WO2023167151A1 - ブロック共重合体、樹脂組成物、硬化物、樹脂フィルム、プリプレグ、積層体、及び電子回路基板用の材料 - Google Patents

ブロック共重合体、樹脂組成物、硬化物、樹脂フィルム、プリプレグ、積層体、及び電子回路基板用の材料 Download PDF

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WO2023167151A1
WO2023167151A1 PCT/JP2023/007144 JP2023007144W WO2023167151A1 WO 2023167151 A1 WO2023167151 A1 WO 2023167151A1 JP 2023007144 W JP2023007144 W JP 2023007144W WO 2023167151 A1 WO2023167151 A1 WO 2023167151A1
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mass
block copolymer
group
parts
component
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PCT/JP2023/007144
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English (en)
French (fr)
Japanese (ja)
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裕太 松岡
剛樹 服部
敬 助川
知宏 近藤
祥文 荒木
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旭化成株式会社
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Priority to JP2024504681A priority Critical patent/JPWO2023167151A1/ja
Priority to KR1020247024183A priority patent/KR20240116955A/ko
Priority to CN202380019016.4A priority patent/CN118613516A/zh
Publication of WO2023167151A1 publication Critical patent/WO2023167151A1/ja

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    • 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
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/082—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising vinyl resins; comprising acrylic resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • 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
    • C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/06—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 by a heterocyclic ring containing nitrogen
    • 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
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C08F283/08—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to polyphenylene oxides
    • 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
    • C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers
    • 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
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/28—Oxygen or compounds releasing free oxygen
    • C08F4/32—Organic compounds
    • C08F4/34—Per-compounds with one peroxy-radical
    • 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
    • C08J5/18—Manufacture of films or sheets
    • 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
    • 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
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
    • 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
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • 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 block copolymers, resin compositions, cured products, resin films, prepregs, laminates, and materials for electronic circuit boards.
  • thermosetting resins such as epoxy resins, which have a low dielectric constant and/or low dielectric loss tangent, and excellent mechanical properties such as strength
  • thermoplastics such as polyphenylene ether resins.
  • Cured resin products containing resin as a main component have been studied and disclosed.
  • the conventionally disclosed materials still have room for improvement from the viewpoint of low dielectric constant and low dielectric loss tangent, and when these are used for printed circuit boards, the amount of information and processing speed are limited. have.
  • Patent Document 1 block copolymers of vinyl aromatic compounds and olefinic alkene compounds and hydrogenated products thereof are disclosed as modifiers for lowering the dielectric loss tangent and the dielectric constant of polyphenylene ether resins. and homopolymers of vinyl aromatic compounds.
  • Patent Document 2 discloses a styrene-based elastomer as a modifier for lowering the dielectric loss tangent and dielectric constant of an epoxy resin.
  • JP 2021-147486 A Japanese Patent Application Laid-Open No. 2020-15861
  • the inventors of the present invention have made intensive studies to solve the above-described problems of the prior art, and found that a cured product of a resin composition containing a block copolymer having a predetermined structure has a low dielectric constant and a low dielectric loss tangent, and has a high strength.
  • the inventors have found that the properties are also excellent, and have completed the present invention. That is, the present invention is as follows.
  • Component (I) the block copolymer described in [1] above; containing at least one component selected from the group consisting of the following components (II) to (IV), Resin composition.
  • a block copolymer and a resin composition containing the block copolymer from which a cured product having a low dielectric constant and a low dielectric loss tangent and excellent strength characteristics can be obtained.
  • the block copolymer of this embodiment is a polymer block (C) composed of vinyl aromatic monomer units and conjugated diene monomer units (hereinafter sometimes referred to as polymer block (C)); Polymer block (A) mainly composed of vinyl aromatic monomer units (hereinafter sometimes referred to as polymer block (A)) and/or polymer block mainly composed of conjugated diene monomer units (B) (hereinafter sometimes referred to as polymer block (B)).
  • the block copolymer of this embodiment satisfies the following conditions (i) to (iv).
  • ⁇ Condition (i)> The mass ratio of vinyl aromatic monomer units to conjugated diene monomer units in the polymer block (C) is vinyl aromatic compound/conjugated diene compound 5/95 to 95/5.
  • ⁇ Condition (iv)> The content of the vinyl aromatic monomer unit is 5 parts by mass or more and 95 parts by mass or less with respect to 100 parts by mass of the block copolymer. According to the block copolymer of the present embodiment, a cured product having a low dielectric constant, a low dielectric loss tangent, and excellent strength characteristics can be obtained.
  • a conjugated diene monomer unit refers to a structural unit derived from a conjugated diene compound in a polymer block or block copolymer produced by polymerizing a conjugated diene compound.
  • a conjugated diene compound is a diolefin having a pair of conjugated double bonds.
  • Examples of conjugated diene compounds include, but are not limited to, 1,3-butadiene, 2-methyl-1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 1,3-cyclohexadiene and the like.
  • 1,3-butadiene and isoprene are preferred, and 1,3-butadiene is more preferred.
  • 1,3-Butadiene and isoprene are widely used and readily available, and are advantageous in terms of cost, and can be easily copolymerized with styrene, which is commonly used as a vinyl aromatic compound described later. These may be used individually by 1 type, and may be used in combination of 2 or more types.
  • the conjugated diene compound may be a biotechnological compound.
  • a vinyl aromatic monomer unit refers to a structural unit derived from a vinyl aromatic compound in a polymer block or block copolymer produced by polymerizing a vinyl aromatic compound.
  • Vinyl aromatic compounds include, but are not limited to, styrene, ⁇ -methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N,N-dimethyl-p-aminoethylstyrene, N , N-diethyl-p-aminoethylstyrene and the like. These may be used individually by 1 type, and may be used in combination of 2 or more types.
  • the polymer block (C) constituting the block copolymer of the present embodiment is a polymer block composed of vinyl aromatic monomer units and conjugated diene monomer units, and other monomers are intentionally added. It has not been.
  • the vinyl aromatic compound and the conjugated diene compound used for forming the vinyl aromatic monomer units and the conjugated diene monomer units contained in the polymer block (C) are the vinyl aromatic compounds and the conjugated dienes described above. Any compound may be used.
  • the distribution state of the vinyl aromatic monomer units in the polymer block (C) is not particularly limited, and the vinyl aromatic monomer units in the polymer block (C) may be uniformly distributed, or It may be distributed in a tapered shape.
  • the polymer block (A) constituting the block copolymer is mainly composed of vinyl aromatic monomer units.
  • the term “mainly” means that it consists essentially of vinyl aromatic monomer units and no other monomers are intentionally added.
  • the polymer block (B) is mainly composed of conjugated diene monomer units. The term “mainly” means that it consists essentially of conjugated diene monomer units, and no other monomers other than conjugated diene monomers are intentionally added.
  • the content of the polymer block (A) in the block copolymer is the block copolymer before hydrogenation or A method using a nuclear magnetic resonance apparatus (NMR) using a hydrogenated block copolymer as a sample (Y. Tanaka, et al., the method described in RUBBER CHEMISTRY and TECHNOLOGY 54, 685 (1981), hereinafter "NMR method” ) can be measured.
  • NMR method nuclear magnetic resonance apparatus
  • the block copolymer of the present embodiment contains the polymer block (B)
  • the content of the polymer block (B) can be measured by NMR method.
  • the block copolymer of this embodiment has a polymer block (C).
  • Polymer block (C) consists of vinyl aromatic monomer units and conjugated diene monomer units.
  • the content of the polymer block (C) in the block copolymer of the present embodiment can be measured by NMR method.
  • the polymer block (C) has a structure in which vinyl aromatic monomer units and conjugated diene monomer units are intentionally used as structural units. It can be distinguished from the united block (B).
  • the resin composition of the present embodiment includes the block copolymer (component (I)) of the present embodiment, the component (II) described later: a radical initiator, the component (III): a polar resin, and Component (IV): Contains at least one component selected from the group consisting of curing agents.
  • Component (II), component (III), and component (IV) have polar groups.
  • vinyl aromatic compounds tend to be more compatible with components (II), (III), and (IV) than conjugated diene compounds, but the block copolymers of the present invention Since the conjugated diene compound is copolymerized, the polymer has less steric hindrance than a block polymer composed only of a vinyl aromatic compound.
  • the polymer block (C) which is a polymer of a vinyl aromatic compound and a conjugated diene compound and is a random block, is present in the block copolymer, so that component (III) and component (IV) is further improved, and the strength of the resin composition and/or cured product of the present embodiment, which will be described later, is improved.
  • the conjugated diene compound has radical reactivity, and as described above, the polymer block (C) has excellent compatibility with the component (II), the component (III), and the component (IV).
  • the conjugated diene monomer unit contained in the polymer block (C) is present in a position close to the component (II), the component (III), and the component (IV), and the conjugated diene monomer unit and these becomes a state in which reaction with the components of is likely to occur.
  • the block copolymer of the present embodiment contains Since the vinyl aromatic monomer units of are amorphous, the reactivity of the conjugated diene monomer units between the molecular chains of different block copolymers tends to be high.
  • the resin composition and the cured product of the present embodiment which will be described later, suppress the decrease in mobility and polarization of the polymer due to an external electric field, and the resin composition and the cured product have a low dielectric Tangent and low dielectric constant tend to be achieved.
