WO2023013715A1 - Curable composition, prepreg, resin sheet, metal foil–clad laminate, and printed wiring board - Google Patents

Curable composition, prepreg, resin sheet, metal foil–clad laminate, and printed wiring board Download PDF

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Publication number
WO2023013715A1
WO2023013715A1 PCT/JP2022/029878 JP2022029878W WO2023013715A1 WO 2023013715 A1 WO2023013715 A1 WO 2023013715A1 JP 2022029878 W JP2022029878 W JP 2022029878W WO 2023013715 A1 WO2023013715 A1 WO 2023013715A1
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Prior art keywords
epoxy
group
curable composition
compound
mass
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PCT/JP2022/029878
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French (fr)
Japanese (ja)
Inventor
和輝 砂川
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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Application filed by 三菱瓦斯化学株式会社 filed Critical 三菱瓦斯化学株式会社
Priority to CN202280054529.4A priority Critical patent/CN117836370A/en
Priority to KR1020247004066A priority patent/KR20240021990A/en
Priority to JP2022571828A priority patent/JP7411170B2/en
Publication of WO2023013715A1 publication Critical patent/WO2023013715A1/en
Priority to JP2023177242A priority patent/JP2024016043A/en

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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/226—Mixtures of di-epoxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/30—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
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4014—Nitrogen containing compounds
    • C08G59/4028—Isocyanates; Thioisocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4014—Nitrogen containing compounds
    • C08G59/4042—Imines; Imides
    • 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
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1535—Five-membered rings
    • C08K5/1539—Cyclic anhydrides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C08L61/14—Modified phenol-aldehyde condensates
    • 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins

Definitions

  • the present invention relates to curable compositions, prepregs, resin sheets, metal foil-clad laminates, and printed wiring boards.
  • Patent Document 1 discloses that a thermosetting resin composition containing a specific maleimide compound, a silicone compound having an epoxy group in the molecular structure, and a compound having a phenolic hydroxyl group is excellent in heat resistance and low thermal expansion. , metal foil-clad laminates and multilayer printed wiring boards.
  • Patent Document 2 polymaleimide, a diglycidylpolysiloxane represented by the following formula (I), and an addition polymer of a diallyl bisphenol represented by the following formula (II), and the following formula (III)
  • a manufacturing method is disclosed in which a resin for encapsulating a semiconductor is obtained by reacting an allylated phenol resin represented by the formula in a predetermined ratio and under predetermined conditions.
  • the resin for semiconductor encapsulation obtained by the above production method has good compatibility with polymaleimide and the addition polymer described above, and furthermore, the composition using the resin for semiconductor encapsulation has good compatibility.
  • component b in the following formula (III) is an important component that reacts with maleimide groups in a resin formation reaction with polymaleimide and improves the compatibility between polymaleimide and polysiloxane. ing.
  • R 1 represents an alkylene group or a phenylene group
  • each R 2 independently represents an alkyl group or a phenyl group
  • n represents an integer of 1 to 100.
  • R4 represents an ether bond, a methylene group, a propylidene group or a direct bond (single bond).
  • a resin composition containing a silicone compound having an epoxy group in its molecular structure and a thermosetting resin such as a maleimide compound is excellent in low thermal expansion.
  • the resin composition has a problem in moldability due to insufficient compatibility between the silicone compound and the thermosetting resin.
  • the present inventors have found that the above resin composition does not have sufficient metal foil peel strength (for example, copper foil peel strength) when used as a metal foil clad laminate.
  • Patent Document 2 the resin composition described in Patent Document 2 is used for semiconductor encapsulation, and low thermal expansion and copper foil peel strength required as characteristics of printed wiring boards have not been studied.
  • the present invention has been made in view of the above problems, and provides a curable composition, a prepreg, a resin sheet, a metal foil-clad laminate, and a printed wiring board having excellent low thermal expansion and copper foil peel strength. for the purpose.
  • a curable composition comprising an alkenylphenol A, an epoxy-modified silicone B, an epoxy compound C other than the epoxy-modified silicone B, and an acid anhydride D.
  • the average number of phenol groups per molecule of the alkenylphenol A is 1 or more and less than 3
  • the average number of epoxy groups per molecule of the epoxy-modified silicone B is 1 or more and less than 3
  • the epoxy compound C has an average number of The curable composition according to [1] above, which has an average number of epoxy groups of 1 or more and less than 3.
  • 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 is , represents an integer from 0 to 100.
  • each R a independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom.
  • the content of the epoxy compound C is 20 to 50% by mass with respect to 100% by mass of the total amount of the epoxy-modified silicone B and the epoxy compound C, according to any one of [1] to [6] above.
  • the acid anhydride D is one or more selected from the group consisting of phthalic anhydride, succinic anhydride, maleic anhydride, nadic anhydride and cis-4-cyclohexene-1,2-dicarboxylic anhydride. , the curable composition according to any one of the above [1] to [7].
  • a curable composition according to [9] above, wherein the polymer E has a weight average molecular weight of 3.0 ⁇ 10 3 to 5.0 ⁇ 10 4 .
  • the content of the structural unit derived from the epoxy-modified silicone B in the polymer E is 20 to 60% by mass with respect to the total mass of the polymer E. curable composition.
  • 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 is , represents an integer from 0 to 100.
  • each R a independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom.
  • the acid anhydride D is one or more selected from the group consisting of phthalic anhydride, succinic anhydride, maleic anhydride, nadic anhydride and cis-4-cyclohexene-1,2-dicarboxylic anhydride. , the curable composition according to any one of the above [9] to [18].
  • each R 13 independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or an alkenyl group having 2 to 3 carbon atoms.
  • each R 14 independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkenyl group having 2 to 3 carbon atoms.
  • any one of the above [1] to [20] further comprising at least one compound F selected from the group consisting of maleimide compounds, cyanate ester compounds, phenol compounds A' other than alkenylphenol A, and alkenyl-substituted nadimide compounds.
  • the maleimide compound is bis(4-maleimidophenyl)methane, 2,2-bis ⁇ 4-(4-maleimidophenoxy)-phenyl ⁇ propane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane,
  • the curable composition according to [21] above which contains at least one selected from the group consisting of a maleimide compound represented by the following formula (3) and a maleimide compound represented by the following formula (3′).
  • 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.
  • the cyanate ester compound contains a compound represented by the following formula (5) excluding the compound represented by the following formula (4) and / or the compound represented by the following formula (4) [21] or The curable composition according to [22].
  • each R6 independently represents a hydrogen atom or a methyl group, and n2 represents an integer of 1 or more.
  • R ya each independently represents an alkenyl group having 2 to 8 carbon atoms or a hydrogen atom
  • each R yb independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom
  • Each R yc independently represents an aromatic ring having 4 to 12 carbon atoms
  • R yc may form a condensed structure with a benzene ring
  • 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, an oxygen atom, represents a sulfur atom or a single bond
  • one benzene ring may have two or more R ya and/or R ya and/or R ya and/
  • each R 7 independently represents a hydrogen atom or a methyl group, and n 3 represents an integer of 1 or more.
  • a prepreg comprising a substrate and the curable composition according to any one of [1] to [27] impregnated or applied to the substrate.
  • a resin sheet comprising a support and the curable composition according to any one of [1] to [27] disposed on the surface of the support.
  • a metal foil clad laminate comprising: [31] an insulating layer formed of one or more selected from the group consisting of the prepreg described in [28] above and the resin sheet described in [29] above; a conductor layer formed on the surface of the insulating layer; A printed wiring board.
  • curable compositions, prepregs, resin sheets, metal foil-clad laminates and printed wiring boards having excellent low thermal expansion and copper foil peel strength.
  • 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.
  • resin solid content refers to the components excluding the solvent and filler in the curable composition of the present embodiment, unless otherwise specified. It means that the total amount of components excluding the solvent and filler in the curable 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 curable composition is 100 mass %.
  • excellent compatibility means a mixture containing alkenylphenol A, epoxy-modified silicone B, epoxy compound C, and acid anhydride D ( For example, it means that liquid phase separation does not occur in the state of varnish.
  • excellent compatibility means that liquid phase separation does not occur in a state of a mixture (for example, varnish) containing the polymer E and other components.
  • the curable composition of the first embodiment comprises alkenylphenol A, epoxy-modified silicone B, epoxy compound C excluding epoxy-modified silicone B (hereinafter also simply referred to as “epoxy compound C”), and acid anhydride D and A curable composition containing these components tends to be more compatible with thermosetting resins (hereinafter also simply referred to as “thermosetting resins”) that are not sufficiently compatible with epoxy-modified silicone B. Due to this, the curable composition of the first embodiment can exhibit more excellent compatibility, and is excellent in low thermal expansion and copper foil peel strength. In addition, when the curable composition is used by partially reacting (polymerizing) each of these components, it is possible to exhibit even better compatibility, and it is possible to exhibit better low thermal expansion and copper foil peel strength. (the curable composition of the second embodiment).
  • 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 curable composition of the present embodiment can exhibit excellent compatibility.
  • 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 invention.
  • 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 invention.
  • 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 more effectively and reliably exhibiting the effects of the present invention, alkenylphenol A preferably has one or two structures in which one or more alkenyl groups are directly bonded to a phenolic aromatic ring, and has two is preferred.
  • Alkenylphenol A may be, for example, a compound represented by formula (1A) or formula (1B) below.
  • 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 each independently represents represents an aromatic ring having 4 to 12 carbon atoms
  • Rxc may form a condensed structure with a benzene ring
  • Rxc may or may not be present
  • A is 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); If it 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 may form a fused structure with a benzene ring, Rxf may or may not be present, and when Rxf is absent, one
  • the benzene ring may have two or more Rxd and/or Rxe groups.
  • alkenyl groups having 2 to 8 carbon atoms represented by Rxa and Rxd are 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, but is, for example, represented by 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 is not particularly limited and 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 invention.
  • alkenylphenol A is preferably alkenylbisphenol in which one alkenyl group is bonded to each of two phenolic aromatic rings of bisphenols.
  • alkenyl bisphenol is diallyl bisphenol in which two phenolic aromatic rings of the bisphenol are respectively bound to one allyl group, and/or two phenolic aromatic rings of the bisphenol are respectively bound to one propenyl group. preferably dipropenyl bisphenol.
  • the diallyl bisphenol is not particularly limited, but for example, o,o'-diallyl bisphenol A ("DABPA", a product of Daiwa Kasei Kogyo Co., Ltd.), o, o'-diallyl bisphenol F, o, o'-diallyl bisphenol S , o,o'-diallylbisphenol fluorene.
  • DABPA o,o'-diallyl bisphenol A
  • F o, o'-diallyl bisphenol F
  • S o,o'-diallylbisphenol fluorene
  • the dipropenyl bisphenol is not particularly limited, and examples thereof include o,o'-dipropenylbisphenol A ("PBA01" from Gunei Chemical Industry Co., Ltd.), o,o'-dipropenylbisphenol F, o,o'- Dipropenyl bisphenol S, o,o'-dipropenyl bisphenol fluorene.
  • the average number of phenol groups per molecule of alkenylphenol A is preferably 1 or more and less than 3, and preferably 1.5 or more and 2.5 or less, from the viewpoint of more effectively and reliably exhibiting the effects of the present invention. more preferred.
  • the average number of phenol groups is calculated by the following formula.
  • A represents the number of phenol groups in alkenylphenol having i phenol groups in the molecule
  • Xi represents the ratio of alkenylphenol having i phenol groups in the molecule to all alkenylphenols
  • 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 curable composition of the present embodiment can exhibit excellent low thermal expansion and copper foil peel strength.
  • 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 invention.
  • the epoxy group-containing group is not particularly limited, but includes, for example, a group represented by the following formula (a1).
  • R 0 represents an alkylene group (e.g., a methylene group, an ethylene group, an alkylene group having 1 to 5 carbon atoms such as a propylene group), and X is a monovalent represented by the following formula (a2) 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 has excellent compatibility with thermosetting resins, and tends to further improve low thermal expansion and copper foil peel strength in a well-balanced manner. It is in. 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 types of epoxy-modified silicones from the viewpoint of further improving compatibility with thermosetting resins and further improving low thermal expansion and copper foil peel strength in a well-balanced manner.
  • the two or more epoxy-modified silicones preferably have different epoxy equivalents, and an epoxy-modified silicone having an epoxy equivalent of 50 to 350 g/mol (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.
  • the average epoxy equivalent is calculated by the following formula.
  • Ei represents the epoxy equivalent of one epoxy-modified silicone among two or more epoxy-modified silicones
  • Wi represents the ratio of the epoxy-modified silicone in epoxy-modified silicone B
  • W 1 +W 2 + . . . W n 1.
  • Epoxy-modified silicone B should contain an epoxy-modified silicone represented by the following formula (1) from the viewpoint of having excellent compatibility with thermosetting resins and further improving low thermal expansion and copper foil peel strength in a well-balanced manner. is preferred.
  • 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. n is preferably 50 or less, more preferably 30 or less, and even more preferably 20, from the viewpoint of better compatibility with thermosetting resins and further improvement of low thermal expansion and copper foil peel strength in a well-balanced manner. It is below.
  • Epoxy-modified silicone B is more excellent in compatibility with the thermosetting resin, and from the viewpoint of further improving low thermal expansion and copper foil peel strength in a well-balanced manner, two or more types of epoxy-modified silicones represented by formula (1) are used. It is preferable to contain. In this case, 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 epoxy-modified silicone B 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 invention. is more preferred.
  • the average number of epoxy groups is calculated by the following formula.
  • 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. By containing the epoxy compound C, the curable composition of the present embodiment can exhibit excellent compatibility, heat resistance, chemical resistance, copper foil peel strength, 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 curable 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. 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 better compatibility, heat resistance, chemical resistance, copper foil peel strength and insulation reliability.
  • the epoxy compound C in the curable 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 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, “ESN-375” and “ESN-475" manufactured by Nippon Steel Chemical Co., Ltd., and the like.
  • 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 curable 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 peel strength, 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 compound 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 compounds 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 peel strength 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.
  • diallylbisphenol type epoxy resins for example, diallylbisphenol A type epoxy resin, diallylbisphenol E type epoxy resin, diallylbisphenol F type epoxy resin, diallylbisphenol S type epoxy resin, etc.
  • diallylbisphenol type epoxy resins for example, diallylbisphenol A type epoxy resin, diallylbisphenol E type epoxy resin, diallylbisphenol F type epoxy resin, dially
  • 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 peel strength 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.
  • the curable composition of the present embodiment contains acid anhydride D.
  • Acid anhydride D reacts with terminal hydroxyl groups and epoxy groups generated by the reaction of alkenylphenol A, epoxy-modified silicone B, and epoxy compound C other than epoxy-modified silicone B to generate terminal carboxyl groups.
  • a large number of carboxyl groups having high reactivity with the thermosetting resin are present, so compatibility and crosslink density are improved, and low thermal expansibility is improved.
  • the acid anhydride D is not particularly limited, and is not particularly limited as long as it has a cyclic structure, and preferably has 4 to 20 carbon atoms because it tends to have better compatibility with thermosetting resins. More preferably an acid anhydride having 4 to 16 carbon atoms, more preferably an acid anhydride having 4 to 10 carbon atoms.
  • Acid anhydride D is, for example, one or more selected from the group consisting of phthalic anhydride, succinic anhydride, maleic anhydride, nadic anhydride and cis-4-cyclohexene-1,2-dicarboxylic anhydride.
  • phthalic anhydride and succinic anhydride are more preferable from the viewpoint of better compatibility with thermosetting resins and further improvement of low thermal expansion and copper foil peel strength in a well-balanced manner.
  • the content of acid anhydride D is 0.00% with respect to 100% by mass of resin solid content, from the viewpoint of better compatibility with the thermosetting resin and further improvement of low thermal expansion and copper foil peel strength in a well-balanced manner. It is preferably 8 to 15% by mass, more preferably 0.9 to 10% by mass, even more preferably 1 to 5% by mass.
  • the curable composition of the present embodiment includes a maleimide compound, a cyanate ester compound, and a phenol compound A other than the alkenylphenol A. ' and at least one compound F selected from the group consisting of alkenyl-substituted nadimide compounds.
  • compound F is not particularly limited, it is preferably bifunctional or higher, and may be trifunctional or higher polyfunctional.
  • the content of compound F in the curable composition of the present embodiment is preferably 10 to 80% by mass, more preferably 20 to 60% by mass, relative to 100% by mass of the resin solid content. Preferably, it is more preferably 30 to 50% by mass.
  • maleimide compound Compound F preferably contains a maleimide compound from the viewpoint of further improving low thermal expansion and copper foil peel strength.
  • the maleimide compound is not particularly limited as long as it is a compound having one or more maleimide groups in one molecule. -hydroxyphenylmaleimide, etc.), polymaleimide compounds having two or more maleimide groups in one molecule (e.g., bis(4-maleimidophenyl)methane, 2,2-bis ⁇ 4-(4-maleimidophenoxy)-phenyl ⁇ propane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, bis(3,5-dimethyl-4-maleimidophenyl)methane, bis(3,5-diethyl-4-maleimidophenyl)methane), m-phenylene bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane
  • n 1 is 1 or more, preferably 1-100, more preferably 1-10.
  • 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.
  • the maleimide compound is bis(4-maleimidophenyl)methane, 2,2-bis ⁇ 4-(4-maleimidophenoxy)-phenyl ⁇ At least one selected from the group consisting of propane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, a maleimide compound represented by formula (3), and a maleimide compound represented by formula (3′) is preferably included.
  • 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-3000-70MT” (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, and preferably 5 to 40 parts by mass, relative to 100 parts by mass of the resin solid content, from the viewpoint of further improving low thermal expansion properties and copper foil peel strength. is more preferable, and 10 to 40 parts by mass is even more preferable.
  • Compound F preferably contains a cyanate ester compound from the viewpoint of further improving low thermal expansion properties and copper foil peel strength.
  • the cyanate ester compound is not particularly limited as long as it is a compound having two or more cyanato groups (cyanate ester groups) in one molecule.
  • novolak-type cyanate ester compounds such as compounds represented by the following formula (5) excluding compounds represented by formula (4), biphenyl aralkyl-type cyanates, diallyl bisphenol-type cyanates compounds, bis(3,3-dimethyl-4-cyanatophenyl)methane, bis(4-cyanatophenyl)methane, 1,3-dicyanatobenzene, 1,4-dicyanatobenzene, 1,3,5- tricyanatobenzene, 1,3-dicyanatonaphthalene, 1,4-dicyanatonaphthalene, 1,6-dicyanatonaphthalene, 1,8-dicyanatonaphthalene, 2,6-dicyanatonaphthalene, 2,7-dicyanato Naphthalene, 1,3,6-tricyanatonaphthalene, 4,4'-dicyanatobiphenyl, bis(4-cyanatophenyl)ether, bis(4-cyanatophenyl)thio
  • the cyanate ester compound is a polyfunctional cyanate ester such as a naphthol aralkyl-type cyanate ester compound and/or a novolac-type cyanate ester compound. It preferably contains a 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, Ryc may form a fused structure with a benzene ring, Ryc may or may not 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, an oxygen atom, and a sulfur atom. or represents a direct bond (single bond), and when Ryc does not exist, one benzene ring may have two or more Rya and/or Ryb groups, n represents an integer of 1-20.
  • the cyanate ester compound preferably contains a compound represented by formula (4) and/or formula (5) from the viewpoint of further improving heat resistance, low thermal expansion, and copper foil peel strength.
  • 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 as compound F is preferably 10 to 70 parts by mass with respect to 100 parts by mass of the resin solid content from the viewpoint of further improving low thermal expansion and copper foil peel strength. , more preferably 10 to 60 parts by mass, even more preferably 10 to 40 parts by mass.
  • a phenol compound A' other than the alkenylphenol A can be contained from the viewpoint of being able to exhibit even better copper foil peel strength.
  • the phenolic compound A′ is not particularly limited, but may be a bisphenol-type phenol resin (e.g., bisphenol A-type resin, bisphenol E-type resin, bisphenol F-type resin, bisphenol S-type resin, etc.), phenolic novolac resin (e.g., phenol novolak resin, naphthol novolac resin, cresol novolak resin, etc.), glycidyl ester type phenol resin, naphthalene type phenol resin, anthracene type phenol resin, dicyclopentadiene type phenol resin, biphenyl type phenol resin, alicyclic phenol resin, polyol type phenol Examples include resins, aralkyl-type phenol resins, phenol-modified aromatic hydrocarbon-formalde
  • the phenolic compound A' preferably contains a bifunctional phenolic compound having two phenolic hydroxyl groups in one molecule from the viewpoint of being able to exhibit even better compatibility and copper foil peel strength.
  • 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 at least one selected from the group consisting of bisphenol, biscresol, and bisphenols having a fluorene skeleton, from the viewpoint of being able to exhibit even better copper foil peel strength.
  • bis-cresol fluorene is preferable as the bisphenols having a fluorene skeleton.
  • aralkyl-type phenolic resins examples include compounds represented by the following formula (c2).
  • Ar 1 each independently represents a benzene ring or naphthalene ring
  • Ar 2 represents a benzene ring, naphthalene ring or biphenyl ring
  • R 2a each independently represents a hydrogen atom or a methyl group
  • m represents an integer of 1 to 50
  • each ring may have a substituent other than a hydroxyl group (eg, an alkyl group having 1 to 5 carbon atoms, a phenyl group, etc.).
  • the compound represented by formula (c2) is a compound in which Ar 1 is a naphthalene ring and Ar 2 is a benzene ring (hereinafter referred to as "naphthol aralkyl Also referred to as “biphenylaralkyl-type phenolic resin”), and in formula (c2), a compound in which Ar 1 is a benzene ring and Ar 2 is a biphenyl ring (hereinafter also referred to as "biphenylaralkyl-type phenolic resin").
  • naphthol aralkyl also referred to as "biphenylaralkyl-type phenolic resin”
  • the naphthol aralkyl-type phenolic resin is preferably a compound represented by the following formula (8).
  • each R 7 independently represents a hydrogen atom or a methyl group, and n 3 represents an integer of 1 or more.
  • n3 represents an integer of 1 or more, preferably an integer of 1-10, more preferably an integer of 1-6.
  • the biphenylaralkyl-type phenolic resin is preferably a compound represented by the following formula (2c).
  • each R 2b independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a phenyl group (preferably a hydrogen atom), m1 is an integer of 1 to 20 (preferably 1 to 6 integer).
  • the phenolic compound A' preferably contains the compound represented by the above formula (8).
  • a commercially available product or a product manufactured by a known method may be used as the aralkyl-type phenol resin.
  • Commercially available aralkyl-type phenolic resins include Nippon Kayaku Co., Ltd.'s "KAYAHARD GPH-65”, “KAYAHARD GPH-78", “KAYAHARD GPH-103” (biphenylaralkyl-type phenolic resin), Nippon Steel Chemical Co., Ltd.
  • the company's product "SN-495" (naphthol aralkyl type phenolic resin) can be mentioned.
  • the content of alkenylphenol A as compound F is 1 part per 100 parts by mass of the total amount of alkenylphenol A, epoxy-modified silicone B, epoxy compound C and phenolic compound A', from the viewpoint of being able to exhibit even better compatibility.
  • the amount is preferably to 50 parts by mass, more preferably 3 to 30 parts by mass, and even more preferably 5 to 20 parts by mass.
  • the content of the epoxy-modified silicone B in the curable composition of the present embodiment is, from the viewpoint of achieving well-balanced expression of even better low thermal expansion and copper foil peel strength, alkenylphenol A, epoxy-modified silicone B, epoxy compound C and 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 phenolic compound A' in the curable composition of the present embodiment is the total amount of the alkenylphenol A, the epoxy-modified silicone B, the epoxy compound C and the phenolic compound A' from the viewpoint of expressing even better copper foil peel strength. 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 100 parts by mass.
  • the contents of alkenylphenol A, epoxy-modified silicone B, and epoxy compound C are the same as those of alkenylphenol A, epoxy-modified silicone B, and epoxy compound C. It represents the content with respect to the total amount of 100 parts by mass.
  • compound F preferably contains an alkenyl-substituted nadimide compound.
  • 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 as compound F is preferably 1 to 40 parts by mass, preferably 5 to 35 parts by mass, relative to 100 parts by mass of the resin solid content. More preferably, 10 to 30 parts by mass is even more preferable.
  • the curable composition of the second embodiment includes a structural unit derived from alkenylphenol A, a structural unit derived from epoxy-modified silicone B, a structural unit derived from an epoxy compound C other than the epoxy-modified silicone B, and an acid A constituent unit derived from the anhydride D, and a polymer E containing a Alkenylphenol A, epoxy-modified silicone B, epoxy compound C and acid anhydride D are as described above.
  • polymer E containing structural units derived from alkenylphenol A, structural units derived from epoxy-modified silicone B, structural units derived from epoxy compound C, and structural units derived from acid anhydride D
  • the curable resin composition of the second embodiment containing is distinguished from the curable composition of the first embodiment described above, which relates to the aspect that does not have the polymer E.
  • Polymer E can exhibit sufficient compatibility even when mixed with a thermosetting resin that has poor compatibility with silicone compounds. Thereby, the curable composition containing the polymer E and the thermosetting resin can give a uniform varnish or cured product.
  • a cured product such as a prepreg obtained by using the curable composition has components uniformly dissolved therein, and variation in physical properties due to non-uniformity of the components is suppressed.
  • the curable composition of the second embodiment contains one or more selected from the group consisting of alkenylphenol A, epoxy-modified silicone B, epoxy compound C and acid anhydride D. good too.
  • the alkenylphenol A, the epoxy-modified silicone B, the epoxy compound C, and the acid anhydride D contained in the curable composition of the second embodiment may be unreacted components remaining after the polymerization of the polymer E. However, it may be a component added again to the synthesized polymer E.
  • the curable composition of the second embodiment may optionally contain the above-described maleimide compound, cyanate ester compound, phenol compound A' other than the alkenylphenol A, and alkenyl-substituted nadimide. It may further contain compound F, which is at least one selected from the group consisting of compounds. The compound F may be an unreacted component remaining after polymerization of the polymer E, or may be a component newly added to the polymer E synthesized.
  • Polymer E contains 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 acid anhydride D, If necessary, it further contains a structural unit derived from at least one compound F selected from the group consisting of a maleimide compound, a cyanate ester compound, a phenol compound A′ other than the alkenylphenol A, and an alkenyl-substituted nadimide compound.
  • the compound F is preferably a bifunctional compound.
  • structural units derived from alkenylphenol A "structural units derived from epoxy-modified silicone B”, “structural units derived from epoxy compound C”, and “structural units derived from acid anhydride D”
  • structural units derived from compound F are structural units obtained by polymerizing each component of alkenylphenol A, epoxy-modified silicone B, epoxy compound C, acid anhydride D and compound F in polymer E.
  • structural units formed by reactions or the like that can give similar structural units are also included.
  • each structural unit is also referred to as structural unit A, B, C, D, and F, respectively.
  • the weight-average molecular weight of the polymer E is preferably 3.0 ⁇ 10 3 to 5.0 ⁇ 10 4 and more preferably 3.0 ⁇ 10 3 to 2.0 ⁇ 10 in terms of polystyrene in gel permeation chromatography. 4 is more preferred. With a weight-average molecular weight of 3.0 ⁇ 10 3 or more, the curable composition of the second embodiment exhibits even better heat resistance, chemical resistance, low thermal expansion, copper foil peel strength, and insulation reliability. tend to be expressed. When the weight average molecular weight is 5.0 ⁇ 10 4 or less, the curable composition of the second embodiment tends to exhibit even better compatibility.
  • the content of the structural unit A in the polymer E is preferably 5 to 50% by mass with respect to the total mass of the polymer E.
  • the content of the structural unit A is within the above range, the curable composition of the second embodiment tends to exhibit even better compatibility.
  • the content of structural unit A is more preferably 10 to 45% by mass, even more preferably 15 to 40% by mass.
  • the content of the structural unit B in the polymer E is preferably 20 to 60% by mass with respect to the total mass of the polymer E.
  • the content of the structural unit B is within the above range, the curable composition of the second embodiment tends to exhibit even better low thermal expansion and copper foil peel strength in a well-balanced manner.
  • the content of structural unit B is more preferably 25 to 55% by mass, even more preferably 30 to 50% 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 E is preferably 5 to 25% by mass, more preferably 7.5 to 20% by mass, relative to the total mass of the polymer E. 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 E is preferably 15 to 55% by mass, more preferably 20 to 52.5% by mass, relative to the total mass of the polymer E. 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 1.7 to 3.5, and 1.9 to 3.1. is more preferable.
  • the curable composition of the second embodiment tends to have improved low thermal expansion and copper foil peel strength.
  • 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 content of the structural unit C in the polymer E is preferably 5 to 40% by mass with respect to the total mass of the polymer E.
  • the curable composition of the second embodiment has better compatibility, better heat resistance, chemical resistance, low thermal expansion, copper foil It tends to be able to develop peel strength 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 curable composition of the second embodiment has even better compatibility, heat resistance, chemical resistance, low thermal expansion, copper Foil peel strength and insulation reliability tend to be further improved.
  • the content of the structural unit D in the polymer E is preferably 3 to 20% by mass with respect to the total mass of the polymer E.
  • the curable composition of the second embodiment tends to exhibit even better low thermal expansion and copper foil peel strength in a well-balanced manner.
  • the content of structural unit D is more preferably 5 to 15% by mass, even more preferably 5 to 10% by mass.
  • the content of the structural unit F in the polymer E is preferably 3 to 40% by mass relative to the total mass of the polymer E.
  • the content of the structural unit F is within the above range, the curable composition of the second embodiment exhibits even better heat resistance, chemical resistance, low thermal expansion, copper foil peel strength, and insulation reliability. tend to be able.
  • the content of structural unit F is preferably 5 to 35% by mass, more preferably 10 to 30% by mass.
  • the content of the structural unit A' in the polymer E is It is preferably 5 to 30% by mass relative to the total mass of E.
  • the content of the structural unit A' is within the above range, the curable composition of the second embodiment has even better heat resistance, chemical resistance, low thermal expansion, copper foil peel strength and insulation reliability. tend to be expressed.
  • the content of the structural unit A' is preferably 10 to 27.5% by mass, more preferably 10 to 25% by mass.
  • the alkenyl group equivalent weight of the polymer E is preferably 300-1500 g/mol.
  • the alkenyl group equivalent is 300 g/mol or more, the cured product of the curable composition of the second embodiment tends to have a further decreased elastic modulus, and as a result, substrates and the like obtained using the cured product There is a tendency that the coefficient of thermal expansion can be further reduced.
