WO2020004229A1 - 積層未硬化シート - Google Patents

積層未硬化シート Download PDF

Info

Publication number
WO2020004229A1
WO2020004229A1 PCT/JP2019/024552 JP2019024552W WO2020004229A1 WO 2020004229 A1 WO2020004229 A1 WO 2020004229A1 JP 2019024552 W JP2019024552 W JP 2019024552W WO 2020004229 A1 WO2020004229 A1 WO 2020004229A1
Authority
WO
WIPO (PCT)
Prior art keywords
resin
sheet
layer
laminated
cured
Prior art date
Application number
PCT/JP2019/024552
Other languages
English (en)
French (fr)
Inventor
長澤　忠
智士 芦浦
智恵 主税
梶田　智
民　保秀
Original Assignee
京セラ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 京セラ株式会社 filed Critical 京セラ株式会社
Priority to CN201980043027.XA priority Critical patent/CN112314063A/zh
Priority to US17/254,881 priority patent/US11426970B2/en
Priority to EP19826177.8A priority patent/EP3817527A4/en
Publication of WO2020004229A1 publication Critical patent/WO2020004229A1/ja

Links

Images

Classifications

    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • 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
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • B32B3/266—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by an apertured layer, the apertures going through the whole thickness of the layer, e.g. expanded metal, perforated layer, slit layer regular cells B32B3/12
    • 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
    • B32B15/085—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 polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/325—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polycycloolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/42—Layered products comprising a layer 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/022—Non-woven fabric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/024—Woven fabric
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/02—Halogenated hydrocarbons
    • C08K5/03—Halogenated hydrocarbons aromatic, e.g. C6H5-CH2-Cl
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/06—Organic materials
    • C09K21/08—Organic materials containing halogen
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/036—Multilayers with layers of different types
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
    • 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
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber 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
    • B32B2255/26—Polymeric 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0261—Polyamide fibres
    • B32B2262/0269—Aromatic polyamide fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/02—Synthetic macromolecular particles
    • B32B2264/0214—Particles made of materials belonging to B32B27/00
    • 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
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • 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
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/101—Glass
    • 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
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/102—Oxide or hydroxide
    • 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
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/104—Oxysalt, e.g. carbonate, sulfate, phosphate or nitrate particles
    • 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
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/107—Ceramic
    • B32B2264/108—Carbon, e.g. graphite particles
    • 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
    • B32B2307/204—Di-electric
    • 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
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/538—Roughness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional 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
    • 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
    • C08J2345/00—Characterised by the use of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Derivatives of such polymers
    • 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2425/02—Homopolymers or copolymers of hydrocarbons
    • C08J2425/04—Homopolymers or copolymers of styrene
    • C08J2425/06—Polystyrene
    • 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
    • H05K2201/012—Flame-retardant; Preventing of inflammation
    • 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
    • H05K2201/0129—Thermoplastic polymer, e.g. auto-adhesive layer; Shaping of thermoplastic 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
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0137—Materials
    • H05K2201/0158—Polyalkene or polyolefin, e.g. polyethylene [PE], polypropylene [PP]
    • 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
    • H05K2201/0183—Dielectric layers
    • H05K2201/0195—Dielectric or adhesive layers comprising a plurality of layers, e.g. in a multilayer structure
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0206—Materials
    • H05K2201/0209—Inorganic, non-metallic particles
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0206—Materials
    • H05K2201/0212—Resin particles
    • 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
    • H05K2201/09—Shape and layout
    • H05K2201/09209—Shape and layout details of conductors
    • H05K2201/095—Conductive through-holes or vias
    • H05K2201/0959—Plated through-holes or plated blind vias filled with insulating material
    • 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
    • H05K3/40—Forming printed elements for providing electric connections to or between printed circuits
    • H05K3/42—Plated through-holes or plated via connections
    • H05K3/425—Plated through-holes or plated via connections characterised by the sequence of steps for plating the through-holes or via connections in relation to the conductive pattern
    • H05K3/427—Plated through-holes or plated via connections characterised by the sequence of steps for plating the through-holes or via connections in relation to the conductive pattern initial plating of through-holes in metal-clad substrates

