JP2023131714A - resin composition - Google Patents

Abstract

To provide a resin composition that can yield a cured product having excellent crack resistance after desmear treatment.SOLUTION: A resin composition contains (A) a styrenic and/or hydrogenated styrenic polymer with a weight average molecular weight of 10000 or less, (B) an epoxy resin, and (C) an active ester compound.SELECTED DRAWING: None

Description

The present invention relates to a resin composition containing an epoxy resin. Furthermore, the present invention relates to a cured product, a sheet-like laminate material, a resin sheet, a printed wiring board, and a semiconductor device obtained using the resin composition.

As a manufacturing technique for printed wiring boards, a manufacturing method using a build-up method in which insulating layers and conductive layers are alternately stacked is known. In the build-up manufacturing method, the insulating layer is generally formed by curing a resin composition. In recent years, there has been a demand for further improvements in dielectric properties such as permittivity of insulating layers, and further improvements in copper adhesion.

Until now, we have been able to lower the dielectric loss tangent of the insulating layer by using an epoxy resin composition containing an active ester compound instead of a general phenolic curing agent as a resin composition for forming the insulating layer. It is known that this can be suppressed (Patent Document 1).

Japanese Patent Application Publication No. 2020-23714

However, when an active ester compound is used, although the dielectric loss tangent can be kept lower, cracks tend to occur more easily after desmear treatment.

An object of the present invention is to provide a resin composition from which a cured product can be obtained that can suppress the occurrence of cracks after desmear treatment.

In order to achieve the objects of the present invention, the inventors of the present invention have conducted intensive studies and found that as components of the resin composition, an epoxy resin and an active ester compound are used, and a styrene polymer having a weight average molecular weight of 10,000 or less is used. The present inventors have surprisingly found that by containing a hydrogenated styrene polymer and/or a hydrogenated styrene polymer, it is possible to obtain a cured product that can suppress the occurrence of cracks after desmear treatment, and have completed the present invention.

That is, the present invention includes the following contents.
[1]
A resin composition comprising (A) a styrenic and/or hydrogenated styrenic 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 [1] above, wherein component (C) has a carbon-carbon double bond.
[3]
The resin composition according to [1] or [2] above, wherein component (C) contains an active ester compound containing a styryl group and a naphthalene structure.
[4]
The resin composition according to any one of [1] to [3] above, further comprising (E) a radically polymerizable compound.
[5]
(E) The resin composition according to the above [4], wherein the radically polymerizable compound contains (E1) a maleimide compound.
[6]
(E1) The resin composition according to [5] above, wherein the maleimide compound includes (E1-2) a maleimide compound containing a trimethylindane skeleton.
[7]
The resin composition according to any one of [1] to [6] above, further comprising (D) an inorganic filler.
[8]
The resin composition according to any one of [1] to [7] above, which is used for forming an interlayer insulating layer of a printed wiring board.
[9]
A cured product of the resin composition according to any one of [1] to [8] above.
[10]
A sheet-like laminate material containing the resin composition according to any one of [1] to [8] above.
[11]
A resin sheet comprising a support and a resin composition layer formed from the resin composition according to any one of [1] to [8] above, provided on the support.
[12]
A printed wiring board comprising an insulating layer made of a cured product of the resin composition according to any one of [1] to [8] above.
[13]
A semiconductor device comprising the printed wiring board according to [12] above.

According to the present invention, a resin composition capable of obtaining a cured product with excellent crack resistance after desmear treatment; a cured product of the resin composition; a sheet-like laminate material and a resin sheet containing the resin composition; and A printed wiring board and a semiconductor device including a cured product of the resin composition can be provided.

Hereinafter, the present invention will be described in detail by showing embodiments and examples. However, the present invention is not limited to the following embodiments and examples, and may be implemented with arbitrary changes within the scope of the claims of the present invention and equivalents thereof.

In the following description, the amounts of each component are those of non-volatile components, unless otherwise specified.
In the following description, "nonvolatile components in the resin composition" may include (D) inorganic fillers, unless otherwise specified, but "resin components" refer to the resin composition, unless otherwise specified. It refers to the non-volatile components contained in (D) excluding the inorganic filler.

<Resin composition>
The resin composition of the present invention contains (A) a styrenic and/or hydrogenated styrenic 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 with excellent crack resistance after desmear treatment can be obtained. Further, in the present invention, the dielectric loss tangent is usually low both in a room temperature range such as 23°C and a high temperature environment such as 90°C. In either case, a cured product having a low dielectric constant and a high glass transition temperature can be obtained.

In addition to (A) a styrenic and/or hydrogenated styrenic polymer having a weight average molecular weight of 10,000 or less, (B) an epoxy resin, and (C) an active ester compound, the resin composition of the present invention further comprises It may contain ingredients. Examples of optional components include (D) an inorganic filler, (E) a radically polymerizable compound, (F) other curing agents, (G) a curing accelerator, (H) other additives, and (K) Examples include organic solvents. In this specification, each of the above components (A) to (K) may also be referred to as "component (A)", "component (B)", etc., respectively. Each component contained in the resin composition will be explained in detail below.

<(A) Styrenic and/or hydrogenated styrenic polymer having 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 it has a weight average molecular weight (Mw) of 10,000 or less. Furthermore, it may contain monomers such as styrene and hydrogenated styrene. In this specification, the component (A) may be simply referred to as "styrenic and/or hydrogenated styrenic polymer."

Since the styrenic and/or hydrogenated styrene polymers having such molecular weights have a relatively small molecular weight, they have low melt viscosity, excellent resin flowability of the resin composition, and can improve moldability. Furthermore, due to its relatively small molecular weight, although it is a styrene-based and/or hydrogenated styrene-based polymer with a hydrophobic skeleton, it is compatible with not only hydrophobic solvents such as toluene and hexane, but also polar solvents such as methyl ethyl ketone. Shows high solubility. Therefore, a varnish-like resin composition (resin varnish) can be easily produced using the maleimide compound having a polar group and methyl ethyl ketone. Furthermore, 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 styrene-based polymer used in this embodiment, a wide range of conventionally known polymers can be used, and is not particularly limited, but specifically, for example, styrene, hydrogenated styrene, styrene derivatives, etc. , styrene such as α-methylstyrene in which some of the hydrogen atoms in the benzene ring are substituted with alkyl groups, styrene in which some of the hydrogen atoms in the vinyl group in styrene are substituted with alkyl groups, vinyltoluene, isopropenyltoluene, etc. Polymers or copolymers obtained by polymerizing or copolymerizing one or more styrenic monomers, and hydrogenated products thereof.

As the styrenic and/or hydrogenated styrenic polymer, specifically, for example, those containing structures represented by the following formulas (A-1) and (A-2) and hydrogenated compounds thereof are preferable. Examples include:

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

In addition, styrenic and/or hydrogenated styrenic copolymers are obtained by copolymerizing one or more styrene monomers and one or more other monomers copolymerizable with the styrenic monomers. It is also possible to use copolymers. The copolymerizable monomer may be an aliphatic hydrocarbon, an aromatic hydrocarbon, or a combination thereof, such as olefins such as α-pinene, β-pinene, and dipentene, and nonconjugated dienes. Examples include unsaturated compounds such as.

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

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

As such styrene-based and/or hydrogenated styrene-based polymers, commercial products can also be used, such as FTR6125 (styrene-aliphatic hydrocarbon-based copolymer, Mw 1950) manufactured by Mitsui Chemicals, Inc. FTR (registered trademark) series such as FTR2140 (styrene-(α-methylstyrene) copolymer, Mw 3230), FTR0100 (α-methylstyrene polymer, Mw 1960), FTR8120 (styrene polymer, Mw 1420); Mitsui FMR series such as FMR0150 (styrene-aromatic hydrocarbon copolymer, Mw 2040) manufactured by Kagaku Co., Ltd.; SX-100 (styrene polymer, Mw 2000), SG-100 (hydrogenated styrene type) manufactured by Yasuhara Chemical Polymer), SG-110 (hydrogenated styrene polymer), etc. may also be used.

The above styrenic and/or hydrogenated styrenic polymers may be used alone or in combination of two or more.

The weight average molecular weight (Mw) of the styrenic and/or hydrogenated styrenic polymer used in this embodiment is 10,000 or less. By including a styrene-based and/or hydrogenated styrene-based polymer having an Mw of 10,000 or less, a cured product with excellent crack resistance after desmear treatment can be obtained. Preferably, it is about 1000 to 9000. More preferably, it is about 1,000 to 7,000, still more preferably about 1,000 to 5,000, even more preferably about 1,000 to 4,000. The weight average molecular weight of component (A) is a polystyrene equivalent weight average molecular weight measured by gel permeation chromatography (GPC).

The content of component (A) is, for example, 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 1 to 1.0% by mass, based on 100% by mass of the nonvolatile components in the resin composition. Above, more preferably 3 to 3.0% by mass or more, still more preferably 4 to 4.0% by mass or more, and for example 15% by mass or less, preferably 10% by mass or less, more preferably 8% by mass or more. to 8.0% by mass or less, more preferably 6.5% by mass or less, even more preferably 5 to 5.0% by mass, particularly preferably 4.5% by mass or less, and specifically, non-aqueous When using an additional styrenic polymer, these contents are suitable, and when using a hydrogenated styrenic polymer, these contents may be used, but suitably, for example, 2 to 4% by mass, preferably may be 2.5 to 3% by mass.

The content of component (A) is, for example, 1% by mass or more, 1.5% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, based on 100% by mass of the resin component in the resin composition. , more preferably 13% by mass or more, even more preferably 15 to 15.0% by mass or more, particularly preferably 16 to 16.0% by mass or more, and for example 30% by mass or less, preferably 25% by mass. % or less, more preferably 23.5% by mass or less, even more preferably 20% by mass or less, and even more preferably 18 to 18.0% by mass. Specifically, the non-hydrogenated styrenic polymer When using, these contents are suitable, and when using a hydrogenated styrene polymer, these contents may be used, but suitably, for example, 3 to 15% by mass, preferably 5 to 10% by mass, More preferably, it may be 5.5 to 6% by mass.

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

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

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

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

As the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferable.

Liquid epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, phenol novolak type epoxy resin, and ester skeleton. Preferred are alicyclic epoxy resins, cyclohexane-type epoxy resins, cyclohexanedimethanol-type epoxy resins, and epoxy resins having a butadiene structure.

