WO2021134945A1 - 一种热固性树脂组合物及使用其的预浸料、层压板和印制线路板 - Google Patents

一种热固性树脂组合物及使用其的预浸料、层压板和印制线路板 Download PDF

Info

Publication number
WO2021134945A1
WO2021134945A1 PCT/CN2020/082287 CN2020082287W WO2021134945A1 WO 2021134945 A1 WO2021134945 A1 WO 2021134945A1 CN 2020082287 W CN2020082287 W CN 2020082287W WO 2021134945 A1 WO2021134945 A1 WO 2021134945A1
Authority
WO
WIPO (PCT)
Prior art keywords
resin
cyclic olefin
resin composition
olefin copolymer
thermosetting resin
Prior art date
Application number
PCT/CN2020/082287
Other languages
English (en)
French (fr)
Inventor
黄增彪
范华勇
许永静
黄坚龙
佘乃东
Original Assignee
广东生益科技股份有限公司
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 广东生益科技股份有限公司 filed Critical 广东生益科技股份有限公司
Priority to US17/788,966 priority Critical patent/US11732123B2/en
Publication of WO2021134945A1 publication Critical patent/WO2021134945A1/zh

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • 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
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/02—Layered products essentially comprising sheet glass, or glass, slag, or like fibres in the form of fibres or filaments
    • B32B17/04—Layered products essentially comprising sheet glass, or glass, slag, or like fibres in the form of fibres or filaments bonded with or embedded in a plastic substance
    • 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
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/067—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of fibres or filaments
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/04—Anhydrides, e.g. cyclic anhydrides
    • C08F222/06—Maleic anhydride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
    • C08F232/08—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/10—Copolymers of styrene with conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • C08L71/126—Polyphenylene oxides modified by chemical after-treatment
    • 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
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0326—Organic insulating material consisting of one material containing O
    • 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
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/034—Organic insulating material consisting of one material containing halogen
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • 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
    • B32B2250/20—All layers 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
    • 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
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • B32B2260/023—Two or more layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/204—Di-electric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/308—Heat 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/726—Permeability to liquids, absorption
    • B32B2307/7265—Non-permeable
    • 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
    • B32B2307/748—Releasability
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2345/00—Characterised by the use of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2351/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2425/02—Homopolymers or copolymers of hydrocarbons
    • C08J2425/04—Homopolymers or copolymers of styrene
    • C08J2425/08—Copolymers of styrene
    • C08J2425/10—Copolymers of styrene with conjugated dienes
    • 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
    • C08J2445/00—Characterised by the use of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2447/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2471/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08J2471/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08J2471/12—Polyphenylene oxides
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0137—Materials
    • H05K2201/0158—Polyalkene or polyolefin, e.g. polyethylene [PE], polypropylene [PP]
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • 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