  • the alkenyl group equivalent is 1500 g/mol or less, the compatibility, heat resistance, chemical resistance, low thermal expansion, copper foil peel strength, and insulation reliability of the curable composition of the second embodiment tend to be further improved. It is in. From the same point of view, the alkenyl group equivalent is preferably 350-1200 g/mol, more preferably 400-1000 g/mol.
  • the content of the polymer E in the curable composition of the second embodiment is preferably 5 to 50% by mass, more preferably 10 to 45% by mass, relative to 100% by mass of the resin solid content. , more preferably 15 to 40% by mass.
  • the curable composition tends to have more excellent compatibility and can exhibit low thermal expansion and copper foil peel strength in a well-balanced manner.
  • Polymer E can be obtained, for example, by reacting alkenylphenol A, epoxy-modified silicone B, epoxy compound C, acid anhydride D, and optionally compound F in the presence of polymerization catalyst G. can get.
  • 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 After the addition reaction with the epoxy group of the epoxy compound C proceeds, the addition reaction between the terminal hydroxyl group and the epoxy group and the acid anhydride D proceeds to obtain the polymer E.
  • the method for producing the curable composition of the present embodiment is obtaining a prepolymer obtained by polymerizing alkenylphenol A, epoxy-modified silicone B, and epoxy compound C; a step of reacting an acid anhydride D with the prepolymer; is preferably included.
  • an acid anhydride D is reacted with this prepolymer to obtain a low thermal expansion property and a copper foil. There is a tendency to obtain curable compositions with even better peel strength.
  • the polymerization catalyst G is not particularly limited, and includes, for example, one or more of imidazole compounds and organophosphorus compounds. These catalysts are used individually by 1 type or in combination of 2 or more types. Among these, imidazole compounds are preferred.
  • the imidazole compound is not particularly limited, and examples include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, -cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1, 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.); Among these, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole and/or 2,4,5-tripheny
  • the amount of the polymerization catalyst G (preferably an imidazole compound) used is not particularly limited. It is 0.1 to 10 parts by mass. From the viewpoint of increasing the weight average molecular weight of the polymer E, the amount of the polymerization catalyst G used is preferably 0.5 parts by mass or more, and more preferably 4.0 parts by mass or less.
  • 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, and 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, acid anhydride D and compound F. .
  • 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 E may be separated and purified from the reaction mixture by a conventional method.
  • the curable composition of the second embodiment may further contain compound F in addition to polymer E, if necessary.
  • the curable composition of the second embodiment tends to further improve heat resistance, chemical resistance, low thermal expansion and copper foil peel strength. .
  • the content of the polymer E in the curable composition of the second embodiment is a total of 100 mass% of the polymer E and the compound F On the other hand, it is preferably 5 to 60% by mass, more preferably 10 to 55% by mass, and even more preferably 20 to 50% by mass.
  • the curable composition tends to have more excellent compatibility and can exhibit low thermal expansion and copper foil peel strength in a well-balanced manner.
  • the content of the compound F in the curable composition of the second embodiment is a total of 100 mass% of the polymer E and the compound F It is preferably 20 to 80% by mass, more preferably 35 to 75% by mass, even more preferably 45 to 65% by mass.
  • the curable composition of the present embodiment may further contain other resins as long as the effects of the present 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 resins include oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, alkyloxetane such as 3,3-dimethyloxetane, 3-methyl-3-methoxymethyloxetane, 3,3- '-di(trifluoromethyl)perfluoxetane, 2-chloromethyloxetane, 3,3-bis(chloromethyl)oxetane, biphenyl type oxetane, products of Toagosei Co., Ltd. "OXT-101", “OXT-121" etc.
  • benzoxazine compound refers to a compound having two or more dihydrobenzoxazine rings in one molecule.
  • benzoxazine compounds include "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 vinyl compounds such as ethylene, propylene, styrene, divinylbenzene, divinylbiphenyl; methyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl ( Monovalent meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. or polyhydric alcohol (meth)acrylates; epoxy (meth)acrylates such as bisphenol A type epoxy (meth)acrylate and bisphenol F type epoxy (meth)acrylate; benzocyclobutene resin and the like.
  • vinyl compounds such as ethylene, propylene, styrene, divinylbenzene
  • the curable composition in the present embodiment preferably further contains an inorganic filler.
  • 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.
  • the curable composition of this embodiment may further contain a silane coupling agent.
  • a silane coupling agent By containing a silane coupling agent, the curable composition of the present embodiment further improves the dispersibility of the inorganic filler, and the components of the curable composition of the present embodiment and the substrate described later. There is a tendency that the adhesive strength 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.
  • the curable composition of this embodiment may further contain a wetting and dispersing agent.
  • the curable composition tends to further improve the dispersibility of the filler by containing a 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.
  • the curable composition of this embodiment may further contain a solvent.
  • a solvent By containing a solvent, the curable composition of the present embodiment has a lower viscosity during preparation of the curable composition, further improved handling properties (handleability), and further improved impregnating properties into the substrate. tend to fall.
  • the solvent is not particularly limited as long as it can dissolve a part or all of each component in the curable composition. 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 curable composition of the present embodiment is not particularly limited, and includes, for example, a method of collectively or sequentially blending each of the components described above 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.
  • the curable composition of the present embodiment has excellent compatibility and can exhibit even better low thermal expansion and copper foil peel strength. Therefore, the curable composition of the present embodiment is suitably used for metal foil-clad laminates and printed wiring boards. That is, the curable composition of this embodiment can be suitably used as a curable composition for printed wiring boards.
  • the curable composition of the second embodiment contains, in addition to the polymer E, at least an epoxy compound C (epoxy compound C existing separately from the structural unit C in the polymer E).
  • the polymer E preferably has units derived from the above-described bifunctional epoxy compound as units derived from the epoxy compound C, and more preferably has units derived from the above-described biphenyl-type epoxy compound.
  • the epoxy compound C present separately from the structural unit C in the polymer E 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 prepreg of this embodiment includes a substrate and the curable composition of this embodiment impregnated or applied to the substrate.
  • the prepreg may be a prepreg obtained by a known method, as described above. It is obtained by semi-curing (to B stage) by heating and drying at.
  • 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 curable composition in the prepreg is preferably 30 to 90% by volume, more preferably 35 to 85% by volume, and still more preferably 40% by volume in terms of the solid content of the prepreg with respect to the total amount of the prepreg. ⁇ 80% by volume.
  • the calculation of the content of the curable composition herein includes the cured product of the curable 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 base material is not particularly limited, and includes, for example, known base materials used as materials for various printed wiring boards.
  • 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. Among these, 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 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 resin sheet of this embodiment includes a support and the curable composition of this embodiment disposed on the surface of the support.
  • the resin sheet of the present embodiment may be formed, for example, by applying the curable composition of the present embodiment to one side or both sides of a support.
  • the resin sheet of the present embodiment can be produced, for example, by directly coating a support such as a metal foil or film with a curable composition used for prepreg or the like and drying the composition.
  • the support is not particularly limited, for example, known materials used in various printed wiring board materials can be used, and a resin sheet or metal foil is preferable.
  • resin sheets and metal foils include resin sheets such as polyimide film, polyamide film, polyester film, polyethylene terephthalate (PET) film, polybutylene terephthalate (PBT) film, polypropylene (PP) film, polyethylene (PE) film, etc. and metal foils such as aluminum foil, copper foil and gold foil.
  • the support is preferably an electrolytic copper foil or a PET film.
  • the resin sheet of the present embodiment can be obtained, for example, by applying the curable composition of the present embodiment to a support and then semi-curing (to B-stage).
  • the method for producing the resin sheet of the present embodiment is generally preferably a method for producing a composite of a B-stage resin and a support. Specifically, for example, after the curable composition is applied to a support such as a copper foil, it is semi-cured by a method of heating for 1 to 60 minutes in a dryer at 100 to 200 ° C. to form a resin sheet. A manufacturing method and the like can be mentioned.
  • the adhesion amount of the curable composition to the support is preferably in the range of 1.0 ⁇ m or more and 300 ⁇ m or less in terms of resin thickness of the resin sheet.
  • the resin sheet of this embodiment can be used as a build-up material for printed wiring boards.
  • the metal foil-clad laminate of the present embodiment includes a laminate formed using one or more selected from the group consisting of the prepreg and the resin sheet of the present embodiment, and a including metal foil.
  • the laminate may be formed of one prepreg or resin sheet, or may be formed of a plurality of prepregs and/or resin sheets.
  • the metal foil may be any metal foil 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 (laminate described above) or a metal foil-clad laminate.
  • the temperature is 100 to 300° C.
  • the pressure is 2 to 100 kgf/cm 2
  • the heating time is 0.05 to 5. Time ranges are common.
  • 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 the present embodiment has an insulating layer formed of one or more selected from the group consisting of the prepreg and the resin sheet of the present embodiment, and a conductor layer formed on the surface of the insulating layer. .
  • the printed wiring board of the present embodiment can be formed, for example, by etching the metal foil of the metal foil-clad laminate of the present embodiment into a predetermined wiring pattern to form a conductor layer.
  • the printed wiring board of the present embodiment can be manufactured, for example, by the following method.
  • 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.
  • 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.), 5.5 parts by mass of biscresol fluorene (BCF, Osaka Gas Chemical Co., Ltd.), epoxy Modified silicone compound A (X-22-163, Shin-Etsu Chemical Co., Ltd., functional group equivalent 200 g / eq.) 4.1 parts by mass, epoxy-modified silicone compound B (KF-105, Shin-Etsu Chemical Co., Ltd., functional Base equivalent 500 g / eq.) 8.4 parts by mass, biphenyl type epoxy compound A (YL-6121HA, Mitsubishi Chemical Corporation) 5.5 parts by mass, propylene glycol monomethyl ether acetate (DOWANOL PMA, Dow Chemical Japan) as a solvent Co., Ltd.) was added, and the mixture was heated to 120° C.
  • DABPA dially
  • diallyl bisphenol A corresponds to "alkenylphenol A”
  • epoxy-modified silicone compound A and epoxy-modified silicone compound B correspond to "epoxy-modified silicone B”
  • biphenyl-type epoxy compound A corresponds to "epoxy compound C Equivalent to The phenoxy polymer solution contained a polymer containing structural units derived from alkenylphenol A, structural units derived from epoxy-modified silicone B, and structural units derived from epoxy compound C.
  • the modified phenoxy polymer solution contains structural units derived from alkenylphenol A, structural units derived from epoxy-modified silicone B, structural units derived from epoxy compound C, and structural units derived from acid anhydride D. It contained a polymer that The polymer modification step can also be performed continuously with the polymer production step.
  • the weight average molecular weight Mw of the modified phenoxy polymer obtained as described above was measured as follows. Analysis was performed by injecting 20 ⁇ L of a solution prepared by dissolving 0.5 g of the modified phenoxy polymer solution in 2 g of THF into a high-performance liquid chromatography (manufactured by Shimadzu Corporation, pump: LC-20AD). 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 modified phenoxy polymer measured as described above was 12,000.
  • a varnish was obtained (varnish production step). This varnish was impregnated and coated on an S glass woven cloth (thickness 100 ⁇ m), dried by heating at 150 ° C. for 3 minutes, and a prepreg having a curable composition solid content (including filler) content of 58.2% by volume was obtained. was obtained (prepreg manufacturing process).
  • Example 2 In the polymer production step, the amount of diallyl bisphenol A added was 5.0 parts by mass to 4.7 parts by mass, the amount of biscresol fluorene added was 5.5 parts by mass to 5.2 parts by mass, and epoxy-modified silicone A was added. The amount added is 4.1 parts by mass to 3.8 parts by mass, the amount of epoxy-modified silicone B added is 8.4 parts by mass to 8.1 parts by mass, and the amount of biphenyl type epoxy compound A added is 5.5 parts by mass. In the same manner as in Example 1, except that the amount of acid anhydride D added in the polymer modification step was changed from 1.5 parts by mass to 5.2 parts by mass, and was changed to 3.0 parts by mass.
  • a prepreg having a curable composition solid content (including filler) content of 58.2% by volume was obtained.
  • the modified phenoxy polymer solution contains structural units derived from alkenylphenol A, structural units derived from epoxy-modified silicone B, structural units derived from epoxy compound C, and structural units derived from acid anhydride D. It contained a polymer that Moreover, the weight average molecular weight Mw of the modified phenoxy polymer in Example 2 measured by the method described above was 12,000.
  • Example 3 In the polymer modification step, the curable composition solid content was adjusted in the same manner as in Example 2, except that the acid anhydride D was replaced with 3.0 parts by mass of succinic anhydride and 3.0 parts by mass of phthalic anhydride. A prepreg with a content of 58.2% by volume (including filler) was obtained.
  • the modified phenoxy polymer solution contains structural units derived from alkenylphenol A, structural units derived from epoxy-modified silicone B, structural units derived from epoxy compound C, and structural units derived from acid anhydride D. It contained a polymer that The weight average molecular weight Mw of the modified phenoxy polymer in Example 3, measured by the method described above, was 12,000.
  • the copper foil clad laminates (Examples 1 to 3) using the curable composition of the present embodiment had excellent low thermal expansion and copper foil peel strength.

Abstract

A curable composition containing an alkenylphenol A, an epoxy-modified silicone B, an epoxy compound C other than the epoxy-modified silicone B, and an acid anhydride D.

Description

硬化性組成物、プリプレグ、レジンシート、金属箔張積層板及びプリント配線板Curable composition, prepreg, resin sheet, metal foil clad laminate and printed wiring board
　本発明は、硬化性組成物、プリプレグ、レジンシート、金属箔張積層板及びプリント配線板に関する。 The present invention relates to curable compositions, prepregs, resin sheets, metal foil-clad laminates, and printed wiring boards.
　近年、電子機器や通信機、パーソナルコンピューター等に広く用いられている半導体パッケージの高機能化、小型化が進むに伴い、半導体パッケージ用の各部品の高集積化や高密度実装化が近年益々加速している。これに伴い、半導体パッケージ用のプリント配線板に求められる諸特性はますます厳しいものとなっている。このようなプリント配線板に求められる特性としては、例えば、低熱膨張性、耐薬品性、ピール強度等が挙げられる。 In recent years, as semiconductor packages, which are widely used in electronic devices, communication devices, and personal computers, have become more sophisticated and smaller, the integration and high-density mounting of each component for semiconductor packages has accelerated in recent years. are doing. Along with this, various characteristics required for printed wiring boards for semiconductor packages are becoming more and more severe. Properties required for such printed wiring boards include, for example, low thermal expansion, chemical resistance, and peel strength.
　特許文献１には、特定のマレイミド化合物と、分子構造中にエポキシ基を有するシリコーン化合物と、フェノール性水酸基を有する化合物とを含有する熱硬化性樹脂組成物は、耐熱性及び低熱膨張性に優れ、金属箔張積層板及び多層プリント配線板に好適に用いられることが開示されている。 Patent Document 1 discloses that a thermosetting resin composition containing a specific maleimide compound, a silicone compound having an epoxy group in the molecular structure, and a compound having a phenolic hydroxyl group is excellent in heat resistance and low thermal expansion. , metal foil-clad laminates and multilayer printed wiring boards.
　特許文献２には、ポリマレイミドと、下記式（Ｉ）で表されるジグリシジルポリシロキサンと、下記式（ＩＩ）で表されるジアリルビスフェノール類との付加重合物と、下記式（ＩＩＩ）で表されるアリル化フェノール樹脂とを所定の割合及び条件にて反応させて半導体封止用樹脂を得る製造方法が開示されている。この文献によれば、上記の製造方法により得られる半導体封止用樹脂は、ポリマレイミドと、上記の付加重合物との相溶性が良いこと、更には半導体封止用樹脂を用いた組成物の硬化物特性（例えば、高いガラス転移温度、耐湿性及び熱時の強度）に優れ、半導体封止用樹脂組成物として信頼性の高いものであることが開示されている。この文献には、下記式（ＩＩＩ）中、ｂ成分は、ポリマレイミドとの樹脂生成反応においてマレイミド基と反応し、ポリマレイミドとポリシロキサンとの相溶性を改善する重要な成分であると開示されている。 In Patent Document 2, polymaleimide, a diglycidylpolysiloxane represented by the following formula (I), and an addition polymer of a diallyl bisphenol represented by the following formula (II), and the following formula (III) A manufacturing method is disclosed in which a resin for encapsulating a semiconductor is obtained by reacting an allylated phenol resin represented by the formula in a predetermined ratio and under predetermined conditions. According to this document, the resin for semiconductor encapsulation obtained by the above production method has good compatibility with polymaleimide and the addition polymer described above, and furthermore, the composition using the resin for semiconductor encapsulation has good compatibility. It is disclosed that the cured product has excellent properties (eg, high glass transition temperature, moisture resistance, and strength under heat) and is highly reliable as a resin composition for semiconductor encapsulation. This document discloses that component b in the following formula (III) is an important component that reacts with maleimide groups in a resin formation reaction with polymaleimide and improves the compatibility between polymaleimide and polysiloxane. ing.
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
（式中、Ｒ１は、アルキレン基又はフェニレン基を表し、Ｒ２は、各々独立して、アルキル基又はフェニル基を表し、ｎは１～１００の整数を表す。） (In the formula, R 1 represents an alkylene group or a phenylene group, each R 2 independently represents an alkyl group or a phenyl group, and n represents an integer of 1 to 100.)
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
（式中、Ｒ４は、エーテル結合、メチレン基、プロピリデン基又は直接結合（単結合）を表す。） (In the formula, R4 represents an ether bond, a methylene group, a propylidene group or a direct bond (single bond).)
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
（上記式中、ａ，ｂ，及びｃは、それぞれ各組成の百分率を表し、０＜ａ，ｂ，ｃ＜１００かつａ＋ｂ＋ｃ＝１００である。） (In the above formula, a, b, and c each represent the percentage of each composition, and 0<a, b, c<100 and a+b+c=100.)
特開２０１２－１４９１５４号公報JP 2012-149154 A 特開平４－４２１３号公報JP-A-4-4213
　特許文献１のように、分子構造中にエポキシ基を有するシリコーン化合物と、マレイミド化合物のような熱硬化性樹脂とを含む樹脂組成物は、低熱膨張性に優れる。しかしながら、本発明者らは、上記樹脂組成物において、上記シリコーン化合物と熱硬化性樹脂との相溶性が十分でないことに起因して成形性に問題があることを見出した。更に、本発明者らは、上記樹脂組成物は、金属箔張積層板とする際の金属箔ピール強度（例えば、銅箔ピール強度）が十分ではないことを見出した。 As in Patent Document 1, a resin composition containing a silicone compound having an epoxy group in its molecular structure and a thermosetting resin such as a maleimide compound is excellent in low thermal expansion. However, the present inventors have found that the resin composition has a problem in moldability due to insufficient compatibility between the silicone compound and the thermosetting resin. Furthermore, the present inventors have found that the above resin composition does not have sufficient metal foil peel strength (for example, copper foil peel strength) when used as a metal foil clad laminate.
　一方、特許文献２に記載の樹脂組成物は、半導体封止用に用いられるものであって、プリント配線板の特性として求められる低熱膨張性及び銅箔ピール強度については検討されていない。 On the other hand, the resin composition described in Patent Document 2 is used for semiconductor encapsulation, and low thermal expansion and copper foil peel strength required as characteristics of printed wiring boards have not been studied.
　本発明は、上記問題点に鑑みてなされたものであり、優れた低熱膨張性及び銅箔ピール強度を有する硬化性組成物、プリプレグ、レジンシート、金属箔張積層板及びプリント配線板を提供することを目的とする。 The present invention has been made in view of the above problems, and provides a curable composition, a prepreg, a resin sheet, a metal foil-clad laminate, and a printed wiring board having excellent low thermal expansion and copper foil peel strength. for the purpose.
　本発明者らは、上記課題を解決するために鋭意検討を重ねた。その結果、アルケニルフェノールと、エポキシ変性シリコーンと、エポキシ変性シリコーン以外のエポキシ化合物と、酸無水物とを含む硬化性組成物、又は、これらを構成単位として有する重合体を含む硬化性組成物であれば、上記課題を解決し得ることを見出し、本発明を完成するに至った。 The inventors have made extensive studies to solve the above problems. As a result, a curable composition containing an alkenylphenol, an epoxy-modified silicone, an epoxy compound other than the epoxy-modified silicone, and an acid anhydride, or a curable composition containing a polymer having these as structural units In other words, the inventors have found that the above problems can be solved, and have completed the present invention.
　すなわち、本発明は次のとおりである。
［１］
　アルケニルフェノールＡと、エポキシ変性シリコーンＢと、前記エポキシ変性シリコーンＢ以外のエポキシ化合物Ｃと、酸無水物Ｄを含有する、硬化性組成物。
［２］
　前記アルケニルフェノールＡの１分子当たりの平均フェノール基数が１以上３未満であり、前記エポキシ変性シリコーンＢの１分子当たりの平均エポキシ基数が１以上３未満であり、前記エポキシ化合物Ｃの１分子当たりの平均エポキシ基数が１以上３未満である、上記［１］に記載の硬化性組成物。
［３］
　前記アルケニルフェノールＡが、ジアリルビスフェノール及び／又はジプロペニルビスフェノールを含有する、上記［１］又は［２］に記載の硬化性組成物。
［４］
　前記エポキシ変性シリコーンＢが、１４０～２５０ｇ／ｍｏｌのエポキシ当量を有するエポキシ変性シリコーンを含有する、上記［１］～［３］のいずれか記載の硬化性組成物。
［５］
　前記エポキシ変性シリコーンＢが、下記式（１）で表されるエポキシ変性シリコーンを含有する、上記［１］～［４］のいずれか記載の硬化性組成物。
Figure JPOXMLDOC01-appb-C000015
 （式中、Ｒ１は、各々独立に、単結合、アルキレン基、アリーレン基又はアラルキレン基を示し、Ｒ２は、各々独立に、炭素数１～１０のアルキル基又はフェニル基を示し、ｎは、０～１００の整数を示す。）
［６］
　前記エポキシ化合物Ｃが、下記式（ｂ２）で表される化合物を含有する、上記［１］～［５］のいずれか記載の硬化性組成物。
Figure JPOXMLDOC01-appb-C000016
 （式中、Ｒａは、各々独立して、炭素数１～１０のアルキル基又は水素原子を表す。）
［７］
　前記エポキシ化合物Ｃの含有量が、前記エポキシ変性シリコーンＢ及び前記エポキシ化合物Ｃの合計量１００質量％に対して、２０～５０質量％である、上記［１］～［６］のいずれか記載の硬化性組成物。
［８］
　前記酸無水物Ｄは、無水フタル酸、無水コハク酸、無水マレイン酸、ナジック酸無水物及びｃｉｓ－４－シクロヘキセン－１，２－ジカルボン酸無水物からなる群より選択される１種以上である、上記［１］～［７］のいずれか記載の硬化性組成物。
［９］
　アルケニルフェノールＡに由来する構成単位と、エポキシ変性シリコーンＢに由来する構成単位と、エポキシ化合物Ｃに由来する構成単位と、酸無水物Ｄに由来する構成単位と、を含有する重合体Ｅを含む、硬化性組成物。
［１０］
　前記重合体Ｅの重量平均分子量が、３．０×１０３～５．０×１０４である、上記［９］に記載の硬化性組成物。
［１１］
　前記重合体Ｅ中の前記エポキシ変性シリコーンＢに由来する構成単位の含有量が、前記重合体Ｅの総質量に対して、２０～６０質量％である、上記［９］又は［１０］に記載の硬化性組成物。
［１２］
　前記重合体Ｅのアルケニル基当量が、３００～１５００ｇ／ｍｏｌである、上記［９］～［１１］のいずれか記載の硬化性組成物。
［１３］
　前記重合体Ｅ中の前記酸無水物Ｄに由来する構成単位の含有量が、前記重合体Ｅの総質量に対して、３～２０質量％である、上記［９］～［１２］のいずれか記載の硬化性組成物。
［１４］
　前記重合体Ｅの含有量が、樹脂固形分１００質量％に対して５～５０質量％である、上記［９］～［１３］のいずれか記載の硬化性組成物。
［１５］
　前記アルケニルフェノールＡが、ジアリルビスフェノール及び／又はジプロペニルビスフェノールを含有する、上記［９］～［１４］のいずれか記載の硬化性組成物。
［１６］
　前記エポキシ変性シリコーンＢが、１４０～２５０ｇ／ｍｏｌのエポキシ当量を有するエポキシ変性シリコーンを含有する、上記［９］～［１５］のいずれか記載の硬化性組成物。
［１７］
　前記エポキシ変性シリコーンＢが、下記式（１）で表されるエポキシ変性シリコーンを含有する、上記［９］～［１６］のいずれか記載の硬化性組成物。
Figure JPOXMLDOC01-appb-C000017
 （式中、Ｒ１は、各々独立に、単結合、アルキレン基、アリーレン基又はアラルキレン基を示し、Ｒ２は、各々独立に、炭素数１～１０のアルキル基又はフェニル基を示し、ｎは、０～１００の整数を示す。）
［１８］
　前記エポキシ化合物Ｃが、下記式（ｂ２）で表される化合物を含有する、上記［９］～［１７］のいずれか記載の硬化性組成物。
Figure JPOXMLDOC01-appb-C000018
 （式中、Ｒａは、各々独立して、炭素数１～１０のアルキル基又は水素原子を表す。）
［１９］
　前記酸無水物Ｄは、無水フタル酸、無水コハク酸、無水マレイン酸、ナジック酸無水物及びｃｉｓ－４－シクロヘキセン－１，２－ジカルボン酸無水物からなる群より選択される１種以上である、上記［９］～［１８］のいずれか記載の硬化性組成物。
［２０］
　さらに、エポキシ化合物Ｃを含み、前記エポキシ化合物Ｃが、下記式（３－３）で表される化合物又は下記式（３－４）で表される化合物を含む、上記［９］～［１９］のいずれか記載の硬化性組成物。
Figure JPOXMLDOC01-appb-C000019
 （式中、Ｒ１３は、各々独立して、水素原子、炭素数１～３のアルキル基又は炭素数２～３のアルケニル基を表す。）
Figure JPOXMLDOC01-appb-C000020
 （式中、Ｒ１４は、各々独立して、水素原子、炭素数１～３のアルキル基又は炭素数２～３のアルケニル基を表す。）
［２１］
　マレイミド化合物、シアン酸エステル化合物、アルケニルフェノールＡ以外のフェノール化合物Ａ’及びアルケニル置換ナジイミド化合物からなる群より選択される少なくとも１種の化合物Ｆを更に含む、上記［１］～［２０］のいずれか記載の硬化性組成物。
［２２］
　前記マレイミド化合物が、ビス（４－マレイミドフェニル）メタン、２，２－ビス｛４－（４－マレイミドフェノキシ）－フェニル｝プロパン、ビス（３－エチル－５－メチル－４－マレイミドフェニル）メタン、下記式（３）で表されるマレイミド化合物及び下記式（３’）で表されるマレイミド化合物からなる群より選ばれる少なくとも１種を含む、上記［２１］に記載の硬化性組成物。
Figure JPOXMLDOC01-appb-C000021
 （式中、Ｒ５は、各々独立して、水素原子又はメチル基を表し、ｎ１は１以上の整数を表す。）
Figure JPOXMLDOC01-appb-C000022
 （式（３’）中、Ｒ１３は各々独立に、水素原子、炭素数１～５のアルキル基、又はフェニル基を示し、ｎ４は１以上１０以下の整数を示す。）
［２３］
　前記シアン酸エステル化合物が、下記式（４）で表される化合物及び／又は下記式（４）で表される化合物を除く下記式（５）で表される化合物を含む、上記［２１］又は［２２］に記載の硬化性組成物。
Figure JPOXMLDOC01-appb-C000023
 （式中、Ｒ６は、各々独立して、水素原子又はメチル基を示し、ｎ２は１以上の整数を表す。）
Figure JPOXMLDOC01-appb-C000024
 （式中、Ｒｙａは、各々独立して、炭素数２～８のアルケニル基又は水素原子を表し、Ｒｙｂは、各々独立して、炭素数１～１０のアルキル基又は水素原子を表し、Ｒｙｃは、各々独立して、炭素数４～１２の芳香環を表し、Ｒｙｃは、ベンゼン環と縮合構造を形成してもよく、Ｒｙｃは、存在していてもよく、存在していなくてもよく、Ａ１ａは、各々独立して、炭素数１～６のアルキレン基、炭素数７～１６のアラルキレン基、炭素数６～１０のアリーレン基、フルオレニリデン基、スルホニル基、酸素原子、硫黄原子又は単結合を表し、Ｒｙｃが存在しない場合は、１つのベンゼン環にＲｙａ及び／又はＲｙｂの基を２つ以上有してもよく、ｎは、１～２０の整数を表す。）
［２４］
　前記フェノール化合物Ａ’が、下記式（８）で表される化合物を含む、上記［２１］～［２３］のいずれか記載の硬化性組成物。
Figure JPOXMLDOC01-appb-C000025
 （式中、Ｒ７は、各々独立して、水素原子又はメチル基を示し、ｎ３は１以上の整数を表す。）
［２５］
　無機充填材を更に含有し、前記無機充填材の含有量が、樹脂固形分１００質量部に対し５０～１０００質量部である、上記［１］～［２４］のいずれか記載の硬化性組成物。
［２６］
　前記無機充填材が、シリカ類、ベーマイト及びアルミナからなる群より選択される１種以上を含む、上記［２５］に記載の硬化性組成物。
［２７］
　プリント配線板用である、上記［１］～［２６］のいずれか記載の硬化性組成物。
［２８］
　基材と、前記基材に含浸又は塗布された上記［１］～［２７］のいずれか記載の硬化性組成物と、を含む、プリプレグ。
［２９］
　支持体と、前記支持体の表面に配置された上記［１］～［２７］のいずれか記載の硬化性組成物と、を含む、レジンシート。
［３０］
　上記［２８］に記載のプリプレグ及び上記［２９］に記載のレジンシートからなる群より選択される１種以上を用いて形成された積層体と、
　前記積層体の片面又は両面に配置された金属箔と、
を含む、金属箔張積層板。
［３１］
　上記［２８］に記載のプリプレグ及び上記［２９］に記載のレジンシートからなる群より選択される１種以上で形成された絶縁層と、
　前記絶縁層の表面に形成された導体層と、
を有する、プリント配線板。
［３２］
　アルケニルフェノールＡと、エポキシ変性シリコーンＢと、エポキシ化合物Ｃと、を重合して得られるプレポリマーを得る工程と、
　前記プレポリマーに対して酸無水物Ｄを反応させる工程と、
を含む、上記［１］～［２７］のいずれかに記載の硬化性組成物の製造方法。 That is, the present invention is as follows.
