Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
  • C09J175/04—Polyurethanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/48—Polyethers
• • 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
  • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
  • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
  • C08G18/4063—Mixtures of compounds of group C08G18/62 with other macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2170/00—Compositions for adhesives
  • C08G2170/20—Compositions for hot melt adhesives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2250/00—Compositions for preparing crystalline polymers
• • 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
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, 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
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
  • Y10T428/31591—Next to cellulosic

Definitions

• the invention relates to modified, one-component, moisture-curing polyurethane hotmelt adhesives and their use for laminating films onto plastic, wood, wood-based materials, metals, stone or similar materials.
• a colored or patterned surface film On the surface of objects such as Window profiles, doors, frames, housings made of plastic, wood, wood-based materials, metals or similar materials are often applied with a colored or patterned surface film in order to firstly protect the surface of the objects against harmful influences, e.g. To protect against corrosion, discoloration through light or mechanical influences. Another reason for applying the surface film may be to make the surface of the object more appealing.
• a surface film applied in this way should protect the surface of the object from environmental influences such as Protect the effects of water, moisture, temperature changes or light, especially sunlight or environmental pollutants in the air.
• plastic profiles in particular profiles made of thermoplastic materials such as polyvinyl chloride (PVC), polypropylene (PP), acrylonitrile-butadiene-styrene copolymers (ABS) have because of their ease of manufacture using the extrusion process, their low costs and found their widespread use properties, whether as full, hollow or core profiles.
• PVC polyvinyl chloride
• PP polypropylene
• ABS acrylonitrile-butadiene-styrene copolymers
• the PVC to be used can be both soft and semi-rigid or in particular hard PVC.
• Surface foils are used either PVC foils, CPL (Continuous Pressure Laminates) and HPL (High Pressure Laminates) foils, (printed) paper, veneer or other flat structures, which usually have a thickness of 0.1 to 1.0 mm to have.
• the adhesion-promoting layer can be carried out with the aid of a plasma or corona pretreatment, but adhesion-promoting primers in the form of primers, e.g. aqueous primers as disclosed in DE-A-19826329 can be made.
• Adhesive-promoting surface pretreatment of the plastic surfaces or plastic films can also be carried out using the cleaning agent described in WO 99/46352.
• the cleaned plastic surfaces can be subjected to a further mechanical, physical, chemical or electrochemical pretreatment prior to bonding. This can in particular be an order from an adhesion promoter or primer, e.g. of the aforementioned type, or a pretreatment can be carried out by flame treatment or by a corona treatment.
• films are increasingly being proposed for the field of outdoor applications.
• these are films based on (meth) acrylates, in particular mixtures of different polymethacrylate homo- and copolymers.
• poly (meth) acrylate films are that films of different hardnesses (from brittle hard to high flexibility) can easily be produced by a suitable choice of the co-monomers.
• Another advantage can be seen in the fact that normal, highly light-fast organic pigments or iron, chromium or nickel-containing pigments can be used to pigment such films.
• EP-A-343491 proposes multilayer films made of a (meth) acrylate base film with a crystal-clear polyacrylate cover film and a further crystal-clear protective film made of polyvinylidene fluoride (PVDF) or polyvinyl fluoride (PVF).
• PVDF polyvinylidene fluoride
• PVF polyvinyl fluoride
• Such single-layer or multilayer surface films based on acrylates or methacrylates have excellent light and weather resistance, but permanent weather-resistant bonding of these films with the aforementioned materials made of thermoplastic polymers, wood, aluminum and the like was not possible with previously known hotmelt adhesives.
• a one-component, moisture-curing polyurethane hotmelt adhesive which contains at least one reaction product with reactive isocyanate groups, which by reacting at least one di- or polyisocyanate with one or more Polyether polyols, partially crystalline or crystalline polyester polyols and / or low molecular weight polymers from olefinically unsaturated monomers and optionally tackifying resins is obtained.
• Another object of the present invention is the use of the above-mentioned polyurethane hotmelt adhesives for bonding single-layer or multilayer (meth) acrylate surface films to substrates made of thermoplastic materials, wood or aluminum.
• thermoplastic materials wood or aluminum.
• PVC, propylene, ABS are used as thermoplastic materials, either as factory-fresh plastics or as recycled material or, where appropriate, mixtures of freshly-made plastics and recyclates.
• the polyurethane hotmelt adhesive according to the invention is used for bonding multilayer films made from a base film based on pigmented (meth) acrylate polymers or (meth) acrylate copolymers and a surface film made from methacrylate copolymers, polyvinylidene fluoride or polyvinyl fluoride or a combination thereof.
