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WO2025115767A1 - Résine d'ester thermodurcissable, son procédé de production, composition de résine thermodurcissable, objet durci formé à partir de celle-ci, préimprégné, feuille de résine, stratifié et matériau pour cartes de circuit imprimé - Google Patents

Résine d'ester thermodurcissable, son procédé de production, composition de résine thermodurcissable, objet durci formé à partir de celle-ci, préimprégné, feuille de résine, stratifié et matériau pour cartes de circuit imprimé Download PDF

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Publication number
WO2025115767A1
WO2025115767A1 PCT/JP2024/041381 JP2024041381W WO2025115767A1 WO 2025115767 A1 WO2025115767 A1 WO 2025115767A1 JP 2024041381 W JP2024041381 W JP 2024041381W WO 2025115767 A1 WO2025115767 A1 WO 2025115767A1
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group
carbon atoms
formula
aromatic
thermosetting
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Japanese (ja)
Inventor
正浩 宗
仲輝 池
起煥 柳
佳英 李
海璃 尹
智雄 金
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Nippon Steel Chemical and Materials Co Ltd
Kukdo Chemical Co Ltd
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Nippon Steel Chemical and Materials Co Ltd
Kukdo Chemical Co Ltd
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Publication of WO2025115767A1 publication Critical patent/WO2025115767A1/fr
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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
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/12—Esters of monohydric alcohols or phenols
    • C08F20/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F20/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • 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
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/20—Esters of polyhydric alcohols or polyhydric phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • 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
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • 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 thermosetting ester resins with excellent dielectric properties, their manufacturing methods, and thermosetting resin compositions, cured products, prepregs, resin sheets, laminates, and circuit board materials that use them.
  • thermosetting resins have excellent adhesive properties, flexibility, heat resistance, chemical resistance, insulation, and curing reactivity, and are therefore used in a wide range of applications, including paints, civil engineering adhesives, casting, electrical and electronic materials, and film materials.
  • thermosetting resins are widely used in printed wiring boards, one type of electrical and electronic material, by imparting flame retardancy to them.
  • thermosetting resin compositions which are materials for electrical and electronic components, are required to have low dielectric properties in line with the need for thinner substrates and higher functionality.
  • Patent Document 1 proposes an epoxy resin composition that contains, as an essential component, a polyester that has an arylcarbonyloxy group at the molecular chain end and is composed of an aromatic polyvalent carboxylic acid residue and an aromatic polyvalent hydroxy compound residue.
  • Patent Document 2 proposes an epoxy resin composition containing, as an essential component, an active ester compound obtained by reacting a specific phenolic resin, an aromatic dicarboxylic acid or its halide, and an aromatic monohydroxy compound.
  • thermosetting resins disclosed in these documents do not fully satisfy the performance requirements based on recent trends toward high functionality, and are insufficient to ensure low dielectric properties and heat resistance.
  • Patent Document 3 proposes an epoxy resin composition that contains 2,6-xylenol-dicyclopentadiene type epoxy resin as an essential component.
  • the problem that the present invention aims to solve is to provide a curable resin composition that exhibits excellent dielectric properties in the cured product and also has excellent heat resistance for use in printed wiring boards.
  • thermosetting resin represented by the following general formula (1) After extensive research to solve the problems, the inventors discovered that the above problems could be solved by using a thermosetting resin represented by the following general formula (1), and thus completed the present invention.
  • the present invention is a thermosetting resin comprising a polyaryloxy unit and a polyarylcarbonyl unit, characterized in that the polyaryloxy unit has a reactive group-containing unit represented by the following formula (1):
  • R1 independently represents a hydrocarbon group having 1 to 8 carbon atoms
  • R2 independently represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms
  • Y independently represents a bonding site with a polyarylcarbonyl unit or a reactive group represented by formula (2)
  • 1 to 99 mol % of all Y's are reactive groups represented by formula (2)
  • R represents a hydrogen atom or an alkyl or alkenyl group having 1 to 8 carbon atoms
  • i is an integer from 0 to 2
  • n represents the number of repetitions, the average of which is a number from 0 to 5.
  • the polyaryloxy unit contains other polyaryloxy units than the unit represented by the above formula (1), and the other polyaryloxy units are preferably units represented by the following formula (3) and/or formula (4).
  • Ar1 is independently an aromatic ring group of any one of a benzene ring, a naphthalene ring, a furan ring, and a biphenyl ring, and these aromatic rings may have an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 11 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an aryloxy group having 6 to 11 carbon atoms, or an aralkyloxy group having 7 to 12 carbon atoms as a substituent.
  • Ar11 is a divalent hydrocarbon group having 1 to 10 carbon atoms or a divalent group represented by formula (3a).
  • R11 is independently a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms.
  • R3 is a divalent group selected from the group consisting of a direct bond, a hydrocarbon group having 1 to 20 carbon atoms, -CO-, -O-, -S-, -SO 2 -, and -C(CF 3 ) 2 -.
  • m indicates the number of repetitions, the average value of which is a number of 1 to 5.
  • r is 1 or 2.
  • k is 0 or 1.
  • the thermosetting ester resin may further contain a monoaryloxy unit, and the monoaryloxy unit is preferably a group represented by the following formula (6).
  • Ar2 is independently an aromatic ring group of any one of a benzene ring, a naphthalene ring, a furan ring, and a biphenyl ring, and these aromatic rings may have, as a substituent, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 11 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an aryloxy group having 6 to 11 carbon atoms, or an aralkyloxy group having 7 to 12 carbon atoms.
  • R4 is a divalent group selected from the group consisting of a direct bond, -CH 2 -, -C(CH 3 ) 2 -, -CH(CH 3 ) -, -CO-, -O-, -S-, -SO 2 -, and -C(CF 3 ) 2 -.
  • R14 is a divalent group selected from the group consisting of a direct bond, -CH 2 -, -C(CH 3 ) 2 -, -CH(CH 3 )-, and -C(CF 3 ) 2 -.
  • k is 0 or 1.
  • the thermosetting ester resin has a polyarylcarbonyl unit, and the polyarylcarbonyl unit is preferably a unit represented by the following formula (7).
  • Ar3 is independently an aromatic ring group of any one of a benzene ring, a naphthalene ring, a furan ring, and a biphenyl ring, and these aromatic rings may have, as a substituent, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 11 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an aryloxy group having 6 to 11 carbon atoms, or an aralkyloxy group having 7 to 12 carbon atoms.
  • R5 is a direct bond, or a divalent group selected from a hydrocarbon group having 1 to 20 carbon atoms, -CO-, -O-, -S-, -SO 2 -, and -C(CF 3 ) 2 -.
  • k is 0 or 1.
  • the present invention is a method for producing the above-mentioned curable ester resin, which is characterized by using, as raw materials, an aromatic polyhydric hydroxy compound (A1) containing a polyhydric hydroxy compound represented by the following formula (11), an unsaturated group-containing carboxylic anhydride (B1) represented by the following formula (12a) or an unsaturated group-containing carboxylic acid halide (B2) represented by the following formula (12b), and an aromatic polyhydric carboxylic acid (C1) represented by the following formula (17a) or an aromatic polyhydric carboxylic acid halide (C2) represented by the following formula (17b).
  • R1, R2, i, and n are each defined as in formula (1) above.
  • R is defined as in the above formula (2)
  • X represents a halogen.
  • Ar3, R5, and k are each defined as in the above formula (7), and X represents a halogen.
  • an aromatic monohydroxy compound (A2) may further be contained, and the aromatic monohydroxy compound (A2) is preferably a compound represented by the following formula (16).
  • Ar2, R4, R14, and k are each defined as in formula (6) above.
  • the present invention is a thermosetting resin composition that contains the above-mentioned thermosetting ester resin as an essential component.
  • the present invention relates to a cured product obtained by curing the above-mentioned thermosetting resin composition, and also to prepregs, resin sheets, laminates, and circuit board materials that use the above-mentioned thermosetting resin composition.
  • thermosetting ester resin of the present invention When the thermosetting ester resin of the present invention is compounded with other thermosetting resins or thermosetting compounds and cured, the cured product exhibits excellent dielectric properties, and furthermore, a thermosetting resin composition with excellent heat resistance for printed wiring board applications is obtained. In particular, it can be suitably used for mobile applications, server applications, and the like, where a low dielectric tangent is strongly required.
  • thermosetting ester resin obtained in Example 1 is a GPC chart of the thermosetting ester resin obtained in Example 1.
  • 1 is an IR chart of the thermosetting ester resin obtained in Example 1.
  • the thermosetting ester resin of the present invention comprises a polyaryloxy unit and a polyarylcarbonyl unit.
  • the polyaryloxy unit essentially contains a reactive group-containing unit represented by formula (1), and may contain a monoaryloxy group.
  • the polyaryloxy unit is a structural unit derived from a raw material aromatic polyhydric hydroxy compound containing the aromatic polyhydric hydroxy compound represented by formula (11), and the polyarylcarbonyl unit is a structural unit derived from a raw material aromatic polyhydric carboxylic acid (aromatic polyhydric carboxylic acid halide).
  • aromatic polyhydric hydroxy compounds and aromatic monohydroxy compounds are sometimes collectively referred to simply as "aromatic hydroxy compounds”.
  • Aromatic polyhydric carboxylic acids or their acid halides and aromatic monocarboxylic acids or their acid halides are sometimes collectively referred to simply as “aromatic carboxylic acids or their acid halides”.
  • reactive group it refers to the reactive group represented by formula (2).
  • monoaralkyloxy groups may also be treated as monoaryloxy units (monoaryloxy groups).
  • thermosetting ester resin of the present invention exhibits high heat resistance while having a low dielectric constant and dielectric tangent when cured. Furthermore, since it has ester bonds in its structure, it can also be used suitably as a curing agent for epoxy resins. Furthermore, since it does not produce highly polar hydroxyl groups during curing, it is possible to lower the dielectric tangent and relative dielectric constant of the cured product. Since it contains many ester bonds inside the molecular chain that are reactive to epoxy groups, the cured product has a high crosslink density and high heat resistance (glass transition temperature: Tg).
  • thermosetting ester resin of the present invention must have a reactive group-containing unit represented by formula (1) as a polyaryloxy unit.
  • R1 independently represents a hydrocarbon group having 1 to 8 carbon atoms, and is preferably an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 8 carbon atoms, an aralkyl group having 7 to 8 carbon atoms, or an allyl group.
  • the alkyl group having 1 to 8 carbon atoms may be linear, branched, or cyclic, and examples thereof include, but are not limited to, methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, pentyl, isopentyl, neopentyl, cyclopentyl, hexyl, methylpentyl, dimethylbutane, cyclohexyl, and methylcyclohexyl groups.
  • aryl groups having 6 to 8 carbon atoms include, but are not limited to, phenyl, tolyl, xylyl, and ethylphenyl groups.
  • aralkyl groups having 7 to 8 carbon atoms include, but are not limited to, benzyl and ⁇ -methylbenzyl groups.
  • substituents from the viewpoints of availability and reactivity when cured, a phenyl group and a methyl group are preferred, and a methyl group is particularly preferred.
  • the substitution position of R1 may be any of the ortho, meta, and para positions relative to the oxy group, but the ortho position is preferred.
  • R2 independently represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and is preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an allyl group.
  • the alkyl group having 1 to 12 carbon atoms may be linear, branched, or cyclic, and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, methylbutyl, cyclopentyl, n-hexyl, methylpentyl, dimethylbutyl, cyclohexyl, n-heptyl, methylhexyl, dimethylpentyl, trimethylbutyl, ethylpentyl,
  • Examples of the alkyl groups include, but are not limited to, cycloheptyl, methylcyclohexyl, n-octyl, isooctyl, methylheptyl, dimethylhexyl, tri
  • Aryl groups having 6 to 12 carbon atoms include, but are not limited to, phenyl, tolyl, xylyl, ethylphenyl, styryl, n-propylphenyl, isopropylphenyl, mesityl, ethynylphenyl, naphthyl, and vinylnaphthyl groups.
