WO2023008079A1 - 硬化性樹脂組成物、および、硬化物 - Google Patents

硬化性樹脂組成物、および、硬化物 Download PDF

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Publication number
WO2023008079A1
WO2023008079A1 PCT/JP2022/026139 JP2022026139W WO2023008079A1 WO 2023008079 A1 WO2023008079 A1 WO 2023008079A1 JP 2022026139 W JP2022026139 W JP 2022026139W WO 2023008079 A1 WO2023008079 A1 WO 2023008079A1
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Prior art keywords
curable resin
group
general formula
resin composition
integer
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PCT/JP2022/026139
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English (en)
French (fr)
Japanese (ja)
Inventor
龍一 松岡
広義 神成
立宸 楊
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DIC Corp
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DIC Corp
Dainippon Ink and Chemicals Co Ltd
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Priority to CN202280052870.6A priority Critical patent/CN117813331A/zh
Priority to US18/577,915 priority patent/US20240317916A1/en
Priority to KR1020237040032A priority patent/KR102955630B1/ko
Priority to JP2023514033A priority patent/JP7306599B2/ja
Publication of WO2023008079A1 publication Critical patent/WO2023008079A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/104—Esters of polyhydric alcohols or polyhydric phenols of tetraalcohols, e.g. pentaerythritol tetra(meth)acrylate
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/104—Esters of polyhydric alcohols or polyhydric phenols of tetraalcohols, e.g. pentaerythritol tetra(meth)acrylate
    • C08F222/1045—Esters of polyhydric alcohols or polyhydric phenols of tetraalcohols, e.g. pentaerythritol tetra(meth)acrylate of aromatic tetraalcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/061—Polyesters; Polycarbonates
    • 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
    • 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
    • C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D135/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D135/02—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • 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
    • C08J2335/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Derivatives of such polymers
    • C08J2335/02—Characterised by the use of homopolymers or copolymers of esters
    • 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
    • C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2351/08—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds

Definitions

  • the present invention relates to a curable resin composition containing a curable resin having a specific structure, and a cured product obtained from the curable resin composition.
  • vinyl group-containing curable resins with various chemical structures have been proposed.
  • curable resins such as divinyl benzyl ether of bisphenol and polyvinyl benzyl ether of novolak have been proposed (see, for example, Patent Documents 1 and 2).
  • these vinyl benzyl ethers cannot give a cured product with sufficiently low dielectric properties, and the resulting cured product has a problem in stable use in a high frequency band.
  • it cannot be said that the heat resistance is sufficiently high.
  • conventional vinyl group-containing curable resins containing polyvinyl benzyl ether can withstand low dielectric loss tangent and lead-free soldering required for electrical insulating material applications, especially for high-frequency electrical insulating material applications. It did not give a cured product having heat resistance.
  • the problem to be solved by the present invention is to provide a curable resin composition and the cured product, which can make the cured product excellent in heat resistance (high glass transition temperature) and dielectric properties (low dielectric properties). to provide.
  • the present inventors have made intensive studies to solve the above problems, and as a result, a curable resin composition characterized by containing a methacryloyloxy group-containing compound and an aromatic vinyl group-containing compound.
  • the inventors have found that the cured product is excellent in heat resistance and low dielectric properties, and have completed the present invention.
  • the present invention provides a curable resin (A) having a structure represented by the following general formula (1), a curable resin (B1) having a structure represented by the following general formula (2-1) and/or or a curable compound (B2) represented by the following general formula (2-2).
  • each Ra is independently an alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group, or a cycloalkyl group
  • M is a methacryloyloxy group
  • h and i are Each independently represents an integer of 1 to 4
  • j represents an integer of 0 to 2.
  • Rb is each independently an alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group, or a cycloalkyl group, and V is a vinyl group.
  • k is an integer of 0 to 4
  • l is an integer of 1 to 4
  • m is an integer of 0 to 2.
  • the present invention relates to a cured product obtained by subjecting the curable resin composition to a curing reaction.
  • the present invention is a curable resin composition containing the curable resin (A) and the curable resin (B1) and/or the curable compound (B2), which is obtained from the curable resin composition
  • Cured products are useful because they can contribute to heat resistance (high glass transition temperature) and dielectric properties (low dielectric properties).
  • the curable resin composition of the present invention is characterized by containing a curable resin (A) having a structure represented by the following general formula (1).
  • each Ra is independently an alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group, or a cycloalkyl group
  • M is a methacryloyloxy group
  • h and i are each Each independently represents an integer of 1-4
  • j represents an integer of 0-2.
  • Ra and M may be bonded to any position on the aromatic ring, and the bonding site with the carbon atom is any position on the aromatic ring. indicates that
  • each Ra independently represents an alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group, or a cycloalkyl group, preferably an alkyl group having 1 to 4 carbon atoms, It is an aryl group or a cycloalkyl group.
  • Ra causes steric hindrance, lowers molecular mobility, and provides a cured product with a low dielectric loss tangent. Furthermore, it is preferable that Ra is positioned ortho to the bridging group M. When at least one Ra is positioned at the ortho position of the cross-linking group M, the steric hindrance of the Ra further reduces the molecular mobility of the cross-linking group M, resulting in a cured product with a lower dielectric loss tangent. preferable.
  • M is a methacryloyloxy group that serves as a cross-linking group.
  • a methacryloyloxy group in the curable resin composition a cured product having a lower dielectric loss tangent than other cross-linking groups (eg, vinylbenzyl ether group, dihydroxybenzene group, etc.) can be obtained.
  • cross-linking group is a methacryloyloxy group
  • steric hindrance increases due to the presence of a methyl group in the structure, and molecular mobility is further reduced, resulting in a cured product with a lower dielectric loss tangent.
  • cross-linking density is increased and the heat resistance is improved.
  • h represents an integer of 1-4, preferably an integer of 1-2, more preferably 2. By being in the said range, reactivity is excellent and it becomes a preferable aspect.
  • i represents an integer of 1-4, preferably an integer of 1-2.
  • j represents an integer of 0 to 2, that is, when j is 0, it is a benzene ring, when j is 1, it is a naphthalene ring, and when j is 2, , an anthracene ring, preferably a benzene ring in which j is 0.
  • it is excellent in solvent solubility and becomes a preferable aspect.
  • At least one Ra on the aromatic ring and M are preferably located at the ortho position.
  • the molecular mobility of the methacryloyloxy group is restricted by the steric hindrance of Ra, and compared with the curable resin having the structure represented by the general formula (1), Dielectric loss tangent becomes low, which is a preferable mode.
  • the above general formula (1) is more preferably represented by the following general formula (1-1). That is, the structural formula described in the following general formula (1-1) is such that h is 2 and j is 1 in the general formula (1), Ra is positioned at the ortho position on both sides of the methacryloyloxy group, and the aromatic The tribal ring is fixed (limited) to the benzene ring.
  • the molecular mobility of the methacryloyloxy group is further restrained compared to the case where Ra is located only on one side, Furthermore, the dielectric loss tangent becomes low, which is a preferable aspect.
  • Ra is the same as Ra in general formula (1) above.
  • curable resin (A) a resin represented by any one of the following general formulas (A1) to (A3) is more preferable from the standpoint of easy availability of industrial raw materials.
  • each Ra is independently an alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group, or a cycloalkyl group
  • W is a hydrocarbon having 2 to 15 carbon atoms
  • n represents an integer of 3-5.
