TW202340306A - Resin composition including a styrenic and/or hydrogenated styrene polymer, an epoxy resin and an active ester compound - Google Patents

Abstract

The present invention provides a resin composition capable of obtaining a cured product having an excellent crack resistance after a desmear treatment. The resin composition includes (A) a styrenic and/or hydrogenated styrene polymer having a weight average molecular weight of 10,000 or less, (B) an epoxy resin and (C) an active ester compound. The active ester compound includes a carbon-to-carbon double bond, or a styrene group and naphthalene. The resin composition further includes a free radical polymeric compound.

Description

resin composition

The present invention relates to a resin composition containing an epoxy resin. Furthermore, it relates to cured products, sheet-like laminated materials, resin sheets, printed wiring boards and semiconductor devices obtained using the resin composition.

As a manufacturing technology of printed wiring boards, a manufacturing method based on a build-up method in which insulating layers and conductor layers are alternately laminated is known. In the manufacturing method based on the stacking method, the insulating layer is usually formed by hardening the resin composition. In recent years, there has been a demand for further improvement in dielectric properties such as dielectric constant of the insulating layer and further improvement in copper adhesion.

It has been known heretofore that the dielectric loss tangent of the insulating layer can be further suppressed by using an epoxy resin composition containing an active ester compound instead of a common phenol-based hardener as a resin composition for forming an insulating layer. is a low value (Patent Document 1). [Prior technical literature] [Patent Document]

Patent Document 1: Japanese Patent Application Publication No. 2020-23714.

[Problem to be solved by the invention]

However, when an active ester compound is used, although the dielectric loss tangent can be further suppressed to a low value, there is a tendency for cracks to easily occur after desmear treatment.

An object of the present invention is to provide a resin composition capable of obtaining a cured product that can suppress the occurrence of cracks after desmearing treatment. [Means used to solve problems]

In order to achieve the object of the present invention, the present inventors conducted in-depth research and found that by using an epoxy resin and an active ester compound as components of the resin composition, a styrenic polymer having a weight average molecular weight of 10,000 or less is included. By hydrogenating styrenic polymers and/or hydrogenating styrene-based polymers, a hardened product that can suppress the occurrence of cracks after desmearing treatment can unexpectedly be obtained, and the present invention was completed.

That is, the present invention includes the following contents. [1] A resin composition containing (A) a styrenic and/or hydrogenated styrene polymer having a weight average molecular weight of 10,000 or less, (B) an epoxy resin, and (C) an active ester compound. [2] The resin composition according to the above [1], wherein the component (C) has a carbon-carbon double bond. [3] The resin composition according to the above [1] or [2], wherein the component (C) contains an active ester compound containing a styrene group and a naphthalene structure. [4] The resin composition according to any one of the above [1] to [3], further containing (E) a radically polymerizable compound. [5] The resin composition according to the above [4], wherein (E) the radically polymerizable compound contains (E1) a maleimide compound. [6] The resin composition according to the above [5], wherein (E1) the maleimide compound contains (E1-2) a maleimide compound containing a trimethylindane skeleton. [7] The resin composition according to any one of the above [1] to [6], further containing (D) an inorganic filler. [8] The resin composition according to any one of the above [1] to [7] is used to form an interlayer insulating layer of a printed wiring board. [9] The cured product of the resin composition according to any one of the above [1] to [8]. [10] A sheet-like laminated material containing the resin composition according to any one of the above [1] to [8]. [11] A resin sheet has a support body, and a resin composition layer formed of the resin composition according to any one of the above [1] to [8] and provided on the support body. [12] A printed wiring board provided with an insulating layer formed of a cured product of the resin composition according to any one of [1] to [8] above. [13] A semiconductor device including the printed wiring board according to the above [12]. [Effects of the invention]

According to the present invention, it is possible to provide: a resin composition capable of obtaining a cured product having excellent crack resistance after desmear treatment; a cured product of the resin composition; a sheet-like laminated material and a resin sheet containing the resin composition ; And, printed wiring boards and semiconductor devices containing a cured product of the resin composition.

Hereinafter, the present invention will be described in detail using embodiments and examples. However, the present invention is not limited to the following embodiments and examples, and can be arbitrarily modified and implemented within the scope of the patentable scope of the present invention and its equivalent range.

In the following description, unless otherwise specified, the amount of each component is the amount of non-volatile components. In the following description, the so-called "non-volatile components in the resin composition", unless otherwise clearly stated, may include (D) inorganic fillers; the so-called "resin components", unless otherwise clearly stated, refer to the resin composition. Components other than (D) inorganic filler among the non-volatile components contained.

＜Resin composition＞ The resin composition of the present invention contains (A) a styrenic and/or hydrogenated styrene polymer having a weight average molecular weight of 10,000 or less, (B) an epoxy resin, and (C) an active ester compound. By using such a resin composition, a cured product having excellent crack resistance after desmearing can be obtained. In addition, in the present invention, it is generally possible to obtain low dielectric loss tangent in any environment such as room temperature or normal temperature ranges such as 23°C and high temperature environments such as 90°C, and low dielectric loss tangent in any environment such as room temperature or normal temperature ranges such as 23°C and 90°C. It is a hardened material with low relative dielectric constant and high glass transition temperature in any environment such as high temperature environment.

The resin composition of the present invention contains (A) a styrenic and/or hydrogenated styrenic polymer with a weight average molecular weight of 10,000 or less, (B) an epoxy resin, and (C) an active ester compound. , may also contain optional ingredients. Examples of optional components include (D) inorganic fillers, (E) radically polymerizable compounds, (F) other hardeners, (G) hardening accelerators, (H) other additives, and (K) organic Solvent. In this specification, each of the above-mentioned components (A) to (K) may be referred to as "component (A)", "component (B)", etc., respectively. Each component contained in the resin composition will be described in detail below.

<(A) Styrenic and/or hydrogenated styrenic polymers with a weight average molecular weight of 10,000 or less> The styrenic and/or hydrogenated styrenic polymer used in the present invention is not particularly limited, as long as the weight average molecular weight (Mw) is 10,000 or less. Monomers such as styrene and hydrogenated styrene may also be included. In this specification, the component (A) may be simply referred to as "styrenic and/or hydrogenated styrenic polymer".

A styrenic and/or hydrogenated styrenic polymer having such a molecular weight has a small molecular weight, and therefore has a low melt viscosity, excellent resin fluidity of the resin composition, and improved moldability. In addition, due to its small molecular weight, although it is a styrene-based and/or hydrogenated styrene-based polymer with a hydrophobic skeleton, it not only exhibits high solubility in hydrophobic solvents such as toluene and hexane, but also exhibits high solubility in methyl It also shows high solubility in polar solvents such as ethyl ketone. Therefore, a paint-like resin composition (resin paint) can be easily produced using methyl ethyl ketone and the maleimide compound having a polar group. In addition, since it is a styrene-based and/or hydrogenated styrene-based polymer, the dielectric properties of the resin composition can be improved.

As the styrene-based and/or hydrogenated styrenic-based polymer used in the present embodiment, conventionally known polymers can be widely used and are not particularly limited. Specific examples include: styrene, hydrogenated styrene, benzene, Ethylene derivatives, products in which part of the hydrogen atoms of the benzene ring in styrene such as α-methylstyrene are substituted with alkyl groups, products in which part of the hydrogen atoms in the vinyl group in styrene are substituted with alkyl groups, Polymers or copolymers obtained by polymerizing or copolymerizing one or more styrenic monomers such as vinyl toluene and isopropenyl toluene, and their hydrogenated products.

Preferable examples of the styrene-based and/or hydrogenated styrenic-based polymer include, for example, those having structures represented by the following formulas (A-1) and (A-2), and their hydrogenated products. example.

In the above formulas (A-1) and (A-2), R ₃₅ to R ₃₇ may each independently be the same group or may be different groups, and each represents a hydrogen atom or an alkyl group. The alkyl group is not particularly limited. For example, an alkyl group having 1 to 18 carbon atoms is preferred, and an alkyl group having 1 to 10 carbon atoms is more preferred. Specific examples include methyl, ethyl, propyl, hexyl, and decyl.

In addition, as the styrene-based and/or hydrogenated styrene-based copolymer, those obtained by copolymerizing “one or more types of styrene-based monomers” and “one or more types of other monomers copolymerizable therewith” can also be used. The resulting copolymer. The copolymerizable monomer may be an aliphatic hydrocarbon, an aromatic hydrocarbon, or a combination thereof, and examples thereof include olefins such as α-pinene, β-pinene, and dipentene, and non-conjugated dienes. unsaturated compounds.

For example, the styrenic and/or hydrogenated styrenic polymer may have a structure represented by the following formula (A-3).

R ₃₈ represents the same group as R ₃₅ to R ₃₇ .

As such styrenic and/or hydrogenated styrenic polymers, commercially available products can also be used. For example, FTR6125 (styrene-aliphatic hydrocarbon copolymer, Mw1950) and FTR2140 manufactured by Mitsui Chemicals Co., Ltd. can be used. FTR (registered trademark) (styrene-(α-methylstyrene) copolymer, Mw3230), FTR0100 (α-methylstyrene polymer, Mw1960), FTR8120 (styrene-based polymer, Mw1420), etc. ) series; FMR series such as FMR0150 (styrene-aromatic hydrocarbon copolymer, Mw2040) made by Mitsui Chemicals Co., Ltd.; SX-100 (styrene-based polymer, made by Yasuhara Chemical Co., Ltd. Mw2000), SG-100 (hydrogenated styrenic polymer), SG-110 (hydrogenated styrenic polymer), etc.

The above-mentioned styrene-based and/or hydrogenated styrenic-based polymers may be used individually by one type or in combination of two or more types.

The weight average molecular weight (Mw) of the styrenic and/or hydrogenated styrenic polymer used in this embodiment is 10,000 or less. By containing a styrene-based and/or hydrogenated styrenic-based polymer with an Mw of 10,000 or less, a cured product having excellent crack resistance after desmearing treatment can be obtained. Preferably it is about 1000-9000. More preferably, it is 1000-7000, Still more preferably, it is 1000-5000, Even more preferably, it is about 1000-4000. The weight average molecular weight of the component (A) is the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

The content of component (A) is, for example, 0.1 mass% or more, preferably 0.5 mass% or more, more preferably 1 or 1.0 mass% or more, and still more preferably 3 mass%, based on 100 mass% of non-volatile components in the resin composition. Or 3.0 mass% or more, more preferably 4 or 4.0 mass% or more, for example 15 mass% or less, preferably 10 mass% or less, more preferably 8 or 8.0 mass% or less, still more preferably 6.5 mass% or less , more preferably 5 or 5.0 mass% or less, particularly preferably 4.5 mass% or less. Specifically, these contents are appropriate when using unhydrogenated styrene-based polymers. When using hydrogenated styrene-based polymers, In the case of a polymer, the content may be these, but it is preferably, for example, 2 to 4% by mass, preferably 2.5 to 3% by mass.

The content of component (A) is, for example, 1 mass % or more, 1.5 mass % or more, preferably 5 mass % or more, more preferably 10 mass % or more, and even more preferably 10 mass % or more of the resin component in the resin composition. It is 13 mass % or more, more preferably 15 or 15.0 mass % or more, particularly preferably 16 or 16.0 mass % or more. In addition, for example, it is 30 mass % or less, preferably 25 mass % or less, more preferably 23.5 mass % or less. , more preferably 20% by mass or less, still more preferably 18 or 18.0% by mass or less. Specifically, these contents are appropriate when using unhydrogenated styrene-based polymers. When using hydrogenated styrene-based polymers, In the case of a polymer, the content may be these, but it is preferably, for example, 3 to 15% by mass, preferably 5 to 10% by mass, and more preferably 5.5 to 6% by mass.

＜(B) Epoxy resin＞ The resin composition of the present invention contains (B) epoxy resin. (B) Epoxy resin refers to a curable resin having an epoxy group.

Examples of (B) epoxy resin include bixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol S type epoxy resin, Phenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl Base - Catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin, cresol Cresol novolac type epoxy resin, phenol aralkyl type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin with butadiene structure, alicyclic epoxy resin , Heterocyclic epoxy resin, epoxy resin containing spiro ring, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, naphthyl ether type epoxy resin, trimethylol type epoxy Resin, tetraphenylethane type epoxy resin, isocyanurate type epoxy resin, phenolphthalimidine type epoxy resin, phenolphthalein type epoxy resin, etc. (B) Epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more types.

The resin composition preferably contains an epoxy resin (B) having two or more epoxy groups per molecule as the epoxy resin (B). The proportion of the epoxy resin having two or more epoxy groups per molecule is preferably 50 mass% or more, more preferably 60 mass% or more, and particularly preferably 100 mass% of the non-volatile content of the epoxy resin (B). It is more than 70% by mass.

Epoxy resins include epoxy resins that are liquid at a temperature of 20°C (hereinafter sometimes referred to as "liquid epoxy resins") and epoxy resins that are solid at a temperature of 20°C (hereinafter sometimes referred to as "solid epoxy resins"). Epoxy resin"). The resin composition of the present invention may contain only liquid epoxy resin as the epoxy resin, or may contain only solid epoxy resin, or may contain liquid epoxy resin and solid epoxy resin in combination. The epoxy resin in the resin composition of the present invention is preferably a solid epoxy resin, or a combination of a liquid epoxy resin and a solid epoxy resin, and is more preferably a solid epoxy resin.

As the liquid epoxy resin, one having two or more epoxy groups per molecule is preferred.

As the liquid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, and glycidyl amine are preferred. type epoxy resin, phenol novolak type epoxy resin, cycloaliphatic epoxy resin with ester skeleton, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin and epoxy with butadiene structure resin.