  • the loss (dielectric constant) due to the polarization of the polymer by an external electric field, and the energy loss (dielectric loss tangent) due to the heat generated by movement, both are compatible with the components (III) and (IV) described later, and the reaction Therefore, the block copolymer of the present embodiment has at least one polymer block (C), the strength of the resin composition and the cured product of the present embodiment. , and leads to a low dielectric loss tangent and a low dielectric constant.
  • the amount of the conjugated diene monomer unit in the polymer block (C) is 5% by mass or more, the reactivity is good, and when it is 95% by mass or less, the polymer exhibits good compatibility and sufficient strength. and the resin composition and the cured product tend to have a low dielectric loss tangent and a low dielectric constant.
  • the block copolymer of the present embodiment The content of the polymer block (C) is 5 parts by mass or more and 95 parts by mass or less with respect to 100 parts by mass of the block copolymer. Moreover, the content of the polymer block (A) and/or the polymer block (B) is preferably 5 parts by mass or more and 95 parts by mass or less with respect to 100 parts by mass of the block copolymer of the present embodiment.
  • the content of the polymer block (C) in the block copolymer of the present embodiment is preferably 10 parts by mass or more and 90 parts by mass or less, more preferably 15 parts by mass with respect to 100 parts by mass of the block copolymer. 85 parts by mass or less, more preferably 20 parts by mass or more and 80 parts by mass or less.
  • the content of the polymer block (A) and/or the polymer block (B) is more preferably 10 parts by mass or more and 90 parts by mass or less, more preferably 15 parts by mass or more and 85 parts by mass or less, Even more preferably, it is 20 parts by mass or more and 80 parts by mass or less.
  • the block copolymer of the present embodiment preferably contains at least one polymer block (B), and the content of the polymer block (B) is It is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and even more preferably 15 parts by mass or more with respect to 100 parts by mass of the block copolymer of the present embodiment.
  • the content of the polymer block (A) is preferably 5 to 95 parts by mass, more preferably 10 to 90 parts by mass, still more preferably 15 to 85 parts by mass, relative to 100 parts by mass of the block copolymer. parts by mass, more preferably 20 to 80 parts by mass, and even more preferably 25 to 80 parts by mass.
  • the block copolymer of this embodiment has at least one polymer block (A) and/or polymer block (B).
  • the block copolymer of the present embodiment preferably has at least one polymer block (B) at its terminal.
  • the polymer block (A) is amorphous because it is a polymer block mainly composed of vinyl aromatic monomer units.
  • the polymer block (B) is a polymer block mainly composed of conjugated diene monomer units, it has radical reactivity.
  • each component (II) to (IV) constituting the resin composition reacts with the block copolymer, or the block copolymers react with each other.
  • the strength of the cured product is improved.
  • the content of vinyl aromatic monomer units and conjugated diene monomer units in the block copolymer of the present embodiment is preferably 5 parts by mass or more with respect to 100 parts by mass of the block copolymer.
  • the block copolymer and other can maintain compatibility with the components of the vinyl aromatic monomer unit can ensure strength by aggregation, and can ensure sufficient reactivity, and the resin composition and cured product exhibit sufficient strength. There is a tendency.
  • the upper limit of the content of the vinyl aromatic monomer unit and the conjugated diene monomer unit with respect to 100 parts by mass of the block copolymer of the present embodiment is the strength of the resin composition and cured product, low dielectric loss tangent, low From the viewpoint of dielectric constant, it is preferably 95 parts by mass or less.
  • the block copolymer of the present embodiment is obtained by adding other monomers copolymerizable with the vinyl aromatic compound and/or the conjugated diene compound to desired dielectric properties, that is, desired low dielectric loss tangent and low dielectric constant properties. may be copolymerized as long as it does not impair the Let the polymer block formed by the said other monomer be a polymer block (D).
  • the content of the polymer block (D) is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, still more preferably 10 parts by mass or less, and still more preferably 100 parts by mass of the block copolymer of the present embodiment. It is preferably 5 parts by mass or less, and more preferably 0 parts by mass. That is, it is preferable not to intentionally add monomers other than the vinyl aromatic compound and the conjugated diene compound.
  • the weight average molecular weight of the block copolymer of this embodiment is 35,000 or less.
  • the weight average molecular weight is a calibration curve obtained by measuring the peak molecular weight of a chromatogram obtained by gel permeation chromatography (GPC) from the measurement of a commercially available standard polystyrene (created using the peak molecular weight of standard polystyrene). It is a weight average molecular weight (Mn) determined based on, specifically, it can be measured by the method described in Examples described later.
  • the molecular weight distribution is the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the weight average molecular weight (Mn).
  • the single-peak molecular weight distribution measured by GPC of the block copolymer of the present embodiment is caused by a rapid decrease in viscosity due to the incorporation of a low-molecular-weight polymer, specifically a polymer having a weight-average molecular weight of 500 or less. From the viewpoint of preventing deterioration of handleability, it is preferably 5.0 or less, more preferably 4.0 or less, still more preferably 3.0 or less, and even more preferably 2.5 or less.
  • the weight average molecular weight of the block copolymer of the present embodiment is 35,000 or less, the crosslinkability is improved, a uniform mesh structure is formed, and a high-strength cured product is obtained. Also, compatibility with component (III) and component (IV), which will be described later, is improved, and there is a tendency to lower the dielectric constant and the dielectric loss tangent.
  • the weight-average molecular weight of the block copolymer of the present embodiment is is 35,000 or less, the block copolymers are uniformly crosslinked and are uniformly compatible with component (III): the polar resin, thereby improving the strength of the cured product containing the block copolymer.
  • component (III): the polar resin the polar resin
  • good permeability into the base material can be obtained, a uniform prepreg can be produced, the strength is improved, the dielectric loss tangent is reduced, and the dielectric There is a tendency for efficiency to be achieved.
  • the weight average molecular weight of the block copolymer of the present embodiment is 35,000 or less, preferably 30,000 or less, more preferably 25,000 or less, and still more preferably 2.0. 10,000 or less, and more preferably 25,000 or less.
  • the lower limit of the weight-average molecular weight of the block copolymer is not particularly limited, it is preferably 500 or more from the viewpoint of suppressing stickiness of the block copolymer and having good handleability.
  • the weight average molecular weight and molecular weight distribution of the block copolymer of the present embodiment can be controlled within the above numerical ranges by adjusting polymerization conditions such as the amount of monomer added, timing of addition, polymerization temperature and polymerization time.
  • the block copolymer of the present embodiment has a vinyl aromatic monomer unit content of 5 parts by mass or more and 95 parts by mass or less with respect to 100 parts by mass of the block copolymer.
  • the compatibility with component (II), component (III), and component (IV), which will be described later is improved from the viewpoint of the solubility parameter.
  • the strength of the resin composition and the cured product of the present embodiment is improved, and the dielectric loss tangent and the dielectric constant tend to be lowered.
  • the content of the vinyl aromatic monomer unit is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, still more preferably 20 parts by mass or more, and even more preferably 25 parts by mass or more. be.
  • the content of vinyl aromatic monomer units is preferably 90 parts by mass or less, more preferably 85 parts by mass or less, and even more preferably 80 parts by mass or less.
  • the content of the vinyl aromatic monomer unit in the block copolymer of the present embodiment can be measured by NMR, and specifically by the method described in the examples below.
  • the content of vinyl aromatic monomer units in the block copolymer of the present embodiment can be controlled within the numerical range described above by adjusting the amount of monomer added in the polymerization step.
  • the conjugated diene monomer units in the polymer block (B) and the polymer block (C) are 1,2-bonds and/or 3,4-bonds.
  • derived unit (a) hereinafter sometimes referred to as unit (a)
  • a unit (b) derived from a 1,4-bond
  • the total content of the conjugated diene monomer units in the polymer block (B) and the polymer block (C) is 100%, it is derived from the 1,2-bond and/or the 3,4-bond
  • the content of the unit (a) is 10 to 95 from the viewpoint of the reactivity between the block copolymers during curing when obtaining a cured product, and the reactivity with the component (III) and component (IV) described later. %, more preferably 15 to 90%, still more preferably 20 to 85%, even more preferably 25 to 80% or less.
  • the total content of 1,2-bonds and 3,4-bonds is the content of unit (a).
  • the content of the unit (a) can be controlled by using a modifier such as a polar compound in the step of polymerizing the block copolymer, and can be calculated by the method described in Examples below.
  • modifiers include tertiary amine compounds and ether compounds. It is preferred to use a tertiary amine compound.
  • a tertiary amine compound is a compound of the general formula R1R2R3N (wherein R1, R2, and R3 are hydrocarbon groups having 1 to 20 carbon atoms or hydrocarbon groups having a tertiary amino group).
  • tertiary amine compounds include, but are not limited to, trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, N-ethylpiperidine, N-methylpyrrolidine, N,N,N',N'- tetramethylethylenediamine, N,N,N',N'-tetraethylethylenediamine, 1,2-dipiperidinoethane, trimethylaminoethylpiperazine, N,N,N',N'',N''-pentamethylethylenetriamine, and N,N'-dioctyl-p-phenylenediamine.
