. t-PA can be protected with Ectoin or its derivatives.
  • European Patent Application EP-A-0 671 161 describes in particular that ectoine and hydroxyectoine are used in cosmetic preparations such as powders, soaps, surfactant-containing cleansing products, lipsticks, blushes, make-ups, skin care creams and sunscreen preparations.
  • a pyrimidinecarboxylic acid according to formula IV below is preferably used.
  • R 1 is a radical H or CI-8-alkyl
  • R 2 is a radical H or C 1-4 -alkyl
  • R 3 , R 4 , R 5 and R 6 are each independently a radical from the group H, OH, NH 2 and C 1-4 -alkyl.
  • Preference is given to using pyrimidinecarboxylic acids in which R 2 is a methyl or an ethyl group and R 1 or R 5 and R 6 are H.
  • pyrimidinecarboxylic acids ectoine ((S) -1, 4,5,6-tetrahydro-2-methyl-4-pyrimidinecarboxylic acid) and hydroxyectoine ((S 1 S) - 1, 4,5, 6- Tetrahydro-5-hydroxy-2-methyl-4-pyrimidine-carboxylic acid) used.
  • the preparations according to the invention preferably contain such pyrimidinecarboxylic acids
  • the compatible solutes are selected from di-myo-inositol phosphate (DIP), cyclic 2,3-diphosphoglycerate (cDPG), 1,1-diglycerol phosphate (DGP), ⁇ -mannosylglycerate ( Firoin), ⁇ -mannosylglyceramide (firoin-A) or / and dimarosyl-di-inositol phosphate (DMIP), ectoine, hydroxyectoine or mixtures thereof.
  • DIP di-myo-inositol phosphate
  • cDPG cyclic 2,3-diphosphoglycerate
  • DGP 1,1-diglycerol phosphate
  • Firoin ⁇ -mannosylglycerate
  • firoin-A ⁇ -mannosylglyceramide
  • DMIP dimarosyl-di-inositol phosphate
  • aryl oximes also preferably used is preferably 2-hydroxy-5-methyllaurophenonoxim, which also as HMLO 1 LPO or
  • preparations for example for therapy psoriasis, various forms of eczema, irritative and toxic dermatitis, UV dermatitis and other allergic and / or inflammatory diseases of the skin and the appendages.
  • Preparations according to the invention which contain an aryloxime, preferably 2-hydroxy-5-methyllaurophenone oxime, show surprising anti-inflammatory suitability.
  • the preparations preferably contain 0.01 to 10% by weight of the aryloxime, and it is particularly preferred if the preparation contains 0.05 to 5% by weight.
  • the preparation according to the invention contains at least one self-tanner.
  • HC O 6-aldo-D-fructose ninhydrin.
  • juglone 5-hydroxy-1,4-naphthoquinone
  • Lawson 2-hydroxy-1,4-naphthoquinone
  • the flavonoid diosmetin and its glycosides or sulfates can also be used. These compounds can be in the form of
  • diosmetin may preferably be used in the form of a chrysanthemum extract.
  • DHA 1, 3-dihydroxyacetone
  • the said self-tanner may be used alone or as a mixture. It is particularly preferred when DHA is used in admixture with another of the above-mentioned self-tanner.
  • the preparations according to the invention may also contain dyes and colored pigments.
  • the dyes and pigments can be selected from the corresponding positive list of the Cosmetics Regulation or EC List of cosmetic colorants. In most cases, they are identical to the food-approved dyes.
  • Color pigments are, for example, titanium dioxide, mica,
  • Iron oxides eg Fe 2 O 3 , Fe 3 O 4 , FeO (OH)
  • Advantageous dyes are, for example, carmine, Berlin blue, chrome oxide green, Ultramarine blue and / or manganese violet. It is particularly advantageous to choose the dyes and / or color pigments from the following list.
  • the Color Index Numbers are taken from the Rowe Color Index, 3rd Edition, Society of Dyers and Colourists, Bradford, England, 1971.
  • the dye one or more substances from the following group:
  • oil-soluble natural dyes such as paprika extract, ß-carotene or cochineal.
  • gel creams containing pearlescent pigments are particularly preferred.
  • Natural pearlescent pigments e.g.