Specific examples of liquid epoxy resins include "HP4032", "HP4032D" and "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC Corporation; "828US", "828EL" and "828EL" manufactured by Mitsubishi Chemical Corporation jER828EL", "825", "EPIKOTE 828EL" (bisphenol A type epoxy resin); "jER807", "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER152" manufactured by Mitsubishi Chemical Corporation "(phenol novolac type epoxy resin); "630", "630LSD", "604" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "ED-523T" (glycyrrhizol) manufactured by ADEKA (Glycirol type epoxy resin); "EP-3950L" and "EP-3980S" (glycidylamine type epoxy resin) manufactured by ADEKA; "EP-4088S" (dicyclopentadiene type) manufactured by ADEKA Epoxy resin); "ZX1059" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd. (a mixture of bisphenol A-type epoxy resin and bisphenol F-type epoxy resin); "EX-721" (glycidol) manufactured by Nagase ChemteX Co., Ltd. ester-based epoxy resin); "Celloxide 2021P" manufactured by Daicel Corporation (alicyclic epoxy resin with an ester skeleton); "PB-3600" manufactured by Daicel Corporation, "JP-100" manufactured by Nippon Soda Corporation ", "JP-200" (epoxy resin with butadiene structure); "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd. )wait. One type of these may be used alone, or two or more types may be used in combination.

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

As the solid epoxy resin, preferred are dixylenol-type epoxy resin, naphthalene-type epoxy resin, naphthalene-type tetrafunctional epoxy resin, naphthol novolak-type epoxy resin, cresol novolac-type epoxy resin, and dicyclopentane. Diene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthyl 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 benzopyrrolidone type epoxy resin, phenolphthalein type epoxy resin.

Specific examples of solid epoxy resins include "HP4032H" (naphthalene-type epoxy resin) manufactured by DIC Corporation; "HP-4700" and "HP-4710" (naphthalene-type tetrafunctional epoxy resin) manufactured by DIC Corporation Resin); "N-690" (cresol novolak type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolac type epoxy resin) manufactured by DIC Corporation; "HP- 7200", "HP-7200HH", "HP-7200H", "HP-7200L" (dicyclopentadiene type epoxy resin); "EXA-7311", "EXA-7311-G3", " EXA-7311-G4", "EXA-7311-G4S", "HP6000" (alkylene ether type epoxy resin); "EPPN-502H" (trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; Japan "NC7000L" (naphthol novolak type epoxy resin) manufactured by Nippon Chemical Industry Co., Ltd.; "NC3000H", "NC3000", "NC3000L", "NC3000FH", "NC3100" (biphenyl type epoxy resin) manufactured by Nippon Chemical Industry Co., Ltd. Resin); "ESN475V" (naphthalene type epoxy resin) manufactured by Nippon Steel Chemical & Materials Co., Ltd.; "ESN485" (naphthol type epoxy resin) manufactured by Nippon Steel Chemical & Materials Co., Ltd.; Nippon Steel Chemical & Materials Co., Ltd. "ESN375" (dihydroxynaphthalene type epoxy resin) manufactured by Materials Co., Ltd.; "YX4000H", "YX4000", "YX4000HK", "YL7890" (bixylenol type epoxy resin) manufactured by Mitsubishi Chemical Corporation; Mitsubishi Chemical "YL6121" (biphenyl-type epoxy resin) manufactured by the company; "YX8800" (anthracene-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX7700" (phenol aralkyl-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Co., Ltd.; "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corporation Resin); "jER1010" (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "WHR991S" manufactured by Nippon Chemical Corporation (phenol benzopyrrolidone type epoxy resin) etc. One type of these may be used alone, or two or more types may be used in combination.

As (B) epoxy resin, when a liquid epoxy resin and a solid epoxy resin are used together, the mass ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin/solid epoxy resin) is not particularly The limit is preferably 10 or less, more preferably 5 or less, and even more preferably 1 or less.

(B) The epoxy equivalent of the epoxy resin is preferably 50g/eq. to 5,000g/eq., more preferably 60g/eq. to 2,000g/eq., further preferably 70g/eq. to 1,000g/eq. , further more preferably 80g/eq. to 500g/eq. Epoxy equivalent is the mass of resin corresponding to 1 equivalent of epoxy group. The epoxy equivalent can be measured in accordance with JIS K7236.

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

The content of component (B) is, for example, 1 mass% or more, preferably 3 mass% or more, more preferably 5 mass% or more, and still more preferably 8 mass%, based on 100 mass% of non-volatile components in the resin composition. Above, more preferably 8.5 mass% or more, for example 30 mass% or less, preferably 20 mass% or less, more preferably 15 mass% or less, still more preferably 10 mass% or less, still more preferably 9 or 9.0 mass% or less.

The content of component (B) is, for example, 10 mass% or more, preferably 15 mass% or more, more preferably 20 mass% or more, still more preferably 25 mass% or more, based on 100 mass% of the resin component in the resin composition. , more preferably 30 mass% or more, particularly preferably 32 mass% or more, and for example, 60 mass% or less, preferably 55 mass% or less, more preferably 50 mass% or less, still more preferably 45 mass% or less, It is more preferably 40% by mass or less, and particularly preferably 36% by mass or less.

＜(C) Active ester compound＞ The resin composition of the present invention contains (C) an active ester compound. (C) The active ester compound may be used individually by 1 type, or may be used in combination of 2 or more types at arbitrary ratios, and the same applies to the (C1) component and (C2) component mentioned later. (C) The active ester compound may react with (B) epoxy resin to cross-link the (B) epoxy resin. (C) The active ester compound may be a compound having a carbon-carbon unsaturated bond. The unsaturated bond is preferably a carbon-carbon double bond. For example, it may be a compound having a carbon-carbon unsaturated bond with the component (C1) described below. Same key.

As (C) the active ester compound, usually, those having two or more reactive compounds per molecule, such as phenol esters, thiophenol esters, N-hydroxylamine esters, esters of heterocyclic hydroxyl compounds, etc., can be preferably used. ester-based compounds. The active ester compound is preferably obtained by a condensation reaction of 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, a phenol compound and/or a naphthol compound is more preferred. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, and the like. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaloline, methylated bisphenol A, and methylated bisphenol F. , methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-di Hydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, phloroglucinol, dicyclopentadienyl dihydroxynaphthalene Phenolic compounds, novolac resin (Phenolic Novolac), etc. Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing one molecule of dicyclopentadiene and two molecules of phenol.

Specifically, (C) the active ester compound is preferably a dicyclopentadiene-type active ester compound, a naphthalene-type active ester compound containing a naphthalene structure, an active ester compound containing an acetate of a novolac resin, or an active ester compound containing a novolak resin. Among the active ester compounds of benzyl chloride, at least one selected from the group consisting of dicyclopentadiene-type active ester compounds and naphthalene-type active ester compounds is more preferred, and dicyclopentadiene-type active ester compounds are even more preferred. As the dicyclopentadiene-type active ester compound, an active ester compound containing a dicyclopentadiene-type diphenol structure is preferred. The "dicyclopentadiene-type diphenol structure" represents a divalent structural unit composed of a phenylene group-dicyclopentylene-phenylene group.

(C) Commercially available active ester compounds include "EXB9451", "EXB9460", "EXB9460S", "EXB-8000L", and "EXB" as active ester compounds containing a dicyclopentadiene-type diphenol structure. -8000L-65M", "EXB-8000L-65TM", "HPC-8000L-65TM", "HPC-8000", "HPC-8000-65T", "HPC-8000H", "HPC-8000H-65TM" ( (manufactured by DIC Corporation); examples of the active ester compound containing a naphthalene structure include "EXB-8100L-65T", "EXB-8150-60T", "EXB-8150-62T", "EXB-9416-70BK", " HPC-8150-60T", "HPC-8150-62T" (manufactured by DIC Corporation); examples of active ester compounds containing phosphorus include "EXB9401" (manufactured by DIC Corporation), and about acetyl compounds that are novolac resins Examples of active ester compounds include "DC808" (manufactured by Mitsubishi Chemical Corporation). Examples of active ester compounds that are benzyl compounds of novolac resins include "YLH1026", "YLH1030", and "YLH1048" (manufactured by Mitsubishi Chemical Corporation). (manufactured by Air Water Co., Ltd.), and examples of the active ester compound containing a styrene group and a naphthalene structure include "PC1300-02-65MA" (manufactured by Air Water Co., Ltd.).

(C) The active ester group equivalent of the active ester compound is preferably 50 g/eq. to 500 g/eq., more preferably 50 g/eq. to 400 g/eq., further preferably 100 g/eq. to 300 g/eq. The active ester group equivalent is the mass of the active ester compound corresponding to 1 equivalent of active ester group.

＜(C1) Compounds containing aromatic ester skeleton and unsaturated bonds＞ As (C) the active ester compound, (C1) a compound containing an aromatic ester skeleton and an unsaturated bond (also referred to as "(C1) component" in this specification) can also be used.

The component (C1) is preferably a compound represented by the following general formula (AE1-1). (In the general formula (AE1-1), Ar ¹¹ each independently represents a monovalent aromatic hydrocarbon group that may have a substituent, Ar ¹² each independently represents a divalent aromatic hydrocarbon group that may have a substituent, and Ar ¹³ each independently represents a divalent aromatic hydrocarbon group that may have a substituent. A divalent aromatic hydrocarbon group as a substituent, a divalent aliphatic hydrocarbon group that may have a substituent, an oxygen atom, a sulfur atom, or a divalent group formed by a combination of these. n represents an integer from 0 to 10.)

Examples of the monovalent aromatic hydrocarbon group represented by Ar ¹¹ include phenyl, furyl, pyrrolyl, thienyl, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, and pyridine Groups obtained by removing one hydrogen atom from a monocyclic aromatic compound such as pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, etc.; naphthyl, anthracenyl, phenalenyl, phenanthreneyl Base, quinolyl, isoquinolinyl, quinazolinyl, phthalazinyl, pteridyl, coumarinyl, indolyl, benzimidazolyl, benzofuranyl, acridinyl, etc. A group obtained by removing one hydrogen atom from a condensed ring aromatic compound; etc., among which, a phenyl group is preferred.

Examples of the divalent aromatic hydrocarbon group represented by Ar ¹² include an aryl group, an aralkylene group, and the like, and an aryl group is preferred. As the aryl group, an aryl group having 6 to 30 carbon atoms is preferred, an aryl group having 6 to 20 carbon atoms is more preferred, and an aryl group having 6 to 10 carbon atoms is still more preferred. Examples of such an aryl group include a phenylene group, a naphthylene group, anthracylene group, and a biphenylene group. Among them, phenylene group is preferred.

Ar ¹³ is preferably a divalent group formed from a combination of these. The divalent aromatic hydrocarbon group represented by Ar ¹³ is the same as the divalent aromatic hydrocarbon group represented by Ar ¹² . As the divalent aliphatic hydrocarbon group represented by Ar ¹³ , a divalent saturated aliphatic hydrocarbon group is more preferred, an alkylene group and a cycloalkylene group are preferred, and a cycloalkylene group is more preferred.

As the cycloalkyl group, a cycloalkyl group having 3 to 20 carbon atoms is preferred, a cycloalkyl group having 3 to 15 carbon atoms is more preferred, and a cycloalkyl group having 5 to 10 carbon atoms is even more preferred. Examples of the cycloalkylene group include cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cyclopentylene, and cycloheptylene, and those represented by the following formulas (a) to (d). The cycloalkyl group represented by formula (c) is preferably the cycloalkyl group represented by formula (c). (In formulas (a) to (d), "*" represents a chemical bond.)

Examples of substituents that the monovalent aromatic hydrocarbon group represented by Ar ¹¹ , the divalent aromatic hydrocarbon group represented by Ar ¹² , the divalent aromatic hydrocarbon group represented by Ar ¹³ and the divalent aliphatic hydrocarbon group may have include unsaturated hydrocarbon groups and carbon atoms. Alkyl groups with 1 to 10 carbon atoms, alkoxy groups with 1 to 10 carbon atoms, halogen atoms, etc. The substituent may be contained individually or in combination of two or more types. Among them, the substituent of Ar ¹¹ preferably contains an unsaturated bond.

When the compound represented by the general formula (AE1-1) is an oligomer or a polymer, n represents the average value.

Specific examples of the component (C1) include the following compounds. Specific examples of the component (C1) include compounds described in paragraphs 0068 to 0071 of International Publication No. 2018/235424 and paragraphs 0113 to 0115 of International Publication No. 2018/235425. . In the formula, s represents an integer of 0 or more than 1, and r represents an integer of 1 to 10.

The weight average molecular weight of component (C1) is preferably 150 or more, more preferably 200 or more, still more preferably 250 or more, preferably 3000 or less, more preferably 2000 or less, from the viewpoint of significantly obtaining the effects of the present invention. Preferably it is 1500 or less. The weight average molecular weight of the component (C1) is the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

The active ester equivalent (unsaturated bond equivalent) of component (C1) is preferably 50 g/eq. or more, more preferably 100 g/eq. or more, and still more preferably 150 g, from the viewpoint of significantly obtaining the effects of the present invention. /eq. or more, preferably 2000 g/eq. or less, more preferably 1000 g/eq. or less, still more preferably 500 g/eq. or less. The active ester equivalent (unsaturated bond equivalent) is the mass of component (C1) containing 1 equivalent of unsaturated bond.

<(C2) An active ester compound having at least one of the groups represented by the following formulas (1) to (3)> As the (C) active ester compound, (C2) having the following formula ( An active ester compound of at least one of the groups represented by 1) to (3) (also referred to as "(C2) component" in this specification.) (In the formula, * represents a chemical bond. In formula (3), n represents an integer from 1 to 5.)

As the component (C2), a compound having at least one of the groups represented by the formulas (1) to (3) and an active ester moiety that can react with the component (A) can be used. As the (C2) component, it is preferable to have at least one of the groups represented by formulas (1) to (3) at the terminal. As the component (C2), both ends may be different groups, or both ends may be the same group.

The methyl group in the group represented by formula (1), the phenyl group in the group represented by formula (2), and the styrene moiety in the group represented by formula (3) are preferably represented by * The chemical bond is bonded to any one of the ortho-position, meta-position and para-position, and is more preferably bonded to the ortho-position.

