Classifications

• • 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
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B15/08—Layered products comprising a layer of metal comprising metal 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F259/00—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00
  • C08F259/08—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing fluorine
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
• • 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
  • C09J127/00—Adhesives based on 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; Adhesives based on derivatives of such polymers
  • C09J127/02—Adhesives based on 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; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
  • C09J127/12—Adhesives based on 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; Adhesives based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms

Definitions

• the present invention relates to a laminate with a fluoropolymer film that has flexibility while maintaining its heat resistance and non- stickiness, and to a film-forming fluoropolymer. More specifically, this invention relates to a laminate with a fluoropolymer and to a film-forming fluoropolymer appropriate for the rolls of copiers, printers, and the like.
• a preferred embodiment of the present invention is a laminate in which the functional group-containing fluoropolymer is a tetrafluoroethylene/trifluorovinyl ether group-containing dihydrogen phosphate ester compound/fluorine-containing comonomer copolymer resin.
• a preferred embodiment of the present invention is a laminate in which the fluorine-containing comonomer is a perfluoro(alkyl vinyl ether) or perfluoroalkyl vinyl.
• a preferred embodiment of the present invention is a laminate in which the functional group-containing fluoropolymer is a composition of a functional group-containing fluoropolymer and a fluoropolymer without functional groups.
• a preferred embodiment of the present invention is a laminate in which the fluoropolymer without functional groups is a tetrafluoroethylene/perfluoro(alkyl vinyl ether) or perfluoroalkyl vinyl copolymer resin.
• a preferred embodiment of the film-forming fluoropolymer composition of the present invention is a fluoropolymer composition in which the phosphate group-containing fluoropolymer is a copolymer resin of tetrafluoroethylene, a perfluoro(alkyl vinyl ether) or perfluoroalkyl vinyl, and a dihydrogen phosphate ester compound expressed by formula (1) below, which resin contains the perfluoro(alkyl vinyl ether) or perfluoroalkyl vinyl component in an amount of 3 to 15 mol%.
• the phosphate group-containing fluoropolymer is a copolymer resin of tetrafluoroethylene, a perfluoro(alkyl vinyl ether) or perfluoroalkyl vinyl, and a dihydrogen phosphate ester compound expressed by formula (1) below, which resin contains the perfluoro(alkyl vinyl ether) or perfluoroalkyl vinyl component in an amount of 3 to 15 mol%.
• Fluoropolymers according to the present invention are polymers made by polymerizing one or more monomers, at least one of which is a fluoromonomer.
• a fluoromonomer according to this invention is an olefin, including vinyl ethers containing at least one fluorine atom bonded to a carbon atom.
• the fluorine is bonded to a carbon atom which is part of the olefinic double bond.
• the functional group-containing fluoropolymer can be obtained, for example, by copolymerizing a functional group-containing fluorinated monomer.
• Examples of functional group-containing fluorinated monomers include the functional group-containing fluorinated monomers cited in U. S Patent No. 6,177,196 and U. S Patent No. 5,780,552.
• a functional group- containing fluoropolymer can also be obtained by reacting, such as by grafting, such a functional group-containing fluorinated monomer to a fluoropolymer.
• CF 2 CF(OR) m (CH 2 )OP(O)(OH) 2 (1)
• the fluoropolymer be a copolymer of tetrafluoroethylene (TFE) and at least one type of fluorine- substituted comonomer, the copolymer being obtained by copolymerization in accordance with a conventional method, such as aqueous emulsion polymerization, or polymerization in a solvent such as fluorinated solvent.
• TFE tetrafluoroethylene
• fluorine- substituted comonomer the copolymer being obtained by copolymerization in accordance with a conventional method, such as aqueous emulsion polymerization, or polymerization in a solvent such as fluorinated solvent.
• the functional group-containing fluoropolymer of the present invention is preferably obtained by copolymerizing a fluorinated monomer that contains the aforementioned functional group units when producing the fluoropolymer by polymerization. It is preferably a copolymer obtained by copolymerizing the aforementioned functional group-containing fluorinated monomer, TFE, and at least one type of fluorine-substituted comonomer in accordance with a conventional method. Polymerization can be done according to procedures known in the art. These include solution polymerization, wherein the solvent is a fluorocarbon or fluorochlorocarbon. Preferred is aqueous dispersion polymerization such as is described herein in the Examples. The concentration of the polymer in the aqueous medium is from abouti O to 50 wt%, preferably about 20 to 40 wt), and more preferably about 25 to 35 wt%.
• the compounds cited above can be given as examples of fluorine- substituted comonomers.
• Perfluoro(alkyl vinyl ethers) and perfluoroalkyl vinyls are especially preferred.
• the melting point of the functional group-containing fluoropolymer , of the present invention is preferably about 200-300 0 C, more preferably about 220-280 0 C.
