Resin composition

Abstract

To provide a resin composition which enables production of a cured product having low dielectric loss tangent and excellent crack resistance.SOLUTION: A resin composition contains (A) an epoxy resin, (B) a curing agent, and (C) a conjugated diene-aromatic vinyl copolymer resin which contains an alkoxysilyl group and may be hydrogenated.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a resin composition. Further, the present invention relates to a cured product of the resin composition; a sheet-like laminated material and a resin sheet containing the resin composition; and a printed wiring board and a semiconductor device containing an insulating layer formed of a cured product of a resin composition layer.

Background Art

[0002] As a manufacturing technique for printed wiring boards, a manufacturing method by a build-up method in which an insulating layer and a conductor layer are alternately laminated is known. In the manufacturing method by the build-up method, generally, the insulating layer is formed of a cured product obtained by curing a resin composition (Patent Document 1).

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0004] The cured product contained in the insulating layer is required to have a low dielectric tangent. However, in a resin composition containing an epoxy resin and a curing agent, when the composition of the resin composition is adjusted so as to lower the dielectric tangent of the cured product, the obtained cured product is brittle and tends to crack (break). For example, when an active ester-based curing agent is used as the curing agent, while the dielectric tangent of the cured product can be lowered, cracks easily occur in the cured product.

[0005] In order to suppress the above-mentioned cracks, the present inventor has tried to blend a flexible component such as polybutadiene or a rubber component into the resin composition. However, in a resin composition in which a conventional flexible component is blended in combination with an epoxy resin and a curing agent, it is difficult to uniformly disperse the flexible component. As a result, the dielectric loss tangent may increase, or the appearance of the resin varnish and the resin sheet may deteriorate. Therefore, it is desired to develop a resin composition capable of obtaining a cured product having a low dielectric loss tangent and excellent crack resistance. Here, "crack resistance" refers to the property of suppressing the occurrence of cracks in the cured product of the resin composition.

[0006] The present invention was devised in view of the above problems, and provides a resin composition capable of obtaining a cured product having a low dielectric loss tangent and excellent crack resistance; a cured product of the resin composition; a sheet-like laminated material containing the resin composition; a resin sheet having a resin composition layer formed of the resin composition; a printed wiring board including an insulating layer containing a cured product of the resin composition; and a semiconductor device including the printed wiring board.

Means for Solving the Problems

[0007] The present inventor has intensively studied to solve the above problems. As a result, the present inventor has found that a resin composition containing (A) an epoxy resin, (B) a curing agent, and (C) a hydrogenated conjugated diene-aromatic vinyl copolymer resin containing an alkoxysilyl group can solve the above problems, and has completed the present invention. That is, the present invention includes the following.

[0008] [1] A resin composition comprising (A) an epoxy resin, (B) a curing agent, and (C) a hydrogenated conjugated diene-aromatic vinyl copolymer resin containing an alkoxysilyl group. [2] The component (C) contains (c1) an optionally hydrogenated conjugated diene compound unit and (c2) an aromatic vinyl compound unit, The resin composition according to [1], wherein an alkoxysilyl group is bonded to a part or all of the (c1) optionally hydrogenated conjugated diene compound unit. [3] The conjugated diene compound unit which may be hydrogenated is a butadiene unit which may be hydrogenated, (c2) The aromatic vinyl compound unit is a styrene unit, The resin composition according to [2]. [4] (c1) The conjugated diene compound unit which may be hydrogenated contains a direct addition unit, An alkoxysilyl group is bonded to a part or all of the side chains of the direct addition unit, The resin composition according to [2] or [3]. [5] (c2) When the amount of the aromatic vinyl compound unit is 100% by mass of the component (C), it is 15% by mass or more and 50% by mass or less, The resin composition according to any one of [2] to [4]. [6] The component (C) contains an (c3) alkenylalkoxysilane unit, The resin composition according to any one of [1] to [5]. [7] The component (C) contains a structure represented by the following formula (1), The resin composition according to any one of [1] to [6].

Chemical formula

[10] The resin composition according to any one of [1] to [9], wherein the curing agent (B) contains an active ester-based curing agent.)

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

[10] , which contains an inorganic filler (D).

[12] The resin composition according to

[11] , wherein the amount of the inorganic filler (D) is 50% by mass or more and 90% by mass or less based on 100% by mass of the non-volatile components of the resin composition.)

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

[12] , which is for forming an insulating layer.)

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

[13] .

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

[13] .

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

[13] on the support.

[17] A printed wiring board including an insulating layer containing a cured product of the resin composition according to any one of [1] to

[13] .

[18] A semiconductor device including the printed wiring board according to

[17] . [Advantages of the Invention]

[0009] According to the present invention, there can be provided a resin composition capable of obtaining a cured product having a low dielectric tangent and excellent crack resistance; a cured product of the resin composition; a sheet-like laminated material containing the resin composition; a resin sheet having a resin composition layer formed of the resin composition; a printed wiring board including an insulating layer containing a cured product of the resin composition; and a semiconductor device including the printed wiring board. [Modes for Carrying Out the Invention]

[0010] Hereinafter, the present invention will be described with reference to embodiments and examples. However, the present invention is not limited to the embodiments and examples shown below, and can be arbitrarily modified and implemented without departing from the scope of the claims and their equivalents.

[0011] [Outline of Resin Composition] The resin composition according to an embodiment of the present invention includes (A) an epoxy resin, (B) a curing agent, and (C) a hydrogenated conjugated diene-aromatic vinyl copolymer resin containing an alkoxysilyl group. The “(C) hydrogenated conjugated diene-aromatic vinyl copolymer resin containing an alkoxysilyl group” as the component (C) may be hereinafter referred to as “(C) silicon-containing resin”. According to the resin composition according to an embodiment of the present invention, a cured product having a low dielectric tangent and excellent crack resistance can be obtained. Further, according to this cured product, an insulating layer excellent in adhesion to a plated conductor layer can usually be formed. The plated conductor layer represents a conductor layer formed by plating unless otherwise specified.

[0012] The inventor speculates on the mechanism by which the above effects are obtained by the resin composition according to this embodiment as follows. However, the technical scope of the present invention is not limited to the mechanism described below.

[0013] The (C) silicon-containing resin contained in the resin composition according to this embodiment has a flexible conjugated diene-aromatic vinyl copolymer skeleton, so the molecule itself is flexible. Therefore, the (C) silicon-containing resin can relieve stress in the cured product of the resin composition, so that cracks in the cured product can be suppressed. In addition, since the (C) silicon-containing resin contains an alkoxysilyl group, it has excellent compatibility with the (A) epoxy resin and the (B) curing agent. Therefore, the occurrence of phase separation in the cured product can be suppressed, so that the formation of the phase interface can be suppressed. Generally, the phase interface tends to be a starting point for fracture due to stress concentration. However, in the cured product of the resin composition according to this embodiment, the formation of the phase interface is suppressed, so the occurrence of fracture starting from the phase interface can be suppressed and cracks can be suppressed.

[0014] Also, generally, a conjugated diene-aromatic vinyl copolymer skeleton may contain a carbon-carbon unsaturated bond. Since this carbon-carbon unsaturated bond may be oxidized to generate a polar group, it could be the cause of an increase in the dielectric tangent due to the polar group. However, in the resin composition according to this embodiment, by containing an alkoxysilyl group, the proportion of carbon-carbon unsaturated bonds in the (C) silicon-containing resin is reduced, and thus the generation ratio of polar groups is reduced, suppressing the increase in the dielectric tangent caused by the generation of polar groups. Therefore, according to the resin composition according to this embodiment, both improvement in crack resistance and reduction in dielectric tangent can be achieved.

[0015] In particular, when the (B) curing agent contains a (B-1) active ester-based curing agent, effective suppression of the dielectric loss tangent is possible. The (B-1) active ester-based curing agent does not generate polar groups by reaction with the (A) epoxy resin. Therefore, since an increase in the dielectric loss tangent due to polar groups can be effectively suppressed, effective reduction of the dielectric loss tangent is possible. Further, the (B-1) active ester-based curing agent has a tendency to be particularly low in compatibility with conventional conjugated diene-aromatic vinyl copolymers. However, since the (C) silicon-containing resin has excellent compatibility with the (B-1) active ester-based curing agent, effective crack suppression is possible.

[0016] Furthermore, since the (C) silicon-containing resin has flexible molecules, it can exert an action of enhancing the toughness of the cured product of the resin composition. Therefore, even when the resin composition contains a (D) inorganic filler, generation of cracks in the cured product can be suppressed. In view of the fact that conventionally, cured products containing inorganic fillers have tended to be brittle and prone to cracking, it is beneficial that a cured product capable of suppressing crack generation can be obtained even when the resin composition according to the present embodiment contains a (D) inorganic filler.

[0017] Also, since the toughness of the cured product of the resin composition can be enhanced as described above, the insulating layer containing the cured product is less likely to be broken by stress. Therefore, when a plated conductor layer is formed on the insulating layer, peeling of the plated conductor layer accompanied by breakage of the insulating layer can be suppressed. Therefore, generally, the adhesion between the insulating layer and the plated conductor layer can be improved.

[0018] The resin composition according to an embodiment of the present invention may further contain an arbitrary component in combination with the components (A) to (C). Examples of the arbitrary component include a (D) inorganic filler, an (E) thermoplastic resin, an (F) curing accelerator, a (G) radically polymerizable compound, an (H) arbitrary additive, and the like. Hereinafter, each component contained in the resin composition according to an embodiment of the present invention will be described in detail.

[0019] [(A) Epoxy resin] The resin composition according to an embodiment of the present invention contains (A) an epoxy resin as component (A). The (A) epoxy resin can be a curable resin having an epoxy group.

[0020] Examples of the (A) epoxy resin include a bixylenol type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a bisphenol AF type epoxy resin, a dicyclopentadiene type epoxy resin, a trisphenol type epoxy resin, a naphthol novolak type epoxy resin, a phenol novolak type epoxy resin, a tert-butyl-catechol type epoxy resin, a naphthalene type epoxy resin, a naphthol type epoxy resin, an anthracene type epoxy resin, a glycidylamine type epoxy resin, a glycidyl ester type epoxy resin, a cresol novolak type epoxy resin, a phenol aralkyl type epoxy resin, a biphenyl type epoxy resin, a linear aliphatic epoxy resin, an epoxy resin having a butadiene structure, an alicyclic epoxy resin, a heterocyclic epoxy resin, a spiro ring-containing epoxy resin, a cyclohexane type epoxy resin, a cyclohexanedimethanol type epoxy resin, a naphthylene ether type epoxy resin, a trimethylol type epoxy resin, a tetraphenylethane type epoxy resin, an isocyanurate type epoxy resin, a phenolphthalimide type epoxy resin, and the like. The (A) epoxy resin may be used alone or in combination of two or more.

[0021] (A) From the viewpoint of obtaining a cured product with excellent heat resistance, the epoxy resin preferably contains an epoxy resin containing an aromatic structure. The aromatic structure is a chemical structure generally defined as aromatic, and includes polycyclic aromatics and aromatic heterocycles. Examples of the epoxy resin containing an aromatic structure include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol novolak type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, biscylenol type epoxy resin, glycidylamine type epoxy resin having an aromatic structure, glycidyl ester type epoxy resin having an aromatic structure, cresol novolak type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin having an aromatic structure, epoxy resin having a butadiene structure with an aromatic structure, alicyclic epoxy resin having an aromatic structure, heterocyclic epoxy resin, spiro ring-containing epoxy resin having an aromatic structure, cyclohexanedimethanol type epoxy resin having an aromatic structure, naphthylene ether type epoxy resin, trimethylol type epoxy resin having an aromatic structure, tetraphenylethane type epoxy resin having an aromatic structure, and the like.

[0022] (A) The epoxy resin preferably contains an epoxy resin having two or more epoxy groups in one molecule. With respect to 100% by mass of the total amount of the (A) epoxy resin, the proportion of the epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more.

[0023] (A) Epoxy resins include liquid epoxy resins (hereinafter sometimes referred to as "liquid epoxy resins") that are liquid at a temperature of 20°C and solid epoxy resins (hereinafter sometimes referred to as "solid epoxy resins") that are solid at a temperature of 20°C. (A) Epoxy resin may be only a liquid epoxy resin, only a solid epoxy resin, or a combination of a liquid epoxy resin and a solid epoxy resin. Among them, (A) epoxy resin is preferably a combination of a liquid epoxy resin and a solid epoxy resin.

[0024] As the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferred.

[0025] As the liquid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin having an ester skeleton, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, epoxy resin having a butadiene structure, epoxy resin containing an alkyleneoxy skeleton and a butadiene skeleton, epoxy resin containing a fluorene structure, dicyclopentadiene type epoxy resin are preferred. Among them, bisphenol A type epoxy resin and bisphenol F type epoxy resin are particularly preferred.

[0026] Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", "HP4032SS" (naphthalene-type epoxy resin) manufactured by DIC Corporation; "828US", "828EL", "jER828EL", "825", "Epicoat 828EL" (bisphenol A-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER807", "1750" (bisphenol F-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol novolac-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "630", "630LSD", "604" (glycidylamine-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "ED-523T" (glycerol-type epoxy resin) manufactured by ADEKA Corporation; "EP-3950L", "EP-3980S" (glycidylamine-type epoxy resin) manufactured by ADEKA Corporation; "EP-4088S" (dicyclopentadiene-type epoxy resin) manufactured by ADEKA Corporation; "ZX1059" (a mixture of bisphenol A-type epoxy resin and bisphenol F-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "EX-721" (glycidyl ester-type epoxy resin) manufactured by Nagase ChemteX Corporation; "Celoxide 2021P" (alicyclic epoxy resin having an ester skeleton) manufactured by Daicel Corporation; "PB-3600", "JP-100", "JP-200" (epoxy resin having a butadiene structure) manufactured by Nippon Soda Co., Ltd.; "ZX1658", "ZX1658GS" (liquid 1,4-glycidylcyclohexane-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd., etc. These may be used alone or in combination of two or more.

[0027] As the solid epoxy resin, a solid epoxy resin having three or more epoxy groups in one molecule is preferred, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is more preferred.

[0028] As the solid epoxy resin, biphenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, naphthol novolak type epoxy resin, cresol novolak type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, phenol aralkyl type epoxy resin, tetraphenylethane type epoxy resin, and phenolphthalimide type epoxy resin are preferred.

