JP2023069752A - resin composition - Google Patents

Abstract

To provide a resin composition capable of giving a cured product excellent in all of smear removability, plating adhesion, and metal foil adhesion.SOLUTION: The resin composition contains (A) an epoxy resin, (B) an active ester compound, (C) an inorganic filler, and (D) a (meth)acrylate having a biphenyl skeleton. The content of the active ester compound (B) is 10 mass% or more based on 100 mass% of a nonvolatile component in the resin composition. The content of the inorganic filler (C) is 60 mass% or more based on 100 mass% of the nonvolatile component in the resin composition.SELECTED DRAWING: None

Description

The present invention relates to resin compositions.

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

JP 2020-23714 A

The cured product contained in the insulating layer is required to have a low dielectric loss tangent. One of the methods for obtaining a cured product with a low dielectric loss tangent is to mix an active ester compound and an inorganic filler at a high concentration in a resin composition. However, when a resin composition containing a high concentration of an active ester compound and an inorganic filler is used, the smear removability, plating adhesion, and metal foil adhesion all tend to be low.

Specifically, when an insulating layer is formed from a cured product of a resin composition, holes such as via holes and through holes are sometimes formed in the insulating layer. When such holes are formed in the insulating layer, smears as resin residues may be formed in the holes. Generally, this smear is desired to be removed. Smear removal is often performed using chemicals. However, when a resin composition containing a high concentration of an active ester compound and an inorganic filler is used, the smear removability tends to be low.

Moreover, when forming a conductor layer on an insulating layer, the conductor layer may be formed by plating. However, when a resin composition containing a high concentration of an active ester compound and an inorganic filler is used, the adhesion between the insulating layer and the conductive layer formed by plating tends to be low.

Furthermore, in the process of manufacturing a printed wiring board, an insulating layer is sometimes formed on a conductor layer as a base using a resin composition. The conductor layer as the base is usually a metal foil at the time of forming the insulating layer. Therefore, the insulating layer is required to have excellent adhesion to the underlying metal foil. However, when a resin composition containing a high concentration of an active ester compound and an inorganic filler is used, the adhesion between the insulating layer and the underlying metal foil tends to be low.

The present invention was invented in view of the above problems, and provides a resin composition capable of obtaining a cured product excellent in all of smear removability, plating adhesion, and metal foil adhesion; A cured product of; A sheet-like laminated material containing the resin composition; A resin sheet having a resin composition layer formed of the resin composition; A printed wiring board provided with an insulating layer containing a cured product of the resin composition; and a semiconductor device comprising the printed wiring board.

The inventors have made extensive studies to solve the above problems. As a result, the present inventor has (A) an epoxy resin, (B) an active ester compound in a specific range amount, (C) an inorganic filler in a specific range amount, and (D) a biphenyl skeleton (meta ) The present inventors have completed the present invention by discovering that a resin composition containing an acrylic acid ester in combination can solve the above problems.
That is, the present invention includes the following.

（式（Ｄ１）において、
Ｒ^１１は、それぞれ独立に、水素原子又はメチル基を表し、
Ｒ^１２は、それぞれ独立に、２価の脂肪族炭化水素基を表し、
ｍ１は、０～５の整数を表し、
ｎ１は、０～６の整数を表し、
Ｒ^２１は、それぞれ独立に、水素原子又はメチル基を表し、
Ｒ^２２は、それぞれ独立に、２価の脂肪族炭化水素基を表し、
ｍ２は、０～５の整数を表し、
ｎ２は、０～６の整数を表す。
ただし、ｍ１＋ｍ２は、１以上である。）
〔４〕 樹脂組成分中の不揮発成分を１００質量％とした場合、（Ｄ）ビフェニル骨格を有する（メタ）アクリル酸エステルの含有量が、０．５質量％以上２５質量％以下である、〔１〕～〔３〕のいずれか一項に記載の樹脂組成物。
〔５〕 フェノール系硬化剤及びカルボジイミド系硬化剤からなる群より選ばれる１種類以上の（Ｅ）硬化剤を含む、〔１〕～〔４〕のいずれか一項に記載の樹脂組成物。
〔６〕 （Ｆ）硬化促進剤を含む、〔１〕～〔５〕のいずれか一項に記載の樹脂組成物。
〔７〕 （Ｇ）熱可塑性樹脂を含む、〔１〕～〔６〕のいずれか一項に記載の樹脂組成物。
〔８〕 絶縁層形成用である、〔１〕～〔７〕のいずれか一項に記載の樹脂組成物。
〔９〕 〔１〕～〔８〕の何れか１項に記載の樹脂組成物の硬化物。
〔１０〕 〔１〕～〔８〕の何れか１項に記載の樹脂組成物を含有する、シート状積層材料。
〔１１〕 支持体と、当該支持体上に〔１〕～〔８〕の何れか１項に記載の樹脂組成物で形成された樹脂組成物層と、を有する樹脂シート。
〔１２〕 〔１〕～〔８〕の何れか１項に記載の樹脂組成物の硬化物を含む絶縁層を備える、プリント配線板。
〔１３〕 〔１２〕に記載のプリント配線板を備える、半導体装置。 [1] A resin composition containing (A) an epoxy resin, (B) an active ester compound, (C) an inorganic filler, and (D) a (meth)acrylic acid ester having a biphenyl skeleton,
When the non-volatile component in the resin composition is 100% by mass, the content of (B) the active ester compound is 10% by mass or more,
A resin composition in which the content of (C) an inorganic filler is 60% by mass or more when the non-volatile component in the resin composition is 100% by mass.
[2] The resin composition of [1], wherein (D) the (meth)acrylic acid ester having a biphenyl skeleton contains a compound containing an ether structure.
[3] The resin composition according to [1] or [2], wherein (D) the (meth)acrylic acid ester having a biphenyl skeleton contains a compound represented by the following formula (D1).

(In formula (D1),
each R ¹¹ independently represents a hydrogen atom or a methyl group;
each R ¹² independently represents a divalent aliphatic hydrocarbon group,
m1 represents an integer from 0 to 5,
n1 represents an integer from 0 to 6,
each R ²¹ independently represents a hydrogen atom or a methyl group;
each R ²² independently represents a divalent aliphatic hydrocarbon group,
m2 represents an integer from 0 to 5,
n2 represents an integer of 0-6.
However, m1+m2 is 1 or more. )
[4] When the non-volatile component in the resin composition is 100% by mass, the content of (D) a (meth)acrylic acid ester having a biphenyl skeleton is 0.5% by mass or more and 25% by mass or less [ 1] The resin composition according to any one of [3].
[5] The resin composition according to any one of [1] to [4], which contains at least one (E) curing agent selected from the group consisting of phenolic curing agents and carbodiimide curing agents.
[6] The resin composition according to any one of [1] to [5], which contains (F) a curing accelerator.
[7] The resin composition according to any one of [1] to [6], which contains (G) a thermoplastic resin.
[8] The resin composition according to any one of [1] to [7], which is used for forming an insulating layer.
[9] A cured product of the resin composition according to any one of [1] to [8].
[10] A sheet-like laminate material containing the resin composition according to any one of [1] to [8].
[11] A resin sheet comprising a support and a resin composition layer formed on the support from the resin composition according to any one of [1] to [8].
[12] A printed wiring board comprising an insulating layer containing a cured product of the resin composition according to any one of [1] to [8].
[13] A semiconductor device comprising the printed wiring board according to [12].

According to the present invention, a resin composition capable of obtaining a cured product excellent in all of smear removability, plating adhesion, and metal foil adhesion; a cured product of the resin composition; containing the resin composition a sheet-like laminated material to be used; a resin sheet having a resin composition layer formed from the resin composition; a printed wiring board provided with an insulating layer containing a cured product of the resin composition; and a semiconductor device provided with the printed wiring board ; can be provided.

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

In the following description, the term "(meth)acrylic acid ester" includes acrylic acid esters, methacrylic acid esters and combinations thereof, unless otherwise specified. In the following description, the term "(meth)acryloyl group" includes acryloyl group, methacryloyl group and combinations thereof unless otherwise specified. Furthermore, in the following description, the term "(meth)acryloyloxy group" includes acryloyloxy groups, methacryloyloxy groups and combinations thereof, unless otherwise specified. Moreover, in the following description, the term "(meth)acrylate" includes acrylate, methacrylate and combinations thereof unless otherwise specified.

[1. Overview of resin composition]
The resin composition according to one embodiment of the present invention contains (A) an epoxy resin, a specific range of amount of (B) an active ester compound, a specific range of amount of (C) an inorganic filler, and (D) a biphenyl skeleton. (meth)acrylic acid esters having According to this resin composition, it is possible to obtain a cured product that is excellent in all of smear removal properties, plating adhesion properties, and metal foil adhesion properties. Also, this cured product can usually have a low dielectric loss tangent. Furthermore, this cured product can usually have a small surface roughness after the roughening treatment. This cured product can be suitably used, for example, as a material for insulating layers of printed wiring boards.

The present inventor conjectures the mechanism by which the cured product of the resin composition according to the present embodiment can obtain such excellent advantages as follows. However, the technical scope of the present invention is not limited by the mechanism described below.

A cured product of a conventional resin composition containing an epoxy resin, a predetermined amount or more of an active ester compound, and a predetermined amount or more of an inorganic filler can usually have a low dielectric loss tangent. However, the cured product of the resin composition generally tends to have low smear removability, plating adhesion, and metal foil adhesion.

On the other hand, the resin composition according to the present embodiment includes (A) an epoxy resin, a specific range of amount of (B) an active ester compound, and a specific range of amount of (C) an inorganic filler, and (D ) in combination with a (meth)acrylic acid ester having a biphenyl skeleton. The (meth)acrylic acid ester having a biphenyl skeleton as the component (D) is hereinafter sometimes referred to as "specific (meth)acrylic acid ester". (D) The carbon-carbon unsaturated bond (ethylenically unsaturated bond) of the (meth)acryloyl group contained in the specific (meth)acrylic acid ester can cause a radical polymerization reaction during curing of the resin composition. (D) Specific (meth)acrylic acid esters can bond to each other. Bonds between the (D) specific (meth)acrylic acid esters contained in this cured product can be easily oxidized and cleaved by the oxidizing agent used for removing smear. Therefore, since the removal of the cured product by the oxidizing agent can be accelerated, the smear removability is improved.

In addition, since the biphenyl skeleton contained in the (D) specific (meth)acrylic acid ester has high rigidity, the action of the (D) specific (meth)acrylic acid ester containing the biphenyl skeleton increases the mechanical strength of the cured product of the resin composition. strength. Therefore, the resistance of the cured product to stress can be enhanced. Therefore, delamination (delamination between layers) that accompanies destruction of the cured product can be suppressed, so that plating adhesion and metal foil adhesion can be improved.

Furthermore, the radical polymerization reaction of the (D) specific (meth)acrylic acid ester usually does not generate a polar group such as a hydroxyl group. Therefore, even if the (D) specific (meth)acrylic acid ester is contained, the cured product can have a low polarity. Therefore, the cured product of the resin composition can usually have a low dielectric loss tangent.

In addition, (D) the specific (meth)acrylic acid ester having a biphenyl skeleton can have excellent affinity with (A) the epoxy resin and (B) the active ester compound. Therefore, the phase separation of the resin components such as the (A) component, the (B) component and the (D) component is suppressed in the resin composition. If the resin component undergoes large phase separation, a large phase domain is formed in the cured product, and each phase domain is detached during the roughening treatment, which may increase the surface roughness. However, in the resin composition according to the present embodiment, since the phase separation of the resin components is suppressed, the formation of large phase domains is suppressed. Therefore, it can usually have a small surface roughness after roughening treatment.

[2. (A) Epoxy resin]
The resin composition according to this embodiment contains (A) an epoxy resin as the (A) component. (A) The epoxy resin may be a curable resin having an epoxy group.

