JP2022108927A - resin composition - Google Patents

Abstract

To provide a resin composition capable of obtaining a cured product which can keep the arithmetic mean roughness (Ra) of an insulating layer surface after roughening treatment low and has excellent copper plating peel strength and smear removability.SOLUTION: There is provided a resin composition which comprises (A) an allyl compound having an alicyclic structure, (B) an epoxy resin and (C) an active ester compound.SELECTED DRAWING: None

Description

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

2. Description of the Related Art As a technique for manufacturing printed wiring boards, a manufacturing method using a build-up method in which insulating layers and conductor layers are alternately stacked is known. In the build-up manufacturing method, the insulating layer is generally formed by curing a resin composition. In recent years, there has been a demand for lowering the dielectric loss tangent of the insulating layer.

It is known that the dielectric loss tangent of the insulating layer can be further reduced by using an epoxy resin composition containing an active ester compound as the resin composition for forming the insulating layer (Patent Reference 1). However, when an epoxy resin composition containing an active ester compound is used, problems such as a decrease in smear removability have arisen. In addition, although the use of a low-molecular-weight (meth)acrylic acid ester compound can improve the smear removal property (Patent Document 2), the arithmetic average roughness (Ra) of the insulating layer surface after roughening treatment and the copper plating There was a problem with peel strength.

Allyl compounds having an alicyclic structure have been known so far (Patent Documents 3 and 4).

JP 2020-23714 A JP 2019-183071 A JP 2019-89967 A JP 2020-136311 A

An object of the present invention is to provide a resin composition that can keep the arithmetic mean roughness (Ra) of the surface of the insulating layer after roughening treatment low and can obtain a cured product with excellent copper plating peel strength and smear removability. It is about providing things.

In order to achieve the object of the present invention, the present inventors conducted intensive studies and found that, in an epoxy resin composition containing (C) an active ester compound, further by using (A) an allyl compound having an alicyclic structure, , Surprisingly, the arithmetic mean roughness (Ra) of the insulating layer surface after roughening treatment can be suppressed low, and a cured product having excellent copper plating peel strength and smear removability can be obtained. The present invention has been completed.

That is, the present invention includes the following contents.
[1] A resin composition containing (A) an allyl compound having an alicyclic structure, (B) an epoxy resin, and (C) an active ester compound.
[2] Component (A) is represented by formula (a-1):

[In the formula, * indicates a binding site. ]
The resin composition according to [1] above, which has a group represented by
[3] Component (A) has the formula (A3):

[Wherein, X represents a single bond, -C(R ⁵ ) ₂ -, -O-, -CO-, -S-, -SO-, or -SO ₂ -, and R ² and R ⁵ are Each independently represents a hydrogen atom or a hydrocarbon group, R ³ and R ⁴ each independently represents a hydrocarbon group, one R ² and at least one of b R ³ , an allyl group, b and c each independently represent an integer of 0 to 3, and * represents a binding site. ]
The resin composition according to [1] or [2] above, which has a group represented by
[4] The resin composition according to any one of [1] to [3] above, wherein the weight average molecular weight of component (A) is 1,000 to 20,000.
[5] The allyl equivalent of component (A) is 200 g/eq. ~2000g/eq. The resin composition according to any one of [1] to [4] above.
[6] The content of component (A) is 0.01% by mass or more when the non-volatile component in the resin composition is 100% by mass. Resin composition.
[7] The resin composition according to any one of [1] to [6] above, wherein the content of component (A) is 5% by mass or less when the non-volatile component in the resin composition is 100% by mass. thing.
[8] The resin composition according to any one of [1] to [7] above, further comprising (D) a (meth)acrylate compound having a molecular weight of less than 1,000.
[9] The resin composition according to [8] above, wherein the mass ratio of component (D) to component (A) (component (D)/component (A)) is from 0.1 to 10.
[10] The resin composition according to any one of [1] to [9] above, wherein the content of component (C) is 10% by mass or more when the non-volatile component in the resin composition is 100% by mass. thing.
[11] The resin composition according to any one of [1] to [10] above, further comprising (E) an inorganic filler.
[12] The resin composition according to [11] above, wherein the content of component (E) is 60% by mass or more when the non-volatile component in the resin composition is taken as 100% by mass.
[13] The resin composition according to any one of [1] to [12] above, further comprising an imidazole curing accelerator.
[14] The resin composition according to any one of [1] to [13] above, further comprising a curing agent selected from the group consisting of phenolic curing agents and carbodiimide curing agents.
[15] The resin according to any one of [1] to [14] above, wherein the cured product of the resin composition has a dielectric loss tangent (Df) of 0.0030 or less when measured at 5.8 GHz and 23°C. Composition.
[16] A cured product of the resin composition according to any one of [1] to [15] above.
[17] A sheet-like laminate material containing the resin composition according to any one of [1] to [15] above.
[18] A resin sheet comprising a support and a resin composition layer formed from the resin composition according to any one of [1] to [15] provided on the support.
[19] A printed wiring board comprising an insulating layer comprising a cured product of the resin composition according to any one of [1] to [15] above.
[20] A semiconductor device including the printed wiring board according to [19] above.

According to the resin composition of the present invention, the arithmetic mean roughness (Ra) of the insulating layer surface after roughening treatment can be kept low, and a cured product having excellent copper plating peel strength and smear removability can be obtained. can be done.

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will now be described in detail with reference to its preferred embodiments. However, the present invention is not limited to the following embodiments and examples, and can be arbitrarily modified without departing from the scope of the claims of the present invention and their equivalents.

<Resin composition>
The resin composition of the present invention contains (A) an allyl compound having an alicyclic structure, (B) an epoxy resin, and (C) an active ester compound. By using such a resin composition, the arithmetic mean roughness (Ra) of the surface of the insulating layer after roughening treatment can be kept low, and a cured product having excellent copper plating peel strength and smear removability can be obtained. be able to.

The resin composition of the present invention may further contain optional components in addition to (A) an allyl compound having an alicyclic structure, (B) an epoxy resin, and (C) an active ester compound. Optional components include, for example, (C′) other curing agents, (D) (meth)acrylic acid ester compounds having a molecular weight of less than 1000, (E) inorganic fillers, and (F) radically polymerizable compounds having a molecular weight of 1000 or more. , (G) a curing accelerator, (H) a thermoplastic resin, (I) other additives, and (J) an organic solvent. Each component contained in the resin composition will be described in detail below.

<(A) Allyl compound having an alicyclic structure>
The resin composition of the present invention contains (A) an allyl compound having an alicyclic structure. (A) Allyl compounds having an alicyclic structure may be used singly or in combination of two or more at any ratio.

(A) The allyl compound having an alicyclic structure preferably has two or more allyl groups in one molecule. In addition, (A) the allyl compound having an alicyclic structure preferably has an aromatic ring, and the allyl group is directly bonded to the aromatic ring, or a heteroatom selected from an oxygen atom, a nitrogen atom, and a sulfur atom ( preferably via an oxygen atom).

An aromatic ring means a ring conforming to Hückel's rule in which the number of electrons contained in the π-electron system on the ring is 4p+2 (p is a natural number). The aromatic ring may be an aromatic carbocyclic ring having a carbon atom as a ring-constituting atom, or an aromatic heterocyclic ring having a heteroatom such as an oxygen atom, a nitrogen atom, a sulfur atom, etc. in addition to a carbon atom as a ring-constituting atom. is preferably an aromatic carbocycle in one embodiment. In one embodiment, the aromatic ring is preferably a 5- to 14-membered aromatic ring, more preferably a 5- to 10-membered aromatic ring. Preferable specific examples of the aromatic ring include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring and the like, more preferably benzene ring or naphthalene ring, particularly preferably benzene ring.

(A) In one embodiment, the allyl compound having an alicyclic structure has the formula (A1):

[In the formula, each R ¹ independently represents a substituent, at least one of a R ¹ is an allyl group or an allyloxy group, a represents an integer of 1 to 4, * indicates the binding site. ]
It is preferable to have a group represented by the formula (A2):

[In the formula, R ² represents a hydrogen atom or a hydrocarbon group, R ³ each independently represents a hydrocarbon group, and at least one of one R ² and b R ³ is , an allyl group, b represents an integer of 0 to 3, and * represents a binding site. ]
It is more preferable to have a group represented by formula (A3):

[Wherein, X represents a single bond, -C(R ⁵ ) ₂ -, -O-, -CO-, -S-, -SO-, or -SO ₂ -, and R ² and R ⁵ are Each independently represents a hydrogen atom or a hydrocarbon group, R ³ and R ⁴ each independently represents a hydrocarbon group, one R ² and at least one of b R ³ , an allyl group, b and c each independently represent an integer of 0 to 3, and * represents a binding site. ]
It is more preferable to have a group represented by (A) The allyl compound having an alicyclic structure preferably has two or more groups represented by the formulas (A1), (A2) or (A3) in one molecule, particularly two groups. preferable.

Each R ¹ independently represents a substituent. Each R ¹ is independently preferably an allyl group, an allyloxy group, a hydroxy group, an alkyl group, an aryl group, an alkyl-oxy group, or an aryl-oxy group, more preferably an allyl group, an allyloxy group, or a hydroxy group.

