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
  • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
  • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
• • 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
  • B29C59/005—Surface shaping of articles, e.g. embossing; Apparatus therefor characterised by the choice of material
• • 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
  • B29C59/026—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing of layered or coated substantially flat surfaces
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B38/00—Ancillary operations in connection with laminating processes
  • B32B38/06—Embossing
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
• • 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
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/70—Other properties
  • B32B2307/746—Slipping, anti-blocking, low friction
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2333/00—Polymers of unsaturated acids or derivatives thereof
  • B32B2333/04—Polymers of esters
  • B32B2333/12—Polymers of methacrylic acid esters, e.g. PMMA, i.e. polymethylmethacrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
• • 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.]
• • 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.]
  • Y10T428/24479—Structurally defined web or sheet [e.g., overall dimension, etc.] including variation in thickness

Definitions

• the invention relates to plastic bodies with a microstructured surface, a process for their production and their uses.
• DE 36 09 541 A1 describes a reduced flow resistance due to a surface with a reduced wall shear stress of a turbulent flow body with grooves running in the flow direction, which are separated from one another by sharp-edged ribs.
• the ribs are not arranged in parallel rows in parallel, but offset from each other.
• EP 0 846 617 A2 describes a surface for a wall over which a flow has a main flow direction, with ribs oriented in the flow direction and laterally spaced from the main flow direction, the height of which is 45 to 60% of the rib spacing.
• the ribs are wedge-shaped with a wedge angle of 20 trained up to 50 °.
• the valleys between the rows can be flat or curved.
• DE 44 07468 A1 describes a process for the extrusion of plastic sheets with a very finely structured surface by means of an extrusion system equipped with an extruder and a three-roll smoothing unit containing a roll with a structuring surface, characterized in that the system is designed for coextrusion and the Plastic sheets are structured on two extruders as a coextrudate from a high-viscosity base molding compound and an extruded low-viscosity molding compound and superficially structured using the three-roller smoothing unit.
• Suitable thermoplastics are polyacrylates, in particular polymethyl methacrylate, polycarbonate, polyolefins, LDPE, HDPE, polypropylene, polyethylene terephthalate, polyvinyl chloride, polystyrene or polyamide.
• the low-viscosity molding compound can consist of the same type of plastic as the basic molding compound, but it can also consist of a plastic that is sufficiently compatible with it.
• the low-viscosity molding compound can advantageously release agents, for. B. higher alcohols in amounts of z. B. up to 0.34 wt .-%.
• the ratio of the melt viscosity index MFR (DIN 57 735 or ASTM 1238-70) of the two molding compositions is approximately 1 to 10.
• the temperature of the embossing roller is preferably up to 70 ° C. above the glass transition temperature of the low-viscosity molding composition. It can be advantageously plastic panels with very fine textures such. B. produce linear or centric Fresnel lenses or semiholograms.
• EP-A 1 189 987 describes an impact-modified polymethacrylate molding composition, characterized by a Vicat softening temperature according to ISO 306 (B 50) of at least 90 ° C., a notched impact strength KSZ (Charpy) according to ISO 179 / 1eA of at least 3.0 KJ / m 2 at 23 ° C, and a melt flow rate MVR (230 ° C / 3.8 kg) according to ISO 1133 of at least 11 min cm 3/10, obtainable by mixing a ) 80 to 98% by weight of an impact modified polymethacrylate molding composition with b) 20 to 2% by weight of a low molecular weight polymethacrylate molding composition in the melt, the schiaggähten molding composition from 70 to 99 wt .-% from a matrix of 80 up to 100% by weight of free-radically polymerized methyl methacrylate units and optionally 0 to 20% by weight of further free-radically polymerizable comonomers and contains 1 to 30% by
• DE 4407468 A1 describes a process for the extrusion of plastic sheets with a very finely structured surface, such as. B. Fresnel lenses. However, it has been shown that even finer structures, in particular microstructures, can no longer be reproduced completely satisfactorily. It was therefore seen as an object to improve the method of DE 4407468 A1 so that it can also be used to produce plastic bodies with finely imaged microstructured surfaces.