[0029] Specific examples of the solid epoxy resin include "HP4032H" (naphthalene-type epoxy resin) manufactured by DIC Corporation; "HP-4700" and "HP-4710" (naphthalene-type tetrafunctional epoxy resin) manufactured by DIC Corporation; "N-690" (cresol novolak-type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolak-type epoxy resin) manufactured by DIC Corporation; "HP-7200", "HP-7200HH", "HP-7200H", and "HP-7200L" (dicyclopentadiene-type epoxy resin) manufactured by DIC Corporation; "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", and "HP6000" (naphthylene ether-type epoxy resin) manufactured by DIC Corporation; "EPPN-502H" (trisphenol-type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC7000L" (naphthol novolak-type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC3000H", "NC3000", "NC3000L", "NC3000FH", and "NC3100" (biphenyl-type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "ESN475V" and "ESN4100V" (naphthalene-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "ESN485" (naphthol-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "ESN375" (dihydroxynaphthalene-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YX4000H", "YX4000", "YX4000HK", and "YL7890" (bixylenol-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL6121" (biphenyl-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX8800" (anthracene-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX7700" (phenol aralkyl-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) manufactured by Mitsubishi Chemical Corporation; "YL7800" (fluorene-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1010" (bisphenol A-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1031S" (tetraphenylethane-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "WHR991S" (phenolphthalimide-type epoxy resin) manufactured by Nippon Kayaku Co., Ltd., and the like.These may be used alone or in combination of two or more.

[0030] (A) When a liquid epoxy resin and a solid epoxy resin are used in combination as the epoxy resin, their mass ratio (liquid epoxy resin:solid epoxy resin) is preferably 20:1 to 1:20, more preferably 10:1 to 1:10, and particularly preferably 7:1 to 1:7.

[0031] (A) The epoxy equivalent of the epoxy resin is preferably 50 g / eq. to 5,000 g / eq., more preferably 60 g / eq. to 3,000 g / eq., still more preferably 80 g / eq. to 2,000 g / eq., and particularly preferably 110 g / eq. to 1,000 g / eq. The epoxy equivalent represents the mass of the resin per equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.

[0032] (A) The weight average molecular weight (Mw) of the epoxy resin is preferably 100 to 5,000, more preferably 250 to 3,000, and still more preferably 400 to 1,500. The weight average molecular weight of the resin can be measured as a value in terms of polystyrene by the gel permeation chromatography (GPC) method.

[0033] When the content of the (A) epoxy resin in the resin composition is based on 100% by mass of the non-volatile components in the resin composition, it is preferably 1% by mass or more, more preferably 2% by mass or more, and particularly preferably 4% by mass or more, and is preferably 25% by mass or less, more preferably 20% by mass or less, and particularly preferably 10% by mass or less. When the amount of the (A) epoxy resin is within the above range, the dielectric tangent and crack resistance of the cured product of the resin composition can be made particularly good, and further, usually, the plating peel strength can be effectively increased. The plating peel strength, unless otherwise specified, represents the force required to peel the plating conductor layer when the plating conductor layer is formed on the insulating layer formed of the cured product of the resin composition. The higher this plating peel strength, the better the adhesion between the insulating layer and the plating conductor layer.

[0034] When the content of the (A) epoxy resin in the resin composition is based on 100% by mass of the resin components in the resin composition, it is preferably 5% by mass or more, more preferably 10% by mass or more, particularly preferably 20% by mass or more, and preferably 70% by mass or less, more preferably 60% by mass or less, particularly preferably 50% by mass or less. The resin components of the resin composition refer to the components excluding the (D) inorganic filler among the non-volatile components of the resin composition. When the amount of the (A) epoxy resin is within the above range, the dielectric tangent and crack resistance of the cured product of the resin composition can be particularly improved, and usually, the plating peel strength can be effectively increased.

[0035] [(B) Curing agent] The resin composition according to one embodiment of the present invention contains a (B) curing agent as the (B) component. This (B) curing agent does not include those corresponding to the above-described (A) component. The (B) curing agent may have a function of curing the (A) epoxy resin. The curing agent may be used alone or in combination of two or more.

[0036] The (B) curing agent preferably contains a (B-1) active ester-based curing agent. When the (B) curing agent contains the (B-1) active ester-based curing agent, the dielectric tangent of the cured product of the resin composition can be effectively reduced. The (B-1) active ester-based curing agent may be used alone or in combination of two or more.

[0037] (B-1) As the active ester curing agent, compounds having two or more highly reactive ester groups in one molecule, such as generally phenolic esters, thiophenolic esters, N-hydroxyamine esters, esters of heterocyclic hydroxy compounds, etc., are preferably used. The active ester curing agent is preferably obtained by a condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound. Particularly from the viewpoint of improving heat resistance, an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester curing agent obtained from a carboxylic acid compound and a phenolic compound and / or a naphthol compound is more preferred. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, etc. Examples of the phenolic compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, 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 compound, phenol novolak, etc. Here, the "dicyclopentadiene type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

[0038] Specifically, as the (B-1) active ester curing agent, a dicyclopentadiene type active ester curing agent, a naphthalene type active ester curing agent containing a naphthalene structure, an active ester curing agent containing an acetylated product of phenol novolak, and an active ester curing agent containing a benzoylated product of phenol novolak are preferable. Among them, at least one selected from a dicyclopentadiene type active ester curing agent and a naphthalene type active ester curing agent is more preferable, and a naphthalene type active ester curing agent is particularly preferable. As the dicyclopentadiene type active ester curing agent, an active ester curing agent containing a dicyclopentadiene type diphenol structure is preferable.

[0039] (B-1) Examples of commercially available active ester curing agents include, as an active ester curing agent containing a dicyclopentadiene type diphenol structure, "EXB9451", "EXB9460", "EXB9460S", "EXB-8000L", "EXB-8000L-65M", "EXB-8000L-65TM", "HPC-8000L-65TM", "HPC-8000", "HPC-8000-65T", "HPC-8000H", "HPC-8000H-65TM" (manufactured by DIC Corporation); as an active ester curing agent containing a naphthalene structure, "HP-B-8151-62T", "EXB-8100L-65T", "EXB-8150-60T", "EXB-8150-62T", "EXB-9416-70BK", "HPC-8150-60T", "HPC-8150-62T", "EXB-8" (manufactured by DIC Corporation); as a phosphorus-containing active ester curing agent, "EXB9401" (manufactured by DIC Corporation); as an active ester curing agent that is an acetylated product of phenol novolak, "DC808" (manufactured by Mitsubishi Chemical Corporation); as an active ester curing agent that is a benzoylated product of phenol novolak, "YLH1026", "YLH1030", "YLH1048" (manufactured by Mitsubishi Chemical Corporation); as an active ester curing agent containing a styryl group and a naphthalene structure, "PC1300-02-65MA" (manufactured by Air Water Inc.), and the like.

[0040] (A) When the epoxy group number of the epoxy resin is set to 1, (B-1) the active ester group number of the active ester-based curing agent is preferably 0.01 or more, more preferably 0.1 or more, still more preferably 1 or more, and preferably 10 or less, more preferably 5 or less, particularly preferably 2 or less. The “epoxy group number of (A) the epoxy resin” represents the total value obtained by summing up all the values obtained by dividing the mass of the non-volatile components of (A) the epoxy resin present in the resin composition by the epoxy equivalent. Further, the “active ester group number of (B-1) the active ester-based curing agent” represents the total value obtained by summing up all the values obtained by dividing the mass of the non-volatile components of (B-1) the active ester-based curing agent present in the resin composition by the active ester group equivalent.

[0041] When the content of the (B-1) active ester-based curing agent in the resin composition is based on 100% by mass of the non-volatile components in the resin composition, it is preferably 1% by mass or more, more preferably 5% by mass or more, particularly preferably 10% by mass or more, and preferably 40% by mass or less, more preferably 30% by mass or less, particularly preferably 20% by mass or less. When the amount of the (B-1) active ester-based curing agent is within the above range, the dielectric tangent and crack resistance of the cured product of the resin composition can be made particularly good, and further, usually, the plating peel strength can be effectively increased.

[0042] When the content of the (B-1) active ester-based curing agent in the resin composition is based on 100% by mass of the resin components in the resin composition, it is preferably 10% by mass or more, more preferably 20% by mass or more, particularly preferably 30% by mass or more, and preferably 80% by mass or less, more preferably 70% by mass or less, particularly preferably 60% by mass or less. When the amount of the (B-1) active ester-based curing agent is within the above range, the dielectric tangent and crack resistance of the cured product of the resin composition can be made particularly good, and further, usually, the plating peel strength can be effectively increased.

[0043] The mass ratio of the (B-1) active ester-based curing agent to the (C) silicon-containing resin in the resin composition ((B-1) active ester-based curing agent / (C) silicon-containing resin) is preferably within a specific range. Specifically, the mass ratio ((B-1) active ester-based curing agent / (C) silicon-containing resin) is preferably 0.1 or more, more preferably 1 or more, particularly preferably 2 or more, and preferably 100 or less, more preferably 50 or less, particularly preferably 30 or less. When the mass ratio ((B-1) active ester-based curing agent / (C) silicon-containing resin) is within the above range, the dielectric tangent and crack resistance of the cured product of the resin composition can be particularly improved, and usually, the plating peel strength can be effectively increased.

[0044] Examples of curing agents other than the (B-1) active ester-based curing agent include phenolic curing agents, carbodiimide-based curing agents, acid anhydride-based curing agents, amine-based curing agents, benzoxazine-based curing agents, cyanate ester-based curing agents, and thiol-based curing agents. These curing agents may be used alone or in combination of two or more. Among them, those selected from the group consisting of phenolic curing agents and carbodiimide-based curing agents are preferred.

[0045] As the phenolic curing agent, a curing agent having one or more, preferably two or more, hydroxyl groups bonded to an aromatic ring such as a benzene ring or a naphthalene ring in one molecule can be used. From the viewpoints of heat resistance and water resistance, a phenolic curing agent having a novolak structure is preferable. Further, from the viewpoint of adhesion, a nitrogen-containing phenolic curing agent is preferable, and a phenolic curing agent containing a triazine skeleton is more preferable. Among them, from the viewpoint of highly improving heat resistance, water resistance, and adhesion, a phenolic novolak resin containing a triazine skeleton is preferable. Specific examples of the phenolic curing agent include, for example, "MEH-7700", "MEH-7810", "MEH-7851" manufactured by Meiwa Kasei Co., Ltd., "NHN", "CBN", "GPH" manufactured by Nippon Kayaku Co., Ltd., "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN-375", "SN-395" manufactured by Nippon Steel Chemical & Material Co., Ltd., "LA-7052", "LA-7054", "LA-3018", "LA-3018-50P", "LA-1356", "TD2090", "TD-2090-60M" manufactured by DIC Corporation, and the like.

[0046] As the carbodiimide-based curing agent, a curing agent having one or more, preferably two or more carbodiimide structures in one molecule can be used. Specific examples of the carbodiimide-based curing agent include aliphatic biscarbodiimides such as tetramethylene-bis(t-butylcarbodiimide) and cyclohexane bis(methylene-t-butylcarbodiimide); biscarbodiimides such as aromatic biscarbodiimides like phenylene-bis(xylylcarbodiimide); aliphatic polycarbodiimides such as polyhexamethylene carbodiimide, polytrimethylhexamethylene carbodiimide, polycyclohexylene carbodiimide, poly(methylenebiscyclohexylene carbodiimide), and poly(isophorone carbodiimide); aromatic polycarbodiimides such as poly(phenylene carbodiimide), poly(naphthylene carbodiimide), poly(tolylene carbodiimide), poly(methyldiisopropylphenylene carbodiimide), poly(triethylphenylene carbodiimide), poly(diethylphenylene carbodiimide), poly(triisopropylphenylene carbodiimide), poly(diisopropylphenylene carbodiimide), poly(xylylene carbodiimide), poly(tetramethylxylylene carbodiimide), poly(methylenediphenylene carbodiimide), and poly[methylenebis(methylphenylene) carbodiimide]. Specific examples of the carbodiimide-based curing agent include "Carbodilite V-02B", "Carbodilite V-03", "Carbodilite V-07", and "Carbodilite V-09" manufactured by Nisshinbo Chemicals Co., Ltd.; "Stabaxol P", "Stabaxol P400", "High Cadil 510", etc. manufactured by Rhein Chemie Co., Ltd.

[0047] Examples of the acid anhydride-based curing agent include curing agents having one or more acid anhydride groups in one molecule, and curing agents having two or more acid anhydride groups in one molecule are preferred. Specific examples of the acid anhydride-based curing agent include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl nadic anhydride, hydrogenated methyl nadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenylsulfone tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]furan-1,3-dione, ethylene glycol bis(anhydrotrimellitate), and polymer-type acid anhydrides such as styrene-maleic acid resin copolymerized from styrene and maleic acid. Commercially available products of the acid anhydride-based curing agent include, for example, "HNA-100", "MH-700", "MTA-15", "DDSA", "OSA" manufactured by Shin Nippon Rika Co., Ltd.; "YH-306", "YH-307" manufactured by Mitsubishi Chemical Corporation; "HN-2200", "HN-5500" manufactured by Hitachi Chemical Co., Ltd.; "EF-30", "EF-40", "EF-60", "EF-80" manufactured by Cray Valley Co., Ltd., and the like.

[0048] As the amine-based curing agent, a curing agent having one or more, preferably two or more, amino groups in one molecule can be used. As the amine-based curing agent, for example, aliphatic amines, polyether amines, alicyclic amines, aromatic amines, etc. can be mentioned, among which aromatic amines are preferred. As the amine-based curing agent, primary amines or secondary amines are preferred, and primary amines are more preferred. Specific examples of amine-based curing agents include 4,4'-methylenebis(2,6-dimethylaniline), 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, and 2,2-bis(3-amino-4-hydroxyphenyl)propane. propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)sulfone, bis(4-(3-aminophenoxy)phenyl)sulfone, and the like. Commercially available amine-based curing agents include, for example, "SEIKACURE-S" manufactured by Seika Corporation; "KAYABOND C-200S", "KAYABOND C-100", "KAYAHARD AA", "KAYAHARD AB", and "KAYAHARD AS" manufactured by Nippon Kayaku Co., Ltd.; "Epicure W" manufactured by Mitsubishi Chemical Corporation; and "DTDA" manufactured by Sumitomo Seika Chemicals Co., Ltd.

[0049] Specific examples of benzoxazine-based curing agents include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemical Corporation; "HFB2006M" manufactured by Showa Polymer Co., Ltd.; and "Pd" and "Fa" manufactured by Shikoku Chemical Industry Co., Ltd.

[0050] Examples of cyanate ester-based curing agents include bifunctional cyanate resins such as bisphenol A dicyanate, polyphenol cyanate (oligo(3-methylen-1,5-phenylene cyanate)), 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4'-ethylidenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4-cyanatephenyl)thioether, and bis(4-cyanatephenyl)ether; polyfunctional cyanate resins derived from phenol novolak and cresol novolak; prepolymers in which part of these cyanate resins is triazine-formed; and the like. Specific examples of cyanate ester-based curing agents include "PT30" and "PT60" (both phenol novolak type polyfunctional cyanate ester resins), "BA230", "BA230S75" (prepolymers in which part or all of bisphenol A dicyanate is triazine-formed to become trimers), etc. manufactured by Lonza Japan Co., Ltd.

