WO2023047782A1 - 樹脂組成物、プリプレグ、金属箔張積層板、樹脂複合シート、プリント配線板、および、半導体装置 - Google Patents

樹脂組成物、プリプレグ、金属箔張積層板、樹脂複合シート、プリント配線板、および、半導体装置 Download PDF

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WO2023047782A1
WO2023047782A1 PCT/JP2022/028443 JP2022028443W WO2023047782A1 WO 2023047782 A1 WO2023047782 A1 WO 2023047782A1 JP 2022028443 W JP2022028443 W JP 2022028443W WO 2023047782 A1 WO2023047782 A1 WO 2023047782A1
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group
compound
resin composition
mass
formula
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PCT/JP2022/028443
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English (en)
French (fr)
Japanese (ja)
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祐司 中島
和弘 橋口
俊介 平野
恵一 長谷部
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三菱瓦斯化学株式会社
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Priority to JP2023501346A priority Critical patent/JP7380943B2/ja
Priority to KR1020247012992A priority patent/KR20240088944A/ko
Priority to CN202280064980.4A priority patent/CN118019799A/zh
Publication of WO2023047782A1 publication Critical patent/WO2023047782A1/ja
Priority to JP2023179632A priority patent/JP2024003007A/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/48—Polymers modified by chemical after-treatment
    • C08G65/485—Polyphenylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/12—Unsaturated polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • 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
    • C08K5/01—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • C08L71/126—Polyphenylene oxides modified by chemical after-treatment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • H01L23/295—Organic, e.g. plastic containing a filler
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement

Definitions

  • the present invention relates to resin compositions, prepregs, metal foil-clad laminates, resin composite sheets, printed wiring boards, and semiconductor devices.
  • Patent Document 1 discloses a novel soluble polyfunctional vinyl aromatic copolymer with improved heat resistance, compatibility, transparency and toughness, a method for producing the same, and a curable composition containing the copolymer. is disclosed.
  • An object of the present invention is to solve the above problems, and a resin composition having excellent moisture absorption and heat resistance while maintaining excellent dielectric properties, as well as a prepreg, a metal foil clad laminate, and a resin composite
  • An object is to provide a sheet, a printed wiring board, and a semiconductor device.
  • a predetermined aromatic vinyl compound has a molecular weight of less than 1000 and contains one organic group containing a carbon-carbon unsaturated bond in the molecule.
  • the above problems can be solved by blending the compound (B). Specifically, the above problems have been solved by the following means. ⁇ 1> a polymer (A) having a structural unit represented by formula (V); A resin composition comprising a compound (B) having a molecular weight of less than 1000 and containing one organic group containing a carbon-carbon unsaturated bond in the molecule.
  • Ar represents an aromatic hydrocarbon linking group.
  • ⁇ 5> Any one of ⁇ 1> to ⁇ 4>, wherein the organic group containing a carbon-carbon unsaturated bond is one selected from the group consisting of a vinyl group, an allyl group, an acrylic group, and a methacrylic group. 1.
  • ⁇ 6> The resin composition according to any one of ⁇ 1> to ⁇ 5>, wherein the compound (B) has a molecular weight of 70 to 500.
  • ⁇ 7> The resin composition according to any one of ⁇ 1> to ⁇ 6>, wherein the compound (B) has a boiling point of 110 to 300°C.
  • ⁇ 8> The resin according to any one of ⁇ 1> to ⁇ 7>, wherein the content of the compound (B) is 1 to 10 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition.
  • Composition. ⁇ 9> Any one of ⁇ 1> to ⁇ 8>, wherein the mass ratio of the polymer (A) and the compound (B) in the resin composition is 1:0.025 to 0.7
  • the described resin composition ⁇ 10>
  • thermosetting compound (C) is a maleimide compound, a polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds, a cyanate ester compound, an epoxy compound, a phenol compound, an alkenyl-substituted nadimide compound,
  • the other thermosetting compound (C) is a compound (M1) represented by formula (M1), a compound represented by formula (M3), a compound represented by formula (M5), and The resin composition according to ⁇ 10>, comprising at least one selected from the group consisting of compounds represented by formula (OP-1).
  • R M1 , R M2 , R M3 , and R M4 each independently represent a hydrogen atom or an organic group.
  • R M5 and R M6 each independently represent a hydrogen atom or an alkyl group.
  • Ar M represents a divalent aromatic group
  • A is a 4- to 6-membered alicyclic group
  • R M7 and R M8 are each independently an alkyl group
  • mx is 1 or 2
  • lx is 0 or 1.
  • R M9 and R M10 each independently represent a hydrogen atom or an alkyl group
  • R M11 , R M12 , R M13 and R M14 each independently represent a hydrogen atom or an organic group
  • R M15 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms , an aryloxy group having 1 to 10 carbon atoms, an arylthio group having 1 to 10 carbon atoms, a halogen atom, a hydroxyl group or a mercapto group
  • px represents an integer of 0 to 3
  • each R 55 independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a phenyl group, and n 5 represents an integer of 1 or more and 10 or less.
  • R 58 each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a phenyl group;
  • R 59 each independently represents a hydrogen atom or a methyl group;
  • n 6 represents an integer of 1 or more.
  • X represents an aromatic group
  • -(YO)n 2 - represents a polyphenylene ether structure
  • R 1 , R 2 and R 3 each independently represents a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group, n1 represents an integer of 1 to 6, n2 represents an integer of 1 to 100, and n3 represents an integer of 2 to 4.
  • the other thermosetting compound (C) is a compound (
  • the resin composition according to ⁇ 10> containing at least one selected from the group consisting of compounds.
  • R M1 , R M2 , R M3 , and R M4 each independently represent a hydrogen atom or an organic group.
  • R M5 and R M6 each independently represent a hydrogen atom or an alkyl group.
  • Ar M represents a divalent aromatic group
  • A is a 4- to 6-membered alicyclic group
  • R M7 and R M8 are each independently an alkyl group
  • mx is 1 or 2 and lx is 0 or 1.
  • R M9 and R M10 each independently represent a hydrogen atom or an alkyl group
  • R M11 , R M12 , R M13 and R M14 each independently represent a hydrogen atom or an organic group
  • R M15 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms , an aryloxy group having 1 to 10 carbon atoms, an arylthio group having 1 to 10 carbon atoms, a halogen atom, a hydroxyl group or a mercapto group
  • px represents an integer of 0 to 3
  • nx represents an integer of 1 to 20.
  • each R 55 independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a phenyl group, and n 5 represents an integer of 1 or more and 10 or less.
  • X represents an aromatic group
  • -(YO)n 2 - represents a polyphenylene ether structure
  • R 1 , R 2 and R 3 each independently represents a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group
  • n1 represents an integer of 1 to 6
  • n2 represents an integer of 1 to 100
  • n3 represents an integer of 2 to 4.
  • thermosetting compound (C) contains at least one selected from the group consisting of compounds represented by the formula (OP-1), and the content thereof is in the resin composition
  • the resin composition according to ⁇ 10> which is 3 to 50 parts by mass with respect to 100 parts by mass of the resin solid content.
  • X represents an aromatic group
  • —(Y—O)n 2 — represents a polyphenylene ether structure
  • R 1 , R 2 , and R 3 each independently represents a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group
  • n1 represents an integer of 1 to 6
  • n2 represents an integer of 1 to 100
  • n3 represents an integer of 2 to 4.
  • ⁇ 16> The resin composition according to any one of ⁇ 1> to ⁇ 15>, further comprising a filler (D).
  • ⁇ 17> The resin composition according to ⁇ 16>, wherein the content of the filler (D) is 10 to 500 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition.
  • the content of the polymer (A) is 5 to 70 parts by mass, and the content of the compound (B) is 1 to 10 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition.
  • the weight average molecular weight of the polymer (A) is 1,000 to 160,000, and the content of the polymer (A) is 5 parts per 100 parts by mass of the resin solid content in the resin composition.
  • the organic group containing a carbon-carbon unsaturated bond is one selected from the group consisting of a vinyl group, an allyl group, an acrylic group, and a methacrylic group
  • the compound (B) The molecular weight is 70 to 500, the boiling point of the compound (B) is 110 to 300 ° C., and the content of the compound (B) is 1 to 1 to 100 parts by mass of the resin solid content in the resin composition.
  • thermosetting compound (C) is a maleimide compound, a polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds.
  • thermosetting compound (C) a cyanate ester compound, an epoxy compound, a phenol compound, an alkenyl-substituted nadimide compound, an oxetane resin, and at least one selected from the group consisting of a benzoxazine compound, per 100 parts by mass of the resin solid content in the resin composition
  • the content of the thermosetting compound (C) is 5 to 95 parts by mass
  • the other thermosetting compound (C) contains at least one selected from the group consisting of compounds represented by formula (OP-1), and the content thereof is in the resin composition
  • the resin composition according to ⁇ 20> which is 3 to 50 parts by mass with respect to 100 parts by mass of the resin solid content.
  • X represents an aromatic group
  • —(Y—O)n 2 — represents a polyphenylene ether structure
  • R 1 , R 2 , and R 3 each independently represents a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group
  • n1 represents an integer of 1 to 6
  • n2 represents an integer of 1 to 100
  • n3 represents an integer of 2 to 4.
  • a metal foil clad laminate comprising at least one layer formed from the prepreg according to ⁇ 23> and a metal foil disposed on one side or both sides of the layer formed from the prepreg.
  • a resin composite sheet comprising a support and a layer formed from the resin composition according to any one of ⁇ 1> to ⁇ 22> disposed on the surface of the support.
  • a printed wiring board comprising an insulating layer and a conductor layer disposed on a surface of the insulating layer, wherein the insulating layer comprises the resin composition according to any one of ⁇ 1> to ⁇ 22>.
  • a printed wiring board comprising layers formed from materials.
  • a semiconductor device including the printed wiring board according to ⁇ 26>.
  • an "alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • the notations that do not describe substituted and unsubstituted are preferably unsubstituted.
  • the dielectric constant indicates the ratio of the dielectric constant of a substance to the vacuum dielectric constant.
  • the relative dielectric constant may be simply referred to as "permittivity”.
  • (meth)acryl represents both or either acryl and methacryl. If the standards shown in this specification differ from year to year in terms of measurement methods, etc., the standards as of January 1, 2021 shall be used unless otherwise specified.
  • the resin solid content refers to the components excluding the filler (D) and the solvent, the polymer (A) having a structural unit represented by the formula (V), and the molecular weight of less than 1000 And, a compound (B) containing one organic group containing a carbon-carbon unsaturated bond in the molecule (B), and other thermosetting compounds (C), elastomers, silane coupling agents, and This is intended to include other resin additive components (additives such as flame retardants, etc.).
  • the resin composition of the present embodiment comprises a polymer (A) having a structural unit represented by formula (V), a molecular weight of less than 1000, and an organic group containing a carbon-carbon unsaturated bond in the molecule. and one compound (B) (hereinafter sometimes simply referred to as "compound (B)").
  • Ar represents an aromatic hydrocarbon linking group. * represents a bonding position.
  • the polymer (A) having the structural unit represented by formula (V) is a polymer and has many vinyl groups in its molecular chain. That is, if the vinyl group remains unreacted during curing, the moisture absorption and heat resistance is deteriorated.
  • the unreacted vinyl groups of the polymer (A) having the structural unit represented by the formula (V) could be capped by blending the compound (B).
  • the number of unreacted vinyl groups in the resulting cured product was reduced, and the moisture absorption and heat resistance was greatly improved.
  • compound (B) is a molecule with a small molecular weight of less than 1000, it is assumed that it has high mobility and diffusibility, and the probability of reacting with unreacted vinyl groups also increases. It was speculated that the capping effect as described above improves the moisture absorption and heat resistance if the functional group caps the vinyl group in the polymer (A) other than the organic group containing a carbon-carbon unsaturated bond. . However, depending on the type of functional group, a highly polar site may remain even after capping, which may adversely affect the dielectric properties of the cured product. In contrast, in the present embodiment, the use of a compound having an organic group containing a carbon-carbon unsaturated bond is presumed to make the obtained cured product less polar.
  • the resin composition of this embodiment contains a polymer (A) having a structural unit 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. * represents a bonding position.
  • the aromatic hydrocarbon linking group may be a group consisting only of an optionally substituted aromatic hydrocarbon, or may be a group consisting of an optionally substituted aromatic hydrocarbon and another linking group.
  • the aromatic hydrocarbon may be a group consisting of a combination of groups, and is preferably a group consisting only of an optionally substituted aromatic hydrocarbon.
  • the substituent that the aromatic hydrocarbon may have is a substituent Z (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.).
  • the aromatic hydrocarbon preferably has no substituents.
  • the aromatic hydrocarbon linking group is generally a divalent linking group.
