Resin composition

Abstract

To provide a resin composition that gives a cured product having reduced unevenness after lamination.SOLUTION: A resin composition contains (A) a compound having a repeating unit represented by formula (1), (B) an epoxy resin, and (C) an active ester compound. (In formula (1), ring A is an optionally substituted nitrogen-containing aromatic ring; ring B and ring C independently represent an optionally substituted aromatic ring; X is a single bond or divalent non-aromatic hydrocarbon group).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a resin composition containing an epoxy resin. Further, the present invention relates to a cured product, a sheet-like laminated material, a resin sheet, a printed wiring board, and a semiconductor device obtained by using the resin composition.

Background Art

[0002] As a manufacturing technique for printed wiring boards, a manufacturing method by a build-up method in which an insulating layer and a conductor layer are alternately laminated is known. In the manufacturing method by the build-up method, generally, the insulating layer is formed by curing a resin composition. It is known that unevenness may occur after the lamination process when the resin composition is laminated on the sheet support substrate.

[0003] Heretofore, resin compositions using polymers of bisphenol ethers containing nitrogen-containing heterocycles have been known (Patent Documents 1 and 2).

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0005] An object of the present invention is to provide a resin composition capable of obtaining a cured product with suppressed unevenness after lamination.

Means for Solving the Problems

[0006] To achieve the object of the present invention, the inventors have conducted intensive studies and as a result, have found that in a resin composition containing (B) an epoxy resin and (C) an active ester compound, by using a compound containing a repeating unit represented by the formula (1) (A), a cured product with suppressed unevenness after lamination can be obtained, and thus the present invention has been completed.

[0007] That is, the present invention includes the following contents. [1] (A) A compound containing a repeating unit represented by the formula (1):

[0008]

Chemical formula

[0009] [In the formula, ring A represents a nitrogen-containing aromatic ring which may have a substituent; ring B and ring C each independently represent an aromatic ring which may have a substituent; X represents a single bond or a divalent non-aromatic hydrocarbon group.] A resin composition containing a compound containing a repeating unit represented by the formula (1), (B) an epoxy resin, and (C) an active ester compound. [2] The component (A) is a compound represented by the formula (1A) or (1B):

[0010]

Chemical formula

[0011] [In the formula, X 1 , X 2 , X 3 and X 4 each independently represent N, CH or CR a , and at least one of X 1 , X 2 , X 3 and X 4 is N; R 1 and R 2 each independently represent a hydrogen atom, an alkyl group or an alkenyl group, or R 1 and R 2combine together and bond to each other to form a cycloalkane ring which may have a group selected from an alkyl group and an alkenyl group, or a cycloalkene ring which may have a group selected from an alkyl group and an alkenyl group; R a , R b and R c each independently represent a substituent; b and c each independently represent an integer from 0 to 3.] The resin composition according to [1] above, which is a compound containing a repeating unit represented by [3] The resin composition according to [1] or [2] above, wherein the content of component (A) is 0.01% by mass to 3% by mass when the non-volatile components in the resin composition are 100% by mass. [4] The resin composition according to any one of [1] to [3] above, wherein component (B) contains a condensed-ring structure-containing epoxy resin (B-1). [5] The resin composition according to [4] above, wherein component (B-1) is a monomeric condensed-ring structure-containing epoxy resin. [6] The resin composition according to any one of [1] to [5] above, wherein the content of component (B) is 1% by mass to 30% by mass when the non-volatile components in the resin composition are 100% by mass. [7] The resin composition according to any one of [1] to [6] above, wherein the mass ratio of component (B) to component (A) ((B) component / (A) component) is 10 to 50. [8] The resin composition according to any one of [1] to [7] above, wherein the content of component (C) is 5% by mass to 30% by mass when the non-volatile components in the resin composition are 100% by mass. [9] The resin composition according to any one of [1] to [8] above, wherein the mass ratio of component (C) to component (A) ((C) component / (A) component) is 30 to 100.

[10] The resin composition according to any one of [1] to [9] above, further comprising (D) an inorganic filler.

[11] The resin composition according to

[10] above, wherein component (D) is silica.

[12] The resin composition according to

[10] or

[11] above, wherein the content of component (D) is 50% by mass or more when the non-volatile components in the resin composition are 100% by mass.

[13] The resin composition according to

[12] above, wherein the content of component (D) is 70% by mass or more when the non-volatile components in the resin composition are 100% by mass.

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

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

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

[14] above, further comprising (F-1) a carbodiimide-based curing agent.

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

[15] above.

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

[15] above.

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

[15] above provided on the support.

[19] A printed wiring board including 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 including the printed wiring board according to

[19] above. [Effect of the Invention]

[0012] According to the resin composition of the present invention, a cured product with suppressed unevenness after lamination can be obtained. [Modes for Carrying Out the Invention]

[0013] Hereinafter, the present invention will be described in detail according to its preferred embodiments. However, the present invention is not limited to the following embodiments and exemplifications, and can be arbitrarily modified and implemented without departing from the scope of the claims of the present invention and its equivalent scope.

[0014] <Resin Composition> The resin composition of the present invention contains (A) a compound containing a repeating unit represented by formula (1), (B) an epoxy resin, and (C) an active ester compound. By using such a resin composition, a cured product with suppressed unevenness after lamination can be obtained. Further, in a specific embodiment, a cured product with a low dielectric tangent (Df) can be obtained. Further, in a specific embodiment, a cured product with good plating adhesion (peel strength of the plated conductor layer) can be obtained.

[0015] The resin composition of the present invention may further contain an arbitrary component in addition to (A) a compound containing a repeating unit represented by formula (1), (B) an epoxy resin, and (C) an active ester compound. Examples of the arbitrary component include (D) an inorganic filler, (E) a radically polymerizable compound, (F) a curing agent, (G) a curing accelerator, (H) other additives, and (I) an organic solvent. Hereinafter, each component contained in the resin composition will be described in detail.

[0016] <(Compound containing a repeating unit represented by formula (1))> The resin composition of the present invention contains (A) formula (1):

[0017]

Chemical formula

[0018] [In the formula, ring A represents a nitrogen-containing aromatic ring which may have a substituent; ring B and ring C each independently represent an aromatic ring which may have a substituent; X represents a single bond or a divalent non-aromatic hydrocarbon group.] and contains a compound containing a repeating unit represented by the formula.

[0019] Ring A represents a nitrogen-containing aromatic ring which may have substituents. The aromatic ring means a ring that follows Hückel's rule where the number of electrons contained in the π electron system on the ring is 4n + 2 (n is a natural number). The nitrogen-containing aromatic ring represented by Ring A has, as ring-constituting atoms, in addition to carbon atoms, one or more (preferably two or more, particularly preferably two) nitrogen atoms, and may further have heteroatoms other than nitrogen atoms such as oxygen atoms and sulfur atoms. The nitrogen-containing aromatic ring represented by Ring A is preferably a 5- to 14-membered nitrogen-containing aromatic ring, more preferably a 5- to 10-membered nitrogen-containing aromatic ring, still more preferably a 5- or 6-membered nitrogen-containing aromatic ring, and particularly preferably a 6-membered nitrogen-containing aromatic ring. The nitrogen-containing aromatic ring represented by Ring A includes not only monocyclic aromatic rings and condensed rings formed by condensation of two or more monocyclic aromatic rings, but also condensed rings formed by condensation of one or more monocyclic non-aromatic rings with one or more monocyclic aromatic rings.

[0020] Preferable specific examples of the nitrogen-containing aromatic ring represented by Ring A include, for example, monocyclic nitrogen-containing aromatic rings such as pyrrole ring, imidazole ring, pyrazole ring, 1,2,3-triazole ring, 1,2,4-triazole ring, tetrazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, 1,2,3-triazine ring, 1,2,4-triazine ring, 1,3,5-triazine ring; condensed rings of monocyclic nitrogen-containing aromatic rings such as indole ring, isoindole ring, benzimidazole ring, indazole ring, benzotriazole ring, quinoxaline ring, cinnoline ring, quinazoline ring, phthalazine ring and benzene ring; condensed rings of monocyclic nitrogen-containing aromatic rings such as pteridine ring, purine ring, 4-azaindole ring, 5-azaindole ring, 6-azaindole ring, 7-azaindole ring, 7-azaindazole ring, pyrazolo[1,5-a]pyrimidine ring, 1,8-naphthyridine ring, pyrido[3,2-d]pyrimidine ring, pyrido[4,3-d]pyrimidine ring, pyrido[3,4-b]pyrazine ring, pyrido[2,3-b]pyrazine ring, etc. Among them, monocyclic nitrogen-containing aromatic rings are preferred, 6-membered monocyclic nitrogen-containing aromatic rings are more preferred, pyrimidine ring or pyridazine ring is still more preferred, and pyrimidine ring is particularly preferred.

[0021] In this specification, the "substituent" is not particularly limited. For example, it includes monovalent substituents such as an alkyl group, an alkenyl group, an aryl group, an alkyl-aryl group (an aryl group substituted with one or more alkyl groups), an aryl-aryl group (an aryl group substituted with one or more aryl groups), an aryl-alkyl group (an alkyl group substituted with one or more aryl groups), 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, an aryl-carbonyl-oxy group, etc. If substitution is possible, it may also include divalent substituents such as an oxo group (=O).

[0022] An alkyl (group) refers to a linear, branched, and / or cyclic monovalent aliphatic saturated hydrocarbon group. The alkyl (group) preferably has 1 to 14 carbon atoms, more preferably 1 to 10 carbon atoms, still more preferably 1 to 6 or 4 to 10 carbon atoms. Examples of the alkyl (group) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a trimethylcyclohexyl group, a cyclopentylmethyl group, a cyclohexylmethyl group, etc. An alkenyl (group) refers to a linear, branched, and / or cyclic monovalent aliphatic unsaturated hydrocarbon group having at least one carbon-carbon double bond. The alkenyl (group) preferably has 2 to 14 carbon atoms, more preferably 2 to 10 carbon atoms, still more preferably 2 to 6 or 4 to 10 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, a cyclohexenyl group, etc. An aryl (group) refers to a monovalent aromatic hydrocarbon group. The aryl (group) preferably has 6 to 14 carbon atoms. Examples of the aryl (group) include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, etc.

[0023] Ring B and ring C each independently represent an aromatic ring which may have a substituent. The aromatic ring represented by ring B or ring C can be a carbocyclic ring having carbon atoms as ring-constituting atoms, or a heterocyclic ring having, in addition to carbon atoms, hetero atoms such as oxygen atoms, nitrogen atoms, sulfur atoms, etc. as ring-constituting atoms. However, in one embodiment, it is preferably a carbocyclic ring. The aromatic ring represented by ring B or ring C is preferably a 5- to 14-membered aromatic ring, more preferably a 5- to 10-membered aromatic ring, still more preferably a 5- or 6-membered aromatic ring, and particularly preferably a 6-membered aromatic ring. The aromatic ring represented by ring B or ring C includes not only a monocyclic aromatic ring and a condensed ring in which two or more monocyclic aromatic rings are condensed, but also a condensed ring in which one or more monocyclic non-aromatic rings are condensed to one or more monocyclic aromatic rings.

[0024] Preferable specific examples of the aromatic ring represented by ring B or ring C include monocyclic aromatic rings such as benzene ring, furan ring, thiophene ring, pyrrole ring, pyrazole ring, oxazole ring, isoxazole ring, thiazole ring, imidazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring; condensed rings in which two or more monocyclic aromatic rings are condensed, such as naphthalene ring, anthracene ring, benzofuran ring, isobenzofuran ring, indole ring, isoindole ring, benzothiophene ring, benzimidazole ring, indazole ring, benzoxazole ring, benzoisoxazole ring, benzothiazole ring, quinoline ring, isoquinoline ring, quinoxaline ring, acridine ring, quinazoline ring, cinnoline ring, phthalazine ring; condensed rings in which one or more monocyclic non-aromatic rings are condensed with one or more monocyclic aromatic rings, such as indane ring, fluorene ring, tetralin ring, etc. Preferably, it is a monocyclic aromatic ring, more preferably a 6-membered monocyclic aromatic ring, and particularly preferably a benzene ring.

[0025] X is a single bond or a divalent non-aromatic hydrocarbon group. The divalent non-aromatic hydrocarbon group represented by X is a saturated or unsaturated straight-chain, branched-chain and / or cyclic divalent non-aromatic hydrocarbon group. The divalent non-aromatic hydrocarbon group represented by X is, for example, a divalent non-aromatic hydrocarbon group having 1 to 100 carbon atoms, preferably 1 to 50 carbon atoms, more preferably 1 to 30 carbon atoms, and even more preferably 1 to 20 carbon atoms.

[0026] X is preferably a divalent non-aromatic hydrocarbon group, and more preferably has the formula (X1):

[0027]

Chemical formula

[0028] [In the formula, R 1 and R 2 each independently represent a hydrogen atom, an alkyl group or an alkenyl group, or R 1 and R 2Combine together and bond to each other to form a cycloalkane ring which may have a group selected from an alkyl group and an alkenyl group, or a cycloalkene ring which may have a group selected from an alkyl group and an alkenyl group; * indicates a bonding site. It is a divalent group represented by, and more preferably, the formulas (X2-1) to (X2-3):

[0029]

Chemical formula

[0030] [In the formula, R 3 , R 4 , and R 5 each independently represents an alkyl group; x represents an integer of 0 to 5 (preferably 1 to 5, more preferably 2 to 4); * indicates a bonding site. It is a divalent group represented by any of, and particularly preferably, the divalent group represented by the formula (X2-1).

