WO2023171554A1 - Resin composition, cured product, prepreg, metal-foil-clad laminate, resin composite sheet, printed circuit board, and semiconductor device - Google Patents

Resin composition, cured product, prepreg, metal-foil-clad laminate, resin composite sheet, printed circuit board, and semiconductor device Download PDF

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Publication number
WO2023171554A1
WO2023171554A1 PCT/JP2023/007986 JP2023007986W WO2023171554A1 WO 2023171554 A1 WO2023171554 A1 WO 2023171554A1 JP 2023007986 W JP2023007986 W JP 2023007986W WO 2023171554 A1 WO2023171554 A1 WO 2023171554A1
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group
formula
compound
mass
resin composition
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PCT/JP2023/007986
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French (fr)
Japanese (ja)
Inventor
和弘 橋口
恵一 長谷部
俊介 平野
宇志 小林
祐司 中島
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三菱瓦斯化学株式会社
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Publication of WO2023171554A1 publication Critical patent/WO2023171554A1/en

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Classifications

    • 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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L39/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions of derivatives of such polymers
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate

Definitions

  • the present invention relates to a resin composition, a cured product, a prepreg, a metal foil-clad laminate, a resin composite sheet, a printed wiring board, and a semiconductor device.
  • Patent Document 1 discloses maleimide resins shown below as maleimide resins suitable for electronic material applications. Further, Patent Document 1 discloses that a curable resin composition blended with an epoxy resin or the like has excellent dielectric properties. Further, Patent Document 2 also describes the following compounds.
  • the present invention aims to solve the above problems, and provides a resin composition that maintains excellent low dielectric properties (Dk and/or Df) and has excellent moisture absorption and heat resistance, and a cured product. , a prepreg, a metal foil-clad laminate, a resin composite sheet, a printed wiring board, and a semiconductor device.
  • R each independently represents a hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a halogen atom
  • R mx each independently represents a methylene group, an ethylidene group, or , 2,2-propylidene group
  • R my is a group selected from the following group (A)
  • m represents an integer of 0 to 3
  • n is the average value of the number of repeats, 1 .00 ⁇ n ⁇ 20.00) (Group (A))
  • R y is each independently an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group which may have a substituent
  • ny is , each independently an integer from 0 to 3
  • * is the bonding position with R mx .
  • Ar represents an aromatic hydrocarbon linking group.
  • 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 represents 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, or an aryl group having 6 to 10 carbon atoms.
  • px represents an integer of 0 to 3.
  • nx represents an integer of 1 to 20.
  • n is 1.05 ⁇ n ⁇ 20.00
  • ⁇ 6> The resin composition according to any one of ⁇ 1> to ⁇ 5>, wherein the compound (M) represented by the formula (M) includes a compound represented by the formula (M-1). .
  • R each independently represents a hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a halogen atom, m represents an integer of 0 to 3, and n represents , is the average value of the number of repetitions, and represents 1.00 ⁇ n ⁇ 20.00.
  • R each independently represents a hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a halogen atom, m represents an integer of 0 to 3, and n represents , is the average value of the number of repetitions, and represents 1.00 ⁇ n ⁇ 20.00.
  • R z each independently represents a hydrocarbon group having 1 to 10 carbon atoms, m represents an integer of 0 to 3, n is the average value of the number of repeats, (Represents 1.00 ⁇ n ⁇ 20.00.)
  • ⁇ 8> Any one of ⁇ 1> to ⁇ 7>, wherein the weight average molecular weight of the polymer (V) having a structural unit represented by the formula (V) is 3,000 to 130,000.
  • ⁇ 9> Any one of ⁇ 1> to ⁇ 8>, wherein the weight average molecular weight of the polymer (V) having a structural unit represented by the formula (V) is 10,000 to 130,000.
  • thermosetting compounds selected from the group consisting of a compound containing a (meth)allyl group (preferably an alkenylnadimide compound) and a polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds.
  • the resin composition according to any one of ⁇ 1> to ⁇ 9>, containing the compound (C).
  • thermosetting compound (C) 1 to 50 parts by mass based on 100 parts by mass of resin solid content in the resin composition.
  • C thermosetting compound
  • ⁇ 12> The resin composition according to any one of ⁇ 1> to ⁇ 11>, further comprising a filler (D).
  • ⁇ 13> The resin composition according to ⁇ 12>, wherein the content of the filler (D) in the resin composition is 10 to 1600 parts by mass based on 100 parts by mass of resin solid content.
  • ⁇ 14> The resin composition according to any one of ⁇ 1> to ⁇ 13>, further comprising a thermoplastic elastomer.
  • the content of the compound (M) represented by the formula (M) is 5 to 50 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition
  • the content of the polymer (V) having the structural unit represented by the formula (V) is 5 to 50 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition
  • the content of the compound (M1) represented by the formula (M1) is 5 to 50 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition
  • the compound (M) represented by the formula (M) includes a compound represented by the formula (M-1), and n is 1.05 ⁇ n ⁇ 20.00,
  • the resin according to any one of ⁇ 1> to ⁇ 14>, wherein the polymer (V) having a structural unit represented by the formula (V) has a weight average molecular weight of 3,000 to 130,000.
  • R each independently represents a hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a halogen atom, m represents an integer of 0 to 3, and n represents , is the average value of the number of repetitions, and represents 1.00 ⁇ n ⁇ 20.00.
  • ⁇ 16> A cured product of the resin composition according to any one of ⁇ 1> to ⁇ 15>.
  • ⁇ 17> A prepreg formed from a base material and the resin composition according to any one of ⁇ 1> to ⁇ 15>.
  • ⁇ 18> A metal foil-clad laminate comprising at least one layer formed from the prepreg according to ⁇ 17> and metal foil disposed on one 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 ⁇ 15>, disposed on the surface of the support.
  • a printed wiring board comprising an insulating layer and a conductor layer disposed on the surface of the insulating layer, wherein the insulating layer is made of the resin composition according to any one of ⁇ 1> to ⁇ 15>.
  • a printed wiring board comprising at least one layer formed from a layer formed from a material.
  • a semiconductor device including the printed wiring board according to ⁇ 20>.
  • the present invention provides a resin composition that maintains excellent low dielectric properties (Dk and/or Df) and has excellent moisture absorption and heat resistance, as well as cured products, prepregs, metal foil-clad laminates, resin composite sheets, and printed wiring. We are now able to provide boards and semiconductor devices.
  • this embodiment a mode for carrying out the present invention (hereinafter simply referred to as "this embodiment") will be described in detail.
  • the present embodiment below is an illustration for explaining the present invention, and the present invention is not limited only to this embodiment.
  • " ⁇ " is used to include the numerical values described before and after it as a lower limit value and an upper limit value.
  • various physical property values and characteristic values are assumed to be at 23° C. unless otherwise stated.
  • the description that does not indicate substituted or unsubstituted includes a group having no substituent (atomic group) as well as a group having a substituent (atomic group).
  • alkyl group includes not only an alkyl group without a substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • the relative dielectric constant refers to the ratio of the dielectric constant to the vacuum dielectric constant of a substance. Further, in this specification, the relative dielectric constant may be simply referred to as "permittivity.”
  • (meth)acrylic represents both or either acrylic and methacrylic.
  • (Meta)allyl represents allyl and/or metaallyl. If the standards shown in this specification differ in measurement methods, etc. depending on the year, unless otherwise stated, the standards as of January 1, 2022 are used.
  • the maleimide group refers to the group represented below.
  • each A independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms. * indicates a bonding position with another site.
  • both A are preferably hydrogen atoms.
  • the number of carbon atoms in the alkyl group is preferably 1 to 3, more preferably 1 to 2, from the viewpoint of suitable curing.
  • the resin solid content refers to the components excluding the filler and the solvent, and refers to the compound (M) represented by the formula (M), the polymer (V ), and the compound (M1) represented by formula (M1), other thermosetting compounds (C) blended as necessary, and other resin additive components (additives such as flame retardants) etc.).
  • the resin composition of the present embodiment includes a compound (M) represented by formula (M), a polymer (V) having a structural unit represented by formula (V), and a compound represented by formula (M1).
  • Compound (M1) R each independently represents a hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a halogen atom, and R mx each independently represents a methylene group, an ethylidene group, or , 2,2-propylidene group, R my is a group selected from the following group (A), m represents an integer of 0 to 3, n is the average value of the number of repeats, 1 .00 ⁇ n ⁇ 20.00) (Group (A)) (In group (A), R y is each independently an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group which may have a substituent, and ny is , each independently an integer from 0 to 3, and * is the
  • 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 represents 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, or an aryl group having 6 to 10 carbon atoms.
  • px represents an integer of 0 to 3.
  • nx represents an integer of 1 to 20.
  • R mxy is a methylene group, an ethylidene group, or a 2,2-propylidene group, and , it is assumed that because two R mx are bonded to one benzene ring, it becomes a more compact structure, so even if the crosslinking reaction progresses, it will not become rigid and will be more compatible with other resin components. be done.
  • the compound (M) represented by formula (M) and the polymer (V) having a structural unit represented by formula (V) low dielectric properties (low dielectric constant, low dielectric loss tangent ( In particular, it is assumed that a low dielectric loss tangent)) is achieved.
  • a compound of formula (M) having a higher curing reaction temperature than these compounds may be used. It is presumed that by compounding the represented compound (M), the progress of the curing reaction is controlled in a well-balanced manner, and as a result, the moisture absorption and heat resistance is improved.
  • the resin composition of this embodiment can have high heat resistance.
  • the resin composition of this embodiment can have high peel strength.
  • the resin composition of this embodiment can have excellent desmear resistance.
  • the resin composition of this embodiment contains a compound (M) represented by formula (M).
  • a compound (M) represented by formula (M) By including the compound (M) represented by formula (M), low dielectric properties (Dk and/or Df) of the resulting resin composition can be effectively achieved.
  • R each independently represents a hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a halogen atom
  • R mx each independently represents a methylene group, an ethylidene group, or , 2,2-propylidene group
  • R my is a group selected from the following group (A)
  • m represents an integer of 0 to 3
  • n is the average value of the number of repeats, 1 .00 ⁇ n ⁇ 20.00) (Group (A))
  • R y is each independently an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group which may have a substituent
  • ny is , each independently an integer from 0 to 3
  • * is the bonding position with R mx .
  • R each independently represents a hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a halogen atom, and an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom. or a phenyl group which may be substituted with a halogen atom, such as a methyl group, an ethyl group, a propyl group (preferably an isopropyl group), or a butyl group (preferably an isopropyl group), which may be substituted with a halogen atom. is more preferably at least one selected from the group consisting of a sec-butyl group, a tert-butyl group, and a phenyl group.
  • the halogen atom is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and more preferably a fluorine atom or a chlorine atom.
  • R is preferably a hydrocarbon group having 1 to 10 carbon atoms that is not substituted with a halogen atom.
  • m represents an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0.
  • R mx is each independently a methylene group, an ethylidene group, or a 2,2-propylidene group.
  • R mx By using a methylene group, ethylidene group, or 2,2-propylidene group as R mx , it has a lower dielectric property (Dk and/or Df) and a flexible structure compared to an aromatic ring. Therefore, even if the crosslinking reaction progresses, it is difficult to become rigid and it is presumed that it becomes compatible with other resin components.
  • Each R mx is preferably an ethylidene group or a 2,2-propylidene group, more preferably a 2,2-propylidene group.
  • R my is a group selected from group (A).
  • R y is each independently an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group which may have a substituent, and a methyl group, It is preferably at least one selected from the group consisting of ethyl group, propyl group, methoxy group, ethoxy group, and phenyl group.
  • ny is each independently an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0.
  • n is the average value of the number of repetitions, and represents 1.00 ⁇ n ⁇ 20.00.
  • n is preferably 1.05 or more (1.05 ⁇ n), more preferably 1.10 or more (1.10 ⁇ n), and 1.20 or more (1.20 ⁇ n). It is more preferably 1.25 or more (1.25 ⁇ n), even more preferably 1.30 or more (1.30 ⁇ n), and even more preferably 1.50 or more (1.25 ⁇ n). It is even more preferable that 50 ⁇ n).
  • the low dielectric properties (Dk and/or Df) of the compound (M) represented by the formula (M) tend to improve, and the resin composition using the same or the resulting cured product
  • the low dielectric properties (Dk and/or Df) of these materials also tend to improve.
  • n is preferably 10.00 or less (n ⁇ 10.00), more preferably 5.00 or less (n ⁇ 5.00), and 3.00 or less (n ⁇ 3.00). ), more preferably 2.75 or less (n ⁇ 2.75), even more preferably 2.50 or less (n ⁇ 2.50).
  • n is, for example, the number average molecular weight determined by gel permeation chromatography (GPC, detector: RI) of the compound (M) represented by formula (M), or the area of each separated peak. It can be calculated from the ratio.
  • the compound (M) represented by formula (M) preferably includes a compound represented by formula (M-1).
  • R each independently represents a hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a halogen atom
  • m represents an integer of 0 to 3
  • n represents , is the average value of the number of repetitions, and represents 1.00 ⁇ n ⁇ 20.00.
  • R, m, and n have the same meanings as R, m, and n in formula (M), respectively, and the preferred ranges are also the same.
  • the compound (M) represented by formula (M) more preferably includes a compound represented by formula (M-2).
  • R z each independently represents a hydrocarbon group having 1 to 10 carbon atoms
  • m represents an integer of 0 to 3
  • n is the average value of the number of repeats, 1.00 ⁇ n ⁇ 20.00
  • R z is a hydrocarbon group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms or a phenyl group, and a methyl group or ethyl group which may be substituted with a halogen atom. , a propyl group (preferably an isopropyl group), a butyl group (preferably a sec-butyl group, a tert-butyl group), and a phenyl group.
  • One of the two terminal maleimide groups and R mx (preferably a 2,2-propylidene group) closest to the maleimide group are located at the meta or ortho position with respect to the benzene ring, and the other maleimide group group
  • a compound (M- C) A compound (M- C).
  • the compound (MA) is mixed with the compound (MB) and the compound (MC), which have a high degree of freedom of rotation of the phenylene maleimide group moiety in the molecule.
  • the degree of freedom in the distribution of crosslinking reaction points in the resin composition during the curing reaction increases, and a cured resin product having a stronger network tends to be formed.
  • the heat resistance for example, glass transition temperature
  • low thermal expansion of the resulting cured product tend to be further improved.
  • the terminal maleimide group and R mx preferably 2,2-propylidene group
  • the compound is preferable that the compound is
  • the proportion of compound (MA) in compound (M) represented by formula (M) is preferably 90 area% or less, and 80 area% or less. It is more preferable that the amount is 70 area % or less, and it may be 50 area % or less, or 30 area % or less. When the content is below the upper limit, crystallinity decreases, so solvent solubility tends to improve. Further, the proportion of the compound (M-A) may be 0 area%, but is more preferably 2 area% or more, even more preferably 5 area% or more, and even more preferably 10 area% or more. It's okay.
  • the proportion of compound (MB) among compound (M) represented by formula (M) is preferably less than 60 area %, and less than 55 area %. It is preferable that there be. By setting it below the above-mentioned upper limit, there is a tendency that it is possible to reduce the manufacturing cost of the compound (M) represented by the formula (M) and the amount of industrial waste. Further, the proportion of the compound (MB) is preferably 30 area % or more, more preferably 35 area % or more, and even more preferably 40 area % or more.
  • the ratio of the compound (MB) in formula (M) preferably satisfies the above range when 1.00 ⁇ n ⁇ 5.00, and 1.00 ⁇ n ⁇ 3.00. In some cases, it is more preferable to satisfy the above range. Further, it is preferable that the above range is satisfied when the compound (MB) contains the following compound as a main component (for example, in a proportion of 30% by mass or more of the compound (M) represented by the formula (M)).
  • the proportion of compound (MC) in compound (M) represented by formula (M) is preferably less than 60 area%, and less than 50 area%. It is preferable that there be. Further, the proportion of the compound (MC) is preferably 15 area % or more, more preferably 25 area % or more. When the proportion of the compound (MC) is 15 area% or more, it has excellent low dielectric properties (Dk and/or Df), and when it is less than 60 area%, it has good curability and adhesion, and it can be used for substrates, etc. Defects during production can be effectively suppressed.
  • Dk and/or Df low dielectric properties
  • the above ratio of compound (MC) preferably satisfies the above range when 1.00 ⁇ n ⁇ 5.00 in formula (M), and 1.00 ⁇ n ⁇ 3.00. In some cases, it is more preferable to satisfy the above range. Further, it is preferable that the above range is satisfied when the compound (MC) contains the following compound as a main component (for example, in a proportion of 15% by mass or more of the compound represented by the formula (M)).
  • the compound (M-A) has a large influence on the problem of crystallinity and the problem of deterioration of electrical properties
  • the compound (M-B) in the compound (M) represented by the formula (M) is preferably 50 area% or more, and 60% by area or more based on the total amount of the compound (MA), the compound (MB), and the compound (MC). It is more preferably at least 70% by area, particularly preferably at least 70% by area.
  • the upper limit may be, for example, 100 area % or less, or even 99 area % or less.
  • it is preferable that the above range is satisfied when 1.00 ⁇ n ⁇ 5.00, and it is more preferable that the above range is satisfied when 1.00 ⁇ n ⁇ 3.00. .
  • the softening point of the compound (M) represented by formula (M) measured by a method according to JIS K-7234 is preferably 50°C or higher, more preferably 80°C or higher, and even more preferably 90°C or higher. °C or higher, particularly preferably 95°C or higher.
  • the softening point is preferably 150°C or lower, more preferably 140°C or lower, even more preferably 130°C or lower, even more preferably 120°C or lower, even if it is 110°C or lower or 100°C or lower. good.
  • the acid value of the compound (M) represented by formula (M) is preferably 30 mgKOH/g or less, more preferably 1 to 15 mgKOH/g.
  • the acid value is high, there are many molecules that are not converted into maleimide, and structures having carboxylic acid become excessive, which affects electrical properties and water resistance.
  • the weight average molecular weight (Mw) of the compound (M) represented by formula (M) is preferably 500 or more, and further may be 600 or more, or 700 or more. When the amount is equal to or more than the lower limit, the resulting cured product tends to have better low dielectric properties (Dk and/or Df) and low water absorption.
  • the upper limit of the weight average molecular weight (Mw) of the compound (M) represented by formula (M) is preferably 10,000 or less, more preferably 9,000 or less, even more preferably 7,000 or less, and even more preferably 5,000 or less. It is more preferably below, even more preferably 3000 or less, even more preferably 1000 or less. By setting it below the above-mentioned upper limit, the heat resistance and handleability of the obtained cured product tend to be further improved.
  • the content of the compound (M) represented by formula (M) is 5 to 50 parts by mass when the resin solid content in the resin composition is 100 parts by mass. preferable.
  • the lower limit of the content of the compound (M) represented by formula (M) is preferably 5 parts by mass or more, and preferably 7 parts by mass or more, based on 100 parts by mass of the resin solid content in the resin composition.
  • the amount is more preferably 10 parts by mass or more, even more preferably 15 parts by mass or more, and even more preferably 18 parts by mass or more.
  • the obtained cured product has low dielectric properties (Dk and/or Df, especially low dielectric loss tangent), and metal foil peelability. Strength tends to improve.
  • the upper limit of the content of the compound (M) represented by formula (M) is preferably 50 parts by mass or less, and 45 parts by mass or less, based on 100 parts by mass of the resin solid content in the resin composition. The amount is more preferably 40 parts by mass or less, even more preferably 35 parts by mass or less, may be 30 parts by mass or less, and may be 25 parts by mass or less.
  • the resin composition in this embodiment may contain only one type of compound (M) represented by formula (M), or may contain two or more types. When two or more types are included, it is preferable that the total amount falls within the above range.
  • the resin composition of this embodiment includes a polymer (V) having a structural unit represented by formula (V).
  • a resin composition having excellent low dielectric properties low dielectric constant, low dielectric loss tangent
  • a cured resin product with a strong network is formed, so it has excellent low dielectric properties (Dk and/or Df) and low heat resistance. It is also presumed to have an excellent coefficient of expansion (low CTE).
  • Ar represents an aromatic hydrocarbon linking group. * represents the bonding position.
  • the aromatic hydrocarbon linking group may be a group consisting only of an aromatic hydrocarbon that may have a substituent, or a group consisting of an aromatic hydrocarbon that may have a substituent and another linking group. It may be a group consisting of a combination of.
  • the aromatic hydrocarbon linking group is preferably a group consisting only of aromatic hydrocarbons that may have substituents.
  • the substituent that the aromatic hydrocarbon may have is a substituent Z (for example, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, hydroxy groups, amino groups, carboxy groups, halogen atoms, etc.). Further, it is preferable that the aromatic hydrocarbon has no substituent.
  • the aromatic hydrocarbon linking group is usually a divalent linking group.
  • aromatic hydrocarbon linking group examples include a phenylene group, a naphthalenediyl group, an anthracenediyl group, a phenanthrenediyl group, a biphenyldiyl group, and a fluorenediyl group, which may have a substituent, Among these, a phenylene group which may have a substituent is preferred.
  • the above-mentioned substituent Z is exemplified as the substituent, but it is preferable that groups such as the above-mentioned phenylene group have no substituent.
  • the structural unit represented by formula (V) is the structural unit represented by the following formula (V1), the structural unit represented by the following formula (V2), and the structural unit represented by the following formula (V3). More preferably, at least one is included. Note that * in the following formula represents the bonding position. Further, hereinafter, the constituent units represented by formulas (V1) to (V3) may be collectively referred to as “constituent unit (a)."
  • L 1 is an aromatic hydrocarbon linking group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms).
  • examples include a phenylene group, a naphthalenediyl group, an anthracenediyl group, a phenanthrenediyl group, a biphenyldiyl group, and a fluorenediyl group, which may have a substituent.
  • a phenylene group is preferred.
  • the above-mentioned substituent Z is exemplified as the substituent, but it is preferable that groups such as the above-mentioned phenylene group have no substituent.
  • the compound forming the structural unit (a) is preferably a divinyl aromatic compound, such as divinylbenzene, bis(1-methylvinyl)benzene, divinylnaphthalene, divinylanthracene, divinylbiphenyl, divinylphenanthrene, etc. It will 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 (V) having the structural unit represented by formula (V) may be a homopolymer of the structural unit (a), but it may also be a copolymer with a structural unit derived from another monomer. It may be a combination.
  • the copolymerization ratio of the structural unit (a) is preferably 3 mol % or more, and 5 mol % or more. % 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. % or less, even more preferably 50 mol% or less, even more preferably 40 mol% or less, even more preferably 30 mol% or less, and furthermore, It may be 25 mol% or less, or 20 mol% or less.
  • the structural unit (b) derived from an aromatic compound having one vinyl group (monovinyl aromatic compound) is exemplified.
  • the structural unit (b) derived from the monovinyl aromatic compound is preferably a structural unit represented by the following formula (V4).
  • L 2 is an aromatic hydrocarbon linking group, and a preferred example is the above-mentioned example 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, its carbon number is preferably 1 to 6, more preferably 1 to 3. R V1 and L 2 may have the above-mentioned substituent Z.
  • the polymer (V) having the structural unit represented by formula (V) is a copolymer containing the structural unit (b) derived from a monovinyl aromatic compound
  • examples of the monovinyl aromatic compound include styrene, Vinyl aromatic compounds such as vinylnaphthalene and vinylbiphenyl; o-methylstyrene, m-methylstyrene, p-methylstyrene, o,p-dimethylstyrene, o-ethylvinylbenzene, m-ethylvinylbenzene, p-ethylvinyl Examples include nuclear alkyl-substituted vinyl aromatic compounds such as benzene, methylvinylbiphenyl, and ethylvinylbiphenyl.
  • the monovinyl aromatic compound exemplified here may have the above-mentioned substituent Z as appropriate. Further, these monovinyl aromatic compounds may be used alone or
  • the copolymerization ratio of the structural unit (b) shall be 10 mol% or more. is preferable, more preferably 15 mol% or more, furthermore 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%. It may be more than that.
  • 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 (V) having the structural unit represented by formula (V) may have other structural units other than the structural unit (a) and the structural unit (b).
  • Examples of other structural units include a structural unit (c) derived from a cycloolefin compound.
  • the cycloolefin compound include hydrocarbons having a double bond in the ring structure.
  • cycloolefin compounds such as cyclobutene, cyclopentene, cyclohexene, and cyclooctene
  • compounds having a norbornene ring structure such as norbornene and dicyclopentadiene
  • cycloolefin compounds condensed with aromatic rings such as indene and acenaphthylene. etc.
  • norbornene compounds include those described in paragraphs 0037 to 0043 of JP-A-2018-39995, the contents of which are incorporated herein.
  • the cycloolefin compound illustrated here may further have the above-mentioned substituent Z.
  • the copolymerization ratio of the structural unit (c) shall be 10 mol% or more. is preferable, more preferably 20 mol% or more, and even more preferably 30 mol% or more.
  • the upper limit is preferably 90 mol% or less, more preferably 80 mol% or less, even more preferably 70 mol% or less, may be 50 mol% or less, and may be 30 mol% or less. It may be the following.
  • the polymer (V) having the structural unit represented by formula (V) further incorporates a structural unit (d) derived from a different polymerizable compound (hereinafter also referred to as other polymerizable compound).
  • a different polymerizable compound hereinafter also referred to as other polymerizable compound.
  • other polymerizable compounds include compounds containing three vinyl groups. Specific examples include 1,3,5-trivinylbenzene, 1,3,5-trivinylnaphthalene, and 1,2,4-trivinylcyclohexane. Alternatively, ethylene glycol diacrylate, butadiene, etc. may be mentioned.
  • the copolymerization ratio of the structural unit (d) derived from another polymerizable compound is preferably 30 mol% or less, more preferably 20 mol% or less, and even more preferably 10 mol% or less. .
  • a polymer containing the structural unit (a) as essential and at least one of the structural units (b) to (d) is Illustrated. Furthermore, an embodiment is exemplified in which the total of structural units (a) to (d) accounts for 95 mol% or more, and further 98 mol% or more of the total structural units.
  • Another embodiment of the polymer (V) having a structural unit represented by formula (V) is a structural unit in which the structural unit (a) is essential and among all the 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 refers to the monomer used to produce the polymer (V) having the structural unit represented by formula (V) (for example, divinyl Aromatic compounds, monovinyl aromatic compounds, etc.) shall originate from one molecule.
  • the method for producing the polymer (V) having the structural unit represented by the formula (V) is not particularly limited and may be any conventional method.
  • a raw material containing a divinyl aromatic compound if necessary, a monovinyl aromatic compound compound, cycloolefin compound, etc.
  • a Lewis acid catalyst a metal fluoride such as boron trifluoride or a complex thereof can be used.
  • the structure of the chain terminal of the polymer (V) having the structural unit represented by the formula (V) is not particularly limited, but when it comes to the group derived from the divinyl aromatic compound, the structure of the following formula (E1) is used.
  • the molecular weight of the polymer (V) having a structural unit represented by formula (V) is preferably a number average molecular weight Mn of 300 or more, more preferably 500 or more, and 1,000 or more. More preferably, it is 1,500 or more.
  • the upper limit is preferably 130,000 or less, more preferably 120,000 or less, even more preferably 110,000 or less, and even more preferably 100,000 or less.
  • the molecular weight of the polymer (V) having a structural unit represented by formula (V) is preferably 3,000 or more, more preferably 5,000 or more, in weight average molecular weight Mw, 10, More preferably, it is 000 or more.
  • the excellent low dielectric properties (Dk and/or Df) of the polymer (V) having the structural unit represented by formula (V), especially Df and the dielectric properties after moisture absorption, can be improved.
  • the upper limit is preferably 130,000 or less, more preferably 100,000 or less, even more preferably 80,000 or less, and even more preferably 50,000 or less.
  • the monodispersity (Mw/Mn) expressed by the ratio of weight average molecular weight Mw to 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 is practically 1.1 or more, preferably 5 or more, more preferably 7 or more, and even more preferably 10 or more.
  • the above Mw and Mn are measured in accordance with the description in the examples below.
  • the resin composition of the present embodiment contains two or more kinds of polymers (V) having structural units represented by formula (V), it is preferable that Mw, Mn, and Mw/Mn of the mixture satisfy the above ranges.
  • the equivalent weight of vinyl groups in the polymer (V) having the structural unit represented by formula (V) is 200 g/eq. or more, preferably 230g/eq. More preferably, it is 250 g/eq. It is more preferable that it is above. Further, the equivalent weight of the vinyl group is 1200 g/eq. It is preferably less than 1000g/eq. It is more preferable that it is less than 800g/eq. Below, 600g/eq. Below, 400g/eq. Below, 300g/eq. It may be the following. By setting it to the above lower limit or more, the storage stability of the resin composition tends to improve, and the fluidity of the resin composition tends to improve.
  • the content of the polymer (V) having a structural unit represented by formula (V) is 5 to 50 parts by mass when the resin solid content in the resin composition is 100 parts by mass.
  • the content of the polymer (V) having a structural unit represented by formula (V) is 5 to 50 parts by mass when the resin solid content in the resin composition is 100 parts by mass.
  • the lower limit of the content of the polymer (V) having a structural unit represented by formula (V) is preferably 7 parts by mass or more when the resin solid content in the resin composition is 100 parts by mass. It is preferably 9 parts by mass or more, more preferably 10 parts by mass or more, even more preferably 15 parts by mass or more.
  • the upper limit of the content of the polymer (V) having a structural unit represented by formula (V) is 45 parts by mass or less when the resin solid content in the resin composition is 100 parts by mass.
  • the amount is more preferably 40 parts by mass or less, even more preferably 35 parts by mass or less, may be 30 parts by mass or less, and may be 25 parts by mass or less.
  • the resulting cured product has excellent low dielectric properties (Dk and/or Df) and desmear resistance. There is a tendency. Further, by setting the amount to be equal to or less than the above upper limit, the metal foil peel strength and moisture absorption heat resistance of the obtained cured product can be effectively improved.
  • the lower limit of the content of the polymer (V) having the structural unit represented by the formula (V) is 20 parts by mass or more with respect to 100 parts by mass of the compound (M) represented by the formula (M).
  • the amount is preferably 30 parts by mass or more, more preferably 40 parts by mass or more, even more preferably 50 parts by mass or more, and furthermore 60 parts by mass or more, 70 parts by mass or more. , preferably 75 parts by mass or more, and 80 parts by mass or more, and may be 85 parts by mass or more, 90 parts by mass or more, or 95 parts by mass or more, depending on the application.
  • the upper limit of the content of the polymer (V) having a structural unit represented by the formula (V) is 600 parts by mass or less per 100 parts by mass of the compound (M) represented by the formula (M).
  • the amount is preferably 500 parts by mass or less, even more preferably 400 parts by mass or less, even more preferably 300 parts by mass or less, furthermore 200 parts by mass or less, and 170 parts by mass or less.
  • the resin composition may contain only one type of polymer (V) having a structural unit represented by formula (V), or may contain two or more types. When two or more types are included, it is preferable that the total amount falls within the above range.
  • the resin composition of this embodiment contains a compound (M1) represented by formula (M1).
  • 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.
  • 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 represents 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, or an aryl group having 6 to 10 carbon atoms.
  • 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, even more preferably an alkyl group having 1 to 6 carbon atoms, and a methyl group, an ethyl group, a propyl group, or a butyl group. More preferred is a methyl group, especially a methyl group.
  • R M1 and R M3 are each independently preferably an alkyl group, and R M2 and R M4 are preferably a hydrogen atom.
  • R M5 and R M6 each independently represent a hydrogen atom or an alkyl group, preferably an alkyl group.
  • the alkyl group here is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group, an ethyl group, a propyl group, or a butyl group, with a methyl group being particularly preferred. preferable.
  • Ar M represents a divalent aromatic group, preferably a phenylene group, a naphthalenediyl group, a phenanthrenediyl group, an anthracenediyl group, more preferably a phenylene group, still more preferably a m-phenylene group.
  • Ar M may have a substituent, and the substituent is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, even more preferably an alkyl group having 1 to 6 carbon atoms, a methyl group, Ethyl group, propyl group, and butyl group are more preferable, and methyl group is particularly preferable.
  • Ar M is unsubstituted.
  • A is a 4- to 6-membered alicyclic group, and more preferably a 5-membered alicyclic group (preferably a group that forms an indane ring when combined with a benzene ring).
  • R M7 and R M8 each independently represent 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, and an alkyl group is more preferred.
  • 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, and still more preferably a methyl group, an ethyl group, a propyl group, or a butyl group, with a methyl group being particularly preferred.
  • R M11 , R M12 , R M13 , and R M14 each independently represent a hydrogen atom or an organic group.
  • the organic group here is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, even more preferably an alkyl group having 1 to 6 carbon atoms, and a methyl group, an ethyl group, a propyl group, or a butyl group. More preferred is a methyl group, especially a methyl group.
  • R M12 and R M13 are each independently preferably an alkyl group, and R M11 and R M14 are preferably a hydrogen atom.
  • R M15 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. represents an aryloxy group, an arylthio group having 6 to 10 carbon atoms, a halogen atom, a hydroxyl group, or a mercapto group, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or a cycloalkyl group having 6 to 10 carbon atoms. is preferably an aryl group.
  • nx represents an integer from 1 to 20.
  • nx may be an integer of 10 or less.
  • the resin composition of the present embodiment may contain only one type of compound (M1) represented by formula (M1), or may contain two or more types of compounds having at least different values of nx. You can stay there. When two or more types are included, the average value of nx (average number of repeating units) 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.
  • n is preferably 10.0 or less, more preferably 8.0 or less, even more preferably 7.0 or less, even more preferably 6.0 or less, and 5. It may be 0 or less. The same applies to equations (M1-2) and the like that will be described later.
  • the compound (M1) represented by formula (M1) is preferably a compound represented by formula (M1-1) below.
  • R M21 , R M22 , R M23 , and R M24 each independently represent a hydrogen atom or an organic group.
  • R M25 and R M26 each independently represent a hydrogen atom or an alkyl
  • R M27 , R M28 , R M29 , and R M30 each independently represent a hydrogen atom or an organic group.
  • R M31 and R M32 each independently represent a hydrogen atom or an alkyl group.
  • R M33 , R M34 , R M35 , and R M36 each independently represent a hydrogen atom or an organic group.
  • R M37 , R M38 , and R M39 each independently represent a hydrogen atom or an alkyl group.
  • nx is Represents an integer between 1 and 20.
  • 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, even more preferably an alkyl group having 1 to 6 carbon atoms, and a methyl group, an ethyl group, a propyl group, or a butyl group. More preferred is a methyl group.
  • R M21 and R M23 are preferably alkyl groups, and R M22 and R M24 are preferably hydrogen atoms.
  • R M25 and R M26 each independently represent a hydrogen atom or an alkyl group, preferably an alkyl group.
  • the alkyl group here is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group, an ethyl group, a propyl group, or a butyl group, with a methyl group being particularly preferred.
  • R M27 , R M28 , R M29 , and R M30 each independently represent a hydrogen atom or an organic group, and preferably a hydrogen atom.
  • the organic group here is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, even more preferably an alkyl group having 1 to 6 carbon atoms, and a methyl group, an ethyl group, a propyl group, or a butyl group. More preferred is a methyl group.
  • R M31 and R M32 each independently represent a hydrogen atom or an alkyl group, preferably an alkyl group.
  • the alkyl group here is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group, an ethyl group, a propyl group, or a butyl group, with a methyl group being particularly preferred.
  • 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, even more preferably an alkyl group having 1 to 6 carbon atoms, and a methyl group, an ethyl group, a propyl group, or a butyl group. More preferred is a methyl 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, and an alkyl group is preferable.
  • 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, and still more preferably a methyl group, an ethyl group, a propyl group, or a butyl group, with a methyl group being particularly preferred.
  • nx represents an integer from 1 to 20. nx may be an integer of 10 or less.
  • RM21 , RM22 , RM23 , RM24 , RM25, RM26 , RM27 , RM28 , RM29 , RM30 , RM31 , RM32 , RM33 , RM34 , R M35 , R M36 , R M37 , R M38 , R M39 , and nx are R M21 , R M22 , R M23 , R M24 , R M25 , R M26 , R M27 in formula (M1-1), respectively; It is synonymous with 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, 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), and more preferably a compound represented by the following formula (M1-4).
  • M1-3 nx represents an integer from 1 to 20.
  • nx may be an integer of 10 or less.
  • nx represents an integer from 1 to 20.
  • nx may be an integer of 10 or less.
  • the molecular weight of the 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 amount is equal to or more than the lower limit, the resulting cured product tends to have better low dielectric properties (Dk and/or Df) and low water absorption. Further, the molecular weight of the compound (M1) represented by formula (M1) is preferably 10,000 or less, more preferably 9,000 or less, even more preferably 7,000 or less, and preferably 5,000 or less. More preferably, it is 4000 or less. By setting it below the above-mentioned upper limit, the heat resistance and handleability of the obtained cured product tend to be further improved.
  • the content of the compound (M1) represented by formula (M1) is 5 to 50 parts by mass when the resin solid content in the resin composition is 100 parts by mass. is preferred.
  • the lower limit of the content of the compound (M1) represented by formula (M1) is preferably 5 parts by mass or more, and 7 parts by mass or more when the resin solid content in the resin composition is 100 parts by mass. It is more preferably 9 parts by mass or more, even more preferably 10 parts by mass or more, and even more preferably 15 parts by mass or more.
  • the upper limit of the content of the compound (M1) represented by formula (M1) is preferably 50 parts by mass or less, and 40 parts by mass or less when the resin solid content in the resin composition is 100 parts by mass.
  • the resulting cured product tends to have excellent heat resistance and moisture absorption heat resistance. Further, by setting the amount to be below the upper limit, the metal foil peel strength and desmear resistance of the obtained cured product can be effectively kept in a good range.
  • the lower limit of the content of the compound (M1) represented by the formula (M1) is preferably 10 parts by mass or more with respect to 100 parts by mass of the compound (M) represented by the formula (M), It is more preferably 20 parts by mass or more, even more preferably 30 parts by mass or more, even more preferably 60 parts by mass or more, even more preferably 70 parts by mass or more, and even more preferably 80 parts by mass or more. It is even more preferable that the amount is at least 85 parts by weight, even more preferably at least 85 parts by weight, even more preferably at least 90 parts by weight, and may be at least 95 parts by weight.
  • the upper limit of the content of the compound (M1) represented by the formula (M1) is preferably 600 parts by mass or less with respect to 100 parts by mass of the compound (M) represented by the formula (M), It is more preferably 500 parts by mass or less, even more preferably 400 parts by mass or less, even more preferably 300 parts by mass or less, furthermore 200 parts by mass or less, 170 parts by mass or less, 150 parts by mass or less. , 140 parts by mass or less, 130 parts by mass or less, 125 parts by mass or less, depending on the use etc., it may be 120 parts by mass or less, 115 parts by mass or less, 110 parts by mass or less, 105 parts by mass or less. good.
  • the content range of the compound (M1) represented by formula (M1) By adjusting the content range of the compound (M1) represented by formula (M1) to the above range, low dielectric properties (Dk and/or Df, especially low dielectric loss tangent), metal foil peel strength, desmear resistance, and moisture absorption can be achieved. It tends to have excellent heat resistance.
  • Only one type of compound (M1) represented by formula (M1) may be contained in the resin composition, or two or more types may be contained in the resin composition. When two or more types are included, it is preferable that the total amount falls within the above range.
  • a compound (M) represented by formula (M), a polymer (V) having a structural unit represented by formula (V), and a polymer represented by formula (M1) The mass ratio of the content of compound (M1) to 100 parts by mass of compound (M) represented by formula (M) is the content of polymer (V) having a structural unit represented by formula (V) and formula
  • the ratio of the compound (M1) represented by (M1) is preferably 30-130:90-400, more preferably 40-130:90-300, and 70-130:90-140. The ratio is more preferably 70 to 110:90 to 110, even more preferably 90 to 105:90 to 105.
  • the content is expressed as the content of the compound (M1) represented by the formula (M1)/the content of the polymer (V) having the structural unit represented by the formula (V).
  • the ratio is preferably 3.0 or less, more preferably 2.5 or less, even more preferably 2.0 or less, even more preferably 1.8 or less, and It is preferably 0.5 or more, and more preferably 0.8 or more.
  • the resin composition of the present embodiment contains a compound (M) represented by formula (M) and a maleimide compound other than the compound (M1) represented by formula (M1), an epoxy compound, a phenol compound, an oxetane resin, and a benzoxazine.
  • a compound (M) represented by formula (M) and a maleimide compound other than the compound (M1) represented by formula (M1) an epoxy compound, a phenol compound, an oxetane resin, and a benzoxazine.
  • It may further contain a curable compound (C).
  • the resin composition of the present embodiment may contain a maleimide compound other than the compound (M) represented by formula (M) and the compound (M1) represented by formula (M1).
  • the resin composition of this embodiment has one or more (preferably 2 to 12, more preferably 2 to 6, still more preferably 2 to 4, even more preferably 2 or 3, even more preferably 2) per molecule.
  • the compound is not particularly limited as long as it has a maleimide group, and a wide variety of compounds commonly used in the field of printed wiring boards can be used.
  • maleimide compounds other than the compound (M) represented by formula (M) and the compound (M1) represented by formula (M1) are the compound represented by formula (M2), the compound represented by formula (M3 ), a compound represented by formula (M4), and a maleimide compound (M6), preferably containing one or more selected from the group consisting of a compound represented by formula (M2), It is more preferable to include one or more selected from the group consisting of a compound represented by formula (M3) and a compound represented by formula (M4).
  • R 54 each independently represents a hydrogen atom or a methyl group, and n 4 represents an integer of 1 or more.
  • n 4 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, and even more preferably 1 or 2.
  • the compound represented by formula (M2) may be a mixture of compounds in which n 4 is different, and is preferably a mixture.
  • R 55 each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group, and n 5 represents an integer of 1 to 10.
  • 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, or phenyl group; One of the methyl groups is more preferable, and a hydrogen atom is even more preferable.
  • n 5 is preferably an integer of 1 or more and 5 or less, more preferably an integer of 1 to 3, and even more preferably 1 or 2.
  • the compound represented by formula (M3) may be a mixture of compounds having different n 5 values, and is preferably a mixture.
  • R 56 each independently represents a hydrogen atom, a methyl group, or an ethyl group
  • R 57 each independently represents a hydrogen atom or a methyl group.
  • the maleimide compound (M6) is a compound having a structural unit represented by formula (M6) and maleimide groups at both ends of the molecular chain.
  • R 61 represents a linear or branched alkylene group having 1 to 16 carbon atoms, or a linear or branched alkenylene group having 2 to 16 carbon atoms.
  • R 62 is R 63 represents a linear or branched alkylene group having 1 to 16 carbon atoms, or a linear or branched alkenylene group having 2 to 16 carbon atoms. Represents a chain or branched alkyl group, or a straight or branched alkenyl group having 2 to 16 carbon atoms.
  • n independently represents an integer of 0 to 10.
  • Maleimide compounds other than the compound (M) represented by formula (M) and the compound (M1) represented by formula (M1) may be produced by a known method, or commercially available products may be used.
  • Commercially available products include, for example, "BMI-2300” manufactured by Daiwa Kasei Kogyo Co., Ltd. as a compound represented by formula (M2), "MIR-3000” manufactured by Nippon Kayaku Co., Ltd. as a compound represented by formula (M3),
  • Examples of the compound represented by formula (M4) include "BMI-70” manufactured by K.I. Kasei Co., Ltd., and "MIZ-001” manufactured by Nippon Kayaku Co., Ltd. as the maleimide compound (M6).
  • maleimide compounds other than those mentioned above include compounds having two or more maleimide groups, specifically 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'-diphenyl ether bismaleimide, 4,4'-diphenylsulfone bis Examples include maleimide, 1,3-bis(3-maleimidophenoxy)benzene, 1,3-bis(4-maleimidophenoxy)benzene, prepolymers thereof, and prepolymers of these maleimides and amines.
  • the lower limit of the content is 100% of the resin solid content in the resin composition. It is preferably 1 part by mass or more, more preferably 5 parts by mass or more, even more preferably 10 parts by mass or more, may be 20 parts by mass or more, and 25 parts by mass. It may be more than that.
  • the content of the maleimide compound other than the compound (M) represented by the formula (M) and the compound (M1) represented by the formula (M1) is 1 part by mass or more, the flame resistance of the obtained cured product is improved. There is a tendency to improve.
  • the upper limit of the content of maleimide compounds other than the compound (M) represented by formula (M) and the compound (M1) represented by formula (M1) is 100 parts by mass of resin solid content in the resin composition. It is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and may be 30 parts by mass or less.
  • the metal foil peel of the cured product obtained by containing a maleimide compound other than the compound (M) represented by the formula (M) and the compound (M1) represented by the formula (M1) is 50 parts by mass or less. Strength and low water absorption tend to improve.
  • the resin composition in this embodiment may contain only one maleimide compound other than the compound (M) represented by formula (M) and the compound (M1) represented by formula (M1), or may contain only one maleimide compound other than the compound (M) represented by formula (M) and the compound (M1) represented by formula (M1), It may contain more than one species. When two or more types are included, it is preferable that the total amount falls within the above range. Moreover, the resin composition in this embodiment can also be made into the structure which does not contain substantially the maleimide compound other than the compound (M) represented by Formula (M).
  • “Substantially free” means that the content of maleimide compounds other than the compound (M) represented by formula (M) and the compound (M1) represented by formula (M1) is 100% of the resin solid content in the resin composition. It means less than 1 part by mass, preferably less than 0.1 part by mass, and more preferably less than 0.01 part by mass.
  • the resin composition of this embodiment may contain an epoxy compound.
  • An epoxy compound is a compound having one or more (preferably 2 to 12, more preferably 2 to 6, still more preferably 2 to 4, even more preferably 2 or 3, even more preferably 2) epoxy groups in one molecule.
  • epoxy compounds include bisphenol A epoxy resin, bisphenol E epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, bisphenol A novolac epoxy resin, glycidyl ester epoxy resin, and aralkyl epoxy resin.
  • Novolac type epoxy resin biphenylaralkyl type epoxy resin, naphthylene ether type epoxy resin, cresol novolac type epoxy resin, multifunctional phenol type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, naphthalene skeleton modified novolac 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, glycidyl amine, glycidyl ester, butadiene, etc.
  • Examples include compounds in which bonds are epoxidized, and compounds obtained by reacting hydroxyl group-containing silicone resins with epichlorohydrin. By using these, the moldability and adhesion of the resin composition are improved.
  • biphenylaralkyl epoxy resins, naphthylene ether epoxy resins, polyfunctional phenol epoxy resins, and naphthalene epoxy resins are preferred; More preferably, it is a type epoxy resin.
  • 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, based on 100 parts by mass of resin solids in the resin composition. It is more preferable that the amount is at least 2 parts by mass, and even more preferably 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 of the resulting cured product tend to improve.
  • the upper limit of the content of the epoxy compound is preferably 50 parts by mass or less, and 30 parts by mass or less, based on 100 parts by mass of resin solids in the resin composition. It is more preferably at most 20 parts by mass, even more preferably at most 10 parts by mass, and may be at most 8 parts by mass, and may be at most 5 parts by mass.
  • the content of the epoxy compound is 50 parts by mass or less, the electrical properties of the obtained cured product tend to improve.
  • the resin composition in this embodiment may contain only one type of epoxy compound, or may contain two or more types of epoxy compounds. When two or more types are included, it is preferable that the total amount falls within the above range.
  • the resin composition in this embodiment can also have a structure that does not 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, based on 100 parts by mass of resin solids in the resin composition. , and even less than 0.001 part by mass.
  • the resin composition of this embodiment may contain a phenol compound.
  • the phenol compound has one or more (preferably 2 to 12, more preferably 2 to 6, still more preferably 2 to 4, even more preferably 2 or 3, even more preferably 2) phenolic hydroxyl groups in one molecule.
  • the phenol compound is not particularly limited, and a wide variety of compounds commonly used in the field of printed wiring boards can be used. Examples of the phenol compound include 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 novolac phenol.
  • Resin biphenylaralkyl type phenolic resin, cresol novolac type phenolic resin, polyfunctional phenolic resin, naphthol resin, naphthol novolak resin, polyfunctional naphthol resin, anthracene type phenolic resin, naphthalene skeleton modified novolak type phenolic resin, phenol aralkyl type phenolic resin,
  • naphthol aralkyl-type phenolic resins dicyclopentadiene-type phenolic resins, biphenyl-type phenolic resins, alicyclic phenolic resins, polyol-type phenolic resins, phosphorus-containing phenolic resins, and hydroxyl group-containing silicone resins.
  • At least one selected from the group consisting of biphenyl aralkyl type phenol resin, naphthol aralkyl type phenol resin, phosphorus-containing phenol resin, and hydroxyl group-containing silicone resin is a seed.
  • 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 part by mass or more, and 1 part by mass or more, based on 100 parts by mass of resin solids in the resin composition. It is more preferable that the amount is at least 2 parts by mass, and even more preferably 2 parts by mass or more. Further, the amount is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, and 5 parts by mass or less. There may be.
  • the resin composition in this embodiment may contain only one type of phenol compound, or may contain two or more types of phenol compounds. When two or more types are included, it is preferable that the total amount falls within the above range.
  • the resin composition in this embodiment can also have a structure that does not substantially contain a phenol compound. “Substantially free” means that the content of the phenol compound is less than 0.1 parts by mass based on 100 parts by mass of resin solids in the resin composition.
  • the resin composition of this embodiment may contain oxetane resin.
  • the oxetane resin is particularly a compound having one or more oxetanyl groups (preferably 2 to 12, more preferably 2 to 6, even more preferably 2 to 4, even more preferably 2 or 3, even more preferably 2).
  • oxetanyl groups preferably 2 to 12, more preferably 2 to 6, even more preferably 2 to 4, even more preferably 2 or 3, even more preferably 2.
  • oxetane resin examples include oxetane, alkyloxetane (for example, 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 (manufactured by Toagosei Co., Ltd.) (manufactured by), etc.
  • alkyloxetane for example, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, 3,3
  • the resin composition of this 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 based on 100 parts by mass of resin solids in the resin composition. More preferably, the amount is 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 of the obtained cured product tend to improve.
  • the upper limit of the content of oxetane resin is preferably 50 parts by mass or less, and 30 parts by mass or less, based on 100 parts by mass of resin solid content in the resin composition. It is more preferably at most 20 parts by mass, even more preferably at most 10 parts by mass, and may be at most 5 parts by mass.
  • the content of the oxetane resin is 50 parts by mass or less, the electrical properties of the resulting cured product tend to improve.
  • the resin composition in this embodiment may contain only one type of oxetane resin, or may contain two or more types of oxetane resin.
  • the resin composition in this embodiment can also be configured to substantially not contain oxetane resin.
  • substantially free means that the content of oxetane resin is less than 0.1 parts by mass based on 100 parts by mass of resin solid content in the resin composition.
  • the resin composition of this embodiment may contain a benzoxazine compound.
  • the benzoxazine compound includes 2 or more (preferably 2 to 12, more preferably 2 to 6, even more preferably 2 to 4, even more preferably 2 or 3, even more preferably 2) dihydrobenzoxazines in one molecule. Any compound having a ring is not particularly limited, and a wide range of compounds commonly used in the field of printed wiring boards can be used.
  • benzoxazine compounds include bisphenol A-type benzoxazine BA-BXZ (manufactured by Konishi Chemical Co., Ltd.), bisphenol F-type benzoxazine BF-BXZ (manufactured by Konishi Chemical Co., Ltd.), and bisphenol S-type benzoxazine BS-BXZ (manufactured by Konishi Chemical Co., Ltd.). ), etc.
  • 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 based on 100 parts by mass of resin solids in the resin composition.
  • the resin composition in this embodiment may contain only one type of benzoxazine compound, or may contain two or more types of benzoxazine compounds. When two or more types are included, it is preferable that the total amount falls within the above range.
  • the resin composition in this embodiment can also be configured to substantially not contain a benzoxazine compound. "Substantially free" means that the content of the benzoxazine compound is less than 0.1 parts by mass based on 100 parts by mass of resin solid content in the resin composition.
  • the resin composition of this embodiment preferably contains a compound containing a (meth)allyl group, and more preferably contains a compound containing an allyl group.
  • the compound containing a (meth)allyl group is preferably a compound containing two or more (meth)allyl groups, and more preferably a compound containing two or more allyl groups.
  • the compound containing a (meth)allyl group preferably contains at least one selected from the group consisting of an allyl isocyanurate compound, an allyl group-substituted nadimide compound, an allyl compound having a glycoluril structure, and diallyl phthalate, It is more preferable to contain at least one selected from the group consisting of an allyl isocyanurate compound, an allyl group-substituted nadimide compound, and an allyl compound having a glycoluril structure, and more preferably an allyl group-substituted nadimide compound, and an alkenyl More preferred are nadimide compounds.
  • the resin composition of the present embodiment contains a compound containing a (meth)allyl group
  • its molecular weight is preferably 195 or more, more preferably 300 or more, and even more preferably 400 or more. , more preferably 500 or more.
  • the molecular weight of the compound containing a (meth)allyl group is also preferably 3,000 or less, more preferably 2,000 or less, even more preferably 1,000 or less, and even more preferably 800 or less.
  • the content thereof is preferably 1 part by mass or more, and 3 parts by mass or more, based on 100 parts by mass of resin solids in the resin composition. It is more preferably at least 5 parts by mass, even more preferably at least 5 parts by mass, and may be at least 10 parts by mass.
  • the upper limit of the content of the compound containing a (meth)allyl group is preferably 40 parts by mass or less, and preferably 30 parts by mass or less, based on 100 parts by mass of the resin solid content in the resin composition. More preferably, the amount is 20 parts by mass or less.
  • the resin composition of this embodiment may contain only one type of compound containing a (meth)allyl group, or may contain two or more types. When two or more types are included, it is preferable that the total amount falls within the above range.
  • the resin composition in this embodiment can also be configured to substantially not contain a compound containing a (meth)allyl group.
  • substantially free means that the content of the compound containing a (meth)allyl group is less than 0.1 part by mass based on 100 parts by mass of resin solid content in the resin composition.
  • allyl isocyanurate compound is not particularly defined as long as it has two or more allyl groups and an isocyanurate ring (nurate skeleton), but a compound represented by formula (TA) is preferable.
  • Formula (TA) (In formula (TA), RA represents a substituent).
  • R A represents a substituent, and a substituent having a formula weight of 15 to 500 is more preferable.
  • a first example of R A is an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 2 to 22 carbon atoms.
  • a resin composition capable of obtaining a cured product having excellent crosslinkability and high toughness by using an allyl compound having an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 2 to 22 carbon atoms. can be provided. Thereby, even if the resin composition does not include a base material such as glass cloth, it is possible to suppress cracking during etching treatment or the like.
  • the number of carbon atoms in the alkyl group and/or alkenyl group is preferably 3 or more, more preferably 8 or more, may be 12 or more, and is preferably 18 or less. It is thought that this improves the resin flowability of the resin composition, resulting in better circuit filling properties when creating a multilayer circuit board or the like using the resin composition of this embodiment.
  • R A is a group containing an allyl isocyanurate group.
  • the compound represented by formula (TA) is preferably a compound represented by formula (TA-1).
  • Formula (TA-1) (In formula (TA-1), R A2 is a divalent linking group.)