Definitions

  • the present disclosure relates to a laminated uncured sheet, a laminated cured sheet, a metal-clad laminate, and a wiring board.
  • the laminated uncured sheet of the present disclosure has a structure in which resin sheet layers and resin layers are alternately laminated, and has a structure in which a through hole penetrating in the laminating direction is formed, and the resin sheet layer is mainly composed of a thermosetting resin.
  • the resin layer is formed of a thermoplastic resin composition containing a thermoplastic resin, and the thermoplastic resin composition adheres to the inner wall surface of the resin sheet layer portion in the through hole.
  • the laminated cured sheet of the present disclosure has a structure in which a cured resin sheet layer and a resin layer are alternately laminated, and a through-hole penetrating in the laminating direction is formed, and the cured resin sheet layer is mainly composed of a thermosetting resin.
  • the resin layer is formed of a thermoplastic resin composition containing a thermoplastic resin, and the thermoplastic resin composition adheres to the inner wall surface of the cured resin sheet layer portion in the through hole.
  • a metal-clad laminate of the present disclosure includes the above-described laminated cured sheet and a metal foil laminated on at least one surface of the laminated cured sheet.
  • a wiring board according to an embodiment of the present disclosure includes a plurality of insulating layers and a conductor layer disposed between the insulating layers, and the insulating layers are configured by the above-described laminated cured sheet.
  • FIG. 1 is a cross-sectional view illustrating a structure of a laminated uncured sheet according to an embodiment of the present disclosure.
  • FIG. 2 is a top view illustrating an embodiment of a layer L portion of the laminated uncured sheet illustrated in FIG. 1.
  • the inner wall surface of the through hole may be roughened with an uneven state.
  • the plating treatment is performed in a state where the inner wall surface of the through hole is roughened, the plating solution easily penetrates into the layer forming the substrate from the inner wall surface of the through hole. Therefore, the plating metal exists in the layer, and the electrical reliability is poor.
  • the laminated uncured sheet of the present disclosure has a structure in which resin sheet layers and resin layers are alternately laminated, and has a structure in which a through hole penetrating in the laminating direction is formed.
  • the thermoplastic resin composition is attached.
  • the unevenness of the inner wall surface of the resin sheet layer portion in the through hole is filled with the thermoplastic resin and becomes relatively smooth, and it is possible to suppress the plating solution from entering the resin sheet layer from the inner wall surface of the through hole. it can. Therefore, when the laminated uncured sheet of the present disclosure is used as a material for a substrate, a wiring substrate having excellent electrical reliability can be obtained.
  • the inner wall surfaces of the through holes of the resin sheet layer 2 may be covered with a thermoplastic resin composition.
  • the laminated uncured sheet of the present disclosure has a structure in which resin sheet layers and resin layers are alternately laminated, and a through-hole penetrating in the laminating direction is formed.
  • the resin sheet layer is formed of a thermosetting resin composition containing a thermosetting resin as a main component, and is in an uncured state or a semi-cured state.
  • thermosetting resin composition is not limited as long as it is a composition containing a thermosetting resin as a main component.
  • thermosetting resin include a thermosetting cyclic olefin resin, an epoxy resin, a phenol resin, an amino resin, and a thermosetting polyimide resin.
  • the cyclic olefin resin is a polyolefin polymer having a cyclic structure, and examples thereof include a copolymer of a cyclic olefin and another monomer copolymerizable with the cyclic olefin.
  • the ratio between the cyclic olefin and the other monomer is not particularly limited.
  • the cyclic olefin may contain 10 to 80% by mass and the other monomer may contain 20 to 90% by mass.
  • Examples of the cyclic olefin include a norbornene-based monomer, a cyclic diene-based monomer, and a vinyl alicyclic hydrocarbon-based monomer.
  • examples of the cyclic olefin include norbornene, vinyl norbornene, phenylnorbornene, dicyclopentadiene, tetracyclododecene, cyclopropene, cyclobutene, cyclopentene, cyclohexene, cyclohexadiene, and cyclooctadiene. These cyclic olefins may be used alone or in combination of two or more.
  • Examples of other monomers copolymerizable with the cyclic olefin include chain olefins, methacrylic acid acrylate, acrylic acid esters, methacrylic acid esters, aromatic vinyl compounds, unsaturated nitriles, and aliphatic conjugated dienes.
  • such monomers include ethylene, propylene, butene, acrylic acid, methacrylic acid, fumaric acid, fumaric anhydride, maleic acid, maleic anhydride, methyl acrylate, ethyl acrylate, propyl acrylate, Isopropyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, styrene, vinyl toluene, acrylonitrile, methacrylonitrile, 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3 -Dimethyl-1,3-butadiene and the like. These other monomers may be used alone or in combination of two or more.
  • Amino resin is obtained by polycondensation of a compound having an amino group with an aldehyde.
  • the compound having an amino group include urea and melamine
  • examples of the aldehyde include formaldehyde.
  • Specific examples of the amino resin include a urea resin and a melamine resin.
  • thermosetting resin may be appropriately used depending on the use of the laminated uncured sheet of the present disclosure. For example, if more excellent electrical properties are required for the laminated uncured sheet of the present disclosure, at least one resin selected from the group consisting of a thermosetting cyclic olefin resin and an epoxy resin may be used.
  • thermosetting cyclic olefin resin epoxy resin, polyimide resin, phenol resin and amino resin (urea resin, melamine resin, etc.) ) May be used at least one resin selected from the group consisting of: Further, in consideration of low hygroscopicity in addition to the above characteristics, it is preferable to use a thermosetting cyclic olefin resin.
  • thermosetting resin composition containing a thermosetting resin as a main component is a resin composition in which the resin component most contained in the thermosetting resin composition is a thermosetting resin.
  • a thermosetting resin composition for example, addition of an antioxidant, an ultraviolet absorber, a coloring agent, a base material (eg, an inorganic filler, glass cloth, aramid nonwoven cloth, glass nonwoven cloth, etc.), a flame retardant, and the like An agent may be included.
  • the content ratio of the base material and the flame retardant may be 0% or more and 40% or less of the area of the cross section of the laminated uncured sheet.
  • the identification of the base material and the flame retardant is performed, for example, in the following procedure.
  • the identification of the base material and the flame retardant is the same as in the case of a laminated cured sheet obtained by curing a laminated uncured sheet, or a metal-clad laminate or a wiring board using this laminated cured sheet, instead of the laminated uncured sheet. Can be done by any method.
  • the cross section of the cut laminated uncured sheet is observed with a scanning electron microscope and photographed. A digital microscope may be used instead of the scanning electron microscope.
  • As a range for photographing for example, about 100 to 150 ⁇ m in length and about 100 to 150 ⁇ m in width are guidelines.
  • the place where the photograph is taken may be an arbitrary part at only one place.
  • the base material and the flame retardant are identified based on the photograph taken.
  • a resin component, a substrate, and a flame retardant are identified by an analyzer (electron beam microanalyzer (EPMA)) attached to the scanning electron microscope.
  • the base material and the flame retardant are identified from the contained inorganic elements (for example, Si, Br, etc.).
  • the resin component is a portion not containing the above elements contained in the base material and the flame retardant.
  • the identification of the resin component, the base material, and the flame retardant can be distinguished from the difference in the color tone that appears in the photograph after specifying the element.
  • portions having the same color tone as the identified resin component, base material and flame retardant are specified as the resin component, base material and flame retardant, respectively.
  • the respective areas can be determined from the specified base material and flame retardant region.
  • the thermosetting resin composition may include at least one of an inorganic filler and a flame retardant in order to improve the flame retardancy of the laminated uncured sheet.
  • the inorganic filler is not particularly limited, and examples thereof include silica, talc, mica, clay, calcium carbonate, titanium oxide, barium titanate, carbon black, glass beads, and glass hollow spheres.
  • the silica includes pulverized silica, fused silica, and the like, and may be used alone or as a mixture of two or more.
  • the average particle size of the inorganic filler is not particularly limited, and may be, for example, 0.01 ⁇ m or more and 10 ⁇ m or less, and may be 0.5 ⁇ m or more and 3 ⁇ m or less.
  • Flame retardants are not particularly limited, for example, melamine phosphate, melam polyphosphate, melem polyphosphate, melamine pyrophosphate, ammonium polyphosphate, red phosphorus, aromatic phosphate, phosphonate, phosphinate, phosphine oxide, Examples include phosphazene, melamine cyanolate, ethylenebispentabromobenzene, and ethylenebistetrabromophthalimide. These flame retardants may be used alone or in combination of two or more.
  • a brominated flame retardant such as ethylenebispentabromobenzene or ethylenebistetrabromophthalimide
  • the average particle size of the flame retardant is not particularly limited, and may be, for example, 0.01 ⁇ m or more and 10 ⁇ m or less, and may be 0.5 ⁇ m or more and 3 ⁇ m or less.
  • the resin layer is formed of a thermoplastic resin composition containing a thermoplastic resin, and is in an uncured state or a semi-cured state.
  • the thermoplastic resin composition is not limited as long as it is a composition containing a thermoplastic resin.
  • the thermoplastic resin for example, a polystyrene resin, a phenylene resin, a Teflon (registered trademark) resin, a liquid crystal polymer, or the like may be used because it is excellent in adhesiveness to the resin sheet layer and hardly forms a solid solution.
  • thermoplastic resin composition containing a thermoplastic resin specifically means a composition containing 5% by mass or more of the thermoplastic resin, and may contain 10% by mass or more of the thermoplastic resin.
  • the thermoplastic resin composition is selected from the group of, for example, the above-mentioned thermosetting resin, the above-mentioned antioxidant and the above-mentioned base material (for example, inorganic filler, glass cloth, aramid nonwoven cloth, glass nonwoven cloth, etc.). At least one additive may be included.
  • the adhesiveness between the resin sheet layer and the resin layer can be enhanced.
  • the laminated uncured sheet 1 shown in FIG. 1 has a five-layer structure in which three resin sheet layers 2 and two resin layers 3 are alternately laminated. Although the laminated uncured sheet 1 shown in FIG. 1 has a five-layer structure, the laminated uncured sheet of the present disclosure is not limited to the five-layer structure.
  • the laminated uncured sheet 1 has a through hole (through hole) 4 penetrating from the upper surface to the lower surface.
  • the thermoplastic resin composition 31 only needs to cover at least the inner wall surface 5 of the resin sheet layer 2 in the through hole 4.
  • thermosetting resin composition When the through-holes 4 are formed in the resin sheet layer 2 containing the above-described thermosetting resin composition, the formed inner wall surface of the through-holes 4 tends to be rough. In this case, a plurality of recesses are formed on the inner wall surface 5 of the through hole 4.
  • the thermoplastic resin composition 31 is attached so as to fill the recess. A plurality of stripes are formed in the thermoplastic resin composition 31 attached to the inner wall surface 5 of the through hole 4 in a direction penetrating the through hole 4. The streaks exert an anchor effect on the plated metal formed in the through-hole 4. As a result, the adhesive strength between the thermoplastic resin composition 31 and the plated metal formed in the through hole 4 can be increased.
