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
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
  • C08J5/124—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives using adhesives based on a macromolecular component
• • 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
  • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
  • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
  • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
• • 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]
  • Y10T428/3154—Of fluorinated addition polymer from unsaturated monomers
• • 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]
  • Y10T428/3154—Of fluorinated addition polymer from unsaturated monomers
  • Y10T428/31544—Addition polymer is perhalogenated
• • 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.]
  • Y10T428/31645—Next to addition polymer from unsaturated monomers
  • Y10T428/31649—Ester, halide or nitrile of addition polymer
• • 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]
  • Y10T428/31652—Of asbestos
  • Y10T428/31663—As siloxane, silicone or silane
• • 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]
  • Y10T428/31652—Of asbestos
  • Y10T428/31667—Next to addition polymer from unsaturated monomers, or aldehyde or ketone condensation product
• • 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]
  • Y10T428/31678—Of metal
  • Y10T428/31692—Next to addition polymer from unsaturated monomers
  • Y10T428/31699—Ester, halide or nitrile of addition polymer

Definitions

• This invention relates to methods and compositions for bonding a fluoropolymer to a substrate.
• a method of bonding a fluoropolymer to a substrate includes providing a bonding composition between a fluoropolymer and a substrate to form a primed article and heating the primed article to a temperature and optionally applying pressure for a sufficient time to bond the fluoropolymer and the substrate to form a bonded article.
• the bonding composition includes an amino-substituted organosilane.
• the primed article may be heated to a temperature between 50 and 300°C, preferably between 100 and 250°C.
• the amino-substituted organosilane may have a hydrolyzable substituent.
• the amino- substituted organosilane may be 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, (a inoethylaminomethyl)phenethyltrimethoxysilane, (aminoethylaminomethyl)phenethyltriethoxysilane, N-(2-aminoethyl)-3- aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltris(2-ethylhexoxy)silane,
• the bonding composition may include a phase transfer catalyst or an acid catalyst.
• the phase transfer catalyst or acid catalyst may be a phosphonium salt, an ammonium salt, a fluoroaliphatic sulfonyl compound, a perfluoroalkylcarboxylic acid, or an arylcarboxylic acid.
• the bonding composition may include a solvent to facilitate applying a coating of the composition to a surface of the fluoropolymer or the substrate, or both. The solvent may be removed, for example, by drying, prior to contacting the substrate and fluoropolymer surfaces. Any solvent, if used may be a fluorinated solvent, for example, a fluorinated solvent having at least one fluorinated moiety. Fluorinated solvents may be effective at promoting wetting of the bonding composition onto either substrate.
• Preferred fluorinated solvents include, for example, hexafluoroxylene, hexafluorobenzene, and the like.
• Bonded multi-layer materials may have combined physical and chemical properties possessed by both fluoropolymers and non-fluorinated polymers, resulting in less expensive, well-performing articles.
• the fluoropolymer component may be used in automotive hose and container constructions, anti-soiling films, low energy surface PSA tapes and coatings for aircraft.
• the bonding process is a mild photochemical lamination that may promote adhesion between a fluoropolymer and a substrate.
• the bonding composition may be used to form a composite article having a fluoropolymer cladding on a conductive and lustrous metal to protect it from corrosion, a fluoropolymer cladding on glass fibers to enhance their physical strength and chemical resistance for telecommunication, or a fluoropolymer layer bonded to a hydrocarbon substrate in a multi-layer materials.
• FIG. 1 is a cross-sectional view of a multi-layer article.
• a fluoropolymer layer may be bonded on one surface of a substrate to form, for example, a laminate.
• the laminate may contain two or more layers.
• the laminate 10 includes fluoropolymer layer 20 and the substrate 30.
• Bonding composition 40 contacts the interface between fluoropolymer layer 20 and substrate 30. Heating the bonding composition promotes bonding between fluoropolymer layer 20 and substrate 30.
• the bonding composition includes an amino-substituted organosilane.
• the bonding composition may include a solvent to facilitate applying a coating of the composition to a surface of the fluoropolymers or the substrate, or both.
• the solvent may be removed, for example, by drying, prior to contacting the substrate and fluoropolymer surfaces.
• the amino- substituted organosilane may have a hydrolyzable substituent; for example, it may be a trialkoxysilane.
• the amino-substituted organosilane may have the formula
• L is a divalent straight chain Cl-12 alkylene , C3-8 cycloalkylene, 3-8 membered ring heterocycloalkylene, Cl-12 alkenylene, C3-8 cycloalkenylene, 3-8 membered ring heterocycloalkenylene, arylene, or heteroarylene.
