WO2020022084A1 - 硬化性組成物、プリプレグ、レジンシート、金属箔張積層板及びプリント配線板 - Google Patents

硬化性組成物、プリプレグ、レジンシート、金属箔張積層板及びプリント配線板 Download PDF

Info

Publication number
WO2020022084A1
WO2020022084A1 PCT/JP2019/027496 JP2019027496W WO2020022084A1 WO 2020022084 A1 WO2020022084 A1 WO 2020022084A1 JP 2019027496 W JP2019027496 W JP 2019027496W WO 2020022084 A1 WO2020022084 A1 WO 2020022084A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
epoxy
mass
curable composition
compound
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2019/027496
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
克哉 富澤
まゆみ 菊地
英利 河合
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Gas Chemical Co Inc
Original Assignee
Mitsubishi Gas Chemical Co Inc
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 Mitsubishi Gas Chemical Co Inc filed Critical Mitsubishi Gas Chemical Co Inc
Priority to JP2020532289A priority Critical patent/JP7488513B2/ja
Priority to CN201980049413.XA priority patent/CN112469758B/zh
Priority to KR1020207033129A priority patent/KR102768029B1/ko
Priority to EP19841212.4A priority patent/EP3828221B1/en
Priority to US17/262,872 priority patent/US11499005B2/en
Publication of WO2020022084A1 publication Critical patent/WO2020022084A1/ja
Anticipated expiration legal-status Critical
Priority to US17/845,200 priority patent/US11718708B2/en
Priority to JP2023220636A priority patent/JP7765749B2/ja
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • C08G59/621—Phenols
    • 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
    • B32B15/092—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 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—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
    • 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
    • B32B5/028—Net structure, e.g. spaced apart filaments bonded at the crossing points
    • 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
    • B32B5/08—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 the fibres or filaments of a layer being of different substances, e.g. conjugate fibres, mixture of different 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
    • 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
    • B32B5/22—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 the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—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 the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—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 the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • 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
    • B32B5/22—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 the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—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 the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—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 the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • B32B5/262—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 the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary characterised by one fibrous or filamentary layer being a woven fabric layer
    • B32B5/263—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 the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary characterised by one fibrous or filamentary layer being a woven fabric layer next to one or more woven fabric layers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/226—Mixtures of di-epoxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/26—Di-epoxy compounds heterocyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
    • C08G59/306—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C08G59/38—Epoxy compounds containing three or more epoxy groups together with di-epoxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4014—Nitrogen containing compounds
    • C08G59/4028—Isocyanates; Thioisocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
    • 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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/315—Compounds containing carbon-to-nitrogen triple bonds
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
    • 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
    • B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
    • 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
    • B32B2255/02—Coating on the layer surface on fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • 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
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0276—Polyester 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/14—Mixture of at least two fibres made of different materials
    • 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
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/12—Mixture of at least two particles made of different materials
    • 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
    • B32B2307/206—Insulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B32B2307/734—Dimensional stability
    • 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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • 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
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • 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
    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/04—Polysiloxanes
    • C08J2383/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • 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
    • H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
    • 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

