WO1997020867A1 - Powdery complexes of hydrogen peroxide and polymers - Google Patents
Powdery complexes of hydrogen peroxide and polymers Download PDFInfo
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- WO1997020867A1 WO1997020867A1 PCT/EP1996/005252 EP9605252W WO9720867A1 WO 1997020867 A1 WO1997020867 A1 WO 1997020867A1 EP 9605252 W EP9605252 W EP 9605252W WO 9720867 A1 WO9720867 A1 WO 9720867A1
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- hydrogen peroxide
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3945—Organic per-compounds
-
- 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
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/22—Peroxides; Oxygen; Ozone
-
- 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
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/817—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions or derivatives of such polymers, e.g. vinylimidazol, vinylcaprolactame, allylamines (Polyquaternium 6)
- A61K8/8176—Homopolymers of N-vinyl-pyrrolidones. Compositions of derivatives of such polymers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q11/00—Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
- C11D3/3776—Heterocyclic compounds, e.g. lactam
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
- D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
- D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
- D06L4/12—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen combined with specific additives
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/80—Process related aspects concerning the preparation of the cosmetic composition or the storage or application thereof
- A61K2800/88—Two- or multipart kits
Definitions
- the present invention relates to a process for the production of powdery hydrogen peroxide complexes based unlös ⁇ Licher polymers of heterocyclic N-Vmylmonomeren.
- US Pat. No. 5,190,749 describes the production of powdery complexes of hydrogen peroxide and PVP from aqueous solutions in a fluidized bed process with subsequent drying. Powders of certain particle size distributions must be used for the fluidized bed process. The hydrogen peroxide addition must be dosed precisely, otherwise rubbery, sticky products are formed.
- US Pat. No. 3,376,110 describes the preparation of polymers with water-insoluble polymers based on heterocyclic N-methyllactams, an aqueous suspension of polymer and hydrogen peroxide being evaporated from the water, for example in a drying oven, to the solid state. Partially, however, is that rubber-like amorphous compositions are formed when completely dried.
- the object of the present invention was to find a simplified process for the production of powdered hydrogen peroxide polymer complexes which provides free-flowing products.
- polymer components which are insoluble are heterocyclic N-vinyl monomers, in particular homopolymers or copolymers of N-vinylmyrrolidone, N-vinylcaprolactam or Nvmylimidazole.
- the polymers can contain up to 80% by weight of further comonomers, for example vinyl esters such as vinyl acetate, vinyl propionate or vinyl butyrate or acrylic acid, methacrylic acid or the Ci-Ci alkyl esters of these acids.
- the polymers can be crosslinked physically or chemically.
- Suitable crosslinkers are, for example, cyclic amides which, in addition to an N Vmyl group, carry a further Vmyl group, for example N, N '-divmylethylene urea, N, N' divmylpropyleneurea, N, N '-divmylimidazolidone (2), N Vmyl-2 -ethylidene-pyrrolidone- (2) or N Vmyl-3-ethylidene-pipe ndmon- (2).
- Insoluble in this context means that the polymers are not soluble in water or in conventional organic solvents, with a proportion of soluble proportions of ⁇ 2% by weight.
- the preferred polymer component according to the invention is insoluble polyvinylpyrrolidone (PVP).
- the preparation of the polymers used is generally known.
- Hydrogen peroxide is used in the form of aqueous solutions, usually in the form of 3 to 70% by weight. -% ⁇ gen, preferably 30 to 60 wt. -% ⁇ gen solutions.
- the way in which hydrogen peroxide and polymer components are mixed is not critical.
- the polymer component can be mixed in solid form or as an aqueous slurry with the hydrogen peroxide solution.
- the mixing can advantageously take place with stirring.
- the formation of the complex can be carried out at temperatures in the range from 0 to 50 ° C., preferably 5 to 25 ° C.
- the duration of the reaction usually depends on the size of the batch and the desired hydrogen peroxide concentration in the Complex and can be easily determined by a person skilled in the art by means of a few simple experiments.
- the proportions are preferably chosen so that the reaction in the presence of 1 to 40, preferably 10 to
- the complex is formed in the presence of one or more surfactants.
- Surfactants are surfactants such as polysorbate fettsaureester, for example polyoxyethylene sorbitanfettsaure- ester (Tween ® 80), further Natnumdodecylsulfat, Dodecylt ⁇ am- ammonium bromide or polyethylene glycols.
- the complex formed is then freed from water by filtration, it being possible for the filtration to be carried out with the aid of conventional filters, for example multi-layer process filters or chamber filter presses.
- the filter cake can be sucked dry with air.
- the powdery complexes obtained in this way generally have water contents of 1 to 10% by weight. If a further drying is desired, this can be carried out in the usual drying devices, for example circulating air dryers or in a fluidized bed.
- the hydrogen peroxide-polymer complexes obtained by the process according to the invention are free-flowing powders with particle sizes in the range from 0.5 to 800 ⁇ m, preferably 0.8 to 125 ⁇ m, with a bulk density of 0.1 g / cm 3 to 0.4 g / cm 3 and a specific surface area (BET) of 0.8 m 2 / g to 6.0 m 2 / g. They contain hydrogen peroxide in a proportion of 0.1 to 40, preferably 0.5 to 25% by weight, particularly preferably 1 to 18% by weight, based on the total weight.
