WO2016208672A1 - 積層体、成形品、導電性パターン、電子回路及び電磁波シールド - Google Patents
積層体、成形品、導電性パターン、電子回路及び電磁波シールド Download PDFInfo
- Publication number
- WO2016208672A1 WO2016208672A1 PCT/JP2016/068661 JP2016068661W WO2016208672A1 WO 2016208672 A1 WO2016208672 A1 WO 2016208672A1 JP 2016068661 W JP2016068661 W JP 2016068661W WO 2016208672 A1 WO2016208672 A1 WO 2016208672A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- metal
- layer
- polyphenylene sulfide
- acid
- metal layer
- Prior art date
Links
- GNKZMNRKLCTJAY-UHFFFAOYSA-N CC(c1ccc(C)cc1)=O Chemical compound CC(c1ccc(C)cc1)=O GNKZMNRKLCTJAY-UHFFFAOYSA-N 0.000 description 1
- OJHMWPKHNHLXEC-UHFFFAOYSA-N Cc(cc1)ccc1-c(cc1)ccc1SC Chemical compound Cc(cc1)ccc1-c(cc1)ccc1SC OJHMWPKHNHLXEC-UHFFFAOYSA-N 0.000 description 1
- CHLICZRVGGXEOD-UHFFFAOYSA-N Cc(cc1)ccc1OC Chemical compound Cc(cc1)ccc1OC CHLICZRVGGXEOD-UHFFFAOYSA-N 0.000 description 1
- YYDNBUBMBZRNQQ-UHFFFAOYSA-N Cc(cc1)ccc1S(C)(=O)=O Chemical compound Cc(cc1)ccc1S(C)(=O)=O YYDNBUBMBZRNQQ-UHFFFAOYSA-N 0.000 description 1
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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
-
- 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
- B32B15/06—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 natural rubber or synthetic rubber
-
- 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
- B32B15/04—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
- B32B15/082—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 comprising vinyl resins; comprising acrylic 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
- 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
- B32B15/095—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 comprising polyurethanes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- 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
- B32B15/098—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 comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines
-
- 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
- B32B25/00—Layered products comprising a layer of natural or synthetic rubber
- B32B25/16—Layered products comprising a layer of natural or synthetic rubber comprising polydienes homopolymers or poly-halodienes homopolymers
-
- 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
- B32B27/28—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
- B32B27/286—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 polysulphones; polysulfides
-
- 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
- B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (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
- 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
-
- 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
- B32B7/10—Interconnection of layers at least one layer having inter-reactive 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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
-
- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
- C08J7/0423—Coating with two or more layers, where at least one layer of a composition contains a polymer binder with at least one layer of inorganic material and at least one layer of a composition containing a polymer binder
-
- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/044—Forming conductive coatings; Forming coatings having anti-static properties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L21/00—Compositions of unspecified rubbers
-
- 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
- C08L27/16—Homopolymers or copolymers or vinylidene fluoride
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
-
- 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
- H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
-
- 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
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
- H05K3/1208—Pretreatment of the circuit board, e.g. modifying wetting properties; Patterning by using affinity patterns
-
- 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
- H05K3/22—Secondary treatment of printed circuits
- H05K3/24—Reinforcing the conductive pattern
- H05K3/245—Reinforcing conductive patterns made by printing techniques or by other techniques for applying conductive pastes, inks or powders; Reinforcing other conductive patterns by such techniques
- H05K3/246—Reinforcing conductive paste, ink or powder patterns by other methods, e.g. by plating
-
- 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
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
-
- 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
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/16—Making multilayered or multicoloured articles
- B29C45/1657—Making multilayered or multicoloured articles using means for adhering or bonding the layers or parts to each other
- B29C2045/1664—Chemical bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/16—Making multilayered or multicoloured articles
- B29C2045/1693—Making multilayered or multicoloured articles shaping the first molding material before injecting the second molding material, e.g. by cutting, folding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
- B29C45/14311—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles using means for bonding the coating to the articles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2009/00—Layered products
-
- 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
- B32B2250/04—4 layers
-
- 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
- B32B2250/24—All layers being polymeric
- B32B2250/246—All polymers belonging to those covered by groups B32B27/32 and B32B27/30
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/06—Coating on the layer surface on metal layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/20—Inorganic coating
- B32B2255/205—Metallic coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2270/00—Resin or rubber layer containing a blend of at least two different 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
- B32B2274/00—Thermoplastic elastomer material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/202—Conductive
-
- 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
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/212—Electromagnetic interference shielding
-
- 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
- B32B2319/00—Synthetic rubber
-
- 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
- B32B2327/00—Polyvinylhalogenides
- B32B2327/12—Polyvinylhalogenides containing fluorine
-
- 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
- B32B2333/00—Polymers of unsaturated acids or derivatives thereof
- B32B2333/04—Polymers of esters
- B32B2333/08—Polymers of acrylic acid esters, e.g. PMA, i.e. polymethylacrylate
-
- 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
-
- 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
-
- 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
- C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
- C08J2381/04—Polysulfides
-
- 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
- C08J2433/00—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2433/14—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
-
- 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
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
- C08J2475/06—Polyurethanes from polyesters
-
- 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
- C08J2491/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
- C08J2491/06—Waxes
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
-
- 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
- H05K2201/0104—Properties and characteristics in general
- H05K2201/0133—Elastomeric or compliant polymer
-
- 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
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
- H05K2203/0703—Plating
- H05K2203/0723—Electroplating, e.g. finish plating
-
- 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
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
- H05K3/1241—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns by ink-jet printing or drawing by dispensing
- H05K3/125—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns by ink-jet printing or drawing by dispensing by ink-jet printing
-
- 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
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/386—Improvement of the adhesion between the insulating substrate and the metal by the use of an organic polymeric bonding layer, e.g. adhesive
Definitions
- the present invention is a conductive pattern provided for wired electronic circuits such as electronic circuits, molded products such as connectors for connecting wiring for optical communication, lamp reflectors, printed boards, electromagnetic wave shields, integrated circuits, organic transistors, etc.
- the present invention relates to a laminate that can be used, a molded article using the laminate, a conductive pattern, and an electronic circuit.
- polyphenylene sulfide is attracting attention as an engineering plastic having heat resistance and chemical resistance, and is used in optical pickups such as Blu-ray and DVD, electronic circuit boards, wiring connectors, film capacitors, and the like.
- optical pickups such as Blu-ray and DVD
- electronic circuit boards wiring connectors, film capacitors, and the like.
- lamp reflectors electrical components, electric motor peripheral members, battery members, and the like.
- polyphenylene sulfide has a problem that its adhesion to a metal film such as metal vapor deposition and metal plating is very low, and it cannot be used sufficiently for the application of forming a metal film on the surface of polyphenylene sulfide. .
- the surface of the polyphenylene sulfide is etched with an etching solution, and after adding a palladium catalyst, electroless copper plating is performed to form a copper plating layer. It has been proposed (see, for example, Patent Document 1). However, this method has a problem that the surface of polyphenylene sulfide is eroded by the etching solution and becomes brittle, and the copper plating layer formed thereon is easily peeled off over time. Therefore, when a conductive pattern is created by this method, there are problems that cause a disconnection of the copper plating layer and a decrease in conductivity (an increase in resistance value).
- polyphenylene sulfide as a support, it has excellent adhesion to metal films such as metal vapor deposition and metal plating formed thereon, connectors for connecting wiring such as electronic circuits and optical communications, molded products such as lamp reflectors, There is a need for a laminate that can be used as a conductive pattern for use in wired electronic circuits such as printed boards, electromagnetic wave shields, integrated circuits, and organic transistors.
- the problem to be solved by the present invention is a laminate in which polyphenylene sulfide is used as a support and a metal plating layer is provided on the support, and is excellent in adhesion to the metal plating layer and exposed to a high temperature environment. Even if it is a case, it is providing the laminated body also provided with the heat resistance which can maintain the outstanding adhesiveness. Moreover, it is providing the molded article, electroconductive pattern, and electronic circuit using the said laminated body.
- a laminate using a support comprising a polyphenylene sulfide resin composition containing a specific amount of elastomer has excellent adhesion to a metal plating layer. And even if it was a case where it exposed to a high temperature environment, it discovered having the heat resistance which can maintain the outstanding adhesiveness.
- a metal layer (B) and a metal plating layer (C) are sequentially laminated on a support (A) comprising a polyphenylene sulfide resin composition containing polyphenylene sulfide (a1) and elastomer (a2).
- the content of the elastomer (a2) in the polyphenylene sulfide resin composition is in the range of 0.3 to 90 parts by mass with respect to 100 parts by mass of the polyphenylene sulfide (a1).
- a conductive pattern and an electronic circuit using the same is possible.
- the laminate of the present invention has excellent adhesion between the support made of the polyphenylene sulfide resin composition and the metal plating layer laminated thereon, and even when exposed to a high temperature environment. Can maintain sex. Therefore, according to the present invention, it is possible to provide a laminate that maintains excellent conductivity without causing disconnection or the like and can be used for a highly reliable conductive pattern or electronic circuit.
- the laminate of the present invention includes, for example, connectors for connecting wiring for electronic circuits, optical communications, optical pickups such as Blu-ray and DVD; lamp reflectors for automobiles, electrical components, electric motor peripheral members, battery members; It can be used for electromagnetic wave shields used in electronic equipment.
- the laminate of the present invention using a film-like polyphenylene sulfide as a support can be used, for example, for forming RFIDs such as flexible printed boards and non-contact IC cards, and for forming each layer and peripheral wiring constituting a film capacitor.
- a metal layer (B) and a metal plating layer (C) are sequentially formed on a support (A) comprising a polyphenylene sulfide resin composition containing polyphenylene sulfide (a1) and elastomer (a2).
- the content of the elastomer (a2) in the polyphenylene sulfide resin composition is in the range of 0.3 to 90 parts by mass with respect to 100 parts by mass of the polyphenylene sulfide (a1). Is.
- the polyphenylene sulfide (a1) has a resin structure having a structure in which an aromatic ring and a sulfur atom are bonded as a repeating unit. Specifically, the structure portion represented by the following general formula (1) is repeated. Resin unit.
- R 1 and R 2 each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a nitro group, an amino group, a phenyl group, a methoxy group, or an ethoxy group.
