Resin composition

Abstract

To provide, e.g., a resin composition capable of yielding a cured product that exhibits excellent crack resistance, high peel strength, and low dielectric loss tangent.SOLUTION: A resin composition comprises: (A) an epoxy resin; (B) an active ester curing agent; (C) one or more curing accelerators selected from the group consisting of compounds represented by the formula (C-1) and compounds represented by the formula (C-2); and (D) a curing accelerator (excluding those corresponding to the component (C)).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a resin composition. The present invention further relates to a resin sheet, a printed wiring board, and a semiconductor device obtained by using the resin composition. [Background technology]

[0002] A known manufacturing technique for printed wiring boards is a build-up method in which insulating layers and conductor layers are alternately stacked. In build-up manufacturing methods, the insulating layers are generally formed by curing a resin composition. For example, the resin composition disclosed in Patent Document 1 is known as such a resin composition. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2016-26261 Summary of the Invention [Problem to be solved by the invention]

[0004] In order to improve electrical properties, insulating layers of printed wiring boards are required to have a low dielectric loss tangent. To achieve this, it has been considered to incorporate an active ester curing agent into the resin composition. However, the incorporation of an active ester curing agent can result in poor crack resistance of the cured product and poor peel strength between the cured product and the conductor layer.

[0005] The present invention has been made in view of the above-mentioned problems, and aims to provide a resin composition that can give a cured product that has excellent crack resistance, high peel strength, and a low dielectric loss tangent; a resin sheet having a resin composition layer that includes the resin composition; a printed wiring board that includes an insulating layer formed from a cured product of the resin composition; and a semiconductor device that includes the printed wiring board. [Means for solving the problem]

[0006] As a result of extensive research into solving the above-mentioned problems, the present inventors have discovered that even when an active ester-based curing agent (B) is used, by combining a curing accelerator (C) having a specific structure with a component (D) as well, it is possible to obtain an unexpected and remarkable effect of obtaining a cured product having excellent crack resistance, high peel strength, and a low dielectric loss tangent, which has led to the completion of the present invention.

[0007] That is, the present invention includes the following. [1] (A) epoxy resin, (B) active ester curing agent, (C) one or more curing accelerators selected from the group consisting of compounds represented by formula (C-1), and (D) A resin composition containing a curing accelerator (excluding those corresponding to component (C)), When the nonvolatile components in the resin composition are 100% by mass, A resin composition in which the following relationship holds, where the content of component (C) is (c) and the content of component (D) is (d). 0.1≦(c) / (d)≦30 (excluding the range 0.5≦(c) / (d)≦5) [C1] TIFF2025176055000001.tif31170 formula (C-1), R 11 , R 12 , R 13 , and R 14 each independently represents a hydrogen atom, an optionally substituted monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms, or an optionally substituted monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms; R 15 represents a divalent aliphatic hydrocarbon group which may have a substituent, or a divalent aromatic hydrocarbon group which may have a substituent. [2] The resin composition according to [1], further comprising (E) an inorganic filler. [3] The resin composition according to [1], wherein the component (D) includes either an imidazole-based curing accelerator or an amine-based curing accelerator. [4] In formula (C-1), R 11 , R 12 , R 13 , and R 14 and each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a phenyl group. [1] The resin composition according to [1]. [5] In formula (C-1), R 15 represents an alkylene group which may have a substituent, or a divalent aromatic hydrocarbon group which may have a substituent. [1] The resin composition according to [1]. [6] The resin composition according to [1], which is for forming an insulating layer. [7] A resin sheet comprising a support and a resin composition layer provided on the support, the resin composition layer comprising the resin composition according to [1]. [8] A printed wiring board comprising an insulating layer formed from a cured product of the resin composition according to [1]. [9] A semiconductor device comprising the printed wiring board according to [8]. [Effects of the Invention]

[0008] According to the present invention, it is possible to provide a resin composition that can give a cured product that has excellent crack resistance, high peel strength, and a low dielectric loss tangent; a resin sheet that has a resin composition layer that includes the resin composition; a printed wiring board that includes an insulating layer formed from a cured product of the resin composition; and a semiconductor device that includes the printed wiring board. DETAILED DESCRIPTION OF THE INVENTION

[0009] The present invention will be described below with reference to embodiments and examples. However, the present invention is not limited to the embodiments and examples shown below, and can be implemented with any modifications within the scope of the claims of the present invention and their equivalents.

[0010] [Resin composition] The resin composition of the present invention comprises (A) an epoxy resin, (B) an active ester curing agent, (C) one or more curing accelerators selected from the group consisting of compounds represented by formula (C-1) and compounds represented by formula (C-2), and (D) a curing accelerator (excluding those corresponding to component (C)). Such a resin composition makes it possible to obtain a cured product with excellent crack resistance, high peel strength, and low dielectric loss tangent. Furthermore, the resin composition can also generally produce a cured product with low surface roughness after roughening treatment. [ka] In formula (C-1), R 11 , R 12 , R 13 , and R 14 each independently represents a hydrogen atom, an optionally substituted monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms, or an optionally substituted monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms; R 15 represents a divalent aliphatic hydrocarbon group which may have a substituent, or a divalent aromatic hydrocarbon group which may have a substituent. In formula (C-2), R 21 , R 22 , R 23 , and R 24 each independently represents a hydrogen atom, an optionally substituted monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms, or an optionally substituted monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms; R 25 represents a single bond, a divalent aliphatic hydrocarbon group which may have a substituent, an oxygen atom, or a sulfonyl group.

[0011] The resin composition may further contain optional components such as (E) an inorganic filler, (F) a thermoplastic resin, (G) a curing agent, (H) a radically polymerizable compound, and (I) other additives, as necessary. Each component contained in the resin composition will be described in detail below.

[0012] In the present invention, the content of each component in the resin composition is a value when the nonvolatile components in the resin composition are 100 mass %, unless otherwise specified, and the nonvolatile components refer to all nonvolatile components in the resin composition excluding the solvent. In addition, in the present invention, the resin components in the resin composition refer to the nonvolatile components of the resin composition excluding the inorganic filler (E).

[0013] <(A) Epoxy resin> The resin composition contains an epoxy resin (A) as component (A). By including the epoxy resin (A) in the resin composition, a cured product with low dielectric properties and excellent peel strength can be obtained. The epoxy resin (A) may be used alone or in combination of two or more.

[0014] Examples of (A) epoxy resins include bixylenol-type epoxy resins, bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, bisphenol S-type epoxy resins, bisphenol AF-type epoxy resins, dicyclopentadiene-type epoxy resins, trisphenol-type epoxy resins, naphthol novolac-type epoxy resins, phenol novolac-type epoxy resins, tert-butyl-catechol-type epoxy resins, naphthalene-type epoxy resins, naphthol-type epoxy resins, anthracene-type epoxy resins, glycidylamine-type epoxy resins, glycidyl ester-type epoxy resins, glycidylcyclohexane-type epoxy resins, cresol novolac-type epoxy resins, biphenyl-type epoxy resins, linear aliphatic epoxy resins, epoxy resins having a butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, spiro ring-containing epoxy resins, cyclohexane-type epoxy resins, cyclohexanedimethanol-type epoxy resins, naphthylene ether-type epoxy resins, trimethylol-type epoxy resins, tetraphenylethane-type epoxy resins, and phenolphthalimidine-type epoxy resins. The epoxy resin may be used alone or in combination of two or more kinds.

[0015] The resin composition preferably contains, as component (A), an epoxy resin having two or more epoxy groups per molecule. From the viewpoint of significantly achieving the desired effects of the present invention, the proportion of the epoxy resin having two or more epoxy groups per molecule relative to 100% by mass of the epoxy resin (A) is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more.

[0016] Epoxy resins include epoxy resins that are liquid at a temperature of 20°C (hereinafter sometimes referred to as "liquid epoxy resins") and epoxy resins that are solid at a temperature of 20°C (hereinafter sometimes referred to as "solid epoxy resins"). The resin composition may contain, as component (A), only a liquid epoxy resin, only a solid epoxy resin, or a combination of a liquid epoxy resin and a solid epoxy resin.

[0017] The liquid epoxy resin is preferably a liquid epoxy resin having two or more epoxy groups in one molecule.

[0018] Preferred liquid epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, naphthalene type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, phenol novolac type epoxy resins, alicyclic epoxy resins having an ester skeleton, cyclohexane type epoxy resins, cyclohexane dimethanol type epoxy resins, glycidyl amine type epoxy resins, epoxy resins having a butadiene structure, glycidyl cyclohexane type epoxy resins, and phenolphthalimidine type epoxy resins, with bisphenol A type epoxy resins being more preferred.

[0019] Specific examples of liquid epoxy resins include "HP4032," "HP4032D," and "HP4032SS" (naphthalene-type epoxy resins) manufactured by DIC Corporation; "828US," "jER828EL," "825," and "Epikote 828EL" (bisphenol A-type epoxy resins) manufactured by Mitsubishi Chemical Corporation; "jER807" and "1750" (bisphenol F-type epoxy resins) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol novolac-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; and "630" and "630LSD" (glycidylamine-type epoxy resins) manufactured by Mitsubishi Chemical Corporation. ); "ZX1059" manufactured by Nippon Steel Chemical & Material Co., Ltd. (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); "EX-721" manufactured by Nagase ChemteX Corporation (a glycidyl ester type epoxy resin); "Celloxide 2021P" manufactured by Daicel Corporation (an alicyclic epoxy resin having an ester skeleton); "PB-3600" manufactured by Daicel Corporation (an epoxy resin having a butadiene structure); and "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd. These may be used alone or in combination of two or more.

[0020] As the solid epoxy resin, a solid epoxy resin having two or more epoxy groups in one molecule is preferred, a solid epoxy resin having three or more epoxy groups in one molecule is more preferred, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is even more preferred.

[0021] Preferred solid epoxy resins include bixylenol-type epoxy resins, naphthalene-type epoxy resins, naphthalene-type tetrafunctional epoxy resins, cresol novolac-type epoxy resins, dicyclopentadiene-type epoxy resins, trisphenol-type epoxy resins, naphthol-type epoxy resins, biphenyl-type epoxy resins, naphthylene ether-type epoxy resins, anthracene-type epoxy resins, bisphenol A-type epoxy resins, bisphenol AF-type epoxy resins, and tetraphenylethane-type epoxy resins, and biphenyl-type epoxy resins are more preferred.

[0022] Specific examples of solid epoxy resins include "HP4032H" (naphthalene type epoxy resin), "HP-4700", "HP-4710" (naphthalene type tetrafunctional epoxy resin), "N-690" (cresol novolac type epoxy resin), "N-695" (cresol novolac type epoxy resin), "HP-7200", "HP-7200HH", "HP-7200H" (dicyclopentadiene type epoxy resin), "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000", "HP6000L" (naphthylene ether type epoxy resin), manufactured by DIC Corporation; "EPPN-502H" (trisphenol type epoxy resin), "NC7000L" (naphthol novolac type epoxy resin), "NC3000H", "NC3000", "NC3000L" manufactured by Nippon Kayaku Co., Ltd.; Examples include "NC3100" (biphenyl-type epoxy resin); "ESN475V" (naphthalene-type epoxy resin) and "ESN485" (naphthol novolac-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YX4000H", "YL6121" (biphenyl-type epoxy resin), "YX4000HK" (bixylenol-type epoxy resin), and "YX8800" (anthracene-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Co., Ltd.; "YL7760" (bisphenol AF-type epoxy resin), "YL7800" (fluorene-type epoxy resin), "jER1010" (solid bisphenol A-type epoxy resin), and "jER1031S" (tetraphenylethane-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; and "WHR-991S" (phenolphthalimidine-type epoxy resin) manufactured by Nippon Kayaku Co., Ltd. These may be used alone or in combination of two or more.

