WO2023027154A1 - Composition de résine - Google Patents

Composition de résine Download PDF

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Publication number
WO2023027154A1
WO2023027154A1 PCT/JP2022/032089 JP2022032089W WO2023027154A1 WO 2023027154 A1 WO2023027154 A1 WO 2023027154A1 JP 2022032089 W JP2022032089 W JP 2022032089W WO 2023027154 A1 WO2023027154 A1 WO 2023027154A1
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Prior art keywords
resin composition
group
optionally substituted
mass
substituent
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PCT/JP2022/032089
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English (en)
Japanese (ja)
Inventor
賢司 川合
二朗 長岡
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味の素株式会社
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Priority to KR1020247005732A priority Critical patent/KR20240044445A/ko
Priority to JP2023543985A priority patent/JPWO2023027154A1/ja
Priority to CN202280057106.8A priority patent/CN117881715A/zh
Publication of WO2023027154A1 publication Critical patent/WO2023027154A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4014—Nitrogen containing compounds
    • C08G59/4042—Imines; Imides
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • C08G59/621—Phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • H01L23/295—Organic, e.g. plastic containing a filler
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement

Definitions

  • the present invention relates to a resin composition containing an epoxy resin. Furthermore, it relates to a resin sheet, a printed wiring board, and a semiconductor device obtained using the resin composition.
  • the insulating layer is generally formed by curing a resin composition.
  • further improvements in dielectric properties such as dielectric loss tangent of insulating layers have been demanded.
  • Patent Document 1 As a resin composition for forming an insulating layer, an epoxy resin composition highly filled with an inorganic filler and an epoxy resin composition containing an active ester compound instead of a general phenolic curing agent have been used.
  • Patent Documents 2 and 3 Various active ester curing agents have been known so far.
  • JP 2020-23714 A Japanese Patent No. 6862701 JP 2021-14545 A
  • An object of the present invention is to provide a resin composition from which a cured product with excellent crack resistance can be obtained.
  • the present inventors have made intensive studies and found that (C) an epoxy resin composition containing an inorganic filler content of 60% by mass or more and (B) an active ester curing agent (B) As the active ester curing agent, by using an active ester curing agent in which a bulky group is introduced at the para-position of the terminal phenoxycarbonyl site, it is possible to unexpectedly obtain a cured product having excellent crack resistance. I found that it can be done, and came to complete the present invention.
  • the content of component (C) is 60% by mass or more when the non-volatile component in the resin composition is 100% by mass
  • (B) component is (B1) formula (B1-1):
  • R 1a and R 1b each independently represent an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group or R 1a and R 1b are joined together to form an optionally substituted non-aromatic carbocyclic ring;
  • R 1c represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group;
  • R 2 each independently represents a substituent; a represents 0, 1, or 2; * indicates the binding site.
  • component (B1) further has formula (B1-2b):
  • R 1a and R 1b each independently represent an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group or R 1a and R 1b are joined together to form an optionally substituted non-aromatic carbocyclic ring;
  • R 1c represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group;
  • R 2 each independently represents a substituent; each R 3 independently represents a hydrogen atom or a methyl group;
  • ring X 1 represents an aromatic carbocyclic ring optionally having a substituent; a represents 0, 1, or 2; * indicates the binding site.
  • Component (B1) is represented by formula (B1c):
  • R 1a and R 1b each independently represent an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group or R 1a and R 1b are joined together to form an optionally substituted non-aromatic carbocyclic ring;
  • R 1c each independently represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group;
  • R 2 each independently represents a substituent; each R 3 independently represents a hydrogen atom or a methyl group;
  • Ring X 1 and Ring Y 1 each independently represent an aromatic carbocyclic ring which may have a substituent; a each independently represents 0, 1, or 2; b represents 0 or an integer of 1 or more;
  • R 4 , R 5 and R 6 are (1) R 4 represents a hydrogen atom, a halogen atom, a methyl group, or R 41 -A-, and R 5 and R 6 each independently represent a hydrogen atom , or represents a substituent, or (2) R 4 and R 5 are joined together to form an aromatic carbocyclic ring, which may have a substituent, and R 6 is a hydrogen atom, or or (3) R 5 and R 6 are combined to form an aromatic carbocyclic ring which may have a substituent, and R 4 is a hydrogen atom or a halogen atom , a methyl group, or R 41 -A-; R 7 and R 8 each independently represent a hydrogen atom or a substituent; R 41 represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group; A represents -CH 2 -, -CH(CH 3 )-, -CO-, or -O-; *
  • a resin sheet comprising a support and a resin composition layer formed from the resin composition according to any one of [1] to [15] provided on the support.
  • a printed wiring board comprising an insulating layer comprising a cured product of the resin composition according to any one of [1] to [15] above.
  • a semiconductor device including the printed wiring board according to [19] above.
  • FIG. 1 shows a GPC chart of active ester A (terminal sterically hindered ester curing agent) of Synthesis Example 1.
  • FIG. 2 shows an IR chart of active ester A (terminal sterically hindered ester curing agent) of Synthesis Example 1.
  • FIG. 1 shows a GPC chart of active ester A (terminal sterically hindered ester curing agent) of Synthesis Example 1.
  • FIG. 2 shows an IR chart of active ester A (terminal sterically hindered ester curing agent) of Synthesis Example 1.
  • the resin composition of the present invention contains (A) an epoxy resin, (B) an active ester curing agent, and (C) an inorganic filler, and the content of component (C) is such that the non-volatile components in the resin composition are When 100% by mass, it is 60% by mass or more, and the component (B) contains (B1) a terminal sterically hindered active ester curing agent. With such a resin composition, a cured product having excellent crack resistance can be obtained.
  • the resin composition of the present invention may further contain optional components in addition to (A) epoxy resin, (B) active ester curing agent, and (C) inorganic filler.
  • Optional components include, for example, (D) a curing accelerator, (E) other additives, and (F) an organic solvent.
  • the resin composition of the present invention contains (A) an epoxy resin.
  • (A) Epoxy resin is a curable resin having an epoxy group.
  • Epoxy resins include, for example, bixylenol type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AF type epoxy resins, dicyclopentadiene type epoxy resins, and trisphenol type epoxy resins.
  • the resin composition preferably contains an epoxy resin having two or more epoxy groups in one molecule as (A) the epoxy resin.
  • the proportion of the epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 100% by mass of the non-volatile components of the epoxy resin. is 70% by mass or more.
  • Epoxy resins include liquid epoxy resins at a temperature of 20° C. (hereinafter sometimes referred to as “liquid epoxy resins”) and solid epoxy resins at a temperature of 20° C. (hereinafter sometimes referred to as “solid epoxy resins”). ).
  • the resin composition of the present invention may contain only a liquid epoxy resin, may contain only a solid epoxy resin, or may contain a combination of a liquid epoxy resin and a solid epoxy resin. However, it is preferable to contain a combination of a liquid epoxy resin and a solid epoxy resin.
  • a liquid epoxy resin having two or more epoxy groups in one molecule is preferable as the liquid epoxy resin.
  • Liquid epoxy resins include glycyrrol type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, naphthalene type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, phenol novolac type epoxy resins.
  • Resins alicyclic epoxy resins having an ester skeleton, cyclohexanedimethanol-type epoxy resins, cycloaliphatic glycidyl ethers, and epoxy resins having a butadiene structure are preferred, and glycyrrol-type epoxy resins, cycloaliphatic glycidyl ethers, and bisphenol A-type epoxy resins. Resins and bisphenol F type epoxy resins are more preferred.
  • liquid epoxy resins include “EX-992L” manufactured by Nagase ChemteX Corporation, “YX7400” manufactured by Mitsubishi Chemical Corporation, "HP4032", “HP4032D”, and “HP4032SS” manufactured by DIC Corporation (naphthalene type epoxy resin ); Mitsubishi Chemical “828US”, “828EL”, “jER828EL”, “825", “Epicoat 828EL” (bisphenol A type epoxy resin); Mitsubishi Chemical “jER807”, “1750” (bisphenol F type epoxy resin); “jER152” (phenol novolak type epoxy resin) manufactured by Mitsubishi Chemical; "630", “630LSD”, “604" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical; ED-523T” (glycirrol type epoxy resin); ADEKA “EP-3950L”, “EP-3980S” (glycidylamine type epoxy resin); ADEKA “EP-4088S” (dicyclopentadiene type epoxy resin ); "ZX1059” manufactured by Nippozed
  • epoxy resin having a butadiene structure epoxy resin
  • epoxy resin epoxy resin
  • EG-280 fluorene structure-containing epoxy resin
  • EX-201 cycloaliphatic glycidyl ether
  • the solid epoxy resin is preferably a solid epoxy resin having 3 or more epoxy groups per molecule, more preferably an aromatic solid epoxy resin having 3 or more epoxy groups per molecule.
  • Solid epoxy resins include bixylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, naphthol novolak type epoxy resin, cresol novolak type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, Naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, phenol aralkyl type epoxy resin, tetraphenylethane type epoxy resin, phenol phthalate A mijin-type epoxy resin is preferred.
  • solid epoxy resins include “HP4032H” (naphthalene-type epoxy resin) manufactured by DIC; “HP-4700” and “HP-4710” (naphthalene-type tetrafunctional epoxy resin) manufactured by DIC; “N-690” (cresol novolac type epoxy resin) manufactured by DIC Corporation; “N-695" (cresol novolak type epoxy resin) manufactured by DIC Corporation; "HP-7200”, “HP-7200HH”, “HP -7200H”, “HP-7200L” (dicyclopentadiene type epoxy resin); DIC's "EXA-7311", “EXA-7311-G3", “EXA-7311-G4", “EXA-7311-G4S” ", "HP6000” (naphthylene ether type epoxy resin); Nippon Kayaku "EPPN-502H” (trisphenol type epoxy resin); Nippon Kayaku “NC7000L” (naphthol novolac type epoxy resin); "NC3
  • the mass ratio thereof (solid epoxy resin: liquid epoxy resin) is preferably 10:1 to 1:50, more preferably. is 5:1 to 1:20, particularly preferably 2:1 to 1:10.
  • the epoxy equivalent of the epoxy resin is preferably 50 g/eq. ⁇ 5,000g/eq. , more preferably 60 g/eq. ⁇ 2,000 g/eq. , more preferably 70 g/eq. ⁇ 1,000 g/eq. , even more preferably 80 g/eq. ⁇ 500 g/eq. is.
  • Epoxy equivalent weight is the mass of resin per equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.
  • the weight average molecular weight (Mw) of the epoxy resin is preferably 100 to 5,000, more preferably 250 to 3,000, still more preferably 400 to 1,500.
  • the weight average molecular weight of the resin can be measured as a polystyrene-equivalent value by a gel permeation chromatography (GPC) method.
  • the content of (A) the epoxy resin in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 30% by mass or less, more preferably 25% by mass. % by mass or less, more preferably 20% by mass or less, even more preferably 15% by mass or less, and particularly preferably 12% by mass or less.
  • the lower limit of the content of (A) the epoxy resin in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 0.01% by mass or more, More preferably 0.1% by mass or more, still more preferably 1% by mass or more, even more preferably 5% by mass or more, and particularly preferably 10% by mass or more.
  • the resin composition of the present invention contains (B) an active ester curing agent.
  • the active ester-based curing agent can function as an epoxy resin curing agent that reacts with (A) the epoxy resin to cure it.
  • the active ester-based curing agent may be used singly or in combination of two or more at any ratio.
  • the active ester curing agent generally contains two highly reactive ester groups per molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds. A compound having one or more is preferably used.
  • the active ester curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and/or a thiocarboxylic acid compound and a hydroxy compound and/or a thiol compound.
