resin composition

Abstract

To provide a resin composition from which a cured product having a reduced relative dielectric constant (Dk) is obtainable.SOLUTION: A resin composition contains (A) a polycarbonate resin and (B) an epoxy resin, where the component (A) contains a polycarbonate resin having a repeated structural unit represented by the following formula (A1). In the formula, a ring A and a ring B each independently represents an aromatic ring that may have a substituent, and a ring X represents a non-aromatic carbon ring that may have a substituent and has 7 or more carbon atoms.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a resin composition containing a polycarbonate resin, and further to a cured product, a sheet-like laminate material, a resin sheet, a printed wiring board, and a semiconductor device obtained using the resin composition. [Background technology]

[0002] A known manufacturing technique for printed wiring boards is the build-up method, in which insulating layers and conductor layers are alternately stacked. In build-up manufacturing methods, the insulating layers are generally formed by curing a resin composition. In recent years, there has been a demand for lowering the dielectric constant (Dk) of the insulating layer.

[0003] Incidentally, polycarbonate resins having an alicyclic structure have been known so far (Patent Document 1). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2018-197282 Summary of the Invention [Problem to be solved by the invention]

[0005] An object of the present invention is to provide a resin composition that can give a cured product having a lower relative dielectric constant (Dk). [Means for solving the problem]

[0006] In order to achieve the objects of the present invention, the present inventors conducted extensive research and unexpectedly found that by using a resin composition comprising (A) a polycarbonate resin and (B) an epoxy resin, in which component (A) contains a polycarbonate resin having a repeating structural unit represented by formula (A1) described below, a cured product with a lower relative dielectric constant (Dk) can be obtained, leading to the completion of the present invention.

[0007] That is, the present invention includes the following. [1] A resin composition comprising (A) a polycarbonate resin and (B) an epoxy resin, The component (A) is a compound represented by the formula (A1):

[0008] [ka]

[0009] [In the formula, Ring A and ring B each independently represent an aromatic ring which may have a substituent; Ring X is a non-aromatic carbocyclic ring having 7 or more carbon atoms, which may have a substituent. A resin composition comprising a polycarbonate resin having a repeating structural unit represented by the formula: [2] The component (A) is a compound represented by the formula (A3):

[0010] [ka]

[0011] [In the formula, R 1 and R 2 each independently represents a hydrogen atom, an alkyl group, or an aryl group; R 3 and R 4 each independently represents an alkyl group or an aryl group; a and b each independently represent 0, 1, 2, 3, or 4; n is an integer of 6 or more. The resin composition according to [1] above, comprising a polycarbonate resin having a repeating structural unit represented by the following formula: [3] The resin composition according to the above [1] or [2], wherein the weight average molecular weight (Mw) of the component (A) is 10,000 or less. [4] The resin composition according to any one of the above [1] to [3], wherein the hydroxyl group content of the component (A) is 0.05 mmol / g or less. [5] The resin composition according to any one of the above [1] to [4], wherein the content of component (A) is 10% by mass or more, based on 100% by mass of the non-volatile components in the resin composition. [6] The resin composition according to any one of the above [1] to [5], wherein the content of component (A) is 50% by mass or less, assuming that the total amount of non-volatile components in the resin composition is 100% by mass. [7] The resin composition according to any one of the above [1] to [6], wherein the content of component (B) is 20% by mass or less, assuming that the total amount of non-volatile components in the resin composition is 100% by mass. [8] The resin composition according to any one of the above [1] to [7], further comprising (C) an inorganic filler. [9] The resin composition according to the above [8], wherein the component (C) is silica.

[10] The resin composition according to [8] or [9] above, wherein the content of component (C) is 40% by mass or more, assuming that the total amount of non-volatile components in the resin composition is 100% by mass.

[11] The resin composition according to any one of the above [1] to

[10] , further comprising (D) an epoxy resin curing agent.

[12] The resin composition according to

[11] above, wherein the component (D) contains an active ester curing agent.

[13] The resin composition according to any one of the above [1] to

[12] , further comprising (E) a radically polymerizable compound.

[14] The resin composition according to any one of the above [1] to

[13] , wherein the dielectric loss tangent (Df) of a cured product of the resin composition is 0.0040 or less when measured at 5.8 GHz and 23°C.

[15] The resin composition according to any one of the above [1] to

[14] , wherein the cured product of the resin composition has a relative dielectric constant (Dk) of 3.1 or less when measured at 5.8 GHz and 23°C.

[16] A cured product of the resin composition according to any one of [1] to

[15] above.

[17] A sheet-like laminate material containing the resin composition according to any one of the above [1] to

[15] .

[18] A resin sheet comprising a support and a resin composition layer formed on the support from the resin composition according to any one of [1] to

[15] above.

[19] A printed wiring board having an insulating layer made of a cured product of the resin composition according to any one of [1] to

[15] above.

[20] A semiconductor device comprising the printed wiring board according to

[19] above. [Effects of the Invention]

[0012] According to the resin composition of the present invention, a cured product having a lower relative dielectric constant (Dk) can be obtained. DETAILED DESCRIPTION OF THE INVENTION

[0013] The present invention will be described in detail below with reference to preferred embodiments thereof. However, the present invention is not limited to the following embodiments and examples, and can be implemented with any modifications within the scope of the claims of the present invention and their equivalents.

[0014] <Resin composition> The resin composition of the present invention comprises (A) a polycarbonate resin and (B) an epoxy resin, and the component (A) is a compound represented by the formula (A1):

[0015] [ka]

[0016] [In the formula, Ring A and ring B each independently represent an aromatic ring which may have a substituent; Ring X is a non-aromatic carbocyclic ring having 7 or more carbon atoms, which may have a substituent. The resin composition contains a polycarbonate resin having a repeating structural unit represented by the formula: By using such a resin composition, it is possible to obtain a cured product having a lower relative dielectric constant (Dk).

[0017] The resin composition of the present invention may further contain optional components in addition to (A) polycarbonate resin and (B) epoxy resin. Examples of optional components include (C) inorganic filler, (D) epoxy resin curing agent, (E) radical polymerizable compound, (F) curing accelerator, (G) radical polymerization initiator, (H) other additives, and (I) organic solvent. Each component contained in the resin composition will be described in detail below.

[0018] <(A) Polycarbonate resin> The resin composition of the present invention contains (A) a polycarbonate resin. (A) The polycarbonate resin is a resin containing a repeating unit having a carbonate ester, and can be obtained, for example, by polycondensation of a diol component and a carbonate diester component.

[0019] (A) Polycarbonate resin has the formula (A1):

[0020] [ka]

[0021] [In the formula, Ring A and ring B each independently represent an aromatic ring which may have a substituent; Ring X is a non-aromatic carbocyclic ring having 7 or more carbon atoms, which may have a substituent. The polycarbonate resin includes a polycarbonate resin having a repeating structural unit represented by the formula (A1): The repeating structural unit represented by the formula (A1) may be of one type or of two or more types in one molecule.

[0022] Ring A and ring B each independently represent an aromatic ring which may have a substituent.

[0023] The aromatic ring refers to a ring that conforms to Hückel's rule, in which the number of electrons contained in the π-electron system on the ring is 4p+2 (p is a natural number). The aromatic ring may be an aromatic carbocyclic ring containing only carbon atoms as ring-constituting atoms, or an aromatic heterocyclic ring containing heteroatoms such as oxygen atoms, nitrogen atoms, and sulfur atoms in addition to carbon atoms as ring-constituting atoms. In one embodiment, the aromatic ring is preferably an aromatic carbocyclic ring. In one embodiment, the aromatic ring is preferably a 5- to 14-membered aromatic ring, more preferably a 6- to 14-membered aromatic ring, and even more preferably a 6- to 10-membered aromatic ring. Specific examples of suitable aromatic rings include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring. A benzene ring or a naphthalene ring is more preferred, and a benzene ring is particularly preferred.

[0024] In the present specification, the substituent is not particularly limited, and examples thereof include monovalent substituents such as an alkyl group, an alkenyl group, an aryl group, an aryl-alkyl group (an alkyl group substituted with an aryl group), an alkyl-aryl group (an aryl group substituted with an alkyl group), an alkyl-oxy group, an alkenyl-oxy group, an aryl-oxy group, an alkyl-carbonyl group, an alkenyl-carbonyl group, an aryl-carbonyl group, an alkyl-oxy-carbonyl group, an alkenyl-oxy-carbonyl group, an aryl-oxy-carbonyl group, an alkyl-carbonyl-oxy group, an alkenyl-carbonyl-oxy group, and an aryl-carbonyl-oxy group, and may also include divalent substituents such as an oxo group (═O) if substitutable.

[0025] The term "alkyl group" refers to a linear, branched, and / or cyclic monovalent aliphatic saturated hydrocarbon group. Unless otherwise specified, the alkyl group is preferably an alkyl group having 1 to 14 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and even more preferably an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, cyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, trimethylcyclohexyl, cyclopentylmethyl, and cyclohexylmethyl. The term "alkenyl group" refers to a linear, branched, and / or cyclic monovalent aliphatic unsaturated hydrocarbon group having at least one carbon-carbon double bond. Unless otherwise specified, 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. Examples of the alkenyl (group) include a vinyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, and a cyclohexenyl group. The aryl (group) refers to a monovalent aromatic hydrocarbon group formed by removing one hydrogen atom from an aromatic carbon ring. Unless otherwise specified, the aryl (group) is preferably an aryl (group) having 6 to 14 carbon atoms, and particularly preferably an aryl (group) having 6 to 10 carbon atoms. Examples of the aryl (group) include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.

[0026] Ring A and Ring B are preferably each independently a benzene ring optionally substituted with a group selected from alkyl groups, alkenyl groups, aryl groups, aryl-alkyl groups, alkyl-aryl groups, alkyl-oxy groups, alkenyl-oxy groups, and aryl-oxy groups; or a naphthalene ring optionally substituted with a group selected from alkyl groups, alkenyl groups, aryl groups, aryl-alkyl groups, alkyl-aryl groups, alkyl-oxy groups, alkenyl-oxy groups, and aryl-oxy groups. Ring A and Ring B are more preferably each independently a benzene ring optionally substituted with a group selected from alkyl groups, aryl groups, aryl-alkyl groups, and alkyl-aryl groups; or a naphthalene ring optionally substituted with a group selected from alkyl groups, aryl groups, aryl-alkyl groups, and alkyl-aryl groups. Ring A and Ring B are even more preferably each independently a benzene ring optionally substituted with a group selected from alkyl groups and aryl groups; or a naphthalene ring optionally substituted with a group selected from alkyl groups and aryl groups. Particularly preferably, ring A and ring B are each independently an (unsubstituted) benzene ring or an (unsubstituted) naphthalene ring.

[0027] Ring X is a non-aromatic carbocyclic ring having 7 or more carbon atoms which may have a substituent.

[0028] A non-aromatic carbocycle is a carbocycle that does not contain an aromatic carbocycle. A non-aromatic carbocycle has only carbon atoms as ring-constituting atoms. A non-aromatic carbocycle may be a saturated carbocycle consisting of only single bonds, or a non-aromatic unsaturated carbocycle having at least one of a double bond and a triple bond, but is preferably a saturated carbocycle consisting of only single bonds. A non-aromatic carbocycle having 7 or more carbon atoms is preferably a non-aromatic carbocycle having 8 to 21 carbon atoms, more preferably a non-aromatic carbocycle having 9 to 17 carbon atoms, even more preferably a non-aromatic carbocycle having 10 to 14 carbon atoms, and even more preferably a non-aromatic carbocycle having 11 to 13 carbon atoms. Specific preferred examples of the non-aromatic carbocyclic ring having 7 or more carbon atoms include, for example, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, a cyclodecane ring, a cycloundecane ring, a cyclododecane ring, a cyclotridecane ring, a cyclotetradecane ring, a cyclopentadecane ring, a cyclohexadecane ring, a cycloheptadecane ring, a cyclooctadecane ring, a cyclononadecane ring, and the like; a bicyclo[ Saturated bicyclic carbocyclic rings with 7 or more carbon atoms, such as bicyclo[2.2.1]heptane ring (norbornane ring), bicyclo[4.4.0]decane ring (decalin 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, and bicyclo[3.3.1]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 or other saturated tricyclic carbocyclic rings having 7 or more carbon atoms; tetracyclo[6.2.1.1 3,6 .0 2,7 ] dodecane ring, etc.; pentacyclo[9.2.1.1 4,7 .0 2,1 0.0 3,8 ] Pentadecane ring, pentacyclo[6.5.1.1 3,6 .0 2,7 .0 9,13]A saturated five-ring carbocyclic ring having 7 or more carbon atoms such as a pentadecane ring (tetrahydrotricyclopentadiene ring) is exemplified, and a saturated monocyclic carbocyclic ring having 7 or more carbon atoms is preferred.