  • the thicknesses of the resin sheet layer 2 and the resin layer 3 are not particularly limited.
  • the thickness of the resin layer 3 may be smaller than the thickness of the resin sheet layer 2.
  • the thickness of the resin layer 3 is Is preferably 4 to 14 as a relative value when the thickness is 100. In this case, it is needless to say that the present invention can be applied to a laminated uncured sheet formed of a resin sheet layer 2 and a resin layer 3 having different thicknesses.
  • the thickness of the resin layer 3 is not particularly limited, and is preferably, for example, about 0.5 ⁇ m or more and 3 ⁇ m or less.
  • the thickness of the resin layer 3 is 0.5 ⁇ m or more, the adhesiveness between the resin sheet layer 2 and the resin layer 3 can be further improved.
  • the thickness of the resin layer 3 is 3 ⁇ m or less, the rigidity of the laminated cured sheet obtained by curing the laminated uncured sheet 1 is further increased, so that it is difficult to bend, and the heat resistance can be further improved.
  • the thickness of the resin layer of the laminated cured sheet obtained by curing the laminated uncured sheet 1 may be 4 to 14 as a relative value when the thickness of the cured resin sheet layer is 100.
  • the resin layer 3 does not need to cover the entire main surface of the resin sheet layer 2.
  • the coverage of the resin layer 3 with respect to the main surface of the resin sheet layer 2 may be 60% or more, and may be 90% or more. It may be 100%.
  • the coverage is 60% or more, even if the through hole 4 is formed at an arbitrary position, the probability that the inner wall surface 5 of the through hole 4 comes into contact with the resin layer 3 increases, and the thermoplastic resin composition 31 Also has no particular problem in that it covers the inner wall surface 5 of the through hole 4.
  • At least one of the resin sheet layer 2 and the resin layer 3 may contain at least one of an inorganic filler and a flame retardant. That is, at least one of the thermosetting resin composition and the thermoplastic resin composition may include at least one of an inorganic filler and a flame retardant.
  • At least one of the resin sheet layer 2 and the resin layer 3 may further include a stress relaxation agent.
  • the stress relaxing agent is not particularly limited, and examples thereof include silicone resin particles.
  • the silicone resin particles include KMP-597 (manufactured by Shin-Etsu Chemical Co., Ltd.) and X-52-875 (manufactured by Shin-Etsu Chemical Co., Ltd.) as silicone rubber powder, and KMP-590 (manufactured by Shin-Etsu Chemical Co., Ltd.). Shin-Etsu Chemical Co., Ltd.) and X-52-1621 (Shin-Etsu Chemical Co., Ltd.). These stress relaxation agents may be used alone or in combination of two or more.
  • the stress relaxing agent one having an average particle size of 10 ⁇ m or less may be used.
  • the stress relaxing agent having such an average particle size when the laminated uncured sheet 1 is used for, for example, a metal-clad laminate or the like, the adhesion to the metal foil can be further improved.
  • the content ratio of the inorganic filler and the flame retardant contained in the resin layer 3 is included in the resin sheet layer 2. May be lower than the content ratio of the inorganic filler and the flame retardant. Specifically, when the content ratio of the inorganic filler and the flame retardant contained in the resin sheet layer 2 is 1, the content ratio of the inorganic filler and the flame retardant contained in the resin layer 3 is 0.1 to 0.9. And may be 0.2 or more and 0.8 or less.
  • the present invention can be applied to a laminated uncured sheet formed of a resin sheet layer 2 and a resin layer 3 having different thicknesses.
  • the laminated cured sheet of the present disclosure is obtained by subjecting the above-described laminated uncured sheet to a pressure and heat treatment.
  • the resin sheet layer 2, the resin layer 3, the through hole 4, the inner wall surface 5, and the thermoplastic resin composition 31 in the uncured resin sheet 1 are formed of the cured resin sheet layer, the resin layer, and the through hole in the laminated cured sheet.
  • the cured resin sheet layer is formed of a thermosetting resin composition containing a thermosetting resin as a main component.
  • the resin layer is formed of a thermoplastic resin composition containing a thermoplastic resin. Further, a thermoplastic resin composition is adhered to the inner wall surface of the cured resin sheet layer portion in the through hole.
  • thermoplastic resin composition is attached to the inner wall surface of the through-hole, the thermoplastic resin composition is dissolved by a slight temperature rise when performing plating or the like on the through-hole, The dissolved thermoplastic resin composition spreads on the inner wall surface of the through hole. Thereby, the inner wall surface of the through hole is covered with the thermoplastic resin composition. Thus, it is possible to make it difficult for the plating solution to enter the cured resin sheet layer through the through holes.
  • the thickness of the resin layer may be smaller than the thickness of the cured resin sheet layer.
  • the thickness of the resin layer is determined by the thickness of the cured resin sheet layer. It is preferable to set the relative value to 4 to 14 when 100 is set. Also in this case, it is needless to say that the present invention can be applied to a laminated cured sheet formed of a cured resin sheet layer and a resin layer having different thicknesses.
  • the thickness of the resin layer is not particularly limited, and is preferably, for example, about 0.5 ⁇ m or more and 3 ⁇ m or less.
  • the thickness of the resin layer is 0.5 ⁇ m or more, the adhesiveness between the cured resin sheet layer and the resin layer can be further improved.
  • the thickness of the resin layer is 3 ⁇ m or less, the rigidity of the laminated cured sheet obtained by curing the laminated cured sheet is further increased, so that it is difficult to bend, and the heat resistance can be further improved.
  • the resin layer does not need to cover the entire main surface of the cured resin sheet layer.
  • the coverage of the resin layer on the main surface of the cured resin sheet layer may be 60% or more, may be 90% or more, and may be 100%. It may be.
  • the coverage is 60% or more, even if a through hole is formed at an arbitrary position, the probability that the inner wall surface of the through hole comes into contact with the resin layer is increased, and the thermoplastic resin composition is formed in the through hole. There is no particular problem in covering the wall.
  • At least one of the cured resin sheet layer and the resin layer may contain at least one of an inorganic filler and a flame retardant. That is, at least one of the thermosetting resin composition and the thermoplastic resin composition may include at least one of an inorganic filler and a flame retardant.
  • the content ratio of the inorganic filler and the flame retardant contained in the resin layer is changed to the inorganic content contained in the cured resin sheet layer. It is better to be less than the content ratio of the filler and the flame retardant.
  • the content ratio of the inorganic filler and the flame retardant contained in the cured resin sheet layer is set to 1, the content ratio of the inorganic filler and the flame retardant contained in the resin layer is 0.1 to 0.9 by mass ratio. Or less, and may be 0.2 or more and 0.8 or less.
  • the thermoplastic resin composition is formed from the resin layer on the inner wall surface of the through hole. It easily flows out and wettability is further improved. Also in this case, it is needless to say that the present invention can be applied to a laminated layered sheet formed of a cured resin sheet layer and a resin layer having different thicknesses.
  • the content of the inorganic filler contained in the resin layer may be smaller than the content of the inorganic filler contained in the cured resin sheet layer.
  • the thermoplastic resin contained in the resin layer is easily melted due to a partial temperature rise when forming the through-hole.
  • the cured resin sheet layer that is, the thermosetting resin composition
  • the cured resin sheet layer may contain more flame retardants. Good.
  • at least one of them may further contain the above-mentioned stress relaxation agent.
  • the method for producing the laminated uncured sheet of the present disclosure is not particularly limited. It is obtained by alternately laminating a resin sheet layer formed of the above-described thermosetting resin composition and a resin layer formed of the above-described thermoplastic resin composition.
  • the resin sheet layer is formed, for example, from a thermosetting resin composition containing a solvent (thermosetting resin varnish).
  • the solvent include xylene.
  • the mass ratio between the solid content (the resin component and the non-resin component) and the solvent is not particularly limited, and for example, they are mixed at a mass ratio of about 60:40 to 20:80.
  • other solvents such as aromatic solvents such as toluene, benzene, and ethylbenzene, hydrocarbon solvents such as normal hexane, cyclohexane, and methylcyclohexane, ketone solvents such as acetone, and tetrahydrofuran and chloroform may be used.
  • Xylene may be used in combination with the other solvents described above.
  • thermosetting resin varnish is formed into a sheet by a bar coater method, a doctor blade method, a die coater method, and the like, and then dried at about 120 to 150 ° C. for about 1 to 10 minutes to obtain an uncured state.
  • a sheet-shaped molded body is obtained.
  • the sheet-shaped molded body may be formed by, for example, an extrusion method or an injection molding method in which the thermosetting resin composition is heated by an extruder or the like.
  • the resin layer is formed, for example, from a thermoplastic resin composition (thermoplastic resin varnish) containing a solvent.
  • the solvent and the amount of the solvent used are as described above, and the detailed description is omitted.
  • the obtained thermoplastic resin varnish is applied to one main surface of a sheet-shaped molded body.
  • another sheet-like molded body to which the thermoplastic resin varnish is not applied is superimposed on the main surface to which the thermoplastic resin varnish is applied, and a three-layer structure of sheet-shaped molded article / thermoplastic resin varnish / sheet-shaped molded article is formed. Is obtained.
  • a thermoplastic resin varnish is applied to the main surface of another stacked sheet-like molded product, and the same operation is repeated until the desired number of layers is obtained.
  • thermoplastic resin varnish a desired number of sheet-like molded bodies coated with the thermoplastic resin varnish may be prepared and then stacked. Specifically, the sheet-shaped molded body is overlapped so that the main surface to which the thermoplastic resin varnish is applied and the main surface to which the thermoplastic resin varnish is not applied are in contact, and finally, the main surface to which the thermoplastic resin varnish is applied. Then, another sheet-like molded body which has not been treated with the thermoplastic resin varnish may be laminated to form a laminate.
  • the thus obtained laminate is subjected to pressure treatment at room temperature under a pressure of about 0.1 to 1 MPa, for example, to obtain a laminated uncured sheet.
  • the laminated uncured sheet of the present disclosure has a thickness of, for example, about 0.01 to 2 mm, depending on the number of layers to be laminated.
  • the laminated cured sheet of the present disclosure is obtained by subjecting the above-described laminated uncured sheet to a pressure and heat treatment.
  • the pressure and heat treatment conditions are, for example, a temperature of about 160 to 230 ° C. and a pressure of about 1 to 10 MPa.
  • the laminated cured sheet thus obtained has a thickness of, for example, about 0.01 to 2 mm.
  • the metal-clad laminate of the present disclosure has a metal foil on at least one surface of the laminated cured sheet of the present disclosure.
  • the metal-clad laminate of the present disclosure is obtained by, for example, laminating a laminated uncured sheet of the present disclosure and a metal foil and subjecting them to a pressure and heat treatment.
  • the conditions for the pressure and heat treatment may be the same as those performed when obtaining the above-mentioned laminated cured sheet.
