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
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/12—Powdering or granulating
• • 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
• • 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
  • B32B15/18—Layered products comprising a layer of metal comprising iron or steel
• • 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
  • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
• • 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
  • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
• • 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
  • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
  • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
• • 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
  • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
  • B32B27/285—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising 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
  • B32B27/30—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
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
  • B32B27/322—Layered products comprising a layer of synthetic resin comprising polyolefins comprising halogenated polyolefins, e.g. PTFE
• • 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
  • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
• • 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
  • B32B5/16—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 formed of particles, e.g. chips, powder or granules
• • 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
• • 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
  • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
  • B32B9/005—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile
• • 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
  • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
  • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B9/041—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of metal
• • 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
  • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
  • C08J5/10—Reinforcing macromolecular compounds with loose or coherent fibrous material characterised by the additives used in the polymer mixture
• • 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
  • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
• • 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
  • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
  • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
  • C08J5/243—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using carbon fibres
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
  • C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or halogen-containing compounds
  • C08L23/283—Iso-olefin halogenated homopolymers or copolymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
  • C08L27/02—Compositions 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; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L27/12—Compositions 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; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
  • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
  • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/03—Use of materials for the substrate
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/03—Use of materials for the substrate
  • H05K1/0313—Organic insulating material
  • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/03—Use of materials for the substrate
  • H05K1/0313—Organic insulating material
  • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
  • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K3/00—Apparatus or processes for manufacturing printed circuits
  • H05K3/0011—Working of insulating substrates or insulating layers
  • H05K3/0014—Shaping of the substrate, e.g. by moulding
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K3/00—Apparatus or processes for manufacturing printed circuits
  • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
  • H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
• • 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
  • B32B2250/00—Layers arrangement
  • B32B2250/44—Number of layers variable across the laminate
• • 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
  • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
  • B32B2260/02—Composition of the impregnated, bonded or embedded layer
  • B32B2260/021—Fibrous or filamentary 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
  • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
  • B32B2260/04—Impregnation, embedding, or binder material
  • B32B2260/046—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
  • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
  • B32B2262/02—Synthetic macromolecular fibres
  • B32B2262/0261—Polyamide fibres
• • 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
  • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
  • B32B2262/10—Inorganic fibres
  • B32B2262/101—Glass fibres
• • 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
  • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
  • B32B2262/10—Inorganic fibres
  • B32B2262/106—Carbon fibres, e.g. graphite fibres
• • 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
  • B32B2307/70—Other properties
  • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
• • 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
  • B32B2457/00—Electrical equipment
  • B32B2457/08—PCBs, i.e. printed circuit boards
• • 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
  • B32B2605/00—Vehicles
  • B32B2605/18—Aircraft
• • 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
  • C08F214/00—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
  • C08F214/18—Monomers containing fluorine
  • C08F214/26—Tetrafluoroethene
• • 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
  • C08F214/00—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
  • C08F214/18—Monomers containing fluorine
  • C08F214/26—Tetrafluoroethene
  • C08F214/262—Tetrafluoroethene with fluorinated vinyl ethers
• • 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
• • 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
  • C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene
• • 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
  • C08J2327/22—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 modified by chemical after-treatment
• • 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
  • C08J2427/00—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
  • C08J2427/02—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
  • C08J2427/12—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
  • C08J2427/18—Homopolymers or copolymers of tetrafluoroethylene
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
  • H05K2201/01—Dielectrics
  • H05K2201/0137—Materials
  • H05K2201/015—Fluoropolymer, e.g. polytetrafluoroethylene [PTFE]
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
  • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
  • H05K2201/0203—Fillers and particles
  • H05K2201/0206—Materials
  • H05K2201/0209—Inorganic, non-metallic particles