• Process for the production of a plastic body with a microstructured surface by producing a composite from a carrier layer made of a thermoplastic or thermoelastic plastic with one or more structural layers, characterized in that the structural layer or the structural layers consist of 1 to 100% by weight of a polymethacrylate molding compound consists of 80 to 100 wt .-% of radically polymerized methyl methacrylate units and 0 to 20 wt .-% of other radically polymerizable comonomers and an average molecular weight (weight average) of 30,000 g / mol to 70,000 g / mol having
• a polymethacrylate molding composition which comprises 80 to 100% by weight of free-radically polymerized methyl methacrylate units and 0 to 20% by weight of further free-radicals polymerizable comonomers and has an average molecular weight (weight average) Mw of 90,000 g / mol to 200,000 g / mol
• the structure layer or the structure layers are microstructured by known structuring processes.
• the invention further relates to the plastic body itself and its uses.
• the solution is based on a modification of the plastic of the structural layer.
• the structural layer can be made wholly or in part from a low molecular weight polymethyl methacrylate molding composition as described in EP-A 1 189 987 for the purpose of modifying the flow properties of impact-modified polymethacrylate molding compositions for injection molding.
• a low molecular weight polymethyl methacrylate molding composition as described in EP-A 1 189 987 for the purpose of modifying the flow properties of impact-modified polymethacrylate molding compositions for injection molding.
• the low molecular weight molding composition described there alone or in a mixture with higher molecular weight molding compositions, would be particularly suitable for transferring microstructures by means of molding processes.
• the method according to the invention comprises the production of a plastic body with a microstructured surface by producing a composite from a carrier layer made of a thermoplastic or thermoelastic plastic with one or more structural layers which have a lower melt viscosity than that of the carrier layer.
• a microstructured surface is to be understood as a surface which has microstructures with geometry sizes in the range from 1 to 1000, preferably 2 to 500, in particular from 5 to 200 ⁇ m. Among geometry sizes are z. B. to understand heights, radii, diameter and / or roughness with which micro structures such. B. grooves, nubs, pyramids, ribs, prism structures and the like can be described.
• the microstructures can have aspect ratios from height to width of 0.3 to 10, preferably 0.5 to 5 and in particular 0.7 to 3
• a microstructured surface should also be understood to mean the design of macrostructures in their microstructure.
• the edge radius or the tip of prism or pyramid macrostructures in turn represent microstructures and can likewise be reproduced very precisely using the method according to the invention.
• the production of a plastic body according to the invention with a microstructured surface is carried out by producing a composite from a backing layer made of a thermoplastic or thermoelastic plastic with one or more structural layers that have or have a lower melt viscosity than that of the backing layer.
• carrier layer and structural layer can be made by means of plastic processing techniques known per se, for. B. by coextrusion, laminating the structural layer on the support layer or painting the structural layer on the support layer.
• the backing layer can be made by means of plastic processing techniques known per se, for. B. by coextrusion, laminating the structural layer on the support layer or painting the structural layer on the support layer.
• the carrier layer supports the structural layer or the structural layers.
• the plastic of the carrier layer generally has a higher melt viscosity than the plastic of a structural layer.
• the carrier layer can have a practically any layer thickness, for. B. in the range of 0.4 to 100, preferably from 0.05 to 10 and particularly preferably from 0.07 to 8 mm.
• the carrier layer can have virtually any shape and z.
• the plastic of the carrier layer can, for. B. cast or extruded polymethyl methacrylate plastic, impact modified polymethyl methacrylate, polycarbonate plastic, polystyrene plastic, styrene-acrylic-nitrile plastic, polyethylene terephthalate plastic, glycol-modified polyethylene terephthalate plastic, polyvinyl chloride plastic, polyolefin plastics such as polyethylene or polypropylene, Acrylonitrile-butadiene-stryrene (ABS) plastic or a mixture (blends) of different thermoplastics.
• ABS Acrylonitrile-butadiene-stryrene
• the carrier layer preferably consists of a polymethyl methacrylate plastic or a plastic compatible with polymethyl methacrylate. This ensures a good connection of the structural layer or the structural layers made of polymethyl methacrylate.
• a carrier layer made of a polymethacrylate molding composition which comprises 80 to 100, preferably 95 to 99% by weight of free-radically polymerized methyl methacrylate units and 0 to 20, preferably 1 to 5% by weight of further free-radically polymerizable comonomers and has an average molecular weight (weight average) Mw of 90,000 to 200,000, in particular from 120,000 to 190,000 (g / mol), particularly preferably from 150,000 to 190,000.
• Preferred comonomers are C 1 -C 4 -alkyl (meth) acrylates, in particular methyl acrylate, ethyl acrylate or butyl methacrylate.
• a molding composition of 95 to 99% by weight of methyl methacrylate and 1 to 5% by weight of methyl acrylate is particularly preferred.