• Another object of the present invention is a method for laminating single or multilayer films of the aforementioned type on molded articles made of thermoplastic, wood or aluminum, characterized by the following essential process steps:
• the surface treatment of the side of the 1- or multilayer film to be glued is usually carried out by flame treatment, corona treatment, primer application or pretreatment with a cleaner or by a combination of the above-mentioned treatment methods, b) the hot-melt adhesive is then applied to the surface film, c) if necessary the molded body surface is pretreated by primer application, with a cleaner or by flame treatment or corona treatment, if necessary followed by flashing off the volatile constituents, possibly with the addition of heat.
• the surface pretreatment of the molded body surface can also consist of a combination of one or more of the aforementioned methods.
• the film is then joined to the shaped body, the film possibly being pressed on by suitable means.
• either the surface pretreatment of the surface film or the pretreatment of the molded body can be omitted.
• the film and / or moldings can be heated before the adhesive is applied or before joining.
• Monomeric di- or polyisocyanates for the purposes of this invention are aromatic, aliphatic or cycloaliphatic diisocyanates whose molecular weight is less than 500.
• aromatic diisocyanates are all isomers of tolylene diisocyanate (TDI) either in isomerically pure form or as a mixture of several isomers, naphthalene-1,5-diisocyanate (NDI), naphthalene-1,4-diisocyanate (NDI) and diphenylmethane-4,4 'diisocyanate (MDI), diphenylmethane-2,4'-diisocyanate and mixtures of 4,4'-diphenylmethane diisocyanate with the 2,4'-isomer, xylylene diisocyanate (XDI), 4,4'-diphenyl-dimethylmethane diisocyanate, di - And tetraalkyl-diphenylmethane diisocyanate, 4,4-dibenzyl diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate (TD
• Suitable cycloaliphatic diisocyanates are the hydrogenation products of the aforementioned aromatic diisocyanates such as 4,4'-dicyclohexylmethane diisocyanate (H12MDI), 1-isocyanatomethyl-3-isocyanato-1, 5,5-trimethylcyclohexane (isophorone diisocyanate, IPDI), cyclohexane 1,4-diisocyanate, hydrogenated xylylene diisocyanate (H ⁇ XDI), 1-methyl-2,4-diisocyanato-cyclohexane, m- or p-tetramethylxylene diisocyanate (m-TMXDI, p-TMXDI) and dimer fatty acid diisocyanate.
• aromatic diisocyanates such as 4,4'-dicyclohexylmethane diisocyanate (H12MDI), 1-isocyanatomethyl-3-isocyanato-1, 5,
• aliphatic diisocyanates are tetramethoxybutane-1,4-diisocyanate, butane-1,4-diisocyanate, hexane-1,6-diisocyanate (HDI), 1,6-diisocyanato-2,2,4-trimethylhexane, 1,6- Diisocyanato-2,4,4-trimethylhexane, lysine diisocyanate and 1, 12-dodecane diisocyanate (C12DI).
• a particularly preferred isocyanate is MDI.
• the known polypropylene glycols or polybutylene glycols are used as polyether polyols.
• Examples are di- and / or trifunctional polypropylene glycols with two or three hydroxyl groups per molecule in the molecular weight range from 400 to 20,000, preferably in the range from 1,000 to 6,000.
• Statistical and / or block copolymers of ethylene oxide and propylene oxide can also be used.
• Another group of polyethers which are preferably to be used are the polytetramethylene glycols (polybutylene glycols, poly (oxytetramethylene) glycol, poly-THF), which are produced, for example, by the acidic polymerization of tetrahydrofuran, the molecular weight range of the polytetramethylene glycols being between 600 and 6000, preferably in the range Range from 800 to 5000.
• At least two polyether polyols are preferably used, a polyether polyol having an average molecular weight above 1000 and a polyether polyol having an average molecular weight below 1000, the preferred molecular weight range for the latter being 400 to 800.
• the polyether polyols in particular the low molecular weight polyols, it is also possible Alkylene diols such as Butanediol, hexanediol, octanediol, decanediol or dodecanediol can be used.
• Suitable polyester polyols are the crystalline or partially crystalline polyesters which are obtained by condensation of di- or tricarboxylic acids, e.g. Adipic acid, sebacic acid, glutaric acid, azelaic acid, suberic acid, undecanedioic acid, dodecanedioic acid, 3,3-dimethylglutaric acid, terephthalic acid, isophthalic acid, hexahydrophthalic acid, dimer fatty acid or their mixtures with low molecular weight diols or triols such as e.g.