  • Aralkyl groups having 7 to 12 carbon atoms include, but are not limited to, benzyl, ⁇ -methylbenzyl, dimethylbenzyl, trimethylbenzyl, naphthylmethyl, phenethyl, and 2-phenylisopropyl groups.
  • alkyl group examples include an indanyl group, a norbornyl group, a decahydronaphthyl group, a dicyclopentenyl group represented by the following formula (1a) or (1b), and a polycyclic structure group such as a cyclopentenyl group represented by the following formula (1c), but are not limited to these.
  • substitution position of R2 may be any of the ortho, meta, and para positions relative to the oxy group.
  • Y independently represents a bonding site with a polyarylcarbonyl unit or a reactive group represented by the following formula (2), and the reactive group accounts for 1 to 99 mol % of all Y, preferably 10 to 80 mol %, more preferably 15 to 70 mol %, and particularly preferably 40 to 60 mol %.
  • R represents a hydrogen atom or an alkyl or alkenyl group having 1 to 8 carbon atoms
  • i represents an integer of 0 to 2
  • n represents the number of repetitions, the average value of which is a number of 0 to 5.
  • R is a hydrogen atom or an alkyl or alkenyl group having 1 to 8 carbon atoms.
  • alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group.
  • alkenyl group include a vinyl group, a reactive group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, and an octenyl group.
  • R is preferably a hydrogen atom or a methyl group.
  • i is the number of substituents R1 and is an integer from 0 to 2, preferably 1 or 2, and more preferably 2.
  • n is the number of repetitions, and is a number equal to or greater than 0, with the average value (number average) being 0 to 5.
  • the average value (number average) being 0 to 5.
  • n is preferably 1.1 to 4.0, and more preferably 1.2 to 3.0.
  • the polyaryloxy unit may contain units other than the reactive group-containing unit represented by the above formula (1) as long as the object of the present invention is not hindered, and such units are preferably units represented by the above formula (3) and/or formula (4).
  • the reactive group-containing polyaryloxy unit represented by the above formula (1) accounts for preferably 20 mol % or more, more preferably 30 mol % or more, and even more preferably 50 mol % or more of the total amount of polyaryloxy units constituting the thermosetting ester resin of the present invention.
  • the total amount of the reactive group-containing polyaryloxy unit represented by formula (1) and the dicyclopentadienylene group-containing polyaryloxy unit represented by formula (3') is preferably 30 mol % or more, more preferably 50 mol % or more.
  • thermosetting ester resin of the present invention can contain, as the polyaryloxy unit, a unit represented by the following formula (3) in addition to the reactive group-containing unit represented by the above formula (1).
  • Ar1 independently represents an aromatic ring group of any one of a benzene ring, a naphthalene ring, a furan ring, and a biphenyl ring. These aromatic rings may consist of only a benzene ring, a naphthalene ring, a furan ring, or a biphenyl ring, or may have a substituent R6.
  • the substituent R6 is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 11 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an aryloxy group having 6 to 11 carbon atoms, or an aralkyloxy group having 7 to 12 carbon atoms.
  • Ar11 is a divalent hydrocarbon group having 1 to 10 carbon atoms or a divalent group represented by the following formula (3a), which represents a linking group of a novolak resin.
  • the divalent hydrocarbon group having 1 to 10 carbon atoms include a methylene group and a dicyclopentadienylene group.
  • m represents the number of repetitions, and the average value is from 1 to 5, preferably from 1.0 to 4.0, more preferably from 1.0 to 3.0, and even more preferably from 1.0 to 2.0.
  • r is the number of oxy groups and is 1 or 2.
  • R11 is independently a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms.
  • the hydrocarbon group having 1 to 8 carbon atoms include an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 8 carbon atoms.
  • a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 7 carbon atoms (more preferably 6 carbon atoms) is preferable, and a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is particularly preferable.
  • the alkyl group having 1 to 6 carbon atoms represents a linear, branched or cyclic alkyl group.
  • Examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a pentyl group, a hexyl group, and a cyclohexyl group.
  • a branched or cyclic alkyl group tends to provide higher heat resistance than a linear alkyl group.
  • the number of carbon atoms is preferably 1 to 4 in the case of a chain alkyl group, and is preferably 6 in the case of a cyclic alkyl group.
  • an isopropyl group, an isobutyl group, a t-butyl group, or a cyclohexyl group is preferable, and a t-butyl group or a cyclohexyl group is more preferable.
  • a methyl group is also preferable because it tends to improve flame retardancy.
  • Examples of the divalent group represented by formula (3a) include, for example, -CH 2 -Ph-CH 2 -, -CH 2 -Ph-Ph-CH 2 -, -CH 2 -Ph-CH 2 -Ph-CH 2 -, -CH 2 -Ph-C(CH 3 ) 2 -Ph-CH 2 -, -CH 2 -Ph-CH(CH 3 )-Ph-CH 2 -, -CH 2 -Ph-CH(C 6 H 5 )-Ph-CH 2 -, -CH 2 -Ph-Flu-Ph-CH 2 -, -CH 2 -Np-CH 2 -, -CH 2 -Np-Np-CH 2 -, -CH 2 -Np-CH 2 -Np-CH 2 - and -CH 2 -Np-Flu-Np-CH 2 - and the like.
  • aromatic rings may further have, as a substituent, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an aralkyloxy group having 7 to 12 carbon atoms.
  • the total number of carbon atoms is 6 to 50, and more preferably, the number of carbon atoms is 6 to 20.
  • Ph represents a phenylene group (-C 6 H 4 -)
  • Np represents a naphthylene group (-C 10 H 6 -)
  • Flu represents a fluorenyl group (-C 13 H 8 -)
  • Ph-Ph represents a biphenylene group.
  • thermosetting ester resin of the present invention can contain, as the polyaryloxy unit, a unit represented by the following formula (4) in addition to the reactive group-containing unit represented by formula (1).
  • the polyaryloxy unit represented by formula (4) is a generalized formula of units represented by the following formulas (4a) to (4h).
  • the monoaryloxy group represented by formula (6) is a generalization of the monoaryloxy groups (units with one oxy group) corresponding to formulas (4a) to (4h)
  • the polyarylcarbonyl unit represented by formula (7) is a generalization of the polyarylcarbonyl units (units with all oxy groups replaced with carbonyl groups) corresponding to formulas (4a) to (4h).
  • R3 has the same meaning as R3 in formula (4) above.
  • R6 is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 11 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an aryloxy group having 6 to 11 carbon atoms, or an aralkyloxy group having 7 to 12 carbon atoms.
  • p is an integer from 0 to 4
  • q is an integer from 0 to 6.
  • Ar1 represents an aromatic ring group of any one of a benzene ring, a naphthalene ring, a furan ring, and a biphenyl ring. These aromatic rings may consist of only a benzene ring, a naphthalene ring, a furan ring, or a biphenyl ring, or may have a substituent R6.
  • the substituent R6 is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 11 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an aryloxy group having 6 to 11 carbon atoms, or an aralkyloxy group having 7 to 12 carbon atoms.
  • Ar1 is preferably a phenylene group, a naphthylene group, or an aromatic ring group in which these are substituted with a methyl group or a 1-phenylethyl group.
  • the alkyl group having 1 to 10 carbon atoms may be linear, branched, or cyclic, and examples thereof include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, isopropyl, sec-butyl, t-butyl, isopentyl, neopentyl, t-pentyl, isohexyl, cyclopentyl, cyclohexyl, cycloheptyl, methylcyclohexyl, cyclooctyl, dimethylcyclohexyl, ethylcyclohexyl, trimethylcyclohexyl, and cyclodecyl.
  • the alkoxy group having 1 to 10 carbon atoms may be linear, branched, or cyclic, and examples thereof include methoxy, ethoxy, n-propoxy, n-butoxy, n-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, isopropoxy, sec-butoxy, t-butoxy, isopentyloxy, neopentyloxy, t-pentyloxy, isohexyloxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, methylcyclohexyloxy, cyclooctyloxy, dimethylcyclohexyloxy, ethylcyclohexyloxy, trimethylcyclohexyloxy, and cyclodecyloxy.
  • aryl or aryloxy groups having 6 to 11 carbon atoms include phenyl, tolyl, ethylphenyl, xylyl, propylphenyl, mesityl, naphthyl, methylnaphthyl, phenoxy, tolyloxy, ethylphenoxy, xylyloxy, propylphenoxy, mesityloxy, naphthyloxy, and methylnaphthyloxy groups.
  • aralkyl or aralkyloxy groups having 7 to 12 carbon atoms include benzyl, methylbenzyl, dimethylbenzyl, trimethylbenzyl, phenethyl, 1-phenylethyl, 2-phenylisopropyl, naphthylmethyl, benzyloxy, methylbenzyloxy, dimethylbenzyloxy, trimethylbenzyloxy, phenethyloxy, 1-phenylethyloxy, 2-phenylisopropyloxy, and naphthylmethyloxy groups.
  • R3 is a direct bond or a divalent group selected from a hydrocarbon group having 1 to 20 carbon atoms, -CO-, -O-, -S-, -SO 2 -, and -C(CF 3 ) 2 -.
  • hydrocarbon group having 1 to 20 carbon atoms examples include -CH2- , -CH(CH3)-, -C2H4- , -C( CH3 ) 2- , cyclohexylene group, methylcyclohexylene group, dimethylcyclohexylene group, methylisopropylcyclohexylene group, cyclohexylcyclohexylene group, cyclohexylidene group, methylcyclohexylidene group, dimethylcyclohexylidene group, trimethylcyclohexylidene group, tetramethylcyclohexylidene group, ethylcyclohexylidene group, isopropylcyclohexylidene group, t-butylcyclohexylidene group, phenylcyclohexylidene group, cyclohexylcyclohexylidene group, (methylcyclohexyl
  • Preferred R3 is a direct bond, -CH 2 -, -CH(CH 3 )-, -C(CH 3 ) 2 -, -CO-, -O-, -S-, -SO 2 -, a trimethylcyclohexylidene group, a cyclooctylidene group, a cyclododecylidene group, a bicyclohexanediyl group, a 9H-fluorene-9,9-diyl group, or a phenylmethylene group.
  • k is 0 or 1.
  • the thermosetting ester resin of the present invention may have a monoaryloxy group at the molecular chain terminal.
  • a group represented by formula (6) is preferable.
  • the amount of monoaryloxy groups used is preferably 1 mol % or more, more preferably 10 mol % or more, and even more preferably 20 mol % or more of the aromatic monohydroxy compound, which is the raw material from which the monoaryloxy unit represented by the above formula (6) is derived, relative to the total amount of aromatic hydroxy compounds used as raw materials.
  • Ar2 is an aromatic ring group similar to Ar1 in formula (4) above, and may have the same substituents, and preferable substituents are also the same.
  • R4 is a divalent group selected from a direct bond, -CH 2 -, -C(CH 3 ) 2 -, -CH(CH 3 )-, -CO-, -O-, -S-, -SO 2 -, and -C(CF 3 ) 2 -.
  • R14 is a divalent group selected from the group consisting of a direct bond, -CH 2 -, -C(CH 3 ) 2 -, -CH(CH 3 )-, and -C(CF 3 ) 2 -.
  • the group represented by formula (6) is a monoaralkyloxy group but is treated as a monoaryloxy group.
  • k is 0 or 1.
  • the polyarylcarbonyl unit is not particularly limited, but is preferably a unit represented by formula (7).
  • Ar3 is an aromatic ring group similar to Ar1 in formula (4), and may have the same substituents as Ar1 in formula (4), and the preferred substituents are also the same.
  • R5 has the same meaning as R3 in formula (4).
  • k is 0 or 1.