[0023] When a liquid epoxy resin and a solid epoxy resin are used in combination as component (A), the ratio by mass between them (liquid epoxy resin:solid epoxy resin) is preferably 1:0.1 to 1:20, more preferably 1:0.3 to 1:10, and particularly preferably 1:0.5 to 1:5. When the ratio between the liquid epoxy resin and the solid epoxy resin is within this range, the desired effects of the present invention can be significantly achieved.

[0024] The epoxy equivalent of component (A) is preferably 50 g / eq. to 5000 g / eq., more preferably 50 g / eq. to 3000 g / eq., even more preferably 80 g / eq. to 2000 g / eq., and even more preferably 110 g / eq. to 1000 g / eq. By keeping it within this range, a cured product of the resin composition can be obtained with sufficient crosslink density. The epoxy equivalent is the mass of an epoxy resin containing one equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.

[0025] From the viewpoint of significantly achieving the desired effects of the present invention, the weight average molecular weight (Mw) of the component (A) is preferably 100 to 5000, more preferably 150 to 3000, and even more preferably 200 to 1500. The weight average molecular weight of the epoxy resin is the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

[0026] From the viewpoint of obtaining a cured product exhibiting good mechanical strength and insulation reliability, the content of component (A) is preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more, and is preferably 75% by mass or less, preferably 70% by mass or less, more preferably 65% ​​by mass or less, and even more preferably 60% by mass or less, assuming that the resin component in the resin composition is 100% by mass.

[0027] The content of component (A) is preferably 3% by mass or more, more preferably 5% by mass or more, and even more preferably 8% by mass or more, based on 100% by mass of the nonvolatile components in the resin composition, from the viewpoint of obtaining a cured product exhibiting good mechanical strength and insulation reliability. The upper limit of the epoxy resin content is preferably 35% by mass or less, more preferably 30% by mass or less, and particularly preferably 25% by mass or less, from the viewpoint of significantly obtaining the desired effects of the present invention.

[0028] <(B) Active ester curing agent> The resin composition contains an active ester curing agent (B) as component (B). This active ester curing agent (B) as component (B) does not include those corresponding to the aforementioned component (A). The active ester curing agent (B) typically reacts with the epoxy resin (A) to form a bond, thereby curing the resin composition. Because the resin composition contains component (B), a cured product with low surface roughness after roughening treatment can be obtained. Furthermore, in the present invention, by using a combination of component (A) and active ester curing agent (B), a cured product with excellent peel strength from plating can be obtained, while also having low dielectric properties. The component (B) may be used alone or in combination of two or more types.

[0029] As the (B) active ester curing agent, compounds having two or more highly reactive ester groups per molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, are generally preferred. The active ester curing agent is preferably one obtained by the condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound. From the viewpoint of improving heat resistance, active ester curing agents obtained from a carboxylic acid compound and a hydroxy compound are preferred, and active ester curing agents obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound are more preferred. Examples of carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of phenol compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalene, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene-type diphenol compounds, and phenol novolak. Here, "dicyclopentadiene-type diphenol compounds" refers to diphenol compounds obtained by condensing one dicyclopentadiene molecule with two phenol molecules.

[0030] Specifically, examples of component (B) include dicyclopentadiene-type active ester curing agents, naphthalene-type active ester curing agents containing a naphthalene structure, active ester curing agents containing an acetylated product of phenol novolac, active ester curing agents containing a benzoylated product of phenol novolac, active ester curing agents that are acetylated products of phenol novolac, and active ester curing agents containing a styryl group and a naphthalene structure. As the dicyclopentadiene-type active ester curing agent, an active ester curing agent containing a dicyclopentadiene-type diphenol structure is preferred. The "dicyclopentadiene-type diphenol structure" refers to a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.

[0031] Among these, component (B) is more preferably at least one selected from active ester curing agents containing a styryl group and a naphthalene structure, and naphthalene-type active ester curing agents containing a naphthalene structure, and even more preferably a naphthalene-type active ester curing agent containing a naphthalene structure.

[0032] Commercially available products of component (B) include active ester curing agents containing a dicyclopentadiene-type diphenol structure, such as "EXB9451," "EXB9460," "EXB9460S," "HPC-8000-65T," "HPC-8000H-65TM," and "EXB-8000L-65TM" (manufactured by DIC Corporation); naphthalene-type active ester curing agents containing a naphthalene structure, such as "HP-B-8151-62T," "EXB9416-70BK," "EXB-8100L-65T," "EXB-8150L-65T," "EXB-815065T," "HPC-815060T," and "HPC-8150-62T" (manufactured by DIC Corporation), and "PC1300-02-65T" (manufactured by Air Water Inc.); and a phosphorus-containing active ester compound, such as "EXB9401" (manufactured by DIC Corporation). "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester-based curing agent containing an acetylated product of phenol novolac; "YLH1026" (manufactured by Mitsubishi Chemical Corporation) as an active ester-based curing agent containing a benzoylated product of phenol novolac; "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester-based curing agent which is an acetylated product of phenol novolac; "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), and "YLH1048" (manufactured by Mitsubishi Chemical Corporation) as active ester-based curing agents which are benzoylated products of phenol novolac; "EXB-8500-65T" (manufactured by DIC Corporation); and "PC1300-02-65MA" (manufactured by Air Water Inc.) as an active ester-based curing agent containing a styryl group and a naphthalene structure.

[0033] From the viewpoint of being able to reduce the dielectric tangent and obtaining a cured product with excellent peel strength, the active ester group equivalent of component (B) is preferably 50 g / eq. to 500 g / eq., more preferably 50 g / eq. to 400 g / eq., and even more preferably 100 g / eq. to 300 g / eq. The active ester group equivalent is the mass of the active ester curing agent containing one equivalent of active ester groups.

[0034] The quantitative ratio of (A) epoxy resin to (B) active ester curing agent, expressed as the ratio of [total number of active groups in active ester curing agent] / [total number of epoxy groups in epoxy resin], is preferably 0.01 or more, more preferably 0.3 or more, even more preferably 0.5 or more, and preferably 5 or less, more preferably 3 or less, and even more preferably 2 or less. Here, the "number of epoxy groups in the epoxy resin" refers to the sum of all values ​​obtained by dividing the mass of the non-volatile components of the epoxy resin present in the resin composition by the epoxy equivalent. Furthermore, the "number of active groups in the active ester curing agent" refers to the sum of all values ​​obtained by dividing the mass of the non-volatile components of the active ester curing agent present in the resin composition by the active ester group equivalent. By setting the quantitative ratio of the epoxy resin to the active ester curing agent within this range, the effects of the present invention can be significantly achieved.

[0035] From the viewpoint of obtaining a cured product with small surface roughness after roughening treatment and excellent peel strength and dielectric loss tangent, the content of component (B) is preferably 20% by mass or more, more preferably 25% by mass or more, even more preferably 30% by mass or more, and preferably 55% by mass or less, more preferably 50% by mass or less, and even more preferably 45% by mass or less, based on 100% by mass of the resin component in the resin composition. Since the resin composition of the present invention contains a combination of components (C) and (D), even if the content of component (B) is increased to lower the dielectric loss tangent, a cured product with excellent crack resistance and peel strength can be obtained.

[0036] From the viewpoint of obtaining a cured product with low surface roughness after roughening treatment and excellent peel strength and dielectric loss tangent, the content of component (B) is preferably 5% by mass or more, more preferably 7% by mass or more, and even more preferably 8% by mass or more, based on 100% by mass of the nonvolatile components in the resin composition. The upper limit is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less. Since the resin composition of the present invention contains a combination of components (C) and (D), even if the content of component (B) is increased to reduce the dielectric loss tangent, a cured product with excellent crack resistance and peel strength can be obtained.

[0037] <(C) One or more curing accelerators selected from the group consisting of compounds represented by formula (C-1) and compounds represented by formula (C-2)> The resin composition contains, as component (C), one or more curing accelerators selected from the group consisting of compounds represented by formula (C-1) and compounds represented by formula (C-2). The one or more curing accelerators selected from the group consisting of compounds represented by formula (C-1) and compounds represented by formula (C-2) as component (C) do not include those corresponding to the aforementioned components (A) and (B). Component (C) typically functions as a catalyst in the reaction between epoxy resin (A) and curing agents such as components (B) and (G), thereby accelerating the curing of the resin composition. In the present invention, by using component (C) in combination with component (D), described below, a cured product with excellent crack resistance and peel strength from plating can be obtained. Component (C) may be used alone or in combination of two or more. [ka] In formula (C-1), R 11 , R 12 , R 13 , and R 14 each independently represents a hydrogen atom, an optionally substituted monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms, or an optionally substituted monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms; R 15 represents a divalent aliphatic hydrocarbon group which may have a substituent, or a divalent aromatic hydrocarbon group which may have a substituent. In formula (C-2), R 21 , R 22 , R 23 , and R 24 each independently represents a hydrogen atom, an optionally substituted monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms, or an optionally substituted monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms; R 25 represents a single bond, a divalent aliphatic hydrocarbon group which may have a substituent, an oxygen atom, or a sulfonyl group.

[0038] In formula (C-1), R 11 , R 12 , R 13 , and R 14 each independently represents a hydrogen atom, an optionally substituted monovalent aliphatic hydrocarbon group of 1 to 5 carbon atoms, or an optionally substituted monovalent aromatic hydrocarbon group of 6 to 10 carbon atoms.

[0039] The monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms, which may have a substituent, is preferably a monovalent aliphatic hydrocarbon group having 1 to 4 carbon atoms, more preferably a monovalent aliphatic hydrocarbon group having 1 to 3 carbon atoms, and even more preferably a monovalent aliphatic hydrocarbon group having 1 or 2 carbon atoms. The number of carbon atoms does not include the number of carbon atoms of the substituent. Specific examples of the monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms, which may have a substituent, include an alkyl group having 1 to 5 carbon atoms, which may have a substituent, an alkenyl group having 2 to 5 carbon atoms, which may have a substituent, and an alkynyl group having 2 to 5 carbon atoms, which may have a substituent. Of these, as the aliphatic hydrocarbon group having 1 to 5 carbon atoms, which may have a substituent, an alkyl group having 1 to 5 carbon atoms, which may have a substituent, is preferred from the viewpoint of significantly achieving the effects of the present invention.

[0040] The alkyl group having 1 to 5 carbon atoms, which may have a substituent, may be linear, branched, or cyclic. The alkyl group is preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably an alkyl group having 1 or 2 carbon atoms. The number of carbon atoms does not include the number of carbon atoms of the substituent. Examples of such an alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, and a pentyl group, with a methyl group and an ethyl group being preferred.

[0041] The alkenyl group having 1 to 5 carbon atoms, which may have a substituent, may be linear, branched, or cyclic. The alkenyl group is preferably an alkenyl group having 2 to 5 carbon atoms, more preferably an alkenyl group having 2 to 4 carbon atoms, and more preferably an alkenyl group having 2 to 3 carbon atoms. The number of carbon atoms does not include the number of carbon atoms of the substituent. Examples of such alkenyl groups include an ethynyl group, a propynyl group, a butynyl group, and a pentynyl group.

[0042] The alkynyl group having 1 to 5 carbon atoms, which may have a substituent, may be linear, branched, or cyclic. The alkynyl group is preferably an alkynyl group having 2 to 5 carbon atoms, more preferably an alkynyl group having 2 to 4 carbon atoms, and more preferably an alkynyl group having 2 to 3 carbon atoms. The number of carbon atoms does not include the number of carbon atoms of the substituent. Examples of such alkynyl groups include an ethynyl group, a propynyl group, a butynyl group, a sec-butynyl group, an isobutynyl group, a tert-butynyl group, and a pentynyl group.