[0051] Examples of thiol-based curing agents include trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), tris(3-mercaptopropyl) isocyanurate, and the like.

[0052] (B) The active group equivalent of the curing agent is preferably 50 g / eq. to 3000 g / eq., more preferably 100 g / eq. to 1000 g / eq., still more preferably 100 g / eq. to 500 g / eq., and particularly preferably 100 g / eq. to 300 g / eq. The active group equivalent represents the mass of the curing agent per equivalent of the active group.

[0053] (A) When the epoxy group number of the epoxy resin is taken as 1, (B) the active group number of the curing agent is preferably 0.01 or more, more preferably 0.1 or more, still more preferably 1 or more, and preferably 10 or less, more preferably 5 or less, particularly preferably 2 or less. The “(B) active group number of the curing agent” represents the total value obtained by adding up all the values obtained by dividing the mass of the non-volatile component of (B) the curing agent present in the resin composition by the active group equivalent.

[0054] When the content of (B) the curing agent in the resin composition is based on 100% by mass of the non-volatile component in the resin composition, it is preferably 3% by mass or more, more preferably 5% by mass or more, still more preferably 8% by mass or more, particularly preferably 10% by mass or more, and preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less, particularly preferably 18% by mass or less. When the amount of (B) the curing agent is within the above range, the dielectric tangent and crack resistance of the cured product of the resin composition can be made particularly good, and further, usually, the plating peel strength can be effectively increased.

[0055] When the content of (B) the curing agent in the resin composition is based on 100% by mass of the resin component in the resin composition, it is preferably 5% by mass or more, more preferably 10% by mass or more, particularly preferably 20% by mass or more, and preferably 80% by mass or less, more preferably 70% by mass or less, particularly preferably 60% by mass or less. When the amount of (B) the curing agent is within the above range, the dielectric tangent and crack resistance of the cured product of the resin composition can be made particularly good, and further, usually, the plating peel strength can be effectively increased.

[0056] [(C) Silicon-containing resin (a conjugated diene-aromatic vinyl copolymer resin which may contain an alkoxysilyl group and may be hydrogenated)] The resin composition according to one embodiment of the present invention contains a (C) silicon-containing resin as the (C) component (that is, a conjugated diene-aromatic vinyl copolymer resin which may contain a (C) alkoxysilyl group and may be hydrogenated).

[0057] The conjugated diene-aromatic vinyl copolymer resin refers to a resin containing a structure obtained by copolymerizing a conjugated diene compound and an aromatic vinyl compound. Further, the conjugated diene-aromatic vinyl copolymer resin containing an alkoxysilyl group refers to a resin having a structure in which an alkoxysilyl group is introduced into a resin containing a structure obtained by copolymerizing a conjugated diene compound and an aromatic vinyl compound. Further, the (C) conjugated diene-aromatic vinyl copolymer resin containing an alkoxysilyl group and optionally hydrogenated (i.e., the (C) silicon-containing resin) includes both a conjugated diene-aromatic vinyl copolymer resin containing an alkoxysilyl group and a resin having a structure in which the carbon-carbon unsaturated bond of the conjugated diene-aromatic vinyl copolymer resin containing the alkoxysilyl group is hydrogenated. However, there is no restriction on the method for producing the (C) silicon-containing resin. Therefore, the (C) silicon-containing resin may be produced by a method other than the method of copolymerizing a conjugated diene compound and an aromatic vinyl compound, introducing an alkoxysilyl group, and hydrogenating if necessary.

[0058] (C) The silicon-containing resin usually contains (c1) a conjugated diene compound unit which may be hydrogenated. In this (c1) conjugated diene compound unit which may be hydrogenated, an alkoxysilyl group may be bonded. The (c1) conjugated diene compound unit which may be hydrogenated may be hereinafter referred to as the "(c1) diene unit".

[0059] The conjugated diene compound unit refers to a structural unit having a structure formed by polymerizing a conjugated diene compound. However, there is no restriction on the method for producing the conjugated diene compound unit. Therefore, the conjugated diene compound unit may be formed by a method other than polymerizing a conjugated diene compound.

[0060] The conjugated diene compound unit which may be hydrogenated includes both a conjugated diene compound unit and a hydrogenated conjugated diene compound unit. The hydrogenated conjugated diene compound unit represents a structural unit having a structure formed by hydrogenating part or all of the carbon-carbon unsaturated bonds of the conjugated diene compound unit. However, there is no limitation on the method for producing the hydrogenated conjugated diene compound unit. Therefore, the hydrogenated conjugated diene compound unit may be formed by a method other than hydrogenating the carbon-carbon unsaturated bond of the conjugated diene compound unit.

[0061] As the conjugated diene compound corresponding to the conjugated diene compound unit, a diene compound having a carbon atom chain containing 4 carbon atoms bonded in this order by a double bond, a single bond, and a double bond can be used. Examples of the conjugated diene compound include butadiene, isoprene, dimethylbutadiene, 1,3-pentadiene, 3-methyl-1,3-pentadiene, and the like. The conjugated diene compound may be used alone or in combination of two or more. Therefore, (c1) the diene unit may be used alone or in combination of two or more.

[0062] Among the conjugated diene compounds, butadiene is preferred. Therefore, as (c1) the diene unit, a butadiene unit which may be hydrogenated is preferred. The butadiene unit represents a structural unit having a structure formed by polymerizing butadiene. The butadiene unit which may be hydrogenated includes both a butadiene unit and a hydrogenated butadiene unit. Further, the hydrogenated butadiene unit represents a structure formed by hydrogenating part or all of the carbon-carbon unsaturated bonds of the butadiene unit. However, there is no limitation on the method for producing the butadiene unit which may be hydrogenated.

[0063] (c1) The amount of the diene unit is preferably 10% by mass or more, more preferably 20% by mass or more, particularly preferably 30% by mass or more, and preferably 70% by mass or less, more preferably 60% by mass or less, particularly preferably 50% by mass or less, based on 100% by mass of the silicon-containing resin (C). The amount of the (c1) diene unit includes both the amount of the (c1) diene unit to which an alkoxysilyl group is bonded and the amount of the (c1) diene unit to which no alkoxysilyl group is bonded.

[0064] It is preferable that an alkoxysilyl group is bonded to part or all of the (c1) diene unit. At this time, the alkoxysilyl group is preferably bonded to at least the direct addition unit among the (c1) diene units. This point will be described in detail below.

[0065] The conjugated diene compound generally has a carbon atom chain containing 4 carbon atoms bonded in this order of double bond, single bond, and double bond. Since the carbon atom chain has the same carbon skeleton as that of 1,3-butadiene, it may be hereinafter referred to as the "butadiene carbon skeleton".

[0066] When the conjugated diene compound polymerizes, generally, a conjugated addition reaction and a direct addition reaction may occur. In the conjugated addition reaction, a 1,4-addition reaction occurs in which the carbon atoms at the 1st and 4th positions of the butadiene carbon skeleton are bonded. Therefore, in the conjugated diene compound unit formed by the conjugated addition reaction, a double bond is included in the main chain that connects carbon atoms that bind to other structural units. The conjugated diene compound unit containing a double bond in the main chain in this way usually contains the same carbon atom chain as 1,4-polybutadiene. Hereinafter, among the (c1) diene units, the conjugated diene compound unit containing a double bond in the main chain and the structural unit having a structure formed by hydrogenating the carbon-carbon unsaturated bond may be referred to as the "conjugated addition unit".

[0067] On the other hand, in the direct addition reaction, a 1,2-addition reaction occurs in which the carbon atoms at the 1-position and 2-position of the butadiene carbon skeleton are bonded. Therefore, in the conjugated diene compound unit formed by the direct addition reaction, there is no double bond in the main chain, and the double bond is included in the side chain. The conjugated diene compound unit containing a double bond in the side chain in this way usually contains the same carbon atom chain as 1,2-polybutadiene. Hereinafter, among the (c1) diene units, a conjugated diene compound unit containing a double bond in the side chain and a structural unit having a structure formed by hydrogenating the carbon-carbon unsaturated bond thereof may be referred to as a "direct addition unit".

[0068] Therefore, the (C) silicon-containing resin may contain a conjugated addition unit and a direct addition unit as the (c1) diene unit. When an alkoxysilyl group is bonded to the (c1) diene unit, it is preferably bonded to at least the direct addition unit. In this case, the alkoxysilyl group is preferably bonded to the side chain of the direct addition unit. Further, an alkoxysilyl group may be bonded to a part of the direct addition units contained in the (C) silicon-containing resin, but it is more preferable that the alkoxysilyl group is bonded to all of the direct addition units. When an alkoxysilyl group is bonded to the direct addition unit, it is possible to effectively reduce the dielectric tangent of the cured product of the resin composition and effectively improve the crack resistance.

[0069] (c1) When an alkoxysilyl group is bonded to a diene unit, the alkoxysilyl group may be directly bonded to the (c1) diene unit or may be indirectly bonded via a divalent linking group. The "divalent linking group" is, for example, a divalent hydrocarbon group which may have a substituent, such as an alkylene group which may have a substituent, an alkenylene group which may have a substituent, an alkynylene group which may have a substituent, an arylene group which may have a substituent; a group represented by -C(=O)O-, a group represented by -C(=O)-, a group represented by -C(=O)NH-, a group represented by -NHC(=O)NH-, a group represented by -NHC(=O)O-, a group represented by -S-, a group represented by -SO-, a group represented by -NH-, and a group formed by combining a plurality of these groups. Examples of the substituent include a halogen atom, a cycloalkyloxy group, an aryloxy group, a monovalent heterocyclic group, an amino 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. As the divalent linking group, a divalent hydrocarbon group which may have a substituent is preferable, and a divalent hydrocarbon group having no substituent is more preferable. Among them, it is preferable that the alkoxysilyl group is directly bonded to the (c1) diene unit.

[0070] (C) The silicon-containing resin usually contains (c2) aromatic vinyl compound units. The (c2) aromatic vinyl compound unit represents a structural unit having a structure formed by polymerizing an aromatic vinyl compound. However, there is no limitation on the production method of the (c2) aromatic vinyl compound unit. Therefore, the (c2) aromatic vinyl compound unit may be formed by a method other than polymerizing an aromatic vinyl compound.

[0071] (c2) As the aromatic vinyl compound corresponding to the aromatic vinyl compound unit, a compound containing an aromatic ring and an optionally substituted vinyl group bonded to the aromatic ring can be used. Examples of the aromatic vinyl compound include styrene, vinyltoluene, ethylstyrene, vinylnaphthalene, 4-tert-butylstyrene, 4-acetoxystyrene, 4-vinylphenol, 4-tert-butoxystyrene, 1-(1-ethoxyethoxy)-4-vinylbenzene, 9-vinylanthracene, and the like. The aromatic vinyl compound may be used alone or in combination of two or more. Therefore, the (c2) aromatic vinyl compound unit may be used alone or in combination of two or more.

[0072] Among the aromatic vinyl compounds, styrene is preferred. Therefore, as the (c2) aromatic vinyl compound unit, a styrene unit is preferred. The styrene unit represents a structural unit having a structure formed by polymerizing styrene. However, there is no limitation on the production method of the styrene unit.

[0073] The amount of the (c2) aromatic vinyl compound unit is preferably 15% by mass or more, more preferably 18% by mass or more, particularly preferably 20% by mass or more, and preferably 60% by mass or less, more preferably 50% by mass or less, particularly preferably 40% by mass or less, based on 100% by mass of the (C) silicon-containing resin.

[0074] In the (C) silicon-containing resin, the mass ratio of the (c1) diene unit to the (c2) aromatic vinyl compound unit ((c1) diene unit / (c2) aromatic vinyl compound unit) is preferably within a specific range. Here, the mass of the (c1) diene unit includes the mass of both the (c1) diene unit to which an alkoxysilyl group is bonded and the (c1) diene unit to which an alkoxysilyl group is not bonded. Specifically, the above mass ratio ((c1) diene unit / (c2) aromatic vinyl compound unit) is preferably 0.1 or more, more preferably 0.5 or more, particularly preferably 1 or more, and preferably 100 or less, more preferably 10 or less, particularly preferably 5 or less.

[0075] (C) The silicon-containing resin may contain (c3) alkenylalkoxysilane units. The (c3) alkenylalkoxysilane unit represents a structural unit having a structure formed by polymerizing an alkenylalkoxysilane compound. The alkenylalkoxysilane compound represents a compound containing an Si atom, one or more alkenyl groups bonded to the Si atom, and one or more alkoxy groups bonded to the Si atom.

[0076] Since the carbon-carbon double bond contained in the alkenyl group of the alkenylalkoxysilane compound can react and polymerize, (c3) alkenylalkoxysilane units can be formed as repeating units of the (C) silicon-containing resin. And this (c3) alkenylalkoxysilane unit may contain an alkoxysilyl group derived from the alkenylalkoxysilane compound. However, there is no limitation on the method for producing the (c3) alkenylalkoxysilane unit. Therefore, the (c3) alkenylalkoxysilane unit may be formed by a method other than polymerizing the alkenylalkoxysilane compound.

[0077] Examples of the alkenylalkoxysilane compound corresponding to the (c3) alkenylalkoxysilane unit include vinyltrimethoxysilane, vinyltriethoxysilane, and octenyltrimethoxysilane. The alkenylalkoxysilane compound may be used alone or in combination of two or more. Therefore, the (c3) alkenylalkoxysilane unit may be used alone or in combination of two or more.

[0078] The (c3) alkenylalkoxysilane unit may have the same structure as the (c1) diene unit to which an alkoxysilyl group is bonded. In this specification, among the structural units contained in the (C) silicon-containing resin, the structural unit that can correspond to both the (c1) diene unit and the (c3) alkenylalkoxysilane unit to which an alkoxysilyl group is bonded is classified as the (c1) diene unit to which an alkoxysilyl group is bonded.

[0079] (c3) The amount of the alkenylalkoxysilane unit may be 0% by mass, may be greater than 0% by mass with respect to 100% by mass of the (C) silicon-containing resin, preferably 10% by mass or more, more preferably 20% by mass or more, particularly preferably 30% by mass or more, preferably 70% by mass or less, more preferably 60% by mass or less, and particularly preferably 50% by mass or less.

[0080] (C) The silicon-containing resin may further contain any structural unit in combination with the above-described (c1) diene unit, (c2) aromatic vinyl compound unit, and (c3) alkenylalkoxysilane unit. However, it is preferable that the (C) silicon-containing resin does not contain any structural unit.

[0081] (C) As the silicon-containing resin, a resin containing a structure represented by the following formula (1) is particularly preferable. Therefore, the (C) silicon-containing resin preferably contains a resin containing a structure represented by the following formula (1), and more preferably contains only a resin containing a structure represented by the following formula (1).

