WO2024090410A1 - Composition de résine, produit durci, préimprégné, carte stratifiée revêtue de feuille métallique, feuille composite de résine et carte de circuit imprimé - Google Patents

Composition de résine, produit durci, préimprégné, carte stratifiée revêtue de feuille métallique, feuille composite de résine et carte de circuit imprimé Download PDF

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Publication number
WO2024090410A1
WO2024090410A1 PCT/JP2023/038272 JP2023038272W WO2024090410A1 WO 2024090410 A1 WO2024090410 A1 WO 2024090410A1 JP 2023038272 W JP2023038272 W JP 2023038272W WO 2024090410 A1 WO2024090410 A1 WO 2024090410A1
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group
compound
resin composition
mass
carbon atoms
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PCT/JP2023/038272
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English (en)
Japanese (ja)
Inventor
直也 ▲徳▼永
克哉 山本
恵一 長谷部
宇志 小林
悠仁 鎌田
将太 古賀
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三菱瓦斯化学株式会社
Ｍｇｃエレクトロテクノ株式会社
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Publication of WO2024090410A1 publication Critical patent/WO2024090410A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/088—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 polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/28—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer impregnated with or embedded in a plastic substance
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/36—Amides or imides
    • C08F222/40—Imides, e.g. cyclic imides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/016—Flame-proofing or flame-retarding additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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

Definitions

  • the present invention relates to a resin composition, a cured product, a prepreg, a metal foil-clad laminate, a resin composite sheet, and a printed wiring board.
  • semiconductor package laminates e.g., metal foil-clad laminates, etc.
  • the main properties required include, for example, peel strength, low water absorption, chemical resistance, desmear resistance, flame resistance, low dielectric properties (low dielectric constant and/or low dielectric tangent), low thermal expansion, heat resistance, etc.
  • Patent Document 1 discloses a resin composition containing a polyfunctional vinyl aromatic polymer (A) and a maleimide compound (B), the maleimide compound (B) containing at least one compound represented by any one of the following formulas (1) to (4).
  • R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a phenyl group, and n1 represents a number of 1 to 10.
  • each R 6 independently represents a methyl group or an ethyl group
  • each R 7 independently represents a hydrogen atom or a methyl group.
  • each R8 independently represents a hydrogen atom, a methyl group, or an ethyl group.
  • each R 9 independently represents a hydrogen atom, a methyl group, or an ethyl group.
  • Patent Document 2 discloses a maleimide having an indane skeleton represented by the following general formula (1).
  • each Ra independently represents an alkyl group, an alkyloxy group, or an alkylthio group having 1 to 10 carbon atoms, an aryl group, an aryloxy group, or an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a nitro group, a hydroxyl group, or a mercapto group;
  • q represents an integer value of 0 to 4.
  • each Ra may be the same or different within the same ring; each Rb independently represents an alkyl group, an alkyloxy group, or an alkylthio group having 1 to 10 carbon atoms, an aryl group, an aryloxy group, or an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a hydroxyl group, or a mercapto group; r represents an integer value of 0 to 3. When r is 2 or 3, each Rb may be the same or different within the same ring; n represents the average number of repeating units and represents a numerical value of 0.95 to 10.0.)
  • the present invention aims to solve these problems, and to provide a novel resin composition that can provide a cured product with low dielectric properties, as well as a cured product, a prepreg, a metal foil-clad laminate, a resin composite sheet, and a printed wiring board.
  • a polymerizable composition comprising a polymaleimide compound (A) and a maleimide compound (B) other than the polymaleimide compound (A),
  • the polymaleimide compound (A) is produced by reacting, as reaction raw materials (1), an aromatic amine compound (a1) having 1 to 3 alkyl groups on an aromatic ring, an aromatic divinyl compound (a2) having two ethenyl groups, and maleic anhydride. Resin composition.
  • ⁇ 2> The resin composition according to ⁇ 1>, in which a cured product of the maleimide compound (B) other than the polymaleimide compound (A) has a dielectric loss tangent (Df) of 0.003 or less at a frequency of 10 GHz, as measured according to a cavity resonator perturbation method, and a relative dielectric constant (Dk) of 2.5 or less.
  • Df dielectric loss tangent
  • Dk relative dielectric constant
  • R M5 and R M6 each independently represent a hydrogen atom or an alkyl group.
  • Ar M represents a divalent aromatic group.
  • A represents a 4- to 6-membered alicyclic group.
  • R M7 and R M8 each independently represent an alkyl group.
  • mx is 1 or 2
  • lx is 0 or 1.
  • R M9 and R M10 each independently represent a hydrogen atom or an alkyl group.
  • R M11 , R M12 , R M13 , and R M14 each independently represent a hydrogen atom or an organic group.
  • Each M15 independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a halogen atom, a hydroxyl group, or a mercapto group.
  • px represents an integer of 0 to 3.
  • nx represents an integer of 1 to 20.
  • ⁇ 4> The resin composition according to any one of ⁇ 1> to ⁇ 3>, wherein the content of the polymaleimide compound (A) is 1 to 90 parts by mass when the resin solid content in the resin composition is 100 parts by mass.
  • ⁇ 5> The resin composition according to any one of ⁇ 1> to ⁇ 4>, wherein a content of the maleimide compound (B) other than the polymaleimide compound (A) is 1 to 90 parts by mass when a resin solid content in the resin composition is 100 parts by mass.
  • ⁇ 6> The resin composition according to any one of ⁇ 1> to ⁇ 5>, further comprising a compound (C) containing two or more polymerizable carbon-carbon unsaturated double bonds.
  • the compound (C) containing two or more polymerizable carbon-carbon unsaturated double bonds includes at least one selected from the group consisting of a compound containing a vinylaryl group, a compound containing a (meth)acryloyl group, and a compound containing a (meth)allyl group.
  • ⁇ 8> The resin composition according to ⁇ 6> or ⁇ 7>, wherein the compound (C) containing two or more polymerizable carbon-carbon unsaturated double bonds includes a compound containing a (meth)allyl group.
  • the compound containing a (meth)allyl group includes at least one selected from the group consisting of an allyl isocyanurate compound, an allyl group-substituted nadimide compound, an allyl compound having a glycoluril structure, and a diallyl phthalate.
  • the filler (E) includes at least one selected from the group consisting of silica, aluminum hydroxide, aluminum nitride, boron nitride, forsterite, titanium oxide, barium titanate, strontium titanate, and calcium titanate.
  • ⁇ 14> The resin composition according to any one of ⁇ 1> to ⁇ 13>, further comprising 0.5 to 30 parts by mass of a monomer or oligomer having an ethylenically unsaturated group per 100 parts by mass of a resin solid content in the resin composition.
  • ⁇ 15> The resin composition according to any one of ⁇ 1> to ⁇ 14>, further comprising a flame retardant, wherein the flame retardant comprises a phosphorus-based flame retardant.
  • the maleimide compound (B) other than the polymaleimide compound (A) contains a compound represented by formula (M1), Further, the compound (C) contains two or more polymerizable carbon-carbon unsaturated double bonds, the compound (C) containing two or more polymerizable carbon-carbon unsaturated double bonds includes at least one selected from the group consisting of a compound containing a vinylaryl group, a compound containing a (meth)acryloyl group, and a compound containing a (meth)allyl group; the content of the polymaleimide compound (A) is 1 to 90 parts by mass relative to 100 parts by mass of a resin solid content in the resin composition, the content of the maleimide compound (B) other than the polymaleimide compound (A) is 1 to 90 parts by mass when the resin solid content in the resin composition is 100 parts by mass, Further, the composition contains a filler (E), The filler (E) contains one or more selected from the group consisting of silica, aluminum hydroxide, aluminum
  • R M1 , R M2 , R M3 , and R M4 each independently represent a hydrogen atom or an organic group.
  • R M5 and R M6 each independently represent a hydrogen atom or an alkyl group.
  • Ar M represents a divalent aromatic group.
  • A represents a 4- to 6-membered alicyclic group.
  • R M7 and R M8 each independently represent an alkyl group.
  • mx is 1 or 2
  • lx is 0 or 1.
  • R M9 and R M10 each independently represent a hydrogen atom or an alkyl group.
  • R M11 , R M12 , R M13 , and R M14 each independently represent a hydrogen atom or an organic group.
  • Each M15 independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a halogen atom, a hydroxyl group, or a mercapto group.
  • px represents an integer of 0 to 3.
  • the compound (C) containing two or more polymerizable carbon-carbon unsaturated double bonds includes a compound containing a (meth)allyl group, the compound containing a (meth)allyl group includes at least one selected from the group consisting of an allyl isocyanurate compound, an allyl group-substituted nadimide compound, an allyl compound having a glycoluril structure, and a diallyl phthalate;
  • each R 1 independently represents an alkyl group having 1 to 10 carbon atoms
  • each R 2 independently represents an alkyl group, alkoxy group, or alkylthio group having 1 to 10 carbon atoms
  • a halogen atom a hydroxyl group; or a mercapto group
  • R 3 , R 4 , R 5 and R 6 each independently represent a hydrogen atom or a methyl group, provided that one of R 3 and R 4 is a hydrogen atom and the other is a methyl group, one of R 5 and R 6 is a hydrogen atom and the other is a methyl group
  • X1 is represented
  • ⁇ 22> The resin composition according to any one of ⁇ 1> to ⁇ 21>, which is for a printed wiring board.
  • ⁇ 23> A cured product of the resin composition according to any one of ⁇ 1> to ⁇ 22>.
  • ⁇ 24> A prepreg formed from a substrate and the resin composition according to any one of ⁇ 1> to ⁇ 21>.
  • ⁇ 25> A metal foil-clad laminate comprising at least one prepreg according to ⁇ 24> and a metal foil arranged on one or both sides of the prepreg.
  • ⁇ 26> A resin composite sheet comprising a support and a layer formed from the resin composition according to any one of ⁇ 1> to ⁇ 21>, which is disposed on a surface of the support.
  • a printed wiring board including an insulating layer and a conductor layer disposed on a surface of the insulating layer, The printed wiring board, wherein the insulating layer includes a layer formed from the resin composition according to any one of ⁇ 1> to ⁇ 21>.
  • the present invention makes it possible to provide a resin composition that can produce a new low-dielectric cured product, as well as a cured product, a prepreg, a metal foil-clad laminate, a resin composite sheet, and a printed wiring board.
  • the present embodiment is an example for explaining the present invention, and the present invention is not limited to the present embodiment.
  • the word "to” is used to mean that the numerical values before and after it are included as the lower limit and upper limit.
  • various physical properties and characteristic values are those at 23° C. unless otherwise specified.
  • groups (atomic groups) in this specification the notation that does not indicate substitution or non-substitution includes both groups (atomic groups) that have no substituents and groups (atomic groups) that have substituents.
  • alkyl group includes not only alkyl groups that have no substituents (unsubstituted alkyl groups) but also alkyl groups that have substituents (substituted alkyl groups).
  • vinyl group includes not only vinyl groups that have no substituents (unsubstituted vinyl groups) but also vinyl groups that have substituents (substituted vinyl groups). In this specification, the notation that does not indicate substitution or non-substitution is preferably non-substituted.
  • (meth)allyl represents both or either of allyl and methallyl, with allyl being preferred
  • (meth)acryloyl represents both or either of acryloyl and methacryloyl, with methacryloyl being preferred.
  • the relative dielectric constant refers to the ratio of the dielectric constant of a substance to the dielectric constant of a vacuum.
  • the relative dielectric constant may be simply referred to as the "dielectric constant.”
  • parts by mass indicates the relative amount of a component
  • % by mass indicates the absolute amount of a component.
  • the resin solids refers to components excluding the filler (E) and the solvent, and is intended to include the polymaleimide compound (A), the maleimide compound (B) other than the polymaleimide compound (A), as well as the compound (C) containing two or more carbon-carbon unsaturated double bonds, other resin components (D), monomers or oligomers having an ethylenically unsaturated group, silane coupling agents, and other components (additives such as dispersants and flame retardants, etc.) that are blended as necessary. If the measurement methods, etc. described in the standards shown in this specification vary from year to year, they will be based on the standards as of January 1, 2022, unless otherwise specified.
  • the polymaleimide compound (A) includes a compound having one or more maleimide groups, and is preferably a compound having two or more maleimide groups.
  • the resin composition of this embodiment contains a polymaleimide compound (A) and a maleimide compound (B) other than the polymaleimide compound (A), and the polymaleimide compound (A) is characterized in that the reaction raw materials (1) are an aromatic amine compound (a1) having 1 to 3 alkyl groups on the aromatic ring, an aromatic divinyl compound (a2) having two ethenyl groups, and maleic anhydride.
  • the reaction raw materials (1) are an aromatic amine compound (a1) having 1 to 3 alkyl groups on the aromatic ring, an aromatic divinyl compound (a2) having two ethenyl groups, and maleic anhydride.
  • the resin composition of the present embodiment contains a polymaleimide compound (A) having, as reaction raw materials (1), an aromatic amine compound (a1) having 1 to 3 alkyl groups on an aromatic ring, an aromatic divinyl compound (a2) having two ethenyl groups, and maleic anhydride.
  • a polymaleimide compound (A) having, as reaction raw materials (1), an aromatic amine compound (a1) having 1 to 3 alkyl groups on an aromatic ring, an aromatic divinyl compound (a2) having two ethenyl groups, and maleic anhydride.
  • the polymaleimide compound (A) is a compound having an aromatic amine compound (a1) having 1 to 3 alkyl groups (hereinafter also referred to as "aromatic amine compound (a1)”), an aromatic divinyl compound (a2) having two ethenyl groups (hereinafter also referred to as aromatic divinyl compound (a2)), and maleic anhydride as reaction raw materials (1).
  • aromatic amine compound (a1) aromatic amine compound having 1 to 3 alkyl groups
  • aromatic divinyl compound (a2) having two ethenyl groups
  • maleic anhydride as reaction raw materials (1).
  • an aromatic monovinyl compound (a3) having one ethenyl group (hereinafter also referred to as aromatic monovinyl compound (a3)) may be further contained in the reaction raw material (1).
  • the polymaleimide compound (A) of this embodiment is preferably a polymaleimide compound having an intermediate amine compound (C) in which aromatic amine compounds (a1) having 1 to 3 alkyl groups are crosslinked with each other via an aromatic divinyl compound (a2) having two ethenyl groups, and maleic anhydride as reaction raw materials (3).
  • the intermediate amine compound (C) is preferably a compound in which an aromatic amine compound (a1) having 1 to 3 alkyl groups, an aromatic divinyl compound (a2) having two ethenyl groups, and an aromatic monovinyl compound (a3) having one ethenyl group added as necessary are used as reaction raw materials (2).
  • the intermediate amine compound (C) in this embodiment preferably has a structure in which a structural unit of an aromatic amine compound (a1) having an aromatic ring to which an amino group (including a substituted amino group in which a hydrogen atom of the amino group is further substituted with an alkyl group having 1 to 6 carbon atoms) is bonded and one to three alkyl groups on the aromatic ring is linked by a chemical bond to a structural unit of an aromatic divinyl compound (a2) having two ethenyl groups, and if necessary, a structural unit of an aromatic monovinyl compound (a3) is chemically bonded to the aromatic ring in the structural unit of the aromatic amine compound (a1).
  • the polymaleimide compound (A) in this embodiment has a structure in which an amino group (including -NH2 and a substituted amino group) bonded to the aromatic ring of the intermediate amine compound (C) is substituted with an N-substituted maleimide ring.
  • the "polymaleimide compound (A)" in this embodiment and the “intermediate amine compound (C)" which is a precursor of the “polymaleimide compound (A)” are polymer compounds which differ in that the amino group (including --NH2 and a substituted amino group) bonded to the aromatic ring is replaced with an N-substituted maleimide ring.
  • the structural unit of the aromatic amine compound (a1) refers to a group obtained by removing two hydrogen atoms from the aromatic ring of the aromatic amine compound (a1).
  • the aromatic amine compound (a1) when the aromatic amine compound (a1) is represented by the formula (a) described below, the group obtained by removing two hydrogen atoms from the benzene ring of the formula (a) is called the structural unit of the aromatic amine compound (a1).
  • the structural unit of the aromatic divinyl compound (a2) refers to a group obtained by cleaving the unsaturated bonds of two ethenyl groups of the aromatic divinyl compound (a2).
  • the aromatic amine compound (a1) having a specific aromatic ring structure is used as the reaction raw material, it becomes easier to control the reaction site with the aromatic divinyl compound (a2) described below, and therefore it becomes easier to obtain a polymaleimide compound (A) having a uniform chemical structure or chain length. As a result, it is possible to provide a polymaleimide compound (A) that exhibits a low moisture absorption rate and a low dielectric tangent when cured.
  • each R 1 independently represents an alkyl group
  • each R 2 independently represents an alkyl group, an alkoxy group, or an alkylthio group having 1 to 10 carbon atoms
  • a halogen atom a hydroxyl group; or a mercapto group
  • R 3 , R 4 , R 5 and R 6 each independently represent a hydrogen atom or a methyl group, provided that one of R 3 and R 4 is a hydrogen atom and the other is a methyl group, one of R 5 and R 6 is a hydrogen atom and the other is a methyl group
  • X1 is represented by the following formula (x): (In formula (x),
  • * in formula (1) represents a bond to another atom.
  • r is the average number of substitutions of X1 per benzene ring to which X1 is bonded and is a number from 0 to 4
  • p is an integer from 1 to 3
  • q is an integer from 0 to 4
  • k is an integer from 1 to 100.
  • the multiple R 1s may be the same or different from each other.
  • q is an integer of 2 or more
  • the multiple R 2s may be the same or different from each other.
  • t is an integer of 2 or more
  • the multiple R 9s may be the same or different from each other.
  • R 1 each independently represents preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, further preferably an alkyl group having 1 to 3 carbon atoms, and may be an alkyl group having 1 to 2 carbon atoms.
  • p is an integer of 2 or more
  • a plurality of R 1 may be the same or different.
  • Preferred R 1 in formula (1) is a methyl group, an ethyl group, or an n-propyl group, and may be a methyl group and/or an ethyl group.
  • the benzene ring to which R 1 in formula (1) is bonded may be the benzene ring of the aromatic amine compound (a1).
  • p preferably represents 1 or 2, and more preferably 1.
  • p 1, the molecular weight distribution of the resulting polymaleimide compound (A) can be increased, and the moisture absorption rate and dimensional change rate of the resulting cured product tend to be reduced.
  • R 1 in formula (1) it is preferable that R 1 is bonded to at least one of the 2nd, 3rd, 4th, 5th or 6th positions relative to the maleimide group, more preferably that R 1 is bonded to at least one of the 2nd, 3rd, 4th or 6th positions, and even more preferably that R 1 is bonded to at least one of the 2nd or 6th positions.
  • R 1 By bonding R 1 to at least one of the 2nd or 6th positions relative to the maleimide group, there is a tendency for low dielectric properties (low dielectric constant and/or low dielectric loss tangent) to be excellent.
  • p 2nd and 6th positions, or the 2nd and 3rd positions relative to the maleimide group.
  • a specific example is, for example, an embodiment in which methyl groups are bonded to the 2nd and 6th positions relative to the maleimide group.
  • R 1 when p is 1, it is preferable that R 1 is bonded to the 2nd position relative to the maleimide group.
  • R 2 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms; an aryl group having 6 to 10 carbon atoms; a cycloalkyl group having 3 to 10 carbon atoms; a halogen atom; or a hydroxyl group, more preferably an alkyl group having 1 to 10 carbon atoms, and even more preferably an alkyl group having 1 to 6 carbon atoms.
  • q is an integer of 2 or more, the multiple R 2s may be the same or different from each other.
  • a preferred R 2 in formula (1) is a methyl group, an ethyl group, or an n-propyl group.
  • the benzene ring to which R 2 in formula (1) is bonded may be the benzene ring of the aromatic divinyl compound (a2).
  • q preferably represents 0, 1, or 2.
  • one of R 3 and R 4 is a hydrogen atom, the other is a methyl group, and one of R 5 and R 6 is a hydrogen atom, the other is a methyl group. This allows the reactivity of the unsaturated bond in the polymaleimide compound (A) itself to be maintained at a high level.
  • R 9 preferably represents, independently of one another, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms; an aryl group having 6 to 10 carbon atoms; a cycloalkyl group having 3 to 10 carbon atoms; a halogen atom; or a hydroxyl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, even more preferably an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms, even more preferably an alkyl group having 1 to 10 carbon atoms, and even more preferably an alkyl group having 1 to 6 carbon atoms.
  • t preferably represents an integer of 0 to 4, and more preferably an integer of 0 to 3.
  • r means the average number of substitutions of X1 per benzene ring to which X1 is bonded, and is a number in the range of 0 to 4, more preferably a number in the range of 0 to 3, and may be a number in the range of 0 to 2.
  • k represents the number of repeating units and is an integer from 1 to 100, preferably an integer from 1 to 90, more preferably an integer from 1 to 80, and may be an integer from 1 to 50 or an integer from 1 to 20.
  • the polymaleimide compound (A) in the present embodiment preferably contains an indane skeleton (or a structural unit having an indane skeleton) in an amount of 10 mass% or less, more preferably 5 mass% or less, even more preferably 3 mass% or less, even more preferably 2 mass% or less, and particularly preferably 0.9 mass% or less, relative to the total amount (100 mass%) of the polymaleimide compound (A).
  • the structural unit having an indane skeleton is preferably represented by the following formula (3).
  • R 31 , R 32 and R 33 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
  • R 34 each independently represent an alkyl group, alkoxy group or alkylthio group having 1 to 10 carbon atoms; an aryl group, aryloxy group or arylthio group having 6 to 10 carbon atoms; a cycloalkyl group having 3 to 10 carbon atoms; a halogen atom; a hydroxyl group; or a mercapto group
  • q 3 represents an integer of 0 to 3
  • q 3 is an integer of 2 or more, a plurality of R 34s may be the same or different from each other.
  • R 34 each independently preferably represents an alkyl group having 1 to 6 carbon atoms, and more preferably represents an alkyl group having 1 to 3 carbon atoms.
  • R 31 , R 32 and R 33 each preferably represent a hydrogen atom or a methyl group.
  • the aromatic amine compound (a1) in this embodiment has an aromatic ring to which an amino group ( -NH2 or a substituted amino group) is bonded, and the aromatic ring has 1 to 3 alkyl groups bonded thereto. Therefore, the aromatic amine compound (a1) can be an amine-based compound.
  • the aromatic ring forming the central structure of the aromatic amine compound (a1) is preferably monocyclic, and includes an aromatic hydrocarbon ring and an aromatic heterocycle.
  • the aromatic hydrocarbon ring is preferably a benzene ring.
  • Examples of the aromatic heterocycle include a hetero six-membered ring such as a pyran ring or a pyridine ring.
  • the aromatic amine compound (a1) in this embodiment more preferably has an aromatic ring to which -NH2 is bonded that does not include a substituted amino group, and the aromatic ring has 1 to 3 alkyl groups bonded thereto.
  • the alkyl group substituted with 1 to 3 hydrogen atoms in the aromatic ring of the aromatic amine compound (a1) may be an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, or may be an alkyl group having 1 to 2 carbon atoms.
  • the alkyl group may be linear, branched, or cyclic.
  • Examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a s-butyl group, and a t-butyl group.
  • the smaller the molecular weight of the alkyl group the more remarkable the effect of the present invention (low dimensional change rate). Also, the higher the molecular weight of the alkyl group, the more remarkable the effect of the present invention (low moisture absorption).
  • the upper limit of the number of alkyl groups bonded to an aromatic ring having an amino group (including -NH2 and a substituted amino group) in the aromatic amine compound (a1) may be a number obtained by subtracting 3 from the number of substitutable ring-constituting atoms in the unsubstituted aromatic ring, from the viewpoint that the aromatic ring has an amino group (including -NH2 and a substituted amino group) and two bonds are used in polymerization.
  • the number of the alkyl groups is 3 or less.
  • the number of alkyl groups substituted on the aromatic ring of the aromatic amine compound (a1) 2 or more it becomes easier to control the reaction site with the aromatic divinyl compound (a2) described below, and therefore it becomes easier to obtain a polymaleimide compound (A) having a uniform chemical structure or chain length.
  • the cured product of the polymaleimide compound (A) tends to exhibit low moisture absorption and excellent high-frequency electrical properties.
  • a preferred embodiment of the aromatic amine compound (a1) in this embodiment will be described taking as an example a case where the aromatic ring of the aromatic amine compound (a1) is a benzene ring.
  • the aromatic ring of the aromatic amine compound (a1) is a benzene ring.
  • the carbon atom having the largest HOMO electron density (Huckel coefficient) among the carbon atoms in the benzene ring constituting the aromatic amine compound (a1) is unsubstituted, the carbocation of the aromatic divinyl compound (a2), which is the cationoid reagent, is likely to react with the carbon atom having the largest HOMO electron density. Therefore, by controlling the number and position of the alkyl groups bonded to the carbon atom of the benzene ring, the bond site or number of bonds with the aromatic divinyl compound (a2) can be adjusted. Therefore, it is speculated that the chemical structure or molecular chain length of the obtained polymaleimide compound (A) can be easily designed.
  • the aromatic amine compound (a1) has an aniline skeleton having one benzene ring and one amino group
  • a cationic reagent formed from an aromatic divinyl compound (a2) described below to attack at least one of the carbon atoms at the 2-, 4- and 6-positions, which are ortho and para positions with high electron density of the aniline nucleus.
  • the bonding site with the aromatic divinyl compound (a2) can be largely controlled, so that a polymaleimide compound (A) with a uniform chemical structure or chain length can be easily obtained.
  • a 2,6-dialkylamine is used as the aromatic amine compound (a1), it is considered that a large amount of polymaleimide compound (A) bonded to the aromatic divinyl compound (a2) at the 4-position can be obtained.
  • aromatic amine compound (a1) of this embodiment include, for example, dimethylaniline (2,3-xylidine, 2,4-xylidine, 2,6-xylidine, 3,4-xylidine, or 3,5-xylidine), diethylaniline (2,3-diethylaniline, 2,4-diethylaniline, 2,6-diethylaniline, 3,4-diethylaniline, or 3,5-diethylaniline), diisopropylaniline (2,3-diisopropylaniline, 2,4-diisopropylaniline, 2,6-diisopropylaniline, 3,4-diisopropylaniline, or 3,5-diisopropylaniline), ethylmethylaniline (for example, methyl groups at one of the 2,3-position, 2,4-position, 2,6-position, 3,4-position, or 3,5-position, and methyl groups at the other positions) and methylaniline (for
  • cyclobutylaniline is an ethyl group
  • cyclobutylaniline is an ethyl group
  • cyclopentylaniline is an cyclohexylaniline, o,m, or p-toluidine, o,m, or p-ethylaniline, o,m, or p-isopropylaniline, o,m, or p-propylaniline, o,m, or p-butylaniline
  • methylisopropylaniline for example, methylisopropylaniline in which one of the 2,3-positions, 2,4-positions, 2,6-positions, 3,4-positions, or 3,5-positions is a methyl group and the other is an isopropyl group
  • ethylbutylaniline for example, ethylbutylaniline in which one of the 2,3-positions, 2,4-positions, 2,6-positions,
  • the benzene ring and the five-membered ring of the maleimide are stable when aligned on the same plane, so stacking is likely to occur, resulting in high crystallinity. This causes poor solvent solubility.
  • an aromatic amine compound (a1) having an alkyl group with 1 to 6 carbon atoms is preferable to use, for example, an aromatic amine compound (a1) having an alkyl group with 1 to 6 carbon atoms.
  • the aromatic amine compound (a1) which is an essential component of the reaction raw material (1) in this embodiment, can be represented, for example, by the following formula (a).
  • R 1a each independently represents an alkyl group
  • p a represents an integer of 1 to 3.
  • a plurality of R 1a may be the same or different.
  • the alkyl group preferably represents an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, further preferably an alkyl group having 1 to 3 carbon atoms, and may be an alkyl group having 1 to 2 carbon atoms.