  • the aromatic hydroxy compound which is an essential raw material for synthesizing the above-mentioned thermosetting ester resin, is an aromatic polyhydroxy compound represented by formula (11).
  • R1, R2, i, and n are each defined as in formula (1) above.
  • the aromatic hydroxy resin represented by the general formula (11) can be obtained, for example, by reacting a substituent-containing phenol represented by the following general formula (5) with dicyclopentadiene in the presence of a Lewis acid such as boron trifluoride ether catalyst.
  • R1 and i have the same meanings as R1 and i in general formula (1), and the preferred substituents are also the same.
  • substituent-containing phenols examples include cresol, ethylphenol, propylphenol, isopropylphenol, n-butylphenol, t-butylphenol, pentylphenol, isopentylphenol, neopentylphenol, cyclopentylphenol, hexylphenol, (methylpentyl)phenol, (dimethylbutane)phenol, cyclohexylphenol, phenylphenol, tolylphenol, xylylphenol, benzylphenol, ⁇ -methylbenzylphenol, allylphenol, dimethylphenol, diethylphenol, dipropylphenol, diisopropylphenol, di(n-butyl)phenol, di(t-butyl)phenol, dipentylphenol, diisopentylphenol, dineopentylphenol, dicyclopentylphenol, dihexylphenol, dicyclohexylphenol, diphenylphenol, di
  • cresol, phenylphenol, benzylphenol, dimethylphenol, diphenylphenol, and dibenzylphenol are preferred, with cresol, phenylphenol, and dimethylphenol being particularly preferred.
  • substitution position is preferably the ortho position, and 2,6-disubstituted phenols having two substituents and represented by the following general formula (5-1) are more preferred.
  • R1 has the same definition as in the above general formula (2).
  • the above 2,6-disubstituted phenols include 2,6-dimethylphenol, 2,6-diethylphenol, 2,6-dipropylphenol, 2,6-diisopropylphenol, 2,6-di(n-butyl)phenol, 2,6-di(t-butyl)phenol, 2,6-dihexylphenol, 2,6-dicyclohexylphenol, 2,6-diphenylphenol, 2,6-ditolylphenol, 2,6-dibenzylphenol, 2,6-bis( ⁇ -methylbenzyl)phenol, 2-ethyl-6-methylphenol, 2-allyl-6-methylphenol, 2-tolyl-6-phenylphenol, etc. From the viewpoints of availability and reactivity when made into a cured product, 2,6-diphenylphenol and 2,6-dimethylphenol are preferred, and 2,6-dimethylphenol is particularly preferred.
  • the catalyst used in the above reaction is a Lewis acid, specifically boron trifluoride, boron trifluoride phenol complex, boron trifluoride ether complex, aluminum chloride, tin chloride, zinc chloride, iron chloride, etc., with boron trifluoride ether complex being preferred due to its ease of handling.
  • the amount of catalyst used is 0.001 to 20 parts by mass, preferably 0.1 to 15 parts by mass, and more preferably 0.5 to 12 parts by mass, per 100 parts by mass of dicyclopentadiene.
  • the ratio of phenols to dicyclopentadiene in the reaction is 0.08 to 0.80 moles of dicyclopentadiene per mole of phenols, preferably 0.09 to 0.60 moles, more preferably 0.10 to 0.50 moles, even more preferably 0.10 to 0.40 moles, and particularly preferably 0.10 to 0.20 moles.
  • This reaction is best carried out by placing the substituted phenol and catalyst in a reactor and then adding dicyclopentadiene dropwise over a period of 1 to 10 hours.
  • the reaction temperature is preferably 50 to 200°C, more preferably 100 to 180°C, and even more preferably 120 to 160°C.
  • the reaction time is preferably 1 to 10 hours, more preferably 3 to 10 hours, and even more preferably 4 to 8 hours.
  • an alkali such as sodium hydroxide, potassium hydroxide, or calcium hydroxide is added to deactivate the catalyst.
  • the desired aromatic hydroxy compound can then be obtained by adding and dissolving in a solvent such as aromatic hydrocarbons such as toluene or xylene, or ketones such as methyl ethyl ketone or methyl isobutyl ketone, washing with water, and recovering the solvent under reduced pressure. It is preferable to react as much of the dicyclopentadiene as possible, leaving a portion of the substituted phenols unreacted, preferably 10% or less, which are then recovered under reduced pressure.
  • solvents such as aromatic hydrocarbons, such as benzene, toluene, and xylene, halogenated hydrocarbons, such as chlorobenzene and dichlorobenzene, and ethers, such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether, may be used in the reaction.
  • the hydroxyl equivalent (g/eq.) of the aromatic hydroxy compound used as a raw material for producing the thermosetting ester resin of the present invention is preferably 150 to 500, more preferably 160 to 400, even more preferably 165 to 300, and most preferably 170 to 250.
  • the average molecular weight is preferably a weight average molecular weight (Mw) of 280 to 1,000, more preferably 300 to 700, and even more preferably 400 to 600, and preferably a number average molecular weight (Mn) of 230 to 1,000, more preferably 300 to 700, and even more preferably 400 to 600.
  • the softening point is preferably from 50 to 100°C, more preferably from 60 to 90°C.
  • aromatic polyhydric hydroxy compounds other than the aromatic hydroxy compound represented by the above formula (11) may be used in combination, as long as the purpose of the present invention is not hindered.
  • the aromatic polyhydric hydroxy compound that may be used in combination with the reactive group-containing aromatic hydroxy compound represented by formula (11) is not particularly limited, but is preferably an aromatic polyhydric hydroxy compound represented by the following formula (13) and/or formula (14).
  • Ar1, Ar11, m, and r are each defined as in formula (3) above.
  • Ar1, R3, and k are each defined as in formula (4) above.
  • Aromatic hydroxy compounds represented by formula (13) include, for example, novolac resins such as phenol novolac resin (e.g., Shownol BRG-555 (manufactured by Aica Kogyo Co., Ltd.)), cresol novolac resin (e.g., DC-5 (manufactured by Nippon Steel Chemical & Material Co., Ltd.)), xylenol novolac resin, biphenol novolac resin, aromatic modified phenol novolac resin, naphthol novolac resin, and the like, as well as reaction products of phenols and dicyclopentadiene (dicyclopentadiene-type phenol resin), reaction products of naphthols and dicyclopentadiene (dicyclopentadiene-type naphthol resin), and reaction products of phenols and terpenes.
  • novolac resins such as phenol novolac resin (e.g., Shownol BRG-555 (manufactured by
  • aralkyl novolak resins include reaction products of phenols and naphthols (terpene-type phenol resins), reaction products of naphthols and terpenes (terpene-type naphthol resins), condensates of phenols and/or naphthols and xylylene glycol (e.g., SN-160, SN-395, SN-485 (all manufactured by Nippon Steel Chemical & Material Co., Ltd.), etc.), condensates of phenols and/or naphthols and isopropenylacetophenone, reaction products of phenols and/or naphthols and divinylbenzene, and condensates of phenols and/or naphthols and biphenyl-based crosslinking agents (e.g., MEH-7851 (manufactured by UBE Co., Ltd.), etc.).
  • MEH-7851 manufactured by UBE Co., Ltd.
  • the aromatic polyhydroxy compound represented by formula (13) When the aromatic polyhydroxy compound represented by formula (13) is used in combination with a large amount of compounds having an average value of m exceeding 1.2, gelation may occur when the compound is dissolved in a solvent to synthesize a thermosetting ester resin. Therefore, when the aromatic polyhydroxy compound represented by formula (13) is used in combination, it is preferable to use one having an average value of m in the range of 1 to 2. Gelling can be prevented by appropriately adjusting the amount of the aromatic polyhydroxy compound represented by formula (14) used according to the value of m. For example, when m is 2, the amount used is preferably 20 mol% or less based on the total amount of the aromatic polyhydroxy compound used. In particular, an aromatic polyhydroxy compound represented by the following formula (13') is preferable. In the formula, m has the same meaning as m in the above formula (3).
  • aromatic dihydroxy compounds represented by formula (14) include dihydroxybenzenes such as catechol, resorcin, methylresorcin, hydroquinone, monomethylhydroquinone, dimethylhydroquinone, trimethylhydroquinone, mono-t-butylhydroquinone, and di-t-butylhydroquinone; naphthalenediols such as naphthalenediol, methylnaphthalenediol, and methylmethoxynaphthalenediol; biphenols such as biphenol, dimethylbiphenol, and tetramethylbiphenol; and bisphenols such as bisphenol A, bisphenol F, bisphenol C, bisphenol K, bisphenol Z, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol S, tetramethylbisphenol Z, dihydroxydiphenyl sulfide, 4,4'-thiobis(3-methyl-6-t-t
  • the aromatic monohydroxy compound to be used in combination is not particularly limited, but is preferably an aromatic monohydroxy compound represented by the following formula (16) (R14 is a direct bond).
  • an aromatic monoalcohol compound may be used instead of an aromatic monophenol compound.
  • the aromatic monoalcohol compound that may be used is not particularly limited, but is preferably an aromatic monoalcohol compound represented by the following formula (16) (wherein R14 is other than a direct bond).
  • Ar2, R4, R14, and k are each defined as in formula (6) above.
  • aromatic monohydroxy compounds represented by formula (16) include phenol, o-cresol, m-cresol, p-cresol, 3,5-xylenol, o-phenylphenol, p-phenylphenol, 2-benzylphenol, 4-benzylphenol, 4-( ⁇ -cumyl)phenol, octylphenol, ⁇ -naphthol, ⁇ -naphthol, etc., benzyl alcohol, tolylmethanol, dimethylbenzyl alcohol, biphenylmethanol, benzylbenzyl alcohol, naphthylmethanol, etc., with ⁇ -naphthol, ⁇ -naphthol, o-phenylphenol, p-phenylphenol, 4-( ⁇ -cumyl)phenol, benzyl alcohol, biphenylmethanol, and naphthylmethanol being preferred.
  • cured products using a thermosetting resin in combination with ⁇ -naphthol, ⁇ -naphthol, o-phenylphenol, p-phenylphenol, or 4-( ⁇ -cumyl)phenol as a curing agent have particularly low dielectric tangents.
  • thermosetting ester resin of the present invention is obtained by reacting an aromatic polyhydric hydroxy compound with an unsaturated group-containing carboxylic acid chloride or an unsaturated group-containing carboxylic acid anhydride and an aromatic polyhydric carboxylic acid or its acid halide.
  • the aromatic hydroxy compound represented by the above formula (11) is an essential component.
  • Examples of the unsaturated group-containing carboxylic acid anhydride or unsaturated group-containing carboxylic acid halide include vinyl group-containing acid anhydrides represented by general formula (12a) or acid halides represented by general formula (12b).
  • R is defined as in formula (2) above, and X represents a halogen.
  • Examples of the acid anhydride of formula (12a) containing a vinyl group include acrylic anhydride, methacrylic anhydride, etc., with methacrylic anhydride being preferred.
  • Examples of the acid halide of formula (12b) containing a vinyl group include acrylic acid chloride, methacrylic acid chloride, methacrylic acid bromide, etc., with methacrylic acid chloride and methacrylic acid bromide being preferred.
  • aromatic polycarboxylic acids or their acid halides examples include aromatic dicarboxylic acids or their halides represented by the following formula (17), and aromatic tricarboxylic acids or their halides such as trimesic acid and trimellitic acid.
  • Aromatic monocarboxylic acids or their acid halides may be used in combination. Chlorine or bromine is generally used as the halogen of the aromatic carboxylic acid halide used.
  • Ar3, R3, and k are defined the same as Ar3, R3, and k in the above formula (7), respectively.
  • aromatic dicarboxylic acids represented by the above formula (17) include phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4-biphenyldicarboxylic acid, 4,4'-methylenebisbenzoic acid, 4,4'-carbonylbisbenzoic acid, 4,4'-isopropylidenedibenzoic acid, and furandicarboxylic acid.