The component (C2) is preferably a compound represented by the following general formula (AE2-1). (In general formula (AE2-1), Ar ¹¹ each independently represents a group represented by formula (1), a group represented by formula (2), or a group represented by formula (3), and Ar ¹² each independently represents a group represented by formula (1), a group represented by formula (2), or a group represented by formula (3). independently represents a divalent aromatic hydrocarbon group which may have a substituent, and Ar ¹³ each independently represents a divalent aromatic hydrocarbon group which may have a substituent, a divalent aliphatic hydrocarbon group which may have a substituent, an oxygen atom, a sulfur atom, or a combination of these A bivalent group formed by combination. a represents an integer from 1 to 6, and b represents an integer from 0 to 10.)

As Ar ¹¹ , a group represented by formula (1) and a group represented by formula (2) are preferred.

Ar ¹² and Ar ¹³ are respectively the same as Ar ¹² and Ar ¹³ in the general formula (AE1-1). The divalent aromatic hydrocarbon group represented by Ar ¹² and the divalent aromatic hydrocarbon group and divalent aliphatic hydrocarbon group represented by Ar ¹³ may have Examples of the substituent include an aryl group having 6 to 20 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a halogen atom. The substituent may be contained individually or in combination of two or more types.

The divalent group represented by Ar ¹³ formed by a combination of these is preferably a divalent aromatic hydrocarbon group that may have a substituent and an oxygen atom, and more preferably one or more divalent aromatic hydrocarbon groups that may have a substituent. A divalent group consisting of a divalent aromatic hydrocarbon group and one or more oxygen atoms alternately combined, and more preferably a divalent group consisting of one or more naphthylene groups which may have a substituent and one or more oxygen atoms alternately combined. Valence group. Therefore, a naphthyloxy group which may have a substituent is further preferred.

When the compound represented by the general formula (AE2-1) is an oligomer or a polymer, a represents the average value. b is the same as n in the general formula (AE1-1), and is preferably 0.

The component (C2) is preferably a compound represented by general formula (AE2-2). (In general formula (AE2-2), Ar ²¹ each independently represents a group represented by formula (1), a group represented by formula (2), or a group represented by formula (3), and Ar ²² each independently represents a group represented by formula (1), a group represented by formula (2), or a group represented by formula (3). Each independently represents a divalent aromatic hydrocarbon group which may have a substituent, and Ar ²³ each independently represents a divalent aromatic hydrocarbon group which may have a substituent. a1 represents an integer of 1 to 6, and c1 represents an integer of 1 to 5.)

Ar ²¹ and Ar ²² are respectively the same as Ar ¹¹ and Ar ¹² in the general formula (AE2-1).

Ar ²³ is the same as the optionally substituted divalent aromatic hydrocarbon group of Ar ¹³ in the general formula (AE2-1). a1 is the same as a in the general formula (AE2-1).

The component (C2) is preferably a compound represented by general formula (AE2-3). (In general formula (AE2-3), Ar ³¹ each independently represents a group represented by formula (1), a group represented by formula (2), or a group represented by formula (3). a2 represents 1 ~6 integers, c2 represents an integer from 1 to 5, and d each independently represents an integer from 0 to 6.)

Ar ³¹ is the same as Ar ¹¹ in the general formula (AE2-1). a2 and c2 are respectively the same as a and c1 in the general formula (AE2-1).

d preferably represents an integer of 1 to 5, and more preferably represents an integer of 1 to 4.

The component (C2) can be synthesized by a known method. For example, it can be synthesized by the method described in the following Examples. The component (C2) can be synthesized by, for example, the method described in International Publication No. 2018/235424 or International Publication No. 2018/235425.

The weight average molecular weight of component (C2) is preferably 150 or more, more preferably 200 or more, still more preferably 250 or more, preferably 4000 or less, more preferably 3000 or less, from the viewpoint of significantly obtaining the effects of the present invention. Preferably it is 2500 or less. The weight average molecular weight of the component (C2) is the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

The active ester equivalent (unsaturated bond equivalent) of component (C2) is the same as that of component (C1).

Regarding the quantitative ratio of component (B) to component (C), the value obtained by adding all the values obtained by dividing the mass of the non-volatile component of component (B) by the epoxy equivalent is denoted as a, and When the value obtained by dividing the mass of the non-volatile component of component (C) by the active ester group equivalent is added together and is expressed as b, b/a is preferably 1.0 or more, more preferably 1.01 or more, and even more preferably 1.03 or more, more preferably 1.05 or more, particularly preferably 1.06 or more. In addition, it is preferably 2.0 or less, more preferably 1.5 or less, still more preferably 1.2 or less, still more preferably 1.18 or less, and particularly preferably 1.17 or less. By setting the quantity ratio of component (B) to component (C) within the above range, the effects of the present invention can be easily obtained.

The content of component (C) is, for example, 3 mass% or more, preferably 5 mass% or more, more preferably 8 mass% or more, and still more preferably 10 mass%, based on 100 mass% of non-volatile components in the resin composition. In addition, for example, it is 30 mass% or less, preferably 25 mass% or less, more preferably 20 mass% or less, still more preferably 15 mass% or less, still more preferably 12 mass% or less.

The content of component (C) is, for example, 30 mass% or more, preferably 35 mass% or more, more preferably 40 mass% or more, still more preferably 42 mass% or more, based on 100 mass% of the resin component in the resin composition. , in addition, for example, it is 70 mass% or less, preferably 60 mass% or less, more preferably 50 mass% or less, still more preferably 45 mass% or less.

＜(D) Inorganic filler＞ The resin composition of the present invention may contain (D) an inorganic filler as an optional component. (D) The inorganic filler is contained in the resin composition in the form of particles. (D) Inorganic filler material may be used individually by 1 type, and may be used in combination of 2 or more types arbitrarily.

As the material of (D) the inorganic filler, an inorganic compound is used. (D) Examples of the inorganic filler material include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, and boron. Stone, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, Bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate and zirconium tungstate phosphate, etc. Among these, silica is particularly preferred. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, and the like. In addition, as the silica, spherical silica is preferred. (D) Inorganic filler material may be used individually by 1 type, and may be used in combination of 2 or more types at arbitrary ratios.

(D) Commercially available products of the inorganic filler include, for example, "SP60-05" and "SP507-05" manufactured by Nippon Steel Chemical Materials Co., Ltd.; "SC2500SQ" and "SC2500SQ" manufactured by Admatechs "SO-C4", "SO-C2", "SO-C1", "YC100C", "YA050C", "YA050C-MJE", "YA010C"; "UFP-30" and "DAW-03" made by DENKA , "FB-105FD"; "Silfil NSS-3N", "Silfil NSS-4N", "Silfil NSS-5N" made by Tokuyama Co., Ltd.; "MGH-005" made by Taiheiyo-Cement Co., Ltd. "; "BA-S" made by Nikko Catalyst Corporation, etc.

(D) The average particle size of the inorganic filler is not particularly limited, but is preferably 10 μm or less, more preferably 5 μm or less, still more preferably 2 μm or less, still more preferably 1 μm or less, particularly preferably 0.7 μm or less. (D) The lower limit of the average particle size of the inorganic filler is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, still more preferably 0.1 μm or more, particularly preferably 0.2 μm or more. (D) The average particle size of the inorganic filler material can be measured using a laser diffraction-scattering method based on Mie scattering theory. Specifically, the measurement can be performed by using a laser diffraction and scattering particle size distribution measuring device to prepare the particle size distribution of the inorganic filler material on a volume basis, and using the median particle size as the average particle size. As a measurement sample, a product obtained by weighing 100 mg of the inorganic filler and 10 g of methyl ethyl ketone into a vial and dispersing the mixture using ultrasonic waves for 10 minutes can be used. For the measurement sample, a laser diffraction particle size distribution measuring device was used, and the wavelength of the light source was set to blue and red, and the volume-based particle size distribution of the inorganic filler was measured by a flow cell method. From the obtained Particle size distribution The average particle size was calculated as the median particle size. Examples of the laser diffraction particle size distribution measuring device include "LA-960" manufactured by Horiba Manufacturing Co., Ltd.

(D) The specific surface area of the inorganic filler is not particularly limited, but is preferably 0.1 m ² /g or more, more preferably 0.5 m ² /g or more, further preferably 1 m ² /g or more, particularly preferably 3 m ² /g or more. (D) The upper limit of the specific surface area of the inorganic filler is not particularly limited, but is preferably 100 m ² /g or less, more preferably 70 m ² /g or less, further preferably 50 m ² /g or less, particularly preferably 40 m ² /g or less. The specific surface area of the inorganic filler material can be obtained by adsorbing nitrogen gas on the surface of the sample 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 multi-point method.

(D) The inorganic filler material is preferably surface-treated with an appropriate surface treatment agent. By performing surface treatment, the moisture resistance and dispersibility of (D) the inorganic filler material can be improved. Examples of surface treatment agents include vinyl-based silane coupling agents such as vinyltrimethoxysilane and vinyltriethoxysilane; 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane Epoxy silane coupling agents such as glycidoxypropyltriethoxysilane; styryl silane coupling agents such as p-styryltrimethoxysilane; 3-methacryloxypropylmethyldimethyl Methoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane Methacrylic silane coupling agents such as oxysilane; acrylic silane coupling agents such as 3-acryloxypropyltrimethoxysilane; N-2-(aminoethyl)-3-aminopropylmethyl Dimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane , 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-benzene Amino silane coupling agents such as -8-aminooctyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane; tris(trimethyl Isocyanurate silane coupling agents such as oxysilylpropyl isocyanurate; ureido silane coupling agents such as 3-ureidopropyltrialkoxysilane; 3-mercaptopropylmethyl Thiol-based silane coupling agents such as dimethoxysilane and 3-mercaptopropyltrimethoxysilane; isocyanate-based silane coupling agents such as 3-isocyanatopropyltriethoxysilane; 3-trimethoxysilylpropyl succinate Anhydride-based silane coupling agents such as acid anhydride; silane coupling agents such as acid anhydride; methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethyl Oxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, Non-silane coupling-alkoxysilane compounds such as decyltrimethoxysilane, 1,6-bis(trimethoxysilyl)hexane, and trifluoropropyltrimethoxysilane. In addition, one type of surface treatment agent may be used alone, or two or more types may be used in combination at an arbitrary ratio.

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

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 predetermined range. Specifically, 100% by mass of the inorganic filler is preferably surface-treated with 0.2% to 5% by mass of the surface treatment agent, more preferably 0.2% to 3% by mass, and even more preferably 0.3% by mass. % to 2% by mass are surface treated.

The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler material. The amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/m ² or more, more preferably 0.1 mg/m ² or more, and even more preferably 0.2 mg from the viewpoint of improving the dispersibility of the inorganic filler. /m ² or more. On the other hand, from the viewpoint of preventing an increase in the melt viscosity of the resin composition and the melt viscosity in the sheet form, it is preferably 1.0 mg/m ² or less, more preferably 0.8 mg/m ² or less, and still more preferably 0.5 mg. /m ² or less.

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

The content of the (D) inorganic filler in the resin composition is not particularly limited. When the non-volatile component in the resin composition is 100% by mass, it may be preferably 90% by mass or less, more preferably 85% by mass or less, and further The content is preferably 80 mass% or less, and more preferably 75 mass% or less. The lower limit of the content of (D) inorganic filler in the resin composition is not particularly limited. When the non-volatile component in the resin composition is 100% by mass, it may be, for example, 0% by mass or more, 1% by mass or more, or 10% by mass. % or more, 20 mass% or more, 30 mass% or more, etc., it can be preferably 40 mass% or more, more preferably 50 mass% or more, still more preferably 60 mass% or more, still more preferably 70 mass% or more, and particularly preferably More than 73% by mass.

＜(E) Radically polymerizable compound＞ The resin composition of the present invention may contain (E) a radically polymerizable compound as an optional component. (E) A radical polymerizable compound may be used individually by 1 type, and may be used in combination of 2 or more types arbitrarily.

The radically polymerizable compound is not particularly limited as long as it has one or more (preferably two or more) radically polymerizable unsaturated groups in one molecule. Examples of radically polymerizable compounds include those having a compound selected from the group consisting of maleimide group, vinyl group, allyl group, styryl group, vinylphenyl group, acrylyl group, methacryloyl group, fumaryl group, and A compound in which one or more maleyl groups serve as radically polymerizable unsaturated groups. Among these, it is preferable to include (E1) a maleimide compound and/or (E2) other radically polymerizable compounds from the viewpoint of easily obtaining a cured product excellent in dielectric properties. (E2) The other radically polymerizable compound is a compound that does not have a maleimide group but has a radically polymerizable unsaturated group other than a maleimide group. Among them, it is preferable to include a compound selected from the group consisting of (E2) base) one or more types of acrylic resin and styrene resin.

(E1) The maleimide compound is any compound having one or more (preferably two or more) maleimide groups (2,5-dihydro-2,5-dioxo-1H) in one molecule. -pyrrol-1-yl), and its type is not particularly limited. Examples of maleimide compounds include "BMI-3000J", "BMI-5000", "BMI-1400", "BMI-1500", "BMI-1700", and "BMI-689" (all Maleimine resin containing an aliphatic skeleton with 36 carbon atoms derived from dimer diamine, such as Designer Molecules Co., Ltd.; described in the Japan Invention Association Technical Publication No. 2020-500211 Maleimide resin containing an indane skeleton; "MIR-3000-70MT", "MIR-5000-60T" (all manufactured by Nippon Kayaku Co., Ltd.), "BMI-4000" (manufactured by Yamato Chemical Co., Ltd.), Maleimide resins including "BMI-80" (manufactured by KI Chemicals Co., Ltd.) and other maleimide resins containing an aromatic ring skeleton directly bonded to the nitrogen atom of the maleimide group.

