WO2023026829A1 - 樹脂組成物、硬化物、プリプレグ、金属箔張積層板、樹脂シート、および、プリント配線板 - Google Patents

樹脂組成物、硬化物、プリプレグ、金属箔張積層板、樹脂シート、および、プリント配線板 Download PDF

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Publication number
WO2023026829A1
WO2023026829A1 PCT/JP2022/030138 JP2022030138W WO2023026829A1 WO 2023026829 A1 WO2023026829 A1 WO 2023026829A1 JP 2022030138 W JP2022030138 W JP 2022030138W WO 2023026829 A1 WO2023026829 A1 WO 2023026829A1
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Prior art keywords
resin composition
group
mass
formula
parts
Prior art date
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Ceased
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PCT/JP2022/030138
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English (en)
French (fr)
Japanese (ja)
Inventor
祐司 中島
宇志 小林
俊介 平野
恵一 長谷部
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Mitsubishi Gas Chemical Co Inc
Original Assignee
Mitsubishi Gas Chemical Co Inc
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Filing date
Publication date
Application filed by Mitsubishi Gas Chemical Co Inc filed Critical Mitsubishi Gas Chemical Co Inc
Priority to JP2023501827A priority Critical patent/JP7255765B1/ja
Priority to CN202280057395.1A priority patent/CN117836341A/zh
Priority to KR1020247003242A priority patent/KR102728882B1/ko
Priority to KR1020237030303A priority patent/KR102634507B1/ko
Priority to US18/685,865 priority patent/US12325770B2/en
Priority to EP22861119.0A priority patent/EP4386022A4/en
Publication of WO2023026829A1 publication Critical patent/WO2023026829A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • 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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
    • C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
    • 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
    • C08F212/00—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 an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • 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
    • C08F212/00—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 an aromatic carbocyclic ring
    • C08F212/34—Monomers containing two or more unsaturated aliphatic radicals
    • C08F212/36—Divinylbenzene
    • 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
    • C08F22/00—Homopolymers and 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
    • C08F22/36—Amides or imides
    • C08F22/40—Imides, e.g. cyclic imides
    • 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
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • 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
    • 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
    • C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
    • 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; 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
    • 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
    • C08L51/003—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 macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H01B3/442—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from aromatic vinyl compounds
    • 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
    • H05K1/0346—Organic insulating material consisting of one material containing N
    • 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
    • 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
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
    • B32B2307/302—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
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/304—Insulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
    • C08J2325/00—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
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
    • C08J2325/04—Homopolymers or copolymers of styrene
    • C08J2325/08—Copolymers of styrene
    • 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
    • C08J2451/00—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
    • C08J2451/08—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 macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2453/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
    • 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
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    • 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

Definitions

  • the present invention relates to resin compositions, cured products, prepregs, metal foil-clad laminates, resin sheets, and printed wiring boards.
  • Patent Document 1 a bifunctional vinylbenzyl compound (a) containing a predetermined polyphenylene ether skeleton, a predetermined maleimide compound (b), a predetermined cyanate ester resin (c), a predetermined epoxy A resin composition for a printed wiring board containing a resin (d) is disclosed.
  • Patent Document 2 discloses a resin composition containing a polyfunctional vinyl aromatic polymer (A) and a thermosetting compound (B) and containing no radical polymerization initiator.
  • the polyfunctional vinyl aromatic polymer (A) is a polymer having a structural unit represented by formula (V). (Wherein, Ar represents an aromatic hydrocarbon linking group. * represents a bonding position.)
  • An object of the present invention is to solve such problems, and a resin composition having a low dielectric constant and dielectric loss tangent before moisture absorption (initial state) and after moisture absorption, and a high metal foil peel strength, and this An object of the present invention is to provide a cured product, a prepreg, a metal foil-clad laminate, a resin sheet, and a printed wiring board used.
  • M1 , R M2 , R M3 , and R M4 each independently represent a hydrogen atom or an organic group.
  • R M5 and R M6 each independently represent a hydrogen atom or an alkyl group.
  • Ar M represents a divalent aromatic group
  • A is a 4- to 6-membered alicyclic group
  • R M7 and R M8 are each independently an alkyl group
  • mx is 1 or 2
  • lx is 0 or 1.
  • R M9 and R M10 each independently represent a hydrogen atom or an alkyl group
  • R M11 , R M12 , R M13 and R M14 each independently represent a hydrogen atom or an organic group
  • R M15 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms , an aryloxy group having 1 to 10 carbon atoms, an arylthio group having 1 to 10 carbon atoms, a halogen atom, a hydroxyl group or a mercapto group
  • px represents an integer of 0 to 3
  • maleimide compounds other than the compound (A) represented by the formula (M1) epoxy compounds, phenol compounds, oxetane resins, benzoxazine compounds, and polyphenylene ethers containing two or more carbon-carbon unsaturated double bonds
  • the resin composition according to any one of ⁇ 1> to ⁇ 3> comprising the compound and at least one other resin component (C) selected from the group consisting of cyanate ester compounds.
  • C resin component selected from the group consisting of cyanate ester compounds.
  • ⁇ 6> The resin composition according to any one of ⁇ 1> to ⁇ 5>, further comprising a filler (D).
  • ⁇ 7> The resin composition according to ⁇ 6>, wherein the content of the filler (D) in the resin composition is 50 to 1600 parts by mass with respect to 100 parts by mass of the resin solid content.
  • ⁇ 8> Any one of ⁇ 1> to ⁇ 7>, wherein the polymer (B) having the structural unit represented by formula (V) has a weight average molecular weight of 3,000 to 130,000. of the resin composition.
  • ⁇ 9> The resin composition according to any one of ⁇ 1> to ⁇ 8>, further comprising an elastomer.
  • ⁇ 12> When the resin solid content in the resin composition is 100 parts by mass, the content of the compound (A) represented by the formula (M1) is 1 to 90 parts by mass, When the resin solid content in the resin composition is 100 parts by mass, the content of the polymer (B) having the structural unit represented by the formula (V) is 1 to 90 parts by mass.
  • ⁇ 14> The resin composition according to any one of ⁇ 1> to ⁇ 13>, further comprising an elastomer.
  • ⁇ 15> The resin composition according to any one of ⁇ 1> to ⁇ 14>, which does not contain a radical polymerization initiator.
  • the monodispersity (Mw/Mn) represented by the ratio of the weight average molecular weight Mw to the number average molecular weight Mn of the polymer (B) having the structural unit represented by the formula (V) is 10 or more. 20 or less, the resin composition according to any one of ⁇ 1> to ⁇ 15>.
  • ⁇ 17> A cured product of the resin composition according to any one of ⁇ 1> to ⁇ 16>.
  • ⁇ 18> A prepreg formed from a substrate and the resin composition according to any one of ⁇ 1> to ⁇ 16>.
  • a metal foil-clad laminate comprising at least one prepreg according to ⁇ 18> and a metal foil disposed on one or both sides of the prepreg.
  • a resin sheet comprising a support and a layer formed from the resin composition according to any one of ⁇ 1> to ⁇ 16> disposed on the surface of the support.
  • ⁇ 21> A printed wiring board comprising an insulating layer and a conductor layer disposed on the surface of the insulating layer, wherein the insulating layer comprises the resin composition according to any one of ⁇ 1> to ⁇ 16>.
  • a semiconductor device including the printed wiring board according to ⁇ 21>.
  • a resin composition having a low dielectric constant and dielectric loss tangent before and after moisture absorption (initial state) and a high metal foil peel strength and a cured product, prepreg, metal foil clad laminate, and resin using the same It became possible to provide sheets and printed wiring boards.
  • an "alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • the notations that do not describe substituted and unsubstituted are preferably unsubstituted. If the standards shown in this specification differ from year to year in terms of measurement methods, etc., the standards as of January 1, 2021 shall be used unless otherwise specified.
  • the dielectric constant indicates the ratio of the dielectric constant of a substance to the vacuum dielectric constant. In addition, in this specification, the relative dielectric constant may be simply referred to as "permittivity".
  • (meth)acryl represents both or either acryl and methacryl.
  • resin solid content refers to components excluding fillers and solvents, and is a compound (A) represented by formula (M1) and a polymer having a structural unit represented by formula (V). (B), and other resin components, elastomers, silane coupling agents, and other resin additive components (additives such as flame retardants, etc.) that are blended as necessary.
  • the resin composition of the present embodiment is characterized by containing a compound (A) represented by formula (M1) and a polymer (B) having a structural unit represented by formula (V).
  • A represented by formula (M1)
  • B a polymer having a structural unit represented by formula (V).
  • R M1 , R M2 , R M3 , and R M4 each independently represent a hydrogen atom or an organic group.
  • R M5 and R M6 each independently represent a hydrogen atom or an alkyl group.
  • Ar M represents a divalent aromatic group
  • A is a 4- to 6-membered alicyclic group
  • R M7 and R M8 are each independently an alkyl group
  • mx is 1 or 2
  • lx is 0 or 1.
  • R M9 and R M10 each independently represent a hydrogen atom or an alkyl group
  • R M11 , R M12 , R M13 and R M14 each independently represent a hydrogen atom or an organic group
  • R M15 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms , an aryloxy group having 1 to 10 carbon atoms, an arylthio group having 1 to 10 carbon atoms, a halogen atom, a hydroxyl group or a mercapto group
  • px represents an integer of 0 to 3
  • nx represents an integer of 1 to 20.
  • Ar represents an aromatic hydrocarbon linking group. * represents a bonding position.
  • a resin composition having a low dielectric constant and a low dielectric loss tangent before (initial state) and after moisture absorption, and a high metal foil peel strength can be obtained.
  • the dielectric constant (Dk) of the resin composition when a resin with a high Dk and a resin with a low Dk are mixed, the dielectric constant tends to correspond to the mass fraction.
  • the dielectric loss tangent (Df) of the resin composition even if a resin with a high Df and a resin with a low Df are mixed, the dielectric loss tangent does not correspond to the mass fraction in many cases.
  • the cured product of the resin composition was able to effectively exhibit the inherently excellent properties of the compound (A) represented by the formula (M1) in terms of metal foil peel strength. .
  • the compound (A) represented by the formula (M1) by adjusting the molecular skeleton such as the molecular structure around the reaction point, it is presumed that the resin components can be easily bonded to each other. be.
  • the molecular weight of the polymer (B) having the structural unit represented by the formula (V) the probability of bonding with the compound (A) represented by the formula (M1) is increased. It is speculated that it could be lower.
  • the resin composition of this embodiment contains a compound (A) represented by formula (M1).
  • a compound (A) represented by formula (M1) By including the compound (A) represented by formula (M1), high metal foil peel strength can be achieved.
  • the compound (A) represented by the formula (M1) is difficult to form a resin bonded to the polymer (B) having a structural unit represented by the formula (V), so the resulting cured product has the formula It is possible to effectively exhibit the inherent low Df of the polymer (B) having the structural unit represented by (V).
  • R M1 , R M2 , R M3 , and R M4 each independently represent a hydrogen atom or an organic group.
  • R M5 and R M6 each independently represent a hydrogen atom or an alkyl group.
  • Ar M represents a divalent aromatic group
  • A is a 4- to 6-membered alicyclic group
  • R M7 and R M8 are each independently an alkyl group
  • mx is 1 or 2 and lx is 0 or 1.
  • R M9 and R M10 each independently represent a hydrogen atom or an alkyl group
  • R M11 , R M12 , R M13 and R M14 each independently represent a hydrogen atom or an organic group
  • R M15 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms , an aryloxy group having 1 to 10 carbon atoms, an arylthio group having 1 to 10 carbon atoms, a halogen atom, a hydroxyl group or a mercapto group
  • px represents an integer of 0 to 3
  • nx represents an integer of 1 to 20.
  • R M1 , R M2 , R M3 and R M4 in the formula each independently represent a hydrogen atom or an organic group.
  • the organic group here is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, a methyl group, an ethyl group, a propyl group, a butyl group. Among them, a methyl group is particularly preferred.