- the hydrogen peroxide complexes produced according to the invention are suitable for a multitude of applications in the field of hygiene, disinfection or for bleaching.
- a variety of everyday items can be equipped with such complexes to kill germs.
- Such articles include, for example disinfecting sponges, disinfect ⁇ ornamental equipped substances in the application example as towels, clothes or bed liner, disinfecting equipped face masks, drapes and curtains.
- insoles particularly in the area of adult incontinence, diapers, monthly hygiene and sterile burn and wound dressings.
- gloves equipped with sterility can be obtained both on the inside and outside by incorporating the products according to the invention.
- the area of application also includes equipping sports shoes, bath mats, head or neck supports. Conventional products such as wipes for the sanitary or household area can also be advantageously equipped with the products according to the invention.
- the products according to the invention can be formulated as powders and can be used both in human and in vetar hygiene or body care.
- tamponades, pads or swabs are possible in acne treatment, oral care, e.g. after extractions, since they are both anesthetic and disinfectant or as a vaginal tamponade.
- acne treatment oral care, e.g. after extractions, since they are both anesthetic and disinfectant or as a vaginal tamponade.
- creams or gels can also be used in the treatment of acne, since in addition to the disinfectant effect, peeling is achieved.
- the products can also be used to formulate cleaning compositions or tablets for cleaning dentures or cleaning braces, e.g. by pressing directly with Starke. Gargle water based on the products according to the invention are also accessible.
- the hydrogen peroxide complexes can also be used for flushing body cavities and for treating fistulas.
- non-adhesive chewing compounds can be formulated for braces wearers.
- plant boxes can be equipped with the complexes according to the invention.
- Stopper or closure materials for bottles or cans which, for example, contain medications but also beverages can also be provided with the products according to the invention and thus ensure a germicidal effect in the packaging, also in combination with desiccants.
- the complexes are also suitable for the filtration of drinks such as mineral water, fruit juices or beer
- the complexes according to the invention can also be used in air filters for air conditioning systems and in clean room technology.
- They are also suitable for bleaching, for example in bleaching creams and gels for cosmetic use, for the bleaching of wood, ivory, feathers, in the fat refining for the bleaching of fats and oils, m of foodstuffs " ⁇ ttel harmony, for example for bleaching of nuts, m the Cosmetics such as hair cosmetics (hair coloring, hair bleaching or oxidation of dyes in hair coloring) and depilation, as a component of washing bleach, as a component of varnish cleaners, as a component of pastes for brightening darkened areas or in development baths for the photo industry.
- hair cosmetics hair coloring, hair bleaching or oxidation of dyes in hair coloring
- depilation as a component of washing bleach
- varnish cleaners as a component of pastes for brightening darkened areas or in development baths for the photo industry.
- Sorbitol solution 70% by weight m H 2 0 10.0 sodium hydroxide 0.4 15 water 76.6
- Sorbitol solution 70% by weight m H 2 0 35.0 Synthetic amorphous silica 20.0 Sodium carboxymethyl cellulose 1.6
- the respective phases were obtained as air-bubble-free gels by mixing the components in a vacuum homogenizer. With the help of a special dispenser, the phases are concentrically required as a toothpaste batch.
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Abstract
The invention relates to a process for the preparation of powdery hydrogen peroxide complexes based on insoluble polymerisates of heterocyclic N-vinyl monomers, characterised in that an aqueous hydrogen peroxide solution is mixed with the polymer constituent and the complex obtained is filtered out.
Description
Pulverformige Komplexe aus Wasserstoffperoxid und PolymerenPowdery complexes of hydrogen peroxide and polymers
Beschreibungdescription
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von pulverformigen Wasserstoffperoxid-Komplexen auf Basis unlös¬ licher Polymerisate aus heterocyclischen N-Vmylmonomeren.The present invention relates to a process for the production of powdery hydrogen peroxide complexes based unlös ¬ Licher polymers of heterocyclic N-Vmylmonomeren.
Es ist allgemein bekannt, daß sich Wasserstoffperoxid bei län¬ gerer Lagerung zersetzt. Daher wurde eine-Vielzahl von Stabili satoren wie beispielsweise Polyvinylpyrrolidon eingesetzt, welche den Zersetzungsprozeß verhindern oder verlangsamen sollen.It is generally known that hydrogen peroxide decomposes on prolonged storage. Therefore, a variety of stabilizers such as polyvinylpyrrolidone were used to prevent or slow down the decomposition process.
Nach der US-A 5 008 093 lassen sich wasserfreie pulverformigeAccording to US Pat. No. 5,008,093, water-free powder can be used
Wasserstoffperoxid-Polyvinylpyrrolidon-Komplexe herstellen, indem Wasserstoffperoxid zu einer Suspension des PVP in einem wasser freien organischen Lösungsmittel gegeben und der sich bildende Komplex abfiltriert wird.Prepare hydrogen peroxide-polyvinylpyrrolidone complexes by adding hydrogen peroxide to a suspension of the PVP in a water-free organic solvent and filtering off the complex that forms.