  • Examples of the alkyl group having 1 to 6 carbon atoms, the alkyl group having 1 to 3 carbon atoms, and the alkyl group having 1 to 2 carbon atoms are the same as those mentioned above.
  • p a is preferably 1 or 2. When there are a plurality of R 1a , they may be the same or different alkyl groups.
  • the aromatic amine compound (a1) represented by the above formula (a) may be used alone or in combination of two or more kinds.
  • the aromatic divinyl compound (a2) in this embodiment has two ethenyl groups (CH 2 ⁇ CH—) (also referred to as vinyl groups) as substituents on an aromatic ring, and can be used without any particular limitation as long as it can react with the aromatic amine compound (a1).
  • the reaction raw material (1) contains a mixture of the aromatic divinyl compound (a2) and the aromatic monovinyl compound (a3).
  • Examples of the aromatic divinyl compound (a2) include divinylbenzene, divinylbiphenyl, divinylnaphthalene, and various compounds in which an aromatic ring of these compounds is substituted with one or more substituents such as an alkyl group, alkoxy group, or alkylthio group having 1 to 10 carbon atoms; an aryl group, aryloxy group, or arylthio group having 6 to 10 carbon atoms; a cycloalkyl group having 3 to 10 carbon atoms; a halogen atom; a hydroxyl group; or a mercapto group.
  • the preferred form of the substituent is the same as R 2 in the above formula (1).
  • the alkyl group may be either a straight-chain type or a branched type.
  • the number of carbon atoms of the alkyl group or alkoxy group is preferably 1 to 4.
  • Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, and an isobutyl group.
  • the alkoxy group include a methoxy group, an ethoxy group, a propyloxy group, and a butoxy group.
  • the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.
  • the aromatic divinyl compound (a2) which is the reaction raw material (1) for the polymaleimide compound (A) in this embodiment is preferably represented by the following formula (b1).
  • R 2b each independently represents an alkyl group, alkoxy group, or alkylthio group having 1 to 10 carbon atoms; an aryl group, aryloxy group, or arylthio group having 6 to 10 carbon atoms; a cycloalkyl group having 3 to 10 carbon atoms; a halogen atom; a hydroxyl group; or a mercapto group, and q 1b represents an integer of 0 to 4.
  • q 1b is an integer of 2 or more, a plurality of R 2b may be the same or different.
  • R 2b in the above formula (b1) can correspond to R 2 in formula (1).
  • R 2b in the above formula (b1) each independently preferably represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, or a hydroxyl group, more preferably an alkyl group having 1 to 10 carbon atoms, and even more preferably an alkyl group having 1 to 6 carbon atoms.
  • q 1b is preferably an integer of 0 to 2.
  • a plurality of R b1 may be the same group or different groups.
  • aromatic divinyl compound (a2) of the present embodiment examples include 1,2-divinylbenzene, 1,3-divinylbenzene, 1,4-divinylbenzene, 2,5-dimethyl-1,4-divinylbenzene, 2,5-diethyl-1,4-divinylbenzene, cis,cis, ⁇ , ⁇ '-diethoxy-m-m-divinylbenzene, 1,4-divinyl-2,5-dibutylbenzene, 1,4-divinyl-2,5-dihexylbenzene, 1,4-divinyl-2,5-dimethoxybenzene, and derivatives thereof.
  • divinylnaphthalenes such as 1,3-divinylnaphthalene, 1,4-divinylnaphthalene, 1,5-divinylnaphthalene, 1,6-divinylnaphthalene, 1,7-divinylnaphthalene, 2,3-divinylnaphthalene, 2,6-divinylnaphthalene, 2,7-divinylnaphthalene, 3,4-divinylnaphthalene, 1,8-divinylnaphthalene, 1,5-dimethoxy-4,8-divinylnaphthalene, and compounds consisting of derivatives thereof, but are not limited thereto.
  • the aromatic divinyl compound (a2) may be used alone or in combination of two or more kinds.
  • the aromatic divinyl compound (a2) is preferably divinylbenzene or a compound having a substituent on its aromatic ring, and more preferably divinylbenzene.
  • the substitution position of the vinyl group of divinylbenzene is not particularly limited, but it is preferable that the meta form is the main component.
  • the content of the meta form in divinylbenzene is preferably 40 mass% or more, more preferably 50 mass% or more, based on the total amount of divinylbenzene.
  • the structural unit of the aromatic divinyl compound (a2) is preferably contained in an amount of 10 to 90 mass%, more preferably 20 to 90 mass%, relative to the total amount (100 mass%) of the polymaleimide compound (A).
  • the structural unit of the aromatic divinyl compound (a2) refers to a group obtained by removing two hydrogen atoms from each of the two ethenyl groups of the aromatic divinyl compound (a2) (a total of four hydrogen atoms).
  • the polymaleimide compound (A) may use other compounds as reaction raw materials in addition to the aromatic amine compound (a1), aromatic divinyl compound (a2) and maleic anhydride.
  • the other compounds include an aromatic monovinyl compound (a3) having one ethenyl group. That is, in the present embodiment, it is preferable to use the aromatic amine compound (a1), the aromatic divinyl compound (a2), the aromatic monovinyl compound (a3) and maleic anhydride as the reaction raw materials (1).
  • the polymaleimide compound (A) is preferably used in the present embodiment, since the cured product of the finally obtained polymaleimide compound (A) is excellent in terms of low dielectric tangent by using the aromatic monovinyl compound (a3) in addition to the aromatic amine compound (a1), aromatic divinyl compound (a2) and maleic anhydride as reaction raw materials.
  • the aromatic monovinyl compound (a3) also generates a carbocation like the aromatic divinyl compound (a2), and therefore is likely to react with the carbon atom having the largest HOMO electron density (Huckel coefficient) among the carbon atoms in the aromatic hydrocarbon ring constituting the aromatic amine compound (a1).
  • Examples of the aromatic monovinyl compound (a3) in this embodiment include vinylbenzene (styrene), vinylbiphenyl, vinylnaphthalene, and various compounds in which an aromatic ring of these compounds is substituted with one or more substituents such as an alkyl group, alkoxy group, or alkylthio group having 1 to 10 carbon atoms; an aryl group, aryloxy group, or arylthio group having 6 to 10 carbon atoms; a cycloalkyl group having 3 to 10 carbon atoms; a halogen atom; a hydroxyl group; or a mercapto group.
  • substituents such as an alkyl group, alkoxy group, or alkylthio group having 1 to 10 carbon atoms; an aryl group, aryloxy group, or arylthio group having 6 to 10 carbon atoms; a cycloalkyl group having 3 to 10 carbon atoms; a halogen atom; a hydroxy
  • the alkyl group may be either a straight-chain type or a branched type, and may have an unsaturated bond in the structure.
  • the alkyl group or the alkoxy group preferably has 1 to 4 carbon atoms.
  • Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, and an isobutyl group.
  • the alkoxy group include a methoxy group, an ethoxy group, a propyloxy group, and a butoxy group.
  • the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.
  • the aromatic monovinyl compound (a3) which can be the reaction raw material (1) of the polymaleimide compound (A) can be represented by the following formula (b2).
  • R 9b each independently represents an alkyl group, alkoxy group, or alkylthio group having 1 to 10 carbon atoms; an aryl group, aryloxy group, or arylthio group having 6 to 10 carbon atoms; a cycloalkyl group having 3 to 10 carbon atoms; a halogen atom; a hydroxyl group; or a mercapto group
  • t 1b represents an integer of 0 to 5.
  • t 1b is an integer of 2 or more, a plurality of R b2 may be the same or different.
  • R 9b in the above formula (b2) may correspond to R 9 in formula (x).
  • R 9b in the above formula (b1) each independently preferably represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, or a hydroxyl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, even more preferably an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms, still more preferably an alkyl group having 1 to 10 carbon atoms, and even more preferably an alkyl group having 1 to 6 carbon atoms.
  • t 1b is preferably 1 to 4. When t 1b is 2 or more, the multiple R 9b may
  • aromatic monovinyl compound (a3) of the present embodiment include, but are not limited to, vinylbenzenes such as styrene, fluorostyrene, vinyl benzyl chloride, alkylvinylbenzenes (o-, m-, p-methylstyrene, o-, m-, p-ethylvinylbenzene), o-, m-, p-(chloromethyl)styrene, and compounds composed of derivatives thereof; biphenyl compounds such as 4-vinylbiphenyl, 4-vinyl-p-terphenyl, and compounds composed of derivatives thereof; and vinylnaphthalenes such as 1-vinylnaphthalene, 2-vinylnaphthalene, and compounds composed of derivatives thereof.
  • vinylbenzenes such as styrene, fluorostyrene, vinyl benzyl chloride, alkylvinylbenzenes (o-, m-
  • alkylvinylbenzenes and compounds having a substituent on the aromatic ring thereof are preferred, with ethylvinylbenzene being more preferred.
  • the substitution positions of the vinyl group and the ethyl group in ethylvinylbenzene are not particularly limited, but it is preferable that the meta isomer is the main component, and the content of the meta isomer in ethylvinylbenzene is more preferably 40 mass% or more, and even more preferably 50 mass% or more, based on the total amount of ethylvinylbenzene.
  • the molar ratio ((a2)/(a3)) of the aromatic monovinyl compound (a3) to the aromatic divinyl compound (a2) in the reaction raw material (1) is preferably 99/1 to 50/50, and more preferably 98/2 to 70/30.
  • the structural unit of the aromatic monovinyl compound (a3) is preferably contained in an amount of 0 to 40 mass%, more preferably 0 to 30 mass%, relative to the total amount (100 mass%) of the polymaleimide compound (A).
  • the structural unit of the aromatic monovinyl compound (a3) refers to a group in which two hydrogen atoms have been removed from one vinyl group of the aromatic monovinyl compound (a3).
  • maleic anhydride is an essential component of the reaction raw material (1) of the polymaleimide compound (A), and is used in a reaction for maleimidizing an amino group (including —NH2 and a substituted amino group) derived from the aromatic amine compound (a1), as will be described later in the section on the production method of the polymaleimide compound (A).
  • the polymaleimide compound (A) is preferably represented by the following formula (2).
  • R 1 's each independently represent an alkyl group
  • R 2 's each independently represent an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms; an aryl group having 6 to 10 carbon atoms; a cycloalkyl group having 3 to 10 carbon atoms; a halogen atom; or a hydroxyl group
  • R 3 , R 4 , R 5 and R 6 each independently represent a hydrogen atom or a methyl group, and one of R 3 and R 4 is a hydrogen atom and the other is a methyl group, one of R 5 and R 6 is a hydrogen atom and the other is a methyl group
  • X1 is represented by the following formula (x):
  • R 7 and R 8 each independently represent a hydrogen atom or a
  • R 1ii represents an alkyl group
  • p ii represents an integer of 0 to 4.
  • p ii is an integer of 2 or more
  • a plurality of R 1ii may be the same or different.
  • R 1iii represents an alkyl group
  • R 9 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms; an aryl group having 6 to 10 carbon atoms; a cycloalkyl group having 3 to 10 carbon atoms; a halogen atom; or a hydroxyl group
  • R 7 and R 8 each independently represent a hydrogen atom or a methyl group, and one of R 7 and R 8 is a hydrogen atom and the other is a methyl group
  • p iii represents an integer of 0 to 3
  • t represents an integer of 0 to 4
  • r 1iii represents X 1 is the average number of substitutions per benzene ring to which X 1 is bonded, and represents a number from 1 to 4, and * represents a bond with another atom.
  • the multiple R 1iii may be the same as or different from each other, and when t is an integer of 2 or more, the multiple R 9 may be the same as or different from each other.
  • r is the average number of substitutions of X 1 per benzene ring to which X 1 is bonded, and represents a number from 0 to 4, p represents an integer from 1 to 3, q represents an integer from 0 to 4, and k represents an integer from 1 to 100.
  • the multiple R 1s when p is an integer of 2 or more, the multiple R 1s may be the same or different from each other, when q is an integer of 2 or more, the multiple R 2s may be the same or different from each other, and when t is an integer of 2 or more, the multiple R 9s may be the same or different from each other.
  • the preferred forms of R 1 to R 9 , X 1 , p, q, r, t and k in the above formula (2) are the same as those in the above formula (1).
  • polymaleimide compound (A) of this embodiment Preferred aspects of the polymaleimide compound (A) of this embodiment will be described below.
  • Examples of the polymaleimide compound (A) of this embodiment include the following first to third embodiments.
  • a preferred example of the aromatic divinyl compound (a2) is divinylbenzene
  • a preferred example of the aromatic vinyl compound (a3) is ethylvinylbenzene.
  • Preferred examples of the arylmaleimide structural unit are structural units derived from 2-ethylaniline and maleic anhydride.
  • a first embodiment of the polymaleimide compound (A) is a compound in which the molar ratio of the total of structural units derived from an aromatic divinyl compound (a2) and/or an aromatic vinyl compound (a3) to arylmaleimide structural units is n:n+1.
  • Examples of the compound having a molar ratio of the total of structural units derived from the aromatic divinyl compound (a2) and/or the aromatic vinyl compound (a3) to the arylmaleimide structural unit of n:n+1 include: Arylmaleimide structural unit-structural unit derived from aromatic divinyl compound (a2)-arylmaleimide structural unit; Arylmaleimide structural unit-structural unit derived from aromatic divinyl compound (a2)-arylmaleimide structural unit-structural unit derived from aromatic divinyl compound (a2)-arylmaleimide structural unit; Examples of the compound include:
  • a second embodiment of the polymaleimide compound (A) is a compound in which the molar ratio of the total of structural units derived from an aromatic divinyl compound (a2) and/or an aromatic monovinyl compound (a3) to an arylmaleimide structural unit is n:n.
  • Examples of the compound having a molar ratio of n:n between the total of structural units derived from the aromatic divinyl compound (a2) and/or the aromatic monovinyl compound (a3) and the arylmaleimide structural unit include: Arylmaleimide structural unit—structural unit derived from an aromatic monovinyl compound (a3); Arylmaleimide structural unit-structural unit derived from an aromatic divinyl compound (a2)-arylmaleimide structural unit-structural unit derived from an aromatic monovinyl compound (a3); Examples of the compound include:
  • a third embodiment of the polymaleimide compound (A) is a compound in which the molar ratio of the total of the structural units derived from an aromatic divinyl compound (a2) and the structural units derived from an aromatic monovinyl compound (a3) to the arylmaleimide structural units is n+1:n.
  • Examples of compounds in which the molar ratio of the sum of the structural units derived from the aromatic divinyl compound (a2) and the structural units derived from the aromatic monovinyl compound (a3) to the arylmaleimide structural units is n+1:n include: Structural unit derived from an aromatic monovinyl compound (a3)-arylmaleimide structural unit-structural unit derived from an aromatic monovinyl compound (a3); Aromatic monovinyl compound (a3)-arylmaleimide structural unit-structural unit derived from aromatic divinyl compound (a2)-arylmaleimide structural unit-aromatic monovinyl compound (a3) unit; Examples of the compound include:
  • the polymaleimide compound (A) of the present embodiment preferably contains compounds corresponding to at least two of the embodiments of the compounds of the first to third embodiments described above, more preferably contains at least a compound corresponding to the first embodiment, and a compound corresponding to the second embodiment and/or a compound corresponding to the third embodiment, and further preferably contains all of the compounds corresponding to the first to third embodiments.
  • the aromatic monovinyl compound (a3) is likely to function as an end-capping agent for the arylmaleimide structural unit.
  • each aromatic ring is a benzene ring.
  • the following chemical structural formula is provided to exemplify the present disclosure, and the scope of the present disclosure is not limited to the following chemical structural formula.
  • the number average molecular weight (Mn) of the polymaleimide compound (A) is preferably 350 or more, more preferably 400 or more, and preferably 2,000 or less, more preferably 1,500 or less.
  • the weight average molecular weight (Mw) of the polymaleimide compound (A) is preferably 400 or more, more preferably 450 or more, and may be 1000 or more, and may be preferably 500,000 or less, more preferably 400,000 or less, and may be 100,000 or less, or may be 10,000 or less.
  • the polymaleimide compound (A) has a molecular weight distribution (weight average molecular weight (Mw)/number average molecular weight (Mn)) calculated from gel permeation chromatography (GPC) measurement of 1.001 or more, more preferably 1.01 or more, and preferably 500 or less, more preferably 400 or less, in view of its excellent low dielectric constant and low dielectric tangent.
  • Mw weight average molecular weight
  • Mn number average molecular weight
  • the molecular weight distribution is wide and there are many high molecular weight components from the GPC chart obtained from the GPC measurement, the proportion of high molecular weight components contributing to flexibility increases, so that a cured product with reduced brittleness and excellent flexibility and pliability can be obtained compared to a cured product using a conventional maleimide, which is a preferred embodiment.
  • the molecular weight distribution equal to or greater than the lower limit of the molecular weight distribution, the moisture absorption rate and dimensional change rate of the obtained cured product can be reduced. Furthermore, there is a tendency for heat resistance and chemical resistance to be improved.
  • the number average molecular weight (Mn), weight average molecular weight (Mw) and molecular weight distribution (weight average molecular weight (Mw)/number average molecular weight (Mn)) of the polymaleimide compound (A) in this embodiment are measured in accordance with the description in paragraph 0072 of Japanese Patent No. 7,160,151, and this description is incorporated herein by reference.
  • the method for producing the polymaleimide compound (A) in this embodiment is not particularly limited, and the compound may be produced in any manner as long as it uses an aromatic amine compound (a1), an aromatic divinyl compound (a2), and maleic anhydride as reaction raw materials (1), or has a structural unit represented by the above formula (1).
  • An example of a method for producing the polymaleimide compound (A) of the present disclosure includes a production method including the following steps (1) and (2).
  • Step (1) A step of reacting an aromatic amine compound (a1) with an aromatic divinyl compound (a2) as a reaction raw material (2) to obtain an intermediate amine compound (C) in the present embodiment
  • Step (2) A step of reacting the intermediate amine compound (C) obtained in the above step (1) with maleic anhydride as the reaction raw material (3) to obtain the polymaleimide compound (A) of the present disclosure.
  • the method for producing the polymaleimide compound (A) in this embodiment preferably includes a step (1) (also referred to as a crosslinking step) of reacting an aromatic amine compound (a1) with an aromatic divinyl compound (a2) in the presence of a solid acid catalyst, and a step (2) (also referred to as a condensation step) of condensing an intermediate amine compound (C) produced in the step (1) with maleic anhydride.
  • a step (1) also referred to as a crosslinking step
  • a step (2) also referred to as a condensation step of condensing an intermediate amine compound (C) produced in the step (1) with maleic anhydride.
  • Step (1) Production step of intermediate amine compound (C)>>>>> The process for producing the intermediate amine compound (C) in this embodiment will be described below.
  • the step (1) in the present embodiment is not particularly limited, but may be, for example, a step of reacting the above-mentioned aromatic amine compound (a1) with the above-mentioned aromatic divinyl compound (a2) (e.g., divinylbenzene) and, if necessary, other compounds such as an aromatic monovinyl compound (a3) (e.g., ethylvinylbenzene) in the presence of an acid catalyst, thereby producing an intermediate amine compound (C).
  • the blending ratio of the aromatic amine compound (a1) and the aromatic divinyl compound (a2) is preferably 0.1 to 10 moles, more preferably 0.2 to 3 moles, as the molar ratio of the aromatic divinyl compound (a2) to 1 mole of the aromatic amine compound (a1), in consideration of the balance of the physical properties of moldability and curability during the production of the cured product obtained.
  • the aromatic monovinyl compound (a3) is used in combination
  • the molar ratio of the total of the aromatic divinyl compound (a2) and the aromatic monovinyl compound (a3) to 1 mole of the aromatic amine compound (a1) is preferably 0.1 to 10 moles, more preferably 0.2 to 3 moles.
  • the raw materials are generally charged at once and reacted at a predetermined temperature, or an aromatic amine compound (a1) and an acid catalyst are charged and reacted while maintaining a predetermined temperature and dropping an aromatic divinyl compound (a2) or other compounds (e.g., aromatic monovinyl compound (a3)).
  • the dropwise addition time is usually 0.1 to 12 hours, and preferably 6 hours or less.
  • the intermediate amine compound (C) can be obtained by distilling off the solvent and unreacted materials as necessary, and when no solvent is used, the intermediate amine compound (C) can be obtained by distilling off the unreacted materials.
  • Examples of the acid catalyst used in step (1) of the present embodiment include inorganic acids such as phosphoric acid, hydrochloric acid, and sulfuric acid; organic acids such as oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid, and fluoromethanesulfonic acid; solid acids such as activated clay, acid clay, silica alumina, zeolite, and strongly acidic ion exchange resins; and heteropolyhydrochloric acid. From the viewpoint of handling, however, solid acids that allow the catalyst to be easily removed by filtration after the reaction are preferred. When other acids are used, it is preferable to neutralize with a base and wash with water after the reaction.
  • inorganic acids such as phosphoric acid, hydrochloric acid, and sulfuric acid
  • organic acids such as oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid, and fluo
  • the amount of the acid catalyst to be mixed is within the range of 1 to 100 parts by mass per 100 parts by mass of the total amount of the raw materials (aromatic divinyl compound (a2) or a mixture of aromatic divinyl compound (a2) and aromatic monovinyl compound (a3), and aromatic amine compound (a1)) to be charged, and from the viewpoint of handling and economic efficiency, 1 to 60 parts by mass is preferred.
  • the reaction temperature is usually within the range of 100 to 270° C., but 100 to 220° C. is preferred in order to suppress the formation of isomeric structures and to avoid side reactions such as thermal decomposition.
  • the reaction time of the mixture of the aromatic divinyl compound (a2) or the mixture of the aromatic divinyl compound (a2) and the aromatic monovinyl compound (a3) with the aromatic amine compound (a1) i.e., the time of the crosslinking reaction
  • the reaction time of the mixture of the aromatic divinyl compound (a2) or the mixture of the aromatic divinyl compound (a2) and the aromatic monovinyl compound (a3) with the aromatic amine compound (a1) i.e., the time of the crosslinking reaction
  • the time of the crosslinking reaction is usually in the range of 1 to 48 hours in total under the above reaction temperature conditions, and preferably in the range of 1 to 30 hours in total, since the reaction does not proceed completely in a short time and side reactions such as thermal decomposition of the product occur in a long time.
  • aniline or a derivative thereof also serves as a solvent, other solvents are not necessarily used, but it is also possible to use a solvent.
  • a method may be adopted in which a solvent capable of azeotropic dehydration such as toluene, xylene, or chlorobenzene is used, and if necessary, water contained in the catalyst or the like is azeotropically dehydrated, and then the solvent is distilled off, followed by reaction within the above reaction temperature range.
  • a solvent capable of azeotropic dehydration such as toluene, xylene, or chlorobenzene
  • the intermediate amine compound (C) obtained in the above step (1) is preferably represented by, for example, the following formula (4).
  • each R 1 independently represents an alkyl group
  • each R 2 independently represents an alkyl group, an alkoxy group, or an alkylthio group having 1 to 10 carbon atoms
  • a halogen atom a hydroxyl group, or a mercapto group
  • R 3 , R 4 , R 5 and R 6 each independently represent a hydrogen atom or a methyl group, provided that one of R 3 and R 4 is a hydrogen atom and the other is a methyl group, one of R 5 and R 6 is a hydrogen atom and the other is a methyl group
  • X1 is represented by the following formula (x): (In formula (x), R 7 and R 8 each
  • the multiple R 1s may be the same or different from each other.
  • q is an integer of 2 or more
  • the multiple R 2s may be the same or different from each other.
  • t is an integer of 2 or more
  • the multiple R 9s may be the same or different from each other.
  • R 1 to R 9 , X 1 , p, q, r, t and k in the above formula (4) are the same as those in the above formula (1).
  • Another preferred form of the intermediate amine compound (C) obtained by the above step (1) is a structure in which the N-substituted maleimide group in the above formula (2), which is also a preferred form of the polymaleimide compound (A), is substituted with an amino group (including --NH2 and a substituted amino group).
  • the amine equivalent of the intermediate amine compound (C) is preferably from 172 to 400 g/equivalent, and more preferably from 172 to 350 g/equivalent.
  • the amine equivalent of the intermediate amine compound (C) is a value measured by a method based on the neutralization titration method specified in JIS K 0070 (1992).
  • Step (2) in this embodiment is a step of reacting the intermediate amine compound (C) obtained in step (1) with maleic anhydride.
  • the amino group (including —NH2 and a substituted amino group) of the intermediate amine compound (C) can be subjected to a maleimidization reaction to form a chemical structure in which the amino group is substituted with an N-substituted maleimide ring, thereby obtaining the polymaleimide compound (A) of the present disclosure.
  • the intermediate amine compound (C) represented by the above formula (4) obtained in step (1) is charged into a reactor, dissolved in a suitable solvent, and then reacted with maleic anhydride in the presence of a catalyst. After the reaction, unreacted maleic anhydride or other impurities are removed by washing with water or the like, and the solvent is removed under reduced pressure to obtain the target polymaleimide compound (A). If necessary, a dehydrating agent may be used during the reaction.
  • the organic solvents used in step (2) of this embodiment include ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, cyclohexanone, acetophenone, etc.; aprotic solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, acetonitrile, sulfolane, etc.; cyclic ethers such as dioxane, tetrahydrofuran, etc.; esters such as ethyl acetate, butyl acetate, etc.; aromatic solvents such as benzene, toluene, xylene, etc.; and these may be used alone or in combination.
  • ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, cyclohexanone,
  • the mixing ratio of intermediate amine compound (C) and maleic anhydride is preferably in the range of 1 to 5, more preferably 1 to 3, in terms of the equivalent ratio of maleic anhydride to the amino equivalent of intermediate amine compound (C), and the reaction is preferably carried out in an organic solvent having a mass ratio of 0.1 to 10, preferably 0.2 to 5, relative to the total amount of intermediate amine compound (C) and maleic anhydride.
  • Catalysts that can be used in step (2) of this embodiment include inorganic salts such as acetates, chlorides, bromides, sulfates, and nitrates of nickel, cobalt, sodium, calcium, iron, lithium, and manganese, inorganic acids such as phosphoric acid, hydrochloric acid, and sulfuric acid, organic acids such as oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid, and fluoromethanesulfonic acid, solid acids such as activated clay, acid clay, silica alumina, zeolite, and strongly acidic ion exchange resins, and heteropolyhydrochloric acids, with toluenesulfonic acid being particularly preferred.
  • inorganic acids such as phosphoric acid, hydrochloric acid, and sulfuric acid
  • organic acids such as oxalic acid, benzenesulfonic acid, toluenes
  • Examples of the dehydrating agent used in step (2) of the present embodiment include lower aliphatic carboxylic acid anhydrides such as acetic anhydride, propionic anhydride, and butyric anhydride; oxides such as phosphorus pentoxide, calcium oxide, and barium oxide; inorganic acids such as sulfuric acid; and porous ceramics such as molecular sieves.
  • acetic anhydride is preferably used.
  • the amounts of the catalyst and dehydrating agent used in step (2) of the present embodiment are not particularly limited, but typically, 0.0001 to 1.0 mol, preferably 0.01 to 0.3 mol, of the catalyst and 1 to 3 mol, preferably 1 to 1.5 mol, of the dehydrating agent are used relative to 1 equivalent of the amino group (—NH 2 ) of the intermediate amine compound (C).
  • step (2) of the present embodiment the reaction conditions for maleimidization are as follows: the intermediate amine compound (C) and maleic anhydride are charged and reacted at a temperature range of 10 to 100° C., preferably 30 to 60° C., for 0.5 to 12 hours, preferably 1 to 4 hours, and then the catalyst is added and the reaction is continued at a temperature range of 90 to 130° C., preferably 105 to 120° C., for 1 to 24 hours, preferably 1 to 10 hours.
  • the polymaleimide compound (A) of this embodiment (preferably a maleimide compound having a structural unit represented by formula (1), more preferably a maleimide compound having a structural unit represented by formula (2)) may be a commercially available product, such as "NE-X-9500" manufactured by DIC Corporation.
