WO2023013711A1 - Composition de résine thermodurcissable, préimprégné, et carte de circuits imprimés - Google Patents

Composition de résine thermodurcissable, préimprégné, et carte de circuits imprimés Download PDF

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Publication number
WO2023013711A1
WO2023013711A1 PCT/JP2022/029871 JP2022029871W WO2023013711A1 WO 2023013711 A1 WO2023013711 A1 WO 2023013711A1 JP 2022029871 W JP2022029871 W JP 2022029871W WO 2023013711 A1 WO2023013711 A1 WO 2023013711A1
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group
epoxy
compound
resin composition
thermosetting resin
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PCT/JP2022/029871
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English (en)
Japanese (ja)
Inventor
尚義 金子
翔平 山口
克哉 富澤
博史 高橋
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三菱瓦斯化学株式会社
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Priority to KR1020237042475A priority Critical patent/KR20240040056A/ko
Priority to CN202280054398.XA priority patent/CN118251457A/zh
Priority to JP2023540403A priority patent/JPWO2023013711A1/ja
Publication of WO2023013711A1 publication Critical patent/WO2023013711A1/fr

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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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/092—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C08G59/245—Di-epoxy compounds carbocyclic aromatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
    • C08G59/306—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • C08G59/621—Phenols
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • 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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
    • 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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/5399—Phosphorus bound to nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08L79/085—Unsaturated polyimide precursors
    • 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

Definitions

  • the present invention relates to thermosetting resin compositions, prepregs and printed wiring boards.
  • Patent Document 1 discloses a curable composition containing an alkenylphenol, an epoxy-modified silicone, and an epoxy compound other than the epoxy-modified silicone, or a curable composition containing a polymer having these as structural units. is applied to prepregs, resin sheets, metal foil clad laminates and printed wiring boards.
  • the present invention has been made in view of the above problems, and aims to provide a thermosetting resin composition, a prepreg, and a printed wiring board that are excellent in heat resistance and low thermal expansion.
  • the inventors have made extensive studies to solve the above problems. As a result, the present inventors have found that the above problems can be solved by using an alkenylphenol, an epoxy-modified silicone, and an epoxy compound other than the epoxy-modified silicone in combination with an aromatic phosphorus compound, and have completed the present invention. .
  • thermosetting resin composition comprising an alkenylphenol A, an epoxy-modified silicone B, an epoxy compound C other than the epoxy-modified silicone B, and an aromatic phosphorus compound P.
  • a polymer D containing a structural unit derived from alkenylphenol A, a structural unit derived from epoxy-modified silicone B, and a structural unit derived from an epoxy compound C other than the epoxy-modified silicone B, and an aromatic phosphorus compound P
  • a thermosetting resin composition containing.
  • the thermosetting resin composition according to [2] further comprising at least one selected from the group consisting of alkenylphenol A, epoxy-modified silicone B, and an epoxy compound C other than the epoxy-modified silicone B.
  • thermosetting resin composition according to [2] or [3], wherein the polymer D has a weight average molecular weight of 3.0 ⁇ 10 3 to 5.0 ⁇ 10 4 .
  • thermosetting resin composition according to .
  • the thermosetting resin composition according to [6], wherein the cyanate ester compound comprises a naphthol aralkyl-type cyanate ester compound and/or a novolak-type cyanate ester compound.
  • the maleimide compound is bis(4-maleimidophenyl)methane, 2,2-bis ⁇ 4-(4-maleimidophenoxy)-phenyl ⁇ propane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane,
  • a thermosetting resin composition is bis(4-maleimidophenyl)methane, 2,2-bis ⁇ 4-(4-maleimidophenoxy)-phenyl ⁇ propane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane.
  • each R 5 independently represents a hydrogen atom or a methyl group, and n 1 represents an integer of 1 or more.
  • each R 13 independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, and n 4 represents an integer of 1 or more and 10 or less.
  • thermosetting resin composition according to any one of [1] to [10], wherein the epoxy compound C contains a naphthalene cresol novolac type epoxy resin and/or a naphthylene ether type epoxy resin.
  • the epoxy compound C contains a biphenyl type epoxy resin represented by the following formula (b2).
  • each Ra independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom.
  • the epoxy-modified silicone B contains an epoxy-modified silicone represented by the following formula (1).
  • each R 1 independently represents a single bond, an alkylene group, an arylene group or an aralkylene group, and each R 2 independently represents an alkyl group having 1 to 10 carbon atoms or a phenyl group. and n is an integer from 0 to 100.
  • the alkenylphenol A contains diallyl bisphenol and/or dipropenyl bisphenol.
  • thermosetting resin composition Any one of [1] to [15], wherein the aromatic phosphorus compound P contains at least one selected from the group consisting of a cyclic phosphazene compound, a phosphate ester compound, a phosphite ester compound and a phosphaphenanthrene compound.
  • the thermosetting resin composition according to . [17] Any one of [1] to [16], wherein the aromatic phosphorus compound P includes an aromatic phosphorus compound P′ represented by the following formulas (P1), (P2), (P3) or (P4). thermosetting resin composition.
  • Ph1, Ph2 and Ph3 represent a substituted or unsubstituted aryl group, and Ph1, Ph2 and Ph3 may be the same or different.
  • Ph1 and Ph2 represent a substituted or unsubstituted aryl group, the Ph1 and Ph2 may be the same or different, and R is an alkyl group having 1 to 30 carbon atoms. or represents an aryl group having 6 to 30 carbon atoms.
  • A is each independently a hydrogen atom, a methyl group, a hydroxyl group, a cyano group, an amino group, a carboxyl group, a glycidyloxy group, a parahydroxyphenyldimethyl group, a paraglycidyloxyphenyldimethyl group.
  • R represents a hydrogen atom, an alkyl group having 2 to 30 carbon atoms, or a substituted or unsubstituted aryl group.
  • thermosetting resin composition according to any one of [1] to [17], wherein the aromatic phosphorus compound P includes an aromatic phosphorus compound P'' represented by the following formula (P5).
  • the inorganic filler contains at least one selected from the group consisting of silicas, boehmite and alumina, and the content of the inorganic filler is 50 to 1000 parts by mass with respect to 100 parts by mass of the resin solid content.
  • [22] [1] A cured product obtained by curing the thermosetting resin composition according to any one of [21].
  • a laminate comprising the prepreg and/or a cured product obtained by curing the prepreg according to [23]; a metal foil arranged on one side or both sides of the laminate;
  • a metal foil clad laminate comprising: [25] an insulating layer containing a cured product obtained by curing the prepreg according to [23]; a conductor layer formed on the surface of the insulating layer; printed wiring boards, including;
  • thermosetting resin composition a prepreg and a printed wiring board that are excellent in heat resistance and low thermal expansion.
  • this embodiment a mode for carrying out the present invention (hereinafter referred to as “this embodiment") will be described in detail, but the present invention is not limited to this, and various modifications can be made without departing from the scope of the invention. It is possible.
  • the term "resin solid content” refers to the components excluding the solvent and filler in the thermosetting resin composition of the present embodiment, unless otherwise specified, and the resin solid content is 100 parts by mass. means that the total of the components excluding the solvent and filler in the thermosetting resin composition is 100 parts by mass. Moreover, 100 mass % of resin solid content means that the sum total of the component except a solvent and a filler in a thermosetting resin composition is 100 mass %.
  • thermosetting resin composition The thermosetting resin composition according to the first aspect of the present embodiment (hereinafter also referred to as “first composition”) comprises alkenylphenol A, epoxy-modified silicone B, and epoxy-modified silicone B other than Epoxy compound C and aromatic phosphorus compound P are contained. Since the first composition is configured in this way, it is excellent in heat resistance and low thermal expansion.
  • a thermosetting resin composition according to a second aspect of the present embodiment (hereinafter also referred to as a “second composition”) comprises a structural unit derived from alkenylphenol A and a structural unit derived from epoxy-modified silicone B.
  • thermosetting resin composition of the present embodiment includes both the “first composition” and the “second composition” unless otherwise specified.
  • Alkenylphenol A is not particularly limited as long as it is a compound having a structure in which one or more alkenyl groups are directly bonded to a phenolic aromatic ring. By containing alkenylphenol A, the thermosetting resin composition of the present embodiment has an improved balance between heat resistance and low thermal expansion.
  • the alkenyl group is not particularly limited, but examples thereof include alkenyl groups having 2 to 30 carbon atoms such as vinyl group, allyl group, propenyl group, butenyl group and hexenyl group. Among them, the alkenyl group is preferably an allyl group and/or a propenyl group, more preferably an allyl group, from the viewpoint of more effectively and reliably exhibiting the effects of the present embodiment.
  • the number of alkenyl groups directly bonded to one phenolic aromatic ring is not particularly limited, and is, for example, 1-4.
  • the number of alkenyl groups directly bonded to one phenolic aromatic ring is preferably 1 to 2, more preferably 1, from the viewpoint of more effectively and reliably exhibiting the effects of the present embodiment.
  • the bonding position of the alkenyl group to the phenolic aromatic ring is not particularly limited, but the ortho positions (2,6 positions) are preferable.
  • a phenolic aromatic ring is one in which one or more hydroxyl groups are directly bonded to an aromatic ring, and includes phenol rings and naphthol rings.
  • the number of hydroxyl groups directly bonded to one phenolic aromatic ring is not particularly limited, and is, for example, 1 to 2, preferably 1.
  • the phenolic aromatic ring may have substituents other than alkenyl groups.
  • substituents include linear alkyl groups having 1 to 10 carbon atoms, branched alkyl groups having 3 to 10 carbon atoms, cyclic alkyl groups having 3 to 10 carbon atoms, linear alkyl groups having 1 to 10 carbon atoms, A chain alkoxy group, a branched alkoxy group having 3 to 10 carbon atoms, a cyclic alkoxy group having 3 to 10 carbon atoms, and a halogen atom.
  • the number of such substituents directly bonded to one phenolic aromatic ring is not particularly limited, and is, for example, 1-2.
  • the bonding position of the substituent to the phenolic aromatic ring is not particularly limited.
  • Alkenylphenol A may have one or more structures in which one or more alkenyl groups are directly bonded to a phenolic aromatic ring. From the viewpoint of achieving the effects of the present embodiment more effectively and reliably, alkenylphenol A preferably has one or two structures in which one or more alkenyl groups are directly bonded to a phenolic aromatic ring. It is preferable to have
  • Alkenylphenol A may be, for example, a compound represented by the following formula (1A) or the following formula (1B).