Definitions

• the present invention relates to a resin powder, a method for its production, a composite, a molded product, a method for producing a ceramic molded product, a metal laminated plate, a printed circuit board and a prepreg.
• a printed circuit board for example, one obtained by laminating a metal foil on a substrate made of an insulating material such as polyimide and forming a circuit by patterning the metal foil, is used.
• Patent Document 1 As a material having a low relative dielectric constant and useful for printed circuit boards, a composite has been proposed, which is obtained by filling a fluoropolymer fine powder having an average particle size in a range of from 0.02 to 5 ⁇ m in a polyimide (Patent Document 1).
• Patent Document 1 a commercially available powder of polytetrafluoroethylene (hereinafter referred to also as “PTFE”) is pulverized by a hammer mill to prepare the fluoropolymer fine powder.
• PTFE polytetrafluoroethylene
• Patent Document 1 JP-A-2005-142572
• the present inventors have found that if it is attempted to pulverize particles composed mainly of a tetrafluoroethylene/perfluoro(alkyl vinyl ether) copolymer (hereinafter referred to also as “PFA”) by a hammer mill, to obtain a powder having an average particle size of at most 50 ⁇ m, there is a problem that the bulk density decreases. Further, as a result of a further study, it has been found that there is a problem similar to above, also with respect to particles composed mainly of a fluorocopolymer having a melting point of from 260 to 320° C. other than PFA. For a powder having a small bulk density with an average particle size of at most 50 ⁇ m, it is necessary to provide an extra storage space when it comes to industrial handling for combining it with other materials.
• PFA tetrafluoroethylene/perfluoro(alkyl vinyl ether) copolymer
• the present inventors have made intensive studies and, as a result, have found that in a case where PFA having a unit containing a specific functional group introduced is used, as PFA, there is a tendency that as compared with the case of using common PFA having no such unit introduced, the average particle size of the pulverized product obtained by conducting mechanical pulverization under the same conditions is small and the bulk density is large. Further, it has been found that there is the same tendency as above, also with respect to a fluorocopolymer having a melting point of from 260 to 320° C. other than PFA, when one having a unit containing a specific functional group introduced, is used. Based on these findings, the present invention has been accomplished.
• the present invention has the following aspects.
• a method for obtaining a resin powder having an average particle size of from 0.02 to 50 ⁇ m which comprises subjecting resin particles (A) having an average particle size of at least 100 ⁇ m to mechanical pulverization treatment, and which is characterized in that the resin particles (A) are made of a material (X) containing the following fluorocopolymer (X1) as the main component:
• Fluorocopolymer (X1) a fluorocopolymer which has a unit (1) containing at least one type of functional group selected from the group consisting of a carbonyl group-containing group, a hydroxy group, an epoxy group and an isocyanate group, and a unit (2) based on tetrafluoroethylene, and which has a melting point of from 260 to 320° C. (2) The method for obtaining a resin powder according to the above (1), wherein the fluorocopolymer (X1) is the following fluorocopolymer (X1-1):
• Fluorocopolymer (X1-1) a fluorocopolymer which has the unit (1), the unit (2) and a unit (3-1) based on a perfluoro(alkyl vinyl ether), wherein to the total of all units, the proportion of the unit (1) is from 0.01 to 3 mol %, the proportion of the unit (2) is from 90 to 99.89 mol %, and the proportion of the unit (3-1) is from 0.1 to 9.99 mol %, and which has a melting point of from 260 to 320° C.
• Fluorocopolymer (X1-2) a fluorocopolymer which has the unit (1), the unit (2) and a unit (3-2) based on hexafluoropropylene, wherein to the total of all units, the proportion of the unit (1) is from 0.01 to 3 mol %, the proportion of the unit (2) is from 90 to 99.89 mol %, and the proportion of the unit (3-2) is from 0.1 to 9.99 mol %, and which has a melting point of from 260 to 320° C.
• the unit (1) includes a unit containing a carbonyl group-containing group, and said carbonyl group-containing group is at least one member selected from the group consisting of a group having a carbonyl group between carbon atoms in a hydrocarbon group, a carbonate group, a carboxy group, a haloformyl group, an alkoxy carbonyl group and an acid anhydride residue group.
• the average particle size of the resin powder is from 0.02 to 10 ⁇ m.
• a method for producing a composite which comprises producing a resin powder by the method for obtaining a resin powder as defined in any one of the above (1) to (6), and dispersing the obtained resin powder in a resin (C) (but excluding the fluorocopolymer (X1)).
• the resin (C) is a thermosetting resin
• the thermosetting resin comprises at least one member selected from the group consisting of a polyimide and an epoxy resin.
• a method for producing a molded product which comprises producing a composite by the method for producing a composite as defined in any one of the above (9) to (12), and molding the obtained composite.
• a method for producing a ceramic molded product which comprises steps of producing a resin powder by the production method as defined in any one of the above (1) to (6), mixing the obtained resin powder and a ceramic powder to obtain a mixture, and molding the mixture to obtain a ceramic molded product.
• a method for producing a metal laminated plate which comprises producing a molded product by the production method as defined in the above (14), and laminating a metal layer on one side or both sides of a substrate made of the obtained molded product.
• a method for producing a printed circuit board which comprises producing a metal laminated plate by the production method as defined in the above (16), and etching the metal layer of the obtained metal laminated plate to form a patterned circuit.
• a method for producing a prepreg which comprises producing a resin powder by the production method as defined in any one of the above (1) to (6), and impregnating at least one member selected from the group consisting of a thermosetting resin composition containing the obtained resin powder and a thermoplastic resin composition containing the obtained resin powder, in a fiber substrate.
• a method for producing an adhesive film which comprises laminating a layer made of the composite obtained by the production method as defined in the above (9) on at least one side of a heat-resistant resin film, wherein the resin powder has an average particle size of from 0.02 to 6 ⁇ m and D90 of at most 8 ⁇ m, and the relative dielectric constant (value measured at a frequency of 2.5 GHz in an environment within a range of 23° C. ⁇ 2° C. and RH of 50 ⁇ 5%) of the adhesive layer is from 2.0 to 3.5.
• a method of producing a metal laminated plate which comprises laminating a metal layer on at least one layer made of the layer of the composite of the adhesive film obtained by the production method as defined in the above (19).
• the fluorocopolymer (X1) has a unit (1) containing at least one type of functional group selected from the group consisting of a carbonyl group-containing group, a hydroxy group, an epoxy group and an isocyanate group, and a unit (2) based on tetrafluoroethylene, and has a melting point of from 260 to 320° C.; the resin powder has an average particle size of from 0.02 to 6 ⁇ m and D90 of at most 8 ⁇ m; and the relative dielectric constant (value measured at a frequency of 2.5 GHz in an environment within a range of 23° C. ⁇ 2° C. and RH of 50 ⁇ 5%) of the adhesive film is from 2.0 to 3.5.
• said composite being a composite in which a resin powder made of a material (X) containing a fluorocopolymer (X1) as the main component is dispersed in a resin (C) (but excluding the fluorocopolymer (X1)), wherein the fluorocopolymer (X1) has a unit (1) containing at least one type of functional group selected from the group consisting of a carbonyl group-containing group, a hydroxy group, an epoxy group and an isocyanate group, and a unit (2) based on tetrafluoroethylene, and has a melting point of from 260 to 320° C.; the resin powder has an average particle size of from 0.02 to 6 ⁇ m and D90 of at most 8 ⁇ m; and the relative dielectric constant (value measured at a frequency of 2.5 GHz in an environment within a range of 23° C. ⁇ 2° C. and RH of 50 ⁇ 5%) of the composite is from 2.0 to 3.5.
• thermosetting resin composition containing a resin powder and a thermoplastic resin composition containing a resin powder, is impregnated in a fiber substrate, wherein
• said at least one member selected from the group consisting of the thermosetting resin composition and the thermoplastic resin composition is a composite in which a resin powder made of a material (X) containing a fluorocopolymer (X1) as the main component is dispersed in a resin (C) (but excluding the fluorocopolymer (X1)); the fluorocopolymer (X1) has a unit (1) containing at least one type of functional group selected from the group consisting of a carbonyl group-containing group, a hydroxy group, an epoxy group and an isocyanate group, and a unit (2) based on tetrafluoroethylene, and has a melting point of from 260 to 320° C.; the resin powder has an average particle size of from 0.02 to 6 ⁇ m and D90 of at most 8 ⁇ m; and the relative dielectric constant (value measured at a frequency of 2.5 GHz in an environment within a range of 23° C. ⁇ 2° C. and RH of 50 ⁇ 5%) of the thermosetting resin
• a “relative dielectric constant” is a value measured at a frequency of 2.5 GHz in an environment within a range of 23° C. ⁇ 2° C. and RH of 50 ⁇ 5% by the SPDR (split post dielectric resonator) method.
• a “unit” represents a unit derived from a monomer, as formed by polymerization of the monomer.
• a unit may be a unit formed directly by a polymerization reaction or may be a unit having part of a unit in a polymer obtained by a polymerization reaction converted to another structure by treating the polymer.
• a “monomer” is a compound having a polymerizable unsaturated bond such as a polymerizable carbon-carbon double bond.
• a “carbonyl group-containing group” is a group containing a carbonyl group (—C( ⁇ O)—) in its structure.
• An “etheric oxygen atom” is one oxygen atom present between carbon-carbon atoms (—C—O—C—).
• a “perfluoroalkyl group” is a group having all hydrogen atoms in an alkyl group substituted by fluorine atoms.
• a “perfluoroalkylene group” is a group having all hydrogen atoms in an alkylene group substituted by fluorine atoms.
• a “(meth)acrylate” means an acrylate or a methacrylate.
• a resin powder having an average particle size of at least 100 ⁇ m via a step of applying a mechanical pulverization treatment (hereinafter referred to also as “pulverization step”) to resin particles (A) having an average particle size of at least 100 ⁇ m, a resin powder having an average particle size of from 0.02 to 50 ⁇ m (hereinafter referred to also as “resin powder (B)”) is obtained.
• pulverization step a mechanical pulverization treatment
• the production method of the present invention may contain, after the pulverization step, a step of classifying the pulverized product obtained in the pulverization step (hereinafter referred to also as “classification step”).
• the resin particles (A) are made of a material (X).
• the material (X) contains a fluorocopolymer (X1) as the main component.
• the material (X) “contains a fluorocopolymer (X1) as the main component” means that the proportion of the fluorocopolymer (X1) to the total amount (100 mass %) of the material (X) is at least 80 mass %.
• the proportion of the fluorocopolymer (X1) to the total amount (100 mass %) of the material (X) is preferably at least 85 mass %, more preferably at least 90 mass %, particularly preferably 100 mass %.
• the fluorocopolymer (X1) is the main component, it is possible to obtain one having a large bulk density as the resin powder (B). The larger the bulk density of the resin powder (B), the better the handling efficiency.
• the fluorocopolymer (X1) to be contained in the material (X) may be of one type, or two or more types in combination.
• the material (X) may further contain another resin (X2) other than the fluorocopolymer (X1), as the case requires, within a range not to impair the effects of the present invention.
• the fluorocopolymer (X1) has the following unit (1) and the following unit (2). As the case requires, it may further have other units in addition to the unit (1) and the unit (2).
• the unit (1) is a unit containing at least one type of functional group selected from the group consisting of a carbonyl group-containing group, a hydroxy group, an epoxy group and an isocyanate group (hereinafter referred to also as “functional group (i)”).
• the carbonyl group-containing group is not particularly limited so long as it is a group containing a carbonyl group in its structure, and, for example, a group having a carbonyl group between carbon atoms in a hydrocarbon group, a carbonate group, a carboxy group, a haloformyl group, an alkoxycarbonyl group, an acid anhydride residue group, a polyfluoroalkoxycarbonyl group, a fatty acid residue group, etc. may be mentioned.
• the hydrocarbon group may, for example, be an alkylene group having from 2 to 8 carbon atoms.
• the number of carbon atoms in the alkylene group is the number of carbon atoms in a state not containing the carbonyl group.
• the alkylene group may be linear or branched.
• the haloformyl group is represented by —C( ⁇ O)—X (where X is a halogen atom).
• X is a halogen atom.
• a fluorine atom or a chlorine atom may, for example, be mentioned, and a fluorine atom is preferred. That is, as the haloformyl group, a fluoroformyl group (referred to also as a carbonyl fluoride group) is preferred.
• the alkoxy group in the alkoxycarbonyl group may be linear or branched, and is preferably an alkoxy group having from 1 to 8 carbon atoms, particularly preferably a methoxy group or an ethoxy group.
• a unit based on a monomer (hereinafter referred to also as “monomer (m1)”) containing a functional group (i) is preferred.
• the functional group (i) in the monomer (m1) may be one, or two or more.
• the monomer has two or more functional groups (i)
• such two or more functional groups (i) may be respectively the same or different.
• the monomer (m1) a compound having one functional group (i) and having one polymerizable double bond, is preferred.
• the monomers (m1) as the monomer containing a carbonyl group-containing group, for example, a cyclic hydrocarbon compound (hereinafter referred to also as “monomer (m11)”) having an acid anhydride residue group and a polymerizable unsaturated bond, a monomer (hereinafter referred to also as “monomer (m12)”) having a carboxy group, a vinyl ester, a (meth)acrylate, CF 2 ⁇ CFOR f1 CO 2 X 1 (wherein R f1 is a C 1-10 perfluoroalkylene group which may have an etheric oxygen atom, and X 1 is a hydrogen atom or an alkyl group having from 1 to 3 carbon atoms), or the like, may be mentioned.
• a cyclic hydrocarbon compound hereinafter referred to also as “monomer (m11)”