The maleimide compound (E1) preferably includes a maleimide compound containing an indan skeleton (also referred to as "(E1-1) specific maleimine compound" in this specification), More preferably, it contains (E1-2) a maleimide compound containing a trimethylindane skeleton. (E1-1) The specific maleimide compound can be produced, for example, by the method described in Japan Invention Society Publication No. 2020-500211. According to the production method described in the Japan Invention Association Technical Publication No. 2020-500211, a maleimide compound with a distribution of the number of repeating units of the trimethylindane skeleton can be obtained. The maleimide compound obtained by this method contains a structure represented by the following formula (M1). Therefore, the maleimide compound (E1) may include a maleimide compound having a structure represented by formula (M1).

(In formula (M1), R ¹ each independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, or an alkylthio group having 1 to 10 carbon atoms. Aryl group with 6 to 10 carbon atoms, aryloxy group with 6 to 10 carbon atoms, arylthio group with 6 to 10 carbon atoms, cycloalkyl group with 3 to 10 carbon atoms, halogen atom, nitro group, hydroxyl group or Mercapto group; R ² each independently represents an alkyl group with 1 to 10 carbon atoms, an alkyloxy group with 1 to 10 carbon atoms, an alkylthio group with 1 to 10 carbon atoms, and an aromatic group with 6 to 10 carbon atoms. group, an aryloxy group with 6 to 10 carbon atoms, an arylthio group with 6 to 10 carbon atoms, a cycloalkyl group with 3 to 10 carbon atoms, a halogen atom, a hydroxyl group or a mercapto group; n ₁ represents 0.95 to 10.0 The average number of repeating units; n ₂ each independently represents an integer from 0 to 4; n ₃ each independently represents an integer from 0 to 3. R ¹ alkyl, alkyloxy, alkylthio, aryl, aryl The hydrogen atoms of R ² alkyl, alkyloxy, alkylthio, aryl, aryloxy, arylthio and The hydrogen atom of the cycloalkyl group may be substituted by a halogen atom. When _{n 2} is 2 to 4, R ¹ may be the same or different in the same ring. When _{n 3} is 2 to 3, R ² may be the same or different in the same ring. different.)

In formula (M1), n ₁ represents the average number of repeating units, which ranges from 0.95 to 10.0. A group of maleimide compounds including a structure represented by formula (M1) can be obtained according to the production method described in the Japan Invention Association Technical Publication No. 2020-500211. Since the average number of repeating units n ₁ in the formula (M1) can be less than 1.00, it can be seen that the maleimide compound containing the structure represented by the formula (M1) obtained as described above can contain a trimethylindane skeleton. A maleimide compound with 0 repeating units. Therefore, from the maleimide compound containing the structure represented by formula (M1), purification is performed to remove the maleimide compound whose trimethylindane skeleton has a repeating unit number of 0, to obtain (E1-1) The specific maleimide compound may be contained only in the resin composition (E1-1). However, even when the resin composition contains a maleimide compound in which the number of repeating units of the trimethylindane skeleton is 0, the effects of the present invention can be obtained. In addition, when purification is omitted, costs can be suppressed. Therefore, it is preferable that the resin composition contains a maleimine compound having a structure represented by formula (M1) without removing the maleimine compound whose trimethylindane skeleton has a repeating unit number of 0.

In the formula (M), the average number of repeating units n ₁ is preferably 0.95 or more, more preferably 0.98 or more, still more preferably 1.0 or more, particularly preferably 1.1 or more, preferably 10.0 or less, more preferably 8.0 or less, still more preferably 7.0 below, and particularly preferably below 6.0. When the average number of repeating units n ₁ is within the aforementioned range, the effects of the present invention can be significantly obtained. In particular, it can effectively increase the glass transition temperature of the resin composition.

Examples of the structure represented by formula (M1) include the following structures.

The maleimide compound containing the structure represented by formula (M1) may further contain the structure represented by the following formula (M2). For example, in the formula (M1), n ₂ is 3 or less, and at least two of the ortho and para positions of the benzene ring to which the maleimide group is bonded with respect to the maleimide group. When R ¹ is not bonded to the position of , the maleimide compound containing the structure represented by formula (M1) may contain not only the structure represented by formula (M1) but also the structure represented by formula (M2).

(In formula (M2), R ^c1 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, or an alkylthio group having 1 to 10 carbon atoms. Aryl group with 6 to 10 carbon atoms, aryloxy group with 6 to 10 carbon atoms, arylthio group with 6 to 10 carbon atoms, cycloalkyl group with 3 to 10 carbon atoms, halogen atom, nitro group, hydroxyl group or Mercapto group; R ^c2 each independently represents an alkyl group with 1 to 10 carbon atoms, an alkyloxy group with 1 to 10 carbon atoms, an alkylthio group with 1 to 10 carbon atoms, and an aromatic group with 6 to 10 carbon atoms. group, an aryloxy group with 6 to 10 carbon atoms, an arylthio group with 6 to 10 carbon atoms, a cycloalkyl group with 3 to 10 carbon atoms, a halogen atom, a hydroxyl group or a mercapto group; n _c1 is the number of repeating units , represents an integer from 1 to 20; n _c2 each independently represents an integer from 0 to 4; n _c3 each independently represents an integer from 0 to 3; * represents a chemical bond. Alkyl group, alkyloxy group, alkyl sulfide of R ^c1 The hydrogen atoms of R ^c2 alkyl, alkyloxy, alkylthio, aryl, and aryloxy groups may be substituted by halogen atoms. , the hydrogen atom of the arylthio group and the cycloalkyl group can be substituted by a halogen atom. When _{n c2} is 2 to 4, R ^c1 can be the same or different in the same ring. When _{n c3} is 2 to 3, R ^{c2 can} be in the same ring. They can be the same or different within a ring.)

The molecular weight distribution Mw/Mn calculated by gel permeation chromatography (GPC) measurement of the maleimide compound containing the structure represented by formula (M1) is preferably within a specific range. The molecular weight distribution is a value obtained by dividing the weight average molecular weight Mw by the number average molecular weight Mn, and is represented by "Mw/Mn". Specifically, the molecular weight distribution Mw/Mn of the maleimide compound containing the structure represented by formula (M1) is preferably 1.0 to 4.0, more preferably 1.1 to 3.8, further preferably 1.2 to 3.6, and particularly preferably 1.3 ~3.4. When the molecular weight distribution Mw/Mn of the maleimide compound containing the structure represented by formula (M1) is within the aforementioned range, the effects of the present invention can be significantly obtained.

In the maleimine compound containing the structure represented by Formula (M1), the amount of the maleimine compound in which the average number of repeating units n ₁ is 0 is preferably within a specific range. When the aforementioned GPC measurement is performed on a maleimine compound containing a structure represented by formula (M1), the amount of the maleimine compound in which the average repeating unit number n ₁ is 0 can be measured based on the area of the GPC measurement result. %express. Specifically, in the chromatogram obtained by the aforementioned GPC measurement, the area of the peak of the maleimide compound in which the average repeating unit number n ₁ is 0 can be determined by comparing the peak area of the maleimide compound with the structure represented by the formula (M1). The ratio (area %) of the total area of the peak of the maleimide compound represents the amount of the maleimide compound in which the average repeating unit number n ₁ is 0. Specifically, the amount of the maleimine compound in which the average repeating unit number n ₁ is 0 is preferably 32 area % relative to 100 area % of the total amount of the maleimine compound containing the structure represented by formula (M1). % or less, more preferably 30 area % or less, still more preferably 28 area % or less. When the amount of the maleimide compound having an average repeating unit number n ₁ of 0 is within the aforementioned range, the effects of the present invention can be significantly obtained.

The maleimide group equivalent of the maleimine compound containing the structure represented by formula (M1) is preferably 50 g/eq. or more, more preferably 100 g/eq. or more, particularly preferably 200 g/eq. or more, It is preferably 2000 g/eq. or less, more preferably 1000 g/eq. or less, and particularly preferably 800 g/eq. or less. The maleimide group equivalent represents the mass of the maleimide compound per 1 equivalent of maleimide group. When the maleimide group equivalent of the maleimine compound containing the structure represented by formula (M1) is within the aforementioned range, the effects of the present invention can be significantly obtained.

The type of (meth)acrylic resin among (E2) other radically polymerizable compounds is not particularly limited as long as it has one or more (preferably two or more) (meth)acrylyl groups in one molecule. . Here, the term "(meth)acrylyl" is a collective term for acrylic and methacryl. Examples of the methacrylic resin include "A-DOG" (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), "DCP-A" (manufactured by Kyeisha Chemical Co., Ltd.), "NPDGA", "FM-400", "R -687", "THE-330", "PET-30", "DPHA" (all manufactured by Nippon Kayaku Co., Ltd.) and other (meth)acrylic resins.

The type of the styrene-based resin is not particularly limited as long as it has one or more (preferably two or more) styrene group groups or vinylphenyl groups in one molecule. Examples of the styrene-based resin include styrene-based resins such as "OPE-2St", "OPE-2St 1200", and "OPE-2St 2200" (all manufactured by Mitsubishi Gas Chemical Co., Ltd.).

The content of (E) radically polymerizable compound in the resin composition may be 0 mass% or more than 0 mass%, preferably 0.01 when the nonvolatile component in the resin composition is 100 mass%. Mass % or more, more preferably 0.1 mass % or more, particularly preferably 0.5 mass % or more, and, for example, 10 mass % or less, preferably 5 mass % or less, more preferably 3 mass % or less, particularly preferably 2 or 2.0 mass% or less.

The content of the (E) radically polymerizable compound in the resin composition may be 0% by mass, or may be greater than 0% by mass, and is preferably 0.1% by mass when the resin component in the resin composition is 100% by mass. % or more, more preferably 1 mass% or more, particularly preferably 1.5 mass% or more, and for example, 20 mass% or less, preferably 10 mass% or less, more preferably 7 mass% or less, still more preferably 5 mass% or less , particularly preferably 3.5% by mass or less.

＜(F)Other hardeners＞ The resin composition of the present invention may contain (F) another hardener as an optional component. This (F) other hardener does not contain substances belonging to the above-mentioned components (A) to (C) and (E). (F) Other hardeners may have a function as an epoxy resin hardener that reacts with (B) epoxy resin to harden the resin composition, similarly to the above-mentioned (C) active ester compound. (F) Other hardeners may be used alone or in combination of two or more.

(F) Other hardeners include, for example, phenol-based hardeners, carbodiimide-based hardeners, acid anhydride-based hardeners, amine-based hardeners, benzoxazine-based hardeners, cyanate ester-based hardeners, and Thiol hardener. Among them, it is preferable to use one or more types of curing agents selected from the group consisting of phenol-based curing agents and carbodiimide-based curing agents.

As the phenolic curing agent, one having one or more, preferably two or more hydroxyl groups bonded to an aromatic ring such as a benzene ring or a naphthalene ring in one molecule can be used. From the viewpoint of heat resistance and water resistance, a phenol-based hardener having a phenolic structure (Novolac structure) is preferred. In addition, from the viewpoint of adhesion, a nitrogen-containing phenol-based curing agent is preferred, and a phenol-based curing agent containing a triazine skeleton is more preferred. Among them, a novolac resin (Phenolic Novolac Resin) containing a triazine skeleton is preferred from the viewpoint of highly satisfying heat resistance, water resistance and adhesion. Specific examples of the phenolic hardener include "MEH-7700", "MEH-7810" and "MEH-7851" manufactured by Meiwa Kasei Co., Ltd., "NHN" and "CBN" manufactured by Nippon Kayaku Co., Ltd. "GPH", "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN-" manufactured by Nippon Steel Chemical Materials Co., Ltd. 375", "SN-395", "LA-7052", "LA-7054", "LA-3018", "LA-3018-50P", "LA-1356", "TD2090", " TD-2090-60M" etc.

As the carbodiimide-based curing agent, one having one or more, preferably two or more carbodiimide structures in one molecule can be used. Specific examples of carbodiimide-based hardeners include tetramethylene-bis(tert-butylcarbodiimide), cyclohexanebis(methylene-tert-butylcarbodiimide), etc. Aliphatic biscarbodiimides; aromatic biscarbodiimides such as phenylene-bis(xylylcarbodiimide) and other biscarbodiimides; polyhexamethylenecarbodiimide, polytrimethylmethane Aliphatic polycarbons such as hexamethylene carbodiimide, polycyclohexylenecarbodiimide, poly(methylenebiscyclohexylenecarbodiimide), poly(isophoronecarbodiimide), etc. Diimines; poly(phenylenecarbodiimide), poly(naphthylenecarbodiimide), poly(tolylenecarbodiimide), poly(methyldiisopropylphenylenecarbodiimide) amine), poly(triethylphenylenecarbodiimide), poly(diethylphenylenecarbodiimide), poly(triisopropylphenylenecarbodiimide), poly(diisopropylphenylenecarbodiimide) methylcarbodiimide), poly(xylylenecarbodiimide), poly(tetramethylxylylenecarbodiimide), poly(methylenediphenylenecarbodiimide), poly(methylenediphenylenecarbodiimide), Methyl bis(methylphenyl)carbodiimide] and other aromatic polycarbodiimides and other polycarbodiimides. Commercially available carbodiimide hardeners include, for example, "CARBODILITE V-02B", "CARBODILITE V-03", "CARBODILITE V-04K", "CARBODILITE V-07" and "CARBODILITE V-07" manufactured by Nisshinbo Chemical Co., Ltd. "CARBODILITE V-09"; "Stabaxol P", "Stabaxol P400", "Hycasyl 510" manufactured by Rhein Chemie, etc.