[0082]

Chemical formula

[0083] (In formula (1), R 1 ~R 31 、R 34 ~R 40 、and R 43 ~R 45 each independently represent a hydrogen atom or a monovalent hydrocarbon group, X represents a single bond or a divalent linking group, R 32 、R 33 、R 41 and R 42 each independently represent a monovalent hydrocarbon group, Ar represents an aryl group which may have a substituent, a, b, c, and d each independently represent an integer of 0 or more, e and f represent integers of 0 or more satisfying e + f ≧ 1, g represents an integer of 1 or more, h and i represent integers from 1 to 3. However, the order of repeating unit a, repeating unit b, repeating unit c, repeating unit d, repeating unit e, repeating unit f, and repeating unit g is arbitrary.)

[0084] In formula (1), R 1 ~R 31 , R 34 ~R 40 , and R 43 ~R 45 each independently represents a hydrogen atom or a monovalent hydrocarbon group. The monovalent hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, but is preferably an aliphatic hydrocarbon group. The aliphatic hydrocarbon group is usually a saturated aliphatic hydrocarbon group. Further, the monovalent hydrocarbon group may be a linear or branched hydrocarbon group or a hydrocarbon group containing a ring. The number of carbon atoms of the monovalent hydrocarbon group is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 6. Examples of the monovalent hydrocarbon group include alkyl groups such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group; aryl groups such as phenyl group, α-naphthyl group, β-naphthyl group; Among them, R 1 ~R 31 , R 34 ~R 40 , and R 43 ~R 45 each independently is preferably a hydrogen atom and an alkyl group, and particularly preferably a hydrogen atom.

[0085] In formula (1), X represents a single bond or a divalent linking group. As the "divalent linking group", those described above can be used. Among them, as the divalent linking group, a divalent hydrocarbon group which may have a substituent, such as an alkylene group which may have a substituent, an alkenylene group which may have a substituent, an alkynylene group which may have a substituent, and an arylene group which may have a substituent, is preferable. The number of carbon atoms of the divalent hydrocarbon group is usually 1 or more, preferably 2 or more, preferably 20 or less, more preferably 12 or less, still more preferably 10 or less, still more preferably 8 or less, and particularly preferably 6 or less. As the alkylene group, an alkylene group having 1 to 10 carbon atoms is preferable, an alkylene group having 1 to 6 carbon atoms is more preferable, and an alkylene group having 1 to 4 carbon atoms is still more preferable. The alkylene group may be linear, branched, or cyclic. Examples of such an alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a 1,1-dimethylethylene group, etc., and a methylene group, an ethylene group, and a 1,1-dimethylethylene group are preferable, and an ethylene group is particularly preferable. As the alkenylene group, an alkenylene group having 2 to 10 carbon atoms is preferable, an alkenylene group having 2 to 6 carbon atoms is more preferable, and an alkenylene group having 2 to 5 carbon atoms is still more preferable. As the arylene group, an arylene group having 6 to 20 carbon atoms is preferable, and an arylene group having 6 to 10 carbon atoms is more preferable. Among them, X is preferably a divalent alkylene group which may have a substituent, and more preferably a divalent alkylene group having no substituent.

[0086] In formula (1), R 32 、R 33 、R 41 、and R 42 each independently represent a monovalent hydrocarbon group. The monovalent hydrocarbon groups represented by R 32 、R 33 、R 41 、and R 42 are R 1 ~R 31 、R 34 ~R 40 、and R 43 ~R 45can be within the same range as the monovalent hydrocarbon group represented by R 32 R 33 R 41 and R 42 are preferably an alkyl group and an aryl group, more preferably an alkyl group, still more preferably a linear alkyl group, and particularly preferably a methyl group and an ethyl group.

[0087] In formula (1), Ar represents an aryl group which may have a substituent. The number of carbon atoms of the aryl group is preferably 6 or more, preferably 14 or less, and more preferably 10 or less. Examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group and the like. Examples of the substituent that the aryl group may have include, for example, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; a monovalent hydrocarbon group such as an alkyl group, an aryl group, an arylalkyl group and the like; a cycloalkyloxy group, an aryloxy group, an arylalkoxy group, a monovalent heterocyclic group, an amino 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 the like. Among them, as the substituent, a monovalent hydrocarbon group is preferable, an alkyl group and an aryl group are more preferable, and an alkyl group is still more preferable. In particular, Ar is preferably an unsubstituted aryl group.

[0088] In formula (1), a, b, c and d each independently represent an integer of 0 or more. Specifically, a and b each independently are usually 0 or more, preferably 1 or more, more preferably 2 or more, and preferably 300 or less, more preferably 200 or less. Also, c and d are usually 0 or more, may be 1 or more, and are preferably 200 or less, more preferably 100 or less.

[0089] In formula (1), e and f represent integers of 0 or more that satisfy e + f ≥ 1. In particular, it is preferable that e is 1 or more. Specifically, e is usually 0 or more, preferably 1 or more, more preferably 2 or more, preferably 200 or less, more preferably 100 or less. Also, f is usually 0 or more, may be 1 or more, and is preferably 100 or less. Further, it is preferable that e + f satisfies 0.02 ≤ (e + f) / (a + b + c + d + e + f + g) < 1.0.

[0090] In formula (1), g represents an integer of 1 or more. Specifically, g is usually 1 or more, preferably 2 or more, preferably 300 or less, more preferably 200 or less, and particularly preferably 100 or less.

[0091] In formula (1), the order of repeating unit a, repeating unit b, repeating unit c, repeating unit d, repeating unit e, repeating unit f, and repeating unit g is arbitrary.

[0092] In formula (1), h and i each independently represent an integer from 1 to 3, preferably 2 to 3, and more preferably 3.

[0093] (C) More preferable specific examples of the silicon-containing resin include resins containing the structure represented by the following formula (2).

[0094] [Chemical formula]

[0095] (In formula (2), Y represents a single bond or a divalent hydrocarbon group, R 46 , and R 47 each independently represent a monovalent hydrocarbon group, j and k represent integers of 0 or more, l and m each independently represent an integer greater than 0, n represents an integer from 1 to 3. However, the order of repeating unit j, repeating unit k, repeating unit l, and repeating unit m is arbitrary.)

[0096] In formula (2), Y represents a single bond or a divalent hydrocarbon group. The divalent hydrocarbon group represented by Y can be within the same range as the divalent hydrocarbon group represented by X in formula (1). Y is preferably a divalent hydrocarbon group, more preferably an alkylene group, and particularly preferably an ethylene group.

[0097] In formula (2), R 46 , and R 47 each independently represent a monovalent hydrocarbon group. The ranges of R 46 , and R 47 can be the same as those of the aforementioned R 32 , R 33 , R 41 , and R 42 .

[0098] In formula (2), j and k each independently represent an integer of 0 or more. Specifically, j represents an integer within the same range as a and b in formula (1). Also, k represents an integer within the same range as c and d in formula (1).

[0099] In formula (2), l and m each independently represent an integer greater than 0. Specifically, l represents an integer within the same range as e in formula (1). Further, it is preferable that 0.02 ≦ l / (j + k + l + m) < 1.0. Also, m represents an integer within the same range as g in formula (1).

[0100] In formula (2), the order of repeating unit j, repeating unit k, repeating unit l, and repeating unit m is arbitrary.

[0101] In formula (2), n represents an integer from 1 to 3, preferably 2 to 3, and more preferably 3.

[0102] In particular, with respect to 100% by mass of the (C) silicon-containing resin, the amount of the unit containing an alkoxysilyl group (such as the repeating unit e, repeating unit f, repeating unit l, etc. described above) is preferably 3% or more.

[0103] There is no limitation on the method for producing the (C) silicon-containing resin. The (C) silicon-containing resin can be produced, for example, by a method including reacting a conjugated diene-aromatic vinyl copolymer such as a butadiene-styrene copolymer with an alkoxysilane compound such as trimethoxysilane, methyldimethoxysilane, dimethylmethoxysilane, triethoxysilane, methyldiethoxysilane, dimethylethoxysilane in the presence of a platinum compound-containing catalyst to obtain a conjugated diene-aromatic vinyl copolymer resin containing an alkoxysilyl group. For this production method, reference can be made to, for example, JP-A-2017-8301. Further, the (C) silicon-containing resin can be produced, for example, by a method including copolymerizing a conjugated diene compound, an aromatic vinyl compound, and an alkenylalkoxysilane compound to obtain a conjugated diene-aromatic vinyl copolymer resin containing an alkoxysilyl group. Furthermore, the production method of the (C) silicon-containing resin may include hydrogenating the resin after obtaining a conjugated diene-aromatic vinyl copolymer resin containing an alkoxysilyl group.

[0104] As the (C) silicon-containing resin, commercially available products may be used. Examples of commercially available products of the (C) silicon-containing resin include "X-12-1281C" and "X-12-1281A" manufactured by Shin-Etsu Chemical Co., Ltd. (resins in which a trimethoxysilyl group is introduced into the side chain of the direct addition unit of a styrene-butadiene copolymer); "X-12-1281A-ES" manufactured by Shin-Etsu Chemical Co., Ltd. (resin in which a triethoxysilyl group is introduced into the side chain of the direct addition unit of a styrene-butadiene copolymer), etc.

[0105] The (C) silicon-containing resin may be used alone or in combination of two or more.

[0106] (C) The number average molecular weight of the silicon-containing resin is preferably 2,000 or more, more preferably 3,000 or more, particularly preferably 4,000 or more, and preferably 40,000 or less, more preferably 35,000 or less, particularly preferably 30,000 or less. The number average molecular weight can be measured as a polystyrene-equivalent value by gel permeation chromatography (GPC).

[0107] When the content of the (C) silicon-containing resin in the resin composition is based on 100% by mass of the non-volatile components in the resin composition, it is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, particularly preferably 0.2% by mass or more, and preferably 10% by mass or less, more preferably 6% by mass or less, particularly preferably 4% by mass or less. When the amount of the (C) silicon-containing resin is within the above range, the dielectric tangent and crack resistance of the cured product of the resin composition can be particularly improved, and usually, the plating peel strength can be effectively increased.

[0108] When the content of the (C) silicon-containing resin in the resin composition is based on 100% by mass of the resin components in the resin composition, it is preferably 0.5% by mass or more, more preferably 1% by mass or more, particularly preferably 2% by mass or more, and preferably 15% by mass or less, more preferably 10% by mass or less, particularly preferably 8% by mass or less. When the amount of the (C) silicon-containing resin is within the above range, the dielectric tangent and crack resistance of the cured product of the resin composition can be particularly improved, and usually, the plating peel strength can be effectively increased.

[0109] [(D) Inorganic filler] The resin composition according to one embodiment of the present invention may further contain, as an optional component, a (D) inorganic filler in combination with the above-described components (A) to (C). The (D) inorganic filler as the component (D) is usually contained in the resin composition in a particulate state. When the (D) inorganic filler is used, the dielectric tangent of the cured product of the resin composition can be effectively reduced.

[0110] (D) As the material of the inorganic filler, an inorganic compound is used. (D) As the material of the inorganic filler, for example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate can be mentioned. Among these, silica and alumina are preferable, and silica is particularly preferable. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Also, spherical silica is preferable as the silica. (D) The inorganic filler may be used alone or in combination of two or more.

[0111] (D) Examples of commercially available products of the inorganic filler include "SP60-05" and "SP507-05" manufactured by Nippon Steel Chemical & Material Co., Ltd.; "SC2500SQ", "SO-C4", "SO-C2", "SO-C1", "YC100C", "YA050C", "YA050C-MJE", and "YA010C" manufactured by Admatechs Co., Ltd.; "UFP-30", "DAW-03", and "FB-105FD" manufactured by Denka Co., Ltd.; "Silfill NSS-3N", "Silfill NSS-4N", and "Silfill NSS-5N" manufactured by Tokuyama Corporation; "Cellfiers" manufactured by Taiheiyo Cement Corporation; and "Esferic" manufactured by JGC Catalysts & Chemicals Ltd.

[0112] (D) From the viewpoint of significantly obtaining the desired effects of the present invention, the average particle size of the inorganic filler is preferably 0.01 μm or more, more preferably 0.05 μm or more, still more preferably 0.1 μm or more, and particularly preferably 0.2 μm or more, and is preferably 10 μm or less, more preferably 5 μm or less, still more preferably 2 μm or less, and particularly preferably 1 μm or less.

[0113] (D) The average particle size of the inorganic filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler is created on a volume basis by a laser diffraction / scattering type particle size distribution measuring device, and the median diameter thereof is used as the average particle size for measurement. As the measurement sample, 100 mg of the inorganic filler and 10 g of methyl ethyl ketone are weighed into a vial and dispersed by ultrasonic waves for 10 minutes. The measurement sample can be used to measure the volume-based particle size distribution of the inorganic filler using a laser diffraction type particle size distribution measuring device with the wavelengths of the light sources used being blue and red and in a flow cell method, and the average particle size can be calculated as the median diameter from the obtained particle size distribution. Examples of the laser diffraction type particle size distribution measuring device include "LA-960" manufactured by Horiba, Ltd.

[0114] (D) From the viewpoint of significantly obtaining the desired effects of the present invention, the specific surface area of the inorganic filler is preferably 0.1 m 2 / g or more, more preferably 0.5 m 2 / g or more, still more preferably 1 m 2 / g or more, particularly preferably 3 m 2 / g or more, and preferably 100 m 2 / g or less, more preferably 70 m 2 / g or less, still more preferably 50 m 2 / g or less, particularly preferably 40 m 2 / g or less. The specific surface area of the inorganic filler can be measured by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech Co., Ltd.) in accordance with the BET method and calculating the specific surface area using the BET multipoint method.

[0115] (D) From the viewpoint of enhancing moisture resistance and dispersibility, the inorganic filler is preferably treated with a surface treatment agent. Examples of the surface treatment agent include fluorine-containing silane coupling agents, aminosilane-based coupling agents, epoxysilane-based coupling agents, mercaptosilane-based coupling agents, silane-based coupling agents, alkoxysilanes, organosilazane compounds, titanate-based coupling agents, and the like. The surface treatment agent may be used alone or in any combination of two or more kinds.

[0116] Examples of commercially available surface treatment agents include "KBM403" (3-glycidoxypropyltrimethoxysilane), "KBM803" (3-mercaptopropyltrimethoxysilane), "KBE903" (3-aminopropyltriethoxysilane), "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), "SZ-31" (hexamethyldisilazane), "KBM103" (phenyltrimethoxysilane), "KBM-4803" (long-chain epoxy type silane coupling agent), "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane), etc. manufactured by Shin-Etsu Chemical Co., Ltd.

