JP7707963B2 - resin composition - Google Patents

Description

The present invention relates to a resin composition. Furthermore, the present invention relates to a cured product of the resin composition; a sheet-like laminate 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.

A known manufacturing technique for printed wiring boards is the build-up method, in which insulating layers and conductor layers are alternately stacked. In build-up manufacturing methods, the insulating layers are generally formed from a cured product obtained by curing a resin composition (Patent Document 1).

JP 2005-039247 A Patent No. 4503239 JP 2009-235165 A

The cured product contained in the insulating layer is required to have a low dielectric tangent. However, when the composition of a resin composition containing an epoxy resin and a curing agent is adjusted to lower the dielectric tangent of the cured product, the resulting cured product tends to be brittle and prone to cracks. For example, when an active ester curing agent is used as the curing agent, the dielectric tangent of the cured product can be lowered, but the cured product is prone to cracks.

In order to suppress the above-mentioned cracks, the present inventors have attempted to blend a soft component such as polybutadiene or a rubber component into the resin composition. However, in resin compositions in which a conventional soft component is blended in combination with an epoxy resin and a curing agent, it is difficult to uniformly disperse the soft component, which can result in a high dielectric tangent and a poor appearance of the resin varnish and resin sheet. Therefore, there is a need to develop a resin composition that can produce a cured product with a low dielectric tangent and excellent crack resistance. Here, "crack resistance" refers to the property of being able to suppress the occurrence of cracks in the cured product of the resin composition.

The present invention was devised in view of the above problems, and aims to provide a resin composition capable of producing a cured product having a low dielectric tangent and excellent crack resistance; a cured product of the resin composition; a sheet-like laminate material containing the resin composition; a resin sheet having a resin composition layer formed from the resin composition; a printed wiring board having an insulating layer including a cured product of the resin composition; and a semiconductor device having the printed wiring board.

The present inventors have conducted extensive research to solve the above-mentioned problems, and as a result, have found that a resin composition containing (A) an epoxy resin, (B) a curing agent, and (C) an alkoxysilyl group-containing, optionally hydrogenated conjugated diene-aromatic vinyl copolymer resin can solve the above-mentioned problems, thereby completing the present invention.
That is, the present invention includes the following.

[1] A resin composition comprising (A) an epoxy resin, (B) a curing agent, and (C) an alkoxysilyl group-containing conjugated diene-aromatic vinyl copolymer resin which may be hydrogenated.
[2] The component (C) contains (c1) an optionally hydrogenated conjugated diene compound unit and (c2) an aromatic vinyl compound unit,
(c1) The resin composition according to [1], in which an alkoxysilyl group is bonded to a part or all of the optionally hydrogenated conjugated diene compound units.
[3] (c1) The optionally hydrogenated conjugated diene compound unit is an optionally hydrogenated butadiene unit,
(c2) The resin composition according to [2], wherein the aromatic vinyl compound unit is a styrene unit.
[4] (c1) The optionally hydrogenated conjugated diene compound unit contains a direct addition unit,
The resin composition according to [2] or [3], wherein an alkoxysilyl group is bonded to a part or all of the side chains of the directly added units.
[5] The resin composition according to any one of [2] to [4], wherein the amount of the aromatic vinyl compound unit (c2) is 15% by mass or more and 50% by mass or less, when the component (C) is 100% by mass.
[6] The resin composition according to any one of [1] to [5], wherein the component (C) contains an alkenylalkoxysilane unit (c3).
[7] The resin composition according to any one of [1] to [6], wherein the component (C) contains a structure represented by the following formula (1):
(In formula (1),
R ¹ to R ³¹ , R ³⁴ to R ⁴⁰ , and R ⁴³ to 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 each represent an integer 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.
[8] The resin composition according to any one of [1] to [7], wherein the component (C) contains a structure represented by the following formula (2):
(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 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.
[9] The resin composition according to any one of [1] to [8], 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.
[10] The resin composition according to any one of [1] to [9], wherein the (B) curing agent includes an active ester curing agent.
[11] The resin composition according to any one of [1] to [10], further comprising (D) an inorganic filler.
[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 laminate material comprising the resin composition according to any one of [1] to [13].
[16] A support;
A resin sheet having a resin composition layer formed on the support using the resin composition according to any one of [1] to [13].
[17] A printed wiring board comprising an insulating layer containing a cured product of the resin composition according to any one of [1] to [13].
[18] A semiconductor device comprising the printed wiring board according to [17].

The present invention can provide a resin composition capable of producing a cured product having a low dielectric tangent and excellent crack resistance; a cured product of the resin composition; a sheet-like laminate material containing the resin composition; a resin sheet having a resin composition layer formed from the resin composition; a printed wiring board having an insulating layer containing a cured product of the resin composition; and a semiconductor device having the printed wiring board.

The present invention will be described below with reference to embodiments and examples. However, the present invention is not limited to the embodiments and examples shown below, and may be modified as desired without departing from the scope of the claims and their equivalents.

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

The inventors speculate as follows about the mechanism by which the resin composition according to this embodiment provides the above-mentioned effects. However, the technical scope of the present invention is not limited to the mechanism described below.

The silicon-containing resin (C) 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 silicon-containing resin (C) can relieve stress in the cured product of the resin composition, so that cracks in the cured product can be suppressed. In addition, the silicon-containing resin (C) contains an alkoxysilyl group, so it has excellent compatibility with the epoxy resin (A) and the curing agent (B). Therefore, the occurrence of phase separation in the cured product can be suppressed, so that the formation of a phase interface can be suppressed. In general, a phase interface tends to be the starting point of destruction due to stress concentration. However, in the cured product of the resin composition according to this embodiment, the formation of a phase interface is suppressed, so that the occurrence of destruction starting from the phase interface can be suppressed, and cracks can be suppressed.

In addition, generally, the conjugated diene-aromatic vinyl copolymer skeleton may contain carbon-carbon unsaturated bonds. These carbon-carbon unsaturated bonds may be oxidized to generate polar groups, which may cause an increase in the dielectric tangent due to the polar groups. However, in the resin composition according to this embodiment, the proportion of carbon-carbon unsaturated bonds in the silicon-containing resin (C) is reduced by containing alkoxysilyl groups, and therefore the proportion of polar groups generated is reduced, suppressing the increase in the dielectric tangent caused by the generation of polar groups. Therefore, with the resin composition according to this embodiment, it is possible to achieve both improved crack resistance and reduced dielectric tangent.

In particular, when the (B) curing agent contains the (B-1) active ester curing agent, it is possible to effectively suppress the dielectric tangent. The (B-1) active ester curing agent does not generate polar groups by reacting with the (A) epoxy resin. Therefore, it is possible to effectively suppress the increase in the dielectric tangent due to the polar groups, and it is possible to effectively reduce the dielectric tangent. In addition, the (B-1) active ester curing agent tends to have low compatibility with conventional conjugated diene-aromatic vinyl copolymers. However, the (C) silicon-containing resin has excellent compatibility with the (B-1) active ester curing agent, making it possible to effectively suppress cracks.

Furthermore, since the silicon-containing resin (C) has flexible molecules, it can enhance the toughness of the cured product of the resin composition. Therefore, even if the resin composition contains the inorganic filler (D), the occurrence of cracks in the cured product can be suppressed. Considering that cured products containing inorganic fillers have traditionally been highly brittle and prone to cracking, it is beneficial that the resin composition according to this embodiment can obtain a cured product that can suppress the occurrence of cracks even if it contains the inorganic filler (D).

In addition, since the toughness of the cured product of the resin composition can be increased as described above, the insulating layer containing the cured product is less likely to break due to stress. Therefore, when a plated conductor layer is formed on the insulating layer, peeling of the plated conductor layer, which is accompanied by destruction of the insulating layer, can be suppressed. Therefore, the adhesion between the insulating layer and the plated conductor layer can usually be improved.

The resin composition according to one embodiment of the present invention may further contain optional components in combination with the components (A) to (C). Examples of optional components include (D) inorganic filler, (E) thermoplastic resin, (F) curing accelerator, (G) radical polymerizable compound, and (H) optional additive. Each component contained in the resin composition according to one embodiment of the present invention will be described in detail below.

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

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

From the viewpoint of obtaining a cured product having excellent heat resistance, it is preferable that the (A) epoxy resin contains an epoxy resin containing an aromatic structure. An aromatic structure is a chemical structure generally defined as aromatic, and also includes polycyclic aromatic rings and aromatic heterocycles. Examples of epoxy resins containing an aromatic structure include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AF type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol type epoxy resins, naphthol novolac type epoxy resins, phenol novolac type epoxy resins, tert-butyl-catechol type epoxy resins, naphthalene type epoxy resins, naphthol type epoxy resins, anthracene type epoxy resins, bisxylenol type epoxy resins, glycidylamine type epoxy resins having an aromatic structure, glycidyl ester type epoxy resins having an aromatic structure, cresol novolac type epoxy resins, biphenyl type epoxy resins, linear aliphatic epoxy resins having an aromatic structure, epoxy resins having a butadiene structure having an aromatic structure, alicyclic epoxy resins having an aromatic structure, heterocyclic epoxy resins, spiro ring-containing epoxy resins having an aromatic structure, cyclohexane dimethanol type epoxy resins having an aromatic structure, naphthylene ether type epoxy resins, trimethylol type epoxy resins having an aromatic structure, and tetraphenylethane type epoxy resins having an aromatic structure.