In the present specification, the "substituent" is not particularly limited, but examples include allyl group, allyloxy group, amino group, hydroxy group, alkyl group, aryl group, alkyl-aryl group (substituted with alkyl group aryl group), aryl-alkyl group (alkyl group substituted with an aryl group), alkyl-oxy group, aryl-oxy group, alkyl-carbonyl group, aryl-carbonyl group, alkyl-oxy-carbonyl group, aryl- Examples include monovalent substituents such as oxy-carbonyl group, alkyl-carbonyl-oxy group, aryl-carbonyl-oxy group, mono- or di(alkyl)amino group, mono- or di(aryl)amino group.

Alkyl (group) means a linear and/or branched monovalent saturated aliphatic hydrocarbon group. Alkyl (group) is preferably an alkyl (group) having 1 to 6 carbon atoms unless otherwise specified. Examples of alkyl (group) include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, cyclopentyl group, cyclohexyl group and the like. mentioned. Aryl (group) means a monovalent aromatic hydrocarbon group. The aryl (group) is preferably an aryl (group) having 6 to 14 carbon atoms unless otherwise specified. Aryl (group) includes, for example, phenyl group, 1-naphthyl group, 2-naphthyl group and the like. A halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

a represents an integer of 1 to 4; a is preferably 1, 2 or 3, more preferably 1 or 2.

^R2 represents a hydrogen atom or a hydrocarbon group. R ² is preferably a hydrogen atom, an allyl group or an alkyl group, more preferably a hydrogen atom or an allyl group. Each R ³ independently represents a hydrocarbon group. R ³ is preferably an allyl group or an alkyl group, more preferably an allyl group.

In the present specification, the "hydrocarbon group" is not particularly limited, and examples thereof include monovalent hydrocarbon groups such as allyl groups, alkyl groups, aryl groups, alkyl-aryl groups, and aryl-alkyl groups. is mentioned.

b represents an integer of 0 to 3; b is preferably 0, 1 or 2, more preferably 0 or 1;

In a first embodiment, preferably ^R2 is an allyl group, ^each R3 is independently a hydrocarbon group, and b is 0, 1 or 2; R ² is an allyl group, R ³ is each independently an alkyl group, and b is 0 or 1; particularly preferably R ² is an allyl group and b is is 0.

In a second embodiment, preferably R ² is a hydrogen atom, each R ³ is independently a hydrocarbon group, b is 1 or 2, and b R ³ at least one of which is an allyl group; more preferably, R ² is a hydrogen atom, R ³ is each independently an allyl group or an alkyl group, b is 1 or 2, and at least one of the b R ³ is an allyl group; particularly preferably R ² is a hydrogen atom, R ³ is an allyl group and b is 1.

X represents a single bond, -C(R ⁵ ) ₂ -, -O-, -CO-, -S-, -SO- or -SO ₂ -. X is preferably a single bond, -C(R ⁵ ) ₂ -, or -O-; more preferably a single bond or -C(R ⁵ ) ₂ -; particularly preferably -C( R ⁵ ) ₂ -.

Each ^R5 independently represents a hydrogen atom or a hydrocarbon group. Each ^R5 is independently preferably a hydrogen atom, an alkyl group, or an aryl group, more preferably a hydrogen atom or an alkyl group, particularly preferably a hydrogen atom.

Each ^R4 independently represents a hydrocarbon group. ^R4 is preferably an allyl group or an alkyl group, more preferably an allyl group.

c represents an integer of 0 to 3; c is preferably 0, 1 or 2, more preferably 0 or 1. In a first embodiment, c is particularly preferably 0. In a second embodiment, c is particularly preferably 1.

(A) The alicyclic structure in the allyl compound having an alicyclic structure is a ring skeleton structure of a non-aromatic ring. (A) The non-aromatic ring in the alicyclic structure of the allyl compound having an alicyclic structure may have a substituent at a substitutable position. The non-aromatic ring may be a saturated ring consisting only of single bonds or a non-aromatic unsaturated ring having either a double bond or a triple bond, but is preferably a saturated ring consisting only of single bonds. The saturated ring may be a saturated carbocyclic ring having carbon atoms as ring-constituting atoms, or a saturated heterocyclic ring having a heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom in addition to carbon atoms as ring-constituting atoms.

The saturated ring is preferably a saturated ring having 3 to 18 carbon atoms, more preferably a saturated ring having 5 to 16 carbon atoms. Examples of saturated rings include monocyclic monocyclic alkane rings such as cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, and cyclododecane ring. saturated carbocyclic ring, bicyclo[2.2.1]heptane ring (norbornane ring), bicyclo[4.4.0]decane ring (decane ring), bicyclo[5.3.0]decane ring, bicyclo[4.3 .0]nonane ring (hydrindane ring), bicyclo[3.2.1]octane ring, bicyclo[5.4.0]undecane ring, bicyclo[3.3.0]octane ring, bicyclo[3.3.1 ] Bicyclic saturated carbocyclic ring such as nonane ring, tricyclo[5.2.1.0 ^2,6 ]decane ring (tetrahydrodicyclopentadiene ring), tricyclo[3.3.1.1 ^3,7 ]decane ring (adamantane ring), tricyclic saturated carbocyclic ring such as tricyclo[6.2.1.0 ^2,7 ]undecane ring, tetracyclo[6.2.1.1 ^3,6 . 0 ^2,7 ]dodecane ring and other saturated carbocyclic rings, pentacyclo[9.2.1.1 ^4,7 . 0 ^2,1 0.0 ^3,8 ]pentadecane ring, pentacyclo[6.5.1.1 ^3,6 . 0 ^{2, 7} . 0 ^9,13 ] saturated carbocyclic ring such as pentacyclic saturated carbocyclic ring such as pentadecane ring (tetrahydrotricyclopentadiene ring) ring; pyrrolidine ring, pyrazolidine ring, imidazolidine ring, tetrahydrofuran ring, 1,3-dioxolane ring, piperidine ring, piperazine ring, tetrahydropyran ring, 1,3-dioxane ring, 1,4-dioxane ring, thiane ring, 1,3-dithiane ring, 1,4-dithiane ring, morpholine ring, thiomorpholine ring, oxazolidine ring Monocyclic saturated heterocycles such as 7-oxabicyclo[4.1.0]heptane ring (1,2-epoxycyclohexane ring), 1-azabicyclo[2.2.2]octane (quinuclidine ring), deca Bicyclic saturated heterocycles such as hydroquinoline ring and decahydroisoquinoline ring, 1-azatricyclo[3.3.1.1 ^3,7 ]decane (1-azaadamantane ring), 2-azatricyclo[3.3. 1.1 Saturated heterocycles such as tricyclic saturated heterocycles such as ^3,7 ]decane (2-azaadamantane ring).

(A) In the allyl compound having an alicyclic structure, the non-aromatic ring is preferably a saturated carbocyclic ring, more preferably a bicyclic or higher saturated carbocyclic ring, a bicyclic saturated carbocyclic ring, a tricyclic A saturated carbocyclic ring system, a tetracyclic saturated carbocyclic ring system, or a pentacyclic saturated carbocyclic ring system are more preferred.

(A) Allyl compounds having an alicyclic structure, in one embodiment, are represented by formulas (a-1) to (a-8) containing a bicyclic or higher saturated carbocyclic ring:

[In the formula, * indicates a binding site. ]
It is preferable to have a group represented by and among them, it is preferable to have a group represented by formula (a-1).

(A) The allyl compound having an alicyclic structure, in one embodiment, preferably includes a carbonate resin having an alicyclic structure and an allyl group, and is not particularly limited, and has the formula (A):

[In the formula,
A ¹ each independently represents a group represented by formula (A3) described above;
A ² are each independently represented by formula (Aa):

(Wherein, Y each independently represents a single bond or an alkylene group, each ring Cy independently represents a non-aromatic ring that may have a substituent, * represents a bond indicate the part.)
A group represented by or formula (Ab):

(Wherein, Z represents a single bond, —C(R ⁸ ) ₂ —, —O—, —CO—, —S—, —SO—, or —SO ₂ —, and R ⁶ and R ⁷ are Each independently represents a hydrocarbon group, R ⁸ each independently represents a hydrogen atom or a hydrocarbon group, e and d each independently represents an integer of 0 to 3, * , indicates the binding site.)
wherein at least one of the n A ² is a group represented by the formula (Aa);
n represents an integer of 0 or more. ]
It is particularly preferable to contain a carbonate resin represented by.

Each Y independently represents a single bond or an alkylene group. Each Y is independently a single bond or a methylene group, more preferably a methylene group.

An alkylene group refers to a linear and/or branched divalent saturated hydrocarbon group. The alkylene group is preferably an alkylene group having 1 to 6 carbon atoms. Examples of alkylene groups include linear alkylene groups such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, and decamethylene; ethylidene; , a propylidene group, an isopropylidene group, an ethylmethylmethylene group, a diethylmethylene group, and other branched alkylene groups.

Each ring Cy independently represents a non-aromatic ring optionally having a substituent. Each ring Cy is independently an optionally substituted bicyclic or higher saturated carbocyclic ring, particularly preferably a tricyclo[5.2.1.0 ^2,6 ]decane ring (tetrahydro dicyclopentadiene ring).