  • the amount of the modifier to be added is preferably 0.1 mol or more, more preferably 0.5 mol or more, and still more preferably 1.0 mol or more with respect to 1 mol of the polymerization initiator described later.
  • the amount of the modifier added is preferably 0.15 mol or more, more preferably 0.5 mol or more, and still more preferably 1 mol per 1 mol of the polymerization initiator described later. .0 mol or more.
  • the block copolymer of the present embodiment may contain a block copolymer in which an aliphatic double bond based on a conjugated diene compound is hydrogenated within a range that does not impair the curing reaction.
  • a method for hydrogenating the block copolymer is not particularly limited, and conventionally known methods can be applied.
  • a hydrogenation catalyst can be used in the hydrogenation reaction.
  • Hydrogenation catalysts include, for example, (1) supported heterogeneous hydrogenation catalysts in which metals such as Ni, Pt, Pd, and Ru are supported on carbon, silica, alumina, diatomaceous earth, etc.; (3) Organometallic compounds such as Ti, Ru, Rh, Zr, etc.
  • Homogeneous hydrogenation catalysts such as so-called organometallic complexes such as Specific examples of hydrogenation catalysts include JP-B-42-8704, JP-B-43-6636, JP-B-63-4841, JP-B-1-37970, JP-B-1-53851.
  • a hydrogenation catalyst described in JP-B-2-9041 can be used.
  • Preferred hydrogenation catalysts include titanocene compounds and reducing organometallic compounds.
  • the titanocene compound compounds described in JP-A-8-109219 can be used.
  • the titanocene compound for example, at least one ligand having a (substituted) cyclopentadienyl skeleton, indenyl skeleton, or fluorenyl skeleton such as biscyclopentadienyltitanium dichloride, monopentamethylcyclopetadienyltitanium trichloride, etc. compounds having one or more.
  • the titanocene compound may contain one of the above skeletons or a combination of two of them.
  • organoalkali metal compounds such as organolithium, organomagnesium compounds, organoaluminum compounds, organoboron compounds, and organozinc compounds. These may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the hydrogenation rate of the block copolymer of the present embodiment can be controlled by appropriately adjusting the reaction temperature, reaction time, hydrogen supply amount, catalyst amount, etc. in the hydrogenation method.
  • the temperature during the hydrogenation reaction is preferably 55 to 200°C, more preferably 60 to 170°C, still more preferably 65 to 160°C.
  • the pressure of hydrogen used in the hydrogenation reaction is usually 0.1-15 MPa, preferably 0.2-10 MPa, more preferably 0.3-5 MPa.
  • the hydrogenation reaction time is usually 3 minutes to 10 hours, preferably 10 minutes to 5 hours.
  • the hydrogenation reaction can use either a batch process, a continuous process, or a combination thereof.
  • the hydrogenation rate of the block copolymer of this embodiment is 5 to 95 from the viewpoint of the balance between curing reactivity and thermal stability. %, more preferably 10 to 90%, still more preferably 13 to 87%.
  • the hydrogenation rate can be arbitrarily selected from 0 to 100% from the viewpoint of compatibility between the block copolymer of the present embodiment and other components. .
  • the block copolymer of the present embodiment can be produced, for example, by living anionic polymerization in a hydrocarbon solvent using a polymerization initiator such as an organic alkali metal compound.
  • hydrocarbon solvents examples include aliphatic hydrocarbons such as n-butane, isobutane, n-pentane, n-hexane, n-heptane and n-octane; hydrocarbons; aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene; and the like.
  • aliphatic hydrocarbon alkali metal compounds As polymerization initiators, aliphatic hydrocarbon alkali metal compounds, aromatic hydrocarbon alkali metal compounds, organic amino alkali metal compounds, which are generally known to have anionic polymerization activity for conjugated diene compounds and vinyl aromatic compounds. and organic alkali metal compounds such as compounds.
  • Alkali metals include lithium, sodium, potassium and the like.
  • Examples of organic alkali metal compounds include aliphatic and aromatic hydrocarbon lithium compounds having 1 to 20 carbon atoms, compounds containing one lithium per molecule, and dilithium containing multiple lithium per molecule. compounds, trilithium compounds, tetralithium compounds.
  • organic alkali metal compounds include n-propyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, n-pentyllithium, n-hexyllithium, benzyllithium, phenyllithium, and tolyllithium. , a reaction product of diisopropenylbenzene and sec-butyllithium, and a reaction product of divinylbenzene, sec-butyllithium and a small amount of 1,3-butadiene. Furthermore, 1-(t-butoxy)propyl lithium disclosed in US Pat.
  • Siloxy group-containing alkyllithium such as 1-(t-butyldimethylsiloxy)hexyllithium disclosed in US Pat. No. 5,527,753, amino group-containing alkyl Aminolithiums such as lithium, lithium diisopropylamide and lithium hexamethyldisilazide can also be used.
  • the polymerization method may be, for example, batch polymerization, continuous polymerization, or a combination thereof. Batch polymerization is particularly suitable for obtaining uniform polymer blocks.
  • the polymerization temperature is preferably 0°C to 180°C, more preferably 30°C to 150°C.
  • the polymerization time varies depending on the conditions, it is usually within 48 hours, preferably 0.1 to 10 hours.
  • an inert gas atmosphere such as nitrogen gas is preferable.
  • the polymerization pressure is not particularly limited, and may be set within a pressure range that can maintain the monomer and solvent in the liquid phase within the above temperature range. Furthermore, care must be taken to prevent impurities such as water, oxygen, and carbon dioxide from entering the polymerization system, which may inactivate the catalyst and living polymer.
  • a necessary amount of a bifunctional or higher coupling agent may be added to perform the coupling reaction within the range of satisfying the above conditions (i) to (iv), but the coupling rate is It is preferably 40% or less, more preferably 30% or less, still more preferably 20% or less, and it is even more preferable that it does not contain a coupling agent.
  • bifunctional coupling agent a conventionally known one can be applied, and it is not particularly limited.
  • bifunctional coupling agents include, but are not limited to, trimethoxysilane, triethoxysilane, tetramethoxysilane, tetraethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, dichlorodimethoxysilane, dichlorodiethoxysilane, trichloro Alkoxysilane compounds such as methoxysilane and trichloroethoxysilane; dihalogen compounds such as dichloroethane, dibromoethane, dimethyldichlorosilane, and dimethyldibromosilane; acid esters such as methyl benzoate, ethyl benzoate, phenyl benzoate, and phthalates etc.
  • a polyfunctional coupling agent having a functionality of 3 or more a conventionally known one can be applied, and it is not particularly limited.
  • tri- or higher polyfunctional coupling agents include, but are not limited to, tri- or higher polyalcohols, epoxidized soybean oil, diglycidyl bisphenol A, 1,3-bis(N—N′-di polyepoxy compounds such as glycidylaminomethyl)cyclohexane; represented by the general formula R 4 -nSiX n (wherein R is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen, and n is an integer of 3 to 4); Silicon halide compounds represented by , for example, methylsilyl chloride, t-butylsilyl chloride, silicon tetrachloride and bromides thereof, etc .; is a hydrocarbon group, X is a halogen, and n is an integer of 3 to 4). mentioned. Also, di
  • catalyst residues can be removed as necessary to separate the block copolymer from the solution.
  • the polymerization initiator in the production of the block copolymer by anionic living polymerization and the compound containing the metal atom in the hydrogenation catalyst in the hydrogenation reaction described above react with moisture in the air in the solvent removal process, etc. It tends to form a certain metal compound and remain in the block copolymer.
  • the dielectric constant and the dielectric loss tangent tend to increase, and further ion migration tends to occur in electronic material applications. It is in.
  • the remaining metal compounds include compounds of metals contained in polymerization initiators and hydrogenation catalysts, such as titanium oxide, amorphous titanium oxide, orthotitanic acid, metatitanic acid, titanium hydroxide, nickel hydroxide, and nickel monoxide.
  • hydrogenation catalysts such as titanium oxide, amorphous titanium oxide, orthotitanic acid, metatitanic acid, titanium hydroxide, nickel hydroxide, and nickel monoxide.
  • the residual amount of the metal compound in the block copolymer is, as the residual metal amount, It is preferably 150 ppm or less, more preferably 130 ppm or less, still more preferably 100 ppm or less, and even more preferably 90 ppm or less.
  • Residual metals generally include Ti, Ni, Li, Co, and the like.
  • a conventionally known method can be applied and is not particularly limited.
  • a method of adding water and carbon dioxide gas after the hydrogenation reaction of the block copolymer to neutralize the hydrogenation catalyst residue; a method of adding an acid in addition to water and carbon dioxide gas to neutralize the hydrogenation catalyst residue. is mentioned.
  • the method described in Japanese Patent Application No. 2014-557427 can be applied.
  • the amount of residual metal is generally about 1 to 15 ppm because water containing the hydroxide of the metal compound is mixed in the solvent removal process of the block copolymer. target. Therefore, it is preferable to remove 20% or more, more preferably 30% or more, still more preferably 40% or more, and even more preferably 50% or more of the amount of metal added to the block copolymer. Removal, even more preferably removal of 60% or more is performed.