- R 1 and R 2 in the general formula (1) are preferably hydrogen atoms because the mechanical strength of the polyphenylene sulfide (a1) is improved.
- the R 1 and R 2 are represented by the following general formula (2).
- those bonded at the meta position represented by the following general formula (3).
- the bond of the sulfur atom to the aromatic ring in the repeating unit has a structure bonded at the para position represented by the general formula (2), and the heat resistance and crystallinity of the polyphenylene sulfide (a1). Is preferable because of improvement.
- the polyphenylene sulfide (a1) includes at least one selected from the structural sites represented by the following general formulas (4) to (7) as well as the structural site represented by the general formula (1). You may have.
- the molar ratio of these structural parts in the polyphenylene sulfide (a1) is 30 mol% because heat resistance and mechanical strength are good. The following is preferable, and 10 mol% or less is more preferable.
- the bond to the repeating unit of the structural moiety represented by the general formula (1) is as follows: It may be a random type or a block type.
- the polyphenylene sulfide (a1) may have a trifunctional structural site represented by the following general formula (8), a naphthyl sulfide bond, and the like in the structure.
- the molar ratio of these structural sites in the polyphenylene sulfide (a1) is preferably 3 mol% or less, and more preferably 1 mol% or less.
- the polyphenylene sulfide (a1) can be produced, for example, by the following methods (1) to (4).
- (1) A method of reacting sodium sulfide with p-dichlorobenzene in an amide solvent such as N-methylpyrrolidone or dimethylacetamide or a sulfone solvent such as sulfolane.
- (2) A method of polymerizing p-dichlorobenzene in the presence of sulfur and sodium carbonate.
- sodium sulfide is dropped, a mixture of sodium hydrosulfide and sodium hydroxide is dropped, or a mixture of hydrogen sulfide and sodium hydroxide is dropped.
- (4) A method by self-condensation of p-chlorothiophenol.
- the method of reacting sodium sulfide and p-dichlorobenzene in an amide solvent such as N-methylpyrrolidone or dimethylacetamide or a sulfone solvent such as sulfolane in method (1) is easy to control the reaction. From the viewpoint of excellent industrial productivity.
- an alkali such as an alkali metal salt of carboxylic acid, an alkali metal salt of sulfonic acid, or a hydroxide in order to adjust the degree of polymerization.
- melt flow rate (hereinafter abbreviated as “MFR”) of the polyphenylene sulfide (a1) is preferably in the range of 1 to 3,000 g / 10 minutes because of excellent moldability and surface strength.
- the range of 2,300 g / 10 minutes is more preferable, and the range of 10 to 1,500 g / 10 minutes is more preferable.
- the melt flow rate is a value measured by ASTM D1238-86 under a load of 316 ° C./5,000 g (orifice: 0.0825 ⁇ 0.002 inch diameter ⁇ 0.315 ⁇ 0.001 inch length). is there.
- the polyphenylene sulfide (a1) can reduce the amount of residual metal ions to improve moisture resistance and reduce the residual amount of low molecular weight impurities by-produced during polymerization, the polyphenylene sulfide (a1) can be reduced. It is preferable to use an acid-treated product and then washed with water.
- acetic acid for example, acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, silicic acid, carbonic acid, and propyl acid are preferable.
- acetic acid and hydrochloric acid are preferred because the amount of residual metal ions can be efficiently reduced without decomposing the polyphenylene sulfide (a1).
- Examples of the acid treatment method include a method of immersing the polyphenylene sulfide (a1) in an acid or an acid aqueous solution. At this time, further stirring or heating may be performed as necessary.
- a method using acetic acid for example, a method using acetic acid is used.
- an aqueous acetic acid solution having a pH of 4 is heated to 80 to 90 ° C., and the polyphenylene sulfide (a1) is immersed in the solution.
- the method of stirring for 40 minutes is mentioned.
- the acid-treated polyphenylene sulfide (a1) is washed several times with water or warm water in order to physically remove the remaining acid and salt.
- the water used at this time is preferably distilled water or deionized water.
- the polyphenylene sulfide (a1) to be subjected to the acid treatment is preferably in the form of powder, and specifically, it may be a granule such as a pellet or in a slurry state after polymerization. Good.
- the elastomer (a2) is used for the purpose of imparting flexibility and low-temperature impact resistance to the polyphenylene sulfide resin composition constituting the support (A).
- the metal layer (B) and primer resin layer described later are used. There is also a function of improving adhesion with (X).
- the elastomer (a2) is preferably one that can be melt kneaded with the polyphenylene sulfide (a1) and can be uniformly mixed and dispersed. Specifically, those having a melting point of 300 ° C. or less and rubber elasticity at room temperature are preferable.
- elastomer (a2) examples include thermoplastic elastomers such as polyolefin elastomers and olefin copolymer elastomers. More specifically, for example, styrene-butadiene rubber (SBR), hydrogenated SBR, ethylene-propylene rubber (EPM), ethylene-propylene-diene rubber (EPDM), butadiene rubber, chloroprene rubber, nitrile. Rubber, butyl rubber, acrylic rubber, silicone rubber, fluorine rubber, urethane rubber and the like.
- SBR styrene-butadiene rubber
- EPM ethylene-propylene rubber
- EPDM ethylene-propylene-diene rubber
- butadiene rubber chloroprene rubber
- Rubber butyl rubber, acrylic rubber, silicone rubber, fluorine rubber, urethane rubber and the like.
- an olefin copolymer elastomer is preferable, an ethylene copolymer elastomer is more preferable, and a glycidyl group is included because adhesion to the metal layer (B) and a primer resin layer (X) described later can be further improved. Those are more preferred.
- These elastomers (a2) can be used alone or in combination of two or more.
- ethylene copolymer elastomer examples include a binary copolymer of ethylene and maleic anhydride or ethylene and an ⁇ , ⁇ -unsaturated carboxylic acid glycidyl ester as a raw material. Furthermore, a ternary copolymer obtained by adding an ⁇ , ⁇ -unsaturated carboxylic acid alkyl ester to the two monomer components of the binary copolymer may also be mentioned. Among these, the terpolymer is preferable because of excellent bending elasticity and tensile elongation.
- the compatibility with the polyphenylene sulfide (a1) can be dramatically improved, and the adhesion with the metal layer (B) and the primer resin layer (X) described later is further improved.
- a terpolymer of ethylene, ⁇ , ⁇ -unsaturated carboxylic acid alkyl ester and ⁇ , ⁇ -unsaturated carboxylic acid glycidyl ester is more preferable.
- the polyphenylene sulfide resin composition has excellent performance balance such as impact strength, tensile elongation and compatibility with the polyphenylene sulfide (a1).
- the mass ratio is preferably [50 to 98/1 to 30/1 to 30], [ In the case of a terpolymer of ethylene / ⁇ , ⁇ -unsaturated carboxylic acid alkyl ester / ⁇ , ⁇ -unsaturated carboxylic acid glycidyl ester], the mass ratio is [50 to 98/1 to 49/1 to 10]. The range of is preferable.
- Examples of the ⁇ , ⁇ -unsaturated carboxylic acid alkyl ester include alkyl esters of unsaturated carboxylic acid having 3 to 8 carbon atoms such as acrylic acid and methacrylic acid. Specific examples include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate, methyl methacrylate, ethyl methacrylate, n methacrylate.
- the content of the elastomer (a2) in the polyphenylene sulfide resin composition is in the range of 0.3 to 90 parts by mass with respect to 100 parts by mass of the polyphenylene sulfide (a1).
- the range of 0.5 to 60 parts by mass is preferable because the workability can be further improved and the adhesion to the metal layer (B) and primer resin layer (X) described later can be further improved. Is more preferable, the range of 2 to 20 parts by mass is further preferable, and the range of 5 to 10 parts by mass is particularly preferable.
- the polyphenylene sulfide resin composition constituting the support (A) further contains a fibrous inorganic filler (a3), whereby heat resistance, The mechanical properties, dimensional stability, crystallization speed and electrical properties are further improved.
- fibrous inorganic filler (a3) examples include glass fiber, carbon fiber, zinc oxide whisker, asbestos fiber, silica fiber, aluminum borate whisker, silica / alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, Examples thereof include inorganic fibers such as potassium titanate fibers; metal fibers such as stainless steel, aluminum, titanium, copper, and brass. Among these, glass fiber is preferable because of its high electrical insulation performance. Moreover, these fibrous inorganic fillers (a3) can be used alone or in combination of two or more.
- the fibrous inorganic filler (a3) is in contact with the polyphenylene sulfide (a1), an ester wax (a4) described later, and other additives by using a material processed with a surface treatment agent or a sizing agent. It is preferable because the property can be improved.
- Examples of the surface treatment agent or sizing agent include silane compounds or titanate compounds having functional groups such as amino groups, epoxy groups, isocyanate groups, and vinyl groups; polymers such as acrylic resins, urethane resins, and epoxy resins. .
- the blending amount of the fibrous inorganic filler (a3) in the polyphenylene sulfide resin composition can sufficiently exhibit the above-described effects. Therefore, it is 10 to 150 with respect to 100 parts by mass of the polyphenylene sulfide (a1).
- the range of parts by mass is preferable, the range of 30 to 100 parts by mass is more preferable, and the range of 50 to 80 parts by mass is more preferable.
- the polyphenylene sulfide resin composition constituting the support (A) includes the fibrous inorganic filler (a3) within a range not impairing the effects of the present invention.
- Other inorganic fillers such as calcium carbonate, magnesium carbonate, talc; high heat-resistant resin fibers such as aramid fiber; polyamide, polysulfone, polyallylsulfone, polyethersulfone, polyarylate, polyphenylene oxide, polyetherketone, poly Ether ether ketone, polyimide, polyamideimide, polyetherimide, silicone resin, phenoxy resin, fluororesin, liquid crystal polymer, polyaryl ether and other resins; various additives such as lubricants, waxes, stabilizers, etc. it can.
- the method for preparing the polyphenylene sulfide resin composition is not particularly limited, and can be prepared by a known production apparatus and method.
- a blend of polyphenylene sulfide (a1), elastomer (a2), fibrous inorganic filler (a3), etc. is mixed in advance with a mixer such as a Henschel mixer or tumbler, and then a single-screw or twin-screw extruder kneader. And the like, and knead at 250 to 350 ° C., granulated and pelletized.