^R6 and ^R7 each independently represent a hydrocarbon group. R ⁶ and R ⁷ are each independently preferably an allyl group or an alkyl group, more preferably an allyl group.

e and d each independently represent an integer of 0 to 3; e and d are each independently preferably 0, 1 or 2, more preferably 0 or 1;

Z represents a single bond, -C(R ⁸ ) ₂ -, -O-, -CO-, -S-, -SO- or -SO ₂ -. Z is preferably a single bond, -C(R ⁸ ) ₂ -, or -O-; more preferably a single bond or -C(R ⁸ ) ₂ -; particularly preferably -C( R ⁸ ) ₂ -.

Each ^R8 independently represents a hydrogen atom or a hydrocarbon group. Each R ⁸ is independently preferably a hydrogen atom, an alkyl group, or an aryl group, more preferably a hydrogen atom or an alkyl group, particularly preferably a hydrogen atom.

n represents an integer of 0 or more. n is preferably an integer of 0-200, more preferably an integer of 0-100. At least one of n A ² is a group represented by formula (Aa). The ratio of the group represented by the formula (Aa) among the n A ² is preferably 20 mol % or more, more preferably 50 mol % or more.

(A) The weight average molecular weight of the allyl compound having an alicyclic structure is preferably 20,000 or less, more preferably 15,000 or less. (A) The lower limit of the weight average molecular weight of the allyl compound having an alicyclic structure is not particularly limited, but is preferably 1,000 or more, more preferably 1,500 or more, and particularly preferably 2,000 or more. The weight average molecular weight of the resin can be measured as a polystyrene-equivalent value by a gel permeation chromatography (GPC) method.

(A) The allyl compound having an alicyclic structure preferably has an allyl equivalent weight of 150 g/eq. ~5000g/eq. , more preferably 200 g/eq. ~2000 g/eq. , more preferably 250 g/eq. ~1500 g/eq. , even more preferably 300 g/eq. ~1200 g/eq. is. Allyl equivalent weight is the mass of allyl compound per equivalent of allyl group.

(A) Commercially available allyl compounds having an alicyclic structure include, for example, "FTC809AE" and "FATC809" manufactured by Gunei Chemical Industry Co., Ltd., and one or more of them can be used. .

The content of (A) the allyl compound having an alicyclic structure in the resin composition is not particularly limited. When 100% by mass, it is preferably 10% by mass or less, more preferably 7% by mass or less, even more preferably 5% by mass or less, even more preferably 4% by mass or less, and particularly preferably 3.5% by mass or less. . The lower limit of the content of (A) the allyl compound having an alicyclic structure in the resin composition is not particularly limited, but the arithmetic average roughness (Ra) of the insulating layer surface after roughening treatment is more than From the viewpoint of keeping it low and further improving the peel strength, when the non-volatile component in the resin composition is 100% by mass, it is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and still more preferably 0% by mass. 0.1% by mass or more, more preferably 0.5% by mass or more, and particularly preferably 1% by mass or more.

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

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

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

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

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

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

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

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

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

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

(B) When a combination of a liquid epoxy resin and a solid epoxy resin is used as the epoxy resin, the mass ratio (liquid epoxy resin:solid epoxy resin) is preferably 10:1 to 1:50, more preferably. is 2:1 to 1:20, particularly preferably 1:1 to 1:10.

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

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

The content of the (B) epoxy resin in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 30% by mass or less, more preferably 25% by mass. % by mass or less, more preferably 20% by mass or less, even more preferably 15% by mass or less, and particularly preferably 10% by mass or less. The lower limit of the content of the (B) epoxy resin in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 0.1% by mass or more, It is more preferably 0.5% by mass or more, still more preferably 1% by mass or more, even more preferably 3% by mass or more, and particularly preferably 5% by mass or more.

The mass ratio of (B) epoxy resin to (A) allyl compound having an alicyclic structure in the resin composition ((B) component/(A) component) is preferably 1 or more, more preferably 1.5 or more. , particularly preferably 2 or more. The upper limit of the mass ratio of (B) epoxy resin to (A) allyl compound having an alicyclic structure in the resin composition (component (B)/component (A)) is preferably 1000 or less, more preferably 100 or less. , particularly preferably 50 or less.

<(C) Active ester compound>
The resin composition of the present invention contains (C) an active ester compound. (C) The active ester compound may be used singly or in combination of two or more at any ratio. (C) The active ester compound can function as an epoxy resin curing agent that reacts with (B) the epoxy resin to cure it.

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

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

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

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

The content of (C) the active ester compound in the resin composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, and even more preferably, when the non-volatile component in the resin composition is 100% by mass. is 5% by mass or more, more preferably 10% by mass or more, and particularly preferably 13% by mass or more. The upper limit of the content of (C) the active ester compound in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 50% by mass or less, or more. It is preferably 40% by mass or less, more preferably 30% by mass or less, even more preferably 25% by mass or less, and particularly preferably 20% by mass or less.

The mass ratio of (C) active ester compound to (A) allyl compound having an alicyclic structure in the resin composition ((C) component/(A) component) is preferably 2 or more, more preferably 3 or more, Especially preferably, it is 4 or more. The upper limit of the mass ratio of (C) active ester compound to (A) allyl compound having an alicyclic structure in the resin composition (component (C)/component (A)) is preferably 2000 or less, more preferably 200. Below, particularly preferably 100 or less.

<(C') Other Curing Agent>
The resin composition of the present invention may further contain a curing agent (C') other than the component (C) as an optional component. (C') Other curing agents may be used singly or in any combination of two or more. (C') Other curing agents, like (C) active ester compounds, may function as epoxy resin curing agents that react with (B) epoxy resins to cure them.

(C') Other curing agents include, but are not limited to, phenol-based curing agents, carbodiimide-based curing agents, acid anhydride-based curing agents, amine-based curing agents, benzoxazine-based curing agents, Examples include cyanate ester-based curing agents and thiol-based curing agents. The resin composition of the present invention particularly preferably contains a curing agent selected from the group consisting of phenolic curing agents and carbodiimide curing agents.

As the phenolic curing agent, a phenolic curing agent having a novolac structure is preferable from the viewpoint of heat resistance and water resistance. From the viewpoint of adhesion to adherends, a nitrogen-containing phenolic curing agent is preferred, and a triazine skeleton-containing phenolic curing agent is more preferred. Among them, a triazine skeleton-containing phenol novolak resin is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion. Specific examples of the phenol-based curing agent include, for example, Meiwa Chemical Co., Ltd. "MEH-7700", "MEH-7810", "MEH-7851", Nippon Kayaku Co., Ltd. "NHN", "CBN", " GPH", "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN- 375", "SN-395", DIC's "LA-7052", "LA-7054", "LA-3018", "LA-3018-50P", "LA-1356", "TD2090", " TD-2090-60M" and the like.

Examples of carbodiimide-based curing agents include curing agents having one or more, preferably two or more carbodiimide structures in one molecule. aliphatic biscarbodiimides such as t-butylcarbodiimide); biscarbodiimides such as aromatic biscarbodiimides such as phenylene-bis(xylylcarbodiimide); polyhexamethylenecarbodiimide, polytrimethylhexamethylenecarbodiimide, polycyclohexylenecarbodiimide, poly(methylene biscyclohexylenecarbodiimide), poly(isophoronecarbodiimide) and other aliphatic polycarbodiimides; poly(phenylenecarbodiimide), poly(naphthylenecarbodiimide), poly(tolylenecarbodiimide), poly(methyldiisopropylphenylenecarbodiimide), poly(triethylphenylene carbodiimide), poly(diethylphenylenecarbodiimide), poly(triisopropylphenylenecarbodiimide), poly(diisopropylphenylenecarbodiimide), poly(xylylenecarbodiimide), poly(tetramethylxylylenecarbodiimide), poly(methylenediphenylenecarbodiimide), poly Examples include polycarbodiimides such as aromatic polycarbodiimides such as [methylenebis(methylphenylene)carbodiimide].

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

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

Amine-based curing agents include curing agents having one or more, preferably two or more amino groups in one molecule. Examples include aliphatic amines, polyether amines, alicyclic amines, Aromatic amines and the like can be mentioned, and among them, aromatic amines are preferable from the viewpoint of achieving the desired effects of the present invention. Amine-based curing agents are preferably primary amines or secondary amines, more preferably primary amines. Specific examples of amine curing agents include 4,4'-methylenebis(2,6-dimethylaniline), 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, and 3,3'-diaminodiphenylsulfone. , m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4′-diaminodiphenyl ether, 3,3′-dimethyl-4,4′-diaminobiphenyl, 2,2′-dimethyl-4,4′ -diaminobiphenyl, 3,3′-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2, 2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4- aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)sulfone, bis(4- (3-aminophenoxy)phenyl)sulfone, and the like. Commercially available amine-based curing agents may be used, for example, Seika "SEIKACURE-S", Nippon Kayaku "KAYABOND C-200S", "KAYABOND C-100", "KAYAHARD AA". , “Kayahard AB”, “Kayahard AS”, “Epicure W” manufactured by Mitsubishi Chemical Corporation, and the like.

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

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

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

(C') The reactive group equivalent of other curing agents is preferably 50 g/eq. ~3000g/eq. , more preferably 100 g/eq. ~1000g/eq. , more preferably 100 g/eq. ~500 g/eq. , particularly preferably 100 g/eq. ~300 g/eq. is. Reactive group equivalent weight is the mass of curing agent per equivalent of reactive group.

