Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/30—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by mixing gases into liquid compositions or plastisols, e.g. frothing with air
• • 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
  • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
  • B29C44/02—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles
  • B29C44/04—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles consisting of at least two parts of chemically or physically different materials, e.g. having different densities
  • B29C44/06—Making multilayered articles
• • 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
  • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
  • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
  • B32B3/266—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by an apertured layer, the apertures going through the whole thickness of the layer, e.g. expanded metal, perforated layer, slit layer regular cells B32B3/12
• • 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
  • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
  • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
• • 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
  • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
  • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
  • B32B5/32—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed at least two layers being foamed and next to each other
• • 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
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/04—Interconnection of layers
  • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
  • B32B7/14—Interconnection of layers using interposed adhesives or interposed materials with bonding properties applied in spaced arrangements, e.g. in stripes
• • 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
  • B32B2255/00—Coating on the layer surface
  • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
  • B32B2255/102—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer synthetic resin or rubber layer being a foamed layer
• • 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
  • B32B2255/00—Coating on the layer surface
  • B32B2255/26—Polymeric coating
• • 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
  • B32B2266/00—Composition of foam
  • B32B2266/02—Organic
  • B32B2266/0214—Materials belonging to B32B27/00
  • B32B2266/0278—Polyurethane
• • 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
  • B32B2305/00—Condition, form or state of the layers or laminate
  • B32B2305/02—Cellular or porous
  • B32B2305/022—Foam
• • 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
  • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
• • 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
  • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
  • B32B2307/51—Elastic
• • 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
  • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
  • B32B2307/546—Flexural strength; Flexion stiffness
• • 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
  • B32B2479/00—Furniture
• • 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
  • B32B2605/00—Vehicles
  • B32B2605/08—Cars
• • 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
  • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
  • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2207/00—Foams characterised by their intended use
  • C08J2207/02—Adhesive
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
  • C08J2375/04—Polyurethanes
• • 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.]
  • Y10T428/24273—Structurally defined web or sheet [e.g., overall dimension, etc.] including aperture
• • 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.]
  • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
  • Y10T428/24826—Spot bonds connect components
• • 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
  • Y10T428/249921—Web or sheet containing structurally defined element or component
  • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
  • Y10T428/249981—Plural void-containing components
• • 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
  • Y10T428/249921—Web or sheet containing structurally defined element or component
  • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
  • Y10T428/249982—With component specified as adhesive or bonding agent