[0031] The cycloalkane ring refers to a cyclic aliphatic saturated hydrocarbon ring. The cycloalkane ring is preferably a cycloalkane ring having 3 to 8 carbon atoms, and more preferably a cycloalkane ring having 5 or 6 carbon atoms. Examples of the cycloalkane ring include a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, etc. The cycloalkene ring refers to a cyclic aliphatic unsaturated hydrocarbon ring having at least one carbon-carbon double bond. The cycloalkene ring is preferably a cycloalkene ring having 4 to 8 carbon atoms, and more preferably a cycloalkene ring having 5 or 6 carbon atoms. Examples of the cycloalkene ring include a cyclobutene ring, a cyclopentene ring, a cyclohexene ring, a cycloheptene ring, a cyclooctene ring, a cyclopentadiene ring, a cyclohexadiene ring, etc.

[0032] (A) The compound containing the repeating unit represented by the formula (1) is preferably the formula (1A) or (1B):

[0033]

Chemical formula

[0034] [wherein, X 1 , X 2 , X 3 and X 4 each independently represents N, CH or CR a (preferably N or CH) and X 1 , X 2 , X 3 and X 4 at least one (preferably at least two, particularly preferably two) of which is N; R a , R b and R c each independently represents a substituent (preferably an alkyl group, an alkenyl group, an aryl group, an alkyl-aryl group, an aryl-aryl group, or an aryl-alkyl group, more preferably an alkyl group, an alkenyl group, or an aryl group, particularly preferably an aryl group); b and c each independently represent an integer of 0 to 3 (preferably 0); and other symbols are the same as in formula (X1).] It is a compound containing a repeating unit represented by, and more preferably, formulas (1A-1) to (1B-3):

[0035] [Chemical formula]

[0036] [wherein, a represents an integer of 0 to 2 (preferably 0); and other symbols are the same as in formulas (1A), (1B) and (X2-1) to (X2-3).] It is a compound containing a repeating unit represented by any of, and particularly preferably, it is a compound containing a repeating unit represented by formula (1A-1).

[0037] (A) The compound containing the repeating unit represented by formula (1) may have reactive groups such as phenolic hydroxyl groups, thiol groups, amino groups, carboxyl groups, and sulfo groups in one embodiment, and preferably may have a phenolic hydroxyl group. In one embodiment, it is preferable to have two or more reactive groups in one molecule.

[0038] (A) In the compound containing the repeating unit represented by formula (1), the number of repeating units is preferably 5 or more, more preferably 10 or more, still more preferably 30 or more, and particularly preferably 50 or more. The upper limit of the number of repeating units is not particularly limited, but can be, for example, 10000 or less, 5000 or less, 3000 or less, 2000 or less, 1000 or less, etc.

[0039] (A) The weight average molecular weight (Mw) of the compound containing the repeating unit represented by formula (1) is not particularly limited, but is preferably 1000 to 200000, more preferably 5000 to 150000, and still more preferably 10000 to 120000. The weight average molecular weight of the resin can be measured as a polystyrene-equivalent value by gel permeation chromatography (GPC) method.

[0040] (A) The glass transition temperature (Tg) of the compound containing the repeating unit represented by formula (1) is not particularly limited, but can be preferably 100 to 300 °C, more preferably 150 to 250 °C.

[0041] (A) The compound containing the repeating unit represented by formula (1) can be synthesized, for example, by using the method described in International Publication No. 2019 / 054335 or International Publication No. 2020 / 021827 or a method analogous thereto.

[0042] The content of the compound containing the repeating unit represented by the formula (1) in the resin composition is not particularly limited, but when the non-volatile components in the resin composition are 100% by mass, it is preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less, even more preferably 1% by mass or less, and particularly preferably 0.5% by mass or less. The lower limit of the content of the compound containing the repeating unit represented by the formula (1) in the resin composition is not particularly limited, but when the non-volatile components in the resin composition are 100% by mass, it is preferably 0.0001% by mass or more, more preferably 0.001% by mass or more, still more preferably 0.01% by mass or more, even more preferably 0.05% by mass or more, and particularly preferably 0.1% by mass or more.

[0043] <(B) Epoxy resin> The resin composition of the present invention contains (B) an epoxy resin. (B) The epoxy resin means a curable resin having an epoxy group. (B) The epoxy resin preferably includes (B-1) a condensed ring structure-containing epoxy resin.

[0044] <(B-1) Condensed ring structure-containing epoxy resin> (B-1) The condensed ring structure-containing epoxy resin means a resin having one or more condensed rings and one or more (preferably two or more) epoxy groups in one molecule. (B-1) The condensed ring structure-containing epoxy resin may be used alone or in combination of two or more in any ratio.

[0045] (B-1) The condensed ring contained in the condensed ring structure-containing epoxy resin is preferably a condensed aromatic carbon ring. The condensed aromatic carbon ring is a bicyclic or higher aromatic carbon ring obtained by condensing two or more benzene rings, and preferably has 10 to 18 carbon atoms, more preferably 10 to 14 carbon atoms. Examples include a naphthalene ring, an anthracene ring, a phenanthrene ring, etc., and particularly preferably a naphthalene ring.

[0046] (B-1) The epoxy resin containing a condensed ring structure may be any of glycidyl ether type, glycidyl amine type, glycidyl ester type, and olefin oxidation (alicyclic) type. Among them, the glycidyl ether type is preferably used.

[0047] (B-1) The epoxy resin containing a condensed ring structure may be monomeric or a repeating structure type. Here, the repeating structure type refers to a polymer structure having an average of three or more repeating units containing one or more condensed rings, and the monomeric type refers to a molecular structure having no repeating unit or having two repeating units containing one or more condensed rings. (B-1) The epoxy resin containing a condensed ring structure is an epoxy resin selected from (B-1-1) monomeric epoxy resin containing a condensed ring structure and (B-1-2) repeating structure type epoxy resin containing a condensed ring structure, and preferably (B-1-1) monomeric epoxy resin containing a condensed ring structure.

[0048] Examples of (B-1-1) monomeric epoxy resin containing a condensed ring structure include monomeric epoxy resin containing a condensed ring structure having one condensed ring in one molecule, such as 1,6-bis(glycidyloxy)naphthalene, 1,5-bis(glycidyloxy)naphthalene, 2,7-bis(glycidyloxy)naphthalene, 2,6-bis(glycidyloxy)naphthalene; monomeric epoxy resin containing a condensed ring structure having two condensed rings in one molecule, such as bis[2-(glycidyloxy)-1-naphthyl]methane, 2,2-bis[2-(glycidyloxy)-1-naphthyl]propane, bis[2,7-bis(glycidyloxy)-1-naphthyl]methane, 2,2-bis[2,7-bis(glycidyloxy)-1-naphthyl]propane, [2,7-bis(glycidyloxy)-1-naphthyl][2-(glycidyloxy)-1-naphthyl]methane, 2-[2,7-bis(glycidyloxy)-1-naphthyl]-2-[2-(glycidyloxy)-1-naphthyl]propane.

[0049] (B-1-1) The monomeric condensed ring structure-containing epoxy resin is, in one embodiment, preferably a monomeric condensed ring structure-containing epoxy resin having one condensed ring in one molecule, and particularly preferably 1,6-bis(glycidyloxy)naphthalene.

[0050] (B-1-1) The monomeric condensed ring structure-containing epoxy resin is preferably a bifunctional to tetrafunctional epoxy resin in one embodiment, more preferably a bifunctional or trifunctional epoxy resin, and particularly preferably a bifunctional epoxy resin.

[0051] (B-1-1) The epoxy equivalent of the monomeric condensed ring structure-containing epoxy resin is not particularly limited, but is preferably 50 g / eq. or more, more preferably 80 g / eq. or more, still more preferably 100 g / eq. or more, even more preferably 120 g / eq. or more, and particularly preferably 130 g / eq. or more. The upper limit of the epoxy equivalent of the monomeric condensed ring structure-containing epoxy resin is not particularly limited, but is preferably 1000 g / eq. or less, more preferably 500 g / eq. or less, still more preferably 300 g / eq. or less, even more preferably 200 g / eq. or less, and particularly preferably 160 g / eq. or less. The epoxy equivalent is the mass of the resin per equivalent of epoxy groups. The epoxy equivalent can be measured according to JIS K7236.

[0052] (B-1-1) The molecular weight of the monomeric condensed ring structure-containing epoxy resin is not particularly limited, but is preferably 2000 or less, more preferably 1000 or less, still more preferably 700 or less, even more preferably 600 or less, and particularly preferably 500 or less.

[0053] Examples of commercially available monomeric condensed ring structure-containing epoxy resins include, for example, "HP-4032D" and "HP-4032SS" manufactured by DIC Corporation (epoxy resins having one naphthalene ring in one molecule); "EXA-4750", "HP-4770", "HP-4700", and "HP-4710" manufactured by DIC Corporation (epoxy resins having two naphthalene rings in one molecule), and the like.

[0054] Examples of repeating structure type condensed ring structure-containing epoxy resins include repeating structure type condensed ring structure-containing epoxy resins having three or more condensed rings in one molecule, such as naphthol novolak type epoxy resins, naphthol-phenol co-condensed novolak type epoxy resins, naphthol-cresol co-condensed novolak type epoxy resins, naphthol aralkyl type epoxy resins, naphthalene diol aralkyl type epoxy resins, and naphthylene ether type epoxy resins.

[0055] The epoxy equivalent of the repeating structure type condensed ring structure-containing epoxy resin is not particularly limited, but is preferably 50 g / eq. or more, more preferably 100 g / eq. or more, still more preferably 200 g / eq. or more, even more preferably 250 g / eq. or more, and particularly preferably 300 g / eq. or more. The upper limit of the epoxy equivalent of the repeating structure type condensed ring structure-containing epoxy resin is not particularly limited, but is preferably 2000 g / eq. or less, more preferably 1000 g / eq. or less, still more preferably 500 g / eq. or less, and even more preferably 400 g / eq. or less.

[0056] As commercially available products of the repeating structure type condensed ring structure-containing epoxy resin, for example, "ESN-155", "ESN-185V", "ESN-175", "ESN-475V", "ESN-485", "TX-1507B" (naphthol aralkyl type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP-6000", "HP-6000-L" (naphthylene ether type epoxy resin) manufactured by DIC Corporation; "NC7000L" (naphthol novolak type epoxy resin) manufactured by Nippon Kayaku Co., Ltd. and the like can be mentioned.

[0057] In addition to the (B-1) condensed ring structure-containing epoxy resin, the resin composition may contain (B-2) other epoxy resins. However, from the viewpoint of significantly obtaining the desired effects of the present invention, when the total epoxy resin in the resin composition is 100% by mass, the content of the (B-1) condensed ring structure-containing epoxy resin in the resin composition is preferably 50% by mass or more, 60% by mass or more, more preferably 70% by mass or more, 80% by mass or more, still more preferably 90% by mass or more, 95% by mass or more, even more preferably 98% by mass or more, 99% by mass or more, and particularly preferably 100% by mass.

[0058] <(B-2) Other epoxy resins> (B-2) Other epoxy resins include, for example, bixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, tris-phenol type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolak type epoxy resin, phenol aralkyl type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, isocyanurate type epoxy resin, phenolphthalimide type epoxy resin, phenolphthalein type epoxy resin, etc. (B-2) Other epoxy resins may be used alone or in combination of two or more.

[0059] The resin composition preferably contains, as (B-2) other epoxy resins, an epoxy resin having two or more epoxy groups in one molecule. The proportion of the epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more with respect to 100% by mass of the non-volatile components of (B-2) other epoxy resins.

[0060] Epoxy resins include epoxy resins that are liquid at 20°C (hereinafter sometimes referred to as "liquid epoxy resins") and epoxy resins that are solid at 20°C (hereinafter sometimes referred to as "solid epoxy resins"). The resin composition of the present invention may contain only a liquid epoxy resin, or only a solid epoxy resin, or a combination of a liquid epoxy resin and a solid epoxy resin as (B-2) other epoxy resins.

[0061] As the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferred.

[0062] As the liquid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin having an ester skeleton, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, and epoxy resin having a butadiene structure are preferred.

[0063] Specific examples of the liquid epoxy resin include "828US", "828EL", "jER828EL", "825", "Epicoat 828EL" (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER807", "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "630", "630LSD", "604" (glycidyl amine type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "ED-523T" (glycerol type epoxy resin) manufactured by ADEKA Corporation; "EP-3950L", "EP-3980S" (glycidyl amine type epoxy resin) manufactured by ADEKA Corporation; "EP-4088S" (dicyclopentadiene type epoxy resin) manufactured by ADEKA Corporation; "ZX1059" (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.; "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX Corporation; "Celoxide 2021P" (alicyclic epoxy resin having an ester skeleton) manufactured by Daicel Corporation; "PB-3600", "JP-100", "JP-200" (epoxy resin having a butadiene structure) manufactured by Nippon Soda Co., Ltd.; "ZX1658", "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., etc. These may be used alone or in combination of two or more.