[0043] Specific examples of the monovalent aromatic hydrocarbon group of 6 to 10 carbon atoms which may have a substituent include an aryl group of 6 to 10 carbon atoms which may have a substituent, and a heteroaryl group of 6 to 10 carbon atoms which may have a substituent. Of these, from the viewpoint of significantly achieving the effects of the present invention, the monovalent aromatic hydrocarbon group of 6 to 10 carbon atoms which may have a substituent is preferably an aryl group of 6 to 10 carbon atoms which may have a substituent.

[0044] Examples of the aryl group having 6 to 10 carbon atoms which may have a substituent include a phenyl group and a naphthyl group, with a phenyl group being preferred.

[0045] Examples of the heteroaryl group having 6 to 10 carbon atoms which may have a substituent include groups obtained by removing one hydrogen atom from pyrrole, furan, thiophene, etc.

[0046] Among them, R 11 , R12 , R 13 , and R 14 preferably each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group of 1 to 5 carbon atoms which may have a substituent, or a phenyl group, more preferably represent a monovalent aliphatic hydrocarbon group of 1 to 5 carbon atoms which may have a substituent, even more preferably represent an alkyl group of 1 to 5 carbon atoms which may have a substituent, and particularly preferably represent a methyl group or an ethyl group.

[0047] R 11 , R 12 , R 13 , and R 14 The monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms and the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms represented by the formula (I) may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkoxy group, an aryl group, an arylalkyl group, a silyl group, an acyl group, an acyloxy group, a carboxy group, a sulfo group, a cyano group, a nitro group, a hydroxy group, a mercapto group, and an oxo group.

[0048] R 15 represents a divalent aliphatic hydrocarbon group which may have a substituent, or a divalent aromatic hydrocarbon group which may have a substituent.

[0049] The optionally substituted divalent aliphatic hydrocarbon group is preferably a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, more preferably a divalent aliphatic hydrocarbon group having 1 to 6 carbon atoms, and even more preferably a divalent aliphatic hydrocarbon group having 1 to 4 carbon atoms. The number of carbon atoms does not include the number of carbon atoms of the substituent. Examples of optionally substituted divalent aliphatic hydrocarbon groups include optionally substituted alkylene groups, optionally substituted alkenylene groups, and optionally substituted alkynylene groups. Of these, optionally substituted divalent aliphatic hydrocarbon groups are preferably optionally substituted alkylene groups, from the viewpoint of significantly achieving the effects of the present invention.

[0050] The alkylene group, which may have a substituent, may be linear, branched, or cyclic, and is preferably a linear or branched hydrocarbon group, more preferably a linear one. The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms. The number of carbon atoms does not include the number of carbon atoms of the substituent. Examples of the alkylene group include a methylene group, an ethylene group, a 1-methylethylene group, a propylene group, an n-butylene group, an s-butylene group, a t-butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, and a decylene group. A methylene group, an ethylene group, a propylene group, an n-butylene group, an s-butylene group, and a t-butylene group are preferred, a methylene group, an ethylene group, a 1-methylethylene group, a propylene group, an n-butylene group, an s-butylene group, and a t-butylene group are more preferred, and a methylene group, an ethylene group, a propylene group, and an n-butylene group are particularly preferred.

[0051] The alkenylene group, which may have a substituent, may be linear, branched, or cyclic, and is preferably a linear or branched hydrocarbon group, more preferably a linear one. The alkenylene group is preferably an alkenylene group having 2 to 10 carbon atoms, more preferably an alkenylene group having 2 to 6 carbon atoms, and even more preferably an alkenylene group having 3 or 4 carbon atoms. The number of carbon atoms does not include the number of carbon atoms of the substituent. Examples of the alkenylene group include an ethenylene group, a propenylene group, a butenylene group, a pentenylene group, a hexenylene group, a heptenylene group, an octenylene group, a nonenylene group, and a decenylene group.

[0052] The alkynylene group, which may have a substituent, may be linear, branched, or cyclic, and is preferably a linear or branched hydrocarbon group, more preferably a linear one. The alkynylene group is preferably an alkynylene group having 2 to 10 carbon atoms, more preferably an alkynylene group having 2 to 6 carbon atoms, and even more preferably an alkynylene group having 3 or 4 carbon atoms. The number of carbon atoms does not include the number of carbon atoms of the substituent. Examples of the alkynylene group include an ethynylene group, a propynylene group, a butynylene group, a pentynylene group, a hexynylene group, a heptynylene group, an octynylene group, a nonynylene group, and a decynylene group.

[0053] The optionally substituted divalent aromatic hydrocarbon group is preferably a divalent aromatic hydrocarbon group having 3 to 20 carbon atoms, more preferably a divalent aromatic hydrocarbon group having 6 to 14 carbon atoms, and even more preferably a divalent aromatic hydrocarbon group having 6 to 10 carbon atoms. The number of carbon atoms does not include the number of carbon atoms of the substituent. Examples of the optionally substituted divalent aromatic hydrocarbon group include an optionally substituted arylene group and an optionally substituted heteroarylene group. Of these, an optionally substituted arylene group is preferred as the optionally substituted divalent aromatic hydrocarbon group from the viewpoint of significantly achieving the effects of the present invention.

[0054] The optionally substituted arylene group is preferably an arylene group having 6 to 20 carbon atoms, more preferably an arylene group having 6 to 14 carbon atoms, and even more preferably an arylene group having 6 to 10 carbon atoms. The number of carbon atoms does not include the number of carbon atoms of the substituent. Examples of the arylene group include a phenylene group, a naphthylene group, and an anthracenylene group, with a phenylene group being preferred.

[0055] The optionally substituted heteroarylene group is preferably a heteroarylene group having 3 to 20 carbon atoms, more preferably a heteroarylene group having 6 to 14 carbon atoms, and even more preferably a heteroarylene group having 6 to 10 carbon atoms. The number of carbon atoms does not include the number of carbon atoms of the substituent. Examples of the optionally substituted heteroarylene group include groups obtained by removing two hydrogen atoms from pyrrole, furan, thiophene, indole, benzofuran, benzothiophene, etc.

[0056] Among them, R 15 As the alkylene group, an alkylene group which may have a substituent or a divalent aromatic hydrocarbon group which may have a substituent is preferred, and an alkylene group which may have a substituent is more preferred.

[0057] R 15 The divalent aliphatic hydrocarbon group and the divalent aromatic hydrocarbon group represented by may have a substituent. 11 These are the same as the substituents that may be possessed by the monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by the formula:

[0058] Examples of the compound represented by formula (C-1) include, but are not limited to, the compound (i) exemplified below. [ka]

[0059] In formula (C-2), R 21 , R 22 , R 23 , and R 24 each independently represents a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms which may have a substituent, or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent, and R in formula (C-1) 11 is the same as

[0060] R 21 , R 22 , R 23 , and R 24preferably each independently represents a hydrogen atom, a divalent aliphatic hydrocarbon group having 1 to 5 carbon atoms which may have a substituent, or a phenyl group, and more preferably represents a hydrogen atom or a phenyl group.

[0061] In formula (C-2), R 25 represents a single bond, a divalent aliphatic hydrocarbon group which may have a substituent, an oxygen atom, or a sulfonyl group, and the divalent aliphatic hydrocarbon group is represented by R 15 is the same as the optionally substituted divalent aliphatic hydrocarbon group represented by

[0062] R 25 As the alkyl group, a divalent aliphatic hydrocarbon group which may have a substituent is preferred, and an alkylene group which may have a substituent is more preferred.

[0063] Examples of the compound represented by formula (C-2) include, but are not limited to, the compound (ii) shown below. [ka]

[0064] Component (C) may be a commercially available product, such as "G-8009L" manufactured by Daiichi Kogyo Seiyaku Co., Ltd. or "P200H50" manufactured by Mitsubishi Chemical Corporation.

[0065] From the viewpoint of obtaining a cured product with excellent crack resistance, the content of component (C) is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.3% by mass or more, and is preferably 5% by mass or less, preferably 4% by mass or less, more preferably 3% by mass or less, and even more preferably 1.5% by mass or less, based on 100% by mass of the resin component in the resin composition.

[0066] From the viewpoint of obtaining a cured product with excellent crack resistance, the content of component (C) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more, and is preferably 1.5% by mass or less, more preferably 1% by mass or less, and particularly preferably 0.5% by mass or less, based on 100% by mass of the non-volatile components in the resin composition.

[0067] When the content of component (A) when the nonvolatile components in the resin composition are taken as 100% by mass is defined as a and the content of component (C) when the nonvolatile components in the resin composition are taken as 100% by mass is defined as c, (c / a) × 100 is preferably 0.1 or more, more preferably 0.5 or more, even more preferably 1 or more, 1.5 or more, from the viewpoint of significantly obtaining the effects of the present invention, and is preferably 15 or less, more preferably 10 or less, even more preferably 5 or less, 3.5 or less.

[0068] When the content of component (B) is b when the nonvolatile components in the resin composition are 100% by mass, (c / b) × 100 is preferably 0.1 or more, more preferably 1 or more, and even more preferably 2.5 or more, from the viewpoint of significantly obtaining the effects of the present invention, and is preferably 15 or less, more preferably 10 or less, and even more preferably 5 or less.

[0069] <(D) Curing accelerator> In addition to the above-mentioned components, the resin composition further contains, as an optional component, a curing accelerator (D) (excluding those corresponding to component (C)). The curing accelerator (D) as component (D) does not include those corresponding to the above-mentioned components (A), (B), and (C). Component (D) typically functions as a catalyst in the reaction between the epoxy resin (A) and curing agents such as components (B) and (G), thereby accelerating the curing of the resin composition. The resin composition of the present invention can obtain a cured product with excellent crack resistance by using a curing accelerator (C) having a group represented by formula (C-1), which has a specific structure, in combination with the curing accelerator (D).

[0070] Examples of component (D) include imidazole-based curing accelerators (excluding compounds represented by formula (C-1) and formula (C-2)), amine-based curing accelerators, guanidine-based curing accelerators, phosphorus-based curing accelerators, and metal-based curing accelerators. Of these, component (D) is preferably either an imidazole-based curing accelerator or an amine-based curing accelerator. Component (D) may be used alone or in combination of two or more.

[0071] Examples of the imidazole curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 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-undecylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2, 4-Diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, Examples of the imidazole compound include imidazole compounds such as 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, as well as adducts of imidazole compounds with epoxy resins, and 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferred.

[0072] As the imidazole-based curing accelerator, a commercially available product may be used, for example, "1B2PZ" manufactured by Shikoku Chemicals Corporation.

[0073] Examples of the amine curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo(5,4,0)-undecene, with 4-dimethylaminopyridine and 1,8-diazabicyclo(5,4,0)-undecene being preferred.

[0074] As the amine-based curing accelerator, commercially available products may be used, for example, "DMAP" manufactured by Tokyo Chemical Industry Co., Ltd.

[0075] 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, and 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene. Examples of suitable biguanide include 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, and 1-(o-tolyl)biguanide. Of these, dicyandiamide and 1,5,7-triazabicyclo[4.4.0]dec-5-ene are preferred.

[0076] Examples of phosphorus-based curing accelerators include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate, with triphenylphosphine and tetrabutylphosphonium decanoate being preferred.