  • R A2 is preferably a divalent linking group having a formula weight of 54 to 250, and a divalent linking group having a formula weight of 54 to 250 and having carbon atoms at both ends. is more preferable, and an aliphatic hydrocarbon group having 2 to 20 carbon atoms is even more preferable (however, the aliphatic hydrocarbon group may contain an ether group, and may have a hydroxyl group). ). More specifically, R A2 is preferably a group represented by any of the following formulas (i) to (iii). (In the formulas (i) to (iii), p c1 represents the number of repeating units of the methylene group and is an integer of 2 to 18.
  • p c2 represents the number of repeating units of the oxyethylene group and is 0 or 1. .* is the binding site.)
  • the p c1 is preferably an integer of 2 to 10, more preferably an integer of 3 to 8, and still more preferably an integer of 3 to 5.
  • the p c2 may be 0 or 1, but is preferably 1.
  • R A2 is the first example.
  • the reactive group (allyl group) equivalent of the compound represented by formula (TA) is 1000 or less. It is considered that if the equivalent is 1000 or less, a high Tg can be obtained more reliably.
  • the alkyl group having 1 to 22 carbon atoms include linear or branched alkyl groups, such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group.
  • alkenyl group having 2 to 22 carbon atoms include an allyl group and a decenyl group.
  • Specific examples of the compound represented by formula (TA) include triallylisocyanurate, 5-octyl-1,3-diallylisocyanurate, 5-dodecyl-1,3-diallylisocyanurate, 5-tetradecyl- 1,3-diallylisocyanurate, 5-hexadecyl-1,3-diallylisocyanurate, 5-octadecyl-1,3-diallylisocyanurate, 5-eicosyl-1,3-diallylisocyanurate, 5-docosyl-1, Examples include 3-diallylisocyanurate and 5-decenyl-1,3-diallylisocyanurate. These may be used alone or in combination of two or more, or may be used as a prepolymer.
  • the method for producing the compound represented by formula (TA) is not particularly limited, but for example, diallylisocyanurate and alkyl halide are mixed in an aprotic polar solvent such as N,N'-dimethylformamide, and sodium hydroxide is added. It can be obtained by reacting at a temperature of about 60°C to 150°C in the presence of a basic substance such as , potassium carbonate, or triethylamine.
  • the molecular weight of the allyl isocyanurate compound (preferably the compound represented by formula (TA)) is preferably 200 or more, more preferably 300 or more, even more preferably 400 or more, and even more preferably 500 or more. It is more preferable that By setting the molecular weight to the lower limit value or more, the resulting cured product tends to have improved low dielectric properties and heat resistance. Further, the molecular weight of the allyl isocyanurate compound (preferably a compound represented by formula (TA)) is preferably 3000 or less, more preferably 2000 or less, even more preferably 1000 or less, More preferably, it is 800 or less. By controlling the molecular weight to be less than or equal to the upper limit value, the resulting cured product tends to have improved low thermal expansion properties.
  • the content thereof is preferably 1 part by mass or more, and 3 parts by mass or more based on 100 parts by mass of resin solids in the resin composition.
  • the amount is more preferably 5 parts by mass or more, and may be 10 parts by mass or more.
  • the upper limit of the content of the allyl isocyanurate compound is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and 20 parts by mass or less, based on 100 parts by mass of the resin solid content in the resin composition. It is more preferably less than parts by mass.
  • the resin composition of this embodiment may contain only one type of allyl isocyanurate, or may contain two or more types of allyl isocyanurate. When two or more types are included, it is preferable that the total amount falls within the above range.
  • allyl-substituted nadimide compounds include compounds having one or more allyl-substituted nadimide groups in the molecule (preferably compounds having one or more alkenyl-substituted nadimide groups in the molecule (alkenylnadimide compounds) ), it is not particularly limited.
  • a specific example thereof is a compound represented by the following formula (AN).
  • R 1 each 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 Represents a naphthylene group or a group represented by formula (AN-2) or (AN-3).
  • Formula (AN-3) (In formula (AN-3), R 4 each independently represents an alkylene group having 1 to 4 carbon atoms or a cycloalkylene group having 5 to 8 carbon atoms.)
  • AN a commercially available compound can also be used as the compound represented by formula (AN).
  • Commercially available compounds include, but are not particularly limited to, compounds represented by the formula (AN-4) (BANI-M (manufactured by Maruzen Petrochemical Co., Ltd.)), compounds represented by the formula (AN-5), Examples include compounds such as BANI-X (manufactured by Maruzen Petrochemical Co., Ltd.). These may be used alone or in combination of two or more.
  • the molecular weight of the allyl group-substituted nadimide compound (preferably the compound represented by formula (AN)) is preferably 400 or more, more preferably 500 or more, and may be 550 or more.
  • the molecular weight of the allyl group-substituted nadimide compound (preferably a compound represented by formula (AN)) is also preferably 1,500 or less, more preferably 1,000 or less, even more preferably 800 or less, It may be 700 or less, or 600 or less.
  • the content thereof is 0 parts by mass based on 100 parts by mass of resin solid content in the resin composition. It is preferably at least .1 part by mass, more preferably at least 1 part by mass, and even more preferably at least 2 parts by mass. Further, the amount is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, and 5 parts by mass or less. There may be.
  • an allyl group-substituted nadimide compound preferably a compound represented by formula (AN)
  • the content thereof is 0 parts by mass based on 100 parts by mass of resin solid content in the resin composition. It is preferably at least .1 part by mass, more preferably at least 1 part by mass, and even more preferably at least 2 parts by mass. Further, the amount is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 10 parts by mass
  • the resin composition of the present embodiment may contain only one type of allyl group-substituted nadimide compound, or may contain two or more types of allyl group-substituted nadimide compounds. When two or more types are included, it is preferable that the total amount falls within the above range.
  • the resin composition in this embodiment can also be configured to substantially not contain the allyl group-substituted nadimide compound. "Substantially free" means that the content of the allyl group-substituted nadimide compound is less than 0.1 part by mass based on 100 parts by mass of resin solid content in the resin composition.
  • each R is independently a hydrogen atom or a substituent, and at least two of R are groups containing an allyl group.
  • each R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkenyl group having 2 to 5 carbon atoms, and an alkenyl group having 2 to 5 carbon atoms.
  • it is an allyl group.
  • R is preferably a group containing three or four allyl groups, and more preferably a group containing four allyl groups.
  • a specific example of the compound represented by formula (GU) is 1,3,4,6-tetraallylglycoluril (a compound in which all R's are allyl groups in formula (GU)).
  • GUI a commercially available one can also be used.
  • Commercially available products include, but are not particularly limited to, TA-G manufactured by Shikoku Kasei Kogyo Co., Ltd., for example.
  • the molecular weight of the allyl compound having a glycoluril structure (preferably a compound represented by formula (GU)) is preferably 195 or more, more preferably 220 or more, even more preferably 250 or more, It may be 300 or more, or 400 or more.
  • the molecular weight of the allyl compound having a glycoluril structure (preferably a compound represented by formula (GU)) is also preferably 1500 or less, more preferably 1000 or less, further preferably 800 or less. It is preferably 700 or less, or may be 600 or less.
  • the content thereof is based on 100 parts by mass of resin solid content in the resin composition. , is preferably 1 part by mass or more, more preferably 3 parts by mass or more, even more preferably 5 parts by mass or more, and may be 10 parts by mass or more.
  • the upper limit of the content of the allyl compound having a glycoluril structure is 40 parts by mass or less based on 100 parts by mass of the resin solid content in the resin composition.
  • the amount is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and may be 20 parts by mass or less.
  • the resin composition of this embodiment may contain only one kind of allyl compound having a glycoluril structure, or may contain two or more kinds. When two or more types are included, it is preferable that the total amount falls within the above range.
  • the resin composition of this embodiment may contain a polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds.
  • the polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds is preferably a polyphenylene ether compound having two or more carbon-carbon unsaturated double bonds at the terminal, and a (meth)acrylic group at the terminal, More preferably, it is a polyphenylene ether compound having two or more groups selected from the group consisting of a maleimide group and a vinylbenzyl group.
  • the polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds is exemplified by a compound 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.
  • the 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 or a phenyl group having 6 or less carbon atoms.
  • R 31 , R 32 , and R 33 may be the same or different and are a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group.
  • -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 (hereinafter referred to as a "modified polyphenylene ether compound (g )" is preferable, and 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 terminal is more preferable.
  • a modified polyphenylene ether compound (g) it becomes possible to further reduce the dielectric loss tangent (Df) of the cured product of the resin composition, and to increase low water absorption and metal foil peel strength. .
  • Df dielectric loss tangent
  • These may be used alone or in combination of two or more.
  • Examples of the modified polyphenylene ether compound (g) include a compound 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 are each independently, Represents a hydrogen atom, an alkyl group, an alkenyl group, or an alkynyl group
  • n 1 represents an integer of 1 to 6
  • n 2 represents an integer of 1 to 100
  • n 3 represents an integer of 1 to 4.
  • the n 2 structural units (YO) and/or the n 3 structural units may be the same or different.
  • n 3 is preferably 2 or more, more preferably 2.
  • the modified polyphenylene ether compound (g) in this embodiment is preferably a compound represented by formula (OP-2).
  • -(O-X-O)- is the formula (OP-3):
  • R 4 , R 5 , R 6 , R 10 , and R 11 may be the same or different and are an alkyl group or a phenyl group having 6 or less carbon atoms.
  • 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.
  • 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, and each has a hydrogen atom and a carbon number of 6 or less. is an alkyl group or phenyl group.
  • -A- is a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms.
  • -(YO)- is the formula (OP-5):
  • R 20 and R 21 may be the same or different and are an alkyl group or a phenyl group having 6 or less carbon atoms.
  • R 22 and R 23 may be the same or different, It is preferably represented by 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 -(YO)- may each independently be an array of one type of structure, or two or more types of structures may be a block or They may be arranged randomly.
  • -A- in formula (OP-4) is, for example, a methylene group, ethylidene group, 1-methylethylidene group, 1,1-propylidene group, 1,4-phenylenebis(1-methylethylidene) group, 1, Examples include, but are not limited to, divalent organic groups such as 3-phenylenebis(1-methylethylidene) group, cyclohexylidene group, phenylmethylene group, naphthylmethylene group, and 1-phenylethylidene group.
  • R 4 , R 5 , R 6 , R 10 , R 11 , R 20 and R 21 are alkyl groups having 3 or less carbon atoms
  • R 7 , R 8 , R 9 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 22 and R 23 are hydrogen atoms or alkyl groups having 3 or less carbon atoms
  • polyphenylene ether Compounds are preferred, and in particular -(O-X-O)- represented by formula (OP-3) or formula (OP-4) is represented by formula (OP-9), formula (OP-10), and/or Formula (OP-11) and -(YO)- represented by formula (OP-5) are preferably formula (OP-12) or formula (OP-13).
  • -(Y-O)- of 2 or more each independently represents a structure in which two or more of formula (OP-12) and/or formula (OP-13) are arranged. Alternatively, it may have a structure in which formula (OP-12) and formula (OP-13) are arranged in blocks or randomly.
  • R 44 , R 45 , R 46 , and R 47 may be the same or different and are a hydrogen atom or a methyl group.
  • -B- is a straight line having 20 or less carbon atoms. It is a chain, branched, or cyclic divalent hydrocarbon group.
  • Specific examples of -B- include the same examples as -A- in formula (OP-4).
  • -B- is a straight chain, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms.
  • Specific examples of -B- include the same examples as -A- in formula (OP-4).
  • JP 2018-016709 for details of the polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds, the description in JP 2018-016709 can be referred to, and the contents thereof are incorporated herein.
  • the number average molecular weight of a polyphenylene ether compound (preferably a modified polyphenylene ether compound (g)) containing two or more carbon-carbon unsaturated double bonds in terms of polystyrene determined by the GPC (gel permeation chromatography) method (details will be given in Examples below) (according to the method described in ) is preferably 500 or more and 3,000 or less.
  • the number average molecular weight is 500 or more, stickiness tends to be further suppressed when the resin composition of this embodiment is formed into a coating film.
  • the number average molecular weight is 3,000 or less, the solubility in a solvent tends to be further improved.
  • the weight average molecular weight of a polyphenylene ether compound (preferably a modified polyphenylene ether compound (g)) containing two or more carbon-carbon unsaturated double bonds (preferably a modified polyphenylene ether compound (g)) in terms of polystyrene by GPC (for details, follow the method described in the Examples below) ) is preferably 800 or more and 10,000 or less, more 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 become lower.
  • the solubility, low viscosity, and moldability of the resin composition in the solvent during production tend to be 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. It is more preferable that By setting it above the lower limit, the relative dielectric constant (Dk) and dielectric loss tangent (Df) of the cured product of the resin composition tend to become lower. By setting it below the above upper limit, the solubility, low viscosity, and moldability of the resin composition in a solvent tend to be further improved.
  • the lower limit of the content of the polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds is , preferably 1 part by mass or more, more preferably 3 parts by mass or more, even more preferably 5 parts by mass or more, and 7 parts by mass, based on 100 parts by mass of resin solids in the resin composition. It is more preferable that the amount is above, and even more preferably that it is 10 parts by mass or more. When the amount is equal to or more than the 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 50 parts by mass or less, and 45 parts by mass or less, based on 100 parts by mass of the resin solid content in the resin composition. It is more preferably at most 40 parts by mass, even more preferably at most 35 parts by mass, even more preferably at most 30 parts by mass, and even more preferably at most 25 parts by mass. Even more preferably, the amount may be 20 parts by mass or less. When the amount is below the upper limit, the heat resistance and chemical resistance of the obtained cured product tend to be further improved.
  • the resin composition in this 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, it is preferable that the total amount falls within the above range.
  • the resin composition in this embodiment can also be configured to substantially not contain a polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds.
  • substantially free means that the content of the polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds is less than 0.1 part by mass based on 100 parts by mass of resin solid content in the resin composition. It is preferably less than 0.01 part by mass, and may even be less than 0.001 part by mass.
  • the content (total amount) is preferably 1 part by mass or more, and 5 parts by mass based on 100 parts by mass of the resin solid content.
  • the amount is more preferably at least 10 parts by mass, even more preferably at least 10 parts by mass, even more preferably at least 20 parts by mass, and may be at least 30 parts by mass.
  • the upper limit of the content of the other thermosetting compound (C) is preferably 50 parts by mass or less, more preferably 45 parts by mass or less, and 40 parts by mass or less, based on 100 parts by mass of the resin solid content. It is more preferably less than parts by mass. By setting it below the above-mentioned upper limit, the low dielectric properties (Dk and/or Df) and low water absorption of the obtained cured product tend to be further improved.
  • the resin composition of this embodiment may contain only one type of other thermosetting compound (C), or may contain two or more types. When two or more types are included, it is preferable that the total amount falls within the above range.
  • the resin composition of this embodiment 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, low thermal expansion, etc. of the resin composition and its cured product can be further improved.
  • the filler (D) used in this embodiment has excellent low dielectric properties (Dk and/or Df).
  • the filler (D) used in this embodiment preferably has a dielectric constant (Dk) of 8.0 or less, and preferably 6.0 or less, at a frequency of 10 GHz measured according to the cavity resonator perturbation method. More preferably, it is 4.0 or less.
  • the lower limit of the relative permittivity is practically, for example, 2.0 or more.
  • the filler (D) used in this embodiment preferably has a dielectric loss tangent (Df) of 0.05 or less, more preferably 0.01 or less, at a frequency of 10 GHz measured according to the cavity resonator perturbation method. preferable.
  • the lower limit value of the dielectric loss tangent is practically, for example, 0.0001 or more.
  • filler (D) used in this embodiment is not particularly limited, and those commonly used in the industry can be suitably used.
  • silicas such as natural silica, fused silica, synthetic silica, amorphous silica, Aerosil, and hollow silica, 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, agglomerated boron nitride, silicon nitride, aluminum nitride, aluminum hydroxide, Heat-treated aluminum hydroxide products (aluminum hydroxide heat-treated to reduce some of the crystal water), metal hydroxides (including hydrates) such as boehmite and magnesium hydroxide, 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, short glass 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.
  • 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 include one or more types, and from the viewpoint of low dielectric properties (Dk and/or Df), it is more preferable to include one or more types selected from the group consisting of silica and aluminum hydroxide. It is further preferred that silica is included. By using these inorganic fillers, properties such as heat resistance, dielectric properties, thermal expansion properties, dimensional stability, and flame retardance 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 depending on the desired characteristics, and is not particularly limited, but the content is based on 100 parts by mass of the resin solid content in the resin composition. It is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, even 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 preferable.
  • the amount is equal to or more than the lower limit, the resulting cured product tends to have improved low thermal expansion and low dielectric loss tangent.
  • the upper limit of the content of the filler (D) is preferably 1,600 parts by mass or less, more preferably 1,000 parts by mass or less, and 500 parts by mass or less, based on 100 parts by mass of the resin solid content.
  • the amount is more preferably 300 parts by mass or less, even more preferably 250 parts by mass or less, and may be 200 parts by mass or less, or 120 parts by mass or less.
  • the content of the filler (D) is 1 to 95% by mass of the components excluding the solvent, and the content of the filler (D) is 30 to 80% by mass. Certain embodiments are preferred.
  • the resin composition of this embodiment may contain only one type of filler (D), or may contain two or more types of filler (D). When two or more types are included, it is preferable that the total amount falls within the above range.
  • a filler (D) when using a filler (D), especially an inorganic filler, it may further contain a silane coupling agent.
  • a silane coupling agent By including a silane coupling agent, the dispersibility of the filler (D) and the adhesive strength between the resin component and the filler (D) and the substrate described below tend to be further improved.
  • Silane coupling agents are not particularly limited, and include silane coupling agents that are generally used for surface treatment of inorganic materials, such as aminosilane compounds (for example, ⁇ -aminopropyltriethoxysilane, N- ⁇ -(aminoethyl) - ⁇ -aminopropyltrimethoxysilane, etc.), epoxysilane compounds (e.g., ⁇ -glycidoxypropyltrimethoxysilane, etc.), vinylsilane compounds (e.g., vinyltrimethoxysilane, etc.), styrylsilane compounds (e.g., p-styryltrimethoxysilane, etc.), acrylic silane compounds (e.g., ⁇ -acryloxypropyltrimethoxysilane, etc.), cationic silane compounds (e.g., N- ⁇ -(N-vinylbenzylaminoethyl)- ⁇ - (aminopropyltrimeth
  • the resin composition of the present embodiment is a low-molecular vinyl compound (hereinafter simply referred to as a "low-molecular vinyl compound”) having a molecular weight of less than 1000 and containing one organic group containing a carbon-carbon unsaturated bond in the molecule. ) may also be included.
  • a low-molecular-weight vinyl compound By blending a low-molecular-weight vinyl compound, the resulting cured product tends to have improved low dielectric properties (Dk and/or Df) and moisture absorption heat resistance.
  • the carbon-carbon unsaturated bonds constituting the organic group containing carbon-carbon unsaturated bonds do not include those included as part of an aromatic ring.
  • An example of a carbon-carbon unsaturated bond included as part of the non-aromatic ring includes a cyclohexenyl group. It is also intended to include portions other than the terminals of linear or branched organic groups, ie, carbon-carbon unsaturated bonds (eg, vinylene groups) contained in the linear or branched chains.
  • X is a hydrogen atom or a methyl group.
  • 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 even more preferably a vinyl group. .
  • the low-molecular-weight vinyl compound used in this embodiment is also preferably composed only of atoms selected from the group consisting of carbon atoms, hydrogen atoms, oxygen atoms, nitrogen atoms, and silicon atoms; More preferably, it is composed only of atoms selected from the group consisting of atoms, oxygen atoms, and silicon atoms, and it is composed only of atoms selected from the group consisting of carbon atoms, hydrogen atoms, and oxygen atoms. It is even more preferable.
  • the low molecular weight vinyl compound used in this embodiment may or may not have a polar group. It is preferable that the low molecular weight vinyl compound used in this embodiment has no polar group. Examples of the polar group include an amino group, a carboxyl group, a hydroxy group, and a nitro group.
  • the molecular weight of the low molecular weight vinyl compound is preferably 70 or more, more preferably 80 or more, and even more preferably 90 or more.
  • the upper limit of the molecular weight of the low molecular vinyl compound is preferably 500 or less, more preferably 400 or less, even more preferably 300 or less, even more preferably 200 or less, and 150 or less. Good too.
  • the effect of increasing the reactivity with the polymer (V) having the structural unit represented by the formula (V) tends to be further improved.
  • the resin composition of the present embodiment contains two or more kinds of low-molecular-weight vinyl compounds, it is preferable that the average molecular weight value of the low-molecular-weight vinyl compounds is within the above range, and the molecular weight of each compound is within the above preferable range. is more preferable.
  • the low molecular weight vinyl compound preferably has a boiling point of 110°C or higher, more preferably 115°C or higher, and even more preferably 120°C or higher.
  • a boiling point of 110°C or higher By setting the value above the lower limit, volatilization of the low molecular weight vinyl compound during thermosetting of the resin composition is suppressed, and the polymer (V) having the structural unit represented by the formula (V) is more effectively produced. It is possible to react the vinyl group possessed by a low-molecular-weight vinyl compound.
  • the boiling point of the low molecular weight vinyl compound is preferably 300°C or lower, more preferably 250°C or lower, and even more preferably 200°C or lower.
  • the amount By controlling the amount to be less than or equal to the upper limit, it is possible to make it difficult for residual solvent to remain in the cured product.
  • the resin composition of the present embodiment contains two or more types of low-molecular-weight vinyl compounds, it is sufficient that the average value of the boiling points falls within the above range, but it is preferable that the boiling point of each compound falls within the above preferable range.
  • low-molecular vinyl compounds examples include (meth)acrylic acid ester 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, vinyl silane compounds (e.g., vinyltrialkoxysilanes, etc.), acrylic silane compounds (e.g., acrylic trialkoxysilanes, etc.), methacrylsilane compounds (for example, methacryltrialkoxysilane, etc.), styrylsilane compounds (for example, styryltrialkoxysilane, etc.), and the like.
  • vinyl silane compounds e.g., vinyltrialkoxysilanes, etc.
  • acrylic silane compounds e.g., acrylic trialkoxysilanes, etc.
  • methacrylsilane compounds for example, methacryltrialkoxysilane, etc.
  • styrylsilane compounds for example, styryltrialkoxysilane, etc.
  • the first forms of low-molecular vinyl compounds include (meth)acrylic acid ester compounds, aromatic vinyl compounds, saturated fatty acid vinyl compounds, vinyl cyanide compounds, ethylenically unsaturated carboxylic acids, ethylenically unsaturated carboxylic acid anhydrides, It is at least one selected from the group consisting of ethylenically unsaturated dicarboxylic acid monoalkyl esters and ethylenically unsaturated carboxylic acid amides.
  • the second form of the low molecular weight vinyl compound is selected from the group consisting of (meth)acrylic acid ester compounds, aromatic vinyl compounds, saturated fatty acid vinyl compounds, vinyl silane compounds, acrylic silane compounds, methacrylic silane compounds, and styryl silane compounds. It is at least one kind, and aromatic vinyl compounds and/or vinyl silane compounds are preferred. Specific examples of low molecular weight vinyl compounds include methylstyrene, ethylvinylbenzene, vinyltrimethoxysilane, and vinyltriethoxysilane.
  • the content of the low molecular weight vinyl compound 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. More preferably, the amount is 5 parts by mass or more.
  • the amount 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. More preferably, the amount is 5 parts by mass or more.
  • the upper limit of the content of the low molecular weight vinyl compound is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and 10 parts by mass or less based on 100 parts by mass of the resin solid content.
  • the resin composition of this embodiment may contain only one type of low-molecular-weight vinyl compound, or may contain two or more types of low-molecular-weight vinyl compounds. When two or more types are included, it is preferable that the total amount falls within the above range.
  • the mass ratio of the polymer (V) having the structural unit represented by formula (V) and the low molecular weight vinyl compound is such that the mass ratio of the polymer (V) having the structural unit represented by formula (V) is It is preferably 0.025 or more, more preferably 0.05 or more, based on 1 of coalescence (V).
  • the upper limit of the mass ratio of the polymer (V) having the structural unit represented by the above formula (V) and the low molecular weight vinyl compound is 1 for the polymer (V) having the structural unit represented by the formula (V). , is preferably 0.7 or less, more preferably 0.5 or less, even more preferably 0.4 or less, even more preferably 0.3 or less, and 0.25 or less. It's okay. By setting it below the above-mentioned upper limit, the low dielectric properties (Dk and/or Df) of the obtained cured product tend to be further improved.
  • ⁇ Oligomer having ethylenically unsaturated group It is also possible to use an oligomer having an ethylenically unsaturated group in the resin composition of this embodiment in order to enhance thermosetting properties and curability by active energy rays (for example, photocurability by ultraviolet rays). .
  • the oligomer having an ethylenically unsaturated group used in this embodiment is not particularly limited as long as it has one or more ethylenically unsaturated group in one molecule.
  • Examples include oligomers having an acryloyl group, etc., and oligomers having a vinyl group are preferred.
  • a compound that corresponds to an oligomer having an ethylenically unsaturated group and also corresponds to a polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds is referred to as a carbon-carbon unsaturated group.
  • the oligomer having an ethylenically unsaturated group is preferably a styrene oligomer.
  • the styrene oligomer according to the present embodiment is preferably formed by polymerizing at least one member selected from the group consisting of styrene, the above-mentioned styrene derivatives, and vinyltoluene.
  • the number average molecular weight of the styrene oligomer is preferably 178 or more, and preferably 1,600 or less. Further, the styrene oligomer is preferably a compound without a branched structure having an average number of aromatic rings of 2 to 14, a total amount of 2 to 14 aromatic rings of 50% by mass or more, and a boiling point of 300° C. or more.
  • styrene oligomer examples include styrene polymer, vinyltoluene polymer, ⁇ -methylstyrene polymer, vinyltoluene- ⁇ -methylstyrene polymer, styrene- ⁇ -styrene polymer, etc. .
  • styrene polymer commercially available products may be used, such as Picolastic A5 (manufactured by Eastman Chemical Company), Picolastic A-75 (manufactured by Eastman Chemical Company), Picotex 75 (manufactured by Eastman Chemical Company), Examples include FTR-8100 (manufactured by Mitsui Chemicals, Inc.) and FTR-8120 (manufactured by Mitsui Chemicals, Inc.). Furthermore, examples of the vinyltoluene- ⁇ -methylstyrene polymer include Picotex LC (manufactured by Eastman Chemical Company).
  • Crystallex 3070 manufactured by Eastman Chemical Company
  • Crystallex 3085 manufactured by Eastman Chemical Company
  • Crystallex 5140 manufactured by Eastman Chemical Company
  • FMR -0100 manufactured by Mitsui Chemicals, Inc.
  • FMR-0150 manufactured by Mitsui Chemicals, Inc.
  • examples of the styrene- ⁇ -styrene polymer include FTR-2120 (manufactured by Mitsui Chemicals, Inc.). These styrene oligomers may be used alone or in combination of two or more.
  • ⁇ -methylstyrene oligomer is preferable because it can be thermally cured well and is excellent in embedding of fine wiring, soldering heat resistance, low dielectric constant, and low dielectric loss tangent.
  • the content thereof is preferably 0.5 parts by mass or more based on 100 parts by mass of resin solids in the resin composition. , more preferably 1 part by mass or more, further preferably 2 parts by mass or more, even more preferably 3 parts by mass or more, and furthermore, may be 5 parts by mass or more.
  • the amount is equal to or more than the lower limit, the resulting cured product tends to have improved low dielectric properties.
  • the upper limit of the content of the oligomer having an ethylenically unsaturated group is preferably 30 parts by mass or less, and preferably 25 parts by mass or less, based on 100 parts by mass of the resin solid content in the resin composition.
  • the content is more preferably 20 parts by mass or less, even more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less.
  • the resin composition of the present embodiment may contain only one kind of oligomer having an ethylenically unsaturated group, or may contain two or more kinds of oligomers having an ethylenically unsaturated group. When two or more types are included, it is preferable that the total amount falls within the above range.
  • the resin composition of this embodiment may contain a thermoplastic elastomer.
  • the thermoplastic elastomer in this embodiment is not particularly limited, and includes, for example, polyisoprene, polybutadiene, styrene butadiene, butyl rubber, ethylene propylene rubber, styrene butadiene ethylene, styrene butadiene styrene, styrene isoprene styrene, styrene ethylene butylene styrene, styrene propylene styrene. , styrene ethylene propylene styrene, fluororubber, silicone rubber, hydrogenated compounds thereof, alkyl compounds thereof, and copolymers thereof.
  • the number average molecular weight of the thermoplastic elastomer used in this embodiment is preferably 50,000 or more. By setting the number average molecular weight to 50,000 or more, the resulting cured product tends to have better low dielectric properties (Dk and/or Df).
  • the number average molecular weight is preferably 60,000 or more, more preferably 70,000 or more, and even more preferably 80,000 or more.
  • the upper limit of the number average molecular weight of the thermoplastic elastomer is preferably 400,000 or less, more preferably 350,000 or less, and even more preferably 300,000 or less. By setting it below the upper limit, the solubility of the thermoplastic elastomer component in the resin composition tends to improve.
  • the resin composition of this embodiment contains two or more types of thermoplastic elastomers, it is preferable that the number average molecular weight of the mixture satisfies the above range.
  • thermoplastic elastomer is preferably a thermoplastic elastomer containing a styrene monomer unit and a conjugated diene monomer unit (hereinafter referred to as "thermoplastic elastomer (E)").
  • thermoplastic elastomer (E) a thermoplastic elastomer containing a styrene monomer unit and a conjugated diene monomer unit
  • the thermoplastic elastomer (E) contains styrene monomer units. By including the styrene monomer unit, 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, etc.
  • styrene ⁇ -methylstyrene, and p-methylstyrene are preferred from the viewpoint of availability and productivity.
  • styrene is particularly preferred.
  • the content of styrene monomer units in the 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 of the total monomer units. The range of is more preferable. If the content of styrene monomer units is 50% by mass or less, the adhesiveness and tackiness to the substrate etc. will be better.
  • thermoplastic elastomer (E) may contain only one type of styrene monomer unit, or may contain two or more types of styrene monomer units. When two or more types are included, it is preferable that the total amount is within the above range.
  • the description in International Publication No. 2017/126469 can be referred to, and the content thereof is incorporated herein. The same applies to the conjugated diene monomer unit, etc., which will be described later.
  • the thermoplastic elastomer (E) contains a conjugated diene monomer unit. By including the conjugated diene monomer unit, the solubility of the thermoplastic elastomer (E) in the resin composition is improved.
  • the conjugated diene monomer is not particularly limited as long as it is a diolefin having one pair of conjugated double bonds.
  • Conjugated diene monomers include, 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 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 or some of the conjugated diene bonds of the thermoplastic elastomer may be hydrogenated, or may not be hydrogenated.
  • the thermoplastic elastomer (E) may or may not contain other monomer units in addition to the styrene monomer unit and the conjugated diene monomer unit.
  • examples of other monomer units include aromatic vinyl compound units other than styrene monomer units.
  • the sum of styrene monomer units and conjugated diene monomer units is preferably 90% by mass or more, more preferably 95% by mass or more of the total monomer units. , more preferably 97% by mass or more, even more preferably 99% by mass or more.
  • thermoplastic elastomer (E) may contain only one type of styrene monomer unit and conjugated diene monomer unit, or may contain two or more types of each. When two or more types are included, it is preferable that the total amount falls within the above range.
  • thermoplastic elastomer (E) used in this embodiment may be a block polymer or a random polymer.
  • the thermoplastic elastomer (E) is an unhydrogenated elastomer.
  • Unhydrogenated elastomer refers to an elastomer in which the proportion of double bonds based on conjugated diene monomer units that are hydrogenated, that is, the hydrogenation rate (hydrogenation rate) is 20% or less. .
  • the hydrogenation rate is preferably 15% or less, more preferably 10% or less, even more preferably 5% or less.
  • thermoplastic elastomers (E) used in this embodiment include SEPTON (registered trademark) 2104 manufactured by Kuraray Co., Ltd. and SEPTON (registered trademark) 2104 manufactured by Asahi Kasei Corporation. O. R. (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 based on 100 parts by mass of the resin solid content, It is more preferably 5 parts by mass or more, even more preferably 10 parts by mass or more, and may be 15 parts by mass or more.
  • the upper limit of the content of the thermoplastic elastomer is preferably 45 parts by mass or less, more preferably 40 parts by mass or less, and 35 parts by mass or less based on 100 parts by mass of the resin solid content.
  • the resin composition of this embodiment may contain only one type of thermoplastic elastomer, or may contain two or more types of thermoplastic elastomer. When two or more types are included, it is preferable that the total amount falls within the above range.
  • the resin composition of this embodiment may contain a flame retardant.
  • the flame retardant include phosphorus-based flame retardants, halogen-based flame retardants, inorganic flame retardants, and silicone-based flame retardants, with phosphorus-based flame retardants being preferred.
  • Known flame retardants can be used, such as 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
  • Examples include flame retardants, silicone-based flame retardants such as silicone rubber, and silicone resin.
  • 1,3-phenylenebis(2,6-dixylenyl phosphate) is preferred because it does not impair low dielectric properties (Dk and/or Df).
  • the content thereof is preferably 1 part by mass or more, and preferably 5 parts by mass or more, based on 100 parts by mass of resin solids in the resin composition. is more preferable, still more preferably 10 parts by mass or more, and may be 15 parts by mass or more. Further, the lower limit of the flame retardant content is preferably 30 parts by mass or less, more preferably 25 parts by mass or less.
  • One kind of flame retardant can be used alone or two or more kinds can be used in combination. When two or more types are used, the total amount falls within the above range.
  • the resin composition of this embodiment may contain an active ester compound within a range that does not impair the effects of the present invention.
  • the active ester compound is not particularly limited, and for example, the description in paragraphs 0064 to 0066 of International Publication No. 2021/172317 can be referred to, the contents of which are incorporated herein.
  • the resin composition of this embodiment contains an active ester compound, it is preferably 1 part by mass or more, and preferably 50 parts by mass or less, based on 100 parts by mass of resin solid content in the resin composition. .
  • the resin composition in this embodiment may contain only one type of active ester compound, or may contain two or more types of active ester compounds. When two or more types are included, it is preferable that the total amount falls within the above range.
  • the resin composition in this embodiment can also be configured to substantially not 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, per 100 parts by mass of resin solids in the resin composition. More preferably, it is less than 0.01 part by mass.
  • the resin composition of this embodiment may contain a dispersant.
  • a dispersant those commonly used for paints can be suitably used, and the type thereof is not particularly limited.
  • a copolymer-based wetting and dispersing agent is used, and specific examples thereof include DISPERBYK®-110, 111, 161, 180, 2009, and 2152 manufactured by BYK Chemie Japan Co., Ltd. , 2155, BYK (registered trademark)-W996, W9010, W903, W940, etc.
  • the lower limit of its content is preferably 0.01 parts by mass or more, and 0.01 parts by mass or more, based on 100 parts by mass of resin solids 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 based on 100 parts by mass of the resin solid content in the resin composition. The following may be sufficient.
  • One type of dispersant can be used alone or two or more types can be used in combination. When two or more types are used, the total amount falls within the above range.
  • the resin composition of this embodiment may further contain a curing accelerator.
  • the curing accelerator include, but are not limited to, imidazoles such as 2-ethyl-4-methylimidazole and triphenylimidazole; benzoyl peroxide, lauroyl peroxide, acetyl peroxide, parachlorobenzoyl peroxide, di- tert-butyl-di-perphthalate, ⁇ , ⁇ '-di(t-butylperoxy)diisopropylbenzene, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 2,5-dimethyl- Organic peroxides such as 2,5-bis(t-butylperoxy)hexyne-3; azo compounds such as azobisnitrile; N,N-dimethylbenzylamine, N,N-dimethylaniline, N,N-dimethyltoluidine , 2-N-
  • the lower limit of its content is preferably 0.005 parts by mass or more with respect to 100 parts by mass of resin solids in the resin composition, and 0. It is more preferably .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, and 2 parts by mass or less, based on 100 parts by mass of resin solids in the resin composition. It is more preferable that the amount is less than 1 part.
  • the curing accelerator can be used alone or in combination of two or more. When two or more types are used, the total amount falls within the above range.
  • the resin composition of this embodiment may contain a solvent, and preferably contains an organic solvent.
  • the resin composition of the present embodiment is in a form (solution or varnish) in which at least a portion, preferably all, of the various resin solid components 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 that can dissolve or be compatible with at least a portion, preferably all, of the various resin solids mentioned above.
  • Examples of the polar organic solvent include ketones, etc.
  • nonpolar organic solvents include aromatic hydrocarbons (e.g., toluene, xylene, etc.).
  • solvent e.g., toluene, xylene, etc.
  • One kind of solvent can be used alone or two or more kinds can be used in combination. When two or more types are used, the total amount falls within the above range.
  • the resin composition of this embodiment may contain various polymeric compounds such as thermoplastic resins and oligomers thereof, and various additives in addition to the above-mentioned components.
  • Additives include ultraviolet absorbers, antioxidants, photopolymerization initiators, optical brighteners, photosensitizers, dyes, pigments, thickeners, fluidity regulators, lubricants, antifoaming agents, leveling agents, and gloss. agents, polymerization inhibitors, etc. These additives can be used alone or in combination of two or more.
  • the resin composition of this embodiment is used as a cured product.
  • the resin composition of this embodiment is suitable as a low dielectric constant material and/or a low dielectric loss tangent material as a resin composition for electronic materials such as insulating layers of printed wiring boards, materials for semiconductor packages, etc. Can be used.
  • the resin composition of this embodiment can be suitably used as a material for prepreg, a metal foil-clad laminate using prepreg, a resin composite sheet, and a printed wiring board.
  • the resin composition of this embodiment preferably has a low dielectric constant (Dk) when molded into a cured plate with a thickness of 0.8 mm.
  • the dielectric constant (Dk) at a frequency of 10 GHz measured according to the cavity resonator perturbation method is preferably 2.60 or less, more preferably 2.50 or less.
  • the lower limit of the dielectric constant (Dk) is not particularly determined, for example, 0.01 or more is practical.
  • the resin composition of this embodiment has a low dielectric loss tangent (Df) when molded into a cured plate with a thickness of 0.8 mm.
  • the dielectric loss tangent (Df) at a frequency of 10 GHz measured according to the cavity resonator perturbation method is preferably 0.0020 or less, more preferably 0.0018 or less, and 0.0014 or less. is even more preferable.
  • the lower limit value of the dielectric loss tangent (Df) is not particularly determined, for example, 0.0001 or more is practical.
  • Such low dielectric properties (Dk and/or Df) are mainly achieved by using a polymer (V) having a structural unit represented by formula (V) and a compound (M1) represented by formula (M1). This is achieved by More specifically, the dielectric constant (Dk) and dielectric loss tangent (Df) of the cured plate are measured by the method described in the Examples described below.
  • the cured product of the resin composition of this embodiment preferably has a glass transition temperature of 230°C or higher, more preferably 250°C or higher, according to DMA (dynamic mechanical measurement).
  • a glass transition temperature is achieved mainly by using a compound (M) represented by formula (M).
  • the practical upper limit of the glass transition temperature is, for example, 350° C. or less. More specifically, the glass transition temperature is measured by the method described in Examples below.
  • the insulating layer obtained using the resin composition of this embodiment is often subjected to a process of forming holes, and preferably has excellent desmear resistance. That is, in removing the smear after the hole-drilling process, it is preferable to suppress deterioration of the insulating layer and to have excellent smear removability.
  • the mass reduction rate in the desmear test is in the range of -4.0% by mass to -2.0% by mass. It is preferable.
  • Desmear resistance is measured according to the description in Examples below.
  • the resin composition of this embodiment is used as a layered material (including film-like, sheet-like, etc.) 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 above-mentioned layered material means the thickness including the glass cloth, for example, when the resin composition of the present embodiment is impregnated into a glass cloth or the like.
  • the material formed from the resin composition of this embodiment may be used for forming a pattern by exposure and development, or may be used for applications that are not exposed and developed. It is particularly suitable for applications that do not involve 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 by, for example, applying the resin composition of the present embodiment to a base material (for example, impregnating and/or coating it), and then heating it (for example, drying it at 120 to 220°C for 2 to 15 minutes). etc.) by semi-curing.
  • the amount of the resin composition adhered to the base material that is, the amount of the resin composition (including filler (D)) relative to the total amount of prepreg after semi-curing, is preferably in the range of 20 to 99% by mass, and 20% by mass. More preferably, the content is 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.
  • the material of the base material include glass fiber (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, etc.), and organic fibers (eg, polyimide, polyamide, polyester, liquid crystal polyester, polytetrafluoroethylene, etc.).
  • the form of the base material is not particularly limited, and examples thereof include woven fabric, nonwoven fabric, roving, chopped strand mat, surfacing mat, and the like. These base materials may be used alone or in combination of two or more.
  • the base material has a thickness of 200 ⁇ m or less, a mass of 250 g/ A glass woven fabric having a size 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 epoxy silane or amino silane is preferable.
  • a silane coupling agent such as epoxy silane or amino silane 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 the base material having a low dielectric constant include a base material having a dielectric constant of 5.0 or less (preferably 3.0 to 4.9).
  • Examples of the low dielectric loss tangent base material include base materials with a dielectric loss tangent of 0.006 or less (preferably 0.001 to 0.005).
  • the relative dielectric constant and dielectric loss tangent are values measured at a frequency of 10 GHz using a perturbation method cavity resonator.
  • the metal foil-clad laminate of this embodiment includes at least one layer formed from the prepreg of this embodiment, and metal foil disposed on one or both sides of the layer formed from the prepreg.
  • a method for producing the metal foil-clad laminate of this embodiment for example, at least one prepreg of this embodiment is arranged (preferably two or more prepregs are stacked), metal foil is arranged on one or both sides of the prepreg, and laminated molding is performed.
  • One method is to do so. More specifically, it can be produced by arranging a metal foil such as copper or aluminum on one or both sides of a prepreg and laminating it.
  • the number of prepreg sheets is preferably 1 to 10 sheets, more preferably 2 to 10 sheets, and even more preferably 2 to 9 sheets.
  • the metal foil is not particularly limited as long as it is used as a material for printed wiring boards, and examples thereof include copper foils 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. Further, when copper foil is used as the metal foil, it is preferable that the roughness Rz of the surface of the copper foil measured according to JIS B0601:2013 is adjusted to 0.2 to 4.0 ⁇ m.
  • the roughness Rz of the copper foil surface By setting the roughness Rz of the copper foil surface to 0.2 ⁇ m or more, the roughness of the copper foil surface becomes appropriate, and the copper foil peel strength tends to be further improved. On the other hand, by setting the roughness Rz of the copper foil surface to 4.0 ⁇ m or less, the roughness of the copper foil surface becomes appropriate, and the dielectric loss tangent characteristics of the obtained cured product tend to be further improved.
  • the roughness Rz of the copper foil surface is more preferably 0.5 ⁇ m or more, still more preferably 0.6 ⁇ m or more, particularly preferably 0.7 ⁇ m or more, and more preferably is 3.5 ⁇ m or less, more preferably 3.0 ⁇ m or less, particularly preferably 2.0 ⁇ m or less.
  • Examples of the lamination molding method include methods normally used when molding laminate boards for printed wiring boards and multilayer boards, and more specifically, multistage press machines, multistage vacuum press machines, continuous molding machines, autoclave molding machines, etc.
  • An example of this is a method of laminated 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 .
  • a multilayer board can be obtained by laminating and molding a combination of the prepreg of this embodiment and a separately produced wiring board for an inner layer.
  • a method for manufacturing a multilayer board for example, copper foil of about 35 ⁇ m is placed on both sides of one sheet of prepreg of this embodiment, and after lamination is formed using the above-mentioned forming method, an inner layer circuit is formed, and this circuit is coated with black. After that, the inner layer circuit board and the prepreg of this embodiment are alternately placed one by one, and a copper foil is placed on the outermost layer, and the above conditions are met.
  • a multilayer board can be produced by lamination molding, preferably under vacuum.
  • the metal foil-clad laminate of this embodiment can be suitably used as a printed wiring board.
  • the metal foil-clad laminate of this embodiment has a peel strength of 0.28 kN/m or more, and 0.38 kN/m or more, as measured in accordance with the provisions of 5.7 "Peel strength" of JIS C6481. It is more preferably at least 0.50 kN/m, and even more preferably at least 0.50 kN/m.
  • the upper limit of the peel strength is not particularly determined, but is, for example, 2.00 kN/m or more. Peel strength is measured according to the description in Examples below.
  • the resin composition for electronic materials obtained using the resin composition of this embodiment has a cured product with low dielectric properties (low dielectric constant, low dielectric constant, low
  • the cured product can have excellent properties such as dielectric loss tangent), moisture absorption and heat resistance, and heat resistance, desmear resistance, metal foil peel strength, crack resistance, appearance of 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, the insulating layer being formed from the resin composition of the present embodiment. and a layer formed from the prepreg of this embodiment.
  • a printed wiring board can be manufactured according to a conventional method, and the manufacturing method is not particularly limited. An example of a method for manufacturing a printed wiring board will be shown below. First, a metal foil-clad laminate such as the above-mentioned copper foil-clad laminate 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 board is subjected to surface treatment to increase adhesive strength as necessary, and then the required number of sheets of prepreg described above are layered on the surface of the inner layer circuit, and then metal foil for the outer layer circuit is laminated on the outside. Then, heat and press to form an integral mold. In this way, a multilayer laminate is produced in which an insulating layer made of the base material and the cured 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 multilayer laminate, a plating metal film is formed on the wall of the hole to conduct the inner layer circuit and the metal foil for the outer layer circuit, and then the outer layer circuit is formed. A printed wiring board is manufactured by performing an etching process on metal foil to form an outer layer circuit.
  • the printed wiring board obtained in the above manufacturing example has an insulating layer and a conductor layer formed on the surface of this insulating layer, and the insulating layer is made of the resin composition of the present embodiment described above and/or a cured product thereof.
  • the configuration includes That is, the prepreg of the present embodiment described above (for example, the prepreg formed from the base material and the resin composition of the present embodiment impregnated or applied thereto), the resin composition of the metal foil-clad laminate of the present embodiment described above. The layer formed from the material becomes the insulating layer of this embodiment.
  • the present embodiment also relates to a semiconductor device including the printed wiring board. For details of the semiconductor device, the descriptions in paragraphs 0200 to 0202 of JP-A-2021-021027 can be referred to, and the contents thereof are incorporated into this specification.
  • the insulating layer formed of the cured product of the resin composition of the present embodiment has a reduced surface roughness after the insulating layer is subjected to roughening treatment.
  • the arithmetic mean roughness Ra of the surface of the insulating layer after the roughening treatment is preferably 200 nm or less, more preferably 150 nm or less, particularly preferably 100 nm or less.
  • the lower limit of the arithmetic mean roughness Ra is not particularly limited, but may be, for example, 10 nm or more.
  • the arithmetic mean roughness Ra of the surface of the insulating layer is measured using a non-contact surface roughness meter in VSI mode using a 50x lens.
  • the non-contact surface roughness meter used is WYKONT3300 manufactured by Beaco Instruments.
  • the resin composite sheet of this embodiment includes a support and a layer formed from the resin composition of this embodiment disposed on the surface of the support.
  • the resin composite sheet can be used as a build-up film or a dry film solder resist.
  • the method for producing the resin composite sheet is not particularly limited, but for example, the resin composite sheet may be produced by applying (coating) a solution of the resin composition of the present embodiment described above in a solvent to a support and drying it. There are several ways to obtain it.
  • Examples of the support used here include polyethylene film, polypropylene film, polycarbonate film, polyethylene terephthalate film, ethylenetetrafluoroethylene copolymer film, and release films in which a release agent is applied to the surface of these films.
  • Examples include organic film base materials such as polyimide film, conductive foils such as copper foil and aluminum foil, plate-like materials such as glass plates, SUS (Steel Use Stainless) plates, and FRP (Fiber-Reinforced Plastics). It is not particularly limited.
  • Examples of the coating method include a method in which a solution of the resin composition of the present embodiment dissolved in a solvent is coated onto the support using a bar coater, die coater, doctor blade, Baker applicator, etc. It will be done. Further, after drying, the support can be peeled off or etched from the resin composite sheet in which the support and the resin composition are laminated, thereby forming a single layer sheet. Note that the support can be used by supplying a solution in which the resin composition of the present embodiment described above is dissolved in a solvent into a mold having a sheet-like cavity and drying it to form it into a sheet. It is also possible to obtain a single layer sheet.
  • the drying conditions for removing the solvent are not particularly limited, but if the temperature is low, the solvent tends to remain in the resin composition, and if the temperature is high, Since curing of the resin composition progresses, the temperature is preferably 20° C. to 200° C. for 1 to 90 minutes.
  • the single layer sheet or the resin composite sheet can be used in an uncured state where the solvent is simply dried, or it can be used in a semi-cured (B-staged) state if necessary.
  • the thickness of the resin layer in the single-layer sheet or resin composite sheet of this embodiment can be adjusted by the concentration of the solution of the resin composition of this embodiment used for application (coating) and the coating thickness, and there are no particular limitations. However, in general, as the coating thickness increases, solvent tends to remain during drying, so 0.1 to 500 ⁇ m is preferable.
  • Liquid pump manufactured by Shimadzu Corporation, LC-20AD
  • differential refractive index detector manufactured by Shimadzu Corporation, RID-10A
  • GPC column manufactured by Showa Denko Corporation, GPC KF-801, 802, 803, 804
  • the experiment was carried out using tetrahydrofuran as the solvent, a flow rate of 1.0 mL/min, a column temperature of 40° C., and a calibration curve using monodisperse polystyrene.
  • the obtained polymer (va) having a structural unit represented by formula (V) had a number average molecular weight Mn of 2,060, a weight average molecular weight Mw of 30,700, and a monodispersity Mw/Mn of 14.9. there were.
  • the polymer (va) having the structural unit represented by formula (V) had resonance lines originating from each monomer unit used as a raw material. observed.
  • the proportion of each monomer unit (constituent unit derived from each raw material) in the polymer (va) having the structural unit represented by formula (V) is as follows. was calculated.
  • Example 1 21.0 parts by mass of a polymer (va) having a structural unit represented by, a maleimide compound (m1a) having the structure shown below (manufactured by DIC Corporation, "NE-X-9470S", represented by formula (M1) compound), 16.0 parts by mass of thermoplastic elastomer (SBS, manufactured by JSR Corporation, TR2250), 21.0 parts by mass of phosphorus flame retardant (PX-200, manufactured by Daihachi Kagaku Co., Ltd.), methyl ethyl ketone ( (solvent) and mixed to obtain a varnish. Note that each amount added above indicates the amount of solid content.
  • n is an integer from 1 to 20.
  • a resin composition powder was obtained by evaporating the solvent from the obtained varnish.
  • a mold with a side of 100 mm and a thickness of 0.8 mm was filled with the resin composition powder, copper foil (3EC-M2S-VLP, manufactured by Mitsui Mining & Mining Co., Ltd.) with a thickness of 12 ⁇ m was placed on both sides, and a pressure of 30 kg/ cm 2 and vacuum pressing at a temperature of 220° C. for 120 minutes to obtain a cured plate with a side of 100 mm and a thickness of 0.8 mm.
  • the obtained cured plates were used to evaluate dielectric constant (Dk), dielectric loss tangent (Df), glass transition temperature (Tg), peel strength, desmear resistance, and moisture absorption heat resistance. The evaluation results are shown in Table 1.
  • ⁇ Measurement method and evaluation method> Relative permittivity (Dk) and dielectric loss tangent (Df) After removing the copper foils on both sides of the obtained cured plate by etching, it was downsized to 10 mm x 1 mm to obtain a sample for evaluation. The obtained evaluation sample was dried at 120° C. for 60 minutes, and then the relative dielectric constant (Dk) and dielectric loss tangent (Df) after drying at a frequency of 10 GHz were measured using a perturbation method cavity resonator. The measurement temperature was 23°C. The perturbation method cavity resonator used was Agilent 8722ES manufactured by Agilent Technologies.
  • Dk Specific permittivity
  • B Over 2.50 and 2.60 or less
  • C 2.60 super dielectric loss tangent
  • S 0.0014 or less
  • C More than 0.0020
  • the glass transition temperature was measured using a dynamic viscoelasticity measuring device on a sample that was downsized to 12.7 mm x 30 mm after removing the copper foil on both sides of the obtained cured plate by etching, and was determined according to JIS-K7244-4:1999 ( Plastics - Test method for dynamic mechanical properties - Part 4: Tensile vibration - Non-resonance method), starting temperature 30°C, ending temperature 400°C, heating rate 5°C/min, measurement frequency 1Hz, under nitrogen atmosphere The dynamic viscoelasticity was measured, and the temperature at which the loss tangent (tan ⁇ ) obtained was the maximum value was taken as the glass transition temperature.
  • the dynamic viscoelasticity measuring device used was EXSTAR6000 DMS6100 manufactured by Seiko Instruments Inc. It was evaluated as follows. A: 230°C or more B: 200°C or more and less than 230°C C: Less than 200°C
  • the mass reduction rate (mass %) of the sample was measured. It was evaluated as follows. A minus sign represents a decrease in mass. A: The mass reduction rate is in the range of -4.0% by mass to -2.0% by mass. B: Mass reduction rate is outside the above range.
  • the obtained cured board was cut into 50 mm x 50 mm (downsizing), all the copper foil on one side was removed by etching, and half of the copper foil on the other side was removed. It was removed by etching to obtain a sample for measuring moisture absorption and heat resistance.
  • the obtained sample was dried at 120°C for 60 minutes, then left to stand for 5 hours at 121°C in the presence of saturated steam at 2 atm using a pressure cooker tester, and then placed in a solder bath at 260°C for 30 seconds. The samples were dipped and visually observed for any abnormalities in appearance.
  • the pressure cooker tester used was model PC-3 manufactured by Hirayama Seisakusho Co., Ltd.
  • Table 2 The results are shown in Table 2.
  • the content of the polymer (va) having the structural unit was changed to 31.5 parts by mass
  • the content of the maleimide compound (m1a) (manufactured by DIC Corporation, "NE-X-9470S”) was changed to 31.5 parts by mass, The rest were done in the same way.
  • the results are shown in Table 2.
  • Example 2 In Example 1, 21.0 parts by mass of a polymer (va) having a structural unit represented by formula (V) was mixed with an equivalent amount of a maleimide compound (manufactured by Nippon Kayaku Co., Ltd., MIR-3000, the structure of which is shown below) .) and did the other things in the same way. The results are shown in Table 2.

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Abstract

Provided are: a resin composition having excellent moisture absorption heat resistance while maintaining excellent low dielectric properties (Dk and/or Df); a cured product; a prepreg; a metal foil-clad laminate; a resin composite sheet; a printed circuit board; and a semiconductor device. The resin composition comprises a compound (M) represented by formula (M), a polymer (V) having a constituent unit represented by formula (V), and a compound (M1) represented by formula (M1). In formula (V), Ar represents an aromatic hydrocarbon linking group.

Description

樹脂組成物、硬化物、プリプレグ、金属箔張積層板、樹脂複合シート、プリント配線板、および、半導体装置Resin compositions, cured products, prepregs, metal foil laminates, resin composite sheets, printed wiring boards, and semiconductor devices
　本発明は、樹脂組成物、硬化物、プリプレグ、金属箔張積層板、樹脂複合シート、プリント配線板、および、半導体装置に関する。 The present invention relates to a resin composition, a cured product, a prepreg, a metal foil-clad laminate, a resin composite sheet, a printed wiring board, and a semiconductor device.