[0064] 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.

[0065] Examples of the solid epoxy resin include a bixylenol type epoxy resin, a cresol novolak type epoxy resin, a dicyclopentadiene type epoxy resin, a trisphenol type epoxy resin, a biphenyl type epoxy resin, a bisphenol A type epoxy resin, a bisphenol AF type epoxy resin, a phenol aralkyl type epoxy resin, a tetraphenylethane type epoxy resin, a phenolphthalimide type epoxy resin, and a phenolphthalein type epoxy resin.

[0066] Specific examples of the solid epoxy resin include "N-690" (cresol novolak type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolak type epoxy resin) manufactured by DIC Corporation; "HP-7200", "HP-7200HH", "HP-7200H", "HP-7200L" (dicyclopentadiene type epoxy resin) manufactured by DIC Corporation; "EPPN-502H" (trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC3000H", "NC3000", "NC3000L", "NC3000FH", "NC3100" (biphenyl type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "YX4000H", "YX4000", "YX4000HK", "YL7890" (bixylenol type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX7700" (phenol aralkyl type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "PG-100", "CG-500" manufactured by Osaka Gas Chemical 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; "WHR991S" (phenolphthalimide type epoxy resin) manufactured by Nippon Kayaku Co., Ltd., and the like. These may be used alone or in combination of two or more.

[0067] (B-2) The epoxy equivalent of other epoxy resins is preferably 50 g / eq. to 5,000 g / eq., more preferably 60 g / eq. to 2,000 g / eq., still more preferably 70 g / eq. to 1,000 g / eq., and even more preferably 80 g / eq. to 500 g / eq.

[0068] (B-2) The weight average molecular weight (Mw) of other epoxy resins is preferably 100 to 5,000, more preferably 300 to 3,000, and still more preferably 400 to 1,500. The weight average molecular weight of the resin can be measured as a value in terms of polystyrene by gel permeation chromatography (GPC) method.

[0069] The content of the (B) epoxy resin in the resin composition is not particularly limited. However, when the non-volatile components in the resin composition are 100% by mass, it is preferably 60% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, even more preferably 20% by mass or less, and particularly preferably 10% by mass or less. The lower limit of the content of the (B) epoxy resin in the resin composition is not particularly limited. However, when the non-volatile components in the resin composition are 100% by mass, it is preferably 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, even more preferably 3% by mass or more, and particularly preferably 5% by mass or more.

[0070] The mass ratio of the (B) epoxy resin to the compound containing the repeating unit represented by the formula (1) (A) in the resin composition ((B) component / (A) component) is not particularly limited. However, it is preferably 1 or more, more preferably 5 or more, still more preferably 10 or more, and particularly preferably 20 or more. The upper limit of the mass ratio of the (B) epoxy resin to the compound containing the repeating unit represented by the formula (1) (A) in the resin composition ((B) component / (A) component) is not particularly limited. However, it is preferably 200 or less, more preferably 100 or less, still more preferably 50 or less, and particularly preferably 30 or less.

[0071] <(C) active ester compound> The resin composition of the present invention contains a (C) active ester compound. Usually, the (C) active ester compound may have a function of reacting with the (B) epoxy resin to cure the resin composition. The (C) active ester compound may be used alone or in combination of two or more in any ratio.

[0072] (C) As the active ester compound, generally, compounds having two or more highly reactive ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, esters of heterocyclic hydroxy compounds, etc., are preferably used. The active ester compound is preferably obtained by a condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound. Particularly from the viewpoint of improving heat resistance, 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, pyromellitic acid, etc. Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzene triol, dicyclopentadiene type diphenol compound, phenol novolak, etc. Here, the "dicyclopentadiene type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

[0073] Specifically, as the (C) active ester compound, a dicyclopentadiene type active ester compound, a naphthalene type active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolak, and an active ester compound containing a benzoylated product of phenol novolak are preferable. Among them, at least one selected from a dicyclopentadiene type active ester compound and a naphthalene type active ester compound is more preferable, and a dicyclopentadiene type active ester compound is even more preferable. As the dicyclopentadiene type active ester compound, an active ester compound containing a dicyclopentadiene type diphenol structure is preferable. The "dicyclopentadiene type diphenol structure" represents a divalent structural unit composed of phenylene-dicyclopentylene-phenylene.

[0074] Examples of commercially available products of the (C) active ester compound include, as the active ester compound containing a dicyclopentadiene type diphenol structure, "EXB9451", "EXB9460", "EXB9460S", "EXB-8000L", "EXB-8000L-65M", "EXB-8000L-65TM", "HPC-8000L-65TM", "HPC-8000", "HPC-8000-65T", "HPC-8000H", "HPC-8000H-65TM" (manufactured by DIC); as the active ester compound containing a naphthalene structure, "EXB-8100L-65T", "EXB-8150-60T", "EXB-8150-62T", "EXB-9416-70BK", "HPC-8150-60T", "HPC-8150-62T" (manufactured by DIC); as the phosphorus-containing active ester compound, "EXB9401" (manufactured by DIC), as the active ester compound which is an acetylated product of phenol novolak, "DC808" (manufactured by Mitsubishi Chemical Corporation), as the active ester compound which is a benzoylated product of phenol novolak, "YLH1026", "YLH1030", "YLH1048" (manufactured by Mitsubishi Chemical Corporation), and as the active ester compound containing a styryl group and a naphthalene structure, "PC1300-02-65MA" (manufactured by Air Water Inc.), etc.

[0075] (C) The active ester group equivalent of the active ester compound is preferably 50 g / eq. to 500 g / eq., more preferably 50 g / eq. to 400 g / eq., still more preferably 100 g / eq. to 300 g / eq. The active ester group equivalent is the mass of the active ester compound per equivalent of the active ester group.

[0076] The content of the (C) active ester compound in the resin composition is not particularly limited. However, when the non-volatile components in the resin composition are taken as 100% by mass, it is preferably 60% by mass or less, more preferably 50% by mass or less, still more preferably 40% by mass or less, even more preferably 30% by mass or less, and particularly preferably 20% by mass or less. The lower limit of the content of the (C) active ester compound in the resin composition is not particularly limited. However, when the non-volatile components in the resin composition are taken as 100% by mass, it is preferably 0.1% by mass or more, more preferably 1% by mass or more, still more preferably 3% by mass or more, even more preferably 5% by mass or more, and particularly preferably 10% by mass or more.

[0077] The mass ratio of the (C) active ester compound to the compound containing the repeating unit represented by the formula (1) ((C) component / (A) component) in the resin composition is not particularly limited, but is preferably 5 or more, more preferably 10 or more, still more preferably 30 or more, and particularly preferably 40 or more. The upper limit of the mass ratio of the (C) active ester compound to the compound containing the repeating unit represented by the formula (1) ((C) component / (A) component) in the resin composition is not particularly limited, but is preferably 500 or less, more preferably 200 or less, still more preferably 100 or less, and particularly preferably 60 or less.

[0078] The mass ratio of the (C) active ester compound to the (B) epoxy resin in the resin composition ((C) component / (B) component) is not particularly limited, but is preferably 0.1 or more, more preferably 0.5 or more, still more preferably 1 or more, and particularly preferably 1.5 or more. The upper limit of the mass ratio of the (C) active ester compound to the (B) epoxy resin in the resin composition ((C) component / (B) component) is not particularly limited, but is preferably 10 or less, more preferably 5 or less, still more preferably 3 or less, and particularly preferably 2 or less.

[0079] <(D) Inorganic filler> The resin composition of the present invention may contain a (D) inorganic filler as an optional component. The (D) inorganic filler is contained in the resin composition in a particulate state.

[0080] As the material of the (D) inorganic filler, an inorganic compound is used. Examples of the material of the (D) inorganic filler 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 zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungsten phosphate. Among these, silica is particularly preferred. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Further, spherical silica is preferred as the silica. The (D) inorganic filler may be used alone or in combination of two or more in any ratio.

[0081] (D) Examples of commercially available inorganic fillers include, for example, "UFP-30" manufactured by Denka Chemical Industry Co., Ltd.; "SP60-05", "SP507-05" manufactured by Nippon Steel & Sumikin Materials Co., Ltd.; "YC100C", "YA050C", "YA050C-MJE", "YA010C" manufactured by Admatechs Co., Ltd.; "UFP-30" manufactured by Denka Co., Ltd.; "Silfill NSS-3N", "Silfill NSS-4N", "Silfill NSS-5N" manufactured by Tokuyama Corporation; "SC2500SQ", "SO-C4", "SO-C2", "SO-C1" manufactured by Admatechs Co., Ltd.; "DAW-03", "FB-105FD" manufactured by Denka Co., Ltd., and the like.

[0082] (D) The average particle size of the inorganic filler is not particularly limited, but is preferably 10 μm or less, more preferably 5 μm or less, still 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 inorganic filler is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, still more preferably 0.1 μm or more, and particularly preferably 0.2 μm or more. The average particle size of the inorganic filler can be measured by the laser diffraction / scattering method based on the Mie scattering theory. Specifically, it can be measured by creating a volume-based particle size distribution of the inorganic filler with a laser diffraction / scattering type particle size distribution measuring device and taking the median diameter thereof as the average particle size. As the measurement sample, 100 mg of the inorganic filler and 10 g of methyl ethyl ketone can be weighed into a vial and dispersed by ultrasonic waves for 10 minutes. The measurement sample can be used to measure the volume-based particle size distribution of the inorganic filler using a laser diffraction type particle size distribution measuring device with the light source wavelengths of blue and red and in a flow cell method, and the average particle size can be calculated as the median diameter from the obtained particle size distribution. Examples of the laser diffraction type particle size distribution measuring device include "LA-960" manufactured by Horiba, Ltd.

[0083] (D) The specific surface area of the inorganic filler is not particularly limited, but is preferably 0.1 m 2 / g or more, more preferably 0.5 m 2 / g or more, still more preferably 1 m 2 / g or more, particularly preferably 3 m 2 / g or more. (D) The upper limit of the specific surface area of the inorganic filler is not particularly limited, but preferably 100 m 2 / g or less, more preferably 70 m 2 / g or less, still more preferably 50 m 2 / g or less, particularly preferably 40 m 2 / g or less. The specific surface area of the inorganic filler can be obtained by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech Co., Ltd.) in accordance with the BET method and calculating the specific surface area using the BET multi-point method.

[0084] (D) The inorganic filler is preferably surface-treated with a suitable surface treatment agent. By being surface-treated, the moisture resistance and dispersibility of the (D) inorganic filler can be enhanced. Examples of the surface treatment agent include vinyl-based silane coupling agents such as vinyltrimethoxysilane and vinyltriethoxysilane; epoxy-based silane coupling agents such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane; styryl-based silane coupling agents such as p-styryltrimethoxysilane; methacryl-based silane coupling agents such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane; acrylic-based silane coupling agents such as 3-acryloxypropyltrimethoxysilane; amino-based silane coupling agents such as N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-8-aminooctyltrimethoxysilane, and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane; isocyanurate-based silane coupling agents such as tris-(trimethoxysilylpropyl)isocyanurate; ureido-based silane coupling agents such as 3-ureidopropyltrialkoxysilane; mercapto-based silane coupling agents such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; isocyanate-based silane coupling agents such as 3-isocyanatopropyltriethoxysilane; acid anhydride-based silane coupling agents such as 3-trimethoxysilylpropylsuccinic anhydride; and other silane coupling agents.Examples of non-silane coupling - alkoxysilane compounds include methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, 1,6-bis(trimethoxysilyl)hexane, trifluoropropyltrimethoxysilane, etc. The surface treatment agent may be used alone or in combination of two or more kinds at any ratio. ;

[0085] Examples of commercially available surface treatment agents include, for example, "KBM-1003", "KBE-1003" (vinyl-based silane coupling agent) manufactured by Shin-Etsu Chemical Co., Ltd.; "KBM-303", "KBM-402", "KBM-403", "KBE-402", "KBE-403" (epoxy-based silane coupling agent); "KBM-1403" (styryl-based silane coupling agent); "KBM-502", "KBM-503", "KBE-502", "KBE-503" (methacrylic-based silane coupling agent); "KBM-5103" (acrylic-based silane coupling agent); "KBM-602", "KBM-603", "KBM-903", "KBE-903", "KBE-9103P", "KBM-573", "KBM-575" (amino-based silane coupling agent); "KBM-9659" (isocyanurate-based silane coupling agent); "KBE-585" (ureido-based silane coupling agent); "KBM-802", "KBM-803" (mercapto-based silane coupling agent); "KBE-9007N" (isocyanate-based silane coupling agent); "X-12-967C" (acid anhydride-based silane coupling agent); "KBM-13", "KBM-22", "KBM-103", "KBE-13", "KBE-22", "KBE-103", "KBM-3033", "KBE-3033", "KBM-3063", "KBE-3063", "KBE-3083", "KBM-3103C", "KBM-3066", "KBM-7103" (non-silane coupling - alkoxysilane compound), etc.

[0086] From the perspective of improving the dispersibility of the inorganic filler, it is preferable that the degree of surface treatment with the surface treatment agent falls within a predetermined range. Specifically, it is preferable that 100% by mass of the inorganic filler is surface-treated with 0.2% to 5% by mass of the surface treatment agent, more preferably surface-treated with 0.2% to 3% by mass, and even more preferably surface-treated with 0.3% to 2% by mass.