  • Rxa each independently represents an alkenyl group having 2 to 8 carbon atoms
  • Rxb each independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom
  • Rxc is , each independently represents an aromatic ring having 4 to 12 carbon atoms
  • Rxc may form a fused structure with a benzene ring
  • Rxc may or may not be present
  • A represents an alkylene group having 1 to 6 carbon atoms, an aralkylene group having 7 to 16 carbon atoms, an arylene group having 6 to 10 carbon atoms, a fluorenylidene group, a sulfonyl group, an oxygen atom, a sulfur atom or a direct bond (single bond).
  • Rxc does not exist, one benzene ring may have two or more Rxa and/or Rxb groups.
  • Rxd each independently represents an alkenyl group having 2 to 8 carbon atoms
  • Rxe each independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom
  • Rxf is , represents an aromatic ring having 4 to 12 carbon atoms
  • Rxf may form a fused structure with a benzene ring
  • Rxf may or may not exist, and when Rxf does not exist , one benzene ring may have two or more Rxd and/or Rxe groups.
  • the alkenyl group having 2 to 8 carbon atoms represented by Rxa and Rxd is not particularly limited, and examples thereof include vinyl group, allyl group, propenyl group, butenyl group and hexenyl group. etc.
  • the alkyl group having 1 to 10 carbon atoms represented by Rxb and Rxe is not particularly limited, and examples thereof include methyl group, ethyl group, propyl group, butyl group, and pentyl group. , straight-chain alkyl groups such as hexyl group, branched alkyl groups such as isopropyl group, isobutyl group and tert-butyl group.
  • the alkylene group having 1 to 6 carbon atoms represented by A is not particularly limited, and examples thereof include methylene group, ethylene group, trimethylene group and propylene group.
  • the aralkylene group having 7 to 16 carbon atoms represented by A is not particularly limited, for example, the formulas: -CH 2 -Ar-CH 2 -, -CH 2 -CH 2 -Ar-CH 2 -CH 2 - , or a group represented by the formula: —CH 2 —Ar—CH 2 —CH 2 — (wherein Ar represents a phenylene group, a naphthylene group, or a biphenylene group).
  • the arylene group having 6 to 10 carbon atoms represented by A is not particularly limited, but includes, for example, a phenylene ring.
  • Rxf is preferably a benzene ring (compound containing a dihydroxynaphthalene skeleton) from the viewpoint of more effectively and reliably exhibiting the effects of the present embodiment.
  • alkenylphenol A is preferably an alkenylbisphenol in which one alkenyl group is bonded to each of two phenolic aromatic rings of a bisphenol.
  • alkenyl bisphenol is diallyl bisphenol in which two phenolic aromatic rings of bisphenols are respectively bonded to one allyl group, and/or bisphenols in which two phenolic aromatic rings are respectively bonded to one propenyl group. Dipropenyl bisphenol is preferred.
  • diallyl bisphenol examples include, but are not limited to, o, o'-diallyl bisphenol A ("DABPA", a product of Daiwa Kasei Kogyo Co., Ltd.), o, o'-diallyl bisphenol F, and o, o'-diallyl bisphenol S. , o,o'-diallylbisphenol fluorene.
  • DABPA o, o'-diallyl bisphenol A
  • F a product of Daiwa Kasei Kogyo Co., Ltd.
  • o, o'-diallyl bisphenol F examples include, but are not limited to, o, o'-diallyl bisphenol F, and o, o'-diallyl bisphenol S. , o,o'-diallylbisphenol fluorene.
  • dipropenyl bisphenol examples include, but are not limited to, o,o'-dipropenylbisphenol A ("PBA01" available from Gunei Chemical Industry Co., Ltd.), o,o'-dipropenylbisphenol F, o,o'- Dipropenyl bisphenol S, o,o'-dipropenyl bisphenol fluorene.
  • PBA01 available from Gunei Chemical Industry Co., Ltd.
  • o,o'-dipropenylbisphenol F o,o'- Dipropenyl bisphenol S
  • o,o'-dipropenyl bisphenol fluorene examples include, but are not limited to, o,o'-dipropenylbisphenol A ("PBA01" available from Gunei Chemical Industry Co., Ltd.), o,o'-dipropenylbisphenol F, o,o'- Dipropenyl bisphenol S, o,o'-dipropenyl bisphenol
  • the average number of phenol groups per molecule of alkenylphenol A is preferably 1 or more and less than 3, and 1.5 or more and 2.5 or less, from the viewpoint of more effectively and reliably exhibiting the effects of the present embodiment. is more preferred.
  • the average number of phenol groups is calculated by the following formula.
  • A represents the number of phenol groups of alkenylphenol having i phenol groups in the molecule
  • Xi represents the ratio of alkenylphenol having i phenol groups in the molecule to the total alkenylphenol
  • X 1 +X 2 + . . . X n 1.
  • Epoxy-modified silicone B is not particularly limited as long as it is a silicone compound or resin modified with an epoxy group-containing group. By containing the epoxy-modified silicone B, the thermosetting resin composition of the present embodiment is excellent in low thermal expansion and chemical resistance.
  • the silicone compound or resin is not particularly limited as long as it is a compound having a polysiloxane skeleton in which siloxane bonds are repeatedly formed.
  • the polysiloxane skeleton may be a linear skeleton, a cyclic skeleton, or a network skeleton. Among these, a linear skeleton is preferred from the viewpoint of more effectively and reliably exhibiting the effects of the present embodiment.
  • Examples of the epoxy group-containing group include, but are not particularly limited to, groups represented by the following formula (a1).
  • R 0 represents an alkylene group (for example, a methylene group, an ethylene group, an alkylene group having 1 to 5 carbon atoms such as a propylene group)
  • X is represented by the following formula (a2). represents a monovalent group or a monovalent group represented by the following formula (a3).
  • Epoxy-modified silicone B preferably contains an epoxy-modified silicone having an epoxy equivalent of 140 to 250 g/mol. Epoxy-modified silicone B tends to be able to further improve the balance between heat resistance and low thermal expansion by containing an epoxy-modified silicone having an epoxy equivalent within the above range. From the same viewpoint, the epoxy equivalent is more preferably 145 to 245 g/mol, still more preferably 150 to 240 g/mol.
  • Epoxy-modified silicone B preferably contains two or more epoxy-modified silicones from the viewpoint of further improving the balance between heat resistance and low thermal expansion.
  • the two or more epoxy-modified silicones preferably have different epoxy equivalents, and an epoxy-modified silicone having an epoxy equivalent of 50 to 350 g/mol (hereinafter also referred to as "low equivalent epoxy-modified silicone B1"). and an epoxy-modified silicone having an epoxy equivalent of 400 to 4000 g/mol (hereinafter also referred to as "high equivalent epoxy-modified silicone B2”), and an epoxy having an epoxy equivalent of 140 to 250 g/mol. More preferably, it contains a modified silicone (low-equivalent epoxy-modified silicone B1′) and an epoxy-modified silicone having an epoxy equivalent of 450 to 3000 g/mol (high-equivalent epoxy-modified silicone B2′).
  • the average epoxy equivalent of the epoxy-modified silicone B is preferably 140 to 3000 g/mol, more preferably 250 to 2000 g/mol. More preferably 300 to 1000 g/mol.
  • Epoxy-modified silicone B preferably contains an epoxy-modified silicone represented by the following formula (1) from the viewpoint of further improving the balance between heat resistance and low thermal expansion.
  • each R 1 independently represents a single bond, an alkylene group, an arylene group or an aralkylene group; each R 2 independently represents an alkyl group having 1 to 10 carbon atoms or a phenyl group; n represents an integer from 0 to 100;
  • the alkylene group represented by R 1 may be linear, branched or cyclic.
  • the number of carbon atoms in the alkylene group is preferably 1-12, more preferably 1-4.
  • Alkylene groups include, for example, a methylene group, an ethylene group, or a propylene group. Among these, R 1 is preferably a propylene group.
  • the arylene group represented by R 1 may have a substituent.
  • the number of carbon atoms in the arylene group is preferably 6-40, more preferably 6-20.
  • the arylene group includes, for example, a phenylene group, a cyclohexylphenylene group, a hydroxyphenylene group, a cyanophenylene group, a nitrophenylene group, a naphthylene group, a biphenylene group, an anthrylene group, a pyrenylene group, a fluorenylene group and the like. These groups may contain an ether bond, a ketone bond or an ester bond.
  • the aralkylene group represented by R 1 preferably has 7 to 30 carbon atoms, more preferably 7 to 13 carbon atoms.
  • Examples of the aralkylene group include groups represented by the following formula (XI). (In formula (XI), * represents a bond.)
  • the group represented by R 1 may further have a substituent.
  • substituents include linear alkyl groups having 1 to 10 carbon atoms, branched alkyl groups, cyclic alkyl groups having 3 to 10 carbon atoms, linear alkoxy groups having 1 to 10 carbon atoms, branched alkoxy groups having 3 to 10 carbon atoms and cyclic alkoxy groups having 3 to 10 carbon atoms. be done.
  • R 1 is particularly preferably a propylene group.
  • each R 2 independently represents an alkyl group having 1 to 10 carbon atoms or a phenyl group.
  • the above alkyl group and phenyl group may have a substituent.
  • the alkyl group having 1 to 10 carbon atoms may be linear, branched or cyclic.
  • Examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl and cyclohexyl groups.
  • R 2 is preferably a methyl group or a phenyl group.
  • n represents an integer of 0 or more, for example, 0 to 100. From the viewpoint of further improving the balance between heat resistance and low thermal expansion, n is preferably 50 or less, more preferably 30 or less, and even more preferably 20 or less.
  • epoxy-modified silicone B preferably contains two or more types of epoxy-modified silicone represented by formula (1).
  • two or more types of epoxy-modified silicones preferably have different values of n. It is more preferable to contain a certain epoxy-modified silicone.
  • the average number of epoxy groups per molecule of the epoxy-modified silicone B is preferably 1 or more and less than 3, and is 1.5 or more and 2.5 or less, from the viewpoint of more effectively and reliably exhibiting the effects of the present embodiment. is more preferable.
  • the content of the epoxy-modified silicone B is 5 to 95% by mass with respect to the total 100% by mass of the epoxy-modified silicone B and the epoxy compound C, from the viewpoint of expressing even better low thermal expansion and chemical resistance. , more preferably 10 to 90% by mass, even more preferably 40 to 85% by mass, even more preferably 50 to 80% by mass.
  • epoxy-modified silicone B a commercially available product may be used, or a product manufactured by a known method may be used. Examples of commercially available products include “X-22-163" and “KF-105" manufactured by Shin-Etsu Chemical Co., Ltd.
  • Epoxy compound C is an epoxy compound other than epoxy-modified silicone B, more specifically, an epoxy compound that does not have a polysiloxane skeleton.
  • the thermosetting resin composition of the present embodiment can exhibit heat resistance, chemical resistance, copper foil adhesion, and insulation reliability.