  • the metal foil is not particularly limited, and examples thereof include a copper foil such as an electrolytic copper foil and a rolled copper foil, an aluminum foil, and a composite foil obtained by laminating these metal foils. Among these metal foils, for example, a copper foil is used.
  • the thickness of the metal foil is not particularly limited, and is, for example, about 5 ⁇ m or more and 105 ⁇ m or less.
  • the surface roughness of the metal foil is not particularly limited, and may be 0.5 ⁇ m or less, or 0.3 ⁇ m or less.
  • the metal-clad laminate of the present disclosure can also be obtained by laminating a desired number of the laminated uncured sheet and the metal foil of the present disclosure, respectively, and subjecting them to heat and pressure molding.
  • the metal-clad laminate of the present disclosure has, for example, a dielectric loss tangent of 0.0017 or less. When the dielectric loss tangent of the metal-clad laminate is 0.0017 or less, sufficient electrical characteristics such as an excellent dielectric constant are exhibited.
  • the metal-clad laminate of the present disclosure is used for, for example, a printed wiring board.
  • a wiring board according to the present disclosure has a basic structure including an insulating layer and a conductor layer disposed on a main surface of the insulating layer.
  • it includes a plurality of insulating layers and a conductor layer disposed between the insulating layers, and the insulating layers are formed of the laminated cured sheet of the present disclosure.
  • the main surface of the insulating layer means a surface having the largest area facing each other among the surfaces constituting the insulating layer, and corresponds to a surface facing the thickness direction of the insulating layer.
  • the wiring board according to the present disclosure is obtained, for example, by laminating a prepreg with an inner layer plate having circuits and through holes formed on the metal-clad laminate of the present disclosure, laminating a metal foil on the surface of the prepreg, and then heating (curing). It is obtained by pressure molding. Further, a circuit and a through hole may be formed in the metal foil on the surface to form a multilayer printed wiring board.
  • the resin sheet layer portion in the through hole Of the inner wall surface or the unevenness of the inner wall surface of the cured resin sheet layer portion are filled with a thermoplastic resin to make it relatively smooth. Therefore, it is possible to suppress the plating solution from entering the resin sheet layer or the cured resin sheet layer from the inner wall surface of the through hole. Thus, a metal-clad laminate and a wiring board with high electrical reliability can be obtained.
  • the inner wall surface of the resin sheet layer portion in the through hole is covered with the thermoplastic resin composition.
  • the inner wall surface of the cured resin sheet layer portion in the through hole is coated with the thermoplastic resin composition.
  • the metal-clad laminate and the wiring board of the present disclosure formed by either one of the laminated uncured sheet and the laminated cured sheet also have unevenness on the inner wall surface of the resin sheet layer portion in the through hole or the cured resin sheet. All the irregularities on the inner wall surface of the layer are in a state of being filled with the thermoplastic resin.
  • thermosetting cyclic olefin copolymer (COC, manufactured by Mitsui Chemicals, Inc.), 25% by mass of silica (average particle size: 1 ⁇ m) as an inorganic filler, and ethylene bispentabromobenzene (average particle size: 1 ⁇ m) as a flame retardant (Trade name: SAYTEX8010, manufactured by Albemarle Co., Ltd.) at a ratio of 25% by mass to obtain a thermosetting resin mixture.
  • SAYTEX8010 flame retardant
  • the obtained resin varnish was applied on a substrate (polyethylene terephthalate film) using a bar coater. After coating on the substrate, it was dried at 150 ° C. for 4 minutes, and peeled off from the substrate to obtain a sheet-like molded body (30 cm ⁇ 30 cm, average thickness: about 28 ⁇ m). A plurality of similar sheet-like molded bodies were produced. The obtained molded body was in an uncured state.
  • thermoplastic resin 10% by mass of polystyrene (PS, manufactured by Nippon Polystyrene Co., Ltd.), 40% by mass of the above COC, 25% by mass of the above silica, and 25% by mass of the above flame retardant were mixed.
  • a thermoplastic resin mixture was obtained.
  • Xylene as a solvent was mixed at a ratio of 80 parts by mass with respect to 100 parts by mass of the total amount of the used polystyrene (PS) and COC to prepare a thermoplastic resin varnish.
  • thermoplastic resin varnish was applied to one main surface of the obtained sheet-like molded body so as to have a thickness of 3 ⁇ m.
  • Three sheet-like molded articles each having a thermoplastic resin varnish applied to one main surface were produced.
  • the obtained three sheet-like molded bodies are overlapped so that the main surface to which the thermoplastic resin varnish is applied and the main surface to which the thermoplastic resin varnish is not applied are in contact, and finally, the thermoplastic resin varnish is not treated.
  • Another sheet-like molded body was overlaid to obtain a laminate.
  • the obtained laminate had a structure in which four layers of a sheet-shaped molded product (resin sheet layer) and three layers of a thermoplastic resin varnish (resin layer) were alternately laminated.
  • the obtained laminate was subjected to a pressure treatment at room temperature at a pressure of 1 MPa to obtain a laminated uncured sheet.
  • the obtained laminated uncured sheet was subjected to a pressure and heat treatment to obtain a laminated cured sheet.
  • the heat treatment under pressure was performed at 200 ° C. under a pressure and heat condition of 4 MPa for 120 minutes.
  • the cured resin sheet layer formed by curing the sheet-shaped molded article had a thickness of 23 ⁇ m, and the resin layer had a thickness of 2 ⁇ m.
  • a part of the resin layer of the obtained laminated cured sheet was taken out as a sample and heated with a sample hot plate. Since the sample was melted by heating, it was determined that the resin layer contained a thermoplastic resin.
  • a copper-clad laminate was obtained by the following method. First, a copper foil having a thickness of 18 ⁇ m was laminated on both surfaces of the laminated uncured sheet. The laminate on which the copper foil was laminated was subjected to a pressure heating treatment under a pressure heating condition of 200 ° C. and 4 MPa for 120 minutes to obtain a copper-clad laminate.
  • thermoplastic resin varnish was prepared in the same procedure as in Sample 1, except that the above PS was used at a ratio of 20% by mass and the above COC was used at a ratio of 30% by mass.
  • a laminated cured sheet, a copper-clad laminate, and a wiring board were obtained in the same procedure as in Sample 1, except that this thermoplastic resin varnish was used.
  • a part of the resin layer of the obtained laminated cured sheet was taken out as a sample, and heated with a sample hot plate. Since the sample was melted by heating, it was determined that the resin layer contained a thermoplastic resin.
  • thermoplastic resin varnish was prepared in the same procedure as in Sample 1, except that the above PS was used at a ratio of 30% by mass and the above COC was used at a ratio of 20% by mass.
  • a laminated cured sheet, a copper-clad laminate, and a wiring board were obtained in the same procedure as in Sample 1, except that this thermoplastic resin varnish was used.
  • a part of the resin layer of the obtained laminated cured sheet was taken out as a sample, and heated with a sample hot plate. Since the sample was melted by heating, it was determined that the resin layer contained a thermoplastic resin.
  • thermoplastic resin varnish was prepared in the same procedure as in Sample 1, except that the above PS was used at a ratio of 40% by mass and the above COC was used at a ratio of 10% by mass.
  • a laminated cured sheet, a copper-clad laminate, and a wiring board were obtained in the same procedure as in Sample 1, except that this thermoplastic resin varnish was used.
  • a part of the resin layer of the obtained laminated cured sheet was taken out as a sample, and heated with a sample hot plate. Since the sample was melted by heating, it was determined that the resin layer contained a thermoplastic resin.
  • thermoplastic resin varnish was prepared in the same procedure as in Sample 1, except that the above PS was used at a ratio of 40% by mass and the above COC was used at a ratio of 60% by mass, and silica and a flame retardant were not used.
  • a laminated cured sheet, a copper-clad laminate, and a wiring board were obtained in the same procedure as in Sample 1, except that this thermoplastic resin varnish was used.
  • a part of the resin layer of the obtained laminated cured sheet was taken out as a sample, and heated with a sample hot plate. Since the sample was melted by heating, it was determined that the resin layer contained a thermoplastic resin.
  • thermoplastic resin varnish was prepared in the same procedure as in Sample 1, except that the above PS was used in an amount of 30% by mass, the above COC was used in an amount of 45% by mass, and silica was used in an amount of 25% by mass, and no flame retardant was used. did.
  • a laminated cured sheet, a copper-clad laminate, and a wiring board were obtained in the same procedure as in Sample 1, except that this thermoplastic resin varnish was used.
  • a part of the resin layer of the obtained laminated cured sheet was taken out as a sample, and heated with a sample hot plate. Since the sample was melted by heating, it was determined that the resin layer contained a thermoplastic resin.
  • thermoplastic resin varnish was prepared in the same procedure as in Sample 1, except that the above PS was used in an amount of 30% by mass, the above COC was used in an amount of 45% by mass, and the flame retardant was used in an amount of 25% by mass, and no inorganic filler was used.
  • a laminated cured sheet, a copper-clad laminate, and a wiring board were obtained in the same procedure as in Sample 1, except that this thermoplastic resin varnish was used.
  • a part of the resin layer of the obtained laminated cured sheet was taken out as a sample, and heated with a sample hot plate. Since the sample was melted by heating, it was determined that the resin layer contained a thermoplastic resin.
  • thermoplastic resin varnish was prepared in the same procedure as in Sample 1, except that the above COC was used at a ratio of 50% by mass and no thermoplastic resin was used.
  • a laminated cured sheet, a copper-clad laminate, and a wiring board were obtained in the same procedure as in Sample 1, except that this thermoplastic resin varnish was used.
  • a part of the resin layer of the obtained laminated cured sheet was taken out as a sample, and heated with a sample hot plate. Since the sample was not melted by heating and was carbonized in a state where the shape was substantially maintained, it was determined that the thermoplastic resin was not contained in the resin layer.
  • each of the laminated cured sheets obtained in Samples 1 to 8 was evaluated for flammability according to the UL94V flammability test. Specifically, a test piece (12.5 mm ⁇ 125 mm) cut from the laminated cured sheet was vertically attached to a clamp. Next, flame contact with a 20 mm flame was performed from below the test piece, and the time when the flame disappeared from the test piece was measured. The test was conducted on five test pieces, and evaluated on three levels: V-not (flammable), V1 and V0 (flame retardant). Table 1 shows the results.
  • TH through holes
  • Table 1 shows the length of copper (the length from the inner wall surface of TH) that has penetrated the deepest into the layer. In Table 1, for example, “ ⁇ 20 ⁇ m” indicates that the length of copper that penetrated the deepest was 20 ⁇ m.
  • the insulation reliability between the TH wall surfaces was evaluated for each of the wiring boards obtained in Samples 1 to 8.
  • TH through holes
  • a reliability test was performed for 1000 hours under an environment of a temperature of 130 ° C. and a humidity of 85% RH while applying a voltage of 5.5 V.
  • the same test was performed on the wiring board on which the TH was formed by changing the distance between the TH wall surfaces to 125 ⁇ m, 150 ⁇ m, 175 ⁇ m, and 250 ⁇ m.
  • Table 1 shows the distance between the wall surfaces that can maintain the insulation reliability between the TH wall surfaces. In Table 1, for example, “ ⁇ 175 ⁇ m” indicates that insulation reliability can be maintained if at least a 175 ⁇ m wall-to-wall distance is provided.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Textile Engineering (AREA)
  • Laminated Bodies (AREA)
  • Production Of Multi-Layered Print Wiring Board (AREA)