As the acid anhydride-based curing agent, one having one or more acid anhydride groups per molecule can be used, and one having two or more acid anhydride groups per molecule is preferred. Specific examples of acid anhydride-based hardeners include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and methylhexahydrophthalic anhydride. Phthalic anhydride, methyl nadic anhydride, hydrogenated methyl nadic anhydride, trialkyl tetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3 -Furyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, naphthalene Tetracarboxylic dianhydride, oxybisphthalic dianhydride, 3,3'-4,4'-diphenyltetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro- 5-(Tetrahydro-2,5-dioxo-3-furyl)-naphtho[1,2-C]furan-1,3-dione, ethylene glycol bis(dehydrated trimellitate) , polymer-type acid anhydrides such as styrene-maleic acid resin copolymerized with styrene and maleic acid. Examples of commercially available acid anhydride-based hardeners include "HNA-100", "MH-700", "MTA-15", "DDSA", and "OSA" manufactured by Shin Nippon Rika Co., Ltd.; Mitsubishi Chemical Corporation's "YH-306", "YH-307"; "HN-2200", "HN-5500" made by Hitachi Chemical Co., Ltd.; "EF-30", "EF-40" made by Cray Valley Co., Ltd. "EF-60", "EF-80", etc.

As the amine-based curing agent, one having one or more, preferably two or more amine groups in one molecule can be used. Examples of amine-based curing agents include aliphatic amines, polyether amines, alicyclic amines, aromatic amines, and the like. Among them, aromatic amines are preferred. The amine-based hardener is preferably a primary amine or a secondary amine, and more preferably a primary amine. Specific examples of the amine-based hardener include: 4,4'-methylenebis(2,6-dimethylaniline), 4,4'-diaminodiphenylmethane, 4,4' -Diaminodiphenyl terine, 3,3'-diaminodiphenyl terine, m-phenylenediamine, m-phenylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl Ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybiphenyl Aniline, 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)sine, bis(4-(3-aminophenoxy)phenyl)sine, etc. Examples of commercially available amine-based hardeners include "SEIKACURE-S" manufactured by SEIKA; "KAYABOND C-200S", "KAYABOND C-100", "KAYAHARD A-A", and "KAYAHARD" manufactured by Nippon Kayaku Co., Ltd. A-B", "KAYAHARD A-S"; "EPICURE W" made by Mitsubishi Chemical Corporation; "DTDA" made by Sumitomo Seika Co., Ltd., etc.

Specific examples of benzoxazine-based hardeners include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemical Co., Ltd.; "HFB2006M" manufactured by Showa Polymer Co., Ltd.; " P-d", "F-a", etc.

Examples of the cyanate-based hardener include bisphenol A dicyanate, polyphenol cyanate (oligo(3-methylene-1,5-phenylene cyanate)), 4 ,4'-methylene bis(2,6-dimethylphenyl cyanate), 4,4'-ethylene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2 , 2-bis(4-cyanato)phenylpropane, 1,1-bis(4-cyanatophenylmethane), bis(4-cyanato-3,5-dimethylbenzene) methyl)methane, 1,3-bis(4-cyanatophenyl-1-(methylethylene))benzene, bis(4-cyanatophenyl)sulfide and bis(4-cyano) Difunctional cyanate ester resins such as acid ester phenyl) ether; multifunctional cyanate ester resins derived from phenol novolak resin and cresol novolac resin; some of these cyanate ester resins are obtained by triazinization prepolymers, etc. Specific examples of cyanate-based hardeners include "PT30" and "PT60" manufactured by Lonza Japan (both are phenol novolac-type polyfunctional cyanate ester resins), "BA230", and "BA230S75" (dual A prepolymer obtained by triazinating part or all of phenol A dicyanate to form a trimer), etc.

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

(F) The active group equivalent of other hardeners is preferably 50g/eq. to 3000g/eq., more preferably 100g/eq. to 1000g/eq., further preferably 100g/eq. to 500g/eq., and particularly preferably It is 100g/eq.～300g/eq.. The active group equivalent represents the mass of the hardener per 1 equivalent of active group.

For the mass ratio of the epoxy resin and the hardener, that is, the mass ratio of "component (B)" to "component (C) and component (F)", divide the mass of the non-volatile component of component (B) by The value obtained by adding all the epoxy equivalents is designated as a. The value obtained by dividing the mass of the non-volatile component of component (C) by the active ester group equivalent is added together and designated as b. , and when the value obtained by dividing the mass of the non-volatile component of the component (F) by the active group equivalent is added together and the value obtained is expressed as c, (b+c)/a is preferably 1.0 or more, and more preferably 1.01 or more, more preferably 1.1 or 1.10 or more, still more preferably 1.15 or more, particularly preferably 1.2 or more, and preferably 2.0 or less, more preferably 1.75 or less, even more preferably 1.5 or less, still more preferably 1.4 or 1.40 below, and particularly preferably below 1.35. By setting the amount ratio of the epoxy resin to the hardener within the above range, the effects of the present invention can be easily obtained.

Regarding the content of (F) other hardeners in the resin composition, when the non-volatile component in the resin composition is 100 mass %, it may be 0 mass %, may be greater than 0 mass %, and is preferably 0.01 mass %. Above, it is 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, and particularly preferably 5% by mass or less.

Regarding the content of (F) other hardeners in the resin composition, when the resin component in the resin composition is 100 mass %, it may be 0 mass % or more than 0 mass %, preferably 0.1 mass % or more. , more preferably 1.0 mass% or more, particularly preferably 4.0 mass% or more, preferably 50 mass% or less, more preferably 20 mass% or less, particularly preferably 10 mass% or less.

＜(G) Hardening accelerator＞ The resin composition of the present invention may contain (G) a hardening accelerator as an optional component.

Examples of the hardening accelerator include phosphorus-based hardening accelerators, urea-based hardening accelerators, guanidine-based hardening accelerators, imidazole-based hardening accelerators, metal-based hardening accelerators, and amine-based hardening accelerators. (G) Hardening accelerator may be used individually by 1 type, or in combination of 2 or more types.

Examples of the phosphorus-based hardening accelerator include tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis (Tetrabutylphosphonium)pyromellitate, tetrabutylphosphonium hydrohexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl Aliphatic phosphonium salts such as ]-4-methylphenolate, di-tert-butylmethylphosphonium tetraphenylborate; methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium Bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra-p-tolylborate, tetraphenylphosphonium tetraphenylborate Salt, tetraphenylphosphonium tetraphenylborate, triphenylethylphosphonium tetraphenylborate, tris(3-methylphenyl)ethylphosphonium tetraphenylborate, tris(2-methoxy) Phenyl)ethylphosphonium tetraphenylborate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, etc. Aromatic phosphonium salts; aromatic phosphine-borane complexes such as triphenylphosphine-triphenylborane; aromatic phosphine-quinone addition reactants such as triphenylphosphine-p-benzoquinone addition reactants; Tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butyl(2-butenyl)phosphine, di-tert-butyl(3-methyl-2-butenyl)phosphine, tricyclohexyl Aliphatic phosphine such as phosphine; dibutylphenylphosphine, di-tert-butylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclohexylphosphine, Triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tris(4-ethylphenyl)phosphine, tris(4-propylphenyl)phosphine, tris(4-isopropyl) phenyl)phosphine, tris(4-butylphenyl)phosphine, tris(4-tert-butylphenyl)phosphine, tris(2,4-dimethylphenyl)phosphine, tris(2,5-di Methylphenyl)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-ethyl) Oxyphenyl)phosphine, tris(4-tert-butoxyphenyl)phosphine, diphenyl-2-pyridylphosphine, 1,2-bis(diphenylphosphine)ethane, 1,3-bis( Diphenylphosphine)propane, 1,4-bis(diphenylphosphine)butane, 1,2-bis(diphenylphosphine)acetylene, 2,2'-bis(diphenylphosphine)diphenyl ether Aromatic phosphines, etc.

Examples of urea-based hardening accelerators include: 1,1-dimethylurea; 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, and 3-cyclohexyl -aliphatic dimethylureas such as 1,1-dimethylurea and 3-cyclooctyl-1,1-dimethylurea; 3-phenyl-1,1-dimethylurea, 3-( 4-Chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-(3-chloro-4-methylbenzene) base)-1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethyl Urea, 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 base)phenyl]-1,1-dimethylurea, 3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trifluoromethyl base)phenyl]-1,1-dimethylurea, N,N-(1,4-phenyl)bis(N',N'-dimethylurea), N,N-(4-methyl Aromatic dimethylureas such as methyl-1,3-phenyl)bis(N',N'-dimethylurea) [toluene bisdimethylurea], etc.

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

Examples of the imidazole-based hardening accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4- Methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methyl Imidazole, 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-diamine Base-6-[2'-Undecyl imidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methyl Imidazolyl-(1') ]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1') ]-ethyl-s-triazine isocyanuride Acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-Dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, Imidazole compounds such as 2-phenylimidazoline and adducts of imidazole compounds and epoxy resins.

As the imidazole-based hardening accelerator, commercially available products can be used, and examples thereof include "1B2PZ", "2MZA-PW", and "2PHZ-PW" manufactured by Shikoku Chemical Industry Co., Ltd., and "P200-H50" manufactured by Mitsubishi Chemical Corporation. wait.

Examples of metal-based hardening accelerators include organic metal complexes or organic metal salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organic metal complex include organic cobalt complexes such as cobalt acetyl acetonate (II) and cobalt acetyl acetonate (III), organic copper complexes such as copper acetyl acetonate (II), Organic zinc complexes such as zinc acetyl acetonate (II), organic iron complexes such as iron acetyl acetonate (III), organic nickel complexes such as nickel acetyl acetonate, manganese acetyl acetonate (II), etc. Organic manganese complexes, etc. Examples of organic metal salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, and the like.

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

As the amine-based hardening accelerator, commercially available products can be used, and examples thereof include "MY-25" manufactured by Ajinomoto Fine-Techno Co., Inc. and the like.

The content of the (G) hardening accelerator in the resin composition is not particularly limited. When the non-volatile component in the resin composition is 100% by mass, it is preferably 15% by mass or less, more preferably 10% by mass or less, and still more preferably It is 5 mass % or less, and it is especially preferable that it is 3 mass % or less. The lower limit of the content of the (G) hardening accelerator in the resin composition is not particularly limited. When the non-volatile component in the resin composition is 100% by mass, it may be, for example, 0% by mass or more, 0.001% by mass or more, or 0.01% by mass. % or more, 0.1 mass% or more, 0.5 mass% or more, etc.

＜(H)Other additives＞ The resin composition of the present invention may further contain optional additives as non-volatile components. Examples of such additives include radical polymerization initiators such as peroxide-based radical polymerization initiators and azo-based radical polymerization initiators; phenol-based hardeners (phenol-based hardeners), naphthols, etc. Hardeners, acid anhydride-based hardeners, thiol-based hardeners, benzoxazine-based hardeners, cyanate ester-based hardeners, carbodiimide-based hardeners, imidazole-based hardeners, etc., other than active ester compounds Epoxy hardener; phenoxy resin, polyvinyl acetal resin, polyolefin resin, polyester resin, polyether resin, polyphenylene ether resin, polycarbonate resin, polyether ether ketone resin, polyester resin and other thermoplastics Resins; organic fillers such as rubber particles; organic metal compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; colorings such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black, etc. Polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and phenothiazine; leveling agents such as polysiloxane leveling agents and acrylic polymer leveling agents; Benton, montmorillonite, etc. and other thickeners; defoaming agents such as polysilicone-based defoaming agents, acrylic-based defoaming agents, fluorine-based defoaming agents, and vinyl resin-based defoaming agents; UV absorbers such as benzotriazole-based UV absorbers; Adhesion improving agents such as urea silane; adhesion-imparting agents such as triazole-based adhesion-imparting agents, tetrazole-based adhesion-imparting agents, and triazine-based adhesion-imparting agents; hindered phenol-based antioxidants, hindered amines Antioxidants such as antioxidants; fluorescent whitening agents such as stilbene derivatives; surfactants such as fluorine-based surfactants and polysiloxane-based surfactants; phosphorus-based flame retardants (such as phosphate ester compounds, phosphazene compounds, Phosphinic acid compounds, red phosphorus), nitrogen-based flame retardants (such as melamine sulfate), halogen-based flame retardants, inorganic-based flame retardants (such as antimony trioxide) and other flame retardants; phosphate ester dispersants, polyoxide Ethylene dispersants, acetylenic dispersants, polysiloxane dispersants, anionic dispersants, cationic dispersants and other dispersants; borate ester stabilizers, titanate ester stabilizers, aluminate ester stabilizers , zirconate-based stabilizers, isocyanate-based stabilizers, carboxylic acid-based stabilizers, carboxylic anhydride-based stabilizers and other stabilizers. (H) Other additives may be used alone or in combination of two or more at any ratio. (H) The content of other additives can be appropriately set by those with ordinary knowledge in the technical field to which the invention belongs.

＜(K) Organic solvent＞ The resin composition of the present invention may further contain an optional organic solvent as a volatile component in addition to the non-volatile components described above. As (K) the organic solvent, a known organic solvent can be used appropriately, and the type thereof is not particularly limited. Examples of (K) organic solvents include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; methyl acetate, ethyl acetate, butyl acetate, and isobutyl acetate. , isoamyl acetate, methyl propionate, ethyl propionate, γ-butyrolactone and other ester solvents; tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, Ether solvents such as dibutyl ether and diphenyl ether; alcohol solvents such as methanol, ethanol, propanol, butanol, and ethylene glycol; 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, Ether ester solvents such as diethylene glycol monoethyl ether acetate, diethylene glycol ethyl ether acetate (ethyl diglycol acetate), γ-butyrolactone, methyl methoxypropionate, etc.; methyl lactate , ethyl lactate, methyl 2-hydroxyisobutyrate and other ester alcohol solvents; 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, diethylene glycol Ether alcohol solvents such as alcohol monobutyl ether (butylcarbitol); N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone and other solvents Amine solvents; dimethyl styrene and other teresine solvents; acetonitrile, propionitrile and other nitrile solvents; hexane, cyclopentane, cyclohexane, methylcyclohexane and other aliphatic hydrocarbon solvents; benzene, toluene , xylene, ethylbenzene, trimethylbenzene and other aromatic hydrocarbon solvents. (K) One type of organic solvent may be used alone, or two or more types may be used in combination at an arbitrary ratio.