[0029] Ring X is preferably a non-aromatic carbocyclic ring having 7 or more carbon atoms which may be substituted with a group selected from an alkyl group, an alkenyl group, an aryl group, an aryl-alkyl group, an alkyl-aryl group, an alkyl-oxy group, an alkenyl-oxy group, an aryl-oxy group, and an oxo group. Ring X is more preferably a non-aromatic carbocyclic ring having 7 or more carbon atoms which may be substituted with a group selected from an alkyl group, an aryl group, an aryl-alkyl group, an alkyl-aryl group, and an oxo group. Ring X is even more preferably a non-aromatic carbocyclic ring having 7 or more carbon atoms which may be substituted with a group selected from an alkyl group and an aryl group. Ring X is particularly preferably an (unsubstituted) non-aromatic carbocyclic ring having 7 or more carbon atoms.

[0030] The (A) polycarbonate resin, in one embodiment, preferably has the formula (A2):

[0031] [ka]

[0032] [In the formula, R 1 and R 2 each independently represents a hydrogen atom, an alkyl group, or an aryl group; n is an integer of 6 or greater; Other symbols are as above.] The polycarbonate resin includes a polycarbonate resin having a repeating structural unit represented by the formula (A2): Only one type of repeating structural unit represented by formula (A2) may be contained in one molecule, or two or more types may be contained in one molecule.

[0033] R 1 and R 2 R each independently represents a hydrogen atom, an alkyl group, or an aryl group. 1and R 2 are preferably each independently a hydrogen atom or an alkyl group, and more preferably a hydrogen atom.

[0034] n represents an integer of 6 or more. n is preferably 7 or more, more preferably 8 or more, even more preferably 9 or more, and still more preferably 10 or more. The upper limit of n is preferably 20 or less, more preferably 16 or less, even more preferably 13 or less, and still more preferably 12 or less. n is particularly preferably 11.

[0035] In one embodiment, the (A) polycarbonate resin is more preferably a polycarbonate resin represented by formula (A3):

[0036] [ka]

[0037] [In the formula, R 3 and R 4 each independently represents an alkyl group or an aryl group; a and b each independently represent 0, 1, 2, 3, or 4; Other symbols are as above.] The polycarbonate resin includes a polycarbonate resin having a repeating structural unit represented by the formula (A3): Only one type of repeating structural unit represented by formula (A3) may be contained in one molecule, or two or more types may be contained in one molecule.

[0038] R 3 and R 4 R each independently represents an alkyl group or an aryl group. 3 and R 4 are each independently preferably an alkyl group.

[0039] a and b each independently represent 0, 1, 2, 3, or 4. a and b each independently represent preferably 0, 1, 2, or 3, more preferably 0, 1, or 2, even more preferably 0 or 1, and particularly preferably 0.

[0040] In one embodiment, the (A) polycarbonate resin is more preferably a polycarbonate resin represented by formula (A4):

[0041] [ka]

[0042] [In the formula, each symbol is as defined above.] The polycarbonate resin includes a polycarbonate resin having a repeating structural unit represented by the formula (A4): Only one type of repeating structural unit represented by formula (A4) may be contained in one molecule, or two or more types may be contained in one molecule.

[0043] In one embodiment, the average number of repetitions (average degree of polymerization) of the repeating structural unit represented by formula (A1) (including the structural units represented by formulae (A2) to (A4)) in the polycarbonate resin (A) is preferably 2 or more, more preferably 2 to 10, even more preferably 2 to 8, still more preferably 3 to 6, and particularly preferably 4 to 5.

[0044] From the viewpoint of further reducing the dielectric loss tangent of the cured product, the (A) polycarbonate resin is preferably a polycarbonate resin in which the terminals of the resin molecules are relatively high in non-functional inactive groups such as naphthyl groups, xylyl groups, tert-butylphenyl groups, and phenyl groups, and the hydroxyl group content (particularly the phenolic hydroxyl group content) is low. From the viewpoint of further reducing the dielectric loss tangent of the cured product, in one embodiment, the hydroxyl group content of the (A) polycarbonate resin is preferably 0.5 mmol / g or less, more preferably 0.1 mmol / g or less, even more preferably 0.05 mmol / g or less, and particularly preferably 0.02 mmol / g or less.

[0045] In one embodiment, the weight average molecular weight (Mw) of the (A) polycarbonate resin is preferably 50,000 or less, more preferably 20,000 or less, even more preferably 10,000 or less, and particularly preferably 5,000 or less. In one embodiment, the lower limit is preferably 1,000 or more, more preferably 2,000 or more, even more preferably 2,500 or more, and particularly preferably 3,000 or more. The weight average molecular weight (Mw) of the resin can be measured as a polystyrene-equivalent value by gel permeation chromatography (GPC).

[0046] In one embodiment, the number average molecular weight (Mn) of the (A) polycarbonate resin is preferably 30,000 or less, more preferably 10,000 or less, even more preferably 5,000 or less, and particularly preferably 3,000 or less. In one embodiment, the lower limit is preferably 1,000 or more, more preferably 1,200 or more, even more preferably 1,400 or more, and particularly preferably 1,500 or more. The number average molecular weight (Mn) of the resin can be measured as a polystyrene-equivalent value by gel permeation chromatography (GPC).

[0047] In one embodiment, the polydispersity (Mw / Mn) of the (A) polycarbonate resin is preferably in the range of 1.1 to 10.0, more preferably in the range of 1.5 to 5.0, and particularly preferably in the range of 2.0 to 3.0.

[0048] (A) Commercially available polycarbonate resins include, for example, "Ph-PCO-BPCDE," "PCO-BPCDE-R," and "PCO-BPCDE" manufactured by Honshu Chemical Industry Co., Ltd., and one or more of these may be used.

[0049] The content of the (A) polycarbonate resin in the resin composition is not particularly limited, but is preferably 70% by mass or less, more preferably 50% by mass or less, even more preferably 40% by mass or less, even more preferably 30% by mass or less, and particularly preferably 20% by mass or less, based on 100% by mass of the nonvolatile components in the resin composition. The lower limit of the content of the (A) polycarbonate resin in the resin composition is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1% by mass or more, even more preferably 5% by mass or more, and particularly preferably 10% by mass or more, based on 100% by mass of the nonvolatile components in the resin composition.

[0050] <(B) Epoxy resin> The resin composition of the present invention contains (B) an epoxy resin, which is a curable resin having an epoxy group.

[0051] Examples of (B) epoxy resins include 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, trisphenol-type epoxy resins, naphthol novolac-type epoxy resins, phenol novolac-type epoxy resins, tert-butyl-catechol-type epoxy resins, naphthalene-type epoxy resins, naphthol-type epoxy resins, anthracene-type epoxy resins, glycidylamine-type epoxy resins, glycidyl ester-type epoxy resins, cresol novolac-type epoxy resins, phenol aralkyl-type epoxy resins, biphenyl-type epoxy resins, linear aliphatic epoxy resins, epoxy resins having a butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, spiro ring-containing epoxy resins, cyclohexane-type epoxy resins, cyclohexane dimethanol-type epoxy resins, naphthylene ether-type epoxy resins, trimethylol-type epoxy resins, tetraphenylethane-type epoxy resins, isocyanurate-type epoxy resins, and phenolphthalimidine-type epoxy resins. The (B) epoxy resin may be used alone or in combination of two or more.

[0052] The resin composition preferably contains, as the (B) epoxy resin, an epoxy resin having two or more epoxy groups per molecule. The proportion of the epoxy resin having two or more epoxy groups per molecule relative to 100% by mass of the non-volatile components of the (B) epoxy resin is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more.

[0053] Epoxy resins include epoxy resins that are liquid at a temperature of 20°C (hereinafter sometimes referred to as "liquid epoxy resins") and epoxy resins that are solid 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 as the epoxy resin, or may contain only a solid epoxy resin, or may contain a combination of a liquid epoxy resin and a solid epoxy resin.

[0054] The liquid epoxy resin is preferably a liquid epoxy resin having two or more epoxy groups in one molecule.

[0055] Preferred liquid epoxy resins include glycerol-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, alicyclic epoxy resins having an ester skeleton, cyclohexanedimethanol-type epoxy resins, cycloaliphatic glycidyl ethers, and epoxy resins having a butadiene structure, and more preferred are glycerol-type epoxy resins, cycloaliphatic glycidyl ethers, bisphenol A-type epoxy resins, and bisphenol F-type epoxy resins.

[0056] Specific examples of liquid epoxy resins include "EX-992L" manufactured by Nagase ChemteX Corporation, "YX7400" manufactured by Mitsubishi Chemical Corporation, "HP4032", "HP4032D", and "HP4032SS" (naphthalene-type epoxy resins) manufactured by DIC Corporation; "828US", "828EL", "jER828EL", "825", and "Epikote 828EL" (bisphenol A-type epoxy resins) manufactured by Mitsubishi Chemical Corporation; and "jER807" and "1750" ( Bisphenol F epoxy resin; Mitsubishi Chemical Corporation's "jER152" (phenol novolac epoxy resin); Mitsubishi Chemical Corporation's "630", "630LSD", and "604" (glycidylamine epoxy resin); ADEKA Corporation's "ED-523T" (glycirol epoxy resin); ADEKA Corporation's "EP-3950L" and "EP-3980S" (glycidylamine epoxy resin); ADEKA Corporation's "EP-4088S" (dicyclopentadiene epoxy resin); Nippon Steel Chemical & Material Corporation's "ZX1059" (mixture of bisphenol A and bisphenol F epoxy resins); Nagase ChemteX Corporation's "EX-721" (glycidyl ester epoxy resin); Nagase ChemteX Corporation's "EX-991L" (epoxy resin containing alkyleneoxy and butadiene skeletons); Daicel Corporation's "Celloxide 2021P" (alicyclic epoxy resin with ester skeleton) ); "PB-3600" manufactured by Daicel Corporation, "JP-100" and "JP-200" manufactured by Nippon Soda Co., Ltd. (epoxy resins having a butadiene structure); "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resins) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "EG-280" (fluorene structure-containing epoxy resin) manufactured by Osaka Gas Chemicals Co., Ltd.; and "EX-201" (cyclic aliphatic glycidyl ether) manufactured by Nagase ChemteX Corporation.

[0057] As the solid epoxy resin, a solid epoxy resin having three or more epoxy groups in one molecule is preferred, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is more preferred.

[0058] Preferred solid epoxy resins include bixylenol-type epoxy resins, naphthalene-type epoxy resins, naphthalene-type tetrafunctional epoxy resins, naphthol novolac-type epoxy resins, cresol novolac-type epoxy resins, dicyclopentadiene-type epoxy resins, trisphenol-type epoxy resins, naphthol-type epoxy resins, biphenyl-type epoxy resins, naphthylene ether-type epoxy resins, anthracene-type epoxy resins, bisphenol A-type epoxy resins, bisphenol AF-type epoxy resins, phenol aralkyl-type epoxy resins, tetraphenylethane-type epoxy resins, and phenolphthalimidine-type epoxy resins.

[0059] Specific examples of solid epoxy resins include DIC Corporation's "HP4032H" (naphthalene-type epoxy resin); DIC Corporation's "HP-4700" and "HP-4710" (naphthalene-type tetrafunctional epoxy resins); DIC Corporation's "N-690" (cresol novolac-type epoxy resin); DIC Corporation's "N-695" (cresol novolac-type epoxy resin); DIC Corporation's "HP-7200," "HP-7200HH," "HP-7200H," and "HP-7200L" (dicyclopentadiene-type epoxy resins); and DIC Corporation's "EXA-7311." "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthylene ether type epoxy resin); "EPPN-502H" (trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC7000L" (naphthol novolac type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC3000H", "NC3000", "NC3000L", "NC3000FH", "NC3100" (biphenyl type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "ESN475V", "ESN4" manufactured by Nippon Steel Chemical & Material Co., Ltd. 100V" (naphthalene-type epoxy resin); "ESN485" (naphthol-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "ESN375" (dihydroxynaphthalene-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YX4000H", "YX4000", "YX4000HK", and "YL7890" (bixylenol-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL6121" (biphenyl-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX8800" (anthracene-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "Y" manufactured by Mitsubishi Chemical Corporation Examples include "X7700" (phenol aralkyl type epoxy resin); "PG-100" and "CG-500" manufactured by Osaka Gas Chemicals Co., Ltd.; "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1010" (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Corporation; and "WHR991S" (phenolphthalimidine type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.These may be used alone or in combination of two or more.

[0060] When a liquid epoxy resin and a solid epoxy resin are used in combination as the (B) epoxy resin, the mass ratio thereof (liquid epoxy resin:solid epoxy resin) is preferably 10:1 to 1:50, more preferably 2:1 to 1:20, and particularly preferably 1:1 to 1:10.