Definitions

  • the invention belongs to the technical field of printed circuit boards, and relates to a thermosetting resin composition and prepregs, laminates and printed circuit boards using the thermosetting resin composition.
  • Cyclic-Olefin Copolymers is a new product of copolymerization of cyclic monomers and non-cyclic olefin monomers.
  • COC may refer to ethylene-norbornene copolymer. Its skeleton structure contains cyclic olefin monomer structure. Compared with polypropylene and polyethylene, it is a new class of amorphous and non-crystalline highly transparent polymer.
  • Typical cyclic olefin copolymer materials have higher modulus than high-density polyethylene and polypropylene, are resistant to moisture, have low water absorption, high transparency, high glass transition temperature and high chemical resistance, so they have attracted much attention.
  • COC as a high-performance plastic, is mainly used in large-scale manufacturing of optical components, packaging materials, electronic components, and medical devices by using its optical properties.
  • CN 103159914A discloses a cycloolefin polymer, which is mainly used to manufacture optical parts, packaging materials, electronic parts, medical appliances, etc. by using the characteristics of the polymer's high light transmittance, high refractive index, and high mechanical strength.
  • CN 104086933A discloses a COC bottle and a preparation method thereof, and COC is used for the preparation of plastic bottles.
  • CN 105884971A By adjusting the content of cyclic olefin structural units in the alkene-cyclic olefin copolymer, and making the copolymer include a two-unit group formed by direct bonding of two cyclic olefin structural units, the resulting copolymer can have tensile strength , Elongation at break, processing performance and other aspects showed good performance.
  • the olefin-cycloolefin copolymer and the polymer composition are used to manufacture optical parts, packaging materials, electronic parts, medical devices, and the like.
  • CN 104672888A provides a polyamide molding material containing cyclic olefin copolymer, that is, a molding compound prepared by amorphous polyamide (as the main body) + cyclic olefin copolymer + additives, which also utilizes its good optical properties (that is, high light transmittance). Rate and low haze) are used in optical devices.
  • CN 107216444A A transparent, high heat-resistant cyclic olefin copolymer and a preparation method thereof. The cyclic olefin copolymer is mainly used in the manufacture of various optics, information, electrical appliances, medical materials, etc.
  • COC mainly uses its high light transmittance, high refractive index, high mechanical strength and other characteristics to be used in the manufacture of optical components, packaging materials, electronic components, medical devices, etc. There is no report on the use of COC in the field of printed circuit boards.
  • the purpose of the present invention is to provide a thermosetting resin composition and a prepreg, laminate and printed circuit board using the thermosetting resin composition.
  • the laminate prepared by using the thermosetting resin composition has both good dielectric properties, peeling strength and heat resistance, and can meet various performance requirements for printed circuit board substrates in the current high-frequency and high-speed communication fields.
  • the present invention adopts the following technical solutions:
  • the present invention provides a thermosetting resin composition
  • the thermosetting resin composition includes a resin component, the resin component includes a modified cycloolefin copolymer, and other unsaturated resins;
  • the modified cyclic olefin copolymer is a reaction product of maleic anhydride and a cyclic olefin copolymer.
  • cycloolefin copolymer has very excellent dielectric properties and heat resistance.
  • the D k (10GHz) of pure COC is about 2.35
  • D f (10GHz) is about 0.0004
  • T g (DSC ) At about 170°C, the 5% thermal weight loss temperature is above 430°C; and the common 2116 cloth is glued with the combination of COC+filler, and the performance of the 4 laminated sheet is: D k (10GHz): 3.5
  • D f (10GHz) 0.0020
  • T g (DSC) 175°C
  • 5% weight loss temperature 430°C or higher.
  • COC has excellent dielectric properties and heat resistance, and is expected to be used in the field of copper clad laminates.
  • the peel strength of ordinary COC is very poor and cannot be directly used in copper clad laminates.
  • the present invention forms a modified cyclic olefin copolymer by introducing polar maleic anhydride groups into the cyclic olefin copolymer, which can be cross-linked with itself or other unsaturated resins to form a thermosetting material, and maintain the cyclic olefin copolymer itself. With excellent dielectric properties, it can also significantly improve the bonding performance. In combination with other unsaturated resins, the modified cyclic olefin copolymer can be used as the resin component of the thermosetting resin composition, so that the prepared laminate has good dielectric properties, peel strength and heat resistance.
  • the cycloolefin copolymer is a copolymerization product of monomer A and monomer B, and the monomer A is selected from norbornene, cyclopentadiene, dicyclopentadiene, tricyclopentadiene Diene and One or a combination of at least two of them; the monomer B is selected from one or a combination of at least two of C2-C3 alkenes and C2-C3 alkynes.
  • the number average molecular weight of the modified cycloolefin copolymer is 1000-150000, for example, it can be 1000, 1200, 1500, 1800, 2000, 2200, 2500, 2800, 3000, 3200, 3500, 3800, 4000, 4200 , 4500, 4800, 5000, 6000, 8000, 10000, 20000, 30000, 40000, 50000, 60000, 70000, 80000, 90000, 100000, 110000, 120000, 130000, 140000 or 150000 etc.; more preferably 1500-6000.
  • the number average molecular weight in the present invention is the number average molecular weight measured by gel permeation chromatography.
  • the modified cyclic olefin copolymer needs to have a suitable molecular weight to ensure that the thermosetting resin composition has good wettability, reactivity and appropriate content of maleic anhydride groups, thereby ensuring that the laminate has a lower dielectric Constant and dielectric loss, higher glass transition temperature and peel strength.
  • the molecular weight of the modified cyclic olefin copolymer is too large, its wettability is poor, the reactivity is low, and the peel strength of the prepared laminate is insufficient; if the molecular weight of the modified cyclic olefin copolymer is too small, the maleic anhydride group is in The high proportion of the modified cycloolefin copolymer will lead to poor dielectric properties of the sheet, and also cause excessive resin crosslinking density, which affects the workability of the sheet.
  • the mass of the maleic anhydride accounts for 10-70% of the mass of the cyclic olefin copolymer; for example, it can be 10%, 12%, 15%, 18%, 20%, 22%, 25%, 28% , 30%, 32%, 35%, 38%, 40%, 45%, 50%, 55%, 60%, 65% or 70% etc.
  • the number of units containing carbon-carbon double bonds accounts for 10-70% of the total structural units of the modified cyclic olefin copolymer, for example, it may be 10%, 12%, 15%, 18%, 20%, 22%, 25%, 28%, 30%, 32%, 35%, 38%, 40%, 45%, 50%, 55%, 60%, 65% or 70% Etc.; further preferably 10-30%.
  • the thermosetting resin composition includes a resin component, and the resin component includes a modified cycloolefin copolymer, and other unsaturated resins.
  • the amount of modified cyclic olefin copolymer and other unsaturated resin in the resin component is not limited, and the amount can be adjusted according to needs. Modified cyclic olefin copolymer can be used as the main resin.
  • the resin component includes the modified cyclic olefin copolymer 5-30wt% (for example, 5wt%, 8wt%, 10wt%, 12wt%, 15wt%, 18wt%, 20wt%, 22wt% %, 25wt%, 28wt% or 30wt%, etc.) and other unsaturated resins 70-95wt% (for example, 70wt%, 72wt%, 75wt%, 78wt%, 80wt%, 82wt%, 85wt%, 88wt%, 90wt%, 92% by weight or 95% by weight, etc.) That is, in the present invention, the thermosetting resin composition includes a resin component, and the resin component includes 5-30% by weight of modified cycloolefin copolymer and 70-95% by weight of other unsaturated resins.
  • the thermosetting resin composition includes a resin component, and the resin component includes 5-30% by weight of modified cycloolefin cop
  • the dielectric properties of other unsaturated resin systems can be maintained, and the bonding properties of the resin system can be significantly improved.
  • the content of the modified cyclic olefin copolymer in the resin component is greater than 30wt%, too many polar maleic anhydride groups will be introduced, which will reduce the dielectric properties of the board and also reduce the T g of the board. If the content of the copolymer is less than 5wt%, the introduced polar groups are too few, and the effect of improving the peel strength cannot be achieved.
  • the other unsaturated resin is selected from unmodified unsaturated cyclic olefin copolymers, polyphenylene ether resins with double bonds in the end groups, modified or unmodified polybutadiene resins, modified or unmodified Polyisoprene resin, bismaleimide resin, cyanate ester resin, allyl modified benzoxazine resin, triallyl isocyanurate, cyanuric triene One or a combination of two or more of the propyl esters.
  • the resin component includes 5-30wt% modified cyclic olefin copolymer, 70-95wt% unmodified unsaturated cyclic olefin copolymer; or the resin component includes 5-30wt% modified cyclic olefin copolymer, 70-95wt % Of polyphenylene ether resins with double bonds in the end groups; or the resin component includes 5-30% by weight of modified cyclic olefin copolymer, 70-95% by weight of modified or unmodified polybutadiene resin; or the resin component includes 5-30wt% modified cyclic olefin copolymer, 70-95wt% modified or unmodified polybutadiene resin and polyphenylene ether resin with double bond in the end group; or the resin component includes 5-30wt% modified Cyclic olefin copolymer, 70-95wt% modified or unmodified polybutadiene resin, polyphenylene ether resin with double bond in the end group