  • the aromatic hydrocarbon linking group specifically includes a phenylene group, a naphthalenediyl group, an anthracenediyl group, a phenanthenediyl group, a biphenyldiyl group, and a fluorenediyl group, which may have a substituent.
  • a phenylene group optionally having a substituent is preferable.
  • the substituent is exemplified by the above-described substituent Z, but the above-described groups such as the phenylene group preferably have no substituent.
  • the structural unit represented by the formula (V) includes a structural unit represented by the following formula (V1), a structural unit represented by the following formula (V2), and a structural unit represented by the following formula (V3). More preferably, at least one is included. In addition, * in the following formula represents a binding position. Further, hereinafter, the structural units represented by formulas (V1) to (V3) may be collectively referred to as "structural unit (a)".
  • L 1 is an aromatic hydrocarbon linking group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, even more preferably 6 to 10 carbon atoms).
  • Specific examples include a phenylene group, a naphthalenediyl group, an anthracenediyl group, a phenanthenediyl group, a biphenyldiyl group, and a fluorenediyl group, which may have a substituent.
  • a phenylene group having a low molecular weight is preferred.
  • the substituent is exemplified by the above-described substituent Z, but the above-described groups such as the phenylene group preferably have no substituent.
  • the compound forming the structural unit (a) is preferably a divinyl aromatic compound, and examples thereof include divinylbenzene, bis(1-methylvinyl)benzene, divinylnaphthalene, divinylanthracene, divinylbiphenyl, and divinylphenanthrene. be done. Among them, divinylbenzene is particularly preferred. One type of these divinyl aromatic compounds may be used, or two or more types may be used as necessary.
  • the polymer (A) having a structural unit represented by formula (V) may be a homopolymer of the structural unit (a) as described above, but may be a copolymer with a structural unit derived from another monomer. It may be a coalescence.
  • the copolymerization ratio of the structural unit (a) is preferably 3 mol% or more, and 5 mol. % or more, more preferably 10 mol % or more, and may be 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, and 60 mol%. % or less, even more preferably 50 mol% or less, even more preferably 40 mol% or less, even more preferably 30 mol% or less, and It may be 25 mol % or less, or 20 mol % or less.
  • structural units derived from other monomers include structural units (b) derived from aromatic compounds having one vinyl group (monovinyl aromatic compounds).
  • the structural unit (b) derived from a monovinyl aromatic compound is preferably a structural unit represented by the following formula (V4).
  • L 2 is an aromatic hydrocarbon linking group, and preferred specific examples thereof include the above-mentioned examples of L 1 .
  • R V1 is a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms (preferably an alkyl group). When R V1 is a hydrocarbon group, it preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms. R V1 and L 2 may have the substituent Z described above.
  • the polymer (A) having a structural unit represented by formula (V) is a copolymer containing a structural unit (b) derived from a monovinyl aromatic compound
  • examples of the monovinyl aromatic compound include styrene. , vinylnaphthalene, vinylaromatic compounds such as vinylbiphenyl; o-methylstyrene, m-methylstyrene, p-methylstyrene, o,p-dimethylstyrene, o-ethylvinylbenzene, m-ethylvinylbenzene, p-ethyl nucleus alkyl-substituted vinyl aromatic compounds such as vinylbenzene, methylvinylbiphenyl and ethylvinylbiphenyl;
  • the monovinyl aromatic compounds exemplified here may optionally have the substituent Z described above. Moreover, one of these monovinyl aromatic compounds may be used,
  • the copolymerization ratio of the structural unit (b) is 10 mol% or more. is preferred, more preferably 15 mol% or more, further 20 mol% or more, 30 mol% or more, 40 mol% or more, 50 mol% or more, 60 mol% or more, 70 mol% or more, 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 (A) having the structural unit represented by formula (V) may have structural units other than the structural unit (a) and the structural unit (b).
  • Examples of other structural units include structural units (c) derived from cycloolefin compounds.
  • Cycloolefin compounds include hydrocarbons having a double bond in the ring structure. Specifically, in addition to monocyclic cyclic olefins such as cyclobutene, cyclopentene, cyclohexene, and cyclooctene, compounds having a norbornene ring structure such as norbornene and dicyclopentadiene, and cycloolefin compounds in which aromatic rings are condensed such as indene and acenaphthylene etc.
  • Examples of norbornene compounds include those described in paragraphs 0037 to 0043 of JP-A-2018-39995, the contents of which are incorporated herein.
  • the cycloolefin compounds exemplified here may further have the substituent Z described above.
  • the copolymerization ratio of the structural unit (c) is 10 mol% or more. is preferred, 20 mol % or more is more preferred, and 30 mol % or more is even more preferred.
  • the upper limit is preferably 90 mol% or less, more preferably 80 mol% or less, even more preferably 70 mol% or less, may be 50 mol% or less, or 30 mol%. It may be below.
  • a polymer (A) having a structural unit represented by formula (V) may further incorporate a structural unit (d) derived from a different polymerizable compound (hereinafter also referred to as another polymerizable compound).
  • Other polymerizable compounds (monomers) include, for example, compounds containing three vinyl groups. Specific examples include 1,3,5-trivinylbenzene, 1,3,5-trivinylnaphthalene, and 1,2,4-trivinylcyclohexane. Alternatively, ethylene glycol diacrylate, butadiene and the like can be used.
  • the copolymerization ratio of structural units (d) derived from other polymerizable compounds is preferably 30 mol% or less, more preferably 20 mol% or less, and even more preferably 10 mol% or less. .
  • a polymer essentially comprising the structural unit (a) and containing at least one of the structural units (b) to (d) is exemplified. Furthermore, an embodiment is exemplified in which the total of structural units (a) to (d) accounts for 95 mol% or more, further 98 mol% or more of all structural units.
  • the structural unit (a) is essential, and among all structural units excluding the terminal, a structural unit containing an aromatic ring is preferably 90 mol % or more, more preferably 95 mol % or more, and may be 100 mol %.
  • one structural unit means a monomer (for example, divinyl aromatic compounds, monovinyl aromatic compounds, etc.).
  • the method for producing the polymer (A) having the structural unit represented by formula (V) is not particularly limited and may be a conventional method. compounds, cycloolefin compounds, etc.) and polymerizing in the presence of a Lewis acid catalyst.
  • a metal fluoride such as boron trifluoride or a complex thereof can be used as the Lewis acid catalyst.
  • the molecular weight of the polymer (A) having the structural unit represented by formula (V) is, in terms of number average molecular weight Mn, preferably 300 or more, more preferably 500 or more, and 1,000 or more. is more preferable, and 1,500 or more is more preferable.
  • the upper limit is preferably 130,000 or less, more preferably 120,000 or less, even more preferably 110,000 or less, even more preferably 100,000 or less.
  • the weight-average molecular weight Mw of the polymer (A) having the structural unit represented by formula (V) is preferably 1,000 or more, more preferably 1,500 or more. It is more preferably 000 or more, more preferably 2,500 or more, even more preferably 3,000 or more, and may be 3,500 or more, or 4,000 or more.
  • the polymer (A) having the structural unit represented by the formula (V) has excellent low dielectric properties, especially Df and dielectric properties after moisture absorption. can be effectively exhibited.
  • the upper limit is preferably 160,000 or less, more preferably 150,000 or less, even more preferably 140,000 or less, even more preferably 130,000 or less, and 120,000 or less. , 110,000 or less.
  • the thickness is equal to or less than the above upper limit, there is a tendency that poor embedding is less likely to occur when the prepreg or resin sheet is laminated on the circuit board.
  • the monodispersity (Mw/Mn) represented by the ratio of the weight average molecular weight Mw to the number average molecular weight Mn is preferably 100 or less, more preferably 50 or less, and even more preferably 20 or less. .
  • the lower limit value is practically 1.1 or more, and may be 5 or more, 7 or more, and even if it is 10 or more, the required performance is satisfied.
  • the above Mw and Mn are measured according to the description of Examples described later.
  • the vinyl group equivalent weight of the polymer (A) having the structural unit represented by formula (V) is 200 g/eq. 230 g/eq. more preferably 250 g/eq. more preferably 300 g/eq. Above, 350g/eq. or more.
  • the equivalent weight of the vinyl group is 1200 g/eq. It is preferably less than or equal to 1000 g/eq. It is more preferably less than or equal to 800 g/eq. 600 g/eq. 500 g/eq. 400 g/eq. Below, 350 g/eq. It may be below.
  • the amount is at least the above lower limit, the storage stability of the resin composition tends to improve, and the fluidity of the resin composition tends to improve.
  • the polymer (A) having the structural unit represented by the formula (V) used in the present embodiment preferably has excellent low dielectric properties in its cured product.
  • the cured product of the polymer (A) having the structural unit represented by the formula (V) used in this embodiment has a dielectric constant (Dk) of 2.80 or less at 10 GHz measured according to the cavity resonator perturbation method. is preferably 2.60 or less, more preferably 2.50 or less, and even more preferably 2.40 or less.
  • the lower limit value of the dielectric constant is practically 1.80 or more, for example.
  • the cured product of the polymer (A) having the structural unit represented by the formula (V) used in the present embodiment has a dielectric loss tangent (Df) at 10 GHz measured according to the cavity resonator perturbation method of 0.0030 or less. It is preferably 0.0020 or less, even more preferably 0.0010 or less. Moreover, the lower limit value of the dielectric loss tangent is practically 0.0001 or more, for example.
  • Dk dielectric constant
  • Df dielectric loss tangent
  • the content of the polymer (A) having the structural unit represented by the formula (V) is 5 to 70 mass. It is preferable that it is a part.
  • the lower limit of the content of the polymer (A) having the structural unit represented by formula (V) is 7 parts by mass or more when the resin solid content in the resin composition is 100 parts by mass.
  • it is 9 parts by mass or more, still 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, and 25 parts by mass. Part or more is particularly preferred.
  • the upper limit of the content of the polymer (A) having the structural unit represented by the formula (V) is 65 parts by mass or less when the resin solid content in the resin composition is 100 parts by mass. is preferably 60 parts by mass or less, more preferably 50 parts by mass or less, even more preferably 40 parts by mass or less, even more preferably 35 parts by mass or less, and 20 parts by mass It may be less than part.
  • the polymer (A) having a structural unit represented by formula (V) may be contained alone or in combination of two or more in the resin composition. When two or more types are included, the total amount is preferably within the above range.
  • the resin composition of the present embodiment contains a compound (B) having a molecular weight of less than 1000 and containing one organic group containing a carbon-carbon unsaturated bond in the molecule (compound (B)). It is speculated that the carbon-carbon unsaturated bond of compound (B) reacts with the vinyl group of polymer (A) having the structural unit represented by formula (V), thereby improving the moisture absorption and heat resistance of the resulting cured product. be done.
  • the carbon-carbon unsaturated bond constituting the organic group containing the carbon-carbon unsaturated bond does not include those included as part of the aromatic ring.
  • carbon-carbon unsaturated bonds contained as part of non-aromatic rings examples include carbon-carbon unsaturated bonds included as part of non-aromatic rings include cyclohexenyl groups in the molecule. It is also meant to include portions other than the terminals of linear or branched organic groups, ie, carbon-carbon unsaturated bonds contained in linear or branched chains.
  • the vinyl group possessed by the polymer (A) having the structural unit represented by the formula (V) can be more effectively It becomes possible to react.
  • the organic group containing a carbon-carbon unsaturated bond is more preferably one selected from the group consisting of a vinyl group, an allyl group, an acrylic group, and a methacrylic group, and more preferably a vinyl group.
  • the compound (B) used in this embodiment is also preferably composed only of atoms selected from carbon atoms, hydrogen atoms, oxygen atoms and silicon atoms.
  • the compound (B) used in this embodiment may or may not have a polar group.
  • the compound (B) used in this embodiment preferably does not have a polar group.
  • Polar groups are exemplified by amino groups, carboxyl groups, hydroxy groups and nitro groups.
  • the molecular weight of compound (B) is preferably 70 or more, more preferably 80 or more, even more preferably 90 or more.
  • the upper limit of the molecular weight of the compound (B) is preferably 500 or less, more preferably 400 or less, still more preferably 300 or less, even more preferably 200 or less, and 150 or less. may By making it equal to or less than the above upper limit, there is a tendency that the effect of increasing the reactivity with the polymer (A) having the structural unit represented by formula (V) is further improved.
  • the average molecular weight value of the compound (B) is preferably included in the above range, and the molecular weight of each compound is included in the preferred range. is more preferred.
  • the boiling point of compound (B) is preferably 110° C. or higher, more preferably 115° C. or higher, even more preferably 120° C. or higher. By making it equal to or higher than the above lower limit, volatilization of the compound (B) during thermosetting of the resin composition is suppressed, and the polymer (A) having the structural unit represented by the formula (V) is more effectively produced.
  • the vinyl group having the compound (B) can be reacted with the compound (B).