The content of (C′) other curing agent in the resin composition is not particularly limited, but when the nonvolatile component in the resin composition is 100% by mass, it is preferably 15% by mass or less, more It is preferably 10% by mass or less, more preferably 7% by mass or less, and particularly preferably 5% by mass or less. The lower limit of the content of (C′) other curing agent in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, for example, 0% by mass or more , 0.01% by mass or more, 0.1% by mass or more, 1% by mass or more, 2% by mass or more, and the like.

The content of (C) the active ester compound in the resin composition is preferably 10 mass when the total of (C) the active ester compound and (C') other curing agent in the resin composition is 100 mass%. % or more, more preferably 30 mass % or more, still more preferably 40 mass % or more, and particularly preferably 50 mass % or more.

<(D) (Meth)acrylic acid ester compound having a molecular weight of less than 1000>
The resin composition of the present invention may further contain (D) a (meth)acrylate compound having a molecular weight of less than 1,000 as an optional component. (D) The (meth)acrylic acid ester compound having a molecular weight of less than 1000 may be used singly or in any combination of two or more.

(D) The (meth)acrylate compound having a molecular weight of less than 1000 is a radically polymerizable compound having one or more acryloyl groups and/or methacryloyl groups in one molecule. (D) The (meth)acrylic acid ester compound having a molecular weight of less than 1000 preferably has two or more acryloyl groups and/or methacryloyl groups in one molecule.

(D) Examples of the (meth)acrylic acid ester compound having a molecular weight of less than 1000 include cyclohexane-1,4-dimethanol di(meth)acrylate, cyclohexane-1,3-dimethanol di(meth)acrylate, tricyclodecanedimethanol di( (Meth)acrylic acid ester compounds with a molecular weight of less than 1000 containing an alicyclic structure with a molecular weight of less than 1000, such as meth)acrylates and dioxane glycol di(meth)acrylate; neopentyl glycol di(meth)acrylate, 1,4-butanediol Di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 3,6-dioxa-1,8-octanediol diol (meth)acrylates, 3,6,9-trioxaundecane-1,11-diol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 9,9-bis[4-( 2-acryloyloxyethoxy)phenyl]fluorene, ethoxylated bisphenol A di(meth)acrylate, propoxylated bisphenol A di(meth)acrylate and other (meth)acrylic acid ester compounds having a molecular weight of less than 1000 that do not contain an alicyclic structure Among them, a (meth)acrylic acid ester compound having a molecular weight of less than 1000 and containing an alicyclic structure is preferred.

(D) The alicyclic structure in the (meth)acrylate compound having a molecular weight of less than 1000 may be a non-aromatic ring skeleton structure. (D) The non-aromatic ring in the alicyclic structure contained in the (meth)acrylate compound having a molecular weight of less than 1000 may have a substituent at a substitutable position. The non-aromatic ring may be a saturated ring consisting only of single bonds or a non-aromatic unsaturated ring having at least one of a double bond and a triple bond, but is preferably a saturated ring consisting only of single bonds. . The saturated ring may be a saturated carbocyclic ring having carbon atoms as ring-constituting atoms, or a saturated heterocyclic ring having a heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom in addition to carbon atoms as ring-constituting atoms. Examples of the saturated ring include those similar to those exemplified above.

(D) In the (meth)acrylic acid ester compound having a molecular weight of less than 1000, the non-aromatic ring is preferably a saturated carbocyclic ring having 3 to 18 carbon atoms or a saturated heterocyclic ring having 3 to 18 carbon atoms. A saturated carbocyclic ring having 5 to 16 carbon atoms or a saturated heterocyclic ring having 5 to 16 carbon atoms is more preferable, and a 1,3-dioxane ring or a tricyclo[5.2.1.0 ^2,6 ]decane ring (tetrahydrodicyclo pentadiene ring) is more preferred.

(D) In one embodiment, the acryloyl group and/or methacryloyl group in the (meth)acrylate compound having a molecular weight of less than 1000 is a hetero atom (preferably an oxygen atom) selected from an oxygen atom, a nitrogen atom, and a sulfur atom, or preferably bonded to a non-aromatic ring via a combination of a hetero atom (preferably an oxygen atom) and an alkylene group (more preferably a hetero atom on the acryloyl group or methacryloyl group side and an alkylene group on the non-aromatic ring side) .

(D) Examples of commercially available (meth)acrylic acid ester compounds having a molecular weight of less than 1000 include "A-DOG" (dioxane glycol diacrylate) manufactured by Shin-Nakamura Chemical Co., Ltd., and "DCP-A" manufactured by Kyoeisha Chemical Co., Ltd. ” (Tricyclodecanedimethanol diacrylate), “DCP” (tricyclodecanedimethanol dimethacrylate), Nippon Kayaku Co., Ltd. “KAYARAD R-684” (tricyclodecanedimethanol diacrylate), “KAYARAD R- 604" (dioxane glycol diacrylate) and the like.

(D) The (meth)acrylic acid ester compound having a molecular weight of less than 1000 preferably has a (meth)acrylic equivalent of 30 g/eq. ~500 g/eq. , more preferably 40 g/eq. ~400 g/eq. , more preferably 50 g/eq. ~300 g/eq. , particularly preferably 75 g/eq. ~200 g/eq. is. (Meth)acrylic equivalent is the mass of the compound per equivalent of acryloyl group and methacryloyl group.

(D) The (meth)acrylate compound having a molecular weight of less than 1,000 preferably has a molecular weight of 800 or less, more preferably 600 or less. Although the lower limit is not particularly limited, it can be, for example, 100 or more.

The content of (D) the (meth)acrylic acid ester compound having a molecular weight of less than 1000 in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably It is 25% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less, even more preferably 7% by mass or less, and particularly preferably 5% by mass or less. The lower limit of the content of (D) the (meth)acrylic acid ester compound having a molecular weight of less than 1000 in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, For example, it is 0% by mass or more, 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, and particularly preferably 1.5% by mass. % or more.

The mass ratio of the (D) (meth)acrylate compound having a molecular weight of less than 1000 to the (A) allyl compound having an alicyclic structure in the resin composition (component (D)/component (A)) is preferably 100. Below, more preferably 50 or less, particularly preferably 10 or less. The lower limit of the mass ratio (component (D)/component (A)) of the (D) (meth)acrylate compound having a molecular weight of less than 1000 to the (A) allyl compound having an alicyclic structure in the resin composition is preferably is 0.01 or more, more preferably 0.05 or more, and particularly preferably 0.1 or more.

<(E) Inorganic filler>
The resin composition of the present invention may further contain (E) an inorganic filler as an optional component. (E) The inorganic filler is contained in the resin composition in the form of particles.

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

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

The average particle size of the (E) inorganic filler is not particularly limited, but is preferably 10 μm or less, more preferably 5 μm or less, still more preferably 2 μm or less, even more preferably 1 μm or less, and particularly preferably 0.001 μm or less. 7 μm or less. (E) The lower limit of the average particle size of the inorganic filler is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, still more preferably 0.1 μm or more, and particularly preferably 0 .2 μm or more. (E) The average particle size of the inorganic filler can be measured by a laser diffraction/scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler is prepared on a volume basis using a laser diffraction/scattering type particle size distribution measuring device, and the median diameter can be used as the average particle size for measurement. A measurement sample can be obtained by weighing 100 mg of an inorganic filler and 10 g of methyl ethyl ketone in a vial and dispersing them with ultrasonic waves for 10 minutes. A measurement sample is measured using a laser diffraction particle size distribution measuring device, the wavelengths of the light source used are blue and red, the volume-based particle size distribution of the inorganic filler is measured by the flow cell method, and from the obtained particle size distribution The average particle diameter was calculated as the median diameter. Examples of the laser diffraction particle size distribution analyzer include "LA-960" manufactured by Horiba, Ltd., and the like.

(E) The specific surface area of the inorganic filler is not particularly limited, but is preferably 0.1 m ² /g or more, more preferably 0.5 m ² /g or more, still more preferably 1 m ² /g or more, Particularly preferably, it is 3 m ² /g or more. (E) The upper limit of the specific surface area of the inorganic filler is not particularly limited, but is preferably 100 m ² /g or less, more preferably 70 m ² /g or less, even more preferably 50 m ² /g or less, and particularly preferably is 40 m ² /g or less. The specific surface area of the inorganic filler is determined by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech) according to the BET method, and calculating the specific surface area using the BET multipoint method. obtained by

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

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

From the viewpoint of improving the dispersibility of the inorganic filler, the degree of surface treatment with the surface treatment agent is preferably within a predetermined range. Specifically, 100% by mass of the inorganic filler is preferably surface-treated with a surface treatment agent of 0.2% to 5% by mass, and is surface-treated with 0.2% to 3% by mass. more preferably 0.3 mass % to 2 mass % of the surface treatment.

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

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

The content of the (E) inorganic filler in the resin composition is not particularly limited when the non-volatile component in the resin composition is 100% by mass, but is preferably 10% by mass or more and 20% by mass. above, more preferably 30% by mass or more, 40% by mass or more, still more preferably 50% by mass or more, 55% by mass or more, even more preferably 60% by mass or more, 63% by mass or more, particularly preferably 65% by mass or more, It is 67% by mass or more. The upper limit of the content of the (E) inorganic filler in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 90% by mass or less, more It is preferably 85% by mass or less, more preferably 80% by mass or less, and particularly preferably 75% by mass or less.