Die Herstellung von Wasserstoffperoxid-PVP-Komplexen in wasser freiem organischen Lösungsmittel wird auch m der US-A 5 008 106 beschrieben.The preparation of hydrogen peroxide-PVP complexes in anhydrous organic solvents is also described in US Pat. No. 5,008,106.
Nachteilig an diesen Verfahren ist jedoch, daß zum einen wasser freie Losungsmittel benotigt werden, zum anderen mit hoch¬ konzentrierten Wasserstoffperoxid-Losungen gearbeitet werden muß. Außerdem kann nicht ausgeschlossen werden, daß die verwendeten organischen Lösungsmittel im Produkt verbleiben.A disadvantage of these processes, however, is that, on the one hand, water-free solvents are required and, on the other hand, highly concentrated hydrogen peroxide solutions have to be used. In addition, it cannot be excluded that the organic solvents used remain in the product.
In der US-A 5 190 749 wird die Herstellung von pulverformigen Komplexen aus Wasserstoffperoxid und PVP aus wäßrigen Losungen in einem Wirbelbettprozeß mit nachgeschalteter Trocknung beschrie¬ ben. Fur den Wirbelbettprozeß müssen Pulver bestimmter Korn- großenverteilungen eingesetzt werden. Die Wasserstoffperoxid zugäbe muß genau dosiert werden, da sonst gummiartige, klebrige Produkte entstehen.US Pat. No. 5,190,749 describes the production of powdery complexes of hydrogen peroxide and PVP from aqueous solutions in a fluidized bed process with subsequent drying. Powders of certain particle size distributions must be used for the fluidized bed process. The hydrogen peroxide addition must be dosed precisely, otherwise rubbery, sticky products are formed.
In der US A 3 376 110 ist die Herstellung von mit wasserun löslichen Polymerisaten auf Basis heterocyclischer N-Vmyllactame beschrieben, wobei eine wäßrige Aufsehlammung von Polymerisat und Wasserstoffperoxid durch Abdampfen des Wassers beispielsweise m einem Trockenofen m den festen Zustand überfuhrt wird. Nach teilig ist πedoch, daß bei vollständiger Trocknung gummiartige amorphe Zusammensetzungen entstehen.
Aufgabe der vorliegenden Erfindung war es, em vereinfachtes Verfahren zur Herstellung von pulverformigen Wasserstoffperoxid Polymer-Komplexen zu finden, welches freifließende Produkte liefert.US Pat. No. 3,376,110 describes the preparation of polymers with water-insoluble polymers based on heterocyclic N-methyllactams, an aqueous suspension of polymer and hydrogen peroxide being evaporated from the water, for example in a drying oven, to the solid state. Partially, however, is that rubber-like amorphous compositions are formed when completely dried. The object of the present invention was to find a simplified process for the production of powdered hydrogen peroxide polymer complexes which provides free-flowing products.
Demgemäß wurde ein Verfahren zur Herstellung von pulverformigen Wasserstoffperoxid-Komplexen auf Basis unlöslicher Polymerisate von heterocyclischen N Vinylmonomeren gefunden, welches dadurch gekennzeichnet ist, daß man eine wäßrige Wasserstoffperoxidlosung mit der Polymerkomponente vermischt und den gebildeten Komplex abfiltriert.Accordingly, a process for the preparation of powdery hydrogen peroxide complexes based on insoluble polymers of heterocyclic N vinyl monomers has been found, which is characterized in that an aqueous hydrogen peroxide solution is mixed with the polymer component and the complex formed is filtered off.
Als Polymerkomponente kommen erfindungsgemaß unlösliche Poly meπsate von heterocyclischen N-Vinylmonomeren in Betracht, vor allem Homo- oder Copolymerisate von N-Vmylpyrrolidon, N-Vinyl- caprolactam oder N Vmylimidazol. Die Polymerisate können bis zu 80 Gew. -% an weiterer Comonomeren enthalten, beispielsweise Vinylester wie Vinylacetat, Vinylpropionat oder Vmylbutyrat oder Acrylsaure, Methacrylsaure oder die Ci-Ci Alkylester dieser Sauren. Die Polymerisate können physikalisch oder chemisch ver netzt sein. Als Vernetzer kommen beispielsweise cyclische Amide, die neben einer N Vmylgruppe eine weitere Vmylgruppe tragen, in Betracht, beispielsweise N,N' -Divmyl-ethylenharnstoff, N,N' Divmylpropylenharnstoff , N,N' -Divmylimidazolidon (2) , N Vmyl-2-ethyliden-pyrrolidon- (2) oder N Vmyl-3 -ethyliden-pipe ndmon- (2) in Betracht. Unlöslich bedeutet in diesem Zusammen hang, daß die Polymerisate weder in Wasser noch in üblichen orga nischen Lösungsmitteln loslich sind, bei einem Anteil an lösli¬ chen Anteilen von < 2 Gew.-%. Bevorzugte Polymerkomponente ist erfindungsgemaß unlösliches Polyvinylpyrrolidon (PVP) .According to the invention, polymer components which are insoluble are heterocyclic N-vinyl monomers, in particular homopolymers or copolymers of N-vinylmyrrolidone, N-vinylcaprolactam or Nvmylimidazole. The polymers can contain up to 80% by weight of further comonomers, for example vinyl esters such as vinyl acetate, vinyl propionate or vinyl butyrate or acrylic acid, methacrylic acid or the Ci-Ci alkyl esters of these acids. The polymers can be crosslinked physically or chemically. Suitable crosslinkers are, for example, cyclic amides which, in addition to an N Vmyl group, carry a further Vmyl group, for example N, N '-divmylethylene urea, N, N' divmylpropyleneurea, N, N '-divmylimidazolidone (2), N Vmyl-2 -ethylidene-pyrrolidone- (2) or N Vmyl-3-ethylidene-pipe ndmon- (2). Insoluble in this context means that the polymers are not soluble in water or in conventional organic solvents, with a proportion of soluble proportions of <2% by weight. The preferred polymer component according to the invention is insoluble polyvinylpyrrolidone (PVP).