[0117] From the viewpoint of improving the dispersibility of the inorganic filler, the degree of surface treatment with the surface treatment agent preferably falls within a specific range. Specifically, it is preferable that 100% by mass of the inorganic filler is surface-treated with 0.2% to 5% by mass of the surface treatment agent, more preferably surface-treated with 0.2% to 3% by mass of the surface treatment agent, and even more preferably surface-treated with 0.3% to 2% by mass of the surface treatment agent.

[0118] 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 preferably 0.02 mg / m 2 or more, more preferably 0.1 mg / m 2 or more, and even more preferably 0.2 mg / m 2The above is more preferable. On the other hand, from the viewpoint of preventing an increase in the melt viscosity of the resin composition, 1.0 mg / m 2 or less is preferable, 0.8 mg / m 2 or less is more preferable, and 0.5 mg / m 2 or less is even more preferable.

[0119] (D) The amount of carbon per unit surface area of the inorganic filler can be measured after washing the surface-treated inorganic filler with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with 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. As the carbon analyzer, "EMIA-320V" manufactured by Horiba, Ltd. can be used.

[0120] When the content of the (D) inorganic filler in the resin composition is based on 100% by mass of the non-volatile components in the resin composition, it may be 0% by mass, or may be more than 0% by mass. Preferably, it is 50% by mass or more, more preferably 60% by mass or more, particularly preferably 70% by mass or more, preferably 90% by mass or less, more preferably 86% by mass or less, and particularly preferably 82% by mass or less. When the amount of the (D) inorganic filler is within the above range, the dielectric tangent and crack resistance of the cured product of the resin composition can be particularly improved, and usually, the plating peel strength can be effectively increased.

[0121] The mass ratio of the (D) inorganic filler to the (C) silicon-containing resin in the resin composition ((D) inorganic filler / (C) silicon-containing resin) is preferably within a specific range. Specifically, the mass ratio ((D) inorganic filler / (C) silicon-containing resin) is preferably 5 or more, more preferably 10 or more, particularly preferably 20 or more, preferably 300 or less, more preferably 200 or less, and particularly preferably 150 or less. When the mass ratio ((D) inorganic filler / (C) silicon-containing resin) is within the above range, the dielectric tangent and crack resistance of the cured product of the resin composition can be particularly improved, and usually, the plating peel strength can be effectively increased.

[0122] [(E) Thermoplastic resin] The resin composition according to an embodiment of the present invention may further contain (E) a thermoplastic resin as an optional component in combination with the above-described components (A) to (D). The (E) thermoplastic resin as this (E) component does not include those corresponding to the above-described components (A) to (D).

[0123] Examples of the (E) thermoplastic resin include phenoxy resin, polyimide resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polycarbonate resin, polyetheretherketone resin, polyester resin, and the like. The (E) thermoplastic resin may be used alone or in combination of two or more.

[0124] Examples of the phenoxy resin include phenoxy resins having one or more skeletons selected from the group consisting of bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene skeleton, and trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group.

[0125] Specific examples of the phenoxy resin include "1256" and "4250" (both are phenoxy resins containing a bisphenol A skeleton) manufactured by Mitsubishi Chemical Corporation; "YX8100" (a phenoxy resin containing a bisphenol S skeleton) manufactured by Mitsubishi Chemical Corporation; "YX6954" (a phenoxy resin containing a bisphenol acetophenone skeleton) manufactured by Mitsubishi Chemical Corporation; "FX280" and "FX293" manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290", "YL7482", and "YL7891BH30" manufactured by Mitsubishi Chemical Corporation; and the like.

[0126] Specific examples of the polyimide resin include "SLK-6100" manufactured by Shin-Etsu Chemical Co., Ltd., "Lica Coat SN20" and "Lica Coat PN20" manufactured by Nippon Rika Chemical Co., Ltd., and the like.

[0127] Examples of the polyvinyl acetal resin include polyvinyl formal resin and polyvinyl butyral resin, and polyvinyl butyral resin is preferred. Specific examples of the polyvinyl acetal resin include "Denka Butyral 4000-2", "Denka Butyral 5000-A", "Denka Butyral 6000-C", "Denka Butyral 6000-EP" manufactured by Denki Kagaku Kogyo Kabushiki Kaisha; the Esrec BH series, BX series (e.g., BX-5Z), KS series (e.g., KS-1), BL series, BM series manufactured by Sekisui Chemical Co., Ltd.; and the like.

[0128] Examples of the polyolefin resin include ethylene-based copolymer resins such as low-density polyethylene, ultra-low-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-methyl acrylate copolymer; polyolefin polymers such as polypropylene and ethylene-propylene block copolymer; and the like.

[0129] Examples of the polybutadiene resin include, for example, a hydrogenated polybutadiene skeleton-containing resin, a hydroxy group-containing polybutadiene resin, a phenolic hydroxyl group-containing polybutadiene resin, a carboxy group-containing polybutadiene resin, an acid anhydride group-containing polybutadiene resin, an epoxy group-containing polybutadiene resin, an isocyanate group-containing polybutadiene resin, a urethane group-containing polybutadiene resin, a polyphenylene ether-polybutadiene resin, and the like.

[0130] Specific examples of the polyamideimide resin include "Vylon HR11NN" and "Vylon HR16NN" manufactured by Toyobo Co., Ltd. Specific examples of the polyamideimide resin also include modified polyamideimides such as "KS9100" and "KS9300" (polyamideimide containing a polysiloxane skeleton) manufactured by Hitachi Chemical Co., Ltd.

[0131] Specific examples of the polyethersulfone resin include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd.

[0132] Specific examples of the polysulfone resin include polysulfones "P1700", "P3500", etc. manufactured by Solvay Advanced Polymers, LLC.

[0133] Specific examples of the polyphenylene ether resin include "NORYL SA90" manufactured by SABIC. Specific examples of the polyetherimide resin include "Ultem" manufactured by GE.

[0134] Examples of the polycarbonate resin include a hydroxy group-containing carbonate resin, a phenolic hydroxyl group-containing carbonate resin, a carboxy group-containing carbonate resin, an acid anhydride group-containing carbonate resin, an isocyanate group-containing carbonate resin, a urethane group-containing carbonate resin, and the like. Specific examples of the polycarbonate resin include "FPC0220" manufactured by Mitsubishi Gas Chemical Company, Inc., "T6002" and "T6001" (polycarbonate diol) manufactured by Asahi Kasei Chemicals Corporation, "C-1090", "C-2090", and "C-3090" (polycarbonate diol) manufactured by Kuraray Co., Ltd. Specific examples of the polyetheretherketone resin include "Sumipro EK" manufactured by Sumitomo Chemical Company, Limited.

[0135] Examples of the polyester resin include a polyethylene terephthalate resin, a polyethylene naphthalate resin, a polybutylene terephthalate resin, a polybutylene naphthalate resin, a polytrimethylene terephthalate resin, a polytrimethylene naphthalate resin, a polycyclohexanedimethylene terephthalate resin, and the like.

[0136] (E) The weight average molecular weight (Mw) of the thermoplastic resin is preferably greater than 5,000, more preferably 8,000 or more, still more preferably 10,000 or more, particularly preferably 20,000 or more, and is preferably 100,000 or less, more preferably 70,000 or less, still more preferably 60,000 or less, particularly preferably 50,000 or less.

[0137] When the non-volatile components in the resin composition are 100% by mass, the content of the (E) thermoplastic resin in the resin composition may be 0% by mass, may be greater than 0% by mass, is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, particularly preferably 0.2% by mass or more, and is preferably 5% by mass or less, more preferably 3% by mass or less, particularly preferably 2% by mass or less.

[0138] When the content of the (E) thermoplastic resin in the resin composition is based on 100% by mass of the resin components in the resin composition, it may be 0% by mass, may be greater than 0% by mass, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, particularly preferably 0.5% by mass or more, preferably 10% by mass or less, more preferably 7.5% by mass or less, and particularly preferably 6% by mass or less.

[0139] [(F) Curing accelerator] The resin composition according to an embodiment of the present invention may further contain, as an optional component, an (F) curing accelerator in combination with the above-described components (A) to (E). The (F) curing accelerator as this (F) component does not include those corresponding to the above-described components (A) to (E). The (F) curing accelerator has a function as a curing catalyst that accelerates the curing of the (A) epoxy resin.

[0140] Examples of the (F) curing accelerator include phosphorus-based curing accelerators, urea-based curing accelerators, guanidine-based curing accelerators, imidazole-based curing accelerators, metal-based curing accelerators, amine-based curing accelerators, and the like. Among them, imidazole-based curing accelerators are preferred. The (F) curing accelerator may be used alone or in combination of two or more.

[0141] Examples of phosphorus-based curing accelerators include aliphatic phosphonium salts such as tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium) pyromellitate, tetrabutylphosphonium hydrogen hexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate, di-tert-butyldimethylphosphonium tetraphenylborate; aromatic phosphonium salts such as methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra-p-tolylborate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, triphenylethylphosphonium tetraphenylborate, tris(3-methylphenyl)ethylphosphonium tetraphenylborate, tris(2-methoxyphenyl)ethylphosphonium tetraphenylborate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate; aromatic phosphine-borane complexes such as triphenylphosphine·triphenylborane; aromatic phosphine-quinone addition reactants such as triphenylphosphine·p-benzoquinone addition reactant; aliphatic phosphines such as tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butyl(2-butenyl)phosphine, di-tert-butyl(3-methyl-2-butenyl)phosphine, tricyclohexylphosphine;Aromatic phosphines such as dibutylphenylphosphine, di-tert-butylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclohexylphosphine, triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tris(4-ethylphenyl)phosphine, tris(4-propylphenyl)phosphine, tris(4-isopropylphenyl)phosphine, tris(4-butylphenyl)phosphine, tris(4-tert-butylphenyl)phosphine, tris(2,4-dimethylphenyl)phosphine, tris(2,5-dimethylphenyl)phosphine, tris(2,6-dimethylphenyl)phosphine, tris(3,5-dimethylphenyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, tris(2,6-dimethyl-4-ethoxyphenyl)phosphine, tris(2-methoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine, tris(4-ethoxyphenyl)phosphine, tris(4-tert-butoxyphenyl)phosphine, diphenyl-2-pyridylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,2-bis(diphenylphosphino)acetylene, 2,2'-bis(diphenylphosphino)diphenylether, etc. are included.;

[0142] Examples of urea-based curing accelerators include, for example, 1,1-dimethylurea; aliphatic dimethylureas such as 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, 3-cyclooctyl-1,1-dimethylurea; aromatic dimethylureas such as 3-phenyl-1,1-dimethylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, 3-(3,4-dimethylphenyl)-1,1-dimethylurea, 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4-methoxyphenyl)-1,1-dimethylurea, 3-(4-nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy)phenyl]-1,1-dimethylurea, 3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trifluoromethyl)phenyl]-1,1-dimethylurea, N,N-(1,4-phenylene)bis(N’,N’-dimethylurea), N,N-(4-methyl-1,3-phenylene)bis(N’,N’-dimethylurea) [toluene bisdimethylurea], and the like.

[0143] Examples of guanidine-based curing accelerators include, for example, dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide, and the like.

[0144] Examples of imidazole-based curing accelerators include imidazole compounds such as 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline, and adducts of imidazole compounds and epoxy resins. Commercially available products of imidazole-based curing accelerators include, for example, "1B2PZ", "2E4MZ", "2MZA-PW", "2MZ-OK", "2MA-OK", "2MA-OK-PW", "2PHZ", "2PHZ-PW", "Cl1Z", "Cl1Z-CN", "Cl1Z-CNS", "C11Z-A" manufactured by Shikoku Kasei Kogyo Co., Ltd.; "P200-H50" manufactured by Mitsubishi Chemical Corporation, etc.

[0145] Examples of metal-based hardening 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 organocobalt complexes such as cobalt(II) acetylacetonate and cobalt(III) acetylacetonate, organocopper complexes such as copper(II) acetylacetonate, organozinc complexes such as zinc(II) acetylacetonate, organoiron complexes such as iron(III) acetylacetonate, organonickel complexes such as nickel(II) acetylacetonate, and organomanganese complexes such as manganese(II) acetylacetonate. Examples of organometallic salts include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

[0146] Examples of amine-based hardening accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene, and the like. As the amine-based hardening accelerator, commercially available products may be used. For example, "MY-25" manufactured by Ajinomoto Fine-Techno Co., Inc. and the like can be mentioned.

[0147] When the non-volatile components in the resin composition are 100% by mass, the content of the (F) hardening accelerator in the resin composition may be 0% by mass, may be greater than 0% by mass, preferably 0.01% by mass or more, more preferably 0.02% by mass or more, particularly preferably 0.03% by mass or more, preferably 1% by mass or less, more preferably 0.5% by mass or less, and particularly preferably 0.3% by mass or less.

[0148] When the resin components in the resin composition are 100% by mass, the content of the (F) hardening accelerator in the resin composition may be 0% by mass, may be greater than 0% by mass, preferably 0.01% by mass or more, more preferably 0.05% by mass or more, particularly preferably 0.1% by mass or more, preferably 2% by mass or less, more preferably 1.5% by mass or less, and particularly preferably 1% by mass or less.

[0149] [(G) Radical polymerizable compound] The resin composition according to an embodiment of the present invention may further contain, as an optional component, (G) an arbitrary radical polymerizable compound in combination with the above-described components (A) to (F). The (G) radical polymerizable compound as the component (G) does not include those corresponding to the above-described components (A) to (F). The (G) radical polymerizable compound may be used alone or in combination of two or more.

[0150] The (G) radical polymerizable compound may have an ethylenically unsaturated bond. The (G) radical polymerizable compound may have, for example, an unsaturated hydrocarbon group such as an allyl group, a 3-cyclohexenyl group, a 3-cyclopentenyl group, a p-vinylphenyl group, an m-vinylphenyl group, an o-vinylphenyl group; an α,β-unsaturated carbonyl group such as an acryloyl group, a methacryloyl group, a maleimide group (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl group); and the like. The (G) radical polymerizable compound preferably has two or more radical polymerizable groups.

[0151] Examples of the (G) radical polymerizable compound include (meth)acrylic radical polymerizable compounds, styrene radical polymerizable compounds, allyl radical polymerizable compounds, maleimide radical polymerizable compounds, and the like.