[1]
A curable composition comprising an alkenylphenol A, an epoxy-modified silicone B, an epoxy compound C other than the epoxy-modified silicone B, and an acid anhydride D.
[2]
The average number of phenol groups per molecule of the alkenylphenol A is 1 or more and less than 3, the average number of epoxy groups per molecule of the epoxy-modified silicone B is 1 or more and less than 3, and the epoxy compound C has an average number of The curable composition according to [1] above, which has an average number of epoxy groups of 1 or more and less than 3.
[3]
The curable composition according to the above [1] or [2], wherein the alkenylphenol A contains diallyl bisphenol and/or dipropenyl bisphenol.
[4]
The curable composition according to any one of [1] to [3] above, wherein the epoxy-modified silicone B contains an epoxy-modified silicone having an epoxy equivalent of 140 to 250 g/mol.
[5]
The curable composition according to any one of [1] to [4] above, wherein the epoxy-modified silicone B contains an epoxy-modified silicone represented by the following formula (1).
Figure JPOXMLDOC01-appb-C000015
 (wherein 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 is , represents an integer from 0 to 100.)
[6]
The curable composition according to any one of [1] to [5] above, wherein the epoxy compound C contains a compound represented by the following formula (b2).
Figure JPOXMLDOC01-appb-C000016
 (In the formula, each R a independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom.)
[7]
The content of the epoxy compound C is 20 to 50% by mass with respect to 100% by mass of the total amount of the epoxy-modified silicone B and the epoxy compound C, according to any one of [1] to [6] above. Curable composition.
[8]
The acid anhydride D is one or more selected from the group consisting of phthalic anhydride, succinic anhydride, maleic anhydride, nadic anhydride and cis-4-cyclohexene-1,2-dicarboxylic anhydride. , the curable composition according to any one of the above [1] to [7].
[9]
A polymer E containing 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 acid anhydride D. , a curable composition.
[10]
The curable composition according to [9] above, wherein the polymer E has a weight average molecular weight of 3.0×10 3 to 5.0×10 4 .
[11]
[9] or [10] above, wherein the content of the structural unit derived from the epoxy-modified silicone B in the polymer E is 20 to 60% by mass with respect to the total mass of the polymer E. curable composition.
[12]
The curable composition according to any one of [9] to [11] above, wherein the polymer E has an alkenyl group equivalent weight of 300 to 1500 g/mol.
[13]
Any of the above [9] to [12], wherein the content of the structural unit derived from the acid anhydride D in the polymer E is 3 to 20% by mass with respect to the total mass of the polymer E. The curable composition according to .
[14]
The curable composition according to any one of [9] to [13] above, wherein the content of the polymer E is 5 to 50% by mass based on 100% by mass of the resin solid content.
[15]
The curable composition according to any one of [9] to [14] above, wherein the alkenylphenol A contains diallyl bisphenol and/or dipropenyl bisphenol.
[16]
The curable composition according to any one of [9] to [15] above, wherein the epoxy-modified silicone B contains an epoxy-modified silicone having an epoxy equivalent of 140 to 250 g/mol.
[17]
The curable composition according to any one of [9] to [16] above, wherein the epoxy-modified silicone B contains an epoxy-modified silicone represented by the following formula (1).
Figure JPOXMLDOC01-appb-C000017
 (wherein 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 is , represents an integer from 0 to 100.)
[18]
The curable composition according to any one of [9] to [17] above, wherein the epoxy compound C contains a compound represented by the following formula (b2).
Figure JPOXMLDOC01-appb-C000018
 (In the formula, each R a independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom.)
[19]
The acid anhydride D is one or more selected from the group consisting of phthalic anhydride, succinic anhydride, maleic anhydride, nadic anhydride and cis-4-cyclohexene-1,2-dicarboxylic anhydride. , the curable composition according to any one of the above [9] to [18].
[20]
[9] to [19] above, further comprising an epoxy compound C, wherein the epoxy compound C comprises a compound represented by the following formula (3-3) or a compound represented by the following formula (3-4) The curable composition according to any one of
Figure JPOXMLDOC01-appb-C000019
 (In the formula, each R 13 independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or an alkenyl group having 2 to 3 carbon atoms.)
Figure JPOXMLDOC01-appb-C000020
 (In the formula, each R 14 independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkenyl group having 2 to 3 carbon atoms.)
[21]
Any one of the above [1] to [20], further comprising at least one compound F selected from the group consisting of maleimide compounds, cyanate ester compounds, phenol compounds A' other than alkenylphenol A, and alkenyl-substituted nadimide compounds. A curable composition as described.
[22]
The maleimide compound is bis(4-maleimidophenyl)methane, 2,2-bis{4-(4-maleimidophenoxy)-phenyl}propane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, The curable composition according to [21] above, which contains at least one selected from the group consisting of a maleimide compound represented by the following formula (3) and a maleimide compound represented by the following formula (3′).
Figure JPOXMLDOC01-appb-C000021
 (In the formula, each R 5 independently represents a hydrogen atom or a methyl group, and n 1 represents an integer of 1 or more.)
Figure JPOXMLDOC01-appb-C000022
 (In 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.)
[23]
The cyanate ester compound contains a compound represented by the following formula (5) excluding the compound represented by the following formula (4) and / or the compound represented by the following formula (4) [21] or The curable composition according to [22].
Figure JPOXMLDOC01-appb-C000023
 (In the formula, each R6 independently represents a hydrogen atom or a methyl group, and n2 represents an integer of 1 or more.)
Figure JPOXMLDOC01-appb-C000024
 (wherein R ya each independently represents an alkenyl group having 2 to 8 carbon atoms or a hydrogen atom, each R yb independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom, Each R yc independently represents an aromatic ring having 4 to 12 carbon atoms, R yc may form a condensed structure with a benzene ring, 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, an oxygen atom, represents a sulfur atom or a single bond, and when R yc does not exist, one benzene ring may have two or more R ya and/or R yb groups, and n represents an integer of 1 to 20 .)
[24]
The curable composition according to any one of [21] to [23] above, wherein the phenol compound A' contains a compound represented by the following formula (8).
Figure JPOXMLDOC01-appb-C000025
 (In the formula, each R 7 independently represents a hydrogen atom or a methyl group, and n 3 represents an integer of 1 or more.)
[25]
The curable composition according to any one of the above [1] to [24], which further contains an inorganic filler, 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. .
[26]
The curable composition according to [25] above, wherein the inorganic filler contains one or more selected from the group consisting of silicas, boehmite and alumina.
[27]
The curable composition according to any one of [1] to [26] above, which is used for printed wiring boards.
[28]
A prepreg comprising a substrate and the curable composition according to any one of [1] to [27] impregnated or applied to the substrate.
[29]
A resin sheet comprising a support and the curable composition according to any one of [1] to [27] disposed on the surface of the support.
[30]
A laminate formed using one or more selected from the group consisting of the prepreg described in [28] above and the resin sheet described in [29] above;
a metal foil disposed on one side or both sides of the laminate;
A metal foil clad laminate comprising:
[31]
an insulating layer formed of one or more selected from the group consisting of the prepreg described in [28] above and the resin sheet described in [29] above;
a conductor layer formed on the surface of the insulating layer;
A printed wiring board.
[32]
obtaining a prepolymer obtained by polymerizing alkenylphenol A, epoxy-modified silicone B, and epoxy compound C;
a step of reacting an acid anhydride D with the prepolymer;
A method for producing a curable composition according to any one of [1] to [27] above.
　本発明によれば、優れた低熱膨張性及び銅箔ピール強度を有する硬化性組成物、プリプレグ、レジンシート、金属箔張積層板及びプリント配線板を提供可能である。 According to the present invention, it is possible to provide curable compositions, prepregs, resin sheets, metal foil-clad laminates and printed wiring boards having excellent low thermal expansion and copper foil peel strength.
　以下、本発明を実施するための形態（以下「本実施形態」という。）について詳細に説明するが、本発明はこれに限定されるものではなく、その要旨を逸脱しない範囲で様々な変形が可能である。 Hereinafter, 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.
　本明細書にいう「樹脂固形分」とは、特段の記載がない限り、本実施形態の硬化性組成物における、溶剤及び充填材を除いた成分をいい、樹脂固形分１００質量部とは、硬化性組成物における溶剤及び充填材を除いた成分の合計が１００質量部であることをいう。また、樹脂固形分１００質量％とは、硬化性組成物における溶剤及び充填材を除いた成分の合計が１００質量％であることをいう。 As used herein, the term "resin solid content" refers to the components excluding the solvent and filler in the curable composition of the present embodiment, unless otherwise specified. It means that the total amount of components excluding the solvent and filler in the curable 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 curable composition is 100 mass %.
　また、後述する第１実施形態の硬化性組成物において、「優れた相溶性」とは、アルケニルフェノールＡと、エポキシ変性シリコーンＢと、エポキシ化合物Ｃと、酸無水物Ｄとを含有する混合物（例えば、ワニス）の状態で、液相分離が生じないことをいう。
　また、後述する第２実施形態の硬化性組成物において、「優れた相溶性」とは、重合体Ｅと他の成分とを含む混合物（例えば、ワニス）の状態で、液相分離が生じないことをいう。
　本実施形態の硬化性組成物は、相溶性に優れることに起因して、成形の過程における液相分離が抑制され、外観に優れる成形体を得られるほか、得られた成形体の物性の等方性にも優れる傾向にある。なお、本明細書において、「本実施形態の硬化性組成物」と称するときは、特段の断りがない限り、「第１実施形態の硬化性組成物」及び「第２実施形態の硬化性組成物」の双方を包含するものとする。 Further, in the curable composition of the first embodiment described later, "excellent compatibility" means a mixture containing alkenylphenol A, epoxy-modified silicone B, epoxy compound C, and acid anhydride D ( For example, it means that liquid phase separation does not occur in the state of varnish.
Further, in the curable composition of the second embodiment described later, the term "excellent compatibility" means that liquid phase separation does not occur in a state of a mixture (for example, varnish) containing the polymer E and other components. Say things.
Due to its excellent compatibility, the curable composition of the present embodiment suppresses liquid phase separation in the process of molding, and can obtain a molded article with excellent appearance, as well as the physical properties of the obtained molded article. It also tends to be excellent in directionality. In this specification, when referring to the "curable composition of the present embodiment", unless otherwise specified, the "curable composition of the first embodiment" and the "curable composition of the second embodiment" shall include both "things".
［第１実施形態：硬化性組成物］
　第１実施形態の硬化性組成物は、アルケニルフェノールＡと、エポキシ変性シリコーンＢと、エポキシ変性シリコーンＢを除くエポキシ化合物Ｃ（以下、単に「エポキシ化合物Ｃ」ともいう。）と、酸無水物Ｄとを含有する。これら成分を含む硬化性組成物は、エポキシ変性シリコーンＢとの相溶性が十分でない熱硬化性樹脂（以下、単に「熱硬化性樹脂」ともいう）との相溶性により優れる傾向がある。これに起因して、第１実施形態の硬化性組成物は、より優れた相溶性が発現可能となり、低熱膨張性及び銅箔ピール強度に優れる。また、硬化性組成物は、これらの成分の各々の一部を反応（重合）させて用いると、更に優れた相溶性が発現可能となり、より優れた低熱膨張性及び銅箔ピール強度が発現可能となる（第２実施形態の硬化性組成物）。 [First embodiment: curable composition]
The curable composition of the first embodiment comprises alkenylphenol A, epoxy-modified silicone B, epoxy compound C excluding epoxy-modified silicone B (hereinafter also simply referred to as “epoxy compound C”), and acid anhydride D and A curable composition containing these components tends to be more compatible with thermosetting resins (hereinafter also simply referred to as “thermosetting resins”) that are not sufficiently compatible with epoxy-modified silicone B. Due to this, the curable composition of the first embodiment can exhibit more excellent compatibility, and is excellent in low thermal expansion and copper foil peel strength. In addition, when the curable composition is used by partially reacting (polymerizing) each of these components, it is possible to exhibit even better compatibility, and it is possible to exhibit better low thermal expansion and copper foil peel strength. (the curable composition of the second embodiment).
［アルケニルフェノールＡ］
　アルケニルフェノールＡは、１つ以上のアルケニル基がフェノール性芳香環に直接結合した構造を有する化合物であれば特に限定されない。本実施形態の硬化性組成物は、アルケニルフェノールＡを含有することにより、優れた相溶性を発現できる。 [Alkenylphenol A]
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 curable composition of the present embodiment can exhibit excellent compatibility.
　アルケニル基としては、特に限定されないが、例えば、ビニル基、アリル基、プロペニル基、ブテニル基、ヘキセニル基等の炭素数２～３０のアルケニル基が挙げられる。なかでも、本発明の作用効果をより有効かつ確実に奏する観点から、アルケニル基は、アリル基及び／又はプロペニル基であることが好ましく、アリル基であることが更に好ましい。１つのフェノール性芳香環に直接結合しているアルケニル基の数は、特に限定されず、例えば、１～４である。本発明の作用効果をより有効かつ確実に奏する観点から、１つのフェノール性芳香環に直接結合しているアルケニル基の数は、好ましくは１～２であり、更に好ましくは１である。また、アルケニル基のフェノール性芳香環への結合位置も特に限定されないが、オルト位（２，６位）であることが好ましい。 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 invention. 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 invention. Also, 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.
　フェノール性芳香環は、１つ以上の水酸基が芳香環に直接結合したものをいい、フェノール環やナフトール環が挙げられる。１つのフェノール性芳香環に直接結合している水酸基の数は、特に限定されず、例えば、１～２であり、好ましくは１である。 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.
　フェノール性芳香環は、アルケニル基以外の置換基を有していてもよい。そのような置換基としては、例えば、炭素数１～１０の直鎖状アルキル基、炭素数３～１０の分岐状アルキル基、炭素数３～１０の環状アルキル基、炭素数１～１０の直鎖状アルコキシ基、炭素数３～１０の分岐状アルコキシ基、炭素数３～１０の環状アルコキシ基、及びハロゲン原子が挙げられる。フェノール性芳香環がアルケニル基以外の置換基を有する場合、１つのフェノール性芳香環に直接結合している当該置換基の数は、特に限定されず、例えば、１～２である。また、当該置換基のフェノール性芳香環への結合位置も特に限定されない。 The phenolic aromatic ring may have substituents other than alkenyl groups. Examples of such 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. When the phenolic aromatic ring has substituents other than alkenyl groups, the number of such substituents directly bonded to one phenolic aromatic ring is not particularly limited, and is, for example, 1-2. Also, the bonding position of the substituent to the phenolic aromatic ring is not particularly limited.
　アルケニルフェノールＡは、１つ以上のアルケニル基がフェノール性芳香環に直接結合した構造を１つ又は複数有してもよい。本発明の作用効果をより有効かつ確実に奏する観点から、アルケニルフェノールＡは、１つ以上のアルケニル基がフェノール性芳香環に直接結合した構造を１つ又は２つ有することが好ましく、２つ有することが好ましい。 Alkenylphenol A may have one or more structures in which one or more alkenyl groups are directly bonded to a phenolic aromatic ring. From the viewpoint of more effectively and reliably exhibiting the effects of the present invention, alkenylphenol A preferably has one or two structures in which one or more alkenyl groups are directly bonded to a phenolic aromatic ring, and has two is preferred.
　アルケニルフェノールＡは、例えば、下記式（１Ａ）又は下記式（１Ｂ）で表される化合物であってもよい。 Alkenylphenol A may be, for example, a compound represented by formula (1A) or formula (1B) below.
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
（式中、Ｒｘａは、各々独立して、炭素数２～８のアルケニル基を表し、Ｒｘｂは、各々独立して、炭素数１～１０のアルキル基又は水素原子を表し、Ｒｘｃは、各々独立して、炭素数４～１２の芳香環を表し、Ｒｘｃは、ベンゼン環と縮合構造を形成してもよく、Ｒｘｃは、存在していてもよく、存在していなくてもよく、Ａは、炭素数１～６のアルキレン基、炭素数７～１６のアラルキレン基、炭素数６～１０のアリーレン基、フルオレニリデン基、スルホニル基、酸素原子、硫黄原子又は直接結合（単結合）を表し、Ｒｘｃが存在しない場合は、１つのベンゼン環にＲｘａ及び／又はＲｘｂの基を２つ以上有してもよい。） (Wherein, 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 each independently represents represents an aromatic ring having 4 to 12 carbon atoms, Rxc may form a condensed structure with a benzene ring, Rxc may or may not be present, and A is 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); If it does not exist, one benzene ring may have two or more Rxa and/or Rxb groups.)
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000027
（式中、Ｒｘｄは、各々独立して、炭素数２～８のアルケニル基を表し、Ｒｘｅは、各々独立して、炭素数１～１０のアルキル基又は水素原子を表し、Ｒｘｆは、炭素数４～１２の芳香環を表し、Ｒｘｆは、ベンゼン環と縮合構造を形成してもよく、Ｒｘｆは、存在していても、存在していなくてもよく、Ｒｘｆが存在しない場合は、１つのベンゼン環にＲｘｄ及び／又はＲｘｅの基を２つ以上有してもよい。） (Wherein, 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; Represents 4 to 12 aromatic rings, Rxf may form a fused structure with a benzene ring, Rxf may or may not be present, and when Rxf is absent, one The benzene ring may have two or more Rxd and/or Rxe groups.)
　式（１Ａ）及び式（１Ｂ）中、Ｒｘａ及びＲｘｄとして表される炭素数２～８のアルケニル基としては、特に制限されないが、例えば、ビニル基、アリル基、プロペニル基、ブテニル基、ヘキセニル基等が挙げられる。 In formulas (1A) and (1B), alkenyl groups having 2 to 8 carbon atoms represented by Rxa and Rxd are not particularly limited, and examples thereof include vinyl group, allyl group, propenyl group, butenyl group and hexenyl group. etc.
　式（１Ａ）及び式（１Ｂ）中、Ｒｘｃ及びＲｘｆで表される基がベンゼン環と縮合構造を形成している場合としては、例えば、フェノール性芳香環として、ナフトール環を含む化合物が挙げられる。また、式（１Ａ）及び式（１Ｂ）中、Ｒｘｃ及びＲｘｆで表される基が存在しない場合としては、例えば、フェノール性芳香環として、フェノール環を含む化合物が挙げられる。 In formulas (1A) and (1B), when the groups represented by Rxc and Rxf form a condensed structure with a benzene ring, examples thereof include compounds containing a naphthol ring as the phenolic aromatic ring. . Further, in the case where the groups represented by Rxc and Rxf are not present in the formulas (1A) and (1B), for example, compounds containing a phenol ring can be mentioned as the phenolic aromatic ring.
　式（１Ａ）及び式（１Ｂ）中、Ｒｘｂ及びＲｘｅとして表される炭素数１～１０のアルキル基としては、特に制限されないが、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基等の直鎖状アルキル基、イソプロピル基、イソブチル基、ｔｅｒｔ－ブチル基等の分岐状アルキル基が挙げられる。 In formulas (1A) and (1B), 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.
　式（１Ａ）中、Ａとして表される炭素数１～６のアルキレン基としては、特に制限されないが、例えば、メチレン基、エチレン基、トリメチレン基、プロピレン基が挙げられる。Ａとして表される炭素数７～１６のアラルキレン基としては、特に制限されないが、例えば、式：－ＣＨ２－Ａｒ－ＣＨ２－、－ＣＨ２－ＣＨ２－Ａｒ－ＣＨ２－ＣＨ２－、又は式：－ＣＨ２－Ａｒ－ＣＨ２－ＣＨ２－（式中、Ａｒは、フェニレン基、ナフチレン基、又はビフェニレン基を表す。）で表される基が挙げられる、Ａとして表される炭素数６～１０のアリーレン基としては、特に制限されないが、例えば、フェニレン環が挙げられる。 In formula (1A), 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, but is, for example, represented by 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 is not particularly limited and includes, for example, a phenylene ring.
　式（１Ｂ）で表される化合物は、本発明の作用効果をより有効かつ確実に奏する観点から、Ｒｘｆがベンゼン環であること（ジヒドロキシナフタレン骨格を含む化合物）が好ましい。 In the compound represented by formula (1B), 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 invention.
　アルケニルフェノールＡは、相溶性を一層向上させる観点から、ビスフェノール類の２つのフェノール性芳香環にそれぞれ１つのアルケニル基が結合したアルケニルビスフェノールであることが好ましい。同様の観点から、アルケニルビスフェノールは、ビスフェノール類の２つのフェノール性芳香環にそれぞれ１つのアリル基が結合したジアリルビスフェノール、及び／又はビスフェノール類の２つのフェノール性芳香環にそれぞれ１つのプロペニル基が結合したジプロペニルビスフェノールであることが好ましい。 From the viewpoint of further improving compatibility, alkenylphenol A is preferably alkenylbisphenol in which one alkenyl group is bonded to each of two phenolic aromatic rings of bisphenols. From a similar point of view, alkenyl bisphenol is diallyl bisphenol in which two phenolic aromatic rings of the bisphenol are respectively bound to one allyl group, and/or two phenolic aromatic rings of the bisphenol are respectively bound to one propenyl group. preferably dipropenyl bisphenol.
　ジアリルビスフェノールとしては、特に制限されないが、例えば、ｏ，ｏ’－ジアリルビスフェノールＡ（大和化成工業株式会社製品の「ＤＡＢＰＡ」）、ｏ，ｏ’－ジアリルビスフェノールＦ、ｏ，ｏ’－ジアリルビスフェノールＳ、ｏ，ｏ’－ジアリルビスフェノールフルオレンが挙げられる。ジプロペニルビスフェノールとしては、特に制限されないが、例えば、ｏ，ｏ’－ジプロペニルビスフェノールＡ（群栄化学工業株式会社の「ＰＢＡ０１」）、ｏ，ｏ’－ジプロペニルビスフェノールＦ、ｏ，ｏ’－ジプロペニルビスフェノールＳ、ｏ，ｏ’－ジプロペニルビスフェノールフルオレンが挙げられる。 The diallyl bisphenol is not particularly limited, but for example, o,o'-diallyl bisphenol A ("DABPA", a product of Daiwa Kasei Kogyo Co., Ltd.), o, o'-diallyl bisphenol F, o, o'-diallyl bisphenol S , o,o'-diallylbisphenol fluorene. The dipropenyl bisphenol is not particularly limited, and examples thereof include o,o'-dipropenylbisphenol A ("PBA01" from Gunei Chemical Industry Co., Ltd.), o,o'-dipropenylbisphenol F, o,o'- Dipropenyl bisphenol S, o,o'-dipropenyl bisphenol fluorene.
　アルケニルフェノールＡの１分子当たりの平均フェノール基数は、本発明の作用効果をより有効かつ確実に奏する観点から、１以上３未満であることが好ましく、１．５以上２．５以下であることがより好ましい。平均フェノール基数は、以下の式により算出される。 The average number of phenol groups per molecule of alkenylphenol A is preferably 1 or more and less than 3, and preferably 1.5 or more and 2.5 or less, from the viewpoint of more effectively and reliably exhibiting the effects of the present invention. more preferred. The average number of phenol groups is calculated by the following formula.
Figure JPOXMLDOC01-appb-M000028
Figure JPOXMLDOC01-appb-M000028
　式中、Ａｉは、分子中にｉ個のフェノール基を有するアルケニルフェノールのフェノール基数を表し、Ｘｉは、分子中にｉ個のフェノール基を有するアルケニルフェノールのアルケニルフェノール全体に占める割合を表し、Ｘ１＋Ｘ２＋…Ｘｎ＝１である。 In the formula, A represents the number of phenol groups in alkenylphenol having i phenol groups in the molecule, Xi represents the ratio of alkenylphenol having i phenol groups in the molecule to all alkenylphenols, and X 1 + X 2 + . . . X n =1.
［エポキシ変性シリコーンＢ］
　エポキシ変性シリコーンＢは、エポキシ基含有基により変性されたシリコーン化合物または樹脂であれば特に限定されない。本実施形態の硬化性組成物は、エポキシ変性シリコーンＢを含有することにより、優れた低熱膨張性及び銅箔ピール強度を発現できる。 [Epoxy-modified silicone B]
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 curable composition of the present embodiment can exhibit excellent low thermal expansion and copper foil peel strength.
　シリコーン化合物または樹脂は、シロキサン結合が繰り返し形成されたポリシロキサン骨格を有する化合物であれば特に限定されない。ポリシロキサン骨格は、直鎖状の骨格であってもよく、環状の骨格であってもよく、網目状の骨格であってもよい。このなかでも、本発明の作用効果をより有効かつ確実に奏する観点から、直鎖状の骨格であることが好ましい。 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 invention.
　エポキシ基含有基としては、特に制限されないが、例えば、下記式（ａ１）で表される基が挙げられる。 The epoxy group-containing group is not particularly limited, but includes, for example, a group represented by the following formula (a1).
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000029
（式中、Ｒ０は、アルキレン基（例えば、メチレン基、エチレン基、プロピレン基等の炭素数１～５のアルキレン基）を表し、Ｘは、下記式（ａ２）で表される１価の基又は下記式（ａ３）で表される１価の基を表す。） (Wherein, R 0 represents an alkylene group (e.g., a methylene group, an ethylene group, an alkylene group having 1 to 5 carbon atoms such as a propylene group), and X is a monovalent represented by the following formula (a2) group or a monovalent group represented by the following formula (a3).)
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000031
　エポキシ変性シリコーンＢは、１４０～２５０ｇ／ｍｏｌのエポキシ当量を有するエポキシ変性シリコーンを含有することが好ましい。エポキシ変性シリコーンＢは、上記範囲内にあるエポキシ当量を有するエポキシ変性シリコーンを含有することにより、熱硬化性樹脂との相溶性に優れ、低熱膨張性及び銅箔ピール強度をバランスよく一層向上できる傾向にある。上記エポキシ当量は、同様の観点から、１４５～２４５ｇ／ｍｏｌであることがより好ましく、１５０～２４０ｇ／ｍｏｌであることが更に好ましい。 Epoxy-modified silicone B preferably contains an epoxy-modified silicone having an epoxy equivalent of 140 to 250 g/mol. By containing an epoxy-modified silicone having an epoxy equivalent within the above range, epoxy-modified silicone B has excellent compatibility with thermosetting resins, and tends to further improve low thermal expansion and copper foil peel strength in a well-balanced manner. It is in. From the same viewpoint, the epoxy equivalent is more preferably 145 to 245 g/mol, still more preferably 150 to 240 g/mol.
　エポキシ変性シリコーンＢは、熱硬化性樹脂との相溶性により一層優れ、低熱膨張性及び銅箔ピール強度をバランスよく一層向上できる観点から、２種以上のエポキシ変性シリコーンを含有することが好ましい。この場合、２種以上のエポキシ変性シリコーンは、それぞれ異なるエポキシ当量を有することが好ましく、５０～３５０ｇ／ｍｏｌのエポキシ当量を有するエポキシ変性シリコーン（以下、「低当量エポキシ変性シリコーンＢ１」ともいう。）と、４００～４０００ｇ／ｍｏｌのエポキシ当量を有するエポキシ変性シリコーン（以下、「高当量エポキシ変性シリコーンＢ２」ともいう。）とを含有することがより好ましく、１４０～２５０ｇ／ｍｏｌのエポキシ当量を有するエポキシ変性シリコーン（低当量エポキシ変性シリコーンＢ１’）と、４５０～３０００ｇ／ｍｏｌのエポキシ当量を有するエポキシ変性シリコーン（高当量エポキシ変性シリコーンＢ２’）とを含有することがさらに好ましい。 Epoxy-modified silicone B preferably contains two or more types of epoxy-modified silicones from the viewpoint of further improving compatibility with thermosetting resins and further improving low thermal expansion and copper foil peel strength in a well-balanced manner. In this case, 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′).
　エポキシ変性シリコーンＢが２種以上のエポキシ変性シリコーンを含有する場合、エポキシ変性シリコーンＢの平均エポキシ当量は、１４０～３０００ｇ／ｍｏｌであることが好ましく、２５０～２０００ｇ／ｍｏｌであることがより好ましく、３００～１０００ｇ／ｍｏｌであることが更に好ましい。平均エポキシ当量は、以下の式により算出される。 When the epoxy-modified silicone B contains two or more epoxy-modified silicones, 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. The average epoxy equivalent is calculated by the following formula.
Figure JPOXMLDOC01-appb-M000032
Figure JPOXMLDOC01-appb-M000032
（式中、Ｅｉは、２種以上のエポキシ変性シリコーンのうちの１種のエポキシ変性シリコーンのエポキシ当量を表し、Ｗｉは、エポキシ変性シリコーンＢ中の上記エポキシ変性シリコーンの割合を表し、Ｗ１＋Ｗ２＋…Ｗｎ＝１である。） (In the formula, Ei represents the epoxy equivalent of one epoxy-modified silicone among two or more epoxy-modified silicones, Wi represents the ratio of the epoxy-modified silicone in epoxy-modified silicone B, and W 1 +W 2 + . . . W n =1.)
　エポキシ変性シリコーンＢは、熱硬化性樹脂との相溶性により優れ、低熱膨張性及び銅箔ピール強度をバランスよく一層向上できる観点から、下記式（１）で表されるエポキシ変性シリコーンを含有することが好ましい。
Figure JPOXMLDOC01-appb-C000033
 Epoxy-modified silicone B should contain an epoxy-modified silicone represented by the following formula (1) from the viewpoint of having excellent compatibility with thermosetting resins and further improving low thermal expansion and copper foil peel strength in a well-balanced manner. is preferred.
Figure JPOXMLDOC01-appb-C000033
　式（１）中、Ｒ１は、各々独立に、単結合、アルキレン基、アリーレン基又はアラルキレン基を示し、Ｒ２は、各々独立に、炭素数１～１０のアルキル基又はフェニル基を示し、ｎは、０～１００の整数を示す。 In formula (1), 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;
　式（１）中、Ｒ１で表されるアルキレン基は、直鎖状、分岐状又は環状のいずれであってもよい。アルキレン基の炭素数は、好ましくは１～１２であり、より好ましくは１～４である。アルキレン基としては、例えば、メチレン基、エチレン基又はプロピレン基が挙げられる。これらの中でも、Ｒ１は、プロピレン基であることが好ましい。 In formula (1), 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.
　式（１）中、Ｒ１で表されるアリーレン基は、置換基を有していてもよい。アリーレン基の炭素数としては、好ましくは６～４０であり、より好ましくは６～２０である。アリーレン基としては、例えば、フェニレン基、シクロヘキシルフェニレン基、ヒドロキシフェニレン基、シアノフェニレン基、ニトロフェニレン基、ナフチリレン基、ビフェニレン基、アントリレン基、ピレニレン基、フルオレニレン基等が挙げられる。これらの基には、エーテル結合、ケトン結合、あるいはエステル結合を含んでいてもよい。 In formula (1), 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.
