EP1492633A1 - Formgebungsverfahren zur herstellung von formk rpern mit zum indest einer oberfl che, die selbstreinigende eigenschaften aufweist sowie mit diesem verfahren hergestellte formk rper - Google Patents
Formgebungsverfahren zur herstellung von formk rpern mit zum indest einer oberfl che, die selbstreinigende eigenschaften aufweist sowie mit diesem verfahren hergestellte formk rperInfo
- Publication number
- EP1492633A1 EP1492633A1 EP03743798A EP03743798A EP1492633A1 EP 1492633 A1 EP1492633 A1 EP 1492633A1 EP 03743798 A EP03743798 A EP 03743798A EP 03743798 A EP03743798 A EP 03743798A EP 1492633 A1 EP1492633 A1 EP 1492633A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- microparticles
- shaping
- elevations
- molded body
- particles
- 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- Withdrawn
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/58—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising fillers only, e.g. particles, powder, beads, flakes, spheres
- B29C70/64—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising fillers only, e.g. particles, powder, beads, flakes, spheres the filler influencing the surface characteristics of the material, e.g. by concentrating near the surface or by incorporating in the surface by force
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B17/00—Methods preventing fouling
- B08B17/02—Preventing deposition of fouling or of dust
- B08B17/06—Preventing deposition of fouling or of dust by giving articles subject to fouling a special shape or arrangement
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B17/00—Methods preventing fouling
- B08B17/02—Preventing deposition of fouling or of dust
- B08B17/06—Preventing deposition of fouling or of dust by giving articles subject to fouling a special shape or arrangement
- B08B17/065—Preventing deposition of fouling or of dust by giving articles subject to fouling a special shape or arrangement the surface having a microscopic surface pattern to achieve the same effect as a lotus flower
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
- B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
- B29C59/022—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing characterised by the disposition or the configuration, e.g. dimensions, of the embossments or the shaping tools therefor
- B29C2059/023—Microembossing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
- B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
- B29C2059/028—Incorporating particles by impact in the surface, e.g. using fluid jets or explosive forces to implant particles
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
- Y10T428/24372—Particulate matter
Definitions
- the present invention relates to molding processes for the production of moldings, with at least one surface which has self-cleaning properties and elevations formed by microparticles, by thermal shaping of materials comprising organic compounds by means of a molding tool, and moldings produced in this way.
- the state of the art for self-cleaning surfaces is that an aspect ratio of greater than 1 and a surface energy of less than 20 mN / m is required for such self-cleaning surfaces.
- the aspect ratio is defined here as the quotient of the medium height to the medium width of the structure.
- the aforementioned criteria are realized in nature, for example in the lotus leaf.
- the surface of a plant formed from a hydrophobic, wax-like material has elevations that are up to a few ⁇ m apart. Water droplets substantially only with the tips of the bumps' in contact. Such water-repellent surfaces have been widely described in the literature.
- the Swiss patent CH-PS 268258 describes a method in which structured surfaces are produced by applying powders such as kaolin, talc, clay or silica gel. The powders are fixed on the surface by oils and resins based on organosilicon compounds.
- hydrophobic materials such as perfluorinated polymers
- Polymers such as polytetrafluoroethylene or copolymers of polytetrafluoroethylene with
- Perfluoroalkyl vinyl ethers create hydrophobic surfaces that are structured and have low adhesion to snow and ice.
- JP 11171592 describes a water-repellent product and its production, the dirt-repellent surface being produced by applying a film to the one to be treated
- Substrate to which the film has been applied are sintered at temperatures above 400 ° C. This method can therefore only be used for substrates that can be heated to temperatures above 400 ° C.
- the object of the present invention was therefore to provide a method for producing to provide self-cleaning surfaces on three-dimensional moldings.
- the simplest possible technique should be used and the durability of the self-cleaning surfaces should be achieved.
- the present invention therefore relates to a shaping process for the production of moldings, having at least one surface which has self-cleaning properties and elevations formed by microparticles, by thermally shaping materials comprising organic compounds by means of a shaping tool, which is characterized in that, before the thermal shaping, microparticles are applied to the inner surfaces of the molding tool and the shaping is then carried out, in which the microparticles are pressed and anchored into the surface of the molding which has not yet solidified.
- the present invention also relates to moldings with at least one surface which has self-cleaning properties and surface structures with elevations, produced by the process according to the invention.
- the method according to the invention has the advantage that it can use existing equipment for the production of moldings by means of thermal shaping.
- Such moldings are usually produced by softening or melting the material to be processed and by molding a mold or a mold with this material.
- the method according to the invention makes use of this method, in which microparticles are applied to the mold or the mold before the actual shaping, which are transferred to the shaped body during shaping, in that the particles are pressed into the softened or melted surface of the shaped body.
- molded articles with self-cleaning Surfaces accessible that have particles with a jagged structure, without the need to apply an additional embossing layer or foreign material carrier layer to the moldings.
- the molded articles according to the invention have the advantage that structure-forming particles are not fixed by a carrier material and thus an unnecessarily high number of material combinations and the associated negative properties are avoided.
- the method according to the invention makes self-cleaning moldings accessible in which self-cleaning is achieved neither by an additional application of material for particle fixation, nor by an additional chemical process.
- Another advantage of the method according to the invention is that scratch-sensitive surfaces are not damaged by subsequent mechanical application of a carrier layer and / or of particles.
- the shaping process according to the invention for the production of moldings with at least one surface which has self-cleaning properties and elevations formed by microparticles, by means of thermal shaping of materials comprising organic compounds by means of a shaping tool is characterized in that prior to the thermal shaping, microparticles are applied to the inner surfaces of the Forming tool are applied and then the shaping is carried out, in which the microparticles are at least partially pressed into the not yet solidified surface of the molded body and anchored.