- polyphenylene sulfide resin composition into the support (A), for example, injection molding, extrusion molding, compression molding using the pellets of the polyphenylene sulfide resin composition obtained by the above preparation method The method of shape
- the shape of the support (A) is not particularly limited, and preferably has a thickness of about 0.5 to 100 mm, more preferably about 0.5 to 10 mm. Moreover, the thing of the solid shape shape
- the support (A) may be a film or a sheet.
- the thickness of the film or sheet is preferably about 1 to 5,000 ⁇ m, more preferably about 1 to 300 ⁇ m. Furthermore, when a relatively flexible material is required as the laminate of the present invention, a material having a thickness of about 1 to 200 ⁇ m is preferable.
- transduction of functional groups, such as a hydroxyl group, a carbonyl group, and a carboxyl group, etc. may be performed.
- a plasma discharge treatment such as a corona discharge treatment, a dry treatment such as an ultraviolet treatment, a wet treatment using an aqueous solution such as water, an acid / alkali, or an organic solvent may be applied.
- the adhesion between the support (A) and the metal layer (B) is sufficiently practical, but the support (A) and the metal layer (B) In order to further improve the adhesion, it is preferable to form a primer resin layer (X) between the support (A) and the metal layer (B).
- the primer resin layer (X) is formed by applying a primer to a part or all of the surface of the support (A) and removing a solvent such as an aqueous medium or an organic solvent contained in the primer. Can do.
- Examples of a method for applying the primer to the surface of the support include a gravure method, a coating method, a screen method, a roller method, a rotary method, a spray method, a dip coating method, and the like.
- a plasma discharge treatment method such as a corona discharge treatment method, an ultraviolet treatment method, or the like.
- the surface treatment is preferably performed by a dry treatment method, a wet treatment method using water, an acidic or alkaline chemical solution, an organic solvent, or the like.
- a method for removing the solvent contained in the coating layer after coating the primer on the surface of the support for example, a method of drying using a dryer and volatilizing the solvent is common. What is necessary is just to set as drying temperature as the temperature of the range which can volatilize the said solvent and does not have a bad influence on the said support body (A).
- the amount of the primer applied onto the support (A) is preferably in the range of 0.01 to 60 g / m 2 with respect to the area of the support because it can provide excellent adhesion and conductivity. In view of the absorbability of the solvent contained in the fluid described later and the production cost, the range of 0.01 to 10 g / m 2 is more preferable.
- the thickness of the primer resin layer (X) varies depending on the use of the laminate of the present invention, but the adhesion between the support (A) and the metal layer (B) can be further improved, so that the thickness is 10 nm to 30 ⁇ m.
- the range is preferably 10 nm to 1 ⁇ m, more preferably 10 nm to 500 nm.
- primer resin layer (B) those containing various resins and solvents can be used.
- the resin examples include urethane resin, vinyl resin, core / shell composite resin having urethane resin as a shell and vinyl resin as a core, imide resin, amide resin, melamine resin, phenol resin, urea formaldehyde resin, and polyisocyanate.
- examples thereof include blocked isocyanates obtained by reacting a blocking agent such as phenol, polyvinyl alcohol, and polyvinylpyrrolidone.
- the core-shell type composite resin having a urethane resin as a shell and a vinyl resin as a core can be obtained, for example, by polymerizing a vinyl monomer in the presence of a urethane resin.
- these resins can be used alone or in combination of two or more.
- a resin that generates a reducing compound by heating is preferable because it can further improve the adhesion to the metal layer (B).
- the reducing compound include a phenol compound, an aromatic amine compound, a sulfur compound, a phosphoric acid compound, and an aldehyde compound. Of these reducing compounds, phenol compounds and aldehyde compounds are preferred.
- the resin that generates a reducing compound by heating When the resin that generates a reducing compound by heating is used as a primer, reducing compounds such as formaldehyde and phenol are generated in the heating and drying step when forming the primer resin layer (X).
- reducing compounds such as formaldehyde and phenol are generated in the heating and drying step when forming the primer resin layer (X).
- Specific examples of the resin that generates the reducing compound by heating include a vinyl resin obtained by polymerizing a monomer containing N-alkylol (meth) acrylamide, and N-alkylol (meth) acrylamide using a urethane resin as a shell.
- examples thereof include resins that formaldehyde by heating such as formaldehyde adducts of meth) acrylamide and melamine resins; resins that generate phenol compounds by heating phenol resins, phenol blocked isocyanates, and the like.
- the core is made of a vinyl resin obtained by polymerizing a monomer containing urethane resin as a shell and N-alkylol (meth) acrylamide.
- -Shell type composite resin, melamine resin, and phenol block isocyanate are preferable.
- (meth) acrylamide refers to one or both of “methacrylamide” and “acrylamide”
- (meth) acrylic acid refers to “methacrylic acid” and “acrylic acid”. One or both.
- the vinyl resin can be obtained by polymerizing a vinyl monomer that generates a reducing compound by heating by a polymerization method such as radical polymerization, anionic polymerization, or cationic polymerization.
- Examples of the vinyl monomer that forms a reducing compound by heating include N-alkylol vinyl monomers, and specifically include N-methylol (meth) acrylamide, N-methoxymethyl (meta ) Acrylamide, N-ethoxymethyl (meth) acrylamide, N-propoxymethyl (meth) acrylamide, N-isopropoxymethyl (meth) acrylamide, Nn-butoxymethyl (meth) acrylamide, N-isobutoxymethyl (meth) Examples include acrylamide, N-pentoxymethyl (meth) acrylamide, N-ethanol (meth) acrylamide, and N-propanol (meth) acrylamide.
- vinyl resin when manufacturing the said vinyl resin, other various vinyl monomers, such as a (meth) acrylic-acid alkylester, may be copolymerized with the vinyl monomer etc. which produce
- a (meth) acrylic-acid alkylester when manufacturing the said vinyl resin, other various vinyl monomers, such as a (meth) acrylic-acid alkylester, may be copolymerized with the vinyl monomer etc. which produce
- a uretdione bond is formed by self-reaction between isocyanate groups, or a functional group possessed by an isocyanate group and other components. And form a bond, thereby forming the primer resin layer (X). Even if the bond is formed before applying the fluid described later, the bond is not formed before the fluid is applied, and the bond is formed by heating after applying the fluid. May be formed.
- blocked isocyanate examples include those having a functional group formed by blocking an isocyanate group with a blocking agent.
- the blocked isocyanate can further improve the adhesion between the support (A) and the primer resin layer (X) and the adhesion between the primer resin layer (X) and the metal layer (B). Those having the functional group in the range of 350 to 600 g / mol per mole of the blocked isocyanate are preferable.
- the functional group preferably has 1 to 10 functional groups, more preferably 2 to 5 in one molecule of the blocked isocyanate because adhesion can be further improved.
- the number average molecular weight of the blocked isocyanate is preferably in the range of 1,500 to 5,000, more preferably in the range of 1,500 to 3,000 because the adhesion can be further improved.
- the blocked isocyanate those having an aromatic ring are preferable because adhesion can be further improved.
- the aromatic ring include a phenyl group and a naphthyl group.
- the blocked isocyanate can be produced by reacting a part or all of the isocyanate groups of the isocyanate compound (a-1) with a blocking agent.
- Examples of the isocyanate compound used as the raw material for the blocked isocyanate include 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, phenylene diisocyanate, tolylene diisocyanate, and naphthalene diisocyanate.
- Polyisocyanate compounds having an aromatic ring aliphatic polyisocyanate compounds such as hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, or poly having an alicyclic structure Isocyanate compounds and the like. Moreover, those burette bodies, isocyanurate bodies, adduct bodies, etc. of the polyisocyanate compounds described above are also included.
- examples of the isocyanate compound include those obtained by reacting the polyisocyanate compound exemplified above with a compound having a hydroxyl group or an amino group.
- polyisocyanate compound having an aromatic ring When introducing an aromatic ring into the blocked isocyanate, it is preferable to use a polyisocyanate compound having an aromatic ring.
- a polyisocyanate compound having an aromatic ring 4,4'-diphenylmethane diisocyanate, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate isocyanurate, and tolylene diisocyanate isocyanurate are preferred.
- Examples of the blocking agent used for the production of the blocked isocyanate include phenol compounds such as phenol and cresol; lactam compounds such as ⁇ -caprolactam, ⁇ -valerolactam, and ⁇ -butyrolactam; formamide oxime, acetoald oxime, acetone oxime, Oxime compounds such as methyl ethyl ketoxime, methyl isobutyl ketoxime, cyclohexanone oxime; 2-hydroxypyridine, butyl cellosolve, propylene glycol monomethyl ether, benzyl alcohol, methanol, ethanol, n-butanol, isobutanol, dimethyl malonate, diethyl malonate, aceto Methyl acetate, ethyl acetoacetate, acetylacetone, butyl mercaptan, dodecyl mercaptan, acetanilide, acetic acid acetate Succinimide
- a blocking agent capable of generating an isocyanate group by dissociation by heating in the range of 70 to 200 ° C. is preferable, and a block capable of generating an isocyanate group dissociating by heating in the range of 110 to 180 ° C.
- An agent is more preferred.
- a phenol compound, a lactam compound, and an oxime compound are preferable.
- the phenol compound is more preferable because it becomes a reducing compound when the blocking agent is eliminated by heating.
- Examples of the method for producing the blocked isocyanate include a method in which the isocyanate compound produced in advance and the blocking agent are mixed and reacted, a method in which the blocking agent is mixed and reacted with raw materials used in the production of the isocyanate compound, and the like. Is mentioned.
- the blocked isocyanate is prepared by reacting the polyisocyanate compound with a compound having a hydroxyl group or an amino group to produce an isocyanate compound having an isocyanate group at a terminal, and then the isocyanate compound and the block. It can manufacture by mixing and making it react with an agent.
- the blocked isocyanate obtained by the above method is preferably contained in the range of 50 to 100% by mass and more preferably in the range of 70 to 100% by mass in the total amount of the resin composition forming the primer resin layer (X). More preferably.
- the resin composition forming the primer resin layer (X) may contain a solvent capable of dissolving or dispersing the solid content such as the blocked isocyanate.
- the solvent for example, an aqueous medium or an organic solvent can be used.