[0061] The epoxy equivalent of the (B) epoxy resin is preferably 50 g / eq. to 5,000 g / eq., more preferably 60 g / eq. to 2,000 g / eq., even more preferably 70 g / eq. to 1,000 g / eq., and even more preferably 80 g / eq. to 500 g / eq. The epoxy equivalent is the mass of the resin per equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.

[0062] The weight average molecular weight (Mw) of the (B) epoxy resin is preferably 100 to 5,000, more preferably 250 to 3,000, and even more preferably 400 to 1,500. The weight average molecular weight of the resin can be measured by gel permeation chromatography (GPC) as a polystyrene-equivalent value.

[0063] The content of the (B) epoxy resin in the resin composition is not particularly limited, but is preferably 30% by mass or less, more preferably 25% by mass or less, even more preferably 20% by mass or less, even more preferably 15% by mass or less, and particularly preferably 10% by mass or less, based on 100% by mass of the nonvolatile components in the resin composition. The lower limit of the content of the (B) epoxy resin in the resin composition is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, even more preferably 0.5% by mass or more, even more preferably 1% by mass or more, and particularly preferably 3% by mass or more, based on 100% by mass of the nonvolatile components in the resin composition.

[0064] The mass ratio of the polycarbonate resin (A) to the epoxy resin (B) in the resin composition (component (A) / component (B)) is not particularly limited, but is preferably 0.1 or more, more preferably 0.5 or more, even more preferably 1 or more, and particularly preferably 2 or more. The upper limit of the mass ratio of the polycarbonate resin (A) to the epoxy resin (B) in the resin composition (component (A) / component (B)) is not particularly limited, but is preferably 1000 or less, more preferably 100 or less, even more preferably 50 or less, and particularly preferably 10 or less.

[0065] <(C) Inorganic filler> The resin composition of the present invention may contain (C) an inorganic filler as an optional component. (C) The inorganic filler is contained in the resin composition in the form of particles.

[0066] (C) Inorganic fillers are inorganic compounds. Examples of (C) inorganic filler materials include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium titanate zirconate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica is particularly preferred. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Spherical silica is preferred. The (C) inorganic filler may be used alone or in combination of two or more kinds in any ratio.

[0067] (C) Examples of commercially available inorganic fillers include "UFP-30" manufactured by Denka Chemical Industry Co., Ltd.; "SP60-05" and "SP507-05" manufactured by Nippon Steel & Sumikin Materials Co., Ltd.; "YC100C", "YA050C", "YA050C-MJE", and "YA010C" manufactured by Admatechs Co., Ltd.; "UFP-30" manufactured by Denka Company Limited; "Silfil NSS-3N", "Silfil NSS-4N", and "Silfil NSS-5N" manufactured by Tokuyama Corporation; "SC2500SQ", "SO-C4", "SO-C2", and "SO-C1" manufactured by Admatechs Co., Ltd.; and "DAW-03" and "FB-105FD" manufactured by Denka Company Limited.

[0068] The average particle size of the (C) inorganic filler is not particularly limited, but is preferably 10 μm or less, more preferably 5 μm or less, even more preferably 2 μm or less, even more preferably 1 μm or less, and particularly preferably 0.7 μm or less. The lower limit of the average particle size of the (C) inorganic filler is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, even more preferably 0.1 μm or more, and particularly preferably 0.2 μm or more. The average particle size of the (C) inorganic filler can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, a particle size distribution of the inorganic filler is created on a volume basis using a laser diffraction / scattering particle size distribution analyzer, and the median diameter is used as the average particle size. A measurement sample can be prepared by weighing 100 mg of inorganic filler and 10 g of methyl ethyl ketone into a vial and dispersing it ultrasonically for 10 minutes. The measurement sample was measured using a laser diffraction particle size distribution analyzer, with blue and red light source wavelengths used, and the particle size distribution of the inorganic filler on a volume basis was measured using a flow cell system, and the average particle size was calculated as the median diameter from the particle size distribution obtained. An example of a laser diffraction particle size distribution analyzer is the "LA-960" manufactured by Horiba, Ltd.

[0069] The specific surface area of ​​the (C) inorganic filler is not particularly limited, but is preferably 0.1 m 2 / g or more, more preferably 0.5m 2 / g or more, more preferably 1m 2 / g or more, particularly preferably 3m 2 The upper limit of the specific surface area of ​​the inorganic filler (C) is not particularly limited, but is preferably 100 m 2 / g or less, more preferably 70m 2 / g or less, more preferably 50m 2 / g or less, particularly preferably 40m 2 The specific surface area of ​​the inorganic filler is obtained according to the BET method by adsorbing nitrogen gas onto the surface of the sample using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech Co., Ltd.) and calculating the specific surface area using the BET multipoint method.

[0070] The (C) inorganic filler is preferably treated with a surface treatment agent from the viewpoint of improving moisture resistance and dispersibility. Examples of the surface treatment agent include a fluorine-containing silane coupling agent, an aminosilane coupling agent, an epoxysilane coupling agent, a mercaptosilane coupling agent, a silane coupling agent, an alkoxysilane, an organosilazane compound, and a titanate coupling agent. The surface treatment agent may be used alone or in any combination of two or more.

[0071] Examples of commercially available surface treatment agents include Shin-Etsu Chemical Co., Ltd.'s "KBM403" (3-glycidoxypropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM803" (3-mercaptopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "SZ-31" (hexamethyldisilazane), Shin-Etsu Chemical Co., Ltd.'s "KBM103" (phenyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM-4803" (long-chain epoxy-type silane coupling agent), and Shin-Etsu Chemical Co., Ltd.'s "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane).

[0072] The degree of surface treatment with the surface treatment agent is preferably within a predetermined range from the viewpoint of improving the dispersibility of the inorganic filler. Specifically, 100% by mass of the inorganic filler is preferably surface-treated with 0.2% to 5% by mass of the surface treatment agent, more preferably 0.2% to 3% by mass, and even more preferably 0.3% to 2% by mass.

[0073] The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of ​​the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of ​​the inorganic filler is set to 0.02 mg / m 2 More than 0.1 mg / m is preferable. 2 More preferably, 0.2 mg / m or more 2 On the other hand, from the viewpoint of preventing an increase in the melt viscosity of the resin composition or the melt viscosity in the form of a sheet, it is more preferable that the melt viscosity is 1.0 mg / m 2 Preferably less than 0.8 mg / m 2 Less than 0.5 mg / m is more preferable. 2 The following is even more preferred:

[0074] (C) 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 (e.g., methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler that has been surface-treated with a surface treatment agent, and ultrasonic cleaning is performed at 25°C for 5 minutes. After removing the supernatant and drying the solid content, the amount of carbon per unit surface area of ​​the inorganic filler can be measured using a carbon analyzer. An "EMIA-320V" manufactured by Horiba, Ltd., or the like can be used as the carbon analyzer.

[0075] The content of the (C) inorganic filler in the resin composition is not particularly limited, but is preferably 95% by mass or less, more preferably 90% by mass or less, even more preferably 85% by mass or less, and particularly preferably 80% by mass or less, based on 100% by mass of the nonvolatile components in the resin composition. The lower limit of the content of the (C) inorganic filler in the resin composition is not particularly limited, but is, based on 100% by mass of the nonvolatile components in the resin composition, for example, 0% by mass or more, 1% by mass or more, preferably 5% by mass or more, 10% by mass or more, more preferably 20% by mass or more, 30% by mass or more, even more preferably 40% by mass or more, 50% by mass or more, even more preferably 55% by mass or more, 60% by mass or more, and particularly preferably 65% ​​by mass or more, 70% by mass or more, or 73% by mass or more.

[0076] The mass ratio of the (A) polycarbonate resin to the (C) inorganic filler in the resin composition ((A) component / (C) component) is not particularly limited, but is preferably 0.001 or more. It is more preferably 0.01 or more, even more preferably 0.05 or more, and particularly preferably 0.1 or more. The upper limit of the mass ratio of the polycarbonate resin (A) to the inorganic filler (C) in the resin composition (component (A) / component (C)) is not particularly limited, but is preferably 10 or less, more preferably 5 or less, even more preferably 1 or less, and particularly preferably 0.5 or less.

[0077] <(D) Epoxy resin curing agent> The resin composition of the present invention may contain an optional component (D) epoxy resin curing agent. The epoxy resin curing agent (D) may be used alone or in any combination of two or more. The epoxy resin curing agent (D) may have the function of reacting with the epoxy resin (B) to cure it.

[0078] The (D) epoxy resin curing agent is not particularly limited, but examples thereof include active ester curing agents, phenolic curing agents, carbodiimide curing agents, acid anhydride curing agents, amine curing agents, benzoxazine curing agents, cyanate ester curing agents, and thiol curing agents. It is particularly preferable that the (D) epoxy resin curing agent contains an active ester curing agent.

[0079] As the active ester curing agent, compounds having two or more highly reactive ester groups per molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, are generally preferred. The active ester compound is preferably one 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. From the viewpoint of improving heat resistance in particular, 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 phenol compound and / or a naphthol compound is more preferred. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of phenol compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalene, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene-type diphenol compounds, and phenol novolak. Here, "dicyclopentadiene-type diphenol compounds" refers to diphenol compounds obtained by condensing one dicyclopentadiene molecule with two phenol molecules.

[0080] Specific examples of the active ester curing agent include dicyclopentadiene-type active ester compounds, naphthalene-type active ester compounds containing a naphthalene structure, active ester compounds containing an acetylated product of phenol novolac, and active ester compounds containing a benzoylated product of phenol novolac. Among these, at least one selected from dicyclopentadiene-type active ester compounds and naphthalene-type active ester compounds is more preferred, and dicyclopentadiene-type active ester compounds are even more preferred. As the dicyclopentadiene-type active ester compound, active ester compounds containing a dicyclopentadiene-type diphenol structure are preferred.

[0081] Commercially available active ester curing agents include active ester compounds containing a dicyclopentadiene-type diphenol structure, such as "EXB9451," "EXB9460," "EXB9460S," "EXB-8000L," "EXB-8000L-65M," "EXB-8000L-65TM," "HPC-8000L-65TM," "HPC-8000," "HPC-8000-65T," "HPC-8000H," and "HPC-8000H-65TM" (manufactured by DIC Corporation); and active ester compounds containing a naphthalene structure, such as "HP-B-8151-62T," "EXB-8100L-65T," "EXB-8150-60T," and "EXB-8150- 62T," "EXB-9416-70BK," "HPC-8150-60T," "HPC-8150-62T," and "EXB-8" (manufactured by DIC Corporation); a phosphorus-containing active ester compound such as "EXB9401" (manufactured by DIC Corporation); an active ester compound which is an acetylated product of phenol novolac such as "DC808" (manufactured by Mitsubishi Chemical Corporation); active ester compounds which are benzoylated products of phenol novolac such as "YLH1026," "YLH1030," and "YLH1048" (manufactured by Mitsubishi Chemical Corporation); and an active ester compound containing a styryl group and a naphthalene structure such as "PC1300-02-65MA" (manufactured by Air Water Inc.).

[0082] As the phenolic curing agent, a phenolic curing agent having a novolac structure is preferred from the viewpoint of heat resistance and water resistance. Also, from the viewpoint of adhesion to an adherend, a nitrogen-containing phenolic curing agent is preferred, and a triazine skeleton-containing phenolic curing agent is more preferred. Among them, a triazine skeleton-containing phenolic novolac resin is preferred from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion. Specific examples of phenolic curing agents include "MEH-7700," "MEH-7810," and "MEH-7851" manufactured by Meiwa Chemical Industry Co., Ltd.; "NHN," "CBN," and "GPH" manufactured by Nippon Kayaku Co., Ltd.; "SN-170," "SN-180," "SN-190," "SN-475," "SN-485," "SN-495," "SN-375," and "SN-395" manufactured by Nippon Steel Chemical & Material Co., Ltd.; and "LA-7052," "LA-7054," "LA-3018," "LA-3018-50P," "LA-1356," "TD2090," and "TD-2090-60M" manufactured by DIC Corporation.

[0083] Examples of carbodiimide curing agents include curing agents having one or more, preferably two or more, carbodiimide structures in one molecule, such as aliphatic biscarbodiimides such as tetramethylene-bis(t-butylcarbodiimide) and cyclohexane-bis(methylene-t-butylcarbodiimide); aromatic biscarbodiimides such as phenylene-bis(xylylcarbodiimide); and aliphatic polycarbodiimides such as polyhexamethylenecarbodiimide, polytrimethylhexamethylenecarbodiimide, polycyclohexylenecarbodiimide, poly(methylenebiscyclohexylenecarbodiimide), and poly(isophoronecarbodiimide). ; aromatic polycarbodiimides such as poly(phenylenecarbodiimide), poly(naphthylenecarbodiimide), poly(tolylenecarbodiimide), poly(methyldiisopropylphenylenecarbodiimide), poly(triethylphenylenecarbodiimide), poly(diethylphenylenecarbodiimide), poly(triisopropylphenylenecarbodiimide), poly(diisopropylphenylenecarbodiimide), poly(xylylenecarbodiimide), poly(tetramethylxylylenecarbodiimide), poly(methylenediphenylenecarbodiimide), and poly[methylenebis(methylphenylene)carbodiimide].