  • the other unsaturated resin contains 40-70% (for example, 40%, 42%, 45%, 48%, 50%, 52%, 55%, 58%, 60% of the mass of the resin component). , 62%, 65%, 68% or 70%, etc.) unmodified unsaturated cyclic olefin copolymer.
  • the resin component includes 5-30% by weight of modified cyclic olefin copolymer, 40-70% by weight of unmodified unsaturated cyclic olefin copolymer, and the remaining amount of polyphenylene ether with a double bond in the terminal group; or resin
  • the components include 5-30% by weight of modified cyclic olefin copolymer, 40-70% by weight of unmodified unsaturated cyclic olefin copolymer, and the remaining amount of modified or unmodified polybutadiene resin; or the resin component includes 5-30wt% modified cyclic olefin copolymer, 40-70wt% unmodified unsaturated cyclic olefin copolymer, and the remaining amount of bismaleimide resin; or the resin component includes 5-30wt% modified cyclic olefin Copolymer, 40-70wt% unmodified unsaturated cyclic olefin copolymer, and
  • the resin component of the present invention preferably contains 5-30wt% of the modified cyclic olefin copolymer and 40-70wt% of the unmodified unsaturated cyclic olefin copolymer to ensure The prepared laminate has both good dielectric properties and high peel strength.
  • unmodified unsaturated cyclic olefin copolymer in the present invention refers to an unsaturated cyclic olefin copolymer that has not been modified with maleic anhydride.
  • the polybutadiene resin may include a polybutadiene homopolymer or copolymer resin.
  • the polybutadiene copolymer resin may be a polybutadiene-styrene copolymer resin.
  • the modified polybutadiene resin may be selected from one or more of hydroxyl-terminated polybutadiene resin, methacrylate-terminated polybutadiene resin, and carboxylated polybutadiene resin.
  • the polyisoprene resin may include a polyisoprene homopolymer or copolymer resin.
  • the polyisoprene copolymer resin may be a polyisoprene-styrene copolymer resin.
  • the modified polyisoprene resin may be a carboxylated polyisoprene resin.
  • polybutadiene resins and polyisoprene resins include homopolymers and copolymers containing units derived from butadiene, isoprene, or a mixture thereof. Units derived from other copolymerizable monomers may also be present in the resin, for example, optionally in grafted form.
  • copolymerizable monomers include, but are not limited to, vinyl aromatic monomers, such as substituted and unsubstituted monovinyl aromatic monomers, such as styrene, 3-methylstyrene, 3,5-diethyl Styrene, 4-n-propylstyrene, ⁇ -methylstyrene, ⁇ -methylvinyltoluene, p-hydroxystyrene, p-methoxystyrene, ⁇ -chlorostyrene, ⁇ -bromostyrene , Dichlorostyrene, dibromostyrene, tetrachlorostyrene, etc.; and substituted and unsubstituted divinyl aromatic monomers, such as divinylbenzene, divinyl toluene, etc.
  • vinyl aromatic monomers such as substituted and unsubstituted monovinyl aromatic monomers, such as styrene, 3-methylstyrene, 3,5-
  • polybutadiene resin includes, but is not limited to, butadiene homopolymer, butadiene-vinyl aromatic copolymer (such as butadiene-styrene, etc.); polyisoprene resin includes but not Limited to isoprene homopolymers, isoprene-vinyl aromatic copolymers (such as isoprene-styrene copolymers, etc.).
  • the styrene-butadiene copolymer Ricon100 from Crayvally, or the polybutadiene B-1000, B-2000, B-3000 and the like from Soda Japan can be selected.
  • polybutadiene resin and polyisoprene resin may be modified.
  • the resin may be hydroxyl-terminated, methacrylate-terminated, carboxylate-terminated, or the like.
  • the polybutadiene resin and polyisoprene resin may be epoxy, maleic anhydride, or urethane modified butadiene or isoprene resin.
  • Polybutadiene resins and polyisoprene resins can also be cross-linked, for example, cross-linked with divinyl aromatic compounds (such as divinylbenzene), such as polybutadiene cross-linked with divinylbenzene- Styrene.
  • Exemplary resins are broadly classified as "polybutadiene” by their manufacturers such as Nippon Soda Co. (Tokyo, Japan) and Cray Valley Hydrocarbon Specialty Chemicals (Exton, Pennsylvania, USA). It is also possible to use mixtures of resins, such as mixtures of polybutadiene homopolymers and poly(butadiene-isoprene) copolymers. Combinations containing syndiotactic polybutadiene can also be used.
  • the polybutadiene or polyisoprene polymer may be carboxy functionalized.
  • Functionalization can be accomplished using multifunctional compounds that have (i) carbon-carbon double bonds or carbon-carbon triple bonds in the molecule; and (ii) one or more carboxyl groups, including carboxylic acids, anhydrides, amides, esters or Acid halide.
  • a specific carboxyl group is a carboxylic acid or an ester.
  • polyfunctional compounds that can provide carboxylic acid functional groups include maleic acid, maleic anhydride, fumaric acid, and citric acid.
  • maleic anhydride-added polybutadiene can be used for thermosetting compositions.
  • Suitable maleic anhydride polybutadiene polymers are commercially available, for example from Cray Valley, under the trade names RICON 130MA8, RICON130MA13, RICON130MA20, RICON131MA5, RICON131MA10, RICON131MA17, RICON131MA20, RICON156MA17.
  • Suitable maleic anhydride polybutadiene-styrene copolymers are commercially available, for example from Crayvally under the trade name RICON184MA6.
  • the polyphenylene ether resin having a double bond in its end group may be one or more of methacrylate-terminated polyarylether and vinyl-terminated polyarylether.
  • the structure of the polyphenylene ether resin with a double bond in its end group is represented by the following formula (1):
  • a and b are each independently an integer from 1 to 30,
  • Z is a group represented by formula (2) or (3):
  • A is an arylene group having 6 to 30 carbon atoms, a carbonyl group, or an alkylene group having 1 to 10 carbon atoms
  • m is an integer of 0 to 10
  • R 1 to R 3 are each Independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms
  • R 4 and R 6 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or a phenyl group; and R 5 and R 7 are each independently a hydrogen atom, a halogen atom , Alkyl or phenyl having 1 to 10 carbon atoms;
  • R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 and R 15 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or Phenyl; and B is an arylene group having 6 to 30 carbon atoms, an alkylene group having 1 to 10 carbon atoms, -O-, -CO-, -SO-, -CS- or -SO 2- .
  • the alkyl group having 1 to 10 carbon atoms is preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably an alkyl group having 1 to 4 carbon atoms. base.
  • Examples of the alkyl group having 1 to 8 carbon atoms may include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl, as well as cyclopropyl, cyclobutyl, cyclopentyl and Cyclohexyl. Where there are isomeric forms, all isomeric forms are included.
  • butyl may include n-butyl, isobutyl, and tert-butyl.
  • Examples of the arylene group having 6 to 30 carbon atoms may include a phenylene group, a naphthylene group, and an anthrylene group.
  • the alkylene group having 1 to 10 carbon atoms is preferably an alkylene group having 1 to 8 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and still more preferably an alkylene group having 1 to 6 carbon atoms.
  • 4 is an alkylene group.
  • alkylene groups having 1 to 10 carbon atoms may include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylidene and Decyl, as well as cyclopropylene, cyclobutylene, cyclopentylene and cyclohexylene. Where there are isomeric forms, all isomeric forms are included.
  • halogen atom may include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the number average molecular weight of the polyphenylene ether resin may be 500 to 10000 g/mol, preferably 800 to 8000 g/mol, more preferably 1000 to 7000 g/mol.
  • Exemplary polyphenylene ether can be methacrylate-modified polyphenylene ether SA9000 from Sabic, or styryl-modified polyphenylene ether St-PPE-1 from Mitsubishi Chemical.
  • the bismaleimide resin is selected from: DDM type, DDS type BMI, and can also be selected from silicone, aliphatic chain or amine chain extended BMI.
  • Cyanate resin is selected from: bisphenol A cyanate, bisphenol E cyanate, bisphenol F cyanate, bisphenol M cyanate, phenolic cyanate (LONZA BA-3000S) , Dicyclopentadiene type cyanate ester, tetramethyl bisphenol F type cyanate ester, bisphenol A type cyanate ester prepolymer.
  • the resin component may also include other saturated resins, such as saturated cyclic olefin copolymers, epoxy resins and the like.
  • the thermosetting resin composition includes: 10-90 parts of resin components, 0-60 parts of fillers and flame retardants 5-20 servings.
  • the weight parts of the resin component can be 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, 28 parts, 30 parts, 32 parts, 35 parts, 38 parts. , 40, 42, 45, 48, 50, 52, 55, 58, 60, 62, 65, 68, 70, 72, 75, 78, 80 Parts, 82 parts, 85 parts, 88 parts or 90 parts, etc.
  • the parts by weight of the filler can be 0 parts, 2 parts, 5 parts, 8 parts, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, 28 parts, 30 parts, 32 parts , 35, 38, 40, 42, 45, 48, 50, 52, 55, 58, 60, etc.
  • the parts by weight of the flame retardant can be 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 12 parts, 13 parts, 15 parts, 16 parts, 18 parts or 20 parts, etc.
  • the filler is an inorganic filler and/or an organic filler.
  • the inorganic filler is selected from aluminum hydroxide, boron nitride, aluminum oxide, silicon nitride, aluminum nitride, silicon dioxide, talc, mica, barium sulfate, lithopone, calcium carbonate, wollastonite , Kaolin, brucite, diatomaceous earth, bentonite and pumice powder any one or a mixture of at least two.