[0152] (Meth)acrylic radical polymerizable compounds are, for example, compounds having one or more, preferably two or more acryloyl groups and / or methacryloyl groups. Examples of (meth)acrylic radical polymerizable compounds include low molecular weight (molecular weight less than 1000) aliphatic (meth)acrylate compounds such as 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-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tetra(meth)acrylate; low molecular weight (molecular weight less than 1000) ether-containing (meth)acrylate compounds such as dioxane glycol di(meth)acrylate, 3,6-dioxa-1,8-octanediol di(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, propoxylated bisphenol A di(meth)acrylate; low molecular weight (molecular weight less than 1000) isocyanurate-containing (meth)acrylate compounds such as tris(3-hydroxypropyl)isocyanurate tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, ethoxylated isocyanuric acid tri(meth)acrylate; high molecular weight (molecular weight 1000 or more) acrylate compounds such as (meth)acrylic-modified polyphenylene ether resin, and the like.Examples of commercially available (meth)acrylic radical polymerizable compounds include, for example, "A-DOG" (dioxane glycol diacrylate) manufactured by Shin-Nakamura Chemical Co., Ltd., "DCP-A" (tricyclodecane dimethanol diacrylate), "DCP" (tricyclodecane dimethanol dimethacrylate) manufactured by Kyoeisha Chemical Co., Ltd., "KAYARAD R-684" (tricyclodecane dimethanol diacrylate), "KAYARAD R-604" (dioxane glycol diacrylate) of Nippon Kayaku Co., Ltd., "SA9000", "SA9000-111" (methacrylic modified polyphenylene ether) manufactured by SABIC Innovative Plastics, etc.

[0153] Styrene-based radical polymerizable compounds are, for example, compounds having one or more, preferably two or more vinyl groups directly bonded to aromatic carbon atoms. Examples of styrene-based radical polymerizable compounds include low molecular weight (molecular weight less than 1000) styrene-based 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, bis(4-vinylphenyl)ether; high molecular weight (molecular weight 1000 or more) styrene-based compounds such as vinylbenzyl-modified polyphenylene ether resin, styrene-divinylbenzene copolymer, etc. Examples of commercially available styrene-based radical polymerizable compounds include, for example, "ODV-XET(X03)", "ODV-XET(X04)", "ODV-XET(X05)" (styrene-divinylbenzene copolymer) manufactured by Nippon Steel Chemical & Material Co., Ltd., "OPE-2St 1200", "OPE-2St 2200" (vinylbenzyl-modified polyphenylene ether resin) manufactured by Mitsubishi Gas Chemical Co., Inc.

[0154] An allyl radical polymerizable compound is, for example, a compound having one or more, preferably two or more allyl groups. Examples of the allyl radical polymerizable compound 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-naphthalenedicarboxylate; allyl ester compounds of isocyanuric acid 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 diallyl diphenylsilane. Examples of commercially available allyl radical polymerizable compounds include "TAIC" (1,3,5-triallyl isocyanurate) manufactured by Nippon Kasei Co., Ltd., "DAD" (diallyl diphenate) manufactured by Nisshu Technofine Chemical Co., Ltd., "TRIAM-705" (triallyl trimellitate) manufactured by Wako Pure Chemical Industries, Ltd., the product name "DAND" (diallyl 2,3-naphthalenedicarboxylate) 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 Kasei Kogyo 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 Kasei Co., Ltd.

[0155] The maleimide-based radically polymerizable compound is, for example, a compound having one or more, preferably two or more maleimide groups. The maleimide-based radically polymerizable compound may be an aliphatic maleimide compound containing an aliphatic amine skeleton or an aromatic maleimide compound containing an aromatic amine skeleton. Examples of commercially available maleimide-based radically polymerizable compounds include "SLK-2600" manufactured by Shin-Etsu Chemical Co., Ltd., "BMI-1500", "BMI-1700", "BMI-3000J", "BMI-689", "BMI-2500" (a dimer diamine structure-containing maleimide compound) manufactured by Designer Molecules, Inc., "BMI-6100" (an aromatic maleimide compound) manufactured by Designer Molecules, Inc., "MIR-5000-60T", "MIR-3000-70MT" (biphenyl aralkyl type maleimide compounds) manufactured by Nippon Kayaku Co., Ltd., "BMI-70", "BMI-80" manufactured by K.I. Kasei Co., Ltd., "BMI-2300", "BMI-TMH" manufactured by Daiwa Kasei Kogyo Co., Ltd., and the like. Further, as the maleimide-based radically polymerizable compound, a maleimide resin (an indane ring skeleton-containing maleimide compound) disclosed in Invention Association Publication Technical Report Publication No. 2020-500211 may be used.

[0156] (G) The ethylene unsaturated bond equivalent of the radically polymerizable compound is preferably 20 g / eq. to 3,000 g / eq., more preferably 50 g / eq. to 2,500 g / eq., still more preferably 70 g / eq. to 2,000 g / eq., and particularly preferably 90 g / eq. to 1,500 g / eq. The ethylene unsaturated bond equivalent represents the mass of the radically polymerizable compound per equivalent of the ethylene unsaturated bond.

[0157] (G) The weight average molecular weight (Mw) of the radically polymerizable compound is preferably 40,000 or less, more preferably 10,000 or less, still more preferably 5,000 or less, and particularly preferably 3,000 or less. The lower limit is not particularly limited, and may be, for example, 150 or more.

[0158] The content of the (G) radically polymerizable compound in the resin composition may be 0% by mass, may be greater than 0% by mass, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, particularly preferably 1% by mass or more, preferably 15% by mass or less, more preferably 10% by mass or less, and particularly preferably 5% by mass or less when the non-volatile components in the resin composition are 100% by mass.

[0159] The content of the (G) radically polymerizable compound in the resin composition may be 0% by mass, may be greater than 0% by mass, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, particularly preferably 1% by mass or more, preferably 15% by mass or less, more preferably 10% by mass or less, and particularly preferably 7.5% by mass or less when the resin components in the resin composition are 100% by mass.

[0160] [(H) Optional Additive] The resin composition according to an embodiment of the present invention may further contain, as an optional non-volatile component, (H) an optional additive in combination with the above-described components (A) to (G). Examples of (H) the optional additive include radical polymerization initiators such as peroxide-based radical polymerization initiators and azo-based radical polymerization initiators; thermosetting resins other than epoxy resins such as epoxy acrylate resins, urethane acrylate resins, urethane resins, cyanate resins, benzoxazine resins, unsaturated polyester resins, phenol resins, melamine resins, and silicone resins; organic fillers such as rubber particles; organometallic compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, and carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and phenothiazine; leveling agents such as silicone-based leveling agents and acrylic polymer-based leveling agents; thickeners such as benton and montmorillonite; antifoaming agents such as silicone-based antifoaming agents, acrylic-based antifoaming agents, fluorine-based antifoaming agents, and vinyl resin-based antifoaming agents; ultraviolet absorbers such as benzotriazole-based ultraviolet absorbers; adhesion improvers such as urea silane; adhesion imparting agents such as triazole-based adhesion imparting agents, tetrazole-based adhesion imparting agents, and triazine-based adhesion imparting agents; antioxidants such as hindered phenol-based antioxidants; fluorescent brighteners such as stilbene derivatives; surfactants such as fluorine-based surfactants and silicone-based surfactants; flame retardants such as phosphorus-based flame retardants (e.g., phosphate ester compounds, phosphazene compounds, phosphinic acid compounds, red phosphorus), nitrogen-based flame retardants (e.g., melamine sulfate), halogen-based flame retardants, and inorganic-based flame retardants (e.g., antimony trioxide); dispersants such as phosphate ester-based dispersants, polyoxyalkylene-based dispersants, acetylene-based dispersants, silicone-based dispersants, anionic dispersants, and cationic dispersants; stabilizers such as borate-based stabilizers, titanate-based stabilizers, aluminate-based stabilizers, zirconate-based stabilizers, isocyanate-based stabilizers, carboxylic acid-based stabilizers, and carboxylic anhydride-based stabilizers. (H) The optional additive may be used alone or in combination of two or more.

[0161] [(I) Solvent] The resin composition according to this embodiment may further contain, as an optional volatile component, (I) a solvent in combination with the above-described non-volatile components such as components (A) to (H). Usually, an organic solvent is used as the (I) solvent. Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, and γ-butyrolactone; ether solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, and anisole; alcohol solvents such as methanol, ethanol, propanol, butanol, and ethylene glycol; ether ester solvents such as 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl diglycol acetate, γ-butyrolactone, and methyl methoxypropionate; ester alcohol solvents such as methyl lactate, ethyl lactate, and methyl 2-hydroxyisobutyrate; ether alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, and diethylene glycol monobutyl ether (butyl carbitol); amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; nitrile solvents such as acetonitrile and propionitrile; aliphatic hydrocarbon solvents such as hexane, cyclopentane, cyclohexane, and methylcyclohexane; and aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene. The (I) solvent may be used alone or in combination of two or more.

[0162] (I) The content of the solvent is not particularly limited. When the total components in the resin composition are 100% by mass, for example, it can be 60% by mass or less, 40% by mass or less, 30% by mass or less, 20% by mass or less, 15% by mass or less, 10% by mass or less, etc., and it may even be 0% by mass.

[0163] [Method for producing the resin composition] The resin composition according to one embodiment of the present invention can be produced, for example, by mixing the above-described components. The above-described components may be mixed partially or entirely simultaneously, or may be mixed in order. During the process of mixing each component, the temperature may be appropriately set, and thus, heating and / or cooling may be performed temporarily or throughout. Also, during the process of mixing each component, stirring or shaking may be performed.

[0164] [Physical properties of the resin composition] The above-described resin composition can be cured by heat. Thus, by thermosetting the resin composition, a cured product of the resin composition can be obtained. Usually, among the components contained in the resin composition, volatile components such as (I) the solvent can be volatilized by the heat during thermosetting, but non-volatile components such as components (A) to (H) are not volatilized by the heat during thermosetting. Thus, the cured product of the resin composition may contain the non-volatile components of the resin composition or reaction products thereof.

[0165] The resin composition according to one embodiment of the present invention can usually obtain a cured product with a low dielectric tangent. For example, when measuring the dielectric tangent of the cured product under the conditions described in the [Dielectric properties] section of the examples described later, a low dielectric tangent can be obtained. The dielectric tangent of the cured product is preferably 0.0040 or less, more preferably 0.0035 or less, and particularly preferably 0.0030 or less. The lower limit is not particularly limited and can be, for example, 0.0001 or more.

[0166] The resin composition according to one embodiment of the present invention can usually obtain a cured product with excellent crack resistance. For example, when the crack resistance of the cured product is judged under the conditions described in the [Crack Resistance] section of the examples described later, a high yield can be obtained. The yield of the cured product is preferably 50% or more, more preferably 75% or more, and particularly preferably 90% or more.

[0167] The resin composition according to one embodiment of the present invention can usually obtain a cured product with excellent adhesion to the plating conductor layer. That is, when a conductor layer is formed by plating on the cured product of the resin composition, high adhesion can be obtained between the conductor layer and the cured product. For example, when the plating peel strength is measured under the conditions described in the [Adhesion to Plating Conductor Layer] section of the examples described later, the plating peel strength can be increased. The plating peel strength represents the magnitude of the force required to peel off the conductor layer formed by plating on the cured product of the resin composition. The greater this plating peel strength, the better the adhesion to the plating conductor layer. The plating peel strength is preferably 0.30 kgf / cm or more, more preferably 0.35 kgf / cm or more, and particularly preferably 0.40 kgf / cm or more.

[0168] [Use of Resin Composition] The resin composition according to one embodiment of the present invention can be used as a resin composition for insulating applications, and in particular, can be preferably used as a resin composition for forming an insulating layer (resin composition for forming an insulating layer). For example, the resin composition according to one embodiment of the present invention can be used as a resin composition for forming an insulating layer of a printed wiring board and can be preferably used as a resin composition for forming an interlayer insulating layer (resin composition for interlayer insulation applications).

[0169] In addition, the resin composition according to an embodiment of the present invention may be used as a resin composition for forming a redistribution layer (resin composition for forming a redistribution layer). The redistribution layer forming layer refers to an insulating layer for forming a redistribution layer. Further, the redistribution layer refers to a conductor layer formed on the redistribution layer forming layer as an insulating layer. For example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition according to the present embodiment may be used as a resin composition for forming a redistribution layer forming layer. Further, when a semiconductor chip package is manufactured through the following steps (1) to (6), a redistribution layer may be further formed on the sealing layer. (1) Step of laminating a temporary fixing film on a substrate, (2) Step of temporarily fixing a semiconductor chip on the temporary fixing film, (3) Step of forming a sealing layer on the semiconductor chip, (4) Step of peeling the substrate and the temporary fixing film from the semiconductor chip, (5) Step of forming a redistribution layer forming layer as an insulating layer on the surface of the semiconductor chip from which the substrate and the temporary fixing film have been peeled, and (6) Step of forming a redistribution layer as a conductor layer on the redistribution layer forming layer

[0170] Furthermore, the resin composition according to an embodiment of the present invention can be widely used in applications where resin compositions are used, such as resin sheets, sheet-like laminated materials such as prepregs, solder resists, underfill materials, die bonding materials, semiconductor encapsulants, hole filling resins, component embedding resins, and the like.

[0171] [Sheet-like laminated material] The resin composition according to an embodiment of the present invention may be applied and used in a varnish state, but industrially, it is preferably used in the form of a sheet-like laminated material containing the resin composition.

[0172] As the sheet-like laminated material, the following resin sheets and prepregs are preferable.

[0173] In one embodiment of the present invention, the resin sheet includes a support and a resin composition layer provided on the support. The resin composition layer is formed of the resin composition according to this embodiment. Therefore, the resin composition layer usually contains the resin composition and preferably contains only the resin composition.

[0174] From the viewpoints of thinning the printed wiring board and providing a cured product having excellent insulating properties even if the cured product of the resin composition is a thin film, the thickness of the resin composition layer is preferably 50 μm or less, more preferably 40 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, but may be 5 μm or more, 10 μm or more, etc.

[0175] Examples of the support include a film made of a plastic material, a metal foil, and a release paper, and a film made of a plastic material and a metal foil are preferred.

[0176] When using a film made of a plastic material as the support, examples of the plastic material include polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"), polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylics such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyethersulfide (PES), polyether ketone, polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

[0177] When using a metal foil as the support, examples of the metal foil include a copper foil and an aluminum foil, and a copper foil is preferred. As the copper foil, a foil made of single metal copper may be used, or a foil made of an alloy of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used.

[0178] The support may be subjected to matting treatment, corona treatment, or antistatic treatment on the surface that is joined to the resin composition layer.

[0179] As the support, a support with a release layer having a release layer on the surface joined to the resin composition layer may be used. Examples of the release agent used for the release layer of the support with a release layer include one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. As the support with a release layer, commercially available products may be used. For example, "SK-1", "AL-5", "AL-7" manufactured by Lintec Corporation, which are PET films having a release layer mainly composed of an alkyd resin-based release agent, "Lumirror T60" manufactured by Toray Industries, Inc., "Purex" manufactured by Teijin Limited, "Unipile" manufactured by Unitika Ltd., etc.

[0180] The thickness of the support is not particularly limited, but a range of 5 μm to 75 μm is preferable, and a range of 10 μm to 60 μm is more preferable. When using a support with a release layer, it is preferable that the total thickness of the support with a release layer is within the above range.