- the molding tool is preferably a mold for the Production of conventional moldings is usually used. Such common forms can e.g. B. consist of two parts, the die and the core.
- the microparticles can be applied to the die (die) and / or to the core (die).
- the microparticles are at least partially pressed into the molding compound and, when the molding compound solidifies, are held and anchored by the molding compound, a particularly stable anchoring being obtained if microparticles which have a fine structure on the surface are used, since the fine structure of the Shaping compound is partially filled and there are many anchoring points after the mass has solidified.
- the surface produced by the method according to the invention with self-cleaning properties and microparticles on the surface which form elevations can be designed in such a way that the surface exclusively contains microparticles, almost exclusively microparticles or else microparticles at a distance of 0 to 10, in particular 0 to 3 Has particle diameters to each other.
- thermal shaping processes can be used in the process according to the invention, in which the molding composition is softened or melted by supplying thermal energy and then a mold or a molding tool is molded with this composition.
- the thermal shaping is preferably selected from blow molding, extrusion blow molding, extrusion stretch blow molding, injection blow molding, injection stretch blow molding, deep drawing, stretch molding with negative pressure, stretch molding with positive pressure and rotary deep drawing.
- blow molding extrusion blow molding, extrusion stretch blow molding, injection blow molding, injection stretch blow molding, deep drawing, stretch molding with negative pressure, stretch molding with positive pressure and rotary deep drawing.
- Descriptions of these thermal molding processes can e.g. B.
- All materials which are suitable for thermal shaping can be used as the material which has organic compounds and is used as the molding compound Have polymers or polymer blends.
- PET or PBT poly (vinylidene fluoride), poly (isobutene), poly (4-methyl-1-pentene), acrylonitrile-butadiene-styrene terpolymers (ABS), polynorbones as homo- or copolymer and mixtures thereof , a rubber, a synthetic rubber or a natural rubber-containing material used in
- thermoplastic polymers are particularly suitable for blow molding PVC and polypropylene, for extrusion blow molding, extrusion stretch blow molding, injection blow molding and injection stretch blow molding, in particular PET, polycarbonates, for. B. Makrolone ® and polypropylene, for deep drawing, stretch forming with negative pressure, stretch forming with positive pressure and rotary deep drawing, in particular polypropylene, ABS and PVC.
- the pressing is preferably carried out in such a way that at least some of the particles, preferably at least 50% of the particles, only to a maximum of 90% of their diameter, preferably with 10 to 70%, preferably with 20 to 50% and very particularly preferably with 30 to 40% of their average particle diameter are pressed into the softened or melted surface of the molded body.
- the surface of the molded body which has not yet solidified and into which the microparticles are pressed and anchored can be the surface of a melt of a material to be molded or the softened surface of a material to be molded.
- microparticles which are pressed into the surface of the shaped body in the method according to the invention are applied to the surface of the mold or the molding tool or at least part of a mold or a molding tool before being pressed in by molding.
- it may be advantageous to apply microparticles only to the surfaces of the shape or the shaped body which, when the later shaped body is shaped, the z. B. can be a vessel or a bottle comes into contact with an outer and / or an inner surface of the molded body. In this way, objects can be produced which have surfaces with self-cleaning properties either on their inner or outer sides or on the inner and outer sides.
- injection stretch blow molding which, for. B.
- microparticles it is preferably applied by spraying.
- the application of the microparticles to the mold is particularly advantageous because the micropowder prevents the material of the molded body from adhering to the mold after the molding process has ended, since the material itself hardly comes into contact with the mold at all, since the microparticles to achieve the preferred distances between the surveys are applied very closely to the mold.
- Spraying the microparticles onto the mold can e.g. B. by spraying microparticle powders containing aerosols or dispersions in addition to
- Microparticles have a blowing agent or a preferably volatile solvent, with the spraying of suspensions being preferred.
- the suspensions used preferably have an alcohol, in particular ethanol or, as the solvent
- Isopropanol ketones such as e.g. B. acetone or methyl ethyl ketone, ether, such as. B. diisopropyl ether, or hydrocarbons such as cyclohexane.
- the suspensions very particularly preferably have alcohols. It can be beneficial if the
- Suspension from 0.1 to 10, preferably from 0.25 to 7.5 and very particularly preferably from
- the molding tool has a mold surface temperature of 30 to 150 ° C.
- the temperature of the molding tool has a mold surface temperature of 30 to 150 ° C.
- microparticles used in the process according to the invention are preferably those which have at least one material selected from silicates, minerals, metal oxides, metal powders, silicas, pigments or polymers.
- Microparticles which have a particle diameter of from 0.02 to 100 ⁇ m, particularly preferably from 0.1 to 50 ⁇ m and very particularly preferably from 0.1 to 30 ⁇ m are preferably used.
- Microparticles with diameters smaller than 500 nm can also be used.
- microparticles which are composed of primary particles to form agglomerates or aggregates with a size of 0.2 to 100 ⁇ m are also suitable.
- microparticles in particular as particles which have an irregular fine structure in the nanometer range on the surface, are those particles which have at least one compound selected from pyrogenic silica, precipitated silica, aluminum oxide, mixed oxides, doped silicates, titanium dioxide or powdery polymers.
- Preferred particles which have an irregular fine structure in the nanometer range on the surface have elevations in this fine structure which have an aspect ratio of greater than 1, particularly preferably greater than 1.5 and very particularly preferably greater than 2.5. The aspect ratio is again defined as the quotient from the maximum height to the maximum width of the survey.
- the microparticles preferably have hydrophobic properties, the hydrophobic properties being able to be attributed to the material properties of the materials present on the surfaces of the particles themselves or can be obtained by treating the particles with a suitable compound.
- the particles can be given hydrophobic properties before or after being pressed into the surface.