• the monomer (m11) may, for example, be an acid anhydride of an unsaturated dicarboxylic acid.
• the acid anhydride of an unsaturated dicarboxylic acid may, for example, be itaconic anhydride (hereinafter referred to also as “IAH”), citraconic anhydride (hereinafter referred to also as “CAH”), 5-norbornene-2,3-dicarboxylic acid anhydride (another name: anhydrous high mix acid, hereinafter referred to also as “NAH”), maleic anhydride, etc.
• IAH itaconic anhydride
• CAH citraconic anhydride
• NAH anhydrous high mix acid
• maleic anhydride etc.
• the monomer (m12) may, for example, be an unsaturated dicarboxylic acid such as itaconic acid, citraconic acid, 5-norbornene-2,3-dicarboxylic acid, maleic acid, etc.; an unsaturated monocarboxylic acid such as acrylic acid, methacrylic acid, etc.; etc.
• an unsaturated dicarboxylic acid such as itaconic acid, citraconic acid, 5-norbornene-2,3-dicarboxylic acid, maleic acid, etc.
• an unsaturated monocarboxylic acid such as acrylic acid, methacrylic acid, etc.
• the vinyl ester may, for example, be vinyl acetate, vinyl chloroacetate, vinyl butanoate, vinyl pivalate, vinyl benzoate, vinyl crotonate, etc.
• the (meth)acrylate may, for example, be a (polyfluoroalkyl) acrylate, a (polyfluoroalkyl) methacrylate, etc.
• the monomer containing a hydroxy group may, for example, be a vinyl ester, a vinyl ether, an allyl ether or a (meth)acrylate compound, and one having one or more hydroxy groups at its terminal or in its side chain, a crotonic acid-modified compound such as hydroxyethyl crotonate, or allyl alcohol, may, for example, be mentioned.
• the monomer containing an epoxy group may, for example, be an unsaturated glycidyl ether (e.g. allyl glycidyl ether, 2-methyl allyl glycidyl ether, vinyl glycidyl ether, etc.), an unsaturated glycidyl ester (e.g. glycidyl acrylate, glycidyl methacrylate, etc.), etc.
• unsaturated glycidyl ether e.g. allyl glycidyl ether, 2-methyl allyl glycidyl ether, vinyl glycidyl ether, etc.
• an unsaturated glycidyl ester e.g. glycidyl acrylate, glycidyl methacrylate, etc.
• the monomer containing an isocyanate group may, for example, be an unsaturated monomer having an isocyanate group, such as 2-(meth)acryloyloxyethyl isocyanate, 2-(2-(meth)acryloyloxyethoxy)ethyl isocyanate, 1,1-bis((meth)acryloyloxymethyl)ethyl isocyanate, etc.
• the monomer (m1) one type may be used alone, or two or more types may be used in combination.
• the unit (1) has at least a carbonyl group-containing group as a functional group (i). Therefore, the monomer (m1) preferably includes a monomer containing a carbonyl group-containing group.
• the monomer (m11) is preferred.
• at least one member selected from the group consisting of IAH, CAH and NAH is particularly preferred.
• IAH, CAH and NAH it is possible to easily produce a fluorocopolymer having an acid anhydride residue group, without necessity of using a special polymerization method (see JP-A-11-193312) which is required when maleic anhydride is used.
• NAH is preferred, since the adhesion between the resin powder (B) and another resin (C) (such as a polyimide) forming the composite will be thereby more excellent.
• the unit (2) is a unit based on tetrafluoroethylene (hereinafter referred to also as “TEE”).
• Other units other than the unit (1) and the unit (2) may, for example, be a unit (3-1), a unit (3-2), a unit (4), etc.
• fluorocopolymer (X1) for example, a tetrafluoroethylene/perfluoro(alkyl vinyl ether) copolymer (PFA), a tetrafluoroethylene/hexafluoropropylene copolymer (FEP), and their modified products, may be mentioned.
• PFA tetrafluoroethylene/perfluoro(alkyl vinyl ether) copolymer
• FEP tetrafluoroethylene/hexafluoropropylene copolymer
• fluorocopolymer (X1) the following fluorocopolymer (X1-1) or fluorocopolymer (X1-2) is preferred, and the fluorocopolymer (X1-1) is particularly preferred.
• the fluorocopolymer (X1-1) has the unit (1), the unit (2) and the following unit (3-1). As the case requires, it may further have the following unit (3-2) and/or unit (4).
• the unit (3-1) is a unit based on a perfluoro(alkyl vinyl ether) (hereinafter referred to also as “PAVE”).
• PAVE may, for example, be CF 2 ⁇ CFOR f2 (wherein R f2 is a C 1-10 perfluoroalkyl group which may contain an etheric oxygen atom).
• the perfluoroalkyl group for R f2 may be linear or branched.
• the number of carbon atoms in R f2 is preferably from 1 to 3.
• CF 2 ⁇ CFOR f2 may, for example, be CF 2 ⁇ CFOCF 3 , CF 2 ⁇ CFOCF 2 CF 3 , CF 2 ⁇ CFOCF 2 CF 2 CF 3 , CF 2 ⁇ CFOCF 2 CF 2 CF 2 CF 3 , CF 2 ⁇ CFO(CF 2 ) 8 F, etc., and CF 2 ⁇ CFOCF 2 CF 2 CF 3 (hereinafter referred to also as “PPVE”) is preferred.
• PPVE CF 2 ⁇ CFOCF 2 CF 2 CF 3
• PAVE one type may be used alone, or two or more types may be used in combination.
• the unit (3-2) is a unit based on hexafluoropropylene (hereinafter referred to also as “HFP”).
• the unit (4) is a unit other than the units (1), (2), (3-1) and (3-2) and may, for example, be a unit based on a monomer other than the monomer (m1), TFE, PAVE and HFP.
• Such other monomer may, for example, be a fluorinated monomer (but excluding the monomer (m1), TFE, PAVE and HFP) (hereinafter referred to also as “monomer (m41)”), a non-fluorinated monomer (but excluding the monomer (m1)) (hereinafter referred to also as “monomer (m42)”), etc.
• a fluorinated compound having one polymerizable double bond is preferred, and, for example, a fluoroolefin (but excluding TFE and HFP) such as vinyl fluoride, vinylidene fluoride (hereinafter referred to also as “VdF”), trifluoroethylene, chlorotrifluoroethylene (hereinafter referred to also as “CTFE”), etc., CF 2 ⁇ CFOR f3 SO 2 X 3 (wherein R f3 is a C 1-10 perfluoroalkylene group, or a C 2-10 perfluoroalkylene group containing an etheric oxygen atom, and X 3 is a halogen atom or a hydroxy group), CF 2 ⁇ CF(CF 2 ) p OCF ⁇ CF 2 (wherein p is 1 or 2), CH 2 ⁇ CX 4 (CF 2 ) q X 5 (wherein X 4 is a hydrogen atom or a fluorine atom,
• the monomer (m41) at least one member selected from the group consisting of VdF, CTFE and CH 2 ⁇ CX 4 (CF 2 ) q X 5 is preferred.
• CH 2 ⁇ CX 4 (CF 2 ) q X 5 may, for example, be CH 2 ⁇ CH(CF 2 ) 2 F, CH 2 ⁇ CH(CF 2 ) 3 F, CH 2 ⁇ CH(CF 2 ) 4 F, CH 2 ⁇ CF(CF 2 ) 3 H, CH 2 ⁇ CF(CF 2 ) 4 H, etc., and CH 2 ⁇ CH(CF 2 ) 4 F or CH 2 ⁇ CH(CF 2 ) 2 F is preferred.
• a non-fluorinated compound having one polymerizable double bond is preferred, and, for example, an olefin having at most 3 carbon atoms, such as ethylene or propylene, may be mentioned. One of them may be used alone, or two or more of them may be used in combination.
• ethylene or propylene is preferred, and ethylene is particularly preferred.
• one type may be used alone, or two or more types may be used in combination.
• two or more monomers (m41) may be used in combination, or two or more monomers (m42) may be used in combination, or at least one monomer (m41) and at least one monomer (m42) may be used in combination.
• the fluorocopolymer (X1-1) may be one composed of the unit (1), the unit (2) and the unit (3-1), or one composed of the unit (1), the unit (2), the unit (3-1) and the unit (3-2), or one composed of the unit (1), the unit (2), the unit (3-1) and the unit (4), or one composed of the unit (1), the unit (2), the unit (3-1), the unit (3-2) and the unit (4).
• fluorocopolymer (X1-1) preferred is a copolymer having the unit based on a monomer containing a carbonyl group-containing group, the unit (2) and the unit (3-1), and particularly preferred is a copolymer having the unit based on the monomer (m11), the unit (2) and the unit (3-1).
• fluorocopolymer (X1-1) may, for example, be a TFE/PPVE/NAH copolymer, a TFE/PPVE/IAH copolymer, a TFE/PPVE/CAH copolymer, etc.
• the fluorocopolymer (X1-1) may have a functional group (i) as a main chain terminal group.
• a functional group (i) as a main chain terminal group an alkoxycarbonyl group, a carbonate group, a carboxy group, a fluoroformyl group, an acid anhydride residue group, a hydroxy group, etc. are preferred.
• Such a functional group may be introduced by suitably selecting a radical polymerization initiator, a chain transfer agent or the like to be used at the time of producing the fluorocopolymer (X1-1).
• the proportion of the unit (1) to the total (100 mol %) of all units constituting the fluorocopolymer (X1-1) is from 0.01 to 3 mol %, preferably from 0.03 to 2 mol %, particularly preferably from 0.05 to 1 mol %.
• the content of the unit (1) is at least the lower limit value in the above range, the bulk density of the resin powder (B) obtainable by mechanical pulverization of the resin particles (A) tends to be large as compared with a case where resin particles with the same average particle size containing PFA as the main component, other than the fluorocopolymer (X1-1), are pulverized under the same conditions.
• adhesion between the resin powder (B) and another resin to form a composite (C), and interlayer adhesion of a laminate (such as a metal laminated plate) obtainable by laminating said composite with another material (such as a metal), will be good.
• a laminate such as a metal laminated plate
• another material such as a metal
• the proportion of the unit (2) to the total of all units constituting the fluorocopolymer (X1-1) is from 90 to 99.89 mol %, preferably from 95 to 99.47 mol %, particularly preferably from 96 to 98.95 mol %.
• the fluorocopolymer (X1-1) will be excellent in electrical characteristics (low relative dielectric constant, etc.), heat resistance, chemical resistance, etc.
• the fluorocopolymer (X1-1) will be excellent in melt moldability, stress cracking resistance, etc.
• the proportion of the unit (3-1) to the total of all units constituting the fluorocopolymer (X1-1) is from 0.1 to 9.99 mol %, preferably from 0.5 to 9.97 mol %, particularly preferably from 1 to 9.95 mol %.
• the fluorocopolymer (X1-1) will be excellent in moldability.
• the total proportion of the units (1), (2) and (3-1) to the total of all units in the fluorocopolymer (X1-1) is preferably at least 90 mol %, more preferably at least 95 mol %, further preferably at least 98 mol %.
• the upper limit of such a total proportion is not particularly limited and may be 100 mol %.
• the content of each unit in the fluorocopolymer (X1-1) can be measured by a NMR analysis such as a molten nuclear magnetic resonance (NMR) analysis, a fluorine content analysis, an infrared absorption spectrum analysis, etc.
• NMR molten nuclear magnetic resonance
• fluorine content analysis a fluorine content analysis
• infrared absorption spectrum analysis etc.
• the fluorocopolymer (X1-2) has the unit (1), the unit (2) and the unit (3-2). As the case requires, it may further contain the unit (3-1) and/or the unit (4).
• the fluorocopolymer (X1-2) may be one composed of the unit (1), the unit (2) and the unit (3-2), or one composed of the unit (1), the unit (2), the unit (3-2) and the unit (3-1), or one composed of the unit (1), the unit (2), the unit (3-2) and the unit (4), or one composed of the unit (1), the unit (2), the unit (3-2), the unit (3-1) and the unit (4).
• fluorocopolymer (X1-2) preferred is a copolymer having the unit based on the monomer containing a carbonyl group-containing group, the unit (2) and the unit (3-2), and particularly preferred is a copolymer having the unit based on the monomer (m11), the unit (2) and the unit (3-2).
• fluorocopolymer (X1-2) may, for example, be a TFE/HFP/NAH copolymer, a TFE/HFP/IAH copolymer, a TFE/HFP/CAH copolymer, etc.
• the fluorocopolymer (X1-2) may have a functional group (i) as a main chain terminal group.
• the functional group (i) may be the same as described above.
• the proportion of the unit (1) to the total (100 mol %) of all units constituting the fluorocopolymer (X1-2) is from 0.01 to 3 mol %, preferably from 0.02 to 2 mol %, particularly preferably from 0.05 to 1.5 mol %.
• the content of the unit (1) is at least the lower limit value in the above range, the bulk density of the resin powder (B) obtainable by mechanical pulverization of the resin particles (A), tends to be large as compared with a case where resin particles with the same average particle size containing FEP as the main component, other than the fluorocopolymer (X1-2), are pulverized under the same conditions.
• adhesion between the resin powder (B) and another resin to form the composite (C), and interlayer adhesion of a laminate (such as a metal laminated plate) obtained by laminating said composite with another material (such as a metal), will be good.
• a laminate such as a metal laminated plate
• another material such as a metal
• the proportion of the unit (2) to the total of all units constituting the fluorocopolymer (X1-2) is from 90 to 99.89 mol %, preferably from 91 to 98 mol %, particularly preferably from 92 to 96 mol %.
• the fluorocopolymer (X1-2) will be excellent in electrical characteristics (low relative dielectric constant, etc.), heat resistance, chemical resistance, etc.
• the fluorocopolymer (X1-2) will be excellent in melt moldability, stress cracking resistance, etc.
• the proportion of the unit (3-2) to the total of all units constituting the fluorocopolymer (X1-2) is from 0.1 to 9.99 mol %, preferably from 1 to 9 mol %, particularly preferably from 2 to 8 mol %.
• the fluorocopolymer (X1-2) will be excellent in moldability.
• the total proportion of the units (1), (2) and (3-2) to the total of all units in the fluorocopolymer (X1-2) is preferably at least 90 mol %, at least 95 mol %, further preferably at least 98 mol %.
• the upper limit for such a total proportion is not particularly limited and may be 100 mol %.
• the melting point of the fluorocopolymer (X1) is from 260 to 320° C., preferably from 280 to 320° C., more preferably from 295 to 315° C., particularly preferably from 295 to 310° C.
• the melting point of the fluorocopolymer (X1) is at least the lower limit value in the above range, the heat resistance will be excellent, and when it is at most the upper limit value in the above range, the melt moldability will be excellent.
• the melting point of the fluorocopolymer (X1) can be adjusted by the types and contents of units constituting the fluorocopolymer (X1), the molecular weight, etc. For example, as the proportion of the unit (2) increases, the melting point tends to rise.
• the melt flow rate (hereinafter referred to as “MFR”) at a temperature higher by at least 20° C. than the melting point of the fluorocopolymer (X1) is preferably from 0.1 to 1,000 g/10 min, more preferably from 0.5 to 100 g/10 min, further preferably from 1 to 30 g/10 min, particularly preferably from 5 to 20 g/10 min.
• the fluorocopolymer (X1) When MFR is at least the lower limit value in the above range, the fluorocopolymer (X1) will be excellent in moldability, and a molded product formed from a composite containing the resin powder (B) will be excellent in surface smoothness and appearance. When MFR is at most the upper limit value in the above range, the fluorocopolymer (X1) will be excellent in mechanical strength, and a molded product formed from a composite containing the resin powder (B) will be excellent in mechanical strength.
• MFR is an index for the molecular weight of the fluoroopolymer (X1), and MFR being large indicates that the molecular weight is small, and MFR being small indicates that the molecular weight is large.