Definitions

  • the present invention relates to a curable composition, a prepreg, a resin sheet, a metal foil-clad laminate, and a printed wiring board.
  • Patent Document 1 discloses that a thermosetting resin composition containing a specific maleimide compound, a silicone compound having an epoxy group in a molecular structure, and a compound having a phenolic hydroxyl group has excellent heat resistance and low thermal expansion property. It is disclosed that it is suitably used for a metal foil-clad laminate and a multilayer printed wiring board.
  • Patent Document 2 discloses an addition polymer of a polymaleimide, a diglycidylpolysiloxane represented by the following formula (I), and a diallylbisphenol represented by the following formula (II):
  • a production method of obtaining a resin for encapsulating a semiconductor by reacting an allylated phenol resin represented by a predetermined ratio and condition is disclosed.
  • the resin for semiconductor encapsulation obtained by the above-described production method has good compatibility between the polymaleimide and the above-mentioned addition polymer, and furthermore, a composition using the resin for semiconductor encapsulation.
  • the cured product has excellent properties (for example, high glass transition temperature, moisture resistance and strength under heat) and is highly reliable as a semiconductor sealing resin composition.
  • the component b is an important component that reacts with a maleimide group in a resin-forming reaction with the polymaleimide and improves the compatibility between the polymaleimide and the polysiloxane. ing.
  • R 1 represents an alkylene group or a phenylene group
  • R 2 each independently represents an alkyl group or a phenyl group
  • n represents an integer of 1 to 100.
  • R 4 represents an ether bond, a methylene group, a propylidene group, or a direct bond (single bond).
  • a resin composition containing a silicone compound having an epoxy group in a molecular structure and a thermosetting resin such as a maleimide compound has excellent low thermal expansion properties.
  • the present inventors have found that in the resin composition, there is a problem in moldability due to insufficient compatibility between the silicone compound and the thermosetting resin. Furthermore, the present inventors have found that the above resin composition has insufficient chemical resistance and metal foil peel strength (for example, copper foil peel strength) when used as a metal foil-clad laminate.
  • Patent Document 2 the resin composition described in Patent Document 2 is used for semiconductor encapsulation, and low thermal expansion properties, chemical resistance, and copper foil peel strength required as characteristics of a printed wiring board have been studied. Absent.
  • the present invention has been made in view of the above problems, and has curable compositions, prepregs, resin sheets, metal foil-clad laminates, and printed wiring boards having excellent compatibility, low thermal expansion properties, and chemical resistance.
  • the purpose is to provide.
  • the present inventors have conducted intensive studies to solve the above-mentioned problems. As a result, the above problems can be solved by a curable composition containing an alkenylphenol, an epoxy-modified silicone, and an epoxy compound other than the epoxy-modified silicone, or a curable composition containing a polymer having these as a constituent unit. The inventors have found that the present invention can be performed, and have completed the present invention.
  • the present invention is as follows. [1] An alkenylphenol A, an epoxy-modified silicone B, and an epoxy compound C other than the epoxy-modified silicone B, Curable composition. [2] The average number of phenol groups per molecule of the alkenyl phenol A is 1 or more and less than 3, the average number of epoxy groups per molecule of the epoxy-modified silicone B is 1 or more and less than 3, The average number of epoxy groups is 1 or more and less than 3; The curable composition according to [1]. [3] The alkenyl phenol A contains diallyl bisphenol and / or dipropenyl bisphenol, The curable composition according to [1] or [2].
  • the epoxy-modified silicone B contains an epoxy-modified silicone having an epoxy equivalent of 140 to 250 g / mol, The curable composition according to any one of [1] to [3].
  • the epoxy-modified silicone B contains an epoxy-modified silicone represented by the following formula (1): The curable composition according to any one of [1] to [4].
  • the epoxy compound C contains an epoxy compound represented by the following formula (2): The curable composition according to any one of [1] to [5]. (Wherein, R a each independently represent an alkyl group or a hydrogen atom having 1 to 10 carbon atoms.) [7] The content of the epoxy compound C is 5 to 50% by mass with respect to 100% by mass of the total of the epoxy-modified silicone B and the epoxy compound C.
  • the curable composition according to any one of [1] to [6].
  • [8] Including a polymer D containing a structural unit derived from alkenylphenol A, a structural unit derived from epoxy-modified silicone B, and a structural unit derived from epoxy compound C, Curable composition.
  • the weight average molecular weight of the polymer D is from 3.0 ⁇ 10 3 to 5.0 ⁇ 10 4 ;
  • the content of the structural unit derived from the epoxy-modified silicone B in the polymer D is 20 to 60% by mass based on the total mass of the polymer D.
  • the alkenyl group equivalent of the polymer D is 300 to 1500 g / mol; The curable composition according to any one of [8] to [10].
  • the content of the polymer D is 5 to 50% by mass based on 100% by mass of the resin solid content.
  • Further containing a thermosetting resin E The curable composition according to any one of [1] to [12].
  • the thermosetting resin E contains at least one member selected from the group consisting of a maleimide compound, a cyanate ester compound, a phenol compound, an alkenyl-substituted nadimide compound, and an epoxy compound.
  • the maleimide compound is bis (4-maleimidophenyl) methane, 2,2-bis ⁇ 4- (4-maleimidophenoxy) -phenyl ⁇ propane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane and Including one or more selected from the group consisting of maleimide compounds represented by the following formula (3): [14] The curable composition according to [14].
  • the cyanate compound includes a compound represented by the following formula (5) excluding a compound represented by the following formula (4) and / or a compound represented by the following formula (4): The curable composition according to [14] or [15].
  • R 6 each independently represents a hydrogen atom or a methyl group, and n 2 represents an integer of 1 or more.
  • Rya each independently represents an alkenyl group having 2 to 8 carbon atoms
  • Ryb each independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom
  • Ryc represents each independently represent an aromatic ring having 4 to 12 carbon atoms
  • RYC may form a benzene ring fused structure
  • RYC may be present, it may be absent
  • a 1a Represents an alkylene group having 1 to 6 carbon atoms, an aralkylene group having 7 to 16 carbon atoms, an arylene group having 6 to 10 carbon atoms, a fluorenylidene group, a sulfonyl group, an oxygen atom, a sulfur atom, or a direct bond (single bond).
  • the epoxy compound contains a compound represented by the following formula (6) or a compound represented by the following formula (7); [14] The curable composition according to any one of [16] to [16].
  • R 13 each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkenyl group having 2 to 3 carbon atoms.
  • each R 14 independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkenyl group having 2 to 3 carbon atoms.
  • the content of the inorganic filler is 50 to 1000 parts by mass with respect to 100 parts by mass of the resin solid content.
  • [20] A substrate, The curable composition according to any one of [1] to [19], impregnated or applied to the substrate.
  • Prepreg. [21] A support, and the curable composition according to any one of [1] to [19] disposed on the surface of the support.
  • [22] A laminate formed of at least one selected from the group consisting of the prepreg according to [20] and the resin sheet according to [21], And a metal foil disposed on one or both sides of the laminate, Metal foil clad laminate.
  • a curable composition a prepreg, a resin sheet, a metal foil-clad laminate and a printed wiring board having excellent compatibility, low thermal expansion property and chemical resistance.
  • the present embodiment a mode for carrying out the present invention (hereinafter, referred to as “the present embodiment”) will be described in detail, but the present invention is not limited thereto, and various modifications may be made without departing from the gist of the present invention. It is possible.
  • ⁇ resin solids '' as used herein means, unless otherwise specified, the components of the curable composition of the present embodiment except for the solvent and the filler, and 100 parts by mass of the resin solids, It means that the total of the components excluding the solvent and the filler in the curable composition is 100 parts by mass.
  • ⁇ refers to the compatibility of the silicone component, polymer D, with other thermosetting resins in the curable composition. Due to the excellent compatibility, the separation of the polymer D during molding is suppressed, and a molded article having excellent appearance can be obtained, and the obtained molded article is also excellent in isotropy in physical properties.
  • the curable composition of the first embodiment contains alkenylphenol A, epoxy-modified silicone B, and epoxy compound C excluding epoxy-modified silicone B (hereinafter, also simply referred to as “epoxy compound C”).
  • a curable composition containing these components tends to be more excellent in compatibility with a thermosetting resin having insufficient compatibility with the epoxy-modified silicone B. Due to this, the curable composition can exhibit more excellent compatibility. Further, when a part of each of these components is reacted (polymerized) and used, the curable composition can exhibit more excellent low thermal expansion property and chemical resistance.
  • alkenylphenol A is not particularly limited as long as it is a compound having a structure in which one or more alkenyl groups are directly bonded to a phenolic aromatic ring.
  • the curable composition can exhibit excellent compatibility by containing alkenylphenol A.
  • the alkenyl group is not particularly limited, but includes, for example, an alkenyl group having 2 to 30 carbon atoms such as a vinyl group, an allyl group, a propenyl group, a butenyl group, and a hexenyl group.
  • the alkenyl group is preferably an allyl group and / or a propenyl group, and more preferably an allyl group, from the viewpoint of more effectively and reliably achieving the effects of the present invention.
  • the number of alkenyl groups directly bonded to one phenolic aromatic ring is not particularly limited, and is, for example, 1 to 4.
  • the number of alkenyl groups directly bonded to one phenolic aromatic ring is preferably from 1 to 2, and more preferably 1, from the viewpoint of more effectively and reliably achieving the effects of the present invention.
  • the phenolic aromatic ring refers to one in which one or more hydroxyl groups are directly bonded to an aromatic ring, and includes a phenol ring and a naphthol ring.
  • the number of hydroxyl groups directly bonded to one phenolic aromatic ring is not particularly limited, and is, for example, 1 to 2, and preferably 1.
  • the phenolic aromatic ring may have a substituent other than an alkenyl group.
  • substituents include a straight-chain alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, and a straight-chain alkyl group having 1 to 10 carbon atoms.
  • Examples include a chain alkoxy group, a branched alkoxy group having 3 to 10 carbon atoms, a cyclic alkoxy group having 3 to 10 carbon atoms, and a halogen atom.
  • the number of the substituent directly bonded to one phenolic aromatic ring is not particularly limited, and is, for example, 1-2. Further, the bonding position of the substituent to the phenolic aromatic ring is not particularly limited.
  • the alkenylphenol A may have one or more structures in which one or more alkenyl groups are directly bonded to a phenolic aromatic ring. From the viewpoint of more effectively and reliably exerting the effects of the present invention, alkenylphenol A preferably has one or two structures in which one or more alkenyl groups are directly bonded to a phenolic aromatic ring, and has two. Is preferred.
  • Alkenylphenol A may be, for example, a compound represented by the following formula (1A) or the following formula (1B).
  • Rxa independently represents an alkenyl group having 2 to 8 carbon atoms
  • Rxb each independently represents an alkyl group having 1 to 10 carbon atoms, or a hydrogen atom
  • Rxc represents Independently represents an aromatic ring having 4 to 12 carbon atoms
  • Rxc may form a condensed structure with a benzene ring, Rxc may or may not be present
  • Rxc does not exist, one benzene ring may have two or more Rxa and / or Rx
  • the alkenyl group having 2 to 8 carbon atoms represented by Rxa and Rxd is not particularly limited, and examples thereof include a vinyl group, an allyl group, a propenyl group, a butenyl group, and a hexenyl group. And the like.
  • examples in which the groups represented by Rxc and Rxf form a condensed structure with a benzene ring include, for example, compounds containing a naphthol ring as a phenolic aromatic ring.
  • examples in which the groups represented by Rxc and Rxf do not exist include, for example, compounds containing a phenol ring as a phenolic aromatic ring.
  • the alkyl group having 1 to 10 carbon atoms represented by Rxb and Rxe is not particularly limited.
  • the alkylene group having 1 to 6 carbon atoms represented by A is not particularly limited, and includes, for example, a methylene group, an ethylene group, a trimethylene group, and a propylene group.
  • the aralkylene group having 7 to 16 carbon atoms, represented as A is not particularly limited, for example, the formula: -CH 2 -Ar-CH 2 - , - CH 2 -CH 2 -Ar-CH 2 -CH 2 - Or a group represented by the formula: —CH 2 —Ar—CH 2 —CH 2 — (wherein, Ar represents a phenylene group, a naphthylene group, or a biphenylene group).
  • the arylene group having 6 to 10 carbon atoms is not particularly limited, but includes, for example, a phenylene ring.
  • the compound represented by the formula (1B) is preferably a compound in which Rxf is a benzene ring (compound containing a dihydroxynaphthalene skeleton), from the viewpoint of more effectively and reliably exhibiting the effects of the present invention.
  • Alkenylphenol A is preferably an alkenylbisphenol in which one alkenyl group is bonded to each of two phenolic aromatic rings of a bisphenol from the viewpoint of further improving compatibility.
  • alkenyl bisphenol is a diallyl bisphenol in which one allyl group is bonded to two phenolic aromatic rings of bisphenols, and / or one propenyl group is bonded to two phenolic aromatic rings of bisphenols.
  • Preferred is dipropenyl bisphenol.
  • the diallyl bisphenol is not particularly restricted but includes, for example, o, o'-diallyl bisphenol A ("DABPA" manufactured by Daiwa Chemical Industry Co., Ltd.), o, o'-diallyl bisphenol F, o, o'-diallyl bisphenol S , O, o'-diallylbisphenolfluorene.
  • DABPA o'-diallyl bisphenol A
  • F o
  • o'-diallyl bisphenol S o, o'-diallyl bisphenol S , O, o'-diallylbisphenolfluorene.
  • the dipropenyl bisphenol is not particularly restricted but includes, for example, o, o'-dipropenyl bisphenol A ("PBA01" of Gunei Chemical Industry Co., Ltd.), o, o'-diallylbisphenol F, o, o'-di And propenylbisphenol S and o, o'-dipropenylbisphenolfluorene.
  • the average number of phenol groups per molecule of alkenyl phenol A is preferably 1 or more and less than 3 and more preferably 1.5 or more and 2.5 or less from the viewpoint of more effectively and reliably achieving the effects of the present invention. More preferred.
  • the average number of phenol groups is calculated by the following equation.
  • Ai represents the number of phenol groups of alkenyl phenol having i phenol groups in the molecule
  • Xi represents the ratio of alkenyl phenol having i phenol groups in the molecule to the whole alkenyl phenol
  • Epoxy-modified silicone B is not particularly limited as long as it is a silicone compound or resin modified with an epoxy group-containing group.
  • the curable composition can exhibit excellent low thermal expansion properties and chemical resistance by containing the epoxy-modified silicone B.
  • the silicone compound or resin is not particularly limited as long as it is a compound having a polysiloxane skeleton in which siloxane bonds are repeatedly formed.
  • the polysiloxane skeleton may be a linear skeleton, a cyclic skeleton, or a network skeleton. Among these, a linear skeleton is preferred from the viewpoint of more effectively and reliably achieving the effects of the present invention.
  • the epoxy group-containing group is not particularly limited, and includes, for example, a group represented by the following formula (a1).
  • R 0 represents an alkylene group (for example, an alkylene group having 1 to 5 carbon atoms such as a methylene group, an ethylene group, and a propylene group)
  • X represents a monovalent group represented by the following formula (a2).
  • the epoxy-modified silicone B preferably contains an epoxy-modified silicone having an epoxy equivalent of 140 to 250 g / mol.