• the plastic of the carrier layer can have a viscosity number ( ⁇ S p / c ) measured in chloroform according to ISO 1628 part 6 in the range from 50 to 80 ml / g, preferably 70-75 ml / g, corresponding to an average molecular weight IVIw (weight average) of 90,000 to 200,000, preferably from 100,000 to 130,000 or from 130,000 to 160,000, in particular from 150,000 to 190,000.
• the carrier layer can also consist of a plastic which is incompatible or poorly compatible with polymethyl methacrylate.
• the incompatibility of the plastics can also be used to separate the bond after the microstructuring has been applied. This can be beneficial to create thin embossed foils the backing layer only serves to absorb the opposing forces during stamping.
• Adhesion-imparting layers have adhesive properties to both plastics to be bonded.
• a polymethyl methacrylate layer can be connected to a plastic which is incompatible with polymethyl methacrylate via an adhesion-promoting layer which, for. B. alcohol or ether functions or epoxy groups z. B. from glycidyl methacrylate residues.
• a suitable adhesion promoter can e.g. B. a silane, such as. B. Methacryloyloxypropyl trimethoxysilane (MEMO). Suitable adhesion promoters for the various plastic combinations are familiar to the person skilled in the art.
• the structural layer is used to image microstructures in the course of producing the composite with the carrier layer, in particular in the coextrusion process, or at any later point in time, preferably when the composite was produced by lamination or painting.
• the support layer can be coated on one or more sides with the structural layer.
• the structure layer can have a layer thickness in the range of z. B. 1 to 1000, preferably from 2 to 500 and particularly preferably from 5 to 200 microns.
• the structural layer consists of 1 to 100, preferably 20 to 80, particularly preferably 30 to 70% by weight of a polymethacrylate molding composition, and 80 to 100, preferably 95 to 100% by weight of free-radically polymerized methyl methacrylate units and contains 0 to 20, preferably 0 to 5% by weight of further free-radically polymerizable comonomers and has an average molecular weight (weight average) I w of 30,000 g / mol to 70,000 g / mol.
• the low molecular weight polymethacrylate molding composition preferably has a viscosity number ( ⁇ S p / c) measured in chloroform according to ISO 1628 part 6 in the range from 25 to 35 ml / g, preferably 27-33 ml / g, corresponding to an average molecular weight Mw (weight average ) from 30,000 to 70,000, especially 40,000 to 60,000.
• ⁇ S p / c viscosity number measured in chloroform according to ISO 1628 part 6 in the range from 25 to 35 ml / g, preferably 27-33 ml / g, corresponding to an average molecular weight Mw (weight average ) from 30,000 to 70,000, especially 40,000 to 60,000.
• the molecular weight can e.g. B. by the differential scanning chromatography method (DSC) or by gel chromatography using Polymethyl methacrylate calibration standards or calibration lines that correlate with the viscosity number are determined.
• DSC differential scanning chromatography method
• Polymethyl methacrylate calibration standards or calibration lines that correlate with the viscosity number are determined.
• the proportion of the above-mentioned low molecular weight molding compound is less than 100% by weight, there is a mixture with up to 99% by weight, preferably 80 to 20, particularly preferably 70 to 30% by weight of a polymethacrylate molding compound which 80 to 100, preferably 80 to 95, in particular 82 to 88% by weight of free-radically polymerized methyl methacrylate units and 0 to 20% by weight of further free-radically polymerizable comonomers and an average molecular weight (weight average) of 90,000 to 200,000, in particular from 100,000 to 150,000 (g / mol).
• a molding composition of 80 to 98, particularly preferably 82 to 88% by weight of methyl methacrylate and 2 to 20, particularly preferably 12 to 18% by weight of methyl acrylate is preferred.
• the higher molecular weight polymethacrylate molding composition preferably has a viscosity number ( ⁇ s / c ) measured in chloroform according to ISO 1628 part 6 in the range from 50 to 80 ml / g, preferably 50-55 ml / g, corresponding to an average molecular weight I w (weight average ) from 90,000 to 200,000, in particular 100,000 to 150,000.
• ⁇ s / c measured in chloroform according to ISO 1628 part 6 in the range from 50 to 80 ml / g, preferably 50-55 ml / g, corresponding to an average molecular weight I w (weight average ) from 90,000 to 200,000, in particular 100,000 to 150,000.