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

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

Solid epoxy resins include bixylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, naphthol novolac type epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, Naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, phenol aralkyl type epoxy resin, tetraphenylethane type epoxy resin, phenolphthalyl Midine type epoxy resins and phenolphthalein type epoxy resins are preferred.

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

(B) When using a liquid epoxy resin and a solid epoxy resin together as the epoxy resin, the mass ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin/solid epoxy resin) is not particularly limited. However, it is preferably 10 or less, more preferably 5 or less, and still more preferably 1 or less.

(B) The epoxy equivalent of the epoxy resin is preferably 50 g/eq. ～5,000g/eq. , more preferably 60g/eq. ~2,000g/eq. , more preferably 70g/eq. ～1,000g/eq. , even more preferably 80 g/eq. ～500g/eq. It is. Epoxy equivalent is the mass of resin per equivalent of epoxy group. This epoxy equivalent can be measured according to JIS K7236.

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

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

The content of component (B) is, for example, 10% by mass or more, preferably 15% by mass or more, more preferably 20% by mass or more, still more preferably 25% by mass, based on 100% by mass of the resin component in the resin composition. Above, even more preferably 30% by mass or more, particularly preferably 32% by mass or more, and, for example, 60% by mass or less, preferably 55% by mass or less, more preferably 50% by mass or less, still more preferably 45% by mass or less. It is not more than 40% by weight, even more preferably not more than 40% by weight, particularly preferably not more than 36% by weight.

<(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 alone or in combination of two or more in any ratio, and the same applies to the components (C1) and (C2) described below. (C) The active ester compound may have the function of reacting with the (B) epoxy resin to crosslink the (B) epoxy resin. (C) The active ester compound may have a carbon-carbon unsaturated bond, and this unsaturated bond is preferably a carbon-carbon double bond, for example, the component (C1) described below. The carbon-carbon unsaturated bond may be the same as the carbon-carbon unsaturated bond that has.

(C) Active ester compounds generally have two or more ester groups with high reaction activity in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds. Compounds having the following properties are preferably used. The active ester compound is preferably one obtained by a condensation reaction between a carboxylic acid compound and/or a thiocarboxylic acid compound and a hydroxy compound and/or a thiol compound. Particularly from the viewpoint of improving heat resistance, active ester compounds obtained from a carboxylic acid compound and a hydroxy compound are preferred, and active ester compounds obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound are more preferred. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of phenolic compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, Examples include benzenetriol, dicyclopentadiene type diphenol compounds, and phenol novolacs. Here, the term "dicyclopentadiene type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

Specifically, the active ester compound (C) includes a dicyclopentadiene type active ester compound, a naphthalene type active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, and a benzoylated product of phenol novolac. Active ester compounds are preferred, and among them, at least one selected from dicyclopentadiene-type active ester compounds and naphthalene-type active ester compounds is more preferred, 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 preferable. "Dicyclopentadiene type diphenol structure" refers to a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.

(C) Commercially available active ester compounds containing a dicyclopentadiene diphenol structure include "EXB9451," "EXB9460," "EXB9460S," "EXB-8000L," and "EXB-8000L-65M. ”, “EXB-8000L-65TM”, “HPC-8000L-65TM”, “HPC-8000”, “HPC-8000-65T”, “HPC-8000H”, “HPC-8000H-65TM”, (Manufactured by DIC ); "EXB-8100L-65T", "EXB-8150-60T", "EXB-8150-62T", "EXB-9416-70BK", "HPC-8150-60T" as active ester compounds containing a naphthalene structure, "HPC-8150-62T" (manufactured by DIC Corporation); "EXB9401" (manufactured by DIC Corporation) as a phosphorus-containing active ester compound; "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester compound that is an acetylated product of phenol novolak , "YLH1026", "YLH1030", "YLH1048" (manufactured by Mitsubishi Chemical Corporation) as active ester compounds which are benzoylated products of phenol novolak, "PC1300-02-65MA" (air) as active ester compounds containing a styryl group and naphthalene structure・Manufactured by Water Co.), etc.

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

<(C1) Aromatic ester skeleton and unsaturated bond-containing compound>
As the active ester compound (C), (C1) a compound containing an aromatic ester skeleton and an unsaturated bond (herein also referred to as "component (C1)") may be used.

（一般式（ＡＥ１－１）中、Ａｒ^１１は、それぞれ独立に置換基を有していてもよい１価の芳香族炭化水素基を表し、Ａｒ^１２は、それぞれ独立に、置換基を有していてもよい２価の芳香族炭化水素基を表し、Ａｒ^１３は、それぞれ独立に、置換基を有していてもよい２価の芳香族炭化水素基、置換基を有していてもよい２価の脂肪族炭化水素基、酸素原子、硫黄原子、又はこれらの組み合わせからなる２価の基を表す。ｎは０～１０の整数を表す。） 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 which may have a substituent, and Ar ¹² each independently has a substituent. 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; Represents a divalent aliphatic hydrocarbon group, an oxygen atom, a sulfur atom, or a divalent group consisting of a combination thereof. n represents an integer from 0 to 10.)

Examples of the monovalent aromatic hydrocarbon group represented by Ar ¹¹ include phenyl group, furanyl group, pyrrolyl group, thiophene group, imidazolyl group, pyrazolyl group, oxazolyl group, isoxazolyl group, thiazolyl group, isothiazolyl group, pyridinyl group, Monocyclic aromatic compounds with one hydrogen atom removed such as pyrimidinyl, pyridazinyl, pyrazinyl, and triazinyl groups; naphthyl, anthracenyl, phenalenyl, phenanthrenyl, quinolinyl, isoquinolinyl, quinazolyl groups, Examples include fused ring aromatic compounds from which one hydrogen atom has been removed, such as a phthalazinyl group, a pteridinyl group, a coumarinyl group, an indole group, a benzimidazolyl group, a benzofuranyl group, and an acridinyl group; among these, a phenyl group is preferred.

Examples of the divalent aromatic hydrocarbon group represented by Ar ¹² include an arylene group and an aralkylene group, with an arylene group being preferred. The arylene group is preferably an arylene group having 6 to 30 carbon atoms, more preferably an arylene group having 6 to 20 carbon atoms, and even more preferably an arylene group having 6 to 10 carbon atoms. Examples of such an arylene group include a phenylene group, a naphthylene group, an anthracenylene group, and a biphenylene group. Among these, a phenylene group is preferred.

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

（式（ａ）～（ｄ）中、「＊」は結合手を表す。） The cycloalkylene group is preferably a cycloalkylene group having 3 to 20 carbon atoms, more preferably a cycloalkylene group having 3 to 15 carbon atoms, and even more preferably a cycloalkylene group having 5 to 10 carbon atoms. Examples of the cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cyclopentylene group, a cycloheptylene group, and a cycloalkylene group represented by the following formulas (a) to (d). are mentioned, and a cycloalkylene group represented by formula (c) is preferred.

(In formulas (a) to (d), "*" represents a bond.)

A monovalent aromatic hydrocarbon group represented by Ar ¹¹ , a divalent aromatic hydrocarbon group represented by Ar ¹² , and a divalent aromatic hydrocarbon group and a divalent aliphatic hydrocarbon group represented by Ar ¹³ are present. Examples of optional substituents include unsaturated hydrocarbon groups, alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, and halogen atoms. The substituents may be contained alone or in combination of two or more types. Among others, the substituent of Ar ¹¹ preferably contains an unsaturated bond.

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

Specific examples of component (C1) include the following compounds. Further, 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 1 or more, 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, even more preferably 250 or more, and preferably 3000 or less, more preferably 2000 or more, from the viewpoint of significantly obtaining the effects of the present invention. It is preferably 1500 or less. The weight average molecular weight of 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 the component (C1) is preferably 50 g/eq or more, more preferably 100 g/eq. Above, more preferably 150g/eq. and preferably 2000g/eq. Below, more preferably 1000g/eq. Below, more preferably 500g/eq. It is as follows. The active ester equivalent (unsaturated bond equivalent) is the mass of component (C1) containing 1 equivalent of unsaturated bond.

（式中、＊は結合手を表す。式（３）中、ｎは１～５の整数を表す。） <(C2) 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) an active ester compound having at least one of the groups represented by the following formulas (1) to (3) (herein also referred to as "component (C2)") ) may be used.

(In the formula, * represents a bond. In formula (3), n represents an integer from 1 to 5.)

As component (C2), a compound having at least one of the groups represented by formulas (1) to (3) and an active ester moiety capable of reacting with component (A) can be used. The component (C2) preferably has at least one of the groups represented by formulas (1) to (3) at its terminal. The component (C2) may have different groups at both ends, or may have the same group at both ends.

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) each correspond to the bond represented by *. It is preferable that the compound be bonded to one of the ortho, meta, and para positions, and more preferably the ortho position.

（一般式（ＡＥ２－１）中、Ａｒ^１１は、それぞれ独立に式（１）で表される基、式（２）で表される基、又は式（３）で表される基を表し、Ａｒ^１２は、それぞれ独立に、置換基を有していてもよい２価の芳香族炭化水素基を表し、Ａｒ^１３は、それぞれ独立に、置換基を有していてもよい２価の芳香族炭化水素基、置換基を有していてもよい２価の脂肪族炭化水素基、酸素原子、硫黄原子、又はこれらの組み合わせからなる２価の基を表す。ａは１～６の整数を表し、ｂは０～１０の整数を表す。） 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), Ar ¹² each 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. Represents a hydrocarbon group, a divalent aliphatic hydrocarbon group which may have a substituent, an oxygen atom, a sulfur atom, or a divalent group consisting of a combination thereof. a represents an integer from 1 to 6. , 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 preferable.

Ar ¹² and Ar ¹³ are the same as Ar ¹² and Ar ¹³ in general formula (AE1-1 ⁾ , respectively, but the divalent aromatic hydrocarbon group represented by Ar ¹² and the 2 Examples of the substituent that the valent aromatic hydrocarbon group and the divalent aliphatic hydrocarbon group may have 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, a halogen atom, and the like. The substituents may be contained alone or in combination of two or more types.

The divalent group consisting of a combination of these represented by Ar ¹³ is preferably a divalent group combining a divalent aromatic hydrocarbon group which may have a substituent and an oxygen atom, and one or more substituents. A divalent aromatic hydrocarbon group that may have a group, and a divalent group that alternately combines one or more oxygen atoms are more preferable, and a naphthylene group that may have one or more substituents. and a divalent group in which one or more oxygen atoms are alternately combined. Therefore, a naphthyleneoxy group which may have a substituent is more preferred.