In one embodiment, the content of the organic solvent (K) is not particularly limited. When all the components in the resin composition are 100% by mass, it may be, for example, 60% by mass or less, 40% by mass or less, 30% by mass or less, or 20% by mass. Mass% or less, 15 mass% or less, 10 mass% or less, etc.

＜Manufacturing method of resin composition＞ The resin composition of the present invention can be produced, for example, by adding (A) a styrene-based styrene having a weight average molecular weight of 10,000 or less to an arbitrary preparation container in an arbitrary order and/or partially or entirely simultaneously, and/or hydrogenating the resin composition of the present invention. Styrenic polymer, (B) epoxy resin and (C) active ester compound, if necessary (D) inorganic filler, if necessary (E) radically polymerizable compound, if necessary (F) other hardening agent, (G) hardening accelerator as needed, (H) other additives as needed and (K) organic solvent as needed, and mix. In addition, in the process of adding each component and mixing, the temperature can be set appropriately, and heating and/or cooling can be performed temporarily or continuously. In addition, during or after the addition and mixing, the resin composition can be stirred or shaken using a stirring device such as a mixer or an oscillating device to uniformly disperse the resin composition. In addition, defoaming can be performed under low-pressure conditions such as vacuum while stirring or shaking.

＜Characteristics of resin composition＞ The resin composition of the present invention contains (A) a styrenic and/or hydrogenated styrene polymer having a weight average molecular weight of 10,000 or less, (B) an epoxy resin, and (C) an active ester compound. By using such a resin composition, it is possible to obtain a cured product that is excellent in crack resistance after desmearing. Preferably, it is possible to obtain a cured product that can withstand any environment such as room temperature such as 23°C or normal temperature range and high temperature environment such as 90°C. It is a hardened material with low dielectric loss tangent, low relative dielectric constant and high glass transition temperature at room temperature or any environment in the normal temperature range or high temperature environment.

The cured product of the resin composition of the present invention may have the characteristic of suppressing the occurrence of cracks after the desmearing process (roughening process). Therefore, in one embodiment, after the circuit board is produced and desmeared as in Test Example 2 below, when 100 copper pad portions of the circuit board are observed, the number of cracks is preferably 10 or less (10% or less). .

The cured product of the resin composition of the present invention can have a characteristic that the dielectric loss tangent (Df) is low even in a high temperature environment such as 90°C. Therefore, in one embodiment, the dielectric loss tangent (Df) of the cured product of the resin composition when measured under the conditions of 5.8 GHz and 90°C as in Test Example 1 below can be preferably 0.020 or less and 0.010 or less. , more preferably 0.009 or less and 0.008 or less, further preferably 0.007 or less and 0.006 or less, particularly preferably 0.005 or less and 0.004 or less.

The cured product of the resin composition of the present invention can have a characteristic that the dielectric loss tangent (Df) is low even at room temperature such as 23° C. or normal temperature. Therefore, in one embodiment, the dielectric loss tangent (Df) of the cured product of the resin composition when measured under the conditions of 5.8 GHz and 23°C as in Test Example 1 below can be preferably 0.020 or less and 0.010 or less. , more preferably 0.009 or less, 0.008 or less, further preferably 0.007 or less, 0.006 or less, still more preferably 0.005 or less, 0.004 or less, particularly preferably 0.003 or less.

The cured product of the resin composition of the present invention can have a characteristic that the relative dielectric constant (Dk) is low even in a high temperature environment such as 90°C. Therefore, in one embodiment, the relative dielectric constant (Dk) of the cured product of the resin composition when measured under the conditions of 5.8 GHz and 90° C. as in Test Example 1 below is preferably 5.0 or less, more preferably 4.0. below, more preferably 3.5 or less. When the inorganic filler (D) contains hollow silica, the above-mentioned relative dielectric constant (Dk) can be further reduced to preferably 5.0 or less, more preferably 4.0 or less, still more preferably 3.5 or less. , particularly preferably 3.0 or less.

The cured product of the resin composition of the present invention may have a characteristic that the relative dielectric constant (Dk) is low even at room temperature such as 23° C. or normal temperature. Therefore, in one embodiment, the relative dielectric constant (Dk) of the cured product of the resin composition when measured under the conditions of 5.8 GHz and 23° C. as in Test Example 1 below is preferably 5.0 or less, more preferably 4.0. below, more preferably 3.5 or less. When the inorganic filler (D) contains hollow silica, the above-mentioned relative dielectric constant (Dk) can be further reduced to preferably 5.0 or less, more preferably 4.0 or less, still more preferably 3.5 or less. , particularly preferably 3.0 or less.

The cured product of the resin composition of the present invention may have a characteristic that the glass transition temperature is high. Therefore, in one embodiment, as in Test Example 3 below, the glass transition temperature (Tg) of the cured product when thermally cured at 190°C for 90 minutes is preferably higher than 135°C, more preferably 140°C or higher, and even more preferably 150°C. °C or above, more preferably 153°C or above. The upper limit is not particularly limited and may be 200° C. or lower. For example, when a hydrogenated styrenic polymer is used as the component (A), the glass transition temperature may meet the conditions.

＜Applications of resin composition＞ The resin composition of the present invention can be suitably used as a resin composition for insulating purposes, particularly a resin composition for forming an insulating layer. Specifically, it can be suitably used as: a resin composition for forming "the insulating layer for forming a conductor layer formed on an insulating layer including a rewiring layer" Resin composition for forming an insulating layer for forming a conductor layer). In addition, in a printed wiring board described below, it can be suitably used as a resin composition for forming an insulating layer of a printed wiring board (a resin composition for forming an insulating layer of a printed wiring board). The resin composition of the present invention can also be used in resin sheets, prepregs and other sheet-like laminate materials, solder resists, underfill materials, die bonding materials, semiconductor sealing materials, filling resins, component embedding resins, etc. where the resin composition is required widely used in applications.

In addition, for example, when a semiconductor wafer package is manufactured through the following steps (1) to (6), the resin composition of the present invention can also be suitably used as an insulating layer for forming a rewiring layer. A resin composition for wiring forming layers (resin composition for forming wiring forming layers), and a resin composition for sealing semiconductor wafers (resin composition for sealing semiconductor wafers). When manufacturing the semiconductor chip package, a rewiring layer may be further formed on the sealing layer. (1) The step of laminating the temporary fixing film on the base material, (2) The step of temporarily fixing the semiconductor wafer on the temporary fixing film, (3) The step of forming a sealing layer on the semiconductor wafer, (4) The step of peeling the base material and the temporary fixing film from the semiconductor wafer, (5) The step of forming a rewiring formation layer as an insulating layer on the surface of the semiconductor wafer from which the base material and the temporary fixing film are peeled off, and (6) A step of forming a rewiring layer as a conductor layer on the rewiring forming layer.

In addition, the resin composition of the present invention can form an insulating layer with good component embedding properties, and therefore can be suitably applied to a case where a printed wiring board is a circuit board with built-in components.

＜Sheet laminated materials＞ The resin composition of the present invention may be applied and used in a paint state, but industrially, it is usually preferably used in the form of a sheet-like laminate material containing the resin composition.

As the sheet-like laminated material, resin sheets and prepregs shown below are preferred.

In one embodiment, the resin sheet includes a support body and a resin composition layer provided on the support body, and the resin composition layer is formed of the resin composition of the present invention.

The thickness of the resin composition layer is preferably 50 μm or less, more preferably 50 μm or less, from the viewpoint of thinning the printed wiring board and being able to provide a cured product having excellent insulation properties even if the cured product of the resin composition is a thin film. It is preferably 40 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, but may generally be 5 μm or more, 10 μm or more, or the like.

Examples of the support include a film, a metal foil, and a release paper made of a plastic material. Preferably, a film or a metal foil made of a plastic material is used.

When using a film made of a plastic material as a support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes referred to as "PET"), polyethylene naphthalate (hereinafter sometimes referred to as "PEN") and other polyesters, polycarbonate (hereinafter sometimes referred to as "PC"), acrylic polymers such as polymethyl methacrylate (PMMA), cyclic polyolefins, triethylene Acetocellulose (TAC), polyether sulfide (PES), polyetherketone, polyimide, etc. Among these, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

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

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

Moreover, as a support body, the support body with a release layer which has a release layer on the surface joined to a resin composition layer can be used. Examples of the release agent used in the release layer of the support with a release layer include alkyd resins, polyolefin resins, urethane resins, and polysiloxane resins. More than 1 release agent in A commercially available product can be used as a support with a release layer. For example, "SK-1" manufactured by Lintec Corporation, which is a PET film having a release layer containing an alkyd resin release agent as a main component, can be used. ", "AL-5", "AL-7", "Lumirror T60" made by Toray, "Purex" made by Teijin, "Unipeel" made by UNITIKA, etc.

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

In one embodiment, the resin sheet may further include optional layers as needed. Examples of the optional layer include a protective film selected according to the support provided on the surface of the resin composition layer that is not bonded to the support (that is, the surface opposite to the support). The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to prevent dust and the like from adhering to the surface of the resin composition layer or causing damage to the surface of the resin composition layer.

The resin sheet can be produced, for example, by directly applying a liquid resin composition onto a support using a die coater or the like, or by dissolving the resin composition in an organic solvent to prepare a resin coating, and applying the resin coating using a die coater or the like. This is applied to a support and dried to form a resin composition layer.

Examples of the organic solvent include the same organic solvents described as components of the resin composition. One type of organic solvent may be used alone, or two or more types may be used in combination.

Drying can be performed by known methods such as heating and blowing hot air. Drying conditions are not particularly limited, and drying is performed so that the content of the organic solvent in the resin composition layer becomes 10 mass% or less, preferably 5 mass% or less. Although it differs depending on the boiling point of the organic solvent in the resin composition or resin paint, for example, when using a resin composition or resin paint containing 30% by mass to 60% by mass of an organic solvent, the temperature can be adjusted to 50°C to 60% by mass. Dry at 150° C. for 3 to 10 minutes to form a resin composition layer.

The resin sheet can be wound into a roll shape 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 can be formed by impregnating a sheet-like fiber base material with the resin composition of the present invention.

The sheet-like fiber base material used for the prepreg is not particularly limited, and base materials commonly used as base materials for prepregs such as glass cloth, aromatic polyamide 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, further 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. Usually above 10μm.

Prepregs can be produced by known methods such as hot melt method and solvent method.

The thickness of the prepreg may be in the same range as the resin composition layer in the above-mentioned resin sheet.

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

＜Printed wiring board＞ The printed wiring board of the present invention includes an insulating layer formed of a cured product obtained by curing the resin composition of the present invention.

The printed wiring board can be produced by a method including the following steps (I) and (II) using the above-mentioned resin sheet, for example. Step (I), laminating the resin sheet on the inner substrate in such a manner that the resin composition layer of the resin sheet is bonded to the inner substrate. Step (II), hardening (for example, thermal hardening) the resin composition layer to form an insulating layer

The "inner layer substrate" used in step (I) refers to a member that becomes the substrate of a printed wiring board, and examples thereof include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, and BT resin substrates. Thermosetting polyphenylene ether substrate, etc. In addition, the substrate may have a conductor layer on one or both sides thereof, and the conductor layer may be patterned. An inner-layer substrate in which a conductor layer (circuit) is formed on one or both sides of the substrate is sometimes called an "inner-layer circuit substrate." In addition, an intermediate product on which an insulating layer and/or a conductor layer is further formed when manufacturing a printed wiring board is also included in the "inner layer substrate" referred to in the present invention. When the printed wiring board is a circuit board with built-in components, an inner substrate with built-in components can be used.

Lamination of the inner-layer substrate and the resin sheet can be performed, for example, by thermally and press-bonding the resin sheet to the inner-layer substrate from the support side. Examples of a member for heat and pressure bonding the resin sheet to the inner substrate (hereinafter also referred to as "heat and pressure bonding member") include a heated metal plate (SUS end plate, etc.) or a metal roller (SUS roller) wait. It should be noted that it is preferable not to directly press the heat-pressing bonding member onto the resin sheet, but to press it through an elastic material such as heat-resistant rubber so that the resin sheet can fully follow the surface irregularities of the inner substrate.

Lamination of the inner substrate and the resin sheet can be performed by a vacuum lamination method. In the vacuum lamination method, the heating and crimping temperature is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C, and the heating and crimping pressure is preferably in the range of 0.098MPa to 1.77MPa, more preferably 0.29MPa to 1.47MPa. The heating and pressure bonding time is preferably in the range of 20 seconds to 400 seconds, and more preferably in the range of 30 seconds to 300 seconds. Lamination can preferably be carried out under reduced pressure conditions of 26.7 hPa or less.

Lamination can be performed with a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum pressure laminator manufactured by Meiki Seisakusho Co., Ltd., a vacuum applicator manufactured by Nikko-Materials, and an intermittent vacuum pressure laminator. .

After lamination, the laminated resin sheets can be smoothed by pressing the heated and pressure-bonded member under normal pressure (atmospheric pressure), for example, from the support side. The pressing conditions of the smoothing treatment can be set to the same conditions as the heating and pressure bonding conditions of the above-mentioned lamination. Smoothing can be performed with a commercially available laminator. In addition, lamination and smoothing processing can be performed continuously using the above-mentioned commercially available vacuum laminator.

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

In step (II), the resin composition layer is hardened (for example, thermally hardened) to form an insulating layer formed of a hardened product of the resin composition. The curing conditions of the resin composition layer are not particularly limited, and conditions generally used when forming an insulating layer of a printed wiring board can be used.

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

Before thermally hardening the resin composition layer, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, before thermally hardening the resin composition layer, the resin composition layer is heated at a temperature of 50°C to 120°C, preferably 60°C to 115°C, and more preferably 70°C to 110°C for 5 minutes or more, preferably 5 minutes. ~150 minutes, more preferably 15 minutes to 120 minutes, further preferably 15 minutes to 100 minutes for preheating.