  • the epoxy compound C is not particularly limited as long as it is an epoxy compound other than the epoxy-modified silicone B.
  • the epoxy compound C in the thermosetting resin composition of the present embodiment is typically a bifunctional epoxy compound having two epoxy groups in one molecule or a polyfunctional epoxy compound having three or more epoxy groups in one molecule. Epoxy compounds can be used. Epoxy compound C preferably contains a bifunctional epoxy compound and/or a polyfunctional epoxy compound from the viewpoint of being able to exhibit even better heat resistance, chemical resistance, copper foil adhesion and insulation reliability.
  • the epoxy compound C in the thermosetting resin composition of the present embodiment is not particularly limited, but a compound represented by the following formula (3a) can be used.
  • Ar 3 each independently represents a benzene ring or naphthalene ring
  • Ar 4 represents a benzene ring, naphthalene ring or biphenyl ring
  • R 3a each independently represents a hydrogen atom.
  • the benzene ring or naphthalene ring in Ar 3 may further have one or more substituents, and the substituent may be a glycidyloxy group (not shown), or other substituents such as It may be an alkyl group having 1 to 5 carbon atoms, a phenyl group, etc.
  • the benzene ring, naphthalene ring or biphenyl ring in Ar 4 may further have one or more substituents, which may be a glycidyloxy group, other substituents such as carbon number It may be an alkyl group of 1 to 5, a phenyl group, or the like.
  • examples of bifunctional epoxy compounds include compounds represented by the following formula (b1).
  • each Ar 3 independently represents a benzene ring or naphthalene ring
  • each Ar 4 represents a benzene ring, naphthalene ring or biphenyl ring
  • each R 3a independently represents a hydrogen atom or represents a methyl group
  • the benzene ring or naphthalene ring in Ar 3 may further have one or more substituents, and the substituents are, for example, a glycidyloxy group such as an alkyl group having 1 to 5 carbon atoms or a phenyl group.
  • the benzene ring, naphthalene ring or biphenyl ring in Ar 4 may further have one or more substituents, and the substituents are, for example, a glycidyloxy group such as an alkyl group having 1 to 5 carbon atoms or a phenyl group. It may be a substituent other than )
  • the compound represented by formula (3a) is preferably a phenolic novolac type epoxy resin in which Ar 4 in formula (3a) is at least substituted with a glycidyloxy group.
  • the phenolic novolak-type epoxy resin is not particularly limited. Epoxy resins may be mentioned.
  • each Ar 31 independently represents a benzene ring or a naphthalene ring
  • each Ar 41 independently represents a benzene ring, a naphthalene ring or a biphenyl ring
  • each R 31a independently represents represents represents a hydrogen atom or a methyl group
  • p represents 1
  • kz represents an integer of 1 to 50
  • each ring represents a substituent other than a glycidyloxy group (for example, an alkyl group having 1 to 5 carbon atoms, a 1 to 5 alkoxy groups or phenyl groups)
  • at least one of Ar 31 and Ar 41 represents a naphthalene ring.
  • Compounds having a structure represented by formula (3-1) include compounds having a structure represented by formula (3-2). (Wherein, R represents a methyl group, and kz is synonymous with kz in the above formula (3-1).)
  • the naphthalene cresol novolak type epoxy resin is not particularly limited, but for example, a cresol/naphthol novolak type epoxy resin represented by the following formula (NE) is preferable.
  • the compound represented by the following formula (NE) is a random copolymer of a cresol novolak epoxy structural unit and a naphthol novolak epoxy structural unit, and both cresol epoxy and naphthol epoxy can be terminals.
  • n and n in the formula (NE) each represent an integer of 1 or more.
  • naphthalene cresol novolac type epoxy resin a commercially available product or a product manufactured by a known method may be used.
  • commercially available products include "NC-7000", “NC-7300” and “NC-7300L” manufactured by Nippon Kayaku Co., Ltd., and "HP-9540” and “HP-9500” manufactured by DIC Corporation. and "HP-9540" is particularly preferred.
  • the compound represented by formula (3a) may be a compound (hereinafter also referred to as "aralkyl epoxy resin") that does not correspond to the phenolic novolac epoxy resins described above.
  • Aralkyl-type epoxy resins include compounds in which Ar 3 is a naphthalene ring and Ar 4 is a benzene ring in the formula (3a) (also referred to as a "naphthol aralkyl- type epoxy resin”); It is preferably a compound in which it is a benzene ring and Ar 4 is a biphenyl ring (also referred to as a "biphenylaralkyl-type epoxy resin”), and more preferably a biphenylaralkyl-type epoxy resin.
  • naphthol aralkyl type epoxy resin a commercially available product or a product manufactured by a known method may be used.
  • Examples of commercially available products include “HP-5000” and “HP-9900” manufactured by DIC Corporation, and “ESN-375” and “ESN-475" manufactured by Nippon Steel Chemical & Materials Co., Ltd.
  • the biphenyl aralkyl type epoxy resin is preferably a compound represented by the following formula (3b). (Wherein, ka represents an integer of 1 or more, preferably 1 to 20, more preferably 1 to 6.)
  • bifunctional epoxy compounds include, for example, compounds in which ka is 1 in formula (3b).
  • biphenyl aralkyl type epoxy resin a commercially available product or a product manufactured by a known method may be used.
  • commercially available products include “NC-3000”, “NC-3000L”, and “NC-3000FH” manufactured by Nippon Kayaku Co., Ltd.
  • the epoxy compound C in the thermosetting resin composition of the present embodiment it is preferable to use a naphthalene-type epoxy resin (excluding those corresponding to the compounds represented by formula (3a)).
  • the naphthalene-type epoxy resin is preferably a naphthylene ether-type epoxy resin from the viewpoint of further improving heat resistance, chemical resistance, copper foil adhesion, and insulation reliability.
  • the naphthylene ether type epoxy resin is a bifunctional epoxy compound represented by the following formula (3-3) or the following formula (3 -4) is preferably a polyfunctional epoxy compound or a mixture thereof.
  • each R 13 is independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms (eg, methyl group or ethyl group), or an alkenyl group having 2 to 3 carbon atoms (eg, vinyl group, allyl group or propenyl group).
  • each R 14 is independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms (e.g., methyl group or ethyl group), or an alkenyl group having 2 to 3 carbon atoms (e.g., vinyl group, allyl group or propenyl group).)
  • a commercially available product or a product manufactured by a known method may be used as the naphthylene ether type epoxy resin.
  • Commercially available naphthylene ether type epoxy resins include, for example, DIC Corporation products "HP-6000", “EXA-7300”, “EXA-7310", “EXA-7311”, “EXA-7311L”, “ EXA7311-G3", “EXA7311-G4", “EXA-7311G4S”, “EXA-7311G5", etc., and HP-6000 is particularly preferred.
  • each R 3b is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms (e.g., methyl group or ethyl group), an aralkyl group, a benzyl group, a naphthyl group, at least one glycidyl represents a naphthyl group containing an oxy group or a naphthylmethyl group containing at least one glycidyloxy group, and n represents an integer of 0 or more (eg, 0 to 2).)
  • each Ra independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom.
  • the alkyl group having 1 to 10 carbon atoms may be linear, branched or cyclic.
  • alkyl groups include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl and cyclohexyl groups.
  • the biphenyl-type epoxy resin may be in the form of a mixture of compounds b2 having different numbers of Ra as alkyl groups. Specifically, it is preferably a mixture of biphenyl-type epoxy resins having different numbers of Ra as alkyl groups. It is more preferred to be a mixture of compounds b2 which are
  • a dicyclopentadiene type epoxy resin (excluding those corresponding to the epoxy compound C described above) can be used.
  • the dicyclopentadiene-type epoxy resin is not particularly limited, but includes, for example, compounds represented by the following formula (3-5). (In the formula, each R 3c independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and k2 represents an integer of 0 to 10.)
  • each R 3c independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms (eg, methyl group or ethyl group).)
  • dicyclopentadiene type epoxy resin A commercially available product or a product manufactured by a known method may be used as the dicyclopentadiene type epoxy resin.
  • Commercial products of dicyclopentadiene type epoxy resin include "EPICRON HP-7200L”, “EPICRON HP-7200”, “EPICRON HP-7200H” and "EPICRON HP-7000HH” manufactured by Dainippon Ink and Chemicals. mentioned.
  • the epoxy compound C is an epoxy compound represented by the formula (3a), a naphthalene-type epoxy resin and a biphenyl, from the viewpoint of being able to exhibit even better heat resistance, chemical resistance, copper foil adhesion and insulation reliability.
  • Epoxy compound C may contain other epoxy compounds that do not correspond to the epoxy compounds described above.
  • other epoxy compounds include, but are not limited to, bisphenol-type epoxy resins, trisphenolmethane-type epoxy resins, anthracene-type epoxy resins, glycidyl ester-type epoxy resins, polyol-type epoxy resins, isocyanurate ring-containing epoxy resins, and fluorene-type epoxy resins.
  • examples thereof include resins, epoxy resins composed of bisphenol A structural units and hydrocarbon structural units, and the like.
  • bisphenol-type epoxy resins can be included.
  • bisphenol-type epoxy resins examples include diallyl Bisphenol type epoxy resins (for example, diallyl bisphenol A type epoxy resin, diallyl bisphenol E type epoxy resin, diallyl bisphenol F type epoxy resin, diallyl bisphenol S type epoxy resin, etc.) and the like can be used.
  • epoxy compound C one of the above-described epoxy compounds and epoxy resins may be used alone, or two or more thereof may be used in combination.
  • the average number of epoxy groups per molecule of the epoxy compound C is preferably 1 or more and less than 3, and 1.5 or more and 2.5 or less, from the viewpoint of more effectively and reliably exhibiting the effects of the present embodiment. is more preferred.
  • the content of the epoxy compound C is, from the viewpoint of being able to exhibit even better heat resistance, chemical resistance, copper foil adhesion and insulation reliability, the total amount of the epoxy-modified silicone B and the epoxy compound C being 100% by mass, It is preferably 5 to 95% by mass, more preferably 10 to 90% by mass, still more preferably 15 to 60% by mass, and particularly preferably 20 to 50% by mass.
  • thermosetting resin composition of the present embodiment contains a maleimide compound, a cyanate ester compound, and a phenol other than the alkenylphenol A. It is preferable to further include at least one compound E selected from the group consisting of compound A' and alkenyl-substituted nadimide compounds.
  • compound E is not particularly limited, it is preferably bifunctional or higher, and may be trifunctional or higher polyfunctional.
  • the content of compound E in the thermosetting resin composition of the present embodiment is preferably 10 to 80% by mass, preferably 20 to 60% by mass, relative to 100% by mass of the resin solid content. is more preferred, and 30 to 50% by mass is even more preferred.