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

（一般式（ＡＥ２－２）中、Ａｒ^２１は、それぞれ独立に式（１）で表される基、式（２）で表される基、又は式（３）で表される基を表し、Ａｒ^２２は、それぞれ独立に、置換基を有していてもよい２価の芳香族炭化水素基を表し、Ａｒ^２３は、それぞれ独立に、置換基を有していてもよい２価の芳香族炭化水素基を表す。ａ１は１～６の整数を表し、ｃ１は１～５の整数を表す。） 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), Ar ²² 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. Represents a hydrocarbon group. a1 represents an integer of 1 to 6, and c1 represents an integer of 1 to 5.)

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

Ar ²³ is the same as the divalent aromatic hydrocarbon group which may have a substituent as Ar ¹³ in general formula (AE2-1).
a1 is the same as a in general formula (AE2-1).

（一般式（ＡＥ２－３）中、Ａｒ^３１は、それぞれ独立に式（１）で表される基、式（２）で表される基、又は式（３）で表される基を表す。ａ２は１～６の整数を表し、ｃ２は１～５の整数を表し、ｄはそれぞれ独立に０～６の整数を表す。） 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 an integer from 1 to 6, 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 general formula (AE2-1). a2 and c2 are the same as a and c1 in general formula (AE2-1), respectively.

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

Component (C2) may be synthesized by a known method, for example, by the method described in the Examples below. Component (C2) can be synthesized, for example, by the method described in International Publication No. 2018/235424 or International Publication No. 2018/235425.

The weight average molecular weight of the component (C2) is preferably 150 or more, more preferably 200 or more, even more preferably 250 or more, and preferably 4000 or less, more preferably 3000 or more, from the viewpoint of significantly obtaining the effects of the present invention. It is preferably 2,500 or less. The weight average molecular weight of 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).

The quantitative ratio of component (B) and component (C) is determined by adding up the mass of the nonvolatile component of component (B) divided by the epoxy equivalent, and setting the mass of the nonvolatile component of component (C) to a. When b is the sum of all the values divided by the active ester group equivalent, b/a is preferably 1.0 or more, more preferably 1.01 or more, even more preferably 1.03 or more, 1 It is even more preferably .05 or more, particularly preferably 1.06 or more, preferably 2.0 or less, more preferably 1.5 or less, even more preferably 1.2 or less, and even more preferably 1.18 or less. More preferably, 1.17 or less is particularly preferable. By controlling the ratio of the components (B) and (C) to within this range, the effects of the present invention can be easily obtained.

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

The content of component (C) is, for example, 30% by mass or more, preferably 35% by mass or more, more preferably 40% by mass or more, even more preferably 42% by mass, based on 100% by mass of the resin component in the resin composition. or more, and is, for example, 70% by mass or less, preferably 60% by mass or less, more preferably 50% by mass or less, still more preferably 45% by 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) The inorganic filler may be used alone or in any combination of two or more types.

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

(D) Commercially available inorganic fillers include, for example, "SP60-05" and "SP507-05" manufactured by Nippon Steel Chemical &Materials; "SC2500SQ", "SO-C4" and "SP507-05" manufactured by Admatex Corporation; "SO-C2", "SO-C1", "YC100C", "YA050C", "YA050C-MJE", "YA010C"; Denka's "UFP-30", "DAW-03", "FB-105FD" ; “Silfill NSS-3N”, “Silfill NSS-4N”, “Silfill NSS-5N” manufactured by Tokuyama; “MGH-005” manufactured by Taiheiyo Cement; “BA-S” manufactured by JGC Catalysts & Chemicals, etc. Can be mentioned.

(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, even more preferably 2 μm or less, even more preferably 1 μm or less, and particularly preferably 0.5 μm or less. It is 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, even more preferably 0.1 μm or more, particularly preferably 0. .2 μm or more. (D) The average particle size of the inorganic filler can be measured by a laser diffraction/scattering method based on Mie scattering theory. Specifically, it can be measured by creating the particle size distribution of the inorganic filler on a volume basis using a laser diffraction scattering type particle size distribution measuring device, and using the median diameter as the average particle size. The measurement sample can be obtained by weighing 100 mg of the inorganic filler and 10 g of methyl ethyl ketone into a vial and dispersing them using ultrasonic waves for 10 minutes. The measurement sample was measured using a laser diffraction particle size distribution measuring device using a light source wavelength of blue and red, and the volume-based particle size distribution of the inorganic filler was measured using a flow cell method. The average particle size was calculated as the median diameter. Examples of the laser diffraction particle size distribution measuring device include "LA-960" manufactured by Horiba, 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, even more preferably 1 m ² /g or more, Particularly preferably, it is 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, even more preferably 50 m ² /g or less, particularly preferably is 40 m ² /g or less. The specific surface area of the inorganic filler is determined by adsorbing nitrogen gas onto the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountec) according to the BET method, and calculating the specific surface area using the BET multipoint method. You can get it by doing that.

(D) The inorganic filler is preferably surface-treated with an appropriate surface treatment agent. The surface treatment can improve the moisture resistance and dispersibility of the inorganic filler (D). Examples of surface treatment agents include vinyl silane coupling agents such as vinyltrimethoxysilane and vinyltriethoxysilane; 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and 3-glycidoxypropylmethyldimethoxysilane. , 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane and other epoxy-based silane coupling agents; styryl-based such as p-styryltrimethoxysilane Silane coupling agent; methacrylic silane coupling agent such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane; Acrylic silane coupling agents such as 3-acryloxypropyltrimethoxysilane; N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane , 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N - Amino-based silane coupling agents such as phenyl-8-aminooctyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane; tris-(trimethoxysilylpropyl)isocyanurate, etc. Isocyanurate-based silane coupling agents; ureido-based silane coupling agents such as 3-ureidopropyltrialkoxysilane; mercapto-based silane coupling agents such as 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc. ; Isocyanate-based silane coupling agents such as 3-isocyanatepropyltriethoxysilane; Acid anhydride-based silane coupling agents such as 3-trimethoxysilylpropylsuccinic anhydride; Silane coupling agents such as methyltrimethoxysilane; Dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltrimethoxysilane Examples include non-silane coupling alkoxysilane compounds such as ethoxysilane, decyltrimethoxysilane, 1,6-bis(trimethoxysilyl)hexane, and trifluoropropyltrimethoxysilane. Furthermore, the surface treatment agents may be used alone or in combination of two or more in any ratio.

Commercially available surface treatment agents include, for example, "KBM-1003", "KBE-1003" (vinyl silane coupling agent); "KBM-303", "KBM-402", and "KBE-1003" manufactured by Shin-Etsu Chemical Co., Ltd. KBM-403", "KBE-402", "KBE-403" (epoxy silane coupling agent); "KBM-1403" (styryl 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-based silane coupling agent); ``KBM-9659'' (isocyanurate-based silane coupling agent); "KBE-585" (ureide silane coupling agent); "KBM-802", "KBM-803" (mercapto silane coupling agent); "KBE-9007N" (isocyanate silane coupling agent); "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.

The degree of surface treatment with the surface treatment agent is preferably within a predetermined range from the viewpoint of improving the dispersibility of the inorganic filler. Specifically, 100% by mass of the inorganic filler is preferably surface-treated with a surface treatment agent of 0.2% by mass to 5% by mass, and preferably 0.2% by mass to 3% by mass. It is more preferable that the surface is treated in an amount of 0.3% by mass to 2% by mass.

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

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

The content of the inorganic filler (D) in the resin composition is not particularly limited, but when the nonvolatile component in the resin composition is 100% by mass, it is preferably 90% by mass or less, more preferably It may be 85% by weight or less, more preferably 80% by weight or less, even more preferably 75% by weight or less. The lower limit of the content of the inorganic filler (D) in the resin composition is not particularly limited, but when the nonvolatile component in the resin composition is 100% by mass, for example, 0% by mass or more, 1% by mass. % or more, 10% by mass or more, 20% by mass or more, 30% by mass or more, etc., preferably 40% by mass or more, more preferably 50% by mass or more, still more preferably 60% by mass or more, even more preferably 70% by mass or more. It can be at least 73% by weight, particularly preferably at least 73% by weight.

<(E) Radical polymerizable compound>
The resin composition of the present invention may contain (E) a radically polymerizable compound as an optional component. (E) The radically polymerizable compound may be used alone or in any combination of two or more.

The type of 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. The radically polymerizable compound includes, for example, one type of radically polymerizable unsaturated group selected from a maleimide group, a vinyl group, an allyl group, a styryl group, a vinylphenyl group, an acryloyl group, a methacryloyl group, a fumaroyl group, and a maleoyl group. Examples include compounds having the above. Among these, it is preferable to contain (E1) a maleimide compound and/or (E2) other radically polymerizable compounds, from the viewpoint of easily obtaining a cured product with excellent dielectric properties. (E2) Other radically polymerizable compounds are compounds that do not have a maleimide group and have a radically polymerizable unsaturated group other than a maleimide group, and among them, one or more types selected from (meth)acrylic resins and styryl resins. It is preferable to include.

(E1) As long as the maleimide compound has one or more (preferably two or more) maleimide groups (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl group) in one molecule, , the type is not particularly limited. Examples of maleimide compounds include "BMI-3000J," "BMI-5000," "BMI-1400," "BMI-1500," "BMI-1700," and "BMI-689" (all from Digicner Molecules). A maleimide resin containing an aliphatic skeleton with 36 carbon atoms derived from dimer diamine, such as "MIR- 3000-70MT", "MIR-5000-60T" (all manufactured by Nippon Kayaku Co., Ltd.), "BMI-4000" (manufactured by Daiwa Kasei Co., Ltd.), "BMI-80" (manufactured by KI Kasei Co., Ltd.), etc. Examples include maleimide resins containing an aromatic ring skeleton that is directly bonded to the nitrogen atom.