[0077] Examples of metal-based curing accelerators include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organic cobalt complexes such as cobalt(II) acetylacetonate and cobalt(III) acetylacetonate, organic copper complexes such as copper(II) acetylacetonate, organic zinc complexes such as zinc(II) acetylacetonate, organic iron complexes such as iron(III) acetylacetonate, organic nickel complexes such as nickel(II) acetylacetonate, and organic manganese complexes such as manganese(II) acetylacetonate. Examples of organometallic salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

[0078] From the viewpoint of significantly achieving the desired effects of the present invention, the content of component (D) is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.3% by mass or more, and is preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 1.5% by mass or less, or 1% by mass or less, when the resin component in the resin composition is taken as 100% by mass.

[0079] From the viewpoint of significantly achieving the desired effects of the present invention, the content of component (D) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more, and is preferably 5% by mass or less, more preferably 1% by mass or less, and even more preferably 0.5% by mass or less, based on 100% by mass of the non-volatile components in the resin composition.

[0080] When the content of the (D) component when the nonvolatile components in the resin composition are taken as 100% by mass is d and the content of the (C) component when the nonvolatile components in the resin composition are taken as 100% by mass is c, from the viewpoint of obtaining a cured product with excellent crack resistance, c / d is preferably 0.1 or more, more preferably 0.5 or more, and even more preferably 1 or more, and is preferably 30 or less, more preferably 18 or less, and even more preferably 10 or less, 5 or less, 4 or less, or 3 or less.

[0081] When the content of component (B) is b when the nonvolatile components in the resin composition are 100 mass %, b / (c+d) is preferably 1 or more, more preferably 5 or more, even more preferably 10 or more, or 15 or more, and is preferably 150 or less, more preferably 50 or less, even more preferably 30 or less, 25 or less, or 20 or less. Because the resin composition of the present invention contains a combination of components (C) and (D), it is possible to obtain a cured product with excellent crack resistance and peel strength even if the content of component (B) is increased in order to lower the dielectric dissipation factor.

[0082] <(E) Inorganic filler> In addition to the components described above, the resin composition may contain an inorganic filler (E) as an optional component. By including the inorganic filler (E) in the resin composition, it becomes possible to obtain a cured product with excellent dielectric properties.

[0083] Inorganic compounds are used as inorganic fillers. Examples of inorganic filler materials include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium titanate zirconate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica is particularly preferred. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Spherical silica is preferred. (E) The inorganic fillers may be used alone or in combination of two or more.

[0084] (E) Examples of commercially available inorganic fillers include "SP60-05" and "SP507-05" manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YC100C," "YA050C," "YA050C-MJE," "YA010C," "SC2500SQ," "SO-C4," "SO-C2," and "SO-C1" manufactured by Admatechs Co., Ltd.; "UFP-30," "DAW-03," and "FB-105FD" manufactured by Denka Co., Ltd.; "Silfil NSS-3N," "Silfil NSS-4N," and "Silfil NSS-5N" manufactured by Tokuyama Corporation; "Cellphears" and "MGH-005" manufactured by Taiheiyo Cement Corporation; and "Sferique" and "BA-1" manufactured by JGC Catalysts and Chemicals Co., Ltd.

[0085] From the viewpoint of significantly achieving the desired effects of the present invention, the average particle size of (E) the inorganic filler is preferably 0.01 μm or more, more preferably 0.05 μm or more, particularly preferably 0.1 μm or more, and is preferably 5 μm or less, more preferably 2 μm or less, and even more preferably 1 μm or less.

[0086] (E) The average particle size of inorganic fillers can be measured using a laser diffraction / scattering method based on Mie scattering theory. Specifically, a volumetric particle size distribution of the inorganic filler is created using a laser diffraction / scattering particle size distribution analyzer, and the median diameter is used as the average particle size. A measurement sample can be prepared by weighing 100 mg of inorganic filler and 10 g of methyl ethyl ketone into a vial and dispersing it ultrasonically for 10 minutes. The volumetric particle size distribution of the inorganic filler is measured using a laser diffraction particle size distribution analyzer with blue and red light source wavelengths using a flow cell system, and the average particle size is calculated as the median diameter from the particle size distribution obtained. Examples of laser diffraction particle size distribution analyzers include the LA-960 manufactured by Horiba, Ltd. and the SALD-2200 manufactured by Shimadzu Corporation.

[0087] The specific surface area of ​​the (E) inorganic filler is preferably 1 m² from the viewpoint of significantly achieving the desired effects of the present invention. 2 / g or more, more preferably 2m 2 / g or more, particularly preferably 3m2 / g or more. There is no particular upper limit, but it is preferably 60m 2 / g or less, 50m 2 / g or less or 40m 2 The specific surface area is measured by using a BET fully automatic specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech Co., Ltd.) to adsorb nitrogen gas onto the surface of the sample and calculate the specific surface area using the BET multipoint method.

[0088] (E) The inorganic filler is preferably treated with a surface treatment agent to improve moisture resistance and dispersibility. Examples of surface treatment agents include fluorine-containing silane coupling agents such as 3,3,3-trifluoropropyltrimethoxysilane; aminosilane coupling agents such as 3-aminopropyltriethoxysilane, N-phenyl-8-aminooctyltrimethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane; epoxysilane coupling agents such as 3-glycidoxypropyltrimethoxysilane; mercaptosilane coupling agents such as 3-mercaptopropyltrimethoxysilane; silane coupling agents; alkoxysilanes such as phenyltrimethoxysilane; organosilazane compounds such as hexamethyldisilazane; and titanate coupling agents. Furthermore, the surface treatment agents may be used alone or in any combination of two or more.

[0089] Examples of commercially available surface treatment agents include Shin-Etsu Chemical Co., Ltd.'s "KBM403" (3-glycidoxypropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM803" (3-mercaptopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "SZ-31" (hexamethyldisilazane), Shin-Etsu Chemical Co., Ltd.'s "KBM103" (phenyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM-4803" (long-chain epoxy-type silane coupling agent), and Shin-Etsu Chemical Co., Ltd.'s "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane).

[0090] The degree of surface treatment with the surface treatment agent is preferably within a predetermined range from the viewpoint of improving the dispersibility of the inorganic filler. Specifically, 100 parts by mass of the inorganic filler is preferably surface-treated with 0.2 to 5 parts by mass of the surface treatment agent, more preferably 0.2 to 3 parts by mass, and even more preferably 0.3 to 2 parts by mass.

[0091] The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of ​​the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of ​​the inorganic filler is set to 0.02 mg / m 2 More than 0.1 mg / m is preferable. 2 More preferably, 0.2 mg / m or more 2 On the other hand, from the viewpoint of suppressing an increase in the melt viscosity of the resin varnish and the melt viscosity in the form of a sheet, it is more preferable that the amount of the resin varnish is 1 mg / m 2 Less than 0.8 mg / m is preferred 2 Less than 0.5 mg / m is more preferable. 2 The following is even more preferred:

[0092] (E) The amount of carbon per unit surface area of ​​the inorganic filler can be measured after the surface-treated inorganic filler is washed with a solvent (e.g., methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler that has been surface-treated with a surface treatment agent, and ultrasonic cleaning is performed at 25°C for 5 minutes. After removing the supernatant and drying the solid content, the amount of carbon per unit surface area of ​​the inorganic filler can be measured using a carbon analyzer. The carbon analyzer that can be used is the "EMIA-320V" manufactured by Horiba, Ltd.

[0093] From the viewpoint of significantly obtaining the effects of the present invention, the content of the (E) inorganic filler is preferably 60% by mass or more, more preferably 70% by mass or more, and even more preferably 75% by mass or more, and is preferably 90% by mass or less, preferably 85% by mass or less, and preferably 80% by mass or less, when the non-volatile components in the resin composition are taken as 100% by mass.

[0094] <(F)Thermoplastic resin> The resin composition of the present invention may further contain a thermoplastic resin (F) as an optional component. The thermoplastic resin (F) as component (F) does not include those corresponding to the above-mentioned components (A) to (D).

[0095] Examples of (F) thermoplastic resins include polyimide resins, phenoxy resins, polyvinyl acetal resins, polyolefin resins, polybutadiene resins, polyamideimide resins, polyetherimide resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, polycarbonate resins, polyetheretherketone resins, and polyester resins. In one embodiment, the (F) thermoplastic resin preferably contains a thermoplastic resin selected from the group consisting of polyimide resins and phenoxy resins, and more preferably contains a phenoxy resin. Furthermore, one type of thermoplastic resin may be used alone, or two or more types may be used in combination.

[0096] Specific examples of polyimide resins include "SLK-6100" manufactured by Shin-Etsu Chemical Co., Ltd., and "Rikacoat SN20" and "Rikacoat PN20" manufactured by New Japan Chemical Co., Ltd.

[0097] Examples of phenoxy resins include phenoxy resins having one or more skeletons selected from the group consisting of bisphenol A, bisphenol F, bisphenol S, bisphenolacetophenone, novolac, biphenyl, fluorene, dicyclopentadiene, norbornene, naphthalene, anthracene, adamantane, terpene, and trimethylcyclohexane. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group.

[0098] Specific examples of phenoxy resins include "1256" and "4250" manufactured by Mitsubishi Chemical Corporation (both of which are phenoxy resins containing a bisphenol A skeleton); "YX8100" manufactured by Mitsubishi Chemical Corporation (phenoxy resin containing a bisphenol S skeleton); "YX6954" manufactured by Mitsubishi Chemical Corporation (phenoxy resin containing a bisphenol acetophenone skeleton); "FX280" and "FX293" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.; and "YL7500BH30," "YX6954BH30," "YX7553," "YX7553BH30," "YL7769BH30," "YL6794," "YL7213," "YL7290," "YL7482," and "YL7891BH30" manufactured by Mitsubishi Chemical Corporation.

[0099] Examples of polyvinyl acetal resins include polyvinyl formal resins and polyvinyl butyral resins, with polyvinyl butyral resins being preferred. Specific examples of polyvinyl acetal resins include Denka Butyral 4000-2, Denka Butyral 5000-A, Denka Butyral 6000-C, and Denka Butyral 6000-EP, manufactured by Denki Kagaku Kogyo Co., Ltd.; and S-LEC BH series, BX series (e.g., BX-5Z), KS series (e.g., KS-1), BL series, and BM series, manufactured by Sekisui Chemical Co., Ltd.

[0100] Examples of polyolefin resins include ethylene copolymer resins such as low-density polyethylene, very low-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-methyl acrylate copolymer; and polyolefin polymers such as polypropylene and ethylene-propylene block copolymer.

[0101] Examples of polybutadiene resins include hydrogenated polybutadiene skeleton-containing resins, hydroxy group-containing polybutadiene resins, phenolic hydroxy group-containing polybutadiene resins, carboxy group-containing polybutadiene resins, acid anhydride group-containing polybutadiene resins, epoxy group-containing polybutadiene resins, isocyanate group-containing polybutadiene resins, urethane group-containing polybutadiene resins, and polyphenylene ether-polybutadiene resins.

[0102] Specific examples of polyamide-imide resins include "Vylomax HR11NN" and "Vylomax HR16NN" manufactured by Toyobo Co., Ltd. Specific examples of polyamide-imide resins also include modified polyamide-imides such as "KS9100" and "KS9300" (polysiloxane skeleton-containing polyamide-imides) manufactured by Hitachi Chemical Co., Ltd.

[0103] A specific example of the polyethersulfone resin is "PES5003P" manufactured by Sumitomo Chemical Co., Ltd.

[0104] Specific examples of polysulfone resins include polysulfones "P1700" and "P3500" manufactured by Solvay Advanced Polymers.

[0105] A specific example of the polyphenylene ether resin is NORYL SA90 manufactured by SABIC, etc. A specific example of the polyetherimide resin is ULTEM manufactured by GE, etc.