  • the thermosetting resin composition of the present embodiment preferably contains a maleimide compound from the viewpoint of further improving heat resistance, low thermal expansion and chemical resistance.
  • the maleimide compound is not particularly limited as long as it is a compound having one or more maleimide groups in one molecule.
  • each R 5 independently represents a hydrogen atom or a
  • n 1 is 1 or more, preferably 1-100, more preferably 1-10.
  • the maleimide compound is preferably a compound having two or more maleimide groups in one molecule, and bis(4-maleimidophenyl)methane , 2,2-bis ⁇ 4-(4-maleimidophenoxy)-phenyl ⁇ propane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, a maleimide compound represented by formula (3), and the following More preferably, it contains at least one selected from the group consisting of maleimide compounds represented by formula (3′).
  • each R 13 independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, and n 4 represents an integer of 1 or more and 10 or less.
  • maleimide compound a commercially available product or a product manufactured by a known method may be used.
  • Commercially available maleimide compounds include "BMI-70", “BMI-80” and “BMI-1000P” manufactured by K.I. -4000", “BMI-5100", “BMI-7000”, “BMI-2300”, Nippon Kayaku Co., Ltd. product "MIR-3000-MT” (R 13 in formula (3') are all hydrogen atoms and n4 is a mixture of 1 to 10.) and the like.
  • the content of the maleimide compound is preferably 1 to 50 parts by mass, preferably 5 to 40 parts by mass, relative to 100 parts by mass of the resin solid content. More preferably, 10 to 40 parts by mass is even more preferable.
  • thermosetting resin composition of the present embodiment preferably contains a cyanate ester compound from the viewpoint of further improving heat resistance, low thermal expansion, copper foil adhesion and chemical resistance.
  • the cyanate ester compound is not particularly limited as long as it is a compound having two or more cyanate groups (cyanate ester groups) in one molecule.
  • cyanate ester compounds are used singly or in combination of two or more.
  • the cyanate ester compound is a naphthol aralkyl type cyanate ester compound and/or a novolac type cyanate ester compound. It preferably contains a functional cyanate ester compound.
  • each R 6 independently represents a hydrogen atom or a methyl group, and n 2 represents an integer of 1 or more.
  • each Rya independently represents an alkenyl group having 2 to 8 carbon atoms or a hydrogen atom
  • each Ryb independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom.
  • Ryc each independently represents an aromatic ring having 4 to 12 carbon atoms or a hydrogen atom, Ryc may form a condensed structure with a benzene ring, Ryc may be present or may be present
  • a 1a each independently represents an alkylene group having 1 to 6 carbon atoms, an aralkylene group having 7 to 16 carbon atoms, an arylene group having 6 to 10 carbon atoms, a fluorenylidene group, a sulfonyl group, and an oxygen atom.
  • one benzene ring may have two or more Rya and/or Ryb groups.n is 1 to represents an integer of 20.
  • the cyanate ester compound includes a compound represented by formula (4) and/or formula (5) from the viewpoint of further improving heat resistance, low thermal expansion, copper foil adhesion and chemical resistance. is preferred.
  • n2 represents an integer of 1 or more, preferably an integer of 1-20, more preferably an integer of 1-10.
  • the alkenyl group having 2 to 8 carbon atoms represented by Rya is not particularly limited, and examples thereof include vinyl group, allyl group, propenyl group, butenyl group, and hexenyl group.
  • the alkyl group having 1 to 10 carbon atoms represented by Ryb is not particularly limited. branched alkyl groups such as isopropyl group, isobutyl group and tert-butyl group;
  • the alkylene group having 1 to 6 carbon atoms represented by A 1a is not particularly limited, but includes methylene group, ethylene group, trimethylene group and propylene group.
  • the aralkylene group having 7 to 16 carbon atoms represented by A 1a is not particularly limited, and examples thereof include formulas: —CH 2 —Ar—CH 2 — and —CH 2 —CH 2 . -Ar-CH 2 -CH 2 -, or a group represented by the formula: -CH 2 -Ar-CH 2 -CH 2 - (wherein Ar represents a phenylene group, a naphthylene group, or a biphenylene group) is mentioned.
  • the arylene group having 6 to 10 carbon atoms represented by A 1a is not particularly limited, but includes, for example, a phenylene ring.
  • n represents an integer of 1-20, preferably an integer of 1-15, more preferably an integer of 1-10.
  • the compound represented by Formula (5) is preferably a compound represented by Formula (c1) below.
  • each Rx independently represents a hydrogen atom or a methyl group
  • each R independently represents an alkenyl group having 2 to 8 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or hydrogen represents an atom
  • n represents an integer from 1 to 10.
  • cyanate ester compounds may be produced according to known methods. Specific production methods include, for example, the method described in JP-A-2017-195334 (particularly paragraphs 0052 to 0057).
  • the content of the cyanate ester compound is preferably 5 to 70 parts by mass with respect to 100 parts by mass of the resin solid content from the viewpoint of further improving heat resistance, low thermal expansion, copper foil adhesion and chemical resistance. It is preferably 10 to 60 parts by mass, even more preferably 10 to 40 parts by mass.
  • the thermosetting resin composition of the present embodiment can contain a phenol compound A' other than alkenylphenol A from the viewpoint of exhibiting even better chemical resistance.
  • the phenolic compound A′ is not particularly limited, but may be a bisphenol-type phenol resin (eg, bisphenol A-type resin, bisphenol E-type resin, bisphenol F-type resin, bisphenol S-type resin, etc.), phenolic novolac resin (e.g., phenol novolac resins, naphthol novolak resins, cresol novolac resins, aminotriazine novolak resins described later, etc.), glycidyl ester type phenolic resins, naphthalene type phenolic resins, anthracene type phenolic resins, dicyclopentadiene type phenolic resins, biphenyl type phenolic resins, alicyclic Phenolic resins, polyol-type phenolic resins,
  • the phenolic compound A' preferably contains a bifunctional phenolic compound having two phenolic hydroxyl groups in one molecule or an aminotriazine novolac resin, from the viewpoint of being able to exhibit even better chemical resistance.
  • bifunctional phenol compound examples include, but are not limited to, bisphenol, biscresol, bisphenols having a fluorene skeleton (e.g., bisphenol having a fluorene skeleton, biscresol having a fluorene skeleton, etc.), biphenols (e.g., p, p'- biphenol, etc.), dihydroxydiphenyl ether (e.g., 4,4'-dihydroxydiphenyl ether, etc.), dihydroxydiphenyl ketone (e.g., 4,4'-dihydroxydiphenyl ketone, etc.), dihydroxydiphenyl sulfide (e.g., 4,4'-dihydroxydiphenyl sulfide) etc.), and dihydroxyarene (eg, hydroquinone, etc.).
  • bisphenol biscresol
  • bisphenols having a fluorene skeleton e.g., bisphenol having a fluorene skeleton, biscre
  • bifunctional phenol compounds are used singly or in combination of two or more.
  • the bifunctional phenol compound preferably contains one or more selected from the group consisting of bisphenol, biscrresol, and bisphenols having a fluorene skeleton, from the viewpoint of being able to exhibit even better chemical resistance. It is more preferable to contain bisphenols having a fluorene skeleton. From the same viewpoint as above, bis-cresol fluorene is preferable as the bisphenols having a fluorene skeleton.
  • the thermosetting resin composition of the present embodiment may contain an aminotriazine novolac resin as the phenol compound A'.
  • the aminotriazine novolak resin When the aminotriazine novolak resin is contained, the terminal hydroxyl group or epoxy group generated by the reaction of the alkenylphenol A, the epoxy-modified silicone B, and the epoxy compound C other than the epoxy-modified silicone B, and the aminotriazine novolac resin are further combined. It tends to react and increase terminal functional groups such as hydroxyl groups and amino groups. As a result, a large number of terminal functional groups having high reactivity with the thermosetting resin are present, so that the compatibility and crosslink density are improved, and the peel strength of the copper foil tends to be improved.
  • the aminotriazine novolak resin is not particularly limited, but from the viewpoint of improving the copper foil peel strength, it is preferably a novolak resin having 2 to 20 phenolic hydroxyl groups per triazine skeleton in the molecule. More preferably, it is a novolac resin having 2 to 15 phenolic hydroxyl groups for one triazine skeleton in the molecule, and a novolac resin having 2 to 10 phenolic hydroxyl groups for one triazine skeleton in the molecule. is more preferred.
  • the content of alkenylphenol A in the thermosetting resin composition of the present embodiment is, from the viewpoint of further improving the balance between heat resistance and low thermal expansion, alkenylphenol A, epoxy-modified silicone B, epoxy compound C and phenol compound. It is preferably 1 to 50 parts by mass, more preferably 3 to 30 parts by mass, and even more preferably 5 to 20 parts by mass, relative to 100 parts by mass of A'.
  • the content of the epoxy-modified silicone B in the thermosetting resin composition of the present embodiment is alkenylphenol A, the epoxy-modified silicone B, and the epoxy compound C, from the viewpoint of expressing even better low thermal expansion and chemical resistance in a well-balanced manner. It is preferably 5 to 70 parts by mass, more preferably 10 to 60 parts by mass, and even more preferably 20 to 55 parts by mass with respect to 100 parts by mass of the total amount of phenol compound A'.
  • the content of the epoxy compound C in the thermosetting resin composition of the present embodiment is, from the viewpoint of expressing even better chemical resistance, copper foil adhesion and insulation reliability, alkenylphenol A, epoxy-modified silicone B, epoxy It is preferably 5 to 50 parts by mass, more preferably 10 to 30 parts by mass, and even more preferably 15 to 25 parts by mass with respect to 100 parts by mass of the total amount of compound C and phenol compound A'. .
  • the content of the phenolic compound A' in the thermosetting resin composition of the present embodiment is, from the viewpoint of being able to exhibit even better chemical resistance, the content of the alkenylphenol A, the epoxy-modified silicone B, the epoxy compound C and the phenolic compound A'. It is preferably 5 to 30 parts by mass, more preferably 10 to 25 parts by mass, even more preferably 15 to 20 parts by mass, based on the total amount of 100 parts by mass.
  • thermosetting resin composition does not contain the phenol compound A′
  • contents of the alkenylphenol A, the epoxy-modified silicone B, and the epoxy compound C are the same as those of the alkenylphenol A, the epoxy-modified silicone B, and the epoxy compound. It represents the content per 100 parts by mass of the total amount of C.
  • the thermosetting resin composition of the present embodiment preferably contains an alkenyl-substituted nadimide compound from the viewpoint of further improving heat resistance.