  • Epoxy-modified silicone B tends to be able to further improve compatibility with a thermosetting resin, low thermal expansion property and chemical resistance in a well-balanced manner by containing an epoxy-modified silicone having an epoxy equivalent within the above range.
  • the epoxy equivalent is more preferably 145 to 245 g / mol, and further preferably 150 to 240 g / mol.
  • Epoxy-modified silicone B preferably contains two or more epoxy-modified silicones from the viewpoint of further improving the compatibility with the thermosetting resin, low thermal expansion and chemical resistance in a well-balanced manner.
  • the two or more epoxy-modified silicones preferably have different epoxy equivalents, and an epoxy-modified silicone having an epoxy equivalent of 50 to 350 g / mol and an epoxy-modified silicone having an epoxy equivalent of 400 to 4000 g / mol.
  • the average epoxy equivalent of the epoxy-modified silicone B is preferably 140 to 3000 g / mol, more preferably 250 to 2000 g / mol, More preferably, it is 300 to 1000 g / mol.
  • the epoxy-modified silicone B contains an epoxy-modified silicone represented by the following formula (1) from the viewpoint that the compatibility with the thermosetting resin, the low thermal expansion property, and the chemical resistance can be further improved in a well-balanced manner.
  • R 1 each independently represents an alkylene group, a phenylene group or an aralkylene group
  • R 2 each independently represents an alkyl group having 1 to 10 carbon atoms or a phenyl group
  • n represents 1 Represents an integer greater than or equal to.
  • R 1 each independently represents an alkylene group, a phenylene group or an aralkylene group.
  • the alkylene group represented by R 1 may be linear, branched, or cyclic.
  • the alkylene group preferably has 1 to 12 carbon atoms, and more preferably 1 to 4 carbon atoms. Although it does not specifically limit as an alkylene group, For example, a methylene group, an ethylene group, or a propylene group is mentioned.
  • the aralkylene group represented by R 1 preferably has 7 to 30 carbon atoms, and more preferably 7 to 13 carbon atoms.
  • the aralkylene group is not particularly limited, and includes, for example, a group represented by the following formula (XI).
  • Formula (XI) (In the formula (XI), * represents a bond)
  • the group represented by R 1 may further have a substituent.
  • substituents include a straight-chain alkyl group having 1 to 10 carbon atoms and a 3 to 10 carbon atoms.
  • R 1 is particularly preferably a propylene group.
  • R 2 independently represents an alkyl group having 1 to 10 carbon atoms or a phenyl group.
  • the alkyl group and the phenyl group may have a substituent.
  • the alkyl group having 1 to 10 carbon atoms may be linear, branched or cyclic. Although it does not specifically limit as an alkyl group, For example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, an isobutyl group, and a cyclohexyl group are mentioned.
  • R 2 is preferably a methyl group or a phenyl group.
  • n represents an integer of 1 or more, for example, 1 to 100. From the viewpoint of further improving the compatibility with the thermosetting resin, low thermal expansion property and chemical resistance in a well-balanced manner, n is preferably 50 or less, more preferably 30 or less, and further preferably 20 or less. .
  • the epoxy-modified silicone B may contain two or more epoxy-modified silicones represented by the formula (1) from the viewpoint of further improving the compatibility with the thermosetting resin, the low thermal expansion property and the chemical resistance in a well-balanced manner. preferable. In this case, it is preferable that the epoxy-modified silicones containing two or more kinds have different n, respectively.
  • the epoxy-modified silicone in which n is 1 to 2 in the formula (1) and the epoxy-modified silicone in which n is 5 to 20 in the formula (1) are preferable. It is more preferable to contain a certain epoxy-modified silicone.
  • the average number of epoxy groups per molecule of the epoxy-modified silicone B is preferably 1 or more and less than 3 and more preferably 1.5 or more and 2.5 or less from the viewpoint of more effectively and reliably achieving the effects of the present invention. Is more preferred.
  • the epoxy compound C is an epoxy compound other than the epoxy-modified silicone B, and more specifically, an epoxy compound having no polysiloxane skeleton. By containing the epoxy compound C, the curable composition can exhibit excellent compatibility, chemical resistance, copper foil adhesion, and insulation reliability.
  • the epoxy compound C is not particularly limited as long as it is an epoxy compound other than the epoxy-modified silicone B. It is preferable that the epoxy compound contains a bifunctional epoxy compound having two epoxy groups in one molecule from the viewpoint of exhibiting more excellent compatibility, chemical resistance, copper foil adhesion and insulation reliability.
  • bisphenol type epoxy resin for example, bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and bisphenol fluorene type epoxy resin
  • phenolic novolak type epoxy resins eg, phenol novolak type epoxy resin, bisphenol A novolak type epoxy resin, cresol novolak type epoxy resin
  • trisphenolmethane type epoxy aralkyl type epoxy resin, biphenyl type containing biphenyl skeleton Epoxy resin, naphthalene type epoxy resin containing naphthalene skeleton, anthracene type epoxy resin containing dihydroanthracene skeleton, glycidyl Stell type epoxy resin, polyol type epoxy resin, isocyanurate ring-containing epoxy resin, dicyclopentadiene type epoxy resin, fluorene type epoxy resin having a fluorene skeleton, epoxy resin comprising bisphenol
  • Ar 3 each independently represents a benzene ring or a naphthalene ring
  • Ar 4 represents a benzene ring, a naphthalene ring, or a biphenyl ring
  • R 3a each independently represents a hydrogen atom or methyl Represents a group, and each ring may have a substituent other than a glycidyloxy group (eg, an alkyl group having 1 to 5 carbon atoms or a phenyl group).
  • the alkyl group having 1 to 10 carbon atoms may be linear, branched or cyclic. Although it does not specifically limit as an alkyl group, For example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, an isobutyl group, and a cyclohexyl group are mentioned.
  • the biphenyl-type epoxy resin may be in the form of a mixture of the compounds b2 having different numbers of Ra as alkyl groups. Specifically, a mixture of biphenyl-type epoxy resins having different numbers of Ra as the alkyl group is preferable, and a compound b2 having 0 the number of Ra as the alkyl group and a compound having 4 the number of Ra as the alkyl group are preferable. Mixtures of b2 are more preferred.
  • R 3b independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms (eg, a methyl group or an ethyl group), an aralkyl group, a benzyl group, a naphthyl group, or a naphthyl containing a glycidyloxy group
  • R 3b independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms (eg, a methyl group or an ethyl group), an aralkyl group, a benzyl group, a naphthyl group, or a naphthyl containing a glycidyloxy group
  • n represents an integer of 0 or more (eg, 0 to 2).
  • each R 3c independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms (eg, a methyl group or an ethyl group).
  • the epoxy resin composed of a bisphenol A-type structural unit and a hydrocarbon-based structural unit is not particularly limited, and examples thereof include a compound represented by the following formula (b5).
  • R 1x and R 2x each independently represent a hydrogen atom or a methyl group
  • R 3x to R 6x each independently represent a hydrogen atom, a methyl group, a chlorine atom, or a bromine atom.
  • X represents an ethyleneoxyethyl group, a di (ethyleneoxy) ethyl group, a tri (ethyleneoxy) ethyl group, a propyleneoxypropyl group, a di (propyleneoxy) propyl group, a tri (propyleneoxy) propyl group, or a group having 2 carbon atoms. Represents up to 15 alkylene groups (eg, a methylene group or an ethylene group).
  • the epoxy compound C is a bisphenol-type epoxy resin, an aralkyl-type epoxy resin, a biphenyl-type epoxy resin, a naphthalene-type, from the viewpoint of exhibiting more excellent compatibility, chemical resistance, copper foil adhesion and insulation reliability. It is preferably at least one selected from the group consisting of an epoxy resin and a dicyclopentadiene type epoxy resin, and more preferably a biphenyl type epoxy resin and / or a naphthalene type epoxy resin.
  • the average number of epoxy groups per molecule of the epoxy compound C is preferably 1 or more and less than 3 and more preferably 1.5 or more and 2.5 or less from the viewpoint of more effectively and reliably achieving the effects of the present invention. More preferred.
  • the content of the epoxy compound C is more preferably 100% by mass with respect to the total amount of the epoxy-modified silicone B and the epoxy compound C from the viewpoint of exhibiting more excellent compatibility, chemical resistance, copper foil adhesion and insulation reliability. It is preferably from 5 to 95% by mass, more preferably from 5 to 90% by mass, still more preferably from 5 to 50% by mass, and particularly preferably from 20 to 50% by mass.
  • the curable composition of the first embodiment preferably contains a phenolic compound F other than alkenylphenol A from the viewpoint of exhibiting more excellent copper foil adhesion.
  • the phenol compound F is not particularly limited, but is a bisphenol-type phenol resin (for example, bisphenol A-type resin, bisphenol E-type resin, bisphenol F-type resin, bisphenol S-type resin, etc.), phenol novolak resin (for example, phenol novolak) Resin, naphthol novolak resin, cresol novolak resin, etc.), glycidyl ester phenol resin, naphthalene phenol resin, anthracene phenol resin, dicyclopentadiene phenol resin, biphenyl phenol resin, alicyclic phenol resin, polyol phenol resin And aralkyl-type phenol resins, phenol-modified aromatic hydrocarbon formaldehyde resins, and fluorene-type phenol resins.
  • the phenolic compound F is preferably a bifunctional phenolic compound having two phenolic hydroxyl groups in one molecule, from the viewpoint of exhibiting better compatibility and copper foil adhesion.
  • bifunctional phenol compound examples include, but are not particularly limited to, bisphenol, biscresol, bisphenols having a fluorene skeleton (eg, bisphenol having a fluorene skeleton, biscresol having a fluorene skeleton), and biphenol (eg, p, p′-).
  • biphenol, etc. dihydroxy diphenyl ether (eg, 4,4'-dihydroxy diphenyl ether, etc.), dihydroxy diphenyl ketone (eg, 4,4'-dihydroxy diphenyl ketone, etc.), dihydroxy diphenyl sulfide (eg, 4,4'-dihydroxy diphenyl sulfide) And the like, and dihydroxyarenes (eg, hydroquinone and the like).
  • the bifunctional phenol compounds are used alone or in combination of two or more.
  • the bifunctional phenol compounds are preferably bisphenols, biscresols, and bisphenols having a fluorene skeleton from the viewpoint of exhibiting even better copper foil adhesion.
  • the content of alkenylphenol A is from 1 to 50 parts by mass based on 100 parts by mass of the total amount of alkenylphenol A, epoxy-modified silicone B, epoxy compound C and phenolic compound F from the viewpoint of exhibiting more excellent compatibility.
  • it is 10 to 45 parts by mass, more preferably 15 to 40 parts by mass.
  • the content of the epoxy-modified silicone B is based on 100 parts by mass of the total amount of the alkenylphenol A, the epoxy-modified silicone B, the epoxy compound C, and the phenol compound F, from the viewpoint of achieving a better balance between low thermal expansion property and chemical resistance.
  • the amount is preferably 5 to 70 parts by mass, more preferably 10 to 60 parts by mass, and even more preferably 40 to 50 parts by mass.
  • the content of the epoxy compound C is the total amount of the alkenylphenol A, the epoxy-modified silicone B, the epoxy compound C, and the phenol compound F from the viewpoint of exhibiting more excellent compatibility, chemical resistance, copper foil adhesion and insulation reliability.
  • the amount is preferably 1 to 50 parts by mass, more preferably 5 to 40 parts by mass, even more preferably 10 to 30 parts by mass with respect to 100 parts by mass.
  • the content of the phenolic compound F is from 1 to 50 parts by mass with respect to 100 parts by mass of the total amount of the alkenylphenol A, the epoxy-modified silicone B, the epoxy compound C, and the phenolic compound F from the viewpoint of exhibiting more excellent copper foil adhesion. , Preferably 5 to 40 parts by mass, more preferably 10 to 30 parts by mass.
  • the contents of the alkenylphenol A, the epoxy-modified silicone B, and the epoxy compound C described above are the total amount of the alkenylphenol A, the epoxy-modified silicone B, and the epoxy compound C. It represents the content based on 100 parts by mass.
  • the curable composition of the second embodiment includes a polymer D containing a structural unit derived from alkenylphenol A, a structural unit derived from epoxy-modified silicone B, and a structural unit derived from epoxy compound C.
  • alkenylphenol A, the epoxy-modified silicone B, and the epoxy compound C those described in the first embodiment can be used.
  • the polymer D can exhibit sufficient compatibility even when mixed with a thermosetting resin having poor compatibility with the silicone compound.
  • the curable composition containing the polymer D and the thermosetting resin can provide a uniform varnish or cured product.
  • a cured product such as a prepreg obtained by using the curable composition is one in which each component is uniformly compatible, and variation in physical properties due to non-uniform components is suppressed.
  • the curable composition of the second embodiment may contain, in addition to the polymer D, at least one selected from the group consisting of alkenylphenol A, epoxy-modified silicone B, and epoxy compound C.
  • the alkenylphenol A, the epoxy-modified silicone B, or the epoxy compound C included in the curable composition of the second embodiment may be an unreacted component remaining after the polymerization of the polymer D, or may be purified. A component added to the polymer D again may be used.
  • Polymer D contains a structural unit derived from alkenylphenol A, a structural unit derived from epoxy-modified silicone B, and a structural unit derived from epoxy compound C, and, if necessary, derived from phenol compound F. You may further contain a structural unit. Hereinafter, each structural unit is also referred to as a structural unit A, B, C, or F, respectively.
  • the curable composition of the second embodiment can exhibit more excellent compatibility, thermal expansion property, chemical resistance, peel strength, and insulation reliability.
  • the weight average molecular weight of the polymer D is in terms of polystyrene by gel permeation chromatography, is preferably from 3.0 ⁇ 10 3 ⁇ 5.0 ⁇ 10 4, 3.0 ⁇ 10 3 ⁇ 2.0 ⁇ 10 4 is more preferable.
  • the weight average molecular weight is 3.0 ⁇ 10 3 or more, the curable composition tends to exhibit more excellent copper foil adhesion and chemical resistance.
  • the weight average molecular weight is 5.0 ⁇ 10 4 or less, more excellent compatibility tends to be exhibited.
  • the content of the structural unit A in the polymer D is preferably 5 to 50% by mass based on the total mass of the polymer D.
  • the content of the structural unit A is more preferably from 10 to 45% by mass, and still more preferably from 15 to 40% by mass.
  • the content of the structural unit B in the polymer D is preferably 20 to 60% by mass based on the total mass of the polymer D.
  • the content of the structural unit B is more preferably 25 to 55% by mass, and still more preferably 30 to 50% by mass.
  • the structural unit B is composed of an epoxy-modified silicone having an epoxy equivalent of 50 to 350 g / mol (hereinafter, also referred to as “low equivalent epoxy-modified silicone B1”) and an epoxy-modified silicone having an epoxy equivalent of 400 to 4000 g / mol (hereinafter, referred to as “epoxy modified silicone B1”). , "Also referred to as” high equivalent weight epoxy-modified silicone B2 ").
  • the content of the structural unit B1 derived from the low equivalent weight epoxy-modified silicone B1 in the polymer D is preferably 5 to 22.5% by mass, and more preferably 10 to 20% by mass based on the total mass of the polymer D. Is more preferable, and more preferably 10 to 17% by mass.
  • the content of the structural unit B2 derived from the high equivalent weight epoxy-modified silicone B2 in the polymer D is preferably 15 to 55% by mass, and more preferably 20 to 52.5% by mass based on the total mass of the polymer D. Is more preferable, and even more preferably 25 to 50% by mass.
  • the mass ratio of the content of the structural unit B2 to the content of the structural unit B1 is preferably 1.5 to 4, more preferably 1.7 to 3.5, and 1.9 to 3.1. Is more preferable.
  • the contents of the structural unit B1 and the structural unit B2 have the above relationship, the copper foil adhesion and chemical resistance tend to be further improved.
  • the content of the structural unit C in the polymer D is preferably 5 to 30% by mass based on the total mass of the polymer D.
  • the content of the structural unit C is preferably from 10 to 25% by mass, and more preferably from 15 to 20% by mass.
  • the content of the structural unit C is preferably from 5 to 95% by mass, more preferably from 5 to 90% by mass, and preferably from 5 to 50% by mass, based on the total mass of the structural units B and C. More preferably, the content is 20% by mass, particularly preferably 20 to 50% by mass.