Die Herstellung der verwendeten Polymere ist allgemein bekannt.The preparation of the polymers used is generally known.
Wasserstoffperoxid kommt in Form wäßriger Losungen zum Einsatz, üblicherweise m Form von 3 bis 70 gew. -%ιgen, vorzugsweise 30 bis 60 gew. -%ιgen Losungen.Hydrogen peroxide is used in the form of aqueous solutions, usually in the form of 3 to 70% by weight. -% ιgen, preferably 30 to 60 wt. -% ιgen solutions.
Die Art der Vermischung von Wasserstoffperoxid und Polymer- komponente ist nicht kritisch. Man kann die Polymerkomponente m fester Form oder als wäßrige Aufschlammung mit der Wasserstoff- peroxidlosung vermischen.The way in which hydrogen peroxide and polymer components are mixed is not critical. The polymer component can be mixed in solid form or as an aqueous slurry with the hydrogen peroxide solution.
Die Vermischung kann vorteilhafterweise unter Ruhren erfolgen. Die Bildung des Komplexes kann bei Temperaturen im Bereich von 0 bis 50°C, vorzugsweise 5 bis 25°C durchgeführt werden. Die Dauer der Umsetzung richtet sich üblicherweise nach der Große des An¬ satzes und der gewünschten Wasserstoffperoxid Konzentration im
Komplex und kann durch einige einfache Versuche vom Fachmann leicht ermittelt werden.The mixing can advantageously take place with stirring. The formation of the complex can be carried out at temperatures in the range from 0 to 50 ° C., preferably 5 to 25 ° C. The duration of the reaction usually depends on the size of the batch and the desired hydrogen peroxide concentration in the Complex and can be easily determined by a person skilled in the art by means of a few simple experiments.
Die Mengenverhältnisse werden vorzugsweise so gewählt, daß die Umsetzung in Gegenwart von 1 bis 40, vorzugsweise 10 bisThe proportions are preferably chosen so that the reaction in the presence of 1 to 40, preferably 10 to
30 Gew. -%, bezogen auf den Feststoffgehalt an Polymerisat, an Wasserstoffperoxid erfolgt.30% by weight, based on the solids content of polymer, takes place in hydrogen peroxide.
In einer Ausfuhrungsform der Erfindung erfolgt die Bildung des Komplexes in Gegenwart von einem oder mehreren Tensiden. AlsIn one embodiment of the invention, the complex is formed in the presence of one or more surfactants. As
Tenside eignen sich oberflächenaktive Substanzen wie Polysorbat- fettsaureester, beispielsweise Polyoxyethylen-sorbitanfettsaure- ester (Tween®80) , weiterhin Natnumdodecylsulfat, Dodecyltπam- moniumbromid oder Polyethylenglykole.Surfactants are surfactants such as polysorbate fettsaureester, for example polyoxyethylene sorbitanfettsaure- ester (Tween ® 80), further Natnumdodecylsulfat, Dodecyltπam- ammonium bromide or polyethylene glycols.
Die oberflächenaktiven Substanzen verbleiben nach der Isolierung in dem pulverformigen Komplex und erhohen die Wirkung des Wasser Stoffperoxids .After isolation, the surface-active substances remain in the powdery complex and increase the effect of the water peroxide.
Der gebildete Komplex wird anschließend durch Filtration von Wasser befreit, wobei die Filtration mit Hilfe von üblichen Filtern, beispielsweise Emschichtenprozeßflltern oder Kammerfil- terpressen erfolgen kann. Der Filterkuchen kann mit Luft trocken- gesaugt werden.The complex formed is then freed from water by filtration, it being possible for the filtration to be carried out with the aid of conventional filters, for example multi-layer process filters or chamber filter presses. The filter cake can be sucked dry with air.
Die so erhaltenen pulverformigen Komplexe weisen im allgemeinen Wassergehalte von 1 bis 10 Gew. -% auf. Falls eine weitere Trock¬ nung gewünscht wird, kann diese m üblichen Trocknungsvorrichtun gen, beispielsweise Umlufttrocknern oder im Wirbelbett durchge- fuhrt werden.The powdery complexes obtained in this way generally have water contents of 1 to 10% by weight. If a further drying is desired, this can be carried out in the usual drying devices, for example circulating air dryers or in a fluidized bed.