  • the alkenyl-substituted nadimide compound is not particularly limited as long as it is a compound having one or more alkenyl-substituted nadimide groups in one molecule, and examples thereof include compounds represented by the following formula (2d).
  • each R 1 independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (e.g., a methyl group or an ethyl group); represents an alkylene group, a phenylene group, a biphenylene group, a naphthylene group, or a group represented by the following formula (6) or (7).
  • R3 represents a methylene group, an isopropylidene group, CO, O, S or SO2 .
  • each R 4 independently represents an alkylene group having 1 to 4 carbon atoms or a cycloalkylene group having 5 to 8 carbon atoms.
  • alkenyl-substituted nadimide compound represented by formula (2d) a commercially available product or a product manufactured according to a known method may be used.
  • Commercially available products include “BANI-M” and “BANI-X” manufactured by Maruzen Petrochemical Co., Ltd.
  • the content of the alkenyl-substituted nadimide compound is preferably 1 to 40 parts by mass, more preferably 5 to 35 parts by mass, based on 100 parts by mass of the resin solid content. , more preferably 10 to 30 parts by mass.
  • the second composition contains polymer D containing structural units derived from alkenylphenol A, structural units derived from epoxy-modified silicone B, and structural units derived from epoxy compound C. Moreover, the polymer D may further contain a structural unit derived from a phenol compound A' other than the alkenylphenol A.
  • structural units derived from alkenylphenol A "structural units derived from epoxy-modified silicone B,””structural units derived from epoxy compound C,” and "phenol compounds A other than alkenylphenol A
  • the description to the effect that it contains a 'structural unit derived from' is a structure in which each component of alkenylphenol A, epoxy-modified silicone B, epoxy compound C and, if necessary, phenol compound A' is polymerized in polymer D. It includes the case of containing a unit and the case of containing a structural unit formed by a reaction or the like that can give a similar structural unit.
  • Alkenylphenol A, epoxy-modified silicone B, epoxy compound C, and phenol compound A' are as described above.
  • a structural unit derived from alkenylphenol A a structural unit derived from epoxy-modified silicone B, a structural unit derived from epoxy compound C, and a structural unit derived from phenol compound A' other than alkenylphenol A, respectively. Also referred to as units A, B, C, and A'.
  • the second composition comprises, in addition to the polymer D and the aromatic phosphorus compound P, optionally the above-described maleimide compound, cyanate ester compound, phenol compound A' other than the alkenylphenol A, and an alkenyl-substituted nadimide compound. It may further contain at least one compound E selected from the group consisting of The compound E may be an unreacted component remaining after polymerization of the polymer D, or may be a component newly added to the synthesized polymer D.
  • the second composition contains at least one selected from the group consisting of the above-described alkenylphenol A, epoxy-modified silicone B and epoxy compound C. good too.
  • the alkenylphenol A, the epoxy-modified silicone B, or the epoxy compound C contained in the second composition may be an unreacted component remaining after the polymerization of the polymer D, or Alternatively, it may be a component added anew.
  • the weight-average molecular weight of polymer D is preferably 3.0 ⁇ 10 3 to 5.0 ⁇ 10 4 , more preferably 3.0 ⁇ 10 3 to 2.0 ⁇ 10 in terms of polystyrene in gel permeation chromatography. 4 is more preferred.
  • a weight average molecular weight of 3.0 ⁇ 10 3 or more the second composition tends to exhibit even better copper foil adhesion and chemical resistance.
  • a weight average molecular weight of 5.0 ⁇ 10 4 or less tends to further improve the balance between heat resistance and low thermal expansion.
  • the content of the structural unit A in the polymer D is preferably 5-50% by mass with respect to the total mass of the polymer D.
  • the second composition tends to further improve the balance between heat resistance and low thermal expansion.
  • the content of structural unit A is more preferably 10 to 45% by mass, even more preferably 10 to 40% by mass.
  • the content of the structural unit B in the polymer D is preferably 20-60% by mass with respect to the total mass of the polymer D.
  • the content of the structural unit B is within the above range, the second composition tends to exhibit even better low thermal expansion and chemical resistance in a well-balanced manner.
  • the content of the structural unit B is more preferably 25 to 55% by mass, even more preferably 30 to 55% by mass.
  • Structural unit B is an epoxy-modified silicone having an epoxy equivalent of 50 to 350 g/mol (low equivalent epoxy-modified silicone B1) and an epoxy-modified silicone having an epoxy equivalent of 400 to 4000 g/mol (high equivalent epoxy-modified silicone B2). It preferably contains a structural unit derived from. Low-equivalent epoxy-modified silicone B1 and high-equivalent epoxy-modified silicone B2 have an epoxy equivalent of 140-250 g/mol (low-equivalent epoxy-modified silicone B1′) and 450-3000 g/mol, respectively. Epoxy-modified silicone (high-equivalent epoxy-modified silicone B2') is more preferable.
  • the content of the structural unit B1 derived from the low-equivalent epoxy-modified silicone B1 in the polymer D is preferably 5 to 25% by mass, more preferably 7.5 to 20% by mass, relative to the total mass of the polymer D. is more preferable, and 10 to 17% by mass is even more preferable.
  • the content of the structural unit B2 derived from the high-equivalent epoxy-modified silicone B2 in the polymer D is preferably 15 to 55% by mass, more preferably 20 to 52.5% by mass, relative to the total mass of the polymer D. and more preferably 25 to 50% by mass.
  • the mass ratio of the content of the structural unit B2 to the content of the structural unit B1 is preferably 1.5 to 4, more preferably 1.5 to 3.5, and 1.5 to 3.3. is more preferable.
  • the contents of the structural unit B1 and the structural unit B2 have the above relationship, the copper foil adhesion and chemical resistance tend to be further improved.
  • the compound represented by the above formula (b1), the compound represented by the above formula (b2), the compound represented by the above formula (b3), and the above formula (b4) It is preferably a unit derived from at least one selected from the group consisting of the compounds represented.
  • the structural unit C in the polymer D is more preferably a unit derived from the compound represented by the above formula (b2).
  • the content of the structural unit C in the polymer D is preferably 5-40% by mass with respect to the total mass of the polymer D.
  • the content of the structural unit C is within the above range, the second composition tends to exhibit even better heat resistance, chemical resistance, copper foil adhesion and insulation reliability.
  • the content of structural unit C is preferably 10 to 30% by mass, more preferably 15 to 25% by mass.
  • the content of the structural unit C is preferably 5 to 95% by mass, more preferably 10 to 90% by mass, relative to the total mass of the structural unit B and the structural unit C, and 15 to 60% by mass. % by mass is more preferred, and 20 to 50% by mass is particularly preferred.
  • the content of the structural unit A' in the polymer D is preferably 5-30% by mass with respect to the total mass of the polymer D.
  • the content of the structural unit A' is preferably 10 to 27.5% by mass, more preferably 10 to 25% by mass, relative to the total mass of the polymer D.
  • the alkenyl group equivalent weight of polymer D is preferably 300 to 1500 g/mol.
  • the alkenyl group equivalent is 300 g/mol or more, the cured product of the second composition tends to have a further decreased elastic modulus, and as a result, the thermal expansion coefficient of the substrate obtained using the cured product decreases. It tends to be even lower.
  • the alkenyl group equivalent is 1500 g/mol or less, the chemical resistance and insulation reliability of the second composition tend to be further improved.
  • the alkenyl group equivalent is preferably 350-1200 g/mol, more preferably 400-1000 g/mol.
  • the content of the polymer D in the second composition is preferably 5 to 50% by mass, more preferably 10 to 45% by mass, relative to 100% by mass of the resin solid content, and 15 to 40% by mass. % by mass is more preferred.
  • the second composition tends to exhibit even better heat resistance, low thermal expansion, chemical resistance, copper foil adhesion and insulation reliability in a well-balanced manner.
  • the second composition may further contain compound E in addition to polymer D, if necessary.
  • the second composition tends to further improve heat resistance, low thermal expansion, chemical resistance and copper foil adhesion.
  • the content of the polymer D in the second composition is 5 to 60% by mass with respect to the total 100% by mass of the polymer D and the compound E. %, more preferably 10 to 55% by mass, even more preferably 20 to 50% by mass.
  • the second composition tends to exhibit even better heat resistance, low thermal expansion, chemical resistance, copper foil adhesion and insulation reliability in a well-balanced manner.
  • the content of the compound E in the second composition is preferably 20 to 80 with respect to the total 100% by mass of the polymer D and the compound E. % by mass is preferable, 35 to 75% by mass is more preferable, and 45 to 65% by mass is even more preferable.
  • Polymer D is obtained, for example, by a step of reacting alkenylphenol A, epoxy-modified silicone B, epoxy compound C, and optionally phenol compound A' in the presence of polymerization catalyst G.
  • the reaction may be performed in the presence of an organic solvent. More specifically, in the above steps, the addition reaction between the epoxy group of the epoxy-modified silicone B and the epoxy compound C and the hydroxyl group of the alkenylphenol A, and the hydroxyl group of the resulting addition reaction product and the epoxy-modified silicone B and
  • the polymer D can be obtained by the progress of an addition reaction with the epoxy group of the epoxy compound C.
  • the polymerization catalyst G is not particularly limited, and includes, for example, imidazole catalysts and phosphorus-based catalysts. These catalysts are used individually by 1 type or in combination of 2 or more types. Among these, imidazole catalysts are preferred.
  • the imidazole catalyst is not particularly limited. -cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1, imidazoles such as 2-a]benzimidazole ("TBZ", a product of Shikoku Kasei Kogyo Co., Ltd.) and 2,4,5-triphenylimidazole ("TPIZ”, a product of Tokyo Kasei Kogyo Co., Ltd.);
  • TZ a product of Shikoku Kasei Kogyo Co., Ltd.
  • TPIZ 2,4,5-triphenylimidazole
  • TPIZ a product of Tokyo Kasei Kogyo Co., Ltd.
  • the amount of the polymerization catalyst G (preferably imidazole catalyst) used is not particularly limited, and for example, 0.1 part per 100 parts by mass of the total amount of alkenylphenol A, epoxy-modified silicone B, epoxy compound C and phenol compound A'. From the viewpoint of increasing the weight average molecular weight of the polymer D, the amount of the polymerization catalyst G used is preferably 0.5 parts by mass or more, and 4.0 parts by mass or less. It is more preferable to have
  • the organic solvent is not particularly limited, and for example, a polar solvent or a non-polar solvent can be used.
  • Polar solvents include, but are not limited to, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; cellosolve solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate; ethyl lactate, methyl acetate, ethyl acetate, and acetic acid; Ester solvents such as butyl, isoamyl acetate, ethyl lactate, methyl methoxypropionate and methyl hydroxyisobutyrate; and amides such as dimethylacetamide and dimethylformamide.