  • W is a hydrocarbon having 2 to 15 carbon atoms, preferably a hydrocarbon having 2 to 10 carbon atoms.
  • the curable resin (A1) becomes a low-molecular-weight body, has a higher cross-linking density than a high-molecular-weight body, and has a glass transition temperature of the obtained cured product. It becomes high, and it is excellent in heat resistance, and it becomes a preferable aspect.
  • the resulting curable resin When the number of carbon atoms is 2 or more, the resulting curable resin has a high molecular weight, and the resulting cured product has a lower crosslink density than when the number of carbon atoms is less than 2, resulting in the formation of a film or the like. In addition to being easy to handle, it tends to be excellent in handleability, flexibility, flexibility, and brittleness resistance. As compared with the case where it exceeds, the ratio of the cross-linking groups (methacryloyloxy groups) in the curable resin (A1) is increased, and accordingly the cross-linking density is improved, and the resulting cured product has excellent heat resistance, which is preferable. .
  • the hydrocarbon is not particularly limited as long as it is a hydrocarbon having 2 to 15 carbon atoms, but is preferably an aliphatic hydrocarbon such as an alkane, an alkene, or an alkyne, and an aromatic hydrocarbon containing an aryl group or the like. , a compound in which an aliphatic hydrocarbon and an aromatic hydrocarbon are combined, and the like.
  • examples of the alkane include ethane, propane, butane, pentane, hexane, and cyclohexane.
  • examples of the alkenes include those containing vinyl group, 1-methylvinyl group, propenyl group, butenyl group, pentenyl group and the like.
  • examples of the alkyne include those containing an ethynyl group, propynyl group, butynyl group, pentynyl group, hexynyl group and the like.
  • examples of the aromatic hydrocarbon include those containing phenyl, tolyl, xylyl, and naphthyl groups as aryl groups.
  • Examples of the compound in which an aliphatic hydrocarbon and an aromatic hydrocarbon are combined include a benzyl group, a phenylethyl group, a phenylpropyl group, a tolylmethyl group, a tolylethyl group, a tolylpropyl group, a xylylmethyl group, a xylylethyl group, and xylyl Examples include those containing a propyl group, naphthylmethyl group, naphthylethyl group, naphthylpropyl group, and the like.
  • Aliphatic hydrocarbons and aromatic hydrocarbons consisting only of carbon atoms and hydrogen atoms have low polarity and can give cured products having low dielectric properties (low dielectric constant and low dielectric loss tangent).
  • Alicyclic hydrocarbons are preferred, and among them, hydrocarbons with very low polarity and industrially employable, such as those represented by the following general formulas (3-1) to (3-6), are preferred, and more preferably: Aliphatic hydrocarbons represented by the following general formulas (3-1) and (3-4).
  • Rc is preferably represented by a hydrogen atom or a methyl group.
  • n is the number of substituents and represents an integer of 3 to 5, preferably 3 or 4, more preferably 4.
  • the curable resin (A1) becomes a low-molecular-weight body, has a higher crosslink density than a high-molecular-weight body, and the resulting cured product has a high glass transition temperature. It becomes excellent in heat resistance and becomes a preferable aspect.
  • n is 3 or more, the number of methacryloyloxy groups, which are cross-linking groups, increases, the cross-linking density of the obtained cured product is high, and sufficient heat resistance can be obtained, which is preferable.
  • n is 5 or less, the crosslink density of the cured product does not become excessively high, so that it is easy to form a film, etc., and the handleability, flexibility, flexibility, and brittleness resistance are excellent. , more preferred.
  • Ra is the same as Ra in general formula (1) above.
  • the curable resin (A2) has the repeating unit (A2a) and the terminal structure (A2b), and in the general formula (A2a) or general formula (A2b), Ra each independently has 1 to 12 carbon atoms. is an alkyl group, aryl group, aralkyl group or cycloalkyl group, X represents a hydrocarbon group, and Y represents any one of the following general formulas (Y1) to (Y3).
  • Z represents an alicyclic group, an aromatic group, or a heterocyclic group.
  • the curable resin (A2) is included in the curable resin (A2) by having a repeating unit represented by the general formula (A2a) and a terminal structure represented by the general formula (A2b). Ester bonds or carbonate bonds have low molecular mobility compared to ether groups and the like, and therefore have low dielectric properties (particularly low dielectric loss tangent). Further, by having a methacryloyloxy group in the curable resin (A2) component, the obtained cured product has excellent heat resistance, and furthermore, by having an ester bond or a carbonate bond with low molecular mobility, A cured product having not only low dielectric properties but also a high glass transition temperature can be obtained.
  • X may be a hydrocarbon group, but due to the availability of industrial raw materials, it is represented by the structures of the following general formulas (4) to (6). In particular, the structure represented by the following general formula (4) is more preferable because it has a good balance between heat resistance and low dielectric properties.
  • R 1 and R 2 are each independently represented by a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group, or a cycloalkyl group, Alternatively, R 1 and R 2 may be joined together to form a cyclic skeleton.
  • n represents an integer of 0-2, preferably an integer of 0-1. When n is within the above range, high heat resistance is obtained, which is a preferred embodiment.
  • Y represents general formula (Y1), (Y2) or (Y3) above, and from the viewpoint of heat resistance, is preferably general formula (Y1) above.
  • Z is an alicyclic group, an aromatic group, or a heterocyclic group in order to obtain a highly heat-resistant cured product.
  • the structure (benzene ring) represented by the following general formula (7) is more preferable from the viewpoint of cost and heat resistance.
  • Ra is common to Ra in the above general formula (1).
  • the curable resin (A2) is characterized by having a repeating unit represented by the general formula (A2a) and a terminal structure represented by the general formula (A2b). ), other repeating units (structures) may be included as long as the characteristics are not impaired.
  • the weight average molecular weight (Mw) of the curable resin (A2) is preferably from 500 to 50,000, more preferably from 1,000 to 10,000, even more preferably from 1,500 to 5,000. Within the above range, the solvent solubility is improved and the processing workability is favorable, which is preferable.
  • the curable resin (A3) has the above repeating unit (A3a) and a terminal structure (A3b), and in the above general formula (A3b), each Ra is independently an alkyl group having 1 to 12 carbon atoms, an aryl group, aralkyl group or cycloalkyl group.
  • the general formula (A3a) has an indane skeleton, an alicyclic structure having an excellent balance between heat resistance and dielectric properties is introduced into the structure of the curable resin (A3), and the curable resin (A3) is The cured product produced using it has an excellent balance between heat resistance and dielectric properties (especially low dielectric loss tangent), and has a methacryloyloxy group in the terminal structure (A3b), so that steric hindrance increases, and low dielectric properties can be expressed.
  • the weight average molecular weight (Mw) of the curable resin (A3) is preferably from 500 to 50,000, more preferably from 1,000 to 10,000, even more preferably from 1,500 to 5,000. Within the above range, the solvent solubility is improved, the processing workability is good, and the cured product to be obtained is excellent in flexibility and softness, which is preferable.
  • the curable resin (A) of the present invention is preferably one or more selected from the group consisting of the curable resins (A1) to (A3).
  • the curable resin composition of the present invention is a curable resin (B1) having a structure represented by the following general formula (2-1) and / or a curing having a structure represented by the following general formula (2-2) It is characterized by containing a sexual compound (B2).
  • Rb and V may be bonded to any position on the aromatic ring, and in the following general formula (2-1), carbon The bonding site with the atom is shown to be any position on the aromatic ring.