  • R M1 and R M3 are each independently preferably an alkyl group, and R M2 and R M4 are preferably hydrogen atoms.
  • RM5 and RM6 each independently represent a hydrogen atom or an alkyl group, preferably an alkyl group.
  • the alkyl group here is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and especially a methyl group.
  • Ar 1 M represents a divalent aromatic group, preferably a phenylene group, a naphthalenediyl group, a phenanthenediyl group or an anthracenediyl group, more preferably a phenylene group, still more preferably an m-phenylene group.
  • Ar M may have a substituent, and the substituent is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, a methyl group, Ethyl group, propyl group and butyl group are more preferred, and methyl group is particularly preferred.
  • Ar M is unsubstituted.
  • A is a 4- to 6-membered alicyclic group, more preferably a 5-membered alicyclic group (preferably a group forming an indane ring in combination with a benzene ring).
  • R 1 M7 and R 1 M8 are each independently an alkyl group, preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group.
  • mx is 1 or 2, preferably 2;
  • lx is 0 or 1, preferably 1;
  • R M9 and R M10 each independently represent a hydrogen atom or an alkyl group, more preferably an alkyl group.
  • the alkyl group here is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and especially a methyl group.
  • R M11 , R M12 , R M13 and R M14 each independently represent a hydrogen atom or an organic group.
  • the organic group here is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, a methyl group, an ethyl group, a propyl group, a butyl group.
  • R M12 and R M13 are each independently preferably an alkyl group, and R M11 and R M14 are preferably hydrogen atoms.
  • R M15 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aryl group having 1 to 10 carbon atoms.
  • aryloxy group, arylthio group having 1 to 10 carbon atoms, halogen atom, hydroxyl group or mercapto group, alkyl group having 1 to 4 carbon atoms, cycloalkyl group having 3 to 6 carbon atoms, or 6 to 10 carbon atoms is preferably an aryl group of px represents an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, and still more preferably 0.
  • nx represents an integer of 1-20. nx may be an integer of 10 or less.
  • the resin composition of the present embodiment may contain only one compound (A) represented by the formula (M1) and having at least different nx values, or may contain two or more compounds.
  • the average value of nx (average repeating unit number) n in the compound (A) represented by formula (M1) in the resin composition has a low melting point (low softening point) and a melt viscosity is preferably 0.92 or more, more preferably 0.95 or more, even more preferably 1.0 or more, and 1.1 or more. More preferably. Also, n is preferably 10.0 or less, more preferably 8.0 or less, still more preferably 7.0 or less, and even more preferably 6.0 or less. It may be 0 or less. The same applies to formula (M1-1) and the like, which will be described later.
  • Compound (A) represented by formula (M1) is preferably a compound represented by formula (M1-1) below.
  • R M21 , R M22 , R M23 and R M24 each independently represent a hydrogen atom or an organic group
  • R M25 and R M26 each independently represent a hydrogen atom or an alkyl
  • R M27 , R M28 , R M29 and R M30 each independently represent a hydrogen atom or an organic group
  • R M31 and R M32 each independently represent a hydrogen atom or an alkyl group
  • R M33 , RM34 , RM35 and RM36 each independently represent a hydrogen atom or an organic group
  • RM37 , RM38 and RM39 each independently represent a hydrogen atom or an alkyl group
  • nx is represents an integer of 1 or more and 20 or less.
  • R M21 , R M22 , R M23 , and R M24 in the formula each independently represent a hydrogen atom or an organic group.
  • the organic group here is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, a methyl group, an ethyl group, a propyl group, a butyl group. More preferred, and a methyl group is particularly preferred.
  • R M21 and R M23 are preferably alkyl groups, and R M22 and R M24 are preferably hydrogen atoms.
  • RM25 and RM26 each independently represent a hydrogen atom or an alkyl group, preferably an alkyl group.
  • the alkyl group here is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and especially a methyl group.
  • R M27 , R M28 , R M29 and R M30 each independently represent a hydrogen atom or an organic group, preferably a hydrogen atom.
  • the organic group here is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, a methyl group, an ethyl group, a propyl group, a butyl group. More preferred, and a methyl group is particularly preferred.
  • R M31 and R M32 each independently represent a hydrogen atom or an alkyl group, preferably an alkyl group.
  • the alkyl group here is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and especially a methyl group.
  • R M33 , R M34 , R M35 and R M36 each independently represent a hydrogen atom or an organic group.
  • the organic group here is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, a methyl group, an ethyl group, a propyl group, a butyl group.
  • R M33 and R M36 are preferably hydrogen atoms, and R M34 and R M35 are preferably alkyl groups.
  • R M37 , R M38 and R M39 each independently represent a hydrogen atom or an alkyl group, preferably an alkyl group.
  • the alkyl group here is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and especially a methyl group.
  • nx represents an integer of 1 or more and 20 or less. nx may be an integer of 10 or less.
  • the compound represented by formula (M1-1) is preferably a compound represented by formula (M1-2) below.
  • R M21 , R M22 , R M23 and R M24 each independently represent a hydrogen atom or an organic group
  • R M25 and R M26 each independently represent a hydrogen atom or an alkyl
  • R M27 , R M28 , R M29 and R M30 each independently represent a hydrogen atom or an organic group
  • R M31 and R M32 each independently represent a hydrogen atom or an alkyl group
  • R M33 , RM34 , RM35 and RM36 each independently represent a hydrogen atom or an organic group
  • RM37 , RM38 and RM39 each independently represent a hydrogen atom or an alkyl group
  • nx is represents an integer of 1 or more and 20 or less.
  • R M21 , R M22 , R M23 , R M24 , R M25 , R M26 , R M27 , R M28 , R M29 , R M30 , R M31 , R M32 , R M33 , R M34 , R M35 , R M36 , R M37 , R M38 , R M39 and nx are respectively R M21 , R M22 , R M23 , R M24 , R M25 , R M26 , R M27 , R M27 , R M26 , R M27 in formula (M1-1) RM28 , RM29 , RM30 , RM31 , RM32 , RM33 , RM34 , RM35 , RM36 , RM37 , RM38 , RM39 , and nx, and the preferred ranges are also the same .
  • the compound represented by the formula (M1-1) is preferably a compound represented by the following formula (M1-3), more preferably a compound represented by the following formula (M1-4). more preferred.
  • M1-3 nx represents an integer of 1 or more and 20 or less.
  • nx may be an integer of 10 or less.
  • the molecular weight of compound (A) represented by formula (M1) is preferably 500 or more, more preferably 600 or more, and even more preferably 700 or more. When the content is at least the above lower limit, the resulting cured product tends to be further improved in low dielectric properties and low water absorption. Further, the molecular weight of the compound (A) represented by formula (M1) is preferably 10000 or less, more preferably 9000 or less, even more preferably 7000 or less, and preferably 5000 or less. More preferably, it is 4,000 or less. By adjusting the amount to the above upper limit or less, the heat resistance and handleability of the resulting cured product tend to be further improved.
  • the cured product of the compound (A) represented by the formula (M1) used in the present embodiment has excellent low dielectric properties.
  • the cured product of compound (A) represented by formula (M1) used in the present embodiment preferably has a dielectric constant (Dk) of 3.00 or less at 10 GHz measured according to the cavity resonance perturbation method. It is more preferably 2.80 or less, and even more preferably 2.60 or less.
  • the lower limit of the dielectric constant is practically 2.00 or more, for example.
  • the cured product of the compound (A) represented by the formula (M1) used in the present embodiment preferably has a dielectric loss tangent (Df) at 10 GHz measured according to the cavity resonance perturbation method of 0.0100 or less.
  • the lower limit value of the dielectric loss tangent is, for example, practically 0.0001 or more, and even if it exceeds 0.0030, the required performance can be satisfied.
  • a dielectric constant (Dk) and a dielectric loss tangent (Df) are measured according to the method described in Examples below.
  • the content of the compound (A) represented by the formula (M1) is 1 to 90 parts by mass when the resin solid content in the resin composition is 100 parts by mass. is preferred.
  • the lower limit of the content of the compound (A) represented by the formula (M1) is preferably 5 parts by mass or more, and 10 parts by mass or more when the resin solid content in the resin composition is 100 parts by mass. More preferably, it may be 20 parts by mass or more.
  • the content is at least the above lower limit, the heat resistance and metal foil peel strength of the obtained cured product tend to be further improved.
  • the upper limit of the content of the compound (A) represented by the formula (M1) is preferably 80 parts by mass or less when the resin solid content in the resin composition is 100 parts by mass, and 70 parts by mass. It is more preferably 55 parts by mass or less, even more preferably 40 parts by mass or less, and may be 35 parts by mass or less. By adjusting the amount to the above upper limit or less, the resulting cured product tends to have a lower water absorbency.
  • the resin composition of the present embodiment may contain only one type of compound (A) represented by formula (M1), or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
  • the resin composition of this embodiment contains a polymer (B) having a structural unit represented by formula (V).
  • a polymer (B) having the structural unit represented by the formula (V) By containing the polymer (B) having the structural unit represented by the formula (V), excellent low dielectric properties can be exhibited. Furthermore, the metal foil peel strength can be increased by using it in combination with the compound (A) represented by the formula (M1).
  • Ar represents an aromatic hydrocarbon linking group. * represents a bonding position.
  • the aromatic hydrocarbon linking group may be a group consisting only of an optionally substituted aromatic hydrocarbon, or may be a group consisting of an optionally substituted aromatic hydrocarbon and another linking group.
  • the aromatic hydrocarbon may be a group consisting of a combination of groups, and is preferably a group consisting only of an optionally substituted aromatic hydrocarbon.
  • the substituent that the aromatic hydrocarbon may have is a substituent Z (for example, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a hydroxy group, an amino group, a carboxy group, a halogen atom, etc.).
  • the aromatic hydrocarbon preferably has no substituents.
  • the aromatic hydrocarbon linking group is generally a divalent linking group.
  • the aromatic hydrocarbon linking group specifically includes a phenylene group, a naphthalenediyl group, an anthracenediyl group, a phenanthenediyl group, a biphenyldiyl group, and a fluorenediyl group, which may have a substituent.
  • a phenylene group optionally having a substituent is preferable.
  • the substituent is exemplified by the above-described substituent Z, but the above-described groups such as the phenylene group preferably have no substituent.
  • the structural unit represented by the formula (V) includes a structural unit represented by the following formula (V1), a structural unit represented by the following formula (V2), and a structural unit represented by the following formula (V3). More preferably, at least one is included. In addition, * in the following formula represents a binding position. Further, hereinafter, the structural units represented by formulas (V1) to (V3) may be collectively referred to as "structural unit (a)".
  • L 1 is an aromatic hydrocarbon linking group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, even more preferably 6 to 10 carbon atoms).
  • Specific examples include a phenylene group, a naphthalenediyl group, an anthracenediyl group, a phenanthenediyl group, a biphenyldiyl group, and a fluorenediyl group, which may have a substituent.
  • a phenylene group having a low molecular weight is preferred.
  • the substituent is exemplified by the above-described substituent Z, but the above-described groups such as the phenylene group preferably have no substituent.
  • the compound forming the structural unit (a) is preferably a divinyl aromatic compound, and examples thereof include divinylbenzene, bis(1-methylvinyl)benzene, divinylnaphthalene, divinylanthracene, divinylbiphenyl, and divinylphenanthrene. be done. Among them, divinylbenzene is particularly preferred. One type of these divinyl aromatic compounds may be used, or two or more types may be used as necessary.
  • the polymer (B) having a structural unit represented by formula (V) may be a homopolymer of the structural unit (a) as described above, but may be a copolymer with a structural unit derived from another monomer. It may be a coalescence. Examples of structural units derived from other monomers include structural units (b) derived from aromatic compounds having one vinyl group (monovinyl aromatic compounds).
  • the copolymerization ratio of the structural unit (a) is preferably 5 mol% or more, and is preferably 10 mol. % or more, more preferably 15 mol % or more. It is practical that the upper limit is 90 mol % or less.