  • the amount of residual metal in the block copolymer can also be reduced by reducing the amount of polymerization initiator and hydrogenation catalyst to be added.
  • the amount of polymerization initiator and hydrogenation catalyst to be added.
  • the strength of the cured product tends to decrease.
  • the amount of the hydrogenation catalyst is reduced in carrying out the hydrogenation reaction, the hydrogenation reaction time will be prolonged and the hydrogenation reaction temperature will be increased, which tends to significantly lower the productivity.
  • a polar solvent such as acetone or alcohol which is a poor solvent for the block copolymer
  • a method of recovering by precipitation a method of pouring the reaction mixture into hot water while stirring and removing the solvent by steam stripping for recovery; a method of directly heating the block copolymer solution to distill off the solvent. be done.
  • stabilizers such as various phenol-based stabilizers, phosphorus-based stabilizers, sulfur-based stabilizers, and amine-based stabilizers can be added to the hydrogenated block copolymer.
  • the block copolymer of the present embodiment may have a "polar group” within a range that does not impair the low dielectric loss tangent property and the low dielectric constant property.
  • "Polar group” includes, but is not limited to, hydroxyl group, carboxyl group, carbonyl group, thiocarbonyl group, acid halide group, acid anhydride group, carboxylic acid group, thiocarboxylic acid group, aldehyde group, thioaldehyde group , carboxylic acid ester group, amide group, sulfonic acid group, sulfonic acid ester group, phosphoric acid group, phosphate ester group, amino group, imino group, nitrile group, pyridyl group, quinoline group, epoxy group, thioepoxy group, sulfide group , an isocyanate group, an isothiocyanate group, a silicon halide group, a silanol group, an alkoxy silicon
  • the "polar group” can be formed using a modifier.
  • Modifiers include, but are not limited to, tetraglycidylmetaxylenediamine, tetraglycidyl-1,3-bisaminomethylcyclohexane, ⁇ -caprolactone, ⁇ -valerolactone, 4-methoxybenzophenone, ⁇ -glycidoxy ethyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyldimethylphenoxysilane, bis( ⁇ -glycidoxypropyl)methylpropoxysilane, 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, N,N'-dimethylpropylene urea, N-methylpyrrolidone, maleic acid, maleic anhydride, maleimide anhydride, fumaric acid, itaconic acid, acrylic acid,
  • a known method can be applied and is not particularly limited. Examples thereof include a melt-kneading method and a method of dissolving or dispersing and mixing each component in a solvent or the like and reacting them. Also, a method of polymerizing by anionic living polymerization using a polymerization initiator having a functional group or an unsaturated monomer having a functional group; A method in which a block copolymer is reacted with an organic alkali metal compound such as an organic lithium compound (metalation reaction), and a modifying agent having a functional group is added to the block copolymer to which the organic alkali metal is added. etc. are also mentioned.
  • the resin composition of the present embodiment contains the block copolymer of the present embodiment (component (I)) and at least one component selected from the group consisting of components (II) to (IV) below.
  • Component (II) Radical initiator
  • Component (III) Polar resin (excluding component (I))
  • Component (IV) Curing agent (excluding component (II))
  • the resin composition of the present embodiment includes component (I): the block copolymer, Component (II): It preferably contains a radical initiator.
  • thermal radical initiators include hydroperoxides such as diisopropylbenzene hydroperoxide (Percmyl P), cumene hydroperoxide (Percumyl H), t-butyl hydroperoxide (Per-butyl H), ⁇ , ⁇ -bis(t-butylperoxy-m-isopropyl)benzene (perbutyl P), dicumyl peroxide (percumyl D), 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane ( perhexa 25B), t-butyl cumyl peroxide (perbutyl C), di-t-butyl peroxide (perbutyl D), 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyne-3 (perhexyne 25B), dialkyl peroxides such as t-buty
  • component (I) a polar resin (excluding component (I)).
  • component (II) radical initiator described above
  • component (II) may not be added.
  • the polar resin having radical reactivity as the component (III) includes, for example, a polymer having at least one vinyl group in the polymer, a homopolymer of a compound containing a halogen element, and any of these and any A copolymer with a compound and the like can be mentioned.
  • the polar resin as the component (III) is preferably a polymer having a vinyl group.
  • the polymer having a vinyl group may be a polymer composed of repeating units having a vinyl group, or may be a polymer of a compound having a vinyl group and a compound having a polar group.
  • compounds having a vinyl group and a polar group include, but are not limited to, (meth)acrylic acid (in the present specification, "(meth)acrylic acid means methacrylic or acrylic"), maleic acid, maleic acid Carboxyl group-containing vinyl monomers such as monoalkyl esters and fumaric acid, sulfone group-containing vinyl monomers such as vinyl sulfonic acid, (meth)allylsulfonic acid, methyl vinyl sulfonic acid, and styrene sulfonic acid, hydroxystyrene, N-methylol (meth) Acrylamide, hydroxyl group-containing vinyl monomers such as hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylate, 2-hydroxyethyl (meth)acryloyl phosphate, phenyl-2-acryloyloxyethyl phosphate
  • amino group-containing vinyl monomers such as aminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, (meth)acrylamide, N-methyl (meth)acrylamide, N- Amide group-containing vinyl monomers such as butylacrylamide, nitrile group-containing vinyl monomers such as (meth)acrylonitrile, cyanostyrene, and cyanoacrylate, epoxy group-containing monomers such as glycidyl methacrylate, tetrahydrofurfuryl (meth)acrylate, and p-vinylphenylphenyl oxide Vinyl monomers are mentioned.
  • Examples of compounds containing halogen elements include, but are not limited to, vinyl chloride, vinyl bromide, vinylidene chloride, allyl chloride, chlorostyrene, bromostyrene, dichlorostyrene, chloromethylstyrene, tetrafluorostyrene, chloroprene and the like.
  • component (IV) curing agent When the radical reactivity of component (III) described above is low, the resin composition of the present embodiment preferably contains component (IV): a curing agent (excluding component (II)) from the viewpoint of reactivity. .
  • Component (IV): curing agent usually has a function of reacting with component (III): polar resin to cure the resin composition.
  • component (III) and component (IV) “react” means that the polar groups of each component have covalent bonding.
  • Component (IV) may be used alone or in combination of two or more.
  • component (III) and component (IV) are not particularly limited, for example, an epoxy group, a carboxy group, a carbonyl group, an ester group, an imidazole group, a hydroxyl group, an amino group, a mercaptan group, a benzoxazine group, a carbodiimide group, and a phenolic hydroxyl group; an amino group, a carboxyl group, a carbonyl group, a hydroxyl group, an acid anhydride group, a sulfonic acid, and an aldehyde group; an isocyanate group, a hydroxyl group, a carboxylic acid, and a phenolic hydroxyl group; an acid anhydride group and a hydroxy group; a silanol group, a hydroxy group, and a carboxylic acid group; a halogen group, a carboxylic acid group, a carboxylic acid ester group, an amino group, a
  • component (III) and the polar group of component (IV) do not react directly, the case where they can react by adding a curing accelerator such as a catalyst is also included in the definition of showing "reactivity".
  • a curing accelerator such as a catalyst
  • component (III) is a polar resin having an epoxy group
  • component (IV) is a curing agent having an acid anhydride group
  • the reactivity between the epoxy group and the acid anhydride group is usually very low.
  • a compound having an amino group as a curing accelerator
  • the epoxy groups of component (III) react with the amino groups, and some or all of the epoxy groups of component (III) become hydroxyl groups. This hydroxyl group reacts with component (IV): the acid anhydride group of the curing agent to cure the resin composition.
  • the curing agent is a curing agent having an ester group, but is not limited to the following, for example, EXB9451, EXB9460, EXB, 9460S, HPC8000-65T, HPC8000H-65TM, EXB8000L-65TM manufactured by DIC. , EXB8150-65T, EXB9416-70BK, and YLH1026, DC808, YLH1026, YLH1030 and YLH1048 manufactured by Mitsubishi Chemical Corporation.
  • Examples of the curing agent having a hydroxyl group include, but are not limited to, MEH-7700, MEH-7810, MEH-7851; SN180, SN190, SN475, SN485, SN495, SN-495V, SN375, TD-2090 manufactured by DIC, LA-7052, LA-7054, LA-1356, LA-3018-50P, EXB-9500 and the like.
  • Examples of the curing agent having a benzoxazine group include, but are not limited to, ODA-BOZ manufactured by JFE Chemical Co., Ltd., HFB2006M manufactured by Showa High Polymer Co., Ltd., and Pd and Fa manufactured by Shikoku Kasei Kogyo Co., Ltd. be done.
  • curing agents having an isocyanate group include, but are not limited to, bisphenol A dicyanate, polyphenolcyanate, oligo(3-methylene-1,5-phenylenecyanate), 4,4′-methylenebis(2,6-dimethyl phenylcyanate), 4,4′-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatophenylmethane), bis(4- cyanato-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatophenyl-1-(methylethylidene))benzene, bis(4-cyanatophenyl)thioether, bis(4-cyanatophenyl)ether, etc.
  • polyfunctional cyanate resins derived from phenol novolacs, cresol novolacs, etc.; prepolymers obtained by partially triazinizing these cyanate resins; and the like.