[0087] 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 perspective of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg / m 2 or more, more preferably 0.1 mg / m 2 or more, and even more preferably 0.2 mg / m 2 or more. On the other hand, from the perspective of preventing an increase in the melt viscosity of the resin composition and the melt viscosity in the sheet form, it is preferably 1.0 mg / m 2 or less, more preferably 0.8 mg / m 2 or less, and even more preferably 0.5 mg / m 2 or less.

[0088] (D) The amount of carbon per unit surface area of the inorganic filler can be measured after washing the surface-treated inorganic filler with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with the surface treatment agent, and ultrasonic cleaning is performed at 25 °C for 5 minutes. After removing the supernatant and drying the solid content, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by Horiba, Ltd. can be used.

[0089] The content of the (D) inorganic filler in the resin composition is not particularly limited. However, when the non-volatile components in the resin composition are taken as 100% by mass, for example, it can be 98% by mass or less, 95% by mass or less, 90% by mass or less, 85% by mass or less. The lower limit of the content of the (D) inorganic filler in the resin composition is not particularly limited. However, when the non-volatile components in the resin composition are taken as 100% by mass, for example, it can be 0% by mass or more, 1% by mass or more, 5% by mass or more, 10% by mass or more, etc., preferably 20% by mass or more, 30% by mass or more, more preferably 40% by mass or more, 50% by mass or more, still more preferably 55% by mass or more, 60% by mass or more, particularly preferably 65% by mass or more, 70% by mass or more, etc.

[0090] <(E) Radical polymerizable compound> The resin composition of the present invention may further contain an (E) radical polymerizable compound as an optional component. The (E) radical polymerizable compound may be used alone or in any combination of two or more.

[0091] (E) The radical polymerizable compound can be, for example, a compound having a radically polymerizable unsaturated group. The radically polymerizable unsaturated group is not particularly limited as long as it is radically polymerizable, but an ethylenically unsaturated group having a carbon-carbon double bond at the terminal or inside is preferred. Specifically, unsaturated aliphatic groups such as allyl group and 3-cyclohexenyl group; aromatic groups containing unsaturated aliphatic groups such as p-vinylphenyl group, m-vinylphenyl group, and styryl group; α,β-unsaturated carbonyl groups such as acryloyl group, methacryloyl group, maleoyl group, and fumaroyl group, etc. (E) The radical polymerizable compound preferably has one or more radically polymerizable unsaturated groups, and more preferably has two or more.

[0092] (E) As the radical polymerizable compound, known radical polymerizable compounds can be widely used and are not particularly limited. For example, (E-1) maleimide-based radical polymerizable compounds, (E-2) vinylphenyl-based radical polymerizable compounds, (E-3) (meth)acrylic-based radical polymerizable compounds, etc. can be mentioned.

[0093] <(E-1) maleimide-based radical polymerizable compound> (E-1) The maleimide-based radical polymerizable compound is an organic compound containing one or more (preferably two or more) maleimide groups (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl groups) in one molecule. The (E-1) maleimide-based radical polymerizable compound may be used alone or in combination of two or more in any ratio. The (E-1) maleimide-based radical polymerizable compound preferably contains at least one maleimide compound selected from, for example, (E-1-1) maleimide-terminated polyimide compounds, (E-1-2) aromatic maleimide compounds, and (E-1-3) aliphatic maleimide compounds.

[0094] <(E-1-1) maleimide-terminated polyimide compound> (E-1-1) The maleimide-terminated polyimide compound is a chain polyimide (a chain polymer containing two or more imide structures) having maleimide groups at both ends. The (E-1-1) maleimide-terminated polyimide compound can be a component that can be obtained, for example, by subjecting a component containing a diamine compound, maleic anhydride, and a tetracarboxylic dianhydride to an imidization reaction.

[0095] In one embodiment, the (E-1-1) maleimide-terminated polyimide compound is, for example, the following formula (2):

[0096] [Chemical formula]

[0097] [In the formula, A 1 each independently represents a divalent organic group composed of two or more (for example, 2 to 3000, 2 to 1000, 2 to 100, 2 to 50) skeletal atoms selected from a carbon atom, an oxygen atom, a nitrogen atom, and a sulfur atom (preferably a divalent ring (for example, an aromatic ring or a non-aromatic ring) containing organic group); A 2each independently represents a single bond or a divalent organic group composed of one or more (for example, 1 to 3000, 1 to 1000, 1 to 100, 1 to 50) skeletal atoms selected from carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms; R p and R q each independently represents a substituent; n represents an integer of 1 or more (preferably an integer of 1 to 100, more preferably an integer of 1 to 50, particularly preferably an integer of 1 to 20); m each independently represents 0 or 1; p and q each independently represent an integer of 0 to 3 (preferably 0).] It is a maleimide-terminated polyimide compound represented by

[0098] A 1 each independently is preferably represented by the following formula (Y1):

[0099]

Chemical formula

[0100] [In the formula, Y 11 each independently represents a single bond, an alkylene group or an alkenylene group; Y 12 each independently represents a single bond, an alkylene group, an alkenylene group, -O-, -CO-, -S-, -SO-, -SO2-, -CONH-, -NHCO-, -COO-, or -OCO-; ring Z 1 each independently represents an optionally substituted non-aromatic ring or an optionally substituted aromatic ring; y1 represents 0 or an integer of 1 or more (preferably 0 or an integer of 1 to 5); * represents a bonding site.] It is a divalent group represented by

[0101] The alkylene group refers to a linear or branched divalent aliphatic saturated hydrocarbon group. The alkylene group is preferably an alkylene group having 1 to 14 carbon atoms. Examples of the alkylene group include linear alkylene groups such as methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, etc.; ethylidene group (-CH(CH3)-), propylidene group (-CH(CH2CH3)-), isopropylidene group (-C(CH3)2-), ethylmethylmethylene group (-C(CH3)(CH2CH3)-), diethylmethylene group (-C(CH2CH3)2-), 2-methyltetramethylene group, 2,3-dimethyltetramethylene group, 1,3-dimethyltetramethylene group, 2-methylpentamethylene group, 2,2-dimethylpentamethylene group, 2,4-dimethylpentamethylene group, 1,3,5-methylpentamethylene group, 2-methylhexamethylene group, 2,2-dimethylhexamethylene group, 2,4-dimethylhexamethylene group, 1,3,5-trimethylhexamethylene group, 2,2,4-trimethylhexamethylene group, 2,4,4-trimethylhexamethylene group and other branched alkylene groups. The alkenylene group refers to a linear or branched divalent aliphatic unsaturated hydrocarbon group having at least one carbon-carbon double bond. The alkenylene group is preferably an alkenylene group having 2 to 14 carbon atoms. Specific examples of the alkenylene group include groups obtained by replacing any carbon-carbon single bond in those specifically exemplified as the alkylene group with a carbon-carbon double bond.

[0102] Ring Z of formula (Y1) 1 The aromatic ring represented by is the same as the aromatic ring represented by ring B or ring C of formula (1). Ring Z of formula (Y1) 1The non-aromatic ring represented by means a ring other than an aromatic ring, and includes a monocyclic non-aromatic ring and a condensed non-aromatic ring formed by condensation of two or more monocyclic non-aromatic rings. The non-aromatic ring can be a carbocyclic ring or a heterocyclic ring, but in one embodiment, it is preferably a carbocyclic ring. The non-aromatic ring may be a saturated ring or an unsaturated ring, but in one embodiment, it is preferably a saturated ring. Examples of the non-aromatic ring include, for example, cycloalkane rings; cycloalkene rings; monocyclic non-aromatic heterocyclic rings such as pyrrolidine rings, tetrahydrofuran rings, dioxane rings, and tetrahydropyran rings (preferably 3- to 10-membered); bicyclic or higher condensed non-aromatic carbocyclic rings such as norbornane rings, decalin rings, adamantane rings, and tetrahydrodicyclopentadiene rings (preferably 8- to 15-membered), etc.

[0103] Specific examples of the divalent group represented by formula (Y1) are not particularly limited, and examples thereof include divalent organic groups represented by the following:

[0104]

Chemical formula

[0105] [In the formula, * indicates the bonding site.].

[0106] A 2 are each independently, preferably, of formula (Y2):

[0107]

Chemical formula

[0108] [In the formula, Y 2 each independently represents a single bond, an alkylene group, an alkenylene group, -O-, -CO-, -S-, -SO-, -SO2-, -CONH-, -NHCO-, -COO-, or -OCO-; ring Z 2 each independently represents a non-aromatic ring which may have a substituent or an aromatic ring which may have a substituent; y2 represents 0 or an integer of 1 or more (preferably 0 or an integer of 1 to 5); * indicates the bonding site.] is a divalent group (including a single bond) represented by the formula. Ring Z of formula (Y2) 2 The aromatic ring and non-aromatic ring represented by the formula are the aromatic ring represented by ring B or ring C of formula (1) and ring Z of formula (Y1), respectively 1 is the same as the non-aromatic ring represented by the formula.

[0109] Specific examples of the divalent group represented by formula (Y2) are not particularly limited, and in addition to -CH2-, -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH2CH3)2-, -O-, -CO-, -S-, -SO-, and -SO2-, divalent organic groups represented by the following can be mentioned:

[0110]

Chemical formula

[0111] [In the formula, * indicates the bonding site.].

[0112] The weight average molecular weight (Mw) of the (E-1-1) maleimide-terminated polyimide compound is preferably 500 to 50,000, more preferably 1,000 to 20,000. The functional group equivalent of the maleimide group of the (E-1-1) maleimide-terminated polyimide compound is preferably 300 g / eq. to 20,000 g / eq., more preferably 500 g / eq. to 10,000 g / eq.

[0113] Examples of commercially available products of the (E-1-1) maleimide-terminated polyimide compound include "BMI-1500", "BMI-1700", "BMI-3000J", "BMI-6000", "BMI-6100", etc. manufactured by Designer Molecules.

[0114] <(E-1-2) Aromatic maleimide compound> (E-1-2) The aromatic maleimide compound is a maleimide compound that does not correspond to the (E-1-1) component, and means a maleimide compound containing one or more aromatic rings and two or more maleimide groups in one molecule. In one embodiment, the (E-1-2) aromatic maleimide compound can be an addition-polymerizable aromatic maleimide compound. The (E-1-2) aromatic maleimide compound may be a maleimide compound having one aromatic ring such as N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, etc., or a maleimide compound having two or more aromatic rings, but it is preferably a maleimide having two or more aromatic rings.

[0115] In one embodiment, the (E-1-2) aromatic maleimide compound is, for example, of formula (3):

[0116]

Chemical formula

[0117] [In the formula, R u each independently represents a substituent; Y 3 each independently represents a single bond, an alkylene group, an alkenylene group, -O-, -CO-, -S-, -SO-, -SO2-, -CONH-, -NHCO-, -COO-, or -OCO- (preferably a single bond or an alkylene group); ring Z 3 each independently represents an optionally substituted non-aromatic ring or an optionally substituted aromatic ring (preferably an optionally substituted aromatic ring, particularly preferably an optionally substituted benzene ring); s represents an integer of 1 or more (preferably an integer from 1 to 100, more preferably an integer from 1 to 50, still more preferably an integer from 1 to 20); t each independently represents 0 or an integer of 1 or more; u each independently represents an integer from 0 to 2 (preferably 0).] It is a maleimide compound represented by, and particularly preferably, formula (3'):

[0118]

Chemical formula

[0119] [In the formula, s is the same as in formula (3).] It is a maleimide compound represented by Ring Z of formula (3). 3 The aromatic ring and the non-aromatic ring represented by are the aromatic ring represented by Ring B or Ring C of formula (1) and Ring Z of formula (Y1), respectively 1 It is the same as the non-aromatic ring represented by

[0120] In one embodiment, as the (E-1-2) aromatic maleimide compound, a novolak type polymaleimide containing a repeating unit including a combination of an N-phenylmaleimide skeleton and a methylene skeleton is preferable, and an aralkyl novolak type polymaleimide containing a repeating unit including a combination of an N-phenylmaleimide skeleton and a methylene skeleton and a combination of an aromatic carbon ring skeleton and a methylene skeleton alternately is more preferable, and a biphenyl aralkyl novolak type polymaleimide containing a repeating unit including a combination of an N-phenylmaleimide skeleton and a methylene skeleton and a combination of a biphenyl skeleton and a methylene skeleton alternately is more preferable.

[0121] The weight average molecular weight (Mw) of the (E-1-2) aromatic maleimide compound is preferably 150 to 5000, more preferably 300 to 2500. The functional group equivalent of the maleimide group of the (E-1-2) aromatic maleimide compound is preferably 50 g / eq. to 2000 g / eq., more preferably 100 g / eq. to 1000 g / eq., still more preferably 150 g / eq. to 500 g / eq., and particularly preferably 200 g / eq. to 300 g / eq.