　近年、携帯端末をはじめ、電子機器や通信機器等に用いられる半導体素子の高集積化および微細化が加速している。これに伴い、半導体素子の高密度実装を可能とする技術が求められており、その重要な位置をしめるプリント配線板についても改良が求められている。
　一方、電子機器等の用途は多様化し拡大をつづけている。これを受け、プリント配線板やこれに用いる金属箔張積層板、プリプレグなどに求められる諸特性も多様化し、かつ厳しいものとなっている。そうした要求特性を考慮しながら、改善されたプリント配線板を得るために、各種の材料や加工法が提案されている。その１つとして、プリプレグや樹脂複合シートを構成する樹脂材料の改良開発が挙げられる。 In recent years, the integration and miniaturization of semiconductor elements used in mobile terminals, electronic equipment, communication equipment, etc. have been accelerating. Along with this, there is a need for technology that enables high-density packaging of semiconductor elements, and improvements are also needed for printed wiring boards, which play an important role.
On the other hand, the uses of electronic devices, etc. continue to diversify and expand. In response to this trend, the characteristics required of printed wiring boards, metal foil-clad laminates, prepregs, etc. used therein are becoming more diverse and demanding. Taking these required characteristics into consideration, various materials and processing methods have been proposed to obtain improved printed wiring boards. One example of this is the development and improvement of resin materials that make up prepregs and resin composite sheets.
　また、特許文献１には、電子材料用途に適したマレイミド樹脂として、下記に示されるマレイミド樹脂が開示されている。さらに、特許文献１には、エポキシ樹脂等とブレンドした硬化性樹脂組成物が誘電特性に優れることが示されている。また、特許文献２にも下記化合物について記載がある。
Further, Patent Document 1 discloses maleimide resins shown below as maleimide resins suitable for electronic material applications. Further, Patent Document 1 discloses that a curable resin composition blended with an epoxy resin or the like has excellent dielectric properties. Further, Patent Document 2 also describes the following compounds.
国際公開第２０２０／０５４６０１号International Publication No. 2020/054601 国際公開第２０２１／１８２３６０号International Publication No. 2021/182360
　上述の通り、電子機器等の用途は多様化し拡大をつづけており、プリプレグ等を構成する樹脂材料についても、新たな材質のものが求められている。特に、優れた低誘電特性（Ｄｋおよび／またはＤｆ）を維持しつつ、吸湿耐熱性に優れた樹脂組成物について、さらなる材料開発が求められている。
　本発明は、上記課題を解決することを目的とするものであって、優れた低誘電特性（Ｄｋおよび／またはＤｆ）を維持しつつ、吸湿耐熱性に優れた樹脂組成物、ならびに、硬化物、プリプレグ、金属箔張積層板、樹脂複合シート、プリント配線板、および、半導体装置を提供することを目的とする。 As mentioned above, the uses of electronic devices and the like continue to diversify and expand, and there is a demand for new resin materials for prepregs and the like. In particular, further material development is required for resin compositions that have excellent moisture absorption and heat resistance while maintaining excellent low dielectric properties (Dk and/or Df).
The present invention aims to solve the above problems, and provides a resin composition that maintains excellent low dielectric properties (Dk and/or Df) and has excellent moisture absorption and heat resistance, and a cured product. , a prepreg, a metal foil-clad laminate, a resin composite sheet, a printed wiring board, and a semiconductor device.
　上記課題のもと、本発明者が検討を行った結果、所定のマレイミド化合物と所定の多官能ビニル芳香族重合体を併用することにより、上記課題を解決しうることを見出した。
　具体的には、下記手段により、上記課題は解決された。
＜１＞式（Ｍ）で表される化合物（Ｍ）と、
式（Ｖ）で表される構成単位を有する重合体（Ｖ）と、
式（Ｍ１）で表される化合物（Ｍ１）と
を含む、樹脂組成物。
（式（Ｍ）中、Ｒは、それぞれ独立に、ハロゲン原子で置換されていてもよい炭素数１～１０の炭化水素基を表し、Ｒｍｘは、それぞれ独立に、メチレン基、エチリデン基、または、２，２－プロピリデン基であり、Ｒｍｙは、下記群（Ａ）から選択される基である。ｍは、０～３の整数を表し、ｎは、繰返し数の平均値であり、１．００≦ｎ≦２０．００を表す。）
（群（Ａ））
(群（Ａ）において、Ｒｙは、それぞれ独立に、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、または、置換基を有してもよいフェニル基であり、ｎｙは、それぞれ独立に０～３の整数であり、＊は、Ｒｍｘとの結合位置である。)
（式（Ｖ）中、Ａｒは芳香族炭化水素連結基を表す。＊は、結合位置を表す。）
（式（Ｍ１）中、ＲＭ１、ＲＭ２、ＲＭ３、およびＲＭ４は、それぞれ独立に、水素原子または有機基を表す。ＲＭ５およびＲＭ６は、それぞれ独立に、水素原子またはアルキル基を表す。ＡｒＭは２価の芳香族基を表す。Ａは、４～６員環の脂環基である。ＲＭ７およびＲＭ８は、それぞれ独立に、アルキル基である。ｍｘは１または２であり、ｌｘは０または１である。ＲＭ９およびＲＭ１０は、それぞれ独立に、水素原子またはアルキル基を表す。ＲＭ１１、ＲＭ１２、ＲＭ１３、およびＲＭ１４は、それぞれ独立に、水素原子または有機基を表す。ＲＭ１５は、それぞれ独立に、炭素数１～１０のアルキル基、炭素数１～１０のアルキルオキシ基、炭素数１～１０のアルキルチオ基、炭素数６～１０のアリール基、炭素数６～１０のアリールオキシ基、炭素数６～１０のアリールチオ基、ハロゲン原子、水酸基またはメルカプト基を表す。ｐｘは０～３の整数を表す。ｎｘは１～２０の整数を表す。）
＜２＞前記樹脂組成物中の樹脂固形分１００質量部に対する、前記式（Ｍ）で表される化合物（Ｍ）の含有量が５～５０質量部である、＜１＞に記載の樹脂組成物。
＜３＞前記樹脂組成物中の樹脂固形分１００質量部に対する、前記式（Ｖ）で表される構成単位を有する重合体（Ｖ）の含有量が５～５０質量部である、＜１＞または＜２＞に記載の樹脂組成物。
＜４＞前記樹脂組成物中の樹脂固形分１００質量部に対する、前記式（Ｍ１）で表される化合物（Ｍ１）の含有量が５～５０質量部である、＜１＞～＜３＞のいずれか１つに記載の樹脂組成物。
＜５＞前記式（Ｍ）で表される化合物（Ｍ）において、ｎが、１．０５≦ｎ≦２０．００である、＜１＞～＜４＞のいずれか１つに記載の樹脂組成物。
＜６＞前記式（Ｍ）で表される化合物（Ｍ）が、式（Ｍ－１）で表される化合物を含む、＜１＞～＜５＞のいずれか１つに記載の樹脂組成物。
（式（Ｍ－１）中、Ｒは、それぞれ独立に、ハロゲン原子で置換されていてもよい炭素数１～１０の炭化水素基を表す。ｍは、０～３の整数を表し、ｎは、繰返し数の平均値であり、１．００≦ｎ≦２０．００を表す。）
＜７＞前記式（Ｍ）で表される化合物（Ｍ）が、式（Ｍ－２）で表される化合物を含む、＜１＞～＜６＞のいずれか１つに記載の樹脂組成物。
（式（Ｍ－２）中、Ｒｚは、それぞれ独立に、炭素数１～１０の炭化水素基を表す。ｍは０～３の整数を表し、ｎは、繰返し数の平均値であり、１．００≦ｎ≦２０．００を表す。）
＜８＞前記式（Ｖ）で表される構成単位を有する重合体（Ｖ）の重量平均分子量が、３，０００～１３０，０００である、＜１＞～＜７＞のいずれか１つに記載の樹脂組成物。
＜９＞前記式（Ｖ）で表される構成単位を有する重合体（Ｖ）の重量平均分子量が、１０，０００～１３０，０００である、＜１＞～＜８＞のいずれか１つに記載の樹脂組成物。
＜１０＞さらに、前記式（Ｍ）で表される化合物（Ｍ）および前記式（Ｍ１）で表される化合物（Ｍ１）以外のマレイミド化合物、エポキシ化合物、フェノール化合物、オキセタン樹脂、ベンゾオキサジン化合物、（メタ）アリル基を含む化合物（好ましくはアルケニルナジイミド化合物）、および、炭素－炭素不飽和二重結合を２以上含むポリフェニレンエーテル化合物からなる群より選択される１種以上の他の熱硬化性化合物（Ｃ）を含む、＜１＞～＜９＞のいずれか１つに記載の樹脂組成物。
＜１１＞前記樹脂組成物中の樹脂固形分１００質量部に対する、前記他の熱硬化性化合物（Ｃ）の含有量が１～５０質量部である、＜１０＞に記載の樹脂組成物。
＜１２＞さらに、充填材（Ｄ）を含む、＜１＞～＜１１＞のいずれか１つに記載の樹脂組成物。
＜１３＞前記樹脂組成物における、前記充填材（Ｄ）の含有量が、樹脂固形分１００質量部に対し、１０～１６００質量部である、＜１２＞に記載の樹脂組成物。
＜１４＞さらに、熱可塑性エラストマーを含む、＜１＞～＜１３＞のいずれか１つに記載の樹脂組成物。
＜１５＞前記樹脂組成物中の樹脂固形分１００質量部に対する、前記式（Ｍ）で表される化合物（Ｍ）の含有量が５～５０質量部であり、
前記樹脂組成物中の樹脂固形分１００質量部に対する、前記式（Ｖ）で表される構成単位を有する重合体（Ｖ）の含有量が５～５０質量部であり、
前記樹脂組成物中の樹脂固形分１００質量部に対する、前記式（Ｍ１）で表される化合物（Ｍ１）の含有量が５～５０質量部であり、
前記式（Ｍ）で表される化合物（Ｍ）が、式（Ｍ－１）で表される化合物を含み、ｎが、１．０５≦ｎ≦２０．００であり、
前記式（Ｖ）で表される構成単位を有する重合体（Ｖ）の重量平均分子量が、３，０００～１３０，０００である、＜１＞～＜１４＞のいずれか１つに記載の樹脂組成物。
（式（Ｍ－１）中、Ｒは、それぞれ独立に、ハロゲン原子で置換されていてもよい炭素数１～１０の炭化水素基を表す。ｍは、０～３の整数を表し、ｎは、繰返し数の平均値であり、１．００≦ｎ≦２０．００を表す。）
＜１６＞＜１＞～＜１５＞のいずれか１つに記載の樹脂組成物の硬化物。
＜１７＞基材と、＜１＞～＜１５＞のいずれか１つに記載の樹脂組成物とから形成された、プリプレグ。
＜１８＞＜１７＞に記載のプリプレグから形成された少なくとも１つの層と、前記プリプレグから形成された層の片面または両面に配置された金属箔とを含む、金属箔張積層板。
＜１９＞支持体と、前記支持体の表面に配置された＜１＞～＜１５＞のいずれか１つに記載の樹脂組成物から形成された層とを含む、樹脂複合シート。
＜２０＞絶縁層と、前記絶縁層の表面に配置された導体層とを含むプリント配線板であって、前記絶縁層が、＜１＞～＜１５＞のいずれか１つに記載の樹脂組成物から形成された層から形成された層の少なくとも一方を含む、プリント配線板。
＜２１＞＜２０＞に記載のプリント配線板を含む半導体装置。 Based on the above-mentioned problems, the present inventor conducted studies and found that the above-mentioned problems can be solved by using a certain maleimide compound and a certain polyfunctional vinyl aromatic polymer together.
Specifically, the above problem was solved by the following means.
<1> A compound (M) represented by formula (M),
A polymer (V) having a structural unit represented by formula (V),
A resin composition comprising a compound (M1) represented by formula (M1).
(In formula (M), R each independently represents a hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a halogen atom, and R mx each independently represents a methylene group, an ethylidene group, or , 2,2-propylidene group, R my is a group selected from the following group (A), m represents an integer of 0 to 3, n is the average value of the number of repeats, 1 .00≦n≦20.00)
(Group (A))
(In group (A), R y is each independently an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group which may have a substituent, and ny is , each independently an integer from 0 to 3, and * is the bonding position with R mx .)
(In formula (V), Ar represents an aromatic hydrocarbon linking group. * represents the bonding position.)
(In formula (M1), R M1 , R M2 , R M3 , and R M4 each independently represent a hydrogen atom or an organic group. R M5 and R M6 each independently represent a hydrogen atom or an alkyl group. Ar M represents a divalent aromatic group. A 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 represents 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, or an aryl group having 6 to 10 carbon atoms. , represents an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a halogen atom, a hydroxyl group or a mercapto group. px represents an integer of 0 to 3. nx represents an integer of 1 to 20. )
<2> The resin composition according to <1>, wherein the content of the compound (M) represented by the formula (M) is 5 to 50 parts by mass based on 100 parts by mass of resin solids in the resin composition. thing.
<3> The content of the polymer (V) having the structural unit represented by the formula (V) is 5 to 50 parts by mass based on 100 parts by mass of the resin solid content in the resin composition, <1> Or the resin composition according to <2>.
<4> The content of the compound (M1) represented by the formula (M1) is 5 to 50 parts by mass based on 100 parts by mass of resin solids in the resin composition, <1> to <3>. Any one of the resin compositions.
<5> In the compound (M) represented by the formula (M), n is 1.05≦n≦20.00, the resin composition according to any one of <1> to <4>. thing.
<6> The resin composition according to any one of <1> to <5>, wherein the compound (M) represented by the formula (M) includes a compound represented by the formula (M-1). .
(In formula (M-1), R each independently represents a hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a halogen atom, m represents an integer of 0 to 3, and n represents , is the average value of the number of repetitions, and represents 1.00≦n≦20.00.)
<7> The resin composition according to any one of <1> to <6>, wherein the compound (M) represented by the formula (M) includes a compound represented by the formula (M-2). .
(In formula (M-2), R z each independently represents a hydrocarbon group having 1 to 10 carbon atoms, m represents an integer of 0 to 3, n is the average value of the number of repeats, (Represents 1.00≦n≦20.00.)
<8> Any one of <1> to <7>, wherein the weight average molecular weight of the polymer (V) having a structural unit represented by the formula (V) is 3,000 to 130,000. The resin composition described.
<9> Any one of <1> to <8>, wherein the weight average molecular weight of the polymer (V) having a structural unit represented by the formula (V) is 10,000 to 130,000. The resin composition described.
<10> Furthermore, maleimide compounds, epoxy compounds, phenol compounds, oxetane resins, benzoxazine compounds other than the compound (M) represented by the formula (M) and the compound (M1) represented by the formula (M1), One or more other thermosetting compounds selected from the group consisting of a compound containing a (meth)allyl group (preferably an alkenylnadimide compound) and a polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds. The resin composition according to any one of <1> to <9>, containing the compound (C).
<11> The resin composition according to <10>, wherein the content of the other thermosetting compound (C) is 1 to 50 parts by mass based on 100 parts by mass of resin solid content in the resin composition.
<12> The resin composition according to any one of <1> to <11>, further comprising a filler (D).
<13> The resin composition according to <12>, wherein the content of the filler (D) in the resin composition is 10 to 1600 parts by mass based on 100 parts by mass of resin solid content.
<14> The resin composition according to any one of <1> to <13>, further comprising a thermoplastic elastomer.
<15> The content of the compound (M) represented by the formula (M) is 5 to 50 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition,
The content of the polymer (V) having the structural unit represented by the formula (V) is 5 to 50 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition,
The content of the compound (M1) represented by the formula (M1) is 5 to 50 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition,
The compound (M) represented by the formula (M) includes a compound represented by the formula (M-1), and n is 1.05≦n≦20.00,
The resin according to any one of <1> to <14>, wherein the polymer (V) having a structural unit represented by the formula (V) has a weight average molecular weight of 3,000 to 130,000. Composition.
(In formula (M-1), R each independently represents a hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a halogen atom, m represents an integer of 0 to 3, and n represents , is the average value of the number of repetitions, and represents 1.00≦n≦20.00.)
<16> A cured product of the resin composition according to any one of <1> to <15>.
<17> A prepreg formed from a base material and the resin composition according to any one of <1> to <15>.
<18> A metal foil-clad laminate comprising at least one layer formed from the prepreg according to <17> and metal foil disposed on one or both sides of the layer formed from the prepreg.
<19> A resin composite sheet comprising a support and a layer formed from the resin composition according to any one of <1> to <15>, disposed on the surface of the support.
<20> A printed wiring board comprising an insulating layer and a conductor layer disposed on the surface of the insulating layer, wherein the insulating layer is made of the resin composition according to any one of <1> to <15>. A printed wiring board comprising at least one layer formed from a layer formed from a material.
<21> A semiconductor device including the printed wiring board according to <20>.
　本発明により、優れた低誘電特性（Ｄｋおよび／またはＤｆ）を維持しつつ、吸湿耐熱性に優れた樹脂組成物、ならびに、硬化物、プリプレグ、金属箔張積層板、樹脂複合シート、プリント配線板、および、半導体装置を提供可能になった。 The present invention provides a resin composition that maintains excellent low dielectric properties (Dk and/or Df) and has excellent moisture absorption and heat resistance, as well as cured products, prepregs, metal foil-clad laminates, resin composite sheets, and printed wiring. We are now able to provide boards and semiconductor devices.
　以下、本発明を実施するための形態（以下、単に「本実施形態」という）について詳細に説明する。なお、以下の本実施形態は、本発明を説明するための例示であり、本発明は本実施形態のみに限定されない。
　なお、本明細書において「～」とはその前後に記載される数値を下限値および上限値として含む意味で使用される。
　本明細書において、各種物性値および特性値は、特に述べない限り、２３℃におけるものとする。
　本明細書における基（原子団）の表記において、置換および無置換を記していない表記は、置換基を有さない基（原子団）と共に置換基を有する基（原子団）をも包含する。例えば、「アルキル基」とは、置換基を有さないアルキル基（無置換アルキル基）のみならず、置換基を有するアルキル基（置換アルキル基）をも包含する。本明細書では、置換および無置換を記していない表記は、無置換の方が好ましい。
　本明細書において、比誘電率とは、物質の真空の誘電率に対する誘電率の比を示す。また、本明細書においては、比誘電率を単に「誘電率」ということがある。
　本明細書において、「（メタ）アクリル」は、アクリルおよびメタクリルの双方、または、いずれかを表す。「（メタ）アリル」は、アリルおよびメタアリルの双方、またはいずれかを表す。
　本明細書で示す規格が年度によって、測定方法等が異なる場合、特に述べない限り、２０２２年１月１日時点における規格に基づくものとする。 Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as "this embodiment") will be described in detail. Note that the present embodiment below is an illustration for explaining the present invention, and the present invention is not limited only to this embodiment.
In addition, in this specification, "~" is used to include the numerical values described before and after it as a lower limit value and an upper limit value.
In this specification, various physical property values and characteristic values are assumed to be at 23° C. unless otherwise stated.
In the description of a group (atomic group) in this specification, the description that does not indicate substituted or unsubstituted includes a group having no substituent (atomic group) as well as a group having a substituent (atomic group). For example, the term "alkyl group" includes not only an alkyl group without a substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). In this specification, for expressions that do not indicate substitution or non-substitution, non-substitution is preferred.
In this specification, the relative dielectric constant refers to the ratio of the dielectric constant to the vacuum dielectric constant of a substance. Further, in this specification, the relative dielectric constant may be simply referred to as "permittivity."
In this specification, "(meth)acrylic" represents both or either acrylic and methacrylic. "(Meta)allyl" represents allyl and/or metaallyl.
If the standards shown in this specification differ in measurement methods, etc. depending on the year, unless otherwise stated, the standards as of January 1, 2022 are used.
　本明細書において、マレイミド基とは、下記で表される基をいう。
（式中、Ａは、それぞれ独立に、水素原子、または炭素数１～４の直鎖状もしくは分岐状のアルキル基を表す。＊は他の部位との結合位置である。）
　Ａは、好適に硬化する点から、両方ともに水素原子であることが好ましい。
　アルキル基の炭素数としては、好適に硬化する点から、１～３であることが好ましく、１～２であることがより好ましい。 In this specification, the maleimide group refers to the group represented below.
(In the formula, each A independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms. * indicates a bonding position with another site.)
From the viewpoint of suitable curing, both A are preferably hydrogen atoms.
The number of carbon atoms in the alkyl group is preferably 1 to 3, more preferably 1 to 2, from the viewpoint of suitable curing.
　本明細書において、樹脂固形分とは、充填材および溶剤を除く成分をいい、式（Ｍ）で表される化合物(Ｍ)、式（Ｖ）で表される構成単位を有する重合体（Ｖ）、および、式（Ｍ１）で表される化合物（Ｍ１）、ならびに、必要に応じて配合される他の熱硬化性化合物（Ｃ）、およびその他の樹脂添加剤成分（難燃剤等の添加剤等）を含む趣旨である。 In this specification, the resin solid content refers to the components excluding the filler and the solvent, and refers to the compound (M) represented by the formula (M), the polymer (V ), and the compound (M1) represented by formula (M1), other thermosetting compounds (C) blended as necessary, and other resin additive components (additives such as flame retardants) etc.).
　本実施形態の樹脂組成物は、式（Ｍ）で表される化合物(Ｍ)と、式（Ｖ）で表される構成単位を有する重合体（Ｖ）と、式（Ｍ１）で表される化合物（Ｍ１）とを含むことを特徴とする。
（式（Ｍ）中、Ｒは、それぞれ独立に、ハロゲン原子で置換されていてもよい炭素数１～１０の炭化水素基を表し、Ｒｍｘは、それぞれ独立に、メチレン基、エチリデン基、または、２，２－プロピリデン基であり、Ｒｍｙは、下記群（Ａ）から選択される基である。ｍは、０～３の整数を表し、ｎは、繰返し数の平均値であり、１．００≦ｎ≦２０．００を表す。）
（群（Ａ））
(群（Ａ）において、Ｒｙは、それぞれ独立に、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、または、置換基を有してもよいフェニル基であり、ｎｙは、それぞれ独立に０～３の整数であり、＊は、Ｒｍｘとの結合位置である。)
（式（Ｖ）中、Ａｒは芳香族炭化水素連結基を表す。＊は、結合位置を表す。）
（式（Ｍ１）中、ＲＭ１、ＲＭ２、ＲＭ３、およびＲＭ４は、それぞれ独立に、水素原子または有機基を表す。ＲＭ５およびＲＭ６は、それぞれ独立に、水素原子またはアルキル基を表す。ＡｒＭは２価の芳香族基を表す。Ａは、４～６員環の脂環基である。ＲＭ７およびＲＭ８は、それぞれ独立に、アルキル基である。ｍｘは１または２であり、ｌｘは０または１である。ＲＭ９およびＲＭ１０は、それぞれ独立に、水素原子またはアルキル基を表す。ＲＭ１１、ＲＭ１２、ＲＭ１３、およびＲＭ１４は、それぞれ独立に、水素原子または有機基を表す。ＲＭ１５は、それぞれ独立に、炭素数１～１０のアルキル基、炭素数１～１０のアルキルオキシ基、炭素数１～１０のアルキルチオ基、炭素数６～１０のアリール基、炭素数１～１０のアリールオキシ基、炭素数１～１０のアリールチオ基、ハロゲン原子、水酸基またはメルカプト基を表す。ｐｘは０～３の整数を表す。ｎｘは１～２０の整数を表す。） The resin composition of the present embodiment includes a compound (M) represented by formula (M), a polymer (V) having a structural unit represented by formula (V), and a compound represented by formula (M1). Compound (M1).
(In formula (M), R each independently represents a hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a halogen atom, and R mx each independently represents a methylene group, an ethylidene group, or , 2,2-propylidene group, R my is a group selected from the following group (A), m represents an integer of 0 to 3, n is the average value of the number of repeats, 1 .00≦n≦20.00)
(Group (A))
(In group (A), R y is each independently an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group which may have a substituent, and ny is , each independently an integer from 0 to 3, and * is the bonding position with R mx .)
(In formula (V), Ar represents an aromatic hydrocarbon linking group. * represents the bonding position.)
(In formula (M1), R M1 , R M2 , R M3 , and R M4 each independently represent a hydrogen atom or an organic group. R M5 and R M6 each independently represent a hydrogen atom or an alkyl group. Ar M represents a divalent aromatic group. A 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 represents 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, or an aryl group having 6 to 10 carbon atoms. , represents 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. )
　このような構成とすることにより、優れた低誘電特性（Ｄｋおよび／またはＤｆ）を維持しつつ、吸湿耐熱性に優れた樹脂組成物が得られる。
　このメカニズムとしては、これに限定されるものではないが、式（Ｍ）で表される化合物（Ｍ）においてＲｍｘｙが、メチレン基、エチリデン基、または、２，２－プロピリデン基であり、且つ、２つのＲｍｘが１つのベンゼン環に結合していることにより、よりコンパクトな構造となるため、架橋反応が進行しても、剛直になりにくく、他の樹脂成分と相溶しやすくなると推測される。特に、式（Ｍ）で表される化合物（Ｍ）と式（Ｖ）で表される構成単位を有する重合体（Ｖ）とを組み合わせることで低誘電特性（低比誘電率、低誘電正接（特に低誘電正接））が達成されると推測される。また、式（Ｍ１）で表される化合物（Ｍ１）と式（Ｖ）で表される構成単位を有する重合体（Ｖ）に対して、これらの化合物より硬化反応温度が高い式(Ｍ)で表される化合物(Ｍ)を複合化することで、硬化反応の進行がバランスよく制御され、結果として吸湿耐熱性が改善すると推測される。
　さらに、本実施形態の樹脂組成物は、耐熱性が高いものとすることができる。また、本実施形態の樹脂組成物はピール強度が高いものとすることができる。さらにまた、本実施形態の樹脂組成物はデスミア耐性に優れているものとすることができる。 With such a configuration, a resin composition having excellent moisture absorption and heat resistance while maintaining excellent low dielectric properties (Dk and/or Df) can be obtained.
This mechanism is not limited to this, but in the compound (M) represented by formula (M), R mxy is a methylene group, an ethylidene group, or a 2,2-propylidene group, and , it is assumed that because two R mx are bonded to one benzene ring, it becomes a more compact structure, so even if the crosslinking reaction progresses, it will not become rigid and will be more compatible with other resin components. be done. In particular, by combining the compound (M) represented by formula (M) and the polymer (V) having a structural unit represented by formula (V), low dielectric properties (low dielectric constant, low dielectric loss tangent ( In particular, it is assumed that a low dielectric loss tangent)) is achieved. Furthermore, with respect to the compound (M1) represented by formula (M1) and the polymer (V) having a structural unit represented by formula (V), a compound of formula (M) having a higher curing reaction temperature than these compounds may be used. It is presumed that by compounding the represented compound (M), the progress of the curing reaction is controlled in a well-balanced manner, and as a result, the moisture absorption and heat resistance is improved.
Furthermore, the resin composition of this embodiment can have high heat resistance. Furthermore, the resin composition of this embodiment can have high peel strength. Furthermore, the resin composition of this embodiment can have excellent desmear resistance.
＜式（Ｍ）で表される化合物（Ｍ）＞
　本実施形態の樹脂組成物は、式(Ｍ)で表される化合物(Ｍ)を含む。式（Ｍ）で表される化合物（Ｍ）を含むことにより、得られる樹脂組成物の低誘電特性（Ｄｋおよび／またはＤｆ）を効果的に達成することができる。
（式（Ｍ）中、Ｒは、それぞれ独立に、ハロゲン原子で置換されていてもよい炭素数１～１０の炭化水素基を表し、Ｒｍｘは、それぞれ独立に、メチレン基、エチリデン基、または、２，２－プロピリデン基であり、Ｒｍｙは、下記群（Ａ）から選択される基である。ｍは、０～３の整数を表し、ｎは、繰返し数の平均値であり、１．００≦ｎ≦２０．００を表す。）
（群（Ａ））
(群（Ａ）において、Ｒｙは、それぞれ独立に、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、または、置換基を有してもよいフェニル基であり、ｎｙは、それぞれ独立に０～３の整数であり、＊は、Ｒｍｘとの結合位置である。) <Compound (M) represented by formula (M)>
The resin composition of this embodiment contains a compound (M) represented by formula (M). By including the compound (M) represented by formula (M), low dielectric properties (Dk and/or Df) of the resulting resin composition can be effectively achieved.
(In formula (M), R each independently represents a hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a halogen atom, and R mx each independently represents a methylene group, an ethylidene group, or , 2,2-propylidene group, R my is a group selected from the following group (A), m represents an integer of 0 to 3, n is the average value of the number of repeats, 1 .00≦n≦20.00)
(Group (A))
(In group (A), R y is each independently an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group which may have a substituent, and ny is , each independently an integer from 0 to 3, and * is the bonding position with R mx .)
　式（Ｍ）中、Ｒは、それぞれ独立に、ハロゲン原子で置換されていてもよい炭素数１～１０の炭化水素基を表し、ハロゲン原子で置換されていてもよい炭素数１～１０のアルキル基、または、ハロゲン原子で置換されていてもよいフェニル基であることが好ましく、ハロゲン原子で置換されていてもよい、メチル基、エチル基、プロピル基（好ましくはイソプロピル基）、ブチル基（好ましくは、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基）、およびフェニル基からなる群より選択される少なくとも１種であることがより好ましい。前記ハロゲン原子は、フッ素原子、塩素原子、臭素原子、または、ヨウ素原子であることが好ましく、フッ素原子、または、塩素原子であることがより好ましい。本実施形態において、Ｒはハロゲン原子で置換されていない炭素数１～１０の炭化水素基であることが好ましい。 In formula (M), R each independently represents a hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a halogen atom, and an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom. or a phenyl group which may be substituted with a halogen atom, such as a methyl group, an ethyl group, a propyl group (preferably an isopropyl group), or a butyl group (preferably an isopropyl group), which may be substituted with a halogen atom. is more preferably at least one selected from the group consisting of a sec-butyl group, a tert-butyl group, and a phenyl group. The halogen atom is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and more preferably a fluorine atom or a chlorine atom. In this embodiment, R is preferably a hydrocarbon group having 1 to 10 carbon atoms that is not substituted with a halogen atom.
　式（Ｍ）中、ｍは、０～３の整数を表し、０～２の整数であることが好ましく、０または１であることがより好ましく、０であることがさらに好ましい。 In formula (M), m represents an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0.
　式（Ｍ）中、Ｒｍｘは、それぞれ独立に、メチレン基、エチリデン基、または、２，２－プロピリデン基である。Ｒｍｘとして、メチレン基、エチリデン基、または、２，２－プロピリデン基を用いることにより、芳香環と比較して、低誘電特性（Ｄｋおよび／またはＤｆ）を有し、かつ柔軟な構造であるため、架橋反応が進行しても、剛直になりにくく、他の樹脂成分と相溶しやすくなると推測される。Ｒｍｘは、それぞれ独立に、エチリデン基、または、２，２－プロピリデン基であることが好ましく、２，２－プロピリデン基であることがより好ましい。 In formula (M), R mx is each independently a methylene group, an ethylidene group, or a 2,2-propylidene group. By using a methylene group, ethylidene group, or 2,2-propylidene group as R mx , it has a lower dielectric property (Dk and/or Df) and a flexible structure compared to an aromatic ring. Therefore, even if the crosslinking reaction progresses, it is difficult to become rigid and it is presumed that it becomes compatible with other resin components. Each R mx is preferably an ethylidene group or a 2,2-propylidene group, more preferably a 2,2-propylidene group.
　式（Ｍ）中、Ｒｍｙは、群（Ａ）から選択される基である。このように、１つのベンゼン環を介して隣接する２つのＲｍｘと結合する構造であることにより、必要以上に剛直な構造にならず、他の樹脂成分と相溶しやすくなる。 In formula (M), R my is a group selected from group (A). In this way, by having a structure in which two adjacent R mx are bonded via one benzene ring, the structure does not become unnecessarily rigid, and it becomes compatible with other resin components.
　群（Ａ）において、Ｒｙは、それぞれ独立に、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、または、置換基を有してもよいフェニル基であり、メチル基、エチル基、プロピル基、メトキシ基、エトキシ基、およびフェニル基からなる群より選択される少なくとも１種であることが好ましい。
　ｎｙは、それぞれ独立に０～３の整数であり、０～２の整数であることが好ましく、０または１であることがより好ましく、０であることがさらに好ましい。 In group (A), R y is each independently an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group which may have a substituent, and a methyl group, It is preferably at least one selected from the group consisting of ethyl group, propyl group, methoxy group, ethoxy group, and phenyl group.
ny is each independently an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0.
　本実施形態においては、群（Ａ）中、
が好ましい。 In this embodiment, in group (A),
is preferred.
　また、式（Ｍ）中、ｎは、繰返し数の平均値であり、１．００≦ｎ≦２０．００を表す。
　ｎは、１．０５以上（１．０５≦ｎ）であることが好ましく、１．１０以上（１．１０≦ｎ）であることがより好ましく、１．２０以上（１．２０≦ｎ）であることがさらに好ましく、１．２５以上（１．２５≦ｎ）であることが一層好ましく、１．３０以上（１．３０≦ｎ）であることがより一層好ましく、１．５０以上（１．５０≦ｎ）であることがさらに一層好ましい。前記下限値以上であることにより、式（Ｍ）で表される化合物（Ｍ）の低誘電特性（Ｄｋおよび／またはＤｆ）が向上する傾向にあり、これを用いる樹脂組成物ないし得られる硬化物の低誘電特性（Ｄｋおよび／またはＤｆ）も向上する傾向にある。特に、１．００≦ｎとすることにより、式（Ｍ）で表される化合物（Ｍ）の結晶性が低下するため、溶剤溶解性が向上する傾向にある。また、ｎは、１０．００以下（ｎ≦１０．００）であることが好ましく、５．００以下（ｎ≦５．００）であることがより好ましく、３．００以下（ｎ≦３．００）であることがさらに好ましく、２．７５以下（ｎ≦２．７５）であることが一層好ましく、２．５０以下（ｎ≦２．５０）であることがより一層好ましい。前記上限値以下であることにより、式（Ｍ）で表される化合物（Ｍ）を含む樹脂組成物の粘度が低下し、含侵性が良好となり、成形性が優れる傾向にある。
　ｎの値は、例えば、式（Ｍ）で表される化合物（Ｍ）のゲルパーミエーションクロマトグラフィ（ＧＰＣ、検出器：ＲＩ）の測定により求められた数平均分子量、あるいは分離したピークの各々の面積比から算出することができる。 Further, in formula (M), n is the average value of the number of repetitions, and represents 1.00≦n≦20.00.
n is preferably 1.05 or more (1.05≦n), more preferably 1.10 or more (1.10≦n), and 1.20 or more (1.20≦n). It is more preferably 1.25 or more (1.25≦n), even more preferably 1.30 or more (1.30≦n), and even more preferably 1.50 or more (1.25≦n). It is even more preferable that 50≦n). By being at least the above lower limit, the low dielectric properties (Dk and/or Df) of the compound (M) represented by the formula (M) tend to improve, and the resin composition using the same or the resulting cured product The low dielectric properties (Dk and/or Df) of these materials also tend to improve. In particular, by setting 1.00≦n, the crystallinity of the compound (M) represented by formula (M) decreases, so that the solvent solubility tends to improve. Further, n is preferably 10.00 or less (n≦10.00), more preferably 5.00 or less (n≦5.00), and 3.00 or less (n≦3.00). ), more preferably 2.75 or less (n≦2.75), even more preferably 2.50 or less (n≦2.50). When it is below the upper limit, the viscosity of the resin composition containing the compound (M) represented by formula (M) decreases, the impregnation property becomes good, and the moldability tends to be excellent.
The value of n is, for example, the number average molecular weight determined by gel permeation chromatography (GPC, detector: RI) of the compound (M) represented by formula (M), or the area of each separated peak. It can be calculated from the ratio.
　本実施形態において、式（Ｍ）で表される化合物（Ｍ）は、式（Ｍ－１）で表される化合物を含むことが好ましい。
（式（Ｍ－１）中、Ｒは、それぞれ独立に、ハロゲン原子で置換されていてもよい炭素数１～１０の炭化水素基を表す。ｍは、０～３の整数を表し、ｎは、繰返し数の平均値であり、１．００≦ｎ≦２０．００を表す。） In this embodiment, the compound (M) represented by formula (M) preferably includes a compound represented by formula (M-1).
(In formula (M-1), R each independently represents a hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a halogen atom, m represents an integer of 0 to 3, and n represents , is the average value of the number of repetitions, and represents 1.00≦n≦20.00.)
　式（Ｍ－１）中、Ｒ、ｍ、およびｎは、それぞれ、式（Ｍ）におけるＲ、ｍ、およびｎと同義であり、好ましい範囲も同様である。 In formula (M-1), R, m, and n have the same meanings as R, m, and n in formula (M), respectively, and the preferred ranges are also the same.
　本実施形態においては、式（Ｍ）で表される化合物（Ｍ）は、式（Ｍ－２）で表される化合物を含むことがより好ましい。
（式（Ｍ－２）中、Ｒｚは、それぞれ独立に、炭素数１～１０の炭化水素基を表す。ｍは０～３の整数を表し、ｎは、繰返し数の平均値であり、１．００≦ｎ≦２０．００を表す。） In this embodiment, the compound (M) represented by formula (M) more preferably includes a compound represented by formula (M-2).
(In formula (M-2), R z each independently represents a hydrocarbon group having 1 to 10 carbon atoms, m represents an integer of 0 to 3, n is the average value of the number of repeats, 1.00≦n≦20.00)
　式（Ｍ－２）中、ｍおよびｎは、それぞれ、式（Ｍ）におけるｍおよびｎと同義であり、好ましい範囲も同様である。
　Ｒｚは、炭素数１～１０の炭化水素基であり、炭素数１～１０のアルキル基、または、フェニル基であることが好ましく、ハロゲン原子で置換されていてもよい、メチル基、エチル基、プロピル基（好ましくはイソプロピル基）、ブチル基（好ましくは、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基）、およびフェニル基からなる群より選択される少なくとも１種であることがより好ましい。 In formula (M-2), m and n have the same meanings as m and n in formula (M), respectively, and the preferred ranges are also the same.
R z is a hydrocarbon group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms or a phenyl group, and a methyl group or ethyl group which may be substituted with a halogen atom. , a propyl group (preferably an isopropyl group), a butyl group (preferably a sec-butyl group, a tert-butyl group), and a phenyl group.
　本実施形態においては、式（Ｍ）で表される化合物（Ｍ）（好ましくは、式（Ｍ）で表される化合物（Ｍ）に含まれるｎ＝１体において）が、２つある末端のマレイミド基と前記マレイミド基に最も近いＲｍｘ（好ましくは２，２－プロピリデン基）とが、いずれも、ベンゼン環に対してパラ位となるように位置している化合物（Ｍ－Ａ）と、２つある末端のマレイミド基の一方と前記マレイミド基に最も近いＲｍｘ（好ましくは２，２－プロピリデン基）が、ベンゼン環に対し、メタ位またはオルト位となるように位置し、他方のマレイミド基と、前記マレイミド基に最も近いＲｍｘ（好ましくは２，２－プロピリデン基）が、ベンゼン環に対してパラ位となるように位置している化合物（Ｍ－Ｂ）と、２つある末端のマレイミド基と前記マレイミド基に最も近いＲｍｘ（好ましくは２，２－プロピリデン基）とが、いずれも、ベンゼン環に対してメタ位またはオルト位となるように位置している化合物（Ｍ－Ｃ）とを含むことが好ましい。このように、化合物（Ｍ－Ａ）と、分子内におけるフェニレンマレイミド基部分の回転の自由度が高い、化合物（Ｍ－Ｂ）および化合物（Ｍ－Ｃ）とが混合する構成とすることにより、硬化反応の際における樹脂組成物中の架橋反応点の分布の自由度が高くなり、より強固なネットワークを有する樹脂硬化物が形成される傾向にある。結果として、得られる硬化物の耐熱性（例えば、ガラス転移温度）や低熱膨張性がより向上する傾向にある。
　上記化合物（Ｍ－Ｂ）および化合物（Ｍ－Ｃ）において、末端のマレイミド基とＲｍｘ（好ましくは２，２－プロピリデン基）とが、ベンゼン環に対し、オルト位となるように位置している化合物であることが好ましい。 In the present embodiment, the compound (M) represented by the formula (M) (preferably in the n=1 compound contained in the compound (M) represented by the formula (M)) has two terminals. A compound (MA) in which a maleimide group and the R mx (preferably a 2,2-propylidene group) closest to the maleimide group are both located at the para position with respect to the benzene ring; One of the two terminal maleimide groups and R mx (preferably a 2,2-propylidene group) closest to the maleimide group are located at the meta or ortho position with respect to the benzene ring, and the other maleimide group group, and a compound (MB) in which R mx (preferably a 2,2-propylidene group) closest to the maleimide group is located at the para position with respect to the benzene ring, and two terminals. A compound (M- C). In this way, by creating a configuration in which the compound (MA) is mixed with the compound (MB) and the compound (MC), which have a high degree of freedom of rotation of the phenylene maleimide group moiety in the molecule, The degree of freedom in the distribution of crosslinking reaction points in the resin composition during the curing reaction increases, and a cured resin product having a stronger network tends to be formed. As a result, the heat resistance (for example, glass transition temperature) and low thermal expansion of the resulting cured product tend to be further improved.
In the above compound (MB) and compound (MC), the terminal maleimide group and R mx (preferably 2,2-propylidene group) are located at the ortho position with respect to the benzene ring. It is preferable that the compound is
　本実施形態においては、ＨＰＬＣ分析において、式（Ｍ）で表される化合物（Ｍ）のうち、化合物（Ｍ－Ａ）の割合は、９０面積％以下であることが好ましく、８０面積％以下であることがより好ましく、７０面積％以下であることがさらに好ましく、５０面積％以下、３０面積％以下であってもよい。前記上限値以下とすることにより、結晶性が低下するため、溶剤溶解性が向上する傾向にある。また、化合物（Ｍ－Ａ）の割合は、０面積％であってもよいが、２面積％以上であることがより好ましく、５面積％以上であることがさらに好ましく、１０面積％以上であってもよい。化合物（Ｍ－Ａ）の割合を２面積％以上とすることにより、反応性の低下を効果的に抑制できる傾向にある。
　上記化合物（Ｍ－Ａ）の割合は、式（Ｍ）において、１．００≦ｎ≦５．００であるときに上記範囲を満たすことが好ましく、１．００≦ｎ≦３．００であるときに上記範囲を満たすことがより好ましく、ｎ＝１の時に上記範囲を満たすことがさらに好ましい。また、化合物（Ｍ－Ａ）が下記化合物を主成分として（例えば、式（Ｍ）で表される化合物（Ｍ）の２面積％以上の割合で）含むときに、上記範囲を満たすことが好ましい。
　本実施形態においては、ＨＰＬＣ分析において、式（Ｍ）で表される化合物（Ｍ）のうち、化合物（Ｍ－Ｂ）の割合は、６０面積％未満であることが好ましく、５５面積％未満であることが好ましい。前記上限値以下とすることにより、式（Ｍ）で表される化合物（Ｍ）の製造コストや産業廃棄物の減少を図ることができる傾向にある。また、化合物（Ｍ－Ｂ）の割合は、３０面積％以上であることが好ましく、３５面積％以上であることがより好ましく、４０面積％以上であることがさらに好ましい。非対称構造を有する化合物（Ｍ－Ｂ）の割合が３０面積％以上であることにより溶剤溶解性が向上するほか、得られる硬化物の低誘電特性（Ｄｋおよび／またはＤｆ）が向上する傾向にある。
　上記、化合物（Ｍ－Ｂ）の割合は、式（Ｍ）において、１．００≦ｎ≦５．００であるときに上記範囲を満たすことが好ましく、１．００≦ｎ≦３．００であるときに上記範囲を満たすことがより好ましい。また、化合物（Ｍ－Ｂ）が下記化合物を主成分として（例えば、式（Ｍ）で表される化合物（Ｍ）の３０質量％以上の割合で）含むときに上記範囲を満たすことが好ましい。
In the present embodiment, in HPLC analysis, the proportion of compound (MA) in compound (M) represented by formula (M) is preferably 90 area% or less, and 80 area% or less. It is more preferable that the amount is 70 area % or less, and it may be 50 area % or less, or 30 area % or less. When the content is below the upper limit, crystallinity decreases, so solvent solubility tends to improve. Further, the proportion of the compound (M-A) may be 0 area%, but is more preferably 2 area% or more, even more preferably 5 area% or more, and even more preferably 10 area% or more. It's okay. By setting the proportion of compound (MA) to 2% by area or more, it tends to be possible to effectively suppress a decrease in reactivity.
The proportion of the compound (MA) in formula (M) preferably satisfies the above range when 1.00≦n≦5.00, and when 1.00≦n≦3.00. It is more preferable that the above range is satisfied when n=1, and even more preferable that the above range is satisfied when n=1. Further, when the compound (M-A) contains the following compound as a main component (for example, in a proportion of 2% by area or more of the compound (M) represented by the formula (M)), it is preferable that the above range is satisfied. .
In this embodiment, in HPLC analysis, the proportion of compound (MB) among compound (M) represented by formula (M) is preferably less than 60 area %, and less than 55 area %. It is preferable that there be. By setting it below the above-mentioned upper limit, there is a tendency that it is possible to reduce the manufacturing cost of the compound (M) represented by the formula (M) and the amount of industrial waste. Further, the proportion of the compound (MB) is preferably 30 area % or more, more preferably 35 area % or more, and even more preferably 40 area % or more. When the proportion of the compound (MB) having an asymmetric structure is 30% by area or more, not only the solvent solubility is improved, but also the low dielectric properties (Dk and/or Df) of the obtained cured product tend to be improved. .
The ratio of the compound (MB) in formula (M) preferably satisfies the above range when 1.00≦n≦5.00, and 1.00≦n≦3.00. In some cases, it is more preferable to satisfy the above range. Further, it is preferable that the above range is satisfied when the compound (MB) contains the following compound as a main component (for example, in a proportion of 30% by mass or more of the compound (M) represented by the formula (M)).
　本実施形態においては、ＨＰＬＣ分析において、式（Ｍ）で表される化合物（Ｍ）のうち、化合物（Ｍ－Ｃ）の割合は、６０面積％未満であることが好ましく、５０面積％未満であることが好ましい。また、化合物（Ｍ－Ｃ）の割合は、１５面積％以上であることが好ましく、２５面積％以上であることがより好ましい。化合物（Ｍ－Ｃ）の割合が、１５面積％以上であることで低誘電特性（Ｄｋおよび／またはＤｆ）により優れ、６０面積％未満であることで硬化性や密着性が良好となり、基板等の作製時の不具合を効果的に抑制できる。
　上記、化合物（Ｍ－Ｃ）の割合は、式（Ｍ）において、１．００≦ｎ≦５．００であるときに上記範囲を満たすことが好ましく、１．００≦ｎ≦３．００であるときに上記範囲を満たすことがより好ましい。また、化合物（Ｍ－Ｃ）が下記化合物を主成分として（例えば、式（Ｍ）で表される化合物の１５質量％以上の割合で）含むときに上記範囲を満たすことが好ましい。
In the present embodiment, in HPLC analysis, the proportion of compound (MC) in compound (M) represented by formula (M) is preferably less than 60 area%, and less than 50 area%. It is preferable that there be. Further, the proportion of the compound (MC) is preferably 15 area % or more, more preferably 25 area % or more. When the proportion of the compound (MC) is 15 area% or more, it has excellent low dielectric properties (Dk and/or Df), and when it is less than 60 area%, it has good curability and adhesion, and it can be used for substrates, etc. Defects during production can be effectively suppressed.
The above ratio of compound (MC) preferably satisfies the above range when 1.00≦n≦5.00 in formula (M), and 1.00≦n≦3.00. In some cases, it is more preferable to satisfy the above range. Further, it is preferable that the above range is satisfied when the compound (MC) contains the following compound as a main component (for example, in a proportion of 15% by mass or more of the compound represented by the formula (M)).
　また、結晶性の問題、および電気特性悪化の問題においては、化合物（Ｍ－Ａ）の影響が大きいことから、式（Ｍ）で表される化合物（Ｍ）中の化合物（Ｍ－Ｂ）と化合物（Ｍ－Ｃ）の合計比率は、化合物（Ｍ－Ａ）、化合物（Ｍ－Ｂ）、および化合物（Ｍ－Ｃ）の合計量に対して、５０面積％以上であることが好ましく、６０面積％以上であることがさらに好ましく、７０面積％以上であることが特に好ましい。上限は、例えば、１００面積％以下、さらには、９９面積％以下であってもよい。
　特に、式（Ｍ）において、１．００≦ｎ≦５．００であるときに上記範囲を満たすことが好ましく、１．００≦ｎ≦３．００であるときに上記範囲を満たすことがより好ましい。 In addition, since the compound (M-A) has a large influence on the problem of crystallinity and the problem of deterioration of electrical properties, the compound (M-B) in the compound (M) represented by the formula (M) The total ratio of the compound (MC) is preferably 50 area% or more, and 60% by area or more based on the total amount of the compound (MA), the compound (MB), and the compound (MC). It is more preferably at least 70% by area, particularly preferably at least 70% by area. The upper limit may be, for example, 100 area % or less, or even 99 area % or less.
In particular, in formula (M), it is preferable that the above range is satisfied when 1.00≦n≦5.00, and it is more preferable that the above range is satisfied when 1.00≦n≦3.00. .
　式（Ｍ）で表される化合物（Ｍ）のＪＩＳ　Ｋ－７２３４に準じた方法で測定した軟化点は、５０℃以上であることが好ましく、より好ましくは８０℃以上であり、さらに好ましくは９０℃以上であり、特に好ましくは９５℃以上である。軟化点は１５０℃以下であることが好ましく、より好ましくは１４０℃以下であり、さらに好ましくは１３０℃以下であり、一層好ましくは１２０℃以下であり、１１０℃以下、１００℃以下であってもよい。 The softening point of the compound (M) represented by formula (M) measured by a method according to JIS K-7234 is preferably 50°C or higher, more preferably 80°C or higher, and even more preferably 90°C or higher. ℃ or higher, particularly preferably 95℃ or higher. The softening point is preferably 150°C or lower, more preferably 140°C or lower, even more preferably 130°C or lower, even more preferably 120°C or lower, even if it is 110°C or lower or 100°C or lower. good.
　式（Ｍ）で表される化合物（Ｍ）の酸価は、３０ｍｇＫＯＨ／ｇ以下であることが好ましく、１～１５ｍｇＫＯＨ／ｇであることがさらに好ましい。酸価が高いと、マレイミド化されていない分子が多く、カルボン酸を有する構造が過剰となってしまうことから、電気特性や耐水性に影響を及ぼす。 The acid value of the compound (M) represented by formula (M) is preferably 30 mgKOH/g or less, more preferably 1 to 15 mgKOH/g. When the acid value is high, there are many molecules that are not converted into maleimide, and structures having carboxylic acid become excessive, which affects electrical properties and water resistance.
　式（Ｍ）で表される化合物（Ｍ）の重量平均分子量（Ｍｗ）は、５００以上であることが好ましく、さらには、６００以上、７００以上であってもよい。前記下限値以上とすることにより、得られる硬化物の低誘電特性（Ｄｋおよび／またはＤｆ）および低吸水性がより向上する傾向にある。式（Ｍ）で表される化合物（Ｍ）の重量平均分子量（Ｍｗ）の上限は、１００００以下であることが好ましく、９０００以下であることがより好ましく、７０００以下であることがさらに好ましく、５０００以下であることが一層好ましく、３０００以下であることがより一層好ましく、１０００以下であることがさらに一層好ましい。前記上限値以下とすることにより、得られる硬化物の耐熱性および取り扱い性がより向上する傾向にある。 The weight average molecular weight (Mw) of the compound (M) represented by formula (M) is preferably 500 or more, and further may be 600 or more, or 700 or more. When the amount is equal to or more than the lower limit, the resulting cured product tends to have better low dielectric properties (Dk and/or Df) and low water absorption. The upper limit of the weight average molecular weight (Mw) of the compound (M) represented by formula (M) is preferably 10,000 or less, more preferably 9,000 or less, even more preferably 7,000 or less, and even more preferably 5,000 or less. It is more preferably below, even more preferably 3000 or less, even more preferably 1000 or less. By setting it below the above-mentioned upper limit, the heat resistance and handleability of the obtained cured product tend to be further improved.
　式（Ｍ）で表される化合物（Ｍ）の合成方法は、国際公開第２０２０－０５４６０１号の記載および国際公開第２０２１－１８２３６０号の記載を参酌でき、これらの内容は本明細書に組み込まれる。これらの公報に記載の方法で、式（Ｍ）で表される化合物（Ｍ）を合成すると、式（Ｍ）で表される化合物（Ｍ）は、化合物（Ｍ－Ａ）と化合物（Ｍ－Ｂ）と化合物（Ｍ－Ｃ）の混合物として得られる。
　また、式（Ｍ）で表される化合物（Ｍ）としては、市販品を用いてもよく、例えば、日本化薬社製、ＭＩＲ－５０００（式（Ｍ－２）において、ｍ＝０の化合物）が挙げられる。ＭＩＲ－５０００も上記公報に記載の方法によって合成できる。 For the synthesis method of compound (M) represented by formula (M), the description in International Publication No. 2020-054601 and the description in International Publication No. 2021-182360 can be considered, and the contents of these are incorporated herein. . When compound (M) represented by formula (M) is synthesized by the method described in these publications, compound (M) represented by formula (M) is synthesized by compound (M-A) and compound (M- B) and compound (MC) are obtained as a mixture.
Furthermore, as the compound (M) represented by the formula (M), a commercially available product may be used. For example, a compound of m=0 in MIR-5000 (formula (M-2) manufactured by Nippon Kayaku Co., Ltd.) ). MIR-5000 can also be synthesized by the method described in the above publication.
　本実施形態の樹脂組成物は、樹脂組成物中の樹脂固形分を１００質量部としたとき、式（Ｍ）で表される化合物（Ｍ）の含有量が５～５０質量部であることが好ましい。式（Ｍ）で表される化合物（Ｍ）の含有量の下限値は、樹脂組成物中の樹脂固形分１００質量部に対し、５質量部以上であることが好ましく、７質量部以上であることがより好ましく、１０質量部以上であることがさらに好ましく、１５質量部以上であることが一層好ましく、１８質量部以上であることがより一層好ましい。式（Ｍ）で表される化合物（Ｍ）の含有量が５質量部以上であることにより、得られる硬化物の低誘電特性（Ｄｋおよび／またはＤｆ、特に低誘電正接性）、金属箔ピール強度が向上する傾向にある。また、式（Ｍ）で表される化合物（Ｍ）の含有量の上限値は、樹脂組成物中の樹脂固形分１００質量部に対し、５０質量部以下であることが好ましく、４５質量部以下であることがより好ましく、４０質量部以下であることがさらに好ましく、３５質量部以下であることが一層好ましく、３０質量部以下であってもよく、２５質量部以下であってもよい。式（Ｍ）で表される化合物（Ｍ）の含有量が５０質量部以下であることにより、得られる硬化物の耐熱性および吸湿耐熱性がより向上する傾向にある。
　本実施形態における樹脂組成物は、式（Ｍ）で表される化合物（Ｍ）を１種のみ含んでいてもよいし、２種以上含んでいてもよい。２種以上含む場合、合計量が上記範囲となることが好ましい。 In the resin composition of the present embodiment, the content of the compound (M) represented by formula (M) is 5 to 50 parts by mass when the resin solid content in the resin composition is 100 parts by mass. preferable. The lower limit of the content of the compound (M) represented by formula (M) is preferably 5 parts by mass or more, and preferably 7 parts by mass or more, based on 100 parts by mass of the resin solid content in the resin composition. The amount is more preferably 10 parts by mass or more, even more preferably 15 parts by mass or more, and even more preferably 18 parts by mass or more. When the content of the compound (M) represented by formula (M) is 5 parts by mass or more, the obtained cured product has low dielectric properties (Dk and/or Df, especially low dielectric loss tangent), and metal foil peelability. Strength tends to improve. Further, the upper limit of the content of the compound (M) represented by formula (M) is preferably 50 parts by mass or less, and 45 parts by mass or less, based on 100 parts by mass of the resin solid content in the resin composition. The amount is more preferably 40 parts by mass or less, even more preferably 35 parts by mass or less, may be 30 parts by mass or less, and may be 25 parts by mass or less. When the content of the compound (M) represented by formula (M) is 50 parts by mass or less, the heat resistance and moisture absorption heat resistance of the obtained cured product tend to be further improved.