(E1) The maleimide compound preferably includes a maleimide compound containing an indane skeleton (herein also referred to as "(E1-1) specific maleimide compound"), and (E1-2) trimethylindan. It is more preferable to include a maleimide compound containing a skeleton. (E1-1) The specific maleimide compound can be produced, for example, by the method described in Japan Institute of Invention and Innovation Publication No. 2020-500211. According to the production method described in Japan Institute of Invention and Innovation Publication Technical Report No. 2020-500211, a maleimide compound having a distribution in the number of repeating units of the trimethylindane skeleton can be obtained. The maleimide compound obtained by this method includes 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 is each independently 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 6 carbon atoms. -10 aryl group, C6-10 aryloxy group, C6-10 arylthio group, C3-10 cycloalkyl group, halogen atom, nitro group, hydroxyl group, or mercapto group R ² is each independently 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, an aryl group having 6 to 10 carbon atoms; group, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a hydroxyl group, or a mercapto group; n ₁ is represents an average repeating unit number of 0.95 to 10.0; n ₂ each independently represents an integer of 0 to 4; n ₃ each independently represents an integer of 0 to 3 ^; The hydrogen atom of the alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, and cycloalkyl group may be substituted with a halogen atom.R2 ^'s alkyl group, alkyloxy group, alkylthio group The hydrogen atom of the group, aryl group, aryloxy group, arylthio group, and cycloalkyl group may be substituted with a halogen atom. When _{n 2} is 2 to 4, R ¹ is the same within the same ring. (They may be present or different. When _{n 3} is 2 to 3, R ² may be the same or different within the same ring.)

In formula (M1), n ₁ represents the average number of repeating units, and its range is 0.95 to 10.0. According to the production method described in Japan Institute of Invention and Innovation Publication No. 2020-500211, a group of maleimide compounds containing the structure represented by formula (M1) can be obtained. As can be seen from the fact that the average number of repeating units n ₁ in formula (M1) can be smaller than 1.00, the maleimide compound containing the structure represented by formula (M1) thus obtained has a repeating trimethylindane skeleton. A maleimide compound having 0 units may be included. Therefore, a specific maleimide compound (E1-1) is obtained by purification from a maleimide compound containing the structure represented by formula (M1), excluding the maleimide compound in which the number of repeating units of the trimethylindane skeleton is 0. (E1-1) The resin composition may contain only the specific maleimide compound. However, even when the resin composition contains a maleimide compound in which the number of repeating units in the trimethylindane skeleton is 0, the effects of the present invention can be obtained. Furthermore, when purification is omitted, costs can be reduced. Therefore, it is preferable that the resin composition contains a maleimide compound having a structure represented by formula (M1) without excluding a maleimide compound having a repeating unit number of 0 in the trimethylindane skeleton.

In formula (M), the average number of repeating units _n1 is preferably 0.95 or more, more preferably 0.98 or more, even more preferably 1.0 or more, particularly preferably 1.1 or more, and preferably 10 .0 or less, more preferably 8.0 or less, still more preferably 7.0 or less, particularly preferably 6.0 or less. When the average number of repeating units _n1 is within the above range, the effects of the present invention can be significantly obtained. In particular, the glass transition temperature of the resin composition can be effectively increased.

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

The maleimide compound containing the structure represented by the formula (M1) may further contain the structure shown by the following formula (M2). For example, a maleimide compound having a structure represented by formula (M1) is such that in formula (M1), n ₂ is 3 or less, and the maleimide group is bonded to the benzene ring at the ortho and para positions with respect to the maleimide group. Two or more of them may contain a structure represented by formula (M2) in combination with a structure represented by formula (M1) when R ¹ is not bonded.

（式（Ｍ２）において、Ｒ^ｃ１は、それぞれ独立に、炭素原子数１～１０のアルキル基、炭素原子数１～１０のアルキルオキシ基、炭素原子数１～１０のアルキルチオ基、炭素原子数６～１０のアリール基、炭素原子数６～１０のアリールオキシ基、炭素原子数６～１０のアリールチオ基、炭素原子数３～１０のシクロアルキル基、ハロゲン原子、ニトロ基、水酸基、又は、メルカプト基を表し；Ｒ^ｃ２は、それぞれ独立に、炭素原子数１～１０のアルキル基、炭素原子数１～１０のアルキルオキシ基、炭素原子数１～１０のアルキルチオ基、炭素原子数６～１０のアリール基、炭素原子数６～１０のアリールオキシ基、炭素原子数６～１０のアリールチオ基、炭素原子数３～１０のシクロアルキル基、ハロゲン原子、水酸基、又は、メルカプト基を表し；ｎ_ｃ１は、繰り返し単位数であり、１～２０の整数を表し；ｎ_ｃ２は、それぞれ独立に、０～４の整数を表し；ｎ_ｃ３は、それぞれ独立に、０～３の整数を表し；＊は、結合手を表す。Ｒ^ｃ１のアルキル基、アルキルオキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、及びシクロアルキル基の水素原子は、ハロゲン原子で置換されていてもよい。Ｒ^ｃ２のアルキル基、アルキルオキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、及びシクロアルキル基の水素原子は、ハロゲン原子で置換されていてもよい。ｎ_ｃ２が２～４の場合、Ｒ^ｃ１は、同一環内で同じであってもよく異なっていてもよい。ｎ_ｃ３が２～３の場合、Ｒ^ｃ２は、同一環内で同じであってもよく異なっていてもよい。）

(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 6 carbon atoms. -10 aryl group, C6-10 aryloxy group, C6-10 arylthio group, C3-10 cycloalkyl group, halogen atom, nitro group, hydroxyl group, or mercapto group R ^c2 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 aryl group having 6 to 10 carbon atoms. group, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a hydroxyl group, or a mercapto group; n _c1 is It is the number of repeating units and 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 bond Represents a hand.The hydrogen atoms of the alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, and cycloalkyl group in R ^c1 may be substituted with a halogen atom.The alkyl in R ^c2 The hydrogen atoms of the group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, and cycloalkyl group may be substituted with a halogen atom. When _{n c2} is 2 to 4, R ^c1 is , may be the same or different within the same ring. When n _c3 is 2 to 3, R ^c2 may be the same or different within the same ring.)

The maleimide compound containing the structure represented by formula (M1) preferably has a molecular weight distribution Mw/Mn calculated from gel permeation chromatography (GPC) measurement 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 expressed as "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, even more preferably 1.2 to 3.6, particularly preferably 1.3 to 3.4. When the molecular weight distribution Mw/Mn of the maleimide compound containing the structure represented by formula (M1) is within the above range, the effects of the present invention can be significantly obtained.

Among the maleimide compounds containing the structure represented by formula (M1), the amount of the maleimide compound having an average repeating unit number n ₁ of 0 is preferably within a specific range. When performing the GPC measurement of the maleimide compound containing the structure represented by formula (M1), the amount of the maleimide compound in which the average number of repeating units n1 is ₀ shall be expressed in area % based on the result of the GPC measurement. I can do it. Specifically, in the chromatogram obtained by the above GPC measurement, the area of the peak of the maleimide compound having an average repeating unit number n ₁ of 0 relative to the total area of the peak of the maleimide compound containing the structure represented by formula (M1) The amount of the maleimide compound having an average repeating unit number n ₁ of 0 can be expressed by the ratio (area %). Specifically, the amount of the maleimide compound having an average repeating unit number n ₁ of 0 is preferably 32 area % or less, and more preferably Preferably it is 30 area % or less, 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 above range, the effects of the present invention can be significantly obtained.

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

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

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

The content of the radically polymerizable compound (E) in the resin composition may be 0% by mass, or may be greater than 0% by mass, when the nonvolatile components in the resin composition are 100% by mass. Preferably 0.01% by mass or more, more preferably 0.1% by mass or more, particularly preferably 0.5% by mass or more, and for example 10% by mass or less, preferably 5% by mass or less, more preferably 3% by mass or less. It is not more than 2% by mass, particularly preferably not more than 2 to 2.0% by mass.

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

<(F) Other curing agents>
The resin composition of the present invention may contain (F) another curing agent as an optional component. This (F) other curing agent does not include those corresponding to the above-mentioned components (A) to (C) and (E). (F) Other curing agents may have a function as an epoxy resin curing agent that reacts with (B) epoxy resin to cure the resin composition, similar to the above-mentioned (C) active ester compound. (F) Other curing agents may be used alone or in combination of two or more.

(F) Other curing agents include, for example, phenolic curing agents, carbodiimide curing agents, acid anhydride curing agents, amine curing agents, benzoxazine curing agents, cyanate ester curing agents, and thiol curing agents. Examples include agents. Among these, it is preferable to use one or more types of curing agent selected from the group consisting of phenolic curing agents and carbodiimide curing agents.

As the phenolic curing agent, a curing agent having one or more, preferably two or more, hydroxyl groups bonded to an aromatic ring such as a benzene ring or a naphthalene ring in one molecule can be used. From the viewpoint of heat resistance and water resistance, a phenolic curing agent having a novolak structure is preferred. Furthermore, from the viewpoint of adhesion, nitrogen-containing phenolic curing agents are preferred, and triazine skeleton-containing phenolic curing agents are more preferred. Among these, triazine skeleton-containing phenol novolac resins are preferred from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion. Specific examples of phenolic curing agents include "MEH-7700", "MEH-7810", and "MEH-7851" manufactured by Meiwa Kasei Co., Ltd., and "NHN", "CBN", and "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. 375'', ``SN-395'', DIC's ``LA-7052'', ``LA-7054'', ``LA-3018'', ``LA-3018-50P'', ``LA-1356'', ``TD2090'', `` TD-2090-60M” and the like.

As the carbodiimide curing agent, a curing agent having one or more, preferably two or more carbodiimide structures in one molecule can be used. Specific examples of carbodiimide curing agents include aliphatic biscarbodiimides such as tetramethylene-bis(t-butylcarbodiimide) and cyclohexanebis(methylene-t-butylcarbodiimide); aromatic curing agents such as phenylene-bis(xylylcarbodiimide); Biscarbodiimides such as biscarbodiimide; aliphatic polycarbodiimides such as polyhexamethylenecarbodiimide, polytrimethylhexamethylenecarbodiimide, polycyclohexylenecarbodiimide, poly(methylenebiscyclohexylenecarbodiimide), poly(isophoronecarbodiimide); poly(phenylenecarbodiimide), Poly(naphthylenecarbodiimide), poly(tolylenecarbodiimide), poly(methyldiisopropylphenylenecarbodiimide), poly(triethylphenylenecarbodiimide), poly(diethylphenylenecarbodiimide), poly(triisopropylphenylenecarbodiimide), poly(diisopropylphenylenecarbodiimide) , poly(xylylenecarbodiimide), poly(tetramethylxylylenecarbodiimide), poly(methylene diphenylenecarbodiimide), poly[methylenebis(methylphenylene)carbodiimide], and other aromatic polycarbodiimides. Commercially available carbodiimide curing agents include, for example, "Carbodilite V-02B", "Carbodilite V-03", "Carbodilite V-04K", "Carbodilite V-07", and "Carbodilite V-09" manufactured by Nisshinbo Chemical Co., Ltd. "Stavaxol P", "Stavaxol P400", "Hikasil 510", etc. manufactured by Rhein Chemie.