  • fish-silver (guanine / hypoxanthine mixed crystals from fish scales)
  • Monocrystalline pearlescent pigments e.g. Bismuth oxychloride (BiOCl)
  • 3rd layer substrate Pigments e.g. Mica / metal oxide
  • pearlescent pigments are, for example, pulverulent pigments or castor oil dispersions of bismuth oxychloride and / or titanium dioxide and also bismuth oxychloride and / or titanium dioxide on mica. Particularly advantageous is e.g. the luster pigment listed under CIN 77163.
  • pearlescent pigment types based on mica / metal oxide are also advantageous, for example, are the following pearlescent pigment types based on mica / metal oxide:
  • pearlescent pigments which are advantageous in the context of the present invention are obtainable in numerous ways known per se.
  • other substrates besides mica can be coated with other metal oxides, such as silica and the like.
  • SiO 2 particles coated with TiO 2 and Fe 2 O 3 which are commercially available from Merck KGaA, Darmstadt, are advantageous
  • pearlescent pigments which are prepared using SiO 2 .
  • Such pigments which may additionally also have goniochromatic effects, for example, under the trade name Sicopearl ® Fantastico from BASF AG, Ludwigshafen,.
  • Colors (yellow, red, green, blue) are available from Flora Tech.
  • the glitter particles are present in mixtures with various auxiliaries and dyes (such as the dyes with the Color Index (Cl) numbers 19140, 77007, 77289, 77491).
  • the dyes and pigments can be present both individually and in a mixture and can be mutually coated with one another, wherein different coating thicknesses generally cause different color effects.
  • the total amount of dyes and coloring pigments is advantageously from the range of z. B. 0.1 wt .-% to 30 wt .-%, preferably from 0.5 to 15 wt .-%, in particular from 1, 0 to 10 wt .-%, each based on the total weight of the preparations.
  • compositions are either known and commercially available or may be synthesized by known methods. Any customary carrier substances, adjuvants and optionally further active ingredients can be added to the preparation.
  • Preferable excipients come from the group of preservatives, antioxidants, stabilizers, solubilizers, vitamins, colorants, odor improvers.
  • Solutions and emulsions may include the customary carriers such as solvents, solubilizers and emulsifiers, for example water, ethanol, isopropanol, ethyl carbonate, ethyl acetate, benzyl alcohol, benzyl benzoate, propylene glycol, 1,3-butylglycol, oils, in particular cottonseed oil, peanut oil, maize germ oil, olive oil, Castor oil and sesame oil, Glycerinfett- acid esters, polyethylene glycols and fatty acid esters of sorbitol or mixtures of these substances.
  • the preparations according to the invention contain hydrophilic surfactants.
  • the hydrophilic surfactants are preferably selected from the group of alkylglucosides, acyl lactylates, betaines and cocoamphoacetates.
  • the alkylglucosides in turn are advantageously selected from the group of alkylglucosides, which are represented by the structural formula
  • R is a branched or unbranched alkyl radical
  • the value DP represents the degree of glucosidation of the alkylglucosides used in the invention and is defined as
  • P 1 , p 2 , P 3 ••• or pi represent the proportion of single, double-threefold-fold glucosylated products in weight percentages.
  • products having degrees of glucosylation of 1-2 are particularly advantageous from 1, 1 to 1, 5, very particularly advantageous from 1, 2-1, 4, in particular selected from 1, 3.
  • the value of DP takes account of the fact that alkylglucosides, as a rule, are mixtures of mono- and oligoglucosides.
  • a relatively high content of monoglucosides typically of the order of 40%, is advantageous.