The resin composition in this embodiment may contain only one type of compound (M) represented by formula (M), or may contain two or more types. When two or more types are included, it is preferable that the total amount falls within the above range.
＜式（Ｖ）で表される構成単位を有する重合体（Ｖ）＞
　本実施形態の樹脂組成物は、式（Ｖ）で表される構成単位を有する重合体（Ｖ）を含む。式（Ｖ）で表される構成単位を有する重合体（Ｖ）を含むことにより、低誘電特性（低誘電率、低誘電正接）に優れた樹脂組成物が得られる。特に、式(Ｍ)で表される化合物(Ｍ)と組み合わせて用いることにより、強固なネットワークを有する樹脂硬化物が形成されるため、低誘電特性（Ｄｋおよび／またはＤｆ）に優れつつ、低熱膨張係数（低ＣＴＥ）にも優れると推測される。
 （式（Ｖ）中、Ａｒは芳香族炭化水素連結基を表す。＊は、結合位置を表す。） <Polymer (V) having a structural unit represented by formula (V)>
The resin composition of this embodiment includes a polymer (V) having a structural unit represented by formula (V). By including the polymer (V) having the structural unit represented by formula (V), a resin composition having excellent low dielectric properties (low dielectric constant, low dielectric loss tangent) can be obtained. In particular, when used in combination with the compound (M) represented by formula (M), a cured resin product with a strong network is formed, so it has excellent low dielectric properties (Dk and/or Df) and low heat resistance. It is also presumed to have an excellent coefficient of expansion (low CTE).
(In formula (V), Ar represents an aromatic hydrocarbon linking group. * represents the bonding position.)
　芳香族炭化水素連結基は、置換基を有していてもよい芳香族炭化水素のみからなる基であってもよいし、置換基を有していてもよい芳香族炭化水素と他の連結基の組み合わせからなる基であってもよい。芳香族炭化水素連結基は、置換基を有していてもよい芳香族炭化水素のみからなる基であることが好ましい。なお、芳香族炭化水素が有していてもよい置換基は、置換基Ｚ（例えば、炭素数１～６のアルキル基、炭素数２～６のアルケニル基、炭素数２～６のアルキニル基、炭素数１～６のアルコキシ基、ヒドロキシ基、アミノ基、カルボキシ基、ハロゲン原子等）が挙げられる。また、上記芳香族炭化水素は、置換基を有さない方が好ましい。
　芳香族炭化水素連結基は、通常、２価の連結基である。 The aromatic hydrocarbon linking group may be a group consisting only of an aromatic hydrocarbon that may have a substituent, or a group consisting of an aromatic hydrocarbon that may have a substituent and another linking group. It may be a group consisting of a combination of. The aromatic hydrocarbon linking group is preferably a group consisting only of aromatic hydrocarbons that may have substituents. The substituent that the aromatic hydrocarbon may have is a substituent Z (for example, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, hydroxy groups, amino groups, carboxy groups, halogen atoms, etc.). Further, it is preferable that the aromatic hydrocarbon has no substituent.
The aromatic hydrocarbon linking group is usually a divalent linking group.
　芳香族炭化水素連結基は、具体的には、置換基を有していてもよい、フェニレン基、ナフタレンジイル基、アントラセンジイル基、フェナントレンジイル基、ビフェニルジイル基、フルオレンジイル基が挙げられ、中でも置換基を有していてもよいフェニレン基が好ましい。置換基は、上述の置換基Ｚが例示されるが、上述したフェニレン基等の基は置換基を有さない方が好ましい。 Specific examples of the aromatic hydrocarbon linking group include a phenylene group, a naphthalenediyl group, an anthracenediyl group, a phenanthrenediyl group, a biphenyldiyl group, and a fluorenediyl group, which may have a substituent, Among these, a phenylene group which may have a substituent is preferred. The above-mentioned substituent Z is exemplified as the substituent, but it is preferable that groups such as the above-mentioned phenylene group have no substituent.
　式（Ｖ）で表される構成単位は、下記式（Ｖ１）で表される構成単位、下記式（Ｖ２）で表される構成単位、および、下記式（Ｖ３）で表される構成単位の少なくとも１つを含むことがより好ましい。なお、下記式中の＊は結合位置を表す。また、以下、式（Ｖ１）～（Ｖ３）で表される構成単位をまとめて、「構成単位（ａ）」ということがある。 The structural unit represented by formula (V) is the structural unit represented by the following formula (V1), the structural unit represented by the following formula (V2), and the structural unit represented by the following formula (V3). More preferably, at least one is included. Note that * in the following formula represents the bonding position. Further, hereinafter, the constituent units represented by formulas (V1) to (V3) may be collectively referred to as "constituent unit (a)."
　式（Ｖ１）～（Ｖ３）中、Ｌ１は芳香族炭化水素連結基（炭素数６～２２が好ましく、６～１８がより好ましく、６～１０がさらに好ましい）である。具体的には、置換基を有していてもよい、フェニレン基、ナフタレンジイル基、アントラセンジイル基、フェナントレンジイル基、ビフェニルジイル基、フルオレンジイル基が挙げられ、中でも置換基を有していてもよいフェニレン基が好ましい。置換基は、上述の置換基Ｚが例示されるが、上述したフェニレン基等の基は置換基を有さない方が好ましい。
　構成単位（ａ）を形成する化合物としては、ジビニル芳香族化合物であることが好ましく、例えば、ジビニルベンゼン、ビス（１－メチルビニル）ベンゼン、ジビニルナフタレン、ジビニルアントラセン、ジビニルビフェニル、ジビニルフェナントレンなどが挙げられる。中でもジビニルベンゼンが特に好ましい。これらのジビニル芳香族化合物は、１種を用いてもよく、必要に応じて２種以上を用いてもよい。 In formulas (V1) to (V3), L 1 is an aromatic hydrocarbon linking group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms). Specifically, examples include a phenylene group, a naphthalenediyl group, an anthracenediyl group, a phenanthrenediyl group, a biphenyldiyl group, and a fluorenediyl group, which may have a substituent. A phenylene group is preferred. The above-mentioned substituent Z is exemplified as the substituent, but it is preferable that groups such as the above-mentioned phenylene group have no substituent.
The compound forming the structural unit (a) is preferably a divinyl aromatic compound, such as divinylbenzene, bis(1-methylvinyl)benzene, divinylnaphthalene, divinylanthracene, divinylbiphenyl, divinylphenanthrene, etc. It will 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.
　式（Ｖ）で表される構成単位を有する重合体（Ｖ）は、上述のとおり、構成単位（ａ）の単独重合体であってもよいが、他のモノマー由来の構成単位との共重合体であってもよい。
　式（Ｖ）で表される構成単位を有する重合体（Ｖ）は、共重合体であるとき、その共重合比は、構成単位（ａ）が３モル％以上であることが好ましく、５モル％以上であることがより好ましく、１０モル％以上であることがさらに好ましく、１５モル％以上であってもよい。上限値としては、９０モル％以下であることが好ましく、８５モル％以下であることがより好ましく、８０モル％以下であることがさらに好ましく、７０モル％以下であることが一層好ましく、６０モル％以下であることがより好ましく、５０モル％以下であることがさらに一層好ましく、４０モル％以下であることがさらによりさらに一層好ましく、３０モル％以下であることが特に一層好ましく、さらには、２５モル％以下、２０モル％以下であってもよい。 As mentioned above, the polymer (V) having the structural unit represented by formula (V) may be a homopolymer of the structural unit (a), but it may also be a copolymer with a structural unit derived from another monomer. It may be a combination.
When the polymer (V) having the structural unit represented by formula (V) is a copolymer, the copolymerization ratio of the structural unit (a) is preferably 3 mol % or more, and 5 mol % or more. % 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. % or less, even more preferably 50 mol% or less, even more preferably 40 mol% or less, even more preferably 30 mol% or less, and furthermore, It may be 25 mol% or less, or 20 mol% or less.
　他のモノマー由来の構成単位としては、１つのビニル基を有する芳香族化合物（モノビニル芳香族化合物）に由来する構成単位（ｂ）が例示される。 As the structural unit derived from other monomers, the structural unit (b) derived from an aromatic compound having one vinyl group (monovinyl aromatic compound) is exemplified.
　モノビニル芳香族化合物に由来する構成単位（ｂ）は、下記式（Ｖ４）で表される構成単位であることが好ましい。 The structural unit (b) derived from the monovinyl aromatic compound is preferably a structural unit represented by the following formula (V4).
　式（Ｖ４）中、Ｌ２は芳香族炭化水素連結基であり、好ましいものの具体例としては、上記Ｌ１の例が挙げられる。
　ＲＶ１は水素原子または炭素数１～１２の炭化水素基（好ましくはアルキル基）である。ＲＶ１が炭化水素基であるとき、その炭素数は１～６が好ましく、１～３がより好ましい。ＲＶ１およびＬ２は上述の置換基Ｚを有していてもよい。 In formula (V4), L 2 is an aromatic hydrocarbon linking group, and a preferred example is the above-mentioned example 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, its carbon number is preferably 1 to 6, more preferably 1 to 3. R V1 and L 2 may have the above-mentioned substituent Z.
　式（Ｖ）で表される構成単位を有する重合体（Ｖ）がモノビニル芳香族化合物に由来する構成単位（ｂ）を含む共重合体であるとき、モノビニル芳香族化合物の例としては、スチレン、ビニルナフタレン、ビニルビフェニルなどのビニル芳香族化合物；ｏ－メチルスチレン、ｍ－メチルスチレン、ｐ－メチルスチレン、ｏ，ｐ－ジメチルスチレン、ｏ－エチルビニルベンゼン、ｍ－エチルビニルベンゼン、ｐ－エチルビニルベンゼン、メチルビニルビフェニル、エチルビニルビフェニルなどの核アルキル置換ビニル芳香族化合物などが挙げられる。ここで例示したモノビニル芳香族化合物は適宜上述の置換基Ｚを有していてもよい。また、これらのモノビニル芳香族化合物は、１種を用いても２種以上を用いてもよい。 When the polymer (V) having the structural unit represented by formula (V) is a copolymer containing the structural unit (b) derived from a monovinyl aromatic compound, examples of the monovinyl aromatic compound include styrene, Vinyl aromatic compounds such as vinylnaphthalene and vinylbiphenyl; o-methylstyrene, m-methylstyrene, p-methylstyrene, o,p-dimethylstyrene, o-ethylvinylbenzene, m-ethylvinylbenzene, p-ethylvinyl Examples include nuclear alkyl-substituted vinyl aromatic compounds such as benzene, methylvinylbiphenyl, and ethylvinylbiphenyl. The monovinyl aromatic compound exemplified here may have the above-mentioned substituent Z as appropriate. Further, these monovinyl aromatic compounds may be used alone or in combination of two or more.
　式（Ｖ）で表される構成単位を有する重合体（Ｖ）が構成単位（ｂ）を含む共重合体であるとき、構成単位（ｂ）の共重合比は、１０モル％以上であることが好ましく、１５モル％以上であることがさらに好ましく、さらには、２０モル％以上、３０モル％以上、４０モル％以上、５０モル％以上、６０モル％以上、７０モル％以上、７５モル％以上であってもよい。上限値としては、９８モル％以下であることが好ましく、９０モル％以下であることがより好ましく、８５モル％以下であることがさらに好ましい。 When the polymer (V) having the structural unit represented by formula (V) is a copolymer containing the structural unit (b), the copolymerization ratio of the structural unit (b) shall be 10 mol% or more. is preferable, more preferably 15 mol% or more, furthermore 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%. It may be more than that. The upper limit is preferably 98 mol% or less, more preferably 90 mol% or less, and even more preferably 85 mol% or less.
　式（Ｖ）で表される構成単位を有する重合体（Ｖ）は、構成単位（ａ）および構成単位（ｂ）以外のその他の構成単位を有していてもよい。その他の構成単位としては、例えば、シクロオレフィン化合物に由来する構成単位（ｃ）などが挙げられる。シクロオレフィン化合物としては、環構造内に二重結合を有する炭化水素類が挙げられる。具体的に、シクロブテン、シクロペンテン、シクロヘキセン、シクロオクテンなどの単環の環状オレフィンの他、ノルボルネン、ジシクロペンタジエンなどのノルボルネン環構造を有する化合物、インデン、アセナフチレンなどの芳香族環が縮合したシクロオレフィン化合物などを挙げることができる。ノルボルネン化合物の例としては、特開２０１８－３９９９５号公報の段落００３７～００４３に記載のものが挙げられ、これの内容は本明細書に組み込まれる。なお、ここで例示したシクロオレフィン化合物はさらに上述の置換基Ｚを有していてもよい。 The polymer (V) having the structural unit represented by formula (V) may have other structural units other than the structural unit (a) and the structural unit (b). Examples of other structural units include a structural unit (c) derived from a cycloolefin compound. Examples of the cycloolefin compound 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 condensed with aromatic rings such as indene and acenaphthylene. etc. can be mentioned. Examples of norbornene compounds include those described in paragraphs 0037 to 0043 of JP-A-2018-39995, the contents of which are incorporated herein. In addition, the cycloolefin compound illustrated here may further have the above-mentioned substituent Z.
　式（Ｖ）で表される構成単位を有する重合体（Ｖ）が構成単位（ｃ）を含む共重合体であるとき、構成単位（ｃ）の共重合比は、１０モル％以上であることが好ましく、２０モル％以上であることがより好ましく、３０モル％以上であることがさらに好ましい。上限値としては、９０モル％以下であることが好ましく、８０モル％以下であることがより好ましく、７０モル％以下であることがさらに好ましく、５０モル％以下であってもよく、３０モル％以下であってもよい。 When the polymer (V) having the structural unit represented by formula (V) is a copolymer containing the structural unit (c), the copolymerization ratio of the structural unit (c) shall be 10 mol% or more. is preferable, more preferably 20 mol% or more, and even more preferably 30 mol% or more. The upper limit is preferably 90 mol% or less, more preferably 80 mol% or less, even more preferably 70 mol% or less, may be 50 mol% or less, and may be 30 mol% or less. It may be the following.
　式（Ｖ）で表される構成単位を有する重合体（Ｖ）には、さらに異なる重合性化合物（以下、他の重合性化合物ともいう）に由来する構成単位（ｄ）が組み込まれていてもよい。他の重合性化合物（単量体）としては、例えば、ビニル基を３つ含む化合物が挙げられる。具体的には、１，３，５－トリビニルベンゼン、１，３，５－トリビニルナフタレン、１，２，４－トリビニルシクロへキサンが挙げられる。あるいは、エチレングリコールジアクリレート、ブタジエン等が挙げられる。他の重合性化合物に由来する構成単位（ｄ）の共重合比は、３０モル％以下であることが好ましく、２０モル％以下であることがより好ましく、１０モル％以下であることがさらに好ましい。 Even if the polymer (V) having the structural unit represented by formula (V) further incorporates a structural unit (d) derived from a different polymerizable compound (hereinafter also referred to as other polymerizable compound). good. Examples of other polymerizable compounds (monomers) include 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, etc. may be mentioned. The copolymerization ratio of the structural unit (d) derived from another polymerizable compound is preferably 30 mol% or less, more preferably 20 mol% or less, and even more preferably 10 mol% or less. .
　式（Ｖ）で表される構成単位を有する重合体（Ｖ）の一実施形態として、構成単位（ａ）を必須とし、構成単位（ｂ）～（ｄ）の少なくとも１種を含む重合体が例示される。さらには、構成単位（ａ）～（ｄ）の合計が、全構成単位の９５モル％以上、さらには９８モル％以上を占める態様が例示される。
　式（Ｖ）で表される構成単位を有する重合体（Ｖ）の他の一実施形態として、構成単位（ａ）を必須とし、末端を除く全構成単位のうち、芳香族環を含む構成単位が９０モル％以上のものであることが好ましく、９５モル％以上のものであることがより好ましく、１００モル％のものであってもよい。
　なお、全構成単位当たりのモル％を算出するにあたり、１つの構成単位とは、式（Ｖ）で表される構成単位を有する重合体（Ｖ）の製造に使用する単量体（例えば、ジビニル芳香族化合物、モノビニル芳香族化合物など）１分子に由来するものとする。 As one embodiment of the polymer (V) having a structural unit represented by the formula (V), a polymer containing the structural unit (a) as essential and at least one of the structural units (b) to (d) is Illustrated. Furthermore, an embodiment is exemplified in which the total of structural units (a) to (d) accounts for 95 mol% or more, and further 98 mol% or more of the total structural units.
Another embodiment of the polymer (V) having a structural unit represented by formula (V) is a structural unit in which the structural unit (a) is essential and among all the structural units excluding the terminal, a structural unit containing an aromatic ring. is preferably 90 mol% or more, more preferably 95 mol% or more, and may be 100 mol%.
In addition, when calculating the mol% per total structural unit, one structural unit refers to the monomer used to produce the polymer (V) having the structural unit represented by formula (V) (for example, divinyl Aromatic compounds, monovinyl aromatic compounds, etc.) shall originate from one molecule.
　式（Ｖ）で表される構成単位を有する重合体（Ｖ）の製造方法は特に限定されず常法によればよいが、例えば、ジビニル芳香族化合物を含む原料を（必要により、モノビニル芳香族化合物、シクロオレフィン化合物等を共存させ）、ルイス酸触媒の存在下で重合させることが挙げられる。ルイス酸触媒としては、三フッ化ホウ素等の金属フッ化物またはその錯体を用いることができる。 The method for producing the polymer (V) having the structural unit represented by the formula (V) is not particularly limited and may be any conventional method. For example, a raw material containing a divinyl aromatic compound (if necessary, a monovinyl aromatic compound compound, cycloolefin compound, etc.) and polymerization in the presence of a Lewis acid catalyst. As the Lewis acid catalyst, a metal fluoride such as boron trifluoride or a complex thereof can be used.
　式（Ｖ）で表される構成単位を有する重合体（Ｖ）の鎖末端の構造は特に限定されないが、上記ジビニル芳香族化合物に由来する基について言うと、以下の式（Ｅ１）の構造を取ることが挙げられる。なお、式（Ｅ１）中のＬ１は上記式（Ｖ１）で規定したものと同じである。＊は結合位置を表す。
　　＊－ＣＨ＝ＣＨ－Ｌ１－ＣＨ＝ＣＨ２　　　（Ｅ１） The structure of the chain terminal of the polymer (V) having the structural unit represented by the formula (V) is not particularly limited, but when it comes to the group derived from the divinyl aromatic compound, the structure of the following formula (E1) is used. One example is taking. Note that L 1 in formula (E1) is the same as defined in formula (V1) above. * represents the bonding position.
*-CH=CH-L 1 -CH=CH 2 (E1)
　モノビニル芳香族化合物に由来する基が鎖末端となったときには、下記式（Ｅ２）の構造を取ることが挙げられる。式中のＬ２およびＲＶ１はそれぞれ前記の式（Ｖ４）で定義したものと同じ意味である。＊は結合位置を表す。
　　＊－ＣＨ＝ＣＨ－Ｌ２－ＲＶ１　　　（Ｅ２） When a group derived from a monovinyl aromatic compound becomes a chain terminal, a structure of the following formula (E2) may be adopted. L 2 and R V1 in the formula each have the same meaning as defined in the above formula (V4). * represents the bonding position.
*-CH=CH-L 2 -R V1 (E2)
　式（Ｖ）で表される構成単位を有する重合体（Ｖ）の分子量は、数平均分子量Ｍｎで、３００以上であることが好ましく、５００以上であることがより好ましく、１，０００以上であることがさらに好ましく、１，５００以上であることがより好ましい。上限としては、１３０，０００以下であることが好ましく、１２０，０００以下であることがより好ましく、１１０，０００以下であることがさらに好ましく、１００，０００以下であることがさらに好ましい。
　式（Ｖ）で表される構成単位を有する重合体（Ｖ）の分子量は、重量平均分子量Ｍｗで、３，０００以上であることが好ましく、５，０００以上であることがより好ましく、１０，０００以上であることがさらに好ましい。前記下限値以上とすることにより、式（Ｖ）で表される構成単位を有する重合体（Ｖ）が持つ優れた低誘電特性（Ｄｋおよび／またはＤｆ）、特にＤｆや吸湿後の誘電特性を、樹脂組成物の硬化物に効果的に発揮させることができる。上限としては１３０，０００以下であることが好ましく、１００，０００以下であることがより好ましく、８０，０００以下であることがさらに好ましく、５０，０００以下であることが一層好ましい。前記上限値以下とすることにより、プリプレグもしくは樹脂シートを回路形成基板に積層した際、埋め込み不良が起こりにくい傾向にある。
　重量平均分子量Ｍｗと数平均分子量Ｍｎの比で表される単分散度（Ｍｗ／Ｍｎ）は、１００以下であることが好ましく、５０以下であることがより好ましく、２０以下であることがさらに好ましい。下限値としては、１．１以上であることが実際的であり、５以上であることが好ましく、７以上であることがより好ましく、１０以上であることがさらに好ましい。
　上記ＭｗおよびＭｎは後述する実施例の記載に従って測定される。
　本実施形態の樹脂組成物が式（Ｖ）で表される構成単位を有する重合体（Ｖ）を２種以上含む場合、混合物のＭｗ、ＭｎならびにＭｗ／Ｍｎが上記範囲を満たすことが好ましい。 The molecular weight of the polymer (V) having a structural unit represented by formula (V) is preferably a number average molecular weight Mn of 300 or more, more preferably 500 or more, and 1,000 or more. More preferably, it is 1,500 or more. The upper limit is preferably 130,000 or less, more preferably 120,000 or less, even more preferably 110,000 or less, and even more preferably 100,000 or less.
The molecular weight of the polymer (V) having a structural unit represented by formula (V) is preferably 3,000 or more, more preferably 5,000 or more, in weight average molecular weight Mw, 10, More preferably, it is 000 or more. By setting the above lower limit value or more, the excellent low dielectric properties (Dk and/or Df) of the polymer (V) having the structural unit represented by formula (V), especially Df and the dielectric properties after moisture absorption, can be improved. , can be effectively exhibited in the cured product of the resin composition. The upper limit is preferably 130,000 or less, more preferably 100,000 or less, even more preferably 80,000 or less, and even more preferably 50,000 or less. By setting it below the above-mentioned upper limit, when a prepreg or a resin sheet is laminated on a circuit forming board, embedding failure tends to occur less easily.
The monodispersity (Mw/Mn) expressed by the ratio of weight average molecular weight Mw to 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 is practically 1.1 or more, preferably 5 or more, more preferably 7 or more, and even more preferably 10 or more.
The above Mw and Mn are measured in accordance with the description in the examples below.
When the resin composition of the present embodiment contains two or more kinds of polymers (V) having structural units represented by formula (V), it is preferable that Mw, Mn, and Mw/Mn of the mixture satisfy the above ranges.
　式（Ｖ）で表される構成単位を有する重合体（Ｖ）のビニル基の当量は、２００ｇ／ｅｑ．以上であることが好ましく、２３０ｇ／ｅｑ．以上であることがより好ましく、２５０ｇ／ｅｑ．以上であることがさらに好ましい。また、ビニル基の当量は、１２００ｇ／ｅｑ．以下であることが好ましく、１０００ｇ／ｅｑ．以下であることがより好ましく、さらには、８００ｇ／ｅｑ．以下、６００ｇ／ｅｑ．以下、４００ｇ／ｅｑ．以下、３００ｇ／ｅｑ．以下であってもよい。前記下限値以上とすることにより、樹脂組成物の保存安定性が向上し、樹脂組成物の流動性が向上する傾向にある。そのため、成形性が向上し、プリプレグ等の形成時にボイドが発生しにくくなり、より信頼性の高いプリント配線板が得られる傾向にある。一方、上記上限値以下とすることにより、得られる硬化物の耐熱性が向上する傾向にある。 The equivalent weight of vinyl groups in the polymer (V) having the structural unit represented by formula (V) is 200 g/eq. or more, preferably 230g/eq. More preferably, it is 250 g/eq. It is more preferable that it is above. Further, the equivalent weight of the vinyl group is 1200 g/eq. It is preferably less than 1000g/eq. It is more preferable that it is less than 800g/eq. Below, 600g/eq. Below, 400g/eq. Below, 300g/eq. It may be the following. By setting it to the above lower limit or more, the storage stability of the resin composition tends to improve, and the fluidity of the resin composition tends to improve. Therefore, moldability is improved, voids are less likely to occur during the formation of prepregs, etc., and a more reliable printed wiring board tends to be obtained. On the other hand, by setting it below the above upper limit, the heat resistance of the obtained cured product tends to improve.
　本明細書において式（Ｖ）で表される構成単位を有する重合体（Ｖ）については、国際公開第２０１７／１１５８１３号の段落００２９～００５８に記載の化合物およびその合成反応条件等、特開２０１８－０３９９９５号公報の段落００１３～００５８に記載の化合物およびその合成反応条件等、特開２０１８－１６８３４７号公報の段落０００８～００４３に記載の化合物およびその合成反応条件等、特開２００６－０７０１３６号公報の段落００１４～００４２に記載の化合物およびその合成反応条件等、特開２００６－０８９６８３号公報の段落００１４～００６１に記載の化合物およびその合成反応条件等、特開２００８－２４８００１号公報の段落０００８～００３６に記載の化合物およびその合成反応条件等を参照することができ、本明細書に組み込まれる。 In this specification, regarding the polymer (V) having a structural unit represented by formula (V), the compounds described in paragraphs 0029 to 0058 of International Publication No. 2017/115813 and their synthesis reaction conditions, etc. Compounds described in paragraphs 0013 to 0058 of JP-A-039995 and their synthesis reaction conditions, etc., compounds described in paragraphs 0008 to 0043 of JP-A-2018-168347 and their synthesis reaction conditions, etc., JP-A-2006-070136 Compounds described in paragraphs 0014 to 0042 of JP-A-2006-089683 and their synthesis reaction conditions, etc., compounds described in paragraphs 0014 to 0061 of JP-A No. 2006-089683 and their synthesis reaction conditions, etc., paragraphs 0008 to 0008 of JP-A-2008-248001. The compounds described in No. 0036, their synthesis reaction conditions, etc. can be referred to and are incorporated herein.
　本実施形態の樹脂組成物は、樹脂組成物中の樹脂固形分を１００質量部としたとき、式（Ｖ）で表される構成単位を有する重合体（Ｖ）の含有量が５～５０質量部であることが好ましい。 In the resin composition of the present embodiment, the content of the polymer (V) having a structural unit represented by formula (V) is 5 to 50 parts by mass when the resin solid content in the resin composition is 100 parts by mass. Preferably.
　式（Ｖ）で表される構成単位を有する重合体（Ｖ）の含有量の下限値は、樹脂組成物中の樹脂固形分を１００質量部としたとき、７質量部以上であることがより好ましく、９質量部以上であることがさらに好ましく、１０質量部以上であることが一層好ましく、１５質量部以上であることがより一層好ましい。他方、式（Ｖ）で表される構成単位を有する重合体（Ｖ）の含有量の上限値は、樹脂組成物中の樹脂固形分を１００質量部としたとき、４５質量部以下であることがより好ましく、４０質量部以下であることがさらに好ましく、３５質量部以下であることが一層好ましく、３０質量部以下であってもよく、２５質量部以下であってもよい。式（Ｖ）で表される構成単位を有する重合体（Ｖ）の含有量を上記下限値以上とすることで、得られる硬化物の低誘電特性（Ｄｋおよび／またはＤｆ）、デスミア耐性に優れる傾向にある。また、前記上限値以下とすることにより、得られる硬化物の金属箔ピール強度、吸湿耐熱性を効果的に高めることができる。 The lower limit of the content of the polymer (V) having a structural unit represented by formula (V) is preferably 7 parts by mass or more when the resin solid content in the resin composition is 100 parts by mass. It is preferably 9 parts by mass or more, more preferably 10 parts by mass or more, even more preferably 15 parts by mass or more. On the other hand, the upper limit of the content of the polymer (V) having a structural unit represented by formula (V) is 45 parts by mass or less when the resin solid content in the resin composition is 100 parts by mass. The amount is more preferably 40 parts by mass or less, even more preferably 35 parts by mass or less, may be 30 parts by mass or less, and may be 25 parts by mass or less. By setting the content of the polymer (V) having a structural unit represented by formula (V) to the above lower limit value or more, the resulting cured product has excellent low dielectric properties (Dk and/or Df) and desmear resistance. There is a tendency. Further, by setting the amount to be equal to or less than the above upper limit, the metal foil peel strength and moisture absorption heat resistance of the obtained cured product can be effectively improved.
　また、式（Ｖ）で表される構成単位を有する重合体（Ｖ）の含有量の下限値は、式（Ｍ）で表される化合物（Ｍ）１００質量部に対し、２０質量部以上であることが好ましく、３０質量部以上であることがより好ましく、４０質量部以上であることがさらに好ましく、５０質量部以上であることが一層好ましく、さらには、６０質量部以上、７０質量部以上、７５質量部以上、８０質量部以上であることが好ましく、用途等に応じて、８５質量部以上、９０質量部以上、９５質量部以上であってもよい。他方、式（Ｖ）で表される構成単位を有する重合体（Ｖ）の含有量の上限値は、式（Ｍ）で表される化合物（Ｍ）１００質量部に対し、６００質量部以下であることが好ましく、５００質量部以下であることがより好ましく、４００質量部以下であることがさらに好ましく、３００質量部以下であることが一層好ましく、さらには、２００質量部以下、１７０質量部以下、１５０質量部以下、１４０質量部以下、１３０質量部以下、１２５質量部以下であることが好ましく、用途等に応じて、１２０質量部以下、１１５質量部以下、１１０質量部以下、１０５質量部以下であってもよい。式（Ｖ）で表される構成単位を有する重合体（Ｖ）の含有量範囲を上記範囲に調整することで、低誘電特性（Ｄｋおよび／またはＤｆ、特に低誘電正接）、金属箔ピール強度、デスミア耐性、吸湿耐熱性に優れる傾向がある。
　式（Ｖ）で表される構成単位を有する重合体（Ｖ）は、樹脂組成物中に、１種のみ含まれていても、２種以上含まれていてもよい。２種以上含まれる場合は、合計量が上記範囲となることが好ましい。 In addition, the lower limit of the content of the polymer (V) having the structural unit represented by the formula (V) is 20 parts by mass or more with respect to 100 parts by mass of the compound (M) represented by the formula (M). The amount is preferably 30 parts by mass or more, more preferably 40 parts by mass or more, even more preferably 50 parts by mass or more, and furthermore 60 parts by mass or more, 70 parts by mass or more. , preferably 75 parts by mass or more, and 80 parts by mass or more, and may be 85 parts by mass or more, 90 parts by mass or more, or 95 parts by mass or more, depending on the application. On the other hand, the upper limit of the content of the polymer (V) having a structural unit represented by the formula (V) is 600 parts by mass or less per 100 parts by mass of the compound (M) represented by the formula (M). The amount is preferably 500 parts by mass or less, even more preferably 400 parts by mass or less, even more preferably 300 parts by mass or less, furthermore 200 parts by mass or less, and 170 parts by mass or less. , 150 parts by mass or less, 140 parts by mass or less, 130 parts by mass or less, 125 parts by mass or less, depending on the use etc., 120 parts by mass or less, 115 parts by mass or less, 110 parts by mass or less, 105 parts by mass. It may be the following. By adjusting the content range of the polymer (V) having the structural unit represented by formula (V) to the above range, low dielectric properties (Dk and/or Df, especially low dielectric loss tangent) and metal foil peel strength can be achieved. , tends to have excellent desmear resistance and moisture absorption and heat resistance.
The resin composition may contain only one type of polymer (V) having a structural unit represented by formula (V), or may contain two or more types. When two or more types are included, it is preferable that the total amount falls within the above range.
＜式（Ｍ１）で表される化合物（Ｍ１）＞
　本実施形態の樹脂組成物は、式（Ｍ１）で表される化合物（Ｍ１）を含む。上述した式（Ｍ）で表される化合物（Ｍ）と併用することにより、硬化反応が適切に進み、得られる樹脂組成物ないし硬化物等の耐熱性、吸湿耐熱性が向上する。
（式（Ｍ１）中、ＲＭ１、ＲＭ２、ＲＭ３、およびＲＭ４は、それぞれ独立に、水素原子または有機基を表す。ＲＭ５およびＲＭ６は、それぞれ独立に、水素原子またはアルキル基を表す。ＡｒＭは２価の芳香族基を表す。Ａは、４～６員環の脂環基である。ＲＭ７およびＲＭ８は、それぞれ独立に、アルキル基である。ｍｘは１または２であり、ｌｘは０または１である。ＲＭ９およびＲＭ１０は、それぞれ独立に、水素原子またはアルキル基を表す。ＲＭ１１、ＲＭ１２、ＲＭ１３、およびＲＭ１４は、それぞれ独立に、水素原子または有機基を表す。ＲＭ１５は、それぞれ独立に、炭素数１～１０のアルキル基、炭素数１～１０のアルキルオキシ基、炭素数１～１０のアルキルチオ基、炭素数６～１０のアリール基、炭素数６～１０のアリールオキシ基、炭素数６～１０のアリールチオ基、ハロゲン原子、水酸基またはメルカプト基を表す。ｐｘは０～３の整数を表す。ｎｘは１～２０の整数を表す。） <Compound (M1) represented by formula (M1)>
The resin composition of this embodiment contains a compound (M1) represented by formula (M1). When used in combination with the compound (M) represented by the formula (M) described above, the curing reaction proceeds appropriately, and the heat resistance and moisture absorption heat resistance of the resulting resin composition or cured product are improved.
(In formula (M1), R M1 , R M2 , R M3 , and R M4 each independently represent a hydrogen atom or an organic group. R M5 and R M6 each independently represent a hydrogen atom or an alkyl group. Ar M represents a divalent aromatic group. A 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 represents 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, or an aryl group having 6 to 10 carbon atoms. , represents an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a halogen atom, a hydroxyl group or a mercapto group. px represents an integer of 0 to 3. nx represents an integer of 1 to 20. )
　式中のＲＭ１、ＲＭ２、ＲＭ３、およびＲＭ４は、それぞれ独立に、水素原子または有機基を表す。ここでの有機基はアルキル基であることが好ましく、炭素数１～１２のアルキル基がより好ましく、炭素数１～６のアルキル基がさらに好ましく、メチル基、エチル基、プロピル基、ブチル基が一層好ましく、中でもメチル基が特に好ましい。ＲＭ１およびＲＭ３は、それぞれ独立に、アルキル基が好ましく、ＲＭ２およびＲＭ４は、水素原子が好ましい。
　ＲＭ５およびＲＭ６は、それぞれ独立に、水素原子またはアルキル基を表し、アルキル基が好ましい。ここでのアルキル基は、炭素数１～１２のアルキル基が好ましく、炭素数１～６のアルキル基がより好ましく、メチル基、エチル基、プロピル基、ブチル基がさらに好ましく、中でもメチル基が特に好ましい。
　ＡｒＭは２価の芳香族基を表し、好ましくはフェニレン基、ナフタレンジイル基、フェナントレンジイル基、アントラセンジイル基であり、より好ましくはフェニレン基であり、さらに好ましくはｍ－フェニレン基である。ＡｒＭは置換基を有していてもよく、置換基としては、アルキル基が好ましく、炭素数１～１２のアルキル基がより好ましく、炭素数１～６のアルキル基がさらに好ましく、メチル基、エチル基、プロピル基、ブチル基が一層好ましく、メチル基が特に好ましい。しかしながら、ＡｒＭは無置換であることが好ましい。
　Ａは、４～６員環の脂環基であり、５員の脂環基（好ましくはベンゼン環と合せてインダン環となる基）がより好ましい。ＲＭ７およびＲＭ８は、それぞれ独立に、アルキル基であり、炭素数１～６のアルキル基が好ましく、炭素数１～３のアルキル基がより好ましく、メチル基が特に好ましい。
　ｍｘは１または２であり、２であることが好ましい。
　ｌｘは０または１であり、１であることが好ましい。
　ＲＭ９およびＲＭ１０は、それぞれ独立に、水素原子またはアルキル基を表し、アルキル基がより好ましい。ここでのアルキル基は、炭素数１～１２のアルキル基が好ましく、炭素数１～６のアルキル基がより好ましく、メチル基、エチル基、プロピル基、ブチル基がさらに好ましく、中でもメチル基が特に好ましい。
　ＲＭ１１、ＲＭ１２、ＲＭ１３、およびＲＭ１４は、それぞれ独立に、水素原子または有機基を表す。ここでの有機基はアルキル基であることが好ましく、炭素数１～１２のアルキル基がより好ましく、炭素数１～６のアルキル基がさらに好ましく、メチル基、エチル基、プロピル基、ブチル基が一層好ましく、中でもメチル基が特に好ましい。ＲＭ１２およびＲＭ１３は、それぞれ独立に、アルキル基が好ましく、ＲＭ１１およびＲＭ１４は、水素原子が好ましい。
　ＲＭ１５は、それぞれ独立に、炭素数１～１０のアルキル基、炭素数１～１０のアルキルオキシ基、炭素数１～１０のアルキルチオ基、炭素数６～１０のアリール基、炭素数６～１０のアリールオキシ基、炭素数６～１０のアリールチオ基、ハロゲン原子、水酸基またはメルカプト基を表し、炭素数１～４のアルキル基、炭素数３～６のシクロアルキル基、または、炭素数６～１０のアリール基であることが好ましい。
　ｐｘは０～３の整数を表し、０～２の整数が好ましく、０または１がより好ましく、０がさらに好ましい。
　ｎｘは１～２０の整数を表す。ｎｘは１０以下の整数であってもよい。
　尚、本実施形態の樹脂組成物は、式（Ｍ１）で表される化合物（Ｍ１）であって、少なくともｎｘの値が異なる化合物を１種のみ含んでいてもよいし、２種以上含んでいてもよい。２種以上含む場合、樹脂組成物中の式（Ｍ１）で表される化合物（Ｍ１）におけるｎｘの平均値（平均繰返単位数）ｎは、低い融点（低軟化点）で、かつ溶融粘度が低く、ハンドリング性に優れたものとするため、０．９２以上であることが好ましく、０．９５以上であることがより好ましく、１．０以上であることがさらに好ましく、１．１以上であることが一層好ましい。また、ｎは、１０．０以下であることが好ましく、８．０以下であることがより好ましく、７．０以下であることがさらに好ましく、６．０以下であることが一層好ましく、５．０以下であってもよい。後述する式（Ｍ１－２）等についても同様である。 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, even more preferably an alkyl group having 1 to 6 carbon atoms, and a methyl group, an ethyl group, a propyl group, or a butyl group. More preferred is a methyl group, especially a methyl group. R M1 and R M3 are each independently preferably an alkyl group, and R M2 and R M4 are preferably a hydrogen atom.
R M5 and R M6 each independently represent a hydrogen atom or an alkyl group, preferably an alkyl group. The alkyl group here is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group, an ethyl group, a propyl group, or a butyl group, with a methyl group being particularly preferred. preferable.
Ar M represents a divalent aromatic group, preferably a phenylene group, a naphthalenediyl group, a phenanthrenediyl group, an anthracenediyl group, more preferably a phenylene group, still more preferably a m-phenylene group. Ar M may have a substituent, and the substituent is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, even more preferably an alkyl group having 1 to 6 carbon atoms, a methyl group, Ethyl group, propyl group, and butyl group are more preferable, and methyl group is particularly preferable. However, it is preferable that Ar M is unsubstituted.
A is a 4- to 6-membered alicyclic group, and more preferably a 5-membered alicyclic group (preferably a group that forms an indane ring when combined with a benzene ring). R M7 and R M8 each independently represent 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, and an alkyl group is more preferred. 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, and still more preferably a methyl group, an ethyl group, a propyl group, or a butyl group, with a methyl group being particularly preferred. preferable.
R M11 , R M12 , R M13 , and R M14 each independently represent a hydrogen atom or an organic group. The organic group here is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, even more preferably an alkyl group having 1 to 6 carbon atoms, and a methyl group, an ethyl group, a propyl group, or a butyl group. More preferred is a methyl group, especially a methyl group. R M12 and R M13 are each independently preferably an alkyl group, and R M11 and R M14 are preferably a hydrogen atom.
R M15 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. represents an aryloxy group, an arylthio group having 6 to 10 carbon atoms, a halogen atom, a hydroxyl group, or a mercapto group, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or a cycloalkyl group having 6 to 10 carbon atoms. is preferably an aryl group.
px represents an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0.
nx represents an integer from 1 to 20. nx may be an integer of 10 or less.
The resin composition of the present embodiment may contain only one type of compound (M1) represented by formula (M1), or may contain two or more types of compounds having at least different values of nx. You can stay there. When two or more types are included, the average value of nx (average number of repeating units) 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. In order to have a low value and excellent handling properties, it is preferably 0.92 or more, more preferably 0.95 or more, even more preferably 1.0 or more, and 1.1 or more. It is more preferable that there be. Further, n is preferably 10.0 or less, more preferably 8.0 or less, even more preferably 7.0 or less, even more preferably 6.0 or less, and 5. It may be 0 or less. The same applies to equations (M1-2) and the like that will be described later.
　式（Ｍ１）で表される化合物（Ｍ１）は、下記の式（Ｍ１－１）で表される化合物であることが好ましい。
（式（Ｍ１－１）中、ＲＭ２１、ＲＭ２２、ＲＭ２３、およびＲＭ２４は、それぞれ独立に、水素原子または有機基を表す。ＲＭ２５およびＲＭ２６は、それぞれ独立に、水素原子またはアルキル基を表す。ＲＭ２７、ＲＭ２８、ＲＭ２９、およびＲＭ３０は、それぞれ独立に、水素原子または有機基を表す。ＲＭ３１およびＲＭ３２は、それぞれ独立に、水素原子またはアルキル基を表す。ＲＭ３３、ＲＭ３４、ＲＭ３５、およびＲＭ３６は、それぞれ独立に、水素原子または有機基を表す。ＲＭ３７、ＲＭ３８、およびＲＭ３９は、それぞれ独立に、水素原子またはアルキル基を表す。ｎｘは１以上２０以下の整数を表す。） The compound (M1) represented by formula (M1) is preferably a compound represented by formula (M1-1) below.
(In 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 , R M34 , R M35 , and R M36 each independently represent a hydrogen atom or an organic group. R M37 , R M38 , and R M39 each independently represent a hydrogen atom or an alkyl group. nx is Represents an integer between 1 and 20.)
　式中のＲＭ２１、ＲＭ２２、ＲＭ２３、およびＲＭ２４は、それぞれ独立に、水素原子または有機基を表す。ここでの有機基はアルキル基であることが好ましく、炭素数１～１２のアルキル基がより好ましく、炭素数１～６のアルキル基がさらに好ましく、メチル基、エチル基、プロピル基、ブチル基が一層好ましく、メチル基が特に好ましい。ＲＭ２１およびＲＭ２３は、アルキル基が好ましく、ＲＭ２２およびＲＭ２４は、水素原子が好ましい。
　ＲＭ２５およびＲＭ２６は、それぞれ独立に、水素原子またはアルキル基を表し、アルキル基が好ましい。ここでのアルキル基は、炭素数１～１２のアルキル基が好ましく、炭素数１～６のアルキル基がより好ましく、メチル基、エチル基、プロピル基、ブチル基がさらに好ましく、中でもメチル基が特に好ましい。
　ＲＭ２７、ＲＭ２８、ＲＭ２９、およびＲＭ３０は、それぞれ独立に、水素原子または有機基を表し、水素原子が好ましい。ここでの有機基はアルキル基であることが好ましく、炭素数１～１２のアルキル基がより好ましく、炭素数１～６のアルキル基がさらに好ましく、メチル基、エチル基、プロピル基、ブチル基が一層好ましく、メチル基が特に好ましい。
　ＲＭ３１およびＲＭ３２は、それぞれ独立に、水素原子またはアルキル基を表し、アルキル基が好ましい。ここでのアルキル基は、炭素数１～１２のアルキル基が好ましく、炭素数１～６のアルキル基がより好ましく、メチル基、エチル基、プロピル基、ブチル基がさらに好ましく、中でもメチル基が特に好ましい。
　ＲＭ３３、ＲＭ３４、ＲＭ３５、およびＲＭ３６は、それぞれ独立に、水素原子または有機基を表す。ここでの有機基はアルキル基であることが好ましく、炭素数１～１２のアルキル基がより好ましく、炭素数１～６のアルキル基がさらに好ましく、メチル基、エチル基、プロピル基、ブチル基が一層好ましく、メチル基が特に好ましい。
　ＲＭ３３およびＲＭ３６は、水素原子が好ましく、ＲＭ３４およびＲＭ３５はアルキル基が好ましい。
　ＲＭ３７、ＲＭ３８、およびＲＭ３９は、それぞれ独立に、水素原子またはアルキル基を表し、アルキル基が好ましい。ここでのアルキル基は、炭素数１～１２のアルキル基が好ましく、炭素数１～６のアルキル基がより好ましく、メチル基、エチル基、プロピル基、ブチル基がさらに好ましく、中でもメチル基が特に好ましい。
　ｎｘは１以上２０以下の整数を表す。ｎｘは１０以下の整数であってもよい。 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, even more preferably an alkyl group having 1 to 6 carbon atoms, and a methyl group, an ethyl group, a propyl group, or a butyl group. More preferred is a methyl group. R M21 and R M23 are preferably alkyl groups, and R M22 and R M24 are preferably hydrogen atoms.
R M25 and R M26 each independently represent a hydrogen atom or an alkyl group, preferably an alkyl group. The alkyl group here is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group, an ethyl group, a propyl group, or a butyl group, with a methyl group being particularly preferred. preferable.
R M27 , R M28 , R M29 , and R M30 each independently represent a hydrogen atom or an organic group, and preferably a hydrogen atom. The organic group here is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, even more preferably an alkyl group having 1 to 6 carbon atoms, and a methyl group, an ethyl group, a propyl group, or a butyl group. More preferred is a methyl group.
R M31 and R M32 each independently represent a hydrogen atom or an alkyl group, preferably an alkyl group. The alkyl group here is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group, an ethyl group, a propyl group, or a butyl group, with a methyl group being particularly preferred. preferable.
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, even more preferably an alkyl group having 1 to 6 carbon atoms, and a methyl group, an ethyl group, a propyl group, or a butyl group. More preferred is a methyl 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, and an alkyl group is preferable. 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, and still more preferably a methyl group, an ethyl group, a propyl group, or a butyl group, with a methyl group being particularly preferred. preferable.
nx represents an integer from 1 to 20. nx may be an integer of 10 or less.
　式（Ｍ１－１）で表される化合物は、下記式（Ｍ１－２）で表される化合物であることが好ましい。
（式（Ｍ１－２）中、ＲＭ２１、ＲＭ２２、ＲＭ２３、およびＲＭ２４は、それぞれ独立に、水素原子または有機基を表す。ＲＭ２５およびＲＭ２６は、それぞれ独立に、水素原子またはアルキル基を表す。ＲＭ２７、ＲＭ２８、ＲＭ２９、およびＲＭ３０は、それぞれ独立に、水素原子または有機基を表す。ＲＭ３１およびＲＭ３２は、それぞれ独立に、水素原子またはアルキル基を表す。ＲＭ３３、ＲＭ３４、ＲＭ３５、およびＲＭ３６は、それぞれ独立に、水素原子または有機基を表す。ＲＭ３７、ＲＭ３８、およびＲＭ３９は、それぞれ独立に、水素原子またはアルキル基を表す。ｎｘは１以上２０以下の整数を表す。） The compound represented by formula (M1-1) is preferably a compound represented by formula (M1-2) below.
(In formula (M1-2), R M21 , R M22 , R M23 , and R M24 each independently represent a hydrogen atom or an organic group. R M25 and R M26 each independently represent a hydrogen atom or an alkyl R M27 , R M28 , R M29 , and R M30 each independently represent a hydrogen atom or an organic group. R M31 and R M32 each independently represent a hydrogen atom or an alkyl group. R M33 , R M34 , R M35 , and R M36 each independently represent a hydrogen atom or an organic group. R M37 , R M38 , and R M39 each independently represent a hydrogen atom or an alkyl group. nx is Represents an integer between 1 and 20.)
　式（Ｍ１－２）中、ＲＭ２１、ＲＭ２２、ＲＭ２３、ＲＭ２４、ＲＭ２５、ＲＭ２６、ＲＭ２７、ＲＭ２８、ＲＭ２９、ＲＭ３０、ＲＭ３１、ＲＭ３２、ＲＭ３３、ＲＭ３４、ＲＭ３５、ＲＭ３６、ＲＭ３７、ＲＭ３８、ＲＭ３９、および、ｎｘは、それぞれ、式（Ｍ１－１）におけるＲＭ２１、ＲＭ２２、ＲＭ２３、ＲＭ２４、ＲＭ２５、ＲＭ２６、ＲＭ２７、ＲＭ２８、ＲＭ２９、ＲＭ３０、ＲＭ３１、ＲＭ３２、ＲＭ３３、ＲＭ３４、ＲＭ３５、ＲＭ３６、ＲＭ３７、ＲＭ３８、ＲＭ３９、および、ｎｘと同義であり、好ましい範囲も同様である。 In formula (M1-2), RM21 , RM22 , RM23 , RM24 , RM25, RM26 , RM27 , RM28 , RM29 , RM30 , RM31 , RM32 , RM33 , RM34 , R M35 , R M36 , R M37 , R M38 , R M39 , and nx are R M21 , R M22 , R M23 , R M24 , R M25 , R M26 , R M27 in formula (M1-1), respectively; It is synonymous with 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, and the preferred ranges are also the same. .
　式（Ｍ１－１）で表される化合物は、下記式（Ｍ１－３）で表される化合物であることが好ましく、下記式（Ｍ１－４）で表される化合物であることがより好ましい。
（式（Ｍ１－３）中、ｎｘは１以上２０以下の整数を表す。）
　ｎｘは１０以下の整数であってもよい。
（式（Ｍ１－４）中、ｎｘは１以上２０以下の整数を表す。）
　ｎｘは１０以下の整数であってもよい。 The compound represented by the formula (M1-1) is preferably a compound represented by the following formula (M1-3), and more preferably a compound represented by the following formula (M1-4).
(In formula (M1-3), nx represents an integer from 1 to 20.)
nx may be an integer of 10 or less.
(In formula (M1-4), nx represents an integer from 1 to 20.)
nx may be an integer of 10 or less.
　式（Ｍ１）で表される化合物（Ｍ１）の分子量は、５００以上であることが好ましく、６００以上であることがより好ましく、７００以上であることがさらに好ましい。前記下限値以上とすることにより、得られる硬化物の低誘電特性（Ｄｋおよび／またはＤｆ）および低吸水性がより向上する傾向にある。また、式（Ｍ１）で表される化合物（Ｍ１）の分子量は、１００００以下であることが好ましく、９０００以下であることがより好ましく、７０００以下であることがさらに好ましく、５０００以下であることが一層好ましく、４０００以下であることがより一層好ましい。前記上限値以下とすることにより、得られる硬化物の耐熱性および取り扱い性がより向上する傾向にある。 The molecular weight of the 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 amount is equal to or more than the lower limit, the resulting cured product tends to have better low dielectric properties (Dk and/or Df) and low water absorption. Further, the molecular weight of the compound (M1) represented by formula (M1) is preferably 10,000 or less, more preferably 9,000 or less, even more preferably 7,000 or less, and preferably 5,000 or less. More preferably, it is 4000 or less. By setting it below the above-mentioned upper limit, the heat resistance and handleability of the obtained cured product tend to be further improved.
　本実施形態の樹脂組成物は、樹脂組成物中の樹脂固形分を１００質量部としたとき、式（Ｍ１）で表される化合物（Ｍ１）の含有量が、５～５０質量部であることが好ましい。式（Ｍ１）で表される化合物（Ｍ１）の含有量の下限値は、樹脂組成物中の樹脂固形分を１００質量部としたとき、５質量部以上であることが好ましく、７質量部以上であることがより好ましく、９質量部以上であることがさらに好ましく、１０質量部以上であることが一層好ましく、１５質量部以上であることがより一層好ましい。他方、式（Ｍ１）で表される化合物（Ｍ１）の含有量の上限値は、樹脂組成物中の樹脂固形分を１００質量部としたとき、５０質量部以下であることが好ましく、４０質量部以下であることがより好ましく、３５質量部以下であることがさらに好ましく、３０質量部以下であってもよく、２５質量部以下であってもよい。式（Ｍ１）で表される化合物（Ｍ１）を上記下限値以上とすることで、得られる硬化物の耐熱性、吸湿耐熱性が優れる傾向にある。また、前記上限値以下とすることにより、得られる硬化物の金属箔ピール強度、デスミア耐性を効果的に良好な範囲とすることができる。 In the resin composition of the present embodiment, the content of the compound (M1) represented by formula (M1) is 5 to 50 parts by mass when the resin solid content in the resin composition is 100 parts by mass. is preferred. The lower limit of the content of the compound (M1) represented by formula (M1) is preferably 5 parts by mass or more, and 7 parts by mass or more when the resin solid content in the resin composition is 100 parts by mass. It is more preferably 9 parts by mass or more, even more preferably 10 parts by mass or more, and even more preferably 15 parts by mass or more. On the other hand, the upper limit of the content of the compound (M1) represented by formula (M1) is preferably 50 parts by mass or less, and 40 parts by mass or less when the resin solid content in the resin composition is 100 parts by mass. It is more preferably at most 35 parts by mass, even more preferably at most 30 parts by mass, and may be at most 25 parts by mass. By controlling the content of the compound (M1) represented by formula (M1) to be at least the above lower limit, the resulting cured product tends to have excellent heat resistance and moisture absorption heat resistance. Further, by setting the amount to be below the upper limit, the metal foil peel strength and desmear resistance of the obtained cured product can be effectively kept in a good range.