Definitions

• the invention relates to a highly flexible laminar composite material comprising a flexible block foam and a surface-connected layer of impact foam made from polyurethane-based dispersions, a process for producing such a composite material and the use thereof.
• Composite materials having a foam-based coating are well known in the art.
• aqueous polyurethane or acrylate dispersions are used which initially obtain a paste-like consistency by intensive stirring or whipping. The process is very similar to the production of whipped cream. For this reason, the term mechanical Schlagschaum is familiar.
• the foams are produced with an air content between 20 and 80 percent by volume. The density of the foams is given as the foam liter weight.
• the aqueous dispersions already readily foam on their own, additives for stabilizing the foams, such as, for example, ammonium stearate or SLES, are required.
• the foams may also comprise other additives customary in the coating, such as color pigments, additives, active ingredients and fillers.
• the dispersions used should have correspondingly high solids contents, so that a sufficient Schaumliterabout can be achieved. With polyurethane dispersions, solids contents of 40 to 60% are customary.
• industrial foam aggregates are used, as they also occur in the food industry. The application of the Schlagschaums is usually done by means of a doctor blade, the set gap width largely determines the wet film thickness.
• the foams must be dried at higher temperatures in order to obtain usable coatings.
• the wet foam is dried in several stages at increasing temperatures in the recirculating air stream, in such a way that the water does not boil and the foam structure is not destroyed.
• the final temperature in the drying process is about 160 0 C.
• the dried foams have closed cell or open cell structures, depending on the employed foam weight per liter on.
• the dry film thickness is usually slightly less than the wet film thickness.
• the layer thicknesses of the coatings are 0.05 to 1.0 mm, but also several millimeters are possible.
• the foams are much finer than the usual foams known from sponges and foam pads.
• foam coating is volume control with low material consumption and weight.
• the coatings are very soft and pleasant to the touch due to the foam structure. Therefore, foams are used in clothing, medical and technical articles, but also for the production of leather-like materials. In some cases, the foam must still be provided against damage and also for design reasons, with other, compact layers.
• the advantage of the use of impact foams is also that they are emission-free or at least very low emission process.
• the viscosity and the foam liter weight are adjusted so that a paste-like consistency is present.
• the type of squeegee which determines the application height, and the residence time until entry into the drying channel have an influence on the penetration depth.
• reverse coating also referred to as transfer coating or release (paper) coating
• the advantage of this method is, on the one hand, the possibility of imparting a defined surface structure, such as a grain, over a precursor of the release paper of the coating.
• the bond to the carrier material can also be better controlled than with the direct coating. Therefore, the articles thus produced are often much softer.
• polyurethane-based whipped-foam composite composites as are known in the art suffer from the disadvantage that they lack sufficient flexibility for many applications. In particular, many such composites, when used, for example, for cladding moving (machine) parts, interfere with their ability to wrinkle over time, thereby promoting faster wear of such composites.
• a sheet-like composite material comprising at least two interconnected foam elements, which is characterized in that it comprises a base material of a flexible block foam and a surface-connected layer of polyurethane-based impact foam.
• a flexible block foam is to be understood as meaning such polyurethane-based flexible foams which usually (but not necessarily) result from the use of polyether polyols having predominantly secondary OH groups as the polyol component.
• block flexible foams those which are obtainable by the process described in EP 0 810 256 A1, for example that of Bayer MaterialScience AG developed Hypemova ® soft foam.
• the flexible block foam is elastic.
• the foam used for the application of the layer of foam foam is made as generally described above.
• the foam is produced starting from polyurethane dispersions.
• one or more foam stabilizer (s), thickener, crosslinker and / or pigment (s) are added to the (usually commercially available) polyurethane dispersion prior to the actual foaming.
• additional diluent may be added if required.
• Polyurethane dispersions used in the context of the present invention particularly preferably and optionally in combination with one another are the following:
• Aliphatic polycarbonate ester polyether polyurethane dispersions It has in particular highlighted the following marketed by Bayer MaterialScience polyurethane dispersion as particularly preferred: Impranil ® DLL) dispersion.
• Impranil ® DLU is a polyurethane based on polycarbonate-polytetramethylene glycol (PC-PTMG), which is characterized by a high resistance.
• PC-PTMG polycarbonate-polytetramethylene glycol
• the product is compatible with the additives commonly used in textile coating and has been developed for the production of high-quality coatings, for example for upholstery material. It can be mechanically foamed or processed as a compact coating.
• the other four products are further developments of existing commercial products, which have an increased solids content of 60%.
• Impranil ® LP RSC 1380 can be used for the production of fashionable coatings and fleece finishing. Apart from the higher solids content of the product characteristics similar to those of Impranil ® DLN. Impranil ® LP RSC 1537 - the properties of which correspond to those of Impranil ® DLP-R - was developed primarily as a soft blending component for the production of upholstery materials, car seats, sports articles and other technical products. Impranil ® LP RSC 1537 is excellently suitable as an adhesive coating and represents an alternative to solventborne products. Impranil ® LP RSC 1554 - the product profile is largely identical to that of Impranil ® DLS - is particularly suitable for mechanical foaming and for the production of fashionable articles and products apparel goods. All of these dispersions are non-reactive, can be but to improve the fastness properties either with suitable melamine resins or water-dispersible polyisocyanates co-crosslink.