  • the organic filler is selected from one or a mixture of at least two of polyether ether ketone (PEEK) powder, polytetrafluoroethylene (PTFE) powder or acrylic resin powder.
  • PEEK polyether ether ketone
  • PTFE polytetrafluoroethylene
  • the median particle size of the filler is 0.05-30 ⁇ m.
  • the flame retardant is selected from bromine-containing flame retardants or halogen-free flame retardants.
  • the flame retardant is selected from phosphate flame retardants (such as OP935), phosphate ester flame retardants (such as PX200 and PX202) and phosphazene flame retardants (such as SPB-100). ) Or a combination of at least two.
  • thermosetting resin composition further includes 0.1-3 parts of initiator.
  • the initiator is an azo initiator or a peroxide initiator; for example, BPO, DCP, or azobisisobutyronitrile.
  • the present invention provides a prepreg comprising a reinforcing material, and the thermosetting resin composition according to the first aspect attached to the reinforcing material after being impregnated and dried.
  • thermosetting resin composition described in the first aspect can be dissolved or dispersed in a solvent to obtain a resin glue solution; then the reinforcing material can be infiltrated with the resin glue solution, The prepreg is obtained after heating and drying.
  • solvents examples include: ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, and primary alcohol; Ethers such as methyl ether and propylene glycol monomethyl ether; esters such as propylene glycol methyl ether acetate and ethyl acetate; aprotic solvents such as N,N-dimethylformamide and N,N-diethylformamide.
  • the above-mentioned solvents can be used alone or in a mixture of multiple types, preferably toluene aromatic hydrocarbon solvents. Those skilled in the art can choose the amount of the solvent to use based on experience, so that the obtained resin glue can reach a suitable viscosity for use. .
  • the reinforcing material can be an inorganic or organic reinforcing material.
  • inorganic reinforcing materials include woven fabrics, non-woven fabrics, or paper such as glass fiber, carbon fiber, boron fiber, and metal.
  • the glass fiber cloth or non-woven cloth may be E-glass, Q-shaped cloth, NE cloth, D-shaped cloth, S-shaped cloth, high silica cloth, and the like.
  • organic reinforcing materials include woven fabrics or non-woven fabrics or paper made of polyester, polyamine, polyacrylic acid, polyimide, aramid, polytetrafluoroethylene, and syndiotactic polystyrene.
  • the temperature of heating and drying may be 80-250°C, preferably 120-180°C; for example, it may be 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C, 200°C, 210°C, 220°C, 230°C, 240°C or 250°C, etc.; time can be 1-30min, preferably 1-10min; for example, it can be 1min, 2min, 3min, 5min, 8min, 10min, 12min, 15min, 18min, 20min, 22min, 25min, 28min or 30min etc.
  • the content of the thermosetting resin composition in the prepreg may be 30-95 wt%, preferably 60-90 wt%; for example, it may be 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt% %, 70wt%, 75wt% or 80wt%, etc.
  • the present invention provides a resin film, which is formed by semi-curing the thermosetting resin composition described in the first aspect after being baked and heated.
  • the present invention provides a resin-coated copper foil obtained by coating the thermosetting resin composition of the first aspect on the copper foil and forming a semi-cured state by heating.
  • the present invention provides a laminated board comprising one or at least two laminated prepregs according to the second aspect.
  • the present invention provides a metal-clad laminate, the metal-clad laminate includes one or at least two laminated prepregs of the second aspect, and a sheet of prepreg Or the metal foil on one or both sides of the laminated prepreg.
  • the present invention has no special restrictions on the preparation method of the metal-clad laminate.
  • the following method can be used: one or more prepregs are cut into a certain size for lamination and then sent to the lamination equipment for lamination.
  • the metal foil is placed on one or both sides of the prepreg, and the prepreg is pressed by hot pressing to form a metal foil-clad laminate.
  • metal foil copper, brass, aluminum, nickel, and alloys or composite metal foils of these metals can be used.
  • the pressing conditions of the laminate can be selected: the lamination temperature is 130-250°C (for example, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C, 200°C, 210°C, 220°C, 230°C , 240 deg.] C, or 250 deg.] C, etc.), a pressure of 3-50kgf / cm 2 (e.g.
  • hot pressing time is 60-240min (e.g. 60min, 70min, 80min, 90min, 100min, 120min, 150min, 180min , 200min, 220min or 240min, etc.).
  • the present invention provides a printed wiring board, which is manufactured by removing part of the metal foil on the surface of the metal-clad laminate as described in the sixth aspect to form a circuit.
  • the present invention has the following beneficial effects:
  • the present invention forms a modified cyclic olefin copolymer by introducing polar maleic anhydride groups into the cyclic olefin copolymer, which can be cross-linked with itself or other unsaturated resins to form a thermosetting material, and maintain the cyclic olefin copolymer itself. With excellent dielectric properties, it can also significantly improve the bonding performance.
  • the modified cyclic olefin copolymer can be used as the resin component of the thermosetting resin composition in combination with other unsaturated resins, and the prepared copper clad laminate can be used as a printed circuit board substrate in the field of high-frequency and high-speed communication.
  • a maleic anhydride modified cyclic olefin copolymer A-1 is provided, and the preparation steps are as follows:
  • Step 1 Synthesis of ethylene-norbornene copolymer: vacuumize the 500mL polymerizer after heating and dry it with nitrogen for two times, then evacuate and then introduce ethylene gas, and then add 4mL methylaluminoxane toluene solution in sequence (1.5mmol/mL), 66mL of toluene after anhydrous and oxygen-free treatment and 20mL of norbornene solution in toluene (2mmol/mL). Under mechanical stirring, 3 atmospheres of ethylene was introduced to saturation, and the pressure was controlled by supplementing ethylene. 3 standard atmospheres and react at 40°C for 2h under this pressure to obtain a cycloolefin copolymer.
  • a maleic anhydride modified cyclic olefin copolymer A-2 is provided, and the preparation steps are as follows:
  • Step 1 Synthesis of TCPD-ethylene copolymer: The 500mL polymerizer after heating and drying was evacuated and vented with nitrogen twice, then ethylene gas was ventilated, and then 4mL of methylaluminoxane in toluene solution (1.5 mmol/mL), 66mL of toluene after anhydrous and oxygen-free treatment, and 20mL of TCPD toluene solution (2mmol/mL), and 3 atmospheres of ethylene was introduced to saturation under mechanical stirring, and the pressure was controlled to 3 standard atmospheres by supplementing ethylene. And reacted at 40°C for 2h under this pressure to obtain an unmodified unsaturated cycloolefin copolymer (B-4).
  • A-2 maleic anhydride modified cyclic olefin copolymer
  • a maleic anhydride modified cyclic olefin copolymer A-3 is provided.
  • the preparation method is different from Preparation Example 2 in that in step (2), hydrogenation is performed until the carbon-carbon double bond content is zero.
  • (C) Filler Spherical silica powder (commodity model SFP-30M, Electric Chemical Industry Co., Ltd.);
  • Examples 1-9 each provide a copper clad laminate, and the preparation method is as follows:
  • component A modified cyclic olefin copolymer, component B other unsaturated resins except modified cyclic olefin copolymer, component C filler, component D flame retardant, and component E initiator are added in proportion Mix evenly in the solvent toluene to obtain a resin glue solution with a solid content of 65%.
  • Hot pressing conditions temperature 210°C, pressure 25kg/cm 2 , The pressing time is 90min.
  • a copper clad laminate is provided.
  • the difference from Example 1 is that the maleic anhydride modified cycloolefin copolymer A-1 is replaced with an unmodified unsaturated cycloolefin copolymer B-4.
  • a copper clad laminate is provided.
  • the difference from Example 3 is that the styrene butadiene resin B-3 is replaced with the epoxy resin B-6.
  • a copper-clad laminate is provided.
  • the difference from Example 4 is that the unmodified unsaturated cyclic olefin copolymer B-4 is replaced with the saturated cyclic olefin copolymer B-5.
  • T d 5% Thermal decomposition temperature
  • the glass transition temperature of the copper-clad laminate prepared by the thermosetting resin composition provided by the present invention reaches 200-225°C, and the temperature at which the thermal weight loss is 5% is 420- At 435°C, the peeling strength reaches 0.91-1.09N/mm, the thermal stratification time is above 60min, the dielectric constant D k (10GHz) is 3.5-3.75, the dielectric loss factor D f (10GHz) is 0.0021-0.003, and the water absorption rate It is 0.018-0.2%, has good heat resistance, dielectric properties, higher peel strength, lower water absorption, and is suitable for high-frequency and high-speed communications.
  • a saturated resin can also be added.
  • an appropriate amount of saturated COC is added, because the COC has good dielectric properties, but the Tg and peel strength of the copper clad laminates prepared therefrom are relatively low.
  • Comparative Example 2 uses epoxy resin instead of unsaturated styrene-butadiene resin, and the prepared copper clad laminate has very poor dielectric properties and heat resistance, which cannot meet high-frequency applications.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)