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

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

Specific examples of benzoxazine curing agents include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemical; "HFB2006M" manufactured by Showa Kobunshi Co., Ltd.; "P-d" manufactured by Shikoku Kasei Kogyo Co., Ltd.; Examples include "Fa".

Examples of cyanate ester curing agents include bisphenol A dicyanate, polyphenol cyanate (oligo(3-methylene-1,5-phenylene cyanate)), 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4, 4'-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate) phenylpropane, 1,1-bis(4-cyanate phenylmethane), bis(4-cyanate-3,5- difunctional cyanate resins such as dimethylphenyl)methane, 1,3-bis(4-cyanatophenyl-1-(methylethylidene))benzene, bis(4-cyanatophenyl)thioether, and bis(4-cyanatophenyl)ether; Examples include polyfunctional cyanate resins derived from phenol novolacs and cresol novolaks, and prepolymers in which these cyanate resins are partially triazine-formed. Specific examples of cyanate ester curing agents include "PT30" and "PT60" (both phenol novolac type polyfunctional cyanate ester resins), "BA230" and "BA230S75" (part of bisphenol A dicyanate) manufactured by Lonza Japan. or a prepolymer completely triazinated to form a trimer).

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

(F) The active group equivalent of the other curing agent is preferably 50 g/eq. ～3000g/eq. , more preferably 100g/eq. ～1000g/eq. , more preferably 100g/eq. ～500g/eq. , particularly preferably 100 g/eq. ～300g/eq. It is. Active group equivalent represents the mass of curing agent per equivalent of active group.

The quantitative ratio of the epoxy resin to the curing agent, that is, the quantitative ratio of the component (B) to the components (C) and (F) is determined by dividing the mass of the nonvolatile component of the component (B) by the epoxy equivalent. The total value is a, the total value of all the values obtained by dividing the mass of the non-volatile components of component (C) by the active ester group equivalent is designated b, and the mass of the non-volatile components of component (F) is divided by the active group equivalent. When c is the sum of all the values, (b+c)/a is preferably 1.0 or more, more preferably 1.01 or more, even more preferably 1.1 to 1.10 or more, and 1. .15 or more is even more preferable, 1.2 or more is particularly preferable, 2.0 or less is preferable, 1.75 or less is more preferable, 1.5 or less is still more preferable, and 1.4 to 1. It is even more preferably 40 or less, and particularly preferably 1.35 or less. By setting the ratio of the epoxy resin to the curing agent within this range, the effects of the present invention can be easily obtained.

The content of the other curing agent (F) in the resin composition may be 0% by mass, or may be greater than 0% by mass, when the nonvolatile components in the resin composition are 100% by mass. Preferably 0.01% by mass or more, more preferably 0.1% by mass or more, particularly preferably 1.0% by mass or more, preferably 20% by mass or less, more preferably 10% by mass or less, particularly preferably 5% by mass or less. % by mass or less.

The content of the other curing agent (F) in the resin composition may be 0% by mass, or may be greater than 0% by mass, when the resin component in the resin composition is 100% by mass. Preferably 0.1% by mass or more, more preferably 1.0% by mass or more, particularly preferably 4.0% by mass or more, preferably 50% by mass or less, more preferably 20% by mass or less, particularly preferably 10% by mass or less. % by mass or less.

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

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

Examples of the phosphorus curing accelerator include tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium)pyromellitate, and tetrabutylphosphonium hydro Aliphatic phosphonium salts such as denhexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate, di-tert-butylmethylphosphonium tetraphenylborate; Methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra-p-tolylborate, tetraphenyl Phosphonium tetraphenylborate, tetraphenylphosphonium tetrap-tolylborate, triphenylethylphosphonium tetraphenylborate, tris(3-methylphenyl)ethylphosphonium tetraphenylborate, tris(2-methoxyphenyl)ethylphosphonium tetraphenylborate, (4 - Aromatic phosphonium salts such as methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate; Aromatic phosphine/borane complexes such as triphenylphosphine/triphenylborane; triphenylphosphine/p-benzoquinone Aromatic phosphine/quinone addition reaction products such as addition reaction products; tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butyl (2-butenyl) phosphine, di-tert-butyl (3-methyl- Aliphatic phosphine such as 2-butenyl)phosphine, tricyclohexylphosphine; dibutylphenylphosphine, di-tert-butylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclohexylphosphine, triphenylphosphine, tri-o -Tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tris(4-ethylphenyl)phosphine, tris(4-propylphenyl)phosphine, tris(4-isopropylphenyl)phosphine, tris(4-butyl) phenyl)phosphine, tris(4-tert-butylphenyl)phosphine, tris(2,4-dimethylphenyl)phosphine, tris(2,5-dimethylphenyl)phosphine, tris(2,6-dimethylphenyl)phosphine, tris( 3,5-dimethylphenyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, tris(2,6-dimethyl-4-ethoxyphenyl)phosphine, tris(2-methoxyphenyl)phosphine, tris(4- methoxyphenyl)phosphine, tris(4-ethoxyphenyl)phosphine, tris(4-tert-butoxyphenyl)phosphine, diphenyl-2-pyridylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis( Examples include aromatic phosphines such as diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,2-bis(diphenylphosphino)acetylene, and 2,2'-bis(diphenylphosphino)diphenyl ether. It will be done.

Examples of the urea-based curing accelerator include 1,1-dimethylurea; 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, 3- Aliphatic dimethylurea such as cyclooctyl-1,1-dimethylurea; 3-phenyl-1,1-dimethylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl) )-1,1-dimethylurea, 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4- methylphenyl)-1,1-dimethylurea, 3-(3,4-dimethylphenyl)-1,1-dimethylurea, 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4- methoxyphenyl)-1,1-dimethylurea, 3-(4-nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy)phenyl]-1,1-dimethylurea, 3- [4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trifluoromethyl)phenyl]-1,1-dimethylurea, N,N-(1,4-phenylene) Aromatic dimethylurea such as bis(N',N'-dimethylurea), N,N-(4-methyl-1,3-phenylene)bis(N',N'-dimethylurea) [toluene bisdimethylurea] etc.

Examples of the guanidine-based curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, Tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0] Dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1 -allyl biguanide, 1-phenyl biguanide, 1-(o-tolyl) biguanide and the like.

Examples of imidazole-based curing accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl- 2-Phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecyl imidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4- Diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2- Phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline , imidazole compounds such as 2-phenylimidazoline, and adducts of imidazole compounds and epoxy resins.

As the imidazole curing accelerator, commercially available products may be used, such as "1B2PZ", "2MZA-PW", "2PHZ-PW" manufactured by Shikoku Chemical Co., Ltd., and "P200-H50" manufactured by Mitsubishi Chemical Corporation. etc.

Examples of the metal hardening accelerator include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. Examples include organic zinc complexes such as , organic iron complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

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

As the amine curing accelerator, commercially available products may be used, such as "MY-25" manufactured by Ajinomoto Fine Techno.

The content of the curing accelerator (G) in the resin composition is not particularly limited, but when the nonvolatile component in the resin composition is 100% by mass, it is preferably 15% by mass or less, more preferably It is 10% by mass or less, more preferably 5% by mass or less, particularly preferably 3% by mass or less. The lower limit of the content of the curing accelerator (E) in the resin composition is not particularly limited, but when the nonvolatile component in the resin composition is 100% by mass, for example, 0% by mass or more, 0% by mass. It may be .001% by mass or more, 0.01% by mass or more, 0.1% by mass or more, 0.5% by mass or more, etc.

<(H) Other additives>
The resin composition of the present invention may further contain arbitrary additives as nonvolatile components. Examples of such additives include radical polymerization initiators such as peroxide-based radical polymerization initiators and azo-based radical polymerization initiators; phenolic curing agents, naphthol-based curing agents, acid anhydride-based curing agents, and thiols. Epoxy curing agents other than active ester compounds such as curing agents, benzoxazine curing agents, cyanate ester curing agents, carbodiimide curing agents, imidazole curing agents; phenoxy resins, polyvinyl acetal resins, polyolefin resins, polysulfone resins, Thermoplastic resins such as ether sulfone resins, polyphenylene ether resins, polycarbonate resins, polyether ether ketone resins, and polyester resins; organic fillers such as rubber particles; organometallic compounds such as organocopper compounds, organozinc compounds, and organocobalt compounds; Coloring agents such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, and carbon black; Polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and phenothiazine; silicone leveling agents, acrylic polymer leveling agents, etc. Leveling agents; Thickeners such as bentone and montmorillonite; Antifoaming agents such as silicone antifoaming agents, acrylic antifoaming agents, fluorine antifoaming agents, and vinyl resin antifoaming agents; Benzotriazole ultraviolet absorbers, etc. UV absorbers; adhesion improvers such as urea silane; adhesion agents such as triazole adhesion agents, tetrazole adhesion agents, triazine adhesion agents; hindered phenolic antioxidants, hindered amines Antioxidants such as antioxidants; Fluorescent brighteners such as stilbene derivatives; Surfactants such as fluorine surfactants and silicone surfactants; Phosphorus flame retardants (e.g. phosphate ester compounds, phosphazene compounds, Flame retardants such as phosphinic acid compounds, red phosphorus), nitrogen-based flame retardants (e.g. melamine sulfate), halogen-based flame retardants, and inorganic flame retardants (e.g. antimony trioxide); phosphate ester-based dispersants, polyoxyalkylene-based dispersants Dispersants such as acetylene dispersants, silicone dispersants, anionic dispersants, cationic dispersants; borate stabilizers, titanate stabilizers, aluminate stabilizers, zirconate stabilizers, isocyanate stabilizers Stabilizers such as carboxylic acid stabilizers, carboxylic acid anhydride stabilizers, and the like can be mentioned. (F) Other additives may be used alone or in combination of two or more in any ratio. (H) The content of other additives can be determined as appropriate by those skilled in the art.