Abstract

本開示の積層未硬化シートは、樹脂シート層と樹脂層とが交互に積層され、積層方向に貫通する貫通孔が形成された構造を有し、樹脂シート層が熱硬化性樹脂を主成分とする熱硬化性樹脂組成物で形成され、樹脂層が熱可塑性樹脂を含む熱可塑性樹脂組成物で形成され、貫通孔における前記樹脂シート層部分の内壁面に熱可塑性樹脂組成物が付着している。

Description

積層未硬化シート
　本開示は、積層未硬化シート、積層硬化シート、金属張積層板および配線基板に関する。
　近年、ＬＳＩの高速化や高集積化、メモリーの大容量化などが進み、それに伴って各種電子部品の小型化、軽量化、薄型化などが急速に進んでいる。このような電子部品の分野で使用される配線基板などには、例えば特許文献１に記載のようにバイアホール用開口（貫通孔）が形成され、めっきなどによって開口が充填されることによってバイアホールが形成されている。
特開平１１－２４３２７７号公報
　本開示の積層未硬化シートは、樹脂シート層と樹脂層とが交互に積層され、積層方向に貫通する貫通孔が形成された構造を有し、樹脂シート層が熱硬化性樹脂を主成分とする熱硬化性樹脂組成物で形成され、樹脂層が熱可塑性樹脂を含む熱可塑性樹脂組成物で形成され、貫通孔における樹脂シート層部分の内壁面に熱可塑性樹脂組成物が付着している。
　本開示の積層硬化シートは、硬化樹脂シート層と樹脂層とが交互に積層され、積層方向に貫通する貫通孔が形成された構造を有し、硬化樹脂シート層が熱硬化性樹脂を主成分とする熱硬化性樹脂組成物で形成され、樹脂層が熱可塑性樹脂を含む熱可塑性樹脂組成物で形成され、貫通孔における硬化樹脂シート層部分の内壁面に熱可塑性樹脂組成物が付着している。
　本開示の金属張積層板は、上記積層硬化シートと、該積層硬化シートの少なくとも一方の面に積層された金属箔とを含む。
　本開示の配線基板は、複数の絶縁層と該絶縁層間に配置された導体層とを具備し、絶縁層が上記積層硬化シートにより構成されている。
本開示の一実施形態に係る積層未硬化シートの構造を示す断面図である。 図１に示す積層未硬化シートの層Ｌ部分の一実施形態を示す上面図である。
　基板に貫通孔を形成する場合、貫通孔の内壁面が凸凹の状態となって粗くなることがある。貫通孔の内壁面が粗くなった状態でめっき処理を施すと、貫通孔の内壁面から基板を形成している層内にめっき液が浸入しやすくなる。そのため、層内にめっき金属が存在することになり、電気的信頼性が乏しくなる。
　本開示の積層未硬化シートは、樹脂シート層と樹脂層とが交互に積層され、積層方向に貫通する貫通孔が形成された構造を有し、貫通孔における樹脂シート層部分の内壁面には、熱可塑性樹脂組成物が付着している。そのため、貫通孔における樹脂シート層部分の内壁面の凸凹が熱可塑性樹脂で埋められて比較的滑らかになり、貫通孔の内壁面から樹脂シート層内にめっき液が浸入するのを抑制することができる。したがって、本開示の積層未硬化シートを基板の材料として使用すると、電気的信頼性に優れた配線基板が得られる。この場合、樹脂シート層２の貫通孔の内壁面は、熱可塑性樹脂組成物で被覆されていてもよい。
　本開示の積層未硬化シートは、樹脂シート層と樹脂層とが交互に積層され、積層方向に貫通する貫通孔が形成された構造を有している。樹脂シート層は、熱硬化性樹脂を主成分とする熱硬化性樹脂組成物で形成されており、未硬化状態または半硬化状態である。
　熱硬化性樹脂組成物は、熱硬化性樹脂を主成分とする組成物であれば限定されない。熱硬化性樹脂としては、例えば、熱硬化型の環状オレフィン樹脂、エポキシ樹脂、フェノール樹脂、アミノ樹脂、熱硬化型のポリイミド樹脂などが挙げられる。
　環状オレフィン樹脂とは、環状構造を有しているポリオレフィン系重合体であり、例えば、環状オレフィンとこの環状オレフィンと共重合可能な他のモノマーとの共重合体が挙げられる。環状オレフィンと他のモノマーとの割合は特に限定されず、例えば、環状オレフィンが１０～８０質量％、他のモノマーが２０～９０質量％含まれていてもよい。
　環状オレフィンとしては、例えば、ノルボルネン系モノマー、環状ジエン系モノマー、ビニル脂環式炭化水素系モノマーなどが挙げられる。具体的には、環状オレフィンとしては、ノルボルネン、ビニルノルボルネン、フェニルノルボルネン、ジシクロペンタジエン、テトラシクロドデセン、シクロプロペン、シクロブテン、シクロペンテン、シクロヘキセン、シクロヘキサジエン、シクロオクタジエンなどが挙げられる。これらの環状オレフィンは、単独で用いてもよく、２種以上が併用されていてもよい。
　環状オレフィンと共重合可能な他のモノマーとしては、例えば、鎖状オレフィン、アクリル酸メタクリル酸、アクリル酸エステル、メタクリル酸エステル、芳香族ビニル化合物、不飽和ニトリル、脂肪族共役ジエンなどが挙げられる。具体的には、このようなモノマーとしては、エチレン、プロピレン、ブテン、アクリル酸、メタクリル酸、フマル酸、無水フマル酸、マレイン酸、無水マレイン酸、アクリル酸メチル、アクリル酸エチル、アクリル酸プロピル、アクリル酸イソプロピル、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸イソプロピル、スチレン、ビニルトルエン、アクリロニトリル、メタクリロニトリル、１，３－ブタジエン、２－メチル－１，３－ブタジエン、２，３－ジメチル－１，３－ブタジエンなどが挙げられる。これらの他のモノマーは、単独で用いてもよく、２種以上を併用してもよい。
　アミノ樹脂とは、アミノ基を有する化合物とアルデヒド類との縮重合によって得られる。アミノ基を有する化合物としては、例えば尿素、メラミンなどが挙げられ、アルデヒド類としては、例えばホルムアルデヒドなどが挙げられる。アミノ樹脂としては、具体的には、尿素樹脂、メラミン樹脂などが挙げられる。
　熱硬化性樹脂は、本開示の積層未硬化シートの用途に応じて適宜使用すればよい。例えば、本開示の積層未硬化シートにより優れた電気特性を求めるのであれば、熱硬化型の環状オレフィン樹脂およびエポキシ樹脂からなる群より選択される少なくとも１種の樹脂を使用すればよい。一方、本開示の積層未硬化シートにより優れた耐熱性および機械的強度を求めるのであれば、熱硬化型の環状オレフィン樹脂、エポキシ樹脂、ポリイミド樹脂、フェノール樹脂およびアミノ樹脂（尿素樹脂、メラミン樹脂など）からなる群より選択される少なくとも１種の樹脂を使用すればよい。さらに、上記の特性に加えて、吸湿性が低いという点を考慮すると、熱硬化型の環状オレフィン樹脂を使用するのがよい。
　熱硬化性樹脂を主成分とする熱硬化性樹脂組成物とは、当該熱硬化性樹脂組成物中に最も多く含まれる樹脂成分が熱硬化性樹脂である樹脂組成物のことである。熱硬化性樹脂組成物には、例えば、酸化防止剤、紫外線吸収剤、着色剤、基材（例えば、無機フィラー、ガラスクロス、アラミド不職布、ガラス不職布など）、難燃剤などの添加剤が含まれていてもよい。この場合、基材および難燃剤の含有割合は、積層未硬化シートの断面における面積の０％以上４０％以下としてもよい。
　基材および難燃剤の同定は、例えば次の手順で行われる。まず、積層未硬化シートを所定の大きさに切断する（例えば、０．５ｍｍ×０．５ｍｍ）。基材および難燃剤の同定は、積層未硬化シートの代わりに、積層未硬化シートを硬化させた積層硬化シート、あるいはこの積層硬化シートを用いた金属張積層板や配線基板であっても同様の方法によって行うことができる。次いで、切断された積層未硬化シートの断面を走査型電子顕微鏡で観察して写真撮影を行う。走査型電子顕微鏡の代わりにデジタルマイクロスコープを用いてもよい。写真撮影する範囲としては、例えば、縦１００～１５０μｍ程度および横１００～１５０μｍ程度が目安となる。写真を撮影する場所は、任意の部分を１ヵ所のみでもよい。
　次いで、撮影した写真に基づいて、基材および難燃剤を同定する。走査型電子顕微鏡写真の場合、走査型電子顕微鏡に付設された分析器（電子線マイクロアナライザ（ＥＰＭＡ））によって、樹脂成分、基材および難燃剤を同定する。この場合、基材および難燃剤は、含まれる無機元素（例えば、Ｓｉ、Ｂｒなど）から同定する。樹脂成分は基材および難燃剤に含まれる上記元素が含まれていない部分となる。樹脂成分、基材および難燃剤の同定は、元素の特定を行った上で、写真に現れたそれぞれの色調の違いから区別することもできる。こうして、写真において、同定した樹脂成分、基材および難燃剤と同様の色調の部分を、それぞれ樹脂成分、基材および難燃剤と特定する。特定した基材および難燃剤の領域から、それぞれの面積を求めることができる。
　熱硬化性樹脂組成物には、積層未硬化シートの難燃性を向上させるために、無機フィラーおよび難燃剤の少なくとも一方が含まれていてもよい。無機フィラーは特に限定されず、例えば、シリカ、タルク、マイカ、クレー、炭酸カルシウム、酸化チタン、チタン酸バリウム、カーボンブラック、ガラスビーズ、ガラス中空球などが挙げられる。例えばシリカとしては、粉砕シリカ、溶融シリカなどが挙げられ、単独または２種以上を混合して用いてもよい。無機フィラーの平均粒子径は特に限定されず、例えば、０．０１μｍ以上１０μｍ以下であり、０．５μｍ以上３μｍ以下であってもよい。
　難燃剤は特に限定されず、例えば、リン酸メラミン、ポリリン酸メラム、ポリリン酸メレム、ピロリン酸メラミン、ポリリン酸アンモニウム、赤燐、芳香族リン酸エステル、ホスホン酸エステル、ホスフィン酸エステル、ホスフィンオキサイド、ホスファゼン、メラミンシアノレート、エチレンビスペンタブロモベンゼン、エチレンビステトラブロモフタルイミドなどが挙げられる。これらの難燃剤は、単独で用いてもよく、２種以上を併用してもよい。この場合、積層未硬化シートを硬化して得られる積層硬化シートの誘電正接を低くすることができるという点から臭素系の難燃剤（エチレンビスペンタブロモベンゼン、エチレンビステトラブロモフタルイミドなど）を用いてもよい。難燃剤の平均粒子径は特に限定されず、例えば、０．０１μｍ以上１０μｍ以下であり、０．５μｍ以上３μｍ以下であってもよい。
　樹脂層は、熱可塑性樹脂を含む熱可塑性樹脂組成物で形成されており、未硬化状態または半硬化状態である。熱可塑性樹脂組成物は、熱可塑性樹脂を含む組成物であれば限定されない。熱可塑性樹脂としては、例えば、樹脂シート層との接着性に優れ、固溶しにくい点で、ポリスチレン樹脂、フェニレン樹脂、テフロン（登録商標）樹脂、液晶ポリマーなどを用いてもよい。
　熱可塑性樹脂を含む熱可塑性樹脂組成物とは、具体的には、熱可塑性樹脂が５質量％以上含まれる組成物を意味し、熱可塑性樹脂が１０質量％以上含まれていてもよい。熱可塑性樹脂組成物は、例えば上述の熱硬化性樹脂や、上述の酸化防止剤および基材（例えば、無機フィラー、ガラスクロス、アラミド不職布、ガラス不職布など）などの群から選ばれる少なくとも１種の添加剤が含まれていてもよい。特に、熱可塑性樹脂組成物に熱硬化性樹脂が含まれていると、樹脂シート層と樹脂層との接着性を高めることができる。
　本開示の積層未硬化シートは、樹脂シート層と樹脂層とが交互に積層されている。一実施形態に係る積層未硬化シートの構造を、図１に基づいて説明する。図１に示す積層未硬化シート１は、３層の樹脂シート層２と２層の樹脂層３とが交互に積層された５層構造を有している。図１に示す積層未硬化シート１は５層構造を有しているが、本開示の積層未硬化シートは５層構造に限定されない。
　積層未硬化シート１には、上面から下面まで貫通する貫通孔（スルーホール）４が形成されている。この場合、熱可塑性樹脂組成物３１は、貫通孔４において少なくとも樹脂シート層２部分の内壁面５を被覆していればよい。
　上記した熱硬化性樹脂組成物を含む樹脂シート層２に貫通孔４を形成する場合、形成される貫通孔４は、その内壁面が粗くなりやすい。この場合、貫通孔４の内壁面５には複数の凹部が形成される。熱可塑性樹脂組成物３１はこの凹部を埋めるように付着している。貫通孔４の内壁面５に付着している熱可塑性樹脂組成物３１には、貫通孔４を貫く方向に複数の筋が形成されている。この筋は、貫通孔４内に形成されるめっき金属に対してアンカー効果を発揮する。その結果、熱可塑性樹脂組成物３１と貫通孔４内に形成されるめっき金属との間の接着強度を高めることができる。
