TW202307058A - resin composition - Google Patents

Abstract

The present invention relates to a resin composition comprising an epoxy resin. The invention further relates to a resin sheet, a printed wiring board and a semiconductor device which are obtained by using the resin composition. The technical problem of the present invention is to provide a resin composition (for forming an interlayer insulating layer of a printed wiring board) which is capable of obtaining a cured product having excellent stain removability and elongation at break while suppressing the dielectric loss tangent to a low level. A resin composition for forming an interlayer insulating layer of a printed wiring board, which contains (A) an epoxy resin, (B) an active ester compound, and (C) an inorganic filler, in which component (A) contains (A-1) an epoxy resin represented by formula (1). In the formula, each symbol is defined in the specification.

Description

resin composition

The present invention relates to a resin composition comprising an epoxy resin. Further, it relates to a resin sheet, a printed wiring board, and a semiconductor device obtained by using the resin composition.

As a manufacturing technique of a printed wiring board, the manufacturing method by the build-up method which laminates|stacks an insulating layer and a conductor layer alternately is known. In the manufacturing method using the build-up method, the insulating layer is usually formed by curing a resin composition. In recent years, it is required to suppress the dielectric tangent of the insulating layer to be lower.

prior art literature patent documents Patent Document 1: Japanese Patent Laid-Open No. 2018-197282 Patent Document 2: International Publication No. 2020/129724.

The problem to be solved by the invention

Hitherto, as a resin composition for forming an insulating layer, it is known that the dielectric tangent of the insulating layer can be suppressed lower by using an epoxy resin composition blended with an active ester compound (Patent Document 1). However, when an epoxy resin composition blended with an active ester compound is used, a decrease in smear removability, a decrease in elongation at break, and the like become problems.

Furthermore, a 2,6-xylenol/dicyclopentadiene type epoxy resin has been known so far (Patent Document 2).

The object of the present invention is to provide a resin composition (for forming an interlayer insulating layer of a printed wiring board) that can obtain a cured product that suppresses the dielectric tangent low and has excellent smear removability and elongation at break point .

means to solve the problem In order to achieve the subject of the present invention, the present inventors conducted intensive studies and found that by using (A) epoxy resin, (B) active ester compound and (C) inorganic filler, and (A) component contains The resin composition of the specific epoxy resin described below can unexpectedly obtain a cured product with a low dielectric tangent and excellent smear removability and elongation at break point, thereby completing the present invention.

That is, the present invention includes the following.

式中， R ¹各自獨立地表示氫原子、式(1a)所示的基或式(1b)所示的基，並且至少1個R ¹為式(1a)所示的基或式(1b)所示的基：

式(1a)及(1b)中，*表示鍵結部位； R ²及R ³各自獨立地表示碳數1～8的烴基； n為0以上的整數且表示重複單元數。 [1] A resin composition for forming an interlayer insulating layer of a printed wiring board, which is a resin composition comprising (A) an epoxy resin, (B) an active ester compound, and (C) an inorganic filler, wherein ( A) component comprises the epoxy resin shown in (A-1) formula (1):

In the formula, R ¹ each independently represent a hydrogen atom, a group represented by formula (1a) or a group represented by formula (1b), and at least one R ¹ is a group represented by formula (1a) or formula (1b) The base shown:

In formulas (1a) and (1b), * represents a bonding site; R ² and R ³ each independently represent a hydrocarbon group having 1 to 8 carbon atoms; n is an integer of 0 or more and represents the number of repeating units.

[2] The resin composition for forming an interlayer insulating layer of a printed wiring board according to the above [1], wherein the average value of n is within a range of 0 to 5.

[3] The resin composition for forming an interlayer insulating layer of a printed wiring board according to the above [1] or [2], wherein the component (A) further contains an epoxy resin that is liquid at a temperature of 20°C.

[4] The resin composition for forming an interlayer insulating layer of a printed wiring board according to any one of the above [1] to [3], wherein when the non-volatile content in the resin composition is 100% by mass, Content of (A) component is 1 mass % - 30 mass %.

[5] The resin composition for forming an interlayer insulating layer of a printed wiring board according to any one of the above [1] to [4], wherein when the non-volatile content in the resin composition is 100% by mass, (B) Content of a component is 5 mass % or more.

[6] The resin composition for forming an interlayer insulating layer of a printed wiring board according to any one of the above [1] to [5], wherein the component (C) is silicon dioxide.

[7] The resin composition for forming an interlayer insulating layer of a printed wiring board according to any one of the above [1] to [6], wherein when the non-volatile content in the resin composition is 100% by mass, (C) Content of a component is 40 mass % or more.

[8] The resin composition for forming an interlayer insulating layer of a printed wiring board according to any one of the above-mentioned [1] to [7], further comprising a phenoxy resin.

[9] The resin composition for forming an interlayer insulating layer of a printed wiring board according to any one of the above [1] to [8], further comprising a phenolic curing agent.

[10] The resin composition for forming an interlayer insulating layer of a printed wiring board according to any one of the above [1] to [9], wherein, when measured at 23° C. in accordance with JIS K7127, the curing rate of the resin composition is The elongation at break point of the material is above 1.0%.

[11] The resin composition for forming an interlayer insulating layer of a printed wiring board according to any one of the above-mentioned [1] to [10], wherein, when measured at 5.8 GHz and 23° C., the curing rate of the resin composition is The dielectric tangent (Df) of the material is 0.0040 or less.

[12] The resin composition for forming an interlayer insulating layer of a printed wiring board according to any one of the above-mentioned [1] to [11], wherein, when measured at 5.8 GHz and 23°C, the curing of the resin composition is The specific permittivity (Dk) of the material is 3.5 or less.

式中， R ¹各自獨立地表示氫原子、式(1a)所示的基，或式(1b)所示的基，並且至少1個R ¹為式(1a)所示的基或式(1b)所示的基：

式(1a)及(1b)中，*表示鍵結部位； R ²及R ³各自獨立地表示碳數1～8的烴基； n為0以上的整數且表示重複單元數。 [13] A resin sheet for forming an interlayer insulating layer of a printed wiring board, which is a resin sheet having a support and a resin composition layer provided on the support, wherein the resin composition layer is made of resin A resin composition layer formed by a composition, the resin composition includes (A) epoxy resin, (B) active ester compound and (C) inorganic filler, (A) component includes (A-1) formula (1) Epoxies shown:

In the formula, R ¹ each independently represent a hydrogen atom, a group shown in formula (1a), or a group shown in formula (1b), and at least one R ¹ is a group shown in formula (1a) or formula (1b ) shown in the base:

In formulas (1a) and (1b), * represents a bonding site; R ² and R ³ each independently represent a hydrocarbon group having 1 to 8 carbon atoms; n is an integer of 0 or more and represents the number of repeating units.

式中， R ¹各自獨立地表示氫原子、式(1a)所示的基，或式(1b)所示的基，並且至少1個R ¹為式(1a)所示的基或式(1b)所示的基：

式(1a)及(1b)中，*表示鍵結部位； R ²及R ³各自獨立地表示碳數1～8的烴基； n為0以上的整數且表示重複單元數。 [14] A printed wiring board comprising an insulating layer comprising a cured product of a resin composition comprising (A) an epoxy resin, (B) an active ester compound, and (C) an inorganic filler. In this resin composition, (A) component comprises the epoxy resin shown in (A-1) formula (1):

In the formula, R ¹ each independently represent a hydrogen atom, a group shown in formula (1a), or a group shown in formula (1b), and at least one R ¹ is a group shown in formula (1a) or formula (1b ) shown in the base:

In formulas (1a) and (1b), * represents a bonding site; R ² and R ³ each independently represent a hydrocarbon group having 1 to 8 carbon atoms; n is an integer of 0 or more and represents the number of repeating units.

[15] A semiconductor device comprising the printed wiring board according to the above [14].

Invention effect According to the resin composition of the present invention, a cured product having low dielectric tangent and excellent smear removability and elongation at break can be obtained.

Hereinafter, the present invention will be described in detail based on preferred embodiments. However, the present invention is not limited to the following embodiments and illustrations, and can be implemented with arbitrarily modified within a range not departing from the claims of the present invention and its equivalents.

＜Resin composition＞ The resin composition of the present invention is a resin composition for forming an interlayer insulating layer of a printed wiring board (a resin composition for forming an interlayer insulating layer of a printed wiring board). In addition, in this invention, the interlayer insulating layer of a printed wiring board also includes the rewiring formation layer of a semiconductor package.

The resin composition of this invention contains (A) epoxy resin, (B) active ester compound, and (C) inorganic filler, (A) component contains (A-1) specific epoxy resin demonstrated below. By using such a resin composition, it is possible to obtain a cured product that suppresses the dielectric tangent low and has excellent smear removability and elongation at break.

The resin composition of the present invention may further contain optional components in addition to (A) epoxy resin, (B) active ester compound, and (C) inorganic filler. Examples of optional components include (B') other curing agents, (D) thermoplastic resins, (E) curing accelerators, (F) other additives, and (G) organic solvents. Each component contained in the resin composition will be described in detail below.

＜(A) Epoxy resin＞ The resin composition of this invention contains (A) epoxy resin. (A) Epoxy resin means curable resin which has an epoxy group of 5,000 g/eq. or less of epoxy equivalent.

式中， R ¹各自獨立地表示氫原子、式(1a)所示的基，或式(1b)所示的基，並且至少1個R ¹為式(1a)所示的基或式(1b)所示的基：

式(1a)及(1b)中，*表示鍵結部位； R ²及R ³各自獨立地表示碳數1～8的烴基； n為0以上的整數且表示重複單元數。 <(A-1) Specific epoxy resin> In the resin composition of the present invention, (A) epoxy resin contains: (A-1) epoxy resin represented by formula (1) (hereinafter sometimes referred to as "specific epoxy resin") Epoxy resin"),

In the formula, R ¹ each independently represent a hydrogen atom, a group shown in formula (1a), or a group shown in formula (1b), and at least one R ¹ is a group shown in formula (1a) or formula (1b ) shown in the base:

In formulas (1a) and (1b), * represents a bonding site; R ² and R ³ each independently represent a hydrocarbon group having 1 to 8 carbon atoms; n is an integer of 0 or more and represents the number of repeating units.

The units indicated by n may be the same or different for each unit.