　また、式（Ｍ１）で表される化合物（Ｍ１）の含有量の下限値は、式（Ｍ）で表される化合物（Ｍ)１００質量部に対し、１０質量部以上であることが好ましく、２０質量部以上であることがより好ましく、３０質量部以上であることがさらに好ましく、６０質量部以上であることが一層好ましく、７０質量部以上であることがより一層好ましく、８０質量部以上であることがさらに一層好ましく、８５質量部以上であることがよりさらに一層好ましく、９０質量部以上であることが特に一層好ましく、９５質量部以上であってもよい。他方、式（Ｍ１）で表される化合物（Ｍ１）の含有量の上限値は、式（Ｍ）で表される化合物（Ｍ)１００質量部に対し、６００質量部以下であることが好ましく、５００質量部以下であることがより好ましく、４００質量部以下であることがさらに好ましく、３００質量部以下であることが一層好ましく、さらには、２００質量部以下、１７０質量部以下、１５０質量部以下、１４０質量部以下、１３０質量部以下、１２５質量部以下であることが好ましく、用途等に応じて、１２０質量部以下、１１５質量部以下、１１０質量部以下、１０５質量部以下であってもよい。式（Ｍ１）で表される化合物（Ｍ１）の含有量範囲を上記範囲に調整することで、低誘電特性（Ｄｋおよび／またはＤｆ、特に低誘電正接）、金属箔ピール強度、デスミア耐性、吸湿耐熱性に優れる傾向がある。
　式（Ｍ１）で表される化合物（Ｍ１）は、樹脂組成物中に、１種のみ含まれていても、２種以上含まれていてもよい。２種以上含まれる場合は、合計量が上記範囲となることが好ましい。 Further, the lower limit of the content of the compound (M1) represented by the formula (M1) is preferably 10 parts by mass or more with respect to 100 parts by mass of the compound (M) represented by the formula (M), It is more preferably 20 parts by mass or more, even more preferably 30 parts by mass or more, even more preferably 60 parts by mass or more, even more preferably 70 parts by mass or more, and even more preferably 80 parts by mass or more. It is even more preferable that the amount is at least 85 parts by weight, even more preferably at least 85 parts by weight, even more preferably at least 90 parts by weight, and may be at least 95 parts by weight. On the other hand, the upper limit of the content of the compound (M1) represented by the formula (M1) is preferably 600 parts by mass or less with respect to 100 parts by mass of the compound (M) represented by the formula (M), It is more preferably 500 parts by mass or less, even more preferably 400 parts by mass or less, even more preferably 300 parts by mass or less, furthermore 200 parts by mass or less, 170 parts by mass or less, 150 parts by mass or less. , 140 parts by mass or less, 130 parts by mass or less, 125 parts by mass or less, depending on the use etc., it may be 120 parts by mass or less, 115 parts by mass or less, 110 parts by mass or less, 105 parts by mass or less. good. By adjusting the content range of the compound (M1) represented by formula (M1) to the above range, low dielectric properties (Dk and/or Df, especially low dielectric loss tangent), metal foil peel strength, desmear resistance, and moisture absorption can be achieved. It tends to have excellent heat resistance.
Only one type of compound (M1) represented by formula (M1) may be contained in the resin composition, or two or more types may be contained in the resin composition. When two or more types are included, it is preferable that the total amount falls within the above range.
　本実施形態の樹脂組成物において、式（Ｍ）で表される化合物（Ｍ）と、式（Ｖ）で表される構成単位を有する重合体（Ｖ）と、式（Ｍ１）で表される化合物（Ｍ１）との含有量の質量比率は、式（Ｍ）で表される化合物（Ｍ）１００質量部に対する、式（Ｖ）で表される構成単位を有する重合体（Ｖ）と、式（Ｍ１）で表される化合物（Ｍ１）の比率が３０～１３０：９０～４００であることが好ましく、４０～１３０：９０～３００であることがより好ましく、７０～１３０：９０～１４０であることが一層好ましく、７０～１１０：９０～１１０であることがより一層好ましく、９０～１０５：９０～１０５であることがさらに一層好ましい。これらのブレンド比を調整することにより、樹脂組成物の硬化が良好に進行し、Ｄｆをより低くすることができ、また、耐デスミア性をより向上させることができる。
　また、本実施形態の樹脂組成物においては、式（Ｍ１）で表される化合物（Ｍ１）の含有量／式（Ｖ）で表される構成単位を有する重合体（Ｖ）の含有量で表される比が、３．０以下であることが好ましく、２．５以下であることがより好ましく、２．０以下であることがさらに好ましく、１．８以下であることが一層好ましく、また、０．５以上であることが好ましく、０．８以上であることがより好ましい。このようなブレンド比を調整することにより、樹脂組成物の硬化が良好に進行し、Ｄｆをより低くすることができ、また、耐デスミア性をより向上させることができる。 In the resin composition of the present embodiment, a compound (M) represented by formula (M), a polymer (V) having a structural unit represented by formula (V), and a polymer represented by formula (M1) The mass ratio of the content of compound (M1) to 100 parts by mass of compound (M) represented by formula (M) is the content of polymer (V) having a structural unit represented by formula (V) and formula The ratio of the compound (M1) represented by (M1) is preferably 30-130:90-400, more preferably 40-130:90-300, and 70-130:90-140. The ratio is more preferably 70 to 110:90 to 110, even more preferably 90 to 105:90 to 105. By adjusting these blend ratios, curing of the resin composition progresses favorably, Df can be lowered, and desmear resistance can be further improved.
In addition, in the resin composition of the present embodiment, the content is expressed as the content of the compound (M1) represented by the formula (M1)/the content of the polymer (V) having the structural unit represented by the formula (V). The ratio is preferably 3.0 or less, more preferably 2.5 or less, even more preferably 2.0 or less, even more preferably 1.8 or less, and It is preferably 0.5 or more, and more preferably 0.8 or more. By adjusting such a blend ratio, curing of the resin composition progresses favorably, Df can be lowered, and desmear resistance can be further improved.
＜他の熱硬化性化合物（Ｃ）＞
　本実施形態の樹脂組成物は、式（Ｍ）で表される化合物（Ｍ）および式（Ｍ１）で表される化合物（Ｍ１）以外のマレイミド化合物、エポキシ化合物、フェノール化合物、オキセタン樹脂、ベンゾオキサジン化合物、（メタ）アリル基を含む化合物（好ましくはアルケニルナジイミド化合物）、および、炭素－炭素不飽和二重結合を２以上含むポリフェニレンエーテル化合物からなる群より選択される１種以上の他の熱硬化性化合物（Ｃ）をさらに含んでいてもよい。このような成分を含むことにより、プリント配線板に求められる所望の性能をより効果的に発揮させることができる。 <Other thermosetting compounds (C)>
The resin composition of the present embodiment contains a compound (M) represented by formula (M) and a maleimide compound other than the compound (M1) represented by formula (M1), an epoxy compound, a phenol compound, an oxetane resin, and a benzoxazine. one or more types of other heat selected from the group consisting of a compound, a compound containing a (meth)allyl group (preferably an alkenylnadimide compound), and a polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds. It may further contain a curable compound (C). By including such components, the desired performance required of the printed wiring board can be more effectively exhibited.
＜＜式（Ｍ）で表される化合物（Ｍ）および式（Ｍ１）で表される化合物（Ｍ１）以外のマレイミド化合物＞＞
　本実施形態の樹脂組成物は、式（Ｍ）で表される化合物（Ｍ）および式（Ｍ１）で表される化合物（Ｍ１）以外のマレイミド化合物を含んでいてもよい。本実施形態の樹脂組成物は、１分子中に１以上（好ましくは２～１２、より好ましくは２～６、さらに好ましくは２～４、一層好ましくは２または３、より一層好ましくは２）のマレイミド基を有する化合物であれば特に限定されず、プリント配線板の分野で通常用いられる化合物を広く用いることができる。
　本実施形態においては、式（Ｍ）で表される化合物（Ｍ）および式（Ｍ１）で表される化合物（Ｍ１）以外のマレイミド化合物は、式（Ｍ２）で表される化合物、式（Ｍ３）で表される化合物、式（Ｍ４）で表される化合物、および、マレイミド化合物（Ｍ６）からなる群より選択される１種以上を含むことが好ましく、式（Ｍ２）で表される化合物、式（Ｍ３）で表される化合物、および、式（Ｍ４）で表される化合物からなる群より選択される１種以上を含むことがより好ましい。
（式（Ｍ２）中、Ｒ５４はそれぞれ独立に、水素原子またはメチル基を表し、ｎ４は１以上の整数を表す。）
　ｎ４は１～１０の整数が好ましく、１～５の整数がより好ましく、１～３の整数がさらに好ましく、１または２であることが一層好ましい。
　式（Ｍ２）で表される化合物は、ｎ４が異なる化合物の混合物であってもよく、混合物であることが好ましい。
（式（Ｍ３）中、Ｒ５５はそれぞれ独立に、水素原子、炭素数１～８のアルキル基またはフェニル基を表し、ｎ５は１以上１０以下の整数を表す。）
　Ｒ５５は、水素原子、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔ－ブチル基、ｎ－ペンチル基、フェニル基であることが好ましく、水素原子およびメチル基の一方であることがより好ましく、水素原子であることがさらに好ましい。
　ｎ５は１以上５以下の整数であることが好ましく、１～３の整数がさらに好ましく、１または２であることが一層好ましい。
　式（Ｍ３）で表される化合物は、ｎ5が異なる化合物の混合物であってもよく、混合物であることが好ましい。
（式（Ｍ４）中、Ｒ５６はそれぞれ独立に水素原子、メチル基またはエチル基を表し、Ｒ５７はそれぞれ独立に水素原子またはメチル基を表す。） <<Maleimide compounds other than the compound (M) represented by formula (M) and the compound (M1) represented by formula (M1)>>
The resin composition of the present embodiment may contain a maleimide compound other than the compound (M) represented by formula (M) and the compound (M1) represented by formula (M1). The resin composition of this embodiment has one or more (preferably 2 to 12, more preferably 2 to 6, still more preferably 2 to 4, even more preferably 2 or 3, even more preferably 2) per molecule. The compound is not particularly limited as long as it has a maleimide group, and a wide variety of compounds commonly used in the field of printed wiring boards can be used.
In this embodiment, maleimide compounds other than the compound (M) represented by formula (M) and the compound (M1) represented by formula (M1) are the compound represented by formula (M2), the compound represented by formula (M3 ), a compound represented by formula (M4), and a maleimide compound (M6), preferably containing one or more selected from the group consisting of a compound represented by formula (M2), It is more preferable to include one or more selected from the group consisting of a compound represented by formula (M3) and a compound represented by formula (M4).
(In formula (M2), R 54 each independently represents a hydrogen atom or a methyl group, and n 4 represents an integer of 1 or more.)
n 4 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, and even more preferably 1 or 2.
The compound represented by formula (M2) may be a mixture of compounds in which n 4 is different, and is preferably a mixture.
(In formula (M3), R 55 each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group, and n 5 represents an integer of 1 to 10.)
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, or phenyl group; One of the methyl groups is more preferable, and a hydrogen atom is even more preferable.
n 5 is preferably an integer of 1 or more and 5 or less, more preferably an integer of 1 to 3, and even more preferably 1 or 2.
The compound represented by formula (M3) may be a mixture of compounds having different n 5 values, and is preferably a mixture.
(In formula (M4), R 56 each independently represents a hydrogen atom, a methyl group, or an ethyl group, and R 57 each independently represents a hydrogen atom or a methyl group.)
　マレイミド化合物（Ｍ６）は、式（Ｍ６）表される構成単位と、分子鎖の両末端にマレイミド基とを有する化合物である。
（式（Ｍ６）中、Ｒ６１は、炭素数１～１６の直鎖状もしくは分岐状のアルキレン基、または炭素数２～１６の直鎖状もしくは分岐状のアルケニレン基を表す。Ｒ６２は、炭素数１～１６の直鎖状もしくは分岐状のアルキレン基、または炭素数２～１６の直鎖状もしくは分岐状のアルケニレン基を表す。Ｒ６３は、それぞれ独立に、炭素数１～１６の直鎖状もしくは分岐状のアルキル基、または炭素数２～１６の直鎖状もしくは分岐状のアルケニル基を表す。ｎは、それぞれ独立に、０～１０の整数を表す。）
　マレイミド化合物（Ｍ６）の詳細およびその製造方法は、国際公開第２０２０／２６２５７７号の段落００６１～００６６の記載を参酌でき、この内容は本明細書に組み込まれる。 The maleimide compound (M6) is a compound having a structural unit represented by formula (M6) and maleimide groups at both ends of the molecular chain.
(In formula (M6), R 61 represents a linear or branched alkylene group having 1 to 16 carbon atoms, or a linear or branched alkenylene group having 2 to 16 carbon atoms. R 62 is R 63 represents a linear or branched alkylene group having 1 to 16 carbon atoms, or a linear or branched alkenylene group having 2 to 16 carbon atoms. Represents a chain or branched alkyl group, or a straight or branched alkenyl group having 2 to 16 carbon atoms. Each n independently represents an integer of 0 to 10.)
For details of the maleimide compound (M6) and its manufacturing method, the description in paragraphs 0061 to 0066 of International Publication No. 2020/262577 can be referred to, the contents of which are incorporated herein.
　式（Ｍ）で表される化合物（Ｍ）および式（Ｍ１）で表される化合物（Ｍ１）以外のマレイミド化合物は、公知の方法で製造してもよく、市販品を用いてもよい。市販品としては、例えば、式（Ｍ２）で表される化合物として大和化成工業社製「ＢＭＩ－２３００」、式（Ｍ３）で表される化合物として日本化薬株式会社製「ＭＩＲ－３０００」、式（Ｍ４）で表される化合物としてケイ・アイ化成社製「ＢＭＩ－７０」、マレイミド化合物（Ｍ６）として、日本化薬社製「ＭＩＺ－００１」が挙げられる。 Maleimide compounds other than the compound (M) represented by formula (M) and the compound (M1) represented by formula (M1) may be produced by a known method, or commercially available products may be used. Commercially available products include, for example, "BMI-2300" manufactured by Daiwa Kasei Kogyo Co., Ltd. as a compound represented by formula (M2), "MIR-3000" manufactured by Nippon Kayaku Co., Ltd. as a compound represented by formula (M3), Examples of the compound represented by formula (M4) include "BMI-70" manufactured by K.I. Kasei Co., Ltd., and "MIZ-001" manufactured by Nippon Kayaku Co., Ltd. as the maleimide compound (M6).
　また、上記以外のマレイミド化合物としては、２つ以上のマレイミド基を有する化合物が例示され、具体的には、ｍ－フェニレンビスマレイミド、２，２－ビス（４－（４－マレイミドフェノキシ）－フェニル）プロパン、４－メチル－１，３－フェニレンビスマレイミド、１，６－ビスマレイミド－（２，２，４－トリメチル）ヘキサン、４，４’－ジフェニルエーテルビスマレイミド、４，４’－ジフェニルスルフォンビスマレイミド、１，３－ビス（３－マレイミドフェノキシ）ベンゼン、１，３－ビス（４－マレイミドフェノキシ）ベンゼン、およびこれらのプレポリマー、これらのマレイミドとアミンのプレポリマー等が挙げられる。 Examples of maleimide compounds other than those mentioned above include compounds having two or more maleimide groups, specifically 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'-diphenyl ether bismaleimide, 4,4'-diphenylsulfone bis Examples include maleimide, 1,3-bis(3-maleimidophenoxy)benzene, 1,3-bis(4-maleimidophenoxy)benzene, prepolymers thereof, and prepolymers of these maleimides and amines.
　式（Ｍ）で表される化合物（Ｍ）および式（Ｍ１）で表される化合物（Ｍ１）以外のマレイミド化合物を含む場合、その含有量の下限値は、樹脂組成物中の樹脂固形分１００質量部に対し、１質量部以上であることが好ましく、５質量部以上であることがより好ましく、１０質量部以上であることがさらに好ましく、２０質量部以上であってもよく、２５質量部以上であってもよい。式（Ｍ）で表される化合物（Ｍ）および式（Ｍ１）で表される化合物（Ｍ１）以外のマレイミド化合物の含有量が１質量部以上であることにより、得られる硬化物の耐燃性が向上する傾向にある。また、式（Ｍ）で表される化合物（Ｍ）および式（Ｍ１）で表される化合物（Ｍ１）以外のマレイミド化合物の含有量の上限値は、樹脂組成物中の樹脂固形分１００質量部に対し、５０質量部以下であることが好ましく、４０質量部以下であることがより好ましく、３０質量部以下であってもよい。式（Ｍ）で表される化合物（Ｍ）および式（Ｍ１）で表される化合物（Ｍ１）以外のマレイミド化合物の含有量が５０質量部以下であることにより、得られる硬化物の金属箔ピール強度および低吸水性が向上する傾向にある。
　本実施形態における樹脂組成物は、式（Ｍ）で表される化合物（Ｍ）および式（Ｍ１）で表される化合物（Ｍ１）以外のマレイミド化合物を１種のみ含んでいてもよいし、２種以上含んでいてもよい。２種以上含む場合、合計量が上記範囲となることが好ましい。
　また、本実施形態における樹脂組成物は、式（Ｍ）で表される化合物（Ｍ）以外のマレイミド化合物を実質的に含まない構成とすることもできる。実質的に含まないとは、式（Ｍ）で表される化合物（Ｍ）および式（Ｍ１）で表される化合物（Ｍ１）以外のマレイミド化合物の含有量が樹脂組成物中の樹脂固形分１００質量部に対し、１質量部未満であることをいい、０．１質量部未満であることが好ましく、０．０１質量部未満であることがより好ましい。 When containing a maleimide compound other than the compound (M) represented by the formula (M) and the compound (M1) represented by the formula (M1), the lower limit of the content is 100% of the resin solid content in the resin composition. It is preferably 1 part by mass or more, more preferably 5 parts by mass or more, even more preferably 10 parts by mass or more, may be 20 parts by mass or more, and 25 parts by mass. It may be more than that. When the content of the maleimide compound other than the compound (M) represented by the formula (M) and the compound (M1) represented by the formula (M1) is 1 part by mass or more, the flame resistance of the obtained cured product is improved. There is a tendency to improve. In addition, the upper limit of the content of maleimide compounds other than the compound (M) represented by formula (M) and the compound (M1) represented by formula (M1) is 100 parts by mass of resin solid content in the resin composition. It is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and may be 30 parts by mass or less. The metal foil peel of the cured product obtained by containing a maleimide compound other than the compound (M) represented by the formula (M) and the compound (M1) represented by the formula (M1) is 50 parts by mass or less. Strength and low water absorption tend to improve.
The resin composition in this embodiment may contain only one maleimide compound other than the compound (M) represented by formula (M) and the compound (M1) represented by formula (M1), or may contain only one maleimide compound other than the compound (M) represented by formula (M) and the compound (M1) represented by formula (M1), It may contain more than one species. When two or more types are included, it is preferable that the total amount falls within the above range.
Moreover, the resin composition in this embodiment can also be made into the structure which does not contain substantially the maleimide compound other than the compound (M) represented by Formula (M). "Substantially free" means that the content of maleimide compounds other than the compound (M) represented by formula (M) and the compound (M1) represented by formula (M1) is 100% of the resin solid content in the resin composition. It means less than 1 part by mass, preferably less than 0.1 part by mass, and more preferably less than 0.01 part by mass.
＜＜エポキシ化合物＞＞
　本実施形態の樹脂組成物は、エポキシ化合物を含んでいてもよい。
　エポキシ化合物は、１分子中に１以上（好ましくは２～１２、より好ましくは２～６、さらに好ましくは２～４、一層好ましくは２または３、より一層好ましくは２）のエポキシ基を有する化合物または樹脂であれば特に限定されず、プリント配線板の分野で通常用いられる化合物を広く用いることができる。
　エポキシ化合物は、例えば、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＥ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、ビスフェノールＡノボラック型エポキシ樹脂、グリシジルエステル型エポキシ樹脂、アラルキルノボラック型エポキシ樹脂、ビフェニルアラルキル型エポキシ樹脂、ナフチレンエーテル型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、多官能フェノール型エポキシ樹脂、ナフタレン型エポキシ樹脂、アントラセン型エポキシ樹脂、ナフタレン骨格変性ノボラック型エポキシ樹脂、フェノールアラルキル型エポキシ樹脂、ナフトールアラルキル型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、ビフェニル型エポキシ樹脂、脂環式エポキシ樹脂、ポリオール型エポキシ樹脂、リン含有エポキシ樹脂、グリシジルアミン、グリシジルエステル、ブタジエン等の二重結合をエポキシ化した化合物、水酸基含有シリコーン樹脂類とエピクロロヒドリンとの反応により得られる化合物等が挙げられる。これらを用いることで、樹脂組成物の成形性、密着性が向上する。これらの中でも、難燃性および耐熱性をより一層向上させる観点から、ビフェニルアラルキル型エポキシ樹脂、ナフチレンエーテル型エポキシ樹脂、多官能フェノール型エポキシ樹脂、ナフタレン型エポキシ樹脂であることが好ましく、ビフェニルアラルキル型エポキシ樹脂であることがより好ましい。 <<Epoxy compound>>
The resin composition of this embodiment may contain an epoxy compound.
An epoxy compound is a compound having one or more (preferably 2 to 12, more preferably 2 to 6, still more preferably 2 to 4, even more preferably 2 or 3, even more preferably 2) epoxy groups in one molecule. Alternatively, there is no particular limitation as long as it is a resin, and a wide variety of compounds commonly used in the field of printed wiring boards can be used.
Examples of epoxy compounds include bisphenol A epoxy resin, bisphenol E epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, bisphenol A novolac epoxy resin, glycidyl ester epoxy resin, and aralkyl epoxy resin. Novolac type epoxy resin, biphenylaralkyl type epoxy resin, naphthylene ether type epoxy resin, cresol novolac type epoxy resin, multifunctional phenol type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, naphthalene skeleton modified novolac 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, glycidyl amine, glycidyl ester, butadiene, etc. Examples include compounds in which bonds are epoxidized, and compounds obtained by reacting hydroxyl group-containing silicone resins with epichlorohydrin. By using these, the moldability and adhesion of the resin composition are improved. Among these, from the viewpoint of further improving flame retardancy and heat resistance, biphenylaralkyl epoxy resins, naphthylene ether epoxy resins, polyfunctional phenol epoxy resins, and naphthalene epoxy resins are preferred; More preferably, it is a type epoxy resin.
　本実施形態の樹脂組成物は、エポキシ化合物を本発明の効果を損なわない範囲で含むことが好ましい。本実施形態の樹脂組成物がエポキシ化合物を含む場合、その含有量は、樹脂組成物中の樹脂固形分１００質量部に対し、０．１質量部以上であることが好ましく、１質量部以上であることがより好ましく、２質量部以上であることがさらに好ましい。エポキシ化合物の含有量が０．１質量部以上であることにより、得られる硬化物の金属箔ピール強度および靭性が向上する傾向にある。エポキシ化合物の含有量の上限値は、本実施形態の樹脂組成物がエポキシ化合物を含む場合、樹脂組成物中の樹脂固形分１００質量部に対し、５０質量部以下であることが好ましく、３０質量部以下であることがより好ましく、２０質量部以下であることがさらに好ましく、１０質量部以下であることが一層好ましく、８質量部以下、５質量部以下であってもよい。エポキシ化合物の含有量が５０質量部以下であることにより、得られる硬化物の電気特性が向上する傾向にある。
　本実施形態における樹脂組成物は、エポキシ化合物を１種のみ含んでいてもよいし、２種以上含んでいてもよい。２種以上含む場合、合計量が上記範囲となることが好ましい。
　また、本実施形態における樹脂組成物は、エポキシ化合物を実質的に含まない構成とすることもできる。実質的に含まないとは、エポキシ化合物の含有量が樹脂組成物中の樹脂固形分１００質量部に対し、０．１質量部未満であることをいい、好ましくは０．０１質量部未満であり、さらには０．００１質量部未満であってもよい。 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. When the resin composition of the present embodiment contains an epoxy compound, the content thereof is preferably 0.1 parts by mass or more, and 1 part by mass or more, based on 100 parts by mass of resin solids in the resin composition. It is more preferable that the amount is at least 2 parts by mass, and even more preferably 2 parts by mass or more. When the content of the epoxy compound is 0.1 parts by mass or more, the metal foil peel strength and toughness of the resulting cured product tend to improve. When the resin composition of this embodiment contains an epoxy compound, the upper limit of the content of the epoxy compound is preferably 50 parts by mass or less, and 30 parts by mass or less, based on 100 parts by mass of resin solids in the resin composition. It is more preferably at most 20 parts by mass, even more preferably at most 10 parts by mass, and may be at most 8 parts by mass, and may be at most 5 parts by mass. When the content of the epoxy compound is 50 parts by mass or less, the electrical properties of the obtained cured product tend to improve.
The resin composition in this embodiment may contain only one type of epoxy compound, or may contain two or more types of epoxy compounds. When two or more types are included, it is preferable that the total amount falls within the above range.
Moreover, the resin composition in this embodiment can also have a structure that does not 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, based on 100 parts by mass of resin solids in the resin composition. , and even less than 0.001 part by mass.
＜＜フェノール化合物＞＞
　本実施形態の樹脂組成物は、フェノール化合物を含んでいてもよい。
　フェノール化合物は、１分子中に１以上（好ましくは２～１２、より好ましくは２～６、さらに好ましくは２～４、一層好ましくは２または３、より一層好ましくは２）のフェノール性水酸基を有するフェノール化合物であれば特に限定されず、プリント配線板の分野で通常用いられる化合物を広く用いることができる。
　フェノール化合物は、例えば、ビスフェノールＡ型フェノール樹脂、ビスフェノールＥ型フェノール樹脂、ビスフェノールＦ型フェノール樹脂、ビスフェノールＳ型フェノール樹脂、フェノールノボラック樹脂、ビスフェノールＡノボラック型フェノール樹脂、グリシジルエステル型フェノール樹脂、アラルキルノボラックフェノール樹脂、ビフェニルアラルキル型フェノール樹脂、クレゾールノボラック型フェノール樹脂、多官能フェノール樹脂、ナフトール樹脂、ナフトールノボラック樹脂、多官能ナフトール樹脂、アントラセン型フェノール樹脂、ナフタレン骨格変性ノボラック型フェノール樹脂、フェノールアラルキル型フェノール樹脂、ナフトールアラルキル型フェノール樹脂、ジシクロペンタジエン型フェノール樹脂、ビフェニル型フェノール樹脂、脂環式フェノール樹脂、ポリオール型フェノール樹脂、リン含有フェノール樹脂、水酸基含有シリコーン樹脂類等が挙げられる。これらの中でも、得られる硬化物の耐燃性をより一層向上させる観点から、ビフェニルアラルキル型フェノール樹脂、ナフトールアラルキル型フェノール樹脂、リン含有フェノール樹脂、および水酸基含有シリコーン樹脂からなる群より選択される少なくとも１種であることが好ましい。 <<Phenol compounds>>
The resin composition of this embodiment may contain a phenol compound.
The phenol compound has one or more (preferably 2 to 12, more preferably 2 to 6, still more preferably 2 to 4, even more preferably 2 or 3, even more preferably 2) phenolic hydroxyl groups in one molecule. The phenol compound is not particularly limited, and a wide variety of compounds commonly used in the field of printed wiring boards can be used.
Examples of the phenol compound include 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 novolac phenol. Resin, biphenylaralkyl type phenolic resin, cresol novolac type phenolic resin, polyfunctional phenolic resin, naphthol resin, naphthol novolak resin, polyfunctional naphthol resin, anthracene type phenolic resin, naphthalene skeleton modified novolak type phenolic resin, phenol aralkyl type phenolic resin, Examples include naphthol aralkyl-type phenolic resins, dicyclopentadiene-type phenolic resins, biphenyl-type phenolic resins, alicyclic phenolic resins, polyol-type phenolic resins, phosphorus-containing phenolic resins, and hydroxyl group-containing silicone resins. Among these, from the viewpoint of further improving the flame resistance of the obtained cured product, at least one selected from the group consisting of biphenyl aralkyl type phenol resin, naphthol aralkyl type phenol resin, phosphorus-containing phenol resin, and hydroxyl group-containing silicone resin. Preferably it is a seed.
　本実施形態の樹脂組成物は、フェノール化合物を本発明の効果を損なわない範囲で含むことが好ましい。本実施形態の樹脂組成物がフェノール化合物を含む場合、その含有量は、樹脂組成物中の樹脂固形分１００質量部に対し、０．１質量部以上であることが好ましく、１質量部以上であることがより好ましく、２質量部以上であることがさらに好ましい。また、５０質量部以下であることが好ましく、３０質量部以下であることがより好ましく、２０質量部以下であることがさらに好ましく、１０質量部以下であることが一層好ましく、５質量部以下であってもよい。
　本実施形態における樹脂組成物は、フェノール化合物を１種のみ含んでいてもよいし、２種以上含んでいてもよい。２種以上含む場合、合計量が上記範囲となることが好ましい。
　また、本実施形態における樹脂組成物は、フェノール化合物を実質的に含まない構成とすることもできる。実質的に含まないとは、フェノール化合物の含有量が樹脂組成物中の樹脂固形分１００質量部に対し、０．１質量部未満であることをいう。 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. When the resin composition of the present embodiment contains a phenol compound, the content is preferably 0.1 part by mass or more, and 1 part by mass or more, based on 100 parts by mass of resin solids in the resin composition. It is more preferable that the amount is at least 2 parts by mass, and even more preferably 2 parts by mass or more. Further, the amount is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, and 5 parts by mass or less. There may be.
The resin composition in this embodiment may contain only one type of phenol compound, or may contain two or more types of phenol compounds. When two or more types are included, it is preferable that the total amount falls within the above range.
Moreover, the resin composition in this embodiment can also have a structure that does not substantially contain a phenol compound. "Substantially free" means that the content of the phenol compound is less than 0.1 parts by mass based on 100 parts by mass of resin solids in the resin composition.
＜＜オキセタン樹脂＞＞
　本実施形態の樹脂組成物は、オキセタン樹脂を含んでいてもよい。
　オキセタン樹脂は、オキセタニル基を１以上（好ましくは２～１２、より好ましくは２～６、さらに好ましくは２～４、一層好ましくは２または３、より一層好ましくは２）有する化合物であれば、特に限定されず、プリント配線板の分野で通常用いられる化合物を広く用いることができる。
　オキセタン樹脂としては、例えば、オキセタン、アルキルオキセタン（例えば、２－メチルオキセタン、２，２－ジメチルオキセタン、３－メチルオキセタン、３，３－ジメチルオキセタン等）、３－メチル－３－メトキシメチルオキセタン、３，３－ジ（トリフルオロメチル）オキセタン、２－クロロメチルオキセタン、３，３－ビス（クロロメチル）オキセタン、ビフェニル型オキセタン、ＯＸＴ－１０１（東亞合成社製）、ＯＸＴ－１２１（東亞合成社製）等が挙げられる。 <<Oxetane resin>>
The resin composition of this embodiment may contain oxetane resin.
The oxetane resin is particularly a compound having one or more oxetanyl groups (preferably 2 to 12, more preferably 2 to 6, even more preferably 2 to 4, even more preferably 2 or 3, even more preferably 2). There are no limitations, and a wide variety of compounds commonly used in the field of printed wiring boards can be used.
Examples of the oxetane resin include oxetane, alkyloxetane (for example, 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 (manufactured by Toagosei Co., Ltd.) (manufactured by), etc.
　本実施形態の樹脂組成物は、オキセタン樹脂を本発明の効果を損なわない範囲で含むことが好ましい。本実施形態の樹脂組成物が、オキセタン樹脂を含む場合、その含有量は、樹脂組成物中の樹脂固形分１００質量部に対し、０．１質量部以上であることが好ましく、１質量部以上であることがより好ましく、２質量部以上であることがさらに好ましい。オキセタン樹脂の含有量が０．１質量部以上であることにより、得られる硬化物の金属箔ピール強度および靭性が向上する傾向にある。オキセタン樹脂の含有量の上限値は、本実施形態の樹脂組成物が、オキセタン樹脂を含む場合、樹脂組成物中の樹脂固形分１００質量部に対し、５０質量部以下であることが好ましく、３０質量部以下であることがより好ましく、２０質量部以下であることがさらに好ましく、１０質量部以下であることが一層好ましく、５質量部以下であってもよい。オキセタン樹脂の含有量が５０質量部以下であることにより、得られる硬化物の電気特性が向上する傾向にある。
　本実施形態における樹脂組成物は、オキセタン樹脂を１種のみ含んでいてもよいし、２種以上含んでいてもよい。２種以上含む場合、合計量が上記範囲となることが好ましい。
　また、本実施形態における樹脂組成物は、オキセタン樹脂を実質的に含まない構成とすることもできる。実質的に含まないとは、オキセタン樹脂の含有量が樹脂組成物中の樹脂固形分１００質量部に対し、０．１質量部未満であることをいう。 The resin composition of this embodiment preferably contains an oxetane resin within a range that does not impair the effects of the present invention. When the resin composition of the present embodiment contains an oxetane resin, the content thereof is preferably 0.1 parts by mass or more, and 1 part by mass or more based on 100 parts by mass of resin solids in the resin composition. More preferably, the amount is 2 parts by mass or more. When the content of the oxetane resin is 0.1 parts by mass or more, the metal foil peel strength and toughness of the obtained cured product tend to improve. When the resin composition of this embodiment contains an oxetane resin, the upper limit of the content of oxetane resin is preferably 50 parts by mass or less, and 30 parts by mass or less, based on 100 parts by mass of resin solid content in the resin composition. It is more preferably at most 20 parts by mass, even more preferably at most 10 parts by mass, and may be at most 5 parts by mass. When the content of the oxetane resin is 50 parts by mass or less, the electrical properties of the resulting cured product tend to improve.
The resin composition in this embodiment may contain only one type of oxetane resin, or may contain two or more types of oxetane resin. When two or more types are included, it is preferable that the total amount falls within the above range.
Moreover, the resin composition in this embodiment can also be configured to substantially not contain oxetane resin. "Substantially free" means that the content of oxetane resin is less than 0.1 parts by mass based on 100 parts by mass of resin solid content in the resin composition.
＜＜ベンゾオキサジン化合物＞＞
　本実施形態の樹脂組成物は、ベンゾオキサジン化合物を含んでいてもよい。
　ベンゾオキサジン化合物としては、１分子中に２以上（好ましくは２～１２、より好ましくは２～６、さらに好ましくは２～４、一層好ましくは２または３、より一層好ましくは２）のジヒドロベンゾオキサジン環を有する化合物であれば特に限定されず、プリント配線板の分野で通常用いられる化合物を広く用いることができる。
　ベンゾオキサジン化合物としては、例えば、ビスフェノールＡ型ベンゾオキサジンＢＡ－ＢＸＺ（小西化学社製）、ビスフェノールＦ型ベンゾオキサジンＢＦ－ＢＸＺ（小西化学社製）、ビスフェノールＳ型ベンゾオキサジンＢＳ－ＢＸＺ（小西化学社製）等が挙げられる。 <<Benzoxazine compound>>
The resin composition of this embodiment may contain a benzoxazine compound.
The benzoxazine compound includes 2 or more (preferably 2 to 12, more preferably 2 to 6, even more preferably 2 to 4, even more preferably 2 or 3, even more preferably 2) dihydrobenzoxazines in one molecule. Any compound having a ring is not particularly limited, and a wide range of compounds commonly used in the field of printed wiring boards can be used.
Examples of benzoxazine compounds include bisphenol A-type benzoxazine BA-BXZ (manufactured by Konishi Chemical Co., Ltd.), bisphenol F-type benzoxazine BF-BXZ (manufactured by Konishi Chemical Co., Ltd.), and bisphenol S-type benzoxazine BS-BXZ (manufactured by Konishi Chemical Co., Ltd.). ), etc.
　本実施形態の樹脂組成物は、ベンゾオキサジン化合物を本発明の効果を損なわない範囲で含むことが好ましい。本実施形態の樹脂組成物がベンゾオキサジン化合物を含む場合、その含有量は、樹脂組成物中の樹脂固形分１００質量部に対し、０．１質量部以上であることが好ましく、５０質量部以下であることが好ましい。
　本実施形態における樹脂組成物は、ベンゾオキサジン化合物を１種のみ含んでいてもよいし、２種以上含んでいてもよい。２種以上含む場合、合計量が上記範囲となることが好ましい。
　また、本実施形態における樹脂組成物は、ベンゾオキサジン化合物を実質的に含まない構成とすることもできる。実質的に含まないとは、ベンゾオキサジン化合物の含有量が樹脂組成物中の樹脂固形分１００質量部に対し、０．１質量部未満であることをいう。 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. When the resin composition of the present embodiment contains a benzoxazine compound, the content thereof is preferably 0.1 parts by mass or more and 50 parts by mass or less based on 100 parts by mass of resin solids in the resin composition. It is preferable that
The resin composition in this embodiment may contain only one type of benzoxazine compound, or may contain two or more types of benzoxazine compounds. When two or more types are included, it is preferable that the total amount falls within the above range.
Moreover, the resin composition in this embodiment can also be configured to substantially not contain a benzoxazine compound. "Substantially free" means that the content of the benzoxazine compound is less than 0.1 parts by mass based on 100 parts by mass of resin solid content in the resin composition.
＜＜（メタ）アリル基を含む化合物＞＞
　本実施形態の樹脂組成物は、（メタ）アリル基を含む化合物を含むことが好ましく、アリル基を含む化合物を含むことがより好ましい。
　また、（メタ）アリル基を含む化合物は、（メタ）アリル基を２以上含む化合物であることが好ましく、アリル基を２以上含む化合物であることがより好ましい。
　（メタ）アリル基を含む化合物としては、アリルイソシアヌレート化合物、アリル基置換ナジイミド化合物、グリコールウリル構造を有するアリル化合物、および、ジアリルフタレートからなる群より選択される少なくとも１種を含むことが好ましく、アリルイソシアヌレート化合物、アリル基置換ナジイミド化合物、および、グリコールウリル構造を有するアリル化合物からなる群より選択される少なくとも１種を含むことがより好ましく、アリル基置換ナジイミド化合物を含むことがさらに好ましく、アルケニルナジイミド化合物がさらに好ましい。 <<Compound containing (meth)allyl group>>
The resin composition of this embodiment preferably contains a compound containing a (meth)allyl group, and more preferably contains a compound containing an allyl group.
Further, the compound containing a (meth)allyl group is preferably a compound containing two or more (meth)allyl groups, and more preferably a compound containing two or more allyl groups.
The compound containing a (meth)allyl group preferably contains at least one selected from the group consisting of an allyl isocyanurate compound, an allyl group-substituted nadimide compound, an allyl compound having a glycoluril structure, and diallyl phthalate, It is more preferable to contain at least one selected from the group consisting of an allyl isocyanurate compound, an allyl group-substituted nadimide compound, and an allyl compound having a glycoluril structure, and more preferably an allyl group-substituted nadimide compound, and an alkenyl More preferred are nadimide compounds.
　本実施形態の樹脂組成物が、（メタ）アリル基を含む化合物を含む場合、その分子量は、１９５以上であることが好ましく、３００以上であることがより好ましく、４００以上であることがさらに好ましく、５００以上であることが一層好ましい。前記下限値以上とすることにより、得られる硬化物の低誘電性および耐熱性がより向上する傾向にある。（メタ）アリル基を含む化合物の分子量は、また、３０００以下であることが好ましく、２０００以下であることがより好ましく、１０００以下であることがさらに好ましく、８００以下であることが一層好ましい。前記上限値以下とすることにより、得られる硬化物の低熱膨張性がより向上する傾向にある。 When the resin composition of the present embodiment contains a compound containing a (meth)allyl group, its molecular weight is preferably 195 or more, more preferably 300 or more, and even more preferably 400 or more. , more preferably 500 or more. When the amount is equal to or more than the lower limit, the resulting cured product tends to have improved low dielectric properties and heat resistance. The molecular weight of the compound containing a (meth)allyl group is also preferably 3,000 or less, more preferably 2,000 or less, even more preferably 1,000 or less, and even more preferably 800 or less. By setting it below the above-mentioned upper limit, the low thermal expansion property of the obtained cured product tends to be further improved.
　本実施形態の樹脂組成物が（メタ）アリル基を含む化合物を含む場合、その含有量は、樹脂組成物中の樹脂固形分１００質量部に対し、１質量部以上であることが好ましく、３質量部以上であることがより好ましく、５質量部以上であることがさらに好ましく、１０質量部以上であってもよい。（メタ）アリル基を含む化合物の含有量を上記下限値以上とすることにより、樹脂組成物の成形性に優れ、得られる硬化物の耐熱性がより向上する傾向にある。また、（メタ）アリル基を含む化合物の含有量の上限値は、樹脂組成物中の樹脂固形分１００質量部に対し、４０質量部以下であることが好ましく、３０質量部以下であることがより好ましく、２０質量部以下であることがさらに好ましい。（メタ）アリル基を含む化合物の含有量を上記上限値以下とすることにより、得られる硬化物の低熱膨張性がより向上する傾向にある。
　本実施形態の樹脂組成物は、（メタ）アリル基を含む化合物を１種のみ含んでいてもよいし、２種以上含んでいてもよい。２種以上含む場合、合計量が上記範囲となることが好ましい。
　また、本実施形態における樹脂組成物は、（メタ）アリル基を含む化合物を実質的に含まない構成とすることもできる。実質的に含まないとは、（メタ）アリル基を含む化合物の含有量が樹脂組成物中の樹脂固形分１００質量部に対し、０．１質量部未満であることをいう。 When the resin composition of the present embodiment contains a compound containing a (meth)allyl group, the content thereof is preferably 1 part by mass or more, and 3 parts by mass or more, based on 100 parts by mass of resin solids in the resin composition. It is more preferably at least 5 parts by mass, even more preferably at least 5 parts by mass, and may be at least 10 parts by mass. By setting the content of the compound containing a (meth)allyl group to the above lower limit or more, the moldability of the resin composition tends to be excellent, and the heat resistance of the resulting cured product tends to be further improved. Further, the upper limit of the content of the compound containing a (meth)allyl group is preferably 40 parts by mass or less, and preferably 30 parts by mass or less, based on 100 parts by mass of the resin solid content in the resin composition. More preferably, the amount is 20 parts by mass or less. By controlling the content of the compound containing a (meth)allyl group to the above-mentioned upper limit or less, the low thermal expansion properties of the resulting cured product tend to be further improved.
The resin composition of this embodiment may contain only one type of compound containing a (meth)allyl group, or may contain two or more types. When two or more types are included, it is preferable that the total amount falls within the above range.
Moreover, the resin composition in this embodiment can also be configured to substantially not contain a compound containing a (meth)allyl group. "Substantially free" means that the content of the compound containing a (meth)allyl group is less than 0.1 part by mass based on 100 parts by mass of resin solid content in the resin composition.
＜＜＜アリルイソシアヌレート化合物＞＞＞
　アリルイソシアヌレート化合物としては、アリル基を２つ以上有し、かつ、イソシアヌレート環（ヌレート骨格）を有する化合物である限り、特に定めるものではないが、式（ＴＡ）で表される化合物が好ましい。
式（ＴＡ）
（式（ＴＡ）中、ＲＡは、置換基を表す）。 <<<Allyl isocyanurate compound>>>
The allyl isocyanurate compound is not particularly defined as long as it has two or more allyl groups and an isocyanurate ring (nurate skeleton), but a compound represented by formula (TA) is preferable. .
Formula (TA)
(In formula (TA), RA represents a substituent).
　式（ＴＡ）中、ＲＡは、置換基を表し、式量１５～５００の置換基であることがより好ましい。 In formula (TA), R A represents a substituent, and a substituent having a formula weight of 15 to 500 is more preferable.
　ＲＡの第一の例は、炭素数１～２２のアルキル基、または、炭素数２～２２のアルケニル基である。炭素数１～２２のアルキル基、または、炭素数２～２２のアルケニル基を有するアリル化合物を使用することによって、架橋性に優れ、かつ、高靱性を有する硬化物を得ることができる樹脂組成物を提供することができる。それにより、樹脂組成物にガラスクロスなどの基材を含めない場合であっても、エッチング処理などの際に割れたりすることを抑制できる。
　前記アルキル基および／またはアルケニル基の炭素数は、ハンドリング性向上の観点から、３以上が好ましく、８以上がより好ましく、１２以上であってもよく、１８以下であることが好ましい。それにより樹脂組成物の樹脂流れ性が良好となり、本実施形態の樹脂組成物を用いて多層回路基板などを作成する際の回路充填性などにより優れるようになると考えられる。 A first example of R A is an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 2 to 22 carbon atoms. A resin composition capable of obtaining a cured product having excellent crosslinkability and high toughness by using an allyl compound having an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 2 to 22 carbon atoms. can be provided. Thereby, even if the resin composition does not include a base material such as glass cloth, it is possible to suppress cracking during etching treatment or the like.
From the viewpoint of improving handling properties, the number of carbon atoms in the alkyl group and/or alkenyl group is preferably 3 or more, more preferably 8 or more, may be 12 or more, and is preferably 18 or less. It is thought that this improves the resin flowability of the resin composition, resulting in better circuit filling properties when creating a multilayer circuit board or the like using the resin composition of this embodiment.
　ＲＡの第二の例は、アリルイソシアヌレート基を含む基である。ＲＡがアリルイソシアヌレート基を含む場合、式（ＴＡ）で表される化合物は、式（ＴＡ－１）で表される化合物であることが好ましい。
式（ＴＡ－１）
（式（ＴＡ－１）中、ＲＡ２は、２価の連結基である。） A second example of R A is a group containing an allyl isocyanurate group. When R A contains an allyl isocyanurate group, the compound represented by formula (TA) is preferably a compound represented by formula (TA-1).
Formula (TA-1)
(In formula (TA-1), R A2 is a divalent linking group.)
　式（ＴＡ－１）中、ＲＡ２は、式量が５４～２５０の２価の連結基であることが好ましく、式量が５４～２５０で、両末端が炭素原子である２価の連結基であることがより好ましく、炭素数２～２０の脂肪族炭化水素基であることがさらに好ましい（但し、脂肪族炭化水素基中にエーテル基を含んでいてもよく、また、水酸基を有していてもよい）。より具体的には、ＲＡ２は、下記式（ｉ）～（iii）のいずれかで表される基であることが好ましい。
（式中（ｉ）～（ｉｉｉ）中、ｐｃ１はメチレン基の繰り返し単位数を表し、２～１８の整数である。ｐｃ２はオキシエチレン基の繰り返し単位数を表し、０または１である。＊は結合部位である。）
　前記ｐｃ１は、好ましくは２～１０の整数、より好ましくは３～８の整数、さらに好ましくは３～５の整数である。
　前記ｐｃ２は、０であってもよいし、１であってもよいが、好ましくは１である。 In formula (TA-1), R A2 is preferably a divalent linking group having a formula weight of 54 to 250, and a divalent linking group having a formula weight of 54 to 250 and having carbon atoms at both ends. is more preferable, and an aliphatic hydrocarbon group having 2 to 20 carbon atoms is even more preferable (however, the aliphatic hydrocarbon group may contain an ether group, and may have a hydroxyl group). ). More specifically, R A2 is preferably a group represented by any of the following formulas (i) to (iii).
(In the formulas (i) to (iii), p c1 represents the number of repeating units of the methylene group and is an integer of 2 to 18. p c2 represents the number of repeating units of the oxyethylene group and is 0 or 1. .* is the binding site.)
The p c1 is preferably an integer of 2 to 10, more preferably an integer of 3 to 8, and still more preferably an integer of 3 to 5.
The p c2 may be 0 or 1, but is preferably 1.
　ＲＡ２は第一の例であることが好ましい。 Preferably, R A2 is the first example.
　本実施形態では、式（ＴＡ）で表される化合物の反応基（アリル基）当量が１０００以下であることが望ましい。前記当量が１０００以下であれば、高いＴｇをより確実に得ることができると考えられる。
　前記炭素数１～２２のアルキル基としては、直鎖状または分岐鎖状のアルキル基が挙げられ、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ドデシル基、テトラデシル基、ヘキサデシル基、オクタデシル基、エイコシル基、ドコシル基等が挙げられる。また、前記炭素数２～２２のアルケニル基としては、例えば、アリル基、デセニル基等が挙げられる。 In this embodiment, it is desirable that the reactive group (allyl group) equivalent of the compound represented by formula (TA) is 1000 or less. It is considered that if the equivalent is 1000 or less, a high Tg can be obtained more reliably.
Examples of the alkyl group having 1 to 22 carbon atoms include linear or branched alkyl groups, such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group. group, nonyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosyl group, docosyl group, and the like. Further, examples of the alkenyl group having 2 to 22 carbon atoms include an allyl group and a decenyl group.
　式（ＴＡ）で表される化合物の具体例としては、例えば、トリアリルイソシアヌレート、５－オクチル－１，３－ジアリルイソシアヌレート、５－ドデシル－１，３－ジアリルイソシアヌレート、５－テトラデシル－１，３－ジアリルイソシアヌレート、５－ヘキサデシル－１，３－ジアリルイソシアヌレート、５－オクタデシル－１，３－ジアリルイソシアヌレート、５－エイコシル－１，３－ジアリルイソシアヌレート、５－ドコシル－１，３－ジアリルイソシアヌレート、５－デセニル－１，３－ジアリルイソシアヌレートなどが挙げられる。これらは１種または２種以上を組み合わせて使用してもよく、プレポリマーとして使用してもよい。 Specific examples of the compound represented by formula (TA) include triallylisocyanurate, 5-octyl-1,3-diallylisocyanurate, 5-dodecyl-1,3-diallylisocyanurate, 5-tetradecyl- 1,3-diallylisocyanurate, 5-hexadecyl-1,3-diallylisocyanurate, 5-octadecyl-1,3-diallylisocyanurate, 5-eicosyl-1,3-diallylisocyanurate, 5-docosyl-1, Examples include 3-diallylisocyanurate and 5-decenyl-1,3-diallylisocyanurate. These may be used alone or in combination of two or more, or may be used as a prepolymer.
　式（ＴＡ）で表される化合物の製造方法は、特に限定はされないが、例えば、ジアリルイソシアヌレートとアルキルハライドとをＮ，Ｎ’－ジメチルホルムアミド等の非プロトン性極性溶剤中において、水酸化ナトリウム、炭酸カリウム、トリエチルアミンなどの塩基性物質の存在下で、６０℃～１５０℃程度の温度で反応させることにより、得ることができる。 The method for producing the compound represented by formula (TA) is not particularly limited, but for example, diallylisocyanurate and alkyl halide are mixed in an aprotic polar solvent such as N,N'-dimethylformamide, and sodium hydroxide is added. It can be obtained by reacting at a temperature of about 60°C to 150°C in the presence of a basic substance such as , potassium carbonate, or triethylamine.
　また、式（ＴＡ）で表される化合物は、市販のものを用いることもできる。市販されているものとしては、特に限定されないが、例えば、四国化成工業(株)製Ｌ－ＤＡＩＣが挙げられる。トリアリルイソシアヌレートとしては、例えば、三菱ケミカル(株)製ＴＡＩＣが挙げられる。式（ＴＡ－１）で表される化合物としては、例えば、四国化成工業(株)製ＤＤ－１が挙げられる。 Furthermore, commercially available compounds can also be used as the compound represented by formula (TA). Commercially available products include, but are not particularly limited to, L-DAIC manufactured by Shikoku Kasei Kogyo Co., Ltd., for example. Examples of triallyl isocyanurate include TAIC manufactured by Mitsubishi Chemical Corporation. Examples of the compound represented by formula (TA-1) include DD-1 manufactured by Shikoku Kasei Kogyo Co., Ltd.
　アリルイソシアヌレート化合物（好ましくは、式（ＴＡ）で表される化合物）の分子量は、２００以上であることが好ましく、３００以上であることがより好ましく、４００以上であることがさらに好ましく、５００以上であることが一層好ましい。前記分子量を上記下限値以上とすることにより、得られる硬化物の低誘電性および耐熱性がより向上する傾向にある。また、アリルイソシアヌレート化合物（好ましくは、式（ＴＡ）で表される化合物）の分子量は、３０００以下であることが好ましく、２０００以下であることがより好ましく、１０００以下であることがさらに好ましく、８００以下であることが一層好ましい。前記分子量を上記上限値以下とすることにより、得られる硬化物の低熱膨張性がより向上する傾向にある。 The molecular weight of the allyl isocyanurate compound (preferably the compound represented by formula (TA)) is preferably 200 or more, more preferably 300 or more, even more preferably 400 or more, and even more preferably 500 or more. It is more preferable that By setting the molecular weight to the lower limit value or more, the resulting cured product tends to have improved low dielectric properties and heat resistance. Further, the molecular weight of the allyl isocyanurate compound (preferably a compound represented by formula (TA)) is preferably 3000 or less, more preferably 2000 or less, even more preferably 1000 or less, More preferably, it is 800 or less. By controlling the molecular weight to be less than or equal to the upper limit value, the resulting cured product tends to have improved low thermal expansion properties.
　本実施形態の樹脂組成物がアリルイソシアヌレート化合物を含む場合、その含有量は、樹脂組成物中の樹脂固形分１００質量部に対し、１質量部以上であることが好ましく、３質量部以上であることがより好ましく、５質量部以上であることがさらに好ましく、１０質量部以上であってもよい。アリルイソシアヌレート化合物の含有量を上記下限値以上とすることにより、樹脂組成物の成形性に優れ、得られる硬化物の耐熱性がより向上する傾向にある。また、アリルイソシアヌレート化合物の含有量の上限値は、樹脂組成物中の樹脂固形分１００質量部に対し、４０質量部以下であることが好ましく、３０質量部以下であることがより好ましく、２０質量部以下であることがさらに好ましい。アリルイソシアヌレート化合物の含有量を上記上限値以下とすることにより、得られる硬化物の低熱膨張性がより向上する傾向にある。
　本実施形態の樹脂組成物は、アリルイソシアヌレートを１種のみ含んでいてもよいし、２種以上含んでいてもよい。２種以上含む場合、合計量が上記範囲となることが好ましい。 When the resin composition of the present embodiment contains an allyl isocyanurate compound, the content thereof is preferably 1 part by mass or more, and 3 parts by mass or more based on 100 parts by mass of resin solids in the resin composition. The amount is more preferably 5 parts by mass or more, and may be 10 parts by mass or more. By setting the content of the allyl isocyanurate compound to the above lower limit or more, the moldability of the resin composition tends to be excellent, and the heat resistance of the resulting cured product tends to be further improved. Further, the upper limit of the content of the allyl isocyanurate compound is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and 20 parts by mass or less, based on 100 parts by mass of the resin solid content in the resin composition. It is more preferably less than parts by mass. By controlling the content of the allyl isocyanurate compound to be less than or equal to the above upper limit, the low thermal expansion properties of the resulting cured product tend to be further improved.
The resin composition of this embodiment may contain only one type of allyl isocyanurate, or may contain two or more types of allyl isocyanurate. When two or more types are included, it is preferable that the total amount falls within the above range.
＜＜＜アリル基置換ナジイミド化合物＞＞＞
　アリル基置換ナジイミド化合物としては、分子中に１個以上のアリル基置換ナジイミド基を有する化合物（好ましくは分子中に１個以上のアルケニル基で置換されたナジイミド基を有する化合物（アルケニルナジイミド化合物））であれば、特に限定されるものではない。その具体例としては下記式（ＡＮ）で表される化合物が挙げられる。
式（ＡＮ）
（式（ＡＮ）中、Ｒ１は、それぞれ独立に、水素原子、または、炭素数１～６のアルキル基を表し、Ｒ２は、炭素数１～６のアルキレン基、フェニレン基、ビフェニレン基、ナフチレン基、または、式（ＡＮ－２）または（ＡＮ－３）で表される基を表す。
式（ＡＮ－２）
（式（ＡＮ－２）中、Ｒ３は、メチレン基、イソプロピリデン基、－Ｃ（＝Ｏ）－、－Ｏ－、－Ｓ－、または、－Ｓ（＝Ｏ）２－で表される基を表す。）
式（ＡＮ－３）
（式（ＡＮ－３）中、Ｒ４は、それぞれ独立に、炭素数１～４のアルキレン基、または、炭素数５～８のシクロアルキレン基を表す。） <<<Allyl group-substituted nadimide compound>>>
Examples of allyl-substituted nadimide compounds include compounds having one or more allyl-substituted nadimide groups in the molecule (preferably compounds having one or more alkenyl-substituted nadimide groups in the molecule (alkenylnadimide compounds)) ), it is not particularly limited. A specific example thereof is a compound represented by the following formula (AN).