　式（１）中、Ｒ１で表されるアラルキレン基の炭素数は、好ましくは７～３０であり、より好ましくは７～１３である。アラルキレン基としては、例えば、下記式(Ｘ－Ｉ)で表される基が挙げられる。
Figure JPOXMLDOC01-appb-C000034
 （式（Ｘ－Ｉ）中、＊は、結合手を表す。） In formula (1), 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).
Figure JPOXMLDOC01-appb-C000034
 (In formula (XI), * represents a bond.)
　式（１）中、Ｒ１で表される基は、更に置換基を有していてもよく、置換基としては、例えば、炭素数１～１０の直鎖状アルキル基、炭素数３～１０の分岐状アルキル基、炭素数３～１０の環状アルキル基、炭素数１～１０の直鎖状アルコキシ基、炭素数３～１０の分岐状アルコキシ基、炭素数３～１０の環状アルコキシ基が挙げられる。これらの中でも、Ｒ１は、プロピレン基であることが特に好ましい。 In formula (1), the group represented by R 1 may further have a substituent. Examples of 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. Among these, R 1 is particularly preferably a propylene group.
　式（１）中、Ｒ２は、各々独立して、炭素数１～１０のアルキル基又はフェニル基を表す。上記アルキル基及びフェニル基は、置換基を有してもよい。炭素数１～１０のアルキル基は、直鎖状、分岐状又は環状のいずれであってもよい。アルキル基としては、特に限定されないが、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、イソプロピル基、イソブチル基、シクロヘキシル基が挙げられる。これらの中でも、Ｒ２は、メチル基又はフェニル基であることが好ましい。 In formula (1), 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. Among these, R 2 is preferably a methyl group or a phenyl group.
　式（１）中、ｎは０以上の整数を表し、例えば、０～１００である。熱硬化性樹脂との相溶性により優れ、低熱膨張性及び銅箔ピール強度をバランスよく一層向上できる観点から、ｎは、好ましくは５０以下であり、より好ましくは３０以下であり、更に好ましくは２０以下である。 In formula (1), n represents an integer of 0 or more, for example, 0 to 100. n is preferably 50 or less, more preferably 30 or less, and even more preferably 20, from the viewpoint of better compatibility with thermosetting resins and further improvement of low thermal expansion and copper foil peel strength in a well-balanced manner. It is below.
　エポキシ変性シリコーンＢは、熱硬化性樹脂との相溶性により一層優れ、低熱膨張性及び銅箔ピール強度をバランスよく一層向上させる観点から、式（１）で表されるエポキシ変性シリコーンを２種類以上含有することが好ましい。この場合、２種類以上含有するエポキシ変性シリコーンは、それぞれ異なるｎを有することが好ましく、式（１）においてｎが１～２であるエポキシ変性シリコーンと、式（１）においてｎが５～２０であるエポキシ変性シリコーンとを含有することがより好ましい。 Epoxy-modified silicone B is more excellent in compatibility with the thermosetting resin, and from the viewpoint of further improving low thermal expansion and copper foil peel strength in a well-balanced manner, two or more types of epoxy-modified silicones represented by formula (1) are used. It is preferable to contain. In this case, 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.
　エポキシ変性シリコーンＢの１分子当たりの平均エポキシ基数は、本発明の作用効果をより有効かつ確実に奏する観点から、１以上３未満であることが好ましく、１．５以上２．５以下であることがより好ましい。平均エポキシ基数は、以下の式により算出される。 The average number of epoxy groups per molecule of epoxy-modified silicone B 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 invention. is more preferred. The average number of epoxy groups is calculated by the following formula.
Figure JPOXMLDOC01-appb-M000035
Figure JPOXMLDOC01-appb-M000035
（式中、Ｂｉは、分子中にｉ個のエポキシ基を有するエポキシ変性シリコーンのエポキシ基数を表し、Ｙｉは、分子中にｉ個のエポキシ基を有するエポキシ変性シリコーンのエポキシ変性シリコーン全体に占める割合を表し、Ｙ１＋Ｙ２＋…Ｙｎ＝１である。） (In the formula, Bi represents the number of epoxy groups of the epoxy-modified silicone having i epoxy groups in the molecule, and Yi represents the ratio of the epoxy-modified silicone having i epoxy groups in the molecule to the total epoxy-modified silicone. and Y 1 + Y 2 + … Y n = 1.)
　エポキシ変性シリコーンＢの含有量は、一層優れた低熱膨張性及び耐薬品性を発現できる観点から、エポキシ変性シリコーンＢ及びエポキシ化合物Ｃの合計１００質量％に対して、５～９５質量％であることが好ましく、１０～９０質量％であることがより好ましく、４０～８５質量％であることが更に好ましく、５０～８０質量％であることが更により好ましい。 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.
　エポキシ変性シリコーンＢとしては、市販品を用いてもよく、公知の方法により製造された製品を用いてもよい。市販品としては、例えば、信越化学工業株式会社製品の「Ｘ－２２－１６３」、「ＫＦ－１０５」が挙げられる。 As the 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.
［エポキシ化合物Ｃ］
　エポキシ化合物Ｃは、エポキシ変性シリコーンＢ以外のエポキシ化合物であり、より具体的には、ポリシロキサン骨格を有しないエポキシ化合物である。本実施形態の硬化性組成物は、エポキシ化合物Ｃを含有することにより、優れた相溶性、耐熱性、耐薬品性、銅箔ピール強度及び絶縁信頼性を発現できる。 [Epoxy compound C]
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. By containing the epoxy compound C, the curable composition of the present embodiment can exhibit excellent compatibility, heat resistance, chemical resistance, copper foil peel strength, and insulation reliability.
　エポキシ化合物Ｃとしては、エポキシ変性シリコーンＢ以外のエポキシ化合物であれば特に限定されない。本実施形態の硬化性組成物におけるエポキシ化合物Ｃとしては、典型的には、１分子中にエポキシ基を２つ有する２官能エポキシ化合物や１分子中にエポキシ基を３つ以上有する多官能エポキシ化合物を使用することができる。エポキシ化合物Ｃは、一層優れた相溶性、耐熱性、耐薬品性、銅箔ピール強度及び絶縁信頼性を発現できる観点から、２官能エポキシ化合物及び／又は多官能エポキシ化合物を含有することが好ましい。 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 curable 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. 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 better compatibility, heat resistance, chemical resistance, copper foil peel strength and insulation reliability.
　本実施形態の硬化性組成物におけるエポキシ化合物Ｃとしては、特に限定されないが、下記式（３ａ）で表される化合物を用いることができる。
Figure JPOXMLDOC01-appb-C000036
 （式（３ａ）中、Ａｒ３は、各々独立して、ベンゼン環又はナフタレン環を表し、Ａｒ４は、ベンゼン環、ナフタレン環又はビフェニル環を表し、Ｒ３ａは、各々独立して、水素原子又はメチル基を表し、ｋは１～５０の整数を表し、
　ここで、Ａｒ３におけるベンゼン環又はナフタレン環は、さらに一又は複数の置換基を有してもよく、当該置換基は、図示しないグリシジルオキシ基であってもよく、その他の置換基、例えば、炭素数１～５のアルキル基、フェニル基等であってもよく、
　Ａｒ４におけるベンゼン環、ナフタレン環又はビフェニル環は、さらに一又は複数の置換基を有してもよく、当該置換基は、グリシジルオキシ基であってもよく、その他の置換基、例えば、炭素数１～５のアルキル基、フェニル基等であってもよい。） The epoxy compound C in the curable composition of the present embodiment is not particularly limited, but a compound represented by the following formula (3a) can be used.
Figure JPOXMLDOC01-appb-C000036
 (In Formula (3a), Ar 3 each independently represents a benzene ring or naphthalene ring, Ar 4 represents a benzene ring, naphthalene ring or biphenyl ring, and R 3a each independently represents a hydrogen atom. or represents a methyl group, k represents an integer of 1 to 50,
Here, 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. )
　上記式（３ａ）で表される化合物中、２官能エポキシ化合物としては、例えば、下記式（ｂ１）で表される化合物が挙げられる。
Figure JPOXMLDOC01-appb-C000037
 （式（ｂ１）中、Ａｒ３は、各々独立して、ベンゼン環又はナフタレン環を表し、Ａｒ４は、ベンゼン環、ナフタレン環又はビフェニル環を表し、Ｒ３ａは、各々独立して、水素原子又はメチル基を表し、
　ここで、Ａｒ３におけるベンゼン環又はナフタレン環は、さらに一又は複数の置換基を有してもよく、当該置換基は、例えば、炭素数１～５のアルキル基やフェニル基等のグリシジルオキシ基以外の置換基であってもよく、
　Ａｒ４におけるベンゼン環、ナフタレン環又はビフェニル環は、さらに一又は複数の置換基を有してもよく、当該置換基は、例えば、炭素数１～５のアルキル基やフェニル基等のグリシジルオキシ基以外の置換基であってもよい。） Among the compounds represented by the above formula (3a), examples of bifunctional epoxy compounds include compounds represented by the following formula (b1).
Figure JPOXMLDOC01-appb-C000037
 (In 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, and each R 3a independently represents a hydrogen atom or represents a methyl group,
Here, 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. It may be a substituent other than
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 )
　式（３ａ）で表される化合物は、式（３ａ）においてＡｒ４が少なくともグリシジルオキシ基で置換された、フェノール類ノボラック型エポキシ樹脂であることが好ましい。フェノール類ノボラック型エポキシ樹脂としては、特に限定されないが、例えば、下記式（３－１）で表される構造を有する化合物（ナフタレン骨格を有するナフタレン骨格含有多官能エポキシ樹脂）や、ナフタレンクレゾールノボラック型エポキシ樹脂が挙げられる。 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.
Figure JPOXMLDOC01-appb-C000038
 （式中、Ａｒ３１は、各々独立して、ベンゼン環又はナフタレン環を表し、Ａｒ４１は、各々独立して、ベンゼン環、ナフタレン環又はビフェニル環を表し、Ｒ３１ａは、各々独立して、水素原子又はメチル基を表し、ｐは１を表し、ｋｚは１～５０の整数を表し、各環は、グリシジルオキシ基以外の置換基（例えば、炭素数１～５のアルキル基、炭素数１～５のアルコキシ基又はフェニル基）を有してもよく、Ａｒ３１及びＡｒ４１の少なくとも一方はナフタレン環を表す。）
Figure JPOXMLDOC01-appb-C000038
 (wherein 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 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 to 5 alkoxy groups or phenyl groups), and at least one of Ar 31 and Ar 41 represents a naphthalene ring.)
　式（３－１）で表される構造を有する化合物としては、式（３－２）で表される構造を有する化合物が挙げられる。
Figure JPOXMLDOC01-appb-C000039
 （式中、Ｒは、メチル基を表し、ｋｚは、上記式（３－１）中のｋｚと同義である。） Compounds having a structure represented by formula (3-1) include compounds having a structure represented by formula (3-2).
Figure JPOXMLDOC01-appb-C000039
 (Wherein, R represents a methyl group, and kz is synonymous with kz in the above formula (3-1).)
　ナフタレンクレゾールノボラック型エポキシ樹脂としては、特に限定されないが、例えば、下記式（ＮＥ）で示されるクレゾール／ナフトールノボラック型エポキシ樹脂が好ましい。なお、下記式（ＮＥ）で示される化合物は、クレゾールノボラックエポキシの構成単位と、ナフトールノボラックエポキシの構成単位とのランダム共重合体であり、クレゾールエポキシ及びナフトールエポキシのいずれもが末端になりうる。
Figure JPOXMLDOC01-appb-C000040
 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.
Figure JPOXMLDOC01-appb-C000040
　前記式（ＮＥ）におけるｍ及びｎは、各々、１以上の整数を表す。ｍ及びｎの上限及びその比については特に限定されないが、低熱膨張性の観点から、ｍ：ｎ（ここで、ｍ＋ｎ＝１００）として、３０～５０：７０～５０であることが好ましく、４５～５５：５５～４５がより好ましい。 m and n in the formula (NE) each represent an integer of 1 or more. The upper limit of m and n and the ratio thereof are not particularly limited, but from the viewpoint of low thermal expansion, m: n (here, m + n = 100) is preferably 30 to 50: 70 to 50, and 45 to 55:55-45 is more preferred.
　ナフタレンクレゾールノボラック型エポキシ樹脂としては、市販品を用いてもよく、公知の方法により製造された製品を用いてもよい。市販品としては、例えば、日本化薬株式会社製品の「ＮＣ－７０００」、「ＮＣ－７３００」、「ＮＣ－７３００Ｌ」や、ＤＩＣ株式会社製品の「ＨＰ－９５４０」、「ＨＰ－９５００」等が挙げられ、「ＨＰ－９５４０」がとりわけ好ましい。 As the naphthalene cresol novolac type epoxy resin, a commercially available product or a product manufactured by a known method may be used. Examples of 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.
　式（３ａ）で表される化合物は、上述したフェノール類ノボラック型エポキシ樹脂に該当しない化合物（以下、「アラルキル型エポキシ樹脂」ともいう。）であってもよい。
　アラルキル型エポキシ樹脂としては、式（３ａ）においてＡｒ３がナフタレン環であり、Ａｒ４がベンゼン環である化合物（「ナフトールアラルキル型エポキシ樹脂」ともいう。）、及び式（３ａ）においてＡｒ３がベンゼン環であり、Ａｒ４がビフェニル環である化合物（「ビフェニルアラルキル型エポキシ樹脂」ともいう。）であることが好ましく、ビフェニルアラルキル型エポキシ樹脂であることがより好ましい。 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.
　ナフトールアラルキル型エポキシ樹脂としては、市販品を用いてもよく、公知の方法により製造された製品を用いてもよい。市販品としては、例えば、ＤＩＣ株式会社製品の「ＨＰ－５０００」、「ＨＰ－９９００」、日鉄ケミカル株式会社製品の「ＥＳＮ－３７５」、「ＥＳＮ－４７５」等が挙げられる。 As the 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, "ESN-375" and "ESN-475" manufactured by Nippon Steel Chemical Co., Ltd., and the like.
　ビフェニルアラルキル型エポキシ樹脂は、下記式（３ｂ）で表される化合物であることが好ましい。
Figure JPOXMLDOC01-appb-C000041
 （式中、ｋａは、１以上の整数を表し、１～２０が好ましく、１～６がより好ましい。） The biphenyl aralkyl type epoxy resin is preferably a compound represented by the following formula (3b).
Figure JPOXMLDOC01-appb-C000041
 (Wherein, ka represents an integer of 1 or more, preferably 1 to 20, more preferably 1 to 6.)
　上記式（３ｂ）で表される化合物中、２官能エポキシ化合物としては、例えば、式（３ｂ）においてｋａが１である化合物が挙げられる。 Among the compounds represented by the above formula (3b), bifunctional epoxy compounds include, for example, compounds in which ka is 1 in formula (3b).
　ビフェニルアラルキル型エポキシ樹脂としては、市販品を用いてもよく、公知の方法により製造された製品を用いてもよい。市販品としては、例えば、日本化薬株式会社製品の「ＮＣ－３０００」、「ＮＣ－３０００Ｌ」、「ＮＣ－３０００ＦＨ」等が挙げられる。 As the biphenyl 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 "NC-3000", "NC-3000L", and "NC-3000FH" manufactured by Nippon Kayaku Co., Ltd.
　また、本実施形態の硬化性組成物におけるエポキシ化合物Ｃとしては、ナフタレン型エポキシ樹脂（式（３ａ）で表される化合物に該当するものを除く。）を用いることが好ましい。ナフタレン型エポキシ樹脂としては、耐熱性、耐薬品性、銅箔ピール強度及び絶縁信頼性を一層向上させる観点から、ナフチレンエーテル型エポキシ樹脂であることが好ましい。 In addition, as the epoxy compound C in the curable 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 peel strength, and insulation reliability.
　ナフチレンエーテル型エポキシ樹脂は、耐熱性、耐薬品性、銅箔ピール強度及び絶縁信頼性を一層向上させる観点から、下記式（３－３）で表される２官能エポキシ化合物又は下記式（３－４）で表される多官能エポキシ化合物、あるいは、それらの混合物であることが好ましい。
Figure JPOXMLDOC01-appb-C000042
 （式中、Ｒ１３は、各々独立して、水素原子、炭素数１～３のアルキル基（例えば、メチル基又はエチル基）、又は炭素数２～３のアルケニル基（例えば、ビニル基、アリル基又はプロペニル基）を表す。）
Figure JPOXMLDOC01-appb-C000043
 （式中、Ｒ１４は、各々独立して、水素原子、炭素数１～３のアルキル基（例えば、メチル基又はエチル基）、又は炭素数２～３のアルケニル基（例えば、ビニル基、アリル基又はプロペニル基）を表す。） From the viewpoint of further improving heat resistance, chemical resistance, copper foil peel strength 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.
Figure JPOXMLDOC01-appb-C000042
 (In the formula, 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).)
Figure JPOXMLDOC01-appb-C000043
 (In the formula, 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).)
　ナフチレンエーテル型エポキシ樹脂は、市販品を用いてもよく、公知の方法により製造された製品を用いてもよい。ナフチレンエーテル型エポキシ樹脂の市販品としては、例えば、ＤＩＣ株式会社製品の「ＨＰ－６０００」、「ＥＸＡ－７３００」、「ＥＸＡ－７３１０」、「ＥＸＡ－７３１１」、「ＥＸＡ－７３１１Ｌ」、「ＥＸＡ７３１１－Ｇ３」、「ＥＸＡ７３１１－Ｇ４」、「ＥＸＡ－７３１１Ｇ４Ｓ」、「ＥＸＡ－７３１１Ｇ５」等が挙げられ、とりわけＨＰ－６０００が好ましい。 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.
　ナフタレン型エポキシ樹脂の上記したもの以外の例としては、以下に限定されないが、下記式（ｂ３）で表される化合物が挙げられる。
Figure JPOXMLDOC01-appb-C000044
 （式（ｂ３）中、Ｒ３ｂは、各々独立して、水素原子、炭素数１～５のアルキル基（例えば、メチル基又はエチル基）、アラルキル基、ベンジル基、ナフチル基、少なくとも１つのグリシジルオキシ基を含有するナフチル基又は少なくとも１つのグリシジルオキシ基を含有するナフチルメチル基を表し、ｎは、０以上の整数（例えば、０～２）を表す。） Examples of naphthalene-type epoxy resins other than those described above include, but are not limited to, compounds represented by the following formula (b3).
Figure JPOXMLDOC01-appb-C000044
 (In the formula (b3), 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).)
　上記式（ｂ３）で表される化合物の市販品としては、例えば、ＤＩＣ株式会社製品の「ＨＰ－４０３２」（上記式（ｂ３）においてｎ＝０）、「ＨＰ－４７１０」（上記式（ｂ３）において、ｎ＝０であり、Ｒ３ｂが少なくとも１つのグリシジルオキシ基を含有するナフチルメチル基）等が挙げられる。 Examples of commercially available products of the compound represented by the above formula (b3) include "HP-4032" (n = 0 in the above formula (b3)) and "HP-4710" (the above formula (b3)) manufactured by DIC Corporation. ) where n=0 and R 3b is a naphthylmethyl group containing at least one glycidyloxy group).
　また、本実施形態の硬化性組成物におけるエポキシ化合物Ｃとしては、ビフェニル型エポキシ化合物（上述したエポキシ化合物Ｃに該当するものを除く。）を用いることが好ましい。
　ビフェニル型エポキシ化合物としては、特に限定されないが、例えば、下記式（ｂ２）で表される化合物（化合物ｂ２）が挙げられる。
Figure JPOXMLDOC01-appb-C000045
 （式（ｂ２）中、Ｒａは、各々独立して、炭素数１～１０のアルキル基又は水素原子を表す。） Moreover, as the epoxy compound C in the curable composition of the present embodiment, it is preferable to use a biphenyl-type epoxy compound (excluding those corresponding to the epoxy compound C described above).
The biphenyl-type epoxy compound is not particularly limited, but includes, for example, a compound represented by the following formula (b2) (compound b2).
Figure JPOXMLDOC01-appb-C000045
 (In formula (b2), each Ra independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom.)
　式（ｂ２）中、炭素数１～１０のアルキル基は、直鎖状、分岐状又は環状のいずれであってもよい。アルキル基としては、特に限定されないが、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、イソプロピル基、イソブチル基、シクロヘキシル基が挙げられる。 In formula (b2), 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.
　ビフェニル型エポキシ化合物が、化合物ｂ２である場合、ビフェニル型エポキシ化合物は、アルキル基であるＲａの数が異なる化合物ｂ２の混合物の形態であってもよい。具体的には、アルキル基であるＲａの数が異なるビフェニル型エポキシ化合物の混合物であることが好ましく、アルキル基であるＲａの数が０である化合物ｂ２と、アルキル基であるＲａの数が４である化合物ｂ２の混合物であることがより好ましい。 When the biphenyl-type epoxy compound is compound b2, the biphenyl-type epoxy compound 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 compounds having different numbers of Ra as alkyl groups. It is more preferred to be a mixture of compounds b2 which are
　また、本実施形態の硬化性組成物におけるエポキシ化合物Ｃとしては、ジシクロペンタジエン型エポキシ樹脂（上述したエポキシ化合物Ｃに該当するものを除く。）を用いることができる。
　ジシクロペンタジエン型エポキシ樹脂としては、特に限定されないが、例えば、下記式（３－５）で表される化合物が挙げられる。
Figure JPOXMLDOC01-appb-C000046
 （式中、Ｒ３ｃは、各々独立し、水素原子又は炭素数１～５のアルキル基を表し、ｋ２は、０～１０の整数を表す。） Moreover, as the epoxy compound C in the curable composition of the present embodiment, 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).
Figure JPOXMLDOC01-appb-C000046
 (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.)
　上記式（３－５）で表される化合物は、特に限定されないが、例えば、下記式（ｂ４）で表される化合物であってもよい。
Figure JPOXMLDOC01-appb-C000047
 （式（ｂ４）中、Ｒ３ｃは、各々独立し、水素原子又は炭素数１～５のアルキル基（例えば、メチル基又はエチル基）を表す。） The compound represented by the above formula (3-5) is not particularly limited, but may be, for example, a compound represented by the following formula (b4).
Figure JPOXMLDOC01-appb-C000047
 (In formula (b4), each R 3c independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms (eg, methyl group or ethyl group).)
　ジシクロペンタジエン型エポキシ樹脂は、市販品を用いてもよく、公知の方法により製造された製品を用いてもよい。ジシクロペンタジエン型エポキシ樹脂の市販品としては、大日本インキ化学工業株式会社製品の「ＥＰＩＣＲＯＮ　ＨＰ－７２００Ｌ」、「ＥＰＩＣＲＯＮ　ＨＰ－７２００」、「ＥＰＩＣＲＯＮ　ＨＰ－７２００Ｈ」、「ＥＰＩＣＲＯＮ　ＨＰ－７０００ＨＨ」等が挙げられる。 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.
　これらの中でも、エポキシ化合物Ｃは、一層優れた耐熱性、耐薬品性、銅箔ピール強度及び絶縁信頼性を発現できる観点から、式（３ａ）で表されるエポキシ化合物、ナフタレン型エポキシ樹脂及びビフェニル型エポキシ化合物からなる群より選択される１種以上であることが好ましく、この場合において、式（３ａ）で表されるエポキシ化合物はナフタレンクレゾールノボラック型エポキシ樹脂を含み、ナフタレン型エポキシ樹脂はナフチレンエーテル型エポキシ樹脂を含むことが好ましい。 Among these, 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 peel strength and insulation reliability. is preferably one or more selected from the group consisting of type epoxy compounds, and in this case, the epoxy compound represented by formula (3a) includes a naphthalene cresol novolac type epoxy resin, and the naphthalene type epoxy resin is naphthylene It preferably contains an ether type epoxy resin.
　エポキシ化合物Ｃとしては、前述したエポキシ化合物に該当しない、他のエポキシ化合物を含んでいてもよい。
　他のエポキシ化合物としては、特に限定されないが、ビスフェノール型エポキシ樹脂、トリスフェノールメタン型エポキシ樹脂、アントラセン型エポキシ樹脂、グリシジルエステル型エポキシ樹脂、ポリオール型エポキシ樹脂、イソシアヌレート環含有エポキシ樹脂、フルオレン型エポキシ樹脂、ビスフェノールＡ型構造単位と炭化水素系構造単位からなるエポキシ樹脂等が挙げられる。
　他のエポキシ化合物としては、上記した中でも、耐熱性、耐薬品性、銅箔ピール強度及び絶縁信頼性を一層向上させる観点から、ビスフェノール型エポキシ樹脂を含むことができ、ビスフェノール型エポキシ樹脂としては、例えば、ジアリルビスフェノール型エポキシ樹脂（例えば、ジアリルビスフェノールＡ型エポキシ樹脂、ジアリルビスフェノールＥ型エポキシ樹脂、ジアリルビスフェノールＦ型エポキシ樹脂、ジアリルビスフェノールＳ型エポキシ樹脂等）等を用いることができる。 Epoxy compound C may contain other epoxy compounds that do not correspond to the epoxy compounds described above.
Examples of 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.
Among the above-described other epoxy compounds, from the viewpoint of further improving heat resistance, chemical resistance, copper foil peel strength, and insulation reliability, bisphenol-type epoxy resins can be included. For example, diallylbisphenol type epoxy resins (for example, diallylbisphenol A type epoxy resin, diallylbisphenol E type epoxy resin, diallylbisphenol F type epoxy resin, diallylbisphenol S type epoxy resin, etc.) can be used.
　エポキシ化合物Ｃとしては、前述したエポキシ化合物及びエポキシ樹脂のうち、１種を単独で、又は２種以上を組み合わせて用いられる。 As the 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.
　エポキシ化合物Ｃの１分子当たりの平均エポキシ基数は、本実施形態の作用効果をより有効かつ確実に奏する観点から、１以上３未満であることが好ましく、１．５以上２．５以下であることがより好ましい。平均エポキシ基数は、以下の式により算出される。
Figure JPOXMLDOC01-appb-M000048
 （上記式中、Ｃｉは、分子中にｉ個のエポキシ基を有するエポキシ化合物のエポキシ基数を表し、Ｚｉは、分子中にｉ個のエポキシ基を有するエポキシ化合物のエポキシ化合物全体に占める割合を表し、Ｚ１＋Ｚ２＋…Ｚｎ＝１である。） 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 average number of epoxy groups is calculated by the following formula.
Figure JPOXMLDOC01-appb-M000048
 (In the above formula, Ci represents the number of epoxy groups in an epoxy compound having i epoxy groups in the molecule, and Zi represents the ratio of the epoxy compounds having i epoxy groups in the molecule to the total number of epoxy compounds. , Z 1 +Z 2 + . . . Z n =1.)
　エポキシ化合物Ｃの含有量は、一層優れた耐熱性、耐薬品性、銅箔ピール強度及び絶縁信頼性を発現できる観点から、エポキシ変性シリコーンＢ及びエポキシ化合物Ｃの合計量１００質量％に対して、５～９５質量％であることが好ましく、１０～９０質量％であることがより好ましく、１５～６０質量％であることが更に好ましく、２０～５０質量％であることが特に好ましい。 The content of the epoxy compound C is, from the viewpoint of being able to exhibit even better heat resistance, chemical resistance, copper foil peel strength 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.
［酸無水物Ｄ］
　本実施形態の硬化性組成物は、酸無水物Ｄを含む。酸無水物Ｄは、アルケニルフェノールＡと、エポキシ変性シリコーンＢと、エポキシ変性シリコーンＢ以外のエポキシ化合物Ｃが反応することで生成した末端水酸基やエポキシ基と反応し、末端カルボキシル基を生成させる。これにより、熱硬化性樹脂との反応性の高いカルボキシル基が多数存在することになるため、相溶性及び架橋密度が向上し、低熱膨張性が向上する。 [Acid anhydride D]
The curable composition of the present embodiment contains acid anhydride D. Acid anhydride D reacts with terminal hydroxyl groups and epoxy groups generated by the reaction of alkenylphenol A, epoxy-modified silicone B, and epoxy compound C other than epoxy-modified silicone B to generate terminal carboxyl groups. As a result, a large number of carboxyl groups having high reactivity with the thermosetting resin are present, so compatibility and crosslink density are improved, and low thermal expansibility is improved.
　酸無水物Ｄとしては特に限定されず、環状構造を有していれば特に限定されることなく、熱硬化性樹脂との相溶性により一層優れる傾向にあることから、好ましくは炭素数４～２０の酸無水物であり、より好ましくは炭素数４～１６の酸無水物であり、さらに好ましくは炭素数４～１０の酸無水物である。 The acid anhydride D is not particularly limited, and is not particularly limited as long as it has a cyclic structure, and preferably has 4 to 20 carbon atoms because it tends to have better compatibility with thermosetting resins. more preferably an acid anhydride having 4 to 16 carbon atoms, more preferably an acid anhydride having 4 to 10 carbon atoms.
　酸無水物Ｄとしては、例えば、無水フタル酸、無水コハク酸、無水マレイン酸、ナジック酸無水物及びｃｉｓ－４－シクロヘキセン－１，２－ジカルボン酸無水物からなる群より選択される１種以上が挙げられ、中でも、熱硬化性樹脂との相溶性により一層優れ、低熱膨張性及び銅箔ピール強度をバランスよく一層向上できる観点から、無水フタル酸、無水コハク酸がより好ましい。 Acid anhydride D is, for example, one or more selected from the group consisting of phthalic anhydride, succinic anhydride, maleic anhydride, nadic anhydride and cis-4-cyclohexene-1,2-dicarboxylic anhydride. Among them, phthalic anhydride and succinic anhydride are more preferable from the viewpoint of better compatibility with thermosetting resins and further improvement of low thermal expansion and copper foil peel strength in a well-balanced manner.
　酸無水物Ｄの含有量は、熱硬化性樹脂との相溶性により一層優れ、低熱膨張性及び銅箔ピール強度をバランスよく一層向上できる観点から、樹脂固形分１００質量％に対して、０．８～１５質量％であることが好ましく、０．９～１０質量％であることがより好ましく、１～５質量％であることが更に好ましくい。 The content of acid anhydride D is 0.00% with respect to 100% by mass of resin solid content, from the viewpoint of better compatibility with the thermosetting resin and further improvement of low thermal expansion and copper foil peel strength in a well-balanced manner. It is preferably 8 to 15% by mass, more preferably 0.9 to 10% by mass, even more preferably 1 to 5% by mass.