  • Rb is each independently an alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group, or a cycloalkyl group, and V is a vinyl group.
  • k is an integer of 0 to 4
  • l is an integer of 1 to 4
  • m is an integer of 0 to 2.
  • Rb is each independently an alkyl group, aryl group, aralkyl group, or cycloalkyl group having 1 to 12 carbon atoms.
  • V represents a vinyl group and an aromatic vinyl group (in this specification, an aromatic vinyl group represents a vinyl group directly bonded to an aromatic ring. )-containing compound has high self-reactivity, the curing reaction proceeds sufficiently, and furthermore, the aromatic vinyl group-containing compound has low polarity, so that the dielectric constant is low and the dielectric loss tangent is suppressed, which is a preferable embodiment.
  • k represents an integer of 0-4, preferably an integer of 0-2.
  • l represents an integer of 1-4, preferably an integer of 1-2.
  • m represents an integer of 0 to 2, that is, when m is 0, it is a benzene ring, and when m is 1, it is a naphthalene ring, When m is 2, it is an anthracene ring, preferably a benzene ring where m is 0.
  • solvent solubility is excellent and it becomes a preferable aspect.
  • the curable resin (B1) can be used without any particular limitation as long as it has a structure represented by the above general formula (2-1).
  • a curable resin that uses at least one selected from methylstyrene, ethylstyrene, isopropylstyrene, 4-tert-butylstyrene, divinylbenzene, vinylnaphthalene, vinylanthracene, vinylbiphenyl, etc. as a raw material is preferred.
  • any compound represented by the general formula (2-2) can be used without particular limitation.
  • Styrene isopropylstyrene, 4-tert-butylstyrene, divinylbenzene, vinylnaphthalene, vinylanthracene, vinylbiphenyl, bis(vinylphenyl)methane, 1,2-bis(vinylphenyl)ethane, 1,2-bis(vinylphenyl) ) butane, 1,6-bis(4-vinylphenyl)hexane, are preferred.
  • the curable resin composition of the present invention includes a curable resin (B1) having a structure represented by the general formula (2-1) and a curable resin having a structure represented by the general formula (2-2). At least one of the compounds (B2) may be contained, and both the curable resins (B1) and (B2) may be contained.
  • the mass of the curable resin (A) and the total mass of the curable resin (B1) and/or the curable compound (B2) are in a mass ratio of 99: 1 to 10. :90.
  • the mass ratio is 99:1 or less, the curing reaction of the cured product proceeds sufficiently, and the obtained cured product has excellent heat resistance, which is preferable.
  • the mass ratio is 10:90 or more, the resulting cured product has a high crosslink density and is excellent in heat resistance, which is preferable.
  • the obtained cured product has low heat resistance, which is not preferable.
  • the curing reaction proceeds sufficiently, and the obtained curing Not only is the material excellent in heat resistance, but it is also possible to achieve both high dielectric properties that could not be achieved in the past.
  • the curable resin (A) and the curable resin (B1) and / or (B2) at a constant mass ratio, the resulting cured product has excellent heat resistance and a higher It is preferred because it provides inductive properties.
  • the curable resin (A) of the present invention is not particularly limited and can be produced by appropriately utilizing conventionally known methods. For example, it can be obtained by a method of reacting a phenol group-containing resin with methacrylic acid, methacrylic anhydride, or methacrylic acid chloride in an organic solvent in the presence of an acidic or basic catalyst.
  • curable resin (A) of the present invention Specific production examples of the curable resin (A) of the present invention will be described below by dividing the curable resin (A1), the curable resin (A2), and the curable resin (A3).
  • Method for producing curable resin (A1) First, the method for producing the curable resin (A1) will be described.
  • the curable resin (A1) can be obtained, for example, by a method including the following steps (Ia) and (Ib).
  • step (Ia) an aldehyde compound or a ketone compound represented by the following general formulas (12) to (17) and a phenol represented by the following general formula (18) or a derivative thereof are mixed, By reacting in the presence of an acid catalyst, an intermediate phenol compound that is a raw material (precursor) of the curable resin (A1) can be obtained.
  • k represents an integer of 0 to 5
  • Ra represents an alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group, or a cycloalkyl group.
  • aldehyde compound or ketone compound include: formaldehyde, acetaldehyde, propionaldehyde, pivalaldehyde, butyraldehyde, pentanal, Hexanal, trioxane, cyclohexylaldehyde, diphenylacetaldehyde, ethylbutyraldehyde, benzaldehyde, glyoxylic acid, 5-norbornene-2-carboxaldehyde, malondialdehyde, succindialdehyde, salicylaldehyde, naphthaldehyde, glyoxal, malondialdehyde, succine aldehyde, glutaraldehyde, crotonaldehyde, phthalaldehyde and the like.
  • aldehyde compounds glyoxal, glutaraldehyde, crotonaldehyde, phthalaldehyde, and the like are preferable because they are easily available industrially.
  • ketone compound cyclohexanedione and diacetylbenzene are preferable, and among them, cyclohexanedione is more preferable because it is easily available industrially.
  • the compound (a) it is not limited to one type, and two or more types can be used in combination.
  • the phenol or derivative thereof (hereinafter sometimes referred to as "compound (b)") is not particularly limited, but specifically includes 2,6-xylenol (2,6-dimethylphenol), 2 , 3,6-trimethylphenol, 2,6-t-butylphenol, 2,6-diphenylphenol, 2,6-dicyclohexylphenol, 2,6-diisopropylphenol and the like. These phenols or derivatives thereof may be used alone or in combination of two or more. Among them, it is more preferable to use a compound such as 2,6-xylenol in which the ortho-position is alkyl-substituted with respect to the phenolic hydroxyl group. However, if the steric hindrance is too large, there is a concern that the reactivity during the synthesis of the intermediate phenol compound may be inhibited. (b) is preferably used.
  • the compound (a) and the compound (b) are added at a molar ratio of the compound (b) to the compound (a) (compound (b)/compound (a )), preferably 0.1 to 10, more preferably 0.2 to 8, and reacted in the presence of an acid catalyst to obtain the intermediate phenol compound.
  • the acid catalyst used in the reaction includes, for example, inorganic acids such as phosphoric acid, hydrochloric acid and sulfuric acid, organic acids such as oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid and fluoromethanesulfonic acid, activated clay, Acidic clay, silica alumina, zeolite, solid acids such as strongly acidic ion exchange resins, heteropolyacids, etc. can be mentioned, but they are homogeneous catalysts that can be easily removed by neutralization with a base and washing with water after the reaction. Preference is given to using inorganic acids, oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid, fluoromethanesulfonic acid.
  • inorganic acids such as phosphoric acid, hydrochloric acid and sulfuric acid
  • organic acids such as oxalic acid
  • the amount of the acid catalyst is 0.001 to 40 parts by mass with respect to the total amount of 100 parts by mass of the compound (a) and the compound (b) which are initially charged raw materials. However, 0.001 to 25 parts by mass is preferable from the viewpoint of handling and economy.
  • the reaction temperature is usually in the range of 30 to 150° C., but in order to suppress the formation of isomer structures, avoid side reactions such as thermal decomposition, and obtain a high-purity intermediate phenol compound, ⁇ 120°C is preferred.
  • reaction time if the reaction time is short, the reaction does not proceed completely, and if the reaction time is long, side reactions such as thermal decomposition of the product occur. 0.5 to 24 hours, preferably 0.5 to 15 hours in total.