  • the content of the structural unit B and the content of the structural unit C have the above relationship, there is a tendency that more excellent compatibility, chemical resistance, copper foil adhesion, and insulation reliability are further improved.
  • the content of the structural unit F in the polymer D is preferably 5 to 30% by mass based on the total mass of the polymer D.
  • the content of the structural unit F is preferably from 10 to 25% by mass, and more preferably from 15 to 20% by mass.
  • the alkenyl group equivalent of the polymer D is preferably 300 to 1500 g / mol.
  • the alkenyl group equivalent is 300 g / mol or more, the cured product of the curable composition tends to have a lower elastic modulus, and as a result, the thermal expansion of a substrate or the like obtained using the cured product is further improved. It tends to decrease.
  • the alkenyl group equivalent is 1500 g / mol or less, the compatibility, chemical resistance, and reliability of the curable composition tend to be further improved.
  • the alkenyl group equivalent is preferably 350 to 1200 g / mol, more preferably 400 to 1000 g / mol.
  • the polymer D is obtained, for example, by a step of reacting an alkenylphenol A, an epoxy-modified silicone B, an epoxy compound C, and, if necessary, a phenol compound F in the presence of a polymerization catalyst G.
  • the reaction may be performed in the presence of an organic solvent. More specifically, in the above step, the addition reaction between the epoxy group of the epoxy-modified silicone B and the epoxy compound C and the hydroxyl group of the alkenylphenol A, and the hydroxyl group of the obtained addition reaction product and the epoxy-modified silicone B and
  • the polymer D can be obtained by the addition reaction with the epoxy group of the epoxy compound C progressing.
  • the polymerization catalyst G is not particularly limited, and includes, for example, an imidazole catalyst and a phosphorus-based catalyst. These catalysts are used alone or in combination of two or more. Among these, an imidazole catalyst is preferred.
  • the imidazole catalyst is not particularly limited, and examples thereof include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, -Cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1, 2-a] imidazoles such as benzimidazole ("TBZ” manufactured by Shikoku Chemicals Co., Ltd.) and 2,4,5-triphenylimidazole ("TPIZ” manufactured by Tokyo Chemical Industry Co., Ltd.).
  • the amount of the polymerization catalyst G (preferably an imidazole catalyst) is not particularly limited, and is, for example, 0.1 to 100 parts by mass of the total amount of alkenylphenol A, epoxy-modified silicone B, epoxy compound C and phenol compound F. 10 parts by mass.
  • the amount of the polymerization catalyst G to be used is preferably equal to or greater than 1.0 part by mass, and more preferably equal to or less than 4.0 parts by mass.
  • the organic solvent is not particularly limited, and for example, a polar solvent or a non-polar solvent can be used.
  • the polar solvent is not particularly limited.
  • ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; cellosolve solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate; ethyl lactate, methyl acetate, ethyl acetate and acetic acid Ester solvents such as butyl, isoamyl acetate, ethyl lactate, methyl methoxypropionate, and methyl hydroxyisobutyrate; and amides such as dimethylacetamide and dimethylformamide.
  • the nonpolar solvent is not particularly limited, and examples thereof include aromatic hydrocarbons such as toluene and xylene. These solvents may be used alone or in combination of two or more.
  • the amount of the organic solvent used is not particularly limited, and is, for example, 50 to 150 parts by mass with respect to 100 parts by mass of the total amount of alkenylphenol A, epoxy-modified silicone B, epoxy compound C and phenol compound F.
  • the heating temperature is not particularly limited, and may be, for example, 100 to 170 ° C.
  • the heating time is also not particularly limited, and may be, for example, 3 to 8 hours.
  • the polymer D may be separated and purified from the reaction mixture by a conventional method.
  • the curable compositions of the first and second embodiments preferably contain a thermosetting resin E.
  • the polymer D having a silicone-based skeleton exhibits excellent compatibility even with a thermosetting resin having poor compatibility with the silicone-based compound. Therefore, even when the polymer D and the thermosetting resin E are combined, each component is excellent in compatibility without being separated in the curable composition.
  • the curable composition of the second embodiment can exhibit more excellent low thermal expansion properties and chemical resistance by containing the polymer D and the thermosetting resin E.
  • the thermosetting resin E is selected from the group consisting of a maleimide compound, a cyanate ester compound, a phenol compound, an alkenyl-substituted nadiimide compound, and an epoxy compound from the viewpoint of further improving low thermal expansion, chemical resistance, and copper foil adhesion. It is preferable to contain at least one selected from the group consisting of a maleimide compound, a cyanate ester compound, a phenol compound and an epoxy compound.
  • the content of the thermosetting resin E is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and more preferably 30 to 75% by mass based on 100% by mass of the resin solid content. Is more preferable.
  • thermosetting resin E contains a maleimide compound from the viewpoint of further improving low thermal expansion property and chemical resistance.
  • the maleimide compound is not particularly limited as long as it is a compound having one or more maleimide groups in one molecule.
  • a monomaleimide compound having one maleimide group in one molecule for example, N-phenylmaleimide, N -Hydroxyphenylmaleimide, etc.
  • polymaleimide compounds having two or more maleimide groups in one molecule eg, bis (4-maleimidophenyl) methane, 2,2-bis ⁇ 4- (4-maleimidophenoxy) -phenyl ⁇ Propane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, bis (3,5-dimethyl-4-maleimidophenyl) methane, bis (3,5-diethyl-4-maleimidophenyl) methane), m-phenylenebismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1,6 ′ -Bismaleimide- (2,2,4-trimethyl) hexane, maleimide compounds represented by the following formula (3), and prepolymers of these maleimide
  • n 1 is 1 or more, preferably 1 to 100, and more preferably 1 to 10.
  • maleimide compounds are used alone or in combination of two or more.
  • maleimide compounds include bis (4-maleimidophenyl) methane and 2,2-bis ⁇ 4- (4-maleimidophenoxy) -phenyl ⁇ propane. , Bis (3-ethyl-5-methyl-4-maleimidophenyl) methane and a maleimide compound represented by the formula (3).
  • maleimide compound a commercially available product may be used, or a preparation prepared by a known method may be used.
  • Commercially available maleimide compounds include “BMI-70”, “BMI-80”, and “BMI-1000P” manufactured by K-I Kasei Co., Ltd., and “BMI-3000” and “BMI-3000” manufactured by Daiwa Kasei Kogyo Co., Ltd. -4000 ",” BMI-5100 ",” BMI-7000 ",” BMI-2300 “,” MIR-3000 “manufactured by Nippon Kayaku Co., Ltd., and the like.
  • the content of the maleimide compound is preferably 1 to 50 parts by mass, and more preferably 5 to 40 parts by mass with respect to 100 parts by mass of the resin solid content from the viewpoint of further improving low thermal expansion property and chemical resistance. More preferably, the amount is 10 to 40 parts by mass.
  • thermosetting resin E preferably contains a cyanate ester compound from the viewpoint of further improving low thermal expansion properties and chemical resistance.
  • the cyanate ester compound is not particularly limited as long as it has two or more cyanato groups (cyanate ester groups) in one molecule.
  • a compound represented by the following formula (4) or a compound represented by the formula (4) A compound represented by the following formula (5) excluding the compound represented by formula (5), biphenylaralkyl-type cyanate ester, bis (3,3-dimethyl-4-cyanatophenyl) methane, bis (4-cyanatophenyl) Methane, 1,3-dicyanatobenzene, 1,4-dicyanatobenzene, 1,3,5-tricyanatobenzene, 1,3-dicyanatonaphthalene, 1,4-dicyanatonaphthalene, 1,6-dicyanato Naphthalene, 1,8-dicyanatonaphthalene, 2,6-dicyanatonaphthalene, 2,7-dicyanatonaphthalene, 1,3,6-tricyanatonaphthalene, 4, 4 ′ Dicyanatobiphenyl, bis (4-cyanatophenyl) ether, bis (4-cyanatophenyl) thioether, bis (4-cyanato
  • R 6 each independently represents a hydrogen atom or a methyl group
  • n 2 represents an integer of 1 or more.
  • Rya each independently represents an alkenyl group having 2 to 8 carbon atoms
  • Ryb each independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom
  • Ryc represents each independently represent an aromatic ring having 4 to 12 carbon atoms
  • RYC may form a benzene ring fused structure
  • RYC may be present, it may be absent
  • a 1a Represents an alkylene group having 1 to 6 carbon atoms, an aralkylene group having 7 to 16 carbon atoms, an arylene group having 6 to 10 carbon atoms, a fluorenylidene group, a sulfonyl group, an oxygen atom, a sulfur atom, or a direct bond (single bond).
  • Ryc does not exist, one
  • the cyanate compound preferably contains a compound represented by the formula (4) and / or the formula (5) from the viewpoint of further improving low thermal expansion property and chemical resistance.
  • n 2 represents an integer of 1 or more, preferably an integer of 1 to 20, and more preferably an integer of 1 to 10.
  • the alkenyl group having 2 to 8 carbon atoms represented by Rya is not particularly limited, and examples thereof include a vinyl group, an allyl group, a propenyl group, a butenyl group, and a hexenyl group.
  • the alkyl group having 1 to 10 carbon atoms represented by Ryb is not particularly limited, but may be, for example, a linear group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group.
  • Branched alkyl group such as isopropyl group, isobutyl group and tert-butyl group.
  • the alkylene group having 1 to 6 carbon atoms represented by A 1a includes, but is not particularly limited to, a methylene group, an ethylene group, a trimethylene group, and a propylene group.
  • the aralkylene group having 7 to 16 carbon atoms, represented as A 1a is not particularly limited, for example, the formula: -CH 2 -Ar-CH 2 - , - CH 2 -CH 2 —Ar—CH 2 —CH 2 —, or a group represented by the formula: —CH 2 —Ar—CH 2 —CH 2 — (wherein, Ar represents a phenylene group, a naphthylene group, or a biphenylene group). Is mentioned.
  • the arylene group having 6 to 10 carbon atoms represented by A 1a is not particularly limited, and includes, for example, a phenylene ring.
  • n represents an integer of 1 to 10, preferably an integer of 1 to 20, and more preferably an integer of 1 to 10.
  • the compound represented by the formula (5) is preferably a compound represented by the following formula (c1).
  • Rx each independently represents a hydrogen atom or a methyl group, and R independently represents an alkenyl group having 2 to 8 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or a hydrogen atom.
  • n represents an integer of 1 to 10.
  • cyanate compounds may be produced according to a known method.
  • a specific production method for example, a method described in JP-A-2017-195334 (particularly, paragraphs 0052 to 0057) and the like can be mentioned.
  • the content of the cyanate ester compound as the thermosetting resin E is preferably 10 to 70 parts by mass with respect to 100 parts by mass of the resin solid content from the viewpoint of further improving low thermal expansion property and chemical resistance. Is preferably 15 to 60 parts by mass, and more preferably 20 to 50 parts by mass.
  • thermosetting resin E preferably contains a phenol compound from the viewpoint of further improving the copper foil adhesion.
  • the phenol compound is not particularly limited as long as it is a compound having two or more phenolic hydroxyl groups in one molecule.
  • phenols having two or more phenolic hydroxyl groups in one molecule bisphenols (for example, bisphenol A, bisphenol E, bisphenol F, bisphenol S, etc.), diallyl bisphenols (eg, diallyl bisphenol A, diallyl bisphenol E, diallyl bisphenol F, diallyl bisphenol S, etc.), phenolic novolak resins (eg, phenol novolak resin, naphthol novolak) Resin, cresol novolak resin, etc.), naphthalene type phenol resin, dihydroanthracene type phenol resin, dicyclopentadiene type phenol resin, biphenyl type phenol resin, Fine aralkyl phenolic resins.
  • bisphenols for example, bisphenol A, bisphenol E, bisphenol F, bisphenol S, etc.
  • diallyl bisphenols eg, diallyl bisphenol A, diallyl bisphenol E, diallyl bisphenol F, diallyl bisphenol S, etc.
  • aralkyl phenolic resin examples include a compound represented by the following formula (c2).
  • Ar 1 each independently represents a benzene ring or a naphthalene ring
  • Ar 2 represents a benzene ring, a naphthalene ring, or a biphenyl ring
  • R 2a each independently represents a hydrogen atom or methyl
  • m represents an integer of 1 to 50
  • each ring may have a substituent other than a hydroxyl group (eg, an alkyl group having 1 to 5 carbon atoms or a phenyl group).
  • the compound represented by the formula (c2) is a compound in which Ar 1 is a naphthalene ring and Ar 2 is a benzene ring (hereinafter, referred to as “naphthol aralkyl”) in the formula (c2) from the viewpoint of further improving the copper foil adhesion.
  • naphthol aralkyl a compound in which Ar 1 is a benzene ring and Ar 2 is a biphenyl ring in the formula (c2) (hereinafter, also referred to as “biphenylaralkyl-type phenol resin”).
  • biphenylaralkyl-type phenol resin a compound in which Ar 1 is a benzene ring and Ar 2 is a biphenyl ring in the formula (c2) from the viewpoint of further improving the copper foil adhesion.
  • the naphthol aralkyl type phenol resin is preferably a compound represented by the following formula (2b).
  • R 2a each independently represents a hydrogen atom or a methyl group (preferably a hydrogen atom), and m represents an integer of 1 to 10 (preferably an integer of 1 to 6).
  • the biphenylaralkyl-type phenol resin is preferably a compound represented by the following formula (2c).
  • R 2b independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a phenyl group (preferably a hydrogen atom), and m1 is an integer of 1 to 20 (preferably 1 to 6 Represents an integer.)
  • aralkyl-type phenol resin a commercially available product may be used, or a product synthesized by a known method may be used.
  • Commercially available aralkyl-type phenolic resins include “KAYAHARD @ GPH-65”, “KAYAHARD @ GPH-78”, “KAYAHARD @ GPH-103” (biphenylaralkyl-type phenolic resin) manufactured by Nippon Kayaku Co., Ltd., Nippon Steel Chemical Co., Ltd. Company product “SN-495” (naphthol aralkyl type phenol resin).
  • the content of the phenol compound as the thermosetting resin E is preferably from 10 to 40 parts by mass, more preferably from 15 to 35 parts by mass, based on 100 parts by mass of the resin solid content, from the viewpoint of further improving the adhesiveness of the copper foil. Parts by mass, more preferably 20 to 30 parts by mass.
  • the thermosetting resin E preferably contains an alkenyl-substituted nadiimide compound from the viewpoint of further improving heat resistance.
  • the alkenyl-substituted nadimide compound is not particularly limited as long as it has one or more alkenyl-substituted nadimide groups in one molecule, and includes, for example, a compound represented by the following formula (2d).
  • R 1 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (eg, a methyl group or an ethyl group);
  • R 2 represents an alkylene group having 1 to 6 carbon atoms; Represents a phenylene group, a biphenylene group, a naphthylene group, or a group represented by the following formula (6) or the following formula (7))
  • R 3 represents a methylene group, an isopropylidene group, CO, O, S, or SO 2.
  • R 4 independently represents an alkylene group having 1 to 4 carbon atoms or a cycloalkylene group having 5 to 8 carbon atoms.
  • alkenyl-substituted nadimide compound represented by the formula (6) or (7) a commercially available product may be used, or a product manufactured according to a known method may be used.
  • Commercially available products include “BANI-M” and “BANI-X” manufactured by Maruzen Petrochemical Co., Ltd.
  • the content of the alkenyl-substituted nadimide compound as the thermosetting resin E is preferably 1 to 40 parts by mass, more preferably 5 to 35 parts by mass, based on 100 parts by mass of the resin solid content. More preferably, it is 30 parts by mass.
  • thermosetting resin E preferably contains an epoxy compound from the viewpoint of further improving chemical resistance, copper foil adhesion and insulation reliability.
  • This epoxy compound refers to an epoxy compound different from the epoxy-modified silicone B and the epoxy compound C constituting the polymer D.
  • the epoxy compound is not particularly limited as long as it is a compound having two or more epoxy groups in one molecule, and examples thereof include bisphenol type epoxy resins (for example, bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol F type resin). Epoxy resin, bisphenol S type epoxy resin), diallyl bisphenol type epoxy resin (for example, diallyl bisphenol A type epoxy resin, diallyl bisphenol E type epoxy resin, diallyl bisphenol F type epoxy resin, diallyl bisphenol S type epoxy resin, etc.), phenols Novolak type epoxy resin (for example, phenol novolak type epoxy resin, bisphenol A novolak type epoxy resin, cresol novolak type epoxy resin), aralkyl type epoxy resin Biphenyl type epoxy resin containing biphenyl skeleton, naphthalene type epoxy resin containing naphthalene skeleton, anthracene type epoxy resin containing dihydroanthracene skeleton, glycidyl ester, polyol type epoxy resin, isocyan