  • the polymaleimide compound (A) used in the present embodiment has an excellent low dielectric property when cured.
  • the cured product of the polymaleimide compound (A) used in this embodiment has a dielectric constant (Dk) of 3.0 or less, more preferably 2.8 or less, and even more preferably 2.6 or less at a frequency of 10 GHz measured according to the cavity resonator perturbation method.
  • the lower limit of the dielectric constant is, for example, 2.0 or more in practical use.
  • the cured product of the polymaleimide compound (A) used in this embodiment has a dielectric loss tangent (Df) of 0.010 or less, more preferably 0.007 or less at a frequency of 10 GHz measured according to the cavity resonator perturbation method.
  • Df dielectric loss tangent
  • the lower limit of the dielectric loss tangent is, for example, 0.0001 or more in practical use.
  • the relative dielectric constant and the dielectric loss tangent can be measured, for example, according to the method described in the examples (curing conditions, measurement conditions).
  • the polymaleimide compound (A) used in this embodiment preferably has high heat resistance in the cured product.
  • the cured product of the polymaleimide compound (A) used in this embodiment preferably has a glass transition temperature measured in accordance with JIS C6481 dynamic viscoelasticity measurement of 180°C or higher, more preferably 200°C or higher, and even more preferably 230°C or higher. By setting the glass transition temperature to be equal to or higher than the lower limit, a cured product with better heat resistance can be obtained. In addition, it is practical for the upper limit of the glass transition temperature to be equal to or lower than 400°C.
  • the "alkyl group” may be any one of linear, branched, and cyclic, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a tert-pentyl group, a neopentyl group, a 1,2-dimethylpropyl group, an n-hexyl group, an isohexyl group, a (n-)heptyl group, a (n-)octyl group, a (n-)nonyl group, a (n-)decyl group, a (n-)undecyl group, a (n-)dodecyl
  • examples of the "cycloalkyl group” include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a norbornyl group, and an adamantyl group.
  • examples of the "alkylthio group” include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, an octylthio group, and a 2-ethylhexylthio group.
  • examples of the "alkenyl group” include an ethynyl group, a 1-propynyl group, a 2-propynyl group, a 2-butynyl group, a pentynyl group, a hexynyl group, a vinyl group, an allyl group, and an isopropenyl group.
  • examples of the "alkoxy group” include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a 2-ethylhexyloxy group, an octyloxy group, and a nonyloxy group.
  • the "aryl group” may be a phenyl group, a 1-naphthyl group, a 2-naphthyl group, or the like.
  • the content of the polymaleimide compound (A) is preferably 1 part by mass or more, more preferably 3 parts by mass or more, even more preferably 4 parts by mass or more, even more preferably 5 parts by mass or more, even more preferably 6 parts by mass or more, even more preferably 8 parts by mass or more, even more preferably 10 parts by mass or more, and may be 15 parts by mass or more, 20 parts by mass or more, 30 parts by mass or more, or 35 parts by mass or more, depending on the application, etc.
  • the content of the polymaleimide compound (A) By setting the content of the polymaleimide compound (A) to be equal to or more than the lower limit, low dielectric properties (low dielectric constant and/or low dielectric tangent) and low thermal expansion properties tend to be further improved.
  • the upper limit of the content of the polymaleimide compound (A) is preferably 90 parts by mass or less, more preferably 70 parts by mass or less, even more preferably 60 parts by mass or less, even more preferably 50 parts by mass or less, even more preferably 45 parts by mass or less, even more preferably 40 parts by mass or less, even more preferably 35 parts by mass or less, and particularly preferably 30 parts by mass or less, and may be 25 parts by mass or less, 20 parts by mass or less, or 15 parts by mass or less, depending on the application, etc.
  • the resin composition of the present embodiment may contain only one type of polymaleimide compound (A), or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.
  • the resin composition of the present embodiment contains a maleimide compound (B) other than the polymaleimide compound (A) (hereinafter, may be simply referred to as "another maleimide compound (B)."
  • another maleimide compound (B) By containing the other maleimide compound (B) in the resin composition of the present embodiment, the obtained cured product has excellent low dielectric properties and low thermal expansion properties, and other physical properties can also be improved.
  • maleimide compound (B) As the other maleimide compound (B), a wide variety of compounds containing one or more (preferably 2 to 12, more preferably 2 to 6, even more preferably 2 to 4, still more preferably 2 or 3, and even more preferably 2) maleimide groups in the molecule can be used, and they are widely selected from compounds commonly used in the field of printed wiring boards depending on the application, etc.
  • the other maleimide compound (B) used in the present embodiment has a cured product with excellent low dielectric properties.
  • the cured product of the maleimide compound (B) used in the present embodiment preferably has a dielectric loss tangent (Df) of 0.003 or less, more preferably 0.0028 or less, at a frequency of 10 GHz, as measured according to a cavity resonance perturbation method.
  • Df dielectric loss tangent
  • the lower limit of the dielectric loss tangent is, for example, practically 0.0001 or more.
  • the cured product of the maleimide compound (B) used in this embodiment preferably has a dielectric constant (Dk) of 2.5 or less, more preferably 2.3 or less, at a frequency of 10 GHz, as measured according to a cavity resonance perturbation method.
  • the lower limit of the dielectric constant is, for example, 1.8 or more in practice.
  • the dielectric constant and dielectric loss tangent can be measured, for example, according to the method described in the examples (curing conditions, measurement conditions).
  • the compound (B) containing two or more carbon-carbon unsaturated double bonds used in this embodiment preferably has a cured product with excellent low dielectric properties.
  • the cured product of the compound (B) containing two or more carbon-carbon unsaturated double bonds used in this embodiment preferably has a dielectric constant (Dk) of 3.0 or less, more preferably 2.6 or less, at a frequency of 10 GHz, measured according to the cavity resonator perturbation method.
  • the lower limit of the dielectric constant is, for example, 2.0 or more in practical use.
  • the cured product of the compound (B) containing two or more carbon-carbon unsaturated double bonds used in this embodiment preferably has a dielectric loss tangent (Df) of 0.010 or less, more preferably 0.007 or less, at a frequency of 10 GHz, measured according to the cavity resonator perturbation method.
  • Df dielectric loss tangent
  • the lower limit of the dielectric loss tangent is, for example, 0.0001 or more in practical use.
  • the dielectric constant and dielectric loss tangent can be measured, for example, according to the method described in the examples (curing conditions, measurement conditions).
  • the other maleimide compound (B) preferably includes one or more selected from the group consisting of a compound represented by formula (M0), a compound represented by formula (M1), a compound represented by formula (M2), a compound represented by formula (M3), a compound represented by formula (M4), a compound represented by formula (M5), and a maleimide compound (M6), and more preferably includes one or more selected from the group consisting of a compound represented by formula (M0), a compound represented by formula (M1), a compound represented by formula (M3), a compound represented by formula (M4), a compound represented by formula (M5), and a maleimide compound (M6).
  • the compound represented by formula (M1) is preferable because it has excellent low dielectric properties, and is even more preferable because it has excellent heat resistance in addition to low dielectric properties.
  • R 51 each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group;
  • R 52 each independently represents a hydrogen atom or a methyl group;
  • n 1 represents an integer of 1 or more.
  • Each R 51 is preferably one selected from the group consisting of a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, and a phenyl group, more preferably a hydrogen atom and/or a methyl group, and further preferably a hydrogen atom.
  • R 52 is preferably a methyl group.
  • n1 is preferably an integer of 1 to 10, more preferably an integer of 1 to 5, even more preferably an integer of 1 to 3, even more preferably 1 or 2, and even more preferably 1.
  • M0 the following compounds are preferred examples of the formula (M0).
  • each R 8 independently represents a hydrogen atom, a methyl group or an ethyl group, with a methyl group being preferred.
  • the compound represented by formula (M0) may be a single type or a mixture of two or more types.
  • Examples of the mixture include a mixture of compounds with different n1 , a mixture of compounds with different types of substituents of R51 and/or R52 , a mixture of compounds with different bonding positions (meta, para, ortho) of the maleimide group and oxygen atom to the benzene ring, and a mixture of compounds combining two or more of the above different points.
  • (In formula (M1), R M1 , R M2 , R M3 , and R M4 each independently represent a hydrogen atom or an organic group.
  • R M5 and R M6 each independently represent a hydrogen atom or an alkyl group.
  • Ar M represents a divalent aromatic group.
  • A represents a 4- to 6-membered alicyclic group.
  • R M7 and R M8 each independently represent an alkyl group.
  • mx is 1 or 2
  • lx is 0 or 1.
  • R M9 and R M10 each independently represent a hydrogen atom or an alkyl group.
  • R M11 , R M12 , R M13 , and R M14 each independently represent a hydrogen atom or an organic group.
  • Each M15 independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a halogen atom, a hydroxyl group, or a mercapto group.
  • px represents an integer of 0 to 3.
  • nx represents an integer of 1 to 20.
  • R M1 , R M2 , R M3 , and R M4 each independently represent a hydrogen atom or an organic group.
  • the organic group here is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, even more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and among these, a methyl group is particularly preferred.
  • R M1 and R M3 each independently are preferably an alkyl group, and R M2 and R M4 are preferably a hydrogen atom.
  • R M5 and R M6 each independently represent a hydrogen atom or an alkyl group, preferably an alkyl group.
  • the alkyl group is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, further preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and particularly preferably a methyl group.
  • Ar M represents a divalent aromatic group, preferably a phenylene group, a naphthalenediyl group, a phenanthrenediyl group, or an anthracenediyl group, more preferably a phenylene group, and even more preferably an m-phenylene group.
  • Ar M may have a substituent, and the substituent is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, even more preferably an alkyl group having 1 to 6 carbon atoms, still more preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and particularly preferably a methyl group.
  • Ar M is unsubstituted.
  • A is a 4- to 6-membered alicyclic group, and more preferably a 5-membered alicyclic group (preferably a group that forms an indane ring together with a benzene ring).
  • R and R are each independently an alkyl group , preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group.
  • mx is 1 or 2, and is preferably 2.
  • lx is 0 or 1, and is preferably 1.
  • R M9 and R M10 each independently represent a hydrogen atom or an alkyl group, more preferably an alkyl group.
  • the alkyl group is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, further preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and particularly preferably a methyl group.
  • R M11 , R M12 , R M13 , and R M14 each independently represent a hydrogen atom or an organic group.
  • the organic group here is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, even more preferably an alkyl group having 1 to 6 carbon atoms, still more preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and particularly preferably a methyl group.
  • R M12 and R M13 each independently represent preferably an alkyl group, and R M11 and R M14 each represent preferably a hydrogen atom.
  • R M15 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a halogen atom, a hydroxyl group, or a mercapto group, and is preferably an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms.
  • nx represents an integer of 1 to 20. nx may be an integer of 10 or less.
  • the resin composition of the present embodiment may contain only one type of compound represented by formula (M1) having at least different values of nx, or may contain two or more types.
  • the average value (average number of repeating units) n of nx in the compound represented by formula (M1) in the resin composition is preferably 0.92 or more, more preferably 0.95 or more, even more preferably 1.0 or more, and even more preferably 1.1 or more, in order to have a low melting point (low softening point), a low melt viscosity, and excellent handleability.
  • n is preferably 10.0 or less, more preferably 8.0 or less, even more preferably 7.0 or less, even more preferably 6.0 or less, and may be 5.0 or less. The same applies to the formula (M1-1) described later.
  • the compound represented by formula (M1) is preferably a compound represented by the following formula (M1-1).
  • R M21 , R M22 , R M23 , and R M24 each independently represent a hydrogen atom or an organic group.
  • R M25 and R M26 each independently represent a hydrogen atom or an alkyl group.
  • R M27 , R M28 , R M29 , and R M30 each independently represent a hydrogen atom or an organic group.
  • R M31 and R M32 each independently represent a hydrogen atom or an alkyl group.
  • R M33 , R M34 , R M35 , and R M36 each independently represent a hydrogen atom or an organic group.
  • R M37 , R M38 , and R M39 each independently represent a hydrogen atom or an alkyl group.
  • nx represents an integer of 1 or more and 20 or less.
  • R M21 , R M22 , R M23 , and R M24 each independently represent a hydrogen atom or an organic group.
  • the organic group here is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, even more preferably an alkyl group having 1 to 6 carbon atoms, still more preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and particularly preferably a methyl group.
  • R M21 and R M23 are preferably an alkyl group, and R M22 and R M24 are preferably a hydrogen atom.
  • R M25 and R M26 each independently represent a hydrogen atom or an alkyl group, preferably an alkyl group.
  • the alkyl group here is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, further preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and particularly preferably a methyl group.
  • R M27 , R M28 , R M29 , and R M30 each independently represent a hydrogen atom or an organic group, preferably a hydrogen atom.
  • the organic group here is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, still more preferably an alkyl group having 1 to 6 carbon atoms, still more preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and particularly preferably a methyl group.
  • R M31 and R M32 each independently represent a hydrogen atom or an alkyl group, preferably an alkyl group.
  • the alkyl group here is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, further preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and particularly preferably a methyl group.
  • R M33 , R M34 , R M35 , and R M36 each independently represent a hydrogen atom or an organic group.
  • the organic group here is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, still more preferably an alkyl group having 1 to 6 carbon atoms, still more preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and particularly preferably a methyl group.
  • R M33 and R M36 are preferably a hydrogen atom, and R M34 and R M35 are preferably an alkyl group.
  • R M37 , R M38 , and R M39 each independently represent a hydrogen atom or an alkyl group, preferably an alkyl group.
  • the alkyl group here is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, further preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and particularly preferably a methyl group.
  • nx represents an integer of 1 to 20. nx may be an integer of 10 or less.
  • the compound represented by formula (M1-1) is preferably a compound represented by the following formula (M1-2).
  • R M21 , R M22 , R M23 , and R M24 each independently represent a hydrogen atom or an organic group.
  • R M25 and R M26 each independently represent a hydrogen atom or an alkyl group.
  • R M27 , R M28 , R M29 , and R M30 each independently represent a hydrogen atom or an organic group.
  • R M31 and R M32 each independently represent a hydrogen atom or an alkyl group.
  • R M33 , R M34 , R M35 , and R M36 each independently represent a hydrogen atom or an organic group.
  • R M37 , R M38 , and R M39 each independently represent a hydrogen atom or an alkyl group.
  • nx represents an integer of 1 or more and 20 or less.
  • R M21 , R M22 , R M23 , R M24 , R M25 , R M26 , R M27 , R M28 , R M29 , R M30 , R M31 , R M32 , R M33 , R M34 , R M35 , R M36 , R M37 , R M38 , R M39 , and nx respectively represent R M21 , R M22 , R M23 , R M24 , R M25 , R M26 , R M27 , R M28 , R M29 , R M30 , R M31 , R M32 , R M33 , R M34 , R M35 , R M36 , R M37 , R M38 , R M39 and nx have the same meanings and preferred ranges.
  • the compound represented by formula (M1-1) is preferably a compound represented by the following formula (M1-3), and more preferably a compound represented by the following formula (M1-4).
  • M1-3 nx represents an integer of 1 or more and 20 or less.
  • nx may be an integer of 10 or less.
  • M1-4 nx represents an integer of 1 or more and 20 or less.
  • nx may be an integer of 10 or less.
  • the compound (B) containing two or more carbon-carbon unsaturated double bonds used in this embodiment may also be a compound having an indane skeleton having a carbon-carbon unsaturated double bond at its terminal.
  • indane skeleton having a carbon-carbon unsaturated double bond at its terminal.
  • the molecular weight of the compound represented by formula (M1) is preferably 500 or more, more preferably 600 or more, and even more preferably 700 or more. By making it equal to or greater than the lower limit, the low dielectric properties and low water absorption of the obtained cured product tend to be further improved. In addition, the molecular weight of the compound represented by formula (M1) is preferably 10,000 or less, more preferably 9,000 or less, even more preferably 7,000 or less, even more preferably 5,000 or less, and even more preferably 4,000 or less. By making it equal to or less than the upper limit, the heat resistance and handleability of the obtained cured product tend to be further improved.
  • the compound represented by formula (M1) preferably has a maleimide group equivalent of 50 g/eq. or more, more preferably 100 g/eq. or more, and even more preferably 200 g/eq. or more.
  • the upper limit of the maleimide equivalent is preferably 2000 g/eq. or less, more preferably 1000 g/eq. or less, and even more preferably 800 g/eq. or less.
  • the maleimide group equivalent represents the mass of the maleimide compound per equivalent of maleimide group.
  • the compound represented by formula (M1) preferably has a molecular weight distribution Mw/Mn calculated from gel permeation chromatography (GPC) measurement of 1.0 to 4.0, more preferably 1.1 to 3.8, even more preferably 1.2 to 3.6, and even more preferably 1.3 to 3.4.
  • Mw/Mn molecular weight distribution calculated from gel permeation chromatography
  • R 54 each independently represents a hydrogen atom or a methyl group, and n 4 represents an integer of 1 or more.
  • n4 is preferably an integer of 1 to 10, more preferably an integer of 1 to 5, even more preferably an integer of 1 to 3, still more preferably 1 or 2, and may be 1.
  • the compound represented by formula (M2) may be, and is preferably, a mixture of compounds having different n4 , or may be a mixture of compounds having different other moieties, as described for the compound represented by formula (M0).
  • R 55 each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group, and n 5 represents an integer of 1 or more and 10 or less.
  • Each R 55 is preferably one selected from the group consisting of a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, and a phenyl group, more preferably a hydrogen atom and/or a methyl group, and further preferably a hydrogen atom.
  • n5 is preferably an integer of 1 or more and 5 or less, more preferably an integer of 1 to 3, and even more preferably 1 or 2.
  • the compound represented by formula (M3) may be, and is preferably, a mixture of compounds having different n5 . As described in the compound represented by formula (M0), the compound may be a mixture of compounds having different other moieties.
  • each R 56 independently represents a hydrogen atom, a methyl group, or an ethyl group, and each R 57 independently represents a hydrogen atom or a methyl group.
  • Each R 56 is preferably independently a methyl group or an ethyl group, more preferably a methyl group or an ethyl group on each of the two benzene rings, and R 57 is preferably a methyl group.
  • R 58 each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group; R 59 each independently represents a hydrogen atom or a methyl group; and n 6 represents an integer of 1 or greater.
  • Each R 58 is preferably one selected from the group consisting of a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, and a phenyl group, more preferably a hydrogen atom and/or a methyl group, and further preferably a hydrogen atom.
  • R 59 is preferably a methyl group.
  • n6 is preferably an integer of 1 to 10, more preferably an integer of 1 to 5, even more preferably an integer of 1 to 3, still more preferably 1 or 2, and may be 1.
  • the compound represented by formula (M5) may be, and is preferably, a mixture of compounds having different n6 . As described in the compound represented by formula (M0), the compound may be a mixture of compounds having different other moieties.
  • the maleimide compound may be produced by a known method, or a commercially available product may be used.
  • Examples of commercially available products include "BMI-80" manufactured by K.I. Kasei Co., Ltd. as a compound represented by formula (M0), "NE-X-9470S” and “NE-X-9480S” manufactured by DIC Corporation as a compound represented by formula (M1), "BMI-2300” manufactured by Daiwa Kasei Kogyo Co., Ltd. as a compound represented by formula (M2), "MIR-3000-70MT” manufactured by Nippon Kayaku Co., Ltd. as a compound represented by formula (M3), "BMI-70” manufactured by K.I. Kasei Co., Ltd. as a compound represented by formula (M4), and "MIR-5000” manufactured by Nippon Kayaku Co., Ltd. as a compound represented by formula (M5).
  • the maleimide compound (M6) is a compound having a structural unit represented by formula (M6) and maleimide groups at both ends of the molecular chain.
  • R 61 represents a linear or branched alkylene group having 1 to 16 carbon atoms, or a linear or branched alkenylene group having 2 to 16 carbon atoms.
  • R 62 represents a linear or branched alkylene group having 1 to 16 carbon atoms, or a linear or branched alkenylene group having 2 to 16 carbon atoms.
  • R 63 each independently represents a linear or branched alkyl group having 1 to 16 carbon atoms, or a linear or branched alkenyl group having 2 to 16 carbon atoms.
  • Each n independently represents an integer of 0 to 10.
  • the weight average molecular weight of the maleimide compound (M6) is preferably 100 or more, more preferably 300 or more, and is preferably 5000 or less, more preferably 4500 or less. By setting it within the above range, a suitable viscosity can be obtained and an increase in the viscosity of the varnish can be suppressed.
  • the weight average molecular weight of the maleimide compound (M6) means the mass average molecular weight calculated using polystyrene standards by gel permeation chromatography (GPC).
  • R 61 represents a linear or branched alkylene group having 1 to 16 carbon atoms, or a linear or branched alkenylene group having 2 to 16 carbon atoms.
  • R 61 is preferably a linear or branched alkylene group, and more preferably a linear alkylene group, from the viewpoints of obtaining a suitable viscosity and controlling the increase in the viscosity of the varnish.
  • the number of carbon atoms in the alkylene group is preferably 2 to 14, and more preferably 4 to 12, from the viewpoints of obtaining a more suitable viscosity and better controlling the increase in the viscosity of the varnish.
  • linear or branched alkylene groups include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, dodecylene, undecylene, tridecylene, tetradecylene, pentadecylene, hexadecylene, neopentylene, dimethylbutylene, methylhexylene, ethylhexylene, dimethylhexylene, trimethylhexylene, methylheptylene, dimethylheptylene, trimethylheptylene, tetramethylheptylene, ethylheptylene, methyloctylene, methylnonylene, methyldecylene, methyldodecylene, methylundecylene, methyltridecylene, methyltetradecylene, methylpentadecylene, and
  • the alkenylene group preferably has 2 to 14 carbon atoms, and more preferably 4 to 12 carbon atoms, in order to obtain a more suitable viscosity and to better control the increase in viscosity of the varnish.
  • linear or branched alkenylene groups include vinylene, 1-methylvinylene, allylene, propenylene, isopropenylene, 1-butenylene, 2-butenylene, 1-pentenylene, 2-pentenylene, isopentylene, cyclopentenylene, cyclohexenylene, and dicyclopentadienylene groups.
  • R 62 represents a linear or branched alkylene group having 1 to 16 carbon atoms, or a linear or branched alkenylene group having 2 to 16 carbon atoms.
  • R 62 is preferably a linear or branched alkylene group, and more preferably a linear alkylene group, from the viewpoints of obtaining a suitable viscosity and controlling the increase in viscosity of the varnish.
  • the number of carbon atoms in the alkylene group is preferably 2 to 14, and more preferably 4 to 12, from the viewpoints of obtaining a more suitable viscosity and better controlling the increase in the viscosity of the varnish.
  • Examples of the linear or branched alkylene group include the same as those mentioned above for R 61 .
  • the alkenylene group preferably has 2 to 14 carbon atoms, and more preferably has 4 to 12 carbon atoms, in that a more suitable viscosity can be obtained and the increase in the viscosity of the varnish can be better controlled.
  • Examples of the linear or branched alkenylene group include the same as those mentioned above for R 61 .
  • R 61 and R 62 may be the same or different, but are preferably the same in terms of facilitating synthesis of the maleimide compound (M6).
  • R 63 each independently represents a linear or branched alkyl group having 1 to 16 carbon atoms, or a linear or branched alkenyl group having 2 to 16 carbon atoms.
  • R 63 is preferably a linear or branched alkyl group having 1 to 16 carbon atoms, from the viewpoint of obtaining a suitable viscosity and controlling the increase in the viscosity of the varnish, and among R 63 , it is preferable that one to five are linear or branched alkyl groups having 1 to 16 carbon atoms, and it is more preferable that one to three are linear or branched alkyl groups having 1 to 16 carbon atoms.
  • the portion other than the linear or branched alkyl group having 1 to 16 carbon atoms is preferably a hydrogen atom.
  • the number of carbon atoms in the alkyl group is preferably from 2 to 14, and more preferably from 4 to 12, in that a more suitable viscosity can be obtained and the increase in viscosity of the varnish can be more controlled.
  • linear or branched alkyl group examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a 2-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, a 2-pentyl group, a tert-pentyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 2,2-dimethylpropyl group, an n-hexyl group, a 2-hexyl group, a 3-hexyl group, a 2-methylpentyl group, a 3-methylpentyl group, a 4-methylpentyl group, and a 2-methylpentan-3-yl group.
  • the number of carbon atoms in the alkenyl group is preferably from 2 to 14, and more preferably from 4 to 12, in that a more suitable viscosity can be obtained and the increase in the viscosity of the varnish can be more controlled.
  • Examples of the linear or branched alkenyl group include a vinyl group, an allyl group, a 4-pentenyl group, an isopropenyl group, and an isopentyl group.
  • each n independently represents an integer from 0 to 10, preferably 1 or more, more preferably 5 or more, and preferably 9 or less, more preferably 7 or less.
  • the maleimide compound (M6) has maleimide groups at both ends of the molecular chain.
  • both ends means both ends of the molecular chain of the maleimide compound (M6), and for example, when the structural unit represented by formula (M6) is at the end of the molecular chain of the maleimide compound (M6), it means that the maleimide group is at the end of the molecular chain of R 61 , at the end of the molecular chain at the N atom of the maleimide ring, or at both ends.
  • the maleimide compound (M6) may have maleimide groups in addition to both ends of the molecular chain.
  • the maleimide groups bonded to the maleimide compound (M6) may be the same or different, but it is preferable that the maleimide groups at both ends of the molecular chain are the same.
  • maleimide compounds examples include maleimide compounds represented by the following formula (M6-1): These may be used alone or in appropriate mixture of two or more.
  • a represents an integer of 1 to 10.
  • the maleimide compound (M6) may be a commercially available product, such as MIZ-001 manufactured by Nippon Kayaku Co., Ltd.
  • the production method of the maleimide compound (M6) can be referred to in paragraphs 0061 to 0066 of WO 2020/262577, the contents of which are incorporated herein by reference.
  • maleimide compounds (B) other than those mentioned above include, for example, N-phenylmaleimide, N-cyclohexylmaleimide, phenylmethanemaleimide oligomers, m-phenylene bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, 4,4'-diphenylether bismaleimide, 4,4'-diphenylsulfone bismaleimide, 1,3-bis(3-maleimidophenoxy)benzene, 1,3-bis(4-maleimidophenoxy)benzene, prepolymers of these, and prepolymers of these maleimides and amines.
  • monofunctional maleimide compounds such as N-phenylmaleimide and N-cyclohexylmaleimide tend to produce resin compositions that can provide cured products with excellent low dielectric properties when used in combination with polymers having the structural unit represented by formula (V) above.
  • the lower limit of the content of the other maleimide compound (B) (preferably a compound represented by formula (M1)) in the resin composition of this embodiment is preferably 1 part by mass or more, more preferably 5 parts by mass or more, even more preferably 10 parts by mass or more, still more preferably 20 parts by mass or more, and even more preferably 25 parts by mass or more, and may be 30 parts by mass or more, 35 parts by mass or more, or 45 parts by mass or more, depending on the application, etc.
  • the content of the other maleimide compound (B) is equal to or more than the above lower limit, the low dielectric properties (low dielectric constant and/or low dielectric tangent), low thermal expansion, low water absorbency, chemical resistance, and heat resistance of the obtained cured product tend to be improved.
  • the upper limit of the content of the other maleimide compound (B) is preferably 90 parts by mass or less, more preferably 80 parts by mass or less, even more preferably 75 parts by mass or less, still more preferably 70 parts by mass or less, and even more preferably 60 parts by mass or less, and may be 50 parts by mass or less, 40 parts by mass or less, or 35 parts by mass or less, depending on the application, etc.
  • the resin composition in the present embodiment may contain only one type of the other maleimide compound (B), or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.
  • the total amount of the polymaleimide compound (A) and the other maleimide compound (B) is preferably 20% by mass or more of the resin solid content in the resin composition, more preferably 30% by mass or more, even more preferably 40% by mass or more, and even more preferably 45% by mass or more, and may be 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, or 95% by mass or more depending on the application.