[0106] Examples of polycarbonate resins include hydroxyl group-containing carbonate resins, phenolic hydroxyl group-containing carbonate resins, carboxyl group-containing carbonate resins, acid anhydride group-containing carbonate resins, isocyanate group-containing carbonate resins, and urethane group-containing carbonate resins. Specific examples of polycarbonate resins include "FPC0220" manufactured by Mitsubishi Gas Chemical Company, Inc., "T6002" and "T6001" (polycarbonate diols) manufactured by Asahi Kasei Chemicals Corporation, and "C-1090," "C-2090," and "C-3090" (polycarbonate diols) manufactured by Kuraray Co., Ltd. Specific examples of polyether ether ketone resins include "Sumiploy K" manufactured by Sumitomo Chemical Co., Ltd.

[0107] Examples of polyester resins include polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin, polybutylene naphthalate resin, polytrimethylene terephthalate resin, polytrimethylene naphthalate resin, and polycyclohexane dimethyl terephthalate resin.

[0108] From the viewpoint of significantly achieving the effects of the present invention, the weight average molecular weight (Mw) of the (F) thermoplastic resin is preferably 5,000 or more, more preferably 8,000 or more, even more preferably 10,000 or more, and particularly preferably 20,000 or more, and is preferably 100,000 or less, more preferably 70,000 or less, even more preferably 60,000 or less, and particularly preferably 50,000 or less.

[0109] From the viewpoint of significantly achieving the desired effects of the present invention, the content of the (F) thermoplastic resin, when the resin component in the resin composition is taken as 100% by mass, is preferably 0.5% by mass or more, more preferably 1% by mass or more, even more preferably 1.5% by mass or more, and is preferably 6% by mass or less, preferably 5% by mass or less, more preferably 4% by mass or less, even more preferably 3% by mass or less.

[0110] From the viewpoint of significantly achieving the desired effects of the present invention, the content of the (F) thermoplastic resin is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more, and is preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 2% by mass or less, when the non-volatile components in the resin composition are taken as 100% by mass.

[0111] <(G) Hardener> In addition to the above-described components, the resin composition may further contain a (G) curing agent as an optional component. The (G) curing agent as this component (G) does not include those corresponding to the above-described components (A) to (F). The (G) curing agent typically reacts with the (A) epoxy resin to form a bond, thereby curing the resin composition. Examples of the (G) curing agent include phenolic curing agents, naphthol curing agents, benzoxazine curing agents, cyanate ester curing agents, and carbodiimide curing agents. Among these, from the viewpoint of improving insulation reliability, the (G) curing agent is preferably one or more of phenolic curing agents, naphthol curing agents, and carbodiimide curing agents, more preferably either a phenolic curing agent or a naphthol curing agent, and even more preferably contains a phenolic curing agent. The (G) curing agents may be used alone or in combination of two or more.

[0112] As the phenol-based curing agent and naphthol-based curing agent, a phenol-based curing agent having a novolac structure or a naphthol-based curing agent having a novolac structure is preferred from the viewpoint of heat resistance and water resistance. Furthermore, from the viewpoint of adhesion to the conductor layer, a nitrogen-containing phenol-based curing agent is preferred, and a triazine skeleton-containing phenol-based curing agent is more preferred.

[0113] Specific examples of phenol-based curing agents and naphthol-based curing agents include "MEH-7700," "MEH-7810," and "MEH-7851" manufactured by Meiwa Chemical Industry Co., Ltd.; "NHN," "CBN," and "GPH" manufactured by Nippon Kayaku Co., Ltd.; "SN170," "SN180," "SN190," "SN475," "SN485," "SN495," "SN-495V," "SN375," and "SN395" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.; and "TD-2090," "LA-7052," "LA-7054," "LA-1356," "LA3018-50P," and "EXB-9500" manufactured by DIC Corporation.

[0114] Specific examples of benzoxazine-based curing agents include "HFB2006M" manufactured by Showa Polymer Co., Ltd., and "Pd" and "Fa" manufactured by Shikoku Chemical Industry Co., Ltd.

[0115] Examples of cyanate ester curing agents include bifunctional cyanate resins such as bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4'-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4-cyanatephenyl)thioether, and bis(4-cyanatephenyl)ether; multifunctional cyanate resins derived from phenol novolac and cresol novolac; and prepolymers in which these cyanate resins are partially converted to triazine. Specific examples of cyanate ester curing agents include "PT30" and "PT60" (phenol novolac type multifunctional cyanate ester resins), "ULL-950S" (multifunctional cyanate ester resin), "BA230" and "BA230S75" (prepolymers in which part or all of bisphenol A dicyanate has been triazine converted to a trimer), all of which are manufactured by Lonza Japan.

[0116] Specific examples of carbodiimide curing agents include "V-03" and "V-07" manufactured by Nisshinbo Chemical Inc.

[0117] When a curing agent is included as component (G), the quantitative ratio of the (A) epoxy resin to the (B) active ester curing agent and (G) curing agent, expressed as the ratio of [total number of epoxy groups in the epoxy resin] to [total number of active groups in the (B) active ester curing agent and (G) curing agent], is preferably in the range of 1:0.01 to 1:5, more preferably 1:0.3 to 1:3, and even more preferably 1:0.5 to 1:2. Here, the "number of epoxy groups in the epoxy resin" refers to the sum of all values ​​obtained by dividing the mass of the non-volatile components of the epoxy resin present in the resin composition by the epoxy equivalent. Furthermore, the "number of active groups in the (B) active ester curing agent and (G) curing agent" refers to the sum of all values ​​obtained by dividing the mass of the non-volatile components of the active ester curing agent and curing agent present in the resin composition by the active group equivalent. By maintaining the quantitative ratio of the (B) component and the (G) component to the epoxy resin within this range, the effects of the present invention can be significantly achieved.

[0118] When a curing agent is included as component (G), the ratio of the amount of epoxy resin to all (G) curing agents, expressed as the ratio of [total number of epoxy groups in the epoxy resin] to [total number of active groups in the (G) curing agent], is preferably in the range of 1:0.01 to 1:1, more preferably 1:0.03 to 1:0.5, and even more preferably 1:0.05 to 1:0.3. Here, the "number of active groups in the (G) curing agent" refers to the total value obtained by dividing the mass of the non-volatile components of the (G) curing agent present in the resin composition by the active group equivalent. By maintaining the ratio of the amount of epoxy resin to the curing agent as component (G) within this range, the effects of the present invention can be significantly achieved.

[0119] From the viewpoint of significantly achieving the desired effects of the present invention, the content of component (G) is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 3% by mass or more, and is preferably 15% by mass or less, preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably 7% by mass or less, when the resin component in the resin composition is taken as 100% by mass.

[0120] To significantly achieve the desired effects of the present invention, the content of the (G) curing agent is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and even more preferably 0.3% by mass or more, based on 100% by mass of the nonvolatile components in the resin composition. The upper limit is preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 2% by mass or less.

[0121] <(H) Radical Polymerizable Compound> The resin composition of the present invention may further contain a (H) radical polymerizable compound as an optional component. The (H) radical polymerizable resin as component (H) does not include those corresponding to the above-mentioned components (A) to (G). The (H) radical polymerizable compound may be used alone or in any combination of two or more.

[0122] In one embodiment, the (H) radical polymerizable compound is a radical polymerizable compound having an ethylenically unsaturated bond. The (H) radical polymerizable compound is not particularly limited, but may have a radical polymerizable group such as an unsaturated hydrocarbon group such as an allyl group, a 3-cyclohexenyl group, a 3-cyclopentenyl group, a p-vinylphenyl group, a m-vinylphenyl group, or an o-vinylphenyl group; or an α,β-unsaturated carbonyl group such as an acryloyl group, a methacryloyl group, or a maleimide group (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl group). The (H) radical polymerizable compound preferably has two or more radical polymerizable groups.

[0123] The (H) radical polymerizable compound may be, for example, a (meth)acrylic radical polymerizable compound, a styrene radical polymerizable compound, an allyl radical polymerizable compound, or a maleimide radical polymerizable compound.

[0124] The (meth)acrylic radical polymerizable compound is, for example, a compound having one or more, preferably two or more, acryloyl groups and / or methacryloyl groups. Examples of the (meth)acrylic radical polymerizable compound include cyclohexane-1,4-dimethanol di(meth)acrylate, cyclohexane-1,3-dimethanol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-octanediol di(meth)acrylate, 1,6-octanedi ...8-octanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1 Low molecular weight (molecular weight less than 1000) aliphatic (meth)acrylic acid ester compounds such as nanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, glycerin tri(meth)acrylate, and pentaerythritol tetra(meth)acrylate; dioxane glycol di(meth)acrylate, 3,6-dioxa-1,8-octanediol di(meth)acrylate, Examples of the ether-containing (meth)acrylic acid ester compounds include low molecular weight (molecular weight less than 1000) ether-containing (meth)acrylic acid ester compounds such as bis(meth)acrylate, 3,6,9-trioxaundecane-1,11-diol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene, ethoxylated bisphenol A di(meth)acrylate, and propoxylated bisphenol A di(meth)acrylate; low molecular weight (molecular weight less than 1000) isocyanurate-containing (meth)acrylic acid ester compounds such as tris(3-hydroxypropyl)isocyanurate tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, and ethoxylated isocyanuric acid tri(meth)acrylate; and high molecular weight (molecular weight 1000 or more) acrylic acid ester compounds such as (meth)acrylic-modified polyphenylene ether resins.Examples of commercially available (meth)acrylic radically polymerizable compounds include "A-DOG" (dioxane glycol diacrylate) manufactured by Shin-Nakamura Chemical Co., Ltd., "DCP-A" (tricyclodecane dimethanol diacrylate) and "DCP" (tricyclodecane dimethanol dimethacrylate) manufactured by Kyoeisha Chemical Co., Ltd., "KAYARAD R-684" (tricyclodecane dimethanol diacrylate) and "KAYARAD R-604" (dioxane glycol diacrylate) manufactured by Nippon Kayaku Co., Ltd., and "SA9000" and "SA9000-111" (methacrylic-modified polyphenylene ether) manufactured by SABIC Innovative Plastics.

[0125] The styrene radical polymerizable compound is, for example, a compound having one or more, preferably two or more, vinyl groups directly bonded to an aromatic carbon atom. Examples of the styrene radical polymerizable compound include low molecular weight (molecular weight less than 1000) styrene compounds such as divinylbenzene, 2,4-divinyltoluene, 2,6-divinylnaphthalene, 1,4-divinylnaphthalene, 4,4'-divinylbiphenyl, 1,2-bis(4-vinylphenyl)ethane, 2,2-bis(4-vinylphenyl)propane, and bis(4-vinylphenyl)ether; and high molecular weight (molecular weight 1000 or more) styrene compounds such as vinylbenzyl-modified polyphenylene ether resin and styrene-divinylbenzene copolymer. Examples of commercially available styrene-based radically polymerizable compounds include "ODV-XET(X03)", "ODV-XET(X04)", and "ODV-XET(X05)" (styrene-divinylbenzene copolymers) manufactured by Nippon Steel Chemical & Material Co., Ltd., and "OPE-2St 1200" and "OPE-2St 2200" (vinylbenzyl-modified polyphenylene ether resins) manufactured by Mitsubishi Gas Chemical Company, Inc.