(A) Epoxy resins include, for example, 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, and trisphenol type epoxy resins. Epoxy resin, naphthol novolak type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin , cresol novolac type epoxy resin, phenol aralkyl type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane-type epoxy resin, cyclohexanedimethanol-type epoxy resin, naphthylene ether-type epoxy resin, trimethylol-type epoxy resin, tetraphenylethane-type epoxy resin, isocyanurate-type epoxy resin, phenolphthalimidine-type epoxy resin, and the like. . (A) Epoxy resins may be used singly or in combination of two or more.

(A) The epoxy resin preferably contains an epoxy resin containing an aromatic structure from the viewpoint of obtaining a cured product having excellent heat resistance. Aromatic structures are chemical structures generally defined as aromatic and also include polycyclic aromatic and heteroaromatic rings. Examples of epoxy resins containing an aromatic structure include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, Naphthol novolak type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, bixylenol type epoxy resin, glycidylamine type epoxy having an aromatic structure Resin, glycidyl ester type epoxy resin having aromatic structure, cresol novolak type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin having aromatic structure, epoxy resin having butadiene structure having aromatic structure, aromatic Structured alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin having aromatic structure, cyclohexane dimethanol type epoxy resin having aromatic structure, naphthylene ether type epoxy resin, having aromatic structure A trimethylol type epoxy resin, a tetraphenylethane type epoxy resin having an aromatic structure, and the like are included.

The resin composition preferably contains an epoxy resin having two or more epoxy groups in one molecule as (A) the epoxy resin. (A) The proportion of the epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 100% by mass of the non-volatile components of the epoxy resin. is 70% by mass or more.

Epoxy resins include liquid epoxy resins at a temperature of 20° C. (hereinafter sometimes referred to as “liquid epoxy resins”) and solid epoxy resins at a temperature of 20° C. (hereinafter sometimes referred to as “solid epoxy resins”). ). As the epoxy resin, the resin composition may contain only a liquid epoxy resin, may contain only a solid epoxy resin, or may contain a combination of a liquid epoxy resin and a solid epoxy resin. good.

A liquid epoxy resin having two or more epoxy groups in one molecule is preferable as the liquid epoxy resin.

Examples of liquid epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolac type epoxy resin, and an ester skeleton. An alicyclic epoxy resin, a cyclohexane type epoxy resin, a cyclohexanedimethanol type epoxy resin, and an epoxy resin having a butadiene structure are preferred.

Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene type epoxy resins) manufactured by DIC; "828US", "828EL", "jER828EL", and "825" manufactured by Mitsubishi Chemical Corporation; ", "Epikote 828EL" (bisphenol A type epoxy resin); "jER807" and "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "630", "630LSD", "604" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "ED-523T" (glycirrol type epoxy resin) manufactured by ADEKA; "EP-3950L" manufactured by ADEKA; "EP-3980S" (glycidylamine type epoxy resin); "EP-4088S" (dicyclopentadiene type epoxy resin) manufactured by ADEKA; Bisphenol F type epoxy resin mixture); "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX; "Celoxide 2021P" manufactured by Daicel (alicyclic epoxy resin having an ester skeleton); Daicel "PB-3600" manufactured by Nippon Soda Co., Ltd., "JP-100" and "JP-200" (epoxy resins having a butadiene structure) manufactured by Nippon Soda Co., Ltd.; 1,4-glycidylcyclohexane type epoxy resin) and the like. These may be used individually by 1 type, and may be used in combination of 2 or more types.

The solid epoxy resin is preferably a solid epoxy resin having 3 or more epoxy groups per molecule, more preferably an aromatic solid epoxy resin having 3 or more epoxy groups per molecule.

Solid epoxy resins include bixylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, naphthol novolak type epoxy resin, cresol novolak type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, Naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, phenol aralkyl type epoxy resin, tetraphenylethane type epoxy resin, phenol phthalate A mijin-type epoxy resin is preferred.

Specific examples of solid epoxy resins include "HP4032H" (naphthalene-type epoxy resin) manufactured by DIC; "HP-4700" and "HP-4710" (naphthalene-type tetrafunctional epoxy resin) manufactured by DIC; "N-690" (cresol novolac type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolak type epoxy resin) manufactured by DIC Corporation; "HP-7200", "HP-7200HH", "HP -7200H", "HP-7200L" (dicyclopentadiene type epoxy resin); DIC's "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S" ", "HP6000" (naphthylene ether type epoxy resin); Nippon Kayaku "EPPN-502H" (trisphenol type epoxy resin); Nippon Kayaku "NC7000L" (naphthol novolac type epoxy resin); "NC3000H", "NC3000", "NC3000L", "NC3000FH", "NC3100" (biphenyl type epoxy resin) manufactured by Nippon Kayaku; epoxy resin); "ESN485" (naphthol type epoxy resin) manufactured by Nippon Steel Chemical &Materials; "ESN375" (dihydroxynaphthalene type epoxy resin) manufactured by Nippon Steel Chemical &Materials; "YX4000H" manufactured by Mitsubishi Chemical, "YX4000", "YX4000HK", "YL7890" (bixylenol type epoxy resin); "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX8800" (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; Mitsubishi "YX7700" (phenol aralkyl type epoxy resin) manufactured by Chemical Company; "PG-100" and "CG-500" manufactured by Osaka Gas Chemicals Co., Ltd.; "YL7760" manufactured by Mitsubishi Chemical Corporation (bisphenol AF type epoxy resin); Mitsubishi Chemical Company "YL7800" (fluorene type epoxy resin); Mitsubishi Chemical Corporation "jER1010" (bisphenol A type epoxy resin); Mitsubishi Chemical Corporation "jER1031S" (tetraphenylethane type epoxy resin); Nippon Kayaku "WHR991S" (phenol phthalimidine type epoxy resin) manufactured by Co., Ltd., and the like. These may be used individually by 1 type, and may be used in combination of 2 or more types.

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

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

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

The content of (A) the epoxy resin in the resin composition is preferably 1% by mass or more, more preferably 2% by mass or more, and particularly preferably 4% by mass, when the non-volatile component in the resin composition is 100% by mass. % or more, preferably 25 mass % or less, more preferably 20 mass % or less, and particularly preferably 10 mass % or less. (A) When the amount of the epoxy resin is within the above range, the smear removability, plating adhesion, metal foil adhesion, dielectric loss tangent, and surface roughness after roughening treatment can be particularly improved.

The content of (A) the epoxy resin in the resin composition is preferably 5% by mass or more, more preferably 10% by mass or more, and particularly preferably 20% by mass, when the resin component in the resin composition is 100% by mass. % or more, preferably 70% by mass or less, more preferably 50% by mass or less, and particularly preferably 30% by mass or less. The resin component of the resin composition represents the non-volatile components of the resin composition excluding (C) the inorganic filler. (A) When the amount of the epoxy resin is within the above range, the smear removability, plating adhesion, metal foil adhesion, dielectric loss tangent, and surface roughness after roughening treatment can be particularly improved.

[3. (B) Active ester compound]
The resin composition according to the present embodiment contains the (B) active ester compound as the (B) component in a content within a specific range. (B) The active ester compound can function as an epoxy resin curing agent that reacts with (A) the epoxy resin to cure the resin composition. (B) The active ester compound may be used singly or in combination of two or more.

(B) The active ester compound generally has two or more highly reactive ester groups per molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds. is preferably used. The active ester compound is preferably 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 compound obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester compound obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferred. Examples of carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of phenol compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucine, Benzenetriol, dicyclopentadiene-type diphenol compound, phenol novolak, and the like. Here, the term "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing one molecule of dicyclopentadiene with two molecules of phenol.

Specifically, the (B) active ester compound includes a dicyclopentadiene-type active ester compound, a naphthalene-type active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolak, and a benzoylated product of phenol novolak. Active ester compounds are preferred, and among them, at least one selected from dicyclopentadiene type active ester compounds and naphthalene type active ester compounds is more preferred. As the dicyclopentadiene-type active ester compound, an active ester compound containing a dicyclopentadiene-type diphenol structure is preferable.

(B) Commercially available active ester compounds include, for example, "EXB9451", "EXB9460", "EXB9460S", "EXB-8000L", and "EXB-8000L" as active ester compounds containing a dicyclopentadiene type diphenol structure. -65M", "EXB-8000L-65TM", "HPC-8000L-65TM", "HPC-8000", "HPC-8000-65T", "HPC-8000H", "HPC-8000H-65TM" (DIC Corporation ); as active ester compounds containing a naphthalene structure, "HP-B-8151-62T", "EXB-8100L-65T", "EXB-8150-60T", "EXB-8150-62T", "EXB-9416- 70BK", "HPC-8150-60T", "HPC-8150-62T", "EXB-8" (manufactured by DIC Corporation); "EXB9401" (manufactured by DIC Corporation) as a phosphorus-containing active ester compound; acetyl of phenol novolak "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester compound that is a compound; "YLH1026", "YLH1030", and "YLH1048" (manufactured by Mitsubishi Chemical Corporation) as active ester compounds that are benzoyl compounds of phenol novolak; styryl group and naphthalene Examples of active ester compounds containing structures include "PC1300-02-65MA" (manufactured by Air Water).

(B) The active ester group equivalent of the active ester compound is preferably 50 g/eq. ~500 g/eq. , more preferably 50 g/eq. ~400 g/eq. , more preferably 100 g/eq. ~300 g/eq. is. The active ester group equivalent represents the mass of the active ester compound per equivalent of active ester group.

When the number of epoxy groups of (A) epoxy resin is 1, the number of active ester groups of (B) active ester compound is preferably 0.1 or more, more preferably 0.5 or more, and still more preferably 1.0 or more. , preferably 5.0 or less, more preferably 4.0 or less, and particularly preferably 3.0 or less. The "number of epoxy groups in (A) the epoxy resin" represents the sum of all the values obtained by dividing the mass of the non-volatile component of the (A) epoxy resin present in the resin composition by the epoxy equivalent. In addition, "(B) the number of active ester groups of the active ester compound" is a value obtained by dividing the mass of the non-volatile component of the (B) active ester compound present in the resin composition by the active ester group equivalent and summing all the values. show.

The content of (B) the active ester compound in the resin composition is usually 10% by mass or more, preferably 11% by mass or more, more preferably 12% by mass, when the non-volatile component in the resin composition is 100% by mass. More preferably 13% by mass or more, particularly preferably 14% by mass or more, preferably 35% by mass or less, more preferably 30% by mass or less, even more preferably 25% by mass or less, particularly preferably 20% by mass or less is. (B) When the amount of the active ester compound is within the above range, particularly good smear removability, plating adhesion, metal foil adhesion, dielectric loss tangent, and surface roughness after roughening treatment can be obtained.

The content of (B) the active ester compound in the resin composition is preferably 25% by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass, when the resin component in the resin composition is 100% by mass. % by mass or more, particularly preferably 50% by mass or more, preferably 90% by mass or less, more preferably 80% by mass or less, even more preferably 70% by mass or less, and particularly preferably 60% by mass or less. (B) When the amount of the active ester compound is within the above range, particularly good smear removability, plating adhesion, metal foil adhesion, dielectric loss tangent, and surface roughness after roughening treatment can be obtained.

[4. (C) Inorganic filler]
The resin composition according to the present embodiment contains (C) an inorganic filler in a content within a specific range. (C) The inorganic filler is usually contained in the resin composition in the form of particles.

(C) An inorganic compound is used as the material of the inorganic filler. (C) Examples of inorganic filler materials include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, and water. Aluminum oxide, 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. As silica, spherical silica is preferable. (C) An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more type.

