JP2019183068A - Resin composition - Google Patents

Abstract

A resin composition capable of obtaining a cured product having excellent smear removability and excellent adhesion to a conductor layer; a resin sheet containing the resin composition; formed using the resin composition A printed wiring board provided with an insulating layer; and a semiconductor device.
A resin composition comprising (A) an epoxy resin, (B) a carbodiimide curing agent, and (C) a (meth) acrylic acid ester, wherein the mass of the component (B) in the resin composition is determined. A resin composition in which b / c is 0.1 or more and 1.5 or less, where b is the mass of component (C) in the resin composition and c is c.
[Selection figure] None

Description

  The present invention relates to a resin composition. Furthermore, the present invention relates to a resin sheet, a printed wiring board, and a semiconductor device containing the resin composition.

  As a printed wiring board manufacturing technique, a manufacturing method by a build-up method in which insulating layers and conductor layers are alternately stacked on an inner layer circuit board is known. The insulating layer is generally formed by curing a resin composition. For example, Patent Document 1 describes a resin composition containing (A) a radical polymerizable compound, (B) an epoxy resin, (C) a curing agent, and (D) a roughening component.

JP 2014-034580 A

  Many proposals of a resin composition suitable for forming an insulating layer of an inner circuit board have been made including the resin composition described in Patent Document 1, but in recent years, there has been a demand for an insulating layer having a low dielectric loss tangent. It is increasing.

  As a result of the study by the present inventors, the cured product of the resin composition containing a material that lowers the dielectric loss tangent is difficult to obtain adhesion with a conductor layer or the like, and has smear removability for ensuring conduction reliability. It has been found that it tends to decrease. In recent years, in the production of multilayer printed wiring boards, a cured product of a resin composition for forming an insulating layer is required to have sufficient adhesion and smear removability even in miniaturization and densification of wiring. However, the current situation is that these have not been fully met.

  The subject of this invention is the resin composition which can obtain the hardened | cured material which is excellent in smear removal property and is excellent in adhesiveness between conductor layers; The resin sheet containing the said resin composition; Using the said resin composition A printed wiring board including the formed insulating layer; and a semiconductor device.

As a result of intensive studies to solve the above-mentioned problems, the present inventor includes (A) an epoxy resin, (B) a carbodiimide-based curing agent, and (C) a (meth) acrylic acid ester in combination. The present invention has been completed by finding that the above-mentioned problems can be solved by a resin composition in which the mass ratio of the system curing agent and (C) (meth) acrylic acid ester is within a predetermined range.
That is, the present invention includes the following contents.

（式（Ｃ−１）中、Ｒ^１及びＲ^４はそれぞれ独立にアクリロイル基又はメタクリロイル基を表し、Ｒ^２及びＲ^３はそれぞれ独立に２価の連結基を表す。環Ａは、２価の環状基を表す。）
［５］ （Ｂ）成分が、下記式（Ｂ−１）で表される構造単位を有する、［１］〜［４］のいずれかに記載の樹脂組成物。

（式（Ｂ−１）中、Ｘは、アルキレン基、シクロアルキレン基又はアリーレン基を表し、これらは置換基を有していてもよい。ｐは、１〜５の整数を表す。Ｘが複数存在する場合、それらは同一でも相異なってもよい。また、＊は、結合手を表す。）
［６］ （Ａ）成分が、液状エポキシ樹脂及び固体状エポキシ樹脂を含む、［１］〜［５］のいずれかに記載の樹脂組成物。
［７］ さらに（Ｄ）無機充填材を含む、［１］〜［６］のいずれかに記載の樹脂組成物。
［８］ （Ｄ）成分の含有量が、樹脂組成物中の不揮発成分を１００質量％とした場合、７０質量％以上である、［７］に記載の樹脂組成物。
［９］ （Ｃ）成分の含有量が、樹脂組成物中の樹脂成分を１００質量％とした場合、１質量％以上２０質量％以下である、［１］〜［８］のいずれかに記載の樹脂組成物。
［１０］ （Ｂ）成分の含有量が、樹脂組成物中の樹脂成分を１００質量％とした場合、１質量％以上１５質量％以下である、［１］〜［９］のいずれかに記載の樹脂組成物。
［１１］ 絶縁用途に用いる、［１］〜［１０］のいずれかに記載の樹脂組成物。
［１２］ 絶縁層形成用である、［１］〜［１１］のいずれかに記載の樹脂組成物。
［１３］ 導体層を形成するための絶縁層形成用である、［１］〜［１２］のいずれかに記載の樹脂組成物。
［１４］ 半導体チップの封止用である、［１］〜［１３］のいずれかに記載の樹脂組成物。
［１５］ 支持体と、該支持体上に設けられた、［１］〜［１４］のいずれかに記載の樹脂組成物を含む樹脂組成物層とを含む、樹脂シート。
［１６］ ［１］〜［１４］のいずれかに記載の樹脂組成物の硬化物により形成された絶縁層を含む、プリント配線板。
［１７］ ［１６］に記載のプリント配線板を含む、半導体装置。 [1] (A) epoxy resin,
(B) a carbodiimide-based curing agent, and (C) a (meth) acrylic acid ester,
A resin composition in which b / c is 0.1 or more and 1.5 or less, where b is the mass of component (B) in the resin composition and c is the mass of component (C) in the resin composition.
[2] The resin composition according to [1], wherein the component (C) has two or more (meth) acryloyl groups per molecule.
[3] The resin composition according to [1] or [2], wherein the component (C) has a cyclic structure.
[4] The resin composition according to any one of [1] to [3], wherein the component (C) has a structure represented by the following formula (C-1).

(In Formula (C-1), R ¹ and R ⁴ each independently represent an acryloyl group or a methacryloyl group, R ² and R ³ each independently represent a divalent linking group. Ring A is a divalent group. Represents a cyclic group.)
[5] The resin composition according to any one of [1] to [4], wherein the component (B) has a structural unit represented by the following formula (B-1).

(In formula (B-1), X represents an alkylene group, a cycloalkylene group, or an arylene group, which may have a substituent. P represents an integer of 1 to 5. X represents a plurality. If present, they may be the same or different, and * represents a bond.)
[6] The resin composition according to any one of [1] to [5], wherein the component (A) includes a liquid epoxy resin and a solid epoxy resin.
[7] The resin composition according to any one of [1] to [6], further including (D) an inorganic filler.
[8] The resin composition according to [7], wherein the content of the component (D) is 70% by mass or more when the nonvolatile component in the resin composition is 100% by mass.
[9] The content of the component (C) is any one of [1] to [8], which is 1% by mass or more and 20% by mass or less when the resin component in the resin composition is 100% by mass. Resin composition.
[10] The content of the component (B) is any one of [1] to [9], which is 1% by mass or more and 15% by mass or less when the resin component in the resin composition is 100% by mass. Resin composition.
[11] The resin composition according to any one of [1] to [10], which is used for insulating purposes.
[12] The resin composition according to any one of [1] to [11], which is for forming an insulating layer.
[13] The resin composition according to any one of [1] to [12], which is for forming an insulating layer for forming a conductor layer.
[14] The resin composition according to any one of [1] to [13], which is used for sealing a semiconductor chip.
[15] A resin sheet comprising a support and a resin composition layer comprising the resin composition according to any one of [1] to [14] provided on the support.
[16] A printed wiring board including an insulating layer formed of a cured product of the resin composition according to any one of [1] to [14].
[17] A semiconductor device comprising the printed wiring board according to [16].

  ADVANTAGE OF THE INVENTION According to this invention, the resin composition which can obtain the hardened | cured material which is excellent in smear removal property and is excellent in adhesiveness between conductor layers; The resin sheet containing the said resin composition; Using the said resin composition A printed wiring board having a formed insulating layer; and a semiconductor device can be provided.

  Hereinafter, the present invention will be described in detail with reference to embodiments and examples. However, the present invention is not limited to the following embodiments and exemplifications, and can be implemented with any modifications without departing from the scope of the claims of the present invention and the equivalents thereof.

[Resin composition]
The resin composition of the present invention is a resin composition containing (A) an epoxy resin, (B) a carbodiimide-based curing agent, and (C) (meth) acrylic acid ester, and is included in the resin composition ( When the mass of the component B) is b and the mass of the component (C) is c, b / c is 0.1 or more and 1.5 or less.

  By using such a resin composition, it is possible to obtain a cured product having excellent smear removability and excellent adhesion to the conductor layer. Furthermore, by using such a resin composition, the dielectric loss tangent of the cured product can usually be lowered, and the arithmetic average roughness (Ra) of the obtained cured product surface after the roughening treatment can be lowered. Is possible.

  The resin composition may further contain an optional component in combination with the components (A) to (C). Examples of optional components include (D) inorganic filler, (E) curing agent, (F) thermoplastic resin, (G) curing accelerator, (H) polymerization initiator, and (I) other additives. Etc. Hereinafter, each component contained in the resin composition will be described in detail.

<(A) Epoxy resin>
Examples of (A) epoxy resins include bixylenol type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AF type epoxy resins, dicyclopentadiene type epoxy resins, and trisphenol types. Epoxy resin, naphthol novolak type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin , Cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having butadiene structure, alicyclic epoxy resin Heterocyclic epoxy resins, spiro ring-containing epoxy resin, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resins, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenyl ethane epoxy resin and the like. An epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more types.

  It is preferable that a resin composition contains the epoxy resin which has a 2 or more epoxy group in 1 molecule as (A) epoxy resin. From the viewpoint of remarkably obtaining the desired effect of the present invention, the ratio of the epoxy resin having two or more epoxy groups in one molecule with respect to 100% by mass of the nonvolatile component (A) of the epoxy resin is preferably 50 masses. % Or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more.

  The epoxy resin may be an epoxy resin that is liquid at a temperature of 20 ° C. (hereinafter sometimes referred to as “liquid epoxy resin”) and an epoxy resin that is a solid at a temperature of 20 ° C. (hereinafter referred to as “solid epoxy resin”). ) The resin composition (A) may contain only a liquid epoxy resin or only a solid epoxy resin as an epoxy resin, but may contain a combination of a liquid epoxy resin and a solid epoxy resin. Is preferred. (A) By using a combination of a liquid epoxy resin and a solid epoxy resin as an epoxy resin, sufficient flexibility is obtained when used in the form of a resin sheet, or the cured product of the resin composition is broken. Strength can be improved.