• the molecular weight of the fluorocopolymer (X1), and thus MFR, can be adjusted by the conditions for producing the fluorocopolymer (X1). For example, if the polymerization time is shortened in the polymerization of the monomer, MFR tends to increase.
• the relative dielectric constant of the fluorocopolymer (X1) is preferably at most 2.5, particularly preferably at most 2.4. Usually, the relative dielectric constant is from 2.0 to 2.4. The lower the relative dielectric constant of the fluorocopolymer (X1), the better the electrical characteristics of a molded product formed from a composite containing the resin powder (B). For example, excellent transmission efficiency is obtainable when the molded product is used as a substrate for a printed circuit board.
• the relative dielectric constant of the fluorocopolymer (X1) can be adjusted by the content of the unit (2).
• the fluorocopolymer (X1) may be produced by a conventional method.
• fluorocopolymer (X1) for example, (a) a method of polymerizing the monomer (m1) and TFE, and, as the case requires, other monomers (PAVE, FEP, other than those, etc.), may be mentioned.
• the polymerization method is not particularly limited, but, for example, a polymerization method using a radical polymerization initiator is preferred.
• a polymerization method bulk polymerization, solution polymerization using an organic solvent such as a fluorinated hydrocarbon, a chlorinated hydrocarbon, a fluorinated chlorinated hydrocarbon, an alcohol or a hydrocarbon, suspension polymerization using an aqueous medium and, as the case requires, a suitable organic solvent, emulsion polymerization using an aqueous medium and an emulsifier, etc. may be mentioned, and among them, solution polymerization is preferred.
• organic solvent such as a fluorinated hydrocarbon, a chlorinated hydrocarbon, a fluorinated chlorinated hydrocarbon, an alcohol or a hydrocarbon
• suspension polymerization using an aqueous medium and, as the case requires, a suitable organic solvent
• emulsion polymerization using an aqueous medium and an emulsifier, etc. may be mentioned, and among them, solution polymerization is preferred.
• radical polymerization initiator preferred is an initiator having a temperature of from 0 to 100° C. at which its half-life is 10 hours, and more preferred is an initiator having such a half-life temperature of from 20 to 90° C.
• azo compound such as azobisisobutyronitrile
• a non-fluorinated diacyl peroxide such as isobutyryl peroxide, octanoyl peroxide, benzoyl peroxide, lauroyl peroxide, etc.
• a peroxydicarbonate such as diisopropyl peroxydicarbonate
• a peroxy ester such as tert-butyl peroxypivalate, tert-butyl peroxyisobutyrate, tert-butyl peroxy acetate, etc.
• a fluorinated diacyl peroxide such as a compound represented by (Z—(CF 2 ) r COO) 2 (wherein Z is a hydrogen atom, a fluorine atom or a chlorine atom, and r is an integer of from 1 to 10)
• an inorganic peroxide such as potassium persulfate, sodium persulfate, ammonium persulfate
• the chain transfer agent may, for example, be an alcohol such as methanol, ethanol, etc., a chlorofluorohydrocarbon such as 1,3-dichloro-1,1,2,2,3-pentafluoropropane, 1,1-dichloro-1-fluoroethane, etc., a hydrocarbon such as pentane, hexane, cyclohexane, etc., acetic acid, an acetic acid derivative such as acetic anhydride, a glycol such as ethylene glycol, propylene glycol, etc.
• an alcohol such as methanol, ethanol, etc.
• a chlorofluorohydrocarbon such as 1,3-dichloro-1,1,2,2,3-pentafluoropropane, 1,1-dichloro-1-fluoroethane, etc.
• a hydrocarbon such as pentane, hexane, cyclohexane, etc.
• acetic acid an
• a compound having a functional group (i) may be used as at least one of a radical polymerization initiator and a chain transfer agent. It is thereby possible to introduce the functional group (i) to a main chain terminal of a fluorocopolymer (X1) to be produced.
• radical polymerization initiator di-n-propyl peroxydicarbonate, diisopropyl peroxycarbonate, t-butylperoxyisopropyl carbonate, bis(4-t-butylcyclohexyl) peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, etc.
• chain transfer agent acetic acid, acetic anhydride, methyl acetate, ethylene glycol, propylene glycol, etc. may be mentioned.
• a perfluorocarbon, a hydrofluorocarbon, a chlorohydrofluorocarbon, a hydrofluoroether, etc. may be mentioned.
• the number of carbon atoms in these solvents is preferably from 4 to 12.
• perfluorocarbon examples include perfluorocyclobutane, perfluoropentane, perfluorohexane, perfluorocyclopentane, a perfluorocyclohexane, etc.
• hydrofluorocarbon examples include 1-hydroperfluorohexane, etc.
• chlorohydrofluorocarbon examples include 1,3-dichloro-1,1,2,2,3-pentafluoropropane, etc.
• hydrofluoroether examples include methyl perfluorobutyl ether, 2,2,2-trifluoroethyl 2,2,1,1-tetrafluoroethyl ether, etc.
• the polymerization conditions are not particularly limited.
• the polymerization temperature is preferably from 0 to 100° C., more preferably from 20 to 90° C.
• the polymerization pressure is preferably from 0.1 to 10 MPa, more preferably from 0.5 to 3 MPa.
• the polymerization time is preferably from 1 to 30 hours.
• the concentration of the monomer (m11) during the polymerization is preferably from 0.01 to 5 mol %, more preferably from 0.1 to 3 mol %, most preferably from 0.1 to 2 mol %, based on the total of all monomers.
• concentration of the monomer (m11) is within the above range, the polymerization rate during production will be proper. If the concentration of the monomer (m11) is too high, the polymerization rate tends to decrease.
• the amount consumed is supplied continuously or intermittently into the polymerization reactor, so as to maintain the concentration of the monomer within the above range.
• the method for producing the fluorocopolymer (X1) is not limited to the above method ( ⁇ ).
• ⁇ a fluorocopolymer having a unit (hereinafter referred to also as “unit (1A)”) containing a functional group (hereinafter referred to also as “functional group (ii)”) to form a functional group (i) by thermal decomposion, and the unit (2), is heated to thermally decompose the functional group (ii) in the unit (1A) to form the functional group (i) (e.g.
• the resin (X2) is another resin other than the fluorocopolymer (X1).
• the resin (X2) is not particularly limited so long as it does not impair the characteristics of electrical reliability, but, it may, for example, be a fluorocopolymer other than the fluorocopolymer (X1), an aromatic polyester, a polyamide-imide, a thermoplastic polyimide, etc.
• the fluorocopolymer other than the fluorocopolymer (X1) may, for example, be polytetrafluoroethylene, a tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer (but excluding the fluorocopolymer (X1)), a tetrafluoroethylene/hexafluoropropylene copolymer (but excluding the fluorocopolymer (X1)), an ethylene/tetrafluoroethylene copolymer, etc.
• One of these may be used alone, or two or more of them may be used in combination.
• the resin (X2) from the viewpoint of electrical reliability, a fluorocopolymer other than the fluorocopolymer (X1) is preferred.
• the fluorocopolymer other than the fluorocopolymer (X1) one having a melting point of at least 280° C. is preferred.
• the melting point is at least 280° C., even if a molded product made of the composite as described later is exposed to a high temperature atmosphere corresponding to solder reflow, swelling (foaming) due to heat tends to be less likely to occur.
• Resin particles (A) are made of the above-mentioned material (X).
• the average particle size of the resin particles (A) is at least 100 ⁇ m, preferably from 100 to 10,000 ⁇ m, particularly preferably from 100 to 50,000 ⁇ m. When the average particle size is at least the above lower limit value, operation efficiency will be good. When the average particle size is at most the upper limit value in the above-mentioned preferred range, a load in the pulverization step will be small.
• the average particle size of the resin particles (A) is obtained by e.g. a sieving method.
• resin particles (A) if desired resin particles are commercially available, such commercial products may be used, or those produced by an appropriate method may be used.
• the method for producing the resin particles (A) may, for example, be
• At least two fluorocopolymers (X1), or at least one fluorocopolymer (X1) and at least one resin (X2)) are melt-kneaded, and the obtained kneaded product is pulverized, and, as the case requires, the obtained pulverized product is classified (sieved, etc.).
• the pulverization step mechanical pulverization treatment is applied to the resin particles (A) to obtain a pulverized product.
• the “mechanical pulverization treatment” means pulverization by means of an apparatus capable of exerting sufficient shear force and/or crush force to break material to be pulverized (resin particles (A), etc.), to smaller pieces.
• Such an apparatus may, for example, be a hammer mill including a disintegrator, a pin mill, a disk mill, a rotary mill, a jet mill, a fluidized bed air jet mill, a jaw crusher, a gyratory crusher, a cage mill, a pan crusher, a ball mill, a pebble mill, a rod mill, a tube mills, a disc attrition mill, an attritor, a disk refiner, etc.
• a hammer mill including a disintegrator, a pin mill, a disk mill, a rotary mill, a jet mill, a fluidized bed air jet mill, a jaw crusher, a gyratory crusher, a cage mill, a pan crusher, a ball mill, a pebble mill, a rod mill, a tube mills, a disc attrition mill, an attritor, a disk refiner, etc.
• the mechanical pulverization treatment is a treatment carried out by using a hammer mill, a pin mill, a disk mill, a rotary mill or a jet mill.
• the mechanical pulverization treatment is a treatment that is conducted after cooling the resin particles (A) to a temperature of at most ⁇ 40° C. (hereinafter referred to also as “low-temperature pulverization treatment”).
• low-temperature pulverization treatment low-temperature brittleness of the fluorocopolymer (X1) is utilized.
• the cooling temperature in the low-temperature pulverization treatment is preferably at most ⁇ 100° C., more preferably at most ⁇ 160° C.
• the pulverization In the low-temperature pulverization treatment, it is preferred to conduct the pulverization after cooling in an atmosphere at a temperature of at most ⁇ 40° C., particularly preferably at most ⁇ 100° C. Thereby, it tends to be possible to further reduce the average particle size.
• the cooling can be carried out, for example, by using solidified carbon dioxide or liquid nitrogen.
• the apparatus to be used for pulverization by the low-temperature pulverization treatment may optionally be selected from among the above-mentioned various apparatus, but from such a viewpoint that it will be thereby easier to reduce the average particle size of the pulverized product, a hammer mill, a pin mill, a disk mill, a rotary mill or a jet mill is preferred.
• the mechanical pulverization treatment is particularly preferably a low-temperature pulverization treatment, or a treatment conducted by means of a jet mill.
• the pulverized product obtainable in the pulverization step may be used as it is, as a resin powder (B), if the average particle diameter is from 0.02 to 50 ⁇ m. As the case requires, it may be subjected to the following classification step.
• a pulverized product obtained in the pulverization step is classified to obtain a resin powder (B).
• Classification is typically a treatment to remove either one or both of too large particles and too small particles.
• the classification method may, for example, be a method by sieving, wind power classification, etc.
• sieving of the pulverized product may be conducted by means of a sieve having any optional sieve size, and the sieved product passed through the sieve may be used as a resin powder (B).
• the classification step may be conducted continuously from the pulverization step, for example, by using an apparatus equipped with a classifier as the apparatus to be used for mechanical pulverization treatment.
• the resin powder (B) is one obtainable by applying a mechanical pulverization treatment to the resin particles (A), and, as the case requires, classifying the pulverized product.
• the resin powder (B) contains, like the resin particles (A), the fluorocopolymer (X1) as the main component.
• the average particle size of the resin powder (B) is from 0.02 to 50 ⁇ m, preferably from 0.02 to 35 ⁇ m, more preferably from 0.02 to 25 ⁇ m, particularly preferably from 0.02 to 10 ⁇ m.
• the resin powder (B) is to be made into a composite as described later, as the average particle size of the resin powder (B) is small, it is possible to increase the filling rate of the resin powder (B) in the resin (C). The higher the filling rate, the better the electrical properties of the composite (low relative dielectric constant, etc.). Further, as the average particle size of the resin powder (B) is small, it is possible to reduce the thickness of the molded product made of the composite.
• the thickness of the molded product can be made thin, for example, to be thin useful for application to a flexible printed circuit board.
• the average particle size of the resin powder (B) is a volume-based cumulative 50% diameter (D50) obtainable by a laser diffraction scattering method. That is, the particle size distribution is measured by a laser diffraction scattering method, and a cumulative curve is obtained by setting the total volume of the group of particles as 100%, whereby a particle diameter at a point where the cumulative volume on the cumulative curve becomes 50% is taken as the average particle size.
• D50 volume-based cumulative 50% diameter
• the loosely packed bulk density of the resin powder (B) is preferably at least 0.18 g/mL, more preferably from 0.18 to 0.85 g/mL, particularly preferably from 0.2 to 0.85 g/mL. In a case where the average particle size of the resin powder (B) is from 0.02 to 10 ⁇ m, the loosely packed bulk density of the resin powder (B) is preferably at least 0.05 g/mL, more preferably from 0.05 to 0.5 g/mL, particularly preferably from 0.08 to 0.5 g/mL.
• the densely packed bulk density of the resin powder (B) is preferably at least 0.25 g/mL, more preferably from 0.25 to 0.95 g/mL, particularly preferably from 0.4 to 0.95 g/mL. In a case where the average particle size of the resin powder (B) is from 0.02 to 10 ⁇ m, the densely packed bulk density of the resin powder (B) is preferably at least 0.05 g/mL, more preferably from 0.05 to 0.8 g/mL, particularly preferably from 0.1 to 0.8 g/mL.
• the loosely packed bulk density and the densely packed bulk density of the resin powder (B) are measured by the methods as described in Examples.
• the resin powder (B) preferably has an average particle size of from 0.02 to 6 ⁇ m and D90 of at most 8 ⁇ m, and more preferably has an average particle size of from 0.02 to 5 ⁇ m and D90 of at most 6 ⁇ m.
• D90 of the resin powder (B) is a volume-based cumulative 90% diameter obtainable by a laser diffraction scattering method. That is, the particle size distribution is measured by a laser diffraction scattering method, and a cumulative curve is obtained by setting the total volume of the group of particles as 100%, whereby a particle diameter at a point where the cumulative volume becomes 90% on the cumulative curve is taken as D90.
• the resin powder (B) is used preferably in the production of a composite, in the production of a ceramic molded product, or in the production of a prepreg, as described later.