When manufacturing the printed wiring board, the steps of (III) opening holes in the insulating layer, (IV) roughening the insulating layer, and (V) forming the conductor layer may be further performed. The above-described steps (III) to (V) can be implemented according to various methods known to those skilled in the art of manufacturing printed wiring boards. It should be noted that when the support is removed after step (II), the removal of the support can be between step (II) and step (III), between step (III) and step (IV), or Implemented between step (IV) and step (V). In addition, if necessary, the formation of the insulating layer and the conductor layer in steps (II) to (V) can be repeated to form a multilayer wiring board.

In other embodiments, the printed wiring board of the present invention can be produced using the above prepreg. The manufacturing method is basically the same as when using a resin sheet.

Step (III) is a step of opening holes in the insulating layer, whereby holes such as through holes and through holes can be formed on the insulating layer. Step (III) can be implemented using, for example, a drill, laser, plasma, etc., depending on the composition of the resin composition used in forming the insulating layer. The size and shape of the hole can be appropriately determined according to the design of the printed wiring board.

Step (IV) is a step of roughening the insulating layer. Usually, in this step (IV), the slag is also removed. The steps and conditions of the roughening treatment are not particularly limited, and known steps and conditions generally used when forming an insulating layer of a printed wiring board can be adopted. For example, the insulating layer can be roughened by sequentially performing swelling treatment using a swelling liquid, roughening treatment using an oxidizing agent, and neutralization treatment using a neutralizing liquid.

The swelling liquid used in the roughening treatment is not particularly limited, and examples thereof include alkaline solutions, surfactant solutions, and the like. Alkaline solutions are preferred, and sodium hydroxide solutions and potassium hydroxide solutions are more preferred as the alkaline solutions. Examples of commercially available swelling solutions include "Swelling Dip Securiganth P" and "Swelling Dip Securiganth SBU" manufactured by ATOTECH JAPAN. The swelling treatment based on the swelling liquid is not particularly limited. For example, the insulation layer can be immersed in a swelling liquid of 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 a moderate level, it is preferable to immerse the insulating layer in a swelling liquid of 40° C. to 80° C. for 5 minutes to 15 minutes.

The oxidizing agent used in the roughening treatment is not particularly limited, and examples thereof include an alkaline permanganic acid solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The roughening treatment by an oxidizing agent such as an alkaline permanganic acid solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60°C to 100°C for 10 to 30 minutes. In addition, the concentration of permanganate in the alkaline permanganic acid solution is preferably 5 to 10 mass%. Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as "Concentrate Compact CP" and "Dosing Solution Securiganth P" manufactured by Atotech Japan.

In addition, the neutralizing liquid used in the roughening treatment is preferably an acidic aqueous solution, and an example of a commercially available product is "Reduction Solution Securiganth P" manufactured by Atotech Japan Co., Ltd.

The treatment by the neutralizing liquid can be performed by immersing the treated surface that has completed the roughening treatment by the oxidizing agent in a neutralizing liquid of 30°C to 80°C for 5 to 30 minutes. From the viewpoint of workability and the like, a method in which the object that has been roughened by an oxidizing agent is immersed in a neutralizing liquid at 40° C. to 70° C. for 5 minutes to 20 minutes is preferred.

Step (V) is a step of forming a conductor layer, and the conductor layer is formed on the insulating layer. The conductor material used in the conductor layer is not particularly limited.

In a preferred embodiment, the conductor layer includes at least one selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium of metal. The conductor layer may be a single metal layer or an alloy layer. Examples of the alloy layer include alloys of two or more metals selected from the above group (for example, nickel-chromium alloy, copper-nickel alloy and copper-titanium alloy). Among them, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or a nickel-chromium alloy is preferred from the viewpoint of versatility, cost, ease of patterning, etc. of conductor layer formation. , an alloy layer of copper-nickel alloy, copper-titanium alloy, more preferably a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel-chromium alloy, further preferably copper single metal layer.

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

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

In one embodiment, the conductor layer may be formed by plating. For example, conventionally known techniques such as a semi-additive method and a fully-additive method can be used to plate the surface of the insulating layer to form a conductor layer having a desired wiring pattern. This is preferred from the viewpoint of ease of production. Formed using the semi-additive method. Hereinafter, an example of forming a conductor layer using a semi-additive method is shown.

First, a plating seed layer is formed on the surface of the insulating layer using electroless plating. Next, on the formed plating seed layer, a mask pattern is formed to expose a part of the plating seed layer in accordance with a desired wiring pattern. On the exposed plating seed layer, a metal layer is formed by electrolytic plating, and then the mask pattern is removed. Then, the unnecessary plating seed layer is removed by etching or the like to form a conductor layer having a desired wiring pattern.

In other embodiments, the conductor layer may be formed using metal foil. When forming the conductor layer using 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 surface of the exposed resin composition layer. The resin composition layer and the metal foil can be laminated by a vacuum lamination method. The conditions for lamination may be the same as those described for step (I). Next, step (II) is performed to form an insulating layer. Then, using the metal foil on the insulating layer, a conductor layer having a desired wiring pattern can be formed by conventionally known techniques such as the subtractive method and the improved semi-additive method.

The metal foil can be produced by known methods such as electrolysis and rolling. Examples of commercially available metal foils include HLP foil and JXUT-III foil manufactured by JX Nippon Mining & Metals Co., Ltd., 3EC-III foil and TP-III foil manufactured by Mitsui Mining & Metals Co., Ltd., and the like.

＜Semiconductor Device＞ The semiconductor device of the present invention includes the printed wiring board of the present invention. The semiconductor device of the present invention can be manufactured using the printed wiring board of the present invention.

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

Hereinafter, the present invention will be specifically described with reference to examples. The present invention is not limited by these examples. It should be noted that in the following, unless otherwise specified, "parts" and "%" indicating amounts refer to "parts by mass" and "% by mass" respectively. The temperature condition when no temperature is specified is room temperature (25°C).

[Synthesis Example 1: Synthesis of active ester compound A] Put 203.0g of isophthalyl chloride (moles of the chloride group: 2.0 moles) and 1400g of toluene into a flask equipped with a thermometer, a dropping funnel, a condenser tube, a fractionating tube, and a stirrer, and carry out experiments on the system. Replace with nitrogen under reduced pressure to dissolve. Next, 113.9 g (0.67 mol) of o-phenylphenol and 240 g (mol number of phenolic hydroxyl groups: 1.33 mol) of benzyl-modified naphthalene compound were charged, and the system was replaced with nitrogen under reduced pressure to dissolve them. . Then, 0.70 g of tetrabutylammonium bromide was dissolved, and while performing nitrogen purging treatment, the system was controlled below 60° C., and 400 g of a 20% sodium hydroxide aqueous solution was added dropwise over 3 hours. Next, stirring was continued under these conditions for 1.0 hours. After the reaction is completed, the mixture is allowed to stand for liquid separation and the water layer is removed. Furthermore, water was added to the toluene layer in which the reactants were dissolved, and the mixture was stirred and mixed for 15 minutes. The mixture was allowed to stand for liquid separation, and the water layer was removed. This operation was repeated until the pH of the water layer became 7. Then, water was removed by decanter dehydration to obtain active ester compound A in a toluene solution state with a non-volatile content of 62% by mass. The active ester equivalent of the obtained active ester compound A was 238 g/eq.

[Synthesis Example 2: Synthesis of Active Ester Compound B] Addition polymerization reaction resin of dicyclopentadiene and phenol (hydroxyl equivalent: 165g/equivalent (eq, softening point 85°C), 134g o-allylphenol (1.0 mol) and 1200g toluene, and replace the system with nitrogen under reduced pressure. Next, 203 g (1.0 mol) of isophthalic acid chloride was charged, and the system was replaced with nitrogen under reduced pressure. 0.6 g of tetrabutylammonium bromide was added, and while purging with nitrogen, the system was controlled below 60°C. 412 g of 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. After the dropwise addition, stirring was performed for 1.0 hours. After the reaction was completed, the aqueous layer was removed by standing and liquid separation. Water was further added to the obtained toluene layer, the mixture was stirred for 15 minutes, and the water layer was removed by liquid separation by standing still. This operation was repeated until the pH of the water layer became 7. Then, the non-volatile content was adjusted to 70% by mass by heating and drying, thereby obtaining an active ester resin represented by the following chemical formula.

In the above chemical formula, S is each independently an integer of 0 or 1 or more, and the average value of r calculated from the charge ratio is 1. In addition, the dotted line in the chemical formula is a structure obtained by reacting isophthalic acid chloride, an addition polymerization reaction resin of phenol, and/or o-allylphenol. The ester group equivalent of the active ester resin was calculated from the charging ratio and was 214 g/equivalent (eq.).

[Example 1] 10 parts of naphthalene-type epoxy resin ("HP-4032-SS" manufactured by DIC Corporation, epoxy equivalent 144g/eq.), naphthalene aralkyl-type epoxy resin ("HP-4032-SS" manufactured by Nippon Steel Chemical Materials Corporation) ESN-475V", epoxy equivalent 330g/eq.) 5 parts, biphenyl aralkyl type epoxy resin (Nihon Kayaku Co., Ltd. "NC-3100", epoxy equivalent 258g/eq.) 5 parts, active 43 parts of ester-based hardener ("HPC-8150-62T", toluene solution with active radical equivalent weight 229g/eq., non-volatile content 61.5% by mass), other hardeners (phenol-based hardener, "LA-3018" manufactured by DIC Corporation -50P", hydroxyl equivalent 151g/eq., 50 mass% non-volatile content of 1-methoxy 2-propanol solution), 5 parts of low molecular weight polystyrene (A) component (manufactured by Yasuhara Chemical Co., Ltd. "SX -100"; Mw2000) 10 parts, inorganic filler (spherical silica (manufactured by Yaduma Corporation, "SO- C2", average particle diameter 0.5 μm, specific surface area 5.8 m ² /g) 135 parts, 0.5 parts of hardening accelerator (manufactured by Shikoku Chemical Industry Co., Ltd., "1B2PZ"), 10 parts of MEK, and 10 parts of cyclohexanone were mixed and used. The high-speed rotating mixer disperses the resin evenly to obtain the resin coating.

[Example 2] In Example 1, 43 parts of the active ester-based hardener ("HPC-8150-62T", active group equivalent 223g/eq., non-volatile content 61.5% by mass, toluene solution) was changed to an active ester-based hardener (DIC Co., Ltd. Prepare 40 parts of "HPC-8000-65T", a toluene solution with an active radical equivalent of 223g/eq. and a non-volatile content of 65% by mass. Except for the above matters, it carried out similarly to Example 1, and obtained the resin coating material.

[Example 3] In Example 1, 43 parts of the active ester-based hardener ("HPC-8150-62T", active group equivalent 223 g/eq., toluene solution of 61.5 mass% non-volatile content) was changed to the active ester obtained in Synthesis Example 1 A (toluene solution with active radical equivalent of 238g/eq. and non-volatile content of 61.5% by mass) 43 parts. Except for the above matters, it carried out similarly to Example 1, and obtained the resin coating material.

[Example 4] In Example 1, 43 parts of the active ester-based hardener ("HPC-8150-62T", active group equivalent 223 g/eq., toluene solution of 61.5 mass% non-volatile content) was changed to the active ester obtained in Synthesis Example 2 B (toluene solution with active radical equivalent of 214g/eq. and non-volatile content of 70% by mass) 37 parts. Except for the above matters, it carried out similarly to Example 1, and obtained the resin coating material.

[Example 5] In Example 1, 43 parts of the active ester-based hardener ("HPC-8150-62T", active group equivalent 223g/eq., non-volatile content 61.5 mass% toluene solution) was changed to an active ester-based hardener (Air Water "PC1300-02-65MA" produced by the company, active group equivalent 199g/eq., non-volatile content 65% by mass of methyl amyl ketone solution) 37 parts. Except for the above matters, it carried out similarly to Example 1, and obtained the resin coating material.

[Example 6] In Example 1, maleimide represented by the following formula (M) synthesized by the method described in Synthesis Example 1 of Japan Invention Association Publication Technical Report No. 2020-500211 was further used. 2 parts of MEK solution (non-volatile content 62% by mass) of compound A (Mw/Mn=1.81, t”=1.47 (mainly 1, 2 or 3)). Except for the above matters, operate in the same manner as in Example 1 , get the resin coating.

[Example 7] In Example 1, 2 parts of another thermosetting resin (maleimide resin ("MIR-5000-60T" manufactured by Nippon Kayaku Co., Ltd., a toluene solution of 60 mass % non-volatile content) was further used. In addition to the above matters Except for this, the same procedure as in Example 1 was carried out to obtain a resin paint.

[Example 8] In Example 1, 2 parts of another thermosetting resin (maleimide resin ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., a toluene/MEK mixed solution with a non-volatile content of 70% by mass) was further used. In addition to Except for the above matters, it carried out similarly to Example 1, and obtained the resin coating material.

[Example 9] In Example 1, 2 parts of another thermosetting resin (maleimide resin ("BMI-689" manufactured by Design Corporation) was further used. Except for the above matters, the same operation as in Example 1 was performed to obtain a resin coating .

[Example 10] In Example 1, 2 parts of another thermosetting resin (acrylate resin ("A-DOG" manufactured by Shin-Nakamura Chemical Co., Ltd.) were further used. Except for the above matters, the same operation as in Example 1 was performed to obtain a resin paint.

[Example 11] In Example 1, 2 parts of another thermosetting resin (styrene-based resin ("OPE-2St-1200" manufactured by Mitsubishi Gas Chemical Co., Ltd., a toluene solution with a non-volatile content of 65% by mass)) was further used. In addition to the above matters, The same operation as in Example 1 was performed to obtain a resin paint.

[Example 12] In Example 1, an inorganic filler (spherical silica (manufactured by Yaduma Corporation, "KBM573" manufactured by Shin-Etsu Chemical Industry Co., Ltd.) was surface-treated with an inorganic filler) SO-C2", average particle diameter 0.5 μm, specific surface area 5.8 m ² /g) was changed from 170 parts to 135 parts, and an inorganic filler having a hollow part (an amine-based alkoxysilane compound (manufactured by Shin-Etsu Chemical Industry Co., Ltd.) was added "KBM573"), except that 35 parts of spherical silica having a hollow portion ("BA-S" manufactured by Nikko Catalyst Chemicals Co., Ltd.) were surface-treated, the same operation was performed as in Example 1 to obtain a resin coating. .