[0122] Examples of commercially available products of the (E-1-2) aromatic maleimide compound include "MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd.; "BMI-50P" manufactured by KI Chemical Industry Co., Ltd.; "BMI-1000", "BMI-1000H", "BMI-1100", "BMI-1100H", "BMI-4000", "BMI-5100" manufactured by Daiwa Kasei Kogyo Co., Ltd.; "BMI-4,4'-BPE", "BMI-70" manufactured by KI Chemical Industry Co., Ltd., "BMI-80" manufactured by KI Chemical Industry Co., Ltd., etc.

[0123] <(E-1-3) aliphatic maleimide compound> (E-1-3) aliphatic maleimide compound is a compound having a non-aromatic hydrocarbon (preferably having 2 to 50 carbon atoms) as a basic skeleton and having two or more (preferably two) maleimide groups in one molecule.

[0124] In one embodiment, the (E-1-3) aliphatic maleimide compound is, for example, the following formula (4):

[0125] [Chemical formula]

[0126] [In the formula, Y 4 each independently represents a single bond, an alkylene group or an alkenylene group (preferably an alkylene group or an alkenylene group); ring Z 4 each independently represents a non-aromatic ring (preferably a cycloalkane ring or a cycloalkene ring which may have a group selected from an alkyl group and an alkenyl group) which may have a group selected from an alkyl group and an alkenyl group; y4 represents 0 or an integer of 1 or more (preferably an integer of 1 or more, particularly preferably 1).] It is a maleimide compound represented by. The non-aromatic ring represented by ring Z of formula (4) 4 is the same as the non-aromatic ring represented by ring Z of formula (Y1) 1 represented by.

[0127] (E-1-3) Specific examples of the aliphatic maleimide compound include chain aliphatic bismaleimide compounds such as N,N'-ethylenedimaleimide, N,N'-tetramethylenedimaleimide, and N,N'-hexamethylenedimaleimide; alicyclic bismaleimide compounds such as 1-maleimide-3-maleimidomethyl-3,5,5-trimethylcyclohexane (IPBM), 1,1'-(cyclohexane-1,3-diylbis(methylene))bis(1H-pyrrole-2,5-dione) (CBM), and 1,1'-(4,4'-methylenebis(cyclohexane-4,1-diyl))bis(1H-pyrrole-2,5-dione) (MBCM); and bismaleimide containing a dimer acid skeleton, etc.

[0128] The bismaleimide containing a dimer acid skeleton means a bismaleimide compound in which two terminal carboxy groups (-COOH) of the dimer acid are replaced with a maleimide group or a maleimidomethyl group (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-ylmethyl group). The dimer acid is a known compound obtained by dimerizing an unsaturated fatty acid (preferably having 11 to 22 carbon atoms, particularly preferably having 18 carbon atoms), and its industrial production process is almost standardized in the industry. The dimer acid is mainly composed of a dimer acid having 36 carbon atoms obtained by dimerizing unsaturated fatty acids having 18 carbon atoms such as oleic acid and linoleic acid, which are particularly inexpensive and easily available, and can be easily obtained. In addition, the dimer acid may contain an arbitrary amount of monomer acid, trimer acid, and other polymerized fatty acids depending on the production method, the degree of purification, etc. Further, although double bonds remain after the polymerization reaction of the unsaturated fatty acid, in this specification, a hydrogenated product obtained by further hydrogenation reaction to reduce the degree of unsaturation is also included in the dimer acid.

[0129] (E-1-3) The molecular weight of the aliphatic maleimide compound is preferably 150 to 5000, more preferably 300 to 1000. The functional group equivalent of the maleimide group of the aliphatic maleimide compound is preferably 50 g / eq. to 2000 g / eq., more preferably 100 g / eq. to 1000 g / eq., still more preferably 200 g / eq. to 600 g / eq., and particularly preferably 300 g / eq. to 400 g / eq.

[0130] Examples of commercially available aliphatic maleimide compounds (E-1-3) include "BMI-689" manufactured by Designer Molecules, Inc.

[0131] <(E-2) Vinylphenyl-based radical polymerizable compound> (E-2) The vinylphenyl-based radical polymerizable compound is a radical polymerizable compound having a vinylphenyl group. The vinylphenyl-based radical polymerizable compound preferably has two or more vinylphenyl groups per molecule. (E-2) The vinylphenyl-based radical polymerizable compound is preferably a vinylbenzyl-modified polyphenylene ether having a vinylbenzyl group and a polyphenylene ether skeleton, and formula (5):

[0132]

Chemical formula

[0133] [In the formula, R 11 , R 12 , R 13 and R 14 each independently represent a hydrogen atom or a substituent (preferably a hydrogen atom or an alkyl group, particularly preferably a hydrogen atom or a methyl group).] It is particularly preferable that it is a repeating unit represented by (the number of repeating units is preferably 2 to 300, more preferably 2 to 100) and a vinylbenzyl-modified polyphenylene ether having a vinylbenzyl group (particularly a both-terminal vinylbenzyl-modified polyphenylene ether in which the hydrogen atoms of the hydroxyl groups at both ends of the polyphenylene ether are replaced by vinylbenzyl groups).

[0134] (E-2) The number average molecular weight of the vinylphenyl-based radical polymerizable compound is preferably 500 to 10,000, more preferably 700 to 5,000. The functional group equivalent of the vinyl group of the vinylphenyl-based radical polymerizable compound is preferably 200 g / eq. to 3,000 g / eq., more preferably 300 g / eq. to 2,000 g / eq.

[0135] Examples of commercially available products of the vinylphenyl-based radical polymerizable compound include "OPE-2St 1200" and "OPE-2St 2200" (vinylbenzyl-modified polyphenylene ether) manufactured by Mitsubishi Gas Chemical Company.

[0136] <(E-3) (Meth)acrylic-based radical polymerizable compound> (E-3) The (meth)acrylic-based radical polymerizable compound is a radical polymerizable compound having an acryloyl group and / or a methacryloyl group. The (meth)acrylic-based radical polymerizable compound preferably has two or more acryloyl groups and / or methacryloyl groups per molecule. The (meth)acrylic-based radical polymerizable compound is preferably a (meth)acrylic-modified polyphenylene ether having an acryloyl group and / or a methacryloyl group and a polyphenylene ether skeleton, and formula (6):

[0137] [Chemical formula]

[0138] [In the formula, R 21 , R 22 , R 23 and R 24 each independently represent a hydrogen atom or a substituent (preferably a hydrogen atom or an alkyl group, particularly preferably a hydrogen atom or a methyl group).] A repeating unit represented by (the number of repeating units is preferably 2 to 300, more preferably 2 to 100), and a (meth)acrylic-modified polyphenylene ether having an acryloyl group and / or a methacryloyl group (particularly a both-terminal (meth)acrylic-modified polyphenylene ether in which the hydrogen atoms of the hydroxyl groups at both ends of the polyphenylene ether are replaced by an acryloyl group and / or a methacryloyl group) is particularly preferred.

[0139] (E-3) The number average molecular weight of the (meth)acrylic radical polymerizable compound is preferably 500 to 10,000, more preferably 700 to 5,000. The functional group equivalent of the acryloyl group and methacryloyl group of the (E-3) (meth)acrylic radical polymerizable compound is preferably 200 g / eq. to 3,000 g / eq., more preferably 300 g / eq. to 2,000 g / eq.

[0140] Examples of commercially available products of the (E-3) (meth)acrylic radical polymerizable compound include "SA9000", "SA9000-111" (methacrylic-modified polyphenylene ether) manufactured by SABIC Innovative Plastics.

[0141] The content of the (E) radical polymerizable compound in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 40% by mass or less, more preferably 20% by mass or less, still more preferably 10% by mass or less, even more preferably 5% by mass or less, and particularly preferably 3% by mass or less. The lower limit of the content of the (E) radical polymerizable compound in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it can be, for example, 0% by mass or more, 0.001% by mass or more, etc., preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, and particularly preferably 0.5% by mass or more, etc.

[0142] <(F) curing agent> The resin composition of the present invention may contain a (F) curing agent as an optional component. The (F) curing agent has a function of curing the resin composition (particularly a function of curing by reacting with the (B) epoxy resin and / or the (E) radically polymerizable compound). The (F) curing agent referred to herein is a component that does not correspond to the components (A) to (E).

[0143] The (F) curing agent is not particularly limited. For example, it includes (F-1) carbodiimide-based curing agents, (F-2) phenolic curing agents and naphtholic curing agents, (F-3) acid anhydride-based curing agents, (F-4) amine-based curing agents, (F-5) benzoxazine-based curing agents, (F-6) cyanate ester-based curing agents, and (F-7) thiol-based curing agents. The (F) curing agent may be used alone or in combination of two or more. In one embodiment, the (F) curing agent preferably contains at least one curing agent selected from the group consisting of (F-1) carbodiimide-based curing agents and (F-2) phenolic curing agents and naphtholic curing agents, and particularly preferably contains a (F-1) carbodiimide-based curing agent. In one embodiment, from the viewpoint of particularly significantly obtaining the desired effects of the present invention, the resin composition of the present invention particularly preferably contains a (F-1) carbodiimide-based curing agent.

[0144] (F-1) Examples of the carbodiimide-based curing agent include curing agents having one or more, preferably two or more carbodiimide structures in one molecule. For example, aliphatic biscarbodiimides such as tetramethylene-bis(t-butylcarbodiimide) and cyclohexane bis(methylene-t-butylcarbodiimide); biscarbodiimides such as aromatic biscarbodiimides like phenylene-bis(xylylcarbodiimide); aliphatic polycarbodiimides such as polyhexamethylene carbodiimide, polytrimethylhexamethylene carbodiimide, polycyclohexylene carbodiimide, poly(methylenebiscyclohexylene carbodiimide), and poly(isophorone carbodiimide); aromatic polycarbodiimides such as poly(phenylene carbodiimide), poly(naphthylene carbodiimide), poly(tolylene carbodiimide), poly(methyldiisopropylphenylene carbodiimide), poly(triethylphenylene carbodiimide), poly(diethylphenylene carbodiimide), poly(triisopropylphenylene carbodiimide), poly(diisopropylphenylene carbodiimide), poly(xylylene carbodiimide), poly(tetramethylxylylene carbodiimide), poly(methylenediphenylene carbodiimide), and poly[methylenebis(methylphenylene) carbodiimide] are included.

[0145] (F-1) Examples of commercially available carbodiimide-based curing agents include, for example, "Carbodilite V-02B", "Carbodilite V-03", "Carbodilite V-04K", "Carbodilite V-07", and "Carbodilite V-09" manufactured by Nisshinbo Chemicals; "Stabaxol P", "Stabaxol P400", "Highcadil 510", etc. manufactured by Rhein Chemie.

[0146] (F-2) As phenolic curing agents and naphtholic curing agents, from the viewpoints of heat resistance and water resistance, phenolic curing agents having a novolak structure or naphtholic curing agents having a novolak structure are preferable. Further, from the viewpoint of adhesion to the adherend, nitrogen-containing phenolic curing agents or nitrogen-containing naphtholic curing agents are preferable, and phenolic curing agents containing a triazine skeleton or naphtholic curing agents containing a triazine skeleton are more preferable. Among them, from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion, phenolic novolak resins containing a triazine skeleton are preferable. Specific examples of the (F-2) phenolic curing agents and naphtholic curing agents include, for example, "MEH-7700", "MEH-7810", "MEH-7851" manufactured by Meiwa Kasei Co., Ltd., "NHN", "CBN", "GPH" manufactured by Nippon Kayaku Co., Ltd., "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN-375", "SN-395" manufactured by Nippon Steel Chemical & Material Co., Ltd., "LA-7052", "LA-7054", "LA-3018", "LA-3018-50P", "LA-1356", "TD2090", "TD-2090-60M" manufactured by DIC Corporation, etc.

[0147] (F-3) The acid anhydride-based hardeners include hardeners having one or more acid anhydride groups in one molecule, and hardeners having two or more acid anhydride groups in one molecule are preferred. Specific examples of the (F-3) acid anhydride-based hardeners 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, benzophenone tetracarboxylic dianhydride, 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 polymer-type acid anhydrides such as styrene-maleic acid resin copolymerized from styrene and maleic acid. Commercially available products of the (F-3) acid anhydride-based hardeners include "HNA-100", "MH-700", "MTA-15", "DDSA", "OSA" manufactured by Shin Nippon Rika Co., Ltd., "YH-306", "YH-307" manufactured by Mitsubishi Chemical Corporation, "HN-2200", "HN-5500" manufactured by Hitachi Chemical Co., Ltd., etc.

[0148] The amine-based curing agent (F-4) may be a curing agent having one or more, preferably two or more, amino groups in one molecule, such as aliphatic amines, polyether amines, alicyclic amines, aromatic amines, etc., and among these, aromatic amines are preferred from the viewpoint of achieving the desired effects of the present invention. The amine-based curing agent (F-4) is preferably a primary amine or secondary amine, more preferably a primary amine. Specific examples of the amine-based curing agent (F-4) 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, 2,2-bis(3-amino-4-hydroxyphenyl) )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. As the amine-based curing agent (F-4), commercially available products may be used. Examples of such curing agents 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.

[0149] Specific examples of the (F-5) benzoxazine-based curing agent 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 Chemical Industry Co., Ltd.