(C) Commercially available inorganic fillers include, for example, "UFP-30" manufactured by Denka Kagaku Kogyo; "SP60-05" and "SP507-05" manufactured by Nippon Steel & Sumikin Materials; "YC100C", "YA050C", "YA050C-MJE", "YA010C"; "UFP-30" manufactured by Denka; 5N”; “SC2500SQ”, “SO-C4”, “SO-C2” and “SO-C1” manufactured by Admatechs; “DAW-03” and “FB-105FD” manufactured by Denka.

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

(C) The average particle size of the inorganic filler can be measured by a laser diffraction/scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler is prepared on a volume basis using a laser diffraction/scattering type particle size distribution measuring device, and the median diameter can be used as the average particle size for measurement. A measurement sample can be obtained by weighing 100 mg of an inorganic filler and 10 g of methyl ethyl ketone in a vial and dispersing them with ultrasonic waves for 10 minutes. A measurement sample is measured using a laser diffraction particle size distribution measuring device, the wavelengths of the light source used are blue and red, the volume-based particle size distribution of the inorganic filler is measured by the flow cell method, and from the obtained particle size distribution The average particle size can be calculated as the median size. Examples of the laser diffraction particle size distribution analyzer include "LA-960" manufactured by Horiba, Ltd., and the like.

(C) The specific surface area of the inorganic filler is preferably 0.1 m ² /g or more, more preferably 0.5 m ² /g or more, and still more preferably 1 m ² from the viewpoint of significantly obtaining the desired effects of the present invention. /g or more, particularly preferably 3 m ² /g or more, 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. be. The specific surface area of the inorganic filler is determined by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech) according to the BET method, and calculating the specific surface area using the BET multipoint method. can be measured by

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

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

From the viewpoint of improving the dispersibility of the inorganic filler, the degree of surface treatment with the surface treatment agent is preferably within a specific range. Specifically, 100% by mass of the inorganic filler is preferably surface-treated with a surface treatment agent of 0.2% to 5% by mass, and a surface treatment agent of 0.2% to 3% by mass. It is more preferably surface-treated, and more preferably surface-treated with 0.3% by mass to 2% by mass of a surface treating 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. 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 more preferably 0.2 mg/m ² from the viewpoint of improving the dispersibility of the inorganic filler. The above is more preferable. On the other hand, from the viewpoint of preventing the melt viscosity of the resin composition from increasing, 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.

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

The content of the inorganic filler (C) in the resin composition is preferably 60% by mass or more, more preferably 65% by mass or more, particularly preferably 70% by mass, when the non-volatile component in the resin composition is 100% by mass. % or more, preferably 86% by mass or less, more preferably 82% by mass or less, and particularly preferably 78% by mass or less. (C) When the amount of the inorganic filler is within the above range, the smear removability, plating adhesion, metal foil adhesion, dielectric loss tangent, and surface roughness after roughening treatment can be particularly improved.

[5. (D) (Meth)acrylic acid ester having a biphenyl skeleton]
The resin composition according to the present embodiment contains (D) a (D) component (meth)acrylic acid ester having a biphenyl skeleton (that is, (D) a specific (meth)acrylic acid ester).

(D) The specific (meth)acrylic acid ester contains a (meth)acryloyloxy group in its molecule. The carbon-carbon unsaturated bond (ethylenically unsaturated bond) contained in the (meth)acryloyloxy group can usually cause a radical polymerization reaction during curing of the resin composition. (D) The number of (meth)acryloyloxy groups contained in the molecule of the specific (meth)acrylic acid ester may be one, or two or more. (D) The specific number of (meth)acryloyloxy groups contained in the molecule of the specific (meth)acrylic acid ester is preferably 1 or more, preferably 6 or less, more preferably 4 or less, and still more preferably 3 or less. , particularly preferably 2 or less.

(D) The specific (meth)acrylic acid ester has a biphenyl skeleton in its molecule. (D) The number of biphenyl skeletons contained in the molecule of the specific (meth)acrylic acid ester may be two or more, but usually one. The (meth)acryloyloxy group may be bonded directly or indirectly via a linking group to the benzene ring of the biphenyl skeleton. (D) When the specific (meth)acrylic acid ester has two or more (meth)acryloyloxy groups, the (meth)acryloyloxy group may be bonded only to one of the two benzene rings of the biphenyl skeleton. , a (meth)acryloyloxy group is preferably bound to each of the two benzene rings of the biphenyl skeleton.

(D) The specific (meth)acrylic acid ester preferably further contains an ether structure in combination with the (meth)acryloyloxy group and biphenyl skeleton. Therefore, (D) the specific (meth)acrylic acid ester preferably contains a compound containing an ether structure. This ether structure does not include an ether structure contained in a (meth)acryloyloxy group. The number of ether structures contained in the molecule of (D) the specific (meth)acrylic acid ester containing an ether structure may be one, or two or more. Also, the ether structure is preferably contained in a connecting group that connects the (meth)acryloyloxy group and the benzene ring of the biphenyl skeleton. Furthermore, at least one oxygen atom contained in the ether structure is preferably directly bonded to the benzene ring.

Furthermore, the linking group that links the (meth)acryloyloxy group and the benzene ring of the biphenyl skeleton preferably contains a divalent aliphatic hydrocarbon group. Therefore, (D) the specific (meth)acrylic acid ester preferably contains a compound containing a linking group containing a divalent aliphatic hydrocarbon group. The divalent aliphatic hydrocarbon group is preferably a chain aliphatic hydrocarbon group, and may be linear or branched. Also, the divalent aliphatic hydrocarbon group is preferably a saturated aliphatic hydrocarbon group. The number of carbon atoms in the divalent aliphatic hydrocarbon group is usually 1 or more, preferably 12 or less, more preferably 6 or less, still more preferably 4 or less, and particularly preferably 2 or less. Examples of preferred divalent aliphatic hydrocarbon groups include methylene group, ethylene group, propylene group, butylene group, pentylene group and hexylene group.

As the specific (meth)acrylate (D), a compound represented by the following formula (D1) is particularly preferable. Therefore, (D) the specific (meth)acrylic acid ester preferably contains a compound represented by the following formula (D1), and more preferably contains only a compound represented by the following formula (D1).

In Formula (D1), each R ¹¹ independently represents a hydrogen atom or a methyl group. In formula (D1), each R ²¹ independently represents a hydrogen atom or a methyl group.

In formula (D1), each R ¹² independently represents a divalent aliphatic hydrocarbon group. In formula (D1), each R ²² independently represents a divalent aliphatic hydrocarbon group. As the divalent aliphatic hydrocarbon group, those within the range described above as the divalent aliphatic hydrocarbon group that may contain a linking group linking the (meth)acryloyloxy group and the benzene ring of the biphenyl skeleton can be used.

In formula (D1), m1 represents an integer of 0 to 5, preferably 0 or 1, particularly preferably 1. In formula (D1), m2 represents an integer of 0 to 5, preferably 0 or 1, particularly preferably 1. However, m1+m2 is 1 or more.

In formula (D1), each n1 independently represents an integer of 0 to 6. In formula (D1), each n2 independently represents an integer of 0 to 6. Specifically, n1 and n2 are usually 0 or more, preferably 1 or more, and usually 6 or less, preferably 4 or less, more preferably 3 or less, and particularly preferably 2 or less. n1 and n2 may be the same or different.

Specific examples of the (D) specific (meth)acrylic acid ester include those represented by the following formulas (d1) to (d4). In the formula below, n represents an integer of 1 or more, preferably 1 to 2, more preferably 1.

(D) Commercial products of specific (meth) acrylic acid esters include, for example, Shin-Nakamura Chemical Co., Ltd. “A-LEN-10” (compound represented by formula (d1)), Honshu Chemical Industry Co., Ltd. “A —BP-2EO” (compound represented by formula (d3)).

(D) The specific (meth)acrylic acid ester may be used alone or in combination of two or more.

The mass ratio W D /W A of the mass W _{A of} (A) the epoxy resin and the mass _{W D} of the (D) specific (meth)acrylic acid ester in the resin composition is preferably 0.1 or more, more preferably 0.3 or more, more preferably 0.5 or more, particularly preferably 0.7 or more, preferably 10 or less, more preferably 5.0 or less, still more preferably 2.0 or less, particularly preferably 1.0 It is below. When the mass ratio W _D /W _A is within the above range, the plating adhesion and metal foil adhesion can be effectively enhanced, and the dielectric loss tangent can generally be effectively lowered.

The mass ratio W _D /W B of the mass W B _of the (B) active ester compound and the mass W _D of the (D) specific (meth)acrylic acid ester in the resin _composition is preferably 0.01 or more, more preferably is 0.05 or more, more preferably 0.10 or more, particularly preferably 0.15 or more, preferably 2.0 or less, more preferably 1.5 or less, still more preferably 1.0 or less, particularly preferably 0.5 or less. When the mass ratio W _D /W _B is within the above range, the plating adhesion and metal foil adhesion can be effectively enhanced, and the dielectric loss tangent can generally be effectively lowered.

The mass ratio of the total mass W _A +W B of (A) the epoxy resin and ( _B ) the active ester compound _{in the resin composition to the mass W D of the (D) specific (meth)acrylic acid ester W D /} (W _A + W _B ) is preferably 0.01 or more, more preferably 0.05 or more, still more preferably 0.10 or more, particularly preferably 0.20 or more, preferably 2.0 or less, more preferably 1.5 Below, more preferably 1.0 or less, particularly preferably 0.5 or less. When the mass ratio W _D /(W _A +W _B ) is within the above range, the plating adhesion and metal foil adhesion can be effectively enhanced, and the dielectric loss tangent can generally be effectively lowered.

The mass ratio WD/ _WC between the mass WC of the ( _C ) inorganic filler and the mass WD of the ( _D ) specific (meth)acrylic acid ester _in the resin composition is preferably 0.001 or more, more preferably is 0.01 or more, more preferably 0.02 or more, particularly preferably 0.03 or more, preferably 0.4 or less, more preferably 0.3 or less, still more preferably 0.2 or less, particularly preferably 0.1 or less. When the mass ratio W _D /W _C is within the above range, the plating adhesion and metal foil adhesion can be effectively enhanced, and the dielectric loss tangent can generally be effectively lowered.

The content of the (D) specific (meth)acrylic acid ester in the resin composition is preferably 0.5% by mass or more, more preferably 1.0% by mass, when the non-volatile component in the resin composition is 100% by mass. % by mass or more, particularly preferably 2.0% by mass or more, preferably 25% by mass or less, more preferably 20% by mass or less, and particularly preferably 10% by mass or less. (D) When the amount of the specific (meth)acrylic acid ester is within the above range, particularly good smear removability, plating adhesion, metal foil adhesion, dielectric loss tangent, and surface roughness after roughening treatment can be obtained.

The content of the (D) specific (meth)acrylic acid ester in the resin composition is preferably 2% by mass or more, more preferably 5% by mass or more, when the resin component in the resin composition is 100% by mass, It is particularly preferably 10% by mass or more, preferably 70% by mass or less, more preferably 40% by mass or less, and particularly preferably 20% by mass or less. (D) When the amount of the specific (meth)acrylic acid ester is within the above range, particularly good smear removability, plating adhesion, metal foil adhesion, dielectric loss tangent, and surface roughness after roughening treatment can be obtained.

[6. (E) optional curing agent]
The resin composition according to the present embodiment may further contain (E) an optional curing agent as an optional component in combination with the above-described components (A) to (D). The (E) optional curing agent as the (E) component does not include those corresponding to the above-described components (A) to (D). The (E) optional curing agent can function as an epoxy resin curing agent that reacts with the (A) epoxy resin to cure the resin composition, like the (B) active ester compound described above. (E) Any curing agent may be used singly or in combination of two or more.

(E) Examples of optional curing agents include phenol-based curing agents, carbodiimide-based curing agents, acid anhydride-based curing agents, amine-based curing agents, benzoxazine-based curing agents, cyanate ester-based curing agents, and thiol-based curing agents. agents. Among them, it is preferable to use one or more curing agents selected from the group consisting of phenolic curing agents and carbodiimide curing agents.