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

(A) Epoxy resins include epoxy resins that are liquid at a temperature of 20°C (hereinafter sometimes referred to as "liquid epoxy resins") and epoxy resins that are solid at a temperature of 20°C (hereinafter sometimes referred to as "solid epoxy resins"). (A) Epoxy resins may be liquid epoxy resins only, solid epoxy resins only, or a combination of liquid epoxy resins and solid epoxy resins. Of these, (A) Epoxy resins are preferably a combination of liquid epoxy resins and solid epoxy resins.

Preferably, the liquid epoxy resin has two or more epoxy groups in one molecule.

Preferred liquid epoxy resins are bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, naphthalene type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, phenol novolac type epoxy resins, alicyclic epoxy resins having an ester skeleton, cyclohexane type epoxy resins, cyclohexane dimethanol type epoxy resins, epoxy resins having a butadiene structure, epoxy resins containing an alkyleneoxy skeleton and a butadiene skeleton, epoxy resins containing a fluorene structure, and dicyclopentadiene type epoxy resins. Among these, bisphenol A type epoxy resins and bisphenol F type epoxy resins are particularly preferable.

Specific examples of liquid epoxy resins include DIC's "HP4032", "HP4032D", and "HP4032SS" (naphthalene type epoxy resins); Mitsubishi Chemical's "828US", "828EL", "jER828EL", "825", and "Epicoat 828EL" (bisphenol A type epoxy resins); Mitsubishi Chemical's "jER807" and "1750" (bisphenol F type epoxy resins); Mitsubishi Chemical's "jER152" (phenol novolac type epoxy resin); Mitsubishi Chemical's "630", "630LSD", and "604" (glycidylamine type epoxy resins); ADEKA's "ED-523T" (glycilol type epoxy resin); ADEKA's "EP-3950L", "EP-3980S" ( glycidylamine type epoxy resin); ADEKA's "EP-4088S" (dicyclopentadiene type epoxy resin); Nippon Steel Chemical & Material Chemical's "ZX1059" (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); Nagase Chemtex's "EX-721" (glycidyl ester type epoxy resin); Daicel's "Celloxide 2021P" (alicyclic epoxy resin with ester structure); Daicel's "PB-3600", Nippon Soda's "JP-100" and "JP-200" (epoxy resin with butadiene structure); Nippon Steel Chemical & Material's "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin). These may be used alone or in combination of two or more.

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

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

Specific examples of solid epoxy resins include DIC's "HP4032H" (naphthalene type epoxy resin); DIC's "HP-4700" and "HP-4710" (naphthalene type tetrafunctional epoxy resin); DIC's "N-690" (cresol novolac type epoxy resin); DIC's "N-695" (cresol novolac type epoxy resin); DIC's "HP-7200", "HP-7200HH", "HP-7200H", and "HP-7200L" (dicyclopentadiene type epoxy resin); and DIC's "EXA-7311". , "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthylene ether type epoxy resin); "EPPN-502H" (trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC7000L" (naphthol novolac type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC3000H", "NC3000", "NC3000L", "NC3000FH", "NC3100" (biphenyl type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "ESN475V", "ESN4 100V (naphthalene type epoxy resin); "ESN485" (naphthol type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "ESN375" (dihydroxynaphthalene type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YX4000H", "YX4000", "YX4000HK", and "YL7890" (bixylenol type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; "YX8800" (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; "YX Examples of epoxy resins include "7700" (phenol aralkyl type epoxy resin); "PG-100" and "CG-500" manufactured by Osaka Gas Chemicals; "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical; "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical; "jER1010" (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical; "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical; and "WHR991S" (phenolphthalimidine type epoxy resin) manufactured by Nippon Kayaku Co., Ltd. These may be used alone or in combination of two or more types.

When a liquid epoxy resin and a solid epoxy resin are used in combination as the (A) epoxy resin, the mass ratio thereof (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.

The epoxy equivalent of the (A) epoxy resin is preferably 50 g/eq. to 5,000 g/eq., more preferably 60 g/eq. to 3,000 g/eq., even 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.

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

The content of the epoxy resin (A) in the resin composition is preferably 1% by mass or more, more preferably 2% by mass or more, particularly preferably 4% by mass or more, and preferably 25% by mass or less, more preferably 20% by mass or less, particularly preferably 10% by mass or less, when the non-volatile components in the resin composition are taken as 100% by mass. When the amount of the epoxy resin (A) is within the above range, the dielectric tangent and crack resistance of the cured product of the resin composition can be particularly good, and furthermore, usually, the plating peel strength can be effectively increased. Unless otherwise specified, the plating peel strength refers to the force required to peel off 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 the plating peel strength, the better the adhesion between the insulating layer and the plating conductor layer.

The content of the (A) epoxy resin in the resin composition is preferably 5% by mass or more, more preferably 10% by mass or more, particularly preferably 20% by mass or more, and is preferably 70% by mass or less, more preferably 60% by mass or less, particularly preferably 50% by mass or less, when the resin components in the resin composition are taken as 100% by mass. The resin components of the resin composition refer to the non-volatile components of the resin composition excluding the (D) inorganic filler. 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 good, and furthermore, usually, the plating peel strength can be effectively increased.

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

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

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

Specifically, the active ester curing agent (B-1) is preferably 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 novolac, or an active ester curing agent containing a benzoylated product of phenol novolac, and among these, 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.

(B-1) Commercially available active ester curing agents include, for example, "EXB9451", "EXB9460", "EXB9460S", "EXB-8000L", "EXB-8000L-65M", "EXB-8000L-65TM", "HPC-8000L-65TM", "HPC-8000", "HPC-8000-65T", "HPC-8000H", and "HPC-8000H-65TM" (manufactured by DIC Corporation) as active ester curing agents containing a dicyclopentadiene-type diphenol structure; and "HP-B-8151-62T", "EXB-8100L-65T", "EXB-8150-60T", and "EXB-8 150-62T", "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 which is an acetylated product of phenol novolac, "DC808" (manufactured by Mitsubishi Chemical Corporation); as active ester curing agents which are benzoylated products of phenol novolac, "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.), etc.

When the number of epoxy groups in the (A) epoxy resin is taken as 1, the number of active ester groups in the (B-1) active ester curing agent is preferably 0.01 or more, more preferably 0.1 or more, even more preferably 1 or more, and preferably 10 or less, more preferably 5 or less, and particularly preferably 2 or less. The "number of epoxy groups in the (A) epoxy resin" refers to the total value obtained by dividing the mass of the non-volatile components of the (A) epoxy resin present in the resin composition by the epoxy equivalent. The "number of active ester groups in the (B-1) active ester curing agent" refers to the total value obtained by dividing the mass of the non-volatile components of the (B-1) active ester curing agent present in the resin composition by the active ester group equivalent.

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

The content of the active ester curing agent (B-1) in the resin composition is preferably 10% by mass or more, more preferably 20% by mass or more, particularly preferably 30% by mass or more, and is preferably 80% by mass or less, more preferably 70% by mass or less, particularly preferably 60% by mass or less, when the resin component in the resin composition is taken as 100% by mass. When the amount of the active ester curing agent (B-1) is within the above range, the dielectric tangent and crack resistance of the cured product of the resin composition can be particularly good, and furthermore, usually, the plating peel strength can be effectively increased.

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

(B-1) Examples of curing agents other than active ester curing agents include phenolic curing agents, carbodiimide curing agents, acid anhydride curing agents, amine curing agents, benzoxazine curing agents, cyanate ester curing agents, and thiol 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 curing agents are preferred.

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

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 carbodiimide-based curing agents include aliphatic biscarbodiimides such as tetramethylene-bis(t-butylcarbodiimide) and cyclohexane bis(methylene-t-butylcarbodiimide); aromatic biscarbodiimides such as phenylene-bis(xylylcarbodiimide); aliphatic polycarbodiimides such as polyhexamethylenecarbodiimide, polytrimethylhexamethylenecarbodiimide, polycyclohexylenecarbodiimide, poly(methylenebiscyclohexylenecarbodiimide), and poly(isophoronecarbodiimide); poly(phenylenecarbodiimide), poly( Examples of polycarbodiimides include aromatic polycarbodiimides such as poly(naphthylenecarbodiimide), poly(tolylenecarbodiimide), poly(methyldiisopropylphenylenecarbodiimide), poly(triethylphenylenecarbodiimide), poly(diethylphenylenecarbodiimide), poly(triisopropylphenylenecarbodiimide), poly(diisopropylphenylenecarbodiimide), poly(xylylenecarbodiimide), poly(tetramethylxylylenecarbodiimide), poly(methylenediphenylenecarbodiimide), and poly[methylenebis(methylphenylene)carbodiimide]. Specific examples of carbodiimide-based curing agents include "Carbodilite V-02B", "Carbodilite V-03", "Carbodilite V-07", and "Carbodilite V-09" manufactured by Nisshinbo Chemical Inc.; "Stavaxol P", "Stavaxol P400", and "Hi-Kasil 510" manufactured by Rhein Chemie.