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

  Liquid epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, naphthalene type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, phenol novolac type epoxy resins, and ester skeletons. An alicyclic epoxy resin, a cyclohexane type epoxy resin, a cyclohexanedimethanol type epoxy resin, a glycidylamine type epoxy resin, and an epoxy resin having a butadiene structure are preferable, and a bisphenol A type epoxy resin and a bisphenol F type epoxy resin are more preferable.

  Specific examples of the liquid epoxy resin include “HP4032”, “HP4032D”, “HP4032SS” (naphthalene type epoxy resin) manufactured by DIC; “828US”, “jER828EL”, “825”, “Epicoat” manufactured by Mitsubishi Chemical Corporation. 828EL "(bisphenol A type epoxy resin);" jER807 "and" 1750 "(bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical;" jER152 "(phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical; "630", "630LSD" (glycidylamine type epoxy resin); "ZX1059" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); "EX" manufactured by Nagase ChemteX Corporation -721 "(glycidyl Steal type epoxy resin); “Celoxide 2021P” manufactured by Daicel Corporation (an alicyclic epoxy resin having an ester skeleton); “PB-3600” manufactured by Daicel Corporation (an epoxy resin having a butadiene structure); manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. “ZX1658”, “ZX1658GS” (liquid 1,4-glycidylcyclohexane type epoxy resin) and the like. These may be used alone or in combination of two or more.

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

  Solid epoxy resins include bixylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl Type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin and tetraphenylethane type epoxy resin are preferable, and naphthalene type epoxy resin is more preferable.

  Specific examples of the solid epoxy resin include “HP4032H” (naphthalene type epoxy resin) manufactured by DIC; “HP-4700” and “HP-4710” (naphthalene type tetrafunctional epoxy resin) manufactured by DIC; "N-690" (cresol novolac type epoxy resin) manufactured by DIC; "N-695" (cresol novolac type epoxy resin) manufactured by DIC; "HP-7200" (dicyclopentadiene type epoxy resin) manufactured by DIC; “HP-7200HH”, “HP-7200H”, “EXA-7311”, “EXA-7311-G3”, “EXA-7311-G4”, “EXA-7311-G4S”, “HP6000” (manufactured by DIC) Naphthylene ether type epoxy resin) “EPPN-502H” (trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd. Resin); “NC7000L” (naphthol novolak type epoxy resin) manufactured by Nippon Kayaku; “NC3000H”, “NC3000”, “NC3000L”, “NC3100” (biphenyl type epoxy resin) manufactured by Nippon Kayaku; Nippon Steel & Sumitomo Metal “ESN475V” (Naphthol type epoxy resin) manufactured by Chemical Co .; “ESN485” (Naphthol novolak type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd .; “YX4000H”, “YX4000”, “YL6121” (Biphenyl type) manufactured by Mitsubishi Chemical Corporation Epoxy resin); “YX4000HK” (bixylenol type epoxy resin) manufactured by Mitsubishi Chemical; “YX8800” (anthracene type epoxy resin) manufactured by Mitsubishi Chemical; “PG-100” and “CG-” manufactured by Osaka Gas Chemical "500"; "YL" manufactured by Mitsubishi Chemical Corporation "760" (bisphenol AF type epoxy resin); "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1010" (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1031S manufactured by Mitsubishi Chemical Corporation" (Tetraphenylethane type epoxy resin) and the like. These may be used alone or in combination of two or more.

  (A) When a liquid epoxy resin and a solid epoxy resin are used in combination as an epoxy resin, the quantitative ratio thereof (liquid epoxy resin: solid epoxy resin) is preferably a mass ratio, preferably 1: 1 to 1:20. More preferably, it is 1: 1.5-1: 15, Most preferably, it is 1: 2-1: 10. When the quantity ratio between the liquid epoxy resin and the solid epoxy resin is within such a range, the desired effect of the present invention can be remarkably obtained. Furthermore, usually, when used in the form of a resin sheet, moderate tackiness is brought about. Moreover, normally, when using with the form of a resin sheet, sufficient flexibility is acquired and a handleability improves. Furthermore, usually, a cured product having a sufficient breaking strength can be obtained.

  (A) The epoxy equivalent of an epoxy resin becomes like this. Preferably it is 50-5000, More preferably, it is 50-3000, More preferably, it is 80-2000, More preferably, it is 110-1000. By being in this range, the crosslinked density of the cured product of the resin composition layer is sufficient, and an insulating layer having a small surface roughness can be provided. Epoxy equivalent is the mass of resin containing 1 equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.

(A) The weight average molecular weight (Mw) of the epoxy resin is preferably 100 to 5000, more preferably 250 to 3000, and still more preferably 400 to 1500 from the viewpoint of remarkably obtaining the desired effect of the present invention.
The weight average molecular weight of the resin can be measured as a value in terms of polystyrene by gel permeation chromatography (GPC).

  (A) The content of the epoxy resin is preferably 1% by mass or more when the nonvolatile component in the resin composition is 100% by mass from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability. Preferably it is 5 mass% or more, More preferably, it is 10 mass% or more. The upper limit of the content of the epoxy resin is preferably 30% by mass or less, more preferably 25% by mass or less, and particularly preferably 20% by mass or less from the viewpoint of remarkably obtaining the desired effect of the present invention. In addition, in this invention, content of each component in a resin composition is a value when the non-volatile component in a resin composition is 100 mass% unless there is separate description.

<(B) Carbodiimide-based curing agent>
The resin composition contains (B) a carbodiimide-based curing agent. The carbodiimide curing agent as the component (B) is a compound having at least one carbodiimide group (—N═C═N—) in one molecule.

  (B) By using a carbodiimide-based curing agent in combination with (C) (meth) acrylic acid ester so as to have a predetermined mass ratio, it is excellent in smear removal and excellent adhesion between the conductor layers. You can get things. (B) As the carbodiimide-based curing agent, a compound having two or more carbodiimide groups in one molecule is preferable from the viewpoint of remarkably obtaining the desired effect of the present invention. Moreover, a carbodiimide type hardening | curing agent may be used individually by 1 type, and may be used in combination of 2 or more types.

  Especially, as (B) carbodiimide type hardening | curing agent, what contains the structural unit represented by a following formula (B-1) is preferable.

（式（Ｂ−１）中、Ｘは、アルキレン基、シクロアルキレン基又はアリーレン基を表し、これらは置換基を有していてもよい。ｐは、１〜５の整数を表す。Ｘが複数存在する場合、それらは同一でも相異なってもよい。また、＊は、結合手を表す。）

(In formula (B-1), X represents an alkylene group, a cycloalkylene group, or an arylene group, which may have a substituent. P represents an integer of 1 to 5. X represents a plurality. If present, they may be the same or different, and * represents a bond.)

  The number of carbon atoms of the alkylene group represented by X is preferably 1 to 20, more preferably 1 to 10, further preferably 1 to 6, particularly preferably 1 to 4, particularly preferably 1 to 3. The number of carbon atoms of the substituent is not included in the number of carbon atoms. Preferable examples of the alkylene group include a methylene group, an ethylene group, a propylene group, and a butylene group.

  The number of carbon atoms of the cycloalkylene group represented by X is preferably 3-20, more preferably 3-12, and even more preferably 3-6. The number of carbon atoms of the substituent is not included in the number of carbon atoms. Preferable examples of the cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, and a cyclohexylene group.

  The arylene group represented by X is a group having a structure in which two hydrogen atoms on an aromatic ring are removed from an aromatic hydrocarbon. The number of carbon atoms of the arylene group is preferably 6 to 24, more preferably 6 to 18, still more preferably 6 to 14, and particularly preferably 6 to 10. The number of carbon atoms of the substituent is not included in the number of carbon atoms. Preferable examples of the arylene group include a phenylene group, a naphthylene group, and an anthracenylene group.

  Among alkylene groups, cycloalkylene groups, and arylene groups, X is preferably an alkylene group or a cycloalkylene group, and more preferably a cycloalkylene group. By using an alkylene group or a cycloalkylene group, the desired effect of the present invention can be remarkably obtained. Furthermore, the surface roughness and adhesion of the insulating layer can usually be improved.

  The alkylene group, cycloalkylene group and aryl group represented by X may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkyloxy group, an aryl group, an aryloxy group, an acyl group, and an acyloxy group.

As a halogen atom as a substituent, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example.
The alkyl group and alkoxy group as a substituent may be either linear or branched. The number of carbon atoms of the alkyl group and alkoxy group as a substituent is preferably 1 to 20, more preferably 1 to 10, still more preferably 1 to 6, particularly preferably 1 to 4, particularly preferably 1 to 3. It is.
The number of carbon atoms of the cycloalkyl group and cycloalkyloxy group as a substituent is preferably 3 to 20, more preferably 3 to 12, and still more preferably 3 to 6.
The aryl group as a substituent is a group having a structure in which one hydrogen atom on an aromatic ring is removed from an aromatic hydrocarbon. The number of carbon atoms of the aryl group is preferably 6 to 24, more preferably 6 to 18, still more preferably 6 to 14, and particularly preferably 6 to 10.
The number of carbon atoms of the aryloxy group as a substituent is preferably 6 to 24, more preferably 6 to 18, still more preferably 6 to 14, and particularly preferably 6 to 10.
The acyl group as a substituent refers to a group represented by the formula (B-2): —C (═O) —R ¹¹ . In this formula (B-2), R ¹¹ represents an alkyl group or an aryl group. The alkyl group represented by R ¹¹ may be linear or branched. The number of carbon atoms of R ¹¹ is preferably 1 to 20, more preferably 1 to 10, further preferably 1 to 6, particularly preferably 1 to 4, particularly preferably 1 to 3. The number of carbon atoms of the aryl group represented by R ¹¹ is preferably 6 to 24, more preferably 6 to 18, still more preferably 6 to 14, and particularly preferably 6 to 10.
The acyloxy group as a substituent refers to a group represented by the formula (B-3): —O—C (═O) —R ¹² . Here, the meaning of R ¹² is the same as the meaning of R ¹¹ in formula (B-2).

  Especially, as a substituent which the alkylene group represented by X, a cycloalkylene group, and an aryl group may have, an alkyl group, an alkoxy group, and an acyloxy group are preferable, and an alkyl group is more preferable.