- microparticles To make the microparticles hydrophobic before or after they are pressed (anchored) into the surface of the shaped body, they can be coated with a compound suitable for hydrophobizing z.
- B. from the group of alkylsilanes, fluoroalkylsilanes or disilazanes, as are offered for example under the name Dynasylan by Degussa AG.
- the microparticles which are preferably used are explained in more detail below.
- the particles used can come from different areas. For example, it can be titanium dioxide, doped silicates, minerals, metal oxides, aluminum oxide, silicas or pyrogenic silicates, Aerosile ® or powdered polymers, such as. B.
- agglomerated emulsions or cryomilled PTFE Particularly suitable particle systems are hydrophobicized pyrogenic silicas, so-called aerosils. In addition to the structure, a hydrophobicity is necessary to generate the self-cleaning surfaces.
- the particles used can themselves be hydrophobic, such as PTFE.
- the particles can be made hydrophobic, such as the Aerosil VPR 411 ® or Aerosil R 8200 ® . However, they can also be made hydrophobic afterwards. It is immaterial whether the particles are hydrophobicized before or after application.
- Such particles to be hydrophobicized are, for example, Aeroperl 90/30 ® , Sipernat silica 350 ® , aluminum oxide C ® , zirconium silicate, vanadium-doped or VP Aeroperl P 25/20 ® .
- the hydrophobization is expediently carried out by treatment with perfluoroalkylsilane compounds and subsequent tempering.
- the method according to the invention can be used to produce moldings with at least one surface which has self-cleaning properties and surface structures with elevations.
- These moldings with at least one surface which has self-cleaning properties are distinguished by the fact that the surface has at least one firmly anchored layer of microparticles which form elevations.
- the at least partially present elevations on the surface of the molded body in combination with a hydrophobicity ensure that these surface areas are difficult to wet and thus have self-cleaning properties.
- the firmly anchored position of microparticles is obtained by applying microparticles as a layer to the molding tool or the mold before shaping and then molding with this tool.
- the microparticles are at least partially pressed into the molding compound and, when the molding compound solidifies, are held and anchored by the molding compound, a particularly stable anchoring being obtained if microparticles which have a fine structure on the surface are used, since the fine structure of the Molding compound is partially filled and there are many anchoring points after the molding compound has solidified.
- a layer of microparticles is understood in the sense of the present invention a collection of microparticles on the surface, which form elevations.
- the layer can be designed such that the surface has exclusively microparticles, almost exclusively microparticles or else also microparticles at a distance of 0 to 10, in particular 0 to 3, particle diameters from one another.
- the surfaces of the moldings with self-cleaning properties preferably have at least one layer with elevations with an average height of 20 nm to 25 ⁇ m and an average distance of 20 nm to 25 ⁇ m, preferably with an average height of 50 nm to 10 ⁇ m and / or average distance of 50 nm to 10 ⁇ m and very particularly preferably with an average height of 50 nm to 4 ⁇ m and / or an average distance of 50 nm to 4 ⁇ m.
- the moldings according to the invention very particularly preferably have surfaces with elevations with an average height of 0.25 to 1 ⁇ m and an average distance of 0.25 to 1 ⁇ m.
- the mean distance between the elevations is understood to mean the distance between the highest elevation of one elevation and the next highest elevation. If an elevation has the shape of a cone, the tip of the cone represents the highest elevation of the elevation. If the elevation is a cuboid, the top surface of the cuboid represents the highest elevation of the elevation.
- the wetting of bodies and thus the self-cleaning property can be described by the contact angle that a drop of water forms with the surface.
- a contact angle of 0 degrees means complete wetting of the surface.
- the static contact angle is generally measured using devices in which the contact angle is optically determined. Static contact angles of less than 125 ° are usually measured on smooth hydrophobic surfaces.
- the present shaped articles with self-cleaning surfaces have static contact angles of preferably greater than 130 °, preferably greater than 140 ° and very particularly preferably greater than 145 °.
- a surface only has good self-cleaning properties if it has a difference between the advancing and retreating angles of at most 10 °, which is why surfaces according to the invention preferably have a difference between the advancing and retracting angles of less than 10 °, preferably less than 5 ° and very particularly preferably have less than 4 °.
- a drop of water is used to determine the advancing angle placed on the surface by means of a cannula and the drops on the surface enlarged by adding water through the cannula. During the enlargement, the edge of the drop glides over the surface and the contact angle is determined as the advancing angle.
- the retraction angle is measured on the same drop, only the water is withdrawn from the drop through the cannula and the contact angle is measured while the drop is being reduced.
- the difference between the two angles is called hysteresis. The smaller the difference, the less the interaction of the water drop with the surface of the surface and the better the lotus effect.
- the surfaces according to the invention with self-cleaning properties preferably have an aspect ratio of the elevations of greater than 0.15.
- the elevations which are formed by the particles themselves preferably have an aspect ratio of 0.3 to 0.9, particularly preferably 0.5 to 0.8.
- the aspect ratio is defined as the quotient of the maximum height and the maximum width of the structure of the surveys.
- the shaped bodies according to the invention with surfaces which have self-cleaning properties and surface structures with elevations are distinguished by the fact that the surfaces are preferably plastic surfaces, in which particles are directly integrated or anchored and are not connected via carrier systems or the like.
- the particles are bound or anchored to the surface by pressing the particles into the molten or softened material of the molded body or the molding compound during shaping.
- the particles preferably more than 50%, preferably more than 75% of the particles, preferably only up to 90% of their diameter, are pressed into the surface of the shaped body.
- the surface therefore preferably has particles which are anchored in the surface at 10 to 90%, preferably 20 to 50% and very particularly preferably from 30 to 40% of their mean particle diameter and thus still protrude from the moldings with parts of their inherently fissured surface , This ensures that the elevations which are formed by the particles themselves have a sufficiently large aspect ratio of preferably at least 0.15.