  • Examples of the organic solvent used to synthesize the intermediate phenol compound include ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, cyclohexanone, and acetophenone, and alcohols such as 2-ethoxyethanol, methanol, and isopropyl alcohol.
  • ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, cyclohexanone, and acetophenone
  • alcohols such as 2-ethoxyethanol, methanol, and isopropyl alcohol.
  • aprotic solvents such as sulfolane, dioxane, cyclic ethers such as tetrahydrofuran, ethyl acetate, butyl acetate and aromatic solvents such as benzene, toluene and xylene, and these may be used singly or in combination.
  • the hydroxyl equivalent (phenol equivalent) of the intermediate phenol compound is preferably 80 to 500 g/eq, more preferably 100 to 300 g/eq, from the viewpoint of heat resistance.
  • the hydroxyl equivalent (phenol equivalent) of the intermediate phenol compound is calculated by a titration method, and refers to a neutralization titration method according to JIS K0070.
  • a curable resin (A1) is obtained by a known method such as reaction of the intermediate phenol compound with methacrylic anhydride or methacrylic acid chloride in the presence of a basic or acidic catalyst. be able to.
  • the methacrylic anhydride and methacrylic acid chloride may be used alone or in combination.
  • the basic catalyst examples include dimethylaminopyridine, tetrabutylammonium bromide (TBAB), alkaline earth metal hydroxides, alkali metal carbonates, and alkali metal hydroxides.
  • the acidic catalyst include sulfuric acid and methanesulfonic acid.
  • dimethylaminopyridine is superior in terms of catalytic activity.
  • the methacrylic anhydride in the reaction between the intermediate phenol compound and the methacrylic anhydride, 1 to 10 mol of the methacrylic anhydride is added to 1 mol of the hydroxyl group contained in the intermediate phenol compound, and 0.01 to 0.01 2 mol of a basic catalyst may be added all at once, or may be added gradually at a temperature of 30 to 150° C. for 1 to 40 hours.
  • the reaction rate in synthesizing the curable resin (A1) can be increased.
  • organic solvents include, but are not limited to, ketones such as acetone and methyl ethyl ketone (MEK), alcohols such as methanol, ethanol, 1-propyl alcohol, isopropyl alcohol, 1-butanol, secondary butanol, and tertiary butanol.
  • Ethers such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxane and diethoxyethane, aprotic polar solvents such as acetonitrile, dimethylsulfoxide and dimethylformamide, toluene etc.
  • aprotic polar solvents such as acetonitrile, dimethylsulfoxide and dimethylformamide, toluene etc.
  • the reaction product is reprecipitated in a poor solvent, and then the precipitate is treated with a poor solvent at a temperature of 20 to 100 ° C. After stirring for 5 hours and filtering under reduced pressure, the precipitate is dried at a temperature of 40 to 80° C. for 1 to 10 hours to obtain the desired curable resin (A1). Hexane etc. are mentioned as a poor solvent.
  • the curable resin (A2) can be obtained by, for example, a method of reacting in an organic solvent such as an interfacial polymerization method, or a method of reacting in a molten state such as melt polymerization.
  • Interfacial polymerization method As the interfacial polymerization method, a solution (organic phase) obtained by dissolving a divalent carboxylic acid halide and a cross-linking group-introducing agent used for introducing a reactive group (cross-linking group) that is a terminal structure in an organic solvent that is incompatible with water. is mixed with an alkaline aqueous solution (aqueous phase) containing a dihydric phenol, a polymerization catalyst and an antioxidant, and the polymerization reaction is carried out at a temperature of 50° C. or less for 1 to 8 hours while stirring.
  • a solution (organic phase) obtained by dissolving a cross-linking group-introducing agent used for introducing a reactive group (cross-linking group), which is a terminal structure, in an organic solvent that is not compatible with water For example, a method of blowing phosgene into an alkaline aqueous solution (aqueous phase) containing a dihydric phenol, a polymerization catalyst and an antioxidant, and conducting the polymerization reaction at a temperature of 50° C. or less for 1 to 8 hours while stirring.
  • organic solvent used for the organic phase a solvent that dissolves polyarylate without being miscible with water is preferable.
  • solvents include methylene chloride, 1,2-dichloroethane, chloroform, carbon tetrachloride, chlorobenzene, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, o-, m-, p- Chlorinated solvents such as dichlorobenzene, aromatic hydrocarbons such as toluene, benzene, and xylene, and tetrahydrofuran, etc., and methylene chloride is preferred because it is easy to use in production.
  • the alkaline aqueous solution used for the aqueous phase includes an aqueous solution of sodium hydroxide and an aqueous solution of potassium hydroxide.
  • Antioxidants are used to prevent oxidation of dihydric phenol components.
  • Antioxidants include, for example, sodium hydrosulfite, L-ascorbic acid, erythorbic acid, catechin, tocopherol, and butylhydroxyanisole. Among them, sodium hydrosulfite is preferable because of its excellent water solubility.
  • polymerization catalysts include quaternary ammonium salts such as tri-n-butylbenzylammonium halide, tetra-n-butylammonium halide, trimethylbenzylammonium halide and triethylbenzylammonium halide; and tri-n-butylbenzylphosphonium halide. , tetra-n-butylphosphonium halide, trimethylbenzylphosphonium halide, triethylbenzylphosphonium halide and the like.
  • tri-n-butylbenzylammonium halide trimethylbenzylammonium halide, tetra-n-butylammonium halide, tri-n-butylbenzylphosphonium halide, tetra -n-butylphosphonium halide is preferred.
  • the amount of the polymerization catalyst added is preferably 0.01 to 5.0 mol%, more preferably 0.1 to 1.0 mol%, relative to the number of moles of the dihydric phenol used for polymerization.
  • the addition amount of the polymerization catalyst is 0.01 mol % or more because the effect of the polymerization catalyst is obtained and the molecular weight of the polyarylate resin is increased.
  • it is 5.0 mol % or less, the hydrolysis reaction of the divalent aromatic carboxylic acid halide is suppressed, and the molecular weight of the polyarylate resin is increased, which is preferable.
  • dihydric phenols examples include 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3,6-dimethylphenyl)propane, 2,2- Bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5,6-trimethylphenyl)propane, 2,2-bis(4-hydroxy-2,3,6- trimethylphenyl)propane, bis(4-hydroxy-3,5-dimethylphenyl)methane, bis(4-hydroxy-3,6-dimethylphenyl)methane, bis(4-hydroxy-3-methylphenyl)methane, bis( 4-hydroxy-3,5,6-trimethylphenyl)methane, bis(4-hydroxy-2,3,6-trimethylphenyl)methane, 1,1-bis(4-hydroxy-3,5-dimethylphenyl)- 1-phenylethane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)
  • Divalent carboxylic acid halides include, for example, terephthalic acid halide, isophthalic acid halide, orthophthalic acid halide, diphenic acid halide, biphenyl-4,4'-dicarboxylic acid halide, 1,4-naphthalenedicarboxylic acid halide, 2,3- Naphthalenedicarboxylic acid halide, 2,6-naphthalenedicarboxylic acid halide, 2,7-naphthalenedicarboxylic acid halide, 1,8-naphthalenedicarboxylic acid halide, 1,5-naphthalenedicarboxylic acid halide, diphenyl ether-2,2'-dicarboxylic acid halide, diphenyl ether-2,3'-dicarboxylic acid halide, diphenyl ether-2,4'-dicarboxylic acid halide, diphenyl ether-3,3'-dicarboxylic acid halide, diphen
  • the terminal structure (general formula (A2b)) of the curable resin (A2) has a methacryloyloxy group, and a cross-linking group-introducing agent can be used to introduce the cross-linking group (methacryloyloxy group).