• L is optionally substituted with Cl-4 alkyl, C2-4 alkenyl, C2-4 alkynyl, Cl-4 alkoxy, hydroxyl, halo, carboxyl, amino, nitro, cyano, C3-6 cycloalkyl, 3-6 membered heterocycloalkyl, monocyclic aryl, 5-6 membered ring heteroaryl, Cl- 4 alkylcarbonyloxy, Cl-4 alkyloxycarbonyl, Cl-4 alkylcarbonyl, formyl, Cl-4 alkylcarbonylamino, or Cl-4 aminocarbonyl.
• L is further optionally interrupted by -O-, -S-, - N(Rc)-, -N(Rc)-C(O)-, -N(Rc)-C(O)-O-, -O-C(O)-N(Rc)-, -N(Rc)-C(O)-N(Rd)-, -O-C(O)-, - C(O)-O-, or -O-C(O)-O-.
• 3-aminopropyltris(methoxyethoxyethoxy)silane 3-aminopropylmethyldiethoxysilane, 3- aminopropyltrimethoxysilane, and aminoundecyltrimethoxysilane.
• the phase transfer catalyst or acid catalyst facilitates effective bonding by, for example, partially dissolving in the fluoropolymer or the substrate or both.
• the phase transfer catalyst may be an ammonium compound, a phosphonium compound, a sulfonium compound, a sulfoxonium compound, an iodonium compound, a fluoroaliphatic sulfonyl compound, a perfluorocarboxylic acid, an arylcarboxylic acid, or combinations thereof. Examples include benzyltriphenylphosphonium chloride, benzyltributylammonium chloride, an arylammonium salt, a triarylsulfonium chloride. Other examples of light-absorbing compounds are described, e.g., in Fukushi, U.S. Patent No. 5,658,671, "Fluoroelastomer Coating Composition," hereby incorporated by reference.
• fluoropolymers typically are fluoroplastics that have melting temperatures ranging from about 100 to about 330°C, more preferably from about 150 to about 270°C.
• Preferred fluoroplastics include interpolymerized units derived from VDF and fluoroethylene and may further include interpolymerized units derived from other fluorine-containing monomers, non- fluorine-containing monomers, or a combination thereof.
• suitable non- fluorine-containing monomers include olefin monomers such as ethylene, propylene, and the like.
• a particularly useful fluoroplastic includes interpolymerized units derived from at least TFE and VDF in which the amount of VDF is at least 0.1% by weight, but less than 20% by weight. Preferably, the amount of VDF ranges from 3-15% by weight, more preferably from 10-15% by weight.
• suitable fluoroelastomers include VDF-HFP copolymers, VDF-HFP-TFE terpolymers, TFE-propylene copolymers, and the like.
• the substrate may include an inorganic substrate, such as a metal or an inorganic glass, or an organic substrate, such as a fluoropolymer or a non-fluorinated polymer.
• the substrate may be an organic-inorganic composite.
• the metal may be copper or stainless steel.
• the inorganic glass may be a silicate.
• the non-fluorinated polymer may be a polyamide, a polyolefin, a polyurethane, a polyester, a polyimide, a polyimide, a polystyrene, a polycarbonate, a polyketone, a polyurea, a polyacrylate, and a polymethyl methacrylate, or a mixture thereof.
• the non-fluorinated polymer may be a non-fluorinated elastomer, such as acrylonitrile-butadiene rubber (NBR), butadiene rubber, chlorinated and chlorosulfonated polyethylene, chloroprene rubber, ethylene-propylene monomer (EPM) rubber, ethylene- propylene-diene monomer (EPDM) rubber, epichlorohydrin (ECO) rubber, polyisobutylene rubber, polyisoprene rubber, polysulfide rubber, polyurethane, silicone rubber, blends of polyvinyl chloride and NBR, styrene butadiene (SBR) rubber, ethylene-acrylate copolymer rubber, and ethylene-vinyl acetate rubber.
• Suitable ethylene-vinyl acetate copolymers include
• Polyamides useful as the non-fluorinated polymer are generally commercially available.
• polyamides such as any of the well-known nylons are available from a number of sources.
• Particularly preferred polyamides are nylon-6, nylon-6,6, nylon- 1 1, and nylon-12.
• nylon-6 and nylon-6,6 offer better heat resistance properties than nylon-11 and nylon-12, whereas nylon-11 and nylon-12 offer better chemical resistance properties.
• other nylon materials such as nylon-6, 12, nylon-6,9, nylon-4, nylon-4,2, nylon-4,6, nylon-7, and nylon-8 may be used, as well as ring-containing polyamides such as nylon-6,T and nylon-6, 1.
• Suitable nylons include VESTAMIDTM L2140, a nylon-12 available from Creanova, Inc. of Somerset, NJ.