• the other comonomers are, in principle, not critical to the feasibility of the invention, provided that they do not contain any other functional groups, such as, for example, the functional vinyl group arising in the radical polymerization.
• Suitable comonomers are e.g. B. esters of methacrylic acid (e.g. ethyl methacrylate, butyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate), esters of acrylic acid (e.g.
• Preferred comonomers are C to C 4 alkyl (meth) acrylates, in particular methyl acrylate, ethyl acrylate or butyl methacrylate.
• the structure layer can have a layer thickness in the range of z. B. 1 to 1000, preferably from 2 to 500 and particularly preferably from 5 to 200 microns.
• the microstructured surface of the structural layer is formed by known structuring methods, e.g. B. embossing, hot stamping, structuring prints or tapes, finite or endless tapes.
• microstructures can be embossed into the structure layer or into the structure layers by means of one or more embossing rollers after the exit of a coextrudate consisting of the melts of the carrier layer and the structure layer from the extrusion nozzle of an extrusion system in the melt state in a connected roller smoothing unit.
• microstructures can also be transferred into the already solidified structural layer by subsequent hot stamping. It offers especially when the composites were produced by laminating or painting.
• Plastic bodies are preferably available that are a composite of a carrier layer and one or more microstructured structural layers. According to the invention, however, plastic bodies are also available which, in the event of subsequent separation of the structural layer and the carrier layer, consist only of the microstructured structural layer.
• the plastic body according to the invention can be a solid plate or a film, a corrugated plate, a hollow chamber plate, in particular a double wall plate, a multiple plate or a truss plate or a tube or a rod in an angular, round, elliptical or oval shape.
• the plastic body according to the invention can advantageously be used, for. B. as components with friction-reducing surfaces for reducing the friction of air or water flows on surfaces of (air, water or land) vehicles or as lines and containers for reducing the friction of fluid flows with fast-flowing fluids in pipes and containers, for the targeted mixing of fluids , for the production of surfaces with modified acoustic properties, for the production of micro- or nanotiter plates, for reducing the adhesion of contaminants on surfaces worth protecting, as antimicrobial Surfaces, as light-guiding, light-directing, refractive and / or diffuse light-scattering surfaces and / or as anti-reflective surfaces.
• the method according to the invention makes it possible to produce plastic bodies with microstructured surfaces on one or more sides.
• finer structures can be reproduced compared to known methods.
• the advantageous improvements in the imaging properties can, for. B. understand microscopically.
• groove widths in the range from 10 to 20 ⁇ m can be easily implemented.
• such grooves can be shown in width when using embossing layers of the prior art, but are undesirably depicted as a whole and especially rounded on the top, so that the aspect ratios mostly remain below 1. Improvements in the imaging of pimple-like depressions in the order of magnitude of z. B. only 1 micron determine, the mountain and valley structures are mapped more regularly and pronounced, so that they almost correspond to the intended embossed structure.
• the good reproducibility of the embossed structures in the structural layer makes it possible to work with comparatively lower embossing pressures than was previously possible. This opens it up to thinner and / or softer backing layers, e.g. B. backing layers of polymethyl methacrylate plastics with lower average molecular weights M w , z. B. from 100,000 to 150,000. This increases the number of suitable material combinations.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Mechanical Engineering (AREA)
• Laminated Bodies (AREA)
• Manufacture Of Macromolecular Shaped Articles (AREA)
• Extrusion Moulding Of Plastics Or The Like (AREA)
• Shaping Of Tube Ends By Bending Or Straightening (AREA)
• Compositions Of Macromolecular Compounds (AREA)

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• 2003
  • 2003-07-02 DE DE10329938A patent/DE10329938A1/de not_active Withdrawn
• 2004
  • 2004-04-21 CN CNA2004800007664A patent/CN1700979A/zh active Pending
  • 2004-04-21 EP EP04728556A patent/EP1651422A1/de not_active Withdrawn
  • 2004-04-21 WO PCT/EP2004/004202 patent/WO2005002830A1/de active Application Filing
  • 2004-04-21 US US10/524,840 patent/US20060121248A1/en not_active Abandoned
  • 2004-04-21 JP JP2006515755A patent/JP2007516857A/ja not_active Withdrawn
  • 2004-04-21 KR KR1020057003620A patent/KR20060026400A/ko not_active Application Discontinuation
  • 2004-04-21 MX MXPA05002126A patent/MXPA05002126A/es unknown
• 2005
  • 2005-02-02 IL IL16667005A patent/IL166670A0/xx unknown

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