  • the polymer (B) having a structural unit represented by formula (V) is a copolymer containing a structural unit (b) derived from a monovinyl aromatic compound
  • examples of the monovinyl aromatic compound include styrene. , vinylnaphthalene, vinylaromatic compounds such as vinylbiphenyl; o-methylstyrene, m-methylstyrene, p-methylstyrene, o,p-dimethylstyrene, o-ethylvinylbenzene, m-ethylvinylbenzene, p-ethyl nucleus alkyl-substituted vinyl aromatic compounds such as vinylbenzene, methylvinylbiphenyl and ethylvinylbiphenyl;
  • the monovinyl aromatic compounds exemplified here may optionally have the substituent Z described above. Moreover, one of these monovinyl aromatic compounds may be used,
  • the structural unit (b) derived from a monovinyl aromatic compound is preferably a structural unit represented by the following formula (V4).
  • L 2 is an aromatic hydrocarbon linking group, and preferred specific examples thereof include the examples of L 1 above.
  • R V1 is a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms (preferably an alkyl group). When R V1 is a hydrocarbon group, it preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms. R V1 and L 2 may have the substituent Z described above.
  • the copolymerization ratio of the structural unit (b) is 10 mol% or more. is preferred, and 15 mol % or more is more preferred.
  • the upper limit is preferably 98 mol % or less, more preferably 90 mol % or less, and even more preferably 85 mol % or less.
  • the polymer (B) having the structural unit represented by formula (V) may have structural units other than the structural unit (a) and the structural unit (b).
  • Examples of other structural units include structural units (c) derived from cycloolefin compounds.
  • Cycloolefin compounds include hydrocarbons having a double bond in the ring structure. Specifically, in addition to monocyclic cyclic olefins such as cyclobutene, cyclopentene, cyclohexene, and cyclooctene, compounds having a norbornene ring structure such as norbornene and dicyclopentadiene, and cycloolefin compounds in which aromatic rings are condensed such as indene and acenaphthylene etc.
  • Examples of norbornene compounds include those described in paragraphs 0037 to 0043 of JP-A-2018-39995, the contents of which are incorporated herein.
  • the cycloolefin compounds exemplified here may further have the substituent Z described above.
  • the copolymerization ratio of the structural unit (c) is 10 mol% or more. is preferred, 20 mol % or more is more preferred, and 30 mol % or more is even more preferred.
  • the upper limit is preferably 90 mol% or less, more preferably 80 mol% or less, even more preferably 70 mol% or less, may be 50 mol% or less, or 30 mol%. It may be below.
  • a polymer (B) having a structural unit represented by formula (V) may further incorporate a structural unit (d) derived from a different polymerizable compound (hereinafter also referred to as another polymerizable compound).
  • Other polymerizable compounds (monomers) include, for example, compounds containing three vinyl groups. Specific examples include 1,3,5-trivinylbenzene, 1,3,5-trivinylnaphthalene, and 1,2,4-trivinylcyclohexane. Alternatively, ethylene glycol diacrylate, butadiene and the like can be used.
  • the copolymerization ratio of structural units (d) derived from other polymerizable compounds is preferably 30 mol% or less, more preferably 20 mol% or less, and even more preferably 10 mol% or less. .
  • a polymer essentially comprising the structural unit (a) and containing at least one of the structural units (b) to (d) is exemplified. Furthermore, an embodiment is exemplified in which the total of structural units (a) to (d) accounts for 95 mol% or more, further 98 mol% or more of all structural units.
  • the structural unit (a) is essential, and among all structural units excluding the terminal, a structural unit containing an aromatic ring is preferably 90 mol % or more, more preferably 95 mol % or more, and may be 100 mol %. In calculating the mol % per all structural units, one structural unit is derived from one molecule of the monomer constituting the polymer (B) having the structural unit represented by the formula (V).
  • the method for producing the polymer (B) having the structural unit represented by formula (V) is not particularly limited and may be a conventional method. compounds, cycloolefin compounds, etc.) and polymerizing in the presence of a Lewis acid catalyst.
  • a metal fluoride such as boron trifluoride or a complex thereof can be used as the Lewis acid catalyst.
  • the molecular weight of the polymer (B) having the structural unit represented by formula (V) is, in terms of number average molecular weight Mn, preferably 300 or more, more preferably 500 or more, and 1,000 or more. is more preferable, and 1,500 or more is more preferable.
  • the upper limit is preferably 130,000 or less, more preferably 120,000 or less, even more preferably 110,000 or less, even more preferably 100,000 or less.
  • the weight-average molecular weight Mw of the polymer (B) having the structural unit represented by formula (V) is preferably 1,000 or more, more preferably 1,500 or more. It is more preferably 000 or more, more preferably 2,500 or more, even more preferably 3,000 or more, and may be 3,500 or more, or 4,000 or more.
  • the excellent low dielectric properties of the polymer (B) having the structural unit represented by the formula (V), especially the Df and the dielectric properties after moisture absorption, can be effectively reduced to the resin composition.
  • the upper limit is preferably 160,000 or less, more preferably 150,000 or less, even more preferably 140,000 or less, even more preferably 130,000 or less, and 120,000 or less. , 110,000 or less.
  • the thickness is equal to or less than the above upper limit, there is a tendency that poor embedding is less likely to occur when the prepreg or resin sheet is laminated on the circuit board.
  • the monodispersity (Mw/Mn) represented by the ratio of the weight average molecular weight Mw to the number average molecular weight Mn is preferably 100 or less, more preferably 50 or less, and even more preferably 20 or less. .
  • the lower limit value is practically 1.1 or more, and may be 5 or more, 7 or more, and even if it is 10 or more, the required performance is satisfied.
  • the above Mw and Mn are measured according to the description of Examples described later.
  • the resin composition of the present embodiment contains two or more polymers (B) having structural units represented by formula (V)
  • Mw, Mn and Mw/Mn of the mixture preferably satisfy the above ranges.
  • the vinyl group equivalent weight of the polymer (B) having the structural unit represented by formula (V) is 200 g/eq. 230 g/eq. more preferably 250 g/eq. more preferably 300 g/eq. Above, 350g/eq. or more.
  • the equivalent weight of the vinyl group is 1200 g/eq. It is preferably less than or equal to 1000 g/eq. It is more preferably less than or equal to 800 g/eq. 600 g/eq. 500 g/eq. 400 g/eq. 350 g/eq. It may be below.
  • the amount is at least the above lower limit, the storage stability of the resin composition tends to improve, and the fluidity of the resin composition tends to improve.
  • the polymer (B) having the structural unit represented by the formula (V) used in the present embodiment preferably has excellent low dielectric properties as a cured product thereof.
  • the cured product of the polymer (B) having the structural unit represented by the formula (V) used in the present embodiment has a dielectric constant (Dk) of 2.80 or less at 10 GHz measured according to the cavity resonance perturbation method. It is preferably 2.60 or less, more preferably 2.50 or less, and even more preferably 2.40 or less.
  • the lower limit of the dielectric constant is practically 1.80 or more, for example.
  • the cured product of the polymer (B) having the structural unit represented by the formula (V) used in the present embodiment has a dielectric loss tangent (Df) of 0.0030 or less at 10 GHz measured according to the cavity resonance perturbation method. is preferably 0.0020 or less, and even more preferably 0.0010 or less. Moreover, the lower limit value of the dielectric loss tangent is practically 0.0001 or more, for example.
  • a dielectric constant (Dk) and a dielectric loss tangent (Df) are measured according to the method described in Examples below.
  • the content of the polymer (B) having the structural unit represented by the formula (V) is 1 to 90 mass parts. It is preferable that it is a part.
  • the lower limit of the content of the polymer (B) having the structural unit represented by formula (V) is preferably 5 parts by mass or more when the resin solid content in the resin composition is 100 parts by mass. , more preferably 10 parts by mass or more, more preferably 15 parts by mass or more, even more preferably 20 parts by mass or more, and may be 30 parts by mass or more.
  • the content of the polymer (B) having the structural unit represented by formula (V) By setting the content of the polymer (B) having the structural unit represented by formula (V) to the above lower limit or more, low dielectric properties, particularly low dielectric constant can be effectively achieved.
  • the upper limit of the content of the polymer (B) having the structural unit represented by formula (V) is 80 parts by mass or less when the resin solid content in the resin composition is 100 parts by mass. is preferably 70 parts by mass or less, more preferably 50 parts by mass or less, even more preferably 40 parts by mass or less, and may be 35 parts by mass or less.
  • cured material can be improved effectively by making it below the said upper limit.
  • the polymer (B) having a structural unit represented by formula (V) may be contained in the resin composition in one type or in two or more types. When two or more types are included, the total amount is preferably within the above range.
  • the total amount of the compound (A) represented by the formula (M1) and the polymer (B) having the structural unit represented by the formula (V) is 20% by mass or more of the resin solid content. , more preferably 30% by mass or more, and even more preferably 40% by mass or more.
  • the content is at least the above lower limit, the heat resistance, low water absorption, low dielectric properties, and metal foil peel strength of the obtained cured product tend to be further improved.
  • the upper limit of the total amount is determined by considering the low dielectric properties of the resulting cured product and properties other than the metal foil peel strength (e.g., heat resistance, low water absorption), and the resin solid content in the resin composition. It may be 90% by mass or less, 70% by mass or less, or 50% by mass or less.
  • the mass ratio of the compound (A) represented by formula (M1) and the polymer (B) having a structural unit represented by formula (V) is 9:1 to 1. :9 is preferred, 8:2 to 2:8 is more preferred, 7:3 to 3:7 is even more preferred, and 6:4 to 4:6 is even more preferred. With such a blend ratio, it is possible to improve both the metal foil peel strength and the low dielectric property in a well-balanced manner.
  • the resin composition of the present embodiment further contains a maleimide compound other than the compound (A) represented by formula (M1), an epoxy compound, a phenol compound, an oxetane resin, a benzoxazine compound, and a carbon-carbon unsaturated double bond.
  • a maleimide compound other than the compound (A) represented by formula (M1) an epoxy compound, a phenol compound, an oxetane resin, a benzoxazine compound, and a carbon-carbon unsaturated double bond.
  • Polyphenylene ether compounds containing two or more and may contain one or more other resin components (C) selected from the group consisting of cyanate ester compounds, compound (A) represented by formula (M1) containing one or more other components selected from the group consisting of maleimide compounds, epoxy compounds, phenol compounds, polyphenylene ether compounds containing two or more carbon-carbon unsaturated double bonds, and cyanate ester compounds other than is preferred.
  • the present embodiment preferably contains a maleimide compound and/or a polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds, and contains a polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds. is more preferable.
  • the resin composition contains a cyanate ester compound.
  • the cured product of the other resin component (C) has excellent low dielectric properties.
  • the other resin component (C) preferably has a dielectric constant (Dk) of 4.0 or less, and preferably 3.5 or less, at 10 GHz measured according to the cavity resonance perturbation method. is more preferable.
  • the lower limit of the dielectric constant (Dk) is practically 2.0 or more, for example.
  • the dielectric loss tangent (Df) of each cured product of the other resin component (C) at 10 GHz measured according to the cavity resonance perturbation method is preferably 0.030 or less, and preferably 0.002 or less. is more preferred.
  • the lower limit of the dielectric loss tangent (Df) is practically 0.0001 or more, for example.
  • the cured product of the other resin component (C) has high heat resistance.
  • the other resin component (C) preferably has a glass transition temperature of 150° C. or higher, preferably 180° C. or higher, measured according to the dynamic viscoelasticity measurement specified in JIS C6481. is more preferable, and 200° C. or higher is even more preferable.
  • a cured product having more excellent heat resistance can be obtained by adjusting the content to be at least the above lower limit.
  • the upper limit of the glass transition temperature is 400° C. or less.
  • the resin composition of the present embodiment may contain an elastomer. Furthermore, the resin composition of the present embodiment may contain an active ester compound. Furthermore, additives commonly used in the technical field of the present invention may be contained within the scope of the present invention. Details of the other resin component (C), the elastomer, and the active ester are described below.
  • the resin composition of the present embodiment may contain a maleimide compound other than the compound (A) represented by formula (M1) (hereinafter sometimes simply referred to as "another maleimide compound").