  • Epoxy compounds among these, from the viewpoint of further improving chemical resistance, copper foil adhesion and insulation reliability, aralkyl type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, and bisphenol A type structural unit And at least one selected from the group consisting of epoxy resins comprising a hydrocarbon-based structural unit, and more preferably a naphthalene-type epoxy resin.
  • Ar 3 each independently represents a benzene ring or a naphthalene ring
  • Ar 4 represents a benzene ring, a naphthalene ring, or a biphenyl ring
  • R 3a each independently represents a hydrogen atom or methyl Represents a group
  • k represents an integer of 1 to 50
  • each ring may have a substituent other than a glycidyloxy group (eg, an alkyl group having 1 to 5 carbon atoms or a phenyl group).
  • the compound represented by the formula (3a) includes a compound in which Ar 3 is a naphthalene ring and Ar 4 is a benzene ring (also referred to as a “naphthalene aralkyl type epoxy resin”), and a compound in which Ar 3 is a benzene ring and Ar is It is preferably a compound in which 4 is a biphenyl ring (also referred to as “biphenylaralkyl epoxy resin”), and more preferably a biphenylaralkyl epoxy resin.
  • the biphenyl aralkyl type epoxy resin is preferably a compound represented by the following formula (3b).
  • ka represents an integer of 1 or more, preferably 1 to 20, more preferably 1 to 6.
  • the aralkyl type epoxy resin may be a compound represented by the following formula (3c). (In the formula, ky represents an integer of 1 to 10.)
  • aralkyl-type epoxy resin a commercially available product may be used, or a preparation prepared by a known method may be used.
  • Commercially available naphthalene aralkyl epoxy resins include, for example, "Epototo (registered trademark) ESN-155", “Epototo (registered trademark) ESN-355", and “Epototo (registered trademark) ESN-” manufactured by Nippon Steel & Sumitomo Metal Corporation. 375 ",” Epototo (registered trademark) ESN-475V “,” Epototo (registered trademark) ESN-485 “,” Epototo (registered trademark) ESN-175 “,” NC-7000 “,” Nippon Kayaku Co., Ltd.
  • NC-7300 and NC-7300L and “HP-5000” and “HP-9900” manufactured by DIC Corporation.
  • Examples of commercially available products of the biphenylaralkyl type epoxy resin include “NC-3000”, “NC-3000L”, and “NC-3000FH” manufactured by Nippon Kayaku Co., Ltd.
  • the naphthalene type epoxy resin is not particularly limited.
  • it is an epoxy resin other than the above naphthalene aralkyl type epoxy resin, and is a naphthalene skeleton-containing polyfunctional epoxy having a naphthalene skeleton represented by the following formula (3-1).
  • the resin include an epoxy resin having a naphthalene skeleton.
  • Specific examples of the naphthalene type epoxy resin include, for example, naphthylene ether type epoxy resin and the like. From the viewpoint of further improving chemical resistance, copper foil adhesion and insulation reliability, naphthylene ether type epoxy resin is used. Is preferred.
  • Ar 31 each independently represents a benzene ring or a naphthalene ring
  • Ar 41 represents a benzene ring, a naphthalene ring, or a biphenyl ring
  • R 31a is each independently a hydrogen atom or methyl Represents a group
  • p is an integer of 0 to 2, preferably 0 or 1
  • kz represents an integer of 1 to 50
  • each ring is a substituent other than a glycidyloxy group (for example, a group having 1 carbon atom).
  • the compound represented by the formula (3-1) includes a compound represented by the formula (3-2). (In the formula, R represents a methyl group, and kz has the same meaning as kz in the above formula (3-1).)
  • naphthalene skeleton-containing polyfunctional epoxy resin a commercially available product may be used, or a preparation prepared by a known method may be used.
  • Commercial products of the naphthalene skeleton-containing polyfunctional epoxy resin include, for example, “HP-9540” and “HP-9500” manufactured by DIC Corporation.
  • the naphthylene ether type epoxy resin is represented by the following formula (3-3) or the following formula (3-4) from the viewpoint of further improving chemical resistance, copper foil adhesion and insulation reliability.
  • the compound is (Wherein, R 13 is each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms (eg, a methyl group or an ethyl group), or an alkenyl group having 2 to 3 carbon atoms (eg, a vinyl group, an allyl group) Group or propenyl group).
  • R 14 is each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms (eg, a methyl group or an ethyl group), or an alkenyl group having 2 to 3 carbon atoms (eg, a vinyl group, an allyl group) Group or propenyl group).
  • naphthylene ether type epoxy resin a commercially available product may be used, or a preparation prepared by a known method may be used.
  • Commercially available naphthylene ether type epoxy resins include, for example, "HP-6000", “EXA-7300", “EXA-7310", “EXA-7311”, “EXA-7311L”, “EXA-7311L” manufactured by DIC Corporation.
  • the dicyclopentadiene type epoxy resin is not particularly limited, and examples thereof include a compound represented by the following formula (3-5).
  • R 3c each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and k2 represents an integer of 0 to 10.
  • dicyclopentadiene type epoxy resin a commercially available product may be used, or a preparation prepared by a known method may be used.
  • Commercially available dicyclopentadiene type epoxy resins include "EPICRON @ HP-7200L”, “EPICRON @ HP-7200”, “EPICRON @ HP-7200H”, and "EPICRON @ HP-7000HH” manufactured by Dainippon Ink and Chemicals, Inc. No.
  • Epoxy resin composed of bisphenol A type structural unit and hydrocarbon type structural unit An epoxy resin comprising a bisphenol A-type structural unit and a hydrocarbon-based structural unit (also referred to as a “specific epoxy resin”) has one or more bisphenol A-type structural units and one or more hydrocarbon-based structural units in a molecule. It has a structural unit.
  • the specific epoxy resin include a compound represented by the following formula (3e). (Wherein, R 1x and R 2x each independently represent a hydrogen atom or a methyl group, and R 3x to R 6x each independently represent a hydrogen atom, a methyl group, a chlorine atom, or a bromine atom.
  • X represents an ethyleneoxyethyl group, a di (ethyleneoxy) ethyl group, a tri (ethyleneoxy) ethyl group, a propyleneoxypropyl group, a di (propyleneoxy) propyl group, a tri (propyleneoxy) propyl group, or a group having 2 carbon atoms. Represents up to 15 alkylene groups, and k3 represents a natural number.
  • K3 represents a natural number, preferably 1 to 100, and more preferably 1 to 10.
  • ⁇ ⁇ As the specific epoxy resin, a commercially available product may be used, or a preparation prepared by a known method may be used. Commercial products of specific epoxy resins include "EPICLON @ EXA-4850-150" and "EPICLON @ EXA-4816" manufactured by DIC Corporation.
  • the content of the epoxy compound as the thermosetting resin E is preferably 10 to 70 parts by mass with respect to 100 parts by mass of the resin solid content from the viewpoint of further improving chemical resistance, copper foil adhesion and insulation reliability. Is preferably 15 to 60 parts by mass, more preferably 20 to 50 parts by mass.
  • thermosetting resin E may further contain other resins as long as the effects in the curable compositions of the first and second embodiments are not impaired.
  • other resins include oxetane resins, benzoxazine compounds, and compounds having a polymerizable unsaturated group. These resins may be used alone or in combination of two or more.
  • oxetane resin examples include alkyl oxetanes such as oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, and 3,3-dimethyloxetane; 3-methyl-3-methoxymethyloxetane; '-Di (trifluoromethyl) perfluoxetane, 2-chloromethyloxetane, 3,3-bis (chloromethyl) oxetane, biphenyl-type oxetane, “OXT-101” and “OXT-121” manufactured by Toagosei Co., Ltd. And the like.
  • alkyl oxetanes such as oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, and 3,3-dimethyloxetane; 3-methyl
  • ⁇ The“ benzoxazine compound ”in the present specification refers to a compound having two or more dihydrobenzoxazine rings in one molecule.
  • the benzoxazine compound include “Bisphenol F-type benzoxazine BF-BXZ” and “Bisphenol S-type benzoxazine BS-BXZ” manufactured by Konishi Chemical Co., Ltd.
  • Examples of the compound having a polymerizable unsaturated group include vinyl compounds such as ethylene, propylene, styrene, divinylbenzene, and divinylbiphenyl; methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl ( Monovalent such as (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate Or (meth) acrylates of polyhydric alcohols; epoxy (meth) acrylates such as bisphenol A type epoxy (meth) acrylate and bisphenol F type epoxy (meth) acrylate S; benzocyclobutene resins.
  • vinyl compounds such as ethylene, prop
  • the content of the polymer D is preferably 5 to 50% by mass, more preferably 10 to 45% by mass, and more preferably 10 to 30% by mass based on 100% by mass of the resin solid content. More preferred. When the content is within the above range, the curable composition tends to exhibit more excellent compatibility, low thermal expansion property, and chemical resistance in a well-balanced manner.
  • the content of the polymer D is preferably 5 to 50% by mass, more preferably 10 to 45% by mass, based on 100% by mass of the total of the polymer D and the thermosetting resin E. And more preferably 10 to 30% by mass.
  • the curable composition tends to exhibit more excellent compatibility, low thermal expansion property, and chemical resistance in a well-balanced manner.
  • the curable compositions of the first and second embodiments preferably further contain an inorganic filler from the viewpoint of further improving low thermal expansion.
  • the inorganic filler is not particularly limited and includes, for example, silicas, silicon compounds (eg, white carbon, etc.), metal oxides (eg, alumina, titanium white, zinc oxide, magnesium oxide, zirconium oxide, etc.), metal nitrides (Eg, boron nitride, aggregated boron nitride, silicon nitride, aluminum nitride, etc.), metal sulfate (eg, barium sulfate, etc.), metal hydroxide (eg, aluminum hydroxide, aluminum hydroxide heat-treated product (eg, Heat treatment of aluminum hydroxide to reduce a part of water of crystallization), boehmite, magnesium hydroxide, etc.), molybdenum compound (eg, molybdenum oxide, zinc molybdate, etc.), zinc compound (
  • the inorganic filler may be used alone or in combination of two or more.
  • the inorganic filler is preferably at least one selected from the group consisting of metal hydroxides and metal oxides from the viewpoint of further improving the low thermal expansion property, and silica, boehmite, and alumina are preferred. More preferably, it contains at least one selected from the group consisting of: and more preferably silica.
  • silicas examples include natural silica, fused silica, synthetic silica, Aerosil, and hollow silica. These silicas may be used alone or in combination of two or more. Among these, fused silica is preferable from the viewpoint of dispersibility, and two or more types of fused silica having different particle sizes are more preferable from the viewpoint of filling properties and fluidity.
  • the content of the inorganic filler is preferably from 50 to 1,000 parts by mass, more preferably from 70 to 500 parts by mass, based on 100 parts by mass of the resin solid content, from the viewpoint of further improving the low thermal expansion property. And more preferably 100 to 300 parts by mass.
  • the curable compositions of the first and second embodiments may further contain a silane coupling agent.
  • the curable compositions of the first and second embodiments further include a silane coupling agent, whereby the dispersibility of the inorganic filler is further improved, and components of the curable compositions of the first and second embodiments. , There is a tendency that the adhesive strength with the base material described later can be further improved.
  • the silane coupling agent is not particularly limited, and includes silane coupling agents generally used for surface treatment of inorganic substances.
  • Aminosilane-based compounds eg, ⁇ -aminopropyltriethoxysilane, N- ⁇ - (aminoethyl) - ⁇ -aminopropyltrimethoxysilane, etc.
  • epoxysilane-based compounds eg, ⁇ -glycidoxypropyltrimethoxysilane, etc.
  • acrylsilane-based compounds eg, ⁇ -acryloxypropyltrimethoxysilane, etc.
  • cationic Examples include silane compounds (eg, N- ⁇ - (N-vinylbenzylaminoethyl) - ⁇ -aminopropyltrimethoxysilane hydrochloride), styrylsilane compounds, phenylsilane compounds, and the like.
  • the silane coupling agents may be used alone or in combination of two or more.
  • the silane coupling agent is preferably an epoxy silane compound.
  • the epoxysilane-based compound include “KBM-403”, “KBM-303”, “KBM-402”, and “KBE-403” manufactured by Shin-Etsu Chemical Co., Ltd.
  • the content of the silane coupling agent is not particularly limited, but may be 0.1 to 5.0 parts by mass with respect to 100 parts by mass of the resin solids.
  • the curable compositions of the first and second embodiments may further contain a wetting and dispersing agent.
  • the curable compositions of the first and second embodiments tend to further improve the dispersibility of the filler by containing a wetting and dispersing agent.
  • the wetting dispersant may be any known dispersant (dispersion stabilizer) used for dispersing the filler, such as DISPER @ BYK-110, 111, 118, 180, manufactured by Big Chemie Japan Ltd. 161, BYK-W996, W9010, W903 and the like.
  • the content of the wetting and dispersing agent is not particularly limited, but is preferably 0.5 parts by mass or more and 5.0 parts by mass or less based on 100 parts by mass of the resin solids.
  • the curable compositions of the first and second embodiments may further contain a solvent. Since the curable compositions of the first and second embodiments contain a solvent, the viscosity at the time of preparing the curable composition decreases, and the handling property (handling property) is further improved, and the impregnation property of the base material is improved. Tend to be further improved.
  • the solvent is not particularly limited as long as a part or all of each component in the curable composition can be dissolved, and examples thereof include ketones (eg, acetone and methyl ethyl ketone) and aromatic hydrocarbons (eg, toluene, Xylene, etc.), amides (eg, dimethylformaldehyde, etc.), propylene glycol monomethyl ether and acetate thereof, and the like. These solvents may be used alone or in combination of two or more.
  • ketones eg, acetone and methyl ethyl ketone
  • aromatic hydrocarbons eg, toluene, Xylene, etc.
  • amides eg, dimethylformaldehyde, etc.
  • propylene glycol monomethyl ether and acetate thereof and the like.
  • a method for producing the curable composition of the first and second embodiments for example, there is a method in which the respective components are mixed together or sequentially in a solvent and stirred. At this time, in order to uniformly dissolve or disperse each component, known processes such as stirring, mixing, and kneading are used.
  • the curable composition of the present embodiment can exhibit excellent compatibility, low thermal expansion, and chemical resistance. For this reason, the curable composition of the present embodiment is suitably used for a metal foil-clad laminate and a printed wiring board.
  • the prepreg of the present embodiment includes a base material and the curable composition of the present embodiment impregnated or applied to the base material.
  • the prepreg may be a prepreg obtained by a known method. Specifically, after the curable composition of the present embodiment is impregnated or coated on a substrate, the prepreg is subjected to a temperature of 100 to 200 ° C. And semi-cured (B-staged) by heating and drying.
  • the prepreg of the present embodiment also includes a cured product obtained by thermally curing a semi-cured prepreg at a heating temperature of 180 to 230 ° C. and a heating time of 60 to 180 minutes.
  • the content of the curable composition in the prepreg is preferably from 30 to 90% by volume, more preferably from 35 to 85% by volume, and still more preferably from 40 to 90% by volume in terms of the solid content of the prepreg, based on the total amount of the prepreg. 8080% by volume.
  • the solid content of the prepreg as used herein refers to a component obtained by removing a solvent from the prepreg.
  • a filler is included in the solid content of the prepreg.
  • the substrate is not particularly limited, and includes, for example, known substrates used for various printed wiring board materials.
  • Specific examples of the substrate include a glass substrate, an inorganic substrate other than glass (for example, an inorganic substrate composed of inorganic fibers other than glass such as quartz), an organic substrate (for example, wholly aromatic polyamide, polyester) , An organic substrate composed of organic fibers such as polyparaphenylenebenzoxazole and polyimide). These substrates are used alone or in combination of two or more.
  • a glass substrate is preferable from the viewpoint of further improving the heating dimensional stability.