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

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. Examples of the amine-based curing agent include aliphatic amines, polyether amines, alicyclic amines, aromatic amines, etc., and among these, aromatic amines are preferred. The amine-based curing agent is preferably a primary amine or secondary amine, and more preferably a primary amine. Specific examples of amine-based curing agents include 4,4'-methylenebis(2,6-dimethylaniline), 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenylether, 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 A-A", "KAYAHARD A-B", and "KAYAHARD A-S" manufactured by Nippon Kayaku Co., Ltd.; "Epicure W" manufactured by Mitsubishi Chemical Corporation; and "DTDA" manufactured by Sumitomo Seika Chemicals Co., Ltd.

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 "P-d" and "F-a" manufactured by Shikoku Chemical Industry Co., Ltd.

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

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

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

When the number of epoxy groups in the (A) epoxy resin is taken as 1, the number of active groups in the (B) curing agent is preferably 0.01 or more, more preferably 0.1 or more, even more preferably 1 or more, and preferably 10 or less, more preferably 5 or less, and particularly preferably 2 or less. The "number of active groups in the (B) curing agent" refers to the total value obtained by dividing the mass of the non-volatile components of the (B) curing agent present in the resin composition by the active group equivalent.

The content of the (B) curing agent in the resin composition is preferably 3% by mass or more, more preferably 5% by mass or more, even more preferably 8% by mass or more, particularly preferably 10% by mass or more, and is preferably 40% by mass or less, more preferably 30% by mass or less, even more preferably 20% by mass or less, particularly preferably 18% by mass or less, assuming that the non-volatile components in the resin composition are 100% by mass. When the amount of the (B) curing agent is within the above range, the dielectric tangent and crack resistance of the cured product of the resin composition can be particularly good, and usually the plating peel strength can be effectively increased.

The content of the (B) curing agent in the resin composition is preferably 5% by mass or more, more preferably 10% by mass or more, particularly preferably 20% by mass or more, and is preferably 80% by mass or less, more preferably 70% by mass or less, particularly preferably 60% by mass or less, when the resin components in the resin composition are taken as 100% by mass. When the amount of the (B) curing agent is within the above range, the dielectric tangent and crack resistance of the cured product of the resin composition can be particularly good, and furthermore, usually, the plating peel strength can be effectively increased.

[(C) Silicon-containing resin (conjugated diene-aromatic vinyl copolymer resin containing an alkoxysilyl group and optionally hydrogenated)]
A resin composition according to one embodiment of the present invention comprises, as component (C), a silicon-containing resin (C) (i.e., (C) a conjugated diene-aromatic vinyl copolymer resin which contains an alkoxysilyl group and which may be hydrogenated).

The term "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. The term "conjugated diene-aromatic vinyl copolymer resin containing an alkoxysilyl group" refers to a resin having a structure in which an alkoxysilyl group has been introduced into a resin containing a structure obtained by copolymerizing a conjugated diene compound and an aromatic vinyl compound. The term "(C) conjugated diene-aromatic vinyl copolymer resin containing an alkoxysilyl group and optionally hydrogenated" (i.e., (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 an 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 as necessary.

The (C) silicon-containing resin usually contains (c1) a conjugated diene compound unit which may be hydrogenated. The (c1) conjugated diene compound unit which may be hydrogenated may have an alkoxysilyl group bonded to it. The (c1) conjugated diene compound unit which may be hydrogenated may be referred to below as the "(c1) diene unit."

The term "conjugated diene compound unit" refers to a structural unit having a structure formed by polymerizing a conjugated diene compound. However, there is no limitation 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.

The conjugated diene compound unit which may be hydrogenated includes both a conjugated diene compound unit and a hydrogenated conjugated diene compound unit. In addition, the hydrogenated conjugated diene compound unit refers to a structural unit having a structure formed by hydrogenating a 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 bonds of the conjugated diene compound unit.

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

Among the conjugated diene compounds, butadiene is preferred. Therefore, as the diene unit (c1), a butadiene unit which may be hydrogenated is preferred. The butadiene unit refers to a structural unit having a structure formed by polymerizing butadiene. The butadiene unit which may be hydrogenated includes both butadiene units and hydrogenated butadiene units. Furthermore, the hydrogenated butadiene unit refers to a structure formed by hydrogenating a part or all of the carbon-carbon unsaturated bonds of the butadiene unit. However, there is no limitation on the manufacturing method of the butadiene unit which may be hydrogenated.

The amount of (c1) diene units is preferably 10% by mass or more, more preferably 20% by mass or more, particularly preferably 30% by mass or more, and is 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 (C) silicon-containing resin. The amount of (c1) diene units includes both the amount of (c1) diene units to which alkoxysilyl groups are bonded and the amount of (c1) diene units to which no alkoxysilyl groups are bonded.

It is preferable that an alkoxysilyl group is bonded to some or all of the diene units (c1). In this case, it is preferable that the alkoxysilyl group is bonded to at least the direct addition unit of the diene units (c1). This point will be described in detail below.

A conjugated diene compound generally has a carbon atom chain containing four carbon atoms bonded by a double bond, a single bond, and a double bond, in that order. Since the carbon atom chain has the same carbon skeleton as the carbon atom chain of 1,3-butadiene, it is sometimes referred to below as the "butadiene carbon skeleton."

When a conjugated diene compound is polymerized, generally, a conjugated addition reaction and a direct addition reaction can occur. In a 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. Thus, in the conjugated diene compound unit generated by the conjugated addition reaction, a double bond is contained in the main chain that connects the carbon atoms that are bonded to other structural units. In this way, a conjugated diene compound unit that contains a double bond in the main chain usually contains the same carbon atom chain as 1,4-polybutadiene. Hereinafter, among the (c1) diene units, a conjugated diene compound unit that contains a double bond in the main chain and a structural unit having a structure formed by hydrogenating the carbon-carbon unsaturated bond may be referred to as a "conjugated addition unit".

On the other hand, in a direct addition reaction, a 1,2 addition reaction occurs in which the carbon atoms at the 1st and 2nd positions of the butadiene carbon skeleton are bonded. Therefore, in the conjugated diene compound units generated in a direct addition reaction, there are no double bonds in the main chain, but the double bonds are contained in the side chains. Conjugated diene compound units containing double bonds in the side chains in this way usually contain the same carbon atom chain as 1,2-polybutadiene. Hereinafter, among the (c1) diene units, conjugated diene compound units containing double bonds in the side chains and structural units having a structure formed by hydrogenating the carbon-carbon unsaturated bonds thereof may be referred to as "direct addition units".

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

When an alkoxysilyl group is bonded to the diene unit (c1), the alkoxysilyl group may be bonded directly to the diene unit (c1) or indirectly via a divalent linking group. Examples of the "divalent linking group" include divalent hydrocarbon groups 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; 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 groups 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 which does not have a substituent is more preferable. Among them, it is preferable that the alkoxysilyl group is directly bonded to the diene unit (c1).

The (C) silicon-containing resin usually contains (c2) an aromatic vinyl compound unit. The (c2) aromatic vinyl compound unit refers to a structural unit having a structure formed by polymerizing an aromatic vinyl compound. However, there is no restriction on the manufacturing 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.

As the aromatic vinyl compound corresponding to the (c2) aromatic vinyl compound unit, a compound containing an aromatic ring and a vinyl group which may be substituted bonded to the aromatic ring can be used. Examples of aromatic vinyl compounds include styrene, vinyl toluene, ethyl styrene, vinyl naphthalene, 4-tert-butyl styrene, 4-acetoxy styrene, 4-vinyl phenol, 4-tert-butoxy styrene, 1-(1-ethoxyethoxy)-4-vinyl benzene, and 9-vinylanthracene. The aromatic vinyl compound may be used alone or in combination of two or more types. Thus, the aromatic vinyl compound unit (c2) may be used alone or in combination of two or more types.

Among aromatic vinyl compounds, styrene is preferred. Therefore, as the aromatic vinyl compound unit (c2), a styrene unit is preferred. A styrene unit refers to a structural unit having a structure formed by polymerizing styrene. However, there is no restriction on the method for producing the styrene unit.

The amount of (c2) aromatic vinyl compound units is preferably 15% by mass or more, more preferably 18% by mass or more, and particularly preferably 20% by mass or more, relative to 100% by mass of (C) silicon-containing resin, and is preferably 60% by mass or less, more preferably 50% by mass or less, and particularly preferably 40% by mass or less.

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 mass ratio ((c1) diene unit/(c2) aromatic vinyl compound unit) is preferably 0.1 or more, more preferably 0.5 or more, and particularly preferably 1 or more, and is preferably 100 or less, more preferably 10 or less, and particularly preferably 5 or less.