The mass ratio of (E) inorganic filler to (A) allyl compound having an alicyclic structure in the resin composition ((E) component/(A) component) is preferably 10 or more, more preferably 15 or more, Especially preferably, it is 20 or more. The upper limit of the mass ratio of (E) inorganic filler to (A) allyl compound having an alicyclic structure in the resin composition (component (E)/component (A)) is preferably 10,000 or less, more preferably 1,000. 400 or less is particularly preferable.

<(F) Radically polymerizable compound having a molecular weight of 1000 or more>
The resin composition of the present invention may contain (F) a radically polymerizable compound having a molecular weight of 1000 or more as an optional component. (F) Radically polymerizable compounds having a molecular weight of 1000 or more may be used singly or in combination of two or more.

(F) The radically polymerizable compound having a molecular weight of 1000 or more is, in one embodiment, a radically polymerizable compound having an ethylenically unsaturated bond. (F) The radically polymerizable compound having a molecular weight of 1000 or more is not particularly limited, but examples thereof include allyl group, 3-cyclohexenyl group, 3-cyclopentenyl group, p-vinylphenyl group and m-vinylphenyl group. , Unsaturated hydrocarbon groups such as o-vinylphenyl groups; α,β- It may have radically polymerizable groups such as unsaturated carbonyl groups. (F) The radically polymerizable compound having a molecular weight of 1000 or more preferably has two or more radically polymerizable groups in one molecule.

(F) The radically polymerizable compound having a molecular weight of 1000 or more may be, for example, a (meth)acrylic radically polymerizable compound, a styrene radically polymerizable compound, a maleimide radically polymerizable compound, or the like.

The (meth)acrylic radically polymerizable compound is, for example, a compound having one or more, preferably two or more acryloyl groups and/or methacryloyl groups. (Meth)acrylic-modified polyphenylene ether resin and the like. Examples of commercially available (meth)acrylic radically polymerizable compounds include “SA9000” and “SA9000-111” (methacrylic-modified polyphenylene ether resins) manufactured by SABIC Innovative Plastics.

The styrene-based radically polymerizable compound is, for example, a compound having one or more, preferably two or more vinyl groups directly bonded to an aromatic carbon atom. Examples of styrene-based radically polymerizable compounds include vinylbenzyl-modified polyphenylene ether resins and styrene-divinylbenzene copolymers. Examples of commercially available styrene-based radical polymerizable compounds include "ODV-XET (X03)", "ODV-XET (X04)", and "ODV-XET (X05)" (styrene -divinylbenzene copolymer), Mitsubishi Gas Chemical Company's "OPE-2St 1200" and "OPE-2St 2200" (vinylbenzyl-modified polyphenylene ether resin).

The maleimide-based radically polymerizable compound is, for example, a compound having one or more, preferably two or more maleimide groups. The maleimide-based radically polymerizable compound may be an aliphatic maleimide compound containing an aliphatic amine skeleton or an aromatic maleimide compound containing an aromatic amine skeleton. "MIR-5000-60T" and "MIR-3000-70MT" (biphenylaralkyl-type maleimide compounds) manufactured by the Company.

(F) The ethylenically unsaturated bond equivalent of the radically polymerizable compound having a molecular weight of 1000 or more is preferably 20 g/eq. ~3000g/eq. , more preferably 50 g/eq. ~2500 g/eq. , more preferably 70 g/eq. ~2000g/eq. , particularly preferably 90 g/eq. ~1500 g/eq. is. The ethylenically unsaturated bond equivalent is the mass of the radically polymerizable compound per equivalent of ethylenically unsaturated bond.

(F) The weight average molecular weight (Mw) of the radically polymerizable compound having a molecular weight of 1,000 or more is preferably 40,000 or less, more preferably 10,000 or less, still more preferably 6,000 or less, and particularly preferably 4,000 or less. The weight average molecular weight of the resin can be measured as a polystyrene-equivalent value by a gel permeation chromatography (GPC) method.

The content of (F) the radical polymerizable compound having a molecular weight of 1000 or more in the resin composition is not particularly limited, but is preferably 25% by mass when the non-volatile component in the resin composition is 100% by mass. 15% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, and particularly preferably 3% by mass or less. The lower limit of the content of (F) the radically polymerizable compound having a molecular weight of 1000 or more in the resin composition is not particularly limited, but when the nonvolatile component in the resin composition is 100% by mass, for example, 0 % by mass or more, preferably 0.001% by mass or more, preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 0.1% by mass or more, and particularly preferably 0.5% by mass That's it.

<(G) Curing accelerator>
The resin composition of the present invention may contain (G) a curing accelerator as an optional component. The (G) curing accelerator functions as a curing catalyst that accelerates the curing of the (B) epoxy resin.

Examples of curing accelerators include phosphorus-based curing accelerators, urea-based curing accelerators, guanidine-based curing accelerators, imidazole-based curing accelerators, metal-based curing accelerators, and amine-based curing accelerators. From the viewpoint of improving crosslinkability, the resin composition of the present invention preferably contains an imidazole curing accelerator. (G) The curing accelerator may be used singly or in combination of two or more.

Phosphorus curing accelerators include, for example, tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium) pyromellitate, tetrabutylphosphonium hydro Aliphatic phosphonium salts such as genhexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate, di-tert-butyldimethylphosphonium tetraphenylborate; methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra-p-tolylborate, tetraphenyl phosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, triphenylethylphosphonium tetraphenylborate, tris(3-methylphenyl)ethylphosphonium tetraphenylborate, tris(2-methoxyphenyl)ethylphosphonium tetraphenylborate, (4 -methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, aromatic phosphonium salts such as butyltriphenylphosphonium thiocyanate; aromatic phosphine/borane complexes such as triphenylphosphine/triphenylborane; triphenylphosphine/p-benzoquinone Aromatic phosphine/quinone addition reaction products such as addition reaction products; 2-butenyl)phosphine, aliphatic phosphines such as tricyclohexylphosphine; -tolylphosphine, tri-m-tolylphosphine, tri-p-tolyl Phosphine, Tris(4-ethylphenyl)phosphine, Tris(4-propylphenyl)phosphine, Tris(4-isopropylphenyl)phosphine, Tris(4-butylphenyl)phosphine, Tris(4-tert-butylphenyl)phosphine, Tris (2,4-dimethylphenyl)phosphine, tris(2,5-dimethylphenyl)phosphine, tris(2,6-dimethylphenyl)phosphine, tris(3,5-dimethylphenyl)phosphine, tris(2,4,6 -trimethylphenyl)phosphine, tris(2,6-dimethyl-4-ethoxyphenyl)phosphine, tris(2-methoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine, tris(4-ethoxyphenyl)phosphine, tris( 4-tert-butoxyphenyl)phosphine, diphenyl-2-pyridylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino) Aromatic phosphines such as butane, 1,2-bis(diphenylphosphino)acetylene, 2,2'-bis(diphenylphosphino)diphenyl ether, and the like can be mentioned.

Urea-based curing accelerators include, for example, 1,1-dimethylurea; 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, 3- Aliphatic dimethylurea such as cyclooctyl-1,1-dimethylurea; 3-phenyl-1,1-dimethylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl )-1,1-dimethylurea, 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4- methylphenyl)-1,1-dimethylurea, 3-(3,4-dimethylphenyl)-1,1-dimethylurea, 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4- methoxyphenyl)-1,1-dimethylurea, 3-(4-nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy)phenyl]-1,1-dimethylurea, 3- [4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trifluoromethyl)phenyl]-1,1-dimethylurea, N,N-(1,4-phenylene) Aromatic dimethylurea such as bis(N',N'-dimethylurea), N,N-(4-methyl-1,3-phenylene)bis(N',N'-dimethylurea) [toluenebisdimethylurea] etc.

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

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

As the imidazole-based curing accelerator, a commercially available product may be used, for example, "1B2PZ", "2MZA-PW", "2PHZ-PW" manufactured by Shikoku Kasei Co., Ltd., "P200-H50" manufactured by Mitsubishi Chemical Corporation. etc.

Metal-based curing accelerators include, for example, organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organocobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organocopper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. organic zinc complexes such as iron (III) acetylacetonate; organic nickel complexes such as nickel (II) acetylacetonate; organic manganese complexes such as manganese (II) acetylacetonate; Examples of organic metal salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

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

As the amine-based curing accelerator, a commercially available product may be used, such as "MY-25" manufactured by Ajinomoto Fine-Techno Co., Ltd., and the like.

The content of (G) the curing accelerator in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 15% by mass or less, more preferably It is 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 1% by mass or less. The lower limit of the content of (G) the curing accelerator in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, for example, 0% by mass or more, 0 It can be 0.001 wt% or more, 0.01 wt% or more, 0.05 wt% or more, and the like.

<(H) Thermoplastic resin>
The resin composition of the present invention may contain (H) a thermoplastic resin as an optional component. The (H) thermoplastic resin described here is a component other than (A) the allyl compound having an alicyclic structure and (F) the radically polymerizable compound having a molecular weight of 1000 or more described above.