  In formula (B-1), p represents an integer of 1 to 5. Among them, p is preferably 2 or more, preferably 4 or less, more preferably 3 or less. When p is in the above range, the desired effect of the present invention can be remarkably obtained. Moreover, usually, the elongation at break, surface roughness and adhesion of the insulating layer can be improved.

  In Formula (B-1), when a plurality of X are present, they may be the same or different. In one preferred embodiment, at least one X is an alkylene group or a cycloalkylene group, and these may have a substituent.

  (B) The amount of the structural unit represented by the formula (B-1) is preferably 50% by mass or more, more preferably 60% by mass or more, with respect to 100% by mass of the entire molecule of the carbodiimide curing agent. More preferably, it is 70 mass% or more, Especially preferably, it is 80 mass% or more, Most preferably, it is 90 mass% or more. Moreover, (B) carbodiimide type hardening | curing agent may become substantially from the structural unit represented by Formula (B-1) except a terminal structure. Examples of the terminal structure of the (B) carbodiimide-based curing agent include an alkyl group, a cycloalkyl group, and an aryl group, and these may have a substituent. The alkyl group, cycloalkyl group, and aryl group used as the terminal structure are an alkyl group, a cycloalkyl group, and an aryl group as a substituent that the group represented by X in formula (B-1) may have. May be the same. In addition, the substituent that the group used as the terminal structure may have may be the same as the substituent that the group represented by X in formula (B-1) may have.

  From the viewpoint of suppressing the occurrence of outgas when curing the resin composition, the weight average molecular weight of the (B) carbodiimide curing agent is preferably 500 or more, more preferably 600 or more, still more preferably 700 or more, and even more preferably. Is 800 or more, preferably 900 or more, particularly preferably 1000 or more. From the viewpoint of obtaining good compatibility, the upper limit of the weight average molecular weight of the (B) carbodiimide-based curing agent is preferably 5000 or less, more preferably 4500 or less, further preferably 4000 or less, and particularly preferably 3500 or less. Preferably it is 3000 or less. (B) The weight average molecular weight of a carbodiimide type | system | group hardening | curing agent can be measured as a value of polystyrene conversion by the gel permeation chromatography (GPC) method.

  (B) A carbodiimide-type hardening | curing agent originates in the manufacturing method, and may contain an isocyanate group (-N = C = O) in a molecule | numerator. From the viewpoint of obtaining a resin composition exhibiting good storage stability, and from the viewpoint of realizing an insulating layer exhibiting desired characteristics, (B) the amount of isocyanate group in the carbodiimide-based curing agent (also referred to as “NCO content”) Is preferably 5% by mass or less, more preferably 4% by mass or less, still more preferably 3% by mass or less, still more preferably 2% by mass or less, and particularly preferably 1% by mass or less, particularly preferably 0.8% by mass. 5% by mass or less.

  (B) A commercially available product may be used as the carbodiimide-based curing agent. Examples of commercially available carbodiimide curing agents include Carbodilite (registered trademark) V-03 (carbodiimide group equivalent: 216), V-05 (carbodiimide group equivalent: 262), V-07 (carbodiimide group equivalent) manufactured by Nisshinbo Chemical Co., Ltd. : 200); V-09 (carbodiimide group equivalent: 200); Stabuxol (registered trademark) P (carbodiimide group equivalent: 302) manufactured by Rhein Chemie.

  A value obtained by dividing the mass of the component (A) by the epoxy equivalent is defined as a1. This value “a1” indicates the equivalent number (eq.) Of the epoxy group contained in the component (A). The value obtained by dividing the mass of the component (B) by the carbodiimide group equivalent is defined as b1. This value “b1” represents the equivalent number (eq.) Of the carbodiimide group contained in the component (B). In this case, b1 / a1 is preferably 0.01 or more, more preferably 0.05 or more, further preferably 0.1 or more, preferably 10 or less, more preferably 5 or less, and still more preferably 1 or less. is there. By setting the quantitative ratio of the component (A) and the component (B) within such a range, it is possible to obtain a cured product having excellent adhesion with the conductor layer. When two or more types of component (A) are contained in the resin composition, the a1 is a value obtained by adding all values obtained by dividing the mass of each epoxy resin present in the resin composition by each epoxy equivalent. When two or more types of component (B) are contained in the resin composition, the above b1 is the sum of all values obtained by dividing the mass of the nonvolatile component of each carbodiimide-based curing agent present in the resin composition by the equivalent of each carbodiimide group. It is the value.

  The content of the (B) carbodiimide curing agent is preferably 1% by mass or more, more preferably 2% by mass or more, and further preferably 3% by mass or more with respect to 100% by mass of the resin component in the resin composition. Preferably, it is 15 mass% or less, More preferably, it is 13 mass% or less, More preferably, it is 10 mass% or less. (B) By making the quantity of a carbodiimide type hardening | curing agent in such a range, it is excellent in adhesiveness between conductor layers, and hardened | cured material with low arithmetic mean roughness can be obtained.

  The “resin component” of the resin composition refers to a component excluding (D) the inorganic filler among the non-volatile components contained in the resin composition.

<(C) (Meth) acrylic acid ester>
The resin composition contains (C) (meth) acrylic acid ester. By including (C) (meth) acrylic acid ester in the resin composition, it is possible to lower the dielectric loss tangent and to obtain a cured product having excellent smear removability. Here, the term “(meth) acrylic acid” includes acrylic acid and methacrylic acid, and combinations thereof.

  (C) The (meth) acrylic acid ester preferably has two or more (meth) acryloyl groups per molecule from the viewpoint of obtaining a cured product having a low dielectric loss tangent and excellent smear removability. The term “(meth) acryloyl group” includes acryloyl and methacryloyl groups and combinations thereof.

  (C) The (meth) acrylic acid ester preferably has a cyclic structure from the viewpoint of obtaining a cured product having a low dielectric loss tangent and excellent smear removability. As the cyclic structure, a divalent cyclic group is preferable. As a bivalent cyclic group, any of the cyclic group containing an alicyclic structure and the cyclic group containing an aromatic ring structure may be sufficient. Especially, it is preferable that it is a cyclic group containing an alicyclic structure from a viewpoint which obtains the desired effect of this invention notably.

  The divalent cyclic group is preferably a 3-membered ring or more, more preferably a 4-membered ring or more, further preferably a 5-membered ring or more, preferably a 20-membered ring, from the viewpoint of remarkably obtaining the desired effect of the present invention. Hereinafter, it is more preferably a 15-membered ring or less, still more preferably a 10-membered ring or less. Further, the divalent cyclic group may be a monocyclic structure or a polycyclic structure.

  In the ring in the divalent cyclic group, a ring skeleton may be constituted by a hetero atom in addition to a carbon atom. Examples of the hetero atom include an oxygen atom, a sulfur atom, and a nitrogen atom, and an oxygen atom is preferable. One hetero atom may be present in the ring, or two or more hetero atoms may be present.

Specific examples of the divalent cyclic group include the following divalent groups (i) to (xi). Among these, as the divalent cyclic group, (x) or (xi) is preferable.

  The divalent cyclic group may have a substituent. Examples of such substituents include halogen atoms, alkyl groups, alkoxy groups, aryl groups, arylalkyl groups, silyl groups, acyl groups, acyloxy groups, carboxy groups, sulfo groups, cyano groups, nitro groups, hydroxy groups, A mercapto group, an oxo group, etc. are mentioned, An alkyl group is preferable.

  The (meth) acryloyl group may be directly bonded to the divalent cyclic group or may be bonded via a divalent linking group. Examples of the divalent linking group include an alkylene group, an alkenylene group, an arylene group, a heteroarylene group, —C (═O) O—, —O—, —NHC (═O) —, and —NC (═O). N—, —NHC (═O) O—, —C (═O) —, —S—, —SO—, —NH— and the like may be mentioned, and a group obtained by combining a plurality of these may be used. The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, an alkylene group having 1 to 5 carbon atoms, or an alkylene group having 1 to 4 carbon atoms. Is more preferable. The alkylene group may be linear, branched or cyclic. Examples of such an alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, and a 1,1-dimethylethylene group. -A dimethylethylene group is preferred. The alkenylene group is preferably an alkenylene group having 2 to 10 carbon atoms, more preferably an alkenylene group having 2 to 6 carbon atoms, and still more preferably an alkenylene group having 2 to 5 carbon atoms. As the arylene group and heteroarylene group, an arylene group or heteroarylene group having 6 to 20 carbon atoms is preferable, and an arylene group or heteroarylene group having 6 to 10 carbon atoms is more preferable. As the divalent linking group, an alkylene group is preferable, and a methylene group and a 1,1-dimethylethylene group are particularly preferable.

（式（Ｃ−１）中、Ｒ^１及びＲ^４はそれぞれ独立にアクリロイル基又はメタクリロイル基を表し、Ｒ^２及びＲ^３はそれぞれ独立に２価の連結基を表す。環Ａは、２価の環状基を表す。） (C) The (meth) acrylic acid ester is preferably represented by the following formula (C-1).

(In Formula (C-1), R ¹ and R ⁴ each independently represent an acryloyl group or a methacryloyl group, R ² and R ³ each independently represent a divalent linking group. Ring A is a divalent group. Represents a cyclic group.)

R ¹ and R ⁴ each independently represents an acryloyl group or a methacryloyl group, and an acryloyl group is preferred.

R ² and R ³ each independently represent a divalent linking group. The divalent linking group is the same as the above divalent linking group.

  Ring A represents a divalent cyclic group. Ring A is the same as the above divalent cyclic group.

  Ring A may have a substituent. The substituent is the same as the substituent that the above divalent cyclic group may have.

Hereinafter, although the specific example of (C) component is shown, this invention is not limited to this.

  As the component (C), commercially available products may be used. For example, “A-DOG” ((meth) acryloyl group equivalent 163) manufactured by Shin-Nakamura Chemical Co., Ltd., “DCP-A” (( (Meth) acryloyl group equivalent 152), Nippon Kayaku Co., Ltd. “NPDGA” ((meth) acryloyl group equivalent 106), “FM-400” ((meth) acryloyl group equivalent 156), “R-687” ((meth)) Acryloyl group equivalent 187), “THE-330” ((meth) acryloyl group equivalent 143), “PET-30” ((meth) acryloyl group equivalent 88), “DPHA” ((meth) acryloyl group equivalent 96), etc. Can be mentioned. (C) A component may be used individually by 1 type and may be used in combination of 2 or more types.