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

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 cyclohexanebis(methylene-t-butylcarbodiimide); biscarbodiimides such as biscarbodiimide; aliphatic polycarbodiimides such as polyhexamethylenecarbodiimide, polytrimethylhexamethylenecarbodiimide, polycyclohexylenecarbodiimide, poly(methylenebiscyclohexylenecarbodiimide), and poly(isophoronecarbodiimide); poly(phenylenecarbodiimide), Poly(naphthylenecarbodiimide), Poly(tolylenecarbodiimide), Poly(methyldiisopropylphenylenecarbodiimide), Poly(triethylphenylenecarbodiimide), Poly(diethylphenylenecarbodiimide), Poly(triisopropylphenylenecarbodiimide), Poly(diisopropylphenylenecarbodiimide) , poly(xylylenecarbodiimide), poly(tetramethylxylylenecarbodiimide), poly(methylenediphenylenecarbodiimide), poly[methylenebis(methylphenylene)carbodiimide] and other aromatic polycarbodiimides. Examples of commercially available carbodiimide curing agents include "Carbodilite V-02B", "Carbodilite V-03", "Carbodilite V-04K", "Carbodilite V-07" and "Carbodilite V-09" manufactured by Nisshinbo Chemical Co., Ltd. "Stabaxol P", "Stabaxol P400", and "Hykasil 510" manufactured by Rhein Chemie.

As the acid anhydride-based curing agent, a curing agent having one or more acid anhydride groups in one molecule can be used, and a curing agent having two or more acid anhydride groups in one molecule is used. preferable. Specific examples of acid anhydride curing agents include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, and hydrogenated methylnadic acid. anhydride, trialkyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trianhydride mellitic acid, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'- Diphenylsulfonetetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-C]furan-1 , 3-dione, ethylene glycol bis(anhydrotrimellitate), polymer-type acid anhydrides such as styrene/maleic acid resin obtained by copolymerizing styrene and maleic acid. Examples of commercially available acid anhydride curing agents include "HNA-100", "MH-700", "MTA-15", "DDSA" and "OSA" manufactured by Shin Nippon Rika; "YH-306", "YH-307" of Hitachi Chemical Co., Ltd. "HN-2200", "HN-5500"; Clay Valley Co., Ltd. "EF-30", "EF-40" "EF-60", "EF-80" and the like.

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 amine-based curing agents include aliphatic amines, polyetheramines, alicyclic amines, aromatic amines, etc. Among them, aromatic amines are preferred. Amine-based curing agents are preferably primary amines or secondary amines, more preferably primary amines. Specific examples of amine curing agents include 4,4'-methylenebis(2,6-dimethylaniline), 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, and 3,3'-diaminodiphenylsulfone. , m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4′-diaminodiphenyl ether, 3,3′-dimethyl-4,4′-diaminobiphenyl, 2,2′-dimethyl-4,4′ -diaminobiphenyl, 3,3′-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2, 2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4- aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)sulfone, bis(4- (3-aminophenoxy)phenyl)sulfone, and the like. Examples of commercially available amine-based curing agents include "SEIKACURE-S" manufactured by Seika; AB", "Kayahard AS"; "Epicure W" manufactured by Mitsubishi Chemical; "DTDA" manufactured by Sumitomo Seika.

Specific examples of benzoxazine-based curing agents include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemical Co., Ltd.; "HFB2006M" manufactured by Showa Polymer Co., Ltd.; Examples include "Fa".

Examples of cyanate ester curing agents include bisphenol A dicyanate, polyphenolcyanate (oligo(3-methylene-1,5-phenylenecyanate)), 4,4'-methylenebis(2,6-dimethylphenylcyanate), 4, 4′-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatophenylmethane), bis(4-cyanate-3,5- Difunctional cyanate resins such as dimethylphenyl)methane, 1,3-bis(4-cyanatophenyl-1-(methylethylidene))benzene, bis(4-cyanatophenyl)thioether, and bis(4-cyanatophenyl)ether, Polyfunctional cyanate resins derived from phenol novolak, cresol novolak, etc., and prepolymers obtained by partially triazine-forming these cyanate resins. Specific examples of cyanate ester curing agents include "PT30" and "PT60" (both phenol novolac type polyfunctional cyanate ester resins), "BA230" and "BA230S75" (part of bisphenol A dicyanate) manufactured by Lonza Japan Co., Ltd. or a prepolymer that is entirely triazined to form a trimer), and the like.

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

(E) The active group equivalent of any curing agent is preferably 50 g/eq. ~3000g/eq. , more preferably 100 g/eq. ~1000 g/eq. , more preferably 100 g/eq. ~500 g/eq. , particularly preferably 100 g/eq. ~300 g/eq. is. Active group equivalents represent the mass of curing agent per equivalent of active groups.

The content of the optional curing agent (E) in the resin composition may be 0% by mass or greater than 0% by mass when the non-volatile component in the resin composition is 100% by mass. It is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, particularly preferably 1.0% by mass or more, preferably 20% by mass or less, more preferably 10% by mass or less, particularly preferably 5% by mass. % by mass or less.

The content of the optional curing agent (E) in the resin composition may be 0% by mass or greater than 0% by mass when the resin component in the resin composition is 100% by mass, It is preferably 0.1% by mass or more, more preferably 1.0% by mass or more, particularly preferably 5.0% by mass or more, preferably 50% by mass or less, more preferably 20% by mass or less, particularly preferably 10% by mass. % by mass or less.

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

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

Phosphorus curing accelerators include, for example, tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium) pyromellitate, tetrabutylphosphonium hydro Aliphatic phosphonium salts such as genhexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate, di-tert-butyldimethylphosphonium tetraphenylborate; methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra-p-tolylborate, tetraphenyl phosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, triphenylethylphosphonium tetraphenylborate, tris(3-methylphenyl)ethylphosphonium tetraphenylborate, tris(2-methoxyphenyl)ethylphosphonium tetraphenylborate, (4 -methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, aromatic phosphonium salts such as butyltriphenylphosphonium thiocyanate; aromatic phosphine/borane complexes such as triphenylphosphine/triphenylborane; triphenylphosphine/p-benzoquinone Aromatic phosphine/quinone addition reaction products such as addition reaction products; 2-butenyl)phosphine, aliphatic phosphines such as tricyclohexylphosphine; -tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tris(4-ethylphenyl)phosphine, tris(4-propylphenyl)phosphine, tris(4-isopropylphenyl)phosphine, tris(4-butyl) phenyl)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. be done.

Urea-based curing accelerators include, for example, 1,1-dimethylurea; 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, 3- Aliphatic dimethylurea such as 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, 3-(3,4-dimethylphenyl)-1,1-dimethylurea, 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4- methoxyphenyl)-1,1-dimethylurea, 3-(4-nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy)phenyl]-1,1-dimethylurea, 3- [4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trifluoromethyl)phenyl]-1,1-dimethylurea, N,N-(1,4-phenylene) Aromatic dimethylurea such as bis(N',N'-dimethylurea), N,N-(4-methyl-1,3-phenylene)bis(N',N'-dimethylurea) [toluenebisdimethylurea] etc.

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

Examples of imidazole 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, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl- 2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecyl imidazolyl-(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 isocyanurate, 2-phenylimidazole isocyanurate, 2-phenyl-4,5-dihydroxymethylimidazole, 2- Phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline , 2-phenylimidazoline and other imidazole compounds, and adducts of imidazole compounds and epoxy resins. Examples of commercially available imidazole curing accelerators include, for example, Shikoku Kasei Co., Ltd. "1B2PZ", "2E4MZ", "2MZA-PW", "2MZ-OK", "2MA-OK", "2MA-OK- PW", "2PHZ", "2PHZ-PW", "Cl1Z", "Cl1Z-CN", "Cl1Z-CNS", "C11Z-A"; 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, and zinc (II) acetylacetonate. and the like, organic iron complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of organic metal salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

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

The content of the (F) curing accelerator in the resin composition may be 0% by mass, or may be greater than 0% by mass, preferably when the non-volatile component in the resin composition is 100% by mass. is 0.01% by mass or more, more preferably 0.02% by mass or more, particularly preferably 0.03% by mass or more, preferably 1.0% by mass or less, more preferably 0.5% by mass or less, especially Preferably, it is 0.1% by mass or less.

The content of the (F) curing accelerator in the resin composition may be 0% by mass, or may be greater than 0% by mass, preferably when the resin component in the resin composition is 100% by mass. is 0.01% by mass or more, more preferably 0.05% by mass or more, particularly preferably 0.1% by mass or more, preferably 2.0% by mass or less, more preferably 1.5% by mass or less, especially Preferably, it is 1.0% by mass or less.

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

(G) Thermoplastic resins include, for example, phenoxy resins, polyimide resins, polyvinyl acetal resins, polyolefin resins, polybutadiene resins, polyamideimide resins, polyetherimide resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, and polycarbonate resins. , polyether ether ketone resin, polyester resin, and the like. (G) The thermoplastic resin may be used alone or in combination of two or more.

Examples of phenoxy resins include 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, and terpene. Examples include phenoxy resins having one or more skeletons selected from the group consisting of skeletons and trimethylcyclohexane skeletons. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. Specific examples of the phenoxy resin include Mitsubishi Chemical's "1256" and "4250" (both bisphenol A skeleton-containing phenoxy resins); Mitsubishi Chemical's "YX8100" (bisphenol S skeleton-containing phenoxy resin); Mitsubishi Chemical "YX6954" (bisphenolacetophenone skeleton-containing phenoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.; "FX280" and "FX293" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.; "YL7769BH30", "YL6794", "YL7213", "YL7290", "YL7482" and "YL7891BH30";

Specific examples of the polyimide resin include “SLK-6100” manufactured by Shin-Etsu Chemical Co., Ltd., “Likacoat SN20” and “Ricacoat PN20” manufactured by Shin Nippon Rika Co., Ltd., and the like.

Examples of polyvinyl acetal resins include polyvinyl formal resins and polyvinyl butyral resins, and polyvinyl butyral resins are 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 Sekisui Chemical Co., Ltd. S-LEC BH series, BX series (eg BX-5Z), KS series (eg KS-1), BL series, BM series;

Examples of polyolefin resins include ethylene-based copolymers such as low-density polyethylene, ultra-low-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-methyl acrylate copolymer. Resin: polyolefin polymers such as polypropylene and ethylene-propylene block copolymers.

Polybutadiene resins include, for example, 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, and isocyanate group-containing resins. Examples include polybutadiene resin, urethane group-containing polybutadiene resin, polyphenylene ether-polybutadiene resin, and the like.

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

Specific examples of the polyethersulfone resin include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd., and the like.

Specific examples of the polysulfone resin include polysulfone "P1700" and "P3500" manufactured by Solvay Advanced Polymers.

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

Examples of polycarbonate resins include hydroxyl group-containing carbonate resins, phenolic hydroxyl group-containing carbonate resins, carboxy group-containing carbonate resins, acid anhydride group-containing carbonate resins, isocyanate group-containing carbonate resins, and urethane group-containing carbonate resins. Specific examples of polycarbonate resins include "FPC0220" manufactured by Mitsubishi Gas Chemical Co., Ltd., "T6002" and "T6001" (polycarbonate diol) manufactured by Asahi Kasei Chemicals, "C-1090" and "C-2090" manufactured by Kuraray Co., Ltd. , “C-3090” (polycarbonate diol) and the like. Specific examples of the polyetheretherketone resin include "Sumiproy K" manufactured by Sumitomo Chemical Co., Ltd., and the like.

Examples of polyester resins include polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin, polybutylene naphthalate resin, polytrimethylene terephthalate resin, polytrimethylene naphthalate resin, polycyclohexanedimethyl terephthalate resin, and the like.