• di- or tricarboxylic acids e.g. Adipic acid, sebacic acid, glutaric acid, azelaic acid, suberic acid, undecanedioic acid, dodecanedioic acid, 3,3-dimethylglutaric acid, terephthalic acid, isophthalic acid, hexahydrophthalic acid, dimer fatty acid or their mixture
• Ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1, 4-butanediol, 1, 6-hexanediol, 1, 8-octanediol, 1,10-decanediol, 1, 12-dodecanediol, dimer fatty alcohol, glycerol, trimethylolpropane or their mixtures can be prepared.
• polyesters to be used according to the invention are the polyesters based on ⁇ -caprolactone, also called “polycaprolactones".
• polyester polyols of oleochemical origin can also be used.
• Such polyester polyols can, for example, by complete Ring opening of epoxidized triglycerides of an at least partially olefinically unsaturated fatty acid-containing fat mixture with one or more alcohols with 1 to 12 carbon atoms and subsequent partial transesterification of the triglyceride derivatives to alkyl ester polyols with 1 to 12 carbon atoms in the alkyl radical.
• Other suitable polyols are polycarbonate polyols and dimer diols (from Henkel) and castor oil and its derivatives.
• the molecular weight data for the aforementioned polyether polyols or polyester polyols are number-average molecular weights which are generally determined by calculation from the hydroxyl number.
• Low molecular weight polymers from olefinically unsaturated monomers are polymers made from one or more comonomers selected from acrylic acid, methacrylic acid, C 1 -C 10 -alkyl esters of acrylic acid, methacrylic acid, esters of (meth) acrylic acid from glycol ethers such as methoxyethanol , Ethoxyethanol, propoxyethanol and / or butoxyethanol, vinyl esters, such as vinyl acetate, vinyl propionate, vinyl esters of highly branched monocarboxylic acids such as Versatic acid (Shell Chemie's product), vinyl ether, fumaric acid ester, maleic acid ester, styrene, alkylstyrene, butadiene or acrylonitrile and mixtures thereof.
• comonomers selected from acrylic acid, methacrylic acid, C 1 -C 10 -alkyl esters of acrylic acid, methacrylic acid, esters of (meth) acrylic acid from glycol ethers such
• these low molecular weight polymers have active hydrogen groups in the form of hydroxyl groups, primary or secondary amino groups, so that these low molecular weight polymers can be chemically incorporated into the polymer matrix of the hot melt adhesive.
• the low molecular weight polymers are usually prepared by radical polymerization or copolymerization of the aforementioned monomers.
• hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate or esters of acrylic acid or methacrylic acid with glycol oligomers or polymers such as di-, tri-, tetra- and / or polyethylene glycol with the above mentioned monomers are copolymerized.
• the corresponding amino-functional comonomers can also be used.
• the molecular weight range of the low molecular weight polymers from olefinically unsaturated monomers is between 10,000 and 150,000 daltons, preferably 20,000 and 80,000 daltons.
• the average molecular weight is determined by standard gel permeation chromatography (GPC), as is customary in the case of radical copolymers, the latter being sometimes also called "size exclusion chromatography" (SEC).
• GPC gel permeation chromatography
• SEC size exclusion chromatography
• the average molecular weight is calibrated against an external polystyrene standard with a certified molecular weight.
• OH-functional polymers When using the OH-functional polymers, they should have an OH number (DIN 53783) of 0.5 to 20, preferably between 1 and 15. Particularly suitable low molecular weight polymers with active hydrogen groups are disclosed in WO 99/28363 on pages 13 to 14. The teaching of this disclosure is expressly part of this application.
• tackifying resins e.g. Abietic acid, abietic acid esters, terpene resins, terpene phenol resins, phenol-modified styrene polymers, phenol-modified ⁇ -methylstyrene polymers or hydrocarbon resins are used.
• these tackifying resins can contain active hydrogen atoms, so that they are incorporated into the binder matrix of the hot melt adhesive during the reaction with the di- or polyisocyanates.
• active hydrogen atoms hydroxy-functional esters of abietic acid or hydroxylated terpene phenol resins.
• polyurethane compositions with no or very low content of monomeric, low molecular weight diisocyanates can be used as polyurethane hot melt adhesives according to the invention.
• Such hot melt adhesive compositions are the subject of WO01 / 40342, for example.
• the teaching of this application with respect to the compositions with low residual monomer content is expressly the subject of the present application.
• the hotmelt adhesives according to the invention can additionally contain stabilizers, adhesion-promoting additives, fillers, pigments, plasticizers and / or catalysts.
• “Stabilizers” in the sense of this invention are, on the one hand, stabilizers which bring about a viscosity stability of the polyurethane prepolymer during manufacture, storage or application.
• stabilizers e.g. monofunctional carboxylic acid chlorides, monofunctional highly reactive isocyanates, but also non-corrosive inorganic acids are suitable, examples being benzoyl chloride, toluenesulfonyl isocyanate, phosphoric acid or phosphorous acid.