  • the boiling point of the compound (B) is preferably 300° C. or lower, more preferably 250° C. or lower, and even more preferably 200° C. or lower.
  • the boiling point average value should be within the above range, but the boiling point of each compound is preferably within the above preferable range.
  • Examples of the compound (B) include (meth)acrylate compounds, aromatic vinyl compounds (preferably styrene compounds), saturated fatty acid vinyl compounds, vinyl cyanide compounds, ethylenically unsaturated carboxylic acids, and ethylenically unsaturated carboxylic acids.
  • Anhydrides ethylenically unsaturated dicarboxylic acid monoalkyl esters, ethylenically unsaturated carboxylic acid amides, vinylsilane compounds (e.g., vinyltrialkoxysilane, etc.), acrylsilane compounds (e.g., acrylictrialkoxysilane, etc.), methacrylsilane compounds ( (e.g., methacryltrialkoxysilane, etc.), styrylsilane compounds (e.g., styryltrialkoxysilane, etc.), and the like, (meth)acrylic acid ester compounds, aromatic vinyl compounds, saturated fatty acid vinyl compounds, vinylsilane compounds, acrylsilane compounds.
  • vinylsilane compounds e.g., vinyltrialkoxysilane, etc.
  • acrylsilane compounds e.g., acrylictrialkoxysilane, etc.
  • methacrylsilane compounds e.g., me
  • compound (B) examples include methylstyrene, ethylvinylbenzene, vinyltrimethoxysilane, and vinyltriethoxysilane.
  • the content of the compound (B) is preferably 1 part by mass or more, more preferably 2 parts by mass or more, based on 100 parts by mass of the resin solid content. It is more preferably 5 parts by mass or more.
  • the upper limit of the content of the compound (B) is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and 10 parts by mass or less with respect to 100 parts by mass of the resin solid content. is more preferably 8 parts by mass or less, and even more preferably 5 parts by mass or less.
  • the resin composition of the present embodiment may contain only one type of compound (B), or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
  • the mass ratio of the polymer (A) and the compound (B) is preferably 0.025 or more, preferably 0.05 or more, with respect to the polymer (A) 1. is more preferably 0.1 or more, even more preferably 0.15 or more, and may be 0.2 or more.
  • the upper limit of the mass ratio of the polymer (A) and the compound (B) is preferably 0.7 or less, more preferably 0.5 or less, and 0.5 or less, relative to 1 of the polymer (A).
  • the content is more preferably 4 or less, even more preferably 0.3 or less, and may be 0.25 or less.
  • the low dielectric properties (Dk and/or Df) of the obtained cured product tend to be further improved.
  • the resin composition of the present embodiment has a molecular weight of less than 1000 and two organic groups having a CH 2 ⁇ C(X)—(X is a hydrogen atom or a methyl group) structure in the molecule.
  • a configuration that does not substantially contain the compound (B′) containing the above can also be used.
  • Specific examples of the compound (B') include aromatic divinyl compounds, particularly divinylbenzene.
  • Substantially free of the compound (B') means that the content of the compound (B') is less than 1 part by mass with respect to 100 parts by mass of the resin solid content in the resin composition. It is preferably less than 0.1 part by mass, more preferably less than 0.01 part by mass, and even more preferably less than 0.001 part by mass.
  • the resin composition of the present embodiment preferably further contains another thermosetting compound (C) that does not correspond to the polymer (A) and the compound (B).
  • another thermosetting compound (C) that does not correspond to the polymer (A) and the compound (B).
  • the weight average molecular weight of the other thermosetting compound (C) is preferably 100 or more, more preferably 200 or more, still more preferably 300 or more.
  • the upper limit of the weight average molecular weight of the other thermosetting compound (C) is preferably 5,000 or less, more preferably 4,000 or less.
  • the functional group equivalent weight of the other thermosetting compound (C) is preferably 100 g/eq.
  • the upper limit of equivalent weight of the functional group of the other thermosetting compound (C) is preferably 1,500 g/eq. Below, more preferably 1,300 g/eq. It is below. In this embodiment, it is particularly preferred that the other thermosetting compound (C) satisfies the above weight average molecular weight and functional group equivalent weight. Such other thermosetting compound (C) tends to have a smaller weight-average molecular weight than the polymer (A) having the structural unit represented by formula (V), and has a higher functional group concentration.
  • the other thermosetting compound (C) is a maleimide compound, a polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds, a cyanate ester compound, an epoxy compound, a phenol compound, an alkenyl-substituted nadimide compound. , an oxetane resin, and preferably contains at least one selected from the group consisting of benzoxazine compounds, and more preferably contains a maleimide compound and/or a polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds.
  • the compound represented by the formula (M1) (M1), the compound represented by the formula (M3), the compound represented by the formula (M5), and the group consisting of the compound represented by the formula (OP-1) It is further preferable to contain at least one selected from the compound represented by the formula (M1) (M1), the compound represented by the formula (M3), and the compound represented by the formula (OP-1) It is more preferable to contain at least one selected from the group consisting of, and from the viewpoint of low dielectric properties, it is even more preferable to contain the compound (M1) represented by 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 is a 4- to 6-membered alicyclic group
  • R M7 and R M8 are each independently an alkyl group
  • mx is 1 or 2 and lx is 0 or 1.
  • R M9 and R M10 each independently represent a hydrogen atom or an alkyl group
  • R M11 , R M12 , R M13 and R M14 each independently represent a hydrogen atom or an organic group
  • R M15 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms , an aryloxy group having 1 to 10 carbon atoms, an arylthio group having 1 to 10 carbon atoms, a halogen atom, a hydroxyl group or a mercapto group
  • px represents an integer of 0 to 3
  • nx represents an integer of 1 to 20.
  • each R 55 independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a phenyl group, and n 5 represents an integer of 1 or more and 10 or less.
  • R 58 each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a phenyl group
  • R 59 each independently represents a hydrogen atom or a methyl group
  • n 6 represents an integer of 1 or more.
  • X represents an aromatic group
  • —(Y—O)n 2 — represents a polyphenylene ether structure
  • R 1 , R 2 , and R 3 each independently represents a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group
  • n1 represents an integer of 1 to 6
  • n2 represents an integer of 1 to 100
  • n3 represents an integer of 2 to 4.
  • the resin composition of this embodiment may contain a maleimide compound.
  • the resin composition of the present embodiment has 1 or more (preferably 2 to 12, more preferably 2 to 6, still more preferably 2 to 4, still more preferably 2 or 3, still more preferably 2) per molecule.
  • the compound is not particularly limited as long as it has a maleimide group, and a wide range of compounds commonly used in the field of printed wiring boards can be used.
  • compounds represented by formulas (M0) to (M5) are preferred
  • compounds represented by formulas (M1) to (M4) are more preferred
  • formula (M1) and/or formula More preferred are compounds represented by M3)
  • even more preferred are compounds (M1) represented by formula (M1).
  • each R 51 independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a phenyl group; each R 52 independently represents a hydrogen atom or a methyl group; n 1 represents an integer of 1 or more.
  • R 51 is preferably a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, phenyl group, hydrogen atom and One of the methyl groups is more preferred, and a hydrogen atom is even more preferred.
  • R 52 is preferably a methyl group.
  • n 1 is preferably an integer of 1 to 10, more preferably an integer of 1 to 5, even more preferably an integer of 1 to 3, more preferably 1 or 2, and even more preferably 1.
  • the compound represented by Formula (M0) may be a single compound or a mixture of two or more compounds. Examples of mixtures include mixtures of compounds with different n 1 , mixtures of compounds with different types of substituents for R 51 and/or R 52 , and the bonding positions of the maleimide group and the oxygen atom to the benzene ring (meta-position, para-position, mixtures of compounds with different ortho positions) and mixtures of compounds in which two or more of the above different points are combined. The same applies to the compounds represented by formulas (M1) to (M5) below.
  • R M1 , R M2 , R M3 , and R M4 each independently represent a hydrogen atom or an organic group.
  • R M5 and R M6 each independently represent a hydrogen atom or an alkyl group.
  • Ar M represents a divalent aromatic group, A is a 4- to 6-membered alicyclic group, R M7 and R M8 are each independently an alkyl group, mx is 1 or 2 and lx is 0 or 1.
  • R M9 and R M10 each independently represent a hydrogen atom or an alkyl group
  • R M11 , R M12 , R M13 and R M14 each independently represent a hydrogen atom or an organic group
  • R M15 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms , an aryloxy group having 1 to 10 carbon atoms, an arylthio group having 1 to 10 carbon atoms, a halogen atom, a hydroxyl group or a mercapto group
  • px represents an integer of 0 to 3
  • nx represents an integer of 1 to 20.
  • R M1 , R M2 , R M3 and R M4 in the formula each independently represent a hydrogen atom or an organic group.
  • the organic group here is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, a methyl group, an ethyl group, a propyl group, a butyl group. Among them, a methyl group is particularly preferred.
  • R M1 and R M3 are each independently preferably an alkyl group, and R M2 and R M4 are preferably hydrogen atoms.
  • RM5 and RM6 each independently represent a hydrogen atom or an alkyl group, preferably an alkyl group.
  • the alkyl group here is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and especially a methyl group.
  • Ar 1 M represents a divalent aromatic group, preferably a phenylene group, a naphthalenediyl group, a phenanthenediyl group or an anthracenediyl group, more preferably a phenylene group, still more preferably an m-phenylene group.
  • Ar M may have a substituent, and the substituent is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, a methyl group, Ethyl group, propyl group and butyl group are more preferred, and methyl group is particularly preferred.
  • Ar M is unsubstituted.
  • A is a 4- to 6-membered alicyclic group, more preferably a 5-membered alicyclic group (preferably a group forming an indane ring in combination with a benzene ring).
  • R 1 M7 and R 1 M8 are each independently an alkyl group, preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group.
  • mx is 1 or 2, preferably 2;
  • lx is 0 or 1, preferably 1;
  • R M9 and R M10 each independently represent a hydrogen atom or an alkyl group, more preferably an alkyl group.
  • the alkyl group here is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and especially a methyl group.
  • R M11 , R M12 , R M13 and R M14 each independently represent a hydrogen atom or an organic group.
  • the organic group here is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, a methyl group, an ethyl group, a propyl group, a butyl group.
  • R M12 and R M13 are each independently preferably an alkyl group, and R M11 and R M14 are preferably hydrogen atoms.
  • R M15 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aryl group having 1 to 10 carbon atoms.
  • aryloxy group, arylthio group having 1 to 10 carbon atoms, halogen atom, hydroxyl group or mercapto group, alkyl group having 1 to 4 carbon atoms, cycloalkyl group having 3 to 6 carbon atoms, or 6 to 10 carbon atoms is preferably an aryl group of px represents an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, and still more preferably 0.
  • nx represents an integer of 1-20.
  • nx may be an integer of 10 or less.
  • the resin composition of the present embodiment may contain only one compound (M1) represented by the formula (M1) and having at least different nx values, or may contain two or more compounds.
  • the average value of nx (average repeating unit number) n in the compound (M1) represented by formula (M1) in the resin composition has a low melting point (low softening point) and a melt viscosity is preferably 0.92 or more, more preferably 0.95 or more, even more preferably 1.0 or more, and 1.1 or more, in order to make it low and excellent in handleability. More preferably. Also, n is preferably 10.0 or less, more preferably 8.0 or less, still more preferably 7.0 or less, and even more preferably 6.0 or less. It may be 0 or less. The same applies to formula (M1-1) and the like, which will be described later.
  • the compound (M1) represented by the 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
  • R M27 , R M28 , R M29 and R M30 each independently represent a hydrogen atom or an organic group
  • R M31 and R M32 each independently represent a hydrogen atom or an alkyl group
  • R M33 , RM34 , RM35 and RM36 each independently represent a hydrogen atom or an organic group
  • RM37 , RM38 and RM39 each independently represent a hydrogen atom or an alkyl group
  • nx is represents an integer of 1 or more and 20 or less.
  • R M21 , R M22 , R M23 , and R M24 in the formula each independently represent a hydrogen atom or an organic group.
  • the organic group here is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, a methyl group, an ethyl group, a propyl group, a butyl group. More preferred, and a methyl group is particularly preferred.
  • R M21 and R M23 are preferably alkyl groups, and R M22 and R M24 are preferably hydrogen atoms.
  • RM25 and RM26 each independently represent a hydrogen atom or an alkyl group, preferably an alkyl group.
  • the alkyl group here is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and especially a methyl group.
  • R M27 , R M28 , R M29 and R M30 each independently represent a hydrogen atom or an organic group, preferably a hydrogen atom.
  • the organic group here is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, a methyl group, an ethyl group, a propyl group, a butyl group. More preferred, and a methyl group is particularly preferred.