[0084] Commercially available carbodiimide curing agents include, for example, "Carbodilite V-02B," "Carbodilite V-03," "Carbodilite V-04K," "Carbodilite V-07," and "Carbodilite V-09" manufactured by Nisshinbo Chemical Inc.; and "Stavaxol P," "Stavaxol P400," and "Hykasil 510" manufactured by Rhein Chemie.

[0085] The acid anhydride curing agent may be a curing agent having one or more acid anhydride groups in one molecule, and a curing agent having two or more acid anhydride groups in one molecule is preferred. Specific examples of the acid anhydride curing agent include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, and benzophenonetetracarboxylic dianhydride. Examples of suitable anhydrides include anhydrides, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenylsulfonetetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-C]furan-1,3-dione, ethylene glycol bis(anhydrotrimellitate), and polymeric anhydrides such as styrene-maleic acid resins, which are copolymers of styrene and maleic acid. Commercially available acid anhydride curing agents include "HNA-100," "MH-700," "MTA-15," "DDSA," and "OSA" manufactured by New Japan Chemical Co., Ltd.; "YH-306" and "YH-307" manufactured by Mitsubishi Chemical Corporation; "HN-2200" and "HN-5500" manufactured by Hitachi Chemical Co., Ltd.; and "EF-30," "EF-40," "EF-60," and "EF-80" manufactured by Clay Valley.

[0086] Examples of the amine curing agent include curing agents having one or more, preferably two or more, amino groups in one molecule, such as aliphatic amines, polyether amines, alicyclic amines, and aromatic amines, among which aromatic amines are preferred from the viewpoint of achieving the desired effects of the present invention. The amine curing agent is preferably a primary amine or a secondary amine, and more preferably a primary amine. Specific examples of amine-based curing agents include 4,4'-methylenebis(2,6-dimethylaniline), 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, and 2,2-bis(3-amino-4-hydroxyphenyl)propane. propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)sulfone, bis(4-(3-aminophenoxy)phenyl)sulfone, and the like. Commercially available amine-based curing agents may be used, and examples thereof include "SEIKACURE-S" manufactured by Seika Corporation, "KAYABOND C-200S", "KAYABOND C-100", "KAYAHARD AA", "KAYAHARD AB", and "KAYAHARD AS" manufactured by Nippon Kayaku Co., Ltd., and "Epicure W" manufactured by Mitsubishi Chemical Corporation.

[0087] Specific examples of benzoxazine curing agents include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemical Corporation; "HFB2006M" manufactured by Showa Polymer Co., Ltd.; and "Pd" and "Fa" manufactured by Shikoku Chemicals Corporation.

[0088] Examples of cyanate ester curing agents include bifunctional cyanate resins such as bisphenol A dicyanate, polyphenol cyanate (oligo(3-methylene-1,5-phenylene cyanate)), 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4'-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4-cyanatephenyl)thioether, and bis(4-cyanatephenyl)ether; multifunctional cyanate resins derived from phenol novolac and cresol novolac; and prepolymers in which these cyanate resins are partially converted to triazine. Specific examples of cyanate ester curing agents include "PT30" and "PT60" (both phenol novolac type multifunctional cyanate ester resins) manufactured by Lonza Japan Co., Ltd., "BA230" and "BA230S75" (prepolymers in which part or all of bisphenol A dicyanate has been triazine converted to a trimer).

[0089] Examples of thiol-based curing agents include trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), and tris(3-mercaptopropyl)isocyanurate.

[0090] The reactive group equivalent of the (D) epoxy resin curing agent is preferably 50 g / eq. to 3000 g / eq., more preferably 100 g / eq. to 1000 g / eq., even more preferably 100 g / eq. to 500 g / eq., and particularly preferably 100 g / eq. to 300 g / eq. The reactive group equivalent is the mass of the (D) epoxy resin curing agent per equivalent of reactive group.

[0091] The content of (D) epoxy resin curing agent in the resin composition is not particularly limited, but is preferably 30% by mass or less, more preferably 20% by mass or less, even more preferably 10% by mass or less, and particularly preferably 7% by mass or less, based on 100% by mass of the nonvolatile components in the resin composition. The lower limit of the content of (D) epoxy resin curing agent in the resin composition is not particularly limited, but may be, for example, 0% by mass or more, 0.01% by mass or more, 0.1% by mass or more, or 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more, and particularly preferably 4% by mass or more, based on 100% by mass of the nonvolatile components in the resin composition.

[0092] <(E) Radical Polymerizable Compound> The resin composition of the present invention may contain (E) a radically polymerizable compound as an optional component. The (E) radically polymerizable compound may be used alone or in any combination of two or more.

[0093] In one embodiment, the (E) radical polymerizable compound is a radical polymerizable compound having an ethylenically unsaturated bond. The (E) radical polymerizable compound is not particularly limited, but may have a radical polymerizable group such as an unsaturated hydrocarbon group such as an allyl group, a 3-cyclohexenyl group, a 3-cyclopentenyl group, a 2-vinylphenyl group, a 3-vinylphenyl group, or a 4-vinylphenyl group; or an α,β-unsaturated carbonyl group such as an acryloyl group, a methacryloyl group, or a maleimide group (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl group). The (E) radical polymerizable compound preferably has two or more radical polymerizable groups.

[0094] In the first embodiment, the (E) radical polymerizable compound preferably contains a thermoplastic resin having a vinylphenyl group and / or a (meth)acryloyl group. The (meth)acryloyl group refers to an acryloyl group or a methacryloyl group. The vinylphenyl group includes a 2-vinylphenyl group, a 3-vinylphenyl group, a 4-vinylphenyl group, or a group in which the aromatic carbon atom of each group is further substituted with one or more alkyl groups. Preferably, each molecule contains two or more vinylphenyl groups and / or (meth)acryloyl groups. Examples of thermoplastic resins include phenoxy resins, polyvinyl acetal resins, polystyrene resins, polyethylene resins, polypropylene resins, polybutadiene resins, polyimide resins, polyamideimide resins, polyetherimide resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, polyetheretherketone resins, and polyester resins. In this embodiment, the (E) radical polymerizable compound contains a modified resin of these resins having a vinylphenyl group and / or a (meth)acryloyl group.

[0095] In the first embodiment, the radical polymerizable compound (E) more preferably contains a resin selected from a modified polyphenylene ether resin having a vinylphenyl group and / or a (meth)acryloyl group, and a modified polystyrene resin having a vinylphenyl group and / or a (meth)acryloyl group, still more preferably contains a modified polyphenylene ether resin having a vinylphenyl group and / or a (meth)acryloyl group, and particularly preferably contains a compound represented by the formula (E-1):

[0096] [ka]

[0097] [In the formula, R 11 and R 12 each independently represents an alkyl group; R 13 , R 14 , R 21 , R 22 , R 23 and R 24each independently represents a hydrogen atom or an alkyl group; R 31 and R 32 each independently represents a vinylphenyl group or a (meth)acryloyl group; Y 1 is a single bond, -C(R y )2-, -O-, -CO-, -S-, -SO-, or -SO2-; R y each independently represents a hydrogen atom or an alkyl group; Y 2 represents a single bond or an alkylene group; p represents 0 or 1; and q and r each independently represent an integer of 1 or greater. The q units and r units may be the same or different for each unit.

[0098] R 11 and R 12 R each independently represents an alkyl group, preferably a methyl group. 13 and R 14 R each independently represents a hydrogen atom or an alkyl group, and is preferably a hydrogen atom. 21 and R 22 R each independently represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group, and more preferably a methyl group. 23 and R 24 each independently represents a hydrogen atom or an alkyl group, and is preferably a hydrogen atom or a methyl group.

[0099] R 31 and R 32 each independently represents a vinylphenyl group or a (meth)acryloyl group, Y 2represents a single bond or an alkylene group. The alkylene group refers to a linear, branched, and / or cyclic divalent aliphatic saturated hydrocarbon group. The alkylene group is preferably an alkylene group having 1 to 14 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 1 to 6 carbon atoms. Examples of the alkylene group include -CH2-, -CH2-CH2-, -CH(CH3)-, -CH2-CH2-CH2-, -CH2-CH(CH3)-, -CH(CH3)-CH2-, and -C(CH3)2-. Preferably, R 31 and R 32 is a vinylphenyl group, and Y 2 is an alkylene group (particularly preferably —CH—), or R 31 and R 32 is a (meth)acryloyl group, and Y 2 is a single bond.

[0100] Y 1 is a single bond, -C(R y )2-, -O-, -CO-, -S-, -SO-, or -SO2-, and preferably represents a single bond, -C(R y )2- or -O-. y each independently represents a hydrogen atom or an alkyl group, and preferably a hydrogen atom or a methyl group. p represents 0 or 1, and preferably 1. q and r each independently represent an integer of 1 or more, and preferably an integer of 1 to 200, and more preferably an integer of 1 to 100.

[0101] Examples of commercially available products of the radically polymerizable compound (E) in the first embodiment include "OPE-2St 1200" and "OPE-2St 2200" (vinylbenzyl-modified polyphenylene ether resins) manufactured by Mitsubishi Gas Chemical Company, Inc.; and "SA9000" and "SA9000-111" (methacrylic-modified polyphenylene ether resins) manufactured by SABIC Innovative Plastics.

[0102] In the second embodiment, the radical polymerizable compound (E) is preferably represented by the formula (E-2′):

[0103] [ka]

[0104] [In the formula, ring C represents a monocycloalkane ring which may have a substituent, or a monocycloalkene ring which may have a substituent; c and d each independently represent an integer of 0 or 1 or greater, and the sum of c and d is 6 or greater; and * represents a bonding site.] The maleimide compound includes a maleimide compound having a partial structure represented by the following formula: The maleimide compound refers to a compound containing at least one maleimide group (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl group) in one molecule. The number of maleimide groups in one molecule of the maleimide compound in the second embodiment is preferably 2 or more, and particularly preferably 2. The maleimide compound in the second embodiment may be used alone or in combination of two or more at any ratio.

[0105] The monocycloalkane ring refers to a monocyclic aliphatic saturated hydrocarbon ring. The monocycloalkane ring is preferably a monocycloalkane ring having 4 to 14 carbon atoms, more preferably a monocycloalkane ring having 4 to 10 carbon atoms, and particularly preferably a monocycloalkane ring having 5 or 6 carbon atoms. Examples of the monocycloalkane ring include a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, and a cyclooctane ring. The monocycloalkene ring refers to a monocyclic aliphatic unsaturated hydrocarbon ring having at least one carbon-carbon double bond. The monocycloalkene ring is preferably a monocycloalkene ring having 4 to 14 carbon atoms, more preferably a monocycloalkene ring having 4 to 10 carbon atoms, and particularly preferably a monocycloalkene ring having 5 or 6 carbon atoms. Examples of the monocycloalkene ring include a cyclobutene ring, a cyclopentene ring, a cyclohexene ring, a cycloheptene ring, a cyclooctene ring, a cyclopentadiene ring, and a cyclohexadiene ring.

[0106] Ring C represents a monocycloalkane ring which may have a substituent, or a monocycloalkene ring which may have a substituent. Ring C is preferably a monocycloalkane ring which may have a substituent selected from an alkyl group and an alkenyl group; or a monocycloalkene ring which may have a substituent selected from an alkyl group and an alkenyl group. Ring C is more preferably a monocycloalkane ring which may have a substituent selected from an alkyl group having 1 to 14 carbon atoms and an alkenyl group having 2 to 14 carbon atoms; or a monocycloalkene ring which may have a substituent selected from an alkyl group having 1 to 14 carbon atoms and an alkenyl group having 2 to 14 carbon atoms.

[0107] c and d each independently represent an integer of 0 or 1 or more, and the sum of c and d is 6 or more (preferably 8 or more, more preferably 10 or more). c and d are preferably each independently an integer of 0 to 20, and the sum of c and d is 6 or more (preferably 8 or more, more preferably 10 or more). c and d are more preferably each independently an integer of 1 to 20, and the sum of c and d is 6 or more (preferably 8 or more, more preferably 10 or more). c and d are further preferably each independently an integer of 5 to 10. c and d are particularly preferably 8.