Abstract

提供了一种热固性树脂组合物及使用其的预浸料、层压板和印制线路板。所述热固性树脂组合物包括树脂组分，所述树脂组分包括改性环烯烃共聚物，以及其他不饱和树脂；所述改性环烯烃共聚物为马来酸酐与环烯烃共聚物的反应产物，所述环烯烃共聚物为单体A与单体B的共聚产物，所述单体A选自降冰片烯、环戊二烯、双环戊二烯、三环戊二烯和（I）中的一种或至少两种的组合；所述单体B选自C2-C3的烯烃和C2-C3炔烃中的一种或至少两种的组合。采用所提供的热固性树脂组合物制备的层压板兼具良好的介电性能、剥离强度和耐热性，可满足当下高频、高速通信领域对印制线路板基材的各项性能要求。

Description

一种热固性树脂组合物及使用其的预浸料、层压板和印制线路板 技术领域
本发明属于印制线路板技术领域，涉及一种热固性树脂组合物及使用其的预浸料、层压板和印制线路板。
背景技术
5G时代的到来，目前对高性能电子设备的需求增加，在使用半导体基材和印刷电路板的领域中需要更高的频率。由于电信号在高频率区的传输损耗和介电损耗与频率成正比，所以传输损耗朝向更高的频率区增加，这不利地影响电子设备的性能、耐久性和生产率。因此，需要开发具有低介电常数和低介电损耗因子特征的材料以减少这些缺陷。
在常规的通信和网络领域中，聚苯醚和聚烯烃树脂也被用作低介电材料，但由于聚苯醚预浸体易破碎而出现可操作性问题，且介电损耗因子不能做到足够低；而聚烯烃树脂也存在一些不足，如C＝C双键的位置会影响固化程度，固化不足会有热氧老化问题—这将是未来高频通信领域最致命的弱点，因此，仍然需要开发在具有足够的机械性能的同时具有低介电常数、低介电损耗、碳碳双键残留少的材料。
环烯烃共聚物，简称COC(Cyclic-Olefin Copolymers)，是环状单体与非环烯烃单体共聚的新产品。常规地，且更具体地，COC可以指乙烯-降冰片烯共聚物。其骨架结构中包含环状烯烃单体结构，相比较聚丙烯和聚乙烯而言，是一类新的无定形非晶态高透明聚合物。典型的环烯烃共聚物材料比高密度聚乙烯和聚丙烯模量高，且防潮湿，吸水率低，具有高透明性，高玻璃化转变温度和高耐化学品性，因此倍受关注。
目前COC作为高性能塑料，主要是利用其光学特性大规模运用于制造光学 部件、包装材料、电子部件、医疗器具等。CN 103159914A公开了一种环烯烃聚合物，其主要是利用该聚合物的高透光率、高折射率、高力学强度等特性运用于制造光学部件、包装材料、电子部件、医疗器具等。CN 104086933A公开了一种COC瓶及其制备方法，将COC用于塑料瓶的制备。CN 105884971A通过在链烯烃-环烯烃共聚物中调节环烯烃结构单元的含量，并使共聚物包含两个环烯烃结构单元直接键合形成的二单元组，可以使得到的共聚物在拉伸强度、断裂伸长率、加工性能等方面表现出良好的性能。但该链烯烃-环烯烃共聚物和该聚合物组合物用于制造光学部件、包装材料、电子部件、医疗器具等。CN 104672888A提供一种包含环烯烃共聚物的聚酰胺模塑材料，即无定型聚酰胺(作为主体)+环烯烃共聚物+添加剂制备的模塑料，也是利用其良好的光学性质(即高透光率和低雾度)用于光学器件。CN 107216444A一种透明、高耐热环烯烃共聚物及其制备方法，该环烯烃共聚物主要运用于制造各种光学、信息、电器、医用材料等。
目前对于COC的开发，主要是利用其高透光率、高折射率、高力学强度等特性，将其运用于制造光学部件、包装材料、电子部件、医疗器具等。目前尚无将COC用于印制线路板领域的报道。
发明内容
针对现有技术存在的不足，本发明的目的在于提供一种热固性树脂组合物及使用其的预浸料、层压板和印制线路板。采用该热固性树脂组合物制备的层压板兼具良好的介电性能、剥离强度和耐热性，可满足当下高频、高速通信领域对印制线路板基材的各项性能要求。
为达此目的，本发明采用以下技术方案：
一方面，本发明提供一种热固性树脂组合物，所述热固性树脂组合物包括 树脂组分，所述树脂组分包括改性环烯烃共聚物，以及其他不饱和树脂；
所述改性环烯烃共聚物为马来酸酐与环烯烃共聚物的反应产物。
发明人通过研究发现，环烯烃共聚物(COC)具有非常优异的介电性能和耐热性，单纯COC的D k(10GHz)在2.35左右，D f(10GHz)在0.0004左右，T g(DSC)在170℃左右，5％热失重温度在430℃以上；而采用COC+填料的组合上胶普通2116布，4层压制板材后其性能达到：D k(10GHz)：3.5，D f(10GHz)：0.0020，T g(DSC)：175℃，5％热失重温度：430℃以上。可见COC具有优异的介电性能和耐热性，有望用于覆铜板领域。但是普通COC的剥离强度非常差，并不能直接用于覆铜板中。
本发明通过在环烯烃共聚物中引入极性的马来酸酐基团，形成了改性环烯烃共聚物，其可以与自身或其他不饱和树脂交联形成热固性材料，在保持环烯烃共聚物本身优异的介电性能的同时，还可以明显提升粘结性能。这种改性环烯烃共聚物与其他不饱和树脂配合，可作为热固性树脂组合物的树脂组分，使制备得到的层压板兼具良好的介电性能、剥离强度和耐热性。
作为本发明的优选技术方案，所述环烯烃共聚物为单体A与单体B的共聚产物，所述单体A选自降冰片烯、环戊二烯、双环戊二烯、三环戊二烯和
Figure PCTCN2020082287-appb-000001
中的一种或至少两种的组合；所述单体B选自C2-C3的烯烃和C2-C3炔烃中的一种或至少两种的组合。
优选地，所述改性环烯烃共聚物的数均分子量为1000-150000，例如可以是1000、1200、1500、1800、2000、2200、2500、2800、3000、3200、3500、3800、4000、4200、4500、4800、5000、6000、8000、10000、20000、30000、40000、50000、60000、70000、80000、90000、100000、110000、120000、130000、140000 或150000等；进一步优选为1500-6000。
需要说明的是，本发明中所述数均分子量均是通过凝胶渗透色谱发测得的数均分子量。
本发明中，改性环烯烃共聚物需要具有合适的分子量，以保证热固性树脂组合物具有良好的浸润性、反应活性和适当的马来酸酐基团含量，进而保证层压板具有较低的介电常数和介电损耗，较高的玻璃化转变温度和剥离强度。若改性环烯烃共聚物的分子量过大，则其浸润性较差，反应活性低，制备的层压板剥离强度不足；若改性环烯烃共聚物的分子量过小，则马来酸酐基团在改性环烯烃共聚物中的比例较高，会导致板材介电性能差，另外也会导致树脂交联密度过大，影响板材加工性等。
优选地，所述马来酸酐的质量占所述环烯烃共聚物质量的10-70％；例如可以是10％、12％、15％、18％、20％、22％、25％、28％、30％、32％、35％、38％、40％、45％、50％、55％、60％、65％或70％等。
优选地，所述改性环烯烃共聚物中，含有碳碳双键的单元数量占所述改性环烯烃共聚物的结构单元总量的10-70％，例如可以是10％、12％、15％、18％、20％、22％、25％、28％、30％、32％、35％、38％、40％、45％、50％、55％、60％、65％或70％等；进一步优选为10-30％。
本发明中，改性环烯烃共聚物主链上优选保留一定含量的碳碳双键，以便于后续的交联固化。若其碳碳双键含量过少，容易导致交联度不足，层压板的玻璃化转变温度和剥离强度较低；若其碳碳双键含量过高，则容易导致制备的层压板的交联密度过高，使得板材过硬，难以加工，此外若交联密度过高，会有部分C＝C双键不能完全交联，残留在板材内部，最终导致板材的热氧老化性能差。
本发明中，热固性树脂组合物包括树脂组分，所述树脂组分包括改性环烯烃共聚物，以及其他不饱和树脂。改性环烯烃共聚物与其他不饱和树脂在树脂组分的用量不限，可以根据需要调整用量。改性环烯烃共聚物可以做主体树脂，添加一定量的其它不饱和树脂，可以获得在D k、耐热性和玻璃强度方面性能优异的高频基材；在树脂组分中其它不饱和树脂也可以做主体树脂，添加一定量的改性环烯烃共聚物，在保持介电性能的同时，能明显提升树脂体系的粘结性能。
作为本发明的优选技术方案，所述树脂组分包括所述改性环烯烃共聚物5-30wt％(例如5wt％、8wt％、10wt％、12wt％、15wt％、18wt％、20wt％、22wt％、25wt％、28wt％或30wt％等)和其他不饱和树脂70-95wt％(例如70wt％、72wt％、75wt％、78wt％、80wt％、82wt％、85wt％、88wt％、90wt％、92wt％或95wt％等)即本发明中，热固性树脂组合物包括树脂组分，所述树脂组分包括5-30wt％改性环烯烃共聚物，70-95wt％其他不饱和树脂。在此范围既可以保持其它不饱和树脂体系的介电性能，又能明显提升树脂体系的粘结性能。当树脂组分中改性环烯烃共聚物的含量大于30wt％时，会引入过多的极性马来酸酐基团，降低板材的介电性能同时也会降低板材T g，如果改性环烯烃共聚物的含量小于5wt％，则引入的极性基团过少，达不到提升剥离强度的作用。
优选地，所述其他不饱和树脂选自未改性不饱和环烯烃共聚物、端基含双键的聚苯醚树脂、改性或未改性的聚丁二烯树脂、改性或未改性的聚异戊二烯树脂、双马来酰亚胺树脂、氰酸酯树脂、烯丙基改性的苯并噁嗪树脂、三烯丙基异氰脲酸酯、三聚氰酸三烯丙基酯中的一种或两种以上组合。例如，树脂组分包括5-30wt％改性环烯烃共聚物，70-95wt％未改性不饱和环烯烃共聚物；或树脂组分包括5-30wt％改性环烯烃共聚物，70-95wt％端基含双键的聚苯醚树脂； 或树脂组分包括5-30wt％改性环烯烃共聚物，70-95wt％改性或未改性的聚丁二烯树脂；或树脂组分包括5-30wt％改性环烯烃共聚物，70-95wt％改性或未改性的聚丁二烯树脂和端基含双键的聚苯醚树脂；或树脂组分包括5-30wt％改性环烯烃共聚物，70-95wt％改性或未改性的聚丁二烯树脂和端基含双键的聚苯醚树脂以及三烯丙基异氰脲酸酯等。