  • Other maleimide compounds have 1 or more (preferably 2 to 12, more preferably 2 to 6, still more preferably 2 to 4, still more preferably 2 or 3, still more preferably 2) maleimide groups in one molecule. It is not particularly limited as long as it has a compound, and a wide range of compounds commonly used in the field of printed wiring boards can be used.
  • Examples of other maleimide compounds include compounds represented by formulas (2M) to (5M), and compounds represented by formulas (2M) to (4M).
  • each R 54 independently represents a hydrogen atom or a methyl group
  • n 4 represents an integer of 1 or more.
  • n4 is preferably an integer of 1-10, more preferably an integer of 1-5, even more preferably an integer of 1-3, and most preferably 1 or 2.
  • the compound (2M) represented by the formula (2M) may contain only one compound having at least a different value of n4 , or may contain two or more compounds.
  • each R 55 independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a phenyl group, and n 5 represents an integer of 1 or more and 10 or less.
  • R 55 is preferably a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, phenyl group, hydrogen atom and One of the methyl groups is more preferred, and a hydrogen atom is even more preferred.
  • n5 is preferably an integer of 1 or more and 5 or less, more preferably an integer of 1 to 3, and even more preferably 1 or 2.
  • each R 56 independently represents a hydrogen atom, a methyl group or an ethyl group
  • each R 57 independently represents a hydrogen atom or a methyl group.
  • R 58 each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a phenyl group
  • R 59 each independently represents a hydrogen atom or a methyl group
  • n 6 represents an integer of 1 or more.
  • R 58 is preferably a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, phenyl group, hydrogen atom and One of the methyl groups is more preferred, and a hydrogen atom is even more preferred.
  • R 59 is preferably a methyl group.
  • n6 is preferably an integer of 1 to 10, more preferably an integer of 1 to 5, even more preferably an integer of 1 to 3, more preferably 1 or 2, and may be 1.
  • the compound represented by formula (5M) may be a mixture of compounds with different n6 , and is preferably a mixture.
  • maleimide compounds are the compounds represented by formulas (2M) to (5M), and among the compounds represented by formulas (2M) to (4M), represented by formula (3M) Compounds are more preferred.
  • Other maleimide compounds may be prepared by known methods or may be commercially available products. Commercially available products include, for example, "MIR-3000-70MT” manufactured by Nippon Kayaku Co., Ltd. as a compound represented by formula (3M), and "BMI-2300” manufactured by Daiwa Kasei Kogyo Co., Ltd. as a compound represented by formula (2M). ”, “BMI-70” manufactured by K-I Kasei Co., Ltd. as a compound represented by formula (4M), and “MIR-5000” manufactured by Nippon Kayaku Co., Ltd. as a compound represented by formula (5M).
  • maleimide compounds other than the above include oligomers of phenylmethanemaleimide, m-phenylenebismaleimide, 2,2-bis(4-(4-maleimidophenoxy)-phenyl)propane, 4-methyl-1 ,3-phenylenebismaleimide, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, 4,4′-diphenyletherbismaleimide, 4,4′-diphenylsulfonebismaleimide, 1,3-bis( 3-maleimidophenoxy)benzene, 1,3-bis(4-maleimidophenoxy)benzene, prepolymers thereof, prepolymers of these maleimides and amines, and the like.
  • the lower limit of the content of the other maleimide compound is 1 part by mass or more with respect to 100 parts by mass of the resin solid content in the resin composition. It is preferably 5 parts by mass or more, more preferably 10 parts by mass or more. When the content of the other maleimide compound is 1 part by mass or more, the resulting cured product tends to have improved flame resistance.
  • the upper limit of the content of the other maleimide compound is preferably 70 parts by mass or less, more preferably 50 parts by mass or less, and 30 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition. It is more preferably not more than 20 parts by mass, and even more preferably not more than 20 parts by mass.
  • the resin composition in the present embodiment may contain only one kind of other maleimide compound, or may contain two or more kinds thereof. When two or more types are included, the total amount is preferably within the above range.
  • the resin composition in the present embodiment can also be configured so as not to substantially contain other maleimide compounds. “Substantially free” means that the content of the other maleimide compound is less than 1 part by mass with respect to 100 parts by mass of the resin solid content in the resin composition.
  • the resin composition of this embodiment may contain an epoxy compound.
  • the epoxy compound is a compound having one or more (preferably 2 to 12, more preferably 2 to 6, still more preferably 2 to 4, still more preferably 2 or 3, still more preferably 2) epoxy groups in one molecule.
  • it is a resin, it is not particularly limited, and a wide range of compounds commonly used in the field of printed wiring boards can be used.
  • Epoxy compounds include, for example, bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolak type epoxy resin, bisphenol A novolak type epoxy resin, glycidyl ester type epoxy resin, aralkyl Novolak type epoxy resin, biphenyl aralkyl type epoxy resin, naphthylene ether type epoxy resin, cresol novolak type epoxy resin, polyfunctional phenol type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, naphthalene skeleton modified novolak type epoxy resin, phenol Aralkyl-type epoxy resin, naphthol-aralkyl-type epoxy resin, dicyclopentadiene-type epoxy resin, biphenyl-type epoxy resin, alicyclic epoxy resin, polyol-type epoxy resin, phosphorus-containing epoxy resin, glycidylamine, glycidyl ester, butadiene, etc.
  • the resin composition of the present embodiment preferably contains an epoxy compound within a range that does not impair the effects of the present invention.
  • the content thereof is preferably 0.1 parts by mass or more, and 1 part by mass or more with respect to 100 parts by mass of the resin solid content in the resin composition. It is more preferable that the amount is 2 parts by mass or more.
  • the content of the epoxy compound is 0.1 parts by mass or more, the metal foil peel strength and toughness tend to be improved.
  • the upper limit of the content of the epoxy compound is preferably 50 parts by mass or less with respect to 100 parts by mass of the resin solid content in the resin composition, and is preferably 30 parts by mass.
  • the resin composition in the present embodiment may contain only one type of epoxy compound, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
  • the resin composition of this embodiment may contain a phenol compound.
  • the phenol compound has 1 or more (preferably 2 to 12, more preferably 2 to 6, more preferably 2 to 4, still more preferably 2 or 3, still more preferably 2) phenolic hydroxyl groups in one molecule.
  • Phenolic compounds include, for example, bisphenol A type phenol resin, bisphenol E type phenol resin, bisphenol F type phenol resin, bisphenol S type phenol resin, phenol novolak resin, bisphenol A novolac type phenol resin, glycidyl ester type phenol resin, aralkyl novolak phenol.
  • the resin composition of the present embodiment preferably contains a phenol compound within a range that does not impair the effects of the present invention.
  • the content is preferably 0.1 parts by mass or more with respect to 100 parts by mass of the resin solid content in the resin composition, and 50 parts by mass The following are preferable.
  • the resin composition in the present embodiment may contain only one type of phenol compound, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
  • the resin composition in the present embodiment can also be configured so as not to substantially contain a phenol compound. “Substantially free” means that the content of the phenol compound is less than 0.1 part by mass with respect to 100 parts by mass of the resin solid content in the resin composition.
  • the resin composition of this embodiment may contain an oxetane resin.
  • the oxetane resin is a compound having one or more oxetanyl groups (preferably 2 to 12, more preferably 2 to 6, still more preferably 2 to 4, still more preferably 2 or 3, still more preferably 2), especially There is no limitation, and a wide range of compounds commonly used in the field of printed wiring boards can be used.
  • oxetane resins include oxetane, alkyloxetane (e.g., 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, 3,3-dimethyloxetane, etc.), 3-methyl-3-methoxymethyloxetane, 3,3-di(trifluoromethyl)oxetane, 2-chloromethyloxetane, 3,3-bis(chloromethyl)oxetane, biphenyl type oxetane, OXT-101 (manufactured by Toagosei Co., Ltd.), OXT-121 (Toagosei Co., Ltd.) made) and the like.
  • alkyloxetane e.g., 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, 3,3-dimethylox
  • the resin composition of the present embodiment preferably contains an oxetane resin within a range that does not impair the effects of the present invention.
  • the content thereof is preferably 0.1 parts by mass or more, and 1 part by mass or more, relative to 100 parts by mass of the resin solid content in the resin composition. and more preferably 2 parts by mass or more.
  • the content of the oxetane resin is 0.1 parts by mass or more, the metal foil peel strength and toughness tend to be improved.
  • the upper limit of the content of the oxetane resin is preferably 50 parts by mass or less with respect to 100 parts by mass of the resin solid content in the resin composition. It is more preferably 20 parts by mass or less, still more preferably 10 parts by mass or less, and even more preferably 8 parts by mass or less.
  • the content of the oxetane resin is 50 parts by mass or less, the resulting cured product tends to have improved electrical properties.
  • the resin composition in the present embodiment may contain only one type of oxetane resin, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
  • the resin composition in the present embodiment can be configured so as not to substantially contain an oxetane resin. “Substantially free” means that the content of the oxetane resin is less than 0.1 part by mass with respect to 100 parts by mass of the resin solid content in the resin composition.
  • the resin composition of this embodiment may contain a benzoxazine compound.
  • a benzoxazine compound 2 or more (preferably 2 to 12, more preferably 2 to 6, still more preferably 2 to 4, still more preferably 2 or 3, still more preferably 2) dihydrobenzoxazines per molecule
  • dihydrobenzoxazines 2 or more (preferably 2 to 12, more preferably 2 to 6, still more preferably 2 to 4, still more preferably 2 or 3, still more preferably 2) dihydrobenzoxazines per molecule
  • benzoxazine compounds include bisphenol A-type benzoxazine BA-BXZ (manufactured by Konishi Chemical Co., Ltd.), bisphenol F-type benzoxazine BF-BXZ (manufactured by Konishi Chemical Co., Ltd.), and bisphenol S-type benzoxazine BS-BXZ (manufactured by Konishi Chemical Co., Ltd.). made) and the like.
  • the resin composition of the present embodiment preferably contains a benzoxazine compound within a range that does not impair the effects of the present invention.
  • the content thereof is preferably 0.1 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the resin solid content in the resin composition.
  • the resin composition in the present embodiment may contain only one kind of benzoxazine compound, or may contain two or more kinds. When two or more types are included, the total amount is preferably within the above range.
  • the resin composition in the present embodiment can be configured so as not to substantially contain a benzoxazine compound. “Substantially free” means that the content of the benzoxazine compound is less than 0.1 part by mass with respect to 100 parts by mass of the resin solid content in the resin composition.
  • the resin composition of the present embodiment may contain a polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds.
  • a polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds is a polyphenylene ether compound having two or more groups selected from the group consisting of (meth)acrylic groups, maleimide groups, and vinylbenzyl groups at the terminals. preferable. These will be described in detail below.
  • Polyphenylene ether compounds containing two or more carbon-carbon unsaturated double bonds are exemplified by compounds having a phenylene ether skeleton represented by the following formula (X1).
  • R 24 , R 25 , R 26 and R 27 may be the same or different and represent an alkyl group having 6 or less carbon atoms, an aryl group, a halogen atom or a hydrogen atom. .
  • a polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds has the formula (X2): (In Formula (X2), R 28 , R 29 , R 30 , R 34 and R 35 may be the same or different and represent an alkyl group having 6 or less carbon atoms or a phenyl group.
  • R 31 , R 32 and R 33 may be the same or different and are a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group.) and/or the formula (X3):
  • R 36 , R 37 , R 38 , R 39 , R 40 , R 41 , R 42 and R 43 may be the same or different, hydrogen atoms, an alkyl group or a phenyl group, and -A- is a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms.).
  • a polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds is a modified polyphenylene ether compound functionalized with an ethylenically unsaturated group at some or all of the terminals (hereinafter referred to as "modified polyphenylene ether compound (g )”), and more preferably a modified polyphenylene ether compound having two or more groups selected from the group consisting of a (meth)acrylic group, a maleimide group, and a vinylbenzyl group at the end.