  • R M31 and R M32 each independently represent a hydrogen atom or an alkyl group, preferably an alkyl group.
  • the alkyl group here is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and especially a methyl group.
  • R M33 , R M34 , R M35 and R M36 each independently represent a hydrogen atom or an organic group.
  • the organic group here is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, a methyl group, an ethyl group, a propyl group, a butyl group.
  • R M33 and R M36 are preferably hydrogen atoms, and R M34 and R M35 are preferably alkyl groups.
  • R M37 , R M38 and R M39 each independently represent a hydrogen atom or an alkyl group, preferably an alkyl group.
  • the alkyl group here is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and especially a methyl group.
  • nx represents an integer of 1 or more and 20 or less. nx may be an integer of 10 or less.
  • the compound represented by formula (M1-1) is preferably a compound represented by formula (M1-2) below.
  • R M21 , R M22 , R M23 and R M24 each independently represent a hydrogen atom or an organic group
  • R M25 and R M26 each independently represent a hydrogen atom or an alkyl
  • R M27 , R M28 , R M29 and R M30 each independently represent a hydrogen atom or an organic group
  • R M31 and R M32 each independently represent a hydrogen atom or an alkyl group
  • R M33 , RM34 , RM35 and RM36 each independently represent a hydrogen atom or an organic group
  • RM37 , RM38 and RM39 each independently represent a hydrogen atom or an alkyl group
  • nx is represents an integer of 1 or more and 20 or less.
  • R M21 , R M22 , R M23 , R M24 , R M25 , R M26 , R M27 , R M28 , R M29 , R M30 , R M31 , R M32 , R M33 , R M34 , R M35 , R M36 , R M37 , R M38 , R M39 and nx are respectively R M21 , R M22 , R M23 , R M24 , R M25 , R M26 , R M27 , R M27 , R M26 , R M27 in formula (M1-1) RM28 , RM29 , RM30 , RM31 , RM32 , RM33 , RM34 , RM35 , RM36 , RM37 , RM38 , RM39 , and nx, and the preferred ranges are also the same .
  • the compound represented by the formula (M1-1) is preferably a compound represented by the following formula (M1-3), more preferably a compound represented by the following formula (M1-4). more preferred.
  • M1-3 nx represents an integer of 1 or more and 20 or less.
  • nx may be an integer of 10 or less.
  • the molecular weight of compound (M1) represented by formula (M1) is preferably 500 or more, more preferably 600 or more, and even more preferably 700 or more. When the content is at least the above lower limit, the resulting cured product tends to be further improved in low dielectric properties and low water absorption. Further, the molecular weight of the compound (M1) represented by the formula (M1) is preferably 10,000 or less, more preferably 9,000 or less, even more preferably 7,000 or less, and 5,000 or less. More preferably, it is 4,000 or less. By adjusting the amount to the above upper limit or less, the heat resistance and handleability of the resulting cured product tend to be further improved.
  • each R 54 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 1-10, more preferably an integer of 1-5, even more preferably an integer of 1-3, and most preferably 1 or 2.
  • each R 55 independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a phenyl group, and n 5 represents an integer of 1 or more and 10 or less.
  • R 55 is preferably a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, phenyl group, hydrogen atom and One of the methyl groups is more preferred, and a hydrogen atom is even more preferred.
  • n5 is preferably an integer of 1 or more and 5 or less, more preferably an integer of 1 to 3, and even more preferably 1 or 2.
  • each R 56 independently represents a hydrogen atom, a methyl group or an ethyl group
  • each R 57 independently represents a hydrogen atom or a methyl group.
  • R 58 each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a phenyl group
  • R 59 each independently represents a hydrogen atom or a methyl group
  • n 6 represents an integer of 1 or more.
  • R 58 is preferably a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, phenyl group, hydrogen atom and One of the methyl groups is more preferred, and a hydrogen atom is even more preferred.
  • R 59 is preferably a methyl group.
  • n6 is preferably an integer of 1 to 10, more preferably an integer of 1 to 5, even more preferably an integer of 1 to 3, more preferably 1 or 2, and may be 1.
  • the compound represented by formula (M5) may be a mixture of compounds in which n6 is different, and is preferably a mixture. Also, as described in the section on the compound represented by formula (M0), it may be a mixture of compounds in which other moieties are different.
  • the maleimide compound may be produced by a known method, or a commercially available product may be used.
  • Commercially available products include, for example, "BMI-80” manufactured by K-I Kasei Co., Ltd. as the compound represented by the formula (M0), and "NE-” manufactured by DIC as the compound (M1) represented by the formula (M1).
  • X-9470S "BMI-2300” manufactured by Daiwa Kasei Kogyo Co., Ltd. as a compound represented by formula (M2), and "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)
  • MIR-5000 manufactured by Nippon Kayaku Co., Ltd. as a compound represented by formula (M5).
  • maleimide compounds other than the above include N-phenylmaleimide, phenylmethanemaleimide oligomers, m-phenylenebismaleimide, 2,2-bis(4-(4-maleimidophenoxy)-phenyl)propane, 4- methyl-1,3-phenylenebismaleimide, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, 4,4'-diphenyletherbismaleimide, 4,4'-diphenylsulfonebismaleimide, 1,3 -bis(3-maleimidophenoxy)benzene, 1,3-bis(4-maleimidophenoxy)benzene, prepolymers thereof, prepolymers of these maleimides and amines, and the like.
  • the lower limit of the content of the maleimide compound is preferably 1 part by mass or more and 5 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition. It is 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.
  • the upper limit of the content of the maleimide compound is preferably 70 parts by mass or less, more preferably 50 parts by mass or less, and 40 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition. It may be below.
  • the resin composition in the present embodiment may contain only one type of maleimide compound, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
  • the resin composition in the present embodiment can be configured so as not to substantially contain a maleimide compound, particularly a monofunctional maleimide compound. “Substantially free” means that the content of the monofunctional maleimide compound, furthermore, the maleimide compound is less than 1 part by mass with respect to 100 parts by mass of the resin solid content in the resin composition, and is 0.1 mass. It is preferably less than 1 part, more preferably less than 0.01 part by mass.
  • the resin composition of the present embodiment may contain a polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds.
  • a polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds is a polyphenylene ether compound having two or more groups selected from the group consisting of (meth)acrylic groups, maleimide groups, and vinylbenzyl groups at the terminals. is preferred.
  • Polyphenylene ether compounds containing two or more carbon-carbon unsaturated double bonds are exemplified by compounds having a phenylene ether skeleton represented by the following formula (X1).
  • R 24 , R 25 , R 26 and R 27 may be the same or different and represent an alkyl group having 6 or less carbon atoms, an aryl group, a halogen atom or a hydrogen atom. )
  • a polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds has the formula (X2): (In Formula (X2), R 28 , R 29 , R 30 , R 34 and R 35 may be the same or different and represent an alkyl group having 6 or less carbon atoms or a phenyl group.
  • R 31 and R 32 , and R33 which may be the same or different, are a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group.) and/or the formula (X3):
  • R 36 , R 37 , R 38 , R 39 , R 40 , R 41 , R 42 and R 43 may be the same or different, hydrogen atom, alkyl having 6 or less carbon atoms or a phenyl group, and -A- is a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms.).
  • a polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds is a modified polyphenylene ether compound functionalized with an ethylenically unsaturated group at some or all of the terminals (hereinafter referred to as "modified polyphenylene ether compound (g )”), and more preferably a modified polyphenylene ether compound having two or more groups selected from the group consisting of a (meth)acrylic group, a maleimide group, and a vinylbenzyl group at the end. preferable.
  • the dielectric loss tangent (Df) of the cured product of the resin composition can be made smaller, and the water absorption can be reduced, and the peel strength of the metal foil can be increased. .
  • Df dielectric loss tangent
  • Modified polyphenylene ether compounds include compounds represented by 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 represents a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group
  • n1 represents an integer of 1 to 6
  • n2 represents an integer of 1 to 100
  • n3 represents an integer of 2 to 4.
  • n2 is an integer of 2 or more
  • n3 structural units (YO ) and/or n3 structural units may be the same or different.
  • n3 is preferably two.
  • the modified polyphenylene ether compound (g) in the present embodiment is preferably a compound represented by formula (OP-2). where -(O-X-O)- is the formula (OP-3): (In 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.) and/or formula (OP-4): (In formula (OP-4), R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 and R 19 may be the same or different, hydrogen atom, carbon number 6 or less is an alkyl group or a phenyl group, and -A- is a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms.).
  • -(Y-O)- is the formula (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, a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group).
  • a and b represent an integer of 0 to 100, at least one of which is not 0, preferably an integer of 0 to 50, more preferably an integer of 1 to 30 preferable.
  • 2 or more -(Y-O)- may each independently be an arrangement of one structure, and two or more structures may be block or They may be arranged randomly.
  • -A- in formula (OP-4) includes, for example, a methylene group, an ethylidene group, a 1-methylethylidene group, a 1,1-propylidene group, a 1,4-phenylenebis(1-methylethylidene) group, 1, Divalent organic groups such as 3-phenylenebis(1-methylethylidene) group, cyclohexylidene group, phenylmethylene group, naphthymethylene group, 1-phenylethylidene group, etc., but are not limited thereto. .
  • 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 and R 8 , R 9 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 22 and R 23 are hydrogen atoms or alkyl groups having 3 or less carbon atoms.
  • —(O—X—O)— represented by formula (OP-3) or formula (OP-4) is formula (OP-9), formula (OP-10), and/or —(Y—O)— represented by formula (OP-11) and represented by formula (OP-5) is preferably formula (OP-12) or formula (OP-13).
  • a and / or b is an integer of 2 or more
  • 2 or more -(YO)- are each independently a structure in which 2 or more of formula (OP-12) and / or formula (OP-13) are arranged or a structure in which the formulas (OP-12) and (OP-13) are arranged in blocks or randomly.
  • R 44 , R 45 , R 46 and R 47 may be the same or different and are a hydrogen atom or a methyl group.
  • -B- is a straight chain having 20 or less carbon atoms. A chain, branched or cyclic divalent hydrocarbon group.
  • Specific examples of -B- are 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- are the same as the specific examples of -A- in formula (OP-4).
  • JP-A-2018-016709 can be referred to for details of the polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds, and the contents thereof are incorporated herein.
  • the polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds (preferably, the modified polyphenylene ether compound (g)) has a polystyrene-equivalent number average molecular weight of 500 or more and 3,000 by GPC (gel permeation chromatography) method. The following are preferred. When the number average molecular weight is 500 or more, stickiness tends to be further suppressed when the resin composition of the present embodiment is formed into a coating film. When the number average molecular weight is 3,000 or less, the solubility in solvents tends to be further improved.
  • the polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds (preferably, the modified polyphenylene ether compound (g)) has a polystyrene-equivalent weight average molecular weight by GPC of 800 or more and 10,000 or less. It is preferably 800 or more and 5,000 or less.
  • the dielectric constant (Dk) and dielectric loss tangent (Df) of the cured product of the resin composition tend to be lower, and by setting it to the above upper limit or less, the varnish or the like described later can be reduced. There is a tendency that the solubility, low viscosity, and moldability of the resin composition in a solvent during production are further improved.
  • the terminal carbon-carbon unsaturated double bond equivalent is preferably 400 to 5000 g per carbon-carbon unsaturated double bond, and 400 to 2500 g. is more preferable.
  • the content is at least the lower limit, the cured product of the resin composition tends to have a lower dielectric constant (Dk) and dielectric loss tangent (Df).
  • Dk dielectric constant
  • Df dielectric loss tangent
  • the lower limit of the content of the polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds is , With respect to 100 parts by mass of the resin solid content in the resin composition, it is preferably 1 part by mass or more, more preferably 3 parts by mass or more, further preferably 5 parts by mass or more, 7 parts by mass It is more preferably 10 parts by mass or more, and even more preferably 10 parts by mass or more.
  • the content is at least the above lower limit, the resulting cured product tends to have improved low water absorption and low dielectric properties (Dk and/or Df).
  • the upper limit of the content of the polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds is preferably 70 parts by mass or less with respect to 100 parts by mass of the resin solid content in the resin composition. It is more preferably 50 parts by mass or less, still more preferably 40 parts by mass or less, even more preferably 35 parts by mass or less, and 25 parts by mass or less. It is even more preferable, and it may be 20 parts by mass or less.
  • the resin composition in the present embodiment may contain only one type of polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
  • the resin composition of the present embodiment may contain a cyanate ester compound.
  • the cyanate ester compound has 1 or more cyanate groups (cyanato groups) per molecule (preferably 2 to 12, more preferably 2 to 6, still more preferably 2 to 4, more preferably 2 or 3, still more preferably is not particularly limited as long as it is a compound containing 2), and a wide range of compounds commonly used in the field of printed wiring boards can be used.