  • a cross-linking group-introducing agent for example, methacrylic anhydride, methacrylic acid chloride, or the like can be reacted. By reacting these, a cross-linking group can be introduced into the curable resin, and thermosetting with a low dielectric constant and a low dielectric loss tangent can be obtained, which is a preferred embodiment.
  • the methacrylic anhydride and methacrylic acid chloride may be used individually or in combination.
  • melt polymerization method a method of acetylating the dihydric phenol as a raw material and then deacetic acid-polymerizing the acetylated dihydric phenol and a dihydric carboxylic acid, or a method of transesterifying the dihydric phenol and a carbonate ester. methods of reacting.
  • an aromatic dicarboxylic acid component, a dihydric phenol component and acetic anhydride are put into a reaction vessel. Thereafter, the mixture is purged with nitrogen and stirred under an inert atmosphere at a temperature of 100 to 240° C., preferably 120 to 180° C., for 5 minutes to 8 hours, preferably 30 minutes to 5 hours, under normal pressure or increased pressure.
  • the molar ratio of acetic anhydride to hydroxyl groups of the dihydric phenol component is preferably 1.00 to 1.20.
  • the deacetic acid polymerization reaction is a polycondensation reaction of acetylated dihydric phenol and dihydric carboxylic acid.
  • a temperature of 240° C. or higher, preferably 260° C. or higher, more preferably 220° C. or higher, and a reduced pressure of 500 Pa or lower, preferably 260 Pa or lower, more preferably 130 Pa or lower, are maintained for 30 minutes or longer, Stir.
  • the temperature is 240° C. or higher, the degree of pressure reduction is 500 Pa or lower, or the holding time is 30 minutes or longer
  • the deacetic acid reaction proceeds sufficiently to reduce the amount of acetic acid in the resulting polyarylate resin. , the entire polymerization time can be shortened, and the deterioration of polymer color tone can be suppressed.
  • catalysts include organic titanate compounds such as tetrabutyl titanate; zinc acetate; alkali metal salts such as potassium acetate; alkaline earth metal salts such as magnesium acetate; organic tin compounds; heterocyclic compounds such as N-methylimidazole;
  • the amount of catalyst added is usually 1.0 mol % or less, more preferably 0.5 mol % or less, and still more preferably 0.2 mol % or less, relative to the total monomer components of the resulting polyarylate resin. is.
  • the reaction is carried out at a temperature of 120 to 260°C, preferably 160 to 200°C, for 0.1 to 5 hours, preferably 0.5 to 6 hours, and a pressure of normal pressure to 1 Torr.
  • transesterification reaction catalyst for example, salts of zinc, tin, zirconium, and lead are preferably used, and these can be used alone or in combination.
  • Specific examples of transesterification catalysts include zinc acetate, zinc benzoate, zinc 2-ethylhexanoate, tin (II) chloride, tin (IV) chloride, tin (II) acetate, tin (IV) acetate, and dibutyltin.
  • Dilaurate, dibutyltin oxide, dibutyltin dimethoxide, zirconium acetylacetonate, zirconium oxyacetate, zirconium tetrabutoxide, lead acetate (II), lead acetate (IV) and the like are used. These catalysts are used in a ratio of 0.000001 to 0.1 mol %, preferably in a ratio of 0.00001 to 0.01 mol %, relative to 1 mol of the dihydric phenol.
  • the dihydric phenol in the interfacial polymerization method described above can be used in the same manner.
  • divalent carboxylic acids include terephthalic acid, isophthalic acid, orthophthalic acid, diphenic acid, biphenyl-4,4′-dicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6 -naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, diphenyl ether-2,2'-dicarboxylic acid, diphenyl ether-2,3'-dicarboxylic acid, diphenyl ether -2,4'-dicarboxylic acid, diphenyl ether-3,3'-dicarboxylic acid, diphenyl ether-3,4'-dicarboxylic acid, diphenyl ether-4,4'-dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid
  • Carbonic acid esters include, for example, diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis(diphenyl) carbonate, diethyl carbonate, dimethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, and the like. be done.
  • the terminal structure (general formula (A2b)) of the curable resin (A2) it has a methacryloyloxy group.
  • the cross-linking group-introducing agent the above-described cross-linking group-introducing agent in the interfacial polymerization method can be used in the same manner.
  • the curable resin (A3) can be obtained, for example, by a method including the following steps (II-a) and (II-b).
  • Step (II-a)> a compound of the following general formula (19) and a compound of any one of the following general formulas (22-1) to (22-3) are reacted in the presence of an acid catalyst to cure. It is possible to obtain an intermediate phenol compound that is a raw material (precursor) of the curable resin (A3).
  • Rc each independently represents a monovalent functional group selected from the group consisting of the following general formulas (20) and (21), and at least one of the two Rc is a hydrogen atom, Rb represents an alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group or a cycloalkyl group, and l represents an integer of 0 to 4.
  • Rb represents an alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group or a cycloalkyl group
  • l represents an integer of 0 to 4.
  • the following general formula (22-1) is when j in the general formula (1) is 0, that is, when the curable resin having an indane skeleton is a benzene ring, and i is 1 or 2. is preferred, and i is more preferably 1.
  • the following general formula (22-2) is the case where j in the above general formula (1) is 1, that is, the case of a naphthalene ring, i is preferably 1 or 2, and i is 1. It is more preferable to have
  • the following general formula (22-3) is a case where j in the above general formula (1) is 2, that is, an anthracene ring, i is preferably 1 or 2, and i is 1.
  • the curable resin having an indane skeleton has a hydroxyl group (phenolic hydroxyl group), it becomes possible to introduce a phenolic hydroxyl group at the end of the structure, which is a preferred embodiment.
  • Ra and h are phenol or a derivative thereof, each of which is similar to the above, and the compound of the general formula (19) and any of the following general formulas (22-1) to (22-3) By reacting the compound in the presence of an acid catalyst, an intermediate phenol compound represented by the following general formula (23) can be obtained.
  • Ra, h, and i in the following general formula (23) are the same as above, and n represents a repeating unit.
  • the following general formula (23) exemplifies the case where j in the above general formula (1) is 0, that is, the case of a benzene ring. (22-1) (22-2) (22-3) (23)
  • the weight average molecular weight (Mw) of general formula (23) is preferably 500 to 50,000, more preferably 1,000 to 10,000, and even more preferably 1,500 to 5,000. Within the above range, the solvent solubility is improved, the processing workability is good, and the cured product to be obtained is excellent in flexibility and softness, which is preferable.
  • the compound represented by the general formula (19) (hereinafter referred to as "compound (c)") used in the present invention is not particularly limited, but typically includes p- and m-diisopropenylbenzene, p- and m-bis( ⁇ -hydroxyisopropyl)benzene ( ⁇ , ⁇ '-dihydroxy-1,3-diisopropylbenzene), p- and m-bis( ⁇ -chloroisopropyl)benzene, 1-( ⁇ -hydroxyisopropyl)-3 - isopropenylbenzene, 1-( ⁇ -hydroxyisopropyl)-4-isopropenylbenzene or a mixture thereof.
  • core alkyl group-substituted products of these compounds such as diisopropenyltoluene and bis( ⁇ -hydroxyisopropyl)toluene can also be used, and further core halogen-substituted products such as chlorodiisopropenylbenzene and chlorobis( ⁇ -hydroxyisopropyl)benzene and the like can also be used.