[0108] In the second embodiment, the radical polymerizable compound (E) is particularly preferably a compound represented by formula (E-2):

[0109] [ka]

[0110] [In the formula, R 5 each independently represents a substituent; each ring D independently represents an aromatic ring which may have a substituent; D 1 and D 2 are each independently a single bond, -C(R x )2-, -O-, -CO-, -S-, -SO-, -SO2-, -CONH-, -NHCO-, -COO-, or -OCO-; Rx each independently represents a hydrogen atom or an alkyl group; each e independently represents 0 or 1; each f independently represents an integer of 0 or 1 or more; each g independently represents 0, 1, or 2; and each m independently represents an integer of 0 or 1 or more; and other symbols are as defined above. The f unit, g unit, and m unit may be the same or different for each unit.

[0111] Each ring D independently represents an aromatic ring which may have a substituent, and is preferably a benzene ring which may have a substituent selected from alkyl groups. 1 and D 2 are each independently a single bond, -C(R x )2-, -O-, -CO-, -S-, -SO-, -SO2-, -CONH-, -NHCO-, -COO-, or -OCO-, and preferably represents a single bond, -C(R x )2- or -O-. x are each independently a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group. e are each independently 0 or 1, preferably 0. f are each independently an integer of 0 or 1 or more, preferably 0, 1, 2 or 3, more preferably 0, 1 or 2. g are each independently 0, 1 or 2, preferably 0. m are each independently an integer of 0 or 1 or more, preferably 0.

[0112] Formula (D) contained in formula (E-2):

[0113] [ka]

[0114] [In the formula, * indicates a binding site; other symbols are as defined above.] The partial structure represented by the formula (D-1) to (D-3):

[0115] [ka]

[0116] [In the formula, * is the same as above.] Examples of the partial structure include:

[0117] Commercially available products of the radically polymerizable compound (E) in the second embodiment include, for example, "BMI-689," "BMI-1500," "BMI-1700," and "BMI-3000J" manufactured by Designer Molecules, Inc.

[0118] In the third embodiment, the radical polymerizable compound (E) is preferably represented by formula (E-3):

[0119] [ka]

[0120] [In the formula, R 6 each independently represents a hydrogen atom or an alkyl group; ring E, ring F, and ring G each independently represent an aromatic ring which may have a substituent; each Z independently represents a single bond, -C(R z )2-, -O-, -CO-, -S-, -SO-, -SO2-, -CONH-, or -NHCO-; R z each independently represents a hydrogen atom or an alkyl group; each s independently represents an integer of 1 or greater; each t independently represents 0 or 1; and each u independently represents 0, 1, 2, or 3. The maleimide compounds according to the third embodiment include maleimide compounds represented by the following formula: The s units and u units may be the same or different for each unit. The maleimide compounds according to the third embodiment may be used singly or in combination of two or more types in any ratio.

[0121] R 6are each independently a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom. Ring E, ring F, and ring G are each independently an aromatic ring which may have a substituent, preferably a benzene ring which may have a substituent, more preferably a benzene ring which may be substituted with a group selected from an alkyl group and an aryl group, and particularly preferably an (unsubstituted) benzene ring.

[0122] Each Z is independently a single bond, -C(R z )2-, -O-, -CO-, -S-, -SO-, -SO2-, -CONH-, or -NHCO-, and preferably a single bond, -C(R z )2- or -O-, and more preferably a single bond or -C(R z )2-, and particularly preferably a single bond. z each independently represents a hydrogen atom or an alkyl group, and is preferably a hydrogen atom or a methyl group.

[0123] s represents an integer of 1 or more, preferably an integer of 1 to 10. Each t independently represents 0 or 1, preferably 1. Each u independently represents 0, 1, 2, or 3, preferably 0, 1, or 2, more preferably 0 or 1, and particularly preferably 1.

[0124] Commercially available products of the radically polymerizable compound (E) in the third embodiment include, for example, "MIR-3000-70MT" and "MIR-5000-60T" manufactured by Nippon Kayaku Co., Ltd.

[0125] The (E) radically polymerizable compound may contain any one of the preferred thermoplastic resins contained in the first embodiment, the preferred maleimide compounds contained in the second embodiment, and the preferred maleimide compounds contained in the third embodiment, alone, or may contain a combination of two or more of these in any ratio.

[0126] The radical polymerizable group equivalent of the (E) radical polymerizable compound is preferably 250 g / eq. to 2500 g / eq., more preferably 300 g / eq. to 1500 g / eq. The radical polymerizable group equivalent of the (E) radical polymerizable compound represents the mass of the resin per equivalent of the radical polymerizable group.

[0127] The weight average molecular weight (Mw) of the (E) radically polymerizable compound is preferably 300 to 40,000, more preferably 300 to 10,000, and particularly preferably 300 to 7,000. The weight average molecular weight of the resin can be measured by gel permeation chromatography (GPC) as a polystyrene-equivalent value.

[0128] The content of the (E) radical polymerizable compound in the resin composition is not particularly limited, but is preferably 30% by mass or less, more preferably 20% by mass or less, even more preferably 10% by mass or less, and particularly preferably 7% by mass or less, based on 100% by mass of the nonvolatile components in the resin composition. The lower limit of the content of the (E) radical polymerizable compound in the resin composition is not particularly limited, but is, for example, 0% by mass or more, 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 3% by mass or more, and particularly preferably 5% by mass or more, based on 100% by mass of the nonvolatile components in the resin composition.

[0129] <(F) Curing accelerator> The resin composition of the present invention may contain, as an optional component, (F) a curing accelerator, which functions as a curing catalyst that accelerates the curing of (B) the epoxy resin.

[0130] Examples of the (F) curing accelerator include 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. The (F) curing accelerator preferably includes an amine-based curing accelerator. The (F) curing accelerators may be used alone or in combination of two or more.

[0131] Examples of the phosphorus-based curing accelerator include aliphatic phosphonium salts such as tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium)pyromellitate, tetrabutylphosphonium hydrogenhexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate, and di-tert-butylmethylphosphonium tetraphenylborate; methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra-p-tolylborate, and tetraphenylphosphonium bromide. aromatic phosphonium salts such as tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, triphenylethylphosphonium tetraphenylborate, tris(3-methylphenyl)ethylphosphonium tetraphenylborate, tris(2-methoxyphenyl)ethylphosphonium tetraphenylborate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate; aromatic phosphine-borane complexes such as triphenylphosphine-triphenylborane; aromatic phosphine-quinone adducts such as triphenylphosphine-p-benzoquinone adduct; aliphatic phosphines such as tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butyl(2-butenyl)phosphine, di-tert-butyl(3-methyl-2-butenyl)phosphine, and tricyclohexylphosphine;Dibutylphenylphosphine, di-tert-butylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclohexylphosphine, triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tris(4-ethylphenyl)phosphine, tris(4-propylphenyl)phosphine, tris(4-isopropylphenyl)phosphine, tris(4-butylphenyl)phosphine, tris(4-tert-butylphenyl)phosphine, tris(2,4-dimethylphenyl)phosphine, tris(2,5-dimethylphenyl)phosphine, tris(2,6-dimethylphenyl)phosphine aromatic phosphines such as benzene, tris(3,5-dimethylphenyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, tris(2,6-dimethyl-4-ethoxyphenyl)phosphine, tris(2-methoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine, tris(4-ethoxyphenyl)phosphine, tris(4-tert-butoxyphenyl)phosphine, diphenyl-2-pyridylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,2-bis(diphenylphosphino)acetylene, and 2,2'-bis(diphenylphosphino)diphenyl ether;

[0132] Examples of the urea-based curing accelerator include 1,1-dimethylurea; aliphatic dimethylureas such as 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, and 3-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, and 3-(3,4-dimethylphenyl)-1,1-dimethylurea. aromatic dimethylureas such as toluene bis(dimethylurea), 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4-methoxyphenyl)-1,1-dimethylurea, 3-(4-nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy)phenyl]-1,1-dimethylurea, 3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trifluoromethyl)phenyl]-1,1-dimethylurea, N,N-(1,4-phenylene)bis(N',N'-dimethylurea), and N,N-(4-methyl-1,3-phenylene)bis(N',N'-dimethylurea) [toluene bisdimethylurea].

[0133] Examples of guanidine curing accelerators include 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, and 1-(o-tolyl)biguanide.

[0134] Examples of the imidazole curing accelerator 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, and 1-benzyl-2-methylimidazole. Phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl -(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct , 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline, and other imidazole compounds, as well as adducts of imidazole compounds with epoxy resins.

[0135] As the imidazole-based curing accelerator, commercially available products may be used, such as "1B2PZ", "2MZA-PW", and "2PHZ-PW" manufactured by Shikoku Chemical Industry Co., Ltd., and "P200-H50" manufactured by Mitsubishi Chemical Corporation.

[0136] Examples of metal-based curing accelerators include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organic cobalt complexes such as cobalt(II) acetylacetonate and cobalt(III) acetylacetonate, organic copper complexes such as copper(II) acetylacetonate, organic zinc complexes such as zinc(II) acetylacetonate, organic iron complexes such as iron(III) acetylacetonate, organic nickel complexes such as nickel(II) acetylacetonate, and organic manganese complexes such as manganese(II) acetylacetonate. Examples of organometallic salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

[0137] Examples of the amine-based curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo(5,4,0)-undecene.

[0138] As the amine-based curing accelerator, commercially available products may be used, for example, "MY-25" manufactured by Ajinomoto Fine-Techno Co., Ltd.

[0139] The content of the (F) curing accelerator in the resin composition is not particularly limited, but is preferably 5% by mass or less, more preferably 1% by mass or less, even more preferably 0.5% by mass or less, and particularly preferably 0.1% by mass or less, based on 100% by mass of the nonvolatile components in the resin composition. The lower limit of the content of the (F) curing accelerator in the resin composition is not particularly limited, but may be, for example, 0% by mass or more, 0.001% by mass or more, 0.01% by mass or more, or 0.03% by mass or more, based on 100% by mass of the nonvolatile components in the resin composition.

[0140] <(G) Radical Polymerization Initiator> The resin composition of the present invention may contain a (G) radical polymerization initiator as an optional component. The (G) radical polymerization initiator may be, for example, a thermal polymerization initiator that generates free radicals upon heating. The (G) radical polymerization initiator may be a polymerization initiator for the radically polymerizable component containing the above-described (E) component. The (G) radical polymerization initiator may be used alone or in any combination of two or more types.

[0141] (G) Examples of the radical polymerization initiator include peroxide radical polymerization initiators, azo radical polymerization initiators, etc. Among these, peroxide radical polymerization initiators are preferred.

[0142] Examples of the peroxide radical polymerization initiator include hydroperoxide compounds such as 1,1,3,3-tetramethylbutyl hydroperoxide; dialkyl peroxide compounds such as tert-butylcumyl peroxide, di-tert-butyl peroxide, di-tert-hexyl peroxide, dicumyl peroxide, 1,4-bis(1-tert-butylperoxy-1-methylethyl)benzene, and 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane; and diacyl peroxide compounds such as dilauroyl peroxide, didecanoyl peroxide, dicyclohexyl peroxydicarbonate, and bis(4-tert-butylcyclohexyl)peroxydicarbonate. peroxyester compounds such as tert-butyl peroxyacetate, tert-butyl peroxybenzoate, tert-butylperoxyisopropyl monocarbonate, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxyneodecanoate, tert-hexylperoxyisopropyl monocarbonate, tert-butyl peroxylaurate, (1,1-dimethylpropyl) 2-ethylperhexanoate, tert-butyl 2-ethylperhexanoate, tert-butyl 3,5,5-trimethylperhexanoate, tert-butylperoxy-2-ethylhexyl monocarbonate, and tert-butylperoxymaleic acid; and the like.

[0143] Examples of the azo radical polymerization initiator include azonitrile compounds such as 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 1-[(1-cyano-1-methylethyl)azo]formamide, and 2-phenylazo-4-methoxy-2,4-dimethyl-valeronitrile; 2,2'-azobis[2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide], and 2,2'-azobis[2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide]. azoamide compounds such as 2,2'-azobis[2-methyl-N-[2-(1-hydroxybutyl)]-propionamide], 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)-propionamide], 2,2'-azobis(2-methylpropionamide) dihydrate, 2,2'-azobis[N-(2-propenyl)-2-methylpropionamide], 2,2'-azobis(N-butyl-2-methylpropionamide), and 2,2'-azobis(N-cyclohexyl-2-methylpropionamide); alkyl azo compounds such as 2,2'-azobis(2,4,4-trimethylpentane) and 2,2'-azobis(2-methylpropane); and the like.