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

The alkenylalkoxysilane compound can form (c3) alkenylalkoxysilane units as repeating units of (C) silicon-containing resin because the carbon-carbon double bonds contained in the alkenyl groups can react and polymerize. The (c3) alkenylalkoxysilane units can contain alkoxysilyl groups derived from the alkenylalkoxysilane compound. However, there are no limitations on the method for producing the (c3) alkenylalkoxysilane units. Thus, the (c3) alkenylalkoxysilane units may be formed by methods other than polymerizing an alkenylalkoxysilane compound.

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

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, structural units that can be classified as both the (c1) diene unit to which an alkoxysilyl group is bonded and the (c3) alkenylalkoxysilane unit are classified as the (c1) diene unit to which an alkoxysilyl group is bonded.

The amount of (c3) alkenylalkoxysilane units may be 0% by mass or may be greater than 0% by mass, and is preferably 10% by mass or more, more preferably 20% by mass or more, particularly preferably 30% by mass or more, and is preferably 70% by mass or less, more preferably 60% by mass or less, particularly preferably 50% by mass or less, relative to 100% by mass of (C) silicon-containing resin.

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

As the silicon-containing resin (C), a resin containing a structure represented by the following formula (1) is particularly preferred. Therefore, the silicon-containing resin (C) 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).

(In formula (1),
R ¹ to R ³¹ , R ³⁴ to R ⁴⁰ , and R ⁴³ to 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 each represent an integer of 0 or more satisfying e+f≧1;
g represents an integer of 1 or more;
h and i each 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.

In formula (1), R ¹ to R ³¹ , R ³⁴ to R ⁴⁰ , and R ⁴³ to R ⁴⁵ each independently represent 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. The monovalent hydrocarbon group may be a linear or branched hydrocarbon group, or may be a hydrocarbon group containing a ring. The number of carbon atoms in 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, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups; and aryl groups such as phenyl, α-naphthyl, and β-naphthyl groups. Among these, R ¹ to R ³¹ , R ^to R ⁴⁰ , and R ⁴³ to R ⁴⁵ are each independently preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom.

In formula (1), X represents a single bond or a divalent linking group. As the "divalent linking group", those as 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, or 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, and preferably 20 or less, more preferably 12 or less, even more preferably 10 or less, even 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 even more preferable. The alkylene group may be linear, branched, or cyclic. Examples of such alkylene groups include methylene, ethylene, propylene, butylene, pentylene, hexylene, and 1,1-dimethylethylene groups, with methylene, ethylene, and 1,1-dimethylethylene groups being preferred, and ethylene being particularly preferred. As the alkenylene group, an alkenylene group having 2 to 10 carbon atoms is preferred, an alkenylene group having 2 to 6 carbon atoms is more preferred, and an alkenylene group having 2 to 5 carbon atoms is even more preferred. As the arylene group, an arylene group having 6 to 20 carbon atoms is preferred, and an arylene group having 6 to 10 carbon atoms is even more preferred. Among these, X is preferably a divalent alkylene group which may have a substituent, and more preferably a divalent alkylene group which does not have a substituent.

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 may be within the same range as the monovalent hydrocarbon groups represented by R ¹ to R ³¹ , R ³⁴ to R ⁴⁰ , and R ⁴³ to R ^45. R ³² , R ³³ , R ⁴¹ , and R ⁴² are preferably alkyl groups and aryl groups, more preferably alkyl groups, even more preferably linear alkyl groups, and particularly preferably methyl groups and ethyl groups.

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, more preferably 10 or less. Examples of the aryl group include a phenyl group, a naphthyl group, and an anthracenyl group. Examples of the substituent that the aryl group may have include halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms; monovalent hydrocarbon groups such as alkyl groups, aryl groups, and arylalkyl groups; cycloalkyloxy groups, aryloxy groups, arylalkoxy groups, monovalent heterocyclic groups, amino groups, silyl groups, acyl groups, acyloxy groups, carboxy groups, sulfo groups, cyano groups, nitro groups, hydroxy groups, and mercapto groups. Among these, the substituent is preferably a monovalent hydrocarbon group, more preferably an alkyl group or an aryl group, and even more preferably an alkyl group. In particular, Ar is preferably an unsubstituted aryl group.

In formula (1), a, b, c, and d each independently represent an integer of 0 or more. In detail, 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, and may be 1 or more, and are preferably 200 or less, more preferably 100 or less.

In formula (1), e and f represent integers of 0 or more that satisfy e+f≧1, and it is particularly preferable that e is 1 or more. In detail, e is usually 0 or more, preferably 1 or more, more preferably 2 or more, and 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. Furthermore, it is preferable that e+f satisfies 0.02≦(e+f)/(a+b+c+d+e+f+g)<1.0.

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

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.

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

A more preferred example of the silicon-containing resin (C) is a resin having a structure shown in the following formula (2).

(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 each 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.

In formula (2), Y represents a single bond or a divalent hydrocarbon group. The divalent hydrocarbon group represented by Y may 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.

In formula (2), R ⁴⁶ and R ⁴⁷ each independently represent a monovalent hydrocarbon group. The ranges of R ⁴⁶ and R ⁴⁷ may be the same as those of R ³² , R ³³ , R ⁴¹ , and R ⁴² described above.

In formula (2), j and k each independently represent an integer of 0 or greater. In particular, j represents an integer in the same range as a and b in formula (1). Furthermore, k represents an integer in the same range as c and d in formula (1).

In formula (2), l and m each independently represent an integer greater than 0. In particular, l represents an integer in the same range as e in formula (1). Furthermore, it is preferable that l satisfies 0.02≦l/(j+k+l+m)<1.0. Furthermore, m represents an integer in the same range as g in formula (1).

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

In formula (2), n represents an integer of 1 to 3, preferably 2 to 3, and more preferably 3.

In particular, the amount of units containing alkoxysilyl groups (such as the repeating units e, f, and l described above) is preferably 3% or more relative to 100% by mass of the silicon-containing resin (C).

There is no limitation on the method for producing the silicon-containing resin (C). The silicon-containing resin (C) can be produced 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, or 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, for example, JP-A-2017-8301 can be referred to. The silicon-containing resin (C) can also be produced 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 method for producing the silicon-containing resin (C) may include hydrogenating the conjugated diene-aromatic vinyl copolymer resin containing an alkoxysilyl group after obtaining the conjugated diene-aromatic vinyl copolymer resin containing an alkoxysilyl group.

As the silicon-containing resin (C), a commercially available product may be used. Examples of commercially available silicon-containing resin (C) include "X-12-1281C" and "X-12-1281A" manufactured by Shin-Etsu Chemical Co., Ltd. (resins in which trimethoxysilyl groups have been introduced into the side chains of the direct addition units of styrene-butadiene copolymer); and "X-12-1281A-ES" manufactured by Shin-Etsu Chemical Co., Ltd. (resins in which triethoxysilyl groups have been introduced into the side chains of the direct addition units of styrene-butadiene copolymer).

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

The number average molecular weight of the silicon-containing resin (C) is preferably 2,000 or more, more preferably 3,000 or more, particularly preferably 4,000 or more, and is 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).

The content of the silicon-containing resin (C) in the resin composition 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 10% by mass or less, more preferably 6% by mass or less, particularly preferably 4% by mass or less, assuming that the non-volatile components in the resin composition are 100% by mass. When the amount of the silicon-containing resin (C) is within the above range, the dielectric tangent and crack resistance of the cured product of the resin composition can be particularly good, and furthermore, usually, the plating peel strength can be effectively increased.

The content of the silicon-containing resin (C) in the resin composition is preferably 0.5% by mass or more, more preferably 1% by mass or more, particularly preferably 2% by mass or more, and is preferably 15% by mass or less, more preferably 10% by mass or less, particularly preferably 8% by mass or less, when the resin components in the resin composition are taken as 100% by mass. When the amount of the silicon-containing resin (C) is within the above range, the dielectric tangent and crack resistance of the cured product of the resin composition can be particularly good, and furthermore, usually, the plating peel strength can be effectively increased.

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

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

(D) Commercially available inorganic fillers include, for example, "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.; "Silfil NSS-3N", "Silfil NSS-4N", and "Silfil NSS-5N" manufactured by Tokuyama Corporation; "Cellpheares" manufactured by Taiheiyo Cement Corporation; and "Sfereek" manufactured by JGC Catalysts and Chemicals Co., Ltd.

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

(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, a particle size distribution of the inorganic filler is created on a volume basis using a laser diffraction/scattering particle size distribution measuring device, and the median diameter is used as the average particle size. The measurement sample can be prepared by weighing 100 mg of inorganic filler and 10 g of methyl ethyl ketone into a vial and dispersing the mixture by ultrasonic waves for 10 minutes. The measurement sample is measured using a laser diffraction particle size distribution measuring device with blue and red light source wavelengths, and the volume-based particle size distribution of the inorganic filler is measured using a flow cell method, and the average particle size can be calculated as the median diameter from the particle size distribution obtained. An example of a laser diffraction particle size distribution measuring device is the "LA-960" manufactured by Horiba, Ltd.

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

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

Commercially available surface treatment agents include, for example, Shin-Etsu Chemical's "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), and "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane).

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

The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. 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 ² or more. On the other hand, from the viewpoint of preventing an increase in the melt viscosity of the resin composition, it is preferably 1.0 mg/m ² or less, more preferably 0.8 mg/m ² or less, and even more preferably 0.5 mg/m ² or less.