  • an active ester compound obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester compound obtained from a carboxylic acid compound and a phenolic compound is more preferred.
  • carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid.
  • phenolic compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, ⁇ -naphthol, ⁇ -naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucine, benzenetriol , dicyclopentadiene-type diphenol compounds, phenol novolacs,
  • the active ester group equivalent of the active ester curing agent is preferably 50 g/eq. ⁇ 500 g/eq. , more preferably 50 g/eq. ⁇ 400 g/eq. , more preferably 100 g/eq. ⁇ 300 g/eq. is.
  • the active ester group equivalent is the mass of the active ester curing agent per equivalent of the ester group capable of reacting with the epoxy resin.
  • the content of (B) the active ester curing agent in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 0.1% by mass or more. , more preferably 1% by mass or more, still more preferably 5% by mass or more, still more preferably 10% by mass or more, even more preferably 12% by mass or more, still more preferably 14% by mass or more, particularly preferably 15% by mass or more is.
  • the upper limit of the content of (B) the active ester curing agent in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 50% by mass or less. , more preferably 40% by mass or less, still more preferably 30% by mass or less, still more preferably 25% by mass or less, and particularly preferably 20% by mass or less.
  • R 1a and R 1b are each independently an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted represents an aryl group, or R 1a and R 1b combine together to form an optionally substituted non - aromatic carbocyclic ring; an alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group; each R 2 independently represents a substituent; 1 or 2 is indicated; * indicates the binding site.
  • R 1a and R 1b each independently represent an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group Alternatively, R 1a and R 1b are joined together to form an optionally substituted non-aromatic carbocyclic ring.
  • Alkyl (group) means a linear, branched and/or cyclic monovalent saturated aliphatic hydrocarbon group.
  • the alkyl (group), unless otherwise specified, is preferably an alkyl (group) having 1 to 14 carbon atoms, more preferably an alkyl (group) having 1 to 10 carbon atoms, and an alkyl (group) having 1 to 6 carbon atoms. More preferred.
  • alkyl (group) examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, sec-pentyl group and neopentyl group. , tert-pentyl group, hexyl group, isohexyl group, heptyl group, isoheptyl group, octyl group, isooctyl group, tert-octyl group, cyclopentyl group, cyclohexyl group and the like.
  • Alkenyl (group) means a linear, branched and/or cyclic monovalent unsaturated aliphatic hydrocarbon group having at least one carbon-carbon double bond.
  • the alkenyl (group) is preferably an alkenyl group having 2 to 14 carbon atoms, more preferably an alkenyl group having 2 to 10 carbon atoms, and even more preferably an alkenyl group having 2 to 6 carbon atoms, unless otherwise specified.
  • alkenyl (group) examples include vinyl group, propenyl group (allyl group, 1-propenyl group, isopropenyl group), butenyl group (1-butenyl group, crotyl group, methallyl group, isocrotyl group, etc.), pentenyl group ( 1-pentenyl group, etc.), hexenyl group (1-hexenyl group, etc.), heptenyl group (1-heptenyl group, etc.), octenyl group (1-octenyl group, etc.), cyclopentenyl group (2-cyclopentenyl group, etc.), cyclo hexenyl group (3-cyclohexenyl group, etc.) and the like.
  • Aryl (group) means a monovalent aromatic hydrocarbon group from which one hydrogen atom is removed from an aromatic carbocyclic ring.
  • the aryl (group) is preferably an aryl (group) having 6 to 14 carbon atoms, more preferably an aryl (group) having 6 to 10 carbon atoms, unless otherwise specified.
  • Aryl (group) includes, for example, phenyl group, 1-naphthyl group, 2-naphthyl group and the like.
  • a non-aromatic carbocyclic ring means a ring other than an aromatic carbocyclic ring having aromaticity throughout the ring.
  • Non-aromatic carbocycles have only carbon atoms as ring atoms.
  • a non-aromatic carbocyclic ring can be a saturated carbocyclic ring consisting only of a single bond, or an unsaturated carbocyclic ring having at least one of a double bond and a triple bond.
  • the non-aromatic carbocyclic ring is preferably a non-aromatic carbocyclic ring having 4 to 20 carbon atoms, more preferably a non-aromatic carbocyclic ring having 5 to 12 carbon atoms.
  • non-aromatic carbocyclic rings include monocyclic rings such as cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, and cyclododecane ring.
  • bicyclo[2.2.1]heptane ring (norbornane ring), bicyclo[4.4.0]decane ring (decane ring), bicyclo[5.3.0]decane ring, bicyclo[4 .3.0]nonane ring (hydrindane ring), bicyclo[3.2.1]octane ring, bicyclo[5.4.0]undecane ring, bicyclo[3.3.0]octane ring, bicyclo[3.3 .1] bicyclic saturated carbocyclic ring such as nonane ring; tricyclo[5.2.1.0 2,6 ]decane ring (tetrahydrodicyclopentadiene ring), tricyclo[3.3.1.1 3,7 ] decane ring (adamantane ring), tricyclo[6.2.1.0 2,7 ]undecane ring and other tricyclic saturated carbocycles; tetracyclo[6.2.1.1 3,6 .
  • non-aromatic carbocyclic ring may be condensed with one or more aromatic carbocyclic rings at a condensable position.
  • Non-aromatic carbocyclic rings fused with aromatic carbocyclic rings include, for example, indane ring, indene ring, tetralin ring, 1,2-dihydronaphthalene ring, 1,4-dihydronaphthalene ring, fluorene ring, 9,10-dihydro Examples include anthracene ring, 9,10-dihydrophenanthrene ring, and the like.
  • Aromatic carbocyclic ring means a hydrocarbon ring that follows Hückel's rule and has 4p+2 electrons (p is a natural number) in the ⁇ electron system on the ring.
  • Aromatic carbocycles have only carbon atoms as ring atoms.
  • the aromatic carbocyclic ring is preferably a 6- to 14-membered aromatic carbocyclic ring, more preferably a 6- to 10-membered aromatic carbocyclic ring.
  • aromatic carbocyclic ring examples include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring and the like, more preferably benzene ring or naphthalene ring, and particularly preferably benzene ring.
  • the “substituent” in the alkyl group and alkenyl group represented by R 1a and R 1b is not particularly limited, but examples include halogen atoms, aryl groups, alkyl-aryl groups ( aryl group), alkenyl-aryl group (aryl group substituted with an alkenyl group), aryl-aryl group (aryl group substituted with an aryl group), alkyl-oxy group, alkenyl-oxy group, aryl-oxy group, alkyl -carbonyl group, alkenyl-carbonyl group, aryl-carbonyl group, alkyl-oxy-carbonyl group, alkenyl-oxy-carbonyl group, aryl-oxy-carbonyl group, alkyl-carbonyl-oxy group, alkenyl-carbonyl-oxy group, aryl-carbonyl-oxy group and the like.
  • the “substituent” in the aryl group represented by R 1a and R 1b is not particularly limited, but examples include halogen atoms, alkyl groups, alkenyl groups, aryl groups, aryl-alkyl groups (substituted with aryl groups alkyl group substituted with an alkyl group), alkyl-aryl-alkyl group (an alkyl group substituted with an aryl group substituted with an alkyl group), alkenyl-aryl-alkyl group (an alkyl group substituted with an aryl group substituted with an alkenyl group ), an aryl-aryl-alkyl group (an alkyl group substituted with an aryl group substituted with an aryl group), an alkyl-aryl group, an alkenyl-aryl group, an aryl-aryl group, an alkyl-oxy group, an alkenyl-oxy group, aryl-oxy group, alkyl-carbonyl group, al
  • the "substituent" in the non-aromatic carbocyclic ring formed by R 1a and R 1b is not particularly limited, but examples include halogen atoms, alkyl groups, alkenyl groups, aryl groups, aryl-alkyl groups, alkyl - aryl-alkyl group, alkenyl-aryl-alkyl group, aryl-aryl-alkyl group, alkyl-aryl group, alkenyl-aryl group, aryl-aryl group, alkyl-oxy group, alkenyl-oxy group, aryl-oxy group, alkyl-carbonyl group, alkenyl-carbonyl group, aryl-carbonyl group, alkyl-oxy-carbonyl group, alkenyl-oxy-carbonyl group, aryl-oxy-carbonyl group, alkyl-carbonyl-oxy group, alkenyl-carbonyl-oxy group, aryl-carbonyl-oxy group, alken
  • a halogen atom is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, preferably a chlorine atom.
  • R 1a and R 1b are each independently, in one embodiment, preferably an optionally substituted alkyl group or an optionally substituted aryl group; more preferably is an optionally substituted alkyl group; more preferably an alkyl group; even more preferably R 1a is a methyl group and R 1b is an alkyl group; even more preferably , R 1a is a methyl group and R 1b is an alkyl group having 2 or more carbon atoms; particularly preferably, R 1a is a methyl group and R 1b is an ethyl group.
  • R 1c represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group.
  • the "substituent” in the alkyl group and alkenyl group represented by R 1c is not particularly limited, but is exemplified as the "substituent” in the alkyl group and alkenyl group represented by R 1a and R 1b The same thing as a thing is mentioned.
  • the “substituent” for the aryl group represented by R 1c is not particularly limited, and examples thereof include those exemplified as the “substituent” for the aryl group represented by R 1a and R 1b . .
  • R 1c is preferably an optionally substituted alkyl group or an optionally substituted aryl group; more preferably an alkyl group; particularly preferably a methyl group.
  • R 1c , R 1c and R 1c and the carbon atom to which they are attached i.e. (R1):
  • each symbol is as described above.
  • Specific examples of the monovalent group represented by include tert-butyl group, tert-pentyl group (tert-amyl group), 1-methylcyclobutyl group, 1,1-dimethylbutyl group, 1-ethyl-1 - Tertiary alkyl such as methylpropyl group, 1-methylcyclopentyl group, 1-ethylcyclobutyl group, 1,1-dimethylpentyl group, 1,1,2-trimethylbutyl group, 1-ethyl-1-methylbutyl group groups; 1-position alkenyl-substituted secondary alkyl groups such as 1,1-dimethyl-2-propenyl group; 1-position aryl-substituted secondary alkyl groups such as ⁇ -cumyl group;
  • Each R 2 independently represents a substituent.
  • the "substituent" represented by R 2 is not particularly limited, but for example, in addition to the monovalent group represented by formula (R1), a halogen atom, an alkyl group, an alkenyl group, an aryl group, aryl-alkyl group, alkyl-aryl-alkyl group, alkenyl-aryl-alkyl group, aryl-aryl-alkyl group, alkyl-aryl group, alkenyl-aryl group, aryl-aryl group, alkyl-oxy group, alkenyl-oxy group , aryl-oxy group, alkyl-carbonyl group, alkenyl-carbonyl group, aryl-carbonyl group, alkyl-oxy-carbonyl group, alkenyl-oxy-carbonyl group, aryl-oxy-carbonyl group, alkyl-carbonyl-oxy group, alkenyl-carbonyl-oxy group, aryl-carbonyl-oxy group and the like
  • Each R 2 is independently, in one embodiment, preferably an alkyl group, an alkenyl group, an aryl group, an aryl-alkyl group, an alkyl-aryl-alkyl group, an alkenyl-aryl-alkyl group, an aryl-aryl-alkyl , an alkyl-aryl group, an alkenyl-aryl group, or an aryl-aryl group.
  • a indicates 0, 1, or 2; a is preferably 0 or 1; more preferably 0, in one embodiment.
  • the component (B1) preferably further has formula (B1-2a):
  • R 1 each independently represents a substituent
  • R 3 each independently represents a hydrogen atom or a methyl group
  • Ring X 1 optionally has a substituent represents an aromatic carbocyclic ring
  • e each independently represents 0, 1, 2, 3, or 4
  • * represents a binding site.