• a resin powder (B) having an average particle size of from 0.02 to 50 ⁇ m by applying a mechanical pulverization treatment to resin particles (A) having an average particle size of at least 100 ⁇ m ones made of material (X) containing a fluorocopolymer (X1) as a main component are used as the resin particles (A), whereby it is possible to obtain a resin powder (B) having a large bulk density, as compared with a case where the same mechanical pulverization treatment is applied to resin particles containing a fluorocopolymer having a melting point of from 260 to 320° C. other than the fluorocopolymer (X1).
• a resin powder (B) is good in handling efficiency.
• the resin powder (B) tends to have a smaller average particle size, as compared with the resin powder obtainable by applying the same mechanical pulverization treatment to the resin particles containing a fluorocopolymer having a melting point of from 260 to 320° C. as a main component other than the fluorocopolymer (X1).
• the average particle size is smaller, it is possible to lower the relative dielectric constant of a composite by increasing the filling rate of the resin powder (B) in the composite having the resin powder (B) dispersed in the resin (C). Further, it is possible to reduce the thickness of a molded product made of the composite.
• the fluorocopolymer (X1) has a high heat resistance and is melt-moldable, and therefore, the resin powder (B) also has a high heat resistance and is melt-moldable.
• the fluorocopolymer (X1) has a functional group (i), adhesion between the resin powder (B) and the resin (C), dispersibility of the resin powder (B) in the composite, interlayer adhesion of a laminate (such as a metal laminated plate) obtainable by laminating a molded product made of the composite and another material (such as a metal), etc., will be good.
• the resin (C) is a thermosetting resin
• a curing heat is generated at the stage of forming the composite. Since the fluorocopolymer (X1) has a melt flowability, by the curing heat, the surface of the resin powder (B) dispersed in the thermosetting resin is likely to be melted and have a low viscosity, and tends to be reactive with the thermosetting resin, whereby it is considered to be easily well dispersed in the thermosetting resin.
• the resin powder (B) is well dispersed in a thermosetting resin composition containing the thermosetting resin, and thus is useful for an application to produce a prepreg having the thermosetting resin composition impregnated in a fiber substrate.
• the metal laminated plate in a case where a powder of the fluorocopolymer having a melting point of from 260 to 320° C., has no functional group (i), if the filling rate in the resin (C) becomes high, the adhesion between the substrate made of the composite and the metal layer will decrease, but by having a functional group (i), even if the filling rate is made high, adhesion between the substrate and the metal layer tends to be less likely to be reduced.
• the substrate and the metal layer are laminated at a temperature near the melting point or exceeding the melting point of the fluorocopolymer (X1), improvement in the interlayer adhesion can be expected, as compared with a case where the conventional PTFE powder is used.
• the resin powder (B) is useful for an application to a printed circuit board.
• it is also useful for an application to a ceramic molded product. Further, it is applicable also to injection molding or extrusion molding where freedom in shaping is high.
• the composite of the present invention is one having the resin powder (B) dispersed in a resin (C) (but excluding the fluorocopolymer (X1)).
• the composite of the present invention may contain an additive (D) (but excluding the resin powder (B)) within a range not to impair the effects of the present invention.
• the content of the resin powder (B) in the composite of the present invention is preferably from 5 to 500 parts by mass, more preferably from 10 to 400 parts by mass, particularly preferably from 20 to 300 parts by mass to 100 parts by mass of the resin (C).
• the content of the resin powder (B) is at least the lower limit value in the above range, the composite will be excellent in electrical properties.
• the content of the resin powder (B) is at most the upper limit value in the above range, the composite will be excellent in mechanical strength.
• the present invention is not limited to this, and such a content may be optionally set depending upon the application, desired properties, etc. of the composite.
• the resin (C) is not particularly limited so long as it is a resin other than the fluorocopolymer (X1), and it may, for example, be a thermoplastic resin, a thermosetting resin, a photosensitive resin, etc.
• the resin (C) is preferably a non-fluorinated resin.
• the thermoplastic resin may, for example, be polycarbonate, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyarylate, polycaprolactone, a phenoxy resin, polysulfone, polyether sulfone, polyether ketone, polyether ether ketone, polyether imide (hereinafter referred to also as “PEI”), semi-aromatic polyamide, polyamide 6, polyamide 66, polyamide 11, polyamide 12, polyamide 610, polyphenylene oxide, polyphenylene sulfide, polytetrafluoroethylene, an acrylonitrile-styrene-butadiene copolymer (ABS), polymethyl methacrylate (PMMA), polypropylene, polyethylene, polybutadiene, a butadiene-styrene copolymer, an ethylene-propylene copolymer, an ethylene-propylene-diene rubber (EPDM), a sty
• thermoplastic resin having a melting point of at least 280° C. is preferred.
• the melting point is at least 280° C., at the time when a molded product made of the composite is exposed to an atmosphere corresponding to the solder reflow, there is a tendency that swelling (foaming) due to the heat can be suppressed.
• thermosetting resin may, for example, be polyimide, an epoxy resin, an acrylic resin, a phenolic resin, a polyester resin, a bismaleimide resin, a polyolefin resin, a polyphenylene ether resin, a fluororesin, etc.
• thermosetting resin is preferably polyimide, an epoxy resin, an acrylic resin, a bismaleimide resin or a polyphenylene ether resin.
• resin (C) is such a thermosetting resin
• such a material may be suitably used for a printed circuit board.
• One of these thermosetting resins may be used alone, or two or more of them may be used in combination.
• thermosetting resin at least one member selected from the group consisting of polyimides and epoxy resins is more preferred.
• aromatic polyimides may be mentioned as preferred examples. Among them, a wholly aromatic polyimide produced by condensation polymerization of an aromatic polycarboxylic acid dianhydride and an aromatic diamine is preferred.
• a polyimide is usually obtained via a polyamic acid (polyimide precursor) by a reaction (polycondensation) of a polyvalent carboxylic acid dianhydride (or its derivative) and a diamine.
• a polyimide in particular, an aromatic polyimide, due to its rigid backbone structure, is insoluble in a solvent, etc. and has a infusible property. Therefore, first, by the reaction of a polyvalent carboxylic acid dianhydride and a diamine, a polyimide precursor (polyamic acid or polyamide acid) soluble in an organic solvent, is synthesized, and at the stage of this polyimide precursor, molding processing is carried out in various ways. And then, polyamic acid is subjected to a dehydration reaction by heating or by a chemical method for cyclization (imidization) to obtain a polyimide.
• a polyimide precursor polyamic acid or polyamide acid
• aromatic polycarboxylic acid dianhydride those described in [0055] of JP-A-2012-145676, etc. may be mentioned.
• non-aromatic polycarboxylic acid dianhydrides such as ethylene tetracarboxylic acid dianhydride and cyclopentane tetracarboxylic acid dianhydride, can also be used to be comparable to the aromatic ones.
• One of them may be used alone, or two or more of them may be used in combination.
• aromatic diamine those described in [0057] of JP-A-2012-145676, etc. may be mentioned. One of them may be used alone, or two or more of them may be used in combination.
• the epoxy resin may, for example, be a cresol novolac type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolak type epoxy resin, an alkylphenol novolac type epoxy resin, a biphenol F type epoxy resin, a naphthalene type epoxy resin, a dicyclopentadiene-type epoxy resin, an epoxidized condensate of a phenol with an aromatic aldehyde having a phenolic hydroxy group, triglycidyl isocyanurate, an alicyclic epoxy resin, etc.
• One of them may be used alone, or two or more of them may be used in combination.
• Epikote 828 manufactured by Shell Chemicals
• EPICLON800 alkyl-modified type compound based on bisphenol A
• EPICLON4050 alkyl-modified type EPICLON1121N
• Show dyne manufactured by Showa Denko K.K.
• a glycidyl ester-based compound such as Araldite CY-183 (manufactured by Ciba-Geigy), novolac type of Epikote 154 (manufactured by Shell Chemicals), DEN431, DEN438 (manufactured by the Dow Chemical Company), cresol novolac type ECN1280, ECN1235 (manufactured by Ciba-Geigy), urethane-modified type EPU-6, EPU-10 (manufactured by ADEKA Co., Ltd.), etc.
• the weight average molecular weight of the epoxy resin is preferably from 100 to 1,000,000, more preferably from 1,000 to 100,000. When the weight average molecular weight of the epoxy resin is within the above range, it is possible to more firmly adhere a molded product of the composite and a metal layer.
• the weight average molecular weight of the epoxy resin can be measured by gel permeation chromatography (GPC).
• the bismaleimide resin may, for example, be a resin composition having a bisphenol A type cyanic acid ester resin and a bismaleimide compound used in combination, as disclosed in e.g. JP-A-7-70315.
• a resin composition is referred to as a BT resin and has excellent properties in e.g. electrical properties, mechanical properties, chemical resistance, etc., whereby it is suitable for use as a sealing material for a semiconductor element.
• a bismaleimide resin a study for reducing the thermal expansion coefficient of its cured product has been made, and, for example, the invention and its background technology as described in WO2013/008667 may be mentioned.
• Such a bismaleimide resin may also be used as the resin (C).
• the photosensitive resin it is possible to use various photosensitive resins which are commonly used for resist materials, etc. For example, an acrylic resin, etc. may be mentioned. Further, it is also possible to use one obtained by imparting photosensitivity to the above-mentioned thermosetting resin.
• a specific example of the photosensitive resin obtained by imparting photosensitivity to the thermosetting resin may be one having a methacrylic group or an acrylic group introduced by reacting the thermosetting group of a thermosetting resin (e.g. the epoxy group in an epoxy resin) with methacrylic acid or acrylic acid.
• the additive (D) is preferably an inorganic filler having a low relative dielectric constant or dielectric loss tangent.
• an inorganic filler silica, clay, talc, calcium carbonate, mica, diatomaceous earth, alumina, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dawsonite, hydrotalcite, calcium sulfate, barium sulfate, calcium silicate, montmorillonite, bentonite, activated clay, sepiolite, imogolite, sericite, glass fiber, glass beads, silica-based balloons, carbon black, carbon nanotubes, carbon nanohorn, graphite, carbon fibers, glass balloons, carbon burn, wood flour, zinc borate, etc. may be mentioned.
• One of such inorganic fillers may be used alone, or two or more of
• the inorganic filler may be porous or non-porous. It is preferably porous in that the relative dielectric constant or dielectric loss tangent is thereby further low.
• the inorganic filler may be one in which a surface treatment with a surface treatment agent such as a silane coupling agent or a titanate coupling agent has been applied in order to improve the dispersibility in the resin (C).
• a surface treatment agent such as a silane coupling agent or a titanate coupling agent
• the content of the inorganic filler in the composite is preferably from 0.1 to 100 parts by mass, more preferably from 0.1 to 60 parts by mass, to 100 parts by mass of the resin (C).
• the relative dielectric constant of the composite of the present invention is preferably from 2.0 to 3.5, particularly preferably from 2.0 to 3.0.
• the composite is useful for an application where a low relative dielectric constant is required, such as an application to a printed circuit board.
• the relative dielectric constant is at least the lower limit value in the above range, both adhesion and electrical properties will be excellent.
• the composite of the present invention can be produced by a conventional method.
• the resin (C) is a thermoplastic resin
• a resin powder (B) and the thermoplastic resin may be blended, followed by melt kneading to obtain a composite.
• a resin powder (B) may be dispersed in a varnish of the thermosetting resin before thermal curing, followed by curing to produce a composite.
• the composite of the present invention an application for producing a metal laminated plate as described below, and an application for producing a printed circuit board as described below, are preferred. Further, the composite may be used to form at least one of an interlayer insulating film, a coverlay film and a solder resist for a printed circuit board.
• An interlayer insulating film, a coverlay film and a solder resist using the composite of the present invention may, respectively, be produced with reference to known methods, for example, methods described in JP-A-2013-21374, WO2014/188856, etc.
• use of the composite of the present invention is not limited thereto, and it may be used for other purposes.
• it is useful for electronics boards, such as radars, network routers, backplanes, wireless infrastructures, etc. for which high-frequency characteristics are required, substrates for various sensors for automobiles, substrates for engine management sensors, etc., and it is particularly useful for an application for the purpose of reducing a transmission loss of a millimeter wave band.
• the adhesive film of the present invention is one in which a layer made of the composite of the present invention is laminated on at least one side of a heat-resistant resin film.
• the layer made of the composite of the present invention may be laminated only on one side of the heat-resistant resin film, or may be laminated on both sides. With a view to suppressing warpage of the adhesive film or obtaining a double-sided metal laminate having excellent electrical reliability, it is preferred that the layer made of the composite of the present invention is laminated on both sides of the heat-resistant resin film.
• the composition and thickness of each layer made of the composite of the present invention may be the same or different. With a view to suppressing warpage of the adhesive film, it is preferred that the composition and thickness made of each layer of the composite of the present invention are the same.
• the heat-resistant resin film is a film comprising one or more heat-resistant resins, and may be a single layered film or a multilayered film. However, the heat-resistant resin film contains no fluoropolymer.