  From the viewpoint of improving smear removability, the content of the component (C) is preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably, when the resin component in the resin composition is 100% by mass. Is 5% by mass or more. The upper limit is preferably 20% by mass or less, more preferably 18% by mass or less, and still more preferably 15% by mass or less.

  The resin composition uses (B) a carbodiimide-based curing agent and (C) (meth) acrylic acid ester in combination so as to have a predetermined mass ratio, thereby providing a cured product having excellent adhesion and low arithmetic average roughness. Can be obtained. When the mass of the component (B) in the resin composition is b and the mass of the component (C) in the resin composition is c, b / c is 0.1 or more, preferably 0.2 or more, More preferably, it is 0.25 or more. The upper limit is 1.5 or less, preferably 1.3 or less, more preferably 1.0 or less. By adjusting the mass ratio of the component (B) and the component (C) so that b / c is within such a range, a cured product having excellent adhesion and low arithmetic average roughness can be obtained. .

  Moreover, the value which remove | divided the mass of (C) component by the (meth) acryloyl group equivalent is set to c1. This value “c1” represents the equivalent number (eq.) Of the (meth) acryloyl group equivalent contained in the component (C). In this case, b1 / c1 is usually 0.06 or more, preferably 0.1 or more, more preferably 0.15 or more. The upper limit is 1.4 or less, preferably 1.3 or less, more preferably 1 or less. By adjusting the amount ratio of the component (B) and the component (C) so that b1 / c1 falls within such a range, a cured product having excellent adhesion and low arithmetic average roughness can be obtained. . When two or more types of component (C) are contained in the resin composition, the above c1 is a value obtained by dividing the mass of each (meth) acrylic ester present in the resin composition by each (meth) acryloyl group equivalent. This is the total value.

<(D) Inorganic filler>
In addition to the components described above, the resin composition may further contain (D) an inorganic filler as an optional component.

  An inorganic compound is used as the material of the inorganic filler. Examples of inorganic filler materials include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, Magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide , Barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Of these, silica is particularly preferred. Examples of the silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Further, as silica, spherical silica is preferable. (D) An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more types.

  (D) Commercially available inorganic fillers include, for example, “UFP-30” manufactured by Denka Kagaku Kogyo Co., Ltd .; “SP60-05” and “SP507-05” manufactured by Nippon Steel & Sumikin Materials Co., Ltd .; “YC100C”, “YA050C”, “YA050C-MJE”, “YA010C”; “UFP-30” manufactured by Denka Co., Ltd .; “Sylfil NSS-3N”, “Sylfil NSS-4N”, “Sylfil NSS-” manufactured by Tokuyama Corporation 5N ";" SC2500SQ "," SO-C4 "," SO-C2 "," SO-C1 "manufactured by Admatechs, and the like.

  (D) The average particle diameter of the inorganic filler is preferably 0.01 μm or more, more preferably 0.05 μm or more, particularly preferably 0.1 μm or more, from the viewpoint of remarkably obtaining the desired effect of the present invention. Preferably it is 5 micrometers or less, More preferably, it is 2 micrometers or less, More preferably, it is 1 micrometer or less.

  (D) The average particle diameter of the inorganic filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, it can be measured by creating a particle size distribution of the inorganic filler on a volume basis with a laser diffraction / scattering particle size distribution measuring device and setting the median diameter as the average particle size. As the measurement sample, 100 mg of an inorganic filler and 10 g of methyl ethyl ketone are weighed in a vial and can be dispersed by ultrasonic for 10 minutes. Particles obtained by measuring the volume-based particle size distribution of the (D) inorganic filler using a flow cell method, using a laser diffraction particle size distribution measuring device as the measurement light source, using blue and red as the light source wavelength. The average particle diameter was calculated as the median diameter from the diameter distribution. Examples of the laser diffraction particle size distribution measuring apparatus include “LA-960” manufactured by Horiba, Ltd.

(D) The specific surface area of the inorganic filler is preferably 1 m ² / g or more, more preferably 2 m ² / g or more, and particularly preferably 3 m ² / g or more from the viewpoint of remarkably obtaining the desired effect of the present invention. is there. Although there is no special restriction | limiting in an upper limit, Preferably it is 60 m < ² > / g or less, 50 m < ² > / g or less, or 40 m < ² > / g or less. The specific surface area can be obtained by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountec Co., Ltd.) according to the BET method, and calculating the specific surface area using the BET multipoint method. .

  (D) It is preferable that the inorganic filler is treated with a surface treatment agent from the viewpoint of improving moisture resistance and dispersibility. Examples of the surface treatment agent include fluorine-containing silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, organosilazane compounds, and titanates. A coupling agent etc. are mentioned. Moreover, a surface treating agent may be used individually by 1 type, and may be used combining two or more types arbitrarily.

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

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

The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. Carbon content per unit surface area of the inorganic filler, from the viewpoint of improving dispersibility of the inorganic filler is preferably 0.02 mg / ^{m 2} or more, 0.1 mg / ^{m 2} or more preferably, 0.2 mg / ^{m 2} The above is more preferable. On the other hand, 1 mg / m ² or less is preferable, 0.8 mg / m ² or less is more preferable, and 0.5 mg / m ² or less is more preferable from the viewpoint of suppressing an increase in the melt viscosity of the resin varnish and the sheet form. preferable.

  The amount of carbon per unit surface area of the inorganic filler can be measured after the surface-treated inorganic filler is washed with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with the surface treatment agent and ultrasonically cleaned at 25 ° C. for 5 minutes. After removing the supernatant and drying the solid, the carbon amount per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, “EMIA-320V” manufactured by HORIBA, Ltd. can be used.

  (D) The content of the inorganic filler is preferably 50% by mass or more, more preferably 100% by mass or more, from the viewpoint of reducing the dielectric loss tangent and improving the smear removability. Is 60% by mass or more, more preferably 70% by mass or more. Moreover, from a viewpoint of maintaining adhesiveness, Preferably it is 90 mass% or less, More preferably, it is 85 mass% or less, More preferably, it is 80 mass% or less. Usually, when the content of the inorganic filler is relatively large, the adhesiveness tends to be lowered, but in the present invention, sufficient adhesiveness can be maintained.

<(E) Curing agent>
The resin composition may further contain (E) a curing agent as an optional component in addition to the components described above. However, (B) carbodiimide type curing agent is not included in (E) curing agent. (E) The curing agent usually has a function of reacting with the component (A) to cure the resin composition. (E) A hardening | curing agent may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.

  (E) As the curing agent, a compound capable of curing the resin composition by reacting with the epoxy resin can be used. For example, a phenolic curing agent, an active ester curing agent, a cyanate ester curing agent, benzo Examples include oxazine-based curing agents, amine-based curing agents, and acid anhydride-based curing agents. Among these, from the viewpoint of remarkably obtaining the desired effect of the present invention, a phenolic curing agent and an active ester curing agent are preferable, and an active ester curing agent is more preferable.

  Examples of the phenolic curing agent include a curing agent having one or more, preferably two or more hydroxyl groups bonded to an aromatic ring (benzene ring, naphthalene ring, etc.) in one molecule. Among these, a compound having a hydroxyl group bonded to a benzene ring is preferable. From the viewpoints of heat resistance and water resistance, a phenolic curing agent having a novolak structure is preferred. Furthermore, from the viewpoint of adhesion, a nitrogen-containing phenol-based curing agent is preferable, and a triazine skeleton-containing phenol-based curing agent is more preferable. In particular, from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion, a triazine skeleton-containing phenol novolac curing agent is preferable.

  Specific examples of the phenol-based curing agent and the naphthol-based curing agent include “MEH-7700”, “MEH-7810”, “MEH-7851”, “MEH-8000H” manufactured by Meiwa Kasei Co., Ltd .; manufactured by Nippon Kayaku Co., Ltd. “NHN”, “CBN”, “GPH”; “SN-170”, “SN-180”, “SN-190”, “SN-475”, “SN-485”, “SN” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. -495 "," SN-495V "," SN-375 "," SN-395 ";" TD-2090 "," TD-2090-60M "," LA-7052 "," LA-7054 "manufactured by DIC Corporation ”,“ LA-1356 ”,“ LA-3018 ”,“ LA-3018-50P ”,“ EXB-9500 ”,“ HPC-9500 ”,“ KA-1160 ”,“ KA-1163 ”,“ KA-1165 ” " Gun Ei Chemical Industry Co., Ltd. of "GDP-6115L", "GDP-6115H", "ELPC75", and the like.

  Examples of the active ester curing agent include a curing agent having one or more active ester groups in one molecule. Among them, as the active ester curing agent, two or more ester groups having high reaction activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, and heterocyclic hydroxy compound esters in one molecule are used. The compound which has is preferable. The active ester curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable. .

  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, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, Benzenetriol, dicyclopentadiene type diphenol compound, phenol novolac and the like can be mentioned. Here, the “dicyclopentadiene type diphenol compound” refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

  Preferable specific examples of the active ester curing agent include an active ester compound containing a dicyclopentadiene type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, and a benzoylated product of phenol novolac. The active ester compound containing is mentioned. Of these, active ester compounds containing a naphthalene structure and active ester compounds containing a dicyclopentadiene type diphenol structure are more preferred. The “dicyclopentadiene type diphenol structure” represents a divalent structure composed of phenylene-dicyclopentylene-phenylene.

  As a commercial product of an active ester type curing agent, as an active ester compound containing a dicyclopentadiene type diphenol structure, “EXB9451”, “EXB9460”, “EXB9460S”, “HPC-8000”, “HPC-8000H”, “ HPC-8000-65T ”,“ HPC-8000H-65TM ”,“ EXB-8000L ”,“ EXB-8000L-65TM ”,“ EXB-8150-65T ”(manufactured by DIC); as an active ester compound containing a naphthalene structure “EXB9416-70BK” (manufactured by DIC); “DC808” (manufactured by Mitsubishi Chemical) as an active ester-based curing agent that is an acetylated product of phenol novolac; “YLH1026” as an active ester-based curing agent that is a benzoylated product of phenol novolac (Mitsubishi ke Manufactured by Cal Co., Ltd.), "YLH1030" (manufactured by Mitsubishi Chemical Co., Ltd.), "YLH1048" (manufactured by Mitsubishi Chemical Co., Ltd.); and the like.