[0144] (G) Commercially available radical polymerization initiators include, for example, "Perbutyl C," "Perbutyl A," "Perbutyl P," "Perbutyl L," "Perbutyl O," "Perbutyl ND," "Perbutyl Z," "Perbutyl I," "Percumyl P," "Percumyl D," "Perhexyl D," "Perhexyl A," "Perhexyl I," "Perhexyl Z," "Perhexyl ND," "Perhexyl O," and "Perhexyl PV," all manufactured by NOF Corporation.

[0145] The content of the (G) radical polymerization initiator in the resin composition is not particularly limited, but is preferably 1% by mass or less, more preferably 0.5% by mass or less, even more preferably 0.1% by mass or less, and particularly preferably 0.05% by mass or less, based on 100% by mass of the nonvolatile components in the resin composition. The lower limit of the content of the (G) radical polymerization initiator in the resin composition is not particularly limited, but is, for example, 0% by mass or more, 0.0001% by mass or more, preferably 0.001% by mass or more, more preferably 0.005% by mass or more, even more preferably 0.01% by mass or more, and particularly preferably 0.02% by mass or more, based on 100% by mass of the nonvolatile components in the resin composition.

[0146] <(H) Other Additives> The resin composition of the present invention may further contain optional additives as non-volatile components. Examples of such additives include thermosetting resins other than epoxy resins, such as epoxy acrylate resins, urethane acrylate resins, urethane resins, cyanate resins, benzoxazine resins, unsaturated polyester resins, phenolic resins, melamine resins, and silicone resins; thermoplastic resins, such as phenoxy resins, polyvinyl acetal resins, polyolefin resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, polycarbonate resins, polyetheretherketone resins, and polyester resins; organic fillers, such as rubber particles; organometallic compounds, such as organocopper compounds, organozinc compounds, and organocobalt compounds; colorants, such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, and carbon black; polymerization inhibitors, such as hydroquinone, catechol, pyrogallol, and phenothiazine; leveling agents, such as silicone-based leveling agents and acrylic polymer-based leveling agents; thickeners, such as bentone and montmorillonite; and silicones. defoaming agents such as benzotriazole-based defoamers, acrylic defoamers, fluorine-based defoamers, and vinyl resin-based defoamers; ultraviolet absorbers such as benzotriazole-based ultraviolet absorbers; adhesion improvers such as urea silanes; adhesion promoters such as triazole-based adhesion promoters, tetrazole-based adhesion promoters, and triazine-based adhesion promoters; antioxidants such as hindered phenol-based antioxidants; fluorescent brighteners such as stilbene derivatives; surfactants such as fluorine-based surfactants and silicone-based surfactants; phosphorus-based flame retardants (e.g., phosphate ester compounds, phosphazene compounds, Examples of the additives include flame retardants such as phosphinic acid compounds, red phosphorus, nitrogen-based flame retardants (e.g., melamine sulfate), halogen-based flame retardants, and inorganic flame retardants (e.g., antimony trioxide); dispersants such as phosphate ester-based dispersants, polyoxyalkylene-based dispersants, acetylene-based dispersants, silicone-based dispersants, anionic dispersants, and cationic dispersants; and stabilizers such as borate-based stabilizers, titanate-based stabilizers, aluminate-based stabilizers, zirconate-based stabilizers, isocyanate-based stabilizers, carboxylic acid-based stabilizers, and carboxylic anhydride-based stabilizers. (H) Other additives may be used singly or in combination of two or more in any ratio.(H) The content of other additives can be appropriately determined by a person skilled in the art.

[0147] <(I) Organic solvent> The resin composition of the present invention may further contain an arbitrary organic solvent as a volatile component in addition to the nonvolatile components described above. (I) As the organic solvent, any known organic solvent can be used appropriately, and the type thereof is not particularly limited. (I) Examples of the organic solvent include ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester-based solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, and γ-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; 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl diglycol acetate, γ-butyrolactone, and methoxypropionic acid. Examples of suitable organic solvents include ether ester solvents such as methyl ether, ester alcohol solvents such as methyl lactate, ethyl lactate, and methyl 2-hydroxyisobutyrate, ether alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, and diethylene glycol monobutyl ether (butyl carbitol), amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone, sulfoxide solvents such as dimethyl sulfoxide, nitrile solvents such as acetonitrile and propionitrile, aliphatic hydrocarbon solvents such as hexane, cyclopentane, cyclohexane, and methylcyclohexane, and aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene. (I) The organic solvent may be used alone or in combination of two or more solvents in any ratio.

[0148] In one embodiment, the content of (I) the organic solvent is not particularly limited, but when all components in the resin composition are taken as 100% by mass, it can be, for example, 60% by mass or less, 40% by mass or less, 30% by mass or less, 20% by mass or less, 15% by mass or less, 10% by mass or less, etc.

[0149] <Method of manufacturing resin composition> The resin composition of the present invention can be produced, for example, by adding (A) polycarbonate resin, (B) epoxy resin, optionally (C) inorganic filler, optionally (D) epoxy resin curing agent, optionally (E) radical polymerizable compound, optionally (F) curing accelerator, optionally (G) radical polymerization initiator, optionally (H) other additives, and optionally (I) organic solvent to any preparation vessel in any order and / or simultaneously in part or in whole, and mixing. Furthermore, the temperature can be appropriately set during the process of adding and mixing each component, and heating and / or cooling may be performed temporarily or throughout the process. Furthermore, during or after the process of adding and mixing, the resin composition may be stirred or shaken using a stirring or shaking device such as a mixer to uniformly disperse the resin composition. Furthermore, degassing may be performed under low-pressure conditions, such as under vacuum, simultaneously with the stirring or shaking.

[0150] <Characteristics of resin composition> The resin composition of the present invention comprises (A) a polycarbonate resin and (B) an epoxy resin, wherein the component (A) comprises a polycarbonate resin having a repeating structural unit represented by formula (A1). By using such a resin composition, a cured product having a lower dielectric constant (Dk) can be obtained.

[0151] A cured product of the resin composition of the present invention may be characterized by a low dielectric constant (Dk). Thus, in one embodiment, the dielectric constant (Dk) of the cured product of the resin composition, as measured at 5.8 GHz and 23°C as in Test Example 1 below, may be preferably 5.0 or less, more preferably 4.0 or less, even more preferably 3.7 or less, still more preferably 3.5 or less, 3.3 or less, and particularly preferably 3.1 or less, 3.0 or less.

[0152] In one embodiment, a cured product of the resin composition of the present invention may be characterized by a low dielectric loss tangent (Df). Thus, in one embodiment, the dielectric loss tangent (Df) of the cured product of the resin composition, as measured at 5.8 GHz and 23°C as in Test Example 1 below, may be preferably 0.0100 or less, 0.0080 or less, more preferably 0.0070 or less, 0.0060 or less, even more preferably 0.0050 or less, 0.0045 or less, and particularly preferably 0.0040 or less, 0.0035 or less.

[0153] In one embodiment, a cured product of the resin composition of the present invention may be characterized by being able to suppress warpage. Thus, in one embodiment, the amount of warpage measured as in Test Example 2 below may preferably be less than 1 cm.

[0154] In one embodiment, the cured product of the resin composition of the present invention may be characterized by excellent copper foil adhesion. Thus, in one embodiment, the copper foil adhesion strength, as measured in the following Test Example 3, may be preferably 0.2 kgf / cm or more, more preferably 0.25 kgf / cm or more, 0.3 kgf / cm or more, even more preferably 0.35 kgf / cm or more, 0.4 kgf / cm or more, and particularly preferably 0.43 kgf / cm or more, 0.45 kgf / cm or more.

[0155] <Applications of resin composition> The resin composition of the present invention can be suitably used as a resin composition for insulating applications, particularly as a resin composition for forming an insulating layer. Specifically, it can be suitably used as a resin composition for forming an insulating layer (resin composition for forming an insulating layer) for forming a conductor layer (including a rewiring layer) formed on the insulating layer. It can also be suitably used as 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) in the printed wiring board described below. The resin composition of the present invention can also be used in a wide range of applications requiring a resin composition, such as sheet-like laminate materials such as resin sheets and prepregs, solder resists, underfill materials, die bonding materials, semiconductor encapsulants, hole-filling resins, and component-embedding resins.

[0156] Furthermore, for example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition of the present invention can be suitably used as a resin composition for a rewiring formation layer (resin composition for forming a rewiring formation layer) as an insulating layer for forming a rewiring layer, and as a resin composition for encapsulating a semiconductor chip (resin composition for encapsulating a semiconductor chip). When a semiconductor chip package is manufactured, a rewiring layer may be further formed on the encapsulating layer. (1) a step of laminating a temporary fixing film on a substrate; (2) a step of temporarily fixing a semiconductor chip on a temporary fixing film; (3) forming an encapsulation layer on the semiconductor chip; (4) peeling the substrate and the temporary fixing film from the semiconductor chip; (5) forming a rewiring formation layer as an insulating layer on the surface of the semiconductor chip from which the base material and the temporary fixing film have been peeled off; and (6) A step of forming a rewiring layer as a conductor layer on the rewiring formation layer.

[0157] Furthermore, the resin composition of the present invention provides an insulating layer with good component embedding properties, and therefore can be suitably used when the printed wiring board is a circuit board with built-in components.

[0158] <Sheet-type laminated material> The resin composition of the present invention can be used by applying it in the form of a varnish, but industrially it is generally preferred to use it in the form of a sheet-like laminate material containing the resin composition.

[0159] As the sheet-like laminate material, the following resin sheets and prepregs are preferred.

[0160] In one embodiment, the resin sheet includes 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.

[0161] The thickness of the resin composition layer is preferably 50 μm or less, more preferably 40 μm or less, from the viewpoint of thinning the printed wiring board and providing a cured product of the resin composition with excellent insulating properties even when the cured product is thin. The lower limit of the thickness of the resin composition layer is not particularly limited, but can usually be 5 μm or more, 10 μm or more, etc.

[0162] Examples of the support include films made of plastic materials, metal foils, and release papers, with films made of plastic materials and metal foils being preferred.

[0163] When a film made of a plastic material is used as the support, examples of the plastic material include polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"), polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylics such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide, etc. Among these, polyethylene terephthalate and polyethylene naphthalate are preferred, with inexpensive polyethylene terephthalate being particularly preferred.

[0164] When a metal foil is used as the support, examples of the metal foil include copper foil and aluminum foil, with copper foil being preferred. The copper foil may be a foil made of a single metal, copper, or an alloy of copper and another metal (e.g., tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.).

[0165] The surface of the support that is to be bonded to the resin composition layer may be subjected to a matte treatment, a corona treatment, or an antistatic treatment.

[0166] The support may also be a support with a release layer, which has a release layer on the surface that bonds to the resin composition layer. Examples of the release agent used in the release layer of the support with a release layer include one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. Commercially available products may also be used as the support with a release layer, including, for example, "SK-1," "AL-5," and "AL-7" manufactured by Lintec Corporation, "Lumirror T60" manufactured by Toray Industries, Inc., "Purex" manufactured by Teijin Limited, and "Uni-Peel" manufactured by Unitika Limited, which are PET films having a release layer primarily composed of an alkyd resin-based release agent.

[0167] The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, more preferably 10 μm to 60 μm. When a support with a release layer is used, it is preferable that the thickness of the entire support with a release layer is in the above range.

[0168] In one embodiment, the resin sheet may further include an optional layer as needed. Examples of such optional layers include a protective film conforming to the support and provided on the surface of the resin composition layer that is not bonded to the support (i.e., the surface opposite the support). The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating the protective film, adhesion of dust and the like to the surface of the resin composition layer and scratches can be suppressed.

[0169] The resin sheet can be produced, for example, by preparing a liquid resin composition as is or a resin varnish by dissolving the resin composition in an organic solvent, applying this onto a support using a die coater or the like, and then drying to form a resin composition layer.

[0170] The organic solvent may be the same as the organic solvent described as a component of the resin composition. The organic solvent may be used alone or in combination of two or more.

[0171] Drying may be carried out by known methods such as heating or hot air blowing. Drying conditions are not particularly limited, but drying is carried out so that the content of organic solvent in the resin composition layer becomes 10% by mass or less, preferably 5% by mass or less. Although this varies depending on the boiling point of the organic solvent in the resin composition or resin varnish, for example, when a resin composition or resin varnish containing 30% by mass to 60% by mass of organic solvent is used, the resin composition layer can be formed by drying at 50°C to 150°C for 3 to 10 minutes.

[0172] The resin sheet can be stored in a rolled state. When the resin sheet has a protective film, it can be used by peeling off the protective film.

[0173] In one embodiment, the prepreg is formed by impregnating a sheet-like fiber substrate with the resin composition of the present invention.