R ¹ each independently represent a hydrogen atom, a group shown in formula (1a), or a group shown in formula (1b), and at least one R ¹ is a group shown in formula (1a) or a group shown in formula (1b) base.

R ² and R ³ each independently represent a hydrocarbon group having 1 to 8 carbon atoms. R ² and R ³ are each independently preferably an alkyl group or a phenyl group having 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group, a propyl group or an isopropyl group, and even more preferably a methyl group.

A hydrocarbon group refers to a monovalent group having only carbon atoms as a skeleton atom, and may include a straight-chain structure, a branched-chain structure, and/or a cyclic structure, and may be a group that does not contain an aromatic ring, or may include an aromatic ring. Examples of hydrocarbon groups having 1 to 8 carbons include alkyl groups having 1 to 8 carbons, alkenyl groups having 2 to 8 carbons, aralkyl groups having 7 or 8 carbons, and alkyl groups having 7 or 8 carbons Aryl, phenyl, etc.

The alkyl group means a linear, branched and/or cyclic monovalent aliphatic saturated hydrocarbon group. The alkyl group having 1 to 8 carbons is preferably an alkyl group having 1 to 6 carbons, more preferably an alkyl group having 1 to 3 carbons. Examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, second butyl, third butyl, pentyl, hexyl, Heptyl, octyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 2,4-dimethylcyclohexyl, cyclopentylmethyl, cyclohexylmethyl, etc.

The alkenyl group means a linear, branched and/or cyclic monovalent aliphatic unsaturated hydrocarbon group having at least one carbon-carbon double bond. The alkenyl having 2 to 8 carbons is preferably an alkenyl having 2 to 6 carbons, more preferably an alkenyl having 2 or 3 carbons. Examples of the alkenyl group having 2 to 8 carbon atoms include vinyl, propenyl (allyl, 1-propenyl, isopropenyl), butenyl (1-butenyl, crotyl, methyl allyl, isocrotyl, etc.), pentenyl (1-pentenyl, etc.), hexenyl (1-hexenyl, etc.), heptenyl (1-heptenyl, etc.), octenyl ( 1-octenyl, etc.), cyclopentenyl (2-cyclopentenyl, etc.), cyclohexenyl (3-cyclohexenyl, etc.) and the like.

The aralkyl group means a monovalent aliphatic saturated hydrocarbon group substituted with a monovalent aromatic hydrocarbon group composed of an aromatic carbocyclic ring. Examples of the aralkyl group having 7 or 8 carbon atoms include benzyl group, phenethyl group and α-methylbenzyl group.

The alkylaryl group means a monovalent aromatic hydrocarbon group composed of an aromatic carbocyclic ring substituted with a monovalent aliphatic saturated hydrocarbon group. Examples of alkylaryl groups having 7 or 8 carbon atoms include 4-methylphenyl, 3-methylphenyl, 2-methylphenyl, 2,4-dimethylphenyl, 3, 4-Dimethylphenyl, 4-ethylphenyl, 3-ethylphenyl, 2-ethylphenyl, etc.

n is an integer of 0 or more and represents the number of repeating units. The average value of n is preferably 0 or more, more preferably 0.01 or more, further preferably 0.1 or more, still more preferably 0.3 or more, still more preferably 0.5 or more, particularly preferably 0.6 or more, and the upper limit is preferably 5 or less, more preferably 2 or less, further preferably 1.5 or less, particularly preferably 1 or less.

(A-1) The epoxy equivalent of the specific epoxy resin is preferably 3,700g/eq. or less, more preferably 2,000g/eq. or less, particularly preferably 700g/eq. or less, the lower limit is not particularly limited, preferably It is 244 g/eq. or more, more preferably 260 g/eq. or more, particularly preferably 270 g/eq. or more. The epoxy equivalent is the mass of resin with respect to 1 equivalent of epoxy group. This epoxy equivalent can be measured in accordance with JIS K7236.

(A-1) The specific epoxy resin can be produced, for example, using the method described in International Publication No. 2020/129724 or a method based thereon.

(A-1) The content of the specific epoxy resin relative to the total non-volatile components in the resin composition is not particularly limited, but when the non-volatile components in the resin composition are 100% by mass, it is preferably 50% by mass or less, More preferably, it is 40 mass % or less, More preferably, it is 30 mass % or less, More preferably, it is 20 mass % or less, Especially preferably, it is 15 mass % or less. (A-1) The lower limit of the content of the specific epoxy resin relative to the total non-volatile components is not particularly limited, but from the viewpoint of obtaining the effects of the present invention more remarkably when the non-volatile components in the resin composition are 100% by mass , preferably at least 0.1% by mass, more preferably at least 0.5% by mass, further preferably at least 1% by mass, still more preferably at least 3% by mass, particularly preferably at least 5% by mass.

(A-1) The content of the specific epoxy resin relative to the total (A) epoxy resin in the resin composition is not particularly limited, and when the total (A) epoxy resin in the resin composition is 100% by mass, it is relatively Preferably, it is 90 mass % or less, More preferably, it is 80 mass % or less, Especially preferably, it is 70 mass % or less. (A-1) The lower limit of the content of the specific epoxy resin relative to the entire (A) epoxy resin is not particularly limited, and when the entire (A) epoxy resin in the resin composition is 100% by mass, the obtained From the viewpoint of the effect of the present invention, it is preferably at least 10% by mass, more preferably at least 30% by mass, particularly preferably at least 50% by mass.

＜(A-2) Other epoxy resins＞ In the resin composition of this invention, (A) epoxy resin may contain (A-2) other epoxy resins as an optional component. (A-2) Other epoxy resins are components other than the (A-1) component.

Examples of other epoxy resins (A-2) include bixylenol type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol type epoxy resins, Phenol AF type epoxy resin, dicyclopentadiene type epoxy resin, triphenol type epoxy resin, naphthol novolak type epoxy resin, phenol novolac epoxy resin, tertiary butylcatechol type ring Oxygen resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolak type epoxy resin, phenol arane Base type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin with butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin Resin, cyclohexane-type epoxy resin, cyclohexanedimethanol-type epoxy resin, naphthyl ether-type epoxy resin, trimethylol-type epoxy resin, tetraphenylethane-type epoxy resin, isocyanuric acid Ester-type epoxy resins, phenolphthalimidine-type epoxy resins, and the like. (A-2) Other epoxy resins may be used alone or in combination of two or more.

It is preferable that a resin composition contains the epoxy resin which has 2 or more epoxy groups in 1 molecule as (A-2) other epoxy resins. The proportion of the epoxy resin having two or more epoxy groups in one molecule is preferably at least 50 mass %, more preferably at least 60 mass %, relative to 100 mass % of non-volatile components of other epoxy resins (A-2) , Especially preferably at least 70% by mass.

Epoxy resins include epoxy resins that are liquid at a temperature of 20°C (hereinafter sometimes referred to as "liquid epoxy resins") and epoxy resins that are solid at a temperature of 20°C (hereinafter sometimes referred to as "solid epoxy resins"). epoxy resin"). (A) The epoxy resin may contain only a liquid epoxy resin or only a solid epoxy resin, or may contain a combination of a liquid epoxy resin and a solid epoxy resin as (A-2) other epoxy resin. (A) The epoxy resin preferably contains a liquid epoxy resin as (A-2) other epoxy resins.

The liquid epoxy resin is preferably a liquid epoxy resin having two or more epoxy groups in one molecule.

As the liquid epoxy resin, glycyrrhizol (glycyrol) type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, Glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin with ester skeleton, cyclohexanedimethanol type epoxy resin, cycloaliphatic epoxy resin The glyceryl ether and the epoxy resin having a butadiene structure are more preferably glycyrrhizyl epoxy resin, cycloaliphatic glycidyl ether, bisphenol A epoxy resin and bisphenol F epoxy resin.

Specific examples of liquid epoxy resins include "EX-992L" manufactured by Nagase ChemteX, "YX7400" manufactured by Mitsubishi Chemical Corporation, "HP4032" manufactured by DIC Corporation, "HP4032D", and "HP4032SS" (naphthalene type epoxy resin); Mitsubishi Chemical Corporation's "828US", "828EL", "jER828EL", "825", "Epikote828EL" (bisphenol A type epoxy resin); Mitsubishi Chemical Corporation's "jER807", " 1750" (bisphenol F type epoxy resin); "jER152" (phenol novolac epoxy resin) manufactured by Mitsubishi Chemical Corporation; "630", "630LSD" and "604" (glycidylamine type) manufactured by Mitsubishi Chemical Corporation Epoxy resin); "ED-523T" (glycyrrhizol type epoxy resin) manufactured by ADEKA Corporation; "EP-3950L" and "EP-3980S" (glycidylamine type epoxy resin) manufactured by ADEKA Corporation; ADEKA Corporation "EP-4088S" (dicyclopentadiene epoxy resin); "ZX1059" (mixture of bisphenol A epoxy resin and bisphenol F epoxy resin) manufactured by Nippon Steel Chemical & Materials Co., Ltd. "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX Co., Ltd.; "EX-991L" (epoxy resin containing an alkyleneoxy skeleton and a butadiene skeleton) manufactured by Nagase ChemteX Corporation; Daicel's "Celloxide 2021P" (alicyclic epoxy resin having an ester skeleton); Daicel's "PB-3600", Nippon Soda's "JP-100" and "JP-200" (with Epoxy resin with diene structure); "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin) manufactured by Nippon Steel Chemical & Materials Co., Ltd.; "ZX1658GS" manufactured by Osaka Gas Chemical Co., Ltd. EG-280" (epoxy resin containing a terpene structure); "EX-201" (cyclic aliphatic glycidyl ether) manufactured by Nagase ChemteX Co., Ltd., etc.

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

As the solid epoxy resin, bixylenol-type epoxy resins, naphthalene-type epoxy resins, naphthalene-type four-functional epoxy resins, naphthol novolak-type epoxy resins, and cresol novolak-type epoxy resins are preferable. , dicyclopentadiene epoxy resin, triphenol epoxy resin, naphthol epoxy resin, biphenyl epoxy resin, naphthyl ether epoxy resin, anthracene epoxy resin, bisphenol A ring Oxygen resin, bisphenol AF type epoxy resin, phenol aralkyl type epoxy resin, tetraphenylethane type epoxy resin, phenol benzopyrrolone type epoxy resin.