  Examples of the cyanate ester curing agent include bisphenol A dicyanate, polyphenol cyanate, oligo (3-methylene-1,5-phenylene cyanate), 4,4′-methylenebis (2,6-dimethylphenyl cyanate), 4,4. '-Ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanatephenylmethane), bis (4-cyanate-3,5-dimethyl) Bifunctional cyanate resins such as phenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, and bis (4-cyanatephenyl) ether; Phenol novolac and Polyfunctional cyanate resin derived from resol novolac; prepolymer these cyanate resin is partially triazine of; and the like. Specific examples of the cyanate ester curing agent include “PT30” and “PT60” (both phenol novolac type polyfunctional cyanate ester resins) manufactured by Lonza Japan; “ULL-950S” (polyfunctional cyanate ester resin); BA230 "," BA230S75 "(a prepolymer in which a part or all of bisphenol A dicyanate is triazine-modified into a trimer); and the like.

  Specific examples of the benzoxazine-based curing agent include “HFB2006M” manufactured by Showa Polymer Co., Ltd. and “Pd” and “Fa” manufactured by Shikoku Kasei Kogyo Co., Ltd.

  Examples of amine-based curing agents include curing agents having one or more amino groups in one molecule, such as aliphatic amines, polyether amines, alicyclic amines, aromatic amines, and the like. Among them, aromatic amines are preferable from the viewpoint of achieving the desired effect of the present invention. The amine-based curing agent is preferably a primary amine or a secondary amine, and more preferably a primary amine. Specific examples of the amine curing agent include 4,4′-methylenebis (2,6-dimethylaniline), diphenyldiaminosulfone, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, 3,3 ′. -Diaminodiphenylsulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl- 4,4′-diaminobiphenyl, 3,3′-dihydroxybenzidine, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane Diamine, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4- (4 Aminophenoxy) phenyl) propane, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4,4 ′ -Bis (4-aminophenoxy) biphenyl, bis (4- (4-aminophenoxy) phenyl) sulfone, bis (4- (3-aminophenoxy) phenyl) sulfone, and the like. Commercially available amine-based curing agents may be used. For example, “KAYABOND C-200S”, “KAYABOND C-100”, “Kayahard A-A”, “Kayahard A-B”, “Kayahard AB” manufactured by Nippon Kayaku Co., Ltd. Kayahard AS, “Epicure W” manufactured by Mitsubishi Chemical Corporation, and the like.

  Examples of the acid anhydride curing agent include a curing agent having one or more acid anhydride groups in one molecule. Specific examples of acid anhydride-based curing agents include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic acid anhydride, hydrogenated methylnadic acid Anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, tri Mellitic acid, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'- Diphenylsulfonetetracarboxylic dianhydride, 1,3,3a, 4,5,9b-hex Hydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-C] furan-1,3-dione, ethylene glycol bis (anhydrotrimellitate), styrene and maleic acid And polymer type acid anhydrides such as styrene / maleic acid resin copolymerized.

  The value obtained by dividing the mass of the component (E) by the reactive group equivalent is defined as e1. This value “e1” indicates the number of equivalents (eq.) Of reactive groups contained in the component (E). In this case, e1 / a1 is preferably 0.1 or more, more preferably 0.3 or more, and further preferably 0.5 or more. The upper limit is preferably 3 or less, more preferably 2 or less, and still more preferably 1 or less. Here, the reactive group of the curing agent is an active hydroxyl group or the like, and varies depending on the type of the curing agent. When two or more types of component (E) are contained in the resin composition, the above e1 is a value obtained by adding up all values obtained by dividing the mass of each component (E) present in the resin composition by the equivalent of each reactive group. is there. By setting the amount ratio of the epoxy resin and the curing agent in such a range, the heat resistance of the cured product of the resin composition is further improved.

  Further, (b1 + e1) / c1 is preferably 1.8 or more, more preferably 1.85 or more, further preferably 1.9 or more, preferably 8 or less, more preferably 7 or less, still more preferably 5 or less. It is. By adjusting the quantity ratio of each component so that (b1 + e1) / c1 falls within such a range, a cured product having excellent adhesion and low arithmetic average roughness can be obtained.

  (E) From the viewpoint of remarkably obtaining the desired effect of the present invention, the content of the curing agent is preferably 1% by mass or more, more preferably 3% by mass, when the nonvolatile component in the resin composition is 100% by mass. More preferably, it is 5% by mass or more, preferably 15% by mass or less, more preferably 13% by mass or less, and still more preferably 10% by mass or less.

  (E) When the mass of the curing agent is e, (b + e) / c is preferably 2.5 or more, more preferably 2.6 or more, still more preferably 2.66 or more, preferably 10 or less. More preferably, it is 8 or less, More preferably, it is 7 or less. By adjusting the mass ratio of each component so that (b + e) / c falls within such a range, a cured product having excellent adhesion and low arithmetic average roughness can be obtained.

<(F) Thermoplastic resin>
In addition to the components described above, the resin composition may further contain (F) a thermoplastic resin as an optional component.

  Examples of the thermoplastic resin as the component (F) include phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, and polyphenylene ether resin. , Polycarbonate resin, polyether ether ketone resin, polyester resin and the like. Among these, a phenoxy resin is preferable from the viewpoint of remarkably obtaining the desired effect of the present invention and a viewpoint of obtaining an insulating layer having a small surface roughness and particularly excellent adhesion to the conductor layer. Moreover, a thermoplastic resin may be used individually by 1 type, or may be used in combination of 2 or more types.

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

  Specific examples of the phenoxy resin include “1256” and “4250” (both bisphenol A skeleton-containing phenoxy resins) manufactured by Mitsubishi Chemical; “YX8100” (bisphenol S skeleton-containing phenoxy resin) manufactured by Mitsubishi Chemical; “YX6954” (bisphenolacetophenone skeleton-containing phenoxy resin) manufactured by Nippon Steel &Chemicals; “FX280” and “FX293” manufactured by Nippon Steel & Sumikin Chemical; “YL7500BH30”, “YX6954BH30”, “YX7553”, “YX7553BH30” manufactured by Mitsubishi Chemical “YL7769BH30”, “YL6794”, “YL7213”, “YL7290”, “YL7482”;

  Examples of the polyvinyl acetal resin include a polyvinyl formal resin and a polyvinyl butyral resin, and a polyvinyl butyral resin is preferable. Specific examples of the polyvinyl acetal resin include “Electrical butyral 4000-2”, “Electrical butyral 5000-A”, “Electrical butyral 6000-C”, and “Electrical butyral 6000-EP” manufactured by Denki Kagaku Kogyo Co., Ltd .; Examples include S-LEC BH series, BX series (for example, BX-5Z), KS series (for example, KS-1), BL series, and BM series;

  Specific examples of the polyimide resin include “Rika Coat SN20” and “Rika Coat PN20” manufactured by Shin Nippon Rika Co., Ltd. Specific examples of the polyimide resin include linear polyimide obtained by reacting a bifunctional hydroxyl group-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride (polyimide described in JP-A-2006-37083), a polysiloxane skeleton. Examples thereof include modified polyimides such as containing polyimide (polyimides described in JP-A Nos. 2002-12667 and 2000-319386).

  Specific examples of the polyamide-imide resin include “Bilomax HR11NN” and “Bilomax HR16NN” manufactured by Toyobo Co., Ltd. Specific examples of the polyamide-imide resin include modified polyamide-imides such as “KS9100” and “KS9300” (polysiloxane skeleton-containing polyamideimide) manufactured by Hitachi Chemical.

  Specific examples of the polyethersulfone resin include “PES5003P” manufactured by Sumitomo Chemical Co., Ltd.

  Specific examples of the polyphenylene ether resin include oligophenylene ether / styrene resin “OPE-2St 1200” manufactured by Mitsubishi Gas Chemical Company.

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

  (F) The weight average molecular weight (Mw) of the thermoplastic resin is preferably 8,000 or more, more preferably 10,000 or more, and particularly preferably 20,000 or more from the viewpoint of remarkably obtaining the desired effect of the present invention. It is preferably 70,000 or less, more preferably 60,000 or less, and particularly preferably 50,000 or less.

  (F) The content of the thermoplastic resin is preferably 0.01% by mass or more, more preferably 100% by mass when the nonvolatile component in the resin composition is 100% by mass from the viewpoint of remarkably obtaining the desired effect of the present invention. Is 0.05% by mass or more, more preferably 0.1% by mass or more, preferably 5% by mass or less, more preferably 3% by mass or less, and still more preferably 1% by mass or less.

<(G) Curing accelerator>
In addition to the components described above, the resin composition may further contain (G) a curing accelerator as an optional component.

  Examples of the curing accelerator include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, and metal-based curing accelerators. Among these, a phosphorus curing accelerator, an amine curing accelerator, an imidazole curing accelerator, and a metal curing accelerator are preferable, and an amine curing accelerator, an imidazole curing accelerator, and a metal curing accelerator are more preferable. A hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more types.

  Examples of phosphorus curing accelerators include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl) triphenylphosphonium thiocyanate. , Tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate and the like, and triphenylphosphine and tetrabutylphosphonium decanoate are preferable.

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

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

  Commercially available products may be used as the imidazole curing accelerator, and examples thereof include “P200-H50” manufactured by Mitsubishi Chemical Corporation.

  Examples of the guanidine curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, Tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Deca-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1 -Allyl biguanide, 1-phenyl biguanide, 1- ( - tolyl) biguanide, and the like, dicyandiamide, 1,5,7-triazabicyclo [4.4.0] dec-5-ene are preferred.

  As a metal type hardening accelerator, the organometallic complex or organometallic salt of metals, such as cobalt, copper, zinc, iron, nickel, manganese, tin, is mentioned, for example. Specific examples of the organometallic complex include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. Organic zinc complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

  (G) The content of the curing accelerator is preferably 0.01% by mass or more, more preferably 100% by mass or more, more preferably, from the viewpoint of remarkably obtaining the desired effect of the present invention. Is 0.03% by mass or more, more preferably 0.05% by mass or more, preferably 0.3% by mass or less, more preferably 0.2% by mass or less, and further preferably 0.1% by mass or less. .