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

The content of the inorganic filler (D) in the resin composition may be 0% by mass or more, and is preferably 50% by mass or more, more preferably 60% by mass or more, particularly preferably 70% by mass or more, and is preferably 90% by mass or less, more preferably 86% by mass or less, particularly preferably 82% by mass or less, when the non-volatile components in the resin composition are taken as 100% by mass. When the amount of the inorganic filler (D) is within the above range, the dielectric tangent and crack resistance of the cured product of the resin composition can be particularly good, and furthermore, usually, the plating peel strength can be effectively increased.

It is preferable that the mass ratio ((D) inorganic filler/(C) silicon-containing resin) of the (D) inorganic filler to the (C) silicon-containing resin in the resin composition is 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, and is preferably 300 or less, more preferably 200 or less, 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 good, and furthermore, usually, the plating peel strength can be effectively increased.

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

(E) Examples of thermoplastic resins include phenoxy resins, polyimide resins, polyvinyl acetal resins, polyolefin resins, polybutadiene resins, polyamideimide resins, polyetherimide resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, polycarbonate resins, polyetheretherketone resins, and polyester resins. (E) Thermoplastic resins may be used alone or in combination of two or more.

Examples of phenoxy resins include phenoxy resins having one or more skeletons selected from the group consisting of bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenolacetophenone 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.

Specific examples of phenoxy resins include Mitsubishi Chemical's "1256" and "4250" (both phenoxy resins containing a bisphenol A skeleton); Mitsubishi Chemical's "YX8100" (phenoxy resin containing a bisphenol S skeleton); Mitsubishi Chemical's "YX6954" (phenoxy resin containing a bisphenol acetophenone skeleton); Nippon Steel Chemical & Material's "FX280" and "FX293"; Mitsubishi Chemical's "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290", "YL7482", and "YL7891BH30".

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

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

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

Examples of polybutadiene resins include hydrogenated polybutadiene skeleton-containing resins, hydroxyl group-containing polybutadiene resins, phenolic hydroxyl group-containing polybutadiene resins, carboxyl group-containing polybutadiene resins, acid anhydride group-containing polybutadiene resins, epoxy group-containing polybutadiene resins, isocyanate group-containing polybutadiene resins, urethane group-containing polybutadiene resins, polyphenylene ether-polybutadiene resins, etc.

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

An example of a polyethersulfone resin is "PES5003P" manufactured by Sumitomo Chemical Co., Ltd.

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

A specific example of a polyphenylene ether resin is NORYL SA90 manufactured by SABIC. A specific example of a polyetherimide resin is ULTEM manufactured by GE.

Examples of polycarbonate resins include hydroxyl group-containing carbonate resins, phenolic hydroxyl group-containing carbonate resins, carboxyl group-containing carbonate resins, acid anhydride group-containing carbonate resins, isocyanate group-containing carbonate resins, and urethane group-containing carbonate resins. Specific examples of polycarbonate resins include Mitsubishi Gas Chemical's "FPC0220," Asahi Kasei Chemical's "T6002" and "T6001" (polycarbonate diols), and Kuraray's "C-1090," "C-2090," and "C-3090" (polycarbonate diols). Specific examples of polyether ether ketone resins include Sumitomo Chemical's "Sumiploy K."

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

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

The content of the (E) thermoplastic resin in the resin composition may be 0% by mass or may be greater than 0% by mass, and 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, assuming that 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 or may be greater than 0% by mass, and is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, particularly preferably 0.5% by mass or more, and is preferably 10% by mass or less, more preferably 7.5% by mass or less, particularly preferably 6% by mass or less, assuming that the resin components in the resin composition are 100% by mass.

[(F) Curing Accelerator]
The resin composition according to one embodiment of the present invention may further contain a curing accelerator (F) as an optional component in combination with the above-mentioned components (A) to (E). The curing accelerator (F) as the component (F) does not include those that fall under the above-mentioned components (A) to (E). The curing accelerator (F) functions as a curing catalyst that accelerates the curing of the epoxy resin (A).

(F) Examples of the curing accelerator include phosphorus-based curing accelerators, urea-based curing accelerators, guanidine-based curing accelerators, imidazole-based curing accelerators, metal-based curing accelerators, and amine-based curing accelerators. Among these, imidazole-based curing accelerators are preferred. (F) Curing accelerators may be used alone or in combination of two or more types.

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 hydrogenhexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate, and di-tert-butyldimethylphosphonium tetraphenylborate; methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, and tetraphenylphosphine. Aromatic phosphonium salts such as sulfonium 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, and butyltriphenylphosphonium thiocyanate; aromatic phosphine-borane complexes such as triphenylphosphine-triphenylborane; aromatic phosphine-quinone addition products such as triphenylphosphine-p-benzoquinone addition products; tributylphosphine, tri- Aliphatic phosphines such as tert-butylphosphine, trioctylphosphine, di-tert-butyl(2-butenyl)phosphine, di-tert-butyl(3-methyl-2-butenyl)phosphine, and tricyclohexylphosphine; dibutylphenylphosphine, di-tert-butylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclohexylphosphine, triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tris(4-ethylphenyl)phosphine, tris(4-propylphenyl)phosphine, tris(4-isopropylphenyl)phosphine, tris(4-butylphenyl)phosphine, tris(4-tert-butylphenyl)phosphine, tris(2,4-dimethylphenyl)phosphine, tris(2,5-dimethylphenyl)phosphine, tris(2,6-dimethylphenyl)phosphine, 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)diphenyl ether and other aromatic phosphines.

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

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

Examples of imidazole-based curing accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, and 1-benzyl-2-furan. phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-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, Examples of imidazole compounds such as 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, and 2-phenylimidazoline, as well as adducts of imidazole compounds and epoxy resins, are given. Commercially available imidazole curing accelerators include, for example, "1B2PZ", "2E4MZ", "2MZA-PW", "2MZ-OK", "2MA-OK", "2MA-OK-PW", "2PHZ", "2PHZ-PW", "Cl1Z", "Cl1Z-CN", "Cl1Z-CNS", and "C11Z-A" manufactured by Shikoku Chemical Industry Co., Ltd.; and "P200-H50" manufactured by Mitsubishi Chemical Corporation.

Metal-based curing accelerators include, for example, 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. Organometallic salts include, for example, zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

Examples of amine-based curing accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo(5,4,0)-undecene. Commercially available amine-based curing accelerators may be used, such as "MY-25" manufactured by Ajinomoto Fine-Techno Co., Ltd.

The content of the (F) curing accelerator in the resin composition may be 0% by mass or may be greater than 0% by mass, and is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, particularly preferably 0.03% by mass or more, and is preferably 1% by mass or less, more preferably 0.5% by mass or less, particularly preferably 0.3% by mass or less, assuming that the non-volatile components in the resin composition are 100% by mass.

The content of the (F) curing accelerator in the resin composition may be 0% by mass or may be greater than 0% by mass, and is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, particularly preferably 0.1% by mass or more, and is preferably 2% by mass or less, more preferably 1.5% by mass or less, particularly preferably 1% by mass or less, assuming that the resin component in the resin composition is 100% by mass.

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

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

(G) Examples of radically polymerizable compounds include (meth)acrylic radically polymerizable compounds, styrene radically polymerizable compounds, allyl radically polymerizable compounds, and maleimide radically polymerizable compounds.

The (meth)acrylic radical polymerizable compound is, for example, a compound having one or more, preferably two or more, acryloyl groups and/or methacryloyl groups. Examples of the (meth)acrylic radical polymerizable compound include cyclohexane-1,4-dimethanol di(meth)acrylate, cyclohexane-1,3-dimethanol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonyl acrylate, 1,2-dimethylphenyl di(meth)acrylate, 1,3-dimethylphenyl di(meth)acrylate, 1,4-dimethylphenyl di(meth)acrylate, 1,5-dimethylphenyl di(meth)acrylate, 1,6-dimethylphenyl di(meth)acrylate, 1,8-dimethylphenyl di(meth)acrylate, 1,9-dimethylphenyl di(meth) ...3-dimethylphenyl di(meth)acrylate, 1,4-dimethylphenyl di(meth)acrylate, 1,5-dimethylphenyl di(meth)acrylate, 1,3-dimethylphenyl di(meth)acrylate, 1,4-dimethylphenyl di(meth)acrylate, 1,5-dimethylphenyl di(meth)acrylate, 1,3-dimethylphenyl di(meth)acrylate, 1,4-dimethylphenyl di(meth)acrylate, 1,5-dimethyl aliphatic (meth)acrylic acid ester compounds having a low molecular weight (molecular weight less than 1000) such as dioxane glycol di(meth)acrylate, 3,6-dioxa-1,8-octanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, glycerin tri(meth)acrylate, and pentaerythritol tetra(meth)acrylate; low molecular weight (molecular weight less than 1000) ether-containing (meth)acrylic acid ester compounds such as 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene, ethoxylated bisphenol A di(meth)acrylate, and propoxylated bisphenol A di(meth)acrylate; low molecular weight (molecular weight less than 1000) isocyanurate-containing (meth)acrylic acid ester compounds such as tris(3-hydroxypropyl)isocyanurate tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, and ethoxylated isocyanuric acid tri(meth)acrylate; and high molecular weight (molecular weight 1000 or more) acrylic acid ester compounds such as (meth)acrylic-modified polyphenylene ether resins. 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) and "DCP" (tricyclodecane dimethanol dimethacrylate) manufactured by Kyoeisha Chemical Co., Ltd., "KAYARAD R-684" (tricyclodecane dimethanol diacrylate) and "KAYARAD R-604" (dioxane glycol diacrylate) manufactured by Nippon Kayaku Co., Ltd., and "SA9000" and "SA9000-111" (methacrylic modified polyphenylene ether) manufactured by SABIC Innovative Plastics.