- the aspect ratio is defined here as the ratio of the maximum height to the maximum width of the elevations.
- microparticles firmly attached to the surface, which form the elevations on the surface of the shaped bodies are preferably selected from silicates, minerals, metal oxides, metal powders, silicas, pigments or polymers, very particularly preferably from pyrogenic silicas, precipitated silicas, aluminum oxide, mixed oxides, doped Silicates, titanium dioxide or powdered polymers.
- Preferred microparticles have a particle diameter of 0.02 to 100 ⁇ m, particularly preferably from 0.1 to 50 ⁇ m and very particularly preferably from 0.1 to 30 ⁇ m. Suitable microparticles can, however, also have a diameter of less than 500 nm or aggregate from primary particles to form agglomerates or aggregates with a size of 0.2 to 100 ⁇ m.
- microparticles which form the elevations of the structured surface of the shaped body according to the invention are those which have an irregular, airy, fissured
- Microparticles with an irregular, airy, fissured fine structure are preferred.
- Elevations with an aspect ratio in the fine structures of greater than 1, particularly preferably greater than 1.5 are again defined as the quotient from the maximum height to the maximum width of the survey.
- Fig. 1 the difference of
- Fine structure are shown schematically.
- the figure shows the surface of a deep-drawn molded body X which has particles P (only one particle is shown to simplify the illustration).
- the elevation formed by the particle itself has an aspect ratio of approx. 0.71, calculated as the quotient from the maximum height of the
- a selected elevation of the elevations E, which are present on the particles due to the fine structure of the particles, has an aspect ratio of 2.5, calculated as a quotient from the maximum height of the elevation mH ′, which is 2.5 and the maximum width mB ', which is 1 in proportion.
- Preferred microparticles which have an irregular fine structure in the nanometer range on the surface are those particles which have at least one compound selected from pyrogenic silica, precipitated silica, aluminum oxide, mixed oxides, doped silicates, titanium dioxide or powdery polymers.
- the microparticles have hydrophobic properties, the hydrophobic properties being able to be traced back to the material properties of the materials present on the surfaces of the particles themselves or can be obtained by treating the particles with a suitable compound.
- the microparticles can have been provided with hydrophobic properties before or after the application or binding to or on the surface of the shaped body.
- they can be treated with a compound which is suitable for hydrophobicizing, for. B. from the group of alkylsilanes, fluoroalkylsilanes or disilazanes.
- the particles can come from different areas.
- it can be silicates, doped silicates, minerals, metal oxides, aluminum oxide, silicas or titanium dioxide, Aerosile ® or powdered polymers, such as. B. spray-dried and agglomerated emulsions or cryomilled PTFE.
- Particularly suitable particle systems are hydrophobicized pyrogenic silicas, so-called Aerosile ® .
- a hydrophobicity is necessary to generate the self-cleaning surfaces.
- the particles used can themselves be hydrophobic, such as powdered polytetrafluoroethylene (PTFE).
- the particles can be made hydrophobic, such as the Aerosil VPR 411 ® or Aerosil R 8200 ® . However, they can also be made hydrophobic afterwards. It is immaterial whether the particles are hydrophobicized before or after application.
- Such particles to be hydrophobized are, for example, Aeroperl 90/30 ® , Sipernat Silica 350 ® , aluminum oxide C ® , zirconium silicate, vanadium-doped or VP Aeroperl 25/20 ® . In the latter case, the hydrophobization is expediently carried out by treatment with perfluoroalkylsilane compounds and subsequent tempering.
- the shaped bodies can have the elevations on all surfaces or only on certain surfaces or on partial areas thereof.
- the shaped bodies according to the invention preferably have the elevations on all surfaces or on the entire inner and / or outer surfaces.
- the moldings themselves can preferably be polymers or polymer blends based on polycarbonates, polyoxymethylenes, poly (meth) acrylates, polyamides, polyvinyl chloride (PVC), polyethylenes, polypropylenes, polystyrenes, polyesters, polyether sulfones, aliphatic linear or branched polyalkenes, cyclic polyalkenes , Polyacrylonitrile or polyalkylene terephthalates and mixtures or copolymers thereof.
- PVC polyvinyl chloride
- the shaped bodies particularly preferably have a material selected from poly (vinylidene fluoride) or other polymers made from poly (ethylene), poly (propylene), poly (isobutene), poly (4-methyl-1-pentene) or polynorbones as homo- or copolymer.
- the moldings very particularly preferably have poly (ethylene), poly (propylene), polymethyl methacrylate, polystyrene, polyester, acrylonitrile-butadiene-styrene terpolymers (ABS), polyethylene terephthalate, polybutylene terephthalate or poly (vinylidene fluoride) as a material for the surface, a rubber, a synthetic rubber or a material comprising natural rubber.
- shaped bodies with a surface that has at least partially self-cleaning properties and surface structures with elevations are accessible.
- the shaped bodies can have any shape that can be produced using the known thermal shaping processes.
- Such shaped bodies can in particular be vessels for holding liquids or pastes.
- such shaped bodies can be selected from vessels, lampshades, bottles, car tires, tires, buckets, storage vessels, barrels, bowls, measuring cups, funnels, tubs and housing parts.
- FIG. 1 schematically shows the surface of a deep-drawn molded body X which has particles P (only one particle is shown to simplify the illustration).
- the survey which is formed by the particle itself, has an aspect ratio of approx. 0.71, calculated as the quotient from the maximum height of the particle mH, which is 5, since only the part of the particle that contributes to the survey protrudes from the surface of the molded body X, and the maximum width mB, which is 7 in relation to it.
- a selected elevation of the elevations E, which are present on the particles due to the fine structure of the particles has an aspect ratio of 2.5, calculated as a quotient from the maximum height of the elevation mH ′, which is 2.5 and the maximum width mB ', which is 1 in proportion.