<(H) Polymerization initiator>
In addition to the components described above, the resin composition may further contain (H) a polymerization initiator as an optional component. (H) The polymerization initiator usually has a function of promoting the crosslinking of the (meth) acryloyl group in the component (C). (H) A polymerization initiator may be used alone or in combination of two or more.

  (H) As a polymerization initiator, for example, t-butylcumyl peroxide, t-butylperoxyacetate, α, α′-di (t-butylperoxy) diisopropylbenzene, t-butylperoxylaurate, t -Peroxides such as butylperoxy-2-ethylhexanoate t-butylperoxyneodecanoate and t-butylperoxybenzoate.

  Examples of commercially available (H) polymerization initiators include “Perbutyl C”, “Perbutyl A”, “Perbutyl P”, “Perbutyl L”, “Perbutyl O”, “Perbutyl ND”, “ Perbutyl Z "and the like.

  The content of the (H) polymerization initiator is preferably 0.01% by mass or more, more preferably 100% by mass, when the nonvolatile component in the resin composition is 100% by mass from the viewpoint of remarkably obtaining the desired effect of the present invention. Is 0.03% by mass or more, more preferably 0.05% by mass or more, preferably 0.5% by mass or less, more preferably 0.3% by mass or less, and further preferably 0.1% by mass or less. .

<(I) Other additives>
The resin composition may further contain other additives as optional components in addition to the components described above. Examples of such additives include organic fillers; resin additives such as thickeners, antifoaming agents, leveling agents, and adhesion-imparting agents. These additives may be used alone or in combination of two or more.

  The present inventor has found that when the resin composition contains (C) (meth) acrylic acid ester, the dielectric loss tangent can be lowered and the smear removability is improved. As a result of further intensive studies, the present inventor has (B) a carbodiimide-based curing agent contained in the resin composition so that the mass ratio with (C) (meth) acrylic acid ester is within a predetermined range. In addition to lowering the dielectric loss tangent and improving smear removability, the arithmetic mean roughness (Ra) of the surface of the cured product obtained after the roughening treatment can be lowered, and the adhesion (peeling) with the plated conductor layer can be reduced. It was found that the strength was also improved. It is considered that this is because the increase in the arithmetic average roughness is suppressed and the peel strength is improved by the increase in the crosslink density in the cured product due to the (B) carbodiimide curing agent.

<Physical properties and uses of resin composition>
A cured product obtained by thermosetting the resin composition at 130 ° C. for 30 minutes and then at 170 ° C. for 30 minutes exhibits the property of being excellent in smear removal properties. Therefore, when a via hole is formed in the cured product, an insulating layer having a maximum smear length at the bottom of the via hole of less than 5 μm is provided. The smear removability can be measured by the method described in Examples described later.

  The roughened surface after roughening the surface of the cured product obtained by thermosetting the resin composition at 130 ° C. for 30 minutes and then at 170 ° C. for 30 minutes exhibits a characteristic that the arithmetic average roughness (Ra) is low. Therefore, the said hardened | cured material brings about an insulating layer with low arithmetic mean roughness. The arithmetic average roughness is preferably 150 nm or less, more preferably 140 nm or less, and still more preferably 130 nm or less. On the other hand, the lower limit value of the arithmetic average roughness may be 1 nm or more. The evaluation of the arithmetic average roughness (Ra) can be measured according to the method described in Examples described later.

  A cured product obtained by thermosetting the resin composition at 130 ° C. for 30 minutes and then at 170 ° C. for 30 minutes exhibits a property of excellent adhesion (peel strength) to the plated conductor layer. Therefore, the said hardened | cured material brings about the insulating layer excellent in adhesiveness with a plating conductor layer. The adhesion strength with the plated conductor layer is preferably 0.2 kgf / cm or more, more preferably 0.3 kgf / cm or more, and further preferably 0.4 kgf / cm or more. On the other hand, the upper limit value of the adhesion strength is not particularly limited, but may be 5 kgf / cm or less. The evaluation of the peel strength can be measured according to the method described in Examples described later.

  A cured product obtained by thermally curing the resin composition at 190 ° C. for 90 minutes usually indicates that the dielectric loss tangent is low. Thus, the cured product provides an insulating layer with a low dielectric loss tangent. The dielectric loss tangent is preferably 0.005 or less, more preferably 0.004 or less and 0.003 or less. On the other hand, the lower limit value of the dielectric loss tangent is not particularly limited, but may be 0.0001 or more. The evaluation of the dielectric loss tangent can be measured according to the method described in Examples described later.

  The resin composition of the present invention can provide an insulating layer excellent in smear removability and adhesion. Therefore, the resin composition of the present invention can be suitably used as a resin composition for insulating purposes. Specifically, a resin composition for forming a conductive layer (including a rewiring layer) formed on the insulating layer (resin for forming an insulating layer for forming a conductive layer) It can be suitably used as a composition.

  Further, in a multilayer printed wiring board to be described later, a resin composition for forming an insulating layer of the multilayer printed wiring board (resin composition for forming an insulating layer of the multilayer printed wiring board) and an interlayer insulating layer of the printed wiring board are formed. Therefore, it can be suitably used as a resin composition (resin composition for forming an interlayer insulating layer of a printed wiring board).

For example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition of the present invention is used for a rewiring layer as an insulating layer for forming a rewiring layer. The resin composition (resin composition for forming a rewiring layer) and a resin composition for sealing a semiconductor chip (resin composition for sealing a semiconductor chip) can be suitably used. When a semiconductor chip package is manufactured, a rewiring layer may be further formed on the sealing layer.
(1) Laminating a temporary fixing film on a substrate;
(2) a step of temporarily fixing the semiconductor chip on the temporary fixing film;
(3) forming a sealing layer on the semiconductor chip;
(4) The process of peeling a base material and a temporary fixing film from a semiconductor chip,
(5) a step of forming a rewiring formation layer as an insulating layer on the surface from which the base material and the temporary fixing film of the semiconductor chip are peeled; and (6) a rewiring layer as a conductor layer on the rewiring formation layer. Forming process

  Moreover, since the resin composition of this invention brings about an insulating layer favorable for component embedding property, it can be used conveniently also when a printed wiring board is a component built-in circuit board.

[Resin sheet]
The resin sheet of the present invention includes a support and a resin composition layer formed on the support and formed of the resin composition of the present invention.

  The thickness of the resin composition layer is preferably 50 μm or less, from the viewpoint of reducing the thickness of the printed wiring board and providing a cured product excellent in insulation even if the cured product of the resin composition is a thin film. Preferably it is 40 micrometers or less, More preferably, it is 30 micrometers or less. Although the minimum of the thickness of a resin composition layer is not specifically limited, Usually, 5 micrometers or more, 10 micrometers or more etc. can be used.

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

  When a film made of a plastic material is used as the support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”) and polyethylene naphthalate (hereinafter abbreviated as “PEN”). .) Polyester, polycarbonate (hereinafter sometimes abbreviated as “PC”), polymethyl methacrylate (PMMA) and other acrylics, cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether Examples include ketones and polyimides. Among these, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

  When using metal foil as a support body, as metal foil, copper foil, aluminum foil, etc. are mentioned, for example, Copper foil is preferable. As the copper foil, a foil made of a single metal of copper may be used, and a foil made of an alloy of copper and another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.). It may be used.

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

  Moreover, as a support body, you may use the support body with a release layer which has a release layer in the surface joined to a resin composition layer. Examples of the release agent used for the release layer of the support with a release layer include one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. . As the support with a release layer, a commercially available product may be used. For example, “SK-1”, “SK-1” manufactured by Lintec Corporation, which is a PET film having a release layer mainly composed of an alkyd resin release agent. AL-5 ”,“ AL-7 ”,“ Lumirror T60 ”manufactured by Toray Industries, Inc.,“ Purex ”manufactured by Teijin Limited,“ Unipeel ”manufactured by Unitika Ltd., and the like.

  Although it does not specifically limit as thickness of a support body, The range of 5 micrometers-75 micrometers is preferable, and the range of 10 micrometers-60 micrometers is more preferable. In addition, when using a 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 other layers as necessary. Examples of such other layers include a protective film according to the support provided on the surface of the resin composition layer that is not joined to the support (that is, the surface opposite to the support). It is done. Although the thickness of a protective film is not specifically limited, For example, they are 1 micrometer-40 micrometers. By laminating the protective film, it is possible to suppress adhesion and scratches of dust and the like on the surface of the resin composition layer.

  The resin sheet is prepared by, for example, preparing a resin varnish in which a resin composition is dissolved in an organic solvent, applying the resin varnish on a support using a die coater or the like, and further drying to form a resin composition layer. Can be manufactured.

  Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone; acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate; cellosolve and butyl carbitol, etc. Carbitols; aromatic hydrocarbons such as toluene and xylene; amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone. An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.

  Drying may be performed by a known method such as heating or hot air blowing. The drying conditions are not particularly limited, but the 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. Depending on the boiling point of the organic solvent in the resin varnish, for example, when using a resin varnish containing 30% by mass to 60% by mass of the organic solvent, the resin composition is dried at 50 ° C. to 150 ° C. for 3 minutes to 10 minutes. A physical layer can be formed.

  The resin sheet can be stored in a roll. 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 of the resin composition of the present invention.

A printed wiring board can be manufactured by the method including the process of following (I) and (II), for example using the above-mentioned resin sheet.
(I) The process of laminating | stacking so that the resin composition layer of a resin sheet may join to an inner layer board | substrate on an inner layer board | substrate (II) The process of thermosetting a resin composition layer and forming an insulating layer

  The “inner layer substrate” used in the step (I) is a member that becomes a printed wiring board substrate, for example, a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate. Etc. Moreover, this board | substrate may have a conductor layer in the single side | surface or both surfaces, and this conductor layer may be patterned. An inner layer substrate having a conductor layer (circuit) formed on one or both sides of the substrate may be referred to as an “inner layer circuit board”. Further, when the printed wiring board is manufactured, an intermediate product in which an insulating layer and / or a conductor layer is to be formed is also included in the “inner layer substrate” in the present invention. When the printed wiring board is a circuit board with a built-in component, an inner layer board with a built-in component can be used.