　樹脂シート層２および樹脂層３の厚みは特に限定されず、例えば、樹脂層３の厚みは樹脂シート層２の厚みよりも薄くてもよい。貫通孔４において樹脂シート層２部分の内壁面が樹脂層３を形成している熱可塑性樹脂組成物で被覆されやすい点、および耐熱性を考慮すると、樹脂層３の厚みは、樹脂シート層２の厚みを１００とした場合の相対値で４～１４とするのがよい。この場合、積層未硬化シートとして、それぞれ厚みの異なる樹脂シート層２および樹脂層３によって形成されているものに対しても適用できることは言うまでもない。樹脂層３の厚みは特に限定されず、例えば０．５μｍ以上３μｍ以下程度とするのがよい。樹脂層３の厚みが０．５μｍ以上であれば、樹脂シート層２と樹脂層３との接着性をより高めることができる。一方、樹脂層３の厚みが３μｍ以下の場合、積層未硬化シート１を硬化させて得られる積層硬化シートの剛性がより高められて曲がりにくくなり、さらに耐熱性をより向上させることができる。積層未硬化シート１を硬化させて得られる積層硬化シートについても、樹脂層の厚みは、硬化樹脂シート層の厚みを１００とした場合の相対値で４～１４であってもよい。
　樹脂層３は、樹脂シート層２の主面全面を被覆している必要はない。例えば図２に示すように、樹脂シート層２が樹脂層３で被覆されていない部分が存在していてもよい。樹脂シート層２と樹脂層３との接着性などを考慮すると、樹脂シート層２の主面に対する樹脂層３の被覆率は６０％以上であればよく、９０％以上であってもよく、もちろん１００％であってもよい。さらに、被覆率が６０％以上であれば、任意の場所に貫通孔４を形成しても、貫通孔４の内壁面５が樹脂層３と接触する確率が高くなり、熱可塑性樹脂組成物３１が貫通孔４の内壁面５を被覆する点においても特に問題はない。
　樹脂シート層２および樹脂層３の少なくとも一方には、無機フィラーおよび難燃剤の少なくとも一方が含まれていてもよい。すなわち、熱硬化性樹脂組成物および熱可塑性樹脂組成物の少なくとも一方には、無機フィラーおよび難燃剤の少なくとも一方が含まれていてもよい。
樹脂シート層２および樹脂層３の少なくとも一方に、応力緩和剤がさらに含まれていてもよい。応力緩和剤は特に限定されず、例えば、シリコーン樹脂粒子などが挙げられる。シリコーン樹脂粒子としては、例えば、シリコンゴムパウダーとして、ＫＭＰ-５９７（信越化学工業（株）製）、Ｘ－５２－８７５（信越化学工業（株）製）、シリコンレジンパウダーとして、ＫＭＰ-５９０（信越化学工業（株）製）、Ｘ－５２－１６２１（信越化学工業（株）製）などが挙げられる。これらの応力緩和剤は、単独で用いてもよく、２種以上を併用してもよい。応力緩和剤としては、１０μｍ以下の平均粒径を有するものを用いてもよい。このような平均粒径を有する応力緩和剤を用いることによって、積層未硬化シート１が、例えば金属張積層板などに用いられる場合に、金属箔との密着性をより向上させることができる。
　樹脂シート層２および樹脂層３の少なくとも一方に、無機フィラーおよび難燃剤の少なくとも一方が含まれている場合、樹脂層３に含まれる無機フィラーおよび難燃剤の含有割合を、樹脂シート層２に含まれる無機フィラーおよび難燃剤の含有割合よりも少なくしてもよい。具体的には、樹脂シート層２に含まれる無機フィラーおよび難燃剤の含有割合を１とした場合、樹脂層３に含まれる無機フィラーおよび難燃剤の含有割合は０．１以上０．９以下であるのがよく、０．２以上０．８以下であってもよい。樹脂層３に含まれる無機フィラーおよび難燃剤の含有割合がこのような比であれば、積層未硬化シート１に貫通孔４を形成した場合に、貫通孔４の内壁面に対する樹脂層３から流出した熱可塑性樹脂組成物３１の濡れ性がをより向上させることができる。この場合、積層未硬化シートとして、それぞれ厚みの異なる樹脂シート層２および樹脂層３によって形成されているものに対しても適用できることは言うまでもない。
　本開示の積層硬化シートは、上記した積層未硬化シートに加圧加熱処理を施すことによって得られる。この場合、上記した未硬化樹脂シート１における樹脂シート層２、樹脂層３、貫通孔４、内壁面５および熱可塑性樹脂組成物３１は、積層硬化シートにおける硬化樹脂シート層、樹脂層、貫通孔、内壁面および熱可塑性樹脂組成物およびその符号にそれぞれ対応するものとなる。つまり、この積層硬化シートは、硬化樹脂シート層と樹脂層とが交互に積層され、積層方向に貫通する貫通孔が形成された構造を有している。この場合、硬化樹脂シート層は熱硬化性樹脂を主成分とする熱硬化性樹脂組成物で形成されている。樹脂層は熱可塑性樹脂を含む熱可塑性樹脂組成物で形成されている。さらに、貫通孔における硬化樹脂シート層部分の内壁面には熱可塑性樹脂組成物が付着した構成となっている。
　積層硬化シートによれば、貫通孔の内壁面に熱可塑性樹脂組成物が付着していることから、貫通孔にめっきなどを行う際のわずかな温度上昇によって熱可塑性樹脂組成物が溶解して、この溶解した熱可塑性樹脂組成物が貫通孔の内壁面に濡れ広がるようになる。これにより貫通孔の内壁面が熱可塑性樹脂組成物によって被覆されるようになる。こうしてめっき液を貫通孔から硬化樹脂シート層側へ浸入し難くすることが可能になる。
　積層硬化シートの場合も樹脂層の厚みは硬化樹脂シート層の厚みよりも薄くしてもよい。貫通孔において硬化樹脂シート層部分の内壁面が樹脂層を形成している熱可塑性樹脂組成物で被覆されやすい点、および耐熱性を考慮すると、樹脂層の厚みは、硬化樹脂シート層の厚みを１００とした場合の相対値で４～１４するのがよい。この場合も、積層硬化シートとして、それぞれ厚みの異なる硬化樹脂シート層および樹脂層によって形成されているものに対しても適用できることは言うまでもない。樹脂層の厚みは特に限定されず、例えば０．５μｍ以上３μｍ以下程度とするのがよい。樹脂層の厚みが０．５μｍ以上であれば、硬化樹脂シート層と樹脂層との接着性をより高めることができる。一方、樹脂層の厚みが３μｍ以下の場合、積層硬化シートを硬化させて得られる積層硬化シートの剛性がより高められて曲がりにくくなり、さらに耐熱性をより向上させることができる。
　硬化樹脂シートの場合も、樹脂層は、硬化樹脂シート層の主面の全面を被覆している必要はない。上記した未硬化樹脂シートの構造と同様、例えば図２に示すように、硬化樹脂シート層が樹脂層で被覆されていない部分が存在していてもよい。硬化樹脂シート層と樹脂層との接着性などを考慮すると、硬化樹脂シート層の主面に対する樹脂層の被覆率は６０％以上であればよく、９０％以上であってもよく、もちろん１００％であってもよい。さらに、被覆率が６０％以上であれば、任意の場所に貫通孔を形成しても、貫通孔の内壁面が樹脂層と接触する確率が高くなり、熱可塑性樹脂組成物が貫通孔の内壁面を被覆する点においても特に問題はない。
　硬化樹脂シート層および樹脂層の少なくとも一方には、無機フィラーおよび難燃剤の少なくとも一方が含まれていてもよい。すなわち、熱硬化性樹脂組成物および熱可塑性樹脂組成物の少なくとも一方には、無機フィラーおよび難燃剤の少なくとも一方が含まれていてもよい。
　硬化樹脂シート層および樹脂層の少なくとも一方に、無機フィラーおよび難燃剤の少なくとも一方が含まれている場合、樹脂層に含まれる無機フィラーおよび難燃剤の含有割合が、硬化樹脂シート層に含まれる無機フィラーおよび難燃剤の含有割合よりも少ない方がよい。具体的には、硬化樹脂シート層に含まれる無機フィラーおよび難燃剤の含有割合を１とした場合、樹脂層に含まれる無機フィラーおよび難燃剤の含有割合は質量比で０．１以上０．９以下とするのがよく、０．２以上０．８以下としてもよい。樹脂層に含まれる無機フィラーおよび難燃剤の含有割合がこのような質量比であれば、積層硬化シートに貫通孔を形成する場合に、貫通孔の内壁面に樹脂層から熱可塑性樹脂組成物が流出しやすくなり濡れ性がより向上する。この場合も、積層層化シートとして、それぞれ厚みの異なる硬化樹脂シート層および樹脂層によって形成されているものに対しても適用できることは言うまでもない。
　この場合、樹脂層（すなわち、熱可塑性樹脂組成物）に含まれる無機フィラーの含有割合を、硬化樹脂シート層に含まれる無機フィラーの含有割合よりも少なくしてもよい。樹脂層に含まれる熱可塑性樹脂が、貫通孔を形成する際の部分的な温度上昇によって溶融しやすくなる。一方、積層硬化シートの耐燃性を向上させるという点から、積層硬化シートの多くの部分を占める硬化樹脂シート層（すなわち、熱硬化性樹脂組成物）は、より多くの難燃剤を含んでいてもよい。硬化樹脂シート層および樹脂層にも、これらのうちの少なくとも一方に、上記した応力緩和剤がさらに含まれていてもよい。
　本開示の積層未硬化シートを製造する方法は特に限定されない。上述の熱硬化性樹脂組成物で形成された樹脂シート層と、上述の熱可塑性樹脂組成物で形成された樹脂層とを、交互に積層して得られる。
　樹脂シート層は、例えば、溶剤を含む熱硬化性樹脂組成物（熱硬化性樹脂ワニス）から形成される。溶剤としては、例えばキシレンを挙げることができる。この場合、固形分（樹脂成分および非樹脂成分）と溶剤との質量比は特に限定されず、例えば６０：４０～２０：８０程度の質量比で混合される。キシレンの他に、トルエン、ベンゼン、エチルベンゼンなどの芳香族系溶剤、ノルマルヘキサン、シクロヘキサン、メチルシクロヘキサンなどの炭化水素系溶剤、アセトンなどのケトン系溶剤、テトラヒドロフラン、クロロホルムなどの他の溶剤を用いてもよく、キシレンと上記の他の溶剤と併用してもよい。
　次いで、得られた熱硬化性樹脂ワニスからシート状成形体を作製する。具体的には、バーコーター法、ドクターブレード法、ダイコーター法などによって、熱硬化性樹脂ワニスをシート状に成形し、その後１２０～１５０℃程度で１～１０分程度乾燥し、未硬化状態のシート状成形体が得られる。シート状成形体は、例えば、熱硬化性樹脂組成物を押出機などによって加熱する押出法あるいは射出成形法で形成されてもよい。
　樹脂層は、例えば、溶剤を含む熱可塑性樹脂組成物（熱可塑性樹脂ワニス）から形成される。溶剤や溶剤の使用量については上述のとおりであり、詳細な説明は省略する。得られた熱可塑性樹脂ワニスをシート状成形体の一方の主面に塗布する。次いで、熱可塑性樹脂ワニスが塗布された主面に、熱可塑性樹脂ワニスが塗布されていない別のシート状成形体を重ね、シート状成形体／熱可塑性樹脂ワニス／シート状成形体の３層構造を有する積層体が得られる。必要に応じて、重ねた別のシート状成形体主面に熱可塑性樹脂ワニスを塗布し、所望の層数となるまで同様の作業が繰り返される。
　あるいは、熱可塑性樹脂ワニスが塗布されたシート状成形体を所望の枚数作製してから重ねてもよい。具体的には、このシート状成形体を、熱可塑性樹脂ワニスが塗布された主面と塗布されていない主面とが接触するように重ね、最後に、熱可塑性樹脂ワニスが塗布された主面に、熱可塑性樹脂ワニスが処理されていない別のシート状成形体を重ねて積層体を作製してもよい。
　このようにして得られた積層体を、例えば室温で０．１～１ＭＰａ程度の圧力で加圧処理することによって積層未硬化シートが得られる。本開示の積層未硬化シートは、積層させる層数にもよるが、例えば、０．０１～２ｍｍ程度の厚みを有している。
　本開示の積層硬化シートは、上述の積層未硬化シートを加圧加熱処理に供することによって得られる。加圧加熱処理条件としては、例えば、温度が１６０～２３０℃程度で圧力が１～１０ＭＰａ程度である。このようにして得られた積層硬化シートは、例えば、０．０１～２ｍｍ程度の厚みを有している。
　次に、本開示の金属張積層板について説明する。本開示の金属張積層板は、本開示の積層硬化シートの少なくとも一方の面に金属箔を備えている。本開示の金属張積層板は、例えば、本開示の積層未硬化シートと金属箔とを重ね合わせ加圧加熱処理して得られる。加圧加熱処理条件としては、上述の積層硬化シートを得る際に行われる条件と同じような条件としてもよい。