Specific examples of solid epoxy resins include "HP4032H" (naphthalene-type epoxy resin) manufactured by DIC Corporation; "HP-4700" and "HP-4710" (naphthalene-type tetrafunctional epoxy resin) manufactured by DIC Corporation; epoxy resin); DIC Corporation's "N-690" (cresol novolak type epoxy resin); DIC Corporation's "N-695" (cresol novolak type epoxy resin); DIC Corporation's "HP -7200", "HP-7200HH", "HP-7200H", "HP-7200L" (dicyclopentadiene type epoxy resin); "EXA-7311", "EXA-7311-G3" manufactured by DIC Corporation , "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthyl ether type epoxy resin); "EPPN-502H" (triphenol type epoxy resin) manufactured by Nippon Kayaku Corporation; Japan "NC7000L" (naphthol novolak type epoxy resin) manufactured by Kayaku Corporation; "NC3000H", "NC3000", "NC3000L", "NC3000FH", "NC3100" (biphenyl type epoxy Resin); "ESN475V" and "ESN4100V" (naphthalene-type epoxy resin) manufactured by Nippon Steel Chemical & Materials Co., Ltd.; "ESN485" (naphthol-type epoxy resin) manufactured by Nippon Steel Chemical & Materials Co., Ltd.; Nippon Steel Chemical & Materials Co., Ltd. "ESN375" (dihydroxynaphthalene-type epoxy resin) manufactured by Materials Corporation; "YX4000H", "YX4000", "YX4000HK", "YL7890" (bixylenol-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; Mitsubishi Chemical "YL6121" (biphenyl type epoxy resin) manufactured by the company; "YX8800" (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX7700" (phenol aralkyl type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Co., Ltd.; "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation; ); "jER1010" (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "WHR991S" ( Phenol benzopyrrolone type epoxy resin), etc. These may be used alone or in combination of two or more.

As (A-2) other epoxy resins, when a liquid epoxy resin and a solid epoxy resin are used in combination, the mass ratio (liquid epoxy resin: solid epoxy resin) is preferably 10:1. ~1:50, more preferably 2:1~1:20, especially preferably 1:1~1:10.

(A-2) The epoxy equivalent of other epoxy resins is preferably 50g/eq.～5,000g/eq., more preferably 60g/eq.～2,000g/eq., further preferably 70g/eq.～ 1,000g/eq., more preferably 80g/eq. to 500g/eq. The epoxy equivalent is the mass of resin with respect to 1 equivalent of epoxy group. This epoxy equivalent can be measured in accordance with JIS K7236.

(A-2) The weight average molecular weight (Mw) of another epoxy resin becomes like this. Preferably it is 100-5,000, More preferably, it is 250-3,000, More preferably, it is 400-1,500. The weight average molecular weight of resin can be measured as the value of polystyrene conversion by the gel permeation chromatography (GPC) method.

(A-2) The content of other epoxy resins relative to the total non-volatile components in the resin composition is not particularly limited, but when the non-volatile components in the resin composition are 100% by mass, it is preferably 30% by mass or less, More preferably, it is 10 mass % or less, Especially preferably, it is 5 mass % or less. (A-2) The lower limit of the content of other epoxy resins relative to the total non-volatile components is not particularly limited, and when the non-volatile components in the resin composition are 100% by mass, for example, it is 0% by mass or more, 0.01% by mass or more , preferably at least 0.1% by mass, more preferably at least 1% by mass, particularly preferably at least 3% by mass.

(A) The content of the epoxy resin relative to the total non-volatile components in the resin composition is not particularly limited, but when the non-volatile components in the resin composition are 100% by mass, it is preferably 70% by mass or less, more preferably 50% by mass or less, more preferably 30% by mass or less, further preferably 20% by mass or less, particularly preferably 15% by mass or less. (A) The lower limit of the content of the epoxy resin relative to the total non-volatile components is not particularly limited, but when the non-volatile components in the resin composition are 100% by mass, it is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, more preferably at least 1% by mass, still more preferably at least 5% by mass, particularly preferably at least 10% by mass.

＜(B) Active ester compound＞ The resin composition of this invention contains (B) active ester compound. (B) The active ester compound may be used individually by 1 type, and may use it combining 2 or more types by arbitrary ratios. (B) The active ester compound may function as an epoxy resin hardener which reacts with (A) epoxy resin and hardens it.

As the (B) active ester compound, it is generally preferable to use esters having two or more highly reactive esters in one molecule, such as phenol esters, thiophenol esters, N-hydroxylamine esters, and esters of heterocyclic hydroxy compounds. base compound. The active ester compound is preferably an active ester compound obtained by condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxyl compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester compound obtained from a carboxylic acid compound and a hydroxyl compound is preferred, and an active ester compound obtained from a carboxylic acid compound, a phenol compound and/or a naphthol compound is more preferred. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, and methylated bisphenol F. , methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-di Hydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, trihydroxybenzene, dicyclopentadiene-type diphenol compounds , Phenol novolac, etc. Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol and one molecule of dicyclopentadiene.

Specifically, as (B) the active ester compound, preferred are dicyclopentadiene-type active ester compounds, naphthalene-type active ester compounds containing a naphthalene structure, active ester compounds containing acetylated phenol novolaks, phenol-novolak-containing Active ester compounds of benzoyl compounds of varnishes, more preferably at least one selected from dicyclopentadiene-type active ester compounds and naphthalene-type active ester compounds, and more preferably dicyclopentadiene-type active ester compounds compound. As the dicyclopentadiene-type active ester compound, an active ester compound containing a dicyclopentadiene-type diphenol structure is preferable.

As commercially available products of (B) active ester compounds, examples of active ester compounds containing a dicyclopentadiene-type diphenol structure include "EXB9451", "EXB9460", "EXB9460S", "EXB-8000L", "EXB- 8000L-65M", "EXB-8000L-65TM", "HPC-8000L-65TM", "HPC-8000", "HPC-8000-65T", "HPC-8000H", "HPC-8000H-65TM", ( DIC Corporation); active ester compounds containing a naphthalene structure include "HP-B-8151-62T", "EXB-8100L-65T", "EXB-8150-60T", "EXB-8150-62T", " EXB-9416-70BK", "HPC-8150-60T", "HPC-8150-62T", "EXB-8" (manufactured by DIC Corporation); examples of phosphorous-containing active ester compounds include "EXB9401" (manufactured by DIC Corporation) Examples of active ester compounds of acetylated phenol novolac include "DC808" (manufactured by Mitsubishi Chemical Corporation), examples of active ester compounds of benzoyl phenol novolak include "YLH1026", "YLH1030", "YLH1048" (manufactured by Mitsubishi Chemical Corporation), and the active ester compound containing a styryl group and a naphthalene structure include "PC1300-02-65MA" (manufactured by Air Water Corporation).

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

When the non-volatile components in the resin composition are 100% by mass, the content of the (B) active ester compound relative to the total non-volatile components in the resin composition is preferably 0.1% by mass or more, more preferably 1% by mass or more , More preferably at least 5% by mass, particularly preferably at least 8% by mass. (B) The upper limit of the content of the active ester compound relative to all non-volatile components is not particularly limited, but when the non-volatile components in the resin composition are 100% by mass, it is preferably 50% by mass or less, more preferably 40% by mass or less, more preferably 30% by mass or less, further preferably 25% by mass or less, particularly preferably 20% by mass or less.

The mass ratio of (B) active ester compound to (A) epoxy resin in the resin composition ((B) component/(A) component) is preferably 0.05 or more, more preferably 0.1 or more, particularly preferably 0.5 above. The upper limit of the mass ratio ((B) component/(A) component) of (B) active ester compound to (A) epoxy resin in the resin composition is preferably 5 or less, more preferably 3 or less, particularly preferably 1 or less.

＜(B’)Other hardeners＞ The resin composition of the present invention may further contain (B') a curing agent other than the component (B) as an optional component. (B') Other curing agents may be used alone or in any combination of two or more. The (B') other curing agent may function as an epoxy resin curing agent that reacts with (A) the epoxy resin and hardens it, similarly to the (B) active ester compound.

(B') Other curing agents are not particularly limited, and examples thereof include phenol-based curing agents, carbodiimide-based curing agents, acid anhydride-based curing agents, amine-based curing agents, benzoxazine-based curing agents, and cyanate esters. Hardeners and mercaptan hardeners. From the viewpoint of further improving the curability of the resin composition, it is particularly preferable that the resin composition of the present invention contains a phenolic curing agent.

The phenolic curing agent is preferably a phenolic curing agent having a novolac structure from the viewpoint of heat resistance and water resistance. In addition, from the viewpoint of adhesiveness to an adherend, a nitrogen-containing phenol-based curing agent is preferred, and a triazine skeleton-containing phenol-based curing agent is more preferred. Among them, a triazine skeleton-containing phenol novolak resin is preferable from the viewpoint of satisfying high heat resistance, water resistance, and adhesiveness. Specific examples of phenolic curing agents include, for example, "MEH-7700", "MEH-7810", and "MEH-7851" manufactured by Meiwa Chemicals Co., Ltd., "NHN" and "CBN" manufactured by Nippon Kayaku Co., Ltd. , "GPH", "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", " SN-375", "SN-395", "LA-7052", "LA-7054", "LA-3018", "LA-3018-50P", "LA-1356", "TD2090" manufactured by DIC Corporation , "TD-2090-60M" and so on.

Examples of carbodiimide-based curing agents include those having one or more, preferably two or more, carbodiimide structures in one molecule, such as tetramethylene-bis(tertbutylene) aliphatic biscarbodiimide), such as cyclohexanebis(methylene-tert-butylcarbodiimide); aromatic bis(xylylcarbodiimide) and other aromatic Biscarbodiimide such as biscarbodiimide; polyhexamethylenecarbodiimide, polytrimethylhexamethylenecarbodiimide, polycyclohexylcarbodiimide, poly(methylene Biscyclohexylcarbodiimide), poly(isophoronecarbodiimide) and other aliphatic polycarbodiimides; poly(phenylenecarbodiimide), poly(naphthylcarbodiimide) ), poly(cresylcarbodiimide), poly(methyldiisopropylenylcarbodiimide), poly(triethylenylcarbodiimide), poly(diethylenylcarbodiimide) diimide), poly(triisopropylphenylenecarbodiimide), poly(diisopropylphenylenecarbodiimide), poly(xylylenecarbodiimide), poly(tetramethylxylene Carbodiimide), poly(methylenebisphenylenecarbodiimide), poly[methylene bis(methylphenylene)carbodiimide] and other aromatic polycarbodiimides Diimine.