• Polyether-containing polyamides such as PEBAXTM polyamides (Atochem North America, Philadelphia, PA), may also be used.
• Useful polyols include polypentyleneadipate glycol, polytetramethylene ether glycol, polyethylene glycol, polycaprolactone diol, poly-l,2-butylene oxide glycol, and combinations thereof. Chain extenders such as butanediol or hexandiol may also be used in the reaction.
• Useful commercially available urethane polymers include
• PN-04 or 3429 from Morton International, Seabrook, NH
• X-4107 from B.F. Goodrich Co., Cleveland, OH.
• Useful polyolefin polymers include homopolymers of ethylene, propylene, and the like, as well as copolymers of these monomers with, for example, acrylic monomers and other ethylenically unsaturated monomers such as vinyl acetate and higher alpha-olefins. Such polymers and copolymers may be prepared by conventional free radical polymerization or catalysis of such ethylenically unsaturated monomers. The degree of crystallinity of the polymer may vary.
• the polymer may, for example, be a semi-crystalline high density polyethylene or may be an elastomeric copolymer of ethylene and propylene.
• Carboxyl, anhydride, or imide functionalities may be incorporated into the polymer by polymerizing or copolymerizing functional monomers such as acrylic acid or maleic anhydride, or by modifying the polymer after polymerization, e.g., by grafting, by oxidation, or by forming ionomers.
• functional monomers such as acrylic acid or maleic anhydride
• Examples include acid modified ethylene acrylate copolymers, anhydride modified ethylene vinyl acetate copolymers, anhydride modified polyethylene polymers, and anhydride modified polypropylene polymers.
• Such polymers and copolymers generally are commercially available, for example, as
• ENGAGETM (Dow-DuPont Elastomers, Wilmington, DE) or EXACTTM (ExxonMobil, Linden, NJ).
• anhydride modified polyethylene polymers are commercially available from E.I. DuPont de Nemours & Co., Wilmington, DE, under the trade designation BY ELTM co- extrudable adhesive resins.
• Useful polyacrylates and polymethacrylates include polymers of acrylic acid, methyl acrylate, ethyl acrylate, acrylamide, methacrylic acid, methyl methacrylate, ethyl methacrylate, and the like.
• An example of a polymethacrylate is EMACTM (Chevron Chemical Co., Houston, TX).
• Useful polyimide polymers include polyimide polymers made from the anhydride of pyromellitic acid and 4,4'-diaminodiphenyl ether available from E.I. DuPont de Nemours and Company under the tradename KAPTONTM. Variations include KAPTONTM H, KAPTONTM E and KAPTONTM V, among others.
• non-fluorinated polymers include polyesters, polycarbonates, polyketones, and polyureas.
• Commercially available examples of such polymers include SELARTM polyester (E.I. DuPont de Nemours & Co., Wilmington, DE),
• LEXANTM polycarbonate General Electric, Pittsfield, MA
• KADELTM polyketone Amoco, Chicago, IL
• SPECTRIMTM polyurea Low Chemical Co., Midland, MI
• elastomers include NIPOLTM 1052 NBR (Zeon Chemical, Louisville, KY), HYDRINTM C2000 epichlorohydrin-ethylene oxide rubber (Zeon Chemical, Louisville, KY), HYPALONTM 48 chlorosulfonated polyethylene rubber (E.I. DuPont de
• the substrate may include a second fluoropolymer.
• the substrate may have one or more surface polar functionality present thereon to enhance bonding, such as, for example, an amino, carboxyl and hydroxyl functionality.
• the bonding composition may be deposited on a surface of the fluoropolymer, the substrate or both.
• the bonding composition may be incorporated into the fluoropolymer, the substrate, or both, such that when the surfaces contact each other, the bonding composition contacts the fluoropolymer and the substrate simultaneously.
• the bonding composition may be incorporated into the fluoropolymer or the substrate by melt mixing or extruding a mixture including the bonding composition.
• the bonding composition may be applied to a surface of the fluoropolymer or substrate by an process such as, for example, spray coating, curtain coating, immersion coating, dip coating, and the like.
• Each of the fluoropolymer and the substrate may be provided as a film or as a molded or shaped article.
• the fluoropolymer and substrate may contact each other, for example, under pressure, and be heated to bond the layers. Heat is applied at a temperature and time suitable to form a bond between the substrate and the fluoropolymer.
• the temperature may be between 50 and 300°C, between 100 and 250°C, between 125 and 225°C, or between 150 and 220°C.
• more than one fluoropolymer layer may contact more than one surface of the substrate.
• two substrates may contact two surfaces of a fluoropolymer.