  • the total amount of the polymaleimide compound (A) and the other maleimide compound (B) is preferably 99.9% by mass or less of the resin solid content in the resin composition, and may be 95% by mass or less, 90% by mass or less, 80% by mass or less, 70% by mass or less, 65% by mass or less, or 60% by mass or less depending on the application.
  • the low dielectric properties low dielectric constant and/or low dielectric tangent
  • low thermal expansion properties tend to be further improved.
  • the mass ratio of the polymaleimide compound (A) to the other maleimide compound (B) is preferably 1:9 to 6:4, more preferably 2:8 to 5:5, and even more preferably 3:7 to 4:6. By using such a blend ratio, it is possible to improve low thermal expansion while maintaining low dielectric properties.
  • the resin composition of the present embodiment preferably contains a compound (C) containing two or more polymerizable carbon-carbon unsaturated double bonds (hereinafter, in this specification, may be simply referred to as "compound (C) containing two or more carbon-carbon unsaturated double bonds").
  • compound (C) containing two or more carbon-carbon unsaturated double bonds is usually a thermosetting compound.
  • the compound (C) containing two or more carbon-carbon unsaturated double bonds used in this embodiment a wide variety of compounds containing two or more carbon-carbon unsaturated double bonds that are commonly used in printed wiring boards can be used.
  • the upper limit of the number of carbon-carbon unsaturated double bonds contained in the compound (C) containing two or more carbon-carbon unsaturated double bonds used in this embodiment is preferably 2000 or less, may be 10 or less, may be 5 or less, and may be particularly 2. By setting the number to the above upper limit or less, moisture absorption and heat resistance tends to be further improved.
  • the compound (C) containing two or more carbon-carbon unsaturated double bonds used in this embodiment preferably has a cured product with excellent low dielectric properties.
  • the cured product of the compound (C) containing two or more carbon-carbon unsaturated double bonds used in this embodiment preferably has a dielectric constant (Dk) of 3.0 or less, more preferably 2.6 or less, at a frequency of 10 GHz, measured according to the cavity resonance perturbation method.
  • the lower limit of the dielectric constant is, for example, 2.0 or more in practical use.
  • the cured product of the compound (C) containing two or more carbon-carbon unsaturated double bonds used in this embodiment preferably has a dielectric loss tangent (Df) of 0.010 or less, more preferably 0.007 or less, at a frequency of 10 GHz, measured according to the cavity resonance perturbation method.
  • Df dielectric loss tangent
  • the lower limit of the dielectric loss tangent is, for example, 0.0001 or more in practical use.
  • the dielectric constant and dielectric loss tangent can be measured, for example, according to the method described in the examples (curing conditions, measurement conditions).
  • the compound (C) containing two or more carbon-carbon unsaturated double bonds used in this embodiment preferably has high heat resistance in its cured product.
  • the cured product of the compound (C) containing two or more carbon-carbon unsaturated double bonds used in this embodiment preferably has a glass transition temperature measured according to JIS C6481 dynamic viscoelasticity measurement of 100°C or higher, more preferably 130°C or higher, even more preferably 150°C or higher, even more preferably 180°C or higher, and even more preferably 200°C or higher.
  • the glass transition temperature By setting the glass transition temperature at or above the lower limit, a cured product with excellent heat resistance can be obtained.
  • it is practical for the upper limit of the glass transition temperature to be 400°C or lower.
  • the compound (C) containing two or more carbon-carbon unsaturated double bonds has a number average molecular weight Mn of 195 or more, more preferably 400 or more, even more preferably 500 or more, even more preferably 800 or more, and may be 1000 or more, 1200 or more, 1500 or more, or 1800 or more, as measured by GPC.
  • Mn number average molecular weight
  • the number average molecular weight Mn of the compound (C) containing two or more carbon-carbon unsaturated double bonds is preferably 130,000 or less, more preferably 120,000 or less, even more preferably 100,000 or less, and may be 50,000 or less, 10,000 or less, 7000 or less, 5000 or less, 3500 or less, 3000 or less, or 2500 or less.
  • the compound (C) containing two or more carbon-carbon unsaturated double bonds has a weight average molecular weight Mw of 195 or more, more preferably 400 or more, even more preferably 500 or more, even more preferably 800 or more, and may be 1,0001200 or more, 1500 or more, or 1800 or more. By making it equal to or greater than the lower limit, the low dielectric properties tend to be further improved.
  • the weight average molecular weight of the compound (C) containing two or more carbon-carbon unsaturated double bonds is preferably equal to or less than 160,000, more preferably equal to or less than 150,000, even more preferably equal to or less than 140,000, even more preferably equal to or less than 130,000, even more preferably equal to or less than 100,000, and may be equal to or less than 80,000, 50,000, or 10,000. By making it equal to or less than the upper limit, the heat resistance tends to be further improved.
  • the carbon-carbon unsaturated double bond contained in the compound (C) containing two or more carbon-carbon unsaturated double bonds used in this embodiment is a polymerizable unsaturated group, and is usually a carbon-carbon unsaturated double bond that undergoes a reaction with some kind of reactive functional group. Furthermore, the compound (C) containing two or more carbon-carbon unsaturated double bonds preferably contains a terminal carbon-carbon unsaturated double bond, and more preferably contains two or more terminal carbon-carbon unsaturated double bonds.
  • the compound (C) containing two or more carbon-carbon unsaturated double bonds used in the present embodiment preferably contains at least one selected from the group consisting of a compound containing a vinylaryl group, a compound containing a (meth)acryloyl group, and a compound containing a (meth)allyl group, more preferably contains at least one selected from the group consisting of a compound containing a vinylaryl group and a compound containing a (meth)allyl group, and further preferably contains a compound containing a (meth)allyl group. More preferably, the compound containing a vinylaryl group is a compound containing a vinylphenyl group, and even more preferably, a compound containing a vinylbenzyl group.
  • the compound containing a (meth)acryloyl group is preferably a compound containing a methacrylate group
  • the compound containing a (meth)allyl group is preferably a compound containing an allyl group.
  • the resin composition of the present embodiment may be configured to be substantially free of a compound containing an allyl group. Substantially free means that the content of the compound containing an allyl group is less than 1 part by mass, preferably less than 0.1 part by mass, per 100 parts by mass of the total of the other resin components (D).
  • the resin composition of the present embodiment may be configured to be substantially free of diallyl bisphenol and its derivatives. Substantially free means that the content of diallyl bisphenol and its derivatives is less than 1 part by mass, preferably less than 0.1 part by mass, per 100 parts by mass of the total of the other resin components (D).
  • one embodiment of the compound (C) containing two or more carbon-carbon unsaturated double bonds used in this embodiment is a polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds, and in particular, a polyphenylene ether compound having a vinylaryl group and/or a polyphenylene ether compound having a (meth)acryloyl group is preferred, with a polyphenylene ether compound having a vinylaryl group being more preferred.
  • Another embodiment of the compound (C) containing two or more carbon-carbon unsaturated double bonds used in this embodiment is a polymer having a structural unit represented by formula (V).
  • Ar represents an aromatic hydrocarbon linking group. * represents a bonding position.
  • Another embodiment of the compound (C) containing two or more carbon-carbon unsaturated double bonds used in this embodiment is a compound containing a (meth)allyl group, and is preferably an allyl-substituted nadimide compound. Details of these preferred embodiments are provided below.
  • the compound (C) containing two or more carbon-carbon unsaturated double bonds used in this embodiment may also contain a structural unit derived from maleic anhydride.
  • a structural unit derived from maleic anhydride refer to the description in International Publication No. 2017/209108, the contents of which are incorporated herein by reference.
  • the compound (C) containing two or more carbon-carbon unsaturated double bonds may contain a structural unit derived from a compound having an acid group and an acid anhydride group.
  • the content (total amount) of the compound (C) containing two or more carbon-carbon unsaturated double bonds is preferably 1 part by mass or more, more preferably 5 parts by mass or more, even more preferably 10 parts by mass or more, still more preferably 20 parts by mass or more, even more preferably 30 parts by mass or more, and still more preferably 35 parts by mass or more, relative to 100 parts by mass of the resin solid content in the resin composition.
  • the upper limit of the content (total amount) of the compound (C) containing two or more carbon-carbon unsaturated double bonds is preferably 90 parts by mass or less, more preferably 85 parts by mass or less, relative to 100 parts by mass of the resin solid content in the resin composition, and may be 80 parts by mass or less, 70 parts by mass or less, 65 parts by mass or less, 60 parts by mass or less, or 55 parts by mass or less depending on the application, etc.
  • the resin composition of the present embodiment may contain only one type of compound (C) containing two or more carbon-carbon unsaturated double bonds, or may contain two or more types. When two or more types are contained, it is preferable that the total amount is in the above range.
  • the compound (C) containing two or more carbon-carbon unsaturated double bonds preferably contains a polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds.
  • the polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds is preferably a polyphenylene ether compound containing two or more vinylbenzyl groups.
  • the polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds preferably contains a carbon-carbon unsaturated double bond at a terminal, and is preferably a polyphenylene ether compound containing two or more vinylbenzyl groups at a terminal.
  • polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds is a compound containing a phenylene ether skeleton represented by the following formula (X1).
  • R 24 , R 25 , R 26 , and R 27 may be the same or different and each represents an alkyl group having 6 or less carbon atoms, an aryl group, a halogen, or a hydrogen atom.
  • the polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds is represented by the formula (X2): (In formula (X2), R 28 , R 29 , R 30 , R 34 , and R 35 may be the same or different and represent an alkyl group having 6 or less carbon atoms or a phenyl group.
  • R 31 , R 32 , and R 33 may be the same or different and represent a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group.) and/or a repeating unit represented by formula (X3):
  • R 36 , R 37 , R 38 , R 39 , R 40 , R 41 , R 42 and R 43 may be the same or different and are a hydrogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group;
  • -A- is a linear, branched or cyclic divalent hydrocarbon having 20 or less carbon atoms.
  • the polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds is preferably a modified polyphenylene ether compound in which a part or all of the terminals are functionalized with an ethylenically unsaturated group (hereinafter, sometimes referred to as "modified polyphenylene ether compound (g)”), more preferably a modified polyphenylene ether compound having two or more groups selected from the group consisting of (meth)acryloyl groups, maleimide groups, (meth)allyl groups, and vinylbenzyl groups at the terminals, even more preferably a modified polyphenylene ether compound having two or more groups selected from the group consisting of (meth)acryloyl groups and vinylbenzyl groups, and even more preferably a modified polyphenylene ether compound having two or more vinylbenzyl groups in terms of excellent chemical resistance and desmear resistance.
  • modified polyphenylene ether compound (g) modified polyphenylene ether compound having two or more groups selected from the group consist
  • modified polyphenylene ether compound (g) By employing such modified polyphenylene ether compound (g), it is possible to further reduce the dielectric tangent (Df) of the cured product of the resin composition. These may be used alone or in combination of two or more. By employing such modified polyphenylene ether compound (g), it is possible to further reduce Df and increase peel strength. These may be used alone or in combination of two or more.
  • the method for producing the modified polyphenylene ether compound (g) is not particularly limited as long as it can obtain the effects of the present invention.
  • those functionalized with an ethylenically unsaturated group (specifically, vinylbenzyl group, etc.) can be produced by dissolving a bifunctional phenylene ether oligomer and vinylbenzyl chloride in a solvent, adding a base under heating and stirring to cause a reaction, and then solidifying the resin.
  • Those functionalized with a carboxy group can be produced, for example, by melt-kneading and reacting an unsaturated carboxylic acid or a functionalized derivative thereof with a polyphenylene ether compound in the presence or absence of a radical initiator.
  • they can be produced by dissolving a polyphenylene ether compound and an unsaturated carboxylic acid or a functionalized derivative thereof in an organic solvent in the presence or absence of a radical initiator, and reacting them in the solution.
  • the ethylenically unsaturated groups contained in the modified polyphenylene ether compound (g) include alkenyl groups such as ethenyl, allyl, methallyl, acryloyl, methacryloyl, propenyl, butenyl, hexenyl, and octenyl, cyclic alkenyl groups such as cyclopentenyl and cyclohexenyl, and vinylaryl groups such as vinylphenyl and vinylnaphthyl. Methacryloyl and/or vinylbenzyl groups are preferred, and vinylbenzyl groups are more preferred in terms of excellent chemical resistance and desmear resistance.
  • vinylbenzyl groups include 4-vinylbenzyl and 3-vinylbenzyl groups.
  • the two or more ethylenically unsaturated groups may be the same functional group or different functional groups.
  • the modified polyphenylene ether compound (g) may be a polyphenylene ether compound represented by the formula (OP).
  • OP polyphenylene ether compound represented by the formula (OP).
  • X represents an aromatic group
  • -(Y-O) n1 - represents a polyphenylene ether structure
  • n1 represents an integer of 1 to 100
  • n2 represents an integer of 1 to 4.
  • Rx is a group represented by formula (Rx-1) or formula (Rx-2).
  • R 1 , R 2 , and R 3 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, or an alkynyl group.
  • * represents a bonding site with an oxygen atom.
  • Each Mc independently represents a hydrocarbon group having 1 to 12 carbon atoms.
  • z represents an integer of 0 to 4.
  • r represents an integer of 0 to 6.
  • the aromatic group represented by X may or may not have a substituent on the benzene ring, but preferably has one.
  • the above-mentioned substituent Z can be exemplified, and it is preferably at least one selected from the group consisting of an alkyl group having 6 or less carbon atoms, an aryl group, and a halogen atom, more preferably an alkyl group having 3 or less carbon atoms, and even more preferably a methyl group.
  • the polyphenylene ether structure represented by -(Y-O)n 1 - may or may not have a substituent on the benzene ring, but preferably has one.
  • the substituent include the above-mentioned substituent Z, and the substituent is preferably an alkyl group or a phenyl group having 6 or less carbon atoms, more preferably an alkyl group having 3 or less carbon atoms, and further preferably a methyl group.
  • n1 and/or n2 are integers of 2 or more, n1 structural units (Y-O) and/or n2 structural units may be the same or different.
  • n2 is preferably 2 or more, and more preferably 2.
  • R 1 , R 2 and R 3 each independently represent a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group.
  • R 1 is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group, and further preferably a hydrogen atom.
  • R2 and R3 each independently represent preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group, and further preferably a hydrogen atom.
  • the number of carbon atoms in the alkyl group, alkenyl group, or alkynyl group represented by R 1 , R 2 , and R 3 is preferably 5 or less, and more preferably 3 or less.
  • r represents an integer from 0 to 6, and may be an integer of 1 or more, and is preferably an integer of 5 or less, more preferably an integer of 4 or less, even more preferably an integer of 3 or less, even more preferably 1 or 2, and even more preferably 1.
  • each Mc independently represents a hydrocarbon group having 1 to 12 carbon atoms, preferably a hydrocarbon group having 1 to 10 carbon atoms, more preferably a linear or branched alkyl group having 1 to 10 carbon atoms, still more preferably a methyl group, ethyl group, isopropyl group, isobutyl group, t-butyl group, pentyl group, octyl group, or nonyl group, and still more preferably a methyl group, ethyl group, isopropyl group, isobutyl group, or t-butyl group.
  • z represents an integer of 0 to 4, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, even more preferably 0 or 1, and still more preferably 0.
  • a specific example of the group represented by formula (Rx-1) is a vinylbenzyl group
  • a specific example of the group represented by formula (Rx-2) is a (meth)acryloyl group.
  • Rx is preferably a group represented by formula (Rx-2).
  • the resin composition of the present embodiment preferably contains, as the polyphenylene ether compound having a terminal carbon-carbon unsaturated double bond, a compound represented by formula (OP), which contains both a polyphenylene ether compound having a group represented by formula (Rx-1) and a compound having a polyphenylene ether group having a group represented by formula (Rx-2).
  • the modified polyphenylene ether compound (g) includes a compound represented by the formula (OP-1).
  • X represents an aromatic group
  • -(Y-O)n 2 - represents a polyphenylene ether structure
  • R 1 , R 2 , and R 3 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, or an alkynyl group
  • n 1 represents an integer of 1 to 6
  • n 2 represents an integer of 1 to 100
  • n 3 represents an integer of 2 to 4.
  • n2 and/or n3 are integers of 2 or more
  • the n2 structural units (Y-O) and/or the n3 structural units may be the same or different.
  • n3 is preferably 2 or more, and more preferably 2.
  • the modified polyphenylene ether compound (g) in the present embodiment is preferably represented by formula (OP-2).
  • -(O-X-O)- represents the formula (OP-3):
  • R 4 , R 5 , R 6 , R 10 and R 11 may be the same or different and are an alkyl group having 6 or less carbon atoms or a phenyl group.
  • R 7 , R 8 and R 9 may be the same or different and are a hydrogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group.
  • -(Y-O)- represents a group represented by formula (OP-5):
  • R 20 and R 21 may be the same or different and are an alkyl group having 6 or less carbon atoms or a phenyl group.
  • R 22 and R 23 may be the same or different and are a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group.
  • a and b at least one of which is not 0, represent an integer of 0 to 100, preferably an integer of 0 to 50, and more preferably an integer of 1 to 30.
  • two or more -(Y-O)- may each independently represent an arrangement of one type of structure, or two or more types of structures may be arranged in a block or random manner.
  • -A- in formula (OP-4) may be, for example, a divalent organic group such as a methylene group, an ethylidene group, a 1-methylethylidene group, a 1,1-propylidene group, a 1,4-phenylenebis(1-methylethylidene) group, a 1,3-phenylenebis(1-methylethylidene) group, a cyclohexylidene group, a phenylmethylene group, a naphthylmethylene group, or a 1-phenylethylidene group, but is not limited to these.
  • a divalent organic group such as a methylene group, an ethylidene group, a 1-methylethylidene group, a 1,1-propylidene group, a 1,4-phenylenebis(1-methylethylidene) group, a 1,3-phenylenebis(1-methylethylid
  • R 4 , R 5 , R 6 , R 10 , R 11 , R 20 and R 21 are alkyl groups having 3 or less carbon atoms, R 7 , R 8 , R 9 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 22 and R
  • a polyphenylene ether compound in which 23 is a hydrogen atom or an alkyl group having 3 or less carbon atoms is preferred, and in particular, -(O-X-O)- represented by formula (OP-3) or formula (OP-4) is more preferably formula (OP-9), formula (OP-10), and/or formula (OP-11), and -(Y-O)- represented by formula (OP-5) is more preferably formula (OP-12) or formula (OP-13), and further more preferably -(O-X-O)- is formula (OP-9) and -(Y-O)- is formula (OP-12).
  • the two or more -(Y-O)- may each independently be a structure in which two or more of formula (OP-12) and/or formula (OP-13) are arranged, or a structure in which formula (OP-12) and formula (OP-13) are arranged in blocks or randomly.
  • R 44 , R 45 , R 46 , and R 47 may be the same or different and each represent a hydrogen atom or a methyl group.
  • -B- represents a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms.
  • Specific examples of -B- include the same as the specific examples of -A- in formula (OP-4).
  • -B- is a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms.
  • Specific examples of -B- include the same as the specific examples of -A- in formula (OP-4).
  • the modified polyphenylene ether compound (g) is more preferably a compound represented by formula (OP-14) and/or a compound represented by formula (OP-15), and even more preferably a compound represented by formula (OP-15).
  • a and b each independently represent an integer from 0 to 100, and at least one of a and b is an integer from 1 to 100.
  • a and b each independently have the same definition as a and b in formula (OP-2), and the preferred ranges are also the same.
  • a and b each independently represent an integer from 0 to 100, and at least one of a and b is an integer from 1 to 100.
  • a and b each independently have the same definition as a and b in formula (OP-2), and the preferred ranges are also the same.
  • the polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds may be produced by a known method, or a commercially available product may be used.
  • commercially available products include "SA9000” manufactured by SABIC Innovative Plastics, which is a modified polyphenylene ether compound having a terminal methacryloyl group.
  • modified polyphenylene ether compounds having a terminal vinylbenzyl group include "OPE-2St1200" and "OPE-2St2200” manufactured by Mitsubishi Gas Chemical.
  • modified polyphenylene ether compounds having a terminal vinylbenzyl group examples include polyphenylene ether compounds having a terminal hydroxyl group such as "SA90" manufactured by SABIC Innovative Plastics, which have been modified to a vinylbenzyl group using vinylbenzyl chloride or the like.
  • the polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds preferably modified polyphenylene ether compound (g)
  • preferably modified polyphenylene ether compound (g) preferably has a polystyrene-equivalent number average molecular weight (details follow the method described in the Examples below) as determined by GPC (gel permeation chromatography) of 500 or more and 3,000 or less.
  • GPC gel permeation chromatography
  • the polystyrene-equivalent weight average molecular weight by GPC of the polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds is preferably 800 to 10,000, more preferably 800 to 5,000.
  • the relative dielectric constant (Dk) and dielectric loss tangent (Df) of the cured product of the resin composition tend to be lower, and by making it equal to or less than the upper limit, the solubility, low viscosity, and moldability of the resin composition in a solvent when preparing a varnish or the like described below tend to be further improved.
  • the terminal carbon-carbon unsaturated double bond equivalent is preferably 400 to 5000 g, more preferably 400 to 2500 g per carbon-carbon unsaturated double bond.
  • the relative dielectric constant (Dk) and dielectric loss tangent (Df) of the cured product of the resin composition tend to be lower.
  • the solubility in the solvent, low viscosity, and moldability of the resin composition tend to be further improved.
  • the functional group equivalent (carbon-carbon unsaturated double bond equivalent) in a polyphenylene ether compound having a terminal carbon-carbon unsaturated double bond is calculated from the reciprocal of the amount of double bonds determined from the results of measurement using an infrared spectrometer.
  • the double bond equivalent [g/eq.] was calculated as follows. The powder of the polyphenylene ether compound is weighed and the weight is recorded. The powder is placed in a measuring flask, and then the measurement sample is prepared by diluting the powder to a predetermined amount with carbon disulfide. The sample liquid is placed in a measurement cell and set in an infrared spectrophotometer (FT/IR-4600, manufactured by JASCO Corporation).
  • Double bond equivalent [g/eq.] powder weight in measurement sample [g] / double bond concentration [mol/L] ⁇ measurement sample liquid volume [L]
  • the functional group equivalent of other compounds can also be measured by following the above method. However, for compounds (monomers) that can be expressed by a single molecular weight, the value of the functional group equivalent calculated by (theoretical molecular weight ⁇ number of functional groups) should be used preferentially.
  • the lower limit of the content of the polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds is preferably 1 part by mass or more, more preferably 5 parts by mass or more, even more preferably 10 parts by mass or more, and may be 15 parts by mass or more, relative to 100 parts by mass of the resin solid content in the resin composition.
  • the upper limit of the content of the polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds is preferably 70 parts by mass or less, more preferably 60 parts by mass or less, even more preferably 50 parts by mass or less, even more preferably 40 parts by mass or less, even more preferably 30 parts by mass or less, and may be 20 parts by mass or less, relative to 100 parts by mass of the resin solid content in the resin composition.
  • the resin composition in the present embodiment may contain only one type of polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds, or may contain two or more types. When two or more types are contained, it is preferable that the total amount is in the above range.
  • the resin composition of the present embodiment preferably contains a polymer having a structural unit represented by formula (V).
  • the polymer having a structural unit represented by formula (V) is a polymer containing two or more carbon-carbon unsaturated double bonds, and is preferably a polymer having two or more structural units represented by formula (V).
  • a resin composition having excellent low dielectric properties low dielectric constant, low dielectric loss tangent
  • Ar represents an aromatic hydrocarbon linking group.
  • the aromatic hydrocarbon linking group may be a group consisting of only aromatic hydrocarbons which may have a substituent, or may be a group consisting of a combination of aromatic hydrocarbons which may have a substituent and other linking groups, and is preferably a group consisting of only aromatic hydrocarbons which may have a substituent.
  • the substituent that the aromatic hydrocarbon may have includes the substituent Z (e.g., an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a hydroxy group, an amino group, a carboxy group, a halogen atom, etc.). It is also preferable that the aromatic hydrocarbon does not have a substituent.
  • the aromatic hydrocarbon linking group is usually a divalent linking group.
  • aromatic hydrocarbon linking groups include phenylene groups, naphthalenediyl groups, anthracenediyl groups, phenanthrenediyl groups, biphenyldiyl groups, and fluorenediyl groups, which may have a substituent, and among these, phenylene groups, which may have a substituent, are preferred.
  • substituent include the above-mentioned substituent Z, but it is preferable that the above-mentioned phenylene groups and other groups do not have a substituent.
  • the structural unit represented by formula (V) more preferably contains at least one of the structural units represented by the following formula (V1), the structural unit represented by the following formula (V2), and the structural unit represented by the following formula (V3).
  • * indicates a bonding position.
  • structural units represented by formulas (V1) to (V3) may be collectively referred to as "structural unit (a)".
  • L1 is an aromatic hydrocarbon linking group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms).
  • aromatic hydrocarbon linking group preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms.
  • Specific examples include phenylene groups, naphthalenediyl groups, anthracenediyl groups, phenanthrenediyl groups, biphenyldiyl groups, and fluorenediyl groups, which may have a substituent, and among these, phenylene groups which may have a substituent are preferred.
  • substituent include the above-mentioned substituent Z, but it is preferable that the above-mentioned phenylene groups and other groups do not have a substituent.
  • the compound forming the structural unit (a) is preferably a divinyl aromatic compound, such as divinylbenzene, bis(1-methylvinyl)benzene, divinylnaphthalene, divinylanthracene, divinylbiphenyl, and divinylphenanthrene.
  • divinylbenzene is particularly preferred.
  • These divinyl aromatic compounds may be used alone or in combination as necessary.
  • the polymer having the structural unit represented by formula (V) may be a homopolymer of the structural unit (a), or may be a copolymer with a structural unit derived from another monomer.
  • the copolymerization ratio of the structural unit (a) is preferably 5 mol% or more, more preferably 10 mol% or more, and even more preferably 15 mol% or more.
  • the upper limit is preferably 90 mol% or less, more preferably 85 mol% or less, even more preferably 80 mol% or less, even more preferably 70 mol% or less, even more preferably 60 mol% or less, even more preferably 50 mol% or less, even more preferably 40 mol% or less, especially more preferably 30 mol% or less, and may be 25 mol% or less.
  • structural unit (b) derived from an aromatic compound having one vinyl group (monovinyl aromatic compound).
  • the structural unit (b) derived from a monovinyl aromatic compound is preferably a structural unit represented by the following formula (V4):
  • L2 is an aromatic hydrocarbon linking group, and preferred specific examples thereof include the examples of L1 mentioned above.
  • R V1 is a hydrogen atom or a hydrocarbon group (preferably an alkyl group) having 1 to 12 carbon atoms.
  • R V1 is a hydrocarbon group, the number of carbon atoms is preferably 1 to 6, and more preferably 1 to 3.
  • R V1 and L 2 may have the above-mentioned substituent Z.
  • the polymer having the structural unit represented by formula (V) is a copolymer containing the structural unit (b) derived from a monovinyl aromatic compound
  • examples of the monovinyl aromatic compound include vinyl aromatic compounds such as styrene, vinylnaphthalene, and vinylbiphenyl; and nuclear alkyl-substituted vinyl aromatic compounds such as o-methylstyrene, m-methylstyrene, p-methylstyrene, o,p-dimethylstyrene, o-ethylvinylbenzene, m-ethylvinylbenzene, p-ethylvinylbenzene, methylvinylbiphenyl, and ethylvinylbiphenyl.
  • the monovinyl aromatic compounds exemplified here may have the aforementioned substituent Z as appropriate. Furthermore, these monovinyl aromatic compounds may be used alone or in combination.