优选地，所述其他不饱和树脂中含有占所述树脂组分质量40-70％(例如40％、42％、45％、48％、50％、52％、55％、58％、60％、62％、65％、68％或70％等)的未改性不饱和环烯烃共聚物。例如本发明中，树脂组分包括5-30wt％改性环烯烃共聚物，40-70wt％未改性不饱和环烯烃共聚物，以及剩余量的端基含双键的聚苯醚；或树脂组分包括5-30wt％改性环烯烃共聚物，40-70wt％未改性不饱和环烯烃共聚物，以及剩余量的改性或未改性的聚丁二烯树脂；或树脂组分包括5-30wt％改性环烯烃共聚物，40-70wt％未改性不饱和环烯烃共聚物，以及剩余量的双马来酰亚胺树脂；或树脂组分包括5-30wt％改性环烯烃共聚物，40-70wt％未改性不饱和环烯烃共聚物，以及剩余量的改性或未改性的聚丁二烯树脂和端基含双键的聚苯醚等。
由于环烯烃共聚物具有优异的介电性能，因此本发明中树脂组分优选含有5-30wt％所述改性环烯烃共聚物和40-70wt％未改性不饱和环烯烃共聚物，以保证制备的层压板同时具有良好的介电性能和较高的剥离强度。
需要说明的是，本发明中所述“未改性不饱和环烯烃共聚物”是指未用马来酸酐改性的不饱和环烯烃共聚物。
可选地，聚丁二烯树脂可以包括聚丁二烯均聚物或共聚物树脂。聚丁二烯共聚物树脂可以是聚丁二烯-苯乙烯共聚物树脂。改性的聚丁二烯树脂可以选自羟基封端的聚丁二烯树脂、甲基丙烯酸酯封端的聚丁二烯树脂和羧基化的聚丁 二烯树脂中的一种或多种。
可选地，聚异戊二烯树脂可以包括聚异戊二烯均聚物或共聚物树脂。聚异戊二烯共聚物树脂可以是聚异戊二烯-苯乙烯共聚物树脂。所述改性的聚异戊二烯树脂可以是羧基化的聚异戊二烯树脂。
具体地，聚丁二烯树脂、聚异戊二烯树脂包括含有源自丁二烯、异戊二烯或其混合物的单元的均聚物和共聚物。源自其他可共聚单体的单元也可以存在于树脂中，例如可选地以接枝的形式存在。示例性的，可共聚单体包括但不限于乙烯基芳香族单体，例如取代和未取代的单乙烯基芳香族单体，如苯乙烯、3-甲基苯乙烯、3,5-二乙基苯乙烯、4-正丙基苯乙烯、α-甲基苯乙烯、α-甲基乙烯基甲苯、对羟基苯乙烯、对甲氧基苯乙烯、α-氯苯乙烯、α-溴苯乙烯、二氯苯乙烯、二溴苯乙烯、四氯苯乙烯等；以及取代的和未取代的二乙烯基芳香族单体，如二乙烯基苯、二乙烯基甲苯等。也可以使用包含至少一种前述可共聚单体的组合物。示例性的，聚丁二烯树脂包括但不限于丁二烯均聚物、丁二烯-乙烯基芳香族共聚物(如丁二烯-苯乙烯等)；聚异戊二烯树脂包括但不限于异戊二烯均聚物、异戊二烯-乙烯基芳香族共聚物(如异戊二烯-苯乙烯共聚物等)。示例性的，可以选择来自Crayvally的苯乙烯-丁二烯共聚物Ricon100，或是来自日本曹达的聚丁二烯B-1000、B-2000、B-3000等。
可选地，聚丁二烯树脂、聚异戊二烯树脂可以被改性，例如树脂可以是羟基封端、甲基丙烯酸酯封端、羧酸酯封端等的树脂。聚丁二烯树脂、聚异戊二烯树脂可以是环氧、顺丁烯酸酐、或尿烷改性的丁二烯或异戊二烯树脂。聚丁二烯树脂、聚异戊二烯树脂也可以被交联，例如经二乙烯基芳香族化合物(如二乙烯基苯)交联，如用二乙烯基苯交联的聚丁二烯-苯乙烯。示例性树脂在广义上被其制造商如Nippon Soda Co.(日本东京)和Cray Valley Hydrocarbon Specialty  Chemicals(美国宾夕法尼亚州埃克斯顿(Exton))分类为“聚丁二烯”。也可以使用树脂的混合物，例如聚丁二烯均聚物和聚(丁二烯-异戊二烯)共聚物的混合物。还可以使用包含间规聚丁二烯的组合。
可选地，聚丁二烯或聚异戊二烯聚合物可以是羧基官能化的。官能化可以利用如下多官能化合物完成：其在分子内具有(i)碳-碳双键或碳-碳三键；和(ii)一个或多个羧基，包括羧酸、酸酐、酰胺、酯或酸性卤化物。一种特定的羧基是羧酸或酯。可提供羧酸官能团的多官能化合物的实例包括顺丁烯二酸、顺丁烯二酸酐、反丁烯二酸、和柠檬酸。特别地，加合顺丁烯二酸酐的聚丁二烯可用于热固性组合物。合适的马来酐化聚丁二烯聚合物可市购获得，例如来自CrayValley，商品名为RICON 130MA8、RICON130MA13、RICON130MA20、RICON131MA5、RICON131MA10、RICON131MA17、RICON131MA20、RICON156MA17。合适的马来酐化聚丁二烯-苯乙烯共聚物可市购获得，例如来自Crayvally，商品名为RICON184MA6。
可选地，端基含双键的聚苯醚树脂可以为甲基丙烯酸酯封端的聚芳醚、含乙烯基封端的聚芳醚中的一种或多种。
可选地，端基含双键的聚苯醚树脂的结构由下式(1)所示：
Figure PCTCN2020082287-appb-000002
式(1)中，a和b各自独立地为1至30的整数，
Z为由式(2)或(3)所示的基团：
Figure PCTCN2020082287-appb-000003
Figure PCTCN2020082287-appb-000004
式(3)中，A为碳原子数为6至30的亚芳基、羰基、或碳原子数为1至10的亚烷基，m为0至10的整数，并且R 1至R 3各自独立地为氢原子或者碳原子数为1至10的烷基；
式(1)中的-(-O-Y-)-为由式(4)所示的基团：
Figure PCTCN2020082287-appb-000005
式(4)中，R 4和R 6各自独立地为氢原子、卤原子、碳原子数为1至10的烷基或苯基；并且R 5和R 7各自独立地为氢原子，卤原子、碳原子数为1至10的烷基或苯基；
式(1)中的-(-O-X-O-)-为由式(5)所示的基团：
Figure PCTCN2020082287-appb-000006
式(5)中，R 8、R 9、R 10、R 11、R 12、R 13、R 14和R 15各自独立地为氢原子，卤原子、碳原子数为1至10的烷基或苯基；并且B为碳原子数为6至30的亚芳基、碳原子数为1至10的亚烷基、-O-、-CO-、-SO-、-CS-或-SO 2-。
碳原子数为1至10的烷基优选为碳原子数为1至8的烷基，再优选为碳原子数为1至6的烷基，再更优选为碳原子数为1至4的烷基。碳原子数为1至8的烷基的实例可以包括甲基、乙基、丙基、丁基、戊基、己基、庚基和辛基， 以及环丙基、环丁基、环戊基和环己基。在存在异构形式的情况下，包含所有的异构形式。例如，丁基可以包括正丁基、异丁基和叔丁基。
碳原子数为6至30的亚芳基的实例可以包括亚苯基、亚萘基和亚蒽基。
碳原子数为1至10的亚烷基优选为碳原子数为1至8的亚烷基，更优选为碳原子数为1至6的亚烷基，再更优选为碳原子数为1至4的亚烷基。碳原子数为1至10的亚烷基的实例可以包括亚甲基、亚乙基、亚丙基、亚丁基、亚戊基、亚己基、亚庚基、亚辛基、亚壬基和亚癸基，以及亚环丙基、亚环丁基、亚环戊基和亚环己基。在存在异构形式的情况下，包含所有的异构形式。
卤原子的实例可以包括氟原子、氯原子、溴原子和碘原子。
优选地，所述聚苯醚树脂的数均分子量可以为500至10000g/mol，优选800至8000g/mol，进一步优选1000至7000g/mol。示例性的聚苯醚可以是来自Sabic的甲基丙烯酸酸酯基改性的聚苯醚SA9000、或是来自三菱化学的苯乙烯基改性的聚苯醚St-PPE-1。
双马来酰亚胺树脂选自：DDM型、DDS型BMI，也可以选自有机硅、脂肪链或胺类扩链的BMI。
氰酸酯树脂选自：双酚A型氰酸酯、双酚E型氰酸酯、双酚F型氰酸酯、双酚M型氰酸酯、酚醛型氰酸酯(LONZA BA-3000S)、双环戊二烯型氰酸酯、四甲基双酚F型氰酸酯、双酚A型氰酸酯预聚体。
优选地，所述树脂组分还可以包括其它饱和树脂，如饱和环烯烃共聚物、环氧树脂等。
作为本发明的优选技术方案，以所述热固性树脂组合物的总重量份数为100份计，所述热固性树脂组合物包括：树脂组分10-90份、填料0-60份和阻燃剂5-20份。
本发明中，所述树脂组分的重量份数可以是10份、12份、15份、18份、20份、22份、25份、28份、30份、32份、35份、38份、40份、42份、45份、48份、50份、52份、55份、58份、60份、62份、65份、68份、70份、72份、75份、78份、80份、82份、85份、88份或90份等。
所述填料的重量份数可以是0份、2份、5份、8份、10份、12份、15份、18份、20份、22份、25份、28份、30份、32份、35份、38份、40份、42份、45份、48份、50份、52份、55份、58份或60份等。
所述阻燃剂的重量份数可以是5份、6份、7份、8份、9份、10份、12份、13份、15份、16份、18份或20份等。
作为本发明的优选技术方案，所述填料为无机填料和/或有机填料。
优选地，所述无机填料选自氢氧化铝、氮化硼、氧化铝、氮化硅、氮化铝、二氧化硅、滑石粉、云母、硫酸钡、立德粉、碳酸钙、硅灰石、高岭土、水镁石、硅藻土、膨润土和浮石粉中的任意一种或者至少两种的混合物。
优选地，所述有机填料选自聚醚醚酮(PEEK)粉、聚四氟乙烯(PTFE)粉或丙烯酸树脂粉中的一种或至少两种的混合物。
优选地，所述填料的中位粒径为0.05-30μm。
优选地，所述阻燃剂选自含溴阻燃剂或无卤阻燃剂。
作为本发明的优选技术方案，所述阻燃剂选自磷酸盐类阻燃剂(如OP935)、磷酸酯类阻燃剂(如PX200和PX202)和磷腈类阻燃剂(如SPB-100)中的一种或至少两种的组合。
优选地，所述热固性树脂组合物还包括0.1-3份引发剂。
优选地，所述引发剂为偶氮类引发剂或过氧化物类引发剂；例如BPO、DCP或偶氮二异丁腈等。
第二方面，本发明提供一种预浸料，所述预浸料包括增强材料，和通过含浸干燥后附着在所述增强材料上的第一方面所述的热固性树脂组合物。
本发明对预浸料的制备方法没有特殊限制，示例性的，可以将第一方面所述的热固性树脂组合物溶解或分散在溶剂中，得到树脂胶液；然后用树脂胶液浸润增强材料，加热干燥后得到预浸料。
其中，可使用的溶剂的实例有：丙酮、甲基乙基酮、甲基异丁基酮等酮类；甲苯、二甲苯等烃类；甲醇、乙醇、伯醇等醇类；乙二醇单甲醚、丙二醇单甲醚等醚类；丙二醇甲醚醋酸酯、乙酸乙酯等酯类；N,N-二甲基甲酰胺、N,N-二乙基甲酰胺等非质子溶剂。上述溶剂可以单独使用，也可以多种混合使用，优选甲苯类芳香烃溶剂，所述溶剂的使用量本领域技术人员可以根据经验来选择，使得到的树脂胶液达到适于使用的粘度即可。
增强材料可为无机或有机增强材料。无机增强材料可列举的有：玻璃纤维、碳纤维、硼纤维、金属等的机织织物或无纺布或纸。其中，玻璃纤维布或无纺布可以是E-glass、Q型布、NE布、D型布、S型布、高硅氧布等。有机增强材料可列举的有：聚酯、聚胺、聚丙烯酸、聚酰亚胺、芳纶、聚四氟乙烯、间规聚苯乙烯等制造的织布或无纺布或纸。