Examples of commercially available carbodiimide curing agents include "Carbodilite V-02B", "Carbodilite V-03", "Carbodilite V-04K", and "Carbodilite V-07" manufactured by Nisshinbo Chemical Co., Ltd. and "CARBODILITE V-09"; "Stabaxol P", "Stabaxol P400", "Hycasyl 510" manufactured by Rhein-Chemie, etc.

Examples of the acid anhydride curing agent include those having one or more acid anhydride groups in one molecule, preferably those having two or more acid anhydride groups in one molecule. Specific examples of acid anhydride hardeners include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, Diformic Anhydride, Methyl Nadic Anhydride, Hydrogenated Methyl Nadic Anhydride, Trialkyltetrahydrophthalic Anhydride, Dodecenyl Succinic Anhydride, 5-(2,5-Dioxotetrahydro-3- Furyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalene tetracarboxylic dicarboxylic acid anhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenyl tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro Copolymerization of -2,5-dioxo-3-furyl)-naphtho[1,2-c]furan-1,3-dione, ethylene glycol bis(trimellitic anhydride), styrene and maleic acid Polymer-type acid anhydrides such as styrene and maleic acid resins. Examples of commercially available acid anhydride curing agents include "HNA-100", "MH-700", "MTA-15", "DDSA", "OSA" manufactured by Shin Nippon Chemical Co., Ltd., and Mitsubishi Chemical Corporation. "YH-306", "YH-307", "HN-2200", "HN-5500" manufactured by Hitachi Chemical Co., Ltd., "EF-30", "EF-40", "EF-60" manufactured by CRAY VALLEY, "EF-80" etc.

Examples of the amine-based curing agent include those having one or more, preferably two or more, amine groups in one molecule, such as aliphatic amines, polyether amines, alicyclic amines, aromatic Among them, aromatic amines are preferred from the viewpoint of achieving the desired effect of the present invention. The amine hardener is preferably a primary amine or a secondary amine, more preferably a primary amine. Specific examples of amine hardeners include 4,4'-methylenebis(2,6-dimethylaniline), 4,4'-diaminodiphenylmethane, 4,4'- Diaminodiphenylene, 3,3'-diaminodiphenylene, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybiphenyl Aniline, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2, 2-bis(4-aminophenoxy)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)pyridine, bis(4-(3-aminophenoxy)phenyl)pyridine, etc. Commercially available amine curing agents can be used, and examples include "SEIKACURE-S" manufactured by SEIKA Corporation, "KAYABOND C-200S" manufactured by Nippon Kayaku Co., Ltd., "KAYABOND C-100", "KAYABOND A-A", " "KAYABOND A-B", "KAYABOND A-S", "Epicure W" manufactured by Mitsubishi Chemical Corporation, etc.

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

Examples of cyanate-based hardeners include bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1,5-phenylene cyanate), 4, 4'-methylene bis(2,6-dimethylphenyl cyanate), 4,4'-ethylene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2, 2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-Bis(4-cyanatephenyl-1-(methylethylene))benzene, bis(4-cyanatephenyl)sulfide, and bis(4-cyanatephenyl) Difunctional cyanate resins such as ethers, polyfunctional cyanate resins derived from phenol novolaks and cresol novolacs, prepolymers of partially triazinated prepolymers of these cyanate resins, and the like. Specific examples of cyanate-based hardeners include "PT30" and "PT60" (both phenol novolak-type polyfunctional cyanate resins), "BA230" and "BA230S75" (two Part or all of phenol A dicyanate is triazinated to form a prepolymer of a trimer) and the like.

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

(B') The reactive group equivalent weight of other curing agents is preferably 50g/eq. to 3000g/eq., more preferably 100g/eq. to 1000g/eq., further preferably 100g/eq. to 500g/eq. , especially preferably 100g/eq. to 300g/eq. The reactive group equivalent is the mass of the curing agent per 1 equivalent of the reactive group.

(B') The content of other curing agents relative to the total non-volatile components in the resin composition is not particularly limited, but when the non-volatile components in the resin composition are 100% by mass, it is preferably at most 20% by mass, more preferably It is 10 mass % or less, More preferably, it is 5 mass % or less, Especially preferably, it is 3 mass % or less. (B') The lower limit of the content of other curing agents relative to the total non-volatile components is not particularly limited, and when the non-volatile components in the resin composition are 100% by mass, for example, it can be 0% by mass or more, 0.01% by mass or more, 0.1% by mass or more, 1% by mass or more, etc.

When the total curing agent in the resin composition (that is, the total of the (B) active ester compound and (B') other curing agents) is 100% by mass, the (B) active ester compound relative to the total curing agent in the resin composition The content of the agent is preferably at least 10% by mass, more preferably at least 30% by mass, further preferably at least 40% by mass, particularly preferably at least 50% by mass.

＜(C) Inorganic filler＞ The resin composition of the present invention contains (C) an inorganic filler. (C) The inorganic filler is contained in the resin composition in the state of particles.

As a material of (C) the inorganic filler, an inorganic compound is used. Examples of materials for the (C) inorganic filler include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, water Aluminum stone, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, Bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium titanate zirconate, barium zirconate, calcium zirconate, zirconium phosphate and zirconium tungstate, etc. Among them, silicon dioxide is particularly suitable. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Moreover, as silica, spherical silica is preferable. (C) The inorganic filler may be used individually by 1 type, and may be used combining 2 or more types by arbitrary ratios.

As commercially available items of (C) inorganic fillers, for example, "UFP-30" manufactured by Denka Chemical Industry Co., Ltd.; "SP60-05" and "SP507-05" manufactured by Nippon Steel & Sumikin Materials Co., Ltd.; "YC100C", "YA050C", "YA050C-MJE", "YA010C" manufactured by the company; "UFP-30" manufactured by Denka Corporation; "Silfil NSS-3N", "Silfil NSS-4N" manufactured by Tokuyama Corporation Silfil NSS-5N"; "SC2500SQ", "SO-C4", "SO-C2", and "SO-C1" manufactured by Admatechs; "DAW-03" and "FB-105FD" manufactured by Denka Corporation.

(C) 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, further preferably 2 μm or less, still more preferably 1 μm or less, particularly preferably 0.7 μm or less. (C) The lower limit of the average particle diameter of the inorganic filler is not particularly limited, but is preferably at least 0.01 μm, more preferably at least 0.05 μm, further preferably at least 0.1 μm, and particularly preferably at least 0.2 μm. (C) The average particle diameter of the inorganic filler can be measured by a laser diffraction/scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be created on a volume basis with a laser diffraction scattering particle size distribution measuring device, and the median diameter can be measured as the average particle size. As a measurement sample, a sample obtained by weighing 100 mg of the inorganic filler and 10 g of methyl ethyl ketone into a vial and ultrasonically dispersing it for 10 minutes can be used. Using a laser diffraction particle size distribution measuring device for the measurement sample, the wavelength of the light source used is set to blue and red, and the volume-based particle size distribution of the inorganic filler is measured by the flow cell method, and the obtained particle size distribution is calculated as Median diameter is the average particle size. As a laser diffraction type particle size distribution measuring apparatus, "LA-960" by Horiba Corporation etc. is mentioned, for example.

(C) The specific surface area of the inorganic filler is not particularly limited, but is preferably at least 0.1 m ² /g, more preferably at least 0.5 m ² /g, further preferably at least 1 m ² /g, particularly preferably at least 3 m ² /g more than g. (C) The upper limit of the specific surface area of the inorganic filler is not particularly limited, but is preferably at most 100 m ² /g, more preferably at most 70 m ² /g, further preferably at most 50 m ² /g, particularly preferably at most 40 m ^{2 /g} below g. The specific surface area of the inorganic filler can be calculated according to the BET method by using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech Co., Ltd.) to adsorb nitrogen gas on the sample surface and calculate the specific surface area using the BET multipoint method.

The (C) inorganic filler is preferably treated with a surface treatment agent from the viewpoint of improving moisture resistance and dispersibility. Examples of surface treatment agents include fluorine-containing silane coupling agents, aminosilane-based coupling agents, epoxysilane-based coupling agents, mercaptosilane-based coupling agents, silane-based coupling agents, alkoxysilanes, and organosilazanes. compound, titanate coupling agent, etc. Moreover, a surface treatment agent may be used individually by 1 type, and may use it in combination of 2 or more types arbitrarily.

Commercially available surface treatment agents include, for example, Shin-Etsu Chemical Co., Ltd. "KBM403" (3-glycidoxypropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM803" (3-mercapto Propyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM573" (N-phenyl-3-aminopropyl Trimethoxysilane), Shin-Etsu Chemical Co., Ltd. "SZ-31" (hexamethyldisilazane), Shin-Etsu Chemical Co., Ltd. "KBM103" (phenyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM -4803" (long-chain epoxy-type silane coupling agent), "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., N-phenyl manufactured by Shin-Etsu Chemical Co., Ltd. -8-Aminooctyltrimethoxysilane, etc.

The degree of surface treatment by the surface treatment agent is preferably controlled 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% to 5% by mass, more preferably 0.2% to 3% by mass, and further preferably 0.3% to 3% by mass. 2% by mass for surface treatment.

The degree of surface treatment with a 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, still more preferably 0.2 mg from the viewpoint of improving the dispersibility of the inorganic filler / ^m2 or more. On the other hand, from the viewpoint of preventing an increase in the melt viscosity of the resin composition or the melt viscosity in the form of a sheet, it is preferably 1.0 mg/m ² or less, more preferably 0.8 mg/m ² or less, and still more preferably 0.8 mg/m 2 or less. 0.5mg/m ² or less.