• the heat-resistant resin means a polymeric compound having a melting point of at least 280° C., or a polymeric compound having a highest continuous use temperature of at least 121° C. as defined in JIS C 4003: 2010 (IEC 60085 2007).
• heat-resistant resin for example, polyimide (aromatic polyimide, etc.), polyarylate, polysulfone, polyallyl sulfone (polyethersulfone, etc.), aromatic polyamide, aromatic polyether amide, polyphenylene sulfide, polyaryl ether ketone, polyamide-imide, liquid crystal polyester, etc. may be mentioned.
• the heat-resistant resin film may be produced, for example, by a method of molding a heat resistant resin or a resin composition containing a heat resistant resin into a film-form by a known molding method (casting, extrusion molding, inflation molding, etc.).
• a known molding method casting, extrusion molding, inflation molding, etc.
• a commercial product may be used as the heat-resistant resin film.
• the surface of the heat-resistant resin film for example, the surface to be laminated with a fluororesin layer, may be subjected to surface treatment.
• the method for such surface treatment is not particularly limited, and may suitably be selected for use from among known surface treatment methods such as corona discharge treatment, plasma treatment, etc.
• a polyimide film is a film composed of polyimide.
• the polyimide film may contain an additive, as the case requires, within a range not to impair the effects of the present invention.
• the molded product of the present invention is made of the composite of the present invention.
• the shape of the molded product is not particularly limited, and may, for example, be sheet-form (plate-form, film-form, etc.), three-dimensionally molded form, tubular, other extrudates, etc. In a case where the molded product is to be used for an application to a metal laminated plate or a printed circuit board, a sheet-form is preferred.
• the thickness of the sheet-form molded product is preferably from 1 to 3,000 ⁇ m. In the case of the application to an electronic substrate, the thickness is preferably from 3 to 2,000 ⁇ m, more preferably from 5 to 1,000 ⁇ m, particularly preferably from 6 to 500 ⁇ m.
• the molded product of the present invention can be produced by the same method as the above-mentioned method for producing the composite. As the case requires, the composite thus obtained may be processed by cutting, grinding, etc. to obtain a molded product of the present invention.
• a metal laminated plate or a printed circuit board as described below is preferred.
• the application of the molded product of the present invention is not limited thereto, and may be used for other purposes.
• the fluorocopolymer (X1) is excellent in corrosion resistance
• a composite in which a resin powder (B) containing it as the main component is dispersed also has an improved corrosion resistance as compared with a case where no resin powder (B) is contained. Therefore, it is possible to suitably use it in all areas where corrosion resistance is required.
• the coated article is not particularly limited, and it is useful for an application utilizing non-tackiness, heat resistance, sliding properties, etc. of the fluorocopolymer.
• cooking utensils such as a frying pan, a pressure cooker, a pan, a grill pan, a cooking kettle, an oven, a hot plate, a bread type, a knife, a gas table, etc.
• kitchen utensils such as an electric kettle, an ice tray, a mold, a range hood, etc.
• food industrial parts such as a kneading roll, a rolling roll, a conveyor, a hopper, etc.
• industrial supplies such as a roll for office automation (OA), a belt for OA, a separating nail for OA, a paper roll, a calender roll for film production, etc.
• tools such as a saw, a file, etc.; household products such as an iron, scissors, a kitchen knife, etc.; a metal foil, a wire, food processing machines, packaging machine, slide bearing for textile machinery; sliding parts for cameras and clocks; automobile parts, such as pipes, valves, bearings, etc.; a shoveling snow shovel, a plow, a chute, a coil wire for a motor, sealing material for electrical and electronical components, an exhaust duct, a plating jig, a basket for a centrifugal separator; etc. may be mentioned.
• the method for producing a ceramic molded product of the present invention comprises a step of mixing the resin powder (B) and the ceramic powder to obtain a mixture (hereinafter referred to also as “mixing step”), and a step of molding the mixture to obtain a ceramic molded product (hereinafter referred to also as “molding step”).
• the material for the ceramic powder may, for example, be forsterite type ceramics, alumina type ceramics, calcium titanate type ceramics, magnesium titanate type ceramics, strontium titanate type ceramics, zirconia-lead-titanium type ceramics, zirconia-tin-titanium type ceramics, barium titanate type ceramics, lead-calcium-zirconia type ceramics, lead-calcium-iron-niobium type ceramics, lead-calcium-magnesium-niobium type ceramics, etc.
• the ceramic powder may be one surface-treated by a surface treatment agent (titanate type, aluminum type, silane type, etc.).
• another component other than the resin powder (B) and the ceramic powder may be further mixed.
• another component it is possible to use one known as an additive to a ceramic molded product.
• mixing of the resin powder (B) and the ceramic powder (and another component, as the case requires) may be carried out by a conventional method.
• a method of blending the resin powder (B) and the ceramic powder uniformly in a solid phase state may be mentioned.
• the content of the resin powder (B) in the mixture obtained in the mixing step is preferably from 5 to 500 parts by mass, more preferably from 20 to 200 parts by mass, to 100 parts by mass of the ceramic powder.
• the molding step may be carried out by a known molding method commonly used for the production of ceramic molded products.
• a method of melt molding exrusion molding, press molding, injection molding, etc.
• a kneaded product obtained by melt-kneading the mixture may be mentioned.
• Applications of the obtainable ceramic molded products may, for example, be antenna components, etc. Particularly preferred are antenna substrates.
• the metal laminated plate of the present invention comprises a substrate and a metal layer laminated on one side or both sides of the substrate.
• the substrate is the above-described molded product of the present invention. Further, like the above-mentioned adhesive film, it may be a laminate of a heat-resistant resin film and a layer made of the composite of the present invention. Or, the substrate may be one obtained by applying the composite of the present invention.
• the preferred range of the thickness of the substrate is the same as the preferred range of the thickness of the sheet-form molded product.
• the structure of the metal laminated plate of the present invention may, for example, be “a layer made of a composite of the present invention/a metal layer”, “a metal layer/a layer made of a composite of the present invention/a metal layer”, “a layer made of a heat-resistant resin film/a layer made of a composite of the present invention/a metal layer”, “a layer made of a composite of the present invention/a layer made of a heat-resistant resin film/a metal layer”, etc.
• these layers may be combined with a layer made of a fluoropolymer (X1) to form structures of “a metal layer/a layer made of a composite of the present invention/a layer made of a heat-resistant resin film/a layer made of a fluoropolymer (X1)/a layer made of a heat-resistant resin film/a layer made of a composite of the present invention/a metal layer”, “a metal layer/a layer made of a heat resistant resin film/a layer of a composite of the present invention/a layer of a fluorocopolymer (X1)/a layer of a composite of the present invention/a layer made of a heat-resistant resin film/a metal layer”, “a metal layer/a layer made of a composite of the present invention/a layer made of a heat resistant resin film/a layer made of a composite of the present invention/a layer made of a fluorocopolymer (X1)/a layer made of a composite of the present invention/al layer made of a heat-resistant resin film/a layer made
• the metal constituting the metal layer is not particularly limited, and it may be suitably set depending on the application.
• the metal may, for example, be copper or a copper alloy, stainless steel or an alloy thereof, nickel or a nickel alloy (including 42 alloy), aluminum or an aluminum alloy, etc.
• the thickness of the metal layer is not particularly limited, and it is preferably selected to be a thickness capable of providing a sufficient function depending on the use of the metal laminated plate.
• the method for producing the laminated plate of the present invention may, for example, be a method of laminating a metal foil and a substrate, or a method of vapor depositing a metal on the surface of a substrate.
• Lamination between the metal foil and the substrate may be carried out, for example, by a casting method or a heat lamination method.
• the method for vapor depositing a metal may be carried out, for example by a vacuum deposition method, a sputtering method or an ion plating method.
• metal foil a commercial product may be used.
• a copper foil such as a rolled copper foil or an electrolytic copper foil is often used and can be preferably used also in the present invention.
• an anticorrosive layer e.g. an oxide film such as a chromate
• a heat-resistant layer may be formed on the surface of the metal foil.
• a coupling agent treatment or the like may be applied to the surface of the metal foil.
• the printed circuit board of the present invention comprises a patterned circuit formed by etching the metal layer of the metal laminated plate of the present invention. That is, it is one comprising a substrate being a molded product of the present invention, and a patterned circuit made of a metal laminated on one side or both sides of the substrate.
• an interlayer insulating film and a patterned circuit made of a metal may be sequentially laminated.
• the interlayer insulating film may be one formed by using a composite of the present invention.
• solder resist may be laminated on the patterned circuit.
• the solder resist may be one formed by using a composite of the present invention.
• a coverlay film may be laminated.
• the coverlay film is typically composed of a substrate film and an adhesive layer formed on its surface, and the adhesive layer side surface is bonded to the printed circuit board.
• the coverlay film may be one formed by using a composite of the present invention.
• the substrate film may be a molded product formed by using a composite of the present invention.
• the printed circuit board of the present invention may be one in which, on the patterned circuit, a composite of the present invention is used as an interlayer insulating film (adhesive layer), and a polyimide film is laminated as a coverlay film.
• a composite of the present invention is used as an interlayer insulating film (adhesive layer), and a polyimide film is laminated as a coverlay film.
• the composite of the present invention is useful as an interlayer insulating film, for example, as one for forming build-up insulating layers of a multilayer printed circuit board, as described in WO2009/035014.
• the prepreg of the present invention is one obtained by impregnating at least one selected from a thermosetting resin composition containing the resin powder of the present invention and a thermoplastic resin composition comprising the resin powder of the present invention, in a fiber substrate.
• thermosetting resin composition contains a thermosetting resin, and the thermosetting resin may be one described in the above resin (C).
• the thermosetting resin an epoxy resin is preferred.
• the thermoplastic resin composition contains a thermoplastic resin, and the thermoplastic resin may be one described in the above resin (C).
• the thermoplastic resin preferred is polyamide 6, polyamide 12, polyphenylene sulfide, polyetherimide, polyethersulfone, a polyaryl ketone (such as PEEK), an aromatic polyester, polyamide-imide, thermoplastic polyimide, etc.
• thermosetting resin composition may contain other components such as acrylic rubbers, in addition to the thermosetting resin and the resin powder of the present invention, as the case requires. The same applies to the thermoplastic resin composition.
• fiber substrate glass fiber, aramid fiber, carbon fiber, etc. may be mentioned.
• the prepreg of the present invention can be prepared by a known production method except that, as a thermosetting resin composition to be impregnated in the fiber substrate, one containing the resin powder of the present invention is used.
• a thermosetting resin composition to be impregnated in the fiber substrate one containing the resin powder of the present invention is used.
• methods for producing prepregs for example, methods described in e.g. JP-A-2003-171480, JP-A-2007-138152, WO2014/050034, etc. may be mentioned.
• a prepreg may be obtained by impregnating a thermosetting resin composition in a fiber substrate, and, as the case requires, followed by heating and drying until a semi-cured state is obtained.
• the prepreg of the present invention may be laminated and molded with a metal foil to form a metal foil-laminated plate. This metal foil-laminated plate is also included in the metal laminated plate of the present invention.
• Such a metal foil-laminated plate, a printed circuit board, etc. may be produced with reference to, for example, JP-A-2003-171480, JP-A-2007-138152, WO2014/050034, etc.
• the prepreg of the present invention may also be used in applications other than the application to electronic components.
• it may be used as a material for a sheet pile required to have durability and light weight, to be used for quay construction, as described in e.g. JP-A-2007-239255.
• the prepreg of the present invention may be used as a material for a fiber reinforced plastic (FRP) made of reinforcing fibers and a matrix resin.
• FRP fiber reinforced plastic
• CFRP carbon fiber reinforced plastic
• the prepreg of the present invention is excellent in mechanical properties, light weight, corrosion resistance, etc. as described in e.g. the background art of WO2013/175581, and thus is widely used as a material for producing members intended for a variety of applications including e.g. aircrafts, automobiles, ships, wind turbines, sport tools, etc.
• the proportion (mol %) of the unit based on NAH was obtained by the following infrared absorption spectrum analysis.
• the proportions of other units were obtained by the melt NMR analysis and fluorine content analysis.
• a fluorocopolymer was press-molded to obtain a film of 200 ⁇ m.
• the absorption peak of the unit based on NAH in a fluorocopolymer appears at 1,778 cm ⁇ 1 in each case.
• the proportion of the unit based on NAH in the fluorocopolymer was obtained.
• the melting peak at the time of heating a fluorocopolymer at a rate of 10° C./min was recorded, and the temperature (° C.) corresponding to the maximum value was adopted as the melting point (Tm).