[0181] In one embodiment, the resin sheet may further include an arbitrary layer as needed. Examples of such an arbitrary layer include a protective film conforming to the support provided on the surface of the resin composition layer that is not joined to the support (i.e., the surface opposite to 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, it is possible to suppress the adhesion of dust and scratches to the surface of the resin composition layer.

[0182] The resin sheet can be produced, for example, by directly using a liquid (varnish-like) resin composition, or by dissolving the resin composition in a solvent to prepare a liquid (varnish-like) resin composition, applying this onto the support using a die coater or the like, and then further drying to form a resin composition layer.

[0183] Examples of the organic solvent include the same solvents as those described as components of the resin composition. The organic solvent may be used alone or in combination of two or more.

[0184] Drying may be carried out by known methods such as heating and hot air blowing. The drying conditions are not particularly limited, but the drying is carried out so that the content of the organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. Although it may vary depending on the boiling point of the organic solvent in the resin varnish, for example, when using a resin varnish containing 30% by mass to 60% by mass of the organic solvent, the resin composition layer can be formed by drying at 50°C to 150°C for 3 minutes to 10 minutes.

[0185] The resin sheet can be wound up in a roll and stored. When the resin sheet has a protective film, it can be used by peeling off the protective film.

[0186] In one embodiment, the prepreg is produced by a method including impregnating a sheet-like fiber base material with the resin composition according to this embodiment.

[0187] As the sheet-like fiber base material used for the prepreg, for example, those commonly used as prepreg base materials such as glass cloth, aramid nonwoven fabric, and liquid crystal polymer nonwoven fabric can be used. From the viewpoint of thinning the printed wiring board, the thickness of the sheet-like fiber base material is preferably 50 μm or less, more preferably 40 μm or less, still more preferably 30 μm or less, and particularly preferably 20 μm or less. The lower limit of the thickness of the sheet-like fiber base material is not particularly limited and is usually 10 μm or more.

[0188] The prepreg can be produced by methods such as the hot melt method and the solvent method.

[0189] The thickness of the prepreg can be in the same range as that of the resin composition layer in the resin sheet described above.

[0190] The sheet-like laminated material can be suitably used for forming the insulating layer of a printed wiring board (for the insulating layer of a printed wiring board), and can be more suitably used for forming the interlayer insulating layer of a printed wiring board (for the interlayer insulating layer of a printed wiring board).

[0191] [Printed Wiring Board] The printed wiring board according to an embodiment of the present invention includes an insulating layer containing a cured product obtained by curing the resin composition according to this embodiment. This printed wiring board can be manufactured, for example, by a method including the following steps (I) and (II). (I) A step of forming a resin composition layer on an inner layer substrate. (II) A step of curing the resin composition layer to form an insulating layer.

[0192] The "inner layer substrate" used in step (I) is a member that becomes the substrate of a printed wiring board. Examples include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, thermosetting polyphenylene ether substrates, and the like. Further, the substrate may have a conductor layer on one or both of its surfaces, and this conductor layer may be pattern-processed. An inner layer substrate with a conductor layer (circuit) formed on one or both surfaces of the substrate is sometimes referred to as an "inner layer circuit board". Also, when manufacturing a printed wiring board, an intermediate product on which an insulating layer and / or a conductor layer are to be further formed is also included in the above-mentioned "inner layer substrate". When the printed wiring board is a component-embedded circuit board, an inner layer substrate with components embedded therein may be used.

[0193] The formation of the resin composition layer on the inner layer substrate is preferably carried out using the resin sheet described above. For example, the resin composition layer can be formed by a method including laminating a resin sheet on the inner layer substrate so that the resin composition layer of the resin sheet is joined to the inner layer substrate. The lamination of the inner layer substrate and the resin sheet can be carried out, for example, by thermocompression bonding the resin sheet to the inner layer substrate from the support side. Examples of the member for thermocompression bonding the resin sheet to the inner layer substrate (hereinafter also referred to as "thermocompression bonding member") include a heated metal plate (such as a SUS mirror plate) or a metal roll (such as a SUS roll). Note that it is preferable to press through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface unevenness of the inner layer substrate instead of directly pressing the thermocompression bonding member against the resin sheet.

[0194] 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 bonding temperature is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C, the thermocompression bonding pressure is preferably in the range of 0.098 MPa to 1.77 MPa, more preferably in the range of 0.29 MPa to 1.47 MPa, and the thermocompression bonding time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. The lamination is preferably carried out under reduced pressure conditions of a pressure of 26.7 hPa or less.

[0195] The lamination can be carried out by a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum pressurization type laminator manufactured by Meiki Seisakusho Co., Ltd., a vacuum applicator manufactured by Nichio Materials Co., Ltd., a batch type vacuum pressurization laminator, and the like.

[0196] After the lamination, under normal pressure (atmospheric pressure), for example, a smoothing treatment of the laminated resin sheet may be carried out by pressing the thermocompression bonding member from the support side. The pressing conditions for the smoothing treatment can be the same as the thermocompression bonding conditions for the above lamination. The smoothing treatment can be carried out by a commercially available laminator. Note that the lamination and the smoothing treatment may be continuously carried out using the above commercially available vacuum laminator.

[0197] The support may be removed between step (I) and step (II), or may be removed after step (II).

[0198] 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 of the resin composition layer is usually carried out by heat curing. Specific curing conditions for the resin composition layer may be those commonly employed when forming an insulating layer of a printed wiring board.

[0199] For example, the heat curing conditions of the resin composition layer vary depending on the type of the resin composition and the like. In one embodiment, the curing temperature is preferably 120°C to 240°C, more preferably 150°C to 220°C, and even more preferably 170°C to 210°C. The curing time may be preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and even more preferably 15 minutes to 100 minutes.

[0200] Before heat curing the resin composition layer, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to heat curing the resin composition layer, the resin composition layer may be preheated at a temperature of 50°C to 150°C, preferably 60°C to 140°C, more preferably 70°C to 130°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.

[0201] When manufacturing a printed wiring board, steps of (III) drilling holes in the insulating layer, (IV) roughening the insulating layer, and (V) forming a conductor layer may be further carried out. These steps (III) to (V) may be carried out according to various methods known to those skilled in the art used for manufacturing a printed wiring board. When the support is removed after step (II), the removal of the support may be carried out between step (II) and step (III), between step (III) and step (IV), or between step (IV) and step (V). Further, if necessary, the formation of the insulating layer and the conductor layer in steps (I) to (V) may be repeatedly carried out to form a multilayer wiring board.

[0202] In other embodiments, the printed wiring board can be manufactured using the prepreg described above. The manufacturing method can be basically the same as the case of using a resin sheet.

[0203] Step (III) is a step of drilling holes in the insulating layer, whereby holes such as via holes and through holes can be formed in the insulating layer. Step (III) may be carried out using, for example, a drill, a laser, a plasma, etc., depending on the composition of the resin composition used for forming the insulating layer. The dimensions and shape of the holes may be appropriately determined according to the design of the printed wiring board.

[0204] Step (IV) is a step of roughening the insulating layer. Usually, smear removal is also carried out in this step (IV). The procedures and conditions for the roughening treatment are not particularly limited, and known procedures and conditions used when forming the insulating layer of the printed wiring board can be adopted. For example, the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order.

[0205] Examples of the swelling liquid used for the roughening treatment include an alkaline solution, a surfactant solution, etc., and an alkaline solution is preferably used. As the alkaline solution, a sodium hydroxide solution and a potassium hydroxide solution are more preferable. Examples of commercially available swelling liquids include "Swelling Dip Security Gun P" and "Swelling Dip Security Gun SBU" manufactured by Atotech Japan Co., Ltd. The swelling treatment with the swelling liquid can be carried out, for example, by immersing the insulating layer in a swelling liquid at 30°C to 90°C for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling liquid at 40°C to 80°C for 5 minutes to 15 minutes.

[0206] Examples of the oxidizing agent used for the roughening treatment include an alkaline permanganate solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. The roughening treatment with an oxidizing agent such as an alkaline permanganate solution is preferably performed by immersing the insulating layer in the oxidizing agent solution heated to 60°C to 100°C for 10 minutes to 30 minutes. Further, the concentration of the permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Security Guard P" manufactured by Atotech Japan Co., Ltd.

[0207] The neutralizing solution used for the roughening treatment is preferably an acidic aqueous solution. Examples of commercially available products include "Reduction Solution Security Guard P" manufactured by Atotech Japan Co., Ltd. The treatment with the neutralizing solution can be performed by immersing the treated surface that has been roughened with the oxidizing agent in the neutralizing solution at 30°C to 80°C for 5 minutes to 30 minutes. From the viewpoint of workability and the like, a method of immersing the object that has been roughened with the oxidizing agent in the neutralizing solution at 40°C to 70°C for 5 minutes to 20 minutes is preferable.

[0208] In one embodiment, the arithmetic mean roughness (Ra) of the surface of the insulating layer after the roughening treatment is preferably 500 nm or less, more preferably 400 nm or less, and still more preferably 300 nm or less. The lower limit is not particularly limited and can be, for example, 1 nm or more, 2 nm or more, etc. Further, the root mean square roughness (Rq) of the surface of the insulating layer after the roughening treatment is preferably 500 nm or less, more preferably 400 nm or less, and still more preferably 300 nm or less. The lower limit is not particularly limited and can be, for example, 1 nm or more, 2 nm or more, etc. The arithmetic mean roughness (Ra) and the root mean square roughness (Rq) of the surface of the insulating layer can be measured using a non-contact surface roughness meter.

[0209] Step (V) is a step of forming a conductor layer, which is formed on an insulating layer. The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer contains one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. The conductor layer may be a single-metal layer or an alloy layer. Examples of the alloy layer include layers formed from alloys of two or more metals selected from the above group (for example, nickel-chromium alloys, copper-nickel alloys, and copper-titanium alloys). Among them, 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 nickel-chromium alloy, copper-nickel alloy, or copper-titanium alloy is preferred, a single-metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of nickel-chromium alloy is more preferred, and a single-metal layer of copper is even more preferred.

[0210] The conductor layer may have a single-layer structure, or may have a multilayer structure in which two or more single-metal layers or alloy layers made of different types of metals or alloys are laminated. When the conductor layer has a multilayer structure, the layer in contact with the insulating layer is preferably a single-metal layer of chromium, zinc, or titanium, or an alloy layer of nickel-chromium alloy.

[0211] The thickness of the conductor layer depends on the design of the desired printed wiring board, but is generally 3 μm to 35 μm, preferably 5 μm to 30 μm.

[0212] In one embodiment, the conductor layer may be formed by plating. For example, by using a conventionally known technique such as a semi-additive method or a full-additive method to plate on the surface of the insulating layer, a conductor layer having a desired wiring pattern can be formed. From the viewpoint of manufacturing simplicity, the semi-additive method is preferred. Hereinafter, an example of forming the conductor layer by the semi-additive method is shown.

[0213] First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern is formed on the formed plating seed layer to expose a part of the plating seed layer corresponding to a desired wiring pattern. After forming a metal layer by electrolytic plating on the exposed plating seed layer, the mask pattern is removed. Thereafter, an unnecessary plating seed layer is removed by etching or the like, and a conductor layer having a desired wiring pattern can be formed.

[0214] In another embodiment, the conductor layer may be formed using a metal foil. When forming the conductor layer using a metal foil, step (V) is preferably carried out between step (I) and step (II). For example, after step (I), the support is removed, and a metal foil is laminated on the surface of the exposed resin composition layer. The lamination of the resin composition layer and the metal foil may be carried out by a vacuum lamination method. The lamination conditions may be the same as those described for step (I). Next, step (II) is carried out to form an insulating layer. Thereafter, using the metal foil on the insulating layer, a conductor layer having a desired wiring pattern can be formed by a conventional known technique such as a subtractive method or a modified semi-additive method.

[0215] The metal foil can be manufactured by known methods such as an electrolytic method or a rolling method. Examples of commercially available metal foils include HLP foil, JXUT-III foil manufactured by JX Nippon Mining & Metals Corporation, 3EC-III foil, TP-III foil manufactured by Mitsui Mining & Smelting Co., Ltd., and the like.

[0216] [Semiconductor Device] A semiconductor device according to an embodiment of the present invention includes the above-described printed wiring board. The semiconductor device can be manufactured using the printed wiring board.

[0217] Examples of the semiconductor device include various semiconductor devices used in electrical products (such as computers, mobile phones, digital cameras, and televisions) and vehicles (such as motorcycles, automobiles, trains, ships, and airplanes).

Example

[0218] Hereinafter, examples of the present invention will be shown and specifically described. However, the present invention is not limited to these examples. In the following, "parts" and "%" representing amounts mean "parts by mass" and "mass%" respectively, unless otherwise specified. Also, the temperature conditions and pressure conditions in the case where the temperature is not specifically designated were room temperature (25°C) and atmospheric pressure (1 atm).

[0219] [Example 1] 5 parts of a liquid epoxy resin ("ZX1059" manufactured by Nippon Steel Chemical & Material Co., a 1:1 mixture (by mass) of bisphenol A type epoxy resin and bisphenol F type epoxy resin, epoxy equivalent: 169 g / eq.), 15 parts of a biphenyl type epoxy resin ("NC3000H" manufactured by Nippon Kayaku Co., epoxy equivalent of about 290 g / eq.) were dissolved by heating with stirring in a mixed solvent of 20 parts of toluene and 20 parts of MEK. After cooling the obtained solution to room temperature, 42 parts of an active ester curing agent ("HP-B-8151-62T" manufactured by DIC, active group equivalent 238 g / eq., toluene solution with a solid content of 62%), 4 parts of a triazine skeleton-containing phenolic curing agent ("LA-3018-50P" manufactured by DIC, hydroxyl group equivalent of about 151 g / eq., 2-methoxypropanol solution with a solid content of 50%), 10 parts of a phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, a 1:1 solution of MEK and cyclohexanone with a non-volatile content of 30% by mass), 1.5 parts of a silicon-containing resin (a resin in which a trimethoxysilyl group is introduced into the side chain of a direct addition unit of a styrene-butadiene copolymer, "X-12-1281C" manufactured by Shin-Etsu Chemical Co., number average molecular weight 5,000), 4 parts of a curing accelerator ("1B2PZ" manufactured by Shikoku Kasei Kogyo Co., MEK solution with a solid content of 10% by mass), 150 parts of an inorganic filler (spherical silica ("SO-C2" manufactured by Admatechs Co., average particle size 0.5 μm, specific surface area 5.8 m 2 / g)) surface-treated with an amine-based silane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co.) were mixed and uniformly dispersed with a high-speed rotary mixer to obtain Resin Composition 1.