• heat, pressure, or combinations thereof may be desired during bonding.
• Suitable heat sources include, but are not limited to, ovens, heated rollers, heated presses, infrared radiation sources, flame, and the like.
• Suitable pressure sources are well known and include presses, nip rollers, and the like.
• wt% means weight percent based on total weight.
• “DyneonTM THVTM 500” refers to a terpolymer of TFE/HFP/VDF, having a melt temperature of 165°C; “DyneonTM THVTM 400” refers to a terpolymer of TFE/HFP/VDF, having a melt temperature of 150°C; “DyneonTM THVTM 200” refers to a terpolymer of TFE/HFP/VDF, having a melt temperature of 120°C; “HTE” refers to a terpolymer of hexafluoropropylene, teterafluoroethylene and ethylene all available from Dyneon, L.L.C. of Oakdale, MN.
• PVDF-HV refers to "PVDF 11010" which is a tradename for a copolymer of hexafluoropropylene and vinylidene fluoride having a melting point of 160°C;
• PVDF-CV refers to SOLEFTM PVDF-CV which is a copolymer of chlorotrifluoroethylene and vinylidene fluoride, both commercially available from Soltex Polymer Corp. of Houston, TX.
• BYNELTM 3101 is an acid modified ethylene-vinyl acetate copolymer
• EL VAXTM 450 is an ethylene-vinyl acetate copolymer havingl ⁇ wt% vinyl acetate and a Vicat softening
• polyimide refers to "KAPTONTM 100HN” film, all commercially available from E.I. DuPont de Nemours of Wilmington DE.
• EMACTM 2202T is a copolymer of ethylene and methyl acrylate, 80/20 by weight available from Chevron Chemical Co. of Houston, TX.
• VESTAMIDTM L2140 refers to nylon 12 having a Vicat softening point of 140°C commercially available from Creanova, Inc. of Somerset, NJ.
• Copper-coated polyimide refers to "KAPTONTM 100HN” film that has been metallized with copper.
• Gold-coated polyimide refers to "KAPTONTM 100HN” film that has been metallized with gold.
• Polycarbonate film refers to polyethylene terephthalate film of about 10 mils (0.25mm) thickness.
• a first bonding composition (BC 1) was prepared by dissolving 3-aminopropyltriethoxysilane (10 wt%) in methanol.
• a second bonding composition (BC 2) was prepared by dissolving 3-aminopropyltriethoxysilane (5 wt%) in methanol.
• a third bonding composition (BC 3) was prepared by mixing 3- aminopropyltriethoxysilane (5 wt%) and a catalytic amount (less than 1 wt%) of nonafluorobutylsulfonamide in methanol. All the above chemicals are available from Aldrich Chemical Co.
• Each substrate was coated with one of the bonding composition solutions. It was not necessary to dry the bonding composition before forming the bond.
• Samples were prepared by contacting a fluoropolymer film surface with the bonding composition-coated substrate surface to form a laminate precursor. A strip of a silicone liner was inserted about 1.3 mm into the space between the films along the short edge for peel testing. In some cases, a slight force was applied to keep good surface contact.
• the laminated multi-layer samples were subjected to hot lamination for 2 minutes at 200°C, except in the case of nylon, for which the hot lamination was performed at 220-250°C. The heating was carried out using a Wabash Hydraulic Press Co. heated platen press to achieve a film thickness of 0.51 mm. After cooling to room temperature by a "cold press", the peel strength was measured (film thickness of 0.51 mm). The heating times are indicated in Tables 1 and 2.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Manufacturing & Machinery (AREA)
• Polymers & Plastics (AREA)
• Laminated Bodies (AREA)
• Adhesives Or Adhesive Processes (AREA)
• Manufacture Of Macromolecular Shaped Articles (AREA)
• Lining Or Joining Of Plastics Or The Like (AREA)
• Organic Insulating Materials (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Glass Compositions (AREA)
• Compositions Of Macromolecular Compounds (AREA)

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• 2001
  • 2001-05-21 US US09/862,124 patent/US6753087B2/en not_active Expired - Lifetime
• 2002
  • 2002-02-25 PT PT02725015T patent/PT1401927E/pt unknown
  • 2002-02-25 JP JP2002592381A patent/JP4166581B2/ja not_active Expired - Fee Related
  • 2002-02-25 AU AU2002255606A patent/AU2002255606A1/en not_active Abandoned
  • 2002-02-25 CA CA 2446158 patent/CA2446158A1/en not_active Abandoned
  • 2002-02-25 WO PCT/US2002/005799 patent/WO2002094911A2/en not_active Ceased
  • 2002-02-25 AT AT02725015T patent/ATE325156T1/de not_active IP Right Cessation
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