[0150] (F-6) Examples of cyanate ester-based 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'-ethylidenediphenyl 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; polyfunctional cyanate resins derived from phenol novolac and cresol novolac; prepolymers in which part of these cyanate resins is triazine-formed; and the like. Specific examples of (F-6) cyanate ester-based curing agents include "PT30" and "PT60" (both phenol novolac type polyfunctional cyanate ester resins), "BA230", and "BA230S75" (prepolymers in which part or all of bisphenol A dicyanate is triazine-formed and becomes a trimer), manufactured by Lonza Japan Co., Ltd.

[0151] (F-7) Examples of thiol-based curing agents include trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), tris(3-mercaptopropyl) isocyanurate, and the like.

[0152] (F) The reaction group equivalent of the curing agent is preferably 50 g / eq. to 3000 g / eq., more preferably 100 g / eq. to 1000 g / eq., still more preferably 100 g / eq. to 500 g / eq., and particularly preferably 100 g / eq. to 300 g / eq. The reaction group equivalent is the mass of the curing agent per 1 equivalent of the reaction group.

[0153] The content of the (F) curing agent in the resin composition is not particularly limited. However, when the non-volatile components in the resin composition are taken as 100% by mass, it is preferably 15% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less, and particularly preferably 3% by mass or less. The lower limit of the content of the (F) curing agent in the resin composition is not particularly limited. However, when the non-volatile components in the resin composition are taken as 100% by mass, for example, it can be 0% by mass or more, 0.01% by mass or more, 0.1% by mass or more, 1% by mass or more, 2% by mass or more, etc.

[0154] <(G) Curing accelerator> The resin composition of the present invention may contain a (G) curing accelerator as an optional component.

[0155] Examples of the curing accelerator include, for example, (G-1) imidazole-based curing accelerators, (G-2) phosphorus-based curing accelerators, (G-3) urea-based curing accelerators, (G-4) guanidine-based curing accelerators, (G-5) metal-based curing accelerators, (G-6) amine-based curing accelerators, etc. In one embodiment, the (G) curing accelerator preferably contains a (G-1) imidazole-based curing accelerator. The (G) curing accelerator may be used alone or in combination of two or more.

[0156] (G-1) Examples of imidazole-based curing accelerators include imidazole compounds such as 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-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 adducts of imidazole compounds and epoxy resins.

[0157] (G-1) As the imidazole-based curing accelerator, commercially available products may be used. Examples include "1B2PZ", "2MZA-PW", "2PHZ-PW" manufactured by Shikoku Kasei Kogyo Co., Ltd., and "P200-H50" manufactured by Mitsubishi Chemical Corporation.

[0158] (G-2) Examples of phosphorus-based hardening accelerators include aliphatic phosphonium salts such as tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium) pyromellitate, tetrabutylphosphonium hydrogen hexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate, di-tert-butylmethylphosphonium tetraphenylborate; aromatic phosphonium salts such as methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra-p-tolylborate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, triphenylethylphosphonium tetraphenylborate, tris(3-methylphenyl)ethylphosphonium tetraphenylborate, tris(2-methoxyphenyl)ethylphosphonium tetraphenylborate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate; aromatic phosphine-borane complexes such as triphenylphosphine·triphenylborane; aromatic phosphine-quinone addition reactants such as triphenylphosphine·p-benzoquinone addition reactant; aliphatic phosphines such as tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butyl(2-butenyl)phosphine, di-tert-butyl(3-methyl-2-butenyl)phosphine, tricyclohexylphosphine;Aromatic phosphines such as 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, 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, 2,2'-bis(diphenylphosphino)diphenylether, etc. are mentioned.;

[0159] (G-3) Examples of urea-based curing accelerators include aliphatic dimethylureas such as 1,1-dimethylurea; 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, 3-cyclooctyl-1,1-dimethylurea; and aromatic dimethylureas such as 3-phenyl-1,1-dimethylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, 3-(3,4-dimethylphenyl)-1,1-dimethylurea, 3-(4-isopropylphenyl)-1,1-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), N,N-(4-methyl-1,3-phenylene)bis(N’,N’-dimethylurea) [toluene bisdimethylurea], etc.

[0160] (G-4) Examples of guanidine-based 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, 1-(o-tolyl)biguanide, etc.

[0161] (G-5) Examples of the metal-based hardening accelerator include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organometallic complexes include organocobalt complexes such as cobalt(II) acetylacetonate and cobalt(III) acetylacetonate, organocopper complexes such as copper(II) acetylacetonate, organozinc complexes such as zinc(II) acetylacetonate, organoiron complexes such as iron(III) acetylacetonate, organonickel complexes such as nickel(II) acetylacetonate, and organomanganese complexes such as manganese(II) acetylacetonate. Examples of the organometallic salts include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

[0162] (G-6) Examples of the amine-based hardening accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene, and the like.

[0163] (G-6) Commercially available products may be used as the amine-based hardening accelerator. For example, "MY-25" manufactured by Ajinomoto Fine-Techno Co., Inc. and the like can be mentioned.

[0164] The content of the (G) hardening accelerator in the resin composition is not particularly limited. However, when the non-volatile components in the resin composition are 100% by mass, it is preferably 15% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less, even more preferably 3% by mass or less, and particularly preferably 1% by mass or less. The lower limit of the content of the (G) hardening accelerator in the resin composition is not particularly limited. However, when the non-volatile components in the resin composition are 100% by mass, it can be, for example, 0% by mass or more, 0.001% by mass or more, 0.01% by mass or more, 0.05% by mass or more, and the like.

[0165] <(H) Other Additives> The resin composition of the present invention may further contain an optional additive as a non-volatile component. Examples of such additives include radical polymerization initiators such as peroxide-based radical polymerization initiators and azo-based radical polymerization initiators; thermoplastic resins such as phenoxy resins, polyvinyl acetal resins, polyolefin resins, polysulfone resins, polyether sulfone resins, polycarbonate resins, polyether ether ketone resins, and polyester resins; organic fillers such as rubber particles; organometallic compounds such as organic copper compounds, organic zinc compounds, and organic cobalt 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 benton and montmorillonite; antifoaming agents such as silicone-based antifoaming agents, acrylic-based antifoaming agents, fluorine-based antifoaming agents, and vinyl resin-based antifoaming agents; ultraviolet absorbers such as benzotriazole-based ultraviolet absorbers; adhesion improvers such as urea silane; adhesion imparting agents such as triazole-based adhesion imparting agents, tetrazole-based adhesion imparting agents, and triazine-based adhesion imparting agents; antioxidants such as hindered phenol-based antioxidants and hindered amine-based antioxidants; fluorescent brighteners such as stilbene derivatives; surfactants such as fluorine-based surfactants and silicone-based surfactants; flame retardants such as phosphorus-based flame retardants (e.g., phosphate ester compounds, phosphazene compounds, phosphinic acid compounds, red phosphorus), nitrogen-based flame retardants (e.g., melamine sulfate), halogen-based flame retardants, and inorganic-based 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; 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, etc. (H) Other additives may be used alone or in combination of two or more in any ratio. (H) The content of other additives can be appropriately set by those skilled in the art.

[0166] <(I) Organic solvent> In addition to the above-mentioned non-volatile components, the resin composition of the present invention may further contain an arbitrary organic solvent as a volatile component. (I) As the organic solvent, known ones can be appropriately used, and the type thereof is not particularly limited. (I) Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, and γ-butyrolactone; ether solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, and diphenyl ether; alcohol solvents such as methanol, ethanol, propanol, butanol, and ethylene glycol; ether ester solvents such as 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl diglycol acetate, γ-butyrolactone, and methyl methoxypropionate; 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; aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene, etc. (I) The organic solvent may be used alone or in combination of two or more in any ratio.

[0167] In one embodiment, the content of the organic solvent is not particularly limited, but when the total components in the resin composition are 100% by mass, for example, it can be 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.

[0168] <Method for producing resin composition> The resin composition of the present invention can be produced, for example, by adding (A) a compound containing a repeating unit represented by formula (1), (B) an epoxy resin, (C) an active ester compound, (D) an inorganic filler as required, (E) a radically polymerizable compound as required, (F) a curing agent as required, (G) a curing accelerator as required, (H) other additives as required, and (I) an organic solvent as required, in any order and / or partially or entirely simultaneously, to an arbitrary preparation container and mixing them. Further, in the process of adding and mixing each component, the temperature can be appropriately set, and heating and / or cooling can be performed temporarily or throughout. Further, in the process of adding and mixing or thereafter, the resin composition may be stirred or shaken using a stirring device or a shaking device such as a mixer to be uniformly dispersed. Further, defoaming may be performed under low-pressure conditions such as under vacuum simultaneously with stirring or shaking.

[0169] <Properties of resin composition> The resin composition of the present invention contains (A) a compound containing a repeating unit represented by formula (1), (B) an epoxy resin, and (C) an active ester compound. By using such a resin composition, a cured product with suppressed unevenness after lamination can be obtained. The unevenness after lamination refers to the unevenness that can appear in the resin composition layer when a sheet-like laminated material such as a resin sheet and an interior substrate are laminated to form a resin composition layer on the inner layer substrate. This unevenness usually appears in the portion where the thickness of the resin composition layer becomes uneven. This unevenness often appeared near the edge of the resin composition layer, but the present inventor surprisingly found that this unevenness can be suppressed by using the resin composition of the present invention. Further, in a specific embodiment, a cured product with a low dielectric tangent (Df) can be obtained. Further, in a specific embodiment, a cured product with good plating adhesion can be obtained.

[0170] In one embodiment, the cured product of the resin composition of the present invention may have the characteristic of a low dielectric tangent (Df). Therefore, in one embodiment, the dielectric tangent (Df) of the cured product of the resin composition when measured at 5.8 GHz and 23 °C as in Test Example 1 below is preferably 0.02 or less, 0.01 or less, more preferably 0.005 or less, 0.004 or less, still more preferably 0.003 or less, 0.0028 or less, particularly preferably 0.0027 or less, 0.0026 or less.

[0171] In one embodiment, the cured product of the resin composition of the present invention may exhibit good plating adhesion. Therefore, in one embodiment, the peel strength of the plated conductor layer of the resin composition after curing measured as in Test Example 4 below is preferably 0.1 kgf / cm or more, more preferably 0.2 kgf / cm or more, still more preferably 0.3 kgf / cm or more. The upper limit can be 10 kgf / cm or less, etc.

[0172] In one embodiment, the cured product of the resin composition of the present invention may have the characteristic that the arithmetic mean roughness (Ra) is low. Therefore, in one embodiment, the arithmetic mean roughness (Ra) of the surface of the insulating layer after roughening treatment measured as in Test Example 3 below is preferably 200 nm or less, more preferably 100 nm or less, still more preferably 50 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) of the surface of the insulating layer can be measured using a non-contact surface roughness meter.

[0173] Also, in one embodiment, the relative dielectric constant (Dk) of the cured product of the resin composition of the present invention, when measured at 5.8 GHz and 23 °C as in Test Example 1 below, can be preferably 5.0 or less, more preferably 4.5 or less, still more preferably 4.0 or less, and particularly preferably 3.5 or less.

[0174] <Uses of the 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 the insulating layer for forming a conductor layer (including a rewiring layer) formed on the insulating layer (resin composition for forming an insulating layer for forming a conductor layer). Also, in a printed wiring board described later, it can be suitably used as a resin composition for forming an insulating layer of the printed wiring board (resin composition for forming an insulating layer of the printed wiring board). The resin composition of the present invention can also be widely used in applications where a resin composition is required, such as sheet-like laminated materials such as resin sheets and prepregs, solder resists, underfill materials, die bonding materials, semiconductor encapsulants, hole filling resins, component embedding resins, etc.

[0175] Also, for example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition of the present invention can also be preferably used as a resin composition for a rewiring formation layer as an insulating layer for forming a rewiring layer (a resin composition for forming a rewiring formation layer) and a resin composition for encapsulating a semiconductor chip (a resin composition for encapsulating a semiconductor chip). When manufacturing a semiconductor chip package, a rewiring layer may be further formed on the encapsulation layer. (1) A step of laminating a temporary fixing film on a substrate; (2) A step of temporarily fixing a semiconductor chip on the temporary fixing film; (3) A step of forming an encapsulation layer on the semiconductor chip; (4) A step of peeling the substrate and the temporary fixing film from the semiconductor chip; (5) A step of forming a rewiring formation layer as an insulating layer on the surface of the semiconductor chip from which the substrate and the temporary fixing film have been peeled, and (6) A step of forming a rewiring layer as a conductor layer on the rewiring formation layer

[0176] In addition, since the resin composition of the present invention provides an insulating layer with good component embedding properties, it can also be preferably used when the printed wiring board is a component-built-in circuit board.

[0177] <Sheet-like laminated material> The resin composition of the present invention can be used by coating it in a varnish state, but industrially, it is generally preferable to use it in the form of a sheet-like laminated material containing the resin composition.

[0178] As the sheet-like laminated material, the resin sheets and prepregs shown below are preferable.

[0179] 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.

[0180] From the viewpoints of thinning the printed wiring board and providing a cured product with excellent insulation even if the cured product of the resin composition is a thin film, the thickness of the resin composition layer is preferably 50 μm or less, more preferably 40 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, but it can usually be 5 μm or more, 10 μm or more, etc.

[0181] Examples of the support include a film made of a plastic material, a metal foil, and a release paper, and a film made of a plastic material and a metal foil are preferred.