  • the copolymerization ratio of the structural unit (b) is preferably 10 mol% or more, more preferably 15 mol% or more, and may be 20 mol% or more, 30 mol% or more, 40 mol% or more, 50 mol% or more, 60 mol% or more, 70 mol% or more, or 75 mol% or more.
  • the upper limit is preferably 98 mol% or less, more preferably 90 mol% or less, and even more preferably 85 mol% or less.
  • the polymer having the structural unit represented by formula (V) may have other structural units other than the structural unit (a) and the structural unit (b).
  • Examples of other structural units include the structural unit (c) derived from a cycloolefin compound.
  • Examples of cycloolefin compounds include hydrocarbons having a double bond in the ring structure.
  • cycloolefin compounds such as cyclobutene, cyclopentene, cyclohexene, and cyclooctene
  • compounds containing a norbornene ring structure such as norbornene and dicyclopentadiene, and cycloolefin compounds in which aromatic rings are condensed such as indene and acenaphthylene
  • norbornene compounds include those described in paragraphs 0037 to 0043 of JP 2018-39995 A, the contents of which are incorporated herein by reference.
  • the cycloolefin compounds exemplified here may further have the above-mentioned substituent Z.
  • the copolymerization ratio of the structural unit (c) is preferably 10 mol% or more, more preferably 20 mol% or more, and even more preferably 30 mol% or more.
  • the upper limit is preferably 90 mol% or less, more preferably 80 mol% or less, and even more preferably 70 mol% or less, and may be 50 mol% or less, or may be 30 mol% or less.
  • the polymer having the structural unit represented by formula (V) may further incorporate a structural unit (d) derived from a different polymerizable compound (hereinafter also referred to as other polymerizable compound).
  • a different polymerizable compound hereinafter also referred to as other polymerizable compound.
  • other polymerizable compounds include compounds containing three vinyl groups. Specific examples include 1,3,5-trivinylbenzene, 1,3,5-trivinylnaphthalene, and 1,2,4-trivinylcyclohexane. Alternatively, examples include ethylene glycol diacrylate, butadiene (e.g., 1,3-butadiene), isoprene, and the like.
  • the copolymerization ratio of the structural unit (d) derived from the other polymerizable compound is preferably 30 mol% or less, more preferably 20 mol% or less, and even more preferably 10 mol% or less.
  • An embodiment of the polymer having the structural unit represented by formula (V) is a polymer essentially containing the structural unit (a) and containing at least one of the structural units (b) to (d). Further, the total of the structural units (a) to (d) is 95 mol % or more, and further 98 mol % or more of the total structural units.
  • the structural unit (a) is essential, and among all structural units excluding the terminals, structural units containing an aromatic ring preferably account for 90 mol % or more, more preferably 95 mol % or more, and may even account for 100 mol %.
  • one structural unit is defined as being derived from one molecule of a monomer (e.g., a divinyl aromatic compound, a monovinyl aromatic compound, etc.) used in the production of a polymer having a structural unit represented by formula (V).
  • a monomer e.g., a divinyl aromatic compound, a monovinyl aromatic compound, etc.
  • the method for producing a polymer having a structural unit represented by formula (V) is not particularly limited and may be a conventional method, but for example, a raw material containing a divinyl aromatic compound (in the coexistence of a monovinyl aromatic compound, a cycloolefin compound, etc., as necessary) may be polymerized in the presence of a Lewis acid catalyst.
  • a Lewis acid catalyst a metal fluoride such as boron trifluoride or a complex thereof can be used.
  • the structure may be that of the following formula (E2), in which L2 and R V1 are the same as defined in the above formula (V4).
  • * represents a bonding position.
  • *-CH CH-L 2 -R V1 (E2)
  • the molecular weight of the polymer having a structural unit represented by formula (V), in terms of number average molecular weight Mn, is preferably 300 or more, more preferably 500 or more, even more preferably 1,000 or more, and still more preferably 1,500 or more.
  • the upper limit of the number average molecular weight Mn is preferably 130,000 or less, more preferably 120,000 or less, even more preferably 110,000 or less, and still more preferably 100,000 or less, and may be 30,000 or less, 10,000 or less, or 5,000 or less.
  • the molecular weight of the polymer having the structural unit represented by formula (V) is preferably 1,000 or more, more preferably 2,000 or more, and even more preferably 3,000 or more, in terms of weight average molecular weight Mw.
  • the excellent low dielectric properties of the polymer having the structural unit represented by formula (V), particularly the low dielectric properties after Df and moisture absorption, can be effectively exhibited in the cured product of the resin composition.
  • the upper limit of the weight average molecular weight Mw is preferably 160,000 or less, more preferably 150,000 or less, even more preferably 140,000 or less, even more preferably 130,000 or less, and may be 80,000 or less, or 50,000 or less.
  • the monodispersity (Mw/Mn), which is expressed by the ratio of the weight average molecular weight Mw to the number average molecular weight Mn, is preferably 100 or less, more preferably 50 or less, even more preferably 20 or less, and may be 15 or less, or may be 12 or less.
  • a practical value is 1.1 or more, preferably 2.0 or more, more preferably 4 or more, even more preferably 5 or more, even more preferably 7 or more, and even more preferably 8 or more.
  • the above Mw and Mn are measured according to the description in the examples described later.
  • the resin composition of the present embodiment contains two or more polymers having a structural unit represented by formula (V), it is preferable that the Mw, Mn and Mw/Mn of the mixture satisfy the above ranges.
  • the vinyl group equivalent of the polymer having the structural unit represented by formula (V) is preferably 200 g/eq. or more, more preferably 230 g/eq. or more, even more preferably 250 g/eq. or more, and may be 300 g/eq. or more or 350 g/eq. or more.
  • the vinyl group equivalent is preferably 1200 g/eq. or less, more preferably 1000 g/eq. or less, and may be 800 g/eq. or less, 600 g/eq. or less, 400 g/eq. or less, or 300 g/eq. or less.
  • the vinyl group equivalent By setting the vinyl group equivalent to the above lower limit or more, the storage stability of the resin composition tends to be improved and the flowability of the resin composition tends to be improved. Therefore, moldability is improved, voids are less likely to occur when forming a prepreg, etc., and a more reliable printed wiring board tends to be obtained. On the other hand, by setting the vinyl group equivalent to the above upper limit or less, the moisture absorption and heat resistance of the obtained cured product tends to be improved.
  • the polymer having the structural unit represented by formula (V) used in this embodiment preferably has a cured product with excellent low dielectric properties.
  • the cured product of the polymer having the structural unit represented by formula (V) used in this embodiment preferably has a relative dielectric constant (Dk) of 2.80 or less at a frequency of 10 GHz measured according to a cavity resonator perturbation method, more preferably 2.60 or less, even more preferably 2.50 or less, and even more preferably 2.40 or less.
  • Dk relative dielectric constant
  • the lower limit of the relative dielectric constant is, for example, 1.80 or more in practical use.
  • the cured product of the polymer having the structural unit represented by formula (V) used in this embodiment preferably has a dielectric loss tangent (Df) of 0.0030 or less at a frequency of 10 GHz measured according to a cavity resonator perturbation method, more preferably 0.0020 or less, even more preferably 0.0019 or less, even more preferably 0.0018 or less, and even more preferably 0.0010 or less.
  • the lower limit of the dielectric loss tangent is, for example, 0.0001 or more in practical use.
  • the dielectric loss tangent (Df) is measured according to the method described in the Examples below.
  • the relative dielectric constant (Dk) is also measured according to the method for measuring Df in the Examples.
  • the lower limit of the content of the polymer having a structural unit represented by formula (V) is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, even more preferably 15 parts by mass or more, even more preferably 20 parts by mass or more, even more preferably 25 parts by mass or more, and may be 35 parts by mass or more, or 40 parts by mass or more, when the resin solid content in the resin composition is 100 parts by mass.
  • the upper limit of the content of the polymer having a structural unit represented by formula (V) is preferably 70 parts by mass or less, more preferably 60 parts by mass or less, even more preferably 55 parts by mass or less, even more preferably 50 parts by mass or less, and may be 45 parts by mass or less, when the resin solid content in the resin composition is 100 parts by mass.
  • the polymer having the structural unit represented by formula (V) may be contained in the resin composition in one type or in two or more types. When two or more types are contained, it is preferable that the total amount is in the above range.
  • the resin composition of the present embodiment preferably contains a compound containing a (meth)allyl group, more preferably a compound containing an allyl group.
  • a compound containing a (meth)allyl group By containing a compound containing a (meth)allyl group, the thermal expansion coefficient of the obtained cured product tends to be further reduced.
  • the compound containing a (meth)allyl group is preferably a compound containing two or more (meth)allyl groups, and more preferably a compound containing two or more allyl groups.
  • the compound containing a (meth)allyl group preferably contains at least one selected from the group consisting of an allyl isocyanurate compound, an allyl group-substituted nadimide compound, an allyl compound having a glycoluril structure, and a diallyl phthalate, more preferably contains at least one selected from the group consisting of an allyl isocyanurate compound, an allyl group-substituted nadimide compound, and an allyl compound having a glycoluril structure, and even more preferably contains an allyl group-substituted nadimide compound.
  • the molecular weight is preferably 195 or more, more preferably 300 or more, even more preferably 400 or more, and even more preferably 500 or more.
  • the molecular weight of the compound containing a (meth)allyl group is also preferably 3000 or less, more preferably 2000 or less, even more preferably 1000 or less, and even more preferably 800 or less. By making the molecular weight equal to or less than the upper limit, low thermal expansion tends to be further improved.
  • the content of the resin composition of the present embodiment contains a compound containing a (meth)allyl group
  • the content is preferably 1 part by mass or more, more preferably 3 parts by mass or more, even more preferably 5 parts by mass or more, even more preferably 8 parts by mass or more, and may be 10 parts by mass or more, relative to 100 parts by mass of the resin solid content in the resin composition.
  • the upper limit of the content of the compound containing a (meth)allyl group is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, and may be 15 parts by mass or less, or 12 parts by mass or less, relative to 100 parts by mass of the resin solid content in the resin composition.
  • the resin composition of the present embodiment may contain only one type of compound containing a (meth)allyl group, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.
  • the total content of the other maleimide compound (B) and the compound containing a (meth)allyl group is preferably 1 part by mass or more, more preferably 3 parts by mass or more, even more preferably 10 parts by mass or more, even more preferably 20 parts by mass or more, even more preferably 30 parts by mass or more, even more preferably 45 parts by mass or more, and may be 50 parts by mass or more depending on the application.
  • the total content of the other maleimide compound (B) and the compound containing a (meth)allyl group is preferably 90 parts by mass or less, more preferably 80 parts by mass or less, even more preferably 70 parts by mass or less, and may be 60 parts by mass or less, or 55 parts by mass or less.
  • the mass ratio of the other maleimide compound (B) to the compound containing a (meth)allyl group is preferably 6:4 to 9:1, more preferably 7:3 to 9:1, and even more preferably 8:2 to 9:1.
  • allyl isocyanurate compounds is not particularly limited as long as it is a compound having two or more allyl groups and an isocyanurate ring (nurate skeleton), but a compound represented by formula (TA) is preferred.
  • Formula (TA) (In formula (TA), R A represents a substituent).
  • R 1 A represents a substituent, and is more preferably a substituent having a formula weight of 15 to 500.
  • a first example of R A is an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 2 to 22 carbon atoms.
  • an allyl compound having an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 2 to 22 carbon atoms it is possible to provide a resin composition that is excellent in crosslinkability and can give a cured product having high toughness. As a result, even if the resin composition does not contain a substrate such as glass cloth, cracking during etching or the like can be suppressed.
  • the number of carbon atoms in the alkyl group and/or alkenyl group is preferably 3 or more, more preferably 8 or more, and may be 12 or more, but is preferably 18 or less. This improves the resin flowability of the resin composition, and is considered to result in superior circuit filling properties when a multilayer circuit board or the like is produced using the resin composition of the present embodiment.
  • R A is a group containing an allyl isocyanurate group.
  • the compound represented by formula (TA) is preferably a compound represented by formula (TA-1).
  • Formula (TA-1) (In formula (TA-1), R A2 is a divalent linking group.)
  • R A2 is preferably a divalent linking group having a formula weight of 54 to 250, more preferably a divalent linking group having a formula weight of 54 to 250 and both ends being carbon atoms, and even more preferably an aliphatic hydrocarbon group having 2 to 20 carbon atoms (however, the aliphatic hydrocarbon group may contain an ether group or may have a hydroxyl group). More specifically, R A2 is preferably a group represented by any of the following formulae (i) to (iii): (In the formulas (i) to (iii), p c1 represents the number of repeating methylene units and is an integer from 2 to 18. p c2 represents the number of repeating oxyethylene units and is 0 or 1. * represents a bonding site.) The p c1 is preferably an integer of 2 to 10, more preferably an integer of 3 to 8, and further preferably an integer of 3 to 5. The p c2 may be 0 or 1, but is preferably 1.
  • R A2 is preferably the first example.
  • the reactive group (allyl group) equivalent of the compound represented by formula (TA) is not more than 1000. If the equivalent is not more than 1000, it is considered that a high Tg can be obtained more reliably.
  • the alkyl group having 1 to 22 carbon atoms include linear or branched alkyl groups, such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, an eicosyl group, a docosyl group, etc.
  • the alkenyl group having 2 to 22 carbon atoms include an allyl group, a decenyl group
  • compounds represented by formula (TA) include triallyl isocyanurate, 5-octyl-1,3-diallyl isocyanurate, 5-dodecyl-1,3-diallyl isocyanurate, 5-tetradecyl-1,3-diallyl isocyanurate, 5-hexadecyl-1,3-diallyl isocyanurate, 5-octadecyl-1,3-diallyl isocyanurate, 5-eicosyl-1,3-diallyl isocyanurate, 5-docosyl-1,3-diallyl isocyanurate, and 5-decenyl-1,3-diallyl isocyanurate. These may be used alone or in combination of two or more, and may be used as a prepolymer.
  • the method for producing the compound represented by formula (TA) is not particularly limited, but for example, the compound can be obtained by reacting diallyl isocyanurate with an alkyl halide in an aprotic polar solvent such as N,N'-dimethylformamide in the presence of a basic substance such as sodium hydroxide, potassium carbonate, or triethylamine at a temperature of about 60°C to 150°C.
  • an aprotic polar solvent such as N,N'-dimethylformamide
  • a basic substance such as sodium hydroxide, potassium carbonate, or triethylamine
  • the compound represented by formula (TA) may be a commercially available product.
  • Commercially available products include, but are not limited to, L-DAIC manufactured by Shikoku Chemical Industry Co., Ltd., and P-DAIC having a phosphorus-based substituent manufactured by Shikoku Chemical Industry Co., Ltd.
  • An example of triallyl isocyanurate is TAIC manufactured by Shinryo Corporation.
  • An example of the compound represented by formula (TA-1) is DD-1 manufactured by Shikoku Chemical Industry Co., Ltd.
  • the molecular weight of the allyl isocyanurate compound (preferably a compound represented by formula (TA)) is preferably 200 or more, more preferably 300 or more, even more preferably 400 or more, and even more preferably 500 or more. By setting the molecular weight to the above lower limit or more, low dielectric properties and heat resistance tend to be further improved.
  • the molecular weight of the allyl isocyanurate compound (preferably a compound represented by formula (TA)) is preferably 3000 or less, more preferably 2000 or less, even more preferably 1000 or less, and even more preferably 800 or less. By setting the molecular weight to the above upper limit or less, the low thermal expansion of the obtained cured product tends to be further improved.
  • the content thereof is preferably 1 part by mass or more, more preferably 3 parts by mass or more, even more preferably 5 parts by mass or more, and may be 10 parts by mass or more, relative to 100 parts by mass of the resin solid content in the resin composition.
  • the upper limit of the content of the allyl isocyanurate compound is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and even more preferably 20 parts by mass or less, relative to 100 parts by mass of the resin solid content in the resin composition.
  • the resin composition of the present embodiment may contain only one type of allyl isocyanurate, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.
  • the allyl-substituted nadimide compound is not particularly limited as long as it has two or more allyl-substituted nadimide groups in the molecule. Specific examples thereof include the compound represented by the following formula (AN).
  • Formula (AN) In formula (AN), R 1 's each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R 2 's each independently represent an alkylene group having 1 to 6 carbon atoms, a phenylene group, a biphenylene group, a naphthylene group, or a group represented by formula (AN-2) or (AN-3).
  • Formula (AN-3) (In formula (AN-3), R 4 each independently represents an alkylene group having 1 to 4 carbon atoms or a cycloalkylene group having 5 to 8 carbon atoms.)
  • the compound represented by formula (AN) may be a commercially available product.
  • commercially available products include, but are not limited to, the compound represented by formula (AN-4) (BANI-M (manufactured by Maruzen Petrochemical Co., Ltd.)) and the compound represented by formula (AN-5) (BANI-X (manufactured by Maruzen Petrochemical Co., Ltd.)). These may be used alone or in combination of two or more.
  • the molecular weight of the allyl-substituted nadiimide compound (preferably a compound represented by formula (AN)) is preferably 400 or more, more preferably 500 or more, and may be 550 or more. By making the molecular weight of the allyl-substituted nadiimide compound equal to or greater than the lower limit above, the low dielectric properties, low thermal expansion properties, and heat resistance tend to be further improved.
  • the molecular weight of the allyl-substituted nadiimide compound (preferably a compound represented by formula (AN)) is also preferably 1500 or less, more preferably 1000 or less, and even more preferably 800 or less, and may be 700 or less, or 600 or less. By making the molecular weight of the allyl-substituted nadiimide compound equal to or less than the upper limit above, the moldability and peel strength tend to be further improved.
  • the content thereof is preferably 1 part by mass or more, more preferably 3 parts by mass or more, even more preferably 5 parts by mass or more, even more preferably 8 parts by mass or more, and may be 10 parts by mass or more, relative to 100 parts by mass of the resin solid content in the resin composition.
  • the upper limit value of the content of the allyl group-substituted nadimide compound is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, even more preferably 25 parts by mass or less, and may further be 20 parts by mass or less, or 15 parts by mass or less, relative to 100 parts by mass of the resin solid content in the resin composition.
  • the resin composition of the present embodiment may contain only one kind of allyl group-substituted nadimide compound, or may contain two or more kinds. When two or more kinds are contained, it is preferable that the total amount is in the above range.
  • the allyl compound having a glycoluril structure is not particularly limited as long as it is a compound containing a glycoluril structure and two or more allyl groups, and is preferably a compound represented by formula (GU-0), and more preferably a compound represented by formula (GU).
  • GUI-0 a compound represented by formula (GU-0)
  • R 1 is each independently a hydrogen atom or a substituent, and at least two R 1s are groups containing a (meth)allyl group.
  • each R 1 is independently preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkenyl group having 2 to 5 carbon atoms, more preferably an alkenyl group having 2 to 5 carbon atoms, more preferably a (meth)allyl group, and even more preferably an allyl group.
  • each R 2 independently is preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, and more preferably a hydrogen atom or a methyl group.
  • R is each independently a hydrogen atom or a substituent, and at least two R are groups containing an allyl group.
  • each R is independently preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkenyl group having 2 to 5 carbon atoms, more preferably an alkenyl group having 2 to 5 carbon atoms, and even more preferably an allyl group.
  • a specific example of a compound represented by formula (GU) is 1,3,4,6-tetraallylglycoluril (a compound in which all R's in formula (GU) are allyl groups).
  • the compound represented by formula (GU) may also be a commercially available product.
  • a commercially available product There is no particular limitation to commercially available products, but an example of such a product is TA-G manufactured by Shikoku Chemical Industries Co., Ltd.
  • the molecular weight of the allyl compound having a glycoluril structure (preferably a compound represented by formula (GU-0), more preferably a compound represented by formula (GU)) is preferably 195 or more, more preferably 220 or more, even more preferably 250 or more, and may be 300 or more, 400 or more.
  • the molecular weight of the allyl compound having a glycoluril structure (preferably a compound represented by formula (GU-0), more preferably a compound represented by formula (GU)) is also preferably 1500 or less, more preferably 1000 or less, even more preferably 800 or less, and may be 700 or less, 600 or less.
  • the content of the allyl compound having a glycoluril structure preferably a compound represented by formula (GU-0), more preferably a compound represented by formula (GU)
  • the content is preferably 1 part by mass or more, more preferably 3 parts by mass or more, even more preferably 5 parts by mass or more, and may be 10 parts by mass or more, relative to 100 parts by mass of the resin solid content in the resin composition.
  • the upper limit of the content of the allyl compound having a glycoluril structure is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, even more preferably 25 parts by mass or less, and may be 20 parts by mass or less, relative to 100 parts by mass of the resin solid content in the resin composition.
  • the resin composition of the present embodiment may contain only one type of allyl compound having a glycoluril structure, or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range.
  • the resin composition of the present embodiment may contain a polyfunctional (meth)acrylate compound.
  • a polyfunctional (meth)acrylate compound that also falls under the category of a polyphenylene ether compound having a terminal carbon-carbon unsaturated double bond is classified as a polyphenylene ether compound having a terminal carbon-carbon unsaturated double bond.
  • the polyfunctional (meth)acrylate compound means a compound containing two or more (meth)acryloyloxy groups in one molecule, and preferably contains three or more (meth)acryloyloxy groups in one molecule.
  • the polyfunctional (meth)acrylate compound is preferably a compound having 3 to 5 (meth)acryloyloxy groups, more preferably a compound having 3 or 4 (meth)acryloyloxy groups, and even more preferably a compound having 3 (meth)acryloyloxy groups.
  • the polyfunctional (meth)acrylate compound is preferably a compound having a methacryloyloxy group. Since the polyfunctional (meth)acrylate compound has a large number of (meth)acrylate groups that serve as crosslinking points, it is strongly cured with the maleimide compound (A) or the like, and a cured product having low dielectric properties (Dk and/or Df) and excellent heat resistance is obtained.
  • a compound represented by the formula (MA) is preferable.
  • Formula (MA) (In formula (MA), R 1 represents a hydrogen atom or a substituent, and R 2 each independently represents a hydrogen atom or a methyl group.)
  • R 1 represents a hydrogen atom or a substituent, and is more preferably a substituent having a formula weight of 15 to 500, more preferably a substituent having a formula weight of 15 to 300, even more preferably a substituent having a formula weight of 15 to 100, and even more preferably a substituent having a formula weight of 15 to 50.
  • R 1 is preferably a hydrocarbon group or a (meth)acryloyloxy group, more preferably a hydrocarbon group having 22 or less carbon atoms, and even more preferably an alkyl group having 1 to 22 carbon atoms, or an alkenyl group having 2 to 22 carbon atoms.
  • a compound having an alkyl group having 1 to 22 carbon atoms, or an alkenyl group having 2 to 22 carbon atoms it is possible to provide a resin composition that is excellent in crosslinkability and can give a cured product having high toughness. As a result, even if the resin composition does not contain a substrate such as glass cloth, cracking during etching or the like can be suppressed.
  • the number of carbon atoms in the alkyl group and/or alkenyl group is preferably 2 or more, and may be 8 or more, or may be 12 or more and 18 or less. This improves the resin flowability of the resin composition, and is considered to result in superior circuit filling properties when a multilayer circuit board or the like is produced using the resin composition of the present embodiment.
  • the (meth)acrylic group equivalent of the compound represented by formula (MA) is 1000 g/eq. or less. If the equivalent is 1000 g/eq. or less, a high Tg tends to be obtained more reliably.
  • the lower limit of the (meth)acrylic group equivalent is, for example, 99 g/eq. or more.
  • the alkyl group having 1 to 22 carbon atoms is preferably a linear alkyl group having 1 to 22 carbon atoms or a branched alkyl group having 3 to 22 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, an eicosyl group, a docosyl group, etc.
  • the alkenyl group having 2 to 22 carbon atoms is preferably an alkenyl group having 2 to 15 carbon atoms, such as an allyl group, a decenyl group, etc.
  • compounds represented by formula (MA) include trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, pentaerythritol tetra(meth)acrylate, etc. These may be used alone or in combination of two or more, and may be used as prepolymers.
  • the compound represented by formula (MA) may be commercially available. Although there is no particular limitation, examples of commercially available trimethylolpropane trimethacrylate include "NK Ester TMPT” manufactured by Shin-Nakamura Chemical Co., Ltd.
  • the molecular weight of the polyfunctional (meth)acrylate compound is preferably 200 or more, more preferably 300 or more, and may be 330 or more, 400 or more, or 500 or more. By setting the molecular weight to the above lower limit or more, the low dielectric properties (Dk and/or Df) and heat resistance of the obtained cured product tend to be further improved.
  • the molecular weight of the polyfunctional (meth)acrylate compound (preferably a compound represented by formula (MA)) is preferably 3000 or less, more preferably 2000 or less, even more preferably 1000 or less, and even more preferably 800 or less. By setting the molecular weight to the above upper limit or less, the low thermal expansion properties of the obtained cured product tend to be further improved.
  • examples of polyfunctional (meth)acrylate compounds that can be used include resins having a (meth)acrylic group described in WO 2022/210095 (e.g., compounds described in Synthesis Examples 5 and 21 of the same publication) and resins having a (meth)acrylic group described in Japanese Patent No. 6962507 (e.g., compounds described in Examples 1 to 9), and compounds described in paragraph 0049 of JP 2019-194312 A, the contents of which are incorporated herein by reference.
  • the content of the polyfunctional (meth)acrylate compound is preferably 1 part by mass or more, more preferably 3 parts by mass or more, even more preferably 5 parts by mass or more, and may be 10 parts by mass or more, relative to 100 parts by mass of the resin solid content in the resin composition.
  • the upper limit of the content of the polyfunctional (meth)acrylate compound is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and may be 20 parts by mass or less, relative to 100 parts by mass of the resin solid content in the resin composition.
  • the resin composition of the present embodiment may contain only one type of polyfunctional (meth)acrylate compound, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.
  • the resin composition of the present embodiment may contain a resin component (D) other than the polymaleimide compound (A), a maleimide compound (B) other than the compound (A), and the compound (C) containing two or more polymerizable carbon-carbon unsaturated double bonds.
  • the resin component (D) is usually a thermosetting compound.
  • the other resin component (D) is preferably selected from one or more selected from the group consisting of epoxy compounds, phenol compounds, oxetane resins, benzoxazine compounds, cyanate ester compounds, thermoplastic elastomers, arylcyclobutene resins, polyamide resins, polyimide resins, perfluorovinyl ether resins, and petroleum resins, and more preferably selected from one or more selected from the group consisting of epoxy compounds, phenol compounds, oxetane resins, benzoxazine compounds, cyanate ester compounds, and thermoplastic elastomers.
  • epoxy compounds phenol compounds, oxetane resins, benzoxazine compounds, cyanate ester compounds, and thermoplastic elastomers.
  • the other resin components (D) preferably have excellent low dielectric properties when cured.
  • the dielectric constant (Dk) of the cured product at a frequency of 10 GHz measured according to the cavity resonator perturbation method is preferably 4.0 or less, more preferably 3.5 or less.
  • the lower limit of the dielectric constant (Dk) is, for example, 2.0 or more in practical use.
  • the other resin components (D) preferably have a dielectric loss tangent (Df) of 0.03 or less, more preferably 0.002 or less, at a frequency of 10 GHz measured according to the cavity resonator perturbation method.
  • the lower limit of the dielectric loss tangent (Df) is, for example, 0.0001 or more in practical use.
  • the dielectric constant and dielectric loss tangent can be measured, for example, according to the method described in the examples (curing conditions, measurement conditions).
  • the cured product of the other resin component (D) has high heat resistance.
  • the glass transition temperature of the cured product of the other resin component (D) measured according to JIS C6481 dynamic viscoelasticity measurement, is preferably 150°C or higher, more preferably 180°C or higher, and even more preferably 200°C or higher.
  • the upper limit of the glass transition temperature it is practical for the upper limit of the glass transition temperature to be 400°C or lower.
  • the total content is preferably 1 part by mass or more, more preferably 5 parts by mass or more, even more preferably 10 parts by mass or more, even more preferably 20 parts by mass or more, and may be 30 parts by mass or more, per 100 parts by mass of the resin solid content in the resin composition.