  • modified polyphenylene ether compound (g) By employing such a modified polyphenylene ether compound (g), it becomes possible to further reduce the dielectric loss tangent (Df) of the cured product of the resin composition and increase the metal foil peel strength. These may be used singly or in combination of two or more.
  • Modified polyphenylene ether compounds include compounds represented by formula (1).
  • X represents an aromatic group
  • —(Y—O)n 2 — represents a polyphenylene ether structure
  • R 1 , R 2 , and R 3 each independently represent a hydrogen atom.
  • n1 represents an integer of 1 to 6
  • n2 represents an integer of 1 to 100
  • n3 represents an integer of 1 to 4.
  • n 2 and/or n 3 is an integer of 2 or more
  • n 2 structural units (Y—O) and/or n 3 structural units may be the same or different.
  • n3 is preferably 2 or more, more preferably 2.
  • the modified polyphenylene ether compound (g) in the present embodiment is preferably a compound represented by Formula (2).
  • -(O-X-O)- is the formula (3):
  • R 4 , R 5 , R 6 , R 10 and R 11 may be the same or different and are alkyl groups having 6 or less carbon atoms or phenyl groups.
  • R 7 , R 8 and R 9 may be the same or different and are a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group.) and/or formula (4): (In formula (4), R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 and R 19 may be the same or different, hydrogen atoms, an alkyl group or a phenyl group, and -A- is a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms.).
  • -(Y-O)- is the formula (5):
  • R 20 and R 21 may be the same or different and are an alkyl group having 6 or less carbon atoms or a phenyl group.
  • R 22 and R 23 may be the same or different, hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group).
  • at least one of a and b represents an integer of 0 to 100 other than 0, preferably an integer of 0 to 50, more preferably an integer of 1 to 30.
  • 2 or more -(Y-O)- may each independently be an arrangement of one structure, and two or more structures may be block or They may be arranged randomly.
  • -A- in formula (4) includes, for example, methylene group, ethylidene group, 1-methylethylidene group, 1,1-propylidene group, 1,4-phenylenebis(1-methylethylidene) group, 1,3- Divalent organic groups such as phenylenebis(1-methylethylidene) group, cyclohexylidene group, phenylmethylene group, naphthylmethylene group, 1-phenylethylidene group, etc., but not limited to these.
  • R 4 , R 5 , R 6 , R 10 , R 11 , R 20 and R 21 are alkyl groups having 3 or less carbon atoms, and R 7 , R 8 , R 9 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 22 and R 23 are hydrogen atoms or alkyl groups having 3 or less carbon atoms;
  • Polyphenylene ether compounds are preferred, and in particular —(O—X—O)— represented by formula (3) or formula (4) is formula (9), formula (10), and/or formula (11).
  • —(Y—O)— represented by formula (5) is preferably formula (12) or formula (13).
  • a and/or b is an integer of 2 or more
  • 2 or more of -(YO)- are each independently a structure in which two or more of formula (12) and/or formula (13) are arranged, or Alternatively, it may be a structure in which formulas (12) and (13) are arranged in blocks or randomly.
  • R 44 , R 45 , R 46 and R 47 may be the same or different and are a hydrogen atom or a methyl group.
  • -B- is a linear chain having 20 or less carbon atoms , a branched or cyclic divalent hydrocarbon group.
  • Specific examples of -B- are the same as the specific examples of -A- in formula (4).
  • Specific examples of -B- are the same as the specific examples of -A- in formula (4).
  • JP-A-2018-016709 can be referred to for details of the polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds, and the contents thereof are incorporated herein.
  • the polyphenylene ether compound used in this embodiment may be an unmodified polyphenylene ether compound having a hydroxyl group at the end.
  • the unmodified polyphenylene ether compound for example, the descriptions in paragraphs 0011 to 0016 of JP-A-2017-119739 can be employed, and the contents thereof are incorporated herein.
  • the polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds (preferably, the modified polyphenylene ether compound (g)) has a polystyrene-equivalent number average molecular weight of 500 or more and 3,000 by GPC (gel permeation chromatography) method. The following are preferred. When the number average molecular weight is 500 or more, stickiness tends to be further suppressed when the resin composition of the present embodiment is formed into a coating film. When the number average molecular weight is 3,000 or less, the solubility in solvents tends to be further improved.
  • the polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds (preferably, the modified polyphenylene ether compound (g)) has a polystyrene-equivalent weight average molecular weight by GPC of 800 or more and 10,000 or less. It is preferably 800 or more and 5,000 or less.
  • the dielectric constant (Dk) and dielectric loss tangent (Df) of the cured product of the resin composition tend to be lower, and by setting it to the above upper limit or less, the varnish or the like described later can be removed. There is a tendency that the solubility, low viscosity, and moldability of the resin composition in a solvent during preparation are further improved.
  • the terminal carbon-carbon unsaturated double bond equivalent is preferably 400 to 5000 g per carbon-carbon unsaturated double bond, and 400 to 2500 g. is more preferable.
  • the content is at least the lower limit, the cured product of the resin composition tends to have a lower dielectric constant (Dk) and dielectric loss tangent (Df).
  • Dk dielectric constant
  • Df dielectric loss tangent
  • the lower limit of the content of the polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds is , With respect to 100 parts by mass of the resin solid content in the resin composition, it is preferably 1 part by mass or more, more preferably 3 parts by mass or more, further preferably 5 parts by mass or more, 7 parts by mass It is more preferable that it is above.
  • the content is at least the above lower limit, the resulting cured product tends to have improved low water absorption and low dielectric properties (Dk and/or Df).
  • the upper limit of the content of the polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds is preferably 80 parts by mass or less with respect to 100 parts by mass of the resin solid content in the resin composition. It is more preferably 60 parts by mass or less, even more preferably 50 parts by mass or less, even more preferably 40 parts by mass or less, 30 parts by mass or less, 25 It may be less than or equal to parts by mass.
  • the resin composition in the present embodiment may contain only one type of polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
  • the resin composition of the present embodiment may contain a cyanate ester compound.
  • the cyanate ester compound has 1 or more cyanate groups (cyanato groups) per molecule (preferably 2 to 12, more preferably 2 to 6, still more preferably 2 to 4, more preferably 2 or 3, still more preferably is not particularly limited as long as it is a compound containing 2), and a wide range of compounds commonly used in the field of printed wiring boards can be used.
  • the cyanate ester compound is preferably a compound in which a cyanate group is directly bonded to an aromatic skeleton (aromatic ring).
  • cyanate ester compounds include phenol novolak-type cyanate ester compounds, naphthol aralkyl-type cyanate ester compounds (naphthol aralkyl-type cyanates), naphthylene ether-type cyanate ester compounds, biphenyl aralkyl-type cyanate ester compounds, and xylene resins.
  • type cyanate ester compound trisphenolmethane type cyanate ester compound, adamantane skeleton type cyanate ester compound, bisphenol M type cyanate ester compound, bisphenol A type cyanate ester compound, and diallylbisphenol A type cyanate ester compound At least one selected from the group is included.
  • phenol novolac type cyanate ester compounds from the viewpoint of further improving the low water absorption of the resulting cured product, phenol novolac type cyanate ester compounds, naphthol aralkyl type cyanate ester compounds, naphthylene ether type cyanate ester compounds, xylene resin type cyanic acid It is preferably at least one selected from the group consisting of an ester compound, a bisphenol M-type cyanate ester compound, a bisphenol A-type cyanate ester compound, and a diallyl bisphenol A-type cyanate ester compound, and a phenol novolak-type cyanate ester.
  • naphthol aralkyl-type cyanate ester compounds more preferably at least one selected from the group consisting of a naphthol aralkyl-type cyanate ester compound, more preferably a naphthol aralkyl-type cyanate ester compound.
  • cyanate ester compounds may be prepared by known methods, or commercially available products may be used.
  • a cyanate ester compound having a naphthol aralkyl skeleton, a naphthylene ether skeleton, a xylene skeleton, a trisphenolmethane skeleton, or an adamantane skeleton has a relatively large number of functional group equivalents, and the number of unreacted cyanate ester groups is small. Therefore, a cured product of a resin composition using these tends to be even more excellent in low water absorption. Also, mainly due to having an aromatic skeleton or adamantane skeleton, the plating adhesion tends to be further improved.
  • a compound represented by the following formula (1) is more preferable.
  • each R 3 independently represents a hydrogen atom or a methyl group, and n3 represents an integer of 1 or more.
  • each R 3 independently represents a hydrogen atom or a methyl group, and among these, a hydrogen atom is preferred.
  • n3 is an integer of 1 or more, preferably an integer of 1 to 20, more preferably an integer of 1 to 10, and even more preferably an integer of 1 to 6. .
  • the novolac-type cyanate ester compound is not particularly limited, but for example, a compound represented by the following formula (VII) is preferable.
  • each R6 independently represents a hydrogen atom or a methyl group, and n7 represents an integer of 1 or more.
  • each R6 independently represents a hydrogen atom or a methyl group, and among these, a hydrogen atom is preferred.
  • n7 is an integer of 1 or more, preferably an integer of 1 to 20, more preferably an integer of 1 to 10, and even more preferably an integer of 1 to 6.
  • bisphenol A type cyanate ester compound one selected from the group consisting of 2,2-bis(4-cyanatophenyl)propane and prepolymers of 2,2-bis(4-cyanatophenyl)propane The above may be used.
  • the resin composition of the present embodiment preferably contains a cyanate ester compound within a range that does not impair the effects of the present invention.
  • the lower limit of the content is preferably 0.1 parts by mass or more with respect to 100 parts by mass of the resin solid content in the resin composition. , more preferably 1 part by mass or more, more preferably 2 parts by mass or more, even more preferably 5 parts by mass or more, and even more preferably 10 parts by mass or more.
  • the content of the cyanate ester compound is 1 part by mass or more, the resulting cured product tends to have improved heat resistance, combustion resistance, chemical resistance, low dielectric constant, low dielectric loss tangent, and insulating properties. .
  • the upper limit of the content of the cyanate ester compound is 70 parts by mass or less with respect to 100 parts by mass of the resin solid content in the resin composition. Preferably, it is 50 parts by mass or less, more preferably 40 parts by mass or less, even more preferably 30 parts by mass or less, and even more preferably 20 parts by mass or less.
  • the resin composition in the present embodiment may contain only one type of cyanate ester compound, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
  • the resin composition in the present embodiment may be configured so as not to substantially contain a cyanate ester compound.
  • Substantially free means that the content of the cyanate ester compound is less than 0.1 parts by mass, preferably less than 0.01 parts by mass, with respect to 100 parts by mass of the resin solid content in the resin composition. and may be less than 0.001 part by mass.
  • the resin composition of this embodiment may contain an elastomer.
  • an elastomer By including an elastomer, low dielectric properties after moisture absorption, metal foil peel strength, and the like can be improved in a well-balanced manner.
  • the elastomer is not particularly limited, and examples include polyisoprene, polybutadiene, styrene butadiene, butyl rubber, ethylene propylene rubber, styrene butadiene ethylene, styrene butadiene styrene, styrene isoprene styrene, styrene ethylene butylene styrene, styrene propylene styrene.
  • styrene ethylene propylene styrene ethylene propylene styrene
  • fluororubbers silicone rubbers
  • hydrogenated compounds thereof alkyl compounds thereof, and copolymers thereof.
  • it may be a thermoplastic elastomer or a thermosetting elastomer, but a thermoplastic elastomer is preferred.
  • the number average molecular weight of the elastomer used in this embodiment is preferably 50,000 or more. By setting the number average molecular weight to 50,000 or more, the low dielectric properties of the obtained cured product tend to be more excellent.
  • the number average molecular weight is preferably 60,000 or more, more preferably 70,000 or more, and even more preferably 80,000 or more.
  • the upper limit of the number average molecular weight of the thermal elastomer is preferably 400,000 or less, more preferably 350,000 or less, and even more preferably 300,000 or less. When the amount is equal to or less than the upper limit, the solubility of the elastomer component in the resin composition tends to be improved.