  • Commercially available products include PT30, PT60, ULL-950S, BA230 and BA230S75 manufactured by Lonza Japan.
  • the curing agent having a carbodiimide group includes, but is not limited to, V-03 and V-07 manufactured by Nisshinbo Chemical Co., Ltd., for example.
  • curing agents having an amino group include, but are not limited to, 4,4'-methylenebis(2,6-dimethylaniline), diphenyldiaminosulfone, 4,4'-diaminodiphenylmethane, 4,4'-diamino diphenylsulfone, 3,3'-diaminodiphenylsulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 3,3-dimethyl-5,5- Diethyl-4,4-diphenylmethanediamine, 2,2-bis(4-aminophen
  • the amino group is preferably a primary amine or a secondary amine, more preferably a primary amine.
  • curing agents having an acid anhydride group include, but are not limited to, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, and methylnadic anhydride.
  • the compound having at least two radical-reactive structures also has the function of curing the resin composition by reacting with the component (III). Such compounds can also be used as curing agents for component (IV).
  • Examples of compounds having at least two radical-reactive structures include, but are not limited to, triallyl isocyanurate (Tyku, manufactured by Mitsubishi Chemical Corporation), tris(2-hydroxyethyl) isocyanurate, diallyl fumarate, and adipine. Examples include allyl monomers such as diallyl acid, triallyl citrate, and diallyl hexahydrophthalate.
  • the component (III): the polar resin can be an epoxy resin, a polyimide resin, a polyphenylene ether resin, At least one selected from the group consisting of liquid crystalline polyester resins and fluorine resins is preferred. More preferably, it is at least one selected from the group consisting of epoxy-based resins, polyimide-based resins, and polyphenylene ether-based resins.
  • polyimide resin any resin having an imide bond in a repeating unit and belonging to the category called polyimide resin may be used.
  • polyimide resin there is a general polyimide structure obtained by polycondensation (imide bond) of tetracarboxylic acid or its dianhydride and diamine. From the viewpoint of curability, it is preferable to have an unsaturated group at the end of the polyimide structure.
  • polyimide resins having unsaturated groups at their terminals include, but are not limited to, maleimide-type polyimide resins, nadimide-type polyimide resins, and allyl nadimide-type polyimide resins.
  • tetracarboxylic acid or dianhydride thereof examples include, but are not limited to, aromatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, aliphatic tetracarboxylic dianhydride, and the like. . These may be used singly or in combination of two or more.
  • diamines include, but are not limited to, aromatic diamines, alicyclic diamines, and aliphatic diamines that are commonly used in the synthesis of polyimides. These may be used individually by 1 type, and may use 2 or more types together.
  • a fluorine group, a trifluoromethyl group may have one or a plurality of at least one functional group selected from the group consisting of a hydroxyl group, a sulfone group, a carbonyl group, a heterocyclic ring, a long-chain alkyl group, and an allyl group.
  • polyimide resin a commercially available polyimide resin may be used, and is not limited to the following. -3G30 (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name), C-3450 (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name), P500 (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name), BT (bis maleimide triazine) resin (manufactured by Mitsubishi Gas Chemical Co., Ltd.), JL-20 (manufactured by Shin Nippon Rika, trade name) (these polyimide resin varnishes may contain silica), Shin Nippon Rika Co., Ltd. Ricacoat SN20, Jamaicacoat PN20, I.M. S.
  • the polyphenylene ether-based resin which is the component (III), may be one that belongs to the category called polyphenylene ether resin, and contains phenylene ether units as repeating structural units. Further, it may contain other constitutional units than the phenylene ether unit.
  • a homopolymer having a phenylene ether unit whether or not the phenylene group in the phenylene unit has a substituent is not particularly limited.
  • substituents include, but are not limited to, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, acrylic group such as tert-butyl group, cyclic alkyl group such as cyclohexyl group, vinyl group, allyl group, isopropenyl group, 1-butenyl group, 1-pentenyl group, p-vinylphenyl group, p-isopropenylphenyl group, m-vinylphenyl group, m-isopropenylphenyl group, o-vinylphenyl group, o - isopropenylphenyl group, p-vinylbenzyl group, p-isoproperbenzyl group, m-vinylbenzyl group, m-isopropenylbenzyl group, o-vinylbenzyl group, o-isopropenylbenzyl group, m
  • the polyphenylene ether-based resin as component (III) has a molecular weight of preferably 100,000 or less, more preferably 50,000 or less, and even more preferably 10,000 or less from the viewpoint of curability of the resin composition of the present embodiment.
  • the polyphenylene ether-based resin may be linear, or may have a crosslinked or branched structure.
  • the liquid crystalline polyester resin that is the component (III) may be a polyester that forms an anisotropic melt phase and belongs to the category called liquid crystalline polyester resin.
  • Examples include, but are not limited to, "X7G” manufactured by Eastman Kodak, Xyday manufactured by Dartco, Econol manufactured by Sumitomo Chemical Co., Ltd., and Vectra manufactured by Celanese.
  • the fluororesin which is the component (III), may be any one that belongs to the category called fluororesin, and is an olefinic polymer containing a fluorine group.
  • the fluororesin include, but are not limited to, polytetrafluoroethylene, perfluoroalkoxyalkane, ethylene-tetrafluoroethylene copolymer, perfluoroethylene-propene copolymer, polyvinylidene fluoride, polychlorotrifluoroethylene, ethylene - chlorotrifluoroethylene copolymers, and the like.
  • Epoxy-based resins as component (III) may be those belonging to the category called epoxy resins, and preferably have two or more epoxy groups in one molecule from the viewpoint of strength.
  • An epoxy resin may be used individually by 1 type, and may combine 2 or more types.
  • Examples of epoxy resins include, but are not limited to, bixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, Trisphenol type epoxy resin, naphthol novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, spiro
  • component (IV) curing agent for example, a carboxy group, an imidazole group, a hydroxyl group, an amino group, a mercaptan group, a benzoxazine group, and a carbodiimide group can be mentioned.
  • a carboxy group, an imidazole group, a hydroxyl group, a benzoxazine group, and a carbodiimide group are preferred, and dielectric performance from the viewpoint of , hydroxyl group, carboxyl group, imidazole group, benzoxazine group and carbodiimide group are more preferred, and hydroxyl group, carboxyl group and carbodiimide group are further preferred.
  • component (II): radical initiator and component (IV): curing agent can be used in combination from the viewpoint of curability. preferable.
  • the resin composition of the present embodiment may not contain component (IV).
  • high-melting-point and high-rigidity resins which are component (III)
  • the resin composition of the present embodiment may further contain various additives such as curing accelerators, fillers and flame retardants as component (V). Further, what is included as an additive of the component (I) block copolymer is also synonymous with the component (V) of the resin composition.
  • the curing accelerator it is added for the purpose of promoting the reactivity between the components described above, and conventionally known ones can be used. Examples thereof include phosphorus curing accelerators, amine curing accelerators, imidazole curing accelerators, guanidine curing accelerators, metal curing accelerators, and the like.
  • the curing accelerator may be used singly or in combination of two or more.
  • Examples of phosphorus-based curing accelerators include, but are not limited to, triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methyl phenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate and the like, with triphenylphosphine and tetrabutylphosphonium decanoate being preferred.
  • amine-based curing accelerators include, but are not limited to, trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, and 2,4,6-tris(dimethylaminomethyl)phenol. , 1,8-diazabicyclo(5,4,0)-undecene and the like, with 4-dimethylaminopyridine and 1,8-diazabicyclo(5,4,0)-undecene being preferred.
  • imidazole-based curing accelerators include, but are not limited to, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1 , 2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl -2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimelli Tate, 1-cyanoethyl-2-phenylim
  • Guanidine-based curing accelerators include, but are not limited to, dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[ 4.4.0] Dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1 -cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, 1-(o-toly
  • Metal-based curing accelerators include, for example, organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin.
  • organometallic complexes include, but are not limited to, cobalt (II) acetylacetonate, organocobalt complexes such as cobalt (III) acetylacetonate, organocopper complexes such as copper (II) acetylacetonate, zinc ( II) Organic zinc complexes such as acetylacetonate, organic iron complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, organic manganese complexes such as manganese (II) acetylacetonate, etc.
  • organic metal salts include, but are not limited to, zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, and the like.
  • fillers include, but are not limited to, silica, calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, calcium sulfate, barium sulfate, carbon black, glass fibers, glass beads, glass balloons, glass flakes, and graphite. , titanium oxide, potassium titanate whiskers, carbon fiber, alumina, kaolin clay, silicic acid, calcium silicate, quartz, mica, talc, clay, zirconia, potassium titanate, alumina, inorganic fillers such as metal particles; wood chips , wood powder, pulp, and organic fillers such as cellulose nanofibers. These may be used individually by 1 type, or may be used in combination of multiple. The shape of these fillers may be scaly, spherical, granular, powdery, amorphous, etc., and is not particularly limited.
  • the resin composition or cured product of the present embodiment is often exposed to high temperatures during molding, etc., but shrinks due to the temperature change, and in order to prevent deformation of the molded product, the filler has a linear expansion Small coefficients are preferred.
  • Silica is preferable as the filler from the viewpoint of lowering the linear expansion coefficient, and examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica.