  • the upper limit of the total content of other resin components (D) is preferably 70 parts by mass or less, more preferably 60 parts by mass or less, even more preferably 50 parts by mass or less, and may be 40 parts by mass or less, per 100 parts by mass of the resin solid content in the resin composition.
  • the resin composition of the present embodiment may contain an epoxy compound.
  • the epoxy compound is not particularly limited as long as it is a compound or resin having one or more (preferably 2 to 12, more preferably 2 to 6, even more preferably 2 to 4, still more preferably 2 or 3, and even more preferably 2) epoxy groups in one molecule, and a wide variety of compounds commonly used in the field of printed wiring boards can be used.
  • the epoxy compound examples include bisphenol A type epoxy resins, bisphenol E type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, phenol novolac type epoxy resins, bisphenol A novolac type epoxy resins, glycidyl ester type epoxy resins, aralkyl novolac type epoxy resins, biphenyl aralkyl type epoxy resins, naphthylene ether type epoxy resins, cresol novolac type epoxy resins, polyfunctional phenol type epoxy resins, naphthalene type epoxy resins, anthracene type epoxy resins, naphthalene skeleton modified novolac type epoxy resins, phenol aralkyl type epoxy resins, naphthol aralkyl type epoxy resins, dicyclopentadiene type epoxy resins, biphenyl type epoxy resins, alicyclic epoxy resins, polyol type epoxy resins, phosphorus-containing epoxy resins, glycidyl amines, glycid
  • biphenyl aralkyl type epoxy resins from the viewpoint of further improving flame retardancy and heat resistance, biphenyl aralkyl type epoxy resins, naphthylene ether type epoxy resins, polyfunctional phenol type epoxy resins, and naphthalene type epoxy resins are preferred, and biphenyl aralkyl type epoxy resins are more preferred.
  • the resin composition of the present embodiment preferably contains an epoxy compound in a range that does not impair the effects of the present invention.
  • the content is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 2 parts by mass or more, relative to 100 parts by mass of the resin solid content in the resin composition.
  • the content of the epoxy compound is 0.1 parts by mass or more, the metal foil peel strength and toughness tend to be improved.
  • the upper limit of the content of the epoxy compound is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, even more preferably 8 parts by mass or less, and even more preferably 5 parts by mass or less, relative to 100 parts by mass of the resin solid content in the resin composition.
  • the content of the epoxy compound is 50 parts by mass or less, the electrical properties tend to be improved.
  • the resin composition in the present embodiment may contain only one type of epoxy compound, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.
  • the resin composition of the present embodiment may be configured to be substantially free of epoxy compounds. Substantially free of epoxy compounds means that the content of the epoxy compounds is less than 0.1 parts by mass per 100 parts by mass of the resin solid content in the resin composition.
  • the resin composition of the present embodiment may contain a phenol compound.
  • the phenol compound is not particularly limited as long as it is a phenol compound having one or more (preferably 2 to 12, more preferably 2 to 6, even more preferably 2 to 4, still more preferably 2 or 3, and even more preferably 2) phenolic hydroxy groups in one molecule, and a wide variety of compounds commonly used in the field of printed wiring boards can be used.
  • phenolic compound examples include bisphenol A type phenolic resin, bisphenol E type phenolic resin, bisphenol F type phenolic resin, bisphenol S type phenolic resin, phenol novolac resin, bisphenol A novolac type phenolic resin, glycidyl ester type phenolic resin, aralkyl novolac phenolic resin, biphenyl aralkyl type phenolic resin, cresol novolac type phenolic resin, multifunctional phenolic resin, naphthol resin, naphthol novolac resin, multifunctional naphthol resin, anthracene type phenolic resin, naphthalene skeleton modified novolac type phenolic resin, phenol aralkyl type phenolic resin, naphthol aralkyl type phenolic resin, dicyclopentadiene type phenolic resin, biphenyl type phenolic resin, alicyclic phenolic resin, polyol type phenolic resin, phosphorus-containing phenolic resin,
  • the resin composition of the present embodiment preferably contains a phenolic compound in an amount not impairing the effects of the present invention.
  • the content of the phenolic compound is preferably 0.1 parts by mass or more and 50 parts by mass or less per 100 parts by mass of the resin solid content in the resin composition.
  • the resin composition in the present embodiment may contain only one type of phenol compound, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.
  • the resin composition of the present embodiment may be configured to be substantially free of phenol compounds. Substantially free means that the content of phenol compounds is less than 0.1 parts by mass per 100 parts by mass of the resin solid content in the resin composition.
  • the resin composition of the present embodiment may contain an oxetane resin.
  • the oxetane resin is not particularly limited as long as it is a compound having one or more oxetanyl groups (preferably 2 to 12, more preferably 2 to 6, even more preferably 2 to 4, still more preferably 2 or 3, and even more preferably 2), and a wide variety of compounds commonly used in the field of printed wiring boards can be used.
  • oxetane resins include oxetane, alkyl oxetane (e.g., 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, 3,3-dimethyloxetane, etc.), 3-methyl-3-methoxymethyloxetane, 3,3-di(trifluoromethyl)perfluorooxetane, 2-chloromethyloxetane, 3,3-bis(chloromethyl)oxetane, biphenyl-type oxetane, OXT-101 (manufactured by Toagosei Co., Ltd.), and OXT-121 (manufactured by Toagosei Co., Ltd.).
  • alkyl oxetane e.g., 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxe
  • the resin composition of the present embodiment preferably contains an oxetane resin in a range that does not impair the effects of the present invention.
  • the content is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 2 parts by mass or more, relative to 100 parts by mass of the resin solid content in the resin composition.
  • the content of the oxetane resin is 0.1 parts by mass or more, the metal foil peel strength and toughness tend to be improved.
  • the upper limit of the content of the oxetane resin is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, and even more preferably 8 parts by mass or less, relative to 100 parts by mass of the resin solid content in the resin composition.
  • the content of the oxetane resin is 50 parts by mass or less, the electrical properties tend to be improved.
  • the resin composition in the present embodiment may contain only one type of oxetane resin, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.
  • the resin composition in the present embodiment may be configured to be substantially free of oxetane resin.
  • substantially free of oxetane resin means that the content of oxetane resin is less than 0.1 parts by mass per 100 parts by mass of resin solid content in the resin composition.
  • the resin composition of the present embodiment may contain a benzoxazine compound.
  • the benzoxazine compound is not particularly limited as long as it has two or more (preferably 2 to 12, more preferably 2 to 6, even more preferably 2 to 4, still more preferably 2 or 3, and even more preferably 2) dihydrobenzoxazine rings in one molecule, and a wide variety of compounds commonly used in the field of printed wiring boards can be used.
  • benzoxazine compound examples include bisphenol A benzoxazine BA-BXZ (manufactured by Konishi Chemical Co., Ltd.), bisphenol F benzoxazine BF-BXZ (manufactured by Konishi Chemical Co., Ltd.), and bisphenol S benzoxazine BS-BXZ (manufactured by Konishi Chemical Co., Ltd.).
  • the resin composition of the present embodiment preferably contains a benzoxazine compound in a range that does not impair the effects of the present invention.
  • the content thereof is preferably 0.1 parts by mass or more and preferably 50 parts by mass or less relative to 100 parts by mass of the resin solid content in the resin composition.
  • the resin composition in the present embodiment may contain only one type of benzoxazine compound, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.
  • the resin composition of the present embodiment may be configured to be substantially free of benzoxazine compounds. Substantially free means that the content of the benzoxazine compounds is less than 0.1 parts by mass per 100 parts by mass of the resin solid content in the resin composition.
  • the resin composition of the present embodiment may contain a cyanate ester compound.
  • the cyanate ester compound is not particularly limited as long as it is a compound containing one or more (preferably 2 to 12, more preferably 2 to 6, even more preferably 2 to 4, still more preferably 2 or 3, and even more preferably 2) cyanate groups (cyanato groups) in the molecule, and a wide variety of compounds commonly used in the field of printed wiring boards can be used.
  • the cyanate ester compound is preferably a cyanate ester compound having two or more aromatic moieties in the molecule substituted with at least one cyanato group, which is commonly used in printed wiring boards.
  • the lower limit of the number of cyanate groups in the cyanate ester compound is preferably 2 or more, more preferably 3 or more. By making the number equal to or more than the above lower limit, the heat resistance tends to be further improved.
  • the upper limit of the number of cyanate groups is preferably 100 or less, more preferably 50 or less.
  • the cyanate ester compound is preferably cured to have excellent low dielectric properties.
  • the lower limit of the dielectric constant is, for example, 2.0 or more, practical.
  • the lower limit of the dielectric loss tangent is, for example, 0.0001 or more, practical.
  • the dielectric constant and dielectric loss tangent can be measured, for example, according to the method described in the examples (curing conditions, measurement conditions).
  • the cured product of the cyanate ester compound has high heat resistance.
  • the cured product of the cyanate ester compound preferably has a glass transition temperature measured according to JIS C6481 dynamic viscoelasticity measurement of 150°C or higher, more preferably 180°C or higher, and even more preferably 200°C or higher. By setting the glass transition temperature at or above the lower limit, a cured product with excellent heat resistance can be obtained.
  • the weight average molecular weight of the cyanate ester compound calculated as polystyrene by the GPC method, is preferably 200 or more, more preferably 300 or more, and even more preferably 400 or more. By setting the weight average molecular weight to the above lower limit or more, heat resistance tends to be further improved. Furthermore, the weight average molecular weight of the cyanate ester compound is preferably 1000 or less, more preferably 900 or less, and even more preferably 800 or less. By setting the weight average molecular weight to the above upper limit or less, moldability and handleability tend to be further improved.
  • cyanate ester compound is a compound represented by the formula (B1).
  • Formula (B1) (In formula (B1), Ar 1 's each independently represent a phenylene group which may have a substituent, a naphthylene group which may have a substituent, or a biphenylene group which may have a substituent.
  • R 6 's each independently represent one of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent, an aryl group having 6 to 12 carbon atoms which may have a substituent, an alkoxy group having 1 to 4 carbon atoms which may have a substituent, an aralkyl group which is an alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 12 carbon atoms which may have a substituent, or an alkylaryl group which is an alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 12 carbon atoms which may have a substituent.
  • n 4 represents the number of cyanato groups bonded to Ar 1 and is an integer of 1 to 3.
  • n 5 represents the number of R 6 bonded to Ar 1 , and is 4-n 4 when Ar 1 is a phenylene group, 6-n 4 when Ar 1 is a naphthylene group, and 8-n 4 when Ar 1 is a biphenylene group.
  • n n 5 and/or n 6 represent the average number of repetitions and are an integer of 0 to 50.
  • the compound represented by formula (B1) may be a mixture of compounds in which n 5 and/or n 6 are different.
  • Each Z is independently selected from any one of a single bond, a divalent organic group having 1 to 50 carbon atoms (wherein a hydrogen atom may be substituted with a heteroatom), and a divalent organic group having 1 to 10 nitrogen atoms (such as -N-R-N-).
  • the substituent in the above formula (B1) is preferably a non-polar group.
  • the alkyl group in R6 of formula (B1) may have at least one of a straight-chain structure, a branched structure, and a cyclic structure (such as a cycloalkyl group).
  • the hydrogen atoms in the alkyl group in formula (B1) and the aryl group in R6 may be substituted with a halogen atom such as a fluorine atom or a chlorine atom, an alkoxy group such as a methoxy group or a phenoxy group, a cyano group, or the like.
  • alkyl group examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, a 1-ethylpropyl group, a 2,2-dimethylpropyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, and a trifluoromethyl group.
  • aryl group examples include a phenyl group, a xylyl group, a mesityl group, a naphthyl group, a phenoxyphenyl group, an ethylphenyl group, an o-, m- or p-fluorophenyl group, a dichlorophenyl group, a dicyanophenyl group, a trifluorophenyl group, a methoxyphenyl group, and an o-, m- or p-tolyl group.
  • alkoxy group examples include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, and a tert-butoxy group.
  • divalent organic group in Z of formula (B1) include a methylene group, an ethylene group, a trimethylene group, a cyclopentylene group, a cyclohexylene group, a trimethylcyclohexylene group, a biphenylylmethylene group, a dimethylmethylene-phenylene-dimethylmethylene group, a fluorenediyl group, a phthalidodiyl group, etc.
  • the hydrogen atom in the divalent organic group may be substituted with a halogen atom such as a fluorine atom or a chlorine atom, an alkoxy group such as a methoxy group or a phenoxy group, a cyano group, etc.
  • a halogen atom such as a fluorine atom or a chlorine atom
  • an alkoxy group such as a methoxy group or a phenoxy group
  • a cyano group etc.
  • Examples of the divalent organic group having 1 to 10 nitrogen atoms in Z of formula (B1) include an imino group, a polyimide group, etc.
  • Z in formula (B1) may be a structure represented by the following formula (B2) or a structure represented by the following formula (B3).
  • Formula (B2) (In formula (B2), Ar 2 is selected from any one of a phenylene group, a naphthylene group, and a biphenylene group.
  • R 7 , R 8 , R 11 , and R 12 are each independently selected from any one of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an aryl group substituted with at least one of a trifluoromethyl group and a phenolic hydroxyl group.
  • R 9 and R 10 are each independently selected from any one of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a hydroxy group.
  • n7 represents an integer of 0 to 5, but the compound represented by formula (B1) may be a mixture of compounds having different n7s.
  • Formula (B3) (In formula (B3), Ar 3 is selected from any one of a phenylene group, a naphthylene group, and a biphenylene group.
  • R 13 and R 14 are each independently selected from any one of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a benzyl group, an alkoxy group having 1 to 4 carbon atoms, and an aryl group substituted with at least one of a hydroxy group, a trifluoromethyl group, and a cyanato group.
  • n 8 represents an integer of 0 to 5, but the compound represented by formula (B1) may be a mixture of compounds in which n 8 is different.
  • Z in formula (B1) may be a divalent group represented by the following formula: (In the formula, n9 represents an integer of 4 to 7. Each R15 independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)
  • Ar 2 in formula (B2) and Ar 3 in formula (B3) include 1,4-phenylene group, 1,3-phenylene group, 4,4'-biphenylene group, 2,4'-biphenylene group, 2,2'-biphenylene group, 2,3'-biphenylene group, 3,3'-biphenylene group, 3,4'-biphenylene group, 2,6-naphthylene group, 1,5-naphthylene group, 1,6-naphthylene group, 1,8-naphthylene group, 1,3-naphthylene group, 1,4-naphthylene group, etc.
  • cyanate ester compound examples include 1,2-dicyanatobenzene, 1,3-dicyanatobenzene, 1,4-dicyanatobenzene, 1,4-dicyanato-2-tert-butylbenzene, 1,4-dicyanato-2,4-dimethylbenzene, 1,4-dicyanato-2,3,4-trimethylbenzene, 1,3-dicyanato-2,4,6-trimethylbenzene, 1,3-dicyanato-5-methylbenzene, 2,2'- dicyanato-1,1'-binaphthyl, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 2,3-, 2,6- or 2,7-dicyanatonaphthalene, 2,2'- or 4,4'-dicyanatobiphenyl, 4,4'-dicyanatooctafluorobiphenyl, 2,4'- or 4,4'-dicyanatodiphenylmethane, bis(4-cyanato-3,5-dimethylphenyl)
  • Preferred cyanate ester compounds include at least one selected from the group consisting of phenol novolac type cyanate ester compounds, naphthol aralkyl type cyanate ester compounds (naphthol aralkyl type cyanates), naphthylene ether type cyanate ester compounds, biphenyl aralkyl type cyanate ester compounds, xylene resin type cyanate ester compounds, trisphenolmethane type cyanate ester compounds, adamantane skeleton type cyanate ester compounds, bisphenol M type cyanate ester compounds, and bisphenol A type cyanate ester compounds.
  • At least one selected from the group consisting of phenol novolac type cyanate ester compounds, naphthol aralkyl type cyanate ester compounds, naphthylene ether type cyanate ester compounds, xylene resin type cyanate ester compounds, bisphenol M type cyanate ester compounds, and bisphenol A type cyanate ester compounds is preferable, at least one selected from the group consisting of phenol novolac type cyanate ester compounds, naphthol aralkyl type cyanate ester compounds, naphthylene ether type cyanate ester compounds, bisphenol A type cyanate ester compounds, and bisphenol M type cyanate ester compounds is more preferable, at least one selected from the group consisting of phenol novolac type cyanate ester compounds, naphthol aralkyl type cyanate ester compounds, and bisphenol A type cyanate ester compounds is even more preferable, naphthol a
  • the compound represented by formula (N1) is more preferred.
  • Formula (N1) (In formula (N1), each R3 independently represents a hydrogen atom or a methyl group, and n3 represents an integer of 1 or more.)
  • each R 3 independently represents a hydrogen atom or a methyl group, and among these, a hydrogen atom is preferred.
  • n3 is an integer of 1 or more, preferably an integer of 1 to 50, more preferably an integer of 1 to 20, even more preferably an integer of 1 to 10, and still more preferably an integer of 1 to 6.
  • the phenol novolac type cyanate ester compound is not particularly limited, but is preferably, for example, a compound represented by formula (VII).
  • R6 each independently represents a hydrogen atom or a methyl group, and n7 represents an integer of 1 or more.
  • each R 6 independently represents a hydrogen atom or a methyl group, and among these, a hydrogen atom is preferred.
  • n7 is an integer of 1 or more, preferably an integer of 1 to 20, more preferably an integer of 1 to 10, and even more preferably an integer of 1 to 6.
  • bisphenol A type cyanate ester compound one or more compounds selected from the group consisting of 2,2-bis(4-cyanatophenyl)propane and prepolymers of 2,2-bis(4-cyanatophenyl)propane may be used.
  • cyanate ester compounds may be prepared by known methods, or commercially available products may be used.
  • cyanate ester compounds having a naphthol aralkyl skeleton, naphthylene ether skeleton, xylene skeleton, trisphenolmethane skeleton, or adamantane skeleton have a relatively large functional group equivalent number and fewer unreacted cyanate ester groups, so resin compositions using these compounds tend to have even better low water absorption.
  • plating adhesion tends to be even better.
  • the lower limit of the content is preferably 1 part by mass or more, more preferably 5 parts by mass or more, even more preferably 10 parts by mass or more, and may be 20 parts by mass or more, relative to 100 parts by mass of the resin solid content in the resin composition.
  • the content of the cyanate ester compound being equal to or more than the above lower limit, there is a tendency for the heat resistance, flame resistance, chemical resistance, low dielectric constant, low dielectric tangent, and insulating properties to be improved.
  • the upper limit of the content of the cyanate ester compound is preferably 70 parts by mass or less, more preferably 60 parts by mass or less, even more preferably 50 parts by mass or less, and may be 40 parts by mass or less, or 30 parts by mass or less, relative to 100 parts by mass of the resin solid content in the resin composition.
  • the resin composition in the present embodiment may contain only one type of cyanate ester compound, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.
  • the resin composition of the present embodiment may contain a thermoplastic elastomer.
  • the thermoplastic elastomer in the present embodiment is not particularly limited, and examples thereof include at least one selected from the group consisting of polyisoprene, polybutadiene, styrene butadiene, butyl rubber, ethylene propylene rubber, styrene butadiene ethylene, styrene butadiene styrene, styrene isoprene styrene, styrene ethylene butylene styrene, styrene propylene styrene, styrene ethylene propylene styrene, fluororubber, silicone rubber, hydrogenated compounds thereof, alkyl compounds thereof, and copolymers thereof.
  • the number average molecular weight of the thermoplastic elastomer used in this embodiment is preferably 50,000 or more. By setting the number average molecular weight to 50,000 or more, the dielectric properties (low dielectric tangent) of the obtained cured product tend to be more excellent.
  • the number average molecular weight is preferably 60,000 or more, more preferably 70,000 or more, and even more preferably 80,000 or more.
  • the upper limit of the number average molecular weight of the thermoplastic elastomer is preferably 400,000 or less, more preferably 350,000 or less, and even more preferably 300,000 or less. By setting it to the upper limit or less, the solubility of the thermoplastic elastomer component in the resin composition tends to be improved.
  • the resin composition of the present embodiment contains two or more thermoplastic elastomers, it is preferable that the number average molecular weight of the mixture thereof falls within the above range.
  • thermoplastic elastomer is preferably a thermoplastic elastomer containing a styrene monomer unit and a conjugated diene monomer unit (hereinafter referred to as "thermoplastic elastomer (e)").
  • thermoplastic elastomer (e) a thermoplastic elastomer containing a styrene monomer unit and a conjugated diene monomer unit
  • the thermoplastic elastomer (e) contains a styrene monomer unit.
  • a styrene monomer unit By containing a styrene monomer unit, the solubility of the thermoplastic elastomer (e) in the resin composition is improved.
  • the styrene monomer include styrene, ⁇ -methylstyrene, p-methylstyrene, divinylbenzene (vinylstyrene), N,N-dimethyl-p-aminoethylstyrene, and N,N-diethyl-p-aminoethylstyrene.
  • styrene ⁇ -methylstyrene, and p-methylstyrene are preferred from the viewpoints of availability and productivity.
  • styrene is particularly preferred.
  • the content of the styrene monomer unit in the thermoplastic elastomer (e) is preferably in the range of 10 to 50% by mass of the total monomer units, more preferably in the range of 13 to 45% by mass, and even more preferably in the range of 15 to 40% by mass. If the content of the styrene monomer unit is 50% by mass or less, the adhesion and tackiness to the substrate and the like will be better.
  • thermoplastic elastomer (e) may contain only one type of styrene monomer unit, or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range.
  • the method for measuring the content of the styrene monomer unit in the thermoplastic elastomer (e) of this embodiment can be found in International Publication No. 2017/126469, the contents of which are incorporated herein by reference. The same applies to the conjugated diene monomer unit and the like described below.
  • the thermoplastic elastomer (e) contains a conjugated diene monomer unit. By containing the conjugated diene monomer unit, the solubility of the thermoplastic elastomer (e) in the resin composition is improved.
  • the conjugated diene monomer is not particularly limited as long as it is a diolefin having one pair of conjugated double bonds.
  • conjugated diene monomer examples include 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, and farnesene, with 1,3-butadiene and isoprene being preferred, and 1,3-butadiene being more preferred.
  • the thermoplastic elastomer (e) may contain only one type of conjugated diene monomer unit, or may contain two or more types of conjugated diene monomer units.
  • thermoplastic elastomer (e) may have all of the conjugated diene bonds of the thermoplastic elastomer hydrogenated, or may have only some of the conjugated diene bonds hydrogenated, or may not have any conjugated diene bonds hydrogenated.
  • the thermoplastic elastomer (e) may or may not contain other monomer units in addition to the styrene monomer units and the conjugated diene monomer units.
  • examples of other monomer units include aromatic vinyl compound units other than the styrene monomer units.
  • the total of styrene monomer units and conjugated diene monomer units preferably accounts for 90 mass % or more of all monomer units, more preferably 95 mass % or more, even more preferably 97 mass % or more, and still more preferably 99 mass % or more.
  • thermoplastic elastomer (e) may contain only one type of styrene monomer unit and one type of conjugated diene monomer unit, or may contain two or more types. When two or more types are contained, it is preferable that the total amount is within the above range.
  • the thermoplastic elastomer (e) used in the present embodiment may be a block polymer or a random polymer.
  • it may be a hydrogenated elastomer in which the conjugated diene monomer unit is hydrogenated, an unhydrogenated elastomer in which the conjugated diene monomer unit is not hydrogenated, or a partially hydrogenated elastomer in which the conjugated diene monomer unit is partially hydrogenated, and is preferably an unhydrogenated elastomer or a partially hydrogenated elastomer.
  • the thermoplastic elastomer (e) is a hydrogenated elastomer.
  • the hydrogenated elastomer means, for example, a thermoplastic elastomer in which double bonds based on conjugated diene monomer units are hydrogenated, and includes elastomers having a hydrogenation rate (hydrogenation rate) of 100% or more as well as elastomers having a hydrogenation rate of 80% or more.
  • the hydrogenation rate in the hydrogenated elastomer is preferably 85% or more, more preferably 90% or more, and even more preferably 95% or more.
  • the hydrogenation rate is calculated from the results of 1H -NMR spectrum measurement.
  • the thermoplastic elastomer (e) is an unhydrogenated elastomer.
  • the unhydrogenated elastomer refers to an elastomer in which the ratio of hydrogenated double bonds based on conjugated diene monomer units in the elastomer, i.e., the hydrogenation rate (hydrogenation rate) is 20% or less.
  • the hydrogenation rate is preferably 15% or less, more preferably 10% or less, and even more preferably 5% or less.
  • the partially hydrogenated elastomer means a thermoplastic elastomer in which some of the double bonds based on the conjugated diene monomer units in the thermoplastic elastomer are hydrogenated, and usually means a hydrogenation rate (hydrogenation rate) of less than 80% and more than 20%.
  • thermoplastic elastomer (e) used in this embodiment examples include SEPTON (registered trademark) 2104, V9461, and S8104 manufactured by Kuraray Co., Ltd., S.O.E. (registered trademark) S1606, S1613, S1609, and S1605 manufactured by Asahi Kasei Corporation, Tuftec (registered trademark) H1041, H1043, P2000, and MP10 manufactured by Asahi Kasei Corporation, and DYNARON (registered trademark) 9901P and TR2250 manufactured by JSR Corporation.
  • the elastomer used in this embodiment may also be a liquid diene.
  • Liquid diene means a liquid elastomer containing a conjugated diene monomer unit.
  • conjugated diene monomers include 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, and farnesene.
  • 1,3-butadiene and isoprene are preferred, and 1,3-butadiene is more preferred.
  • liquid diene examples include liquid polybutadiene, liquid polyisoprene, modified liquid polybutadiene, modified liquid polyisoprene, liquid acrylonitrile-butadiene copolymer, and liquid styrene-butadiene copolymer.
  • the number average molecular weight of the liquid diene is not particularly limited as long as it is liquid at 20° C., but is preferably 500 or more and 10,000 or less.
  • the content is preferably 1 part by mass or more, more preferably 5 parts by mass or more, even more preferably 10 parts by mass or more, and even more preferably 12 parts by mass or more, relative to 100 parts by mass of the resin solid content in the resin composition.
  • the dielectric properties low dielectric tangent
  • the upper limit of the content of the thermoplastic elastomer is preferably 45 parts by mass or less, more preferably 40 parts by mass or less, even more preferably 35 parts by mass or less, even more preferably 32 parts by mass or less, and even more preferably 28 parts by mass or less, relative to 100 parts by mass of the resin solid content in the resin composition.
  • the resin composition of the present embodiment may contain only one type of thermoplastic elastomer, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.
  • the resin composition of the present embodiment preferably contains a filler (E).
  • the filler (E) By containing the filler (E), the resin composition and its cured product can have improved physical properties such as low dielectric properties (low dielectric constant, low dielectric loss tangent, etc.), flame resistance, and low thermal expansion.
  • the filler (E) used in this embodiment is preferably excellent in low dielectric properties.
  • the filler (E) used in this embodiment has a relative dielectric constant (Dk) of 8.0 or less at a frequency of 10 GHz measured according to the cavity resonator perturbation method, more preferably 6.0 or less, and even more preferably 4.0 or less.
  • the lower limit of the relative dielectric constant is, for example, 2.0 or more in practical use.
  • the filler (E) used in this embodiment has a dielectric loss tangent (Df) of 0.05 or less at a frequency of 10 GHz measured according to the cavity resonator perturbation method, more preferably 0.01 or less.
  • the lower limit of the dielectric loss tangent is, for example, 0.0001 or more in practical use.
  • the filler (E) used in this embodiment is not particularly limited in type, and can be suitably used in the industry.