  • the resin composition of the present embodiment contains two or more types of elastomers, the number average molecular weight of the mixture thereof preferably satisfies the above range.
  • the elastomer is preferably a thermoplastic elastomer containing styrene monomer units and conjugated diene monomer units (hereinafter referred to as "thermoplastic elastomer (E)").
  • thermoplastic elastomer (E) a thermoplastic elastomer containing styrene monomer units and conjugated diene monomer units
  • the thermoplastic elastomer (E) contains styrene monomer units. By including styrene monomer units, the solubility of the thermoplastic elastomer (E) in the resin composition is improved.
  • Styrene monomers include styrene, ⁇ -methylstyrene, p-methylstyrene, divinylbenzene (vinylstyrene), N,N-dimethyl-p-aminoethylstyrene, N,N-diethyl-p-aminoethylstyrene and the like.
  • thermoplastic elastomer (E) is preferably in the range of 10 to 50% by mass, more preferably in the range of 13 to 45% by mass, and more preferably in the range of 15 to 40% by mass. Ranges are more preferred. If the content of styrene monomer units is 50% by mass or less, the adhesiveness and adhesiveness to substrates and the like will be better.
  • thermoplastic elastomer (E) may contain only one type of styrene monomer unit, or may contain two or more types. When two or more kinds are included, the total amount is preferably within the above range.
  • the description in International Publication No. 2017/126469 can be referred to, the content of which is incorporated herein. The same applies to the conjugated diene monomer unit and the like, which will be described later.
  • the thermoplastic elastomer (E) contains conjugated diene monomer units. Containing the conjugated diene monomer unit improves the solubility of the thermoplastic elastomer (E) in the resin composition.
  • the conjugated diene monomer is not particularly limited as long as it is a diolefin having a pair of conjugated double bonds.
  • Conjugated diene monomers are, for example, 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl- Examples include 1,3-pentadiene, 1,3-hexadiene, and farnesene, with 1,3-butadiene and/or isoprene being preferred, and 1,3-butadiene being more preferred.
  • the thermoplastic elastomer (E) may contain only one type of conjugated diene monomer unit, or may contain two or more types.
  • thermoplastic elastomer (E) all of the conjugated diene bonds of the thermoplastic elastomer may be hydrogenated, partially hydrogenated, or not hydrogenated.
  • the thermoplastic elastomer (E) may or may not contain other monomer units in addition to the styrene monomer units and the conjugated diene monomer units.
  • examples of other monomer units include aromatic vinyl compound units other than styrene monomer units.
  • the total amount of styrene monomer units and conjugated diene monomer units is preferably 90% by mass or more, more preferably 95% by mass or more, of all monomer units. It is more preferably 97% by mass or more, and even more preferably 99% by mass or more.
  • thermoplastic elastomer (E) may contain only one kind of styrene monomer units and conjugated diene monomer units, or may contain two or more kinds thereof. When two or more types are included, the total amount is preferably within the above range.
  • the thermoplastic elastomer (E) may be a block polymer or a random polymer. Moreover, even if the conjugated diene monomer unit is a hydrogenated elastomer in which the conjugated diene monomer unit is hydrogenated, it may be an unhydrogenated elastomer in which it is not hydrogenated, or a partially hydrogenated elastomer in which it is partially hydrogenated. good. In one embodiment of this embodiment, the thermoplastic elastomer (E) is a hydrogenated elastomer.
  • the hydrogenated elastomer means, for example, a thermoplastic elastomer in which double bonds based on conjugated diene monomer units are hydrogenated, and the hydrogenation rate (hydrogenation rate) is 100%.
  • the hydrogenation rate of the hydrogenated elastomer is preferably 85% or more, more preferably 90% or more, and even more preferably 95% or more.
  • the degree of hydrogenation is calculated from the results of 1 H-NMR spectrometry.
  • the thermoplastic elastomer (E) is an unhydrogenated elastomer.
  • the non-hydrogenated elastomer refers to the ratio of hydrogenated double bonds based on conjugated diene monomer units in the elastomer, that is, the hydrogenation rate (hydrogenation rate) is 20% or less. It is intended to include things.
  • the hydrogenation rate of the unhydrogenated elastomer is preferably 15% or less, more preferably 10% or less, and even more preferably 5% or less.
  • the partially hydrogenated elastomer means a thermoplastic elastomer in which part of the double bonds based on the conjugated diene monomer units in the thermoplastic elastomer is hydrogenated, and usually has a hydrogenation rate (hydrogenation rate) of 80. % or more than 20%.
  • the hydrogenation rate is measured by 1 H-NMR. More specifically, it is measured according to paragraph 0130 of JP-A-2022-054761.
  • thermoplastic elastomer (E) used in this embodiment include SEPTON (registered trademark) 2104 manufactured by Kuraray Co., Ltd., S.E.M. O.D. E. (registered trademark) S1606, S1613, S1609, S1605, manufactured by JSR Corporation, DYNARON (registered trademark) 9901P, TR2250, and the like.
  • the content thereof is preferably 1 part by mass or more with respect to 100 parts by mass of the resin solid content, and 3 parts by mass. It is more preferably 7 parts by mass or more, still more preferably 10 parts by mass or more, and even more preferably 12 parts by mass or more.
  • the upper limit of the content of the elastomer is preferably 35 parts by mass or less, more preferably 30 parts by mass or less, and 25 parts by mass or less relative to 100 parts by mass of the resin solid content.
  • the resin composition of the present embodiment may contain only one type of elastomer, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
  • the resin composition of this embodiment may contain an active ester compound.
  • the active ester compound is not particularly limited. 2) includes compounds having an active ester group.
  • the active ester compound may be a linear or branched or cyclic compound.
  • an active ester compound obtained by reacting a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxy compound and/or a thiol compound is preferable from the viewpoint of further improving the heat resistance of the resulting cured product.
  • An active ester compound obtained by reacting a carboxylic acid compound with one or more compounds selected from the group consisting of a phenol compound, a naphthol compound, and a thiol compound is more preferred, and has a carboxylic acid compound and a phenolic hydroxyl group.
  • An aromatic compound obtained by reacting an aromatic compound and having two or more active ester groups in one molecule is more preferable.
  • An aromatic compound obtained by reacting with a group compound and having two or more active ester groups in one molecule is particularly preferred.
  • carboxylic acid compound examples include one or more selected from the group consisting of benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid.
  • benzoic acid acetic acid
  • succinic acid maleic acid, itaconic acid
  • phthalic acid isophthalic acid
  • terephthalic acid pyromellitic acid.
  • one or more selected from the group consisting of succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, and terephthalic acid are preferred, isophthalic acid and One or more selected from the group consisting of terephthalic acid is more preferred.
  • the above thiocarboxylic acid compound includes one or more selected from thioacetic acid and thiobenzoic acid.
  • the phenolic compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- cresol, p-cresol, catechol, ⁇ -naphthol, ⁇ -naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucine, One or more selected from the group consisting of benzenetriol, dicyclopentadienyldiphenol, and phenol novolak, and from the viewpoint of further improving the heat resistance and
  • the thiol compound includes one or more selected from the group consisting of benzenedithiol and triazinedithiol.
  • the active ester compound is preferably a compound having at least two or more carboxylic acids in one molecule and containing an aliphatic chain. From the viewpoint of further improvement, compounds having an aromatic ring are preferable. More specific active ester compounds include active ester compounds described in JP-A-2004-277460.
  • a commercial product may be used for the active ester compound, or it may be prepared by a known method.
  • Commercially available products include compounds containing a dicyclopentadienyldiphenol structure (e.g., EXB9451, EXB9460, EXB9460S, HPC-8000-65T (all manufactured by DIC), etc.), acetylated phenol novolaks (e.g., DC808 ( Mitsubishi Chemical Corp.)), and benzoyl compounds of phenol novolak (e.g., YLH1026, YLH1030, YLH1048 (all manufactured by Mitsubishi Chemical Corp.)).
  • EXB9460S is preferable from the viewpoint of further improving the low thermal expansion property of the material).
  • An active ester compound can be prepared by a known method, for example, by condensation reaction between a carboxylic acid compound and a hydroxy compound.
  • Specific examples include (a) a carboxylic acid compound or its halide, (b) a hydroxy compound, and (c) an aromatic monohydroxy compound, per mol of the carboxy group or acid halide group of (a), (b) 0.05 to 0.75 mol of the phenolic hydroxyl group of (c) and 0.25 to 0.95 mol of (c).
  • the active ester compound is preferably contained within a range that does not impair the effects of the present invention.
  • the resin composition of the present embodiment contains an active ester compound, it is preferably 1 part by mass or more and preferably 90 parts by mass or less with respect to 100 parts by mass of the resin solid content in the resin composition.
  • the resin composition in the present embodiment may contain only one type of active ester compound, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
  • the resin composition in the present embodiment may be configured so as not to substantially contain an active ester compound. “Substantially free” means that the content of the active ester compound is less than 1 part by mass with respect to 100 parts by mass of the resin solid content in the resin composition.
  • the resin composition of the present embodiment preferably contains a filler (D). Addition of the filler (D) can further improve the low dielectric constant, low dielectric loss tangent, flame resistance, and low thermal expansion of the resin composition.
  • the filler (D) used in this embodiment preferably has excellent low dielectric properties.
  • the filler (D) used in the present embodiment preferably has a dielectric constant (Dk) of 8.0 or less, more preferably 6.0 or less, measured according to the cavity resonance perturbation method.
  • the lower limit of the dielectric constant is practically 2.0 or more, for example.
  • the dielectric loss tangent (Df) of the filler (D) used in the present embodiment measured according to the cavity resonance perturbation method, is preferably 0.05 or less, more preferably 0.01 or less. Moreover, the lower limit value of the dielectric loss tangent is practically 0.0001 or more, for example.
  • the type of the filler (D) used in this embodiment is not particularly limited, and those commonly used in the industry can be suitably used.
  • silicas such as natural silica, fused silica, synthetic silica, amorphous silica, aerosil, hollow silica, alumina, white carbon, titanium white, zinc oxide, magnesium oxide, metal oxides such as zirconium oxide, boron nitride , aggregated boron nitride, silicon nitride, nitrides such as aluminum nitride, aluminum hydroxide, heat-treated aluminum hydroxide (aluminum hydroxide heat-treated to reduce some of the water of crystallization), boehmite, magnesium hydroxide Molybdenum compounds such as molybdenum oxide and zinc molybdate, zinc borate, zinc stannate, barium sulfate, clay, kaolin, talc, calcined clay, calcined kaolin, calcined talc
  • Examples include organic fillers such as powder, silicone rubber powder, and silicone composite powder. Among these, one or more selected from the group consisting of silicas, aluminum hydroxide, boehmite, magnesium oxide and magnesium hydroxide is suitable. By using these fillers, properties such as thermal expansion properties, dimensional stability and flame retardancy of the resin composition are improved.
  • the content of the filler (D) in the resin composition of the present embodiment can be appropriately set according to the desired properties, and is not particularly limited. It is preferably 10 parts by mass or more, more preferably 25 parts by mass or more, still more preferably 35 parts by mass or more, even more preferably 50 parts by mass or more, and more preferably 75 parts by mass or more. Further, it is preferably 1,600 parts by mass or less, more preferably 1,200 parts by mass or less, still more preferably 1,000 parts by mass or less, and still more preferably 750 parts by mass or less, relative to 100 parts by mass of the resin solid content in the resin composition.
  • the content of the filler (D) is 30% by mass to 80% by mass of the components excluding the solvent.
  • the resin composition in the present embodiment may contain only one filler (D), or may contain two or more fillers (D). When two or more types are included, the total amount is preferably within the above range.
  • the filler (D) when using the filler (D) in the resin composition of the present embodiment, it may further contain a silane coupling agent.
  • a silane coupling agent By containing the silane coupling agent, the dispersibility of the filler (D) and the adhesive strength between the resin component and the filler (D) and the substrate described later tend to be further improved.
  • the resin composition of this embodiment may contain a flame retardant.