[0174] The sheet-like fiber substrate used for the prepreg is not particularly limited, and commonly used prepreg substrates such as glass cloth, aramid nonwoven fabric, and liquid crystal polymer nonwoven fabric can be used. From the viewpoint of thinning the printed wiring board, the thickness of the sheet-like fiber substrate is preferably 50 μm or less, more preferably 40 μm or less, even more preferably 30 μm or less, and particularly preferably 20 μm or less. The lower limit of the thickness of the sheet-like fiber substrate is not particularly limited. It is usually 10 μm or more.

[0175] The prepreg can be produced by a known method such as a hot melt method or a solvent method.

[0176] The thickness of the prepreg may be in the same range as that of the resin composition layer in the resin sheet described above.

[0177] The sheet-like laminate 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 can be more suitably used for forming an interlayer insulating layer of a printed wiring board (for an interlayer insulating layer of a printed wiring board).

[0178] <Printed wiring board> 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.

[0179] The printed wiring board can be produced, for example, by using the above-mentioned resin sheet by a method including the following steps (I) and (II). (I) A step of laminating a resin sheet on an inner layer substrate so that the resin composition layer of the resin sheet is bonded to the inner layer substrate. (II) A step of curing (e.g., thermally curing) the resin composition layer to form an insulating layer.

[0180] The "inner layer substrate" used in step (I) is a member that will become the substrate of a printed wiring board, and examples thereof include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, and thermosetting polyphenylene ether substrates. The substrate may have a conductor layer on one or both sides, and this conductor layer may be patterned. An inner layer substrate having a conductor layer (circuit) formed on one or both sides of the substrate may be referred to as an "inner layer circuit board." Furthermore, the "inner layer substrate" of the present invention also includes intermediate products on which an insulating layer and / or a conductor layer is to be further formed during the production of a printed wiring board. When the printed wiring board is a circuit board with built-in components, an inner layer substrate with built-in components may be used.

[0181] The inner layer substrate and the resin sheet can be laminated, for example, by thermocompression bonding the resin sheet to the inner layer substrate from the support side. Examples of a member for thermocompression bonding the resin sheet to the inner layer substrate (hereinafter also referred to as a "thermocompression bonding member") include a heated metal plate (such as a SUS end plate) or a metal roll (SUS roll). Note that rather than pressing the thermocompression bonding member directly onto the resin sheet, it is preferable to press it via an elastic material such as heat-resistant rubber so that the resin sheet can sufficiently conform to the surface irregularities of the inner layer substrate.

[0182] The lamination of the inner layer substrate and the resin sheet may be carried out by a vacuum lamination method. In the 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 in the range of 0.098MPa to 1.77MPa, more preferably 0.29MPa to 1.47MPa, and the thermocompression time is preferably in the range of 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. The lamination may be carried out under reduced pressure conditions, preferably at a pressure of 26.7hPa or less.

[0183] The lamination can be performed using a commercially available vacuum laminator, such as a vacuum pressure laminator manufactured by Meiki Seisakusho Co., Ltd., a vacuum applicator manufactured by Nikko Materials Co., Ltd., or a batch vacuum pressure laminator.

[0184] After lamination, 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 conditions for lamination. The smoothing treatment may be performed using a commercially available laminator. Note that lamination and smoothing treatment may be performed consecutively using the commercially available vacuum laminator.

[0185] The support may be removed between step (I) and step (II), or may be removed after step (II).

[0186] In step (II), the resin composition layer is cured (for example, by heat curing) to form an insulating layer made of a cured product of the resin composition. The curing conditions for the resin composition layer are not particularly limited, and conditions typically employed for forming insulating layers for printed wiring boards may be used.

[0187] For example, the thermal curing conditions for the resin composition layer vary depending on the type of resin composition, 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 170° C. to 210° C. The curing time is preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and even more preferably 15 minutes to 100 minutes.

[0188] Before thermally curing the resin composition layer, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermally curing the resin composition layer, the resin composition layer may be preheated 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, preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and even more preferably 15 minutes to 100 minutes.

[0189] When manufacturing a printed wiring board, the following steps may be further performed: (III) drilling holes in the insulating layer, (IV) roughening the insulating layer, and (V) forming a conductor layer. These steps (III) to (V) may be performed according to various methods known to those skilled in the art and used in manufacturing printed wiring boards. When the support is removed after step (II), the removal of the support may be performed between steps (II) and (III), between steps (III) and (IV), or between steps (IV) and (V). Furthermore, if necessary, the formation of the insulating layer and the conductor layer in steps (II) to (V) may be repeated to form a multilayer wiring board.

[0190] In another embodiment, the printed wiring board of the present invention can be produced using the above-mentioned prepreg. The production method is basically the same as when a resin sheet is used.

[0191] Step (III) is a step of drilling holes in the insulating layer, thereby forming holes such as via holes and through holes in the insulating layer. Step (III) may be performed using, for example, a drill, a 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 determined appropriately depending on the design of the printed wiring board.

[0192] Step (IV) is a step of roughening the insulating layer. Typically, smear removal is also performed in this step (IV). The roughening treatment procedure and conditions are not particularly limited, and known procedures and conditions commonly used in forming insulating layers for printed wiring boards can be adopted. For example, the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order.

[0193] The swelling liquid used in the roughening treatment is not particularly limited, but examples thereof include alkaline solutions and surfactant solutions, and is preferably an alkaline solution, with sodium hydroxide solution and potassium hydroxide solution being more preferred. Commercially available swelling liquids include "Swelling Dip Securigance P" and "Swelling Dip Securigance SBU" manufactured by Atotech Japan. The swelling treatment using a swelling liquid is not particularly limited, but can be carried out by, for example, immersing the insulating layer in a swelling liquid at 30°C to 90°C for 1 to 20 minutes. To keep the swelling of the resin in 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 to 15 minutes.

[0194] The oxidizing agent used in the roughening treatment is not particularly limited, but examples thereof include alkaline permanganate solutions prepared by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. Roughening treatment using an oxidizing agent such as 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 concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Securigance P" manufactured by Atotech Japan.

[0195] The neutralizing solution used in the roughening treatment is preferably an acidic aqueous solution, and examples of commercially available products include "Reduction Solution Securigant P" manufactured by Atotech Japan.

[0196] Treatment with a neutralizing solution can be carried out by immersing the surface that has been roughened with an oxidizing agent in a neutralizing solution at 30° C. to 80° C. for 5 to 30 minutes. From the standpoint of workability, etc., a method in which the object that has been roughened with an oxidizing agent is immersed in a neutralizing solution at 40° C. to 70° C. for 5 to 20 minutes is preferred.

[0197] In one embodiment, the arithmetic mean roughness (Ra) of the insulating layer surface after the roughening treatment is not particularly limited, but 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, etc. Furthermore, the root mean square roughness (Rq) of the insulating layer surface after the 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, etc. 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.

[0198] Step (V) is a step of forming a conductor layer, and the conductor layer is formed on the insulating layer. The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer contains one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. The conductor layer may be a single metal layer or an alloy layer. Examples of alloy layers include layers formed from alloys of two or more metals selected from the above group (e.g., nickel-chromium alloys, copper-nickel alloys, and copper-titanium alloys). Among these, from the viewpoints of versatility in forming the conductor layer, cost, ease of patterning, etc., a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of a nickel-chromium alloy, a copper-nickel alloy, or a copper-titanium alloy is preferred, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of a nickel-chromium alloy is more preferred, and a single metal layer of copper is even more preferred.

[0199] 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 types of metals or alloys are laminated. When the conductor layer has a multi-layer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc, or titanium, or an alloy layer of a nickel-chromium alloy.

[0200] The thickness of the conductor layer depends on the desired design of the printed wiring board, but is generally 3 μm to 35 μm, preferably 5 μm to 30 μm.

[0201] In one embodiment, the conductor layer may be formed by plating. For example, a conductor layer having a desired wiring pattern can be formed by plating the surface of the insulating layer using a conventionally known technique such as a semi-additive method or a full-additive method. From the viewpoint of ease of production, it is preferable to form the conductor layer by a semi-additive method. An example of forming the conductor layer by a semi-additive method will be described below.

[0202] First, a plating seed layer is formed on the surface of an insulating layer by electroless plating. Next, a mask pattern is formed on the formed plating seed layer, exposing a portion of the plating seed layer corresponding to the desired wiring pattern. After a metal layer is formed on the exposed plating seed layer by electrolytic plating, the mask pattern is removed. Thereafter, unnecessary plating seed layer is removed by etching or the like, thereby forming a conductor layer having the desired wiring pattern.

[0203] In another embodiment, the conductor layer may be formed using a metal foil. When a metal foil is used to form the conductor layer, step (V) is preferably performed between steps (I) and (II). For example, after step (I), the support is removed, and a metal foil is laminated on the exposed surface of the resin composition layer. The resin composition layer and the metal foil may be laminated by a vacuum lamination method. The lamination conditions may be the same as those described for step (I). Next, step (II) is performed to form an insulating layer. Thereafter, a conductor layer having a desired wiring pattern can be formed using the metal foil on the insulating layer by a conventionally known technique such as a subtractive method or a modified semi-additive method.

[0204] The metal foil can be produced by a known method such as an electrolytic method, a rolling method, etc. Examples of commercially available metal foils include HLP foil and JXUT-III foil manufactured by JX Nippon Mining & Metals Corporation, and 3EC-III foil and TP-III foil manufactured by Mitsui Mining & Smelting Co., Ltd.

[0205] <Semiconductor device> The 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.

[0206] Examples of semiconductor devices include various semiconductor devices used in electrical appliances (for example, computers, mobile phones, digital cameras, and televisions) and vehicles (for example, motorcycles, automobiles, trains, ships, and aircraft). [Example]

[0207] The present invention will be described in more detail below with reference to examples. The present invention is not limited to these examples. In the following, "parts" and "%" representing amounts mean "parts by mass" and "% by mass", respectively, unless otherwise specified. Unless otherwise specified, the temperature and pressure conditions are room temperature (23°C) and atmospheric pressure (1 atm), respectively.

[0208] Example 1: Preparation of resin composition 1 40 parts of polycarbonate oligomer ("Ph-PCO-BPCDE" manufactured by Honshu Chemical Industry Co., Ltd., weight-average molecular weight 4080, hydroxyl group content 0.01 mmol / g, main component: polycarbonate resin having a repeating structural unit represented by the following formula (A)), 10 parts of bixylenol-type epoxy resin ("YX4000H" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent approximately 190 g / eq.), and 5 parts of bisphenol A-type epoxy resin ("828US" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent approximately 180 g / eq.) were heated and dissolved in 60 parts of MEK with stirring. After cooling to room temperature, 32 parts of an active ester curing agent (DIC Corporation's "HPC-8150-62T," active ester group equivalent weight approximately 220 g / eq., non-volatile content 62% by mass in toluene solution), 4 parts of a curing accelerator (4-dimethylaminopyridine (DMAP), MEK solution with a solid content of 5% by mass), and spherical silica (Admatechs Co., Ltd.'s "SO-C2," specific surface area 5.9 m) surface-treated with N-phenyl-8-aminooctyl-trimethoxysilane (Shin-Etsu Chemical Co., Ltd., molecular weight 325.2) were added. 2 225 parts of cellulose acetate (1 / g, average particle size 0.77 μm) were mixed and uniformly dispersed in a high-speed rotary mixer, and then filtered through a cartridge filter ("SHP020" manufactured by ROKITECHNO) to prepare Resin Composition 1 (resin varnish).

[0209] [ka]

[0210] Example 2: Preparation of resin composition 2 In Example 1, 32 parts of the active ester curing agent (DIC Corporation's "HPC-8150-62T," active ester group equivalent weight approximately 220 g / eq., toluene solution with non-volatile content of 62% by mass) was changed to 31 parts of an active ester curing agent (DIC Corporation's "HPC-8000-65T," active ester group equivalent weight approximately 223 g / eq., toluene solution with non-volatile content of 65% by mass). Resin composition 2 (resin varnish) was prepared in the same manner as in Example 1, except for the above-mentioned changes.

[0211] Example 3: Preparation of resin composition 3 In Example 1, the amount of polycarbonate oligomer ("Ph-PCO-BPCDE", manufactured by Honshu Chemical Industry Co., Ltd., weight average molecular weight 4080, hydroxyl group content 0.01 mmol / g) was changed from 40 parts to 200 parts. Resin composition 3 (resin varnish) was prepared in the same manner as in Example 1 except for the above.

[0212] Example 4: Preparation of resin composition 4 In Example 1, 1) Spherical silica ("SO-C2", manufactured by Admatechs Co., Ltd., specific surface area 5.9 m) surface-treated with N-phenyl-8-aminooctyl-trimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., molecular weight 325.2). 2 / g, average particle size 0.77 μm) from 225 parts to 290 parts, 2) 29 parts of biphenylaralkyl novolac maleimide ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., MEK / toluene mixed solution with a non-volatile content of 70%) was added, 3) 0.5 parts of a polymerization initiator (NOF Corporation's "Perhexyl D", an MEK solution with a solid content of 20% by mass) was added. Resin composition 4 (resin varnish) was prepared in the same manner as in Example 1 except for the above.