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

(C) The content of the inorganic filler relative to the total non-volatile components in the resin composition is not particularly limited. When the non-volatile components in the resin composition are 100% by mass, it is preferably 90% by mass or less, more preferably It is 85 mass % or less, More preferably, it is 80 mass % or less, Especially preferably, it is 75 mass % or less. (C) The lower limit of the content of the inorganic filler relative to the total non-volatile components is not particularly limited, but when the non-volatile components in the resin composition are 100% by mass, it is preferably 40% by mass or more, more preferably 50% by mass Above, more preferably at least 60% by mass, still more preferably at least 65% by mass, particularly preferably at least 70% by mass.

(C) The mass ratio of the inorganic filler to the (A) epoxy resin in the resin composition ((C) component/(A) component) is preferably 0.5 or more, more preferably 1 or more, particularly preferably 3 above. (C) The upper limit of the mass ratio ((C) component/(A) component) of the inorganic filler to the (A) epoxy resin in the resin composition is preferably 50 or less, more preferably 30 or less, particularly preferably 10 or less.

＜(D) Thermoplastic resin＞ The resin composition of the present invention may further contain (D) a thermoplastic resin as an optional component. (D) The thermoplastic resin demonstrated here is a component which does not belong to (A) epoxy resin.

Examples of (D) thermoplastic resins include polyimide resins, phenoxy resins, polyvinyl acetal resins, polyolefin resins, polybutadiene resins, polyamide imide resins, polyether acetal resins, and polyamide imide resins. Imine resin, polyresin, polyether resin, polyphenylene ether resin, polycarbonate resin, polyether ether ketone resin, polyester resin, etc. In one embodiment, the resin composition of the present invention preferably includes a thermoplastic resin selected from the group consisting of polyimide resin and phenoxy resin, more preferably includes phenoxy resin. Moreover, a thermoplastic resin may be used individually by 1 type, or may use it in combination of 2 or more types.

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

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

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

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

Examples of polyolefin resins include low-density polyethylene, ultra-low-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-methyl acrylate copolymer. It is a copolymer resin; polyolefin polymers such as polypropylene and ethylene-propylene block copolymer, etc.

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

Specific examples of the polyimide resin include "VYLOMAX HR11NN" and "VYLOMAX HR16NN" manufactured by Toyobo Corporation. Specific examples of polyamideimide resins include modified polyamideimide resins such as "KS9100" and "KS9300" (polyamideimide containing a polysiloxane skeleton) manufactured by Hitachi Chemical Co., Ltd. imine.

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

Specific examples of the polycarbonate resin include polycarbonate "P1700" and "P3500" manufactured by Solvay Advanced Polymers Co., Ltd., and the like.

Specific examples of the polyphenylene ether resin include "NORYL SA90" manufactured by SABIC, and the like. As a specific example of polyetherimide resin, "ULTEM" by GE company etc. are mentioned.

Examples of polycarbonate resins include: hydroxyl-containing carbonate resins, phenolic hydroxyl-containing carbonate resins, carboxyl-containing carbonate resins, acid anhydride-containing carbonate resins, isocyanate-containing carbonate resins, Urethane-based carbonate resins, etc. Specific examples of polycarbonate resins include "FPC0220" manufactured by Mitsubishi Gas Chemical Co., Ltd., "T6002" and "T6001" (polycarbonate diol) manufactured by Asahi Kasei Chemical Co., Ltd., and "C- 1090", "C-2090", "C-3090" (polycarbonate diol), etc. Specific examples of the polyether ether ketone resin include "SUMIPLOY K" manufactured by Sumitomo Chemical Co., Ltd., and the like.

As the polyester resin, for example, polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin, polybutylene naphthalate resin, polyethylene terephthalate resin, Trimethylene phthalate resin, polytrimethylene naphthalate resin, polycyclohexanedimethyl terephthalate resin, etc.

From the viewpoint of remarkably obtaining the effect of the present invention, the weight average molecular weight (Mw) of the (D) thermoplastic resin is preferably 5,000 or more, more preferably 8,000 or more, further preferably 10,000 or more, particularly preferably 20,000 or more, and more preferably Preferably it is 100,000 or less, more preferably 70,000 or less, further preferably 60,000 or less, particularly preferably 50,000 or less.

(D) The content of the thermoplastic resin relative to the total non-volatile components in the resin composition is not particularly limited, but when the non-volatile components in the resin composition are 100% by mass, it is preferably 20% by mass or less, more preferably 15% by mass or less, more preferably 10% by mass or less, further preferably 5% by mass or less, particularly preferably 3% by mass or less. (D) The lower limit of the content of the thermoplastic resin relative to the total non-volatile components is not particularly limited, and when the non-volatile components in the resin composition are taken as 100% by mass, for example, it may be 0% by mass or more, 0.01% by mass or more, 0.1% by mass or more. Mass % or more, 1 mass % or more, etc.

＜(E) Hardening Accelerator＞ The resin composition of the present invention may further contain (E) a hardening accelerator as an optional component. (E) The hardening accelerator has a function as a hardening catalyst which accelerates hardening of (A) epoxy resin.

(E) 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. (E) The curing accelerator preferably includes a curing accelerator selected from imidazole-based curing accelerators and amine-based curing accelerators, and particularly preferably includes an amine-based curing accelerator. (E) The curing accelerator may be used alone or in combination of two or more.

Examples of phosphorus-based hardening accelerators include tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium caprate, tetrabutylphosphonium laurate, bis (Tetrabutylphosphonium) pyromellitate, tetrabutylphosphonium hydrogen hexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl ]-4-methylphenolate, di-tert-butylmethylphosphonium tetraphenylborate and other aliphatic phosphonium salts; methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenyl bromide phosphonium, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra-p-tolyl borate, tetraphenylphosphonium tetraphenylboronic acid salt, tetraphenylphosphonium tetra-p-tolylborate, triphenylethylphosphonium tetraphenylborate, tris(3-methylphenyl)ethylphosphonium tetraphenylborate, tris(2-methoxy Phenyl)ethylphosphonium tetraphenylborate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate and other aromatic Phosphonium salts; aromatic phosphine and borane complexes such as triphenylphosphine and triphenylborane; aromatic phosphine and benzoquinone addition reactants such as triphenylphosphine and p-benzoquinone; tributyl Base phosphine, tri-tertiary butyl phosphine, trioctyl phosphine, di-tertiary butyl (2-butenyl) phosphine, di-tertiary butyl (3-methyl-2-butenyl) phosphine, tricyclic Aliphatic phosphine such as hexylphosphine; dibutylphenylphosphine, di-tert-butylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclohexylphosphine , triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tri(4-ethylphenyl)phosphine, tri(4-propylphenyl)phosphine, tri (4-isopropylphenyl)phosphine, tri(4-butylphenyl)phosphine, tri(4-tert-butylphenyl)phosphine, tri(2,4-dimethylphenyl)phosphine, tri (2,5-Dimethylphenyl)phosphine, Tris(2,6-Dimethylphenyl)phosphine, Tris(3,5-Dimethylphenyl)phosphine, Tris(2,4,6-tris Methylphenyl)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)ethyl alkane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,2-bis(diphenylphosphino)acetylene, 2,2'- Aromatic phosphines such as bis(diphenylphosphino)diphenyl ether, etc.

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

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

Examples of imidazole-based hardening 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-methyl Imidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2- Ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl- 2-Phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-di Amino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'- Methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine Oxyzine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxyl Methylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazolium imidazoline, 2-phenylimidazoline and other imidazole compounds and adducts of imidazole compounds and epoxy resins.

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

Examples of metal-based hardening accelerators include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organocobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organocopper complexes such as copper (II) acetylacetonate, and Organic zinc complexes such as zinc (II) acetylacetonate, organic iron complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, organic manganese (II) acetylacetonate, etc. Manganese complexes, etc. Examples of organic metal salts include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate and the like.

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

A commercial item can be used as an amine hardening accelerator, For example, "MY-25" by Ajinomoto Fine-Techno Co., Ltd. etc. are mentioned.

The content of the (E) hardening accelerator in the resin composition is not particularly limited, but when the non-volatile components in the resin composition are 100% by mass, it is preferably 5% by mass or less, more preferably 1% by mass or less, and further Preferably it is 0.5 mass % or less, Especially preferably, it is 0.1 mass % or less. The lower limit of the content of the (E) hardening accelerator in the resin composition is not particularly limited, and when the non-volatile content in the resin composition is 100% by mass, for example, it may be 0% by mass or more, 0.001% by mass or more, 0.01% by mass or more. Mass% or more, etc.

＜(F)Other additives＞ The resin composition of the present invention may further contain optional additives as nonvolatile components. Examples of such additives include epoxy acrylate resins, urethane acrylate resins, urethane resins, cyanate resins, benzoxazine resins, unsaturated polyester resins, phenol Resin, melamine resin, silicone resin, epoxy resin and other thermosetting resins; with 4-vinylphenyl, acryl, methacryl, maleimide (2,5-dihydro -2,5-two side oxygen-1H-pyrrol-1-yl) radical polymerizable compounds; free radical polymerization initiators such as peroxide-based radical polymerization initiators, azo-based radical polymerization initiators, etc.; Organic filling materials such as rubber particles; organometallic compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, and carbon black; Polymerization inhibitors such as hydroquinone, catechol, gallol, and phenothiazine; leveling agents such as silicone-based leveling agents and acrylic polymer-based leveling agents; organic clay, montmorillonite, etc. Thickeners; Silicone-based defoamers, acrylic-based defoamers, fluorine-based defoamers, vinyl resin-based defoamers and other defoamers; benzotriazole-based UV absorbers and other UV absorbers; urea Adhesion improving agents such as silanes; Adhesion imparting agents such as triazole-based adhesion-imparting agents, tetrazole-based adhesion-imparting agents, triazine-based adhesion-imparting agents; hindered phenolic antioxidants and other antioxidants; Fluorescent whitening agents such as stilbene derivatives; surfactants such as fluorine-based surfactants and polysiloxane-based surfactants; phosphorus-based flame retardants (such as phosphoric acid ester compounds, , red phosphorus), nitrogen-based flame retardants (such as melamine sulfate), halogen-based flame retardants, inorganic-based flame retardants (such as antimony trioxide) and other flame retardants; phosphate-based dispersants, polyoxyalkylene-based dispersants , acetylene-based dispersant, polysiloxane-based dispersant, anionic dispersant, cationic dispersant and other dispersants; borate-based stabilizers, titanate-based stabilizers, aluminate-based stabilizers, zirconate-based stabilizers Stabilizers such as isocyanate-based stabilizers, carboxylic acid-based stabilizers, carboxylic anhydride-based stabilizers, etc. (F) Other additives may be used alone or in combination of two or more in arbitrary ratios. (F) The content of other additives can be appropriately set by those skilled in the art.