- a suspension of Aerosil R8200 ® (1% by weight in ethanol) is applied to a deep-drawing mold in a deep-drawing machine (725, CRCarke & Co) and the solvent (ethanol) is then evaporated.
- a mold plate (0.5 mm) made of Vinnolit S 3257, a PVC with a K value of 57, is applied to the mold prepared in this way and heated to the processing temperature customary for PVC.
- the softened mold plate is deep-drawn by applying a vacuum. After sufficient cooling, the vacuum pump is switched to bubbles and the molded body obtained is separated from the mold. A molded body is obtained which has microparticles which are anchored in the surface of the molded body.
- the roll-off angle for a drop of water on the surface of the molded body thus produced is determined by applying a drop to the surface and determining the angle at which the drop rolls off the surface by increasingly inclining the injection molded body. For a 40 ⁇ l drop of water, the roll angle is 7.7 °. In addition, a progression angle of approx. 152 ° and a retreat angle of 149.9 ° are determined. These values show that the process according to the invention can be used to produce moldings which are self-cleaning Have surfaces.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Mechanical Engineering (AREA)
- Moulds For Moulding Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Prevention Of Fouling (AREA)
- Containers Having Bodies Formed In One Piece (AREA)
- Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10210666A DE10210666A1 (de) | 2002-03-12 | 2002-03-12 | Formgebungsverfahren zur Herstellung von Formkörpern mit zumindest einer Oberfläche, die selbstreinigende Eigenschaften aufweist sowie mit diesem Verfahren hergestellte Formkörper |
DE10210666 | 2002-03-12 | ||
PCT/EP2003/001028 WO2003076090A1 (de) | 2002-03-12 | 2003-02-03 | Formgebungsverfahren zur herstellung von formkörpern mit zumindest einer oberfläche, die selbstreinigende eigenschaften aufweist sowie mit diesem verfahren hergestellte formkörper |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1492633A1 true EP1492633A1 (de) | 2005-01-05 |
Family
ID=27797661
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP03743798A Withdrawn EP1492633A1 (de) | 2002-03-12 | 2003-02-03 | Formgebungsverfahren zur herstellung von formk rpern mit zum indest einer oberfl che, die selbstreinigende eigenschaften aufweist sowie mit diesem verfahren hergestellte formk rper |
Country Status (7)
Country | Link |
---|---|
US (1) | US20050112326A1 (de) |
EP (1) | EP1492633A1 (de) |
JP (1) | JP4334356B2 (de) |
AU (1) | AU2003210199B2 (de) |
CA (1) | CA2478834A1 (de) |
DE (1) | DE10210666A1 (de) |
WO (1) | WO2003076090A1 (de) |
Families Citing this family (46)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10118346A1 (de) * | 2001-04-12 | 2002-10-17 | Creavis Tech & Innovation Gmbh | Textile Flächengebilde mit selbstreinigender und wasserabweisender Oberfläche |
DE10134477A1 (de) * | 2001-07-16 | 2003-02-06 | Creavis Tech & Innovation Gmbh | Selbstreinigende Oberflächen durch hydrophobe Strukturen und Verfahren zu deren Herstellung |
DE10160055A1 (de) * | 2001-12-06 | 2003-06-18 | Degussa | Diffus reflektierende Oberflächen zu deren Herstellung |
DE10205007A1 (de) * | 2002-02-07 | 2003-08-21 | Creavis Tech & Innovation Gmbh | Verfahren zur Herstellung von Schutzschichten mit schmutz- und wasserabweisenden Eigenschaften |
DE10210671A1 (de) * | 2002-03-12 | 2003-09-25 | Creavis Tech & Innovation Gmbh | Entformungsmittel, welches hydrophobe, nanoskalige Partikel aufweist sowie Verwendung dieser Entformungsmittel |
DE10242560A1 (de) * | 2002-09-13 | 2004-03-25 | Creavis Gesellschaft Für Technologie Und Innovation Mbh | Herstellung von selbstreinigenden Oberflächen auf textilen Beschichtungen |
DE10250328A1 (de) * | 2002-10-29 | 2004-05-13 | Creavis Gesellschaft Für Technologie Und Innovation Mbh | Herstellung von Suspensionen hydrophober Oxidpartikel |
DE10308379A1 (de) * | 2003-02-27 | 2004-09-09 | Creavis Gesellschaft Für Technologie Und Innovation Mbh | Dispersion von Wasser in hydrophoben Oxiden zur Herstellung von hydrophoben nanostrukturierten Oberflächen |
DE10315128A1 (de) * | 2003-04-03 | 2004-10-14 | Creavis Gesellschaft Für Technologie Und Innovation Mbh | Verfahren zur Unterdrückung von Schimmelbildung unter Verwendung hydrophober Stoffe sowie ein schimmelpilzhemmendes Mittel für Gebäudeteile |
DE10321851A1 (de) * | 2003-05-15 | 2004-12-02 | Creavis Gesellschaft Für Technologie Und Innovation Mbh | Verwendung von mit Fluorsilanen hydrophobierten Partikeln zur Herstellung von selbstreinigenden Oberflächen mit lipophoben, oleophoben, laktophoben und hydrophoben Eigenschaften |
DE202004009546U1 (de) * | 2004-06-16 | 2004-09-02 | Friedr. Dick Gmbh & Co. Kg | Messer |