  • the “substituent” for R 1 is not particularly limited, but includes the same “substituent” as exemplified for R 2 .
  • Each R 1 independently represents a substituent.
  • Each R 1 is independently, in one embodiment, preferably an alkyl group, an alkenyl group, an aryl group, an aryl-alkyl group, an alkyl-aryl-alkyl group, an alkenyl-aryl-alkyl group, an aryl-aryl-alkyl group, an alkyl-aryl group, an alkenyl-aryl group, an aryl-aryl group, or a monovalent group represented by the formula (R1); more preferably a monovalent group represented by the formula (R1) be.
  • Each R3 independently represents a hydrogen atom or a methyl group.
  • Each R 3 is independently, in one embodiment, preferably a hydrogen atom.
  • Ring X 1 represents an aromatic carbocyclic ring optionally having a substituent.
  • the “substituent” for the aromatic carbocyclic ring represented by ring X 1 is not particularly limited, but is the same as those exemplified as the “substituent” for the aryl group represented by R 1a and R 1b . is mentioned.
  • Ring X 1 is preferably a benzene ring optionally having a substituent or a naphthalene ring optionally having a substituent; more preferably (1) an alkyl group, a benzene ring optionally substituted by a group selected from an alkenyl group, an aryl group, an aryl-alkyl group and an alkyl-aryl group, or (2) an alkyl group, an alkenyl group, an aryl group, an aryl-alkyl group and an alkyl - naphthalene ring optionally substituted by a group selected from an aryl group; more preferably (1) a benzene ring optionally substituted by an alkyl group, or (2) optionally substituted by an alkyl group more preferably a benzene ring optionally substituted with an alkyl group; particularly preferably a (unsubstituted) benzene ring.
  • e each independently represents 0, 1, 2, 3, or 4; Each e is independently, in one embodiment, preferably 0, 1, 2, or 3; more preferably 0, 1, or 2; more preferably 0, or 1 particularly preferably 0.
  • the component (B1) more preferably further has formula (B1-2b):
  • component (B1) has the formula (B1a):
  • ring X each independently represents an optionally substituted aromatic carbocyclic ring or an optionally substituted non-aromatic carbocyclic ring
  • Z 1 each independently represents an optionally substituted aromatic carbocyclic ring
  • X a each independently represents a single bond, —C(R a ) 2 —, —O—, —CO—, —S—, —SO—, —SO 2 —, —CONH—, or —NHCO—
  • each R a is independently a hydrogen atom, optionally substituted alkyl or an optionally substituted aryl group, or two R a are joined together to form a non-aromatic carbocyclic ring optionally having substituents
  • b is 0, or an integer of 1 or more
  • c is each independently 0, 1, 2, or 3
  • d is each independently 0 or 1; As above.
  • the b unit and c unit may be the same or different for each structural unit.
  • Each ring X independently represents an optionally substituted aromatic carbocyclic ring or an optionally substituted non-aromatic carbocyclic ring.
  • the "substituent" for the aromatic carbocyclic ring represented by ring X is not particularly limited, but is the same as those exemplified as the "substituent” for the aryl group represented by R 1a and R 1b . mentioned.
  • the "substituent” for the non-aromatic carbocyclic ring formed by ring X is not particularly limited, but the “substituent” for the non-aromatic carbocyclic ring formed by R 1a and R 1b may be the same as those exemplified as the "substituent" for the non-aromatic carbocyclic ring formed by R The same can be mentioned.
  • ring X is preferably an optionally substituted aromatic carbocyclic ring; more preferably an optionally substituted benzene ring or a substituted more preferably (1) a benzene ring optionally substituted with a group selected from an alkyl group, an alkenyl group, an aryl group, an aryl-alkyl group, and an alkyl-aryl group, or (2) A naphthalene ring optionally substituted with a group selected from an alkyl group, an alkenyl group, an aryl group, an aryl-alkyl group, and an alkyl-aryl group; still more preferably an alkyl group, an alkenyl group, and an aryl is a benzene ring optionally substituted by a group selected from a group, an aryl-alkyl group, and an alkyl-aryl group; still more preferably a benzene ring optionally substituted by an alkyl group; particularly preferably
  • Each ring Y 1 independently represents an aromatic carbocyclic ring which may have a substituent.
  • the "substituent" for the aromatic carbocyclic ring represented by ring Y 1 is not particularly limited, but is the same as those exemplified as the "substituent” for the aryl group represented by R 1a and R 1b . is mentioned.
  • Each ring Y 1 is independently, in one embodiment, preferably a benzene ring optionally having a substituent or a naphthalene ring optionally having a substituent; more preferably ( 1) a benzene ring optionally substituted with a group selected from an alkyl group, an alkenyl group, an aryl group, an aryl-alkyl group, and an alkyl-aryl group; or (2) an alkyl group, an alkenyl group, an aryl group, an aryl- A naphthalene ring optionally substituted by a group selected from an alkyl group and an alkyl-aryl group; more preferably (1) a benzene ring optionally substituted by an alkyl group, or (2) an alkyl group It is a naphthalene ring which may be substituted; more preferably a benzene ring which may be substituted with an alkyl group; particularly preferably a (unsubstituted
  • Each ring Z 1 independently represents an aromatic carbocyclic ring which may have a substituent.
  • the “substituent” for the aromatic carbocyclic ring represented by ring Z 1 is not particularly limited, and examples thereof include those exemplified as the “substituent” for R 2 .
  • Each ring Z 1 is independently, in one embodiment, preferably a benzene ring optionally having a substituent or a naphthalene ring optionally having a substituent; more preferably ( 1) Alkyl group, alkenyl group, aryl group, aryl-alkyl group, alkyl-aryl-alkyl group, alkenyl-aryl-alkyl group, aryl-aryl-alkyl group, alkyl-aryl group, alkenyl-aryl group, aryl-aryl and a benzene ring optionally substituted by a group selected from monovalent groups represented by formula (R1), or (2) an alkyl group, an alkenyl group, an aryl group, an aryl-alkyl group, an alkyl-aryl -A group selected from an alkyl group, an alkenyl-aryl-alkyl group, an aryl-aryl-alkyl group, an alkyl-aryl group, an
  • Each X a is independently a single bond, -C(R a ) 2 -, -O-, -CO-, -S-, -SO-, -SO 2 -, -CONH-, or -NHCO- indicates Each X a is independently, in one embodiment, preferably a single bond, —C(R a ) 2 —, or —O—; more preferably —C(R a ) 2 — particularly preferably -C(R 3 )(CH 3 )-.
  • Each R a independently represents a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aryl group, or two R a to form a non-aromatic carbocyclic ring which may have a substituent.
  • the "substituent" in the alkyl group represented by R a is not particularly limited, but the same as those exemplified as the "substituent” in the alkyl group represented by R 1a and R 1b and the alkenyl group things are mentioned.
  • the "substituent” for the aryl group represented by R a is not particularly limited, and examples thereof include those exemplified as the "substituent” for the aryl group represented by R 1a and R 1b . .
  • the “substituent” for the non-aromatic carbocyclic ring formed by R a is not particularly limited, and the “substituent” for the non-aromatic carbocyclic ring formed by R 1a and R 1b may be the same as those exemplified as the “substituent” for the non-aromatic carbocyclic ring formed by R The same can be mentioned.
  • Each R a is independently, in one embodiment, preferably a hydrogen atom or an optionally substituted alkyl group; preferably a hydrogen atom, or optionally a substituent A hydrogen atom or an alkyl group is more preferred; a hydrogen atom or a methyl group is particularly preferred.
  • b represents 0 or an integer of 1 or more. In one embodiment, b is preferably 0, or an integer from 1 to 100; more preferably 0, or an integer from 1 to 10; particularly preferably 0, or an integer from 1 to 5 be.
  • c each independently represents 0, 1, 2, or 3; Each c is independently, in one embodiment, preferably 0, 1, or 2; more preferably 0, or 1;
  • Each d independently represents 0 or 1. Each d is independently preferably 1 in one embodiment.
  • component (B1) has the formula (B1b):
  • component (B1) has the formula (B1c):
  • each R x independently represents an alkyl group, an alkenyl group, an aryl group, an aryl-alkyl group, or an alkyl-aryl group; other symbols as above.
  • structures represented by formulas (X-1) to (X-3) are preferred, and in one embodiment, particularly preferably, formula (X-2) is the structure represented.
  • Each R x is independently, in one embodiment, preferably an alkyl group.
  • Each x is independently, in one embodiment, preferably 0 or 1; more preferably 0.
  • R y each independently represents an alkyl group, alkenyl group, aryl group, aryl-alkyl group, or alkyl-aryl group; y each independently represents 0, 1, or 2; other symbols as above. ] etc., among which the structure represented by Formula (Y-2) is preferred.
  • Each R y is independently, in one embodiment, preferably an alkyl group.
  • Each y is independently, in one embodiment, preferably 0 or 1; more preferably 0.
  • Component (B1) is a resin represented by formula (B1a), (B1b) or (B1c) and a reaction intermediate resin produced during synthesis (for example, one end or both ends are hydroxy groups and/or carboxy groups), It may contain resins and the like derived from raw material impurities.
  • the (B1) component may be a commercially available product, or may be synthesized using a known method or a method equivalent thereto.
  • the content of component (B1) in the resin composition is not particularly limited. %, more preferably 20% by mass or less, and from the viewpoint of further improving the glass transition temperature of the cured product, it is even more preferably 15% by mass or less, particularly preferably 10% by mass or less.
  • the lower limit of the content of the component (B1) in the resin composition is not particularly limited, but from the viewpoint of obtaining the desired effect of the present invention more significantly, the non-volatile component in the resin composition is 100% by mass. , it is preferably 0.1% by mass or more, more preferably 1% by mass or more, still more preferably 3% by mass or more, even more preferably 5% by mass or more, and particularly preferably 7% by mass or more.
  • the content of component (B1) in the active ester curing agent (B) may be 100% by mass when the active ester curing agent (B) is 100% by mass, but the glass transition of the cured product may be From the viewpoint of further improving the temperature, it is preferably 95% by mass or less, more preferably 90% by mass or less, still more preferably 80% by mass or less, even more preferably 70% by mass or less, and particularly preferably 60% by mass or less. be.
  • the lower limit of the content of component (B1) in (B) the active ester curing agent is not particularly limited, but from the viewpoint of obtaining the desired effects of the present invention more remarkably, (B) the active ester curing agent
  • the curing agent is 100% by mass, it is preferably 1% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, still more preferably 30% by mass or more, and particularly preferably 40% by mass or more. be.
  • the mass ratio of component (B1) to epoxy resin (A) in the resin composition (component (B1)/component (A)) is not particularly limited, but is preferably 0.05 or more, more preferably It is 0.1 or more, more preferably 0.5 or more.
  • the upper limit of the mass ratio of component (B1) to epoxy resin (A) in the resin composition (component (B1)/component (A)) is not particularly limited, but is preferably 10 or less, more preferably It is 5 or less, and more preferably 1 or less from the viewpoint of further improving the glass transition temperature of the cured product.
  • the active ester curing agent may further contain an active ester curing agent other than the component (B1) (hereinafter sometimes referred to as "(B2) other active ester curing agent").