＜(G)Organic solvent＞ The resin composition of the present invention may further contain an optional organic solvent as a volatile component in addition to the above-mentioned non-volatile components. As (G) organic solvent, a well-known organic solvent can be used suitably, and the kind is not specifically limited. (G) Organic solvents include, for example, ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; methyl acetate, ethyl acetate, butyl acetate, and isobutyl acetate; Esters, isoamyl acetate, methyl propionate, ethyl propionate, γ-butyrolactone and other ester solvents; tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, Dibutyl ether, diphenyl ether, anisole and other ether solvents; methanol, ethanol, propanol, butanol, ethylene glycol and other alcohol solvents; 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate , diethylene glycol monoethyl ether acetate, ethyl diglycol acetate, γ-butyrolactone, methyl methoxypropionate and other ether ester solvents; methyl lactate, ethyl lactate Esters, methyl 2-hydroxyisobutyrate and other ester alcohol solvents; 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, diethylene glycol monobutyl Ether alcohol solvents such as base ether (butyl carbitol); N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone and other amides Acetonitrile-based solvents such as dimethylsulfide; nitrile-based solvents such as acetonitrile and propionitrile; aliphatic hydrocarbon-based solvents such as hexane, cyclopentane, cyclohexane, and methylcyclohexane; benzene, toluene, Aromatic hydrocarbon solvents such as xylene, ethylbenzene, trimethylbenzene, etc. (G) The organic solvent may be used individually by 1 type, and may use it combining 2 or more types by arbitrary ratios.

The content of the (G) organic solvent in the varnish-like resin composition before drying is not particularly limited, and when all the components in the resin composition are taken as 100% by mass, for example, it is 40% by mass or less, 30% by mass or less. Preferably, it is 20 mass % or less, More preferably, it is 10 mass % or less, More preferably, it is 8 mass % or less, Especially preferably, it is 6 mass % or less. The content of the (G) organic solvent in the resin composition forming the dried resin composition layer in the resin sheet is not particularly limited, but when all the components in the resin composition are taken as 100% by mass, it is preferably 5% by mass. % or less, more preferably 3 mass % or less, further preferably 2 mass % or less, particularly preferably 1 mass % or less.

＜Manufacturing method of resin composition＞ The resin composition of the present invention, for example, can be prepared by adding (A) epoxy resin, (B) active ester compound, (C) inorganic filler in any order and/or partly or all at the same time in any preparation container. (D) thermoplastic resin, if necessary (E) hardening accelerator, if necessary (F) other additives, and if necessary (G) organic solvent, are mixed and manufactured. In addition, in the process of adding and mixing each component, the temperature may be set appropriately, and heating and/or cooling may be performed temporarily or constantly. In addition, during or after adding and mixing, the resin composition may be stirred or shaken using a stirring device such as a mixer or an oscillating device to uniformly disperse it. In addition, defoaming may be performed under low-pressure conditions such as under vacuum while stirring or shaking.

＜Characteristics of resin composition＞ The resin composition of this invention contains (A) epoxy resin, (B) active ester compound, and (C) inorganic filler, (A) component contains (A-1) specific epoxy resin demonstrated above. By using such a resin composition, it is possible to obtain a cured product that suppresses the dielectric tangent low and has excellent smear removability and elongation at break.

The cured product of the resin composition of the present invention can be characterized by excellent elongation at break. Therefore, in one embodiment, when measured at 23°C in accordance with JIS K7127 as in Test Example 3 below, the elongation at break of the cured product of the resin composition of the present invention is preferably 0.5% or more, more preferably 0.5% or more. 0.8% or more, more preferably 1.0% or more, still more preferably 1.2% or more, particularly preferably 1.4% or more. The upper limit of the elongation at breaking point can usually be set to 10% or less, 5% or less, or the like.

The cured product of the resin composition of the present invention can have excellent smear removability. Therefore, in one embodiment, a via hole having a diameter of 50 μm at the top of the surface of the hardened product and a diameter of 40 μm at the bottom of the via hole is formed as in Test Example 2 below, and the surface of the via hole bottom is measured after the roughening treatment. When the maximum smear length is raised, the maximum smear length can be less than 5 μm.

The cured product of the resin composition of the present invention can have a low dielectric tangent (Df). Therefore, in one embodiment, the dielectric tangent (Df) of the cured product of the resin composition when measured at 5.8 GHz and 23° C. is preferably 0.0100 or less, 0.0080 or less, more preferably It is 0.0070 or less, 0.0060 or less, more preferably 0.0050 or less, 0.0045 or less, particularly preferably 0.0040 or less, 0.0035 or less.

In one embodiment, the cured product of the resin composition of the present invention is characterized by a low specific permittivity (Dk). Therefore, in one embodiment, the specific permittivity (Dk) of the cured product of the resin composition when measured at 5.8 GHz and 23° C. as in Test Example 1 below may be preferably 5.0 or less, more preferably 4.5 or less, more preferably 4.0 or less, still more preferably 3.7 or less, particularly preferably 3.5 or less, 3.4 or less.

＜Resin sheet＞ The resin composition of the present invention can also be coated and used in a varnish state, but industrially it is generally suitable to use it in the form of a resin sheet containing the resin composition.

The resin sheet of the present invention is a resin sheet for forming an interlayer insulating layer of a printed wiring board (a resin sheet for forming an interlayer insulating layer of a printed wiring board).

In one embodiment, the resin sheet has a support body and a resin composition layer provided on the support body, and the resin composition layer is formed of the resin composition described above.

The thickness of the resin composition layer is preferably 50 μm or less, more preferably 40 μm or less, from the viewpoint of thinning the printed wiring board and providing a cured product with excellent insulation properties even if the cured product of the resin composition is a thin film. . The lower limit of the thickness of the resin composition layer is not particularly limited, and usually it can be 5 μm or more, 10 μm or more, or the like.

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

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

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

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

Moreover, as a support body, the support body with a mold release layer which has a mold release layer on the surface bonded to a resin composition layer can be used. As the release agent used in the release layer of the support body with a release layer, for example, one or more selected from alkyd resins, polyolefin resins, urethane resins, and silicone resins can be mentioned. Release agent. Commercially available products can be used as the support with a release layer, for example, a PET film having a release layer mainly composed of an alkyd resin release agent, that is, "SK-1" manufactured by LINTEC Corporation, "AL-5", "AL-7", "Lumirror T60" manufactured by Toray Corporation, "Purex" manufactured by Teijin Corporation, "Unipeel" manufactured by UNITIKA Corporation, etc.

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. Furthermore, when using the support body with a release layer, it is preferable that the thickness of the whole support body with a release layer is the said range.

In one embodiment, the resin sheet may further include an optional layer as necessary. Examples of the optional layer include a support-based protective film provided on the surface of the resin composition layer that is not bonded to the support (ie, the surface opposite to the support). The thickness of the protective film is not particularly limited, and is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to suppress adhesion of dust and the like or generation of scratches on the surface of the resin composition layer.

The resin sheet can be formed, for example, by applying a liquid resin composition directly or by preparing a resin varnish obtained by dissolving the resin composition in an organic solvent, coating it on a support with a die coater, etc., and drying it. Resin composition layer to manufacture.

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

Drying can be implemented by known methods such as heating and blowing hot air. The drying conditions are not particularly limited, and drying is performed so that the content of the organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. It also differs 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 an organic solvent, it can be heated at 50°C to 150°C. The resin composition layer is formed by drying at °C for 3 minutes to 10 minutes.

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

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

A printed wiring board can be manufactured by the method including the following (I) and (II) process using the said resin sheet, for example.

(1) Step of laminating the resin sheet on the inner substrate so that the resin composition layer of the resin sheet is bonded to the inner substrate (II) Step of hardening (for example, thermosetting) the resin composition layer to form an insulating layer The "inner layer substrate" used in the step (I) refers to a member that is a substrate of a printed wiring board, for example, a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, Thermosetting polyphenylene ether substrate, etc. In addition, the substrate may have a conductor layer on one or both sides thereof, and the conductor layer may be patterned. An inner layer substrate in which a conductor layer (circuit) is formed on one or both surfaces of the substrate may be referred to as an "inner layer circuit board". In addition, an intermediate product in which an insulating layer and/or a conductor layer is further formed at the time of manufacturing a printed wiring board is also included in the "inner layer substrate" in the present invention. When the printed wiring board is a circuit board with built-in components, an inner layer substrate with built-in components can also be used.

The lamination of the inner layer substrate and the resin sheet can be performed, for example, by thermocompression-bonding the resin sheet to the inner layer substrate from the side of the support. As a member for thermocompression-bonding a grease sheet to an inner substrate (hereinafter also referred to as "thermocompression bonding member"), for example, a heated metal plate (SUS end plate, etc.) or a metal roller (SUS roller), etc. Furthermore, instead of directly pressing the thermocompression bonding member on the resin sheet, it is preferably pressed through an elastic material such as heat-resistant rubber, so that the resin sheet can fully follow the surface irregularities of the inner substrate.

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

Lamination can be performed with a commercially available vacuum laminator. As a commercially available vacuum laminator, a vacuum pressure laminator manufactured by Meiki Seisakusho Co., Ltd., a vacuum applicator manufactured by Nikko-Materials, a batch type vacuum pressure laminator, etc. are mentioned, for example.

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

The support body can be removed between step (I) and step (II), and can also be removed after step (II).

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

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

Before thermosetting the resin composition layer, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, before thermally curing the resin composition layer, the resin composition layer may be preheated 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, Preferably, it is 5 minutes - 150 minutes, More preferably, it is 15 minutes - 120 minutes, More preferably, it is 15 minutes - 100 minutes.

When manufacturing a printed wiring board, (III) the step of opening a hole in the insulating layer, (IV) the step of roughening the insulating layer, and (V) the step of forming a conductor layer may be further carried out. These steps (III) to (V) can be implemented according to various methods known to those skilled in the art used for the manufacture of a printed wiring board. Furthermore, when the support is removed after step (II), the removal of the support can be between step (II) and step (III), between step (III) and step (IV), or step (IV) ) and step (V) between implementation. In addition, the formation of the insulating layer and the conductor layer of step (II) to step (V) may be repeated as necessary to form a multilayer wiring board.