[0126] The allyl radical polymerizable compound is, for example, a compound having one or more, preferably two or more, allyl groups. Examples of allyl radical polymerizable compounds include aromatic carboxylic acid allyl ester compounds such as diallyl diphenate, triallyl trimellitate, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl 2,6-naphthalenedicarboxylate, and diallyl 2,3-naphthalenecarboxylate; isocyanuric acid allyl ester compounds such as 1,3,5-triallyl isocyanurate and 1,3-diallyl-5-glycidyl isocyanurate; epoxy-containing aromatic allyl compounds such as 2,2-bis[3-allyl-4-(glycidyloxy)phenyl]propane; benzoxazine-containing aromatic allyl compounds such as bis[3-allyl-4-(3,4-dihydro-2H-1,3-benzoxazin-3-yl)phenyl]methane; ether-containing aromatic allyl compounds such as 1,3,5-triallyl ether benzene; and allyl silane compounds such as diallyldiphenylsilane. Commercially available allyl radical polymerizable compounds include "TAIC" (1,3,5-triallyl isocyanurate) manufactured by Nippon Kasei Chemical Industry Co., Ltd., "DAD" (diallyl diphenate) manufactured by Nisshoku Techno Fine Chemical Co., Ltd., "TRIAM-705" (triallyl trimellitate) manufactured by Wako Pure Chemical Industries, Ltd., "DAND" (2,3-diallyl naphthalenecarboxylate) manufactured by Nippon Distillation Industry Co., Ltd., "ALP-d" (bis[3-allyl-4-(3,4-dihydro-2H-1,3-benzoxazin-3-yl)phenyl]methane) manufactured by Shikoku Chemical Industry Co., Ltd., "RE-810NM" (2,2-bis[3-allyl-4-(glycidyloxy)phenyl]propane) manufactured by Nippon Kayaku Co., Ltd., and "DA-MGIC" (1,3-diallyl-5-glycidyl isocyanurate) manufactured by Shikoku Chemical Industry Co., Ltd.

[0127] The maleimide radical polymerizable compound is, for example, a compound having one or more, preferably two or more maleimide groups. The maleimide-based radical polymerizable compound may be an aliphatic maleimide compound containing an aliphatic amine skeleton, or an aromatic maleimide compound containing an aromatic amine skeleton. Commercially available products include, for example, "SLK-2600" manufactured by Shin-Etsu Chemical Co., Ltd.; "BMI-1500," "BMI-1700," "BMI-3000J," "BMI-689," and "BMI-2500" (dimer diamine structure-containing maleimide compounds) manufactured by Designer Molercules Inc.; "BMI-6100" (aromatic maleimide compound) manufactured by Designer Molercules Inc.; "MIR-5000-60T" and "MIR-3000-70MT" (biphenylaralkyl maleimide compounds) manufactured by Nippon Kayaku Co., Ltd.; "BMI-70" and "BMI-80" manufactured by K.I. Chemical Industry Co., Ltd.; and "BMI-2300" and "BMI-TMH" manufactured by Daiwa Kasei Kogyo Co., Ltd. Furthermore, as the maleimide radical polymerizable compound, a maleimide resin (maleimide compound containing an indane ring skeleton) disclosed in the Japan Institute of Invention and Innovation's Technical Disclosure No. 2020-500211 may be used.

[0128] The ethylenically unsaturated bond equivalent of the radically polymerizable compound (H) is preferably 20 g / eq. to 3000 g / eq., more preferably 50 g / eq. to 2500 g / eq., even more preferably 70 g / eq. to 2000 g / eq., and particularly preferably 90 g / eq. to 1500 g / eq. The ethylenically unsaturated bond equivalent is the mass of the radically polymerizable compound per equivalent of the ethylenically unsaturated bond.

[0129] The weight average molecular weight (Mw) of the radical polymerizable compound (H) is preferably 40,000 or less, more preferably 10,000 or less, even more preferably 5,000 or less, and particularly preferably 3,000 or less. The lower limit is not particularly limited, but may be, for example, 150 or more.

[0130] From the viewpoint of significantly achieving the desired effects of the present invention, the content of component (H) is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more, and is preferably 15% by mass or less, preferably 10% by mass or less, and more preferably 8% by mass or less, when the resin component in the resin composition is taken as 100% by mass.

[0131] From the viewpoint of significantly achieving the desired effects of the present invention, the content of component (H) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more, and is preferably 5% by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less, when the non-volatile components in the resin composition are taken as 100% by mass.

[0132] <(I) Other additives> In addition to the components described above, the resin composition may further contain other additives as optional components. Examples of such additives include elastomers (excluding those corresponding to component (F)), organic fillers, thickeners, antifoaming agents, leveling agents, adhesion promoters, and flame retardants. These may be used alone or in combination of two or more in any ratio.

[0133] The resin composition can be produced, for example, by mixing the above-mentioned components in any order. Furthermore, heating and / or cooling may be performed by appropriately adjusting the temperature during the process of mixing the components. Furthermore, stirring may be performed using a stirring device such as a mixer during or after mixing the components to uniformly disperse the components. Furthermore, the resin composition may be subjected to a degassing treatment, if necessary.

[0134] <Physical properties and applications of resin compositions> The resin composition contains a combination of components (A), (B), (C), and (D), and therefore can provide a cured product with excellent crack resistance, high peel strength, and low dielectric loss tangent. Furthermore, the resin composition can also provide a cured product with low surface roughness after roughening treatment.

[0135] The cured product obtained by curing the resin composition at 100°C for 30 minutes, 170°C for 30 minutes, and then 190°C for 1 hour exhibits excellent crack resistance. This results in an insulating layer with excellent crack resistance. Specifically, a layer made of the cured product of the resin composition is formed on an inner layer circuit board on which 25 copper patterns have been formed. The layer made of the cured product is subjected to a roughening treatment, and a copper plating layer is formed on the roughened surface. At this time, the number of cracks present in the 25 copper patterns is preferably 2 or less, more preferably 1 or less, and even more preferably 0. Crack resistance can be measured by the method described in the Examples below.

[0136] A cured product obtained by curing the resin composition at 100°C for 30 minutes, 170°C for 30 minutes, and then 190°C for 1 hour can have high peel strength with the plating. Therefore, when an insulating layer is formed using this cured product, an insulating layer with high peel strength with the conductor layer can be obtained. The peel strength between the insulating layer and the conductor layer is preferably 0.4 kgf / cm or more, more preferably 0.5 kgf / cm or more. The upper limit of the peel strength is not particularly limited, but can be, for example, 10.0 kgf / cm or less. The peel strength can be measured by the method described in the Examples below.

[0137] The cured product obtained by thermally curing the resin composition at 200°C for 90 minutes has a low dielectric loss tangent. Therefore, when an insulating layer is formed using this cured product, an insulating layer with a low dielectric loss tangent can be obtained. The dielectric loss tangent of the cured product is preferably less than 0.0035, more preferably less than 0.0030, and even more preferably 0.0030 or less, less than 0.0030, 0.0025 or less, or less than 0.0025. The lower limit is not particularly limited, but can be 0.0001 or more. The dielectric loss tangent can be measured by the method described in the Examples below.

[0138] A cured product of the resin composition usually exhibits the characteristic that the arithmetic mean roughness (Ra) of the insulating layer surface after roughening treatment is low. The arithmetic mean roughness (Ra) of the insulating layer surface after roughening treatment is preferably less than 400 nm, more preferably less than 200 nm, even more preferably 100 nm or less, and even more preferably less than 100 nm. 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) can be measured by the method described in the examples below.

[0139] The resin composition of the present invention is suitable as a resin composition for insulating applications, and particularly suitable as a resin composition for forming an insulating layer. Therefore, for example, the resin composition is suitable as a resin composition for forming an insulating layer of a printed wiring board (a resin composition for forming an insulating layer of a printed wiring board). The resin composition is suitable as a resin composition for forming an interlayer insulating layer of a printed wiring board (a resin composition for forming an interlayer insulating layer of a printed wiring board). The resin composition is also suitable as a resin composition for forming an insulating layer (a resin composition for forming an insulating layer for forming a conductor layer) to form a conductor layer (including a rewiring layer) formed on an insulating layer. The resin composition can also be used in a wide range of applications where a resin composition can be used, such as sheet-like laminate materials such as resin sheets and prepregs, solder resists, underfill materials, die bonding materials, semiconductor encapsulants, hole-filling resins, component-embedding resins, multi-chip packages, package-on-packages, wafer-level packages, panel-level packages, and system-in-packages.

[0140] Furthermore, for example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition according to this embodiment is also suitable as a resin composition for forming a rewiring formation layer as an insulating layer for forming a rewiring layer (resin composition for forming a rewiring formation layer), and as a resin composition for encapsulating a semiconductor chip (resin composition for encapsulating a semiconductor chip). When a semiconductor chip package is manufactured, a rewiring layer may be further formed on the encapsulation layer. (1) a step of laminating a temporary fixing film on a substrate; (2) a step of temporarily fixing a semiconductor chip on a temporary fixing film; (3) forming an encapsulation layer on the semiconductor chip; (4) peeling the substrate and the temporary fixing film from the semiconductor chip; (5) forming a rewiring formation layer as an insulating layer on the surface of the semiconductor chip from which the base material and the temporary fixing film have been peeled off; and (6) A step of forming a rewiring layer as a conductor layer on the rewiring formation layer.

[0141] The above-mentioned resin composition can also be used when the printed wiring board is a circuit board with built-in components.

[0142] [Resin sheet] The resin sheet of the present invention includes a support and a resin composition layer formed from the resin composition of the present invention and provided on the support.

[0143] The thickness of the resin composition layer is preferably 50 μm or less, more preferably 40 μm or less, and even more preferably 30 μm or less, from the viewpoint of making the printed wiring board thinner and being able to provide a cured product of the resin composition that has excellent insulating properties even when the cured product is thin. The lower limit of the thickness of the resin composition layer is not particularly limited, but can usually be 5 μm or more.

[0144] Examples of the support include films made of plastic materials, metal foils, and release papers, with films made of plastic materials and metal foils being preferred.

[0145] When a film made of a plastic material is used as the support, examples of the plastic material include polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"), polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylics such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide, etc. Among these, polyethylene terephthalate and polyethylene naphthalate are preferred, with inexpensive polyethylene terephthalate being particularly preferred.

[0146] When a metal foil is used as the support, examples of the metal foil include copper foil and aluminum foil, with copper foil being preferred. The copper foil may be a foil made of a single metal, copper, or an alloy of copper and another metal (e.g., tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.).

[0147] The surface of the support that is to be bonded to the resin composition layer may be subjected to a matte treatment, a corona treatment, or an antistatic treatment.

[0148] The support may also be a support with a release layer, which has a release layer on the surface that bonds to the resin composition layer. Examples of the release agent used in the release layer of the support with a release layer include one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. Commercially available products may also be used as the support with a release layer, including, for example, "SK-1," "AL-5," and "AL-7" manufactured by Lintec Corporation, "Lumirror T60" manufactured by Toray Industries, Inc., "Purex" manufactured by Teijin Limited, and "Uni-Peel" manufactured by Unitika Limited, which are PET films having a release layer primarily composed of an alkyd resin-based release agent.

[0149] The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, more preferably 10 μm to 60 μm. When a support with a release layer is used, it is preferable that the thickness of the entire support with a release layer is in the above range.

[0150] In one embodiment, the resin sheet may further include other layers as necessary. Examples of such other layers include a protective film conforming to the support and provided on the surface of the resin composition layer that is not bonded to the support (i.e., the surface opposite the support). The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating the protective film, adhesion of dust and the like to the surface of the resin composition layer and scratches can be suppressed.

[0151] The resin sheet can be produced, for example, by preparing a resin varnish by dissolving a resin composition in an organic solvent, applying this resin varnish to a support using a die coater or the like, and then drying it to form a resin composition layer.

[0152] Examples of organic solvents include ketones such as acetone, methyl ethyl ketone (MEK), and cyclohexanone; acetate esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitols such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; and amide solvents such as dimethylformamide, dimethylacetamide (DMAc), and N-methylpyrrolidone. The organic solvents may be used alone or in combination of two or more.