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

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

<Method for manufacturing resin composition>
For example, the resin composition of the present invention can be prepared by adding (A) a styrenic and/or hydrogenated styrenic polymer having a weight average molecular weight of 10,000 or less, (B) an epoxy resin, and (C) an active ester compound to an arbitrary preparation container. , as necessary (D) inorganic filler, as necessary (E) radically polymerizable compound, as necessary (F) other curing agent, as necessary (G) curing accelerator, as necessary It can be produced by adding and mixing (H) other additives and, if necessary, (K) an organic solvent in any order and/or some or all at the same time. Further, in the process of adding and mixing each component, the temperature can be set appropriately, and heating and/or cooling may be performed temporarily or throughout. In addition, during or after the addition and mixing process, the resin composition may be stirred or shaken using a stirring device or shaking device such as a mixer to uniformly disperse the resin composition. Moreover, simultaneously with stirring or shaking, defoaming may be performed under low pressure conditions such as under vacuum.

<Characteristics of resin composition>
The resin composition of the present invention contains (A) a styrenic and/or hydrogenated styrenic 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 with excellent crack resistance after desmear treatment, and preferably in a room temperature range such as 23°C or a high temperature environment such as 90°C. Also, it is possible to obtain a cured product which has a low dielectric loss tangent, a low relative permittivity both at room temperature, a normal temperature range, and a high temperature environment, and a high glass transition temperature.

The cured product of the resin composition of the present invention may have a feature of being able to suppress the occurrence of cracks after desmear treatment (roughening treatment). Therefore, in one embodiment, after manufacturing and desmearing a circuit board as in Test Example 2 below, if 100 copper pads of the circuit board are observed, preferably there are 10 or less (10% or less) cracks. could be.

The cured product of the resin composition of the present invention may be characterized by a low dielectric loss tangent (Df) 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 at 5.8 GHz and 90° C. as in Test Example 1 below is preferably 0.020 or less, 0.010 or less. , more preferably 0.009 or less, 0.008 or less, further preferably 0.007 or less, 0.006 or less, particularly preferably 0.005 or less, 0.004 or less.

The cured product of the resin composition of the present invention may be characterized by a low dielectric loss tangent (Df) even at room temperature such as 23°C. Therefore, in one embodiment, the dielectric loss tangent (Df) of the cured product of the resin composition when measured at 5.8 GHz and 23° C. as in Test Example 1 below is preferably 0.020 or less, 0.010 or less. , more preferably 0.009 or less, 0.008 or less, further preferably 0.007 or less, 0.006 or less, even 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 may have a characteristic of having a low dielectric constant (Dk) even in a high temperature environment such as 90°C. Therefore, in one embodiment, the dielectric constant (Dk) of the cured resin composition when measured at 5.8 GHz and 90° C. as in Test Example 1 below is preferably 5.0 or less, more preferably It can be 4.0 or less, more preferably 3.5 or less, and can be further lowered when containing hollow silica as the (D) inorganic filler, preferably 5.0 or less, more preferably 4.0 or less. , 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 of having a low dielectric constant (Dk) even at room temperature such as 23° C. or room temperature. Therefore, in one embodiment, the dielectric constant (Dk) of the cured resin composition when measured at 5.8 GHz and 23° C. as in Test Example 1 below is preferably 5.0 or less, more preferably It can be 4.0 or less, more preferably 3.5 or less, and can be further lowered when containing hollow silica as the (D) inorganic filler, preferably 5.0 or less, more preferably 4.0 or less. , more preferably 3.5 or less, particularly preferably 3.0 or less.

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

<Applications of resin composition>
The resin composition of the present invention can be suitably used as a resin composition for insulation purposes, particularly as a resin composition for forming an insulation layer. Specifically, a resin composition for forming an insulating layer (including a rewiring layer) formed on an insulating layer (a resin for forming an insulating layer for forming a conductor layer) is used. composition). Further, in a printed wiring board to be described later, it can be suitably used as a resin composition for forming an insulating layer of a printed wiring board (resin composition for forming an insulating layer of a printed wiring board). The resin composition of the present invention can also be used in sheet-like laminated materials such as resin sheets and prepregs, solder resists, underfill materials, die bonding materials, semiconductor encapsulating materials, hole-filling resins, component embedding resins, etc. that require resin compositions. Can be used in a wide range of applications.

Further, for example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition of the present invention can be used as a rewiring formation layer as an insulating layer for forming a rewiring layer. It can also be suitably used as a resin composition (resin composition for forming a rewiring formation layer) and a resin composition for sealing a semiconductor chip (resin composition for semiconductor chip sealing). When the semiconductor chip package is manufactured, a rewiring layer may be further formed on the sealing layer.
(1) The step of laminating a temporary fixing film on the base material,
(2) Temporarily fixing the semiconductor chip on the temporary fixing film,
(3) forming a sealing layer on the semiconductor chip;
(4) Peeling the base material and temporary fixing film from the semiconductor chip,
(5) Forming a rewiring layer as an insulating layer on the surface of the semiconductor chip from which the base material and the temporary fixing film have been peeled; and (6) Forming a rewiring layer as a conductive layer on the rewiring layer. Forming process

Moreover, since the resin composition of the present invention provides an insulating layer with good component embeddability, it can be suitably used even when the printed wiring board is a component-embedded circuit board.

<Sheet-like laminated material>
Although the resin composition of the present invention can be used by applying it in the form of a varnish, it is generally preferable for industrial use to use it in the form of a sheet-like laminate material containing the resin composition.

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

In one embodiment, the resin sheet includes a support and a resin composition layer provided on the support, and the resin composition layer is formed from 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 making the printed wiring board thinner and providing a cured product with excellent insulation even if the cured product of the resin composition is a thin film. Preferably it is 40 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, but can usually be 5 μm or more, 10 μm or more, etc.

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

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

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

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

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

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

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

The resin sheet can be made, for example, by using a liquid resin composition as it is, or by preparing a resin varnish by dissolving the resin composition in an organic solvent, applying it onto a support using a die coater, and then drying it. It can be manufactured by forming a resin composition layer.

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

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

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

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

Prepreg can be manufactured by a known method such as a hot melt method or a solvent method.

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

The sheet-like 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 for forming an interlayer insulating layer of a printed wiring board (for a printed wiring board). It can be suitably used for interlayer insulating layers of wiring boards).

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

A printed wiring board can be manufactured, for example, using the above-mentioned resin sheet by a method including the following steps (I) and (II).
(I) Step of laminating the resin sheet on the inner layer substrate so that the resin composition layer of the resin sheet is bonded to the inner layer substrate. (II) Forming an insulating layer by curing (e.g., thermosetting) the resin composition layer. process of doing

The "inner layer substrate" used in step (I) is a member that becomes a substrate of a printed wiring board, and includes, for example, a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. etc. Further, the substrate may have a conductor layer on one or both sides, and this conductor layer may be patterned. An inner layer board having a conductor layer (circuit) formed on one or both sides of the board is sometimes referred to as an "inner layer circuit board." Further, when manufacturing a printed wiring board, an intermediate product on which an insulating layer and/or a conductive layer is further formed is also included in the "inner layer substrate" as referred to in the present invention. If the printed wiring board is a circuit board with built-in components, an inner layer board with built-in components may be used.

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

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

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

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

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

In step (II), the resin composition layer is cured (for example, thermally cured) to form an insulating layer made of a cured product of the resin composition. The curing conditions for the resin composition layer are not particularly limited, and conditions commonly employed for forming an insulating layer of a printed wiring board may be used.

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

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

When manufacturing a printed wiring board, the steps of (III) drilling holes in the insulating layer, (IV) roughening the insulating layer, and (V) forming a conductor layer may be further carried out. These steps (III) to (V) may be performed according to various methods known to those skilled in the art that are used in the manufacture of printed wiring boards. Note that when the support is removed after step (II), the support may be removed between step (II) and step (III), between step (III) and step (IV), or during step (IV). IV) and step (V). Further, if necessary, the formation of the insulating layer and the conductive layer in steps (II) to (V) may be repeated to form a multilayer wiring board.

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

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

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

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

The oxidizing agent used in the roughening treatment is not particularly limited, but includes, for example, an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The roughening treatment with 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 minutes to 30 minutes. Further, the concentration of permanganate in the alkaline permanganic acid solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Securigance P" manufactured by Atotech Japan.

Further, as the neutralizing liquid used for the roughening treatment, an acidic aqueous solution is preferable, and a commercially available product includes, for example, "Reduction Solution Securigant P" manufactured by Atotech Japan.

The treatment with the neutralizing liquid can be carried out by immersing the treated surface, which has been roughened with an oxidizing agent, in the neutralizing liquid at 30° C. to 80° C. for 5 minutes to 30 minutes. From the viewpoint of workability, it is preferable to immerse the object that has been roughened with an oxidizing agent in a neutralizing solution at 40° C. to 70° C. for 5 minutes to 20 minutes.

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

In a preferred embodiment, the conductor layer includes one or more selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. Contains metal. The conductor layer may be a single metal layer or an alloy layer, and the alloy layer may be, for example, an alloy of two or more metals selected from the above group (for example, a nickel-chromium alloy, a copper-chromium alloy, a copper-chromium alloy, etc.). nickel alloys and copper-titanium alloys). Among these, from the viewpoint of versatility in forming conductor layers, cost, ease of patterning, etc., monometallic layers of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, nickel-chromium alloys, copper, etc. An alloy layer of nickel alloy or copper/titanium alloy is preferable, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel/chromium alloy is more preferable, and a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper is more preferable. More preferred is a metal layer.

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

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

In one embodiment, the conductor layer may be formed by plating. For example, a conductor layer having a desired wiring pattern can be formed by plating the surface of an insulating layer using a conventionally known technique such as a semi-additive method or a fully additive method. It is preferable to form by a method. An example of forming a conductor layer by a semi-additive method will be shown below.

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

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

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

<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 (eg, computers, mobile phones, digital cameras, televisions, etc.), vehicles (eg, motorcycles, automobiles, trains, ships, aircraft, etc.), and the like.

Hereinafter, the present invention will be specifically explained with reference to Examples. The present invention is not limited to these examples. In addition, in the following, "parts" and "%" representing amounts mean "parts by mass" and "% by mass", respectively, unless otherwise specified. The temperature condition when there is no particular temperature specification is room temperature (25° C.).