  • examples of the compound (c) include 2-chloro-1,4-diisopropenylbenzene, 2-chloro-1,4-bis( ⁇ -hydroxyisopropyl)benzene, 2-bromo-1,4-di Isopropenylbenzene, 2-bromo-1,4-bis( ⁇ -hydroxyisopropyl)benzene, 2-bromo-1,3-diisopropenylbenzene, 2-bromo-1,3-bis( ⁇ -hydroxyisopropyl)benzene , 4-bromo-1,3-diisopropylbenzene, 4-bromo-1,3-bis( ⁇ -hydroxyisopropyl)benzene, 5-bromo-1,3-diisopropenylbenzene, 5-bromo-1,3- Bis( ⁇ -hydroxyisopropyl)benzene, 2-methoxy-1,4-diisopropenylbenzene, 2-methoxy-1,4-di
  • the substituent contained in the compound (c) is not particularly limited, and the compounds exemplified above can be used.
  • the obtained intermediate phenol compounds are less likely to be stacked with each other, and the intermediate phenol compounds are less likely to be crystallized.
  • compound (d) is phenol or a derivative thereof, and is not particularly limited. Specifically, 2,6-xylenol (2,6-dimethylphenol), 2,3,6-trimethylphenol, 2,6-t-butylphenol, 2,6-diphenylphenol, 2,6-dicyclohexylphenol, 2 , 6-diisopropylphenol and the like. These phenols or derivatives thereof may be used alone or in combination of two or more.
  • the compound (c) and the compound (d) are combined in a molar ratio of the compound (d) to the compound (c).
  • the acid catalyst used in the reaction includes, for example, inorganic acids such as phosphoric acid, hydrochloric acid and sulfuric acid, organic acids such as oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid and fluoromethanesulfonic acid, activated clay, Acidic clay, silica alumina, zeolite, solid acids such as strongly acidic ion exchange resins, heteropolyhydrochloric acid, etc. can be mentioned, but they are homogeneous catalysts that can be easily removed by neutralization with a base and washing with water after the reaction. Preference is given to using oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid, fluoromethanesulfonic acid.
  • inorganic acids such as phosphoric acid, hydrochloric acid and sulfuric acid
  • organic acids such as oxalic acid, benz
  • the amount of the acid catalyst is 0.001 to 40 parts by mass with respect to 100 parts by mass of the total amount of the compound (c) and the compound (d) which are initially charged as raw materials. However, 0.001 to 25 parts by mass is preferable from the viewpoint of handling and economy.
  • the reaction temperature is usually in the range of 50 to 300° C., but in order to suppress the formation of isomer structures, avoid side reactions such as thermal decomposition, and obtain a high-purity intermediate phenol compound, ⁇ 200°C is preferred.
  • reaction time if the reaction time is short, the reaction does not proceed completely, and if the reaction time is long, side reactions such as thermal decomposition of the product occur. 0.5 to 24 hours, preferably 0.5 to 12 hours in total.
  • phenol or its derivative also serves as a solvent
  • a solvent capable of azeotropic dehydration such as toluene, xylene, or chlorobenzene is used.
  • the solvent is distilled off and then the reaction is carried out within the above reaction temperature range.
  • Examples of the organic solvent used for synthesizing the intermediate phenol compound include ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, cyclohexanone, and acetophenone, N,N-dimethylformamide, N,N-dimethylacetamide. , dimethyl sulfoxide, N-methyl-2-pyrrolidone, acetonitrile, sulfolane and other aprotic solvents, dioxane, tetrahydrofuran and other cyclic ethers, ethyl acetate, butyl acetate and other esters, benzene, toluene, xylene and other aromatics. system solvents, etc., and these may be used alone or in combination.
  • ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, cyclohexanone, and
  • the hydroxyl equivalent (phenol equivalent) of the intermediate phenol compound is preferably 200 to 2000 g/eq, more preferably 220 to 500 g/eq, from the viewpoint of heat resistance.
  • the hydroxyl equivalent (phenol equivalent) of the intermediate phenol compound is calculated by a titration method, and refers to a neutralization titration method according to JIS K0070.
  • step (II-b)> in the presence of a basic or acidic catalyst, the intermediate phenol compound is subjected to a known method such as reaction with methacrylic anhydride or methacrylic acid chloride to form a curable resin (A3). can be obtained.
  • the methacrylic anhydride and methacrylic acid chloride may be used alone or in combination.
  • the basic catalyst include dimethylaminopyridine, alkaline earth metal hydroxides, alkali metal carbonates, and alkali metal hydroxides.
  • the acidic catalyst include sulfuric acid and methanesulfonic acid.
  • dimethylaminopyridine is superior in terms of catalytic activity.
  • organic solvents include, but are not limited to, ketones such as acetone and methyl ethyl ketone; alcohols such as methanol, ethanol, 1-propyl alcohol, isopropyl alcohol, 1-butanol, secondary butanol and tertiary butanol; cellosolves such as cellosolve and ethyl cellosolve; ethers such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxane and diethoxyethane; aprotic polar solvents such as acetonitrile, dimethylsulfoxide and dimethylformamide; be done. These organic solvents may be used alone, or two or more of them may be used in combination to adjust the polarity.
  • the reaction product is washed with water, and then unreacted methacrylic anhydride and the organic solvent used in combination are distilled off under heating and reduced pressure conditions. Furthermore, in order to further reduce hydrolyzable halogen in the obtained curable resin having an indane skeleton, the curable resin having an indane skeleton is dissolved again in an organic solvent such as toluene, methyl isobutyl ketone, methyl ethyl ketone, and hydroxylated. Further reaction can be carried out by adding an aqueous solution of an alkali metal hydroxide such as sodium or potassium hydroxide.
  • an alkali metal hydroxide such as sodium or potassium hydroxide.
  • a phase transfer catalyst such as a quaternary ammonium salt or crown ether may be present for the purpose of improving the reaction rate.
  • the amount used is preferably in the range of 0.1 to 10% by mass relative to the curable resin having an indane skeleton.
  • the curable resin (B1) of the present invention is not particularly limited and can be produced by appropriately utilizing conventionally known methods.
  • a polyfunctional vinyl aromatic compound obtained by polymerizing a divinyl aromatic compound or a monovinyl aromatic compound in an organic solvent in the presence of a Lewis acid catalyst. polymers.
  • the curable resin composition of the present invention contains the curable resin (A), the curable resin (B1) and/or the curable compound (B2).
  • the curable resin (A), the curable resin (B1), and the curable compound (B2) are used alone, the obtained cured product has low heat resistance, which is not preferable.
  • the curing reaction proceeds sufficiently, and the obtained curing Not only is the material excellent in heat resistance, but it is also possible to achieve both high dielectric properties that could not be achieved in the past.
  • the curable resin (A), the curable resin (B1) and/or the curable compound (B2) at a constant mass ratio, the obtained cured product has further heat resistance. It is preferable because it is excellent and can obtain higher inductive properties.
  • the curable resin composition of the present invention may contain a thermoplastic resin within a range that does not impair the purpose.
  • a thermoplastic resin for example, styrene-butadiene resin, styrene-butadiene-styrene block resin, styrene-isoprene-styrene resin, styrene-maleic anhydride resin, acrylonitrile-butadiene resin, polybutadiene resin or hydrogenated resins thereof, acrylic resin, silicone resin, etc.