  • Alkylglylcosides used particularly advantageously according to the invention are selected from the group octylglucopyranoside, nonylglucopyranoside, decylglucopyranoside, undecylglucopyranoside, dodecylglucopyranoside, tetradecylglucopyranoside and hexadecylglucopyranoside.
  • R 1 denotes a branched or unbranched alkyl radical having 1 to 30 carbon atoms and M + is selected from the group of the alkali ions and the group of the ammonium ions substituted by one or more alkyl and / or by one or more hydroxyalkyl radicals or corresponds to half the equivalent of an alkaline earth metal ion.
  • sodium is advantageous, for example the product Pathionic ® ISL from the American Ingredients Company.
  • R 2 is a branched or unbranched alkyl radical having 1 to 30 carbon atoms.
  • R 2 is a branched or unbranched alkyl radical having 6 to 12 carbon atoms.
  • Capramidopropylbetaine for example the product Tego ® Betaine is advantageous, for example 810 from Th. Goldschmidt AG.
  • sodium elected cocoamphoacetate invention beneficial as under the name Miranol ® Ultra C32 from Miranol Chemical Corp. is available.
  • the preparations according to the invention are advantageously characterized in that the hydrophilic surfactant or surfactants in concentrations of 0.01 -20 wt .-%, preferably 0.05-10 wt .-%, particularly preferably 0.1-5 wt .-%, respectively based on the total weight of the composition, is present or present.
  • the cosmetic and dermatological preparations according to the invention are applied to the skin and / or the hair in a sufficient amount in the manner customary for cosmetics.
  • the preparation may contain cosmetic adjuvants which are commonly used in this type of preparations, e.g.
  • Thickening agents emollients, humectants, surfactants, emulsifiers, preservatives, antifoaming agents, perfumes, waxes, lanolin, propellants, dyes and / or pigments which color the agent itself or the skin, and other ingredients commonly used in cosmetics.
  • dispersion or solubilizing agent an oil, wax or other fatty substance, a low monoalcohol or a low polyol or mixtures thereof.
  • Particularly preferred monoalcohols or polyols include ethanol, i-propanol, propylene glycol, glycerine and sorbitol.
  • a preferred embodiment of the invention is an emulsion which is present as a protective cream or milk and contains, for example, fatty alcohols, fatty acids, fatty acid esters, in particular triglycerides of fatty acids, lanolin, natural and synthetic oils or waxes and emulsifiers in the presence of water.
  • the customary propellants such as alkanes, fluoroalkanes and chlorofluoroalkanes, are generally used.
  • the cosmetic preparation may also be used to protect the hair against photochemical damage to prevent changes in hues, discoloration or damage of a mechanical nature.
  • it is suitably carried out as a shampoo, lotion, gel or emulsion for rinsing, wherein the respective preparation before or after shampooing, before or after dyeing or decolorization or before or after the permanent wave is applied.
  • It can also be a preparation as a lotion or gel for styling and Treat, as a lotion or gel for brushing or laying a water wave, as a hair lacquer, permanent wave, dyeing or decolorizing the hair can be selected.
  • the photoprotective composition may contain various adjuvants used in this type of mediator, such as surfactants, thickeners, polymers, emollients, preservatives, foam stabilizers,
  • Electrolytes organic solvents, silicone derivatives, oils, waxes, anti-grease agents, dyes and / or pigments which dye the agent itself or the hair, or other ingredients commonly used for hair care.
  • the preparations according to the invention can be prepared using techniques which are well known to the person skilled in the art.
  • the substances according to the invention can be incorporated directly into cosmetic preparations without further preparatory measures.