[0213] Example 5: Preparation of resin composition 5 In Example 4, 29 parts of biphenylaralkyl novolac maleimide ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., MEK / toluene mixed solution with a non-volatile content of 70%) was changed to 20 parts of a maleimide liquid curing agent ("BMI689" manufactured by Designer Molecules, Inc., maleimide group equivalent: 345 g / eq.). Resin composition 5 (resin varnish) was prepared in the same manner as in Example 4, except for the above-mentioned changes.

[0214] Example 6: Preparation of resin composition 6 In Example 4, 29 parts of biphenylaralkyl novolac maleimide ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., MEK / toluene mixed solution with a non-volatile content of 70%) was changed to 20 parts of methacrylic-modified polyphenylene ether ("SA9000-111" manufactured by SABIC Innovative Plastics). Resin composition 6 (resin varnish) was prepared in the same manner as in Example 4 except for the above-mentioned points.

[0215] Example 7: Preparation of resin composition 7 In Example 4, 29 parts of biphenylaralkyl novolac maleimide ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., MEK / toluene mixed solution with a non-volatile content of 70%) was changed to 31 parts of vinylbenzyl-modified polyphenylene ether ("OPE-2St 2200" manufactured by Mitsubishi Gas Chemical Co., Ltd., toluene solution with a non-volatile content of 65%). Resin composition 7 (resin varnish) was prepared in the same manner as in Example 4 except for the above-mentioned points.

[0216] Comparative Example 1: Preparation of Resin Composition 8 In Example 1, 40 parts of polycarbonate oligomer ("Ph-PCO-BPCDE" manufactured by Honshu Chemical Industry Co., Ltd., weight-average molecular weight 4080, hydroxyl group content 0.01 mmol / g) was changed to 40 parts of polycarbonate ("FPC2136" manufactured by Mitsubishi Gas Chemical Co., Ltd., weight-average molecular weight 20895, main component: polycarbonate resin having repeating structural units represented by the following formula (A'-1) and repeating structural units represented by the following formula (A'-2)). Resin composition 8 (resin varnish) was prepared in the same manner as in Example 1, except for the above-mentioned changes.

[0217] [ka]

[0218] <Test Example 1: Measurement and Evaluation of Relative Dielectric Constant (Dk) and Dielectric Loss Tangent (Df)> (1) Preparation of a resin sheet having a resin composition layer thickness of 40 μm A polyethylene terephthalate film ("AL5" manufactured by Lintec Corporation, thickness 38 μm) with a release layer was prepared as a support. The resin compositions obtained in the Examples and Comparative Examples were uniformly applied onto the release layer of this support so that the thickness of the resin composition layer after drying would be 40 μm. Thereafter, the resin composition was dried at 80°C to 100°C (average 90°C) for 4 minutes to obtain a resin sheet including the support and the resin composition layer.

[0219] (2) Preparation of cured product for evaluation The resin sheet obtained in (1) above was cured in an oven at 200°C for 90 minutes. The resin sheet was removed from the oven and the support was peeled off to obtain a cured resin composition layer. The cured product was cut into a length of 80 mm and a width of 2 mm to be used as a cured product for evaluation.

[0220] (3) Measurement of relative permittivity and dielectric loss tangent The cured evaluation product obtained in (2) above was measured for its relative permittivity (Dk) and dielectric loss tangent (Df) by the cavity resonance perturbation method using a cavity resonator perturbation dielectric constant measuring device "CP521" manufactured by Kanto Applied Electronics Development Co., Ltd. and an "HP8362B" manufactured by Agilent Technologies, Inc., at a measurement frequency of 5.8 GHz and a measurement temperature of 23°C. Measurements were carried out on three test pieces, and the average was calculated and evaluated according to the following evaluation criteria.

[0221] Evaluation criteria "○": When the relative dielectric constant is 3.1 or less and the dielectric loss tangent is 0.0040 or less "X": When the relative dielectric constant exceeds 3.1 or the dielectric loss tangent exceeds 0.0040

[0222] <Test Example 2: Measurement and Evaluation of Warpage> (1) Laminating resin sheets A resin sheet prepared in the same manner as in Test Example 1(1) was cut into a 9.5 cm square piece and laminated onto the roughened surface of a 10 cm square piece of Mitsui Mining & Smelting's copper foil "3EC-III (thickness: 35 μm)" using a batch-type vacuum pressure laminator (Nikko Materials Co., Ltd., two-stage build-up laminator, CVP700). The pressure was reduced for 30 seconds to 13 hPa or less, and the laminate was then pressed at 120°C for 30 seconds at a pressure of 0.74 MPa to produce a metal foil with a resin composition layer, after which the PET film was peeled off.

[0223] (2) Curing of the resin composition layer The four sides of the metal foil with the resin composition layer obtained in (1) above were attached to a 1 mm thick SUS plate with polyimide tape so that the resin composition layer was on top, and the resin composition layer was cured under curing conditions of 190°C and 90 minutes.

[0224] (3) Measurement of warpage The polyimide tape was peeled off from three of the four sides of the metal foil with the resin composition layer obtained in (2) above, and the height of the highest point from the SUS plate was measured to determine the warpage value. The magnitude of the warpage was also evaluated according to the following criteria. "Good": The warp is less than 1 cm "△": When the warp is 1cm or more but less than 3cm "×": The warp is 3cm or more

[0225] <Test Example 3: Measurement and Evaluation of Copper Foil Adhesion> (1) Copper foil surface preparation The shiny side of Mitsui Mining & Smelting Co., Ltd.'s "3EC-III" (electrolytic copper foil, 35 μm) was etched by 1 μm with a micro-etching agent (MEC Co., Ltd.'s "CZ8101") to roughen the copper surface, and then an anti-rust treatment (CL8300) was applied. Furthermore, the foil was heated in an oven at 130°C for 30 minutes. This copper foil is called CZ copper foil.

[0226] (2) Preparation of inner layer board Both sides of a glass cloth-based epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.4 mm, Panasonic "R1515A") with an inner layer circuit formed on it were etched 1 μm deep with a microetching agent (MEC "CZ8101") to roughen the copper surface.

[0227] (3) Laminating copper foil and forming an insulating layer The protective film was peeled off from a resin sheet prepared in the same manner as in Test Example 1(1) to expose the resin composition layer. Using a batch-type vacuum pressure laminator (Nikko Materials Co., Ltd., two-stage build-up laminator "CVP700"), the resin composition layer was laminated on both sides of the inner layer substrate prepared in (2) above so that the resin composition layer was in contact with the inner layer substrate. Lamination was performed by reducing the pressure for 30 seconds to 13 hPa or less, followed by pressure bonding at 120°C and a pressure of 0.74 MPa for 30 seconds. Next, a heat press was performed at 100°C and a pressure of 0.5 MPa for 60 seconds. The treated side of CZ copper foil was laminated onto the resin composition layer under the same conditions as above. The resin composition layer was then cured at 200°C for 90 minutes to form an insulating layer, thereby producing an evaluation substrate.

[0228] (4) Measurement of copper foil adhesion The evaluation board prepared in (3) above was cut into small pieces measuring 150 x 30 mm. A cutter was used to make a 10 mm wide, 100 mm long cut in the copper foil portion of each small piece, and one end of the copper foil was peeled off and gripped with a gripper. The peel strength was determined by measuring the load (kgf / cm) when 35 mm was peeled off vertically at a rate of 50 mm / min at room temperature. A tensile tester (TSE "AC-50C-SL") was used for the measurement. The measurement was performed in accordance with the Japanese Industrial Standard (JIS C6481), and the copper foil adhesion (adhesion strength) was evaluated according to the following criteria. "Good": Adhesion strength is 0.40kgf / cm or more "X": Adhesion strength is less than 0.40 kgf / cm

[0229] The non-volatile component contents of the resin compositions of the Examples and Comparative Examples, and the measurement results and evaluation results of the Test Examples are shown in Table 1 below.

[0230] [Table 1]

[0231] As shown in Table 1, by using a resin composition containing (A) a polycarbonate resin and (B) an epoxy resin, where component (A) contains a polycarbonate resin having a repeating structural unit represented by formula (A1) described above, it is possible to obtain a cured product with a lower relative dielectric constant (Dk). Furthermore, it is found that such a cured product has a low dielectric loss tangent (Df), is less prone to warping, and has high copper foil adhesion.

Claims

1. A resin composition comprising (A) a polycarbonate resin, (B) an epoxy resin, and (C) an inorganic filler, The component (A) is represented by the formula (A1): 【Chemistry 1】 [In the formula, Ring A and ring B each independently represent an aromatic ring which may have a substituent; Ring X represents a non-aromatic carbocyclic ring having 7 or more carbon atoms which may have a substituent. The polycarbonate resin contains a repeating structural unit represented by The weight average molecular weight of the component (A) is 3,000 or more, The hydroxyl group content of component (A) is 0.05 mmol / g or less, The content of the component (A) is 10% by mass or more and 50% by mass or less, when the total amount of non-volatile components in the resin composition is 100% by mass, The content of the (B) component is 3% by mass or more and 20% by mass or less, when the total amount of non-volatile components in the resin composition is 100% by mass, The content of the component (C) is 40% by mass or more and 80% by mass or less, when the total amount of nonvolatile components in the resin composition is 100% by mass, the total content of the (A) component, the (B) component, and the (C) component is 73% by mass or more and 98% by mass or less, the mass ratio of the polycarbonate resin (A) to the inorganic filler (C) (component (A) / component (C)) is 0.1 or more and 1 or less, the dielectric loss tangent (Df) of a cured product of the resin composition is 0.0040 or less when measured at 5.8 GHz and 23°C; A resin composition, wherein the relative dielectric constant (Dk) of a cured product of the resin composition is 3.1 or less when measured at 5.8 GHz and 23°C.

2. The component (A) is represented by the formula (A3): 【Chemistry 2】 [In the formula, R １ and R ２ each independently represents a hydrogen atom, an alkyl group, or an aryl group; R ３ and R ４ each independently represents an alkyl group or an aryl group; a and b each independently represent 0, 1, 2, 3, or 4; n represents an integer of 6 or more. The resin composition according to claim 1, comprising a polycarbonate resin having a repeating structural unit represented by the formula:

3. The resin composition according to claim 1 or 2, wherein the weight average molecular weight (Mw) of the component (A) is 10,000 or less.

4. A resin composition comprising (A) a polycarbonate resin, (B) an epoxy resin, and (C) an inorganic filler, The component (A) is represented by the formula (A1): 【Transformation 3】 [In the formula, Ring A and ring B each independently represent an aromatic ring which may have a substituent; Ring X represents a non-aromatic carbocyclic ring having 7 or more carbon atoms which may have a substituent. The polycarbonate resin contains a repeating structural unit represented by The weight average molecular weight of the component (A) is 3,000 or more, The hydroxyl group content of component (A) is 0.05 mmol / g or less, The content of the component (A) is 10% by mass or more and 30% by mass or less, when the total amount of non-volatile components in the resin composition is 100% by mass, The content of the (B) component is 3% by mass or more and 20% by mass or less, when the total amount of non-volatile components in the resin composition is 100% by mass, The content of the component (C) is 50% by mass or more and 80% by mass or less, when the total amount of non-volatile components in the resin composition is 100% by mass, the total content of the (A) component, the (B) component, and the (C) component is 73% by mass or more and 98% by mass or less, the mass ratio of the polycarbonate resin (A) to the inorganic filler (C) (component (A) / component (C)) is 0.1 or more and 0.5 or less; the dielectric loss tangent (Df) of a cured product of the resin composition is 0.0040 or less when measured at 5.8 GHz and 23°C; A resin composition, wherein the relative dielectric constant (Dk) of a cured product of the resin composition is 3.1 or less when measured at 5.8 GHz and 23°C.

5. The resin composition according to any one of claims 1 to 4, wherein the component (C) is silica.

6. The resin composition according to any one of claims 1 to 5, further comprising (D) an epoxy resin curing agent.

7. The resin composition according to claim 6 , wherein the component (D) comprises an active ester curing agent.

8. The resin composition according to any one of claims 1 to 7, further comprising (E) a radically polymerizable compound.

9. A cured product of the resin composition according to any one of claims 1 to 8.

10. A sheet-like laminate material comprising the resin composition according to any one of claims 1 to 8.

11. A resin sheet comprising: a support; and a resin composition layer formed from the resin composition according to any one of claims 1 to 8 provided on the support.

12. A printed wiring board comprising an insulating layer made of a cured product of the resin composition according to any one of claims 1 to 8.

13. A semiconductor device comprising the printed wiring board according to claim 12.

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