  • the nonpolar solvent is not particularly limited, but examples thereof include aromatic hydrocarbons such as toluene and xylene. These solvents are used singly or in combination of two or more.
  • the amount of the organic solvent used is not particularly limited, and is, for example, 50 to 150 parts by mass with respect to 100 parts by mass of the total amount of alkenylphenol A, epoxy-modified silicone B, epoxy compound C, and phenol compound A'.
  • the reaction temperature is not particularly limited, and may be, for example, 100-170°C.
  • the reaction time is also not particularly limited, and may be, for example, 3 to 8 hours.
  • polymer D may be separated and purified from the reaction mixture by a conventional method.
  • thermosetting resin composition of this embodiment may further contain other resins as long as the effects of this embodiment are not impaired.
  • Other resins include, for example, oxetane resins, benzoxazine compounds, compounds having polymerizable unsaturated groups, and the like. These resins are used singly or in combination of two or more.
  • oxetane resin examples include, but are not limited to, oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, alkyloxetane such as 3,3-dimethyloxetane, 3-methyl-3-methoxy Methyloxetane, 3,3'-di(trifluoromethyl)perfluoxetane, 2-chloromethyloxetane, 3,3-bis(chloromethyl)oxetane, biphenyl type oxetane, "OXT-101" manufactured by Toagosei Co., Ltd. , “OXT-121” and the like.
  • benzoxazine compound refers to a compound having two or more dihydrobenzoxazine rings in one molecule.
  • benzoxazine compound examples include, but are not limited to, "Bisphenol F-type benzoxazine BF-BXZ” and "Bisphenol S-type benzoxazine BS-BXZ” manufactured by Konishi Chemical Co., Ltd., and the like.
  • Examples of compounds having a polymerizable unsaturated group include, but are not limited to, vinyl compounds such as ethylene, propylene, styrene, divinylbenzene, and divinylbiphenyl; methyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate; , 2-hydroxypropyl (meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate ) monohydric or polyhydric alcohol (meth)acrylates such as acrylate; epoxy (meth)acrylates such as bisphenol A type epoxy (meth)acrylate and bisphenol F type epoxy (meth)acrylate; benzocyclobutene resin, etc. be done.
  • vinyl compounds such as ethylene,
  • thermosetting resin composition of the present embodiment further contains an aromatic phosphorus compound P from the viewpoint of further improving low thermal expansion properties.
  • the aromatic phosphorus compound P is not particularly limited as long as it contains a phosphorus atom in its molecule and exhibits aromaticity.
  • the aromatic phosphorus compound P is at least selected from the group consisting of cyclic phosphazene compounds, phosphate ester compounds, phosphite ester compounds and phosphaphenanthrene compounds. It is preferred that one species is included.
  • the aromatic phosphorus compound P more preferably contains at least one selected from the group consisting of a cyclic phosphazene compound, a phosphate ester compound, and a phosphite ester compound, from the viewpoint of further increasing copper foil adhesion. More preferably, it contains at least one selected from the group consisting of a cyclic phosphazene compound and a phosphate ester compound.
  • the aromatic phosphorus compound P is represented by the following formulas (P1) and (P2) , (P3) or (P4).
  • P1 and P2 represent a substituted or unsubstituted aryl group
  • Ph1, Ph2 and Ph3 may be the same or different.
  • P2 Ph1 and Ph2 represent a substituted or unsubstituted aryl group
  • the Ph1 and Ph2 may be the same or different
  • R is an alkyl group having 1 to 30 carbon atoms. or represents an aryl group having 6 to 30 carbon atoms.
  • A is each independently a hydrogen atom, a methyl group, a hydroxyl group, a cyano group, an amino group, a carboxyl group, a glycidyloxy group, a parahydroxyphenyldimethyl group, a paraglycidyloxyphenyldimethyl group.
  • R represents a hydrogen atom, an alkyl group having 2 to 30 carbon atoms, or a substituted or unsubstituted aryl group.
  • the aromatic phosphorus compound P is an aromatic phosphorus compound P′ represented by the following formula (P5). ' is preferably included.
  • the content of the aromatic phosphorus compound P in the thermosetting resin composition of the present embodiment is 3 to 15 parts by mass with respect to 100 parts by mass of the resin solid content, from the viewpoint of achieving both low thermal expansion and copper foil adhesion. parts, more preferably 3 to 12 parts by mass, even more preferably 4 to 10 parts by mass.
  • the thermosetting resin composition of the present embodiment preferably further contains an inorganic filler from the viewpoint of further improving low thermal expansion properties.
  • the inorganic filler is not particularly limited, and examples thereof include silicas, silicon compounds (e.g., white carbon, etc.), metal oxides (e.g., alumina, titanium white, zinc oxide, magnesium oxide, zirconium oxide, etc.), metal nitrides.
  • boron nitride aggregated boron nitride, silicon nitride, aluminum nitride, etc.
  • metal sulfates e.g., barium sulfate, etc.
  • metal hydroxides e.g., aluminum hydroxide, aluminum hydroxide heat-treated products (e.g., aluminum hydroxide heat-treated to reduce a portion of the water of crystallization), boehmite, magnesium hydroxide, etc.
  • molybdenum compounds e.g., molybdenum oxide, zinc molybdate, etc.
  • zinc compounds e.g., zinc borate, zinc stannate, etc.
  • the inorganic filler is preferably at least one selected from the group consisting of silicas, metal hydroxides and metal oxides, from the viewpoint of further improving low thermal expansion properties. Silicas, boehmite and alumina, and more preferably silicas.
  • silicas examples include natural silica, fused silica, synthetic silica, aerosil, and hollow silica. These silicas are used individually by 1 type or in combination of 2 or more types. Among these, fused silica is preferable from the viewpoint of dispersibility, and two or more types of fused silica having different particle sizes are more preferable from the viewpoint of filling properties and fluidity.
  • the content of the inorganic filler is preferably 50 to 1000 parts by mass, more preferably 70 to 500 parts by mass, based on 100 parts by mass of the resin solid content, from the viewpoint of further improving the low thermal expansion property. , more preferably 100 to 300 parts by mass.
  • thermosetting resin composition of this embodiment may further contain a silane coupling agent.
  • a silane coupling agent By containing a silane coupling agent, the thermosetting resin composition of the present embodiment further improves the dispersibility of the filler, the components of the thermosetting resin composition of the present embodiment, and the base described later. There is a tendency that the adhesive strength with the material can be further improved.
  • the silane coupling agent is not particularly limited, and includes silane coupling agents generally used for surface treatment of inorganic substances, aminosilane compounds (eg, ⁇ -aminopropyltriethoxysilane, N- ⁇ -(aminoethyl) - ⁇ -aminopropyltrimethoxysilane, etc.), epoxysilane compounds (eg, ⁇ -glycidoxypropyltrimethoxysilane, etc.), acrylsilane compounds (eg, ⁇ -acryloxypropyltrimethoxysilane, etc.), cationic Examples include silane compounds (eg, N- ⁇ -(N-vinylbenzylaminoethyl)- ⁇ -aminopropyltrimethoxysilane hydrochloride), styrylsilane compounds, phenylsilane compounds, and the like.
  • aminosilane compounds eg, ⁇ -aminopropyltriethoxysilane, N-
  • a silane coupling agent is used individually by 1 type or in combination of 2 or more types.
  • the silane coupling agent is preferably an epoxysilane compound.
  • epoxysilane compounds include Shin-Etsu Chemical Co., Ltd. products "KBM-403", “KBM-303", “KBM-402”, and "KBE-403".
  • the content of the silane coupling agent is not particularly limited, but may be 0.1 to 5.0 parts by mass with respect to 100 parts by mass of the resin solid content.
  • thermosetting resin composition of this embodiment may further contain a wetting and dispersing agent.
  • the thermosetting resin composition of the present embodiment tends to further improve the dispersibility of the filler by containing the wetting and dispersing agent.
  • any known dispersing agent used to disperse the filler may be used. 161, BYK-W996, W9010, W903 and the like.
  • the content of the wetting and dispersing agent is not particularly limited, it is preferably 0.5 parts by mass or more and 5.0 parts by mass or less with respect to 100 parts by mass of the resin solid content.
  • thermosetting resin composition of this embodiment may further contain a solvent.
  • a solvent By containing a solvent, the thermosetting resin composition of the present embodiment has a lower viscosity during preparation of the thermosetting resin composition, further improving handling properties (handling properties), and impregnating the substrate. tends to improve further.
  • the solvent is not particularly limited as long as it can dissolve some or all of the components in the thermosetting resin composition, but examples include ketones (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbons (e.g., toluene, xylene, etc.), amides (eg, dimethylformaldehyde, etc.), propylene glycol monomethyl ether and its acetate, and the like. These solvents are used singly or in combination of two or more.
  • the method for producing the thermosetting resin composition of the present embodiment is not particularly limited, and includes, for example, a method of collectively or sequentially blending each component with a solvent and stirring the mixture. At this time, in order to uniformly dissolve or disperse each component, known treatments such as stirring, mixing, and kneading are used.
  • thermosetting resin composition of the present embodiment can exhibit excellent heat resistance and low thermal expansion. Therefore, the thermosetting resin composition of the present embodiment is suitably used for metal foil-clad laminates and printed wiring boards.
  • the thermosetting resin composition of the present embodiment can be applied to the above-mentioned uses by curing. That is, the cured product of the present embodiment is obtained by curing the thermosetting resin composition of the present embodiment.
  • the second composition contains, in addition to the polymer D and the aromatic phosphorus compound P, at least an epoxy compound C (an epoxy compound C existing separately from the structural unit C in the polymer D). preferably included.
  • the polymer D preferably has units derived from the bifunctional epoxy compound described above as units derived from the epoxy compound C, and more preferably has units derived from the biphenyl type epoxy resin described above.
  • the epoxy compound C present separately from the structural unit C in the polymer D the above-mentioned naphthylene ether type epoxy resin (commercially available products, for example, "HP-6000” manufactured by DIC Corporation) and / Or naphthalene cresol novolak type epoxy resin (commercially available, for example, "HP-9540" manufactured by DIC Corporation) is preferably included.
  • the cyanate equivalent/epoxy equivalent value in the second composition is less than 0.8.
  • the cyanate equivalent/epoxy equivalent (functional group equivalent ratio) is the equivalent of the cyanate group in the cyanate ester compound that may be contained in the second composition, and the "polymer D It is the equivalent ratio of the epoxy group in the epoxy compound C that exists separately from the structural unit C in the inside, and is calculated by the following formula (1). In the present embodiment, it is possible to use two or more types of either the cyanate ester compound or the epoxy compound.