[Example 13] In Example 1, 10 parts of low molecular weight polystyrene ("SX-100" manufactured by Yasuhara Chemical Co., Ltd.) as the component (A) was not used, and styrene-(α-methyl) as the component (A) was added instead. A resin coating was obtained in the same manner as in Example 1, except that 10 parts of styrene)-based polymer ("FTR-0100" manufactured by Mitsui Chemicals Co., Ltd.; Mw1960) was used.

[Example 14] In Example 1, 10 parts of low molecular weight polystyrene ("SX-100" manufactured by Yasuhara Chemical Co., Ltd.) as the component (A) was not used, and a styrene-aromatic hydrocarbon polymer (SX-100) as the component (A) was added instead. Except for 10 parts of "FMR-0150" (Mw2040) manufactured by Mitsui Chemicals Co., Ltd., the same operation was performed as in Example 1 to obtain a resin coating.

[Example 15] In Example 1, 10 parts of low molecular weight polystyrene ("SX-100" manufactured by Yasuhara Chemical Co., Ltd.) as the component (A) was changed to 1 part, and the inorganic filler (with amine-based alkoxy Spherical silica ("SO-C2" manufactured by Yaduma Co., Ltd., average particle diameter 0.5 μm, specific surface area 5.8 m ² /g) surface-treated with a silane compound ("KBM573" manufactured by Shin-Etsu Chemical Industry Co., Ltd.) 170 The resin coating was obtained in the same manner as in Example 1 except that the parts were changed to 145 parts.

[Example 16] In Example 1, 10 parts of low molecular weight polystyrene ("SX-100" manufactured by Yasuhara Chemical Co., Ltd.) as the component (A) was changed to 15 parts, and the inorganic filler (with amine-based alkoxy Spherical silica ("SO-C2" manufactured by Yaduma Co., Ltd., average particle diameter 0.5 μm, specific surface area 5.8 m ² /g) surface-treated with a silane compound ("KBM573" manufactured by Shin-Etsu Chemical Industry Co., Ltd.) 170 The resin coating was obtained in the same manner as in Example 1 except that the parts were changed to 185 parts.

[Comparative example 1] In Example 1, except that 10 parts of low molecular weight polystyrene ("SX-100" manufactured by Yasuhara Chemical Co., Ltd.) was not used as the component (A), the same operation was performed as in Example 1 to obtain a resin coating.

[Comparative example 2] In Example 1, 10 parts of low molecular weight polystyrene ("SX-100" manufactured by Yasuhara Chemical Co., Ltd.) as the component (A) was not used, and (A') other polystyrene (GPPS manufactured by PS Japan Co., Ltd.) was added instead. ; Mw 190,000), except that a resin coating was produced in the same manner as in Example 1. However, the components were incompatible and the coating became gel-like, so evaluation could not be performed.

[Example 21] In Example 1, instead of 10 parts of low molecular weight polystyrene ("SX-100" manufactured by Yasuhara Chemical Co., Ltd.) as the component (A), hydrogenated styrene (Yasuhara Chemical Co., Ltd.) was added as the component (A). Prepare 3 parts of "SG-110" hydrogenated styrene or hydrogenated styrene-based polymer, Mw2000), and surface-treat the inorganic filler (with an amine-based alkoxysilane compound ("KBM573" manufactured by Shin-Etsu Chemical Industry Co., Ltd.) The same procedure as in Example 1 was performed except that 170 parts of spherical silica (manufactured by Yaduma Corporation, "SO-C2", average particle diameter 0.5 μm, specific surface area 5.8 m ² /g) was changed to 155 parts. , get the resin coating.

[Example 22] In Example 21, 43 parts of the active ester-based hardener ("HPC-8150-62T", active group equivalent 223g/eq., non-volatile content 61.5% by mass, toluene solution) was changed to an active ester-based hardener (DIC Co., Ltd. Prepare 40 parts of "HPC-8000-65T", a toluene solution with an active radical equivalent of 223g/eq. and a non-volatile content of 65% by mass. Except for the above matters, it carried out similarly to Example 21, and obtained the resin coating material.

[Example 23] In Example 21, 43 parts of the active ester-based hardener ("HPC-8150-62T", active group equivalent 223 g/eq., toluene solution of 61.5 mass% non-volatile content) was changed to the active ester obtained in Synthesis Example 1 A (toluene solution with active radical equivalent of 238g/eq. and non-volatile content of 61.5% by mass) 43 parts. Except for the above matters, it carried out similarly to Example 21, and obtained the resin coating material.

[Example 24] In Example 21, 43 parts of the active ester-based hardener ("HPC-8150-62T", active group equivalent 223 g/eq., toluene solution of 61.5 mass% non-volatile content) was changed to the active ester obtained in Synthesis Example 2 B (toluene solution with active radical equivalent of 214g/eq. and non-volatile content of 70% by mass) 37 parts. Except for the above matters, it carried out similarly to Example 21, and obtained the resin coating material.

[Example 25] In Example 21, 43 parts of active ester hardener ("HPC-8150-62T", active group equivalent 223g/eq., toluene solution of 61.5 mass% non-volatile content) was changed to active ester hardener (Air Water "PC1300-02-65MA" produced by the company, active group equivalent 199g/eq., non-volatile content 65% by mass of methyl amyl ketone solution) 37 parts. Except for the above matters, it carried out similarly to Example 21, and obtained the resin coating material.

[Example 26] In Example 21, maleimide represented by the following formula (M) synthesized by the method described in Synthesis Example 1 of Japan Invention Association Publication No. 2020-500211 was further used. 2 parts of MEK solution (non-volatile content 62% by mass) of compound A (Mw/Mn=1.81, t”=1.47 (mainly 1, 2 or 3)). Except for the above matters, the same operation as in Example 21 , get the resin coating.

[Example 27] In Example 21, 2 parts of another thermosetting resin (maleimide resin ("MIR-5000-60T" manufactured by Nippon Kayaku Co., Ltd., a toluene solution with a non-volatile content of 60% by mass)) was further used. In addition to the above matters Except for this, the same procedure as in Example 21 was carried out to obtain a resin paint.

[Example 28] In Example 21, 2 parts of another thermosetting resin (maleimide resin ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., a toluene/MEK mixed solution with a non-volatile content of 70% by mass) was further used. In addition to Except for the above matters, it carried out similarly to Example 21, and obtained the resin coating material.

[Example 29] In Example 21, 2 parts of another thermosetting resin (acrylate resin ("A-DOG" manufactured by Shin-Nakamura Chemical Co., Ltd.)) were further used. Except for the above matters, the same operation as in Example 21 was performed to obtain a resin coating.

[Example 30] In Example 21, 2 parts of another thermosetting resin (styrene-based resin ("OPE-2St-1200" manufactured by Mitsubishi Gas Chemical Co., Ltd., a toluene solution with a non-volatile content of 65% by mass)) was further used. In addition to the above matters, The same procedure as in Example 21 was carried out to obtain a resin paint.

[Example 31] In Example 21, the inorganic filler (spherical silica (manufactured by Yaduma Corporation, "SO-C2", average particle diameter 0.5 μm, specific surface area 5.8 m ² /g) was changed from 155 parts to 125 parts, and an inorganic filler having a hollow part (an amine-based alkoxysilane compound (manufactured by Shin-Etsu Chemical Industry Co., Ltd.) was added "KBM573"), except that 30 parts of spherical silica having a hollow portion ("BA-S" manufactured by Nikko Catalyst Chemicals Co., Ltd.) was surface-treated, the same operation was performed as in Example 21 to obtain a resin coating. .

<Test Example 1: Measurement of dielectric constant and dielectric loss tangent> (1) Preparation of resin sheet A with a resin composition layer thickness of 40 μm As a support, a polyethylene terephthalate film ("AL5" manufactured by Lintec Corporation, thickness 38 μm) having a release layer was prepared. On the release layer of the support, the resin paint obtained in the Examples and Comparative Examples was uniformly applied so that the thickness of the dried resin composition layer became 40 μm. Then, the resin composition is dried at 80°C to 100°C (average 90°C) for 4 minutes to obtain a resin sheet A including a support and a resin composition layer.

(2) Preparation of hardened material The resin sheet A obtained in the Examples and Comparative Examples was cured in an oven at 190° C. for 90 minutes. The support is peeled off from the resin sheet A taken out from the oven, thereby obtaining a cured product of the resin composition layer. The hardened material was cut into a size of 80 mm in length and 2 mm in width to prepare a hardened material for evaluation.

(3) Measurement of dielectric constant and dielectric loss tangent For each hardened product for evaluation, the dielectric constant and dielectric loss angle were measured using the resonant cavity perturbation method using "HP8362B" manufactured by Agilent Technologies at a measurement frequency of 5.8 GHz and a measurement temperature of 23°C and 90°C. Tangent value (Dk value, Df value). Measurement was performed on two test pieces, and the average value was calculated.

<Test Example 2: Evaluation of crack resistance after desmear treatment> (1) Preparation of resin sheet B with a resin composition layer thickness of 25 μm As a support, a polyethylene terephthalate film ("AL5" manufactured by Lintec Corporation, thickness 38 μm) having a release layer was prepared. On the release layer of the support, the resin coating obtained in the Examples and Comparative Examples was evenly applied so that the thickness of the dried resin composition layer became 25 μm, and the process was carried out at 70°C to 80°C (average 75°C) for 2.5 minutes. After drying, a resin sheet B including a support and a resin composition layer is obtained.

(2) Evaluation of crack resistance after desmearing: Circular copper pads (copper thickness: 35 μm) with a diameter of 350 μm were formed into a grid shape at intervals of 400 μm so that the residual copper rate became 60%. On both sides of the core material ("E705GR" manufactured by Hitachi Chemical Industry Co., Ltd., thickness 400 μm), an intermittent vacuum pressure laminator (2-stage stacking laminator "CVP700" manufactured by Nikko-Materials Co., Ltd.) is used, and the resin composition layer is In the aforementioned method of bonding the inner layer substrates, the resin sheet B with a thickness of 25 μm produced above is laminated on both sides of the inner layer substrate. This lamination was performed by depressurizing for 30 seconds until the air pressure became 13 hPa or less, and then performing pressure bonding for 30 seconds under the conditions of a temperature of 100° C. and a pressure of 0.74 MPa. This was put into an oven at 130°C and heated for 30 minutes, and then transferred to an oven at 170°C and heated for 30 minutes. Furthermore, the support layer was peeled off, and the obtained circuit board was immersed in Swelling Dip Securiganth P of Atotech Japan Co., Ltd. as a swelling liquid at 60° C. for 10 minutes. Next, it was immersed in Atotech Japan Co., Ltd.'s Concentrate Compact P (aqueous solution of KMnO ₄ : 60 g/L, NaOH: 40 g/L) as a roughening liquid at 80° C. for 30 minutes. Finally, it was immersed in Reduction Solution Securiganth P of Atotech Japan Co., Ltd. as a neutralizing solution at 40° C. for 5 minutes. 100 copper pad portions of the circuit board after the roughening treatment were observed to confirm whether there were cracks in the resin composition layer. If the number of cracks is 10 or less, the evaluation is "0", and if the number of cracks is more than 10, the evaluation is "×".

<Test Example 3: Measurement of glass transition temperature (Tg)> The resin sheet A obtained in Test Example 1 was cured in an oven at 190° C. for 90 minutes, and further peeled from the support to obtain a cured film. The cured film was cut into a size of 20 mm in length and 6 mm in width to prepare an evaluation sample. For this evaluation sample, the glass transition temperature (Tg) was measured by raising the temperature from 25°C to 250°C at a temperature increase rate of 5°C/min using a TMA device (thermomechanical analysis device) manufactured by Rigaku Corporation. Measure the same test piece twice and record the second value.

Table 1 below shows the usage amounts (parts by mass) of components (A) to (G) including volatile components in the resin compositions of Examples and Comparative Examples, and the measurement results of the test examples. In Table 1, the nonvolatile content (mass %) of each component is shown in the "N.V." column.

From the above, it can be understood that by using a resin composition containing (A) a styrenic and/or hydrogenated styrene polymer having a weight average molecular weight of 10,000 or less, (B) an epoxy resin, and (C) an active ester compound, A hardened product with excellent crack resistance after desmear treatment can be obtained. It is also found that this hardened product has a low dielectric loss tangent (Df) in any environment including room temperature or normal temperature ranges such as 23°C and high temperature environments such as 90°C. In any environment, the relative dielectric constant (Dk) is low and the glass transition temperature is high.

Claims (13)

A resin composition containing: (A) Styrenic and/or hydrogenated styrenic polymers with a weight average molecular weight of 10,000 or less, (B) Epoxy resin, and (C) Active ester compound. The resin composition of claim 1, wherein the component (C) has a carbon-carbon double bond. The resin composition of claim 1, wherein the component (C) contains: an active ester compound containing a styrene group and a naphthalene structure. The resin composition of claim 1, further comprising (E) a radically polymerizable compound. The resin composition of claim 4, wherein (E) the radically polymerizable compound contains: (E1) a maleimide compound. The resin composition of claim 5, wherein (E1) the maleimide compound contains: (E1-2) a maleimide compound containing a trimethylindane skeleton. The resin composition of claim 1, further comprising (D) an inorganic filler. The resin composition of claim 1 is used to form an interlayer insulating layer of a printed wiring board. A cured product of the resin composition according to any one of claims 1 to 8. A sheet-like laminated material containing the resin composition according to any one of claims 1 to 8. A resin sheet having: support, and A resin composition layer formed of the resin composition according to any one of claims 1 to 8 provided on the support. A printed wiring board provided with an insulating layer formed of a cured product of the resin composition according to any one of claims 1 to 8. A semiconductor device including the printed wiring board according to claim 12.