  • the active ester-based curing agent is (B2) another active ester-based curing agent represented by the formula (B2-1):
  • R 4 , R 5 and R 6 are: (1) R 4 represents a hydrogen atom, a halogen atom, a methyl group, or R 41 -A-, and R 5 and R 6 each independently represents a hydrogen atom or a substituent, or (2) R 4 and R 5 are combined to form an aromatic carbocyclic ring optionally having a substituent, and R 6 is represents a hydrogen atom or a substituent, or (3) R 5 and R 6 are combined to form an optionally substituted aromatic carbocyclic ring, and R 4 is hydrogen an atom, a halogen atom, a methyl group, or R 41 -A-; R 7 and R 8 each independently represent a hydrogen atom or a substituent; R 41 may have a substituent A may be an alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group; A represents -CH 2 -, -CH(CH 3 )-, -CO- , or -O-;
  • R 4 represents a hydrogen atom, a halogen atom, a methyl group, or R 41 -A- when it does not form an aromatic carbocyclic ring.
  • R 4 does not form an aromatic carbocyclic ring, in one embodiment, it is preferably a hydrogen atom, a methyl group, or R 41 -A-; more preferably a hydrogen atom, or R 41 -A- be.
  • A represents -CH 2 -, -CH(CH 3 )-, -CO-, or -O-. In one embodiment, A is preferably -CH 2 - or -CH(CH 3 )-; more preferably -CH(CH 3 )-.
  • R 41 represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group.
  • the “substituent” in the alkyl group and alkenyl group represented by R 41 is not particularly limited, but is exemplified as the “substituent” in the alkyl group and alkenyl group represented by R 1a and R 1b The same thing as a thing is mentioned.
  • the “substituent” for the aryl group represented by R 41 is not particularly limited, and examples thereof include those exemplified as the “substituent” for the aryl group represented by R 1a and R 1b . .
  • R 41 is preferably an optionally substituted aryl group; more preferably an aryl group; particularly preferably a phenyl group.
  • R 5 and R 6 each independently represent a hydrogen atom or a substituent when not forming an aromatic carbocyclic ring.
  • the “substituent” for R 5 and R 6 is not particularly limited, and includes the same as those exemplified as the “substituent” for the aryl group for R 1a and R 1b . .
  • R 5 and R 6 do not form an aromatic carbocyclic ring, each independently, in one embodiment, preferably a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aryl-alkyl group, or an alkyl-aryl more preferably a hydrogen atom, an alkyl group, an aryl group, or an aryl-alkyl group.
  • R 4 , R 5 and R 6 form an aromatic carbocyclic ring
  • R 4 and R 5 or R 5 and R 6 are bonded together to form an optionally substituted aromatic carbon form a ring.
  • the “substituent” for the aromatic carbocyclic ring formed by R 4 , R 5 and R 6 is not particularly limited, but is exemplified as the “substituent” for the aryl group represented by R 1a and R 1b The same thing as a thing is mentioned.
  • R 4 and R 5 or R 5 and R 6 are linked together and preferably have a substituent.
  • a benzene ring which may be substituted; more preferably forming a benzene ring which may be substituted with a group selected from an alkyl group, an alkenyl group, an aryl group, an aryl-alkyl group, and an alkyl-aryl group. more preferably form a (unsubstituted) benzene ring.
  • R7 and R8 each independently represent a hydrogen atom or a substituent.
  • the "substituent" for R 7 and R 8 is not particularly limited, and includes the same as those exemplified as the "substituent” for the aryl group for R 1a and R 1b . .
  • R 7 and R 8 are each independently, in one embodiment, preferably a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aryl-alkyl group, or an alkyl-aryl group; more preferably hydrogen It is an atom, an alkyl group, an aryl group, or an aryl-alkyl group.
  • R 4 , R 5 , R 7 and R 8 are hydrogen atoms, and R 6 is an alkyl group or an aryl group; more preferably R 4 , R 5 , R7 and R8 are hydrogen atoms, and R6 is a methyl group or a phenyl group.
  • R 4 is a hydrogen atom, or R 41 -A-, A is -CH 2 -, or -CH(CH 3 )-, and R 41 is aryl and R 5 , R 6 , R 7 and R 8 are hydrogen atoms or aryl-alkyl groups (especially preferably R 4 is R 41 -A- and/or R 5 , R 6 , at least one of R 7 and R 8 is an aryl-alkyl group); more preferably, R 4 is a hydrogen atom, or R 41 -A- and A is -CH(CH 3 ) -, R 41 is a phenyl group, and R 5 , R 6 , R 7 and R 8 are hydrogen atoms or ⁇ -methylbenzyl groups (particularly preferably, R 4 is R 41 -A - and/or at least one of R 5 , R 6 , R 7 and R 8 is an ⁇ -methylbenzyl group).
  • R 4 and R 5 are joined together to form a benzene ring
  • R 6 , R 7 and R 8 are hydrogen atoms
  • R 5 and R6 are joined together to form a benzene ring
  • R4 , R7 and R8 are hydrogen atoms.
  • component (B2) has the formula (B2a):
  • ring X′ each independently represents an optionally substituted aromatic carbocyclic ring or an optionally substituted non-aromatic carbocyclic ring
  • ring Y 2 and Ring Z 2 each independently represents an optionally substituted aromatic carbocyclic ring
  • X b each independently represents a single bond, —C(R b ) 2 —, —O— , —CO—, —S—, —SO—, —SO 2 —, —CONH—, or —NHCO—
  • R b each independently may have a hydrogen atom or a substituent represents an alkyl group or an optionally substituted aryl group, or two R b are bonded together to form a non-aromatic carbocyclic ring optionally having substituents
  • b′ represents 0 or an integer of 1 or more
  • c′ each independently represents 0, 1, 2, or 3
  • d′ each independently represents 0 or 1;
  • Other symbols are as above.
  • Each ring X' independently represents an optionally substituted aromatic carbocyclic ring or an optionally substituted non-aromatic carbocyclic ring.
  • the "substituent" for the aromatic carbocyclic ring represented by ring X' is not particularly limited, but is similar to those exemplified as the "substituent” for the aryl group represented by R 1a and R 1b . is mentioned.
  • the "substituent” in the non-aromatic carbocyclic ring represented by ring X' is not particularly limited, but those exemplified as the "substituent” in the non-aromatic carbocyclic ring formed by R 1a and R 1b and similar ones.
  • Each ring X′ is independently, in one embodiment, preferably a benzene ring optionally having a substituent, a naphthalene ring optionally having a substituent, or having a substituent more preferably (1) substituted with a group selected from an alkyl group, an alkenyl group, an aryl group, an aryl-alkyl group, and an alkyl-aryl group; (2) a naphthalene ring optionally substituted by a group selected from an alkyl group, an alkenyl group, an aryl group, an aryl-alkyl group, and an alkyl-aryl group; or (3) an alkyl group, alkenyl a non-aromatic carbocyclic ring having 5 to 12 carbon atoms (particularly preferably a tetrahydrodicyclopentadiene ring) which may be substituted with a group selected from groups, aryl groups, aryl-alkyl groups, alkyl-ary
  • Ring Y 2 each independently represents an optionally substituted aromatic carbocyclic ring.
  • the "substituent" for the aromatic carbocyclic ring represented by ring Y 2 is not particularly limited, but is the same as those exemplified as the "substituent” for the aryl group represented by R 1a and R 1b . is mentioned.
  • Ring Y 2 is each independently, in one embodiment, preferably a benzene ring optionally having a substituent or a naphthalene ring optionally having a substituent; more preferably ( 1) a benzene ring optionally substituted with a group selected from an alkyl group, an alkenyl group, an aryl group, an aryl-alkyl group, and an alkyl-aryl group; or (2) an alkyl group, an alkenyl group, an aryl group, an aryl- It is a naphthalene ring optionally substituted with a group selected from an alkyl group and an alkyl-aryl group.
  • Each ring Z2 independently represents an aromatic carbocyclic ring which may have a substituent.
  • the “substituent” for the aromatic carbocyclic ring represented by ring Z 2 is not particularly limited, but is the same as those exemplified as the “substituent” for the aryl group represented by R 1a and R 1b . is mentioned.
  • Each ring Z 2 is independently, in one embodiment, preferably a benzene ring optionally having a substituent or a naphthalene ring optionally having a substituent; more preferably ( 1) a benzene ring optionally substituted with a group selected from an alkyl group, an alkenyl group, an aryl group, an aryl-alkyl group, and an alkyl-aryl group; or (2) an alkyl group, an alkenyl group, an aryl group, an aryl- It is a naphthalene ring optionally substituted with a group selected from an alkyl group and an alkyl-aryl group.
  • Each X b is independently a single bond, -C(R b ) 2 -, -O-, -CO-, -S-, -SO-, -SO 2 -, -CONH-, or -NHCO- indicates Each X b is independently, in one embodiment, preferably a single bond, —C(R b ) 2 —, or —O—; more preferably a single bond, or —O—.
  • Each R b independently represents a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aryl group, or two R b together to form a non-aromatic carbocyclic ring which may have a substituent.
  • the “substituent” in the alkyl group represented by R b is not particularly limited, but the same as those exemplified as the “substituent” in the alkyl group represented by R 1a and R 1b and the alkenyl group things are mentioned.
  • the “substituent” for the aryl group represented by R b is not particularly limited, and examples thereof include those exemplified as the “substituent” for the aryl group represented by R 1a and R 1b .
  • the “substituent” for the non-aromatic carbocyclic ring formed by R b is not particularly limited, and the “substituent” for the non-aromatic carbocyclic ring formed by R 1a and R 1b may be the same as those exemplified as the “substituent” for the non-aromatic carbocyclic ring formed by R The same can be mentioned.
  • Each R b is independently, in one embodiment, preferably a hydrogen atom or an optionally substituted alkyl group; more preferably a hydrogen atom or an alkyl group; particularly preferably is a hydrogen atom or a methyl group.
  • b' represents 0 or an integer of 1 or more.
  • b′ is preferably 0, or an integer from 1 to 100; more preferably 0, or an integer from 1 to 10; particularly preferably 0, or an integer from 1 to 5 is.
  • c' each independently represents 0, 1, 2, or 3; Each c' is independently, in one embodiment, preferably 0, 1, or 2; more preferably 0, or 1.
  • d' each independently represents 0 or 1.
  • Examples of the partial structure represented by include structures represented by formulas (Y-1) to (Y-12).
  • the component (B2) includes, together with the resin represented by the formula (B2a), a resin that is a reaction intermediate generated during synthesis (for example, one end or both ends are hydroxy groups and/or carboxy groups), a resin derived from raw material impurities, and the like. may contain.
  • the (B2) component may be a commercially available product, or may be synthesized using a known method or a method equivalent thereto.
  • Commercially available products of component (B2) include "EXB9451”, “EXB9460”, “EXB9460S”, “HPC-8000-65T” and “HPC-8000L-65TM” as active ester compounds containing a dicyclopentadiene type diphenol structure.
  • the content of component (B2) in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 40% by mass or less, more preferably 20% by mass. % or less, more preferably 15 mass % or less, even more preferably 10 mass % or less, and particularly preferably 8 mass % or less.
  • the lower limit of the content of the component (B2) in the resin composition is not particularly limited. % or more, preferably 1% by mass or more, more preferably 3% by mass or more, and particularly preferably 5% by mass or more, from the viewpoint of further improving the glass transition temperature of the cured product.
  • the mass ratio of component (B2) to epoxy resin (A) in the resin composition (component (B2)/component (A)) is not particularly limited, but is preferably 10 or less, more preferably 5 or less. , more preferably 1 or less.
  • the lower limit of the mass ratio of component (B2) to epoxy resin (A) in the resin composition (component (B2)/component (A)) is, for example, 0 or more, from the viewpoint of further improving the glass transition temperature of the cured product. Therefore, it is preferably 0.1 or more, more preferably 0.5 or more.
  • the resin composition of the present invention may further contain a curing agent (B') other than the component (B) as an optional component.
  • (B') Other curing agents may be used singly or in any combination of two or more.
  • the (B') other curing agent can function as an epoxy resin curing agent that reacts with (A) the epoxy resin to cure it, similarly to the (B) active ester curing agent.