- the melamine resin examples include mono- or polymethylol melamine in which 1 to 6 mol of formaldehyde is added to 1 mol of melamine; (poly) methylol melamine such as trimethoxymethylol melamine, tributoxymethylol melamine, and hexamethoxymethylol melamine.
- Examples include etherified products (the degree of etherification is arbitrary); urea-melamine-formaldehyde-methanol condensate, and the like.
- a method of adding a reducing compound to the resin can also be mentioned.
- the reducing compound to be added include phenolic antioxidants, aromatic amine antioxidants, sulfur antioxidants, phosphate antioxidants, vitamin C, vitamin E, and ethylenediaminetetraacetic acid. Examples thereof include sodium, sulfite, hypophosphorous acid, hypophosphite, hydrazine, formaldehyde, sodium borohydride, dimethylamine borane, and phenol.
- the method of adding a reducing compound to the resin ultimately reduces the electrical properties due to residual low molecular weight components and ionic compounds.
- a method using a resin that forms a compound is more preferable.
- the primer resin layer (X) preferably contains 1 to 70% by mass of the resin in the primer, and more preferably contains 1 to 20% by mass because the coatability is improved.
- examples of the solvent that can be used for the primer include various organic solvents and aqueous media.
- examples of the organic solvent include toluene, ethyl acetate, methyl ethyl ketone, cyclohexanone, and the like.
- examples of the aqueous medium include water, an organic solvent miscible with water, and a mixture thereof.
- organic solvent miscible with water examples include alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, ethyl carbitol, ethyl cellosolve, butyl cellosolve; ketone solvents such as acetone and methyl ethyl ketone; ethylene glycol, diethylene glycol, propylene And alkylene glycol solvents such as glycol; polyalkylene glycol solvents such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol; and lactam solvents such as N-methyl-2-pyrrolidone.
- alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, ethyl carbitol, ethyl cellosolve, butyl cellosolve
- ketone solvents such as acetone and methyl ethyl ketone
- the resin may have a crosslinkable functional group such as an alkoxysilyl group, a silanol group, a hydroxyl group, or an amino group, if necessary.
- a crosslinkable functional group such as an alkoxysilyl group, a silanol group, a hydroxyl group, or an amino group, if necessary.
- the crosslinked structure formed by these crosslinkable functional groups may already form a crosslinked structure before the fluid is applied, and after the fluid is applied, for example, a firing step or the like
- a crosslinked structure may be formed by heating at.
- primer resin layer (X) known materials such as a cross-linking agent, a pH adjuster, a film forming aid, a leveling agent, a thickener, a water repellent, and an antifoaming agent are appropriately used as necessary. You may add and use.
- crosslinking agent examples include metal chelate compounds, polyamine compounds, aziridine compounds, metal salt compounds, isocyanate compounds and the like, and thermal crosslinking agents that react at a relatively low temperature of about 25 to 100 ° C. to form a crosslinked structure; Thermal crosslinking agents that react at a relatively high temperature of 100 ° C. or higher, such as melamine compounds, epoxy compounds, oxazoline compounds, carbodiimide compounds, and blocked isocyanate compounds, to form a crosslinked structure; and various photocrosslinking agents.
- the cross-linking agent varies depending on the type, etc., it is excellent in adhesion and conductivity, and can form a conductive pattern excellent in the durability. Therefore, with respect to a total of 100 parts by mass of the resin contained in the primer, It is preferably used in the range of 0.01 to 60 parts by mass, more preferably in the range of 0.1 to 10 parts by mass, and still more preferably in the range of 0.1 to 5 parts by mass.
- a crosslinked structure may be formed in the primer resin layer (X) by heating in a firing step or the like.
- the metal layer (B) is formed on the support (A) or the primer resin layer (X), and the metal constituting the metal layer (B) is a transition metal or a compound thereof.
- ionic transition metals are preferable.
- the ionic transition metal include copper, silver, gold, nickel, palladium, platinum, cobalt, and chromium.
- copper, silver, and gold are preferable because they have a low electrical resistance and provide a conductive pattern that is resistant to corrosion.
- the metal layer (B) is preferably porous, and in this case, the metal layer (B) has voids.
- examples of the metal constituting the metal plating layer (C) include copper, nickel, chromium, cobalt, tin and the like. Among these, copper is preferable because a conductive pattern having low electric resistance and strong against corrosion can be obtained.
- the voids present in the metal layer (B) are filled with the metal constituting the metal plating layer (C), and the support (A) and the metal layer ( The metal layer (B) and the metal plating layer are filled with the metal constituting the metal plating layer (C) up to the gap in the metal layer (B) existing in the vicinity of the interface with B). Since adhesiveness with (C) improves more, it is preferable.
- the fluid containing a nanosize metal powder and a dispersing agent is apply
- An example is a method in which an organic compound containing a dispersing agent is removed to form a void to form a porous metal layer (B), and then the metal plating layer (C) is formed by electrolysis or electroless plating. .
- the shape of the nano-sized metal powder used to form the metal layer (B) is not particularly limited as long as the metal layer becomes porous, but is preferably in the form of particles or fibers.
- the size of the metal powder is nano-sized. Specifically, when the shape of the metal powder is particulate, a fine conductive pattern can be formed, and the resistance value after firing is further reduced. Therefore, the average particle size is preferably in the range of 1 to 100 nm, more preferably in the range of 1 to 50 nm.
- the “average particle size” is a volume average value measured by a dynamic light scattering method after diluting the conductive substance with a good dispersion solvent. For this measurement, “Nanotrack UPA-150” manufactured by Microtrack Co. can be used.
- the fiber diameter is preferably in the range of 5 to 100 nm, and in the range of 5 to 50 nm. Is more preferable.
- the fiber length is preferably in the range of 0.1 to 100 ⁇ m, and more preferably in the range of 0.1 to 30 ⁇ m.
- a fluid in which the nano-sized metal powder is dispersed in a solvent is placed on the primer resin layer (X).
- a coating method is preferred.
- the content ratio of the nano-sized metal powder in the fluid is preferably in the range of 5 to 90% by mass, and more preferably in the range of 10 to 60% by mass.
- the components to be blended in the fluid include a dispersant and a solvent for dispersing the nano-sized metal powder in the solvent, and, if necessary, a surfactant, a leveling agent, a viscosity modifier, and a film formation described later.
- Organic compounds such as auxiliaries, antifoaming agents and preservatives are included.
- a low molecular weight or high molecular weight dispersant is used.
- the dispersant include dodecanethiol, 1-octanethiol, triphenylphosphine, dodecylamine, polyethylene glycol, polyvinylpyrrolidone, polyethyleneimine, polyvinylpyrrolidone; fatty acids such as myristic acid, octanoic acid, stearic acid; cholic acid, Examples thereof include polycyclic hydrocarbon compounds having a carboxyl group such as glycyrrhizic acid and avintinic acid.
- a polymer dispersant is preferable because the adhesion between the metal layer (B) and a metal plating layer (C) described later can be improved by increasing the void size in the metal layer (B).
- the polymer dispersant is preferably a polyalkyleneimine such as polyethyleneimine or polypropyleneimine, or a compound obtained by adding polyoxyalkylene to the polyalkyleneimine.
- the void size formed by removing the dispersant in the metal layer (B) can be increased as compared with the low-molecular dispersant. It is possible to form voids having a size of nano-order to sub-micron order.
- the voids are easily filled with the metal constituting the metal plating layer (C), which will be described later, and the filled metal serves as an anchor, greatly improving the adhesion between the metal layer (B) and the metal plating layer (C). Can be improved.
- the amount of the dispersant used for dispersing the nano-sized metal powder is preferably 0.01 to 50 parts by weight, and 0.01 to 10 parts by weight with respect to 100 parts by weight of the nano-sized metal powder. Is more preferable.
- the nano The amount is preferably 0.1 to 10 parts by weight, and more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the size of the metal powder.
- an aqueous medium or an organic solvent can be used as the solvent used for the fluid.
- the aqueous medium include distilled water, ion exchange water, pure water, and ultrapure water.
- the organic solvent include alcohol compounds, ether compounds, ester compounds, and ketone compounds.
- Examples of the alcohol include methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol, sec-butanol, tert-butanol, heptanol, hexanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetra Decanol, pentadecanol, stearyl alcohol, allyl alcohol, cyclohexanol, terpineol, terpineol, dihydroterpineol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol mono Spotted Ether, tetraethylene glycol monobutyl ether, propylene glycol monomethyl ether
- ethylene glycol, diethylene glycol, 1,3-butanediol, isoprene glycol and the like can be used for the fluid as necessary.
- a general surfactant can be used.
- di-2-ethylhexylsulfosuccinate, dodecylbenzenesulfonate, alkyldiphenylether disulfonate, alkylnaphthalenesulfonate, hexametalin Examples include acid salts.
- leveling agent a general leveling agent can be used, and examples thereof include silicone compounds, acetylenic diol compounds, and fluorine compounds.
- a general thickener can be used, for example, an acrylic polymer or synthetic rubber latex that can be thickened by adjusting to an alkaline property, and can be thickened by association of molecules.
- examples include urethane resin, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, polyvinyl alcohol, water-added castor oil, amide wax, oxidized polyethylene, metal soap, and dibenzylidene sorbitol.
- a general film forming aid can be used.
- an anionic surfactant dioctylsulfosuccinic acid ester soda salt, etc.
- a hydrophobic nonionic surfactant sorbitan monooleate
- polyether-modified siloxane silicone oil, and the like.
- a general antifoaming agent can be used, and examples thereof include silicone-based antifoaming agents, nonionic surfactants, polyethers, higher alcohols, and polymer-based surfactants.
- preservatives can be used, for example, isothiazoline preservatives, triazine preservatives, imidazole preservatives, pyridine preservatives, azole preservatives, iodine preservatives, Examples include pyrithione preservatives.
- the viscosity of the fluid is preferably in the range of 0.1 to 500,000 mPa ⁇ s, more preferably in the range of 0.5 to 10,000 mPa ⁇ s. .
- the viscosity is preferably in the range of 5 to 20 mPa ⁇ s.
- Examples of the method for applying the fluid on the primer resin layer (X) include an inkjet printing method, a reverse printing method, a screen printing method, an offset printing method, a spin coating method, a spray coating method, a bar coating method, Examples thereof include a die coating method, a slit coating method, a roll coating method, and a dip coating method.