DE102004036073A1 (de) * | 2004-07-24 | 2006-02-16 | Degussa Ag | Verfahren zur Versiegelung von Natursteinen |
DE102004062742A1 (de) * | 2004-12-27 | 2006-07-06 | Degussa Ag | Textile Substrate mit selbstreinigenden Eigenschaften (Lotuseffekt) |
DE102004062739A1 (de) * | 2004-12-27 | 2006-07-06 | Degussa Ag | Selbstreinigende Oberflächen mit durch hydrophobe Partikel gebildeten Erhebungen, mit verbesserter mechanischer Festigkeit |
DE102004062740A1 (de) * | 2004-12-27 | 2006-07-13 | Degussa Ag | Verfahren zur Erhöhung der Wasserdichtigkeit von textilen Flächengebilden, so ausgerüstete textile Flächengebilde sowie deren Verwendung |
DE102004062743A1 (de) * | 2004-12-27 | 2006-07-06 | Degussa Ag | Verfahren zur Erhöhung der Wasserdichtigkeit von textilen Flächengebilden, so ausgerüstete textile Flächengebilde sowie deren Verwendung |
US7790658B2 (en) * | 2005-05-27 | 2010-09-07 | University of Florida Research Foundaction, Inc. | Inert wear resistant PTFE-based solid lubricant nanocomposite |
DE102006001641A1 (de) * | 2006-01-11 | 2007-07-12 | Degussa Gmbh | Substrate mit bioziden und/oder antimikrobiellen Eigenschaften |
IL175477A (en) * | 2006-05-08 | 2013-09-30 | Efraim Kfir | A kit for lifting the sinus membranes for use in dental implant surgery |
DE102006027480A1 (de) * | 2006-06-14 | 2008-01-10 | Evonik Degussa Gmbh | Kratz- und abriebfeste Beschichtungen auf polymeren Oberflächen |
DE102007009590A1 (de) * | 2007-02-26 | 2008-08-28 | Evonik Degussa Gmbh | Glänzender und kratzfester Nagellack durch Zusatz von Sol-Gel-Systemen |
DE102007009589A1 (de) * | 2007-02-26 | 2008-08-28 | Evonik Degussa Gmbh | Glänzender und kratzfester Nagellack durch Zusatz von Silanen |
US8153834B2 (en) * | 2007-12-05 | 2012-04-10 | E.I. Dupont De Nemours And Company | Surface modified inorganic particles |
EP2098359A1 (de) * | 2008-03-04 | 2009-09-09 | Lm Glasfiber A/S | Eigenschaften zur Flächenregeneration von Verbundstoffen |
WO2013019257A1 (en) | 2011-08-03 | 2013-02-07 | Massachusetts Institute Of Technology | Articles for manipulating impinging liquids and methods of manufacturing same |
MY163331A (en) | 2011-08-05 | 2017-09-15 | Massachusetts Inst Technology | Liquid-impregnated surfaces, methods of making and devices incorporating the same |
KR20140105480A (ko) * | 2011-11-21 | 2014-09-01 | 도요세이칸 그룹 홀딩스 가부시키가이샤 | 점성 유체의 배출에 이용하는 주출 부재 |
BR112014023436B1 (pt) | 2012-03-23 | 2021-05-04 | Massachusetts Institute Of Technology | recipiente tendo superfície impregnada com líquido e seu processo de fabricação |
US9309162B2 (en) | 2012-03-23 | 2016-04-12 | Massachusetts Institute Of Technology | Liquid-encapsulated rare-earth based ceramic surfaces |
US9625075B2 (en) | 2012-05-24 | 2017-04-18 | Massachusetts Institute Of Technology | Apparatus with a liquid-impregnated surface to facilitate material conveyance |
US20130337027A1 (en) | 2012-05-24 | 2013-12-19 | Massachusetts Institute Of Technology | Medical Devices and Implements with Liquid-Impregnated Surfaces |
JP2015525132A (ja) | 2012-06-13 | 2015-09-03 | マサチューセッツ インスティテュート オブ テクノロジー | 表面上の液体を浮上させるための物品および方法ならびにそれを組み入れたデバイス |
JP2014000968A (ja) * | 2012-06-17 | 2014-01-09 | Toyo Aluminium Kk | 撥水性表面を有する樹脂成形品の製造方法 |
US20140178611A1 (en) | 2012-11-19 | 2014-06-26 | Massachusetts Institute Of Technology | Apparatus and methods employing liquid-impregnated surfaces |
KR20150086522A (ko) | 2012-11-19 | 2015-07-28 | 메사추세츠 인스티튜트 오브 테크놀로지 | 액체-함침된 표면을 사용하는 장치 및 방법 |
WO2014127304A1 (en) | 2013-02-15 | 2014-08-21 | Massachusetts Institute Of Technology | Grafted polymer surfaces for dropwise condensation, and associated methods of use and manufacture |
BR112015025890A8 (pt) | 2013-04-16 | 2020-01-14 | Massachusetts Inst Technology | método para separar duas ou mais fases de mistura de emulsão |
US9585757B2 (en) | 2013-09-03 | 2017-03-07 | Massachusetts Institute Of Technology | Orthopaedic joints providing enhanced lubricity |
EP3083282A4 (de) | 2013-12-18 | 2017-08-02 | Bridgestone Americas Tire Operations, LLC | Reifen und andere objekte mit aerodynamischer/hydrodynamischer oberflächenbehandlung |
WO2015095660A1 (en) | 2013-12-20 | 2015-06-25 | Massachusetts Institute Of Technology | Controlled liquid/solid mobility using external fields on lubricant-impregnated surfaces |
US9947481B2 (en) | 2014-06-19 | 2018-04-17 | Massachusetts Institute Of Technology | Lubricant-impregnated surfaces for electrochemical applications, and devices and systems using same |
US10221321B2 (en) | 2015-08-28 | 2019-03-05 | Battelle Memorial Institute | Paintable hydrophobic and lubricant-infused surface coatings and processes for making and using same |