  • the thermoplastic resin it is possible to provide the cured product with the properties attributed to the resin, which is a preferred embodiment.
  • the properties that can be imparted can contribute to moldability, high frequency characteristics, conductor adhesiveness, solder heat resistance, adjustment of glass transition temperature, coefficient of thermal expansion, impartation of smear removability, and the like.
  • the curable resin composition of the present invention may be blended with a non-halogen flame retardant that does not substantially contain halogen atoms in order to exhibit flame retardancy.
  • non-halogen flame retardants include phosphorus flame retardants, nitrogen flame retardants, silicone flame retardants, inorganic flame retardants, organic metal salt flame retardants, etc. These are used alone or in combination. be able to.
  • the curable resin composition of the present invention may optionally contain an inorganic filler.
  • the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide.
  • fused silica When the amount of the inorganic filler compounded is particularly large, it is preferable to use fused silica.
  • the fused silica may be crushed or spherical, but in order to increase the blending amount of fused silica and suppress the increase in the melt viscosity of the molding material, it is better to mainly use spherical fused silica. preferable.
  • the curable resin composition of the present invention may optionally contain various compounding agents such as silane coupling agents, release agents, pigments and emulsifiers.
  • the present invention relates to a cured product obtained by subjecting the curable resin composition to a curing reaction.
  • the curable resin composition uniformly contains each component such as the flame retardant described above according to the purpose. It is obtained by mixing, and can be easily cured by a method similar to a conventionally known method.
  • the cured product include molded cured products such as laminates, cast products, adhesive layers, coating films, and films.
  • Examples of the curing reaction include heat curing and ultraviolet curing reactions. Among them, the heat curing reaction can be easily carried out even without a catalyst.
  • the cured product obtained from the curable resin composition of the present invention is excellent in heat resistance and dielectric properties, it can be suitably used for heat-resistant members and electronic members.
  • it can be suitably used for varnishes, prepregs, circuit boards, semiconductor sealing materials, semiconductor devices, build-up films, build-up substrates, adhesives, resist materials, and the like used in the production of prepregs.
  • it can be suitably used as a matrix resin for fiber-reinforced resins, and is particularly suitable as a highly heat-resistant prepreg.
  • the heat-resistant members and electronic members obtained in this way can be suitably used for various applications, for example, industrial machine parts, general machine parts, automobile/railroad/vehicle parts, aerospace-related parts, electronic/electrical parts, Building materials, containers/packaging members, daily necessities, sports/leisure goods, housing members for wind power generation, etc., but not limited to these.
  • the present invention relates to a varnish obtained by diluting the curable resin composition with an organic solvent.
  • a method for preparing the varnish a known method can be used, and the curable resin composition can be dissolved (diluted) in an organic solvent to obtain a resin varnish.
  • organic solvent examples include toluene, xylene, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, methyl ethyl ketone (MEK), methyl isobutyl ketone, dioxane, tetrahydrofuran, and the like. , can be used alone or as a mixed solvent of two or more.
  • the present invention relates to a prepreg having a reinforcing substrate and semi-curing of said varnish impregnating said reinforcing substrate.
  • a prepreg having a reinforcing substrate and semi-curing of said varnish impregnating said reinforcing substrate.
  • the reinforcing substrate to be impregnated with the varnish examples include inorganic fibers such as glass fiber, polyester fiber and polyamide fiber, woven fabrics and non-woven fabrics made of organic fibers, mats, paper, etc., which may be used alone or , can be used in combination.
  • the mass ratio of the curable resin composition and the reinforcing base material in the prepreg is not particularly limited, but usually the curable resin composition (the resin content therein) in the prepreg is 20 to 60% by mass. preferably prepared.
  • the conditions for the heat treatment of the prepreg are appropriately selected depending on the type and amount of the organic solvent, catalyst, and various additives used. This is done under such conditions.
  • the present invention relates to a circuit board obtained by laminating the prepreg and copper foil and thermocompression molding. Specifically, as a method for obtaining a circuit board from the curable resin composition of the present invention, the above prepreg is laminated by a conventional method, appropriately overlaid with copper foil, and heated at 170 to 300 ° C. under a pressure of 1 to 10 MPa. for 10 minutes to 3 hours at a temperature of about 10 minutes to 3 hours to obtain a circuit board.
  • the semiconductor sealing material preferably contains the curable resin composition.
  • the curable resin composition is further added with a compounding agent such as an inorganic filler, which is an optional component, if necessary.
  • a method of sufficiently melt-mixing using an extruder, a kneader, a roll, or the like until the mixture becomes uniform is exemplified.
  • fused silica is usually used as the inorganic filler, but when it is used as a high thermal conductive semiconductor encapsulant for power transistors and power ICs, crystalline silica, alumina, and nitride, which have higher thermal conductivity than fused silica, are used. It is preferable to use silicon or the like.
  • the filling rate is preferably in the range of 30 to 95 parts by mass of the inorganic filler per 100 parts by mass of the curable resin composition. In order to reduce the coefficient, it is more preferably 70 parts by mass or more, and even more preferably 80 parts by mass or more.
  • the semiconductor device preferably contains a cured product obtained by heating and curing the semiconductor sealing material.
  • the semiconductor encapsulant is cast, or molded using a transfer molding machine, an injection molding machine, or the like. A method of heat curing at 50 to 250° C. for 2 to 10 hours can be mentioned.
  • a method of obtaining a build-up substrate from the curable resin composition of the present invention includes a method involving steps 1 to 3.
  • step 1 first, the curable resin composition appropriately blended with rubber, filler, etc. is applied to a circuit board having a circuit formed thereon by using a spray coating method, a curtain coating method, or the like, and then cured.
  • step 2 if necessary, the circuit board to which the curable resin composition has been applied is drilled with a predetermined through hole or the like, treated with a roughening agent, and the surface is washed with hot water. Concavo-convex portions are formed on the substrate and plated with a metal such as copper.
  • step 3 the operations of steps 1 and 2 are repeated as desired to alternately build up resin insulating layers and conductor layers having a predetermined circuit pattern to form a buildup board.
  • the build-up board in the present invention is obtained by heat-pressing a copper foil with a resin obtained by semi-curing the resin composition on a copper foil onto a wiring board on which a circuit is formed at 170 to 300 ° C. It is also possible to produce a build-up board by omitting the steps of forming a hardened surface and plating.
  • the build-up film preferably contains the curable resin composition.
  • the curable resin composition is applied onto a support film and then dried to form a resin composition layer on the support film. method.
  • the film softens under the laminating temperature conditions (usually 70 to 140° C.) in the vacuum lamination method, and is present on the circuit board at the same time as the circuit board is laminated. It is essential to exhibit fluidity (resin flow) that enables resin filling in via holes or through holes, and it is preferable to blend the above components so as to exhibit such properties.
  • the diameter of the through hole of the circuit board is usually 0.1 to 0.5 mm, and the depth is usually 0.1 to 1.2 mm, and it is usually preferable to allow resin filling within this range.
  • the through holes When both sides of the circuit board are laminated, it is desirable to fill the through holes by about half.
  • the varnished resin composition is applied to the surface of the support film (Y). and then drying the organic solvent by heating or blowing hot air to form the resin composition layer (X).
  • organic solvent used here examples include ketones such as acetone, methyl ethyl ketone and cyclohexanone, acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, cellosolve and butyl carbitol.
  • ketones such as acetone, methyl ethyl ketone and cyclohexanone
  • acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, cellosolve and butyl carbitol.