- inkjet printing in the case of forming the metal layer (B) patterned in a thin line shape of about 0.01 to 100 ⁇ m, which is required when realizing high density of electronic circuits or the like, inkjet printing is used. It is preferable to use the reverse printing method.
- an ink jet printer As the ink jet printing method, what is generally called an ink jet printer can be used. Specific examples include Konica Minolta EB100, XY100 (manufactured by Konica Minolta Co., Ltd.), Dimatics Material Printer DMP-3000, Dimatics Material Printer DMP-2831 (manufactured by Fuji Film Co., Ltd.), and the like.
- the fluid is applied to the surface of various blankets and brought into contact with a plate from which a non-image portion protrudes, By selectively transferring a fluid corresponding to a non-image area to the surface of the plate, the pattern is formed on the surface of the blanket or the like, and then the pattern is formed on the support (A) ( And a method of transferring to the surface).
- the metal layer (B) can be obtained, for example, by applying a fluid containing metal powder and then performing a firing step.
- the metal layer (B) which has electroconductivity can be formed by closely_contact
- the firing step is preferably performed at a temperature of 80 to 300 ° C. for about 2 to 200 minutes.
- the firing step may be performed in the air, but a part or all of the firing step may be performed in a reducing atmosphere in order to prevent all of the metal powder from being oxidized.
- the particulate or fibrous metal powders used for forming the metal layer (B) are in close contact with each other, and the organic compound such as a dispersant contained in the fluid. By removing, the metal layer (B) becomes porous.
- the baking step can be performed using, for example, an oven, a hot air drying furnace, an infrared drying furnace, laser irradiation, microwave, light irradiation (flash irradiation apparatus), or the like.
- the amount of adhesion of the metal layer (B) obtained by the firing step is preferably in the range of 1 to 30,000 mg / m 2 in view of the adhesion to the metal plating layer (C) described later, and 50 to 10 , more preferably in the range of 000mg / m 2, further preferably in the range of 50 ⁇ 5,000mg / m 2.
- the organic compound such as a dispersant contained in the fluid that could not be removed even in the above baking step is a plasma discharge treatment method, an electromagnetic wave irradiation treatment method, a laser irradiation treatment method, water or an organic solvent.
- the organic compound containing can be removed by a dissolution treatment method in which the organic compound is dissolved again and dissolved. These treatment methods are preferable because they can be used alone or in combination of two or more, and the organic compound can be removed more efficiently by combining two or more.
- the organic compound referred to here is a component contained in the fluid, and includes organic substances such as a dispersant, a solvent, a surfactant, a leveling agent, a viscosity modifier, a film forming aid, an antifoaming agent, and an antiseptic.
- organic substances such as a dispersant, a solvent, a surfactant, a leveling agent, a viscosity modifier, a film forming aid, an antifoaming agent, and an antiseptic.
- Examples of the plasma discharge treatment method include an atmospheric pressure plasma discharge treatment method such as a corona discharge treatment method, a vacuum plasma discharge treatment method such as a glow discharge treatment method and an arc discharge treatment method performed under vacuum or reduced pressure, and the like.
- Examples of the normal pressure plasma discharge treatment method include a plasma discharge treatment method in an atmosphere having an oxygen concentration of about 0.1 to 25% by volume.
- the metal layer (B) and the metal plating layer (C) are easily filled with the metal constituting the metal plating layer (C) in the voids of the porous metal layer (B).
- the oxygen concentration is preferably in the range of 10 to 22% by volume, more preferably about 21% by volume (in an air atmosphere).
- the atmospheric pressure plasma discharge treatment method can be performed in an environment containing an inert gas together with the oxygen without giving excessive irregularities to the surface of the metal layer (B).
- the metal plating layer (C) are more preferable because the adhesion can be further improved.
- the inert gas include argon and nitrogen.
- Examples of an apparatus that can be used for the treatment by the atmospheric pressure plasma discharge treatment method include an atmospheric pressure plasma treatment apparatus “AP-T01” manufactured by Sekisui Chemical Co., Ltd.
- the flow rate of gas such as air is preferably in the range of 5 to 50 liters / minute.
- the output is preferably in the range of 50 to 500W.
- the treatment time is preferably in the range of 1 to 500 seconds.
- a corona discharge treatment method As an apparatus that can be used in the corona discharge treatment method, for example, a corona surface modification evaluation apparatus “TEC-4AX” manufactured by Kasuga Electric Co., Ltd. may be mentioned.
- the output is preferably in the range of 5 to 300 W.
- the treatment time is preferably in the range of 0.5 to 600 seconds.
- the plasma discharge treatment method can remove the organic compound existing in the metal layer (B) to a deep portion, and is present in the vicinity of the interface between the support (A) and the metal layer (B). It is preferable because even the organic compound present in the metal layer (B) can be removed.
- the metal plating layer (C) is formed by using the plasma discharge treatment method described above, the metal constituting the metal plating layer (C) is filled in the voids of the porous metal layer (B).
- the metal constituting the metal plating layer (C) is more preferably filled up to the voids in the metal layer (B) existing in the vicinity of the interface between the support (A) and the metal layer (B). It becomes easy. Accordingly, the metal constituting the metal plating layer (C) enters a deeper portion of the metal layer (B) and exhibits a larger anchor effect. Therefore, the metal layer (B) and the metal plating layer Adhesion with (C) can be greatly improved.
- the metal layer (B) is heated at a high temperature by irradiating the metal layer (B) with electromagnetic waves, whereby the organic compound can be decomposed and removed.
- the dispersant can be selectively removed using electromagnetic wave absorption resonance.
- the wavelength of the electromagnetic wave that resonates with the organic compound present in the metal layer (B) is set in advance, and the electromagnetic wave having the wavelength set in the metal layer (B) is irradiated. Thereby, since the absorption to the organic compound increases (resonance), only the dispersant can be removed by adjusting the intensity of the electromagnetic wave.
- the organic compound in the metal layer (B) can be decomposed and removed by irradiating the metal layer (B) with a laser.
- a laser capable of laser scribing treatment can be used.
- the laser that can be laser-scribed include a YAG laser, a CO 2 laser, and an excimer laser, and a YAG laser is particularly preferable.
- a YAG laser is particularly preferable.
- a YAG laser preferably uses a pulsed laser in order to obtain a high peak power and a high frequency.
- a laser beam output from a laser light source is condensed by a lens while conveying the metal layer (B), and the metal layer (B ).
- the laser beam is moved using a polygon mirror, and the surface of the metal layer (B) being conveyed is scanned with the laser beam.
- the said metal layer (B) can be heated at high temperature.
- the output of the laser beam is 0.1 to 100 kW
- the pulse transmission frequency (oscillation frequency) is several kHz to several tens kHz
- the duration (pulse width) of one pulse is 90 to 100 nanoseconds. It is preferable.
- the dissolution treatment method is a method of removing the organic compound existing in the metal layer (B) by redispersing it and dissolving it in water or an organic solvent.
- the organic solvent include alcohol solvents such as methanol, ethanol and isopropyl alcohol; aprotic polar solvents such as dimethyl sulfoxide, dimethylformamide and N-methylpyrrolidone; tetrahydrofuran, methyl ethyl ketone, ethyl acetate and ecamide (organic solvent manufactured by Idemitsu Kosan Co., Ltd.) ) And the like.
- an acid or an alkali in order to re-disperse and dissolve the organic compound, it is preferable to use an acid or an alkali, and more preferably to use an alkali.
- the acid include sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, oxalic acid, acetic acid, formic acid, propionic acid, succinic acid, glutaric acid, tartaric acid, adipic acid and the like.
- strong acids such as sulfuric acid, nitric acid, and hydrochloric acid.
- the metal plating layer (C) is formed by an electrolytic copper plating process using copper sulfate, it is preferable to use sulfuric acid so as not to bring impurities into the subsequent process.
- alkali examples include organic amines such as sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, ammonia, triethylamine, pyridine and morpholine; alkanolamines such as monoethanolamine. Among these, it is preferable to use a strong alkali such as sodium hydroxide or potassium hydroxide.
- a surfactant can be used to re-disperse and dissolve the organic compound.
- a general surfactant can be used, and examples thereof include di-2-ethylhexyl sulfosuccinate, alkyl sulfate, alkyl benzene sulfonate, and alkyl diphenyl ether disulfonate. Since these surfactants show alkalinity when dissolved in water, they are more preferable because they easily remove the organic compound.
- the metal layer (B) The laminated body of this invention can be obtained by forming the said metal plating layer (C) on it.
- the metal plating layer (C) forms a highly reliable wiring pattern capable of maintaining good electrical conductivity without causing disconnection or the like over a long period of time when the laminate is used for a conductive pattern or the like. It is a layer provided for the purpose of doing.
- the metal plating layer (C) is a layer formed on the metal layer (B), and the formation method is preferably a method of forming by plating.
- the plating treatment include wet plating methods such as electrolytic plating methods and electroless plating methods, and dry plating methods such as sputtering methods and vacuum deposition methods. Further, the metal plating layer (C) may be formed by combining two or more of these plating methods.
- the metal constituting the metal plating layer (C) is easily filled in the voids of the porous metal layer (B), and the metal layer (B) and the metal plating layer (C) Therefore, wet plating methods such as an electrolytic plating method and an electroless plating method are preferred, and an electrolytic plating method is more preferred.
- the metal constituting the metal layer (B) is brought into contact with an electroless plating solution, thereby depositing a metal such as copper contained in the electroless plating solution from the metal film.
- This is a method of forming an electroless plating layer (film).
- Examples of the electroless plating solution include those containing a metal such as copper, nickel, chromium, cobalt, and tin, a reducing agent, and a solvent such as an aqueous medium and an organic solvent.
- reducing agent examples include dimethylaminoborane, hypophosphorous acid, sodium hypophosphite, dimethylamine borane, hydrazine, formaldehyde, sodium borohydride, phenol and the like.
- monocarboxylic acids such as acetic acid and formic acid
- dicarboxylic acid compounds such as malonic acid, succinic acid, adipic acid, maleic acid, and fumaric acid
- malic acid lactic acid, glycol Hydroxycarboxylic acid compounds such as acid, gluconic acid and citric acid
- amino acid compounds such as glycine, alanine, iminodiacetic acid, arginine, aspartic acid and glutamic acid
- iminodiacetic acid nitrilotriacetic acid, ethylenediaminediacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, etc.