Die nach dem erfindungsgemaßen Verfahren erhaltenen Wasserstoff¬ peroxid-Polymer Komplexe sind gut rieselfahige Pulver mit Korn¬ großen im Bereich von 0,5 bis 800 μm, vorzugsweise 0,8 bis 125 μm, bei einer Schuttdichte von 0,1 g/cm3 bis 0,4 g/cm3 und einer spe zifischen Oberflache (BET) von 0,8 m2/g bis 6,0 m2/g. Sie enthal¬ ten Wasserstoffperoxid m einem Anteil von 0,1 bis 40, vorzugs¬ weise 0,5 bis 25 Gew.-%, besonders bevorzugt 1 bis 18 Gew. -%, bezogen auf das Gesamtgewicht.The hydrogen peroxide-polymer complexes obtained by the process according to the invention are free-flowing powders with particle sizes in the range from 0.5 to 800 μm, preferably 0.8 to 125 μm, with a bulk density of 0.1 g / cm 3 to 0.4 g / cm 3 and a specific surface area (BET) of 0.8 m 2 / g to 6.0 m 2 / g. They contain hydrogen peroxide in a proportion of 0.1 to 40, preferably 0.5 to 25% by weight, particularly preferably 1 to 18% by weight, based on the total weight.
Die nach dem erfindungsgemaßen hergestellten Wasserstoffperoxid- Komplexe eignen sich fur eme Vielzahl von Anwendungen im Bereich der Hygiene, Desinfektion oder zur Bleichung.The hydrogen peroxide complexes produced according to the invention are suitable for a multitude of applications in the field of hygiene, disinfection or for bleaching.
So können beispielsweise eine Vielzahl von Artikeln des täglichen Bedarfs mit solchen Komplexen keimtötend ausgerüstet werden.
Solche Artikel umfassen z.B. desinfizierende Schwämme, desinfi¬ zierend ausgerüstete Stoffe in der Anwendung z.B. als Handtucher, Kleidungsstücke oder Bettauskleidung, desinfizierend ausgerüstete Gesichtsmasken, Gardinen und Vorhange. Ferner ist die Ausrüstung von Einlagen insbesondere im Bereich der adulter Inkontinenz, Windeln, in der Monatshygiene sowie bei sterilen Brand- und Wundauflagen möglich. Ebenso lassen sich steril ausgerüstete Handschuhe sowohl auf der Innen- und Außenseite durch Ein¬ arbeitung der erfindungsgemaßen Produkte erhalten. Das Einsatz- gebiet beinhaltet auch die Ausrüstung von Sportschuhen, Bade¬ matten, Kopf oder Nackenstützen. Auch konventionelle Produkte wie Wischtucher fur den sanitären oder Haushaltsbereich lassen sich mit den erfindungsgemaßen Produkten vorteilhaft ausrüsten.For example, a variety of everyday items can be equipped with such complexes to kill germs. Such articles include, for example disinfecting sponges, disinfect ¬ ornamental equipped substances in the application example as towels, clothes or bed liner, disinfecting equipped face masks, drapes and curtains. It is also possible to equip insoles, particularly in the area of adult incontinence, diapers, monthly hygiene and sterile burn and wound dressings. Likewise, gloves equipped with sterility can be obtained both on the inside and outside by incorporating the products according to the invention. The area of application also includes equipping sports shoes, bath mats, head or neck supports. Conventional products such as wipes for the sanitary or household area can also be advantageously equipped with the products according to the invention.
Ebenso können die erfindungsgemaßen Produkte als Puder formuliert werden und sowohl in der Human- als auch m der Vetennarhygiene bzw. Korperpflege eingesetzt werden.Likewise, the products according to the invention can be formulated as powders and can be used both in human and in vetar hygiene or body care.
Der Einsatz m Tamponaden, Pads oder Tupfern ist in der Akne- Behandlung, der Versorgung im oralen Bereich z.B nach Extrak tionen da sie sowohl astnngierend als auch desinfizierend wirken oder als vaginal Tamponade möglich. So lassen sich z.B. auch Wat testabchen mit den erfindungsgemaßen Wasserstoffperoxid-Komplexen ausrüsten. Bei der Akne-Behandlung können auch Cremes oder Gele eingesetzt werden, da neben der desinfizierenden Wirkung ein pee- lmg erreicht wird. In der Mundhygiene lassen sich mit den Pro¬ dukten auch Reinigungsmassen oder Tabletten fur die Gebißreini- gung oder die Reinigung von Zahnspangen formulieren z.B. durch Direktverpressen mit Starke. Gurgelwasser auf Basis der erfindungsgemaßen Produkte sind ebenfalls zuganglich. Auch fur die Spulung von Korperhohlen und zur Behandlung von Fisteln sind die Wasserstoffperoxid-Komplexe einsetzbar. Weiterhin lassen sich nicht klebende Kaumassen fur Zahnspangentrager formulieren.The use of tamponades, pads or swabs is possible in acne treatment, oral care, e.g. after extractions, since they are both anesthetic and disinfectant or as a vaginal tamponade. For example, also equip Wat testabchen with the hydrogen peroxide complexes according to the invention. Creams or gels can also be used in the treatment of acne, since in addition to the disinfectant effect, peeling is achieved. In oral hygiene, the products can also be used to formulate cleaning compositions or tablets for cleaning dentures or cleaning braces, e.g. by pressing directly with Starke. Gargle water based on the products according to the invention are also accessible. The hydrogen peroxide complexes can also be used for flushing body cavities and for treating fistulas. Furthermore, non-adhesive chewing compounds can be formulated for braces wearers.