  • Carbitols, toluene, aromatic hydrocarbons such as xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. are preferably used, and the nonvolatile content
  • the thickness of the resin composition layer (X) to be formed should normally be greater than or equal to the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 ⁇ m, the thickness of the resin composition layer (X) is preferably 10 to 100 ⁇ m.
  • the resin composition layer (X) in the present invention may be protected with a protective film to be described later. By protecting the surface of the resin composition layer with a protective film, it is possible to prevent the surface of the resin composition layer from being dusted or scratched.
  • the support film and the protective film include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate, polycarbonates, polyimides, and metal foils such as release paper, copper foil, and aluminum foil. etc. can be mentioned.
  • the support film and protective film may be subjected to a release treatment in addition to mud treatment and corona treatment.
  • the thickness of the support film is not particularly limited, it is usually 10 to 150 ⁇ m, preferably 25 to 50 ⁇ m. Also, the thickness of the protective film is preferably 1 to 40 ⁇ m.
  • the support film (Y) is peeled off after lamination on the circuit board, or after heat curing to form an insulating layer. If the support film (Y) is peeled off after the resin composition layer constituting the build-up film is cured by heating, it is possible to prevent the adhesion of dust and the like during the curing process. When peeling after curing, the support film is normally subjected to a release treatment in advance.
  • a multilayer printed circuit board can be produced from the build-up film obtained as described above.
  • the resin composition layer (X) is protected by a protective film, after removing these, the resin composition layer (X) is placed on one or both sides of the circuit board so as to be in direct contact with the circuit board.
  • the method of lamination may be a batch type or a continuous roll type. If necessary, the build-up film and the circuit board may be heated (preheated) before lamination.
  • the conditions for lamination are preferably a pressure bonding temperature (laminating temperature) of 70 to 140° C.
  • Examples of the method of obtaining the conductive paste from the curable resin composition of the present invention include a method of dispersing conductive particles in the composition.
  • the conductive paste can be a paste resin composition for circuit connection or an anisotropic conductive adhesive, depending on the type of conductive particles used.
  • Measuring device "HLC-8320 GPC” manufactured by Tosoh Corporation Column: guard column “HXL-L” manufactured by Tosoh Corporation + “TSK-GEL G2000HXL” manufactured by Tosoh Corporation + “TSK-GEL G2000HXL” manufactured by Tosoh Corporation + “TSK-GEL G3000HXL” manufactured by Tosoh Corporation + Tosoh Corporation Made by “TSK-GEL G4000HXL” Detector: RI (differential refractometer) Data processing: "GPC Workstation EcoSEC-WorkStation” manufactured by Tosoh Corporation Measurement conditions: Column temperature 40°C Developing solvent tetrahydrofuran Flow rate 1.0 ml/min Standard: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of the aforementioned "GPC Workstation EcoSEC-WorkStation".
  • reaction liquid After completion of the reaction, the resulting reaction mixture (reaction liquid) was cooled to room temperature (25° C.), 200 ml of toluene was added to the reaction liquid, and then 200 mL of water was used to wash the reaction liquid. After that, the obtained organic phase was poured into 500 mL of hexane, and the precipitated solid was separated by filtration and vacuum-dried to obtain 22 g (0.039 mol) of an intermediate phenol compound. 20 g of toluene and 22 g (0.039 mol) of the intermediate phenol compound were mixed in a 200 mL flask equipped with a thermometer, condenser, and stirrer, and the temperature was raised to about 85°C.
  • reaction liquid was cooled to room temperature (25° C.), 200 ml of toluene was added to the reaction liquid, and then washed with 200 mL of water. After that, the obtained organic phase was poured into 500 mL of hexane, and the precipitated solid was separated by filtration and vacuum-dried to obtain 32.2 g (0.039 mol) of an intermediate phenol compound. 20 g of toluene and 32.2 g (0.039 mol) of the intermediate phenol compound were mixed in a 200 mL flask equipped with a thermometer, condenser, and stirrer, and the temperature was raised to about 85°C.
  • the aqueous phase was previously stirred, and the organic phase was added to the aqueous phase under strong stirring and reacted at 20° C. for 5 hours. After that, stirring was stopped, the aqueous phase and the organic phase were separated, and the organic phase was washed with pure water ten times. Thereafter, methylene chloride was distilled from the organic phase under reduced pressure using an evaporator to dry the polymer. The obtained polymer was dried under reduced pressure to obtain a curable resin (A-3) having the following repeating unit and a terminal methacryloyloxy group and a weight average molecular weight of 3100.
  • curable compound (B-3) As a curable resin, commercially available 2-vinylnaphthalene (manufactured by Sigma-Aldrich) was used as curable compound (B-3).
  • a curable resin (B-4) containing a vinylbenzyl group and having a weight average molecular weight of 40,000 was obtained.
  • curable resin (A-7) As a curable resin, commercially available 4,4'-isopropylidenediphenol dimethacrylate (manufactured by Sigma-Aldrich) was used as a curable resin (A-7). and
  • ⁇ Preparation of curable resin composition> Using the curable resin or curable compound obtained in the above production example, a curable resin composition having the formulation contents (raw materials, compounding amount) shown in Table 1 or Table 2 below, and the conditions shown below (temperature , time, etc.), evaluation samples (resin films (cured products)) were prepared and evaluated as examples and comparative examples.
  • the curable resin composition was placed in a 5 cm square square mold, sandwiched between stainless steel plates, and set in a vacuum press. It was pressurized to 1.5 MPa under normal pressure and normal temperature. Next, the pressure was reduced to 10 torr, and then heated to a temperature 50° C. higher than the thermosetting temperature over 30 minutes. After standing still for 2 hours, it was gradually cooled to room temperature to obtain a uniform resin film (cured product) having an average thickness of 100 ⁇ m.
  • the dielectric constant and dielectric loss tangent at a frequency of 10 GHz were measured by the split-post dielectric resonator method using a network analyzer N5247A manufactured by Keysight Technologies. was measured. If the dielectric loss tangent is 10.0 ⁇ 10 ⁇ 3 or less, there is no practical problem, preferably 3.0 ⁇ 10 ⁇ 3 or less, more preferably 2.5 ⁇ 10 ⁇ 3 or less. be. Particularly preferably, it is 2.0 ⁇ 10 ⁇ 3 or less. Also, if the dielectric constant is 3 or less, there is no practical problem, preferably 2.7 or less, more preferably 2.5 or less.
  • the resulting resin film (cured product) was measured using a TG-DTA device (TG-8120) manufactured by Rigaku Co., Ltd. under a nitrogen flow of 20 mL/min at a heating rate of 20 ° C./min. Weight loss temperature (Td5) was measured.
  • the cured products obtained by using the desired curable resin compositions can achieve both heat resistance and low dielectric properties. It has been confirmed that the level is practically acceptable. On the other hand, it was confirmed that Comparative Examples 1 and 2 had a high dielectric loss tangent because the compound did not have a substituent that inhibits the molecular mobility of the methacryloyloxy group. Moreover, in Comparative Examples 1 to 3, it was confirmed that the heat resistance of the cured product was lowered because only one of the methacryloyloxy group-containing compound and the aromatic vinyl group-containing compound was included.

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WO2026023296A1 (ja) * 2024-07-26 2026-01-29 パナソニックＩｐマネジメント株式会社 樹脂組成物、プリプレグ、樹脂付きフィルム、樹脂付き金属箔、金属張積層板、及び配線板

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