  • isophthalic acid chloride and terephthalic acid chloride are preferred from the viewpoint of the balance between solvent solubility and heat resistance.
  • aromatic monocarboxylic acid halides include halides of aromatic monocarboxylic acids represented by the following formula (18): When aromatic monocarboxylic acid halides are used in combination, part of the molecular chain terminals becomes an arylcarbonyloxy group.
  • Ar2, R4, and k are defined the same as Ar2, R4, and k in the above formula (6), respectively.
  • aromatic monocarboxylic acid represented by the formula (18) include benzoic acid, 1-naphthalenecarboxylic acid, 2-naphthalenecarboxylic acid, biphenylcarboxylic acid, and furancarboxylic acid.
  • the reaction between an aromatic polyhydric hydroxy compound, an unsaturated group-containing carboxylic anhydride or its acid halide, and an aromatic polycarboxylic acid or its acid halide can be carried out by reacting the aromatic polyhydric hydroxy compound in a solvent in the presence of a basic compound.
  • a basic compound it is preferable to charge the aromatic polyhydric hydroxy compound, the unsaturated group-containing carboxylic anhydride or its acid halide, and the aromatic polycarboxylic acid or its acid halide in a reactor, dissolve them, and then add the basic compound to carry out the reaction.
  • the aromatic polyhydric hydroxy compound may also be reacted in stages with the aromatic polycarboxylic acid or its acid halide, and the unsaturated group-containing carboxylic anhydride or its acid halide.
  • the ratio of the aromatic polyhydric hydroxy compound, the unsaturated group-containing carboxylic anhydride or acid halide, and the aromatic polyhydric carboxylic acid or its acid halide to be used is preferably 0.1 to 2.0 equivalents, more preferably 0.8 to 1.5 equivalents, of the total of the unsaturated group-containing carboxylic anhydride or acid halide and the aromatic polyhydric carboxylic acid or its acid halide, per 1 equivalent of the phenolic hydroxyl group of the aromatic polyhydric hydroxy compound.
  • the alkaline catalysts that can be used here include inorganic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate, and sodium carbonate, and organic bases such as triethylamine, diisopropylethylamine, dimethylaminopyridine, and pyridine, of which sodium hydroxide and potassium hydroxide are preferred due to their superior reactivity and cost.
  • inorganic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate, and sodium carbonate
  • organic bases such as triethylamine, diisopropylethylamine, dimethylaminopyridine, and pyridine, of which sodium hydroxide and potassium hydroxide are preferred due to their superior reactivity and cost.
  • the above reaction can be carried out by mixing an aromatic hydroxy compound with an aromatic carboxylic acid or its acid halide in the presence of an organic solvent and adding the above-mentioned alkaline catalyst.
  • the amount of alkaline catalyst added is preferably 0.9 to 2.0 moles per mole of phenolic hydroxyl group of the aromatic hydroxy compound.
  • the organic solvent used in the above reaction includes toluene, dichloromethane, chloroform, etc., with toluene being preferred from the viewpoints of cost, availability and ease of separation.
  • a hydrophobic organic solvent such as toluene
  • an aqueous solution of an inorganic base such as sodium hydroxide may separate, and therefore it is desirable to add a phase transfer catalyst such as tetra-n-butylammonium bromide (TBAB) in order to rapidly react with the phenolic resin dissolved in the organic solvent.
  • TBAB tetra-n-butylammonium bromide
  • reaction solution is neutralized and washed with water to obtain the desired resin.
  • the active ester equivalent of the thermosetting ester resin of the present invention is preferably 200 to 3000 g/eq., more preferably 500 to 2000 g/eq., and even more preferably 500 to 1500 g/eq. If it is less than this range, there is a risk of the dielectric properties being deteriorated, and if it is greater, there is a risk of the heat resistance and adhesiveness being reduced.
  • the active ester group refers to the aryloxycarbonyl group in the thermosetting ester resin.
  • the reaction temperature when producing the thermosetting ester resin of the present invention is usually 0 to 150°C, and preferably 10 to 50°C.
  • the reaction time is usually 0.5 to 10 hours, preferably 1 to 8 hours, and particularly preferably 1 to 5 hours. A reaction time of 0.5 hours or more allows the reaction to proceed sufficiently, and a reaction time of 10 hours or less makes it possible to keep the amount of by-products produced low.
  • polymerization inhibitors such as quinones, nitro compounds, nitrophenols, nitroso compounds, nitrone compounds, phenols, and oxygen may be used.
  • the solvent can be distilled off under reduced pressure with heating, or the product can be dissolved in a ketone solvent having 4 to 7 carbon atoms (e.g., methyl isobutyl ketone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone, etc.) or an aromatic hydrocarbon such as benzene, toluene, or xylene without being distilled off, and then washed with water, a lower alcohol such as methanol, or a mixture of these solvents, which have low solubility in the target product, to remove by-product salts and impurities.
  • a ketone solvent having 4 to 7 carbon atoms e.g., methyl isobutyl ketone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone, etc.
  • an aromatic hydrocarbon such as benzene, tol
  • thermosetting ester resin of the present invention is usually carried out while blowing an inert gas such as nitrogen into the system (in air or in liquid).
  • an inert gas such as nitrogen
  • the amount of inert gas blown in per unit time varies depending on the volume of the vessel used in the reaction, and it is preferable to adjust the amount of inert gas blown in per unit time so that the volume of the vessel can be replaced in, for example, 0.5 to 20 hours.
  • thermosetting resin composition of the present invention can be obtained.
  • thermosetting resin composition of the present invention contains the above-mentioned thermosetting ester resin as an essential component, and may contain other thermosetting resins.
  • some or all of the thermosetting resins are the thermosetting ester resin of the present invention, and the thermosetting resin of the present invention is preferably at least 30% by mass of the total thermosetting resins, more preferably 50% by mass or more, and even more preferably 75% by mass or more. If it is less than this, there is a risk of the dielectric properties being deteriorated.
  • any ordinary epoxy resin having two or more epoxy groups in the molecule can be used.
  • bisphenol A type epoxy resins bisphenol F type epoxy resins, tetramethylbisphenol F type epoxy resins, hydroquinone type epoxy resins, biphenyl type epoxy resins, bisphenol fluorene type epoxy resins, bisphenol S type epoxy resins, bisthioether type epoxy resins, resorcinol type epoxy resins, biphenyl aralkylphenol type epoxy resins, naphthalenediol type epoxy resins, phenol novolac type epoxy resins, styrenated phenol novolac type epoxy resins, cresol novolac type epoxy resins, alkyl novolac type epoxy resins, bisphenol novolac type epoxy resins,
  • epoxy resins that can be used include, but are not limited to, naphthol novolac type epoxy resins, ⁇ -naphthol aralkyl type epoxy resin
  • naphthalene diol type epoxy resins phenol novolac type epoxy resins, aromatic modified phenol novolac type epoxy resins, cresol novolac type epoxy resins, ⁇ -naphthol aralkyl type epoxy resins, dicyclopentadiene type epoxy resins, phosphorus-containing epoxy resins, and oxazolidone ring-containing epoxy resins.
  • thermosetting ester resin of the present invention one or more commonly used curing agents such as various phenolic resins, acid anhydrides, amines, hydrazides, and acidic polyesters may be used in combination as necessary.
  • the amount of the curing agent used in combination is preferably 70 mass% or less of the total curing agent, more preferably 50 mass% or less, and even more preferably 25 mass% or less. If the proportion of the curing agent used in combination is too high, the dielectric properties of the thermosetting resin composition may deteriorate.
  • the active hydrogen groups of the curing agent are preferably 0.2 to 1.5 moles per mole of epoxy groups of the epoxy resin, more preferably 0.3 to 1.4 moles, even more preferably 0.5 to 1.3 moles, and particularly preferably 0.8 to 1.2 moles. Outside this range, curing may be incomplete and good cured properties may not be obtained.
  • the active hydrogen groups are mixed in an approximately equimolar amount per epoxy group.
  • an acid anhydride-based curing agent is used in combination, 0.5 to 1.2 moles, preferably 0.6 to 1.0 moles, of acid anhydride groups are mixed in 1 mole of epoxy groups.
  • the amount used is in the range of 0.5 to 1.5 moles per mole of epoxy resin, and preferably 0.9 to 1.1 moles.
  • the active hydrogen group in the present invention refers to a functional group having active hydrogen reactive with an epoxy group (including a functional group having latent active hydrogen that generates active hydrogen by hydrolysis or the like, and a functional group that exhibits an equivalent curing action), and specifically includes an ester group, an acid anhydride group, a carboxyl group, an amino group, a phenolic hydroxyl group, and the like.
  • an acid anhydride group 1 mole of a carboxyl group or a phenolic hydroxyl group
  • an amino group (NH 2 ) is calculated as 2 moles.
  • the active hydrogen equivalent of the curing agent used can be determined by reacting a monoepoxy resin such as phenyl glycidyl ether, whose epoxy equivalent is known, with a curing agent, whose active hydrogen equivalent is unknown, and measuring the amount of the consumed monoepoxy resin.
  • a monoepoxy resin such as phenyl glycidyl ether, whose epoxy equivalent is known
  • curing agent whose active hydrogen equivalent is unknown
  • phenols hydroxynaphthalenes such as trihydroxynaphthalene, phosphorus-containing phenolic hardeners such as LC-950PM60 (manufactured by Shin-AT&C), phenol novolac resins, cresol novolac resins, aromatic modified phenol novolac resins, bisphenol A novolac resins, trishydroxyphenylmethane novolac resins such as Resitop TPM-100 (manufactured by Gun-ei Chemical Industry Co., Ltd.), naphthols, and/or bisphenols,
  • phenol compounds that can be used include phenol compounds called novolak phenol resins, such as condensates of phenols, naphthols, and/or bisphenols and xylylene glycol, condensates of phenols and/or naphthols and isopropenylacetophenone, reactants of phenols, naphthols, and/or bisphenols and dicyclopentadiene, and con
  • examples of phenols include phenol, cresol, xylenol, butylphenol, amylphenol, nonylphenol, butylmethylphenol, trimethylphenol, phenylphenol, etc.
  • examples of naphthols include 1-naphthol, 2-naphthol, etc., and other examples include the above-mentioned bisphenols.
  • aldehydes examples include formaldehyde, acetaldehyde, propylaldehyde, butyraldehyde, valeraldehyde, capronaldehyde, benzaldehyde, chloraldehyde, bromoaldehyde, glyoxal, malonaldehyde, succinaldehyde, glutaraldehyde, adipic aldehyde, pimeline aldehyde, sebacic aldehyde, acrolein, crotonaldehyde, salicylaldehyde, phthalaldehyde, hydroxybenzaldehyde, etc.
  • biphenyl-based crosslinking agents include bis(methylol)biphenyl, bis(methoxymethyl)biphenyl, bis(ethoxymethyl)biphenyl, and bis(chloromethyl)biphenyl.
  • acid anhydride curing agents include methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, phthalic anhydride, trimellitic anhydride, and methylnadic anhydride.
  • amine-based hardeners include amine-based compounds such as diethylenetriamine, triethylenetetramine, metaxylenediamine, isophoronediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiphenylether, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, dicyandiamide, and polyamidoamines, which are condensates of acids such as dimer acid and polyamines.
  • amine-based compounds such as diethylenetriamine, triethylenetetramine, metaxylenediamine, isophoronediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiphenylether, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, dicyandiamide, and polyamidoamines, which are condensates
  • hardeners include phosphine compounds such as triphenylphosphine, phosphonium salts such as tetraphenylphosphonium bromide, imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, and 1-cyanoethyl-2-methylimidazole, imidazole salts that are salts of imidazoles with trimellitic acid, isocyanuric acid, boron, or the like, quaternary ammonium salts such as trimethylammonium chloride, diazabicyclo compounds, salts of diazabicyclo compounds with phenols or phenol novolac resins, complex compounds of boron trifluoride with amines or ether compounds, aromatic phosphonium, or iodonium salts, etc.