  • molybdenum compounds such as molybdenum oxide and zinc molybdate, barium sulfate, 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, short glass fibers (including fine glass powders such as E-glass, T-glass, D-glass, S-glass, and Q-glass), hollow glass, and spherical glass, as well as organic fillers such as styrene-type, butadiene-type, and acrylic-type rubber powders, core-shell type rubber powders, silicone resin powder, silicone rubber powder, and silicone composite powder.
  • organic fillers such as styrene-type, butadiene-type, and acrylic-type rubber powders, core-shell type rubber powders, silicone resin powder, silicone rubber powder, and silicone composite powder.
  • the filler (E) preferably contains an inorganic filler, more preferably contains one or more selected from the group consisting of silica, aluminum hydroxide, aluminum nitride, boron nitride, forsterite, titanium oxide, barium titanate, strontium titanate, and calcium titanate, and from the viewpoint of low dielectric property, more preferably contains one or more selected from the group consisting of silica and aluminum hydroxide, and further preferably contains silica.By using these fillers, the properties such as heat resistance, low dielectric property, thermal expansion property, dimensional stability, and flame retardancy of the cured product of the resin composition are further improved.
  • the content of the filler (E) in the resin composition of this embodiment can be appropriately set according to the desired properties, and is not particularly limited. It is preferably 1 part by mass or more, more preferably 5 parts by mass or more, even more preferably 10 parts by mass or more, and even more preferably 15 parts by mass or more, and may be 30 parts by mass or more, 50 parts by mass or more, 80 parts by mass or more, 100 parts by mass or more, or 120 parts by mass or more, depending on the application.
  • By setting the content of the filler (E) to the above lower limit or more low thermal expansion and low dielectric loss tangent tend to be further improved.
  • the upper limit of the content of the filler (E) is preferably 1600 parts by mass or less, more preferably 1200 parts by mass or less, even more preferably 800 parts by mass or less, even more preferably 500 parts by mass or less, even more preferably 300 parts by mass or less, and even more preferably 200 parts by mass or less, relative to 100 parts by mass of the resin solid content.
  • the content of the filler (E) is 1 to 95 mass% of the components excluding the solvent, and preferably 5 mass% to 30 mass%.
  • the resin composition of the present embodiment may contain only one type of filler (E), or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.
  • a silane coupling agent may be further included.
  • a silane coupling agent By including a silane coupling agent, the dispersibility of the filler (E) and the adhesive strength between the resin component and the filler (E) and the substrate described later tend to be further improved.
  • the silane coupling agent is not particularly limited, and examples thereof include silane coupling agents generally used for surface treatment of inorganic substances, such as aminosilane-based compounds (e.g., ⁇ -aminopropyltriethoxysilane, N- ⁇ -(aminoethyl)- ⁇ -aminopropyltrimethoxysilane, etc.), epoxysilane-based compounds (e.g., ⁇ -glycidoxypropyltrimethoxysilane, etc.), vinylsilane-based compounds (e.g., vinyltrimethoxysilane, etc.), styrylsilane-based compounds (e.g., p-styryltrimethoxysilane, etc.), acrylsilane-based compounds (e.g., ⁇ -acryloxypropyltrimethoxysilane, etc.), cationic silane-based compounds (e.g., N- ⁇ -(N-vinylbenzylaminoeth
  • the silane coupling agents may be used alone or in combination of two or more.
  • at least one selected from the group consisting of vinylsilane compounds, acrylicsilane compounds, and styrylsilane compounds as the silane coupling agent, and by using a compound containing a vinylaryl group (particularly a polymer having a structural unit represented by formula (V)), the low dielectric properties tend to be further improved.
  • the low dielectric properties tend to be further improved.
  • the content of the silane coupling agent is not particularly limited, but may be 0.1 to 5.0 parts by mass per 100 parts by mass of the resin solid content in the resin composition.
  • the resin composition of this embodiment can also be used in combination with a monomer or oligomer having an ethylenically unsaturated group.
  • the oligomer or monomer having an ethylenically unsaturated group used in this embodiment is not particularly limited as long as it is an oligomer or monomer having one or more ethylenically unsaturated groups in one molecule, but examples thereof include monomers or oligomers having a vinyl group, an allyl group, a (meth)acryloyl group, etc., and a monomer or oligomer having a vinyl group is preferred.
  • a compound which corresponds to a monomer or oligomer having an ethylenically unsaturated group and which also corresponds to a polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds is defined as a polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds.
  • the monomer having an ethylenically unsaturated group may be a compound (F1) (compound (F1)) having a molecular weight of less than 1,000 and containing one organic group having an ethylenically unsaturated bond in the molecule.
  • the ethylenically unsaturated bond constituting the organic group containing the ethylenically unsaturated bond does not include those contained as part of an aromatic ring.
  • the ethylenically unsaturated bond contained as part of a non-aromatic ring is included.
  • An example of an ethylenically unsaturated bond contained as part of a non-aromatic ring is a cyclohexenyl group in a molecule.
  • the ethylenically unsaturated bond is also included in the part other than the terminal of a linear or branched organic group, that is, the ethylenically unsaturated bond contained in a linear or branched chain.
  • the organic group containing an ethylenically unsaturated bond is more preferably one selected from the group consisting of a vinyl group, an isopropenyl group, an allyl group, an acryloyl group, a methacryl group, and a vinylene group, more preferably one selected from the group consisting of a vinyl group, an isopropenyl group, an allyl group, an acryloyl group, and a methacryl group, and even more preferably a vinyl group.
  • a compound which is a monomer or oligomer having an ethylenically unsaturated group and which also corresponds to a silane coupling agent is referred to as a silane coupling agent.
  • the compound (F1) used in the present embodiment is preferably composed only of atoms selected from carbon atoms, hydrogen atoms, oxygen atoms, and silicon atoms, and more preferably composed only of atoms selected from carbon atoms, hydrogen atoms, and oxygen atoms.
  • the compound (F1) used in this embodiment may or may not have a polar group. It is preferable that the compound (F1) used in this embodiment does not have a polar group.
  • Examples of the polar group include an amino group, a carboxyl group, a hydroxyl group, and a nitro group.
  • the molecular weight of the compound (F1) is preferably 70 or more, more preferably 80 or more, and even more preferably 90 or more.
  • the upper limit of the molecular weight of the compound (F1) is preferably 500 or less, more preferably 400 or less, even more preferably 300 or less, even more preferably 200 or less, and may be 150 or less. By making it equal to or less than the upper limit, there is a tendency that the effect of increasing the reactivity with other thermoplastic resin components is further improved.
  • the resin composition of the present embodiment contains two or more types of compound (F1)
  • the average molecular weight value of compound (F1) falls within the above range
  • the boiling point of the compound (F1) is preferably 110°C or higher, more preferably 115°C or higher, and even more preferably 120°C or higher. By making it equal to or higher than the lower limit, the volatilization of the compound (F1) during thermal curing of the resin composition is suppressed, and the thermosetting resin (C) and the compound (F1) can be reacted.
  • the boiling point of the compound (F1) is preferably 300°C or lower, more preferably 250°C or lower, and even more preferably 200°C or lower. By making it equal to or lower than the upper limit, it is possible to make it difficult for the compound (F1) to remain as a residual solvent in the cured product.
  • the resin composition of the present embodiment contains two or more types of compound (F1), it is sufficient that the average boiling point falls within the above range, but it is preferable that the boiling point of each compound falls within the above preferred range.
  • compound (F1) examples include (meth)acrylic acid ester compounds, aromatic vinyl compounds (preferably styrene-based compounds), saturated fatty acid vinyl compounds, vinyl cyanide compounds, ethylenically unsaturated carboxylic acids, ethylenically unsaturated carboxylic acid anhydrides, ethylenically unsaturated dicarboxylic acid monoalkyl esters, ethylenically unsaturated carboxylic acid amides, etc., and at least one selected from the group consisting of (meth)acrylic acid ester compounds, aromatic vinyl compounds, and saturated fatty acid vinyl compounds is preferred, with aromatic vinyl compounds being more preferred.
  • compounds (F1) that are aromatic vinyl compounds include methylstyrene (e.g., 4-methylstyrene), ethylvinylbenzene, diethyl 4-vinylbenzylphosphonate, 4-vinylbenzyl glycidyl ether, ⁇ -methylstyrene, 4-tert-butylstyrene, divinylbenzene, 1,2-bis(4-vinylphenyl)ethane (BVPE), and vinylbenzyl ether.
  • methylstyrene e.g., 4-methylstyrene
  • ethylvinylbenzene diethyl 4-vinylbenzylphosphonate
  • 4-vinylbenzyl glycidyl ether ⁇ -methylstyrene
  • 4-tert-butylstyrene divinylbenzene
  • 1,2-bis(4-vinylphenyl)ethane BVPE
  • Examples of such compounds include methylstyrene (e.g., 4-methylstyrene), ethylvinylbenzene, diethyl 4-vinylbenzylphosphonate, 4-vinylbenzyl glycidyl ether, ⁇ -methylstyrene, and the like.
  • compound (F1) the descriptions in paragraphs 0046 and 0049 of JP-A-2019-194312 can be referred to, the contents of which are incorporated herein by reference.
  • specific examples thereof are preferably acenaphthylene and pyracylene, and more preferably acenaphthylene.
  • a compound that corresponds to a compound having a vinylene group such as an imidazole compound described later, but is explicitly stated as a component other than a compound having a vinylene group (e.g., a curing accelerator) is not considered to be a compound having a vinylene group.
  • the resin composition according to this embodiment preferably contains a styrene oligomer (F2) in order to improve the low dielectric constant and low dielectric loss tangent.
  • the styrene oligomer (F2) according to this embodiment is preferably obtained by polymerizing at least one selected from the group consisting of styrene, the above-mentioned styrene derivatives, and vinyltoluene.
  • the number average molecular weight of the styrene oligomer (F2) is preferably 178 or more, and preferably 1600 or less.
  • the styrene oligomer (F2) is preferably a compound having an average number of aromatic rings of 2 to 14, a total amount of the aromatic rings of 2 to 14 being 50 mass% or more, and a boiling point of 300°C or more, with no branched structure.
  • styrene oligomer (F2) used in this embodiment examples include styrene polymer, vinyl toluene polymer, ⁇ -methyl styrene polymer, vinyl toluene- ⁇ -methyl styrene polymer, styrene- ⁇ -styrene polymer, etc.
  • styrene polymer commercially available products may be used, such as Picolastic A5 (manufactured by Eastman Chemical Co.), Picolastic A-75 (manufactured by Eastman Chemical Co.), Picotex 75 (manufactured by Eastman Chemical Co.), FTR-8100 (manufactured by Mitsui Chemicals, Inc.), and FTR-8120 (manufactured by Mitsui Chemicals, Inc.).
  • an example of the vinyl toluene- ⁇ -methyl styrene polymer is Picotex LC (manufactured by Eastman Chemical Co.).
  • Examples of the ⁇ -methylstyrene polymer include CRYSTALEX 3070 (manufactured by Eastman Chemical Co.), CRYSTALEX 3085 (manufactured by Eastman Chemical Co.), CRYSTALEX (3100), CRYSTALEX 5140 (manufactured by Eastman Chemical Co.), FMR-0100 (manufactured by Mitsui Chemicals, Inc.), and FMR-0150 (manufactured by Mitsui Chemicals, Inc.).
  • Examples of the styrene- ⁇ -styrene polymer include FTR-2120 (manufactured by Mitsui Chemicals, Inc.). These styrene oligomers may be used alone or in combination of two or more kinds. In the resin composition of the present embodiment, ⁇ -methylstyrene oligomer is preferred because it is well thermoset, has good embedding properties for fine wiring, solder heat resistance, low relative dielectric constant, and low dielectric loss tangent.
  • the resin composition according to the present embodiment preferably contains a divinyl compound (F3) as a monomer having an ethylenically unsaturated group in order to improve low dielectric constant and low dielectric loss tangent.
  • the divinyl compound is a low molecular weight compound having two vinyl groups. The two vinyl groups provide a good crosslinking density that is not too high, and as a result, the free volume of the molecule is increased, so that the dielectric loss tangent (Df) of the resulting cured product can be kept small.
  • the divinyl compound (F3) is used as a substitute for the polymaleimide compound (A), other maleimide compounds (B), and compounds (C) containing two or more carbon-carbon unsaturated double bonds, as well as a part of the other resin components (D), it is believed that the reduction in the content of the components having polar groups also contributes to the reduction of the dielectric loss tangent (Df).
  • the two functional groups of the divinyl compound are both vinyl groups, the reactivity with the polymaleimide compound (A), other maleimide compounds (B), and compounds (C) containing two or more carbon-carbon unsaturated double bonds becomes good, and as a result, it is believed that there is a tendency for the heat resistance to be easily improved.
  • the divinyl compound (F3) here refers to one having a molecular weight of less than 195, and the practical lower limit of the molecular weight is 54.
  • Examples of the divinyl compound (F3) include divinylbenzene and 1,3-vinyltetramethylsiloxane.
  • a resin composition having excellent moisture absorption and heat resistance while maintaining excellent low dielectric properties can be obtained.
  • a monomer or oligomer having an ethylenically unsaturated group and a compound containing a vinylaryl group particularly a polymer having a structural unit represented by formula (V)
  • a resin composition having excellent moisture absorption and heat resistance while maintaining excellent low dielectric properties can be obtained.
  • the content is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, even more preferably 2 parts by mass or more, even more preferably 3 parts by mass or more, and even more preferably 5 parts by mass or more, relative to 100 parts by mass of the resin solid content in the resin composition.
  • the content is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, even more preferably 2 parts by mass or more, even more preferably 3 parts by mass or more, and even more preferably 5 parts by mass or more, relative to 100 parts by mass of the resin solid content in the resin composition.
  • the upper limit of the content of the monomer or oligomer having an ethylenically unsaturated group is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less, relative to 100 parts by mass of the resin solid content in the resin composition.
  • heat resistance tends to be further improved.
  • low dielectric constant, low dielectric loss tangent, and chemical resistance tend to be further improved.
  • the resin composition of the present embodiment may contain only one type of monomer or oligomer having an ethylenically unsaturated group, or may contain two or more types. When two or more types are contained, it is preferable that the total amount is in the above range.
  • the resin composition of the present embodiment may contain an active ester compound.
  • the active ester compound is not particularly limited, and examples thereof include compounds having two or more (preferably 2 to 12, more preferably 2 to 6, even more preferably 2 to 4, still more preferably 2 or 3, and even more preferably 2) active ester groups in one molecule.
  • the active ester compound may be a straight-chain, branched or cyclic compound.
  • the active ester compound obtained by reacting a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxy compound and/or a thiol compound is preferred, the active ester compound obtained by reacting a carboxylic acid compound with one or more compounds selected from the group consisting of a phenol compound, a naphthol compound and a thiol compound is more preferred, the aromatic compound obtained by reacting a carboxylic acid compound with an aromatic compound having a phenolic hydroxyl group and having two or more active ester groups in one molecule is more preferred, and the aromatic compound obtained by reacting a compound having two or more carboxylic acids in one molecule with an aromatic compound having a phenolic hydroxyl group and having two or more active ester groups in one molecule is particularly preferred.
  • the above-mentioned carboxylic acid compound may be one or more selected from the group consisting of benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid.
  • benzoic acid acetic acid
  • succinic acid maleic acid, itaconic acid
  • phthalic acid isophthalic acid
  • terephthalic acid pyromellitic acid.
  • one or more selected from the group consisting of succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, and terephthalic acid are preferred, and one or more selected from the group consisting of isophthalic acid and terephthalic acid are more preferred.
  • the thiocarboxylic acid compound may be one or more selected from thioacetic acid and thiobenzoic acid.
  • the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, ⁇ -naphthol, ⁇ -naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinone, benzenetrihydroxybenzophenone, tetra ...
  • examples of the phenol include one or more selected from the group consisting of phenol, dicyclopentadienyldiphenol, and phenol novolak.
  • examples of the phenol include bisphenol A, bisphenol F, bisphenol S, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, catechol, ⁇ -naphthol, ⁇ -naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, fluorocarbon, and the like.
  • the compound is one or more selected from the group consisting of dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadienyl diphenol, and phenol novolac, and particularly preferably, the compound is one or more selected from the group consisting of dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadienyl diphenol, and phenol novolac (preferably, one or more selected from the group consisting of dicyclopentadienyl diphenol and phenol novolac, more preferably dicyclopentadienyl diphenol).
  • the thiol compound may be one or more selected from the group consisting of benzenedithiol and triazinedithiol.
  • the active ester compound is preferably a compound having two or more carboxylic acids in one molecule and containing an aliphatic chain, and from the viewpoint of further improving the heat resistance, it is preferably a compound having an aromatic ring. More specific examples of the active ester compound include the active ester compounds described in JP-A-2004-277460.
  • the active ester compound may be a commercially available product or may be prepared by a known method.
  • Commercially available products include compounds containing a dicyclopentadienyldiphenol structure (e.g., EXB9451, EXB9460, EXB9460S, HPC-8000-65T (all manufactured by DIC Corporation)), acetylated phenol novolac (e.g., DC808 (manufactured by Mitsubishi Chemical Corporation)), and benzoylated phenol novolac (e.g., YLH1026, YLH1030, YLH1048 (all manufactured by Mitsubishi Chemical Corporation)). From the viewpoint of further improving the storage stability of the varnish and the low thermal expansion of the cured resin composition (cured product), EXB9460S is preferred.
  • the active ester compound can be prepared by known methods, for example, by a condensation reaction between a carboxylic acid compound and a hydroxy compound.
  • a specific example is a method in which (a) a carboxylic acid compound or its halide, (b) a hydroxy compound, and (c) an aromatic monohydroxy compound are reacted in a ratio of 0.05 to 0.75 moles of the phenolic hydroxyl group of (b) and 0.25 to 0.95 moles of (c) to 1 mole of the carboxyl group or acid halide group of (a).
  • the active ester compound is preferably contained within a range that does not impair the effects of the present invention.
  • the amount of the active ester compound is preferably 1 part by mass or more and 50 parts by mass or less per 100 parts by mass of the resin solid content in the resin composition.
  • the resin composition in the present embodiment may contain only one type of active ester compound, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.
  • the resin composition in the present embodiment may be configured to be substantially free of an active ester compound. Substantially free means that the content of the active ester compound is less than 1 part by mass, preferably less than 0.1 part by mass, and more preferably less than 0.01 part by mass, per 100 parts by mass of the resin solid content in the resin composition.
  • the resin composition of the present embodiment may contain a dispersant.
  • a dispersant those generally used for paints can be suitably used, and the type is not particularly limited.
  • a copolymer-based wetting dispersant is preferably used, and specific examples thereof include DISPERBYK (registered trademark)-110, 111, 161, 180, 2009, 2152, 2155, BYK (registered trademark)-W996, W9010, W903, and W940 manufactured by BYK Japan Co., Ltd.
  • the lower limit of the content is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and may be 0.1 parts by mass or more, relative to 100 parts by mass of the resin solid content in the resin composition.
  • the upper limit of the content of the dispersant is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, even more preferably 3 parts by mass or less, more preferably 2 parts by mass or less, and may be 1 part by mass or less, relative to 100 parts by mass of the resin solid content in the resin composition.
  • the dispersant may be used alone or in combination of two or more. When two or more types are used, the total amount falls within the above range.
  • the resin composition of the present embodiment may further contain a curing accelerator.
  • the curing accelerator is not particularly limited, but examples thereof include imidazoles such as 2-ethyl-4-methylimidazole and triphenylimidazole; organic peroxides such as benzoyl peroxide, bis(1-methyl-1-phenylethyl)peroxide, di-t-butyl peroxide, lauroyl peroxide, acetyl peroxide, parachlorobenzoyl peroxide, di-tert-butyl-di-perphthalate, ⁇ , ⁇ '-di(t-butylperoxy)diisopropylbenzene, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, and 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyne-3; azo compounds such as azobisnitrile (e.g., azobisis
  • tertiary amines such as tri-n-butylamine, pyridine, quinoline, N-methylmorpholine, triethanolamine, triethylenediamine, tetramethylbutanediamine, and N-methylpiperidine; phenols such as phenol, xylenol, cresol, resorcin, and catechol; high-temperature decomposition type radical generators such as 2,3-dimethyl-2,3-diphenylbutane; organic metal salts such as lead naphthenate, lead stearate, zinc naphthenate, zinc octylate, manganese octylate, tin oleate, dibutyltin maleate, manganese naphthenate, cobalt naphthenate, and iron acetylacetonate; compounds obtained by dissolving these organic metal salts in hydroxyl group-containing compounds such as phenol and bisphenol; inorganic metal salts such as tin chloride,
  • the curing accelerator is preferably at least one selected from the group consisting of imidazoles, organic peroxides, and organic metal salts, more preferably at least one selected from the group consisting of organic peroxides and organic metal salts, and both the organic peroxides and the organic metal salts may be used in combination.
  • the composition may be configured to be substantially free of a polymerization initiator such as an organic peroxide, an azo compound, etc. "Substantially free" means that the content of the polymerization initiator is less than 0.1 parts by mass per 100 parts by mass of the resin solid content in the resin composition.
  • the lower limit of the content is preferably 0.005 parts by mass or more, more preferably 0.01 parts by mass or more, and even more preferably 0.1 parts by mass or more, relative to 100 parts by mass of the resin solid content in the resin composition.
  • the upper limit of the content of the curing accelerator is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably 2 parts by mass or less, relative to 100 parts by mass of the resin solid content in the resin composition.
  • the curing accelerator may be used alone or in combination of two or more. When two or more types are used, the total amount falls within the above range.
  • the resin composition of the present embodiment may contain a flame retardant.
  • the flame retardant include phosphorus-based flame retardants, halogen-based flame retardants, inorganic flame retardants, and silicone-based flame retardants, and phosphorus-based flame retardants are preferred.
  • halogen-based flame retardants such as brominated epoxy resin, brominated polycarbonate, brominated polystyrene, brominated styrene, brominated phthalimide, tetrabromobisphenol A, pentabromobenzyl (meth)acrylate, pentabromotoluene, tribromophenol, hexabromobenzene, decabromodiphenyl ether, bis-1,2-pentabromophenylethane, chlorinated polystyrene, and chlorinated paraffin, red phosphorus, tricresyl phosphate, triphenyl phosphate, and cresyl diphenyl phosphe phosphorus-based flame retardants such as phosphate, trixylenyl phosphate, trialkyl phosphate, dialkyl phosphate, tris(chloroethyl)phosphate, phosphazen
  • the content thereof is preferably 1 part by mass or more, and more preferably 3 parts by mass or more, per 100 parts by mass of the resin solid content in the resin composition.
  • the lower limit of the content of the flame retardant is preferably 25 parts by mass or less, more preferably 20 parts by mass or less, even more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less.
  • the flame retardants may be used alone or in combination of two or more. When two or more types are used, the total amount falls within the above range.
  • the resin composition of the present embodiment may contain a solvent, and preferably contains an organic solvent.
  • a solvent is contained, the resin composition of the present embodiment is in a form (solution or varnish) in which at least a part, preferably all, of the above-mentioned various resin solids are dissolved or compatible in the solvent.
  • the solvent is not particularly limited as long as it is a polar organic solvent or a non-polar organic solvent that can dissolve or compatible at least a part, preferably all, of the above-mentioned various resin solids.
  • polar organic solvents examples include ketones (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), cellosolves (e.g., propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc.), esters (e.g., ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, methyl methoxypropionate, methyl hydroxyisobutyrate, etc.), amides (e.g., dimethoxyacetamide, dimethylformamides, etc.), and examples of non-polar organic solvents include aromatic hydrocarbons (e.g., toluene, xylene, etc.). The solvent may be used alone or in combination of two or more. When two or more types are used, the total amount falls within the above range.
  • ketones
  • the resin composition of the present embodiment may contain various polymeric compounds such as thermoplastic resins and their oligomers, and various additives.
  • additives include ultraviolet absorbers, antioxidants, photopolymerization initiators, fluorescent brighteners, photosensitizers, dyes, pigments, thickeners, flow regulators, lubricants, defoamers, leveling agents, gloss agents, and polymerization inhibitors. These additives may be used alone or in combination of two or more.
  • the resin composition of the present embodiment is used as a cured product.
  • the resin composition of the present embodiment can be suitably used as a low dielectric constant material and/or a low dielectric tangent material, such as an insulating layer for a printed wiring board, a material for a semiconductor package, or a resin composition for electronic materials.
  • the resin composition of the present embodiment can be suitably used as a material for a prepreg, a metal foil-clad laminate using a prepreg, a resin composite sheet, and a printed wiring board.
  • the resin composition of the present embodiment is used as a layered material (including film, sheet, etc.) such as a prepreg or a resin composite sheet that becomes an insulating layer of a printed wiring board, and when it is used as such a layered material, its thickness is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more.
  • the upper limit of the thickness is preferably 200 ⁇ m or less, more preferably 180 ⁇ m or less.
  • the thickness of the layered material means the thickness including the glass cloth, for example, when the resin composition of the present embodiment is impregnated into a glass cloth or the like.
  • the material formed from the resin composition of the present embodiment may be used for applications in which a pattern is formed by exposure and development, or for applications in which no exposure and development is required. It is particularly suitable for applications in which no exposure and development is required.
  • the prepreg of this embodiment is formed from a substrate (prepreg substrate) and the resin composition of this embodiment.
  • the prepreg of this embodiment can be obtained, for example, by applying the resin composition of this embodiment to the substrate (for example, by impregnating and/or coating), and then semi-curing by heating (for example, by drying at 120 to 220°C for 2 to 15 minutes, etc.).
  • the amount of the resin composition attached to the substrate that is, the amount of the resin composition (including the filler (E)) relative to the total amount of the semi-cured prepreg, is preferably in the range of 20 to 99% by mass, more preferably in the range of 20 to 80% by mass.
  • the substrate is not particularly limited as long as it is a substrate used in various printed wiring board materials.
  • the substrate material include glass fibers (e.g., E-glass, D-glass, L-glass, S-glass, T-glass, Q-glass, UN-glass, NE-glass, spherical glass, etc.), inorganic fibers other than glass (e.g., quartz, etc.), and organic fibers (e.g., polyimide, polyamide, polyester, liquid crystal polyester, polytetrafluoroethylene, etc.).
  • the form of the substrate is not particularly limited, and examples thereof include woven fabric, nonwoven fabric, roving, chopped strand mat, surfacing mat, etc. These substrates may be used alone or in combination of two or more.
  • the substrate is preferably a glass woven fabric having a thickness of 200 ⁇ m or less and a mass of 250 g/m 2 or less, and from the viewpoint of moisture absorption and heat resistance, a glass woven fabric that has been surface-treated with a silane coupling agent such as epoxy silane or amino silane is preferred.
  • a silane coupling agent such as epoxy silane or amino silane is preferred.
  • a low dielectric glass cloth made of glass fibers exhibiting a low relative dielectric constant and a low dielectric loss tangent, such as L-glass, NE-glass, or Q-glass is more preferable.
  • An example of a substrate having a low dielectric constant is a substrate having a dielectric constant of 5.0 or less (preferably, 3.0 to 4.9).
  • An example of a substrate having a low dielectric loss tangent is a substrate having a dielectric loss tangent of 0.006 or less (preferably, 0.001 to 0.005).
  • the dielectric constant and dielectric loss tangent are values measured at a frequency of 10 GHz using a perturbation method cavity resonator.
  • the metal foil-clad laminate of this embodiment includes at least one layer formed from the prepreg of this embodiment and a metal foil arranged on one or both sides of the layer formed from the prepreg.
  • the method for producing the metal foil-clad laminate of this embodiment includes, for example, a method in which at least one prepreg of this embodiment is arranged (preferably two or more sheets are stacked), a metal foil is arranged on one or both sides of the prepreg, and laminated molding is performed. More specifically, the laminate can be produced by arranging a metal foil such as copper or aluminum on one or both sides of the prepreg and laminating and molding it.
  • the number of prepregs is preferably 1 to 10 sheets, more preferably 2 to 10 sheets, and even more preferably 2 to 9 sheets.
  • the metal foil is not particularly limited as long as it is used as a material for printed wiring boards, and examples of the metal foil include copper foil such as rolled copper foil and electrolytic copper foil.