[Synthesis Example 1: Synthesis of active ester compound A]
203.0 g of isophthalic acid chloride (number of moles of acid chloride group: 2.0 mol) and 1400 g of toluene were charged into a flask equipped with a thermometer, dropping funnel, condenser tube, fractionator tube, and stirrer, and the pressure inside the system was reduced. The mixture was replaced with nitrogen and dissolved. Next, 113.9 g (0.67 mol) of ortho-phenylphenol and 240 g (mol number of phenolic hydroxyl group: 1.33 mol) of a benzyl-modified naphthalene compound were charged, and the inside of the system was replaced with nitrogen under reduced pressure to dissolve them. Thereafter, 0.70 g of tetrabutylammonium bromide was dissolved, and 400 g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours while controlling the inside of the system to 60° C. or lower while purging with nitrogen gas. Stirring was then continued under these conditions for 1.0 hour. After the reaction was completed, the mixture was allowed to stand still for liquid separation, and the aqueous layer was removed. Further, water was added to the toluene layer in which the reactants were dissolved, and the mixture was stirred and mixed for 15 minutes, and the mixture was allowed to stand still for liquid separation to remove the aqueous layer. This operation was repeated until the pH of the aqueous layer reached 7. Thereafter, water was removed by dehydration using a decanter to obtain active ester compound A in the form of a toluene solution with a nonvolatile content of 62% by mass. The active ester equivalent of the obtained active ester compound A was 238 g/eq. Met.

[Synthesis Example 2: Synthesis of active ester compound B]
In a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube, and a stirrer, 165 g of polyaddition reaction resin of dicyclopentadiene and phenol (hydroxyl equivalent: 165 g/eq, softening point 85°C) and ortho 134 g (1.0 mol) of allylphenol and 1200 g of toluene were charged, and the inside of the system was purged with nitrogen under reduced pressure. Next, 203 g (1.0 mol) of isophthalic acid chloride was charged, and the inside of the system was purged with nitrogen under reduced pressure. 0.6 g of tetrabutylammonium bromide was added, the inside of the system was controlled to below 60° C. while being purged with nitrogen gas, and 412 g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. After the addition was completed, 1. Stirred for 0 hours. After the reaction was completed, the aqueous layer was removed by static separation. Water was further added to the obtained toluene layer, stirred for 15 minutes, and the aqueous layer was removed by static separation. This operation was repeated until the pH of the aqueous layer became 7. Then, by heating and drying to adjust the nonvolatile content to 70% by mass, an active ester resin represented by the following chemical formula was obtained.

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 preparation ratio is 1. Moreover, the broken line in the chemical formula is a structure obtained by reacting isophthalic acid chloride, a polyaddition reaction resin of phenol, and/or orthoallylphenol. The ester group equivalent of the obtained active ester resin was calculated from the charging ratio and was 214 g/eq.

[Example 1]
10 parts of naphthalene type epoxy resin ("HP-4032-SS" manufactured by DIC Corporation, epoxy equivalent 144 g/eq.), naphthalene aralkyl type epoxy resin ("ESN-475V" manufactured by Nippon Steel Chemical & Materials, epoxy equivalent 330 g/eq. .) 5 parts, biphenylaralkyl epoxy resin (Nippon Kayaku Co., Ltd. "NC-3100", epoxy equivalent 258 g/eq.) 5 parts, active ester curing agent ("HPC-8150-62T", active group equivalent 229 g) /eq., toluene solution with non-volatile content of 61.5% by mass), 43 parts of other curing agent (phenolic curing agent, “LA-3018-50P” manufactured by DIC Corporation, hydroxyl equivalent: 151 g/eq., non-volatile content: 50 mass) % 1-methoxy 2-propanol solution), 10 parts of low molecular weight polystyrene (Yasuhara Chemical Co., Ltd. "SX-100"; Mw 2000) as component (A), inorganic filler (amine-based alkoxysilane compound (Shin-Etsu Chemical Co., Ltd.) 135 parts of spherical silica (manufactured by Admatex, "SO-C2", average particle size 0.5 μm, specific surface area 5.8 m ² /g) surface-treated with KBM573 (manufactured by Admatex), curing accelerator (Shikoku Kasei Kogyo) A resin varnish was obtained by mixing 0.5 parts of "1B2PZ" manufactured by Co., Ltd., 10 parts of MEK, and 10 parts of cyclohexanone and uniformly dispersing the mixture using a high-speed rotating mixer.

[Example 2]
In Example 1, 43 parts of an active ester curing agent ("HPC-8150-62T", a toluene solution with an active group equivalent of 223 g/eq. and a non-volatile content of 61.5% by mass) was added to an active ester curing agent (manufactured by DIC Corporation). "HPC-8000-65T", active group equivalent: 223 g/eq., toluene solution with non-volatile content: 65% by mass) was changed to 40 parts. A resin varnish was obtained in the same manner as in Example 1 except for the above matters.

[Example 3]
In Example 1, 43 parts of an active ester curing agent ("HPC-8150-62T", active group equivalent: 223 g/eq., non-volatile content: 61.5% by mass, toluene solution) was added to the active ester obtained in Synthesis Example 1. The amount was changed to 43 parts of A (a toluene solution with an active group equivalent of 238 g/eq. and a non-volatile content of 61.5% by mass). A resin varnish was obtained in the same manner as in Example 1 except for the above matters.

[Example 4]
In Example 1, 43 parts of an active ester curing agent ("HPC-8150-62T", active group equivalent: 223 g/eq., non-volatile content: 61.5% by mass, toluene solution) was added to the active ester obtained in Synthesis Example 2. The amount was changed to 37 parts of B (a toluene solution with an active group equivalent of 214 g/eq. and a non-volatile content of 70% by mass). A resin varnish was obtained in the same manner as in Example 1 except for the above matters.

[Example 5]
In Example 1, 43 parts of an active ester curing agent ("HPC-8150-62T", a toluene solution with an active group equivalent of 223 g/eq. and a non-volatile content of 61.5% by mass) was mixed with an active ester curing agent (air/water). The solution was changed to 37 parts of "PC1300-02-65MA" manufactured by Co., Ltd., a methyl amyl ketone solution with an active group equivalent of 199 g/eq. and a non-volatile content of 65% by mass. A resin varnish was obtained in the same manner as in Example 1 except for the above matters.

[Example 6]
In Example 1, maleimide compound A represented by the following formula (M) (Mw/Mn=1.81 , t''=1.47 (mainly 1, 2 or 3)) (2 parts by weight of non-volatile components) were used. A resin varnish was obtained in the same manner as in Example 1 except for the above matters.

[Example 7]
In Example 1, 2 parts of another thermosetting resin (maleimide resin (MIR-5000-60T manufactured by Nippon Kayaku Co., Ltd., toluene solution with non-volatile content of 60% by mass) was used. Other than the above matters were carried out. A resin varnish was obtained in the same manner as in Example 1.

[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 used.The above matters A resin varnish was obtained in the same manner as in Example 1 except for this.

[Example 9]
In Example 1, 2 parts of another thermosetting resin (maleimide resin ("BMI-689" manufactured by Designer Molecules)) was used.A resin varnish was prepared in the same manner as in Example 1 except for the above. Obtained.

[Example 10]
In Example 1, 2 parts of another thermosetting resin (acrylate resin ("A-DOG" manufactured by Shin-Nakamura Chemical Co., Ltd.)) was further used.A resin varnish was obtained in the same manner as in Example 1 except for the above matters. .

[Example 11]
In Example 1, 2 parts of another thermosetting resin (styryl resin ("OPE-2St-1200" manufactured by Mitsubishi Gas Chemical Co., Ltd., toluene solution with non-volatile content of 65% by mass) was used. Other than the above matters were carried out. A resin varnish was obtained in the same manner as in Example 1.

[Example 12]
In Example 1, spherical silica (manufactured by Admatex, "SO-C2", average particle size 0.5 μm, surface-treated with an inorganic filler (amine-based alkoxysilane compound ("KBM573", manufactured by Shin-Etsu Chemical Co., Ltd.)) Spherical silica having a hollow part whose surface was treated with an inorganic filler having a hollow part (amine-based alkoxysilane compound ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.)) was prepared by changing 170 parts (specific surface area 5.8 m ² /g) to 135 parts. ("BA-S" manufactured by JGC Catalysts & Chemicals Co., Ltd.)) A resin varnish was obtained in the same manner as in Example 1 except that 35 parts of the resin was added.

[Example 13]
In Example 1, instead of using 10 parts of low molecular weight polystyrene ("SX-100" manufactured by Yasuhara Chemical Co., Ltd.) as component (A), styrene-(α-methylstyrene)-based polymer (Mitsui Chemicals) was used as component (A). A resin varnish was obtained in the same manner as in Example 1, except that 10 parts of "FTR-0100" (Mw1960) manufactured by Co., Ltd. was added.

[Example 14]
In Example 1, instead of using 10 parts of low molecular weight polystyrene ("SX-100" manufactured by Yasuhara Chemical Co., Ltd.) as the component (A), a styrene-aromatic hydrocarbon polymer (manufactured by Mitsui Chemicals, Inc.) was used as the component (A). A resin varnish was obtained in the same manner as in Example 1 except that 10 parts of "FMR-0150" (Mw2040) was added.

[Example 15]
In Example 1, as component (A), 10 parts of low molecular weight polystyrene ("SX-100" manufactured by Yasuhara Chemical Co., Ltd.) was changed to 1 part, and an inorganic filler (amine-based alkoxysilane compound ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) ) Surface-treated spherical silica (manufactured by Admatex, "SO-C2", average particle size 0.5 μm, specific surface area 5.8 m ² /g) Same as Example 1 except that 170 parts was changed to 145 parts. A resin varnish was obtained in the same manner.

[Example 16]
In Example 1, as component (A), 10 parts of low molecular weight polystyrene ("SX-100" manufactured by Yasuhara Chemical Co., Ltd.) was changed to 15 parts, and an inorganic filler (amine-based alkoxysilane compound ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) ) Surface-treated spherical silica (manufactured by Admatex, "SO-C2", average particle size 0.5 μm, specific surface area 5.8 m ² /g) Same as Example 1 except that 170 parts was changed to 185 parts. A resin varnish was obtained in the same manner.

[Comparative example 1]
A resin varnish was obtained in the same manner as 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).

[Comparative example 2]
In Example 1, instead of using 10 parts of low molecular weight polystyrene (“SX-100” manufactured by Yasuhara Chemical Co., Ltd.) as component (A), (A′) other polystyrene (GPPS manufactured by PS Japan Co., Ltd.; Mw 190,000) was used. A resin varnish was prepared in the same manner as in Example 1 except for the addition of the above ingredients, but the components were not compatible with each other and the varnish became gel-like, so it could not be evaluated.