Ferner ist der Einsatz in der Haustier-Hygiene vorteilhaft. So z.B. im Streugut und Auslagematerial fur Käfige und in Hunde- halsbandern.Use in pet hygiene is also advantageous. So e.g. in grit and display material for cages and in dog collars.
Auch m der Pflanzenzucht können Pflanzkasten mit dem erfindungs gemäßen Komplexen ausgestattet werden.Also in plant breeding, plant boxes can be equipped with the complexes according to the invention.
Stopfen- oder Verschlußmaterialien fur Flaschen oder Dosen die z.B. Medikamente aber auch Getränke enthalten lassen sich eben falls mit den erfindungsgemaßen Produkten ausstatten und sorgen so fur eine keimtötende Wirkung m der Verpackung, auch in Kombi nation mit Trockenmitteln.
Ebenso eignen sich die Komplexe zur Filtration von Getranken wie Mineralwässern, Fruchtsaften oder BierStopper or closure materials for bottles or cans which, for example, contain medications but also beverages can also be provided with the products according to the invention and thus ensure a germicidal effect in the packaging, also in combination with desiccants. The complexes are also suitable for the filtration of drinks such as mineral water, fruit juices or beer
Die erfindungsgemaßen Komplexe können weiterhin m Luftfiltern fur Klimaanlagen und m der Reinraumtechnologie angewendet werden.The complexes according to the invention can also be used in air filters for air conditioning systems and in clean room technology.
Weiterhin eignen sie sich zur Bleichung, beispielsweise in Bleichcremes und -gelen fur kosmetische Anwendung, zum Bleichen von Holz, Elfenbein, Federn, in der Fettraffination zur Bleichung von Fetten und Ölen, m der Lebensm"ιttelbehandlung, z.B. zum Bleichen von Nüssen, m der Kosmetik z.B. Haarkosmetik (Haar- farbung, Haarbleichung oder Oxidation von Farbstoffen m der Haarfarbung) und Depilation, als Bestandteil von Waschebleich mitteln, als Bestandteil von Lackreinigern, als Bestandteil von Pasten zur Aufhellung nachgedunkelter Gemaide oder in Entwick- lungsbadern fur die Fotoindustrie.They are also suitable for bleaching, for example in bleaching creams and gels for cosmetic use, for the bleaching of wood, ivory, feathers, in the fat refining for the bleaching of fats and oils, m of foodstuffs "ιttelbehandlung, for example for bleaching of nuts, m the Cosmetics such as hair cosmetics (hair coloring, hair bleaching or oxidation of dyes in hair coloring) and depilation, as a component of washing bleach, as a component of varnish cleaners, as a component of pastes for brightening darkened areas or in development baths for the photo industry.
Sie eignen sich auch zur Anwendung m Systemen zur portionsweisen Wasserentkeimung in Katastrophenfallen und Notfallsituationen, als Bestandteil regenerierbarer Desinfektionsmitteldepots m Wasserbehandlungs und aufbereitungssystemen, zur Entkeimung von Aufbewahrungsflussigkeiten fur medizinische Geratschaften, fur Sehhilfen (z.B. weiche und feste Kontaktlinsen) , als Bestandteil von Zigarettenfiltern oder als feste Komponente fur chemische Reaktionen wie Polymerisationen, Oxidationen, bei der Epoxidierung oder der Hydroxi1ierung, zur Vulkanisation von Elastomeren als Waschmittelzusatz und m anderen Lösungsmittel als Wasser, da der beladene Trager mit anderen Losungsmitteln gespult werden kann.They are also suitable for use in systems for portion-wise water disinfection in catastrophes and emergencies, as part of regenerable disinfectant depots in water treatment and treatment systems, for the disinfection of storage fluids for medical devices, for visual aids (e.g. soft and solid contact lenses), as part of cigarette filters or as solid Component for chemical reactions such as polymerizations, oxidations, during epoxidation or hydroxylation, for the vulcanization of elastomers as detergent additives and solvents other than water, since the loaded carrier can be rinsed with other solvents.