(H) Thermoplastic resins include, for example, polyimide resins, phenoxy resins, polyvinyl acetal resins, polyolefin resins, polybutadiene resins, polyamideimide resins, polyetherimide resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, and polycarbonate resins. , polyether ether ketone resin, polyester resin, and the like. (H) The thermoplastic resin, in one embodiment, preferably contains a thermoplastic resin selected from the group consisting of a polyimide resin and a phenoxy resin, and more preferably contains a phenoxy resin. Further, the thermoplastic resin may be used singly or in combination of two or more.

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

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

Specific examples of the phenoxy resin include Mitsubishi Chemical's "1256" and "4250" (both bisphenol A skeleton-containing phenoxy resins); Mitsubishi Chemical's "YX8100" (bisphenol S skeleton-containing phenoxy resin); Mitsubishi Chemical "YX6954" (bisphenolacetophenone skeleton-containing phenoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.; "FX280" and "FX293" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.; "YL7769BH30", "YL6794", "YL7213", "YL7290", "YL7482" and "YL7891BH30";

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

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

Examples of polybutadiene resins include hydrogenated polybutadiene skeleton-containing resins, hydroxyl group-containing polybutadiene resins, phenolic hydroxyl group-containing polybutadiene resins, carboxy group-containing polybutadiene resins, acid anhydride group-containing polybutadiene resins, epoxy group-containing polybutadiene resins, and isocyanate group-containing resins. Examples include polybutadiene resin, urethane group-containing polybutadiene resin, polyphenylene ether-polybutadiene resin, and the like.

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

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

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

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

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

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

(H) The weight-average molecular weight (Mw) of the thermoplastic resin is preferably 5,000 or more, more preferably 8,000 or more, still more preferably 10,000 or more, and particularly preferably from the viewpoint of significantly obtaining the effects of the present invention. is 20,000 or more, preferably 100,000 or less, more preferably 70,000 or less, even more preferably 60,000 or less, and particularly preferably 50,000 or less.

The content of (H) the thermoplastic resin in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, the desired effect of the present invention is remarkably obtained. From the viewpoint, it is preferably 20% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less, still more preferably 3% by mass or less, and particularly preferably 1% by mass or less. The lower limit of the content of (H) thermoplastic resin in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, for example, 0% by mass or more, 0 0.01% by weight or more, 0.1% by weight or more, 0.3% by weight or more, and the like.

<(I) Other Additives>
The resin composition of the present invention may further contain optional additives as non-volatile components. Examples of such additives include radical polymerization initiators such as peroxide radical polymerization initiators and azo radical polymerization initiators; epoxy acrylate resins, urethane acrylate resins, urethane resins, cyanate resins, benzoxazine resins, Thermosetting resins other than epoxy resins such as unsaturated polyester resins, phenolic resins, melamine resins and silicone resins; organic fillers such as rubber particles; organic metal compounds such as organic copper compounds, organic zinc compounds and organic cobalt compounds; Colorants such as blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, phenothiazine; silicone leveling agents, acrylic polymer leveling agents, etc. leveling agents; thickeners such as bentone and montmorillonite; UV absorbers; adhesion improvers such as urea silane; adhesion promoters such as triazole-based adhesion promoters, tetrazole-based adhesion promoters, and triazine-based adhesion promoters; oxidation such as hindered phenol-based antioxidants Inhibitors; fluorescent brighteners such as stilbene derivatives; surfactants such as fluorine-based surfactants and silicone-based surfactants; , flame retardants such as nitrogen flame retardants (e.g. melamine sulfate), halogen flame retardants, inorganic flame retardants (e.g. antimony trioxide); phosphate ester dispersants, polyoxyalkylene dispersants, acetylene dispersants, Dispersants such as silicone dispersants, anionic dispersants, cationic dispersants; borate stabilizers, titanate stabilizers, aluminate stabilizers, zirconate stabilizers, isocyanate stabilizers, carboxylic acid stabilizers , stabilizers such as carboxylic acid anhydride-based stabilizers, and the like. (I) Other additives may be used singly or in combination of two or more at any ratio. (I) The content of other additives can be appropriately set by those skilled in the art.

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

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

<Method for producing resin composition>
The resin composition of the present invention can be, for example, placed in any preparation vessel (A) an allyl compound having an alicyclic structure, (B) an epoxy resin, (C) an active ester compound, and optionally (C') other Curing agent, optionally (D) a (meth)acrylic acid ester compound having a molecular weight of less than 1,000, optionally (E) an inorganic filler, optionally (F) a radically polymerizable compound having a molecular weight of 1,000 or more, necessary optionally (G) a curing accelerator, optionally (H) a thermoplastic resin, optionally (I) other additives, and optionally (J) an organic solvent, in any order and / Or by adding and mixing partly or wholly at the same time. Also, during the process of adding and mixing each component, the temperature can be set appropriately, and heating and/or cooling may be performed temporarily or over time. In addition, during or after the addition and mixing, the resin composition may be stirred or shaken using a stirring or shaking device such as a mixer to uniformly disperse. Moreover, simultaneously with stirring or shaking, defoaming may be performed under low pressure conditions such as vacuum.

<Characteristics of resin composition>
The resin composition of the present invention contains (A) an allyl compound having an alicyclic structure, (B) an epoxy resin, and (C) an active ester compound. By using such a resin composition, the arithmetic mean roughness (Ra) of the surface of the insulating layer after roughening treatment can be kept low, and a cured product having excellent copper plating peel strength and smear removability can be obtained. be able to.

The cured product of the resin composition of the present invention can have a feature that the arithmetic mean roughness (Ra) of the surface after roughening treatment is low. Therefore, in one embodiment, the arithmetic mean roughness (Ra) of the surface of the cured product after roughening treatment measured as in Test Example 2 below is preferably 250 nm or less, more preferably 200 nm or less, and still more preferably 170 nm. Below, more preferably 150 nm or less, particularly preferably 130 nm or less. The lower limit is not particularly limited, and may be, for example, 1 nm or more, 2 nm or more.

The cured product of the resin composition of the present invention can have a feature of being excellent in copper plating peel strength. Therefore, in one embodiment, a copper-plated conductor layer is formed on a cured product as in Test Example 3 below, and the copper-plated peel strength calculated from the load when the copper-plated conductor layer is peeled off in the vertical direction is preferably is 0.2 kgf/cm or more, more preferably 0.25 kgf/cm or more, still more preferably 0.3 kgf/cm or more, particularly preferably 0.35 kgf/cm or more, and 0.38 kgf/cm or more. Although the upper limit is not particularly limited, it can be, for example, 10 kgf/cm or less.

A cured product of the resin composition of the present invention can have a feature of being excellent in smear removability. Therefore, in one embodiment, as in Test Example 1 below, a via hole having a top diameter of 50 μm on the surface of the cured product and a diameter of 40 μm on the bottom surface of the via hole is formed, and after roughening treatment, the maximum smear length from the wall surface of the bottom of the via hole is When measured, the maximum smear length can be less than 5 μm.

In one embodiment, the cured product of the resin composition of the present invention may be characterized by a low dielectric loss tangent (Df). Therefore, in one embodiment, the dielectric loss tangent (Df) of the cured product of the resin composition when measured at 5.8 GHz and 23° C. as in Test Example 4 below is preferably 0.0200 or less and 0.0100 or less. , more preferably 0.0080 or less, 0.0070 or less, 0.0060 or less, 0.0050 or less, more preferably 0.0040 or less, 0.0035 or less, 0.0030 or less, particularly preferably 0.0028 or less, It can be 0.0026 or less.

<Application of resin composition>
The resin composition of the present invention can be suitably used as a resin composition for insulation, particularly as a resin composition for forming an insulation layer. Specifically, a resin composition for forming an insulating layer for forming a conductor layer (including a rewiring layer) formed on an insulating layer (resin for forming an insulating layer for forming a conductor layer composition). Moreover, in the printed wiring board described later, it can be suitably used as a resin composition for forming an insulating layer of a printed wiring board (resin composition for forming an insulating layer of a printed wiring board). The resin composition of the present invention also includes resin sheets, sheet laminate materials such as prepreg, solder resists, underfill materials, die bonding materials, semiconductor encapsulants, hole-filling resins, component-embedding resins, and the like. It can be used in a wide range of applications.

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

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

<Sheet-like laminated material>
Although the resin composition of the present invention can be applied in the form of a varnish, it is industrially preferably used in the form of a sheet-like laminated material containing the resin composition.

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

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

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

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

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

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

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

Further, as the support, a support with a release layer having a release layer on the surface to be bonded to the resin composition layer may be used. The release agent used in the release layer of the release layer-attached support includes, for example, one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. . As the support with a release layer, a commercially available product may be used, for example, "SK-1" manufactured by Lintec Co., Ltd., "SK-1", " AL-5", "AL-7", Toray's "Lumirror T60", Teijin's "Purex", and Unitika's "Unipeel".

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

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

The resin sheet is produced by, for example, using a liquid resin composition as it is or preparing a resin varnish by dissolving the resin composition in an organic solvent, coating it on a support using a die coater or the like, and drying it. It can be produced by forming a resin composition layer.