- a complexing agent such as an organic compound such as an aminopolycarboxylic acid compound or a soluble salt (sodium salt, potassium salt, ammonium salt, etc.) of these organic acids, or an amine compound such as ethylenediamine, diethylenetriamine, or triethylenetetramine. It can be used for.
- the electroless plating solution is preferably used in the range of 20 to 98 ° C.
- the metal constituting the metal layer (B) or the surface of the electroless plating layer (film) formed by the electroless treatment is energized in a state where the electrolytic plating solution is in contact with the surface.
- a metal such as copper contained in the electrolytic plating solution is made of a conductive substance constituting the metal layer (B) installed on the cathode or an electroless plating layer (film) formed by the electroless treatment. It is a method of forming an electrolytic plating layer (metal film) by depositing on the surface.
- Examples of the electrolytic plating solution include those containing metal sulfides such as copper, nickel, chromium, cobalt, and tin, sulfuric acid, and an aqueous medium. Specifically, what contains copper sulfate, sulfuric acid, and an aqueous medium is mentioned.
- the electrolytic plating solution is preferably used in the range of 20 to 98 ° C.
- a sputtering method, a vacuum deposition method, or the like can be used as the dry plating process.
- an inert gas mainly argon
- negative ions are applied to the material for forming the metal plating layer (C) to generate glow discharge
- the inert gas Atoms are ionized
- gas ions are struck violently at the surface of the material for forming the metal plating layer (C) at a high speed, and atoms and molecules constituting the material for forming the metal plating layer (C) are ejected vigorously.
- Examples of the material for forming the metal plating layer (C) by sputtering include chrome, copper, titanium, silver, platinum, gold, nickel-chromium alloy, stainless steel, copper-zinc alloy, indium tin oxide (ITO), and dioxide.
- Examples include silicon, titanium dioxide, niobium oxide, and zinc oxide.
- a magnetron sputtering apparatus or the like When performing the plating process by the sputtering method, for example, a magnetron sputtering apparatus or the like can be used.
- the thickness of the metal plating layer (C) is preferably in the range of 1 to 50 ⁇ m.
- the thickness of the metal plating layer (C) is adjusted by controlling the processing time, current density, the amount of plating additive used, etc. in the plating process when forming the metal plating layer (C). Can do.
- the laminate of the present invention obtained by the above method can be used as a conductive pattern.
- a fluid containing the metal powder is applied to form the metal layer (B) at a position corresponding to a desired pattern shape to be formed, or By printing and baking, a conductive pattern having a desired pattern can be manufactured.
- the conductive pattern may be, for example, a photolithographic etching method such as a subtractive method or a semi-additive method in which a conductive layer is formed by etching a metal layer (B) or a metal plating layer (C) from a solid metal film, Or it can manufacture by the method of plating on the printing pattern of a metal layer (B).
- a photolithographic etching method such as a subtractive method or a semi-additive method in which a conductive layer is formed by etching a metal layer (B) or a metal plating layer (C) from a solid metal film, Or it can manufacture by the method of plating on the printing pattern of a metal layer (B).
- an etching resist layer having a shape corresponding to a desired pattern shape is formed on the metal plating layer (C) constituting the laminate of the present invention that has been manufactured in advance, and by subsequent development processing,
- a desired pattern is formed by dissolving and removing the metal plating layer (C) and the metal layer (B) in the removed portion of the resist with a chemical solution.
- a chemical solution a chemical solution containing copper chloride, iron chloride or the like can be used.
- the metal layer (B) is formed directly or after forming the primer resin layer (X) on the support (A), and the metal layer (B) is formed as necessary by plasma discharge treatment or the like.
- a plating resist layer having a shape corresponding to a desired pattern is formed on the surface of the obtained metal layer (B).
- a metal plating layer (C) is formed by plating or electroless plating, a desired pattern is formed by dissolving and removing the plating resist layer and the metal layer (B) in contact therewith in a chemical solution or the like. It is a method to do.
- the method of plating on the printed pattern of the metal layer (B) is the method of forming the primer resin layer (X) directly or on the support (A), and then using the inkjet method, the reverse printing method, or the like.
- the metal layer (B) obtained by printing the pattern of the metal layer (B) and removing the organic compound containing the dispersant present in the metal layer (B) by plasma discharge treatment or the like, if necessary.
- a desired pattern is formed by forming the metal plating layer (C) on the surface by electrolytic plating or electroless plating.
- the conductive pattern obtained by the above method is excellent in adhesion between the polyphenylene sulfide serving as a support for the conductive pattern and the metal plating layer provided thereon, even in a state where a voltage is applied in a high temperature environment. It can be used for circuit forming substrates, organic solar cells, electronic terminals, organic EL devices, organic transistors, flexible printed boards, peripheral wirings constituting RFID, electromagnetic wave shields, etc. used in electronic circuits and integrated circuits.
- the conductive pattern can be used, for example, for optical pickups such as Blu-ray and DVD; electrical components for hybrid vehicles and electric vehicles, electric motor peripheral members, battery members; electromagnetic wave shields used in various electronic devices.
- a conductive pattern using a film-like polyphenylene sulfide as a support can be used, for example, for forming each layer or peripheral wiring constituting a flexible printed circuit board, an RFID such as a non-contact IC card, or a film capacitor.
- a laminate in which a molded product obtained by molding the polyphenylene sulfide resin composition is used as a support (A), and the metal layer (B) and the metal plating layer (C) are sequentially laminated thereon It can be used for molded products such as connectors for connecting wiring for electronic circuits, optical communications, and lamp reflectors for automobiles.
- Polyester polyol (polyester polyol obtained by reacting 1,4-cyclohexanedimethanol, neopentyl glycol and adipic acid) in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer 100 Parts by weight, 17.6 parts by weight of 2,2-dimethylolpropionic acid, 21.7 parts by weight of 1,4-cyclohexanedimethanol and 106.2 parts by weight of dicyclohexylmethane-4,4′-diisocyanate, and 178 parts by weight of methyl ethyl ketone To obtain a urethane prepolymer solution having an isocyanate group at the terminal.
- the urethane prepolymer was chain-extended by adding 8.8 parts by mass of a 25% by mass ethylenediamine aqueous solution to the aqueous dispersion of the urethane prepolymer obtained above and stirring. Next, an aqueous dispersion of urethane resin (non-volatile content: 30% by mass) was obtained by aging and solvent removal.
- the urethane resin had a weight average molecular weight of 53,000.
- the mixture was further stirred at the same temperature for 60 minutes, and then the temperature in the reaction vessel was cooled to 40 ° C., diluted with deionized water so that the nonvolatile content became 20% by mass, and then 200 mesh filter cloth.
- the resin composition for primer resin layer (X-1) which is a core-shell type composite resin in which the urethane resin is used as a shell layer and a vinyl resin using methyl methacrylate as a raw material is used as a core layer. An aqueous dispersion was obtained.
- Preparation Example 1 Preparation of fluid (1)
- a nano-sized metal A fluid containing powder and dispersant was prepared.
- the fluid (1) which is a conductive ink for inkjet printing was prepared by adding ion-exchange water and surfactant to the obtained fluid, and adjusting a viscosity to 10 mPa * s.
- Example 1 100 parts by mass of linear polyphenylene sulfide (MFR according to ASTM D1238-86: 600 g / 10 min), 54.5 parts by mass of chopped glass fiber (“FT562” manufactured by Asahi Fiber Glass Co., Ltd., fibrous inorganic filler), glycidyl methacrylate modification Uniformly distribute 0.5 parts by mass of ethylene-methyl acrylate copolymer elastomer (“Bond First 7L” manufactured by Sumitomo Chemical Co., Ltd.) and 0.8 parts by mass of montanic acid composite ester wax (“Recove WE40” manufactured by Clariant Japan Co., Ltd.) After mixing, the mixture was melt kneaded at 290 to 330 ° C.
- MFR linear polyphenylene sulfide
- FT562 manufactured by Asahi Fiber Glass Co., Ltd., fibrous inorganic filler
- glycidyl methacrylate modification Uniformly distribute 0.5 parts by mass of
- the obtained polyphenylene sulfide resin composition was molded with an injection molding machine to obtain a support (A-1) having a size of 50 mm ⁇ 105 mm ⁇ 2 mm.
- the aqueous dispersion of the resin composition (X-1) for primer resin layer obtained in Production Example 1 is dried using a spin coater.
- the primer resin layer was formed on the support (A-1) by coating so as to have a thickness of 0.1 ⁇ m, and then drying for 5 minutes at 80 ° C. using a hot air dryer.
- the fluid (1) obtained in Preparation Example 1 is applied to the entire surface of the primer resin layer with an ink jet printer (“Inkjet Tester EB100” manufactured by Konica Minolta, Inc., evaluation printer head KM512L, discharge amount 42 pL). It applied using. Then, the silver layer (thickness about 0.1 micrometer) equivalent to a metal layer (B) was formed by baking for 30 minutes at 200 degreeC.
- Inkjet Tester EB100 manufactured by Konica Minolta, Inc., evaluation printer head KM512L, discharge amount 42 pL.
- the surface of the silver layer obtained above is placed on the cathode, phosphorous copper is placed on the anode, and electroplating is performed for 40 minutes at a current density of 2.5 A / dm 2 using an electroplating solution containing copper sulfate.
- a copper plating layer having a thickness of 15 ⁇ m was laminated on the surface of the silver layer.
- the electroplating solution copper sulfate 70 g / liter, sulfuric acid 200 g / liter, chloride ion 50 mg / liter, Top Lucina SF (brightener manufactured by Okuno Pharmaceutical Co., Ltd.) 5 g / liter was used.
- Examples 2 to 4 The polyphenylene sulfide resin composition used for the support was changed to the composition shown in Table 1 to obtain supports (A-2) to (A-5), and the primer resin layer resin composition (X-1) was used as a primer.
- a support (A), primer resin layer (X), metal layer (B) and metal plating layer (C) were prepared in the same manner as in Example 1 except that the resin composition for resin layer (X-2) was changed. ) Were sequentially laminated to obtain laminates (2) to (5).