A styrene-based radical polymerizable compound is, for example, a compound having one or more, preferably two or more, vinyl groups directly bonded to an aromatic carbon atom. Examples of 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, and bis(4-vinylphenyl)ether; high molecular weight (molecular weight 1000 or more) styrene-based compounds such as vinylbenzyl-modified polyphenylene ether resin and styrene-divinylbenzene copolymer. Commercially available styrene-based radical polymerizable compounds include, for example, "ODV-XET (X03)", "ODV-XET (X04)", and "ODV-XET (X05)" (styrene-divinylbenzene copolymers) manufactured by Nippon Steel Chemical & Material Co., Ltd., and "OPE-2St 1200" and "OPE-2St 2200" (vinylbenzyl-modified polyphenylene ether resins) manufactured by Mitsubishi Gas Chemical Co., Inc.

An allyl-based 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-naphthalenecarboxylate; isocyanuric acid allyl ester compounds such as 1,3,5-triallyl isocyanurate and 1,3-diallyl-5-glycidyl isocyanurate; epoxy-containing aromatic allyl compounds such as 2,2-bis[3-allyl-4-(glycidyloxy)phenyl]propane; benzoxazine-containing aromatic allyl compounds such as bis[3-allyl-4-(3,4-dihydro-2H-1,3-benzoxazin-3-yl)phenyl]methane; ether-containing aromatic allyl compounds such as 1,3,5-triallyl ether benzene; and allyl silane compounds such as diallyl diphenyl silane. Commercially available allyl radical polymerizable compounds include, for example, "TAIC" (1,3,5-triallyl isocyanurate) manufactured by Nippon Kasei Chemical Industry Co., Ltd., "DAD" (diallyl diphenate) manufactured by Nisshoku Techno Fine Chemical Co., Ltd., "TRIAM-705" (triallyl trimellitate) manufactured by Wako Pure Chemical Industries, Ltd., "DAND" (2,3-diallyl naphthalene carboxylate) 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 Corporation, "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 Corporation.

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

The ethylenically unsaturated bond equivalent of the radical polymerizable compound (G) is preferably 20 g/eq. to 3,000 g/eq., more preferably 50 g/eq. to 2,500 g/eq., even more preferably 70 g/eq. to 2,000 g/eq., and particularly preferably 90 g/eq. to 1,500 g/eq. The ethylenically unsaturated bond equivalent represents the mass of the radical polymerizable compound per equivalent of the ethylenically unsaturated bond.

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

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

The content of the radical polymerizable compound (G) in the resin composition may be 0% by mass or may be greater than 0% by mass, and is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, particularly preferably 1% by mass or more, and is preferably 15% by mass or less, more preferably 10% by mass or less, particularly preferably 7.5% by mass or less, assuming that the resin component in the resin composition is 100% by mass.

(H) Optional Additives
The resin composition according to one embodiment of the present invention may further contain an optional additive (H) as an optional non-volatile component in addition to the above-mentioned components (A) to (G). (H) Examples of optional additives 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, phenolic resins, melamine resins, and silicone resins; organic fillers such as rubber particles; organometallic compounds such as organocopper compounds, organozinc compounds, and organocobalt compounds; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, and carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and phenothiazine; leveling agents such as silicone-based leveling agents and acrylic polymer-based leveling agents; thickeners such as bentone and montmorillonite; defoamers such as silicone-based defoamers, acrylic defoamers, fluorine-based defoamers, and vinyl resin-based defoamers. 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 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 acid anhydride-based stabilizers. The optional additives (H) may be used alone or in combination of two or more kinds.

[(I) Solvent]
The resin composition according to the present embodiment may further contain a solvent (I) as an optional volatile component in combination with the non-volatile components such as the components (A) to (H) described above. As the solvent (I), an organic solvent is usually used. Examples of the organic solvent include ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester-based solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, and γ-butyrolactone; ether-based solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, and anisole; alcohol-based solvents such as methanol, ethanol, propanol, butanol, and ethylene glycol; 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl diglycol acetate, γ-butyrolactone, and methyl methoxypropionate. Examples of suitable solvents include ether ester solvents such as ethyl acetate, 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 (butylcarbitol), 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 solvent (I) may be used alone or in combination of two or more.

(I) The content of the solvent is not particularly limited, but when all components in the resin composition are taken as 100% by mass, it may be, for example, 60% by mass or less, 40% by mass or less, 30% by mass or less, 20% by mass or less, 15% by mass or less, 10% by mass or less, or it may even be 0% by mass.

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

[Physical Properties of Resin Composition]
The above-mentioned resin composition can be cured by heat. Therefore, a cured product of the resin composition can be obtained by thermally curing the resin composition. Generally, among the components contained in the resin composition, volatile components such as (I) solvent can be volatilized by the heat during thermal curing, but non-volatile components such as components (A) to (H) do not volatilize by the heat during thermal curing. Therefore, the cured product of the resin composition can contain the non-volatile components of the resin composition or their reaction products.

The resin composition according to one embodiment of the present invention can usually give a cured product with a low dielectric tangent. For example, when the dielectric tangent of the cured product is measured under the conditions described in the [Dielectric Properties] section of the Examples below, 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. There is no particular lower limit, and it can be, for example, 0.0001 or more.

The resin composition according to one embodiment of the present invention can usually give 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 section [Crack Resistance] of the Examples below, 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.

The resin composition according to one embodiment of the present invention can generally provide a cured product with excellent adhesion to a plated conductor layer. That is, when a conductor layer is formed on a cured product of the resin composition by plating, high adhesion between the conductor layer and the cured product can be obtained. For example, when the plating peel strength is measured under the conditions described in the section [Adhesion to Plated Conductor Layer] of the Examples described later, the plating peel strength can be increased. The plating peel strength indicates the magnitude of the force required to peel off the conductor layer formed on the cured product of the resin composition by plating, and the higher the plating peel strength, the better the adhesion to the plated 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.

[Uses of resin composition]
The resin composition according to one embodiment of the present invention can be used as a resin composition for insulating purposes, and can be particularly 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).

The resin composition according to one embodiment of the present invention may be used as a resin composition for forming a rewiring formation layer (resin composition for forming a rewiring formation layer). The rewiring formation layer refers to an insulating layer for forming a rewiring layer. The rewiring layer refers to a conductor layer formed on the rewiring formation 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 this embodiment may be used as a resin composition for forming a rewiring formation layer. When a semiconductor chip package is manufactured through the following steps (1) to (6), a rewiring layer may be further formed on the sealing layer.
(1) A step of laminating a temporary fixing film on a substrate;
(2) A step of temporarily fixing a semiconductor chip on a temporary fixing film;
(3) forming an encapsulation layer on the semiconductor chip;
(4) peeling the substrate and the temporary fixing film from the semiconductor chip;
(5) forming a rewiring formation layer as an insulating layer on the surface of the semiconductor chip from which the base material and the temporary fixing film have been peeled off; and (6) forming a rewiring layer as a conductor layer on the rewiring formation layer.

Furthermore, the resin composition according to one embodiment of the present invention can be used in a wide range of applications where resin compositions are used, such as sheet-like laminate materials such as resin sheets and prepregs, solder resists, underfill materials, die bonding materials, semiconductor encapsulation materials, hole filling resins, and component embedding resins.

[Sheet-like laminate material]
The resin composition according to one embodiment of the present invention may be used by coating in the form of a varnish, but from an industrial perspective, it is preferable to use the resin composition in the form of a sheet-like laminate material containing the resin composition.

The following resin sheets and prepregs are preferred as sheet-like laminate materials.

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 from the resin composition according to this embodiment. Thus, the resin composition layer usually includes a resin composition, and preferably includes only a resin composition.

The thickness of the resin composition layer is preferably 50 μm or less, more preferably 40 μm or less, from the viewpoint of making the printed wiring board thinner and being able to provide a cured product with excellent insulating properties even if the cured product of the resin composition is a thin film. 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.

Examples of the support include films made of plastic materials, metal foils, and release paper, with films made of plastic materials and metal foils being preferred.

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

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

The support may be subjected to a matte treatment, corona treatment, or antistatic treatment on the surface that is to be bonded to the resin composition layer.