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

The content of the (G) thermoplastic resin in the resin composition may be 0% by mass, or may be greater than 0% by mass, preferably when the non-volatile component in the resin composition is 100% by mass. is 0.01% by mass or more, more preferably 0.10% by mass or more, particularly preferably 0.20% by mass or more, preferably 5.0% by mass or less, more preferably 2.0% by mass or less, especially Preferably, it is 1.0% by mass or less.

The content of the (G) thermoplastic resin in the resin composition may be 0% by mass, or may be greater than 0% by mass, preferably when the resin component in the resin composition is 100% by mass. is 0.01% by mass or more, more preferably 0.10% by mass or more, particularly preferably 0.50% by mass or more, preferably 10% by mass or less, more preferably 5.0% by mass or less, particularly preferably It is 3.0% by mass or less.

[9. (H) radically polymerizable compound]
The resin composition according to the present embodiment may further contain (H) any radically polymerizable compound as an optional component in combination with the components (A) to (G) described above. The (H) radically polymerizable compound as the (H) component does not include those corresponding to the above-described components (A) to (G). (H) Radically polymerizable compounds may be used singly or in combination of two or more.

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

(H) Radically polymerizable compounds include, for example, (meth)acrylic radically polymerizable compounds, styrene radically polymerizable compounds, allyl radically polymerizable compounds, and maleimide radically polymerizable compounds.

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

The styrene-based radically 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 radically polymerizable compounds include divinylbenzene, 2,4-divinyltoluene, 2,6-divinylnaphthalene, 1,4-divinylnaphthalene, 4,4′-divinylbiphenyl, 1,2-bis(4 -vinylphenyl)ethane, 2,2-bis(4-vinylphenyl)propane, bis(4-vinylphenyl)ether and other low molecular weight (molecular weight less than 1000) styrene compounds; vinylbenzyl-modified polyphenylene ether resin, styrene- High-molecular weight (molecular weight 1000 or more) styrene compounds such as divinylbenzene copolymers can be used. Examples of commercially available styrene-based radical polymerizable compounds include "ODV-XET (X03)", "ODV-XET (X04)", and "ODV-XET (X05)" (styrene -divinylbenzene copolymer), Mitsubishi Gas Chemical Company's "OPE-2St 1200" and "OPE-2St 2200" (vinylbenzyl-modified polyphenylene ether resin).

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

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

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

(H) The weight average molecular weight (Mw) of the radically polymerizable compound 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 can be, for example, 150 or more.

The content of the (H) radically polymerizable compound in the resin composition may be 0% by mass or greater than 0% by mass when the non-volatile component in the resin composition is 100% by mass. Preferably 0.01% by mass or more, more preferably 0.1% by mass or more, particularly preferably 1.0% by mass or more, preferably 16% by mass or less, more preferably 12% by mass or less, particularly preferably 8 0% by mass or less.

The content of (H) the radically polymerizable compound in the resin composition may be 0% by mass or greater than 0% by mass when the resin component in the resin composition is 100% by mass. Preferably 0.01% by mass or more, more preferably 0.10% by mass or more, particularly preferably 1.0% by mass or more, preferably 25% by mass or less, more preferably 20% by mass or less, particularly preferably 15% by mass % by mass or less.

[10. (I) optional additive]
The resin composition according to the present embodiment may further contain (I) an optional additive as an optional non-volatile component in combination with the components (A) to (H) described above. (I) Optional additives include, for example, radical polymerization initiators such as peroxide-based radical polymerization initiators and azo-based radical polymerization initiators; epoxy acrylate resins, urethane acrylate resins, urethane resins, cyanate resins, benzoxazine Thermosetting resins other than epoxy resins such as resins, unsaturated polyester resins, phenolic resins, melamine resins and silicone resins; organic fillers such as rubber particles; organic metal compounds such as organic copper compounds, organic zinc compounds and organic cobalt compounds Colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, phenothiazine; silicone leveling agents, acrylic polymer leveling agents leveling agents such as; thickeners such as bentone and montmorillonite; defoaming agents such as silicone-based defoaming agents, acrylic defoaming agents, fluorine-based defoaming agents, and vinyl resin-based defoaming agents; benzotriazole-based ultraviolet absorbers UV absorbers such as UV absorbers; adhesion improvers such as urea silane; adhesion promoters such as triazole-based adhesion promoters, tetrazole-based adhesion promoters, and triazine-based adhesion promoters; antioxidants; fluorescent brighteners such as stilbene derivatives; surfactants such as fluorine-based surfactants and silicone-based surfactants; phosphorus), nitrogen flame retardants (e.g. melamine sulfate), halogen flame retardants, inorganic flame retardants (e.g. antimony trioxide); phosphate ester dispersants, polyoxyalkylene dispersants, acetylene dispersants agent, silicone dispersant, anionic dispersant, cationic dispersant; borate stabilizer, titanate stabilizer, aluminate stabilizer, zirconate stabilizer, isocyanate stabilizer, carboxylic acid stabilizer Stabilizers, stabilizers such as carboxylic acid anhydride-based stabilizers. (I) Optional additives may be used singly or in combination of two or more.

[11. (J) Solvent]
The resin composition according to the present embodiment may contain (J) a solvent as an optional volatile component in combination with the non-volatile components such as components (A) to (I) described above. (J) As the solvent, an organic solvent is usually used. Examples of organic solvents include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ester solvents; ether solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, anisole; alcohol solvents such as methanol, ethanol, propanol, butanol, ethylene glycol; acetic acid Ether ester solvents such as 2-ethoxyethyl, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl diglycol acetate, γ-butyrolactone, methyl methoxypropionate; methyl lactate, ethyl lactate, methyl 2-hydroxyisobutyrate, etc. ester alcohol solvents; 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, diethylene glycol monobutyl ether (butyl carbitol) and other ether alcohol solvents; N,N-dimethylformamide, N, Amide solvents such as N-dimethylacetamide and N-methyl-2-pyrrolidone; sulfoxide solvents such as dimethylsulfoxide; nitrile solvents such as acetonitrile and propionitrile; aliphatics such as hexane, cyclopentane, cyclohexane, and methylcyclohexane Hydrocarbon-based solvents: aromatic hydrocarbon-based solvents such as benzene, toluene, xylene, ethylbenzene, trimethylbenzene, and the like can be mentioned. (J) The solvent may be used alone or in combination of two or more.

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

[12. Method for producing a resin composition]
The resin composition according to this embodiment can be produced, for example, by mixing the components described above. Some or all of the components described above may be mixed at the same time, or may be mixed in order. During the course of mixing each component, the temperature may be set accordingly, and thus may be temporarily or permanently heated and/or cooled. Moreover, you may perform stirring or shaking in the process of mixing each component.

[13. Physical properties of the resin composition]
The resin composition according to the present embodiment can give a cured product with excellent smear removability. For example, when the smear removal property is evaluated under the conditions described in the section [Evaluation method of smear removal property and arithmetic mean roughness (Ra)] in Examples described later, smear extending from the wall surface of the bottom of the via hole The maximum smear length can be less than 5 μm. In general, the shorter the maximum smear length, the better the smear removal properties.

A cured product having excellent plating adhesion can be obtained from the resin composition according to the present embodiment. That is, when a conductor layer is formed on a cured product of a resin composition by plating, high adhesion can be obtained between the conductor layer and the cured product. For example, when the plating peel strength is measured under the conditions described in the section [Method for measuring plating adhesion (plating peel strength)] in Examples to be described later, the plating peel strength can be increased. The plating peel strength represents the magnitude of the force required to peel off the conductor layer formed by plating on the cured product of the resin composition, and the greater the plating peel strength, the better the plating adhesion. show. The plating peel strength is preferably 0.45 kgf/cm or more, more preferably 0.50 kgf/cm or more, and particularly preferably 0.53 kgf/cm or more.

The resin composition according to the present embodiment can provide a cured product with excellent adhesion to metal foil. That is, when the resin composition is laminated on a metal foil and cured to form a cured product, high adhesion can be obtained between the metal foil and the cured product. For example, the copper foil peeling strength can be increased when the copper foil peeling strength is measured under the conditions described in the section [Evaluation Method for Metal Foil Adhesion] in Examples described later. The copper foil peeling strength represents the magnitude of the force required to peel off the copper foil as the metal foil from the cured product of the resin composition. Represents excellence. The copper foil peel strength is preferably 0.50 kgf/cm or more, more preferably 0.60 kgf/cm or more, and particularly preferably 0.70 kgf/cm or more.

The resin composition according to the present embodiment can usually obtain a cured product with a low dielectric loss tangent. For example, a low dielectric loss tangent can be obtained when the dielectric loss tangent of the cured product is measured under the conditions described in the section [Method for measuring dielectric loss tangent] in Examples described later. The dielectric loss tangent of the cured product is preferably 0.0040 or less, more preferably 0.0035 or less, and particularly preferably 0.0030 or less.

A cured product of the resin composition according to the present embodiment can usually have a small surface roughness when subjected to a roughening treatment. For example, when the arithmetic average roughness Ra of the cured product after roughening treatment is measured under the conditions described in the section [Method for evaluating smear removability and arithmetic mean roughness (Ra)] in Examples described later, , a small arithmetic mean roughness Ra can be obtained. The arithmetic mean roughness Ra is preferably 120 nm or less, more preferably 110 nm or less, and particularly preferably 100 nm or less. The lower limit is not particularly limited, and may be 30 nm or more, 40 nm or more, and the like.

[14. Applications of the resin composition]
The resin composition according to the present embodiment can be used as a resin composition for insulation, and in particular can be suitably used as a resin composition for forming an insulation layer (resin composition for forming an insulation layer). . For example, the resin composition according to the present embodiment can be used as a resin composition for forming an insulating layer of a printed wiring board, and a resin composition for forming an interlayer insulating layer (resin composition for interlayer insulation). can be suitably used as

Further, the resin composition according to the present embodiment may be used as a resin composition for forming a rewiring layer (resin composition for forming a rewiring layer). A rewiring formation layer represents an insulating layer for forming a rewiring layer. Further, the rewiring layer represents a conductor layer formed on a rewiring forming layer as an insulating layer. For example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition according to the present embodiment may be used as a resin composition for forming a rewiring layer. . Further, when the semiconductor chip package is manufactured by 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) temporarily fixing the semiconductor chip on the temporary fixing film;
(3) forming a sealing layer on the semiconductor chip;
(4) a step of peeling the substrate and the temporary fixing film from the semiconductor chip;
(5) Forming a rewiring layer as an insulating layer on the surface of the semiconductor chip from which the base material and the temporary fixing film have been removed; and (6) Forming a rewiring layer as a conductor layer on the rewiring layer. forming process

Furthermore, the resin composition according to the present embodiment includes, for example, a resin sheet, a sheet-like laminated material such as prepreg, a solder resist, an underfill material, a die bonding material, a semiconductor sealing material, a hole-filling resin, a part-embedding resin, etc. It can be used in a wide range of applications in which the composition is used.

[15. Sheet laminated material]
Although the resin composition according to the present embodiment may be applied in the form of a varnish, it is industrially preferable to use it in the form of a sheet-like laminated material containing the resin composition.

As the sheet-like laminate material, resin sheets and prepregs shown below are preferable.

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

The thickness of the resin composition layer is preferably 50 μm or less, more It is preferably 40 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, but may be 5 μm or more, 10 μm or more, or the like.

Examples of the support include a film made of a plastic material, a metal foil, and a release paper, and a film made of a plastic material and a metal foil are preferable.

When a film made of a plastic material is used as the support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"). ), polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylic such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketones, polyimides, and the like. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

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 of copper may be used, and a foil made of an alloy of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. may be used.