加热干燥的温度可以为80-250℃，优选120-180℃；例如可以是80℃、90℃、100℃、110℃、120℃、130℃、140℃、150℃、160℃、170℃、180℃、190℃、200℃、210℃、220℃、230℃、240℃或250℃等；时间可以为1-30min，优选1-10min；例如可以是1min、2min、3min、5min、8min、10min、12min、15min、18min、20min、22min、25min、28min或30min等。
预浸料中的热固性树脂组合物的含量可以为30-95wt％，优选60-90wt％；例如可以是30wt％、35wt％、40wt％、45wt％、50wt％、55wt％、60wt％、65 wt％、70wt％、75wt％或80wt％等。
第三方面，本发明提供一种树脂膜，所述树脂膜由第一方面所述的热固性树脂组合物经烘烤加热后半固化而成。
第四方面，本发明提供一种涂树脂铜箔，所述涂树脂铜箔是通过将第一方面所述的热固性树脂组合物涂覆于铜箔上，并经由加热形成半固化态而得到。
第五方面，本发明提供一种层压板，所述层压板包括一张或至少两张叠合的第二方面所述的预浸料。
第六方面，本发明提供一种覆金属箔层压板，所述覆金属箔层压板包括一张或至少两张叠合的第二方面所述的预浸料，以及覆于一张预浸料或叠合后的预浸料的一侧或两侧的金属箔。
本发明对覆金属箔层压板的制备方法没有特殊限制，示例性的，可以采用如下方法：将一个或多个预浸料裁剪成一定尺寸进行叠片后送入层压设备中进行层压，同时将金属箔放置在半固化片的一侧或两侧，通过热压成型将半固化压制形成覆金属箔层压板。
其中，金属箔可以使用铜、黄铜、铝、镍、以及这些金属的合金或复合金属箔。
层压板的压制条件可以选择：层压温度为130-250℃(例如130℃、140℃、150℃、160℃、170℃、180℃、190℃、200℃、210℃、220℃、230℃、240℃或250℃等)，压力为3-50kgf/cm 2(例如3kgf/cm 2、5kgf/cm 2、10kgf/cm 2、15kgf/cm 2、20kgf/cm 2、25kgf/cm 2、30kgf/cm 2、35kgf/cm 2、40kgf/cm 2、45kgf/cm 2或50kgf/cm 2等)，热压时间为60-240min(例如60min、70min、80min、90min、100min、120min、150min、180min、200min、220min或240min等)。
第七方面，本发明提供一种印制线路板，所述印制线路板是通过去除第六 方面所述的覆金属箔层压板表面的部分金属箔而形成电路的方法制得。
与现有技术相比，本发明具有以下有益效果：
本发明通过在环烯烃共聚物中引入极性的马来酸酐基团，形成了改性环烯烃共聚物，其可以与自身或其他不饱和树脂交联形成热固性材料，在保持环烯烃共聚物本身优异的介电性能的同时，还可以明显提升粘结性能。这种改性环烯烃共聚物与其他不饱和树脂配合，可作为热固性树脂组合物的树脂组分，制备的覆铜板可用作高频、高速通信领域的印制线路板基材。
具体实施方式
下面通过具体实施例来进一步说明本发明的技术方案。本领域技术人员应该明了，所述实施例仅仅是帮助理解本发明，不应视为对本发明的具体限制。
制备例1
提供一种马来酸酐改性的环烯烃共聚物A-1，其制备步骤如下：
步骤1、乙烯-降冰片烯共聚物的合成：将经过加热干燥后的500mL聚合釜抽真空通氮气两次，再抽真空后通入乙烯气体，然后依次加入甲基铝氧烷的甲苯溶液4mL(1.5mmol/mL)、经过无水无氧处理的甲苯66mL以及降冰片烯的甲苯溶液20mL(2mmol/mL)，并在机械搅拌下通入3个大气压乙烯至饱和，通过补充乙烯控制压力为3个标准大气压，并在此压力下于40℃反应2h，得到环烯烃共聚物。
步骤2、在步骤1的基础上，加入占步骤1得到的环烯烃共聚物质量10％的马来酸酐单体，反应3h，保证C＝C双键剩余15％，由于马来酸酐中含有C＝C双键，因此可以与环烯烃共聚物中的双键反应而接枝到环烯烃共聚物分子链上，反应结束将反应液倒入无水甲醇中，析出大量白色聚合物，过滤得到的产品以丙酮洗涤3次后放入真空烘箱中40℃下干燥12小时，得到马来酸酐改性的环烯 烃共聚物，记为A-1。
采用凝胶渗透色谱检测得知，数均分子量M n为3510，分子量分布指数M w/M n为1.52。
制备例2
提供一种马来酸酐改性的环烯烃共聚物A-2，其制备步骤如下：
步骤1、TCPD-乙烯共聚物的合成：将经过加热干燥后的500mL聚合釜抽真空通氮气两次，再抽真空后通入乙烯气体，然后依次加入甲基铝氧烷的甲苯溶液4mL(1.5mmol/mL)、经过无水无氧处理的甲苯66mL以及TCPD的甲苯溶液20mL(2mmol/mL)，并在机械搅拌下通入3个大气压乙烯至饱和，通过补充乙烯控制压力为3个标准大气压，并在此压力下于40℃反应2h，得到未改性不饱和环烯烃共聚物(B-4)。
步骤2、在步骤1的基础上，加入占步骤1得到的环烯烃共聚物质量30％的马来酸酐单体，反应3h，保证C＝C双键剩余30％，由于马来酸酐中含有C＝C双键，因此可以与环烯烃共聚物中的双键反应而接枝到环烯烃共聚物分子链上，反应结束将反应液倒入无水甲醇中，析出大量白色聚合物。过滤得到的产品以丙酮洗涤3次后放入真空烘箱中40℃下干燥12小时，得到马来酸酐改性的环烯烃共聚物，记为A-2。
采用凝胶渗透色谱检测得知，数均分子量M n为5120，分子量分布指数M w/M n为1.63。
制备例3
提供一种马来酸酐改性的环烯烃共聚物A-3，其制备方法与制备例2的区别在于，步骤(2)中加氢至碳碳双键含量为0。
下述实施例中采用的原料种类和来源如下：
(A)环烯烃共聚物
A-1马来酸酐改性的环烯烃共聚物(制备例1制备)；
A-2马来酸酐改性的环烯烃共聚物(制备例2制备)；
A-3马来酸酐改性的环烯烃共聚物(制备例3制备)；
(B)其他树脂
B-1烯丙基改性聚苯醚树脂(商品型号PP501，台湾晋一)；
B-2聚丁二烯(商品型号日本曹达B-3000)；
B-3丁苯树脂(商品型号Ricon 100)；
B-4未改性不饱和性环烯烃共聚物(为制备例2的中间产物)
B-5饱和环烯烃共聚物(商品型号TOPAS 6017)
B-6环氧树脂(商品型号E-51环氧树脂)；
(C)填料：球形硅微粉(商品型号SFP-30M，电气化学工业株式会社)；
(D)阻燃剂：苯氧基磷腈化合物(商品型号SPB-100，日本大塚化学株式会社)；
(E)引发剂：过氧化二异丙苯(上海高桥)。
实施例1-9
实施例1-9各提供一种覆铜箔层压板，其制备方法如下：
(1)树脂胶液的制备
将组分A改性环烯烃共聚物、组分B除改性环烯烃共聚物之外的其他不饱和树脂、组分C填料、组分D阻燃剂，以及组分E引发剂按比例加入溶剂甲苯中，混合均匀，得到固含量为65％的树脂胶液。
(2)半固化片的制备
用2116#玻纤布作为增强材料，浸润配制好的树脂胶液，在155℃烘箱中烘 烤3min，制成半固化片(粘结片)。
(3)覆铜箔层压板的制备
按照一定尺寸裁剪半固化片，6张叠合整齐，双面覆上35μm厚的电解铜箔，在真空压机中加压加热固化，制备覆铜板热压条件：温度210℃，压力25kg/cm 2，压制时间90min。
对比例1
提供一种覆铜箔层压板，与实施例1的区别在于，将马来酸酐改性的环烯烃共聚物A-1替换为未改性不饱和性环烯烃共聚物B-4。
对比例2
提供一种覆铜箔层压板，与实施例3的区别在于，将丁苯树脂B-3替换为环氧树脂B-6。
对比例3
提供一种覆铜箔层压板，与实施例4的区别在于，将未改性不饱和环烯烃共聚物B-4替换为饱和环烯烃共聚物B-5。
实施例1-9和对比例1-3中采用的原料种类、用量(重量份)和得到的覆铜箔层压板的性能数据如下表1和表2所示：
表1
Figure PCTCN2020082287-appb-000007
Figure PCTCN2020082287-appb-000008
表2
Figure PCTCN2020082287-appb-000009
Figure PCTCN2020082287-appb-000010
上述性能的测试方法如下：
(1)玻璃化转变温度(T g)：使用DSC测试，按照IPC-TM-650 2.4.24所规定的DSC测试方法进行测定；
(2)燃烧性：按照UL94所规定的燃烧性方法进行测定；
(3)热分层时间：用TMA仪，按照IPC-TM-650 2.4.24.1所规定的T288测试方法进行测定；
(4)剥离强度：按照IPC-TM-650 2.4.8方法进行测试；
(5)热分解温度(T d5％)：使用TGA测试，按照IPC-TM-650 2.4.24.6所规定的TGA测试方法进行测定，以热失重5％时的温度作为热分解温度；
(6)吸水率：按照IPC-TM-650 2.6.2.1所规定的吸水性测试方法进行测定；
(7)介电常数(D k)和介电损耗因子(D f)：按照SPDR方法测定；
由上述表1和表2的测试结果可以看出，采用本发明提供的热固性树脂组合物制备的覆铜箔层压板的玻璃化转变温度达到200-225℃，热失重5％的温度 为420-435℃，剥离强度达到0.91-1.09N/mm，热分层时间在60min以上，介电常数D k(10GHz)为3.5-3.75，介电损耗因子D f(10GHz)为0.0021-0.003，吸水率为0.018-0.2％，具有良好的耐热性、介电性能，较高的剥离强度，较低的吸水率，适合用于高频、高速通信领域。
在本发明中还可以添加饱和树脂，例如实施例5中添加适量的饱和COC，因该COC具有良好的介电性能，但是由其制备的覆铜板的Tg和剥离强度偏低。
其中，与实施例1相比，对比例1中采用未改性的不饱和COC替换马来酸酐改性的COC，由于其没有极性基团，因此制备的覆铜板的剥离强度差。
与实施例3相比，对比例2由于采用环氧树脂代替不饱和的丁苯树脂，制备的覆铜板的介电性能及耐热性都非常差，不能满足高频应用。
与实施例4相比，对比例3只采用了商品化的非改性环烯烃共聚物TOPAS6017，而没有其它不饱和树脂，由于无可反应的C＝C，不能形成三维交联网络，所以采用其的覆铜板的Tg、耐浸焊等耐热性能，以及剥离强度较差。
申请人声明，以上所述仅为本发明的具体实施方式，但本发明的保护范围并不局限于此，所属技术领域的技术人员应该明了，任何属于本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到的变化或替换，均落在本发明的保护范围和公开范围之内。