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

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

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

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

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

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

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

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

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

A printed wiring board can be manufactured, for example, using the resin sheet described above by a method including the following steps (I) and (II).
(I) A step of laminating a resin sheet on the inner layer substrate so that the resin composition layer of the resin sheet is bonded to the inner layer substrate (II) Curing (for example, thermosetting) the resin composition layer to form an insulating layer process

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Moreover, as a neutralization liquid used for the roughening treatment, an acidic aqueous solution is preferable, and as a commercial product, for example, "Reduction Solution Securigant P" manufactured by Atotech Japan Co., Ltd. can be mentioned.

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

In one embodiment, the root-mean-square roughness (Rq) of the insulating layer surface after roughening is preferably 400 nm or less, more preferably 350 nm or less, and even more preferably 300 nm or less. Although the lower limit is not particularly limited, it is preferably 0.5 nm or more, more preferably 1 nm or more. The root-mean-square roughness (Rq) of the insulating layer surface can be measured using a non-contact surface roughness meter.

Step (V) is a step of forming a conductor layer, in which the conductor layer is formed on the insulating layer. The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer contains one or more selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. Contains metal. The conductor layer may be a single metal layer or an alloy layer, and the alloy layer may be, for example, an alloy of two or more metals selected from the above group (for example, a nickel-chromium alloy, a copper- nickel alloys and copper-titanium alloys). Among them, from the viewpoint of versatility of conductor layer formation, cost, ease of patterning, etc., single metal layers of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, nickel-chromium alloys, copper- Nickel alloys and copper/titanium alloy alloy layers are preferred, and single metal layers of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or nickel/chromium alloy alloy layers are more preferred, and copper single metal layers are preferred. A metal layer is more preferred.

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

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

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

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

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

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

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

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

EXAMPLES Hereinafter, the present invention will be specifically described with reference to Examples. The invention is not limited to these examples. In the following, "parts" and "%" representing amounts mean "parts by mass" and "% by mass", respectively, unless otherwise specified. Unless otherwise specified, temperature conditions and pressure conditions are room temperature (23° C.) and atmospheric pressure (1 atm), respectively.

<Example 1>
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 of about 169 g / eq.) 2 parts, and naphthol type epoxy resin (Nippon Steel & Sumikin Chemical Co., Ltd. "ESN475V" (epoxy equivalent: about 330 g/eq.) was heated and dissolved in 5 parts of solvent naphtha with stirring. This was cooled to room temperature to prepare an epoxy resin dissolved composition. A 50% MEK solution 4 of an allyl compound having an alicyclic structure ("FATC-809" manufactured by Gun Ei Chemical Industry Co., Ltd., weight average molecular weight of about 10000, allyl equivalent weight of about 400 g/eq.) was added to this epoxy resin solution composition. Part, acrylic acid ester (“A-DOG” manufactured by Shin-Nakamura Chemical Co., Ltd., (meth) acryloyl group equivalent of about 156 g / eq.) 4 parts, active ester compound (manufactured by DIC “HPC-8000-65T”, active ester group Equivalent weight of about 223 g / eq., non-volatile content of 65% toluene solution) 30 parts, silane coupling agent ("KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd.) surface-treated spherical silica ("SO- C2”, average particle size 0.5 μm, specific surface area 5.8 m ² /g) 90 parts, triazine skeleton-containing phenolic curing agent (“LA-3018-50P” manufactured by DIC, active group equivalent of about 151 g/eq., 2-methoxypropanol solution with a non-volatile content of 50%) 2 parts, carbodiimide curing agent ("V-03" manufactured by Nisshinbo Chemical Co., Ltd., active group equivalent of about 216 g / eq., non-volatile content of 50% toluene solution) 5 parts , imidazole-based curing accelerator (manufactured by Shikoku Kasei Co., Ltd. "1B2PZ", 1-benzyl-2-phenylimidazole) 0.1 part, phenoxy resin (manufactured by Mitsubishi Chemical Corporation "YX7553BH30", MEK and cyclohexanone with a nonvolatile content of 30% by mass 1:1 solution) were mixed and uniformly dispersed in a high-speed rotating mixer to prepare a resin composition (resin varnish).

<Example 2>
Acrylic ester (“A-DOG” manufactured by Shin-Nakamura Chemical Co., Ltd.) Instead of 4 parts of acrylic ester (“DCP-A” manufactured by Kyoeisha Chemical Co., (meth) acryloyl group equivalent of about 152 g / eq.) 4 parts used, instead of 30 parts of the active ester compound ("HPC-8000-65T" manufactured by DIC), an active ester compound ("HPC-8150-62T" manufactured by DIC, active ester group equivalent of about 220 g / eq., non-volatile A resin composition (resin varnish) was prepared in the same manner as in Example 1 except that 30 parts of a toluene solution with a component ratio of 62% by mass was used and the phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation) was not used. prepared.

<Example 3>
The amount of a 50% MEK solution of an allyl compound having an alicyclic structure ("FATC-809" manufactured by Gun Ei Chemical Industry Co., Ltd.) was changed from 4 parts to 8 parts, and an active ester compound ("HPC-8000" manufactured by DIC Co., Ltd. -65T”) instead of 30 parts of the active ester compound (“HPC-8150-62T” manufactured by DIC, active ester group equivalent of about 220 g / eq., non-volatile component rate of 62% by mass, using 30 parts of toluene solution) , The amount of acrylic acid ester (“A-DOG” manufactured by Shin-Nakamura Chemical Co., Ltd.) was changed from 4 parts to 2 parts, and the phenoxy resin (“YX7553BH30” manufactured by Mitsubishi Chemical Corporation) was not used. A resin composition (resin varnish) was prepared in the same manner as in 1.

<Example 4>
The amount of spherical silica (“SO-C2” manufactured by Admatechs Co., Ltd.) surface-treated with a silane coupling agent (“KBM-573” manufactured by Shin-Etsu Chemical Co., Ltd.) was changed from 90 parts to 92 parts, and an alicyclic Instead of 4 parts of a 50% MEK solution of an allyl compound having a structure ("FATC-809" manufactured by Gun Ei Chemical Industry Co., Ltd.), an allyl compound having an alicyclic structure ("FTC-809AE" manufactured by Gun Ei Chemical Industry Co., Ltd., Allyl equivalent of about 1000 g / eq.) using 4 parts of 50% MEK solution, instead of 30 parts of active ester compound (DIC "HPC-8000-65T"), active ester compound (DIC "HPC- 8150-62T", an active ester group equivalent of about 220 g/eq., a toluene solution with a nonvolatile content of 62% by mass) was used in the same manner as in Example 1, except that 30 parts of the resin composition (resin varnish) was prepared. did.

<Example 5>
The amount of spherical silica (“SO-C2” manufactured by Admatechs Co., Ltd.) surface-treated with a silane coupling agent (“KBM-573” manufactured by Shin-Etsu Chemical Co., Ltd.) was changed from 90 parts to 92 parts, and the acrylic acid ester ("A-DOG" manufactured by Shin-Nakamura Chemical Co., Ltd.) without using 4 parts, instead of 30 parts of the active ester compound ("HPC-8000-65T" manufactured by DIC), the active ester compound (manufactured by DIC "HPC- 8150-62T", an active ester group equivalent of about 220 g/eq., a toluene solution with a nonvolatile content of 62% by mass) was used in the same manner as in Example 1, except that 30 parts of the resin composition (resin varnish) was prepared. did.

<Example 6>
The amount of spherical silica (“SO-C2” manufactured by Admatechs Co., Ltd.) surface-treated with a silane coupling agent (“KBM-573” manufactured by Shin-Etsu Chemical Co., Ltd.) was changed from 90 parts to 93 parts, and biphenyl aralkyl Using 2 parts of novolac maleimide (“MIR-3000-70MT” manufactured by Nippon Kayaku Co., Ltd., MEK / toluene mixed solution with a non-volatile content of 70%), an active ester compound (“HPC-8000-65T” manufactured by DIC) Instead of 30 parts, except for using 30 parts of an active ester compound ("HPC-8150-62T" manufactured by DIC, active ester group equivalent of about 220 g / eq., non-volatile content of 62% by mass in toluene solution). A resin composition (resin varnish) was prepared in the same manner as in Example 1.

<Example 7>
Instead of 2 parts of biphenyl aralkyl novolak type maleimide (manufactured by Nippon Kayaku Co., Ltd. "MIR-3000-70MT"), 2 parts of methacrylic modified polyphenylene ether (manufactured by SABIC Innovative Plastics Co., Ltd. "SA9000-111") were used. A resin composition (resin varnish) was prepared in the same manner as in Example 6.

<Example 8>
Instead of 2 parts of biphenyl aralkyl novolac type maleimide (“MIR-3000-70MT” manufactured by Nippon Kayaku Co., Ltd.), vinylbenzyl-modified polyphenylene ether (“OPE-2St 2200” manufactured by Mitsubishi Gas Chemical Co., Ltd., non-volatile component rate of 65% toluene solution) was used, and the amount of imidazole-based curing accelerator ("1B2PZ" manufactured by Shikoku Kasei Kogyo Co., Ltd.) was changed from 0.1 part to 0.5 part in the same manner as in Example 6. , to prepare a resin composition (resin varnish).