The support may be subjected to matte treatment, corona treatment, or antistatic treatment on the surface 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. The release agent used in the release layer of the release layer-attached support includes, for example, one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. . As the support with a release layer, a commercially available product may be used, for example, "SK-1", " AL-5", "AL-7", Toray's "Lumirror T60", Teijin's "Purex", and Unitika's "Unipeel".

The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, more preferably in the range of 10 μm to 60 μm. When a release layer-attached support is used, the thickness of the release layer-attached support as a whole is preferably within the above range.

In one embodiment, the resin sheet may further contain any layer as necessary. Examples of such an optional layer include a protective film conforming to the support provided on the surface of the resin composition layer not bonded to the support (that is, the surface opposite to the support). be done. Although the thickness of the protective film is not particularly limited, it is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to suppress adhesion of dust and scratches on the surface of the resin composition layer.

For the resin sheet, for example, a liquid (varnish) resin composition is used as it is, or a liquid (varnish) resin composition is prepared by dissolving the resin composition in a solvent, and this is coated using a die coater or the like. It can be produced by coating on a support and further drying to form a resin composition layer.

Examples of the solvent include the same solvents as those described as components of the resin composition. A solvent may be used individually by 1 type, and may be used in combination of 2 or more types.

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

The resin sheet can be wound into a roll and stored. When the resin sheet has a protective film, it can be used by peeling off the protective film.

In one embodiment, the prepreg is formed by impregnating a sheet-like fiber base material with the resin composition according to the present embodiment.

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

A prepreg can be produced by a hot melt method, a solvent method, or the like.

The thickness of the prepreg may 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 for forming an insulating layer of a printed wiring board (for an insulating layer of a printed wiring board), and for forming an interlayer insulating layer of a printed wiring board (for a printed wiring board). for interlayer insulating layers).

[16. Printed wiring board]
A printed wiring board according to one embodiment of the present invention includes an insulating layer containing a cured product obtained by curing the resin composition according to the present embodiment. This printed wiring board can be manufactured, for example, using the resin sheet described above by a method including the following steps (I) and (II).
(I) A step of laminating a resin sheet on the inner layer substrate such that the resin composition layer of the resin sheet is bonded to the 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 serves as a printed wiring board substrate, and includes, for example, a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. etc. The substrate may also have a conductor layer on one or both sides thereof, and the conductor layer may be patterned. An inner layer substrate having conductor layers (circuits) formed on one side or both sides of the substrate is sometimes referred to as an "inner layer circuit board." Further, an intermediate product on which an insulating layer and/or a conductor layer are further formed when manufacturing a printed wiring board is also included in the above-mentioned "inner layer board". When the printed wiring board is a circuit board with built-in components, an inner layer board with built-in components may be used.

The lamination of the inner layer substrate and the resin sheet can be performed, for example, by thermocompression bonding the resin sheet to the inner layer substrate from the support side. Examples of the member for thermocompression bonding the resin sheet to the inner layer substrate (hereinafter also referred to as "thermocompression bonding member") include heated metal plates (such as SUS end plates) and metal rolls (SUS rolls). Instead of pressing the thermocompression member directly onto the resin sheet, it is preferable to press through an elastic material such as heat-resistant rubber so that the resin sheet can sufficiently follow the uneven surface of the inner layer substrate.

Lamination of the inner layer substrate and the resin sheet may be performed by a vacuum lamination method. In the vacuum lamination method, the thermocompression temperature is preferably in the range of 60° C. to 160° C., more preferably 80° C. to 140° C., and the thermocompression pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0. .29 MPa to 1.47 MPa, and the heat pressing time is preferably 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. Lamination is preferably carried out under reduced pressure conditions with a pressure of 26.7 hPa or less.

Lamination can be done with a commercially available vacuum laminator. Commercially available vacuum laminators include, for example, a vacuum pressurized laminator manufactured by Meiki Seisakusho, a vacuum applicator manufactured by Nikko Materials, a batch vacuum pressurized laminator, and the like.

After lamination, the laminated resin sheets may be smoothed under normal pressure (atmospheric pressure), for example, by pressing a thermocompression member from the support side. Pressing conditions for the smoothing treatment may be the same as the thermocompression bonding conditions for the lamination described above. Smoothing treatment can be performed with a commercially available laminator. Lamination and smoothing may be performed continuously using the above-mentioned 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. Curing of the resin composition layer is usually performed by heat curing. As the specific curing conditions for the resin composition layer, the conditions that are usually employed when forming the insulating layer of a printed wiring board may be used.

For example, the thermosetting conditions for the resin composition layer vary depending on the type of resin composition and the like. It is preferably 170°C to 210°C. Curing time may preferably be from 5 minutes to 120 minutes, more preferably from 10 minutes to 100 minutes, even more preferably from 15 minutes to 100 minutes.

Before thermosetting the resin composition layer, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermosetting the resin composition layer, the resin composition layer is cured at a temperature of 50° C. to 150° C., preferably 60° C. to 140° C., more preferably 70° C. to 130° C. for 5 minutes or more, It may be preheated for preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, even more preferably 15 minutes to 100 minutes.

When manufacturing a printed wiring board, (III) the step of drilling holes in the insulating layer, (IV) the step of roughening the insulating layer, and (V) the step of 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 support may be removed between step (II) and step (III), between step (III) and step (IV), or step ( It may be carried out between IV) and step (V). If necessary, the steps (I) to (V) of forming the insulating layer and the conductor layer may be repeated to form a multilayer wiring board.

In other embodiments, printed wiring boards can be manufactured using the prepregs described above. The manufacturing method can be basically the same as in the case of using a resin sheet.

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

Step (IV) is a step of roughening the insulating layer. Smear is usually also removed in this step (IV). The procedure and conditions of the roughening treatment are not particularly limited, and known procedures and conditions that are commonly used in forming insulating layers of printed wiring boards can be employed. For example, the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralizing treatment with a neutralizing liquid in this order.

The swelling liquid used for the roughening treatment includes, for example, an alkaline solution, a surfactant solution, etc., preferably an alkaline solution. 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 with 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 minute to 20 minutes. From the viewpoint of suppressing swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling liquid at 40° C. to 80° C. for 5 minutes to 15 minutes.

Examples of the oxidizing agent used for the roughening treatment include an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The roughening treatment with 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 permanganate concentration in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Security P" manufactured by Atotech Japan.

As the neutralizing solution used for the roughening treatment, an acidic aqueous solution is preferable, and commercially available products include, for example, "Reduction Solution Securigant P" manufactured by Atotech Japan. The treatment with the neutralizing solution can be carried out by immersing the treated surface roughened with the oxidizing agent in the neutralizing solution at 30° C. to 80° C. for 5 to 30 minutes. From the viewpoint of workability, etc., a method of immersing an object roughened with an oxidizing agent in a neutralizing solution at 40° C. to 70° C. for 5 to 20 minutes is preferable.

In one embodiment, the arithmetic mean roughness (Ra) of the insulating layer surface after 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 can be, for example, 1 nm or more, 2 nm or more. The root mean square roughness (Rq) of the surface of the insulating layer after 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 can be, for example, 1 nm or more, 2 nm or more. 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, in which 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 selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. Contains metal. The conductor layer may be a single metal layer or an alloy layer, and the alloy layer may be, for example, an alloy of two or more metals selected from the above group (for example, a nickel-chromium alloy, a copper- nickel alloys and copper-titanium alloys). Among them, from the viewpoint of versatility of conductor layer formation, cost, ease of patterning, etc., single metal layers of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, nickel-chromium alloys, copper- Nickel alloys and copper/titanium alloy alloy layers are preferred, and single metal layers of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or nickel/chromium alloy alloy layers are more preferred, and copper single metal layers are preferred. A metal layer is more preferred.

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

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

In one embodiment, the conductor layer may be formed by plating. For example, a conductive layer having a desired wiring pattern can be formed by plating the surface of the insulating layer by a conventionally known technique such as a semi-additive method or a full-additive method. A semi-additive method is preferable from the viewpoint of manufacturing simplicity. An example of forming a conductor layer by a semi-additive method is shown below.

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 a desired wiring pattern. After forming a metal layer on the exposed plating seed layer by electroplating, the mask pattern is removed. After that, the unnecessary plating seed layer is removed by etching or the like, and a conductor layer having a desired wiring pattern can be formed.

In other embodiments, the conductor layer may be formed using a metal foil. When forming the conductor layer using a metal foil, step (V) is preferably performed between step (I) and step (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. Lamination of the resin composition layer and the metal foil may be carried out by a vacuum lamination method. The lamination conditions may be the same as those described for step (I). Then, step (II) is performed to form an insulating layer. After that, using the metal foil on the insulating layer, a conductor layer having a desired wiring pattern can be formed by conventional known techniques such as the subtractive method and the modified semi-additive method.

A metal foil can be manufactured by a known method such as an electrolysis method or a rolling method. Commercially available metal foils include, for example, HLP foil and JXUT-III foil manufactured by JX Nippon Mining & Metals Co., Ltd., 3EC-III foil and TP-III foil manufactured by Mitsui Kinzoku Mining Co., Ltd., and the like.

[17. semiconductor device]
A semiconductor device according to an embodiment of the present invention includes the printed wiring board described above. A semiconductor device can be manufactured using a printed wiring board.

Examples of semiconductor devices include various semiconductor devices used in electrical appliances (eg, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (eg, motorcycles, automobiles, trains, ships, aircraft, etc.).

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

[Example 1]
Biphenyl-type epoxy resin ("NC3000L" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of about 269 g / eq.) 8 parts, and naphthalene-type epoxy resin ("HP-4032-SS" manufactured by DIC, 1,6-bis(glycidyl 2 parts of oxy)naphthalene (epoxy equivalent: about 145 g/eq.) were heated and dissolved in 15 parts of solvent naphtha with stirring. This was cooled to room temperature to prepare an epoxy resin dissolved composition.

To this epoxy resin dissolved composition, 40 parts of an active ester compound ("HPC-8000-65T" manufactured by DIC, an active ester group equivalent of about 223 g/eq., a toluene solution with a nonvolatile content of 65%), a silane coupling agent (“KBM-573” manufactured by Shin-Etsu Chemical Co., Ltd.) surface-treated spherical silica (“SO-C2” manufactured by Admatechs, average particle size 0.5 μm, specific surface area 5.8 m ² /g) 120 parts, biphenyl Skeleton-containing acrylic ester (Shin-Nakamura Chemical Co., Ltd. "A-LEN-10", (meth) acryloyl group equivalent of about 268 g / eq.) 4 parts, triazine skeleton-containing phenolic curing agent (DIC Corporation "LA-3018 -50P", active group equivalent of about 151 g / eq., 2-methoxypropanol solution with a non-volatile content of 50%) 2 parts, carbodiimide curing agent (manufactured by Nisshinbo Chemical Co., Ltd. "V-03", active group equivalent of about 216 g / eq. ., toluene solution with a non-volatile content of 50%) 5 parts, imidazole-based curing accelerator ("1B2PZ" manufactured by Shikoku Kasei Kogyo Co., Ltd., 1-benzyl-2-phenylimidazole) 0.1 parts, phenoxy resin (Mitsubishi Chemical Co., Ltd. Two parts of "YX7553BH30", a 1:1 solution of MEK having a non-volatile content of 30% by mass and cyclohexanone) were mixed and uniformly dispersed with a high-speed rotating mixer to prepare a resin composition.

[Example 2]
Instead of 40 parts of the active ester compound ("HPC-8000-65T" manufactured by DIC, active ester group equivalent weight of about 223 g / eq., toluene solution with a non-volatile content of 65%), an active ester compound (manufactured by DIC "HPC- 8150-62T", an active ester group equivalent of about 220 g/eq., and a toluene solution with a non-volatile content of 62% by mass) was used. In addition, instead of 4 parts of biphenyl skeleton-containing acrylic acid ester (“A-LEN-10” manufactured by Shin-Nakamura Chemical Industry Co., Ltd., (meth) acryloyl group equivalent of about 268 g / eq.), biphenyl skeleton-containing acrylic acid ester (Honshu Chemical 4 parts of "A-BP-2EO" manufactured by Kogyo Co., Ltd. were used. A resin composition was prepared in the same manner as in Example 1 except for the above matters.