[0153] Drying may be carried out by known methods such as heating or hot air blowing. Drying conditions are not particularly limited, but drying is carried out so that the content of organic solvent in the resin composition layer becomes 10% by mass or less, preferably 5% by mass or less. Although this varies depending on the boiling point of the organic solvent in the resin varnish, for example, when a resin varnish containing 30% by mass to 60% by mass of organic solvent is used, the resin composition layer can be formed by drying at 50°C to 150°C for 3 to 10 minutes.

[0154] The resin sheet can be stored in a rolled state. When the resin sheet has a protective film, it can be used by peeling off the protective film.

[0155] [Printed wiring board] A printed wiring board according to one embodiment of the present invention includes an insulating layer formed of a cured product obtained by curing the above-described resin composition.

[0156] The printed wiring board can be produced, for example, by using the above-mentioned resin sheet by a method including the following steps (I) and (II). (I) A step of laminating a resin sheet on an inner layer substrate so that the resin composition layer of the resin sheet is bonded to the inner layer substrate. (II) Step of curing the resin composition layer to form an insulating layer

[0157] The "inner layer substrate" used in step (I) is a member that will become the substrate of a printed wiring board, and examples thereof include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, and thermosetting polyphenylene ether substrates. The substrate may have a conductor layer on one or both sides, and this conductor layer may be patterned. An inner layer substrate having a conductor layer formed on one or both sides of the substrate is sometimes referred to as an "inner layer circuit board." Furthermore, intermediate products on which an insulating layer and / or a conductor layer is to be further formed during the production of a printed wiring board are also included in the "inner layer substrate." When the printed wiring board is a circuit board with built-in components, an inner layer substrate with built-in components may be used.

[0158] The inner layer substrate and the resin sheet can be laminated, for example, by thermocompression bonding the resin sheet to the inner layer substrate from the support side. Examples of a member for thermocompression bonding the resin sheet to the inner layer substrate (hereinafter also referred to as a "thermocompression bonding member") include a heated metal plate (such as a SUS plate) or a metal roll (such as a SUS roll). Note that rather than pressing the thermocompression bonding member directly onto the resin sheet, it is preferable to press it via an elastic material such as heat-resistant rubber so that the resin sheet can sufficiently conform to the surface irregularities of the inner layer substrate.

[0159] The lamination of the inner layer substrate and the resin sheet may be carried out by a vacuum lamination method. In the vacuum lamination method, the thermocompression temperature is preferably in the range of 60°C to 160°C, more preferably 80°C to 140°C, the thermocompression pressure is preferably in the range of 0.098MPa to 1.77MPa, more preferably 0.29MPa to 1.47MPa, and the thermocompression time is preferably in the range of 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. The lamination may be carried out under reduced pressure conditions, preferably at a pressure of 26.7hPa or less.

[0160] The lamination can be performed using a commercially available vacuum laminator, such as a vacuum pressure laminator manufactured by Meiki Seisakusho Co., Ltd., a vacuum applicator manufactured by Nikko Materials Co., Ltd., or a batch vacuum pressure laminator.

[0161] After lamination, the laminated resin sheets may be smoothed under atmospheric pressure, for example, by pressing a thermocompression member from the support side. The pressing conditions for the smoothing treatment may be the same as the thermocompression conditions for the lamination. The smoothing treatment may be performed using a commercially available laminator. Note that the lamination and smoothing treatment may be performed consecutively using the commercially available vacuum laminator.

[0162] The support may be removed between step (I) and step (II), or may be removed after step (II).

[0163] In step (II), the resin composition layer is cured to form an insulating layer made of a cured product of the resin composition. The curing conditions for the resin composition layer are not particularly limited, and the conditions employed for forming an insulating layer of a printed wiring board may be used. The resin composition layer may be cured by irradiation with active energy rays such as ultraviolet rays, but is usually thermally cured by heating.

[0164] For example, the thermal curing conditions for the resin composition layer vary depending on the type of resin composition, but in one embodiment, the curing temperature is preferably 120° C. to 240° C., more preferably 150° C. to 220° C., and even more preferably 170° C. to 210° C. The curing time is preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and even more preferably 15 minutes to 100 minutes.

[0165] Before thermally curing the resin composition layer, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermally curing the resin composition layer, the resin composition layer may be preheated at a temperature of 50°C to 120°C, preferably 60°C to 115°C, more preferably 70°C to 110°C for 5 minutes or more, preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and even more preferably 15 minutes to 100 minutes.

[0166] The method for producing a printed wiring board may further include the steps of (III) drilling holes in the insulating layer, (IV) roughening the insulating layer, and (V) forming a conductor layer. When the support is removed after step (II), the support may be removed between steps (II) and (III), between steps (III) and (IV), or between steps (IV) and (V). Furthermore, the formation of the insulating layer and the conductor layer in steps (I) to (V) may be repeated to form a multilayer wiring board, as necessary.

[0167] Step (III) is a step of drilling holes in the insulating layer, thereby forming holes such as via holes and through holes in the insulating layer. Step (III) may be performed using, for example, a drill, a laser, plasma, or the like, depending on the composition of the resin composition used to form the insulating layer. The dimensions and shape of the holes may be determined appropriately depending on the design of the printed wiring board.

[0168] Step (IV) is a step of roughening the insulating layer. Usually, smear removal is also performed in this step (IV). The procedure and conditions of the roughening treatment are not particularly limited. 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.

[0169] Examples of swelling solutions used in the roughening treatment include alkaline solutions and surfactant solutions, with alkaline solutions being preferred. Examples of alkaline solutions include sodium hydroxide solutions and potassium hydroxide solutions. Examples of commercially available swelling solutions include "Swelling Dip Securigance P" and "Swelling Dip Securigance SBU" manufactured by Atotech Japan. The swelling treatment using a swelling solution is not particularly limited, but can be carried out, for example, by immersing the insulating layer in a swelling solution at 30°C to 90°C for 1 to 20 minutes. From the viewpoint of suppressing swelling of the resin in the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling solution at 40°C to 80°C for 5 to 15 minutes.

[0170] Examples of oxidizing agents used in the roughening treatment include alkaline permanganate solutions prepared by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. Roughening treatment using an oxidizing agent such as alkaline permanganate solution is preferably carried out by immersing the insulating layer in an oxidizing agent solution heated to 60°C to 100°C for 10 to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Securigance P" manufactured by Atotech Japan.

[0171] The neutralizing solution used in the roughening treatment is preferably an acidic aqueous solution, and a commercially available product such as "Reduction Solution Securigant P" manufactured by Atotech Japan can be cited. Treatment with a neutralizing solution can be carried out by immersing the surface that has been roughened with an oxidizing agent in a neutralizing solution at 30°C to 80°C for 5 to 30 minutes. From the standpoint of workability, a preferred method is to immerse the object that has been roughened with an oxidizing agent in a neutralizing solution at 40°C to 70°C for 5 to 20 minutes.

[0172] In one embodiment, the arithmetic mean roughness Ra of the insulating layer surface after roughening treatment is preferably less than 400 nm, more preferably less than 200 nm, even more preferably 100 nm or less, and even more preferably less than 100 nm. 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 insulating layer surface can be measured using a non-contact surface roughness meter.

[0173] Step (V) is a step of forming a conductor layer, and the conductor layer is formed on the insulating layer. The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer contains one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. The conductor layer may be a single metal layer or an alloy layer. Examples of alloy layers include layers formed from alloys of two or more metals selected from the above group (e.g., nickel-chromium alloys, copper-nickel alloys, and copper-titanium alloys). Among these, from the viewpoints of versatility in forming the conductor layer, cost, ease of patterning, etc., a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of a nickel-chromium alloy, a copper-nickel alloy, or a copper-titanium alloy is preferred, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of a nickel-chromium alloy is more preferred, and a single metal layer of copper is even more preferred.

[0174] The conductor layer may have a single layer structure, or a multi-layer structure in which two or more single metal layers or alloy layers made of different types of metals or alloys are laminated. When the conductor layer has a multi-layer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc, or titanium, or an alloy layer of a nickel-chromium alloy.

[0175] The thickness of the conductor layer depends on the desired design of the printed wiring board, but is generally 3 μm to 35 μm, preferably 5 μm to 30 μm.

[0176] The conductor layer is preferably formed by plating. For example, a conductor layer having a desired wiring pattern can be formed by plating the surface of the insulating layer using a method such as a semi-additive method or a full-additive method. From the viewpoint of ease of production, the conductor layer is preferably formed by a semi-additive method. An example of forming a conductor layer by a semi-additive method will be described below.

[0177] 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, exposing a portion of the plating seed layer corresponding to the desired wiring pattern. A metal layer is formed on the exposed plating seed layer by electrolytic plating, and then the mask pattern is removed. Thereafter, unnecessary plating seed layer is removed by etching or the like, thereby forming a conductor layer having the desired wiring pattern.

[0178] [Semiconductor Devices] A semiconductor device according to one embodiment of the present invention includes the above-described printed wiring board, and can be manufactured using the above-described printed wiring board.

[0179] Examples of semiconductor devices include various semiconductor devices used in electrical appliances (for example, computers, mobile phones, digital cameras, and televisions) and vehicles (for example, motorcycles, automobiles, trains, ships, and aircraft). [Example]

[0180] The present invention will be specifically described below with reference to examples. However, the present invention is not limited to the following examples. In the following description, "parts" and "%" representing amounts mean "parts by mass" and "% by mass", respectively, unless otherwise specified. Furthermore, the operations described below were carried out in an environment of normal temperature and pressure, unless otherwise specified.

[0181] Example 1 15 parts of biphenyl epoxy resin (Nippon Kayaku Co., Ltd. "NC-3000H"), 5 parts of bisphenol epoxy resin (Nippon Steel Chemical & Material Co., Ltd. "ZX1059"), 2 parts of aminotriazine-based cresol novolac resin (DIC Corporation "LA-3018-50P"), 26 parts of active ester curing agent (DIC Corporation "HP-B-8151-62T", containing 62% solids by mass and 38% toluene by mass), 26 parts of phenoxy resin (Mitsubishi Chemical Corporation "YX6954BH30"), 15 parts of bisphenol epoxy resin (Nippon Steel Chemical & Material Co., Ltd. "ZX1059"), 2 parts of aminotriazine-based cresol novolac resin (DIC Corporation "LA-3018-50P"), 26 parts of active ester curing agent (DIC Corporation "HP-B-8151-62T", containing 62% solids by mass and 38% toluene by mass), 26 parts of phenoxy resin (Mitsubishi Chemical Corporation "YX6954BH30"), 26 parts of bisphenol A epoxy resin (Nippon Kayaku Co., Ltd. "ZX1059"), 2 parts of bisphenol B epoxy resin (Nippon Kayaku Co., Ltd. "ZX1059"), 2 parts of aminotriazine-based cresol novolac resin (DIC Corporation "LA-3018-50P"), 2 parts of bisphenol B epoxy resin (DIC Corporation "HP-B-8151-62T", containing 62% solids by mass and 38% toluene by mass), 26 parts of bisphenol A epoxy resin (Mitsubishi Chemical Corporation "YX6954BH30"), 26 parts of bisphenol B epoxy resin (Mitsubishi Chemical Corporation "YX69 ), 150 parts of spherical silica (100 parts of "SOC2" manufactured by Admatechs Co., Ltd. was surface-treated with 0.6 parts of a silane coupling agent having an N-phenyl-3-aminopropyl group ("KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd.), average particle size 0.5 μm), 0.2 parts of 4-dimethylaminopyridine ("DMAP" manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.5 parts of a curing accelerator ("G-8009L" manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), and the mixture was stirred at room temperature until a homogeneous solution was obtained, thereby obtaining a resin varnish.

[0182] The obtained resin varnish was applied to the release-treated surface of a PET film (thickness: 38 μm) using an applicator, and then dried for 180 seconds in a gear oven at 100° C. to volatilize the solvent. In this way, a resin sheet having a thickness of 25 μm and a resin composition on the PET film was obtained.