  • the preparations according to the invention contain further UV filter substances, the total amount of filter substances being e.g. 0.1 to 30 wt .-%, preferably 0.5 to 10 wt .-%, in particular 1 to 6 wt .-%, based on the total weight of the preparations.
  • preparations according to the invention can also be used as pharmaceutical agents for the preventive treatment of inflammations and allergies of the skin as well as in certain cases for the prevention of certain types of cancer.
  • the pharmaceutical agent of the invention may be administered orally or topically.
  • Example 1 Preparation of a silica capsule containing diethylamino hydroxybenzoyl hexyl benzoates
  • a solution of 33.5 g of Uvinul A Plus, 66.5 g of dibutyl adipate and 17.7 g of tetraethyl orthosilicate is added under cooling with the aid of an emulsifying tool (Ultra Turax) in a surfactant solution (58.2 g of demineralized water and 0.69 g Cetyltrimethylammonium chloride) emulsified.
  • a surfactant solution 58.2 g of demineralized water and 0.69 g Cetyltrimethylammonium chloride
  • Residue was adjusted to 3.8 - 4.0 and filled up with deionised water.
  • the active ingredient content of the suspension is 50% by weight.
  • the incorporation into the cosmetic preparation can take place in this form.
  • the isolation of the silica capsule containing Uvinul A Plus is carried out by spray drying. A white powder is obtained.
  • a solution of 36 g of 2- (4-diethylamino-2-hydroxybenzoyl) - benzoic acid hexylester (Uvinul A Plus ®, BASF AG.), 64 g methoxycinnamate (for example Eusolex 2292; Merck). and 26.5 g of tetraethyl orthosilicate is emulsified with cooling by means of an emulsifying tool (Ultra Turax) in a surfactant solution (58.2 g of demineralized water and 0.69 g of cetyltrimethylammonium chloride). The finished emulsion is added to hydrochloric acid with stirring.
  • the resulting mixture is stirred for at least 24 h at room temperature and then allowed to stand again for at least 24 h without stirring. Thereafter, the ethanol formed during the hydrolysis of the alkylsilanes is depleted by distillation. With Na citrate solution, the pH of the residue is adjusted to 3.8-4.0. 4 g of PVP solution with 50% by weight of polyvinylpyrrolidone are added and made up to 200 g with deionized water. The active ingredient content of the suspension is 50% by weight.
  • a solution of 25 g 2- (4-diethylamino-2-hydroxybenzoyl) - benzoic acid hexylester (Uvinul A Plus ®; Fa. BASF AG), 75 g of 2-ethylhexyl (Eusolex® OS; from Merck.) And 17.7 Tetraethylorthosilicate is emulsified with cooling with the aid of an emulsifying tool (Ultra Turax) in a surfactant solution (58.2 g of deionised water and 0.69 g of cetyltrimethylammonium chloride). The finished emulsion is added to hydrochloric acid with stirring.
  • the resulting mixture is stirred for 24 h at room temperature and then allowed to stand again without stirring for 24 h. Thereafter, the ethanol formed during the hydrolysis of the alkylsilane is depleted by distillation. With Na citrate solution, the pH of the residue is adjusted to 3.8-4.0. There are 4 g of PVP solution with 50 wt.% Polyvinylpyrrolidone added and with deionized water on 200g filled. The active ingredient content of the suspension is 50% by weight.
  • Example 3a The preparation of a silica capsule containing diethylamino hydroxybenzoyl hexyl benzoate and 3,3,5-trimethylcyclohexyl salicylate (for example Eusolex® HMS) is carried out analogously to Example 3.
  • Example 6 Composition for lip care
  • Example 7 Composition for lip care
  • Example 8 Composition for Sunblocker with Micropigments
  • Example 9 Composition for sunblock with micropigments (% by weight) ad 100% water
  • Example 12 Sunscreen (SPF 20) (% By weight) ad 100 water
  • CETEARYL ALCOHOL 1 00 AQUA (WATER) 70.45 KAOLIN 8.00