  • the fibers constituting the glass substrate include fibers such as E glass, D glass, S glass, T glass, Q glass, L glass, NE glass, and HME glass.
  • the fibers constituting the glass substrate are made of E glass, D glass, S glass, T glass, Q glass, L glass, NE glass, and HME glass from the viewpoint of further improving strength and low water absorption. It is preferably one or more fibers selected from the group.
  • the form of the substrate is not particularly limited, and examples thereof include forms such as woven fabric, nonwoven fabric, roving, chopped strand mat, and surfacing mat.
  • the weaving method of the woven fabric is not particularly limited, but, for example, plain weaving, seaweed weaving, twill weaving, and the like are known, and can be appropriately selected and used depending on the intended use or performance from these known ones. . Further, those obtained by subjecting them to fiber opening treatment and glass woven fabrics surface-treated with a silane coupling agent or the like are preferably used.
  • the thickness and mass of the substrate are not particularly limited, but usually those having a thickness of about 0.01 to 0.1 mm are preferably used.
  • the resin sheet of the present embodiment includes a support and the curable composition of the present embodiment disposed on the surface of the support.
  • the resin sheet of the present embodiment may be formed, for example, by applying the curable composition of the present embodiment to one or both surfaces of a support.
  • the resin sheet of the present embodiment can be produced, for example, by directly applying and drying a curable composition used for a prepreg or the like on a support such as a metal foil or a film.
  • the support is not particularly limited. For example, a known support used for various printed wiring board materials can be used, and a resin sheet or a metal foil is preferable.
  • the resin sheet and the metal foil examples include resin sheets such as a polyimide film, a polyamide film, a polyester film, a polyethylene terephthalate (PET) film, a polybutylene terephthalate (PBT) film, a polypropylene (PP) film, and a polyethylene (PE) film.
  • resin sheets such as a polyimide film, a polyamide film, a polyester film, a polyethylene terephthalate (PET) film, a polybutylene terephthalate (PBT) film, a polypropylene (PP) film, and a polyethylene (PE) film.
  • metal foils such as aluminum foil, copper foil, and gold foil.
  • the support is preferably an electrolytic copper foil or a PET film.
  • the resin sheet of the present embodiment is obtained, for example, by applying the curable composition of the present embodiment to a support and then semi-curing (B-stage).
  • the method for producing the resin sheet of the present embodiment is preferably a method for producing a composite of a B-stage resin and a support. Specifically, for example, after applying the curable composition to a support such as a copper foil, the composition is semi-cured by heating in a dryer at 100 to 200 ° C. for 1 to 60 minutes, and the resin sheet is cured. Manufacturing method and the like.
  • the amount of the curable composition adhered to the support is preferably in the range of 1.0 ⁇ m to 300 ⁇ m in terms of the resin thickness of the resin sheet.
  • the resin sheet of the present embodiment can be used as a build-up material for a printed wiring board.
  • the metal foil-clad laminate of the present embodiment is a laminate formed of at least one selected from the group consisting of the prepreg and the resin sheet of the present embodiment, and a metal foil disposed on one or both surfaces of the laminate. And The laminate may be formed of one prepreg or resin sheet, or may be formed of a plurality of prepregs and / or resin sheets.
  • the metal foil may be any metal foil used for various printed wiring board materials, and examples thereof include metal foils such as copper and aluminum.
  • metal foils such as copper and aluminum.
  • the copper metal foil include rolled copper foil and electrolytic copper. Copper foil such as foil.
  • the thickness of the conductor layer is, for example, 1 to 70 ⁇ m, and preferably 1.5 to 35 ⁇ m.
  • the method for forming the metal foil-clad laminate and the molding conditions are not particularly limited, and the methods and conditions for general laminates for printed wiring boards and multilayer boards can be applied.
  • a multi-stage press, a multi-stage vacuum press, a continuous molding machine, an autoclave molding machine, or the like can be used.
  • the temperature is generally 100 to 300 ° C.
  • the pressure is 2 to 100 kgf / cm 2
  • the heating time is generally 0.05 to 5 hours. It is.
  • post-curing can be performed at a temperature of 150 to 300 ° C., if necessary.
  • the temperature is preferably 200 ° C. to 250 ° C.
  • the pressure is 10 to 40 kgf / cm 2
  • the heating time is 80 minutes to 130 minutes
  • the temperature is 215 ° C.
  • the temperature is 235 ° C.
  • the pressure is 25 to 35 kgf / cm 2
  • the heating time is 90 to 120 minutes.
  • a multilayer board can be formed by combining and laminating the above-described prepreg and a separately prepared wiring board for an inner layer.
  • the printed wiring board of the present embodiment has an insulating layer formed of at least one selected from the group consisting of the prepreg and the resin sheet of the present embodiment, and a conductor layer formed on the surface of the insulating layer.
  • the printed wiring board of the present embodiment can be formed, for example, by etching the metal foil of the metal foil-clad laminate of the present embodiment into a predetermined wiring pattern to form a conductor layer.
  • the printed wiring board of the present embodiment can be manufactured, for example, by the following method.
  • a metal foil-clad laminate of the present embodiment is prepared.
  • the metal foil of the metal foil-clad laminate is etched into a predetermined wiring pattern to create an inner substrate having a conductor layer (inner circuit).
  • a predetermined number of insulating layers and a metal foil for the outer layer circuit are laminated in this order on the surface of the conductor layer (interior circuit) of the inner layer substrate, and are heated and pressed to form an integrated body (laminated molding). Obtain a laminate.
  • the method of lamination molding and the molding conditions are the same as the lamination molding method and the molding conditions for the above-described laminate and metal foil-clad laminate.
  • the laminated body is subjected to a drilling process for through holes and via holes, and a plated metal film for electrically connecting the conductor layer (interior circuit) and the metal foil for the outer layer circuit to the wall surface of the hole thus formed.
  • an outer layer substrate having a conductor layer (outer layer circuit) is prepared by etching the metal foil for the outer layer circuit into a predetermined wiring pattern.
  • a printed wiring board is manufactured.
  • a printed circuit board may be manufactured by forming a conductor layer serving as a circuit on the insulating layer. At this time, an electroless plating technique can be used for forming the conductor layer.
  • Example 1 In a three-necked flask equipped with a thermometer and a Dimroth, 5.3 parts by mass of diallyl bisphenol A (DABPA, Daiwa Kasei Kogyo Co., Ltd.), 5.8 parts by mass of biscresol fluorene (BCF, Osaka Gas Chemical Co., Ltd.), epoxy 4.4 parts by mass of modified silicone b1 (X-22-163, Shin-Etsu Chemical Co., Ltd., functional group equivalent 200 g / mol), epoxy-modified silicone b2 (KF-105, Shin-Etsu Chemical Co., Ltd., functional group equivalent 490 g) 8.7 parts by mass, 5.8 parts by mass of biphenyl type epoxy compound c1 (YL-6121H, Mitsubishi Chemical Corporation), propylene glycol monomethyl ether acetate (DOWANOL PMA, Dow Chemical Japan Co., Ltd.) as a solvent 30 parts by mass was added, and the mixture was heated and stirred to 120 ° C.
  • the phenoxy polymer solution contains a polymer D containing a structural unit derived from alkenylphenol A, a structural unit derived from epoxy-modified silicone B, and a structural unit derived from epoxy compound C.
  • the polymer D is also referred to as a phenoxy polymer.
  • Example 2 In the polymer production step, the solid content of the resin composition (including the filler) was changed in the same manner as in Example 1 except that the addition amount of the imidazole catalyst g1 was changed to 1.2 parts by mass instead of 0.3 parts by mass. A prepreg having a content of 46% by mass was obtained.
  • Example 3 In the polymer production step, the addition amount of diallyl bisphenol A was changed to 5.0 parts by mass instead of 5.3 parts by mass, and the addition amount of biscresol fluorene was changed to 5.5 parts by mass instead of 5.8 parts by mass.
  • the addition amount of the modified silicone b1 was changed to 3.7 parts by mass instead of 4.4 parts by mass, the addition amount of the epoxy-modified silicone b2 was changed to 11 parts by mass instead of 8.7 parts by mass, and the addition of the biphenyl type epoxy compound c1 was performed.
  • Example 2 In the same manner as in Example 1, except that the amount was changed to 4.9 parts by mass instead of 5.8 parts by mass, and the addition amount of the imidazole catalyst g1 was changed to 1.2 parts by mass instead of 0.30 part by mass. A prepreg having a resin composition solid content (including a filler) content of 46% by mass was obtained.
  • Example 4 In the polymer production step, the same as Example 1 except that instead of adding 0.3 parts by mass of the imidazole catalyst g1, 1.2 parts by mass of the imidazole catalyst g2 (TPIZ, Tokyo Chemical Industry Co., Ltd.) was added. Thus, a prepreg having a resin composition solid content (including a filler) content of 46% by mass was obtained.
  • Example 5 In the polymer production step, except that 5.8 parts by mass of the biphenyl type epoxy compound c1 was added instead of adding 5.8 parts by mass of the biphenyl type epoxy compound c1 (YX-4000, Mitsubishi Chemical Corporation). In the same manner as in Example 1, a prepreg having a resin composition solid content (including a filler) of 46% by mass was obtained. In addition, the biphenyl type epoxy compound c2 corresponds to "epoxy compound C".
  • Example 6 In the polymer production step, the addition amount of diallylbisphenol A was changed to 5.3 parts by mass to 10 parts by mass, biscresol fluorene was not added, and the addition amount of epoxy-modified silicone b1 was changed to 4.4 parts by mass. 0.5 parts by mass, 9.1 parts by mass instead of 8.7 parts by mass of the epoxy-modified silicone b2, and 6.0 parts by mass instead of 5.8 parts by mass of the biphenyl-type epoxy compound c1. And containing the resin composition solids (including the filler) in the same manner as in Example 1 except that the amount of the imidazole catalyst g1 was changed to 1.2 parts by mass instead of 0.3 part by mass. A prepreg having an amount of 46% by mass was obtained.
  • Example 7 In the polymer production step, the amount of the epoxy-modified silicone b2 was changed to 7.0 parts by mass instead of 11 parts by mass, and the epoxy-modified silicone b3 (X-22-163A, Shin-Etsu Chemical Co., Ltd., functional group equivalent: 1000 g / mol) was added in the same manner as in Example 3 except that 4.0 parts by mass of prepreg was added to obtain a prepreg having a solid content of the resin composition (including the filler) of 46% by mass.
  • the epoxy-modified silicone b3 corresponds to “epoxy-modified silicone B”.
  • Example 8 In the polymer production step, the addition amount of diallyl bisphenol A was changed to 1.7 parts by mass instead of 5.3 parts by mass, and the addition amount of biscresol fluorene was changed to 1.8 parts by mass instead of 5.8 parts by mass.
  • Modified silicone Epoxy-modified silicone b1 was added at 1.2 parts by mass instead of 4.4 parts by mass, and epoxy-modified silicone b2 was added at 3.7 parts by mass instead of 8.7 parts by mass.
  • the addition amount of the epoxy compound c1 was 1.6 parts by mass instead of 5.8 parts by mass
  • the addition amount of the solvent was 10 parts by mass instead of 30 parts by mass
  • the addition amount of the imidazole catalyst g1 was 0.3 parts by mass.
  • Phenoxy polymer solution (solid content: 50% by mass) was obtained in the same manner as in Example 1 except that 0.4 parts by mass was used instead of the above.
  • the addition amount of the ⁇ -naphthol aralkyl type cyanate compound was 33 parts by mass instead of 26 parts by mass
  • the addition amount of the novolak type maleimide compound was 22 parts by mass instead of 17 parts by mass.
  • the content of the resin composition solids (including the filler) was 46 parts by mass. % Prepreg was obtained.
  • Example 9 In the varnish production step, the addition amount of the ⁇ -naphthol aralkyl cyanate ester compound was changed to 26 parts by mass to 50 parts by mass, the novolak type maleimide compound was not added, and the addition amount of the naphthylene ether type epoxy compound was 27 parts by mass.
  • a prepreg having a resin composition solids content (including a filler) of 46% by mass was obtained in the same manner as in Example 3 except that the amount was changed to 50 parts by mass instead of the parts.
  • Example 10 In the varnish formation step, the ⁇ -naphthol aralkyl type cyanate compound was not added, the addition amount of the novolak type maleimide compound was changed to 17 parts by mass to 40 parts by mass, and the naphthylene ether type epoxy compound was not added.
  • Example 11 In the varnish forming step, the ⁇ -naphthol aralkyl type cyanate compound was not added, the addition amount of the novolak type maleimide compound was changed to 17 parts by mass, and the addition amount of the naphthylene ether type epoxy compound was changed to 27 parts by mass. Parts, and 26 parts by mass of a phenol compound (GPH-103, Nippon Kayaku Co., Ltd.) was added in the same manner as in Example 3 except that 26 parts by mass of the resin composition (including a filler) was added. A prepreg having a content of 46% by mass was obtained.
  • a phenol compound GPH-103, Nippon Kayaku Co., Ltd.
  • This varnish was impregnated and coated on an S glass woven cloth (thickness: 100 ⁇ m) and dried by heating at 150 ° C. for 3 minutes to obtain a prepreg having a resin composition solid content (including a filler) of 46% by mass. .
  • Example 4 In the polymer production step, the procedure of Example 1 was repeated except that 5.8 parts by mass of a maleimide compound (BMI-70, K-I Kasei Co., Ltd.) was added instead of 5.8 parts by mass of the biphenyl epoxy compound c1. In the same manner as in Example 4, a prepreg having a resin composition solid content (including a filler) content of 46% by mass was obtained.
  • a maleimide compound BMI-70, K-I Kasei Co., Ltd.
  • This varnish was impregnated and coated on an S glass woven cloth (thickness: 100 ⁇ m) and dried by heating at 150 ° C. for 3 minutes to obtain a prepreg having a resin composition solid content (including a filler) of 46% by mass. .
  • Comparative Example 7 Comparative Example 6 was repeated except that 30 parts by mass of the epoxy-modified silicone b1 was added and 30 parts by mass of the epoxy-modified silicone b2 (KF-105, Shin-Etsu Chemical Co., Ltd., functional group equivalent: 490 g / mol) was added. Thus, a prepreg having a resin composition solid content (including a filler) content of 46% by mass was obtained.
  • Table 1 shows various physical properties of the phenoxy polymer obtained in each of the examples and comparative examples.
  • the weight average molecular weight shown in Table 1 was determined by GPC using polystyrene as a standard substance.
  • the longitudinal linear thermal expansion coefficient of the glass cloth was measured for the insulating layer of the laminate according to the TMA method (Thermo-mechanical analysis) specified in Jls C 6481. Specifically, after removing the copper foil on both surfaces of the copper-clad laminate (5 mm ⁇ 5 mm ⁇ 0.8 mm) obtained above by etching, the copper foil was heated in a constant temperature bath at 220 ° C. for 2 hours, and the stress caused by molding was removed. Was removed. Thereafter, the temperature was raised from 40 ° C. to 320 ° C.
  • thermomechanical analyzer manufactured by TA Instruments
  • CTE linear thermal expansion coefficient
  • the number of epoxy groups / the number of phenol groups refers to the total amount of the number of epoxy groups of the epoxy-modified silicone B and the epoxy compound C with respect to the number of phenol groups of the alkenylphenol A used for preparing the polymer D.
  • B / D represents the content (% by mass) of the structural unit derived from the epoxy-modified silicone B with respect to the polymer D in the phenoxy polymer solution, and the polymer D contains an imidazole catalyst and a solvent. Is not included.
  • C / (B + C) means the content (% by mass) of the structural units derived from the epoxy compound C with respect to the total amount of the structural units derived from the epoxy-modified silicone B and the structural units derived from the epoxy compound C.
  • the present invention has industrial applicability as a curable composition used as a material for prepregs, resin sheets, metal foil-clad laminates, printed wiring boards, and the like.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Textile Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Epoxy Resins (AREA)
  • Reinforced Plastic Materials (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
PCT/JP2019/027496 2018-07-26 2019-07-11 硬化性組成物、プリプレグ、レジンシート、金属箔張積層板及びプリント配線板 Ceased WO2020022084A1 (ja)