［化合物Ｆ］
　本実施形態の硬化性組成物は、耐熱性、耐薬品性、低熱膨張性及び銅箔ピール強度をより一層向上させる観点から、マレイミド化合物、シアン酸エステル化合物、前記アルケニルフェノールＡ以外のフェノール化合物Ａ’及びアルケニル置換ナジイミド化合物からなる群より選択される少なくとも１種の化合物Ｆを更に含むことが好ましい。化合物Ｆとしては、特に限定されないが、２官能以上であることが好ましく、３官能以上の多官能であってもよい。 [Compound F]
From the viewpoint of further improving heat resistance, chemical resistance, low thermal expansion and copper foil peel strength, the curable composition of the present embodiment includes a maleimide compound, a cyanate ester compound, and a phenol compound A other than the alkenylphenol A. ' and at least one compound F selected from the group consisting of alkenyl-substituted nadimide compounds. Although compound F is not particularly limited, it is preferably bifunctional or higher, and may be trifunctional or higher polyfunctional.
　本実施形態の硬化性組成物中の化合物Ｆの含有量は、樹脂固形分１００質量％に対して、好ましくは１０～８０質量％であることが好ましく、２０～６０質量％であることがより好ましく、３０～５０質量％であることが更に好ましい。 The content of compound F in the curable composition of the present embodiment is preferably 10 to 80% by mass, more preferably 20 to 60% by mass, relative to 100% by mass of the resin solid content. Preferably, it is more preferably 30 to 50% by mass.
（マレイミド化合物）
　化合物Ｆとしては、低熱膨張性及び銅箔ピール強度を一層向上させる観点から、マレイミド化合物を含有することが好ましい。マレイミド化合物としては、１分子中に１つ以上のマレイミド基を有する化合物であれば特に限定されないが、例えば、１分子中にマレイミド基を１つ有するモノマレイミド化合物（例えば、Ｎ－フェニルマレイミド、Ｎ－ヒドロキシフェニルマレイミド等）、１分子中にマレイミド基を２つ以上有するポリマレイミド化合物（例えば、ビス（４－マレイミドフェニル）メタン、２，２－ビス｛４－（４－マレイミドフェノキシ）－フェニル｝プロパン、ビス（３－エチル－５－メチル－４－マレイミドフェニル）メタン、ビス（３，５－ジメチル－４－マレイミドフェニル）メタン、ビス（３，５－ジエチル－４－マレイミドフェニル）メタン）、ｍ－フェニレンビスマレイミド、４－メチル－１，３－フェニレンビスマレイミド、１，６’－ビスマレイミド－（２，２，４－トリメチル）ヘキサン、下記式（３）で表されるマレイミド化合物、下記式（３’）で表されるマレイミド化合物、これらのマレイミド化合物とアミン化合物とのプレポリマー等が挙げられる。
Figure JPOXMLDOC01-appb-C000049
 （式（３）中、Ｒ５は、各々独立して、水素原子又はメチル基を表し、ｎ１は１以上の整数を表す。） (maleimide compound)
Compound F preferably contains a maleimide compound from the viewpoint of further improving low thermal expansion and copper foil peel strength. The maleimide compound is not particularly limited as long as it is a compound having one or more maleimide groups in one molecule. -hydroxyphenylmaleimide, etc.), polymaleimide compounds having two or more maleimide groups in one molecule (e.g., bis(4-maleimidophenyl)methane, 2,2-bis{4-(4-maleimidophenoxy)-phenyl} propane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, bis(3,5-dimethyl-4-maleimidophenyl)methane, bis(3,5-diethyl-4-maleimidophenyl)methane), m-phenylene bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, a maleimide compound represented by the following formula (3), Maleimide compounds represented by the formula (3′), prepolymers of these maleimide compounds and amine compounds, and the like are included.
Figure JPOXMLDOC01-appb-C000049
 (In formula (3), each R 5 independently represents a hydrogen atom or a methyl group, and n 1 represents an integer of 1 or more.)
　ｎ１は、１以上であり、好ましくは１～１００であり、より好ましくは１～１０である。 n 1 is 1 or more, preferably 1-100, more preferably 1-10.
Figure JPOXMLDOC01-appb-C000050
 (式（３’）中、Ｒ１３は各々独立に、水素原子、炭素数１～５のアルキル基、又はフェニル基を示し、ｎ４は１以上１０以下の整数を示す。）
Figure JPOXMLDOC01-appb-C000050
 (In 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.)
　これらのマレイミド化合物は、１種を単独で、又は２種以上を組み合わせて用いられる。これらの中でも、低熱膨張性及び銅箔ピール強度をより一層向上させる観点から、マレイミド化合物は、ビス（４－マレイミドフェニル）メタン、２，２－ビス｛４－（４－マレイミドフェノキシ）－フェニル｝プロパン、ビス（３－エチル－５－メチル－４－マレイミドフェニル）メタン、式（３）で表されるマレイミド化合物及び式（３’）で表されるマレイミド化合物からなる群より選ばれる少なくとも１種を含むことが好ましい。 These maleimide compounds are used singly or in combination of two or more. Among these, from the viewpoint of further improving low thermal expansion and copper foil peel strength, the maleimide compound is bis(4-maleimidophenyl)methane, 2,2-bis{4-(4-maleimidophenoxy)-phenyl} At least one selected from the group consisting of propane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, a maleimide compound represented by formula (3), and a maleimide compound represented by formula (3′) is preferably included.
　マレイミド化合物は、市販品を用いてもよく、公知の方法により製造された製品を用いてもよい。マレイミド化合物の市販品としては、ケイ・アイ化成株式会社製品の、「ＢＭＩ－７０」、「ＢＭＩ－８０」、「ＢＭＩ－１０００Ｐ」、大和化成工業株式会社製品の「ＢＭＩ－３０００」、「ＢＭＩ－４０００」、「ＢＭＩ－５１００」、「ＢＭＩ－７０００」、「ＢＭＩ－２３００」、日本化薬株式会社製品の「ＭＩＲ－３０００－７０ＭＴ」（式（３’）中のＲ１３が全て水素原子であり、ｎ４が１～１０の混合物である。）等が挙げられる。 As the 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-3000-70MT” (R 13 in formula (3′) are all hydrogen atoms and n4 is a mixture of 1 to 10.) and the like.
　マレイミド化合物の含有量は、低熱膨張性及び銅箔ピール強度を一層向上させる観点から、樹脂固形分１００質量部に対して、好ましくは１～５０質量部であり、５～４０質量部であることがより好ましく、１０～４０質量部であることが更に好ましい。 The content of the maleimide compound is preferably 1 to 50 parts by mass, and preferably 5 to 40 parts by mass, relative to 100 parts by mass of the resin solid content, from the viewpoint of further improving low thermal expansion properties and copper foil peel strength. is more preferable, and 10 to 40 parts by mass is even more preferable.
（シアン酸エステル化合物）
　化合物Ｆとしては、低熱膨張性及び銅箔ピール強度を一層向上させる観点から、シアン酸エステル化合物を含有することが好ましい。シアン酸エステル化合物としては、１分子中に２つ以上のシアナト基（シアン酸エステル基）を有する化合物であれば特に限定されないが、例えば、下記式（４）で表される化合物等のナフトールアラルキル型シアン酸エステル化合物、式（４）で表される化合物を除く下記式（５）で表される化合物等のノボラック型シアン酸エステル化合物、ビフェニルアラルキル型シアン酸エステル、ジアリルビスフェール型シアン酸エステル化合物、ビス（３，３－ジメチル－４－シアナトフェニル）メタン、ビス（４－シアナトフェニル）メタン、１，３－ジシアナトベンゼン、１，４－ジシアナトベンゼン、１，３，５－トリシアナトベンゼン、１，３－ジシアナトナフタレン、１，４－ジシアナトナフタレン、１，６－ジシアナトナフタレン、１，８－ジシアナトナフタレン、２，６－ジシアナトナフタレン、２、７－ジシアナトナフタレン、１，３，６－トリシアナトナフタレン、４、４’－ジシアナトビフェニル、ビス（４－シアナトフェニル）エーテル、ビス（４－シアナトフェニル）チオエーテル、ビス（４－シアナトフェニル）スルホン、２、２－ビス（４－シアナトフェニル）プロパンが挙げられる。これらのシアン酸エステル化合物は、１種を単独で、又は２種以上を組み合わせて用いられる。本実施形態においては、耐熱性、低熱膨張性、銅箔ピール強度の観点から、シアン酸エステル化合物が、ナフトールアラルキル型シアン酸エステル化合物及び／又はノボラック型シアン酸エステル化合物等の多官能シアン酸エステル化合物を含むことが好ましい。
Figure JPOXMLDOC01-appb-C000051
 （式（４）中、Ｒ６は、各々独立して、水素原子又はメチル基を示し、ｎ２は１以上の整数を表す。）
Figure JPOXMLDOC01-appb-C000052
 （式（５）中、Ｒｙａは、各々独立して、炭素数２～８のアルケニル基又は水素原子を表し、Ｒｙｂは、各々独立して、炭素数１～１０のアルキル基又は水素原子を表し、Ｒｙｃは、各々独立して、炭素数４～１２の芳香環を表し、Ｒｙｃは、ベンゼン環と縮合構造を形成してもよく、Ｒｙｃは、存在していてもよく、存在していなくてもよく、Ａ１ａは、各々独立して、炭素数１～６のアルキレン基、炭素数７～１６のアラルキレン基、炭素数６～１０のアリーレン基、フルオレニリデン基、スルホニル基、酸素原子、硫黄原子又は直接結合（単結合）を表し、Ｒｙｃが存在しない場合は、１つのベンゼン環にＲｙａ及び／又はＲｙｂの基を２つ以上有してもよい。ｎは、１～２０の整数を表す。） (Cyanate ester compound)
Compound F preferably contains a cyanate ester compound from the viewpoint of further improving low thermal expansion properties and copper foil peel strength. The cyanate ester compound is not particularly limited as long as it is a compound having two or more cyanato groups (cyanate ester groups) in one molecule. type cyanate ester compounds, novolak-type cyanate ester compounds such as compounds represented by the following formula (5) excluding compounds represented by formula (4), biphenyl aralkyl-type cyanates, diallyl bisphenol-type cyanates compounds, bis(3,3-dimethyl-4-cyanatophenyl)methane, bis(4-cyanatophenyl)methane, 1,3-dicyanatobenzene, 1,4-dicyanatobenzene, 1,3,5- tricyanatobenzene, 1,3-dicyanatonaphthalene, 1,4-dicyanatonaphthalene, 1,6-dicyanatonaphthalene, 1,8-dicyanatonaphthalene, 2,6-dicyanatonaphthalene, 2,7-dicyanato Naphthalene, 1,3,6-tricyanatonaphthalene, 4,4'-dicyanatobiphenyl, bis(4-cyanatophenyl)ether, bis(4-cyanatophenyl)thioether, bis(4-cyanatophenyl)sulfone , 2,2-bis(4-cyanatophenyl)propane. These cyanate ester compounds are used singly or in combination of two or more. In the present embodiment, from the viewpoint of heat resistance, low thermal expansion, and copper foil peel strength, the cyanate ester compound is a polyfunctional cyanate ester such as a naphthol aralkyl-type cyanate ester compound and/or a novolac-type cyanate ester compound. It preferably contains a compound.
Figure JPOXMLDOC01-appb-C000051
 (In formula (4), each R 6 independently represents a hydrogen atom or a methyl group, and n 2 represents an integer of 1 or more.)
Figure JPOXMLDOC01-appb-C000052
 (In formula (5), each Rya independently represents an alkenyl group having 2 to 8 carbon atoms or a hydrogen atom, and 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, Ryc may form a fused structure with a benzene ring, Ryc may or may not 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, an oxygen atom, and a sulfur atom. or represents a direct bond (single bond), and when Ryc does not exist, one benzene ring may have two or more Rya and/or Ryb groups, n represents an integer of 1-20. )
　シアン酸エステル化合物は、これらの中でも、耐熱性、低熱膨張性及び銅箔ピール強度を一層向上させる観点から、式（４）及び／又は式（５）で表される化合物を含むことが好ましい。 Among these, the cyanate ester compound preferably contains a compound represented by formula (4) and/or formula (5) from the viewpoint of further improving heat resistance, low thermal expansion, and copper foil peel strength.
　式（４）中、ｎ２は、１以上の整数を表し、１～２０の整数であることが好ましく、１～１０の整数であることがより好ましい。 In formula (4), n2 represents an integer of 1 or more, preferably an integer of 1-20, more preferably an integer of 1-10.
　式（５）中、Ｒｙａとして表される炭素数２～８のアルケニル基としては、特に限定されないが、例えば、ビニル基、アリル基、プロペニル基、ブテニル基、ヘキセニル基等が挙げられる。 In formula (5), 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.
　式（５）中、Ｒｙｂとして表される炭素数１～１０のアルキル基としては、特に限定されないが、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基等の直鎖状アルキル基；イソプロピル基、イソブチル基、ｔｅｒｔ－ブチル基等の分岐状アルキル基が挙げられる。 In formula (5), 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;
　式（５）中、Ａ１ａとして表される炭素数１～６のアルキレン基としては、特に限定されないが、メチレン基、エチレン基、トリメチレン基、プロピレン基が挙げられる。また、式（５）中、Ａ１ａとして表される炭素数７～１６のアラルキレン基としては、特に限定されないが、例えば、式：－ＣＨ２－Ａｒ－ＣＨ２－、－ＣＨ２－ＣＨ２－Ａｒ－ＣＨ２－ＣＨ２－、又は式：－ＣＨ２－Ａｒ－ＣＨ２－ＣＨ２－（式中、Ａｒは、フェニレン基、ナフチレン基、又はビフェニレン基を表す。）で表される基が挙げられる。さらに、Ａ１ａとして表される炭素数６～１０のアリーレン基としては、特に限定されないが、例えば、フェニレン環が挙げられる。 In formula (5), 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. In formula (5), 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. Furthermore, the arylene group having 6 to 10 carbon atoms represented by A 1a is not particularly limited, but includes, for example, a phenylene ring.
　式（５）中、ｎは、１～２０の整数を表し、１～１５の整数であることが好ましく、１～１０の整数であることがより好ましい。 In formula (5), n represents an integer of 1-20, preferably an integer of 1-15, more preferably an integer of 1-10.
　式（５）で表される化合物は、下記式（ｃ１）で表される化合物であることが好ましい。
Figure JPOXMLDOC01-appb-C000053
 （式（ｃ１）中、Ｒｘは、各々独立して、水素原子又はメチル基を表し、Ｒは、各々独立して、炭素数２～８のアルケニル基、炭素数１～１０のアルキル基又は水素原子を表し、ｎは、１～１０の整数を表す。） The compound represented by Formula (5) is preferably a compound represented by Formula (c1) below.
Figure JPOXMLDOC01-appb-C000053
 (In formula (c1), 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, and n represents an integer from 1 to 10.)
　これらのシアン酸エステル化合物は、公知の方法に準じて製造してもよい。具体的な製造方法としては、例えば、特開２０１７－１９５３３４号公報（特に段落００５２～００５７）等に記載の方法が挙げられる。 These 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).
　化合物Ｆとしてのシアン酸エステル化合物の含有量は、低熱膨張性及び銅箔ピール強度を一層向上させる観点から、樹脂固形分１００質量部に対して、好ましくは１０～７０質量部であることが好ましく、１０～６０質量部であることがより好ましく、１０～４０質量部であることが更に好ましい。 The content of the cyanate ester compound as compound F is preferably 10 to 70 parts by mass with respect to 100 parts by mass of the resin solid content from the viewpoint of further improving low thermal expansion and copper foil peel strength. , more preferably 10 to 60 parts by mass, even more preferably 10 to 40 parts by mass.
（アルケニルフェノールＡ以外のフェノール化合物Ａ’）
　化合物Ｆとしては、一層優れた銅箔ピール強度を発現できる観点から、アルケニルフェノールＡ以外のフェノール化合物Ａ’を含有することができる。フェノール化合物Ａ’としては、特に限定されないが、ビスフェノール型フェノール樹脂（例えば、ビスフェノールＡ型樹脂、ビスフェノールＥ型樹脂、ビスフェノールＦ型樹脂、ビスフェノールＳ型樹脂等、）、フェノール類ノボラック樹脂（例えば、フェノールノボラック樹脂、ナフトールノボラック樹脂、クレゾールノボラック樹脂等）、グリシジルエステル型フェノール樹脂、ナフタレン型フェノール樹脂、アントラセン型フェノール樹脂、ジシクロペンタジエン型フェノール樹脂、ビフェニル型フェノール樹脂、脂環式フェノール樹脂、ポリオール型フェノール樹脂、アラルキル型フェノール樹脂、フェノール変性芳香族炭化水素ホルムアルデヒド樹脂、フルオレン型フェノール樹脂等が挙げられる。これらのフェノール化合物は、１種を単独で、又は２種以上を組み合わせて用いられる。 (Phenolic compound A' other than alkenylphenol A)
As the compound F, a phenol compound A' other than the alkenylphenol A can be contained from the viewpoint of being able to exhibit even better copper foil peel strength. The phenolic compound A′ is not particularly limited, but may be a bisphenol-type phenol resin (e.g., bisphenol A-type resin, bisphenol E-type resin, bisphenol F-type resin, bisphenol S-type resin, etc.), phenolic novolac resin (e.g., phenol novolak resin, naphthol novolac resin, cresol novolak resin, etc.), glycidyl ester type phenol resin, naphthalene type phenol resin, anthracene type phenol resin, dicyclopentadiene type phenol resin, biphenyl type phenol resin, alicyclic phenol resin, polyol type phenol Examples include resins, aralkyl-type phenol resins, phenol-modified aromatic hydrocarbon-formaldehyde resins, and fluorene-type phenol resins. These phenol compounds are used singly or in combination of two or more.
　これらの中でも、フェノール化合物Ａ’は、一層優れた相溶性及び銅箔ピール強度を発現できる観点から、１分子中にフェノール性水酸基を２つ有する２官能フェノール化合物を含むことが好ましい。 Among these, the phenolic compound A' preferably contains a bifunctional phenolic compound having two phenolic hydroxyl groups in one molecule from the viewpoint of being able to exhibit even better compatibility and copper foil peel strength.
　２官能フェノール化合物としては、特に限定されないが、ビスフェノール、ビスクレゾール、フルオレン骨格を有するビスフェノール類（例えば、フルオレン骨格を有するビスフェノール、フルオレン骨格を有するビスクレゾール等）、ビフェノール（例えば、ｐ、ｐ’－ビフェノール等）、ジヒドロキシジフェニルエーテル（例えば、４，４’－ジヒドロキシジフェニルエーテル等）、ジヒドロキシジフェニルケトン（例えば、４，４’－ジヒドロキシジフェニルケトン等）、ジヒドロキシジフェニルスルフィド（例えば、４，４’－ジヒドロキシジフェニルスルフィド等）、ジヒドロキシアレーン（例えば、ハイドロキノン等）が挙げられる。これらの２官能フェノール化合物は、１種を単独で、又は２種以上を組み合わせて用いられる。これらの中でも、２官能フェノール化合物は、一層優れた銅箔ピール強度を発現できる観点から、ビスフェノール、ビスクレゾール、及びフルオレン骨格を有するビスフェノール類からなる群より選択される少なくとも１種を含むことが好ましい。上記と同様の観点から、フルオレン骨格を有するビスフェノール類としては、ビスクレゾールフルオレンが好ましい。 Examples of the bifunctional phenol compound 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.). These bifunctional phenol compounds are used singly or in combination of two or more. Among these, the bifunctional phenol compound preferably contains at least one selected from the group consisting of bisphenol, biscresol, and bisphenols having a fluorene skeleton, from the viewpoint of being able to exhibit even better copper foil peel strength. . From the same viewpoint as above, bis-cresol fluorene is preferable as the bisphenols having a fluorene skeleton.
　アラルキル型フェノール樹脂としては、例えば、下記式（ｃ２）で表される化合物が挙げられる。 Examples of aralkyl-type phenolic resins include compounds represented by the following formula (c2).
Figure JPOXMLDOC01-appb-C000054
Figure JPOXMLDOC01-appb-C000054
（式中、Ａｒ１は、各々独立して、ベンゼン環又はナフタレン環を表し、Ａｒ２は、ベンゼン環、ナフタレン環、又はビフェニル環を表し、Ｒ２ａは、各々独立して、水素原子又はメチル基を表し、ｍは、１～５０の整数を表し、各環は、水酸基以外の置換基（例えば、炭素数１～５のアルキル基又はフェニル基等）を有してもよい。） (wherein Ar 1 each independently represents a benzene ring or naphthalene ring, Ar 2 represents a benzene ring, naphthalene ring or biphenyl ring, R 2a each independently represents a hydrogen atom or a methyl group, m represents an integer of 1 to 50, and each ring may have a substituent other than a hydroxyl group (eg, an alkyl group having 1 to 5 carbon atoms, a phenyl group, etc.).)
　式（ｃ２）で表される化合物は、銅箔ピール強度を一層向上させる観点から、式（ｃ２）中、Ａｒ１がナフタレン環であり、Ａｒ２がベンゼン環である化合物（以下、「ナフトールアラルキル型フェノール樹脂」ともいう。）、及び式（ｃ２）中、Ａｒ１がベンゼン環であり、Ａｒ２がビフェニル環である化合物（以下、「ビフェニルアラルキル型フェノール樹脂」ともいう。）であることが好ましい。 From the viewpoint of further improving copper foil peel strength, the compound represented by formula (c2) is a compound in which Ar 1 is a naphthalene ring and Ar 2 is a benzene ring (hereinafter referred to as "naphthol aralkyl Also referred to as "biphenylaralkyl-type phenolic resin"), and in formula (c2), a compound in which Ar 1 is a benzene ring and Ar 2 is a biphenyl ring (hereinafter also referred to as "biphenylaralkyl-type phenolic resin"). preferable.
　ナフトールアラルキル型フェノール樹脂は、下記式（８）で表される化合物であることが好ましい。 The naphthol aralkyl-type phenolic resin is preferably a compound represented by the following formula (8).
Figure JPOXMLDOC01-appb-C000055
Figure JPOXMLDOC01-appb-C000055
（式中、Ｒ７は、各々独立して、水素原子又はメチル基を示し、ｎ３は１以上の整数を表す。） (In the formula, each R 7 independently represents a hydrogen atom or a methyl group, and n 3 represents an integer of 1 or more.)
　式（８）中、ｎ３は１以上の整数を表し、１～１０の整数であることが好ましく、１～６の整数であることがより好ましい。 In formula (8), n3 represents an integer of 1 or more, preferably an integer of 1-10, more preferably an integer of 1-6.
　ビフェニルアラルキル型フェノール樹脂は、下記式（２ｃ）で表される化合物であることが好ましい。 The biphenylaralkyl-type phenolic resin is preferably a compound represented by the following formula (2c).
Figure JPOXMLDOC01-appb-C000056
Figure JPOXMLDOC01-appb-C000056
（式中、Ｒ２ｂは、各々独立して、水素原子、炭素数１～５のアルキル基又はフェニル基（好ましくは水素原子）を表し、ｍ１は、１～２０の整数（好ましくは１～６の整数）を表す。） (In the formula, each R 2b independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a phenyl group (preferably a hydrogen atom), m1 is an integer of 1 to 20 (preferably 1 to 6 integer).)
　フェノール化合物Ａ’は、低熱膨張性及び銅箔ピール強度を一層向上させる観点から、上記式（８）で表される化合物を含むことが好ましい。 From the viewpoint of further improving the low thermal expansion property and copper foil peel strength, the phenolic compound A' preferably contains the compound represented by the above formula (8).
　アラルキル型フェノール樹脂は、市販品を用いてもよく、公知の方法により製造された製品を用いてもよい。アラルキル型フェノール樹脂の市販品としては、日本化薬株式会社製品の「ＫＡＹＡＨＡＲＤ　ＧＰＨ－６５」、「ＫＡＹＡＨＡＲＤ　ＧＰＨ－７８」、「ＫＡＹＡＨＡＲＤ　ＧＰＨ－１０３」（ビフェニルアラルキル型フェノール樹脂）、新日鐵化学株式会社製品の「ＳＮ－４９５」（ナフトールアラルキル型フェノール樹脂）が挙げられる。 A commercially available product or a product manufactured by a known method may be used as the aralkyl-type phenol resin. Commercially available aralkyl-type phenolic resins include Nippon Kayaku Co., Ltd.'s "KAYAHARD GPH-65", "KAYAHARD GPH-78", "KAYAHARD GPH-103" (biphenylaralkyl-type phenolic resin), Nippon Steel Chemical Co., Ltd. The company's product "SN-495" (naphthol aralkyl type phenolic resin) can be mentioned.
　化合物ＦとしてのアルケニルフェノールＡの含有量は、一層優れた相溶性を発現できる観点から、アルケニルフェノールＡ、エポキシ変性シリコーンＢ、エポキシ化合物Ｃ及びフェノール化合物Ａ’の総量１００質量部に対して、１～５０質量部であることが好ましく、３～３０質量部であることがより好ましく、５～２０質量部であることが更に好ましい。 The content of alkenylphenol A as compound F is 1 part per 100 parts by mass of the total amount of alkenylphenol A, epoxy-modified silicone B, epoxy compound C and phenolic compound A', from the viewpoint of being able to exhibit even better compatibility. The amount is preferably to 50 parts by mass, more preferably 3 to 30 parts by mass, and even more preferably 5 to 20 parts by mass.
　本実施形態の硬化性組成物におけるエポキシ変性シリコーンＢの含有量は、一層優れた低熱膨張性及び銅箔ピール強度をバランスよく発現できる観点から、アルケニルフェノールＡ、エポキシ変性シリコーンＢ、エポキシ化合物Ｃ及びフェノール化合物Ａ’の総量１００質量部に対して、５～７０質量部であることが好ましく、１０～６０質量部であることがより好ましく、２０～５５質量部であることが更に好ましい。 The content of the epoxy-modified silicone B in the curable composition of the present embodiment is, from the viewpoint of achieving well-balanced expression of even better low thermal expansion and copper foil peel strength, alkenylphenol A, epoxy-modified silicone B, epoxy compound C and 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'.
　本実施形態の硬化性組成物におけるエポキシ化合物Ｃの含有量は、一層優れた相溶性、耐熱性、耐薬品性、銅箔ピール強度及び絶縁信頼性を発現できる観点から、アルケニルフェノールＡ、エポキシ変性シリコーンＢ、エポキシ化合物Ｃ及びフェノール化合物Ａ’の総量１００質量部に対して、５～５０質量部質量部であることが好ましく、１０～３０質量部質量部であることがより好ましく、１５～２５質量部質量部であることが更に好ましい。 The content of the epoxy compound C in the curable composition of the present embodiment, alkenylphenol A, epoxy-modified Based on 100 parts by mass of the total amount of silicone B, epoxy compound C and phenolic compound A', it is preferably 5 to 50 parts by mass, more preferably 10 to 30 parts by mass, and 15 to 25 parts by mass. Parts by mass are more preferred.
　本実施形態の硬化性組成物におけるフェノール化合物Ａ’の含有量は、一層優れた銅箔ピール強度を発現できる観点から、アルケニルフェノールＡ、エポキシ変性シリコーンＢ、エポキシ化合物Ｃ及びフェノール化合物Ａ’の総量１００質量部に対して、５～３０質量部であることが好ましく、１０～２５質量部質量部であることがより好ましく、１５～２０質量部質量部であることが更に好ましい。 The content of the phenolic compound A' in the curable composition of the present embodiment is the total amount of the alkenylphenol A, the epoxy-modified silicone B, the epoxy compound C and the phenolic compound A' from the viewpoint of expressing even better copper foil peel strength. 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 100 parts by mass.
　なお、硬化性組成物が、フェノール化合物Ａ’を含有しない場合、上述したアルケニルフェノールＡ、エポキシ変性シリコーンＢ及びエポキシ化合物Ｃの各含有量は、アルケニルフェノールＡ、エポキシ変性シリコーンＢ及びエポキシ化合物Ｃの総量１００質量部に対する含有量を表す。 In addition, when the curable composition does not contain phenol compound A′, the contents of alkenylphenol A, epoxy-modified silicone B, and epoxy compound C are the same as those of alkenylphenol A, epoxy-modified silicone B, and epoxy compound C. It represents the content with respect to the total amount of 100 parts by mass.
（アルケニル置換ナジイミド化合物）
　化合物Ｆとしては、耐熱性をより一層向上させる観点から、アルケニル置換ナジイミド化合物を含有することが好ましい。アルケニル置換ナジイミド化合物は、１分子中に１つ以上のアルケニル置換ナジイミド基を有する化合物であれば特に限定されないが、例えば、下記式（２ｄ）で表される化合物が挙げられる。
Figure JPOXMLDOC01-appb-C000057
 （式（２ｄ）中、Ｒ１は、各々独立して、水素原子、又は炭素数１～６のアルキル基（例えば、メチル基又はエチル基）を表し、Ｒ２は、炭素数１～６のアルキレン基、フェニレン基、ビフェニレン基、ナフチレン基、又は下記式（６）若しくは下記式（７）で表される基を表す。）
Figure JPOXMLDOC01-appb-C000058
 （式（６）中、Ｒ３は、メチレン基、イソプロピリデン基、ＣＯ、Ｏ、Ｓ又はＳＯ２を表す。）
Figure JPOXMLDOC01-appb-C000059
 （式（７）中、Ｒ４は、各々独立して、炭素数１～４のアルキレン基、又は炭素数５～８のシクロアルキレン基を表す。） (Alkenyl-Substituted Nadimide Compound)
From the viewpoint of further improving heat resistance, compound F preferably contains an alkenyl-substituted nadimide compound. 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).
Figure JPOXMLDOC01-appb-C000057
 (In 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).)
Figure JPOXMLDOC01-appb-C000058
 (In formula (6), R3 represents a methylene group, an isopropylidene group, CO, O, S or SO2 .)
Figure JPOXMLDOC01-appb-C000059
 (In formula (7), each R 4 independently represents an alkylene group having 1 to 4 carbon atoms or a cycloalkylene group having 5 to 8 carbon atoms.)
　式（２ｄ）で表されるアルケニル置換ナジイミド化合物は、市販品を用いてもよく、公知の方法に準じて製造された製品を用いてもよい。市販品としては、丸善石油化学株式会社製品の「ＢＡＮＩ－Ｍ」、及び「ＢＡＮＩ－Ｘ」が挙げられる。 As the 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.