  • the cyanate ester compound is preferably a compound in which a cyanate group is directly bonded to an aromatic skeleton (aromatic ring).
  • cyanate ester compounds include phenol novolak-type cyanate ester compounds, naphthol aralkyl-type cyanate ester compounds (naphthol aralkyl-type cyanates), naphthylene ether-type cyanate ester compounds, biphenyl aralkyl-type cyanate ester compounds, and xylene resins.
  • type cyanate ester compound trisphenolmethane type cyanate ester compound, adamantane skeleton type cyanate ester compound, bisphenol M type cyanate ester compound, bisphenol A type cyanate ester compound, and diallylbisphenol A type cyanate ester compound At least one selected from the group is included.
  • phenol novolac type cyanate ester compounds from the viewpoint of further improving the low water absorption of the resulting cured product, phenol novolac type cyanate ester compounds, naphthol aralkyl type cyanate ester compounds, naphthylene ether type cyanate ester compounds, xylene resin type cyanic acid It is preferably at least one selected from the group consisting of an ester compound, a bisphenol M-type cyanate ester compound, a bisphenol A-type cyanate ester compound, and a diallyl bisphenol A-type cyanate ester compound, and a phenol novolak-type cyanate ester.
  • naphthol aralkyl-type cyanate ester compounds more preferably at least one selected from the group consisting of a naphthol aralkyl-type cyanate ester compound, more preferably a naphthol aralkyl-type cyanate ester compound.
  • cyanate ester compounds may be prepared by known methods, or commercially available products may be used.
  • a cyanate ester compound having a naphthol aralkyl skeleton, a naphthylene ether skeleton, a xylene skeleton, a trisphenolmethane skeleton, or an adamantane skeleton has a relatively large number of functional group equivalents, and the number of unreacted cyanate ester groups is small. Therefore, a cured product of a resin composition using these tends to be even more excellent in low water absorption. Also, mainly due to having an aromatic skeleton or adamantane skeleton, the plating adhesion tends to be further improved.
  • a compound represented by the following formula (1) is more preferable.
  • each R 3 independently represents a hydrogen atom or a methyl group, and n3 represents an integer of 1 or more.
  • each R 3 independently represents a hydrogen atom or a methyl group, and among these, a hydrogen atom is preferred.
  • n3 is an integer of 1 or more, preferably an integer of 1 to 20, more preferably an integer of 1 to 10, and even more preferably an integer of 1 to 6. .
  • the novolac-type cyanate ester compound is not particularly limited, but for example, a compound represented by the following formula (VII) is preferable.
  • each R6 independently represents a hydrogen atom or a methyl group, and n7 represents an integer of 1 or more.
  • each R6 independently represents a hydrogen atom or a methyl group, and among these, a hydrogen atom is preferred.
  • n7 is an integer of 1 or more, preferably an integer of 1 to 20, more preferably an integer of 1 to 10, and even more preferably an integer of 1 to 6.
  • bisphenol A type cyanate ester compound one selected from the group consisting of 2,2-bis(4-cyanatophenyl)propane and prepolymers of 2,2-bis(4-cyanatophenyl)propane The above may be used.
  • the resin composition of the present embodiment preferably contains a cyanate ester compound within a range that does not impair the effects of the present invention.
  • the lower limit of the content is preferably 0.1 parts by mass or more with respect to 100 parts by mass of the resin solid content in the resin composition. , more preferably 0.2 parts by mass or more, more preferably 0.5 parts by mass or more.
  • the content of the cyanate ester compound is 0.1 parts by mass or more, the obtained cured product has improved heat resistance, combustion resistance, chemical resistance, low dielectric constant, low dielectric loss tangent, and insulating properties. There is a tendency.
  • the upper limit of the content of the cyanate ester compound is 70 parts by mass or less with respect to 100 parts by mass of the resin solid content in the resin composition.
  • it is 50 parts by mass or less, more preferably 40 parts by mass or less, even more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, and 10 parts by mass.
  • it may be 5 parts by mass or less.
  • the resin composition in the present embodiment may contain only one type of cyanate ester compound, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
  • the resin composition of this embodiment may contain an epoxy compound.
  • the epoxy compound is a compound having one or more (preferably 2 to 12, more preferably 2 to 6, still more preferably 2 to 4, still more preferably 2 or 3, still more preferably 2) epoxy groups in one molecule.
  • it is a resin, it is not particularly limited, and a wide range of compounds commonly used in the field of printed wiring boards can be used.
  • Epoxy compounds include, for example, bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolak type epoxy resin, bisphenol A novolak type epoxy resin, glycidyl ester type epoxy resin, aralkyl Novolak type epoxy resin, biphenyl aralkyl type epoxy resin, naphthylene ether type epoxy resin, cresol novolak type epoxy resin, polyfunctional phenol type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, naphthalene skeleton modified novolak type epoxy resin, phenol Aralkyl-type epoxy resin, naphthol-aralkyl-type epoxy resin, dicyclopentadiene-type epoxy resin, biphenyl-type epoxy resin, alicyclic epoxy resin, polyol-type epoxy resin, phosphorus-containing epoxy resin, glycidylamine, glycidyl ester, butadiene, etc.
  • the resin composition of the present embodiment preferably contains an epoxy compound within a range that does not impair the effects of the present invention.
  • the content thereof is preferably 0.1 parts by mass or more, and 1 part by mass or more with respect to 100 parts by mass of the resin solid content in the resin composition. It is more preferable that the amount is 2 parts by mass or more.
  • the content of the epoxy compound is 0.1 parts by mass or more, the metal foil peel strength and toughness tend to be improved.
  • the upper limit of the content of the epoxy compound is preferably 50 parts by mass or less with respect to 100 parts by mass of the resin solid content in the resin composition, and is preferably 30 parts by mass.
  • the resin composition in the present embodiment may contain only one type of epoxy compound, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range. In addition, the resin composition in the present embodiment may be configured so as not to substantially contain an epoxy compound.
  • Substantially free means that the content of the epoxy compound is less than 0.1 parts by mass, preferably less than 0.01 parts by mass, with respect to 100 parts by mass of the resin solid content in the resin composition. , or even less than 0.001 part by mass.
  • the resin composition of this embodiment may contain a phenol compound.
  • the phenol compound has 1 or more (preferably 2 to 12, more preferably 2 to 6, more preferably 2 to 4, still more preferably 2 or 3, still more preferably 2) phenolic hydroxyl groups in one molecule.
  • Phenolic compounds include, for example, bisphenol A type phenol resin, bisphenol E type phenol resin, bisphenol F type phenol resin, bisphenol S type phenol resin, phenol novolak resin, bisphenol A novolac type phenol resin, glycidyl ester type phenol resin, aralkyl novolak phenol.
  • the resin composition of the present embodiment preferably contains a phenol compound within a range that does not impair the effects of the present invention.
  • the content is preferably 0.1 parts by mass or more with respect to 100 parts by mass of the resin solid content in the resin composition, and 50 parts by mass The following are preferred.
  • the resin composition in the present embodiment may contain only one type of phenol compound, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
  • the resin composition in the present embodiment can also be configured so as not to substantially contain a phenol compound. “Substantially free” means that the content of the phenol compound is less than 0.1 part by mass with respect to 100 parts by mass of the resin solid content in the resin composition.
  • alkenyl-substituted nadimide compound is not particularly limited as long as it is a compound having one or more alkenyl-substituted nadimide groups in the molecule.
  • the compound represented by Formula (AN-1) is preferable.
  • each R 1 independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
  • R 2 represents an alkylene group having 1 to 6 carbon atoms, a phenylene group, a biphenylene group, a naphthylene group, a group represented by formula (AN-2), or a group represented by formula (AN-3).
  • each R 4 independently represents an alkylene group having 1 to 4 carbon atoms or a cycloalkylene group having 5 to 8 carbon atoms.
  • the compounds represented by the formula (AN-1) are preferred.
  • the thermal expansion coefficient of the resulting cured product tends to be further lowered and the heat resistance tends to be further improved.
  • alkenyl-substituted nadimide compounds can also be used.
  • Commercially available products are not particularly limited. and the compound represented by the formula (AN-5)).
  • the resin composition of the present embodiment preferably contains an alkenyl-substituted nadimide compound within a range that does not impair the effects of the present invention.
  • the content thereof is preferably 0.1 parts by mass or more with respect to 100 parts by mass of the resin solid content in the resin composition. It is preferably no more than parts by mass.
  • the resin composition in the present embodiment may contain only one alkenyl-substituted nadimide compound, or may contain two or more alkenyl-substituted nadimide compounds. When two or more types are included, the total amount is preferably within the above range.
  • the resin composition in the present embodiment may be configured so as not to substantially contain the alkenyl-substituted nadimide compound. “Substantially free” means that the content of the alkenyl-substituted nadimide compound is less than 0.1 part by mass with respect to 100 parts by mass of the resin solid content in the resin composition.
  • the resin composition of this embodiment may contain an oxetane resin.
  • the oxetane resin is a compound having one or more oxetanyl groups (preferably 2 to 12, more preferably 2 to 6, more preferably 2 to 4, still more preferably 2 or 3, still more preferably 2), especially There is no limitation, and a wide range of compounds commonly used in the field of printed wiring boards can be used.
  • oxetane resins include oxetane, alkyloxetane (e.g., 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, 3,3-dimethyloxetane, etc.), 3-methyl-3-methoxymethyloxetane, 3,3-di(trifluoromethyl)oxetane, 2-chloromethyloxetane, 3,3-bis(chloromethyl)oxetane, biphenyl type oxetane, OXT-101 (manufactured by Toagosei Co., Ltd.), OXT-121 (Toagosei Co., Ltd.) made) and the like.
  • alkyloxetane e.g., 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, 3,3-dimethylox
  • the resin composition of the present embodiment preferably contains an oxetane resin within a range that does not impair the effects of the present invention.
  • the content thereof is preferably 0.1 parts by mass or more, and 1 part by mass or more, with respect to 100 parts by mass of the resin solid content in the resin composition. and more preferably 2 parts by mass or more.
  • the content of the oxetane resin is 0.1 parts by mass or more, the metal foil peel strength and toughness tend to be improved.
  • the upper limit of the content of the oxetane resin is preferably 50 parts by mass or less with respect to 100 parts by mass of the resin solid content in the resin composition. It is more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, and even more preferably 8 parts by mass or less.
  • the content of the oxetane resin is 50 parts by mass or less, the resulting cured product tends to have improved electrical properties.
  • the resin composition in the present embodiment may contain only one type of oxetane resin, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
  • the resin composition in the present embodiment can be configured so as not to substantially contain an oxetane resin. “Substantially free” means that the content of the oxetane resin is less than 0.1 part by mass with respect to 100 parts by mass of the resin solid content in the resin composition.
  • the resin composition of this embodiment may contain a benzoxazine compound.
  • a benzoxazine compound 2 or more (preferably 2 to 12, more preferably 2 to 6, still more preferably 2 to 4, still more preferably 2 or 3, still more preferably 2) dihydrobenzoxazines in one molecule
  • dihydrobenzoxazines 2 or more (preferably 2 to 12, more preferably 2 to 6, still more preferably 2 to 4, still more preferably 2 or 3, still more preferably 2) dihydrobenzoxazines in one molecule
  • benzoxazine compounds include bisphenol A-type benzoxazine BA-BXZ (manufactured by Konishi Chemical Co., Ltd.), bisphenol F-type benzoxazine BF-BXZ (manufactured by Konishi Chemical Co., Ltd.), bisphenol S-type benzoxazine BS-BXZ (manufactured by Konishi Chemical Co., Ltd.). made) and the like.
  • the resin composition of the present embodiment preferably contains a benzoxazine compound within a range that does not impair the effects of the present invention.
  • the content thereof is preferably 0.1 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the resin solid content in the resin composition.
  • the resin composition in the present embodiment may contain only one kind of benzoxazine compound, or may contain two or more kinds. When two or more types are included, the total amount is preferably within the above range.
  • the resin composition in the present embodiment may be configured so as not to substantially contain a benzoxazine compound. “Substantially free” means that the content of the benzoxazine compound is less than 0.1 part by mass with respect to 100 parts by mass of the resin solid content in the resin composition.
  • the content (total amount) is preferably 3 parts by mass or more, and 5 parts by mass or more, relative to 100 parts by mass of the resin solid content. More preferably 10 parts by mass or more, still more preferably 20 parts by mass or more, even more preferably 25 parts by mass or more, and further preferably 30 parts by mass or more More preferred.
  • the content is at least the above lower limit, heat resistance, plating adhesion, low thermal expansion, etc. tend to be further improved.
  • the upper limit of the content of the thermosetting compound (C) is preferably 95 parts by mass or less, more preferably 85 parts by mass or less, relative to 100 parts by mass of the resin solid content, and 75 parts by mass.