  • curing agents include, but are not limited to, phenol-based curing agents, carbodiimide-based curing agents, acid anhydride-based curing agents, amine-based curing agents, benzoxazine-based curing agents, Examples include cyanate ester-based curing agents and thiol-based curing agents. Among them, a curing agent selected from the group consisting of phenolic curing agents and carbodiimide curing agents is preferred.
  • a phenolic curing agent having a novolac structure is preferable from the viewpoint of heat resistance and water resistance.
  • a nitrogen-containing phenolic curing agent is preferred, and a triazine skeleton-containing phenolic curing agent is more preferred.
  • a triazine skeleton-containing phenol novolak resin is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion.
  • Specific examples of the phenol-based curing agent include, for example, Meiwa Chemical Co., Ltd. "MEH-7700", “MEH-7810", “MEH-7851”, Nippon Kayaku Co., Ltd.
  • carbodiimide-based curing agents include curing agents having one or more, preferably two or more carbodiimide structures in one molecule.
  • biscarbodiimides such as aromatic biscarbodiimides such as phenylene-bis(xylylcarbodiimide); polyhexamethylenecarbodiimide, polytrimethylhexamethylenecarbodiimide, polycyclohexylenecarbodiimide, poly(methylene biscyclohexylenecarbodiimide), poly(isophoronecarbodiimide) and other aliphatic polycarbodiimides; poly(phenylenecarbodiimide), poly(naphthylenecarbodiimide), poly(tylenecarbodiimide), poly(methyldiisopropylphenylenecarbodiimide), poly(triethylphenylene carbodiimide), poly(diethylphenylenecarbodiimide), poly(triisopropylphenylenecarbodiimide),
  • carbodiimide curing agents examples include “Carbodilite V-02B”, “Carbodilite V-03”, “Carbodilite V-04K”, “Carbodilite V-07” and “Carbodilite V-09” manufactured by Nisshinbo Chemical Co., Ltd. "Stabaxol P”, “Stabaxol P400”, and “Hykasil 510” manufactured by Rhein Chemie.
  • the acid anhydride curing agent includes curing agents having one or more acid anhydride groups in one molecule, preferably curing agents having two or more acid anhydride groups in one molecule.
  • Specific examples of acid anhydride curing agents include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, and hydrogenated methylnadic acid.
  • acid anhydride-based curing agents include “HNA-100”, “MH-700”, “MTA-15”, “DDSA” and “OSA” manufactured by Shin Nippon Rika Co., Ltd., and " YH-306", “YH-307”, Hitachi Chemical "HN-2200”, “HN-5500”, Clay Valley “EF-30”, “EF-40” “EF-60”, “EF -80” and the like.
  • Amine-based curing agents include curing agents having one or more, preferably two or more amino groups in one molecule. Examples include aliphatic amines, polyether amines, alicyclic amines, Aromatic amines and the like can be mentioned, and among them, aromatic amines are preferable from the viewpoint of achieving the desired effects of the present invention. Amine-based curing agents are preferably primary amines or secondary amines, more preferably primary amines.
  • amine curing agents include 4,4'-methylenebis(2,6-dimethylaniline), 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, and 3,3'-diaminodiphenylsulfone.
  • amine-based curing agents may be used, for example, "SEIKACURE-S” manufactured by Seika, "KAYABOND C-200S”, “KAYABOND C-100” and “Kayahard AA” manufactured by Nippon Kayaku. , “Kayahard AB”, “Kayahard AS”, “Epicure W” manufactured by Mitsubishi Chemical Corporation, and the like.
  • benzoxazine-based curing agents include “JBZ-OP100D” and “ODA-BOZ” manufactured by JFE Chemical Co., Ltd.; “HFB2006M” manufactured by Showa Polymer Co., Ltd.; Examples include “Fa”.
  • cyanate ester curing agents include bisphenol A dicyanate, polyphenolcyanate (oligo(3-methylene-1,5-phenylenecyanate)), 4,4'-methylenebis(2,6-dimethylphenylcyanate), 4, 4′-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatophenylmethane), bis(4-cyanate-3,5- Difunctional cyanate resins such as dimethylphenyl)methane, 1,3-bis(4-cyanatophenyl-1-(methylethylidene))benzene, bis(4-cyanatophenyl)thioether, and bis(4-cyanatophenyl)ether, Polyfunctional cyanate resins derived from phenol novolak, cresol novolak, etc., and prepolymers obtained by partially triazine-forming these cyan
  • cyanate ester curing agents include “PT30” and “PT60” (both phenol novolac type polyfunctional cyanate ester resins), “BA230” and “BA230S75” (part of bisphenol A dicyanate) manufactured by Lonza Japan Co., Ltd. or a prepolymer that is entirely triazined to form a trimer), and the like.
  • thiol-based curing agents examples include trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), tris (3-mercaptopropyl) isocyanurate, and the like.
  • the reactive group equivalent of other curing agents is preferably 50 g/eq. ⁇ 3000g/eq. , more preferably 100 g/eq. ⁇ 1000 g/eq. , more preferably 100 g/eq. ⁇ 500 g/eq. , particularly preferably 100 g/eq. ⁇ 300 g/eq. is.
  • Reactive group equivalent weight is the mass of curing agent per equivalent of reactive group.
  • a reactive group means a group that reacts with an epoxy resin, and is a phenolic hydroxyl group in the case of a phenol-based curing agent, and a carbodiimide group in the case of a carbodiimide-based curing agent, and varies depending on the type of curing agent.
  • the content of (B') other curing agent in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 15% by mass or less, or more. It is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less.
  • the lower limit of the content of (B′) other curing agent in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, for example, 0% by mass or more , 0.01% by mass or more, 0.1% by mass or more, 1% by mass or more, 1.5% by mass or more, and the like.
  • the content of (B) the active ester-based curing agent in the resin composition is 100% by mass of the active ester-based curing agent (B) and (B′) other curing agent in the resin composition. It is preferably 10% by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, and particularly preferably 50% by mass or more.
  • the ratio of the total number of molar equivalents of epoxy groups in (A) the epoxy resin in the resin composition to the total number of molar equivalents of curing agent reactive groups in (B) the active ester curing agent and (B') other curing agents in the resin composition is preferably in the range of 0.2 to 2, more preferably in the range of 0.5 to 1.8, and even more preferably in the range of 1 to 1.5.
  • Total molar equivalent number of epoxy groups in (A) epoxy resin indicates the sum of values obtained by dividing the mass of (A) epoxy resin present in the resin composition by the epoxy equivalent.
  • the total number of molar equivalents of the curing agent reactive groups in (B) the active ester curing agent and (B') the other curing agent is the mass of the (B) active ester curing agent present in the resin composition. is divided by the active ester group equivalent, and (B') the sum of the values obtained by dividing the mass of other curing agents by the reactive group equivalent.
  • the resin composition of the present invention contains (C) an inorganic filler.
  • the inorganic filler is contained in the resin composition in the form of particles.
  • An inorganic compound is used as the material for the inorganic filler.
  • inorganic filler materials include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, and water.
  • silica is particularly suitable.
  • examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. As silica, spherical silica is preferable.
  • Inorganic fillers may be used singly or in combination of two or more at any ratio.
  • inorganic fillers include, for example, "SP60-05” and “SP507-05” manufactured by Nippon Steel Chemical &Materials; “YC100C”, “YA050C” and “YA050C-” manufactured by Admatechs MJE", “YA010C”; “UFP-30” manufactured by Denka; “Silfil NSS-3N”, “Silfil NSS-4N”, “Silfil NSS-5N” manufactured by Tokuyama; “SC2500SQ” manufactured by Admatechs , “SO-C4”, “SO-C2”, “SO-C1”; “DAW-03” and “FB-105FD” manufactured by Denka; “BA-S” manufactured by JGC Catalysts and Chemicals, etc. .
  • the average particle size of the inorganic filler (C) is not particularly limited, but is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, even more preferably 4 ⁇ m or less, even more preferably 3 ⁇ m or less, and particularly preferably 2.0 ⁇ m or less. 7 ⁇ m or less.
  • the lower limit of the average particle size of the inorganic filler is not particularly limited, but is preferably 0.01 ⁇ m or more, more preferably 0.05 ⁇ m or more, still more preferably 0.1 ⁇ m or more, and particularly preferably 0 .2 ⁇ m or more.
  • the average particle size of the inorganic filler can be measured by a laser diffraction/scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler is prepared on a volume basis using a laser diffraction/scattering type particle size distribution measuring device, and the median diameter can be used as the average particle size for measurement.
  • a measurement sample can be obtained by weighing 100 mg of an inorganic filler and 10 g of methyl ethyl ketone in a vial and dispersing them with ultrasonic waves for 10 minutes.
  • a measurement sample is measured using a laser diffraction particle size distribution measuring device, the wavelengths of the light source used are blue and red, the volume-based particle size distribution of the inorganic filler is measured by the flow cell method, and from the obtained particle size distribution The average particle diameter was calculated as the median diameter.
  • the laser diffraction particle size distribution analyzer include "LA-960" manufactured by Horiba, Ltd., and the like.
  • the specific surface area of the inorganic filler is not particularly limited, but is preferably 0.1 m 2 /g or more, more preferably 0.5 m 2 /g or more, still more preferably 1 m 2 /g or more, Particularly preferably, it is 3 m 2 /g or more.
  • the upper limit of the specific surface area of the inorganic filler (C) is not particularly limited, it is preferably 100 m 2 /g or less, more preferably 70 m 2 /g or less, even more preferably 50 m 2 /g or less, and particularly preferably is 40 m 2 /g or less.
  • the specific surface area of the inorganic filler is determined by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech) according to the BET method, and calculating the specific surface area using the BET multipoint method. obtained by
  • the inorganic filler is a non-hollow inorganic filler (preferably non-hollow silica) with a porosity of 0% by volume, or a hollow inorganic filler with a porosity of more than 0% by volume (preferably hollow silica) may be, or may include both.
  • the inorganic filler contains only a hollow inorganic filler (preferably hollow silica), or a non-hollow inorganic filler (preferably non-hollow silica) and a hollow inorganic filler, from the viewpoint of keeping the dielectric constant lower. (preferably hollow silica).
  • the porosity of the hollow inorganic filler is preferably 70% by volume or less, more preferably 50% by volume or less, and particularly preferably 30% by volume or less.
  • the lower limit of the porosity of the inorganic filler can be, for example, more than 0% by volume, 1% by volume or more, 5% by volume or more, or 10% by volume or more.
  • the porosity P (% by volume) of the inorganic filler is the volume-based ratio of the total volume of one or more pores present inside the particle to the volume of the entire particle based on the outer surface of the particle (the number of pores total volume/particle volume), e.g., the measured actual density D M (g/cm 3 ) of the inorganic filler and the theoretical material density D T (g/cm 3 ) of the material forming the inorganic filler. /cm 3 ), it is calculated by the following formula (1).
  • the actual density of the inorganic filler can be measured using, for example, a true density measuring device.
  • a true density measuring device examples include ULTRAPYCNOMETER 1000 manufactured by QUANTACHROME. Nitrogen, for example, is used as the measuring gas.
  • the inorganic filler is preferably treated with a surface treatment agent from the viewpoint of enhancing moisture resistance and dispersibility.
  • surface treatment agents include fluorine-containing silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, organosilazane compounds, and titanate compounds.
  • a coupling agent etc. are mentioned.
  • one type of surface treatment agent may be used alone, or two or more types may be used in combination.
  • Examples of commercially available surface treatment agents include “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM803” (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu Chemical Industry Co., Ltd. "KBE903” (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM573” (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.