  • the number of functional groups (that is, the equivalent weight of cyanate groups and the equivalent weight of epoxy groups) is calculated, and these values are summed up to calculate the equivalent weight of all cyanate groups and the equivalent weight of all epoxy groups.
  • the functional group equivalent ratio is a value obtained by dividing the equivalent weight of all cyanate groups by the equivalent weight of all epoxy groups.
  • the number of functional groups is a value obtained by dividing the parts by mass of a component by the functional group equivalent of the component.
  • thermosetting resin composition of the present embodiment is suitably used for prepreg.
  • the prepreg of the present embodiment includes a substrate and the thermosetting resin composition of the present embodiment impregnated or applied to the substrate. Since the prepreg of the present embodiment is configured as described above, it is excellent in heat resistance and low thermal expansion when applied to metal foil-clad laminates and printed wiring boards.
  • the prepreg of this embodiment includes a base material and a thermosetting resin composition impregnated or applied to the base material.
  • the prepreg may be a prepreg obtained by a known method, and as a specific example, the thermosetting resin composition of the present embodiment is impregnated or applied to a substrate, and then subjected to conditions of 100 to 200 ° C. It is obtained by semi-curing (to B-stage) by drying with heat.
  • the prepreg of the present embodiment also includes the form of a cured product obtained by thermally curing a semi-cured prepreg under conditions of a heating temperature of 180 to 230° C. and a heating time of 60 to 180 minutes.
  • the content of the thermosetting resin composition in the prepreg is preferably 30 to 90% by volume, more preferably 35 to 85% by volume, more preferably 35 to 85% by volume, based on the total amount of the prepreg, in terms of the solid content of the prepreg. is 40 to 80% by volume.
  • the calculation of the content of the thermosetting resin composition herein includes the cured product of the thermosetting resin composition of the present embodiment.
  • the solid content of the prepreg as used herein refers to a component obtained by removing the solvent from the prepreg.
  • the filler is included in the solid content of the prepreg.
  • the substrate is not particularly limited, and examples thereof include known substrates used as materials for various printed wiring boards.
  • Specific examples of the substrate include glass substrates, inorganic substrates other than glass (for example, inorganic substrates composed of inorganic fibers other than glass such as quartz), organic substrates (for example, wholly aromatic polyamide, polyester , polyparaphenylenebenzoxazole, and organic base materials composed of organic fibers such as polyimide). These substrates are used singly or in combination of two or more.
  • a glass substrate is preferable from the viewpoint of being more excellent in dimensional stability under heating.
  • Fibers constituting the glass substrate include, for example, E glass, D glass, S glass, T glass, Q glass, L glass, NE glass, HME glass, and the like.
  • the fibers constituting the glass substrate are the group consisting of E glass, D glass, S glass, T glass, Q glass, L glass, NE glass and HME glass, from the viewpoint of being more excellent in strength and low water absorption.
  • One or more selected fibers are preferred.
  • the form of the substrate is not particularly limited, but examples thereof include forms such as woven fabric, nonwoven fabric, roving, chopped strand mat, and surfacing mat.
  • the weaving method of the woven fabric is not particularly limited, but for example, plain weave, Nanako weave, twill weave, etc. are known, and it is possible to appropriately select and use from these known ones depending on the intended use and performance. .
  • glass woven fabrics surface-treated with a silane coupling agent or the like are preferably used.
  • the thickness and mass of the base material are not particularly limited, but usually about 0.01 to 0.1 mm is suitably used.
  • the metal foil-clad laminate of the present embodiment includes a laminate containing the prepreg of the present embodiment and/or a cured product obtained by curing the prepreg, and a metal foil disposed on one or both sides of the laminate. .
  • the laminate may contain one prepreg and/or cured product, or may contain a plurality of prepregs and/or cured products.
  • the metal foil may be any metal foil that is used for various printed wiring board materials, and examples thereof include metal foils of copper, aluminum, and the like. Copper foil, such as foil, is mentioned.
  • the thickness of the conductor layer is, for example, 1 to 70 ⁇ m, preferably 1.5 to 35 ⁇ m.
  • the molding method and molding conditions for the metal foil-clad laminate are not particularly limited, and general techniques and conditions for printed wiring board laminates and multilayer boards can be applied.
  • a multistage press machine, a multistage vacuum press machine, a continuous molding machine, an autoclave molding machine, or the like can be used when molding a laminate or a metal foil-clad laminate.
  • the temperature is generally 100 to 300° C.
  • the pressure is 2 to 100 kgf/cm 2
  • the heating time is generally in the range of 0.05 to 5 hours.
  • post-curing can be performed at a temperature of 150-300°C.
  • the temperature is preferably 200° C. to 250° C.
  • the pressure is 10 to 40 kgf/cm 2
  • the heating time is 80 minutes to 130 minutes
  • the temperature is 215° C. to 215° C., from the viewpoint of sufficiently accelerating the curing of the prepreg.
  • the temperature is 235° C.
  • the pressure is 25 to 35 kgf/cm 2
  • the heating time is 90 to 120 minutes.
  • the printed wiring board of this embodiment has an insulating layer containing a cured product obtained by curing the prepreg of this embodiment, and a conductor layer formed on the surface of the insulating layer.
  • the printed wiring board of the present embodiment can be formed, for example, by etching the metal foil of the metal foil-clad laminate of the present embodiment into a predetermined wiring pattern to form a conductor layer.
  • the printed wiring board of the present embodiment can be manufactured, for example, by the following method.
  • An inner layer board having a conductor layer (inner layer circuit) is produced by etching the metal foil of the metal foil clad laminate into a predetermined wiring pattern.
  • a laminate is obtained.
  • the laminate molding method and molding conditions are the same as the laminate molding method and molding conditions for the laminate and the metal foil-clad laminate described above.
  • the laminate is perforated for through holes and via holes, and the wall surfaces of the holes thus formed are plated with a metal film for conducting the conductor layer (internal circuit) and the metal foil for the outer layer circuit.
  • the metal foil for the outer layer circuit is etched into a predetermined wiring pattern to form an outer layer substrate having a conductor layer (outer layer circuit). A printed wiring board is thus manufactured.
  • a printed wiring board may be produced by forming a conductor layer that becomes a circuit on the insulating layer. At this time, an electroless plating technique can be used to form the conductor layer.
  • the electrical conductivity of the wastewater after the fifth washing was 5 ⁇ S/cm, confirming that the ionic compounds that could be removed by washing with water were sufficiently removed.
  • the organic phase after washing with water is concentrated under reduced pressure and finally concentrated to dryness at 90° C. for 1 hour to obtain the desired 1-naphthol aralkyl cyanate ester compound (SN495V-CN, cyanate group equivalent: 261 g/eq. ) (orange viscous substance) 331 g were obtained.
  • the infrared absorption spectrum of the obtained SN495V-CN showed absorption at 2250 cm -1 (cyanate group) and no absorption of hydroxy group.
  • R 2a represents a hydrogen atom and m represents an integer of 1 to 10.
  • Example 1 In a three-necked flask equipped with a thermometer and a Dimroth, 5.0 parts by mass of diallyl bisphenol A (DABPA, Daiwa Kasei Kogyo Co., Ltd.), 5.4 parts by mass of biscresol fluorene (BCF, Osaka Gas Chemical Co., Ltd.), epoxy Modified silicone b1 (X-22-163, Shin-Etsu Chemical Co., Ltd., functional group equivalent 200 g / mol) 3.7 parts, epoxy-modified silicone b2 (KF-105, Shin-Etsu Chemical Co., Ltd., functional group equivalent 490 g /mol) 11.0 parts by mass, biphenyl type epoxy resin c1 (YL-6121H, Mitsubishi Chemical Corporation) 4.9 parts by mass, propylene glycol monomethyl ether acetate (DOWANOL PMA, Dow Chemical Japan Co., Ltd.) as a solvent 30 parts by mass was added, and the mixture was heated and stirred to 120° C.
  • diallyl bisphenol A corresponds to "alkenylphenol A”
  • epoxy-modified silicone b1 and epoxy-modified silicone b2 correspond to "epoxy-modified silicone B”
  • biphenyl type epoxy resin c1 corresponds to "epoxy compound C”.
  • the phenoxy polymer solution contained a polymer D containing a structural unit derived from alkenylphenol A, a structural unit derived from epoxy-modified silicone B, and a structural unit derived from epoxy compound C.
  • polymer D is also referred to as phenoxy polymer.
  • the content of structural unit B with respect to polymer D was 48.8% by mass.
  • the content of structural unit C with respect to the total amount of structural unit B and structural unit C was 25% by mass.
  • the weight average molecular weight Mw of the phenoxy polymer obtained as described above was measured as follows. 20 ⁇ L of a solution prepared by dissolving 0.5 g of the phenoxy polymer solution in 2 g of THF was injected into a high-performance liquid chromatography (manufactured by Shimadzu Corporation, pump: LC-20AD) for analysis. The columns were Shodex GPC KF-804 (length 30 cm x inner diameter 8 mm) manufactured by Showa Denko, Shodex GPC KF-803 (length 30 cm x inner diameter 8 mm), Shodex GPC KF-802 (length 30 cm x inner diameter 8 mm), Shodex GPC.
  • the weight average molecular weight Mw was obtained by GPC method using standard polystyrene as a standard substance.
  • the weight average molecular weight Mw of the phenoxy polymer measured as described above was 12,000.
  • naphthalene cresol novolak type epoxy resin HP-9540, DIC Corporation, functional group equivalent 244 g/mol
  • phenol novolak type cyanate ester compound PT-30, Lonza, functional group equivalent 127 g/mol) mol
  • phosphate ester compound PX-200, Daihachi Chemical Industry Co., Ltd.
  • slurry silica as filler SC-2050MB, Admatechs Co., Ltd.
  • wet dispersion A varnish was obtained by mixing 1 part by mass of an agent (DISPERBYK-161, BYK-Chemie Japan Co., Ltd.) and 5 parts by mass of a silane coupling agent (KBM-403, Shin-Etsu Chemical Co., Ltd.) (varnish production step).
  • thermosetting resin composition solid content (including filler) is 58.2% by volume. of prepreg was obtained (prepreg manufacturing process).
  • Example 2 A prepreg having a thermosetting resin composition solid content (including filler) content of 58.2% by volume was obtained in the same manner as in Example 1, except for the following points. That is, 14 parts by mass of SN495V-CN was used instead of PT-30 in the varnish production step.
  • Example 3 A prepreg having a thermosetting resin composition solid content (including filler) content of 58.2% by volume was obtained in the same manner as in Example 1, except for the following points. That is, in the varnish production step, the amount of BMI-2300 used was changed to 16.5 parts by mass, the amount of BMI-80 used was changed to 5.5 parts by mass, and 15 parts of SN495V-CN was used instead of PT-30. The amount of HP-9540 was changed to 28 parts by mass, the amount of PX-200 was changed to 5 parts by mass, and the amount of SC-2050MB was changed to 200 parts by mass. Furthermore, in the prepreg manufacturing process, the heat drying conditions were changed to 155° C. for 5 minutes.