  • the thickness of the metal foil (preferably copper foil) is not particularly limited and may be about 1.5 to 70 ⁇ m.
  • the copper foil is preferably adjusted to have a surface roughness Rz of 0.2 to 4.0 ⁇ m as measured according to JIS B0601:2013.
  • the surface roughness Rz of the copper foil By setting the surface roughness Rz of the copper foil to 0.2 ⁇ m or more, the surface roughness of the copper foil becomes moderate, and the copper foil peel strength tends to be further improved. On the other hand, by setting the surface roughness Rz of the copper foil to 4.0 ⁇ m or less, the surface roughness of the copper foil becomes moderate, and the dielectric loss tangent characteristics of the obtained cured product tend to be further improved.
  • the surface roughness Rz of the copper foil is more preferably 0.5 ⁇ m or more, even more preferably 0.6 ⁇ m or more, particularly preferably 0.7 ⁇ m or more, and more preferably 3.5 ⁇ m or less, even more preferably 3.0 ⁇ m or less, and particularly preferably 2.0 ⁇ m or less.
  • the lamination molding method include methods that are commonly used when forming laminates and multilayer boards for printed wiring boards.
  • a method of lamination molding using a multi-stage press machine, a multi-stage vacuum press machine, a continuous molding machine, an autoclave molding machine, etc., at a temperature of about 180 to 350 ° C., a heating time of about 100 to 300 minutes, and a surface pressure of about 20 to 100 kg / cm 2 or about 1 to 10 MPa can be mentioned.
  • a multilayer board can be made by combining and laminating the prepreg of this embodiment and a separately prepared wiring board for an inner layer.
  • a manufacturing method for a multilayer board for example, copper foil of about 35 ⁇ m is placed on both sides of one prepreg of this embodiment, and the laminate is formed by the above molding method, and then an inner layer circuit is formed, and this circuit is blackened to form an inner layer circuit board, and then this inner layer circuit board and the prepreg of this embodiment are arranged alternately one by one, and copper foil is further arranged on the outermost layer, and laminate molding is preferably performed under vacuum under the above conditions to produce a multilayer board.
  • the metal foil-clad laminate of this embodiment can be suitably used as a printed wiring board.
  • the metal foil-clad laminate of this embodiment preferably has a low dielectric constant (Dk) measured using a laminate in which the metal foil is removed by etching.
  • the dielectric constant (Dk) at a frequency of 10 GHz measured according to the cavity resonator perturbation method in accordance with JIS C2138:2007 using a sample in which the metal foil is removed from the metal foil-clad laminate by etching is preferably less than 3.00, more preferably less than 2.90, and even more preferably less than 2.80.
  • the lower limit of the dielectric constant (Dk) is not particularly specified, but for example, 0.1 or more is practical.
  • the dielectric constant is measured in accordance with the description in the Examples section described later.
  • the metal foil-clad laminate of this embodiment preferably has a low dielectric loss tangent (Df) measured using a laminate in which the metal foil is removed by etching.
  • the dielectric loss tangent (Df) at a frequency of 10 GHz measured according to the cavity resonator perturbation method in accordance with JIS C2138:2007 using a sample in which the metal foil is removed from the metal foil-clad laminate by etching is preferably 0.0025 or less, more preferably 0.0022 or less, and even more preferably 0.0020 or less.
  • the lower limit of the dielectric loss tangent (Df) is not particularly specified, but for example, 0.0001 or more is practical.
  • the dielectric loss tangent is measured in accordance with the description in the Examples section described later.
  • the resin composition of the present embodiment preferably has a small coefficient of thermal expansion (CTE) measured using a laminate in which the metal foil has been removed by etching.
  • the coefficient of thermal expansion (CTE) in the longitudinal direction is preferably 165 (ppm/°C) or less, more preferably 150 (ppm/°C) or less, even more preferably 140 (ppm/°C) or less, even more preferably 130 (ppm/°C) or less, and even more preferably 100 (ppm/°C) or less.
  • the lower limit of the coefficient of thermal expansion (CTE) is not particularly specified, but a value of 1 (ppm/°C) or more is practical.
  • the coefficient of thermal expansion (CTE) was measured in accordance with the description in the Examples section described later.
  • the metal foil-clad laminate of this embodiment has a high metal foil peel strength (preferably copper foil peel strength).
  • the measured value obtained in accordance with JIS C6481:1996 is preferably 0.4 kN/m or more, and more preferably 0.5 kN/m or more.
  • the metal foil peel strength is no particular upper limit for the metal foil peel strength, but for example, 1.4 kN/m or less is practical.
  • the resin composition for electronic materials obtained using the resin composition of this embodiment can have excellent properties in the form of a cured product, such as low dielectric properties (low dielectric tangent), moisture absorption and heat resistance, crack resistance, cured product appearance, and low thermal expansion.
  • the printed wiring board of the present embodiment is a printed wiring board including an insulating layer and a conductor layer disposed on the surface of the insulating layer, and the insulating layer includes at least one of a layer formed from the resin composition of the present embodiment and a layer formed from the prepreg of the present embodiment.
  • a printed wiring board can be manufactured according to a conventional method, and the manufacturing method is not particularly limited.
  • an example of a method for manufacturing a printed wiring board will be described. First, a metal foil-clad laminate such as the above-mentioned copper foil-clad laminate is prepared. Next, an etching treatment is performed on the surface of the metal foil-clad laminate to form an inner layer circuit, and an inner layer substrate is manufactured.
  • a surface treatment is performed on the inner layer circuit surface of this inner layer substrate to increase the adhesive strength, and then a required number of the above-mentioned prepregs are stacked on the surface of the inner layer circuit, and a metal foil for an outer layer circuit is further stacked on the outside thereof, and the laminate is heated and pressed to form an integral body.
  • a multi-layer laminate is manufactured in which an insulating layer made of a base material and a cured product of a resin composition is formed between the inner layer circuit and the metal foil for the outer layer circuit.
  • this multi-layer laminate is subjected to a drilling process for through holes and via holes, and then a plated metal film that provides electrical conductivity between the inner layer circuit and the metal foil for the outer layer circuit is formed on the wall surface of the hole, and the metal foil for the outer layer circuit is further etched to form the outer layer circuit, thereby producing a printed wiring board.
  • the printed wiring board obtained in the above manufacturing example has an insulating layer and a conductor layer formed on the surface of the insulating layer, and the insulating layer contains the above-mentioned resin composition of the present embodiment and/or its cured product. That is, the above-mentioned prepreg of the present embodiment (for example, a prepreg formed from a base material and the resin composition of the present embodiment impregnated or applied thereto) and the layer formed from the resin composition of the above-mentioned metal foil-clad laminate of the present embodiment are the insulating layer of the present embodiment.
  • the present embodiment also relates to a semiconductor device including the printed wiring board. For details of the semiconductor device, refer to paragraphs 0200 to 0202 of JP 2021-021027 A, the contents of which are incorporated herein by reference.
  • the insulating layer formed of the cured product of the resin composition of this embodiment has a small surface roughness after roughening treatment.
  • the arithmetic mean roughness Ra of the surface of the insulating layer after roughening treatment is preferably 200 nm or less, more preferably 150 nm or less, and particularly preferably 100 nm or less.
  • the lower limit of the arithmetic mean roughness Ra is not particularly limited, but may be, for example, 10 nm or more.
  • the arithmetic mean roughness Ra of the surface of the insulating layer is measured using a non-contact surface roughness meter in VSI mode with a 50x lens.
  • the non-contact surface roughness meter used is a WYKONT3300 manufactured by Veeco Instruments.
  • the resin composite sheet of the present embodiment includes a support and a layer formed from the resin composition of the present embodiment arranged on the surface of the support.
  • the resin composite sheet can be used as a build-up film or a dry film solder resist.
  • the method for producing the resin composite sheet is not particularly limited, but for example, a method of obtaining a resin composite sheet by applying (coating) a solution in which the resin composition of the present embodiment is dissolved in a solvent to a support and drying the solution can be mentioned.
  • the support used here may be, for example, a polyethylene film, a polypropylene film, a polycarbonate film, a polyethylene terephthalate film, an ethylene tetrafluoroethylene copolymer film, as well as release films obtained by applying a release agent to the surface of these films, organic film substrates such as polyimide film, conductive foils such as copper foil and aluminum foil, glass plates, SUS (Steel Use Stainless) plates, FRP (Fiber-Reinforced Plastics), and other plate-shaped substrates, but is not particularly limited thereto.
  • organic film substrates such as polyimide film, conductive foils such as copper foil and aluminum foil, glass plates, SUS (Steel Use Stainless) plates, FRP (Fiber-Reinforced Plastics), and other plate-shaped substrates, but is not particularly limited thereto.
  • Examples of application methods include a method in which a solution in which the resin composition of this embodiment is dissolved in a solvent is applied onto a support using a bar coater, die coater, doctor blade, baker applicator, or the like.
  • a single-layer sheet can be obtained by peeling or etching the support from a resin composite sheet in which the support and the resin composition are laminated. Note that a single-layer sheet can also be obtained without using a support by supplying a solution in which the resin composition of this embodiment is dissolved in a solvent into a mold having a sheet-shaped cavity and drying it to form it into a sheet.
  • the drying conditions for removing the solvent are not particularly limited, but since low temperatures tend to leave the solvent in the resin composition, and high temperatures cause the resin composition to harden, a temperature of 20°C to 200°C for 1 to 90 minutes is preferred.
  • the monolayer sheet or resin composite sheet can be used in an uncured state in which the solvent has simply been dried, or can be used in a semi-cured (B-stage) state as necessary.
  • the thickness of the resin layer in the monolayer sheet or resin composite sheet of this embodiment can be adjusted by the concentration of the solution of the resin composition of this embodiment used for application (coating) and the coating thickness, and is not particularly limited, but since a thicker coating thickness generally tends to leave the solvent when drying, a thickness of 0.1 to 500 ⁇ m is preferred.
  • Synthesis Example 1 Synthesis of modified polyphenylene ether compound ⁇ Synthesis of bifunctional phenylene ether oligomer>> CuBr2 was added to a 12 L vertical reactor equipped with a stirrer, a thermometer, an air inlet tube, and a baffle plate.
  • the resulting solution was concentrated with an evaporator, dropped into methanol to solidify, and the solid was collected by filtration and dried in vacuum to obtain 450.1 g of a modified polyphenylene ether compound.
  • the number average molecular weight of the modified polyphenylene ether compound in terms of polystyrene by the GPC method was 2250, the weight average molecular weight in terms of polystyrene by the GPC method was 3920, and the vinyl group equivalent was 1189 g / vinyl group.
  • the obtained polymer (va) having a structural unit represented by formula (V) had a number average molecular weight Mn of 2,060, a weight average molecular weight Mw of 30,700, and a monodispersity Mw/Mn of 14.9.
  • the polymer (va) having a structural unit represented by formula (V) was observed to have resonance lines derived from each monomer unit used as a raw material.
  • the proportion of each monomer unit (structural unit derived from each raw material) in the polymer (va) having a structural unit represented by formula (V) was calculated as follows.
  • Structural units derived from divinylbenzene 20.9 mol% (24.3 mass%)
  • the content of structural units having residual vinyl groups derived from divinylbenzene was 16.7 mol % (18.5 mass %).
  • the vinyl group equivalent was 241 g/eq.
  • the weight average molecular weight (Mw) and number average molecular weight (Mn) were measured by gel permeation chromatography (GPC) using a liquid delivery pump (Shimadzu Corporation, LC-20AD), a differential refractive index detector (Shimadzu Corporation, RID-10A), and a GPC column (Showa Denko K.K., GPC KF-801, 802, 803, 804), tetrahydrofuran as a solvent, a flow rate of 1.0 ml/min, a column temperature of 40° C., and a calibration curve based on monodisperse polystyrene.
  • GPC gel permeation chromatography
  • Example 1 5 parts by mass of the modified polyphenylene ether compound obtained in Synthesis Example 1 above, 12 parts by mass of a maleimide compound (NE-X-9500, manufactured by DIC Corporation, corresponding to a polymaleimide compound having a structural unit represented by formula (1)), 40 parts by mass of a maleimide compound (NE-X-9470S, manufactured by DIC Corporation, corresponding to a compound represented by formula (M1), the cured product having a dielectric loss tangent (Df) of 0.003 or less at a frequency of 10 GHz and a relative dielectric constant (Dk) of 2.5 or less), 3 parts by mass of a maleimide compound (BMI-2300, manufactured by Daiwa Chemical Industry Co., Ltd., corresponding to a compound represented by formula (M2)), 35 parts by mass of the polymer (va) having a structural unit represented by formula (V) obtained in Synthesis Example 2, 5 parts by mass of a phosphate ester flame retardant (PX-200, manufactured by Daihachi Chemical Industry
  • This varnish was impregnated and coated on a 0.1 mm thick NE glass woven fabric (2013 S101S, manufactured by Nitto Boseki Co., Ltd.) and dried by heating at 165° C. for 5 minutes to obtain a prepreg (thickness 0.1 mm) with a resin composition content of 60% by mass.
  • the properties of the NE glass woven fabric used are as follows: IPC applicable varieties: 2013 Density (stack/25mm) Vertical: 46 Density (stack/25mm) Width: 44.1 Thickness (mm): 0.070 Mass (g/ m2 ): 80.7 Eight sheets of the obtained prepreg were stacked, and 12 ⁇ m thick electrolytic copper foil (3EC-M3-VLP, manufactured by Mitsui Mining & Smelting Co., Ltd.) was placed on both sides. The resulting laminate was vacuum pressed at a pressure of 30 kgf/ cm2 and a temperature of 220°C for 120 minutes to obtain a copper foil clad laminate with an insulating layer thickness of 0.8 mm as a metal foil clad laminate.
  • electrolytic copper foil 3EC-M3-VLP, manufactured by Mitsui Mining & Smelting Co., Ltd.
  • the obtained copper foil-clad laminate was evaluated for dielectric constant (Dk), dielectric tangent (Df), and coefficient of thermal expansion (CTE-Z).
  • Dielectric constant (Dk) and dielectric loss tangent (Df) The copper foil of the copper foil-clad laminate obtained above was removed by etching to obtain a laminate A. The laminate A was dried at 120° C. for 60 minutes, and then the dielectric constant (Dk) and dielectric loss tangent (Df) after drying were measured at a frequency of 10 GHz using a perturbation method cavity resonator. The measurement temperature was 23° C. The perturbation method cavity resonator used was Agilent 8722ES manufactured by Agilent Technologies.
  • CTE-Z Coefficient of thermal expansion
  • CTE-Z linear thermal expansion coefficient (ppm / ° C) from 50 ° C to 280 ° C was measured by increasing the temperature from 40 ° C to 320 ° C at a rate of 10 ° C per minute using a thermomechanical analyzer (manufactured by TA Instruments).
  • the evaluation was as follows: S: 100 (ppm/°C) or less A: More than 100 (ppm/°C) and 130 (ppm/°C) or less B: More than 130 (ppm/°C) and 165 (ppm/°C) or less C: More than 165 (ppm/°C)
  • Example 2 In Example 1, the modified polyphenylene ether compound obtained in the above Synthesis Example 1, the maleimide compound (manufactured by Daiwa Chemical Industry Co., Ltd., BMI-2300, corresponding to the compound represented by formula (M2)), and DCP (dicumyl peroxide, curing accelerator) were not blended, the blending amount of the polymer (va) having a structural unit represented by formula (V) obtained in the above Synthesis Example 2 was changed to 30 parts by mass, and further, 8 parts by mass of a compound containing a (meth)allyl group (manufactured by Maruzen Petrochemical Co., Ltd., BANI-M, compound represented by formula (AN-4)) was blended, and further, 0.1 parts by mass of manganese octylate (manufactured by Nippon Chemical Industry Co., Ltd.) was blended. The same procedure as in Example 1 was repeated.
  • the maleimide compound manufactured by Daiwa Chemical Industry Co., Ltd., BMI-2300,
  • Example 3 The same procedure as in Example 1 was repeated, except that the amount of the maleimide compound (NE-X-9500 manufactured by DIC Corporation, corresponding to a polymaleimide compound having a structural unit represented by formula (1)) was changed from 12 parts by mass to 40 parts by mass, and the amount of the maleimide compound (NE-X-9470S manufactured by DIC Corporation, corresponding to a compound represented by formula (M1)) was changed from 40 parts by mass to 12 parts by mass.
  • the amount of the maleimide compound NE-X-9500 manufactured by DIC Corporation, corresponding to a polymaleimide compound having a structural unit represented by formula (1)
  • M1 a compound represented by formula
  • Example 4 The same procedure as in Example 1 was repeated, except that the amount of the maleimide compound (NE-X-9500 manufactured by DIC Corporation, corresponding to a polymaleimide compound having a structural unit represented by formula (1)) was changed from 12 parts by mass to 5 parts by mass, and the amount of the maleimide compound (NE-X-9470S manufactured by DIC Corporation, corresponding to a compound represented by formula (M1)) was changed from 40 parts by mass to 47 parts by mass.
  • the amount of the maleimide compound NE-X-9500 manufactured by DIC Corporation, corresponding to a polymaleimide compound having a structural unit represented by formula (1)
  • M1 a compound represented by formula
  • Example 5 The same procedure as in Example 1 was repeated except that the amount of the maleimide compound (NE-X-9500 manufactured by DIC Corporation, corresponding to a polymaleimide compound having a structural unit represented by formula (1)) blended was changed from 12 parts by mass to 40 parts by mass, no maleimide compound (NE-X-9470S manufactured by DIC Corporation, corresponding to the compound represented by formula (M1)) was blended, and 12 parts by mass of an aliphatic maleimide compound (MIZ-001 manufactured by Nippon Kayaku Co., Ltd., corresponding to maleimide compound (M6)) was blended.
  • the maleimide compound NE-X-9500 manufactured by DIC Corporation, corresponding to a polymaleimide compound having a structural unit represented by formula (1)
  • M1 no maleimide compound
  • M6 an aliphatic maleimide compound
  • Example 6 Example 1 was carried out in the same manner as in Example 1, except that the modified polyphenylene ether compound obtained in Synthesis Example 1 above was not blended, and 5 parts by mass of a modified polyphenylene ether compound having a terminal methacryloyl group (SA9000, manufactured by SABIC Innovative Plastics) was blended.
  • SA9000 a modified polyphenylene ether compound having a terminal methacryloyl group
  • Example 7 Example 1 was carried out in the same manner as in Example 1, except that the modified polyphenylene ether compound obtained in Synthesis Example 1 was not blended, and 5 parts by mass of triallyl isocyanurate (manufactured by Mitsubishi Chemical Corporation, TAIC) was blended.
  • TAIC triallyl isocyanurate
  • Example 8 Example 1 was carried out in the same manner as in Example 1, except that the amount of the modified polyphenylene ether compound obtained in Synthesis Example 1 was changed from 5 parts by mass to 40 parts by mass, and the polymer (va) having a structural unit represented by formula (V) obtained in Synthesis Example 2 was not blended.
  • Example 9 The same procedure as in Example 1 was repeated except that the amount of the maleimide compound (NE-X-9500 manufactured by DIC Corporation, corresponding to a polymaleimide compound having a structural unit represented by formula (1)) was changed from 12 parts by mass to 22 parts by mass, the amount of the maleimide compound (NE-X-9470S manufactured by DIC Corporation, corresponding to a compound represented by formula (M1)) was changed from 40 parts by mass to 70 parts by mass, and the modified polyphenylene ether compound obtained in Synthesis Example 1 above and the polymer (va) having a structural unit represented by formula (V) obtained in Synthesis Example 2 above were not blended.
  • the maleimide compound NE-X-9500 manufactured by DIC Corporation, corresponding to a polymaleimide compound having a structural unit represented by formula (1)
  • Example 10 The same procedures as in Example 1 were carried out except that the blending amount of the maleimide compound (NE-X-9500 manufactured by DIC Corporation, corresponding to a polymaleimide compound having a structural unit represented by formula (1)) was changed from 12 parts by mass to 11 parts by mass, the blending amount of the maleimide compound (NE-X-9470S manufactured by DIC Corporation, corresponding to the compound represented by formula (M1)) was changed from 40 parts by mass to 36 parts by mass, and further 5 parts by mass of a thermoplastic elastomer (TR2250 manufactured by JSR Corporation) was blended.
  • the maleimide compound NE-X-9500 manufactured by DIC Corporation, corresponding to a polymaleimide compound having a structural unit represented by formula (1)
  • Example 1 instead of the maleimide compound (NE-X-9500 manufactured by DIC Corporation, corresponding to a polymaleimide compound having a structural unit represented by formula (1)), the same amount of maleimide compound (MIR-3000-70MT manufactured by Nippon Kayaku Co., Ltd., a compound represented by formula (M3)) was used, 0.1 parts by mass of manganese octoate was blended, and DCP (dicumyl peroxide, Percumyl D manufactured by NOF Corporation, a curing accelerator) was not blended, and the rest was the same.
  • M3 a compound represented by formula (M3)
  • DCP dicumyl peroxide, Percumyl D manufactured by NOF Corporation, a curing accelerator
  • Example 2 Comparative Example 2 In Example 1, the same procedures were carried out except that neither the maleimide compound (NE-X-9470S manufactured by DIC Corporation, corresponding to the compound represented by formula (M1)) nor the maleimide compound (BMI-2300 manufactured by Daiwa Chemical Industry Co., Ltd., corresponding to the compound represented by formula (M2)) was used, the amount of the maleimide compound (NE-X-9500 manufactured by DIC Corporation, corresponding to a polymaleimide compound having a structural unit represented by formula (1)) was changed to 55 parts by mass, and the amount of DCP (dicumyl peroxide, Percumyl D manufactured by NOF Corporation, curing accelerator) was changed to 1.0 part by mass.
  • DCP dicumyl peroxide, Percumyl D manufactured by NOF Corporation, curing accelerator

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Abstract

L'invention concerne une composition de résine avec laquelle peut être obtenu un nouveau produit durci. L'invention concerne également le produit durci, un préimprégné, une carte stratifiée revêtue d'une feuille métallique, une feuille composite de résine et une carte de circuit imprimé. La composition de résine comprend un composé polymaléimide (A) et un composé maléimide (B) autre que le composé polymaléimide (A). Le composé polymaléimide (A) sert de charge d'alimentation de réaction (1) obtenue en faisant réagir : un composé amine aromatique (a1) ayant de 1 à 3 groupes alkyle sur un cycle aromatique ; un composé divinyle aromatique (a2) ayant deux groupes éthényle ; et de l'anhydride maléique.
PCT/JP2023/038272 2022-10-26 2023-10-24 Composition de résine, produit durci, préimprégné, carte stratifiée revêtue de feuille métallique, feuille composite de résine et carte de circuit imprimé WO2024090410A1 (fr)

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JP2022171864 2022-10-26
JP2022-171864 2022-10-26
JP2022207666 2022-12-23
JP2022-207666 2022-12-23
JP2023004511 2023-01-16
JP2023-004511 2023-01-16

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Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019230945A1 (fr) * 2018-06-01 2019-12-05 三菱瓦斯化学株式会社 Composition de résine, préimprégné, stratifié revêtu d'une feuille métallique, feuille de résine et carte imprimée
WO2020004211A1 (fr) * 2018-06-27 2020-01-02 三菱瓦斯化学株式会社 Composition de résine et ses applications
WO2020054601A1 (fr) * 2018-09-12 2020-03-19 日本化薬株式会社 Résine de maléimide, composition de résine durcissable, et produit durci de celle-ci
CN113121999A (zh) * 2019-12-31 2021-07-16 广东生益科技股份有限公司 一种树脂组合物及使用它的预浸料、层压板和印制电路板
WO2021149733A1 (fr) * 2020-01-24 2021-07-29 三菱瓦斯化学株式会社 Composition de résine, feuille de résine, préimprégné et carte de câblage imprimée
JP7160151B1 (ja) * 2021-07-01 2022-10-25 Dic株式会社 ポリマレイミド化合物、硬化性組成物、硬化物、プリプレグ、回路基板、ビルドアップフィルム、半導体封止材及び半導体装置。
WO2023171554A1 (fr) * 2022-03-11 2023-09-14 三菱瓦斯化学株式会社 Composition de résine, produit durci, préimprégné, stratifié revêtu d'une feuille métallique, feuille composite de résine, carte de circuit imprimé et dispositif à semi-conducteur
WO2023171553A1 (fr) * 2022-03-11 2023-09-14 三菱瓦斯化学株式会社 Composition de résine, produit durci, préimprégné, stratifié revêtu d'une feuille métallique, feuille composite de résine, carte de circuit imprimé et dispositif à semi-conducteur
WO2023176766A1 (fr) * 2022-03-14 2023-09-21 三菱瓦斯化学株式会社 Résine, composition de résine, produit durci, préimprégné, stratifié plaqué de feuille métallique, feuille composite de résine, carte de circuit imprimé et dispositif à semi-conducteur
WO2023176764A1 (fr) * 2022-03-14 2023-09-21 三菱瓦斯化学株式会社 Composition de résine, produit durci, préimprégné, stratifié revêtu d'une feuille métallique, feuille composite de résine, carte de circuits imprimés et dispositif à semi-conducteurs
WO2023176763A1 (fr) * 2022-03-14 2023-09-21 三菱瓦斯化学株式会社 Composition de résine, produit durci, préimprégné, stratifié revêtu d'une feuille métallique, feuille composite de résine, carte de circuits imprimés et dispositif à semi-conducteurs

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019230945A1 (fr) * 2018-06-01 2019-12-05 三菱瓦斯化学株式会社 Composition de résine, préimprégné, stratifié revêtu d'une feuille métallique, feuille de résine et carte imprimée
WO2020004211A1 (fr) * 2018-06-27 2020-01-02 三菱瓦斯化学株式会社 Composition de résine et ses applications
WO2020054601A1 (fr) * 2018-09-12 2020-03-19 日本化薬株式会社 Résine de maléimide, composition de résine durcissable, et produit durci de celle-ci
CN113121999A (zh) * 2019-12-31 2021-07-16 广东生益科技股份有限公司 一种树脂组合物及使用它的预浸料、层压板和印制电路板
WO2021149733A1 (fr) * 2020-01-24 2021-07-29 三菱瓦斯化学株式会社 Composition de résine, feuille de résine, préimprégné et carte de câblage imprimée
JP7160151B1 (ja) * 2021-07-01 2022-10-25 Dic株式会社 ポリマレイミド化合物、硬化性組成物、硬化物、プリプレグ、回路基板、ビルドアップフィルム、半導体封止材及び半導体装置。
WO2023171554A1 (fr) * 2022-03-11 2023-09-14 三菱瓦斯化学株式会社 Composition de résine, produit durci, préimprégné, stratifié revêtu d'une feuille métallique, feuille composite de résine, carte de circuit imprimé et dispositif à semi-conducteur
WO2023171553A1 (fr) * 2022-03-11 2023-09-14 三菱瓦斯化学株式会社 Composition de résine, produit durci, préimprégné, stratifié revêtu d'une feuille métallique, feuille composite de résine, carte de circuit imprimé et dispositif à semi-conducteur
WO2023176766A1 (fr) * 2022-03-14 2023-09-21 三菱瓦斯化学株式会社 Résine, composition de résine, produit durci, préimprégné, stratifié plaqué de feuille métallique, feuille composite de résine, carte de circuit imprimé et dispositif à semi-conducteur
WO2023176764A1 (fr) * 2022-03-14 2023-09-21 三菱瓦斯化学株式会社 Composition de résine, produit durci, préimprégné, stratifié revêtu d'une feuille métallique, feuille composite de résine, carte de circuits imprimés et dispositif à semi-conducteurs
WO2023176763A1 (fr) * 2022-03-14 2023-09-21 三菱瓦斯化学株式会社 Composition de résine, produit durci, préimprégné, stratifié revêtu d'une feuille métallique, feuille composite de résine, carte de circuits imprimés et dispositif à semi-conducteurs

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