• the loosely packed bulk density and densely packed bulk density of the resin particles were measured by using a sample container with a volume of 100 mL by means of the A.B.D powder characteristics measuring device (ABD-100 type) manufactured by TSUTSUI SCIENTIFIC INSTRUMENTS CO., LTD.
• the mass of the resin particles in the sample container was calculated from the mass of the sample container (sample container+resin particles) measured by the following method (6 ⁇ ) and the mass of the sample container which had been measured before supplying the resin particles, the density (g/mL) was calculated from the obtained value, and the value was adopted as a loosely packed bulk density.
• the density (g/mL) was calculated in the same manner as above, except that instead of the mass of the sample container measured by the method of (6 ⁇ ), the mass of the sample container measured by the following method (6 ⁇ ) was used, and its value was adopted as the densely packed bulk density.
• a sample (resin particles (A)) was placed thereon and sieved by a shaker for 30 minutes. Thereafter, the mass of the sample remaining on each sieve was measured, and the cumulative transit mass for each eye opening value was represented in a graph, whereby a particle size at the time when the cumulative transit mass became 50% was adopted as the average particle size of the sample.
• the double-sided copper-clad laminate or the single-sided copper-clad laminate was cut in a size of a length 100 mm and a width 10 mm, to prepare a test specimen.
• the copper foil and the substrate were peeled from one end in the longitudinal direction of the test specimen to a position of 50 mm.
• the relative dielectric constant at a frequency of 2.5 GHz was obtained by the split post dielectric resonator method (SPDR method).
• Equipments used in the relative dielectric constant measurement were nominal fundamental frequency of 2.5 GHz type split post dielectric resonator manufactured by QWED Company, vector network analyzer E8361C manufactured by Keysite Technologies and 85071E option 300 relative dielectric constant calculation software manufactured by Keysite Technologies.
• a fluorocopolymer (X1-1) was produced in the following procedure by using NAH (anhydrous high-mix acid, manufactured by Hitachi Chemical Co., Ltd.) as a monomer to form the unit (1) and PPVE (CF 2 ⁇ CFO(CF 2 ) 3 F, manufactured by Asahi Glass Company, Limited) as a monomer to form the unit (3).
• NAH anhydrous high-mix acid, manufactured by Hitachi Chemical Co., Ltd.
• PPVE CF 2 ⁇ CFO(CF 2 ) 3 F, manufactured by Asahi Glass Company, Limited
• AK225cb 1,3-dichloro-1,1,2,2,3-pentafluoropropane
• PPVE 1,3-dichloro-1,1,2,2,3-pentafluoropropane
• a polymerization initiator solution was prepared by dissolving (perfluoro butyryl) peroxide at a concentration of 0.36 mass % and PPVE at a concentration of 2 mass % in AK225cb, and 3 L of the polymerization initiator solution was continuously added at a rate of 6.25 mL per minute into the polymerization vessel, to carry out polymerization. Further, TFE was continuously charged in order to maintain the pressure in the polymerization vessel during the polymerization reaction to be 0.89 MPa/G. Further, a solution prepared by dissolving NAH at a concentration of 0.3 mass % in AK225cb was charged continuously by an amount corresponding to 0.1 mol % based on moles of TFE to be charged during the polymerization.
• the average particle size of the fluorocopolymer (X1-1) was 1,554 ⁇ m. This fluorocopolymer (X1-1) was used as the resin particles (A-1).
• resin particles (A-2) commercially available granular PFA (product name “Fluon (registered trademark) PFA 63P”, manufactured by Asahi Glass Company, Limited) was used.
• PFA constituting the resin particles (A-2) is one containing no functional group (i), and the melting point was 300° C., the dielectric constant was 2.1, and MFR was 12.8 g/10 min.
• the resin particles (A-1) were pulverized at a rotational speed of 1,300 r ⁇ m.
• the obtained pulverized material was sieved, and one passed through a sieve size of 0.5 mm was recovered to obtain a resin powder (B-1).
• the characteristics (average particle size, loosely packed bulk density and densely packed bulk density) of the resin powder (B-1) were measured. The results are shown below.
• Average particle size 22.08 ⁇ m.
• Densely packed bulk density 0.686 g/mL.
• a resin powder (B-2) was obtained in the same manner as in Example 1 except that the resin particles (A-2) were used instead of the resin particles (A-1).
• Average particle size 33.56 ⁇ m.
• Densely packed bulk density 0.205 g/mL.
• the resin particles (A-1) were cooled to ⁇ 196° C. with liquid nitrogen, and then, using a hammer mill (Rin Rex Mill LX-0, manufactured by Hosokawa Micron Co., Ltd. and Liquid Gas Co., Ltd.), they were pulverized in an environment of ⁇ 160° C. at a rotation speed of 80 m/s under a condition of a processing amount of 3 kg/hour, to obtain a resin powder (B-3).
• Average particle size 6.2 ⁇ m.
• Densely packed bulk density 0.243 g/mL.
• the resin particles (A-1) were pulverized under conditions of a pulverization pressure of 0.5 MPa and a treatment speed of 1 kg/hr to obtain a resin powder (B-4).
• Average particle size 2.58 ⁇ m.
• Densely packed bulk density 0.328 g/mL.
• the resin powder (B-4) was classified under a condition of a treating amount of 0.5 kg/hr by means of a high efficiency precision air classifier (Classy Le N-01 type manufactured by Seishin Enterprise Co. Ltd.) in order to obtain a resin powder (B-5) having a particle size of at most 10 ⁇ m.
• the yield of the resin powder (B-5) obtained by the classification was 89.4%, the average particle size was 1.8 ⁇ m, and D90 was 4.6 ⁇ m.
• a resin powder (B-6) was obtained in the same manner as in Example 4 except that the resin powder (B-3) was used instead of the resin powder (B-4).
• the yield of the resin powder (B-6) was 65.1%, the average particle size was 2.9 ⁇ m, and D90 was 6.6 ⁇ m.
• the resin particles (A-2) were pulverized under conditions of a pulverization pressure of 0.5 MPa and a treating speed of 1 kg/hr, to obtain a resin powder (B-8).
• Average particle size 7.6 ⁇ m.
• the resin powder (B-8) was classified under a condition of a treating amount of 0.5 kg/hr by means of a high efficiency precision air classifier (Classy Le N-01 type, manufactured by Seishin Enterprise Co. Ltd.) in order to obtain a resin powder (B-9) having a particle size of at most 10 ⁇ m, whereby clogging occurred during the classification, and the yield of the resin powder (B-9) was only 41° A.
• the average particle size of the resin powder (B-9) was 6.8 ⁇ m.
• NMP N-methylpyrrolidone
• this solution composition After the vacuum degassing treatment, in this solution composition, no aggregation of the resin powder was observed on appearance.
• This solution composition was subjected to a filtration with a 100 mesh filter, and it was possible to filter the solution composition with no aggregation at the filter portion.
• Drying conditions drying was carried out by heating in an oven at 90° C. for 5 minutes, then at 120° C. for 5 minutes, and finally at 150° C. for 5 minutes.
• a solution composition was obtained in the same manner as in Example 7 except that the resin powder (B-5) was used instead of the resin powder (B-4).
• this solution composition After the vacuum degassing treatment, in this solution composition, no aggregation of the resin powder was observed on appearance.
• This solution composition was subjected to filtration with a 100 mesh filter, whereby it was possible to filter the solution composition with no aggregation at the filter portion.
• Example 7 By carrying out the same operation and drying as in Example 7, a single-sided copper-clad laminate with a structure of copper foil/substrate was obtained. With respect to the obtained single-sided copper-clad laminate, the presence or absence of aggregates in the substrate was visually confirmed, whereby no aggregates were observed.
• a solution composition was obtained in the same manner as in Example 7 except that the resin powder (B-6) was used instead of the resin powder (B-4).
• this solution composition After the vacuum degassing treatment, in this solution composition, no aggregation of the resin powder was observed on appearance.
• This solution composition was subjected to filtration with a 100 mesh filter, whereby it was possible to filter the solution composition with no aggregation at the filter portion.
• Example 7 By carrying out the same operation and drying as in Example 7, a single-sided copper-clad laminate with a structure of copper foil/substrate was obtained. With respect to the obtained single-sided copper-clad laminate, the presence or absence of aggregates in the substrate was visually confirmed, whereby aggregates were slightly observed.
• a solution composition was obtained in the same manner as in Example 7 except that the resin powder (B-7) was used instead of the resin powder (B-4).
• this solution composition After the vacuum degassing treatment, in this solution composition, no aggregation of the resin powder was observed on appearance.
• This solution composition was subjected to filtration with a 100 mesh filter, whereby it was possible to filter the solution composition with no aggregation at the filter portion.
• Example 7 By carrying out the same operation and drying as in Example 7, a single-sided copper-clad laminate with a structure of copper foil/substrate was obtained. With respect to the obtained single-sided copper-clad laminate, the presence or absence of aggregates in the substrate was visually confirmed, whereby aggregates were slightly observed.
• a solution composition was obtained in the same manner as in Example 7 except that the resin powder (B-8) was used instead of the resin powder (B-4).
• this solution composition After the vacuum degassing treatment, in this solution composition, aggregation of the resin powder was observed on appearance.
• This solution composition was subjected to filtration with a 100 mesh filter, whereby aggregates were observed at the filter portion, and filter clogging occurred, whereby it was not possible to reach the step of preparing a single-sided copper-clad laminate as in Examples 7 to 10.
• an electrolytic copper foil having a thickness of 12 ⁇ m (CF-T4X-SVR-12, manufactured by Fukuda Metal Foil & Powder Co., Ltd., surface roughness (Rz) 1.2 ⁇ m) was overlaid and vacuum-pressed under conditions of a temperature of 220° C. and 3 MPa for 60 minutes to obtain a double-sided copper-clad laminate.
• thermosetting modified polyimide varnish having an epoxy group (solvent NMP, manufactured by PI R&D CO., LTD., solid content 15 mass %) was subjected to filtration with a 100 mesh filter to obtain a solution composition.
• the obtained solution composition was applied and dried, under the same conditions as in Example 7, on the same electrolytic copper foil as in Example 7, to obtain a single-sided copper clad laminate with a structure of copper foil/substrate.
• Example 11 a double-sided copper clad laminate was obtained in the same manner as in Example 11 except that instead of the single-sided copper-clad laminate prepared in Example 8, the single-sided copper clad laminate obtained above, was used.
• a solution composition was obtained in the same manner as in Example 7 except that the resin powder (B-5) was used instead of the resin powder (B-4).
• this solution composition After the vacuum degassing treatment, in this solution composition, no aggregation of the resin powder was observed on appearance, and this solution composition was subjected to filtration with a 100 mesh filter, whereby it was possible to filter the solution composition with no aggregation observed at the filter portion.
• the solution composition filtered through the filter was applied and dried to form a coating film so that the thickness of the coating film (thermosetting modified polyimide layer) after drying under the following conditions would be 25 ⁇ m, to obtain a laminate with a structure of polyimide film/thermosetting modified polyimide layer.
• Drying conditions Drying was carried out by heating in an oven at 90° C. for 5 minutes, then at 120° C. for 5 minutes, and finally at 150° C. for 5 minutes.
• thermosetting modified polyimide layer With respect to the obtained laminate, the presence or absence of aggregates in the thermosetting modified polyimide layer, was visually confirmed, whereby no aggregates were observed.
• thermosetting modified polyimide layer surface of the laminate prepared in Example 12 an electrolytic copper foil having a thickness of 12 ⁇ m (CF-T4X-SVR-12, manufactured by Fukuda Metal Foil & Powder Co. Ltd., surface roughness (Rz) 1.2 ⁇ m) was overlaid and vacuum-pressed under conditions of a temperature of 220° C. and 3 MPa for 60 minutes to obtain a single-sided copper-clad laminate.
• CF-T4X-SVR-12 manufactured by Fukuda Metal Foil & Powder Co. Ltd., surface roughness (Rz) 1.2 ⁇ m
• a laminate with a structure of polyimide film/thermosetting modified polyimide layer was obtained in the same manner as in Example 12 except that the resin powder (B-5) was not added.
• a single-sided copper-clad laminate was obtained in the same manner as in Example 13 except that after carrying out drying under the same drying conditions as in Example 7, the laminate obtained above was used instead of the laminate prepared in Example 12.
• the fluorocopolymer (X1-1) was extrusion-molded at a die temperature of 340° C. by means of a 30 mm ⁇ single screw extruder having a 750 mm width coat hanger die, to obtain a fluororesin film having a thickness of 50 ⁇ m (hereinafter referred to as “film 1”).
• film 1 The film 1 and a polyimide film having a thickness of 25 ⁇ m (product name “Kapton (registered trademark)”, manufactured by Du Pont-Toray Co., Ltd.) were laminated in the order of polyimide film/film 1/polyimide film and vacuum-pressed at a temperature of 360° C. under a pressure of 3.7 MPa for 10 minutes, to obtain a “laminated film 1”.
• Example 8 two sheets of the single-sided copper-clad laminate obtained in Example 8 and the laminated film 1, were vacuum-pressed in the order of single-sided copper clad laminate/laminated film 1/single-sided copper foil laminate under conditions of a temperature of 220° C. and 3 MPa for 60 minutes, to prepare a double-sided copper-clad laminate.
• the surface of the single-sided copper-clad laminate to be bonded to the laminate film 1 was the surface of the coating film (substrate).
• the relative dielectric constant was measured and found to be 2.86.
• Example 8 Two sheets of the single-sided copper-clad laminate obtained in Example 8 and the film 1 obtained in Example 14, were vacuum-pressed in the order of single-sided copper clad laminate/film 1/single-sided copper foil laminate under conditions of a temperature of 220° C. and 3 MPa for 60 minutes, to prepare a double-sided copper-clad laminate.
• the surface of the single-sided copper-clad laminate to be bonded to the film 1 was the surface of the coating film (substrate).
• the relative dielectric constant was measured and found to be 2.47.
• the composite, molded product, ceramic molded product, metal laminated plate, printed circuit board, prepreg, etc. to be formed by using the resin powder obtained by the present invention can be used as antenna components, printed circuit boards, aircraft parts, automotive parts, sports equipment, food industrial products, saws, coated articles such as sliding bearings, etc.