Claims (10)

  1. 一种热固性树脂组合物，其特征在于，所述热固性树脂组合物包括树脂组分，所述树脂组分包括改性环烯烃共聚物，以及其他不饱和树脂；
    所述改性环烯烃共聚物为马来酸酐与环烯烃共聚物的反应产物。
  2. 根据权利要求1所述的热固性树脂组合物，其特征在于，所述环烯烃共聚物为单体A与单体B的共聚产物，所述单体A选自降冰片烯、环戊二烯、双环戊二烯、三环戊二烯和
    Figure PCTCN2020082287-appb-100001
    中的一种或至少两种的组合；所述单体B选自C2-C3的烯烃和C2-C3炔烃中的一种或至少两种的组合；
    优选地，所述改性环烯烃共聚物的数均分子量为1000-150000，进一步优选为1500-6000；
    优选地，所述马来酸酐的质量占所述环烯烃共聚物质量的10-70％；
    优选地，所述改性环烯烃共聚物中，含有碳碳双键的单元数量占所述改性环烯烃共聚物的结构单元总量的10-70％，进一步优选为10-30％。
  3. 根据权利要求1或2所述的热固性树脂组合物，其特征在于，所述树脂组分包括所述改性环烯烃共聚物5-30wt％和其他不饱和树脂70-95wt％；
    优选地，所述其他不饱和树脂选自未改性不饱和环烯烃共聚物、端基含双键的聚苯醚树脂、改性或未改性的聚丁二烯树脂、改性或未改性的聚异戊二烯树脂、双马来酰亚胺树脂、氰酸酯树脂、烯丙基改性的苯并噁嗪树脂、三烯丙基异氰脲酸酯、三聚氰酸三烯丙基酯中的一种或两种以上组合；
    优选地，所述其他不饱和树脂中含有占所述树脂组分质量40-70％的未改性不饱和环烯烃共聚物。
    优选地，所述树脂组分还包括饱和树脂。
  4. 根据权利要求1-3任一项所述的热固性树脂组合物，其特征在于，以所 述热固性树脂组合物的总重量份数为100份计，所述热固性树脂组合物包括树脂组分10-90份、填料0-60份和阻燃剂5-20份；
    优选地，所述填料为无机填料和/或有机填料；
    优选地，所述无机填料选自氢氧化铝、氮化硼、氧化铝、氮化硅、氮化铝、二氧化硅、滑石粉、云母、硫酸钡、立德粉、碳酸钙、硅灰石、高岭土、水镁石、硅藻土、膨润土和浮石粉中的任意一种或者至少两种的混合物；
    优选地，所述有机填料选自聚醚醚酮粉、聚四氟乙烯粉或丙烯酸树脂粉中的一种或至少两种的混合物；
    优选地，所述填料的中位粒径为0.05-30μm；
    优选地，所述阻燃剂选自含溴阻燃剂或无卤阻燃剂；
    优选地，所述无卤阻燃剂选自磷酸酯类阻燃剂、磷腈类阻燃剂和磷酸盐类阻燃剂中的一种或至少两种的组合；
    优选地，所述热固性树脂组合物还包括0.1-3份引发剂；
    优选地，所述引发剂为偶氮类引发剂或过氧化物类引发剂；
    优选地，所述引发剂为BPO、DCP或偶氮二异丁腈。
  5. 一种预浸料，其特征在于，所述预浸料包括增强材料，和通过含浸干燥后附着在所述增强材料上的如权利要求1-4任一项所述的热固性树脂组合物。
  6. 一种树脂膜，其特征在于，所述树脂膜由权利要求1-4任一项所述的热固性树脂组合物经烘烤加热后半固化而成。
  7. 一种涂树脂铜箔，其特征在于，所述涂树脂铜箔是通过将权利要求1-4任一项所述的热固性树脂组合物涂覆于铜箔上，并经由加热形成半固化态而得到。
  8. 一种层压板，其特征在于，所述层压板包括一张或至少两张叠合的如权 利要求5所述的预浸料。
  9. 一种覆金属箔层压板，其特征在于，所述覆金属箔层压板包括一张或至少两张叠合的如权利要求5所述的预浸料，以及覆于一张预浸料或叠合后的预浸料的一侧或两侧的金属箔。
  10. 一种印制线路板，其特征在于，所述印制线路板是通过去除权利要求9所述的覆金属箔层压板表面的部分金属箔而形成电路的方法制得。
PCT/CN2020/082287 2019-12-31 2020-03-31 一种热固性树脂组合物及使用其的预浸料、层压板和印制线路板 WO2021134945A1 (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US17/788,966 US11732123B2 (en) 2019-12-31 2020-03-31 Thermosetting resin composition, and prepreg, laminate and printed circuit board using same

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201911410412.1A CN113121943B (zh) 2019-12-31 2019-12-31 一种热固性树脂组合物及使用其的预浸料、层压板和印制线路板
CN201911410412.1 2019-12-31

Publications (1)

Publication Number Publication Date
WO2021134945A1 true WO2021134945A1 (zh) 2021-07-08

Family

ID=76686313

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2020/082287 WO2021134945A1 (zh) 2019-12-31 2020-03-31 一种热固性树脂组合物及使用其的预浸料、层压板和印制线路板

Country Status (4)

Country Link
US (1) US11732123B2 (zh)
CN (1) CN113121943B (zh)
TW (1) TWI729761B (zh)
WO (1) WO2021134945A1 (zh)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI825805B (zh) * 2022-06-24 2023-12-11 南亞塑膠工業股份有限公司 橡膠樹脂材料及金屬基板

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1854173A (zh) * 2005-04-29 2006-11-01 三星电机株式会社 采用改性环烯烃共聚物的织物增强体和印刷电路板用树脂基板
CN101115348A (zh) * 2006-07-24 2008-01-30 南亚塑胶工业股份有限公司 聚丁二烯热固性树脂印刷电路载板组成及其制法
CN103467967A (zh) * 2013-09-16 2013-12-25 广东生益科技股份有限公司 一种热固性树脂组合物及其用途
CN108148332A (zh) * 2016-12-02 2018-06-12 臻鼎科技股份有限公司 树脂组合物及应用该树脂组合物的胶片及电路板
CN108395538A (zh) * 2017-02-08 2018-08-14 臻鼎科技股份有限公司 树脂组合物、膜层及两者对应的制备方法、电路板
CN108623974A (zh) * 2017-03-15 2018-10-09 臻鼎科技股份有限公司 低介电树脂组合物及应用其的胶片及电路板
CN109294223A (zh) * 2018-09-21 2019-02-01 上海金发科技发展有限公司 一种具有高介电强度的阻燃组合物及其制备方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998018837A1 (fr) * 1996-10-29 1998-05-07 Nippon Zeon Co., Ltd. Polymere norbornene thermoplastique modifie et procede de production
CN107771125B (zh) 2015-06-09 2020-07-28 罗杰斯公司 电路材料和由其形成的制品
WO2018016527A1 (ja) 2016-07-22 2018-01-25 京セラ株式会社 有機絶縁体、金属張積層板および配線基板

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1854173A (zh) * 2005-04-29 2006-11-01 三星电机株式会社 采用改性环烯烃共聚物的织物增强体和印刷电路板用树脂基板
CN101115348A (zh) * 2006-07-24 2008-01-30 南亚塑胶工业股份有限公司 聚丁二烯热固性树脂印刷电路载板组成及其制法
CN103467967A (zh) * 2013-09-16 2013-12-25 广东生益科技股份有限公司 一种热固性树脂组合物及其用途
CN108148332A (zh) * 2016-12-02 2018-06-12 臻鼎科技股份有限公司 树脂组合物及应用该树脂组合物的胶片及电路板
CN108395538A (zh) * 2017-02-08 2018-08-14 臻鼎科技股份有限公司 树脂组合物、膜层及两者对应的制备方法、电路板
CN108623974A (zh) * 2017-03-15 2018-10-09 臻鼎科技股份有限公司 低介电树脂组合物及应用其的胶片及电路板
CN109294223A (zh) * 2018-09-21 2019-02-01 上海金发科技发展有限公司 一种具有高介电强度的阻燃组合物及其制备方法

Also Published As

Publication number Publication date
TW202126742A (zh) 2021-07-16
US11732123B2 (en) 2023-08-22
TWI729761B (zh) 2021-06-01
US20230063436A1 (en) 2023-03-02
CN113121943B (zh) 2022-11-29
CN113121943A (zh) 2021-07-16

Similar Documents

Publication Publication Date Title
CN107771125B (zh) 电路材料和由其形成的制品
US9890276B2 (en) Composite material, high-frequency circuit substrate made therefrom and making method thereof
TWI778506B (zh) 一種熱固性樹脂組成物、使用其的半固化片與覆銅箔層壓板
TWI658083B (zh) 一種熱固性樹脂組合物及使用其製作的半固化片與覆金屬箔層壓板
TWI730599B (zh) 覆銅層壓板及印刷電路板
TWI658054B (zh) 一種熱固性樹脂組合物及使用其製作的半固化片與覆金屬箔層壓板
WO2013029271A1 (zh) 无卤树脂组合物以及使用其制作覆铜板的方法
TWI740445B (zh) 一種熱固性樹脂組合物及使用其的預浸料、層壓板及印刷電路板
CN110527037B (zh) 一种无卤聚苯醚树脂组合物及使用其制作的半固化片和层压板
WO2015120650A1 (zh) 一种无卤树脂组合物及其用途
CN113088061B (zh) 一种热固性树脂组合物及使用其的预浸料、层压板和覆金属箔层压板
TWI729761B (zh) 一種熱固性樹脂組合物及使用其的預浸料、層壓板及印刷電路板
JP2020183525A (ja) ブロックコポリマー組成物、それから作製されたプリプレグ及び積層体
CN114106267B (zh) 含苯乙烯化合物的热固性树脂组合物及其制备方法和应用
CN114230787B (zh) 改性苯并噁嗪预聚物及其制备方法、树脂组合物及其固化产物和电子产品组件
CN112236464A (zh) 树脂组合物、预浸料、覆金属箔层叠板、树脂片及印刷电路板
CN116285378A (zh) 一种树脂组合物及包含其的粘结片、覆金属箔层压板
TWI763402B (zh) 一種熱固性樹脂組成物及其應用
WO2015120651A1 (zh) 一种无卤树脂组合物及其用途
CN116285192A (zh) 一种树脂组合物及包含其的预浸料、覆金属箔层压板
CN118043384A (zh) 预浸料、层叠板及印刷电路板

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: 20910155

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20910155

Country of ref document: EP

Kind code of ref document: A1