• TFE/perfluoro(alkyl vinyl ether) copolymer resins and TFE/perfluoroalkyl vinyl copolymer resins among them are preferred.
• the admixture of the fluoropolymer and the functional group- containing fluoropolymer can also be accomplished by forming particles that have a core/shell structure as cited in U. S Patent No. 5,780,552.
• the shell comprises the functional group-containing fluoropolymer
• the core is the fluoropolymer.
• Particles that have such a core/shell structure can be manufactured through a polymerization process that produces fluoropolymer.
• a fluoropolymer is produced as the core by copolymerizing tetrafluoroethylene (TFE) with a perfluoro(alkyl vinyl ether), perfluoroalkyl vinyl, or another fluorine-substituted comonomer, and polymer particles that have a shell that contains a fluorinated monomer with functional groups can be pr ⁇ dirced by adding and further copolymerizing a fluorinated monomer that has the aforementioned functional groups in a stage near the end of copolymerization.
• TFE tetrafluoroethylene
• emulsion polymerization emulsion polymerization
• suspension polymerization emulsion polymerization
• the particles that have a core/shell structure obtained in this way are also a preferred embodiment of the functional group-containing fluoropolymer of the present invention.
• the quantities of the fluoropolymer and functional group-containing fluoropolymer produced can be calculated from the quantities of monomers polymerized when particles with a core/shell structure are produced by polymerization.
• the overall composition and content of the particles with a core/shell structure can be determined by 19 F-NMR, and the melting point can be measured by means of differential scanning calorimetry (DSC).
• the functional group-containing fluoropolymer of the present invention can be used as a film-forming fluoropolymer.
• the substrate is a material that constructs a roll, it may have a cylindrical shape or may be a cylinder shaped as part of the roller.
• the substrate is a sheet, it may be a molded product molded into a certain shape.
• the functfo ⁇ al group-containing fluoropolymer of the present invention can be used especially appropriately on rubber (elastomer) roller-shaped substrates that contain a metal oxide.
• the particle size range of metal oxide according to this invention is from about 0.01 to 50 ⁇ m, preferably from about 0.1 to 10 ⁇ m.
• a second layer of fluoropolymer can be formed on the external surface of the laminate that has a functional group-containing fluoropolymer formed as a film on the substrate to which a metal oxide has been added in accordance with the present invention.
• the functional group-containing fluoropolymer on the substrate functions as a primer.
• the laminate formed in this way has good interlayer adhesion because the functional group-containing fluoropolymer adheres firmly to the substrate, and the second layer of fluoropolymer adheres to the functional group-containing fluoropolymer.
• a laminate in which a fluoropolymer layer is formed on the substrate with an interposed functional group-containing fluoropolymer film layer is a preferred embodiment of the present invention.
• the substrate is a roller
• a laminate in which a fluoropolymer layer is formed on the roller with an interposed functional group-containing fluoropolymer film layer can be used appropriately in copiers and the like because such a roller can withstand high temperatures.
• Examples of methods for forming a fluoropolymer layer on a roller with an interposed functional group-containing fluoropolymer film layer . . include a method of forming a functional group-containing fluoropolymer film on a roller and covering the roller with a fluoropolymer tube, a method of forming a functional group-containing fluoropolymer film on the inner surface of a fluoropolymer tube and covering the roller with the tube, and a method of forming a functional group-containing fluoropolymer layer on the inner surface of a tube by coextrusion and covering the roller with the tube when the fluoropolymer tube is produced by extrusion molding.
• the present invention makes it possible to provide a base material in which a fluoropolymer film endowed both with flexibility and with the chemical resistance and low friction property of fluoropolymers is formed on the surface of a flexible substrate such as an elastomer.
• this solid contains 12 wt% PEVE and 0.6 wt% EVE-P.
• the primary melting point is 269 0 C and the secondary melting point is 257 0 C.
• the primer prepared as described above is applied 3-5 ⁇ m thick and dried (125 0 C for 20 min) on the surface of the rubber substrate pieces produced as described above by an ordinary application method (such as spray coating or immersion).
• a Fluoropolymer topcoat (40 wt% solids, composition shown below) is next applied and dried at 125°C for 20 minutes to yield a 25 ⁇ m thick coating.
• a film is then obtained by heating the coated substrate for 30 minutes at 300 0 C.

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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)
• Laminated Bodies (AREA)
• Paints Or Removers (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

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• 2005
  • 2005-07-28 EP EP05777477A patent/EP1915433A1/en not_active Withdrawn
  • 2005-07-28 JP JP2008523854A patent/JP2009502568A/ja active Pending
  • 2005-07-28 CN CN2005800512193A patent/CN101228241B/zh active Active
  • 2005-07-28 WO PCT/US2005/026964 patent/WO2007018515A1/en active Application Filing
  • 2005-07-28 KR KR1020087004651A patent/KR101301321B1/ko active IP Right Grant

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