Formula (AN)
(In formula (AN), R 1 each 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, Represents a naphthylene group or a group represented by formula (AN-2) or (AN-3).
Formula (AN-2)
(In formula (AN-2), R 3 is represented by a methylene group, an isopropylidene group, -C(=O)-, -O-, -S-, or -S(=O) 2 - (Represents a group.)
Formula (AN-3)
(In formula (AN-3), R 4 each independently represents an alkylene group having 1 to 4 carbon atoms or a cycloalkylene group having 5 to 8 carbon atoms.)
　また、式（ＡＮ）で表される化合物は、市販のものを用いることもできる。市販されているものとしては、特に限定されないが、例えば、式（ＡＮ－４）で表される化合物（ＢＡＮＩ－Ｍ（丸善石油化学（株）製））、式（ＡＮ－５）で表される化合物（ＢＡＮＩ－Ｘ（丸善石油化学（株）製））などが挙げられる。これらは１種または２種以上を組み合わせて使用してもよい。
式（ＡＮ－４）
式（ＡＮ－５）
Moreover, a commercially available compound can also be used as the compound represented by formula (AN). Commercially available compounds include, but are not particularly limited to, compounds represented by the formula (AN-4) (BANI-M (manufactured by Maruzen Petrochemical Co., Ltd.)), compounds represented by the formula (AN-5), Examples include compounds such as BANI-X (manufactured by Maruzen Petrochemical Co., Ltd.). These may be used alone or in combination of two or more.
Formula (AN-4)
Formula (AN-5)
　アリル基置換ナジイミド化合物（好ましくは式（ＡＮ）で表される化合物）の分子量は、４００以上であることが好ましく、５００以上であることがより好ましく、５５０以上であってもよい。アリル基置換ナジイミド化合物の分子量を上記下限値以上とすることにより、得られる硬化物の、低誘電性、低熱膨張性、および、耐熱性がより向上する傾向にある。アリル基置換ナジイミド化合物（好ましくは式（ＡＮ）で表される化合物）の分子量は、また、１５００以下であることが好ましく、１０００以下であることがより好ましく、８００以下であることがさらに好ましく、７００以下、６００以下であってもよい。アリル基置換ナジイミド化合物の分子量を上記上限値以下とすることにより、樹脂組成物の成形性、および、得られる硬化物のピール強度がより向上する傾向にある。 The molecular weight of the allyl group-substituted nadimide compound (preferably the compound represented by formula (AN)) is preferably 400 or more, more preferably 500 or more, and may be 550 or more. By setting the molecular weight of the allyl group-substituted nadimide compound to the above lower limit or more, the resulting cured product tends to have improved low dielectricity, low thermal expansion, and heat resistance. The molecular weight of the allyl group-substituted nadimide compound (preferably a compound represented by formula (AN)) is also preferably 1,500 or less, more preferably 1,000 or less, even more preferably 800 or less, It may be 700 or less, or 600 or less. By controlling the molecular weight of the allyl group-substituted nadimide compound to be less than or equal to the above upper limit, the moldability of the resin composition and the peel strength of the obtained cured product tend to be further improved.
　本実施形態の樹脂組成物がアリル基置換ナジイミド化合物（好ましくは式（ＡＮ）で表される化合物）を含む場合、その含有量は、樹脂組成物中の樹脂固形分１００質量部に対し、０．１質量部以上であることが好ましく、１質量部以上であることがより好ましく、２質量部以上であることがさらに好ましい。また、５０質量部以下であることが好ましく、３０質量部以下であることがより好ましく、２０質量部以下であることがさらに好ましく、１０質量部以下であることが一層好ましく、５質量部以下であってもよい。アリル基置換ナジイミド化合物の含有量を上記上限値以下とすることにより、樹脂組成物の成形性、および、得られる硬化物のピール強度がより向上する傾向にある。
　本実施形態の樹脂組成物は、アリル基置換ナジイミド化合物を１種のみ含んでいてもよいし、２種以上含んでいてもよい。２種以上含む場合、合計量が上記範囲となることが好ましい。
　また、本実施形態における樹脂組成物は、アリル基置換ナジイミド化合物を実質的に含まない構成とすることもできる。実質的に含まないとは、アリル基置換ナジイミド化合物の含有量が樹脂組成物中の樹脂固形分１００質量部に対し、０．１質量部未満であることをいう。 When the resin composition of the present embodiment contains an allyl group-substituted nadimide compound (preferably a compound represented by formula (AN)), the content thereof is 0 parts by mass based on 100 parts by mass of resin solid content in the resin composition. It is preferably at least .1 part by mass, more preferably at least 1 part by mass, and even more preferably at least 2 parts by mass. Further, the amount is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, and 5 parts by mass or less. There may be. By controlling the content of the allyl group-substituted nadimide compound to be less than or equal to the above upper limit, the moldability of the resin composition and the peel strength of the obtained cured product tend to be further improved.
The resin composition of the present embodiment may contain only one type of allyl group-substituted nadimide compound, or may contain two or more types of allyl group-substituted nadimide compounds. When two or more types are included, it is preferable that the total amount falls within the above range.
Moreover, the resin composition in this embodiment can also be configured to substantially not contain the allyl group-substituted nadimide compound. "Substantially free" means that the content of the allyl group-substituted nadimide compound is less than 0.1 part by mass based on 100 parts by mass of resin solid content in the resin composition.
＜＜＜グリコールウリル構造を有するアリル化合物＞＞＞
　グリコールウリル構造を有するアリル化合物としては、グリコールウリル構造とアリル基を２つ以上含む化合物であれば、特に定めるものではなく、式（ＧＵ）で表される化合物が好ましい。
　式（ＧＵ）
（式（ＧＵ）中、Ｒは、それぞれ独立に、水素原子または置換基であり、Ｒの少なくとも２つは、アリル基を含む基である。）
　式（ＧＵ）中、Ｒは、それぞれ独立に、水素原子、炭素数１～５のアルキル基、または、炭素数２～５のアルケニル基であることが好ましく、炭素数２～５のアルケニル基であることが好ましく、アリル基であることが好ましい。
　式（ＧＵ）中、Ｒは、３つまたは４つがアリル基を含む基であることが好ましく、４つがアリル基を含む基であることがより好ましい。 <<<Allyl compound having glycoluril structure>>>
The allyl compound having a glycoluril structure is not particularly limited as long as it contains a glycoluril structure and two or more allyl groups, and a compound represented by formula (GU) is preferred.
Formula (GU)
(In formula (GU), each R is independently a hydrogen atom or a substituent, and at least two of R are groups containing an allyl group.)
In formula (GU), each R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkenyl group having 2 to 5 carbon atoms, and an alkenyl group having 2 to 5 carbon atoms. Preferably, it is an allyl group.
In formula (GU), R is preferably a group containing three or four allyl groups, and more preferably a group containing four allyl groups.
　式（ＧＵ）で表される化合物の具体例としては、１，３，４，６－テトラアリルグリコールウリル（式（ＧＵ）において、Ｒが全てアリル基である化合物）が挙げられる。 A specific example of the compound represented by formula (GU) is 1,3,4,6-tetraallylglycoluril (a compound in which all R's are allyl groups in formula (GU)).
　また、式（ＧＵ）で表される化合物は、市販のものを用いることもできる。市販されているものとしては、特に限定されないが、例えば、四国化成工業社製ＴＡ－Ｇが挙げられる。 Further, as the compound represented by formula (GU), a commercially available one can also be used. Commercially available products include, but are not particularly limited to, TA-G manufactured by Shikoku Kasei Kogyo Co., Ltd., for example.
　グリコールウリル構造を有するアリル化合物（好ましくは式（ＧＵ）で表される化合物）の分子量は、１９５以上であることが好ましく、２２０以上であることがより好ましく、２５０以上であることがさらに好ましく、３００以上、４００以上であってもよい。グリコールウリル構造を有するアリル化合物の分子量を上記下限値以上とすることにより、得られる硬化物の低誘電性および耐熱性がより向上する傾向にある。グリコールウリル構造を有するアリル化合物（好ましくは式（ＧＵ）で表される化合物）の分子量は、また、１５００以下であることが好ましく、１０００以下であることがより好ましく、８００以下であることがさらに好ましく、７００以下、６００以下であってもよい。グリコールウリル構造を有するアリル化合物の分子量を上記上限値以下とすることにより、得られる硬化物の低熱膨張性がより向上する傾向にある。 The molecular weight of the allyl compound having a glycoluril structure (preferably a compound represented by formula (GU)) is preferably 195 or more, more preferably 220 or more, even more preferably 250 or more, It may be 300 or more, or 400 or more. By setting the molecular weight of the allyl compound having a glycoluril structure to the above lower limit or more, the resulting cured product tends to have improved low dielectric properties and heat resistance. The molecular weight of the allyl compound having a glycoluril structure (preferably a compound represented by formula (GU)) is also preferably 1500 or less, more preferably 1000 or less, further preferably 800 or less. It is preferably 700 or less, or may be 600 or less. By controlling the molecular weight of the allyl compound having a glycoluril structure to be less than or equal to the above upper limit, the resulting cured product tends to have better low thermal expansion properties.
　本実施形態の樹脂組成物がグリコールウリル構造を有するアリル化合物（好ましくは式（ＧＵ）で表される化合物）を含む場合、その含有量は、樹脂組成物中の樹脂固形分１００質量部に対し、１質量部以上であることが好ましく、３質量部以上であることがより好ましく、５質量部以上であることがさらに好ましく、１０質量部以上であってもよい。グリコールウリル構造を有するアリル化合物の含有量を上記下限値以上とすることにより、得られる硬化物の低誘電性および耐熱性がより向上する傾向にある。また、グリコールウリル構造を有するアリル化合物（好ましくは式（ＧＵ）で表される化合物）の含有量の上限値は、樹脂組成物中の樹脂固形分１００質量部に対し、４０質量部以下であることが好ましく、３０質量部以下であることがより好ましく、２５質量部以下であることがさらに好ましく、２０質量部以下であってもよい。グリコールウリル構造を有するアリル化合物の含有量を上記上限値以下とすることにより、得られる硬化物の低熱膨張性がより向上する傾向にある。
　本実施形態の樹脂組成物は、グリコールウリル構造を有するアリル化合物を１種のみ含んでいてもよいし、２種以上含んでいてもよい。２種以上含む場合、合計量が上記範囲となることが好ましい。 When the resin composition of the present embodiment contains an allyl compound having a glycoluril structure (preferably a compound represented by formula (GU)), the content thereof is based on 100 parts by mass of resin solid content in the resin composition. , is preferably 1 part by mass or more, more preferably 3 parts by mass or more, even more preferably 5 parts by mass or more, and may be 10 parts by mass or more. By setting the content of the allyl compound having a glycoluril structure to the above lower limit or more, the resulting cured product tends to have improved low dielectric properties and heat resistance. Further, the upper limit of the content of the allyl compound having a glycoluril structure (preferably a compound represented by formula (GU)) is 40 parts by mass or less based on 100 parts by mass of the resin solid content in the resin composition. The amount is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and may be 20 parts by mass or less. By controlling the content of the allyl compound having a glycoluril structure to the above upper limit or less, the low thermal expansion property of the obtained cured product tends to be further improved.
The resin composition of this embodiment may contain only one kind of allyl compound having a glycoluril structure, or may contain two or more kinds. When two or more types are included, it is preferable that the total amount falls within the above range.
＜＜炭素－炭素不飽和二重結合を２以上含むポリフェニレンエーテル化合物＞＞
　本実施形態の樹脂組成物は、炭素－炭素不飽和二重結合を２以上含むポリフェニレンエーテル化合物を含んでいてもよい。
　炭素－炭素不飽和二重結合を２以上含むポリフェニレンエーテル化合物は、末端に、炭素－炭素不飽和二重結合を２以上有するポリフェニレンエーテル化合物であることが好ましく、末端に、（メタ）アクリル基、マレイミド基、ビニルベンジル基からなる群から選ばれる基を２以上有するポリフェニレンエーテル化合物であることがより好ましい。これらのポリフェニレンエーテル化合物を用いることにより、プリント配線板等の誘電特性と低吸水性等をより効果的に向上させることができる傾向がある。
　以下、これらの詳細を説明する。 <<Polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds>>
The resin composition of this embodiment may contain a polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds.
The polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds is preferably a polyphenylene ether compound having two or more carbon-carbon unsaturated double bonds at the terminal, and a (meth)acrylic group at the terminal, More preferably, it is a polyphenylene ether compound having two or more groups selected from the group consisting of a maleimide group and a vinylbenzyl group. By using these polyphenylene ether compounds, there is a tendency that the dielectric properties, low water absorption, etc. of printed wiring boards and the like can be more effectively improved.
These details will be explained below.
　炭素－炭素不飽和二重結合を２以上含むポリフェニレンエーテル化合物は、下記式（Ｘ１）で表されるフェニレンエーテル骨格を有する化合物が例示される。 The polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds is exemplified by a compound having a phenylene ether skeleton represented by the following formula (X1).
（式（Ｘ１）中、Ｒ２４、Ｒ２５、Ｒ２６、および、Ｒ２７は、同一または異なってもよく、炭素数６以下のアルキル基、アリール基、ハロゲン原子、または、水素原子を表す。） (In 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. )
　炭素－炭素不飽和二重結合を２以上含むポリフェニレンエーテル化合物は、式（Ｘ２）：
（式（Ｘ２）中、Ｒ２８、Ｒ２９、Ｒ３０、Ｒ３４、および、Ｒ３５は、同一または異なってもよく、炭素数６以下のアルキル基またはフェニル基を表す。Ｒ３１、Ｒ３２、および、Ｒ３３は、同一または異なってもよく、水素原子、炭素数６以下のアルキル基またはフェニル基である。）
で表される繰り返し単位、および／または、式（Ｘ３）：
（式（Ｘ３）中、Ｒ３６、Ｒ３７、Ｒ３８、Ｒ３９、Ｒ４０、Ｒ４１、Ｒ４２、および、Ｒ４３は、同一または異なってもよく、水素原子、炭素数６以下のアルキル基またはフェニル基である。－Ａ－は、炭素数２０以下の直鎖、分岐または環状の２価の炭化水素基である。）で表される繰り返し単位をさらに含んでもよい。 The 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 or a phenyl group having 6 or less carbon atoms. R 31 , R 32 , and R 33 may be the same or different and are a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group.)
A repeating unit represented by and/or formula (X3):
(In 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. -A- is a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms.
　炭素－炭素不飽和二重結合を２以上含むポリフェニレンエーテル化合物は、末端の一部または全部が、エチレン性不飽和基で官能基化された変性ポリフェニレンエーテル化合物（以下、「変性ポリフェニレンエーテル化合物（ｇ）」ということがある）であることが好ましく、末端に、（メタ）アクリル基、マレイミド基、ビニルベンジル基からなる群から選ばれる基を２以上有する変性ポリフェニレンエーテル化合物であることがより好ましい。このような変性ポリフェニレンエーテル化合物（ｇ）を採用することにより、樹脂組成物の硬化物の誘電正接（Ｄｆ）をより小さくし、かつ、低吸水性、金属箔ピール強度を高めることが可能になる。これらは１種または２種以上を組み合わせて用いてもよい。 A polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds is a modified polyphenylene ether compound (hereinafter referred to as a "modified polyphenylene ether compound (g )" is preferable, and 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 terminal is more preferable. By employing such a modified polyphenylene ether compound (g), it becomes possible to further reduce the dielectric loss tangent (Df) of the cured product of the resin composition, and to increase low water absorption and metal foil peel strength. . These may be used alone or in combination of two or more.
　変性ポリフェニレンエーテル化合物（ｇ）としては、式（ＯＰ－１）で表される化合物が挙げられる。
（式（ＯＰ－１）中、Ｘは芳香族基を表し、－（Ｙ－Ｏ）ｎ２－はポリフェニレンエーテル構造を表し、Ｒ１、Ｒ２、および、Ｒ３は、それぞれ独立して、水素原子、アルキル基、アルケニル基またはアルキニル基を表し、ｎ１は１～６の整数を表し、ｎ２は１～１００の整数を表し、ｎ３は１～４の整数を表す。）
　ｎ２および／またはｎ３が２以上の整数の場合、ｎ２個の構成単位（Ｙ－Ｏ）および／またはｎ３個の構成単位は、それぞれ同一であっても異なっていてもよい。ｎ３は、２以上が好ましく、より好ましくは２である。 Examples of the modified polyphenylene ether compound (g) include a compound represented by formula (OP-1).
(In formula (OP-1), X represents an aromatic group, -(Y-O)n 2 - represents a polyphenylene ether structure, and R 1 , R 2 and R 3 are each independently, Represents a hydrogen atom, an alkyl group, an alkenyl group, or an alkynyl group, n 1 represents an integer of 1 to 6, n 2 represents an integer of 1 to 100, and n 3 represents an integer of 1 to 4.)
When n 2 and/or n 3 are integers of 2 or more, the n 2 structural units (YO) and/or the n 3 structural units may be the same or different. n 3 is preferably 2 or more, more preferably 2.
　本実施形態における変性ポリフェニレンエーテル化合物（ｇ）は、式（ＯＰ－２）で表される化合物であることが好ましい。
　ここで、－（Ｏ－Ｘ－Ｏ）－は、式（ＯＰ－３）：
（式（ＯＰ－３）中、Ｒ４、Ｒ５、Ｒ６、Ｒ１０、および、Ｒ１１は、同一または異なってもよく、炭素数６以下のアルキル基またはフェニル基である。Ｒ７、Ｒ８、および、Ｒ９は、同一または異なってもよく、水素原子、炭素数６以下のアルキル基またはフェニル基である。）
および／または式（ＯＰ－４）：
（式（ＯＰ－４）中、Ｒ１２、Ｒ１３、Ｒ１４、Ｒ１５、Ｒ１６、Ｒ１７、Ｒ１８、および、Ｒ１９は、同一または異なってもよく、水素原子、炭素数６以下のアルキル基またはフェニル基である。－Ａ－は、炭素数２０以下の直鎖、分岐または環状の２価の炭化水素基である。）で表されることが好ましい。 The modified polyphenylene ether compound (g) in this embodiment is preferably a compound represented by formula (OP-2).
Here, -(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 or a phenyl group having 6 or less carbon atoms. 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, and each has a hydrogen atom and a carbon number of 6 or less. is an alkyl group or phenyl group. -A- is a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms.
　また、－（Ｙ－Ｏ）－は、式（ＯＰ－５）：
（式（ＯＰ－５）中、Ｒ２０、Ｒ２１は、同一または異なってもよく、炭素数６以下のアルキル基またはフェニル基である。Ｒ２２、Ｒ２３は、同一または異なってもよく、水素原子、炭素数６以下のアルキル基またはフェニル基である。）で表されることが好ましい。
　式（ＯＰ－２）において、ａ、ｂは、少なくともいずれか一方が０でない、０～１００の整数を表し、０～５０の整数であることが好ましく、１～３０の整数であることがより好ましい。ａおよび／またはｂが２以上の整数の場合、２以上の－（Ｙ－Ｏ）－は、それぞれ独立に、１種の構造が配列したものであってよく、２種以上の構造がブロックまたはランダムに配列していてもよい。 Moreover, -(YO)- is the formula (OP-5):
(In formula (OP-5), R 20 and R 21 may be the same or different and are an alkyl group or a phenyl group having 6 or less carbon atoms. R 22 and R 23 may be the same or different, It is preferably represented by a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group.
In formula (OP-2), 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. When a and/or b is an integer of 2 or more, 2 or more -(YO)- may each independently be an array of one type of structure, or two or more types of structures may be a block or They may be arranged randomly.
　式（ＯＰ－４）における－Ａ－としては、例えば、メチレン基、エチリデン基、１－メチルエチリデン基、１，１－プロピリデン基、１，４－フェニレンビス（１－メチルエチリデン）基、１，３－フェニレンビス（１－メチルエチリデン）基、シクロヘキシリデン基、フェニルメチレン基、ナフチルメチレン基、１－フェニルエチリデン基等の２価の有機基が挙げられるが、これらに限定されるものではない。 -A- in formula (OP-4) is, for example, a methylene group, ethylidene group, 1-methylethylidene group, 1,1-propylidene group, 1,4-phenylenebis(1-methylethylidene) group, 1, Examples include, but are not limited to, divalent organic groups such as 3-phenylenebis(1-methylethylidene) group, cyclohexylidene group, phenylmethylene group, naphthylmethylene group, and 1-phenylethylidene group. .
　上記変性ポリフェニレンエーテル化合物（ｇ）のなかでは、Ｒ４、Ｒ５、Ｒ６、Ｒ１０、Ｒ１１、Ｒ２０、および、Ｒ２１が炭素数３以下のアルキル基であり、Ｒ７、Ｒ８、Ｒ９、Ｒ１２、Ｒ１３、Ｒ１４、Ｒ１５、Ｒ１６、Ｒ１７、Ｒ１８、Ｒ１９、Ｒ２２、および、Ｒ２３が水素原子または炭素数３以下のアルキル基であるポリフェニレンエーテル化合物が好ましく、特に式（ＯＰ－３）または式（ＯＰ－４）で表される－（Ｏ－Ｘ－Ｏ）－が、式（ＯＰ－９）、式（ＯＰ－１０）、および／または式（ＯＰ－１１）であり、式（ＯＰ－５）で表される－（Ｙ－Ｏ）－が、式（ＯＰ－１２）または式（ＯＰ－１３）であることが好ましい。ａおよび／またはｂが２以上の整数の場合、２以上の－（Ｙ－Ｏ）－は、それぞれ独立に、式（ＯＰ－１２）および／または式（ＯＰ－１３）が２以上配列した構造であるか、あるいは式（ＯＰ－１２）と式（ＯＰ－１３）がブロックまたはランダムに配列した構造であってよい。 In the modified polyphenylene ether compound (g), R 4 , R 5 , R 6 , R 10 , R 11 , R 20 and R 21 are alkyl groups having 3 or less carbon atoms, and R 7 , R 8 , R 9 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 22 and R 23 are hydrogen atoms or alkyl groups having 3 or less carbon atoms, polyphenylene ether Compounds are preferred, and in particular -(O-X-O)- represented by formula (OP-3) or formula (OP-4) is represented by formula (OP-9), formula (OP-10), and/or Formula (OP-11) and -(YO)- represented by formula (OP-5) are preferably formula (OP-12) or formula (OP-13). When a and/or b are integers of 2 or more, -(Y-O)- of 2 or more each independently represents a structure in which two or more of formula (OP-12) and/or formula (OP-13) are arranged. Alternatively, it may have a structure in which formula (OP-12) and formula (OP-13) are arranged in blocks or randomly.
（式（ＯＰ－１０）中、Ｒ４４、Ｒ４５、Ｒ４６、および、Ｒ４７は、同一または異なってもよく、水素原子またはメチル基である。－Ｂ－は、炭素数２０以下の直鎖、分岐または環状の２価の炭化水素基である。）
　－Ｂ－は、式（ＯＰ－４）における－Ａ－の具体例と同じものが具体例として挙げられる。
（式（ＯＰ－１１）中、－Ｂ－は、炭素数２０以下の直鎖、分岐または環状の２価の炭化水素基である。）
　－Ｂ－は、式（ＯＰ－４）における－Ａ－の具体例と同じものが具体例として挙げられる。
 (In formula (OP-10), 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 line having 20 or less carbon atoms. It is a chain, branched, or cyclic divalent hydrocarbon group.)
Specific examples of -B- include the same examples as -A- in formula (OP-4).
(In formula (OP-11), -B- is a straight chain, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms.)
Specific examples of -B- include the same examples as -A- in formula (OP-4).
　その他、炭素－炭素不飽和二重結合を２以上含むポリフェニレンエーテル化合物の詳細は、特開２０１８－０１６７０９号公報の記載を参酌でき、これらの内容は本明細書に組み込まれる。 In addition, for details of the polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds, the description in JP 2018-016709 can be referred to, and the contents thereof are incorporated herein.
　炭素－炭素不飽和二重結合を２以上含むポリフェニレンエーテル化合物（好ましくは、変性ポリフェニレンエーテル化合物（ｇ））のＧＰＣ（ゲルパーミエーションクロマトグラフィ）法によるポリスチレン換算の数平均分子量（詳細は後述する実施例に記載の方法に従う）は、５００以上３，０００以下であることが好ましい。数平均分子量が５００以上であることにより、本実施形態の樹脂組成物を塗膜状にする際にべたつきがより一層抑制される傾向にある。数平均分子量が３，０００以下であることにより、溶剤への溶解性がより一層向上する傾向にある。
　また、炭素－炭素不飽和二重結合を２以上含むポリフェニレンエーテル化合物（好ましくは、変性ポリフェニレンエーテル化合物（ｇ））のＧＰＣによるポリスチレン換算の重量平均分子量（詳細は後述する実施例に記載の方法に従う）は、８００以上１０，０００以下であることが好ましく、８００以上５，０００以下であることがより好ましい。前記下限値以上とすることにより、樹脂組成物の硬化物の比誘電率（Ｄｋ）および誘電正接（Ｄｆ）がより低くなる傾向にあり、上記上限値以下とすることにより、後述するワニス等を作製する際の溶剤への樹脂組成物の溶解性、低粘度性および成形性がより向上する傾向にある。
　さらに、変性ポリフェニレンエーテル化合物（ｇ）である場合の、末端の炭素－炭素不飽和二重結合当量は、炭素－炭素不飽和二重結合１つあたり４００～５０００ｇであることが好ましく、４００～２５００ｇであることがより好ましい。前記下限値以上とすることにより、樹脂組成物の硬化物の比誘電率（Ｄｋ）および誘電正接（Ｄｆ）がより低くなる傾向にある。上記上限値以下とすることにより、溶剤への樹脂組成物の溶解性、低粘度性および成形性がより向上する傾向にある。 The number average molecular weight of a polyphenylene ether compound (preferably a modified polyphenylene ether compound (g)) containing two or more carbon-carbon unsaturated double bonds in terms of polystyrene determined by the GPC (gel permeation chromatography) method (details will be given in Examples below) (according to the method described in ) is preferably 500 or more and 3,000 or less. When the number average molecular weight is 500 or more, stickiness tends to be further suppressed when the resin composition of this embodiment is formed into a coating film. When the number average molecular weight is 3,000 or less, the solubility in a solvent tends to be further improved.
In addition, the weight average molecular weight of a polyphenylene ether compound (preferably a modified polyphenylene ether compound (g)) containing two or more carbon-carbon unsaturated double bonds (preferably a modified polyphenylene ether compound (g)) in terms of polystyrene by GPC (for details, follow the method described in the Examples below) ) is preferably 800 or more and 10,000 or less, more preferably 800 or more and 5,000 or less. By setting the above lower limit or more, the dielectric constant (Dk) and dielectric loss tangent (Df) of the cured product of the resin composition tend to become lower. By setting the above upper limit or less, the varnish etc. described below The solubility, low viscosity, and moldability of the resin composition in the solvent during production tend to be further improved.
Further, in the case of the modified polyphenylene ether compound (g), 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. It is more preferable that By setting it above the lower limit, the relative dielectric constant (Dk) and dielectric loss tangent (Df) of the cured product of the resin composition tend to become lower. By setting it below the above upper limit, the solubility, low viscosity, and moldability of the resin composition in a solvent tend to be further improved.
　本実施形態の樹脂組成物が、炭素－炭素不飽和二重結合を２以上含むポリフェニレンエーテル化合物を含む場合、炭素－炭素不飽和二重結合を２以上含むポリフェニレンエーテル化合物の含有量の下限値は、樹脂組成物中の樹脂固形分１００質量部に対し、１質量部以上であることが好ましく、３質量部以上であることがより好ましく、５質量部以上であることがさらに好ましく、７質量部以上であることが一層好ましく、１０質量部以上であることがより一層好ましい。前記下限値以上とすることにより、得られる硬化物の低吸水性および低誘電特性（Ｄｋおよび／またはＤｆ）がより向上する傾向にある。また、炭素－炭素不飽和二重結合を２以上含むポリフェニレンエーテル化合物の含有量の上限値は、樹脂組成物中の樹脂固形分１００質量部に対し、５０質量部以下であることが好ましく、４５質量部以下であることがより好ましく、４０質量部以下であることがさらに好ましく、３５質量部以下であることが一層好ましく、３０質量部以下であることがより一層好ましく、２５質量部以下であることがさらに一層好ましく、２０質量部以下であってもよい。前記上限値以下とすることにより、得られる硬化物の耐熱性および耐薬品性がより向上する傾向にある。
　本実施形態における樹脂組成物は、炭素－炭素不飽和二重結合を２以上含むポリフェニレンエーテル化合物を１種のみ含んでいてもよいし、２種以上含んでいてもよい。２種以上含む場合、合計量が上記範囲となることが好ましい。 When the resin composition of the present embodiment contains a polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds, the lower limit of the content of the polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds is , preferably 1 part by mass or more, more preferably 3 parts by mass or more, even more preferably 5 parts by mass or more, and 7 parts by mass, based on 100 parts by mass of resin solids in the resin composition. It is more preferable that the amount is above, and even more preferably that it is 10 parts by mass or more. When the amount is equal to or more than the lower limit, the resulting cured product tends to have improved low water absorption and low dielectric properties (Dk and/or Df). Further, the upper limit of the content of the polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds is preferably 50 parts by mass or less, and 45 parts by mass or less, based on 100 parts by mass of the resin solid content in the resin composition. It is more preferably at most 40 parts by mass, even more preferably at most 35 parts by mass, even more preferably at most 30 parts by mass, and even more preferably at most 25 parts by mass. Even more preferably, the amount may be 20 parts by mass or less. When the amount is below the upper limit, the heat resistance and chemical resistance of the obtained cured product tend to be further improved.
The resin composition in this 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, it is preferable that the total amount falls within the above range.
　また、本実施形態における樹脂組成物は、炭素－炭素不飽和二重結合を２以上含むポリフェニレンエーテル化合物を実質的に含まない構成とすることもできる。実質的に含まないとは、炭素－炭素不飽和二重結合を２以上含むポリフェニレンエーテル化合物の含有量が樹脂組成物中の樹脂固形分１００質量部に対し、０．１質量部未満であることをいい、好ましくは０．０１質量部未満であり、さらには０．００１質量部未満であってもよい。 Furthermore, the resin composition in this embodiment can also be configured to substantially not contain a polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds. "Substantially free" means that the content of the polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds is less than 0.1 part by mass based on 100 parts by mass of resin solid content in the resin composition. It is preferably less than 0.01 part by mass, and may even be less than 0.001 part by mass.
　本実施形態の樹脂組成物が他の熱硬化性化合物（Ｃ）を含む場合、その含有量（総量）は、樹脂固形分１００質量部に対し、１質量部以上であることが好ましく、５質量部以上であることがより好ましく、１０質量部以上であることがさらに好ましく、２０質量部以上であることが一層好ましく、３０質量部以上であってもよい。前記下限値以上とすることにより、得られる硬化物の、耐熱性、めっき密着性、および、低熱膨張性等がより向上する傾向にある。また、他の熱硬化性化合物（Ｃ）の含有量の上限値は、樹脂固形分１００質量部に対し、５０質量部以下であることが好ましく、４５質量部以下であることがより好ましく、４０質量部以下であることがさらに好ましい。前記上限値以下とすることにより、得られる硬化物の低誘電特性（Ｄｋおよび／またはＤｆ）および低吸水性がより向上する傾向にある。
　本実施形態の樹脂組成物は、他の熱硬化性化合物（Ｃ）を１種のみ含んでいてもよいし、２種以上含んでいてもよい。２種以上含む場合、合計量が上記範囲となることが好ましい。 When the resin composition of the present embodiment contains another thermosetting compound (C), the content (total amount) is preferably 1 part by mass or more, and 5 parts by mass based on 100 parts by mass of the resin solid content. The amount is more preferably at least 10 parts by mass, even more preferably at least 10 parts by mass, even more preferably at least 20 parts by mass, and may be at least 30 parts by mass. By setting it to the above lower limit or more, the heat resistance, plating adhesion, low thermal expansion, etc. of the obtained cured product tend to be further improved. Further, the upper limit of the content of the other thermosetting compound (C) is preferably 50 parts by mass or less, more preferably 45 parts by mass or less, and 40 parts by mass or less, based on 100 parts by mass of the resin solid content. It is more preferably less than parts by mass. By setting it below the above-mentioned upper limit, the low dielectric properties (Dk and/or Df) and low water absorption of the obtained cured product tend to be further improved.
The resin composition of this embodiment may contain only one type of other thermosetting compound (C), or may contain two or more types. When two or more types are included, it is preferable that the total amount falls within the above range.
＜充填材（Ｄ）＞
　本実施形態の樹脂組成物は、充填材（Ｄ）を含むことが好ましい。充填材（Ｄ）を含むことにより、樹脂組成物やその硬化物の誘電特性（低誘電率性、低誘電正接性等）、耐燃性、低熱膨張性等の物性をより向上させることができる。
　また、本実施形態で用いる充填材（Ｄ）は、低誘電特性（Ｄｋおよび／またはＤｆ）に優れることがより好ましい。例えば、本実施形態で用いる充填材（Ｄ）は、空洞共振器摂動法に従って測定した周波数１０ＧＨｚにおける比誘電率（Ｄｋ）が８．０以下であることが好ましく、６．０以下であることがより好ましく、４．０以下であることがさらに好ましい。また、比誘電率の下限値は、例えば、２．０以上が実際的である。また、本実施形態で用いる充填材（Ｄ）は、空洞共振器摂動法に従って測定した周波数１０ＧＨｚにおける誘電正接（Ｄｆ）が０．０５以下であることが好ましく、０．０１以下であることがより好ましい。また、誘電正接の下限値は、例えば、０．０００１以上が実際的である。 <Filler (D)>
It is preferable that the resin composition of this embodiment contains a filler (D). By including the filler (D), physical properties such as dielectric properties (low dielectric constant, low dielectric loss tangent, etc.), flame resistance, low thermal expansion, etc. of the resin composition and its cured product can be further improved.
Moreover, it is more preferable that the filler (D) used in this embodiment has excellent low dielectric properties (Dk and/or Df). For example, the filler (D) used in this embodiment preferably has a dielectric constant (Dk) of 8.0 or less, and preferably 6.0 or less, at a frequency of 10 GHz measured according to the cavity resonator perturbation method. More preferably, it is 4.0 or less. Moreover, the lower limit of the relative permittivity is practically, for example, 2.0 or more. Further, the filler (D) used in this embodiment preferably has a dielectric loss tangent (Df) of 0.05 or less, more preferably 0.01 or less, at a frequency of 10 GHz measured according to the cavity resonator perturbation method. preferable. Further, the lower limit value of the dielectric loss tangent is practically, for example, 0.0001 or more.
　本実施形態で使用される充填材（Ｄ）としては、その種類は特に限定されず、当業界において一般に使用されているものを好適に用いることができる。具体的には、天然シリカ、溶融シリカ、合成シリカ、アモルファスシリカ、アエロジル、中空シリカ等のシリカ類、アルミナ、ホワイトカーボン、チタンホワイト、酸化チタン、酸化亜鉛、酸化マグネシウム、酸化ジルコニウム等の金属酸化物、ホウ酸亜鉛、錫酸亜鉛、フォルステライト、チタン酸バリウム、チタン酸ストロンチウム、チタン酸カルシウム等の複合酸化物、窒化ホウ素、凝集窒化ホウ素、窒化ケイ素、窒化アルミニウム等の窒化物、水酸化アルミニウム、水酸化アルミニウム加熱処理品（水酸化アルミニウムを加熱処理し、結晶水の一部を減じたもの）、ベーマイト、水酸化マグネシウム等の金属水酸化物（水和物を含む）、酸化モリブデンやモリブデン酸亜鉛等のモリブデン化合物、硫酸バリウム、クレー、カオリン、タルク、焼成クレー、焼成カオリン、焼成タルク、マイカ、Ｅ－ガラス、Ａ－ガラス、ＮＥ－ガラス、Ｃ－ガラス、Ｌ－ガラス、Ｄ－ガラス、Ｓ－ガラス、Ｍ－ガラスＧ２０、ガラス短繊維（Ｅガラス、Ｔガラス、Ｄガラス、Ｓガラス、Ｑガラス等のガラス微粉末類を含む。）、中空ガラス、球状ガラスなど無機系の充填材の他、スチレン型、ブタジエン型、アクリル型などのゴムパウダー、コアシェル型のゴムパウダー、シリコーンレジンパウダー、シリコーンゴムパウダー、シリコーン複合パウダーなど有機系の充填材などが挙げられる。
　本実施形態においては、無機充填材が好ましく、シリカ、水酸化アルミニウム、窒化アルミニウム、窒化ホウ素、フォルステライト、酸化チタン、チタン酸バリウム、チタン酸ストロンチウム、および、チタン酸カルシウムからなる群より選択される１種以上を含むことがより好ましく、低誘電特性（Ｄｋおよび／またはＤｆ）の観点からは、シリカ、および、水酸化アルミニウム、からなる群より選択される１種以上を含むことがより好ましく、シリカを含むことがさらに好ましい。これらの無機充填材を使用することで、樹脂組成物の硬化物の耐熱性、誘電特性、熱膨張特性、寸法安定性、難燃性などの特性がより向上する。 The type of 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, 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, agglomerated boron nitride, silicon nitride, aluminum nitride, aluminum hydroxide, Heat-treated aluminum hydroxide products (aluminum hydroxide heat-treated to reduce some of the crystal water), metal hydroxides (including hydrates) such as boehmite and magnesium hydroxide, 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, short glass fibers (including fine glass powders such as E glass, T glass, D glass, S glass, and Q glass), hollow glass, and spherical glass. Other examples include 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.
In this embodiment, 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 include one or more types, and from the viewpoint of low dielectric properties (Dk and/or Df), it is more preferable to include one or more types selected from the group consisting of silica and aluminum hydroxide. It is further preferred that silica is included. By using these inorganic fillers, properties such as heat resistance, dielectric properties, thermal expansion properties, dimensional stability, and flame retardance of the cured product of the resin composition are further improved.
　本実施形態の樹脂組成物における充填材（Ｄ）の含有量は、所望する特性に応じて適宜設定することができ、特に限定されないが、樹脂組成物中の樹脂固形分１００質量部に対し、１０質量部以上であることが好ましく、２０質量部以上であることがより好ましく、４０質量部以上であることがさらに好ましく、６０質量部以上であることが一層好ましく、８０質量部以上であることがより一層好ましい。前記下限値以上とすることにより、得られる硬化物の低熱膨張性および低誘電正接性がより向上する傾向にある。また、充填材（Ｄ）の含有量の上限値は、樹脂固形分１００質量部に対し、１６００質量部以下であることが好ましく、１０００質量部以下であることがより好ましく、５００質量部以下であることがさらに好ましく、３００質量部以下であることが一層好ましく、２５０質量部以下であることがより一層好ましく、２００質量部以下、１２０質量部以下であってもよい。前記上限値以下とすることにより、樹脂組成物の成形性がより向上する傾向にある。
　本実施形態の樹脂組成物において、好ましい実施形態の一例として、充填材（Ｄ）の含有量が溶剤を除く成分の１～９５質量％である態様が例示され、３０質量％～８０質量％である態様が好ましい。
　本実施形態の樹脂組成物は、充填材（Ｄ）を１種のみ含んでいてもよいし、２種以上含んでいてもよい。２種以上含む場合、合計量が上記範囲となることが好ましい。 The content of the filler (D) in the resin composition of the present embodiment can be appropriately set depending on the desired characteristics, and is not particularly limited, but the content is based on 100 parts by mass of the resin solid content in the resin composition. It is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, even 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 preferable. When the amount is equal to or more than the lower limit, the resulting cured product tends to have improved low thermal expansion and low dielectric loss tangent. Further, the upper limit of the content of the filler (D) is preferably 1,600 parts by mass or less, more preferably 1,000 parts by mass or less, and 500 parts by mass or less, based on 100 parts by mass of the resin solid content. The amount is more preferably 300 parts by mass or less, even more preferably 250 parts by mass or less, and may be 200 parts by mass or less, or 120 parts by mass or less. By setting it below the above upper limit, the moldability of the resin composition tends to be further improved.
In the resin composition of the present embodiment, as an example of a preferable embodiment, the content of the filler (D) is 1 to 95% by mass of the components excluding the solvent, and the content of the filler (D) is 30 to 80% by mass. Certain embodiments are preferred.
The resin composition of this embodiment may contain only one type of filler (D), or may contain two or more types of filler (D). When two or more types are included, it is preferable that the total amount falls within the above range.
　本実施形態の樹脂組成物において、充填材（Ｄ）、特に無機充填材を用いる際、シランカップリング剤をさらに含んでもよい。シランカップリング剤を含むことにより、充填材（Ｄ）の分散性、樹脂成分と、充填材（Ｄ）および後述する基材との接着強度がより向上する傾向にある。
　シランカップリング剤としては特に限定されず、一般に無機物の表面処理に使用されるシランカップリング剤が挙げられ、アミノシラン系化合物（例えば、γ－アミノプロピルトリエトキシシラン、Ｎ－β－（アミノエチル）－γ－アミノプロピルトリメトキシシラン等）、エポキシシラン系化合物（例えば、γ－グリシドキシプロピルトリメトキシシラン等）、ビニルシラン系化合物（例えば、ビニルトリメトキシシラン等）、スチリルシラン系化合物（例えば、ｐ－スチリルトリメトキシシラン等）、アクリルシラン系化合物（例えば、γ－アクリロキシプロピルトリメトキシシラン等）、カチオニックシラン系化合物（例えば、Ｎ－β－（Ｎ－ビニルベンジルアミノエチル）－γ－アミノプロピルトリメトキシシラン塩酸塩等）、フェニルシラン系化合物等が挙げられる。シランカップリング剤は、１種を単独で、または２種以上を組み合わせて用いられる。
　シランカップリング剤の含有量は、特に限定されないが、樹脂固形分１００質量部に対して、０．１～５．０質量部であってよい。 In the resin composition of this embodiment, when using a filler (D), especially an inorganic filler, it may further contain a silane coupling agent. By including a silane coupling agent, the dispersibility of the filler (D) and the adhesive strength between the resin component and the filler (D) and the substrate described below tend to be further improved.
Silane coupling agents are not particularly limited, and include silane coupling agents that are generally used for surface treatment of inorganic materials, such as aminosilane compounds (for example, γ-aminopropyltriethoxysilane, N-β-(aminoethyl) -γ-aminopropyltrimethoxysilane, etc.), epoxysilane compounds (e.g., γ-glycidoxypropyltrimethoxysilane, etc.), vinylsilane compounds (e.g., vinyltrimethoxysilane, etc.), styrylsilane compounds (e.g., p-styryltrimethoxysilane, etc.), acrylic silane compounds (e.g., γ-acryloxypropyltrimethoxysilane, etc.), cationic silane compounds (e.g., N-β-(N-vinylbenzylaminoethyl)-γ- (aminopropyltrimethoxysilane hydrochloride, etc.), phenylsilane compounds, etc. The silane coupling agents may be used alone or in combination of two or more.
The content of the silane coupling agent is not particularly limited, but may be 0.1 to 5.0 parts by weight based on 100 parts by weight of the resin solid content.
＜分子量が１０００未満であり、かつ、炭素－炭素不飽和結合を含む有機基を分子内に１つ含む低分子ビニル化合物＞
　本実施形態の樹脂組成物は、分子量が１０００未満であり、かつ、炭素－炭素不飽和結合を含む有機基を分子内に１つ含む低分子ビニル化合物（以下、単に、「低分子ビニル化合物」ということがある）を含んでいてもよい。低分子ビニル化合物を配合することにより、得られる硬化物の低誘電特性（Ｄｋおよび／またはＤｆ）、および、吸湿耐熱性がより向上する傾向にある。
　ここで、前記炭素－炭素不飽和結合を含む有機基を構成する炭素－炭素不飽和結合は、芳香環の一部として含まれるものは含まない趣旨である。一方、非芳香環の一部として含まれる炭素－炭素不飽和結合は含む趣旨である。非芳香環の一部として含まれる炭素－炭素不飽和結合の例としては、シクロヘキセニル基などが挙げられる。また、直鎖または分岐鎖の有機基の末端以外の部分、すなわち、直鎖または分岐鎖中に含まれる炭素－炭素不飽和結合（例えば、ビニレン基）も含む趣旨である。
　本実施形態においては、前記炭素－炭素不飽和結合を含む有機基が、ＣＨ２＝Ｃ（Ｘ）－（Ｘは水素原子またはメチル基である）構造を有することが好ましい。このように、分子の端部に炭素－炭素不飽和結合を含む化合物を採用することにより、より効果的に式（Ｖ）で表される構成単位を有する重合体（Ｖ）が有するビニル基と反応させることが可能になる。
　前記炭素－炭素不飽和結合を含む有機基は、ビニル基、アリル基、アクリル基、および、メタアクリル基からなる群より選ばれる１つであることがより好ましく、ビニル基であることがさらに好ましい。 <Low molecular vinyl compound with a molecular weight of less than 1000 and containing one organic group containing a carbon-carbon unsaturated bond in the molecule>
The resin composition of the present embodiment is a low-molecular vinyl compound (hereinafter simply referred to as a "low-molecular vinyl compound") having a molecular weight of less than 1000 and containing one organic group containing a carbon-carbon unsaturated bond in the molecule. ) may also be included. By blending a low-molecular-weight vinyl compound, the resulting cured product tends to have improved low dielectric properties (Dk and/or Df) and moisture absorption heat resistance.
Here, the carbon-carbon unsaturated bonds constituting the organic group containing carbon-carbon unsaturated bonds do not include those included as part of an aromatic ring. On the other hand, it is meant to include carbon-carbon unsaturated bonds included as part of non-aromatic rings. An example of a carbon-carbon unsaturated bond included as part of the non-aromatic ring includes a cyclohexenyl group. It is also intended to include portions other than the terminals of linear or branched organic groups, ie, carbon-carbon unsaturated bonds (eg, vinylene groups) contained in the linear or branched chains.
In this embodiment, the organic group containing the carbon-carbon unsaturated bond preferably has a structure of CH 2 =C(X)- (X is a hydrogen atom or a methyl group). In this way, by employing a compound containing a carbon-carbon unsaturated bond at the end of the molecule, it is possible to more effectively interact with the vinyl group of the polymer (V) having the structural unit represented by formula (V). 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 even more preferably a vinyl group. .
　本実施形態で用いる低分子ビニル化合物は、また、炭素原子、水素原子、酸素原子、窒素原子、およびケイ素原子からなる群より選択される原子のみで構成されていることが好ましく、炭素原子、水素原子、酸素原子、およびケイ素原子からなる群より選択される原子のみで構成されていることがより好ましく、炭素原子、水素原子、および酸素原子からなる群より選択される原子のみで構成されていることがさらに好ましい。
　本実施形態で用いる低分子ビニル化合物は、また、極性基を有していてもよいし、有していなくてもよい。本実施形態で用いる低分子ビニル化合物は、極性基を有していない方が好ましい。極性基としては、アミノ基、カルボキシル基、ヒドロキシ基、ニトロ基が例示される。 The low-molecular-weight vinyl compound used in this embodiment is also preferably composed only of atoms selected from the group consisting of carbon atoms, hydrogen atoms, oxygen atoms, nitrogen atoms, and silicon atoms; More preferably, it is composed only of atoms selected from the group consisting of atoms, oxygen atoms, and silicon atoms, and it is composed only of atoms selected from the group consisting of carbon atoms, hydrogen atoms, and oxygen atoms. It is even more preferable.
The low molecular weight vinyl compound used in this embodiment may or may not have a polar group. It is preferable that the low molecular weight vinyl compound used in this embodiment has no polar group. Examples of the polar group include an amino group, a carboxyl group, a hydroxy group, and a nitro group.
　本実施形態において、低分子ビニル化合物の分子量は７０以上であることが好ましく、８０以上であることがより好ましく、９０以上であることがさらに好ましい。前記下限値以上とすることにより、本実施形態の樹脂組成物やその硬化物等からの低分子ビニル化合物の揮発を抑制できる傾向にある。低分子ビニル化合物の分子量の上限は、５００以下であることが好ましく、４００以下であることがより好ましく、３００以下であることがさらに好ましく、２００以下であることが一層好ましく、１５０以下であってもよい。前記上限値以下とすることにより、式（Ｖ）で表される構成単位を有する重合体（Ｖ）との反応性を高める効果がより向上する傾向にある。
　本実施形態の樹脂組成物が低分子ビニル化合物を２種以上含む場合、低分子ビニル化合物の平均分子量値が上記範囲に含まれることが好ましく、それぞれの化合物の分子量が上記好ましい範囲に含まれることがより好ましい。 In this embodiment, the molecular weight of the low molecular weight vinyl compound is preferably 70 or more, more preferably 80 or more, and even more preferably 90 or more. By setting it to the above-mentioned lower limit or more, there is a tendency that volatilization of the low molecular weight vinyl compound from the resin composition of the present embodiment, its cured product, etc. can be suppressed. The upper limit of the molecular weight of the low molecular vinyl compound is preferably 500 or less, more preferably 400 or less, even more preferably 300 or less, even more preferably 200 or less, and 150 or less. Good too. By setting it below the above-mentioned upper limit, the effect of increasing the reactivity with the polymer (V) having the structural unit represented by the formula (V) tends to be further improved.
When the resin composition of the present embodiment contains two or more kinds of low-molecular-weight vinyl compounds, it is preferable that the average molecular weight value of the low-molecular-weight vinyl compounds is within the above range, and the molecular weight of each compound is within the above preferable range. is more preferable.
　本実施形態において、低分子ビニル化合物は沸点が１１０℃以上であることが好ましく、１１５℃以上であることがより好ましく、１２０℃以上であることがさらに好ましい。前記下限値以上とすることにより、樹脂組成物を熱硬化させる際の低分子ビニル化合物の揮発が抑制され、より効果的に式（Ｖ）で表される構成単位を有する重合体（Ｖ）が有するビニル基と低分子ビニル化合物とを反応させることができる。低分子ビニル化合物の沸点は、３００℃以下であることが好ましく、２５０℃以下であることがより好ましく、２００℃以下であることがさらに好ましい。前記上限値以下とすることにより、硬化物中に残溶剤として残りにくくすることができる。
　本実施形態の樹脂組成物が低分子ビニル化合物を２種以上含む場合、沸点の平均値が上記範囲に入ればよいが、それぞれの化合物の沸点が上記好ましい範囲に含まれることが好ましい。 In this embodiment, the low molecular weight vinyl compound preferably has a boiling point of 110°C or higher, more preferably 115°C or higher, and even more preferably 120°C or higher. By setting the value above the lower limit, volatilization of the low molecular weight vinyl compound during thermosetting of the resin composition is suppressed, and the polymer (V) having the structural unit represented by the formula (V) is more effectively produced. It is possible to react the vinyl group possessed by a low-molecular-weight vinyl compound. The boiling point of the low molecular weight vinyl compound is preferably 300°C or lower, more preferably 250°C or lower, and even more preferably 200°C or lower. By controlling the amount to be less than or equal to the upper limit, it is possible to make it difficult for residual solvent to remain in the cured product.
When the resin composition of the present embodiment contains two or more types of low-molecular-weight vinyl compounds, it is sufficient that the average value of the boiling points falls within the above range, but it is preferable that the boiling point of each compound falls within the above preferable range.
　低分子ビニル化合物としては、（メタ）アクリル酸エステル化合物、芳香族ビニル化合物（好ましくはスチレン系化合物）、飽和脂肪酸ビニル化合物、シアン化ビニル化合物、エチレン性不飽和カルボン酸、エチレン性不飽和カルボン酸無水物、エチレン性不飽和ジカルボン酸モノアルキルエステル、エチレン性不飽和カルボン酸アミド、ビニルシラン化合物（例えば、ビニルトリアルコキシシラン等）、アクリルシラン化合物（例えば、アクリルトリアルコキシシラン等）、メタアクリルシラン化合物（例えば、メタアクリルトリアルコキシシラン等）、スチリルシラン化合物（例えば、スチリルトリアルコキシシラン等）などが例示される。
　低分子ビニル化合物の第一の形態は、（メタ）アクリル酸エステル化合物、芳香族ビニル化合物、飽和脂肪酸ビニル化合物、シアン化ビニル化合物、エチレン性不飽和カルボン酸、エチレン性不飽和カルボン酸無水物、エチレン性不飽和ジカルボン酸モノアルキルエステル、および、エチレン性不飽和カルボン酸アミドからなる群より選択される少なくとも１種である。
　低分子ビニル化合物の第二の形態は、（メタ）アクリル酸エステル化合物、芳香族ビニル化合物、飽和脂肪酸ビニル化合物、ビニルシラン化合物、アクリルシラン化合物、メタアクリルシラン化合物、スチリルシラン化合物からなる群より選ばれる少なくとも１種であり、芳香族ビニル化合物および／またはビニルシラン化合物が好ましい。
　低分子ビニル化合物の具体例としては、メチルスチレン、エチルビニルベンゼン、ビニルトリメトキシシラン、ビニルトリエトキシシランが例示される。 Examples of low-molecular vinyl compounds include (meth)acrylic acid ester 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, vinyl silane compounds (e.g., vinyltrialkoxysilanes, etc.), acrylic silane compounds (e.g., acrylic trialkoxysilanes, etc.), methacrylsilane compounds (for example, methacryltrialkoxysilane, etc.), styrylsilane compounds (for example, styryltrialkoxysilane, etc.), and the like.
The first forms of low-molecular vinyl compounds include (meth)acrylic acid ester compounds, aromatic vinyl compounds, saturated fatty acid vinyl compounds, vinyl cyanide compounds, ethylenically unsaturated carboxylic acids, ethylenically unsaturated carboxylic acid anhydrides, It is at least one selected from the group consisting of ethylenically unsaturated dicarboxylic acid monoalkyl esters and ethylenically unsaturated carboxylic acid amides.
The second form of the low molecular weight vinyl compound is selected from the group consisting of (meth)acrylic acid ester compounds, aromatic vinyl compounds, saturated fatty acid vinyl compounds, vinyl silane compounds, acrylic silane compounds, methacrylic silane compounds, and styryl silane compounds. It is at least one kind, and aromatic vinyl compounds and/or vinyl silane compounds are preferred.
Specific examples of low molecular weight vinyl compounds include methylstyrene, ethylvinylbenzene, vinyltrimethoxysilane, and vinyltriethoxysilane.