  • phosphine compounds such as triphenylphosphine
  • phosphonium salts such as
  • Cure accelerators include, for example, amines, imidazoles, organic phosphines, Lewis acids, and organic peroxides. Specific examples include tertiary amines such as 1,8-diazabicyclo(4.4.0)undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, 4-dimethylaminopyridine, 2-(dimethylaminomethyl)phenol, and tris(dimethylaminomethyl)phenol; imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole, and 2-undecylimidazole; tributylphosphine, methyldiphenylphosphine, and triphenyl Examples of the
  • thermosetting resin composition of the present invention a known and commonly used epoxy resin curing accelerator can be used as necessary.
  • curing accelerators that can be used include urea compounds such as 3-phenyl-1,1-dimethylurea, 3-(3-methylphenyl)-1,1-dimethylurea, chlorophenylurea, 3-(3-chlorophenyl)-1,1-dimethylurea, and 3-(3,4-dichlorophenyl)-1,1-dimethylurea, as well as quaternary phosphonium salts such as TBP-DA, TBP-3PC, TBP-3S, and TPP-phthalic acid manufactured by Hokko Chemical Industry Co., Ltd., and metal compounds such as tin octylate.
  • These curing accelerators may be used alone or in combination of two or more types. Among these, 4-dimethylaminopyridine and imidazoles are preferred.
  • a curing accelerator When a curing accelerator is used, its amount may be appropriately selected depending on the purpose of use, but 0.01 to 15 parts by mass are used as necessary, with 0.02 to 10 parts by mass being preferred, 0.05 to 8 parts by mass being more preferred, and 0.1 to 5 parts by mass being even more preferred, per 100 parts by mass of the epoxy resin component in the thermosetting resin composition.
  • a curing accelerator By using a curing accelerator, it is possible to lower the curing temperature and shorten the curing time.
  • a maleimide compound can be used as necessary.
  • the maleimide compound that can be used is not particularly limited as long as it is a compound having one or more maleimide groups in one molecule.
  • maleimide compounds can be used alone or in combination of two or more.
  • the maleimide compounds represented by the following general formula (19) are preferred.
  • R7 independently represents an alkyl group or an aromatic group having 1 to 5 carbon atoms.
  • R8 independently represents a hydrogen atom or a methyl group.
  • a represents an integer of 0 to 4, with 0 or 1 being preferred.
  • b represents an integer of 0 to 3, with 0 or 1 being preferred.
  • c and d are 0 or 1.
  • e is the number of repetitions, the average value of which is from 1 to 10, preferably from 1 to 7, and more preferably from 1 to 5.
  • the resin composition of the present invention may contain one or more of various allyl ether compounds, if necessary. However, it is preferable that the thermosetting resin of the present invention accounts for 30% by mass, and more preferably 50% by mass or more. If it is less than this, the dielectric properties may deteriorate.
  • Allyl ether compounds that can be used in combination with the thermosetting resin of the present invention include, for example, allyl ether compounds obtained by allyl etherifying bisphenols such as bisphenol A, bisphenol F, bisphenol C, bisphenol K, bisphenol Z, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol S, tetramethylbisphenol Z, dihydroxydiphenyl sulfide, and 4,4'-thiobis(3-methyl-6-t-butylphenol); allyl ether compounds obtained by allyl etherifying dihydroxybenzenes such as catechol, resorcin, methylresorcin, hydroquinone, monomethylhydroquinone, dimethylhydroquinone, trimethylhydroquinone, mono-t-butylhydroquinone, and di-t-butylhydroquinone; allyl ether compounds obtained by allyl etherifying hydroxynaphthalen
  • novolac resins examples include phenol novolac resins such as phenol novolac resins (manufactured by Nippon Steel Chemical & Material Co., Ltd.), cresol novolac resins such as DC-5 (manufactured by Nippon Steel Chemical & Material Co., Ltd.), aromatic modified phenol novolac resins, bisphenol A novolac resins, trishydroxyphenylmethane type novolac resins such as Resitop TPM-100 (manufactured by Gun-ei Chemical Industry Co., Ltd.), naphthol novolac resins and other condensates of phenols, naphthols and/or bisphenols with aldehydes, and phenols such as SN-160, SN-395, and SN-485 (manufactured by Nippon Steel Chemical & Material Co., Ltd.).
  • phenol novolac resins such as phenol novolac resins (manufactured by Nippon Steel Chemical & Material Co.,
  • allyl ether compounds obtained by allylic etherifying polyhydric hydroxyl resins such as so-called novolak phenol resins, such as condensates of phenols, naphthols and/or bisphenols with xylylene glycol, condensates of phenols and/or naphthols with isopropenylacetophenone, reactants of phenols, naphthols and/or bisphenols with dicyclopentadiene, and condensates of phenols, naphthols and/or bisphenols with biphenyl-based crosslinking agents, and triallyl isocyanurate.
  • allyl ether compounds obtained by allylic etherifying bisphenols such as bisphenol A and bisphenol F, are preferred.
  • Thermosetting resin compositions can contain organic solvents or reactive diluents to adjust the viscosity.
  • organic solvents examples include amides such as N,N-dimethylformamide and N,N-dimethylacetamide, ethers such as ethylene glycol monomethyl ether, dimethoxydiethylene glycol, ethylene glycol diethyl ether, diethylene glycol diethyl ether, and triethylene glycol dimethyl ether, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, alcohols such as methanol, ethanol, 1-methoxy-2-propanol, 2-ethyl-1-hexanol, benzyl alcohol, ethylene glycol, propylene glycol, butyl diglycol, and pine oil, and vinegar.
  • amides such as N,N-dimethylformamide and N,N-dimethylacetamide
  • ethers such as ethylene glycol monomethyl ether, dimethoxydiethylene glycol, ethylene glycol diethyl
  • esters examples include acetates such as butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, cellosolve acetate, ethyl diglycol acetate, propylene glycol monomethyl ether acetate, carbitol acetate, and benzyl alcohol acetate; benzoate esters such as methyl benzoate and ethyl benzoate; cellosolves such as methyl cellosolve, cellosolve, and butyl cellosolve; carbitols such as methyl carbitol, carbitol, and butyl carbitol; aromatic hydrocarbons such as benzene, toluene, and xylene; dimethyl sulfoxide, acetonitrile, and N-methylpyrrolidone, but are not limited to these.
  • acetates such as butyl acetate, methoxybutyl acetate, methyl cellosolve a
  • Reactive diluents include, but are not limited to, monofunctional glycidyl ethers such as allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, and tolyl glycidyl ether; bifunctional glycidyl ethers such as resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, and propylene glycol diglycidyl ether; polyfunctional glycidyl ethers such as glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, tri
  • organic solvents or reactive diluents are preferably used alone or in a mixture of multiple types at 90% or less by weight as non-volatile matter, with the appropriate type and amount being selected as appropriate depending on the application.
  • polar solvents with a boiling point of 160°C or less, such as methyl ethyl ketone, acetone, and 1-methoxy-2-propanol, are preferred, with the amount of non-volatile matter being 40 to 80% by weight.
  • ketones, acetates, carbitols, aromatic hydrocarbons, dimethylformamide, dimethylacetamide, and N-methylpyrrolidone are preferred, with the amount of non-volatile matter being 30 to 60% by weight.
  • Thermosetting resin compositions may be blended with other thermosetting resins or thermoplastic resins to the extent that the properties are not impaired.
  • examples include, but are not limited to, phenolic resins, acrylic resins, petroleum resins, indene resins, coumarone-indene resins, phenoxy resins, polyurethane resins, polyester resins, polyamide resins, polyimide resins, polyamideimide resins, polyetherimide resins, polyphenylene ether resins, modified polyphenylene ether resins, polyethersulfone resins, polysulfone resins, polyetheretherketone resins, polyphenylene sulfide resins, and polyvinyl formal resins.
  • thermosetting resin composition of the present invention can be blended with vinyl resins and other thermosetting resins.
  • examples include vinyl ester resins, polyvinylbenzyl resins, polyallyl resins, epoxy resins, oxetane resins, maleimide resins, acrylate resins, polyester resins, polyurethane resins, polycyanate resins, phenolic resins, and benzoxazine resins.
  • thermoplastic resins such as polystyrene resin, polyphenylene ether resin, polyetherimide resin, polyethersulfone resin, PPS resin, polycyclopentadiene resin, and polycycloolefin resin
  • thermoplastic elastomers such as styrene-ethylene-propylene copolymer, styrene-ethylene-butylene copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, hydrogenated styrene-butadiene copolymer, and hydrogenated styrene-isoprene copolymer
  • rubbers such as polybutadiene and polyisoprene.
  • the type is not particularly limited.
  • the vinyl compounds may be any compounds that can form crosslinks and harden by reacting with the thermosetting resin of the present invention. It is more preferable that the polymerizable unsaturated hydrocarbon group is a carbon-carbon unsaturated double bond, and more preferable that the compound has two or more carbon-carbon unsaturated double bonds in the molecule.
  • the average number of carbon-carbon unsaturated double bonds (the number of vinyl groups (including substituted vinyl groups); also called the number of terminal double bonds) per molecule of vinyl compounds as curable resins varies depending on the Mw of the vinyl compounds, but is preferably, for example, 1 to 20, and more preferably 2 to 18. If the number of terminal double bonds is too low, it tends to be difficult to obtain sufficient heat resistance of the cured product. If the number of terminal double bonds is too high, the reactivity becomes too high, and problems such as reduced storage stability and reduced fluidity of the composition may occur.
  • vinyl compounds include trialkenyl isocyanurate compounds such as triallyl isocyanurate (TAIC), modified polyphenylene ethers (PPE) whose ends are modified with (meth)acryloyl or styryl groups, polyfunctional (meth)acrylate compounds having two or more (meth)acryloyl groups in the molecule, vinyl compounds having two or more vinyl groups in the molecule such as polybutadiene (polyfunctional vinyl compounds), and vinylbenzyl compounds such as styrene and divinylbenzene.
  • TAIC triallyl isocyanurate
  • PPE modified polyphenylene ethers
  • PPE polyphenylene ethers
  • vinyl compounds having two or more vinyl groups in the molecule such as polybutadiene (polyfunctional vinyl compounds)
  • vinylbenzyl compounds such as styrene and divinylbenzene.
  • compounds having two or more carbon-carbon double bonds in the molecule are preferred, and specific examples include TAIC, polyfunctional (meth)acrylate compounds, modified PPE resins, polyfunctional vinyl compounds, and divinylbenzene compounds. It is believed that the use of these compounds allows crosslinking to be more suitably formed by the curing reaction, and the heat resistance of the cured product of the resin composition can be further improved. These compounds may be used alone or in combination of two or more. Compounds having one carbon-carbon unsaturated double bond in the molecule may also be used in combination. Compounds having one carbon-carbon unsaturated double bond in the molecule include compounds having one vinyl group in the molecule (monovinyl compounds).
  • thermosetting resin composition various known flame retardants can be used to improve the flame retardancy of the resulting cured product.
  • flame retardants that can be used include halogen-based flame retardants, phosphorus-based flame retardants, nitrogen-based flame retardants, silicone-based flame retardants, inorganic flame retardants, and organic metal salt-based flame retardants. From an environmental perspective, halogen-free flame retardants are preferred, and phosphorus-based flame retardants are particularly preferred. These flame retardants may be used alone or in combination of two or more types.
  • inorganic and organic phosphorus compounds can be used as phosphorus-based flame retardants.
  • inorganic phosphorus compounds include red phosphorus, ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate, and inorganic nitrogen-containing phosphorus compounds such as phosphoric acid amide.