Herstellung von Wasserstoffperoxid-KomplexenProduction of hydrogen peroxide complexes
Beispiel 1example 1
400 g unlösliches Polyvinylpyrrolidon wurde bei Raumtemperatur (20°C) zu 550 g 50gew. %ιger wäßriger Wasserstoffperoxid-Losung gegeben und 1 h gerührt. Anschließend wurde das Wasser durch eine Siebfllternutsche abfiltriert und der pulverformige Komplex trocken gesaugt. Anschließend wurde der Komplex durch Umluft trocknung getrocknet und auf die gewünschte Wasserstoffperoxid- Konzentration eingestellt. Nach 2 h bei 80 °C enthielt der pulver¬ formige Komplex 25 Gew. -% Wasserstoffperoxid
Formulierung einer Zahncreme400 g of insoluble polyvinylpyrrolidone was at room temperature (20 ° C) to 550 g 50gew. % ιger aqueous hydrogen peroxide solution and stirred for 1 h. The water was then filtered off through a sieve and the powdery complex was sucked dry. The complex was then dried by forced air drying and adjusted to the desired hydrogen peroxide concentration. After 2 hours at 80 ° C., the powdery complex contained 25% by weight of hydrogen peroxide Formulation of a toothpaste
Beispiel 2Example 2
5 Formulierung einer Zweiphasen-Zahncreme5 Formulation of a two-phase toothpaste
Innere Gelphase:Inner gel phase:
Zusammensetzung in Gew. -%Composition in% by weight
1010
PVP-H202 Komplex gemäß Beispiel 1 12,0 Polyacrylsäure 1,0PVP-H 2 0 2 complex according to Example 1 12.0 polyacrylic acid 1.0
Sorbitlosung, 70 Gew. -%ιg m H20 10,0 Natriumhydroxid 0,4 15 Wasser 76,6Sorbitol solution, 70% by weight m H 2 0 10.0 sodium hydroxide 0.4 15 water 76.6
Äußere PutzkorperphaseOuter body phase
Zusammensetzung in Gew.-%Composition in% by weight
2020th
Wasser 37,7Water 37.7
Sorbitlosung, 70 Gew-%ιg m H20 35,0 Synthetische amorphe Kieselsaure 20,0 Natrium-carboxymethylcellulose 1,6Sorbitol solution, 70% by weight m H 2 0 35.0 Synthetic amorphous silica 20.0 Sodium carboxymethyl cellulose 1.6
25 Saccharin 0, Titandioxid 0, wäßrige NaOH-Losung, 10 Gew. -%ιg 2, Dinatrlummonofluorphosphat 1, Aromaol 0,525 saccharin 0, titanium dioxide 0, aqueous NaOH solution, 10% by weight ig 2, disodium monofluorophosphate 1, aroma oil 0.5
30 mikrokristallinen Kieselsaure 1,5 Natriumlaurylsulfat 1,030 microcrystalline silica 1.5 sodium lauryl sulfate 1.0
Die jeweiligen Phasen wurden durch Vermischen der Komponenten im Vakuumhomogenisator als luftblasenfreie Gele erhalten. Mit Hilfe 35 eines speziellen Spenders werden die Phasen konzentrisch als Zahnpastastrang gefordert.The respective phases were obtained as air-bubble-free gels by mixing the components in a vacuum homogenizer. With the help of a special dispenser, the phases are concentrically required as a toothpaste batch.
Beispiel 3Example 3
40 78 g Wasser, 10 g Propylenglykol und 10 g aus nach Beispiel 1 erhaltenen Komplexes wurden zu einer Suspension verarbeitet, mit 2 g Polyacrylsäure (Carbopol® 940, Fa. Goodrich) versetzt und im Vakuumhomogenisator zu einem luftblasenfreien Gel verarbeitet.40 78 g water, 10 g of propylene glycol and 10 g of complex obtained in accordance with Example 1 were processed to a suspension, mixed with 2 g polyacrylic acid (Carbopol ® 940, Fa. Goodrich) and processed in the Vakuumhomogenisator to a bubble-free gel.
45
45
Claims
1. Verfahren zur Herstellung von pulverförmigen Wasserstoff¬ peroxid-Komplexen auf Basis unlöslicher Polymerisate von heterocyclischen N-Vinylmonomeren, dadurch gekennzeichnet, daß man eine wäßrige Wasserstoffperoxid-Lösung mit der Polymerkomponente vermischt und den gebildeten Komplex abfiltriert.1. A process for the preparation of powdered hydrogen peroxide complexes based on insoluble polymers of heterocyclic N-vinyl monomers, characterized in that an aqueous hydrogen peroxide solution is mixed with the polymer component and the complex formed is filtered off.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Bildung des Komplexes in Gegenwart einer oberflächenaktiven Substanz erfolgt.2. The method according to claim 1, characterized in that the formation of the complex takes place in the presence of a surface-active substance.