US11168276B2 (en) | 2015-08-28 | 2021-11-09 | Battelle Memorial Institute | Reinforced composites with repellent and slippery properties |
US10577511B2 (en) | 2016-01-20 | 2020-03-03 | Battelle Memorial Institute | Stretchable hydrophobic materials and methods for making the same |
JP6524180B2 (ja) * | 2017-11-01 | 2019-06-05 | 東洋アルミニウム株式会社 | 包装材料 |
CN114163806A (zh) * | 2021-11-29 | 2022-03-11 | 浙江大学台州研究院 | 一种抗菌多糖外表面改性tpu医用导管及其制备方法 |
Family Cites Families (34)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2572023A1 (fr) * | 1984-10-23 | 1986-04-25 | Arib | Procede de realisation d'un revetement retroreflechissant a surface lisse sur une piece moulee ainsi qu'un element moule obtenu selon ledit procede |
US4963388A (en) * | 1987-04-17 | 1990-10-16 | Mobil Oil Corporation | Method for forming particle-impregnated one-sided cling stretch wrap film |
WO1997045502A1 (fr) * | 1996-05-31 | 1997-12-04 | Toto Ltd. | Element anti-encrassement et composition pour revetement anti-encrassement |
DE19923175A1 (de) * | 1999-05-20 | 2000-11-23 | Borsi Kg F | Verfahren zum Beschichten einer Kunststoffträgerplatte und diese umfassendes Displayelement |
DE19928863A1 (de) * | 1999-06-24 | 2001-01-04 | Continental Ag | Fahrzeugreifen |
DE29911349U1 (de) * | 1999-06-30 | 2000-11-16 | Witte plusprint Druckmedien GmbH, 48163 Münster | Plakette, insbesondere Zulassungs-, Prüf-, Siegel- oder Mautplakette für Kraftfahrzeuge |
DE19944169B4 (de) * | 1999-09-15 | 2006-02-16 | Georg Gros | Mittel zur Herstellung von selbstreinigenden dünnen Oberflächenbeschichtungen und dafür geeignete Verfahren |
DE10016215A1 (de) * | 2000-03-31 | 2001-10-04 | Basf Ag | Verfahren zur Beschichtung von Apparaten und Apparateteilen für den chemischen Anlagenbau |
DE20006010U1 (de) * | 2000-03-31 | 2000-07-13 | CREAVIS Gesellschaft für Technologie und Innovation mbH, 45772 Marl | Behälter mit strukturierten flüssigkeitsabweisenden und flüssigkeitsbenetzenden Teilbereichen der inneren Oberfläche |
DE10022246A1 (de) * | 2000-05-08 | 2001-11-15 | Basf Ag | Beschichtungsmittel für die Herstellung schwer benetzbarer Oberflächen |
DE10063739B4 (de) * | 2000-12-21 | 2009-04-02 | Ferro Gmbh | Substrate mit selbstreinigender Oberfläche, Verfahren zu deren Herstellung und deren Verwendung |
DE10065797A1 (de) * | 2000-12-30 | 2002-07-04 | Creavis Tech & Innovation Gmbh | Vorrichtung zur Kondensationsbeschleunigung mit Hilfe strukturierter Oberflächen |
DE10100383A1 (de) * | 2001-01-05 | 2002-07-11 | Degussa | Verfahren zur Aufbringung einer fluoralkylfunktionellen Organopolysiloxan-Beschichtung mit beständigen Wasser und Öl abweisenden Eigenschaften auf polymere Substrate |
DE10110589A1 (de) * | 2001-03-06 | 2002-09-12 | Creavis Tech & Innovation Gmbh | Geometrische Formgebung von Oberflächen mit Lotus-Effekt |
DE10118351A1 (de) * | 2001-04-12 | 2002-10-17 | Creavis Tech & Innovation Gmbh | Selbstreinigende Oberflächen durch hydrophobe Strukturen und Verfahren zu deren Herstellung |
DE10118349A1 (de) * | 2001-04-12 | 2002-10-17 | Creavis Tech & Innovation Gmbh | Selbstreinigende Oberflächen durch hydrophobe Strukturen und Verfahren zu deren Herstellung |
DE10118345A1 (de) * | 2001-04-12 | 2002-10-17 | Creavis Tech & Innovation Gmbh | Eigenschaften von Strukturbildnern für selbstreinigende Oberflächen und die Herstellung selbiger |
DE10118346A1 (de) * | 2001-04-12 | 2002-10-17 | Creavis Tech & Innovation Gmbh | Textile Flächengebilde mit selbstreinigender und wasserabweisender Oberfläche |
DE10134477A1 (de) * | 2001-07-16 | 2003-02-06 | Creavis Tech & Innovation Gmbh | Selbstreinigende Oberflächen durch hydrophobe Strukturen und Verfahren zu deren Herstellung |
DE10139574A1 (de) * | 2001-08-10 | 2003-02-20 | Creavis Tech & Innovation Gmbh | Erhalt des Lotus-Effektes durch Verhinderung des Mikrobenwachstums auf selbstreinigenden Oberflächen |
DE10159767A1 (de) * | 2001-12-05 | 2003-06-18 | Degussa | Verfahren zur Herstellung von Gegenständen mit antiallergischen Oberflächen |
DE10160055A1 (de) * | 2001-12-06 | 2003-06-18 | Degussa | Diffus reflektierende Oberflächen zu deren Herstellung |
DE10205007A1 (de) * | 2002-02-07 | 2003-08-21 | Creavis Tech & Innovation Gmbh | Verfahren zur Herstellung von Schutzschichten mit schmutz- und wasserabweisenden Eigenschaften |
DE10205783A1 (de) * | 2002-02-13 | 2003-08-21 | Creavis Tech & Innovation Gmbh | Formkörper mit selbstreinigenden Eigenschaften und Verfahren zur Herstellung solcher Formkörper |
DE10210027A1 (de) * | 2002-03-07 | 2003-09-18 | Creavis Tech & Innovation Gmbh | Hydrophile Oberflächen |
DE10210671A1 (de) * | 2002-03-12 | 2003-09-25 | Creavis Tech & Innovation Gmbh | Entformungsmittel, welches hydrophobe, nanoskalige Partikel aufweist sowie Verwendung dieser Entformungsmittel |