• antioxidants, UV stabilizers or hydrolysis stabilizers are to be understood as stabilizers in the sense of this invention.
• antioxidants possibly in combination with UV protection agents.
• examples of these are the commercially available sterically hindered phenols and / or thioethers and / or substituted benzotriazoles or the sterically hindered amines of the HALS type ("hindered amine light stabilizer").
• hydrolysis stabilizers e.g. of the carbodiimide type can be used.
• Catalysts containing can accelerate the formation of the polyurethane prepolymer during its production and / or the moisture crosslinking after application of the adhesive in a manner known per se.
• Suitable catalysts according to the invention are in particular the organotin and / or amine catalysts mentioned in the aforementioned WO01 / 40342 on pages 11 to 13 in the amounts specified therein.
• the polyurethane hotmelt adhesives according to the invention contain
• a diisocyanate preferably diphenylmethane diisocyanate
• the aforementioned reactive products can be prepared separately by reaction with the diisocyanate, and the separately isocyanate-functional reactants thus produced can then be mixed in the desired amount. Further possibilities of production are disclosed in WO 99/28363 on page 16 and page 17, which are expressly part of the disclosure content of this application.
• the polyurethane hotmelt adhesives according to the invention are produced in a one-step reaction or, when functional low molecular weight polymers are used, the total amount of the low molecular weight polymer is mixed in a small amount of one or more of the polyols, followed by the addition of the total amount of the polyisocyanate. When this reaction is complete, the remaining amount of the polyols or polyol mixtures is added.
• a reactive hot melt adhesive composition with free isocyanate groups was produced from the following components in a heatable stirred tank:
• Polypropylene glycol MW 400, OH number 260 4.87%
• Acrylic copolymer MW 34000, OH number 2.1 24.38% hydroxylated tackifier resin, OH number 75 4.87%
• the hotmelt adhesive composition was conventionally filled into moisture-tight containers and had the following key figures:
• the reactive hotmelt adhesive according to Example 1 was used to bond a multilayer window decoration film based on a pigmented acrylic film with transparent, colorless acrylic / polyvinylidene fluoride coextrusion film as a surface layer with a standard PVC window profile.
• the acrylate side was used as the adhesive side of the decorative film.
• the bonding was carried out on a standard profile wrapping machine, of the Friz type, DTC-2, the PVC profile being pretreated with a solvent-based primer 6-B-23 from Henkel Dorus.
• the doctor blade gap of the coating machine was 50 ⁇ m
• the hot melt adhesive temperature was 130 ° C.
• the temperature of the PVC profile was 55 ° C.
• the bond was tested for its peel strength after 10 minutes, 1 hour, 1 day, 7 days and after aging (7 days, 70 ° C. with water exposure). The results are summarized in the table below.
• QR5305 Purmelt QR5305, from Henkel KGaA
• QR3530-24 Purmelt QR3530-24, from Henkel KGaA
• FAST multilayer film a.
• MBAS 2 standard PVC film
• the hotmelt adhesive according to Example 1 is superior to commercially available polyurethane hotmelt adhesives (QR 5305) or commercially available acrylate-containing hotmelt adhesives (QR 3530 - 24) in terms of both the initial peel strength and the final peel strength, even after aging, if the highly light-resistant multi-layer foils based on acrylic base foils are used for bonding.
• the hotmelt adhesive according to the invention according to Example 1 is also suitable for bonding conventional PVC films (see Example 6).

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Adhesives Or Adhesive Processes (AREA)
• Laminated Bodies (AREA)

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• 2001
  • 2001-10-05 DE DE10149142A patent/DE10149142A1/de not_active Withdrawn
• 2002
  • 2002-09-26 PL PL02367492A patent/PL367492A1/xx not_active Application Discontinuation
  • 2002-09-26 KR KR10-2004-7004900A patent/KR20040045471A/ko not_active Ceased
  • 2002-09-26 BR BR0213123-4A patent/BR0213123A/pt not_active IP Right Cessation
  • 2002-09-26 WO PCT/EP2002/010804 patent/WO2003031490A1/de not_active Ceased
  • 2002-09-26 CN CNB028195760A patent/CN1331907C/zh not_active Expired - Fee Related
  • 2002-09-26 CA CA002462830A patent/CA2462830A1/en not_active Abandoned
  • 2002-09-26 JP JP2003534472A patent/JP2005504867A/ja active Pending
  • 2002-09-26 EP EP02772349A patent/EP1432748A1/de not_active Withdrawn
  • 2002-09-26 MX MXPA04003025A patent/MXPA04003025A/es active IP Right Grant
• 2004
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