  • the resin composition of the present embodiment may contain only one type of thermosetting compound (C), or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
  • the resin composition of the present embodiment preferably contains a filler (D).
  • a filler (D) By including the filler (D), physical properties such as dielectric properties (low dielectric constant, low dielectric loss tangent, etc.), flame resistance, and low thermal expansion of the resin composition and its cured product can be further improved. Further, it is more preferable that the filler (D) used in the present embodiment has excellent low dielectric properties.
  • the filler (D) used in the present embodiment preferably has a dielectric constant (Dk) of 8.0 or less, more preferably 6.0 or less, measured according to the cavity resonator perturbation method. It is more preferably 4.0 or less.
  • the lower limit value of the dielectric constant is practically 2.0 or more, for example.
  • the dielectric loss tangent (Df) of the filler (D) used in the present embodiment measured according to the cavity resonator perturbation method, is preferably 0.05 or less, more preferably 0.01 or less. Moreover, the lower limit value of the dielectric loss tangent is practically 0.0001 or more, for example.
  • the type of the filler (D) used in this embodiment is not particularly limited, and those commonly used in the industry can be suitably used. Specifically, silicas such as natural silica, fused silica, synthetic silica, amorphous silica, aerosil, and hollow silica, and metal oxides such as alumina, white carbon, titanium white, titanium oxide, zinc oxide, magnesium oxide, and zirconium oxide.
  • complex oxides such as zinc borate, zinc stannate, forsterite, barium titanate, strontium titanate, calcium titanate, nitrides such as boron nitride, aggregated boron nitride, silicon nitride, aluminum nitride, aluminum hydroxide, Aluminum hydroxide heat-treated product (aluminum hydroxide heat-treated to reduce some of the water of crystallization), boehmite, metal hydroxides such as magnesium hydroxide (including hydrates), molybdenum oxide and molybdic acid Molybdenum compounds such as zinc, barium sulfate, clay, kaolin, talc, calcined clay, calcined kaolin, calcined talc, mica, E-glass, A-glass, NE-glass, C-glass, L-glass, D-glass, Inorganic fillers such as S-glass, M-glass G20, glass short fibers (including fine glass powders such as E-glass,
  • organic fillers such as styrene-type, butadiene-type, acrylic-type rubber powders, core-shell type rubber powders, silicone resin powders, silicone rubber powders, and silicone composite powders can be used.
  • inorganic fillers are preferred and are selected from the group consisting of silica, aluminum hydroxide, aluminum nitride, boron nitride, forsterite, titanium oxide, barium titanate, strontium titanate, and calcium titanate. It is more preferable to contain one or more kinds, and from the viewpoint of low dielectric properties, it is more preferable to contain one or more kinds selected from the group consisting of silica and aluminum hydroxide, and it is even more preferable to contain silica. .
  • properties such as heat resistance, dielectric properties, thermal expansion properties, dimensional stability and flame retardancy of the cured product of the resin composition are further improved.
  • the content of the filler (D) in the resin composition of the present embodiment can be appropriately set according to the desired properties, and is not particularly limited. It is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, still more preferably 40 parts by mass or more, even more preferably 60 parts by mass or more, and 80 parts by mass or more. is even more preferred. By making it more than the said lower limit, there exists a tendency for the low thermal expansion property and the low dielectric tangent property to improve more.
  • the upper limit of the content of the filler (D) is preferably 500 parts by mass or less, more preferably 300 parts by mass or less, and 200 parts by mass or less with respect to 100 parts by mass of the resin solid content.
  • the content of the filler (D) is 30% by mass to 80% by mass of the components excluding the solvent.
  • the resin composition of the present embodiment may contain only one filler (D), or may contain two or more fillers (D). When two or more types are included, the total amount is preferably within the above range.
  • the resin composition of the present embodiment may further contain a silane coupling agent when using a filler (D), particularly an inorganic filler.
  • a silane coupling agent when using a filler (D), particularly an inorganic filler.
  • the silane coupling agent is not particularly limited, and includes silane coupling agents generally used for surface treatment of inorganic substances, aminosilane compounds (eg, ⁇ -aminopropyltriethoxysilane, N- ⁇ -(aminoethyl) - ⁇ -aminopropyltrimethoxysilane, etc.), epoxysilane compounds (eg, ⁇ -glycidoxypropyltrimethoxysilane, etc.), vinylsilane compounds (eg, vinyltrimethoxysilane, etc.), styrylsilane compounds, acrylic silanes.
  • aminosilane compounds eg, ⁇ -aminopropyltriethoxysilane, N- ⁇ -(aminoethyl) - ⁇ -aminopropyltrimethoxysilane, etc.
  • epoxysilane compounds eg, ⁇ -glycidoxypropyltrimethoxysilane, etc.
  • vinylsilane compounds
  • silane-based compounds eg, ⁇ -acryloxypropyltrimethoxysilane, etc.
  • cationic silane compounds eg, N- ⁇ -(N-vinylbenzylaminoethyl)- ⁇ -aminopropyltrimethoxysilane hydrochloride, etc.
  • phenyl Examples include silane-based compounds.
  • a silane coupling agent is used individually by 1 type or in combination of 2 or more types.
  • the content of the silane coupling agent is not particularly limited, but may be 0.1 to 5.0 parts by mass with respect to 100 parts by mass of the resin solid content.
  • the resin composition of this embodiment may contain an elastomer.
  • the elastomer is not particularly limited, and examples include polyisoprene, polybutadiene, styrene butadiene, butyl rubber, ethylene propylene rubber, styrene butadiene ethylene, styrene butadiene styrene, styrene isoprene styrene, styrene ethylene butylene styrene, styrene propylene styrene.
  • styrene ethylene propylene styrene ethylene propylene styrene
  • fluororubbers silicone rubbers
  • hydrogenated compounds thereof alkyl compounds thereof, and copolymers thereof.
  • it may be a thermoplastic elastomer or a thermosetting elastomer, but a thermoplastic elastomer is preferred.
  • the number average molecular weight of the elastomer used in this embodiment is preferably 50,000 or more. By setting the number average molecular weight to 50,000 or more, the low dielectric properties of the obtained cured product tend to be more excellent.
  • the number average molecular weight is preferably 60,000 or more, more preferably 70,000 or more, and even more preferably 80,000 or more.
  • the upper limit of the number average molecular weight of the thermal elastomer is preferably 400,000 or less, more preferably 350,000 or less, even more preferably 300,000 or less. When the amount is equal to or less than the upper limit, the solubility of the elastomer component in the resin composition tends to be improved.
  • the resin composition of the present embodiment contains two or more elastomers, the number average molecular weight of the mixture thereof preferably satisfies the above range.
  • the elastomer is preferably a thermoplastic elastomer containing styrene monomer units and conjugated diene monomer units (hereinafter referred to as "thermoplastic elastomer (E)").
  • thermoplastic elastomer (E) a thermoplastic elastomer containing styrene monomer units and conjugated diene monomer units
  • the thermoplastic elastomer (E) contains styrene monomer units. By including styrene monomer units, the solubility of the thermoplastic elastomer (E) in the resin composition is improved.
  • Styrene monomers include styrene, ⁇ -methylstyrene, p-methylstyrene, divinylbenzene (vinylstyrene), N,N-dimethyl-p-aminoethylstyrene, N,N-diethyl-p-aminoethylstyrene and the like.
  • thermoplastic elastomer (E) is preferably in the range of 10 to 50% by mass, more preferably in the range of 13 to 45% by mass, and more preferably in the range of 15 to 40% by mass. Ranges are more preferred. If the content of styrene monomer units is 50% by mass or less, the adhesiveness and adhesiveness to substrates and the like will be better.
  • thermoplastic elastomer (E) may contain only one type of styrene monomer unit, or may contain two or more types. When two or more kinds are included, the total amount is preferably within the above range.
  • the description in International Publication No. 2017/126469 can be referred to, the content of which is incorporated herein. The same applies to the conjugated diene monomer unit and the like, which will be described later.
  • the thermoplastic elastomer (E) contains conjugated diene monomer units. Containing the conjugated diene monomer unit improves the solubility of the thermoplastic elastomer (E) in the resin composition.
  • the conjugated diene monomer is not particularly limited as long as it is a diolefin having a pair of conjugated double bonds.
  • Conjugated diene monomers are, for example, 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl- Examples include 1,3-pentadiene, 1,3-hexadiene, and farnesene, with 1,3-butadiene and/or isoprene being preferred, and 1,3-butadiene being more preferred.
  • the thermoplastic elastomer (E) may contain only one type of conjugated diene monomer unit, or may contain two or more types.
  • thermoplastic elastomer (E) all of the conjugated diene bonds of the thermoplastic elastomer may be hydrogenated, partially hydrogenated, or not hydrogenated.
  • the thermoplastic elastomer (E) may or may not contain other monomer units in addition to the styrene monomer units and the conjugated diene monomer units.
  • examples of other monomer units include aromatic vinyl compound units other than styrene monomer units.
  • the total amount of styrene monomer units and conjugated diene monomer units is preferably 90% by mass or more, more preferably 95% by mass or more, of all monomer units. It is more preferably 97% by mass or more, and even more preferably 99% by mass or more.
  • thermoplastic elastomer (E) may contain only one kind of styrene monomer units and conjugated diene monomer units, or may contain two or more kinds thereof. When two or more types are included, the total amount is preferably within the above range.
  • the thermoplastic elastomer (E) may be a block polymer or a random polymer. Moreover, even if the conjugated diene monomer unit is a hydrogenated elastomer in which the conjugated diene monomer unit is hydrogenated, it may be an unhydrogenated elastomer in which it is not hydrogenated, or a partially hydrogenated elastomer in which it is partially hydrogenated. good. In one embodiment of this embodiment, the thermoplastic elastomer (E) is a hydrogenated elastomer.
  • the hydrogenated elastomer means, for example, a thermoplastic elastomer in which double bonds based on conjugated diene monomer units are hydrogenated, and the hydrogenation rate (hydrogenation rate) is 100%.
  • the hydrogenation rate of the hydrogenated elastomer is preferably 85% or more, more preferably 90% or more, and even more preferably 95% or more.
  • the degree of hydrogenation is calculated from the results of 1 H-NMR spectrometry.
  • the thermoplastic elastomer (E) is an unhydrogenated elastomer.
  • the non-hydrogenated elastomer refers to the ratio of hydrogenated double bonds based on conjugated diene monomer units in the elastomer, that is, the hydrogenation rate (hydrogenation rate) is 20% or less. It is intended to include things.
  • the hydrogenation rate of the unhydrogenated elastomer is preferably 15% or less, more preferably 10% or less, and even more preferably 5% or less.
  • the partially hydrogenated elastomer means a thermoplastic elastomer in which part of the double bonds based on the conjugated diene monomer units in the thermoplastic elastomer is hydrogenated, and usually has a hydrogenation rate (hydrogenation rate) of 80. % or more than 20%.
  • thermoplastic elastomer (E) used in this embodiment include SEPTON (registered trademark) 2104 manufactured by Kuraray Co., Ltd., S.E.M. O. E. (registered trademark) S1606, S1613, S1609, S1605, manufactured by JSR Corporation, DYNARON (registered trademark) 9901P, TR2250, and the like.
  • the content thereof is preferably 1 part by mass or more with respect to 100 parts by mass of the resin solid content, and 5 parts by mass. It is more preferably 10 parts by mass or more, still more preferably 15 parts by mass or more, and even more preferably 20 parts by mass or more. When the content is equal to or higher than the lower limit, low dielectric properties tend to be further improved.
  • the upper limit of the content of the elastomer is preferably 45 parts by mass or less, more preferably 40 parts by mass or less, and 35 parts by mass or less relative to 100 parts by mass of the resin solid content.
  • the resin composition of the present embodiment may contain only one type of elastomer, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
  • the resin composition of this embodiment may contain an active ester compound.
  • the active ester compound is not particularly limited. 2) includes compounds having an active ester group.
  • the active ester compound may be a linear or branched or cyclic compound.
  • an active ester compound obtained by reacting a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxy compound and/or a thiol compound is preferable from the viewpoint of further improving the heat resistance of the resulting cured product.
  • An active ester compound obtained by reacting a carboxylic acid compound with one or more compounds selected from the group consisting of a phenol compound, a naphthol compound, and a thiol compound is more preferred, and has a carboxylic acid compound and a phenolic hydroxyl group.
  • An aromatic compound obtained by reacting with an aromatic compound and having two or more active ester groups in one molecule is more preferable, and a compound having two or more carboxylic acids in one molecule and a phenolic hydroxyl group.
  • An aromatic compound obtained by reacting with an aromatic compound and having two or more active ester groups in one molecule is particularly preferred.
  • carboxylic acid compound examples include one or more selected from the group consisting of benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid.