　化合物Ｆとしてのアルケニル置換ナジイミド化合物の含有量は、耐熱性を向上させる観点から、樹脂固形分１００質量部に対して、好ましくは１～４０質量部であり、５～３５質量部であることがより好ましく、１０～３０質量部であることが更に好ましい。 From the viewpoint of improving heat resistance, the content of the alkenyl-substituted nadimide compound as compound F is preferably 1 to 40 parts by mass, preferably 5 to 35 parts by mass, relative to 100 parts by mass of the resin solid content. More preferably, 10 to 30 parts by mass is even more preferable.
［第２実施形態：硬化性組成物］
　第２実施形態の硬化性組成物は、アルケニルフェノールＡに由来する構成単位と、エポキシ変性シリコーンＢに由来する構成単位と、該エポキシ変性シリコーンＢ以外のエポキシ化合物Ｃに由来する構成単位と、酸無水物Ｄに由来する構成単位と、を含有する重合体Ｅを含む。アルケニルフェノールＡ、エポキシ変性シリコーンＢ、エポキシ化合物Ｃ及び酸無水物Ｄについては、上記にて説明した通りである。以下、アルケニルフェノールＡに由来する構成単位と、エポキシ変性シリコーンＢに由来する構成単位と、エポキシ化合物Ｃに由来する構成単位と、酸無水物Ｄに由来する構成単位と、を含有する重合体Ｅを含む第２実施形態の硬化性樹脂組成物は、重合体Ｅを有しない態様に係る上述した第１実施形態の硬化性組成物とは区別される。 [Second embodiment: curable composition]
The curable composition of the second embodiment includes a structural unit derived from alkenylphenol A, a structural unit derived from epoxy-modified silicone B, a structural unit derived from an epoxy compound C other than the epoxy-modified silicone B, and an acid A constituent unit derived from the anhydride D, and a polymer E containing a Alkenylphenol A, epoxy-modified silicone B, epoxy compound C and acid anhydride D are as described above. Hereinafter, polymer E containing structural units derived from alkenylphenol A, structural units derived from epoxy-modified silicone B, structural units derived from epoxy compound C, and structural units derived from acid anhydride D The curable resin composition of the second embodiment containing is distinguished from the curable composition of the first embodiment described above, which relates to the aspect that does not have the polymer E.
　重合体Ｅは、シリコーン系化合物との相溶性に乏しい熱硬化性樹脂と混合した場合においても、十分な相溶性を発揮し得る。これにより、重合体Ｅと熱硬化性樹脂を含む硬化性組成物は、均一なワニスや硬化物を与えることができる。当該硬化性組成物を用いて得られるプリプレグ等の硬化物は、各成分が均一に相溶したものであり、成分の不均一による物性のばらつきが抑制されたものとなる。 Polymer E can exhibit sufficient compatibility even when mixed with a thermosetting resin that has poor compatibility with silicone compounds. Thereby, the curable composition containing the polymer E and the thermosetting resin can give a uniform varnish or cured product. A cured product such as a prepreg obtained by using the curable composition has components uniformly dissolved therein, and variation in physical properties due to non-uniformity of the components is suppressed.
　なお、第２実施形態の硬化性組成物は、重合体Ｅに加えて、アルケニルフェノールＡ、エポキシ変性シリコーンＢ、エポキシ化合物Ｃ及び酸無水物Ｄからなる群より選ばれる１種以上を含んでいてもよい。この場合、第２実施形態の硬化性組成物に含まれるアルケニルフェノールＡ、エポキシ変性シリコーンＢ、エポキシ化合物Ｃ及び酸無水物Ｄは、重合体Ｅの重合後に残存した未反応成分であってもよいし、合成した重合体Ｅに対して、改めて添加した成分であってもよい。 In addition to the polymer E, the curable composition of the second embodiment contains one or more selected from the group consisting of alkenylphenol A, epoxy-modified silicone B, epoxy compound C and acid anhydride D. good too. In this case, the alkenylphenol A, the epoxy-modified silicone B, the epoxy compound C, and the acid anhydride D contained in the curable composition of the second embodiment may be unreacted components remaining after the polymerization of the polymer E. However, it may be a component added again to the synthesized polymer E.
　また、第２実施形態の硬化性組成物は、重合体Ｅに加えて、必要に応じて、上述した、マレイミド化合物、シアン酸エステル化合物、前記アルケニルフェノールＡ以外のフェノール化合物Ａ’及びアルケニル置換ナジイミド化合物からなる群より選択される少なくとも１種である化合物Ｆを更に含んでいてもよい。化合物Ｆは、重合体Ｅの重合後に残存した未反応成分であってもよいし、合成した重合体Ｅに対して、改めて添加した成分であってもよい。 In addition to the polymer E, the curable composition of the second embodiment may optionally contain the above-described maleimide compound, cyanate ester compound, phenol compound A' other than the alkenylphenol A, and alkenyl-substituted nadimide. It may further contain compound F, which is at least one selected from the group consisting of compounds. The compound F may be an unreacted component remaining after polymerization of the polymer E, or may be a component newly added to the polymer E synthesized.
［重合体Ｅ］
　重合体Ｅは、アルケニルフェノールＡに由来する構成単位と、エポキシ変性シリコーンＢに由来する構成単位と、エポキシ化合物Ｃに由来する構成単位と、酸無水物Ｄに由来する構成単位とを含有し、必要に応じて、マレイミド化合物、シアン酸エステル化合物、前記アルケニルフェノールＡ以外のフェノール化合物Ａ’及びアルケニル置換ナジイミド化合物からなる群より選択される少なくとも１種の化合物Ｆに由来する構成単位を更に含有してもよい。重合体Ｅが化合物Ｆに由来する構成単位を有する場合、化合物Ｆとしては２官能の化合物であることが好ましい。なお、本明細書において、「アルケニルフェノールＡに由来する構成単位」、「エポキシ変性シリコーンＢに由来する構成単位」、「エポキシ化合物Ｃに由来する構成単位」、「酸無水物Ｄに由来する構成単位」及び「化合物Ｆに由来する構成単位」とは、重合体Ｅ中にアルケニルフェノールＡ、エポキシ変性シリコーンＢ、エポキシ化合物Ｃ、酸無水物Ｄ及び化合物Ｆの各成分を重合させた構成単位を含むことに加えて、同様の構成単位を与えうる反応等で形成した構成単位を含むこととする。以下、各構成単位をそれぞれ構成単位Ａ、Ｂ、Ｃ、Ｄ、Ｆともいう。重合体Ｅを用いることにより、第２実施形態の硬化性組成物は、より一層優れた相溶性を有し、耐熱性、耐薬品性、低熱膨張性、銅箔ピール強度及び絶縁信頼性により一層優れる。 [Polymer E]
Polymer E contains 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 acid anhydride D, If necessary, it further contains a structural unit derived from at least one compound F selected from the group consisting of a maleimide compound, a cyanate ester compound, a phenol compound A′ other than the alkenylphenol A, and an alkenyl-substituted nadimide compound. may When the polymer E has structural units derived from the compound F, the compound F is preferably a bifunctional compound. In the present specification, "structural units derived from alkenylphenol A", "structural units derived from epoxy-modified silicone B", "structural units derived from epoxy compound C", and "structural units derived from acid anhydride D "unit" and "structural unit derived from compound F" are structural units obtained by polymerizing each component of alkenylphenol A, epoxy-modified silicone B, epoxy compound C, acid anhydride D and compound F in polymer E. In addition to including, structural units formed by reactions or the like that can give similar structural units are also included. Hereinafter, each structural unit is also referred to as structural unit A, B, C, D, and F, respectively. By using the polymer E, the curable composition of the second embodiment has much better compatibility, heat resistance, chemical resistance, low thermal expansion, copper foil peel strength and insulation reliability. Excellent.
　重合体Ｅの重量平均分子量は、ゲルパーミエーションクロマトグラフィーにおけるポリスチレン換算で、３．０×１０３～５．０×１０４であることが好ましく、３．０×１０３～２．０×１０４であることがより好ましい。重量平均分子量が３．０×１０３以上であることにより、第２実施形態の硬化性組成物は、一層優れた耐熱性、耐薬品性、低熱膨張性、銅箔ピール強度及び絶縁信頼性を発現できる傾向にある。重量平均分子量が５．０×１０４以下であることにより、第２実施形態の硬化性組成物は、一層優れた相溶性を発現できる傾向にある。 The weight-average molecular weight of the polymer E is preferably 3.0×10 3 to 5.0×10 4 and more preferably 3.0×10 3 to 2.0×10 in terms of polystyrene in gel permeation chromatography. 4 is more preferred. With a weight-average molecular weight of 3.0×10 3 or more, the curable composition of the second embodiment exhibits even better heat resistance, chemical resistance, low thermal expansion, copper foil peel strength, and insulation reliability. tend to be expressed. When the weight average molecular weight is 5.0×10 4 or less, the curable composition of the second embodiment tends to exhibit even better compatibility.
　重合体Ｅ中の構成単位Ａの含有量は、重合体Ｅの総質量に対して、５～５０質量％であることが好ましい。構成単位Ａの含有量が上記範囲内であることにより、第２実施形態の硬化性組成物は、一層優れた相溶性を発現できる傾向にある。同様の観点から、構成単位Ａの含有量は、１０～４５質量％であることがより好ましく、１５～４０質量％であることが更に好ましい。 The content of the structural unit A in the polymer E is preferably 5 to 50% by mass with respect to the total mass of the polymer E. When the content of the structural unit A is within the above range, the curable composition of the second embodiment tends to exhibit even better compatibility. From the same point of view, the content of structural unit A is more preferably 10 to 45% by mass, even more preferably 15 to 40% by mass.
　重合体Ｅ中の構成単位Ｂの含有量は、重合体Ｅの総質量に対して、２０～６０質量％であることが好ましい。構成単位Ｂの含有量が上記範囲内であることにより、第２実施形態の硬化性組成物は、一層優れた低熱膨張性及び銅箔ピール強度をバランスよく発現できる傾向にある。同様の観点から、構成単位Ｂの含有量は、２５～５５質量％であることがより好ましく、３０～５０質量％であることが更に好ましい。 The content of the structural unit B in the polymer E is preferably 20 to 60% by mass with respect to the total mass of the polymer E. When the content of the structural unit B is within the above range, the curable composition of the second embodiment tends to exhibit even better low thermal expansion and copper foil peel strength in a well-balanced manner. From the same point of view, the content of structural unit B is more preferably 25 to 55% by mass, even more preferably 30 to 50% by mass.
　構成単位Ｂは、５０～３５０ｇ／ｍｏｌのエポキシ当量を有するエポキシ変性シリコーン（低当量エポキシ変性シリコーンＢ１）と、４００～４０００ｇ／ｍｏｌのエポキシ当量を有するエポキシ変性シリコーン（高当量エポキシ変性シリコーンＢ２）に由来する構成単位とを含むことが好ましい。低当量エポキシ変性シリコーンＢ１、高当量エポキシ変性シリコーンＢ２は、それぞれ、１４０～２５０ｇ／ｍｏｌのエポキシ当量を有するエポキシ変性シリコーン（低当量エポキシ変性シリコーンＢ１’）、４５０～３０００ｇ／ｍｏｌのエポキシ当量を有するエポキシ変性シリコーン（高当量エポキシ変性シリコーンＢ２’）であることがより好ましい。 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.
　重合体Ｅ中の低当量エポキシ変性シリコーンＢ１に由来する構成単位Ｂ１の含有量は、重合体Ｅの総質量に対して、５～２５質量％であることが好ましく、７．５～２０質量％であることがより好ましく、１０～１７質量％であることが更に好ましい。 The content of the structural unit B1 derived from the low-equivalent epoxy-modified silicone B1 in the polymer E is preferably 5 to 25% by mass, more preferably 7.5 to 20% by mass, relative to the total mass of the polymer E. is more preferable, and 10 to 17% by mass is even more preferable.
　重合体Ｅ中の高当量エポキシ変性シリコーンＢ２に由来する構成単位Ｂ２の含有量は、重合体Ｅの総質量に対して、１５～５５質量％であることが好ましく、２０～５２．５質量％であることがより好ましく、２５～５０質量％であることが更に好ましい。 The content of the structural unit B2 derived from the high-equivalent epoxy-modified silicone B2 in the polymer E is preferably 15 to 55% by mass, more preferably 20 to 52.5% by mass, relative to the total mass of the polymer E. and more preferably 25 to 50% by mass.
　構成単位Ｂ１の含有量に対する構成単位Ｂ２の含有量の質量比は、１．５～４であることが好ましく、１．７～３．５であることがより好ましく、１．９～３．１であることが更に好ましい。構成単位Ｂ１及び構成単位Ｂ２の含有量が上記関係を有することにより、第２実施形態の硬化性組成物は、低熱膨張性及び銅箔ピール強度がより向上する傾向にある。 The mass ratio of the content of the structural unit B2 to the content of the structural unit B1 is preferably 1.5 to 4, more preferably 1.7 to 3.5, and 1.9 to 3.1. is more preferable. When the contents of the structural unit B1 and the structural unit B2 have the above relationship, the curable composition of the second embodiment tends to have improved low thermal expansion and copper foil peel strength.
　重合体Ｅ中の構成単位Ｃとしては、上記式（ｂ１）で表される化合物、上記式（ｂ２）で表される化合物、上記式（ｂ３）で表される化合物及び上記式（ｂ４）で表される化合物からなる群より選択される少なくとも１種に由来する単位であることが好ましい。 As the structural unit C in the polymer E, 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.
　重合体Ｅ中の構成単位Ｃの含有量は、重合体Ｅの総質量に対して、５～４０質量％であることが好ましい。構成単位Ｃの含有量が上記範囲内であると、第２実施形態の硬化性組成物は、一層優れた相溶性を有し、一層優れた耐熱性、耐薬品性、低熱膨張性、銅箔ピール強度及び絶縁信頼性を発現できる傾向にある。同様の観点から、構成単位Ｃの含有量は、１０～３０質量％であることが好ましく、１５～２５質量％であることが更に好ましい。 The content of the structural unit C in the polymer E is preferably 5 to 40% by mass with respect to the total mass of the polymer E. When the content of the structural unit C is within the above range, the curable composition of the second embodiment has better compatibility, better heat resistance, chemical resistance, low thermal expansion, copper foil It tends to be able to develop peel strength and insulation reliability. From the same point of view, the content of structural unit C is preferably 10 to 30% by mass, more preferably 15 to 25% by mass.
　また、構成単位Ｃの含有量は、構成単位Ｂ及び構成単位Ｃの総質量に対して、５～９５質量％であることが好ましく、１０～９０質量％であることがより好ましく、１５～６０質量％であることが更に好ましく、２０～５０質量％であることが特に好ましい。構成単位Ｂ及び構成単位Ｃの含有量が上記関係を有することにより、第２実施形態の硬化性組成物は、一層優れた相溶性を有し、耐熱性、耐薬品性、低熱膨張性、銅箔ピール強度及び絶縁信頼性がより一層向上する傾向にある。 Further, 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. When the contents of the structural unit B and the structural unit C have the above relationship, the curable composition of the second embodiment has even better compatibility, heat resistance, chemical resistance, low thermal expansion, copper Foil peel strength and insulation reliability tend to be further improved.
　重合体Ｅ中の構成単位Ｄの含有量は、重合体Ｅの総質量に対して、３～２０質量％であることが好ましい。構成単位Ｄの含有量が上記範囲内であることにより、第２実施形態の硬化性組成物は、一層優れた低熱膨張性及び銅箔ピール強度をバランスよく発現できる傾向にある。同様の観点から、構成単位Ｄの含有量は、５～１５質量％であることがより好ましく、５～１０質量％であることが更に好ましい。 The content of the structural unit D in the polymer E is preferably 3 to 20% by mass with respect to the total mass of the polymer E. When the content of the structural unit D is within the above range, the curable composition of the second embodiment tends to exhibit even better low thermal expansion and copper foil peel strength in a well-balanced manner. From the same point of view, the content of structural unit D is more preferably 5 to 15% by mass, even more preferably 5 to 10% by mass.
　重合体Ｅが化合物Ｆに由来する構成単位を有する場合、重合体Ｅ中の構成単位Ｆの含有量は、重合体Ｅの総質量に対して、３～４０質量％であることが好ましい。構成単位Ｆの含有量が上記範囲内であることにより、第２実施形態の硬化性組成物は、一層優れた耐熱性、耐薬品性、低熱膨張性、銅箔ピール強度及び絶縁信頼性を発現できる傾向にある。同様の観点から、構成単位Ｆの含有量は、５～３５質量％であることが好ましく、１０～３０質量％であることが更に好ましい。 When the polymer E has structural units derived from the compound F, the content of the structural unit F in the polymer E is preferably 3 to 40% by mass relative to the total mass of the polymer E. When the content of the structural unit F is within the above range, the curable composition of the second embodiment exhibits even better heat resistance, chemical resistance, low thermal expansion, copper foil peel strength, and insulation reliability. tend to be able. From the same point of view, the content of structural unit F is preferably 5 to 35% by mass, more preferably 10 to 30% by mass.
　重合体ＥがアルケニルフェノールＡ以外のフェノール化合物Ａ’に由来する構成単位（以下、「構成単位Ａ’」ともいう）を有する場合、重合体Ｅ中の構成単位Ａ’の含有量は、重合体Ｅの総質量に対して、５～３０質量％であることが好ましい。構成単位Ａ’の含有量が上記範囲内であることにより、第２実施形態の硬化性組成物は、一層優れた耐熱性、耐薬品性、低熱膨張性、銅箔ピール強度及び絶縁信頼性を発現できる傾向にある。同様の観点から、構成単位Ａ’の含有量は、１０～２７．５質量％であることが好ましく、１０～２５質量％であることが更に好ましい。 When the polymer E has a structural unit derived from a phenol compound A' other than alkenylphenol A (hereinafter also referred to as "structural unit A'"), the content of the structural unit A' in the polymer E is It is preferably 5 to 30% by mass relative to the total mass of E. When the content of the structural unit A' is within the above range, the curable composition of the second embodiment has even better heat resistance, chemical resistance, low thermal expansion, copper foil peel strength and insulation reliability. tend to be expressed. From the same point of view, the content of the structural unit A' is preferably 10 to 27.5% by mass, more preferably 10 to 25% by mass.
　重合体Ｅにおけるアルケニル基当量は、３００～１５００ｇ／ｍｏｌであることが好ましい。アルケニル基当量が３００ｇ／ｍｏｌ以上であることにより、第２実施形態の硬化性組成物の硬化物は、弾性率が一層低下する傾向にあり、その結果、硬化物を用いて得られる基板等の熱膨張率を一層低下できる傾向にある。アルケニル基当量が１５００ｇ／ｍｏｌ以下であることにより、第２実施形態の硬化性組成物の相溶性、耐熱性、耐薬品性、低熱膨張性、銅箔ピール強度及び絶縁信頼性が一層向上する傾向にある。同様の観点から、アルケニル基当量は、３５０～１２００ｇ／ｍｏｌであることが好ましく、４００～１０００ｇ／ｍｏｌであることが更に好ましい。 The alkenyl group equivalent weight of the polymer E is preferably 300-1500 g/mol. When the alkenyl group equivalent is 300 g/mol or more, the cured product of the curable composition of the second embodiment tends to have a further decreased elastic modulus, and as a result, substrates and the like obtained using the cured product There is a tendency that the coefficient of thermal expansion can be further reduced. When the alkenyl group equivalent is 1500 g/mol or less, the compatibility, heat resistance, chemical resistance, low thermal expansion, copper foil peel strength, and insulation reliability of the curable composition of the second embodiment tend to be further improved. It is in. From the same point of view, the alkenyl group equivalent is preferably 350-1200 g/mol, more preferably 400-1000 g/mol.
　第２実施形態の硬化性組成物における重合体Ｅの含有量は、樹脂固形分１００質量％に対して、５～５０質量％であることが好ましく、１０～４５質量％であることがより好ましく、１５～４０質量％であることが更に好ましい。含有量が上記範囲内であると、硬化性組成物は、一層優れた相溶性を有し、低熱膨張性及び銅箔ピール強度をバランスよく発現できる傾向にある。 The content of the polymer E in the curable composition of the second embodiment is preferably 5 to 50% by mass, more preferably 10 to 45% by mass, relative to 100% by mass of the resin solid content. , more preferably 15 to 40% by mass. When the content is within the above range, the curable composition tends to have more excellent compatibility and can exhibit low thermal expansion and copper foil peel strength in a well-balanced manner.
　重合体Ｅは、例えば、アルケニルフェノールＡと、エポキシ変性シリコーンＢと、エポキシ化合物Ｃと、酸無水物Ｄと、必要に応じて化合物Ｆとを、重合触媒Ｇの存在下にて反応させる工程により得られる。当該反応は、有機溶媒の存在下で行ってもよい。
　より具体的には、上記工程において、エポキシ変性シリコーンＢ及びエポキシ化合物Ｃが有するエポキシ基とアルケニルフェノールＡが有する水酸基との付加反応と、得られた付加反応物が有する水酸基とエポキシ変性シリコーンＢ及びエポキシ化合物Ｃが有するエポキシ基との付加反応などが進行した後、さらに、末端水酸基及びエポキシ基と酸無水物Ｄとの付加反応が進行することで、重合体Ｅを得ることができる。 Polymer E can be obtained, for example, by reacting alkenylphenol A, epoxy-modified silicone B, epoxy compound C, acid anhydride D, and optionally compound F in the presence of polymerization catalyst G. can get. 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 After the addition reaction with the epoxy group of the epoxy compound C proceeds, the addition reaction between the terminal hydroxyl group and the epoxy group and the acid anhydride D proceeds to obtain the polymer E.
　本実施形態の硬化性組成物（特に第２実施形態の硬化性組成物）の製造方法は、
　アルケニルフェノールＡと、エポキシ変性シリコーンＢと、エポキシ化合物Ｃとを重合して得られるプレポリマーを得る工程と、
　前記プレポリマーに対して酸無水物Ｄを反応させる工程と、
を含むことが好ましい。
　アルケニルフェノールＡと、エポキシ変性シリコーンＢと、エポキシ化合物Ｃとを重合して得られるプレポリマーを生成した後、このプレポリマーに対して酸無水物Ｄを反応させることで、低熱膨張性及び銅箔ピール強度により一層優れた硬化性組成物が得られる傾向にある。 The method for producing the curable composition of the present embodiment (especially the curable composition of the second embodiment) is
obtaining a prepolymer obtained by polymerizing alkenylphenol A, epoxy-modified silicone B, and epoxy compound C;
a step of reacting an acid anhydride D with the prepolymer;
is preferably included.
After producing a prepolymer obtained by polymerizing alkenylphenol A, epoxy-modified silicone B, and epoxy compound C, an acid anhydride D is reacted with this prepolymer to obtain a low thermal expansion property and a copper foil. There is a tendency to obtain curable compositions with even better peel strength.
［重合触媒Ｇ］
　重合触媒Ｇとしては、特に限定されず、例えば、イミダゾール化合物及び有機リン化合物のいずれか１種以上が挙げられる。これらの触媒は１種を単独で、又は２種以上を組み合わせて用いられる。これらの中でも、イミダゾール化合物が好ましい。 [Polymerization catalyst G]
The polymerization catalyst G is not particularly limited, and includes, for example, one or more of imidazole compounds and organophosphorus compounds. These catalysts are used individually by 1 type or in combination of 2 or more types. Among these, imidazole compounds are preferred.
　イミダゾール化合物としては、特に限定されず、例えば、２－メチルイミダゾール、２－エチル－４－メチルイミダゾール、２－フェニルイミダゾール、１－シアノエチル－２－フェニルイミダゾール、１－シアノエチル－２－フェニルイミダゾール、１－シアノエチル－２－エチル－４－メチルイミダゾール、２－フェニル－４，５－ジヒドロキシメチルイミダゾール、２－フェニル－４－メチル－５－ヒドロキシメチルイミダゾール、２，３－ジヒドロ－１Ｈ－ピロロ［１，２－ａ］ベンゾイミダゾール（四国化成工業株式会社製品の「ＴＢＺ」）、２，４，５－トリフェニルイミダゾール（東京化成工業株式会社製品の「ＴＰＩＺ」）等のイミダゾール類が挙げられる。このなかでも、エポキシ成分の単独重合を防ぐ観点から、２，３－ジヒドロ－１Ｈ－ピロロ［１，２－ａ］ベンゾイミダゾール及び／又は２，４，５－トリフェニルイミダゾールが好ましい。 The imidazole compound is not particularly limited, and examples include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, -cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1, 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.); Among these, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole and/or 2,4,5-triphenylimidazole are preferred from the viewpoint of preventing homopolymerization of the epoxy component.
　重合触媒Ｇ（好ましくはイミダゾール化合物）の使用量は、特に限定されず、例えば、アルケニルフェノールＡ、エポキシ変性シリコーンＢ、エポキシ化合物Ｃ、酸無水物Ｄ及び化合物Ｆの総量１００質量部に対して、０．１～１０質量部である。重合体Ｅの重量平均分子量を大きくする観点から、重合触媒Ｇの使用量は、０．５質量部以上であることが好ましく、４．０質量部以下であることがより好ましい。 The amount of the polymerization catalyst G (preferably an imidazole compound) used is not particularly limited. It is 0.1 to 10 parts by mass. From the viewpoint of increasing the weight average molecular weight of the polymer E, the amount of the polymerization catalyst G used is preferably 0.5 parts by mass or more, and more preferably 4.0 parts by mass or less.
［有機溶媒］
　有機溶媒としては、特に限定されず、例えば、極性溶剤又は無極性溶剤を用いることができる。極性溶剤としては、特に制限されないが、例えば、アセトン、メチルエチルケトン、メチルイソブチルケトン等のケトン類；プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート等のセロソルブ系溶媒；乳酸エチル、酢酸メチル、酢酸エチル、酢酸ブチル、酢酸イソアミル、乳酸エチル、メトキシプロピオン酸メチル、ヒドロキシイソ酪酸メチル等のエステル系溶媒；ジメチルアセトアミド、ジメチルホルムアミド等のアミド類等が挙げられる。無極性溶剤としては、特に制限されないが、例えば、トルエン、キシレン等の芳香族炭化水素等が挙げられる。これらの溶媒は、１種を単独で、又は２種以上を組み合わせて用いられる。 [Organic solvent]
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, and examples thereof include aromatic hydrocarbons such as toluene and xylene. These solvents are used singly or in combination of two or more.
　有機溶媒の使用量は、特に限定されず、例えば、アルケニルフェノールＡ、エポキシ変性シリコーンＢ、エポキシ化合物Ｃ、酸無水物Ｄ及び化合物Ｆの総量１００質量部に対して、５０～１５０質量部である。 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, acid anhydride D and compound F. .
　反応温度は、特に限定されず、例えば、１００～１７０℃であってよい。反応時間もまた特に限定されず、例えば、３～８時間であってよい。 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.
　本工程における反応終了後、慣用の方法にて反応混合物から重合体Ｅを分離精製してもよい。 After completion of the reaction in this step, polymer E may be separated and purified from the reaction mixture by a conventional method.
上述したように、第２実施形態の硬化性組成物は、重合体Ｅに加えて、必要に応じて、化合物Ｆを更に含有してもよい。重合体Ｅに加えて、化合物Ｆを更に含有することにより、第２実施形態の硬化性組成物は、耐熱性、耐薬品性、低熱膨張性及び銅箔ピール強度がより一層向上する傾向にある。 As described above, the curable composition of the second embodiment may further contain compound F in addition to polymer E, if necessary. By further containing the compound F in addition to the polymer E, the curable composition of the second embodiment tends to further improve heat resistance, chemical resistance, low thermal expansion and copper foil peel strength. .
　第２実施形態の硬化性組成物が重合体Ｅ及び化合物Ｆを含む場合、第２実施形態の硬化性組成物における重合体Ｅの含有量は、重合体Ｅ及び化合物Ｆの合計１００質量％に対して、５～６０質量％であることが好ましく、１０～５５質量％であることがより好ましく、２０～５０質量％であることが更に好ましい。含有量が上記範囲内であると、硬化性組成物は、一層優れた相溶性を有し、低熱膨張性及び銅箔ピール強度をバランスよく発現できる傾向にある。 When the curable composition of the second embodiment contains the polymer E and the compound F, the content of the polymer E in the curable composition of the second embodiment is a total of 100 mass% of the polymer E and the compound F On the other hand, it is preferably 5 to 60% by mass, more preferably 10 to 55% by mass, and even more preferably 20 to 50% by mass. When the content is within the above range, the curable composition tends to have more excellent compatibility and can exhibit low thermal expansion and copper foil peel strength in a well-balanced manner.
　第２実施形態の硬化性組成物が重合体Ｅ及び化合物Ｆを含む場合、第２実施形態の硬化性組成物における化合物Ｆの含有量は、重合体Ｅ及び化合物Ｆの合計１００質量％に対して、好ましくは２０～８０質量％であることが好ましく、３５～７５質量％であることがより好ましく、４５～６５質量％であることがさらに好ましい。 When the curable composition of the second embodiment contains the polymer E and the compound F, the content of the compound F in the curable composition of the second embodiment is a total of 100 mass% of the polymer E and the compound F It is preferably 20 to 80% by mass, more preferably 35 to 75% by mass, even more preferably 45 to 65% by mass.
　本実施形態における硬化性組成物は、本実施形態における効果を阻害しない限り、その他の樹脂をさらに含有してもよい。その他の樹脂としては、例えば、オキセタン樹脂、ベンゾオキサジン化合物及び重合可能な不飽和基を有する化合物等が挙げられる。これらの樹脂は、１種を単独で、又は２種以上を組み合わせて用いられる。 The curable composition of the present embodiment may further contain other resins as long as the effects of the present 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.
　オキセタン樹脂としては、例えば、オキセタン、２－メチルオキセタン、２，２－ジメチルオキセタン、３－メチルオキセタン、３，３－ジメチルオキセタン等のアルキルオキセタン、３－メチル－３－メトキシメチルオキセタン、３，３’－ジ（トリフルオロメチル）パーフルオキセタン、２－クロロメチルオキセタン、３，３－ビス（クロロメチル）オキセタン、ビフェニル型オキセタン、東亜合成株式会社製品の「ＯＸＴ－１０１」、「ＯＸＴ－１２１」等が挙げられる。 Examples of oxetane resins include oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, alkyloxetane such as 3,3-dimethyloxetane, 3-methyl-3-methoxymethyloxetane, 3,3- '-di(trifluoromethyl)perfluoxetane, 2-chloromethyloxetane, 3,3-bis(chloromethyl)oxetane, biphenyl type oxetane, products of Toagosei Co., Ltd. "OXT-101", "OXT-121" etc.