As the support, a support with a release layer having a release layer on the surface to be bonded to the resin composition layer may be used. Examples of the release agent used in the release layer of the support with a release layer include one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. The support with a release layer may be a commercially available product, such as "SK-1", "AL-5", and "AL-7" manufactured by Lintec Corporation, "Lumirror T60" manufactured by Toray Industries, "Purex" manufactured by Teijin Limited, and "Unipeel" manufactured by Unitika Limited, which are PET films having a release layer mainly composed of an alkyd resin-based release agent.

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

In one embodiment, the resin sheet may further include an optional layer as necessary. For example, such an optional layer may be a protective film similar to the support provided on the surface of the resin composition layer that is not bonded to the support (i.e., the surface opposite 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 adhesion of dirt and scratches on the surface of the resin composition layer.

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

The organic solvent may be, for example, the same as the solvent described as a component of the resin composition. One type of organic solvent may be used alone, or two or more types may be used in combination.

Drying may be performed by known methods such as heating or blowing hot air. There are no particular limitations on the drying conditions, but drying is performed so that the content of organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. Although this 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 organic solvent, the resin composition layer can be formed by drying at 50°C to 150°C for 3 to 10 minutes.

The resin sheet can be stored in a roll. If the resin sheet has a protective film, it can be used by peeling off the protective film.

In one embodiment, the prepreg is produced by a method that includes impregnating a sheet-like fiber substrate with the resin composition according to this embodiment.

The sheet-like fiber substrate used for the prepreg may be, for example, a commonly used substrate for prepregs, such as glass cloth, aramid nonwoven fabric, or liquid crystal polymer nonwoven fabric. From the viewpoint of thinning the printed wiring board, the thickness of the sheet-like fiber substrate is preferably 50 μm or less, more preferably 40 μm or less, even more preferably 30 μm or less, and particularly preferably 20 μm or less. There is no particular lower limit to the thickness of the sheet-like fiber substrate, and it is usually 10 μm or more.

Prepregs can be manufactured using methods such as the hot melt method and the solvent method.

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

The sheet-like laminate material can be suitably used to form an insulating layer of a printed wiring board (for the insulating layer of a printed wiring board), and can be even more suitably used to form an interlayer insulating layer of a printed wiring board (for the interlayer insulating layer of a printed wiring board).

[Printed wiring board]
The printed wiring board according to one embodiment of the present invention includes an insulating layer including a cured product obtained by curing the resin composition according to the present embodiment. The printed wiring board can be produced, 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.

The "inner layer substrate" used in step (I) is a member that will be the substrate of the printed wiring board, and examples thereof include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, and thermosetting polyphenylene ether substrates. The substrate may have a conductor layer on one or both sides, and the conductor layer may be patterned. An inner layer substrate having a conductor layer (circuit) formed on one or both sides of the substrate is sometimes called an "inner layer circuit substrate." In addition, intermediate products on which an insulating layer and/or a conductor layer is to be formed during the manufacture of a printed wiring board are 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 a component embedded may be used.

The resin composition layer is preferably formed on the inner layer substrate using the above-mentioned resin sheet. 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 bonded to the inner layer substrate. The lamination of the inner layer substrate and the resin sheet can be performed, for example, by hot pressing the resin sheet to the inner layer substrate from the support side. Examples of the member for hot pressing the resin sheet to the inner layer substrate (hereinafter also referred to as the "hot pressing member") include a heated metal plate (such as a SUS panel) or a metal roll (SUS roll). It is preferable to press the hot pressing member through an elastic material such as heat-resistant rubber so that the resin sheet can sufficiently follow the surface irregularities of the inner layer substrate, rather than directly pressing the resin sheet.

The lamination of the inner layer substrate and the resin sheet may be performed by a vacuum lamination method. In the vacuum lamination method, the heat-pressure 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 heat-pressure bonding pressure is preferably in the range of 0.098MPa to 1.77MPa, more preferably in the range of 0.29MPa to 1.47MPa, and the heat-pressure 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 performed under reduced pressure conditions of 26.7hPa or less.

Lamination can be performed using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum pressure laminator manufactured by Meiki Seisakusho Co., Ltd., a vacuum applicator manufactured by Nikko Materials Co., Ltd., and a batch type vacuum pressure laminator.

After lamination, the laminated resin sheets may be smoothed under normal pressure (atmospheric pressure), for example by pressing a heat-pressure bonding member from the support side. The pressing conditions for the smoothing treatment may be the same as the heat-pressure bonding conditions for the lamination. The smoothing treatment may be performed using a commercially available laminator. Note that lamination and smoothing treatment may be performed consecutively using the commercially available vacuum laminator.

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

In step (II), the resin composition layer is cured to form an insulating layer made of a cured product of the resin composition. The resin composition layer is usually cured by thermal curing. The specific curing conditions for the resin composition layer may be the conditions usually adopted when forming an insulating layer for a printed wiring board.

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

Before the resin composition layer is thermally cured, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermally curing the resin composition layer, the resin composition layer may be preheated at a temperature of 50°C to 150°C, preferably 60°C to 140°C, and 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.

When manufacturing a printed wiring board, the 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 that are used in the manufacture of printed wiring boards. When the support is removed after step (II), the removal of the support may be carried out between steps (II) and (III), between steps (III) and (IV), or between steps (IV) and (V). Furthermore, the formation of the insulating layer and the conductor layer in steps (I) to (V) may be repeated as necessary to form a multilayer wiring board.

In another embodiment, the printed wiring board can be manufactured using the above-mentioned prepreg. The manufacturing method can be basically the same as when a resin sheet is used.

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

Step (IV) is a step of roughening the insulating layer. Usually, smears are also removed in this step (IV). The procedure and conditions of the roughening treatment are not particularly limited, and known procedures and conditions used in forming insulating layers of printed wiring boards can be adopted. For example, the insulating layer can be roughened by carrying out a swelling treatment using a swelling liquid, a roughening treatment using an oxidizing agent, and a neutralization treatment using a neutralizing liquid in this order.

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

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

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

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

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

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

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

In one embodiment, the conductor layer may be formed by plating. For example, a conductor layer having a desired wiring pattern can be formed by plating the surface of the insulating layer using a conventionally known technique such as a semi-additive method or a full-additive method. From the viewpoint of ease of production, the semi-additive method is preferred. Below, an example of forming a conductor layer by a semi-additive method is shown.

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

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

Metal foils can be manufactured by known methods such as electrolysis and rolling. Commercially available metal foils include HLP foil and JXUT-III foil manufactured by JX Nippon Mining & Metals Corporation, and 3EC-III foil and TP-III foil manufactured by Mitsui Mining & Smelting Co., Ltd.

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

Semiconductor devices include various semiconductor devices used in electrical appliances (e.g., computers, mobile phones, digital cameras, and televisions) and vehicles (e.g., motorcycles, automobiles, trains, ships, and aircraft).

The present invention will be specifically explained below with reference to examples. However, the present invention is not limited to these examples. In the following, "parts" and "%" representing amounts mean "parts by mass" and "% by mass", respectively, unless otherwise specified. In addition, the temperature and pressure conditions, unless otherwise specified, were room temperature (25°C) and atmospheric pressure (1 atm).

[Example 1]
Five parts of a liquid epoxy resin ("ZX1059" manufactured by Nippon Steel Chemical & Material Co., Ltd., a 1:1 mixture (mass ratio) of bisphenol A type epoxy resin and bisphenol F type epoxy resin, epoxy equivalent: 169 g/eq.) and 15 parts of a biphenyl type epoxy resin ("NC3000H" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: approximately 290 g/eq.) were dissolved in a mixed solvent of 20 parts of toluene and 20 parts of MEK by heating with stirring. The resulting solution was cooled to room temperature, and then mixed with 42 parts of an active ester curing agent ("HP-B-8151-62T" manufactured by DIC Corporation, 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 Corporation, hydroxyl group equivalent approximately 151 g/eq., 2-methoxypropanol solution with a solid content of 50%), and 1 part 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). 0 parts of a silica-containing resin (a resin having a trimethoxysilyl group introduced into the side chain of a directly added unit of a styrene-butadiene copolymer, Shin-Etsu Chemical Co., Ltd.'s "X-12-1281C", number average molecular weight 5,000), 1.5 parts of a curing accelerator (Shikoku Chemical Co., Ltd.'s "1B2PZ", MEK solution with a solid content of 10 mass %), and 150 parts of an inorganic filler (spherical silica (Admatechs Co., Ltd.'s "SO-C2", average particle size 0.5 μm, specific surface area 5.8 m ² /g) surface-treated with an amine-based silane coupling agent (Shin-Etsu Chemical Co., Ltd.'s "KBM573")) were mixed and uniformly dispersed in a high-speed rotating mixer to obtain resin composition 1.

[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 Chemical Co., Ltd.'s "V-03", active group equivalent of about 216 g/eq., toluene solution with a solid content of 50%) was added.

[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 (SA9000, a (meth)acrylic radical polymerizable compound manufactured by SABIC Innovative Plastics, a toluene solution with a solid content of 50%) was added.

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

[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 Inc., active group equivalent 199 g/eq., methyl amyl ketone solution with a solid content of 65% by mass) was used instead of 42 parts of an active ester curing agent ("HP-B-8151-62T" manufactured by DIC Corporation, active group equivalent 238 g/eq., toluene solution with a solid content of 62%).