Priority Applications (7)

Application Number Priority Date Filing Date Title
JP2020532289A JP7488513B2 (ja) 2018-07-26 2019-07-11 硬化性組成物、プリプレグ、レジンシート、金属箔張積層板及びプリント配線板
CN201980049413.XA CN112469758B (zh) 2018-07-26 2019-07-11 固化性组合物、预浸料、树脂片、覆金属箔层叠板和印刷电路板
KR1020207033129A KR102768029B1 (ko) 2018-07-26 2019-07-11 경화성 조성물, 프리프레그, 레진 시트, 금속박 피복 적층판 및 프린트 배선판
EP19841212.4A EP3828221B1 (en) 2018-07-26 2019-07-11 Curable composition, prepreg, resin sheet, metal foil-clad laminate and printed wiring board
US17/262,872 US11499005B2 (en) 2018-07-26 2019-07-11 Curable composition, prepreg, resin sheet, metal foil-clad laminate and printed wiring board
US17/845,200 US11718708B2 (en) 2018-07-26 2022-06-21 Curable composition, prepreg, resin sheet, metal foil-clad laminate and printed wiring board
JP2023220636A JP7765749B2 (ja) 2018-07-26 2023-12-27 硬化性組成物、プリプレグ、レジンシート、金属箔張積層板及びプリント配線板