　本明細書にいう「ベンゾオキサジン化合物」とは、１分子中に２個以上のジヒドロベンゾオキサジン環を有する化合物をいう。ベンゾオキサジン化合物としては、小西化学株式会社製品の「ビスフェノールＦ型ベンゾオキサジンＢＦ－ＢＸＺ」「ビスフェノールＳ型ベンゾオキサジンＢＳ－ＢＸＺ」等が挙げられる。 The term "benzoxazine compound" as used herein refers to a compound having two or more dihydrobenzoxazine rings in one molecule. Examples of benzoxazine compounds include "Bisphenol F-type benzoxazine BF-BXZ" and "Bisphenol S-type benzoxazine BS-BXZ" manufactured by Konishi Chemical Co., Ltd., and the like.
　重合可能な不飽和基を有する化合物としては、例えば、エチレン、プロピレン、スチレン、ジビニルベンゼン、ジビニルビフェニル等のビニル化合物；メチル（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、トリメチロールプロパンジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート等の１価又は多価アルコールの（メタ）アクリレート類；ビスフェノールＡ型エポキシ（メタ）アクリレート、ビスフェノールＦ型エポキシ（メタ）アクリレート等のエポキシ（メタ）アクリレート類；ベンゾシクロブテン樹脂等が挙げられる。 Examples of compounds having a polymerizable unsaturated group include vinyl compounds such as ethylene, propylene, styrene, divinylbenzene, divinylbiphenyl; methyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl ( Monovalent meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. or polyhydric alcohol (meth)acrylates; epoxy (meth)acrylates such as bisphenol A type epoxy (meth)acrylate and bisphenol F type epoxy (meth)acrylate; benzocyclobutene resin and the like.
［無機充填材］
　本実施形態における硬化性組成物は、低熱膨張性を一層向上させる観点から、無機充填材を更に含有することが好ましい。無機充填材としては、特に限定されず、例えば、シリカ類、ケイ素化合物（例えば、ホワイトカーボン等）、金属酸化物（例えば、アルミナ、チタンホワイト、酸化亜鉛、酸化マグネシウム、酸化ジルコニウム等）、金属窒化物（例えば、窒化ホウ素、凝集窒化ホウ素、窒化ケイ素、窒化アルミニウム等）、金属硫酸化物（例えば、硫酸バリウム等）、金属水酸化物（例えば、水酸化アルミニウム、水酸化アルミニウム加熱処理品（例えば、水酸化アルミニウムを加熱処理し、結晶水の一部を減じたもの）、ベーマイト、水酸化マグネシウム等）、モリブデン化合物（例えば、酸化モリブデン、モリブデン酸亜鉛等）、亜鉛化合物（例えば、ホウ酸亜鉛、錫酸亜鉛等）、クレー、カオリン、タルク、焼成クレー、焼成カオリン、焼成タルク、マイカ、Ｅ－ガラス、Ａ－ガラス、ＮＥ－ガラス、Ｃ－ガラス、Ｌ－ガラス、Ｄ－ガラス、Ｓ－ガラス、Ｍ－ガラスＧ２０、ガラス短繊維（Ｅガラス、Ｔガラス、Ｄガラス、Ｓガラス、Ｑガラス等のガラス微粉末類を含む。）、中空ガラス、球状ガラス等が挙げられる。これらの無機充填材は、１種を単独で、又は２種以上を組み合わせて用いられる。これらの中でも、無機充填材は、低熱膨張性を一層向上させる観点から、シリカ類、金属水酸化物及び金属酸化物からなる群より選択される少なくとも１種であることが好ましく、シリカ類、ベーマイト及びアルミナからなる群より選択される１種以上を含むことがより好ましく、シリカ類であることが更に好ましい。 [Inorganic filler]
From the viewpoint of further improving the low thermal expansion property, the curable composition in the present embodiment preferably further contains an inorganic filler. 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. substances (e.g., 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.), clay, kaolin, talc, calcined clay, calcined kaolin, calcined talc, mica, E-glass, A-glass, NE-glass, C-glass, L-glass, D-glass, S-glass , M-Glass G20, glass short fibers (including fine glass powders such as E glass, T glass, D glass, S glass, Q glass, etc.), hollow glass, spherical glass, and the like. These inorganic fillers are used individually by 1 type or in combination of 2 or more types. Among these, 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.
　シリカ類としては、例えば、天然シリカ、溶融シリカ、合成シリカ、アエロジル、中空シリカ等が挙げられる。これらのシリカ類は１種を単独で、又は２種以上を組み合わせて用いられる。これらの中でも、分散性の観点から、溶融シリカであることが好ましく、充填性及び流動性の観点から、異なる粒度を持つ２種類以上の溶融シリカであることがより好ましい。 Examples of silicas 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.
　無機充填材の含有量は、低熱膨張性を一層向上させる観点から、樹脂固形分１００質量部に対して、５０～１０００質量部であることが好ましく、７０～５００質量部であることがより好ましく、１００～３００質量部であることが更に好ましい。 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.
［シランカップリング剤］
　本実施形態の硬化性組成物は、シランカップリング剤を更に含有してもよい。本実施形態の硬化性組成物は、シランカップリング剤を含有することにより、無機充填材の分散性が一層向上したり、本実施形態の硬化性組成物の成分と、後述する基材との接着強度が一層向上したりできる傾向にある。 [Silane coupling agent]
The curable composition of this embodiment may further contain a silane coupling agent. By containing a silane coupling agent, the curable composition of the present embodiment further improves the dispersibility of the inorganic filler, and the components of the curable composition of the present embodiment and the substrate described later. There is a tendency that the adhesive strength can be further improved.
　シランカップリング剤としては特に限定されず、一般に無機物の表面処理に使用されるシランカップリング剤が挙げられ、アミノシラン系化合物（例えば、γ－アミノプロピルトリエトキシシラン、Ｎ－β－（アミノエチル）－γ－アミノプロピルトリメトキシシラン等）、エポキシシラン系化合物（例えば、γ－グリシドキシプロピルトリメトキシシラン等）、アクリルシラン系化合物（例えば、γ－アクリロキシプロピルトリメトキシシラン等）、カチオニックシラン系化合物（例えば、Ｎ－β－（Ｎ－ビニルベンジルアミノエチル）－γ－アミノプロピルトリメトキシシラン塩酸塩等）、スチリルシラン系化合物、フェニルシラン系化合物等が挙げられる。シランカップリング剤は、１種を単独で、又は２種以上を組み合わせて用いられる。これらの中でも、シランカップリング剤は、エポキシシラン系化合物であることが好ましい。エポキシシラン系化合物としては、例えば、信越化学工業株式会社製品の「ＫＢＭ－４０３」、「ＫＢＭ－３０３」、「ＫＢＭ－４０２」、「ＫＢＥ－４０３」等が挙げられる。 The silane coupling agent is not particularly limited, and includes silane coupling agents generally used for surface treatment of inorganic substances, aminosilane compounds (eg, γ-aminopropyltriethoxysilane, N-β-(aminoethyl) -γ-aminopropyltrimethoxysilane, etc.), epoxysilane compounds (eg, γ-glycidoxypropyltrimethoxysilane, etc.), acrylsilane compounds (eg, γ-acryloxypropyltrimethoxysilane, etc.), cationic Examples include silane compounds (eg, N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane hydrochloride), styrylsilane compounds, phenylsilane compounds, and the like. A silane coupling agent is used individually by 1 type or in combination of 2 or more types. Among these, the silane coupling agent is preferably an epoxysilane compound. Examples of epoxysilane compounds include Shin-Etsu Chemical Co., Ltd. products "KBM-403", "KBM-303", "KBM-402", and "KBE-403".
　シランカップリング剤の含有量は、特に限定されないが、樹脂固形分１００質量部に対して、０．１～５．０質量部であってよい。 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.
［湿潤分散剤］
　本実施形態の硬化性組成物は、湿潤分散剤を更に含有してもよい。硬化性組成物は、湿潤分散剤を含有することにより、充填材の分散性が一層向上する傾向にある。 [Wetting and dispersing agent]
The curable composition of this embodiment may further contain a wetting and dispersing agent. The curable composition tends to further improve the dispersibility of the filler by containing a wetting and dispersing agent.
　湿潤分散剤としては、充填材を分散させるために用いられる公知の分散剤（分散安定剤）であればよく、例えば、ビックケミー・ジャパン（株）製のＤＩＳＰＥＲ　ＢＹＫ－１１０、１１１、１１８、１８０、１６１、ＢＹＫ－Ｗ９９６、Ｗ９０１０、Ｗ９０３等が挙げられる。 As the wetting and dispersing agent, any known dispersing agent (dispersion stabilizer) used to disperse the filler may be used. 161, BYK-W996, W9010, W903 and the like.
　湿潤分散剤の含有量は、特に限定されないが、樹脂固形分１００質量部に対して、０．５質量部以上５．０質量部以下であることが好ましい。 Although 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.
［溶剤］
　本実施形態の硬化性組成物は、溶剤を更に含有してもよい。本実施形態の硬化性組成物は、溶剤を含むことにより、硬化性組成物の調製時における粘度が下がり、ハンドリング性（取り扱い性）が一層向上したり、基材への含浸性が一層向上したりする傾向にある。 [solvent]
The curable composition of this embodiment may further contain a solvent. By containing a solvent, the curable composition of the present embodiment has a lower viscosity during preparation of the curable composition, further improved handling properties (handleability), and further improved impregnating properties into the substrate. tend to fall.
　溶剤としては、硬化性組成物中の各成分の一部又は全部を溶解可能であれば、特に限定されないが、例えば、ケトン類（アセトン、メチルエチルケトン等）、芳香族炭化水素類（例えば、トルエン、キシレン等）、アミド類（例えば、ジメチルホルムアルデヒド等）、プロピレングリコールモノメチルエーテル及びそのアセテート等が挙げられる。これらの溶剤は、１種を単独で、又は２種以上を組み合わせて用いられる。 The solvent is not particularly limited as long as it can dissolve a part or all of each component in the curable composition. 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.
　本実施形態の硬化性組成物の製造方法としては、特に限定されるものではなく、例えば、上記した各成分を一括的に又は逐次的に溶剤に配合し、撹拌する方法が挙げられる。この際、各成分を均一に溶解又は分散せるために、撹拌、混合、混練処理等の公知の処理が用いられる。 The method for producing the curable composition of the present embodiment is not particularly limited, and includes, for example, a method of collectively or sequentially blending each of the components described above 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.
［用途］
　本実施形態の硬化性組成物は、上記の通り、優れた相溶性を有し、一層優れた低熱膨張性及び銅箔ピール強度を発現できる。このため、本実施形態の硬化性組成物は、金属箔張積層板及びプリント配線板に好適に用いられる。すなわち、本実施形態の硬化性組成物は、プリント配線板用の硬化組成物として、好適に用いることができる。 [Use]
As described above, the curable composition of the present embodiment has excellent compatibility and can exhibit even better low thermal expansion and copper foil peel strength. Therefore, the curable composition of the present embodiment is suitably used for metal foil-clad laminates and printed wiring boards. That is, the curable composition of this embodiment can be suitably used as a curable composition for printed wiring boards.
　なお、とりわけ上記した用途において、第２実施形態の硬化性組成物は、重合体Ｅに加え、少なくともエポキシ化合物Ｃ（重合体Ｅ中の構成単位Ｃとは別に存在するエポキシ化合物Ｃ）を含むことが好ましい。
　この場合において、重合体Ｅは、エポキシ化合物Ｃに由来する単位として、前述した２官能エポキシ化合物に由来する単位を有することが好ましく、より好ましくは前述したビフェニル型エポキシ化合物に由来する単位を有し、さらに好ましくは上記式（ｂ２）で表される化合物（化合物ｂ２）に由来する単位を有し、一層好ましくはＲａの数が０である化合物ｂ２と、アルキル基であるＲａの数が４である化合物ｂ２（市販品としては、例えば、三菱ケミカル（株）製の商品名「ＹＬ－６１２１ＨＡ」等）に由来する単位を有する。
　また、重合体Ｅ中の構成単位Ｃとは別に存在するエポキシ化合物Ｃとしては、前述したナフチレンエーテル型エポキシ樹脂（市販品としては、例えば、ＤＩＣ株式会社製品の「ＨＰ－６０００」等）及び／又はナフタレンクレゾールノボラック型エポキシ樹脂（市販品としては、例えば、ＤＩＣ株式会社製品の「ＨＰ－９５４０」等）を含むことが好ましい。 In particular, in the applications described above, the curable composition of the second embodiment contains, in addition to the polymer E, at least an epoxy compound C (epoxy compound C existing separately from the structural unit C in the polymer E). is preferred.
In this case, the polymer E preferably has units derived from the above-described bifunctional epoxy compound as units derived from the epoxy compound C, and more preferably has units derived from the above-described biphenyl-type epoxy compound. More preferably, a compound b2 having a unit derived from the compound (compound b2) represented by the above formula (b2), more preferably the number of R a is 0, and the number of R a being an alkyl group is 4 (commercially available, for example, "YL-6121HA" manufactured by Mitsubishi Chemical Corporation).
Further, as the epoxy compound C present separately from the structural unit C in the polymer E, 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.
［プリプレグ］
　本実施形態のプリプレグは、基材と、基材に含浸又は塗布された本実施形態の硬化性組成物とを含む。プリプレグは、前述の通り、公知の方法によって得られるプリプレグであってもよく、具体的には、本実施形態の硬化性組成物を基材に含浸又は塗布させた後、１００～２００℃の条件にて加熱乾燥させることにより半硬化（Ｂステージ化）させることにより得られる。 [Prepreg]
The prepreg of this embodiment includes a substrate and the curable composition of this embodiment impregnated or applied to the substrate. The prepreg may be a prepreg obtained by a known method, as described above. It is obtained by semi-curing (to B stage) by heating and drying at.
　本実施形態のプリプレグは、半硬化状態のプリプレグを１８０～２３０℃の加熱温度及び６０～１８０分の加熱時間の条件で熱硬化させて得られる硬化物の形態も包含する。 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.
　プリプレグにおける硬化性組成物の含有量は、プリプレグの総量に対して、プリプレグの固形分換算で、好ましくは３０～９０体積％であり、より好ましくは３５～８５体積％であり、更に好ましくは４０～８０体積％である。硬化性組成物の含有量が上記範囲内であることにより、成形性がより向上する傾向にある。なお、ここでいう硬化性組成物の含有量計算には、本実施形態の硬化性組成物の硬化物も含む。また、ここでいうプリプレグの固形分は、プリプレグ中から溶剤を取り除いた成分をいい、例えば、充填材は、プリプレグの固形分に含まれる。 The content of the curable composition in the prepreg is preferably 30 to 90% by volume, more preferably 35 to 85% by volume, and still more preferably 40% by volume in terms of the solid content of the prepreg with respect to the total amount of the prepreg. ~80% by volume. When the content of the curable composition is within the above range, moldability tends to be further improved. The calculation of the content of the curable composition herein includes the cured product of the curable composition of the present embodiment. Further, the solid content of the prepreg as used herein refers to a component obtained by removing the solvent from the prepreg. For example, the filler is included in the solid content of the prepreg.
　基材としては、特に限定されず、例えば、各種プリント配線板の材料に用いられている公知の基材が挙げられる。基材の具体例としては、ガラス基材、ガラス以外の無機基材（例えば、クォーツ等のガラス以外の無機繊維で構成された無機基材）、有機基材（例えば、全芳香族ポリアミド、ポリエステル、ポリパラフェニレンベンズオキサゾール、ポリイミド等の有機繊維で構成された有機基材）等が挙げられる。これらの基材は、１種を単独で、又は２種以上を組み合わせて用いられる。これらの中でも、加熱寸法安定性に一層優れたりする観点から、ガラス基材が好ましい。 The base material is not particularly limited, and includes, for example, known base materials 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. Among these, a glass substrate is preferable from the viewpoint of being more excellent in dimensional stability under heating.
　ガラス基材を構成する繊維としては、例えば、Ｅガラス、Ｄガラス、Ｓガラス、Ｔガラス、Ｑガラス、Ｌガラス、ＮＥガラス、ＨＭＥガラス等の繊維が挙げられる。これらの中でも、ガラス基材を構成する繊維は、強度と低吸水性に一層優れる観点から、Ｅガラス、Ｄガラス、Ｓガラス、Ｔガラス、Ｑガラス、Ｌガラス、ＮＥガラス及びＨＭＥガラスからなる群より選択される１種以上の繊維であることが好ましい。 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. Among these, 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.
　基材の形態としては、特に限定されないが、例えば、織布、不織布、ロービング、チョップドストランドマット、サーフェシングマット等の形態が挙げられる。織布の織り方としては、特に限定されないが、例えば、平織り、ななこ織り、綾織り等が知られており、これら公知のものから目的とする用途や性能により適宜選択して使用することができる。また、これらを開繊処理したものやシランカップリング剤等で表面処理したガラス織布が好適に使用される。基材の厚さや質量は、特に限定されないが、通常は０．０１～０．１ｍｍ程度のものが好適に用いられる。 The form of the substrate is not particularly limited, but examples 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. . In addition, 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.
［レジンシート］
　本実施形態のレジンシートは、支持体と、支持体の表面に配置された本実施形態の硬化性組成物とを含む。本実施形態のレジンシートは、例えば、本実施形態の硬化性組成物を支持体の片面又は両面に塗布することにより形成されたものであってもよい。本実施形態のレジンシートは、例えば、金属箔やフィルム等の支持体に、直接、プリプレグ等に用いられる硬化性組成物を塗布及び乾燥して製造できる。 [Resin sheet]
The resin sheet of this embodiment includes a support and the curable composition of this embodiment disposed on the surface of the support. The resin sheet of the present embodiment may be formed, for example, by applying the curable composition of the present embodiment to one side or both sides of a support. The resin sheet of the present embodiment can be produced, for example, by directly coating a support such as a metal foil or film with a curable composition used for prepreg or the like and drying the composition.
　支持体としては、特に限定されないが、例えば、各種プリント配線板材料に用いられている公知のものを使用することができ、樹脂シート又は金属箔であることが好ましい。樹脂シート及び金属箔としては、例えば、ポリイミドフィルム、ポリアミドフィルム、ポリエステルフィルム、ポリエチレンテレフタレート（ＰＥＴ）フィルム、ポリブチレンテレフタレート（ＰＢＴ）フィルム、ポリプロピレン（ＰＰ）フィルム、ポリエチレン（ＰＥ）フィルム等の樹脂シート、及びアルミニウム箔、銅箔、金箔等の金属箔が挙げられる。支持体は、これらの中でも、電解銅箔、ＰＥＴフィルムが好ましい。 Although the support is not particularly limited, for example, known materials used in various printed wiring board materials can be used, and a resin sheet or metal foil is preferable. Examples of resin sheets and metal foils include resin sheets such as polyimide film, polyamide film, polyester film, polyethylene terephthalate (PET) film, polybutylene terephthalate (PBT) film, polypropylene (PP) film, polyethylene (PE) film, etc. and metal foils such as aluminum foil, copper foil and gold foil. Among these, the support is preferably an electrolytic copper foil or a PET film.
　本実施形態のレジンシートは、例えば、本実施形態の硬化性組成物を支持体に塗布後、半硬化（Ｂステージ化）させることにより得られる。本実施形態のレジンシートの製造方法は、一般にＢステージ樹脂及び支持体の複合体を製造する方法が好ましい。具体的には、例えば、上記硬化性組成物を銅箔などの支持体に塗布した後、１００～２００℃の乾燥機中で、１～６０分加熱させる方法などにより半硬化させ、レジンシートを製造する方法などが挙げられる。支持体に対する硬化性組成物の付着量は、レジンシートの樹脂厚で１．０μｍ以上３００μｍ以下の範囲が好ましい。本実施形態のレジンシートは、プリント配線板のビルドアップ材料として使用可能である。 The resin sheet of the present embodiment can be obtained, for example, by applying the curable composition of the present embodiment to a support and then semi-curing (to B-stage). The method for producing the resin sheet of the present embodiment is generally preferably a method for producing a composite of a B-stage resin and a support. Specifically, for example, after the curable composition is applied to a support such as a copper foil, it is semi-cured by a method of heating for 1 to 60 minutes in a dryer at 100 to 200 ° C. to form a resin sheet. A manufacturing method and the like can be mentioned. The adhesion amount of the curable composition to the support is preferably in the range of 1.0 μm or more and 300 μm or less in terms of resin thickness of the resin sheet. The resin sheet of this embodiment can be used as a build-up material for printed wiring boards.
［金属箔張積層板］
　本実施形態の金属箔張積層板は、本実施形態のプリプレグ及びレジンシートからなる群より選択される１種以上を用いて形成された積層体と、該積層体の片面又は両面に配置された金属箔とを含む。該積層体は１つのプリプレグ又はレジンシートで形成されていてよく、複数のプリプレグ及び／又はレジンシートで形成されていてよい。 [Metal foil clad laminate]
The metal foil-clad laminate of the present embodiment includes a laminate formed using one or more selected from the group consisting of the prepreg and the resin sheet of the present embodiment, and a including metal foil. The laminate may be formed of one prepreg or resin sheet, or may be formed of a plurality of prepregs and/or resin sheets.
　金属箔（導体層）としては、各種プリント配線板材料に用いられる金属箔であればよく、例えば、銅、アルミニウム等の金属箔が挙げられ、銅の金属箔としては、圧延銅箔、電解銅箔等の銅箔が挙げられる。導体層の厚みは、例えば、１～７０μｍであり、好ましくは１．５～３５μｍである。 The metal foil (conductor layer) 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 μm, preferably 1.5 to 35 μm.
　金属箔張積層板の成形方法及びその成形条件は、特に限定されず、一般的なプリント配線板用積層板及び多層板の手法及び条件を適用することができる。例えば、積層板（上述した積層体）又は金属箔張積層板の成形時には多段プレス機、多段真空プレス機、連続成形機、オートクレーブ成形機等を用いることができる。また、積層板（上述した積層体）又は金属箔張積層板の成形（積層成形）において、温度は１００～３００℃、圧力は面圧２～１００ｋｇｆ／ｃｍ2、加熱時間は０．０５～５時間の範囲が一般的である。さらに、必要に応じて、１５０～３００℃の温度で後硬化を行うこともできる。特に多段プレス機を用いた場合は、プリプレグの硬化を十分に促進させる観点から、温度２００℃～２５０℃、圧力１０～４０ｋｇｆ／ｃｍ2、加熱時間８０分～１３０分が好ましく、温度２１５℃～２３５℃、圧力２５～３５ｋｇｆ／ｃｍ2、加熱時間９０分～１２０分がより好ましい。また、上述のプリプレグと、別途作成した内層用の配線板とを組み合わせて積層成形することにより、多層板とすることも可能である。 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. For example, 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 (laminate described above) or a metal foil-clad laminate. In the molding of a laminate (laminate described above) or a metal foil-clad laminate (lamination molding), the temperature is 100 to 300° C., the pressure is 2 to 100 kgf/cm 2 , and the heating time is 0.05 to 5. Time ranges are common. Furthermore, if desired, post-curing can be performed at a temperature of 150-300°C. Particularly when a multistage press is used, 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, and the temperature is 215° C. to 215° C., from the viewpoint of sufficiently accelerating the curing of the prepreg. More preferably, the temperature is 235° C., the pressure is 25 to 35 kgf/cm 2 , and the heating time is 90 to 120 minutes. Moreover, it is also possible to form a multi-layer board by combining the above-mentioned prepreg and a wiring board for an inner layer separately prepared and performing lamination molding.
［プリント配線板］
　本実施形態のプリント配線板は、本実施形態のプリプレグ及びレジンシートからなる群より選択される１種以上で形成された絶縁層と、該絶縁層の表面に形成された導体層と、を有する。本実施形態のプリント配線板は、例えば、本実施形態の金属箔張積層板の金属箔を所定の配線パターンにエッチングして導体層とすることにより形成できる。 [Printed wiring board]
The printed wiring board of the present embodiment has an insulating layer formed of one or more selected from the group consisting of the prepreg and the resin sheet of the present embodiment, and a conductor layer formed on the surface of the insulating layer. . The printed wiring board of the present embodiment can be formed, for example, by etching the metal foil of the metal foil-clad laminate of the present embodiment into a predetermined wiring pattern to form a conductor layer.
　本実施形態のプリント配線板は、具体的には、例えば、以下の方法により製造することができる。まず、本実施形態の金属箔張積層板を用意する。金属箔張積層板の金属箔を所定の配線パターンにエッチングして導体層（内層回路）を有する内層基板を作成する。次に、内層基板の導体層（内装回路）表面に、所定数の絶縁層と、外層回路用の金属箔とをこの順序で積層し、加熱加圧して一体成形（積層成形）することにより、積層体を得る。尚、積層成形の方法及びその成形条件は、上記の積層板及び金属箔張積層板における積層成形の方法及びその成形条件と同様である。次に、積層体にスルーホール、バイアホール用の穴あけ加工を施し、これにより形成された穴の壁面に導体層（内装回路）と、外層回路用の金属箔とを導通させるためのめっき金属皮膜を形成する。次に、外層回路用の金属箔を所定の配線パターンにエッチングして導体層（外層回路）を有する外層基板を作成する。このようにしてプリント配線板が製造される。 Specifically, the printed wiring board of the present embodiment can be manufactured, for example, by the following method. First, the metal foil-clad laminate of this embodiment is prepared. 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. Next, on the surface of the conductor layer (internal circuit) of the inner layer substrate, a predetermined number of insulating layers and a metal foil for the outer layer circuit are laminated in this order, and heat-pressed for integral molding (laminate molding). 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. Next, 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. to form Next, 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.
　また、金属箔張積層板を用いない場合には、上記絶縁層に、回路となる導体層を形成しプリント配線板を作製してもよい。この際、導体層の形成に無電解めっきの手法を用いることもできる。 In addition, when a metal foil-clad laminate is not used, 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.
　以下、実施例によって本発明を更に詳細に説明するが、本発明はこれらの実施例に限定されるものではない。 The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.
（実施例１）
　温度計、ジムロートを取り付けた三口フラスコに、ジアリルビスフェノールＡ（ＤＡＢＰＡ、大和化成工業（株））５．０質量部、ビスクレゾールフルオレン（ＢＣＦ、大阪ガス化学（株））５．５質量部、エポキシ変性シリコーン化合物Ａ（Ｘ－２２－１６３、信越化学工業（株）、官能基当量２００ｇ／ｅｑ．）４．１質量部、エポキシ変性シリコーン化合物Ｂ（ＫＦ－１０５、信越化学工業（株）、官能基当量５００ｇ／ｅｑ．）８．４質量部、ビフェニル型エポキシ化合物Ａ（ＹＬ－６１２１ＨＡ、三菱ケミカル（株））５．５質量部、溶媒としてプロピレングリコールモノメチルエーテルアセテート（ＤＯＷＡＮＯＬ ＰＭＡ、ダウ・ケミカル日本（株））３０．０質量部を加え、オイルバスにて１２０℃まで加熱撹拌した。原料が溶媒に溶解したことを確認し、イミダゾール触媒Ａ（ＴＢＺ、四国化成工業（株））０．３質量部を加え１４０℃まで昇温したのち、５時間撹拌し、冷却してフェノキシポリマー溶液（固形分５０質量％）を得た（ポリマー生成工程）。なお、ジアリルビスフェノールＡは、「アルケニルフェノールＡ」に相当し、エポキシ変性シリコーン化合物Ａ及びエポキシ変性シリコーン化合物Ｂは、「エポキシ変性シリコーンＢ」に相当し、ビフェニル型エポキシ化合物Ａは、「エポキシ化合物Ｃ」に相当する。フェノキシポリマー溶液には、アルケニルフェノールＡに由来する構成単位と、エポキシ変性シリコーンＢに由来する構成単位と、エポキシ化合物Ｃに由来する構成単位とを含有する重合体が含まれていた。 (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.), 5.5 parts by mass of biscresol fluorene (BCF, Osaka Gas Chemical Co., Ltd.), epoxy Modified silicone compound A (X-22-163, Shin-Etsu Chemical Co., Ltd., functional group equivalent 200 g / eq.) 4.1 parts by mass, epoxy-modified silicone compound B (KF-105, Shin-Etsu Chemical Co., Ltd., functional Base equivalent 500 g / eq.) 8.4 parts by mass, biphenyl type epoxy compound A (YL-6121HA, Mitsubishi Chemical Corporation) 5.5 parts by mass, propylene glycol monomethyl ether acetate (DOWANOL PMA, Dow Chemical Japan) as a solvent Co., Ltd.) was added, and the mixture was heated to 120° C. with stirring in an oil bath. After confirming that the raw materials were dissolved in the solvent, 0.3 parts by mass of imidazole catalyst A (TBZ, Shikoku Kasei Kogyo Co., Ltd.) was added and the temperature was raised to 140° C., followed by stirring for 5 hours and cooling to obtain a phenoxy polymer solution. (solid content: 50% by mass) was obtained (polymer production step). In addition, diallyl bisphenol A corresponds to "alkenylphenol A", epoxy-modified silicone compound A and epoxy-modified silicone compound B correspond to "epoxy-modified silicone B", and biphenyl-type epoxy compound A corresponds to "epoxy compound C Equivalent to The phenoxy polymer solution contained a polymer containing structural units derived from alkenylphenol A, structural units derived from epoxy-modified silicone B, and structural units derived from epoxy compound C.
　このフェノキシポリマー溶液をオイルバスにて１００℃まで加熱したのち、酸無水物Ｄとして無水コハク酸１．５質量部を加えて、２時間攪拌し、冷却後、変性フェノキシポリマー溶液（固形分５０質量％）を得た（ポリマー変性工程）。変性フェノキシポリマー溶液には、アルケニルフェノールＡに由来する構成単位と、エポキシ変性シリコーンＢに由来する構成単位と、エポキシ化合物Ｃに由来する構成単位と、酸無水物Ｄに由来する構成単位とを含有する重合体が含まれていた。ポリマー変性工程はポリマー生成工程と連続して行うこともできる。 After heating this phenoxy polymer solution to 100° C. in an oil bath, 1.5 parts by mass of succinic anhydride was added as acid anhydride D and stirred for 2 hours. After cooling, the modified phenoxy polymer solution (solid content: 50 mass %) was obtained (polymer modification step). The modified phenoxy polymer solution contains structural units derived from alkenylphenol A, structural units derived from epoxy-modified silicone B, structural units derived from epoxy compound C, and structural units derived from acid anhydride D. It contained a polymer that The polymer modification step can also be performed continuously with the polymer production step.