  • flame retardants examples include halogen-based flame retardants such as bromine compounds, phosphorus-based flame retardants such as aromatic compounds, metal hydroxides, alkylsulfonates, antimony trioxide, aluminum hydroxide, magnesium hydroxide, and boric acid.
  • flame retardants containing aromatic bromine compounds such as zinc, hexabromobenzene, decabromodiphenylethane, 4,4-dibromobiphenyl, and ethylenebistetrabromophthalimide. These flame retardants are used singly or in combination of two or more.
  • the above-mentioned flame retardants also include so-called flame retardant aids, which exhibit a synergistic effect when used in combination with other flame retardants, although they have a low flame retardancy effect on their own.
  • the filler and flame retardant may also be of a type that has been previously surface-treated with a surface-treating agent such as a silane coupling agent.
  • a surface-treating agent such as a silane coupling agent.
  • surface treatment agents include fluorine-containing silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, organosilazane compounds, and titanate compounds.
  • a coupling agent etc. are mentioned. These may be used singly or in combination.
  • additives are not particularly limited as long as they are generally used for compounding resin compositions and cured products.
  • Other additives include, but are not limited to, pigments and/or colorants such as carbon black, titanium oxide; stearic acid, behenic acid, zinc stearate, calcium stearate, magnesium stearate, ethylene bis stearo Lubricants such as amides; release agents; fatty acid esters such as organic polysiloxanes, phthalate ester compounds, adipate ester compounds, and azelaic acid ester compounds; plasticizers such as mineral oil; Antioxidants such as; hindered amine light stabilizers; benzotriazole ultraviolet absorbers; antistatic agents; organic fillers; thickeners; agents or mixtures thereof.
  • the resin composition of the present embodiment contains a pigment, a coloring agent, a lubricant, a release agent, and an antistatic agent. It tends to be preferable not to
  • the resin composition in the present embodiment may be obtained by melt-kneading each component, or may be obtained by dissolving each component in a soluble solvent and stirring (hereinafter, “varnish”).
  • Varnish is preferable from the viewpoint of handleability.
  • solvents include, but are not limited to, ketones such as acetone, methyl ethyl ketone (MEK), cyclohexanone, and ⁇ -butyrolactone; ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate, and diethyl glycol.
  • acetic esters such as monoacelate
  • carbitols such as cellosolve and butyl carbitol
  • aromatic hydrocarbons such as toluene and xylene
  • amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone, etc. can be mentioned.
  • An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the cured product of the present embodiment contains the block copolymer of the present embodiment described above.
  • the cured product of the present embodiment is obtained by subjecting the resin composition of the present embodiment to a curing reaction at any temperature and time.
  • the term “cured product” is a concept that includes not only a completely cured product, but also a mode (semi-cured product) in which only a part of the resin composition is cured to contain uncured components.
  • a step of further curing the cured product may be carried out in the manufacturing process of the laminate, which will be described later.
  • the reaction temperature in the step of curing the cured product of the present embodiment is preferably 80° C. or higher, more preferably 100° C. or higher, and even more preferably 120° C. or higher.
  • the reaction time is preferably 10 to 240 minutes, more preferably 20 to 230 minutes, even more preferably 30 to 220 minutes.
  • a curing reaction after removing the solvent by drying.
  • a drying method a conventionally known method such as heating or blowing hot air may be used, and it is preferable to carry out the drying at a temperature lower than the curing reaction temperature. is preferably 10% by mass or less, more preferably 5% by mass or less.
  • the resin film of this embodiment is made of the resin composition of this embodiment.
  • the resin film of the present embodiment is obtained by stretching the varnish made of the resin composition of the present embodiment described above into a uniform thin film, drying it as described above to remove the solvent, and then forming it into a roll. It can be rolled up and stored.
  • the resin film of this embodiment may have a structure in which a predetermined protective film is laminated, and in such a case, it becomes usable by peeling off the protective film.
  • the prepreg of this embodiment includes a substrate and the resin composition of this embodiment impregnated or applied to this substrate. That is, the prepreg of the present embodiment is a composite of the resin composition of the present embodiment and a substrate.
  • the prepreg can be obtained, for example, by impregnating a base material such as glass cloth with the varnish, which is the resin composition of the present embodiment, and then removing the solvent by the drying method described above.
  • a base material such as glass cloth with the varnish, which is the resin composition of the present embodiment
  • Various glass cloths such as roving cloths, cloths, chopped mats, surfacing mats; asbestos cloths, metal fiber cloths, and other synthetic or natural inorganic fiber cloths; wholly aromatic polyamide fibers, wholly aromatic polyesters.
  • the solid content of the resin composition of the present embodiment in the prepreg is preferably 30 to 80% by mass, more preferably 40 to 70% by mass. When the ratio is 30% by mass or more, the insulation reliability tends to be further improved when the prepreg is used for an electronic substrate or the like. When the proportion is 80% by mass or less, mechanical properties such as rigidity tend to be more excellent in applications such as electronic substrates.
  • the laminated body of this embodiment has the resin film and metal foil which were mentioned above.
  • the laminate of the present embodiment includes the above-described cured prepreg and metal foil.
  • the laminate of the present embodiment can be produced, for example, by laminating a resin film made of the resin composition of the present embodiment on a substrate to form a resin layer, obtaining a prepreg (a), and heating and heating the resin layer. It can be manufactured through a step (b) of flattening by pressing to obtain a cured prepreg and a step (c) of further forming a predetermined wiring layer made of metal foil on the resin layer.
  • the method of laminating the resin film on the substrate is not particularly limited, and examples thereof include a method of laminating using a multistage press, a vacuum press, a normal pressure laminator, and a laminator that heats and presses under vacuum.
  • a method using a laminator that heats and presses under vacuum is preferred. According to the method using this laminator, even if the target electronic circuit board has a fine wiring circuit on its surface, the spaces between the circuits can be filled with resin without causing voids.
  • the lamination may be of a batch type or a continuous type using a roll or the like.
  • Examples of the base material of the above-described laminate include, in addition to the above-described base material constituting the prepreg, glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, polyphenylene ether substrates, fluororesin substrates, and the like.
  • the surface of the substrate on which the resin layer is laminated may be roughened in advance, and the number of substrate layers is not limited.
  • the resin film and the base material laminated in the step (a) are pressed under heating to flatten.
  • the conditions can be arbitrarily adjusted depending on the type of base material and the composition of the resin film, but are preferably, for example, a temperature of 100 to 300° C., a pressure of 0.2 to 20 MPa, and a time of 30 to 180 minutes.
  • a predetermined wiring layer made of a metal foil is further formed on the resin layer produced by pressing the resin film and the base material under heating.
  • the forming method is not particularly limited, and conventionally known methods can be used. Examples thereof include etching methods such as subtractive methods, semi-additive methods, and the like.
  • an etching resist layer having a shape corresponding to the desired pattern shape is formed on the metal layer, and the metal layer where the resist has been removed is dissolved and removed with a chemical solution by subsequent development processing.
  • This is a method of forming desired wiring.
  • a metal film is formed on the surface of a resin layer by electroless plating, a plating resist layer having a shape corresponding to a desired pattern is formed on the metal film, and then a metal layer is formed by electroplating.
  • an unnecessary electroless plated layer is removed with a chemical solution or the like after formation, and a desired wiring layer is formed.
  • holes such as via holes may be formed in the resin layer as necessary, and the method for forming the holes is not particularly limited, and conventionally known methods can be used.
  • a method for forming holes for example, an NC drill, carbon dioxide laser, UV laser, YAG laser, plasma, or the like can be used.
  • the laminate in this embodiment described above may be plate-shaped or may be a flexible laminate having flexibility.
  • the laminate of this embodiment may be a metal-clad laminate.
  • the metal-clad laminate is obtained by laminating the resin composition of the present embodiment or the prepreg of the present embodiment with a metal foil and curing, and a part of the metal foil is removed from the metal-clad laminate.
  • the metal-clad laminate preferably has a form in which a cured prepreg (also referred to as a "cured composite") and a metal foil are laminated and adhered, and is suitably used as a material for electronic circuit boards. be done.
  • the metal foil examples include aluminum foil and copper foil, and among these, copper foil is preferable because of its low electrical resistance.
  • the cured prepreg to be combined with the metal foil may be one sheet or a plurality of sheets, and depending on the application, the metal foil is laminated on one side or both sides of the cured material and processed into a laminate.
  • a method for producing the laminate for example, a prepreg composed of the resin composition of the present embodiment and a base material is formed, and after stacking this with a metal foil, the resin composition is cured to obtain a prepreg. and a method of obtaining a laminate in which a cured product of (1) and a metal foil are laminated.
  • One of the particularly preferred uses of said laminates is printed wiring boards.
  • the printed wiring board can be produced by using the prepreg of the present embodiment described above and performing pressurization and heat molding.
  • the base material the same material as described above with respect to the prepreg can be used.
  • the printed wiring board has excellent strength and electrical properties (low dielectric constant and low dielectric loss tangent), and furthermore, the electrical property fluctuations due to environmental changes are suppressed. It is suppressible and has excellent insulation reliability and mechanical properties.
  • the material for the electronic circuit board of the present embodiment includes a cured product of the resin composition of the present embodiment.