  • Known flame retardants can be used, for example, brominated epoxy resin, brominated polycarbonate, brominated polystyrene, brominated styrene, brominated phthalimide, tetrabromobisphenol A, pentabromobenzyl (meth)acrylate, pentabromo Halogen flame retardants such as toluene, tribromophenol, hexabromobenzene, decabromodiphenyl ether, bis-1,2-pentabromophenylethane, chlorinated polystyrene, chlorinated paraffin, red phosphorus, tricresyl phosphate, triphenyl phosphate , cresyl diphenyl phosphate, trixylenyl phosphate, trialkyl phosphate, dialkyl phosphate, tris(chloroethyl) phosphate, phospha
  • silicone-based flame retardants such as silicone rubbers, silicone resins, etc.; These flame retardants may be used alone or in combination of two or more.
  • 1,3-phenylene bis(2,6-dixylenyl phosphate) is preferable because it does not impair low dielectric properties.
  • the content thereof is preferably 0.1% by mass or more of the resin composition, and is preferably 20% by mass or less, and 10% by mass or less. is more preferable.
  • a flame retardant can be used individually by 1 type or in combination of 2 or more types. When using two or more kinds, the total amount is within the above range.
  • the resin composition of this embodiment may contain a dispersant.
  • a dispersant those generally used for paints can be suitably used, and the type thereof is not particularly limited.
  • the dispersant is preferably a copolymer-based wetting and dispersing agent, and specific examples thereof include DISPERBYK (registered trademark)-110, 111, 161, 180, 2009, and 2152 manufactured by BYK-Chemie Japan Co., Ltd. , 2155, BYK®-W996, W9010, W903, W940 and the like.
  • the lower limit of the content is preferably 0.01 parts by mass or more with respect to 100 parts by mass of the resin solid content in the resin composition. It is more preferably 1 part by mass or more, and may be 0.3 parts by mass or more.
  • the upper limit of the content of the dispersant is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and 3 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition. Part or less is more preferable.
  • a dispersing agent can be used individually by 1 type or in combination of 2 or more types. When using two or more kinds, the total amount is within the above range.
  • the resin composition of this embodiment may further contain a curing accelerator.
  • the curing accelerator is not particularly limited, but for example, 2-ethyl-4-methylimidazole, imidazoles such as triphenylimidazole; benzoyl peroxide, lauroyl peroxide, acetyl peroxide, parachlorobenzoyl peroxide, di- organic peroxides such as tert-butyl-di-perphthalate; azo compounds such as azobisnitrile (especially azobisisobutyronitrile); N,N-dimethylbenzylamine, N,N-dimethylaniline, N, Tertiary compounds such as N-dimethyltoluidine, 2-N-ethylanilinoethanol, tri-n-butylamine, pyridine, quinoline, N-methylmorpholine, triethanolamine, triethylenediamine, tetramethylbutanediamine, N-methylpiperidine Amines; phenol
  • the lower limit of the content is preferably 0.005 parts by mass or more with respect to 100 parts by mass of the resin solid content in the resin composition. It is more preferably at least 0.01 part by mass, and even more preferably at least 0.1 part by mass.
  • the upper limit of the content of the curing accelerator is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, with respect to 100 parts by mass of the resin solid content in the resin composition. It is more preferably not more than parts by mass.
  • a hardening accelerator can be used individually by 1 type or in combination of 2 or more types. When using two or more kinds, the total amount is within the above range.
  • the resin composition of the present embodiment can be configured substantially free of organic peroxides (for example, organic peroxides having a molecular weight of 30 to 500). “Substantially free” means less than 0.1 parts by mass, preferably 0.01 parts by mass or less, relative to 100 parts by mass of resin solids contained in the resin composition of the present embodiment. . By setting it as such a range, the hardened
  • the resin composition of the present embodiment can be configured so as not to substantially contain an azo compound (for example, an azo compound having a molecular weight of 30 to 500).
  • “Substantially free” means less than 0.1 parts by mass, preferably 0.01 parts by mass or less, relative to 100 parts by mass of resin solids contained in the resin composition of the present embodiment. . By setting it as such a range, the hardened
  • the resin composition of the present embodiment may contain a solvent, and preferably contains an organic solvent.
  • a solvent is contained, the resin composition of the present embodiment is in a form (solution or varnish) in which at least part, preferably all of the various resin solids described above are dissolved or compatible with the solvent.
  • the solvent is not particularly limited as long as it is a polar organic solvent or a non-polar organic solvent capable of dissolving or dissolving at least part, preferably all, of the various resin solids described above. Examples of polar organic solvents include ketones.
  • nonpolar organic solvents include aromatic hydrocarbons (e.g., toluene, xylene, etc.).
  • a solvent can be used individually by 1 type or in combination of 2 or more types. When using two or more kinds, the total amount is within the above range.
  • the resin composition of the present embodiment may contain thermoplastic resins, various polymer compounds such as oligomers thereof, and various additives.
  • Additives include ultraviolet absorbers, antioxidants, polymerization initiators (e.g., photopolymerization initiators), fluorescent brighteners, photosensitizers, dyes, pigments, thickeners, fluidity modifiers, lubricants, Foaming agents, leveling agents, brighteners, polymerization inhibitors and the like are included. These additives can be used singly or in combination of two or more.
  • the resin composition of the present embodiment can also be configured substantially free of a radical polymerization initiator.
  • substantially free of radical polymerization initiator means that the content of the radical polymerization initiator is less than 1 part by mass and less than 0.5 parts by mass with respect to 100 parts by mass of the resin solid content. is preferable, less than 0.3 parts by mass is more preferable, and less than 0.1 parts by mass is even more preferable.
  • the amount of the radical polymerization initiator in the resin composition of the present embodiment is preferably less than 0.01% by mass with respect to 100% by mass of non-volatile components in the resin composition, and is 0.005% by mass or less. more preferably 0.001% by mass or less, and even more preferably 0% by mass (not including the radical polymerization initiator). Such a configuration tends to further improve electrical characteristics.
  • the resin composition of this embodiment is used as a cured product.
  • the resin composition of the present embodiment is suitably used as a low dielectric constant material and/or a low dielectric loss tangent material as a resin composition for electronic materials such as an insulating layer of a printed wiring board and a semiconductor package material. be able to.
  • the resin composition of the present embodiment can be suitably used as a material for prepregs, metal foil-clad laminates using prepregs, resin sheets, and printed wiring boards.
  • the resin composition of the present embodiment is used as a layered (film-like, sheet-like, etc.) material such as prepreg, resin sheet, etc., which becomes an insulating layer of a printed wiring board.
  • the thickness is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more.
  • the upper limit of the thickness is preferably 200 ⁇ m or less, more preferably 180 ⁇ m or less.
  • the thickness of the layered material means the thickness including the glass cloth, for example, when the resin composition of the present embodiment is impregnated into the glass cloth or the like.
  • the material formed from the resin composition of the present embodiment may be used for applications in which a pattern is formed by exposure and development, or may be used in applications without exposure and development. In particular, it is suitable for applications that do not require exposure and development.
  • the prepreg of this embodiment is formed from a base material (prepreg base material) and the resin composition of this embodiment.
  • the prepreg of the present embodiment can be produced, for example, by applying (for example, impregnating and/or applying) the resin composition of the present embodiment to a substrate and then heating (for example, drying at 120 to 220° C. for 2 to 15 minutes. etc.).
  • the amount of the resin composition adhered to the base material that is, the amount of the resin composition (including the filler (D)) relative to the total amount of the prepreg after semi-curing is preferably in the range of 20 to 99% by mass. It is more preferably in the range of ⁇ 80% by mass.
  • the base material is not particularly limited as long as it is a base material used for various printed wiring board materials.
  • materials for the base material include glass fibers (e.g., E-glass, D-glass, L-glass, S-glass, T-glass, Q-glass, UN-glass, NE-glass, spherical glass, etc.). , inorganic fibers other than glass (eg, quartz), and organic fibers (eg, polyimide, polyamide, polyester, liquid crystal polyester, polytetrafluoroethylene, etc.).
  • the form of the substrate is not particularly limited, and includes woven fabric, nonwoven fabric, roving, chopped strand mat, surfacing mat, and the like. These substrates may be used alone or in combination of two or more.
  • a woven fabric subjected to super-spreading treatment and stuffing treatment is preferable.
  • a glass woven fabric having a thickness of m 2 or less is preferable, and from the viewpoint of moisture absorption and heat resistance, a glass woven fabric surface-treated with a silane coupling agent such as epoxysilane or aminosilane is preferable.
  • a low dielectric glass cloth made of glass fibers exhibiting a low dielectric constant and a low dielectric loss tangent, such as L-glass, NE-glass, and Q-glass is more preferable.
  • Examples of low dielectric constant substrates include substrates having a relative dielectric constant of 5.0 or less (preferably 3.0 to 4.9).
  • low dielectric loss tangent substrates include substrates having a dielectric loss tangent of 0.006 or less (preferably 0.001 to 0.005).
  • the dielectric constant and dielectric loss tangent are values measured at 10 GHz using a perturbation method cavity resonator.
  • the metal foil-clad laminate of the present embodiment includes at least one sheet of the prepreg of the present embodiment and a metal foil arranged on one side or both sides of the prepreg.
  • a method for producing the metal foil-clad laminate of the present embodiment for example, at least one sheet of the prepreg of the present embodiment is arranged (preferably two or more sheets are stacked), a metal foil is arranged on one or both sides thereof, and lamination molding is performed. method. More specifically, the prepreg can be produced by arranging a metal foil such as copper or aluminum on one side or both sides of the prepreg and laminating the prepreg.
  • the number of prepregs is preferably 1 to 10, more preferably 2 to 10, and even more preferably 2 to 9.
  • the metal foil is not particularly limited as long as it is used as a material for printed wiring boards, and examples thereof include copper foil such as rolled copper foil and electrolytic copper foil.
  • the thickness of the metal foil (preferably copper foil) is not particularly limited, and may be about 1.5 to 70 ⁇ m.
  • Examples of the molding method include methods commonly used for molding laminates and multilayer boards for printed wiring boards, and more specifically, using a multi-stage press machine, a multi-stage vacuum press machine, a continuous molding machine, an autoclave molding machine, and the like.
  • a multilayer board can also be obtained by combining the prepreg of the present embodiment and a wiring board for an inner layer, which is separately prepared, and performing lamination molding.
  • a method for producing a multilayer board for example, copper foil of about 35 ⁇ m is placed on both sides of one prepreg of the present embodiment, laminated by the above molding method, an inner layer circuit is formed, and black is applied to this circuit.
  • the inner layer circuit board and the prepreg of the present embodiment are alternately arranged one by one, and copper foil is arranged on the outermost layer to satisfy the above conditions.
  • a multi-layer board can be produced by lamination molding, preferably under vacuum.
  • the metal foil-clad laminate of this embodiment can be suitably used as a printed wiring board.
  • the metal foil-clad laminate of the present embodiment preferably has a low dielectric constant (Dk) measured using a cured plate from which the metal foil has been removed by etching.
  • the dielectric constant (Dk) of the cured plate at 10 GHz measured according to the cavity resonance perturbation method is preferably 3.5 or less, more preferably 3.0 or less, and 2.5 or less. is more preferable.
  • the lower limit of the dielectric constant (Dk) is not particularly defined, for example, 2.0 or more is practical.
  • the metal foil-clad laminate of the present embodiment preferably has a low dielectric loss tangent (Df) measured using a cured plate from which the metal foil has been removed by etching.
  • the dielectric loss tangent (Df) at 10 GHz measured according to the cavity resonance perturbation method is preferably 0.0040 or less, more preferably 0.0030 or less, and further preferably 0.0020 or less. preferable. Although the lower limit of the dielectric loss tangent (Df) is not particularly defined, for example, 0.0001 or more is practical.
  • a dielectric constant (Dk) and a dielectric loss tangent (Df) are measured according to the method described in Examples below.
  • the resin composition for electronic materials obtained by using the resin composition of the present embodiment has heat resistance, low dielectric properties (low dielectric (low dielectric constant, low dielectric loss tangent), excellent low water absorption, chemical resistance, and desmear resistance.