3. Pulverförmige Komplexe aus Wasserstoffperoxid und unlöslichen Polymerisaten aus N-Vinylmonomeren, erhältlich nach dem Verfahren gemäß Anspruch 2. 3. Powdery complexes of hydrogen peroxide and insoluble polymers of N-vinyl monomers, obtainable by the process according to claim 2.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19545380.8 | 1995-12-05 | ||
DE19545380A DE19545380A1 (en) | 1995-12-05 | 1995-12-05 | Powdered complexes of hydrogen peroxide and polymers |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1997020867A1 true WO1997020867A1 (en) | 1997-06-12 |
Family
ID=7779259
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1996/005252 WO1997020867A1 (en) | 1995-12-05 | 1996-11-28 | Powdery complexes of hydrogen peroxide and polymers |
Country Status (2)
Country | Link |
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DE (1) | DE19545380A1 (en) |
WO (1) | WO1997020867A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20170007856A1 (en) * | 2013-12-23 | 2017-01-12 | L'oreal | Process for treating keratin fibers using a packaging article comprising an envelope and an anhydrous composition comprising an oxidizing agent |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0951901A3 (en) * | 1998-01-20 | 2001-07-11 | Intramed AG | Gel containing hydrogen peroxide |
JP2007008874A (en) * | 2005-06-30 | 2007-01-18 | Gc Corp | Pasty dental bleaching material |
FR2917972B1 (en) | 2007-06-29 | 2009-10-16 | Oreal | PASTE-FORMED ANHYDROUS COMPOSITION FOR KERATIN FIBER DECOLORATION |
FR2917974B1 (en) * | 2007-06-29 | 2009-10-16 | Oreal | ANHYDROUS COMPOSITION COMPRISING AT LEAST ONE DIRECT COLOR, AT LEAST ONE HYDROGEN PEROXIDE COMPLEX AND A PARTICULAR POLYMER AND METHOD OF COLORING USING THE SAME |
FR2917967B1 (en) * | 2007-06-29 | 2009-10-16 | Oreal | ANHYDROUS COMPOSITION IN PULVERULENT FORM COMPRISING AT LEAST ONE BENZENIC OXIDATION DYE, AT LEAST ONE COMPLEX OF HYDROGEN PEROXIDE AND A PARTICULAR POLYMER AND METHOD OF COLORING USING THE SAME |
FR2917973B1 (en) * | 2007-06-29 | 2009-10-16 | Oreal | PULLEY ANHYDROUS COMPOSITION COMPRISING AT LEAST ONE OXIDATION DYE, AT LEAST ONE HYDROGEN PEROXIDE COMPLEX AND A PARTICULAR POLYMER, AND A COLORING PROCESS USING THE SAME |
EP2011474A1 (en) | 2007-06-29 | 2009-01-07 | L'Oréal | Wasserfreie Zusammensetzung enthaltend mindestens einen Oxidationsfarbstoff und mindestens einen Komplex von Wasserstoffperoxid mit einem spezifischen Polymer, sowie Färbeverfahren mit dieser Zusammensetzung |
FR3015231B1 (en) | 2013-12-23 | 2017-02-24 | Oreal | PACKAGING ARTICLE COMPRISING AN ENVELOPE ANHYDROUS COLORING COMPOSITION COMPRISING A DIRECT COLOR, USE AND METHOD FOR COLORING KERATINIC FIBERS |
FR3015232B1 (en) | 2013-12-23 | 2016-01-08 | Oreal | PACKAGING ARTICLE COMPRISING AN ENVELOPE ANHYDROUS COLORING COMPOSITION COMPRISING AN OXIDATION COLOR, USE AND METHOD FOR COLORING KERATIN FIBERS |
FR3037795B1 (en) | 2015-06-25 | 2018-08-17 | L'oreal | PACKAGING ARTICLE COMPRISING AN ENVELOPE AND ANHYDROUS COLORING, COLORING OR OXIDIZING COMPOSITION COMPRISING A FIBROUS CLAY, AND A COMPOUND SELECTED FROM A COLORING AGENT AND / OR AN OXIDIZING AGENT; USE AND METHOD FOR COLORING AND / OR DECOLORIZING KERATIN FIBERS |
FR3060333B1 (en) | 2016-12-20 | 2020-01-17 | L'oreal | SOLID ANHYDROUS COMPOSITION FOR COLORING KERATINIC FIBERS COMPRISING A METABISULPHITE |
FR3060360B1 (en) | 2016-12-20 | 2019-05-24 | L'oreal | ANHYDROUS SOLID COMPOSITION FOR COLORING KERATIN FIBERS COMPRISING A POLYMER COMPRISING AT LEAST ONE VINYL HETEROCYCLIC MONOMER |
FR3089794B1 (en) | 2018-12-18 | 2021-01-29 | Oreal | Solid composition for dyeing or lightening keratin fibers comprising a phospholipid |
KR20210143887A (en) | 2019-04-30 | 2021-11-29 | 로레알 | Soluble packages of pre-measured powdered hair bleach |
FR3118707B1 (en) | 2021-01-08 | 2024-01-12 | Oreal | Solid composition for dyeing and/or lightening keratinous fibers |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3376110A (en) * | 1967-01-30 | 1968-04-02 | Gen Aniline & Film Corp | Solid stabilized hydrogen peroxide compositions |
WO1991007184A1 (en) * | 1989-11-08 | 1991-05-30 | Gaf Chemicals Corporation | SUBSTANTIALLY ANHYDROUS COMPLEXES OF PVP and H2O¿2? |
-
1995
- 1995-12-05 DE DE19545380A patent/DE19545380A1/en not_active Withdrawn
-
1996
- 1996-11-28 WO PCT/EP1996/005252 patent/WO1997020867A1/en active Application Filing
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3376110A (en) * | 1967-01-30 | 1968-04-02 | Gen Aniline & Film Corp | Solid stabilized hydrogen peroxide compositions |
WO1991007184A1 (en) * | 1989-11-08 | 1991-05-30 | Gaf Chemicals Corporation | SUBSTANTIALLY ANHYDROUS COMPLEXES OF PVP and H2O¿2? |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20170007856A1 (en) * | 2013-12-23 | 2017-01-12 | L'oreal | Process for treating keratin fibers using a packaging article comprising an envelope and an anhydrous composition comprising an oxidizing agent |
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