[Example 3]
The amount of biphenyl-type epoxy resin (“NC3000L” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of about 269 g/eq.) was changed from 8 parts to 10 parts. Also, a naphthalene-type epoxy resin ("HP-4032-SS" manufactured by DIC, 1,6-bis(glycidyloxy)naphthalene, epoxy equivalent of about 145 g/eq.) was not used. Furthermore, instead of 40 parts of the active ester compound ("HPC-8000-65T" manufactured by DIC, active ester group equivalent weight of about 223 g / eq., toluene solution with a non-volatile content of 65%), an active ester compound (manufactured by DIC "HPC-8150-62T", an active ester group equivalent of about 220 g/eq., a toluene solution with a nonvolatile content of 62% by mass) was used. Also, the amount of biphenyl skeleton-containing acrylic acid ester (“A-LEN-10” manufactured by Shin-Nakamura Chemical Co., Ltd., (meth)acryloyl group equivalent of about 268 g/eq.) was changed from 4 parts to 8 parts. A resin composition was prepared in the same manner as in Example 1 except for the above matters.

[Example 4]
A biphenyl-type epoxy resin (“NC3000L” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of about 269 g/eq.) was not used. Also, the amount of naphthalene-type epoxy resin ("HP-4032-SS" manufactured by DIC, 1,6-bis(glycidyloxy)naphthalene, epoxy equivalent of about 145 g/eq.) was changed from 2 parts to 10 parts. Furthermore, instead of 40 parts of the active ester compound ("HPC-8000-65T" manufactured by DIC, active ester group equivalent weight of about 223 g / eq., toluene solution with a non-volatile content of 65%), an active ester compound (manufactured by DIC "HPC-8150-62T", an active ester group equivalent of about 220 g/eq., a toluene solution with a nonvolatile content of 62% by mass) was used. Also, the amount of biphenyl skeleton-containing acrylate (“A-LEN-10” manufactured by Shin-Nakamura Chemical Co., Ltd., (meth)acryloyl group equivalent weight: about 268 g/eq.) was changed from 4 parts to 2 parts. A resin composition was prepared in the same manner as in Example 1 except for the above matters.

[Example 5]
Active ester compound ("HPC-8000-65T" manufactured by DIC Corporation, active ester group equivalent weight of about 223 g / eq., toluene solution with a non-volatile content of 65%) instead of 40 parts of an active ester compound ("HPC- 8150-62T", an active ester group equivalent of about 220 g/eq., and a toluene solution with a non-volatile content of 62% by mass) was used. Further, 4 parts of a biphenyl aralkyl novolac type maleimide compound (“MIR-3000-70MT” manufactured by Nippon Kayaku Co., Ltd., MEK/toluene mixed solution with a non-volatile content of 70%) was added to the resin composition. A resin composition was prepared in the same manner as in Example 1 except for the above matters.

[Example 6]
Instead of 40 parts of the active ester compound ("HPC-8000-65T" manufactured by DIC, active ester group equivalent weight of about 223 g / eq., toluene solution with a non-volatile content of 65%), an active ester compound (manufactured by DIC "HPC- 8150-62T", an active ester group equivalent of about 220 g/eq., and a toluene solution with a non-volatile content of 62% by mass) was used. Further, 4 parts of methacrylic-modified polyphenylene ether ("SA9000-111" manufactured by SABIC Innovative Plastics) was added to the resin composition. A resin composition was prepared in the same manner as in Example 1 except for the above matters.

[Example 7]
Instead of 40 parts of the active ester compound ("HPC-8000-65T" manufactured by DIC, active ester group equivalent weight of about 223 g / eq., toluene solution with a non-volatile content of 65%), an active ester compound (manufactured by DIC "HPC- 8150-62T", an active ester group equivalent of about 220 g/eq., and a toluene solution with a non-volatile content of 62% by mass) was used. Further, 4 parts of vinylbenzyl-modified polyphenylene ether (“OPE-2St 2200” manufactured by Mitsubishi Gas Chemical Co., Ltd., a toluene solution with a non-volatile content of 65%) was added to the resin composition. A resin composition was prepared in the same manner as in Example 1 except for the above matters.

[Comparative Example 1]
A biphenyl-type epoxy resin (“NC3000L” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of about 269 g/eq.) was not used. Also, the amount of naphthalene-type epoxy resin ("HP-4032-SS" manufactured by DIC, 1,6-bis(glycidyloxy)naphthalene, epoxy equivalent of about 145 g/eq.) was changed from 2 parts to 10 parts. Furthermore, instead of 4 parts of biphenyl skeleton-containing acrylic acid ester ("A-LEN-10" manufactured by Shin-Nakamura Chemical Co., Ltd., (meth)acryloyl group equivalent of about 268 g / eq.), acrylic acid ester (manufactured by Shin-Nakamura Chemical Co., Ltd. 10 parts of "A-DOG", (meth)acryloyl group equivalent of about 156 g/eq.) were used. A resin composition was prepared in the same manner as in Example 1 except for the above matters.

[Comparative Example 2]
The amount of biphenyl-type epoxy resin (“NC3000L” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of about 269 g/eq.) was changed from 8 parts to 10 parts. Also, a naphthalene-type epoxy resin ("HP-4032-SS" manufactured by DIC, 1,6-bis(glycidyloxy)naphthalene, epoxy equivalent of about 145 g/eq.) was not used. Furthermore, instead of 40 parts of the active ester compound ("HPC-8000-65T" manufactured by DIC, active ester group equivalent weight of about 223 g / eq., toluene solution with a non-volatile content of 65%), an active ester compound (manufactured by DIC "HPC-8150-62T", an active ester group equivalent of about 220 g/eq., a toluene solution with a nonvolatile content of 62% by mass) was used. In addition, instead of 4 parts of biphenyl skeleton-containing acrylic acid ester ("A-LEN-10" manufactured by Shin-Nakamura Chemical Industry Co., Ltd., (meth) acryloyl group equivalent of about 268 g / eq.), acrylic acid ester (manufactured by Kyoeisha Chemical Co., Ltd. "DCP-A", (meth)acryloyl group equivalent weight about 152 g/eq.) was used. Furthermore, 4 parts of a biphenyl aralkyl novolac type maleimide compound (“MIR-3000-70MT” manufactured by Nippon Kayaku Co., Ltd., MEK/toluene mixed solution with a non-volatile content of 70%) was added to the resin composition. A resin composition was prepared in the same manner as in Example 1 except for the above matters.

[Comparative Example 3]
The amount of biphenyl-type epoxy resin (“NC3000L” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of about 269 g/eq.) was changed from 8 parts to 10 parts. Also, a naphthalene-type epoxy resin ("HP-4032-SS" manufactured by DIC, 1,6-bis(glycidyloxy)naphthalene, epoxy equivalent of about 145 g/eq.) was not used. Furthermore, instead of 40 parts of the active ester compound ("HPC-8000-65T" manufactured by DIC, active ester group equivalent weight of about 223 g / eq., toluene solution with a non-volatile content of 65%), an active ester compound (manufactured by DIC "HPC-8150-62T", an active ester group equivalent of about 220 g/eq., a toluene solution with a nonvolatile content of 62% by mass) was used. Also, no biphenyl skeleton-containing acrylate (“A-LEN-10” manufactured by Shin-Nakamura Chemical Co., Ltd., (meth)acryloyl group equivalent of about 268 g/eq.) was used. A resin composition was prepared in the same manner as in Example 1 except for the above matters.

[Production of resin sheet]
As a support, a polyethylene terephthalate film (“AL5” manufactured by Lintec Corporation, thickness 38 μm) provided with a release layer was prepared. On the release layer of this support, the resin compositions obtained in Examples and Comparative Examples were uniformly applied so that the thickness of the resin composition layer after drying was 40 μm. Thereafter, the resin composition was dried at 80° C. to 100° C. (average 90° C.) for 4 minutes to obtain a resin sheet including a support and a resin composition layer. Using the resin sheet thus obtained, evaluation was performed by the following method.

[Method for evaluating smear removability and arithmetic mean roughness (Ra)]
<Preparation of Evaluation Board A>
(1) Surface treatment of interior substrate:
As an inner layer substrate, a glass cloth-based epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.8 mm, “R1515A” manufactured by Panasonic Corporation) having copper foil on the surface was prepared. The copper foil on the surface of the inner layer substrate was roughened by etching with a microetching agent (“CZ8101” manufactured by MEC Co., Ltd.) at a copper etching amount of 1 μm. After that, drying was performed at 190° C. for 30 minutes.

(2) Lamination and curing of resin sheets:
The resin sheets obtained in the above-described Examples and Comparative Examples are processed using a batch-type vacuum pressure laminator (2-stage build-up laminator "CVP700" manufactured by Nikko Materials Co., Ltd.) so that the resin composition layer is the inner layer substrate. Both sides of the inner layer substrate were laminated so as to be bonded. This lamination was carried out by pressure bonding for 30 seconds at a temperature of 100° C. and a pressure of 0.74 MPa after reducing the pressure to 13 hPa or less for 30 seconds.

Then, the laminated resin sheet was hot-pressed for 60 seconds at 100° C. under atmospheric pressure and a pressure of 0.5 MPa for smoothing. Further, this was put into a 130° C. oven and heated for 30 minutes, then transferred to a 170° C. oven and heated for 30 minutes. By these heatings, the resin composition layer was thermally cured to obtain an insulating layer as a cured product layer made of a cured product of the resin composition.

(3) Formation of via holes:
Using a CO ₂ laser processing machine (“LK-2K212/2C” manufactured by Via Mechanics Co., Ltd.), the insulating layer is processed under the conditions of a frequency of 2000 Hz, a pulse width of 3 μs, an output of 0.95 W, and the number of shots of 3. Via holes were formed through the layers. The top diameter (diameter) of the via hole on the surface of the insulating layer was 50 μm, and the diameter of the via hole on the bottom surface of the insulating layer was 40 μm. After that, the support was peeled off to obtain an intermediate substrate having a layer structure of insulating layer/inner layer substrate/insulating layer.

(4) Roughening treatment:
The intermediate substrate was immersed in a swelling liquid, Swelling Dip Securigant P manufactured by Atotech Japan, at 60° C. for 10 minutes. Next, it was immersed at 80° C. for 20 minutes in a roughening liquid Concentrate Compact P (KMnO ₄ : 60 g/L, NaOH: 40 g/L aqueous solution) manufactured by Atotech Japan. Finally, it was immersed at 40° C. for 5 minutes in Reduction Solution Securigant P manufactured by Atotech Japan Co., Ltd., which is a neutralizing solution. The obtained substrate was designated as an evaluation substrate A.

<Evaluation of Smear Removability>
The periphery of the bottom of the via hole of the evaluation board A was observed with a scanning electron microscope (SEM). From the image obtained by observation, the maximum smear length of the smear extending from the bottom wall of the via hole was measured and evaluated according to the following criteria.
"Good": The maximum smear length is less than 5 μm.
"X": The maximum smear length is 5 μm or more.

<Measurement of arithmetic mean roughness (Ra)>
The arithmetic average roughness Ra of the insulating layer surface of the evaluation substrate A is measured using a non-contact surface roughness meter ("WYKO NT3300" manufactured by Bikoinstruments) in VSI mode with a 50x lens, measuring range 121 μm × 92 μm. measured as The measurement was performed at 10 randomly selected points, and the average value was calculated and shown in the table described later.