In another embodiment, the printed wiring board of this invention can be manufactured using the said prepreg. The manufacturing method is basically the same as the case of using a resin sheet.

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

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

The swelling solution used in the roughening treatment is not particularly limited, and examples thereof include an alkali solution, a surfactant solution, and the like, preferably an alkali solution, and more preferably a sodium hydroxide solution or a potassium hydroxide solution as the alkali solution. As a commercially available swelling liquid, "Swelling Dip Securiganth P" and "Swelling Dip Securiganth SBU" manufactured by Atotech Japan Co., Ltd., etc. are mentioned, for example. The swelling treatment using a swelling liquid is not particularly limited, and can be performed, for example, by immersing the insulating layer in a swelling liquid at 30° C. to 90° C. for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling liquid at 40° C. to 80° C. for 5 minutes to 15 minutes.

It does not specifically limit as an oxidizing agent used for a roughening process, For example, the alkaline permanganate solution which dissolved potassium permanganate or sodium permanganate in the aqueous solution of sodium hydroxide is mentioned. 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. In addition, the concentration of permanganate in the alkaline permanganic acid solution is preferably 5% by mass to 10% by mass. As a commercially available oxidizing agent, alkaline permanganate solutions, such as "Concentrate Compact CP" and "Dosing Solution Securiganth P" manufactured by Atotech Japan Co., Ltd., are mentioned, for example.

Moreover, as a neutralization liquid used for a roughening process, an acidic aqueous solution is preferable, and as a commercial item, "Reduction Solution Securiganth P" by ATOTECH JAPAN company is mentioned, for example.

The treatment with the neutralizing solution can be performed by immersing the surface to be roughened with an oxidizing agent in a neutralizing solution at 30° C. to 80° C. for 5 minutes to 30 minutes. From the viewpoint of workability etc., the method of immersing the object roughened with an oxidizing agent in the neutralization liquid of 40 degreeC - 70 degreeC for 5 minutes - 20 minutes is preferable.

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

The step (V) is a step of forming a conductor layer, and the conductor layer is formed on the insulating layer. The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer contains one or more metals selected from gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. The conductor layer can be a single metal layer or an alloy layer, and the alloy layer can be, for example, an alloy of two or more metals selected from the above (for example, nickel-chromium alloy, copper-nickel alloy and copper-titanium alloy) ) layer formed. Among them, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or a single metal layer of nickel is preferable from the viewpoint of the versatility of conductor layer formation, cost, and ease of patterning.・Alloy layer of chromium alloy, copper-nickel alloy, copper-titanium alloy, more preferably single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or alloy layer of nickel-chromium alloy , further preferably a single metal layer of copper.

Even if the conductor layer has a single-layer structure, it may have a multi-layer structure in which two or more single metal layers or alloy layers made of different types of metals or alloys are laminated. When the conductor layer has a 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 design of the printed wiring board, and is usually 3 μm to 35 μm, preferably 5 μm to 30 μm.

In one embodiment, the conductor layer can be formed by plating. For example, the surface of the insulating layer can be plated by conventionally known techniques such as semi-additive method and full-additive method to form a conductor layer with a desired wiring pattern. Jia is formed by the semi-additive method. Hereinafter, an example of forming a conductor layer by a semi-additive method will be shown.

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

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

Metal foil can be manufactured by known methods, such as an electrolysis method and a rolling method, for example. Examples of commercially available metal foils include HLP foil and JXUT-III foil manufactured by JX Nikko Nippon Metal Co., Ltd., 3EC-III foil and TP-III foil manufactured by Mitsui Metal Mining Co., Ltd., and the like.

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

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

Hereinafter, the present invention will be specifically described by way of examples. The present invention is not limited by these Examples. In addition, in the following, "parts" and "%" indicating the amount mean "parts by mass" and "% by mass", respectively, unless otherwise specified. The temperature conditions in the following description are normal temperature (25° C.) unless the temperature is specified, and the pressure conditions are normal pressure (1 atm) unless the pressure is specified.

<Synthesis Example 1: Synthesis of Epoxy Resin A> 95 parts of 2,6-xylenol was placed in a reaction apparatus consisting of a glass separable flask equipped with a stirrer, a thermometer, a nitrogen gas injection tube, a dropping funnel, and a cooling tube. , 6.3 parts of 47% BF ₃ ether complex, heated to 70°C while stirring. While maintaining at the same temperature, 58.8 parts of dicyclopentadiene (0.56 times mole relative to 2,6-xylenol) was added dropwise over 1 hour. After further reacting at a temperature of 115 to 125°C for 3 hours, 69.2 parts of dicyclopentadiene (0.67 times the mole relative to 2,6-xylenol) was added dropwise at the same temperature over 1 hour, and at 115°C The reaction was carried out at a temperature of ~125°C for 2 hours. 1.0 parts of calcium hydroxide was added, and 2.0 parts of 10% oxalic acid aqueous solution was further added. Thereafter, it was heated to 160° C. for dehydration, and then heated to 200° C. under a reduced pressure of 5 mmHg to evaporate and remove unreacted raw materials. 520 parts of MIBK was added thereto, the product was dissolved, 150 parts of warm water at 80° C. was added and washed with water, and the lower aqueous layer was separated and removed. Then, MIBK was evaporated and removed by heating to 160° C. under a reduced pressure of 5 mmHg to obtain 221 parts of reddish-brown phenol resin A. The hydroxyl equivalent is 377, the softening point is 102°C, and the absorption ratio (A ₃₀₄₀ /A ₁₂₁₀ ) is 0.18.

180 parts of phenol resin A, 221 parts of epichlorohydrin, and 33 parts of diethylene glycol dimethyl ether were added to a reaction device equipped with a stirrer, a thermometer, a nitrogen blowing tube, a dropping funnel, and a cooling tube, and heated to 65°C. Under a reduced pressure of 125 mmHg, 39 parts of 49% sodium hydroxide aqueous solution were dripped over 4 hours, maintaining at the temperature of 63-67 degreeC. During this period, epichlorohydrin and water are azeotropic, and the water that flows out is removed outside the system successively. After the reaction, epichlorohydrin was recovered under the conditions of 5 mmHg and 180° C., and 482 parts of MIBK were added to dissolve the product. Then, 146 parts of water was added to dissolve the by-produced salt, left to stand, and the lower layer of salt water was separated and removed. After neutralizing with an aqueous phosphoric acid solution, the resin solution was washed with water until the washing solution became neutral, and then filtered. It was heated to 180° C. under a reduced pressure of 5 mmHg, and MIBK was distilled off to obtain 200 parts of a reddish-brown transparent 2,6-xylenol-dicyclopentadiene type epoxy resin (epoxy resin A). It is a resin with an epoxy equivalent of 446g/eq., a total chlorine content of 431ppm, and a softening point of 91°C.

<Example 1: Preparation of resin composition 1> 20 parts of epoxy resin A (epoxy equivalent 446g/eq.) synthesized in Synthesis Example 1, bisphenol-based epoxy resin ("ZX-1059" manufactured by Nippon Steel Chemical & Materials Co., Ltd., epoxy equivalent about 165g/eq. .) 5 parts, and 5 parts of biphenyl aralkyl type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 194g/eq.) were stirred in 30 parts of naphtha and 10 parts of cyclohexanone Heat aside to dissolve. Thereby, an epoxy resin solution was obtained.

After cooling to room temperature, an inorganic filler (Spherical Dioxane manufactured by Admatechs Co., Ltd., surface-treated with N-phenyl-8-aminooctyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) was mixed into the epoxy resin solution. Silicon oxide "SO-C2", specific surface area: 5.8m ² /g, average particle diameter: 0.5μm) 150 parts, active ester hardener ("HPC-8150-62T" manufactured by DIC Corporation, active group equivalent: about 229g/ eq., a toluene solution with a solid content of 62% by mass) 32 parts, a phenolic hardener ("LA-3018-50P" manufactured by DIC Corporation, an active group equivalent of about 151 g/eq., and a solid content of 50% 2-methoxy Propanol solution) 5 parts, thermoplastic resin (“YX7553BH30”, manufactured by Mitsubishi Chemical Corporation, a 1:1 solution of MEK with a solid content of 30% by mass and cyclohexanone) 17 parts, and a hardening accelerator (4-dimethylamine pyridine (DMAP), 0.6 parts of MEK solution with a solid content of 5% by mass), uniformly dispersed with a high-speed rotary mixer, and filtered with a cartridge filter ("SHP020" manufactured by ROKITECHNO Co., Ltd.) to prepare a varnish-like resin Composition 1.

<Example 2: Preparation of resin composition 2> In Example 1, instead of 32 parts of the active ester-based hardener (“HPC-8150-62T” manufactured by DIC Corporation, a toluene solution with an active group equivalent of about 229 g/eq. and a solid content of 62% by mass), an active ester-based hardener was used. 31 parts of agent ("HPC-8000-65T" manufactured by DIC Corporation, about 223 g/eq. of active group equivalent, 65 mass % of solid content in toluene solution). A varnish-like resin composition 2 was prepared in the same manner as in Example 1 except for the above.

<Comparative Example 1: Preparation of Resin Composition 3> In Example 1, instead of 20 parts of epoxy resin A (epoxy equivalent 446g/eq.), bisphenol AF type epoxy resin ("NC-3000", made by Nippon Kayaku Co., Ltd., epoxy equivalent about 275g/eq.) was used. eq.) 20 parts. A varnish-like resin composition 3 was prepared in the same manner as in Example 1 except for the above.

<Comparative Example 2: Preparation of Resin Composition 4> In Example 1, instead of 20 parts of epoxy resin A (epoxy equivalent 446g/eq.), naphthol aralkyl type epoxy resin ("ESN-475V" manufactured by Nippon Steel Chemical & Materials Co., Ltd., epoxy equivalent About 330g/eq.) 20 parts. A varnish-like resin composition 4 was prepared in the same manner as in Example 1 except for the above.