  • the printed wiring board of the present embodiment is a printed wiring board including an insulating layer and a conductor layer disposed on the surface of the insulating layer, wherein the insulating layer is formed from the resin composition of the present embodiment. It includes at least one of a layer and a layer formed from the prepreg of this embodiment.
  • Such a printed wiring board can be manufactured according to a conventional method, and the manufacturing method is not particularly limited. An example of a method for manufacturing a printed wiring board is shown below. First, a metal foil-clad laminate such as the metal foil-clad laminate described above is prepared. Next, the surface of the metal foil-clad laminate is etched to form an inner layer circuit, thereby producing an inner layer substrate.
  • the surface of the inner layer circuit of this inner layer substrate is subjected to a surface treatment to increase the adhesive strength as necessary, and then the required number of prepregs described above are laminated on the surface of the inner layer circuit, and a metal foil for the outer layer circuit is laminated on the outer side. Then, heat and pressure are applied for integral molding. In this manner, a multi-layer laminate is produced in which an insulating layer composed of the substrate and the cured product of the resin composition is formed between the inner layer circuit and the metal foil for the outer layer circuit. Next, after drilling holes for through holes and via holes in this multi-layer laminate, a plated metal film is formed on the walls of the holes for conducting the inner layer circuit and the metal foil for the outer layer circuit, and further the outer layer circuit. A printed wiring board is manufactured by etching the metal foil for the purpose to form an outer layer circuit.
  • the printed wiring board obtained in the above production example has an insulating layer and a conductor layer formed on the surface of the insulating layer, and the insulating layer is the resin composition of the present embodiment and / or a cured product thereof.
  • the configuration includes That is, the prepreg of the present embodiment described above (for example, a prepreg formed from a substrate and the resin composition of the present embodiment impregnated or applied thereto), and the resin composition of the metal foil clad laminate of the present embodiment described above.
  • a layer formed from a material serves as an insulating layer in this embodiment.
  • the present embodiment relates to a semiconductor device including the printed wiring board.
  • the description in paragraphs 0200 to 0202 of JP-A-2021-021027 can be referred to, and the contents thereof are incorporated into this specification.
  • the resin sheet of the present embodiment includes a support and a layer formed from the resin composition of the present embodiment arranged on the surface of the support.
  • the resin sheet can be used as a build-up film or dry film solder resist.
  • the method for producing the resin sheet is not particularly limited, but for example, a method of obtaining a resin sheet by applying (coating) a solution obtained by dissolving the resin composition of the present embodiment in a solvent on a support and drying the solution. is mentioned.
  • Examples of the support used here include polyethylene film, polypropylene film, polycarbonate film, polyethylene terephthalate film, ethylenetetrafluoroethylene copolymer film, and a release film obtained by applying a release agent to the surface of these films, Organic film substrates such as polyimide films, conductor foils such as copper foils and aluminum foils, glass plates, SUS (Steel Use Stainless) plates, FRP (Fiber-Reinforced Plastics) and other plate-like substrates. It is not particularly limited.
  • Examples of the coating method include a method in which a solution obtained by dissolving the resin composition of the present embodiment in a solvent is applied onto a support using a bar coater, a die coater, a doctor blade, a baker applicator, or the like. be done. Further, after drying, a single-layer sheet can be obtained by peeling or etching the support from the resin sheet in which the support and the resin composition are laminated. It should be noted that a solution obtained by dissolving the resin composition of the present embodiment in a solvent is supplied into a mold having a sheet-like cavity and dried to form a sheet, thereby using a support. It is also possible to obtain a single layer sheet without
  • the drying conditions for removing the solvent are not particularly limited. A temperature of 20° C. to 200° C. and a time of 1 to 90 minutes are preferable because the curing of the composition proceeds. Further, the single-layer sheet or resin sheet can be used in an uncured state by simply drying the solvent, or can be used in a semi-cured (B-staged) state as necessary. Furthermore, the thickness of the resin layer in the single-layer sheet or resin sheet of the present embodiment can be adjusted by the concentration of the solution of the resin composition of the present embodiment used for coating (coating) and the coating thickness, and is not particularly limited. However, in general, the thicker the coating, the more likely the solvent will remain during drying.
  • the resulting polymer (va) having a structural unit represented by formula (V) had a number average molecular weight Mn of 2,060, a weight average molecular weight Mw of 30,700, and a monodispersity Mw/Mn of 14.9. there were.
  • Mn number average molecular weight
  • Mw weight average molecular weight
  • Mw/Mn monodispersity
  • Structural unit derived from divinylbenzene 20.9 mol% (24.3% by mass)
  • Structural unit derived from ethylvinylbenzene 9.1 mol% (10.7% by mass)
  • Structural unit derived from styrene 70.0 mol% (65.0% by mass)
  • the structural unit having a residual vinyl group derived from divinylbenzene was 16.7 mol % (18.5 mass %).
  • Resin "A” had a polystyrene-equivalent number-average molecular weight of 1975, a polystyrene-equivalent weight-average molecular weight of 3514, and a hydroxyl equivalent of 990 by GPC.
  • the resulting solution was concentrated by an evaporator and added dropwise to methanol for solidification, and the solid was collected by filtration and vacuum dried to obtain 450.1 g of a modified polyphenylene ether compound.
  • the modified polyphenylene ether compound had a polystyrene-equivalent number average molecular weight by GPC method of 2250, a polystyrene-equivalent weight average molecular weight by GPC method of 3920, and a vinyl group equivalent of 1189 g/vinyl group.
  • the resulting organic phase was washed 5 times with 1300 g of water.
  • the electrical conductivity of the wastewater after the fifth washing was 5 ⁇ S/cm, and it was confirmed that the ionic compounds that could be removed were sufficiently removed by washing with water.
  • the organic phase after washing with water was concentrated under reduced pressure and finally concentrated to dryness at 90° C. for 1 hour to obtain 331 g of the objective naphthol aralkyl cyanate compound (SNCN) (orange viscous substance).
  • the weight average molecular weight of the obtained SNCN was 600.
  • the IR spectrum of SNCN showed absorption at 2250 cm -1 (cyanate ester group) and did not show absorption of hydroxy group.
  • the weight average molecular weight and number average molecular weight were measured by a gel permeation chromatography (GPC) method.
  • GPC gel permeation chromatography
  • a liquid feed pump manufactured by Shimadzu Corporation, LC-20AD
  • a differential refractive index detector manufactured by Shimadzu Corporation, RID-10A
  • a GPC column manufactured by Showa Denko Corporation, GPC KF-801, 802, 803, 804.
  • tetrahydrofuran was used as the solvent
  • the flow rate was 1.0 ml/min
  • the column temperature was 40° C.
  • a calibration curve using monodisperse polystyrene was used.
  • Example 1 Maleimide compound (ma) (manufactured by DIC, "X9-470", compound represented by formula (M1)) 50 parts by mass, represented by formula (V) obtained in Synthesis Example 1 50 parts by mass of polymer (va) having a structural unit and 0.25 parts by mass of 2-ethyl-4-methylimidazole (catalyst) were dissolved in methyl ethyl ketone and mixed to obtain a varnish. In addition, each addition amount mentioned above shows a solid content amount.
  • n is an integer from 1 to 20;
  • ⁇ Measurement method and evaluation method> Relative permittivity (Dk) and dielectric loss tangent (Df)
  • the copper foil of the cured plate was removed by etching, cut to a width of 1.0 mm, dried at 120 ° C. for 60 minutes, and then measured at 10 GHz using a perturbation method cavity resonator. ) and dielectric loss tangent (Df) were measured.
  • the measurement temperature was 23°C.
  • Agilent 8722ES manufactured by Agilent Technologies was used as the perturbation method cavity resonator.
  • Dk and Df after moisture absorption were measured.
  • a pressure cooker tester a model PC-3 manufactured by Hirayama Seisakusho Co., Ltd. was used.
  • Example 2 In Example 1, the compounding amount of the maleimide compound (ma) was changed to 80 parts by mass, and the compounding amount of the polymer (va) having the structural unit represented by the formula (V) was changed to 20 parts by mass. .
  • Example 3 In Example 1, the compounding amount of the maleimide compound (ma) was changed to 30 parts by mass, and the compounding amount of the polymer (va) having the structural unit represented by the formula (V) was changed to 70 parts by mass. .
  • Example 4 In Example 1, the compounding amount of the maleimide compound (ma) was 30 parts by mass, and the compounding amount of the polymer (va) having the structural unit represented by the formula (V) was 30 parts by mass. 5 parts by mass of the modified polyphenylene ether compound obtained, 5 parts by mass of a maleimide compound (MIR-3000-70MT manufactured by Nippon Kayaku Co., Ltd.) having the structure shown below, and the naphthol aralkyl-type cyanate ester compound obtained in Synthesis Example 3 (SNCN) 5 parts by mass, thermoplastic elastomer (SBS, manufactured by JSR, TR2250) 15 parts by mass, phosphorus flame retardant (manufactured by Daihachi Chemical Industry Co., Ltd., PX-200, 1,3-phenylenebis (2,6 -Dixylenyl phosphate))) was blended, and other operations were carried out in the same manner. MIR-3000-70MT
  • Example 5 In Example 1, the compounding amount of the maleimide compound (ma) was 40 parts by mass, the compounding amount of the polymer (va) having the structural unit represented by the formula (V) was 40 parts by mass, and the thermoplastic elastomer (SBS, 20 parts by mass of TR2250 (manufactured by JSR Corporation) was blended, and the rest was carried out in the same manner.
  • SBS thermoplastic elastomer
  • Example 1 was repeated except that the maleimide compound (ma) was added in an amount of 100 parts by mass and the polymer (va) having the structural unit represented by formula (V) was not added.
  • Comparative example 2 In Example 1, the maleimide compound (ma) was not blended, and the blending amount of the polymer (va) having the structural unit represented by formula (V) was changed to 100 parts by mass.
  • Example 4 the maleimide compound (ma) and the polymer (va) having a structural unit represented by formula (V) were not blended, and 35 parts by mass of a modified polyphenylene ether compound and a maleimide compound (Nippon Kayaku Co., Ltd. company's MIR-3000-70MT.
  • the cured product of the resin composition of the present embodiment had low Dk and Df. It can be said that there is a significant difference when Dk decreases by 0.1 and when Df decreases by 0.001. It can be seen that remarkably excellent low dielectric properties are achieved compared to the cured product of . Moreover, although the cured product of the resin composition of Comparative Example 2 was excellent in low dielectric properties, the copper foil peel strength was remarkably low. The cured product of the resin composition of the present embodiment achieves low dielectric properties, particularly excellent low dielectric properties after moisture absorption, while achieving high copper foil peel strength.

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WO2025187617A1 (ja) * 2024-03-08 2025-09-12 三菱瓦斯化学株式会社 樹脂組成物、硬化物、プリプレグ、金属箔張積層板、樹脂複合シート、プリント配線板、および、半導体装置
WO2025192017A1 (ja) * 2024-03-15 2025-09-18 パナソニックＩｐマネジメント株式会社 難燃剤、樹脂組成物、プリプレグ、樹脂付きフィルム、樹脂付き金属箔、金属張積層板、及び配線板
WO2025204033A1 (ja) * 2024-03-26 2025-10-02 パナソニックＩｐマネジメント株式会社 難燃剤、樹脂組成物、プリプレグ、樹脂付きフィルム、樹脂付き金属箔、金属張積層板、及び配線板

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JP7710267B2 (ja) 2023-03-06 2025-07-18 ナミックス株式会社 樹脂組成物、並びに接着フィルム、積層基板、電子部品、及び半導体装置
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WO2024195718A1 (ja) * 2023-03-20 2024-09-26 Ｍｇｃエレクトロテクノ株式会社 プリント配線板の製造方法
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WO2025192017A1 (ja) * 2024-03-15 2025-09-18 パナソニックＩｐマネジメント株式会社 難燃剤、樹脂組成物、プリプレグ、樹脂付きフィルム、樹脂付き金属箔、金属張積層板、及び配線板
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