  • the degree of surface treatment with the surface treatment agent is preferably within a predetermined range. Specifically, 100% by mass of the inorganic filler is preferably surface-treated with a surface treatment agent of 0.2% to 5% by mass, and is surface-treated with 0.2% to 3% by mass. more preferably 0.3 mass % to 2 mass % of the surface treatment.
  • the degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler.
  • the amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/m 2 or more, more preferably 0.1 mg/m 2 or more, and more preferably 0.2 mg/m 2 from the viewpoint of improving the dispersibility of the inorganic filler. The above is more preferable.
  • it is preferably 1.0 mg/m 2 or less, more preferably 0.8 mg/m 2 or less, and 0.5 mg/m 2 or less . More preferred are:
  • the amount of carbon per unit surface area of the inorganic filler can be measured after the surface-treated inorganic filler is washed with a solvent (eg, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with the surface treatment agent, and ultrasonic cleaning is performed at 25° C. for 5 minutes. After removing the supernatant liquid and drying the solid content, a carbon analyzer can be used to measure the amount of carbon per unit surface area of the inorganic filler. As a carbon analyzer, "EMIA-320V" manufactured by Horiba Ltd. can be used.
  • EMIA-320V manufactured by Horiba Ltd.
  • the content of (C) the inorganic filler in the resin composition is not particularly limited. It may be 85% by mass or less, more preferably 80% by mass or less, and particularly preferably 75% by mass or less.
  • the lower limit of the content of the inorganic filler (C) in the resin composition is not particularly limited. , or 10% by mass or more, more preferably 20% by mass or more, or 30% by mass or more, more preferably 40% by mass or more, or 50% by mass or more, even more preferably 55% by mass or more, or 60% by mass or more, Particularly preferably, it is 65% by mass or more, or 70% by mass or more.
  • the resin composition of the present invention may contain (D) a curing accelerator as an optional component.
  • the curing accelerator functions as a curing catalyst that accelerates the curing of the (A) epoxy resin.
  • Curing accelerators include, for example, phosphorus-based curing accelerators, urea-based curing accelerators, guanidine-based curing accelerators, imidazole-based curing accelerators, metal-based curing accelerators, and amine-based curing accelerators. .
  • a curing accelerator preferably containing an imidazole-based curing accelerator.
  • the curing accelerator may be used singly or in combination of two or more.
  • Phosphorus curing accelerators include, for example, tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium) pyromellitate, tetrabutylphosphonium hydro Aliphatic phosphonium salts such as genhexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate, di-tert-butyldimethylphosphonium tetraphenylborate; methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltripheny
  • Urea-based curing accelerators include, for example, 1,1-dimethylurea; 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, 3- Aliphatic dimethylurea such as cyclooctyl-1,1-dimethylurea; 3-phenyl-1,1-dimethylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl )-1,1-dimethylurea, 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4- methylphenyl)-1,1-dimethylurea, 3-(3,4-dimethylphenyl)-1,1-dimethylurea, 3-(4-isopropylphenyl)-1,1-dimethyl
  • Guanidine curing accelerators include, for example, dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, Tetramethylguanidine, Pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0] Dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1 -allylbiguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide and
  • imidazole curing accelerators examples include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl- 2-phenylimidazolium trimellitate, 2,4-d
  • imidazole-based curing accelerator a commercially available product may be used. "P200-H50" of.
  • metal-based curing accelerators include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin.
  • organometallic complexes include organocobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organocopper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate.
  • organic zinc complexes such as iron (III) acetylacetonate; organic nickel complexes such as nickel (II) acetylacetonate; organic manganese complexes such as manganese (II) acetylacetonate;
  • organic metal salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.
  • amine curing accelerators examples include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo (5,4,0)-undecene and the like.
  • amine-based curing accelerator a commercially available product may be used, such as "MY-25” manufactured by Ajinomoto Fine-Techno Co., Ltd., and the like.
  • the content of the (D) curing accelerator in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 15% by mass or less, more preferably It is 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 2% by mass or less.
  • the lower limit of the content of (D) the curing accelerator in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, for example, 0% by mass or more, 0 It can be 0.001 wt% or more, 0.01 wt% or more, and the like.
  • the resin composition of the present invention may further contain optional additives.
  • additives include radically polymerizable additives having a vinylphenyl group, an acryloyl group, a methacryloyl group, a maleimide group (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl group), and the like.
  • radical polymerization initiators such as peroxide radical polymerization initiators and azo radical polymerization initiators
  • melamine sulfate melamine sulfate
  • halogen flame retardants e.g. antimony trioxide
  • phosphate ester dispersants polyoxyalkylene dispersants, acetylene dispersants Dispersants such as dispersants, silicone dispersants, anionic dispersants, cationic dispersants; borate stabilizers, titanate stabilizers, aluminate stabilizers, Stabilizers such as zirconate-based stabilizers, isocyanate-based stabilizers, carboxylic acid-based stabilizers, and carboxylic acid anhydride-based stabilizers are included.
  • Other additives may be used singly or in combination of two or more at any ratio.
  • the content of other additives can be appropriately set by those skilled in the art.
  • the resin composition of the present invention may further contain any organic solvent.
  • organic solvent a known one can be used as appropriate, and the type thereof is not particularly limited.
  • organic solvents include ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; Ester-based solvents such as butyrolactone; Ether-based solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, and anisole; Alcohol-based solvents such as methanol, ethanol, propanol, butanol, and ethylene glycol Solvent; Ether ester solvents such as 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol
  • the content of the (F) organic solvent in the varnish-like resin composition before drying is not particularly limited, but when all components in the resin composition are 100% by mass, for example, 40% by mass 30% by mass or less, preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 8% by mass or less, and particularly preferably 6% by mass or less.
  • the content of the (F) organic solvent in the resin composition that forms the resin composition layer after drying in the resin sheet is not particularly limited, but all components in the resin composition are 100% by mass. is preferably 5% by mass or less, more preferably 3% by mass or less, even more preferably 2% by mass or less, and particularly preferably 1% by mass or less.
  • the resin composition of the present invention for example, in any preparation container (A) epoxy resin, (B) active ester curing agent, (C) inorganic filler, optionally (D) curing accelerator, optionally It can be manufactured by adding and mixing (E) other additives and (F) an organic solvent, if necessary, in any order and/or partly or wholly at the same time. Also, during the process of adding and mixing each component, the temperature can be set appropriately, and heating and/or cooling may be performed temporarily or over time. In addition, during or after the addition and mixing, the resin composition may be stirred or shaken using a stirring or shaking device such as a mixer to uniformly disperse. Moreover, simultaneously with stirring or shaking, defoaming may be performed under low pressure conditions such as vacuum.
  • the resin composition of the present invention contains (A) an epoxy resin, (B) an active ester curing agent, and (C) an inorganic filler, and the content of component (C) is such that the non-volatile components in the resin composition are When 100% by mass, it is 60% by mass or more, and the component (B) contains (B1) a terminal sterically hindered active ester curing agent. With such a resin composition, a cured product having excellent crack resistance can be obtained.
  • the cured product of the resin composition of the present invention can have the characteristic of being able to suppress the occurrence of cracks after desmear treatment (roughening treatment). Therefore, in one embodiment, when 100 copper pad portions of the circuit board are observed after manufacturing and desmearing the circuit board as in Test Example 3 below, the number of cracks is preferably 10 or less (10% or less). could be.
  • the cured product of the resin composition of the present invention can be characterized by a low dielectric loss tangent (Df). Therefore, in one embodiment, the dielectric loss tangent (Df) of the cured product of the resin composition when measured at 5.8 GHz and 23° C. as in Test Example 1 below is preferably 0.010 or less, more preferably 0. 0.008 or less, more preferably 0.007 or less, even more preferably 0.005 or less, or 0.003 or less, and particularly preferably 0.0025 or less, or 0.002 or less.
  • Df dielectric loss tangent
  • the cured product of the resin composition of the present invention can be characterized by having a high glass transition point (Tg). Therefore, in one embodiment, the glass transition temperature (Tg) when measured as in Test Example 2 below is preferably 100° C. or higher, more preferably 120° C. or higher, still more preferably 130° C. or higher, and even more preferably It can be 140° C. or higher, particularly preferably 150° C. or higher.
  • the resin composition of the present invention can be suitably used as a resin composition for insulation, particularly as a resin composition for forming an insulation layer.
  • a resin composition for forming an insulating layer for forming a conductor layer (including a rewiring layer) formed on an insulating layer (resin for forming an insulating layer for forming a conductor layer composition).
  • a resin composition for forming an insulating layer of a printed wiring board (resin composition for forming an insulating layer of a printed wiring board).
  • the resin composition of the present invention also includes resin sheets, sheet laminate materials such as prepreg, solder resists, underfill materials, die bonding materials, semiconductor encapsulants, hole-filling resins, component-embedding resins, and the like. It can be used in a wide range of applications.
  • the resin composition of the present invention is used as an insulating layer for forming a rewiring layer.
  • a resin composition for forming a rewiring layer and a resin composition for sealing a semiconductor chip (a resin composition for semiconductor chip sealing).
  • a rewiring layer may be further formed on the encapsulation layer when the semiconductor chip package is manufactured.
  • the resin composition of the present invention provides an insulating layer with good part-embedding properties, it can be suitably used when the printed wiring board is a component-embedded circuit board.
  • the resin composition of the present invention can be applied in the form of a varnish, it is industrially preferably used in the form of a sheet-like laminated material containing the resin composition.
  • the resin sheets and prepregs shown below are preferable.
  • the resin sheet comprises a support and a resin composition layer provided on the support, and the resin composition layer is formed from the resin composition of the present invention.
  • the thickness of the resin composition layer is preferably 50 ⁇ m or less, more It is preferably 40 ⁇ m or less.
  • the lower limit of the thickness of the resin composition layer is not particularly limited, it can be usually 5 ⁇ m or more, 10 ⁇ m or more, or the like.
  • the support examples include a film made of a plastic material, a metal foil, and a release paper, and a film made of a plastic material and a metal foil are preferable.
  • plastic material examples include polyethylene terephthalate (hereinafter sometimes abbreviated as "PET”) and polyethylene naphthalate (hereinafter sometimes abbreviated as “PEN”).
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • PC polycarbonate
  • acrylic such as polymethyl methacrylate (PMMA)
  • PMMA polymethyl methacrylate
  • TAC triacetyl cellulose
  • PES polyether sulfide
  • polyether ketones polyimides, and the like.
  • polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.
  • examples of the metal foil include copper foil and aluminum foil, with copper foil being preferred.
  • a foil made of a single metal of copper may be used, and a foil made of an alloy of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. may be used.
  • the support may be subjected to matte treatment, corona treatment, or antistatic treatment on the surface to be bonded to the resin composition layer.
  • a support with a release layer having a release layer on the surface to be bonded to the resin composition layer may be used.
  • the release agent used in the release layer of the release layer-attached support includes, for example, one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins.
  • a commercially available product may be used, for example, "SK-1” manufactured by Lintec Co., Ltd., “SK-1", “ AL-5”, “AL-7”, Toray's "Lumirror T60", Teijin's "Purex", and Unitika's "Unipeel”.
  • the thickness of the support is not particularly limited, it is preferably in the range of 5 ⁇ m to 75 ⁇ m, more preferably in the range of 10 ⁇ m to 60 ⁇ m.
  • the thickness of the release layer-attached support as a whole is preferably within the above range.
  • the resin sheet may further contain any layer as necessary.
  • an optional layer include a protective film conforming to the support provided on the surface of the resin composition layer not bonded to the support (that is, the surface opposite to the support). be done.
  • the thickness of the protective film is not particularly limited, it is, for example, 1 ⁇ m to 40 ⁇ m.