　金属箔としては特に限定されず、例えば、電解銅箔、圧延銅箔などの銅箔、アルミニウム箔、これらの金属箔を重ね合わせた複合箔などが挙げられる。これらの金属箔の中でも、例えば銅箔が用いられる。金属箔の厚みは特に限定されず、例えば５μｍ以上１０５μｍ以下程度である。金属箔の表面粗さは特に限定されず、０．５μｍ以下であってもよく、０．３μｍ以下であってもよい。
　本開示の金属張積層板は、本開示の積層未硬化シートと金属箔とをそれぞれ所望の枚数重ね合わせ、加熱加圧成形しても得られる。本開示の金属張積層板は、例えば、０．００１７以下の誘電正接を有している。このように金属張積層板の誘電正接が０．００１７以下であれば、優れた誘電率など十分な電気特性が発揮される。本開示の金属張積層板は、例えばプリント配線基板などに用いられる。
　次に、本開示の配線基板について説明する。本開示の配線基板は、絶縁層と、該絶縁層の主面に配置された導体層とを具備するものを基本的な構造とする。言い換えると、複数の絶縁層と該絶縁層間に配置された導体層とを具備しており、絶縁層が本開示の積層硬化シートで形成されている。ここで、絶縁層の主面とは、上記の絶縁層を構成する面のうち、互いに向かい合う最も面積が大きい面を意味し、絶縁層の厚み方向に対向する面が該当する。本開示の配線基板は、例えば、本開示の金属張積層板に回路およびスルーホールが形成された内層板とプリプレグとを重ね合わせ、プリプレグの表面に金属箔を積層させた後、加熱（硬化）加圧成形して得られる。さらに、表面の金属箔に回路およびスルーホールを形成して、多層プリント配線基板としてもよい。
　本開示の金属張積層板および配線基板によれば、上記した積層未硬化シートおよび積層硬化シートの箇所において説明したように、金属張積層板および配線基板の場合も、貫通孔における樹脂シート層部分の内壁面の凹凸あるいは硬化樹脂シート層部分の内壁面の凹凸が熱可塑性樹脂で埋められて比較的滑らかになっている。このため貫通孔の内壁面から樹脂シート層あるいは硬化樹脂シート層内にめっき液が浸入するのを抑えることができる。これにより電気的信頼性の高い金属張積層板および配線基板を得ることができる。
　上記したように、本開示の積層未硬化シートは、貫通孔における樹脂シート層部分の内壁面が熱可塑性樹脂組成物で被覆されている。本開示の積層硬化シートは、貫通孔における硬化樹脂シート層部分の内壁面が熱可塑性樹脂組成物で被覆されている。このため、これら積層未硬化シートおよび積層硬化シートのうちのいずれか一方によって形成される本開示の金属張積層板および配線基板も、貫通孔における樹脂シート層部分の内壁面の凸凹あるいは硬化樹脂シート層の内壁面の凹凸は、いずれもが熱可塑性樹脂で埋められた状態である。その結果、金属張積層板および配線基板の場合も、貫通孔の内壁面から樹脂シート層内あるいは硬化樹脂シート層内にめっき液が浸入するのを抑えることができる。こうして電気的信頼性に優れた金属張積層板および配線基板を得ることができる。
　以下、実施例を挙げて本開示の実施形態を具体的に説明するが、本開示の実施形態はこれらの実施例に限定されるものではない。
（試料１）
　熱硬化型の環状オレフィンコポリマー（ＣＯＣ、三井化学（株）製）を５０質量％、無機フィラーとしてシリカ（平均粒子径１μｍ）を２５質量％、難燃剤としてエチレンビスペンタブロモベンゼン（平均粒子径１μｍ、アルベマール社製、商品名：ＳＡＹＴＥＸ８０１０）を２５質量％の割合で混合して熱硬化性樹脂混合物を得た。用いた環状オレフィンコポリマー１００質量部に対して、溶媒としてキシレンを８０質量部の割合で混合して熱硬化性樹脂ワニスを調製した。
　次に、バーコーターを用いて、得られた樹脂ワニスを基材（ポリエチレンテレフタレートフィルム）上に塗布した。基材に塗布後、１５０℃で４分間乾燥し、基材から剥がしてシート状成形体（３０ｃｍ×３０ｃｍ、平均厚み：約２８μｍ）を得た。同様のシート状成形体を複数枚作製した。得られた成形体は未硬化の状態であった。
　次いで、熱可塑性樹脂としてポリスチレン（ＰＳ、日本ポリスチレン（株）製）を１０質量％、上記のＣＯＣを４０質量％、上記のシリカを２５質量％、上記の難燃剤を２５質量％の割合で混合して熱可塑性樹脂混合物を得た。用いたポリスチレン（ＰＳ）とＣＯＣとの合計量１００質量部に対して、溶媒としてキシレンを８０質量部の割合で混合して熱可塑性樹脂ワニスを調製した。
　得られたシート状成形体の一方の主面に、得られた熱可塑性樹脂ワニスを３μｍの厚みとなるように塗布した。熱可塑性樹脂ワニスが一方の主面に塗布されたシート状成形体を３枚作製した。次いで、得られた３枚のシート状成形体を、熱可塑性樹脂ワニスが塗布された主面と塗布されていない主面とが接触するように重ね、最後に熱可塑性樹脂ワニスが処理されていない別のシート状成形体を重ねて積層体を得た。得られた積層体は、４層のシート状成形体（樹脂シート層）と３層の熱可塑性樹脂ワニス（樹脂層）とが交互に積層された構造を有していた。得られた積層体を室温下、１ＭＰａの圧力で加圧処理に供し、積層未硬化シートを得た。
　得られた積層未硬化シートを加圧加熱処理に供し、積層硬化シートを得た。加圧加熱処理は、２００℃、４ＭＰａの加圧加熱条件下で、１２０分間行った。積層硬化シートは、シート状成形体の硬化により形成された硬化樹脂シート層が２３μｍの厚みを有し、樹脂層が２μｍの厚みを有していた。
　得られた積層硬化シートの樹脂層の一部を試料として取り出し、試料ホットプレートで加熱した。加熱によって試料は溶融したため、樹脂層には熱可塑性樹脂が含まれていると判断した。
　次いで、銅張積層板を次の方法によって得た。まず、積層未硬化シートの両面に１８μｍの厚みを有する銅箔を積層した。銅箔が積層された積層体を、２００℃、４ＭＰａ、１２０分間保持の加圧加熱条件下で加圧加熱処理に供し、銅張積層板を得た。
　さらに、得られた銅張積層板を４枚積層し、２００℃および４ＭＰａの加圧加熱条件下で加圧加熱処理に供し、配線基板を得た。
（試料２）
　上記のＰＳを２０質量％および上記のＣＯＣを３０質量％の割合で使用した以外は、試料１と同様の手順で熱可塑性樹脂ワニスを調製した。この熱可塑性樹脂ワニスを使用した以外は、試料１と同様の手順で積層硬化シート、銅張積層板および配線基板を得た。得られた積層硬化シートの樹脂層の一部を試料として取り出し、試料ホットプレートで加熱した。加熱によって試料は溶融したため、樹脂層には熱可塑性樹脂が含まれていると判断した。
（試料３）
　上記のＰＳを３０質量％および上記のＣＯＣを２０質量％の割合で使用した以外は、試料１と同様の手順で熱可塑性樹脂ワニスを調製した。この熱可塑性樹脂ワニスを使用した以外は、試料１と同様の手順で積層硬化シート、銅張積層板および配線基板を得た。得られた積層硬化シートの樹脂層の一部を試料として取り出し、試料ホットプレートで加熱した。加熱によって試料は溶融したため、樹脂層には熱可塑性樹脂が含まれていると判断した。
（試料４）
　上記のＰＳを４０質量％および上記のＣＯＣを１０質量％の割合で使用した以外は、試料１と同様の手順で熱可塑性樹脂ワニスを調製した。この熱可塑性樹脂ワニスを使用した以外は、試料１と同様の手順で積層硬化シート、銅張積層板および配線基板を得た。得られた積層硬化シートの樹脂層の一部を試料として取り出し、試料ホットプレートで加熱した。加熱によって試料は溶融したため、樹脂層には熱可塑性樹脂が含まれていると判断した。
（試料５）
　上記のＰＳを４０質量％および上記のＣＯＣを６０質量％の割合で使用し、シリカおよび難燃剤を使用しなかった以外は、試料１と同様の手順で熱可塑性樹脂ワニスを調製した。この熱可塑性樹脂ワニスを使用した以外は、試料１と同様の手順で積層硬化シート、銅張積層板および配線基板を得た。得られた積層硬化シートの樹脂層の一部を試料として取り出し、試料ホットプレートで加熱した。加熱によって試料は溶融したため、樹脂層には熱可塑性樹脂が含まれていると判断した。
（試料６）
　上記のＰＳを３０質量％、上記のＣＯＣを４５質量％およびシリカを２５質量％の割合で使用し、難燃剤を使用しなかった以外は、試料１と同様の手順で熱可塑性樹脂ワニスを調製した。この熱可塑性樹脂ワニスを使用した以外は、試料１と同様の手順で積層硬化シート、銅張積層板および配線基板を得た。得られた積層硬化シートの樹脂層の一部を試料として取り出し、試料ホットプレートで加熱した。加熱によって試料は溶融したため、樹脂層には熱可塑性樹脂が含まれていると判断した。
（試料７）
　上記のＰＳを３０質量％、上記のＣＯＣを４５質量％および難燃剤を２５質量％の割合で使用し、無機フィラーを使用しなかった以外は、試料１と同様の手順で熱可塑性樹脂ワニスを調製した。この熱可塑性樹脂ワニスを使用した以外は、試料１と同様の手順で積層硬化シート、銅張積層板および配線基板を得た。得られた積層硬化シートの樹脂層の一部を試料として取り出し、試料ホットプレートで加熱した。加熱によって試料は溶融したため、樹脂層には熱可塑性樹脂が含まれていると判断した。
（試料８）
　上記のＣＯＣを５０質量％の割合で使用し、熱可塑性樹脂を使用しなかった以外は、試料１と同様の手順で熱可塑性樹脂ワニスを調製した。この熱可塑性樹脂ワニスを使用した以外は、試料１と同様の手順で積層硬化シート、銅張積層板および配線基板を得た。得られた積層硬化シートの樹脂層の一部を試料として取り出し、試料ホットプレートで加熱した。加熱によって試料は溶融せずに、形状をほぼ維持した状態で炭化したため、樹脂層には熱可塑性樹脂が含まれていないと判断した。
　まず、作製した試料１～８の配線基板の断面を、分析器を付設した走査型電子顕微鏡により撮影した。撮影した断面の画像から、無機フィラーおよび難燃剤の合計した割合を面積比として求めたところ、無機フィラーおよび難燃剤の面積割合はいずれの試料も１０％以下であった。
　次に、試料１～８で得られた積層硬化シートそれぞれについて、ＵＬ９４Ｖ燃焼性試験に準拠して燃焼性の評価を行った。具体的には、積層硬化シートから切り取った試験片（１２．５ｍｍ×１２５ｍｍ）をクランプに垂直に取り付けた。次いで、試験片の下から２０ｍｍ炎による接炎を行い、試験片から炎が消えた時間を測定した。５個の試験片について試験を行い、Ｖ－ｎｏｔ（燃えやすい）、Ｖ１およびＶ０（難燃性）の３段階で評価した。結果を表１に示す。
　次いで、試料１～８で得られた配線基板ぞれぞれに、２５０μｍの直径を有するスルーホール（ＴＨ）を１０個形成し、ＴＨに無電解銅めっき処理を施した。めっき後、ＴＨの内壁面から積層硬化シートを形成している層内に、めっき金属（銅）が侵入しているか否かを検証した。層内に最も深く侵入していた銅の長さ（ＴＨの内壁面からの長さ）を表１に示す。表１において、例えば「≦２０μｍ」は最も深く侵入していた銅の長さが２０μｍであったことを示す。
　さらに、試料１～８で得られた配線基板のぞれぞれについて、ＴＨ壁面間の絶縁信頼性を評価した。まず、得られた配線基板に、２５０μｍの直径を有するスルーホール（ＴＨ）を１００μｍの間隔を設けて（ＴＨ壁面間の距離が１００μｍ）１０個形成し、ＴＨに無電解銅めっき処理を施した。次いで、温度１３０℃および湿度８５％ＲＨの環境下で、５．５Ｖの電圧をかけて１０００時間信頼性試験を行った。ＴＨ壁面間の距離を１２５μｍ、１５０μｍ、１７５μｍおよび２５０μｍに変更してＴＨを形成した配線基板についても、同様の試験を行った。ＴＨ壁面間の絶縁信頼性が保持できる壁面間距離を表１に示す。表１において、例えば「≧１７５μｍ」は少なくとも１７５μｍの壁面間距離を設ければ、絶縁信頼性が保持できることを示す。
Figure JPOXMLDOC01-appb-T000001
　表１に示すように、試料１～７では、めっき処理を施した場合に、めっき金属が層内に侵入しにくいことがわかる。さらに、絶縁信頼性について、ＴＨの間隔が狭くても（ＴＨ壁面間が短くても）、絶縁性が保持されていることがわかる。
　１　　積層未硬化シート
　２　　樹脂シート層
　３　　樹脂層
　３１　樹脂層に由来する熱可塑性樹脂組成物
　４　　貫通孔（スルーホール）
　５　　貫通孔の内壁面