  Lamination | stacking of an inner layer board | substrate and a resin sheet can be performed by heat-pressing a resin sheet to an inner layer board | substrate from the support body side, for example. Examples of the member that heat-presses the resin sheet to the inner layer substrate (hereinafter, also referred to as “heat-pressing member”) include a heated metal plate (SUS end plate) or a metal roll (SUS roll). It is preferable that the thermocompression-bonding member is not pressed directly on the resin sheet, but is pressed through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface irregularities of the inner layer substrate.

  Lamination of the inner layer substrate and the resin sheet may be performed by a vacuum laminating method. In the vacuum laminating 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 0.098 MPa to 1.77 MPa, more preferably 0. 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 is preferably performed under reduced pressure conditions with a pressure of 26.7 hPa or less.

  Lamination can be performed with a commercially available vacuum laminator. Examples of the commercially available vacuum laminator include a vacuum pressurizing laminator manufactured by Meiki Seisakusho, a vacuum applicator manufactured by Nikko Materials, and a batch vacuum pressurizing laminator.

  After lamination, the laminated resin sheets may be smoothed under normal pressure (atmospheric pressure), for example, by pressing a thermocompression bonding member from the support side. The pressing conditions for the smoothing treatment can be the same conditions as the thermocompression bonding conditions for the laminate. The smoothing treatment can be performed with a commercially available laminator. In addition, you may perform lamination | stacking and a smoothing process continuously using said commercially available vacuum laminator.

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

  In step (II), the resin composition layer is thermally cured to form an insulating layer. The thermosetting conditions for the resin composition layer are not particularly limited, and the conditions normally employed when forming the insulating layer of the printed wiring board may be used.

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

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

  When manufacturing a printed wiring board, you may further implement (III) the process of drilling in an insulating layer, (IV) the process of roughening an insulating layer, and (V) the process of forming a conductor layer. These steps (III) to (V) may be carried out according to various methods known to those skilled in the art, which are used for manufacturing printed wiring boards. In addition, when removing a support body after process (II), removal of this support body is performed between process (II) and process (III), between process (III) and process (IV), or process ( It may be carried out between IV) and step (V). Moreover, if necessary, the formation of the insulating layer and the conductor layer in steps (II) to (V) may be repeated to form a multilayer wiring board.

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

  Step (IV) is a step of roughening the insulating layer. Usually, in this step (IV), smear is also removed. The procedure and conditions for the roughening treatment are not particularly limited, and known procedures and conditions that are usually used when forming an insulating layer of a printed wiring board can be employed. For example, the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order. The swelling liquid used for the roughening treatment is not particularly limited, and examples thereof include an alkaline solution and a surfactant solution, and an alkaline solution is preferable. Examples of the alkaline solution include a sodium hydroxide solution and a potassium hydroxide solution. preferable. Examples of commercially available swelling liquids include “Swelling Dip Securigans P” and “Swelling Dip Securigans SBU” manufactured by Atotech Japan. Although the swelling process by a swelling liquid is not specifically limited, For example, it can perform by immersing an insulating layer for 1 minute-20 minutes in 30 degreeC-90 degreeC swelling liquid. From the viewpoint of suppressing the swelling of the resin in the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling liquid at 40 ° C. to 80 ° C. for 5 minutes to 15 minutes. Although it does not specifically limit as an oxidizing agent used for a roughening process, For example, the alkaline permanganate solution which melt | dissolved potassium permanganate and 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 to 100 ° C. for 10 to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizers include alkaline permanganate solutions such as “Concentrate Compact CP” and “Dosing Solution Securigans P” manufactured by Atotech Japan. Moreover, as a neutralization liquid used for a roughening process, acidic aqueous solution is preferable, As a commercial item, "Reduction Solution Securigant P" by Atotech Japan is mentioned, for example. The treatment with the neutralizing solution can be performed by immersing the treated surface subjected to the roughening treatment with the oxidizing agent in the neutralizing solution at 30 to 80 ° C. for 1 to 30 minutes. From the viewpoint of workability and the like, a method of immersing an object subjected to roughening treatment with an oxidizing agent in a neutralizing solution at 40 ° C. to 70 ° C. for 5 minutes to 20 minutes is preferable.

  In one embodiment, the arithmetic average roughness (Ra) of the surface of the insulating layer after the roughening treatment is preferably 150 nm or less, more preferably 135 nm or less, and further preferably 120 nm or less. Although it does not specifically limit about a minimum, Preferably it is 30 nm or more, More preferably, it is 40 nm or more, More preferably, it is 50 nm or more. The arithmetic average roughness (Ra) of the insulating layer surface can be measured using a non-contact type surface roughness meter.

  Step (V) is a step of forming a conductor layer, and a 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 is one or more selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. Contains metal. The conductor layer may be a single metal layer or an alloy layer. As the alloy layer, for example, an alloy of two or more metals selected from the above group (for example, nickel-chromium alloy, copper- A layer formed from a nickel alloy and a copper / titanium alloy). Among them, from the viewpoint of versatility of conductor layer formation, cost, ease of patterning, etc., single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or nickel / chromium alloy, copper / An alloy layer of nickel alloy or copper / titanium alloy is preferable, and a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel / chromium alloy is more preferable, and a single layer of copper is preferable. A metal layer is more preferred.

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

  Although the thickness of a conductor layer is based on the design of a desired printed wiring board, generally it is 3 micrometers-35 micrometers, Preferably it is 5 micrometers-30 micrometers.

  In one embodiment, the conductor layer may be formed by plating. For example, a conductive layer having a desired wiring pattern can be formed by plating on the surface of the insulating layer by a conventionally known technique such as a semi-additive method or a full additive method. It is preferable to form by a method. Hereinafter, an example in which the conductor layer is formed by a semi-additive method will be described.

  First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern that exposes a part of the plating seed layer corresponding to a desired wiring pattern is formed on the formed plating seed layer. A metal layer is formed by electrolytic plating on the exposed plating seed layer, and then the mask pattern is removed. Thereafter, an unnecessary plating seed layer can be removed by etching or the like to form a conductor layer having a desired wiring pattern.

[Semiconductor device]
The semiconductor device of the present invention includes the printed wiring board of the present invention. The semiconductor device of the present invention can be manufactured using the printed wiring board of the present invention.

  Examples of the semiconductor device include various semiconductor devices used for electrical products (for example, computers, mobile phones, digital cameras, and televisions) and vehicles (for example, motorcycles, automobiles, trains, ships, and aircrafts).

  The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) on a conductive portion of a printed wiring board. The “conduction location” is a “location where an electrical signal is transmitted on a printed wiring board”, and the location may be a surface or an embedded location. The semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

  The semiconductor chip mounting method for manufacturing the semiconductor device is not particularly limited as long as the semiconductor chip functions effectively. Specifically, the wire bonding mounting method, the flip chip mounting method, and the bumpless buildup layer are used. (BBUL) mounting method, anisotropic conductive film (ACF) mounting method, non-conductive film (NCF) mounting method, and the like. Here, “a mounting method using a build-up layer without a bump (BBUL)” means “a mounting method in which a semiconductor chip is directly embedded in a recess of a printed wiring board and the semiconductor chip and wiring on the printed wiring board are connected”. It is.

  Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to the following examples. In the following description, “parts” and “%” representing amounts mean “parts by mass” and “% by mass”, respectively, unless otherwise specified. Further, the operations described below were performed in an environment of normal temperature and pressure unless otherwise specified.

[Example 1]
10 parts of bisphenol type epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., 1: 1 mixture of bisphenol A type and bisphenol F type, epoxy equivalent 169), and naphthol type epoxy resin (“ESN475V” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) , Epoxy equivalent of about 330) was dissolved in 40 parts of solvent naphtha with stirring. This was cooled to room temperature to prepare an epoxy resin dissolution composition.

To this epoxy resin solution composition, a phenolic curing agent having 5 parts of phenoxy resin (“YX7553BH30” manufactured by Mitsubishi Chemical Corporation, 1: 1 solution of MEK and cyclohexanone having a nonvolatile content of 30% by mass), a triazine skeleton and a novolac structure ( DIC "LA3018-50P", reactive group equivalent of about 151, 2-methoxypropanol solution with 50% non-volatile content, active ester curing agent (DIC "HPC-8000-65T", reactive group equivalent of about 223, 70 parts by weight of a toluene solution having a nonvolatile content of 65% by weight, 20 parts of (meth) acrylic acid ester (“A-DOG” manufactured by Shin-Nakamura Chemical Co., Ltd., (meth) acryloyl group equivalent 156), carbodiimide-based curing agent (Nisshinbo Chemical) "V-03" manufactured by the company, carbodiimide group equivalent 216, non-volatile content 50 mass% toluene solution) 1 Parts, curing accelerator (1-benzyl-2-phenylimidazole (1B2PZ), MEK solution having a nonvolatile content of 10% by mass), polymerization initiator (Park Mill D (manufactured by NOF Corporation, MEK solution having a nonvolatile content of 20%)) ) Spherical silica (average particle size 0.5 μm, specific surface area 5.9 m ² / g, surface-treated with an amine-based alkoxysilane compound (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.)), “SO-” manufactured by Admatechs C2 ") 470 parts, 10 parts of cyclohexanone and 10 parts of MEK were mixed and dispersed uniformly with a high-speed rotary mixer to prepare a resin varnish.

  As a support, a polyethylene terephthalate (PET) film (“LIN5”, 38 μm thickness) provided with a release layer was prepared. On the release layer of this support, the resin varnish was uniformly applied so that the resin composition layer after drying had a thickness of 25 μm. Thereafter, the resin varnish was dried at 80 ° C. to 100 ° C. (average 90 ° C.) for 4 minutes to obtain a resin sheet including a support and a resin composition layer.

A-DOG has the structure shown below.

[Example 2]
In Example 1, 20 parts of (meth) acrylic acid ester (“A-DOG” manufactured by Shin-Nakamura Chemical Co., Ltd., (meth) acryloyl group equivalent 156) was replaced with (meth) acrylic acid ester (“DCP-A manufactured by Kyoeisha Chemical Co., Ltd.). ”, (Meth) acryloyl group equivalent 152) 20 parts. Except for the above, a resin varnish and a resin sheet were produced in the same manner as in Example 1.

DCP-A has the structure shown below.