  • organic phosphorus compounds include general-purpose organic phosphorus compounds such as aliphatic phosphorus esters, phosphorus ester compounds, condensed phosphorus esters such as PX-200 (manufactured by Daihachi Chemical Industry Co., Ltd.), phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphorane compounds, and organic nitrogen-containing phosphorus compounds, as well as metal salts of phosphinic acid.
  • general-purpose organic phosphorus compounds such as aliphatic phosphorus esters, phosphorus ester compounds, condensed phosphorus esters such as PX-200 (manufactured by Daihachi Chemical Industry Co., Ltd.), phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphorane compounds, and organic nitrogen-containing phosphorus compounds, as well as metal salts of phosphinic acid.
  • organic phosphorus compounds include cyclic organic phosphorus compounds such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, and 10-(2,7-dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, and phosphorus-containing epoxy resins and phosphorus-containing curing agents, which are derivatives of these compounds reacted with compounds such as epoxy resins and phenolic resins.
  • cyclic organic phosphorus compounds such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, and 10-(2,7-dihydroxynaphthyl)-10H-9-oxa-10-pho
  • the amount of flame retardant to be added is appropriately selected depending on the type of phosphorus-based flame retardant, the components of the thermosetting resin composition, and the desired level of flame retardancy.
  • the phosphorus content in the organic components (excluding organic solvents) in the thermosetting resin composition is preferably 0.2 to 4 mass%, more preferably 0.4 to 3.5 mass%, and even more preferably 0.6 to 3 mass%. If the phosphorus content is low, it may be difficult to ensure flame retardancy, and if it is too high, it may have a negative effect on heat resistance.
  • a flame retardant assistant such as magnesium hydroxide may be used in combination.
  • fillers can be used in the thermosetting resin composition. Specifically, fused silica, crystalline silica, alumina, silicon nitride, aluminum hydroxide, boehmite, magnesium hydroxide, talc, mica, calcium carbonate, calcium silicate, calcium hydroxide, magnesium carbonate, barium carbonate, barium sulfate, boron nitride, carbon, carbon fiber, glass fiber, alumina fiber, silica alumina fiber, silicon carbide fiber, polyester fiber, cellulose fiber, aramid fiber, ceramic fiber, fine rubber particles, thermoplastic elastomer, pigments, etc.
  • the reason for using fillers in general is the effect of improving impact resistance.
  • metal hydroxides such as aluminum hydroxide, boehmite, and magnesium hydroxide
  • they act as flame retardant assistants and have the effect of improving flame retardancy.
  • the amount of these fillers is preferably 1 to 150 mass%, more preferably 10 to 70 mass%, of the entire thermosetting resin composition. If the amount is too large, the adhesiveness required for laminate use may decrease, and the cured product may become brittle and sufficient mechanical properties may not be obtained. If the amount blended is small, the effects of the filler blend, such as improving the impact resistance of the cured product, may not be achieved.
  • Thermosetting resin composition may further contain various additives such as silane coupling agents, antioxidants, release agents, defoamers, emulsifiers, thixotropic agents, smoothing agents, flame retardants, and pigments, if necessary.
  • additives such as silane coupling agents, antioxidants, release agents, defoamers, emulsifiers, thixotropic agents, smoothing agents, flame retardants, and pigments, if necessary.
  • the amount of these additives to be added is preferably in the range of 0.01 to 20% by mass of the thermosetting resin composition.
  • thermosetting resin composition of the present invention is obtained by uniformly mixing the above-mentioned components.
  • the thermosetting resin composition which is a mixture of a thermosetting resin, an epoxy resin, and various other materials as necessary, can be cured in the same manner as known thermosetting resin compositions to obtain a thermosetting resin cured product.
  • cured products include molded cured products such as laminates, cast products, molded products, adhesive layers, insulating layers, and films.
  • Methods for obtaining a cured product can be the same as known thermosetting resin compositions, and methods such as casting, injection, potting, dipping, drip coating, transfer molding, compression molding, etc., or laminating in the form of a resin sheet, resin-coated copper foil, prepreg, etc., and curing under heat and pressure to obtain a laminate are preferably used.
  • the method of curing a thermosetting resin composition varies depending on the components and amounts in the thermosetting resin composition, but the curing temperature is usually 80 to 300°C and the curing time is 10 to 360 minutes.
  • This heating is preferably performed in two stages: a first heating at 80 to 180°C for 10 to 90 minutes and a second heating at 120 to 200°C for 60 to 150 minutes.
  • Tg glass transition temperature
  • thermosetting resin composition When producing a resin sheet, a resin-coated copper foil, a prepreg, or other semi-cured resin product, the curing reaction of the thermosetting resin composition is usually allowed to proceed to an extent that the shape can be maintained by heating or the like.
  • the thermosetting resin composition contains a solvent, most of the solvent is usually removed by methods such as heating, decompression, and air drying, but 5% or less by weight of the solvent may remain in the semi-cured resin product.
  • Uncured or partially cured sheets of the thermosetting resin composition of the present invention can be suitably used, for example, as build-up films, bonding sheets, coverlay sheets, bump sheets for flip-chip bonders, and insulating layers or adhesive layers for substrates.
  • Thermosetting resin compositions can be used in a variety of fields, including as circuit board materials, sealing materials, casting materials, conductive pastes, adhesives, and insulating materials, and are particularly useful as insulating casting, lamination materials, and sealing materials in the electrical and electronic fields.
  • Examples of applications include printed wiring boards, flexible wiring boards, laminates for electrical and electronic circuits such as capacitors, resin-coated metal foils, adhesives such as film adhesives and liquid adhesives, semiconductor sealing materials, underfill materials, interchip fill materials for 3D-LSI, insulating materials for circuit boards, insulating sheets, prepregs, heat dissipation substrates, and resist inks, but are not limited to these.
  • it can be used as a printed wiring board material, insulating material for circuit boards, and adhesive film for build-up, where passive components such as capacitors and active components such as IC chips are embedded in the board, so to speak, as an insulating material for boards with built-in electronic components.
  • a printed wiring board material due to its characteristics such as high flame retardancy, high heat resistance, and solvent solubility, it is preferable to use it as a printed wiring board material, a thermosetting resin composition for flexible wiring boards, a material for circuit boards (laminates) such as an interlayer insulating material for build-up boards, and a semiconductor encapsulation material.
  • the filler used is preferably fibrous in terms of dimensional stability and bending strength, and glass cloth, glass mat, and glass roving cloth are more preferred.
  • Thermosetting resin composition can be impregnated into a fibrous reinforcing base material to produce a prepreg for use in printed wiring boards, etc.
  • fibrous reinforcing base materials include, but are not limited to, inorganic fibers such as glass, and woven or nonwoven fabrics of organic fibers such as polyester resin, polyamine resin, polyacrylic resin, polyimide resin, and aromatic polyamide resin.
  • the method of producing a prepreg from a thermosetting resin composition is not particularly limited, and for example, the thermosetting resin composition is adjusted to an appropriate viscosity with an organic solvent to produce a resin varnish, and the resin varnish is impregnated into the fibrous reinforcing substrate, which is then heated and dried to semi-cure (B-stage) the resin component.
  • the heating temperature is preferably 50 to 200°C, and more preferably 100 to 170°C, depending on the type of organic solvent used.
  • the heating time is adjusted depending on the type of organic solvent used and the curing property of the prepreg, and is preferably 1 to 40 minutes, and more preferably 3 to 20 minutes.
  • the mass ratio of the thermosetting resin composition and the reinforcing substrate used is not particularly limited, but it is usually preferable to adjust it so that the resin content in the prepreg is 20 to 80 mass%.
  • thermosetting resin composition of the present invention can be used by forming it into a sheet or film. In this case, it can be made into a sheet or film by using a conventionally known method.
  • the method for producing a resin sheet is not particularly limited, but for example, (1) An extrusion molding method in which a thermosetting resin composition is kneaded in an extruder, extruded, and molded into a sheet using a T-die, a circular die, or the like; (2) A casting molding method in which a thermosetting resin composition is dissolved or dispersed in a solvent such as an organic solvent, and then cast into a sheet shape; (3) Other conventionally known sheet forming methods and the like can be mentioned.
  • the thickness ( ⁇ m) of the resin sheet is not particularly limited, but is preferably 10 to 300, more preferably 25 to 200, and even more preferably 40 to 180.
  • the thickness of the resin sheet when used in the build-up method is particularly preferably 40 to 90 ⁇ m. If the thickness is 10 ⁇ m or more, insulation can be obtained, and if it is 300 ⁇ m or less, the distance of the circuit between the electrodes will not be longer than necessary.
  • the content of the solvent in the resin sheet is not particularly limited, but is preferably 0.01 to 5 mass% with respect to the entire thermosetting resin composition.
  • the content of the solvent in the film is 0.01 mass% or more with respect to the entire thermosetting resin composition, adhesion and adhesiveness are easily obtained when laminated to a circuit board, and if it is 5 mass% or less, flatness after heat curing is easily obtained.
  • a more specific method for producing an adhesive sheet is to apply a varnish-like thermosetting resin composition containing the organic solvent onto a supporting base film that is not soluble in organic solvents using a coater such as a reverse roll coater, comma coater or die coater, and then heat and dry to bring the resin components to the B stage. If necessary, another supporting base film can be placed on the applied surface (adhesive layer) as a protective film, and then dried to obtain an adhesive sheet with release layers on both sides of the adhesive layer.
  • a coater such as a reverse roll coater, comma coater or die coater
  • the supporting base film examples include metal foils such as copper foil, polyolefin films such as polyethylene film and polypropylene film, polyester films such as polyethylene terephthalate film, polycarbonate film, silicone film, polyimide film, etc.
  • polyethylene terephthalate film is preferred because it is free of defects, has excellent dimensional accuracy, and is cost-effective.
  • Metal foils, especially copper foil, are preferred because they are easy to form into multilayer laminates.
  • the thickness of the supporting base film is preferably 10 to 150 ⁇ m, more preferably 25 to 50 ⁇ m, as it has the strength to serve as a support and is less likely to cause lamination defects.
  • the thickness of the protective film is not particularly limited, but is generally 5 to 50 ⁇ m. In order to easily peel off the molded adhesive sheet, it is preferable to perform a surface treatment with a release agent beforehand.
  • the thickness of the applied resin varnish after drying is preferably 5 to 200 ⁇ m, and more preferably 5 to 100 ⁇ m.
  • the heating temperature is preferably 50 to 200°C, more preferably 100 to 170°C, depending on the type of organic solvent used.
  • the heating time is adjusted depending on the type of organic solvent used and the curing properties of the prepreg, and is preferably 1 to 40 minutes, more preferably 3 to 20 minutes.
  • the resin sheet obtained in this manner is usually an insulating adhesive sheet having insulating properties, but a conductive adhesive sheet can also be obtained by mixing conductive metal or metal-coated fine particles into the thermosetting resin composition.
  • the supporting base film is peeled off after lamination onto the circuit board or after heat curing to form an insulating layer. Peeling off the supporting base film after heat curing the adhesive sheet can prevent the adhesion of dirt and the like during the curing process.
  • the insulating adhesive sheet is also an insulating sheet.
  • a resin sheet is produced by forming a multifunctional vinyl resin composition into a sheet shape on a support film by a coating method or the like, and then heating to dry or semi-cure it.
  • This resin sheet is overlaid on a substrate (first substrate), the support film is peeled off from the resin sheet, and another substrate (second substrate) is overlaid. That is, the first substrate, the resin sheet (multifunctional vinyl resin composition), and the second substrate are laminated in this order. Then, by heating and curing, the first substrate and the second substrate are bonded via the cured product of the multifunctional vinyl resin composition.
  • the resin-attached metal foil obtained from the thermosetting resin composition of the present invention will be described.