[0182] When using a film made of a plastic material 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), polyethersulfide (PES), polyether ketone, polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

[0183] When using a metal foil as the support, examples of the metal foil include a copper foil and an aluminum foil, and a copper foil is preferred. As the copper foil, a foil made of single metal copper may be used, or a foil made of an alloy of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used.

[0184] The support may be subjected to a mat treatment, a corona treatment, or an antistatic treatment on the surface that joins the resin composition layer.

[0185] Further, as the support, a support with a release layer having a release layer on the surface that bonds to the resin composition layer may be used. Examples of the release agent used for 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. As the support with a release layer, a commercially available product may be used. For example, "SK-1", "AL-5", "AL-7" manufactured by Lintec Corporation, which are PET films having a release layer mainly composed of an alkyd resin-based release agent, "Lumirror T60" manufactured by Toray Industries, Inc., "Purex" manufactured by Teijin Limited, "Unipile" manufactured by Unitika Ltd., etc. may be mentioned.

[0186] The thickness of the support is not particularly limited, but a range of 5 μm to 75 μm is preferable, and a range of 10 μm to 60 μm is more preferable. When using a support with a release layer, it is preferable that the total thickness of the support with a release layer is within the above range.

[0187] In one embodiment, the resin sheet may further include an optional layer as needed. Examples of such an optional layer include a protective film similar to the support provided on the surface of the resin composition layer that is not bonded to the support (i.e., the surface opposite to the support). The thickness of the protective film is not particularly limited, but for example, it is 1 μm to 40 μm. By laminating the protective film, it is possible to suppress the adhesion of dust and scratches to the surface of the resin composition layer.

[0188] The resin sheet can be produced, for example, by directly using the liquid resin composition or preparing a resin varnish by dissolving the resin composition in an organic solvent, applying this onto the support using a die coater or the like, and further drying to form a resin composition layer.

[0189] Examples of the organic solvent include the same ones as those described as components of the resin composition. The organic solvent may be used alone or in combination of two or more.

[0190] Drying may be carried out by known methods such as heating and hot air blowing. The drying conditions are not particularly limited, but the drying is carried out so that the content of the organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. Although it varies depending on the boiling point of the organic solvent in the resin composition or resin varnish, for example, when using a resin composition or resin varnish containing 30% by mass to 60% by mass of the organic solvent, the resin composition layer can be formed by drying at 50°C to 150°C for 3 minutes to 10 minutes.

[0191] The resin sheet can be wound up and stored in a roll shape. When the resin sheet has a protective film, it can be used by peeling off the protective film.

[0192] In one embodiment, the prepreg is formed by impregnating a sheet-shaped fiber base material with the resin composition of the present invention.

[0193] The sheet-shaped fiber base material used for the prepreg is not particularly limited, and those commonly used as prepreg base materials such as glass cloth, aramid nonwoven fabric, and liquid crystal polymer nonwoven fabric can be used. From the viewpoint of thinning the printed wiring board, the thickness of the sheet-shaped fiber base material is preferably 50 μm or less, more preferably 40 μm or less, still more preferably 30 μm or less, and particularly preferably 20 μm or less. The lower limit of the thickness of the sheet-shaped fiber base material is not particularly limited. Usually, it is 10 μm or more.

[0194] The prepreg can be manufactured by known methods such as the hot melt method and the solvent method.

[0195] The thickness of the prepreg can be in the same range as the resin composition layer in the above-mentioned resin sheet.

[0196] The sheet-shaped laminated material of the present invention can be suitably used for forming the insulating layer of a printed wiring board (for the insulating layer of a printed wiring board), and can be more suitably used for forming the interlayer insulating layer of a printed wiring board (for the interlayer insulating layer of a printed wiring board).

[0197] <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.

[0198] The printed wiring board can be manufactured, for example, by a method including the following steps (I) and (II) using the above resin sheet. (I) A step of laminating a resin sheet on an inner layer substrate so that the resin composition layer of the resin sheet is joined to the inner layer substrate (II) A step of curing (for example, thermosetting) the resin composition layer to form an insulating layer

[0199] The "inner layer substrate" used in step (I) is a member that serves as a substrate for the printed wiring board. Examples include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, thermosetting polyphenylene ether substrates, and the like. Further, the substrate may have a conductor layer on one or both sides thereof, and this conductor layer may be pattern-processed. An inner layer substrate having a conductor layer (circuit) formed on one or both sides of the substrate is sometimes referred to as an "inner layer circuit board". Also, in the production of a printed wiring board, an intermediate product on which an insulating layer and / or a conductor layer is to be further formed is also included in the "inner layer substrate" referred to in the present invention. When the printed wiring board is a component-embedded circuit board, an inner layer substrate incorporating components may be used.

[0200] The lamination of the inner layer substrate and the resin sheet can be performed, for example, by thermocompression bonding the resin sheet to the inner layer substrate from the support side. Examples of the member for thermocompression bonding the resin sheet to the inner layer substrate (hereinafter also referred to as the "thermocompression bonding member") include a heated metal plate (such as a SUS mirror plate) or a metal roll (such as a SUS roll). Note that it is preferable to press through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface unevenness of the inner layer substrate, rather than pressing the thermocompression bonding member directly against the resin sheet.

[0201] 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 heat-pressing temperature is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C, the heat-pressing pressure is preferably in the range of 0.098 MPa to 1.77 MPa, more preferably in the range of 0.29 MPa to 1.47 MPa, and the heat-pressing time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. The lamination can preferably be carried out under reduced pressure conditions of a pressure of 26.7 hPa or less.

[0202] The lamination can be carried out by a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum pressure type laminator manufactured by Meiki Seisakusho Co., Ltd., a vacuum applicator manufactured by Nichco Materials Co., Ltd., a batch type vacuum pressure laminator, and the like.

[0203] After the lamination, under normal pressure (atmospheric pressure), for example, by pressing the heat-pressing member from the support side, a smoothing treatment of the laminated resin sheet may be performed. The pressing conditions for the smoothing treatment can be the same as the heat-pressing conditions for the above lamination. The smoothing treatment can be carried out by a commercially available laminator. Note that the lamination and the smoothing treatment may be continuously carried out using the above commercially available vacuum laminator.

[0204] The support may be removed between step (I) and step (II), or may be removed after step (II).

[0205] In step (II), the resin composition layer is cured (for example, thermally cured) to form an insulating layer made of a cured product of the resin composition. The curing conditions of the resin composition layer are not particularly limited, and conditions usually employed when forming an insulating layer of a printed wiring board may be used.

[0206] For example, the thermosetting conditions of the resin composition layer vary depending on the type of the resin composition and the like. 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 can be preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and even more preferably 15 minutes to 100 minutes.

[0207] Before thermosetting the resin composition layer, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermosetting 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.

[0208] When manufacturing a printed wiring board, the steps of (III) drilling holes in the insulating layer, (IV) roughening the insulating layer, and (V) forming the conductor layer may be further carried out. These steps (III) to (V) may be carried out according to various methods known to those skilled in the art used for manufacturing printed wiring boards. When removing the support after step (II), the removal of the support may be carried out between step (II) and step (III), between step (III) and step (IV), or between step (IV) and step (V). Further, if necessary, the formation of the insulating layer and the conductor layer in steps (I) to (V) may be repeated to form a multilayer wiring board.

[0209] In other embodiments, the printed wiring board of the present invention can be manufactured using the above-described prepreg. The manufacturing method is basically the same as the case of using a resin sheet.

[0210] Step (III) is a step of drilling holes in the insulating layer, whereby holes such as via holes and through holes can be formed in the insulating layer. Step (III) may be carried out using, for example, a drill, a laser, a plasma, etc., depending on the composition of the resin composition used for forming the insulating layer. The dimensions and shapes of the holes may be appropriately determined according to the design of the printed wiring board.

[0211] Step (IV) is a step of roughening the insulating layer. Usually, smear removal is also carried out in this step (IV). The procedures and conditions for the roughening treatment are not particularly limited, and known procedures and conditions commonly used when forming the insulating layer of a printed wiring board 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.

[0212] The swelling liquid used for the roughening treatment is not particularly limited, and examples thereof include an alkaline solution and a surfactant solution, preferably an alkaline solution, and more preferably a sodium hydroxide solution or a potassium hydroxide solution as the alkaline solution. Commercially available swelling liquids include, for example, "Swelling Dip Security Gun P" and "Swelling Dip Security Gun SBU" manufactured by Atotech Japan Co., Ltd. The swelling treatment with the swelling liquid is not particularly limited, but can be carried out, for example, by immersing the insulating layer in a swelling liquid at 30°C to 90°C for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling liquid at 40°C to 80°C for 5 minutes to 15 minutes.

[0213] The oxidizing agent used for the roughening treatment is not particularly limited. For example, an alkaline permanganate solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide can be mentioned. The roughening treatment with an oxidizing agent such as an alkaline permanganate solution is preferably carried out by immersing the insulating layer in the oxidizing agent solution heated to 60°C to 100°C for 10 minutes to 30 minutes. Further, the concentration of the permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Security Guard P" manufactured by Atotech Japan Co., Ltd.

[0214] In addition, as the neutralizing solution used for the roughening treatment, an acidic aqueous solution is preferable. Examples of commercially available products include "Reduction Solution Security Guard P" manufactured by Atotech Japan Co., Ltd.

[0215] The treatment with the neutralizing solution can be carried out by immersing the treated surface that has been roughened with the oxidizing agent in the neutralizing solution at 30°C to 80°C for 5 minutes to 30 minutes. From the viewpoint of workability and the like, a method of immersing the object that has been roughened with the oxidizing agent in the neutralizing solution at 40°C to 70°C for 5 minutes to 20 minutes is preferable.

[0216] 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 the alloy layer include layers formed from alloys of two or more metals selected from the above group (for example, nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy). Among them, from the viewpoints of versatility, cost, ease of patterning, etc. of forming the conductor layer, a single-metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of nickel-chromium alloy, copper-nickel alloy, or 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 nickel-chromium alloy is more preferred, and a single-metal layer of copper is even more preferred.

[0217] The conductor layer may have a single-layer structure or a multilayer 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 multilayer 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 nickel-chromium alloy.

[0218] The thickness of the conductor layer depends on the design of the desired printed wiring board, but is generally 3 μm to 35 μm, preferably 5 μm to 30 μm.

[0219] In one embodiment, the conductor layer may be formed by plating. For example, by plating on the surface of the insulating layer by a conventionally known technique such as the semi-additive method or the full-additive method, a conductor layer having a desired wiring pattern can be formed. From the viewpoint of manufacturing simplicity, it is preferably formed by the semi-additive method. Hereinafter, an example of forming the conductor layer by the semi-additive method is shown.

[0220] First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern is formed on the formed plating seed layer to expose a part of the plating seed layer corresponding to a desired wiring pattern. After forming a metal layer by electroplating on the exposed plating seed layer, the mask pattern is removed. Then, an unnecessary plating seed layer can be removed by etching or the like to form a conductor layer having a desired wiring pattern.

[0221] In another embodiment, the conductor layer may be formed using a metal foil. When forming the conductor layer using a metal foil, step (V) is preferably carried out between step (I) and step (II). For example, after step (I), the support is removed, and a metal foil is laminated on the surface of the exposed resin composition layer. The lamination of the resin composition layer and the metal foil may be carried out by a vacuum lamination method. The lamination conditions may be the same as those described for step (I). Next, step (II) is carried out to form an insulating layer. Then, using the metal foil on the insulating layer, a conductor layer having a desired wiring pattern can be formed by a conventional known technique such as a subtractive method or a modified semi-additive method.

[0222] The metal foil can be manufactured by known methods such as an electrolytic method or a rolling method. Examples of commercially available metal foils include HLP foil, JXUT-III foil manufactured by JX Nippon Mining & Metals Corporation, 3EC-III foil, TP-III foil manufactured by Mitsui Mining & Smelting Co., Ltd., and the like.

[0223] <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.

[0224] Examples of semiconductor devices include various semiconductor devices used in electrical products (such as computers, mobile phones, digital cameras, and televisions) and vehicles (such as motorcycles, automobiles, trains, ships, and airplanes).

Examples

[0225] Hereinafter, the present invention will be specifically described 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 "mass %", respectively, unless otherwise specified. The temperature conditions and pressure conditions in the absence of a specific temperature designation are room temperature (25°C) and atmospheric pressure (1 atm).

[0226] <Synthesis Example 1> Into a four-necked flask, 894.96 mmol of dichloropyrimidine, 900.00 mmol of 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1.2 mol of potassium carbonate, and N-methyl-2-pyrrolidone (450 g) were added. After purging the inside of the flask with nitrogen, the contents of the flask were heated at 130°C for 6 hours, and the water generated during heating was removed from the Dean-Stark tube as needed. After cooling the contents of the flask to room temperature, the precipitated solid was filtered off, methanol was added to the filtrate, the precipitated solid was washed with methanol, and these solids were dried to obtain a polymer compound represented by the following formula (1') (weight average molecular weight (Mw); 87000 (polystyrene conversion value)). The obtained compound was 13 measured by C-NMR to confirm the product.