　本実施形態の樹脂組成物において、低分子ビニル化合物の含有量は、樹脂固形分１００質量部に対し、１質量部以上であることが好ましく、２質量部以上であることがより好ましく、２．５質量部以上であることがさらに好ましい。前記下限値以上とすることにより、得られる硬化物中の未反応官能基が減少し、得られる硬化物の吸湿耐熱性が改善する傾向にある。また、低分子ビニル化合物の含有量の上限値は、樹脂固形分１００質量部に対し、３０質量部以下であることが好ましく２０質量部以下であることがより好ましく、１０質量部以下であることがさらに好ましく、８質量部以下であることが一層好ましく、５質量部以下であることがより一層好ましい。前記上限値以下とすることにより、得られる硬化物の低誘電特性（Ｄｋおよび／またはＤｆ）がより向上する傾向にある。
　本実施形態の樹脂組成物は、低分子ビニル化合物を１種のみ含んでいてもよいし、２種以上含んでいてもよい。２種以上含む場合、合計量が上記範囲となることが好ましい。 In the resin composition of the present embodiment, the content of the low molecular weight vinyl compound 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. More preferably, the amount is 5 parts by mass or more. By setting the amount to be equal to or more than the lower limit, the amount of unreacted functional groups in the obtained cured product tends to decrease, and the moisture absorption and heat resistance of the obtained cured product tends to improve. Further, the upper limit of the content of the low molecular weight vinyl compound is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and 10 parts by mass or less based on 100 parts by mass of the resin solid content. is more preferable, even more preferably 8 parts by mass or less, even more preferably 5 parts by mass or less. By setting it below the above-mentioned upper limit, the low dielectric properties (Dk and/or Df) of the obtained cured product tend to be further improved.
The resin composition of this embodiment may contain only one type of low-molecular-weight vinyl compound, or may contain two or more types of low-molecular-weight vinyl compounds. When two or more types are included, it is preferable that the total amount falls within the above range.
　本実施形態の樹脂組成物においては、式（Ｖ）で表される構成単位を有する重合体（Ｖ）と低分子ビニル化合物の質量比率が、式（Ｖ）で表される構成単位を有する重合体（Ｖ）１に対し、０．０２５以上であることが好ましく、０．０５以上であることがより好ましい。前記下限値以上とすることにより、得られる硬化物中の未反応官能基が減少し、得られる硬化物の吸湿耐熱性が改善する傾向にある。上記式（Ｖ）で表される構成単位を有する重合体（Ｖ）と低分子ビニル化合物の質量比率の上限は、式（Ｖ）で表される構成単位を有する重合体（Ｖ）１に対し、０．７以下であることが好ましく、０．５以下であることがより好ましく、０．４以下であることがさらに好ましく、０．３以下であることが一層好ましく、０．２５以下であってもよい。前記上限値以下とすることにより、得られる硬化物の低誘電特性（Ｄｋおよび／またはＤｆ）がより向上する傾向にある。 In the resin composition of the present embodiment, the mass ratio of the polymer (V) having the structural unit represented by formula (V) and the low molecular weight vinyl compound is such that the mass ratio of the polymer (V) having the structural unit represented by formula (V) is It is preferably 0.025 or more, more preferably 0.05 or more, based on 1 of coalescence (V). By setting the amount to be equal to or more than the lower limit, the amount of unreacted functional groups in the obtained cured product tends to decrease, and the moisture absorption and heat resistance of the obtained cured product tends to improve. The upper limit of the mass ratio of the polymer (V) having the structural unit represented by the above formula (V) and the low molecular weight vinyl compound is 1 for the polymer (V) having the structural unit represented by the formula (V). , is preferably 0.7 or less, more preferably 0.5 or less, even more preferably 0.4 or less, even more preferably 0.3 or less, and 0.25 or less. It's okay. By setting it below the above-mentioned upper limit, the low dielectric properties (Dk and/or Df) of the obtained cured product tend to be further improved.
＜エチレン性不飽和基を有するオリゴマー＞
　本実施形態の樹脂組成物には、熱硬化性および活性エネルギー線による硬化性（例えば紫外線による光硬化性等）を高めるために、エチレン性不飽和基を有するオリゴマーを併用することも可能である。本実施形態に用いるエチレン性不飽和基を有するオリゴマーは、１分子中に１個以上のエチレン性不飽和基を有するオリゴマーであれば、特に限定されないが、例えば、ビニル基、アリル基、（メタ）アクリロイル基等を有するオリゴマーが挙げられ、ビニル基を有するオリゴマーが好ましい。
　尚、本明細書においては、エチレン性不飽和基を有するオリゴマーに該当する化合物であって、炭素－炭素不飽和二重結合を２以上含むポリフェニレンエーテル化合物にも該当する化合物は、炭素－炭素不飽和二重結合を２以上含むポリフェニレンエーテル化合物とする。
　エチレン性不飽和基を有するオリゴマーは、スチレンオリゴマーが好ましい。本実施形態に係るスチレンオリゴマーとは、スチレンおよび上記スチレン誘導体、ビニルトルエンからなる群より選択される少なくとも１種を重合してなることが好ましい。スチレンオリゴマーの数平均分子量は、１７８以上であることが好ましく、また、１６００以下であることが好ましい。また、スチレンオリゴマーは、平均の芳香環数が２～１４、芳香環数の２～１４の総量が５０質量％以上、沸点が３００℃以上である分岐構造のない化合物であることが好ましい。 <Oligomer having ethylenically unsaturated group>
It is also possible to use an oligomer having an ethylenically unsaturated group in the resin composition of this embodiment in order to enhance thermosetting properties and curability by active energy rays (for example, photocurability by ultraviolet rays). . The oligomer having an ethylenically unsaturated group used in this embodiment is not particularly limited as long as it has one or more ethylenically unsaturated group in one molecule. ) Examples include oligomers having an acryloyl group, etc., and oligomers having a vinyl group are preferred.
In this specification, a compound that corresponds to an oligomer having an ethylenically unsaturated group and also corresponds to a polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds is referred to as a carbon-carbon unsaturated group. A polyphenylene ether compound containing two or more saturated double bonds.
The oligomer having an ethylenically unsaturated group is preferably a styrene oligomer. The styrene oligomer according to the present embodiment is preferably formed by polymerizing at least one member selected from the group consisting of styrene, the above-mentioned styrene derivatives, and vinyltoluene. The number average molecular weight of the styrene oligomer is preferably 178 or more, and preferably 1,600 or less. Further, the styrene oligomer is preferably a compound without a branched structure having an average number of aromatic rings of 2 to 14, a total amount of 2 to 14 aromatic rings of 50% by mass or more, and a boiling point of 300° C. or more.
　本実施形態に用いられるスチレンオリゴマーとしては、例えば、スチレン重合体、ビニルトルエン重合体、α－メチルスチレン重合体、ビニルトルエン－α－メチルスチレン重合体、スチレン－α－スチレン重合体等が挙げられる。スチレン重合体としては、市販品を用いてもよく、例えばピコラスチックＡ５（イーストマンケミカル社製）、ピコラスチックＡ－７５（イーストマンケミカル社製）、ピコテックス７５（イーストマンケミカル社製）、ＦＴＲ－８１００（三井化学（株）製）、ＦＴＲ－８１２０（三井化学（株）製）が挙げられる。また、ビニルトルエン－α－メチルスチレン重合体としては、ピコテックスＬＣ（イーストマンケミカル社製）が挙げられる。また、α－メチルスチレン重合体としてはクリスタレックス３０７０（イーストマンケミカル社製）、クリスタレックス３０８５（イーストマンケミカル社製）、クリスタレックス（３１００）、クリスタレックス５１４０（イーストマンケミカル社製）、ＦＭＲ－０１００（三井化学（株）製）、ＦＭＲ－０１５０（三井化学（株）製）が挙げられる。また、スチレン－α－スチレン重合体としてはＦＴＲ－２１２０（三井化学（株）製）が挙げられる。これらのスチレンオリゴマーは単独で用いても、２種以上を併用してもよい。
　本実施形態の樹脂組成物においては、α－メチルスチレンオリゴマーが、良好に熱硬化し、良好な微細配線の埋め込み性および半田耐熱性、低比誘電率、低誘電正接に優れることから好ましい。 Examples of the styrene oligomer used in this embodiment include styrene polymer, vinyltoluene polymer, α-methylstyrene polymer, vinyltoluene-α-methylstyrene polymer, styrene-α-styrene polymer, etc. . As the styrene polymer, commercially available products may be used, such as Picolastic A5 (manufactured by Eastman Chemical Company), Picolastic A-75 (manufactured by Eastman Chemical Company), Picotex 75 (manufactured by Eastman Chemical Company), Examples include FTR-8100 (manufactured by Mitsui Chemicals, Inc.) and FTR-8120 (manufactured by Mitsui Chemicals, Inc.). Furthermore, examples of the vinyltoluene-α-methylstyrene polymer include Picotex LC (manufactured by Eastman Chemical Company). In addition, as α-methylstyrene polymers, Crystallex 3070 (manufactured by Eastman Chemical Company), Crystallex 3085 (manufactured by Eastman Chemical Company), Crystallex (3100), Crystallex 5140 (manufactured by Eastman Chemical Company), FMR -0100 (manufactured by Mitsui Chemicals, Inc.) and FMR-0150 (manufactured by Mitsui Chemicals, Inc.). Furthermore, examples of the styrene-α-styrene polymer include FTR-2120 (manufactured by Mitsui Chemicals, Inc.). These styrene oligomers may be used alone or in combination of two or more.
In the resin composition of the present embodiment, α-methylstyrene oligomer is preferable because it can be thermally cured well and is excellent in embedding of fine wiring, soldering heat resistance, low dielectric constant, and low dielectric loss tangent.
　本実施形態の樹脂組成物がエチレン性不飽和基を有するオリゴマーを含む場合、その含有量は、樹脂組成物中の樹脂固形分１００質量部に対し、０．５質量部以上であることが好ましく、１質量部以上であることがより好ましく、２質量部以上であることがさらに好ましく、３質量部以上であることが一層好ましく、さらには、５質量部以上であってもよい。前記下限値以上とすることにより、得られる硬化物の低誘電性がより向上する傾向にある。また、エチレン性不飽和基を有するオリゴマーの含有量の上限値は、樹脂組成物中の樹脂固形分１００質量部に対し、３０質量部以下であることが好ましく、２５質量部以下であることがより好ましく、２０質量部以下であることがさらに好ましく、１５質量部以下であることが一層好ましく、１０質量部以下であることがより一層好ましい。前記上限値以下とすることにより、得られる硬化物の耐熱性がより向上する傾向にある。また、得られる硬化物の、低誘電率性、低誘電正接性、および、耐薬品性がより向上する傾向にある。
　本実施形態の樹脂組成物は、エチレン性不飽和基を有するオリゴマーを１種のみ含んでいてもよいし、２種以上含んでいてもよい。２種以上含む場合、合計量が上記範囲となることが好ましい。 When the resin composition of the present embodiment contains an oligomer having an ethylenically unsaturated group, the content thereof is preferably 0.5 parts by mass or more based on 100 parts by mass of resin solids in the resin composition. , more preferably 1 part by mass or more, further preferably 2 parts by mass or more, even more preferably 3 parts by mass or more, and furthermore, may be 5 parts by mass or more. When the amount is equal to or more than the lower limit, the resulting cured product tends to have improved low dielectric properties. Further, the upper limit of the content of the oligomer having an ethylenically unsaturated group is preferably 30 parts by mass or less, and preferably 25 parts by mass or less, based on 100 parts by mass of the resin solid content in the resin composition. The content is more preferably 20 parts by mass or less, even more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less. By setting it below the upper limit, the heat resistance of the obtained cured product tends to be further improved. Furthermore, the resulting cured product tends to have improved low dielectric constant, low dielectric loss tangent, and chemical resistance.
The resin composition of the present embodiment may contain only one kind of oligomer having an ethylenically unsaturated group, or may contain two or more kinds of oligomers having an ethylenically unsaturated group. When two or more types are included, it is preferable that the total amount falls within the above range.
＜熱可塑性エラストマー＞
　本実施形態の樹脂組成物は、熱可塑性エラストマーを含んでいてもよい。
　本実施形態における熱可塑性エラストマーは、特に限定されず、例えば、ポリイソプレン、ポリブタジエン、スチレンブタジエン、ブチルゴム、エチレンプロピレンゴム、スチレンブタジエンエチレン、スチレンブタジエンスチレン、スチレンイソプレンスチレン、スチレンエチレンブチレンスチレン、スチレンプロピレンスチレン、スチレンエチレンプロピレンスチレン、フッ素ゴム、シリコーンゴム、それらの水添化合物、それらのアルキル化合物、およびそれらの共重合体からなる群より選択される少なくとも１種が挙げられる。 <Thermoplastic elastomer>
The resin composition of this embodiment may contain a thermoplastic elastomer.
The thermoplastic elastomer in this embodiment is not particularly limited, and includes, for example, polyisoprene, polybutadiene, styrene butadiene, butyl rubber, ethylene propylene rubber, styrene butadiene ethylene, styrene butadiene styrene, styrene isoprene styrene, styrene ethylene butylene styrene, styrene propylene styrene. , styrene ethylene propylene styrene, fluororubber, silicone rubber, hydrogenated compounds thereof, alkyl compounds thereof, and copolymers thereof.
　本実施形態で用いる熱可塑性エラストマーの数平均分子量は、５万以上であることが好ましい。数平均分子量を、５万以上とすることにより、得られる硬化物の低誘電特性（Ｄｋおよび／またはＤｆ）がより優れる傾向にある。数平均分子量は、６万以上であることが好ましく、７万以上であることがより好ましく、８万以上であることがさらに好ましい。熱可塑性エラストマーの数平均分子量の上限は、４０万以下であることが好ましく、３５万以下であることがより好ましく、３０万以下であることがさらに好ましい。前記上限値以下とすることにより、熱可塑性エラストマー成分の樹脂組成物への溶解性が向上する傾向にある。
　本実施形態の樹脂組成物が２種以上の熱可塑性エラストマーを含む場合、それらの混合物の数平均分子量が上記範囲を満たすことが好ましい。 The number average molecular weight of the thermoplastic elastomer used in this embodiment is preferably 50,000 or more. By setting the number average molecular weight to 50,000 or more, the resulting cured product tends to have better low dielectric properties (Dk and/or Df). The number average molecular weight is preferably 60,000 or more, more preferably 70,000 or more, and even more preferably 80,000 or more. The upper limit of the number average molecular weight of the thermoplastic elastomer is preferably 400,000 or less, more preferably 350,000 or less, and even more preferably 300,000 or less. By setting it below the upper limit, the solubility of the thermoplastic elastomer component in the resin composition tends to improve.
When the resin composition of this embodiment contains two or more types of thermoplastic elastomers, it is preferable that the number average molecular weight of the mixture satisfies the above range.
　本実施形態において、熱可塑性エラストマーは、スチレン単量体単位と、共役ジエン単量体単位を含む熱可塑性エラストマー（以下、「熱可塑性エラストマー（Ｅ）」と称する）が好ましい。このような熱可塑性エラストマー（Ｅ）を用いることにより、得られる硬化物の低誘電特性（Ｄｋおよび／またはＤｆ）がより優れる。 In this embodiment, the thermoplastic elastomer is preferably a thermoplastic elastomer containing a styrene monomer unit and a conjugated diene monomer unit (hereinafter referred to as "thermoplastic elastomer (E)"). By using such a thermoplastic elastomer (E), the obtained cured product has better low dielectric properties (Dk and/or Df).
　上記熱可塑性エラストマー（Ｅ）は、スチレン単量体単位を含む。スチレン単量体単位を含むことにより、熱可塑性エラストマー（Ｅ）の樹脂組成物への溶解性が向上する。スチレン単量体としては、スチレン、α－メチルスチレン、ｐ－メチルスチレン、ジビニルベンゼン（ビニルスチレン）、Ｎ，Ｎ－ジメチル－ｐ－アミノエチルスチレン、Ｎ，Ｎ－ジエチル－ｐ－アミノエチルスチレン等が例示され、これらの中でも、入手性および生産性の観点から、スチレン、α－メチルスチレン、ｐ－メチルスチレンが好ましい。これらの中でもスチレンが特に好ましい。
　上記熱可塑性エラストマー（Ｅ）におけるスチレン単量体単位の含有量は、全単量体単位の１０～５０質量％の範囲が好ましく、１３～４５質量％の範囲がより好ましく、１５～４０質量％の範囲がさらに好ましい。スチレン単量体単位の含有量が５０質量％以下であれば、基材等との密着性、粘着性がより良好になる。また、１０質量％以上であれば、粘着昂進を抑制でき、糊残りやストップマークが生じにくく、粘着面同士の易剥離性が良好になる傾向にあるため好ましい。
　熱可塑性エラストマー（Ｅ）はスチレン単量体単位を１種のみ含んでいてもよいし、２種以上含んでいてもよい。２種以上含む場合、合計量が上記範囲であることが好ましい。
　本実施形態の熱可塑性エラストマー（Ｅ）中のスチレン単量体単位の含有量の測定方法は、国際公開第２０１７／１２６４６９号の記載を参酌でき、この内容は本明細書に組み込まれる。後述する、共役ジエン単量体単位等についても同様である。 The thermoplastic elastomer (E) contains styrene monomer units. By including the styrene monomer unit, the solubility of the thermoplastic elastomer (E) in the resin composition is improved. Styrene monomers include styrene, α-methylstyrene, p-methylstyrene, divinylbenzene (vinylstyrene), N,N-dimethyl-p-aminoethylstyrene, N,N-diethyl-p-aminoethylstyrene, etc. Among these, styrene, α-methylstyrene, and p-methylstyrene are preferred from the viewpoint of availability and productivity. Among these, styrene is particularly preferred.
The content of styrene monomer units in the 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 of the total monomer units. The range of is more preferable. If the content of styrene monomer units is 50% by mass or less, the adhesiveness and tackiness to the substrate etc. will be better. Further, if it is 10% by mass or more, it is preferable because it is possible to suppress the increase in adhesion, it is difficult to form adhesive residue or stop marks, and the easy peelability between adhesive surfaces tends to be good.
The thermoplastic elastomer (E) may contain only one type of styrene monomer unit, or may contain two or more types of styrene monomer units. When two or more types are included, it is preferable that the total amount is within the above range.
For the method of measuring the content of styrene monomer units in the thermoplastic elastomer (E) of the present embodiment, the description in International Publication No. 2017/126469 can be referred to, and the content thereof is incorporated herein. The same applies to the conjugated diene monomer unit, etc., which will be described later.
　上記熱可塑性エラストマー（Ｅ）は、共役ジエン単量体単位を含む。共役ジエン単量体単位を含むことにより、熱可塑性エラストマー（Ｅ）の樹脂組成物への溶解性が向上する。共役ジエン単量体としては、１対の共役二重結合を有するジオレフィンである限り、特に限定されない。共役ジエン単量体は、例えば、１，３－ブタジエン、２－メチル－１，３－ブタジエン（イソプレン）、２，３－ジメチル－１，３－ブタジエン、１，３－ペンタジエン、２－メチル－１，３－ペン タジエン、１，３－ヘキサジエン、および、ファルネセンが挙げられ、１，３－ブタジエン、および、イソプレンが好ましく、１，３－ブタジエンがより好ましい。
　熱可塑性エラストマー（Ｅ）は共役ジエン単量体単位を１種のみ含んでいてもよいし、２種以上含んでいてもよい。 The thermoplastic elastomer (E) contains a conjugated diene monomer unit. By including the conjugated diene monomer unit, the solubility of the thermoplastic elastomer (E) in the resin composition is improved. The conjugated diene monomer is not particularly limited as long as it is a diolefin having one pair of conjugated double bonds. Conjugated diene monomers include, 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 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.
　上記熱可塑性エラストマー（Ｅ）においては、スチレン単量体単位と共役ジエン単量体単位との質量比率が、スチレン単量体単位／共役ジエン単量体単位＝５／９５～８０／２０の範囲であることが好ましく、７／９３～７７／２３の範囲であることがより好ましく、１０／９０～７０／３０の範囲であることがさらに好ましい。スチレン重合体単位と共役ジエン単量体単位の質量比率が、５／９５～８０／２０の範囲であれば、粘着昂進を抑制し粘着力を高く維持でき、粘着面同士の易剥離性が良好になる。 In the thermoplastic elastomer (E), the mass ratio of styrene monomer units to conjugated diene monomer units is in the range of styrene monomer units/conjugated diene monomer units = 5/95 to 80/20. It is preferably in the range of 7/93 to 77/23, and even more preferably in the range of 10/90 to 70/30. If the mass ratio of the styrene polymer unit to the conjugated diene monomer unit is in the range of 5/95 to 80/20, it is possible to suppress the increase in adhesion and maintain high adhesion, and the easy peelability between adhesive surfaces is good. become.
　上記熱可塑性エラストマー（Ｅ）は、熱可塑性エラストマーの共役ジエン結合の全部が水素添加されていてもよいし、一部水素添加されていてもよいし、水素添加されていなくてもよい。 In the thermoplastic elastomer (E), all or some of the conjugated diene bonds of the thermoplastic elastomer may be hydrogenated, or may not be hydrogenated.
　上記熱可塑性エラストマー（Ｅ）は、スチレン単量体単位および共役ジエン単量体単位に加え、他の単量体単位を含んでいてもよいし、含んでいなくてもよい。他の単量体単位としては、スチレン単量体単位以外の芳香族ビニル化合物単位などが例示される。
　上記熱可塑性エラストマー（Ｅ）は、スチレン単量体単位および共役ジエン単量体単位の合計が全単量体単位の９０質量％以上であることが好ましく、９５質量％以上であることがより好ましく、９７質量％以上であることがさらに好ましく、９９質量％以上であることが一層好ましい。
　上述の通り、熱可塑性エラストマー（Ｅ）は、スチレン単量体単位および共役ジエン単量体単位を、それぞれ、１種のみ含んでいてもよいし、２種以上含んでいてもよい。２種以上含む場合、合計量が上記範囲となることが好ましい。 The thermoplastic elastomer (E) may or may not contain other monomer units in addition to the styrene monomer unit and the conjugated diene monomer unit. Examples of other monomer units include aromatic vinyl compound units other than styrene monomer units.
In the thermoplastic elastomer (E), the sum of styrene monomer units and conjugated diene monomer units is preferably 90% by mass or more, more preferably 95% by mass or more of the total monomer units. , more preferably 97% by mass or more, even more preferably 99% by mass or more.
As mentioned above, the thermoplastic elastomer (E) may contain only one type of styrene monomer unit and conjugated diene monomer unit, or may contain two or more types of each. When two or more types are included, it is preferable that the total amount falls within the above range.
　本実施形態で用いる熱可塑性エラストマー（Ｅ）は、ブロック重合体であっても、ランダム重合体であってもよい。また、共役ジエン単量体単位が水素添加された水添エラストマーであっても、水素添加されていない未水添エラストマーであっても、部分的に水素添加された部分水添エラストマーであってもよい。
　本実施形態の一実施形態においては、熱可塑性エラストマー（Ｅ）は、未水添エラストマーである。
　未水添エラストマーとは、エラストマー中の共役ジエン単量体単位に基づく二重結合のうち、水素添加されているものの割合、すなわち、水素添加率（水添率）が２０％以下のものをいう。前記水添率は、１５％以下が好ましく、１０％以下がより好ましく、５％以下がさらに好ましい。 The thermoplastic elastomer (E) used in this embodiment may be a block polymer or a random polymer. In addition, even if it is a hydrogenated elastomer in which the conjugated diene monomer unit is hydrogenated, an unhydrogenated elastomer in which the conjugated diene monomer unit is not hydrogenated, or a partially hydrogenated elastomer in which the conjugated diene monomer unit is partially hydrogenated, good.
In one embodiment of the present embodiment, the thermoplastic elastomer (E) is an unhydrogenated elastomer.
Unhydrogenated elastomer refers to an elastomer in which the proportion of double bonds based on conjugated diene monomer units that are hydrogenated, that is, the hydrogenation rate (hydrogenation rate) is 20% or less. . The hydrogenation rate is preferably 15% or less, more preferably 10% or less, even more preferably 5% or less.
　本実施形態で用いる熱可塑性エラストマー（Ｅ）の市販品としては、株式会社クラレ製のＳＥＰＴＯＮ（登録商標）２１０４、旭化成株式会社製、Ｓ．Ｏ．Ｒ．（登録商標）Ｓ１６０６、Ｓ１６１３、Ｓ１６０９、Ｓ１６０５、ＪＳＲ株式会社製、ＤＹＮＡＲＯＮ（登録商標）９９０１Ｐ、ＴＲ２２５０、等が例示される。 Commercially available thermoplastic elastomers (E) used in this embodiment include SEPTON (registered trademark) 2104 manufactured by Kuraray Co., Ltd. and SEPTON (registered trademark) 2104 manufactured by Asahi Kasei Corporation. O. R. (registered trademark) S1606, S1613, S1609, S1605, manufactured by JSR Corporation, DYNARON (registered trademark) 9901P, TR2250, and the like.
　本実施形態の樹脂組成物が熱可塑性エラストマー（好ましくは、熱可塑性エラストマー（Ｅ））を含む場合、その含有量は、樹脂固形分１００質量部に対し、１質量部以上であることが好ましく、５質量部以上であることがより好ましく、１０質量部以上であることがさらに好ましく、１５質量部以上であってもよい。前記下限値以上とすることにより、得られる硬化物の低誘電特性（Ｄｋおよび／またはＤｆ）がより向上する傾向にある。また、熱可塑性エラストマーの含有量の上限値は、樹脂固形分１００質量部に対し、４５質量部以下であることが好ましく、４０質量部以下であることがより好ましく、３５質量部以下であることがさらに好ましく、３０質量部以下であることが一層好ましく、２５質量部以下であってもよい。前記上限値以下とすることにより、得られる硬化物の耐熱性がより向上する傾向にある。
　本実施形態の樹脂組成物は、熱可塑性エラストマーを１種のみ含んでいてもよいし、２種以上含んでいてもよい。２種以上含む場合、合計量が上記範囲となることが好ましい。 When the resin composition of the present embodiment contains a thermoplastic elastomer (preferably thermoplastic elastomer (E)), the content thereof is preferably 1 part 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, even more preferably 10 parts by mass or more, and may be 15 parts by mass or more. By setting it to the above lower limit or more, the low dielectric properties (Dk and/or Df) of the obtained cured product tend to be further improved. Further, the upper limit of the content of the thermoplastic elastomer is preferably 45 parts by mass or less, more preferably 40 parts by mass or less, and 35 parts by mass or less based on 100 parts by mass of the resin solid content. It is more preferably 30 parts by mass or less, even more preferably 25 parts by mass or less. By setting it below the above-mentioned upper limit, the heat resistance of the obtained cured product tends to be further improved.
The resin composition of this embodiment may contain only one type of thermoplastic elastomer, or may contain two or more types of thermoplastic elastomer. When two or more types are included, it is preferable that the total amount falls within the above range.
＜難燃剤＞
　本実施形態の樹脂組成物は、難燃剤を含んでいてもよい。難燃剤としては、リン系難燃剤、ハロゲン系難燃剤、無機系難燃剤およびシリコーン系難燃剤が例示され、リン系難燃剤が好ましい。
　難燃剤としては、公知のものが使用でき、例えば、臭素化エポキシ樹脂、臭素化ポリカーボネート、臭素化ポリスチレン、臭素化スチレン、臭素化フタルイミド、テトラブロモビスフェノールＡ、ペンタブロモベンジル（メタ）アクリレート、ペンタブロモトルエン、トリブロモフェノール、ヘキサブロモベンゼン、デカブロモジフェニルエーテル、ビス－１，２－ペンタブロモフェニルエタン、塩素化ポリスチレン、塩素化パラフィン等のハロゲン系難燃剤、赤リン、トリクレジルホスフェート、トリフェニルホスフェート、クレジルジフェニルホスフェート、トリキシレニルホスフェート、トリアルキルホスフェート、ジアルキルホスフェート、トリス（クロロエチル）ホスフェート、ホスファゼン、１，３－フェニレンビス（２，６－ジキシレニルホスフェート）、１０－（２，５－ジヒドロキシフェニル）－１０Ｈ－９－オキサ－１０－ホスファフェナントレン－１０－オキサイド等のリン系難燃剤、水酸化アルミニウム、水酸化マグネシウム、部分ベーマイト、ベーマイト、ホウ酸亜鉛、三酸化アンチモン等の無機系難燃剤、シリコーンゴム、シリコーンレジン等のシリコーン系難燃剤が挙げられる。
　本実施形態においては、これらの中でも、１，３－フェニレンビス（２，６－ジキシレニルホスフェート）が低誘電特性（Ｄｋおよび／またはＤｆ）を損なわないことから好ましい。 <Flame retardant>
The resin composition of this embodiment may contain a flame retardant. Examples of the flame retardant include phosphorus-based flame retardants, halogen-based flame retardants, inorganic flame retardants, and silicone-based flame retardants, with phosphorus-based flame retardants being preferred.
Known flame retardants can be used, such as 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 phosphate), 10-(2,5- Phosphorous flame retardants such as (dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, inorganic types such as aluminum hydroxide, magnesium hydroxide, partial boehmite, boehmite, zinc borate, and antimony trioxide. Examples include flame retardants, silicone-based flame retardants such as silicone rubber, and silicone resin.
In this embodiment, among these, 1,3-phenylenebis(2,6-dixylenyl phosphate) is preferred because it does not impair low dielectric properties (Dk and/or Df).
　本実施形態の樹脂組成物が難燃剤を含む場合、その含有量は、樹脂組成物中の樹脂固形分１００質量部に対し、１質量部以上であることが好ましく、５質量部以上であることがより好ましく、１０質量部以上であることが更に好ましく、１５質量部以上であってもよい。また、難燃剤の含有量の下限値は、３０質量部以下であることが好ましく、２５質量部以下であることがより好ましい。
　難燃剤は、１種を単独で、または２種以上を組み合わせて用いることができる。２種以上用いる場合は、合計量が上記範囲となる。 When the resin composition of the present embodiment contains a flame retardant, the content thereof is preferably 1 part by mass or more, and preferably 5 parts by mass or more, based on 100 parts by mass of resin solids in the resin composition. is more preferable, still more preferably 10 parts by mass or more, and may be 15 parts by mass or more. Further, the lower limit of the flame retardant content is preferably 30 parts by mass or less, more preferably 25 parts by mass or less.
One kind of flame retardant can be used alone or two or more kinds can be used in combination. When two or more types are used, the total amount falls within the above range.
＜活性エステル化合物＞
　本実施形態の樹脂組成物は、本発明の効果を損なわない範囲で活性エステル化合物を含んでいてもよい。活性エステル化合物としては、特に限定されず、例えば、国際公開第２０２１／１７２３１７号の段落００６４～００６６の記載を参酌でき、この内容は本明細書に組み込まれる。 <Active ester compound>
The resin composition of this embodiment may contain an active ester compound within a range that does not impair the effects of the present invention. The active ester compound is not particularly limited, and for example, the description in paragraphs 0064 to 0066 of International Publication No. 2021/172317 can be referred to, the contents of which are incorporated herein.
　本実施形態の樹脂組成物が活性エステル化合物を含む場合、樹脂組成物中の樹脂固形分１００質量部に対し、１質量部以上であることが好ましく、また、５０質量部以下であることが好ましい。
　本実施形態における樹脂組成物は、活性エステル化合物を１種のみ含んでいてもよいし、２種以上含んでいてもよい。２種以上含む場合、合計量が上記範囲となることが好ましい。
　また、本実施形態における樹脂組成物は、活性エステル化合物を実質的に含まない構成とすることもできる。実質的に含まないとは、活性エステル化合物の含有量が樹脂組成物中の樹脂固形分１００質量部に対し、１質量部未満であることいい、０．１質量部未満であることが好ましく、０．０１質量部未満であることがさらに好ましい。 When the resin composition of this embodiment contains an active ester compound, it is preferably 1 part by mass or more, and preferably 50 parts by mass or less, based on 100 parts by mass of resin solid content in the resin composition. .
The resin composition in this embodiment may contain only one type of active ester compound, or may contain two or more types of active ester compounds. When two or more types are included, it is preferable that the total amount falls within the above range.
Moreover, the resin composition in this embodiment can also be configured to substantially not 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, per 100 parts by mass of resin solids in the resin composition. More preferably, it is less than 0.01 part by mass.
＜分散剤＞
　本実施形態の樹脂組成物は、分散剤を含んでいてもよい。分散剤としては、一般に塗料用に使用されているものを好適に用いることができ、その種類は特に限定されない。分散剤は、好ましくは、共重合体ベースの湿潤分散剤が使用され、その具体例としては、ビックケミー・ジャパン（株）製のＤＩＳＰＥＲＢＹＫ（登録商標）－１１０、１１１、１６１、１８０、２００９、２１５２、２１５５、ＢＹＫ（登録商標）－Ｗ９９６、Ｗ９０１０、Ｗ９０３、Ｗ９４０などが挙げられる。 <Dispersant>
The resin composition of this embodiment may contain a dispersant. As the dispersant, those commonly used for paints can be suitably used, and the type thereof is not particularly limited. As the dispersant, preferably a copolymer-based wetting and dispersing agent is used, and specific examples thereof include DISPERBYK®-110, 111, 161, 180, 2009, and 2152 manufactured by BYK Chemie Japan Co., Ltd. , 2155, BYK (registered trademark)-W996, W9010, W903, W940, etc.
　本実施形態の樹脂組成物が分散剤を含む場合、その含有量の下限値は、樹脂組成物中の樹脂固形分１００質量部に対し、０．０１質量部以上であることが好ましく、０．１質量部以上であることがより好ましく、０．３質量部以上であってもよい。また、分散剤の含有量の上限値は、樹脂組成物中の樹脂固形分１００質量部に対し、１０質量部以下であることが好ましく、５質量部以下であることがより好ましく、３質量部以下であってもよい。
　分散剤は、１種を単独で、または２種以上を組み合わせて用いることができる。２種以上用いる場合は、合計量が上記範囲となる。 When the resin composition of the present embodiment contains a dispersant, the lower limit of its content is preferably 0.01 parts by mass or more, and 0.01 parts by mass or more, based on 100 parts by mass of resin solids in the resin composition. It is more preferably 1 part by mass or more, and may be 0.3 parts by mass or more. Further, 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 based on 100 parts by mass of the resin solid content in the resin composition. The following may be sufficient.
One type of dispersant can be used alone or two or more types can be used in combination. When two or more types are used, the total amount falls within the above range.
＜硬化促進剤＞
　本実施形態の樹脂組成物は、硬化促進剤をさらに含んでもよい。硬化促進剤としては、特に限定されないが、例えば、２－エチル－４－メチルイミダゾール、トリフェニルイミダゾール等のイミダゾール類；過酸化ベンゾイル、ラウロイルパーオキサイド、アセチルパーオキサイド、パラクロロベンゾイルパーオキサイド、ジ－ｔｅｒｔ－ブチル－ジ－パ－フタレート、α，α’－ジ（ｔ－ブチルペルオキシ）ジイソプロピルベンゼン、２，５－ジメチル－２，５－ジ（ｔ－ブチルペルオキシ）ヘキサン、２，５－ジメチル－２，５－ビス（ｔ－ブチルペルオキシ）ヘキシン－３などの有機過酸化物；アゾビスニトリルなどのアゾ化合物；Ｎ，Ｎ－ジメチルベンジルアミン、Ｎ，Ｎ－ジメチルアニリン、Ｎ，Ｎ－ジメチルトルイジン、２－Ｎ－エチルアニリノエタノール、トリ－ｎ－ブチルアミン、ピリジン、キノリン、Ｎ－メチルモルホリン、トリエタノールアミン、トリエチレンジアミン、テトラメチルブタンジアミン、Ｎ－メチルピペリジンなどの第３級アミン類；フェノール、キシレノール、クレゾール、レゾルシン、カテコールなどのフェノール類；２，３－ジメチル－２，３－ジフェニルブタンなどの高温分解型ラジカル発生剤；ナフテン酸鉛、ステアリン酸鉛、ナフテン酸亜鉛、オクチル酸亜鉛、オクチル酸マンガン、オレイン酸錫、ジブチル錫マレート、ナフテン酸マンガン、ナフテン酸コバルト、アセチルアセトン鉄などの有機金属塩；これら有機金属塩をフェノール、ビスフェノールなどの水酸基含有化合物に溶解してなるもの；塩化錫、塩化亜鉛、塩化アルミニウムなどの無機金属塩；ジオクチル錫オキサイド、その他のアルキル錫、アルキル錫オキサイドなどの有機錫化合物などが挙げられる。
　好ましい硬化促進剤は、イミダゾール類および有機金属塩であり、イミダゾール類および有機金属塩の両方を組み合わせて用いることがより好ましい。 <Curing accelerator>
The resin composition of this embodiment may further contain a curing accelerator. Examples of the curing accelerator include, but are not limited to, imidazoles such as 2-ethyl-4-methylimidazole and triphenylimidazole; benzoyl peroxide, lauroyl peroxide, acetyl peroxide, parachlorobenzoyl peroxide, di- tert-butyl-di-perphthalate, α,α'-di(t-butylperoxy)diisopropylbenzene, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 2,5-dimethyl- Organic peroxides such as 2,5-bis(t-butylperoxy)hexyne-3; azo compounds such as azobisnitrile; N,N-dimethylbenzylamine, N,N-dimethylaniline, N,N-dimethyltoluidine , 2-N-ethylanilinoethanol, tri-n-butylamine, pyridine, quinoline, N-methylmorpholine, triethanolamine, triethylenediamine, tetramethylbutanediamine, N-methylpiperidine and other tertiary amines; phenol , xylenol, cresol, resorcin, catechol, and other phenols; high-temperature decomposition type radical generators such as 2,3-dimethyl-2,3-diphenylbutane; lead naphthenate, lead stearate, zinc naphthenate, zinc octylate, Organometallic salts such as manganese octylate, tin oleate, dibutyltin malate, manganese naphthenate, cobalt naphthenate, iron acetylacetonate, etc.; Products obtained by dissolving these organometallic salts in hydroxyl group-containing compounds such as phenol and bisphenol; tin chloride , inorganic metal salts such as zinc chloride and aluminum chloride; and organic tin compounds such as dioctyltin oxide, other alkyltins, and alkyltin oxides.
Preferred curing accelerators are imidazoles and organometallic salts, and it is more preferred to use both imidazoles and organometallic salts in combination.
　本実施形態の樹脂組成物が硬化促進剤を含む場合、その含有量の下限値は、樹脂組成物中の樹脂固形分１００質量部に対し、０．００５質量部以上であることが好ましく、０．０１質量部以上であることがより好ましく、０．１質量部以上であることがさらに好ましい。また、硬化促進剤の含有量の上限値は、樹脂組成物中の樹脂固形分１００質量部に対し、１０質量部以下であることが好ましく、５質量部以下であることがより好ましく、２質量部以下であることがさらに好ましい。
　硬化促進剤は、１種を単独で、または２種以上を組み合わせて用いることができる。２種以上用いる場合は、合計量が上記範囲となる。 When the resin composition of the present embodiment contains a curing accelerator, the lower limit of its content is preferably 0.005 parts by mass or more with respect to 100 parts by mass of resin solids in the resin composition, and 0. It is more preferably .01 part by mass or more, and even more preferably 0.1 part by mass or more. Further, the upper limit of the content of the curing accelerator is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and 2 parts by mass or less, based on 100 parts by mass of resin solids in the resin composition. It is more preferable that the amount is less than 1 part.
The curing accelerator can be used alone or in combination of two or more. When two or more types are used, the total amount falls within the above range.
＜溶剤＞
　本実施形態の樹脂組成物は、溶剤を含有してもよく、有機溶剤を含むことが好ましい。溶剤を含有する場合、本実施形態の樹脂組成物は、上述した各種樹脂固形分の少なくとも一部、好ましくは全部が溶剤に溶解または相溶した形態（溶液またはワニス）である。溶剤としては、上述した各種樹脂固形分の少なくとも一部、好ましくは全部を溶解または相溶可能な極性有機溶剤または無極性有機溶剤であれば特に限定されず、極性有機溶剤としては、例えば、ケトン類（例えば、アセトン、メチルエチルケトン、メチルイソブチルケトン等）、セロソルブ類（例えば、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート等）、エステル類（例えば、乳酸エチル、酢酸メチル、酢酸エチル、酢酸ブチル、酢酸イソアミル、乳酸エチル、メトキシプロピオン酸メチル、ヒドロキシイソ酪酸メチル等）、アミド類（例えば、ジメトキシアセトアミド、ジメチルホルムアミド類等）が挙げられ、無極性有機溶剤としては、芳香族炭化水素（例えば、トルエン、キシレン等）が挙げられる。
　溶剤は、１種を単独で、または２種以上を組み合わせて用いることができる。２種以上用いる場合は、合計量が上記範囲となる。 <Solvent>
The resin composition of this embodiment may contain a solvent, and preferably contains an organic solvent. When containing a solvent, the resin composition of the present embodiment is in a form (solution or varnish) in which at least a portion, preferably all, of the various resin solid components 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 that can dissolve or be compatible with at least a portion, preferably all, of the various resin solids mentioned above. Examples of the polar organic solvent include ketones, etc. (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), cellosolves (e.g., propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc.), esters (e.g., ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, acetic acid) isoamyl, ethyl lactate, methyl methoxypropionate, methyl hydroxyisobutyrate, etc.), amides (e.g., dimethoxyacetamide, dimethylformamide, etc.), and nonpolar organic solvents include aromatic hydrocarbons (e.g., toluene, xylene, etc.).
One kind of solvent can be used alone or two or more kinds can be used in combination. When two or more types are used, the total amount falls within the above range.
＜その他の成分＞
　本実施形態の樹脂組成物は、上記の成分以外に、熱可塑性樹脂およびそのオリゴマー等の種々の高分子化合物、各種添加剤を含有してもよい。添加剤としては、紫外線吸収剤、酸化防止剤、光重合開始剤、蛍光増白剤、光増感剤、染料、顔料、増粘剤、流動調整剤、滑剤、消泡剤、レベリング剤、光沢剤、重合禁止剤等が挙げられる。これらの添加剤は、１種を単独で、または２種以上を組み合わせて用いることができる。 <Other ingredients>
The resin composition of this embodiment may contain various polymeric compounds such as thermoplastic resins and oligomers thereof, and various additives in addition to the above-mentioned components. Additives include ultraviolet absorbers, antioxidants, photopolymerization initiators, optical brighteners, photosensitizers, dyes, pigments, thickeners, fluidity regulators, lubricants, antifoaming agents, leveling agents, and gloss. agents, polymerization inhibitors, etc. These additives can be used alone or in combination of two or more.
＜用途＞
　本実施形態の樹脂組成物は、硬化物として用いられる。具体的には、本実施形態の樹脂組成物は、低比誘電率材料および／または低誘電正接材料として、プリント配線板の絶縁層、半導体パッケージ用材料等、電子材料用樹脂組成物として好適に用いることができる。本実施形態の樹脂組成物は、プリプレグ、プリプレグを用いた金属箔張積層板、樹脂複合シート、およびプリント配線板用の材料として好適に用いることができる。 <Application>
The resin composition of this embodiment is used as a cured product. Specifically, the resin composition of this embodiment is suitable as a low dielectric constant material and/or a low dielectric loss tangent material as a resin composition for electronic materials such as insulating layers of printed wiring boards, materials for semiconductor packages, etc. Can be used. The resin composition of this embodiment can be suitably used as a material for prepreg, a metal foil-clad laminate using prepreg, a resin composite sheet, and a printed wiring board.
　本実施形態の樹脂組成物は、厚さ０．８ｍｍの硬化板に成形したときの比誘電率（Ｄｋ）が低いことが好ましい。具体的には、空洞共振器摂動法に従って測定した周波数１０ＧＨｚにおける比誘電率（Ｄｋ）が２．６０以下であることが好ましく、２．５０以下であることがより好ましい。比誘電率（Ｄｋ）の下限値については、特に定めるものではないが、例えば、０．０１以上が実際的である。
　また、本実施形態の樹脂組成物は、厚さ０．８ｍｍの硬化板に成形したときの誘電正接（Ｄｆ）が低いことが好ましい。具体的には、空洞共振器摂動法に従って測定した周波数１０ＧＨｚにおける誘電正接（Ｄｆ）が０．００２０以下であることが好ましく、０．００１８以下であることがより好ましく、０．００１４以下であることがさらに好ましい。誘電正接（Ｄｆ）の下限値については、特に定めるものではないが、例えば、０．０００１以上が実際的である。
　このような低誘電特性（Ｄｋおよび／またはＤｆ）は、主に、式（Ｖ）で表される構成単位を有する重合体（Ｖ）および式（Ｍ１）で表される化合物（Ｍ１）を用いることにより達成される。
　上記硬化板の比誘電率（Ｄｋ）および誘電正接（Ｄｆ）は、より具体的には、後述する実施例に記載の方法で測定される。 The resin composition of this embodiment preferably has a low dielectric constant (Dk) when molded into a cured plate with a thickness of 0.8 mm. Specifically, the dielectric constant (Dk) at a frequency of 10 GHz measured according to the cavity resonator perturbation method is preferably 2.60 or less, more preferably 2.50 or less. Although the lower limit of the dielectric constant (Dk) is not particularly determined, for example, 0.01 or more is practical.
Moreover, it is preferable that the resin composition of this embodiment has a low dielectric loss tangent (Df) when molded into a cured plate with a thickness of 0.8 mm. Specifically, the dielectric loss tangent (Df) at a frequency of 10 GHz measured according to the cavity resonator perturbation method is preferably 0.0020 or less, more preferably 0.0018 or less, and 0.0014 or less. is even more preferable. Although the lower limit value of the dielectric loss tangent (Df) is not particularly determined, for example, 0.0001 or more is practical.
Such low dielectric properties (Dk and/or Df) are mainly achieved by using a polymer (V) having a structural unit represented by formula (V) and a compound (M1) represented by formula (M1). This is achieved by
More specifically, the dielectric constant (Dk) and dielectric loss tangent (Df) of the cured plate are measured by the method described in the Examples described below.
　本実施形態の樹脂組成物の硬化物は、ＤＭＡ（動的機械測定）に従ったガラス転移温度が、２３０℃以上であることが好ましく、２５０℃以上であることがより好ましい。このような高いガラス転移温度は、主に、式(Ｍ)で表される化合物(Ｍ)を用いることにより達成される。ガラス転移温度の上限値は、例えば、３５０℃以下が実際的である。ガラス転移温度は、より具体的には、後述する実施例に記載の方法で測定される。 The cured product of the resin composition of this embodiment preferably has a glass transition temperature of 230°C or higher, more preferably 250°C or higher, according to DMA (dynamic mechanical measurement). Such a high glass transition temperature is achieved mainly by using a compound (M) represented by formula (M). The practical upper limit of the glass transition temperature is, for example, 350° C. or less. More specifically, the glass transition temperature is measured by the method described in Examples below.
　また、本実施形態の樹脂組成物を用いて得られる絶縁層には、孔をあける加工を施すことが多く、デスミア耐性に優れていることが好ましい。すなわち、孔をあける加工後のスミア除去において、絶縁層の劣化を抑制しつつ、スミアの除去性に優れることが好ましい。具体的には、本実施形態の樹脂組成物を厚さ０．８ｍｍの硬化板に成形したときのデスミア試験における質量減少率が－４．０質量％～-２．０質量％の範囲であることが好ましい。デスミア耐性は後述する実施例の記載に従って測定される。 Furthermore, the insulating layer obtained using the resin composition of this embodiment is often subjected to a process of forming holes, and preferably has excellent desmear resistance. That is, in removing the smear after the hole-drilling process, it is preferable to suppress deterioration of the insulating layer and to have excellent smear removability. Specifically, when the resin composition of this embodiment is molded into a cured plate with a thickness of 0.8 mm, the mass reduction rate in the desmear test is in the range of -4.0% by mass to -2.0% by mass. It is preferable. Desmear resistance is measured according to the description in Examples below.
　本実施形態の樹脂組成物は、プリント配線板の絶縁層となる、プリプレグ、樹脂複合シート等の層状（フィルム状、シート状等を含む趣旨である）の材料として用いられるが、かかる層状の材料としたとき、その厚さは、５μｍ以上であることが好ましく、１０μｍ以上であることがより好ましい。厚さの上限値としては、２００μｍ以下であることが好ましく、１８０μｍ以下であることがより好ましい。尚、上記層状の材料の厚さは、例えば、本実施形態の樹脂組成物をガラスクロス等に含浸させたものである場合、ガラスクロスを含む厚さを意味する。
　本実施形態の樹脂組成物から形成される材料は、露光現像してパターンを形成する用途に用いてもよいし、露光現像しない用途に用いてもよい。特に、露光現像しない用途に適している。 The resin composition of this embodiment is used as a layered material (including film-like, sheet-like, etc.) such as prepreg, resin composite sheet, etc., which becomes an insulating layer of a printed wiring board. In this case, the thickness is preferably 5 μm or more, more preferably 10 μm or more. The upper limit of the thickness is preferably 200 μm or less, more preferably 180 μm or less. In addition, the thickness of the above-mentioned layered material means the thickness including the glass cloth, for example, when the resin composition of the present embodiment is impregnated into a glass cloth or the like.
The material formed from the resin composition of this embodiment may be used for forming a pattern by exposure and development, or may be used for applications that are not exposed and developed. It is particularly suitable for applications that do not involve exposure and development.
＜＜プリプレグ＞＞
　本実施形態のプリプレグは、基材（プリプレグ基材）と、本実施形態の樹脂組成物とから形成される。本実施形態のプリプレグは、例えば、本実施形態の樹脂組成物を基材に適用（例えば、含浸および／または塗布）させた後、加熱（例えば、１２０～２２０℃で２～１５分乾燥させる方法等）によって半硬化させることにより得られる。この場合、基材に対する樹脂組成物の付着量、すなわち半硬化後のプリプレグの総量に対する樹脂組成物量（充填材（Ｄ）を含む）は、２０～９９質量％の範囲であることが好ましく、２０～８０質量％の範囲であることがより好ましい。 <<Prepreg>>
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 by, for example, applying the resin composition of the present embodiment to a base material (for example, impregnating and/or coating it), and then heating it (for example, drying it at 120 to 220°C for 2 to 15 minutes). etc.) by semi-curing. In this case, the amount of the resin composition adhered to the base material, that is, the amount of the resin composition (including filler (D)) relative to the total amount of prepreg after semi-curing, is preferably in the range of 20 to 99% by mass, and 20% by mass. More preferably, the content is in the range of 80% by mass.
　基材としては、各種プリント配線板材料に用いられている基材であれば特に限定されない。基材の材質としては、例えば、ガラス繊維（例えば、Ｅ－ガラス、Ｄ－ガラス、Ｌ－ガラス、Ｓ－ガラス、Ｔ－ガラス、Ｑ－ガラス、ＵＮ－ガラス、ＮＥ－ガラス、球状ガラス等）、ガラス以外の無機繊維（例えば、クォーツ等）、有機繊維（例えば、ポリイミド、ポリアミド、ポリエステル、液晶ポリエステル、ポリテトラフルオロエチレン等）が挙げられる。基材の形態としては、特に限定されず、織布、不織布、ロービング、チョップドストランドマット、サーフェシングマット等が挙げられる。これらの基材は、単独で用いても、２種以上を併用してもよい。これらの基材の中でも、寸法安定性の観点から、超開繊処理、目詰め処理を施した織布が好ましく、強度と低吸水性の観点から、基材は、厚み２００μｍ以下、質量２５０ｇ／ｍ２以下のガラス織布が好ましく、吸湿耐熱性の観点から、エポキシシラン、アミノシランなどのシランカップリング剤等により表面処理されたガラス織布が好ましい。電気特性の観点から、Ｌ－ガラスやＮＥ－ガラス、Ｑ－ガラス等の低比誘電率、低誘電正接を示すガラス繊維からなる、低誘電ガラスクロスがより好ましい。
　低比誘電率性の基材とは、例えば、比誘電率が５．０以下（好ましくは、３．０～４．９）の基材が例示される。低誘電正接性の基材とは、例えば、誘電正接が０．００６以下（好ましくは、０．００１～０．００５）の基材が例示される。比誘電率および誘電正接は、摂動法空洞共振器により、周波数１０ＧＨｚで測定した値とする。 The base material is not particularly limited as long as it is a base material used for various printed wiring board materials. Examples of the material of the base material include glass fiber (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, etc.), and organic fibers (eg, polyimide, polyamide, polyester, liquid crystal polyester, polytetrafluoroethylene, etc.). The form of the base material is not particularly limited, and examples thereof include woven fabric, nonwoven fabric, roving, chopped strand mat, surfacing mat, and the like. These base materials may be used alone or in combination of two or more. Among these base materials, from the viewpoint of dimensional stability, woven fabrics subjected to ultra-opening treatment and packing treatment are preferable, and from the viewpoints of strength and low water absorption, the base material has a thickness of 200 μm or less, a mass of 250 g/ A glass woven fabric having a size 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 epoxy silane or amino silane is preferable. From the viewpoint of electrical properties, 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 the base material having a low dielectric constant include a base material having a dielectric constant of 5.0 or less (preferably 3.0 to 4.9). Examples of the low dielectric loss tangent base material include base materials with a dielectric loss tangent of 0.006 or less (preferably 0.001 to 0.005). The relative dielectric constant and dielectric loss tangent are values measured at a frequency of 10 GHz using a perturbation method cavity resonator.
＜＜金属箔張積層板＞＞
　本実施形態の金属箔張積層板は、本実施形態のプリプレグから形成された少なくとも１つの層と、前記プリプレグから形成された層の片面または両面に配置された金属箔とを含む。本実施形態の金属箔張積層板の作製方法としては、例えば、本実施形態のプリプレグを少なくとも１枚配置し（好ましくは２枚以上重ね）、その片面または両面に金属箔を配置して積層成形する方法が挙げられる。より詳細には、プリプレグの片面または両面に銅、アルミニウム等の金属箔を配置して積層成形することにより作製できる。プリプレグの枚数としては、１～１０枚が好ましく、２～１０枚がより好ましく、２～９枚がさらに好ましい。
　金属箔としては、プリント配線板用材料に用いられるものであれば特に限定されないが、例えば、圧延銅箔、電解銅箔等の銅箔が挙げられる。金属箔（好ましくは、銅箔）の厚さは、特に限定されず、１．５～７０μｍ程度であってもよい。また、金属箔として銅箔を用いる場合、銅箔としては、ＪＩＳ　Ｂ０６０１：２０１３に従って測定した銅箔表面の粗度Ｒｚが、０．２～４．０μｍに調整されていることが好ましい。銅箔表面の粗度Ｒｚを０．２μｍ以上とすることにより、銅箔表面の粗度が適度な大きさとなり、銅箔ピール強度がより向上する傾向にある。一方、銅箔表面の粗度Ｒｚを４．０μｍ以下とすることにより、銅箔表面の粗度が適度な大きさとなり、得られる硬化物の誘電正接特性がより向上する傾向にある。銅箔表面の粗度Ｒｚは、誘電正接低減の観点から、より好ましくは０．５μｍ以上であり、さらに好ましくは０．６μｍ以上であり、特に好ましくは０．７μｍ以上であり、また、より好ましくは３．５μｍ以下であり、さらに好ましくは３．０μｍ以下であり、特に好ましくは２．０μｍ以下である。 <<Metal foil clad laminate>>
The metal foil-clad laminate of this embodiment includes at least one layer formed from the prepreg of this embodiment, and metal foil disposed on one or both sides of the layer formed from the prepreg. As a method for producing the metal foil-clad laminate of this embodiment, for example, at least one prepreg of this embodiment is arranged (preferably two or more prepregs are stacked), metal foil is arranged on one or both sides of the prepreg, and laminated molding is performed. One method is to do so. More specifically, it can be produced by arranging a metal foil such as copper or aluminum on one or both sides of a prepreg and laminating it. The number of prepreg sheets is preferably 1 to 10 sheets, more preferably 2 to 10 sheets, and even more preferably 2 to 9 sheets.