  • Example 4 A prepreg having a thermosetting resin composition solid content (including filler) content of 58.2% by volume was obtained in the same manner as in Example 2, except for the following points. That is, in the varnish production step, the amount of SC-2050MB used was changed to 200 parts by mass. Furthermore, in the prepreg manufacturing process, the heat drying conditions were changed to 155° C. for 5 minutes.
  • Example 5 A prepreg having a thermosetting resin composition solid content (including filler) content of 58.2% by volume was obtained in the same manner as in Example 4, except for the following points. That is, in the varnish production step, 30 parts by mass of a naphthylene ether type epoxy resin (HP-6000, DIC Corporation, functional group equivalent: 250 g/mol) is used instead of HP-9540, and the amount of SN495V-CN used is reduced to was changed to 15 parts by mass, and the amount of PX-200 used was changed to 5 parts by mass.
  • a naphthylene ether type epoxy resin HP-6000, DIC Corporation, functional group equivalent: 250 g/mol
  • Example 6 A prepreg having a thermosetting resin composition solid content (including filler) content of 58.2% by volume was obtained in the same manner as in Example 2, except for the following points. That is, in the varnish production step, the amount of BMI-2300 used was changed to 13 parts by mass, the amount of BMI-80 used was changed to 4 parts by mass, the amount of HP-9540 used was changed to 21 parts by mass, and SN495V The amount of -CN used was changed to 22 parts by mass. Furthermore, in the prepreg manufacturing process, the heat drying conditions were changed to 155° C. for 5 minutes.
  • Example 7 A prepreg having a thermosetting resin composition solid content (including filler) content of 58.2% by volume was obtained in the same manner as in Example 2, except for the following points. That is, in the varnish production step, instead of PX-200, a phosphorus compound (10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, HCA-HQ, 10 parts by mass of Sanko Co., Ltd. was used, and the amount of SC-2050MB used was changed to 200 parts by mass. Furthermore, in the prepreg manufacturing process, the heat drying conditions were changed to 155° C. for 3.5 minutes.
  • Example 8 A prepreg having a thermosetting resin composition solid content (including filler) content of 58.2% by volume was obtained in the same manner as in Example 1, except for the following points. That is, in the polymer production step, the amount of DABPA used was changed to 5.1 parts by mass, the amount of BCF used was changed to 5.6 parts by mass, and the amount of X-22-163 used was changed to 4.2 parts by mass. The amount of KF-105 used was changed to 8.5 parts by mass, and the amount of YL-6121H used was changed to 5.6 parts by mass to obtain a phenoxy polymer solution. After heating this phenoxy polymer solution to 100° C.
  • Example 9 A prepreg having a thermosetting resin composition solid content (including filler) content of 58.2% by volume was obtained in the same manner as in Example 8, except for the following points. That is, in the varnish production step, the amount of BMI-2300 used was changed to 7 parts by mass, the amount of BMI-80 used was changed to 7 parts by mass, the amount of HP-9540 used was changed to 24 parts by mass, and SN495V was changed to 22 parts by mass, and the amount of PX-200 was changed to 10 parts by mass.
  • Example 10 A prepreg having a thermosetting resin composition solid content (including filler) content of 58.2% by volume was obtained in the same manner as in Example 5, except for the following points. That is, in the varnish production step, 5 parts by mass of cyclic cyanophenoxyphosphazene (Rabitol FP-300, Fushimi Pharmaceutical Co., Ltd.) was used in place of PX-200. Furthermore, in the prepreg manufacturing process, the heat drying conditions were changed to 165° C. for 5 minutes.
  • Example 11 A prepreg having a thermosetting resin composition solid content (including filler) content of 58.2% by volume was obtained in the same manner as in Example 10, except for the following points. That is, in the varnish production step, 5 parts by mass of a phosphoric acid ester compound (ADEKA STAB HP-10, ADEKA Corporation) was used in place of FP-300.
  • a phosphoric acid ester compound ADEKA STAB HP-10, ADEKA Corporation
  • Example 12 A prepreg having a thermosetting resin composition solid content (including filler) content of 58.2% by volume was obtained in the same manner as in Example 10, except for the following points. That is, in the varnish production step, 5 parts by mass of a phosphoric acid ester compound (ADEKA STAB 2112, ADEKA Corporation) was used in place of FP-300.
  • a phosphoric acid ester compound ADEKA STAB 2112, ADEKA Corporation
  • thermosetting resin composition solid content (including filler) content of 58.2% by volume was obtained in the same manner as in Example 1, except for the following points. That is, in the varnish production step, the amount of HP-9540 used was changed to 32 parts by mass, the amount of PT-30 used was changed to 18 parts by mass, and PX-200 was not used.
  • thermosetting resin composition solid content (including filler) content of 58.2% by volume was obtained in the same manner as in Comparative Example 1, except for the following points. That is, in the varnish production step, the amount of BMI-2300 used was changed to 15 parts by mass, and the amount of SC-2050MB used was changed to 200 parts by mass. Furthermore, in the prepreg manufacturing process, the heat drying conditions were changed to 155° C. for 5 minutes.
  • thermosetting resin composition solid content (including filler) content of 58.2% by volume was obtained in the same manner as in Example 8, except for the following points. That is, in the varnish production step, the amount of BMI-2300 used was changed to 9 parts by mass, the amount of BMI-80 used was changed to 9 parts by mass, and 27 parts by mass of HP-6000 was used instead of HP-9540. , SN495V was changed to 25 parts by mass, and PX-200 was not used. Furthermore, in the prepreg manufacturing process, the heat drying conditions were changed to 140° C. for 3 minutes.
  • thermosetting resin composition solid content (including filler) content of 58.2% by volume was obtained in the same manner as in Example 3, except for the following points. That is, in the varnish production step, the amount of BMI-2300 used was changed to 16 parts by mass, the amount of BMI-80 used was changed to 5.5 parts by mass, and the amount of HP-9540 used was changed to 32.5 parts by mass. changed, the amount of SN495V-CN used was changed to 16 parts by mass, and PX-200 was not used.
  • thermosetting resin composition solid content (including filler) content of 58.2% by volume was obtained in the same manner as in Example 1, except for the following points. That is, in the varnish production step, the amount of BMI-2300 used was changed to 17 parts by mass, BMI-80 was not used, 27 parts by mass of HP-6000 was used in place of HP-9540, and PT-30 was replaced with SN495V-CN was used in an amount of 26 parts by mass, and PX-200 was not used.
  • Tg glass transition temperature
  • Examples 1-12 are superior to Comparative Examples 1-3 in heat resistance and low thermal expansion. Further, from Table 2 above, it can be seen that Examples 1 to 6 and 10 to 12 are superior to Comparative Examples 1 to 3 in copper foil adhesion.
  • a cyclic phosphazene compound or a phosphate ester compound was used as the aromatic phosphorus compound, whereas a phosphaphenanthrene compound was used as the aromatic phosphorus compound in Example 7. It is presumed that Examples 1 to 6 and 10 to 12 resulted in better adhesion to the copper foil because of the fact that they were used.
  • Examples 8 and 9 The copper foil adhesion of Examples 8 and 9 has not been measured, but since the oxazolidone structure formed by the reaction of the cyanate ester compound and the epoxy compound tends to have excellent metal adhesion, Examples 1 to 6 and 10 12 are presumed to be superior in copper foil adhesion to Examples 8 and 9 (however, the reason is not limited to this).
  • the present invention has industrial applicability as a thermosetting resin composition used as materials for prepregs, resin sheets, metal foil-clad laminates, printed wiring boards, and the like.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Epoxy Resins (AREA)

Abstract

L'invention concerne une composition de résine thermodurcissable qui comprend un alcénylphénol (A), une silicone (B) modifiée par un époxy, un composé époxy (C) autre que la silicone (B) modifiée par un époxy, et un composé phosphore aromatique (P).
PCT/JP2022/029871 2021-08-05 2022-08-04 Composition de résine thermodurcissable, préimprégné, et carte de circuits imprimés WO2023013711A1 (fr)

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CN202280054398.XA CN118251457A (zh) 2021-08-05 2022-08-04 热固化性树脂组合物、预浸料和印刷电路板
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH044213A (ja) * 1990-04-23 1992-01-08 Sumitomo Bakelite Co Ltd 半導体封止用樹脂の製造方法
JPH06136093A (ja) * 1992-09-08 1994-05-17 Fujitsu Ltd エポキシ樹脂組成物
JPH08176280A (ja) * 1994-12-27 1996-07-09 Matsushita Electric Works Ltd 液状エポキシ樹脂組成物及びその製法
JP2009007467A (ja) * 2007-06-28 2009-01-15 Shin Etsu Chem Co Ltd 実装用難燃性サイドフィル材及び半導体装置
WO2018124161A1 (fr) * 2016-12-28 2018-07-05 三菱瓦斯化学株式会社 Composition de résine de carte de circuit imprimé, préimprégné, feuille de résine, plaque stratifiée, plaque stratifiée avec gainage de feuille métallique, carte de circuit imprimé, et carte de circuit imprimé multicouche
WO2020022084A1 (fr) * 2018-07-26 2020-01-30 三菱瓦斯化学株式会社 Composition durcissable, préimprégné, feuille de résine, stratifié plaqué d'une feuille métallique et carte de circuit imprimé

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH044213A (ja) * 1990-04-23 1992-01-08 Sumitomo Bakelite Co Ltd 半導体封止用樹脂の製造方法
JPH06136093A (ja) * 1992-09-08 1994-05-17 Fujitsu Ltd エポキシ樹脂組成物
JPH08176280A (ja) * 1994-12-27 1996-07-09 Matsushita Electric Works Ltd 液状エポキシ樹脂組成物及びその製法
JP2009007467A (ja) * 2007-06-28 2009-01-15 Shin Etsu Chem Co Ltd 実装用難燃性サイドフィル材及び半導体装置
WO2018124161A1 (fr) * 2016-12-28 2018-07-05 三菱瓦斯化学株式会社 Composition de résine de carte de circuit imprimé, préimprégné, feuille de résine, plaque stratifiée, plaque stratifiée avec gainage de feuille métallique, carte de circuit imprimé, et carte de circuit imprimé multicouche
WO2020022084A1 (fr) * 2018-07-26 2020-01-30 三菱瓦斯化学株式会社 Composition durcissable, préimprégné, feuille de résine, stratifié plaqué d'une feuille métallique et carte de circuit imprimé

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TW202321375A (zh) 2023-06-01

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