[Example 3]
In Example 1, the amount of the carbodiimide-based curing agent (“V-03” manufactured by Nisshinbo Chemical Co., Ltd., carbodiimide group equivalent 216, toluene solution having a nonvolatile content of 50% by mass) was changed from 15 parts to 10 parts. Except for the above, a resin varnish and a resin sheet were produced in the same manner as in Example 1.

[Example 4]
In Example 1, 20 parts of acrylic acid ester (“A-DOG” manufactured by Shin-Nakamura Chemical Co., Ltd., (meth) acryloyl group equivalent 156) was changed to 15 parts. Except for the above, the same operation as in Example 1 was performed to produce an adhesive film.

[Example 5]
In Example 1, the amount of carbodiimide-based curing agent (“V-03” manufactured by Nisshinbo Chemical Co., Ltd., carbodiimide group equivalent 216, toluene solution having a nonvolatile content of 50% by mass) was changed from 15 parts to 20 parts, and (meth) acrylic acid The amount of ester (“A-DOG” manufactured by Shin-Nakamura Chemical Co., Ltd., (meth) acryloyl group equivalent 156) was changed from 20 parts to 10 parts. Except for the above, a resin varnish and a resin sheet were produced in the same manner as in Example 1.

[Comparative Example 1]
In Example 1, 15 parts of a carbodiimide-based curing agent (“V-03” manufactured by Nisshinbo Chemical Co., Ltd., a carbodiimide group equivalent 216, a toluene solution having a nonvolatile content of 50 mass%) was not used. Except for the above, a resin varnish and a resin sheet were produced in the same manner as in Example 1.

[Comparative Example 2]
In Example 2, 15 parts of a carbodiimide-based curing agent (“V-03” manufactured by Nisshinbo Chemical Co., Ltd., carbodiimide group equivalent 216, toluene solution having a nonvolatile content of 50 mass%) was not used. A resin varnish and a resin sheet were produced in the same manner as in Example 2 except for the above items.

[Comparative Example 3]
In Example 1, an amine ester alkoxysilane compound (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) was used without using 20 parts of an acrylic ester (“A-DOG” manufactured by Shin-Nakamura Chemical Co., Ltd., (meth) acryloyl group equivalent 156). The amount of the surface-treated spherical silica (average particle size 0.5 μm, “SO-C2” manufactured by Admatechs) was changed from 470 parts to 400 parts. Except for the above, a resin varnish and a resin sheet were produced in the same manner as in Example 1.

[Comparative Example 4]
In Example 1, the amount of a carbodiimide-based curing agent (“V-03” manufactured by Nisshinbo Chemical Co., Ltd., carbodiimide group equivalent 216, toluene solution having a nonvolatile content of 50 mass%) was changed from 15 parts to 3 parts. Except for the above, a resin varnish and a resin sheet were produced in the same manner as in Example 1.

[Comparative Example 5]
In Example 1, the amount of carbodiimide-based curing agent (“V-03” manufactured by Nisshinbo Chemical Co., Ltd., carbodiimide group equivalent 216, toluene solution having a nonvolatile content of 50% by mass) was changed from 15 parts to 20 parts, and (meth) acrylic acid The amount of ester (“A-DOG” manufactured by Shin-Nakamura Chemical Co., Ltd., (meth) acryloyl group equivalent 156) was changed from 20 parts to 5 parts. Except for the above, a resin varnish and a resin sheet were produced in the same manner as in Example 1.

[Evaluation of smear removability and arithmetic average roughness (Ra)]
(1) Ground treatment of interior substrate As inner layer substrate, glass cloth base epoxy resin double-sided copper-clad laminate with copper foil on the surface (copper foil thickness 18 μm, substrate thickness 0.8 mm, Panasonic R1515A )). The copper foil on the surface of the inner layer substrate was etched using a microetching agent (“CZ8101” manufactured by MEC) with a copper etching amount of 1 μm to perform a roughening treatment. Thereafter, drying was performed at 190 ° C. for 30 minutes.

(2) Lamination and curing of resin sheet The resin sheets obtained in the above-described examples and comparative examples were obtained by using a batch-type vacuum pressure laminator (2-stage build-up laminator “CVP700” manufactured by Nikko Materials). Lamination was performed on both surfaces of the inner layer substrate so that the composition layer was bonded to the inner layer substrate. This lamination was carried out by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressure bonding for 30 seconds at a temperature of 100 ° C. and a pressure of 0.74 MPa.

  Next, the laminated resin sheet was smoothed by hot pressing at 100 ° C. and a pressure of 0.5 MPa for 60 seconds under atmospheric pressure. Further, this was put into an oven at 130 ° C. and heated for 30 minutes, then transferred to an oven at 170 ° C. and heated for 30 minutes.

(3) Via hole formation By using a CO ₂ laser processing machine (LK-2K212 / 2C) manufactured by Via Mechanics, an insulating layer was processed under the conditions of a frequency of 2000 Hz, a pulse width of 3 μsec, an output of 0.95 W, and a shot number of 3. A via hole having a top diameter (diameter) of 50 μm on the surface of the insulating layer and a diameter of 40 μm on the bottom surface of the insulating layer was formed. Thereafter, the PET film was peeled off.

(4) Roughening treatment The inner layer substrate was immersed in a swelling dip securigant P manufactured by Atotech Japan for 10 minutes at 60 ° C. Next, a roughening solution Atotech Japan Co. concentrate Compact P was immersed at 80 ° C. 20 minutes _{(KMnO 4:: 60g / L} , NaOH aqueous solution of 40 g / L). Finally, it was immersed at 40 ° C. for 5 minutes in a reduction solution securigant P manufactured by Atotech Japan, which is a neutralizing solution. The obtained substrate was designated as evaluation substrate A.

<Evaluation of smear removability>
The periphery of the bottom of the via hole of the evaluation substrate A was observed with a scanning electron microscope (SEM), 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 criteria.
○: The maximum smear length is less than 5 μm.
X: The maximum smear length is 5 μm or more.

<Measurement of arithmetic average roughness (Ra)>
Using a non-contact type surface roughness meter (WYKO NT3300 manufactured by BECOL Instruments Co., Ltd.) for the evaluation substrate A, the arithmetic average roughness (Ra) is obtained by a numerical value obtained by measuring the measurement range as 121 μm × 92 μm with a VSI mode and a 50 × lens. Asked. Each was measured by determining the average value of 10 points selected at random.

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

<Measurement of peel strength>
A portion of the conductor layer of the evaluation board B that does not include a via hole is cut into a portion having a width of 10 mm and a length of 150 mm, and one end thereof is peeled off to grasp a grip (manufactured by TS E Corp., Autocom type tester, AC -50C-SL), and the load (kgf / cm) when 100 mm was peeled off in the vertical direction at a speed of 50 mm / min at room temperature (25 ° C.) was measured. In addition, when the evaluation board | substrate B was produced and the conductor layer swelled and peel strength was not able to be measured, it evaluated as "swelling."

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

表中、「（Ｂ）成分の含有量」は、樹脂組成物中の樹脂成分を１００質量％とした場合の（Ｂ）成分の含有量を表し、「（Ｃ）成分の含有量」は、樹脂組成物中の樹脂成分を１００質量％とした場合の（Ｃ）成分の含有量を表し、「（Ｄ）成分の含有量」は、樹脂組成物中の不揮発成分を１００質量％とした場合の（Ｄ）成分の含有量を表す。「ｂ／ｃ」は、（Ｂ）成分の質量ｂを（Ｃ）成分の質量ｃで除した値を表す。

In the table, “content of component (B)” represents the content of component (B) when the resin component in the resin composition is 100 mass%, and “content of component (C)” The content of the component (C) when the resin component in the resin composition is 100% by mass is expressed, and “the content of the component (D)” is when the nonvolatile component in the resin composition is 100% by mass. Represents the content of component (D). “B / c” represents a value obtained by dividing the mass b of the component (B) by the mass c of the component (C).

  In Examples 1-5, even if it is a case where it does not contain (D) component-(H) component, although it has a difference in a grade, it has confirmed that it results in the same result as the said Example.

Claims (17)

(A) epoxy resin,
(B) a carbodiimide-based curing agent, and (C) a (meth) acrylic acid ester,
A resin composition in which b / c is 0.1 or more and 1.5 or less, where b is the mass of component (B) in the resin composition and c is the mass of component (C) in the resin composition.   The resin composition according to claim 1, wherein the component (C) has two or more (meth) acryloyl groups per molecule.   The resin composition according to claim 1 or 2, wherein the component (C) has a cyclic structure. The resin composition according to any one of claims 1 to 3, wherein the component (C) has a structure represented by the following formula (C-1).

(In Formula (C-1), R ¹ and R ⁴ each independently represent an acryloyl group or a methacryloyl group, R ² and R ³ each independently represent a divalent linking group. Ring A is a divalent group. Represents a cyclic group.) (B) The resin composition of any one of Claims 1-4 in which a component has a structural unit represented by a following formula (B-1).

(In formula (B-1), X represents an alkylene group, a cycloalkylene group, or an arylene group, which may have a substituent. P represents an integer of 1 to 5. X represents a plurality. If present, they may be the same or different, and * represents a bond.)   (A) The resin composition of any one of Claims 1-5 in which a component contains a liquid epoxy resin and a solid epoxy resin.   Furthermore, the resin composition of any one of Claims 1-6 containing an inorganic filler (D).   (D) The resin composition of Claim 7 whose content of a component is 70 mass% or more when the non-volatile component in a resin composition is 100 mass%.   The resin composition according to any one of claims 1 to 8, wherein the content of the component (C) is 1% by mass or more and 20% by mass or less when the resin component in the resin composition is 100% by mass. object.   (B) Resin composition of any one of Claims 1-9 whose content of a component is 1 mass% or more and 15 mass% or less when the resin component in a resin composition is 100 mass%. object.   The resin composition of any one of Claims 1-10 used for an insulation use.   The resin composition according to any one of claims 1 to 11, which is used for forming an insulating layer.   The resin composition according to any one of claims 1 to 12, which is used for forming an insulating layer for forming a conductor layer.   The resin composition according to any one of claims 1 to 13, which is used for sealing a semiconductor chip.   The resin sheet containing the support body and the resin composition layer provided on this support body containing the resin composition of any one of Claims 1-14.   The printed wiring board containing the insulating layer formed with the hardened | cured material of the resin composition of any one of Claims 1-14.   A semiconductor device comprising the printed wiring board according to claim 16.