• high-solids 60% polyurethane dispersions are free of organic cosolvents, thickeners and external emulsifiers.
• the "high-solid" dispersions offer the end user a number of advantages compared to the commonly used polyurethane dispersions with solids contents between 35 and 50%, for example the achievement of high solid deposits in an order and thereby a significant cost saving by increasing the machine utilization and a Reduction of energy costs.
• foam stabilizers thickeners, crosslinkers and pigments
• the products well known in the art can be used.
• Foam stabilizers Stokal ® STA
• Pigments all water-soluble Euderm ® pigments
• the base material of the flexible foam and the layer of whipped foam can be connected in various ways.
• selective fixings of both foam materials by, for example, seams, Rivets or staples comes in particular a punctiform or planar adhesive layer into consideration.
• such composite materials retain the particularly favorable properties of constituents making up the same.
• such composite materials are highly flexible structures that do not tend to wrinkle even with prolonged use.
• the foam layer with a perforation, in particular a microperforation (see, for example, www.wista.com).
• a microperforation is to be understood as such a perforation, which has holes with a diameter in a range of 0.1 to 2 mm and a hole density of 10 pin / cm 2 .
• a microperforation is preferred insofar as it is characterized by an extremely high water vapor permeability, against liquid water, that is, in particular water droplets, but as good as impermeable, and thus helps prevent moisture in the block foam layer.
• the layer thickness of the impact foam is preferably in a range of 0.2 to 1.0 mm, in particular from 0.5 to 0.8 mm.
• the above-described upper limits in the layer thicknesses of the slabstock foam or the blown foam are particularly advantageous insofar as the material consumption can be limited to a minimum - above these limits, the mechanical properties of the composite material do not significantly improve.
• the said lower limits are particularly preferred inasmuch as the mechanical properties of the composite material deteriorate correspondingly when they fall below, which is particularly true for the wear resistance of both layers.
• the combination of the flexible block foam and the impact foam is preferably carried out by a broken or uninterrupted adhesive layer, in particular by an adhesive layer based on an aqueous polyurethane dispersion, such as, for example, Impranil LP RSC 4002 or Impranil DLP- R.
• aqueous polyurethane dispersion such as, for example, Impranil LP RSC 4002 or Impranil DLP- R.
• An adhesive layer ensures a permanent and reliable connection of both foam materials.
• An adhesive layer based on an aqueous polyurethane dispersion has the particular advantage that the adhesive layer forming after the composite also has a very high flexibility and thus does not adversely affect the mechanical properties of the composite material.
• the object underlying the invention is achieved by a method for producing a composite material, which is characterized in that one connects a flexible block foam with a layer of whipped foam.
• the method is carried out in such a way that it comprises the following steps: a) full or partial application of a blown foam, in particular a blown foam with a density in a range of 200 to 800 g / L, on a release paper; b) curing the impact foam layer applied by step a), in particular at elevated temperature in a range from 70 to 170 ° C., to form the layer of the impact foam; c) applying an adhesive layer, in particular an adhesive layer based on an aqueous polyurethane dispersion, to the layer of the blown foam and / or the block foaming foam; d) applying the flexible foam to the foam; e) curing the adhesive layer; f) Remove the release paper.
• the polyurethane dispersions used to produce the foam in step a) preferably have a solids content of> 50% by mass, since they have the advantage of being miscible with water in any ratio, drying faster and also setting very high Schaumliterthee to allow.
• the method just described leads to a reliable and permanent connection of both foam materials and also offers the advantage that a structure can be introduced into the side facing away from the slab soft foam side of the Schlagschaum Mrs by the use of a release paper.
• the above method is carried out so that the steps a) to f) are carried out in one operation.
• the object underlying the invention is achieved by the use of a composite material as just described for cladding and / or covering of movable or immovable objects and / or apparatuses. It can also be used, for example, as furniture, furniture cover or in the automotive sector, for example as a seat cover.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Laminated Bodies (AREA)
• Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

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Applications Claiming Priority (2)

Publications (1)

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Family Applications (1)

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Citations (8)

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• 2008
  • 2008-02-15 DE DE102008009192A patent/DE102008009192A1/de not_active Ceased
• 2009
  • 2009-02-04 MX MX2010008619A patent/MX2010008619A/es unknown
  • 2009-02-04 ES ES09711509T patent/ES2376274T3/es active Active
  • 2009-02-04 JP JP2010546238A patent/JP5596564B2/ja not_active Expired - Fee Related
  • 2009-02-04 WO PCT/EP2009/000714 patent/WO2009100837A1/de not_active Ceased
  • 2009-02-04 AT AT09711509T patent/ATE536994T1/de active
  • 2009-02-04 CN CN200980105148.9A patent/CN101945758B/zh not_active Expired - Fee Related
  • 2009-02-04 CA CA 2715528 patent/CA2715528A1/en not_active Abandoned
  • 2009-02-04 EP EP20090711509 patent/EP2247442B1/de not_active Not-in-force
  • 2009-02-04 PL PL09711509T patent/PL2247442T3/pl unknown
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