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2018-140494 2018-07-26
JP2018140494 2018-07-26

Related Child Applications (2)

Application Number Title Priority Date Filing Date
US17/262,872 A-371-Of-International US11499005B2 (en) 2018-07-26 2019-07-11 Curable composition, prepreg, resin sheet, metal foil-clad laminate and printed wiring board
US17/845,200 Continuation US11718708B2 (en) 2018-07-26 2022-06-21 Curable composition, prepreg, resin sheet, metal foil-clad laminate and printed wiring board

Publications (1)

Publication Number Publication Date
WO2020022084A1 true WO2020022084A1 (ja) 2020-01-30

Family

ID=69181494

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2019/027496 Ceased WO2020022084A1 (ja) 2018-07-26 2019-07-11 硬化性組成物、プリプレグ、レジンシート、金属箔張積層板及びプリント配線板

Country Status (7)

Country Link
US (2) US11499005B2 (enExample)
EP (1) EP3828221B1 (enExample)
JP (2) JP7488513B2 (enExample)
KR (1) KR102768029B1 (enExample)
CN (1) CN112469758B (enExample)
TW (1) TWI815923B (enExample)
WO (1) WO2020022084A1 (enExample)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022032073A3 (en) * 2020-08-07 2022-03-31 Casma Therapeutics, Inc. Trpml modulators
WO2023013710A1 (ja) * 2021-08-05 2023-02-09 三菱瓦斯化学株式会社 プリプレグ、金属箔張積層板及びプリント配線板
WO2023013712A1 (ja) * 2021-08-05 2023-02-09 三菱瓦斯化学株式会社 硬化性組成物、プリプレグ、金属箔張積層板、及びプリント配線板
JPWO2023013715A1 (enExample) * 2021-08-05 2023-02-09
WO2023013716A1 (ja) * 2021-08-05 2023-02-09 三菱瓦斯化学株式会社 硬化性組成物、プリプレグ、レジンシート、金属箔張積層板及びプリント配線板
WO2023013711A1 (ja) * 2021-08-05 2023-02-09 三菱瓦斯化学株式会社 熱硬化性樹脂組成物、プリプレグ及びプリント配線板
WO2023013717A1 (ja) * 2021-08-05 2023-02-09 三菱瓦斯化学株式会社 硬化性組成物、プリプレグ、金属箔張積層板及びプリント配線板

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH044213A (ja) 1990-04-23 1992-01-08 Sumitomo Bakelite Co Ltd 半導体封止用樹脂の製造方法
JPH04314723A (ja) * 1991-04-15 1992-11-05 Fujitsu Ltd エポキシ樹脂組成物
JPH06136093A (ja) * 1992-09-08 1994-05-17 Fujitsu Ltd エポキシ樹脂組成物
JP2012149154A (ja) 2011-01-18 2012-08-09 Hitachi Chemical Co Ltd 熱硬化性樹脂組成物並びにこれを用いたプリプレグ、積層板及び多層プリント配線板
JP2017195334A (ja) 2016-04-22 2017-10-26 三菱瓦斯化学株式会社 プリント配線板用樹脂組成物、プリプレグ、レジンシート、積層板、金属箔張積層板、及びプリント配線板
JP2018140494A (ja) 2015-07-23 2018-09-13 コニカミノルタ株式会社 機能性フィルム及びこれを備えた電子デバイス

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02202910A (ja) * 1989-02-02 1990-08-13 Sumitomo Bakelite Co Ltd 封止用樹脂組成物
US5659004A (en) * 1990-08-27 1997-08-19 Fujitsu Limited Epoxy resin composition
JP3463075B2 (ja) * 1993-03-18 2003-11-05 ナガセケムテックス株式会社 エポキシ樹脂組成物の射出成形方法及びエポキシ樹脂組成物
TW296400B (enExample) * 1994-11-17 1997-01-21 Shinetsu Chem Ind Co
JP2005097448A (ja) * 2003-09-25 2005-04-14 Matsushita Electric Works Ltd 半導体封止用液状エポキシ樹脂組成物及び半導体装置
JP2009097014A (ja) * 2007-09-27 2009-05-07 Hitachi Chem Co Ltd 封止用液状樹脂組成物、電子部品装置及びウエハーレベルチップサイズパッケージ
SG11201407874QA (en) * 2012-06-12 2014-12-30 Mitsubishi Gas Chemical Co Resin composition, prepreg, metal foil-clad laminate and printed wiring board
CN103540101B (zh) 2012-07-17 2016-01-20 台光电子材料(昆山)有限公司 无卤素树脂组合物及应用其的铜箔基板及印刷电路板
SG11201503925QA (en) * 2012-11-28 2015-06-29 Mitsubishi Gas Chemical Co Resin composition, prepreg, laminate, metallic foil clad laminate, and printed circuit board
US10815349B2 (en) * 2015-07-06 2020-10-27 Mitsubishi Gas Chemical Company, Inc. Resin composition, prepreg, resin sheet, metal foil-clad laminate, and printed circuit board
JP6760281B2 (ja) * 2015-07-06 2020-09-23 三菱瓦斯化学株式会社 樹脂組成物、プリプレグ、レジンシート、金属箔張積層板及びプリント配線板
CN106633675B (zh) 2016-12-01 2019-02-19 陕西生益科技有限公司 一种高导热树脂组合物及其应用
WO2018124161A1 (ja) * 2016-12-28 2018-07-05 三菱瓦斯化学株式会社 プリント配線板用樹脂組成物、プリプレグ、レジンシート、積層板、金属箔張積層板、プリント配線板、及び多層プリント配線板

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH044213A (ja) 1990-04-23 1992-01-08 Sumitomo Bakelite Co Ltd 半導体封止用樹脂の製造方法
JPH04314723A (ja) * 1991-04-15 1992-11-05 Fujitsu Ltd エポキシ樹脂組成物
JPH06136093A (ja) * 1992-09-08 1994-05-17 Fujitsu Ltd エポキシ樹脂組成物
JP2012149154A (ja) 2011-01-18 2012-08-09 Hitachi Chemical Co Ltd 熱硬化性樹脂組成物並びにこれを用いたプリプレグ、積層板及び多層プリント配線板
JP2018140494A (ja) 2015-07-23 2018-09-13 コニカミノルタ株式会社 機能性フィルム及びこれを備えた電子デバイス
JP2017195334A (ja) 2016-04-22 2017-10-26 三菱瓦斯化学株式会社 プリント配線板用樹脂組成物、プリプレグ、レジンシート、積層板、金属箔張積層板、及びプリント配線板

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3828221A4

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022032073A3 (en) * 2020-08-07 2022-03-31 Casma Therapeutics, Inc. Trpml modulators
WO2023013710A1 (ja) * 2021-08-05 2023-02-09 三菱瓦斯化学株式会社 プリプレグ、金属箔張積層板及びプリント配線板
WO2023013712A1 (ja) * 2021-08-05 2023-02-09 三菱瓦斯化学株式会社 硬化性組成物、プリプレグ、金属箔張積層板、及びプリント配線板
JPWO2023013715A1 (enExample) * 2021-08-05 2023-02-09
WO2023013715A1 (ja) * 2021-08-05 2023-02-09 三菱瓦斯化学株式会社 硬化性組成物、プリプレグ、レジンシート、金属箔張積層板及びプリント配線板
WO2023013716A1 (ja) * 2021-08-05 2023-02-09 三菱瓦斯化学株式会社 硬化性組成物、プリプレグ、レジンシート、金属箔張積層板及びプリント配線板
WO2023013711A1 (ja) * 2021-08-05 2023-02-09 三菱瓦斯化学株式会社 熱硬化性樹脂組成物、プリプレグ及びプリント配線板
WO2023013717A1 (ja) * 2021-08-05 2023-02-09 三菱瓦斯化学株式会社 硬化性組成物、プリプレグ、金属箔張積層板及びプリント配線板
JPWO2023013717A1 (enExample) * 2021-08-05 2023-02-09
JPWO2023013716A1 (enExample) * 2021-08-05 2023-02-09
JP7276674B1 (ja) * 2021-08-05 2023-05-18 三菱瓦斯化学株式会社 プリプレグ、金属箔張積層板及びプリント配線板
JP7284945B1 (ja) * 2021-08-05 2023-06-01 三菱瓦斯化学株式会社 硬化性組成物、プリプレグ、金属箔張積層板、及びプリント配線板
TWI819735B (zh) * 2021-08-05 2023-10-21 日商三菱瓦斯化學股份有限公司 預浸體、覆金屬箔疊層板及印刷配線板
KR20230174284A (ko) 2021-08-05 2023-12-27 미츠비시 가스 가가쿠 가부시키가이샤 경화성 조성물, 프리프레그, 금속박 피복 적층판, 및 프린트 배선판
KR20230174283A (ko) * 2021-08-05 2023-12-27 미츠비시 가스 가가쿠 가부시키가이샤 경화성 조성물, 프리프레그, 금속박 피복 적층판 및 프린트 배선판
JP7411170B2 (ja) 2021-08-05 2024-01-11 三菱瓦斯化学株式会社 硬化性組成物、プリプレグ、レジンシート、金属箔張積層板及びプリント配線板
JP7428981B2 (ja) 2021-08-05 2024-02-07 三菱瓦斯化学株式会社 硬化性組成物、プリプレグ、レジンシート、金属箔張積層板及びプリント配線板
KR20240021990A (ko) * 2021-08-05 2024-02-19 미츠비시 가스 가가쿠 가부시키가이샤 경화성 조성물, 프리프레그, 레진 시트, 금속박 피복 적층판 및 프린트 배선판
JP7449498B2 (ja) 2021-08-05 2024-03-14 三菱瓦斯化学株式会社 硬化性組成物、プリプレグ、金属箔張積層板及びプリント配線板
KR20240040056A (ko) 2021-08-05 2024-03-27 미츠비시 가스 가가쿠 가부시키가이샤 열경화성 수지 조성물, 프리프레그 및 프린트 배선판
KR20240043744A (ko) 2021-08-05 2024-04-03 미츠비시 가스 가가쿠 가부시키가이샤 프리프레그, 금속박 피복 적층판 및 프린트 배선판
KR102674714B1 (ko) 2021-08-05 2024-06-13 미츠비시 가스 가가쿠 가부시키가이샤 경화성 조성물, 프리프레그, 금속박 피복 적층판 및 프린트 배선판
KR102688208B1 (ko) 2021-08-05 2024-07-25 미츠비시 가스 가가쿠 가부시키가이샤 경화성 조성물, 프리프레그, 레진 시트, 금속박 피복 적층판 및 프린트 배선판
KR102725378B1 (ko) 2021-08-05 2024-11-04 미츠비시 가스 가가쿠 가부시키가이샤 경화성 조성물, 프리프레그, 금속박 피복 적층판, 및 프린트 배선판

Also Published As

Publication number Publication date
JP7488513B2 (ja) 2024-05-22
JPWO2020022084A1 (ja) 2021-08-19
JP7765749B2 (ja) 2025-11-07
TW202010791A (zh) 2020-03-16
EP3828221B1 (en) 2023-05-10
US20220325034A1 (en) 2022-10-13
KR20210037606A (ko) 2021-04-06
JP2024050556A (ja) 2024-04-10
EP3828221A4 (en) 2021-08-25
CN112469758B (zh) 2025-10-28
US11499005B2 (en) 2022-11-15
US20210261722A1 (en) 2021-08-26
KR102768029B1 (ko) 2025-02-13
CN112469758A (zh) 2021-03-09
EP3828221A1 (en) 2021-06-02
TWI815923B (zh) 2023-09-21
US11718708B2 (en) 2023-08-08

Similar Documents

Publication Publication Date Title
JP7765749B2 (ja) 硬化性組成物、プリプレグ、レジンシート、金属箔張積層板及びプリント配線板
JP7428981B2 (ja) 硬化性組成物、プリプレグ、レジンシート、金属箔張積層板及びプリント配線板
JP2024154932A (ja) 熱硬化性樹脂組成物、硬化物、プリプレグ、樹脂シート、金属箔張積層板及びプリント配線板
WO2023013711A1 (ja) 熱硬化性樹脂組成物、プリプレグ及びプリント配線板
JP7411170B2 (ja) 硬化性組成物、プリプレグ、レジンシート、金属箔張積層板及びプリント配線板
JP7284945B1 (ja) 硬化性組成物、プリプレグ、金属箔張積層板、及びプリント配線板
JP7276674B1 (ja) プリプレグ、金属箔張積層板及びプリント配線板
JP7449498B2 (ja) 硬化性組成物、プリプレグ、金属箔張積層板及びプリント配線板
JP2024156371A (ja) 熱硬化性樹脂組成物、硬化物、プリプレグ、樹脂シート、金属箔張積層板及びプリント配線板
JP2024151496A (ja) 熱硬化性組成物、硬化物、プリプレグ、樹脂シート、金属箔張積層板、及びプリント配線板

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: 19841212

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2020532289

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 2019841212

Country of ref document: EP

WWG Wipo information: grant in national office

Ref document number: 201980049413.X

Country of ref document: CN