  • the metal foil a single metal foil, an alloy foil, or a composite metal foil of copper, aluminum, brass, nickel, etc. can be used. It is preferable to use a metal foil with a thickness of 9 to 70 ⁇ m.
  • the method for producing the resin-attached metal foil from the thermosetting resin composition and metal foil of the present invention is no particular limitation on the method for producing the resin-attached metal foil from the thermosetting resin composition and metal foil of the present invention.
  • the resin-attached metal foil can be obtained by applying a resin varnish obtained by adjusting the viscosity of the thermosetting resin composition with a solvent to one side of the metal foil using a roll coater or the like, and then heating and drying the resin component to semi-cure (B-stage) and form a resin layer.
  • a resin varnish obtained by adjusting the viscosity of the thermosetting resin composition with a solvent
  • the resin component to semi-cure (B-stage) and form a resin layer.
  • it can be heated and dried at 100 to 200°C for 1 to 40 minutes.
  • it is preferable to form the resin portion of the resin-attached metal foil to a thickness of 5 to 110 ⁇ m.
  • a laminate hardening method generally used in manufacturing printed wiring boards can be used, but is not limited to this.
  • one or more prepregs are laminated and metal foil is placed on one or both sides to form a laminate, which is then pressurized and heated to harden and integrate the prepregs, thereby obtaining a laminate.
  • the metal foil used here can be a single, alloy, or composite metal foil of copper, aluminum, brass, nickel, etc.
  • the conditions for heating and pressing the laminate may be adjusted appropriately to the conditions under which the thermosetting resin composition cures, but if the pressure is too low, air bubbles may remain inside the resulting laminate, which may reduce the electrical properties, so it is preferable to pressurize under conditions that satisfy moldability.
  • the heating temperature is preferably 160 to 250°C, more preferably 170 to 220°C.
  • the pressure is preferably 0.5 to 10 MPa, more preferably 1 to 5 MPa.
  • the heating and pressing time is preferably 10 minutes to 4 hours, more preferably 40 minutes to 3 hours. If the heating temperature is low, the curing reaction may not proceed sufficiently, and if the pressure is high, thermal decomposition of the cured product may occur.
  • the pressure is low, air bubbles may remain inside the resulting laminate, which may reduce the electrical properties, and if the pressure is high, the resin may flow before curing, and a laminate of the desired thickness may not be obtained. If the heating and pressing time is short, the curing reaction may not proceed sufficiently, and if it is long, thermal decomposition of the cured product may occur.
  • a multilayer board can be made using the single-layer laminate obtained in this way as the inner layer material.
  • a circuit is formed on the laminate using an additive method or subtractive method, and the surface of the formed circuit is blackened by treating it with an acid solution to obtain the inner layer material.
  • An insulating layer is formed on one or both circuit-forming surfaces of this inner layer material using prepreg, resin sheet, insulating adhesive sheet, or resin-coated metal foil, and a conductor layer is formed on the surface of the insulating layer to form a multilayer board.
  • one or more prepreg sheets are placed on the circuit-forming surface of the inner layer material, and metal foil is placed on the outside to form a laminate.
  • This laminate is heated and pressurized to form an integral body, forming the cured prepreg as an insulating layer and the outer metal foil as a conductor layer.
  • the metal foil used here can be the same as that used for the laminate used as the inner layer material. Heat and pressure molding can be performed under the same conditions as for molding the inner layer material.
  • the surface of the multilayer laminate thus formed can be further subjected to via hole formation and circuit formation by additive or subtractive methods to form a printed wiring board. By repeating the above process using this printed wiring board as the inner layer material, a multilayer board with more layers can be formed.
  • an insulating adhesive sheet is placed on the circuit formation surfaces of multiple inner layer materials to form a laminate.
  • an insulating adhesive sheet is placed between the circuit formation surface of the inner layer material and a metal foil to form a laminate.
  • This laminate is then heated and pressurized to form an integral molding, thereby forming the cured insulating adhesive sheet as an insulating layer and forming a multi-layered inner layer material.
  • the cured insulating adhesive sheet is formed as an insulating layer between the inner layer material and the metal foil that is the conductor layer.
  • the same metal foil as that used in the laminate used as the inner layer material can be used.
  • the heating and pressurizing molding can be carried out under the same conditions as those for molding the inner layer material.
  • thermosetting resin composition When forming an insulating layer by applying a thermosetting resin composition to a laminate, the thermosetting resin composition is applied to a thickness of preferably 5 to 100 ⁇ m, and then heated and dried at 100 to 200°C, preferably 150 to 200°C, for 1 to 120 minutes, preferably 30 to 90 minutes, to form a sheet. This is generally formed by a method called the casting method.
  • the thickness after drying is preferably 5 to 150 ⁇ m, preferably 5 to 80 ⁇ m.
  • the viscosity of the thermosetting resin composition is preferably 10 to 40,000 mPa ⁇ s at 25°C, and more preferably 200 to 30,000 mPa ⁇ s, because a sufficient film thickness is obtained and uneven coating or streaks are unlikely to occur.
  • a printed wiring board can be formed by forming via holes and circuits on the surface of the multilayer laminate formed in this way using an additive method or a subtractive method. By repeating the above method using this printed wiring board as an inner layer material, a further multilayer laminate can be formed.
  • thermosetting resin composition of the present invention can be used to produce sealing materials suitable for tape-shaped semiconductor chips, potting-type liquid sealing, underfill, and semiconductor interlayer insulating films.
  • semiconductor package molding can be achieved by casting the thermosetting resin composition or molding it using a transfer molding machine or injection molding machine, and then heating it at 50 to 200°C for 2 to 10 hours to obtain a molded product.
  • thermosetting resin composition for use as a semiconductor encapsulation material
  • the thermosetting resin composition may be premixed with compounding agents such as inorganic fillers, and additives such as coupling agents and mold release agents, which are added as needed, and then melt-mixed thoroughly until homogeneous using an extruder, kneader, rolls, etc.
  • silica is usually used as the inorganic filler, and in this case, it is preferable to mix the inorganic filler in the thermosetting resin composition in a proportion of 70 to 95 mass %.
  • thermosetting resin composition thus obtained When used as a tape-shaped sealant, it can be heated to produce a semi-cured sheet, which is then turned into a sealant tape, which is then placed on a semiconductor chip, heated to 100-150°C to soften and mold, and then completely cured at 170-250°C.
  • thermosetting resin composition When used as a potting-type liquid sealant, the obtained thermosetting resin composition can be dissolved in a solvent as necessary, applied to a semiconductor chip or electronic component, and directly cured.
  • thermosetting resin composition of the present invention can also be used as a resist ink.
  • a vinyl monomer having an ethylenically unsaturated double bond and a cationic polymerization catalyst as a curing agent are blended with the thermosetting resin composition, and a pigment, talc, and a filler are further added to form a resist ink composition, which is then applied to a printed circuit board by screen printing to form a cured resist ink.
  • the curing temperature in this case is preferably in the range of about 20 to 250°C.
  • thermosetting resin composition was prepared, and the laminate and cured product were evaluated after heat curing. As a result, it was found that the cured product exhibited excellent low dielectric properties, and furthermore, a thermosetting resin composition with excellent heat resistance for use in printed wiring boards was provided.
  • Hydroxyl equivalent The measurement was carried out in accordance with JIS K0070 standard, and the unit was expressed as "g/eq.” Unless otherwise specified, the hydroxyl group equivalent of an aromatic polyhydric hydroxy compound means the phenolic hydroxyl group equivalent.
  • Softening point The softening point was measured in accordance with the ring and ball method of JIS K7234. Specifically, an automatic softening point apparatus (ASP-MG4, manufactured by Meitec Corporation) was used.
  • ASP-MG4 automatic softening point apparatus
  • Dielectric constant and dielectric loss tangent The dielectric constant and the dielectric loss tangent at a frequency of 1 GHz were evaluated by a capacitance method using a material analyzer (manufactured by AGILENT Technologies) in accordance with IPC-TM-650 2.5.5.9.
  • Glass transition temperature (Tg) In accordance with IPC-TM-650 2.4.25.c, the DSC Tgm (the intermediate temperature of the displacement curve with respect to the tangent line between the glassy state and the rubbery state) was measured using a differential scanning calorimeter (Hitachi High-Tech Science Corporation, EXSTAR6000 DSC6200) at a temperature rise rate of 20°C/min.
  • GPC Gel Permeation Chromatography
  • a column (TSKgelG4000H XL , TSKgelG3000H XL , TSKgelG2000H XL , manufactured by Tosoh Corporation) was used in series in the main body (HLC-8220GPC, manufactured by Tosoh Corporation), and the column temperature was set to 40 ° C.
  • Tetrahydrofuran (THF) was used as the eluent, the flow rate was set to 1 mL / min, and a differential refractive index detector was used as the detector.
  • the measurement sample was 50 ⁇ L of a sample obtained by dissolving 0.1 g of sample in 10 mL of THF and filtering through a microfilter.
  • Mw and Mn were calculated by conversion from the calibration curve obtained from standard polystyrene (PStQuick Kit-H, manufactured by Tosoh Corporation).
  • Data processing was performed using GPC-8020 model II version 6.00 manufactured by Tosoh Corporation.
  • IR The absorbance was measured at wave numbers of 650 to 4000 cm ⁇ 1 using a Fourier transform infrared spectrophotometer (Spectrum One FT-IR Spectrometer 1760X, manufactured by Perkin Elmer Precisly) and a diamond ATR.
  • Spectrum One FT-IR Spectrometer 1760X manufactured by Perkin Elmer Precisly
  • PH1 Aromatic hydroxy compound obtained in Synthesis Example 1
  • PH2 Aromatic hydroxy compound obtained in Synthesis Example 2
  • PH3 1-naphthol
  • PH4 Biphenyl aralkyl type polyhydric hydroxy resin (MEH-7851, manufactured by Meiwa Kasei Co., Ltd., phenolic hydroxyl group equivalent: 223)
  • E1 Phenol-dicyclopentadiene type epoxy resin (Kokuto Chemical Co., Ltd., KDCP-130, epoxy equivalent 254, softening point 72°C)
  • Synthesis Example 1 A reaction apparatus consisting of a separable glass flask equipped with a stirrer, a thermometer, a nitrogen inlet tube, a dropping funnel, and a cooling tube was charged with 2,6-xylenol (structural formula below). 500 parts of 47% BF3 ether complex and 7.3 parts of 47% BF3 were charged and heated to 100°C with stirring. While maintaining the temperature, dicyclopentadiene (structural formula below) 67.6 parts (0.12 times the moles relative to 2,6-xylenol) were added dropwise over 1 hour. The mixture was further reacted at a temperature of 115 to 125°C for 4 hours, and 11 parts of calcium hydroxide were added.
  • the aromatic hydroxy compound (PH1) thus obtained had a hydroxyl equivalent of 195 and a softening point of 73° C.
  • Synthesis Example 2 In a reaction apparatus similar to that of Synthesis Example 1, 400 parts of phenol and 7.5 parts of 47% BF3 ether complex were charged and heated to 70°C while stirring. While maintaining the temperature, 70.2 parts of dicyclopentadiene were dropped over 2 hours. The mixture was further reacted at a temperature of 125 to 135°C for 4 hours, and 11.7 parts of calcium hydroxide were added. Furthermore, 20 parts of a 10% aqueous oxalic acid solution were added. After that, the mixture was heated to 160°C for dehydration, and then heated to 200°C under a reduced pressure of 5 mmHg to evaporate and remove the unreacted raw materials.
  • Example 1 A reaction apparatus equipped with a stirrer, a thermometer, a nitrogen inlet, a dropping funnel, and a cooling tube was charged with 100 parts of the reactive group-containing aromatic hydroxy compound (PH1) obtained in Synthesis Example 1, 1.7 parts of tetra-n-butylammonium bromide (TBAB), 20.8 parts of isophthalic acid chloride (B1) as an aromatic carboxylic acid halide (0.20 equivalents relative to the hydroxyl group equivalent of PH1), 400 parts of toluene (TL) were added and heated to 50° C. to dissolve. While controlling the temperature in the system to 20° C.