  • the material for the electronic circuit board of this embodiment can be produced using the resin composition and/or varnish of this embodiment described above.
  • the material for the electronic circuit board of the present embodiment includes a cured product of the resin composition described above, a resin film containing the resin composition of the present embodiment or a cured product thereof, and a composite of a substrate and a resin composition. At least one selected from the group consisting of certain prepregs is included.
  • the electronic circuit board material of the present embodiment can be used as a printed wiring board having a resin-coated metal foil.
  • the average molecular weight obtained from the molecular weight of each peak and the composition ratio of each peak was used as the molecular weight when there were multiple peaks in the chromatogram. Further, the molecular weight distribution is the ratio (Mw/Mn) of the obtained weight average molecular weight (Mw) and number average molecular weight (Mn).
  • a sample for measurement was measured by a gas chromatography (GC-14B manufactured by Shimadzu Corporation) equipped with a backed column supporting Apiezon grease, and from the previously obtained calibration curve of butadiene monomer and styrene monomer, was obtained, and it was confirmed that the polymerization rate of butadiene monomer and styrene monomer was 100%. Therefore, the compositional ratio of the vinyl aromatic monomer unit and the conjugated diene monomer unit in the polymer block (C) was set to the same value as the mass ratio of the added vinyl aromatic monomer and the conjugated diene monomer unit. .
  • the polymerization rate of butadiene was measured at a constant 90° C., and the polymerization rate of styrene was measured under the conditions of 90° C. (hold for 10 minutes) to 150° C. rising (10° C./min).
  • Tables 1 and 2 show the composition of the polymer block (C). The sum of these values is the content (parts by mass) of the polymer block (C) with respect to 100 parts by mass of the block copolymer.
  • Component (I) block copolymer A block copolymer of a vinyl aromatic compound and a conjugated diene was prepared as follows. Tables 1 and 2 show the structure and physical properties of each block copolymer. In the table, (A) indicates a polymer block (A) mainly composed of vinyl aromatic monomer units, and (B) indicates a polymer block (B) mainly composed of conjugated diene monomer units. ), and (C) indicates a polymer block (C) composed of vinyl aromatic monomer units and conjugated diene monomer units.
  • TMEDA tetramethylethylenediamine
  • Block copolymer (1) obtained as described above has a styrene content of 70% by mass, a weight average molecular weight of 1.5 ⁇ 10 4 , a molecular weight distribution of 1.10, 1,2-bonds and/or 3,
  • the content of units (a) derived from 4-bonds (amount of vinyl bonds: units (a)/conjugated diene monomer units in polymer block (C)) was 70%.
  • TMEDA tetramethylethylenediamine
  • a cyclohexane solution (concentration: 20% by mass) containing 70 parts by mass of styrene and 15 parts by mass of butadiene was added and polymerized at 70° C. for 30 minutes. After that, methanol was added to terminate the polymerization reaction to obtain a block copolymer.
  • the block copolymer (2) obtained as described above has a styrene content of 70% by mass, a weight average molecular weight of 1.5 ⁇ 10 4 , a molecular weight distribution of 1.10, 1,2-bonds and/or 3,
  • the content of units (a) derived from 4-bonds (vinyl bond amount: units (a)/(polymer block (B) + conjugated diene monomer unit in polymer block (C))) is 70% Met.
  • TMEDA tetramethylethylenediamine
  • a cyclohexane solution (concentration: 20% by mass) containing 70 parts by mass of styrene and 10 parts by mass of butadiene was added and polymerized at 70° C. for 30 minutes.
  • a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of butadiene was added and polymerized for 15 minutes.
  • methanol was added to terminate the polymerization reaction to obtain a block copolymer.
  • the block copolymer (3) obtained as described above has a styrene content of 70% by mass, a weight average molecular weight of 1.5 ⁇ 10 4 , a molecular weight distribution of 1.10, 1,2-bonds and/or 3,
  • the content of units (a) derived from 4-bonds (amount of vinyl bonds: units (a)/(polymer block (B) + conjugated diene monomer unit in polymer block (C))) was 71%. Met.
  • TMEDA tetramethylethylenediamine
  • the block copolymer (4) obtained as described above has a styrene content of 10% by mass, a weight average molecular weight of 1.5 ⁇ 10 4 , a molecular weight distribution of 1.10, 1,2-bonds and/or 3,
  • the content of units (a) derived from 4-bonds (amount of vinyl bonds: units (a)/conjugated diene monomer units in polymer block (C)) was 69%.
  • TMEDA tetramethylethylenediamine
  • a cyclohexane solution (concentration: 20% by mass) containing 35 parts by mass of styrene and 15 parts by mass of butadiene was added and polymerized at 70° C. for 20 minutes.
  • a cyclohexane solution (concentration: 20% by mass) containing 25 parts by mass of butadiene was added and polymerized for 15 minutes.
  • methanol was added to terminate the polymerization reaction to obtain a block copolymer.
  • the block copolymer (5) obtained as described above has a styrene content of 35% by mass, a weight average molecular weight of 1.5 ⁇ 10 4 , a molecular weight distribution of 1.10, 1,2-bonds and/or 3,
  • the content of units (a) derived from 4-bonds (vinyl bond amount: units (a)/(polymer block (B) + conjugated diene monomer unit in polymer block (C)))) is 70% Met.
  • TMEDA tetramethylethylenediamine
  • a cyclohexane solution (concentration: 20% by mass) containing 55 parts by mass of styrene and 15 parts by mass of butadiene was added and polymerized at 70° C. for 30 minutes.
  • a cyclohexane solution (concentration: 20% by mass) containing 15 parts by mass of butadiene was added and polymerized for 15 minutes.
  • methanol was added to terminate the polymerization reaction to obtain a block copolymer.
  • the block copolymer (6) obtained as described above has a styrene content of 55% by mass, a weight average molecular weight of 1.5 ⁇ 10 4 , a molecular weight distribution of 1.10, 1,2-bonds and/or 3,
  • the content of units (a) derived from 4-bonds (vinyl bond amount: units (a)/(polymer block (B) + conjugated diene monomer unit in polymer block (C)))) is 70% Met.
  • ⁇ Block copolymer (7) Batch polymerization was carried out using a tank reactor (inner volume 10 L) equipped with a stirrer and a jacket. First, a cyclohexane solution (concentration of 20% by mass) containing 5 parts by mass of butadiene was added. Next, 0.65 parts by mass of n-butyllithium and 0.8 mol of tetramethylethylenediamine (TMEDA) per 1 mol of n-butyllithium were added to 100 parts by mass of all the monomers, and Polymerized for a minute.
  • TMEDA tetramethylethylenediamine
  • a cyclohexane solution (concentration: 20% by mass) containing 90 parts by mass of styrene and 5 parts by mass of butadiene was added and polymerized at 70° C. for 35 minutes. After that, methanol was added to terminate the polymerization reaction to obtain a block copolymer.
  • the block copolymer (7) obtained as described above has a styrene content of 90% by mass, a weight average molecular weight of 1.5 ⁇ 10 4 , a molecular weight distribution of 1.10, 1,2-bonds and/or 3,
  • the content of units (a) derived from 4-bonds (vinyl bond amount: units (a)/(polymer block (B) + conjugated diene monomer unit in polymer block (C)))) is 70% Met.
  • Block copolymer (8) A polymerization reaction was carried out in the same manner as for the block copolymer (3), except that 0.23 parts by mass of n-butyllithium was added to 100 parts by mass of all the monomers.
  • the block copolymer (8) obtained as described above has a styrene content of 70% by mass, a weight average molecular weight of 3.0 ⁇ 10 4 , a molecular weight distribution of 1.10, 1,2-bonds and/or 3,
  • the content of units (a) derived from 4-bonds (vinyl bond amount: units (a)/(polymer block (B) + conjugated diene monomer unit in polymer block (C))) is 70% Met.
  • ⁇ Block copolymer (9)> A polymerization reaction was carried out in the same manner as for the block copolymer (3), except that 0.29 parts by mass of n-butyllithium was added to 100 parts by mass of all the monomers.
  • the block copolymer (9) obtained as described above has a styrene content of 70% by mass, a weight average molecular weight of 2.5 ⁇ 10 4 , a molecular weight distribution of 1.10, 1,2-bonds and/or 3,
  • the content of units (a) derived from 4-bonds (vinyl bond amount: units (a)/(polymer block (B) + conjugated diene monomer unit in polymer block (C)))) is 70% Met.
  • Block copolymer (10)> A polymerization reaction was carried out in the same manner as for the block copolymer (3), except that 1.4 parts by mass of n-butyllithium was added to 100 parts by mass of all the monomers.
  • Block copolymer (10) obtained as described above has a styrene content of 70% by mass, a weight average molecular weight of 0.5 ⁇ 10 4 , a molecular weight distribution of 1.10, 1,2-bonds and/or 3,
  • the content of units (a) derived from 4-bonds (vinyl bond amount: units (a)/(polymer block (B) + conjugated diene monomer unit in polymer block (C))) is 70% Met.
  • Block copolymer (11) A polymerization reaction was carried out in the same manner as for the block copolymer (3), except that 0.1 mol of TMEDA was added per 1 mol of n-butyllithium.