[Method for measuring plating adhesion (plating peel strength)]
<Preparation of Evaluation Board B>
Evaluation substrate A was immersed in an electroless plating solution containing PdCl ₂ at 40° C. for 5 minutes, and then immersed in an electroless copper plating solution at 25° C. for 20 minutes. After annealing by heating at 150° C. for 30 minutes, an etching resist was formed, and after pattern formation by etching, copper sulfate electroplating was performed to form a plated conductor layer with a thickness of 30 μm. Next, an annealing treatment was performed at 200° C. for 60 minutes, and the obtained substrate was designated as an evaluation substrate B.

<Measurement of peel strength (peel strength) of plated conductor layer>
An incision was made in a portion of the plated conductor layer of the evaluation substrate B not including the via hole to surround a portion having a width of 10 mm and a length of 150 mm. One end of this portion was peeled off and gripped with a gripper of a tensile tester (Autocom type tester "AC-50C-SL" manufactured by TSE Co., Ltd.). At room temperature (25° C.), the plate was pulled vertically at a speed of 50 mm/min, and the load [kgf/cm] when 100 mm was peeled off was measured as the plating peel strength.

[Method of measuring dielectric loss tangent]
The resin sheet obtained in each example and each comparative example was thermally cured at 190° C. for 90 minutes, and the support was peeled off to obtain a sheet-like cured product. The cured product was cut to obtain a test piece having a width of 2 mm and a length of 80 mm. This test piece was measured by the cavity resonance method using a cavity resonator perturbation method dielectric constant measurement device "CP521" manufactured by Kanto Applied Electronics Development Co., Ltd. and a network analyzer "E8362B" manufactured by Agilent Technologies at a frequency of 5.8 GHz. , the dielectric loss tangent (tan δ) was measured. Two test pieces were measured, and the average value was calculated.

[Evaluation method for metal foil adhesion]
The metal foil adhesion was evaluated by measuring the copper foil peel strength according to the following procedure.

<Preparation of evaluation board>
(1) Surface treatment of copper foil:
The glossy surface of the electrolytic copper foil (“3EC-III” manufactured by Mitsui Kinzoku Mining Co., Ltd., thickness 35 μm) is etched by 1 μm with a microetching agent (“CZ8101” manufactured by MEC Co., Ltd.) to roughen the copper surface. An antirust treatment (CL8300) was applied. The copper foil having the surface etched with the micro-etching agent in this way is sometimes referred to as "CZ copper foil" hereinafter. Further, this copper foil was heat-treated in an oven at 130° C. for 30 minutes to obtain a copper foil I having a roughened treated surface.

(2) Preparation of inner layer substrate:
Prepare a double-sided copper-clad laminate made of glass cloth base epoxy resin (copper foil thickness 18 μm, substrate thickness 0.4 mm, manufactured by Panasonic "R1515A") with copper foil on the surface and an inner layer circuit formed. bottom. Both sides of the glass cloth-based epoxy resin double-sided copper-clad laminate were etched by 1 μm with a microetching agent (“CZ8101” manufactured by MEC) to roughen the copper foil surface. As a result, an inner layer substrate having a CZ copper foil with a treated surface on its surface was obtained.

(3) Lamination of resin composition layer:
The resin sheets produced in Examples and Comparative Examples were laminated on both sides of the inner layer substrate. This lamination was performed using a batch-type vacuum pressure laminator (2-stage build-up laminator "CVP700" manufactured by Nikko Materials Co., Ltd.) so that the resin composition layer was in contact with the inner layer substrate. The lamination was carried out by reducing the pressure for 30 seconds to adjust the air pressure to 13 hPa or less, and then pressing for 30 seconds at 120° C. and a pressure of 0.74 MPa. Then, the laminated resin sheet was hot-pressed at 100° C. and a pressure of 0.5 MPa for 60 seconds. After that, the support was peeled off to expose the resin composition layer.

(4) Lamination of copper foil and curing of resin composition layer:
The treated surface of the copper foil I was laminated on the exposed resin composition layer under the same conditions as in "(3) Lamination of resin composition layer". Then, the resin composition layer was cured under curing conditions of 200° C. for 90 minutes to form an insulating layer containing the cured product of the resin composition. By the above operation, an evaluation substrate C having CZ copper foils laminated on both sides of the insulating layer was obtained. This evaluation substrate C had a layer structure of copper foil I/insulating layer/inner layer substrate/insulating layer/copper foil I.

<Measurement of Copper Foil Peeling Strength>
Evaluation board C was cut into 150 mm×30 mm pieces. A small piece of copper foil I was cut with a cutter to enclose a portion 10 mm wide and 100 mm long. One end of this portion was peeled off and gripped with a gripper of a tensile tester (Autocom universal testing machine "AC-50C-SL" manufactured by TSE Co., Ltd.). At room temperature (25° C.), the copper foil was pulled vertically at a speed of 50 mm/min, and the load [kgf/cm] when 35 mm was peeled off was measured as the copper foil peel strength. The measurement was performed according to Japanese Industrial Standard JIS C6481.

[result]
The results of the examples and comparative examples described above are shown in the table below.

In the examples, it was confirmed that even if the components (E) to (H) were not contained, the results were similar to those of the above examples, although there was a difference in degree.

（式（Ｄ１）において、
Ｒ^１１は、それぞれ独立に、水素原子又はメチル基を表し、
Ｒ^１２は、それぞれ独立に、２価の脂肪族炭化水素基を表し、
ｍ１は、０～５の整数を表し、
ｎ１は、０～６の整数を表し、
Ｒ^２１は、それぞれ独立に、水素原子又はメチル基を表し、
Ｒ^２２は、それぞれ独立に、２価の脂肪族炭化水素基を表し、
ｍ２は、０～５の整数を表し、
ｎ２は、０～６の整数を表す。
ただし、ｍ１＋ｍ２は、１以上である。）
〔４〕 樹脂組成物中の不揮発成分を１００質量％とした場合、（Ｄ）ビフェニル骨格を有する（メタ）アクリル酸エステルの含有量が、０．５質量％以上２５質量％以下である、〔１〕～〔３〕のいずれか一項に記載の樹脂組成物。
〔５〕 フェノール系硬化剤及びカルボジイミド系硬化剤からなる群より選ばれる１種類以上の（Ｅ）硬化剤を含む、〔１〕～〔４〕のいずれか一項に記載の樹脂組成物。
〔６〕 （Ｆ）硬化促進剤を含む、〔１〕～〔５〕のいずれか一項に記載の樹脂組成物。
〔７〕 （Ｇ）熱可塑性樹脂を含む、〔１〕～〔６〕のいずれか一項に記載の樹脂組成物。
〔８〕 絶縁層形成用である、〔１〕～〔７〕のいずれか一項に記載の樹脂組成物。
〔９〕 〔１〕～〔８〕の何れか１項に記載の樹脂組成物の硬化物。
〔１０〕 〔１〕～〔８〕の何れか１項に記載の樹脂組成物を含有する、シート状積層材料。
〔１１〕 支持体と、当該支持体上に〔１〕～〔８〕の何れか１項に記載の樹脂組成物で形成された樹脂組成物層と、を有する樹脂シート。
〔１２〕 〔１〕～〔８〕の何れか１項に記載の樹脂組成物の硬化物を含む絶縁層を備える、プリント配線板。
〔１３〕 〔１２〕に記載のプリント配線板を備える、半導体装置。 [1] A resin composition containing (A) an epoxy resin, (B) an active ester compound, (C) an inorganic filler, and (D) a (meth)acrylic acid ester having a biphenyl skeleton,
When the non-volatile component in the resin composition is 100% by mass, the content of (B) the active ester compound is 10% by mass or more,
A resin composition in which the content of (C) an inorganic filler is 60% by mass or more when the non-volatile component in the resin composition is 100% by mass.
[2] The resin composition of [1], wherein (D) the (meth)acrylic acid ester having a biphenyl skeleton contains a compound containing an ether structure.
[3] The resin composition according to [1] or [2], wherein (D) the (meth)acrylic acid ester having a biphenyl skeleton contains a compound represented by the following formula (D1).

(In formula (D1),
each R ¹¹ independently represents a hydrogen atom or a methyl group;
each R ¹² independently represents a divalent aliphatic hydrocarbon group,
m1 represents an integer from 0 to 5,
n1 represents an integer from 0 to 6,
each R ²¹ independently represents a hydrogen atom or a methyl group;
each R ²² independently represents a divalent aliphatic hydrocarbon group,
m2 represents an integer from 0 to 5,
n2 represents an integer of 0-6.
However, m1+m2 is 1 or more. )
[4] When the non-volatile component in the resin composition is 100% by mass, the content of (D) the (meth)acrylic acid ester having a biphenyl skeleton is 0.5% by mass or more and 25% by mass or less [ 1] The resin composition according to any one of [3].
[5] The resin composition according to any one of [1] to [4], which contains at least one (E) curing agent selected from the group consisting of phenolic curing agents and carbodiimide curing agents.
[6] The resin composition according to any one of [1] to [5], which contains (F) a curing accelerator.
[7] The resin composition according to any one of [1] to [6], which contains (G) a thermoplastic resin.
[8] The resin composition according to any one of [1] to [7], which is used for forming an insulating layer.
[9] A cured product of the resin composition according to any one of [1] to [8].
[10] A sheet-like laminate material containing the resin composition according to any one of [1] to [8].
[11] A resin sheet comprising a support and a resin composition layer formed on the support from the resin composition according to any one of [1] to [8].
[12] A printed wiring board comprising an insulating layer containing a cured product of the resin composition according to any one of [1] to [8].
[13] A semiconductor device comprising the printed wiring board according to [12].

Claims (13)

A resin composition containing (A) an epoxy resin, (B) an active ester compound, (C) an inorganic filler, and (D) a (meth)acrylic acid ester having a biphenyl skeleton,
When the non-volatile component in the resin composition is 100% by mass, the content of (B) the active ester compound is 10% by mass or more,
A resin composition in which the content of (C) an inorganic filler is 60% by mass or more when the non-volatile component in the resin composition is 100% by mass. 2. The resin composition according to claim 1, wherein (D) the (meth)acrylic acid ester having a biphenyl skeleton contains a compound containing an ether structure. 3. The resin composition according to claim 1, wherein (D) the (meth)acrylic acid ester having a biphenyl skeleton contains a compound represented by the following formula (D1).

(In formula (D1),
each R ¹¹ independently represents a hydrogen atom or a methyl group;
each R ¹² independently represents a divalent aliphatic hydrocarbon group,
m1 represents an integer from 0 to 5,
n1 represents an integer from 0 to 6,
each R ²¹ independently represents a hydrogen atom or a methyl group;
each R ²² independently represents a divalent aliphatic hydrocarbon group,
m2 represents an integer from 0 to 5,
n2 represents an integer of 0-6.
However, m1+m2 is 1 or more. ) When the non-volatile component in the resin composition is 100% by mass, the content of (D) the (meth)acrylic acid ester having a biphenyl skeleton is 0.5% by mass or more and 25% by mass or less. 4. The resin composition according to any one of 3. The resin composition according to any one of claims 1 to 4, comprising one or more (E) curing agents selected from the group consisting of phenolic curing agents and carbodiimide curing agents. (F) The resin composition according to any one of claims 1 to 5, comprising a curing accelerator. (G) The resin composition according to any one of claims 1 to 6, comprising a thermoplastic resin. The resin composition according to any one of claims 1 to 7, which is used for forming an insulating layer. A cured product of the resin composition according to any one of claims 1 to 8. A sheet-like laminate material containing the resin composition according to any one of claims 1 to 8. A resin sheet comprising a support and a resin composition layer formed on the support from the resin composition according to any one of claims 1 to 8. A printed wiring board comprising an insulating layer containing a cured product of the resin composition according to any one of claims 1 to 8. A semiconductor device comprising the printed wiring board according to claim 12 .