[Example 21]
In Example 1, instead of 10 parts of low molecular weight polystyrene ("SX-100" manufactured by Yasuhara Chemical Co., Ltd.) as component (A), hydrogenated styrene ("SG-110" hydrogenated styrene manufactured by Yasuhara Chemical Co., Ltd. or 3 parts of hydrogenated styrene polymer, Mw2000) was added, and spherical silica (Admatex, SO-C2) was surface-treated with an inorganic filler (amine-based alkoxysilane compound (Shin-Etsu Chemical Co., Ltd., "KBM573")). A resin varnish was obtained in the same manner as in Example ¹ except that 155 parts were used instead of 170 parts.

[Example 22]
In Example 21, 43 parts of an active ester curing agent ("HPC-8150-62T", a toluene solution with an active group equivalent of 223 g/eq. and a non-volatile content of 61.5% by mass) was added to an active ester curing agent (manufactured by DIC Corporation). "HPC-8000-65T", active group equivalent: 223 g/eq., toluene solution with non-volatile content: 65% by mass) was changed to 40 parts. A resin varnish was obtained in the same manner as in Example 21 except for the above matters.

[Example 23]
In Example 21, 43 parts of an active ester curing agent ("HPC-8150-62T", active group equivalent: 223 g/eq., toluene solution with non-volatile content of 61.5% by mass) was added to the active ester obtained in Synthesis Example 1. The amount was changed to 43 parts of A (a toluene solution with an active group equivalent of 238 g/eq. and a non-volatile content of 61.5% by mass). A resin varnish was obtained in the same manner as in Example 21 except for the above matters.

[Example 24]
In Example 21, 43 parts of an active ester curing agent ("HPC-8150-62T", active group equivalent: 223 g/eq., toluene solution with non-volatile content of 61.5% by mass) was added to the active ester obtained in Synthesis Example 2. The amount was changed to 37 parts of B (a toluene solution with an active group equivalent of 214 g/eq. and a non-volatile content of 70% by mass). A resin varnish was obtained in the same manner as in Example 21 except for the above matters.

[Example 25]
In Example 21, 43 parts of an active ester curing agent ("HPC-8150-62T", active group equivalent 223 g/eq., toluene solution with non-volatile content 61.5% by mass) was mixed with an active ester curing agent (air/water). The solution was changed to 37 parts of "PC1300-02-65MA" manufactured by Co., Ltd., a methyl amyl ketone solution with an active group equivalent of 199 g/eq. and a non-volatile content of 65% by mass. A resin varnish was obtained in the same manner as in Example 21 except for the above matters.

[Example 26]
In Example 21, maleimide compound A represented by the following formula (M) (Mw/Mn=1.81 , t''=1.47 (mainly 1, 2 or 3)) (2 parts by weight of non-volatile components) were used. A resin varnish was obtained in the same manner as in Example 21 except for the above matters.

[Example 27]
In Example 21, 2 parts of another thermosetting resin (maleimide resin (MIR-5000-60T, manufactured by Nippon Kayaku Co., Ltd., toluene solution with non-volatile content of 60% by mass) was used.Other than the above, the procedure was carried out. A resin varnish was obtained in the same manner as in Example 21.

[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 nonvolatile content of 70% by mass) was used.The above matters A resin varnish was obtained in the same manner as in Example 21 except for this.

[Example 29]
In Example 21, 2 parts of another thermosetting resin (acrylate resin ("A-DOG" manufactured by Shin Nakamura Chemical Co., Ltd.)) was further used.A resin varnish was obtained in the same manner as in Example 21 except for the above matters. .

[Example 30]
In Example 21, 2 parts of another thermosetting resin (styryl resin ("OPE-2St-1200" manufactured by Mitsubishi Gas Chemical Co., Ltd., toluene solution with non-volatile content of 65% by mass) was used. Other than the above matters were carried out. A resin varnish was obtained in the same manner as in Example 21.

[Example 31]
In Example 1, spherical silica (manufactured by Admatex, "SO-C2", average particle size 0.5 μm, surface-treated with an inorganic filler (amine-based alkoxysilane compound ("KBM573", manufactured by Shin-Etsu Chemical Co., Ltd.)) Specific surface area 5.8 m ² /g) 155 parts was changed to 125 parts, and the hollow part was surface-treated with an inorganic filler (amine-based alkoxysilane compound ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.)) having a hollow part. A resin varnish was obtained in the same manner as in Example 1, except that 30 parts of spherical silica ("BA-S" manufactured by JGC Catalysts & Chemicals) was added.

<Test Example 1: Measurement of permittivity and dielectric loss tangent>
(1) Production of resin sheet A with a resin composition layer having a thickness of 40 μm A polyethylene terephthalate film (“AL5” manufactured by Lintec Corporation, thickness 38 μm) provided with a release layer was prepared as a support. The resin varnishes obtained in Examples and Comparative Examples were uniformly applied onto the release layer of this support so that the thickness of the resin composition layer after drying was 40 μm. Thereafter, the resin composition was dried at 80° C. to 100° C. (average 90° C.) for 4 minutes to obtain a resin sheet A including a support and a resin composition layer.

(2) Creation of cured product Resin sheet A obtained in Examples and Comparative Examples was cured in an oven at 190°C for 90 minutes. By peeling off the support from the resin sheet A taken out of the oven, a cured product of the resin composition layer was obtained. The cured product was cut out into pieces with a length of 80 mm and a width of 2 mm and used as a cured product for evaluation.

(3) Measurement of dielectric constant and dielectric loss tangent For each cured product for evaluation, using HP8362B manufactured by Agilent Technologies, the measurement frequency was 5.8 GHz and the measurement temperature was 23°C and 90°C by the cavity resonance perturbation method. The dielectric constant and dielectric loss tangent values (Dk value and Df value) were measured. Measurements were performed using two test pieces, and the average thereof was calculated.

<Test Example 2: Evaluation of crack resistance after desmear treatment>
(1) Production of resin sheet B with a resin composition layer having a thickness of 25 μm A polyethylene terephthalate film (“AL5” manufactured by Lintec Corporation, thickness 38 μm) provided with a release layer was prepared as a support. On the release layer of this support, the resin varnishes obtained in Examples and Comparative Examples were uniformly applied so that the thickness of the resin composition layer after drying was 25 μm, and the coating was applied at 70°C to 80°C (average 75° C.) for 2.5 minutes to obtain a resin sheet B including a support and a resin composition layer.

(2) Evaluation of crack resistance after desmear treatment The resin sheet B with a thickness of 25 μm prepared above is arranged in a lattice pattern with circular copper pads (copper thickness 35 μm) with a diameter of 350 μm at 400 μm intervals so that the residual copper ratio is 60%. The resin composition was applied to both sides of the core material (“E705GR” manufactured by Hitachi Chemical Co., Ltd., thickness 400 μm) formed using a batch type vacuum pressure laminator (two-stage build-up laminator “CVP700” manufactured by Nikko Materials Co., Ltd.). Both sides of the inner layer substrate were laminated so that the material layer was bonded to the inner layer substrate. This lamination was carried out by reducing the pressure for 30 seconds to bring the atmospheric pressure to 13 hPa or less, and then press-bonding at a temperature of 100° C. and a pressure of 0.74 MPa for 30 seconds. This was placed in an oven at 130°C and heated for 30 minutes, 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 a swelling liquid, Swelling Dip Securigant P manufactured by Atotech Japan Co., Ltd., at 60° C. for 10 minutes. Next, it was immersed in Concentrate Compact P (KMnO4: 60 g/L, NaOH: 40 g/L aqueous solution) from Atotech Japan Co., Ltd., which is a roughening liquid, at 80° C. for 30 minutes. Finally, it was immersed in a neutralizing solution, Reduction Solution Securigant P manufactured by Atotech Japan Co., Ltd., at 40° C. for 5 minutes. After the roughening treatment, 100 copper pad portions of the circuit board were observed to confirm the presence or absence of cracks in the resin composition layer. If the number of cracks was 10 or less, it was marked as "○", and if there were more than 10 cracks, it was marked as "x".

<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 off from the support to obtain a cured film. This cured film was cut out to a length of 20 mm and a width of 6 mm and used as an evaluation sample. The glass transition temperature (Tg) of this evaluation sample was measured from 25°C to 250°C at a heating rate of 5°C/min using a Rigaku TMA device (Thermomechanical Analyzer). Measurements were taken twice on the same specimen and the second value was recorded.

Table 1 below shows the amounts used (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 Test Examples. In Table 1, the nonvolatile content (% by mass) of each component is shown in the "N.V." column.

As described above, by using a resin composition containing (A) a styrenic and/or hydrogenated styrenic polymer having a weight average molecular weight of 10,000 or less, (B) an epoxy resin, and (B) an active ester compound, desmear It was found that a cured product with excellent crack resistance after treatment could be obtained. Furthermore, this cured product has a low dielectric loss tangent (Df) both in a room temperature range such as 23°C and a high temperature environment such as 90°C, and has a relative dielectric constant (Dk ) and a high glass transition temperature.

Claims (13)

A resin composition comprising (A) a styrenic and/or hydrogenated styrenic polymer having a weight average molecular weight of 10,000 or less, (B) an epoxy resin, and (C) an active ester compound. The resin composition according to claim 1, wherein component (C) has a carbon-carbon double bond. The resin composition according to claim 1 or 2, wherein component (C) contains an active ester compound containing a styryl group and a naphthalene structure. The resin composition according to any one of claims 1 to 3, further comprising (E) a radically polymerizable compound. The resin composition according to claim 4, wherein (E) the radically polymerizable compound includes (E1) a maleimide compound. The resin composition according to claim 5, wherein (E1) the maleimide compound includes (E1-2) a maleimide compound containing a trimethylindane skeleton. The resin composition according to any one of claims 1 to 6, further comprising (D) an inorganic filler. The resin composition according to any one of claims 1 to 7, which is used for forming an interlayer insulation 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 laminate material containing the resin composition according to any one of claims 1 to 8. A resin sheet comprising a support and a resin composition layer formed from the resin composition according to any one of claims 1 to 8 provided on the support. A printed wiring board comprising an insulating layer made of a cured product of the resin composition according to any one of claims 1 to 8. A semiconductor device comprising the printed wiring board according to claim 12.