[0220] [Example 2] Resin composition 2 was obtained in the same manner as in Example 1, except that 6 parts of a carbodiimide-based curing agent (Nisshinbo Chemicals, Inc.'s "V-03", active group equivalent of about 216 g / eq., toluene solution with a solid content of 50%) was added.

[0221] [Example 3] Resin composition 3 was obtained in the same manner as in Example 1, except that 6 parts of a thermosetting resin having a phenylene ether structure ((meth)acrylic radical polymerizable compound "SA9000" manufactured by SABIC Innovative Plastics, toluene solution with a solid content of 50%) was added.

[0222] [Example 4] Resin composition 4 was obtained in the same manner as in Example 1, except that 3 parts of a maleimide compound ("BMI-689" manufactured by Designer Molecules, maleimide group equivalent of 345 g / eq.) was added.

[0223] [Example 5] Resin composition 5 was obtained in the same manner as in Example 2, except that 40 parts of an active ester curing agent ("PC1300-02-65MA" manufactured by Air Water, active group equivalent of 199 g / eq., methyl amyl ketone solution with a solid content of 65 mass%) was used instead of 42 parts of an active ester curing agent ("HP-B-8151-62T" manufactured by DIC, active group equivalent of 238 g / eq., toluene solution with a solid content of 62%).

[0224] [Example 6] Resin composition 6 was obtained in the same manner as in Example 2, except that the amount of the silicon-containing resin ("X-12-1281C" manufactured by Shin-Etsu Chemical Co., Ltd.) was changed from 1.5 parts to 4.5 parts.

[0225] [Example 7] Resin composition 7 was obtained in the same manner as in Example 2, except that 1.5 parts of the silicon-containing resin ("X-12-1281C" manufactured by Shin-Etsu Chemical Co., Ltd.) was replaced with 1.5 parts of another silicon-containing resin (a resin in which a trimethoxysilyl group was introduced into the side chain of the direct addition unit of a styrene-butadiene copolymer, "X-12-1281A" manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight of 9,000).

[0226] [Example 8] Instead of 1.5 parts of a silicon-containing resin (“X-12-1281C” manufactured by Shin-Etsu Chemical Co., Ltd.), 1.5 parts of another silicon-containing resin (a resin in which a triethoxysilyl group is introduced into the side chain of a direct addition unit of a styrene-butadiene copolymer, “X-12-1281A-ES” manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight 9,500. It has a structure represented by formula (2), where j = 52, k = 0, l = 22, m = 29, n = 3, Y is an ethylene group, and R 46 is a resin that may correspond to a structure having an ethyl group.) was used. Resin composition 8 was obtained in the same manner as in Example 5 except for this substitution.

[0227] [Comparative Example 1] Comparative resin composition 1 was obtained in the same manner as in Example 1 except that 1.5 parts of a silicon-containing resin (“X-12-1281C” manufactured by Shin-Etsu Chemical Co., Ltd.) was not used.

[0228] [Comparative Example 2] Instead of 1.5 parts of a silicon-containing resin (“X-12-1281C” manufactured by Shin-Etsu Chemical Co., Ltd.), 1.4 parts of a styrene-diene copolymer (“Ricon 184” manufactured by Cray Valley) and 0.1 part of an alkoxysilane compound (epoxysilane “KBM403” manufactured by Shin-Etsu Chemical Co., Ltd.) were used. An attempt was made to prepare comparative resin composition 2 in the same manner as in Example 1, but the miscibility was poor and a uniform resin composition could not be obtained.

[0229] [Production of Resin Sheet] As a support, a polyethylene terephthalate film (“Lumirror R80” manufactured by Toray Industries, Inc., thickness 38 μm, softening point 130 °C) that had been subjected to a release treatment with an alkyd resin-based release agent (“AL-5” manufactured by Lintec Corporation) was prepared.

[0230] Resin compositions 1 to 8 and Comparative Resin Composition 1 were each uniformly applied onto a support using a die coater so that the thickness of the resin composition layer after drying would be 30 μm, and then dried at 70°C to 95°C for 3 minutes to form a resin composition layer on the support. Next, the rough surface of a polypropylene film (Alphan MA-411, thickness 15 μm, manufactured by Oji Fibrex Co., Ltd.) was laminated as a protective film onto the surface of the resin composition layer that was not joined to the support. As a result, a resin sheet A having a support, a resin composition layer, and a protective film in this order was obtained.

[0231] [Adhesion to the plating conductor layer] (1) Preparation of the inner layer substrate A glass cloth base epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.4 mm, "R1515A" manufactured by Panasonic Corporation) having inner layer circuits formed of copper on both sides was prepared as the inner layer substrate. Both sides of the inner layer substrate were etched with a micro-etching agent ("CZ8101" manufactured by Meck Co., Ltd.) by 1 μm to perform roughening treatment of the copper surface.

[0232] (2) Lamination of the resin sheet The protective film was peeled off from the resin sheet A to expose the resin composition layer. Using a batch-type vacuum pressure laminator (a two-stage build-up laminator "CVP700" manufactured by Nichco Materials Co., Ltd.), it was laminated onto both sides of the inner layer substrate so that the resin composition layer would be in contact with the inner layer substrate. The lamination was carried out by adjusting the pressure to 13 hPa or less under reduced pressure for 30 seconds and then performing pressure bonding at 120°C and a pressure of 0.74 MPa for 30 seconds. Next, a hot press was performed at 100°C and a pressure of 0.5 MPa for 60 seconds.

[0233] (3) Thermal curing of the resin composition layer Thereafter, the inner layer substrate laminated with the resin sheet was placed in an oven at 130°C and heated for 30 minutes, and then transferred to an oven at 180°C and heated for 30 minutes to thermally cure the resin composition layer and form an insulating layer composed of a cured product of the resin composition. Thereafter, the support was peeled off to obtain a cured substrate A having an insulating layer, an inner layer substrate, and an insulating layer in this order.

[0234] (4) Roughening treatment Desmear treatment as a roughening treatment was performed on the insulating layer of the cured substrate A. As the desmear treatment, the following wet desmear treatment was carried out.

[0235] (Wet desmear treatment) The cured substrate A was immersed in a swelling solution (aqueous solution of "Swelling Dip Securigant P" manufactured by Atotech Japan Co., Ltd., diethylene glycol monobutyl ether and sodium hydroxide) at 60 °C for 5 minutes, then immersed in an oxidizing agent solution (aqueous solution of "Concentrate Compact CP" manufactured by Atotech Japan Co., Ltd., potassium permanganate concentration of about 6% and sodium hydroxide concentration of about 4%) at 80 °C for 20 minutes, and then immersed in a neutralizing solution (aqueous solution of sulfuric acid and "Reduction Solution Securigant P" manufactured by Atotech Japan Co., Ltd.) at 40 °C for 5 minutes, and then dried at 80 °C for 15 minutes.

[0236] (5) Formation of conductor layer According to the semi-additive method, a conductor layer was formed on the roughened surface of the insulating layer. That is, the cured substrate A after the roughening treatment was immersed in an electroless plating solution containing PdCl2 at 40 °C for 5 minutes, and then immersed in an electroless copper plating solution at 25 °C for 20 minutes. Then, annealing treatment was performed by heating at 150 °C for 30 minutes, and then an etching resist was formed, and patterning was performed by etching. Thereafter, copper sulfate electrolytic plating was performed to form a conductor layer with a thickness of 30 μm, and annealing treatment was performed at 200 °C for 60 minutes. The obtained substrate is referred to as "evaluation substrate B".

[0237] (6) Evaluation of adhesion to plated conductor layer The measurement of the peel strength between the insulating layer and the plated conductor layer was carried out in accordance with Japanese Industrial Standard (JIS C6481). Specifically, a cut was made in the conductor layer of the evaluation substrate B to surround a rectangular portion with a width of 10 mm and a length of 100 mm. One end of this rectangular portion was peeled off and grasped with a gripping tool, and the load (kgf / cm) when it was peeled off vertically by 35 mm at a speed of 50 mm / min at room temperature was measured to obtain the peel strength (plating peel strength). A tensile testing machine ("AC-50C-SL" manufactured by TSE) was used for the measurement.

[0238] [Dielectric properties] The protective film was peeled off from the resin sheet A prepared in the examples and comparative examples, and heated at 200 °C for 90 minutes to thermoset the resin composition layer. Then, the support was peeled off to obtain a cured product of the resin composition. The obtained cured product was designated as "evaluation cured product C". The evaluation cured product C was cut to obtain test pieces with a width of 2 mm and a length of 80 mm. For these test pieces, the dielectric tangent was measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23 °C by the cavity resonance perturbation method using "HP8362B" manufactured by Agilent Technologies. The measurement was performed on three test pieces, and the average value was calculated.

[0239] [Crack resistance] (1) Lamination of resin sheets An inner layer substrate ("MCL-E700G" manufactured by Hitachi Chemical Co., Ltd., conductor layer thickness 35 μm, total thickness 0.4 mm, residual copper ratio 40%) having circuit conductors (copper) with a line / space (L / S) of 8 μm / 8 μm formed on both sides was prepared. The resin sheet A with the protective film peeled off was laminated on both sides of this inner layer substrate so that the resin composition layer was in contact with the inner layer substrate. Such lamination was carried out using a vacuum pressure laminator ("MVLP-500" manufactured by Meiki Seisakusho Co., Ltd.). After vacuum suction at 120 °C for 30 seconds, it was pressed for 30 seconds from above the support through a heat-resistant rubber under the conditions of a temperature of 120 °C and a pressure of 0.7 MPa. Next, under atmospheric pressure, pressing was performed for 60 seconds using a SUS mirror plate under the conditions of a temperature of 120 °C and a pressure of 0.55 MPa.

[0240] (2) Thermal curing of the resin composition layer Thereafter, the inner layer substrate laminated with the resin sheet was put into an oven at 130°C and heated for 30 minutes, then transferred to an oven at 180°C and heated for 30 minutes to thermoset the resin composition layer, thereby forming an insulating layer made of a cured product of the resin composition. Thereafter, the support was peeled off to obtain a cured substrate D having an insulating layer, an inner layer substrate, and an insulating layer in this order.

[0241] (3) Roughening treatment The cured substrate D was subjected to a desmear treatment as a roughening treatment. The desmear treatment was carried out in the same manner as the (wet desmear treatment) described in the above [Adhesion with the plated conductor layer] column.

[0242] (4) Evaluation of crack resistance Among the surfaces of the insulating layer after the desmear treatment, the surface of the insulating layer directly above the wiring pattern (L / S = 8 μm / 8 μm) of the inner layer substrate was observed. For 100 samples, it was confirmed whether cracks occurred on the surface of the insulating layer along the pattern shape of the inner layer substrate, and the ratio of the samples without cracks was obtained. This ratio was calculated as the "yield", and a yield of 50% or more was evaluated as "○", and less than 50% was evaluated as "×".

[0243] [Results] The results of the above-described examples and comparative examples are shown in Tables 1 and 2 below. Note that for Comparative Example 2, neither the peel strength, the dielectric tangent, nor the crack resistance could be evaluated.

[0244] [Table 1]

[0245] [Table 2]

Claims

1. (A) an epoxy resin, (B) a curing agent, and (C) a hydrogenated conjugated diene-aromatic vinyl copolymer resin which may contain an alkoxysilyl group, and component (C) contains (c1) a conjugated diene compound unit which may be hydrogenated and (c2) an aromatic vinyl compound unit, an alkoxysilyl group is bonded to part or all of the (c1) conjugated diene compound unit which may be hydrogenated, when the resin component in the resin composition is 100% by mass, the content of component (A) is 5% by mass or more and 50% by mass or less, a resin composition wherein when the resin component in the resin composition is 100% by mass, the content of component (C) is 0.5% by mass or more and 15% by mass or less.

2. the (c1) conjugated diene compound unit which may be hydrogenated is a butadiene unit which may be hydrogenated, the resin composition according to claim 1, wherein the (c2) aromatic vinyl compound unit is a styrene unit.

3. the (c1) conjugated diene compound unit which may be hydrogenated contains a direct addition unit, the resin composition according to claim 1 or 2, which is part or all of the side chain of the direct addition unit.

4. the resin composition according to any one of claims 1 to 3, wherein when component (C) is 100% by mass, the amount of the (c2) aromatic vinyl compound unit is 15% by mass or more and 50% by mass or less.

5. (A) an epoxy resin, (B) a curing agent, and (C) a hydrogenated conjugated diene-aromatic vinyl copolymer resin which may contain an alkoxysilyl group, and component (C) contains (c3) an alkenylalkoxysilane unit, when the resin component in the resin composition is 100% by mass, the content of component (A) is 5% by mass or more and 50% by mass or less, a resin composition wherein when the resin component in the resin composition is 100% by mass, the content of component (C) is 0.5% by mass or more and 15% by mass or less.

6. the resin composition according to any one of claims 1 to 5, wherein component (C) contains a structure represented by the following formula (1). 【Chemical 1】 (In formula (1), R １ to R ３１ , R ３４ to R ４０ , and R ４３ to R ４５ each independently represents a hydrogen atom or a monovalent hydrocarbon group, X represents a single bond or a divalent linking group, R ３２ 、 R ３３ 、 R ４１ and R ４２ each independently represents a monovalent hydrocarbon group, Ar represents an aryl group which may have a substituent, a, b, c and d each independently represent an integer of 0 or more, e and f represent integers of 0 or more satisfying e + f ≧ 1, g represents an integer of 1 or more, h and i each independently represent an integer of 1 to 3.) However, the order of the repeating unit a, the repeating unit b, the repeating unit c, the repeating unit d, the repeating unit e, the repeating unit f, and the repeating unit g is arbitrary.)

7. The resin composition according to any one of claims 1 to 6, wherein the component (C) contains a structure represented by the following formula (2). 【Chemical 2】 (In formula (2), Y represents a single bond or a divalent hydrocarbon group, R ４６ and R ４７ each independently represents a monovalent hydrocarbon group, j and k each independently represent an integer of 0 or more, l and m each independently represent an integer greater than 0, n represents an integer of 1 to 3. However, the order of the repeating unit j, the repeating unit k, the repeating unit l, and the repeating unit m is arbitrary.)

8. The resin composition according to any one of claims 1 to 7, wherein the amount of the component (C) is 0.01% by mass or more and 10% by mass or less based on 100% by mass of the non-volatile components of the resin composition.

9. The resin composition according to any one of claims 1 to 8, wherein the curing agent (B) contains an active ester-based curing agent.

10. The resin composition according to any one of claims 1 to 9, which contains an inorganic filler (D).

11. The resin composition according to claim 10, wherein the amount of the inorganic filler (D) is 50% by mass or more and 90% by mass or less based on 100% by mass of the non-volatile components of the resin composition.

12. The resin composition according to any one of claims 1 to 11, which is for forming an insulating layer.

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

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

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

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

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

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