Landscapes

• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Manufacturing & Machinery (AREA)
• Materials Engineering (AREA)
• Microelectronics & Electronic Packaging (AREA)
• Ceramic Engineering (AREA)
• Inorganic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Wood Science & Technology (AREA)
• General Chemical & Material Sciences (AREA)
• Laminated Bodies (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Developing Agents For Electrophotography (AREA)
• Processes Of Treating Macromolecular Substances (AREA)
• Reinforced Plastic Materials (AREA)

Priority Applications (1)

Applications Claiming Priority (5)

Related Parent Applications (1)

Related Child Applications (1)

Publications (1)

Family

ID=55217695

Family Applications (2)

Family Applications After (1)

Country Status (6)

Cited By (20)

Families Citing this family (52)

Citations (4)

Family Cites Families (19)

• 2015
  • 2015-07-31 CN CN201910434395.9A patent/CN110105597B/zh active Active
  • 2015-07-31 KR KR1020167033953A patent/KR102468437B1/ko active Active
  • 2015-07-31 JP JP2016538464A patent/JP6642433B2/ja active Active
  • 2015-07-31 CN CN201580041455.0A patent/CN106574055B/zh active Active
  • 2015-07-31 TW TW104124946A patent/TWI690548B/zh active
  • 2015-07-31 WO PCT/JP2015/071803 patent/WO2016017801A1/fr not_active Ceased
• 2017
  • 2017-01-24 US US15/414,212 patent/US20170130009A1/en not_active Abandoned
• 2019
  • 2019-12-10 US US16/709,049 patent/US11041053B2/en active Active
  • 2019-12-25 JP JP2019234583A patent/JP2020063451A/ja active Pending

Patent Citations (4)

Also Published As

Similar Documents

Legal Events