  • a liquid (varnish) resin composition is used as it is, or a liquid (varnish) resin composition is prepared by dissolving the resin composition in an organic solvent, which is then coated using a die coater or the like. It can be produced by applying it on a support by drying, and then drying it to form a resin composition layer.
  • organic solvent examples include the same organic solvents as those described as components of the resin composition.
  • An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.
  • Drying may be carried out by known methods such as heating and blowing hot air.
  • the drying conditions are not particularly limited, but the resin composition layer is dried so that the content of the organic solvent is 10% by mass or less, preferably 5% by mass or less. Although it varies depending on the boiling point of the organic solvent in the resin composition, for example, when using a resin composition containing 30% by mass to 60% by mass of the organic solvent, drying at 50 ° C. to 150 ° C. for 3 to 10 minutes A resin composition layer can be formed.
  • the resin sheet can be rolled up and stored.
  • the resin sheet has a protective film, it can be used by peeling off the protective film.
  • the prepreg is formed by impregnating a sheet-like fiber base material with the resin composition of the present invention.
  • the sheet-like fiber base material used for the prepreg is not particularly limited, and those commonly used as prepreg base materials such as glass cloth, aramid nonwoven fabric, and liquid crystal polymer nonwoven fabric can be used.
  • the thickness of the sheet-like fiber base material is preferably 50 ⁇ m or less, more preferably 40 ⁇ m or less, still more preferably 30 ⁇ m or less, and particularly preferably 20 ⁇ m or less.
  • the lower limit of the thickness of the sheet-like fiber base material is not particularly limited. Usually, it is 10 ⁇ m or more.
  • a prepreg can be manufactured by a known method such as a hot melt method or a solvent method.
  • the thickness of the prepreg can be in the same range as the resin composition layer in the resin sheet described above.
  • the sheet-like laminated material of the present invention can be suitably used for forming an insulating layer of a printed wiring board (for an insulating layer of a printed wiring board), and for forming an interlayer insulating layer of a printed wiring board (for a printed wiring board). for interlayer insulating layers of wiring boards).
  • the printed wiring board of the present invention includes an insulating layer made of a cured product obtained by curing the resin composition of the present invention.
  • a printed wiring board can be manufactured, for example, using the resin sheet described above by a method including the following steps (I) and (II).
  • (I) A step of laminating a resin sheet on the inner layer substrate so that the resin composition layer of the resin sheet is bonded to the inner layer substrate
  • (II) Curing (for example, thermosetting) the resin composition layer to form an insulating layer process
  • the “inner layer substrate” used in step (I) is a member that serves as a printed wiring board substrate, and includes, for example, a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. etc.
  • the substrate may also have a conductor layer on one or both sides thereof, and the conductor layer may be patterned.
  • An inner layer substrate having conductor layers (circuits) formed on one side or both sides of the substrate is sometimes referred to as an "inner layer circuit board.”
  • an intermediate product on which an insulating layer and/or a conductor layer are to be further formed when manufacturing a printed wiring board is also included in the "inner layer substrate" as used in the present invention.
  • an inner layer board with built-in components may be used.
  • Lamination of the inner layer substrate and the resin sheet can be performed, for example, by heat-pressing the resin sheet to the inner layer substrate from the support side.
  • the member for thermocompression bonding the resin sheet to the inner layer substrate include heated metal plates (such as SUS end plates) and metal rolls (SUS rolls).
  • thermocompression bonding member instead of pressing the thermocompression member directly onto the resin sheet, it is preferable to press through an elastic material such as heat-resistant rubber so that the resin sheet can sufficiently follow the uneven surface of the inner layer substrate.
  • Lamination of the inner layer substrate and the resin sheet may be performed by a vacuum lamination method.
  • the thermocompression temperature is preferably in the range of 60° C. to 160° C., more preferably 80° C. to 140° C.
  • the thermocompression pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0. .29 MPa to 1.47 MPa
  • the heat pressing time is preferably 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds.
  • Lamination can be carried out under reduced pressure conditions, preferably at a pressure of 26.7 hPa or less.
  • Lamination can be done with a commercially available vacuum laminator.
  • Commercially available vacuum laminators include, for example, a vacuum pressurized laminator manufactured by Meiki Seisakusho, a vacuum applicator manufactured by Nikko Materials, a batch vacuum pressurized laminator, and the like.
  • the laminated resin sheets may be smoothed under normal pressure (atmospheric pressure), for example, by pressing a thermocompression member from the support side.
  • the pressing conditions for the smoothing treatment may be the same as the thermocompression bonding conditions for the lamination described above.
  • Smoothing treatment can be performed with a commercially available laminator. Lamination and smoothing may be performed continuously using the above-mentioned commercially available vacuum laminator.
  • the support may be removed between step (I) and step (II), or may be removed after step (II).
  • step (II) the resin composition layer is cured (for example, thermally cured) to form an insulating layer made of the cured resin composition.
  • Curing conditions for the resin composition layer are not particularly limited, and conditions that are usually employed when forming an insulating layer of a printed wiring board may be used.
  • the thermosetting conditions for the resin composition layer vary depending on the type of resin composition, etc., but in one embodiment, the curing temperature is preferably 120° C. to 240° C., more preferably 150° C. to 220° C., and even more preferably 150° C. to 220° C. is between 170°C and 210°C.
  • the curing time can be preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, even more preferably 15 minutes to 100 minutes.
  • the resin composition layer may be preheated at a temperature lower than the curing temperature before thermally curing the resin composition layer.
  • the resin composition layer is cured at a temperature of 50° C. to 120° C., preferably 60° C. to 115° C., more preferably 70° C. to 110° C. for 5 minutes or more, It may be preheated for preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, even more preferably 15 minutes to 100 minutes.
  • steps (III) to (V) may be carried out according to various methods known to those skilled in the art that are used in the manufacture of printed wiring boards.
  • the support is removed after step (II), the support may be removed between step (II) and step (III), between step (III) and step (IV), or step ( It may be carried out between IV) and step (V). If necessary, the steps (II) to (V) of forming the insulating layer and the conductor layer may be repeated to form a multilayer wiring board.
  • the printed wiring board of the present invention can be manufactured using the prepreg described above.
  • the manufacturing method is basically the same as in the case of using a resin sheet.
  • the step (III) is a step of drilling holes in the insulating layer, whereby holes such as via holes and through holes can be formed in the insulating layer.
  • Step (III) may be performed using, for example, a drill, laser, plasma, or the like, depending on the composition of the resin composition used to form the insulating layer. The dimensions and shape of the holes may be appropriately determined according to the design of the printed wiring board.
  • Step (IV) is a step of roughening the insulating layer. Smear is usually also removed in this step (IV).
  • the procedure and conditions of the roughening treatment are not particularly limited, and known procedures and conditions that are commonly used in forming insulating layers of printed wiring boards can be employed.
  • the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralizing treatment with a neutralizing liquid in this order.
  • the swelling liquid used in the roughening treatment is not particularly limited, but examples thereof include alkaline solutions, surfactant solutions, etc., preferably alkaline solutions, more preferably sodium hydroxide solutions and potassium hydroxide solutions. preferable.
  • Examples of commercially available swelling liquids include "Swelling Dip Securigans P" and "Swelling Dip Securigans SBU” manufactured by Atotech Japan.
  • the swelling treatment with the swelling liquid is not particularly limited, but can be performed, for example, by immersing the insulating layer in the swelling liquid at 30.degree. C. to 90.degree. C. for 1 to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling liquid at 40° C. to 80° C. for 5 minutes to 15 minutes.
  • the oxidizing agent used for the roughening treatment is not particularly limited, but examples include an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide.
  • the roughening treatment with an oxidizing agent such as an alkaline permanganate solution is preferably carried out by immersing the insulating layer in an oxidizing agent solution heated to 60° C. to 100° C. for 10 to 30 minutes.
  • the permanganate concentration in the alkaline permanganate solution is preferably 5% by mass to 10% by mass.
  • Examples of commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Security P" manufactured by Atotech Japan.
  • an acidic aqueous solution is preferable, and commercially available products include, for example, "Reduction Solution Securigant P" manufactured by Atotech Japan.
  • the treatment with the neutralizing solution can be performed by immersing the treated surface roughened with the oxidizing agent in the neutralizing solution at 30°C to 80°C for 5 to 30 minutes. From the viewpoint of workability, etc., a method of immersing an object roughened with an oxidizing agent in a neutralizing solution at 40° C. to 70° C. for 5 to 20 minutes is preferable.
  • the arithmetic mean roughness (Ra) of the insulating layer surface after roughening treatment is not particularly limited, but is preferably 500 nm or less, more preferably 400 nm or less, and still more preferably 300 nm or less. .
  • the lower limit is not particularly limited, and may be, for example, 1 nm or more, 2 nm or more.
  • the root mean square roughness (Rq) of the surface of the insulating layer after roughening treatment is preferably 500 nm or less, more preferably 400 nm or less, and even more preferably 300 nm or less.
  • the lower limit is not particularly limited, and may be, for example, 1 nm or more, 2 nm or more.
  • the arithmetic mean roughness (Ra) and root mean square roughness (Rq) of the insulating layer surface can be measured using a non-contact surface roughness meter.
  • the step (V) is a step of forming a conductor layer, and forms the conductor layer on the insulating layer.
  • the conductor material used for the conductor layer is not particularly limited.
  • the conductor layer contains one or more selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. Contains metal.
  • the conductor layer may be a single metal layer or an alloy layer, and the alloy layer may be, for example, an alloy of two or more metals selected from the above group (for example, a nickel-chromium alloy, a copper- nickel alloys and copper-titanium alloys).
  • single metal layers of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, nickel-chromium alloys, copper- Nickel alloys and copper/titanium alloy alloy layers are preferred, and single metal layers of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or nickel/chromium alloy alloy layers are more preferred, and copper single metal layers are preferred.
  • a metal layer is more preferred.
  • the conductor layer may have a single layer structure or a multi-layer structure in which two or more single metal layers or alloy layers made of different kinds of metals or alloys are laminated.
  • the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc or titanium, or an alloy layer of nickel-chromium alloy.
  • the thickness of the conductor layer is generally 3 ⁇ m to 35 ⁇ m, preferably 5 ⁇ m to 30 ⁇ m, depending on the desired printed wiring board design.
  • the conductor layer may be formed by plating.
  • a conductive layer having a desired wiring pattern can be formed by plating the surface of an insulating layer by a conventionally known technique such as a semi-additive method or a full-additive method. It is preferably formed by a method.
  • a semi-additive method is shown below.
  • a plating seed layer is formed on the surface of the insulating layer by electroless plating.
  • a mask pattern is formed on the formed plating seed layer to expose a portion of the plating seed layer corresponding to a desired wiring pattern.
  • the mask pattern is removed. After that, the unnecessary plating seed layer is removed by etching or the like, and a conductor layer having a desired wiring pattern can be formed.
  • the conductor layer may be formed using metal foil.
  • step (V) is preferably performed between step (I) and step (II).
  • step (I) the support is removed and a metal foil is laminated on the exposed surface of the resin composition layer.
  • Lamination of the resin composition layer and the metal foil may be carried out by a vacuum lamination method. The lamination conditions may be the same as those described for step (I).
  • step (II) is performed to form an insulating layer.
  • a conductor layer having a desired wiring pattern can be formed by conventional known techniques such as the subtractive method and the modified semi-additive method.
  • a metal foil can be manufactured by a known method such as an electrolysis method or a rolling method.
  • Commercially available metal foils include, for example, HLP foil and JXUT-III foil manufactured by JX Nippon Mining & Metals Co., Ltd., 3EC-III foil and TP-III foil manufactured by Mitsui Kinzoku Mining Co., Ltd., and the like.
  • a semiconductor device of the present invention includes the printed wiring board of the present invention.