[0227]

Chemical formula

[0228] <Example 1> 2 parts of the polymer compound obtained in Synthesis Example 1 (cyclohexanone solution with a non-volatile component ratio of 20%), 10 parts of a naphthalene-type epoxy resin ("HP-4032-SS" manufactured by DIC, 1,6-bis(glycidyloxy)naphthalene, epoxy equivalent about 145 g / eq.), 30 parts of an active ester compound ("HPC-8000-65T" manufactured by DIC, active ester group equivalent about 223 g / eq., toluene solution with a non-volatile component ratio of 65%), spherical silica surface-treated with a silane coupling agent ("KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd.) ("SO-C2" manufactured by Admatechs Co., Ltd., average particle size 0.5 μm, specific surface area 5.8 m2 2 parts of a triazine skeleton-containing phenolic curing agent (DIC's "LA-3018-50P", a 2-methoxypropanol solution with an active group equivalent of approximately 151 g / eq. and a non-volatile component ratio of 50%), 5 parts of a carbodiimide curing agent (Nisshinbo Chemical's "V-03", a toluene solution with an active group equivalent of approximately 216 g / eq. and a non-volatile component ratio of 50%), and 0.1 part of an imidazole-based curing accelerator (Shikoku Chemical's "1B2PZ", 1-benzyl-2-phenylimidazole) were mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin composition.

[0229] <Example 2> A resin composition was prepared in the same manner as in Example 1, except that 30 parts of an active ester compound (DIC's "HPC-8150-62T", a toluene solution with an active ester group equivalent of approximately 220 g / eq. and a non-volatile component ratio of 62 mass%) was used instead of 30 parts of the active ester compound (DIC's "HPC-8000-65T").

[0230] <Example 3> A resin composition was prepared in the same manner as in Example 2, except that the amount of spherical silica (Admatechs' "SO-C2") surface-treated with a silane coupling agent (Shin-Etsu Chemical's "KBM-573") was changed from 90 parts to 92 parts, and 2 parts of a biphenyl aralkyl novolak-type maleimide (Nippon Kayaku's "MIR-3000-70MT", a MEK / toluene mixed solution with a non-volatile component ratio of 70%) was used.

[0231] <Example 4> A resin composition was prepared in the same manner as in Example 2, except that the amount of spherical silica (Admatechs' "SO-C2") surface-treated with a silane coupling agent (Shin-Etsu Chemical's "KBM-573") was changed from 90 parts to 93 parts, the amount of the imidazole-based curing accelerator (Shikoku Chemical's "1B2PZ") was changed from 0.1 part to 0.5 part, and 1 part of a maleimide-terminated polyimide compound (DMI's "BMI-1500") was used.

[0232] <Example 5> The amount of spherical silica (manufactured by Admatechs Co., Ltd., "SO-C2") surface-treated with a silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-573") was changed from 90 parts to 93 parts, and a resin composition was prepared in the same manner as in Example 2, except that 2 parts of a methacryl-modified polyphenylene ether (manufactured by SABIC Innovative Plastics, "SA9000-111") was used.

[0233] <Example 6> The amount of spherical silica (manufactured by Admatechs Co., Ltd., "SO-C2") surface-treated with a silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-573") was changed from 90 parts to 93 parts, the amount of an imidazole-based curing accelerator (manufactured by Shikoku Kasei Kogyo Co., Ltd., "1B2PZ") was changed from 0.1 part to 0.5 part, and a resin composition was prepared in the same manner as in Example 2, except that 2 parts of a vinylbenzyl-modified polyphenylene ether (manufactured by Mitsubishi Gas Chemical Co., Inc., "OPE-2St 2200", a toluene solution with a non-volatile component ratio of 65%) was used.

[0234] <Comparative Example 1> Instead of 2 parts of the polymer compound obtained in Synthesis Example 1 (a cyclohexanone solution with a non-volatile component ratio of 20%), 1.5 parts of a phenoxy resin (manufactured by Mitsubishi Chemical Corporation, "YX7553BH30", a 1:1 solution of MEK and cyclohexanone with a non-volatile component ratio of 30%) was used, and a resin composition was prepared in the same manner as in Example 1, except that the amount of an imidazole-based curing accelerator (manufactured by Shikoku Kasei Kogyo Co., Ltd., "1B2PZ") was changed from 0.1 part to 0.5 part.

[0235] <Comparative Example 2> Instead of 2 parts of the polymer compound obtained in Synthesis Example 1 (a cyclohexanone solution with a non-volatile component ratio of 20%), 1.5 parts of a phenoxy resin (manufactured by Mitsubishi Chemical Corporation, "YX7553BH30", a 1:1 solution of MEK and cyclohexanone with a non-volatile component ratio of 30%) was used, and a resin composition was prepared in the same manner as in Example 2, except that the amount of an imidazole-based curing accelerator (manufactured by Shikoku Kasei Kogyo Co., Ltd., "1B2PZ") was changed from 0.1 part to 0.5 part.

[0236] <Test Example 1: Measurement of Relative Permittivity and Dielectric Loss Tangent> (1) Preparation of Resin Sheet A with a Resin Composition Layer Thickness of 40 μm As a support, a polyethylene terephthalate film (「AL5」manufactured by Lintec Corporation, thickness 38 μm) provided with a release layer was prepared. On the release layer of this support, the resin compositions obtained in the examples and comparative examples were uniformly coated 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 A including the support and the resin composition layer.

[0237] (2) Preparation of Cured Product B for Evaluation The resin sheet A was cured in an oven at 190°C for 90 minutes. By peeling off the support from the resin sheet A taken out of the oven, a cured product of the resin composition layer was obtained. The cured product was cut into pieces with a length of 80 mm and a width of 2 mm to obtain a cured product B for evaluation.

[0238] (3) Measurement of Relative Permittivity and Dissipation Factor Regarding the cured product B for evaluation, using 「HP8362B」manufactured by Agilent Technologies, the value of relative permittivity (Dk value) and the value of dissipation factor (Df value) were measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23°C by the cavity resonance perturbation method. The measurement was carried out with two test pieces, and the average was calculated.

[0239] <Test Example 2: Evaluation of Mura after Lamination> (1) Preparation of Inner Layer Substrate Both sides of a glass cloth base epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.4 mm, 「R1515A」manufactured by Panasonic Corporation) on which an inner layer circuit was formed were etched with a micro-etching agent (「CZ8101」manufactured by Meck Corporation) by 1 μm to perform roughening treatment of the copper surface.

[0240] (2) Lamination of Resin Sheet A Using a batch-type vacuum pressure laminator (manufactured by Nikkō Materials Co., Ltd., two-stage build-up laminator "CVP700"), the resin sheet A obtained in Test Example 1(1) was laminated on both sides of the inner layer substrate such that the resin composition layer was in contact with the inner layer substrate. The lamination was carried out by reducing the pressure for 30 seconds to adjust the atmospheric pressure to 13 hPa or less, and then crimping at 120°C and a pressure of 0.74 MPa for 30 seconds. Subsequently, a hot press was performed at 100°C and a pressure of 0.5 MPa for 60 seconds.

[0241] (3) Evaluation of unevenness after lamination After lamination, those in which a depression of the resin was observed along the periphery of the inner layer substrate were evaluated as "present", and those in which no depression was observed were evaluated as "absent".

[0242] <Test Example 3: Measurement of arithmetic mean roughness (Ra)> (1) Thermosetting of the resin composition layer The inner layer substrate laminated with the resin sheet A in Test Example 2(2) was placed in an oven at 130°C and heated for 30 minutes, and then transferred to an oven at 170°C and heated for 30 minutes to thermoset the resin composition layer and form an insulating layer. Thereafter, the support was peeled off to obtain a cured substrate A having an insulating layer, an inner layer substrate, and an insulating layer in this order.

[0243] (2) Roughening treatment A desmear treatment as a roughening treatment was performed on the cured substrate A. As the desmear treatment, the following wet desmear treatment was carried out.

[0244] (Wet desmear treatment) The cured substrate A was immersed in a swelling solution (aqueous solution of "Swelling Dip Securigant P" manufactured by Atotech Japan, diethylene glycol monobutyl ether, and sodium hydroxide) at 60°C for 5 minutes, and then immersed in an oxidizing agent solution (aqueous solution of "Concentrate Compact CP" manufactured by Atotech Japan, potassium permanganate concentration of about 6%, and sodium hydroxide concentration of about 4%) at 80°C for 20 minutes. Subsequently, it was immersed in a neutralizing solution (aqueous solution of "Reduction Solution Securigant P" manufactured by Atotech Japan, sulfuric acid) at 40°C for 5 minutes, and then dried at 80°C for 15 minutes.

[0245] (3) Measurement of the arithmetic mean roughness (Ra) of the surface of the insulating layer after roughening treatment The arithmetic mean roughness (Ra) of the surface of the insulating layer after roughening treatment was determined by the numerical values obtained with a non-contact surface roughness meter (WYKO NT3300 manufactured by Bruker) in VSI mode and a 50x lens with a measurement range of 121 μm × 92 μm. The measurement was performed by obtaining the average value of 10 points each.

[0246] <Test Example 4: Measurement of peel strength> (1) Formation of the conductor layer According to the semi-additive method, a conductor layer was formed on the roughened surface of the insulating layer in the cured substrate A roughened in Test Example 3(2). That is, the substrate after roughening treatment was immersed in an electroless plating solution containing PdCl2 at 40°C for 5 minutes, and then immersed in an electroless copper plating solution at 25°C for 20 minutes. Subsequently, it was heated at 150°C for 30 minutes for annealing treatment, then an etching resist was formed, and patterning was performed by etching. Thereafter, electrolytic copper sulfate plating was performed to form a conductor layer with a thickness of 25 μm, and annealing treatment was performed at 190°C for 60 minutes. The obtained substrate was designated as "Evaluation Substrate B".

[0247] (2) Measurement of the peel strength of the plated conductor layer The measurement of the peel strength between the insulating layer and the conductor layer was carried out in accordance with Japanese Industrial Standard (JIS C6481). Specifically, a cut was made in the conductor layer of the evaluation substrate B in a portion with a width of 10 mm and a length of 100 mm. One end of this was peeled off and grasped with a gripping tool, and the load (kgf / cm) when it was peeled off vertically by 35 mm at a speed of 50 mm / min at room temperature was measured to obtain the peel strength. A tensile testing machine (“AC-50C-SL” manufactured by TSE) was used for the measurement.

[0248] The amounts of the non-volatile components 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.

[0249]

Table 1

[0250] It was found that by using (A) a compound containing a repeating unit represented by formula (1), (B) an epoxy resin, and (C) an active ester compound, a cured product with a low dielectric tangent (Df), good peel strength, and suppressed unevenness after lamination could be obtained.

Claims

1. (A) Formula (1A-1) to (1B-3): 【Chemical 1】 [In the formula, R3, R4, and R5 each independently represent an alkyl group; Ra each independently represents an alkyl group, an alkenyl group, an aryl group, an alkyl-aryl group, an aryl-aryl group, an aryl-alkyl group, an alkyl-oxy group, an alkenyl-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, or an aryl-carbonyl-oxy group; Rb and Rc each independently represent a substituent; a represents an integer from 0 to 2; b and c each independently represent an integer from 0 to 3; x represents an integer from 0 to 5.] A resin composition comprising a compound containing a repeating unit represented by at least any one of the above, (B) an epoxy resin, (C) an active ester compound, and (D) an inorganic filler, wherein the content of component (A) is 0.01% by mass to 3% by mass when the non-volatile components in the resin composition are 100% by mass. The resin composition.

2. The resin composition according to claim 1, wherein component (B) contains (B-1) an epoxy resin containing a condensed ring structure.

3. The resin composition according to claim 2, wherein component (B-1) is a monomeric epoxy resin containing a condensed ring structure.

4. The resin composition according to any one of claims 1 to 3, wherein the content of component (B) is 1% by mass to 30% by mass when the non-volatile components in the resin composition are 100% by mass.

5. The resin composition according to any one of claims 1 to 4, wherein the mass ratio of component (B) to component (A) ((B) component / (A) component) is 10 to 50.

6. The resin composition according to any one of claims 1 to 5, wherein the content of component (C) is 5% by mass to 30% by mass when the non-volatile components in the resin composition are 100% by mass.

7. The resin composition according to any one of claims 1 to 6, wherein the mass ratio of component (C) to component (A) ((C) component / (A) component) is 30 to 100.

8. The resin composition according to any one of claims 1 to 7, wherein component (D) is silica.

9. The resin composition according to any one of claims 1 to 8, wherein the content of component (D) is 50% by mass or more when the non-volatile components in the resin composition are 100% by mass.

10. The resin composition according to claim 9, wherein the content of component (D) is 70% by mass or more when the non-volatile components in the resin composition are 100% by mass.

11. The resin composition according to any one of claims 1 to 10, further comprising (E) a radically polymerizable compound.

12. The resin composition according to any one of claims 1 to 11, further comprising (F-1) a carbodiimide-based curing agent.

13. A cured product of the resin composition according to any one of claims 1 to 12.

14. A sheet-like laminated material containing the resin composition according to any one of claims 1 to 12.

15. A resin sheet having a support and a resin composition layer formed from the resin composition according to any one of claims 1 to 12 provided on the support.

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

17. A semiconductor device including the printed wiring board according to claim 16.

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