  • benzoic acid acetic acid
  • succinic acid maleic acid, itaconic acid
  • phthalic acid isophthalic acid
  • terephthalic acid pyromellitic acid.
  • one or more selected from the group consisting of succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, and terephthalic acid are preferred, isophthalic acid and One or more selected from the group consisting of terephthalic acid is more preferred.
  • the above thiocarboxylic acid compound includes one or more selected from thioacetic acid and thiobenzoic acid.
  • the phenolic compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- cresol, p-cresol, catechol, ⁇ -naphthol, ⁇ -naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucine, One or more selected from the group consisting of benzenetriol, dicyclopentadienyldiphenol, and phenol novolak, and from the viewpoint of further improving the heat resistance and
  • the thiol compound includes one or more selected from the group consisting of benzenedithiol and triazinedithiol.
  • the active ester compound is preferably a compound having two or more carboxylic acids in one molecule and containing an aliphatic chain. From the viewpoint of improvement, compounds having an aromatic ring are preferable. More specific active ester compounds include active ester compounds described in JP-A-2004-277460.
  • a commercial product may be used for the active ester compound, or it may be prepared by a known method.
  • Commercially available products include compounds containing a dicyclopentadienyldiphenol structure (e.g., EXB9451, EXB9460, EXB9460S, HPC-8000-65T (all manufactured by DIC), etc.), acetylated phenol novolaks (e.g., DC808 ( Mitsubishi Chemical Corp.)), and benzoyl compounds of phenol novolak (e.g., YLH1026, YLH1030, YLH1048 (all manufactured by Mitsubishi Chemical Corp.)).
  • EXB9460S is preferable from the viewpoint of further improving the low thermal expansion property of the material).
  • An active ester compound can be prepared by a known method, for example, by condensation reaction between a carboxylic acid compound and a hydroxy compound.
  • Specific examples include (a) a carboxylic acid compound or its halide, (b) a hydroxy compound, and (c) an aromatic monohydroxy compound, per mol of the carboxy group or acid halide group of (a), (b) 0.05 to 0.75 mol of the phenolic hydroxyl group of (c) and 0.25 to 0.95 mol of (c).
  • the active ester compound is preferably contained within a range that does not impair the effects of the present invention.
  • the resin composition of the present embodiment contains an active ester compound, it is preferably 1 part by mass or more and preferably 90 parts by mass or less with respect to 100 parts by mass of the resin solid content in the resin composition.
  • the resin composition in the present embodiment may contain only one type of active ester compound, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
  • the resin composition in the present embodiment may be configured so as not to substantially contain an active ester compound.
  • Substantially free means that the content of the active ester compound is less than 1 part by mass, preferably less than 0.1 part by mass, with respect to 100 parts by mass of the resin solid content in the resin composition. More preferably, it is less than 0.01 part by mass.
  • the resin composition of this embodiment may contain a flame retardant.
  • flame retardants include phosphorus flame retardants, halogen flame retardants, inorganic flame retardants and silicone flame retardants, with phosphorus flame retardants being preferred.
  • Known flame retardants can be used, for example, brominated epoxy resin, brominated polycarbonate, brominated polystyrene, brominated styrene, brominated phthalimide, tetrabromobisphenol A, pentabromobenzyl (meth)acrylate, pentabromo Halogen flame retardants such as toluene, tribromophenol, hexabromobenzene, decabromodiphenyl ether, bis-1,2-pentabromophenylethane, chlorinated polystyrene, chlorinated paraffin, red phosphorus, tricresyl phosphate, triphenyl phosphate , cresyl diphenyl phosphate, trixylenyl phosphate, trialkyl phosphate, dialkyl phosphate, tris(chloroethyl) phosphate, phosphazene, 1,3-phenylenebis(2,6-dixylenyl
  • Phosphorus-based flame retardants aluminum hydroxide, magnesium hydroxide, partial boehmite, boehmite, zinc borate, antimony trioxide, etc.
  • Silicone-based flame retardants such as flame retardants, silicone rubbers, and silicone resins can be used.
  • 1,3-phenylenebis(2,6-dixylenyl phosphate) is preferable because it does not impair low dielectric properties.
  • the content thereof is preferably 1 part by mass or more, and 5 parts by mass or more with respect to 100 parts by mass of the resin solid content in the resin composition. is more preferred.
  • 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.
  • a flame retardant can be used individually by 1 type or in combination of 2 or more types. When using two or more kinds, the total amount is within the above range.
  • the resin composition of this embodiment may contain a dispersant.
  • a dispersant those generally used for paints can be suitably used, and the type thereof is not particularly limited.
  • the dispersant is preferably a copolymer-based wetting and dispersing agent, and specific examples thereof include DISPERBYK (registered trademark)-110, 111, 161, 180, 2009, and 2152 manufactured by BYK-Chemie Japan Co., Ltd. , 2155, BYK®-W996, W9010, W903, W940 and the like.
  • the lower limit of the content is preferably 0.01 parts by mass or more with respect to 100 parts by mass of the resin solid content in the resin composition. It is more preferably 1 part by mass or more, and may be 0.3 parts by mass or more.
  • the upper limit of the content of the dispersant is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and 3 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition. Part or less is more preferable.
  • a dispersing agent can be used individually by 1 type or in combination of 2 or more types. When using two or more kinds, the total amount is within the above range.
  • the resin composition of this embodiment may further contain a curing accelerator.
  • the curing accelerator is not particularly limited, but for example, 2-ethyl-4-methylimidazole, imidazoles such as triphenylimidazole; benzoyl peroxide, lauroyl peroxide, acetyl peroxide, parachlorobenzoyl peroxide, di- organic peroxides such as tert-butyl-di-perphthalate; azo compounds such as azobisisobutyronitrile; N,N-dimethylbenzylamine, N,N-dimethylaniline, N,N-dimethyltoluidine, 2- Tertiary amines such as N-ethylanilinoethanol, tri-n-butylamine, pyridine, quinoline, N-methylmorpholine, triethanolamine, triethylenediamine, tetramethylbutanediamine, N-methylpiperidine; phenol, xylenol
  • Organic metal salts products obtained by dissolving these organic metal salts in hydroxyl group-containing compounds such as phenol and bisphenol; inorganic metal salts such as tin chloride, zinc chloride and aluminum chloride; dioctyltin oxide, other alkyltin and alkyltin oxides and organic tin compounds such as Preferred curing accelerators are imidazoles and organometallic salts, more preferably both imidazoles and organometallic salts are used in combination.
  • the resin composition of the present embodiment can be configured substantially free of organic peroxides (for example, organic peroxides having a molecular weight of 30 to 500).
  • “Substantially free” means less than 0.1 parts by mass, preferably 0.01 parts by mass or less, relative to 100 parts by mass of resin solids contained in the resin composition of the present embodiment. . By setting it as such a range, the hardened
  • the resin composition of the present embodiment can be configured so as not to substantially contain an azo compound (for example, an azo compound having a molecular weight of 30 to 500). “Substantially free” means less than 0.1 parts by mass, preferably 0.01 parts by mass or less, relative to 100 parts by mass of resin solids contained in the resin composition of the present embodiment. . By setting it as such a range, the hardened
  • the lower limit of the content is preferably 0.005 parts by mass or more with respect to 100 parts by mass of the resin solid content in the resin composition. It is more preferably 0.01 part by mass or more, and even more preferably 0.1 part by mass or more.
  • the upper limit of the content of the curing accelerator is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, with respect to 100 parts by mass of the resin solid content in the resin composition. It is more preferably not more than parts by mass.
  • a hardening accelerator can be used individually by 1 type or in combination of 2 or more types. When using two or more kinds, the total amount is within the above range.
  • the resin composition of the present embodiment may contain a solvent, and preferably contains an organic solvent.
  • a solvent is contained, the resin composition of the present embodiment is in a form (solution or varnish) in which at least part, preferably all of the various resin solids described above are dissolved or compatible with the solvent.
  • the solvent is not particularly limited as long as it is a polar organic solvent or a non-polar organic solvent capable of dissolving or dissolving at least a part, preferably all, of the various resin solids described above. Examples of polar organic solvents include ketones.
  • nonpolar organic solvents include aromatic hydrocarbons (e.g., toluene, xylene, etc.).
  • a solvent can be used individually by 1 type or in combination of 2 or more types. When using two or more kinds, the total amount is within the above range.
  • the resin composition of the present embodiment may contain thermoplastic resins, various polymer compounds such as oligomers thereof, and various additives.
  • Additives include UV absorbers, antioxidants, photopolymerization initiators, fluorescent brighteners, photosensitizers, dyes, pigments, thickeners, flow control agents, lubricants, antifoaming agents, leveling agents, gloss agents, polymerization inhibitors, and the like. These additives can be used singly or in combination of two or more.
  • the resin composition of the present embodiment can also be configured so as not to substantially contain a polymerization initiator.
  • “Substantially free” means that the content of the polymerization initiator is less than 0.1 parts by mass with respect to 100 parts by mass of the resin solid content contained in the resin composition of the present embodiment, and 0.01 mass parts It is preferably less than or equal to parts. By setting it as such a range, the hardened
  • the resin composition of this embodiment is used as a cured product.
  • the resin composition of the present embodiment is a low dielectric constant material and/or a low dielectric loss tangent material, and is suitable as a resin composition for electronic materials such as an insulating layer of a printed wiring board and a semiconductor package material. can be used.
  • the resin composition of the present embodiment can be suitably used as a material for prepregs, metal foil-clad laminates using prepregs, resin composite sheets, and printed wiring boards.
  • the resin composition of the present embodiment preferably has a low dielectric constant (Dk) when molded into a cured plate having a thickness of 0.8 mm.
  • the dielectric constant (Dk) of the hardened plate at 10 GHz measured according to the cavity resonator perturbation method is preferably 2.50 or less, more preferably 2.45 or less.
  • the lower limit of the dielectric constant (Dk) is not particularly defined, for example, 0.01 or more is practical.
  • the resin composition of the present embodiment preferably has a low dielectric loss tangent (Df) when molded into a cured plate having a thickness of 0.8 mm.
  • the dielectric loss tangent (Df) at 10 GHz measured according to the cavity resonator perturbation method is preferably 0.0020 or less, more preferably 0.0018 or less.
  • the lower limit of the dielectric loss tangent (Df) is not particularly defined, for example, 0.0001 or more is practical. More specifically, the relative dielectric constant (Dk) and dielectric loss tangent (Df) of the cured plate are measured by the methods described in Examples below.
  • the resin composition of the present embodiment is used as a layered (film-like, sheet-like, etc.) material such as prepreg, resin composite sheet, etc., which becomes an insulating layer of a printed wiring board.
  • the thickness is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more.
  • the upper limit of the thickness is preferably 200 ⁇ m or less, more preferably 180 ⁇ m or less.
  • the thickness of the layered material means the thickness including the glass cloth, for example, when the resin composition of the present embodiment is impregnated into the glass cloth or the like.
  • the material formed from the resin composition of the present embodiment may be used for applications in which a pattern is formed by exposure and development, or may be used in applications without exposure and development. In particular, it is suitable for applications that do not require exposure and development.
  • the prepreg of this embodiment is formed from a base material (prepreg base material) and the resin composition of this embodiment.
  • the prepreg of the present embodiment can be produced, for example, by applying (for example, impregnating and/or coating) the resin composition of the present embodiment to a substrate and then heating (for example, drying at 120 to 220° C. for 2 to 15 minutes. etc.).
  • the amount of the resin composition adhered to the base material that is, the amount of the resin composition (including the filler (D)) relative to the total amount of the prepreg after semi-curing is preferably in the range of 20 to 99% by mass. It is more preferably in the range of ⁇ 80% by mass.
  • the base material is not particularly limited as long as it is a base material used for various printed wiring board materials.
  • materials for the base material include glass fibers (e.g., E-glass, D-glass, L-glass, S-glass, T-glass, Q-glass, UN-glass, NE-glass, spherical glass, etc.). , inorganic fibers other than glass (eg, quartz), and organic fibers (eg, polyimide, polyamide, polyester, liquid crystal polyester, polytetrafluoroethylene, etc.).
  • the form of the substrate is not particularly limited, and includes woven fabric, nonwoven fabric, roving, chopped strand mat, surfacing mat, and the like. These substrates may be used alone or in combination of two or more.
  • a woven fabric subjected to super-spreading treatment and stuffing treatment is preferable.
  • a glass woven fabric having a thickness of m 2 or less is preferable, and from the viewpoint of moisture absorption and heat resistance, a glass woven fabric surface-treated with a silane coupling agent such as epoxysilane or aminosilane is preferable.
  • a low dielectric glass cloth made of glass fibers exhibiting a low dielectric constant and a low dielectric loss tangent, such as L-glass, NE-glass, and Q-glass is more preferable.
  • Examples of low dielectric constant substrates include substrates having a dielectric constant of 5.0 or less (preferably 3.0 to 4.9).