- Example 5 The polyphenylene sulfide resin composition used for the support was changed to the composition shown in Table 1 to obtain a support (A-5), and the primer resin layer resin composition (X-1) was used as the primer resin layer resin composition. A laminate in which the support (A), the primer resin layer (X), the metal layer (B), and the metal plating layer (C) were sequentially laminated in the same manner as in Example 1 except that (X-3) was changed. Body (5) was obtained.
- Example 6 Using the support (A-3) obtained in Example 3, a silver layer was formed directly on the support (A-3) without using the resin composition (X-1) for the primer resin layer. Except for the above, a laminate (6) in which the support (A), the metal layer (B), and the metal plating layer (C) were sequentially laminated was obtained in the same manner as in Example 1.
- peel strength was measured using "Autograph AGS-X 500N" by Shimadzu Corporation.
- the lead width used for measurement was 5 mm, and the peel angle was 90 °. Further, the peel strength tends to show a higher value as the thickness of the metal plating layer becomes thicker, but the measurement of the peel strength in the present invention was carried out based on the measurement value at a thickness of 15 ⁇ m of the metal plating layer.
- Table 1 shows the compositions of the polyphenylene sulfide resin compositions constituting the supports used in Examples 1 to 6 and Comparative Examples 1 and 2, the peel strength measurement results before and after heating, and the heat resistance evaluation results.
- the laminates (1) to (6) obtained in Examples 1 to 6, which are laminates of the present invention have high peel strength and a slight decrease in peel strength after heating. Further, the retention of the peel strength after heating was high, and it was confirmed that it had excellent heat resistance.
- the laminate (R1) obtained in Comparative Example 1 is an example in which the polyphenylene sulfide resin composition constituting the support does not contain the elastomer that is an essential component of the present invention. It was confirmed that it was very low.
- (R2) obtained in Comparative Example 2 is an example in which the polyphenylene sulfide resin composition constituting the support exceeded the upper limit of the content of the elastomer of the present invention, but the peel strength before heating was compared. It was confirmed that the peel strength after heating was remarkably lowered.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Laminated Bodies (AREA)
- Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
- Non-Insulated Conductors (AREA)
Abstract
Description
(1)N-メチルピロリドン、ジメチルアセトアミド等のアミド系溶剤やスルホラン等のスルホン系溶媒中で硫化ナトリウムとp-ジクロロベンゼンとを反応させる方法。
(2)p-ジクロロベンゼンを硫黄と炭酸ソーダの存在下で重合させる方法。
(3)極性溶媒とp-ジクロロベンゼンとの混合溶媒に、硫化ナトリウムを滴下するか、水硫化ナトリウムと水酸化ナトリウムとの混合物を滴下するか、又は、硫化水素と水酸化ナトリウムとの混合物を滴下して重合させる方法。
(4)p-クロロチオフェノールの自己縮合による方法。
温度計、窒素ガス導入管、攪拌器を備えた窒素置換された容器中で、ポリエステルポリオール(1,4-シクロヘキサンジメタノールとネオペンチルグリコールとアジピン酸とを反応させて得られたポリエステルポリオール)100質量部、2,2―ジメチロールプロピオン酸17.6質量部、1,4-シクロヘキサンジメタノール21.7質量部及びジシクロヘキシルメタン-4,4’-ジイソシアネート106.2質量部を、メチルエチルケトン178質量部の混合溶剤中で反応させることによって、末端にイソシアネート基を有するウレタンプレポリマー溶液を得た。
還流冷却器、温度計、撹拌機を備えた反応フラスコに、37質量%ホルムアルデヒドと7質量%メタノールを含むホルマリン600質量部に、水200質量部及びメタノール350質量部を加えた。次いで、この水溶液に25質量%水酸化ナトリウム水溶液を加え、pH10に調整した後、メラミン310質量部を加え、液温を85℃まで上げ、メチロール化反応を1時間行った。
温度計、窒素ガス導入管、攪拌器を備え、窒素置換された反応容器に、2,2-ジメチロールプロピオン酸9.2質量部、ポリメチレンポリフェニルポリイソシアネート(東ソー株式会社製「ミリオネートMR-200」)57.4質量部及びメチルエチルケトン233質量部を仕込み、70℃で6時間反応させ、イソシアネート化合物を得た。次いで、反応容器内にブロック化剤としてフェノール26.4質量部を供給し、70℃で6時間反応させた。その後、40℃まで冷却し、ブロックイソシアネートの溶液を得た。
エチレングリコール45質量部及びイオン交換水55質量部の混合溶媒に、分散剤としてポリエチレンイミンにポリオキシエチレンが付加した化合物を用いて平均粒径30nmの銀粒子を分散させることによって、ナノサイズの金属粉及び分散剤を含有する流動体を調製した。次いで、得られた流動体に、イオン交換水及び界面活性剤を加えて粘度を10mPa・sに調整することによって、インクジェット印刷用導電性インクである流動体(1)を調製した。
リニア型ポリフェニレンスルフィド(ASTM D1238-86によるMFR:600g/10分)100質量部、チョップドガラス繊維(旭ファイバーグラス株式会社製「FT562」、繊維状無機充填剤)54.5質量部、グリシジルメタクリレート変性エチレン-アクリル酸メチル共重合エラストマー(住友化学株式会社製「ボンドファースト7L」)0.5質量部及びモンタン酸複合エステルワックス(クラリアントジャパン株式会社製「リコルブWE40」)0.8質量部を均一に混合した後、35mmφの2軸押出機を用いて290~330℃で溶融混錬し、ポリフェニレンスルフィド樹脂組成物を得た。得られたポリフェニレンスルフィド樹脂組成物を射出成形機で成形することにより、50mm×105mm×2mmのサイズの支持体(A-1)を得た。
支持体に用いるポリフェニレンスルフィド樹脂組成物を表1に示した組成にして、支持体(A-2)~(A-5)を得て、プライマー樹脂層用樹脂組成物(X-1)をプライマー樹脂層用樹脂組成物(X-2)に変更した以外は、実施例1と同様の方法によって、支持体(A)、プライマー樹脂層(X)、金属層(B)及び金属めっき層(C)を順次積層した積層体(2)~(5)を得た。
支持体に用いるポリフェニレンスルフィド樹脂組成物を表1に示した組成にして、支持体(A-5)を得て、プライマー樹脂層用樹脂組成物(X-1)をプライマー樹脂層用樹脂組成物(X-3)に変更した以外は、実施例1と同様の方法によって、支持体(A)、プライマー樹脂層(X)、金属層(B)及び金属めっき層(C)を順次積層した積層体(5)を得た。
実施例3で得られた支持体(A-3)を用いて、プライマー樹脂層用樹脂組成物(X-1)を用いずに、支持体(A-3)上に直接銀層を形成した以外は、実施例1と同様の方法によって、支持体(A)、前記金属層(B)及び金属めっき層(C)を順次積層した積層体(6)を得た。
支持体に用いるポリフェニレンスルフィド樹脂組成物を表1に示した組成にして、支持体(A-6)を得て、プライマー樹脂層用樹脂組成物(X-1)をプライマー樹脂層用樹脂組成物(X-2)に変更した以外は、実施例1と同様の方法によって、支持体(A)、プライマー樹脂層(X)、金属層(B)、金属めっき層(C)を順次積層した積層体(R1)を得た。
支持体に用いるポリフェニレンスルフィド樹脂組成物を表1に示した組成にして、支持体(A-7)を得て、プライマー樹脂層用樹脂組成物(X-1)を用いずに、支持体(A-3)上に直接銀層を形成した以外は、実施例1と同様の方法によって、支持体(A)、前記金属層(B)及び金属めっき層(C)を順次積層した積層体(R2)を得た。
上記で得られた各積層体について、株式会社島津製作所製「オートグラフAGS-X 500N」を用いてピール強度を測定した。なお、測定に用いるリード幅は5mm、そのピールの角度は90°とした。また、ピール強度は、金属めっき層の厚さが厚くなるほど高い値を示す傾向にあるが、本発明でのピール強度の測定は、金属めっき層の厚さ15μmにおける測定値を基準として実施した。
上記で得られた各積層体について、それぞれ150℃に設定した乾燥機内に168時間保管して加熱した。加熱後、上記と同様の方法でピール強度を測定した。
上記で測定した加熱前後のピール強度値を用いて、加熱前後での保持率を算出し、下記の基準にしたがって耐熱性を評価した。
A:保持率が80%以上である。
B:保持率が70%以上80%未満である。
C:保持率が50%以上70%未満である。
D:保持率が50%未満である。
Claims (11)
- ポリフェニレンスルフィド(a1)及びエラストマー(a2)を含有するポリフェニレンスルフィド樹脂組成物からなる支持体(A)の上に、金属層(B)及び金属めっき層(C)が順次積層された積層体であって、前記ポリフェニレンスルフィド樹脂組成物中のエラストマー(a2)の含有量が、前記ポリフェニレンスルフィド(a1)100質量部に対して、0.3~90質量部の範囲であることを特徴とする積層体。
- 前記エラストマーが、オレフィン共重合体系エラストマーである請求項1記載の積層体。
- 前記支持体(A)と前記金属層(B)とが、プライマー樹脂層(X)を介して積層されたものである請求項1記載の積層体。
- 前記プライマー樹脂層(X)を構成する樹脂が、加熱により還元性化合物を生成するものである請求項3記載の積層体。
- 前記金属層(B)を構成する金属が、パラジウム、ニッケル、クロム及び銀からなる群から選ばれる少なくとも1種である請求項1記載の積層体。
- 前記金属層(B)の付着量が、1~30,000mg/m2の範囲である請求項1記載の積層体。
- 前記金属めっき層(C)が、電解めっき法、無電解めっき法又はこれらの組み合わせにより形成されたものである請求項1記載の積層体。
- 請求項1~7のいずれか1項記載の積層体からなることを特徴とする成形品。
- 請求項1~7のいずれか1項記載の積層体からなることを特徴とする導電性パターン。
- 請求項9記載の導電性パターンを有することを特徴とする電子回路。
- 請求項1~7のいずれか1項記載の積層体からなることを特徴とする電磁波シールド。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2017524968A JP6213801B2 (ja) | 2015-06-26 | 2016-06-23 | 積層体、成形品、導電性パターン、電子回路及び電磁波シールド |
KR1020187001692A KR20180022813A (ko) | 2015-06-26 | 2016-06-23 | 적층체, 성형품, 도전성 패턴, 전자 회로 및 전자파 실드 |
EP16814441.8A EP3315302B1 (en) | 2015-06-26 | 2016-06-23 | Laminated body, molded article, electroconductive pattern, electronic circuit, and electromagnetic shield |