[0183] <Examples 2 to 19 and Comparative Examples 1 to 3> The components were mixed in the proportions shown in the table below and stirred at room temperature until a uniform solution was obtained to prepare a resin varnish. A resin sheet was also obtained in the same manner as in Example 1.

[0184] [Table 1]

[0185] [Table 2] *In the table, the contents of components (A) to (H) represent the contents when the total nonvolatile components in the resin composition is taken as 100 mass %.

[0186] The abbreviations in the table are as follows: Component (A) ZX1059: Bisphenol-type epoxy resin (Nippon Steel Chemical & Material Co., Ltd. "ZX1059") NC3000H: Biphenyl-type epoxy resin (Nippon Kayaku "NC3000H") (B) Component HP-B-8151-62T: Active ester curing agent (DIC Corporation "HP-B-8151-62T", containing 62% solids and 38% toluene) PC-1300-02-65MA: Active ester curing agent (Air Water Corporation's "PC-1300-02-65MA", containing 65% solids and 35% toluene) (C) Component P200H50: (Mitsubishi Chemical Corporation, compound represented by the following structural formula) [ka] G-8009L: (Dai-ichi Kogyo Seiyaku Co., Ltd., compound represented by the following structural formula) [ka] (D) Component DMAP: 4-dimethylaminopyridine ("DMAP" manufactured by Tokyo Chemical Industry Co., Ltd.) 1B2PZ: 1-benzyl-2-phenylimidazole (Shikoku Chemicals Corporation "1B2PZ") (E) Component SO-C2: Spherical silica (100 parts by mass of "SO-C2" manufactured by Admatechs Co., Ltd. was surface-treated with 0.6 parts by mass of a silane coupling agent having an N-phenyl-3-aminopropyl group ("KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd.), average particle size 0.5 μm) (F) Component YX7553BH30: Phenoxy resin (Mitsubishi Chemical Corporation's "YX7553BH30", containing 30% solids by mass, 35% methyl ethyl ketone, and 35% cyclohexanone by mass) (G) Component LA-3018-50P: Aminotriazine-based cresol novolac resin (DIC Corporation's "LA-3018-50P," containing 50% solids and 50% propylene glycol monoethyl ether) V-03: Carbodiimide resin-containing liquid (Nisshinbo Chemical's "V-03", containing 50% solids and 50% toluene) (H) Component SA9000: Polyphenylene ether resin (SABIC "SA9000") BMI689: Maleimide resin (Designer Molercules Inc. "BMI689") Component (I) U-CAT SA810: Thermal base generator (U-CAT SA810 manufactured by San-Apro Co., Ltd.) U-CAT SA506: Thermal base generator (U-CAT SA506 manufactured by San-Apro Co., Ltd.)

[0187] [Evaluation of crack resistance, peel strength, and arithmetic mean roughness (Ra)] <Sample Preparation> The copper foil on both sides of a glass cloth-based epoxy resin double-sided laminate (copper foil thickness 18 μm, substrate thickness 0.3 mm, size 500 mm × 500 mm, Panasonic "R5715ES") with an inner layer circuit formed was etched to create 25 copper patterns with L / S of 1 mm / 1 mm and a length of 5 cm, obtaining a textured substrate. The copper surface was then roughened by etching 1 μm using a MEC "CZ8100" to obtain an inner layer circuit board.

[0188] The resin sheets obtained in each example and comparative example were laminated on both sides of an inner layer circuit board using a batch-type vacuum pressure laminator (Nichigo-Morton, two-stage build-up laminator CVP700). Lamination was performed by reducing the pressure to 13 hPa or less for 30 seconds, followed by pressure bonding at 100°C and a pressure of 0.74 MPa for 30 seconds. Next, a heat press was performed at 100°C and a pressure of 0.5 MPa for 60 seconds.

[0189] The laminated resin sheets were heated at 100°C for 30 minutes, and then at 170°C for 30 minutes to thermally cure the resin composition layer and form an insulating layer. The resulting laminated sample is referred to as "Laminated Sample A."

[0190] Next, the obtained laminate sample A was subjected to the following swelling treatment, roughening treatment, and electroless plating treatment.

[0191] Swelling treatment: The laminated sample A was placed in a swelling solution at 60°C (aqueous solution containing "Swelling Dip Securigant P" manufactured by Atotech Japan and "sodium hydroxide" manufactured by Wako Pure Chemical Industries, Ltd.) and swung at a swelling temperature of 60°C for 10 minutes. Thereafter, it was washed with pure water.

[0192] Roughening treatment (permanganate treatment): The swollen laminated sample was placed in an 80°C sodium permanganate roughening solution (Concentrate Compact CP, manufactured by Atotech Japan, Sodium Hydroxide, manufactured by Wako Pure Chemical Industries, Ltd.) and swirled for 20 minutes at a roughening temperature of 80°C. It was then washed for 10 minutes with a 40°C cleaning solution (Reduction Securigant P, manufactured by Atotech Japan, Sulfuric Acid, manufactured by Wako Pure Chemical Industries, Ltd.), and then further washed with pure water to obtain laminated sample B.

[0193] Electroless plating process: The surface of laminated sample B was treated with an alkaline cleaner (Atotech Japan's "Cleaner Securigant 902") at 60°C for 5 minutes to degrease and clean. After cleaning, the cured product was treated with a pre-dip solution (Atotech Japan's "Pre-dip Neogant B") at 25°C for 2 minutes. The cured product was then treated with an activator solution (Atotech Japan's "Activator Neogant 834") at 40°C for 5 minutes to attach a palladium catalyst. Next, laminated sample B was treated with a reducing solution (Atotech Japan's "Reducer Neogant WA") at 30°C for 5 minutes.

[0194] Next, laminated sample B was placed in a chemical copper solution ("Basic Printganth MSK-DK," "Copper Printganth MSK," "Stabilizer Printganth MSK," and "Reducer Cu," all manufactured by Atotech Japan), and electroless plating was performed until the plating thickness reached approximately 0.1 μm. After electroless plating, annealing was performed at 120°C for 30 minutes to remove any remaining hydrogen gas. All steps up to the electroless plating step were performed using 2 L of treatment solution in a beaker while shaking laminated sample B.

[0195] Next, electrolytic plating was performed on the electroless plated laminate sample B until the plating thickness reached 25 μm. For the electrolytic copper plating, a copper sulfate solution ("Copper sulfate pentahydrate" manufactured by Wako Pure Chemical Industries, Ltd., "Sulfuric acid" manufactured by Wako Pure Chemical Industries, Ltd., "Basic Leveler Cupracid HL" manufactured by Atotech Japan, and "Correction Agent Cupracid GS" manufactured by Atotech Japan) was used, and the plating was performed at 0.6 A / cm 2 Electrolytic plating was carried out by passing a current of 1000 kJ / min until the plating thickness reached approximately 25 μm. After the copper plating process, the cured product was heated at 190°C for 1 hour to further harden the cured product. In this way, laminate sample C, which had a copper plating layer laminated on the upper surface, was obtained.

[0196] <Crack resistance evaluation> The presence or absence of cracks on the surface of the laminated sample C was confirmed using an optical microscope, and the sample was evaluated according to the following criteria. O: No cracks on 25 copper patterns. △: 25 copper patterns have 1 to 2 cracks. ×: Three or more cracks were found among 25 copper patterns.

[0197] <Evaluation of peel strength> A 10 mm wide notch was made in the surface of the copper plating layer of Laminate Sample C. Then, using a tensile tester ("AC-50C-SL" manufactured by TSE Corporation), the load (kgf / cm) when 35 mm was peeled off in the vertical direction at a rate of 50 mm / min at room temperature was measured, and the peel strength was evaluated according to the following criteria. ◎: Peel strength is 0.5kgf / cm or more ○: Peel strength is less than 0.4kgf / cm and 0.5kgf / cm ×: Peel strength is less than 0.4 kgf / cm

[0198] <Measurement of arithmetic mean roughness (Ra)> The arithmetic mean roughness of the insulating layer surface of laminate sample B was determined as the Ra value using a non-contact surface roughness meter (VYKO NT3300 manufactured by Veeco Instruments) in VSI mode with a 50x lens over a measurement range of 121 μm x 92 μm. The Ra value was calculated by averaging 10 randomly selected points and evaluating them according to the following criteria. ◎: Arithmetic mean roughness (Ra) is less than 100 nm ○: Arithmetic mean roughness (Ra) is 100 nm or more and less than 200 nm △: Arithmetic mean roughness (Ra) is 200nm or more and less than 400nm ×: Arithmetic mean roughness (Ra) is 400 nm or more

[0199] [Evaluation of dielectric loss tangent] <Preparation of evaluation samples> The resin compositions obtained in each example and comparative example were uniformly coated onto a release-treated PET film ("PET501010" manufactured by Lintec Corporation) using a die coater so that the thickness of the resin composition layer after drying would be 40 μm, and then dried at 90 to 130°C (average 110°C) for 5 minutes. The film was then heat-treated at 200°C for 90 minutes in a nitrogen atmosphere and peeled off from the support to obtain a cured product (thickness 40 μm). The cured product was cut into a length of 80 mm and a width of 2 mm to serve as an evaluation sample.

[0200] <Evaluation of dielectric loss tangent> The dielectric loss tangent of the evaluation sample was measured using an HP8362B manufactured by Agilent Technologies by the cavity resonance perturbation method (ASTM D2520) at a measurement frequency of 5.8 GHz and a measurement temperature of 23° C. Measurements were performed on two test pieces, and the average value was calculated and evaluated according to the following criteria. ◎: Dielectric tangent is less than 0.0025 ○: Dielectric tangent is 0.0025 or more and less than 0.0030 △: Dielectric tangent is 0.0030 or more and less than 0.0035 ×: Dielectric tangent is 0.0035 or more

[0201] [Table 3]

[0202] [Table 4]

[0203] In Examples 1 to 19, it was confirmed that even when components (E) to (G) were not contained, the same results as those in the above Examples were obtained, although to different degrees.

Claims

1. (A) an epoxy resin, (B) an active ester curing agent, (C) one or more curing accelerators selected from the group consisting of compounds represented by formula (C-1), and (D) A resin composition containing a curing accelerator (excluding those corresponding to component (C)), When the nonvolatile components in the resin composition are 100% by mass, A resin composition in which the following relationship holds, where the content of the (C) component is (c) and the content of the (D) component is (d): 0.1≦(c) / (d)≦30 (excluding the range of 0.5≦(c) / (d)≦5) 【Chemistry 1】 In formula (C-1), R １１ , R １２ , R １３ , and R １４ each independently represents a hydrogen atom, an optionally substituted monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms, or an optionally substituted monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms; R １５ represents a divalent aliphatic hydrocarbon group which may have a substituent, or a divalent aromatic hydrocarbon group which may have a substituent.

2. The resin composition according to claim 1 , further comprising (E) an inorganic filler.

3. The resin composition according to claim 1, wherein the component (D) comprises either an imidazole-based curing accelerator or an amine-based curing accelerator.

4. In formula (C-1), R １１ , R １２ , R １３ , and R １４ and each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a phenyl group.

5. In formula (C-1), R １５ The resin composition according to claim 1 , wherein represents an alkylene group which may have a substituent, or a divalent aromatic hydrocarbon group which may have a substituent.

6. The resin composition according to claim 1, which is used to form an insulating layer.

7. A resin sheet comprising: a support; and a resin composition layer provided on the support, the resin composition layer comprising the resin composition according to claim 1.

8. A printed wiring board comprising an insulating layer formed from a cured product of the resin composition according to claim 1.

9. A semiconductor device comprising the printed wiring board according to claim 8.

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