  • Block copolymer (11) obtained as described above has a styrene content of 70% by mass, a weight average molecular weight of 1.5 ⁇ 10 4 , a molecular weight distribution of 1.10, 1,2-bonds and/or 3,
  • the content of units (a) derived from 4-bonds (amount of vinyl bonds: units (a)/polymer block (B) + conjugated diene monomer units in polymer block (C))) is 30%. there were.
  • ⁇ Block copolymer (12)> The same procedure as for the block copolymer (3) was performed except that 2 mol of TMEDA was added to 1 mol of n-butyllithium, the polymerization temperature was set to 50° C., and the polymerization time for each block was extended by 10 minutes.
  • the block copolymer (12) obtained as described above has a styrene content of 70% by mass, a weight average molecular weight of 1.5 ⁇ 10 4 , a molecular weight distribution of 1.13, 1,2-bonds and/or 3,
  • the content of units (a) derived from 4-bonds (vinyl bond amount: units (a)/(polymer block (B) + conjugated diene monomer unit in polymer block (C)))) is 85% Met.
  • ⁇ Block copolymer (13)> A polymerization reaction was carried out in the same manner as for the block copolymer (3). Using the obtained block copolymer, the hydrogenation catalyst prepared as described above was added at 50 ppm based on Ti per 100 parts by mass of the block copolymer, and hydrogenation was performed at a hydrogen pressure of 0.7 MPa and a temperature of 80 ° C. The reaction was carried out for about 0.5 hours to obtain a hydrogenated block copolymer (13).
  • the hydrogenated block copolymer (13) obtained as described above has a styrene content of 70% by mass, a weight average molecular weight of 1.5 ⁇ 10 4 , a molecular weight distribution of 1.10, 1,2-bonds and/or
  • the content of units (a) derived from 3,4-bonds (amount of vinyl bonds: units (a)/(polymer block (B) + conjugated diene monomer unit in polymer block (C)))) is 70%, and the hydrogenation rate was 50%.
  • ⁇ Block copolymer (14)> The same operation as for block copolymer (13) was performed, except that the hydrogenation reaction was carried out for about 0.25 hours.
  • the hydrogenated block copolymer (14) obtained as described above has a styrene content of 70% by mass, a weight average molecular weight of 1.5 ⁇ 10 4 , a molecular weight distribution of 1.10, 1,2-bonds and/or
  • the content of units (a) derived from 3,4-bonds is 70%, and the hydrogenation rate was 22%.
  • ⁇ Block copolymer (15)> The same operation as for block copolymer (13) was performed except that the hydrogenation reaction was carried out for about 0.75 hours.
  • the hydrogenated block copolymer (15) obtained as described above has a styrene content of 70% by mass, a weight average molecular weight of 1.5 ⁇ 10 4 , a molecular weight distribution of 1.10, 1,2-bonds and/or
  • the content of units (a) derived from 3,4-bonds is 71%, and the hydrogenation rate was 69%.
  • Block copolymer (16)> A polymerization reaction was carried out in the same manner as for block copolymer (1), except that 0.18 parts by mass of n-butyllithium was added to 100 parts by mass of all the monomers.
  • the block copolymer (16) obtained as described above has a styrene content of 70% by mass, a weight average molecular weight of 4.0 ⁇ 10 4 , a molecular weight distribution of 1.10, 1,2-bonds and/or 3,
  • the content of units (a) derived from 4-bonds (amount of vinyl bonds: units (a)/conjugated diene monomer units in polymer block (C)) was 71%.
  • ⁇ Block copolymer (17)> A polymerization reaction was carried out in the same manner as for the block copolymer (2), except that 0.18 parts by mass of n-butyllithium was added to 100 parts by mass of all the monomers.
  • the block copolymer (17) obtained as described above has a styrene content of 70% by mass, a weight average molecular weight of 4.0 ⁇ 10 4 , a molecular weight distribution of 1.10, 1,2-bonds and/or 3,
  • the content of units (a) derived from 4-bonds (vinyl bond amount: units (a)/(polymer block (B) + conjugated diene monomer unit in polymer block (C)))) is 70% Met.
  • ⁇ Block copolymer (18)> A polymerization reaction was carried out in the same manner as for the block copolymer (3), except that 0.18 parts by mass of n-butyllithium was added to 100 parts by mass of all the monomers.
  • the block copolymer (18) obtained as described above has a styrene content of 70% by mass, a weight average molecular weight of 4.0 ⁇ 10 4 , a molecular weight distribution of 1.10, 1,2-bonds and/or 3,
  • the content of units (a) derived from 4-bonds (amount of vinyl bonds: units (a)/(polymer block (B) + conjugated diene monomer unit in polymer block (C))) was 71%. Met.
  • TMEDA tetramethylethylenediamine
  • the block copolymer (19) obtained as described above has a styrene content of 70% by mass, a weight average molecular weight of 1.5 ⁇ 10 4 , a molecular weight distribution of 1.10, 1,2-bonds and/or 3,
  • the content of units (a) derived from 4-bonds (amount of vinyl bonds: units (a)/conjugated diene monomer units in polymer block (C)) was 70%.
  • TMEDA tetramethylethylenediamine
  • the block copolymer (20) obtained as described above has a styrene content of 70% by mass, a weight average molecular weight of 1.5 ⁇ 10 4 , a molecular weight distribution of 1.10, 1,2-bonds and/or 3,
  • the content of units (a) derived from 4-bonds (vinyl bond content: units (a)/polymer block (B)) was 70%.
  • TMEDA tetramethylethylenediamine
  • the block copolymer (21) obtained as described above has a styrene content of 70% by mass, a weight average molecular weight of 1.5 ⁇ 10 4 , a molecular weight distribution of 1.10, 1,2-bonds and/or 3,
  • the content of units (a) derived from 4-bonds (vinyl bond content: units (a)/polymer block (B)) was 70%.
  • TMEDA tetramethylethylenediamine
  • the block copolymer (22) obtained as described above has a styrene content of 70% by mass, a weight average molecular weight of 1.5 ⁇ 10 4 , a molecular weight distribution of 1.10, 1,2-bonds and/or 3,
  • the content of units (a) derived from 4-bonds (vinyl bond amount: units (a)/(polymer block (B) + conjugated diene monomer unit in polymer block (C)))) is 69%. Met.
  • TMEDA tetramethylethylenediamine
  • a cyclohexane solution (concentration: 20% by mass) containing 20 parts by mass of styrene and 20 parts by mass of butadiene was added and polymerized at 70° C. for 30 minutes. After that, methanol was added to terminate the polymerization reaction to obtain a block copolymer.
  • the block copolymer (23) obtained as described above has a styrene content of 70% by mass, a weight average molecular weight of 2.6 ⁇ 10 4 , a molecular weight distribution of 1.10, 1,2-bonds and/or 3,
  • the content of units (a) derived from 4-bonds (amount of vinyl bonds: units (a)/polymer block (B) + conjugated diene monomer units in polymer block (C)))) is 70%. there were.
  • Component (III): polar resin a polyphenylene ether resin (PPE) was polymerized as follows. A 1.5 liter jacketed reactor equipped with a sparger for oxygen-containing gas introduction at the bottom of the reactor, stirred turbine blades and baffles, and a reflux condenser in the vent gas line at the top of the reactor was loaded with 0.2512 g of chloride.
  • cupric dihydrate 1.1062 g of 35% hydrochloric acid, 3.6179 g of di-n-butylamine, 9.5937 g of N,N,N',N'-tetramethylpropanediamine, 211.63 g of methanol and 493.80 g of n-butanol and 180.0 g of 2,6-dimethylphenol containing 5 mol % of 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane were charged.
  • Examples 1 to 31 and Comparative Examples 1 to 22 demonstrate that the block copolymers of the present invention are excellent in balance between dielectric performance and strength when cured. In particular, it was found that the cured product of the present invention is suitable for printed wiring boards using glass cloth and metal laminates.
  • the cured film was used as an evaluation sample.
  • a resin composition was prepared according to the following preparation method using the following components.
  • a polyimide resin which is a polar resin, and a cyanate ester curing agent and/or a diamine curing agent are dissolved at 160° C. in the proportions shown in Tables 9 and 10 below, and reacted for 6 hours while stirring.
  • a maleimide triazine resin oligomer was obtained.
  • the obtained bismaleimide triazine resin oligomer was dissolved in toluene, and the rest of the components were added, stirred and dissolved to prepare a varnish with a concentration of 20% to 50% by mass.
  • the varnish was applied onto the release-treated Kapton film at a speed of 30 mm/sec. Then, it was dried at 100° C.
  • Examples 48 to 58 and Comparative Examples 38 to 54 demonstrate that the block copolymers of the present invention are excellent in balance between dielectric performance and strength when cured. It was found that the cured product of the present invention is suitable for use in printed wiring boards using glass cloth and metal laminates.
  • the block copolymer of the present invention, the resin composition containing the block copolymer, and the cured product have industrial applicability as materials for films, prepregs, electronic circuit boards, and next-generation communication boards.

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PCT/JP2023/007144 2022-03-04 2023-02-27 ブロック共重合体、樹脂組成物、硬化物、樹脂フィルム、プリプレグ、積層体、及び電子回路基板用の材料 WO2023167151A1 (ja)

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