  • low dielectric loss tangent substrates include substrates having a dielectric loss tangent of 0.006 or less (preferably 0.001 to 0.005).
  • the dielectric constant and dielectric loss tangent are values measured at 10 GHz using a perturbation method cavity resonator.
  • the metal foil-clad laminate of this embodiment includes at least one layer formed from the prepreg of this embodiment, and a metal foil disposed on one side or both sides of the layer formed from the prepreg.
  • a method for producing the metal foil-clad laminate of the present embodiment for example, at least one sheet of the prepreg of the present embodiment is arranged (preferably two or more sheets are stacked), a metal foil is arranged on one or both sides thereof, and lamination molding is performed. method. More specifically, the prepreg can be produced by arranging a metal foil such as copper or aluminum on one side or both sides of the prepreg and laminating the prepreg.
  • the number of prepregs is preferably 1 to 10, more preferably 2 to 10, and even more preferably 2 to 9.
  • the metal foil is not particularly limited as long as it is used as a material for printed wiring boards, and examples thereof include copper foil such as rolled copper foil and electrolytic copper foil.
  • the thickness of the metal foil (preferably copper foil) is not particularly limited, and may be about 1.5 to 70 ⁇ m.
  • Examples of the molding method include methods commonly used for molding laminates for printed wiring boards. A method of laminate molding 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 can be used.
  • a multilayer board can also be obtained by combining the prepreg of the present embodiment and a wiring board for an inner layer, which is separately prepared, and performing lamination molding.
  • a method for producing a multilayer board for example, copper foil of about 35 ⁇ m is placed on both sides of one prepreg of the present embodiment, laminated by the above molding method, an inner layer circuit is formed, and black is applied to this circuit. After that, the inner layer circuit board and the prepreg of the present embodiment are alternately arranged one by one, and copper foil is arranged on the outermost layer to satisfy the above conditions.
  • a multi-layer board can be produced by lamination molding, preferably under vacuum.
  • the metal foil-clad laminate of this embodiment can be suitably used as a printed wiring board.
  • the resin composition for electronic materials obtained by using the resin composition of the present embodiment has a cured product having dielectric properties (low dielectric loss tangent), moisture absorption, In addition to heat resistance, it can have excellent properties such as crack resistance, appearance of the cured product, 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, wherein the insulating layer is formed from the resin composition of the present embodiment. It includes at least one of a layer and a layer formed from the prepreg of this embodiment.
  • Such a printed wiring board can be manufactured according to a conventional method, and the manufacturing method is not particularly limited. An example of a method for manufacturing a printed wiring board is shown below. First, a metal foil-clad laminate such as the metal foil-clad laminate described above is prepared. Next, the surface of the metal foil-clad laminate is etched to form an inner layer circuit, thereby producing an inner layer substrate.
  • the surface of the inner layer circuit of this inner layer substrate is subjected to a surface treatment to increase the adhesive strength as necessary, and then the required number of prepregs described above are laminated on the surface of the inner layer circuit, and a metal foil for the outer layer circuit is laminated on the outer side. Then, heat and pressurize to integrally mold. In this manner, a multi-layer laminate is produced in which an insulating layer composed of the substrate and the cured product of the resin composition is formed between the inner layer circuit and the metal foil for the outer layer circuit. Next, after drilling holes for through holes and via holes in this multi-layer laminate, a plated metal film is formed on the walls of the holes for conducting the inner layer circuit and the metal foil for the outer layer circuit, and further the outer layer circuit. A printed wiring board is manufactured by etching the metal foil for the purpose to form an outer layer circuit.
  • the printed wiring board obtained in the above production example has an insulating layer and a conductor layer formed on the surface of the insulating layer, and the insulating layer is the resin composition of the present embodiment and / or a cured product thereof.
  • the configuration includes That is, the prepreg of the present embodiment described above (for example, a prepreg formed from a substrate and the resin composition of the present embodiment impregnated or applied thereto), and the resin composition of the metal foil clad laminate of the present embodiment described above.
  • a layer formed from a material serves as an insulating layer in this embodiment.
  • the present embodiment relates to a semiconductor device including the printed wiring board.
  • the description in paragraphs 0200 to 0202 of JP-A-2021-021027 can be referred to, and the contents thereof are incorporated into this specification.
  • the resin 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 dry film solder resist.
  • the method for producing the resin composite sheet is not particularly limited, but for example, a solution obtained by dissolving the resin composition of the present embodiment in a solvent is applied (coated) to a support and dried to form a resin composite sheet. method to obtain.
  • Examples of the support used here include polyethylene film, polypropylene film, polycarbonate film, polyethylene terephthalate film, ethylenetetrafluoroethylene copolymer film, and a release film obtained by applying a release agent to the surface of these films, Organic film substrates such as polyimide films, conductor foils such as copper foils and aluminum foils, glass plates, SUS (Steel Use Stainless) plates, FRP (Fiber-Reinforced Plastics) and other plate-like substrates. It is not particularly limited.
  • Examples of the coating method include a method in which a solution obtained by dissolving the resin composition of the present embodiment in a solvent is applied onto a support using a bar coater, a die coater, a doctor blade, a baker applicator, or the like. be done. Also, after drying, a single-layer sheet can be obtained by peeling or etching the support from the resin composite sheet in which the support and the resin composition are laminated. It should be noted that a solution obtained by dissolving the resin composition of the present embodiment in a solvent is supplied into a mold having a sheet-like cavity and dried to form a sheet, thereby using a support. It is also possible to obtain a single layer sheet without
  • the drying conditions for removing the solvent are not particularly limited. A temperature of 20° C. to 200° C. and a time of 1 to 90 minutes are preferable because the curing of the resin composition proceeds. Further, the single-layer sheet or resin composite sheet can be used in an uncured state by simply drying the solvent, or can be used in a semi-cured (B-staged) state as necessary. Furthermore, the thickness of the resin layer in the single-layer sheet or resin composite sheet of the present embodiment can be adjusted by the concentration of the solution of the resin composition of the present embodiment used for coating (coating) and the thickness of the coating. However, the thickness is preferably 0.1 to 500 ⁇ m, because the solvent tends to remain during drying when the coating thickness is thick.
  • Solution 1 was added dropwise over 1.5 hours to 300 g of a 0.93 mol chloroform solution of cyanogen chloride charged in the reactor, and the mixture was stirred for 30 minutes after completion of the dropwise addition. Thereafter, a mixed solution of 0.1 mol of triethylamine and 30 g of chloroform was added dropwise into the reactor and stirred for 30 minutes to complete the reaction. After the by-produced triethylamine hydrochloride was filtered off from the reaction solution, the resulting filtrate was washed with 500 mL of 0.1N hydrochloric acid, and then washed with 500 mL of water four times. After drying this with sodium sulfate, it is evaporated at 75° C.
  • Resin "A” had a polystyrene-equivalent number-average molecular weight of 1975, a polystyrene-equivalent weight-average molecular weight of 3514, and a hydroxyl equivalent of 990 by GPC.
  • the modified polyphenylene ether compound had a polystyrene-equivalent number average molecular weight by GPC method of 2250, a polystyrene-equivalent weight average molecular weight by GPC method of 3920, and a vinyl group equivalent of 1189 g/vinyl group.
  • the weight average molecular weight (Mw) and number average molecular weight (Mn) were measured by a gel permeation chromatography (GPC) method.
  • a liquid feed pump (manufactured by Shimadzu Corporation, LC-20AD), a differential refractive index detector (manufactured by Shimadzu Corporation, RID-10A), a GPC column (manufactured by Showa Denko Corporation, GPC KF-801, 802, 803, 804).
  • tetrahydrofuran was used as the solvent
  • the flow rate was 1.0 ml/min
  • the column temperature was 40°C
  • a calibration curve using monodisperse polystyrene was used.
  • the resulting polymer (va) having a structural unit represented by formula (V) had a number average molecular weight Mn of 2,060, a weight average molecular weight Mw of 30,700, and a monodispersity Mw/Mn of 14.9. there were.
  • the polymer (va) having the structural unit represented by the formula (V) has resonance lines derived from each monomer unit used as a raw material. observed.
  • the ratio of each monomer unit (structural unit derived from each raw material) in the polymer (va) having the structural unit represented by formula (V) is as follows.
  • Structural unit derived from divinylbenzene 20.9 mol% (24.3% by mass)
  • Structural unit derived from ethylvinylbenzene 9.1 mol% (10.7% by mass)
  • Structural unit derived from styrene 70.0 mol% (65.0% by mass)
  • the structural unit having a residual vinyl group derived from divinylbenzene was 16.7 mol % (18.5 mass %).
  • Example 1 Maleimide compound (ma) (manufactured by DIC, "NE-X-9470S", compound represented by formula (M1)) 30 parts by mass, maleimide compound (manufactured by Nippon Kayaku Co., Ltd., MIR-3000) -70MT, corresponding to the compound represented by formula (M3)) 1 part by mass, cyanate ester compound (naphthol aralkyl-type cyanate ester compound (SNCN) obtained in Synthesis Example 1) 1 part by mass, Synthesis Example 2 above 15 parts by mass of the modified polyphenylene ether compound obtained in , 15 parts by mass of a phosphorus-based flame retardant (PX-200, Daihachi Chemical Industry Co., Ltd.), unhydrogenated styrene thermoplastic elastomer (SBS, TR2250, Mn115000, JSR Corporation 25 parts by mass, 10 parts by mass of the polymer (va) having the structural unit represented by the formula (V) obtained in Synthesis Example 3, 3
  • n is an integer from 1 to 20;
  • ⁇ Measurement method and evaluation method> Relative permittivity (Dk) and dielectric loss tangent (Df) After removing the copper foil of the cured plate by etching and drying at 120 ° C. for 60 minutes, using a perturbation method cavity resonator, the dielectric constant (Dk) and dielectric loss tangent (Df) after drying at 10 GHz were measured. It was measured. The measurement temperature was 23°C. Agilent 8722ES manufactured by Agilent Technologies was used as the perturbation method cavity resonator.
  • Example 2 In Example 1, 4-methylstyrene was replaced with the same amount of vinyltrimethoxysilane (KBM-1003, manufactured by Shin-Etsu Chemical Co., Ltd., boiling point 123° C.), but the other operations were carried out in the same manner.
  • KBM-1003 vinyltrimethoxysilane
  • Example 3 In Example 1, the content of the polymer (va) having the structural unit represented by the formula (V) obtained in Synthesis Example 3 was changed to 20 parts by mass, and maleimide compound (ma) (manufactured by DIC, The content of "NE-X-9470S", the compound represented by the formula (M1)) was changed to 20 parts by mass, and the rest was carried out in the same manner.
  • Comparative example 1 In Example 1, without blending 4-methylstyrene, the content of the maleimide compound (MIR-3000-70MT manufactured by Nippon Kayaku Co., Ltd., corresponding to the compound represented by formula (M3)) was changed to 4 parts by mass. changed and others did as well.
  • MIR-3000-70MT manufactured by Nippon Kayaku Co., Ltd. corresponding to the compound represented by formula (M3)
  • Comparative example 2 In Comparative Example 1, the content of the polymer (va) having the structural unit represented by the formula (V) obtained in Synthesis Example 3 was changed to 20 parts by mass, and maleimide compound (ma) (manufactured by DIC, The content of "NE-X-9470S", the compound represented by the formula (M1)) was changed to 20 parts by mass, and the rest was carried out in the same manner.
  • Comparative example 3 In Comparative Example 1, the polymer (va) having the structural unit represented by formula (V) obtained in Synthesis Example 3 was not blended, and the content of the modified polyphenylene ether compound obtained in Synthesis Example 2 was changed to 25 Parts were changed to parts by mass, and other operations were carried out in the same manner.
  • Comparative example 4 In Example 1, 4-methylstyrene was not blended, and 3 parts by mass of 3-glycidoxypropyltrimethoxysilane ("KBM-403" manufactured by Shin-Etsu Silicone Co., Ltd.) was blended.
  • KBM-403 3-glycidoxypropyltrimethoxysilane

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JP7460816B1 (ja) 2022-11-11 2024-04-02 南亞塑膠工業股▲分▼有限公司 樹脂組成物
WO2025142301A1 (ja) * 2023-12-26 2025-07-03 三菱瓦斯化学株式会社 樹脂組成物、硬化物、プリプレグ、樹脂シート、積層板、金属箔張積層板、及びプリント配線板

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WO2025173457A1 (ja) * 2024-02-16 2025-08-21 パナソニックＩｐマネジメント株式会社 難燃剤、樹脂組成物、プリプレグ、樹脂付きフィルム、樹脂付き金属箔、金属張積層板、及び配線板
TWI884749B (zh) * 2024-03-28 2025-05-21 台光電子材料股份有限公司 樹脂組合物及使用其製成之物品

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