<Comparative Example 3: Preparation of Resin Composition 5> In Comparative Example 2, instead of 32 parts of the active ester-based hardener (“HPC-8150-62T” manufactured by DIC Corporation, a toluene solution with an active group equivalent of about 229 g/eq. and a solid content of 62% by mass), an active ester-based hardener was used. 31 parts of agent ("HPC-8000-65T" manufactured by DIC Corporation, about 223 g/eq. of active group equivalent, 65 mass % of solid content in toluene solution). A varnish-like resin composition 5 was prepared in the same manner as in Comparative Example 2 except for the above.

＜Production example 1: Production of resin sheet＞ As a support, a PET film ("Lumirror R80" manufactured by Toray Co., Ltd., thickness 38 μm, softening point 130° C. Sometimes called "release PET").

The resin compositions prepared in Examples and Comparative Examples were uniformly coated on release PET with a die coater in such a way that the thickness of the dried resin composition layer was 25 μm, and dried at 80° C. for 1 minute. This forms a resin composition layer on the release PET. Next, on the surface of the resin composition layer that is not bonded to the support, as a protective film, a polypropylene film ("Alphan MA-411" manufactured by Oji F-Tex Co., Ltd., thickness 15μm) rough surface. In this manner, a resin sheet composed of release PET (support), a resin composition layer, and a protective film in this order was produced.

<Test example 1: Measurement and evaluation of specific permittivity and dielectric tangent> The protective film was peeled off from the resin sheet produced in Production Example 1, and the resin composition layer was thermally cured by heating at 200° C. for 90 minutes, and then the support was peeled off. The obtained cured product was cut into a test piece having a width of 2 mm and a length of 80 mm. For this test piece, specific permittivity (Dk) and dielectric tangent (Df) were measured by the cavity resonance perturbation method at a measurement frequency of 5.8 GHz and a measurement temperature of 23° C. using “HP8362B” manufactured by Agilent Technologies. It measured about 3 test pieces, calculated the average value, and evaluated by the following evaluation criteria based on this average value.

Evaluation benchmark "〇": When the specific permittivity (Dk) is 3.5 or less and the dielectric tangent (Df) is 0.0040 or less "×": When the specific permittivity (Dk) is greater than 3.5 or the dielectric tangent (Df) is greater than 0.0040 <Test Example 2: Evaluation of Smear Removal> (1) Substrate processing for built-in substrates A glass cloth base epoxy resin double-sided copper-clad laminate (thickness of copper foil: 18 μm, thickness of substrate: 0.8 mm, “R1515A” manufactured by Panasonic Corporation) having copper foil on the surface was prepared as an inner layer substrate. The copper foil on the surface of the inner layer substrate was etched with a microetchant ("CZ8101" manufactured by MEC Corporation) with a copper etching amount of 1 µm to perform a roughening treatment. Then, drying was performed at 190° C. for 30 minutes.

(2) Lamination and hardening of resin sheets The resin sheet produced in Production Example 1 was bonded to the inner layer substrate by using a batch vacuum pressure laminator (two-stage build-up laminator "CVP700" manufactured by Nikko-Materials Co., Ltd.) Laminate on both sides of the inner substrate. This lamination was carried out by pressure-bonding at a temperature of 100° C. and a pressure of 0.74 MPa for 30 seconds after reducing the pressure to an air pressure of 13 hPa or less for 30 seconds. Next, the laminated resin sheet was smoothed by hot pressing for 60 seconds at 100° C. and a pressure of 0.5 MPa under atmospheric pressure. Furthermore, this was put into the oven of 100 degreeC and heated for 30 minutes, and then transferred to the oven of 170 degreeC and heated for 30 minutes. Thereby, an insulating layer made of a cured product of the resin composition is formed.

(3) Via hole formation: Using a CO ₂ laser processing machine (LK-2K212/2C) manufactured by Via Mechanics, under the conditions of frequency 2000Hz, pulse width 3μs, output 0.95W, and number of shots 3, it is located on the inner layer The insulating layer on one side of the substrate was processed to form via holes with a diameter (diameter) of 50 μm at the top of the surface of the insulating layer and a diameter of 50 μm at the bottom of the insulating layer. Furthermore, the support body was peeled off after that, and the circuit board was obtained.

(4) Roughening treatment The surface of the insulating layer of the circuit board was immersed in Swelling Dip Securiganth P of ATOTECH JAPAN Co., Ltd. as a swelling solution at 60° C. for 10 minutes. Next, the insulating layer surface of the circuit board was immersed in Concentrate Compact P (KMnO ₄ : 60 g/L, NaOH: 40 g/L aqueous solution) as a roughening solution at 80° C. for 25 minutes. Finally, the surface of the insulating layer of the circuit board was immersed in Reduction Solution Securiganth P of ATOTECH JAPAN Co., Ltd. as a neutralizing solution at 40° C. for 5 minutes.

(5) Evaluation of residue at the bottom of the via hole The periphery of the bottom of the three via holes was observed with a scanning electron microscope (SEM), and the maximum smear length from the wall surface of the bottom of the via hole was measured from the obtained image, and evaluated according to the following evaluation criteria.

Evaluation benchmark "○": The maximum smear length is less than 5 μm (that is, the smear length of any of the three via holes is not more than 5 μm, and the smear removability is good) "×": The maximum smear length is 5 μm or more (that is, if the smear length of at least one of the 3 via holes is 5 μm or more, the smear removal property is poor) <Test Example 3: Measurement and evaluation of elongation at breaking point> The evaluation of brittleness was carried out by measuring the elongation at break in the following procedure. For the hardened product A for evaluation, a tensile test was performed with a Tensilon universal testing machine ("RTC-1250A" manufactured by Orientec Co., Ltd.) in accordance with Japanese Industrial Standard JIS K7127, and the elongation at break (%) was measured according to the following evaluation criteria Make an evaluation.

Evaluation benchmark "○": The elongation at breaking point is above 1.0% "×": The elongation at breaking point is less than 1.0%.

。 The content of non-volatile components of the resin compositions of Examples and Comparative Examples, and the measurement results and evaluation results of Test Examples are shown in Table 1 below.

.

As shown in Table 1, it can be seen that by using (A) epoxy resin, (B) active ester compound and (C) inorganic filler, and (A) component contains the above-mentioned (A-1) specific epoxy resin The resin composition can obtain a cured product with a low dielectric tangent and excellent smear removability and elongation at break.

Claims (15)

A resin composition for forming an interlayer insulating layer of a printed wiring board, which is a resin composition comprising (A) an epoxy resin, (B) an active ester compound, and (C) an inorganic filler, wherein (A) component Contain the epoxy resin shown in (A-1) formula (1):

In the formula, R ¹ each independently represent a hydrogen atom, a group represented by formula (1a) or a group represented by formula (1b), and at least one R ¹ is a group represented by formula (1a) or formula (1b) The base shown:

In formulas (1a) and (1b), * represents a bonding site; R ² and R ³ each independently represent a hydrocarbon group having 1 to 8 carbon atoms; n is an integer of 0 or more and represents the number of repeating units. The resin composition for forming an interlayer insulating layer of a printed wiring board according to Claim 1, wherein the average value of n is within the range of 0-5. The resin composition for forming an interlayer insulating layer of a printed wiring board according to claim 1, wherein the component (A) further contains an epoxy resin that is liquid at a temperature of 20°C. The resin composition for forming an interlayer insulating layer of a printed wiring board according to Claim 1, wherein the content of the component (A) is 1% by mass to 30% by mass when the non-volatile components in the resin composition are taken as 100% by mass. quality%. The resin composition for forming an interlayer insulating layer of a printed wiring board according to claim 1, wherein the content of component (B) is 5% by mass or more when the non-volatile components in the resin composition are 100% by mass. The resin composition for forming an interlayer insulating layer of a printed wiring board according to claim 1, wherein the component (C) is silicon dioxide. The resin composition for forming an interlayer insulating layer of a printed wiring board according to claim 1, wherein the content of component (C) is 40% by mass or more when the non-volatile components in the resin composition are 100% by mass. The resin composition for forming an interlayer insulating layer of a printed wiring board according to claim 1, further comprising a phenoxy resin. The resin composition for forming an interlayer insulating layer of a printed wiring board according to claim 1, further comprising a phenolic hardener. The resin composition for forming an interlayer insulating layer of a printed wiring board according to claim 1, wherein the cured product of the resin composition has an elongation at break of 1.0% or more when measured at 23°C in accordance with JIS K7127. The resin composition for forming an interlayer insulating layer of a printed wiring board according to Claim 1, wherein the cured product of the resin composition has a dielectric tangent (Df) of 0.0040 or less when measured at 5.8 GHz and 23°C. The resin composition for forming an interlayer insulating layer of a printed wiring board according to claim 1, wherein when measured at 5.8 GHz and 23° C., the specific permittivity (Dk) of the cured product of the resin composition is 3.5 or less . A resin sheet for forming an interlayer insulating layer of a printed wiring board, which is a resin sheet having a support and a resin composition layer provided on the support, wherein the resin composition layer is formed of a resin composition The resin composition layer, the resin composition comprises (A) epoxy resin, (B) active ester compound and (C) inorganic filler material, and (A) component comprises (A-1) represented by formula (1) Epoxy resin:

In the formula, R ¹ each independently represent a hydrogen atom, a group shown in formula (1a), or a group shown in formula (1b), and at least one R ¹ is a group shown in formula (1a) or formula (1b ) shown in the base:

In formulas (1a) and (1b), * represents a bonding site; R ² and R ³ each independently represent a hydrocarbon group having 1 to 8 carbon atoms; n is an integer of 0 or more and represents the number of repeating units. A printed wiring board comprising an insulating layer comprising a cured product of a resin composition comprising (A) an epoxy resin, (B) an active ester compound, and (C) an inorganic filler, the In the resin composition, (A) component comprises the epoxy resin shown in (A-1) formula (1):

In the formula, R ¹ each independently represent a hydrogen atom, a group shown in formula (1a), or a group shown in formula (1b), and at least one R ¹ is a group shown in formula (1a) or formula (1b ) shown in the base:

In formulas (1a) and (1b), * represents a bonding site; R ² and R ³ each independently represent a hydrocarbon group having 1 to 8 carbon atoms; n is an integer of 0 or more and represents the number of repeating units. A semiconductor device comprising the printed wiring board according to claim 14.