  • the semiconductor device of the present invention can be manufactured using the printed wiring board of the present invention.
  • semiconductor devices examples include various semiconductor devices used in electrical products (such as computers, mobile phones, digital cameras, televisions, etc.) and vehicles (such as motorcycles, automobiles, trains, ships, aircraft, etc.).
  • IR Infrared spectroscopic analysis (IR) of active ester A
  • An IR chart of active ester A is shown in FIG.
  • the measurement conditions are as follows. Measuring device: FT/IR-4600 manufactured by JASCO Corporation Measurement method: KBr plate method, permeation measurement Sample and measurement: A sample was prepared by diluting with a tetrahydrofuran solution so that the resin solid content was 10% by mass. 0.1 ml of the sample was dropped onto a KBr plate, and the THF and H 2 O were dried in an oven at 100° C. for 10 minutes, and then the transmission measurement was performed.
  • benzyl-modified naphthalene compound (A-1) was obtained.
  • the resulting benzyl-modified naphthalene compound (A-1) was a black solid and had a hydroxyl equivalent weight of 180 g/equivalent.
  • a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube, and a stirrer was charged with 203.0 g of isophthaloyl chloride (moles of acid chloride group: 2.0 mol) and 1400 g of toluene, and the system was evacuated. It was dissolved under nitrogen substitution. Next, 72.4 g (0.67 mol) of ortho-cresol and 240 g of benzyl-modified naphthalene compound (A-1) (number of moles of phenolic hydroxyl group: 1.33 mol) were charged, and the system was decompressed and replaced with nitrogen to dissolve. .
  • Example 1 6 parts of epoxy resin "ESN475V” (manufactured by Nippon Steel Chemical & Material, epoxy equivalent: about 330 g/eq.) and epoxy resin "HP-4032-SS” (manufactured by DIC, epoxy equivalent: about 144 g/eq.) 4 parts was dissolved in 10 parts of methyl ethyl ketone (MEK) to obtain an epoxy resin solution.
  • ESN475V manufactured by Nippon Steel Chemical & Material, epoxy equivalent: about 330 g/eq.
  • HP-4032-SS manufactured by DIC, epoxy equivalent: about 144 g/eq.
  • KBM573 surface-treated Add 65 parts of spherical silica (“SO-C2” manufactured by Admatechs, average particle size 0.77 ⁇ m) and 0.2 parts of an imidazole curing accelerator (“1B2PZ” manufactured by Shikoku Kasei Co., Ltd.) and mix uniformly with a high-speed rotating mixer. A varnish-like resin composition was prepared by dispersion.
  • Example 2 Naphthol-terminated active ester-based curing agent (manufactured by DIC Corporation "HPC-8150-62T”) instead of 11 parts of naphthol-terminated active ester-based curing agent (manufactured by DIC Corporation "HPC-8000-65T", active ester equivalent 223, A varnish-like resin composition was prepared in the same manner as in Example 1, except that 11 parts of a toluene solution having a nonvolatile content of 65% by mass was used.
  • Example 3 The amount of spherical silica (“SO-C2” manufactured by Admatechs Co., Ltd.) was changed from 65 parts to 70 parts, and the amount of imidazole curing accelerator (“1B2PZ” manufactured by Shikoku Kasei Co., Ltd.) was changed from 0.2 parts to 0. 02 parts, and 2 parts of a phenol-based curing agent (DIC's "LA-3018-50P", phenol equivalent of 151, non-volatile content of 50% by mass in 1-methoxy-2 propanol solution), and a carbodiimide-based curing agent.
  • SO-C2 spherical silica
  • 1B2PZ imidazole curing accelerator
  • 1B2PZ imidazole curing accelerator
  • a varnish-like resin composition was prepared in the same manner as in Example 1, except that 1 part of ("V-03" manufactured by Nisshinbo Chemical Co., Ltd., a toluene solution having a nonvolatile content of 50% by mass) was added.
  • Example 4 The amount of spherical silica (“SO-C2” manufactured by Admatechs Co., Ltd.) was changed from 65 parts to 70 parts, and the amount of imidazole curing accelerator (“1B2PZ” manufactured by Shikoku Kasei Co., Ltd.) was changed from 0.2 parts to 0. 02 parts, and 2 parts of a phenol-based curing agent (DIC's "LA-3018-50P", phenol equivalent of 151, non-volatile content of 50% by mass in 1-methoxy-2 propanol solution), and a carbodiimide-based curing agent.
  • SO-C2 spherical silica
  • 1B2PZ imidazole curing accelerator
  • 1B2PZ imidazole curing accelerator
  • a varnish-like resin composition was prepared in the same manner as in Example 2, except that 1 part of ("V-03" manufactured by Nisshinbo Chemical Co., Ltd., a toluene solution with a non-volatile content of 50% by mass) was added.
  • Example 5 The amount of spherical silica ("SO-C2" manufactured by Admatechs) was changed from 70 parts to 35 parts, and hollow silica ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) surface-treated with an amine-based alkoxysilane compound ( A varnish-like resin composition was prepared in the same manner as in Example 3, except that 35 parts of "BA-S” manufactured by Nikki Shokubai Kasei Co., Ltd., average particle size 2.6 ⁇ m, porosity 25% by volume) was added. .
  • Example 6 Without using a terminal naphthol-type active ester curing agent ("HPC-8150-62T" manufactured by DIC), the amount of active ester A (terminal sterically hindered ester curing agent) obtained in Synthesis Example 1 was reduced to 11.
  • a varnish-like resin composition was prepared in the same manner as in Example 5, except that the amount was changed from 1 part to 22 parts.
  • Example 7 Active ester B obtained in Synthesis Example 2 (terminal ortho-cresol type active ester curing agent, non-volatile content 65 mass % toluene solution) was used in the same manner as in Example 1, to prepare a varnish-like resin composition.
  • Example 8 Active ester C obtained in Synthesis Example 3 instead of 11 parts of naphthol-terminated active ester-based curing agent (manufactured by DIC "HPC-8150-62T") (terminal ortho-phenylphenol-based active ester-based curing agent, non-volatile content 65 A varnish-like resin composition was prepared in the same manner as in Example 1, except that 11 parts of the toluene solution (% by mass) was used.
  • ⁇ Production Example 1 Resin sheet having a resin composition layer with a thickness of 40 ⁇ m>
  • a polyethylene terephthalate film (“AL5” manufactured by Lintec Corporation, thickness 38 ⁇ m) provided with a release layer was prepared.
  • the resin compositions obtained in Examples and Comparative Examples were uniformly applied so that the thickness of the resin composition layer after drying was 40 ⁇ m. Thereafter, the resin composition was dried at 80° C. to 100° C. (average 90° C.) for 4 minutes to obtain a resin sheet including a support and a resin composition layer.
  • ⁇ Production Example 2 Resin sheet with resin composition layer having a thickness of 25 ⁇ m>
  • the resin compositions obtained in Examples and Comparative Examples were uniformly applied so that the thickness of the resin composition layer after drying was 25 ⁇ m, and the temperature was 70° C. to 80° C. (average 75° C.). for 2.5 minutes to obtain a resin sheet containing the support and the resin composition layer.
  • ⁇ Test Example 1 Measurement of dielectric loss tangent (Df) and dielectric constant (Dk)>
  • the 40 ⁇ m-thick resin sheet produced in Production Example 1 was heated at 190° C. for 90 minutes to thermally cure the resin composition layer. After that, the support was peeled off to obtain a cured product of the resin composition. This cured product was cut into test pieces having a width of 2 mm and a length of 80 mm.
  • the dielectric loss tangent (Df) and dielectric constant (Dk) of the test piece were measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23° C. by the cavity resonance perturbation method using “HP8362B” manufactured by Agilent Technologies. Three test pieces were measured, and the average values are shown in Table 1 below.
  • Tg glass transition temperature
  • Test Example 2 Measurement of glass transition temperature (Tg)>
  • the cured product prepared in Test Example 1 was cut into a piece having a length of 20 mm and a width of 6 mm to obtain an evaluation sample.
  • the glass transition temperature (Tg) of each evaluation sample was measured from 25° C. to 250° C. at a heating rate of 5° C./min using a TMA apparatus manufactured by Rigaku. Two measurements were made on the same specimen and the second value was recorded.
  • a core material (Hitachi Chemical Co., Ltd.) is made by forming circular copper pads (thickness of copper: 35 ⁇ m) with a diameter of 350 ⁇ m in a grid shape at intervals of 400 ⁇ m so that the resin sheet with a thickness of 25 ⁇ m prepared in Production Example 2 has a residual copper rate of 60%.
  • "E705GR”, thickness 400 ⁇ m) on both sides of the resin composition layer using a batch-type vacuum pressure laminator (2-stage build-up laminator "CVP700” manufactured by Nikko Materials Co., Ltd.)
  • the resin composition layer is bonded to the inner layer substrate. It was laminated on both sides of the inner layer substrate as shown.
  • This lamination was carried out by pressure bonding for 30 seconds at a temperature of 100° C. and a pressure of 0.74 MPa after reducing the pressure to 13 hPa or less for 30 seconds. This was placed in an oven at 130° C. and heated for 30 minutes, then transferred to an oven at 170° C. and heated for 30 minutes. Further, the support layer was peeled off, and the resulting circuit board was immersed in a swelling liquid, Swelling Dip Securigant P (Atotech Japan Co., Ltd.), at 60° C. for 10 minutes.
  • Table 1 summarizes the amount of raw material used in the resin composition of each example and comparative example, the measurement results and evaluation results of test examples.

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Abstract

La présente invention aborde le problème de la fourniture d'une composition de résine à partir de laquelle un produit durci ayant une excellente résistance à la fissuration peut être obtenu. La présente invention concerne une composition de résine comprenant (A) une résine époxy, (B) un agent de durcissement à base d'ester actif et (C) une charge inorganique, la teneur en composant (C) étant d'au moins 60 % en masse lorsqu'un composant non volatil dans la composition de résine est de 100 % en masse ; et le composant (B) comprenant (B1) un agent de durcissement à base d'ester actif ayant une structure représentée par la formule (B1-1). Chaque symbole est tel que défini dans la description.
PCT/JP2022/032089 2021-08-26 2022-08-25 Composition de résine WO2023027154A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018173500A1 (fr) * 2017-03-24 2018-09-27 Dic株式会社 Composition d'ester actif
JP2021004297A (ja) * 2019-06-25 2021-01-14 味の素株式会社 樹脂組成物
JP2021085030A (ja) * 2019-11-29 2021-06-03 味の素株式会社 樹脂組成物
JP2021107507A (ja) * 2019-12-27 2021-07-29 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

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Publication number Priority date Publication date Assignee Title
FR2865734B1 (fr) 2004-02-03 2006-05-19 Servier Lab NOUVAEUX DERIVES DE BENZO[b]CHROMENO-NAPHTHYRIDIN-7-ONE ET DE PYRANO[2'3':7,8]QUINO[2,3-b]QUINOXALIN-7-ONE, LEUR PROCEDE DE PREPARATION ET LES COMPOSITIONS PHARMACEUTIQUES QUI LES CONTIENNENT
JP2021014545A (ja) 2019-07-12 2021-02-12 味の素株式会社 樹脂組成物
JP2020023714A (ja) 2019-10-24 2020-02-13 積水化学工業株式会社 樹脂材料及び多層プリント配線板

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018173500A1 (fr) * 2017-03-24 2018-09-27 Dic株式会社 Composition d'ester actif
JP2021004297A (ja) * 2019-06-25 2021-01-14 味の素株式会社 樹脂組成物
JP2021085030A (ja) * 2019-11-29 2021-06-03 味の素株式会社 樹脂組成物
JP2021107507A (ja) * 2019-12-27 2021-07-29 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

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