  • TBAB tetra-n-butylammonium bromide
  • B1 isophthalic acid chloride
  • TL toluene
  • thermosetting ester resin (A1) The active ester equivalent of the obtained thermosetting ester resin (A1) calculated from the amount of the raw materials was 660.
  • the reactive groups in all Y in the general formula (1) were 60 mol %.
  • the GPC and FT-IR of the obtained thermosetting ester resin (A1) are shown in FIG. 1 and FIG. 2, respectively.
  • Example 2 A reaction apparatus equipped with a stirrer, a thermometer, a nitrogen inlet, a dropping funnel, and a cooling tube was charged with 100 parts of the aromatic hydroxy compound (PH1) obtained in Synthesis Example 1, 1.7 parts of tetra-n-butylammonium bromide (TBAB), 10.4 parts of isophthalic acid chloride (B1) as an aromatic carboxylic acid halide (0.10 equivalents relative to the hydroxyl group equivalent of PH1), 400 parts of toluene (TL) were added and heated to 50° C. to dissolve. While controlling the temperature in the system to 20° C.
  • TBAB tetra-n-butylammonium bromide
  • B1 isophthalic acid chloride
  • TL toluene
  • Example 3 The same operation as in Example 2 was carried out except that the amount of isophthalic acid chloride (B1) was changed to 20.8 parts and the amount of methacrylic acid chloride was changed to 38.6 parts, to obtain 213 parts of a thermosetting ester resin (A3).
  • the active ester equivalent of the obtained resin (A3) calculated from the amount of the raw materials was 660.
  • the reactive group in the total X in the general formula (1) was 60 mol %.
  • Example 4 The same operation as in Example 2 was carried out, except that the amount of isophthalic acid chloride (B1) was changed to 26.0 parts and the amount of methacrylic acid chloride was changed to 32.2 parts, to obtain 212 parts of a thermosetting ester resin (A4).
  • the active ester equivalent of the obtained resin (A4) calculated from the amount of the raw materials charged was 530.
  • the reactive group in all X in the general formula (1) was 50 mol %.
  • Example 5 The same operation as in Example 2 was carried out, except that the isophthalic acid chloride (B1) was replaced with 20.8 parts of terephthalic acid chloride (B2) and 38.6 parts of methacrylic acid chloride, to obtain 213 parts of a thermosetting ester resin (A5).
  • the active ester equivalent of the obtained resin (A5) calculated from the amount of the raw materials charged was 660.
  • the reactive groups in all X in the general formula (1) were 60 mol %.
  • Example 6 The same operation as in Example 2 was carried out, except that 7.4 parts of 1-naphthol (PH3) was added per 100 parts of aromatic hydroxy compound (PH1), and 1.8 parts of tetra n-butylammonium bromide (TBAB), 22.9 parts of isophthalic acid chloride (B1), 42.5 parts of methacrylic acid chloride, and 430 parts of toluene were used, to obtain 231 parts of thermosetting ester resin (A6).
  • the active ester equivalent of the obtained resin (A6) calculated from the amount of the raw materials charged was 650.
  • the reactive group in all X in general formula (1) is 60 mol%.
  • Example 7 The same operation as in Example 2 was carried out, except that 14.8 parts of 1-naphthol (PH3) was added per 100 parts of aromatic hydroxy compound (PH1), 2.0 parts of tetra n-butylammonium bromide (TBAB), 25.0 parts of isophthalic acid chloride (B1), 46.3 parts of methacrylic acid chloride, and 460 parts of toluene were used, to obtain 248 parts of thermosetting ester resin (A7).
  • the active ester equivalent of the obtained resin (A7) calculated from the amount of the raw materials charged was 640.
  • the reactive group in all X in general formula (1) is 60 mol%.
  • Example 8 100 parts of aromatic hydroxy compound (PH2) was added to 100 parts of aromatic hydroxy compound (PH1), 3.5 parts of tetra n-butylammonium bromide (TBAB), 43.8 parts of isophthalic acid chloride (B1) (0.20 equivalents relative to the hydroxyl group equivalents of PH1 and PH2), and 81.1 parts of methacrylic acid chloride (0.72 equivalents relative to the hydroxyl group equivalents of PH1 and PH2), except that toluene was changed to 800 parts, the same operation as in Example 2 was performed to obtain 432 parts of thermosetting ester resin (A8). For the obtained resin (A8), the active ester equivalent calculated from the amount of raw material charged was 630.
  • the reactive group in the total X of general formula (1) is 60 mol%.
  • Example 9 100 parts of aromatic hydroxy compound (PH4) was added to 100 parts of aromatic hydroxy compound (PH1), 3.1 parts of tetra n-butylammonium bromide (TBAB), 39.0 parts of isophthalic acid chloride (B1) (0.20 equivalents relative to the hydroxyl group equivalents of PH1 and PH2), and 72.3 parts of methacrylic acid chloride (0.72 equivalents relative to the hydroxyl group equivalents of PH1 and PH2), except that toluene was changed to 800 parts, the same operation as in Example 2 was performed to obtain 420 parts of thermosetting ester resin (A9). For the obtained resin (A9), the active ester equivalent calculated from the amount of raw material charged was 690.
  • the reactive group in the total X of general formula (1) is 60 mol%.
  • thermosetting ester resin (A10) was obtained by carrying out the same operation as in Example 1, except that the aromatic hydroxy compound (PH1) was 100 parts, 1-naphthol (PH3) was 24.4 parts, tetra n-butylammonium bromide (TBAB) was 1.9 parts, isophthalic acid chloride (B1) was 69.2 parts, 20% aqueous sodium hydroxide solution (20% NaOH) was 136 parts, and toluene (TL) was 480 parts, and methacrylic anhydride was not added. Note that, since methacrylic anhydride is not added, the reaction proceeds even in a low concentration NaOH aqueous solution.
  • the active ester equivalent of the obtained resin (A10) was 248, calculated from the amounts of the raw materials charged.
  • thermosetting ester resin (A11) was obtained by carrying out the same operation as in Example 1, except that the aromatic hydroxy compound (PH2) was 100 parts, 1-naphthol (PH3) was 26.9 parts, tetra n-butylammonium bromide (TBAB) was 2.1 parts, isophthalic acid chloride (B1) was 76.3 parts, 20% aqueous sodium hydroxide solution (20% NaOH) was 150 parts, and toluene (TL) was 510 parts, and methacrylic anhydride was not added. Since methacrylic anhydride is not added, the reaction proceeds even in a low-concentration aqueous NaOH solution.
  • the active ester equivalent of the obtained resin (A11) was 235, calculated from the amounts of the raw materials charged.
  • Example 10 In terms of solid content, 100 parts of the thermosetting ester resin (A1) obtained in Example 1, 100 parts of the vinyl resin (E), and 1.0 part of PO as a curing accelerator were mixed and dissolved in toluene to obtain a thermosetting resin composition varnish so that the non-volatile content was 50%.
  • the obtained thermosetting resin composition varnish was impregnated into glass cloth (manufactured by Nitto Boseki Co., Ltd., WEA 7628 XS13, 0.18 mm thick). The impregnated glass cloth was dried in a hot air circulating oven at 150 ° C for 5 minutes to obtain a prepreg.
  • the obtained prepreg was loosened and sieved to obtain prepreg powder with a 100 mesh pass.
  • the obtained prepreg powder was placed in a fluororesin mold and vacuum pressed at 2 MPa under temperature conditions of 130°C x 15 minutes + 210°C x 80 minutes to obtain a test piece of 50 mm square x 2 mm thick.
  • the results of the relative dielectric constant and dielectric tangent of the test piece are shown in Table 2.
  • Example 11 to 19 Comparative Examples 1 to 6
  • the components were mixed in the amounts (parts) shown in Table 1, and the same operations as in Example 10 were carried out to obtain prepregs and test pieces.
  • the results of the relative dielectric constant and dielectric loss tangent of the test pieces obtained are shown in Table 2.
  • the amounts of A1 to A11, etc., are shown as solid content converted values.
  • thermosetting ester resin and resin composition of the present invention are applicable in various fields such as coating materials, civil engineering adhesion, casting, electric and electronic materials, film materials, etc. In particular, they are useful for printed wiring boards, which are one type of electric and electronic material.

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Abstract

L'invention concerne : une composition de résine thermodurcissable qui présente d'excellentes caractéristiques de faible constante diélectrique et qui présente une excellente résistance à la chaleur dans des applications telles que des cartes de circuit imprimé ; et une résine thermodurcissable qui permet d'obtenir la composition de résine thermodurcissable. La résine thermodurcissable comprend un motif polyaryloxy et un motif polyarylcarbonyle, et est caractérisée en ce qu'elle comprend un motif contenant un groupe réactif représenté par la formule (1) en tant que motif polyaryloxy. Dans la formule (1), R1 représente un groupe hydrocarboné en C1-C8, R2 représente un atome d'hydrogène ou un groupe hydrocarboné en C1-C12, Y représente un site de combinaison avec un motif polyarylcarbonyle ou représente un groupe réactif représenté par la formule (2), de 1 à 99 % en moles de toutes les fractions Y étant le groupe réactif représenté par la formule (2), R représente un atome d'hydrogène ou un groupe alkyle ou alcényle en C1-C8, i représente un nombre entier de 0 à 2, et n indique le nombre de répétitions et représente un nombre de 0 à 5 en moyenne.
PCT/JP2024/041381 2023-11-30 2024-11-22 Résine d'ester thermodurcissable, son procédé de production, composition de résine thermodurcissable, objet durci formé à partir de celle-ci, préimprégné, feuille de résine, stratifié et matériau pour cartes de circuit imprimé Pending WO2025115767A1 (fr)

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Citations (6)

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Publication number Priority date Publication date Assignee Title
CN106811023A (zh) * 2016-12-06 2017-06-09 嘉兴市新大陆机电有限公司 一种环保型风力发电机用vpi浸渍树脂及其制备方法
CN108977005A (zh) * 2018-08-07 2018-12-11 嘉兴市嘉盛绝缘材料有限公司 一种环保绝缘浸渍漆及其制备方法
JP2021014577A (ja) * 2019-07-12 2021-02-12 味の素株式会社 樹脂組成物
JP2021055005A (ja) * 2019-10-01 2021-04-08 Dic株式会社 エポキシ（メタ）アクリレート樹脂組成物、硬化性樹脂組成物、硬化物及び物品
JP2021054954A (ja) * 2019-09-30 2021-04-08 太陽インキ製造株式会社 硬化性樹脂組成物、ドライフィルム、樹脂付き銅箔、硬化物、及び電子部品
JP6955232B2 (ja) * 2018-03-29 2021-10-27 Dic株式会社 硬化性組成物及びその硬化物

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106811023A (zh) * 2016-12-06 2017-06-09 嘉兴市新大陆机电有限公司 一种环保型风力发电机用vpi浸渍树脂及其制备方法
JP6955232B2 (ja) * 2018-03-29 2021-10-27 Dic株式会社 硬化性組成物及びその硬化物
CN108977005A (zh) * 2018-08-07 2018-12-11 嘉兴市嘉盛绝缘材料有限公司 一种环保绝缘浸渍漆及其制备方法
JP2021014577A (ja) * 2019-07-12 2021-02-12 味の素株式会社 樹脂組成物
JP2021054954A (ja) * 2019-09-30 2021-04-08 太陽インキ製造株式会社 硬化性樹脂組成物、ドライフィルム、樹脂付き銅箔、硬化物、及び電子部品
JP2021055005A (ja) * 2019-10-01 2021-04-08 Dic株式会社 エポキシ（メタ）アクリレート樹脂組成物、硬化性樹脂組成物、硬化物及び物品

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