〔重量平均分子量Ｍｗの測定方法〕
　上記のようにして得られた変性フェノキシポリマーの重量平均分子量Ｍｗを、以下のようにして測定した。変性フェノキシポリマー溶液０．５ｇを２ｇのＴＨＦに溶解させた溶液２０μＬを高速液体クロマトグラフィー（島津製作所製、ポンプ：ＬＣ－２０ＡＤ）に注入して分析を実施した。カラムは、昭和電工製Ｓｈｏｄｅｘ　ＧＰＣ　ＫＦ－８０４（長さ３０ｃｍ×内径８ｍｍ）、Ｓｈｏｄｅｘ　ＧＰＣ　ＫＦ－８０３（長さ３０ｃｍ×内径８ｍｍ）、Ｓｈｏｄｅｘ　ＧＰＣ　ＫＦ－８０２（長さ３０ｃｍ×内径８ｍｍ）、Ｓｈｏｄｅｘ　ＧＰＣ　ＫＦ－８０１（長さ３０ｃｍ×内径８ｍｍ）、の計４本使用し、移動相としてＴＨＦ（溶媒）を用いて、流速を１ｍＬ／ｍｉｎとし、検出器はＲＩＤ－１０Ａを用いた。重量平均分子量Ｍｗは、ＧＰＣ法により標準ポリスチレンを標準物質として求めた。
　上記のようにして測定された変性フェノキシポリマーの重量平均分子量Ｍｗは、１２，０００であった。 [Measurement method of weight average molecular weight Mw]
The weight average molecular weight Mw of the modified phenoxy polymer obtained as described above was measured as follows. Analysis was performed by injecting 20 μL of a solution prepared by dissolving 0.5 g of the modified phenoxy polymer solution in 2 g of THF into a high-performance liquid chromatography (manufactured by Shimadzu Corporation, pump: LC-20AD). 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. A total of 4 tubes of KF-801 (length 30 cm x inner diameter 8 mm) were used, THF (solvent) was used as the mobile phase, the flow rate was 1 mL/min, and RID-10A was used as the detector. 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 modified phenoxy polymer measured as described above was 12,000.
　この変性フェノキシポリマー溶液に、ナフトールアラルキル型フェノール化合物（ＳＮ－４９５Ｖ、日鉄ケミカル＆マテリアル(株)）２５質量部、ノボラック型マレイミド化合物（ＢＭＩ－２３００、大和化成工業（株））９質量部、フェニレンエーテル型マレイミド化合物（ＢＭＩ－８０、大和化成工業（株））９質量部、ナフチレンエーテル型エポキシ化合物（ＨＰ－６０００、ＤＩＣ（株））２７質量部、球状シリカ（ＳＣ－２０５０ＭＢ、アドマテックス（株））２００質量部、湿潤分散剤（ＤＩＳＰＥＲＢＹＫ－１６１、ビックケミー・ジャパン（株））１質量部、シランカップリング剤（ＫＢＭ－４０３、信越化学工業（株））５質量部を混合してワニスを得た（ワニス生成工程）。このワニスをＳガラス織布（厚さ１００μｍ）に含浸塗工し、１５０℃で３分間加熱乾燥して、硬化性組成物固形分（充填材を含む）の含有量５８．２体積％のプリプレグを得た（プリプレグ製造工程）。 In this modified phenoxy polymer solution, 25 parts by mass of a naphthol aralkyl-type phenol compound (SN-495V, Nippon Steel Chemical & Materials Co., Ltd.), 9 parts by mass of a novolac-type maleimide compound (BMI-2300, Daiwa Kasei Kogyo Co., Ltd.), Phenylene ether-type maleimide compound (BMI-80, Daiwa Kasei Kogyo Co., Ltd.) 9 parts by weight, naphthylene ether-type epoxy compound (HP-6000, DIC Corporation) 27 parts by weight, spherical silica (SC-2050MB, Admatex Co., Ltd.) 200 parts by mass, a wetting and dispersing agent (DISPERBYK-161, BYK-Chemie Japan Co., Ltd.) 1 part by mass, and a silane coupling agent (KBM-403, Shin-Etsu Chemical Co., Ltd.) 5 parts by mass. A varnish was obtained (varnish production step). This varnish was impregnated and coated on an S glass woven cloth (thickness 100 μm), dried by heating at 150 ° C. for 3 minutes, and a prepreg having a curable composition solid content (including filler) content of 58.2% by volume was obtained. was obtained (prepreg manufacturing process).
（実施例２）
　ポリマー生成工程において、ジアリルビスフェノールＡの添加量を５．０質量部から４．７質量部とし、ビスクレゾールフルオレンの添加量を５．５質量部から５．２質量部とし、エポキシ変性シリコーンＡの添加量を４．１質量部から３．８質量部とし、エポキシ変性シリコーンＢの添加量を８．４質量部から８．１質量部とし、ビフェニル型エポキシ化合物Ａの添加量を５．５質量部から５．２質量部とし、ポリマー変性工程において、酸無水物Ｄの添加量を、１．５質量部に代えて３．０質量部としたこと以外は、実施例１と同様にして、硬化性組成物固形分（充填材を含む）の含有量５８．２体積％のプリプレグを得た。
　変性フェノキシポリマー溶液には、アルケニルフェノールＡに由来する構成単位と、エポキシ変性シリコーンＢに由来する構成単位と、エポキシ化合物Ｃに由来する構成単位と、酸無水物Ｄに由来する構成単位とを含有する重合体が含まれていた。
　また、前述の方法により測定される、実施例２における変性フェノキシポリマーの重量平均分子量Ｍｗは、１２，０００であった。 (Example 2)
In the polymer production step, the amount of diallyl bisphenol A added was 5.0 parts by mass to 4.7 parts by mass, the amount of biscresol fluorene added was 5.5 parts by mass to 5.2 parts by mass, and epoxy-modified silicone A was added. The amount added is 4.1 parts by mass to 3.8 parts by mass, the amount of epoxy-modified silicone B added is 8.4 parts by mass to 8.1 parts by mass, and the amount of biphenyl type epoxy compound A added is 5.5 parts by mass. In the same manner as in Example 1, except that the amount of acid anhydride D added in the polymer modification step was changed from 1.5 parts by mass to 5.2 parts by mass, and was changed to 3.0 parts by mass. A prepreg having a curable composition solid content (including filler) content of 58.2% by volume was obtained.
The modified phenoxy polymer solution contains structural units derived from alkenylphenol A, structural units derived from epoxy-modified silicone B, structural units derived from epoxy compound C, and structural units derived from acid anhydride D. It contained a polymer that
Moreover, the weight average molecular weight Mw of the modified phenoxy polymer in Example 2 measured by the method described above was 12,000.
（実施例３）
　ポリマー変性工程において、酸無水物Ｄを、無水コハク酸３．０質量部に代えて無水フタル酸３．０質量部としたこと以外は、実施例２と同様にして、硬化性組成物固形分（充填材を含む）の含有量５８．２体積％のプリプレグを得た。
　変性フェノキシポリマー溶液には、アルケニルフェノールＡに由来する構成単位と、エポキシ変性シリコーンＢに由来する構成単位と、エポキシ化合物Ｃに由来する構成単位と、酸無水物Ｄに由来する構成単位とを含有する重合体が含まれていた。
　また、前述の方法により測定される、実施例３における変性フェノキシポリマーの重量平均分子量Ｍｗは、１２，０００であった。 (Example 3)
In the polymer modification step, the curable composition solid content was adjusted in the same manner as in Example 2, except that the acid anhydride D was replaced with 3.0 parts by mass of succinic anhydride and 3.0 parts by mass of phthalic anhydride. A prepreg with a content of 58.2% by volume (including filler) was obtained.
The modified phenoxy polymer solution contains structural units derived from alkenylphenol A, structural units derived from epoxy-modified silicone B, structural units derived from epoxy compound C, and structural units derived from acid anhydride D. It contained a polymer that
The weight average molecular weight Mw of the modified phenoxy polymer in Example 3, measured by the method described above, was 12,000.
（比較例１）
　ポリマー生成工程において、ジアリルビスフェノールＡの添加量を５．０質量部から５．３質量部とし、ビスクレゾールフルオレンの添加量を５．５質量部から５．８質量部とし、エポキシ変性シリコーンＡの添加量を４．１質量部から４．４質量部とし、エポキシ変性シリコーンＢの添加量を８．４質量部から８．７質量部とし、ビフェニル型エポキシ化合物Ａの添加量を５．５質量部から５．８質量部とし、イミダゾール触媒Ａの添加量を０．３０質量部から１．２質量部として、ポリマー変性工程を行わなかった以外は実施例１と同様にして樹脂組成固形分（充填剤を含む）の含有率５８．２体積％のプリプレグを得た。
　前述の方法により測定される、比較例１におけるフェノキシポリマーの重量平均分子量Ｍｗは、１２，０００であった。 (Comparative example 1)
In the polymer production step, the amount of diallyl bisphenol A added was 5.0 parts by mass to 5.3 parts by mass, the amount of biscresol fluorene added was 5.5 parts by mass to 5.8 parts by mass, and epoxy-modified silicone A was added. The amount added is 4.1 parts by mass to 4.4 parts by mass, the amount of epoxy-modified silicone B added is 8.4 parts by mass to 8.7 parts by mass, and the amount of biphenyl type epoxy compound A added is 5.5 parts by mass. The solid content of the resin composition ( A prepreg with a content of 58.2% by volume (including filler) was obtained.
The weight average molecular weight Mw of the phenoxy polymer in Comparative Example 1 measured by the method described above was 12,000.
　各実施例１～３及び比較例１にて得られたプリプレグを、２枚重ね、さらに１２μｍの厚さを有する電解銅箔（３ＥＣ－Ｍ２Ｓ－ＶＬＰ、三井金属鉱業（株）製）を上下に配置し、圧力３０ｋｇｆ／ｃｍ２、温度２２０℃で１２０分間の積層成形を行い、金属箔張積層板として、０．２ｍｍの厚さを有する絶縁層を含む銅箔張積層板を得た。得られた銅箔張積層板の特性を以下に示す方法にて評価した。評価結果を表１に示す。 Two sheets of the prepreg obtained in each of Examples 1 to 3 and Comparative Example 1 are stacked, and an electrolytic copper foil (3EC-M2S-VLP, manufactured by Mitsui Kinzoku Mining Co., Ltd.) having a thickness of 12 μm is placed on top and bottom. Lamination molding was performed at a pressure of 30 kgf/cm 2 and a temperature of 220° C. for 120 minutes to obtain a copper foil clad laminate including an insulating layer having a thickness of 0.2 mm as a metal foil clad laminate. The properties of the obtained copper foil clad laminates were evaluated by the methods described below. Table 1 shows the evaluation results.
［銅箔ピール強度］
　上記方法で得られた銅箔張積層板（１０ｍｍ×１５０ｍｍ×０．２ｍ）を用い、ＪＩＳ　Ｃ６４８１に準じて、銅箔ピール強度（単位：ｋＮ／ｍ）を測定した。 [Copper foil peel strength]
Using the copper foil clad laminate (10 mm×150 mm×0.2 m) obtained by the above method, the copper foil peel strength (unit: kN/m) was measured according to JIS C6481.
［線熱膨張係数（ＣＴＥ）］
　積層板の絶縁層についてガラスクロスの縦方向の線熱膨張係数を測定した。具体的には、上記方法で得られた銅箔張積層板（１０ｍｍ×６ｍｍ×０．２ｍｍ）の両面の銅箔をエッチングにより除去した後に、２２０℃の恒温槽で２時間加熱して、成形による応力を除去した。その後、熱膨張率測定装置（リンザイス製水平ディラトメーター）を用いて４０℃から３２０℃まで毎分１０℃で昇温して、６０℃から２６０℃における線熱膨張係数（ＣＴＥ）（単位：ｐｐｍ／℃）を測定した。 [Coefficient of linear thermal expansion (CTE)]
The coefficient of linear thermal expansion in the longitudinal direction of the glass cloth was measured for the insulating layer of the laminate. Specifically, after removing the copper foil on both sides of the copper foil-clad laminate (10 mm × 6 mm × 0.2 mm) obtained by the above method by etching, it is heated in a constant temperature bath at 220 ° C. for 2 hours and molded. removed the stress due to After that, using a thermal expansion coefficient measuring device (Linseis horizontal dilatometer), the temperature was raised from 40 ° C. to 320 ° C. at 10 ° C. per minute, and the linear thermal expansion coefficient (CTE) (unit: ppm/°C) was measured.
Figure JPOXMLDOC01-appb-T000060
Figure JPOXMLDOC01-appb-T000060
　上記表１に示すとおり、本実施形態の硬化性組成物を用いた銅箔張積層板（実施例１～３）は、優れた低熱膨張性及び銅箔ピール強度を有していた。 As shown in Table 1 above, the copper foil clad laminates (Examples 1 to 3) using the curable composition of the present embodiment had excellent low thermal expansion and copper foil peel strength.
　本出願は、２０２１年８月５日に日本国特許庁へ出願された日本特許出願（特願２０２１－１２８７４３）に基づくものであり、その内容はここに参照として取り込まれる。 This application is based on a Japanese patent application (Japanese Patent Application No. 2021-128743) filed with the Japan Patent Office on August 5, 2021, the contents of which are incorporated herein by reference.

Claims (34)

  1. 　アルケニルフェノールＡと、エポキシ変性シリコーンＢと、前記エポキシ変性シリコーンＢ以外のエポキシ化合物Ｃと、酸無水物Ｄを含有する、硬化性組成物。 A curable composition containing an alkenylphenol A, an epoxy-modified silicone B, an epoxy compound C other than the epoxy-modified silicone B, and an acid anhydride D.
  2. 　前記アルケニルフェノールＡの１分子当たりの平均フェノール基数が１以上３未満であり、前記エポキシ変性シリコーンＢの１分子当たりの平均エポキシ基数が１以上３未満であり、前記エポキシ化合物Ｃの１分子当たりの平均エポキシ基数が１以上３未満である、請求項１に記載の硬化性組成物。 The average number of phenol groups per molecule of the alkenylphenol A is 1 or more and less than 3, the average number of epoxy groups per molecule of the epoxy-modified silicone B is 1 or more and less than 3, and the epoxy compound C has an average number of 2. The curable composition according to claim 1, wherein the average number of epoxy groups is 1 or more and less than 3.
  3. 　前記アルケニルフェノールＡが、ジアリルビスフェノール及び／又はジプロペニルビスフェノールを含有する、請求項１又は２に記載の硬化性組成物。 The curable composition according to claim 1 or 2, wherein the alkenylphenol A contains diallyl bisphenol and/or dipropenyl bisphenol.
  4. 　前記エポキシ変性シリコーンＢが、１４０～２５０ｇ／ｍｏｌのエポキシ当量を有するエポキシ変性シリコーンを含有する、請求項１又は２に記載の硬化性組成物。 The curable composition according to claim 1 or 2, wherein the epoxy-modified silicone B contains an epoxy-modified silicone having an epoxy equivalent of 140 to 250 g/mol.
  5. 　前記エポキシ変性シリコーンＢが、下記式（１）で表されるエポキシ変性シリコーンを含有する、請求項１又は２に記載の硬化性組成物。
    Figure JPOXMLDOC01-appb-C000001
     （式中、Ｒ１は、各々独立に、単結合、アルキレン基、アリーレン基又はアラルキレン基を示し、Ｒ２は、各々独立に、炭素数１～１０のアルキル基又はフェニル基を示し、ｎは、０～１００の整数を示す。）     The curable composition according to claim 1 or 2, wherein the epoxy-modified silicone B contains an epoxy-modified silicone represented by the following formula (1).
    Figure JPOXMLDOC01-appb-C000001
     (wherein 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 is , represents an integer from 0 to 100.)
  6. 　前記エポキシ化合物Ｃが、下記式（ｂ２）で表される化合物を含有する、請求項１又は２に記載の硬化性組成物。
    Figure JPOXMLDOC01-appb-C000002
     （式中、Ｒａは、各々独立して、炭素数１～１０のアルキル基又は水素原子を表す。）     The curable composition according to claim 1 or 2, wherein the epoxy compound C contains a compound represented by the following formula (b2).
    Figure JPOXMLDOC01-appb-C000002
     (In the formula, each R a independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom.)
  7. 　前記エポキシ化合物Ｃの含有量が、前記エポキシ変性シリコーンＢ及び前記エポキシ化合物Ｃの合計量１００質量％に対して、２０～５０質量％である、請求項１又は２に記載の硬化性組成物。 The curable composition according to claim 1 or 2, wherein the content of the epoxy compound C is 20 to 50% by mass with respect to 100% by mass of the total amount of the epoxy-modified silicone B and the epoxy compound C.
  8. 　前記酸無水物Ｄは、無水フタル酸、無水コハク酸、無水マレイン酸、ナジック酸無水物及びｃｉｓ－４－シクロヘキセン－１，２－ジカルボン酸無水物からなる群より選択される１種以上である、請求項１又は２の硬化性組成物。 The acid anhydride D is one or more selected from the group consisting of phthalic anhydride, succinic anhydride, maleic anhydride, nadic anhydride and cis-4-cyclohexene-1,2-dicarboxylic anhydride. The curable composition of claim 1 or 2.
  9. 　アルケニルフェノールＡに由来する構成単位と、エポキシ変性シリコーンＢに由来する構成単位と、エポキシ化合物Ｃに由来する構成単位と、酸無水物Ｄに由来する構成単位と、を含有する重合体Ｅを含む、硬化性組成物。 A polymer E containing 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 acid anhydride D. , a curable composition.
  10. 　前記重合体Ｅの重量平均分子量が、３．０×１０３～５．０×１０４である、請求項９に記載の硬化性組成物。 10. The curable composition according to claim 9, wherein the polymer E has a weight average molecular weight of 3.0×10 3 to 5.0×10 4 .
  11. 　前記重合体Ｅ中の前記エポキシ変性シリコーンＢに由来する構成単位の含有量が、前記重合体Ｅの総質量に対して、２０～６０質量％である、請求項９又は１０に記載の硬化性組成物。 The curability according to claim 9 or 10, wherein the content of the constituent units derived from the epoxy-modified silicone B in the polymer E is 20 to 60% by mass with respect to the total mass of the polymer E. Composition.
  12. 　前記重合体Ｅのアルケニル基当量が、３００～１５００ｇ／ｍｏｌである、請求項９又は１０に記載の硬化性組成物。 The curable composition according to claim 9 or 10, wherein said polymer E has an alkenyl group equivalent weight of 300 to 1500 g/mol.
  13. 　前記重合体Ｅ中の前記酸無水物Ｄに由来する構成単位の含有量が、前記重合体Ｅの総質量に対して、３～２０質量％である、請求項９又は１０に記載の硬化性組成物。 The curability according to claim 9 or 10, wherein the content of structural units derived from the acid anhydride D in the polymer E is 3 to 20% by mass with respect to the total mass of the polymer E. Composition.
  14. 　前記重合体Ｅの含有量が、樹脂固形分１００質量％に対して５～５０質量％である、請求項９又は１０に記載の硬化性組成物。 The curable composition according to claim 9 or 10, wherein the content of the polymer E is 5 to 50% by mass with respect to 100% by mass of the resin solid content.
  15. 　前記アルケニルフェノールＡが、ジアリルビスフェノール及び／又はジプロペニルビスフェノールを含有する、請求項９又は１０に記載の硬化性組成物。 The curable composition according to claim 9 or 10, wherein said alkenylphenol A contains diallyl bisphenol and/or dipropenyl bisphenol.
  16. 　前記エポキシ変性シリコーンＢが、１４０～２５０ｇ／ｍｏｌのエポキシ当量を有するエポキシ変性シリコーンを含有する、請求項９又は１０に記載の硬化性組成物。 The curable composition according to claim 9 or 10, wherein the epoxy-modified silicone B contains an epoxy-modified silicone having an epoxy equivalent of 140 to 250 g/mol.
  17. 　前記エポキシ変性シリコーンＢが、下記式（１）で表されるエポキシ変性シリコーンを含有する、請求項９又は１０に記載の硬化性組成物。
    Figure JPOXMLDOC01-appb-C000003
     （式中、Ｒ１は、各々独立に、単結合、アルキレン基、アリーレン基又はアラルキレン基を示し、Ｒ２は、各々独立に、炭素数１～１０のアルキル基又はフェニル基を示し、ｎは、０～１００の整数を示す。）     The curable composition according to claim 9 or 10, wherein the epoxy-modified silicone B contains an epoxy-modified silicone represented by the following formula (1).
    Figure JPOXMLDOC01-appb-C000003
     (wherein 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 is , represents an integer from 0 to 100.)
  18. 　前記エポキシ化合物Ｃが、下記式（ｂ２）で表される化合物を含有する、請求項９又は１０に記載の硬化性組成物。
    Figure JPOXMLDOC01-appb-C000004
     （式中、Ｒａは、各々独立して、炭素数１～１０のアルキル基又は水素原子を表す。）     The curable composition according to claim 9 or 10, wherein the epoxy compound C contains a compound represented by the following formula (b2).
    Figure JPOXMLDOC01-appb-C000004
     (In the formula, each R a independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom.)
  19. 　前記酸無水物Ｄは、無水フタル酸、無水コハク酸、無水マレイン酸、ナジック酸無水物及びｃｉｓ－４－シクロヘキセン－１，２－ジカルボン酸無水物からなる群より選択される１種以上である、請求項９又は１０の硬化性組成物。 The acid anhydride D is one or more selected from the group consisting of phthalic anhydride, succinic anhydride, maleic anhydride, nadic anhydride and cis-4-cyclohexene-1,2-dicarboxylic anhydride. 11. The curable composition of claim 9 or 10.
  20. 　さらに、エポキシ化合物Ｃを含み、前記エポキシ化合物Ｃが、下記式（３－３）で表される化合物又は下記式（３－４）で表される化合物を含む、請求項９又は１０に記載の硬化性組成物。
    Figure JPOXMLDOC01-appb-C000005
     （式中、Ｒ１３は、各々独立して、水素原子、炭素数１～３のアルキル基又は炭素数２～３のアルケニル基を表す。）
    Figure JPOXMLDOC01-appb-C000006
     （式中、Ｒ１４は、各々独立して、水素原子、炭素数１～３のアルキル基又は炭素数２～３のアルケニル基を表す。）     Further comprising an epoxy compound C, the epoxy compound C comprises a compound represented by the following formula (3-3) or a compound represented by the following formula (3-4), according to claim 9 or 10 Curable composition.
    Figure JPOXMLDOC01-appb-C000005
     (In the formula, each R 13 independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or an alkenyl group having 2 to 3 carbon atoms.)
    Figure JPOXMLDOC01-appb-C000006
     (In the formula, each R 14 independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkenyl group having 2 to 3 carbon atoms.)
  21. 　マレイミド化合物、シアン酸エステル化合物、アルケニルフェノールＡ以外のフェノール化合物Ａ’及びアルケニル置換ナジイミド化合物からなる群より選択される少なくとも１種の化合物Ｆを更に含む、請求項１又は９に記載の硬化性組成物。 The curable composition according to claim 1 or 9, further comprising at least one compound F selected from the group consisting of maleimide compounds, cyanate ester compounds, phenol compounds A' other than alkenylphenol A, and alkenyl-substituted nadimide compounds. thing.
  22. 　前記マレイミド化合物が、ビス（４－マレイミドフェニル）メタン、２，２－ビス｛４－（４－マレイミドフェノキシ）－フェニル｝プロパン、ビス（３－エチル－５－メチル－４－マレイミドフェニル）メタン、下記式（３）で表されるマレイミド化合物及び下記式（３’）で表されるマレイミド化合物からなる群より選ばれる少なくとも１種を含む、請求項２１に記載の硬化性組成物。
    Figure JPOXMLDOC01-appb-C000007
     （式中、Ｒ５は、各々独立して、水素原子又はメチル基を表し、ｎ１は１以上の整数を表す。）
    Figure JPOXMLDOC01-appb-C000008
     （式（３’）中、Ｒ１３は各々独立に、水素原子、炭素数１～５のアルキル基、又はフェニル基を示し、ｎ４は１以上１０以下の整数を示す。）     The maleimide compound is bis(4-maleimidophenyl)methane, 2,2-bis{4-(4-maleimidophenoxy)-phenyl}propane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, The curable composition according to claim 21, comprising at least one selected from the group consisting of a maleimide compound represented by the following formula (3) and a maleimide compound represented by the following formula (3').
    Figure JPOXMLDOC01-appb-C000007
     (In the formula, each R 5 independently represents a hydrogen atom or a methyl group, and n 1 represents an integer of 1 or more.)
    Figure JPOXMLDOC01-appb-C000008
     (In 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.)
  23. 　前記シアン酸エステル化合物が、下記式（４）で表される化合物及び／又は下記式（４）で表される化合物を除く下記式（５）で表される化合物を含む、請求項２１に記載の硬化性組成物。
    Figure JPOXMLDOC01-appb-C000009
     （式中、Ｒ６は、各々独立して、水素原子又はメチル基を示し、ｎ２は１以上の整数を表す。）
    Figure JPOXMLDOC01-appb-C000010
     （式中、Ｒｙａは、各々独立して、炭素数２～８のアルケニル基又は水素原子を表し、Ｒｙｂは、各々独立して、炭素数１～１０のアルキル基又は水素原子を表し、Ｒｙｃは、各々独立して、炭素数４～１２の芳香環を表し、Ｒｙｃは、ベンゼン環と縮合構造を形成してもよく、Ｒｙｃは、存在していてもよく、存在していなくてもよく、Ａ１ａは、各々独立して、炭素数１～６のアルキレン基、炭素数７～１６のアラルキレン基、炭素数６～１０のアリーレン基、フルオレニリデン基、スルホニル基、酸素原子、硫黄原子又は単結合を表し、Ｒｙｃが存在しない場合は、１つのベンゼン環にＲｙａ及び／又はＲｙｂの基を２つ以上有してもよく、ｎは、１～２０の整数を表す。）     According to claim 21, wherein the cyanate ester compound includes a compound represented by the following formula (5) excluding the compound represented by the following formula (4) and/or the compound represented by the following formula (4). curable composition.
    Figure JPOXMLDOC01-appb-C000009
     (In the formula, each R6 independently represents a hydrogen atom or a methyl group, and n2 represents an integer of 1 or more.)
    Figure JPOXMLDOC01-appb-C000010
     (wherein R ya each independently represents an alkenyl group having 2 to 8 carbon atoms or a hydrogen atom, each R yb independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom, Each R yc independently represents an aromatic ring having 4 to 12 carbon atoms, R yc may form a condensed structure with a benzene ring, 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, an oxygen atom, represents a sulfur atom or a single bond, and when R yc does not exist, one benzene ring may have two or more R ya and/or R yb groups, and n represents an integer of 1 to 20 .)
  24. 　前記フェノール化合物Ａ’が、下記式（８）で表される化合物を含む、請求項２１に記載の硬化性組成物。
    Figure JPOXMLDOC01-appb-C000011
     （式中、Ｒ７は、各々独立して、水素原子又はメチル基を示し、ｎ３は１以上の整数を表す。）     The curable composition according to claim 21, wherein the phenolic compound A' contains a compound represented by the following formula (8).
    Figure JPOXMLDOC01-appb-C000011
     (In the formula, each R 7 independently represents a hydrogen atom or a methyl group, and n 3 represents an integer of 1 or more.)
  25. 　無機充填材を更に含有し、前記無機充填材の含有量が、樹脂固形分１００質量部に対し５０～１０００質量部である、請求項１又は９に記載の硬化性組成物。 The curable composition according to claim 1 or 9, which further contains an inorganic filler, 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.
  26. 　前記無機充填材が、シリカ類、ベーマイト及びアルミナからなる群より選択される１種以上を含む、請求項２５に記載の硬化性組成物。 The curable composition according to claim 25, wherein the inorganic filler contains one or more selected from the group consisting of silicas, boehmite and alumina.
  27. 　プリント配線板用である、請求項１又は９に記載の硬化性組成物。 The curable composition according to claim 1 or 9, which is for printed wiring boards.
  28. 　基材と、前記基材に含浸又は塗布された請求項１又は９に記載の硬化性組成物と、を含む、プリプレグ。 A prepreg comprising a base material and the curable composition according to claim 1 or 9 impregnated or applied to the base material.
  29. 　支持体と、前記支持体の表面に配置された請求項１又は９に記載の硬化性組成物と、を含む、レジンシート。 A resin sheet comprising a support and the curable composition according to claim 1 or 9 disposed on the surface of said support.
  30. 　請求項２８に記載のプリプレグを用いて形成された積層体と、
    　前記積層体の片面又は両面に配置された金属箔と、
    を含む、金属箔張積層板。     A laminate formed using the prepreg according to claim 28;
    a metal foil disposed on one side or both sides of the laminate;
    A metal foil clad laminate comprising:
  31. 　請求項２９に記載のレジンシートを用いて形成された積層体と、
    　前記積層体の片面又は両面に配置された金属箔と、
    を含む、金属箔張積層板。     A laminate formed using the resin sheet according to claim 29,
    a metal foil disposed on one side or both sides of the laminate;
    A metal foil clad laminate comprising:
  32. 　請求項２８に記載のプリプレグを用いて形成された絶縁層と、
    　前記絶縁層の表面に形成された導体層と、
    を有する、プリント配線板。     an insulating layer formed using the prepreg according to claim 28;
    a conductor layer formed on the surface of the insulating layer;
    A printed wiring board.
  33. 　請求項２９に記載のレジンシートを用いて形成された絶縁層と、
    　前記絶縁層の表面に形成された導体層と、
    を有する、プリント配線板。     An insulating layer formed using the resin sheet according to claim 29,
    a conductor layer formed on the surface of the insulating layer;
    A printed wiring board.
  34. 　アルケニルフェノールＡと、エポキシ変性シリコーンＢと、エポキシ化合物Ｃと、を重合して得られるプレポリマーを得る工程と、
    　前記プレポリマーに対して酸無水物Ｄを反応させる工程と、
    を含む、請求項１又は９に記載の硬化性組成物の製造方法。     obtaining a prepolymer obtained by polymerizing alkenylphenol A, epoxy-modified silicone B, and epoxy compound C;
    a step of reacting an acid anhydride D with the prepolymer;
    A method for producing a curable composition according to claim 1 or 9, comprising.
PCT/JP2022/029878 2021-08-05 2022-08-04 Curable composition, prepreg, resin sheet, metal foil–clad laminate, and printed wiring board WO2023013715A1 (en)

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JPH0547964A (en) * 1990-12-25 1993-02-26 Sumitomo Bakelite Co Ltd Resin composition for semiconductor sealing
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