<Comparative Example 1>
The amount of spherical silica (“SO-C2” manufactured by Admatechs Co., Ltd.) surface-treated with a silane coupling agent (“KBM-573” manufactured by Shin-Etsu Chemical Co., Ltd.) was changed from 90 parts to 85 parts, and an alicyclic Without using 4 parts of a 50% MEK solution of an allyl compound having a structure (“FATC-809” manufactured by Gunei Chemical Industry Co., Ltd.), further acrylic acid ester (“DCP-A” manufactured by Kyoeisha Chemical Co., Ltd., (meth) acryloyl group Equivalent about 152 g / eq.) 4 parts was not used, and the amount of imidazole curing accelerator ("1B2PZ" manufactured by Shikoku Kasei Kogyo Co., Ltd.) was changed from 0.1 part to 0.5 part. A resin composition (resin varnish) was prepared in the same manner as in 1.

<Comparative Example 2>
Instead of 30 parts of the active ester compound ("HPC-8000-65T" manufactured by DIC), an active ester compound ("HPC-8150-62T" manufactured by DIC, active ester group equivalent weight of about 220 g / eq., non-volatile content of 62 A resin composition (resin varnish) was prepared in the same manner as in Comparative Example 1, except that 30 parts of a toluene solution (% by mass) was used.

<Comparative Example 3>
Acrylic acid ester ("DCP-A" manufactured by Kyoeisha Chemical Co., Ltd., (meth) acryloyl group equivalent of about 152 g / eq.) was changed from 4 parts to 10 parts, and an active ester compound (manufactured by DIC "HPC-8000-65T" ) instead of 30 parts of the active ester compound ("HPC-8150-62T" manufactured by DIC, active ester group equivalent of about 220 g / eq., non-volatile content of 62% by mass, except for using 30 parts of a toluene solution). A resin composition (resin varnish) was prepared in the same manner as in Comparative Example 1.

<Test Example 1: Evaluation of Smear Removability>
(1) Production of Resin Sheet As a support, a polyethylene terephthalate film (“AL5” manufactured by Lintec Corporation, thickness 38 μm) provided with a release layer was prepared. On the release layer of this support, the resin compositions obtained in Examples and Comparative Examples were uniformly applied so that the thickness of the resin composition layer after drying was 40 μm. Thereafter, the resin composition was dried at 80° C. to 100° C. (average 90° C.) for 4 minutes to obtain a resin sheet including a support and a resin composition layer.

(2) Surface treatment of interior substrate As an inner layer substrate, a glass cloth-based epoxy resin double-sided copper-clad laminate having a copper foil on the surface (copper foil thickness 18 μm, substrate thickness 0.8 mm, Panasonic “R1515A” ”) was prepared. The copper foil on the surface of the inner layer substrate was roughened by etching with a microetching agent (“CZ8101” manufactured by MEC Co., Ltd.) at a copper etching amount of 1 μm. After that, drying was performed at 190° C. for 30 minutes.

(3) Lamination and curing of resin sheet The resin sheet obtained in (1) above is coated with a batch type vacuum pressure laminator (2-stage build-up laminator "CVP700" manufactured by Nikko Materials Co., Ltd.) to form a resin composition layer. was laminated on both sides of the inner layer substrate so that the was bonded to the inner layer substrate. This lamination was carried out by pressure bonding for 30 seconds at a temperature of 100° C. and a pressure of 0.74 MPa after reducing the pressure to 13 hPa or less for 30 seconds.

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

(4) Via hole formation Using a CO ₂ laser processing machine (LK-2K212/2C) manufactured by Via Mechanics Co., Ltd., the insulating layer is processed under the conditions of a frequency of 2000 Hz, a pulse width of 3 μs, an output of 0.95 W, and the number of shots of 3. Then, 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. After that, the PET film was peeled off.

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

(6) Evaluation of smear removal property The periphery of the bottom of the via hole of the evaluation substrate A was observed with a scanning electron microscope (SEM), and the maximum smear length from the wall surface of the bottom of the via hole was measured from the obtained image. evaluated with
Good: The maximum smear length is less than 5 μm.
x: The maximum smear length is 5 μm or more.

<Test Example 2: Measurement of arithmetic mean roughness (Ra)>
The evaluation substrate A obtained in (5) of Test Example 1 is measured using a non-contact surface roughness meter (WYKO NT3300 manufactured by Bcoinstruments, Inc.) in VSI mode with a 50-fold lens to obtain a measurement range of 121 μm × 92 μm. Arithmetic mean roughness (Ra) values were obtained from numerical values. Each was measured by calculating the average value of 10 randomly selected points.

<Test Example 3: Measurement of copper plating peel strength>
Evaluation board A obtained in (5) of Test Example 1 was immersed in an electroless plating solution containing PdCl ₂ at 40° C. for 5 minutes, and then immersed in an electroless copper plating solution at 25° C. for 20 minutes. After annealing by heating at 150° C. for 30 minutes, an etching resist was formed, and after pattern formation by etching, copper sulfate electroplating was performed to form a conductor layer with a thickness of 30 μm. Next, an evaluation substrate B was obtained by performing an annealing treatment at 200° C. for 60 minutes.

An incision of 10 mm width and 150 mm length is made in the portion of the conductor layer of evaluation board B that does not include via holes, and one end of this cut is peeled off and gripped (manufactured by TSE Co., Autocom type testing machine AC- 50C-SL), and the load (kgf/cm) when peeling off 100 mm in the vertical direction at a speed of 50 mm/min at room temperature (25° C.) was measured.

<Test Example 4: Measurement of Dielectric Loss Tangent>
The resin sheet obtained in (1) of Test Example 1 was 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 with a width of 2 mm and a length of 80 mm. The dielectric loss tangent (tan δ) was measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23°C. Two test pieces were measured, and the average value was calculated.

Table 1 below shows the amount of raw materials used and the content of non-volatile components in the resin compositions of Examples and Comparative Examples, and the measurement results of Test Examples.

As shown in Table 1, in Comparative Examples 1 and 2 in which the active ester compound was used, the smear removability was low. In addition, in Comparative Example 3 in which a low-molecular-weight (meth)acrylic acid ester compound was used together with the active ester compound, the smear removal property was excellent, but the arithmetic average roughness (Ra) of the insulating layer surface after the roughening treatment was high and low copper plating peel strength. On the other hand, when the resin composition of the present invention containing (A) an allyl compound having an alicyclic structure is used together with an active ester compound, the arithmetic mean roughness (Ra) of the insulating layer surface after roughening treatment is A result was obtained that it was possible to keep it low and achieve excellent copper plating peel strength and smear removability.

Claims (20)

A resin composition comprising (A) an allyl compound having an alicyclic structure, (B) an epoxy resin, and (C) an active ester compound. Component (A) has the formula (a-1):

[In the formula, * indicates a binding site. ]
The resin composition according to claim 1, which has a group represented by (A) component is the formula (A3):

[Wherein, X represents a single bond, -C(R ⁵ ) ₂ -, -O-, -CO-, -S-, -SO-, or -SO ₂ -, and R ² and R ⁵ are Each independently represents a hydrogen atom or a hydrocarbon group, R ³ and R ⁴ each independently represents a hydrocarbon group, one R ² and at least one of b R ³ , an allyl group, b and c each independently represent an integer of 0 to 3, and * represents a binding site. ]
The resin composition according to claim 1 or 2, having a group represented by: The resin composition according to any one of claims 1 to 3, wherein component (A) has a weight average molecular weight of 1,000 to 20,000. The allyl equivalent of component (A) is 200 g/eq. ~2000 g/eq. The resin composition according to any one of claims 1 to 4. The resin composition according to any one of claims 1 to 5, wherein the content of component (A) is 0.01% by mass or more when the non-volatile component in the resin composition is 100% by mass. The resin composition according to any one of claims 1 to 6, wherein the content of component (A) is 5% by mass or less when the non-volatile components in the resin composition are taken as 100% by mass. 8. The resin composition according to any one of claims 1 to 7, further comprising (D) a (meth)acrylate compound having a molecular weight of less than 1,000. The resin composition according to claim 8, wherein the mass ratio of component (D) to component (A) (component (D)/component (A)) is 0.1-10. The resin composition according to any one of claims 1 to 9, wherein the content of component (C) is 10% by mass or more when the non-volatile component in the resin composition is 100% by mass. (E) The resin composition according to any one of claims 1 to 10, further comprising an inorganic filler. 12. The resin composition according to claim 11, wherein the content of component (E) is 60% by mass or more when the non-volatile component in the resin composition is 100% by mass. The resin composition according to any one of claims 1 to 12, further comprising an imidazole curing accelerator. The resin composition according to any one of claims 1 to 13, further comprising a curing agent selected from the group consisting of phenolic curing agents and carbodiimide curing agents. The resin composition according to any one of claims 1 to 14, wherein the cured resin composition has a dielectric loss tangent (Df) of 0.0030 or less when measured at 5.8 GHz and 23°C. A cured product of the resin composition according to any one of claims 1 to 15. A sheet-like laminate material containing the resin composition according to any one of claims 1 to 15. A resin sheet comprising a support and a resin composition layer formed from the resin composition according to any one of claims 1 to 15 provided on the support. A printed wiring board comprising an insulating layer comprising a cured product of the resin composition according to any one of claims 1 to 15. A semiconductor device comprising the printed wiring board according to claim 19 .