Landscapes

  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Dermatology (AREA)
  • Cosmetics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne des capsules de filtres anti-UV contenant au moins une hydroxybenzophénone aminosubstituée, leur utilisation pour préparer des formulations ou préformulations cosmétiques ou dermatologiques, ainsi que des formulations cosmétiques ou dermatologiques contenant ces capsules et des procédés pour les préparer.
EP07702770A 2006-02-13 2007-01-15 Capsule de filtre anti-uv contenant une hydroxybenzophenone aminosubstituee Withdrawn EP1986598A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102006006413A DE102006006413A1 (de) 2006-02-13 2006-02-13 UV-Filter-Kapsel
PCT/EP2007/000304 WO2007093252A1 (fr) 2006-02-13 2007-01-15 Capsule de filtre anti-uv contenant une hydroxybenzophénone aminosubstituée

Publications (1)

Publication Number Publication Date
EP1986598A1 true EP1986598A1 (fr) 2008-11-05

Family

ID=37983418

Family Applications (1)

Application Number Title Priority Date Filing Date
EP07702770A Withdrawn EP1986598A1 (fr) 2006-02-13 2007-01-15 Capsule de filtre anti-uv contenant une hydroxybenzophenone aminosubstituee

Country Status (5)

Country Link
US (1) US20090035238A1 (fr)
EP (1) EP1986598A1 (fr)
JP (1) JP2009526125A (fr)
DE (1) DE102006006413A1 (fr)
WO (1) WO2007093252A1 (fr)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102007035567A1 (de) * 2007-07-26 2009-01-29 Basf Se UV-Filter-Kapsel
JP6150451B2 (ja) * 2007-12-14 2017-06-21 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ カラー顔料を含むサンスクリーン組成物
US9283160B2 (en) 2009-01-29 2016-03-15 Basf Se Stabilization of cosmetic compositions
JPWO2010110020A1 (ja) * 2009-03-26 2012-09-27 株式会社 資生堂 日焼け止め化粧料
US20130040817A1 (en) 2010-04-20 2013-02-14 Basf Se Capsule comprising active ingredient
US9549891B2 (en) 2012-03-19 2017-01-24 The Procter & Gamble Company Superabsorbent polymers and sunscreen actives for use in skin care compositions
JP6077216B2 (ja) * 2012-03-26 2017-02-08 株式会社 資生堂 油性化粧料
JPWO2015037493A1 (ja) * 2013-09-12 2017-03-02 株式会社ダイセル 無機酸化物微粒子分散組成物、及び水系化粧料
CN107787222B (zh) 2015-06-29 2020-12-04 宝洁公司 用于护肤组合物中的超吸收聚合物和淀粉粉末

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2755856B1 (fr) * 1996-11-21 1999-01-29 Merck Clevenot Laboratoires Microcapsules de chitine ou de derives de chitine contenant une substance hydrophobe, notamment un filtre solaire et procede de preparation de telles microcapsules
US6238650B1 (en) * 1999-05-26 2001-05-29 Sol-Gel Technologies Ltd. Sunscreen composition containing sol-gel microcapsules
US6468509B2 (en) * 1998-12-18 2002-10-22 Sol-Gel Technologies Ltd. Sunscreen composition containing sol-gel microcapsules
DE19917906A1 (de) * 1999-04-20 2000-10-26 Basf Ag Verwendung von aminosubstituierten Hydroxybenzophenonen als photostabile UV-Filter in kosmetischen und pharmazeutischen Zubereitungen
FR2842419A1 (fr) * 2002-07-19 2004-01-23 Oreal Procede d'elargissement du spectre d'absorption uv d'un filtre solaire uv-a et materiau obtenu par voie sol-gel contenant ledit filtre
US20080031909A1 (en) * 2004-12-10 2008-02-07 Dsm Ip Assets B.V. Encapsulated Cosmetic Materials

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2007093252A1 *

Also Published As

Publication number Publication date
JP2009526125A (ja) 2009-07-16
WO2007093252A1 (fr) 2007-08-23
US20090035238A1 (en) 2009-02-05
DE102006006413A1 (de) 2007-08-23

Similar Documents

Publication Publication Date Title
EP2170253B1 (fr) Capsule filtrant les uv
EP1660592B1 (fr) Agent anti-uv nanoparticulaire pourvu d'un revetement de dioxyde de silicium
EP1848507B1 (fr) Composition contenant un agent anti-uv nanoparticulaire
EP1763383B1 (fr) Particule fonctionnalisee avec des composes organiques
EP1720510B1 (fr) Filtre uv sous forme de poudre
EP1986598A1 (fr) Capsule de filtre anti-uv contenant une hydroxybenzophenone aminosubstituee
WO2005074897A2 (fr) Auxiliaires de formulation
EP2004136B1 (fr) Utilisation de flavonoïdes
WO2006018104A1 (fr) Filtre uv
WO2006018078A1 (fr) Complexes de flavonoides
DE102005013380A1 (de) Extraktionsverfahren
WO2007014614A1 (fr) Procede de bronzage
DE102004011111A1 (de) Formulierung zur Stabilisierung von UV-Filtern
EP1846429A2 (fr) Complexes de flavonoïdes comprenant des cyclodextrines
DE102007041854A1 (de) Bifunktionelle DHA-Derivate
DE102004045482A1 (de) UV-Filter-Mischung
WO2007065524A1 (fr) Ester d’erythrulose en tant que filtre uv

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20080326

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

RIN1 Information on inventor provided before grant (corrected)

Inventor name: DRILLER, HANSJUERGEN

Inventor name: PFLUECKER, FRANK

17Q First examination report despatched

Effective date: 20081212

DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20120606