Claims (10)

  1. 　樹脂シート層と樹脂層とが交互に積層され、積層方向に貫通する貫通孔が形成された構造を有し、
    　前記樹脂シート層が、熱硬化性樹脂を主成分とする熱硬化性樹脂組成物で形成され、
    　前記樹脂層が、熱可塑性樹脂を含む熱可塑性樹脂組成物で形成され、
    　前記貫通孔における前記樹脂シート層部分の内壁面に、前記熱可塑性樹脂組成物が付着している、
    ことを特徴とする積層未硬化シート。
  2. 　前記樹脂層の厚みが、前記樹脂シート層の厚みを１００とした場合の相対値で４～１４である請求項１に記載の積層未硬化シート。
  3. 　前記熱硬化性樹脂組成物および前記熱可塑性樹脂組成物の少なくとも一方が、無機フィラーおよび難燃剤の少なくとも一方をさらに含む請求項１または２に記載の積層未硬化シート。
  4. 　前記樹脂層に含まれる無機フィラーおよび難燃剤の含有割合が、前記樹脂シート層に含まれる無機フィラーおよび難燃剤の含有割合よりも少ない請求項１～３のいずれかに記載の積層未硬化シート。
  5. 　硬化樹脂シート層と樹脂層とが交互に積層され、積層方向に貫通する貫通孔が形成された構造を有し、
    　前記硬化樹脂シート層が、熱硬化性樹脂を主成分とする熱硬化性樹脂組成物で形成され、
    　前記樹脂層が、熱可塑性樹脂を含む熱可塑性樹脂組成物で形成され、
    　前記貫通孔における前記硬化樹脂シート層部分の内壁面に、前記熱可塑性樹脂組成物が付着している、
    ことを特徴とする積層硬化シート。
  6. 　前記樹脂層の厚みが、前記硬化樹脂シート層の厚みを１００とした場合の相対値で４～１４である請求項５に記載の積層硬化シート。
  7. 　前記熱硬化性樹脂組成物および前記熱可塑性樹脂組成物の少なくとも一方が、無機フィラーおよび難燃剤の少なくとも一方をさらに含む請求項５または６に記載の積層硬化シート。
  8. 　前記樹脂層に含まれる無機フィラーおよび難燃剤の含有割合が、前記硬化樹脂シート層に含まれる無機フィラーおよび難燃剤の含有割合よりも少ない請求項５～７のいずれかに記載の積層硬化シート。
  9. 　請求項５～８のいずれかに記載の積層硬化シートと、該積層硬化シートの少なくとも一方の面に積層された金属箔とを含むことを特徴とする金属張積層板。
  10. 　絶縁層と、該絶縁層の主面に配置された導体層とを具備し、前記絶縁層が請求項５～８のいずれかに記載の積層硬化シートにより構成されていることを特徴とする配線基板。
PCT/JP2019/024552 2018-06-28 2019-06-20 積層未硬化シート WO2020004229A1 (ja)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201980043027.XA CN112314063A (zh) 2018-06-28 2019-06-20 层叠未固化片材
US17/254,881 US11426970B2 (en) 2018-06-28 2019-06-20 Laminated uncured sheet
EP19826177.8A EP3817527A4 (en) 2018-06-28 2019-06-20 LAYERED UNCURED SHEET

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2018123234A JP7237478B2 (ja) 2018-06-28 2018-06-28 積層未硬化シート
JP2018-123234 2018-06-28

Publications (1)

Publication Number Publication Date
WO2020004229A1 true WO2020004229A1 (ja) 2020-01-02

Family

ID=68984968

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2019/024552 WO2020004229A1 (ja) 2018-06-28 2019-06-20 積層未硬化シート

Country Status (5)

Country Link
US (1) US11426970B2 (ja)
EP (1) EP3817527A4 (ja)
JP (1) JP7237478B2 (ja)
CN (1) CN112314063A (ja)
WO (1) WO2020004229A1 (ja)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2020004225A1 (ja) 2018-06-26 2021-07-08 京セラ株式会社 有機基板、金属張積層板および配線基板
JPWO2021215382A1 (ja) * 2020-04-23 2021-10-28

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11186677A (ja) * 1997-12-25 1999-07-09 Shin Etsu Polymer Co Ltd プリント配線板用積層板
JPH11243277A (ja) 1998-02-26 1999-09-07 Ibiden Co Ltd フィルドビア構造を有する多層プリント配線板
JP2005026587A (ja) * 2003-07-04 2005-01-27 Fujikura Ltd 多層基板用基材、多層基板およびその製造方法
JP2008103640A (ja) * 2006-10-20 2008-05-01 Ngk Spark Plug Co Ltd 多層配線基板
JP2014127716A (ja) * 2012-12-26 2014-07-07 Samsung Electro-Mechanics Co Ltd コア基板及びその製造方法、並びに電子部品内蔵基板及びその製造方法

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09187910A (ja) * 1996-01-11 1997-07-22 Dainippon Printing Co Ltd 積層化粧材の製造方法
JP2005136050A (ja) * 2003-10-29 2005-05-26 Kyocera Corp 配線基板及びその製造方法
KR100968278B1 (ko) * 2008-03-28 2010-07-06 삼성전기주식회사 절연시트 및 그 제조방법과 이를 이용한 인쇄회로기판 및그 제조방법
TW201139643A (en) * 2010-01-29 2011-11-16 Nitto Denko Corp Thermal conductive sheet
US20140079913A1 (en) * 2011-03-28 2014-03-20 Tomoo Nishiyama Multilayer resin sheet, resin sheet laminate, cured multilayer resin sheet and method for producing same, multilayer resin sheet with metal foil, and semiconductor device
WO2013042749A1 (ja) * 2011-09-22 2013-03-28 日立化成株式会社 積層体、積層板、多層積層板、プリント配線板及び積層板の製造方法
WO2014174827A1 (ja) * 2013-04-26 2014-10-30 株式会社デンソー 多層基板、多層基板を用いた電子装置、多層基板の製造方法、基板、および基板を用いた電子装置
JP6452335B2 (ja) * 2013-08-09 2019-01-16 日鉄ケミカル＆マテリアル株式会社 エポキシ樹脂組成物及びその硬化物
FR3059201B1 (fr) * 2016-11-18 2019-06-21 Safran Electrical & Power Circuit imprime a isolation renforcee et procede de fabrication

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11186677A (ja) * 1997-12-25 1999-07-09 Shin Etsu Polymer Co Ltd プリント配線板用積層板
JPH11243277A (ja) 1998-02-26 1999-09-07 Ibiden Co Ltd フィルドビア構造を有する多層プリント配線板
JP2005026587A (ja) * 2003-07-04 2005-01-27 Fujikura Ltd 多層基板用基材、多層基板およびその製造方法
JP2008103640A (ja) * 2006-10-20 2008-05-01 Ngk Spark Plug Co Ltd 多層配線基板
JP2014127716A (ja) * 2012-12-26 2014-07-07 Samsung Electro-Mechanics Co Ltd コア基板及びその製造方法、並びに電子部品内蔵基板及びその製造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3817527A4

Also Published As

Publication number Publication date
JP2020004852A (ja) 2020-01-09
JP7237478B2 (ja) 2023-03-13
EP3817527A1 (en) 2021-05-05
EP3817527A4 (en) 2022-04-06
CN112314063A (zh) 2021-02-02
US11426970B2 (en) 2022-08-30
US20210260847A1 (en) 2021-08-26

Similar Documents

Publication Publication Date Title
KR101001529B1 (ko) 다층 프린트 배선판의 층간 절연용 수지 조성물, 접착필름 및 프리프레그
KR101814992B1 (ko) 에폭시 수지 조성물
TWI443015B (zh) 絕緣樹脂片積層體、由該絕緣樹脂片積層體所積層而成之多層印刷配線板
KR101677461B1 (ko) 에폭시 수지 조성물
CN103650649B (zh) 粘接膜、使用了该粘接膜的多层印制电路板、及该多层印制电路板的制造方法
JP5936794B2 (ja) 剥離樹脂層付金属箔及びプリント配線板
JP6811240B2 (ja) 有機絶縁体、金属張積層板および配線基板
WO2018179682A1 (ja) 接着剤付き銅箔、銅張積層板および配線基板
US4029845A (en) Printed circuit base board and method for manufacturing same
JP5772314B2 (ja) 多層プリント配線板用接着フィルム
US9888580B2 (en) Method for manufacturing multilayer substrate, multilayer insulation film, and multilayer substrate
WO2020004229A1 (ja) 積層未硬化シート
TW201412864A (zh) 熱硬化性樹脂組成物、ｂ階段（半硬化階段）化的樹脂薄膜、金屬箔、覆銅箔板及多層增層基板
JP6884207B2 (ja) 有機絶縁体、金属張積層板および配線基板
KR20160052423A (ko) 회로 기판 및 이의 제조 방법
JP7181231B2 (ja) 有機絶縁体、金属張積層板および配線基板
US11661495B2 (en) Organic board, metal-clad laminate, and wiring board
JP4214573B2 (ja) 積層板の製造方法
JP6983603B2 (ja) 有機絶縁体、金属張積層板および配線基板
WO2021215382A1 (ja) 有機樹脂フィルム
US11879049B2 (en) Organic insulating body, metal-clad laminate, and wiring board
JP5831027B2 (ja) 接着フィルム、該接着フィルムを用いた多層プリント配線板、及び該多層プリント配線板の製造方法
JP6187567B2 (ja) 多層プリント配線板の製造方法
JPH0260195A (ja) アディティブ法配線板の製造方法
JP2005347701A (ja) 多層プリント配線板の製造方法

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: 19826177

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 2019826177

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 2019826177

Country of ref document: EP

Effective date: 20210128