US15/739,599 US20180162106A1 (en) | 2015-06-26 | 2016-06-23 | Laminated body, molded article, electroconductive pattern, electronic circuit, and electromagnetic shield |
CN201680037194.XA CN107708997A (zh) | 2015-06-26 | 2016-06-23 | 层叠体、成型品、导电性图案、电子电路和电磁波屏蔽体 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2015128836 | 2015-06-26 | ||
JP2015-128836 | 2015-06-26 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2016208672A1 true WO2016208672A1 (ja) | 2016-12-29 |
Family
ID=57585075
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2016/068661 WO2016208672A1 (ja) | 2015-06-26 | 2016-06-23 | 積層体、成形品、導電性パターン、電子回路及び電磁波シールド |
Country Status (7)
Country | Link |
---|---|
US (1) | US20180162106A1 (ja) |
EP (1) | EP3315302B1 (ja) |
JP (1) | JP6213801B2 (ja) |
KR (1) | KR20180022813A (ja) |
CN (1) | CN107708997A (ja) |
TW (1) | TW201707973A (ja) |
WO (1) | WO2016208672A1 (ja) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2017154879A1 (ja) * | 2016-03-11 | 2017-09-14 | Dic株式会社 | 積層体の製造方法 |
JP2018168226A (ja) * | 2017-03-29 | 2018-11-01 | 三菱マテリアル株式会社 | ペースト状銀粉組成物、接合体の製造方法および銀膜の製造方法 |
WO2019013038A1 (ja) * | 2017-07-10 | 2019-01-17 | Dic株式会社 | 積層体、それを用いたプリント配線板、フレキシブルプリント配線板及び成形品 |
WO2019013039A1 (ja) * | 2017-07-10 | 2019-01-17 | Dic株式会社 | 積層体、それを用いたプリント配線板、フレキシブルプリント配線板及び成形品 |
WO2020003879A1 (ja) * | 2018-06-26 | 2020-01-02 | Dic株式会社 | 金属パターンを有する成形体の製造方法 |
WO2020040120A1 (ja) * | 2018-08-23 | 2020-02-27 | Dic株式会社 | 積層体、成形品、導電性パターン及び電子回路 |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2021070591A1 (ja) * | 2019-10-10 | 2021-04-15 | Dic株式会社 | 積層体、成形品、プリント配線板及び電磁波シールド |
KR20220101661A (ko) * | 2019-11-26 | 2022-07-19 | 디아이씨 가부시끼가이샤 | 폴리아릴렌설파이드 수지 조성물, 성형품, 적층체 및 그들의 제조 방법 |
CN113301714A (zh) * | 2021-05-25 | 2021-08-24 | 安徽鑫泰电子科技有限公司 | 一种适用于铜浆印制的电路板基板及其制作方法 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH05320506A (ja) * | 1992-05-26 | 1993-12-03 | Dainippon Ink & Chem Inc | ランプリフレクタ |
WO2007001036A1 (ja) * | 2005-06-28 | 2007-01-04 | Dainippon Ink And Chemicals, Inc. | ポリフェニレンスルフィド樹脂構造体 |
JP2011178031A (ja) * | 2010-03-01 | 2011-09-15 | Furukawa Electric Co Ltd:The | フィルム状成形体及び積層体 |
WO2011132542A1 (ja) * | 2010-04-22 | 2011-10-27 | 三菱樹脂株式会社 | 積層ポリエステルフィルム |
JP2012224754A (ja) * | 2011-04-20 | 2012-11-15 | Rikkyo Gakuin | ポリフェニレンエーテルを含む樹脂組成物およびその製造方法 |
WO2013147050A1 (ja) * | 2012-03-30 | 2013-10-03 | Dic株式会社 | 積層体、導電性パターン、電気回路及び積層体の製造方法 |
JP2015066735A (ja) * | 2013-09-27 | 2015-04-13 | 東レ株式会社 | ポリフェニレンスルフィド樹脂組成物からなる成形品と金属箔を接合した複合成形品および複合成形品の製造方法 |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5484648A (en) * | 1993-08-11 | 1996-01-16 | Shin-Etsu Polymer Co., Ltd. | Heat-sealable connector and method for the preparation thereof |
US11274223B2 (en) * | 2013-11-22 | 2022-03-15 | C3 Nano, Inc. | Transparent conductive coatings based on metal nanowires and polymer binders, solution processing thereof, and patterning approaches |
-
2016
- 2016-06-23 CN CN201680037194.XA patent/CN107708997A/zh active Pending
- 2016-06-23 KR KR1020187001692A patent/KR20180022813A/ko not_active Application Discontinuation
- 2016-06-23 US US15/739,599 patent/US20180162106A1/en not_active Abandoned
- 2016-06-23 EP EP16814441.8A patent/EP3315302B1/en active Active
- 2016-06-23 WO PCT/JP2016/068661 patent/WO2016208672A1/ja active Application Filing
- 2016-06-23 JP JP2017524968A patent/JP6213801B2/ja active Active
- 2016-06-24 TW TW105119846A patent/TW201707973A/zh unknown
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH05320506A (ja) * | 1992-05-26 | 1993-12-03 | Dainippon Ink & Chem Inc | ランプリフレクタ |
WO2007001036A1 (ja) * | 2005-06-28 | 2007-01-04 | Dainippon Ink And Chemicals, Inc. | ポリフェニレンスルフィド樹脂構造体 |
JP2011178031A (ja) * | 2010-03-01 | 2011-09-15 | Furukawa Electric Co Ltd:The | フィルム状成形体及び積層体 |
WO2011132542A1 (ja) * | 2010-04-22 | 2011-10-27 | 三菱樹脂株式会社 | 積層ポリエステルフィルム |
JP2012224754A (ja) * | 2011-04-20 | 2012-11-15 | Rikkyo Gakuin | ポリフェニレンエーテルを含む樹脂組成物およびその製造方法 |
WO2013147050A1 (ja) * | 2012-03-30 | 2013-10-03 | Dic株式会社 | 積層体、導電性パターン、電気回路及び積層体の製造方法 |
JP2015066735A (ja) * | 2013-09-27 | 2015-04-13 | 東レ株式会社 | ポリフェニレンスルフィド樹脂組成物からなる成形品と金属箔を接合した複合成形品および複合成形品の製造方法 |
Non-Patent Citations (1)
Title |
---|
See also references of EP3315302A4 * |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2017154879A1 (ja) * | 2016-03-11 | 2017-09-14 | Dic株式会社 | 積層体の製造方法 |
EP3427943A4 (en) * | 2016-03-11 | 2019-10-16 | DIC Corporation | METHOD FOR PRODUCING A LAMINATE |
JP2018168226A (ja) * | 2017-03-29 | 2018-11-01 | 三菱マテリアル株式会社 | ペースト状銀粉組成物、接合体の製造方法および銀膜の製造方法 |
WO2019013038A1 (ja) * | 2017-07-10 | 2019-01-17 | Dic株式会社 | 積層体、それを用いたプリント配線板、フレキシブルプリント配線板及び成形品 |
WO2019013039A1 (ja) * | 2017-07-10 | 2019-01-17 | Dic株式会社 | 積層体、それを用いたプリント配線板、フレキシブルプリント配線板及び成形品 |
JPWO2019013038A1 (ja) * | 2017-07-10 | 2019-11-07 | Dic株式会社 | 積層体、それを用いたプリント配線板、フレキシブルプリント配線板及び成形品 |
CN110753617A (zh) * | 2017-07-10 | 2020-02-04 | Dic株式会社 | 层叠体、使用其的印刷布线板、挠性印刷布线板及成形品 |
WO2020003879A1 (ja) * | 2018-06-26 | 2020-01-02 | Dic株式会社 | 金属パターンを有する成形体の製造方法 |
JPWO2020003879A1 (ja) * | 2018-06-26 | 2020-09-24 | Dic株式会社 | 金属パターンを有する成形体の製造方法 |
TWI820152B (zh) * | 2018-06-26 | 2023-11-01 | 日商Dic股份有限公司 | 具有金屬圖案的成形體之製造方法 |
WO2020040120A1 (ja) * | 2018-08-23 | 2020-02-27 | Dic株式会社 | 積層体、成形品、導電性パターン及び電子回路 |
JPWO2020040120A1 (ja) * | 2018-08-23 | 2021-03-11 | Dic株式会社 | 積層体、成形品、導電性パターン及び電子回路 |
Also Published As
Publication number | Publication date |
---|---|
US20180162106A1 (en) | 2018-06-14 |
EP3315302A4 (en) | 2018-06-20 |
KR20180022813A (ko) | 2018-03-06 |
JP6213801B2 (ja) | 2017-10-18 |
CN107708997A (zh) | 2018-02-16 |
EP3315302B1 (en) | 2022-02-23 |
EP3315302A1 (en) | 2018-05-02 |
JPWO2016208672A1 (ja) | 2017-10-05 |
TW201707973A (zh) | 2017-03-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6213801B2 (ja) | 積層体、成形品、導電性パターン、電子回路及び電磁波シールド | |
TWI671189B (zh) | 積層體之製造方法 | |
TWI820152B (zh) | 具有金屬圖案的成形體之製造方法 | |
JP7361699B2 (ja) | 積層体、成形品、導電性パターン及び電子回路 | |
JP6667119B1 (ja) | プリント配線板用積層体及びそれを用いたプリント配線板 | |
TW202007240A (zh) | 印刷配線板之製造方法 | |
TW202002738A (zh) | 印刷配線板之製造方法 | |
JP6432761B2 (ja) | 積層体、導電性パターン、電子回路及び積層体の製造方法 | |
WO2020130071A1 (ja) | プリント配線板の製造方法 | |
TW202020222A (zh) | 具有金屬圖案的成形體之製造方法 | |
JP7205672B2 (ja) | 金属皮膜形成方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 16814441 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2017524968 Country of ref document: JP Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 15739599 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20187001692 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2016814441 Country of ref document: EP |