DE10235758A1 (de) * | 2002-08-05 | 2004-02-26 | Degussa Ag | Dotiertes Zinkoxidpulver, Verfahren zu seiner Herstellung und Verwendung |
US6858856B2 (en) * | 2002-10-24 | 2005-02-22 | Royal Consumer Information Products, Inc. | Counterfeit detector cash register |
DE10250328A1 (de) * | 2002-10-29 | 2004-05-13 | Creavis Gesellschaft Für Technologie Und Innovation Mbh | Herstellung von Suspensionen hydrophober Oxidpartikel |
DE10311645A1 (de) * | 2003-03-14 | 2004-09-23 | Degussa Ag | Nanoskaliges Indium-Zinn-Mischoxidpulver |
EP1475426B1 (de) * | 2003-04-24 | 2006-10-11 | Goldschmidt GmbH | Verfahren zur Herstellung von ablösbaren schmutz- und wasserabweisenden flächigen Beschichtungen |
DE102004036073A1 (de) * | 2004-07-24 | 2006-02-16 | Degussa Ag | Verfahren zur Versiegelung von Natursteinen |
DE202006015495U1 (de) * | 2006-10-09 | 2007-02-01 | Degussa Ag | Elektrolumineszent ausgestattete Artikel |
DE102007009589A1 (de) * | 2007-02-26 | 2008-08-28 | Evonik Degussa Gmbh | Glänzender und kratzfester Nagellack durch Zusatz von Silanen |
-
2002
- 2002-03-12 DE DE10210666A patent/DE10210666A1/de not_active Withdrawn
-
2003
- 2003-02-03 WO PCT/EP2003/001028 patent/WO2003076090A1/de active Application Filing
- 2003-02-03 US US10/506,993 patent/US20050112326A1/en not_active Abandoned
- 2003-02-03 AU AU2003210199A patent/AU2003210199B2/en not_active Ceased
- 2003-02-03 EP EP03743798A patent/EP1492633A1/de not_active Withdrawn
- 2003-02-03 CA CA002478834A patent/CA2478834A1/en not_active Abandoned
- 2003-02-03 JP JP2003574349A patent/JP4334356B2/ja not_active Expired - Fee Related
Non-Patent Citations (1)
Title |
---|
See references of WO03076090A1 * |
Also Published As
Publication number | Publication date |
---|---|
JP2005526636A (ja) | 2005-09-08 |
WO2003076090A1 (de) | 2003-09-18 |
DE10210666A1 (de) | 2003-10-02 |
AU2003210199A1 (en) | 2003-09-22 |
AU2003210199B2 (en) | 2008-06-19 |
JP4334356B2 (ja) | 2009-09-30 |
US20050112326A1 (en) | 2005-05-26 |
CA2478834A1 (en) | 2003-09-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1492633A1 (de) | Formgebungsverfahren zur herstellung von formk rpern mit zum indest einer oberfl che, die selbstreinigende eigenschaften aufweist sowie mit diesem verfahren hergestellte formk rper | |
EP1483104B1 (de) | Spritzgusskörper mit selbstreinigenden eigenschaften und verfahren zur herstellung solcher spritzgusskörper | |
EP1515805B1 (de) | Durch spritzgussverfahren hergestellte vorrichtung zur aufbewahrung von flüssigkeiten und zugehöriges herstellungsverfahren | |
DE10210674A1 (de) | Flächenextrudate mit selbstreinigenden Eigenschaften und Verfahren zur Herstellung solcher Extrudate | |
EP1249467B1 (de) | Selbstreinigende Oberflächen durch hydrophobe Strukturen und Verfahren zu deren Herstellung | |
AU2003206817B2 (en) | Release agents comprising hydrophobic, nanoscalar particles, and the use of these mold release agents | |
EP1249280B2 (de) | Selbstreinigende Oberflächen durch hydrophobe Strukturen und Verfahren zu deren Herstellung | |
WO2003068486A1 (de) | Formkörper mit selbstreinigenden eigenschaften und verfahren zur herstellung solcher formkörper | |
EP1249281A2 (de) | Selbstreinigende Oberfläche mit hydrophober Oberflächenstruktur und Verfahren zu deren Herstellung | |
DE10210667A1 (de) | Herstellung von Bahnenwaren mit selbstreinigenden Oberflächen mittels eines Kalandrierprozesses, Bahnenwaren selbst und die Verwendung dieser | |
EP1623066A1 (de) | Verwendung von mit fluorsilanen hydrophobierten partikeln zur herstellung von selbstreinigenden oberflächen mit lipophoben, oleophoben, laktophoben und hydrophoben eigenschaften | |
DE102009051598B4 (de) | Verfahren zur Herstellung von Vorrichtungen mit Mikrostrukturen aus Kunststoff mittels Verstreckung zum Zwecke der Selbstreinigung, derartige Vorrichtungen und deren Verwendung | |
DE10205782A1 (de) | Formkörper mit selbstreinigenden Eigenschaften und Verfahren zur Herstellung solcher Formkörper | |
WO2003013731A1 (de) | Pipettenspitzen mit teilweise strukturierten oberflächen mit verbesserten pipettiereigenschaften |
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: 20040819 |
|
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 IT LI LU MC NL PT SE SI SK TR |
|
AX | Request for extension of the european patent |
Extension state: AL LT LV MK RO |
|
RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: DEGUSSA GMBH |
|
17Q | First examination report despatched |
Effective date: 20060223 |
|
RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: EVONIK DEGUSSA GMBH |
|
RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: EVONIK DEGUSSA GMBH |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN |
|
18W | Application withdrawn |
Effective date: 20090901 |