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

[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 is introduced into the side chain of a directly added unit of a styrene-butadiene copolymer, "X-12-1281A" manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight 9,000).

[Example 8]
Resin composition 8 was obtained in the same manner as in Example 5, 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 triethoxysilyl group is introduced into the side chain of a directly added unit of a styrene-butadiene copolymer, "X-12-1281A-ES" manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight 9,500. It may correspond to a resin containing a structure represented by formula (2), in which j = 52, k = 0, l = 22, m = 29, n = 3, Y is an ethylene group, and R ⁴⁶ is an ethyl group).

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

[Comparative Example 2]
Comparative resin composition 2 was prepared in the same manner as in Example 1, except that 1.4 parts of a styrene-diene copolymer (Clay Valley's Ricon 184) and 0.1 parts of an alkoxysilane compound (Shin-Etsu Chemical's epoxy silane KBM403) were used instead of 1.5 parts of the silicon-containing resin (Shin-Etsu Chemical's X-12-1281C). However, the mixture was poor and a uniform resin composition was not obtained.

[Preparation 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.

Resin compositions 1 to 8 and comparative resin composition 1 were each uniformly applied to a support using a die coater so that the thickness of the resin composition layer after drying was 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 (Oji F-Tex Co., Ltd. "Alphan MA-411", thickness 15 μm) was attached as a protective film to the surface of the resin composition layer that was not joined to the support. This resulted in a resin sheet A having a support, a resin composition layer, and a protective film in this order.

[Adhesion to plated conductor layer]
(1) Preparation of inner layer substrate A glass cloth-based epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.4 mm, Panasonic "R1515A") with copper inner layer circuits formed on both sides was prepared as an inner layer substrate. Both sides of the inner layer substrate were etched by 1 μm with a microetching agent (Mec "CZ8101") to roughen the copper surface.

(2) Lamination of 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 (two-stage build-up laminator "CVP700" manufactured by Nikko Materials Co., Ltd.), the resin composition layer was laminated on both sides of the inner layer substrate so that it was in contact with the inner layer substrate. The lamination was performed by reducing the pressure for 30 seconds to adjust the air pressure to 13 hPa or less, and then pressing at 120°C and a pressure of 0.74 MPa for 30 seconds. Next, a heat press was performed at 100°C and a pressure of 0.5 MPa for 60 seconds.

(3) Thermal curing of resin composition layer The inner layer substrate with the resin sheet laminated thereon was then 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 made of a cured product of the resin composition. The support was then peeled off to obtain a cured substrate A having an insulating layer, an inner layer substrate, and an insulating layer in this order.

(4) Roughening Treatment A desmear treatment was performed as a roughening treatment on the insulating layer of the cured substrate A. As the desmear treatment, the following wet desmear treatment was performed.

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

(5) Formation of Conductive Layer According to the semi-additive method, a conductive 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. Next, after heating at 150 ° C for 30 minutes and performing an annealing treatment, an etching resist was formed, and a pattern was formed by etching. Then, copper sulfate electrolytic plating was performed to form a conductive layer having a thickness of 30 μm, and an annealing treatment was performed at 200 ° C for 60 minutes. The obtained substrate is called "evaluation substrate B".

(6) Evaluation of Adhesion with Plated Conductive Layer The peel strength of the insulating layer and the plated conductor layer was measured in accordance with the Japanese Industrial Standards (JIS C6481). Specifically, a cut was made in the conductor layer of evaluation board B to surround a rectangular portion having a width of 10 mm and a length of 100 mm. One end of this rectangular portion was peeled off and gripped with a gripper, and the load (kgf/cm) was measured when 35 mm was peeled off in the vertical direction at a speed of 50 mm/min at room temperature, to determine the peel strength (plated peel strength). A tensile tester ("AC-50C-SL" manufactured by TSE) was used for the measurement.

[Dielectric properties]
The protective film was peeled off from the resin sheet A produced in the examples and comparative examples, and the resin composition layer was thermally cured by heating at 200°C for 90 minutes. The support was then peeled off to obtain a cured product of the resin composition. The obtained cured product is referred to as "evaluation cured product C". The evaluation cured product C was cut to obtain a test piece having a width of 2 mm and a length of 80 mm. The dielectric tangent of the test piece was measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23°C by a cavity resonance perturbation method using an Agilent Technologies "HP8362B". Measurements were performed on three test pieces, and the average value was calculated.

[Crack resistance]
(1) Lamination of resin sheet 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) formed on both sides in a wiring pattern of line/space (L/S) = 8 μm/8 μm was prepared. Resin sheet A from which the protective film had been 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. This lamination was performed by using a vacuum pressure laminator ("MVLP-500" manufactured by Meiki Seisakusho Co., Ltd.) to perform vacuum suction at a temperature of 120°C for 30 seconds, and then pressing from above the support via heat-resistant rubber at a temperature of 120°C and a pressure of 0.7 MPa for 30 seconds. Next, pressing was performed for 60 seconds at atmospheric pressure using a SUS end plate at a temperature of 120°C and a pressure of 0.55 MPa.

(2) Thermal curing of resin composition layer The inner layer substrate with the resin sheet laminated thereon was placed in an oven at 130° C. and heated for 30 minutes, 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 made of a cured product of the resin composition. The support was then peeled off to obtain a cured substrate D having the insulating layer, the inner layer substrate, and the insulating layer in this order.

(3) Roughening Treatment A desmear treatment was performed as a roughening treatment on the cured substrate D. The desmear treatment was performed in the same manner as the (wet desmear treatment) described in the above section [Adhesion to plated conductor layer].

(4) Evaluation of crack resistance The insulating layer surface immediately above the wiring pattern (L/S=8 μm/8 μm) of the inner layer substrate was observed after the desmear treatment. For 100 samples, it was confirmed whether or not cracks occurred on the insulating layer surface along the pattern shape of the inner layer substrate, and the ratio of samples without cracks was calculated. This ratio was calculated as the "yield", and a yield of 50% or more was evaluated as "○" and a yield of less than 50% was evaluated as "×".

[result]
The results of the above-mentioned Examples and Comparative Examples are shown in the following Tables 1 and 2. Note that for Comparative Example 2, none of the peel strength, dielectric tangent, and crack resistance could be evaluated.

Claims (17)

(A) an epoxy resin, (B) a curing agent, and (C) an alkoxysilyl group-containing conjugated diene-aromatic vinyl copolymer resin which may be hydrogenated,
The component (C) contains (c1) an optionally hydrogenated conjugated diene compound unit and (c2) an aromatic vinyl compound unit,
(c1) an alkoxysilyl group is bonded to a part or all of the optionally hydrogenated conjugated diene compound units,
The content of the component (A) is 5% by mass or more and 50% by mass or less, when the resin component in the resin composition is 100% by mass,
A resin composition, wherein the content of the (C) component is 0.5% by mass or more and 15% by mass or less, when the resin component in the resin composition is 100% by mass. (c1) the optionally hydrogenated conjugated diene compound unit is an optionally hydrogenated butadiene unit,
The resin composition according to claim 1 , wherein the aromatic vinyl compound unit (c2) is a styrene unit. (c1) The optionally hydrogenated conjugated diene compound unit contains a direct addition unit,
The resin composition according to claim 1 or 2 , wherein the direct addition unit is a part or all of a side chain of the direct addition unit. The resin composition according to any one of claims 1 to 3 , wherein the amount of the aromatic vinyl compound unit (c2) is 15% by mass or more and 50% by mass or less, when the component (C) is 100% by mass. (A) an epoxy resin, (B) a curing agent, and (C) an alkoxysilyl group-containing conjugated diene-aromatic vinyl copolymer resin which may be hydrogenated,
The component (C) contains an alkenylalkoxysilane unit (c3) ,
The content of the component (A) is 5% by mass or more and 50% by mass or less, when the resin component in the resin composition is 100% by mass,
A resin composition, wherein the content of the (C) component is 0.5% by mass or more and 15% by mass or less, when the resin component in the resin composition is 100% by mass . The resin composition according to any one of claims 1 to 5 , wherein the component (C) comprises a structure represented by the following formula (1):
(In formula (1),
R ¹ to R ³¹ , R ³⁴ to R ⁴⁰ , and R ⁴³ to 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 each represent an integer 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. 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):
(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 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. 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. The resin composition according to any one of claims 1 to 8 , wherein the (B) curing agent comprises an active ester curing agent. The resin composition according to any one of claims 1 to 9 , further comprising (D) an inorganic filler. 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. The resin composition according to any one of claims 1 to 11 , which is for forming an insulating layer. A cured product of the resin composition according to any one of claims 1 to 12 . A sheet-like laminate material comprising the resin composition according to any one of claims 1 to 12 . A support;
A resin sheet comprising: a support; and a resin composition layer formed from the resin composition according to any one of claims 1 to 12 on the support. A printed wiring board comprising an insulating layer comprising a cured product of the resin composition according to any one of claims 1 to 12 . A semiconductor device comprising the printed wiring board according to claim 16 .