The metal foil is not particularly limited as long as it is used as a material for printed wiring boards, and examples thereof include copper foils 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 μm. Further, when copper foil is used as the metal foil, it is preferable that the roughness Rz of the surface of the copper foil measured according to JIS B0601:2013 is adjusted to 0.2 to 4.0 μm. By setting the roughness Rz of the copper foil surface to 0.2 μm or more, the roughness of the copper foil surface becomes appropriate, and the copper foil peel strength tends to be further improved. On the other hand, by setting the roughness Rz of the copper foil surface to 4.0 μm or less, the roughness of the copper foil surface becomes appropriate, and the dielectric loss tangent characteristics of the obtained cured product tend to be further improved. From the viewpoint of reducing the dielectric loss tangent, the roughness Rz of the copper foil surface is more preferably 0.5 μm or more, still more preferably 0.6 μm or more, particularly preferably 0.7 μm or more, and more preferably is 3.5 μm or less, more preferably 3.0 μm or less, particularly preferably 2.0 μm or less.
　積層成形の方法としては、プリント配線板用積層板および多層板を成形する際に通常用いられる方法が挙げられ、より詳細には多段プレス機、多段真空プレス機、連続成形機、オートクレーブ成形機等を使用して、温度１８０～３５０℃程度、加熱時間１００～３００分程度、面圧２０～１００ｋｇ／ｃｍ２程度で積層成形する方法が挙げられる。また、本実施形態のプリプレグと、別途作製した内層用の配線板とを組み合わせて積層成形することにより、多層板とすることもできる。多層板の製造方法としては、例えば、本実施形態のプリプレグ１枚の両面に３５μｍ程度の銅箔を配置し、上記の成形方法にて積層形成した後、内層回路を形成し、この回路に黒化処理を実施して内層回路板を形成し、この後、この内層回路板と本実施形態のプリプレグとを交互に１枚ずつ配置し、さらに最外層に銅箔を配置して、上記条件にて好ましくは真空下で積層成形することにより、多層板を作製することができる。本実施形態の金属箔張積層板は、プリント配線板として好適に使用することができる。 Examples of the lamination molding method include methods normally used when molding laminate boards for printed wiring boards and multilayer boards, and more specifically, multistage press machines, multistage vacuum press machines, continuous molding machines, autoclave molding machines, etc. An example of this is a method of laminated 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 . Furthermore, a multilayer board can be obtained by laminating and molding a combination of the prepreg of this embodiment and a separately produced wiring board for an inner layer. As a method for manufacturing a multilayer board, for example, copper foil of about 35 μm is placed on both sides of one sheet of prepreg of this embodiment, and after lamination is formed using the above-mentioned forming method, an inner layer circuit is formed, and this circuit is coated with black. After that, the inner layer circuit board and the prepreg of this embodiment are alternately placed one by one, and a copper foil is placed on the outermost layer, and the above conditions are met. A multilayer 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.
　本実施形態の金属箔張積層板は、ＪＩＳ　Ｃ６４８１の５．７　「引きはがし強さ」の規定に準じて測定したピール強度が０．２８ｋＮ／ｍ以上であることが好ましく、０．３８ｋＮ／ｍ以上であることがより好ましく、０．５０ｋＮ／ｍ以上であることがさらに好ましい。ピール強度の上限は、特に定めるものでは無いが、例えば、２．００ｋＮ／ｍ以上である。
　ピール強度は後述する実施例の記載に従って測定される。 It is preferable that the metal foil-clad laminate of this embodiment has a peel strength of 0.28 kN/m or more, and 0.38 kN/m or more, as measured in accordance with the provisions of 5.7 "Peel strength" of JIS C6481. It is more preferably at least 0.50 kN/m, and even more preferably at least 0.50 kN/m. The upper limit of the peel strength is not particularly determined, but is, for example, 2.00 kN/m or more.
Peel strength is measured according to the description in Examples below.
　以上のように、本実施形態の樹脂組成物（特定成分の組合せからなる樹脂組成物）を用いて得られる電子材料用樹脂組成物は、その硬化物が、低誘電特性（低誘電率、低誘電正接）、吸湿耐熱性のほか、耐熱性、デスミア耐性、金属箔ピール強度、耐クラック性、硬化物の外観、低熱膨張性に優れる特性を有するものとすることができる。 As described above, the resin composition for electronic materials obtained using the resin composition of this embodiment (resin composition consisting of a combination of specific components) has a cured product with low dielectric properties (low dielectric constant, low dielectric constant, low In addition to heat resistance, heat resistance, desmear resistance, metal foil peel strength, crack resistance, appearance of cured product, and low thermal expansion properties, the cured product can have excellent properties such as dielectric loss tangent), moisture absorption and heat resistance, and heat resistance, desmear resistance, metal foil peel strength, crack resistance, appearance of cured product, and low thermal expansion.
＜＜プリント配線板＞＞
　本実施形態のプリント配線板は、絶縁層と、前記絶縁層の表面に配置された導体層とを含むプリント配線板であって、前記絶縁層が、本実施形態の樹脂組成物から形成された層および本実施形態のプリプレグから形成された層の少なくとも一方を含む。このようなプリント配線板は、常法に従って製造でき、その製造方法は特に限定されない。以下、プリント配線板の製造方法の一例を示す。まず上述した銅箔張積層板等の金属箔張積層板を用意する。次に、金属箔張積層板の表面にエッチング処理を施して内層回路の形成を行い、内層基板を作製する。この内層基板の内層回路表面に、必要に応じて接着強度を高めるための表面処理を行い、次いでその内層回路表面に上述したプリプレグを所要枚数重ね、さらにその外側に外層回路用の金属箔を積層し、加熱加圧して一体成形する。このようにして、内層回路と外層回路用の金属箔との間に、基材および樹脂組成物の硬化物からなる絶縁層が形成された多層の積層板が製造される。次いで、この多層の積層板にスルーホールやバイアホール用の穴あけ加工を施した後、この穴の壁面に内層回路と外層回路用の金属箔とを導通させるめっき金属皮膜を形成し、さらに外層回路用の金属箔にエッチング処理を施して外層回路を形成することで、プリント配線板が製造される。 <<Printed wiring board>>
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, the insulating layer being formed from the resin composition of the present embodiment. 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 will be shown below. First, a metal foil-clad laminate such as the above-mentioned copper foil-clad laminate 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 board is subjected to surface treatment to increase adhesive strength as necessary, and then the required number of sheets of prepreg described above are layered on the surface of the inner layer circuit, and then metal foil for the outer layer circuit is laminated on the outside. Then, heat and press to form an integral mold. In this way, a multilayer laminate is produced in which an insulating layer made of the base material and the cured 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 multilayer laminate, a plating metal film is formed on the wall of the hole to conduct the inner layer circuit and the metal foil for the outer layer circuit, and then the outer layer circuit is formed. A printed wiring board is manufactured by performing an etching process on metal foil to form an outer layer circuit.
　上記の製造例で得られるプリント配線板は、絶縁層と、この絶縁層の表面に形成された導体層とを有し、絶縁層が上述した本実施形態の樹脂組成物および／またはその硬化物を含む構成となる。すなわち、上述した本実施形態のプリプレグ（例えば、基材およびこれに含浸または塗布された本実施形態の樹脂組成物から形成されたプリプレグ）、上述した本実施形態の金属箔張積層板の樹脂組成物から形成された層が、本実施形態の絶縁層となる。
　また、本実施形態は、前記プリント配線板を含む半導体装置にも関する。半導体装置の詳細は、特開２０２１－０２１０２７号公報の段落０２００～０２０２の記載を参酌でき、これらの内容は本明細書に組み込まれる。 The printed wiring board obtained in the above manufacturing example has an insulating layer and a conductor layer formed on the surface of this insulating layer, and the insulating layer is made of the resin composition of the present embodiment described above and/or a cured product thereof. The configuration includes That is, the prepreg of the present embodiment described above (for example, the prepreg formed from the base material and the resin composition of the present embodiment impregnated or applied thereto), the resin composition of the metal foil-clad laminate of the present embodiment described above. The layer formed from the material becomes the insulating layer of this embodiment.
The present embodiment also relates to a semiconductor device including the printed wiring board. For details of the semiconductor device, the descriptions in paragraphs 0200 to 0202 of JP-A-2021-021027 can be referred to, and the contents thereof are incorporated into this specification.
　また、本実施形態の樹脂組成物の硬化物で形成された絶縁層は、その絶縁層の粗化処理後の表面粗さを小さくすることが好ましい。具体的には、粗化処理後の絶縁層の表面の算術平均粗さＲａは、好ましくは２００ｎｍ以下、より好ましくは１５０ｎｍ以下、特に好ましくは１００ｎｍ以下である。算術平均粗さＲａの下限値は、特に限定されないが、例えば、１０ｎｍ以上でありうる。絶縁層の表面の算術平均粗さＲａの測定は、非接触型表面粗さ計を用いて、ＶＳＩモード、５０倍レンズを用いて測定して求める。
　非接触型表面粗さ計は、ビーコインスツルメンツ社製ＷＹＫＯＮＴ３３００を用いる。 Further, it is preferable that the insulating layer formed of the cured product of the resin composition of the present embodiment has a reduced surface roughness after the insulating layer is subjected to roughening treatment. Specifically, the arithmetic mean roughness Ra of the surface of the insulating layer after the roughening treatment is preferably 200 nm or less, more preferably 150 nm or less, particularly preferably 100 nm or less. The lower limit of the arithmetic mean roughness Ra is not particularly limited, but may be, for example, 10 nm or more. The arithmetic mean roughness Ra of the surface of the insulating layer is measured using a non-contact surface roughness meter in VSI mode using a 50x lens.
The non-contact surface roughness meter used is WYKONT3300 manufactured by Beaco Instruments.
＜＜樹脂複合シート＞＞
　本実施形態の樹脂複合シートは、支持体と、前記支持体の表面に配置された本実施形態の樹脂組成物から形成された層を含む。樹脂複合シートは、ビルドアップ用フィルムまたはドライフィルムソルダーレジストとして使用することができる。樹脂複合シートの製造方法としては、特に限定されないが、例えば、上記の本実施形態の樹脂組成物を溶剤に溶解させた溶液を支持体に塗布（塗工）し乾燥することで樹脂複合シートを得る方法が挙げられる。 <<Resin composite sheet>>
The resin composite sheet of this embodiment includes a support and a layer formed from the resin composition of this embodiment disposed on the surface of the support. The resin composite sheet can be used as a build-up film or a dry film solder resist. The method for producing the resin composite sheet is not particularly limited, but for example, the resin composite sheet may be produced by applying (coating) a solution of the resin composition of the present embodiment described above in a solvent to a support and drying it. There are several ways to obtain it.
　ここで用いる支持体としては、例えば、ポリエチレンフィルム、ポリプロピレンフィルム、ポリカーボネートフィルム、ポリエチレンテレフタレートフィルム、エチレンテトラフルオロエチレン共重合体フィルム、ならびに、これらのフィルムの表面に離型剤を塗布した離型フィルム、ポリイミドフィルム等の有機系のフィルム基材、銅箔、アルミ箔等の導体箔、ガラス板、ＳＵＳ（Steel Use Stainless）板、ＦＲＰ（Fiber-Reinforced Plastics）等の板状のものが挙げられるが、特に限定されるものではない。 Examples of the support used here include polyethylene film, polypropylene film, polycarbonate film, polyethylene terephthalate film, ethylenetetrafluoroethylene copolymer film, and release films in which a release agent is applied to the surface of these films. Examples include organic film base materials such as polyimide film, conductive foils such as copper foil and aluminum foil, plate-like materials such as glass plates, SUS (Steel Use Stainless) plates, and FRP (Fiber-Reinforced Plastics). It is not particularly limited.
　塗布方法（塗工方法）としては、例えば、本実施形態の樹脂組成物を溶剤に溶解させた溶液を、バーコーター、ダイコーター、ドクターブレード、ベーカーアプリケーター等で支持体上に塗布する方法が挙げられる。また、乾燥後に、支持体と樹脂組成物が積層された樹脂複合シートから支持体を剥離またはエッチングすることで、単層シートとすることもできる。なお、上記の本実施形態の樹脂組成物を溶剤に溶解させた溶液を、シート状のキャビティを有する金型内に供給し乾燥する等してシート状に成形することで、支持体を用いることなく単層シートを得ることもできる。 Examples of the coating method (coating method) include a method in which a solution of the resin composition of the present embodiment dissolved in a solvent is coated onto the support using a bar coater, die coater, doctor blade, Baker applicator, etc. It will be done. Further, after drying, the support can be peeled off or etched from the resin composite sheet in which the support and the resin composition are laminated, thereby forming a single layer sheet. Note that the support can be used by supplying a solution in which the resin composition of the present embodiment described above is dissolved in a solvent into a mold having a sheet-like cavity and drying it to form it into a sheet. It is also possible to obtain a single layer sheet.
　なお、本実施形態の単層シートまたは樹脂複合シートの作製において、溶剤を除去する際の乾燥条件は、特に限定されないが、低温であると樹脂組成物中に溶剤が残り易く、高温であると樹脂組成物の硬化が進行することから、２０℃～２００℃の温度で１～９０分間が好ましい。また、単層シートまたは樹脂複合シートは溶剤を乾燥しただけの未硬化の状態で使用することもできるし、必要に応じて半硬化（Ｂステージ化）の状態にして使用することもできる。さらに、本実施形態の単層シートまたは樹脂複合シートにおける樹脂層の厚みは、塗布（塗工）に用いる本実施形態の樹脂組成物の溶液の濃度と塗布厚みにより調整することができ、特に限定されないが、一般的には塗布厚みが厚くなると乾燥時に溶剤が残り易くなることから、０．１～５００μｍが好ましい。 In the production of the single-layer sheet or resin composite sheet of this embodiment, the drying conditions for removing the solvent are not particularly limited, but if the temperature is low, the solvent tends to remain in the resin composition, and if the temperature is high, Since curing of the resin composition progresses, the temperature is preferably 20° C. to 200° C. for 1 to 90 minutes. Further, the single layer sheet or the resin composite sheet can be used in an uncured state where the solvent is simply dried, or it can be used in a semi-cured (B-staged) state if necessary. Further, the thickness of the resin layer in the single-layer sheet or resin composite sheet of this embodiment can be adjusted by the concentration of the solution of the resin composition of this embodiment used for application (coating) and the coating thickness, and there are no particular limitations. However, in general, as the coating thickness increases, solvent tends to remain during drying, so 0.1 to 500 μm is preferable.
　以下に実施例を挙げて本発明をさらに具体的に説明する。以下の実施例に示す材料、使用量、割合、処理内容、処理手順等は、本発明の趣旨を逸脱しない限り、適宜、変更することができる。従って、本発明の範囲は以下に示す具体例に限定されるものではない。
　実施例で用いた測定機器等が廃番等により入手困難な場合、他の同等の性能を有する機器を用いて測定することができる。 The present invention will be explained in more detail with reference to Examples below. The materials, usage amounts, proportions, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.
If the measuring equipment used in the examples is difficult to obtain due to discontinuation or the like, measurement can be performed using other equipment with equivalent performance.
＜重量平均分子量および数平均分子量の測定＞
　下記式（Ｖ）で表される構成単位を有する重合体（ｖａ）等の重量平均分子量（Ｍｗ）および数平均分子量（Ｍｎ）は、ゲルパーミエーションクロマトグラフィ（ＧＰＣ）法によって測定した。送液ポンプ（島津製作所社製、ＬＣ－２０ＡＤ）、示差屈折率検出器（島津製作所社製、ＲＩＤ－１０Ａ）、ＧＰＣカラム（昭和電工社製、ＧＰＣ　ＫＦ－８０１、８０２、８０３、８０４）を使用し、溶媒にテトラヒドロフラン、流量１．０ｍＬ／分、カラム温度４０℃、単分散ポリスチレンによる検量線を用いて行った。 <Measurement of weight average molecular weight and number average molecular weight>
The weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymer (va) having a structural unit represented by the following formula (V) were measured by gel permeation chromatography (GPC). Liquid pump (manufactured by Shimadzu Corporation, LC-20AD), differential refractive index detector (manufactured by Shimadzu Corporation, RID-10A), GPC column (manufactured by Showa Denko Corporation, GPC KF-801, 802, 803, 804) The experiment was carried out using tetrahydrofuran as the solvent, a flow rate of 1.0 mL/min, a column temperature of 40° C., and a calibration curve using monodisperse polystyrene.
＜合成例１　式（Ｖ）で表される構成単位を有する重合体（ｖａ）の合成＞
　ジビニルベンゼン２．２５モル（２９２．９ｇ）、エチルビニルベンゼン１．３２モル（１７２．０ｇ）、スチレン１１．４３モル（１１９０．３ｇ）、酢酸ｎ－プロピル１５．０モル（１５３２．０ｇ）を反応器内に投入し、７０℃で６００ミリモルの三フッ化ホウ素のジエチルエーテル錯体を添加し、４時間反応させた。重合反応を炭酸水素ナトリウム水溶液で停止させた後、純水で３回油層を洗浄し、６０℃で減圧脱揮し、式（Ｖ）で表される構成単位を有する重合体（ｖａ）を回収した。得られた式（Ｖ）で表される構成単位を有する重合体（ｖａ）を秤量して、式（Ｖ）で表される構成単位を有する重合体（ｖａ）８６０．８ｇが得られたことを確認した。 <Synthesis Example 1 Synthesis of polymer (va) having a structural unit represented by formula (V)>
2.25 moles (292.9 g) of divinylbenzene, 1.32 moles (172.0 g) of ethylvinylbenzene, 11.43 moles (1190.3 g) of styrene, and 15.0 moles (1532.0 g) of n-propyl acetate. The mixture was placed in a reactor, and 600 mmol of boron trifluoride diethyl ether complex was added at 70°C, followed by reaction for 4 hours. After stopping the polymerization reaction with an aqueous sodium hydrogen carbonate solution, the oil layer was washed three times with pure water and devolatilized under reduced pressure at 60°C to recover a polymer (va) having a structural unit represented by formula (V). did. The obtained polymer (va) having a structural unit represented by formula (V) was weighed, and 860.8 g of a polymer (va) having a structural unit represented by formula (V) was obtained. It was confirmed.
　得られた式（Ｖ）で表される構成単位を有する重合体（ｖａ）の数平均分子量Ｍｎは２，０６０、重量平均分子量Ｍｗは３０，７００、単分散度Ｍｗ／Ｍｎは１４．９であった。１３Ｃ－ＮＭＲおよび１Ｈ－ＮＭＲ分析を行うことにより、式（Ｖ）で表される構成単位を有する重合体（ｖａ）には、原料として用いた各単量体単位に由来する共鳴線が観察された。ＮＭＲ測定結果、および、ＧＣ分析結果に基づき、式（Ｖ）で表される構成単位を有する重合体（ｖａ）における各単量体単位（各原料に由来する構成単位）の割合は以下のように算出された。
ジビニルベンゼン由来の構成単位：２０．９モル％（２４．３質量％）
エチルビニルベンゼン由来の構成単位：９．１モル％(１０．７質量％)
スチレンに由来する構成単位：７０．０モル％（６５．０質量％）
　また、ジビニルベンゼン由来の残存ビニル基をもつ構成単位は、１６．７モル％（１８．５質量％）であった。 The obtained polymer (va) having a structural unit represented by formula (V) had a number average molecular weight Mn of 2,060, a weight average molecular weight Mw of 30,700, and a monodispersity Mw/Mn of 14.9. there were. By performing 13 C-NMR and 1 H-NMR analysis, it was found that the polymer (va) having the structural unit represented by formula (V) had resonance lines originating from each monomer unit used as a raw material. observed. Based on the NMR measurement results and the GC analysis results, the proportion of each monomer unit (constituent unit derived from each raw material) in the polymer (va) having the structural unit represented by formula (V) is as follows. was calculated.
Constituent unit derived from divinylbenzene: 20.9 mol% (24.3 mass%)
Constituent unit derived from ethylvinylbenzene: 9.1 mol% (10.7 mass%)
Structural unit derived from styrene: 70.0 mol% (65.0 mass%)
Furthermore, the amount of structural units having residual vinyl groups derived from divinylbenzene was 16.7 mol % (18.5 mass %).
実施例１
　式（Ｍ－２）で表される化合物であってｍ＝０である化合物（日本化薬社製、「ＭＩＲ－５０００」）２１．０質量部、合成例１で得られた式（Ｖ）で表される構成単位を有する重合体（ｖａ）２１．０質量部、下記に構造を示すマレイミド化合物（ｍ１ａ）（ＤＩＣ社製、「ＮＥ－Ｘ－９４７０Ｓ」、式（Ｍ１）で表される化合物）２１．０質量部、熱可塑性エラストマー（ＳＢＳ、ＪＳＲ社製、ＴＲ２２５０）１６．０質量部、リン系難燃剤（ＰＸ－２００、大八化学社製）２１．０質量部を、メチルエチルケトン（溶剤）に溶解させて混合し、ワニスを得た。なお、上述の各添加量は、固形分量を示す。 Example 1
21.0 parts by mass of a compound represented by formula (M-2) where m = 0 (manufactured by Nippon Kayaku Co., Ltd., "MIR-5000"), formula (V) obtained in Synthesis Example 1 21.0 parts by mass of a polymer (va) having a structural unit represented by, a maleimide compound (m1a) having the structure shown below (manufactured by DIC Corporation, "NE-X-9470S", represented by formula (M1) compound), 16.0 parts by mass of thermoplastic elastomer (SBS, manufactured by JSR Corporation, TR2250), 21.0 parts by mass of phosphorus flame retardant (PX-200, manufactured by Daihachi Kagaku Co., Ltd.), methyl ethyl ketone ( (solvent) and mixed to obtain a varnish. Note that each amount added above indicates the amount of solid content.
マレイミド化合物（ｍ１ａ）
ｎは、１～２０の整数である。 Maleimide compound (m1a)
n is an integer from 1 to 20.
＜厚さ０．８ｍｍの硬化板の試験片の製造＞
　得られたワニスから溶剤を蒸発留去することで樹脂組成物粉末を得た。樹脂組成物粉末を１辺１００ｍｍ、厚さ０．８ｍｍの型に充填し、両面に厚さ１２μｍの銅箔（３ＥＣ－Ｍ２Ｓ－ＶＬＰ、三井金属鉱業（株）製）を配置し、圧力３０ｋｇ／ｃｍ２、温度２２０℃で１２０分間真空プレスを行い、１辺１００ｍｍ、厚さ０．８ｍｍの硬化板を得た。
　得られた硬化板を用いて、比誘電率（Ｄｋ）、誘電正接（Ｄｆ）、ガラス転移温度（Ｔｇ）、ピール強度、デスミア耐性および吸湿耐熱性の評価を行った。評価結果を表１に示す。 <Manufacture of a cured plate test piece with a thickness of 0.8 mm>
A resin composition powder was obtained by evaporating the solvent from the obtained varnish. A mold with a side of 100 mm and a thickness of 0.8 mm was filled with the resin composition powder, copper foil (3EC-M2S-VLP, manufactured by Mitsui Mining & Mining Co., Ltd.) with a thickness of 12 μm was placed on both sides, and a pressure of 30 kg/ cm 2 and vacuum pressing at a temperature of 220° C. for 120 minutes to obtain a cured plate with a side of 100 mm and a thickness of 0.8 mm.
The obtained cured plates were used to evaluate dielectric constant (Dk), dielectric loss tangent (Df), glass transition temperature (Tg), peel strength, desmear resistance, and moisture absorption heat resistance. The evaluation results are shown in Table 1.
＜測定方法および評価方法＞
（１）比誘電率（Ｄｋ）および誘電正接（Ｄｆ）
　得られた硬化板の両面の銅箔をエッチングにより除去後、１０ｍｍｘ１ｍｍにダウンサイジングして、評価用サンプルを得た。得られた評価用サンプルを、１２０℃で、６０分間乾燥させた後、摂動法空洞共振器を用いて、周波数１０ＧＨｚにおける乾燥後の比誘電率（Ｄｋ）および誘電正接（Ｄｆ）を測定した。測定温度は２３℃とした。
　摂動法空洞共振器は、アジレントテクノロジー社製、Ａｇｉｌｅｎｔ８７２２ＥＳを用いた。
比誘電率（Ｄｋ）
Ａ：２．５０以下
Ｂ：２．５０超２．６０以下
Ｃ：２．６０超
誘電正接（Ｄｆ）
Ｓ：０．００１４以下
Ａ：０．００１４超０．００１８以下
Ｂ：０．００１８超０．００２０以下
Ｃ：０．００２０超 <Measurement method and evaluation method>
(1) Relative permittivity (Dk) and dielectric loss tangent (Df)
After removing the copper foils on both sides of the obtained cured plate by etching, it was downsized to 10 mm x 1 mm to obtain a sample for evaluation. The obtained evaluation sample was dried at 120° C. for 60 minutes, and then the relative dielectric constant (Dk) and dielectric loss tangent (Df) after drying at a frequency of 10 GHz were measured using a perturbation method cavity resonator. The measurement temperature was 23°C.
The perturbation method cavity resonator used was Agilent 8722ES manufactured by Agilent Technologies.
Specific permittivity (Dk)
A: 2.50 or less B: Over 2.50 and 2.60 or less C: 2.60 super dielectric loss tangent (Df)
S: 0.0014 or less A: More than 0.0014 and less than 0.0018 B: More than 0.0018 and less than 0.0020 C: More than 0.0020
（２）ガラス転移温度（Ｔｇ）
　ガラス転移温度は、得られた硬化板の両面の銅箔をエッチングにより除去後、１２．７ｍｍ×３０ｍｍにダウンサイジングしたサンプルについて、動的粘弾性測定装置を用い、ＪＩＳ－Ｋ７２４４－４：１９９９（プラスチック－動的機械特性の試験方法－第４部：引張振動－非共振法）に準拠し、開始温度３０℃、終了温度４００℃、昇温速度５℃／分、測定周波数１Ｈｚ、窒素雰囲気下において、動的粘弾性を測定し、その際得られた損失正接（ｔａｎδ）の最大値となる温度をガラス転移温度とした。
　動的粘弾性測定装置は、セイコーインスツル株式会社製、ＥＸＳＴＡＲ６０００　ＤＭＳ６１００を用いた。
　以下の通り評価した。
Ａ：２３０℃以上
Ｂ：２００℃以上２３０℃未満
Ｃ：２００℃未満 (2) Glass transition temperature (Tg)
The glass transition temperature was measured using a dynamic viscoelasticity measuring device on a sample that was downsized to 12.7 mm x 30 mm after removing the copper foil on both sides of the obtained cured plate by etching, and was determined according to JIS-K7244-4:1999 ( Plastics - Test method for dynamic mechanical properties - Part 4: Tensile vibration - Non-resonance method), starting temperature 30°C, ending temperature 400°C, heating rate 5°C/min, measurement frequency 1Hz, under nitrogen atmosphere The dynamic viscoelasticity was measured, and the temperature at which the loss tangent (tan δ) obtained was the maximum value was taken as the glass transition temperature.
The dynamic viscoelasticity measuring device used was EXSTAR6000 DMS6100 manufactured by Seiko Instruments Inc.
It was evaluated as follows.
A: 230°C or more B: 200°C or more and less than 230°C C: Less than 200°C
（３）ピール強度
　上記のようにして得られた硬化板（１０ｍｍ×１００ｍｍ×０．８ｍｍ）を用い、ＪＩＳ　Ｃ６４８１の５．７　「引きはがし強さ」の規定に準じて、銅箔ピール強度（接着力）を２回測定し、平均値を求めた。測定温度は２３℃とした。
　以下の通り評価した。
Ｓ：０．５０ｋＮ／ｍ以上
Ａ：０．３８ｋＮ／ｍ以上０．５０ｋＮ／ｍ未満
Ｂ：０．２８ｋＮ／ｍ以上０．３８ｋＮ／ｍ未満
Ｃ：０．２８ｋＮ／ｍ未満 (3) Peel strength Using the cured plate (10 mm x 100 mm x 0.8 mm) obtained as described above, the copper foil peel strength ( The adhesive strength) was measured twice and the average value was determined. The measurement temperature was 23°C.
It was evaluated as follows.
S: 0.50kN/m or more A: 0.38kN/m or more and less than 0.50kN/m B: 0.28kN/m or more and less than 0.38kN/m C: Less than 0.28kN/m
（４）デスミア耐性
　得られた硬化板の両面の銅箔をエッチングにより除去後、ダウンサイジング（５０ｍｍ×５０ｍｍ）したサンプルを用いて、以下の浸漬処理を行った。まず、得られたサンプルを膨潤液（アトテックジャパン社製、スウェリングディップセキュリガントＰ）に８０℃で１０分間浸漬した。次に、浸漬したサンプルを粗化液（アトテックジャパン社製、コンセントレートコンパクトＣＰ）に８０℃で５分間浸漬した。次に、浸漬したサンプルを中和液（アトテックジャパン社製、リダクションコンディショナーセキュリガントＰ５００）に４５℃で１０分間浸漬した。この浸漬処理を２回行った後のサンプルの質量減少率（質量％）を測定した。
　以下の通り評価した。マイナス記号は質量が減少していることを表す。
Ａ：質量減少率が、－４．０質量％～－２．０質量％の範囲である。
Ｂ：質量減少率が上記範囲以外である。 (4) Desmear resistance After removing the copper foil on both sides of the obtained cured plate by etching, the following immersion treatment was performed using a downsized (50 mm x 50 mm) sample. First, the obtained sample was immersed in a swelling liquid (Swelling Dip Securigant P, manufactured by Atotech Japan) at 80° C. for 10 minutes. Next, the immersed sample was immersed in a roughening solution (Concentrate Compact CP, manufactured by Atotech Japan) at 80° C. for 5 minutes. Next, the immersed sample was immersed in a neutralizing solution (Reduction Conditioner Securigant P500, manufactured by Atotech Japan) at 45° C. for 10 minutes. After performing this immersion treatment twice, the mass reduction rate (mass %) of the sample was measured.
It was evaluated as follows. A minus sign represents a decrease in mass.
A: The mass reduction rate is in the range of -4.0% by mass to -2.0% by mass.
B: Mass reduction rate is outside the above range.
（５）吸湿耐熱性
　得られた硬化板を５０ｍｍ×５０ｍｍに切断（ダウンサイジング）し、片面側の銅箔を全てエッチングにより除去し、もう一方の面側においては、面の半分の銅箔をエッチングにより除去して、吸湿耐熱性測定用サンプルを得た。得られたサンプルを１２０℃で、６０分間乾燥させた後、プレッシャークッカー試験機を用いて、１２１℃、２気圧の飽和水蒸気存在下、５時間静置し、さらに２６０℃の半田槽に３０秒間浸漬（ディップ）させて、外観変化の異常の有無を目視にて観察した。プレッシャークッカー試験機は、平山製作所社製、ＰＣ－３型を用いた。各測定は、それぞれ３枚ずつ試験を行い、その３枚において、膨れが０枚であった場合には「Ａ」、膨れが１～２枚見られた場合には「Ｂ」、膨れが３枚見られた場合には「Ｃ」と評価した。外観の観察は、５人の専門家が行い多数決とした。 (5) Moisture absorption and heat resistance The obtained cured board was cut into 50 mm x 50 mm (downsizing), all the copper foil on one side was removed by etching, and half of the copper foil on the other side was removed. It was removed by etching to obtain a sample for measuring moisture absorption and heat resistance. The obtained sample was dried at 120°C for 60 minutes, then left to stand for 5 hours at 121°C in the presence of saturated steam at 2 atm using a pressure cooker tester, and then placed in a solder bath at 260°C for 30 seconds. The samples were dipped and visually observed for any abnormalities in appearance. The pressure cooker tester used was model PC-3 manufactured by Hirayama Seisakusho Co., Ltd. For each measurement, three sheets were tested, and if there were no bulges among the three sheets, it would be ``A'', if 1 or 2 bulges were observed, it would be ``B'', and if 3 sheets had bulges, it would be ``B''. If a sheet was seen, it was rated "C". The appearance was observed by five experts and a majority vote was taken.
実施例２
　実施例１において、式（Ｍ－２）で表される化合物であってｍ＝０である化合物（日本化薬社製、「ＭＩＲ－５０００」）の含有量を１８．９質量部、合成例１で得られた式（Ｖ）で表される構成単位を有する重合体（ｖａ）の含有量を２１．８質量部、マレイミド化合物（ｍ１ａ）（ＤＩＣ社製、「ＮＥ－Ｘ－９４７０Ｓ」）の含有量を２２．３質量部に変更し、他は同様に行った。結果を表１に示した。 Example 2
In Example 1, the content of the compound represented by formula (M-2) where m = 0 (manufactured by Nippon Kayaku Co., Ltd., "MIR-5000") was 18.9 parts by mass, and the synthesis example The content of the polymer (va) having the structural unit represented by the formula (V) obtained in 1 was 21.8 parts by mass, and the maleimide compound (m1a) (manufactured by DIC Corporation, "NE-X-9470S") The content was changed to 22.3 parts by mass, and the other procedures were carried out in the same manner. The results are shown in Table 1.
実施例３
　実施例１において、式（Ｍ－２）で表される化合物であってｍ＝０である化合物（日本化薬社製、「ＭＩＲ－５０００」）の含有量を２０．９質量部、合成例１で得られた式（Ｖ）で表される構成単位を有する重合体（ｖａ）の含有量を１６．８質量部、マレイミド化合物（ｍ１ａ）（ＤＩＣ社製、「ＮＥ－Ｘ－９４７０Ｓ」）の含有量を２５．３質量部に変更し、他は同様に行った。結果を表１に示した。 Example 3
In Example 1, the content of the compound represented by formula (M-2) where m = 0 (manufactured by Nippon Kayaku Co., Ltd., "MIR-5000") was 20.9 parts by mass, and the synthesis example The content of the polymer (va) having the structural unit represented by the formula (V) obtained in 1 was 16.8 parts by mass, and the maleimide compound (m1a) (manufactured by DIC Corporation, "NE-X-9470S") The content was changed to 25.3 parts by mass, and the other procedures were carried out in the same manner. The results are shown in Table 1.
実施例４
　実施例１において、式（Ｍ－２）で表される化合物であってｍ＝０である化合物（日本化薬社製、「ＭＩＲ－５０００」）の含有量を１３．０質量部、合成例１で得られた式（Ｖ）で表される構成単位を有する重合体（ｖａ）の含有量を５．０質量部、マレイミド化合物（ｍ１ａ）（ＤＩＣ社製、「ＮＥ－Ｘ－９４７０Ｓ」）の含有量を４５．０質量部に変更し、他は同様に行った。結果を表１に示した。 Example 4
In Example 1, the content of the compound represented by formula (M-2) where m = 0 (manufactured by Nippon Kayaku Co., Ltd., "MIR-5000") was 13.0 parts by mass, and the synthesis example The content of the polymer (va) having the structural unit represented by the formula (V) obtained in 1 was 5.0 parts by mass, and the maleimide compound (m1a) (manufactured by DIC Corporation, "NE-X-9470S") The content was changed to 45.0 parts by mass, and the other procedures were the same. The results are shown in Table 1.
実施例５
　実施例１において、式（Ｍ－２）で表される化合物であってｍ＝０である化合物（日本化薬社製、「ＭＩＲ－５０００」）の含有量を２４．０質量部、合成例１で得られた式（Ｖ）で表される構成単位を有する重合体（ｖａ）の含有量を３４．０質量部、マレイミド化合物（ｍ１ａ）（ＤＩＣ社製、「ＮＥ－Ｘ－９４７０Ｓ」）の含有量を５．０質量部に変更し、他は同様に行った。結果を表１に示した。 Example 5
In Example 1, the content of the compound represented by formula (M-2) where m = 0 (manufactured by Nippon Kayaku Co., Ltd., "MIR-5000") was 24.0 parts by mass, and the synthesis example The content of the polymer (va) having the structural unit represented by the formula (V) obtained in 1 was 34.0 parts by mass, and the maleimide compound (m1a) (manufactured by DIC Corporation, "NE-X-9470S") The content was changed to 5.0 parts by mass, and the other procedures were carried out in the same manner. The results are shown in Table 1.
実施例６
　実施例１において、式（Ｍ－２）で表される化合物であってｍ＝０である化合物（日本化薬社製、「ＭＩＲ－５０００」）の含有量を５．０質量部、合成例１で得られた式（Ｖ）で表される構成単位を有する重合体（ｖａ）の含有量を２９．０質量部、マレイミド化合物（ｍ１ａ）（ＤＩＣ社製、「ＮＥ－Ｘ－９４７０Ｓ」）の含有量を２９．０質量部に変更し、他は同様に行った。結果を表１に示した。 Example 6
In Example 1, the content of the compound represented by formula (M-2) where m = 0 (manufactured by Nippon Kayaku Co., Ltd., "MIR-5000") was 5.0 parts by mass, and the synthesis example The content of the polymer (va) having the structural unit represented by the formula (V) obtained in 1 was 29.0 parts by mass, and the maleimide compound (m1a) (manufactured by DIC Corporation, "NE-X-9470S") The content was changed to 29.0 parts by mass, and the other procedures were carried out in the same manner. The results are shown in Table 1.
実施例７
　実施例１において、式（Ｍ－２）で表される化合物であってｍ＝０である化合物（日本化薬社製、「ＭＩＲ－５０００」）の含有量を１８．０質量部、合成例１で得られた式（Ｖ）で表される構成単位を有する重合体（ｖａ）の含有量を４０．０質量部、マレイミド化合物（ｍ１ａ）（ＤＩＣ社製、「ＮＥ－Ｘ－９４７０Ｓ」）の含有量を５．０質量部に変更し、他は同様に行った。結果を表１に示した。 Example 7
In Example 1, the content of the compound represented by formula (M-2) where m = 0 (manufactured by Nippon Kayaku Co., Ltd., "MIR-5000") was 18.0 parts by mass, and the synthesis example The content of the polymer (va) having the structural unit represented by the formula (V) obtained in 1 was 40.0 parts by mass, and the maleimide compound (m1a) (manufactured by DIC Corporation, "NE-X-9470S") The content was changed to 5.0 parts by mass, and the other procedures were carried out in the same manner. The results are shown in Table 1.
比較例１
　実施例１において、式（Ｍ－２）で表される化合物であってｍ＝０である化合物（日本化薬社製、「ＭＩＲ－５０００」）および式（Ｖ）で表される構成単位を有する重合体（ｖａ）を用いず、マレイミド化合物（ｍ１ａ）（ＤＩＣ社製、「ＮＥ－Ｘ－９４７０Ｓ」）の含有量を６３．０質量部に変更し、他は同様に行った。結果を表２に示した。 Comparative example 1
In Example 1, a compound represented by formula (M-2) where m=0 (manufactured by Nippon Kayaku Co., Ltd., "MIR-5000") and a structural unit represented by formula (V) were The same procedure was carried out except that the polymer (va) was not used, and the content of the maleimide compound (m1a) (manufactured by DIC, "NE-X-9470S") was changed to 63.0 parts by mass. The results are shown in Table 2.
比較例２
　実施例１において、式（Ｖ）で表される構成単位を有する重合体（ｖａ）およびマレイミド化合物（ｍ１ａ）（ＤＩＣ社製、「ＮＥ－Ｘ－９４７０Ｓ」）を用いず、式（Ｍ－２）で表される化合物であってｍ＝０である化合物（日本化薬社製、「ＭＩＲ－５０００」）含有量を６３．０質量部に変更し、他は同様に行った。結果を表２に示した。 Comparative example 2
In Example 1, the polymer (va) having the structural unit represented by the formula (V) and the maleimide compound (m1a) (manufactured by DIC, "NE-X-9470S") were not used, and the formula (M-2 ) in which m=0 (manufactured by Nippon Kayaku Co., Ltd., "MIR-5000") content was changed to 63.0 parts by mass, and the same procedure was followed except that the content was changed to 63.0 parts by mass. The results are shown in Table 2.
比較例３
　実施例１において、式（Ｍ－２）で表される化合物であってｍ＝０である化合物（日本化薬社製、「ＭＩＲ－５０００」）およびマレイミド化合物（ｍ１ａ）（ＤＩＣ社製、「ＮＥ－Ｘ－９４７０Ｓ」）を用いず、式（Ｖ）で表される構成単位を有する重合体（ｖａ）の含有量を６３．０質量部に変更し、他は同様に行った。結果を表２に示した。 Comparative example 3
In Example 1, a compound represented by formula (M-2) where m=0 (manufactured by Nippon Kayaku Co., Ltd., "MIR-5000") and a maleimide compound (m1a) (manufactured by DIC Corporation, "NE-X-9470S") was not used, and the content of the polymer (va) having the structural unit represented by formula (V) was changed to 63.0 parts by mass, and the same procedure was performed except that the content of the polymer (va) having the structural unit represented by formula (V) was changed to 63.0 parts by mass. The results are shown in Table 2.
比較例４
　実施例１において、式（Ｍ－２）で表される化合物であってｍ＝０である化合物（日本化薬社製、「ＭＩＲ－５０００」）の含有量を３１．５質量部、マレイミド化合物（ｍ１ａ）（ＤＩＣ社製、「ＮＥ－Ｘ－９４７０Ｓ」）の含有量を３１．５質量部に変更し、式（Ｖ）で表される構成単位を有する重合体（ｖａ）を用いず、他は同様に行った。結果を表２に示した。 Comparative example 4
In Example 1, the content of the compound represented by formula (M-2) where m = 0 (manufactured by Nippon Kayaku Co., Ltd., "MIR-5000") was 31.5 parts by mass, and the content of the maleimide compound was 31.5 parts by mass. (m1a) (manufactured by DIC Corporation, "NE-X-9470S") content was changed to 31.5 parts by mass, and the polymer (va) having the structural unit represented by formula (V) was not used. The rest were done in the same way. The results are shown in Table 2.
比較例５
　実施例１において、式（Ｍ－２）で表される化合物であってｍ＝０である化合物（日本化薬社製、「ＭＩＲ－５０００」）を用いず、式（Ｖ）で表される構成単位を有する重合体（ｖａ）の含有量を３１．５質量部、マレイミド化合物（ｍ１ａ）（ＤＩＣ社製、「ＮＥ－Ｘ－９４７０Ｓ」）の含有量を３１．５質量部に変更し、他は同様に行った。結果を表２に示した。 Comparative example 5
In Example 1, the compound represented by formula (M-2) where m = 0 (manufactured by Nippon Kayaku Co., Ltd., "MIR-5000") was not used, and the compound represented by formula (V) was used. The content of the polymer (va) having the structural unit was changed to 31.5 parts by mass, the content of the maleimide compound (m1a) (manufactured by DIC Corporation, "NE-X-9470S") was changed to 31.5 parts by mass, The rest were done in the same way. The results are shown in Table 2.
比較例６
　実施例１において、式（Ｖ）で表される構成単位を有する重合体（ｖａ）２１．０質量部を等量のマレイミド化合物（日本化薬株式会社製、ＭＩＲ－３０００、下記に構造を示す。）に変更し、他は同様に行った。結果を表２に示した。
Comparative example 6
In Example 1, 21.0 parts by mass of a polymer (va) having a structural unit represented by formula (V) was mixed with an equivalent amount of a maleimide compound (manufactured by Nippon Kayaku Co., Ltd., MIR-3000, the structure of which is shown below) .) and did the other things in the same way. The results are shown in Table 2.

Claims (21)

  1. 式（Ｍ）で表される化合物（Ｍ）と、
    式（Ｖ）で表される構成単位を有する重合体（Ｖ）と、
    式（Ｍ１）で表される化合物（Ｍ１）と
    を含む、樹脂組成物。
    （式（Ｍ）中、Ｒは、それぞれ独立に、ハロゲン原子で置換されていてもよい炭素数１～１０の炭化水素基を表し、Ｒｍｘは、それぞれ独立に、メチレン基、エチリデン基、または、２，２－プロピリデン基であり、Ｒｍｙは、下記群（Ａ）から選択される基である。ｍは、０～３の整数を表し、ｎは、繰返し数の平均値であり、１．００≦ｎ≦２０．００を表す。）
    （群（Ａ））
    (群（Ａ）において、Ｒｙは、それぞれ独立に、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、または、置換基を有してもよいフェニル基であり、ｎｙは、それぞれ独立に０～３の整数であり、＊は、Ｒｍｘとの結合位置である。)
    （式（Ｖ）中、Ａｒは芳香族炭化水素連結基を表す。＊は、結合位置を表す。）
    （式（Ｍ１）中、ＲＭ１、ＲＭ２、ＲＭ３、およびＲＭ４は、それぞれ独立に、水素原子または有機基を表す。ＲＭ５およびＲＭ６は、それぞれ独立に、水素原子またはアルキル基を表す。ＡｒＭは２価の芳香族基を表す。Ａは、４～６員環の脂環基である。ＲＭ７およびＲＭ８は、それぞれ独立に、アルキル基である。ｍｘは１または２であり、ｌｘは０または１である。ＲＭ９およびＲＭ１０は、それぞれ独立に、水素原子またはアルキル基を表す。ＲＭ１１、ＲＭ１２、ＲＭ１３、およびＲＭ１４は、それぞれ独立に、水素原子または有機基を表す。ＲＭ１５は、それぞれ独立に、炭素数１～１０のアルキル基、炭素数１～１０のアルキルオキシ基、炭素数１～１０のアルキルチオ基、炭素数６～１０のアリール基、炭素数６～１０のアリールオキシ基、炭素数６～１０のアリールチオ基、ハロゲン原子、水酸基またはメルカプト基を表す。ｐｘは０～３の整数を表す。ｎｘは１～２０の整数を表す。）     A compound (M) represented by formula (M),
    A polymer (V) having a structural unit represented by formula (V),
    A resin composition comprising a compound (M1) represented by formula (M1).
    (In formula (M), R each independently represents a hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a halogen atom, and R mx each independently represents a methylene group, an ethylidene group, or , 2,2-propylidene group, R my is a group selected from the following group (A), m represents an integer of 0 to 3, n is the average value of the number of repeats, 1 .00≦n≦20.00)
    (Group (A))
    (In group (A), R y is each independently an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group which may have a substituent, and ny is , each independently an integer from 0 to 3, and * is the bonding position with R mx .)
    (In formula (V), Ar represents an aromatic hydrocarbon linking group. * represents the bonding position.)
    (In formula (M1), R M1 , R M2 , R M3 , and R M4 each independently represent a hydrogen atom or an organic group. R M5 and R M6 each independently represent a hydrogen atom or an alkyl group. Ar M represents a divalent aromatic group. A 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 represents 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, or an aryl group having 6 to 10 carbon atoms. , represents an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a halogen atom, a hydroxyl group or a mercapto group. px represents an integer of 0 to 3. nx represents an integer of 1 to 20. )
  2. 前記樹脂組成物中の樹脂固形分１００質量部に対する、前記式（Ｍ）で表される化合物（Ｍ）の含有量が５～５０質量部である、請求項１に記載の樹脂組成物。 The resin composition according to claim 1, wherein the content of the compound (M) represented by the formula (M) is 5 to 50 parts by mass based on 100 parts by mass of resin solid content in the resin composition.
  3. 前記樹脂組成物中の樹脂固形分１００質量部に対する、前記式（Ｖ）で表される構成単位を有する重合体（Ｖ）の含有量が５～５０質量部である、請求項１または２に記載の樹脂組成物。 According to claim 1 or 2, the content of the polymer (V) having the structural unit represented by the formula (V) is 5 to 50 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition. The resin composition described.
  4. 前記樹脂組成物中の樹脂固形分１００質量部に対する、前記式（Ｍ１）で表される化合物（Ｍ１）の含有量が５～５０質量部である、請求項１または２に記載の樹脂組成物。 The resin composition according to claim 1 or 2, wherein the content of the compound (M1) represented by the formula (M1) is 5 to 50 parts by mass based on 100 parts by mass of the resin solid content in the resin composition. .
  5. 前記式（Ｍ）で表される化合物（Ｍ）において、ｎが、１．０５≦ｎ≦２０．００である、請求項１または２に記載の樹脂組成物。 The resin composition according to claim 1 or 2, wherein in the compound (M) represented by the formula (M), n is 1.05≦n≦20.00.
  6. 前記式（Ｍ）で表される化合物（Ｍ）が、式（Ｍ－１）で表される化合物を含む、請求項１または２に記載の樹脂組成物。
    （式（Ｍ－１）中、Ｒは、それぞれ独立に、ハロゲン原子で置換されていてもよい炭素数１～１０の炭化水素基を表す。ｍは、０～３の整数を表し、ｎは、繰返し数の平均値であり、１．００≦ｎ≦２０．００を表す。）     The resin composition according to claim 1 or 2, wherein the compound (M) represented by formula (M) includes a compound represented by formula (M-1).
    (In formula (M-1), R each independently represents a hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a halogen atom, m represents an integer of 0 to 3, and n represents , is the average value of the number of repetitions, and represents 1.00≦n≦20.00.)
  7. 前記式（Ｍ）で表される化合物（Ｍ）が、式（Ｍ－２）で表される化合物を含む、請求項１または２に記載の樹脂組成物。
    （式（Ｍ－２）中、Ｒｚは、それぞれ独立に、炭素数１～１０の炭化水素基を表す。ｍは０～３の整数を表し、ｎは、繰返し数の平均値であり、１．００≦ｎ≦２０．００を表す。）     The resin composition according to claim 1 or 2, wherein the compound (M) represented by formula (M) includes a compound represented by formula (M-2).
    (In formula (M-2), R z each independently represents a hydrocarbon group having 1 to 10 carbon atoms, m represents an integer of 0 to 3, n is the average value of the number of repeats, (Represents 1.00≦n≦20.00.)
  8. 前記式（Ｖ）で表される構成単位を有する重合体（Ｖ）の重量平均分子量が、３，０００～１３０，０００である、請求項１または２に記載の樹脂組成物。 The resin composition according to claim 1 or 2, wherein the polymer (V) having the structural unit represented by the formula (V) has a weight average molecular weight of 3,000 to 130,000.
  9. 前記式（Ｖ）で表される構成単位を有する重合体（Ｖ）の重量平均分子量が、１０，０００～１３０，０００である、請求項１または２に記載の樹脂組成物。 The resin composition according to claim 1 or 2, wherein the polymer (V) having the structural unit represented by the formula (V) has a weight average molecular weight of 10,000 to 130,000.
  10. さらに、前記式（Ｍ）で表される化合物（Ｍ）および前記式（Ｍ１）で表される化合物（Ｍ１）以外のマレイミド化合物、エポキシ化合物、フェノール化合物、オキセタン樹脂、ベンゾオキサジン化合物、（メタ）アリル基を含む化合物、および、炭素－炭素不飽和二重結合を２以上含むポリフェニレンエーテル化合物からなる群より選択される１種以上の他の熱硬化性化合物（Ｃ）を含む、請求項１または２に記載の樹脂組成物。 Furthermore, a maleimide compound, an epoxy compound, a phenol compound, an oxetane resin, a benzoxazine compound, (meth) other than the compound (M) represented by the formula (M) and the compound (M1) represented by the formula (M1) Claim 1 or 2, comprising one or more other thermosetting compounds (C) selected from the group consisting of a compound containing an allyl group and a polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds. 2. The resin composition according to 2.
  11. 前記樹脂組成物中の樹脂固形分１００質量部に対する、前記他の熱硬化性化合物（Ｃ）の含有量が１～５０質量部である、請求項１０に記載の樹脂組成物。 The resin composition according to claim 10, wherein the content of the other thermosetting compound (C) is 1 to 50 parts by mass based on 100 parts by mass of resin solid content in the resin composition.
  12. さらに、充填材（Ｄ）を含む、請求項１または２に記載の樹脂組成物。 The resin composition according to claim 1 or 2, further comprising a filler (D).
  13. 前記樹脂組成物における、前記充填材（Ｄ）の含有量が、樹脂固形分１００質量部に対し、１０～１６００質量部である、請求項１２に記載の樹脂組成物。 The resin composition according to claim 12, wherein the content of the filler (D) in the resin composition is 10 to 1600 parts by mass based on 100 parts by mass of resin solid content.
  14. さらに、熱可塑性エラストマーを含む、請求項１または２に記載の樹脂組成物。 The resin composition according to claim 1 or 2, further comprising a thermoplastic elastomer.
  15. 前記樹脂組成物中の樹脂固形分１００質量部に対する、前記式（Ｍ）で表される化合物（Ｍ）の含有量が５～５０質量部であり、
    前記樹脂組成物中の樹脂固形分１００質量部に対する、前記式（Ｖ）で表される構成単位を有する重合体（Ｖ）の含有量が５～５０質量部であり、
    前記樹脂組成物中の樹脂固形分１００質量部に対する、前記式（Ｍ１）で表される化合物（Ｍ１）の含有量が５～５０質量部であり、
    前記式（Ｍ）で表される化合物（Ｍ）が、式（Ｍ－１）で表される化合物を含み、ｎが、１．０５≦ｎ≦２０．００であり、
    前記式（Ｖ）で表される構成単位を有する重合体（Ｖ）の重量平均分子量が、３，０００～１３０，０００である、請求項１に記載の樹脂組成物。
    （式（Ｍ－１）中、Ｒは、それぞれ独立に、ハロゲン原子で置換されていてもよい炭素数１～１０の炭化水素基を表す。ｍは、０～３の整数を表し、ｎは、繰返し数の平均値であり、１．００≦ｎ≦２０．００を表す。）     The content of the compound (M) represented by the formula (M) is 5 to 50 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition,
    The content of the polymer (V) having the structural unit represented by the formula (V) is 5 to 50 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition,
    The content of the compound (M1) represented by the formula (M1) is 5 to 50 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition,
    The compound (M) represented by the formula (M) includes a compound represented by the formula (M-1), and n is 1.05≦n≦20.00,
    The resin composition according to claim 1, wherein the polymer (V) having the structural unit represented by the formula (V) has a weight average molecular weight of 3,000 to 130,000.
    (In formula (M-1), R each independently represents a hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a halogen atom, m represents an integer of 0 to 3, and n represents , is the average value of the number of repetitions, and represents 1.00≦n≦20.00.)
  16. 請求項１、２または１５に記載の樹脂組成物の硬化物。 A cured product of the resin composition according to claim 1, 2 or 15.
  17. 基材と、請求項１、２または１５に記載の樹脂組成物とから形成された、プリプレグ。 A prepreg formed from a base material and the resin composition according to claim 1, 2 or 15.
  18. 請求項１７に記載のプリプレグから形成された少なくとも１つの層と、前記プリプレグから形成された層の片面または両面に配置された金属箔とを含む、金属箔張積層板。 A metal foil-clad laminate comprising at least one layer formed from the prepreg according to claim 17 and a metal foil disposed on one or both sides of the layer formed from the prepreg.
  19. 支持体と、前記支持体の表面に配置された請求項１、２または１５に記載の樹脂組成物から形成された層とを含む、樹脂複合シート。 A resin composite sheet comprising a support and a layer formed from the resin composition according to claim 1, 2 or 15 disposed on the surface of the support.
  20. 絶縁層と、前記絶縁層の表面に配置された導体層とを含むプリント配線板であって、前記絶縁層が、請求項１、２または１５に記載の樹脂組成物から形成された層から形成された層の少なくとも一方を含む、プリント配線板。 A printed wiring board comprising an insulating layer and a conductor layer disposed on a surface of the insulating layer, the insulating layer being formed from a layer formed from the resin composition according to claim 1, 2, or 15. A printed wiring board comprising at least one of the layers.
  21. 請求項２０に記載のプリント配線板を含む半導体装置。 A semiconductor device comprising the printed wiring board according to claim 20.
PCT/JP2023/007986 2022-03-11 2023-03-03 Resin composition, cured product, prepreg, metal-foil-clad laminate, resin composite sheet, printed circuit board, and semiconductor device WO2023171554A1 (en)

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